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History and progress in the accurate determination of the Avogadro constant
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INSTITUTE OF PHYSICS PUBLISHING REPORTS ON PROGRESS IN PHYSICS
Rep. Prog. Phys. 64 (2001) 19452008 PII: S0034-4885(01)12689-8
History and progress in the accurate determination of
the Avogadro constant
Peter Becker
Physikalisch-Technische Bundesanstalt, Braunschweig, Germany
Received 24 September 2001
Published 15 November 2001
Online at stacks.iop.org/RoPP/64/1945
Abstract
The Avogadro constant, N
A
, is a fundamental physical constant that relates any quantity at
the atomic scale to its corresponding macroscopic scale. Inspired by the kinetic gas theory
Avogadro proposed his hypothesis in 1811, in order to describe chemical reactions as an
atomic process between atoms or molecules. Starting from his pioneering ndings, the
determination of this large number has fascinated generations of scientists up to this day.
The review of methods aimed at nding a value for N
A
starts with the calculations made
by Loschmidt (1865; N
A
72 10
23
mol
1
) who evaluated the number of molecules in
a given gas volume, derived from estimates of molecular diameters and the mean free path
length. Consideration of Brownian motion led to some more accurate determinations of N
A
around the beginning of the 20th century (Perrin (1908); N
A
6.7 10
23
mol
1
). Other
methods developed in the following years are based on Millikans oil drop experiment (1917,
N
A
6.064(6) 10
23
mol
1
), on the counting of alpha particles emitted from radium or
uranium (Rutherford (1909); N
A
6.16 10
23
mol
1
) and on investigations of molecular
monolayers on liquids (Nuoy (1924); N
A
6.004 10
23
mol
1
).
A modern method to derive N
A
from the density, the relative atomic mass, and the unit
cell length was introduced by Bragg in 1913. It makes use of the diffraction of x-rays by
the interatomic spacings of a crystal lattice and its periodic arrangement. The accuracy
of this method is extremely affected by the fact that the lattice scale of the structurally
imperfect lattice can be calibrated only approximately in SI units. Data of N
A
were,
therefore, found to be in disagreement with other fundamental constants (Bearden (1931);
N
A
6.019(3) 10
23
mol
1
). A break though was achieved with perfect crystals of silicon
and x-ray interferometry making available very precise data of atomic distances, expressed in
SI units (Bonse and Hart 1965).
Today, metrology has re-discovered the Avogadro constant and uses it as one of several
possible routes to a re-denition of the kilogram because the old platinum iridium artefact
exhibits long-termstability problems. This application of the Avogadro constant presupposes a
nal measurement uncertaintyof about 110
8
, a challenge for the experimental determination
of the quantities involved, i.e. macroscopic density, isotopic composition, and unit cell volume
of a silicon crystal. Many years of research work were centred on the problem of how far the
perfection of a real crystal is away from the ideal state. At present, it is widely accepted that,
0034-4885/01/121945+64$90.00 2001 IOP Publishing Ltd Printed in the UK 1945
1946 P Becker
in the limits of the desired uncertainty, the lattice parameter, and thus the unit cell volume
of silicon, can be seen as an invariant quantity when the inuence of residual defects, for
example impurities, is taken into account. Up to a relative measurement uncertainty of a few
parts in 10
7
it has recently been shown that the molar volume, the ratio of molar mass to
density, is constant, too. The combination of data from several independent measurements
of the unit cell and the molar volumes has led to a value for the Avogadro constant of
N
A
= 6.022 1335(30) 10
23
mol
1
(De Bi` evre et al 2001) recommended by the national
metrology institutes involved in this research project (Becker 2001).
Prominent examples of the signicance of the research work reviewed here are the use of
N
A
as an input independent of other data, for the adjustment of a consistent set of fundamental
constants, and the accompanying outstanding experimental developments acting as spin-offs
in the eld of technology to make macroscopic dimensions traceable to the atomic scale.
History and progress in the accurate determination of the Avogadro constant 1947
Contents
Page
1. Introduction 1948
2. Todays signicance of the Avogadro constant 1948
3. Experimental determinations 1949
3.1. Avogadros hypothesis and the kinetic gas theory 1949
3.2. Early measurements on solid solutions in liquids 1950
3.3. Avogadros hypothesis and the Brownian motion 1950
3.4. The oil drop method 1951
3.5. The early x-ray/crystal density approach 1953
3.6. Discrepancies in x-ray data 1955
4. Establishing the link of the lattice parameter to the meter by x-ray interferometry 1955
4.1. Former XRCD key experiments 1956
5. Avogadros hypothesis: the XRCD method 1957
5.1. Material characterization 1958
5.2. The silicon lattice parameteran invariant quantity of nature? 1968
5.3. Determination of the molar mass 1979
5.4. Density of silicon volume standards 1983
5.5. Summary of N
A
results 1994
5.6. New developments 1996
6. Indirect determinations of the Avogadro constant from measurements of fundamental
physical constants 1999
7. Spin-offs in the eld of metrology and solid state physics 2001
8. The role of N
A
in the SI, present state and outlook 2003
Acknowledgments 2004
References 2004
1948 P Becker
1. Introduction
The development of the kinetic gas theory in physics, chiey due to Clausius, Maxwell and
Boltzmann, and the development of a modern understanding of the atom or molecule in
chemistry towards the end of the 18th century were the roots of the Avogadro constant. At that
time, chemistry stood on the verge of becoming an accurate science. John Dalton (17661844)
declared in 1808 that the atoms of each element did not differ from one another, that they had
the same properties and a characteristic atomic weight. These ndings hold also for molecules
in a chemical compound. He also stated that the mass of an atom can be measured relative to
the mass of a hydrogen atom by their atomic weights. Around this time, in 1809, Joseph Louis
Gay-Lussac (17781850) studied the chemical reaction of gases. He found experimentally that
the internal energy of an ideal gas was independent of its volume and that the ratios of volumes
of the reacting gases were small integer numbers. Amedeo Avogadro (17761856) gave a
more precise description of the reacting particles and distinguished between atoms as parts of
a molecule. Avogadro stated in 1811 that equal volumes of all gases at the same temperature
and pressure contain the same number of molecules, which is well known as Avogadros
principle. Avogadros work was almost completely neglected until it was forcefully presented
by Stanislao Cannizarro. In 1858 he published a consistent system of atomic weights and
chemical formulae of all elements based upon the principles laid down by Avogadro.
In the following years, Avogadros hypothesis was taken as a starting point, from which,
as logical as may be, the ideas of molecular weight, atomic weight, valency, radicals, etc were
developed, and from which, nally, the challenge was developed to estimate the number of
particles in that volume and to comprehend the size of such a large number.
The term Avogadro constant was rst used in a paper entitled Brownian Movement and
Molecular Reality and published by Jean Perrin (18701942) in 1909. In his paper he wrote:
The invariable number N is a universal constant, which may be appropriately designated
Avogadros constant and is reserved nowadays for the number of particles (entities) in a
mole, N
A
, even though Avogadro made no quantitative estimate of that constant. The term
Loschmidts number is used then for the number of molecules in a cubic centimetre of a gas
under standard conditions, N
L
. Because the molar volume of an ideal gas is 22.4 litres, the
value of the Avogadro constant is 22.4 times that of Loschmidts number.
Avogadro died in 1856 without his central hypothesis being recognized.
The aim of this paper is to review and update the evolution of the determination of the
Avogadro constant fromthe early days of molecular theory to the present state of high-precision
evaluation derived from perfect silicon crystals. The structure of the paper is as follows:
section 2 treats the signicance of the Avogadro constant from the metrological and scientic
points of view. Section 3 is devoted to early experimental methods for studying the value of
N
A
, from the kinetic gas theory to the x-ray method. Section 4 describes the basic concept of
x-ray interferometry as a break-through of todays highly precise evaluation of the Avogadro
constant, which is described in detail in section 5. The nal chapters connect the Avogadro
constant with other fundamental constants and with spin-offs in science and technology.
Historical developments of this fundamental constant were also dealt with in the past by
Virgo (1932), and in great detail by Deslattes (1980), Mathieu (1984) and, recently, by Mana
and Zosi in 1995.
2. Todays signicance of the Avogadro constant
The Avogadro constant has long been known as the scale factor between the macroscopic and
the atomic worlds. It helps to see the numerical value of a quantity in the macroscopic world
as being a multiple of the same quantity on the atomic scale. This is one of the reasons why
the Avogadro constant has been introduced into the International System of Units, the SI, in
terms of which physical and chemical quantities must be expressed. The concept of a physical
quantity was introduced by J C Maxwell in 1860: Every expression of a quantity consists of
two factors or components. One of these is the quantity of the same kind as the quantity to
be expressed, which is taken as a standard of reference. The other component is the number
of times the standard is to be taken in order to make the required quantity. The chemical
quantity, called amount of substance, was introduced as a base quantity of the SI in 1971 and
its assigned unit, the mole, is currently dened as: The amount of substance of a systemwhich
contains as many elementary entities as there are atoms in 0.012 kg of
12
C. When the mole is
used, the elementary entities must be specied and may be atoms, molecules, ions, electrons,
or other particles or specied groups of particles. The number of entities in 12 g of
12
C is the
Avogadro number. A determination of the Avogadro constant, therefore, is a realization of the
base unit, mole.
There is yet another signicance to the Avogadro constant: the present SI base unit for
mass is the prototype kilogram kept at S` evres. However, the mass of that primary standard
of mass is not stable. The estimated instability has been m/m 5 10
8
(Quinn 1991)
over the past 100 years. The suggestion has, therefore, been made to change the denition of
the kilogram following again the well known requirement by J C Maxwell that the physical
units should not be founded on macroscopic quantities but on the properties of, for example,
imperishable and unalterable molecules (Maxwell 1870). If a determination of N
A
succeeded
to better than 5 10
8
, in relative values, the denition could be changed from the mass of
the prototype of the kilogram into the mass of 10
3
{N
A
} atoms of
12
C.
As a fundamental physical quantity, the Avogadro constant is related to other constants and
can be determined indirectly from the measurements of these. N
A
, then, appears to be, both
an input and an output of an overall least-squares adjustment of the fundamental constants.
Through this approach, internal criticism among parts of physical theory is provided and a
consistent set of numerical values for the constants is obtained.
3. Experimental determinations
In chemistry, the concept of Avogadro and the mole emerged through a historical process.
Over the years before 1860, the chemical community had been unable to come to agreements,
neither on concepts nor on terminology. In physics, more than 50 years after a rst calculation
by Loschmidt of the number proposed by Avogadro, the numerical evaluation became really
important.
3.1. Avogadros hypothesis and the kinetic gas theory
Concepts for atoms and molecules and their magnitudes can be found in the works of Newton
dating back to 1704. The foundations of Daltons atomic theory (Dalton 1808) were denitely
laid on considerations arising fromstudies of chemical changes. It may be added that people at
that time were much concerned with relative weights of particles, but questions as to absolute
data of the particles of matter had no appeal for them.
One of the rst investigations into this subject can be found in the work by Young published
in 1807. He concluded that the diameter or distance of the particles of water is between
0.125 10
8
and 0.025 10
8
cm.
Avogadro proposed his hypothesis in 1811. At that time there was no data at all on the
number of particles in a mole, or an agreement on any atomic weights. The rst estimates which
1950 P Becker
could give an approximative value for Avogadros number were deduced from observations
of the Brownian motion by Brown in 1828. Cannizarro (1856) used Avogadros principle to
develop a defensible set of atomic weights based on 1/16 of the atomic weight of oxygen, in
contrast to the above-mentioned denition of the mole by a number of carbon atoms.
In 1850 and 1856, Clausius (182288) and Kronig (182279), respectively, developed
the idea that the motion of the gas molecules should be linear, except during collision with
themselves or with the container. They found that each molecule has its own hard elastic sphere
with a certain radius and that the ratio of the free path length to the diameter of the molecule
and the ratio of the volume of the molecular sphere and the volume of the container are of
equal magnitude. Loschmidt gave rst estimates of the size and the number density, deduced
from the mean free path length (1865). He calculated the number of molecules in one cubic
centimetre of a gaseous substance under ordinary conditions of temperature and pressure to
be somewhere around 2.6 10
19
molecules cm
3
. He was also able to obtain a molecular
diameter of the order of 1 nm using the new kinetic molecular theory which described the
molecules as rigid spheres. This is usually known as Loschmidts constant.
The results of similar experiments performed by many authors were published without
any measurement uncertainties being stated. This was due to an insuffcient development of
the kinetic gas theory rather than to experimental difculties. The gas theory has shown a way
towards the determination of the Avogadro constant and its order of magnitude but was not
able to provide more precise data.
3.2. Early measurements on solid solutions in liquids
Many characteristics of the thermal motion in gases can also be found in liquids. As the
number of molecules in a certain liquid volume is by a factor of a thousand larger than in a gas
volume, the free path lengths are much smaller and the mutual effects between the molecules
can no longer be neglected either. First attempts at establishing a quantitative analogy between
uids and gases were made by vant Hoff in 1877 and by van der Waals in 1881 when they
investigated osmotic phenomina. In 1890, R ontgen and Rayleigh investigated thin molecular
lms on water and obtained for molecules diameters of about 0.6 to 1 nm, resulting in a number
density of 67 10
23
particles in a mole. Later on, by an improved analysis, DuNouy found
a value of 6.003 10
23
mol
1
in 1924.
In 1890 a rst attempt was made to introduce the concept of a volume related number
density into chemistry. In Ostwalds textbook Grundriss der allgemeinen Chemie (1889),
the expression number in 1 l, N is still used. In the third, improved edition the term Mol
with the meaning molecular weight in gram can be found for the rst time (Oswald, 1899).
At the end of the 19th century, a value of N
L
= 2.8 10
19
cm
3
was used.
3.3. Avogadros hypothesis and the Brownian motion
In early 1827, Brown found out that solid particles in a uid are in continuous motion (Brown
1928) which can be described as an irregular and independent lateral and tilt movement. Two
macroscopic phenomena characterized this movement, the diffusion as a drive to balance
particle concentration and the particles vertical distribution due to gravity in the uid. As
the macroscopic objects were measurable and connections to the molecular entities could be
established by a well-dened statistical analysis, properties of the molecules, e.g. their masses,
could be inferred in a rather direct way.
Later on, a new signicance to the Avogadro constant was given through the contributions
of four great physicists: two theoreticians, M Planck (1901) and A Einstein (1906), and two
experimentalists, E Rutherford (1909) and J Perrin (1909).
First investigations were performed by Einstein in 1905 and Smoluchowski in 1906.
Einsteins analysis started fromthe hypothesis of equipartition of energy among kinetic degrees
of freedom of a system in equilibrium from which he deduced a new determination of
molecular dimensions. After some correction, a revised value of 6.56 10
23
particles/g
at.wt. for the Avogadro constant was published by him in 1911. Plancks calculation (1901)
of the three fundamental constants h, k, N
L
, was done in the context of the presentation of his
Verteilungsgesetz.
Einsteins deduction of an exponential density distribution with respect to height was
experimentally proven by Perrin in 1909. Perrin demonstrated that, in an emulsion of particles
visible under the microscope, the equilibrium repartition along a vertical axis was exponential,
similar to an ideal gas under the inuence of gravity. The repartition equation led to an
Avogadro constant close to N
A
= 6.7 10
23
particles/g at.wt. Perrin expressed his results
in terms of a different unit, which he called Avogadros number or constant. This unit, which
soon came into general use, is dened as the number of molecules in one gram-molecular
volume (namely 22.4 l) of a gas under normal conditions.
The work of Einstein and Perrin yielded some of the rst specic evidence of the
existence of molecules. Subsequent to the work of Loschmidt and Perrin, many scientists
carried out numerous experiments using a variety of techniques to measure the value of the
Avogadro constant as accurately as possible. As nearly all scientists paid more attention to
the determination of the molecular diameter than to the number density, it is difcult to assign
to these measurements also an index of accuracy, u
r
. But, investigations of the movement
of mercury droplets or spherical micro-organisms performed by Fletcher (1911), Nordlund
(1914), Westgreen (1914), and by Shaxby in 1923 resulted in more precise values for the
Avogadro constant. One of the last attempts to determine N
A
by movements of particles was
published by Kappler in 1931, who observed the Brownian motion of a torsion balance from
which he obtained a value of N
A
= 6.059 10
23
particles/g at.wt. (u
r
1%).
In summary, improvements of the kinetic gas theory and the Brownian motion, and
experiments on the sedimentation equilibria of colloidal particles led to remarkable values:
N
A
= (6.03 0.12) 10
23
particles/g at.wt. At the beginning of the 20th century the
Avogadro constant was increasingly derived no longer by investigations of gas molecules; the
principle was applied more and more to uids and solid samples, mainly due to the discovery
of x-rays.
3.4. The oil drop method
When the Brownian motion had been investigated also with charged particles, one was able
to obtain values for the product N e. These experiments, initiated by Townsend (1898) and
carried on by Thomson (1898) and Wilson (1903), were based on the condensation of clouds of
charged droplets. In 1909 it was pointed out that these determinations were adversely affected
by two fundamental difculties: one of them concerned the limitation of the law itself, derived
by Stokes in 1850, the other was due to evaporation from the droplets during the fall of the
cloud. In 1908, Millikan began his long-lasting efforts to eliminate these two sources of errors
by his balanced-drop method holding the cloud in a stationary position by an electric eld
sufciently strong to prevent its fall under gravity. The development of the oil drop method
was extended and improved year by year. Finally, in 1917, Millikan was able to establish an
accurate value for the fundamental electric charge, and he proved that all electrons have exactly
the same charge. The experimental improvements directed to investigations of the Brownian
movements of individual droplets also provided the means for obtaining accurate values for
the Avogadro constant: 6.03 10
23
mol
1
(Schidlof 1915). In contrast to this, the indirect
1952 P Becker
Table 1. Values of N
A
and their uncertainties as determined from 1865. Data 117 are derived
mainly from atomic or molecular movement in gases or uids, data 1824 mainly from x-ray
wavelengths, and data 2535 from the XRCD approach, together with least-squares adjustments
of fundamental constants.
N
A
Year First author Method 10
23
mol
1
u
rel
1 1865 J Loschmidt Mean free path 72 1 10
0
2 1873 J D van der Waals Kin. gas theory 11 5 10
1
3 1890 W R R ontgen Atom. lms on water 7 1 10
0
4 1890 J W S Rayleigh Atom. lms on water 6.08 1 10
2
5 1901 M Planck R/k 6.16 1 10
2
6 1903 H A Wilson Oil drop method 9.3 1 10
0
7 1904 J J Thomson Oil drop method 8.7 1 10
0
8 1908 A Einstein Diffusion theory 6 1 10
0
9 1908 J Perrin Brownian movement 6.7 3 10
1
10 1909 E Rutherford -particle theory 6.16 6 10
2
12 1914 T Fletcher Brownian movement 6.0 2 10
1
13 1914 I Nordlund Diffusion in uids 5.91 1 10
2
14 1915 A Westgreen Diffusion in uids 6.06 2 10
1
15 1917 R A Millikan Oil drop method 6.064 6 10
3
16 1923 T W Shaxby Diffusion in uids 5.9
17 1924 P L du Nouy Thin lms 6.004 8 10
3
18 1929 R T Birge X-ray diffraction 6.064 4 6 10
3
19 1931 J A Bearden X-ray gratings/plane 6.019 3 10
3
20 1941 R T Birge Calcite, NaCl, KCl, . . . 6.022 83 1 10
4
21 1945 R T Birge Diamond, LiF 6.023 38 2 10
4
22 1948 J W M DuMond X-gratings/concave 6.023 2 1 10
4
23 1949 M E Straumanis Calcite crystals 6.024 03 3 10
4
24 1951 J W M DuMond 6.025 44 1 10
4
25 1965 J A Bearden XRCD, Si 6.022 088 2 10
5
26 1965 E R Cohen LS. adjustment 6.022 52 9 10
5
27 1973 E R Cohen LS. adjustment 6.022 045 3 10
5
28 1974 R D Deslattes XRCD, Si 6.022 094 3 1 10
6
29 1987 R D Deslattes XRCD 6.022 134 1 10
6
30 1987 E R Cohen LS. adjustment 6.022 136 7 6 10
7
31 1992 P Seyfried XRCD 6.022 136 3 1 10
6
32 1994 G Basile XRCD 6.022 137 9 4 10
7
33 1995 P De Bi` evre XRCD 6.022 136 5 6 10
7
34 1999 K Fujii XRCD 6.022 155 0 3 10
7
35 2001 P De Bi` evre XRCD 6.022 133 9 4 10
7
determination from the electron charge, taking into account the actual value of the Faraday
constant, yielded N
A
= 6.064(6) 10
23
mol
1
(Birge 1935).
At the beginning of the 20th century, shortly after the discovery of radioactivity, two
of determinations of the Avogadro constant were published, based on the production of
helium from radium (cf Rutherford (1909)), and derived from the half-life period of radium
(cf Gleditsch (1919)). Selected values of N
A
, from 1865 until today, are presented in table 1,
together with their uncertainty level. A graphical picture of the evolution of the uncertainty of
N
A
is also given by De Bi` evre and Peiser (1994) and De Bi` evre (1996). It shows a reduction
of the uncertainty on N
A
by a factor of 10 every 15 years in the period from 1850 to 2000.
3.5. The early x-ray/crystal density approach
During the 18th century the atomic theory was introduced in crystallography by Ha uy (1801).
He described crystals as an entity of individual molecules of parallelepipedal shape. Later on,
this picture was improved by Bravais (1848), Sch onies (1891) and Barlow(1898) who showed
in detail the various arrangements of the lattices and their formation procedure. These ndings
became of great importance through the discovery of x-rays by R ontgen in 1895. Since then,
the following milestones for todays determinations of the Avogadro constant were found: in
1900, the electro-magnetic nature of x-rays was postulated. A theory for x-ray diffraction by
crystals was developed and investigated by v Laue and co-workers (Friedrich et al 1912) and
by W L Bragg in 1913. W H Bragg was the rst to use the results published for the Avogadro
constant to calculate the atomic distances or lattice parameter of an NaCl crystal by means of
the ansatz (Bragg 1914)
a
0
=
_
n M
N
A
_
1/3
, (1)
where M is the mean molar mass of the atoms and n their number in the unit (cell) with a
volume of a
3
0
, and the macroscopic crystal density. At the same time, W L Bragg (1912)
made a particular interpretation of v Laues theory, namely a relationship between the lattice
spacings and the wavelength of the diffracted x-rays:
d
hkl
=

2 sin
, (2)
with
d
hkl
=
a
0
h
2
+ k
2
+ l
2
, (3)
where h, k, l are Miller indices.
The pioneering experimental work by Mosely in 1914 quickly made it evident that relative
magnitudes of x-ray wavelengths or lattice spacings could be much more precisely determined
than the value of a
0
in Braggs expression (1). For an NaCl crystal an atomic distance of
2.814 10
10
m was deduced with an uncertainty mainly due to the improper knowledge of
the Avogadro constant. As a consequence, Siegbahn (1919) suggested dening a local x-ray
unit scale, assuming that the numerical values available at that time were exact, in terms of a
new unit, XU. The value recommended for the X unit was
1X = d(NaCl; 18
C)/2814 000 . . . . (4)

Fromour knowledge it seems that it was adventurous to base the Xscale on crystals with highly
imperfect lattice structures. This was obvious when absolute wavelength data corresponding to
certain x-ray spectral lines became available through experiments using gratings with a repeat
distance known in the unit of length, the meter, and the precise measurement of the diffraction
angles (Br acklin 1928). Selected data for N
A
derived fromsuch measurements were rst found
by Birge in (1929), see Birge (1945), Bearden in (1931), and DuMond in (1948), see DuMond
(1959). They reached measurement uncertainties in the order of 10
4
. A comparison between
wavelengths measured in the meter unit,
m
, and corresponding data derived from the X unit,
X
, showed a discrepancy of approximately 0.2%. This error was obvious, because the values
of e from the Millikan oil drop experiment and, consequently, of N
A
, as well, were affected
by an error. To take this discrepancy into account, a conversion factor ,
=
m
/
X
(5)
1954 P Becker
was introduced. But it soon became clear that the conversion factor was not stable; its
value was affected by crystal imperfections such as impurities; more over, the measurement
techniques had meanwhile been improved.
Using , it was now possible to obtain new data for the Avogadro constant by inverting
the above-mentioned equation (1):
3
N
A
=
n M
a
3
0

(6)
where a
0
is measured in X units and is a geometrical quantity which depends on the slope of
the crystal faces. In such a way, N
A
was derived from the lattice parameter, density and molar
mass of an NaCl crystal by Birge in 1945: N
A
= (6.024 01 0.000 52) 10
23
mol
1
.
However, since x-ray spectral lines have a relative width of more than 3 10
4
, at their
narrowest, and also internal structures, it was very unlikely that they could be used successfully
in any measurement technique at a precision level of the order of 1 10
6
.
The determination of N
A
using x-rays, once the lattice parameters are known, also requires
the determination of the mean molar mass and the macroscopic density of the crystal. Early in
the 20th century, the rst density measurements were carried out by hydrostatically weighing
the crystals in samples of water whose density had been precisely determined previously.
Molar masses were rst determined by chemical methods, and since about 1950 from physical
measurements of nuclear masses combined with abundance determinations. Since 1970,
isotopic abundances have been directly established for the specimens used.
Almost all of the early work was carried out using calcite crystals, taking the lattice
parameter a
0
= 3029.040 XU of the purest calcite crystal as a basis. The trouble with this
denition was that there was no recipe for knowing how to dene the purest calcite sample.
The wide variation from one sample of natural crystals to the other was known, and calcite
was not an exception. In 1940, different samples were shown by Ievins and Straumanis
to exhibit wide uctations of a
0
over a range exceeding 100 10
6
. Birge also presented
in his paper measurements on diamond, LiF, KCl and calcite, showing an average value of
N
A
= 6.023 38 (23) mol
1
. Later measurements carried out by Straumanis in 1949 on calcite
crystals resulted in N
A
= 6.024 03 (18) mol
1
.
A vital source of uncertainty in these data was the wavelength of the characteristic x-
ray line used to measure the crystal lattice spacing. One part was due to the uncertainty in
deniteness and reproducibility (approx. 3 10
4
) of the centre of the x-ray lines limiting
the applicability of the XRCD method. Another source of error originated in the absolute
data for molybdenum and copper radiation, which were discrepant by about 40 10
6
. To
overcome these difculties, Bearden (1965) proposed to take the result that emerged for the
characteristic tungsten x-ray line as a new fundamental standard: WK
1
0.209 0100 A
.
The unit A* was numerically close to 1 , but it was operationally an x-ray, not an optical,
unit. The problem of expressing the unit A
in centimetres, however, did not differ from the

problem of relating X-units in centimetres. Density determinations by hydrostatic weighing
also introduced signicant errors due to surface tension effects, corrosion etc, when the attempt
was made to approach a precision level of 1 10
6
. The chemical methods for determining
molar masses were not very accurate as well. Furthermore, when silicon or germanium came
into use, material with a relatively low content of crystal defects, the measurement uncertainty
could not be reduced signicantly. Work by Henins and Bearden in 1964, in which 17 silicon
crystal samples were studied yielded N
A
3
= (6.059 770.000 15)10
23
mol
1
. The major
uncertainty in this determination was contributed by the calculation of the atomic weight of
silicon. So, in total, the level of precision reached at about 1960 converged at a value of about
70 10
6
, and, seemingly, did not improve further.
Figure 1. Schematic view of the x-ray interferometer for lattice parameter determination.
3.6. Discrepancies in x-ray data
The Avogadro constant belongs to the set of fundamental constants of physics, see section 6.
Each of the values can be expressed in terms of a few constants serving as unknowns. This
allowed experimental or theoretical results to be checked or improved. In 1955, a rst attempt
was made by Cohen et al (published in 1957) to recommend a set of adjusted values of the
fundamental constants. After 1965, revised versions were published (Cohen and DuMond
1965, Cohen and Taylor 1973) mainly due to the fact that a new scale of atomic weights (m
at
(
12
C) = 12 g) had been adopted by international organizations in 1960. In this adjustment the
authors did not feel too well satised with some of the discrepancies which that least-squares
adjustment had revealed, particularly in the domain of x-ray measurements and thus for N
A
.
At that time the general level of precision in other elds of physics had overtaken the precision
of the x-ray work. As a consequence, they decided to exclude completely fromthe calculations
all data derived from x-ray measurements.
The unsatisfactory situation as regards knowledge of the Avogadro constant was
highlighted by the very large differences between values recommended by further least-squares
adjustments, where data derived from macroscopic quantum properties have been included.
This problem could be solved only when, with the development of x-ray interferometry a
method was invented by which x-ray wavelength and lattice parameter could be measured
directly in meters, the unit of length, and a separate x-ray unit thus became superuous.
4. Establishing the link of the lattice parameter to the meter by x-ray interferometry
The most important characteristic of the x-ray interferometric method developed by Bonse and
Hart in 1965 is its ability to establish a lattice parameter without limitations to accuracy due
to the properties of the x-ray lines. The principle of measuring the lattice spacing of silicon
directly in terms of the meter is described in gure 1:
1956 P Becker
When x-rays pass through the rst crystal S, they are diffracted, and this happens again
in the second (M) and third crystal (A) which are mounted so that their crystal planes are very
accurately parallel to one another. The x-rays diffracted by the rst two crystals produce a
region of stationary wavefronts at the locus of the third crystal. This crystal also diffracts the
x-rays, and the diffracted beams are monitored by a detector D. In a Gedankenexperiment,
the third crystal is then moved through the stationary wave pattern, parallel to the diffraction
vector. When the atomic planes of the third crystal are in line with those of the rst two, a
maximum of the counting rate of the detector occurs while at half a repeat distance a minimum
is found. Attachment of a length ruler to the movable part of the crystal interferometer allows
the displacement to be monitored very precisely. Simultaneously, the number of x-ray fringes
per unit length can be counted and the crystal lattice period d determined in absolute values
with extremely high precision when optical interferometric means are applied to measure the
crystal displacement (indicated by open arrows).
4.1. Former XRCD key experiments
Three technically distinct efforts towards such a combination of x-ray/optical interferometry
(COXI) were rst described at a conference on precision measurements and fundamental
constants in 1970 by Bonse et al (1971), Hart (Curtis et al 1971) and Deslattes (1971).
Work in this direction was also initiated by Tarbeyev (1984) at the D I Mendeleyev Institute
for Metrology (VNIIM) in St. Petersburg, Russian Federation. With the exception of the
basic principle, which all approaches had in common, there were differences in the technical
realization of the design of the x-ray interferometer, of the type of the optical interferometer
providing the SI unit, the meter, and of the performance of the translation mechanism. Bonse
and Deslattes used x-ray interferometers with the third crystal mounted separately on a special
translation stage in which the elastic deformation of spring elements facilitated the necessary
smooth translation. Hart used a monolithic interferometer which had an elastic spring strip
device as part of the same silicon crystal. For the measurement of the displacement, the rst two
groups used a multiple-beaminterferometer of the FabryPerot type with extra optical mirrors,
the third group a two-beam interferometer of the Michelson type with silicon mirrors polished
directly onto the interferometer crystal. The experiments were performed at the University of
M unster, at the National Physical Laboratory in Teddington and the former National Bureau
of Standards (NBS) in Gaithersburg where, in 1973, a relative measurement accuracy in the
determination of the lattice parameter of 0.15 10
6
was achieved (Deslattes and Henins
1973).
While work at Teddington was stopped after a couple of years, the NBScontinued its work,
including the necessary experiments on molar mass and density for a determination of N
A
.
Since 1970, the Physikalisch-Technische Bundesanstalt, PTB, in Braunschweig has carried
on the measurements started by the University of M unster. Later on, national metrology
institutes in Italy (Istituto di Metrologia G Colonnetti, IMGC, Turin), in Japan (National
Research Laboratory of Metrology, NRLM, Tsukuba), in Australia (CSIRO, Sydney) as well
as the Central Bureau for Nuclear Measurements (now the Institute for Reference Materials
and Measurements IRMM) joined PTB and NBS (now the National Institute of Standards
and Technology, NIST) rst in scientic competition but today in a cooperative project under
the umbrella of the Bureau International des Poids et Mesures (BIPM) to concentrate and
coordinate their activities for a precise determination of the Avogadro constant.
In order to avoid the problems arising with naturally grown crystals, work was carried
out with silicon single-crystal material. The main reason was that Si can be grown in large
quantities with a high degree of perfection. Any application of the dynamical theory of x-ray
diffraction (Laue and Ewald) to experimental results obtained on silicon at that time pointed to
an almost ideal perfection of the crystal lattice. In further experiments it became evident that
the degree of perfection is, of course, a question of the measurement uncertainty achieved.
Another candidate for the XRCD method, germanium, was also taken into consideration.
It is a semiconductor material also used for electronic devices. Indeed, the rst transistor was
fabricated from Ge. Soon after that, however, Si replaced Ge because it offered two main
advantages: for metrological application, compared to Ge, silicon has a thermal expansion
coefcient smaller by a factor of three and a more stable surface oxide layer. Today, since
silicon crystals are produced by the ton; the costs are therefore reasonably low and availability
of the material is high. Thousands of scientic papers about silicon have been published to
date, therefore, silicon is the material best investigated world-wide.
5. Avogadros hypothesis: the XRCD method
The Avogadro constant as a link between atomic and microscopic scales represents the number
of entities in a mole. To overcome the problems which accompany the direct counting of such
a great number with high precision, the XRCD method described here shows an alternative
way which makes use of the high perfection of a single crystal. For the determination of N
A
,
equation (6) can be rewritten without any correction factors:
N
A
=
n M
a
3
0
. (7)
N
A
is nothing else than the ratio of the molar volume V
mol
and the atomic volume V
at
or, in
other words, the ratio of the molar mass M
mol
and the atomic mass m
at
:
N
A
=
V
mol
V
at
, (8a)
and
N
A
=
M
mol
m
at
, (8b)
respectively. The following quantities must be measured:
(1) The volume occupied by a single Si atom, derived fromthe knowledge of the structure and
the lattice spacing of a highly perfect, highly pure silicon crystal. These measurements
therefore include precise investigations into the content of impurity atoms and self-point
defects,
(2) the macroscopic density of the same crystal, and
(3) the molar mass and, thus, the isotopic composition of the Si crystal (Si has three stable
isotopes:
28
Si,
29
Si,
30
Si).
The last task is actively pursued by the Institute for Reference Materials and Measurements
(IRMM) of the European Union in Geel (Belgium).
In various reports and at conferences, the national metrology laboratories and institutes
give information about their activities and the present state of their research work. A
symposium related to this work is held within the framework of the Conference on
Precision Electromagnetic Measurements (CPEM) every 2 years. A detailed summary of
the experimental state around 1994 was published by Basile et al (1994) (special issue of
Metrologia) and, in a compact version, by Becker (1997).
1958 P Becker
5.1. Material characterization
The counting of silicon atoms by the XRCDmethod presupposes knowledge of the number of
impurities and their inuence on mass and volume. A precise determination of N
A
, therefore,
requires by all means (1) the identication of the type and the content of the impurity and (2)
the evaluation of the inuence on mass and lattice parameter. These tasks are described in the
followng sections.
All semiconductor-grade siliconis producedbyconvertingsiliconcompounds toelemental
silicon by chemical vapour deposition (CVD). For approx. 75%of the world CVDproduction,
trichlorosilane (Cl
3
SiH) is used as the silicon compound (for example by Wacker, MEMC,
Tokuyama, Kyundo), and silane (SiH
4
) (for example by ASiMI, ethyl) is used for the remaining
25%. The polycrystalline material shows signicant differences in grain size and impurity
concentration: silicon fromsilane is purer and of ner grain size than that fromtrichlorosilane.
As will be described later, in the case of silane the CVD process gives rise to a remarkable
isotopic separation effect. For the production of silicon single crystals, two crystal growth
methods are commonly used: the Czochralski (CZ) method which yields about 85% of all
single crystalline silicon, and the oat-zone (FZ) method with a share of 15%.
Generally, all classes of crystal defects can be found in silicon as well. But if we focus our
discussion on selected undoped crystals grown under extreme metrological conditions, only
zero-dimensional point defects occur in signicant concentrations. In particular, in silicon the
low packing density of the diamond latticein contrast to the face-centred cubic lattice of
metalsenables the incorporation of interstitial atoms. Parameters which can inuence both
the silicon lattice parameter and the density are: temperature, pressure and lattice defects, such
as impurity atoms, self-point defects mainly incorporated into the lattice during the growth
process, and the isotopic silicon composition. Only 1 10
8
% of the atoms are foreign
atoms (Zulehner et al 1993). This negligibly small amount is achieved by the highly efcient
purication process during the oating zone (FZ) renement of the crystal growth. The key
parameter of this process is the distribution coefcient k
, which is the ratio of the impurity

concentrations in the crystal and in the melt. For k
< 1, the crystal will be puried during

the growth process. In addition, a small percentage of some impurities, such as O, P, SiO, can
be eliminated by evaporation.
How perfect can a silicon crystal be? For the application discussed here, the following defects
must be taken into account:
(1) impurity atoms occurring on regular lattice sites by the substitution of silicon atoms,
(2) impurities on interstitial lattice sites, which increase the average number of atoms per unit
cell,
(3) Si vacancies and Si self-interstitials favoured by the relatively small packing density of
the lattice (only 36% of the volume is lled up).
In all cases, the defects can occur as point-like defects or as agglomerates such as swirls,
voids or precipitates with concentrations produced mostly during the crystal growth process.
On these assumptions, the average number, n, of atoms per unit cell in equation (7) is no longer
an integral number, and, consequently, the lattice parameters a and n must be slightly modied
by a and n = (N
o
n), with N
o
= 8 and n being a correction for the impurity content well
below 1 10
7
.
At present, the concentration of the main residual impurities in undoped FZ-puried Si,
either electrically active or inactive, can be measured by optical (IR) spectroscopy. For inactive
impurities the method is not so sensitive, and the detection limits are close to the residual Cand
Oconcentrations inthe best crystals (<110
15
cm
3
). For concentrations below510
11
cm
3
,
electrically active impurities can be detected, for example, by electron spin or photothermal
ionization spectroscopy. Oxygen concentrations below10
13
cm
3
were recently determined by
means of phonon spectroscopy (Zeller et al 1999) with superconducting tunnelling junctions.
Besides optical spectroscopy, a wide range of mass spectroscopy methods can also be used to
obtain impurity concentrations.
Carbon and oxygen have already been introduced into the rawmaterial, the polycrystalline
rod, which is fabricated by CVD. Carbon with k
= 0.07 can be reduced by multiple FZ-

renement. For oxygen, k
is close to 1 and the amount of O cannot, therefore, be reduced by

segregation during crystal growth but effectively by evaporation. Oxygen can also penetrate
into the crystal when the growth atmosphere is not free of humidity. In the FZ-material used
in our experiments, the carbon and oxygen content is of the order of several times 10
15
cm
3
and can be detected by IR spectroscopy with a detection limit of 5 10
13
cm
3
for C and
2 10
14
cm
3
for O.
Nitrogen occupies interstitial lattice sites and is a doping material which prevents the
agglomeration of self-point defects such as swirls, and forms N-vacancy or N-self-interstitial
complexes. The mechanism of binding is not yet fully understood, but this model concept is
supported by the fact that the N-concentration necessary for the suppression of swirls, and the
vacancy concentration, are of the same order of magnitude. In general, this kind of N-doping
leads to a lattice expansion as is also found in the case of vacancies (Biernacki and Becker
1999). The nitrogen is added to the growth atmosphere during the pulling process. Usually, a
doping rate of several 10
14
cm
3
is needed (Wolf et al 1996). When IR spectroscopy is used,
the detection limit is 1.5 10
14
cm
3
.
The radial distribution of self-point defects is dened by the growth conditions and depends
strongly on the growth rate (Chikawa et al 1986). For instance, a rate of 2.5 mm min
1
for
crystals 100 mm in diameter leads to a concentric ring structure of point defects with an
alternative surplus of vacancies (D-swirls) or self-interstitials (A-swirls) separated by a neutral
zone (0-zone) (Chikawa and Matsui 1993). An increase in the pulling speed is generally
accompanied by a radial expansion of the vacancy-enriched central range. In contrast to this,
sufcient speed reduction leads to a completely interstitial-dominated crystal. This behaviour
is probably detectable in all FZ-materials and can be made visible in nitrogen-free crystals
by preferential etching or, in the case of nitrogen-doped crystals, for example by lithium ion
drifting (Knowlton et al 1996).
In the case of vacancies and self-interstitials, investigations into their equilibrium
concentrations and diffusion are more difcult as their actual concentrations at room
temperature are unknown. From calculations, values around 10
11
cm
3
are to be expected
because of the very strong covalent binding conditions, but these data are uncertain within
several orders of magnitude (Zulehner 1991a)! The following experimental methods were
applied to determine and calibrate the in situ point defect density:
Positron annihilation: if a specimen contains vacancy-type defects, there is a nite
probability of positrons being trapped by them. The lifetime of the positrons reects
the density of electrons in the places where positrons are annihilated. A brief introduction
to this method can be found in Krause-Rehberg et al (1994).
Diffusion experiments, either with silicon isotopes
30
Si,
31
Si or with tracer elements such
as boron, phosphorus, or diffusion of metal atoms during growth: a comparison of the
experimental diffusion proles with the simulation of the diffusion mechanism(Knowlton
et al 1995) or the determination of the concentration of the incorporated atoms yields an
estimate of the vacancy concentration (Lembke and Zulehner 1999).
In an annihilation experiment, positron lifetime measurements in electron-irradiated
1960 P Becker
samples show an increase by 3 ps at low temperature. In native Si, only an increase of
1 ps was found. From that, vacancy-like defects could be derived, with an upper limit of
a defect concentration of 1 10
14
cm
3
in the native silicon crystals (Gebauer et al 1999).
Depending on doping with nitrogen, vacancies remained as single defects or formed voids
about 200 nmin diameter and between 10
5
and 10
6
cm
3
in density, with overall concentrations
between 6 10
13
and 1 10
14
cm
3
. The calculations are in agreement with the positron
annihilation measurements and density comparisons of samples cut from different swirl
zones, cf section 5.1.3.
The concentration of interstitial Si at room temperature is unknown. But if we take into
account that vacancies and interstitials are almost in a state of equilibrium, the inuence of
mass and lattice parameter changes is further reduced. Grown-in voids were also simulated
as spherical clusters of vacancies that nucleate homogeneously in a temperature range from
1100 to 950
C (Vanhellemont et al 1997). The density and the size of the clusters are
inuenced by the cooling rate and the initial vacancy concentration. For the solidmelt
interface the simulation results predict concentrations of vacancies and self-interstitials in
the same order of 10
15
cm
3
and, with decreasing temperature, show a signicant reduction
by mutual recombination. The recombination process stops at temperatures below 1250
C
and self-interstitial lattice sites are almost completely depleted (von Ammon and Dornberger
1999).
Hydrogen as an interstitial impurity diffuses very rapidly, and the maximum solubility is
rather low. At room temperature, diffusibility and solubility data show an H-density in argon-
grown Si of between 10
5
and 2 10
7
cm
3
. This hydrogenation takes place during chemical
etching or when a semiconductor sample in water is simply boiled (Pearton et al 1992).
Typically, these techniques lead to maximumhydrogen near-surface (a fewm) concentrations
of about 10
16
cm
3
. In the case of 1 kg silicon spheres, the surface volume fraction of about
3 10
4
would simulate an average hydrogen density of 3 10
12
cm
3
. Crystals grown
fromsilane poly-material showa high concentration of hydrogen, which could be qualitatively
identied in the ambient argon gas. Apercentage of hydrogen in the growth atmosphere, added
in the past to suppress the formation of swirls, can cause small voids lled with hydrogen under
high pressure, which are perfectly enclosed by the host lattice.
In order to investigate the inuence of hydrogen on density, crystals were grown in argon
atmosphere containing a percentage of hydrogen (max. 2%), see section 5.1.3. A well-
established method to detect voids larger than 20 nm is laser scattering tomography (LST),
see for example Moriyama et al 1989. A typical result of hydrogen-induced voids in perfect
silicon is shown in gure 2 (Becker 1999).
Argon-related defects in silicon have been detected recently by Ulyashin et al (2000),
stimulated by hydrogen implantation. The results obtained show that argon is present as an
unintentional impurity in FZ-Si after material growth in the argon gas ambience. To investigate
quantitatively this inuence in our as-grown silicon, crystals were grown in atmospheres of
different argon pressure and, for comparison, in vacuum. Density and lattice parameters of
these crystals were measured and compared with one another. Within the experimental limits
(2.5 10
8
rel.) no indication of the inuence of argon on lattice parameter and density was
found (Martin et al 1999), see also table 23.
Accurate measurements of the lattice parameter of a
28
Si enriched (99.02%) single crystal
and the results of rst principle calculations of the dependence of the Si lattice parameter
on temperature and on the isotopic composition were reported by Becker et al (1995). The
enriched crystals lattice parameter is larger than that of a naturally composed Si crystal by
about 2 10
6
. Even though the isotopic composition varies from crystal to crystal by
more than 3 10
6
, the inuence of differences in the natural isotopic composition on the
(1)
(2)
Figure 2. LST images of bulk silicon voids, (1) CZ-grown by Wacker with a high number of voids,
typical diameter of about 0.1 m. (2) FZ-grown by IKZ in Ar atmosphere with 2% of H
2
.
lattice parameter can, at present, be neglected when silicon material is used for metrological
applications.
A typical defect concentration in the best puried FZ-silicon material commercially
available is summarized in table 2 (Zulehner 1999). The comparison with the defect density
in the polycrystalline material after the chemical vapour deposition process also shown gives
an impression of the high degree of purication of the material by FZ-pulling.
Reduction of carbon and oxygen content in FZ-Si. Silicon material with an impurity
concentration of about 1 10
15
cm
3
is commercially available today and suitable for
metrological applications. To our present knowledge, the carbon and oxygen content in almost
pure silicon can be reduced by one order of magnitude. If this can infact be achieved, it would
lead to a crystal material with a lattice parameter showing a relative stability of better than
110
8
(Martin et al 1998). This reduction is possible because the growing process for silicon
material can be improved to higher chemical purity and perfection. Then impurity corrections
would no longer be necessary.
1962 P Becker
Table 2. Typical concentrations of impurities in CVD and FZ-silicon. Source: WackerSiltronic.
RT = room temperature.
CVD-poly-Si FZ-Si (argon)
Point defect/impurity ratio ratio
Mono & di-vacancies 2 10
9
at RT
Self-interstitials 1 10
9
at RT
C 4 10
8
4 10
8
N <2 10
9
<1 10
9
or <2 10
8
doped
O <1 10
8
4 10
8
B 2 10
12
2 10
12
Al 1 10
10
1 10
12
P 2 10
12
2 10
12
As 2 10
12
3 10
13
Sb 1 10
13
5 10
14
Na 2 10
11
1 10
12
K <1 10
11
<1 10
11
Ge 1 10
10
1 10
10
Ti <5 10
11
<1 10
12
Cr 1 10
11
<2 10
14
Mn <1 10
11
<1 10
11
Fe <2 10
11
<1 10
13
Co 1 10
13
<1 10
14
Ni <5 10
13
<1 10
13
Cu 2 10
12
<2 10
13
Zn <5 10
13
<2 10
13
Zr <1 10
11
<5 10
13
Mo <2 10
13
<2 10
13
Ag 3 10
12
<1 10
14
Au 1 10
14
1 10
15
Total chemical purity
Inclusive of C, N, O 7 N 7 N
Exclusive 9.5 N 10 N
In collaboration with Wacker-Siltronic in Burghausen and the Institut f ur Kristallz uchtung
(IKZ) in Berlin, the PTBhas initiated a scientic programme for the improvement of the purity
of silicon crystals. The carbon content of silicon material, mainly due to the C contamination
in the polycrystal rod, can be reduced by multiple FZ-pulling. By technical improvements
a small percentage of C can also be eliminated. (The oil diffusion pumps usually used can
be replaced by molecular pumping systems which prevent the growth atmosphere from being
contaminatedbythe pumpoil.) Oxygenwill diffuse intothe lattice whenthe growthatmosphere
is contaminated by residual water vapour and can be reduced by growing in vacuum. This is
generally possible, but the diameter of the pulling rods is limited due to conduction problems.
In test crystals 40 mm in diameter, an oxygen concentration of 1 10
14
cm
3
was reached
(Zulehner 1997), cf data for M and of sample VW3A in the following tables.
Determination of the effective size of impurity atoms in silicon. Impurities effect mass and
volume changes in the silicon unit cell and therefore exert a strong inuence on the value of
the Avogadro constant. After the measurement of their number density has been described
in the previous section, the parameters of correlation between the impurity concentration and
lattice parameter and density must be evaluated. Similar investigations were rst published by
Baker et al (1968) who achieved a sensitivity of 510
15
atoms cm
3
. Today, atomic fractions
of less than 10
8
in a cubic centimetre can be detected for elements which play an important
role as dopants in silicon.
When impurity atoms enter regular lattice sites, the real silicon lattice parameter is affected
by the difference in atomic size between the atoms of the host lattice and the impurities. In
the case of crystals with diamond structure, each atom has four close neighbours, their bonds
are covalent, with some ionic character, and their interatomic distances are determined by the
corresponding covalent radii. In the case of a substitutional replacement of silicon atoms, the
value of the covalent radius r compared with that of silicon, r
Si
, directly shows the trend of
the volume change of the unit cell, and this changes linearly with the atomic concentration N
i
of the impurities, well known as Vegards law (Vegard 1921):
d/d = N
i
(9)
with:
=
r
r
Si
N
Si
(9a)
and
r = r
i
r
Si
(9b)
with r
Si
= 0.117 nm and N
Si
= 5 10
22
cm
3
for the covalent radius and atomic density of
silicon.
A similar discussion leads to density corrections for impurities
=
_
M
M
Si
N
Si
3
_
N
x
=
vol
N
x
, (10)
where M is equal either to M
x
M
Si
(substitutional atoms) or to M
x
(interstitial atoms).
If the impurities enter interstices between the host silicon atoms, prediction of quantitative
size factors is more complicated, because the development is affected by the electronic
structure, mist strains and elastic coefcients.
The coefcient , which is a measure of the inuence which impurities exert on the
structure of silicon crystals (Verges et al 1982), was quantitatively determined in the following
way: the data compiled in table 3 were derived from accurate comparisons between the lattice
spacing of doped crystals and that of a pure silicon reference material (Becker 1986). The
doping rate was determined by IRspectroscopy against calibrated standards. The material was
carefully checked for a homogeneous distribution of the foreign atoms. The experimental data
in column 3 are in excellent agreement with the concept of covalent radii of the crystals, derived
from the chemical bond theory (Pauling 1960) and displayed in column 2. The effective size
parameters derived from these results (Zulehner 1991), including investigations of lattice
strains by interstitial nitrogen and oxygen in silicon, are summarized in column 5 and compared
(column 4) with data published by Pietsch and Unger in 1983.
The principle of the x-ray method is based on the 1st derivative of the Bragg equation
where differences in lattice spacings are correlated with differences in the Bragg angles. In
practice, a double-source double-crystal arrangement shown in gure 3 was chosen, which
offers the following advantages.
When Bragg reections from the front side and from the opposite side of the lattice
planes are simultaneously used (reections by the reciprocal lattice vectors h and h), relative
differences in lattice spacings are directly proportional to angular differences of their diffracting
intensity proles. The absolute determination of macroscopic angles is thus avoided. Rotation
of the sample through 180
about the yaw axis cancels out the inuence of lattice plane
bending.
1964 P Becker
Table 3. Effective radius r and lattice strain parameters of impurity atoms in FZ-Si. The data
calculated for an Si-vacancy have been taken from Schefer et al (1985).
1 2 3 4 5
r (nm) r (nm) (10
24
cm
3
) (10
24
cm
3
)
Atom theor. exp. theor. exp.
C 0.077 0.077 6.9 6.9 0.2
O (interst.) 0.142 +4.4 0.5
N (interst.) 0.150 +5.7 1.0
B 0.088 0.084 5.1 5.6 0.2
P 0.110 0.109 1.4 1.3 0.2
As 0.118 0.117 0 0.07 0.5
Sb 0.136 0.133 +3.0 +2.8 0.2
Vac 0.129 0.1274 +2 +1.7 0.5
Si 0.117 0.1176
Figure 3. Schematic of ray tracing of the PTB lattice parameter comparator (Martin 1998).
Chromatic dispersion of the x-ray wavelength can be neglected if the relative difference
in lattice spacing is no greater than 10
4
.
The intensity proles (rocking curves) are always symmetric: a detailed prole analysis
is not necessary.
Basic principle. The two beams leaving the two x-ray sources (foci 1 and 2) are rst Bragg-
reected in Laue geometry by the reference crystal, simultaneously by its h and h lattice
planes. The two reected waves meet together at the entrance surface of the test sample and
overlap inside the crystal, where the difference in lattice parameters is measured. In contrast
to this, defects in the reference crystal may inuence the measured differences which must
be treated as a constant offset in subsequent comparisons. This type of comparator was rst
proposed and developed by Hart (1969). The advantage of the design is that a monochromating
system with well dened x-ray wavelength is not needed.
The reference crystal and the sample under investigation are mounted on the two axes of a
double-crystal diffractometer, and when the sample is rotated about the yawaxis , see gure 3,
two rocking curves are obtained. If both crystals have the same lattice spacing d, both curves
will appear simultaneously at the same angular setting. When the crystals lattice spacings
differ by d, the rocking curves have an angular offset which is twice the difference in
Bragg angles,
R
and
S
, of the two crystals and linked to the differences d in lattice spacings
Table 4. Assessment of errors, PTB approach.
u
rel
Distribution (parts in 10
9
)
Misalignment , Rectangular 2.5
Temperature Rectangular 2.5
Data processing Rectangular 2.5
Angle measurement Rectangular 1
Statistic Gaussian 2.5
5.1 Total
a
a
Root-sum-of-squares (rss).
by
= 2 (
R

S
) (11)
and
d
d
=
1
2
cot
B
. (11a)
In this way, the measurements of small differences in lattice spacings are converted into angular
measurements. As double-crystal rocking curves are almost free of wavelength dispersion,
they may be angularly narrow. Using high-order reections combined with a short x-ray
wavelength, e.g. AgK radiation and Si(880) reection, an angular range of 10
7
rad full
width at half height of the curve is easily obtained. If the peak position can be xed to within
1%, then relative differences of 10
9
rad in Bragg angle can be measured.
Misalignments. The relationship in (11a) holds only if the x-ray beams and the diffraction
vectors for both crystals are coplanar, i.e. if they are in the same plane of diffraction. When
the sample is misorientated about the pitch axis (see gure 3) by an angle or/and when one
of the measuring x-ray beam paths, beams F1D1 and F2D2 in gure 3, are out of plane
characterized by the diffracting vectors h and hby an angle , then the rocking curves are
also separated by an angle :
= 2
2
tan
B
. (12)
Combining equations (11) and (12) we obtain
d
d
=
1
2
cot
B
(2
2
tan
B
) (13)
(: angle in the vertical plane between the normals of the reecting lattice planes; : departure
from coplanarity between the two x-ray beams). Samples with different impurity contents
were investigated using the (880) reection and AgK radiation. Differences in the lattice
spacing with respect to a reference crystal were detected with an uncertainty of 5 10
9
.
Error budget. The total measurement uncertainty of a lattice parameter comparison can be
derived from the single uncertainties summarized in table 4. Measurement uncertainties
based on inhomogeneities of the lattice spacing due to impurities, isotopic composition or
macroscopic structure defects have not been included in the table. They must be taken into
account in the assessment of the individual comparison.
A similar set-up is currently used at NIST (Kessler et al 1994). Its special features are
the Bragg angle measurement by an optical angle interferometer, the easy exchange of crystal
samples and the comparison of four samples in a single set-up. Differences in lattice spacings
1966 P Becker
Table 5. Assessment of errors, NIST approach.
u
rel
Systematic effect (parts in 10
9
)
Optical wavelength and 1st crystal orientation 7
Temperature 3
Crystal misalignment 2
Nonlinearity of interferometry 5
9 Total
a
a
Root-sum-of-squares (rss).
Table 6. Impurities in crystals used for the Avogadro experiments (in 10
15
cm
3
).
Producer Dow chemical Wacker MEMC Shin-Etsu
Label Perfex WASO 4.2 WASO 17 WASO 04 MO SH1
Laboratory NIST PTB PTB PTB, IMGC, CSIRO IMGC NRLM
Impurities in 10
15
cm
3
Carbon 39 4.3 1.2 4.5 1.2 2.5 0.5 13.7 0 5.6 0.9
Oxygen 60 1.0 0.5 5.2 1.5 1.2 0.7 0.4 0.1 2.0 0.2
Nitrogen 0.62 0.11 <2
Vacancies <1 <1 <1
Self-interstitials <1 <1 <1
Boron p-dot. <0.001 0.13 <0.001
Phosphorus <0.003 0.01
with a relative uncertainty of 1 10
8
, see table 5, were reported by Kessler et al (1997) but
showed a 6 10
8
discrepancy to PTB data over many years. Recent comparisons of relative
measurements carried out at PTB and NIST on the same samples now indicate a consistency
between both set-ups within an uncertainty of about 1 10
8
(Kessler et al 1999).
Temperature and pressure. The dependence of the lattice parameter on temperature and pres-
sure is obvious and should be mentioned here: the changes due to temperature and pressure can
be traced back to the linear expansion coefcient of 2.5610
6
K
1
and to the volumetric com-
pression coefcient of 1.02 10
6
/bar, respectively. The rst inuence is rather critical: the
absolute temperature must be known to within 1 mKif a measurement uncertainty of 10
8
is re-
quired. The inuence on pressure can be avoided when the measurements are made in vacuum.
The crystals used in the XRCD approach. Both CZ and FZ silicon material from
different suppliers was used for the determination of the Avogadro constant. The measured
concentrations of the main chemical impurities of the most signicant crystals are given in
table 6. As can be deduced from the data, there are no signicant differences in the purity of
the material, except for the MEMC sample used at IMGC. After correction for the relatively
high amount of carbon, the deduced lattice parameter agrees very well with the other ones, a
quite excellent indication of the perfection of the selected material and, in particular, of the
invariability of the lattice parameter.
Most of the material was grown 10 or more years ago and information about growing
conditions etc are no longer available. Only in the case of the WASO 04 crystal, delivered in
1995, are the growth process and the impurity proles along the crystal ingot well supported by
documents. The homogeneity of the lattice parameter along the growth axis was investigated
by Becker et al (1999) at PTB and by Deslattes et al (1999) at NIST. NIST comparison data of
three regions of the ingot show that this material is uniform to within about 2 10
8
. Radial
10 15 20 25 30 35 40 45 50
-1,0
-0,5
0,0
0,5
1,0
1,5
A zone O zone D zone
length position 121,5 cm
length position 73,5 cm
d
/
d

[
1
0
-
8
]
radial position [mm]
Figure 4. Radial variation of the lattice parameter investigated in WASO04 silicon at two different
axial positions and at three different radial positions D, O, and A according to the three different
swirl defects areas.
-0,3
0
0,3
D O A
(
(
D
i
)
)

/

i
n

1
0
-
6
Figure 5. Density differences of three samples cut
from different zones of the slightly nitrogen-doped
WASO 04 crystal.
investigation of the different swirl zones A, D, and 0 shows no signicant variation of either
the lattice parameter (see gure 4), or the density (see gure 5).
From the total number density of the point defects in that material, the average number
of atoms in the unit cell n = (N
o
n), with N
o
= 8 and n = 1 10
7
, a correction for
the interstitial impurity portion, can be derived for the WASO 04 crystal with a measurement
uncertainty for n of about 10%.
Besides the crystals listed in table 6, other silicon materials were included in the
experiments. For comparison of data in this report, the corresponding values for density,
molar mass and lattice spacing are labelled in the following by the same identication code.
In most cases the location of the individual samples in the crystal boules are well supported
by documents, as has recently been shown by Fujii and coworkers (1999) in the case of the
NRLM experiment.
Molar volume anomaly of sample SH1. For the sample SH1, a signicantly lower density and
thus a signicantly higher molar volumetaking into account the isotopic compositionin
1968 P Becker
relation to other material were found, by about 3 10
6
(Becker 1999). These ndings could
not be conrmed by any material made available by the same supplier and by others, and they
are not related to changes in the lattice periods. Small voids are, therefore, suspected as the
cause of this difference in this particular sample. Laser scattering tomography, secco-etching,
electron spin resonance, small-angle scattering, and x-ray topography are being applied to the
SH1 sample by different laboratories to detect voids or nano-voids. Concerning the detection of
voids in sample SH1 results so far using x-ray topography are not convincing. This is because
the reported size of the defects of about 50 m (Deslattes et al 1999) is not in agreement
with the null-result measurements carried out by laser tomography (Nakayama et al 2001).
The observed defects can be related to defects at or close to the surface possibly generated by
improper sample preparation (Tuomi et al 2001). Since the density number and the size of the
voids are unknown parameters, the sensitivity of the IR method, with a resolution currently of
20 nm, will be increased to a few nanometres to allow nano-voids to be observed.
To further investigate the density anomaly, PTB has collaborated with the IKZ in Berlin.
Special FZpuriedsiliconsingle crystals were grownfromSiHCl
3
andSiH
4
siliconcompounds
toinvestigate the inuence of growthparameters of the molar volume. These include the growth
speed, growth in different atmospheres (vacuum, argon at different pressures (1 and 3 bar), with
a percentage of nitrogen and/or deuterium, as discussed in section 5.1), isotopic distribution,
and grain size in the raw material. Recently, indications were found of molar mass separations
in the order of 10
5
M
Si
in SiH
4
-deposited polycrystals 2 m in length. They are probably the
consequence of small mass differences of 3%between the three silicon compounds, in contrast
to differences of 0.7%in the case of triclorosilane. Recent results of density comparisons of FZ-
crystals made of two different poly-crystal materials showed a slight dependence of the molar
volume on the raw material, but they did not show any signicant molar volume differences
due to different growing conditions (Basile 2000), an indication that the overall perfection of
the crystals will not suffer from variations of the growth conditions. The origin of the reported
molar volume anomaly in SH1 is still unknown, and investigations and measurements are still
under way.
5.2. The silicon lattice parameteran invariant quantity of nature?
Four high-precision measurements of the (220) silicon lattice spacing have so far been
completed, at NIST, PTB, IMGCand NRLM. The principles of these measurements are similar
and the basic components are shown in gure 1.
As discussed before, up to a resolution of several femtometres (1 fm = 10
15
m), the
purity of semiconductor-grade silicon is high enough so that no correction for imperfections
must be made. When the 10
15
fm boundary is bridged, the actual content of impurity
atoms, self-point defects and, less important, the actual isotopic composition must be taken
into account. Since the element-specic analysis of the impurities made by spectroscopic
means (see section 3.1.2), the impurities inuences on lattice homogeneity, and the average
interatomic distance measured with special x-ray crystal arrangements are sufciently exact,
the general procedure is to correct for the measured lattice parameter in order to obtain data
for an ideal crystal structure. (This case is denoted by C, O 0 in the following tables for
carbon and oxygen reaching zero concentration.)
The rst outstanding measurement made by Deslattes was a milestone on the way to
referring x-ray data to an absolute scale and showed the way to all other experimental groups.
The NIST approach. A detailed description of the experimental arrangements and the
measurement procedure for the lattice parameter determination was given by Deslattes (1980a).
An iodine-stabilized HeNe-laser was used in the optical interferometrical part of the apparatus
Figure 6. Diagram of the linear motion stage and of interferometers used in the NBS (NIST)
experiment to determine the Si lattice parameter.
(gure 6). The wavelength of the laser stabilized to the inverse Lamb dip was 632 990.079 pm
(0.004 10
6
). The output power from the laser was 100 W. Radiation passed through
mode-matching optics, circular polarizers, and decoupling attenuators before being used in
the hemispherical FabryPerot interferometer (OI) for the displacement measurement. High
reectivity coatings were used to produce narrow FabryPerot fringe signals of a nesse close
to 1500, i.e. the full width of a fringe corresponded to a change of about 316 nm in the plate
separation. Since the x-ray fringe period is approximately 0.2 nm a pointing precision of
0.001 nm was achieved.
Precise and rectilinear motion of the movable component of the silicon crystal
interferometer, and precise relative orientation to ensure satisfactory x-ray fringe contrast
were achieved by a special mechanical device shown in gure 6. The structure also allowed
four rotational adjustments about two orthogonal axes to be made. The device was machined
from a solid block and, due to an arrangement of cuts and holes, it was equivalent to a series
of levers and pivots. Translation motion was achieved by a uid-lled bellows device driving
a pin which entered the structure at point O and actuated lever I through a cone-shaped socket.
The pin was provided with a piezo-electric element permitting motions on the picometre scale
under active feedback control. The motion of the micrometer screw thus was reduced by a
another factor of about 300. This device permitted displacement rates as small as 0.1 nm per
minute. Excursions of the movable part of the interferometer by about 10 m were necessary
to achieve observations with an uncertainty of 0.2 10
6
.
The requirement to align the three silicon crystals (SiI) very accurately with respect to
1970 P Becker
Table 7. Uncertainty budget for XROI experiment at NBS (NIST).
u
rel
Parameter (10
8
d
220
)
Aligment XROI 4
Temperature 2
Fresnel phase shift 1
Mirror radius 2
Laser 13
Bulk modulus 1
Statistics 3
Total (rss) 15
one another was met by fabricating them from a single block of silicon and mounting them on
their respective supports. Fortunately, a narrow feature was found in the centre of the rocking
curve, when the two separated crystal parts were tilted around the Bragg position with respect
to one another. It allowed a very high alignment sensitivity in the order of 0.01 arc sec to
be achieved. Later on, Bonse and Teworte (1980) were able to explain this very narrow ne
structure as an interference effect inside the crystals due to Pendell osung fringes.
Essentially, the measurement consisted in counting x-ray and optical interference fringes
while the system was made to traverse a common base line. The number of x-ray fringes n,
corresponding to m optical half-wavelengths /2, is written as
d = m/n(m)/2 (14)
with
n(m) = N(m) + f (m). (14a)
First, the integer part of n(m), N(m), was determined by slow scans back and forth over a few
optical wavelengths and by counting of the total number of fringes. Knowledge of the fractional
part f (m) then was improved by tracing the progression of the x-ray phase as a function of the
order number of the optical interference fringes. In the experiment, N(1) 1648, depending
on the ambient experimental conditions (air; 22
C). The standard deviation due to statistical

effects corresponded to 0.04 10
6
.
Deslattes and Henins (1973) measured the d(220) lattice spacing of a vacuum oat-zone-
rened specimen of silicon (Deslattes 1980c) at temperatures between 22 and 23
C. A value
of 2.56 10
6
K
1
was used as the appropriate coefcient of expansion of Si, and the nal
result wirth an uncertainty of 0.1 10
6
(Deslattes 1980b), was
d(220)
NBS
= 0.192 017 07(2) nm at 25
C and in air. (15)

The contributions to the measurement uncertainty are listed in table 7. The total uncertainty was
mainly due to xing of the order number and of the estimated rst-derivative lock instability.
There were, however, systematic effects, attributable in particular to a problem with the
trajectory of the analyser crystal, which was only partially controlled. In a new version of the
experiment, specic steps were taken to ensure a more sensitive and precise determination of
the x-ray phase and on-line measurements of trajectory errors, in particular so-called cosine
and Abbe errors. First, a frequency-agile local oscillator laser was introduced, enabling the
systemto scan an entire x-ray period. Secondly, a four-beaminterferometer of the polarization-
encoded type was added whose signals could be processed to yield tilt angles independent of
displacement. Changes in the x-ray phase due to deliberate pitch and yaw motions were used
to measure the Abbe errors. Re-measurements reported by Deslattes et al (1987) produced
results of the lattice parameter, which were from1.6 to 1.710
6
smaller than those previously
obtained:
d(220)
NIST
= 192 015.54(2) fm, (22.5
C, 0 Pa). (16)
The PTB approach. The PTB approach shown schematically in gure 7 differed completely
from the NIST set-up with respect to technical details. The crystal interferometer had the
following special features: the front faces of the crystals were polished to form optical mirrors
parallel to the measured lattice spacings, high enough to nullify the offset between the optical
and x-ray baselines. By this, the mirrors used for the optical measurement of the displacement
were part of the crystal lattice itself. The two entirely separated crystals were supported by
three steel spheres, each resting on supports S
a
and S
b
, without being glued to them in order
to facilitate exchanges of the crystals. A Lamb-dip-stabilized HeNe laser was used in the
optical interferometer. Its frequency was on-line controlled separately during the experiment
by a
127
I
2
-stabilized HeNe laser in order to check at the same time the stability of the built-in
meter ruler. Optical feedback was avoided by a light trap (>30 dB attenuation). The two-
beam interferometer of the Michelson type was developed after Curtis et al (1971) with the
following features: the interferometer signals were invariant with respect to a common rotation
or translation of the whole x-ray interferometer. The two incident beams were polarized
perpendicular to each other by means of a half-wave plate. The phase difference of the beams
caused by the displacement was determined by electro-optical modulation in a Pockels cell and
synchronous detection. Thus a measuring uncertainty of 0.01 nmwas obtained. The long-time
stability of the interferometer signal was better than about 0.01 nmh
1
. The translation motion
was guided on a double parallel spring manufactured from one plate of high-quality steel. A
piezo-electric actuator was used as a drive for a 40 m displacement range. As the relative
phase between optical and x-ray interferometer signals was measured as a function of different
alignments, the point of impact of the laser beam onto the crystal mirrors was optimized until
the Abbe errors vanished. Residual guiding errors of the translation device were magnetically
compensated. Computer-aided on-line evaluation, as well as detailed data-processing allowed
the detection of f (m) as small as 10
3
of an x-ray fringe. The measurement procedure followed
the NIST scheme. A detailed description of the experimental procedures was published in two
PTB-reports by Rademacher et al (1980) and Hanen et al (1981).
Measurements were carried out between 22.42 and 22.50
C in vacuum. Each result was

reduced to 22.50
C by correcting for the thermal expansion coefcient = (2.56 0.03)

10
6
K
1
, measured separately on the same Si material. The results of 170 measurements are
shown in gure 8. The mean value of n/m and the standard deviation
m
were obtained by
tting a Gaussian distribution
_
n
m
_
=

2d
= 1648.281 626 (17)
with
m
= 0.000 007.
The development of the mean values with time and the corresponding standard deviations were
also checked (Siegert and Becker 1984). No signicant time-dependent systematic effects were
detected.
Several systematic corrections to the mean value of n/m had to be taken into account.
(1) The laser wavelength was = (632 991 415 5) fm. The beam prole was Gaussian,
with a radius in the waist of w
0
= (0.52 0.02) mm. The Fresnel phase shift in the beam
led to a correction
1
= (3.8 0.2) 10
8
n/m.
1972 P Becker
Figure 7. Principle of the PTB x-ray interferometer (1) with (a) movable, and (b) xed silicon
crystals; optical interferometer (2) with /4-plates (c), /2-plate (d), compensation plate (e), phase
modulator (f) and polarizer (g).
(2) Misaligment duringtranslationof the movable crystal was
2
= (0.10.2)10
8
n/m.
(3) Tilting of the crystal during motion combined with a lateral offset of the laser beam
impingement point on the mirror of the movable crystal with respect to the centre of the
crystal was
3
= 3.0 10
8
n/m.
Figure 8. Histogram of the results of 170 measurements. The full curve is a least-squares t to a
Gaussian curve.
(4) Uncertainty of crystal temperature (0.02 K) and thermal expansion coefcient (3
10
8
K
1
) led to
4
= 5.1 10
8
n/m.
The nal result for the lattice spacing d(220) at 22.50
C and in vacuum (Becker et al

1981) was
d(220)
PTB
= 192 015.560(12) fm. (18)
In a second series of 336 single measurements the above value was conrmed with an
improved accuracy of 0.02 10
6
(Becker et al 1982). In a third series of measurements,
from the spacings of a whole set of equivalent (220) lattice planes related by symmetry, the
axial lengths, axial angles and the volume of the unit cell of a highly pure silicon sample
were obtained. Crystal-to-crystal comparisons (see section 5.1.2) led to the detection of
relative deviations from the cubic shape, in particular in 022 and 202 directions, of the
order of +2 10
7
and 2 10
7
(relative values) respectively. Using an average value
d(220) = (192 015.558 0.018) fm, a volume of the unit cell (at 22.50
C) of
V
0
= (0.160 193 259 0.000 000 044) nm
3
(19)
under vacuum conditions was obtained (Siegert et al 1984). Within the uncertainty limits the
value d(220) given in (18) and the average value d(220) were identical, an indication that
although the unit cell of highly pure silicon might be deformed by residual impurities; the
volume of the cell, however, seems to be unchanged.
For the determination of the Avogadro constant, different materials were used, named
WASO 17 in 1992, and WASO 04 in 2000. The individual lattice spacings were compared
with the WASO4.2 sample measured in absolute terms by the PTBlattice comparator described
above. Former comparisons by Windisch and Becker (1990) were made with a transfer crystal,
WASO
ref
, current measurements with crystals cut from WASO 04. The results obtained and
compiled in table 8 are in excellent agreement with previous ones.
The IMGC approach. The IMGC adopted a similar experimental set-up as the PTB, but in
contrast to PTB they used a classical set-up of the Michelson interferometer and a simple
1974 P Becker
Table 8. Relative differences in lattice parameter of PTBcrystals used for N
A
. (d
Test
-d
Ref
)/d
Ref

d/d, compared with reference crystal WASO 04 (C = 3 10
15
cm
3
, O = 1 10
15
cm
3
);
WASO
REF
(C < 0.7 10
15
cm
3
, O < 0.3 10
15
cm
3
) reference sample used before 1990.
d/d[10
9
] WASO
REF
WASO 4.2a WASO 17
As grown 22 10 1 6 22 10
C, O 0 11 10 10 7 15 10
Figure 9. Schematic drawing of the combined x-ray and optical interferometer used at IMGC.
parallel spring was used, see gure 9. The laser beam (
127
I
2
-stabilized HeNe laser) was
provided by a single-mode preserving bre polarization ensuring simple and stable remote
alignment and positioning of the beam. Position-sensitive detectors, P and Q, were used in
the x-ray part and in the optical part in order to measure and compensate on-line parasitic tilts
of the translation stage. The xed components of the x-ray and optical interferometer, C
2
and
M, were placed on a silicon base plate. The front faces of the crystals were optically polished
and metal-coated in order to enlarge the silicon reectivity and to prevent laser heating of
the crystal as well. The combination of nite-element analysis and active control allowed
millimetre displacements S to be achieved by constructing an elastic translation stage capable
of scan velocities ranging from1 pms
1
to 0.1 mms
1
and translations by up to 2 mm, smooth
to within 1 pm, with yawing and pitching to within 1 nrad (Mana 1989). The crystal was grown
and puried by FZ melting by MEMC electronic materials. The experiment was carried out
in vacuum; the crystal temperature was measured to within 3 mK using a platinum resistance
thermometer calibrated in accordance with ITS-90.
Adetailed theoretical analysis of the achievable resolution and accuracy was undertaken by
Basile et al (1991). Departures froman ideal experiment, such as limited machining accuracy,
chemical etching and imperfect guiding, had been taken in account. Focusing conditions of the
x-rays as well as thickness and alignment of the movable crystal changed with displacement.
Accoto et al (1994) simulated these inuences by calculating amplitude and phase of the
interfering x-rays using the dynamical theory of x-ray diffraction in a distorted mode.
High resolution and a brief observation time were achieved by a long scan, by the servo-
control of crystal motion, and, in the nal measurement, by data recording at the end points
of translation only. The nal data were collected in 196 runs, showing a 0.8 10
8
standard
deviation of the mean. Reproducibility was investigated by analysing 92 runs by re-assembling
part of the experimental set-up.
Table 9. Corrections and uncertainties of the IMGC d(220) determination.
Correction u
rel
Item (10
8
d
220
) (10
8
d
220
)
Statistics 0 0.5
Laser beam wavelength 0.2 0.2
Laser beam diffraction 2.5 0.8
Laser beam alignment 0.3 0.5
Crystal temperature 0.5 0.8
Crystal movement 0 1.8
Crystal attitude 0 0.8
Crystal geometry 0 0.8
Crystal impurities 9.3 1.4
Total (rss) 12.4 2.9
The nal results for n/m and the lattice spacing d(220) at 22.50
C and in vacuum
(Basile et al 1994) were
_
n
m
_
=

2d
= 1648.281 626 (20)
and
d(220)
IMGC
= 192 015.569(6) fm. (21)
Going beyond the PTB approach the data were obtained by rening x-ray and optical
interferometers to allow crystal position and attitude to be simultaneously measured, and
by means of a detailed analysis of different portions of the interference pattern in both
interferometers. Corrections and uncertainties of these measurements have been summarized
in table 9.
Based on these measurements, the IMGC researchers began work on improving the
measurement conditions to make measurements of a particular crystal with a relative
uncertainty at the 1 10
9
level. The issues addressed so far include the theory of scanning
x-ray interferometers, beam astigmatism in laser interferometry, and the problem of how to
manage an analyser displacement by up to 2 mmcorresponding to about 107 optical fringes. A
new translation stage was developed. Results of a new series of measurements of n/m carried
out with the same x-ray interferometer were reported by Bergamin et al (1999), who achieved
a relative standard deviation of the mean n/m value of about 1 10
9
, see gure 10.
The NRLM approach. The improvements of the NRLM device in comparison with the devices
previously used were the on-line correction of guiding errors during crystal motion and a
further miniaturization of the whole equipment (Nakayama et al 1992, Fujimoto et al 1995).
The nal experimental set-up shown in gure 11 was described by Nakayama and Fujimoto in
1997. It featured the combination of two laser systems that measure simultaneously the angle,
i.e. the lateral and the horizontal motion, between two crystals of the x-ray interferometer.
The crystal shape and the alignment procedure were similar to those used at PTB and IMGC.
The translation stage PAR consisted of a large and a small quadrilateral of links connected by
a exure-pivoted lever system. The stage was put in a rectangular frame that surrounded the
base of the stage. A PZT pushed the stage at lever L in a horizontal plane through the lower
pivots of the exure hinges. Two additional hinge devices, M for pitch and B for yaw, were
mounted on the stage to compensate pitch and yaw errors.
The trajectory interferometer measured pitch, yaw and roll angles as well as vertical and
lateral shifts of the stage during translation. Pitch error signals of the stage measured on-line
1976 P Becker
Figure 10. Histogram of 45 consecutive measurement results of n, the number of x-ray fringes
per optical period (reduced to 22.5
C). Solid curve is the best t to a Gaussian distribution

(measurement time 100 min).
Figure 11. Schematic diagram of the NRLM lattice spacing measurement device; M, B: tilting
devices for pitch and yaw corrections, L: application point of driving system.
were fed into a computer which calculated the input voltage to an amplier and fed the driving
voltage into a PZT for compensation of the tilting stage M. The same procedure was used
for yaw and roll errors. The displacement interferometer was of the Michelson type, too, and
used polarization beam splitters to generate four parallel beams. The dimensions of the glass
Table 10. Corrections and uncertainties of the NRLM d
220
experiment.
Correction u
rel
Item (10
8
d
220
) (10
8
d
220
)
Statistics 0 5
Laser beam wavelength 0 0.2
Abbe correction 0 1.0
Cosine correction 0.8 0.2
Crystal temperature 0 0.5
Crystal movement 0.5 0
Crystal impurities 3.0 0
Fresnel diffraction 16.0 0.8
Total (rss) 20.3 5.2
components were kept as small as possible in order to minimize the optical path length in
the interferometer. x-ray and optical interference signals were recorded by a computer. After
scanning of several x-ray fringes, the feedback loop for yaw and pitch were switched off and
the crystal moved to the next optical order. This procedure was repeated at the 0th, 107th,
and 217th or 0th, 100th and 200th optical order. The x-ray phase fraction at each optical node
was calculated by tting a sinusoidal function to the x-ray signal during displacement. The
histogram over 829 accumulated n/m data showed a Gaussian distribution, and the value is
n/m = 1648.240 524 0.000 083 (22)
in vacuum and at 22.50
C. Length measurements carried out with the optical interferometer

were affected by errors of different origin, such as laser misalignment with respect to the mirror
surface of the x-ray interferometer, the deviation of the direction of movement fromthe surface
normal of the mirror surface, the mode of the laser beam, and the Abbe offset. Compensation
for the change in the lattice parameter due to impurities was also included. The corrections
and uncertainties used in the deduction of the lattice spacing are summarized in table 10. The
resultant lattice spacing was (Nakayama and Fujimoto 1997)
d(220)
NRLM
= 192 015.593(10) fm. (23)
Results and comparisons of d(220) lattice spacings. Recent comparison measurements of
the material used by Martin et al 1998 in the metrological experiments have shown that
the distances between the silicon atoms in these samples do not differ by more than a few
parts in 10
8
, taking into account the different contents of impurities and different isotopic
compositions. These results lead to the assumption that the average interatomic distance in
ultra-pure siliconunder constant ambient conditionscan be seen as an invariant quantity
of nature. These investigations also covered material from h/m
n
experiments reported by
Kr uger et al 1995, which link the ne-structure constant with the wavelength and velocity of
thermal neutrons.
Table 12 shows the lattice spacings (in fm) of the most important silicon samples. Data
14 of the table, taken from equations (16), (18), (21) and (23), are referred to the ITS-90 and
show small, though signicant differences which are not due to improper investigations of the
impurity content. In contrast, the direct comparison (data 513) of the lattice spacings of the
samples used so far allows the conclusion to be drawn that the data derived from imperfect
crystals for a perfect Si crystal are constant within 2 10
8
d. Within these uncertainty
limits it may be assumed that the actual lattice spacing in samples of oat-zoned, highly pure
and almost perfect Si crystals is strongly related to the residual concentration of carbon and
1978 P Becker
Table 11. Relative differences in lattice spacings of selected samples used for the absolute
determination of fundamental constants. (d
Test
d
Ref
)/d
Ref
d/d
exp
, with WASO 04 =
reference crystal and C = 3 10
15
cm
3
, O = 1 10
15
cm
3
.
Fundam. d/d
exp
d/d
C,O0
Crystals constant Institute [10
9
] [10
9
]
WASO 04
ref
WASO 4.2a N
A
PTB 1 6 6 8
SH1(Shin-Etsu) N
A
NRLM 23 6 6 8
MO
4 (MEMC) N
A
IMGC 103 12 27 13
WASO Si5 h/m
n
PTB 25 16 10 17
Table 12. d
220
lattice spacings extrapolated from measurements of different crystals. Samples
14, absolute determinations by x-ray interferometry; 513, values obtained by comparison with
WASO 04; 14, data obtained by adjustment of fundamental constants in 1998 (Mohr and Taylor
2000).
Value in fm
Sample Institute (C, O0) Remarks
1 WASO 4.2 PTB 192 015.563(12) Absolute in t
90
2 Mo*4 IMGC 192 015.551(6) Absolute in t
90
3 SH1 NRLM 192 015.587(11) Absolute in t
90
4 PFX NIST 192 015.54(2) Absolute in t
90
5 WASO 04 PTB 192 015.566(12) Relative to WASO 4.2
6 WASO 17 PTB 192 015.566(12) Relative to WASO 04
7 Si5 PTB 192 015.568(12)
8 Mo*4 IMGC 192 015.562(12)
9 WG IMGC 192 015.568(12)
10 W3 IMGC 192 015.566(12)
11 SH1 NRLM 192 015.565(12)
12 PFX NIST 192 015.570(12)
13 ISC-X NIST 192 015.544(18)
14 CODATA 192 015 5845(56) Adjustment 1998
oxygen. This is an indication of the absence of signicant residual systematic effects caused,
for example, by self-point defects.
The measurements compiled in table 12 are shown graphically in gure 12 together
with the CODATA value for d
220
recommended in 1998. The upper part of the gure
shows the results of the comparisons and the lower part the data measured in absolute
terms.
They exhibit differences larger than the individual error bars. A best value for a silicon
lattice parameter is proposed to be based on WASO04 with which all other signicant materials
were compared.
To decide which material represents the real or best lattice parameterbeside the
excellent metrological work spent on the absolute measurementsother material parameters
should be taken into account. In the past, the material used in the different Avogadro projects
was not selected giving due regard to crystal quality: the IMGCmaterial, Mo
4, suffers froma
remarkably high carbon content, the Japanese material SH1 shows a remarkably lower density
than other silicon materials, which might be related to small voids as discussed by Deslattes
et al (1999) and Becker (1999). Only the Wacker material was investigated thoroughly for
purity and homogeneity and meets rather well the stated requirements. A hypothetically ideal,
192015,53 192015,55 192015,57 192015,59 192015,61
1
2
3
4
5
6
7
8
9
10
11
12
13
14
CODATA 98
ISC-X
-
+2x10
-8
PFX
SH1
W3
WG
Mo*4
Si5
Waso 17
Waso 04
PFX
SH1
Mo*4
Waso 4.2a
M
e
a
s
u
r
e
m
e
n
t
Si d
220
lattice parameter [fm]
Figure 12. Comparison of selected silicon lattice spacings. absolute measurement, relative
measurement by comparison and least-squares adjustment.
perfect crystal can, therefore, be deduced from WASO 04 if a C and O correction of 1610
9
is applied with a relative standard deviation of 1.2 10
8
, which includes the measurement
uncertainty due to Cand Ocorrections, and the uncertainty of 1010
9
which can be achieved
if the requirements for a highly pure FZ crystal growth process are fullled:
d
220
(ideal) = (d
WASO 04
+ 16 10
9
) 12 10
9
(24)
with
d
WASO 04
= (d
absolute
+ d
relative
), (24a)
d
absolute
being the value of a lattice spacing measured in absolute terms, and d
relative
the value
derived from a comparison of lattice spacings. Temperature and pressure conditions must be
fullled, as well as the content of selected types of point defects must be minimized, mainly
by means of the growth procedure. Doping is to be avoided. Two comparators, at the National
Institute of Standards and Technology (NIST, Kessler et al (1994)) and at PTB, are at present
being used to ensure traceability of the silicon lattice parameter. Similar experiments are under
way in other national institutes.
5.3. Determination of the molar mass
Absolute measurements of the silicon molar mass require absolute measurements of the isotope
abundances f
i
of the three stable isotopes with atomic masses M(
i
Si), i = 28, 29, 30:
M(Si) = f
28
M
28
+ f
29
M
29
+ f
30
M
30
= f
i
M(
i
Si) (25)
with f
i
= 1 and f
28
= 0.9223, f
29
= 0.0467 and f
30
= 0.0310 for natural composition.
From equation (25) we can derive:
M(Si) = M(
28
Si){1 + } (25a)
1980 P Becker
Figure 13. Schematic diagram of a mass spectrometer for isotope abundance measurements.
the fraction having to be measured with an uncertainty of at least 10
8
.
The abundance ratio measurements were performed by means of an isotope-ratio gas
mass spectrometer shown schematically in gure 13, which compares the number of atoms
of the various isotopes with one another through precise measurements of the ratios of the
isotopes ion currents. Application of this method requires that samples from the single
crystals be converted to the gaseous compound, SiF
4
. The ratio measurements are corrected
for systematic errors and calibrated against mixtures of enriched Si isotopes which have been
gravimetrically prepared. Up to nowonly two institutes world-wide had, or have, the capability
and the capacity needed to perform these measurements: the former NBS and the IRMM.
The NIST approach. The determination of the molar mass at the former NBS was carried out
in two steps. First, absolute isotope abundances were determined for a large boule of silicon.
This implied mass-spectrometric comparisons with a set of synthetic mixtures prepared from
the separated isotopes so as to span approximately the region covering abundance values of
naturally composed samples (Barnes et al 1975). For calibration, a solution of
28
Si and
30
Si
isotopes was prepared in the form of uorosilicic acid (H
2
SiF
6
), then assayed by gravimetric
determination of Cs
2
SiF
6
, followed by spectro-photometric determination of soluble silicon.
The synthetic mixtures were then prepared from weighed portions of these solutions. After
mixing, the silicon was precipitated as BaSiF
6
which was thermally decomposed to yield SiF
4
for isotopic measurement. The large sample was wafered and made publicly available for
relative measurements through the NIST Standard Reference Material Program as SRM 990
(Deslattes et al 1974).
Then, the abundance measurements of the specimens used were carried out relative to SRM
990. In a magnetic-sector mass spectrometer, ions were produced by electron bombardment of
SiF
4
in the gas phase. The results obtained for the three specimens designated by D
1
, D
2
, D
3
and used in the determination of N
A
are given in table 13. The estimated total uncertainty of
M
Si
was 0.65 10
6
, originating from the uncertainty of the chemical analysis (0.3 10
6
),
the uncertainty of the SRM 990 mass (0.5 10
6
), and uncertainties in the analysis of the
separated isotopes (0.3 10
6
).
The IRMM approach. The isotopic composition of the silicon single crystals of PTB, IMGC,
NRLM and CSIRO was determined by mass spectrometry at the Institute for Reference
Materials and Measurements (IRMM) of the Europan Union in Geel, Belgium. The mass
spectrometric measurements on SiF
4
gas included a chemical preparation similar to that made
by the NIST group. The chemical treatments at IRMM were described by De Bi` evre et al
Table 13. Molar masses of the reference material SRM 990 and of the silicon specimens D
1
, D
2
,
D
3
used at NIST(NBS).
Molar mass
Institute Crystal code (g/mol)
NBS/NIST SRM 990 28.085 525 8(15)
D1 28.085 400(18)
D2 28.085 379(18)
D3 28.085 507(18)
(1994 and 1995). The spectrometer ensured ionization of the molecules, their transmission
and mass separation in an analyser, and counting of the separated isotopes by electromagnetic
scanning over a single Faraday collector. Although the measurement of two ratios would
dene the three-isotope system, three ratios were measured. They made the measurement
system redundant and enabled one to verify whether the product of the measured ratios
n(
29
SiF
4
)/n(
28
SiF
4
) n(
28
SiF
4
)/n(
30
SiF
4
) n(
30
SiF
4
)/n(
29
SiF
4
) (26)
was equal to 1. Any deviation from exactly 1 was indicative of systematic errors in the
measurement of at least one ion beam. = 0.000 002 was in fact reached. Synthetic mixtures
of enriched isotopes were also prepared for calibration purposes, but nowfromall three isotopes
28
Si,
29
Si,
30
Si. The gas ow into the spectrometer through a pin-holed gold foil (20 m in
diameter) implieda change fromviscous tomolecular owand, consequently, a time-dependent
mass fractionation as kinetic gas theory prescribes. The corrections for the performance of
the mass spectrometer (MAT 271) were smaller than 10
4
(relative value). For this purpose a
correction factor K for residual systematic errors was dened as the ratio of the best estimate
of the true abundance ratio to the ion current ratio after the latter has been corrected for
kinetic gas theory mass discrimination at leak. Since the ion current ratio varied with time
from the moment of rst admission of the gas through the foil towards the ion source, the
observed ratio was extrapolated to zero time before differing isotope rates had distorted the
original isotopic composition of the sample. The evidence for the validity of this analysis was
four-fold (Gonantini et al 1997):
(1) The diffusion of the gas to the ion source is governed by the kinetic gas theory. The time
constants, , for diffusion are proportional to

M(
i
Si). The ratios of experimentally
determined values were in excellent agreement with theoretical values (table 14). The
agreement was rather gratifying (De Bi` evre and Valkiers 1994).
(2) The evolution of the values for repeat measurement cycles of the same sample provided a
quantitative measure of the elimination of so-called memory effects in the spectrometer.
(3) A correction factor K was determined which connected the measured ion current ratios
to the intended amount ratios of the Si isotopes. The factor K corrected for differences
in ionization probabilities of the isotopes, for differences in mass discrimination in the
inlet system and for differences in fragmentation of the SiF
4
isotopes in the ion source. A
residual K factor for the preparation of synthetic mixtures was close to unity. Moreover,
when independence of isotopic composition was assumed and the rst estimate of K was
applied to highly enriched isotope carrier compounds, a two-step re-iteration calculation
converged rapidly to a uniform factor K consistently applicable to all silicon samples of
different isotopic composition.
(4) Adsorption and desorption effects in the spectrometer inlet were investigated. The model
was based on the formation of a monolayer of adsorbed molecules, as proposed by
1982 P Becker
Table 14. Theoretical ratios compared with the observed ratios.
Kinetic gas theory Experiments
[M(
29
SiF
4
)/M(
28
SiF
4
]
0.5
1.004 80 (
29
SiF
4
)/(
28
SiF
4
) 1.004 62(12)
[M(
30
SiF
4
)/M(
29
SiF
4
]
0.5
1.004 75 (
30
SiF
4
)/(
29
SiF
4
) 1.004 42(10)
[M(
30
SiF
4
)/M(
28
SiF
4
]
0.5
1.009 57 (
30
SiF
4
)/(
28
SiF
4
) 1.009 11(14)
450
500
550
600
650
1 ppm
(radial distribution)
Shin-Etsu (Japan)
Wacker (Germany)
Wacker (Germany)
2
8
.
0
8
5
.
.
.

g

m
o
l
-
1
Axial position / cm
0 20 40 60 80 100 120 140 160 180 200
Figure 14. Molar mass values for selected materials; Shin-Etsu data taken from Fujii et al (1999)
and Wacker presented by Becker (2000).
Langmuir in 1918, and allowed information to be derived that enabled the selection of
optimal operational conditions. The parameters governingthe kinetics of gas effusionwere
derived from long mass spectrometric measurements up to 24 h where the gas ow was
reduced to less than 1% of the initial amount. Compared to the linear K extrapolation, the
consideration of the adsorption effect led to a silicon molar mass lower by about 1 10
6
(Gonantini 1996).
Compared with the large dimensions of the silicon crystal used for the measurement of
lattice parameter and density, the amount of material needed for the molar mass determination
is rather small: 50 mg only. The homogeneity of the material with respect to the isotopic
composition must, therefore, be checked. Due to their different origin, each crystal has its
own composition. In many crystals, a slight dependence of M of up to 1 10
6
on the axial
position was observed, see gure 14. Therefore, 1015 measurements were usually carried
out on samples collected in different sites of the silicon crystal in order to extrapolate with a
high degree of certainty the true molar mass at any site of the sample.
Results of molar mass determinations for the PTB crystal WASO 17 were improved in
the past 10 years, from 0.82 10
6
in 1989 to 0.13 10
6
. The nal result (De Bi` evre, et al
1995) for this specic sample was
M(Si)
WASO17
= (28.085 3842 0.000 0035) g mol
1
. (27)
To surpass the uncertainty attained, improvements of the mass spectrometer analysis (multi-
collector mode), the use of Si isotopes of higher enrichment and the development of an
Table 15. The molar mass M of the samples used in the international comparison measurements,
taken from De Bi` evre et al (2001). With the exception of samples VW3A (grown in vacuum) and
V2413BK (grown in an argon atmosphere of 1 bar), all samples have been cut from material grown
at approx. 3 bar argon pressure.
Molar mass
Institute Crystal code (g/mol)
PTB WASO 17 28.085 382(11)
WASO 04 28.085 521(11)
WASO 05 28.085 529(11)
VW3 28.085 335(11)
V2413BK 28.085 312(11)
Si2 (PTB) 28.085 283(11)
Si5 (PTB) 28.085 507(11)
Si7 (PTB) 28.085 318(11)
IMGC IMGC-MO 28.085 564(11)
IMGC-WG 28.085 379(11)
IMGC-W3 28.085 422(11)
IMGC-WP 28.085 421(11)
IMGC-CZ 28.085 421(11)
NRLM NRLM S3 28.085 284(11)
NRLM S1,S2 28.085 415(11)
NRLM S4,S5 28.085 583 85(520)
independent method for the determination of isotope abundances are needed. At PTB, a new
method for determining the isotopic composition and residual impurities derived from prompt
(n, ) spectra is being developed (Richter et al 1994, R ottger et al 1997). The sensitivity of
this method is well below the 10
8
level. Calibration of selected material against standards is
in progress, see section 5.6.
Table 15 shows the results based on the IRMM approach for selected samples. The data
spread, ranging from 28.085 283 g mol
1
to 28.085 584 g mol
1
, in part reects the natural
composition of silicon on Earth, showing a relative variation of 1 10
5
, by a factor of 100
larger than the measurement uncertainty required. In some cases, an axial gradient in molar
mass was measured, in particular in the Sin-Etsu crystal which was used by the NRLM for the
preparation of spheres S4 and S5. (The S4 and S5 spheres and the SH1 sample have been cut
from the same boule.) Along a part of the crystal 250 mm in length a gradient of 0.5 10
6
in the isotopic composition was measured. Similar observations could not be made in the
Wacker material. A possible explanation can be found in the different methods of CVD of
the compounds as mentioned in section 5.1. For Wacker samples, trichlorosilane, Cl
3
SiH,
was used which may not lead to an isotopic separation during the thermodiffusion process for
polycrystal preparation because of the innitesimally small mass difference of the different
isotopic molecules. If silane, SiH
4
, is used, the differences in the three molecular masses are
larger and can give rise to a mass separation effect. These ndings are still under investigation.
5.4. Density of silicon volume standards
In the early XRCDexperiments, the density of the silicon crystals was derived fromhydrostatic
weighings using water as a standard. Two main limitations to this method signalled that there
was a need for establishing newdensity standards. One has to do with the fact that a suspension
wire must penetrate the surface of the liquid and that water has a very high surface tension.
1984 P Becker
In addition, water carefully prepared for density measurements is fairly corrosive to some
materials, and its density is unstable with respect to the redissolution of atmospheric gases.
Uncertainties better than 5 10
6
could not be expected with water standards.
Highly accurate density measurementswithin the scope of the investigations discussed
hereare, therefore, performed either directly by determining the mass and volume of silicon
spheres and cubes of almost perfect geometrical shape, or they are traced back to established
volume or density standards. These standards serve to compare unknown specimens by
hydrostatic weighing or by the otation method, where an almost ideal shape is not necessary.
A suitable three-dimensional artefact, the volume of which can be accurately calculated,
is a sphere. Cubes and cylinders have sharp edges and corners that are susceptible to damage.
The mass of such a body should be comparable to the 1 kg prototype; so 1 kg silicon volume
standards are needed. As regards the uncertainties in target size, diameters of about 10 cm are
measured with subnanometre resolution. The surface quality of the bodies must, therefore,
be checked with the same accuracy. The ultimate roundness achievable on a 90 mm diameter
sphere made from single-crystal silicon depends largely on the mechanics of the grinding
and polishing processes. It is also necessary to have roundness and roughness measurement
capabilities to resolve and reliably characterize surface topography down to the nanometre
level. The best spheres deviate from ideal roundness by amounts in the order of 50 nm, their
surface roughness being about 0.5 nm (peak-to-valley). A residual asphericity is due to the
crystallographic directions of the crystal lattice, which have different degrees of hardness.
This can be avoided by using cubes, the surfaces of which have been cut parallel to the lattice
planes (Kunzmann 1991). Spheres and cubes made of Zerodur, steel and silicon are currently
used.
Two methods are at present applied in size measurements: mechanical probing using three
coordinate measuring techniques, and optical interferometric length measurement of diameters
may be combined with a large number of accurate mechanical roundness measurements. Last
reports show an overall relative uncertainty in the order of 1 10
7
and 3 10
8
(Fujii
et al 1995). In the case of the probing process the accuracy is limitedin contrast to pure
displacement measurementswhen a body is measured from two opposite sides. In this case,
the mean sources of systematic errors are
the phase jump at the air/object boundary layer, which must be known with sufcient
accuracy,
parasitic interferences in the case of transparent bodies and,
the uncertainty with which the probing ball diameter is known and attening of the ball
in the case of mechanical probing, leading to uncertainties of length measurements of
approx. 10 nm, in spite of reproducibilities of a few nanometres.
Additional sources of errors are the comparable contributions related to the body to be
measured, such as shape deviations (atness, roundness, etc), roughness and notches in the
edges. Today, the various laboratories state relative uncertainties of about 0.11 10
6
for
the volume of such standards.
Figure 15 shows a schematic diagram of the interferometer developed and used by
Saunders (1972) to measure the diameter of the silicon spheres. The sphere is placed in a
quartz etalon consisting of plates with either plane or spherical surfaces. A light beam from
a frequency-stabilized HeNe laser is divided into two beams pointing at opposite ends of
the interferometer. From the phase difference of the interfering beams, with and without the
sphere, the diameter can be determined. In order to t the wavefronts to the curvature of the
balls, two different modications are made: one uses light beams with a very small beam
diameter collimated by a lens so that concentric circular fringes are observed, or expanded
Figure 15. Principle of the optical interferometer used to measure the diameter of spheres.
light beams with spherical wavefronts in order to obtain simultaneously a topographical map
of many diameters.
Two methods available today are suitable for transferring the density of the three-
dimensional artefacts measured in absolute values in length and mass units from one sample
to another: a density comparison by means of hydrostatic weighing (Sacconi et al 1989) or,
in the case of silicon, oatation in a uid of the same density (Kozdon et al 1990, Kozdon and
Spieweck 1992).
Figure 16 shows a schematic drawing of a hydrostatic weighing system. A sample under
test is weighed by immersing it in a liquid of density
Fl
, and the buoyancy effect of the body
in the liquid, proportional to its volume, V, is measured from the apparent loss of mass. At
PTB and NRLM, FC 40 and tridecane (C
13
H
28
) were mostly used as a transfer liquid, whereas
at IMGC in most cases bidistilled water was used. The samples were weighed alternately
using a weight exchange mechanism. Arrangement of the samples between two standards on a
vertical lift system cancel the effect of the vertical density gradient introduced by temperature
and gravity gradients in the liquid (PTB, NRLM). At NIST and IMGC, the samples and
standards were arranged on a roundabout in order to verify a horizontal baseline.
Both, density and diameter measurements are inuenced by the real structure of the
surfaces. Between the Si-oxide layer that forms the boundary between the surrounding vacuum
or air andthe perfect siliconlattice inside the ball, there maybe several transitionlayers showing
various degrees of lattice distortion, from a totally destroyed lattice with a mosaic structure to
an elastically strained, almost perfect lattice. There are a large number of analytical methods
for investigating the surface structure: scanning tunnelling microscopy, ellipsometry, IRand x-
ray spectroscopy and reectometry, low-energy electron diffraction, etc. With a spectroscopic
ellipsometer, oxide layers with a thickness in the order of 5 nm are found on polished surfaces.
It is not yet known to what extent the polishing and grinding process inuences the layer
1986 P Becker
Figure 16. Hydrostatic weighing apparatus used at PTB for determination of silicon density; for
details see gure 26 in Bortfeld and Kramer (1992).
thickness. As already mentioned, the oxide layer also produces a phase retardation on the
reecting laser beam. In the case of silicon, this phase jump simulates a sphere diameter
which is smaller by some nanometres.
The masses of the silicon volume standards are compared with the national kilogramusing
the so-called prototype balances, set-ups with an extremely low measuring uncertainty level.
Weighing in air requires a buoyancy correction, and in vacuum the effect of water molecules
adsorbed on the sample surfaces remains to be studied. At present, a total uncertainty of
4 10
8
can be reached.
The NIST approach. The density was determined using precise steel spheres about 63 mm in
diameter as local temporary standards of density. Their mass was determined with reference
to the US national standard kilogram using single-pan, two-knife balances commercially
available. Results of mass comparisons among different laboratories performed in air indicated
systematic errors. Great emphasis was placed, therefore, on the air buoyancy correction which
was to make possible the equivalent to weighing in vacuum. The correction requires knowledge
of the density of air. Weights of different shape and density but with the same surface area
were fabricated for experimental investigations and compared. Another attempt at resolving
the probleminvolved the development of a newequation of state for moist air, containing terms
of the rst-order virial coefcients.
Volumes were desired from diameter measurements using optical interferometry inside
a FabryPerot etalon. The fringes were produced by radiation from an iodine-stabilized
HeNe laser whose wavelength was known with respect to that of a
86
Kr lamp which at that
time realized the unit of length. Data were obtained from measurements of the diameter of
interference fringes on the photographic lm, followed by least-squares tting to determine
the fringe fraction in the centre. These data were combined with the empty-etalon length L to
obtain the apparent sphere diameter D
D = L (d
L
+ d
R
). (28)
The empty etalon length was determined by three-colour interferometry and the integer parts
of d
L
and d
R
estimated from a mechanical measurement of D. The results obtained for ten
diameters were averaged with equal weight to obtain the mean diameter.
The phase shift problem in dimensional measurement. Recovery of a mechanical dimension
of the determination by an optical method as described above required that the difference
between the phase change of reection from the steel and that from the etalon quartz plate
be known. On the basis of ellipsometric measurements, shifts from quartz are customarily
assumed to be 180
whereas those from steel are assumed to range between 202
and 205
.
For a measurement uncertainty of 0.05 10
6
, the difference of about 23
must be known
within 1.8
. Departure from the 180
phase shift in the case of quartz was veried using

the Fresnel equation
r
01
=
n
0
N
1
n
0
+ N
1
(29)
where N
1
are the optical constants of quartz and n
0
is the refractive index of air. When the
complex refractive index of quartz is denoted by N
1
= n
1
ik
1
, the total phase retardation
on the reection at the quartz surface is given by
tan =
2n
0
k
1
n
2
0
n
2
1
k
2
1
. (29a)
It was shown that the phase shift differs negligibly from 180
.
The established density standards were compared with a group of silicon transfer standards
by hydrostatic weighing in uor carbon liquid. Finally, the densities of D
1
, D
2
, D
3
were
determined by reference to the silicon transfer standards. The results are given in table 16.
The observed densities had to be corrected for the presence of impurities, especially C and O,
in D
1
and D
2
.
When the results for the average molar mass M
0
in (27) and the density were combined,
it was found that
(M
0
/)
NBS
= (12.059 0427 0.000 0113) cm
3
mol
1
at 25
C (30)
was constant for all samples within the uncertainty stated. In 1999, considering the results
of comparison measurements with density standards of other metrology institutes, the NBS
data appeared to be incorrect. After removal of a former cleaning correction for the silicon
1988 P Becker
Table 16. Densities, statistical
m
and total measurement uncertainty
T
of the silicon samples
D
1
, D
2
, and D
3
.
Impurity conc. u
rel
Sample (10
16
cm
3
) Density (g cm
3
) (in 10
6
)
n
C
n
O

obs

m

T
D
1
3.9 6.0 2.328 991 7 2.328 991 0 0.22 0.48
D
2
3.9 6.0 2.328 990 6 2.328 989 9 0.44 0.62
D
3
0 0 2.329 000 3 2.392 000 3 0.94 1.04
Table 17. Densities at 20
C and 10
5
Pa of solid samples. g: results derived from mass and
diameter measurements, h: from hydrostatic comparison.
Volume Mass Density
Sample code (cm
3
) (g) (g cm
3
) Method
C1 394.700 65(19) 999.611 95(10) 2.532 586 47(36) g
C2 394.539 39(19) 999.211 22(10) 2.532 601 88(36) g
WASO 17.3 349.120 22(22) 813.128 76(12) 2.329 079 54(43) h
WASO 17.5 349.122 43(22) 813.133 86(12) 2.329 079 37(43) h
samples previously applied, a value for M/ was reached, which was by 1.64 10
6
lower
(Deslattes and Kessler 1999) than the previous one, which is in agreement with other data
recently published and compiled in table 22:
(M
0
/)
NIST
= (12.058 7895 0.000 0113) cm
3
mol
1
at 22.5
C. (31)
The PTB approach. For the determination of the density the method of hydrostatic comparison
with a standard of known density was used, similar to the NBS approach. Two cubes, C1 and
C2, made of Zerodur, with an approximate mass of 1 kg were prepared as standards. The
dimensions of the cubes were measured with a Tsugami interferometer and a displacement
comparator using mechanical probing. Details of these measurements were described by
Balhorn et al (1982), and nal results for the density are given in table 17.
Zerodur has a small expansion coefcient, and its density is close to that of silicon.
The surface properties of Zerodur are close to those of silicon, covered with a layer of SiO
x
,
x = 1, 2, 3 . . . . Ahydrostatic density measuring apparatus was constructed in order to achieve
a relative uncertaintyof less than10
7
. Fluorinert FC-40was used(surface tension: 16nNm
1
,
density: 1900 kg m
3
, compressibility: 1.310
9
Pa
1
, thermal expansion: 1.210
3
K
1
).
The solids were accurately positioned in height (1 mm). The temperature eld in the vessel
was monitored to 0.3 mK. Weighing was done with a Mettler constant load 1 kg balance
(HK1000MC) with a sensitivity of 1 g and a typical standard deviation for double substitution
weighing below 20 g.
The following corrections were applied to the results of the weighings.
Elimination of the mass of the empty suspension frame, calculation of the buoyancy of
air according to the BIPM density formula (Giacomo 1982), correction for density gradients
in FC-40, temperature gradients, dissolution of air in FC-40, correction for the liquid density
at the locus of Si samples, compensation of drifts in liquid density, temperature, pressure,
humidity of air, change of gravity with height, corrections for the impurity contents.
The result for the density of the silicon crystal at 22.5
C, 0 Pa was (Seyfried et al 1992)
Si
= (2329.032 05 0.001 70) kg m
3
. (32)
Table 18. Sources of uncertainty in the PTB density determination of the Zerodur standards.
u
r
Parameter (parts in 10
7
)
1 Relative uncertainty of mean density 5
2 Shrinkage of Zerodur 3
3 Nonlinearity in density gradient of buoyancy providing liquid (FC-40) 3
4 Random error 2
5 Uncertainty of built-in balance weights 1.5
Temperature
measurement
Barometer
(air pressure)
vertical movement
(hydrostatic pressure)
PRT
Thermostat
water bath
liquid mixture
teflon cage
lever to lock
sample
Si sample
stirrer
Figure 17. Schematic diagram of the PTB density comparator.
The uncertainty u
r
of about 0.7 10
6
was mainly due to the uncertainty of the Zerodur
standards, see table 18.
Extrapolation to pure silicon without impurities (22.50
C, 0 Pa) yielded
0,Si
= (2329.031 95 0.001 80) kg m
3
. (33)
With the molar mass reported in table 15 one obtains
(M/)
PTB
= (12.058 8224 0.000 0115) cm
3
mol
1
. (34)
For very precise silicon density comparisons, a oatation method was developed at PTB. The
experimental set-up is schematically shown in gure 17.
Two silicon samples with densities
s1
and
s2
were immersed in a liquid 1:2 mixture (of
1,2-dibromoethane and 1,2,3-tribromopropane) of nearly the same density,
f

s
. Then the
hydrostatic pressure (in previous measurements the temperature of the bath) was varied, rst
until sample 1 was freely oating,
f
(p
1
) =
s1
, and, secondly when sample 2 was freely
oating,
f
(p
2
) =
s2
. The state of free otation was observed with a CCD camera and a
monitor.
The temperature of the thermostated water bath and the pressure of the air were monitored
to take into account changes of the liquid density due to temperature or air pressure variations.
A lever was used to lock one sample while the other one was measured. The coefcient
f
/p was calibrated by measuring the density change
f
due to the pressure change
p compared with a density change
f
due to a temperature change t , where the thermal
expansion coefcient was known from hydrostatic weighings.
1990 P Becker
Table 19. Density of solid samples used at PTB. Si2, 5, 7 are silicon spheres used as national
density standards. Data reduced to 22.5
C and vacuum.
Density
Institute Crystal code (g cm
3
)
PTB WASO 17.3 2.329 031 9(18)
WASO 04 2.329 045 56(170)
WASO 05 2.329 045 48(170)
VW3 2.329 027 65(170)
V2413 2.329 027 23(170)
Si2 (PTB) 2.329 025 41(160)
Si5 (PTB) 2.329 043 48(160)
Si7 (PTB) 2.329 025 59(160)
The sensitivity of this comparison was well belowthe 10
8
level but limited by instabilities
of the equilibrium condition and instabilities in the density of the uid which was a mixture of
organic compounds. Results of density comparisons of selected PTB samples were discussed
by Seyfried et al (1987) and are given in table 19.
The development of a similar pressure-of-oatation apparatus is described by Waseda and
Fujii at NRLM. At present, a relative uncertainty of about 1 10
7
is achieved (Waseda and
Fujii 2001).
Oxide layer and phase shift problem. To the PTB measurements reported so far no corrections
for the natural oxide layer have been applied. A detailed characterization of the layer requires
in particular knowledge of the chemical composition of the layer in order to t the optical
constants of the material with sufcient accuracy. In this case, the natural oxide layer of the
WASO 04 sphere will be replaced by a thermally produced oxide. The chemical structure will
be characterized by the XPS method and the thickness of the layer will be calibrated on wafer
discs prepared in a similar way against the Si lattice spacing using an electron microscope of
atomic resolution (Danzebrink and G uttler 1999).
In order to avoid an increase in uncertainty due to transfer standards, other metrology
institutes prefer to determine the silicon density directly by measuring the mass and volume
of a 1 kg silicon sphere. Fabrication and sphericity measurements of the single-crystal silicon
spheres were rst carried out by Leistner and Zosi (1987) at CSIRO, Australia. The ultimate
roundness achievable for a sphere 90 mm in diameter largely depends on the mechanics of the
grinding and polishing processes. They were carried out in three basic steps:
(1) rough shaping using diamond tools and coarse, loose abrasives (silicon carbide);
(2) ne grinding with loose abrasives (usually aluminium oxide), down to 1 m;
(3) polishing using a matrix, such as pitch, with a suitable oxide slurry for nishing.
The roundness deviation is referred to the centre of the tted least-squares sphere (LSS). The
character of the error surface strongly reects the cubic structure of the silicon crystal, with
peaks often associated with the 111 crystal axis and valleys associated with the 100 crystal
axis. Using optical ellipsometry, the oxide layer was measured to be 10 and 7 nm in the 111
and 100 orientations, respectively (Collins et al 1997).
Sphericity is determined from 3D data sets of 2D roundness proles measured on
regularly sampled great circles with a standard uncertainty below 3 nm. Computer-animated
visualizations of the sphericity error surface are used to enhance its topography, resulting in
very clear views of the cubic symmetries arising fromthe fabrication processes and the physical
crystal properties. After polishing, the sphere errors based on a tted LSS are reduced to less
than 30 nm. The volume of such nearly perfect spheres can be calculated accurately fromthe
means of a certain number of diameters distributed nearly uniformly over all directions. For a
new generation of spheres made from WASO 04, the oxide layer thickness was minimized by
application of careful polishing techniques, and a signicant dependence on orientation was
no longer observed (Leistner 2000).
The NRLM/IMGC/CSIRO approach. Modied Saunders interferometers were used at IMGC,
NRLMand CSIRO. At IMGC(Sacconi et al 1995) all diameter measurements were performed
in air, at NRLM(Fujii et al 1993) the spheres were measured in vacuum, and at CSIRO(Kenny
et al 2001) in an helium environment at 5 kPa in order to avoid the inuence of atmospheric
pressure and air composition on the optical wavelength. The shape error contribution was
checked at IMGC by additional roundness measurements using mechanical proler data,
whereas at NRLMand CSIROthe shape was derived optically by measuring up to 70 diameters
as a function of the spherical coordinates and . The spheres were supported at three points
on a cone of a horizontal goniometer for automatic azimuthal orientation and could be tilted
automatically by a remote-controlled mechanism. NRLM introduced a high-precision phase
reading method by scanning the etalon normal to the surface in order to read d
L
and d
R
(equation (28)), and also, by using intensity modulation by acousto-optical modulation. The
integer number of the interference fringes, initially predicted by mechanical probing, was
nally determined by combining two interferometers, using HeNe and HeCd lasers. In the
CSIROsetup, the laser source was tunable between 630 and 640 nmand stabilized to absorption
lines at 633 and 640 nm in molecular iodine. The fringe fractions of each gap and of the etalon
were measured by phase shift interferometry.
Investigations have shown that an exactly spherical shape is not a fundamental requirement
for the volume determination, since this can be precisely calculated from dimensional
measurements in several ways. A rst technique is based on the expansion of the diameter,
D(, ), in spherical harmonics (Mana 1994):
D(, ) =
q
n=0
n
m=0
(A
nm
cos m
i
+ B
nm
sin m
i
) P
m
n
(cos
i
) (35)
where A
nm
and B
nm
are amplitudes of each spherical harmonic of degree n and order m,
i
and
i
are polar and azimuthal angles, P
m
n
is the associated Legendre function, and q is the
maximum degree of spherical harmonics. The volume is then given by the series
V =
4
3
A
3
00
_
1 + 3
n=1
n
m=n
A
nm
A
00
2
+
_
(36)
where A
nm
is the amplitude of the spherical harmonic, Y
m
n
(, ). The coefcients A
nm
can be
evaluated by numerical integration or least-squares tting. However, in the case of a nearly
perfect geometry, an accurate value of V can be obtained from the diameter A
00
:
V =
4
3
A
3
00
, (37)
an evaluation used by NRLM and IMGC.
Johnson (1974) from NBS proposed a second technique where the volume of an
approximate sphere could be accurately derived in terms of measured breadths, the distance
between parallel planes tangent to opposite sides. A set of ten breadths was taken by the
CSIRO group at the apex points of an icosahedron to obtain an mean value for the diameter.
A third approach is based on the application of the B-spline functions to a three-
dimensional object (Gardini and Mana 1998).
The surface of the spheres have an oxide layer several nanometres thick. This thickness is
greater than that of the native oxide layer typically observed on semiconductor silicon, and it
1992 P Becker
is dependent on the polishing technique used. It is essential to characterize the layer, including
impurities and chemical composition because of its effect on density and on the optical phase
jump. Cleaning procedures, too, inuence the layer thickness. A typical decrease by 0.5
0.7 nm was observed. Main impurities are hydrocarbons introduced by the vacuum pumping
system of the interferometer chamber (Kenny 2000).
Oxide layer and phase shift. Fujii et al (1999) developed a model for the structure near the
surface of the silicon spheres covered by an oxide layer of thickness h, according to the NBS
ansatz of equation (29). For the chemical composition of the layer, a homogeneous distribution
of SiO
2
with a refractive index of n
1
= 1.46 was assumed. For silicon, the complex refractive
index was denoted by N
2
= n
2
ik
2
. From Fresnel equations, a departure from was
derived:
= tan
1
_
|r
12
| (1 r
2
01
) sin(
12
2)
r
01
(1 + |r
12
|
2
) + |r
12
|(1 + r
2
01
) cos(
12
2)
_
(38)
r
01
being the reection coefcient at the interface between vacuum and oxide layer, r
12
=
|r
12
|e
i
12
the reection coefcient at the interface between oxide layer and the silicon bulk,
= 2hn
1
/
0
the phase factor including the multiple reection effect in the layer, and
0
the
wavelength in vacuum.
To calculate , the thickness h was measured by an ellipsometer. Instead of measuring the
angle of incidence , the wavelength was varied between 400 and 650 nm, and both, h and ,
were calculated by a least-squares method with the input parameters
0
= 633 nm, refractive
indices of vacuum n
0
= 1 and of the oxide layer n
1
= 1.46; complex refractive index of Si N
2
with n
2
= 3.88, and k
2
= 0.019.
Measurements from 50 directions have shown that the thickness h is (5.170.58) nm for
the sphere S5. When the diameter is measured with a 633 nm wavelength, the phase delay
on reection is (0.0156 0.0016) nm for S5. This means that the real diameter of sphere S5
is by (9.84 1.07) nm larger than the observed one. On the assumption that the density of the
layer is close to that of Si, the density of the Si sphere was determined from mass and volume,
including the oxide layer.
Results. Table 20 shows the main contributions to the error budgets for the working standards
as published by the individual laboratories (Basile et al 1995). Deformations of the spheres
due to gravity as a function of crystal orientation and support devices were investigated by
nite-element structural analysis. It turned out that the gravity inuence can be neglected.
It can be seen that the total uncertainties are dominated by incorrect knowledge of the
refractive index of the air, by the measurement of temperature in absolute units and by
insufcient characterization of the surface parameters. A signicant reduction of the overall
uncertainty can be achieved by measuring the volume in vacuum, by improving the temperature
measurement and by a better analysis of the surface layer.
Table 21 gives a survey of volume and mass measurements of selected standard spheres.
The volumes of spheres Si3 (IMGC) and S1 (NRLM) were measured between 1993 and 1995
and reduced to 20
C and 101 325 Pa. The data of S4 (IMGC) and WASO 04 (CSIRO),
measured in 1999, were reduced to 22.5
C and 0 Pa, without impurity corrections. Density

data derived from mass and volume were corrected for inuences due to surface layers and
impurities.
Table 22 shows density determinations derived fromcomparisons made either by oatation
(f) or by hydrostatic (h) means. IMGC sample W3 and sphere Si3 were cut from the same
crystal ingot. All data have been reduced to 22.5
C, 0 bar and C, O 0. The density of the

samples listed in tables 19, 21, and 22 were routinely measured in several intercomparisons to
Table 20. Uncertainty budget of the density determination, in parts in 10
8
.
u
r
NRLM u
r
IMGC u
r
CSIRO
Parameter (S4) (Si3) (WASO 04)
Volume
Statistical error 7 7.8
Of-roundness
Wavelength 2.4 0.96
Refractive index of air (vacuum) 2.7
Temperature 4 9.0
Oxide layer 3.4 6.0 3.4
Thermal expansion of sphere 0.6
Thermal expansion of etalon 0.2
Fresnel phase shift 0.1
Alignment interferometer 0.02 3.9
Combined u
r
9 14 10
Mass
Repeatability 0.8
Mass standards 1.3
Density of air 4.1
Combined u
r
6 4.4 7.5
Impurities 0 0.5
Total density 11 15 12.5
Table 21. Results of volume and mass measurements of silicon 1 kg spheres at IMGC, NRLM,
and CSIRO.
Volume (cm
3
) Mass (g) Density
Institute Crystal code 429 + 1000 + (g cm
3
)
IMGC Si3 0.647 784(56) 0.685 892(44) 2.329 083 50(36)
NRLM S1 1.527 578(146) 2.734 69(4) 2.329 083 2(8)
S4 0.609 966(39) 0.578 90(6) 2.329 040 13(25)
CSIRO WASO 04 0.838 826(45) 1.132 893(75) 2.329 044 364(302)
Table 22. Results of density comparisons of crystals used at the IMGC, reduced to 22.5
C and
vacuum, N
C
and N
O
0.
Density
Institute Crystal code (g cm
3
)
IMGC MO 2.329 047 5(9)
f
WG 2.329 032 3(7)
f
CZ 2.329 035 5(8)
h
WP 2.329 033 8(4)
h
W3 2.329 036 1(4)
know the state of mutual compatibility and to prove the accuracy and stability of these density
standards. The results showed agreement among the partner institutes in relative uncertainties
for mass, volume and density well below the 10
7
level.
1994 P Becker
Table 23. Data of the silicon molar volume of samples used for the recommended N
A
value, see
gure 18.
Molar volume Rel. uncertainty
Institute Crystal code (cm
3
/mol) u
r
[parts in 10
7
]
PTB WASO 17 12.058 822 4 8.7
WASO 04 12.058 811 3 8.3
WASO 05 12.058 815 2 8.3
VW3 12.058 824 2 8.3
V2413 12.058 816 5 8.3
Si2 (PTB) 12.058 813 5 7.9
Si5 (PTB) 12.058 816 1 7.9
Si7 (PTB) 12.058 827 6 7.9
IMGC IMGC- MO 12.058 819 5 5.4
IMGC-WG 12.058 818 8 4.9
IMGC-W3 12.058 832 1 4.2
IMGC-WP 12.058 829 3 4.3
IMGC-CZ 12.058 820 8 5.2
NRLM NRLM S3 12.058 825 6 5.3
NRLM S1 12.058 820 4 4.7
5.5. Summary of N
A
results
Within the framework of the CPEM 2000 conference, all data available from the past 25 years
were re-evaluated and combined to a value recommended for the Avogadro constant (De Bi` evre
et al 2001). The molar volume of the samples on which the recommendation is based are
listed in table 23. The density data have been derived from absolute determinations of mass
and volume of silicon artefacts or deduced by comparison in a hydrostated or in a oatation
equipment as described above. The molar mass data have been taken from table 15.
The molar volumes derived from the above 15 samples differ within 4.5 10
7
(relative
standard deviation). Newmeasurement results of the NRLMderived froma different Shin-Etsu
material (S1 in table 21) have been included which prove that crystals from Wacker, Shin-Etsu
and other companies have the same characteristics.
The value derived from the slope of the function M
Si
= f () as shown in gure 18 leads
to what can be considered our best knowledge of the molar volume in single-crystal silicon,
namely,
M
Si
/ = 12.058 8207(54) cm
3
mol
1
. (39)
The combination of this value with the CODATAvalue of the Si lattice parameter recommended
in 1998 (Mohr and Taylor 2001), which takes into account the complete knowledge about this
quantity as discussed in section 5, i.e.
d
220
= 192 015.5845(56) fm(22.5
C, vacuum) (40)
leads to an Avogadro constant
N
A
= 6.022 1339(27) 10
23
mol
1
, (41)
a candidate for consideration in future adjustments of the values of the fundamental constants
by CODATAput forward by the Working Group on the Avogadro constant (Becker, Chairman)
of the Consultative Committee for Mass and Related Quantities (CCM) of the International
Committee for Weights andMeasures (Becker 2001). This value deviates bymore than110
6
2,329020 2,329025 2,329030 2,329035 2,329040 2,329045 2,329050
28,08525
28,08530
28,08535
28,08540
28,08545
28,08550
28,08555
28,08560
M
o
l
a
r

m
a
s
s

[
g
/
m
o
l
]
Density [g/cm
3
]
Figure 18. Molar mass versus density of Si single-crystal samples. The result for the molar volume
derived from the linear data t is M
Si
/ = 12.058 8207(54) cm
3
mol
1
. (This gure has been
taken from De Bi` evre et al (2001) and includes three data points from NRLM, ve from IMGC
and eight from PTB.)
Table 24. Data of crystals not included in the recommended table (22.5
C, 0 bar).
Molar mass Density
Institute Crystal code (g/mol) (g cm
3
)
PTB WASO 04 28.085 521(11) 2.329 045 56(170)
CSIRO WASO 04 28.085 521(11) 2.329 044 36(30)
NBS/NIST D
2
28.085 379(18) 2.328 990 6(23)
NRLM S4; S5 28.085 583 85(520) 2.329 040 51(25)
(relative value) from the CODATA value for N
A
recommended in 1998, which is based on
Plancks constant as determined above all by watt balance experiments.
Data not included are summarized in table 24 and compared with data derived from the
WASO 04 sample. The corrected NBS/NIST value and the recently published new CSIRO
data, too, are in agreement with the recommended value.
An important result that remains to be discussed is the molar volume deviation
(M
Si
/)/(M
Si
/) = 3.2 10
6
in one particular crystal (SH1 in table 12 and S4 in ta-
ble 21) from the mean value, which has led to intensive investigations into the perfection of
that particular sample (Deslattes et al 1999b, Tuomi et al 2001, Nakayama et al 2001). Since
the Conference on Precision Electromagnetic Measurements (CPEM) in Boulder in 1994, the
unexpected discrepancy in the molar volume value observed in this Si single-crystal has ham-
pered the progress of the x-ray crystal density (XRCD) route to a newdenition of the kilogram.
In conclusion, the following can be stated: rst, no measurement errors were found in
the measurement procedures to explain the discrepant result. Sample density and volume
standards of PTB, IMGC and NRLM were checked in an international comparison and found
1996 P Becker
to be in very good agreement. Fully consistent results for the differences in the molar mass
of all samples were obtained by two independent measurement techniques applied at IRMM
and IMR (Institute of Mineral Resources in Beijing). Samples from the WASO 17.2 crystal
were re-measured at IRMM, too, to conrm the absolute scale. According to our present
knowledge, in situ crystal imperfections such as nano-voids may be responsible for the smaller
molar volume of the NRLMsample, but the existence of such voids or nano-voids in the sample
has not yet been conrmed.
Secondly, all other re-measurements have conrmed the 1986 CODATA value
recommended for the Avogadro constant, which was derived from measurements on silicon
similar to those described here, and in no experiment could an inconsistency similar to that of
the only offending sample be detected.
The recommendation of the Working Group, therefore, is not to include the result obtained
for the discrepant NRLM samples, S4 and S5, in the statistical analysis of data concerning the
Avogadro constant unless the reason for the anomaly in the molar volume is understood. In
the early XRCD research projects, not enough effort was devoted to the investigation of the
characteristics of single-crystal siliconandthe selectionof suitable samples tomeet the required
metrological specications. It is, therefore, necessary to continue theoretical and experimental
work in order to increase the understanding of crystal growth and the mechanisms of defect
formation.
Clearly, the growth process plays an important role when silicon material is selected for
a precise determination of the Avogadro constant. A check list might be useful: is the growth
process of the crystal, including the CVD process, known? Was there any treatment of the
material after growth? The members of the Avogadro Working Group still believe in the
usefulness of the crystal approach which represents a direct route to a new denition of the
kilogram. They furthermore think that the cause of the inconsistency in the molar volume is
attributable to the existence of small holes in that particular material.
5.6. New developments
Newdevelopments are necessary to go beyond the experimental bounds which can bar the way
chosen to arrive at a new denition of the kilogram, such as the determination of the volume
of silicon spheres and, in particular, of the isotopic composition of silicon.
Material: enriched silicon isotopes. At PTB an attempt was made to overcome the problems
resulting from the isotopic composition by using enriched silicon single crystals. The degree
of enrichment required for the application of the XRCD method to silicon containing mainly
the isotope
28
Si, can be derived from equation (25):
M(Si) = M
28
_
1 +
M
29
M
28
M
28
f
29
+
M
30
M
28
M
28
f
30
_
(42)
M
28
{1 + }, (43)
on the assumption that f
29
f
30
:
= 3
1 f
29
2M
28
. (44)
If the uncertainty aimed for in the determination of the Avogadro constant is 1 10
8
and the
inuence of the isotopic composition is to be eliminated, the isotopic purity of the
28
Si should
be 99.9998%.
Takyu et al reported in 1999 the growth and characterization of an isotopically enriched
28
Si single crystal with an enrichment of 99.924% of
28
Si. Separation was carried out by
the gas centrifuge technique and crystal growth by the oating-zone method. At PTB, lattice
parameter, density, and molar mass of an isotopically highly enriched silicon-28 crystal were
investigated. The goal was to obtain an independent value of the Avogadro constant, of an
accuracy equal or superior to the currently best values obtained from similar measurements of
very pure and highly perfect silicon single crystals of natural isotopic composition.
A rst crystal, 215 mm in length and 30 mm in diameter, with an 2 10
3
at.% content
of boron, was described by Becker et al (1995b). A second crystal cylinder, 4 50 mm
2
, with
aluminium impurities in the range of 1 10
3
at.% has been reported recently by Bulanov
et al (2000). Within the scope of an international cooperation initiated by PTB, a third crystal
in vacuum with high crystal perfection was grown.
(1) About 1284 g of
28
SiO
2
grains have been converted to a single crystal in collaboration
with the Wacker-Chemitronic company. The following technical and chemical processes
were selected:
Reduction of SiO
2
to Si with high-purity aluminium powder at 1100
C in a closed
system: 3SiO
2
+ 4Al 3Si + 2Al
2
O
3
.
Separation of the two products using a chemical gas transport reaction in the presence
of Te.
Growth of a single crystal from the
28
Si melt in a quartz crucible. A small natural Si
crystal was used as a seed crystal. For further renement, the CZ crystal was melted
and grown again, but now with an enriched seed crystal.
In a nal step, the crystal was FZ-rened.
(2) For the growth of the second crystal a crucible-free pre-growth procedure was employed
commonly used for the growth of high T
c
oxide superconductors. SiF
4
was converted to
SiO
2
, and the process then followed the above-described procedure. The
28
Si powder was
pressed at 3000 kg m
2
and sintered at 1200
C in pure argon. In a nal step, the material

was FZ-grown.
(3) The highly pure SiF
4
gas was enriched using the centrifuge method. On its basis, poly-
crystalline
28
Si was obtained. Two charges were converted to crystalline silicon by the
CZ method, followed by multiple FZ renements.
The rst attempt failed because the crystal was found to contain a residual boron concentra-
tion of 1.610
18
cm
3
, clearly too high to be called semiconductor grade, and the enrichment
turned out to be 99.02%too low for the improvement of the standard uncertainty. For the
second and third attempts, a newproject was initiated under the leadership of VITCONproject
consulting, Jena, Germany, in collaboration with several Russian atomic research institutes to
improve the observed insufciencies. In the third step, two small enriched crystals about 10 g
in mass were grown, one by the CZ method followed by FZ renement in argon atmosphere,
the second by multiple FZ renement in vacuum. The isotopic enrichment was 99.8588 and
99.872
28
Si, respectively. A next step will cover the preparation of an almost perfect
28
Si crys-
tal, 10 g in mass and of 99.99%enrichment. The nal goal of the project is the growth of a
28
Si
crystal in kilogram dimensions, which is suitable for the determination of the Avogadro con-
stant as well as for application as monochromator material in synchrotron x-ray experiments
and for investigations aimed at reducing the thermal heat load in semiconductor devices.
Molar mass: prompt n/ -spectroscopy. Prompt -ray spectroscopy after thermal neutron
capture is a method suited to detect all isotopes in any sample. In one method the sample is
activated for a dened time in a high neutron ux with energies up to 8 MeV near a reactor
core, followed by an off-line measurement. In contrast prompt (n, )-spectroscopy is an on-
line method with a much lower neutron ux (for example at the end of a neutron guide tube)
1998 P Becker
Figure 19. Schematic view of the spherical Fizeau interferometer for diameter determinations of
spheres at PTB.
and with thermal neutrons (E
n
25 meV), thereby excluding any kind of resonant captures.
During the experiment the sample is exposed to the thermal neutron beam of known ux
density. The -rays are detected by a couple of large high-purity germanium detectors at a
well-dened solid angle and are analysed by ultra-high-rate electronics with sampling ADCs.
The -ray energy ranges up to 12 MeV. It is used to identify all nuclides and to determine
atomic mass differences.
In rst experiments the dominant energies and transition probabilities of the
28
Si(n, )
29
Si
reaction were measured and compared with data published by Kennett et al (1986) and Raman
et al in 1992. In most cases the uncertainty could be improved. Direct comparisons of silicon
crystals (S1, S5 and Si2) showed within the uncertainty of 7 10
5
reached so far, that their
molar masses are the same. With the data for the transition probabilities and the capture cross
sections included, the molar mass of a sample of enriched silicon
28
Si was determined for the
rst time with an uncertainty of 110
4
. Moreover, atomic mass differences of some isotopes,
including the stable silicon isotopes, could be measured with an uncertainty of about 10
9
(Paul
et al 2001). The method was developed into a measuring arrangement set up at the Institut
LaueLangevin (Grenoble, France) for the non-destructive qualitative and quantitative analysis
of the nuclear composition of any sample. Further investigations attributed to calibration with
different enriched samples will be continued at the neutron facilities in Geesthacht, Germany.
Density: Fizeau interferometry. A new spherical Fizeau interferometer (gure 19) that allows
the interference pattern to be evaluated by phase-stepping interferometry has been developed.
This technique is based on a special algorithm for Fizeau interferences and requires four phase
steps of one quarter of an interference order, which are achieved by frequency tuning over a
range of 12 GHz. The laser frequency can be calibrated with a measurement uncertainty of a
few 100 kHz at any measurement position. The interferometers eld of view covers an angle
of about 60
imaged onto an electronic camera with about 512512 pixels so that the variation
of the diameter is measured with high angular resolution. For the measurement, the sphere rests
on a three-point support. The sphere can be lifted and rotated about two perpendicular axes
by means of a motor-driven manipulation device so that it can be positioned in well-dened
orientations (Nicolaus and B onsch 1997).
Two measurements are necessary, the rst with the empty etalon, a spherical Fizeau
interferometer with a spacing of about 151 mm. Measurements are possible from both sides,
one at a time, with the other beam interrupted. In the case of equal optical path lengths,
both results must agree perfectly. First investigations show agreements within 1 nm. With the
second measurement, with the sphere placed inside, one gets two newsystems of interferences:
Fizeau interferences between the surface of the sphere and the corresponding reference surface
Table 25. An abbreviated list of the CODATA recommended values of the fundamental constants
of physics and chemistry based on the 1998 adjustment.
Rel. std.
Symbol Numerical value Unit uncert. u
r
e 1.602 176 462(63) 10
19
C 3.9 10
8
m
e
9.109 381 88(72) 10
31
kg 7.9 10
8
h 6.626 068 76(52) 10
34
J s 7.8 10
8
c 299 792 458 m s
1
exact
N
A
6.022 141 99(47) 10
23
mol
1
7.9 10
8
m
p
1.672 621 58(13) 10
27
kg 7.9 10
8
k 1.380 650 3(24) 10
23
J K
1
1.7 10
6
G 6.673(10) 10
11
m
3
kg
1
s
2
1.5 10
3
7.297 352 533(27) 10
3
3.7 10
9
of the Fizeau lens. For the temperature measurement, an mK-measuring technique has been
developed with a well calibrated Pt-25 reference thermometer and pairs of thermocouples
serving as a bridge between Pt-25 and the silicon sphere. Test experiments on a black glass
sphere show that measurement uncertainties at nanometre level can be reached (B onsch and
Nicolaus 1998).
6. Indirect determinations of the Avogadro constant from measurements of
fundamental physical constants
The measurement uncertainty achieved in the direct determination of the Avogadro constant
described here is probably limited by problems associated with the preparation of a silicon
crystal. A value of that constant determined on the basis of an analysis of the consistency of
all data available for the physical constants will certainly be affected by a signicantly lower
uncertainty. This indirect value is based primarily on the values of the Rydberg constant R
,
the ne structure constant , and the Plancks constant h, which were given by Taylor (1994);
an analysis of recent data was prepared by Cohen in 1997.
The group of constants that are conventionally known as the fundamental physical
constants includes the elementary charge e, the electron mass m
e
, Plancks constant h, the
velocity of electromagnetic radiation c, the Avogadro constant N
A
, and the proton mass m
p
.
The addition of another two constants, the Boltzmann constant k and the universal gravitational
constant G, leads to the larger group known as the group of fundamental constants of physics,
see table 25.
The expressions to be used for calculating indirect values of N
A
are derived as follows:
the molar Planck constant, N
A
h, is found from the expression for the Rydberg constant R
:
R
= m
e
c
2
/2h =
M
p
c
2
2(m
p
/m
e
)N
A
h
. (45)
Using the values recommended by CODATA 1998, including the proton molar mass,
M
p
= N
A
m
p
(46)
one nds N
A
h = 3.990 312 689(30) 10
10
J s mol
1
, u
r
= 7.6 10
9
.
In this the uncertainty in N
A
is linked to the measurement uncertainty of h.
Equation (45) can be rewritten as follows:
N
A
=

0
c
2
M
p
(2e/h)
2
16R
(m
p
/m
e
)
(47)
2000 P Becker
where
0
is the permeability of vacuum. There are a number of ways of measuring h or 2e/h
in SI units. Nearly all depend on the Josephson and/or quantum Hall effects (JE and QHE,
respectively). The JE with the relation 2e/h = K
J
, the Josephson constant, provides the basis
for measuring an electrical potential in terms of a frequency, and it allows a volt standard to
be maintained in terms of a nominal frequency by dening
K
J
= 2e/h 483 597.898(19) GHz V
1
90
(48)
where V
90
is a conventional unit of voltage. In a similar way, the QHE has provided a standard
realization of the ohm using the denition of the quantum Hall resistance R
K
:
R
K
= h/e
2
25 812.807 572(95) . (49)
On January 1, 1990, conventional values of K
J
and R
K
were adopted for practical use:
K
J-90
= 483 597.9 GHz V
1
exactly (50)
and
R
K-90
= 25 812.807 exactly. (51)
From this, a value for the Avogadro constant based on the international realizations of the ohm
and the volt can be derived:
N
A
=
M
p
c
2
K
2
J-90
R
K-90
32R
(m
p
/m
e
)
. (52)
(1) Faraday constant. The Faraday constant F = N
A
e provides a value of N
A
if one has an
independent value for e. Use of equation (50) and (51) leads to
N
A
=
1
2
R
K
K
J
F. (53)
(2) Proton gyromagnetic ratio. The proton has a magnetic moment
p
and an angular
momentum J
p
, and consequently, in a magnetic ux density B, the gyromagnetic ratio of
the spin-ip angular frequency
p
to B is
p
=
p
/B. The gyromagnetic ratio can be
determined by measuring the proton precession frequency. The experimental conditions are
taken into account by introducing an effective resonant frequency
p
:
p
=
p
/B. The
momentum
p
can be expressed as a multiple of the nuclear magnetron,
N
= eh/4m
p
, or
of the Bohr magnetron,
B
= eh/4m
e
. The so-called low-eld evaluation of
p
measures the
ux density B produced by a known current in a solenoid, whereas the high-eld evaluation
measured the mechanical force on the solenoid due to B, produced by an electromagnet. The
gyromagnetic ratio is closely related to the Faraday constant F:
p
=
N
F
M
p
(54)
and thus
N
A
=
K
J
R
K
M
p
p
2(
p
/
g
)(m
p
/m
e
)
. (55)
Equation (54) can be expressed as
2
p
=
p
(hi)
p
(lo). (56)
From this, N
A
can be derived as
N
A
=
p
(hi)
p
(lo)
0
R
M
p
3
(
p
/
B
)
2
(m
p
/m
e
)
. (57)
Determination of h:
Table 26. Determinations of the Avogadro constant by different methods.
N
A
Source 10
23
mol
1
Ref. u
r
10
6
1 XRCD 6.022 133 9 0.46
2 F, NIST 6.022 144 5 1.33
3
p
(hi), NPL 6.022 136 0 1.01
4
p
, NIM 6.022 144 0 1.71
5 K
J
, CSIRO, NML 6.022 142 3 0.54
6 K
J
, PTB 6.022 141 7 0.54
7 h (watt balance, NIST) 6.022 141 85 0.087
8 h (watt balance, NPL) 6.022 142 3 0.2
9 CODATA 1986 6.022 136 7 0.59
10 CODATA 1998 6.022 141 99 0.078
(a) Watt balance. Consider an electrical conductor carrying a current in a magnetic ux
density. The force of the conductor can be measured by balancing it against the
gravitational force actingona mass. The experiment is carriedout intwosteps: (1) Ina rst
step (force mode) the attracting electro-magnetic force between two coils is compensated
by the gravitational force. In a second step (velocity mode) the coils will be moved with
respect to one another with constant velocity v causing an induced voltage U. Then h can
be derived from
h =
4
K
2
J
R
K
=
4{mgv}
SI
K
2
J-90
R
K-90
{U I}
90
(58)
{}
90
denotes that the quantities have to be measured using JE and QHE.
(b) h/mmeasurements. In the case of neutrons, the quotient h/m
n
was measured with an
accuracy of 8 10
7
by diffracting neutrons from a silicon crystal. A second experiment
is based on photon recoil using laser-cooled Cs atoms and atomic interferometry with a
reported uncertainty of 1 10
7
.
The values of N
A
derived indirectly from other constants are compiled in table 26. The input
data were compiled in 1997 within the framework of the CODATA1998 adjustment and differ,
therefore, slightly from those published.
The data, comparedgraphicallyingure 20, canbe dividedintwogroups. The rst groupis
in good agreement with the 1998 CODATAvalue which is based on the watt balance approach;
the other group agrees well with the former 1986 CODATA value (Cohen and Taylor 1987).
Compared with the 1986 adjustment, the values recommended in 1998 are evaluated
mainly on the basis of three new results, a value of the ne-structure constant (from the
electron-magnetic moment anomaly), of the Planck constant h (from the moving-coil watt
balance experiment) and of the molar gas constant R (from the speed of sound in argon). The
data that will contribute most to the indirect value of N
A
are electrical data. A systematic error
in these data not yet detected cannot be excluded (Taylor 2000).
7. Spin-offs in the eld of metrology and solid state physics
Material and measurement methods used for the determination of the Avogadro constant were
selected within the scope of investigations aimed at replacing the kilogram artefact. The
desired ultra-high relative accuracy of the order of 1 10
8
has made it necessary to improve
and develop techniques with sensitivities and accuracies to the highest technical realizable
2002 P Becker
6,02212 6,02213 6,02214 6,02215 6,02216
CODATA 1998
CODATA 1986
h (Watt bal.), NPL
h (Watt bal.), NIST
K
J
, PTB
K
J
, CSIRO, NML
p
', NIM
p
'(hi), NPL
F, NIST
XRCD
S
o
u
r
c
e
N
A
[10
23
mol
-1
]
Figure 20. Graphical comparison of the indirect derived values of N
A
with one another and with
the values recommended in 1986 and 1998 and the recommended XRCD N
A
value.
level. The rst problem, the growth of silicon crystals of the required quality, in the present
state is related to the exact knowledge of the actual number of self-point defects in the silicon
samples. For this purpose, single siliconcrystals were grownunder different growthconditions,
and a variety of experimental methods were applied in order to investigate the silicon vacancy
defect concentration and to check theoretical predictions. Positron annihilation spectroscopy
at the University of HalleWittenberg has been improved in order to reduce the measurement
uncertainty. For FZ-silicon of high chemical purity an average lifetime of (216.5 0.2) ps
could be found. Thus, an upper limit of 3 10
15
cm
3
for the vacancy-type concentration can
be estimated, corresponding to a maximal density change by 0.0610
6
. These results were
conrmed by simulation of grown-in voids and have widely been accepted. The investigations
are directly related to the search for a better quality of silicon required for higher integrated
electronic devices.
X-ray interferometry and the silicon machining required for it, have been successfully
introduced in the eld of nanometrology. Special devices have been developed which, in the
so-called Angstrom ruler, use the silicon lattice spacing as a unit of length for measurements
and calibrations with subnanometre resolution. Two applications are: The operation of a
combination of an optical interferometer with an x-ray interferometer, where the latter acts
as a subdivider of the optical orders (Basile et al 2000, Yacoot and Downs 2000), and
the combination of an x-ray interferometer with a scanning tunnelling microscope for the
calibration of holographic diffraction gratings for dimensional metrology (Wang et al 2000).
The acquired expertise in measurement instrumentation and measurement procedures
for determinations of Si isotope amount ratios can be extended to more general use in
measurements of isotope amount ratios, i.e. in other elements. It can also be combined
with isotope dilution. The latter combination opens up the possibility of realizing direct
traceability of an amount-of-substance measurement procedure and instrumentation leading
to the Avogadro constant. This opens the way to develop traceability to the mole, i.e. to the
SI (De Bi` evre et al 1998).
Within the framework of the determination of the Avogadro constant it becomes obvious
that the silicon density could be used as a standard in the wider eld of metrology. Before
the silicon investigations were carried out, only water ( 1 g cm
3
) and mercury
( 13.5 g cm
3
) served as density standards. Silicon offered an opportunity to use its
density as an intermediate value, and to raise the stated relative uncertainties from a level of
10
5
to the 10
7
level.
During the long years of work on silicon spheres a high stability and reproducibility in
density with time was found. This observation implies that, in contrast to the kilogram artefact
at S` evres, the silicon sphere has a stable crystallographic state and a stable surface layer, and
that there is no chemical reaction with the environment. Therefore, the silicon 1 kg sphere
now acts in several metrology institutes as a monitor for instabilities of the national kilogram
prototype (Quinn 2000).
8. The role of N
A
in the SI, present state and outlook
There is general agreement that, if the international prototype of the kilogram can be related
to an invariant quantity of nature such as the Planck constant h or the Avogadro constant N
A
with a relative combined standard uncertainty u
r
of 1 10
8
, then one should give serious
consideration to a redenition of the unit of mass in the SI, thereby eliminating the last material
artefact from the SI. At present, two experimental approaches appear to have the potential of
achieving such a relative uncertainty, within the next decade: the determination of h by the
moving-coil Watt balance, and the determination of N
A
by the XRCD method. In fact, several
years ago a denition of the kilogram was proposed that, together with the existing denition
of the mole, xes the value of N
A
:
The kilogram is the mass of 5.018 . . . 10
25
free
12
C atoms
at rest in their ground state.
It then follows from this denition that the mass of the
12
C atom is exactly m(
12
C) =
1 kg/(5.018 . . . 10
25
), and from the denition of the mole it follows that the value of
the Avogadro constant is xed at:
N
A
=
12M
0
m(
12
C)
=
12 10
3
kg mol
1
1 kg/(5.018 . . . 10
25
)
= 6.022 . . . 10
23
mol
1
. (59)
In this way, the newdenition of the unit of mass is traced back to an atomic mass unit, a straight
forward development, because the Si route to the Avogadro constant is fully independent of
input data of other fundamental constants. The Si route ensures redundancy in the measurement
of the Avogadro constant, a rather important requirement in metrology.
At present the metrology institutes involved are engaged in reducing the relative
measurement uncertainty from the 10
7
to the 10
8
level. The effects of very small
uncertainties of individual parameters playing a role in the determination of the Avogadro
constant with a target combined uncertainty of 10
8
have been summarized in table 27.
A look at these data shows the enormity of this task, and the achievement of this goal is a
big challenge to all metrology laboratories. The conclusion is that the work on N
A
is based on
continuous interaction between physics and technology at their highest levels and that it has
contributed to strengthening the edice of the fundamental physical constants.
2004 P Becker
Table 27. Example of nal uncertainties required to reach 1 10
8
N
A
.
Effect on N
A
Parameter Uncertainty (parts in 10
8
)
Molar mass 0.1 g mol
1
0.36
Mass 4 g 0.40
Diameter 0.11 nm 0.33
Temperature 0.08 mK 0.36
Oxide layer <0.1 nm 0.56
Lattice parameter 0.2 10
3
fm 0.31
Atoms/unit cell 2 10
8
0.25
Total (rss) 1.00
Acknowledgments
I wish to express my sincere thanks to W Zulehner and H Riemann for their permanent
assistance in preparing and characterizing silicon, to B N Taylor for many helpful discussions,
and to ERCohen for his contribution as regards the relationship between the Avogadro constant
and other fundamental constants, to P De Bi` evre and U Bonse for continued scientic advice
and co-operation and for having critically read the manuscript.
It is obvious that a large number of persons have contributed to this overall story in many,
many ways. Without the collaboration among these metrology institutes, a great part of the
results described would not have been obtained.
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History and progress in the accurate determination of the Avogadro constant

C)/2814 000 . . . . (4)

in centimetres, however, did not differ from the

, which is the ratio of the impurity

< 1, the crystal will be puried during

= 0.07 can be reduced by multiple FZ-

is close to 1 and the amount of O cannot, therefore, be reduced by

C). The standard deviation due to statistical

C and in air. (15)

C in vacuum. Each result was

C by correcting for the thermal expansion coefcient = (2.56 0.03)

C and in vacuum (Becker et al

C). Solid curve is the best t to a Gaussian distribution

C. Length measurements carried out with the optical interferometer

whereas those from steel are assumed to range between 202

. Departure from the 180

phase shift in the case of quartz was veried using

C, 0 Pa was (Seyfried et al 1992)

C and 0 Pa, without impurity corrections. Density

C, 0 bar and C, O 0. The density of the

C in pure argon. In a nal step, the material

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