Second-harmonic generation in dry powders: A simple experimental method to

determine nonlinear efficiencies under strong light scattering

I. Aramburu, J. Ortega, C. L. Folcia, and J. Etxebarria

Citation: Applied Physics Letters 104, 071107 (2014); doi: 10.1063/1.4866160

View online: http://dx.doi.org/10.1063/1.4866160
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 APPLIED PHYSICS LETTERS 104, 071107 (2014)

Second-harmonic generation in dry powders: A simple experimental method

to determine nonlinear efficiencies under strong light scattering
I. Aramburu,1 J. Ortega,2 C. L. Folcia,3 and J. Etxebarria3
1
Department of Applied Physics I, Faculty of Engineering (ETSI), University of the Basque Country,
UPV/EHU, Alda Urquijo s/n, 48013 Bilbao, Spain
2
Department of Applied Physics II, University of the Basque Country, UPV/EHU, 48080 Bilbao, Spain
3
Department of Condensed Matter Physics, University of the Basque Country, UPV/EHU, 48080 Bilbao, Spain

(Received 10 December 2013; accepted 3 February 2014; published online 20 February 2014)
A simple experimental method for determining the efficiency of second harmonic generation
(SHG) using small amounts of dry crystalline powder is described. Contrary to previous
techniques, the light scattering effects are explicitly accounted for, and a procedure to eliminate
their influence is proposed. The method also permits to assess whether a particular crystal is phase
matchable or not. Second-order susceptibility coefficients of eight relevant materials for SHG are
determined, and the agreement with the single-crystal data is, in general, fairly good. For
polycrystalline ZnSe samples, a situation of the so-called random quasiphase matching is
evidenced. V C 2014 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4866160]

Recently, the Kurtz-Perry method1 for assessing the effi-
ciency of second-harmonic generation (SHG) in powder
samples has been subjected to criticism.2 Most of the objec-
tions derive from the lack of consideration in the theory of
the light scattering effects during the SHG process. These
effects are very important and can give rise to errors in the
determination of nonlinear optical (NLO) coefficients of up
to one order of magnitude. Incorrect conclusions can even be
drawn about the very existence of the phase matching (PM)
condition in the crystal (see Table V in Ref. 2). Many prob-
lems of the measurements of SHG in powders arise from
oversimplifications of the original Kurtz-Perry method but
are, however, common practices in actual experiments: Lack
of use of index matching liquid, no control of the powder
packing fraction, omission of the influence of the refractive
indices in the SHG magnitude, or collection of only a (non-
representative) fraction of the total scattered SHG signal. As
a result of these factors, many of the experimental works that
make use of the Kurtz-Perry technique are of scarce value
and should be revised.
In this paper, we propose an alternative technique to
obtain quantitatively the efficiency for SHG in powders. The
method is based on the theory developed in Ref. 2 and con-
siders the light scattering by the powder particles explicitly.
In contrast with other procedures that use samples in the
form of powder crystal monolayers,3 the method is not
affected by possible preferential orientations of the powder
particles on a surface. It is not necessary to use any index
matching fluid (dry powder) and only very small amount of
material is required. The method is therefore quite appropri-
ate for a quick review of the potentialities of NLO materials.
To explain the technique, we start recalling that the
SHG by a powder sample can be formally written as2
I2 fGr Sr; f I1 2 ; (1)
where I2 is the total integrated SHG flux, I1 is the intensity of
the fundamental beam, f is the volume packing fraction, and
r is the particle size of the crystalline powder. G(r) is a
function of the second-order susceptibility coefficients dij
and refractive indices (G(r) is proportional to g(r)/r in Eq.
(38) of Ref. 2), and S(r,f) accounts for the light scattering
effects. In its turn, S(r,f) is a complicated function that
involves the grain size, the packing fraction, the sample
thickness, and the refractive indices of the crystal and the
medium where the powder is immersed (air or
index-matching fluid). The SHG light emitted in the back-
ward or forward directions can be expressed in an analogous
way by substituting S(r,f) in (1) by the corresponding func-
tions for back and forward scattering. Those functions have
also been computed in Ref. 2.
The key point of the method lies on the fact that, for any
detection geometry (back, forward, or integrated), the SHG
signal can be factored as a part due to the scattering and
another term, G(r), where all the NLO parameters are con-
tained. Usually SHG measurements are carried out as a func-
tion of r. Thus, it is impossible to make a measurement
without simultaneously altering the scattering effects and the
NLO response. The separation, however, can be worked out
with a two-component sample. A similar idea was proposed
some years ago,4 with only partial success. In our samples,
the test material was prepared as powder of different grain
size and was uniformly mixed at low concentration (about
1% w/w) in a matrix inert from the point of view of NLO.
As a matrix, we used glass spheres of 100 lm of diameter
(Cospheric). In this kind of samples, the NLO effect arises
from the test material, while the scattering effects are essen-
tially due to the glass spheres and can be calibrated easily.
The SHG signal results
I2 fm GrSrg ; fg I1 2 ; (2)
where fm and fg are the volume packing fraction of the active
material and glass, respectively, and rg is the diameter of the
glass spheres.
If the size and packing fraction of the glass particles are
constant, the scattering function is also a constant, and the
NLO efficiencies can be deduced straightforwardly if SHG

0003-6951/2014/104(7)/071107/4/$30.00 104, 071107-1 C 2014 AIP Publishing LLC

V

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 071107-2 Aramburu et al. Appl. Phys. Lett. 104, 071107 (2014)

signals measured under the same scattering conditions and

detection geometry are compared. There is no need for any
integrating sphere or special measurement attachment.
The samples were prepared in the form of disks of
15 mm of diameter and 0.5 mm of thickness. The NLO crys-
tal was ground with an agate mortar and the particle diameter
was determined using sieves. The crystalline powder and
glass spheres were then mixed and pressed firmly into the
sample holder (Fig. 1). Due to the spherical shape of the
glass particles, the different samples were found to have a
rather constant packing fraction (fg  0.55). This assures the
reproducibility of the scattering effects in the different sam-
ples and permits to eliminate its influence in the SHG
experiments.
A collimated Nd:YAG Q-switched laser operating at
1064 nm was used as a light source. The detector was placed
at about 50 mm from the sample, and the light was collected
near back reflection. The spot diameter was about 5 mm.
This large spot assures that a representative set of grains of
the test compound is illuminated. Moreover, the measure-
ment statistics was improved by proving both sides of the
sample and translating the disks along a direction perpendic-
ular to the laser beam in order to illuminate different regions
of the sample. The final SHG signal was the average of the
intensities generated by 6 different illuminated areas.
The function G(r) contains all the information about the
NLO behavior of the test material. In practice, there are
essentially two types of G(r) functions depending on the
character (non-phase matchable or phase matchable) of the
studied material. For non-phase-matchable materials, numer-
ical calculations2 show that G(r) oscillates as a function of r,
with a period equal to two times the average coherence
length, similarly to the behavior found by Kurtz and Perry1
for the SHG signal in the absence of scattering. FIG. 2. Blue circles: Experimental SHG intensities vs. grain size r for (a)
Superimposed to the oscillatory behavior, there is a r1 de- quartz and (b) KDP powders. The continuous lines are theoretical fits using
pendence for large r (see the continuous curve in Fig. 2(a) as the scale factor as the only fit parameter. The red squares in (a) are averages
of the theoretical predictions over r ranges determined by the experimental
dispersion of r.

a typical example). If there is dispersion of particle sizes, the

FIG. 1. Schematic view of the experimental setup. Graded particles of the
test material (yellow hexagons) are mixed in a small proportion with glass
spheres of 100 lm of diameter (gray circles). The mixture is sandwiched and
pressed between two glass plates separated by a teflon annular spacer
(0.5 mm thick, 15 mm inner diameter). The SHG light is detected near back
reflection.
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oscillations are damped because of an averaging effect. The
shape of G(r) in a phase-matchable material is completely
different (continuous line in Fig. 2(b)). There are different
possibilities depending on the precise values of the refractive
indices, but in general, G(r) grows quickly from zero for
small r and stabilizes to a constant value for particle sizes
larger than a few tens of microns. For the case of uniaxial
materials, the asymptotic value of G(r) can be obtained ana-
lytically (see Eqs. (5), (22), (37), and (38), and Tables IIV
of Ref. 2).
As a basic validation of our technique, we present the
results for a non-phase-matchable material (quartz, Fig. 2(a))
and a phase-matchable material [KH2PO4 (KDP), Fig. 2(b)].
The r dispersion in the powder particles is not enough to
wipe out the oscillations of G(r), especially for quartz. The
continuous curves are the theoretical fits obtained with only
one fit parameter (the scale factor). As can be seen, the shape
of the curves is reproduced satisfactorily. The relative mag-
nitudes of the scale factors give information about the dij
coefficients. Taking as a reference d11(quartz) 0.30 pm/V
 071107-3 Aramburu et al. Appl. Phys. Lett. 104, 071107 (2014)

TABLE I. Second-order susceptibility coefficients of some relevant crystals for SHG at k 1064 nm. The refractive indices were taken from: Ref. 14 (quartz),
Ref. 15 (KDP and ADP), Ref. 16 (urea), Ref. 8 (POM), Ref. 17 (BBO), Ref. 18 (KTP), and Ref. 19 (ZnSe).

I2sat
Material Point group I2sat KDP
dij (pm/V)a dij (pm/V)b dij (pm/V)c

Quartz 32 d11 0.30 d11 0.305

KH2PO4 (KDP) 
42m 1.0 d14 0.35 d14 0.395
Urea 
42m 4.9 d14 1.8 d14 1.26,7 d d14 2.39,10
3-methyl-4-nitropyridine 1-oxide (POM) 222 113 d14 9.1 d14 6.08 e d14 108 f
d14 9.210
d14 1011
d14 9.712
b-BaB2O4 (BBO) 3m 9.1 d22 2.7g d22 2.25
NH4H2PO4 (ADP) 
42m 1.2 d14 0.41 d14 0.475
KTiOPO4 (KTP) mm2 36.0 deff 2.1h deff 3.05 deff 2.013
ZnSe 
43m d14 d14 305

a
This work.
b
Recommended value.
c
Further references.
d
Measured at k 600 nm.
e
The modern reference d11(quartz) 0.30 pm/V was adopted.
f
The old reference d11(quartz) 0.50 pm/V, used in the original work, was maintained.
g
d31 and d33 were assumed negligible according to Ref. 5.
h
deff for KTP was defined as the square root of the ratio of the SHG intensities of KTP and KDP, multiplied by d14(KDP). deff is a complicated function of d31,
d32, d33, and the refractive indices.

we obtain d14(KDP) 0.35 pm/V, in good agreement with
the data from the literature.
Other crystals were also studied and the results are col-
lected in Table I. Only commercially available materials
with technological interest for which there exists a reasona-
ble consensus about their dij coefficients were selected.
Except for quartz and ZnSe, all are phase matchable, and the
dij coefficients were deduced using just the asymptotic value
of the SHG intensity (I2sat ) (in general, I2 vs. r is essentially a
constant in these materials). The literature values for dij (fifth
column of Table I) are those most commonly accepted
among researches. When possible, the recommended stand-
ards of the NLO coefficients have been given.5 In the cases
of discrepancies, additional references have been provided
which show better accordance with our results. The agree-
ment is in general fairly good.
ZnSe deserves a separate mention. This material is cubic
(crystal class 43m). The function g(r) can be shown to be
given by
is a real situation of PM. This PM condition is unusual and is
called random quasi-phase matching (RQPM).20,21 It can be
attained in highly transparent polycrystalline cubic samples.
We obtained the ZnSe crystalline powder by crushing a
sheet of chemically vapor deposited ZnSe, supplied by
Aldrich. Contrary to our initial assumption, we found that
the powder particles themselves were, in fact, polycrystalline
(see Fig. 4). The presence of domains oriented randomly is a
basic requirement for the RQPM to occur. In addition, the re-
fractive indices must not show any jump between adjacent
domains to avoid scattering losses and permit a high SHG ef-
ficiency. That condition occurs automatically in cubic crys-
tals because the indices are isotropic and polarization

8d142
sin2 Dkr=2
g r ; (3)
7e0 cn2 n21 n2  n1 2

where e0 is the vacuum permittivity, c is the speed of light,

n1 and n2 are the refractive indices at k and k/2, respectively,
and Dk p/lc. The small size of the coherence length
(lc 1.3 lm for k 1064 nm) produces short-period oscilla-
tions in the theoretical curve G(r) (continuous line in Fig. 3).
Due to the dispersion in the grain sizes, one would expect to
observe experimentally the average curve of all these oscilla-
tions (dashed line in Fig. 3). However, surprisingly, the
FIG. 3. Blue circles: Experimental SHG intensities vs. grain size r for ZnSe.
measurements reveal a completely different behavior that The continuous line is the theoretical prediction taking the data from Ref. 5
reminds us that of a phase matchable material (dots in Fig. (d14 30 pm/V) and Ref. 17. The dashed line represents the average of the
3). The explanation to this phenomenon is that, in fact, there short-period oscillations.

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 071107-4 Aramburu et al.
FIG. 4. X-ray diffraction pattern of a particle of the ZnSe powder used for
the SHG measurements. The particle had approximate dimensions 150 
100  50 lm3. Diffraction rings are evident, indicating the presence of
many domains in the particle. The convergence of the beam was 103 rad,
which implies that every randomly oriented single crystal should produce a
spot on the innermost (111) ring with a probability of about 1%.22 The num-
ber of spots observed on that ring (more than 20) gives a rough idea of the
order of magnitude of the average domain size ld < 6 lm.
independent. Under these conditions, the efficiency of the
NLO generation of light grows linearly with the number of
domains in each powder particle (r/ld),20,21 where ld is the
average domain size. In other words, I2 is proportional to
G(r)(r/ld), or I2 / g(r)/ld. Moreover, if the dispersion of do-
main sizes is larger than (2lc) then the function g(r) must be
substituted by its average value in (3), i.e., g(lc)/2. Therefore,
in this situation, I2 must be independent of r, as is experi-
mentally observed. On the other hand, the magnitude of the
SHG signal is connected with d14 and ld. The accordance
with the d14 result by Shoji et al.5 would imply ld  3 lm.
This is the right order of magnitude obtained by X-ray dif-
fraction (see Fig. 4).
In conclusion, we have proposed a simple method to
study quantitatively the efficiency of SHG in powder sam-
ples. The scattering effects are eliminated effectively by
using samples with only a small proportion of test material.
Eight materials have been studied, and in general, the results
for the dij coefficients are good. A situation of RQPM has
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Appl. Phys. Lett. 104, 071107 (2014)
also been revealed in a ZnSe polycrystalline sample. The
method is an adequate alternative for a systematic survey of
NLO materials.
This work was supported by the MEC of Spain (Project
No. MAT2012-38538-C03-02) and by the Basque
Government (Project Nos. GI/IT-449-10 and GIC12/146).
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