Facultad de Fsica

Departamento de Fsica Aplicada

Master's dissertation

Effects of high-pressure on the structural, vibrational and electronic properties of monazite-type PbCrO4

Student: Enrico Bandiello Supervisor: Prof. Daniel Errandonea

Valencia, July 2012

Eect of high-pressure on the structural, vibrational and electronic properties of monazite-type PbCrO4
Student: Enrico Bandiello July 2012

Supervisor: Prof. Daniel Errandonea

To my wife Karina and to my son Francesco, who is almost here...

Contents

Acknowledgements 1 Methodology and experimental setting 1.1 Diamond-anvil cells . . . . . . . . . . 1.2 Ruby uorescence as a pressure gauge 1.3 Samples and experimental setups . . 1.3.1 Samples . . . . . . . . . . . . 1.3.2 Optical measurements . . . . 1.3.3 X-ray diraction experiments 1.3.4 Raman experiments . . . . .

v 1 1 1 2 2 3 4 5 7 7 8 9 9 12 15 15 17 20 23 27 27 29 30 31 33 33 35 35 37 37 41

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Characterization of PbCrO4 at ambient conditions 2.1 AXO4 monazite-type compounds . . . . . . . . 2.2 A general description of PbCrO4 . . . . . . . . 2.3 Crystal structure at ambient pressure . . . . . 2.4 Raman spectrum at ambient pressure . . . . . 2.5 Optical absorption at ambient pressure . . . . Experimental results and conclusions 3.1 High-pressure X-ray diraction experiments 3.2 High-pressure Raman experiments . . . . . . 3.3 High-pressure optical-absorption experiments 3.4 Conclusions . . . . . . . . . . . . . . . . . .

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A Space groups A.1 Space groups . . . . . . . . . . . . . A.1.1 Wycko positions . . . . . . A.2 Monoclinic P 21 /n space group . . . A.3 Orthorhombic P 21 21 21 space group

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B Raman spectroscopy and notation. B.1 Raman Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B.1.1 Mullikens symbols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B.2 Raman tensors for PbCrO4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C Software C.1 Software tools . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References

List of Figures
1.1 1.2 1.3 1.4 2.1 2.2 2.3 2.4 2.5 2.6 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 Scheme [1] and photo of a DAC. . . . . . . . . . . . . . . . . Ruby uorescence spectra . . . . . . . . . . . . . . . . . . . . XFR analysis of PbCrO4 natural samples and surface of the 650. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Experimental setup for the optical-absorption experiments. . . . . . . . . . . . original . . . . . . . . . . . . . . . . . . crystal . . . . . . . . . . . . . . . . . . . . . . . . at . . . . . . . . . . . . . . . . 2 3 3 5 7 8 9 10 11 12 15 16 17 18 18 21 22 23 30 31

Schematic view of an AXO4 monazite. . . . . . . . . . . . . . . . . . . . . Monazite projected down [001] . . . . . . . . . . . . . . . . . . . . . . . . Photo of the sample in the DAC at ambient pressure and at P = 3.5 GPa XRD pattern for PbCrO4 at ambient pressure . . . . . . . . . . . . . . . Raman spectrum for PbCrO4 at ambient pressure . . . . . . . . . . . . . Optical-absorption spectrum for PbCrO4 at ambient pressure. . . . . . .

X-ray patterns at selected pressures . . . . . . . . . . . . . . . . . . . . . . . . . Pressure evolution of the unit-cell parameters of PbCrO4 for the low-pressure phase. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Pressure evolution of the volume of the unit cell. . . . . . . . . . . . . . . . . . . Raman spectra of PbCrO4 at dierent pressures. . . . . . . . . . . . . . . . . . . Evolution of Raman active modes for PbCrO4 under compression. . . . . . . . . Absorption spectra of PbCrO4 at selected pressures. . . . . . . . . . . . . . . . . Pressure dependence of Eg for PbCrO4 . . . . . . . . . . . . . . . . . . . . . . . Schematic band structure of monazite-type PbCrO4 . . . . . . . . . . . . . . . .

A.1 P 21 /n space group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.2 P 21 21 21 space group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

ii

List of Tables
2.1 2.2 2.3 Lattice parameters and atomic position for PbCrO4 at ambient pressure. . . . . Bond lengths for the CrO4 and PbO9 polyhedra at ambient pressure. . . . . . . Raman active modes for PbCrO4 at ambient conditions, pressure coecients and Grneisen parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . u Bond lengths for the polyhedral units at 5.2 GPa. . . . . . . . . . Lattice parameters for PbCrO4 for the HP phase . . . . . . . . . . Raman active modes at 6.4 GPa for the HP monoclinic phase of pressure coecients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . PbCrO4 . . . . . . . . . . . and . . . 10 10 13 16 17 20 28 29 31 35

3.1 3.2 3.3

A.1 Resume of 3D Bravais lattice and related parameters. . . . . . . . . . . . . . . . A.2 Wycko sites for the monoclinic P m space group. . . . . . . . . . . . . . . . . . A.3 Wycko sites for the monoclinic P 21 /n space group. . . . . . . . . . . . . . . . . B.1 Mullikens symbols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

iii

Acknowledgements
First of all I would like to thank my supervisor, Prof. Daniel Errandonea, for his invaluable help and his patience during the realization of this work. I am very grateful to him for the assistance in the realization of the experiments, the data analysis and the corrections of the various revisions of the manuscript. Above all, I would like to thank him for all the opportunities he gave me, such as the participations in the EHPRG Conferences and the co-authoring of articles. Thanks to Prof. Domingo Mart nez, Prof. Javier Manjn, Prof. Alfredo Segura and o Dr. David Santamar for the collaboration in the realization of this work. a Thanks to Dr. Javier Ru for the hints in the normalization of the optical spectra z and for the serious answers to my naive questions (once more!).

1. Methodology and experimental setting

Introduction
Our main goal is the study of the physical properties of monazite-type PbCrO4 under compression and the relation they have with the structural changes occurring in the mineral because of hydrostatic pressure. Various experimental techniques have been used in this study, such as optical absorption spectroscopy, Raman spectroscopy and X-ray diraction. In Chapter1 we will describe some experimental details while Chapter 2 is devoted to a general description of monazite-type AXO4 compounds and to a characterization of our PbCrO4 samples at ambient conditions. Finally, in Chapter 3 the result of our high-pressure experiments and their physical interpretations are presented. Appendices A and B contain some very informal notes about space groups and Raman spectroscopy, while Appendix C reports the list of the software tools that have been used in this work.

1.1. Diamond-anvil cells

Diamond-Anvil Cells (or DACs) are the most commonly used devices in the study of physical behavior of crystal samples upon high-pressure conditions (up to 300 GPa1 ). They basically consists in a pair of diamonds that are cut leaving on each of them a small culet. A pre-indented steel gasket acts as a separator between the facing culets, forming a sealed chamber where the sample is placed together with a pressure medium. To generate the needed pressure on the sample, the assembly is inserted into a metal cylinder where a metallic membrane, slowly inated with Helium (He), exerts a force F on the diamonds. The pressure P on the culets thus rises according to equation P = F/A, where A is their area. Ideally hydrostatic pressure conditions are obtained by means of the pressure medium. Figure 1.1 gives a schematic representation and a photo of one of the DAC used in our experiments.

1.2. Ruby uorescence as a pressure gauge

The measurement of the pressure inside the DAC is done indirectly, by means of the ruby (Al2 O3 :Cr3+ ) uorescence technique. Small ruby chips are loaded together with the sample inside the pressure chamber. Ruby uorescence is excited with a green laser2
1 2

100 kPa=104 GPa 1 atm (ambient pressure). = 523 nm in our case.

1. Methodology and experimental setting

Figure 1.1.: Scheme [1] and photo of a DAC.

and a doublet R1 , R2 is generated. Wavelengths at ambient pressure are respectively 0 1 = 694.3 nm and 0 2 = 692.7 nm [2] ; these lines regularly redshift with increasing R R pressure, as can be seen in Fig. 1.2. There are several empirical expressions of R1 (P ); however in our pressure range (100 kPa21 GPa) they give pressure that dier by less than 1%. The following expression has been used [2] in our experiments: P (R1 ) [GPa] = 1904 [GPa] 7.665 R1 [nm] 694.38 [nm]
7.665

1 .

(1.1)

The uorescence spectra were taken using an OCEAN OPTICS HR2000 Si spectrometer equipped with a holographic grating with a groove density of 1800, which covers the spectral range from 600 to 755 nm with an optical resolution of 0.1 nm.

1.3. Samples and experimental setups

Some experimental details are given in this section. We have used similar DACs trough all the experiments, despite the dierent techniques that were employed. The diameter of the culets was 500 m while the pressure medium was either a 16:3:1 methanol-ethanolwater or a 4:1 methanol-ethanol mixture [3] (they provide a similar pressure environment). High-pressure experiments were performed at room temperature. Additionally , all the experiments have been carried out also at ambient pressure, outside the DAC.

1.3.1. Samples
Our samples were obtained from natural crystals, originated from the Red Lead Mine in Australia. In rst place, a visual and chemical microanalysis of the samples was performed, to check for the presence and nature of impurities. This was made using a PHILIPS XL-30 ESEM scanning electron microscope situated at the Electron Mi-

1.3. Samples and experimental setups

2,500

P=1.59 GPa

P=13.34 GPa

Intensity (Arb. Units)

2,000

1,500

1,000

500

0 692 694

Wavelength (nm)

696

698

700

Figure 1.2.: Ruby uorescence spectra. The pressure corresponding to each spectrum is indicated.

Figure 1.3.: XFR analysis of PbCrO4 natural samples and surface of the original crystal at 650.

croscopy Section of SCSIE3 , UV. The results of the analysis are resumed in Fig. 1.3: it shows some crystals of PbCrO4 at 650 and an X-ray uorescence spectrum of our sample. Only a negligible amount of Fe (0.06%) is present in some regions of the sample, likely due to ferrous oxides incorporated in the mineral during its growth. For our experiments, we selected microcrystals of PbCrO4 with undetectable amount of impurities. The samples used in optical-absorption and Raman experiments were crystals about 20 m thick, while X-ray diraction experiment have been performed on nely ground powder samples obtained from single crystals (grain size < 1 m).

1.3.2. Optical measurements

The optical-absorption experiments were performed on single crystals in a DAC using a 16:3:1 methanol-ethanol-water mixture as pressure medium. This medium provides
3

Servei Central de Suport a la Investigaci Experimental (Central Support Service for the Experimental o Research).

1. Methodology and experimental setting quasi-hydrostatic conditions in the pressure range covered by our experiments [4] . Our experimental setup for these experiments is depicted in Fig. 1.4. There, O1 and O2 are two Cassegrain objectives, each one mounted on a two-axis micrometric slide. Objective O1 is needed to concentrate the light from the halogen lamp (resp. the laser) in a small spot and to focus it on the sample (resp. the ruby), while O2 serves to focus on the detector the light transmitted by the sample. The optical measurements spanned a fairly broad spectral range. This required the use of two dierent detectors, in particular an OCEAN OPTICS HR4000 Si spectrometer for the range 5001100 nm and a JOBIN-YVON H25 monocromator coupled with a Ge detector for the range 9501800 nm. Schematically, each optical measurement involves the following steps: 1. choose a suitable value for the pressure on the sample. 2. focus the laser beam on a ruby, with the aid of the ocular and the screen. 3. pump He in the DAC until the chosen pressure is achieved. Meanwhile, pressure value is checked in real-time using the laser and the spectrophotometer (Section 1.2). 4. replace laser with the He lamp and focus the light spot ( 20 m) outside the sample. Take a reference spectrum of the direct beam. 5. focus the light on the sample and take the spectrum of the transmitted light. 6. the ratio between the rst spectrum and the second one is then the transmittance of the sample at the chosen pressure. 7. the transmittance spectrum is transformed into an absorption spectrum (the absorption coecient as a function of energy), considering the thickness of the sample and its refraction index [5] . The absorption spectra were determined at selected pressures, both upstroke and downstroke, up to a maximum of about 21 GPa. We couldnt go any further in pressure due both to the strong opacization of the samples and to the limitations of our detector. Both factors factors made very dicult the obtainment of accurate spectra beyond 21 GPa. The optical-absorption experiments allowed us to determine the evolution of the band gap of PbCrO4 with pressure and to relate it with the changes in the crystal structure of the mineral evidenced by the other techniques.

1.3.3. X-ray diraction experiments

X-ray diraction patterns have been obtained performing powder diraction in a DAC using Molybdenium K1 :K2 wavelengths (0.7101 and 0.7144 respectively) in an AGA A ILENT TECHNOLOGIES Xcalibur diractometer, equipped with an ATLAS CCD. The pressure medium was a 4:1 methanol-ethanol mixture. The experiments were performed up to a maximum of 13 GPa.

1.3. Samples and experimental setups

Mirror Laser diode

Lens

Halogen lamp PC Optical fiber

Spectrophotometer

Lens

O1

O2

Prism

Optical fiber

Mirror Diaphragm DAC (with sample, ruby and pressure medium) Detector with diaphragm

Ocular

Screen

Figure 1.4.: Experimental setup for the optical-absorption experiments.

The diraction experiments allowed us to study the evolution of the crystallographic parameters and the volume of the unit cell of PbCrO4 under compression. In particular, the data relative to the volume were tted using the Birch-Murnaghan third-order equation of state [6] P V V0 = 1.5B0 V V0
7/3

V V0

5/3

1+

3 (B1 4) 4

V V0

2/3

(1.2)

where V0 and V are respectively the volume of the unit cell at ambient pressure and at pressure P . The t of the volume data with Eq. (1.2) gives directly the bulk modulus B0 4 and its pressure derivative B1 . Furthermore, the X-ray diraction patterns allowed us to identify structural changes and to propose a crystalline structure for the high-pressure phase of PbCrO4 .

1.3.4. Raman experiments

Raman experiments were performed in the backscattering geometry using a 30 mW HeNe laser, with = 632.81 nm and a Horiba Jobin Yvon LabRAM high-resolution ultraviolet (UV) microspectrometer in combination with a thermoelectrically cooled multi4

The bulk modulus B0 is a measure of the ability of a substance to withstand changes in volume when under hydrostatic compression. It is equal to the quotient of the applied pressure divided by the relative deformation of the material: P B0 = V . V

1. Methodology and experimental setting channel CCD that allowed for spectral resolution below 2 cm1 . An edge lter was used to remove the contribution of the laser in the low-frequency range. By analyzing the Raman spectra we obtained the frequencies of the phonons of the crystal at ambient pressure (0 ) and their evolution upon compression, determined by their pressure coecients (d/dP ). Also the Grneisen parameter5 of each phonon was u determined, using the value of B0 obtained in the XRD experiments [Eq. (1.2)]. Finally, the study of the evolution the Raman patterns with pressure was useful to localize the phase transitions and also as an independent conrmation of the hypothesis about the high-pressure crystalline structure of PbCrO4 .

The Grneisen parameter describes the eect that changing the volume of a crystal lattice has on u its vibrational properties and is related to the thermal expansion properties of a material. When the restoring force acting on an atom displaced from its equilibrium position is linear in the atoms displacement, the frequencies i of individual phonons do not depend on the volume of the crystal or on the presence of other phonons, and the thermal expansion (and thus ) is zero. When the restoring force is non-linear in the displacement, the phonon frequencies i change with the volume. The Grneisen parameter of an individual vibrational mode can then be dened as: u i = ln (i ) ln(i ) = B0 . ln(V ) P

2. Characterization of PbCrO4 at ambient conditions

2.1. AXO4 monazite-type compounds
The name monazite is given to some phosphates containing light rare-earth metals, commonly indicated by RE(PO4 ) (RE=La to Gd). All these compounds crystallize in a monoclinic lattice with symmetry elements proper of the P 21 /n space group (Z = 4). It is customary to name monazite-type compounds all the crystalline materials sharing the same crystal structure, not all of them being phosphates. Monazite-type oxides form an extended family with interesting physical and chemical properties; these allow for a large number of applications such as in coating and diusion barriers, geochronology, light emitters and so on [7] . On the other hand, the knowledge of the behavior of monazite under high-pressure conditions can be relevant for mineral physics, chemistry, petrology and geology [7] .

Figure 2.1.: Schematic view of an AXO4 monazite.

The crystal structure of monazite-type AXO4 is based on the ninefold coordination of the A cation and the fourfold coordination of the X cation. Figure 2.1 shows the unit cell of a monazite, with the position of atoms inside it. The whole structure is formed by [001] chains of slightly distorted XO4 tetrahedra separated by irregular AO9 polyhedra. The chains extend along [001] by sharing tetrahedral edges with AO9 polyhedra. There are four chains per unit cell. They are linked laterally, in the (001) plane, by sharing edges

2. Characterization of PbCrO4 at ambient conditions

Figure 2.2.: Monazite projected down [001]. An AO9 polyhedron is outlined.

of adjacent AO9 polyhedra. This is the most notable characteristic of the monazite structure and has a strong inuence on its behavior under compression. Figure 2.2 shows a polyhedral representation of the crystal structure projected onto the (001) plane, putting in evidence the monazite chains. Studies performed on monazite-type phosphates have shown that their crystalline structure is stable up to approximately 30 GPa [8,9] ; anyway, cation substitution (particularly with magnetic cations, like Cr) can contribute to the reduction of the transition pressure in zircon-type oxides (a tetragonal structure, closely related to the monoclinic monazite structure) [10,11] ; consequently, we expect the appearance of phase transitions at a relatively low pressure in ACrO4 monazite-type chromates.

2.2. A general description of PbCrO4

In general chromates with monazite structure are translucent materials with a band gap between 2 and 2.8 eV [12] . Their crystals are biaxial, having two optic axes. The birefringence of these materials is usually of the order of 0.05 and the average index of refraction is approximately 2.4. Lead chromate (PbCrO4 , crocoite) is one of such minerals, given that it commonly crystallizes at ambient conditions in a monazite structure [13] , though also an orthorhombic variety of PbCrO4 exists [14] . It is commonly used in some pyrotechnic compositions and as a pigment in some paints, being it practically insoluble in water. It can also be used as a photocatalyst and has been proposed as a potential laser-host material. Crocoite is a quite toxic substance (LD50 > 12 g/Kg1 ) if swallowed or inhaled, so it has to be properly handled. It is quite rare in nature but it can be grown in laboratory [15] .
1

In toxicology, the median lethal dose, LD50 (abbreviation for lethal dose, 50%) of a toxin, radiation, or pathogen is the dose required to kill half the members of a tested population after a specied test duration.

2.3. Crystal structure at ambient pressure

Figure 2.3.: Photo of the sample in the DAC at ambient pressure (left) and at P = 3.5 GPa (right).

Very few studies have been performed on this compound, mainly centered on its crystal structure: for example, no accurate experimental determinations of the band gap of monocrystalline PbCrO4 have been published until now. Figure 2.3 shows two photos of one of our samples, one at ambient conditions and at one P = 3.5 GPa. The tiny transparent sphere right under the sample is the ruby used for the determination of the pressure.

2.3. Crystal structure at ambient pressure

The renement of the ambient-pressure XRD spectrum for the PbCrO4 powder samples is shown in Fig. 2.4. From this renement we obtained the lattice parameters of monazite-type PbCrO4 . They are listed in Table 2.1, along with the values given in the literature [16] ; Table 2.1 also lists the atomic positions inside of the unit cell, in fraction of the lattice parameters. Both sets of values are in good agreement with those given in the literature [16,17] . In this monazite structure Cr is coordinated with 4 oxygens and Pb with 9 oxygens; the bonds for the CrO4 sub-structure form a distorted tetrahedron and their lengths can be calculated on the basis of the value in Table 2.1. The same can be done for the bonds in the PbO9 sub-structure, that in turn form an irregular polyhedron. The lengths for all bonds are reported in Table 2.2. A 10th oxygen atom is listed in Table 2.2 as coordinated with Pb; in rst approximation we can consider it as isolated, because of its distance from Pb (+10% with respect to O9 ). On the other hand, its presence could favor a coordination increase under compression, as we will see in the following.

2.4. Raman spectrum at ambient pressure

The Raman spectrum of PbCrO4 at ambient pressure is shown in Fig. 2.5. Given that the lattice of PbCrO4 can be thought as constituted by a set of two separate structures, CrO4 tetrahedra and PbO9 polyhedra, the analysis of this Raman spectrum can be

2. Characterization of PbCrO4 at ambient conditions

(a)

Intensity (arb. units)

5

10

15

20

25

30

35

2 (degrees)

Figure 2.4.: XRD pattern for PbCrO4 at ambient pressure (dots). Solid line: rened prole. Dotted line: resduals. Ticks: calculated positions of the Bragg reections.

a [] A Exp. Lit. 7.098(7) 7.127(2) x/a Pb Cr O1 O2 O3 O4 0.2247(3) 0.1984(2) 0.2561(3) 0.1201(2) 0.0274(1) 0.3859(4)

Lattice parameters b [] A c [] A 7.410(7) 6.779(7) 7.438(2) 6.799(2) Atomic positions y/b z/c 0.1515(2) 0.4044(5) 0.1643(2) 0.8845(9) 0.0047(1) 0.0568(1) 0.3415(4) -0.0057(1) 0.1047(2) 0.6858(7) 0.2152(3) 0.7872(8)

[ ] 102.4(2) 102.43(2) Site 4e 4e 4e 4e 4e 4e

Table 2.1.: Lattice parameters and atomic position for PbCrO4 at ambient pressure.

Atom Cr Pb Atom Cr Pb

O1 1.650(8) 2.562(8) O6 2.644(1)

Bond lengths [] A O2 O3 O4 1.650(8) 1.662(7) 1.667(4) 2.576(1) 2.590(2) 2.620(5) O7 O8 O9 2.647(8) 2.741(2) 3.062(1)

O5 2.631(1) (O10 ) 3.382(6)

Table 2.2.: Bond lengths for the CrO4 and PbO9 polyhedra at ambient pressure.

10

2.4. Raman spectrum at ambient pressure

x5

Intensity (arb. units)

0

100

200

300

400

500

600

700

800

900

1000 1100

Raman shift (cm-1)

Figure 2.5.: Raman spectrum for PbCrO4 at ambient pressure. Ticks indicate phonon frequencies.

carried out in terms of two complementary sub-lattices, formed respectively by Pb atoms and CrO4 molecules; thus, the vibration modes of the lattice can be classied as internal and external modes of the CrO4 units. The external modes are pure translation (T) or rotation (R) modes of the CrO4 molecule as a whole, while the internal modes con be decomposed into four types of motion i (i = 1, . . . , 4) corresponding to stretching (1 , 3 ) and bending (2 , 4 ) vibrations. Symmetry considerations predict the existence of 36 active Raman modes for this monazite. The representation at the point in the standard notation is = 18Ag + 18Bg and the classication in external and internal modes yields = Ag (6T, 3R, 1 , 22 , 33 , 34 ) + Bg (6T, 3R, 1 , 22 , 33 , 34 ). In previous works [18] up to 10 Raman active modes have been observed for PbCrO4 , while usually monazites dont show more than 22 modes of the 36 theoretically expected [19] , due to the fact that some of them could be too weak or damped to be observed experimentally. In our experiments we could observe up to 26 active modes for PbCrO4 at ambient pressure. Under compression, 4 further modes show up, due to peak splitting. In the low frequency range, the presence of the lter made impossible for us to observe the peak reported by Wilkins [20] at 36 cm1 . In general, all the modes in the lowest frequency range were weak and therefore acquisition time in the low-frequency region was multiplied by 5 (see Fig. 2.5). All in all, we could observe 19 new modes never reported before, mainly located in the low-frequency part of the spectrum. All the modes that we have observed are reported in Table 2.3. The assignments in Table 2.3 can be understood as follows. Intuitively, the ve modes in the high-frequency range can be attributed to the stretching motions inside the CrO4 units, due to the low weight of the Cr and O atoms, while the 10 modes in the middlefrequency range are probably due to bending vibrations inside the CrO4 units. The assignments for these ranges, with less modes, were done in the already cited work by Frost [18] . Finally, the 15 low-frequency modes are due to lattice vibrations, probably

11

2. Characterization of PbCrO4 at ambient conditions

2,500

2,000

(cm-1)

1,500

1,000

500

0 1.20 1.40 1.60

Energy (eV)

1.80

2.00

2.20

2.40

Figure 2.6.: Optical-absorption spectrum for PbCrO4 at ambient pressure.

with contributions due to the motions of the heavy Pb atoms.

2.5. Optical absorption at ambient pressure

The optical-absorption spectrum for PbCrO4 , shown in Fig. 2.6, is typical of a direct band-gap semiconductor. The dependence of the absorption coecient on the photon energy h is mainly exponential, though it also shows a weak low-energy absorption band below the band gap. This band has been observed also in other ane compounds, as PbWO4 , and it can be attributed to defects or impurities in the crystal [21] . The exponential absorption tail follows the Urbachs rule, i.e. the spectra can be tted by the empirical equation (E) = 0 exp (E Eg ) kB T (2.1)

where T is the absolute temperature, kB is the Boltzmann constant, 0 and are dimensionless temperature depending parameters and nally Eg is the band gap. The three parameters are characteristic of each material and 0 is assumed as pressure independent [22] . On the other hand, determines the shape of the absorption tail and indirectly gives indications on the presence of defects in the crystal structure [22] . In Eq. (2.1) 0 and Eg are clearly correlated. Therefore, we determined 0 at ambient pressure (0 = 130(1) cm-1 ) assuming that Eg = 2.3 eV [12] and that 0 is constant under compression. This method can lead to small uncertainties on the absolute value of Eg , but it is very accurate to determine its pressure evolution. The t of Urbachs rule to our experimental data is quite good, as can be seen in Fig. 2.6.

12

2.5. Optical absorption at ambient pressure

Suggested assignements Lattice modes

0 [cm1 ] 42* 45 57 62 73 81* 83 95 99* 110 116 136 149 178 185 327 338 347 359 378 402 407 440 451 479 801 825 840 856 879

[cm1

d/dP GPa1 ] 0.7 1.0 3.7 1.6 -0.2 -1.8 4.2 0.4 2.8 4.2 6.8 5.5 5.2 7.7 4.3 -0.5 1.8 1.5 1.0 2.8 0.8 3.7 3.9 2.2 5.4 4.3 3.3 1.9 3.5 3.2

0.96 1.27 3.70 1.47 -0.16 -1.27 2.87 0.24 1.61 2.18 3.35 2.31 1.99 2.46 1.32 -0.09 0.30 0.25 0.16 0.42 0.11 0.52 0.51 0.28 0.64 0.31 0.23 0.13 0.23 0.21

Bending of CrO4

Stretching of CrO4

Table 2.3.: Raman active modes for PbCrO4 at ambient conditions (0 ), pressure coecients d/dP and Grneisen parameters . The phonons marked with and asterisk are u extrapolations of the high pressure data down to ambient pressure.

13

3. Experimental results and conclusions

3.1. High-pressure X-ray diraction experiments
The evolution of the X-ray patterns under compression for pressures up to13 GPa is shown in Fig. 3.1. We can analyze it in therms of the dierent pressure ranges.

1 bar (r)

12 GPa

Intensity (arb. units)

9.1 GPa

7.2 GPa

6.1 GPa

5.2 GPa

4.4 GPa

3.25 GPa

0.55 GPa

10

15

2 (degrees)

Figure 3.1.: X-ray patterns at selected pressures. Arrows indicate changes induced by the rst phase transition. Ticks indicates Bragg reections.

In the range 03.25 GPa the spectra retain the shape corresponding to the original structure i.e. the mineral is stable up to 3.25 GPa. When pressure rises beyond this value, and up to 5.2 GPa, some peaks begin to split. This doesnt necessarily imply a structural phase change but it is likely due to a distortion of the low-pressure phase, as we will see in a moment. Starting from 5.2 GPa there are evident changes in the patterns and this trend is maintained up to 9.1 GPa. These changes are now due to an eective phase transition, that take places at about 6.1 GPa and that is fully completed at 9.1 GPa. In the range 5.29.1 GPa the two phases then coexist. Finally, in the range 9.112 GPa the diraction pattern doesnt change with increasing pressure so no new structural phase transitions are observed. The transition at 6.1 GPa is reversible, given that the diraction pattern recovers its original shape when reverting to ambient

15

3. Experimental results and conclusions

102.5

7.4

Lattice parameter ()

102.0

b
7

angle (degrees)

7.2

101.5

101.0

6.8

a
6.6

100.5

c
100.0

Pressure (GPa)

Pressure (GPa)

Figure 3.2.: Pressure evolution of the unit-cell parameters of PbCrO4 for the low-pressure phase.

Atom Cr Pb Atom Cr Pb

O1 1.590(3) 2.489(8) O6 2.591(2)

Bond lengths [A] O2 O3 O4 1.613(3) 1.616(7) 1.642(4) 2.506(8) 2.517(6) 2.538(6) O7 O8 O9 2.612(1) 2.655(8) 3.012(1)

O5 2.557(1) O10 3.267(4)

Table 3.1.: Bond lengths for the polyhedral units at 5.2 GPa.

pressure. This also indicates that pressure does not induce the decomposition of PbCrO4 into binary oxides. The evolution of the crystallographic parameters as a function of pressure for the lowpressure phase is plotted in Fig. 3.2, together with the corresponding ts. It is clear that the compressibility of PbCrO4 is not isotropic, given that the a, b axes are more compressible than the c axis. This is due to the relative arrangement of the CrO4 and PbO9 polyhedra in PbCrO4 (see Section 2.3), that alternate in the c direction giving place to structures less compressible than the void space that exist between the polyhedral units along the other directions. The evolution of the 4 parameters is linear up to 3.5 GPa, where there is a change in the trend for c and . This is related to to the aforementioned changes in the diraction patterns and indicates that the reduction of inter-atomic distances causes an atomic reordering with changes in the local coordination; in particular the coordination of the Pb atoms increase from 9 to 10 (see also Section 2.3); the diraction patterns are still compatible with a monoclinic structure with monazite symmetry, so this is a distortion of the original monazite structure. Given that the angle decreases with pressure, we can expect an increase in the symmetry of the crystal: this is reasonable [8] and is also reected in the lower number of peaks in the diraction patterns at higher pressures. Using the data relative to the cell parameters, we could also study the evolution of the

16

3.2. High-pressure Raman experiments

0

Pressure (GPa)

1.00

1.02

1.04

V0/V (adim)

1.06

1.08

1.10

1.12

Figure 3.3.: Pressure evolution of the volume of the unit cell.

Lattice parameters (HP phase) a [] A b [] A c [] A V [3 ] A 6.95(6) 6.11(6) 6.63(6) 282(8)

Z 4

Table 3.2.: Lattice parameters for PbCrO4 for the high-pressure phase.

volume of the unit cell (Fig. 3.3) and determine the bulk-modulus B0 of PbCrO4 . The t of the data in Fig. 3.3 with Eq. (1.2) resulted in a bulk modulus B0 = (58 1) GPa (and B0 = 3.1 0.4). For comparison, monazite phosphates often have bulk moduli larger than 100 GPa [8] , so monazite chromates appear to be much more compressible than phosphates. The reference to phosphates is mandatory, given that no other monazite-type chromates, like for example LaCrO4 or SrCrO4 , have been studied under compression. Regarding the high-pressure phase, i.e. beyond 9.1 GPa, we have found that the diraction pattern is compatible with an orthorhombic unit cell with the parameters given in Table 3.2. Moreover, the systematical extinctions in the diraction patterns allowed us to assign the P 21 21 21 space-group symmetry to this phase. This is compatible with theoretical and empirical arguments (Bastides diagram [23] ). In short, the high-pressure phase is likely to be a strongly distorted barite [24] . Lead coordination increases up to 12 and the structure is formed CrO4 and PbO12 polyhedra; the results of Raman and optical-absorption experiments are compatible with this hypothesis, as we will see in a moment.

3.2. High-pressure Raman experiments

The Raman spectra of PbCrO4 for pressures up to 13 GPa are showed in Fig. 3.4, while the pressure evolution of the detected phonons is showed in Fig. 3.5.

17

3. Experimental results and conclusions

1 bar (r) 13 GPa 11.6 GPa

Intensity (arb. units)

9.4 GPa 7.5 GPa 5.3 GPa

3.5 GPa

2.5 GPa

1.5 GPa

1 bar

200

400

600

800

1000

1200

Raman shift (cm-1)

Figure 3.4.: Raman spectra of PbCrO4 at dierent pressures.

Figure 3.5.: Evolution of Raman active modes for PbCrO4 under compression.

18

3.2. High-pressure Raman experiments At very low pressure the evolution of the Raman spectra is characterized by the splitting of several modes: this is undoubtedly due to the anisotropic compressibility of PbCrO4 (see Section 3.1). This anisotropy breaks the ambient pressure degeneracy of some modes that are very near in frequency and makes them to evolve dierently. Upon further compression there are changes in the Raman patterns, mainly located in the lowfrequency range (indicating the intervening changes in the crystallographic parameters, given that these frequencies correspond to lattice vibrations, as shown in Table 2.3). The mode at 42 cm1 is visible only beyond 2 GPa, due to the presence of the edge lter. Its position at ambient pressure is an extrapolation of the high-pressure data. For most of the observed phonons their evolution consist in a monotonic, linear hardening1 . Some of the modes, though, show an unusual behavior. In particular the modes at 73, 81 and 327 cm1 clearly soften under compression. This behavior may be related to the onset of the phase transition (atomic reordering) that was detected by means of the XRD experiments in the range 3.255.2 GPa. Up to 4.5 GPa there are not other qualitative changes in the Raman spectra. However, some modes show a nonlinear behavior in this range and three extra weak modes, at 60, 930 and 950 GPa, appear beyond 3.5 GPa. In the range 5.310.1 GPa the Raman spectra change drastically, likely due to the completion of the monoclinic-to-monoclinic phase transition detected in diraction experiments beyond 3.25 GPa. In particular, we can observe a general decrease in the intensity of the spectra together with an increase in the number of the high-frequency modes and a decrease on the mid-range modes. This is evident in both Fig. 3.4 and 3.5. The increase of the high-frequency modes can be attributed to a distortion of the CrO4 tetrahedra of the structure resulting from the rst phase transition: some of the modes can, in fact, be degenerate in the low-pressure monoclinic phase but not in the high-pressure monoclinic phase. As a last remark, it is important to note that the extra peaks in the range 3.5-3.3 GPa correlate well with phonons of the high-pressure monoclinic phase. So, their presence and the evolution change of nonlinear modes can be hints of the onset of the monoclinic-to-monoclinic transition. No other important changes occur in this range, but for the appearance of some weak modes in the low- and intermediate-frequency range. This can be associated with the coexistence of the two phases detected in the XDR experiments. The Raman modes for the high-pressure monoclinic phase are reported in Table 3.3, together with their pressure coecients. Beyond 10.1 GPa no substantial changes occurs in the Raman spectra; on the other hand, a sudden drop of the Raman signal at pressures beyond 11.6 GPa and a corresponding reduction in the number of modes is compatible with the completion of the second phase transition. The decrease in the number of modes is compatible with the increase in the symmetry of the crystal from the monoclinic phase to the observed orthorhombic phase. Upon further compression and up 17.9 GPa (the highest pressure reached in our Raman experiments) no other changes are visible in the Raman spectra. Upon the subsequent decompression, the original phonons are recovered, so this is another conrmation of the
1

In Raman spectroscopy, hardening (softening) modes are modes with a positive (negative) derivative, with respect to a physical variable (pressure, in our case).

19

3. Experimental results and conclusions 0 [cm1 ] 44 59 70 85 101 116 139 168 200 217 338 351 d/dP [cm1 GPa1 ] 0.9 0.4 0.7 -0.8 4.0 3.7 1.8 3.4 4.0 8.2 2.9 0.9 0 [cm1 ] 370 386 466 746 815 834 847 857 916 928 933 d/dP [cm1 GPa1 ] 0.9 1.0 0.8 0.4 1.0 1.4 1.5 3.4 1.6 -0.3 1.0 -

Table 3.3.: Raman active modes at 6.4 GPa for the high-pressure monoclinic phase of PbCrO4 (0 ) and pressure coecients (d/dP ).

reversibility of the two phase transitions. Parameters such as the phonon frequencies at ambient pressure 0 , pressure coecients d/dP and the Grneisen parameters have been calculated from the data in Fig. u 3.4 and 3.5 and are listed in Table 2.3. A comparison of the data in Table 2.3 and Table 3.3, related respectively to the original monoclinic phase and the high-pressure monoclinic phase, shows that the phonons with similar frequencies also have similar pressure coecients. This can be regarded as a conrmation of the similarity of the two monoclinic phases.

3.3. High-pressure optical-absorption experiments

We have performed optical-absorption experiments in ve dierent samples. All of them showed the same optical behavior under compression. The absorption spectra at selected pressures are shown in Fig. 3.6. At every pressure in our experimental range the spectra show the typical aspect of a direct band gap semiconductor, with the exponential dependency given in Eq. (2.1). Upon compression the absorption edge gradually redshifts until, when reaching 3.4 GPa, a sudden collapse of the band gap takes place and, correspondingly, the color of the sample turns from orange to red-violet, as in Fig. 2.3. This change in the optical properties of PbCrO4 is probably related to the rst phase transition (monoclinic to HP monoclinic) put in evidence by XRD and Raman experiments at similar pressures. Upon further compression beyond 3.4 GPa the absorption still shows an exponential dependence and its pressure evolution is again toward lower energies. At a pressure of about 12 GPa all the samples became completely opaque in the optical wavelength range, because the absorption edge lay completely in the near IR range. This change is likely due to the HP monoclinic to orthorhombic phase transition seen at the

20

3.3. High-pressure optical-absorption experiments

4.3 GPa 5 GPa

2.0
14.3 GPa 11 GPa 12.8 GPa 13.7 GPa 9.6 GPa 8.8 GPa

3.4GPa

18.1 GPa

1.5

(10 cm-1)

1.0

0.5

0.0 1.0 1.5 2.0 2.5

Figure 3.6.: Absorption spectra of PbCrO4 at selected pressures.

same pressure in the XRD and Raman experiments. Beyond 12 GPa the spectra retain their exponential dependence on energy, with no signicant changes in the behavior of the absorption edge. The maximum pressure that we could reach was about 21 GPa, due to experimental limitations and to the formation of a large number of defects in the crystal. Both factors made very dicult the obtainment of satisfactory spectra. Upon pressure release the changes in the spectra are reversible, similarly to what happens in Raman and XDR. One thing that worth noting is that a small hysteresis in the recuperation of the original monazite phase is observed in all the experiments. The dependence of the energy gap Eg with pressure is shown in Fig. 3.7, that has been obtained under the hypothesis that the fundamental gap of PbCrO4 is direct in every phase and thus that Eg can be calculated using Eq. (2.1). The evolution of Eg is linear up to 3 GPa, with dEg /dP = 48(2) meV/GPa. From 3 to 3.5 GPa Eg decreases abruptly with Eg = 0.4 eV and then its evolution is linear again up to 15 GPa, with a pressure coecient of -45 meV/GPa. Apparently a second, smaller 0.1 eV collapse of Eg is visible at this pressure. Its presence is still unconrmed, though reasonable. In the range 1521 GPa the pressure coecient changes to -67(2) meV/GPa, while the evolution of Eg is still linear. The variations of in Eq. (2.1) are comparable with the error of this parameter, so no conclusions can be drawn. The results of these experiments can be understood with reference to the theoretical band structure of PbCrO4 [12] , represented in Fig. 3.8. According to it, in PbCrO4 the main contribution at the bottom of the conduction band results from the non bonding interaction between the Cr(3d) orbitals and the O(2p) orbitals. The upper portion of the

16.1 GPa 14.8 GPa

20.8 GPa

19.1 GPa

Energy (eV)

6.8 GPa

2.9 GPa

0.4 GPa

21

3. Experimental results and conclusions

2.5

2.0

E g (eV)

1.5

1.0

0.5

10

15

20

Pressure (GPa)
Figure 3.7.: Pressure dependence of Eg for PbCrO4 . Dierent symbols denote dierent samples. Closed symbols are pressure upstroke, open symbols for pressure downstroke.

conduction band results primarily from the interaction between empty Pb(6p) orbitals and O(2p) orbitals. Also a minimum contribution from the Pb(6p) orbitals is observed at the bottom of the conduction band, since the space group symmetry permits mixing of the Pb(6p) and Cr(3d) orbitals. On the other hand, the top of valence band is mainly compose of O(2p) non bonding orbitals with a small contribution of Pb(6s) orbitals.We could attempt an explication of our results based on an analogy to what happens for the scheelite phase PbWO4 [25] , whose band structure is similar to that of PbCrO4 [12] ; under compression, the decrease in Cr-O and Pb-O distances causes an increase in the crystal eld acting on Cr(3d) and Pb(6s) states. Because of the dierent coordination of Pb and Cr, the Pb(6s) states shift toward higher energy faster than the Cr(3d) states and so the band gap closes, as a consequence of the reduction of the dierence in energy between the top of the valence band and the bottom of the conduction band. The collapse of Eg at 3.5 GPa could be caused by the structural changes related to the monoclinic-to-monoclinic phase transition occurring at this pressure, according to XRD and Raman experiments. In particular, the coordination of the Pb cation increases from 9 to 10 and this could be the reason behind the sudden decrease of Eg . From 3.5 to 14 GPa the linear decrease in energy gap is caused by the same facts than in the low pressure range. Upon further compression the ocurrence of the monoclinicorthorhombic transition leads to the small collapse and slight change in the slope of Eg that is observed at 15 GPa. This is reasonable, given that the second transition would imply a further increase in the coordination of Pb from 10 to 12 (see Section 3.1). The conrmation of this hypothesis requires some theoretical calculations that are not available at the moment. On a side note, the opacication of the samples at 12 GPa suggests a possible metallic character of the orthorhombic phase. The conrmation of

22

3.4. Conclusions

4.2

Pb(6p) Cr(3d) - O(2p)

2.3

Energy (eV)

2.3 eV 0.0

Pb(6s) - O(2p) O(2p) Cr(3d) - O(2p) Pb(6s) - O(2p)

-8.0

Figure 3.8.: Schematic band structure of monazite-type PbCrO4

this hypothesis would come from the complete collapse of the energy gap at a suitable pressure. The optical absorption experiments in the range 1221 GPa did not show any evidence for a such collapse. Unpublished third party electrical measurements show indeed that the resistivity of powder samples decreases at least one order of magnitude upon compression, reaching a minimum of about 1.5 cm at 13 GPa. On the other hand, not only this value is much higher than those typical of a metal (105 106 cm), but those same experiments show also that upon further compression and up to 35 GPa the resistivity of the samples increases again up to 10 cm [26] .

3.4. Conclusions
A fairly complete characterization of monazite-type PbCrO4 at ambient pressure and under compression has been presented in this work. The study involves several dierent experimental techniques that complement each other in the conrmation of the results. By means of structural XRD studies we could determine the unit cell parameters of monazite-type PbCrO4 and their pressure evolution, along with that of the unit cell volume and the equation of state at room temperature. On the other hand, these measurements showed the existence of two phase transition in our pressure range: the rst is detected at 3.255.3 GPa, depending on the characterization technique, and is a a monoclinic-to-monoclinic transition, i.e. the second phase possesses the same crystal symmetry than the rst one but a dierent local atomic arrangement. The second transition takes place at 915 GPa and is a monoclinic-to-orthorhombic transition, associated

23

3. Experimental results and conclusions thus with an increase in the crystal symmetry. In correspondence with the second transition a strong opacication of the crystal is observed, but our initial hypothesis about the metallization of the mineral has been discarded on the basis of subsequent optical and electrical experiments. Raman spectroscopy conrmed the results of the XRD studies. The transitions occur at similar pressures in both experiments and the ne details of the Raman patterns are compatible with the crystal structure that was hypothesized on the basis of XRD. The evolution of Raman modes has been reported for the low pressure and high pressure monoclinic phases. Moreover, we could improve some previous studies on the Raman spectrum of PbCrO4 at ambient pressure, individuating some phonons that had never been detected before. Finally, the evolution of energy gap has been studied through optical absorption experiments up to 15 GPa. The band gap collapse of 0.4 eV corresponding to the rst phase transition is clearly visible, while an unconrmed smaller collapse should be associated to the second transition. An explication of the results has been thus attempted using the theoretical band structure model and by analogy with an ane semiconductor, the scheelite-type PbWO4 . Even if the experimental picture is pretty coherent, theres is room for some theoretical speculations: a set of detailed ab initio calculations of the crystal structure and the band structure of PbCrO4 under compression could denitively conrm some of our qualitative and phenomenological conclusions. The results here reported have already been published [E. Bandiello, D. Errandonea, et al., PRB 85, 024108 (2012)] and presented in two posters at the 49th (Budapest) and 50th (Thessaloniki) EHPRG Conferences.

24

Appendices

25

A. Space groups
A.1. Space groups
For the complete description of the crystal structure of a particular substance the knowledge of the contents of the unit cell is required. The translational symmetry of the lattice then builds the crystal by propagating the structure of the unit cell. On the other hand, other symmetry elements dierent from translations are normally found in the unit cell of a crystal, so often it is not necessary to describe the whole unit cell, but only one part of it, given that the additional symmetry elements within the unit cell determine the remainder of its content. Symmetry can be used to shorten considerably the description of the structure of a crystal; more importantly, a knowledge of the crystal symmetries reduces the number of atomic coordinates that have to be found in the determination of a crystal structure. The HermannMauguin (H-M) notation is one of the the standards in crystallography to represent the symmetry elements of a crystal. Here we will report some informal notes about the H-M notation, particularized to the two space groups we are dealing with in this thesis. It is useful to start the discussion by giving some common denitions: Lattice System: This is the shape of the bare unit cell of a crystal. In 3D exist 7 dierent lattice systems; they are listed in Table A.1. Bravais Lattice: A set of equivalent lattice points. They are generated combining each lattice system with one of the following lattice types (in the H-M notation): P (primitive), I (body centered), F (face centered), A, B, C (nodes at the center of each yz, xz and zy face respectively), R (rhombohedral). Point Group(or Crystal class): A set of geometric symmetries (isometries) that keep at least one point xed. Space Group: The complete description of the symmetries of a particular crystal. There are 14 Bravais lattices in 3D, constructed from the simplest translational symmetries applied to the seven crystal systems. All crystal systems have P lattices, but not all the systems have the other type of lattices. This is because there is degeneracy when all the lattice types are applied to all the crystal systems. Because of these degeneracies the number of possible Bravais lattice is reduced to 14. Point groups are in number of 32 and they are the results of the combinations of the following three symmetry elements: Rotation Axes: an n-fold rotation axis is denoted by n in the H-M notation. It is dened by the condition that a rotation by an angle of 360/n with respect to the axis

27

A. Space groups Crystal System Triclinic Monoclinic Orthorhombic Tetragonal Rhombohedral Hexagonal Cubic Lattice types P P, C P , C, I, F P, I P P P , I, F Parameters a = b = c, = = = 90 a = b = c, = = 90 = a = b = c, = = = 90 a = b = c, = = = 90 a = b = c, = = = 90 a = b = c, = = 90, = 120 a = b = c, = = =90

Table A.1.: Resume of 3D Bravais lattice and related parameters.

leaves the crystal invariant. The requested compatibility with the translational symmetry only allows for n =1, 2, 3, 4, 6. Inversion Axes: Inversion axes are the same as rotation axes, except that after the 360/n rotation the object is projected through a inversion center on the axis. The H-M symbol for a n-fold inversion axes is n. Mirror Planes: a mirror plane simply creates a reected image of the crystal with respect to itself. It is indicated by m. Not all the combinations are permitted, only those compatible with the fundamental translational symmetry of the crystal system. Intuitively point-group symmetries can be thought of as attached to some particular points of the unit cell. These points depends on the lattice systems: they are the corners of the unit cell in the P lattices, while for an I lattice they are situated at the body center of the cell as well as at the corners and so on for the other lattice types. There are two further symmetry operations occurring in crystals, that are not part of the 32 point groups because they involve translations: Screw Axes: Indicated by nz , a screw axis generates a rotation of 360/n around itself, followed by a translation by z translations of z/n x, where x is a lattice vector parallel to the screw axis. Glide Plane: A glide plane operates a mirror operation followed by a translation. The symbols for glide planes are a, b, c for a glide translation along a/2, b/2, c/2, n for a glide translation along with half a face diagonal (the same symbol for all the faces), d for for a glide translation along with a quarter of a face diagonal and nally e for two glides along the same glide planes and a translation along two dierent half lattice vectors. Finally a space group is a combination of the translational symmetry of a lattice together with other symmetry elements such as point group symmetries, screw axes and glide planes. Once taken in account the degeneracies due to dierent choices of axes and their orientations, we are left with a total of 230 dierent space groups. A visual depiction of each space group is achieved using a set of standard crystallographic symbols [27] .

28

A.1. Space groups Multiplicity 2 1 1 Wycko letter c b a Site symmetry m 1 1 Coordinates (1) x, y, z (2) x, y , z 1 x, 2 , y x, 0, y

Table A.2.: Wycko sites for the monoclinic P m space group.

The H-M notation uses a set of two to four symbols to completely identify a space group. The rst symbol is always a single letter specifying the Bravais lattice (P, C, I, F, R) while the next three symbols the symmetry elements related to certain directions (point group and translation elements) as combination of the symbols 1, 2, 3, 4, 5, 6, a, b, c, e, n, /, , that have been described before. Two kinds of notations are used when specifying a given space group: the full H-M symbol shows both rotation/screw axes which run parallel to the specied direction, as well as any mirror/glide plane perpendicular to the same direction. These two symbols will be separated by a /; the short H-M symbol is a more condensed notation that depends on the symmetry constraints of each lattice type and/or the existence of some special axis (in the monoclinic lattice, for example, theres only one unique axis that is perpendicular to the other two, so unambiguous short symbols can be used; conversely, in the cubic system all the axes are equivalent and the full H-M symbols are needed). The two forms are equivalent, i.e. they can be converted in each other. Finally, the H-M symbol for a given space group can also depend on the choice of the unit cell (when this is not unique) and on the possible orientations/permutations of the three base axes.

A.1.1. Wycko positions

Associated to each space group there are some particular positions, called Wycko positions or sites, that physically indicate where the atoms in the unit cell can be found. The information that they provide is how many atoms are generated through the symmetry elements of the crystal when an atoms is placed in a given position (multiplicity) and where they are. They are indicated by a number, the multiplicity of the site, and a letter label. As a classical example to understand how Wycko positions work is useful to examine the monoclinic P 1m1 space group (P m, in the short H-M notation). This space group has only two symmetry elements, i.e. two mirror planes respectively at y = 0 and y = 1 . If we place an atom at an arbitrary position x, y, z then symmetry generates 2 a second atom at x, y , z (multiplicity is 2; y stands for y, as customary in crystallog raphy). On the other hand, if the atom is placed right on one of the mirror planes, for 1 example x, 2 , z, then no other atoms are generated (multiplicity is 1). The complete list of the Wycko sites for the monoclinic P m lattice is listed in Table A.2. Even if it is referred to a particular space group, the scheme of the Table A.2 is completely general. The multiplicity column gives the number of equivalent positions per unit cell, while the coordinates column shows the relations between corresponding positions. The letters are simply labels, with no physical meaning. They are assigned

29

A. Space groups

Figure A.1.: P 21 /n space group [28] .

alphabetically from the bottom up. The symmetry column tells us what symmetry elements the atom resides upon. The uppermost Wycko position, corresponding to an atom at an arbitrary position, never resides upon any symmetry elements. This Wycko position is called the general position. All of the remaining Wycko positions are called special positions. They correspond to atoms which lie upon one of more symmetry elements and because of this they always have a smaller multiplicity than the general position. Furthermore, at least one of their fractional coordinates must be xed.

A.2. Monoclinic P 21 /n space group

The full H-M symbol for this group is P 121 /n1; the short form P 21 /n is unambiguous if the unique axis is specied. In our case case this is the b axis. The symmetry elements of this space groups are then 21 screw axes parallel to b and glide planes perpendicular to it. The graphical representation of the space group is given in Fig. A.1. The b axis is directed along c a. The following symmetry elements are represented in Fig. A.1:
2-fold screw axes parallel to b. Symbol: . inversion centers. Symbol: . two diagonal glide planes orthogonal to b, situated at 1 b and 4
1 4

1 2

b. Symbol:

The circles represent the position of the atoms in the cell. The + symbol indicates the initial point, i.e. an atom at an arbitrary position with z > 0 (z < 0 for - ). The remaining symbols represent the atoms generated by the symmetry operations acting 1 on the initial point. The 2 symbols are atoms related by symmetry to + but now at a height z 1 . The symbol indicates a change of handedness with respect 2

30

A.3. Orthorhombic P 21 21 21 space group to the initial point, with the same meaning for the superscripts. The complete Wycko positions for P 21 /n are listed in the Table A.3 below [27] . Multiplicity 4 2 2 2 2 Wycko letter e d c b a Site symmetry 1 1 1 1 1 Coordinates (1)x, y, z (3), y , z x
1 2 , 0, 0 1 1 2 , 0, 2 1 0, 0, 2 1 (2) + 2 , y + 2 , z + x 1 1 1 (4)x, y + 2 , z + 2 1 2

0, 0, 0

1 1 0, 2 , 2 0, 1 , 0 2 1 1 , 2, 0 2 1 1 1 2, 2, 2

Table A.3.: Wycko sites for the monoclinic P 21 /n space group.

A.3. Orthorhombic P 21 21 21 space group

Crystals with P 21 21 21 space group have 21 screw axes, directed along the three base vector. The schematic representation of this space group is given in Fig. A.2, in which the c vector is directed toward the reader; the notation is the same as in Fig. A.1, except for the arrows, which symbolize the direction of a 2-fold screw axis when it is parallel to the plane of the projection. A fractional h attached to such a symbol indicates two axes with heights h and h + 1 . No fraction stands for h = 0 and h = 1 . 2 2 There is only one Wycko position, the general one, indexed 4a and with 1 symmetry. Its coordinates are given in Fig. A.2.

Figure A.2.: P 21 21 21 space group [28] .

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B. Raman spectroscopy and notation.

B.1. Raman Spectroscopy
Raman scattering is caused by the change in the polarizability of molecules or susceptibility of crystal when subject to a time-varying electric eld. Quantum mechanically this process can be viewed as a two-particles interaction between a phonon and an optical photon. Energy-momentum conservation gives 0 (q) = 0, k0 k q = 0, (B.1a) (B.1b)

where 0 , k0 and , k characterize the incident and scattered photon respectively, while (q) and q are the angular frequency and momentum of the phonon. For the light in the visible region of the spectrum k0 and k are of the order of 103 times a reciprocal lattice vector; this means that only excitations in the center of the Brillouin zone (q 0) can take part in Raman scattering. In the Eq. (B.1a) and (B.1b) the + sign is for phonon generation and the - sign is for absorption. The interaction of the visible light with solid occurs via the polarizability of the valence electrons. The electric eld E 0 induces, via the susceptibility tensor , a polarization P , i.e.1 P = 0 E 0 or Pi = 0 ij Ej0 . (B.2) The periodic modulation in P leads, in turn, to the emission of a wave, the scattered wave, that in a classical approximation can be regarded ad dipole radiation from the oscillating dipole P . The oscillatory nature of the electric eld interacting with the atoms in a crystal lattice makes the vibrational analysis easier if it is conducted on the basis of the normal modes of the crystal, i.e. a set of motions in which all parts of the system move sinusoidally with the same frequency and with a xed phase relation, one frequency and one phase for each mode. The most general motion of a system can thus be described as a superposition of its normal modes. The modes are normal in the sense that they are independent, that is to say that an excitation of one mode will not cause motion of a dierent mode. In this respect, the susceptibility tensor is conveniently written as a function of the so-called normal coordinates Qk , that refer to the position of atoms away from their equilibrium position. Each normal coordinate, relative to a single normal mode, is a
1

The Einstein notation for summation has been used: when an index appears twice in a single term it implies summation of that term over all the values of the index.

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B. Raman spectroscopy and notation. linear combination of the cartesian displacement coordinates of the positions of the atoms. Given that we expect an harmonic motion of each atom, the normal coordinates relative to the induced vibrations [(q), (q)] can be written as Qk = Qk0 cos((q)t), considering that q 0. On the other hand, the oscillating electric eld is given by E 0 = E 0 cos(0 t) and so, performing a rst order Taylor expansion of 0 + Qk Qk or ij
0

(ij )0 +

ij Qk

Qk ,
0

the polarizability P given in Eq. (B.2) can be expressed as: Pi = +

0 (ij )0 Ej0 cos(0 t)+

1 2

ij Qk

Qk0 Ej0 [cos(0 + (q)t) + cos(0 (q)t)] .

0

(B.3)

The scattered radiation thus contains an elastic contribution of frequency 0 (Rayleigh scattering) and two further terms, called Raman side bands, with frequencies 0 (q). The plus and minus sign correspond to scattered light quanta that have absorbed and, respectively, lost the energy of the elementary excitation [(q), q]. The component of frequency 0 (q) are called Stokes, and anti -Stokes the components with frequency 0 + (q). For the anti-Stokes components to exist, is necessary that already excited phonon are present in the solid. At ambient temperature the intensity of anti-Stokes emission is then much reduced (106 times the Stokes radiation), because the elementary excitations are mainly in their ground state. The term jl /Qk in Eq. (B.3) is called the Raman tensor and is often written simply as ijk . The i, j indexes range from 1 to 3, while the k index ranges from 0 to 3N 3, that is the number of optical modes with q = 0 for a crystal with N atoms in the unit cell. The Raman tensor which refers to all zone-center vibrations has thus rank 3. For an individual mode this tensor is given by a 3 3 matrix Rk determined from the derived susceptibilities. This matrix is called the Raman tensor of a particular mode. The intensity Ik of the scattered light for a particular mode is proportional to the square of its Raman tensor. If ei and es are the unit vectors of the incoming and scattered light, it can be proven that the Raman scattering intensity is proportional to Ik |ei Rk es |2 . (B.4)

From Eq. (B.3) it is clear that prerequisite for the observation of a Raman line is that the susceptibility has a non-vanishing derivative with respect to the coordinate Qk of the elementary excitation. By means of the group theory, knowing the point group of a crystal and the Wycko positions occupied by the atoms in the unit cell, it can be determined which components of the Raman tensor are dierent to 0 and so if the mode is or not Raman active.

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B.2. Raman tensors for PbCrO4 Symbol A, B E, T Xg , X u X,X X1 , X 2 Meaning Singly degenerate state, symmetric (A) or anti-symmetric (B) with respect to rotation about the principal n axis Doubly (E) or triply (T) degenerate state The state is symmetric (g, gerade) or anti-symmetric (u, . ungerade) with respect to a an inversion 1 The state is symmetric () or anti-symmetric () with respect to a mirror plane m The state is symmetric (1) or anti-symmetric (2) with respect to additional n or m
Table B.1.: Mullikens symbols

B.1.1. Mullikens symbols

Each particular Raman mode, represented by an Rk matrix, is characterized by its symmetries relative to the normal coordinates and by its degeneracy, that depend on the point group of the crystal under examination and on the Wycko positions occupied by the atoms in the unit cell. The symmetries can be determined experimentally by means of polarized Raman measurements performed on properly oriented monocristalline samples. A set of symbols, introduced by Mulliken [29] , are used to label the modes with respect to symmetries/degeneracy. They are listed in Table B.1. For each crystal system, the vibrational modes can have only denite symmetries: A, B for triclinic, monoclinic and orthorhombic system; A, B, E for the tetrahedral, rhombohedral and hexagonal system and nally A, E, T for cubic crystals. Symmetric g modes are Raman active, while anti-symmetric u modes are IR active.

B.2. Raman tensors for PbCrO4

In the case of monoclinic PbCrO4 the space group is P 21 /n and the Wycko positions of the atoms are all 4e, with site symmetry 1. These data allow software tools like SAM2 , hosted on the Bilbao Crystallographic Server [30] , to predict the theoretical number of phonons and their symmetries/degeneracy. In our case 3 Ag modes and 3 Bg modes per atom are expected, so a total of 36 Raman modes (18+18). In the so-called mechanical notation this is written as = 18Ag + 18Bg .
2

(B.5)

Spectral Active Modes

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B. Raman spectroscopy and notation. The character of the individual modes can be specied, when needed. Finally, the explicit expressions of the matrices Ag and Bg are: a d 0 0 0 e A g = d b 0 , Bg = 0 0 f . (B.6) 0 0 c e f 0

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C. Software
C.1. Software tools
The following is the list of the software used for this work. Qtiplot 0.9.8.8 and OriginPro 8.6 for data plots and analysis.

[32] for the analysis of the Raman spectra. Inkscape 0.48.3.1 for SVG graphic. The Gimp 2.8.0 for the editing of photos and images. LibreOce 3.5.4.2 for some data processing and text editing. A Final document composed using the TEXLive distribution of L TEX 2 , in conintegrated Latex environment. junction with Kile 2.1.0 Operating system was Sid Debian GNU/Linux with KDE 4.8.4 environment. The items marked with are GPL software.
Fityk 0.9.8

Vesta 3.1.0 [31] for the crystallographic plots and calculations.

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Bibliography
[1] B. Palosz, S. Gierlotka, S. Stelmakh, R. Pielaszek, P. Zinn, M. Winzenick, U. Bismayer, and H. Boysen. High-pressure high-temperature in situ diraction studies of nanocrystalline ceramic materials at hasylab. Journal of Alloys and Compounds, 286(12):184 194, 1999. [2] W.B. Holzapfel. Renement of the ruby luminescence pressure scale. Journal of Applied Physics, 93:18131818, Feb 2003. [3] S. Klotz, J.C. Chervin, P. Munsch, and G. Le Marchand. Hydrostatic limits of 11 pressure transmitting media. Journal of Physics D: Applied Physics, 42(7):075413, 2009. [4] D. Errandonea, Y. Meng, M. Somayazulu, and D. Husermann. Pressure-induced a transition in titanium metal: a systematic study of the eects of uniaxial stress. Physica B: Condensed Matter, 355(14):116 125, 2005. [5] R. Lacomba-Perales. Estudio de las propiedades pticas bajo presin de las scheelo o itas de PbWO4 y BaWO4 y la wolframita de ZnWO4 . Masters thesis, Universidad de Valencia, 2007. [6] J-P Poirier. Introduction to the Physics of the Earths Interior. Cambridge University Press, 2nd edition, 2000. [7] N. Clavier, R. Podor, and N. Dacheux. Crystal chemistry of the monazite structure. Journal of the European Ceramic Society, 31(6):941 976, 2011. [8] R. Lacomba-Perales, D. Errandonea, Y. Meng, and M. Bettinelli. High-pressure stability and compressibility of APO4 (A=La, Nd, Eu, Gd, Er and Y) orthophosphates: An X-ray diraction study using synchrotron radiation. Phys. Rev. B, 81:064113, Feb 2010. [9] T. Huang, J.-S. Lee, J. Kung, and C.-M. Lin. Study of monazite under high pressure. Solid State Communications, 150(3738):1845 1850, 2010. [10] Y.W. Long, L.X. Yang, Y. Yu, F.Y. Li, R.C. Yu, S. Ding, Y. L. Liu, and C.Q. Jin. High-pressure Raman scattering and structural phase transition in YCrO4 . Phys. Rev. B, 74:054110, Aug 2006. [11] D. Errandonea, R. Kumar, J. Lpez-Solano, P. Rodr o guez-Hernndez, A. Muoz, a n M.G. Rabie, and R. Sez Puche. Experimental and theoretical study of structural a

39

Bibliography properties and phase transitions in YAsO4 and YCrO4 . Phys. Rev. B, 83:134109, Apr 2011. [12] M.W. Stoltzfus. Structure-property relationships in solid state materials: A computational approach emphasizing chemical bonding. PhD thesis, The Ohio State University, 2007. [13] S. Quareni and R. de Pieri. A three-dimensional renement of the structure of crocoite, PbCrO4 . Acta Crystallographica, 19(2):287289, Aug 1965. [14] G. Collotti, L. Conti, and M. Zocchi. The structure of the orthorhombic modication of lead chromate PbCrO4 . Acta Crystallographica, 12(5):416, May 1959. [15] F.E. Rosztoczy. The growth of crocoite single crystals. American Mineralogist, 50(5-6):755758, May-June 1965. [16] H. Eenberger and F. Pertlik. Four monazite type structures: comparison of SrCrO4 , SrSeO4 , PbCrO4 (crocoite), and PbSeO4 . Zeitschrift fr Kristallographie, u 176(1-2):7583, 1986. [17] D. Santamar Prez. Private communication. 2011. a e [18] R.L. Frost. Raman microscopy of selected chromate minerals. Journal of Raman Spectroscopy, 35(2):153158, 2004. [19] E. N. Silva, A. P. Ayala, I. Guedes, C. W. A. Paschoal, R. L. Moreira, C.-K. Loong, and L. A. Boatner. Vibrational spectra of monazite-type rare-earth orthophosphates. Optical Materials, 29(23):224 230, 2006. [20] R.W.T. Wilkins. The Raman spectrum of crocoite. Mineralogical Magazine, 38:249 250, 1971. [21] Q. Lin, X. Feng, Z. Man, Z. Shi, and Q. Zhang. Formation of the 350 nm intrinsic color center in PbWO4 crystals. Physica Status Solidi (a), 181(1):R1R3, 2000. [22] J. Ruiz-Fuertes, D. Errandonea, F.J. Manjon, D. Martinez-Garcia, A. Segura, V. V. Ursaki, and I. M. Tiginyanu. High-pressure eects on the optical-absorption edge of CdIn2 S4 , MgIn2 S4 , and MnIn2 S4 thiospinels. Journal of Applied Physics, 103(6):063710 0637105, Mar 2008. [23] D. Errandonea and F.J. Manjn. Pressure eects on the structural and electronic o properties of ABX4 scintillating crystals. Progress in Materials Science, 53(4):711 773, 2008. [24] D. Santamar erez, L. Gracia, G. Garbarino, A. Beltrn, R. Chuli-Jordn, a-P a a a O. Gomis, D. Errandonea, Ch. Ferrer-Roca, D. Mart nez-Garc and A. Segura. a, High-pressure study of the behavior of mineral barite by X-ray diraction. Phys. Rev. B, 84:054102, Aug 2011.

40

Bibliography [25] D. Errandonea, D. Mart nez-Garc R. Lacomba-Perales, J. Ruiz-Fuertes, and a, A. Segura. Eects of high pressure on the optical absorption spectrum of scintillating PbWO4 crystals. Applied Physics Letters, 89(9):091913, Aug 2006. [26] J.J. Hamlin. Private communication. 2011. [27] T. Hahn, editor. The 230 space groups, volume A of International Tables for Crystallography, chapter 7.1, pages 112217. 2006. [28] 1999 Birkbeck College, University of London. [29] R.S. Mulliken. Report on notation for the spectra of polyatomic molecules. The Journal of Chemical Physics, 23(11):19972011, 1955. [30] E. Kroumova, M.I. Aroyo, J.M. Perez-Mato, A. Kirov, C. Capillas, S. Ivantchev, and H. Wondratschek. Bilbao crystallographic server : Useful databases and tools for phase-transition studies. Phase Transitions, 76(1-2):155170, 2003. [31] K. Momma and F. Izumi. VESTA3 for three-dimensional visualization of crystal, volumetric and morphology data. Journal of Applied Crystallography, 44(6):1272 1276, Dec 2011. [32] M. Wojdyr. Fityk: a general-purpose peak tting program. Journal of Applied Crystallography, 43(5 Part 1):11261128, Oct 2010.

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