Trabajo de Grado

A study of optical properties of crocoite (PbCrO4) under compression

Julio de 2011 Alumno: Enrico Bandiello Tutor (1): Domingo Martnez Garca Tutor (2): Daniel Errandonea

To my parents.

Abstract
This thesis deals with the study of optical properties of the semiconductor crocoite (PbCrO4 , band gap energy Eg 2.2 eV) under high-pressure conditions, up to about 12 GPa. The experiments lead to the discovery of two phase transitions in the considered pressure range, both reversible. Also, the pressure dependence of the band gap has been studied. It seems that at pressures around 11 GPa this semiconductor is likely to assume a metallic behavior. The study has been performed on natural samples obtained from the Red Lead Mine (Australia); it has been carried out using optical absorption measurements, performed in a diamond anvil cell (DAC). X-ray diraction (XRD) and Raman spectroscopy (RS) have been also performed to support the conclusions obtained in the optical studies. This work has been carried out under the supervision of Prof. Domingo Mart nez Garc and a Prof. Daniel Errandonea, from the Department of Applied Physics and Electromagnetism of the University of Valencia (Spain).

Resumen
El objeto de esta tesis es el estudio de las propiedades pticas del semiconductor crocoite (PbCrO4 , o energ de la banda prohibida Eg 2.2 eV) bajo condiciones de alta presin, hasta 12 GPa. Los a o experimentos muestran la presencia de dos transiciones de fase en nuestro rango de presiones, ambas reversibles. Adems, ha sido analizado el comportamiento del band gap y se ha visto que a a presiones alrededor de 11 GPa el semiconductor probablemente adquiere un comportamiento metlico. a El estudio ha sido realizado sobre muestras naturales que provienen de las minas Red Lead (Australia) y se ha desarrollado por medio de experimentos de absorcin ptica en celdas de o o diamantes (DAC). Tambin se han realizado experimentos de difraccin de rayos X (XRD) y e o espectroscopia Raman (RS) para apoyar las conclusiones obtenidas en las medidas pticas. o Este trabajo ha sido realizado bajo la supervisin de los Profesores Domingo Mart o nez Garc y a Daniel Errandonea, del Departamento de F sica Aplicada y Electromagnetismo de la Universidad de Valencia (Espaa). n

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Acknowledgements
First of all thanks to my tutors, Prof. Domingo Mart nez Garc and Prof. Daniel Errandonea, a for their help and their patience during the entire realization of this work, in particular in the realization of the experiments, the data analysis and interpretation and the various revisions of the manuscript. Above all, the opportunity to work and learn from them in my rst approach to a real scientic research has been a great privilege. Thanks to Javier Ru Fuertes for the picture of crocoite structure in 2.2 and for the hints in z the normalization of the spectra; whats more important, Im grateful to him for the encouragement and for the serious answers to my frequent naive questions. Thanks to Dr. David Santamar Prez for the assistance in X-ray diraction experiments. a e Dulcis in fundo, thanks to my fantastic wife Karina for supporting me every day, putting up with my moods, patiently listening to my complaints about almost everything in the World and, above all, for often believing in me more than I did myself.

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Contents
1 Methodology and experimental setup 1.1 Diamond anvil cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2 Ruby uorescence as a pressure gauge . . . . . . . . . . . . . . . . . . . . . . . . . 1.3 Experimental setup, sample and measurements . . . . . . . . . . . . . . . . . . . . 2 Properties of PbCrO4 at ambient conditions 2.1 General description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2 Lattice properties and constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3 Optical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 Experimental results, data analysis and conclusions 3.1 Experimental results . . . . . . . . . . . . . . . . . . . . . . 3.2 Data analysis . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3 Dependence of Eg and on P . . . . . . . . . . . . . . . . . 3.4 Physical interpretation . . . . . . . . . . . . . . . . . . . . . 3.4.1 Phase I - Monazite (100 kPa 3.5 GPa) . . . . . . . 3.4.2 Phase I - Phase II transition (3.5 GPa 7.5 GPa) . 3.4.3 Phase II - Phase III transition (7.5 GPa 12.0 GPa) 3.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6 Conclusiones . . . . . . . . . . . . . . . . . . . . . . . . . . Appendices A XRD and Raman experiments A.1 X-ray diraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.2 Raman spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B Software tools B.1 Free Software . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Bibliography 1 1 1 2 5 5 5 6 7 7 8 9 11 12 12 12 13 13 14 15 15 16 17 17 19

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List of Figures
1.1 1.2 1.3 A typical DAC (scheme and photo). . . . . . . . . . . . . . . . . . . . . . . . . . . Experimental setup. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Photo of the sample in the DAC at ambient pressure (L) and at P = 3.5 GPa (R). v 2 3 3

2.1 2.2 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8

XFR analysis of PbCrO4 natural samples (L) and surface of the original crystal magnied at 650x (R). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Crocoite lattice structure, (011) plane. . . . . . . . . . . . . . . . . . . . . . . . . . Absorption spectra of PbCrO4 in the range 1.2 eV < E < 1.9 eV (L) and 1.5 eV < E < 2.4 eV (R) (increasing pressure). . . . . . . . . . . . . . . . . . . . . . . . . . . Absorption spectra of PbCrO4 (decreasing pressure). . . . . . . . . . . . . . . . . . Semi-logarithmic plot of the curves in Figure 3.1 (same ranges). . . . . . . . . . . . Fit of the absorption curve for PbCrO4 at ambient pressure. . . . . . . . . . . . . . Eg (P ) for increasing pressure (L) and decreasing pressure (R). . . . . . . . . . . . Eg (P ) for both increasing (circles) and decreasing pressure (boxes). The dashed line is the data tting for decreasing pressure. . . . . . . . . . . . . . . . . . . . . . Variation of with P . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Schematic band structure of PbCrO4 . . . . . . . . . . . . . . . . . . . . . . . . . .

5 6

7 8 9 9 10 10 11 12 15

A.1 X-ray diraction patterns (L), Raman spectra (R). . . . . . . . . . . . . . . . . . .

List of Tables
2.1 Lattice parameters and atomic position for PbCrO4 at ambient pressure. . . . . . . 6

vi

Chapter 1

Methodology and experimental setup

Objectives
Our main goal is the study of the optical behavior of PbCrO4 crystal under compression and its relation with the structural changes of the mineral. For this, in Chapters 1 and 2 we give a brief description of our instruments and methods and a summary description of the mineral that we have been investigating, while in Chapter 3 our results and their physical interpretation are presented. Finally, Appendix A shows additional experimental results supporting some of our conclusions.

1.1

Diamond anvil cells

Diamond Anvil Cells (DACs) are the most commonly used instruments in the study of physical behavior of crystal samples upon high-pressure conditions (up to 300 GPa). A DAC basically consists in a pair of diamonds that are cut leaving on each a small culet. A metal gasket acts as a separator between the facing culets, forming a sealed chamber where the sample is placed. This assembly is then inserted into a metal cylinder where a metallic membrane, being slowly inated with compressed helium, exerts a force (F ) on the diamonds. The pressure (P ) on the culets of the diamonds thus rises according to equation P = F/A, where A is the area of the culet. The uniaxial pressure supplied by the diamonds on the inner chamber is then transformed into hydrostatic pressure using a uid pressure medium (a gas or a liquid; in our case the medium was a 16:3:1 mixture of methanol, ethanol, water [1] ). Figure 1.1 gives a schematic representation of a DAC along with a photo of the cell used in our experiment.

1.2

Ruby uorescence as a pressure gauge

To measure pressure inside the DAC the ruby (Al2 O3 :Cr) uorescence technique is used. Small ruby chips are loaded together with the sample inside the pressure chamber. Ruby uorescence is excited with a laser ( = 523 nm in our case) producing a doublet R1 , R2 whose wavelengths at ambient conditions are R1 (100 kPa) = 694.3 nm and R2 (100 kPa) = 692.7 nm [2] ; these lines regularly redshifts with increasing pressure1 . Being the result of a data t, there are many expressions of R1 (P ), R2 (P ), according to dierent authors; this notwithstanding, in our pressure range (100 kPa - 12 GPa) the dierences due to the dierent expression of R1 (P ) are < 1%. In our analysis the following expression has
1 100 kPa=104

GPa

1 atm (ambient pressure).

CHAPTER 1. METHODOLOGY AND EXPERIMENTAL SETUP

Figure 1.1: A typical DAC (scheme and photo). been used [2] : P (R1 ) [GPa] = 1904 [GPa] 7.665 R1 [nm] 694.38 [nm]

7.665

(1.1)

1.3

Experimental setup, sample and measurements

Our experimental setup for the optical absorption experiments is depicted in Figure 1.2. There, O1 and O2 are two Cassegrain objectives, each mounted on micrometric slide with two axis (XY). 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) under examination, while O2 serves to focus the light from the sample on the detector. Schematically, each 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 helium slowly in the DAC, until the chosen pressure is achieved. Meanwhile, pressure value is checked in real-time using the laser and the spectrophotometer (1.2) 4. replace laser with the helium lamp and focus the light spot (about 20 m in diameter) outside the sample. Take a reference spectrum of the direct beam. 5. focus the light on the sample and take another spectrum 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 [3] . In this experiment, two dierent samples of PbCrO4 have been used, with a thickness of 20 m. We recorded transmission spectra for both samples increasing and, subsequently, decreasing pressure.

1.3. EXPERIMENTAL SETUP, SAMPLE AND MEASUREMENTS

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 1.2: Experimental setup. In this experiment at pressures around 10 GPa the sample becomes strongly opaque, so it is dicult to obtain good transmittance spectra in the optical range. Because of this, the maximum pressure we reached was 12 GPa. Figure 1.3 shows photos of one of the samples at ambient pressure and at P = 3.5 GPa. Theres an evident change in color associated to a phase transition. A detailed explication will be given in the text. The little sphere right under the sample is the ruby used for the determination of the pressure.

Figure 1.3: Photo of the sample in the DAC at ambient pressure (L) and at P = 3.5 GPa (R).

CHAPTER 1. METHODOLOGY AND EXPERIMENTAL SETUP

Chapter 2

Properties of PbCrO4 at ambient conditions

2.1 General description

Lead chromate (PbCrO4 , crocoite) is a mineral that crystallizes at ambient conditions in a monoclinic structure belonging to P 21 /n space group (monazite structure) [4] . It is commonly used in some pyrotechnic compositions and as a pigment in some paints, because it is practically insoluble in water. It can also be used as a photocatalyst and has been proposed as a potential laser-host material. PbCrO4 is a very toxic substance. Its quite rare in nature but it can be created in laboratory. Our samples were obtained from natural crystals, originated from the Red Lead Mine (Australia). Because of this, we performed an elemental microanalysis in a scanning electron microscope (SEM), to check for the presence and nature of impurities. Figure 2.1 (right) shows some crystals of PbCrO4 at 650x, while Figure 2.1 (left), is an X-ray uorescence spectrum of our sample, that conrms its purity. Only a small amount of Fe is present in some regions, probably due to ferrous oxides in the soil where the crystal growth took place). For our experiments, we selected microcrystals of PbCrO4 with undetectable amount of impurities.

Figure 2.1: XFR analysis of PbCrO4 natural samples (L) and surface of the original crystal magnied at 650x (R).

2.2

Lattice properties and constants

We performed X-ray diraction on crocoite powder with Mo K radiation ( = 0.7093 ). The A obtained lattice parameters are listed in Table 2.1 [5] together with the values given in the literature [6] . Our measurements are in good agreement with the literature data. Table 2.1 also lists 5

CHAPTER 2. PROPERTIES OF PBCRO4 AT AMBIENT CONDITIONS

Figure 2.2: Crocoite lattice structure, (011) plane. Lattice parameters b [] A c [] A

a [] A Exp. Lit.

[ ] 102.42(0) 102.43(2)

7.098(1) 7.410(1) 6.778(8) 7.127(2) 7.438(2) 6.799(2) Atomic positions x/a y/b z/c .2218 .2010 .0354 .1247 .2534 .3887 .1450 .1651 .0989 .3461 .4982 .2173 .3974 .8800 .6944 .9869 .4540 .7810

Pb Cr O(1) O(2) O(3) O(4)

Table 2.1: Lattice parameters and atomic position for PbCrO4 at ambient pressure. the atomic positions inside of the unit cell, in fraction of the lattice parameters [4] . In monazite structure Cr is coordinated with 4 oxygens forming regular tetrahedra and Pb is coordinated with 9 oxygens forming irregular polihedra, as shown in Figure 2.2.

2.3

Optical properties

Chromates with the monazite structure are translucent materials with a band gap between 2 and 2.8 eV [7] . 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. Among this family, PbCrO4 is one of the less studied compounds and its band gap and other properties have not been accurately determined yet.

Chapter 3

Experimental results, data analysis and conclusions

3.1 Experimental results

3,500 11 9 13 16 10

4.79 Gpa

Optical measurements have been performed on two independent samples. Figures 3.1 and 3.2 show the absorption spectra for one of the samples as a function of energy at selected pressures (pressure increases). Graphs in Figure 3.1 show that PbCrO4 at ambient pressure presents an absorption tail starting around E 2.2 eV. This likely accounts for the orange color of the samples at ambient conditions. When pressure increases between ambient pressure and 3 GPa the absorption front edge slowly shifts towards smaller energies . The value of Eg then abruptly decreases at a pressure of 3.5 GPa (spectrum 8 in Figure 3.1) and correspondingly, as we already anticipated at the end of 1.3, the color of the sample shift from orange to reddish (it undergoes a phase transition). If the pressure continues to rise, Eg gradually decreases and the sample becomes more and more opaque, until reaching P 12 GPa, when the quality of the transmittance spectra becomes very poor. This is the reason for the high noise in the spectra taken at pressures 10 GPa1 .
3,500 12 11 9 10 6
7 5 4

1 1 .8 1 GPa 1 1 .1 5 1 0 .8 4 0GPa GPa GPa 1 .1 5 9 .5 0 GPa

3,000 8 - 3.50 GPa 9 - 4.79 GPa 10 - 4.96 GPa 11 - 5,83 GPa 12 - 6.50 GPa 13 - 8.39 GPa 14 - 9.50 GPa 15 - 10.15 GPa 16 - 10.84 GPa 17 - 11.84 GPa 15

14

12

3,000 15 2,500 16 (arbitrary u nits) 2,000

17

14

2,500 (arbitrary u nits )

13

2,000

1 - 0.26 GPa 2 - 0.46 GPa 3 - 0.97 GPa 4 - 1.56 GPa 3 5 - 1.98 GPa 2 1 6 - 2.58 GPa 7 - 2.93 GPa 8 - 3.50 GPa 9 - 4.79 GPa 10 - 4.96 GPa 11 - 5,83 GPa 12 - 6.50 GPa 13 - 8.39 GPa 14 - 9.50 GPa 15 - 10.15 GPa 16 - 10.84 GPa 17 - 11.84 GPa

6 7 54 3 21

17

1,500

1,500

1,000

1,000

500

500

0 1.20 1.40 1.60 Ene rgy (e V) 1.80

0 1.60 1.80 2.00 Energy (e V) 2.20 2.40

Figure 3.1: Absorption spectra of PbCrO4 in the range 1.2 eV < E < 1.9 eV (L) and 1.5 eV < E < 2.4 eV (R) (increasing pressure).
1 10 GPa

105 atm.

CHAPTER 3. EXPERIMENTAL RESULTS, DATA ANALYSIS AND CONCLUSIONS

The absorption spectra exhibit a steep absorption, characteristic of a direct band gap, plus a low energy absorption band, which envelops partially with the fundamental absorption. This low-energy absorption tail has been observed in related compounds and seems to be due to the presence of defects. On the other hand, the steep absorption has an exponential dependence on the photons energy, following Urbachs law (see 3.2). This dependence is typical of direct absorption edges with excitonic eects [8] . When releasing pressure Eg grows and suddenly, at about 1.8 GPa, the sample returns to its original orange color but becomes fragmented. This causes very high diusion of the light beam that in turn is the reason of the degradation of the absorption spectra, as can be seen in Figure 3.2. Looking at graph in Figure 3.2 it is evident that the sample seems to recover its original phase. Anyway, the poor quality of the spectra didnt allow a quantitative conrmation.
3,500 6 3,000 5 7

2,500 1 - 10.15 GPa 2 - 8.96 GPa 3 - 7.66 GPa 4 - 6.13 GPa 5 - 4.98 GPa 6 - 3.74 GPa 7 - 2.64 GPa 8 - 1.83 GPa 9 - 0.87 GPa 10 - 0.46 GPa (arbitrary u nits )

1
9 10 3 8

2,000

1,500

1,000

500

0 1.00 1.20 1.40 1.60 1.80 2.00 2.20 2.40

Ene rgy (e V)

Figure 3.2: Absorption spectra of PbCrO4 (decreasing pressure).

3.2

Data analysis

To analyze the absorption data we used Urbachs rule, i.e. the spectra can be described by the equation: (E) = 0 exp (E Eg ) (3.1) kB T where T is the absolute temperature, kB is the Boltzmann constant, 0 and are dimensionless temperature depending parameters and nally Eg is the energy gap. The three parameters are characteristic of each material, being 0 usually assumed as pressure independent [9] . On the other hand, determines the shape of the absorption tail and indirectly gives indications on the presence of defects in the crystal structure [9] . In our case, the experiment was realized at ambient temperature, so T 298 K and kB T 0.0256 eV. Equation (3.1) implies that the curves in Figures 3.1 and 3.2, when plotted in a semilogarithmic graph, should be nearly parallel lines2 whose relative distances are due to the variation of Eg with the pressure. Such a semi-logarithmic plot, conrming the validity of (3.1), is depicted in Figure 3.3 (for the curves in Figure 3.1). In Equation (3.1) 0 and Eg are clearly correlated. Therefore, we determined 0 at ambient pressure (0 = 130 1) considering Eg = 2.2 eV [7] and assumed that 0 is not modied under
2 At

least in the region where E > Eg .

3.3. DEPENDENCE OF Eg AND ON P

10 10

9
8 - 3.50 GPa 9 - 4.79 GPa 10 - 4.96 Gpa 11 - 5.83 GPa 12 - 6.50 GPa 13 - 8.39 GPa 14 - 9.50 GPa 15 - 10.15 GPa 16 - 10.84 GPa 17 - 11.81 GPa 15 14 16 16 17
13

9
12 11 10 9 8 ln() (arbitrary u nits ) 15 14 8 - 3.50 GPa 9 - 4.79 GPa 12 11 10 - 4.96 Gpa 8 10 9 11 - 5.83 GPa 7 5 4 12 2 6.50 GPa - 1 13 - 8.39 GPa 14 - 9.50 GPa 15 - 10.15 GPa 16 - 10.84 GPa 17 - 11.81 GPa

8
ln() (arbitrary u nits )

8
17

16

13

54 3 21

1.20

1.40

1.60 Ene rgy (e V)

1.80

1.60

1.80

2.00 Ene rgy (e V)

2.20

2.40

Figure 3.3: Semi-logarithmic plot of the curves in Figure 3.1 (same ranges).
3,000

2,500

2,000 (arbitrary u nits )

1,500

1,000

500

0 1.20 1.40 1.60 1.80 Ene rgy (e V) 2.00 2.20 2.40

Figure 3.4: Fit of the absorption curve for PbCrO4 at ambient pressure. 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 Figure 3.4.

3.3

Dependence of Eg and on P

We studied separately Eg (P ) for increasing and decreasing pressure. The results are shown in Figure 3.5, where the dierent symbols denote the two samples, while Figure 3.6 shows both graphs in the same plot (now the circles and the boxes denote respectively increasing and decreasing pressure). Looking at the graph it is clear that generally Eg (P ) is a linearly decreasing function of P . Starting with a value of Eg (100 kPa) 2.2 eV and up to 3.0 GPa we found that dEg = (4.3 0.2) 102 eV GPa1 dP (3.2)

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2.40

CHAPTER 3. EXPERIMENTAL RESULTS, DATA ANALYSIS AND CONCLUSIONS

1.90

2.20

1.80

2.00

1.70
1.80

Eg (eV) 1.60 1.50 1.40

0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00

Eg (e V)

1.60

1.40

1.20

0.00

2.00

4.00

6.00 Pressu re (GPa)

8.00

10.00

12.00

Pre s s u re (GPa)

Figure 3.5: Eg (P ) for increasing pressure (L) and decreasing pressure (R). while past 3.0 GPa, as we already anticipated in 3.1, we can observe one phase transition: Eg decreases abruptly with Eg 0.35 eV and then it continues to decrease with a slope given by dEg = (4.2 0.1) 102 eV GPa1 dP The values in (3.2) and (3.3) can be considered the same within their error bars.
2.40

(3.3)

2.20

2.00

Eg (eV)

1.80

1.60

1.40

1.20 0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00

Pressu re (GPa)

Figure 3.6: Eg (P ) for both increasing (circles) and decreasing pressure (boxes). The dashed line is the data tting for decreasing pressure. When pressure decreased and went back to ambient (100 kPa) we observed that dEg = (3.99 0.3) 102 eV GPa1 dP (3.4)

Again, the value in (3.4), within the error range, is the same value given in (3.2) and (3.3). This is an evidence that the pressure-induced changes in the mineral structure are reversibles, although we can observe an hysteresis phenomenon, given that Eg doesnt go back to its original

3.4. PHYSICAL INTERPRETATION

1.00

11

0.80

(dim ensionless)

0.60

0.40

0.20

0.00 0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00

Pressu re (GPa)

Figure 3.7: Variation of with P . value 2.2 eV when pressure decreases down to ambient (see Figure 3.6). The fragmentation of the sample that we mentioned in 3.1 made impossible for us to investigate further on this issue. It is now interesting to observe the variation of with pressure. Looking at Figure 3.7 it is evident that somehow mimics the behavior of Eg . In the range 100 kPa - 3 GPa it grows with P with a slope given by d = (1.8 0.6) 102 GPa1 dP while at pressure above 3.5 GPa the slope becomes negative and its value is d = (1.7 0.5) 102 GPa1 dP (3.6) (3.5)

Again, when P goes back to ambient pressure3 , we can observe for the same reversibility that manifested Eg , given that now the variation of with P is given by d = (1.5 0.7) 102 GPa1 dP and the values given in (3.7) and (3.6) are the same within the error bars. (3.7)

3.4

Physical interpretation

The band gap collapse found beyond 3 GPa is possibly caused by a structural phase transformation. This hypothesis has been conrmed by XRD and Raman experiments (see Appendix A). According with theoretical calculations [7] , in PbCrO4 the main contribution of the bottom of the conduction band results from the antibonding interaction between the Cr(3d) orbitals and the O(2p) orbitals. The upper portion of the conduction band results primarily from the interaction between empty Pb(6p) orbitals and O(2p) orbitals. Since the space group symmetry permits mixing of the Pb(6p) and Cr(3d) orbitals, a minimum contribution from the Pb(6p) orbitals is observed at the bottom of the conduction band. 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. See Figure 3.8 for a visual representation of PbCrO4 band structure [7] .
3 The

corresponding plot is not reported here, for brevitys sake.

12

CHAPTER 3. EXPERIMENTAL RESULTS, DATA ANALYSIS AND CONCLUSIONS

4.1

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

2.2

Energy (eV)

2.2 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 PbCrO4 .

As we said before, we could observe up to three dierent phases in the mineral, in three dierent ranges of pressure. Lets see in more detail what happens at dierent pressure ranges, trying to justify our observations with some hypothesis on the changes occurring in PbCrO4 structure.

3.4.1

Phase I - Monazite (100 kPa 3.5 GPa)

In this rst range we suppose that, as usually happens, the bond distances are reduced with increasing pressure, while the lattice retains its monazite structure. For this, theres an increase of the crystal eld acting on Cr(3d) and O(2p) states. As a result, theres a reduction in Eg , since O(2p) states shift towards higher energies faster than Cr(3d) states. A similar behavior has been observed in lead wolframate, PbWO4 [10] .

3.4.2

Phase I - Phase II transition (3.5 GPa 7.5 GPa)

In this range of pressures theres an atomic reordering, as can be noted in diraction peaks changing their height (see A.1 in Appendix A). The point group symmetry of the crystal gets lower and produces a band gap decrease. The mineral undergoes a transition to a dierent phase (unknown, at the present time). This fact is conrmed by XRD and Raman experiments (Appendix A). The behavior of Eg in phase II is similar to that of phase I, so electronic structure is probably still determined by Cr(3d) and O(2p) states. Theoretical calculations are needed to conrm this hypothesis.

3.4.3

Phase II - Phase III transition (7.5 GPa 12.0 GPa)

In this pressure range Raman spectroscopy and X-ray diraction experiments (A.2 in Appendix A) show another phase transition around 10 GPa. However in our optical measurements this phase transition is not evident due to the high opacity of the sample. This could be due to a metallic character of phase III. This hypothesis is supported by the fact that others related compounds end exhibiting metallic behavior beyond a certain pressure [11] .

3.5. CONCLUSIONS

13

3.5

Conclusions

This work has to be considered an original rst approach to a more complete study of PbCrO4 properties under pressure. This semiconductor has almost never been studied before, so the results obtained in this rst phase are interesting per se. First of all, we put in evidence that PbCrO4 undergoes up to two phase transitions in a relatively reduced pressure range. Also, these transformations appear to be completely reversible, showing a small hysteresis phenomenon. The rst phase transition is clearly observable by means of the optical measurements, while the second transition is evidenced clearly by powder diraction and Raman spectroscopy. Physical interpretations of the results have been attempted, partially supported by comparison with other related compounds, in particular PbWO4 . However, further studies and experiments are necessary. In particular, some of these would be: detailed Raman spectroscopy, to better localize transition pressures. another set of optical measurements, with better resolution in pressure, to obtain more detailed data about Eg behavior near the transitions. exhaustive powder diraction experiments, to obtain the structures of phases II and III, together with the evolution of lattice parameters with pressure. resistivity measurements under compression; in particular these experiments are needed to prove right or wrong the hypothesis about the metallic properties of phase III. All these matters will eventually be the subject of a future Master thesis. This work has been done in the framework of a Beca de Colaboracin (collaboration grant) o with the High Pressure Research Group of the University of Valencia. The extension of this study will be published in an international journal.

3.6

Conclusiones

Este trabajo se tiene que considerar un primer planteamiento para un estudio ms completo de a las propiedades de PbCrO4 bajo presin. Este semiconductor prcticamente no ha sido estudiado o a anteriormente y por ello los resultados obtenidos en esta primera fase son interesantes de por si. Primero de todo, hemos puesto en evidencia que el PbCrO4 est sujeto a hasta dos transiciones a de fase en un rango de presiones relativamente reducido. Adems, estas transformaciones parecen a ser completamente reversibles, a parte un pequeo fenmeno de histresis. La primera transicin n o e o de fase es observable de forma clara por medio de las medidas de absorcin ptica, mientras que o o las segunda es ms evidente en los experimentos de difraccin de rayos X y espectroscopia Raman. a o Se han intentado interpretaciones a nivel f sico de los resultados, por comparacin con otros o cristales anes, en particular PbWO4 . Sin embargo, se necesitan ulteriores estudios y experimentos. En particular, algunos de estos ser an: espectroscopia Raman detallada, para localizar mejor las presiones de transicin. o otro conjunto de medidas pticas, con mejor resolucin en presin, para obtener datos ms o o o a detallados sobre el comportamiento de Eg cerca de las presiones de transicin. o experimentos exhaustivos de difraccin de rayos X, con el objeto de encontrar las estructuras o cristalinas de las fases II y III, junto con la evolucin de los parmetros de celda en funcin o a o de la presin. o medidas de resistividad elctricas bajo presin; en particular, estos experimentos se necesitan e o para para conrmar o desmentir la hiptesis acerca de las propiedades metlicas de la fase o a III.

14

CHAPTER 3. EXPERIMENTAL RESULTS, DATA ANALYSIS AND CONCLUSIONS

Todo esto ser eventualmente el objeto de una futura tesis de Mster. Este trabajo ha sido realizado a a en el marco de una Beca de Colaboracin con el Grupo de Altas Presiones de la Universidad de o Valencia. La extensin de este estudio ser publicada en una revista internacional. o a

Appendix A

XRD and Raman experiments

A.1 X-ray diraction

Figure A.1 (left) shows the evolution of X-ray diraction patterns collected at dierent pressures. They have been obtained performing powder diraction in DAC using Mo K wavelength ( = 0.7093 ) in an Xcalibur diractometer (Agilent Technologies, former Oxford Diraction Ltd.) A with an Atlas charge coupled device (CCD). Some hints of the rst phase transition can be seen at a pressure between 3.25 and 4.43 GPa, when the peak at 2 11 begins to split in two separate peaks and the set of peaks at 2 15 fuse together. This is what we called phase II.

PbCrO4

13 GPa - Phase III 11.6 GPa - Phase III 9.4 GPa - Phases II & III

7.5 GPa - Phase II

Intensity (arb. units)

10 15

9.1 GPa phase III

Intensity (arb. units)

5.3 GPa - Phase II

8.1 GPa phase II + III

3.5 GPa - Monazite

7.2 GPa phase II + III

6.1 GPa phase II + III

5.2 GPa phase II + III

2.5 GPa - Monazite

4.43 GPa phase II

1.5 GPa - Monazite

3.25 GPa monazite

1.5 GPa monazite

0.95 GPa - Monazite

0.55 GPa monazite

500

600

700

800

900
-1

1000

1100

2 tetha (degrees)

Raman shift (cm )

Figure A.1: X-ray diraction patterns (L), Raman spectra (R). The subsequent phase transitions, leading to phase III, begins to happen immediately after 15

16

APPENDIX A. XRD AND RAMAN EXPERIMENTS

4.43 GPa: some peaks begin to disappear (i.e. the one at 2 9 ), while others become visible (2 13 ). Phases II and III then coexist until 9.1 GPa, when the second transition appears to be complete. This is consistent with the result of our experiments in optical absorption. The changes observablesin the XRD patterns suggest a symmetry increase in phase III.

A.2

Raman spectroscopy

Raman experiments were performed in the back scattering geometry using a 632.8 nm He-Ne laser and an Horiba Jobin-Yvon LabRAM high-resolution spectrometer, in combination with a thermoelectrically cooled multichannel CCD with spectral resolution below 2 cm1 . Results similar to those in A.1 are found in our Raman experiments. Figure A.1 (right) shows the Raman spectra at selected pressures. Phase I appears to be stable until at least 3.5 GPa. Phase II and III then coexist until about 9.4 GPa and nally, at a pressure of about 11.6 GPa, only phase III is observable.

For the moment, the only purpose of these results is to support the conclusions following the optical measurements. An exhaustive analysis of these data is out of the scope of an undergraduate thesis but, nevertheless, they can be a starting point for future investigations regarding PbCrO4 .

Appendix B

Software tools
B.1 Free Software

But for Figures 2.1, 2.2, and A.1, exclusively Free Software has been used in this work: Qtiplot for data plots and analysis (http://soft.proindependent.com/qtiplot.html). Inkscape for SVG graphics (http://www.inkscape.org/). The Gimp for photos and images editing (http://www.gimp.org). LibreOce for some data processing and text editing (http://www.libreoffice.org/).
A Final document written using L TEX 2 (http://www.latex-project.org/) in conjunction with Kile editor (http://kile.sourceforge.net/).

Operating system was Sid Debian GNU/Linux (http://www.debian.org) with KDE environment (http://www.kde.org).

17

18

APPENDIX B. SOFTWARE TOOLS

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