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    Born effective charge tensors, dielectric permitivity tensors, the phonon frequencies at the Bril- louin zone center and mode oscillator strengths are calculated using density func tional perturbation theory.

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    Born effective charge tensors, dielectric permitivity tensors, the phonon frequencies at the Bril- louin zone center and mode oscillator strengths are calculated using density func tional perturbation theory.

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    © All Rights Reserved
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    26 views68 pages

    Ab Initio Calculations On Electronic

    Uploaded by

    Ahmet Emre
    Born effective charge tensors, dielectric permitivity tensors, the phonon frequencies at the Bril- louin zone center and mode oscillator strengths are calculated using density func tional perturbation theory.

    Copyright:

    © All Rights Reserved
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    AB INITIO CALCULATIONS ON ELECTRONIC AND LATTICE DYNAMICAL PROPERTIES OF COPPER INDIUM DISELENIDE AND COPPER INDIUM DISULPHIDE by Cihan Parlak (234992 ‘THE GRADUATE SCHOOL OF NATURAL AND APPLIED SCIENCES OF THE ABANT IZZET BAYSAL UNIVERSITY ‘THESIS SUBMITTED TO IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE IN THE DEPARTMENT OF PHYSICS ve viusexoe ca Bolu, Turkey July 2002 Approval of the Graduate School of Natural Sciences — 2 1 Lv Prof. Dr. Nihet Celebi Director certify that this thesis satisfies all the requirements as a thesis for the degree of Prof. Dr. Ahmet Turan Alan ) Head of Physics Department Master of Science. ‘This is to certify that we have read this thesis and that in our opinion it is fully adequate, in scope and quality as a thesis for the degree of Master of Science. Assistant Prof. at Supervisor ‘Examining Committee Members 1. Assist. Prof. Dr. Resul Eryigit ba Leja 2. Assoc. Prof. Dr. Ayge Morkan 3. Assist. Prof. Dr. Cabir Terziogiu ii To My Family ... ABSTRACT Ab initio Calculations on Electronic and Lattice Dynamical Properties of CulnSe, and CulnS, Cihan Parlak Master of Science, Department of Physics Supervisor: Assist. Prof. Dr. Resul Eryigit July 2002, 68 pages We have performed a first-principles study of structural, dynamical, dielec- tric and electronic properties of chalcopyrite semiconductors CulnSe, and CulnS». ‘The calculations have been carried out within the local density functional approx- imation using norm-conserving pseudopotentials and a plane-wave basis. Elec- tronic band structure of both compounds found to be similar. Born effective charge tensors, dielectric permitivity tensors, the phonon frequencies at the Bril- louin zone center and mode oscillator strengths are calculated using density func- tional perturbation theory. The calculated properties agree with some measure- ments. Keywords: Chalcopyrite semiconductors, electronic band structures, Born ef- fective charges, phonon frequencies, dielectric permitivity tensors. iv 6ZET CulnSe; ve CulnS,’iin Elektronik ve Orgii Dinamigi Ozellikleri Uzerine Ab initio Hesaplamalar Cihan Parlak Yiiksek Lisans, Fizik Béliimit Tez Danigmam: Yrd. Dog. Dr. Resul Eryigit, ‘Temmuz 2002, 68 sayfa Bu teade chalcopyrite yar iletkenler CulnSe, ve CulnS, ‘iin yapisal, dinamik, dielektirik ve elektronik zelliklerini inceledik. Oncelikle hesaplarda yerel yogunluk yaklagum, norm-korunumlu pseudopotential ve diizlem dalga taban) kullanild Elekronik band yapilan ikki madde iginde benzer bulundu. Born etkin yiik tensérleri, dielektirik gecirgenlik tensdrleri, Brillouin bélgesi merkezindeki fonon frekanslart ve mod titresim giicleri hesapland:. Bu degerler literatiirdeki deerlerle karglastirilarak baz verilerle uyumlu oldugu gorildi Anahtar Kelimeler: Chalcopyrite yaniiletkenler, elektronik band yapilan, Born ektin yiik tensérleri, fonon frekanslan, dilektrik gegirgenlik tensérleri, ACKNOWLEDGEMENTS I would like to thank my advisor, Dr. Resul Eryigit for his support, guidance, patience and encouragement during years of my work as a graduate student at AIBU. I am obliged for his continuous guidance and support and thank to him for his help in the revision of scientific content and style of this dissertation And I want to thank him not only for guidance for scientific content’ but also his guidance for all contents of life I would like to thank my friends, colleagues and teachers in physics department for their friendship and encouragement all trough my years at AIBU. Tam grateful to Dr. Ayge Morkan and Dr. Cabir Terzioglu along with my advisor for serving on my dissertation. Tam grateful to "Teknik Bilgisayar ve Hizmetleri” for their computer support. Tam thankful to my family, for their support, patience, understanding and financial support. TD upekOGRETIN KOETL pac MARTASYON MERIT TABLE OF CONTENTS ABSTRACT OZET ee eee eee ACKNOWLEDGEMENTS 1 INTRODUCTION . 2 DENSITY FUNCTIONAL THEORY .. . 2.1. The Plane-Wave Pseudopotential Method 2.2 Plane-Wave Solution of Kohn-Sham Equations: 3 REVIEW OF EXPERIMENTAL STUDIES 4 ELECTRONIC STRUCTURE OF CHALCOPYRITES .. . . . 4.1 Pseudopotentials 4.2 Convergence Issues 4.3 Atomic Structure - 4.4 Electronic Structure 5 LATTICE DYNAMICS RESULTS 5.1 Born Effective Charge Tensors . 5.2 Phonons .. . 5.3 Lattice Dielectric Tensors 6 CONCLUSION . REFERENCES . iv vi 3.1 3.2 33 41 42 43 44 45 46 47 48 49 4.10 411 4.12 413 ald 415 4.16 5.1 5.2 53 54 LIST OF FIGURES Conventional unit cell of chalcopyrite crystal structure. 15 Conventional unit cell of zinc-blende crystal structure 15 ‘Tetragonal chalcopyrite primitive unit-cell 16 Energy Levels of Cu, In and Se atoms. 24 Energy Levels of Cu, In and $ atoms. : sees BB ‘The ‘Troulliers Martin pseudopotentials for Cu... +... 26 ‘The Troulliers Martin pseudopotentials for In 27 The Troulliers Martin pseudopotentials for Se 28 ‘The Troulliers Martin pseudopotentials for 8 29 ‘Wave functions of Copper valance orbitals. 30 ‘The band structure of CulnSe,. .. . . . 32 ‘The band structure of CulnS2. . . BB Details of the high valance and low conduction states of CulnSe,. 34 Details of the high valance and low conduction states of CulnS; . 35 ‘Modulus square of the wave functions of CulnSe,-first band 36 Modulus square of the wave functions of CulnSey-sixth band... 37 Modulus square of the wave functions of CulnSey-10 band 38 Modulus square of the wave functions of CulnSe,-28" band 39 Modulus square of the wave functions of CulnSe,-29" band 40 Reflectance spectra obtained by using sum form of the model di- electric function for El}c polarization . 47 Reflectance spectra obtained by using sum form of the model di- electric function for E-Le polarization . . 8 Reflectance spectra obtained by using product form of the model dielectric function for Elle polarization ............... 48 Reflectance spectra obtained by using product form of the model dielectric function for Elle polarization .... 2.2.0.2... 50 wa ze, VouSEKGGRETIM KURULD LIST OF TABLES 3.1 Coordinates of the atoms of chalcopyrite primitive unit cell . 4.1 Convergence study on total energy of CulnSe, and Culn$a. 4.2 Calculated structural parameters of CulnSea : 4.3 Band-Gaps of CulnSe, and CulnS, . . Calculated Born effective charges of CulnSe, Frequencies of phonons at the I’ point . Reanalyzed reflectivity data 5.4 Static and high frequency dielectric tensor components of CulnSes. 5.5 Oscillator strength tensor, magnitude of mode-effective charge ve tors and LO frequencies of CulnSez .........- 20.005 CHAPTER 1 INTRODUCTION ‘The increasing energy demand, dwindling fossil-fuel resources and a growing trend towards so called clean-energy have been fuelling the research for high-efficiency solar materials for last three decades. Among the promising solar-cell materials, Cu-based chalcopyrite (CH) semiconductors have been shown to have the highest conversion efficiency of 18 % (1, 2] As experimental work on these compounds continues, a better theoretical understanding of their electronic properties need to be provided. ‘This thesis is about the electronic and lattice properties of two of these group of semiconductors, namely CulnSez and CulnS, Nowadays the standard tool of theoretical condensed matter physics to deal with the electronic and lattice properties of solids is density functional theory (DFT) of Kohn-Sham [3] and Hohenberg-Kohn [4]. This extremely successful and simple theory, which was established almost 40 years ago has been immensely popular, first in physics and chemistry and for last 10 years also for biology. Density functional theory, in its many forms helped in understanding many different. properties of systems as simple as atoms to very complicated surface structures. In condensed matter applications, it is generally used within so called local density approximation (LDA) and pseudopotentials to account: for the inter- action between the valance electrons and the nuclei. In Section 2, we will review the basics of this theory and its implementation with a plane-wave basis. One should also mention the dramatic increase in computing power and de- velopment of very efficient algorithms and programs to solve the differential equa- 1 tions of density functional theory. These two factors made it possible to solve problems, that could not be solved on a supercomputer 10 years ago, on a per- sonal computer. This trend, if continues as it is, will make the first principles calculations possible for much more complicated structures, within next decade. We have set the stage for the possibility of obtaining the quantum mechanical properties of moderately complicated chalcopyrite semiconductors. For solar en- ergy applications, the most important property is of course, the band structure of the material. Band-structure of material determines the allowed energy values for the electrons of the crystal. For semiconducting systems, the band structure has a typical forbidden band between the valance bands which are completely full at 0 °K, and conduction bands, which are completely empty at 0 °K. For a good absorber of sun-light, one needs a material with a spectrum of sun-light. Of course, the band-gap photon energy match is not enough for high-efficiency absorption. Absorption /emission process involves an energy and a momentum transfer and so called direct band-gap materials would have higher efficiencies. All Cu-based ternary semiconductors have direct band-gaps at the Brillouin zone center (I point). In this thesis we investigate the electronic band structure of CulnSe, and CulnS; with density functional theory within local density approx- imation using norm-conserving pseudopotentials and a plane-wave basis set for expansion of the wave function. Actually, these settings for the calculations are not the best ones possible. It is well-known that DFT-LDA underestimates the band-gap of semiconductors. This property has been thoroughly investigated over the last 15 years and it is well understood. A different theory, so called GW approximation is needed in solids{5]. Unfortunately, GW approach is computationally extremely demanding. But over the years, it has been well established that the GW band structure and DFT-LDA band structure can be brought to agreement by a k-independent shifting (so called "scissor approximation") of DFT-LDA valance bands. ‘As the electronic structure is important for the way photons absorbed and emitted, the lattice dynamical properties of solids are very important for the thermal properties such as thermal expansion coefficient, heat capacity and ther- modynamical Griineisen parameters. The phonon frequencies for the wave vector at the center of the Brillouin zone are also very important diagnostic properties. Optical diagnostic tools, such as Raman and Infrared reflectivity spectroscopies can be used to measure symmetry allowed modes at the zone center. This infor- mation can be used as a guide for the quality of the crystal. Lattice dynamical studies, experimental as well as theoretical have been the standard tools of solid state physics for last 60 years. On the experimental scene the main improvement came from the development of lasers, 40 years ago, and better detectors, such as charge coupled devices (CCD) in 1980's and 90’s. The major theoretical development in this field came in last 15 years like almost every other development in computational condensed matter physics; impressive developments in computing power was one of driving forces. Theoretical studies in this field can be broadly divided into two classes; the so called phenomenological models and ab initio methods. Phenomenological models try to guess the most important interactions between the constituent atoms compromising the system and tries to find the parameters of the interaction by fitting the frequencies of the model with the experimentally measured ones. Because of this empirical nature, the predictions of phenomenological models are not always good. Contrary to phenomenological models, ad initio methods do not assume any form for the interactions of the atoms of the system and tries to calculate ev- erything from first-principles quantum mechanical quantities. There are number of different ad initio approaches with respective advantage and disadvantages. Partly because of its computational ease, the so called frozen-phonon method (6] was the first ab initio phonon method. This method tried to find the phonon dis- placement pattern and calculate the energy difference between the perfect crystal and the crystal where the atoms are displaced according to particular phonon pattern, This technique is good for phonons at high symmetry points of the Bril- louin zone. For a phonon at an arbitrary point in Brillouin zone, the displacement pattern would require a large unit cell and calculation becomes prohibitively large A completely different approach to ab initio phonon problem is so called linear response approach {7]. In this approach, one considers phonon as a perturbation an the electronic density of the crystal and phonon frequencies are computed from the linear response of the crystal. This method has the added advantage that one can consider other perturbations, such as electrical field, which is important for the longitudinal optical modes of polar materials. Lattice dynamical properties of CulnSe have been investigated experimen- tally by many groups over the last thirty years (8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18). Phonon frequencies at the I point have been measured by all possi- ble spectroscopies, Gan et al. (9], Bodnar et al. [8], Rincon et al. (14), Bacewicz et al. (15), Tanino et al. {18] report Raman measurements at 100 °K and 300 °K while Bodnar et al. [8], Gan et al. [9], Riede et al. [10], Neuman et al. (11), report infrared measurements at ~ 4°K and Derollez et al. (17] reported Neutron measurements. Unfortunately, the picture that arises from these reports is one of confusion. Even the frequencies measured by different groups using the same technique show considerable discrepancies for some of modes. Same confusion persist for the dielectric properties that can be measured by infrared reflectivity methods. 4 ec vunst: uM KCURUS ‘DOKUMANIASYON So we combine the predictive power of ab initio methods with linear response approach to try to shed some light on the question of the zone center phonon frequencies and dielectric tensors of chalcopyrite CulnSey semiconductor. The plan of the thesis is as follows; in Section 2, we give a brief overview of the main theory of density functional theory in pseudopotential plane-wave im- plementation. Section 3 review previous experimental as well as theoretical work on lattice dynamical and electronic properties of CulnSe, and CulnS,, The main ingredients of the calculation and electronic band structure and wave function of the system are displayed and discussed in Section 4. Section 5 is about the calcu- lated phonon, Born effective charges and dielectric properties. Thesis concludes with discussion and further research suggestion in Section 6. CHAPTER 2 DENSITY FUNCTIONAL THEORY From the standpoint of quantum mechanics, a crystal can be considered as system of nuclei and electrons interacting through Coulombic forces. The standard way of entangling the nuclear degrees of freedom is called "adiabatic approximation” which is based on the fact that the mass of electrons is much smaller than nucleic mass. With this approximation, one transforms the problem into two parts; the problem of electrons as if the nuclei are stationary and problems of nuclei moving on a potential energy surface determined by the electronic distribution. ‘The solution of the first problem would give the electronic energy band struc- ture and electronic wave functions of the crystal, while the solution to second problem are the vibrational properties of the crystal. Let us start with the first problem, here we have N interacting electrons in an extemal potential, created by stationary nuclei. This system is described quantum mechanically by the solutions of Schrédinger many body equation; HY(F, Fv) = BVA, Fn) (2.1) where H in the Hamiltonian: (2.2) os Veal) + & oy A 2 = 7] where #{ is the position of the i electron and Vize(fi) is the external potential that act on the electron i. In these formulas we are using atomic units, where 6 1; ifm, = } and e* = 2 then the energies are in Rydberg (Ryd) or if m, = 1, 1, energies are in Hartree (Ha) ‘Unfortunately, the solution of Equation (2.1) cannot be found analytically or numerically, because Coulombic form couples all the electronic degrees of freedom. The usual practice, for last four decades, to overcome this problem has been to forget about the many body wave function to find the ground-state charge density, which can also be used to calculate the observable ground-state properties of the crystal. In practice, Equation (2.2) is replaced by equation derived from density func- tional theory (DFT) of Hohenberg and Kohn (4]. This theory shows that the external potential acting on electrons is a functional of the ground-state charge density. This potential, in turn, determines the ground-state wave-function and therefore all the ground-state properties of the electronic system are functionals of the electronic density. An important ground-state observable is the total energy of the system. Charge density can be found as the function that minimizes the total energy functional as demonstrated by Kohn and Sham (KS) (3] Formally, one can write the ground-state energy of the many-body system as the expectation value of the Hamiltonian as; Gtr] =< voll > (23) Let us specialize the situation to properties of periodic solids, where nuclear position are fixed by the introduction of Bravais lattice vectors K,, and by the choice of basis vectors 7, which characterize the positions of the nuclei inside the unit cell so that the total energy of the electrons and the nuclei can be written as; Eo = Ex + G[n) (2.4) where B,.; , the Coulombic potential energy of the ionic subsystem which can be computed as; where Z,, the charge of nucleus at r, and prime on summation indicates that =v and s = $1 term is omitted from the sum. Kohn and Sham introduced a new functional G{n] with help of wave-functions of independent electron gas with the same density as the interacting system. Within this approach, let |y > be the single particle wave functions of non- interacting system, then the kinetic energy would be T EEDA calves > 26) where f, is the Fermi function, which is equal to 2 (taking into account spin degeneracy) if the energy of the i* level is less than Fermi energy and equals 0 if it is higher. The density of same non-interacting system would be; nf) =D Ala? (2.7) this density, by construction, is same as the density of the interacting system. So Ey would include a Coulombic term of the form; Bun f ie rgd, MEE (2.8) External interaction would give; Eze =D) fi < VilVeatlvi > (2.9) In practice Veg is the effect of nuclei. If these terms are extracted from the total energy of the interacting system one would get a functional that includes all the many-particle effects. This part of the total energy is known as the exchange- correlation energy of the system Ezeln = G{n| = Bee —T — En (2.10) If E,c{n] was known, the ground state density could be computed by min- imizing total ground state energy. This minimization is alone with respect to single-particle wave function ¥;(r) with the orthogonality constraint; < Pils >= 5 (2.11) which leads to Kohn-Sham equations; [aac + al) + Vel) + Veal] LAD = ewieCA) (212) The solutions of this equation are used to build up charge density n(F) in Equation (2.7) in Equation (2.12); 2 iE an 2D, (2.13) and Vae(7) = oat (2.14) ‘The physical observables of KS are total ground-state energy and ground-state density. 2.1 The Plane-Wave Pseudopotential Method Ina periodic solid, Equation (2.12) can be solved by expanding ¥i(7) in a complete set of basis functions, such as plane waves (PW), gaussian functions or atomic orbitals. We will discuss only the plane wave expansion because of its conceptual simplicity and computational advantages. Because of lattice periodicity, plane ‘waves are natural basis and they don’t suffer from basis towards atomic positions. Hartree potential is easier to compute with PW, and one can systematically increase the resolution of the computation by increasing the number of plane waves used to expand ¥(7). Since V.zs(F) is the muclear potential, the wave functions if electrons close to nuclei would have highly oscillatory structure, which is very difficult to reproduce with a limited number of plane waves. One possible solution of this problem causes from the realization that the energies of care states are orders of magnitude larger than the valence states and the electrons that are important in bonding are valence electrons. So, core electrons can be eliminated from Equation (2.12) This approximation amounts to substitution of nuclear potential with a pseu- dopotential whose lowest energies coincides with the valence all-electron energies and whose wave-functions coincide with all-electron wave functions in regions far away from the nucleus. Pseudopotential theory has been developed to great accuracies in last three decades In practice, the pseudopotential of nuclei s is written as loa VA) = V+ YVR (2.15) Ss where P; is the projector 10

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