Electronic Structure and Defect Modeling of III-V(Sb)Superlattices with hybrid DFT

Tristan Garwood April 26, 2013

Introduction

Infrared detectors are widely used in both military and civilian applications and have been researched extensively in the last two decades. Such applications include detection and tracking of hot objects at a long range, passive night vision, nding people in collapsed buildings, astronomy, and bio-medical imaging. The IR portion spans a wavelength range from 1.0 to around 300 m and is loosely further classied into near-IR (1-5 m), mid-wave IR (5-12 m), longwave IR (12 -25 m), and far IR (25-300 m). Transitions between vibrational quantum states typically occur in the infrared. Thus, in applications that desire the observation and identication of chemical species using point detection or stand-o detection, such as pollution monitoring, gas leak detection, gas sensing, and spectroscopy, one needs to work in these wavelength bands. The spectrum of black-body radiation has a peak of around 10m at room temperature. This makes detectors that have a range between 8-12m very helpful to identify heat radiation from a target at around 300K. Earlier military applications withstood the expense of the less stable and more convenient HgCdTe alloy. The extremely small change of lattice constant with composition makes it possible to grow high quality layers and heterostructure. However, there are multiple problems associated with HsCdTe IR detectors such as large tunneling dark currents caused by the narrow band gap (less than 0.1 eV). InAs/GaSb type-II strained layer superlattices (SLS) have attracted considerable research interest for use as IR photodetectors due to their suppressed Auger recombination relative to bulk mercury-cadmium-telluride (MCT) materials which leads to improved temperature limits of spectral detectivities[18]. Superior performance of InAs/GaSb SLS has been theoretically expected, but is yet to be observed experimentally. It is believed that this is a result of Shockley-Read-Hall (SRH) recombination which causes increased levels of dark current. The eventual goal of my research project for the REU program at CHTM is to apply Sandia Labs Socorro code to InAs/GaSb SLS structures and obtain physically accurate results for ideal structures and to then incorporate defects in

Figure 1: HRTEM image of an InAs/GaSb SLS grown at CHTM

the SLS. The results of these calculations will then be compared to experimental data to see if we can get a better idea of what kind of defects are causing the high levels of dark current associated with our InAs/GaSb detectors.

1.1

InAs/GaSb type-II strained layer superlattices

A superlattice is a periodic structure of layers of two or more materials, the layers of which tend to be on the order of several nanometers. The materials used to grow a superlattice are typically semiconductors with dierent bandgaps. This technique creates a set of selection rules which aects the conditions for charges to ow through the structure. Due to the periodic structure of superlattice, it has periodic potential. To simplify the physical picture of SL, we can consider a set of quantum wells with nite barrier height U. The current standard for classifying superlattices is to group them by their connement energy schemes. These connement schemes are usually labeled type I and type II. In type I superlattices, the electrons and holes are both conned within the same layers. Type II superlattices are composed of spatially indirect band gap semiconductors which connes the electrons and holes in dierent layers. The Type II InAs/GaSb superlattice was rst introduced by the Nobel laureate L. Esaki in the 1970s [9] and then proposed for infrared detection applications by Smith and Mailhiot in 1987. Since then, the Type II Sb-based superlattice has evolved drastically with many variants for dierent purposes. It can be grown uniformly on comparatively large GaSb wafers with precise control of the SLS structures and has a higher electron eective mass rendering lower tunneling currents. In a InAs/GaSb SLS the valence band of GaSb is above the conduction band for InAs which creates minibands in the superlattice region by the coupling of electron wavefunctions. Infrared detection will be done by the intersubband transitions between two minibands. The mechanism for SRH recombination in InAs/GaSb SLS is unknown, however it appears to involve transitions to energy levels in the middle of the band-gap and gallium 2

Figure 2: Illustration of a InAs/GaSb SLS

is believed to be a limiting factor as gallium-free SLS structures exhibit longer carrier lifetimes. It has been suspected that the SRH mechanism is due to defects in the crystal lattice of the SLS structures, but it is not known what type of defect could be causing shorter carrier lifetimes. Every solid has defects in its structure. In the case of crystals there are characteristic defects (because of periodicity) such as: point defects, like vacancies and interstitials; one-dimensional defects, like dislocations; and two-dimensional defects, like grain boundaries, or interfaces. Trap assisted recombination occurs when an electron falls into a trap, an energy level within the band-gap caused by the presence of a foreign atom or a structural defect. Once the trap is lled it can not accept another electron. The electron occupying the trap energy can in a second step fall into an empty state in the valence band, thereby completing the recombination process and possibly producing dark current. In physics and in electronic engineering, dark current is the relatively small electric current that ows through photosensitive devices such as a photo-multiplier tube, photo-diode, or charge-coupled device even when no photons are entering the device. Accurate defect level calculations are needed to determine whether these account for the SRH mechanism or whether there could be some other type of defect such as anti-site bonding, interstitial atoms, etc. Reasonably accurate ab initio electronic structure calculations have been performed using density functional theory (DFT) with hybrid functionals [2]. Calculation of defects in semiconductor superlattices necessitates high-performance, parallel computation as a unit cell size of a few hundred atoms may be needed to suciently localize the defect states.

1.2

Density Functional Theory

For the present purposes, we dene the modern electronic structure problem as nding the ground-state energy of non-relativistic electrons for arbitrary positions of nuclei within the Born-Oppenheimer approximation [3]. If we can 3

perform many of these calculations in a reasonable time-frame, properties of arbitrary materials can be predicted. Many traditional approaches to solving this dicult many-body problem begin with the HartreeFock (HF) approximation, in which is approximated by a single Slater determinant of orbitals (singleparticle wave-functions)[15] and the energy is minimized [16]. Other approaches use reduced descriptions, such as the density matrix or Greens function, which leads to an innite set of coupled equations that must somehow be truncated. Density functional theory is a successful approach to nding solutions to the Schr odinger equation in practical settings, and is rapidly becoming a standard tool for materials modeling problems in physics, chemistry, and materials science. The situation we are interested in, where multiple electrons are interacting with multiple nuclei, is a very complicated system to model. With each electron in the system, 3 dimensions are added to the problem, so if we are interested in a cluster of 100 Pt atoms, the full wave function requires more than 23,000 dimensions. The fundamental tenet of density functional theory is that any property of a system of many interacting particles can be viewed as a functional of the ground state density n0 (r); that is, one scalar function of position n0 (r), in principle, determines all the information in the many-body wave-functions for the ground state and all excited states[5]. The modern formulation of DFT originated from a paper written by P. Hohenberg and W. Kohn in 1964 [7]. The paper shows that the electron density can be thought of as a basic variable used to determine all properties of the system; i.e. all the properties of the system can be thought of as functionals of the ground state density. This formulation can be used for any system of interacting particles in an external potential Vext (r). In our case we are interested in the problem of electrons and xed nuclei, where the Hamiltonian can be written as: 1 h2 = i + Vext + H 2me i=0 2 1 |ri rj | (1)

i=j

(the nuclei-nuclei interaction can be added later). DFT is based on two theorems rst proved by Hohenberg and Kohn [7]. Theorem 1: For any system of interacting particles in an external potential Vext (r), the potential Vext (r) is determined uniquely, except for a constant, by the ground state particle density n0 (r) [5]. Once we have Vext (r), the Hamiltonian is then determined, except for a constant energy. If we know the Hamiltonian then we know the many-body wavefunctions for all states, therefore all properties are determined by the electron density n0 (r). Theorem 2: A universal functional for the energy E[n] in terms of the density n(r) can be dened, valid for any external potential Vext (r).

For any particular Vext (r), the exact ground state energy of the system is the global minimum value of this functional, and the density n(r) that minimizes the functional is the exact ground state density n0 (r) [5]. We can then use this ground state density to determine the Hamiltonian and all the properties of the system. Thus it has been established that a functional can be dened for any density (subject to certain conditions), and that by minimizing this functional one would nd the exact density and energy of the true interacting many-body system. The problem that we are faced with is approximating these functionals since no one has provided a method of constructing the exact functionals. The main reason DFT is so widely used today is because of the approach proposed by Kohn and Sham in 1965 [8]. The idea of the Kohn-Sham approach is to replace the original many-body problem obeying the Hamiltonian by an auxiliary independent particle problem that can be solved more easily. This approach leads to independent-particle equations for the non-interacting system with all the dicult many-body terms incorporated into an exchange-correlation functional of the density. By solving these equations one can determine the ground state properties of the original system with the accuracy only limited by the approximations in the exchange-correlation functional. I wont go into much detail as far as the derivation, but essentially the Kohn-Sham approach is to rewrite the Hohenberg-Kohn expression for the ground state energy functional in the form: EKS = Ts [n] + dr Vext (r)n(r) + EHartree [n] + EII + Exc [n] where Vext is the external potential due to the nuclei and any external elds and EII is the interaction between nuclei [5]. Vext , EHartree and EII are all well dened so we just need to nd Exc [n] (Ts is given explicitly as a functional of the orbitals). If the universal functional Exc [n] were known, then the exact ground state energy and density of the many-body electron problem could be found by solving the Kohn-Sham equations. As long as we can make a good approximation of Exc [n] we then have a useful approach to calculating ground state electronic properties of a many-body system. The remarkable successes of the local density approximation (LDA) and the generalized-gradient approximation (GGA) functionals within the Kohn-Sham approach have led to widespread interest in density functional theory as the most promising approach for accurate, practical methods in the theory of materials. 1.2.1 The Local Density Approximation

The true form of the exchange-correlation functional, whose existence is guaranteed by the Hohenberg-Kohn theorem, is simply not known. There is however, one case where this functional can be derived exactly: the homogeneous electron gas. In this situation, the electron density is a constant at all points in space (i.e. n(r) = C ). This approximation only uses the local density to dene the approximate exchange-correlation functional, so it is called the local density approximation (LDA) [6]. The LDA may seem limited for use in materials science since variations in n(r) are what dene chemical bonds and properties, but the homogeneous electron gas does provide a practical way to actually use 5

As Sb N P As O S Se S Se

0.331 0.384 0.608 0.397 0.399 0.4469 0.3977 0.3867 0.3624 0.3533

10.6 14.4 9.3 9.6 12.3 3.7 5.1 5.4 5.5 6.2

7 6 5 6 6 5 5 5 4 4

0.42 0.00 0.00 0.43 0.00 0.60 1.64 0.82 0.77 0.24

1.16 0.51 1.77 1.55 0.76 3.87 3.75 2.63 2.62 1.65

1.17 0.52 1.79 1.54 0.78 3.23 3.64 2.46 2.63 1.63

0.34 0.70 0.00 0.00 0.38 0.00 0.00 0.40 0.00 0.42

1.52 0.81 1.89 1.42 0.42 3.44 3.78 2.82 2.58 1.83

perimental gaps for BN range from 6.0 to 6.5 eV. A recent result from Ref. 37 is used here for compari. Figure 3: Illustration of how inaccurate LDA can be for band gap calculations semiconductor was used as a reference for the model parameters. [19]

crepancy remains. The standard deviation ut 0.35 eV compared with the original deand gaps of greater than 1 eV. ther, we examine the consequences includorder correction. The second-order term in er, includes the interaction between s. As stated previously, this interaction is a ear-neighbor bonds but nevertheless must peal to some physical property in the ab Here we shall associate it with the bandr valence-band p-type states because these prototypical bonding orbitals in the tetraemiconductors, and their near-neighbor inn directly related to the tight-binding bandecognize that a number of semiconductors of local-eld effects in their dielectric den accurate GW corrections. These tend to semiconductors C, BN, etc., so, on this nably expected to be related to the bandion of this effect at the level of a linear introduces a single additional parameter quent correction of the form

FIG. 1. Theoretical bands gaps calculated within the LDA of the semiconductors listed in Table I. Circles, diamonds, and squares represent group IV, group III-V, and group II-VI semiconductors, respectively.

the Kohn-Sham equations. The LDA is also often surprisingly accurate and for systems with slowly varying charge densities generally gives very good results. However, it is a well known problem that the LDA leads to a substantial underestimate of calculated band gaps in semiconductors and insulators (g.3). Thus, the LDA method isnt accurate enough for our purposes. 1.2.2 The Generalized Gradient Approximation

The best known class of functionals after LDA uses information about the local gradient in the electron density as well as the local electron density. This approach is called the generalized gradient approximation (GGA). There are a large number of dierent GGA functionals because there many ways to form the gradient of the electron density. Two of the most widely used GGA functionals are the Perdew-Wang functional (PW91)[10] and the Perdew-Burke-Ernzerhof functional (PBE) [2]. The local density approximation can be considered to be the zeroth order approximation to the semi-classical expansion of the density matrix in terms of the density and its derivatives. A natural progression beyond the LDA is thus to the gradient expansion approximation (GEA) in which rst order gradient terms in the expansion are included. In the GGA a functional form is adopted which ensures the normalization condition and that 6

with N-1 electrons only (so called the self interaction problem [9]). In the DFT in the LDA approximation all occupied bands are pushed up in energy by this interaction which has for a consequence an onsite/diagonal Coulomb/Exchange repulsion. This leads to too small energy band gap in DFT-LDA. On the exchange is negative This leads to an energy functional that the the other hole hand, indenite. Hartree-Fock (HF) theory depends on both the density and its gradient but retains the analytic properCoulomb and correlation exchange interactions cancels exactly, ties of the exchange hole inherent in the LDA. The GGA improves signicantly the LDAs description of the binding energy of molecules. i.e. Jii = on Kii , so there is no self interaction. HF theory 1.2.3 Hybrid Functionals overestimates band gaps due to the lack of dynamical The hybrid approach to constructing density functional approximations was screening. It appears energy with gaps predicted introduced by Axel Becke in 1993 that [11]. Hybridization Hartree-Fock (exact)with exchange provides a simple scheme improving HF many molecular properties, hybrid functionals withfor ~20% and ~80% DFT such as atomization energies, bond lengths and vibration frequencies, which tend exchange, exactly the proportions optimised for use in to be poorly described with simple ab initio functionals [12]. Hybrid DFT functionals mix results from dierent functionals to get the Exchange-correlation the calculation of ground state energetics energy. The results are combined with a weighted sum, with the coecientsin are the B3LYP functional, are also in good agreement with Figure 4: Comparison of calculated band-gap (eV) vs. experimental using hyexperimentally measured ones. brid functionals [20]
7 6
Energy gap (theor.) (eV)

exchange compensa the exch constant; lattice co in a cova the use o shorter bo F small spin is remark and expe constants overall ag more sop theories t

5 4 3
6 7 9 10 8 11

Lattice constant (theory) (A)

B3LYP PBE0

12

2 1 0
12 3 5 4

(a)

1 InSb 2 InAs 3 InN (wz) 4 GaSb 5 GaAs 6 InP 7 AlSb 8 AlAs 9 GaP 10 AlP 11 GaN (wz) 12 AlN (wz)

B3LYP PBE0 GGA

7 8

6
5 34 1 2

(b)

1 GaP 2 AlP 3 GaAs 4 AlAs 5 InP 6 InAs 7 GaSb 8 AlSb 9 InSb

2 3 4 5 Energy gap (exp.) (eV)

6 Lattice constant (exp) (A)

I methodol large sca reliably p the electr

to be determined by reference to a system which the exact result is known. FIGURE 1. A comparison of for experimental energy gaps (a) Hybrid functionals of this type are now very widely used for chemistry and and experimental lattice binding constants (b), with and those predicted physics applications. Computed energies, geometries frequencies are systematically more reliable than the best and GGA GGA functionals. One example The using DFT with B3LYP, PBE0, functionals. of a successful hybrid functional is the Becke, three-parameter, Lee-Yang-Parr energy are computed at the experimental lattice functionalgaps (B3LYP). B 3LY P LDA HF LDA GGA LDA GGA LDA constant. Exc = Exc + a0 (Ex Ex ) + ax (Ex Ex ) + ac (Ec Ec )

It has been shown previously, that the B3LYP functional, can provide a remarkable agreement with measured energy gaps, for most of the III-V semiconductor binaries 7 [10]. In figure 1(a) the calculated energy gaps of 9 representative ZB binaries and 3 group IIIN WZ materials are shown for the B3LYP and PBE0 hybrid functionals. The B3LYP functional provides slightly better agreement with the

(2) Unfortunately, although the results obtained with these functionals are usually suciently accurate for most applications, there is no systematic way of improving them. Hence in the current DFT approach it is not possible to estimate the error of the calculations without comparing them to other methods or experiments.

1. S. Kur 75, 889 2. C.M. Saunde 1873 ( 3. B. Mo Dovesi 4. R. Dov of Tori 5. C.L. B and N. (2008)

1.2.4

Pseudopotentials

We have simplied our quantum problem so that we just need to solve a singleparticle equation (Kohn-Sham approach), but we need to solve for enough states for every electron. The core electrons spend all their time near the nucleus. They repel the outer electrons, so the outer electrons feel a weaker potential from the nucleus, but otherwise they dont aect the chemical properties etc. Provided we reproduce this screening eect, we can ignore these core electrons altogether! We consider each atoms nucleus and core electrons as an ion (LDA), and produce a pseudopotential that has the same eect on the outer electrons. Not only have pseudopotentials reduced the cut-o energy we need, they have also let us concentrate on the valence electrons, reducing the number of states we need from our Schrdinger equation. Figure 5: Comparison of a wavefunction in the Coulomb potential of the nucleus (blue) to the one in the pseudopotential (red). The real and the pseudo wavefunction and potentials match above a certain cuto radius rc .

Activities So Far

When I applied for the REU program at CHTM, I was hoping to get an idea of what grad school would be like and at the same time start learning about some of the problems that modern science is currently taking on. Most of my time working at CHTM so far has been spent building up background knowledge in the hopes that I could actually start understanding what these problems even are. Looking back on my educational career so far, I cant think of any time in my life that I have learned so much. The research project I have been working on with Dr. Greg Von Winckel is, in his words not appropriate

for an undergraduate, but I feel that I have ourished from being thrown in the deep end. Along with building up my knowledge on materials science, I have been evaluating various DFT calculation packages.

2.1

DFT software

There is a wide spectrum of software packages to choose from that can perform ab initio DFT calculations. A quick internet search reveals a few dozen pieces of software for solving these systems. Each one comes with its own learning curves, availability of documentation, and quirks. In an eort to narrow down the software that we thought would suit our needs we set a benchmark that the given software package should be able to make band gap calculations for III-V semiconductors withing a reasonable deviation (20 percent) of the experimental values. 2.1.1 ADF computational chemistry package

The rst software package that I tried out was the Amsterdam Density Functional (ADF) computational chemistry package. ADF has a free trial so I was able to try out dierent DFT calculations for a variety of materials. The documentation for ADF is the best that I have come across so far in the realm of DFT software, but I was still left confused about a few important details (like how to form a superlattice). ADF also has a good GUI that is fairly intuitive (when compared to other DFT software). None of the calculations I performed for GaAs gave the current band-gap within even 20 percent accuracy, so I ended up moving on to try other software. This is probably because ADF is meant more for use by chemists (who would be doing calculations for complex organic molecules for example) and not materials science. 2.1.2 Abinit

Abinit was developed using the popular Kohn-Sham formulation of DFT. It is currently run by Xavier Gonze and written in FORTRAN. Dozens of variables are available for customizing the input conditions of a system. This makes Abinit fairly versatile, but also provides a hard learning-curve. Abinit has two dierent pseudo-potentials built into it for each element. Additionally, it has multiple algorithms to calculate a new pseudo-potential if one is desired. Once I was nally able to get Abinit working on my computer at work, I wasnt able to calculate a band-gap for GaAs that was close enough to the experimental value to suit our needs. 2.1.3 Gaussian

Gaussian was originally developed by Nobel laureate John Pople in 1971 at Carnegie Mellon in FORTRAN. Initially, the program was open source and freely distributed to any university that wanted to use it. However, more recently the program has become very closed-source and is sold by Gaussian Inc. 9

under an extremely restrictive license. Various stipulations of the license are: not being allowed to disclose how fast the program is, work on any competing program, or allow anyone that is banned from using Gaussian to use your copy. The ocial list of people banned from using Gaussian can be found at www.bannedbygaussian.org which includes Princeton, CalTech, and the creator of Gaussian himself (John Pople). Since it is illegal to discuss how fast the program is, and how accurate it is, it is hard to determine whether it is worth the price of $4500-36,000 (academic and industry prices respectively). It is especially hard to justify this price when there are open-source programs that are freely available. Since there is no trial, we selected not to use Gaussian. 2.1.4 VASP

VASP is a plane-wave code for ab-initio density-functional calculations. It attempts to match the accuracy of the most advanced all-electron codes by using a projector-augmented-wave approach (PAW) [13] for describing the electronion interaction. In VASP, central quantities, like the one-electron orbitals, the electronic charge density, and the local potential are expressed in plane wave basis sets. The interactions between the electrons and ions are described using norm-conserving or ultra-soft pseudo-potentials, or the projector-augmentedwave method. VASP implements all of the common DFT methods including hybrid functionals. Greens functions methods and many-body perturbation theory are also available in VASP. I emailed VASP and they assured me that it could calculate reasonably accurate band-gaps for GaAs and other III-V semiconductors. We were thinking of going with VASP, but after talking with Normand Modine from Sandia Labs we decided to use Soccoro instead for various reasons.

2.2

Collaboration with CINT

Socorro is a modular, object oriented code for performing self-consistent electronic-structure calculations utilizing the Kohn-Sham formulation of densityfunctional theory and is being developed by researchers at Sandia National Laboratories, Vanderbilt University, and Wake Forest University under a GNU General Public License. Since we were looking for software that would need to t to a specic set of requirements, we decided that using Soccoro would be the right choice since we can work closely with Sandia to modify it to suit our needs. In early February we submitted a CINT Rapid Access proposal, which was then accepted. In the six weeks since the Rapid Access proposal was accepted, we have worked with CINT Scientist Normand Modine to demonstrate that we can use the Socorro code and hybrid functionals incorporating a suitable fraction of the exact exchange to obtain band gaps that agree well with experimental results for InAs and GaAs. In the case of InAs, we found that the optimized eective potential method implemented in Socorro did not converge reliably to the correct ground state due to the nearly vanishing Kohn-Sham band gap of this system. As a result, Dr. Modine implemented the Generalized Kohn-Sham

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approach to hybrid calculations using a recently proposed compact representation of the exchange-operator[14]. For the cases that we have tested, we nd that this approach converges robustly and rapidly to the ground state while maintaining the computational eciency of the optimized eective potential method. Based on these results, we conclude that the Socorro code will likely be able to provide an accurate model of InAs/GaSb SLS.

Plans For the Future

The goal of this work is two-fold: (1) to apply the Socorro code to InAs/GaSb SLS structures and obtain physically accurate results for an ideal structure. In particular, we will calculate the band osets and electronic structure for several layer thicknesses of interest and compare it to experimentally measured parameters from structures grown at CHTM, and (2) to incorporate defects in the SLS. To do so, we will introduce intrinsic point defects at various locations in the SLS, relax the defect structures, and calculate the defect formation energies as well as the defect energy levels within the superlattice band gap. Adequately resolving these localized energy states due to defects is computationally challenging, as it requires that the unit cell be suciently large that a defect not interact too strongly with its images in adjacent super cells. This, coupled with the SLS structure itself, necessitates a much larger unit cell than is typical in semiconductor band structure calculations. We will continue work with Dr. Modine to evaluate the applicability of Socorro to simulating InAs/GaSb SLS and determine whether additional hybrid functionals will need to be implemented. Dr. Von Winckel will assist in the development of Socorro improve computational eciency as needed to handle larger unit cells.

References

[1] N. Gautam, M. Naydenkov, S. Myers, A.V. Barve, E. Plis, T. Rotter, L.R. Dawson, S. Krishna Appl. Phys. Lett., 98 (2011), p. 121106. [2] G. Kresse, F. Tran, Y.S. Kim, M. Marsman, and P. Blaha. Towards ecient band structure and eective mass calculations for III-V direct band-gap semiconductors. Phys. Rev. B, 82:205212, (2012). [3] M. Born, R. Oppenheimer, Ann. Phys. 1927, 389, 457. [4] K. Burke, LO. Wagner, Int. J. Quantum Chem. 2013, 113, 96101. DOI: 10.1002/qua.24259. [5] Electronic Structure: Basic Theory and Practical Methods (Vol 1) (26 April 2004) by Richard M. Martin. [6] Jungwirth, P. (2010), Density Functional Theory. A Practical Introduction. By David Sholl and Janice A. Steckel. Angew. Chem. Int. Ed., 49: 485. doi: 10.1002/anie.200905551. [7] P. Hohenberg and W. Kohn, Inhomogenous Electron Gas phys. Rev. 136:B864-871, 1964.

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[8] Kohn, Walter; Sham, Lu Jeu (1965). Physical Review 140 (4A): A1133A1138. doi:10.1103/PhysRev.140.A1133. [9] G. A. Sai-Halasz, R. Tsu, and L. Esaki, A new semiconductor superlattice,Appl. Phys. Lett., vol. 30, no. 12, pp. 651653, Jun. 1977. [10] J.P. Perdew, in Electronic Structure of Solids 91, edited by P. Ziesche and H. Eschrig (Akademie Verlag, Berlin, 1991), p. 11. [11] A.D. Becke (1993). J. Chem. Phys. 98 (2): 13721377. doi:10.1063/1.464304. [12] John P. Perdew, Matthias Ernzerhof and Kieron Burke (1996). J. Chem. Phys. 105 (22): 99829985. doi:10.1063/1.472933. [13] Bl ochl, P. E. Phys Rev B 1994, 50, 17 953. [14] I. Duchemin and F. Gygi, Computer Physics Communications, 181:855, (2010) [15] J. C. Slater, Phys. Rev. 1929, 34, 1293. [16] D. R. Hartree, W. Hartree, Proc. R. Soc. London. Ser. A Math. Phys. Sci. 1935, 150, 9. [17] Hai Xiao, Jamil Tahir-Kheli, and William A. Goddard, J. Phys. Chem. Lett. 2011, 2, 212217. DOI: 10.1021/jz101565j [18] C.H. Grein, M.E. Flatte, H. Ehrenreich, R.H. Miles, J. Appl. Phys. 74 (1993) 4774; [19] Elena Plis, et al. Infrared Physics & Technology. DOI:10.1016/j.infrared.2009.09.008 [20] Kurt A. Johnson, N. W. Ashcroft Phys. Rev. B 12/1998; 58(23). DOI:10.1103 [21] S. Tomic, B. Montanari, N.M.Harrison Physica E, 40(2008), p.2125

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