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Introduction to Pseudopotential Method

**An introduction to the empirical pseudopotential method
**

Aaron J. Danner

Created at the University of Illinois at Urbana-Champaign, Urbana, IL 61801 in 2004 Last edited on January 31, 2011

Abstract: Using some of the first published papers from the 1960’s on the pseudopotential method, a program was completed which allows fully vectorial electronic band structure calculations on diamond and zincblende materials, including Si and GaAs. This article introduces the pseudopotential method from first principles and illustrates its use with Si, GaAs, and AlAs. Using more recent published data on the properties of AlAs, appropriate pseudopotential form factors were determined using an iterative method and the complete band structure is calculated from the obtained results.

1. Useful downloads Right click to download a Mathematica program useful in performing pseudopotential method calculations. Left click to go to the download site for MathReader, free software which allows Mathematica code to be viewed for study even if Mathematica is not installed. Right click to download a Mathcad implementation for calculating a silicon band diagram, generously provided by Mr. Pierre Tomasini of Arizona State University. 2. Introduction The empirical pseudopotential method was developed in the 1960’s [1-3] as a way to solve Schrodinger’s equation for bulk crystals without knowing exactly the potential experienced by an electron in the lattice. Since electrons are interacting with the crystal lattice, an electronic band structure calculation is a many body problem (unlike the situation in photonic crystal calculations, for example [4]). Although other methods existed at the time for approximating electronic band structures, the pseudopotential method gives surprisingly accurate results considering the computing time and effort involved. The basic scheme is to assume that the core electrons are tightly bound to their nuclei, and the valence and conduction band electrons are influenced only by the remaining potential. Since the potential can be Fourier expanded in plane waves, an eigenvalue equation for determining an E-k relationship can be established. Although the Fourier coefficients for the potentials are not known, they can be empirically determined for a given crystal by fitting calculated crystal parameters to known measurements. Cohen and Bergstresser followed these steps to determine band structures of several diamond and III-V zincblende structures [5]. In this term paper, I repeat the original steps taken by Cohen and Bergstresser in formulating the pseudopotential method, then carry out calculations using a computer program I wrote to construct the electronic band diagrams of Si and GaAs using their form factors. Then, I apply the method to AlAs, for which form factors are essentially unavailable, and construct a plausible E-k diagram for the compound using known parameters. Limitations on the method used are discussed, as well as more powerful methods of determining accurate band structures. 3. Theoretical basis This development is essentially identical to that followed by Cohen and Bergstresser [5] and others [6, 7]. Starting out with the time-independent Schrodinger equation,

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(1) we use Bloch’s theorem to restate the wavefunctions in terms of plane waves (because the crystal is a periodic structure). (2) Because of the periodic nature of both the wavefunction and the potential, plane wave expansion can be used to write each as an infinite series, summed over reciprocal lattice vectors.

(3) (4) In Equations (3) and (4), the parameters A and V represent Fourier coefficients for given reciprocal lattice vectors. Substituting Equations (3) and (4) into the Schrodinger equation, the result is the following: (5) Equation (5) is then multiplied by an orthogonal function and integrated over the volume of the crystal. This creates Kronecker delta functions where previously there were exponentials. (6) In Equation (6), one summation in each term can be eliminated. For example, in the first term, h and l must be equal in order for the term to be non-zero. Thus the summation over h includes only one non-zero term. Likewise, a summation can be eliminated from each of the other two terms. (7) Equation (7) can be cast as an eigenvalue equation with the following matrix form, where H represents the Hamiltonian matrix element. If the Fourier series were not truncated, then the matrix would be infinite in size. In calculations that will be carried out later, it was found that a 124 x 124 matrix resulted in reasonable accuracy. Reference (6) shows a matrix only involving positive values of l and h, which seems to be incorrect. This type of Fourier expansion should be symmetric about the origin. If this were not the case, then the eigenvalues would not be guaranteed to be real.

(8) To solve Equation (8), the Hamiltonian matrix must be diagonalized, which can be accomplished using standard numerical routines. The eigenvalues of the matrix are the possible values of energy E(k). For each k vector in a

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band diagram, the matrix must be diagonalized. Equation (9) allows the calculation of each element in the matrix. The remaining problem is to find appropriate values for the potential function V. (9) Because there are two atoms per cell in the fcc structure for zincblende or diamond materials, the potential must include the contribution of both. The convention of Cohen and Bergstresser will be followed, taking the point halfway between the atoms as the origin of each cell in the fcc structure. The potential itself can be split into symmetric and antisymmetric parts, as in Equation (10), (10) where represents the absolute offset of an atom from the origin of each cell in the fcc lattice. (One atom is located at the cell origin offset by , and the other atom is offset by - .) For the materials considered here, (11) The terms and are known as the form factors, and are usually determined empirically, although there are some first principles approaches reported [8]. It has been found that only six terms are necessary for reasonable accuracy, which eases the task of pinpointing their values empirically. Form factor determination will be discussed further in the next section. Equations (1) through (11) represent the local pseudopotential theory. They were used to create band diagram software (see Appendix) using Mathematica, although any language (especially those including linear algebra libraries) could be used. Although the eigenmatrix can be determined from Equations (9) and (10), the task of properly ordering the reciprocal lattice vectors correctly in the matrix can appear daunting. I have created a generating function that can carry out the task. Because the reciprocal lattice vectors K are based on the basis reciprocal lattice vectors (i.e. K = hb1 + kb2+ lb3 , where h, k, and l are integers), care must be taken to ensure that the three integer variables are properly incremented from the center of the matrix along the columns so that all states are included and none are skipped. Refer to the documented source code in the Appendix, where it is apparent that K can be written as a function of only matrix row. 4. Application: Si and GaAs band structure calculations Table 1 shows form factors as given by Cohen and Bergstresser [5] (except silicon [9]). These were used as inputs (along with lattice constant) to the band structure program (Appendix) to confirm their results. The form factors for Ge have been included to illustrate the method that was used to originally determine the form factors for GaAs. Because Ge lies between Ga and As in the periodic table, it is reasonable that its symmetric form factor should be the same (charge balanced at each fcc cell in the same way for the symmetric term). However, because the atoms are no longer the same, there is an antisymmetric term that enters Equation (10). Note that this causes the eigenmatrix to be complex. Nevertheless the eigenvalues are guaranteed to be real. Table 1: Form factors found in literature (circa 1965), given in Rydbergs

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Form factor VS3 VS8 VS11 VA 3 VA 4 VA 11

Si [9] -0.21 0.04 0.08 0 0 0

Ge [5] -0.23 0.01 0.06 0 0 0

GaAs [5] -0.23 0.01 0.06 0.07 0.05 0.01

The actual calculation of the energy eigenvalues for a single k point took less than a minute on a 733 MHz Pentium III machine. I have included the L, G, X, K, and W symmetry points in the band diagrams, shown in Figures 2 and 3. The distances along the k axes between symmetry points were calculated based on the actual distance moved in k space through the Brillouin zone, which is why, for example the distance from G to X is much larger than the distance from X to W. Figures 2 and 3 show good agreement with published band structures [5]. Although the band structures agree almost perfectly with the original work of Cohen and Bergstresser, they do not include localized effects or spin-orbit coupling. For example, at the G point in GaAs the split off band is not lowered correctly. The reason for this is that the pseudopotential is not just dependent on the energy, but also on the angular momentum components from electrons in the core states. These interactions have been neglected in the above development and can be included by adding correction terms to the Hamiltonian matrix element [9], but this is beyond the scope of this term paper.

Fig. 1

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Fig. 2 5. Determination of AlAs form factors I was only able to find form factors for AlAs from one source (“DAMOCLES”) [7], and using them in a band structure calculation did not result in the correct energy gaps at symmetry points, as shown in Table 2. The discrepancies should be qualified: DAMOCLES values might be used in more complicated formulations, where spin-orbit interactions are included as well as non-local phenomena which could alter the main pseudopotential terms. However that information was not available since DAMOCLES data was obtained from an internet site advertising its capabilities, not necessarily a trusted publication. It is apparent that the base pseudopotentials do change when adding correction terms. Nonetheless the data quoted in Table 2 was the only data on AlAs available, except for a first principles calculation (OPW method) carried out at a time when little experimental data was available for confirmation [10]. Table 2: Primary gaps from (a) theoretical IBM project, (b) trusted experimental source, and (c) my pseudopotential calculation Parameter (a) (b) (c) DAMOCLES [7] Experimental [8] Fitted 2.39 eV 2.991 eV 2.97 eV E G

G EGX EGL

2.21 eV 1.77 eV

2.164 eV 2.36 eV

2.09 eV 2.38 eV

AlAs form factors were iteratively found by measuring the resulting energy gaps against the experimentally measured energy gaps shown in Table 2. I began with the average symmetric form factors of Si and Ge (following the technique of Reference 5 for compound semiconductors), and first varied the asymmetric form factors until the values were close. Then and iteration process was carried out that results in less than 0.1 eV variation from experimentally measured values in the worst case (Table 2c). The form factors found are shown in Table 3. Finally, a full electronic band structure was created using the form factors, as shown in Fig. 3. There is

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no guarantee that it is correct because of the inability to find more data on AlAs, but the main energy gaps are correct and it shows the characteristic indirect behavior as well as the offset X-valley minimum. Table 3. Comparison of possible form factors for AlAs, and those of GaAs Form factor VS3 VS8 VS11 VA 3 VA 4 VA 11 GaAs -0.23 0.01 0.06 0.07 0.05 0.01 DAMOCLES AlAs -0.22 0.043 0.06 0.013 0.055 0.02 Fitted AlAs -0.221 0.025 0.07 0.08 0.05 -0.004

Fig. 3 In conclusion, the empirical pseudopotential method was used to calculate three band diagrams, including AlAs, for which the form factors were not previously known. 6. References 1. J.C. Phillips, “Energy-Band Interpolation Scheme Based on a Pseudopotential,” Phys. Rev. 112, 685 (1958). 2. J.C. Phillips and L. Kleinman, “New Method for Calculating Wave Functions in Crystals and Molecules,” Phys. Rev. 116, 287 (1959). 3. L. Kleinman and J.C. Phillips, “Crystal Potential and Energy Bands of Semiconductors. III. SelfConsistent Calculations for Silicon,” Phys. Rev. 118, 1153 (1960). 4. A.A. Maradudin, and A.R. McGurn, “Out of plane propagation of electromagnetic waves in a twowww.ece.nus.edu.sg/stf page/eleadj/pseudopotential.htm 6/7

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dimensional periodic dielectric medium,” J. of Mod. Optics, 41, 275 (1994). 5. Marvin L. Cohen and T.K. Bergstresser, “Band Structures and Pseudopotential Form Factors for Fourteen Semiconductors of the Diamond and Zinc-blende Structures,” Phys. Rev. 141, 2, p. 789 (1966). 6. Umberto Ravaioli and Singh T. Junior, “The Empirical Pseudopotential Method,” http://wwwncce.ceg.uiuc.edu/tutorials/bandstructure/pseudo.html, downloaded November, 1995 (link now inactive). 7. DAMOCLES: Numerical algorithms – Band structure and scattering rates. http://www.research.ibm.com/DAMOCLES/html_files/numerics.html, downloaded November 6, 2002. 8. I. Vurgaftman, J.R. Meyer, and L.R. Ram-Mohan, “Band parameters for III-V compounds and their alloys,” J. of Appl. Phys. 89, 11 (2001). 9. James R. Chelikowsky and Marvin L. Cohen, “Nonlocal pseudopotential calculations for the electronic structure of eleven diamond and zincblende semiconductors,” Phys. Rev. B 14, 2 (1976). 10. D.J. Stukel and R.N. Euwema, “Energy-Band Structure of Aluminum Arsenide,” Phys. Rev. 188, 3 (1969). 7. Acknowledgements Thanks to Emmanuel Van Kerschaver, for pointing out a mistake in the orthogonal function (Jan. 10, 2008), and to Tim Saucer at the University of Michigan for correcting a reference mistake (Jan 30, 2011).

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