kp perturbation theory

In solid-state physics, kp perturbation theory is an approximation scheme for calculating the band structure (particularly effective mass) and optical properties of crystalline solids.[1][2][3] It is pronounced "k dot p", and is also called the "kp method". This theory has been applied specifically in the framework of the LuttingerKohn model (after Joaquin Mazdak Luttinger and Walter Kohn), and of the Kane model (after Evan O. Kane).

Contents

1 Background and derivation o 1.1 Bloch's theorem and wavevectors o 1.2 Perturbation theory o 1.3 Expression for a nondegenerate band 1.3.1 Effective mass o 1.4 kp model with spin-orbit interaction o 1.5 Calculation in degenerate case 2 Notes and references 3 See also

Background and derivation

Bloch's theorem and wavevectors
See also: Bloch wave According to quantum mechanics (in the single-electron approximation), the electrons in any material have wavefunctions which can be described by the following Schrdinger equation:

where p is the quantum-mechanical momentum operator, V is the potential, and m is the mass of an electron. (This equation neglects the spin-orbit effect; see below.) In a crystalline solid, V is a periodic function, with the same periodicity as the crystal lattice. Bloch's theorem proves that the solutions to this differential equation can be written as follows:

where k is a vector (called the wavevector), n is a discrete index (called the band index), and un,k is a function with the same periodicity as the crystal lattice.

For any given n, the associated states are called a band. In each band, there will be a relation between the wavevector k and the energy of the state En,k, called the band dispersion. Calculating this dispersion is one of the primary applications of kp perturbation theory.

Perturbation theory
See also: Perturbation theory (quantum mechanics) The periodic function un,k satisfies the following Schrdinger-type equation:[1-Cardona]

where the Hamiltonian is

Note that k is a vector consisting of three real numbers with units of inverse length, while p is a vector of operators; to be explicit,

In any case, we write this Hamiltonian as the sum of two terms:

This expression is the basis for perturbation theory. The "unperturbed Hamiltonian" is H0, which in fact equals the exact Hamiltonian at k=0 (i.e., at the Gamma point). The "perturbation" is the term . The analysis that results is called "kp perturbation theory", due to the term proportional to kp. The result of this analysis is an expression for En,k and un,k in terms of the energies and wavefunctions at k=0. Note that the "perturbation" term gets progressively smaller as k approaches zero. Therefore, kp perturbation theory is most accurate for small values of k. However, if enough terms are included in the perturbative expansion, then the theory can in fact be reasonably accurate for any value of k in the entire Brillouin zone.

Expression for a nondegenerate band

For a nondegenerate band (i.e., a band which has a different energy at k=0 from any other band), with an extremum at k=0, and with no spin-orbit coupling, the result of kp perturbation theory is (to lowest nontrivial order):[1]

The parameters that are required to do these calculations, namely En,0 and , are typically inferred from experimental data. (The latter are called "optical matrix elements".) In practice, the sum over n' often includes only the nearest one or two bands, since these tend to be the most important (due to the denominator). However, for improved accuracy, especially at larger k, more bands must be included, as well as more terms in the perturbative expansion than the ones written above. Effective mass Main article: Effective mass (solid-state physics) Using the expression above for the energy dispersion relation, a simplified expression for the effective mass in the conduction band of a semiconductor can be found.[3] To approximate the dispersion relation in the case of the conduction band, take the energy En0 as the minimum conduction band energy Ec0 and include in the summation only terms with energies near the valence band maximum, where the energy difference in the denominator is smallest. (These terms are the largest contributions to the summation.) This denominator is then approximated as the band gap Eg, leading to an energy expression:

The effective mass in direction is then:

Ignoring the details of the matrix elements, the key consequences are that the effective mass varies with the smallest bandgap and goes to zero as the gap goes to zero.[3] A useful approximation for the matrix elements in direct gap semiconductors is:[4]

which applies within about 15% or better to most group-IV, III-V and II-VI semiconductors.[5]

In contrast to this simple approximation, in the case of valence band energy the spin-orbit interaction must be introduced (see below) and many more bands must be individually considered. The calculation is provided in Yu and Cardona.[6] In the valence band the mobile carriers are holes. One finds there are two types of hole, named heavy and light, with anisotropic masses.

kp model with spin-orbit interaction

Including the spin-orbit interaction, the Schrdinger equation for u is:[2]

where

where is a vector consisting of the three Pauli matrices. This Hamiltonian can be subjected to the same sort of perturbation-theory analysis as above.

Calculation in degenerate case

For degenerate or nearly degenerate bands, in particular the valence bands in certain materials such as gallium arsenide, the equations can be analyzed by the methods of degenerate perturbation theory.[1][2] Models of this type include the "Luttinger-Kohn model" (a.k.a. "KohnLuttinger model"),[7] and the "Kane model".[8]

Notes and references

1. ^ a b c d P. Yu, M. Cardona (2005). Fundamentals of Semiconductors: Physics and Materials Properties (3rd ed.). Springer. Section 2.6, pp. 68 ff'. ISBN 3-540-25470-6. 2. ^ a b c C. Kittel (1987). Quantum Theory of Solids (Second Revised Printing ed.). New York: Wiley. pp. 186190. ISBN 0-471-62412-8. 3. ^ a b c W.P. Harrison (1989) [1980]. Electronic Structure and the Properties of Solids (Reprint ed.). Dover Publications. pp. 158 ff. ISBN 0-486-66021-4. 4. ^ A direct gap semiconductor is one where the valence band maximum and conduction band minimum occur at the same position in k-space, usually the so-called -point where k = 0. 5. ^ See Table 2.22 in Yu & Cardona, op. cit. 6. ^ See Yu & Cardona, op. cit. pp. 75-82 7. ^ J. M. Luttinger, W. Kohn (1955). "Motion of Electrons and Holes in Perturbed Periodic Fields". Physical Review 97: 869. Bibcode:1955PhRv...97..869L. doi:10.1103/PhysRev.97.869.

8. ^ Evan O. Kane (1957). "Band Structure of Indium Antimonide". Journal of Physics and Chemistry of Solids 1: 249. Bibcode:1957JPCS....1..249K. doi:10.1016/00223697(57)90013-6.

3.7 The kp method

Using the kp method [Bir74,Yu03] one can obtain analytical expressions for the band dispersion and the effective masses. It allows the extrapolation of the band structure over the entire Brillouin zone from the energy gaps and optical matrix elements at the zone center. While the kp theory has been frequently used to model the valence band of semiconductors, we will additionally apply it to model the impact of strain on the conduction band minimum. The kp method can be derived from the one-electron Schrdinger equation

(3.58)

Here

denotes the one-electron Hamilton operator and

the periodic lattice potential. The and

wavefunction of an electron in an eigenstate labeled

and its energy are denoted by

, respectively. In a periodic potential Bloch's theorem applies, and the solutions of (3.58) can be expressed as (3.59)

where

is the band index,

a wave vector, and

has the periodicity of the lattice. into (3.58) to obtain an

Assuming that the potential equation for

is local3.1, one can substitute

(3.60)

Considering any fixed wavevector eigenfunctions

, the above equation yields a complete set of

, which completely span the space of lattice periodic functions in the real at can be expanded in terms of (3.61)

space. Hence, the wavefunction

Once,

and

are known, the functions

and the eigenenergies

at any

vector in the vicinity of can be obtained by treating the term in (3.60) as a perturbation. Either degenerate or nondegenerate perturbation theory has to be used. The method has been first applied by Seitz [Seitz35] and was later extended to study the band structure of semiconductors [Luttinger55,Kane56,Cardona66]. This method for calculating the band structure is known as the kp method. It works best for small and can be applied to calculate the band structure near any given point provided

that the matrix elements of

between the wavefunctions (or the wavefunctions themselves) and

the energies at are known. When using a sufficiently large number of to approximate a complete set of basis functions, the band structure over the entire first Brillouin zone can be calculated by diagonalizing (3.60) numerically [Cardona66]. In the following, a nondegenerate kp theory will be used to derive the band dispersion and the effective masses for the nondegenerate conduction band of Si. To analyze the effect of shear strain on the lowest conduction band since the , a degenerate kp method is adopted in Section 3.7.2, (zone boundary)

conduction band is expanded around the symmetry point conduction band.

where it touches the

3.5.2 The k.p Method

The k.p method allows to derive analytical expressions for the energy dispersion and the effective masses [161]. It enables the extrapolation of the band structure over the entire Brillouin

zone from the energy gaps and matrix elements at the zone center. In addition to the common use of the k.p method to model the valence band of semiconductors, it is also well suited to describe the influence of strain on the conduction band minimum. The k.p method can be derived from the one-electron Schrdinger equation as follows:

(3.26)

denotes the periodic lattice potential and

the one-electron Hamilton operator.

describes the one-electron wave function in an eigenstate and the eigenenergy for the eigenstate . Due to the periodicity of the lattice potential (3.26) the Bloch theorem is applicable and the solution can be written in the form of: (3.27)

The wave function

can be expressed as the product of a plane wave and the function denotes the band index and

, which reflects the periodicity of the lattice.

represents a wave vector. If the given potential only depends on one spatial coordinate (also called local), (3.27) can be substituted in (3.26). Luttinger [173] showed that it is possible to use the eigenfunctions of the ground states as a complete set of eigenfunctions and that the wave function can be expanded by (3.28)

for

. Inserting (3.28) into (3.26) yields:

(3.29)

This way, for any fixed wave vector complete set of eigenfunctions

, (3.29) for the unperturbed system, delivers a , which completely cover the space of the lattice periodic at , for the full system, can be

functions in real space. Therefore, the wave function expressed via

(3.30)

As soon as the eigenenergy eigenfunctions

and the

of the unperturbed system are determined, the can be calculated for any in the

and eigenenergies

vicinity of by accounting the term in (3.29) as a perturbation. This method has been introduced by Seitz [174] and extended by [172,173,175] to study the band structure of semiconductors.

Due to the energies at

term in (3.29) this method is also known as the k.p method. Provided that the and that the matrix elements of between the wave functions, or the wave

functions themselves, are known, the band structure for small 's around can be calculated. The entire first Brillouin zone can be calculated by diagonalizing (3.29) numerically, provided a sufficiently large set of used [172]. to approximate the complete set of basis functions is

The following subsections will explain the effective masses for the non-degenerate conduction band of silicon and the energy dispersion utilizing a non-degenerate k.p theory. In order to analyze the effects of shear strain on the two lowest conduction bands method is adapted to enable degeneracy, due to the coincidence of the point. and and , the k.p bands at the

3.5.2.1 Effective Electron Mass in Unstrained Silicon

The conduction band minima of silicon reside on the axes at a distance of from the symmetry points. By means of non-degenerate perturbation theory and the knowledge of the eigenenergies eigenvalues and the wave functions at neighboring points at the conduction band minima . , the

can be expanded to second order terms in

(3.31 )

Scalar products Dirac's notation

are expressed via index notation

and the matrix elements with

(3.32)

The linear terms in

can be set to zero under the assumption that

is a minimum. The

expression for the effective mass tensor

can be derived from the dispersion relation (3.31) (3.33)

The effective mass tensor for the lowest conduction band

in diamond crystal structures is valley the effective

characterized by two masses. In the principal coordinate system for the masses can be written as

(3.34)

and

(3.35)

denotes the band index can be formulated as:

of the lowest conduction band. Therefore, the energy dispersion

(3.36)

From the derived equations follows that due to the coupling between electronic states in different bands (via k.p term), an electron in a solid has a different mass than a free electron. The coupling terms are related to the following criteria:

The bigger the energetic gap between two bands, the smaller is the effect on the effective mass. The relative importance of a band to the effective mass of band is controlled by the energy gap between the two bands. All bands with non-zero matrix elements can be found via the matrix element theorem [176] by group theoretical considerations checking all possible symmetries for .

It is possible to calculate numerically all matrix elements and subsequently the effective masses from (3.33) via the empirical pseudo potential method [177].

3.5.2.2 The Silicon Conduction Band Minimum's Dependence on Strain

(3.55) only requires the direction of the vector, indicating the location of the valley, to describe the shift of the valley minima. Hence, the valley shift is independent of the exact value of the wave vector and all points belonging to a particular valley experience the same shift. Since the effective mass is given by the second derivative of the energy dispersion and (3.16) does not change the curvature of the energy band, the formula predicts no change in the effective electron mass due to strain. However, there is a clear experimental proof that shear strain changes the effective masses of electrons in the lowest conduction band[170] and the exciton spectrum of silicon[171]. In order to explain this behavior one has to take the splitting of the lowest two conduction bands at the symmetry point by shear strain into account. The lifting of the degeneracy can be calculated

with the deformation potential constant

via (3.20). (3.20) is only valid at the

symmetry . In order to symmetry

point and cannot be used to predict the effect of strain on the valley minima circumvent this obstacle a degenerate k.p theory has to be applied around the point.

A different approach was adapted in [161]. The Hamiltonian at the be described via the theory of invariants:

points can

(3.37)

where, (3.38)

and

are the Pauli's matrices and

and

denote scalar constants (3.39)

and

The scalar constants , , and through

, and

are connected to the deformation potential constants

(3.40)

From (3.37) eigenvalues can be calculated which represent the energy dispersion for the first and second conduction band (3.41)

where denotes the energy dispersion of and that of . Under the assumption that this description is valid around the point up to the minimum of the lowest conduction band at , and can be related to each other via (3.42)

describes the distance of the conduction band minimum of unstrained silicon to the point. can be determined from (3.42) (3.43)

The effect of shear strain on the shape of the lowest conduction band is examined in the following section.

3.5.2.3 The Conduction Band Minimum of Silicon and its Energy Dispersion under Strain
Up to now it has been assumed that the conduction band minima are located at . This is only valid for small shear strain. The minimum of the conduction band moves towards the point in conjunction with an increasing splitting between the conduction bands, when the shear strain rises (as can be seen in Fig. 3.2). This causes a change in the shape of the conduction bands and the assumption that the minima lie fixed at does not hold anymore. Therefore, a model which is able to cover the effects of shear strain on the effective masses has to take the movement of the conduction band as a function of strain into account. In the following a model will be derived that takes this movement of Starting with (3.41) and setting relation into account.

the minimum can be found from the dispersion

(3.44)

The constants and are replaced with the relations (3.43) and (3.36), and describes the position of the conduction band minimum measured from the zone boundary Setting the first derivative of (3.44) to zero, relation between and shear strain. , and solving for

results in the desired

(3.45)

Here potential

is introduced and represents the ratio between the shear deformation and the band separation between the two lowest conduction bands at zero shear

strain (Fig. 3.3). (3.45) shows that for strain smaller than towards the point. At

, the minimum position shifts point ( ).

, the minimum is located at the does not shift

Increasing shear strain above

anymore. The change of shape of

the two lowest conduction bands and and accordingly the position change of the minimum with increasing shear strain can be seen in Fig. 3.2. The strain dependent longitudinal mass can be calculated from (3.44) with

(3.46)

After some algebraic manipulations the strain dependent mass

can be expressed as

(3.47)

Accordingly to (3.45) the dependence of the longitudinal masses is different for a strain level above or below . For the derivation of the transversal masses we rotate the principal coordinate system by around the z-axis with the following transformation: (3.48)

The energy dispersion in the rotated coordinate system is (3.49)

The effective mass in the

and

directions is defined by (3.50)

and (3.51)

Applying (3.50) and (3.51) to (3.49) gives for the

direction (3.52)

and

(3.53)

for the

direction with the parameter

and

is defined by (3.54)

As can be seen along the , while for the

direction the effective mass is reduced (mobility is enhanced) for direction the effective mass is increased (the mobility is reduced) for the effective mass is a

increasing shear strain ( ). For shear strain above constant which depends on the sign of the strain. The analytical valley shift induced by shear strain Substituting the expression for

(given in (3.22)) can now be calculated.

from (3.45) into equation (3.44) delivers the equation for and the valley pairs or due

shear strain.The shift between the valley pair along to can be obtained in the form of

(3.55)