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Heterojunction band offsets and effective masses in III-V quaternary alloys

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Semicond. Sci. Technol. 6 (1991) 2731. Printed in the UK

Heterojunction band offsets and effective masses in Ill-V quaternary alloys

M P C M Krijn Philips Research Laboratories, PO Box 80000, 5600 J A Eindhoven. T h e Netherlands
Received 23 April 1990, in final form 30 August 1990, accepted for publication 17 SeDtember 1990
Abstract. Estimates o valence-band and conduction-band offsets for latticef

matched and pseudomorphic strained heterostructures o six technologically f important Ill-V quaternary alloys are presented. Valence-band offsets are obtained via interpolation of the theory-based results of Van d e Walle's 'model-solid' approach for the binary constituents. Estimates for band gap differences are obtained via interpolation of the experimental band gap energies of the ternary constituents. Adding t h e valence-band offset and band gap difference gives an estimate of the conduction-band offset. Band-edge effective masses at r are determined from a linear interpolation of t h e effective masses of t h e binary constituents, obtained from self-consistent ab initio band structure calculations. Results are shown to agree well with the outcome of experiments.

1 . Introduction

The design and modelling of optoelectronic devices requires a knowledge of various material parameters. What is essential is a knowledge of the heterojunction band offset (also known as band discontinuity, band alignment or band line-up), i.e. the relative position of the band edges of the semiconductors constituting the heterojunction. This relative position determines the confinement of the electrons and holes and depends on the composition of the constituents and the amount of strain due to lattice mismatch. Equally important are the band gap energy and the conduction-band and valence-band effective masses. The hand gap energy determines the operating wavelength whereas the effective masses determine the electron and hole mobility [IJ. The commercially attractive 0.5-4 pm wavelength range may be covered by heterojunction devices constructed from 111-V quaternary alloys. Notably, AIGalnP, AIGaInAs, AIGaAsSh, GaInPAs, GaInAsSb and InPAsSh. These quaternary alloys include most ternary alloys. A lack of knowledge of the dependence of the various material parameters on alloy composition has hampered a systematic approach to the design of tailor-made optoelectronic devices. The determination of band offsets in particular poses a problem. Recently it has been recognized that, for the class o f 111-V semiconductor heterojunctions, the band offset is largely determined by the hulk properties of the semiconductors constituting the heterojunction; band offsets are found to be orientation independent and transitiue [2-41. However, it is in general not possible to measure or 0268-1242/91/010027+05$03.50@ 1991 IOP Publishing
Ltd

calculate hulk band-edge energy levels on an absolute scale. Van de Walle [SI has circumvented this problem by relating the energy levels in hulk semiconductors which he obtained from self-consistent ab initio band structure calculations, to a common reference level. This reference level was chosen to he the average electrostatic potential in a semi-infinite 'model-solid'. The modelsolid was built up from a superposition of neutral atoms which were required to mimic the bulk electron density. This approach also makes it possible to calculate the shift of energy levels due to strain. The model-solid results for the binary constituents and estimates for some of the ternary constituents of the aforementioned quaternary alloys were shown to agree well with the outcome of experiments [2, 51. Band structure calculations of material properties require the presence of ordering, which is absent from or unknown in most alloys (some alloys exhibit ordering in the (1 11) directions, however [6-81). Consequently, there is as yet no reliable method available to calculate the dependence of the various material parameters on alloy composition. The best one can d o is to combine the available theoretical and experimental data on the binary and ternary constituents of the quaternary alloys and employ an interpolation scheme to obtain an estimate for the various material parameters. The aim of this paper is to present estimates of the relative position of conduction-hand and valence-band edges and effective masses as a function of alloy composition and lattice mismatch. Results are tabulated so that a systematic search for device characteristics and trends is straightforward,
27

M P C M Krijn

2. Theory

k 1/2), and spin-orbit split-off (Eso;J bands:

1/2, m, = f 1/2)

We closely follow Van de Walle [SI in describing the dependence on strain of the valence- and conductionband edges in 111-V semiconductors. Pseudomorphic (or commensurate) growth of strained layers on a substrate subjects these layers to a biaxial strain ell parallel to the plane of the interface and a uniaxial strain e , perpendicular to it:

Wava,(2q + ~d =
and similarly for the conduction band energy
AEtY= a,(2q

(44

(46) where a, and a, are the hydrostatic deformation potentials for the valence band and conduction band, respectively. The shear contribution couples to the spin-orbit interaction and leads to an additional splitting of the valence-hand energies. In the case of growth on a (001) or (111) substrate, the energy shifts relative to E,, = E,,,, + A0/3 (Ao is the spin-orbit splitting in the absence of strain) are given by [S, 91
=

+ cl),

Here, a, denotes the lattice constant of the substrate and a the equilibrium lattice constant of the layer material. D depends on the elastic constants c of the layer material and on the interface orientation:

- +SESh - +Ao + +SEsh

++[Ai

(54

AE;; =

+ A0SE'" + ~(6EPh)2]1'Z

(56)

AE;: = - $Ao + +&ESh (Sc) The strain-dependent shift SESh depends on the interface orientation:
sh)2]1'2.

- +[Ai

+ AOSEsh+ q(6E
- ell)
j$dSd(&i -Ell).

!he eqni!ibinm !actice ccnstzfits and elastic constants of the relevant 111-V binary semiconductors. The effect of strain on energy levels can be decomposed into hydrostatic and shear contributions. In the following we separately discuss the effect of both contributions to the conduction band and valence band for zincblende-type semiconductors at The hydrostatic strain component leads to a shift of the average valence-band energy E,,,, = (Ehh+ E,, EJ3, i.e. of the average of the energies of the heavy-hole (E,,; J = 3/2, m, = +3/2), light-hole (E,,; J = 3/2, m, =
Spp gf

ta.h!e !for a !is!

~ ~ 0 O l . = s h

(64 (6b)

,jElll.sh

=Z

r.

The quantities b and d are the tetragonal and rhombohedral shear deformation potentials, respectively. In the absence of strain, equation (5) leads to the correct spin-orbit splitting Ao. Conduction bands at r are not affected by the shear contribution to the strain. Once E,,,, is known on an absolute scale (only physically meaningful relative to E", in related semiconductors), the valence-band and conduction-band edge

Table 1. Material parameters for various zincbiende-type semiconductors. Lattice constant a (in A) at room temperature and hydrostatic deformation and elastic constants cI,, Cl2and c (in IO" dyn cm-'; [15]). Valence-band average , potentials a, and a,(T) as calculated within Van de Walle's model-solid approach (in eV; [5]). Spin-orbit splittings A o , band gaps ,(I-). EJX), EJL) (at room temperature) and shear deformation potentials b a n d d (in eV; [151 and (221, except where indicated).

AIP AlAs AiSb

5.451 5.660 6.136 5.451 5.653 6.096 5.869 6.058 6.479

1.32 1.25

0.88
1.41 1.18

0.63 0.53 0.43 0.62 0.54 0.40 0.58 0.45 0.36

0.62 0.54 0.41 0.70 0.59 0.43 0.46 0.40 0.30

-8.09 -7.49 -6.66

-7.40 -6.92 -6.25 -7.04 -6.67 -6.09

0.07' 0.28 0.65

3.58 2.95 2.22 2.74 1.42 0.72 1.35 0.36 0.17

2.45 2.16' 1.61' 2.26 1.91' 1.05' 2.21" 1.37' 1.63''

3.11. 2.80' 2.21' 2.63 1.73b 0.76' 2.05' 1.07* 0.93"

3.15 2.47 1.38 1.70 1.16 0.79 1.27 1.00 0.36

-5.54 -5.64 -6.97

-7.14 -7.17 -6.85 -5.04 -5.08 -6.17

-1.6' -1.5' -1.4 -1.5 -1.7 -2.0 -1.6 -1.8 -2.1

-4.3 -4.6 -4.6 -4.8 -4.2 -3.6 -5.0

GaP GaAs GaSb

inP lnAs lnSb
a

0.08
0.34 0.82 0.11 0.38

0.88
1.02 0.83 0.66

08 .1

Present work 1161,

'1171. = 1211.

*IlO].
28

Heterojunction band offsetsand eflective masses energies E , and E,, respectively, are obtained on an absolute scale from Band gap (at r) and spin-orbit splitting bowing parameters.
Table 2.

E , = E,,,,
E , = E,,,,

A, + - + AE;:*" + max(AEL!, 3 A, + - + E, + AE4Y 3

AE;:)

(7a)
AIAs.Sb. " AI,Ga, _,P
I - ^
I

C(E,)

C(A,)
0.15 0.0 0.0 0.30 0.0
0.15

Reference
1181

(7b)

AI,Ga,-,As AI,Ga,_,Sb
A l h - .P Al,ln, _,AS

0.84 0.0 0.37 0.47

izoj

where E",*",A,, and E , (band gap energy) refer to unstrained bulk properties. The strain contribution is incorporated in AE:Yav, AE;;, AE;,"and AEF. Values for E,,,, as calculated b Van de Walk y together with values for A,, E,, a,, a,, b and d are listed in table 1. These data enable one to calculate the band offset at the interface by directly comparing the values of E, and E, of the semiconductors constituting the heterojunction. Equations (4), ( 5 ) and (6) were arrived at by treating the effect of strain as a small perturbation, and are therefore only valid in the case of small lattice mismatch. The mismatch attainable in pseudomorphic heterojunctions composed of 111-V alloys is expected to fall within this range of validity.

0.0
0.70

[17, 271 [21] 122, 181

[22, 181

GaP,As,-. GaAs,Sb, Ga,ln, -,P G a h , - .As Ga,ln,-,Sb

~

0.21 1.2 0.79 0.38

0.42

0.0 0.60

P I
[22, 181 [22, 281

0.0 0.15 0.0

0.10

123, 2 1 9 i2 21
124, 1 1 8

InP,As,

InP.Sb. ~" InAs,Sb,_,

~,

0.28 1.3 0.58

0.75
1.2

125,1 1 8 izz,zg]

3. Interpolation scheme

non-lattice matched binaries, one material should be regarded as being expanded, whereas the other is compressed. For E",+, this leads to a bowing parameter that depends on the hydrostatic deformation potentials of the binary constituents [ll]

Material parameters of quaternary alloys ( Q ) with compositions of the form AB,C,D,_,-, or A,B,-,C,D,_, can be estimated by interpolating the parameters of the binary ( E ) or ternary ( T ) alloys, depending on which information is available. Estimates of Q are readily obtained from a linear interpolation of the E's. This is known to be a valid procedure for the variation of the lattice constant with alloy composition (Vegard's law [l]). Parameters such as e.g. E, and A, in ternary alloys of the form AB,C,_,, can be approximated well by the quadratic expression TABC(X) XBAn =

where Aa, = a,(AB) - a,(AC) and Aa = a(AB) - a(AC). For convenience, results for E,,,,, A,, and E, will be presented in the form of tables of coefficients of an expansion of Q in a product polynomial in x and y

+ (1 - XPAC - 1)cAnc (8) t x(X

In the case of AB,C,D1_,_,, Q can be expressed as

Q(x, Y) = XBAB YEA,+ (1 - x - Y W A D - xYcABC f
- x(l - x - Y)cABD

- Y(I

In the case of A,B,_,C,D,_y, the coefficients C , are obtained from fitting equation (12) to equation (10) in a least-squares sense. The error introduced by this fitting procedure is estimated to be 20.025 eV for the 111-V alloys considered. Similarly, results for AE?*", AEkY, and SEsh are written as an expansion that is linear in the lattice mismatch

- Y)cACD
[IO]

(9)

Equally, in the case of A,B,-,C,D,-,

where Aa(x, y) = a, - a(x, y) is the lattice mismatch (a(x, y ) is the equilibrium lattice constant of the alloy obtained from Vegard's law, whereas a, is the lattice constant of the substrate),
4. Results and discussion

In the latter case, Q reduces to Ton the quaternary plane boundaries (x = 0, 1; y = 0, 1) and to the average of the Ts at the midpoint (x = 0.5; y = 0.5). The constant C in equation (8) is known as the bowing parameter. Experimentally determined bowing parameters for E , and A, are listed in table 2. In ternary alloys constituted from

The coefficients of an expansion of E,,,,, A. and E, (at room temperature) in a product polynomial as represented by equation (12), are listed in table 3. The effects of strain are incorporated in AEFav, AEty and 6ESh.The expansion according to equation (13) leads to the coefficients listed in table 4.
29

M P C M Krijn
spin-orbit splitting A. and band gap EJT)

Table 3. Coefficients of an expansion of the valence-band average according l o equation 112).

C?,

C,,
-0.573 -0.378 0.035 -0.006 -0.162 -0.404

C,,

C2.3
-0.453 -0.324 0.011 -0.049 -0.085 -0.294

C2,

c2 2

AI,Ga,ln, - r - v P AI,Ga,l n, - - ,As AI,Ga, - .As,Sb, Ga,ln, _,P,As, --y Ga,ln, -,As,Sb, - - y InP.As,Sb,
~

-7.040 -6.670 -6.250 -6.670 -6.090 -6.090

-0.240 -0,201 -0.570 -0.341 -0.442 -0,442

-0.120 -0.049 -0.100 -0.029 -0.138 -0.138

-0.597 -0.496 -0.421 -0,201 -0.075 -0.656

-0.188 -0.033 0.036

0.007 -0.069 0.034

-0.013 -0,002 0.002

0.110 0.380 0.823 0.381 0.814 0.810 -0.030 -0.190 -1.022 -0.357 -1.537 -1.630

A0 AI,Ga,ln, - x - y P AI,Ga,ln, _,_,As &Gal _,As,Sb, --I Ga,ln,-.P,As,-, Ga,ln, -,As,Sb, --y InP,As,Sb, _ _
E&) AI,Ga,ln, - - i _ - y P AI,Ga,ln, _,_,As AI,Ga, _.As,Sb, - - y Ga,ln, - .P,As, Ga,ln, _,As,Sb, _ y InP,As,Sb,

0.000 0.150 0.540 0.087 1.109 1.200

0.790 0.380 1.114 0.242 0.588 0.580

-0.040 -0.250 -0.441 -0.178 0.023 -1,450

0.000 0.300 1.803 0.480 2.242 1.850

0.790 0.710 3.285 1.658 2.610 1.600

-1.435 -0.343 -2.411

0.000 0.150 0.269 0.138 -0.015 0.750

-1.325 -0.389 -1.802

1.067 0.261 1.920

-~-

1.350 0.360 0.725 0.361 0.173 0.170

0.600 0.680 -0.414 0.751 -0.399 -0.390

2.230 1.890 1.071 0.676 0.167 -0.120

0.000
-3.158 -1.667 -2.053 0.700 0.428 0.384 0.385 1.300 -2.961 -1.271 -2.606 2.863 1.610 2.560

Consider a pseudomorphic strained heterostructure A/B where B is the unstrained substrate. A knowledge of the alloy composition of A and B, together with the information contained in table 3 and table 4 suffices to obtain an estimate of the conduction-band and valence-

Table 4. Coefficients of an expansion of the straininduced shift of the valence-band average AE;:.,, conduction-band AE,(r)y and C ~ E ~ (defined in equation . ~ (5)) according to equation (13).

AEFaW AI,Ga,ln P AI,Ga,ln, -,-,As AI,Ga, .As,Sb, _ Ga,ln, -.P,As, GaJn, _.As,Sb, --y InP,As,Sb, - - x - - y

1.10 0.90 0.86 0.91 0.33 0.33

0.67 0.31 0.40 0.18 0.58 0.59

2.13 1.86 0.53 0.35 0.52 0.79

0.33 0.13 1.01 0.40 -0.16 -0.02

6.81 7.51 7.65 7.52 8.73 8.74

-4.39 -4.62 -7.47 -4.61 -5.67 -5.68

-3.17 -3.02 -0.39 0.29 1.10 1.05

-1.37 -1.81 0.41 -3.17 -1.78 1.29

-0.43 -0.53 0.95 -0.27 -1.45 -0.03

Ga,l n - .P,As, Ga.ln, . - , .As.Sb. . - , InP,As,Sb, _ I _ y

30

,.

-1.11 - 1.07 -1.17 -0.72 -1.22 -1.21

-0.55 -1.98 -2.05 -1.05 -1.10 -1.92

0.03 0.09 1.14 -0.04

0.06
-0.01

band ofset: equation (7) and the information in table 3 allow one to calculate E: and E:, From Vegards law one readily obtains the lattice mismatch a t the interface. Together with the information listed in table 4, one is able to calculate E: and E:. Consequently, the conduction-band and valence-band offsets are simply AEv = E: - E t and AEc = E: - E:, respectively. As an example we consider InGaAsP lattice matched to InP. For this heterostructure we arrive at AEJAE, 0.41 throughout the entire compositional range. This agrees favourably with the experimental results AEJAE, = 0.39 (capacitance-voltage technique [lZ]). As an example of a strained heterostructure we consider In.Ga, _ . As/AI,,Ga,,,As (reliable experimental results ~ on strained quaternary alloy heterostructures are not available). We obtain values for AEJAE, varying linearly from 50.66 for x = 0 to -0.63 for x = 0.2. Debbar et al[13] obtained values varying from 20.58 for x = 0 to 20.71 for x = 0.2 (extrapolated from their deep-level transient spectroscopy results). Again there is a quantitative agreement. A linear interpolation of q r ) ,E , ( X ) and E,(L), as included in table I, is helpful in predicting whether the alloy under consideration exhibits a direct band gap or not. From equation ( 5 ) it follows that the uppermost valence-band in a layer material in biaxial compression ( E , ~< 0) is heavy-hole-like, whereas in biaxial extension > 0) it is light-hole-like. In semiconductor quantumwell lasers, the heavy-hole subband has a parallel mass generally smaller than that of the light-hole subband. Placing the active layer under biaxial compression results in the lowering of the uppermost light-hole subband with

Heterojunction band offsets and effective masses Effective masses lin fractions of the eleCtrOn mass) of spin-orbit split-off (so), light-hole (Ih). heavy-hole ( h h ; along [OOI]and [Ill]) and conduction (c)electrons at r. as calculated with the ab initio ASW band structure method.
Table 5.
SO

References

Ih

hh""

hh"'

c
0.22 0.13 0.079" 0.15 0.070
003 .3'

AIP
AlAs AlSb

0.34 0.28 0.26 0.23 0.17 0.17 0.19 0.15 0.20

0.22 0.14 0.12 0.18 0.073 0.054 0.14 0.055

0.52
0.44

0.29 0.41 0.35 0.23 0.48 0.39 0.26

1.35 1.13 0.72

10 .1

GaP
GaAs GaSb

0.87
0.57

InP
lnAs

lnSb
a

0.062

1.13 0.98 0.68

0.064' 0.031e

0.030"

Relativistic Corrections included.

respect to the uppermost heavy-hole subband. Consequently, the reduced interaction (repulsion) between the two subbands allows the latter to have a reduced parallel mass and a parabolic dispersion over a larger energy range than in the absence of strain. As a result, Auger recombination, inter-valence-band absorption, and threshold current density are reduced [30, 311. Effective masses a t r for the binaries under consideration were calculated from a n expansion of the band structure in a polynomial in the vicinity of r. The coefficient of the quadratic term renders the effective mass. T h e band structures were calculated by means of the self-consistent ab initio augmented spherical wave (ASW)method [14]. Spherical atoms with zero nuclear charge were included at the interstitial sites. Results are listed in table 5. T h e electron effective masses compare well with accurately known experimental results [lS]. Valence-band effective masses must essentially be obtained from theoretical calculations. N o t e the strong anisotropy in the heavy-hole effective mass. Estimates for quaternary alloys are readily obtained from a linear interpolation of the masses of the related binaries. The effects of strain o n effective masses are assumed to be insignificant. I n summary, this paper provides a self-contained description for a systematic comparison of heterojunction band offsets and effective masses of various 111-V quaternary alloys.

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__
L .

__

Lasers, Parr B: Materials and Operaring Chnracrerisrics (New York: Academic)

Acknowledgment

The support of Professor M F H Schuurmans is gratefully acknowledged.

[23] Marlin J-Y, Charasse M N and Sermage B 1985 Phys. Reo. B 31 8298 1241 Bodnar I V, Lukomskii A I and Smirnova G F 1976 Phys. Status Solidi a 37 K173 [25] Re-estimated from [26] with the bowing parameters of [22] and 1241 [26] Fukui T and Horikoshi Y 1981 Japan. J . Appl. Phys. 20 587 [27] Van Vechten J A, Berolo 0 and Woolley J C 1972 Phys. Reti. Lett. 29 1400 [28] Alibert C, Bordure G, Laugier A and Chevallier J 1972 Phys. Reu. B 6 I301 [29] Berolo 0, Woolley J C and Van Vechten J A 1973 Phys. Reu. B 8 3794 f301 Yahlonovitch E and Kane E 0 1986 IEEE J. Liahrwaue Techno/. 4 504 [31] Adams A R 1986 Electron. Lefr. 22 249

- -

31