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J. F. HUNTERal.

: Band Structure of GaAsl-,P, et


phys. stat. sol. (b) 46, 679 (1971) Subject classification: 13.1 ; 22.2.4

and Inl-,Ga,P

679

Department o Applied Mathematics and Mathematical Physics, f University College, Cardiff

Band Structures of GaAsl-Jz and Inl-,GaJ


BY J. 3. HUNTER^), G . BALL, D. J. MORGAN and
The band structures of GaAsl -,P2 and In1-.Ga,P are calculated in the virtual crystal approximation using the empirical pseudopotential method. The effects of disorder and of spin-orbit coupling are neglected. The lattice parameter is assumed to vary linearly with the mole fraction of one compound x and the six non-zero pseudopotential form factors V,(x) ( j= 1 to 6) are assumed to vary as V,(x) = V,(O) ( V , ( l ) - V,(O)) x x ((1 - a ) x a x2), where a is a constant independent of j. It is found that the calculated bowing parameter of the lowest direct band gap E, (l?y5 - l varies linearly ? : ) with a, and this enables a value for a to be found. Results are presented for the bowing parameters of the indirect gaps, and for the values of x at which two of the gaps become equal. Graphs of the variation of effective masses with x are also given. The results indicate that, contrary to what has been reported in the literature, the empirical pseudopotential method is applicable to alloy systems.

Die Bandstrukturen von GaAsl -,P2 und In1 -,Ga,P werden in der virtuellen Kristallniiherung mit der empirischen Pseudopotentialmethode berechnet. Fehlordnungseffekte und Spin-Bahnkopplung werden vernachlitssigt. Es wird angenommen, da.B der Gitterparameter linear mit dem Molanteil x einer Verbindung variiert, und daD die sechs von null verschiedenen Pseudopotential-Formfaktoren V , ( z )( j = 1 bis 6) wie V,?) = VAO) (V,(l) - V j ( 0 ) )((1 - a ) x a x2)variieren, wobei a eine v o n j unabhangige Konstante ist. Es wird gefunden, d a B der berechnete Krummungsparameter der niedrigsten direkten Energielucke E, ( Iy6- IF) linear mit a variiert und somit einen Wert fur a zu bestimmen gestattet. Ergebnisse fur die Krummungsparameter der indirekten Bandlucken und fur den Wert von x, bei dem zwei der Bandlucken gleich werden, werden angegeben. Diagramme der h d e r u n g der effektiven Massen mit x werden ebenfalls mitgeteilt. Die Ergebnisse zeigen, daB im Gegensatz zu den Veroffentlichungen in der Literatur die empirische Pseudopotentialmethode fiir Legierungssysteme anwendbar ist.

1. Introduction It has been shown experimentallythat the lowest direct band gap Eo ( - I?;) in many alloys of 111-V compounds has an approximately quadratic dependence on the mole fraction of one compound x [l to 31,
where
Eo(4 = EO(0)

+ [Eo(1)- EO(0)l 1 - B) x + B x21

(1.1)

(1.2) B = co [Eo(1)- Eo(0)l-l and c0 is the bowing parameter, i.e. four times the deviation of E,, from linearity at the equimolar concentration x = 0.5. c0 has been calculated for many alloys by Van Vechten and Bergstresser [4] using the dielectric method of band structure calculation [ 5 , 6 ] . These authors
l) On leave of absence from: Mathematics Department, University College of Townsville, Queensland, Australia.

680

J.F. HUNTER, BALL, D. J. MORGAN G. and

also carried out a n empirical pseudopotential calculation assuming that the form factors varied linearly with x. The value of c, obtained by this latter method was found t o be extremely sensitive t o the values of the form factors used for the pure compounds, and the method was considered t o be unsuitable for application t o alloy systems. Using a dielectric screening point of view, these authors then illustrated the fact that the pseudopotential form factor values should not vary strictly linearly with composition. The possible application of the empirical pseudopotential method t o alloy systems is here investigated further by assuming that the form factors have a quadratic dependence on x. Ideally, a different quadratic dependence for each of the six non-zero form factors is needed, but this would lead to a n unmanageable set of six unknown parameters. The form factors V,(x)(j = 1 t o 6) are therefore assumed t o vary as

(1.3) where a is a constant independent of i and whose value is t o be obtained from the known value of c,. This precludes the possibility of using the method t o predict values of c, unless, of course, an empirical relationship between a and the end-point form factors (or energy gaps) can be found.
9

V,(4 = V,(O)

+ [V,(l) - V,(O)l [ ( I - a) x + a x21

2. Method of Calculation
The empirical pseudopotential method is here applied to the alloy systems GaAsl-,P, and Inl-,Ga,P. The pseudopotential form factors for the pure compounds are given in Table 1 where, in the notation of Cohen and Bergstresser [7],

V3S = V t - Vf , V3A V8S = , VllS

= =

v;

Vz + Vf , Vyl- Vfl ,

V4A = V$ , V l l A = VFl

+ Vf1,
VllA
0.090
0.078 0.057

Table 1 Pseudopotential form factor (in Ryd)

I
GaAs Gap InP

V3S
-0.298 -.3 031 -0.310

V3A
-0.186 -0.166 -0.188

V4A 0.041 001 .6 0.062

V8S 0.006 0.024 0.016

VllS
0.064 0.068 0.046

The values given in Table 1 were obtained, in a n attempt t o get better agreement with experiment, from those of [7] using a procedure analogous t o that described by Walter and Cohen [8]. It should be noted that in the empirical pseudopotential method the values obtained for the form factors (by comparing the results of the calculation with a number ofexperimenta.1energy gaps) depend on the method used t o form, and on the size of the Hamiltonian matrices. For a n a.lloy the lattice parameter was assumed t o vary linearly with x

(2.2) and the six non-zero form factors were assumed t o have the quadratic dependence on x given in equation (1.3). The Hamiltonian matrices (one for each of the different symmetry types a t I?) were then set up as functions of a and x. Several values of a were chosen and the direct gap bowing parameter c,(a) cal-

44 = 4 0 ) + [41) - 4 0 ) l x ,

Band Structure of GaAsl - P and Inl -,Ga,P ,Z

681

culated in each case. It was found that co(a) had a linear dependence on a,
c~(u.) = b

+d a

(2.3)

where the coefficients b and d obviously depend on the values of the form factors used for the pure compounds. Because of the neglect of disorder, the value of a used in the calculations was that which resulted in a value for co which was approximately equal to the intririsic bowing parameter ci calculated for the alloy by Van Vechten and Bergstresser [4]. Using this value of a, the Hamiltonian matrices for the points X and L in the first Brillouin zone (again one for each of the different symmetry types a t X and a t L) were then set up as functions of x . The bowing parameters c, and c, for the El ( - X;) E, ( -L;) and indirect gaps, the effective masses mrI(x), m f : ( x ) , mL;(x),m F ( x ) and the coII efficients A ( x ) ,B ( z ) ,Cz(x)for the';?I level [9] were then calculated. No attempt was made to calculate the effective masses a t the minimum in the conduction band which occurs a little way inside the first Brillouin zone from the symmetry point X.

3. Results and Discussion


The values of a, co, cl, and c, obtained by the method described above are given in Table 2. Also shown in this table are the values of ci obtained in [4].
Table 2 Calculated bowing parameters (in eV)

GaAsl - P ,z In1 -,Ga,P

1 :::: 1 1 1 1
0.1525 0.3103 0.22 0.39 0.13 0.16

ci

a -

co

ci

cz

0.18 0.23

The results show that in order of increasing bowing the gaps are El (; - X;), I' ? E, ( I - L;), and Eo (rL- I?;). ? ; ' Each of the above bowing parameters was then put into an equation of the form E,(x) = E,(O) [E,(1) - E,(O)I x C? x ( x - 1 ) (3.1)

and the values of x and E,(x) found for the compositions at which two of t,he gaps became equal. The results of such calculations are given in Table 3 and 4. In these tables xij is the value of x a t which Et = E,. Also given in
Table 3 GaAsl-,P,: Critical compositions and energies (ineV) at which two of the gaps become equal. The values in brackets are from [a]
x = l 1.5 1.9 1.7 1.91 2.01 2.01 2.06 2.06 2.12 (2.08) (2.08) 2.35 2.15 2.35 2.8 2.3 2.7

682

J. F. HUNTER, G. BALL, and D. J. MORGAN

Eo(x)
E,(z) E,(z)

1.4 2.3 2.0

1.93 2.26 2.26

2.27 (2.25) 2.27 (2.25) 2.43

2.59 2.28 2.59

2.8 2.3 2.7

these tables are the values of xO1 and Eo(xoJ obtained in [4]. It can be seen that the agreement between the two sets of results is very good. The energy gaps for the pure compounds were taken from [7]. The experimental values for xol are 0.60 for Inl-,Ga,P [lo] and 0.45 to 0.50 for GaAsl-,P, [ll, 121. The variation of the virtual crystal conduction band effective masses with composition is shown in Fig. 1, and that of the A, B, C2 coefficients for the I'y5 level in Fig. 2. If the variation of one of these quantities with x is approximated by an expression of the form

f ( 4 = f(0)

+ "1

- f(0)l 2

+y

x (z- 1)

(34

the dimensionless bowing parameter y then has the value given in Table 5. Table 5 Values of the dimensionless bowing parameter y (equation (3.2))

I
G a h l -sPl, Inl-,Ga,P

mr;
0.034 0.066

m: :

0.018 0.032

1 ;8: 1

mi'

my

0.024 0.080

A
0.174 0.116

B
0.382 0.298

CB
0.246 0.102

Obviously the value of ci obtained by the method described above depends on the values of the form factors used for the pure compounds. It may happen, therefore, that any slight changes in the values of the end-point form factors will be compensated by an appropriate change in the value of a, and hence that different sets of end-point form factors will lead to essentially the same results for the alloy. This aspect, however, has not been investigated by the present authors.
4. Conclusions

Without the introduction of another parameter into the theory, the empirical pseudopotential method is unsuited for calculating (in the virtual crystal approximation and with the assumption of a linear variation of form factors with composition) the bowing parameters of band gaps in semiconductor alloys because of the sensitivity of the bowing to the values of the form factors used for the pure compounds. The results presented here, however, indicate that if the intrinsic bowing parameter of the direct band gap is known and another parameter ( u ) is introduced into the theory to enable this intrinsic bowing to be reproduced, then the empirical pseudopotential method can be used to cal-

Band Structure of GaAsl-$,


Fig. 1. Virtual crystal conduction band effective masses vs. z
(a) mrf(z)/mr?(l) ,

and Inl_,Ga,P

683

(b) mx&/mX:(l),

(c) m;~(z)/m;I(l).
(d) mL;(z)/mL:(l)

X-

Gap

-X

lnP

culate the bowing parameters of other gaps, etc. The pseudopotential wavefunctions could then possibly be used in a calculation of the effects of disorder. Obviously, further investigation of the method is needed. In particular, an investigation is called for of the changes in the value of a produced by different sets of end-point form factors, and of whether or not one would obtain essentially the same results for an alloy by using different sets of (end-point form factors +a).

References
[l] A. G. THOMPSON J. C. WOOLLEY, and Canad. J. Phys. 46,255 (1967). [2] M.CARDONA,Phys. Rev. 129, 69 (1963). R. and Phys. Rev. 108,587 (1957). [3] S.LARACH, E. SCFIRADER, C. F. STOCKER, and Phys. [4] J. A. VANVECHTEN T. K. BERQSTRESSER, Rev. B1,3351 (1970). and Phys. Rev. Letters 22, 705 (1969). [5] J. C. PHILLIPS J. A. VANVECHTEN, [6] J. A. VANVECHTEN, Phys. Rev. 187, 1007 (1969). [7] M.L.COHEN and T. I.BERGSTREWEB, ( Phys. Rev. 141,789 (1966). and [8] J. P. WALTER M. L. COHEN, Phys. Rev. 183, 763 (1969). [9] J. CALLAWAY,Energy Band Theory, Academic Press, 1964 (p. 161). [lo] A. M.WHITE, E. W. WILLIAMS,P. PORTEOUS, C. HILSUM,J. Phys. D, Appl. and Phys. 3, 1322 (1970). [ll] M.G.CRAFORD, G. E. STILLMAN, A. R ~ S S Iand N. HOLONYAE, Phys. Rev. J. , JR., 188, 867 (1968). [12] J. W. ALLEN and J. W. HODBY, Proc. Phys. SOC. (London) 82, 315 (1963).
(Received March 19, 1971)
44.