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Band offsets of semiconductor heterostructures: A hybrid density functional study Amita Wadehra , Jeremy W.

Band offsets of semiconductor heterostructures: A hybrid density functional study

Citation: Appl. Phys. Lett. 97, 092119 (2010); doi: 10.1063/1.3487776

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APPLIED PHYSICS LETTERS 97, 092119 2010

Amita Wadehra, a Jeremy W. Nicklas, and John W. Wilkins

Department of Physics, The Ohio State University, Columbus, Ohio 43210, USA

Received 15 July 2010; accepted 17 August 2010; published online 3 September 2010

We demonstrate the accuracy of the Heyd–Scuseria–Ernzerhof HSE06 hybrid functional for computing the band offsets of semiconductor alloy heterostructures. The highlight of this study is the computation of conduction band offsets with a reliability that has eluded standard density functional theory. A special quasirandom structure models an infinite random pseudobinary alloy for constructing heterostructures along the 001 growth direction. Our results for a variety of heterostructures establish HSE06’s relevance to band engineering of high-performance electrical and optoelectronic devices. © 2010 American Institute of Physics. doi:10.1063/1.3487776

Heterostructures are ubiquitous in semiconductor tech- nology. For instance, AlInAs/GaInAs is used for quantum

cascade lasers QCLs , 1 infrared photodetectors, and high

electron mobility transistors HEMTs ;

GaInP/AlGaAs for

HEMTs, heterojunction bipolar transistors HBTs , and

phototransistors;

AlInAs/InP for HEMTs; 4 GaInP/GaAs

for HBTs;

photodiodes; 6 and AlInP/GaInP and disordered/ordered GaInP for solar cells. 7 Among the most important properties that determine the feasibility and performance of heterostruc- ture devices are the band offsets. These are the discontinui- ties between the valence band maxima VBM or conduction band minima of each semiconductor at their common inter- face, and act as barriers to electrical transport across the interface. Band engineering of devices with desired proper- ties, particularly QCLs and quantum dot-based devices, criti- cally require a precise knowledge of band offsets. However, reliable measurements and predictions of band offsets con- tinue to be challenging despite extensive theoretical and ex- perimental efforts. Density functional theory DFT is an efficient method for calculating electronic structure. The accuracy of DFT cal- culations is controlled by the exchange-correlation XC functional. Local and semilocal functionals such as local density approximation and Perdew–Burke–Ernzerhof PBE Ref. 11 underestimate band gaps, and in extreme cases pre- dict small gap semiconductors as metals. Hybrid XC func- tionals, that include a fraction of Hartree–Fock HF ex- change, provide a promising alternative. In this letter, we demonstrate the success of a hybrid functional Heyd– Scuseria–Ernzerhof HSE06 Ref. 12 in computing band offsets of several technologically important heterostructures. HSE06 includes a fraction, , of screened, short-range HF exchange to improve the derivative discontinuity of the Kohn–Sham potential for integer electron numbers default HSE06 uses =0.25 . This functional was recently used to predict the band alignments throughout the composition range of InGaN. 13 Figure 1 highlights the success of HSE06 in computing valence and conduction band offsets of the classic Al 0.5 Ga 0.5 As / GaAs heterostructure in close agreement with

2

3

5

GaInAs/InP for single-photon avalanche

810

a Author to whom correspondence should be addressed. Electronic mail:

amita@mps.ohio-state.edu.

experiment. HSE06 also shows significant improvement over PBE for computing accurate lattice constants, band gaps, and cation outermost d -orbital binding energies for the bulk

III–V compound semiconductors. 14 These results signal ad- vantages of HSE06 over traditional functionals for comput- ing electronic properties. Since the percentage of HF exchange in a hybrid func- tional is not a universal constant and the optimal value may be system-dependent, it is worthwhile to study the variation in band gaps as a function of in HSE06. Figure 2 demon- strates close agreement between the computed and experi- mental direct band gaps for III–V phosphides and arsenides using the default HSE06 functional. Since =0.30 describes the band gaps of both AlAs and GaAs so well, a reasonable choice for in the AlGaAs alloy would be 0.30, which we refer to as mod-HSE06. For all other systems we use the default =0.25 as no other value will work for both compo- nents of the alloy. We employ the average electrostatic potential technique 21 to compute the band offsets of the heterostruc- tures S1/S2, where S1 and S2 are the semiconductors con- structing a heterostructure. The bulk valence band edges are aligned through a reference potential calculated across the interface of the heterostructure. The difference in VBM of S2 and S1 is E VBM . The discontinuity in this reference poten- tial across the heterostructure interface is defined as V step . The valence band offset, E v , is calculated as

mod−HSE06 Experiment 0.42 0.31 2.19 1.52 2.10 1.52 (ind) (ind) 0.26 0.27 AlGaAs GaAs AlGaAs
mod−HSE06
Experiment
0.42
0.31
2.19
1.52
2.10
1.52
(ind)
(ind)
0.26
0.27
AlGaAs
GaAs
AlGaAs
GaAs
PBE 1.52 1.12 (ind) 0.18 0.21 AlGaAs GaAs
PBE
1.52 1.12
(ind)
0.18
0.21
AlGaAs
GaAs

FIG. 1. Band alignments for Al 0.5 Ga 0.5 As / GaAs heterostructure computed with mod-HSE06 =0.30, see text and PBE, in comparison with experi- ment see Ref. 9 The direct and indirect band gaps are shown for GaAs and Al 0.5 Ga 0.5 As, respectively. The hybrid functional shows significant improve- ment over PBE for bulk band gaps and both valence and conduction band offsets of the heterostructure.

0003-6951/2010/97 9 /092119/3/$30.00

97 , 092119-1

© 2010 American Institute of Physics

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Bandgap (eV)

092119-2

Wadehra, Nicklas, and Wilkins

4 (a) AlAs 3 AlAs(i) 2 GaAs 1 InAs 0 0 0.1 0.2 0.3 0.4
4
(a)
AlAs
3
AlAs(i)
2
GaAs
1
InAs
0
0
0.1
0.2
0.3
0.4
PBE
α HSE06
Bandgap (eV)
5 (b) AlP 4 3 GaP AlP(i) GaP(i) 2 InP 1 0 0 0.1 0.2
5
(b)
AlP
4
3
GaP
AlP(i)
GaP(i)
2
InP
1
0
0 0.1
0.2
0.3
0.4
PBE
α HSE06

FIG. 2. Color online Calculated direct band gaps open symbols vs frac- tion of HF mixing in HSE06 functional for III–V a arsenides and b phosphides. The vertical line passes through =0.25, the default fraction for HSE06. PBE results are shown at =0. Filled partially filled red symbols indicate direct indirect experimental band gaps. The experimental band gaps do not vary with but are positioned according to the needed in HSE06 to reproduce those values. Default HSE06 gives band gaps close to experimental values for InAs, GaP, and InP. An optimal value of =0.3 is required for both AlAs and GaAs.

1

The conduction band offset is determined from E v and the difference in bulk band gaps, E g , as

2

Table I shows the success of HSE06 over PBE in computing conduction and valence band offsets of 11 important semi- conductor heterostructures in excellent agreement with ex- periments. All the pseudobinary alloys in this study are of the form A 0.5 B 0.5 C. The error in E c mainly stems from the error in band gaps see Eq. 2 , the reason behind PBE’s failure. HSE06 predicts the accurate nature and magnitude of band gaps and hence band offsets. Sampling Table I, we start with AlSb/GaSb. PBE underestimates the band gaps of both constituents, 14 predicts GaSb metallic, and produces a large E c . HSE06 corrects the band gaps as well as offsets. A major success of HSE06 is evident for the more complex heterostructures such as AlInP/GaInP; HSE06 predicts AlInP as indirect band gap material, 14 in agreement with experi- ment, and computes accurate offsets. PBE predicts AlInP as a direct gap semiconductor and gives incorrect E c . Although both HSE06 and PBE give similar band offsets for AlInAs/ GaInAs, the latter is misleading since PBE makes GaInAs a metal; 14 likewise for InP/GaInAs. The predictive power of HSE06 for optoelectronic materials, demonstrated here for

E v

S2-S1 = E VBM

S2-S1 + V step

S2-S1 .

E c

S2-S1 = E g S2-S1 + E v S2-S1 .

Appl. Phys. Lett. 97 , 092119 2010

TABLE I. Comparison of HSE06 and PBE calculated valence band offsets E v eV and conduction band offsets E c eV of III–V binary and pseudo- binary alloy heterostructures with experiment values. All the pseudobinary alloys in the present study are of the form A 0.5 B 0.5 C. The band offsets computed with HSE06 show much better agreement with experimental val- ues than PBE. Asterisks indicate that mod-HSE06 =0.30 is used instead of the default HSE06 functional =0.25 . A positive value of E v E c for a heterostructure S1/S2 implies that the valence conduction band edge of semiconductor S2 lies higher than that of the semiconductor S1. The valence and conduction band offsets have opposite signs for type-I straddling het- erostructures and the same sign for type-II staggered heterostructures.

Heterostructure

E v eV

 

E c eV

 

S1/S2

HSE06

PBE

Expt.

HSE06

PBE

Expt.

 

AlAs/GaAs AlP b /GaP b AlSb b /GaSb AlGaAs b /GaAs GaInP/GaAs InP/GaInAs InP/AlInAs AlInP b /GaInP AlInAs/GaInAs GaInP/AlGaAs d/o GaInP k

0.52

0.45

0.53

a

−1.02

1.08

1.05

a

0.54

0.49

0.55

c

0.58

0.57

0.38

c

0.38

0.35

0.38

a

0.67

 

1.21

0.51

d

0.26

0.21

0.27

a

−0.42

1.12

0.31

a

0.32

0.26

0.31

a

0.24

0.34

0.18

a

0.36

0.27

0.34

e

0.38

0.42

0.27

e

0.16

0.14

0.17

f

0.22

0.17

0.25

f

0.22

0.19

0.24

g

0.23

0.74

0.26

g

0.23

0.18

0.22

h

0.57

0.54

0.51

h

0.11

0.08

0.09

i

0.25

0.19

0.28

j

0.01

0.02

0.24

 

0.18

0.15

l

a From Ref. 9 and references therein.

b Indirect band gaps of these semiconductors are used to get E c . c From Ref. 15. d No expt. data; E c calculated from expt. E v and E g . e From Ref. 16. f From Ref. 17. g From Ref. 18. h From Ref. 10 and references therein.

i No expt. data; E v calculated from expt. E c and E g . j From Ref. 19. k d=disordered and o=ordered with Cu–Pt L1 1 ordering. l From Ref. 20.

heterostructure band offsets, holds also for the alloy concen- tration of direct-indirect band gap crossovers for pseudobin- ary alloys. 22 We use the plane wave projector augmented-wave method 23 with PBE and HSE06 functionals in the VASP code. 2426 We use a plane wave energy cut-off of 500 eV and treat the outermost d electrons of cations as valence. The Brillouin zone integration for the III–V binaries and their heterostructures is performed on a -centered 8 8 8 and 8 8 1 k-point meshes, respectively. For the pseudobinary alloys and their heterostructures, 4 8 4 and 4 8 2 -centered k-point meshes are used, respectively. We relax

the interfacial atoms only when the anions are different in the two semiconductors making a heterostructure. The computation of an infinite random alloy requires a large supercell and is arduous, particularly with the hybrid functional. In order to simulate such an alloy using a finite supercell with reasonable computational effort, we employ a

generated using the

special quasirandom structure SQS ,

alloy theoretic automated toolkit. 28 Only the 16 cations on a fcc sublattice were distributed according to the SQS con- struction, whereas the 16 anions are located on the separate sublattice that makes up the 32 atom zinc blende supercell. We search all possible 16-atom fcc supercells with two lattice-vectors orthogonal to 001 for easy construction of a heterostructure in a 001 growth direction. The degree to

14

27

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092119-3

Wadehra, Nicklas, and Wilkins

which this SQS matches an infinite perfect random alloy is based on the behavior of the first few radial pair-correlation functions. The SQS employed in this work has radial corre- lation functions that match the perfect random alloy up to the fourth nearest neighbor pairs. The heterostructures of alloys binary III–V’s are modeled as 4+4-layer thick supercells, 64 atoms 16 atoms with a 001 interface. For either func- tional, the substrate lattice constant and average of the lattice constants of the nearly lattice-matched bulk materials, com- puted with that particular functional, are used for the pseudo- binary and binary alloy heterostructures, respectively. To conclude, DFT originally created for ground state properties has recently been extended to conduction states, especially important for optoelectronic property predictions, through the use of hybrid exchange correlation functionals. Here HSE06 has been extensively exploited for semiconduc- tor alloy heterostructures mimicked by appropriately con- structed SQSs. For a broad selection of technologically im- portant heterostructures, HSE06 succeeds in predicting i the magnitude of optically direct band gap and ii band off- sets, especially the conduction band offset, so important to optoelectronic properties. These achievements greatly extend the utility of DFT for technological relevance. More compu- tational resources may conquer strained and lattice- mismatched interfaces increasingly being used for advanced devices.

This work was supported by DOE-BES-DMS Grant No. DE-FG02-99ER45795 . We used computational resources of the NERSC, supported by the U.S. DOE Grant No. DE- AC02-05CH11231 , and the OSC. We thank Steven A. Rin- gel, Siddharth Rajan, and Richard G. Hennig for useful sug- gestions, and Georg Kresse for the beta version, VASP5.1.

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