Structural, elastic and thermo physical properties of group III-nitrides in zinc-blend structure

Madhu Sarwan and Sadhna Singh

High Pressure Lab, Department of Physics, Barkatullah University, Bhopal 462026, India Corresponding author E mail: drsadhna_in@rediffmail.com

The pressure induced crystal properties of group III-nitrides have been investigated by means of interaction potential model (IPM) which consists of Coulomb, three-body, and short-range overlap repulsive up to second neighbour ions, covalency effect and van der Waals interactions. These compounds exhibit first-order phase transition from their initial ZnS-type structure to NaCl-type structure at pressures 555, 21, 37 and 8.2 GPa for BN, AlN, GaN and InN respectively. Their equation of state shows volume collapse of 3.6, 16.93, 16.53 and 2.5%. The elastic constants and thermo physical properties have also been obtained at zero and high pressures. The results are in good agreement with the experimental and theoretical data where available. This model is capable of explaining the phase transition, Cauchys discrepancy, and elastic and thermo physical properties successfully. Keywords: semiconductors, anisotropy, crystal structure, elasticity, phase transitions, highpressure.

1. Introduction Group III-nitrides are promising semiconductor material which posses increasing scientific and technological applications in wide band gap semiconductors due to outstanding mechanical properties such as the high melting point, high thermal conductivity, mechanical stability and large bulk moduli. The group III-nitrides crystallize in the wurtzite (W) structure, but the zinc-blend (ZB) structure has been grown using heteroepitaxy on cubic substrates. The wurtzite (W) structure is more stable than zinc-blend (ZB) structure, but the ZB phase has several advantages for smaller band gap, device applications, easy cleavage and higher carrier motilities [1]. Cubic BN exhibits three different structures hexagonal, cubic zinc-blend structure and wurtzite structure. But in zinc-blend structure the priorities of BN such as high melting point, high thermal conductivity and extreme hardness make it useful for protective coatings which are related to their mixed ionic and covalent bonding [2]. The transformation mechanism from zinc-blend (ZB) to rock-salt (RS) in semiconductors has been studied extensively. Various first-principle investigations performed on group IIInitrides [2-7]. For BN transition from ZBRS phase occur at pressure 1088GPa [5], Zaoui et al. Found that the transition pressure from ZBRS is 550 GPa by using FP-LAPW method [8] Furthermore N.E. Christensen et al concluded that the pressure was 850 GPa by using muffin-tin orbital (LMTO) calculation [9]. The transformations from ZBRS have also been reported by Serrano at pressure 7.1, 42.1 and 10.5 GPa for AlN, GaN and InN [10]. N.E.

Christensen et. al have been studied the optical and structural properties of III-V nitrides by using band structure and total energy calculations. These calculations were made by means of the linier muffin tin orbital (LMTO) method. They conclude that all nitrides transform from W RS phase at pressure 16.6, 51.8 and 21.6 GPa and BN transform from ZBRS at pressure 850 GPa. Furthermore Shouxin Cui et.al [5] have been investigated the structural electronic and elastic properties of the cubic BN by a first-principle pseudo potential method. This calculation shows that BN transform from ZBRS phase at pressure 1088 GPa with a volume reduction of 3.1%. The studies on elastic properties and phase stability of all III-V compounds have been done by using first-principle plane-wave pseudo potential calculations [11]. It is seen that the anisotropy factor A are larger than 202 prefer the W structure for IIInitrides. H.Y. Xiao et.al [7] have been carried out to study pressure-induced phase transition from ZBRS structure in AlN and GaN. They have been shown that there is certain effect on the transition pressure by Ga-3d electrons and also effect the pressure coefficient of band gap slightly. M.B. Kanoun et.al [2] was studied the pressure dependence of elastic constants of BN, AlN, GaN and InN by using first -principle full potential augmented-plane wave plus local orbital (FP-APW+lo) calculations with density functional theory in local density approximation. On the other hand experimental studies on III-nitrides are less reported. Among these four nitrides the phase transition pressure and elastic constants at zero pressure have been performed experimentally for BN. Various first-principle calculations have studied the structural, mechanical and electronic properties successfully for III- nitrides. Inspite of the above electronic, structure calculations, there is no study available using phenomenological model. The nature of interatomic forces is not well understood in these compounds and phenomenological model based on various interatomic interaction energies to determine stable structure and chemical trends in the atomic characteristics becomes important. In the present study, we applied interaction potential model to these compounds to study high pressure phase transition, elastic and mechanical properties. In the present model we have included three-body interaction(TBI) forces, which is developed by Singh and coworkers[12-14] has been found to be successful in giving the description of structural and elastic properties of ionic and semiconductor crystal [15]. These properties could also be explained by two-body potential model, but this model could not explain Cauchy violations (C12C44). This TBI approach has been extended to include the Hafemeister-Flygare (HF) type [16] overlap repulsion operative up to the second neighbour ions for describing, the lattice static and mechanical properties of binary ionic solids and alloys. Also Tosi and coworkers [17] have demonstrated the significance of van der Waals (vdW) attraction due to the dipole-dipole (d-d) and dipole-quadruple (d-q) interaction to describe the cohesion in ionic solids and they are generally ignored in the first principle calculations. Since these compounds are partially covalent in nature hence Coulomb interaction and covalency effect become quit important at high pressure. The present model calculations are valuable in the case where quantum mechanical modelling cannot be applied, e.g., in finite temperature simulations etc. In such cases, the DFT based quantum mechanically approach is extremely costly. Hence the present interaction potential model (IPM) are important looking to its ability to explain a variety of crystal properties by taking same set of parameters. In the

section 2 method of computation has been presented. It is followed by results and discussion in section 3 and conclusion in section 4. 2. Method of computation The application of pressure on the crystal causes the decrease in their volume, which in turn leads to an increased charge transfer (or exchange) between the overlapping electron shells of the adjacent ions. This overlapping leads to the transfer of charges which when interacts with other distant charges gives rise to many body interactions (MBI), the dominant part of MBI is three-body interactions [12]. These TBP effects have been incorporated in the Gibbs free energy (G=U+PV-TS). Here, U is the internal energy which at T=0K is equivalent to the lattice energy, S is the vibrational entropy at absolute temperature T. At T=0K and pressure P, the Gibbs free energy for the zinc-blend (B3, real) and NaCl (B1, hypothetical) structures are given by
G B 3 ( r ) = U B 3 ( r ) + PV B 3

(1)
G B1 ( r ' ) = U B1 ( r ' ) + PV B1

(2) With V
B3

(3.08 r ) and VB1 ( 2.00 r)

as unit cell volumes for B3 and B1 phases,

respectively.

The first term in (1) and (2) are lattice energies for B 3 and B1

structures and they are expressed as

U B 3 (r ) = M e 2 Z 2 4 M e 2 Zf m ( r ) C D 6 + 8 + 4b ij exp( ri + r j rij / ) r r r r + 6b ii exp( 2ri 1.63rij / ) + 6b jj exp( 2r j 1.63rij / )

(3)

U B1 ( r ) =

' M e 2 Z 2 6 ' M e 2 Zf m ' (r ) C D 6 + 8 + 6bij exp( ri + r j r ' ij / ) r' r' r' r' + 6bii exp( 2ri 1.414 r ' ij / ) + 6b jj exp( 2r j 1.414 r 'ij / )

(4) With M and M as the madelung constants for ZnS and NaCl structures, coefficients of B 3 (B1)

respectively. C (C) and D (D) are overall van der Waal

phases, ij ( i,j = 1,2 ) are the Pauling coefficients defined as ij = 1 + (Zi/ni) +(Zj/nj) with Zi (Zj ) and ni (nj ) are the valence and the number of electrons of the i (j)th ion. Ze is

the ionic charge and b () are the hardness (range) parameters, r(r) are the nearest neighbour separation for ZnS (NaCl) structure. fm(r) is the modified three-body force parameter which includes the covalency effect with three-body interaction r i (rj) are the ionic radii of ions i (j). These lattice energies consist of long range Coulomb energy (first term ), modified three-body interactions corresponding to the nearest neighbour separation r (r) (second term ), van der Waal interaction (third term ), energy due to the overlap repulsion represented by Hafemeister and Flygare ( HF) type potential and extended up to the second neighbour ions (forth, fifth and sixth terms ). We have included the effect of covalent forces in three-body force parameter f(r) on the lines of Motida [18]. In the present model fm(r) is assumed to be constructed by two parts, i.e. 1. due to covelancy fcov (r) 2. due to overlap distorted effect (three-body interaction) fTBI(r) Now modified three-body parameter fm(r) becomes
f m ( r ) = f TBI ( r ) + f cov ( r )

(5) Where fTBI (r) is determined by the equation:

f TBI (r ) = f 0 e r /

The f (r) due to covalency (fcov) is given by

f cov (r ) = 4V 2 sp e 2 / rEg3
V 2 sp / Eg 2 = 1 es / e 12
(6)
*

E g = E I + ( 2 1)e 2 / r

With Vsp is the transfer matrix between the outer most P orbital of anion and lowest excited state of cation, Eg is the transfer energy of electron from anion to cation. Denoting the static and optical phonon frequency at zone centre by t, es represented as

(es ) 2 = 9 ( 0 ) / 4N ( + 2) 2 t (es / e) 2 = 9 0 0 ) / 4e 2 ( + 2) 2 (
* 2

(7)

where denotes the unit cell volume: 2r, r equilibrium value of the separation of the nearest neighbouring ions, 0 the static dielectric constants, ions, and 0 the infrared dispersion frequency. 3. Result and discussions 3.1 structural properties The present interaction potential model (IPM) contains three model parameters b, and f m(r), namely hardness, range and modified three-body interaction parameter. These parameters are calculated by using the first derivative of cohesive energy (U) and equilibrium condition expressed as:
dU dr =0
r =r 0

reduced mass of the

(8) (9)

B1 + B2 = -1.261Z [Z+8fm(r)]

To test the reliability of the IPM, we have investigated the structural stability by calculating the cohesive energy for ZB and RS structures for all four compounds and found that ZB-type structure possesses minimum energy and thus most stable at an ambient pressure. The calculated cohesive energy as a function of volume for ZB and RS structure are shown in Fig. 1(a) - 1(d). The phase transition pressure is thus determined by calculating the Gibbs free energy G=U+PVTS for the two phases. The Gibbs free energy becomes equal to the enthalpy H=U+PV at T=0K. The values of the thermo dynamical potential G or H have been computed using the values of the three model parameters, (b, r and fm(r)), which have been evaluated from the equation (8) and (9). The values of required input data and computed model parameters have been listed in Table 1. While estimating, the structural phase transition of the IIInitrides semiconductors, we first minimize the Gibbss free energies GB3(r) and GB1(r) by equation (1) and (2) at different pressures in order to obtain the interionic separations r and r corresponding to B3 and B1 phases associated with minimum energies. Fig. 2(a)-2(d) illustrates the Gibbss free energies for B3 and B1phases have been plotted as functions of pressure (P). Let us summarize the results of the plots. At zero pressure, the Gibbs free energy for B3 crystal phase is more negative therefore it is thermodynamically and mechanically stable, while the B1 is not. The pressures at which Gibbs free energy of two phases are equal and a cross to each other is the phase transition pressure Pt. As pressure increases, beyond the phase transition pressure (Pt), the Gibbs free energy for B1 system becomes more negative than B3 phase, so B1 will be more mechanically and thermodynamically stable. The binary semiconductors BN, AlN, GaN and InN in ZB structure at low and moderate pressures and a crystallographic transition from B3B1occurs. Fig. 2(a)-2(d) shows the phase transition pressure for ZB-type (B3) to RS-type (B1) structures in BN at 550 GPa, AlN at 21.0 GPa, GaN at 37.0 GPa and InN at 8.2 GPa respectively. The present values of phase transition pressure illustrated by arrows in Fig. 2.

and have been listed in Table 2 and compared with their other theoretical results. It is clear from Fig. 2 and Table 2 that the phase transition pressures (Pt) obtained from IPM are in good agreement with other theoretical results [4-5, 8-10, 19-22]. The values of the relative volumes V (P)/V (0) associated with various compressions have been computed. Values of the pressure-dependent radii r (r) for both the structures (B3 and B1) have been used to compute the values of V(P)/V(0) and are plotted them against the pressure (P) as given in Fig. 3(a)-3(d) for group III-nitrides. The magnitudes of the discontinuity in volume collapse [-V (Pt)/V (0)] at the transition pressure are obtained from the phase diagram and the values are listed in Table 2 and compared with corresponding theoretical results [5, 9-10, 19, 22]. The experimental values of volume collapse are not available for the comparison. It is clear that during the phase transition from ZB to RS, the volume discontinuity identify the first order phase transition and same trend as the other theoretical approach. In Fig. 4(a)-4(d), we have shown the variation of B-B, Al-Al, Ga-Ga and In-In and B-N, AlN, Ga-N and In-N distance with pressure for these compounds. The distance between X and N is listed in Table 2 at the ambient condition. The bond between X and N is found to be partially covalent, the X-N distance are larger than the sum of covalent radii of X and covalent radii of N and smaller than the sum of atomic radius of X and covalent radius of N. It is clear from this Fig. 4(a)-4(d), the value of next nearest neighbour distance show an abrupt decline at pt while the nearest neighbour distance increase abruptly at pt. The increase in interionic distance gives rise to weakening of Coulomb force in RS phase and next nearest neighbour distance shows decrease with pressure. Similar trend is found in other compounds [23]. 3.2 Elastic properties The elastic constants are important properties of solids which provide a link between the mechanical and dynamic behaviours of crystals. They provide information on the elasticity, stability and stiffness of crystals and give important information about nature of forces operating in solids. A study of elastic properties for materials is also essential to understand the chemical bonds and cohesion of material. Since the forces and the elastic constants are functions of first and second derivatives of the interionic potential, their calculation will provide a further check on an accuracy of the calculated values of forces in solids. The expressions of second order elastic constants and the effect of pressure on them essential especially, for understanding interatomic interactions, mechanical stability, phase transition mechanisms. 3.3 Mechanical properties The traditional mechanical stability conditions on the elastic constants in cubic crystal are known as C11-C12 >0, C11>0, C44>0, C11+2C12>0 and C12<B<C11. Our calculated results for elastic constants satisfy these stability conditions.

References

[1] K.H. Ploog, O. Brandt, H. Yang, J. Menniger, R. Klann, Solid State Electron. 41 (1997) 235. [2] M.B. Kanoun, A.E. Merad, G. Merad, J. Cibert, H. Aourag, Solid State Electron. 48 (2004) 1601-1606. [3] M. Durandurdu, J. Phys. Chem. Solids, 69 (2008) 2894-2897. [4] H.Y. Xiao, Fei Gao, X.T. Zu, W.J. Weber, J. Alloys and Comp., 490 (2010) 537-540. [5] S. Cui, W. Feng, H. Hu, Z. Feng, Cent. Euro. J. Phys., 8(4) (2010) 628-633. [6] U.P. Verma, P.S. Bisht, Solid State Sciences, 12 (2010) 665-669. [7] H.Y. Xiao, X.D. Jiang, G. Duan, Fei Gao, X.T. Zu, W.J. Weber, Comput. Mater. Sci. 48 (2010) 768-772. [8] A. Zaoui, F. El Haj Hassan, J. Phys. Cond. Mat. 13( 2001) 253. [9] N.E. Christensen, I. Gorczyca, Phys. Rev. B 50 (1994) 4397. [10] J. Serrano, A. Rubio, E. Hernandez, A. Munoz, A. Mujica, Phys. Rev. B 62 (2000) 16612. [11] S.Q. Wang, H.Q. Ye, Phys. Stat. Sol.(b) 240 (2003) 45-54. [12] R. K. Singh, Phys Rep. 85 (1982) 259. [13] R. K. Singh, S. Singh, Phys. Rev. B 39 (1989) 671. [14] P. Bhardwaj, S. Singh, N.K. Gaur, Mater. Res. Bull. 44 (2009) 1366-1374. [15] R. K. Singh, S. Singh, Phys. Rev. B 45 (1992) 1019; S. Singh, R. K. Singh, R. Rai, B.P. Singh, J. Phys. Soc. Jpn. 68 (1999) 1269. [16] D.W. Hafemiester, H. F. Flygare, J. Chem. Phys. 43 (1965) 795. [17] M.P. Tosi, F.G. Fumi, J. Phys. Chem. Solids 23 (1962) 359; M.P. Tosi, Solid State Phys. 16 (1964) 1. [18] K. Motida, J. Phys. Soc. Jpn. 55 (1986) 1636. [19] M. Ueno, A. Onodera, O. Shimomura, K. Takemura, Phys. Rev. B 45 (1992) 10123. [20] I. Gorczyca, N.E. Christensen, Solid State Commun. 79 (1991) 1033. [21] S. Adachi, Properties of Group- IV, II-V and II-VI Semiconductors, Weiley, U.K. 2005. [22] H. Xia, Q. Xia, and A.L. Ruoff, Phys. Rev. B 47, (1993) 12 925. [23] G. Pagre, S.P. Sanyal, P.K. Jha, J.Alloys and Comp. 398 (2005) 16-19. [24]

Table 1. Input data and Model parameter for each compound.

Input parameters () ri rj a Model parameters b (10-12 ergs.) () f(r) fm(r)

a

BN 1.2 1.71 3.615a 0.076 0.314 -0.0647 -0.0053

AlN 0.39 1.71 4.37b 0.2111 0.250 -0.0821 -0.0981

GaN 0.62 1.71 4.50b 0.1557 0.160 -0.0234 -0.0364

InN 0.81 1.71 4.98b 0.5612 0.270 -0.0422 -0.0472

Ref [5] Ref [9]

Table 2. Phase transition, volume collapse and elastic constants.

Phase transition pressure (GPa) BN 555 1088a , 555c , 850d

Volume collapse 3.6 3.1a, 4d

Ref. Present Other calc.

AlN

21 7.1e, 22.9f, 16-17g, 14-22.9h

17 20.4e, 18f 16.53 17i, 15.2e

Present Other calc. Present Other calc.

GaN

37 37i, 34j, 42.1e

InN

8.2 8.2, 10.5e

17.79 17.6e

Present Other calc.

Ref. [5]

Ref. [8] Ref. [9] Ref. [10] Ref. [19]. Ref. [20]. Ref. [21]. Ref. [22]. Ref. [4].

Table 3. Elastic constants (GPa) C11 Pres. Exp. e Othr. d C12 Pres. Exp. e Others C44 Pres. Exp.e Others. f C12-C44 70.0 70.5 76.3 -7.7 59.8 59.2 63.4 -7.8 42.3 43.2 46.2 -2.8
f

138.4 141.2 150.7

120.4 118.1 124.2

92.8 88.4 92.7

62.3 62.5 62.8

52.0 52.3 51.4

39.5 40.3 46.2

Radius ratio Pres. Others g 0.292 0.290 0.279 0.280 0.253 0.250

-8000

(a) BN

-8500

Total energy (kJ/mol)

-9000

-9500

-10000

RS phase

-10500 4 6 8

ZB phase
10 12
0

14

16

18

Volume ( )

(b)
-8800

Total energy (kJ/mol.)

AlN
-9200

RS Phase
-9600

ZB Phase

12

16

20

Volume()

-7500

(c)
-8000

GaN

Total energy (kJ/mol)

-8500

-9000

ZB phase
-9500

RS phase
-10000

12

14

16

18

20

22
0

24

26

28

30

32

Volume ( )

-6500

(d)
-7000

InN Total energy (kJ/mol)

-7500

-8000

ZB phase
-8500

RS phase
-9000 15 20 25 30
0

35

40

Volume( )

Fig. 1 (a, b, c, d)

-6000 -9000

-7000

Z B p h a se R S p hase

-9100 -9200

Z B p h a se R S p h a se

Gibb's energy (kJ/mol)

BN

Gibb's energy (kJ/mol)

-8000

-9300 -9400 -9500 -9600 -9700

A lN

-9000

(a )

(b )

-10000

-11000 0

100

200

300

400

500

600

700

800

10

20

30

40

50

P r e ssu r e (G P a )
-8300

P r e ss u r e (G P a ) Z B p h a se R S p h a se
-8400

-9300

Z B p hase R S p h a se

Gibb's energy (kJ/mol)

G aN
-9600

Gibb's energy (kJ/mol)

InN
-8500

(c )

(d )

-8600

-9900 -8700 0 0 10 20 30 40 50 60 5 10 15 20 25

P r e ssu r e (G P a )

P r e ssu r e (G P a )

Fig. 2 (a-d)