CHIN.PHYS.LETT.

Vol. 25, No. 6 (2008) 2158

Theoretical Hardness of Wurtzite-Structured Semiconductors

GUO Xiao-Ju(
1

)1 , XU Bo( HE Ju-Long(

)1 , LIU Zhong-Yuan( )1 , GUO Li-Cong(

) , YU Dong-Li( )
1 2

)1 ,

State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 College of Materials Science and Engineering, Hebei University of Science and Technology, Shijiazhuang 050018

(Received 11 March 2008)

Vickers hardness calculations of eleven wurtzite-structured semiconductors are performed based on the microscopic hardness model. All the parameters are obtained from rst-principles calculations. There are two types of chemical bonds in wurtzite-structured crystals. The overlap populations of the two types of chemical bonds in lonsdaleite are chosen as Pc for wurtzite structure. The calculated bond ionicity values of the wurtzite-structured semiconductors are in good agreement with the ionicities from the dielectric denition. When the hardness of wurtzite-structured crystal is higher than 20 GPa, our calculated Vickers hardness is within 10% accuracy. Therefore, the hardness of novel wurtzite-structured crystal could be estimated from rst-principles calculations.

PACS: 62. 20. Qp, 71. 15. Mb, 81. 05. Zx Semiconductors have attracted a great deal of attention because of their extensive applications in industry. Most semiconductors can crystallize in either zinc-blende or wurtzite structure or even in both structures. The well-known semiconductors such as AlN, GaN, InN, BeO, ZnO, and CdS are stably crystallized in wurtzite structure, while diamond, Si, SiC, BN, and ZnS are stably crystallized in zinc-blende structure. The tetrahedral coordination resulting from the sp 3 hybridization is the basic feature of these two structures. Generally speaking, the sp 3 bonding is composed of main covalent component and partial ionic component. The similarity of the crystal structures makes isomeric compounds in these two structures always have comparable properties such as almost identical densities, electron energy band gaps, elastic properties, etc.[14] Traditionally, bulk and shear moduli are used to estimate the hardness of materials by using semiempirical relations.[5] From this point of view, the similar bulk and shear modulus between zinc-blende and wurtzite polymorphs should result in comparable hardness. The Vickers hardness of diamond single crystal is about 96 GPa.[6] Since the experimental hardness value of lonsdaleite is exiguous, theoretical estimation of the lonsdaleite hardness is imperative. Recently, Gao et al.[7] proposed a semiempirical method to calculate the hardness of pure and polar covalent crystals. Hardness calculations of zinc-blende materials,[7] boron-rich compounds,[8] and so on[9,10] have conrmed that this semiempirical method is effective. However, such kind of calculations is still absent for wurtzite-structured crystals to our knowledge. In order to calculate the hardness for wurtzitestructured crystals using the microscopic hardness model, the only parameter missed is the bond ionicity. All the others such as bond length and valence electron density can be easily obtained by rst-principles calculations. In the hardness calculation of the zinc-blende structured materials,[7] the bond ionicities are determined semiempirically. Ionicity originates from spatially asymmetric charge distribution between two bonded atoms. The spatial charge distribution not only is correlated with the types of bonded atoms but also depends on the chemical environment around the chemical bond. Therefore, the ionicity values of a chemical bond in dierent structures are always different. Unlike the single bond in zinc-blende semiconductors, there are two types of chemical bonds in wurtzite semiconductors. For these two dierent chemical bonds, the bond ionicities should be dierent because of the dierent bond parameters. The dielectric scale of ionicity proposed by Phillips[11] was successfully used in the interpretation of some basic physical and chemical properties. However, the bond ionicities of wurtzite-structured semiconductors based on the dielectric scale gave the same value for these two types of chemical bonds.[11] Recently, a novel overlap population ionicity scale[12] was proposed, which tted with the Phillips ionicity very well by a conversional equation. According to this scale, the only parameter used in ionicity calculation is the bond overlap population, which can be deduced from rst principles calculations. Thus the hardness calculations of the wurtzite-structured semiconductors are achievable. In

Supported by the National Natural Science Foundation of China under Grant Nos 50532020 and 50672081, the National Basic Research Programme of China under Grant No 2005CB724400, and the Science Foundation of Yanshan University for the Excellent PhD Students. Email: hjl@ysu.edu.cn c 2008 Chinese Physical Society and IOP Publishing Ltd

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this work, we perform a systematic calculation for hardness of the wurtzite-structured semiconductors. The rst-principles calculations were performed with CASTEP code based on the density functional theory. All the crystal structures of wurtzite semiconductors were optimized by BFGS algorism.[13] The geometry optimization were performed for a 2 2 1 super cell. The ultra-soft Vanderbilt potentials[14] were used and the exchange-correlation terms were considered by the PerdewBerkeErnzerhof form of the generalized gradient approximation (GGA-PBE).[15] The Mesh parameters for Brillouin zone sampling were determined to keep the actual spacing about 0.04 1 A according to MonkhorstPack grid.[16] Mulliken overlap populations were integrated by a distance cuto 3 for 2 2 1 super cells. The optimizaA tion was performed until the forces on the atoms less than 0.01 eV/, all the stress component less than A 0.02 GPa, and the variation of total energy less than 5.0 107 eV/atom. The calculations of elastic constants were performed based on the primitive cell. The calculated Mulliken overlap populations of the chemical bonds in the wurtzite semiconductors are used to estimate their Phillips ionicity values by converting from population ionicity scale,[12] fi = (1 e|Pc P |/P )0.735 , (1)

The crystal structure of wurtzite semiconductors is schemed in Fig. 1. Two types of chemical bonds in wurtzite structure are clearly demonstrated. The rst type (X Y ) includes all of the chemical bonds parallel to c axis. And all the other bonds (X Y ) belong to the second type. The calculated lattice constants a and c, unit cell volumes V , elastic constants, and bulk moduli B of eleven wurtzite semiconductors are listed in Table 1. Here, AlN, GaN, InN, BeO, ZnO, and CdS are stably crystallized in wurtzite structure and the others are metastable.[1] The lattice parameters of the eleven semiconductors in wurtzite structure are in good agreement with the experimental or theoretical results. From the results listed in Table 1, we nd that the elastic constants and bulk moduli of wurtzite-structured semiconductors are similar to that of the corresponding zinc-blende-structured semiconductors. Unlike the case in diamond and silicon (the

where P is the overlap population of a bond, Pc is the overlap population of the bond in a pure covalent crystal of identical coordinate structure of wurtzite semiconductors.

Fig. 1. Schematic unit cell of the wurtzite structured semiconductors. The two types of the bonds are indicated by dierent grey levels.

Table 1. The lattice parameters a and c, volume per unit cell (the comparison values are calculated from the comparing lattice parameters a and c), elastic constants, and bulk modulus (the unmarked values are calculated from the cited elastic constants by using B = [c33 (c11 + c12 ) 2c2 ][c11 + c12 + 2c33 4c13 ]1 ). 13 a () A c () A V (3 ) A c11 (GPa) c12 (GPa) c13 (GPa) c33 (GPa) c44 (GPa) B (GPa) 2.486 4.138 22.147 1236.3 89.6 2.3 1353.1 482.5 446.0 2.490a 4.144a 22.251 1222.5g 106.8g 47.5g 1326.3g 459.4g 463.9g wurtzite-Si 3.798 6.261 78.334 189.0 46.6 53.9 213.6 51.4 108.7 3.800a 6.269a 78.396 194.0g 55.3g 42.0g 206.5g 44.8g 97g Moissanite 2H 3.035 4.980 39.735 536 101.7 45.1 574.3 167.7 225.6 3.072b 5.041b 41.199 223h BN 2.532 4.189 23.256 959.0 120.3 45.9 1041.6 347.8 376 2.534c 4.191c 1.656 982c 134c 74c 1077c 388c 401c AlN 3.063 4.911 39.881 406.2 127.1 94.3 386.3 126.8 203 3.112c 4.995c 41.893 398c 142c 112c 383c 127c 212c GaN 3.206 5.221 46.456 335.6 114.1 79.3 366.3 92.9 176 3.210c 5.237c 46.733 350c 140c 104c 376c 101c 197c InN 3.586 5.801 64.586 210 93.7 72.9 216.3 48.8 124 3.536a 5.709a 61.818 190i 104i 121i 182i 10i 139i BeO 2.741 4.454 28.980 412.7 116.0 83.8 446.3 128.7 204 2.723d 4.376d 28.100 460.6j 126.5j 88.5j 491.6j 147.7j 224j ZnO 3.258 5.262 48.384 197.8 106.6 93.6 209.9 40.3 132.6 3.250e 5.207e 47.630 206e 118e 118e 211e 44e 148e ZnS 3.900 6.405 83.332 104.7 35.6 24.9 117.5 28.6 55.3 3.811f 6.234f 78.411 122.2k 59.1k 46.0k 138.5k 28.2k 76k CdS 4.190 6.817 103.572 80.5 45.0 37.1 87.0 15.2 54 4.137f 6.714f 99.514 85.3l 48l 45.2l 93.8l 15.2l 60.1l a Ref. [2], b Ref. [5], c Ref. [3], d Ref. [17], e Ref. [18], f Ref. [19], g Ref. [20], h Ref. [21], i Ref. [22], j Ref. [23], k Ref. [24], l Ref. [25]. Crystal Lonsdaleite

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overlap populations are both 0.75), the overlap populations for the two types of the chemical bonds in lonsdaleite and wurtzite Si are dierent. The overlap population of CC bond is 0.65 and the overlap population of CC bond is 0.91 in lonsdaleite, while the overlap population of SiSi bond is 0.66 and the overlap population of SiSi bond is 0.81 in wurtzite Si. In order to determine the Pc values for these two types of the chemical bonds in wurtzite structure, we plot the contour map of the charge densities in lonsdaleite and wurtzite Si in Fig. 2. For the CC bonds in lonsdaleite, the charge distribution is symmetrical between two C atoms, while the charge excursion happens between two Si atoms as shown in Fig. 2(b). The SiSi bonds here show the ionicity character to some extent. Thus, the overlap population P1 and P2 of the chemical bonds in lonsdaleite are chosen as the two Pc employed in formula (1) for wurtzite structure.

The calculated chemical bond ionicities in the selected eleven wurtzite-structured semiconductors are listed in Table 2. The ionicities of two X Y bonds in wurtzite-structured crystals are always dierent. The Phillips ionicity in Ref. [23] for the chemical bond in zinc-blende and wurtzite crystal also list in Table 2. In Refs. [11,26], they did not point out whether the ionicity calculated was for the chemical bond in zincblende structure or wurtzite structure. Here we suppose that the ionicities they calculated are for the stable phases. For AlN, GaN, InN, BeO, ZnO, and CdS, which are stably crystallized in wurtzite structures, the bond ionicities obtained here are in good agreement with the ionicity values obtained by using the dielectric scale. The obtained ionicity values conrm the validation of the selection of the two Pc in wurtzite structure. For wurtzite structured Si, Moissanite-2H, BN, and ZnS, the ionicities of the corresponding chemical bond in zinc-blende structure[12] are listed in Table 2 for comparison. Except for wurtzite-Si, the ionicities we obtained of the chemical bonds in moissanite-2H, BN, and ZnS are smaller than those of the corresponding zinc-blende crystals. According to the microscopic denition of hardness, the hardness of wurtzite-structured semiconductors can be calculated by[7] HV = 556
XY 1.191fi Na e dXY
XY

Fig. 2. Contour maps of the charge density distribution of (a) the CCC strain in lonsdaleite and (b) SiSiSi strain in Moissanite 2H.

Table 2. Bond overlap population and the Phillips ionicity of the chemical bonds in the eleven wurtzite-structured semiconductors. The Phillips ionicities for comparison are taken from Ref. [24]. The ionicities of wurtzite structured crystals are marked by asterisk and the others are for the corresponding zinc-blende structured crystals. Crystal Lonsdaleite Wurtzite-Si Moissanite-2H BN AlN GaN InN BeO ZnO ZnS CdS Bond type CC CC SiSi SiSi Si-C Si-C B-N B-N Al-N Al-N Ga-N Ga-N In-N In-N Be-O Be-O Zn-O Zn-O Zn-S Zn-S Cd-S Cd-S P 0.91 0.65 0.81 0.66 0.83 0.63 0.79 0.57 0.63 0.48 0.60 0.49 0.53 0.45 0.52 0.36 0.40 0.42 0.56 0.54 0.48 0.41
fi 0 0 0.205 0.046 0.173 0.078 0.237 0.224 0.471 0.411 0.513 0.391 0.611 0.471 0.625 0.647 0.786 0.530 0.569 0.289 0.680 0.550

XY Na e1.191fi dXY

XY

1/4

(2)

fi 0 0 0 0.177 0.256 0.449* 0.500* 0.578* 0.602* 0.653* 0.621 0.679*

XY XY where Na and Na are the bond densities of X Y and X Y , respectively, dXY (or dXY ) is the bond length of X Y (or X Y ). The bond parameters and the calculated hardness values are listed in Table 3. From Table 3 and Ref. [8], the bond lengths, bond densities, and ionicities of the eleven semiconductors in zinc-blende and wurtzite structures are close to each other. Thus, the semiempirical hardness values of these crystals in zinc-blende and wurtzite structures are comparative. The calculated hardness of the stably crystallized wurtzite semiconductors is in good agreement with the experimental results. For the semiconductors stably crystallizing in zinc-blende structure, the experimental hardness of the wurtzite structure is unavailable. Here we use the experimental hardness of zinc-blende structure as a reference. From the hardness values in Table 3, we nd that the hardness of wurtzite-structured crystals is as high as that of the zinc-blende-structured crystals. This phenomenon can be easily interpreted by the similar determinative factors[7] of hardness in wurtzite and zinc-blende polymorphs.

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Table 3. Bond parameters and calculated hardness of the eleven wurtzite structured crystals. The asterisk marked hardness values (from Ref. [9] and references therein) are for the corresponding crystal in zinc-blende structure. Bond type N CC 6 lonsdaleite CC 2 SiSi 6 wurtzite-Si SiSi 2 Si-C 6 Moissanite-2H Si-C 2 B-N 6 BN B-N 2 Al-N 6 AlN Al-N 2 Ga-N 6 GaN Ga-N 2 In-N 6 InN In-N 2 Be-O 6 BeO Be-O 2 Zn-O 6 ZnO Zn-O 2 Zn-S 6 ZnS Zn-S 2 Cd-S 6 CdS Cd-S 2 a Ref. [27], b Ref. [28], c Ref. [29], d Ref. Crystal
d () A Ne (electron 3 ) A 1.526 0.731 1.55 0.698 2.333 0.205 2.338 0.203 1.858 0.404 1.868 0.398 1.553 0.693 1.569 0.672 1.861 0.302 1.874 0.296 1.97 0.259 1.977 0.256 2.187 0.186 2.196 0.184 1.674 0.277 1.682 0.273 1.986 0.166 1.995 0.164 2.348 0.098 2.408 0.091 2.56 0.074 2.567 0.076 [30], e Ref. [31] fi 0 0 0.205 0.046 0.173 0.078 0.237 0.224 0.471 0.411 0.513 0.391 0.611 0.471 0.625 0.647 0.786 0.530 0.569 0.289 0.680 0.550 Hv 98.8 92.1 11.5 13.7 33.1 36.2 68.9 66.7 19.1 19.8 14.2 16.1 7.8 9.1 19.5 18.6 7.5 9.9 4.5 5.6 2.6 3.1

Hv calc 97.1 12.0 33.9 68.3 19.3 14.6 8.1 19.3 8.0 4.7 2.7

Hv expt 96* 12* 34* 66* 18a 15.1b 15c 7.2d 2.6e

In summary, we have calculated the Vickers hardness of the eleven wurtzite-structured semiconductors by using the microscopic hardness model. By selecting the two bond populations of lonsdaleite as the corresponding Pc values for the wurtzite structure, the Phillips ionicity converted from the population ionicity is in good agreement with the Phillips ionicity value from dielectric ionicity scale. The theoretical hardness of the wurtzite-structured semiconductors is in 10% accuracy with experiments when its hardness is higher than 20 GPa.

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