PHYSICAL REVIEW B

VOLUME 56, NUMBER 19

15 NOVEMBER 1997-I
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Ab initio calculation of the structure of the random alloys Snx Ge1

Jianhua Shen, Jian Zi, and Xide Xie

Surface Physics Laboratory, Fudan University, Shanghai 200433, Peoples Republic of China

Ping Jiang
CCAST (World Laboratory), P.O. Box 8730, Beijing 100080, Peoples Republic of China and Surface Physics Laboratory, Fudan University, Shanghai 200433, Peoples Republic of China Received 16 June 1997 We present a theoretical analysis for the system of random alloys Snx Ge1 x x 0.25, 0.50, and 0.75 . An ab initio pseudopotential total-energy calculation is performed to determine the structure of the system. It is found that the equilibrium lattice constant of this kind of alloy is close to a linear average of the lattice constants of its constituent elements, i.e., Ge and -Sn with composition x and the possibility of forming a SnGe zinc-blende-type compound is only slightly favorable energetically. Both bond-length and bond-angle distributions are determined. The topological rigidity parameter a ** of the alloy is found to be 0.69 0.02 . The 0.03 average value of bond angle for each alloy calculated is approximately unchanged from 109.5, while the specic angles such as Ge-Ge-Ge, Sn-Sn-Sn, etc. are different from each other and increase with Sn composition x from one alloy to the other. S0163-1829 97 02643-X

The semiconductor alloys with the composition of elements Sn and Ge of group-IV, Snx Ge1 x , have attracted great attention in recent years. Theoretical calculations suggest that the Snx Ge1 x alloys may have direct energy gaps continuously tunable from 0.55 to 0 eV with composition x from 0.2 to 0.6, and very small electron effective masses.1,2 Moreover it is shown that this kind of alloy might be compatible with the most technologically developed materials Si and Ge. Therefore recently they appear as promising candidates in the fabrication of Si or Ge based long-wavelength infrared optoelectronic devices with a high response. Although metastable random alloys Snx Ge1 x of a diamondlike structure have been successfully obtained with x up to 0.34 without Sn segregation by an ion-assisted molecular-beam epitaxy technique,1,2 there is still a lack of detailed structure data of the alloys either from experimental measurements or from theoretical calculations. In this report we present an ab initio total-energy calculation for random alloys Snx Ge1 x x 0.25, 0.50, and 0.75 for the determination of their structural properties. We model Snx Ge1 x alloy with a supercell consisting of 72 atoms. The supercell is considered to have 3 periodicity along both 10 and 110 , and 8 periodicity along the 1 001 direction. In the initial conguration each atom, either Sn or Ge, is assumed to locate randomly at a lattice point of diamond lattice under the restriction of chemical composition x. The calculation is based on the density-functional theory in the local-density approximation LDA including the Ceperley-Alder correction scheme.3,4 Electron-ion interaction has been treated by the ghost free norm-conserving pseudopotential in Kleinman-Bylanders fully separable form.58 The wave functions are expanded in the plane-wave basis set with the cutoff energy at 10 Ry. The Kohn-Sham equation is solved self-consistently by using the CarParrinello approach9,10 with k-points sampled in the Brillouin zone following Chadi and Cohen.11 All atoms in the supercell are allowed to relax by Hellmann-Feynman force
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according to the damping steep-descent method.12 The optimized atomic geometries correspond to the minimum of total energy with the remaining forces acting on each atom less than 0.004 Ry/. At rst, the equilibrium lattice constants of crystalline Ge and -Sn are determined to be 5.555 and 6.375 , respectively. In comparison with the experimental values, there exists a negative deviation of less than 1.7% which comes from the LDA inherently. The total energies with all atoms relaxed for Snx Ge1 x alloys x 0.25, 0.50, and 0.75 have been calculated and are given in Fig. 1. It can be seen that the equilibrium lattice constants of these alloys are 5.780, 5.969, and 6.175 , respectively, which are close to the compositionally weighted average of the calculated values of crystalline Ge and -Sn just mentioned with deviations as low as 0.02, 0.004, and 0.005 for x equal to 0.25, 0.50, and 0.75, respectively. The bulk moduli of the alloys are also obtained as 63.4, 56.2, and 50.8 GPa, respectively. In Fig. 1 the total energies of zinc-blende-type SnGe compound are also presented with open circles and dashed curve, which are less than 1 mRy per atom smaller than those of random alloy Sn0.50Ge0.50. This result shows that the possibility of forming zinc-blende-type SnGe compound is only slightly favorable energetically. The topology of our model is determined through the bond-length distributions and bond-angle distributions. Five different initial random congurations have been sampled for each composition x in order to assure the reliability of the calculation. The bond-length distributions are shown in Fig. 2: there are three peaks in each curve, which correspond to the Ge-Ge, Sn-Ge, and Sn-Sn bond, respectively, as one moves from left to right. It can be shown from the theory of probability that the appearance probabilities of the Sn-Sn, Sn-Ge, and Ge-Ge bond in the Snx Ge1 x alloy should be x 2 , 2x(1 x), and (1 x) 2 , respectively, and this is conrmed by the areas of the peaks in Fig. 2. From Fig. 2 the average sampling accuracy which is dened as the ratio of the per12 084 1997 The American Physical Society

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FIG. 1. Total energy of Snx Ge1 x x 0.25, 0.50, and 0.75 versus lattice constant. The circles are theoretical results obtained from present ab initio calculations and the curves are tted by the Murnsghan equation of state.

centage area of each peak the peak area divided by the total area under the whole curve to the corresponding theoretical probability is determined to be 99.2% for x 0.25, 99.0% for x 0.50, and 95.0% for x 0.75. This convinces us that our sampling number ve for each composition x for determining bond length is reasonable. It can be seen from Fig. 2 that the mean bond lengths of Ge-Ge, Sn-Ge, and Sn-Sn increase with composition x monotonically and the bond lengths of Ge-Ge and Sn-Sn shown in the gure deviate from the natural values of crystalline Ge and -Sn remarkably. Since there exist no experimental data of Snx Ge1 x alloy available, we compare the calculated Ge-Ge bond-length variations with the well-studied Six Ge1 x alloy13 in Table I. As shown in Table I the relative deviations of Ge-Ge bond lengths in Snx Ge1 x alloys from the natural Ge-Ge bond length in crystalline Ge are almost 3 times larger than those in the Six Ge1 x alloys. This is understandable from the fact that the lattice mismatch between crystalline a-Sn and Ge 13% is much larger than that between crystalline Si and Ge 4.2% . Meanwhile a topological rigidity parameter a ** dened analytically by Cai and Thorpe14,15 is adopted to measure the rigidity of the lattice. For Snx Ge1 x alloys the denition of the topological rigidity parameter a ** can be shown as

FIG. 2. Bond-length distributions for Snx Ge1 x : a x 0.25, b x 0.50, and c x 0.75. The histograms are the values from our calculation for ve random samplings, and the curves are obtained from Gaussian tting.

L GeGe L SnSn L SnGe

0 0 L e xa ** L SnSn L GeGe ,

L GeGe 1 2

0 0 a ** L SnSn L GeGe ,

L GeGe

L SnSn ,

0 L e xL SnSn

0 1 x L GeGe,

0 0 where L GeGe and L SnSn are the Ge-Ge and Sn-Sn bond lengths calculated for crystalline Ge and -Sn, respectively, and L GeGe , L SnGe , and L SnSn are the Ge-Ge, Sn-Ge, and Sn-Sn mean bond lengths in Snx Ge1 x alloy of composition x. By tting our calculated data with these expressions the topological rigidity parameter a ** determined is 0.69 0.02 0.03 for our model structure which is larger than that of the Six Ge1 x alloy 0.63 0.08 determined by the extended x-ray0.13 absorption ne-structure EXAFS measurement13 . According to Thorpes theory the topological rigidity parameter a ** is generally determined by the coordinate number of the alloy. For semiconductor alloys a ** is usually around

TABLE I. Relative deviations of Ge-Ge bond length in Snx Ge1 x and Six Ge1 x alloy from its natural value in crystalline Ge. The data of Snx Ge1 x are calculated from the present work and the data of Six Ge1 x are from the EXAFS measurement Ref. 13 . x Snx Ge1 Sex Ge1
x x

0.25 1.6

0.26 0.4

0.31 0.6

0.41 0.6

0.50 2.5

0.64 0.8

0.75 3.8

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FIG. 3. Bond-angle distributions for Snx Ge1 x . The solid curves represent x 0.25, the dashed curves represent x 0.50, and the dotted curves represent x 0.75. The arrows indicate the tetrahedral bond angle, 109.5.

0.75.16 For a lower value of a ** the alloy will be more rigid. Therefore the alloy Snx Ge1 x is less rigid than the alloy Six Ge1 x which is consistent with the fact that a-Sn is obviously oppier than crystalline Si. The result of our bondlength calculation is in good agreement with Cai and Thorpes analytical result for mismatched semiconductor alloys except our Ge-Ge bond-length distribution for x 0.75 is a little more scattered. The angle distributions are determined for all possible nearest-neighbor congurations and the results are shown in Fig. 3. Obviously the curves look more complicated than the bond-length distributions. In this report the notation GGG stands for the bond angle between bond Ge-Ge and bond Ge-Ge, GSG stands for the bond angle between bond Ge-Sn and bond Sn-Ge, etc. The appearance probabilities of GGG, GSG, SGG, SGS, SSG, and SSS in the alloy Snx Ge1 x should be (1 x) 3 , x(1 x) 2 , 2x(1 x) 2 , x 2 (1 x), 2x 2 (1 x), and x 3 , respectively. As for the bond-length distribution, we obtain the average sampling accuracies for bondangle distributions from each curve in Fig. 3 as 92.3%, 95.6%, and 86.6% for x of 0.25, 0.50, and 0.75. Although they do not look as good as those for the bond-length distributions, we believe that our calculation based on the random sampling described above is effective to determine the bondangle distribution in Snx Ge1 x alloys. We list the average bond angles and its standard deviations of Snx Ge1 x alloys in Table II, together with those of Si0.50Ge0.50 alloy

and amorphous a-Si for comparison. It is interesting that the average bond angle we obtained is nearly unchanged from 109.5 for all three Snx Ge1 x alloys investigated and is almost the same as that of Si0.50Ge0.50 or a-Si, while the standard deviations of bond angles in Snx Ge1 x alloys are obviously larger than that in Si0.50Ge0.50 and less than that in a-Si. This shows that the distortion of bond angle is consistent with the degree of lattice mismatch in the semiconductor random alloy, however, the bond-angle distortion introduced by the lattice mismatch is much smaller than that due to amorphization. The mean values of the specic angles e.g., GGG and SSG, etc. are listed in Table III. It can be seen that the mean value of bond-angle GGG and GSG is larger than 109.5, whereas the mean value of bond-angle SSS and SGS is smaller than 109.5 regardless of the composition x. The mean values of different bond angles of SSS, SGS, SGG, SSG, GSG, and GGG vary from small to large for each alloy. We have noticed all these mean bond angles increase with Sn composition x. Since there is no experimental data available we are not able to compare the results with experiments for the time being. However we believe lattices in Snx Ge1 x alloys should be distorted remarkably due to the very large difference between the lattice constants and elastic constants of crystalline Ge and -Sn, which would result in the bond-angle deviation from the tetrahedral angle 109.5. In summary, the structures of random alloys Snx Ge1 x x 0.25, 0.50, and 0.75 have been studied by using the ab

TABLE II. Average values and the standard deviations of bond angles in the Six Ge1 x , Snx Ge1 x alloys, and amorphous a-Si. The data of Snx Ge1 x are from this work and those of Six Ge1 x and a-Si are from Mousseau and Thorpe Ref. 15 . Si0.50Ge0.50 deg deg 110.05 0.77 Sn0.25Ge0.75 109.50 2.82 Sn0.50Ge0.50 109.42 3.30 Sn0.75Ge0.25 109.23 2.56 a-Si 109.17 11

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BRIEF REPORTS TABLE III. Mean values of specic bond angles in Snx Ge1 GGG Sn0.25Ge0.25 Sn0.50Ge0.50 Sn0.75Ge0.25 110.47 111.71 114.10 GSG 110.29 110.99 112.05 SSG 109.00 109.85 110.45 SGG 108.64 109.36 110.41
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12 087 alloys in degrees . SGS 106.11 107.15 108.66 SSS 105.80 106.57 108.02

initio pseudopotential total-energy minimization method. The results show that the lattice constant of the alloy is close to a linear average of the lattice constants of the two constituent elements with composition x and the possibility of forming the zinc-blende-type structure is only slightly favorable energetically. All the mean bond lengths Ge-Ge, SnGe, and Sn-Sn bond increase with Sn composition as expected. The topological rigidity parameter a ** is obtained as 0.69 0.02 . The average bond angle of the Snx Ge1 x alloy is 0.03 nearly unchanged for different Sn composition x, while the

mean values of each bond angle possibly existing in Snx Ge1 x increase with x. The sequence is listed as SSS, SGS, SGG, SSG, GSG, and GGG from small to large for each alloy. This work was supported by National Natural Science Foundation of China. One of the authors, Jianhua Shen, would like to thank CHPCC China High Performance Computing Center for supplying part of computer resources on IBM SP2.

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