JOURNAL OF THE PHYSICAL SOCIETY OF JAPAN, Vol. 41, No. 5, NovEMBER, 1976 Band Theory of Graphite. I. Formalism of a New Method of Calculation and the Fermi Surface of Graphite* Hideo NaGayosut,** Kenji Nakao and Yasutada UrMuRa Department of Physies, Faculty of Science, University of Tokyo, Hongo, Tokyo (Received May 11, 1976) ‘The complicated Fermi surface of graphite has been constructed successfully by using a new method of ab initio energy band calculation. The new method has been developed for the purpose of obtaining detailed band structures of layer- type crystals, in which the total wavefunction is constructed by two-dimensional OPW’s in a layer plane and by one-dimensional Bloch functions for a virtual crystal in the direction perpendicular to the layer. ‘The Slonczewski-Weiss band model has been found to be fully adequate for the description of the Fermi surface of graphite. Theoretical values of the param- eters yo~7s and 4 in this band model have been obtained, being in good agree- ‘ment with experimental ones. §1. Introduction Graphite is a typical layer-type crystal, for which much theoretical and experimental work has been made. Particular attention has been paid to the strong anisotropy observed in various physical properties, which is surely due to the layer structure of the crystal. The energy band structure of graphite has been investigated as a basis for the study of its electronic properties. The overall band structure throughout the Brillouin zone has been studied by the tight-binding (TB) or the linear-combination-of-atomic-orbitals (LCAO) method,“ and a recent ab initio LCAO calculation by Painter and Ellis has succeeded in obtaining an energy band structure which is consistent with the measured optical spec- tra in many respects. Much work has also been made for the Fermi surface of graphite, which is located in a small region around the H-K-H axis of the Brillouin zone and whose fine structure is determined by the weak layer-layer interaction. Slonczewski- Weiss (SW) band model”® is widely used for the description of the band structure near the Fermi surface. The band parameters * This paper is based on part of a thesis presented to the University of Tokyo by H. Nagayoshi in partial fulfillment of the degree of Doctor of Science. ** Present address: General Education Depart- ‘ment, Kyushu University, Ropponmatsu, Fukuoka. Yo~ys and 4, which are defined in the k-p perturbation theory around the H-K-H axis and in the semiempirical TB scheme in the direction perpendicular to the layer, have been evaluated from many experiments such as de Haas-van_ Alphen effect,” cyclotron _reso- nance,'®) magnetoreftection'") and infrared thermoreffection.'?” The values of the five parameters yo~73 have been determined ex- perimentally, while there are still some un- certainties about those of ys and 4, especially as to their signs. On the other hand there have been very few attempts to calculate these Fermi surface parameters (SW parameters) from first. prin- ciples. Furthermore there have been almost no attempts to confirm the validity of the SW model, ie., for example, to make clear to what distance in k space from the H-K-H axis the kp theory is valid. The LCAO calculation by Painter and Ellis?’ is inconsistent with experiments for example as to the sign of y, in spite of their success in reproducing the overall band structure, The calculation by the pseudopotential method has also been made by Haeringen and Junginger,'?) who have obtained a very large value of 4 inconsistent with experiments. The “combined OPW-TB method” has been contrived in previous papers'*“!®) for the accurate band calculation of layer-type crystals, but the numerical cal- culation for graphite has not given satisfactory 14801976) results, either. All these failures seem to be due to the difficulty associated with treating the very weak inter-layer interaction, for which the high accuracy in the calculation is required to construct the very complicated Fermi surface. In a previous paper'® a preliminary report was presented on an accurate band calculation of graphite by a new method developed for layer-type crystals, in which the total wave- function is constructed by combining two- dimensional OPW’s (orthogonalized plane waves) in the layer plane and one-dimensional Bloch functions for a virtual crystal in the direction perpendicular to the layer. Theoreti- cal values of the SW parameters were obtained from the energy levels calculated by that method, and the results were fairly in agree- ment with experimental ones. In the present paper and following ones the details of the new method of calculation and many numerical results for graphite are given. In §2 a formal description is presented for the new method of band calculation. Although the calculation of the overall band structure of graphite is not our main concern in this paper, numerical results for it are given in §3, so as to obtain appropriate values of some adjustable parameters of the model potential used in the band calculation. The numerical results for the detailed band structure near the Fermi surface of graphite and for the theoretical values of the ‘SW band parameters are presented in §4. §2. Method of Band Calculation In a layer-type crystal such as graphite an electron seems to move nearly freely in the direction parallel to the layer plane, while it seems to be considerably localized within each layer. This is confirmed by estimating overlap integrals between the atomic orbitals on the adjacent atomic sites. For example a calculation using the 2p, Slater orbital of a carbon atom gives rise to 0.3 and 0.05 as the values of overlap integrals between the adjacent atomic sites in graphite crystal in the parallel and perpendicular directions to the layer, respectively. Thus the nearly-free-electron pic- ture seems adequate for the parallel direction. Although the wavefunction is supposed to be considerably localized within each layer plane, the localization is not so strong that the TB method may conviniently be used for the ac- Band Theory of Graphite. 1 14g curate ab initio calculation. These are the fundamental motivation to our new method of band calculation for layer-type crystals, which is described in detail below in case of graphite. The plane-wave-like basis functions PaselPs fil) Teer (+@)-p) are used in our method for the band calculation at the point [k, k.] in the Brillouin zone. Here- after the notation p=(x,») and k=(ky, k,) are used for the two-dimensional co-ordinate and wavenumber vectors, respectively. Three- dimensional vectors are expressed as [p, 2] and [k, k,]. In the definition (1) of the basis functions, S is the area of the layer plane and G denotes a two-dimensional reciprocal lattice vector. The z-dependent part f,_1(z) is chosen as the L-th solution for a virtual crystal with ‘one-dimensional potential V(z). Namely it is defined by —(h? /2m)fi.2)+ VOM) = Fnethe under the Bloch condition Sal2 +.) =Exp (ick) fe), GB) where c is the lattice constant in the z direction. The potential V(2) in (2) is defined as an average of the actual three-dimensional potential Vp, 2) as follows: tl) (2) P= § | [Po axe. 6 Since the averaged potential V(z) has no information about the inequivalence of the two kinds of layer planes in graphite crystal, it is a periodic function with fundamental period ¢2 (not ¢). Therefore the solution f.,,(2) of eq. (2) for given k,(—n/e o id where the coefficients Ayg are to be deter- mined.* If V(z) in eq. (2) were constant, Py.r6 would be simple plane wave as in the usual OPW method. In this sense our method may be named “generalized OPW method.” The layer structure of the crystal is taken into account in the z-dependent part f,,1(2) of the basis func- tion, The convergence of energies in this method ‘is expected to be much faster than in the usual OPW method, because our basis functions are considered to be better approximate solutions in the direction perpendicular to the layer than the plane waves in the usual OPW method On the other hand our method has no such difficulties as the LCAO-like methods have in the treatment of the continuum states of each atom and the overlaps between far-separated atomic orbitals. This is an important point especially when highly accurate calculations are needed in the study of the band structure near the Fermi surface of graphite. §3. Numerical Results for the Monolayer Model of Graphite Although our method of band calculation is described in §2 for the real multilayer gra- * The details of the actual calculations by this method are described in the thesis by one of the authors. (AN).1976) Phite, it can also be applied to the monolayer graphite with a slight modification. This model is useful, when one is not interested in the detailed band structure in the small region in the k space but interested in the crude one throughout the Brillouin zone. In this case one has to solve f(z) in eq. (2) under the boundary condition Silt 0)=0 (10) instead the Bloch condition (3). Here we are concerned only with the bound states. Calculation for the monolayer graphite is presented here, mainly because we want to determine the suitable values of the adjustable parameters R and £, so that they give rise to a reasonable overall band structure. The numerical results for (R, E,)=(1-lap, —272 eV) are shown in Fig. 2.* Three f,(z) and 48 two-dimensional plane waves are used in the calculation, The parameter values (R, £.)=(I.la,, —272 eV) have turned out to give the most reasonable overall band structure. One can test the validity of the band structure in Fig. 2 by comparing the experimental optical data*-®) with the ca -30) Fig. 2. Calculated band structure by the monolayer model for (R,£.)=(I-1dp, —272 eV). Solid and dashed lines represent o and x bands, respectively. For the monolayer graphite our method of band calculation proves to be the same as the combined OPW-TB method in the previous papers.'*~!) The ‘numerical results reported in refs. 14 and 15 for the same values of parameters are, however, somewhat different from the present ones. A crude interpolation ‘was used there inconsistently for the evaluation of the hamiltonian matrix elements, though there are no description about it in refs. 14 and 15. Such an inter- polation is not used here. Therefore the present results are more reliable than the previous ones. Band Theory of Graphite. I. 1483 Table I. Important characteristic energies of graphite (Unit eV) (1): Valence bandwidth. (2): Overlap of and z valence bands. (3): o band gap at I (4)~ (O: wx, o-¢ and o-m transition energies at M, respectively.). Results by Painter and Ellis” (PE) are also shown, Experimental are the typical ones in literature. THEORY present PE a BU) B33 195 @ Es) 22024 @ Ere)-E02) 3122 @ EMz)-EIM3) 3.946 (6) E(Mi)—E(M3) 15.7163 @ EM)-EM) 148 213 B(M3)—E(Mi) 184165155 culated transition energies at the critical points in the Brillouin zone. According to Table I fairly satisfactory agreement is obtained except, for the ¢-1 transition energies at the M point, which can be observed in the spectrum of the imaginary part of the dielectric function for an electric field perpendicular to the layer plane. The discrepancy in o-m transition energies is found also in the energy band calculation performed by other authors; there might be some problems to be solved in the analysis of experiments. Our band structure shown in Fig. 2 is as a whole very similar to Painter and Ellis’ one® except for the higher part of @ conduction bands. It is to be particularly noted that both our plane-wave-like method and their LCAO one give a similar result as to the band structure of the monolayer graphite. This fact can be regarded to show the reliability of both cal- culations, §4. Slonczewski-Weiss Band Parameters of Graphite The Fermi surface of graphite lies along the vertical edge H-K-H of the Brillouin zone shown in Fig. 3, Slonczewski-Weiss (SW) band model”-®? is usually used for the descrip- tion of the energy band structure near the Fermi surface of graphite and for the analysis of many experiments. The SW model is given by 4x4 effective hamiltonian, which is obtained by the k-p perturbation theory around the H-K-H axis of the Brillouin zone. The wavevector measured from this axis is here denoted by x. The k,1484 Fig. 3. Brillouin zone of graphite, dependence of energy levels is treated by the semi-empirical tight-binding (TB) method. The diagonal elements of the SW hamiltonian ma- trix, namely the energies on the H-K-H axis, are expressed by truncated Fourier series of ke Ex=Aty,0 +4507 yal? (degenerate), ay where [ means 2 cos (ck,/2). This is the de- finition of the SW band parameters 7, Yo, ys and 4. Therefore they can be evaluated through the band calculation on the zone edge H-K-H. Numerically obtained energy bands by the method developed in §2 for (R, E,)= (lla, —272 eV) are shown in Fig. 4, Here 32 fi(2) and 48 two-dimensional plane waves are used in the calculation. As is well known, the P; band in Fig. 4 is nearly half-filled and multilayer graphite behaves as a semimental. Since the order of the characteristic energy for the band structure near the Fermi surface (for example 72) is 10~? eV, energy levels are to be calculated, in principle, in accuracy of this order. Although the accuracy of each energy level in the present calculation is about 0.1 eV, energy differences of various levels are convergent in accuracy of 0.005 eV. The four SW parameters can be determined from the calculated values of Ey, E, and Ey at ck,/2x=0 (K point) and 1/2 (H_ point). The results are y,=0.32 eV, y2=—0.019 eV, ys=0.021 eV and 4=—0.017 eV. The validity of truncation of the Fourier series (11) for Ey is then examined in comparing the actually obtained energies at other k, in the band cal- culation with the energies calculated by the Hideo Nacavosnt, Kenji Nakao and Yasutada Urmuna, (Vol. 41, wi os. 04 02 0.0! -0.2. “0.4 Fig. 4. Calculated energy band structure on the zone edge H-K obtained for (R, F.)=(1.1ag, —272 eV). Energy band Ps is doubly degenerate, truncated Fourier series with the above values of parameters. The errors due to the truncation are found to be less than 0,005 eV. Therefore one can conclude that the truncation for E, in expression (11) is valid for the purpose of analyzing the Fermi surface of graphite. The off-diagonal elements of the SW hamil- tonian are the matrix elements of x-p, which determine the energy dispersion in the k, and. k, directions, They contain the band parameters Yor Js and ),. To determine their values, one is to calculate the energy dispersions in the k, and k, directions and to fit the results to those in the SW model, In principle one should carry out the fitting at many k, and for many directions. For simplicity, however, we carry it out at k,=0 (around the K point) and for a=0 (KI direction) and a=z/3 (K-M direction). Our results are directly connected to the electron Fermi surface. The calculated energy disper- sions near the K point for these directions are shown in Fig. 5, To examine the validity of the SW model and to obtain the values of the band parameters, the following quantities are defined as func- tions of the reduced wavenumber in the ky and k, directions defined by o=(J/3/2)alx|:1976) Band Theory of Graphite. 1. 1485 (E5()- ES AO NES(0) + E5(0)—E}—Es) F*00) 2Ey— (Edo) + ES x0) > © where E#(c) are the energies for the direction a and at the distance from the K point (see Fig. 5). They are essentially the energy dif- ferences E (a) —E¥}3(0) which are the measure of trigonal warping of the electron Fermi surface. They can be evaluated from the results of band calculation, According to the SW model, on the other hand, one can prove that f*(¢) are just proportional to ¢: Sf*()= 2y30. (13) ‘Therefore one can obtain the value of y3 from the slopes of their graphs. Calculated results for f*(c) are shown in Fig. 6. They can be well fitted to straight lines in the region o< 0.06, and their slopes are equal to each other. As is observed in Fig. 5, the value of ¢ on the Fermi surface is less than 0.06. Therefore one can conclude that the SW model is valid at least for the k points inside the electron Fermi sur- face. The value of y, thus obtained is 0.29 eV. Nextly one constructs the following quan- wh | (ese oa, \ Exle) o 0 ~~ "0.06 REDUCED WAVENUMBER Fig. 5. Calculated energy band structure around the K point, Solid and dashed lines correspond to a=0 (K-I' direction) and a=x/3 (K-M direction), respectively. Value of the Fermi energy Ey indicated here is calculated from the SW parameters evaluated later. 0a Fig. 6. Fitting of the functions f*(¢) to the SW band model. The circles indicate the calculated results, and the straight lines correspond to the SW model with 73=0.29 eV. tities g*(o?) as function of 0? 9° (0°) =(Eg (0) — E;)(+2y30+ Eg (o*)—E;). (4) According to the SW model they are pro- portional to a?: 9*(07)=(Yot274)'0?. (sy Calculated results are shown in Fig. 7. They can be well fitted to straight lines in the region ¢<0.06. This is also an aspect of the validity of the SW model. From their slopes yo=2.73 eV and 7, =0.15 eV are obtained. Calculated values of the SW band parameters are listed in Table I. The effective mass parame- ters yo, 7 and 74 can also be calculated from the definition of the SW hamiltonian, namely as the matrix elements of momentum operator taken between the wavefunctions on the Fig. 7. Fitting of the functions g#(o?) to the SW model, The circles indicate the calculated results, and the straight lines correspond to the SW model with yo=2.73 eV and 94=0.15 eV.1486 Table I of graphite. around the K point of the Brillouin zone. Value culation of momentum matrix elements at ok Hideo Nacavosut, Kenji Nakao and Yasutada Urmura (Vol. 41, Slonezewski-Weiss band parameters (Unit eV) and the de Haas periods (Unit 10-* Gauss~*) Theoretical values of yo, 7s and ys in column (1) are obtained by the fitting of energy levels in columns (2) and (3) are obtained through the cal- =0 and 0.5, respectively. Theoretical values by Painter and Ellis (PE)” and by Haeringen and Junginger (HJ)* are also shown for 71,72, 7s and 4. Experimental values are from McClure’s review!” and some periods are after Williamson et al.” 2 e) % 273 269 2.72 n 032 ” =0.019 ” 0.29 029 % ous 4 Ys 0.021 4 0.017 Ee ~0.021 1.65 2.26 recent estimates. Experimental values of the de Haas PE HD 0.28 oat 03 ~04 0.022 0.043 —0.018~— 0.023, 0.2 ~03 0.12 ~0.25 0,003 0.033 0.02 ~0.02 0.09 0.42 0.02 ~0.02 151 2.08 H-K-H axis. One can obtain the value of yo through the calculation at ck,/2n=0.5 (H point), and yo, 73 and 74 through ck,/2x=0 (K point). The results are added in Table II. They are nearly equal to the values obtained in the fitting procedure of energy levels near the K point. Using these theoretical values of the SW Parameters, one can calculate the Fermi energy E;. Then one can obtain the theoretical values of the de Haas-van Alphen (dHvA) periods P, (for electron) and P, (for hole) for the magnetic field perpendicular to the layer plane, by calculating the extremal cross- sectional area of the Fermi surface. The results are also given in Table II. Experimental values of the SW parameters in Table II are after MuClure’s review! and some recent estimates. One may conclude that our theoretical values of the band parameters are in remarkable agreement with experimental ones, if one recalls that the energy levels have been calculated from first principles with the same potential which can also explain optical properties fairly well. For constructing the Fermi surface we have used no adjustable parameters. Finally let us note the signs of the SW parameters. The sign of 7p is meaningless in the SW model, and it is usually taken to be positive. The sign of y, is calculated to be negative, which produces electron Fermi sur- face around the K point and hole Fermi sur- face near the H point. This agrees with the recent assignment used in the analysis of experiments. The parameters 7, and 7, which are usually assumed to be positive on the ground of the tight-binding (TB) picture, are also positive in the present calculation. The sign of 4 is obtained to be negative, namely the level H, is lower than Hy. This fact is important for the minority carrier (hole) which is supposed to be located at the H point. §5. Summary ‘A new method of band calculation has been developed for layer-type crystals. Numeri- cal results for graphite by this method are consistent with experiments in many respects. In particular the experimental results as to the locations of the electron and hole Fermi surfaces and the prominent trigonal warping of the electron Fermi surface have been con- firmed theoretically. The calculated values of the SW parameters are nearly in agreement with the experimental ones. Although one may find smalll discrepancies, between the present results and recent ex- perimental ones in the magnitudes of the SW parameters especially as to yo and »,,* there * Recent experiments are favorable fo large values of ys and 7; (for example y; =3.1 eV and y;=0.40 eV).1976) is no room for doubt in the powerfulness of the present method of band calculation. These discrepancies could be taken off by a careful choice of the parameters in the potential used in the numerical calculation. The present method will predict. many interesting physical properties of graphite from purely theoretical point of view. For example the effect of pressure on the band structure can be studied from first principles through the calculation with various values of the lattice constants. Such studies will be presented in following papers. It is also in- teresting to apply this method of band cal- culation to other layer-type crystals such as GaSe, Bil, and many kinds of transition metal dischalcogenides. Acknowledgement The authors are grateful to Professor H. Kamimura and Dr. M, Tsukada for valuable discussions. Suggestions by Professor M. S. Dresselhaus, Dr. G. Dresselhaus and Professor J. W. McClure are also appreciated. This work was partially supported by Japan Society for the Promotion of Science. Numerical caleula- tions were made on HITAC 8800/8700 at the Computer Center of the University of Tokyo. References 1). R. Wallace: Phys. Rev. 71 (1947) 622. 2) F, Bassani and G. Pastori Parravicini: Nuovo Band Theory of Graphite. I. » 4 » 9 ” 8) 9) 10) w 12) 13) 14) 15) 16) 17 18) 19) 1487 Cimento SOB (1967) 95, G. S. Painter and D. E. Ellis: Phys. Rev. BL (4970) 4747. E, A. Taft and H.R. Philipp: Phys. Rev. 138 (1965) A197. K. Zeppenfeld: Z. Phy. 211 (1968) 391 R. Klucker, M. Skibowski and W. Steinmann: Phys, Status Solidi B65 (1974) 703 4. C. Slonezewski and P. R. Weiss: Phys. Rev. 109 (1958) 272. J. W. McClure: Phys. Rev. 108 (1957) 612. S. J. Williamson, 8. Foner and M. S. Dresselhaus: Phys, Rev. 140 (1965) A1429, H. Suematsu and S, Tanuma: J. Phys. Soc. Japan 33 (1972) 1619; Their experiment was analyzed fon the SW band model by Ushio ef al. (H. Ushio, T. Uda and Y. Uemura: J. Phys. Soc. Japan 33 (4972) 1551). P. R. Schroeder, M. S. Dresselhaus and A. Javan: J. Phys, Chem. 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