Physica 138A (1986) 557-572 North-Holland, Amsterdam NONEQUILIBRIUM GREEN’S FUNCTIONS AND KINETIC EQUATIONS FOR HIGHLY EXCITED SEMICONDUCTORS II. APPLICATION TRANSPORT TO THE STUDY OF NONLINEAR OPTICAL AND PROPERTIES OF THE MANY-EXCITON SYSTEM K. HENNEBERGER, Sektion MathematiklPhysik der Piidagogischen G. MANZKE, Hochschule GDR V. MAY “ Liselotte Herrmann”, 2600 Giistrow, R. ZIMMERMANN Zentralinstitut fCr Elektronenphysik Hausvogteiplatz der Akademie der Wissenschaften 5-7, 1086 Berlin, GDR Received 17 December der DDR, 1985 Nonequilibrium Green’s function technique is applied to the many-exciton system under the action of an externally driven light field. Starting with Dyson’s equation for the nonequilibrium exciton propagator the shift and damping of exciton-levels due to exciton-exciton interaction are calculated in a local approximation with respect to the density of excitons. As a consequence, the Boltzmann equation of excitons contains many-exciton contributions in the diffusion- and driftterm as well as in the collision integral. The corresponding diffusion equation is derived yielding a diffusion coefficient decreasing with increasing density and a density dependent source term due to the action of the light field. Numerical calculations are carried out for A,_,-excitons of a CdS platelet considering a two-beam as well as a one-beam experiment. For the two-beam case we present the density-profile resulting from nonlinear diffusion and the corresponding reflection spectrum around the A,=,-level. For the one-beam case solving the diffusion equation and Maxwell’s equations simultaneously an optical bistability just below the Mott-transition is predicted. 1. Introduction In highly excited direct semiconductors the intermediate density region, where individual excitons are present but already strongly interacting, is still a matter of actual interest. Due to material specifics and experimental conditions there is an interference between different complications in this case: (1) many particle interaction including, e.g., Mott transition; (2) resonant, i.e. far from equilibrium excitation of excitons; (3) spatially inhomogeneous; and (4) non0378-4371/86/$03.50 0 Elsevier Science Publishers B.V. (North-Holland Physics Publishing Division) 558 K. HENNEBERGER et al. stationary behaviour. Even as a consequence of this interference several interesting phenomena, as e.g. optical bi- or multistability and domain formation and migration can be expected and has been discussed in a more or less phenomenological way ’ ‘“). In this paper we are going to describe the optical and transport behaviour of a dense gas of excitons starting with a consequent microscopic approach. In section 2 the nonequilibrium Green’s function technique3’4.5’6) is applied to the electron-hole pair propagator yielding a Dyson equation governing the spectral and kinetic behaviour of the exciton gas’). The self-energy diagrams are considered up to second order in the Born collision approximation7’x) and the Dyson equation is approximated up to first order derivatives concerning the local variables r = (r, + r,.)/2 and t = (t, + t,,)/2 4,6) . Instead of completely solving the kinetics a local thermodynamic equilibrium is assumed and with this in section 3 the local spectral properties of excitons, i.e. density dependent energy and damping, are calculated within a quasiparticle approximation up to first order in the exciton density’.‘). In section 4 the electromagnetic field is explicitely taken into account semiclassically”). An externally driven light field obeying Maxwell’s equations is introduced leading to a corresponding source term in the exciton kinetics. Light propagation as well as exciton generation are governed by a nonequilibrium, i.e. local density dependent dielectric function E(W, n). In it as well as in the drift and field terms of the Boltzmann-like transport equation all quantities involved, as e.g. velocity and force fields, occur renormalized due to the density dependence of exciton parameters. Correspondingly the well-known diffusion approximation leads to a density dependent diffusion coefficient D(n). Due to Van der Waals attraction between excitons D decreases with increasing density and becomes even negative at densities well below the Mott condition. In section 5 numerical results for CdS concerning unusual diffusion behaviour as well as nonlinear optical properties are given”). Beside the limiting cases of hindered (D = 0), low density (D = Do) and effective (D = 00) diffusion the cases of “near resonant” and “far from resonant” excitation are shown, whereby an optical multistability is indicated in the former case. 2. Nonequilibrium Green’s function technique Following7.‘) the nonequilibrium two-time electron-hole pair propagator (1) GREEN’S FUNCTIONS FOR EXCITED SEMICONDUCTORS II 559 is introduced, where e’ (h’) denote electron (hole) creation operators in the Heisenberg representation, 1, (lh) comprise electron (hole) momentum k, (-k,,) and spin S, (-s,,), (Y,p equal to + (-) denote positive (negative) branch of the double time contour3*5X6), and (. . *) means expectation value of operators time-ordered along %. By inspection of the equation of motion hierarchy a Dyson equation has been established in ref. 7 for the exciton representation of the electron-hole pair propagator c j-d2 (Gz-‘(1,2) Y - &,(l, 2))G,,(2,1’) = &(l, 1’). In it G represents the full exciton propagator, G,’ the inverse of the single exciton propagator and on the rhs F contains beside a &contribution also Pauli-blocking factors resulting from real occupation of electron (hole) states (phase-space occupation factor). 1 is the shortening for the quantum number LYE of internal exciton state, wave vector k, and time rl. The self-energy 2 will be considered within the second order Born collision approximation with respect to the exciton-exciton interaction. It is diagramatitally shown in the electron-hole pair representation in fig. 1. Note, that the diagrams contain in each order a direct as well as an exchange contribution with respect to electron-hole pairs. Furthermore, the r-vertex comprises a direct interaction between all electrons and holes involved minus the same but with electrons exchanged. By this electron, hole and electron-hole pair exchange is included in a consistent way. In order to separate the matrix Dyson equation (2) into a spectral and a kinetic part we write it by components: Fig. 1. First and second order self-energy diagrams of the electron-hole pair propagator K. The r-vertex comprises the direct interaction between two electron-hole pairs as well as the interaction combined by electron exchange. (r* follows by shifting the electron exchange from the left to the right of the y-boxes.) The Coulomb-interaction of the electron and the hole is contained in the y-vertex. 560 K. HENNEBERGER d2 (G,‘(l, d2 W,‘(L et al 2) - s(ret’adv)(l, 2))GCretiadv)(2, I’) = ~(1, 1’) , 1’) - Z”(1, 211-Z;‘,“;,GZ(2, , 2)GCad”(2, I’)} = 0, where the propagators G = G _ + , G < = - G + _ and retarded (advanced) functions G cret) = G,, + G+_ (Gcad”) = G - G _+) have been introduced. As has been demonstrated explicitly+& refs. 6, 7, 9, 10 we introduce in (3) and (4) the variable set (kwrt) instead of (1, 1’) and assume all characteristic functions to be slowly varying with respect to the local variables (rt) and diagonal with respect to cz (characterizing the internal state of excitons). Then the solution of (3) exact up to first order in the derivatives (Vr , d ldt) is G(ret’adv)(A, W) = F(A) /(fiw - H(ret’adv)( A, w) + i&) (A = ok, rt) (5) (for the proof see ref. 6), which determines locally the spectral properties supposed the self-energy to be given. H is an effective exciton hamiltonian defined by the single exciton energy E,, and the self-energy zPet’adv)( A, w) = E,,(ak) + 2 (ret’adv)( A, w) . (54 With the same procedure applied to (4) we arrive at an equation for G”( A, 0) (see (3.2,6) of ref. 6) representing a kinetic equation for excitons supposed the selfenergies Z “(A, w) to be given. We renounce giving this equation explicitly, because it will not be used in this general shape. Instead we introduce in the next section the quasiparticle approximation for the spectral part and the local equilibrium for the kinetic part. The corresponding approximations of (4) will be given in section 4. 3. Density dependent exciton parameters In the following we consider the spectral problem (5) within a quasiparticle approximation, i.e. we expand the self-energy at the poles of the retarded propagator G”““( A, o), E,(A) - iT( A) 12 = H’““( A, W)(~o=E,-i~/Z , (6) defining locally the renormalized energy E, and damping r. In the self-energy all diagrams of fig. 1 are to be taken into account. GREEN’S FUNCTIONS FOR EXCITED SEMICONDUCTORS 561 II By inspection of the corresponding analytical expressions, which are given e.g. by eqs. (29) of ref. 7, one realizes the spectral problem (6) to depend on the solution GZ(A, w) of the kinetic equation. Therefore we consider the kinetic problem in the following way. First we introduce a frequency dependent distribution function cp(h, w) by the ansatz G’(A, w> = @A, o>(l + cp(A, w)), G’(A, w) = G(A, o)cp(A, w) . (7) Here the spectral function G = G’ - G’ = G”“” - GCad’) has been introduced, which is in the quasiparticle approximation given by G( A, o) = -iF( A)T( A)l((no - E,(A))* + r2( A) /4) . (8) Let the damping in the spirit of a quasiparticle picture be small enough and, hence, the spectral function very well localized. Then upon integration over frequency G’( A, 0) reduces to the Wigner-distribution of excitons NJ A) = -1 z G<(A,w> =~(A)cp(A,41nm=4 (9) and, at the same time, the kinetic equation for G’( A, w) reduces to the one for the Wigner-distribution = ; s:‘(A, dlfiw=& + N,(A)) - $S’(A, w)j,,=,XNX(A). (10) Note the occurrence of the renormalized energy E, in the definitions of group velocity V,E,ln, force field -V,E, and in the collision terms of (10). Especially even when an external scalar field is absent an internal force may be created by the gradient of the exchange and correlation contributions of self-energy to the quasiparticle energy E,. Such contributions have been introduced intuitively, e.g. in ref. 12. For the time being, we renounce solving e.g. (10) with respect to the k-dependence of N,(A). Instead we suppose a local thermodynamic equilibrium for excitons produced by an efficient scattering either with each other or with phonons. Furthermore we assume a unique global temperature T* characterizing this local equilibrium, i.e. we neglect thermodiffusion at all. In this case the Wigner distribution (9) reduces further to a Bose distribution. In all cases considered here we use a Boltzmann distribution for excitons over the 1s ground state only, 562 K. HENNEBERGER et al (11) In consequence of this assumption we can use the results of refs. 7, 8, 9 for the self-energy, where the homogeneous exciton density there is to be understood as the local one in our connection. The local exciton density n(rt) has still to be determined, of course by the kinetic equation (10) summed up over ak. This will be done in the next section for the more general case, where the exciting light source is explicitly taken into account. 4. Explicit consideration of light source in kinetics Till now we neglected simply the coupling of electrons and holes to the transverse electromagnetic field. It is well known, however, that this coupling is essential in several respects even in highly excited direct semiconductors. Generally it affects the spectral properties as well as the kinetic behaviour. In subsequent papers13’14 a systematic approach to related problems as, e.g., to the propagation of intense laser light in the interband frequency region’5”6 and to the kinetics of polaritons and light scattering”“’ will be given. For the investigation to be made here we take into account the transverse electromagnetic field semiclassically, i.e. by adding an external perturbation 2 E(k, t)P:(k, &x,(t) = - ; k (12) t) to the Hamiltonian, where P, is the interband or excitonic polarization operator and E is the electric field strength obeying Maxwells equation ($+c’k’)E(k,t)=-4 T $ (Pdk, t) + (P,(k, In (13) P, = x,E represents a background introduced. Now the whole formalism developed here inclusion of (12) in the Hamiltonian and the the simplest case, i.e. if we neglect the effect ation at all, the result is very easily understood polarization holds from (P,(k 4) = c 1dt’ ,C(kt, k’t’)E(k’t’) k’ , t))) polarization (13) phenomenologically has to be supplemented by the investigation of (P,) in (13). In of E on the spectral renormaliz(for the details see ref. 10). The (14) GREEN’S FUNCTIONS FOR EXCITED SEMICONDUCTORS II 563 where + Gcad’)(a- k’t’, a’ - kt)) (15) ( p, - transition dipole moment of excitons) looks, indeed, like a linear response susceptibility; it depends however via the self-energies in e.g. (5) on the on density-dependent exciton kinetic stage, i.e. in our approximation parameters. The kinetic equation (4) has to be supplemented by replacing -W, 2)+P(l, 2) + Zrad(l, 2) ) (16) where the radiative self-energy 2rad(1, 2, = ; j- d3 F(1,3)$(3)8*(2) (17) with is to be added. &ad in (16) describes the action of light as a source in exciton kinetics. If one introduces (16) into (4), the kinetic equation (10) is transformed into = P(A) - (y +1) &(A) + Rcinto)(A) . (19) ret In the rhs of e.g. (19) P(A) represents a generation rate for excitons formulated with Srradand 6. The second term gives the net rate of scattering out of the state c& (here an additional recombination contribution is phenomenologitally considered), whereas the third term is the spontaneous scattering into the state czk. In the following we refer mainly to the locally defined density of excitons, (20) 564 K. HENNEBERGER for which a balance equation is obtained $ n(rt) + V&t) et al. by summing up (19) over ak, = p(rt) - n(d) h,,, . (21) In (21) the collision contributions of (10) due to exciton-exciton interaction have cancelled in consequence of the k-integration. VJ results from integrating the drift and field terms of (lo), where the excitonic current density is given by (22) The generation rate for excitons reads explicitly as (23) In (23) 6 is to be understood as acting via its arguments k and o as a differential operator on the Fourier-transformed version of (18) (8 contains additionally the factor F). 5. Approximative treatment of basic equations If a macroscopic homogeneous and stationary situation is realized, the kinetic equation (19) simplifies essentially (vanishing of the Ihs) and can be better solved directly without regarding (21). This has been done for the cases of a macrooccupation (resonantly excited) and a completely relaxed Boltzmann distribution of excitons in ref. 10. Now we consider the still stationary but spatially inhomogeneous case. Then Maxwell’s equation (13) and the kinetics (19) have to be solved simultaneously. Concerning the former one spatial dispersion effects in (14) will be neglected and, hence, (13) becomes for a monochromatic, linear polarized wave of frequency w: E = d?(r) x exp(-iot) + c.c., A&r) + $ E(O, n(r))&) =0 . E = 1 + 47rx follows from (15) in the stationary, local approximation, using (5) in the vicinity of the 1S excitonic ground state, e(k = 00, r) = F=l+:n. E, ( l- or explicit AEd fiw - HcTet)(a = 1Sk = 00, r) > ’ (25) GREEN’S FUNCTIONS FOR EXCITED SEMICONDUCTORS II 565 In (25) the background dielectric constant E,, the longitudinal transverse splitting AE,, and the locally density dependent effective exciton hamiltonian have been introduced. In the density region of interest the consideration of Pauli-blocking (factor F, a,-Bohr radius of excitons) is not necessary (see ref. 10). Concerning the exciton kinetics, the rhs of e.g. (19) is considered in a relaxation time approximation, whereas on the Ihs N, is approximated by its local equilibrium shape (11). Thus, the deviation SN, = N, - Nr’ follows according to 6N f V,E,V, - V,E, ; V, Np’ = ---L 7relax ’ (26) (27) Now the results of refs. 8, 9 for density dependent used up to first order in their density dependence, E,(lSR, r) = E,,(lSk) r(lSk, exciton parameters i.e. - an(r) , r) = r, + j+r(r) . (28) (29) If then (28) and (29) are used in (26) and (17) and the corresponding inserted into (22), one finds a generalized diffusion approximation where the density dependent will be SN, is diffusion coefficient is given through D(n) = L&(1 - anlk,T*)/(l + m/r,> (31) with D, = hk,T* /2M& (32) the low density diffusivity. It is interesting to note, that D decreases wth increasing density and can even become negative if the density becomes sufficiently high. This tendency is produced mainly by the red shift (28) of the exciton energy and reflects the fact, that the corresponding Van der Waals attraction acts against diffusion in order to contract the excitonic gas into a liquid (dielectric) state. K. HENNEBERGER 566 Having e.g. (30) for the current, equation (19) the balance equation approximate still the generation rate the interband dielectric function and et al. we can solve instead of the Boltzmann (21) for the local density. In (21) we (23) consistently with expression (25) for obtain P(r) = Im E(O, n(r))I@r)12/7rtc , with again w the frequency 6. Numerical (33) of the incident monochromatic light wave. results for CdS and discussion We present numerical results for A,,,-excitons of a CdS-platelet of thickness d. Assuming the spatial inhomogeneity in x-direction only, we have as basic equations d%(X) + 02E(0, n(x)) 2J%) dX2 C ; ( dn(x) dx w+)) ) + =0 ) (34) 1%912 Im E(O, n(x)) 7 44 o - 7 = , ret (35) which have to be solved simultaneously with the well-known boundary conditions. Previous results to this problem have been published in ref. 19, to which we refer for further details. In contrast to ref. 19, where density dependencies in (34) and (35) have been considered only in the damping r of the dielectric function E, the real part of self-energy according to (28) and the diffusivity according to (31) will be taken into account too. The parameter set used in numerics is given in table I. Note that our density linearized theory predicts for that set of parameters the Mott-transition at about n = 4 X 1017 cmp3 ‘). First we discuss a two beam experiment, where the platelet is non-resonantly excited by e.g. interband absorption and probed near the exciton resonance. TABLE I 2 =0.2 T*=30K II E, = AE,, 8 = 1.9 meV E,,= 2.5528 eV r, = 0.2 meV if = 3.63 X 10-l’ cm3 meV 7 = 4.06 x 10-l’ cm3 meV 7_ = 0.5 x w9 s L=e==0.5p.m GREEN’S FUNCTIONS FOR EXCITED SEMICONDUCTORS II 567 Then the generation rate in the diffusion equation (35) does not follow from solving (34) but corresponds essentially to the absorption profile of the interband excitation, which has to be used as an input in (35). In fig. 2 density profiles for a generation rate of excitons p(x) = Zo~pe-“~” (1 laP = 0.1 km) are shown in dependence on different excitation intensities (in photons per cm2 and sec.) and compared with those of conventional diffusion (D = Do). Because D is decreasing with n, the diffusion profile becomes more pronounced near the x = 0 plane at higher Z,, and, correspondingly n(0) and n(d) deviate increasingly from their conventional values (inset). The reflectivity spectrum, fig. 3, exhibits essential differences from the conventional one (a) as \ \ I 9” 16 i.. 0 4 .5 k-(m)- Fig. 2. Diffusion profile in the case of nonresonant pumping for different pump intensities Z0 (in 10zl cmW2 s-l). Absorption length of the pump beam 0.1 pm. Inset shows the density at the forward (x = 0) and backward (x = d) surface of the platelet in dependence of I,,. - - - - D = D,; D = D(n). K. HENNEBERGER 568 et al. Fig. 3. Pumped reflectivity for different diffusion profiles (l/a, = 0,l pm; I, = 2.5 X lo*’ cm-‘s-l) (a) D = D,; (b) D = D(n); (c) constant density of 1.25 x 1Ol6cmm3 (the arrow indicates the shifted exciton position). well as from the homogeneous one (c). This results from averaging over local density dependent resonance energies of the exciton. Similar behaviour as that of curve (b) cannot be obtained by an effective damping constant because of the presence of interference structures. For similar transmission spectra we refer to ref. 22. In the remaining we consider a one-beam experiment with frequency of incident light 3 meV below the 1s exciton resonance. If diffusion is neglected at all (D = 0) we arrive at a local connection between n(x) and the light intensity Z(X) = c@(X)[*/AJ. From (35) follows in this case locally n=ZwIm.z(~,n)lc. (36) This dependence is shown in fig. 4 and compared with the case of very effective diffusion (D-+w), where the exciton distribution becomes homogeneous, i.e. n(x) = const. and IZcan be obtained from the incident intensity I,, simply by the conservation law - n 7ret = 2 (1 - R(n) - T(n)) (37) derived in ref. 19 (R (T) - reflectivity (transmission) of the platelet). Corresponding curves for d = 0.1 pm and d = 1 pm are shown also in fig. 4. It is seen that diffusion tends to destroy the bistable behaviour obtained for D = 0. The numerical solution of the complete system (34), (35) has been obtained in nearly the same way as it was done in ref. 19. In fig. 5 the profiles of density GREEN’S FUNCTIONS FOR EXCITED SEMICONDUCTORS II 569 29 22 23 20 Fig. 4. Exciton density in dependence of Z0for nearly resonant pumping (60 = E,, - 3 me? The curve labeled with “local” shows the local IO-dependence of 12(D = 0). The two other curvesstand for the case of very effective diffusion (D = m) and different platelet thicknesses d. and current of excitons for a fixed incident intensity Z,,are given and compared with those for conventional diffusion (D = DAO).Here the modulation of j corresponds to the interference structure of /E(x))’ and, hence, compensates structures in the shape of n. The difference between both cases, i.e. the influence of unconventional diffusion, is evident. Fig. 5. Density and current profile within the platelet for resonant pumping (fiw = E,, - 3 meV, z0 = 5 x 102’ cm-’ s-l); - - - D = D,; D = D(n). K. HENNEBERGER 570 et al. Fig. 6. Transmitted intensity I, versus incoming intensity IO for fiw = E,, - 3 meV. - - - D = m (constant n); D = D(n) (cross-line indicates vanishing of D(n)). Fig. 6 shows the transmitted versus incident intensity and represents the main result of this section. The characteristics resulting from a fictive homogeneous exciton density (dashed line) exhibits already bistable behaviour. This is amplified in the real characteristics (full line) where additional loops appear due to interference structures. Unfortunately, the curves in fig. 6 are reasonable only up to a definite intensity I,, (see mark in fig. 6) where the diffusion coefficient becomes zero and negative according to (31). After that intensity the numerics zero and negative according to (31). After that intensity the numerics failed to produce a stable solution. We expect nonstationary behaviour of density e.g. movement of domains as has been discussed, e.g., in ref. 20 for another physical situation. In order to continue the curve further the calculations were done with a fictious small but positive diffusion coefficient of D,l 100. 7. Concluding remarks In this paper a straightforward way from the microscopic quantum mechanical equations to observable nonlinear effects in optical and transport properties of the many exciton system has been presented. Thereby it was the main purpose to demonstrate the ability and power of the nonequilibrium Green’s function technique in principle rather than to obtain rigorous results. Thus a lot GREEN’S FUNCTIONS FOR EXCITED SEMICONDUCTORS II 571 of approximations were to be used in order to get the formalism tractable. One can divide them into two groups. The first group is related to the general theoretical framework and should be accepted here as standard without further inspection. Such standard approximations are, e.g., the derivation of Dyson’s equation, Boltzmann and other transport equations (linear in the differential operator L3) 6), evaluation of spectral functions, self-energies, etc. The second group of approximations concerns more directly the system under consideration and has to be viewed more critically, because they influence the numerical results remarkably. First the evaluation of the selfenergy linear in density fails certainly at excitation intensities high enough. Also the numerical evaluation of the corresponding graphs in refs. 7, 8 is not yet conclusive enough to believe the red shift predicted by (28) to be correct. The neglection of biexciton formation at all might be also questionable. Due to the induced absorption process excitation energy can be accumulated in the biexciton subsystem leading to important modifications of exciton kinetics. 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