Solid State Communications, Printed in Great Britain.

Vo1.49,No.9,

pp.867-870,

1984

0038-1098/84 $3.00 + .OO Pergamon Press Ltd.

CORE-EXCITON

INDUCED RESONANT PHOTOEMISSION BLACK PHOSPHORUS

IN THE COVALENT

SEMICONDUCTOR

M.Taniguchi, S.Suga, M.Seki, H.Sakamoto and H.Kanzaki Synchrotron Radiation Laboratory, Institute for Solid State Physics, The University of Tokyo, Tanashi, Tokyo 188. and Y.Akahama and S.Endo High Pressure Research Laboratory, Faculty of Engineering Science, Osaka University, Toyonaka, Osaka 560. and S.Terada and S.Narita High Pressure Research Laboratory and Department of Material Physics, Faculty of Engineering Science, Osaka University, Toyonaka, Osaka 560. (Received 22 November 1983 by H.Kamimura)

Valence band photoemission spectra of black phosphorus have shown anomalous behavior at the excitation of 2p core-excitons. The intensity of the 2.7 eV peak shows a clear Fano type interference due to a direct recombination of core-excitons leaving one hole in valence bands. Besides, strong enhancement of the 10.8 eV peak is interpreted as due to a core-exciton induced resonance with two-hole final states. The role of core-excitons as intermediate states for photoemission processes is newly revealed in the experiments.

The inner core-level spectroscopy is a powerful means for studying final state interactions as well as dynamical many body problems in solids. Core excitations in transition metal and rare-earth systems have been extensively studied by resonant photoemission experiments."2'3 In these systems with narrow bands of d or f electrons, the electron correlation effect is very strong due to localized characters of the core-hole as well as d or f electrons. Accordingly, the observed interference effects have been analyzed so far on the basis of atomic pictures.' In this letter, however, we report resonant photoemission experiments for a covalent semiconductor, black phosphorus(P), characterized by the wide valence bands with rather delocalized The resonances observed for final nature. states with one and two holes in the valence bands at the excitation of the 2p core threshold are interpreted as due to the formation of core-excitons as intermediate states of photoemission processes in semiconductors. The present experiments were performed by making use of synchrotron radiation from SORRING(an electron storage ring operated at 380 A combination of a double stage MeV). cylindrical-mirror analyzer and a modified Rowland monochromator was used to obtain angleintegrated photoemission spectra. Samples were high purity single crystals of black P, whose in situ cleaved a-c plane4 was used for measurements. The working pressure was below l~lO_'~ Torr. Figure l-(a) shows the valence band photoemission spectra of black P measured at various excitation photon energies&w). The spectral intensity is normalized to the incident photon flux. The structures in photoemission spectra for fiw below 129 eV are classified into two 867

Three peaks at EB groups as shown below. (binding energy with respect to the valence band maximum)=2.7, 4.7 and 6.6 eV are due to 3p-orbitals, slightly hybridized with 3sorbitals (hereafter called sp bands). On the other hand, two peaks at 10.8 and ~15.4 eV originate mainly from 3s-orbitals.5 At the excitation near the 2p core threshold (fwfi130 eV), one notices remarkably strong changes of the spectral shape and intensity. The intensity of the peak at EB=lO.8 eV is markedly enhanced without change of its peak position for the excitation between hw129.55 and% Above f1~131 eV, we have observed 130.80 eV. an additional structure on the higher binding energy side of this peak. From the energy shift of the new peak against hw, this structure is assigned to the Lz,sW Auger One can easily recognize that the structure. Ls,sW Auger peak in black P demonstrates the dominance of the p-p process over the s-p or ss final states,6 by taking the energy position and the band width into consideration. For higher hw, the Auger peak is well separated from the valence band structures as shown in Fig.l-(b). Here, the energies of the peak and the low energy threshold of the Auger spectrum are evaluated as 21.7 and 13.5 eV. The spectral shape of the valence band structures in this spectrum is very similar to that for non-resonant excitations below hw=129 eV. Figure 2 shows the intensity(peak height from the zero line) of the structures at EB =10.8 and 2.7 eV as a function of hw. These results are compared with optical spectra. The lower curve of Fig.3 shows the near-normal incidence reflectance spectrum measured with very high resolution(sl00 meV) for the polarization ET//a by use of a Vodar monochromator. The remarkably sharp doublet

CORE-EXCITON

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PHOTOEMISSION

Vol. 49, No. 9

Black P

Black P
I

r-

10.8eV-peak 2.7eV-peak

/ t, f \1 i ),

20

II

11

I
135

125 Photon

130 Energy (eV 1

Figure 2 Plots of 10.8(dashed curve) and 2.7 eV(solid curve) intensities as a function of excitation photon energy.

Black P 20 15 10 5 0 Binding Energy (eV 1 Eli a

BLack P 1

A
I(b),
40

trlu =140.99 w

)-m-m
0.05I

0.18 _ tn r 0.16 !j

)_,
0
I

20 30 10 Binding Energy (eV )

Ju
1 I I I I I I I I

-0.08

Figure 1 (a) Angle-integrated photoemission spectra of black P for excitation photon energy between 120 and 134 eV. The spectral intensities are normalized to the incident The arrows indicate the L2,3 photon flux. VV Auger structure. (b) Angle-integrated photoemission spectra of black P for 140.89 eV photon energy. The L2,3VV Auger peak and its lower binding energy edge are indicated by arrows at 21.7 and 13.5 eV binding energies, respectively. structure at 130.33 and 131.20 eV has been assigned as the spin-orbit partner of the 2p The upper curve of core-exciton structure. Fig.3 shows the partial yield spectrum measured with lower resolution(s1 eV) in the present experiment, where the fine structures of the spin-orbit split components are smeared out. According to the comparison of Fig.2 with Fig.3, one notices that the resonant behavior of the photoemission has strong correlation

125

130 135 Photon Energy ( eV )

Figure 3 Partial yield spectrum(upper) and nearnormal incidence reflectance spectrum taken with very high resolution(lower) for The remarkably sharp doublet ENa. structure at 130.33 and 131.20 eV is assigned as the 2p core-exciton structure. with the core-exciton excitation. First, we discuss the resonance of the ED =2.7 eV peak, whose intensity has shown a Fano type antiresonance with a weak dip and a small hump on the lower and higher energy sides of the 2p core threshold. In this case, the contribution of the L2,aW Auger structure to this antiresonant behavior can be discarded, because the overlap of the tail of the Auger structure with the Eg=2.7 eV peak is negligibly small at the 2p core threshold excitation as judged from the Auger line shape shown before. We assign this clear antiresonance to an

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interference between the direct recombination process of the 2p core-excitons providing kinetic electrons from the 3p bands and the direct excitation process of the 3p valence electrons, which provide the same final state. This direct recombination process is considered to be benefited from the localized character of the core-exciton with a large binding energy.' Although the present type of interference is supposed to take place in the whole valence band region, the interference may be obscured in the higher binding energy region by the overlap with the L2,3W Auger structure as well as by the resonant enhancement of the EB=10.8 eV peak. Now we move to a discussion of the strong enhancement of the intensity of the peak at EB It is clear that this resonance =10.8 eV. takes place when the Lz,~W Auger structure One may conapproaches this energy region. jecture that the intensity of the Lz,jW Auger structure increases when hw-matches the coreexciton excitation energy, since the number of 2p core holes is increased due to the coreThe resemblance of the exciton formation. resonant behavior shown in Fig.2 with the spectra in Fig.3 suggests that this coreexciton Lz,jW Auger process is a candidate for the origin of the observed resonant behavior. In order to check the resonant behavior in more detail, we evaluated the difference spectra by subtracting the non-resonant spectrum at hw The ~126.30 eV from the spectra in Fig.l-(a). difference spectra have demonstrated that resonant enhancement takes place at a constant binding energy around EB=10.8 eV for hw from In addition, the line 129.55 to ~130.80 eV. shape of the enhanced structure is found to be equivalent to the non-resonant Lp,aW Auger peak structure shown before. As is well known, the ordinary L2,3W Auger structure is observable at a constant kinetic energy for the excitation of the 2p On the core electron into conduction bands. contrary, a special situation is realized at The the core-exciton excitation threshold. Auger process under these circumstances is described as 2p6Vn + hw(threshold) + 2p5Vnb' 2p6 v n-2b + el 2p5Vnb' 3 (1) (2)

where Vn represents the valence charge and b' and b denote the conduction electron bound to the photoexcited 2p core hoie and unbound electron around the bottom of conduction bands, The el stands for the kinetic respectively. Auger electron to be detected by photoelectron spectroscopy. One recognizes that the 2p core electron can be excited into the core-exciton band with large density of states at various photon energies which cover the band width due to the life time broadening of the core-exciton state.

Here, the core-exciton life time is dominated by the Auger life time of the core hole state. When the Auger filling of the core hole takes place through the core-exciton Lz,~W Auger process, the core-exciton simultaneously Then, we have one kinetic disappears. electron, one electron around the bottom of conduction bands as well as two valence holes in the final state. Thus, the extent of tiw correlated with the core-exciton band width is directly reflected to the energy of the kinetic Consequently, this core-exciton electron. LP,~W Auger peak is observable at a constant binding energy, because of the energy conserThis type of core-exciton vation rule. induced resonant photoemission process is supposed to be a main source of the resonance.' In addition, there is another weak contribution In the energy region of to the resonance.' the 2p core-exciton excitation, we have always an overlap with a smooth background associated with the excitation of valence electrons to high energy region of the conduction bands. If we consider a direct recombination of these kinetic electrons in the high energy conduction bands with valence holes, the 2p core electrons can be excited into the core-exciton states (this process corresponds to an inverse process of the direct recombination of core-excitons). Then, these core-excitons couple and interfere with the directly excited 2p core-excitons. Here, the 2p core-excitons are possibly excited at hw even below(or above) the core-exciton excitation threshold. By employing appropriate values for the energy positions and band width of the sp bands as well as for the interaction energies, the observed resonant behavior is quite well exThe coinciplained in the case of black P.' dence of EB for the resonant peak with that for upper 3s band is rather accidental in this case. Finally, we have extended these resonant photoemission experiments to the covalent semiconductor Pl_xAsx(x=0.5) mixed crystal with We have observed similar black P structure. resonances at the core excitation thresholds of The binding both As 3d and P 2p cores. energies of the enhanced structures are found to be almost the same for these two different Besides, their spectral shapes excitations. are slightly different to each other. We conclude that the core-exciton induced process, proposed for the first time, is the most probable candidate for the origin of resonance in covalent semiconductors with wide valence bands. Acknowledgement-The authors would like to express their sincere thanks to Prof.A.Kotani, Prof. K.Nasu and Dr.K.L.I.Kobayashi for their fruitful discussions and to staff of Synchrotron Radiation Laboratory for technical support.

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PHOTOEMISSION

vol. 49, No. 9

1) L.C.Davis 2)
(3)

4) 5)

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and S.Narita, Solid State Commun. 4-5, 59 (1983). 6) D.R.Jennison, Phys. Rev. Lett. 4_0, 807 (1978). 7) M.Taniguchi, M.Seki, S.Suga, A.Mikuni, H.Kanzaki, Y.Akahama, S.Endo and S.Narita, Phys. Rev. Ba, 1165 (1983). H.Daimon and Y.Murata, 8) K.L.I.Kobayashi, Phys. Rev. Lett. lo, 1701 (1983). 9) A.Kotani and T.Nakano, private communications; in preparation for publication.