Thin Solid Films, 123 (1985) 289 296

ELECTRONICSAND OPTICS

289

S P I N - C O A T E D A M O R P H O U S C H A L C O G E N I D E FILMS: PHOTOINDUCED EFFECTS G. C. CHERN* AND I. LAUKS'~

Center for Chemical Electronics, University o[" Pennsylvania, Moore School of Eh, ctrical Engineering, Philadelphia, PA 19104 (U.S.A.)
K. H.

NORIAN

Department of Electrical and Computer Engineering, 304 Packard Laboratory 19, Lehigh University, Bethlehem, PA 18015 (U.S.A.)

(Received June 11. 1984; accepted November 23. 1984) Photoinduced effects in spin-coated arsenic sulfide films were investigated by UV-visible spectroscopy, X-ray diffractometry, transmission electron microscopy and IR spectroscopy. Reversible effects as well as irreversible effects were observed. The photoinduced decrease in the joint density of states between the conduction and valence bands, which can be recovered by thermal annealing, is believed to be compensated by an increase in the defects in the energy gap. The decomposition, crystallization, oxidation and grain growth of the material under UV illumination were associated with the irreversible photobleaching effect.

1. INTRODUCTION In recent years amorphous chalcogenide thin films have attracted research attention because of their potential in a number of technological applications. Photographic effects on thin film chalcogenide glasses prepared by melt quenching 1"2 or vapor deposition 2-12 have been investigated. Some researchers have reported that the absorption coefficients at the absorption edge and the refractive index of As2S 3 films increase after band gap illumination 1-5. Brandes et al. ~ attributed the transmission loss to an increase in scattering. Keneman 3 suggested that the photostorage of holograms in A s / S 3 thin films can be erased by heat in a reversible reaction. Berkes et al. 4 and Ohmachi and Igo 5 speculated that the photodecomposition resulting in the growth of arsenic clusters in the film is responsible for the photodarkening effect. DeNeufville et al. 2 proposed two kinds of photoeffects: one is a photostructural change, which accounts for the shifts in both the absorption edge and the refractive index and is caused by the polymerization of the as-deposited molecular (As4S 6 or As4Se6) glass through illumination; the other is a photodarkening effect, which accounts for the shift in the absorption edge without a significant change in the refractive index and is caused by excess trapped * Present address: Commodore SemiconductorSystems,950 Rittenhouse Road, Norristown, PA 19403, U.S.A. t Present address: Integrated lonics Inc., 1011 State Road, Princeton, NJ 08540, U.S.A. 0040-6090/85/$3.30 (C),ElsevierSequoia/Printed in The Netherlands

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G . C . C H E R N , I. L A U K S , K. H. N O R I A N

non-equilibrium electrons and holes whose electrostatic attraction constitutes a local deformation and could affect the joint density of lone pair and conduction band states at energies near the optical gap energy. However, Tanaka and coworkers 6 12 found both a decrease and an increase in the absorption coefficient and refractive index of arsenic sulfide films depending on their preparation. The photobleaching effects were attributed to photodecomposition and then oxidation of the film 6' 7. The photodarkening effects were explained by the rearrangement of the atoms within the distance of short-range order through illumination, resulting in a quasi-equilibrium atomic configuration of the system with a shorter average molecular distance s. The dynamic change in the refractive index ofAs~Sloo x fibns induced by band gap illumination, which can be recovered by irradiation at a lower photoenergy, is positive for AsxSloo x, x > 35, and is negative otherwise 9, They speculated that the existence of a defect causing a single broad trap level near the conduction band is responsible for the change in refractive index accompanied by photodarkening effects 9 12. A configuration diagram of a single-well electron excited state and a double-well electron ground state with a barrier height of 0.5-1.5 eV was proposed 11,12 In a number of previous publications 13 17 we have demonstrated that chalcogenide glasses can also be deposited by spin coating from solution. The mechanism of dissolution of chalcogenides in amines (RNH2) has been investigated 13'1~. The results favor a mechanism of dissolution in which the continuous network of the solid chalcogenide is attacked by the amine by the breaking of weak bonds at defect sites with the bond rupture then extending to neighboring bonds in a continuous manner. In this way macromolecules of chalcogenide (with molecular weights of about 100000) are formed. These macromolecules are terminated at their surfaces by - - S - R N H 3 groups. We call this material alkyl a m m o n i u m arsenic sulfide. During bakeout after spin deposition of these materials, R N H 2 was evolved leaving hydrogenated chalcogenide clusters in the solid phase. Further annealing of the material at a higher temperature caused cross-linking of the clusters with release of H2S 15-17 In this paper photobleaching, decomposition, crystallization and oxidation of spin-coated arsenic sulfide films are investigated by transmission electron microscopy (TEM), X-ray diffractometry and IR and UV-visible spectroscopy. 2.
P R E P A R A T I O N OF MATERIALS

For T E M experiments a solution of 1 g As2S 3 in 100 ml butylamine was spun onto oxidized polished silicon wafers at about 5000 rev min 1 for 30 s. This resulted in As2S 3 films 50 nm thick. These were separated from the substrate by immersion in deionized water and were placed onto copper specimen grids both before and after UV exposure. Samples for X-ray diffraction were prepared by dropping some solution of 2.5 g AszS 3 in 10 ml butylamine onto Si(100) substrates and then baking at 40 C for 24 h and at 90 C for 0.5 h in a vacuum oven. This resulted in a film with a thickness of a few tenths of a millimeter. Materials for IR spectroscopy were prepared from a solution of 2 g As2S 3 in

SPIN-COATED AMORPHOUS CHALCOGENIDE FILMS

291

10 ml butylamine by spinning at 2000 rev min 1 for 20 s on KRS-5 substrates and then annealing at 50 C for 100 min. For UV-visible transmission measurements films of As2S 3 0.3 lam thick were prepared on quartz substrates from a solution of 1 g As2S 3 in I0 ml butylamine by spinning at about 3000 rev min - 1 for 30 s. The films were baked at 45 C for 12 h and at 90 C for 0.5 h in a vacuum oven. 3.
EXPERIMENTS AND RESULTS

The thin film morphology was examined with a Philips EM400T transmission electron microscope. Figure l(a) shows the result for the as-deposited material. Clearly resolved were dark clusters corresponding to heavy atoms such as arsenic and sulfur with dimensions of 5-7 nm interspersed among light areas corresponding to light atoms of the intercluster organic content or voids. This agrees with previous results 16. After UV exposure at 12 J cm -2 grain growth and crystallization of the material were observed (Fig, l(b)). Selected area transmission electron diffraction results for the as-deposited material show halos (Fig. 2(a)) corresponding to amorphous material, while the results for the UV-exposed material show sharp spots (Fig. 2(b)) identified as crystalline arsenic (synthetic hexagonal; space group

R3m).

(a)

(b)

Fig. 1. Transmission electron micrographs of butyl a m m o n i u m arsenic sulfide films: (a) as-deposited; (b) after UV exposure at 12 J cm - 2.

X-ray diffraction data were obtained using a Philips diffractometer with Cu K s radiation. Figure 3 shows the results. The unexposed material exhibits three broad amorphous peaks, consistent with the previous results 13. After 4 h of UV exposure a number of sharp peaks corresponding to crystallization of the material appeared in

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C;. C. C H E R N , 1. L A U K S , K. H. N O R I A N

(a)

(b)

Fig. 2. Selected area transmission electron diffraction patterns of butyl ammonium arsenic sulfide films: (a) as-deposited; (b) after UV exposure at 12 J cm 2. tO0

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4o 30 20 20 (deg) Fig. 3, X-ray diffraction spectra of butyl ammonium arsenic sulfide before (exposure at 250 J cm 2.

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UV

a d d i t i o n to the three a m o r p h o u s peaks. Peaks at 20 = 13.7 , 27.4 , 27.9 and 32.3 are identical with t h o s e of m o n o c l i n i c and cubic A s 2 0 3 . P e a k s at 20 = 32.2 , 48.4 and 59.3 c o r r e s p o n d to synthetic h e x a g o n a l arsenic. A l s o s h o w n are unidentified p e a k s at 20 = 20.1 , 35.2 , 39.7 , 42.3 , 46.3 , 55.0 , 57.6 and 64.7 . T h e effect of U V i l l u m i n a t i o n on the IR t r a n s m i s s i o n spectrum was studied

SPIN-COATED AMORPHOUS CH

, COGENIDE FILMS

293

using a Beckman IR 4250 sp,. rometer. Figure 4 shows the IR transmission spectra of the material before and aft ;" UV exposure at about 40 J c m 2. The main change in the IR transmission spect.: um in the range 4000-650cm-~ is the presence of a ,~tcong absorption peak at 800cm -1 after UV exposure, which probably correads t o A s 2 0 3 1 8 . In the range 650-200 c m - ~ the material without UV exposure s a broad absorption peak at 305cm ~ corresponding to antisymmetric st~ ',:hing of the As2S3 unit 19'2, a shoulder at 340cm ~ corresponding to symmetric stretching of the As2S3 unit, and unassigned absorption peaks at 415,479 and 544 cm 1. After UV exposure at about 40 J cm 2 new peaks appear at 565 and 625 cm-~, and there are changes in the absorptions at 305, 340, 415, 479 and 544 cm-~. The absorption peaks at 305 and 415 cm ~ decrease while the absorption peaks at 479 and 544 cm ~ increase, and the shoulder at 340 cm ~ becomes a strong absorption peak which might indicate the decomposition of the AszS 3 network.

1001
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I I I I I 2000 1600 1200 800 600 WAVENUMBER(cm-') Fig. 4i IR transmission spectra of butyl a m m o n i u m arsenic sulfide before ( exposure at 40J cm 2.

20101-

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The results of UV visible transmission measured on a Perkin-Elmer 553 spectr'~photometer are shown in Fig. 5. The inset shows the quantity (~ho~)~/2 plotted against h~o, where h(,~ is the photon energy and ~ the absorption coefficient. The results are in accordance with the often observed band edge behavior in chalcogenide glasses -

B(hoh~o

Eopt) 2

(1)

where Eop I is the extrapolated optical band gap 21. The absorption coefficient was obtained as described previously 16. The extrapolated optical band gap decreases from 2.42 eV for the 45 C softbaked material to 2.33 eV after annealing at 90 ~C, in agreement with the results reported previously 16. After a 72 J cm - 2 UV exposure the absorption edge shifts to higher photon energy showing the photobleaching effect. Further annealing of the sample at 100 ~C for 3 h in a vacuum oven shifts the absorption edge back to lower photon energy. These effects are opposite to those reported by other researchers 1 5. These results do not correspond to a simple reversible photographic effect since the thickness of the material was reduced after thermal annealing t6 and no significant change in thickness was observed after UV exposure.

294

G. C . C H E R N , I. L A U K S , K. H. N O R I A N

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Fig. 5. U V visible transmission spectra of butyl a m m o n i u m arsenic sullide after a sequence of a n n e a l s at various t e m p e r a t u r e s and U V exposure: - - , after a 45 C a n n e a l for 0.5 h; - - -, after a 9 0 C a n n e a l for 0.5h; ,afterUVexposureat72Jcm-2; ..... , a f t e r a l 0 0 C a n n e a l for 3 h,

4. DISCUSSION We have shown that UV illumination on the spin-cast arsenic sulfide film produces photobleaching, crystallization, oxidation and grain growth. On the basis of these results we suggest a model for the mechanism of the photographic effects which is similar to that presented by Tanaka and Kikuchi 6. Decomposition under UV exposure of As2S3 and oxidation of arsenic occur according to the reactions AsES 3 ~ As 2 + As 2 _xS3 4 A s + 302 ~ 2As203 0 < x < 2 (2) (3)

We assume that other unknown reactions associated with the amine salt component of the material account for the unidentified crystallization peaks of the X-ray diffraction spectrum. During the decomposition, the liberation of arsenic atoms is followed by their migration in the film to form small crystals which then oxidize into As203 crystals. These crystals are sufficiently small and scattered in the film that they have almost no effect on the measurement of the overall UV-visible transmission 6. The rest of the material consists of clusters containing amorphous sulfur-rich arsenic sulfide, which is consistent wi)h the shift in the absorption edge to a higher photon energy after UV exposure. This agrees with observations on the

S P I N - C O A T E D A M O R P H O U S C H A L C O G E N I D E FILMS

295

absorption edge of bulk arsenic sulfide glass which shifts to a higher photon energy with an increase in the sulfur content 22. Tanaka and Kikuchi 6 postulated that the incident photons absorbed by the film excite valence electrons from their bonding states and locally produce a weaker chemical bond than the initial unirradiated bond in the network. Since our material has a structure containing clusters, photodecomposition may occur more easily by exciting A s - - S and S--organic bonds at cluster boundaries, and the ensuing reaction is responsible for the formation of unknown crystals and cross-linking between clusters causing grain growth. Further investigation of the film properties is necessary to identify the unknown crystals caused by UV illumination. Although the above photodecomposition, crystallization and oxidation reactions which occur in spin-coated As2S3 films are irreversible, other reversible changes also occur in the films. As shown in Fig. 5, the decrease in the slope of the (oth~o) 1/2 versus h~o plot after UV exposure indicates a decrease in the joint density of states between conduction and valence bands. This decrease in the joint density of states is possibly compensated by an increase in defect states in the energy gap, which we presume to be the same C3 + C1 - pairs discussed elsewhere 17 for the silver photodoping phenomena. The increased defect states may modify the energy band structure near band tails. We believe that this will not influence the value of Eop t which is an extrapolated value based on eqn. (1). This equation is derived by assuming parabolic bands and is valid only for energies not too close to the band tails. The increase in states near band tails should not decrease the "extrapolated" energy gap but should cause an increase in the absorption coefficients in the low absorption region, i.e. at photon energies n e a r Eop t. In this region the change in absorption is difficult to observe in our measurements on thin films because of light interference caused by multiple reflections. However, others have attributed the Eopt decreases of the photodarkening effect to a change in band tail density 9 11. Thermal annealing of the material after UV exposure not only increased the absorption but also increased the slope of the (0~h(t)) 1/2 v e r s u s h~o plot almost back to its original value, This may indicate an increase in the joint density of states with thermal annealing after UV exposure and is believed to be accompanied by a decrease in the defect state density.
ACKNOWLEDGMENTS

The authors would like to thank Drs. S. Rabii, B. Singh and J. N. Zemel for their valuable discussions. This work is supported by the U.S. Air Force Office of Scientific Research under Grant 81-0201.
REFERENCES

1 R.G. Brandes, F. P. Lamingand A. D. Pearson, Appl. Opt., 9 (1970) 1712. 2 J.P. DeNeufville,S. C. Moss and S. R. Ovshinsky,J. Non-Cryst, Solids, 13 (1974) 191. 3 S.A. Keneman,Appl. Phys. Lett., i9 (1971) 205.
4 J.S. Berkes, S.W. lng, Jr.,andW. J. Hillegas, J. Appl. Phys.,42(1972)4908.

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Y. Ohmachi and Y. Igo, Appl. Phys. Lett., 20 (1972) 506. K. Tanaka and M. Kikuchi, Solid State Commun., 11 (1972) 1311. K. Tanaka and M. Kikuchi, Solid State Commun.. 12 (1973) 195. K. Tanaka, Appl. Phys. Lett., 26 (1975) 243. K. Tanaka, Solid State Commun., 28 (1978) 541. K. Tanaka, Solid State Commun., 34 (1980) 201. K. Tanaka and A. Odajima, J. Non-Co,st. Solids, 46 (1981) 259. K. Tanaka, J. Non-Cryst. Solids, 59-60 (1983) 925. G C. Chern and I. Lauks, J. Appl. Phys., 53 (1982) 6979; 54 (1983) 2701. R. Zallen, M. L. Slade, G. C. Chern and I. Lauks, Bull. Am. Phys. Soc., 28 (1983) 327. G . C . Chern, 1. Lauks and A. R. McGhie, J. Appl. Phys., 54 (1983) 4596. K . H . Norian, G. C. Chern and I. Lauks, J. Appl. Phys., 55 (1984) 3795. G . C . Chern, Ph.D. Dissertation, Department of Electrical Engineering, University of Pennsylvania, 1984. A.Bert~uzza,M.A.M~re~iandC.Fagan~LinceiRend.Sci.Fis.Mat.Nat.(~taly~,52(~972)923. G. Lucovsky and R. M. Martin, J. Non-Cryst. Solids, 8 10 (1972) 185. G. Lucovsky, Phys. Rev. B, 6 (1972) 1480. N . F . Mott and E. A. Davis, Electronic Process in Non-Crystalline Materials, Clarendon, Oxford, 1979, p. 29 I. F. Kosek and J. Tauc, Czech. J. Phys. B, 20 (1970) 94.