Correlation of Raman and photoluminescence of porous silicon

R. Tsu H Shena) and M Dutta

spectra

University of North Carolina at Charlotte, Charlotte, North Carolina 28223 U.S. Army Electronics Technology and Devices Laboratory, Fort Monmouth, New Jersey 077034601

(Received 13 September 199 1; accepted for publication 6 November 199 1) The discovery of luminescence in electrochemically etched porous silicon is an extremely important scientific breakthrough with enormous technological implications. It opens the door for silicon, the most important microelectronic material, as a possible material for optoelectronics applications. Our result, a correlation of Raman and photoluminescence spectra, shows that the observed luminescence is originated from extremely small microstructures. As the luminescent peak increases in photon energy, the Raman feature shifts to lower energy, remaining sharp, and eventually splits, developing into TO and LO modes. No peak at 480 cm- is observed, which indicates no substantial contribution from an amorphous region. These data provide strong evidence of the role of microstructures in porous silicon. A year ago in March, Lehmann and Gosele submitted their work to Applied Physics Letters on the optical absorption of microporous silicon by electrochemical etching in an electrolyte consisting of a 1:l ratio of ethanol and HF. They observed the upshift of the apparent absorption edge from 1.1 eV, the indirect gap of crystalline silicon, to as high as 1.76 eV. This was attributed to the dramatic two-dimensional quantum-confinement effect in quantum wires. Independently and shortly afterwards Canham reported the striking room-temperature luminescence spectra of microporous silicon having a peak position of 1.58 eV with a luminescence efficiency far greater than the usual phonon-assisted transition. The observation of luminescence in microporous silicon is also attributed to quantum confinement of needlelike structures having a diameter in the order of 30 A. Very recently electroluminescence3 in the visible range was observed during the anodic oxidation of porous silicon. This is an extremely important scientific breakthrough with enormous technological implications, since it opens the door for silicon, the most important microelectronic material, being useful for optoelectronics applications. There appears to be an important fundamental issue, which is the role of momentum conservation in optical transitions in indirect band-gap semiconductors. Crystalline silicon has a conduction-band minimum at the A point of the Brillouin zone (BZ), while the valence-band maximum is at the zone center of the BZ. With an indirect energy gap of 1.1 eV, crystalline silicon is not expected to emit light in the visible. Using the Heisenberg uncertainty principle, a microstructure of 30 A is not small enough to significantly relax the momentum conservation allowing transition without the assistance of phonon. Therefore, one possible origin of the 1.7 eV is from the pseudo-direct gap of amorphous silicon (a-Si). With a large surface-to-volume ratio in the highly porous structure, it seems likely that the significant fraction of the surface tissue region
L GEO-Centers, Inc., NJ. Operations, Lake Hopatcong, NJ 07849. 112 Appl. Phys. Lett. 60 (l), 6 January 1992

being amorphous is responsible for the observed luminescence. Although the transmission experiment of Lehmann and GBsele does support the bulk behavior, a careful Raman study of the phonon structure should provide added support to the bulk phenomena. In this letter we present a correlated Raman and photoluminescence (PL) study of microporous silicon. The downshift of the Raman peaks correlated well with the upshift of the photoluminescence peak; a splitting of the LO and TO phonon was also observed in a sample with the highest observed luminescence peak located at 1.86 eV. The average size from the splitting data was deduced to be in the order of 20 A. The present experimental results discard the possibility of the luminescence from the a-Si surface tissue region, since it is difficult to understand why such a correlation would exist for a-Si. Single-crystalline silicon wafers (5 a cm, p type) were etched using the procedures described in Ref. 1. The best results (judged by the intensity of photoluminescence) were found to be similar to the condition given, i.e., 55 mA/cm2 electrochemically etch in an electrolyte of one to one 98% ethanol and 48% HF. All samples were etched for 20 min at room temperature. The surface of the etched sample looks brown. Although reasonable care was taken to insure a uniform etch, such as keeping the sample parallel with the platinum screen, however, due to the presence of a meniscus and possible bubbles, some nonuniformity was noticeable near the top of the meniscus. All optical measurements were made at room temperature, using an Ar + laser as an excitation with a wavelength at 4579 A. The power used was 50 mW. Samples were mounted on an X-Y stage. Both Raman and photoluminescence spectra were taken at the same spot and during the same run. At each spot, three spectra, parallel, crossed polarized4 Raman, and unpolarized PL, were taken. In contrast to the reference silicon, Raman scattering from the porous silicon was unpolarized, indicating a complete breakdown of the polarization selection rules for
@I 1992 American Institute of Physics 112

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s 1 I .B z H a

I.8

2 Photon Energy (ev)

2.2

2.4

FIG. 1. Room-temperature photoluminescence spectra from porous silicon: A, B, C are the spectra taken at different spots of one sample.

(100) surface. In fact, the walls of porous silicon have orientation other than (loo), which definitely voids the ( 100) polarization selection rules for Raman signal. Therefore, only the crossed polarized Raman spectra were discussed below. Spectra (both Raman and PL) from different spots were different, especially near the top of the meniscus. Luminescence from regions on the sample closer to the meniscus usually peaked at higher energy, indicating a smaller average size of the microstructure. Shown in Fig. 1 is the PL spectra from three different spots of one sample. Spectrum A with a peak at 1.65 eV was taken at a point farther away from the meniscus, while spectrum C with a peak at 1.86 eV was taken from a spot close to the edge of meniscus. Spectrum B was taken in between. During the electrochemical etch, the electric field lines made an angle to the (100) surface of the wafer within the meniscus, and then presumably resulting in smaller microstructures. The detailed mechanism of this phenomena is not fully understood. Figure 2 gives the Raman spectra of the same sample at spots A and C. Also plotted in Fig. 2 is the Raman

7;
c-Si

~
490 500 510 520

i\ x10 I' I \I I

530

Raman Shift (cm- )

FIG. 2. Room-temperature Raman spectra from porous silicon (solid lines) and crystalline silicon (dashed line): A, C were taken at different spots of one porous silicon sample. 113 Appl. Phys. Lett., Vol. 60, No. 1, 6 January 1992

spectrum from reference crystalline silicon, which is peaked at 522 cm ~ 2 and has a full width at half maxima (FWHM) of 3.0 cm - I. Raman intensity is 10 times stronger from porous silicon than from crystalline silicon, perhaps due to the surface enhancement5 or resonance effect,6 which is under further investigation. The peak position of PL from sample A shifts downward by more than 3 cm -. . At spot C the Raman peak further shifts to 5 18 cm - and shows an additional peak at 510 cm r. All the Raman peaks from porous silicon remain reasonably sharp (FWHM = 5 cm - ) . The reason that Raman peaks shift to lower energy for smaller microstructure is due to the confinement of optical phonons. A finite particle size I corresponds to a momentum q = f2~/1. Therefore, the position of the Raman peak reflects the position of the phonon dispersion at q = =l=2r/Z. For large structure, q = 0, hence only the zone center phonons are allowed in Raman scattering. Since the optical phonons (LO and TO) of silicon are degenerate at q = 0, only one peak at 522 cm - is seen in the Raman spectrum for crystalline silicon. If q#O is allowed, then it should be possible to observe both LO and TO provided that the linewidth is narrower than the separation of the LO and TO phonons. With silicon, for LO = 5 18 cm - and TO = 510 cm - , phonon dispersion7 gives I= 20 A. However, simple momentum relaxation modelsY9does not predict this behavior. For example, in a PC-silicon of characteristic size 20 A, the broadening parameter8y9 is FWHM = 13 cm - , which is too large to observe the separated LO and TO phonons in Raman spectra. In addition, we did not observe a broad peak at 480 cm- , indicating that there is no substantial contribution to the Raman intensity from possible a-Si in the tissue region near the surface. These facts indicate that the microstructure is surprisingly free of disorder. Our conclusion supports the basic model promoted by Refs. 1 and 2, that the source of the luminescence is due to the quantum confinement of microstructure having a characteristic dimension of 20-30 A. Originally the origin of the 1.7-eV pseudo-direct gap of a-Si was attributed to the I-L gap of c-S& and the luminescence in the porous silicon was attributed to the same origin. We want to state with emphasis that our present experiments have dispelled this model. Simple application of the Heisenberg principle does not allow significant optical transitions even for a 20-W microstructure. However, in forming quantum confinement, enough mixing of states occurs for different k, making the optical transition possible. In conclusion, we have presented a correlated Raman and photoluminescence study of porous silicon made by electrochemical etching. As the luminescent peak increases in photon energy, the Raman feature shifts to lower energy, remaining sharp, and eventually splits, developing into TO and LO modes. No peak at 480 cm ~ is observed, which indicates no substantial contribution from an amorphous region. These data provide strong evidence of the existence of microstructures in the order of 20-30 A. The work of R. Tsu was performed at the U.S. Army ETDL, Fort Monmouth, under the sponsorship of the Scientific Service Program of GEO-Centers Inc. His work is
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also partially supported by AR0 and NOR. We are grateful to U. G6sele for helpful discussions, and to R. Zeto and R. Piekarz for their assistance in electrochemical etching.
V. Lehmann and U. Gijsele, Appl. Phys. Lett. 58, 856 (1991). L. T. Canham, Appl. Phys. Lett. 57, 1046 (1990). s A. Halimaoui, C Oules, G. Bomchil, A. Bsiesy, F. Gaspard, R. Herino, M. Ligeon, and F. Muller, Appl. Phys. Lett. 59, 304 (1991). See, for example, E. Anastassakis, in Dynamical Properties of Solid, edited by G. K. Horton and A. A. Maradudin (North-Holland, Amsterdam, 1982), Chap. 3.

5See, for example, A. Otto, in Light Scattering in Solid Iv, edited by M. Cardona and G. Guntherodt (Springer, New York, 1984), p. 289. 6See, for example, M. Cardona, in Light Scattering in Solid II, edited by M. Cardona and G. Guntherodt (Springer, New York, 1982), p. 19. G. Nolsson and G. Nelin, Phys. Rev. B 6, 3777 ( 1972). *H. Richter, Z. P. Wang, and L. Ley, Solid State Commun. 39, 625 (1981). 9R. Tsu, S. S. Chao, M. Ize, S. R. Ovshinsky, G. J. Jan, and F. H. Pollak, J. Phys. (Paris) 42, 269 (1981). J E. Smith, Jr., M. H. Brodsky, and D. Weaire, Phys. Rev. Lett. 30, I.141 (1973). R. Tsu, P. Menna, and A. H. Maban, Solar Cells 21, 189 (1987).

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