Angle-dependent photoluminescence spectra of hydrogenated amorphous silicon thin films

D. C. Marra, E. S. Aydil, S.-J. Joo, E. Yoon, and V. I. Srdanov Citation: Appl. Phys. Lett. 77, 3346 (2000); doi: 10.1063/1.1326837 View online: http://dx.doi.org/10.1063/1.1326837 View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v77/i21 Published by the American Institute of Physics.

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APPLIED PHYSICS LETTERS

VOLUME 77, NUMBER 21

20 NOVEMBER 2000

Angle-dependent photoluminescence spectra of hydrogenated amorphous silicon thin lms

D. C. Marra and E. S. Aydila)
Department of Chemical Engineering, University of California Santa Barbara, Santa Barbara, California 93106

S.-J. Joo and E. Yoon

School of Materials Science and Engineering, Seoul National University, Seoul 151-742, Korea

V. I. Srdanova)
Center for Polymers and Organic Solids, University of California Santa Barbara, Santa Barbara, California 93106

Received 18 July 2000; accepted for publication 19 September 2000 Multiple sharp peaks were observed in the visible photoluminescence spectra of amorphous silicon thin lms, prepared by ultrahigh vacuum electron cyclotron resonance chemical vapor deposition on oxidized silicon substrates. The angular dependence of the photoluminescence, measured by a home-built ber-optics device, revealed that the origin of these sharp features was due to Fabry rot cavity interference effects. The interference is enhanced by deposition on thermally grown Pe oxide layers with relatively smooth surfaces. We also consider how thin-lm interference effects can add to the already existing confusion regarding the photoluminescence PL mechanism of porous and other luminescent forms of silicon and propose angle-dependent PL spectroscopy as a remedy for identifying spectral features due to interference effects. 2000 American Institute of Physics. S0003-69510000247-3

The synthesis of stable, luminescent silicon lms has received renewed attention during the past decade.1,2 One of the driving forces behind this renewed interest is the possibility of combining mature silicon processing technology with promising, but still controversial, optical properties of silicon nanostructures. To date, researchers have prepared numerous photoluminescent and electroluminescent devices from porous silicon and carefully studied their emission spectra.1,2 Despite prolic research, progress in this area has been hindered by complications in identifying the origin of the emission spectra.1,2 Although quantum connement of excitons seems consistent with much of the data, in many instances other emission sources could not be ruled out. The situation can be further complicated by macroscopic thin lm interference effects3,4 that may be confused with molecular vibrations and/or lattice optical phonons coupled to the excitonic emission. In this letter, we report the observation of discrete emission peaks in the photoluminescence PL spectra of hydrogenated amorphous Si( a -Si:H) lms deposited on Si substrates with or without thermally grown SiO2. Similar features in the PL spectra of porous and a -Si:H have been attributed to coupling of excitons to vibrational modes of Si species,5,6 as well as to microcavity interference.3,4 Herein, we report multiple sharp peaks in the visible PL of a -Si:H thin lms and show, through angleresolved PL spectroscopy, that these features are due to rot cavity interference effects. We propose that anFabryPe gular dependence of the luminescence may help identify the origin of features in PL spectra.
a

Authors to whom correspondence should be addressed; electronic mail: Aydil@engineering.ucsb.edu, srdanov@chem.ucsb.edu 3346

The a -Si:H lms were deposited using ultrahigh vacuum electron cyclotron resonance chemical vapor deposition. The details of the apparatus7,8 and sample preparation9 can be found in separate publications. In all cases, the SiH4 ow rate was diluted in H2 at a ratio of 50:1. The substrates were either pristine or oxidized silicon 100 wafers with 100 nm thick SiO2. Room temperature PL spectra were excited with 10 mW of 488 nm radiation from an Ar ion laser and recorded in a backscattering geometry. Angle-resolved PL spectra were collected using a 1 mm diam optical ber, attached to a 50 mm diam rotating stage with the luminescent sample mounted at its center. The other side of the ber was coupled to a 0.5 m monochromator equipped with a grating blazed at 500 nm and a charge coupled device detector. In this way, the angle-dependent PL spectra could be obtained in the 090 range with 2 resolution. A typical PL spectrum of an a -Si:H lm, deposited on a Si substrate with a thermally grown SiO2 layer, is shown in Fig. 1. This spectrum was collected at 0 with respect to the surface normal and shows remarkably sharp features for a luminescent Si PL spectrum. Although PL from a -Si:H and porous silicon lms is typically broad and featureless, occasionally there have been reports of discrete emission features in the luminescence spectra of these materials. For example, using confocal microscopy, Mason et al.5 observed wellresolved features separated by approximately the vibrational frequency of the SiO stretching mode in the PL spectrum of single porous Si nanoparticles. The origin of these features was ascribed to coupling of conned excitons with SiO vibrational modes. Low temperature PL spectra, resembling Fig. 1, were also detected in thin a -Si:H layers deposited by plasma deposition on the Si 100 substrate.6 The temperature and power dependence of the PL intensity was found to
2000 American Institute of Physics

0003-6951/2000/77(21)/3346/3/$17.00

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Appl. Phys. Lett., Vol. 77, No. 21, 20 November 2000

Marra et al.

3347

FIG. 1. PL spectrum of an a -Si:H lm on a SiO2-coated Si wafer. The rot microcavity effect. narrow features are attributed to a FabryPe

be consistent with exciton emission. Based on these reports, it would be prudent to consider the molecular origin of the discrete luminescence peaks in Fig. 1, particularly since Si OSi vibrational modes have been identied in the infrared spectra of these samples.9 Nevertheless, prompted by reports in the literature3,4 and the fact that some of our spectra resembled those found in conjugated polymer microcavities,10 we examined the possibility that the spectrum in Fig. 1 can be explained by interference phenomena occurring in a rot e talon. FabryPe rot equation The FabryPe m 2 dn cos , 1

FIG. 2. Angular dependence of the PL spectra. The baselines of the spectra have been offset for clarity. The shift in emission to lower wavelength with rot equation. Detection angle increasing detection angle obeys the FabryPe measured with respect to the surface normal decreases in increments of 10 from 60 to 10 in the direction of the arrow.

denes conditions for constructive interference of electromagnetic radiation undergoing multiple internal reections talon. In Eq. 1, m is the interferin a solid thin lm or an e ence order, is the wavelength of the propagating radiation, talon thickness, n is the etalon index of refraction, d is the e and is the wave-front propagation angle with respect to the surface normal. For monochromatic light, a discrete set of propagation angles are allowed, each associated with a different cavity mode m; similarly, for a xed angle and a white light source there will be a set of allowed wavelengths that satisfy Eq. 1, each associated with a cavity mode. A thin lm of luminescent a -Si:H deposited on a smooth, reective substrate is not only a source of light but rot e talon, and thus create optical can also act as a FabryPe interference. The multiple reection of the emitted light arises from the contrast in refractive indices of the luminescent lm with the substrate and vacuum. The waveguiding in the lm is better and the cavity modes are sharper when the differences in the refractive indices of the lm and the surrounding materials are larger. If the discrete luminescence peaks in Fig. 1 are due to macroscopic interference phenomena, their wavelength should change with the propagation angle according to Eq. 1. In contrast, the locations of the spectral features in the PL spectra should be independent of the propagation angle if these luminescent peaks are due to conned excitons coupled to molecular vibrations or lattice optical phonons. If one observes the emitted light through a mobile orice, at some distance from the thin lm surface, it is possible to detect changes in the PL spectrum with the observation angle. If the spectral features shift with the ob-

servation angle, then the origin of the sharp features are con rot interference. If no such shift is clusively due to FabryPe observed, then explanations of the features with mechanisms involving coupling of excitons to molecular or lattice vibrations should be considered. Figure 2 shows the angular dependence of the PL spectra of an a -Si:H lm grown on an oxidized Si substrate. Clearly, angular dependence of the PL spectra conclusively rules out the molecular nature of the sharp luminescence peaks. The sharp features in Figs. 1 and rot interference. 2 are due to FabryPe The propagation angle and the observation angle in our experiment are related through Snells law, n sin sin . Substitution of Snells law in Eq. 1 yields m 2 d n 2 sin2 , 2 a relationship between the observation angle and the cavity mode wavelength . The refractive index itself also depends on the wavelength .11 From the experimental data, it is pos talon and the sible to determine both the thickness of the e index of refraction of the material, as well as the correct cavity mode numbering. In practice, one nds that all three parameters are strongly correlated in a least square t,12 requiring some of the parameters to be determined in independent experiments. The lm thickness of the a -Si:H lm in Fig. 2 is 1.3 m, as determined by scanning electron microscopy. The index of refraction is modeled using nA C B , 2 4 3

where A, B, and C are constants and n is 3.1 at 632 nm. This model provides a good t of the refractive index in the spectral region of interest 500900 nm. Using these data in Eq. 2 reveals unambiguously the correct cavity mode numbering as shown in Fig. 3. The sharpness of the observed cavity modes is determined by the cavity quality factor Q, which in turn is determined by the smoothness of the lmsubstrate and lm vacuum interfaces. The PL spectra of two a -Si:H samples, grown under identical experimental conditions but deposited

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3348

Appl. Phys. Lett., Vol. 77, No. 21, 20 November 2000

Marra et al.

FIG. 3. PL emission wavelength as a function of detection angle for the cavity modes. The experimental data are shown as symbols while the solid lines represent the model predictions based on Eq. 2.

on different substrates, are shown in Fig. 4. Sample a is grown on a smooth, oxidized silicon wafer, whereas sample b is deposited on a pristine Si wafer cleaned by hydrogen plasma prior to deposition. Even though the lms were deposited using identical conditions, the difference in their PL spectra is striking. As suggested by Curtis et al.,3 thin or poor quality optical cavities would produce broad and fewer interference fringes that could be incorrectly attributed to

luminescence properties inherent to the material. Also, in very thin lms exhibiting strong microcavity effects, the sharp intrinsic luminescence may be completely quenched at certain observation angles. Hence, the microcavity interference effects must be considered with great caution whenever interpretation of the luminescence spectra of thin lms is attempted. In conclusion, hydrogenated amorphous silicon lms, grown on a smooth and oxidized silicon substrate, can act as optical microcavities. The sharp interference pattern, obtained in the luminescence spectra of such lms, can be confused with narrow excitonic or vibronic spectral features. Silicon lms grown on rough interfaces with no oxide layer give rise to poor microcavities characterized by broad cavity modes that resemble PL spectra with broad spectral features. Peak shifts in lm-thickness dependent weakly modulated PL spectra of luminescent Si lms could be erroneously attributed to quantum connement effects and broad features may be interpreted as PL arising from different sources. Using a simple ber-optic device, which allows detection of spectrally and angle-resolved luminescence, it is possible to recognize artifacts arising from the microcavity interference effects. This research was supported by the NSF/DoE Partnership for Basic Plasma Science and Engineering Award No. DMR 97-13280 and the Camille and Henry Dreyfus Foundation. V.I.S. acknowledges the NSF Grant No. DMR9520970 for support.
A. G. Cullis, L. T. Canham, and P. D. J. Calcott, J. Appl. Phys. 82, 909 1997. 2 Light Emission in Silicon: From Physics to Devices, edited by D. J. Lockwood Academic, San Diego, CA, 1998, Vol. 49. 3 C. L. Curtis, V. V. Doan, G. M. Credo, and M. J. Sailor, J. Electrochem. Soc. 140, 3492 1993. 4 D. J. Lockwood, J.-M. Baribeau, and B. T. Sullivan, J. Vac. Sci. Technol. B 16, 1707 1998. 5 M. D. Mason, G. M. Credo, K. D. Weston, and S. K. Buratto, Phys. Rev. Lett. 80, 5405 1998. 6 K. S. R. K. Rao, A. K. Sreedhar, H. L. Bhat, R. A. Singh, G. C. Dubey, and V. Kumar, Appl. Phys. Lett. 68, 1458 1996. 7 H.-S. Tae, S.-H. Hwang, S.-J. Park, E. Yoon, and K.-W. Whang, Appl. Phys. Lett. 64, 1021 1994. 8 S.-J. Joo, K.-H. Hwang, S.-H. Hwang, E. Yoon, and K.-W. Whang, Mater. Res. Soc. Symp. Proc. 379, 433 1995. 9 S. J. Joo, S. H. Lim, E. Yoon, W. C. Choi, E. E. Kim, D. C. Marra, and E. S. Aydil, J. Korean Phys. Soc. 35, S1025 1998. 10 J. Gruner, F. Cacialli, I. D. W. Samuel, and R. H. Friend, Synth. Met. 76, 137 1996. 11 D. E. Aspnes, Thin Solid Films 89, 249 1982. 12 D. L. Albritton, A. L. Schmeltekopf, and R. N. Zare, J. Mol. Spectrosc. 67, 132 1977.
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FIG. 4. The PL spectra of two a -Si:H lms deposited on different substrate materials using identical plasma conditions. Sample a was deposited on 100 nm of SiO2 on Si, while sample b was grown on a pristine Si wafer.

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