Thin Solid Films 511 512 (2006) 394 398 www.elsevier.

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Defect states in microcrystalline silicon probed by photoluminescence spectroscopy

T. Merdzhanova a,b,*, R. Carius a, S. Klein a, F. Finger a, D. Dimova-Malinovska b
b a Institut fu r Photovoltaik, Forschungszentrum Ju lich GmbH, 52425 Ju lich, Germany Central Laboratory for Solar Energy and New Energy Sources, Bulgarian Academy of Sciences, 72 Tzarigradsko Chaussee, 1784 Sofia, Bulgaria

Available online 24 January 2006

Abstract Photoluminescence (PL) spectroscopy is used to investigate defects and localized band tail states within the band gap of hydrogenated microcrystalline silicon (Ac-Si:H) prepared by plasma enhanced chemical vapor deposition (PECVD) and hot wire chemical vapor deposition (HWCVD). The effect of the substrate temperature (T S), which influences mainly the defect density, and silane concentration (SC), as the key parameter to control the microstructure of the material were varied. In high quality Ac-Si:H films (T S = 185 200 -C) a PL band (FAc_-Si-band) is observed at 0.9 1.05 eV which is attributed to radiative recombination via localized band tail states in the microcrystalline phase. In Ac-Si:H films prepared at higher T S (> 300 -C), an additional PL band at 0.7 eV with a width of 0.17 eV is found for both PECVD and HWCVD material. This band maintains its position at 0.7 eV with increasing SC in contrast to the observed shift of the FAc_-Si-band to higher energies. Studies of the temperature dependences of the PL peak energy and intensity for the two bands show: (i) the PL band at 0.7 eV remains unaffected upon increasing temperature, while the FAc_-Si-band shifts to lower energies, (ii) a much weaker quenching for the 0.7 eV band compared to the FAc_-Si-band. It was also found that the PL band at 0.7 eV exhibits a slightly stronger temperature dependence of the PL intensity compared to Fdefect_ band at 0.9 eV in a-Si:H suggesting similar recombination transition via deeper trap states. Due to a similar PL properties of the emission band previously observed in Czochralski-grown silicon (Cz Si), the 0.7 eV band in Ac-Si:H is assigned tentatively to defect-related transitions in the crystalline phase. D 2005 Elsevier B.V. All rights reserved.
Keywords: Photoluminescence; Defect states; Silicon; Temperature-dependent measurements

1. Introduction High-quality microcrystalline silicon (Ac-Si:H) for solar cell applications can be prepared at low substrate temperatures T S on glass, stainless steel and plastics by using plasma enhanced (PE-) and hot wire (HW-) chemical vapor deposition (CVD) deposition techniques [1,2]. Studies of the PL properties of such materials have identified a PL band located below the band gap of crystalline silicon that shifts to higher energies with increasing silane concentration (SC), i.e. decreasing crystalline volume fraction [3 6]. It was proposed that this PL band originated from transitions between localized band tail states similar to those in a-Si:H [7,8]. Previous studies on AcSi:H thin films deposited at higher T S (> 300 -C) by the two techniques reveal higher spin densities (up to 1017 cm 3) and higher optical sub-gap absorption resulting in a moderate
* Corresponding author. Tel.: +49 2461 61 3177; fax: +49 2461 61 3735. E-mail address: t.merdzhanova@fkf.mpg.de (T. Merdzhanova). 0040-6090/$ - see front matter D 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.tsf.2005.12.114

performance of solar cells prepared under such conditions [2,5,9]. Here, we report on new results of a PL study on such Ac-Si:H thin films. 2. Experimental Intrinsic Ac-Si:H thin films were prepared on Corning glass substrates or rough quartz using PECVD at 95 MHz at substrate temperatures (T S) of 200 -C and 325 -C, or HWCVD at T S of 185 -C and 330 -C, with filament temperature (T F) of 1650 -C and 1850 -C. The film thickness of the samples ranged from 0.4 Am to 1 Am (HWCVD), and from 0.5 Am to 3 Am (PECVD). The microstructure of the films was modified by varying the dilution of the silane in hydrogen in the process gas, i.e. silane concentration SC = [SiH4] / [SiH4 + H2]. Details of the deposition parameters are published elsewhere [1,2,9]. For excitation of the luminescence, as well as for Raman scattering experiment, a laser wavelength of 488 nm of an Ar+ laser with a power density of 5 W/cm2 was used.

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Therefore, a similar sample volume is probed by the two experiments, except for a small variation due to the temperature dependence of absorption coefficient. The integrated RS intensity ratio I C = (I 520 + I 500) / (I 520 + I 500 + I 480) of the crystalline peaks (520 cm 1 and 500 cm 1) and the amorphous peak (480 cm 1) was used as a semi-quantitative measure for the crystalline volume fraction [10]. Photoluminescence spectra were recorded at temperatures of 10 200 K using a Fourier transform (FT) spectrometer (Bruker FS66v) and a liquid nitrogen (LN2) cooled Ge or an InAs detector, applying lock-in technique to enhance signal-to-noise ratio. 3. Results In Fig. 1(a, b), photoluminescence (PL) spectra (measured at 10 K) of Ac-Si:H thin films, prepared by HWCVD and PECVD at high substrate temperatures (T S) of 330 -C and 325 -C with various silane concentrations (SC) between 9% and 25% are compared. All PL spectra are shifted vertically by 0.1 r.u. for clarity. In Fig. 1(a), the PL spectra of the HWCVD material with SC (10 17.5%) reveal two emission bands, a high-energy PL band at 0.97 eV and a full width at half maximum (FWHM) of 0.14 eV (FAc_-Si-band), attributed to the microcrystalline phase [3 7] and a low-energy emission band centred at about 0.7 eV. The latter is very similar to the emission band previously observed in poly-Si thin films on glass and denoted as Fdefect_ PL band [11]. The following can be considered as distinctive features of the _defect_ band upon increasing SC: (i) the PL band maintains the spectral maximum at about 0.7 eV and the FWHM also holds a constant value of 0.17 eV, while the FAc_-Si-band

shifts to higher energies; and (ii) the PL intensity is slightly higher than the intensity of the FAc-Si-band and it increases continuously until the broader ( 0.3 eV) emission band at 1.26 eV, appears at SC = 17.5%. This well-known PL band in a-Si:H thin films is related to radiative recombination between the band tail states (Fa_-Si-band) [12]. The inset in Fig. 1(a) shows similar increase of the PL intensities of the Fdefect_ Ac-Si and the FAc_-Si band upon increasing SC, i.e. almost the same ratio between the two bands is kept until the contribution of the Fa_-Si-band becomes significant at SC ! 18.5%, followed by a substantial decrease of the PL intensity of the FAc_-Si-band and the PL signal at 0.7 eV disappears. The luminescence spectra of Ac-Si:H films, prepared by PECVD are shown in Fig. 1(b), for comparison. All three emission bands with maxima at 0.7 eV (Fdefect_ Ac-Si), 1.01 1.03 eV (FAc_-Si) and 1.26 eV (Fa_-Si) were identified even for films with lower SC between 9% and 13%. For material with a SC of 15%, which reveals a PL spectrum dominated by the signal at 1.26 eV, there is still a small contribution from the Fdefect_ Ac-Si-band and the FAc_-Si-band, while for SC = 17% the PL spectrum is entirely dominated by the Fa_-Si-band. Similar to HWCVD films, the Fdefect_ Ac-Siband remains unchanged, while the FAc_-Si-band shifts to higher energies, upon increasing SC. The dependence of the luminescence intensity of the FAc_-Si- and the Fdefect_ Ac-Si bands on the SC is also shown in the inset in Fig. 1(b). In contrast to HWCVD, the PL intensities of the two emission bands do not increase continuously with increasing SC and the intensity of the Fdefect_ Ac-Si-band is slightly lower, while the FAc_-Si-band reveals improved efficiency (compare inset in Fig. 1(a)).

Fig. 1. Photoluminescence spectra of Ac-Si:H thin films, prepared by (a) HWCVD at T S = 330 -C and T F = 1850 -C and (b) PECVD at T S = 325 -C with indicated SC. Solid lines are measured PL data at 10 K with E x = 2.54 eV, the dashed lines are the fitting curves with Gaussian line shape. Insets (a, b): dependence of the PL intensity of Fdefect_ Ac-Si-band and FAc_-Si-band on the SC.

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1.1

PL energy (eV)

c-Si-band

0.9

PECVD TS=325oC HWCVD TS=330oC

0.8
defectc-Si-band

0.7 0 0.2 0.4 0.6 0.8 1

Raman intensity ratio IcRS

Fig. 2. PL peak energy of Fdefect_ Ac-Si-band and FAc_-Si-band vs. FRaman RS crystallinity_, I C , for two sample series, prepared by PECVD (T S = 325 -C) and HWCVD (T S = 330 -C, T F = 1850 -C). The solid lines are guides to the eye.

As the crystalline volume fraction has been shown to be a valuable tool to parameterise Ac-Si:H thin films, the PL peak energy of the FAc_-Si and Fdefect_ Ac-Si bands are shown in RS Fig. 2 as a function of I C for the two sample series shown in Fig. 1(a, b). Note, a few additional points have been added for the HWCVD series, from PL spectra which were omitted for clarity in Fig. 1(b). While the FAc_-Si-band shows an increase RS of the PL peak energy with decreasing I C , the Fdefect_ Ac-Siband retains its spectral maximum at about 0.7 eV for all series studied. The PECVD series (see Fig. 1(b)) exhibits slightly higher values for the PL peak energy of the FAc_-Si-band compared to the HWCVD series. In addition a higher PL intensity of the FAc_-Si-band is observed for the PECVD series compared to HWCVD material. A competition between radiative and non-radiative recombination transitions as a function of measurement temperature

provides information on the recombination processes involved. Therefore, the PL spectra in the temperature range (10 200 K) for two samples, one with equal contributions of microcrystalRS 0.5 (SC = 9%) (see Fig. 1(b)) line and amorphous phase I C and a second with fully amorphous microstructure (PECVD, T S = 200 -C) are displayed semi-logarithmically in Fig. 3(a, b). Three emission bands at 0.7 eV (Fdefect_ Ac-Si), at 1.01 eV (FAc_-Si-) and at 1.26 eV (Fa_-Si-) characterize the PL RS spectrum at 10 K for the film with I C 0.5 shown in Fig. 3(a). Referring to Fig. 3(a), there is a slight decrease in the PL intensity of the FAc_-Si-band and slight increase in the intensity of the Fdefect_ Ac-Si- and Fa_-Si band below 40 K. Further increase of the temperature results in a much weaker quenching of the Fdefect_ Ac-Si-band compared to the rapid quenching of the FAc_-Si-band and the Fa_-Si-band. At 160 K the Fa_-Si-band has disappeared while the FAc_-Si-band is visible up to 160 K. Above 180 K, the Fdefect_ Ac-Si-band dominates the PL spectra. In Fig. 3(b), the PL spectrum (at 10 K) for the amorphous film consists of two emission bands, one at 0.9 eV with halfwidth of 0.35 eV and the Fa_-Si-band. The low-energy band has been attributed to recombination transitions via electronically active defect states identified as dangling bonds, thus we denote it here as (Fdefect_ a-Si-) ([12], and references therein). With increasing temperature, the PL intensity of the Fdefect_ aSi-band reveals a much weaker decrease compared to that observed for the Fa_-Si-band, and dominates the PL spectra at 200 K. With increasing temperature the PL peak energy of the Fdefect_ a-Si-band and the Fdefect_ Ac-Si band (see Fig. 3(a)) retain a spectral maximum at 0.9 eV and 0.7 eV, in contrast to the observed shift of the main PL bands (Fa_-Si- and FAc_-Siband) to lower energy due to the rapid decrease in the in the high-energy part of the spectrum. The temperature dependence of the PL intensity of the main and the defect related emission bands are summarized in Fig. 4 in an Arrhenius plot for different microcrystalline films and the amorphous sample (see Fig. 3(b)). For the high quality Ac-Si:H

RS Fig. 3. PL spectra at indicated temperatures for a samples, prepared by (a) PECVD at T S = 325 -C; SC = 9% (I C 0.5) as shown in Fig. 1(b) and (b) PECVD at T S = 200 -C with fully amorphous microstructure. The luminescence was excited with photons of energy E x = 2.54 eV.

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(HWCVD, T S = 185 -C), Raman spectra indicate a predomiRS nantly crystalline structure with I C 0.6 and the corresponding PL spectra exhibit only the FAc_-Si-band [5,6], while for Ac-Si:H films (PECVD, T S = 325 -C) the additional PL band at 0.7 eV is found. The PL spectra of the fully amorphous films reveal only the Fa_-Si-band (HWCVD, T S = 185 -C). To show the temperature dependence of the PL intensity of the Fdefect_ a-Si-band at 0.9 eV, a sample deposited by PECVD was chosen (see Fig. 3(b)). The temperature dependence of the PL intensity for the FAc_-Siband shows a rapid quenching by three orders of magnitude starting at 40 K. The Fa_-Si-band exhibit an almost constant PL intensity up to 80 K before it starts to decrease. Similar to Fdefect_ band in a-Si:H, the PL intensity of Fdefect_ band in AcSi:H does not show a significant decrease for temperatures below 80 K but a stronger decrease as the Fdefect_ a-Si-band. No single activation energy was found for Ac-Si:H thin films in a manner similar to a-Si:H [12]. Fig. 5 shows the temperature dependence of the PL peak energy for the same sample series shown in Fig. 4. Upon increasing temperature, the two Fdefect_ bands maintain at a peak position of 0.7 eV for the Ac-Si:H films (at T S > 300 -C) and at 0.9 eV for the a-Si:H films studied. The half-width of the Fdefect_ Ac-Si- and Fdefect_ a-Si-bands also holds constant values of 0.17 eV and 0.35 eV over a range of temperatures (10 200 K) (data not shown). For Ac-Si:H thin films with RS IC 0.6, a continuous shift of the PL peak energy towards lower energies is observed with increasing temperature. All these films show a similar temperature coefficient of 1.1 10 3 eV/K for the PL peak energy above 40 K. Above 80 K, the shift of the PL peak energy is much stronger for

Fig. 5. Temperature dependences of the PL peak energy of the FAc_-Si-, Fa_-Si-, Fdefect_ Ac-Si-, Fdefect_ a-Si-bands for the same samples as shown in Fig. 4. The temperature coefficients for the shift of the FAc_-Si-band ( 1.1 10 3 eV/K) and the Fa_-Si-band ( 1.6 10 3 eV/K) is given.

highly amorphous films with a temperature coefficient of 1.6 10 3 eV/K, which is in agreement with values reported for a-Si:H ([12], and references therein). 4. Discussion In Ac-Si:H thin films prepared at substrate temperatures higher than 300 -C, an emission band at about 0.7 eV with a half-width of about 0.17 eV was observed in addition to the main band located at 0.9 1.05 eV (FAc_-Si-band), irrespectively of the preparation method used (see Fig. 1(a, b)). This emission band was not detected for Ac-Si:H prepared at lower T S, which is identified as high quality material. Fig. 2 shows clearly that the new emission band maintains a spectral maximum at about 0.7 eV, while the FAc_-Si-band shifts to higher energies with changing the structural composition from RS crystalline (I C 0.74) to predominantly amorphous, i.e. RS decreasing crystalline volume fraction, I C . The main band in Ac-Si:H is attributed to the radiative recombination via localized band tail states in the microcrystalline phase in a manner similar to a-Si:H [7,8]. A reduction of the density of the band tail states due to structural relaxation of the Ac-Si:H network by hydrogenated amorphous silicon surrounding the crystalline phase was proposed as a cause for the shift of the FAc_-Si-band to higher energies [6,7]. The PL band at 0.7 eV RS remains unaffected upon decreasing I C (see Fig. 2) and in addition the PL peak energy was found to be independent of the measurement temperature (Fig. 3(a)) as was observed for the Fdefect_ band at 0.9 eV in a-Si:H (see Fig. 3(b)). This suggests that band tail states are very likely not involved in the recombination transition at 0.7 eV in Ac-Si:H. In agreement with this is the weaker temperature dependence of the PL intensity for the 0.7 eV band as compared to the main emission

Fig. 4. Temperature dependence of the PL intensity of the FAc_-Si-, Fa_-Si-, Fdefect_ Ac-Si-, Fdefect_ a-Si-band for samples, prepared by different deposition methods and T S. The PL intensity for the FAc_-Si- (at 40 K) and Fa_-Si-bands (at 80 K) are normalized with respect to the highest PL intensity achieved for high quality films (HWCVD, T S = 185 -C).

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band (see Fig. 4). In a manner similar to a-Si:H, the temperature quenching of the main band in Ac-Si:H is very likely due to thermally enhanced emission of carriers trapped in the band tail states and subsequent non-radiative recombination via capture at defect states. The more rapid quenching of the PL intensity of the FAc_-Si-band in comparison to the Fa_-Siband (Fig. 4) points to shallower trap states, i.e. steeper band tails in Ac-Si:H. This is in line with the weaker shift of the FAc_Si-band with temperature coefficient of 1.1 10 3 eV/K, while the Fa_-Si-band is shifted stronger (1.6 10 3 eV/K) upon increasing temperature (see Fig. 5). The Fdefect_ band in a-Si:H at about 0.9 eV found in the material of high defect density in addition to the main Fa_-Siband at 1.3 1.4 eV is considered to be due to recombination transitions from the band edge to intrinsic defects (dangling bonds). The weaker temperature dependence of the PL intensity as compared to the Fa_-Si-band is related to one of the carriers being deeply trapped at a dangling bond [12]. The similar but slightly stronger temperature dependence of the PL intensity of the 0.7 eV band in Ac-Si:H suggests that a similar recombination process could be involved, i.e. transition into deep trap states. An emission band with similar PL properties that maintains spectral maximum at about 0.65 eV between 4.2 K and 300 K and quenched from 90 K has been previously observed for hydrogenated poly-Si on glass deposited at 625 -C or 550 -C, which is similar to Ac-Si:H thin films studied in this work [11]. There the defect-related emission band at 0.7 eV in Ac-Si:H is tentatively assigned to recombination transitions via defect states in the crystalline phase. Similar PL properties of the emission band were also observed in Cz Si annealed at 450 -C and attributed to thermal donors related to oxygen precipitates in silicon [13,14]. We therefore propose that similar deep defects exist in Ac-Si:H. It is interesting to note that no indication for a contribution of the Fdefect_ a-Si-band in the defect-rich Ac-Si:H films is found, even in samples where a significant contribution of the Fa_-Si-band in addition to the Fdefect_ Ac-Si-band is observed. 5. Conclusions In addition to a main emission band at 0.9 1.05 eV, a new emission band at 0.7 eV was found for Ac-Si:H thin films (T S > 300 -C) with high spin density (1017 cm 3) and higher optical sub-gap absorption. Since the 0.7 eV emission band remains unaffected, while the main PL band shifts to

higher energies upon decreasing crystalline volume fraction and, in addition the PL peak energy, was found to be independent of the measurement temperature, we conclude that localized band tail states are not involved in the recombination transition at 0.7 eV. The similar but slightly stronger temperature dependence of the PL intensity of the 0.7 eV band in Ac-Si:H, compared to Fdefect_ PL band at 0.9 eV in a-Si:H originating from recombination transitions from the band edge into dangling bonds, suggests that a similar recombination process is involved, i.e. transition of one of the carriers into deep trap states. The PL band at 0.7 eV is tentatively assigned to defect-related transitions in the crystalline phase, by comparison with a PL band previously observed in Cz Si attributed to recombination processes involving defects connected to thermal donors which are related to oxygen precipitates. Acknowledgments We are grateful to Markus Hu lsbeck and Josef Klomfass for their contributions to this paper. References
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