DEEP LEVEL TRANSIENT SPECTROSCOPY STUDIES OF ELECTRICALLY ACTIVE CENTERS IN SOLAR-GRADE SI

Monakhov E. , Syre M. , Tang C.K. , Mayandi J. , Olaisen B. , Snden R. , Svensson B.G. and Holt A. 1 Solar Energy Department, Institute for Energy Technology, Kjeller, Norway 2 Physics Department, University of Oslo, Oslo, Norway ABSTRACT In this work we have employed deep level transient spectroscopy (DLTS) for studies of electrically active centers in solar-grade Si. The purpose of the work is to develop robust experimental routines for detecting and identifying the dominant recombination centers. DLTS measurements have been performed prior and after heat treatments corresponding to such technological processes as contact firing and rapid thermal processing (RTP). Multi-crystalline (mc-Si) and Cz-Si with p-type doping and the resistivity in the 1-6 Ohm range have been investigated. Firstly, the effect of Fe has been investigated. In order to ensure that the carrier recombination is determined by Fe, the samples have been intentionally enriched by Fe via in-diffusion from the surface. It has been observed by DLTS that a heat treatment corresponding to the contact firing process leads to activation of Fe in the interstitial form (Fei) with a donor state at 0.43 eV above the valence band. Secondly, RTP has received a considerable attention recently due to increasing control in diffusion profile for the emitter formation in solar cells. However, electrically active defects and impurities may be introduced or activated by RTP due to the high temperatures of the treatment followed by rapid cooling, when the impurities can be quenched with concentrations above the solubility level. It o is found that RTP at 1000 C for 2 minutes results in formation of two dominant hole traps at ~0.3 and ~0.4 eV above the valence band edge with concentrations in the 12 13 -3 range 5x10 -510 cm . The observed levels exhibit Poole-Frankel effect suggesting the acceptor nature of the centers. INTRODUCTION In silicon based solar cells, iron contamination induces recombination centers which reduce the minority carrier life-time and hence the diffusion length. This is detrimental to the solar cell efficiency. Iron in p-type Si can be present in two electrically active states: interstitial iron (Fei) and iron boron pairs (FeB). For functioning solar cells, minority carrier diffusion lengths should be equal to or exceed the wafer thickness. Based on this consideration, the concentration of FeB which limits the diffusion length to the thickness of a 300-m wafer can be estimated in the 11 -3 order of 5x10 cm [1]. This estimate is in agreement with experimental observations that FeB with a concentration 11 -3 of 5x10 cm can decrease the efficiency of CZ solar cells by 3%4% [2].
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Rapid thermal processing (RTP) has received a considerable attention recently due to increasing control of dopant diffusion for the emitter formation in solar cells. Activation of dopants from ion implantation using RTP can minimize the diffusion time and enable ultra shallow emitters which will put less stringent criteria for surface passivation in solar cells [3]. However, electrically active defects and impurities may be introduced or activated by RTP due to the high temperatures of the treatment followed by rapid cooling. In fact, impurities can be quenched with concentrations well above the solubility level and in particular, transition metals, which can reduce the minority carrier lifetime considerably, may dissolve from grain boundaries in multicrystalline silicon (mc-Si) [4]. Although the concentrations of metals in single crystalline silicon are much lower in comparison with mc-Si, defects with characteristics of transition metals have been observed after a RTP treatment and proposed as residuals [5]. Deep level transient spectroscopy (DLTS) is a technique capable of direct observation of electrically active defects in semiconductors. However, the absolute sensitivity of DLTS measurements is determined as a fraction of the doping level, and is high in the samples with high resistivity. The detection limit of DLTS, depending on experimental conditions, can reach the range down to -5 -6 Nt/Nd=10 10 . Due to this limitation and corresponding technical difficulties, DLTS studies of iron and other impurities in p-type Si have been normally done on lower 14 15 -3 doped materials with the doping 10 - 10 cm and lower. Very few DLTS studies are reported in p-Si with the 15 doping relevant for solar cell application, i.e., 10 16 -3 10 cm . In this work we report on DLTS studies of electrically active centers in solar-grade Si. The observed centers are induced by fast thermal processes, such as firing and RTP, relevant for solar cell fabrication. EXPERIMENTAL P-type monocrystalline Czochralski (CZ) Si wafers with 15 -3 resistivity ~10 Ohm-cm (doping ~2x10 cm ) were intentionally contaminated with iron. The samples were dipped into FeCl3 solution mixed with ethanol, and dried at o 200 C for 10 minutes. The samples were subsequently o annealed at 700 C for 15 to 120 minutes, to drive in different amounts of Fe. After Fe in-diffusion the samples o were annealed in a belt oven at 1000 C for 1 min followed by quenching with a cooling rate of ~30 K/s. For DLTS measurements Schottky diodes were made by thermal evaporation of Al. Prior to the deposition, the samples

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were etched in a mixture of HNO3:CH3COOH:HF, followed o by a 10 min anneal at 200 C and a dip in HF to remove the native oxide. The annealing was performed in order to split the FeB pairs. The rapid thermal annealing was performed using the RTP system AS-Micro from AnnealSys, where the samples were contained in a SiC-coated graphite susceptor. Heating was provided by infrared tubular halogen lamps and the cooling rate was about 30K/s. Samples cut from multicrystalline (mc) Si and Cz-Si with boron doping 16 3 15 3 concentration of ~1x10 cm and ~2x10 cm , o respectively, were heat treated at 1000 C for 2 min. For DLTS measurements Schottky diodes were deposited by thermal evaporation of Al. DLTS was performed in the temperature range from 30 K to 300K. The DLTS signal was extracted using lock-in weighting function, and six rate-windows ranging from 1 1 (20ms) to (640ms) were used. A detailed description of the DLTS setup can be found elsewhere [6]. RESULTS AND DISCUSSION Iron detection

DLTS spectra measured for samples with different indiffusion times are presented in Fig. 2. One can see that 11 -3 Fei concentrations in the 10 cm range can be detected. It is interesting to note that no correlation between the indiffusion time and the amplitude of Fei is observed. This indicates that the amount of Fe introduced during the indiffusion exceeds the solid solubility limit and the fraction of active Fei is limited by the solid solubility.

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Fig. 1 demonstrates DLTS spectra of a sample after 90 min of Fe in-diffusion and the subsequent quenching. The spectra represent measurements for the as-prepared o sample, including the heat treatment at 200 C for 10 min (solid red curve), and after storage in dark for 3 weeks at room temperature (dashed blue curve). For the asprepared sample one can observe a dominant peak with an activation energy of 0.43 eV identified as Fei. The 12 concentration of Fei deduced from the spectra is 3x10 -3 cm . After the storage the DLTS measurement reveals disappearance of the Fei peak and formation of a peak with an activation energy of 0.1 eV identified as FeB. The magnitude of the peaks show that all Fe that is present initially as Fei has been converted after the storage to FeB pairs.
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Figure 2 DLTS spectra of the as-prepared samples with different iron in-diffusion times.

Defect centers induced by RTP Fig. 3 shows DLTS spectra for mc-Si samples with a 16 -3 boron concentration of 1x10 cm without RTP and after o RTP at 1000 C for 2 min. Two dominant hole traps with activation energies of 0.24 eV and 0.35 eV are observed in the samples after RTP. The spectra presented in Fig. 3 are measured for samples with different life-time values. 13 -3 The concentration of the traps is in the 10 cm range with a higher concentration in the sample with shorter lifetime. Although there is an apparent correlation between the life-time measurements and the concentration of the traps, more data are needed to confirm the correlation. In order to investigate the observed hole traps, DLTS studies of the RTP effect have been performed for lower doped Cz-Si. The DLTS measurement with a reverse bias of -5 has been performed for Cz-Si samples after RTP (Fig. 4). Similarly to mc-Si, two peaks are observed for RTP samples and labelled H(0.3) and H(0.4), whereas no peaks are observed in the as-grown sample. However, the energy level position for these traps is observed to be higher as compared to mc-Si: 0.27 eV and 0.38 eV. Defect concentration and apparent capture cross-section extracted from the Arrhenius plot for H(0.3) are found to 12 3 15 2 be 6x10 cm and 5x10 cm , respectively. For the 13 3 H(0.4) a peak defect concentration of 5x10 cm and an 15 2 apparent capture cross-section of 1x10 cm have been determined.

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Figure 1 DLTS spectra of the as-prepared sample (solid red) and after storage allowing the FeB pairs to form (dashed blue).

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shorter life-time longer life-time no RTP 0.24 eV

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Figure 3 DLTS spectra for mc-Si samples without RTP o and after RTP at 1000 C for 2 min. The samples are cut from the same wafer but from different regions with different carrier life-times. We have also performed a DLTS measurement with a higher bias of -20V (Fig. 4). It is observed that the positions of both peaks are shifted towards lower temperature. No other peaks are revealed for Cz-Si in the temperature range of 77 K to 300 K. The temperature-axis in Fig. 4 is shortened in order to emphasize the shift of DLTS signal towards lower temperature when larger reverse bias is applied.

the peak position shifts to a lower temperature, the emission rate of the trap has increased, indicating that the energy barrier for charge carrier emission is lowered. Under an external electric field, this can occur through a Poole-Frenkel effect when Coulomb interaction exists between the emitted charge carrier and the trap [ 7 ]. According to the model [7], the change in the energy barrier, E, is proportional to the square root of the electric -4 -1/2 1/2 field times a constant of 3.9x10 eV V cm for Si. Fig. 5 shows the Arrhenius plot for H(0.3) and H(0.4) with different averaged electric field in the depletion region. In addition to a shift, it can be seen that the gradient (which is proportional to the energy barrier) decreases with increasing electric field. We have found that the change of the activation energy is indeed can be described by the Poole-Frankel effect with the proportionality constant for -4 -1/2 1/2 the field-dependence ~4x10 eV V cm . This is in close agreement with that predicted in Ref. [7]. Hence, both H(0.3) and H(0.4) are considered to be traps of acceptor nature.

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Figure 5 Arrhenius plots for H(0.3) and H(0.4) in different electric field. The experimental conditions for 15 3 the plots are: (squares) Va=5V, NA=2x10 cm ; 15 3 (circles) Va=20V, NA=2x10 cm ; (triangle) Va=5V, 16 3 NA=1x10 cm .
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Figure 4 DLTS spectra of Cz-Si after RTP at 1000 C for 2 min taken with reverse bias of -20V and -5V, showing a shift in the peak position of the DLTS signal. The two spectra reveal two electrically active defects with energy level position of EV+0.3 eV and EV+0.4 eV. In addition, DLTS spectrum for sample without RTP treatment (as-grown) is shown. Each peak in the DLTS spectra can be related to a specific emission rate, given a rate-window and a weighting function, which is characteristic to a trap. When

It can be speculated that observed traps are related to a fast diffusing impurity such as Fe, Co, Ni or Cu. First principle calculations have predicted that both substitutional Cu and Ni have acceptor levels close to H(0.4) [8 ]. However, substitutional Cu and Ni are also predicted to have donor-like energy levels close to EV, which will in this case appear in the DLTS spectra with equal amplitude as H(0.4). Such levels are not observed in our samples, as discussed below. From experiments related to nickel, several deep levels in the lower half of the band gap have been reported in the literature [9,10]. In agreement with the theoretical work in Ref. [8], Kitagawa and Nakashima [10] ascribed a donor level to substitutional Ni at EV+0.18 eV, which is not found in this study.

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Similar to Ni, Cu has been observed experimentally with several deep levels in the lower half of the band gap [11]. The earliest reported energy levels were the ones at EV +0.24 eV and EV+0.49 eV and regarded as originating from substitutional Cu [ 12 ]. From Hall effect measurements on intentionally Cu-contaminated p- and ntype Si samples which showed an amphoteric behavior of Cu, Collins and Carlsen [12] concluded that the former and the latter energy level were of donor- and acceptortype, respectively. Similar results were obtained by Brotherton et al. [ 13 ] using DLTS in a later study. In addition, they found a clear correlation between the two levels in terms of concentration and concluded that the levels arised from one defect with different charge states. Consequently, if H(0.3) and H(0.4) were due to substitutional Cu, a field-dependent emission should be minimal for H(0.3) and the concentrations of H(0.3) and H(0.4) should be equal. CONCLUSIONS We have investigated electrically active centers in solargrade Si induced by rapid thermal processes. Interstitial Fe and FeB pairs have been detected with concentrations 11 -3 in the range 10 cm . It is shown that rapid thermal processing can result in activation of metallic impurities that are gettered in previous technological steps. Moreover, rapid thermal processing may lead to formation of acceptor-like centers with energy levels at ~0.3 eV and ~0.4 eV above the valence band. ACKNOWLEDGEMENT This project has been funded by REC Wafer, REC Solar, Elkem Solar and the Norwegian Research Council through the KMB project Defect engineering for crystalline silicon solar cells. REFERENCES G. Zoth, W. Bergholz, J. Appl. Phys. 67, 1990, pp. 6764 J.H. Reiss, R.R. King, K.W. Mitchell, Appl. Phys. Lett. 68, 1996, pp. 3302 3 J. Zhao, A.Wang, and M.A. Green, Prog. Photovolt. Res. Appl. 1, 1993, pp. 193 4 T. Buonassisis, A.A. Istratov, S. Peters, C. Ballif, J. Isenberg, S. Riepe, W. Warta, R. Schindler, G. Willeke, B.L.Z. Cai, and E.R. Weber, Appl. Phys. Lett. 87, 2005, pp. 121918 5 D. Barbier, M. Remram, J. Oly, and A. Laugier, J. Appl. Phys. 61, 1987, pp. 156 6 B.G. Svensson, K.H. Ryden, and B.M.S. Lewerentz, J. Appl. Phys. 66, 1989, pp. 1699 7 J. Frenkel, Phys. Rev. 54, 1938, pp. 647 8 F. Beeler, O.K. Andersen, and M. Scheffler, Phys. Rev. B 41, 1990, pp. 1603 9 H. Indusekhar and V. Kumar, J. Appl. Phys. 61, 1987, pp. 1449 10 H. Kitagawa and H. Nakashima, Jap. J. Appl. Phys. 28, 1989, pp. 305
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A.A. Istratov and E.R.Weber, Appl. Phys. A 66, 1998, pp. 123 12 C.B. Collins and R.O. Carlsen, Phys. Rev. 108, 1957, pp. 1409 13 S.D. Brotherton, J.R. Ayres, A. Gill, H.W. van Kesteren, and F. J.A.M. Greidanus, J. Appl. Phys. 62, 1987, pp. 1826

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