Toward the fast deposition of highly crystallized microcrystalline silicon films with low defect density for Si thin-film solar cells

In this study, employing a high-density, low-temperature SiH₄–H₂ mixture microwave plasma, we investigate the influence of source gas supply configuration on deposition rate and structural properties of microcrystalline silicon (μc-Si) films, and demonstrate the plasma parameters for fast deposition of highly crystallized μc-Si films with low defect density. A fast deposition rate of 65 Å/s has been achieved for a SiH₄ concentration of 67% diluted in H₂ with a high Raman crystallinity of X_c > 65% and a low defect density of (1–2) × 10¹⁶ cm⁻³ by adjusting source gas supply configuration and plasma conditions. A sufficient supply of deposition precursors, such as SiH₃, as well as atomic hydrogen H on film growing surface is effective for the high-rate synthesis of highly crystallized μc-Si films, for the reduction in defect density, and for the improvement in film homogeneity and compactability. A preliminary result of p–i–n structure μc-Si thin-film solar cells using the resulting μc-Si films as an intrinsic absorption layer is presented.     

Preferential segregation of dopants in μc-Si:H

Electronic and structural properties of heavily B-doped μc-Si:H films prepared by rf glow discharge technique have been studied by Raman scattering, IR absorption, SIMS and conductivity measurements. It is found that boron atoms in μc-Si:H tend to segregate in the amorphous tissue. The remarkable difference in doping efficiency between B- and P-doped μc-Si:H was interpreted in terms of the different degree of dopant segregation in the amorphous phase.     

Investigation of gap states in phosphorous-doped ultra-thin a-Si:H by near-UV photoelectron spectroscopy

A variant of photoelectron spectroscopy with near-UV light excitation was established and applied to an n-type doping series of ultra-thin a-Si:H layers (layer thickness ～10 nm). Using this technique, the position of the surface Fermi level E_Fs is obtained and the density of recombination active defect states in the a-Si:H band gap down to ～10¹⁵ states/cm³ can be detected. Defect densities are generally about one order of magnitude higher than in the bulk of thicker (several 100 nm) layers, and the minimum achievable distance of E_Fs from the conduction band is ～360 mV for doping with 10⁴ ppm PH₃. The optimum doping for the fabrication of solar cells is almost one order of magnitude lower. This discrepancy may be explained by enhanced recombination at the a-Si:H/c-Si interface at high doping levels, and in addition by an efficient recombination pathway where charge carriers tunnel from c-Si via a-Si:H band tail states into the a-Si:H and subsequently recombine at dangling bond states.     

Influence of the amorphous/crystalline silicon heterostructure properties on planar conductance measurements

We report a quasi-analytical calculation describing the heterojunction between hydrogenated amorphous silicon (a-Si:H) and crystalline silicon (c-Si) at equilibrium. It has been developed and used to determine the carrier sheet density in the strongly inverted layer at the a-Si:H/ c-Si interface. The model assumes an exponential band tail for the defect distribution in a-Si:H. The effects of the different parameters involved in the calculation are investigated in detail, such as the Fermi level position in a-Si:H, the density of states and the band offsets. The calculation was used to interpret temperature dependent planar conductance measurements carried out on (n) a-Si:H/ (p) c-Si and (p) a-Si:H/(n) c-Si structures, which allowed us to confirm a previous evaluation of the conduction band offset, ?E_C = 0.18 ± 0.05 eV, and to evaluate the valence band offset: ?E_V = 0.36 ± 0.05 eV at the a-Si:H/ c-Si heterojunction. The results are placed in the frame of recent publications.     

Medium-range ordering in glass structures as a background of photosensitivity in silica fibers

Using picosecond stimulated Raman scattering (SRS) in silica-based fibers as a spectroscopic tool, some correlations between medium-range ordering and photosensitivity in silica glasses were experimentally established. Apart from the fundamental Raman-active vibrations attributed to the silica tetrahedra and dopant groups and their overtones, the intense Raman combination bands were observed. Based on the overtone band sequences, the vibrational anharmonicity constants were calculated and analyzed, including the ones corresponding to the 570 cm⁻¹ band. This band is forbidden in Raman scattering in silica crude selection rules are used. However, the transition is activated owing to the tetrahedron distortions by outer shells of the first and second peripheral atoms in a silica network. It is the intensity of the 570 cm⁻¹ Stokes band that grows enormously in the SRS spectra of germanium-doped silica fibers as a result of photoinduced changes in the glass structure resulting in second harmonic generation (SHG). The experimental data are interpreted using a modern glass theory. Practical applications of picosecond SRS spectroscopy for glass microstructural studies are discussed.     

Vibrational Spectra of Liquid Crystals. XII

Abstract

Recent papers by Gray et al.¹ have discussed the synthesis, structure, and properties of the mesomorphic 4-cyano, 4′-alkyl (or alkoxy) biphenyls. The reports on these materials have made mention of the existence of solid state dimorphism for certain homologs. This paper discusses this dimorphism as it manifests itself in the Raman spectrum of the octyloxy homolog (hereinafter referred to as 80CB) in the CN stretching region.

The approach used involves direct measurement of the Raman spectrum as a function of temperature, as well as computation of a correlation function obtained from the Raman band envelope by means of Fourier transformation. The application of this correlation function technique to this system has been discussed by us recently in detail.^2,3

Gray and Mosley,⁴ in a recent study of the Raman spectrum of 4-cyano, 4′-pentylbiphenyl note that the CN stretch of this compound is a doublet in the solid phase (2224 and 2233 cm^?1), but only the 2224 cm^?1 band appears in the nematic phase. They further report that only a single band appears in the CN stretching spectrum of solid 4'-heptyl-, -hexyl-, and -butyl-derivative. They speculate that the doublet might appear in the spectrum of the metastable solid phase of the heptyl homolog.

In this work, we show that for 80CB this is not the case. Rather, a doublet is observed for the stable solid but not for the metastable. The origin of this doublet is discussed, and all of the CN stretches for stable solid, metastable solid, and smectic liquid crystal are analyzed from the viewpoint of the vibrational relaxation correlation function.     

EELS measurements of boron concentration profiles in p-a-Si and nip a-Si solar cells

The p-type Si layer in a-Si and μc-Si solar cells on foil needs to fulfil several important requirements. The layer is necessary to create the electric field that separates the photo-generated charge carriers; the doping also increases the conductivity to conduct the photocurrent to the front contact; on the other hand, the p-layer should transmit the incident light efficiently to the intrinsic absorber layer. We show that it is possible to study TEM samples prepared, for analysis of possible layer defects, by focussed ion beam milling to detect boron and carbon concentrations as low as 10²⁰ cm^-3, using core-loss EELS combined with numerical analysis. We control the band gap and activation energy of p-a-SiC by varying the B₂H₆ and CH₄ flow during deposition in the process chamber. We have found a linear relation between the activation energy of the dark conductivity E_act and the optical band gap E₀₄. Modelling shows that the optimum efficiency in nip solar cells is obtained when the p-a-SiC band gap is slightly larger than the band gap of the absorber layer. We have assessed the potential of core-loss EELS for detecting B and C concentrations as low as 10²⁰ cm^-3 in a spatially resolved manner, and of low-loss EELS as a probe of the local variations in plasmon energy.     

Microstructures of high-growth-rate (up to 8.3 nm/s) microcrystalline silicon photovoltaic layers and their influence on the photovoltaic performance of thin-film solar cells

Microstructures of microcrystalline silicon (μc-Si) deposited at a high-growth-rate have been investigated in order to apply to the photovoltaic i-layer. μc-Si films were prepared by very-high-frequency (100 MHz) plasma-enhanced chemical vapor deposition at 180 °C. High growth rates of 3.3–8.3 nm/s have been achieved utilizing high deposition pressures up to 24 Torr and large input powers. Applying μc-Si to n–i–p junction solar cells, as the optimum result in this experimental series, a conversion efficiency of 6.30% (J_SC: 22.1 mA/cm², V_OC: 0.470 V, and FF: 60.7%) has been achieved employing the i-layer deposited at 8.1 nm/s. Raman scattering and X-ray diffraction measurements revealed the crystalline volume fraction of around 50% with the (2 2 0) crystallographic preferential orientation, respectively. The cross-sectional transmission electron microscope image shows densely columnar structure grown directly on the underlying n-layer. These structural features are basically in good agreement those of low-growth-rate μc-Si used for a high efficiency solar cell as previously reported, implying advantages of the use of high pressures with regard to providing the photovoltaic i-layers. Finally, the implication is discussed from the photovoltaic performance as a function of the crystalline volume fraction of i-layer, and current problems in improving the photovoltaic performance are extracted.     

X-ray emission spectra and electronic structure of amorphous silicon

X-ray K and L emission bands of c-Si and a-Si are reported and compared with available XPS and UPS measurements. The experimental results for a-Si are found to be consistent and in excellent agreement. From comparison of the experimental results with available electron density-of-states calculations based on different structure models of the amorphous state, we conclude that only ST-12 structure and the Polk-Boudreaux model provide results that are compatible with experiment.Furthermore we have studied the high energy L satellite band of c-Si and a-Si.     

Growth and properties of microcrystalline germanium–carbide alloys grown using electron cyclotron resonance plasma processing

We report on the growth and properties of a new material, microcrystalline (Ge, C), which has potentially important optical, electrical and structural properties. The material was grown using a remote, low pressure electron cyclotron resosnance (ECR) plasma process on glass, stainless steel and c-Si substrates. The growth was done with hydrogen dilution and ion bombardment at temperatures of 350–400°C. We discovered that the optical absorption curve parallels that of c-Ge, with increased bandgaps as C is incorporated. We obtained up to 2% C incorporation, which increased the gap to 1.1 eV. At comparable bandgaps, the absorption coefficient of the (Ge, C) material is much larger than that of c-Si. Raman and X-ray measurements detected microcrystalline structure, and a dependence of grain size on the substrate used. The lattice constant contracted with C incorporation, approximately obeying Vegard’s law. Both undoped and n-doped materials were grown.     

NMR study of μc-Si:H

The behavior of hydrogen in glow-discharge (GD) μc-Si:H has been characterized by ¹H NMR. The ¹H spectra consist of two components with different linewidths. The linewidth (FWHM) of the narrow component is about 0.5 kHz at ν₀ = 90 MHz, being much narrower than has been observed in GD a-Si:H deposited under a conventional low RF-power condition. It has been demonstrated that the 0.5-kHz FWHM component originates from the hydrogens in motional narrowing state, and such fast-moving hydrogens are incorporated both in μc-Si:H and high-power deposited a-Si:H.     

Electron paramagnetic resonance and raman spectroscopy characterization of diamond films fabricated by HF CVD method

Thin polycrystalline diamond films were synthesized on silicon substrate by Hot Filament Chemical Vapor Deposition (HF CVD) technique from a mixture of hydrogen and different content of methyl alcohol. A comparative study on the Electron Paramagnetic Resonance (EPR), Raman spectroscopy and Scanning Electron Microscopy (SEM) were performed. It was shown that EPR signal, Raman spectra and morphology, studied by SEM, strongly depend on the ratio of CH₃OH/H₂ in the HF CVD reactor. The peak‐to‐peak line‐width in EPR signal varies from 0.09 to 0.8 mT depending on diamond quality. The Raman spectra of our diamond film showed, except well defined diamond Raman lines positioned at 1332 cm^‐1 with different Full Width at Half Maximum (FWHM), a broad band having maximum at around 1530 cm^‐1 which is characteristic for amorphous carbon phase. The obtained results show that EPR, SEM and Raman spectroscopy yield complementary results about the defects present in CVD diamond films. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Why does the open-circuit voltage in a micro-crystalline silicon PIN solar cell decrease with increasing crystalline volume fraction?

In hydrogenated micro-crystalline silicon (μc-Si:H) thin film solar cells, the open-circuit voltage (V_OC) shows a decline when the crystalline volume fraction (F_c) of the intrinsic μc-Si:H layer increases from 60% to over 90%. In this article we have simulated the experimental characteristics of solar cells, having intrinsic layers of different degrees of crystallinity to understand the reasons why. In order to model all aspects of the characteristics, we had to assume (a) wider band tails, (b) a higher mid-gap defect density and (c) a lower band gap for the more crystallized material. Modeling reveals that all three factors lower the field in the volume of the device and hence V_OC, due to higher photo-generated hole-trapping close to the P/I interface. The third factor brings the quasi-Fermi levels closer to the band-edges, resulting in higher free and trapped carrier densities throughout the device, with the trapped hole population particularly high at the P/I interface. We further show that V_OC is higher in a crystalline silicon PN cell, in spite of a sharply reduced band gap, because the lower effective density of states at the band-edges and sharply reduced band gap defect density overcome the effect of the smaller band gap.     

Low concentrator hetero-junction microcrystalline silicon solar cells

Multi-junction silicon-based thin-film solar cells are attractive materials for further cost-reduction and high efficiency. Meanwhile, it is also well considered that a concentrator solar cell is another alternative approach to enhance the conversion efficiency. In concentrator solar cells, the photocurrent linearly increases with the concentration ratio of incident light. At the same time, the open-circuit voltage (V_oc) of solar cells increases logarithmically with the photocurrent. This leads to an increase in efficiency with increasing sunlight intensity.We proposed a novel hetero-junction structure microcrystalline silicon (μc-Si:H) solar cell structure using wide-gap microcrystalline silicon oxide (μc-Si_1 ? xO_x:H) as p-layer and it has some advantages over conventional homo-junction μc-Si:H solar cells under low concentrations. It was observed that wide-gap doped layers can reduce carrier recombination rate especially in p-layer and at the p/i interface and V_oc enhancement with increasing light intensity improves as the band gap of p-layer is increased. Our best solar cell has efficiencies of 9.2% at 1 sun and 10.4% at 11.8 suns. We also investigated the degradation behavior of hetero-junction μc-Si:H solar cells. The degradation in efficiency for this type of solar cell was less than 6%. Therefore, hetero-junction μc-Si:H solar cell is the promising alternative for low-light concentration.     

Dependence of nanocrystalline SnO2 particle size on synthesis route

Very fine SnO₂ powders were produced by (a) slow and (b) forced hydrolysis of aqueous SnCl₄ solutions and (c) hydrolysis of tin(IV)-isopropoxide dissolved in isopropanol (sol-gel route) and then characterized by X-ray powder diffraction, Fourier transform infrared and laser Raman spectroscopies, TEM and BET. The XRD patterns showed the presence of the cassiterite structure. As found from XRD line broadening the crystallite sizes of all powders were in the nanometric range. TEM results also showed that the sizes of SnO₂ particles in all powders are in nanometric range. Very fine SnO₂ powders showed different features in the FT-IR spectra, depending on the route of their synthesis. The reference Raman spectrum of SnO₂ showed four bands at 773, 630, 472 and 86 (shoulder) cm⁻¹, as predicted by group theory. Very fine SnO₂ powders showed additional Raman bands, in dependence on their synthesis. The broad Raman band at 571 cm⁻¹ was ascribed to amorphous tin(IV)-hydrous oxide. The additional Raman bands at 500, 435 and 327 cm⁻¹ were recorded for nanosized SnO₂ particles produced by forced hydrolysis of SnCl₄ solutions. However, these additional Raman bands were not observed for nanosized SnO₂ particles produced by slow hydrolysis of SnCl₄ solution or the sol-gel route. The aggregation effects of nanosized particles were considered in the interpretation of the Raman band at 327 cm⁻¹. The method of low frequency Raman scattering was applied for SnO₂ particle size determination. On the basis of these measurements it was concluded that the size of SnO₂ particles was also in the nanometric range and that, the sol-gel particles heated to 400 °C consisted of several SnO₂ crystallites.     

Study of anomalous behavior of steady state photoconductivity in highly crystallized undoped microcrystalline Si films

The photoconductivity (σ_ph) of highly crystallized dense undoped hydrogenated microcrystalline silicon (μc-Si:H) films was measured as a function of light illumination over a wide temperature range (∼15–325 K). A thermal quenching behavior in σ_ph was observed at ∼240 K. The photoconductivity exponent (γ) was found to be sublinear with γ as low as 0.13. A density of states (DOS) profile having a steep conduction band tail, and valence band tail with two distinct distributions was found to be necessary to understand the electronic transport behavior in the inherently heterogeneous μc-Si:H films.     

H NMR in μc-Si:H

NMR, IR, ESR, Raman scattering and X-ray diffraction measurements were performed in μc-Si:H prepared by various methods. Results of H NMR in some films are qualitatively similar to those i n a-Si:H, but the NMR lines exhibit a motional narrowing. Other films which exhibit sharp IR peaks exhibit H NMR signal shape different from that in a-Si:H.     

Computational and Raman studies of phospho-tellurite glasses as ultrabroad Raman gain media

Molecular orbital calculations of two phospho-tellurite model clusters were performed to clarify the origins of the Raman bands in the Stokes region of over 1000 cm^− 1 in phospho-tellurite glasses. The Raman bands could be attributed to two components of 900-1050 cm^− 1 of symmetrical stretching vibrations of PO₄ units and 1050-1200 cm^− 1 of anti-symmetrical stretching vibrations of PO₄ units. It was also clarified that the top of the valence band of phospho-tellurite glasses consists of the lone pair electrons in a TeO_4 + 1 unit and the bottom of the conduction band of the glass consists of the antibonding hybrids of Te 5p and O 2p orbitals in the equatorial plane of a TeO₄ unit.We have developed new phospho-tellurite glasses which have the Raman gain peak of 30 times as large as silica glass or the Raman gain bandwidth of more than 1200 cm^− 1.     

AMPS-1D simulation studies of electronic transport in n+-μc-Si:H thin films

To study the electronic transport in highly n-doped microcrystalline silicon (n⁺-μc-Si:H) thin films, grain-boundary trapping model is implemented in AMPS (analysis of microelectronic and photonic structure)-1D. This approach is based on the traditional thermionic-emission model and considering the electronic transport parallel to the substrate. In spite of its simplicity, the model leads to the simulated values of activation energy, free carrier concentration, interface trap charge density and mobility which are in good agreement with the referred Hall effect measurement results for electron cyclotron resonance-chemical vapor deposited (ECR-CVD) highly n-doped μc-Si:H thin films.     

Hydrogenated microcrystalline silicon thin films deposited by RF-PECVD under low ion bombardment energy using voltage waveform tailoring

We present experimental results for hydrogenated amorphous and microcrystalline silicon (a-Si:H and μc-Si:H) thin films deposited by PECVD while using a voltage waveform tailoring (VWT) technique to create an electrical asymmetry in the reactor. VWT dramatically modifies the mean ion bombardment energy (IBE) during growth, and we show that for a constant peak-to-peak excitation voltage (V_PP), waveforms resembling “peaks” or “valleys” result in very different material properties. Using Raman scattering spectroscopy, we show that the crystallinity of the material depends strongly on the IBE, as controlled by VWT. A detailed examination of the Raman scattering spectra reveals that the narrow peak at 520 cm^? 1 is disproportionately enhanced by lowering the IBE through the VWT technique. We examine this effect for a range of process parameters, varying the pressure, hydrogen–silane dilution ratio, and total flow of H₂. In addition, the SiH_X bonding in silicon thin films deposited using VWT is characterised for the first time, showing that the hydrogen bonding character is changed by the IBE. These results demonstrate the potential for VWT in controlling the IBE during thin film growth, thus ensuring that application-appropriate film densities and crystallinities are achieved, independent of the injected RF power.