Temperature-dependent properties of nc-Si thin films synthesized in low-pressure, thermally nonequilibrium, high-density inductively coupled plasmas

Silicon thin films were synthesized simultaneously on single-crystal silicon and glass substrates by lowpressure, thermally nonequilibrium, high-density inductively coupled plasma-assisted chemical vapor deposition from the silane precursor gas without any additional hydrogen dilution in a broad range of substrate temperatures from 100 to 500 °C. The effect of the substrate temperature on the morphological, structural and optical properties of the synthesized silicon thin films is systematically studied by X-ray diffractometry, Raman spectroscopy, UV-vis spectroscopy, and scanning electron microscopy. It is shown that the formation of nanocrystalline silicon (nc-Si) occurs when the substrate temperature is higher than 200 °C and that all the deposited nc-Si films have a preferential growth along the (111) direction. However, the mean grain size of the (111) orientation slightly and gradually decreases while the mean grain size of the (220) orientation shows a monotonous increase with the increased substrate temperature from 200 to 500 °C. It is also found that the crystal volume fraction of the synthesized nc-Si thin films has a maximum value of ∼69.1% at a substrate temperature of 300 rather than 500 °C. This rather unexpected result is interpreted through the interplay of thermokinetic surface diffusion and hydrogen termination effects. Furthermore, we have also shown that with the increased substrate temperature from 100 to 500 °C, the optical bandgap is reduced while the growth rates tend to increase. The maximum rates of change of the optical bandgap and the growth rates occur when the substrate temperature is increased from 400 to 500 °C. These results are highly relevant to the development of photovoltaic thin-film solar cells, thin-film transistors, and flat-panel displays.

Rapid, low-temperature synthesis of nc-Si in high-density, non-equilibrium plasmas : enabling nanocrystallinity at very low hydrogen dilution

Nanocrystalline silicon thin films were deposited on single-crystal silicon and glass substrates simultaneously by inductively coupled plasma-assisted chemical vapor deposition from the reactive silane reactant gas diluted with hydrogen at a substrate temperature of 200 °C. The effect of hydrogen dilution ratio X (X is defined as the flow rate ratio of hydrogen to silane gas), ranging from 1 to 20, on the structural and optical properties of the deposited films, is extensively investigated by Raman spectroscopy, X-ray diffraction, Fourier transform infrared absorption spectroscopy, UV/VIS spectroscopy, and scanning electron microscopy. Our experimental results reveal that, with the increase of the hydrogen dilution ratio X, the deposition rate Rd and hydrogen content CH are reduced while the crystalline fraction Fc, mean grain size δ and optical bandgap ETauc are increased. In comparison with other plasma enhanced chemical vapor deposition methods of nanocrystalline silicon films where a very high hydrogen dilution ratio X is routinely required (e.g. X > 16), we have achieved nanocrystalline silicon films at a very low hydrogen dilution ratio of 1, featuring a high deposition rate of 1.57 nm/s, a high crystalline fraction of 67.1%, a very low hydrogen content of 4.4 at.%, an optical bandgap of 1.89 eV, and an almost vertically aligned columnar structure with a mean grain size of approximately 19 nm. We have also shown that a sufficient amount of atomic hydrogen on the growth surface essential for the formation of nanocrystalline silicon is obtained through highly-effective dissociation of silane and hydrogen molecules in the high-density inductively coupled plasmas. © 2009 The Royal Society of Chemistry.

The diphasic nc-Si/a-Si : H thin film with improved medium-range order

A series of silicon film samples were prepared by plasma enhanced chemical vapor deposition (PECVD) near the threshold from amorphous to nanocrystalline state by adjusting the plasma parameters and properly increasing the reactions between the hydrogen plasma and the growing surface. The microstucture of the films was studied by micro-Raman and Fourier transform infrared (FTIR) spectroscopy. The influences of the hydrogen dilution ratio of silane (R-H = [H-2]/[SiH4]) and the substrate temperature (T-s) on the microstructural and photoelectronic properties of silicon films were investigated in detail. With the increase of RH from 10 to 100, a notable improvement in the medium-range order (MRO) of the films was observed, and then the phase transition from amorphous to nanocrystalline phase occurred, which lead to the formation of diatomic hydrogen complex, H-2* and their congeries. With the increase of T-s from 150 to 275 degreesC, both the short-range order and the medium range order of the silicon films are obviously improved. The photoconductivity spectra and the light induced changes of the films show that the diphasic nc-Si/a-Si:H films with fine medium-range order present a broader light spectral response range in the longer wavelength and a lower degradation upon illumination than conventional a-Si:H films. (C) 2004 Elsevier B.V. All rights reserved.

Preferred growth of nanocrystalline silicon in boron-doped nc-Si : H Films

Preferred growth of nanocrystalline silicon (nc-Si) was first found in boron-doped hydrogenated nanocrystalline (nc-Si:H) films prepared using plasma-enhanced chemical vapor deposition system. The films were characterized by high-resolution transmission electron microscope, X-ray diffraction (XRD) spectrum and Raman Scattering spectrum. The results showed that the diffraction peaks in XRD spectrum were at 2theta approximate to 47degrees and the exponent of crystalline plane of nc-Si in the film was (220). A considerable reason was electric field derived from dc bias made the bonds of Si-Si array according to a certain orient. The size and crystalline volume fraction of nc-Si in boron-doped films were intensively depended on the deposited parameters: diborane (B2H6) doping ratio in silane (SiH4), silane dilution ratio in hydrogen (H-2), rf power density, substrate's temperature and reactive pressure, respectively. But preferred growth of nc-Si in the boron-doped nc-Si:H films cannot be obtained by changing these parameters. (C) 2004 Elsevier Ltd. All rights reserved.

NIP a-Si : H solar cells on stanless steel with p-type nc-Si : H window layer

The successful application of boron-doped hydrogenated nanocrystalline silicon as window layer in a-Si: H nip solar cells on stainless steel foil with a thickness of 0.05 mm is reported. Open circuit voltage and fill factor of the fabricated solar cell were 0.90V and 0.70 respectively. The optical and structural properties of the p-layers have been investigated by using UV-VIS and Raman spectroscopy. It is confirmed that the p-layer is hydrogenated nanocrystalline silicon with a wide optical gap due to quantum size effect.

Nonlinear optical response of nc-Si-SiO2 films studied with femtosecond four-wave mixing technique

Nonlinear optical properties of silicon nanocrystals (nc-Si) embedded in SiO2 films are investigated using time-resolved four-wave mixing technique with a femtosecond laser. the off-resonant third-order nonlinear susceptibility chi((3)) is observed to be 1.3 x 10(-10) esu at 800 nm. The relaxation time of the film is fast as short as 50 fs. The off-resonant nonlinearity is predominantly electronic in origin and enhanced due to quantum confinement.

Study on variable capacitance diode of (p)nc-Si : H/(n)c-Si heterojunction

Hydrogenated nanocrystalline silicon (nc-Si:H) layers of boron-doped increasing step by step was deposited on n-type crystalline silicon substrate using Plasma Enhanced Chemical Vapor Deposition (PECVD) system. After evaporating Ohm contact electrode on the side of substrate and on the side of nc-Si:H film, a structure of electrode/ (p)nc-Si:H/(n)c-Si/electrode was obtained. It is confirmed by electrical measurement such as I-V curve, C-V curve and DLTS that this is a variable capacitance diode. (C) 2003 Elsevier Science Ltd. All rights reserved.

Preparation and characterization of the stable nc-Si/a-Si : H films

High-quality nc-Si/a-Si:H diphasic films with improved stability were prepared by using the plasma-enhanced chemical vapor deposition technology. In comparison with typical amorphous silicon, the diphasic silicon films possess higher photoconductivity (two orders larger than that of the amorphous silicon film) and fairly good photosensitivity(the ratio of the photo-to dark-conductivity is about 10) and higher stability (the degradation of the photoconductivity is less than 10% after 24h long light soaking with 50 mW/cm(2) intensity at room temperature). In addition, the diphasic silicon film has a better light spectra response in the longer wavelength range. The improvement in photoelectronic properties may be attributed to: the existence of the disorder within the amorphous matrix, which breaks the momentum selection rule in the optical transition and, consequently, results in the large light absorption coefficient and high photosensitivity; the improved medium range order and low gap states density. Excess carriers generated in the amorphous matrix tend to recombine in the embedded crystallites, which suppresses nonradiative recombination within the amorphous matrix and reduces the subsequent defect creation.

Influence of coupling between Er3+, nc-Si and nonradiative centers on photoluminescence from Er3+-doped nc-Si/SiO2 films

Con-elation between nc-Si, Er3+ and nonradiative defects in Er-doped nc-Si/SiO2 films is studied. Upon the 514.5 run laser excitation, the samples exhibit a nanocrystal-related spectrum centered at around 750 nm and an Er3+ luminescence line at 1.54mum. With increasing Er3+ content in the films,the Er3+ emission becomes intense while the photoluminescence at 750 nm decreases. Hydrogen passivation of the samples is shown to result in increases of the two luminescence peaks. However, the effect of hydrogen treatment is different for the samples annealed at different temperatures. The experimental results show that the coupling between Er3+, nc-Si and noradiative centers has a great influence on photoluminescence from nc-Si/SiO2 < Er > films.

Numerical simulation of nc-Si : H/c-Si heterojunction solar cells

AMPS simulator, which was developed by Pennsylvania State University, has been used to simulate photovoltaic performances of nc-Si:H/c-Si solar cells. It is shown that interface states are essential factors prominently influencing open circuit voltages (V-OC) and fill factors (FF) of these structured solar cells. Short circuit current density (J(SC)) or spectral response seems more sensitive to the thickness of intrinsic a-Si:H buffer layers inserted into n(+)-nc-Si:H layer and p-c-Si substrates. Impacts of bandgap offset on solar cell performances have also been analyzed. As DeltaE(C) increases, degradation of VOC and FF owing to interface states are dramatically recovered. This implies that the interface state cannot merely be regarded as carrier recombination centres, and impacts of interfacial layer on devices need further investigation. Theoretical maximum efficiency of up to 31.17% (AM1.5,100mW/cm(2), 0.40-1.1mum) has been obtained with BSF structure, idealized light-trapping effect(R-F=0, R-B=1) and no interface states.

Study on optical band gap of boron-doped nc-Si : H film

The optical band gap (E-g) of the boron (B)-doped hydrogenated nano-crystalline silicon (nc-Si:H) films fabricated using plasma enhanced chemical vapor deposition (PECVD) was investigated in this work. The transmittance of the films were measured by spectrophotometric and the E-g was evaluated utilizing three different relations for comparison, namely: alphahnu=C(hnu-E-g)(3), alphahnu=B-0(hnu-E-g)(2), alphahnu=C-0(hnu-E-g)(2). Result showed that E-g decreases with the increasing of Boron doping ratio, hydrogen concentration, and substrate's temperature (T-s), respectively. E-g raises up with rf power density (P-d) from 0.45W.cm(-2) to 0.60w.cm(-2) and then drops to the end. These can be explained for E-g decreases with disorder in the films.

Impact of wide bandgap p-type nc-Si on the performance of a-Si solar cells

This paper reports the impact of a wide bandgap p-type hydrogenated nanocrystalline silicon (nc-Si:H) on the performances of hydrogenated amorphous silicon (a-Si:H) based solar cells. The player consists of nanometer-sized Si crystallites and has a wide effective bandgap determined mainly by the quantum size-confinement effect (QSE). By incorporation of this p-layer into the devices we have obtained high performances of a-Si:H top solar cells with V-infinity=1.045 V and FF=70.3 %, and much improved mid and bottom a-SiGe:H cells, deposited on stainless steel (SS) substrate. The effects of the band-edge mismatch at the p/i-interface on the I-V characteristics of the solar cells arc discussed on the bases of the density-functional approach and the AMPS model.

Carrier transport properties of the (n)nc-Si : H/(p)c-Si heterojunction

Phosphor-doped nano-crystalline silicon ((n))nc-Si:H) films are successfully grown on the p-type (100) oriented crystal silicon ((p) c-Si) substrate by conventional plasma-enhanced chemical vapor deposition method. The films are obtained using high H-2 diluted SiH4 as a reaction gas source and using PH3 as the doping gas source of phosphor atoms. Futhermore, the heterojunction diodes are also fabricated by using (n)nc-Si:H films and (p)c-Si substrate. I-V properties are investigated in the temperature range of 230-420K. The experimental results domenstrate that (n)nc-Si:H/(p) c-Si heterojunction is a typical abrupt heterojunction having good rectifing and temperature properties. Carrier transport mechanisms are tunneling - recombination model at forward bias voltages. In the range of low bias voltages ( V-F< 0.8 V), the current is determined by recombination at the (n)nc-Si:H side of the space charge region, while the current becomes tunneing at higher bias voltages( V-F>1.0 V). The present heterojunction has high reverse breakdown voltage ( > - 75 V) and low reverse current (approximate to nA).

Improved diphasic nc-si/a-si : H I-layer materials using PECVD

Two series of films has been prepared by using a new regime of plasma enhanced chemical vapor deposition (PECVD) in the region adjacent to the phase transition from amorphous to crystalline state. The photoelectronic properties of the films have been investigated as a function of crystalline fraction. In comparison with typical a-Si:H, these diphasic films with a crystalline fraction less than 0.3 show a similar optical absorption coefficient, higher mobility life-time product ( LT) and higher stability upon light soaking. By using the diphasic nc-Si/a-Si films as the intrinsic layer, a p-i-n junction solar cell has been prepared with an initial efficiency of 9. 10 % and a stabilized efficiency of 8.56 % (AM 1.5, 100 mW/cm(2)).

Z扫描法研究nc-Si/SiN_x多量子阱材料非线性光学特性

采用射频磁控反应溅射技术与热退火处理制备了nc-Si/SiN_x多量子阱材料.对样品进行了小角度XRD、Raman光谱、吸收光谱测试,研究了其结构和光学性质.采用皮秒脉冲激光单光束Z-扫描技术研究了样品在非共振吸收区的三阶非线性光学特性.实验结果表明,其非线性折射率为负值,非线性吸收属于双光子吸收.由实验数据计算得材料三阶非线性极化率为7.50×10~(-8)esu,该值比体硅材料的三阶非线性极化率大4个数量级.对材料光学非线性产生的机理进行了探讨,认为材料的非线性极化率的增加来源于材料量子限制效应增强.