The interpretation of the electric and optical properties of a-Si:H films produced by rf glow discharge through dark conductivity,photoconductivity and pulse controlled capacitance-voltage measurements

This paper deals with the interpretation of transport properties of amorphous silicon hydrogenated films (a-Si:H) through dark conductivity, photoconductivity and pulse controlled capacitance-voltage measurements. a-Si:H films were produced by rf glow discharge coupled either inductively or capacitively to a 3% SiH₄/Ar mixture at different crossed electromagnetic static fields. The data concerned with the dark activation energy, photoactivation energy, variation of the density of localized states and photosensitivity, (σ_ph/σ_d)_25°C, of a-Si:H films can account for their optoelectronic properties which are strongly dependent on the deposition parameters. We also observed that crossed electromagnetic static fields applied during film formation influences hydrogen incorporation in a different manner than previously proposed.     

Fractional composition of large crystallite grains: A unique microstructural parameter to explain conduction behavior in single phase undoped microcrystalline silicon

We have studied the dark conductivity of a broad microstructural range of plasma deposited single phase undoped microcrystalline silicon (μc-Si:H) films in a wide temperature range (15–450 K) to identify the possible transport mechanisms and the interrelationship between film microstructure and electrical transport behavior. Different conduction behaviors seen in films with different microstructures are explained in the context of underlying transport mechanisms and microstructural features, for above and below room temperature measurements. Our microstructural studies have shown that different ranges of the percentage volume fraction of the constituent large crystallite grains (F_cl) of the μc-Si:H films correspond to characteristically different and specific microstructures, irrespective of deposition conditions and thicknesses. Our electrical transport studies demonstrate that each type of μc-Si:H material having a different range of F_cl shows different electrical transport behaviors.     

利用快速热退火法制备多晶硅薄膜

为了制备优质的多晶硅薄膜,该论文研究了非晶硅薄膜的快速热退火(RTA)技术.先利用PECVD设备沉积非晶硅薄膜,然后把其放入快速热退火炉中进行退火.退火前后的薄膜利用X射线衍射(XRD)仪、Raman光谱仪及扫描电子显微镜(SEM)测试其晶体结构及表面形貌,利用电导率测试设备测试其暗电导率.研究表明退火温度、退火时间以及沉积时的衬底温度对非晶硅薄膜的晶化都有很大的影响.     

Improvement of photoconductivity in Silicon Tin (SiSn) thin films

Hydrogenated-amorphous silicon tin alloy (a-SiSn (C:H)) films have been prepared by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD) technique. We present investigations of the absorption and photoconductivity characteristics of a-SiSn(C:H) thin films as a function of the tin concentration, which could be a pivotal feature for the bottom solar cell development. We demonstrate that the photoconductivity is significantly improved by the film growth under enhanced hydrogen dilution. The results suggest that the hydrogen dilution plays an important role in development of high quality a-SiSn(C:H) photosensitive thin films.     

Effect of Silane flow rate on microstructure of Silicon films deposited by HWCVD

Hydrogenated silicon films ranging from pure amorphous to those containing small crystallites in large crystalline fraction are prepared using the HWCVD technique without using any hydrogen dilution which is supposed to be necessary for the deposition of nanocrystalline Si films. The only parameter that is varied is Silane flow rate. The deposition rate ranges from 6–27 Å/s. The band gap of the films (1.8–2.0 eV) is high compared to the regular films, which is attributed to the improved short and medium range order as well as the presence of low density amorphous tissues in the grain boundary regions. The films show improved stability under long term light exposure due to more ordered structure and presence of hydrogen mostly as strong Si―H bonds.     

Surface wave attenuation by silicon,hydrogen, and deuterium in amorphous silicon films

Motions of silicon, hydrogen, and deuterium in sputtered thin films of a-Si, a-Si:H, and a-Si:D were studied by measurements of the attenuation of surface acoustic waves propagating along the surface of piezoelectric crystals which were covered by the thin films. It is concluded that there are H and D atoms (ions) which are not directly associated with the Si bonds. Some of the H and D atoms (ions) are configurationally rearranged at room temperature. A part of the hydrogen (deuterium) or argon is located in voids.     

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.     

Effect of hydrogen on the intrinsic stress in ion beam sputtered amorphous silicon films

The results of measurements of the intrinsic stress in hydrogenated amorphous silicon (a-Si:H) films deposited by ion beam sputtering are presented. The data show that the total intrinsic stress is composed of growth stress and hydrogen induced stress. At high hydrogen concentration (> 24%), an abrupt decrease in stress is observed which correlates with a microstructural change as shown by SEM and spectrosoopic ellipsometry measurements. The change in microstructure is accompanied by a modification in the IR transmission spectrum at 2000 cm⁻¹ indicating a change in hydrogen bonding configuration or in local environment near SiH bonds. A model is proposed which reconciles the observation of both tensile and compressive stress in unhydrogenated silicon reported in the literature.     

沉积温度对等离子体化学气相沉积制备硅氧薄膜微结构的影响

利用13.56 MHz的射频等离子体化学气相沉积设备(RF-PECVD)在不同沉积温度(50~400 ℃)下制备了一系列氢化硅氧(SiO_x:H)薄膜材料,并研究了薄膜材料性能与微结构的变化规律。随着沉积温度的增加,薄膜内的氧含量(C_O)下降,晶化率(X_C)也下降,折射率(n)上升,此外,薄膜的结构因子(R)下降,氢含量(C_H)先上升后下降,由此在合适的中间温度下可以获得最大的氢含量。通过实验结果分析提出了不同沉积温度下制备硅氧薄膜的内在微结构模型:低温下沉积的硅氧薄膜是以氢化非晶硅氧(a-SiO_x:H)相为主体并嵌入氢化纳米晶硅(nc-Si:H)的复合材料,而在高温下沉积的硅氧薄膜则是以氢化非晶硅(a-Si:H)相为主体并嵌入越来越少的nc-Si:H相和a-SiO_x:H相的复合材料。由上可知,要制备太阳电池通常采用的晶化率X_C高、氧含量C_O高的氢化纳米晶硅氧(nc-SiO_x:H)材料,需要采用相对较低的沉积温度。     

CVD金刚石薄膜亚表面层氢杂质对表面活化反应的影响

采用密度泛函理论平面波赝势法研究了氢杂质位于氢终止金刚石薄膜亚表面层中三种不同位点处时金刚石的结构变化,以及氢原子在三种金刚石薄膜表面上的吸附难易程度,并对表面活化反应进行了过渡态搜索以探究化学气相沉积(CVD)过程中金刚石薄膜亚表面层氢杂质对表面活化的影响.对比计算结果发现:生长过程中,亚表面层的氢杂质使其附近的金刚...     

Hydrogenated amorphous silicon produced by laser induced chemical vapor deposition of silane

a-Si:H films deposited by laser induced CVD (LICVD) have been characterized and the growth process modelled. Growth rates are exponentially dependent on gas temperature and film properties follow the equilibrium hydrogen content, exponentially dependent on substrate temperature.     

Remote plasma deposition of microcrystalline silicon thin-films: Film structure and the role of atomic hydrogen

Microcrystalline silicon films grown in an expanding thermal plasma, i.e. in the absence of ion bombardment, are found to be porous and rich in nano-sized voids. By carrying out an extensive investigation on the material quality of films deposited in the amorphous-to-microcrystalline transition regime, on the microcrystalline silicon growth development, and on the influence of the substrate temperature, it is concluded that the inferior material quality is related to the lack of a sufficient amount of amorphous silicon tissue. As possible cause for the insufficient amount of amorphous silicon tissue, the interaction of atomic hydrogen with amorphous silicon films has been studied in order to highlight a possible competition between film growth and H-induced etching of amorphous silicon, and between film growth and H-induced surface/film modification. The etch rates obtained are too low to compete with film growth. Furthermore, atomic H cannot be considered responsible for the poor quality of amorphous tissue present in the microcrystalline silicon films, as the H up-take mainly takes place in divacancies. These results suggest that ion bombardment may be a necessary condition to provide good quality microcrystalline silicon films.     

Properties of a-Si : H : F deposited in SiF4/SiH4/Ar Gas mixtures by a glow-discharge technique

Films of silicon-hydrogen-fluorine alloys (a-Si : H : F) were prepared by capacitive coupling rf glow discharge in an SiF₄/SiH₄/Ar gas mixture. Up to 4% fluorine can be incorporated in films prepared with a gas mixture of SiF₄/(SiF₄ + SiH₄) = 0.72. The hydrogen concentration decreases as fluorine concentration increases but there is still more hydrogen than fluorine in films with the highest density of fluorine, which is in sharp contrast to the best films produced by the Madan and co-workers. Both dark conductivity and photoconductivity decrease as fluorine increases, though improvement of doping efficiency was observed in films with moderate concentrations of fluorine. The influence of hydrogen is more important than the influence of fluorine in the present silicon-hydrogen-fluorine alloys.     

Dark conductivity in amorphous undoped silicon films

The temperature dependence of the dark conductivity was investigated in amorphous undoped silicon films deposited by glow-discharge in a SiCl₄H₂ mixture. Different transport processes were indentified according to the investigated temperature range. The dependence of the dark conductivity was also examined as a function of some deposition parameters. The experimental results are discussed in terms of the two-phase structure of the film.     

Eine spektroskopische Methode zur Untersuchung des Anfangsstadiums der Metallschichtbildung auf Glas

A simple detection of light metallic deposits (e. g. nickel) on oxidic surfaces can be achieved by means of the spectroscopical measurement of the concentration of hydrogen atoms in the positive column of a glow discharge. – The kinetics analysis of the experimental results shows that the velocity of forming as well as the heterogeneous recombination of hydrogen atoms depend on the amount of nickel being deposited on the surface area. The kinetic data allow conclusions to be drawn concerning the process and velocity of metallic deposits on glass surfaces. The initial phase of film forming, hitherto experimentally difficult to follow, can thus be studied. Measurements of the electrical resistance show the island structure of the thin nickel films. Due to the surface diffusion of hydrogen atoms such a discontinuous film exhibits the same catalytic activity for the recombination of hydrogen atoms as a continuous film.     

Normal and anti Meyer–Neldel rule in conductivity of highly crystallized undoped microcrystalline silicon films

We have studied the electrical conductivity behavior of highly crystallized undoped hydrogenated microcrystalline silicon (μc-Si:H) films having different microstructures. The dark conductivity is seen to follow Meyer–Neldel rule (MNR) in some films and anti-MNR in others, which has been explained on the basis of variation in the film microstructure and the corresponding changes in the effective density of states distributions. A band tail transport and statistical shift of Fermi level are used to explain the origin of MNR as well as anti-MNR in our samples. The observation of MNR and anti-MNR in electrical transport behavior of μc-Si:H is discussed in terms of the basic underlying physics of their origin and the significance of these relationships.     

Optical properties of hydrogenated amorphous silicon films doped with fluorinated gases

Doped amorphous silicon films were prepared by plasma-enhanced chemical vapour deposition of silane and hydrogen mixtures, using phosphorus pentafluoride (PF₅) and boron trifluoride (BF₃) as dopant precursors. The films were studied by UV-vis spectroscopy and their photo and dark conductivity were measured, the latter as a function of temperature. The optical gap of the n-type samples, doped with PF₅, diminished as the concentration of this gas in the plasma was increased. However, the optical gap of p-type samples, doped with BF₃, did not show any appreciable optical gap decrease as the concentration of BF₃ was varied from 0.04% to 4.7%. The dark conductivity of the p-type films at these extremes of the doping range were 7.6 × 10⁻¹⁰ and 3.5 × 10⁻¹ Ω⁻¹ cm⁻¹, respectively.     

Isochronal Studies of α‐Si:H Crystallization and the Performance of it's Schottky Barriers

Hydrogenated amorphous silicon films (α‐Si:H) were crystallized employing a metal induced crystalline (MIC) technique. Structural changes during annealing these films at 300 °C for different periods (0‐300 minutes) were obtained by XRD. Al was used as a metal induced crystalline for α‐Si:H produced by ultra high vacuum (UHV) plasma enhanced chemical vapor deposition (PECVD). XRD shows that crystallization of the interacted α‐Si:H film underneath Al initiates at 300 °C for 15 minutes. A complete crystallization was obtained after annealing for 60 minutes. A gold dot was evaporated onto α‐Si:H films, which annealed for different periods to form Schottky barriers. Electrical properties of Au/α‐Si:H were calculated such as the ideality factor, n, barrier height, Φ_B, donor concentration, N_D, and the diffusion voltage, V_d, as a function of the annealing time of α‐Si:H films. All these parameters were carried out through the current voltage characteristics (J‐V) and the capacitance voltage measurements (C‐V). The results were presented a discussed on the basis of XRD performance and the thermionic emission theory.     

Study of in-gap defects in intrinsic and B-doped a-Si1−xCx:H by photo-induced optical absorption and photoluminescence

The infrared (IR) absorption dependence on visible light illumination has been measured in doped and undoped hydrogenated amorphous silicon carbide (a-Si_1−xC_x:H) films grown by plasma enhanced chemical vapour deposition. The measurements were made by a highly sensitive technique which exploits properly designed a-Si_1−xC_x:H/ZnO test waveguides for lengthening the interaction region between the IR and visible (VIS) radiations in the material. Experimental data show that boron doping strongly enhances the VIS light induced variation of the IR absorption, whereas the increase in carbon content has a quenching effect on the phenomenon. The a-SiC:H films have been also characterized by photoluminescence measurements. The spectra are dominated by a photoluminescence band, ranging between 1.4 eV and 1.9 eV. This band is enhanced by the increase in carbon content, while is strongly quenched with increasing B-doping level. On the basis of these results, a correlation is found between the measurements of optical absorption, photo-induced absorption and photoluminescence. The type and the density of defects induced in the films by the different growth conditions have been recognized as the origin of the different behaviors observed.     

High-rate deposition of nanocrystalline silicon using the expanding thermal plasma technique

Nanocrystalline silicon films have been deposited at very high deposition rates using the expanding thermal plasma technique and their structural properties have been analyzed. The crystallinity and crystallite size and orientation have been determined for various hydrogen-to-silane dilution ratios and it is shown that films with a crystalline fraction of 60–80% can be deposited at deposition rates within the range 1.5–3.0 nm/s. The hydrogen concentration and atomic densities in the film have been investigated by infrared spectroscopy and elastic recoil detection/Rutherford backscattering revealing underestimation of the hydrogen content by infrared spectroscopy as well as a reduced atomic film density for the nanocrystalline silicon films.