Distribution of hydrogen in low temperature passivated amorphous silicon (a-Si:H) films from neutron reflectivity

Hydrogen plays a critical role in the passivation of dangling bonds in hydrogenated amorphous silicon (a-Si:H) to enable acceptable semiconducting characteristics during operation in devices. Low temperature processing enables fabrication of high performance transistors on flexible substrates such as plastic or stainless steel foils, but also leads to a decrease in the stability of the electronic performance. Generation of defects at the a-Si:H/insulator (hydrogenated silicon nitride, SiN:H) during electrical use due to localized heating will lead to decreased performance unless the dangling bonds are passivated in-situ by residual hydrogen. For this reason, the distribution of hydrogen within a-Si:H may be critical to understanding their aging phenomena. Here the distribution of hydrogen within both a-Si:H and SiN:H layers is probed with sub-nanometer resolution using neutron reflectivity. The hydrogen concentration within the bulk of the a-Si:H (11 ± 2 at.%) and SiN:H (18 ± 3 at.%) agree well with previous reports, but the increased resolution of the neutron measurement is able to identify an approximate three fold increase in the concentration within 2 nm of the semiconductor-insulator interface. This enhanced hydrogen content may act in the short-term as a sink to passivate any dangling bonds formed during operation.     

Voids in hydrogenated amorphous silicon materials

Effusion measurements of hydrogen and of implanted helium are used to characterize the presence of voids in hydrogenated amorphous silicon (a-Si:H) materials as a function of substrate temperature, hydrogen content, etc. For undoped plasma-grown a-Si:H, interconnected voids are found to prevail at hydrogen concentrations exceeding 15–20 at.%, while isolated voids which act as helium traps appear at hydrogen concentrations ≤ 15 at.%. The concentration of such isolated voids is estimated to some 10¹⁸/cm³ for device-grade undoped a-Si:H deposited at a substrate temperature near 200 °C. Higher values are found for, e.g., doped material, hot wire grown a-Si:H and hydrogen-implanted crystalline Si. The results do not support recent suggestions of predominant incorporation of hydrogen in a-Si:H in (crystalline silicon type) divacancies, since such models predict a concentration of voids (which act as helium traps) in the range of 10²¹/cm³ and a correlation between void and hydrogen concentrations which is not observed.     

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.     

Properties of hydrogenated amorphous silicon prepared by chemical vapor deposition

Properties of hydrogenated amorphous silicon (a-Si:H) prepared by chemical vapor deposition (CVD) are reported and compared to corresponding properties of glow discharge a-Si:H. The CVD material was produced from mixtures of silane, disilane, trisilane and higher polysilanes in hydrogen carrier gas at one atmosphere total pressure, at substrate temperatures from 420 to 530 °C. The photovoltaic properties of our present CVD a-Si:H are somewhat inferior to those of the best glow discharge a-Si:H. However, as discussed below, there are some indications that higher quality CVD a-Si:H may be possible.     

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.     

Improvement of amorphous silicon n-i-p solar cells by incorporating double-layer hydrogenated nanocrystalline silicon structure

We develop a double-layer p-type hydrogenated nanocrystalline silicon (p-nc-Si:H) structure consisting of a low hydrogen diluted i/p buffer layer and a high hydrogen diluted p-layer to improve the hydrogenated amorphous silicon (a-Si:H) n-i-p solar cells. The electrical, optical and structural properties of p-nc-Si:H films with different hydrogen dilution ratio (R_H) are investigated. High conductivity, low activation energy and wide band gap are achieved for the thin films. Raman spectroscopy and high-resolution transmission electron microscopy (HRTEM) analyses indicate that the thin films contain nanocrystallites with grain size around 3-5 nm embedded in the amorphous silicon matrix. By inserting a p-nc-Si:H buffer layer at the i/p interface, the overall performance of the solar cell is improved significantly compared to the bufferless cell. The improvement is correlated with the reduction of the density of defect states at the i/p interface.     

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.     

Experimental evidence for extended hydrogen diffusion in silicon thin films during light-soaking

We have used mass spectrometry to detect hydrogen effusing from silicon thin films exposed to light. Our results indicate a long range diffusion of hydrogen through the whole film, which ends with its release into the vacuum system. The changes in the film properties are characterized by dark and photoconductivity and hydrogen exodiffusion measurements. From the evolution of dark conductivity measurements after turning off the light, we show that this long range motion of hydrogen is not due to the heating of the sample. A comparison of hydrogen exodiffusion spectra of as-deposited and light-soaked samples shows that the weakly-bonded hydrogen content decreases by 30% for a-Si:H films and that the tightly-bonded hydrogen migrates to grain boundaries of crystalline regions in the case of pm-Si:H films. These results clearly demonstrate the long range motion of hydrogen during light soaking.     

Effect of ex-situ hydrogen passivation on the structural properties of e-beam evaporated amorphous silicon thin film for solar cell applications

Thin-film photovoltaics greatly reduce the semiconductor material content in the finished product, using 150–200 times less material as compared with conventional Si wafer based cells. Electron beam evaporation (e-beam), a non-ultra-high vacuum technique has the potential for being inexpensive, and simpler process for a-Si deposition. It offers specific advantages such as high Si deposition rate (up to 1 μm/min), excellent Si source material usage, avoidance of toxic gases, and simple sample preparation conditions. In this work, we report the growth of a-Si films using e-beam at a growth rate exceeding 30 Å/s (1–5 Å/s for conventional PECVD process). We report the effect of hydrogen passivation on amorphous silicon network and on silicon-bonded hydrogen configuration under ex-situ hydrogenation in hydrogen plasma. The hydrogen concentration and silicon-hydrogen bonding configuration was evaluated using nuclear reaction analysis (NRA) and Fourier transform infrared spectroscopy (FTIR). Hydrogen plasma treatment shows an increase in the monohydride bond concentration with substrate temperature, and is corroborated by our FTIR investigation, in addition to reducing clustered monohydride bonds or polyhydride bonds in a-Si:H film. Raman analysis indicates reduction in silicon bond angle as well as the bond distance, both leading to significant structural improvement in short-range and medium range order in the amorphous phase. Thus, ex-situ hydrogenation clearly demonstrates the possibility of comparable hydrogen passivation in e‐beam evaporated a-Si films with high growth rate. One can easily extrapolate this result to microcrystalline film growth, assuming the structural improvement of the silicon network preceding the microcrystalline nucleation, where ex-situ passivation is most effective. Thus ex-situ hydrogenation opens up new possibilities in minutely tailoring the a:Si film properties especially for solar cell applications.     

Thirty years trajectory of amorphous and nanocrystalline silicon materials and their optoelectronic devices

A review is given on research trajectory of hydrogenated amorphous and nanocrystalline silicon (a-Si:H and nc-Si) materials with their device applications ongoing since the period of 1970. A brief explanation on the motivation to start amorphous semiconductors research is given to produce a new kind of synthetic semiconductor having continuous energy gap controllability with valency electron controllability. Due to the result of some basic research on the film quality improvement of a-Si:H and nc-Si, some innovative devices had been developed since middle of 1980s in R&D phase such as a-SiC/a-Si heterojunction solar cells, a-Si/a-SiGe and also a-Si/nc-Si tandem type solar cells. Finally, the state of the art on the industrialization of the new devices is introduced and discussed.     

Optical absorption edge in structure-inhomogeneous a-Si:H-based alloys

In this paper we measure microstructure and optical absorption edge of a-Si:H and silicon-rich a-SiN_r:H films prepared at deposition rates ∼0.8 nm/s by radio frequency plasma enhanced chemical vapor deposition method from hydrogen diluted SiH₄ and SiH₄ + NH₃ mixtures, respectively. Microstructure of films was studied by atomic force microscopy and infrared spectroscopy. Both a-Si:H and a-SiN_r:H films are inhomogeneous on a scale of ∼50 nm and contain Si-rich islands with hydrogen (in a-Si:H) or hydrogen and nitrogen (in a-SiN_r:H) collected at their boundaries. It was found that different atomic configurations of N and H determined from IR data should be attributed to such islands and their boundaries. It was established that the optical gap is determined by the concentration of hydrogen (in a-Si:H) or nitrogen (in a-SiN_r:H) in the islands while it is insensitive to variations of content of these alloy atoms at island boundaries. These results are interpreted in terms of a quantum well model modified to take into account structure of alloy atoms.     

Characterization of hydrogenated amorphous silicon thin films prepared by magnetron sputtering

Magnetron sputtered hydrogenated amorphous silicon (a-Si:H) thin films have been characterized. Hydrogen (H₂) with argon (Ar) was introduced into the sputtering chamber to create the plasma. A sudden increase in the deposition rate occurred when the hydrogen was added. The maximum hydrogen content of 16 atomic percent (at.%) was achieved and a bandgap of about 2.07 eV was determined from the spectral investigations of the hydrogenated films. The effect of radio frequency (RF) power on the deposition rate, as well as on the hydrogen content was investigated. To change the hydrogen content in the films, the hydrogen flow rate was varied while keeping the argon flow rate constant. The hydrogen content in the films increased with increasing hydrogen flow rate up to the maximum content of 16 at.% and then decreased for further increases in hydrogen flow.     

Ellipsometry characterization of a-Si:H layers for thin-film solar cells

In order to determine microscopic structures of hydrogenated amorphous silicon (a-Si:H) layers incorporated in a-Si:H-based thin-film solar cells, the spectroscopic ellipsometry (SE) analysis of a-Si:H layers prepared by plasma-enhanced chemical vapor deposition has been performed. In particular, we have characterized the a-Si:H layers by applying a new dielectric function model that allows the evaluation of the SiH₂ bond densities in a-Si:H networks. This model is based on our finding that the a-Si:H dielectric functions in the visible/ultraviolet region vary systematically with the formation of SiH₂-clustered microvoids. We have applied this model to estimate the SiH₂ content in a-Si:H layers fabricated on glass substrates, on which the characterization of the SiH₂ bonding is generally difficult. The validity of the SE analysis has been confirmed from the direct characterization of the SiH_n local structures using infrared ellipsometry.     

Electronic states in a-Si:H/c-Si heterostructures

We have investigated PECVD-deposited ultrathin intrinsic a-Si:H layers on c-Si substrates using UV-excited photoemission spectroscopy (hν = 4–8 eV) and surface photovoltage measurements. For samples deposited at 230 °C, the Urbach energy is minimal, the Fermi level closest to midgap and the interface recombination velocity has a minimum. The a-Si:H/c-Si interface density of states is comparable to that of thermally oxidized silicon interfaces. However, the measured a-Si:H dangling bond densities are generally higher than in thick films and not correlated with the Urbach energy. This is ascribed to additional disorder induced by the proximity of the a-Si:H/c-Si interface and H-rich growth in the film/substrate interface region.     

Local bonding of hydrogen in a-Si:H,a-Ge:H and a-Si,Ge:H alloy films

This paper reviews the local bonding of hydrogen (and deuterium) in a-Si:H(D), a-Ge:H(D) and a-Si, Ge:H(D) alloy films. We specify the types of atomic environments that have been identified through vibrational spectroscopy, primarily infrared (IR) absorption. We emphasize local modes and discuss the atomic motions that are responsible for the various spectral features. We discuss correlations between the occurrence of specific local bonding groups, e.g., polysilane and polygermane configurations, and the deposition techniques and parameters, including the substrate temperature (T_s), the gas mixtures and the RF power into a glow discharge, etc. We include a discussion of the theoretical approaches that have been used to treat vibrational modes in these materials. We emphasize the approximations that are valid because of the relatively light mass of the hydrogen and deuterium atoms compared with those of the silicon and germanium atoms. Finally we highlight the effects of neighboring alloy or impurity atoms on the frequencies of hydrogen vibrations in a-Si:H, and point out the differences between oxygen atom incorporation in a-Si and a-Ge alloys.     

A computational study of elastic properties of disordered systems with voids

We present a computational study of elastic properties of disordered systems with voids. The influence of hydrogen and voids on the elastic properties has been investigated by means of atomistic simulations using empirical potentials for hydrogenated amorphous silicon. The elastic constants have been obtained from the fluctuations of the simulation cell in Monte Carlo simulations at constant pressure and temperature. Our results indicate that the softening of the elastic constants of a-Si:H observed experimentally upon increasing hydrogen content cannot be explained by a weakening of the network induced by the reduced coordination but should be attributed instead to the formation of voids. A simple relation between Young’s modulus and the density is presented.     

Spatially localized current-induced crystallization of amorphous silicon films

Field-enhanced metal-induced solid phase crystallization (FE-MISPC) at room temperature is employed to create microscopic crystalline regions at predefined positions in hydrogen-rich amorphous silicon (a-Si:H) films. Electric field is applied locally using a sharp conductive tip in atomic force microscope (AFM) and nickel electrode below the a-Si:H film. The process is driven by a constant current of ?50 pA to ?500 pA while controlling the amount of transferred energy (1–300 nJ) as a function of time. Passing current leads to a formation of nanoscale pits in the a-Si:H films. Depending on the energy amount and rate the pits exhibit lower or orders of magnitude higher conductivity as detected by current-sensing AFM. High conductivity is attributed to a local crystallization of the films. This is confirmed by micro-Raman spectroscopy.     

热丝辅助MW ECR CVD技术高速沉积高质量氢化非晶硅薄膜

氢化非晶硅薄膜具有优异的光电特性,在制备薄膜太阳能电池中有重要的应用.本文采用热丝辅助MWECR CVD技术,通过调整各种工艺参数,制备了高沉积速率(DR＞2.5nm/s)及高光敏性(σph/σD＞105)的氢化非晶硅薄膜.实验表明,在衬底表面温度的分布中,热丝辐射和离子轰击引起的温度对薄膜的光敏性影响较大;在薄膜沉积的最后几分钟适当加大H2稀释率,有利于薄膜光电特性的改善.     

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。     

Defects and microvoids in a-Si and a-Si:H

We report the first measurements of positron-annihilation spectra of samples of both pure and hydrogenated amorphous silicon. Comparison of these spectra with that of crystalline silicon indicates that the lowest-lifetime component can be identified as the contribution mainly from valence-band electrons. Both the pure (a-Si) and the hydrogenated (a-Si:H) samples exhibit a component with intermediate lifetime, which we attribute to small vacancies consisting of about 4 missing atoms. Finally, only a-Si:H shows a significant long-lived line (τ > 5 ns), which arises from large microvoids, with ～ 100 missing atoms. The existence of these microvoids in a-Si:H is consistent with recent reports of the presence of occluded H₂ gas under high pressure in such films.