Light-induced defects in hydrogenated amorphous silicon germanium alloys

A selected survey of the phenomenon of light-induced deep defect creation in the hydrogenated amorphous silicon–germanium is presented. First a general review of the early studies that established the key salient features of light-induced degradation in a-Si,Ge:H is given. This is followed by a discussion of a couple of complicating issues that have more recently come to light; namely, the possibility that charged defects play a more central role in the alloys, and that both Si and Ge metastable dangling bonds may be playing a significant role in the alloys with germanium fractions below 20 at%. Following this, the results of some recent studies are summarized that have been focusing on the details of degradation in the low Ge fraction alloys to gain insight into the fundamentals of degradation of amorphous silicon materials in general. This review concludes with an overall assessment of the level of our understanding of degradation in the a-Si,Ge:H alloys and where some key issues are still remaining to be resolved.     

High-rate deposition of hydrogenated amorphous silicon films using inductively coupled silane plasma

Inductively coupled plasma (ICP) generated at 13.56 MHz has been employed for high-rate deposition of device-quality hydrogenated amorphous silicon (a-Si:H). It has been shown that an increase in the flow rate of a monosilane gas enhances the generation rate of deposition precursors, while the ion flux decreases and becomes saturated. The defect density reaches the minimum at a deposition rate of 2.3 nm/s. It has also been demonstrated that even at deposition rates around 4 nm/s, a-Si:H deposited at 150°C exhibits a subgap defect density lower than 6×10¹⁶ cm⁻³ after 12 h AM1 (100 mW/cm²) light soaking.     

Effect of annealing on the electrical, optical and structural properties of hydrogenated amorphous silicon films deposited in an asymmetric R.F. plasma CVD system at room temperature

This paper reports the effect of annealing on hydrogenated amorphous silicon films (a-Si : H) deposited by r.f. self-bias technique on cathode in an asymmetric r.f. plasma CVD system at room temperature. Detailed study of the variation of the dark and photoconductivity (σ_D and σ_ph) as a function of temperature and light intensity, surface morphology, hydrogen evolution, optical absorption, subgap absorption and related parameters, thermal and structural disorder on the optical-absorption edge, IR vibrational modes and bonded hydrogen content have been carried out on unannealed and annealed samples at different temperatures (T_a) from 100°C to 550°C. It is found that the values of σ_ph increase and that of Urbach energy (E_o), subgap defect density (N_d) and the polyhydride to monohydride ratio decrease upto T_a=250°C and beyond 250°C the values of σ_ph decrease and that of E_o, N_d and the polyhydride to monohydride ratio increase. The best opto-electronic properties with much improved σ_ph and σ_ph/σ_D and dominant monohydride bonding are obtained after annealing the room temperature deposited film at 250°C for 1 h. The σ_D data obeys a Meyer Neldel rule in annealed a-Si : H films. The value of optical band gap is found to be related to the E_o and the hydrogen content. The Urbach energy (E_o) which is a measure of the disorder is the sum of structural and thermal disorder. The structural disorder part decreases with the annealing temperature upto 300°C and thereafter it increases. The curves of optical absorption coefficient versus photon energy at different T_a converge to a common point.     

Study on hydrogenated silicon nitride for application of high efficiency crystalline silicon solar cells

The hydrogenated silicon nitride films (SiN_x:H) deposited by plasma enhanced chemical vapor deposition (PECVD) technique is commonly used as an antireflection coating as well as surface passivating layer of crystalline silicon solar cells. The refractive indices of SiN_x:H films could be changed by varying the growth gas ratio R(=NH₃/SiH₄+NH₃) and annealing temperature. For optimum SiN_x:H film, the optical and chemical characterization tools by varying the film deposition and annealing condition were employed in this study. Metal-insulator-semiconductor (MIS) devices were fabricated using SiN_x:H as an insulator layer and they were subjected to capacitance-voltage (C-V) and current-voltage (I-V) measurements for electrical characterization. The effect of rapid thermal annealing (RTA) on the surface passivation as well as antireflection properties of the SiN_x:H films deposited at various process conditions were also investigated for the fabrication of low cost and high efficiency silicon solar cells.     

Suppression of photo-induced dilation in cyanide treated hydrogenated amorphous silicon films

Effects of cyanide (CN) treatment with hydrogenated amorphous silicon (a-Si:H) films have been investigated. The decrease of ΔV/V was observed in cyanide treated a-Si:H films and the successive thermal annealing at 200°C after CN treatment induced the further reduction of the ΔV/V. XPS spectra show the indirect evidence that the cyanide species is present within 10 nm from the hydrogenated amorphous silicon surface. The results of CN treatment with a-Si:H solar cells are demonstrated.     

Stability of thin film solar cells having less-hydrogenated amorphous silicon i-layers

In this study, highly stabilized hydrogenated amorphous silicon films and their solar cells were developed. The films were fabricated using the triode deposition system, where a mesh was installed between the cathode and the anode (substrate) in a plasma-enhanced chemical vapor deposition system. At a substrate temperature of 250 °C, the hydrogen concentration of the resulting film (Si–H=4.0 at%, Si–H₂<1×10²⁰ cm⁻³) was significantly less than that of conventionally prepared films. The films were used to develop the i-layers of solar cells that exhibited a significantly low degradation ratio of 7.96%.     

Mechanisms of metastability in hydrogenated amorphous silicon

We survey theoretical approaches to understanding the diverse metastable behavior in hydrogenated amorphous silicon. We discuss a recently developed network-rebonding model involving bonding rearrangements of silicon and hydrogen atoms. Using tight-binding molecular dynamics we find non-radiative recombination can break weak silicon bonds with low activation energies, producing dangling bond–floating bond pairs. The transient floating bonds annihilate generating local hydrogen motion and leaving behind isolated dangling bonds. Charged defects are also observed. Major experimental features of metastability including electron-spin resonance, t^1/3 kinetics, dangling-bond H anti-correlation, and hysteretic annealing are explained. In the second part we focus on large metastable structural changes observed in a-Si:H. We find H atoms have a local metastability involving the flipping of the H to the backside of the Si–H bond that results in a local increase of strain and increase of dipole moments. This naturally explains the larger infrared absorption found after light soaking, and may be related to other large structural changes in the network. Directions for future research are surveyed.     

Electrical properties of Cl incorporated hydrogenated amorphous silicon

The electrical properties of chlorine incorporated hydrogenated amorphous silicon films were studied. The samples were deposited with dichlosilane/silane mixtures. The conductivity of these chlorine-incorporated hydrogenated amorphous silicon films decreases with increasing dichlosilane to silane ratio. The Fermi level shifts toward the valence band with increasing chlorine content, resulting in a corresponding conductivity activation energy and room temperature conductivity decrease. However, the defect density and Urbach energy are noot significantly changed in films containing chlorine.     

Crystalline silicon surface passivation by amorphous silicon carbide films

This article reviews the surface passivation of n- and p-type crystalline silicon by hydrogenated amorphous silicon carbide films, which provide surface recombination velocities in the range of 10 cm s⁻¹. Films are deposited by plasma-enhanced chemical vapor deposition from a silane/methane plasma. We determine the passivation quality measuring the injection level (Δn)-dependent lifetime (τ_eff(Δn)) by the quasi-steady-state photoconductance technique. We analyze the experimental τ_eff(Δn)-curves using a physical model based on an insulator/semiconductor structure and an automatic fitting routine to calculate physical parameters like the fundamental recombination velocities of electrons and holes and the fixed charge created in the film. In this way, we get a deeper insight into the effect of the deposition temperature, the gas flow ratio, the doping density of the substrate and the film thickness on surface passivation quality.     

Evolution of microstructure and phase in amorphous, protocrystalline, and microcrystalline silicon studied by real time spectroscopic ellipsometry

Real time spectroscopic ellipsometry has been applied to develop deposition phase diagrams that can guide the fabrication of hydrogenated silicon (Si:H) thin films at low temperatures (<300°C) for highest performance electronic devices such as solar cells. The simplest phase diagrams incorporate a single transition from the amorphous growth regime to the mixed-phase (amorphous+microcrystalline) growth regime versus accumulated film thickness [the a→(a+μc) transition]. These phase diagrams have shown that optimization of amorphous silicon (a-Si:H) intrinsic layers by RF plasma-enhanced chemical vapor deposition (PECVD) at low rates is achieved using the maximum possible flow ratio of H₂ to SiH₄ that can be sustained while avoiding the a→(a+μc) transition. More recent studies have suggested that a similar strategy is appropriate for optimization of p-type Si:H thin films. The simple phase diagrams can be extended to include in addition the thickness at which a roughening transition is detected in the amorphous film growth regime. It is proposed that optimization of a-Si:H in higher rate RF PECVD processes further requires the maximum possible thickness onset for this roughening transition.     

First-principles analysis of electrochemical hydrogen storage behavior for hydrogenated amorphous silicon thin film in high-capacity proton battery

Silicon material electrodes as proton carriers for high-capacity proton battery have only been proposed for such a short period of time that their physicochemical properties and electrochemical hydrogen storage behavior during charge and discharge processes remain nearly uncharted territory. Herein, the hydrogenated amorphous silicon (a-Si:H) thin film electrodes are prepared by radio frequency sputtering followed by ex-situ hydrogenation. The electrochemical properties of a-Si:H electrodes are tested experimentally, and the electrochemical hydrogen storage behaviors of a-Si:H electrodes are analyzed by first-principles calculations. The results show that the hydrogenation process significantly increases the electrochemical capacity of the electrodes and reduces the band gap of the electrode structure. The electrode exhibits weak conductivity during the initial charging, but the instability of the electrode electronic structure during the later charging results in a slight fluctuation of the electrochemical charging process. The a-Si:H electrode have better electrochemical hydrogen storage/release reversibility than non-hydrogenated electrodes, but this reversibility is weakened by oxygen atoms covered on the electrode surface. The electrochemical hydrogen storage process is easier to accomplish than the electrochemical desorption process of hydrogen evolution reaction for the a-Si:H electrodes. The a-Si:H thin film electrode is more stable on the Ni(111) substrate surface and the good conductivity of the electrode/substrate interface provides convenient conditions for the free transport of electrons in the electrochemical charge/discharge processes. We believe that these results perfectly explain the microscopic mechanisms responsible for the electrode reaction and electrochemical behavior of a-Si:H electrodes in this type of proton battery, and have a certain reference value in understanding the physicochemical properties and electrochemical hydrogen storage behavior of silicon material electrodes applied to other types of batteries during charge/discharge processes.     

Electrode distance dependence of photo-induced degradation in hydrogenated amorphous silicon

Electrode distance between cathode and anode is one of the important parameters for fabricating hydrogenated amorphous silicon (a-Si:H) using plasma-enhanced chemical-vapor-deposition system with parallel plate electrodes. In this work, we have investigated the relationship between electrode distance and stability of a resulting a-Si:H. The stability is improved with decreasing electrode distance. At shorter electrode distance, formation of higher silane-related-reactive species is suppressed by heating effect of gas molecules near the cathode due to a proximity to the heated anode. Using cathode heating method, the stability of a-Si:H is improved even at long electrode distances.     

Tin induced crystallisation of hydrogenated amorphous silicon thin films

Abstract

The present article focuses on the effect of annealing temperatures about the Sn induced crystallisation of hydrogenated amorphous Si (a-Si:H) thin films, which are used to fabricate polycrystalline Si (poly-Si) film. The a-Si:H thin films are coated onto Sn metal thin film and subsequently annealed from various temperatures. These are crystallised by annealing for 1 h at 300°C and identified by XRD spectroscopy for the investigation of each phase. Process temperature for crystallisation should not be high because a eutectic temperature of Si–Sn is ～232°C. Si crystal patterns of the prepared samples showed the tendency of changing from (111) to (002) with increasing temperature. It indicates that the crystal phases depend strongly on the annealing temperature of Sn induced a-Si:H thin films for the preparation of poly-Si film. Semiconducting type of Sn induced poly-Si films were shown in n-type through Hall effect measurement.     

Effect of halogen additives on the stability of a-Si:H films deposited at a high-growth rate

We deposited a-Si : H,F films at a high-growth rate (15 Å/s) using a SiH₄ and SiF₄ gas mixture to examine the effect of halogen additives on the film stability against light exposure. Fluorinated a-Si : H films show a high conductivity over 5×10⁻⁵ S/cm and the Schottky cells made with fluorinated films exhibit an improved fill factor after light-soaking. SIMS measurements show an increased oxygen incorporation into the film at a SiF₄ flow of 5 sccm or larger, while virtually no increase is seen when a small SiF₄ flow rate of 1 sccm is used. This is presumably an indication that a small amount of SiF₄ can actually help improve the stability of a-Si : H films against light exposure.     

Hydrogenated amorphous silicon films with significantly improved stability

A new regime of plasma-enhanced chemical-vapor deposition (PECVD), referred to as “uninterrupted growth/annealing” method, has been proposed for preparation of high-quality hydrogenated amorphous silicon (a-Si:H) films. By using this regime, the deposition process no longer needs to be interrupted, as done in the chemical annealing or layer by layer deposition, while the growing surface is continuously subjected to an enhanced annealing treatment with atomic hydrogen created in the hydrogen-diluted reactant gas mixture at a relatively high plasma power. The intensity of the hydrogen plasma treatment is controlled at such a level that the deposition conditions of the resultant films approach the threshold for microcrystal formation. In addition, a low level of B-compensation is used to adjust the position of the Fermi level close to the midgap. Under these conditions, we find that the stability and optoelectronic properties of a-Si:H films have been significantly improved.     

Interface effects on the carrier transport and photovoltaic properties of hydrogenated amorphous silicon/crystalline silicon solar cells

Current-voltage-temperature (I-V-T) characteristics evaluated near 150K and 300K were used to study the photovoltaic property variations in hydrogenated amorphous silicon (a-Si:H)/crystalline silicon (c-Si) solar cells. The possible carrier transport mechanisms in such devices were examined from the I-V-T data which indicated a significant influence of the amorphous /crystalline interface on the short-circuit current density (J_sc) and open-circuit voltage (V_oc) of the solar cells. Carrier transport near 300K for forward biases was by a multi-tunneling mechanism and became space charge limited with increasing bias. For devices having low J_sc and V_oc an additional region was seen in both forward and reverse biases, at low temperatures, where the current simply varied linearly with the applied bias. This characteristic manifested in both high and low temperatures region for devices with still lower photovoltaic properties, which has been reasoned to be due to a higher interface density. Passivating the c-Si surface with HF just prior to the amorphous layer deposition resulted in a large improvement in the properties. The most significant effect was on the J_sc which improved by an order of magnitude. The treatment also affected the lower temperature I-V-T data in that the current fell to very low levels. The spectral response of the treated solar cells showed enhanced blue/violet response compared with the unpassivated devices. The interface passivation plus reducing a-Si thickness has improved the solar cell efficiency from 0.39% to 9.5%.     

Study of the solid phase crystallization behavior of amorphous sputtered silicon by X-ray diffraction and electrical measurements

In situ X-ray diffraction (XRD) measurements have been used to study the amorphous-to-crystalline transformation in hydrogenated amorphous silicon (a-Si:H) thin films deposited by DC-Magnetron Sputtering at 300°C. The a-Si:H layers of 2.85 μm thickness were solid phase crystallized (SPC) and the crystallization kinetic was studied from in situ XRD measurements and also by in situ electrical conductance measurements during isothermal annealing at 630°C. The apparition and the evolution of the (1 1 1) peak in the XRD spectra during the annealing of the layer permit to follow the SPC kinetic which is the same as the electrical conductance kinetic (G=f(t)) performed in the same annealing conditions as in the XRD experiment. Several isothermal annealings at different temperatures permit to extract the characteristic parameters of the crystallization from the G=f(t) evolutions. These parameters are the thermally activated crystallization characteristic time and its activation energy.     

Nanocrystalline silicon thin films deposited by high-frequency sputtering at low temperature

Intrinsic and n-type hydrogenated nanocrystalline silicon thin films (nc-Si:H) were deposited at a temperature as low as 95 °C by high-frequency (HF) sputtering, with hydrogen dilution percentage varying from 31% to 73%. In order to study the properties of the films prepared by this method, the samples were examined by infrared absorption spectroscopy (IR), X-ray diffraction (XRD), SEM, spectroscopic ellipsometry (SE), laser Raman spectrometry and atomic force microscopy (AFM). XRD measurements showed that this film has a new microstructure, which is different from the films deposited by other methods. In addition, an n-type nc-Si:H/p-type c-Si heterojunction solar cell, which has an open circuit voltage (V_oc) of 370 MV and a short-circuit current intensity (J_sc) of 6.5 mA/cm², was produced on the nanocrystalline silicon thin film. After 10 h light exposure under AM1.5 (100 MW/cm²) light intensity at room temperature, radiation degradation has not been found for the device.     

Electrical properties of a-Si:H thin films as a function of bonding configuration

Hydrogenated amorphous silicon (a-Si:H) thin films were fabricated by Radio Frequency (RF) magnetron sputtering. For solar-cell applications, a-Si:H layers are required to show low dark conductivity and high photoconductivity and, thus, high photosensitivity. Hydrogen flow ratio and working pressure were mainly adjusted to control bonding configurations and hydrogen concentration in the films. At a high working pressure of 12 mTorr, all of the prepared amorphous and microcrystalline silicon films showed a dominant IR absorption peak at 2100 cm⁻¹, which indicates a Si-H₂ stretching mode, grain boundaries and microvoids. When the working pressure was decreased to as low as 3 mTorr with a hydrogen flow ratio of 0.1, the bonding configuration of the films was mainly Si-H as determined by the dominant IR absorption peak at 2000 cm^−1, and the photosensitivity of the films was maximized to 760.     

Effect of hydrogen on stability of amorphous silicon thin films

This paper presents results of the investigation of hydrogen influence on the stability of low pressure chemical vapour deposition a-Si films. We measured boron- or phosphorus-doped films post-hydrogenated by ion implantation with different hydrogen doses. The dark conductivity after fast quenching and slow cooling and the isothermal relaxation were measured at different annealing temperatures. It was found that higher hydrogen concentration causes greater metastable changes but shorter relaxation time of defects.