We have studied light-soaking effects, such as photoconductivity (PC) degradation kinetics, the changes of conductivity activation energy, Ea, and the defect density of states (DOS) in a-Si:H films deposited by hot-wire CVD. Films were deposited in a substrate temperature range from 280 to 440 °C for filament temperatures of 1900 and 2100 °C. We find that (a) the photodegradation kinetics does not follow the stretched exponential rule for all of the samples; (b) the Fermi level position moves up after light-soaking for most samples; and (c) the metastable defect DOS deduced from sub-band gap absorption is not consistent with that deduced from the electron mobility-lifetime product. The results are discussed according to the possible mechanism in which charged defects exist in hot-wire a-Si:H films.a

Deposition of n and p-type amorphous (a-Si:H) and microcrystalline (µc-Si:H) silicon thin films on polyethylene terephthalate (PET) at substrate temperatures (Tsub) of 100°C and 25°C (RT) prepared by hot-wire (HW) chemical vapor deposition and radio-frequency (RF) plasma-enhanced chemical vapor deposition is studied as a function of hydrogen dilution. Doping is achieved by addition of phosphine (ntype) and diborane (p-type) to the gas phase reactive mixture. At Tsub=100°C, n-type a-Si:H is obtained by HW with dark conductivity σd10−4 ω−1cm−1 and by RF with σd~10−3 ω−1cm−1. P-type a-Si:H is obtained by HW with σd=8×10−7 ω−1cm−1 and by RF with σd=6×10−7 ω−1cm−1. Decreasing the temperature of deposition to 25°C decreases the sd of RF n-type amorphous samples to 5×10−5 ω−1cm−1 but the σd of p-type samples remains unchanged. RT HW a-Si:H films show a decrease of sd both for ntype film (σd=4×10−6 ω−1cm−1) and p-type film (σd=1.2×10−7 ω−1cm−1). N-type µc-Si:H was obtained by HW with σd=7×10−2 ω−1cm−1 and by RF with σd>10−2 ω−1cm−1 at 100°C. Using the same Tsub, p-type µc-Si:H was deposited by HW and by RF with σd~0.5 ω−1cm−1. At RT, only p-type µc-Si:H films could be prepared using HW (σd~1 ω−1cm−1) and RF (σd=4×10−3 ω−1cm−1). The structural properties of the films were studied using Raman spectroscopy. The structural and transport properties were correlated.

It is instructive to reflect on the past research of an entirely new material such as hydrogenated amorphous silicon in order to analyze which impediments lay in the way of reaching our present understanding. What in retrospect appears to be clear and important evidence was often not recognized as such and, therefore, not incorporated into a coherent picture for a surprisingly long time. One reason for the inability to see and understand is one's mode of thinking, which is conditioned by training and prior experience. Other impediments to progress are some persuasive, but erroneous, views of respected members of the scientific community. A third factor that tends to slow progress is a false sense of competition which, for example, prevents research laboratories from a fruitful exchange of materials and samples. It appears that human faults run neck to neck with nature's intricacies in slowing the pace of our understanding.

This paper presents the experimental results of selective Si epitaxial growth from 650 °C to 700 °C on (100) silicon wafers with oxide patterns using reduced pressure chemical vapor deposition with the SiH4-HCl-H2 gas system. In addition, an HCl etching process is introduced and the conditions of the deposition and etching processes are addressed to sustain the selectivity. As a result, we noted that the addition of HCl serves not only to reduce the growth rate on bare Si, but also to suppress the nucleation on SiO2. In these experiments it has been also observed that the Si layer was grown to 3 nm while sustaining the selectivity. Moreover, further introduction of the HCl etching process following the deposition allowed a 50 nm-thick film to sustain the selectivity for twenty periods.

Hydrogenated amorphous silicon has been deposited by Plasma Enhanced Chemical Vapor Deposition (PECVD) with a square wave amplitude modulated rf signal of 50 MHz. We studied the dependence of the deposition rate on the modulation frequency, using optical emission spectroscopy and plasma modeling. We observed an enhancement in deposition rate by modulating the plasma. This behavior is explained by the characteristics of the electronenergy distribution during the periodical onset of the plasma. According to a one-dimensional fluid model, high-energy electrons cause a large production of radicals at the onset. The heating occurs over the whole plasma volume, leading to an increase of the homogeneity of the layers. The discharge structure is changed completely. A comparison is made between results obtained at 13.56 MHz and at 50 MHz deposition voltages.

A review is given on a research trajectory of amorphous and microcrystalline semiconductors and their device applications proceeded since 1970. A brief explanation on the motivation to start amorphous semiconductor research is given to produce a new kind of synthetic semiconductor having continuous energy gap controllability with valency electron controllability through our experience of modulation spectroscopy in semiconductors.

The first material we have challenged is Si-As-Te chalcogenide semiconductor which has a very wide vitreous region in Gibb's Triangle. A series of systematic experiments has been carried out in the terrestrial environment since 1971, and also within the TT-500A rocket experiment in 1980, and the Spacelab. J experiments FMPT (First Material Processing Test) project in 1992. The second material is hydrogenated amorphous silicon (a-Si:H) and its alloys started in 1976 just after the Garmisch Partenkirchen ICALS-6. With some basic research on the a-Si:H film deposition technology and film quality improvement, our continuous effort to improve the efficiency bore the tandem type solar cells in 1979, and also new products of a-SiC:H and a-SiGe:H in the early period of 1980s are described. These innovative device structures and materials have bloomed in the middle of 1980s in R & D phase such as a-SiC/a-Si heterojunction solar cells, a-Si/a-SiGe and also a-Si/poly-Si tandem type solar cells, and industrialized in recent few years. New kind of trials on full-color thin film light emitting devices has also been recently initiated with wide range of band gap controllability of a-SiC:H.

The third material is microcrystalline silicon (µc-Si) and their alloys which gathers a tremendous R & D effort as a promised candidate for the bottom cell of the a-Si/µc-Si tandem solar cells aimed for the all-round plasma CVD process for the next age thin film photovoltaic devices. In the final part of presentation, a brief discussion will be given on a technological evolution from “bulk crystalline age” to “multilayered thin film age” in the semiconductor optoelectronics toward 21 century.

Degradation properties of a-Si:H and a-Si:D by pairs of intense light pulse pairs are examined. By varying the delay time between pulses in a pair while keeping the total illumination time and dose constant, the time scales involved in the light-induced defect creation are investigated. In nanosecond pulse case, we find a sharp drop in degradation efficiency with delay time, followed by further gradual decrease at much longer times. For microsecond pulses, the degradation efficiency varies with the delay time in microseconds. The recombination proceeds bimolecularly and is largely completed during the pulse. It is suggested that the first stage of degradation is related to bimolecular recombination that takes place during the pulse. The second stage is possibly related to longer-living metastable species.

One- and two-dimensional numerical simulations have been used to determine the parameters critical to high rate growth of high quality polycrystalline silicon via hot-wire chemical vapor deposition at silane partial pressures of 1-70 mTorr and a wire temperature of 2000°C. The Direct Simulation Monte Carlo method [1] was used, including gas-phase chemistry relevant for growth. Model predictions agree both qualitatively and quantitatively with experimental measurements.

The role of the deposition pressure (p) and the type of filaments (tungsten, W or tantalum, Ta) used to produce large area (10cm×10cm) n-type Si:H films by hot wire chemical vapour (HW-CVD) deposition technique was investigated. The data show that the electro-optical properties of the films produced are dependent on the gas pressure used. In the pressure range of 1×10-3 Torr to 1.0 Torr, the room dark conductivity (σd) varies from 1×10-8 to 2 S/cm for films produced at the same hydrogen dilution and filament temperature (Tfil.). On the other hand, the hydrogen concentration (CH) decreases from 10% to 2%, while the growth rate (R) shows an exponential increase, from 1 to 9 Å/s. The SIMS analysis, within the detection limits, does not reveal the existence of any significant W or Ta contamination in the films produced.

Nickel Metal-Induced-Lateral-Crystallization (MILC) has been used to enlarge the grain size and improve the quality of (poly-Si) Thin-Film-Transistors (TFTs). However, the MILC temperature is still low and the grain size is still small. The feasibility of forming very large grains (single crystal like) from amorphous silicon (a-Si) by combining MILC with ramp annealing has been studied. It has been found that the grain size after ramp annealing is remarkably enhanced and can reach of the order of several ten's of microns. The velocity of MILC with ramp annealing is faster than that of MILC with isothermal annealing. The grain size becomes maximal at around 625°C/2hrs, and saturates at higher temperatures of 625- 1000°C. The effect of temperature, time and other parameters has also been studied in order to maximize the grain size and quality. MILC with ramp annealing at 625°C can greatly lower the process time and reduce the need of subsequent annealing to enhance the grain size. The new technology can have numerous novel applications such as providing a low cost alternative to form silicon-on-insulator (SOI) substrates and a breakthrough for high performance TFTs and novel multi-layers SOI like devices and circuits.

The effects of gas temperature gradient, pulse discharge modulation, hydrogen dilution, gas flow, and substrate materials on growth of clusters below about 10 nm in size in silane parallelplate RF discharges are studied using a high-sensitivity photon-counting laser-light-scattering (PCLLS) method. Thermophoretic force due to the gas temperature gradient between the electrodes drives neutral clusters above a few nm in size toward the cool RF electrode. Pulse discharge modulation is much more effective in reducing the cluster density when it is combined with the gas temperature gradient, and clusters above a few nm in size cannot be detected by the PCLLS method even for the discharge over a few hours. Hydrogen dilution and gas flow are also effective in suppressing growth of clusters, when the H2/SiH4 concentration ratio is above about 5 and the flow velocity is above about 6 cm/s, respectively. Cluster growth rate with a glass or Si substrate is found to be considerably higher than that without the substrate.

The in-situ ESR technique is applied to a plasma-enhanced chemical vapor deposition (PECVD) system in order to investigate the surface microchemical reactions during the growth of hydrogenated amorphous silicon (a-Si:H) and plasma treatments of H2 and Ar gases on a- Si:H. The growth model of a-Si:H and the role of H atoms on a-Si:H films are discussed using the experimental results. The recent results on the dynamic surface reactions of crystalline silicon with oxygen molecules in an ultra-high-vacuum ESR system are introduced.

We report on a detailed analysis of paramagnetic states in a doping series of microcrystalline silicon, μc-Si:H, by pulsed electron spin resonance. We identify two dangling bond like structures at g = 2.0052 (db1) and g = 2.0043 (db2). Whereas db1 is evenly distributed in the gap, the db2 state is found to be localized in the lower part of the gap. The CE resonance at g ≈ 1.998 is assigned to electrons in conduction band tail states. In p-doped samples, we observe a broad structure CH at g ≈ 2.08 which we identify with holes trapped in valence band tail states. It is shown that the CH state behaves very similar on illumination as the CE resonance. In n-type samples a pair of hyperfine split lines (A ≈ 11 mT) is found which apparently does not originate from 31P-donor states. On the basis of our results we propose a qualitative model for paramagnetic states in μc-Si:H.

The pixel cross-talk is investigated in two-dimensional amorphous silicon (a-Si:H) imager arrays based on the new high fill factor design. In this configuration a continuous a-Si:H sensor extends over the whole surface of the imager, and a buried insulator material with low dielectric constant is used to separate the sensor from the underlying active matrix readout circuit. We find that the lateral conduction between neighboring pixels is mainly determined by the quality of the buried insulator-sensor interface, rather than the specific buried material itself. Minimum cross-talk values below 1% are obtained for different insulator materials including silicon oxynitride and thicker polymer based resins. The quality of this interface also affects trapping and recombination of the photogenerated carriers, influencing important imager properties such as sensitivity and image lag.

Thin μc-Si films doped with P and B are grown on glass at temperatures between 300 °C and 400 °C by electron cyclotron resonance chemical vapor deposition (ECR-CVD). Hall mobilities in the films are found to be temperature-activated with activation energies being correlated to the doping concentrations. The in-grain mobility as determined by an electron spin resonance investigation is much higher than the Hall mobility the values of which are typically near 1 cm2/Vs at 300 K. The experimental results suggest that transport is dominated by potential barriers at the grain boundaries. An extended Seto model is used to probe the interface trap distribution. We obtained the best fitting results by assuming band-tail states decaying exponentially from the respective band edges.

Tritiated amorphous silicon was used for the intrinsic layer of a p-i-n hydrogenated amorphous silicon diode. Current versus voltage measurements were carried out on the diode over time under dark and illuminated conditions. There was a decrease in the forward characteristic of the diode when measured under dark conditions and there was a decrease in photovoltaic power. These changes can be explained by the creation of dangling bonds when bonded tritium atoms decay. By annealing the diode at 125 °C, most of its photovoltaic properties could be recovered. It was also found that luminescence could be recovered in tritiated amorphous silicon by thermal annealing.

Undoped hydrogenated microcrystalline silicon (νc-Si:H) layers and solar cells have been deposited by plasma-enhanced chemical vapour at low temperature and at different values of VHF plasma power and silane to hydrogen dilution ratios. Transport and defect density measurements on layers suggest that structural properties (e.g. crystallite shape and size) only marginally influence the electronic transport properties. The latter are influenced strongly by the Fermi level, which depends on the oxygen impurity content. Furthermore, they are best described by the quality parameter ν0τ0 (deduced from photoconductivity and ambipolar diffusion length). Cell efficiency correlates better with νoτ0 than with the defect density as determined from subbandgap absorption. Anisotropy of the transport properties in some νc-Si:H is also demonstrated but does not seem to play a major role in νc-Si:H cells deposited at high rates under VHF glow discharge conditions.

Magnetic susceptibility is predicted to be sensitive to structural disorder in the group IV elemental semiconductors. A proton nuclear magnetic resonance (NMR) technique is shown to precisely measure bulk magnetic susceptibilities (χ) of hot-wire (HW) CVD a-Si:H films as- deposited on quartz substrates. Differences in χ correlate with growth rate, but not with hydrogen content or deposition temperature. Qualitative agreement is found between smaller diamagnetic susceptibility (less average disorder) and desirable electronic properties measured by photo- and dark conductivity on the same samples. Comparing films with similar hydrogen distribution and content (as evidenced by the NMR spectra) allows the unambiguous identification of the importance of overall Si network structural disorder in the metastability of a-Si:H.

The structure of undoped Si:H films deposited at a high rate of 6-9 Å/s in an RF (13.56 MHz) plasma from hydrogen-silane gas mixtures at various substrate temperatures was studied using TEM (with in-situ annealing), XRD, Raman spectroscopy, optical absorption and hydrogen effusion. It is found that under our conditions the amorphous to crystalline transition occurs in a relatively narrow range of parameters, influenced mainly by hydrogen dilution and to a lesser degree by the substrate temperature. In the crystalline range the material is found to be nanocrystalline (average grain size 20 nm) and the crystals are essentially stable up to 800°C annealing. The crystal structure of a mixed amorphousnanocrystalline phase of samples deposited near the edge of crystallinity is also found to be rather stable. Nanocrystalline Si films deposited under these latter deposition conditions reveal in hydrogen effusion a relatively compact material and show high solar cell efficiencies (6-8%) when incorporated as i-layers in pin solar cells.

Electroreflectance spectroscopy measurements have been performed on light-emitting porous Si (LEPSi). The transmission electron microscope measurements reveal that LEPSi includes Si nanocrystals with a mean crystal size of 1–2 nm. The ER features are observed at a transition energy of 3.4 eV in all of the samples, giving that LEPSi still keeps the threedimensional (3D) electronic structure. Changes in the transition energies are not found for LEPSi with the different mean crystal sizes. Furthermore, we directly observed interband transitions of quantized states due to quantum-confined electron-hole (e-h) pairs in LEPSi as two or three extra ER features being located between 1.2 and 3.1 eV which are never observed in bulk crystalline Si. Employing a simple effective mass approximation model, we have evaluated the reduced mass, the kinetic energies and the Coulomb attraction energies of the quantumconfined e-h pairs. We also found that the energy distance between the transition energies at the ground state and the photoluminescence (PL) peak energies basically corresponds to the Coulomb attraction energies. Finally, we propose a new luminescent model based on interband transitions involving the quantum-confined dense e-h plasma.