Determination of the optical parameters of a-Si:H thin films deposited by hot wire–chemical vapour deposition technique using transmission spectrum only

Three demonstration samples of intrinsic hydrogenated amorphous silicon (a-Si:H) films were deposited using hot wire–chemical vapour deposition (HW–CVD) technique. The optical parameters and the thickness were determined from the extremes of the interference fringes of transmission spectrum in the range of 400–2500 nm using the envelope method. The calculated values of the refractive index (n) were fitted using the two-term Cauchy dispersion relation and the static refractive index values (n ₀) obtained were 2.799, 2.629 and 3.043 which were in the range of the reported values. The calculated thicknesses for all samples were cross-checked with Taly-Step profilometer and found to be almost equal. Detailed analysis was carried out to obtain the optical band gap (E _g) using Tauc’s method and the estimated values were 1.99, 2.01 and 1.75 eV. The optical band gap values were correlated with the hydrogen content (C _H) in the samples calculated from Fourier transform infrared (FTIR) analysis. An attempt was made to apply Wemple–DiDomenico single-effective oscillator model to the a-Si:H samples to calculate the optical parameters. The optical band gap obtained by Tauc’s method and the static refractive index calculated from Cauchy fitting are in good agreement with those obtained by the single-effective oscillator model. The real and the imaginary parts of dielectric constant (ε _r, ε _i), and the optical conductivity (σ) were also calculated.     

Electric-field-enhanced metal-induced crystallization of hydrogenated amorphous silicon at room temperature

A novel simple method of crystallization of hydrogenated amorphous silicon (a-Si:H) thin films is described. Namely, we studied a metal-induced crystallization enhanced by a dc electric field in sandwich p⁺–i–n⁺structures. The samples were fabricated from wide-bandgap a-Si:H with high hydrogen content (13–51 at. % H). Macroscopic islands of a-Si:H (up to ∼1 mm in diameter) in the region between upper (CrNi) and lower (ITO) contacts crystallize instantaneously when a sufficiently high dc electric field (≳10⁵ V cm^-1) is applied. The crystallization sets in at room temperature and ambient atmosphere and is spatially selective. A proposed microscopic mechanism of such an easy macroscopic crystallization consists in easy diffusion of Ni and/or Ni silicides (representing nucleation sites) through a dense network of voids in hydrogen-rich a-Si:H. Received: 30 November 2000 / Accepted: 3 May 2001 / Published online: 27 June 2001     

Kinetics of laser-induced oxidation of silicon near room temperature

The growth of ultra-thin (<6 nm) silicon-dioxide films on Si(100):H, Si(111):H, and a-Si:H surfaces in a dry oxygen atmosphere (0.1–10 Pa) at low temperatures (35–200 °C) was investigated. Oxidation was induced by pulsed F₂-laserradiation at 157 nm. The thickness and composition of the growing films were monitored in real time by spectroscopic ellipsometry in the photon energy range of 1.15–4.75 eV. The kinetics of low-temperature oxidation was similar for the Si surfaces investigated and differs from that of high-temperature thermal oxidation (900–1200 °C) that can be described by the Deal–Grove model. To explain the faster growth at the initial stage, it is proposed that oxidation occurs by diffusion of oxygen atoms O and/or ions O^-rather than oxygen molecules. The recombination of diffusive species to oxygen molecules limits their penetration into the bulk. A diffusion model is developed for low-temperature oxidation which takes into account the recombination process of the diffusive species. Good agreement between theory and experiment is found. The activation energy of diffusion of the active species was found to be 0.15 eV, in agreement with previous results and recent calculations for O^- ions. PACS 82.65.+r; 07.60.Fs; 81.65.Mq; 82.50.Hp     

Angular distribution of intensity of reflected radiation investigations of the influence of CO2 laser treatment on optical properties of hydrogenated amorphous silicon

Thin films of hydrogenated amorphous silicon (a-Si:H) were annealed using CO₂ laser radiation (λ=10.6 μm). Changes of optical properties of the treated a-Si:H were investigated using optical transmittance spectroscopy and the angular distribution of intensity of reflected radiation (ADIRR). The CO₂ laser annealing influences the spectral characteristics of the real part of refractive index n and absorption coefficient α of light in a-Si:H. This treatment increases the n and α values as well as the Urbach energy of a-Si:H. Simultaneously it decreases the optical energy gap of this material. The changes of optical parameters at the interfaces of a-Si:H–glass substrate and a-Si:H–air were established.     

On formation of thin SiO2/a-Si:H interface when biased oxidized semiconductor surface interacts with plasma or liquid solution

In this paper we present the results of research into a relation(s) between the bias voltage of an oxide/a-Si:H/c-Si sample during formation of very-thin and thin oxides and the resulting distribution of oxide/semiconductor interface states in the a-Si:H band gap. Two oxygen plasma sources were used for the first time in our laboratories for formation of oxide layers on a-Si:H: i) inductively coupled plasma in connection with its application at plasma anodic oxidation; ii) rf plasma as the source of positive oxygen ions for the plasma immersion ion implantation process. The oxide growth on a-Si:H during plasma anodization is also simply described theoretically. Properties of plasmatic structures are compared to ones treated by chemical oxidation that uses 68 wt% nitric acid aqueous solutions. We have confirmed that three parameters of the oxide growth process — kinetic energy of interacting particles, UV-VIS-NIR light emitted by plasma sources, and bias of the samples — determine the distribution of defect states at both the oxide/a-Si:H interface and the volume of the a-Si:H layer, respectively. Additionally, a bias of the sample applied during the oxide growth process has a similar impact on the distribution of defect states as it can be observed during the bias-annealing of similar MOS structure outside of the plasma reactor. Presented at 5-th International Conference Solid State Surfaces and Interfaces, November 19–24, 2006, Smolenice Castle, Slovakia     

Temperature dependence of photoluminescence in amorphous Si1-xCx:H films

We have investigated the temperature dependence of photoluminescence in hydrogenated amorphous silicon-carbon alloys a-Si_1-xC_x:H prepared by glow discharge in the low-power regime. The radiative recombination process, due to photocarriers trapped on band-edge states, is in competition with the thermal escape of the photocarriers into the mobility bands. The model gives a quantitative fit with experiment, without any adjustable parameter, provided the width of the band-edge distribution of states is taken as the width of the conduction band only (measured by “photo-induced infra-red spectroscopy”) and not as the Urbach energy, as it is usually assumed.     

Hydrogen-induced-intrinsic transport in undoped microcrystalline silicon

It is demonstrated that microcrystalline silicon (μc-Si:H) of intrinsic character can be produced by post-growth atomic hydrogen treatment. Undoped μc-Si:H films with a dark-conductivity activation energy (E _a) of about 0.20 eV were grown by plasma-enhanced chemical vapor deposition, and then subsequently exposed to an atomic hydrogen plasma. The hydrogen treatment is shown to result in a gradual increase in the E _a with increasing treatment time, followed by saturation at about 0.57 eV, a value observed for truly intrinsic μc-Si:H films. In the saturated state, the dark conductivity is on the order of 10⁻⁷ S/cm. The dark conductivity prefactor is found to follow the Meyer–Neldel rule. It is proposed that charge transport takes place in amorphous-like tissue surrounding the crystalline grains. The results are attributed to the Fermi level shift due to a change in the gap state distribution.     

Photoinduced self-limited low-temperature growth of ultra-thin silicon-oxide films with water vapor

The growth of ultra-thin (<2 nm) silicon-oxide films was investigated on Si(100):H, Si(111):H, and a-Si:H surfaces in a pure water atmosphere (0.1–10 Pa) at low temperatures of 30–250 °C. Oxidation was induced photochemically by pulsed F₂-laser radiation at 157 nm. The thickness and composition of the growing oxide films were monitored in real time by spectroscopic ellipsometry in the photon energy range of 1.15–4.75 eV. The mechanism of laser-induced silicon oxidation in a H₂O atmosphere is shown to differ fundamentally from the classical Deal–Grove mechanism of thermal oxidation at 900–1200 °C, as well as from the photoinduced low-temperature oxidation in an O₂ atmosphere. In particular, the film thickness essentially does not depend on temperature below 250 °C. A kinetic model is developed for low-temperature silicon oxidation in a H₂O atmosphere. According to this model, the growth is limited at small thicknesses by the oxidation reaction and at larger thicknesses by reactions of the diffusing oxidizing species in the oxide layer. Very good agreement is established between this kinetic model and the ellipsometric measurements and the temperature and pressure dependence of the water oxidation process. PACS 82.65.+r; 07.60.Fs; 81.65.Mq; 82.50.Hp     

Influence of oxygen on the resonant photoacoustic signal from methane excited at the <Emphasis Type="Italic">ν</Emphasis><Subscript>3</Subscript> mode

This paper shows that, when samples of methane in dry air are irradiated with an OPO tuned at the ν ₃ mode at 3019 cm⁻¹, the photoacoustic signal is lower than in mixtures in pure nitrogen. In order to explain this change, we developed a rate-equation-based model which describes the methane excitation and relaxation to heat by collisions with the buffer. In particular, we reduced the problem to a system of six energy levels taking into account the fast energy exchange between methane and oxygen resonant states and the slow relaxation rate of oxygen. Thus, the photoacoustic signal is calculated for methane–nitrogen and methane–air systems and a very good agreement is found with the experimental results.     

Synthesis and dielectric characteristics of La0.5Bi0.5MnO3 ceramics

La_0.5Bi_0.5MnO₃ ceramics with a single phase were prepared by a solid-state reaction method, and their dielectric properties were characterized. Two dielectric relaxations with a giant dielectric constant were identified in the temperature range from 125 to 350 K. The electron hopping between Mn³⁺ and Mn⁴⁺ was found to be the origin of the dielectric relaxation at low temperatures (125–200 K) with an activation energy of 0.18 eV. The high temperature (200–350 K) dielectric relaxation can be attributed to the conduction.     

Upconversion due to energy transfer involving Pr<Superscript>3+</Superscript> ions in pairs

Upconversion luminescence in triply ionized praseodymium-doped TeO₂–Li₂O glass using excitation at ∼590 nm into the ¹D₂ level from a dye laser pumped with the second harmonic of a pulsed Nd:YAG laser has been reported. The mechanism involved in the upconversion emission observed at ∼480 nm indicates that the most important contribution is energy transfer among praseodymium ions in pairs followed by the dipole–dipole interaction. The rate-equation model for the emission at ∼480 nm that provides direct information to determine the energy-transfer rates containing the pair of states involved in the upconversion process has been explored.     

Photoluminescence of very thin oxide/a-Si:H structures passivated in HCN solutions

In this contribution we present new experimental facts concerning evolution of the a-Si:H photoluminescence (PL) spectra, recorded at 6 K, induced by both formation of very thin oxide layer in the surface region of the semiconductor by nitric acid solutions and passivation of a-Si:H defect states using HCN aqueous solutions. a-Si:H layers were deposited on both n-type of crystalline Si and the Corning glass. The analysis of the set of PL spectra - their interpretation - indicates that two explanations of blue shifts of the PL band maxima are possible. The first is connected with formation of several structurally different a-Si:H-based phases inside the amorphous matrix and/or with the Street model of recombination of localized electron-hole pairs coupled with the optical phonon in Si.Additionally, as it was stated, the wet chemical oxidation of 1 μm thick a-Si:H layers deposited on the glass can induce formation of hydrogenated micro-sized a-Si grains. Passivation procedure performed in the HCN solution can transform an equivalent part of the a-Si:H semiconductor to a-Si:CN. If the multiphase model is accepted for interpretation of the PL spectra then the following main PL transitions related with different phases were observed: 1.20, 1.25, 1.38, 1.41, 1.44, and 1.48 eV.     

Post-transit-time analysis of time-of-flight photocurrents

It is shown how the density of localized gap states in amorphous semiconductors can be deduced from time-of-flight photocurrents on the basis of the trap-limited band transport model, post-transit currents giving information on deep-state densities; and how strong deep-trapping of the photo-induced excess carriers invalidates the analysis. Results from a-Si:H, p-type a-Si:H, a-Si,S:H and a-Si,C:H samples are used to illustrate these points.     

Optical and IR studies on r.f. magnetron sputtered ultra-thin MoO3 films

Ultra-thin MoO₃ films were deposited onto glass and Si substrates by r.f. magnetron sputtering. The optical and IR properties of the films were studied in the range of 250 to 1000 nm and 400 to 1500 cm⁻¹, respectively. The optical transmission spectra show a significant shift in absorption edge. The energy gap of the films deposited at 373 K and 0.1 mbar was found to be 3.93 eV, and it decreases with increasing substrate temperature and decreasing sputtering pressure. The IR transmittance spectra shows strong modes of vibrations of Mo=O and Mo–O–Mo units of MoO₃ molecule. A significant change in energy gap and a shift in frequency of IR modes were observed in ultra-thin MoO₃ films.     

Dielectric breakdown of rubber materials by femtosecond irradiation

We report the reversible micro-structuring of a synthetic rubber polymer (cis1,4-polybutadiene (PB)) by femtosecond laser illumination. Visco-elastic relaxation of the optically damaged region was observed. The recovery time, typically 10²–10⁴ ms, can be varied by changing the irradiation pulse energy. Multi-shot-induced damage recovers on the much longer scale of 10¹–10² s. It was found that the doping of PB by 4 wt. % of pentazadiene ([4-NO₂]–phenyl–N=N–N(C₃H₇)–N=N–phenyl–[4-NO₂]) reduces the threshold of light-induced photo-modification by 20%. This is explained by photo-induced (homolytic) cleavage of the pentazadiene bonds and formation of gaseous N₂, which facilitates material failure at the irradiated spot. The recovery of optical transmission can be applied to optical memory, optical and micro-mechanical applications. The underlying mechanism of the phenomenon is discussed in terms of anelastic α- and β-relaxation (polymer backbone and chains/coils relaxation, respectively). Received: 11 October 2001 / Accepted: 9 July 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +81-88/656-7598, E-mail: misawa@eco.tokushima-u.ac.jp     

Long-term evolution of photoinduced light absorption in C60 films

It is found that photoinduced absorption in the energy range 0.6–2.1 eV in C₆₀ films grown by the same method can differ by a factor of 100. This change is attributable a 10⁶-fold increase in the relaxation time τ of electron-hole photoexcitations after working with the films for several months. It is established that the bimolecular recombination mechanism for photoexcitations (triplet excitons and polarons), which is typical of as-prepared and partially aged films, is superseded in fully aged films by thermally activated tunneling of localized photoexcitations. An investigation of the film transmission spectra in the photon energy range 0.2–5.0 eV shows that the long-time variations of the optical properties are associated with a decrease in the concentration of defects forming shallow tails of the density of states. An abrupt decrease of the relaxation time τ and the photoinduced absorption is observed in both types of films at T⩾80 K. Fiz. Tverd. Tela (St. Petersburg) 39, 1303–1309 (July 1997)     

Large supercell molecular dynamics study of defect formation in hydrogenated amorphous silicon

We have performed molecular dynamics simulations of the defect formation associated with the Staebler-Wronski (SW) effect in a-Si:H using 224 and 231 atom supercells and employing semiempirical Si-Si and Si-H total energy functionals. The role of hydrogen in the defect formation within the bond breaking model of the SW effect has been investigated for both large supercells. The results suggest that, within this model, H can be important in weakening the normal Si-Si bonds which break to produce defects in the SW effect.     

a-Si/SiN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> multilayered light absorber for solar cell

40 alternate a-Si/SiN _x multilayer are incorporated as an absorber layer in a p–i–n solar cell. The device is fabricated using hot-wire chemical vapor deposition (HWCVD) technique. The structure of the multilayer film is examined by high resolution transmission electron microscopy (HR-TEM) which shows distinct formation of alternate a-Si and SiN _x layers. The a-Si and SiN _x layers have thickness of ~3.5 and 4 nm, respectively. The photoluminescence (PL) of multilayer film shows bandgap energy of ~2.52 eV, is larger than that of the c-Si and a-Si. Dark and illuminated current–voltage (I–V) characterization of the ML films shows that these ML are photosensitive. In the present work, it is seen that the p–i–n structure with i-layer as ML quantum well (QW) structures show photovoltaic effect with relatively high open-circuit voltage (V _OC). The increment of bandgap energy in PL and high V _OC of the device is attributed to the quantum confinement effect (QCE).     

A thin-film transistor with a very thin a-Si:H layer and its application for an LC panel

One of the disadvantages of applying an a-Si:H thin-film transistor (TFT) to an active matrix-addressed liquid crystal (LC) panel is that a TFT with an a-Si:H has a very large photo-leakage current because of the high photo-conductivity of an a-Si:H itself.We have tried decreasing the photo-leakage current by varying the thickness of an a-Si:H layer (L) in TFTs and investigated the characteristics of TFTs, mainly drain voltage versus drain current containing photo-leakage current (I _ph).As a result, it is shown that lnI _ph is proportional to InL, and its gradient is 1.5–2.0. We assume that the thinner an a-Si:H layer is, the more effective the recombination of carriers at the interface states is forI _ph.We have applied TFT with a very thin a-Si:H layer (30nm) to a full-color active matrix-addressed LC panel for a moving picture display and realized a display of good quality under illuminated condition of 5×10⁴lx without a shading layer in it.