Hydrogen-induced crystallization of amorphous silicon clusters in a plasma reactor

In the present study, the mechanism of hydrogenated silicon particle nucleation in a plasma reactor is investigated using quantum molecular dynamics (MD) simulations. We can realistically simulate the nanoparticle growth in the plasma by successive collisions of SiH₃ and SiH₄ molecules at room temperature impact energies. Our method permits the simulation of the experimental plasma reactions more realistically than most former investigations, which were mainly limited to minimum energy searches to determine possible Si_nH_m structures, neglecting all dynamical effects of the cluster growth. Consequently, even the formation of metastable amorphous structures (as during powder formation) can be simulated with our method. Our simulations show that cluster growth in a pure silane plasma at room temperature always leads to amorphous silicon structures that are very rich in hydrogen. By exposing those amorphous clusters to atomic hydrogen, however, we observe their crystallization. During the atomic hydrogen exposure, the nanostructures pass through multiple metastable configurations until they eventually fall into a minimum energy configuration. In this case, we obtain Si_nH_m structures that correspond remarkably well to the minimum energy structures predicted by ab initio calculations. To evaluate this striking result more quantitatively, we display the corresponding atomic radial distribution functions. The present method is a new way to investigate realistic nanostructure growth in a less empirical and thus more realistic manner.     

Substrate temperature dependence of microcrystalline silicon growth by PECVD technique

Undoped hydrogenated silicon films have been prepared from a gas mixture of silane and hydrogen, varying substrate temperature from 180–380 °C in an ultrahigh vacuum system using RFPECVD technique. XRD and Raman measurements enable us to know that the films are microcrystalline throughout the substrate temperature range. Bond formation of the SiH films at different substrate temperature is studied through different characterisation techniques like Fourier transform infrared spectroscopy and hydrogen evolution study. The infrared absorption spectroscopy and hydrogen evolution study reveal two types of growth: the formation of a void rich material at low T_s (∼180 °C) and a compact material at comparatively higher T_s.     

Formation kinetics and control of microcrystallite in μc-Si:H from glow discharge plasma

The formation kinetics of μc-Si:H has been investigated through the film depositions and plasma diagnoses in widely-scanned glow discharge plasma conditions; RF power density, SiH₄/H₂ ratio and substrate temperature. The roles of H and SiH_x adsorbed on the surface as well as impinging ions have been discussed in relation to volume fraction and crystallite size of μc films, and continuous control of crystallite size has been demonstrated using a triode system. Hall mobility of the deposited μc-Si:H films has also been presented as a function of the volume fraction of μc.     

Effect of an inter-electrode distance in VHF-PECVD and gas flow ratios on a-SiGeC:H films and solar cells by using monomethyl germane as a germanium source

Hydrogenated amorphous silicon–germanium–carbide (a-SiGeC:H) has been fabricated by monomethyl germane (MMG, GeH₃CH₃) under various deposition conditions, inter-electrode distance (d_ele) in VHF-PECVD and gas flow ratios. With decreasing d_ele, it is observed from optical emission spectroscopy (OES) that the generation of atomic hydrogen in plasma gradually increases. It is also found that the enhanced atomic hydrogen tends to take both Ge and C away from growing surfaces, leading to the decrease in Ge and C contents. The total content of hydrogen bonds increases as a result of the increase in both SiH and GeH bonds as the d_ele decreases. Consequently, the a-SiGeC:H solar cells fabricated at narrower d_ele exhibit the improved performance. Even though the optical band gap (E_opt) of the a-SiGeC:H increases with decreasing d_ele, the quantum efficiency (QE) spectra reveal even an increasing trend of long wavelength regions because of the significant improvement in i-layers. It is also confirmed that a lot lower MMG/SiH₄ was needed for the films having certain E_opt, when fabricated near amorphous-to-crystalline transition, and the solar cell fabricated near the transition region shows the better performance.     

Influence of hydrogen on structural and optical properties of low temperature polycrystalline Ge films deposited by RF magnetron sputtering

To improve the properties of polycrystalline Ge thin films, which are a candidate material for the bottom cells of low cost monolithic tandem solar cells, ∼300 nm in situ hydrogenated Ge (Ge:H) thin films were deposited on silicon nitride coated glass by radio-frequency magnetron sputtering. The films were sputtered in a mixture of 15 sccm argon and 10 sccm hydrogen at a variety of low substrate temperatures (T_s)≤450 °C. Structural and optical properties of the Ge:H thin films were measured and compared to those of non-hydrogenated Ge thin films deduced in our previous work. Raman and X-ray diffraction spectra revealed a structural evolution from amorphous to crystalline phase with increase in T_s. It is found that the introduction of hydrogen gas benefits the structural properties of the polycrystalline Ge film, sputtered at 450 °C, although the onset crystallization temperature is ∼90 °C higher than in those sputtered without hydrogen. Compared with non-hydrogenated Ge thin films, hydrogen incorporated in the films leads to broadened band gaps of the films sputtered at different T_s.     

InOx semiconductor films deposited on glass substrates for transparent electronics

Transparent undoped semiconductor indium oxide films were deposited by radio frequency (rf) plasma enhanced reactive thermal evaporation (rf-PERTE) of indium at low substrate temperature. It was experimentally verified that the variation of rf power density has a strong influence on the electrical and structural properties of the films. The thickness of the InO_x films is of about 100 nm. Results show that InO_x films show an average visible transmittance of about 85% and energy gap of about 2.6 eV. Structural and electrical conductivity measurements show that films are polycrystalline and there exists a linear variation of conductivity logarithm vs reciprocal of temperature. Electrical conductivity variation of 17.6 to 5.8 × 10⁻³ (Ω cm)⁻¹ for films produced at rf power densities ranging from 3.9 to 78.1 mW cm⁻³ was obtained. This controllable semiconductor behavior can therefore satisfy the requirement of a particular application for these type of films.     

Synthesis of nonstoichiometric zirconium carbide whiskers by chemical vapor deposition

Nonstoichiometric zirconium carbide crystals with various compositions were prepared by chemical vapor deposition. Two gaseous mixtures, zirconium tetrachloride and argon, toluene and hydrogen, were introduced to the reaction zone where a graphite substrate was heated between 1200 and 1400°C. The deposition rate was proportional to the partial pressure of toluene. The compositional ratio of n_C/n_Zr in the gaseous mixture from 2.0 to 6.0 was found to be optimum for producing needle-like crystals. Needle-like crystal with smaller size were formed when the ratio of n_C/n_Zr was smaller than 2.0, and less needle-like crystals accompanied with more carbon were also produced when the ratio of n_C/n_Zr was larger than 6.0. The temperature of the substrate suitable for the growth of needle crystals was in the range from 1250 to 1300°C. The lattice constants of the products varied as a function of the ratio of n_C/n_Zr in the gaseous mixtures.     

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.     

Self-assembling of supramolecular erbium–oxygen clusters in magnetron plasma,and the optimization of erbium luminescence in a-SiOx:H〈Er, O〉 films

Films of erbium-doped amorphous hydrogenated silicon a-SiO_x:H〈Er, O〉 were fabricated by dc-magnetron sputtering at different concentrations of oxygen in the magnetron plasma and different areas of erbium metallic target. It was demonstrated that the increase of oxygen concentration in the plasma gaseous phase above ∼5 mol% leads to a sharp rise in the amount of oxygen bound to erbium in the a-SiO_x:H〈Er, O〉 films. Simultaneously, a smooth increase in the concentration of oxygen bound to matrix-forming elements (silicon, hydrogen) is observed. The increase of the area of erbium target, corresponding to the rise of concentration of erbium ions in the plasma, also favors the binding of erbium with oxygen. However, the content of erbium in the a-SiO_x:H〈Er, O〉 film (in atomic percents) significantly drops with intense binding of erbium with oxygen. These facts point to the formation of erbium–oxygen clusters, with a large number of oxygen atoms, which are probably formed in the magnetron plasma but are deposited as a separate species on the substrate in the reaction chamber. The intensity of erbium photoluminescence rises significantly in the region of formation of these large erbium–oxygen clusters. A ‘phase-transition’ model is formulated, describing the properties of a-SiO_x:H〈Er, O〉 films, based on the assumption of the formation of large erbium–oxygen clusters in the magnetron plasma. The size and composition of these clusters are determined. The model is semi-quantitatively consistent with all the experimental findings.     

Non-crystalline Se thin films deposited from controlled vapor-preparation,crystallization and optical properties

Films of amorphous Se were prepared in well-defined conditions: the temperature and composition of the Se vapor just before its deposition and the temperature of the polished quartz substrate were carefully controlled. By measuring (a) the thickness of the films and (b) their reflection and transmission coefficients in the range $\text{λ = 4000–7000}\text{A}\text{?}$, the values of n, k and of an optical gap E_opt were obtained; E_opt seems to be characteristic of the preparation. Initial results concerning crystallization of the thin films are also discussed.     

Control of the optical band gap of hydrogenated amorphous boron: The use of the B2H6–BF3 gas mixtures

Amorphous boron thin films have been produced by the glow discharge decomposition of diborane, boron trifluoride, and hydrogen gas mixtures. The optical band gap of these films was controlled by changing the relative proportions of diborane and boron trifluoride. Films with band gaps of approximately 1.45 eV can be obtained by using a B₂H₆ : BF₃ gas volume ratio of 8 : 1 and a substrate temperature of 225°C. The electron paramagnetic resonance spectrum shows a pronounced shift in the g factor, giving evidence of fluorine incorporated into the amorphous matrix.     

Microstructure and optical properties of (Pb,Ca)TiO3 films grown on Si(1 0 0) substrates by a simple sol-gel process

Amorphous and polycrystalline (Pb_0.76Ca_0.24)TiO₃ (PCT) thin films deposited on an Si(1 0 0) substrate have been prepared by a simple sol-gel process. The microstructure and surface morphologies of the thin films have been studied by X-ray diffraction (XRD) and atomic force microscopy (AFM). The polycrystalline PCT film on the Si(1 0 0) substrate has a tetragonal perovskite structure with grain size from 60 to 110 nm. AFM reveals smooth surfaces and root mean square (rms) roughness of 0.17 and 4.4 nm for amorphous and polycrystalline films, respectively. The refractive index n and extinction coefficient k of the amorphous and polycrystalline thin films was obtained by spectroscopic ellipsometry as a function of the photon energy in the range from 2.0 to 5.4 eV. The maximum n and direct bandgap energies of amorphous and polycrystalline thin films were 2.66 and 4.11 eV, 2.64 and 3.84 eV, respectively.     

Characterizations of GaN film growth by ECR plasma chemical vapor deposition

The electron cyclotron resonance plasma-enhanced metalorganic chemical vapor deposition technology (ECR–MOPECVD) is adopted to grow GaN films on (0 0 0 1) α-Al₂O₃ substrate. The gas sources are pure N₂ and trimethylgallium (TMG). Optical emission spectroscopy (OES) and thermodynamic analysis of GaN growth are applied to understand the GaN growth process. The OES of ECR plasma shows that TMG is significantly dissociated in ECR plasma. Reactants N and Ga in the plasma, obtained easily under the self-heating condition, are essential for the GaN growth. They contribute to the realization of GaN film growth at a relatively low temperature. The thermodynamic study shows that the driving force for the GaN growth is high when N₂:TMG>1. Furthermore, higher N₂:TMG flow ratio makes the GaN growth easier. Finally, X-ray diffraction, photoluminescence, and atomic force microscope are applied to investigate crystal quality, morphology, and roughness of the GaN films. The results demonstrate that the ECR–MOPECVD technology is favorable for depositing GaN films at low temperatures.     

等离子体增强CVD法沉积的微晶硅薄膜的微结构研究

本文系统研究了PECVD法沉积μc-Si薄膜中衬低温度、氢气稀释率和射频功率等参数对μc-Si薄膜结构特性的影响.表明:随着衬低温度的增加、氢气稀释率的增大、射频功率的提高,薄膜的晶化率增大.沉积薄膜的晶化率最大可达80;,表面粗糙度大约为30nm.通过对反应过程中的能量变化进行了分析,得到反应为放热反应,且非晶结构对沉积参数比较敏感.     

Thermoelectric Power of Polycrystalline Sb2Te3 Films

Polycrystalline stochiometric films of Sb₂Te₃ with different thickness were prepared on glass substrates by a flash evaporation technique at constant substrate temperature of 423 K. The thermoelectric power of these films was determined by measuring integrally the developed thermo — e.m.f. at different temperature differences between the hot and cold ends. The thermoelectric power of Sb₂Te₃ films was determined as a function of the temperature and thickness of the films. It was found that the Fermi level becomes pinned at higher temperatures. The values of γ, E₀, and A parameters were determined as functions of the thickness of the films. The dependence of the thermoelectric power on the reciprocal thickness of the films was explained on the basis of the grain size effect.     

New preparation method of diamond like carbon – the layer-by-layer method

A new method––the layer-by-layer method––is used to prepare diamond like carbon (DLC) films. The layer-by-layer method is a cyclic process for the deposition of DLC by a rf magnetron sputtering using Ar gas and with alternate the atomic hydrogen treatment, which samples are called LL-DLC. A DLC sample without atomic hydrogen treatment and an atomic-hydrogen-treated DLC sample are prepared to compare with LL-DLC. LL-DLC samples are prepared with the substrate temperature from RT to 400 °C. The data of the electrical conductivity including Fermi level E_F, optical energy gap E_O4, X-ray photoelectron spectroscopy, sp³ fraction obtained by Raman spectra, infrared absorption coefficient spectra and atomic force microscope are used to characterize these DLC films. These results are also discussed comparing with amorphous carbon nitride a-CN_X and the layer-by-layer prepared amorphous carbon nitride LLa-CN_X.     

Deposition of microcrystalline Ge films using hot-wire technique without toxic gases

To investigate the deposition of Ge films without toxic gas such as germane, we have studied the Ge films prepared by the hot-wire technique, which utilize the reaction between a Ge target and hydrogen atoms generated by the hot-wire decomposition of H₂ gas. The films deposited on Si substrate were microcrystalline Ge films and the mean crystallite size of the films increased from 13.3 to 24.8 nm with increasing the substrate temperature from 300 to 500 °C. Moreover, the deposition rate of Ge films deposited on Si substrate was higher than that of Ge films deposited on Corning 1737 substrate. It was found that the substrate temperature and the kind of substrate are key parameters for the preparation of microcrystalline Ge films by the hot-wire technique.     

Transition from amorphous semiconductor to amorphous insulator in hydrogenated carbon–germanium films investigated by IR spectroscopy

Thin a-Ge_XC_1?X:H plasma polymerized films, depending on deposition conditions, can be produced in two very different structures, namely amorphous semiconductor and amorphous insulator. The transition from amorphous insulator to amorphous semiconductor is related to the formation of germanium nanoclusters due to ions bombarding the surface of the growing material. This paper concentrates on investigations of the transition by means of IR spectroscopy. To this end a quantitative analysis of IR spectra obtained for thin films deposited on silicon substrate has been described and used for estimation of hydrogen atom concentration and bonding in the investigated material. It was found that the probability that a given H atom is bonded to a germanium or to a carbon atom is almost the same. This conclusion is true both for a-S and a-I films. The average concentration of hydrogen in the investigated material was found to be about 2.4–3.4 × 10²² cm^?2 which means that there are two times more atoms of the carbon family than hydrogen atoms in the film structure.     

Structural study of undoped and (Mn, In)-doped SnO2 thin films grown by RF sputtering

Undoped and 5%(Mn, In)-doped SnO₂ thin films were deposited on Si(1 0 0) and Al₂O₃ (R-cut) by RF magnetron sputtering at different deposition power, sputtering gas mixture and substrate temperature. X-ray reflectivity was used to determine the films thickness (10–130 nm) and roughness (～1 nm). The combination of X-ray diffraction and Mössbauer techniques evidenced the presence of Sn⁴⁺ in an amorphous environment, for as-grown films obtained at low power and temperature, and the formation of crystalline SnO₂ for annealed films. As the deposition power, substrate temperature or O₂ proportion are increased, SnO₂ nanocrystals are formed. Epitaxial SnO₂ films are obtained on Al₂O₃ at 550 °C. The amorphous films are quite uniform but a more columnar growth is detected for increasing deposition power. No secondary phases or segregation of dopants were detected.     

Transport properties of hydrogenated amorphous silicon deposited by dc glow discharge decomposition

Conductivity and thermoelectric power measurements have been made as a function of temperature on a series of hydrogenated amorphous silicon samples. The samples were prepared by the dc glow discharge decomposition of silane and silane phosphine mixtures. The activation energy for conduction varied with the substrate temperature and discharge condition for undoped specimens. The difference in the activation energy for conduction as well as the dependence of photoconductivity and optical gap on the activation energy for conduction among undoped specimens can be explained by introducing centers acting as donors or by change transfer between the island and hydrogen rich interfacial region. The kinks in the log σ versus inverse temperature curves always appear at about 430 K for the undoped specimens prepared at 300°C, while they are absent for low substrate temperature specimens. The downward kinks with increasing temperature can be explained by a two-phase material model. A revised two-channel conduction path model including material heterogeneity is applied to interpret the conductivity and thermopower versus inverse temperature curves of doped a-Si:H films, and to determine the position of phosphorus donor levels. The levels are found to lie at about 0.47 eV below E_c, the mobility edge at the conduction band.