Influence of substrate direct current bias voltage on microcrystalline silicon growth during radio-frequency magnetron sputtering

Hydrogenated microcrystalline silicon (μc-Si:H) thin films were prepared on glass, aluminum-covered glass and Si wafer substrates at various substrate bias voltages (V_sb) between -400 and +50 V, and the influence of V_sb on their structural properties was investigated. The crystallinity (crystalline volume fraction and crystallite size) of the μc-Si:H films deposited on glass remained unchanged with respect to V_sb. For μc-Si:H films deposited on aluminum within the V_sb range of -20 to +50 V, the crystallinity also remained unchanged and showed the same crystallinity as that of the films deposited on glass substrate. However, the crystallinity of the μc-Si:H films deposited on aluminum-covered substrate was reduced as V_sb decreased from -20 to -100 V, and the film at V_sb=-400 V was completely amorphous.     

X-ray determination of strain and texture in sputtered molybdenum and titanium films on silicon

Molybdenum and titanium films prepared with a rotating r.f. diode system were examined by X-ray diffraction for strain and texture. Both films were deposited onto (111)-oriented silicon crystal substrates. Molybdenum films 1.13 μm thick sputtered with a target voltage of -2.7 kV, a zero substrate bias and an average temperature of 180°C were in compression on cooling to room temperature. Pole density plots for the (200), (211), (220), (222), (301) and (321) planes gave relatively sharp peaks. The (220) plane showed a strong peak parallel to the (111) plane on silicon. In contrast, a 1.25 μm titanium film was found to be in tension after sputtering at -2.7 kV, a substrate bias of -50 V and an average temperature of 180°C. Relatively broad pole density plots were found for the (002) and (110) planes. The (100) and (110) planes gave peaks parallel to (111) Si. Intrinsic strains from embedded argon were determined from χ scan X-ray data.     

Preferential growth of μc-Ge : H along the crystallographic axes of Si and Ge substrates by ECR plasma CVD

Hydrogenated microcrystalline germanium (μc-Ge : H) films have been grown on crystalline (c-) Si and Ge substrates in a temperature range from 25 to 313 °C, by means of electron-cyclotron-resonance plasma chemical vapor deposition. An increase in substrate temperature induced an amorphous to microcrystalline phase transition at around 50 °C, and increased the crystalline volume fraction of μc-Ge : H on both c-Si and c-Ge. A volume fraction of nearly 100% was realized at 200 °C. Above this, (1 0 0) preferential growth of μc-Ge : H was observed on both c-Si(1 0 0) and c-Ge(1 0 0). For c-Si(1 1 1) and c-Ge(1 1 1) substrates, the growth direction was mainly (1 1 1), but containing (1 1 0) and (3 1 1) components, attributed to twin formation. The dependence of the film-surface roughness on the substrate temperature was also examined. The peak energy and magnitude of the photoluminescence decreased with increasing substrate temperature.     

Polycrystalline silicon films fabricated by rapid thermal annealing

Poly-crystalline silicon (poly-Si) films were fabricated by rapid thermal annealing (RTA) of amorphous silicon films which were deposited on quartz by hot wire chemical vapor deposition. An insertion of Cr layer can significantly suppress the peeling of Si films during the RTA process. The effect of RTA parameters on the structural properties of poly-Si films was investigated by Raman spectroscopy, X-ray diffraction and scanning electron microscopy. The results show that the crystallinity of the poly-Si films is increased with the increase of RTA temperature and duration. A sharp peak at about 520?cm^?1 is observed in the Raman spectra of poly-Si films annealed at 900 and 1,100?°C for 15?s indicating the excellent crystallinity of the poly-Si films fabricated by RTA. Poly-Si films with high crystalline fraction of 97.3?% were obtained by RTA at 1,100?°C for 20?s.     

Low temperature crystallization of amorphous silicon carbide thin films for p–n junction devices fabrication

Metal induced crystallization technique was used to crystallize hydrogenated amorphous silicon carbide (a-SiC:H) thin films at low temperatures. Two types of substrates, silicon and silicon carbide were considered and the substrate effects on the final crystallized film were studied. About 200 nm a-SiC:H films were deposited and crystallized successfully on n-type Si and n-type 6H SiC substrates at a temperature of 600 °C. Fourier Transform Infrared (FTIR) spectroscopy and transmission electron microscopy (TEM) analysis confirmed the crystallization of a-SiC:H film. Current–voltage (I–V) and capacitance–voltage (C–V) measurement confirms the formation of p–n junction with rectification over five orders of magnitude from ?2 V to 2 V.     

Mechanical properties of amorphous and microcrystalline silicon films

Hydrogen-free amorphous silicon (a-Si) films with thickness of 4.5-6.5 μm were prepared by magnetron sputtering of pure silicon. Mechanical properties (hardness, intrinsic stress, elastic modulus), and film structure (Raman spectra, electron diffraction) were investigated in dependence on the substrate bias and temperature. The increasing negative substrate bias or Ar pressure results in simultaneous reducing compressive stress, the film hardness and elastic modulus. Vacuum annealing or deposition of a-Si films at temperatures up to 600 °C saving amorphous character of the films, results in reducing compressive stress and increasing the hardness and elastic modulus. The latter value was always lower than that for monocrystalline Si(111). The crystalline structure (c-Si) starts to be formed at deposition temperature of ∼ 700 °C. The hardness and elastic modulus of c-Si films were very close to monocrystalline Si(111). Phase transformations observed in the samples at indentation depend not only on the load and loading rate but also on the initial phase of silicon. However, the film hardness is not too sensitive to the presence of phase transformations.     

Gradient etching of silicon-based thin films for depth-resolved measurements: The example of Raman crystallinity

An etching procedure was applied to microcrystalline silicon (μc-Si:H) thin films in order to obtain a wedge-shaped profile for depth-resolved characterization. A microfluidic flow cell that merges deionized water with a potassium hydroxide solution (KOH_aq) was utilized. The samples consisted of texture-etched ZnO:Al on a Corning Glass substrate, a microcrystalline p-doped layer serving as seed layer and the investigated intrinsic microcrystalline or amorphous silicon (a-Si:H). Along the etched profiles, microscopic Raman spectroscopy was used to estimate the crystalline volume fraction X_c for samples deposited with intentionally varied silane concentration to investigate the a-Si:H/μc-Si:H and μc-Si:H/a-Si:H transition.     

Substrate bias voltage influenced structural, electrical and optical properties of dc magnetron sputtered Ta2O5 films

Tantalum oxide (Ta₂O₅) films were formed on silicon (111) and quartz substrates by dc reactive magnetron sputtering of tantalum target in the presence of oxygen and argon gases mixture. The influence of substrate bias voltage on the chemical binding configuration, structural, electrical and optical properties was investigated. The unbiased films were amorphous in nature. As the substrate bias voltage increased to −50 V the films were transformed into polycrystalline. Further increase of substrate bias voltage to −200 V the crystallinity of the films increased. Electrical characteristics of Al/Ta₂O₅/Si structured films deposited at different substrate bias voltages in the range from 0 to −200 V were studied. The substrate bias voltage reduced the leakage current density and increased the dielectric constant. The optical transmittance of the films increased with the increase of substrate bias voltage. The unbiased films showed an optical band gap of 4.44 eV and the refractive index of 1.89. When the substrate bias voltage increased to −200 V the optical band gap and refractive index increased to 4.50 eV and 2.14, respectively due to the improvement in the crystallinity and packing density of the films. The crystallization due to the applied voltage was attributed to the interaction of the positive ions in plasma with the growing film.     

Influence of annealing temperature on the properties of polycrystalline silicon films formed by rapid thermal annealing of a-Si:H films

In this work, rapid thermal annealing (RTA) was employed to crystallize the amorphous silicon films deposited by hot-wire chemical vapor deposition. The influence of annealing temperature on structural and electrical properties was studied by Raman spectroscopy, X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy and temperature-dependent conductivity measurement. The results show that the amorphous silicon films can be successfully crystallized by RTA in a very short time. The crystallinity and electrical properties of the poly-Si films was greatly improved as the RTA temperature increasing. When the temperature higher than 900 °C, the poly-Si films obtained the crystalline fraction above 95 %, and the hydrogen atoms almost disappeared in the poly-Si films. At the temperature of 1,100 °C, polycrystalline silicon films with conductivity of 16.4 S cm^?1 is obtained, which is seven orders in magnitude higher than that of the film annealed at 700 °C.     

On the processing-structure-property relationship of ITO layers deposited on crystalline and amorphous Si

Indium-tin-oxide (ITO) antireflection coatings were deposited on crystalline Si (c-Si), amorphous hydrogenated Si (a-Si:H) and glass substrates at room temperature (RT), 160 °C and 230 °C by magnetron sputtering. The films were characterised using atomic force microscopy, transmission electron microscopy, angle resolved X-ray photoelectron spectroscopy, combined with resistance and transmittance measurements. The conductivity and refractive index as well as the morphology of the ITO films showed a significant dependence on the processing conditions. The films deposited on the two different Si substrates at higher temperatures have rougher surfaces compared to the RT ones due to the development of crystallinity and growth of columnar grains.     

Effects of annealing and deposition temperature on the structural and optical properties of AZO thin films

Al-doped ZnO (AZO) thin films were deposited on p- type Si(100) substrate by r.f magnetron sputtering at 200, 300 and 400 °C substrate temperatures. The deposited films were annealed in air atmosphere for 1 h at temperatures of 700, 800 and 900 °C. The deposition temperature and post-deposition annealing effects on structural and optical properties of the AZO samples were analyzed using X-ray diffraction, atomic force microscope and photoluminescence (PL). After annealing, the value of full width half maximum of the diffraction peaks was decreased as well as, the intensity of visible and strong UV PL emission peaks were increased with temperature. However, the deep-level emission related with zinc point defects was removed by annealing of the samples. Results revealed that all of the as-deposited and annealed AZO films have hexagonal structure along (002) direction and their crystallinity were improved with the increased deposition and post-growth annealing temperatures. In addition, the surface roughness and the particle size of the films were increased with increased deposition and annealing temperatures.     

Characterization of defects in hydrogenated amorphous silicon deposited on different substrates by capacitance techniques

Hydrogenated amorphous silicon (a-Si:H) thin films deposited on crystalline silicon and Corning glass substrate were analyzed using different capacitance techniques. The distribution of localized states and some electronic properties were studied using the temperature, frequency and bias dependence of the Schottky barrier capacitance and deep level transient spectroscopy. Our results show that the distribution of the gap states depends on the type of substrate. We have found that the films deposited on c-Si substrate represent only one positively charged or prerelaxed neutral deep state and one interface state, while the films deposited on glass substrate have one interface state and three types of deep defect states, positively or prerelaxed neutral, neutral and negatively charged.     

Structural investigation of silicon films chemically vapour deposited onto amorphous SiO2 substrates

The influence of substrate temperature and the silane-to-nitrogen ratio on the structure of silicon films 0.5–0.6 μm thick deposited onto amorphous SiO₂ substrates was investigated by X-ray diffraction. The investigations were carried out for silicon films deposited at various temperatures in the range 500–750 °C and with various silane-to-nitrogen ratios in the range 3.04 × 10^-4-2.84 × 10^-3 by volume. The silicon films deposited at 500 °C were amorphous while the films deposited at 550 °C were randomly oriented polycrystalline. The films deposited in the temperature range 600–700 °C were polycrystalline with a preferred orientation that changed from 〈110〉 through 〈100〉 to 〈111〉. The structure of the films deposited at 750 °C was randomly oriented polycrystalline. Investigations of the influence of the silane-to-nitrogen ratio on the silicon film structure revealed that the structure of films deposited at a substrate temperature of 500 °C was independent of the silane-to-nitrogen ratio. The structure of the films deposited at 600 °C depended on the silane-to-nitrogen ratio and changed from polycrystalline with a 〈110〉 preferred orientation to randomly oriented polycrystalline when the ratio was increased. The structure of films deposited at 700 °C also depended on the silane-to-nitrogen ratio and changed from randomly oriented polycrystalline to polycrystalline with double preferred orientation (〈100〉 and 〈111〉) when the ratio was increased.     

Optical and mechanical properties of diamond like carbon films deposited by microwave ECR plasma CVD

Diamond like carbon (DLC) films were deposited on Si (111) substrates by microwave electron cyclotron resonance (ECR) plasma chemical vapour deposition (CVD) process using plasma of argon and methane gases. During deposition, a d.c. self-bias was applied to the substrates by application of 13·56 MHz rf power. DLC films deposited at three different bias voltages (−60 V, −100 V and −150 V) were characterized by FTIR, Raman spectroscopy and spectroscopic ellipsometry to study the variation in the bonding and optical properties of the deposited coatings with process parameters. The mechanical properties such as hardness and elastic modulus were measured by load depth sensing indentation technique. The DLC film deposited at −100 V bias exhibit high hardness (∼ 19 GPa), high elastic modulus (∼ 160 GPa) and high refractive index (∼ 2·16–2·26) as compared to films deposited at −60 V and −150 V substrate bias. This study clearly shows the significance of substrate bias in controlling the optical and mechanical properties of DLC films.     

Microstructures of microcrystalline silicon thin films prepared by hot wire chemical vapor deposition

Undoped hydrogenated microcrystalline silicon (μc-Si:H) thin films were prepared at low temperature by hot wire chemical vapor deposition (HWCVD). Microstructures of the μc-Si:H films with different H₂/SiH₄ ratios and deposition pressures have been characterized by infrared spectroscopy X-ray diffraction (XRD), Raman scattering, Fourier transform (FTIR), cross-sectional transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). The crystallization of silicon thin film was enhanced by hydrogen dilution and deposition pressure. The TEM result shows the columnar growth of μc-Si:H thin films. An initial microcrystalline Si layer on the glass substrate, instead of the amorphous layer commonly observed in plasma enhanced chemical vapor deposition (PECVD), was observed from TEM and backside incident Raman spectra. The SAXS data indicate an enhancement of the mass density of μc-Si:H films by hydrogen dilution. Finally, combining the FTIR data with the SAXS experiment suggests that the Si---H bonds in μc-Si:H and in polycrystalline Si thin films are located at the grain boundaries.     

Microstructure characterization of microcrystalline silicon thin films deposited by very high frequency plasma-enhanced chemical vapor deposition by spectroscopic ellipsometry

We applied ex situ spectroscopic ellipsometry (SE) on silicon thin films across the a-Si:H/μc-Si:H transition deposited using different hydrogen dilutions at a high pressure by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD). The optical models were based on effective medium approximation (EMA) and effective to estimate the thickness of the amorphous incubation layer and the volume fractions of amorphous, microcrystalline phase and void in μc-Si:H thin films. We obtained an acceptable data fit and the SE results were consistent with that from Raman spectroscopy and atomic force microscopy (AFM). We found a thick incubation layer in μc-Si:H thin films deposited at a high rate of ~ 5 Å/s and this microstructure strongly affected their conductivity.     

Diffusion of nickel in silicon below 475 °C

Nickel films were deposited on (100) and (111) surfaces of single-crystal silicon and were then annealed. The conditions under which the nickel is deposited determine whether or not an NiSi compound forms on annealing. It is postulated that defects are necessary for the formation of an NiSi compound at annealing temperatures below at least 475 °C, although the presence of defects may not necessarily cause the formation of a silicide. For substrate temperatures below 70 °C, defects are created during the vapor deposition of nickel on silicon. These defects always result in the formation of nickel silicide when the sample is annealed at higher temperatures. When nickel is deposited on defect-free silicon at temperatures of about 250 °C no defects are generated and, although interdiffusion of nickel and silicon occurs, silicide formation does not take place upon subsequent annealing below 475 °C. The activation energies for the diffusion of nickel into (100) silicon and (111) silicon were determined.     

Effect of hydrogen radical on growth of μc-Si in hetero-structured SiCx alloy films

The changes of the crystallinity of μc-Si phase are studied in samples deposited with hydrogen dilution ratio, H₂/SiH₄, from 9.0 to 19.0 by hot-wire CVD (Cat-CVD). In the samples deposited at filament temperature, T_f, of 1850 °C, the crystalline fraction and the crystallite size of μc-Si phase increased with increasing the H₂/SiH₄. The carbon content, C/(Si+C), was almost constant. In the XRD patterns, the intensity of Si(1 1 1) peak decreased and that of Si(2 2 0) peak increased with increasing the H₂/SiH₄. In the samples deposited at T_f of 2100 °C with H₂/SiH₄ over 11.4, the μc-Si phase was not formed and the C/(Si+C) increased. The growth mechanism of μc-Si in hetero-structured SiC_x alloy films is discussed.     

热丝CVD法低温制备的多晶硅薄膜质量对衬底依赖性的研究

以SiH4和H2作为反应气体,采用HWCVD的方法分别在石英玻璃、AZO、Si（100）和Si（111）衬底上制备了多晶硅薄膜。利用X射线衍射（XRD）,拉曼（Raman）光谱和傅里叶红外（FT-IR）吸收光谱研究了不同衬底对多晶硅薄膜的择优取向、晶化率和应力的影响,用SEM观察了多晶硅薄膜的表面形貌。研究发现在4种衬底上生长的多晶硅薄膜均为（111）择优取向。单晶硅片对多晶硅薄膜有很强的诱导作用,并且Si（111）的诱导作用优于Si（100）的诱导作用。AZO对多晶硅薄膜生长也有一定的诱导作用。通过计算薄膜晶态比,得到除以石英为衬底的样品外,其它3种样品的晶态比均在90%以上,尤其以单晶硅片为衬底的样品更高。石英玻璃、AZO和Si（100）上生长的多晶硅薄膜中均存在压应力。     

Effects of annealing on the structural properties of indium rich InGaN films

Indium rich (In-rich) InGaN films were grown on Ge (111) substrate by plasma assisted molecular beam epitaxy with thin GaN as a buffer layer. The effects of annealing temperature and annealing time on the structural properties of In-rich InGaN films were investigated by X-ray diffraction (XRD). XRD results indicate that the as-grown InGaN films annealed at different temperatures for 1 min and 1 h respectively did not improve the film crystalline quality. But with the annealing at 750 °C and 800 °C for 1 min respectively the metallic indium was desorbed from the InGaN structure. The InGaN films annealed at higher than 660 °C for 1 h also showed the indium desorption. The InGaN film has the best film quality after annealed at 660 °C for 6 h with the full-width at half-maximum of InGaN (002) peak to be 879 arcsec. The InGaN crystalline quality started to degrade after annealed at the temperatures higher than 660 °C for 6 h.