Revisiting the B-factor variation in a-SiC:H deposited by HWCVD

In order to understand material properties in a better way, it is always desirable to come up with new variables that might be related to the film properties. The B-parameter is such a variable, which relates to the quality of a-SiC:H films both in terms of electronic and optical properties. B (scaling factor) is essentially the slope of the straight-line part of the (E)^1/2–E (Tauc plot). Due to dependence on a large number of parameters and no detailed research, many previous authors have surmised that B has an ambiguous correlation with carbon content. We have made an attempt to establish the relation between the B-parameter as a quality-indicating factor of a-SiC:H films in both carbon- and silicon-rich material. For this we studied a-SiC:H films deposited by the HWCVD method with broad deposition parameters of substrate temperature (T_s), filament temperature (T_F) and C₂H₂ fraction. Our results indicate that the B-parameter varies considerably with process conditions such as T_F, total gas pressure and carbon content. An attempt is made to correlate the B-parameter with an opto-electronic parameter, such as the mobility edge, which has relevance to the device-quality aspects of a-SiC:H films prepared by HWCVD.     

Amorphous silicon carbide thin films (a-SiC:H) deposited by plasma-enhanced chemical vapor deposition as protective coatings for harsh environment applications

We investigated amorphous silicon carbide (a-SiC:H) thin films deposited by plasma-enhanced chemical vapor deposition (PECVD) as protective coatings for harsh environment applications. The influence of the deposition parameters on the film properties was studied. Stoichiometric films with a low tensile stress after annealing (< 50 MPa) were obtained with optimized parameters. The stability of a protective coating consisting of a PECVD amorphous silicon oxide layer (a-SiO_x) and of an a-SiC:H layer was investigated through various aging experiments including annealing at high temperatures, autoclave testing and temperature cycling in air/water vapor environment. A platinum-based high-temperature metallization scheme deposited on oxidized Si substrates was used as a test vehicle. The a-SiO_x/a-SiC:H stack showed the best performance when compared to standard passivation materials as amorphous silicon oxide or silicon nitride coatings.     

Two-step annealing of hot wire chemical vapor deposited a-Si:H films

A two-step annealing process was used to investigate the effect of dehydrogenation on crystallization and grain growth of low and high hydrogen content hot wire chemical vapor deposited (HWCVD) a-Si:H films. A low temperature pre-annealing followed by a rapid thermal annealing step at 600 °C was carried out. For the high hydrogen content film XRD (111) peak narrowed quite a bit, while opposite effect was observed for the low hydrogen content film. According to the grain sizes as calculated from TEM images, grain sizes of both of the two-step annealed high and low hydrogen content films are smaller than that of the single stage annealed film.     

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.     

XPS study of carbon nitride films deposited by hot filament chemical vapor deposition using carbon filament

Amorphous carbon nitride, a-CN_x, thin films were deposited by hot filament CVD using a carbon filament with dc negative bias voltage on the substrate. The effects of the negative bias and the filament components on the binding structure of the films are investigated by XPS. The composition ratio of graphite to amorphous carbon in the filaments affects the bonding structure of carbon and nitrogen in the films, although the nitrogen content in the films is almost same as 0.1. The nitrogen content in the films changes from 0.1 to 0.3 as the negative bias changes from 0 to − 300 V.     

Hot wire chemical vapour deposition (HWCVD) of boron carbide thin films from ortho-carborane for neutron detection application

Detection of neutrons is possible if suitable converters such as Li, LiF or ¹⁰B in the form of thin films are used along with the semiconductor device. The use of boron (¹⁰B) in some host matrix as a neutron detector is attractive due to its large neutron capture cross-section. Boron carbide (BC) films are deposited on silicon substrates by HWCVD technique using solid ortho-carborane (o-C₂B₁₀H₁₂) precursor with argon as carrier gas. The films contain ¹⁰B required for neutron detection as confirmed by the Secondary Ion Mass Spectroscopy. Variations in its structure as well as the chemical bonding configurations using Fourier Transform Infra-Red, Raman and X-ray diffraction spectroscopy have been studied.     

Multi-phase structured silicon carbon nitride thin films prepared by hot-wire chemical vapour deposition

In this work, Silicon Carbon Nitride (Si-C-N) thin films were deposited by Hot Wire Chemical Vapour Deposition (HWCVD) technique from a gas mixture of silane (SiH₄), methane (CH₄) and nitrogen (N₂). Six sets of Si-C-N thin films were produced and studied. The component gas flow rate ratio (SiH₄:CH₄:N₂) was kept constant for all film samples. The total gas flow-rate (SiH₄ + CH₄ + N₂) was changed for each set of films resulting in different total gas pressure which represented the deposition pressure for each of these films ranging from 40 to 100 Pa. The effects of deposition pressure on the chemical bonding, elemental composition and optical properties of the Si-C-N were studied using Fourier transform infrared (FTIR) spectroscopy, Auger Electron Spectroscopy (AES) and optical transmission spectroscopy respectively. This work shows that the films are silicon rich and multi-phase in structure showing significant presence of hydrogenated amorphous silicon (a-Si:H) phase, amorphous silicon carbide (a-SiC), and amorphous silicon nitride (a-SiN) phases with Si-C being the most dominant. Below 85 Pa, carbon content is low, and the films are more a-Si:H like. At 85 Pa and above, the films become more Si-C like as carbon content is much higher and carbon incorporation influences the optical properties of the films. The properties clearly indicated that the films underwent a transition between two dominant phases and were dependent on pressure.     

Ultrafast deposition of silicon nitride and semiconductor silicon thin films by hot wire chemical vapor deposition

The technology of Hot Wire Chemical Vapor Deposition (HWCVD) or Catalytic Chemical Vapor Deposition (Cat-CVD) has made great progress during the last couple of years. This review discusses examples of significant progress. Specifically, silicon nitride deposition by HWCVD (HW-SiN_x) is highlighted, as well as thin film silicon single junction and multijunction junction solar cells. The application of HW-SiN_x at a deposition rate of 3 nm/s to polycrystalline Si wafer solar cells has led to cells with 15.7% efficiency and preliminary tests of our transparent and dense material obtained at record high deposition rates of 7.3 nm/s yielded 14.9% efficiency. We also present recent progress on Hot-Wire deposited thin film solar cells. The cell efficiency reached for (nanocrystalline) nc-Si:H n-i-p solar cells on textured Ag/ZnO presently is 8.6%. Such cells, used in triple junction cells together with Hot-Wire deposited proto-Si:H and plasma-deposited SiGe:H, have reached 10.9% efficiency. Further, in our research on utilizing the HWCVD technology for roll-to-roll production of flexible thin film solar cells we recently achieved experimental laboratory scale tandem modules with HWCVD active layers with initial efficiencies of 7.4% at an aperture area of 25 cm².     

Initiated chemical vapor deposition of pH responsive poly(2-diisopropylamino)ethyl methacrylate thin films

Poly(2-(diisopropylamino)ethyl methacrylate) (PDPAEMA) thin films were deposited on low temperature substrates by initiated chemical vapor deposition (iCVD) method using tertbutyl peroxide as an initiator. Very high deposition rates up to 38 nm/min were observed at low filament temperatures due to the use of the initiator. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy show the formation of PDPAEMA films with high retention of tertiary amine functionality which is responsible for pH induced changes in the wetting behavior of the surfaces. As-deposited PDPAEMA thin films on flat Si surface showed a reversible switching of water contact angle values between 87° and 28°; after successive treatments of high and low pH water solutions, respectively. Conformal and non-damaging nature of iCVD allowed to functionalize fragile and rough electrospun poly(methyl methacrylate) fiber mat surfaces by PDPAEMA, which creates a surface with a switching behavior between superhydrophobic and approaching superhydrophilic with contact angle values of 155 ± 3°and 22 ± 5°, respectively.     

Thermal conductivity and sound velocity measurements of plasma enhanced chemical vapor deposited a-SiC:H thin films

We report ultrafast optical measurements of the thermal conductivity and longitudinal sound velocity for a-SiC:H thin films deposited by plasma enhanced chemical vapor deposition (PECVD). Porous and non-porous films with mass densities ranging from 1.0-2.5 g/cm³ were obtained by intentionally varying the PECVD process conditions. The longitudinal sound velocities for these materials as determined by picosecond ultrasonics ranged from 2370 m/s to 10460 m/s, and the Young's modulus determined from the sound velocity measurements ranged from 5-200 GPa. Time domain thermoreflectance measurements determined the thermal conductivity to range from 0.0009 W/cmK to 0.042 W/cmK.     

Aluminum-induced crystallization of amorphous silicon films deposited by hot wire chemical vapor deposition on glass substrates

Aluminum-induced crystallization of amorphous silicon films is discussed. Amorphous Si films were deposited by hot wire chemical vapor deposition onto Al coated glass substrates at 430 °C. Complete crystallization of a-Si films was achieved during a-Si deposition by controlling Al and Si layer thicknesses. The grain structure of the poly-Si films formed on glass substrate was evaluated by optical and electron microscopy. Continuous poly-Si films were obtained using Al layers with a thickness of 500 nm or less. The average grain size was found to be 10-15 μm, corresponding to a grain size/thickness ratio greater than 20.     

The role of hydrogen in hot wire chemical vapor deposition of Ge-Sb-Te thin films

Ge-Sb-Te (GST) thin films were deposited by hot wire chemical vapor deposition using metalorganic Ge, Sb, and Te precursors. The hydrogen flow was varied in order to investigate the hydrogen influence on the deposition of GST films. A decrease of the temperature (from 450 to 350 °C) and an increase of the hydrogen concentration (from 0 to 50%) of the total gas flow result in a lowering of the deposition rate. Additionally, a higher hydrogen flow can be used to obtain smooth GST films (mean roughness—5 nm). The chemical composition of the films significantly depends on the hydrogen content. The tellurium content decreases and the antimony content increases with increasing hydrogen flow.     

Optical and structural properties of silicon oxynitride deposited by plasma enhanced chemical vapor deposition

We present an overview of the properties of silicon oxynitride material (SiON) deposited by plasma enhanced chemical vapor deposition (PECVD) for photovoltaic applications. SiON films were deposited using silane (SiH₄), ammonia (NH₃) and nitrogen protoxide (N₂O) as precursor gases in a low frequency PECVD. Varying the gas flow mixture leads to a whole range of SiON layers starting from the silicon oxide to the silicon nitride with unique stoichiometries and properties. Thanks to spectroscopic ellipsometry measurements we have confirmed the suitability of SiON for antireflection coating layers due to the range of the refractive indexes attainable. SiON structure was analyzed by X-ray photo-electron spectroscopy. We have thus highlighted the critical role of oxygen behavior on the SiON network and the progressive replacement of nitrogen by oxygen atoms when the oxygen precursor increases. The type of chemical bonds present in SiON layers was also investigated by infrared spectroscopy. The SiON layers also contain a non-negligible amount of hydrogen which might be useful for passivation applications. The behavior of hydrogen content was thus analyzed by elastic recoil decay analysis and desorption characterization. A typical rapid thermal annealing was performed on the SiON samples in order to simulate the solar cells contact annealing and to investigate its impact on the dielectric film properties. It was found that hydrogen becomes weakly bonded to the films and strongly decreases in quantity with the annealing. The surface passivation effect is presented in the last part of this paper. The trend before and after a rapid thermal annealing showed opposite results which could be explained by the high porosity of the layers and the formation of Si-O bonds.     

Role of argon in hot wire chemical vapor deposition of hydrogenated nanocrystalline silicon thin films

Structural, optical and electrical properties of hydrogenated nanocrystalline silicon (nc-Si:H) films, deposited from silane (SiH₄) and argon (Ar) gas mixture without hydrogen by hot wire chemical vapor deposition (HW-CVD) method were investigated. Film properties are carefully and systematically studied as a function of argon dilution of silane (R_Ar). We observed that the deposition rate is much higher (4-23 Å/s) compared to conventional plasma enhanced chemical vapor deposited nc-Si:H films using Ar dilution of silane (0.5-0.83 Å/s). Characterization of these films with Raman spectroscopy revealed that Ar dilution of silane in HW-CVD endorses the growth of crystallinity and structural order in the nc-Si:H films. The Fourier transform infrared spectroscopic analysis showed that with increasing Ar dilution, the hydrogen bonding in the films shifts from di-hydrogen (Si-H₂) and (Si-H₂)_n complexes to mono-hydrogen (Si-H) bounded species. The hydrogen content in the films increases with increasing Ar dilution and was found to be < 4 at.% over the entire range of Ar dilutions of silane studied. However, the band gap shows decreasing trend with increase in Ar dilution of silane and it has been attributed to the decrease in the percentage of the amorphous phase in the film. The microstructure parameter was found to be > 0.4 for the films deposited at low Ar dilution of silane and ~ 0.1 or even less for the films deposited at higher Ar dilution, suggesting that there is an enhancement of structural order and homogeneity in the film. From the present study it has been concluded that the Ar dilution of silane is a key process parameter to induce the crystallinity and to improve the structural ordering in the nc-Si:H films deposited by the HW-CVD method.     

Electrical characterization of amorphous silicon carbide thin films deposited via polymeric source chemical vapor deposition

Polymeric source chemical vapor deposition (PS-CVD) was used to synthesize amorphous silicon carbide (a-SiC) thin films. The PS-CVD process was conducted at temperatures between 750 and 1000 °C. The substrates used were silicon single crystal wafers of p-type and n-type, and thermally grown silicon dioxide substrates. The chemical and electrical properties of the films were studied by various techniques, including Fourier transform infrared spectroscopy, elastic recoil detection (ERD), and capacitance-voltage technique. A correlation was observed between the average concentration of oxygen in the films and the deposition temperature, linking a low oxygen concentration to a high deposition temperature. However, the concentration of oxygen in the films deposited at the same temperature is independent of the substrate. The thin films deposited at low temperature showed insulating behaviour, while the semiconducting behaviour is obtained at high deposition temperatures. Ohmic contacts were obtained on the deposited semiconductor thin film by evaporating nickel contacts, followed by annealing of the sample at 800 °C for 2 min.     

Pressure dependent structural and optical properties of silicon carbide thin films deposited by hot wire chemical vapor deposition from pure silane and methane gases

Silicon carbide (SiC) thin films were deposited using hot wire chemical vapor deposition technique from silane (SiH₄) and methane (CH₄) gas precursors. The effect of deposition pressure on structural and optical properties of SiC films was investigated. Various spectroscopic methods including Fourier transform infrared spectroscopy, Raman scattering spectroscopy, Auger electron spectroscopy, and UV–Vis–NIR spectroscopy were used to study these properties. Films deposited at low deposition pressure were Si-rich, and were embedded with nano-crystals of silicon. These films showed strong absorption in the visible region and had low energy band gaps. Near stoichiometric SiC film, were formed at intermediate deposition pressure and these films were transparent in the visible region and exhibited a wide optical band gap. High deposition pressures caused inhomogeneity in the film as reflected by the increase in disorder parameter and low refractive index of the films. This was shown to be due to formation of sp ² carbon clusters in the film structure.     

Hot wire chemical vapor deposited multiphase silicon carbide (SiC) thin films at various filament temperatures

Influence of filament temperature (T_Fil) on the structural, morphology, optical and electrical properties of silicon carbide (SiC) films deposited by using hot wire chemical vapor deposition technique has been investigated. Characterization of these films by low angle XRD, Raman scattering, XPS and TEM revealed the multiphase structure SiC films consisting of 3C–SiC and graphide oxide embedded in amorphous matrix. FTIR spectroscopy analysis show an increase in Si–C, Si–H, and C–H bond densities and decrease in hydrogen content with increase in T_Fil. The C–H bond density was found higher than the of Si–H and Si–C bond densities suggesting that H preferably get attached to C than Si. AFM investigations show decrease in rms surface roughness and grain size with increase in T_Fil. SEM studies show that films deposited at low T_Fil has spherulites-like morphology while at high T_Fil has cauliflower-like structure. Band gap values E_Tauc and E₀₄ increases from 1.76 to 2.10 eV and from 1.80 to 2.21 eV respectively, when T_Fil was increased from 1500 to 2000 °C. These result show increase in band tail width (E₀₄–E_Tauc) of multiphase SiC films. Electrical properties revealed that σ_Dark increases from ~7.87 × 10^?10 to 1.54 × 10^?5 S/cm and E_act decreases from 0.67 to 0.41 eV, which implies possible increase in unintentional doping of oxygen or nitrogen due to improved crystallinity and Si–C bond density with increase in T_Fil. The deposition rate for the films was found moderately high (21 < r_dep < 30 Å/s) over the entire range of T_Fil studied.     

Effect of thermal annealing on the properties of a-SiCN:H films by hot wire chemical vapor deposition using hexamethyldisilazane

We investigated the effect of thermal annealing on the properties of a-SiCN:H films prepared by HWCVD using hexamethyldisilazane focusing on the change in the passivation quality. We found that annealing a-SiCN:H films at the temperature around 600 °C led to an effective hydrogen diffusion, resulting in the enhancement of the passivation effect. The performance of cast polycrystalline silicon solar cells using a-SiCN:H films showed a strong dependence on the contact firing temperature. The best efficiency of 13.75% was achieved at the firing temperature of 750 °C.     

Initiated chemical vapor deposition (iCVD) of copolymer thin films

Initiated chemical vapor deposition (iCVD) represents a novel hot-wire CVD variant for producing copolymer thin films. iCVD copolymerization was characterized by a conventional liquid-phase free radical copolymerization equation when applied to methacrylic acid copolymers. FTIR peak shifts with changing comonomer ratios in the copolymers further supported a copolymerization mechanism. Crosslinked methacrylic acid copolymers provided pH-dependent swelling behavior that enabled an enteric release of active core material when the copolymer was used as an encapsulation coating.     

Properties of aluminum oxide thin films deposited by pulsed laser deposition and plasma enhanced chemical vapor deposition

The chemical, structural, mechanical and optical properties of thin aluminum oxide films deposited at room temperature (RT) and 800 °C on (100) Si and Si-SiO₂ substrates by pulsed laser deposition and plasma enhanced chemical vapor deposition are investigated and compared. All films are smooth and near stoichiometric aluminum oxide. RT films are amorphous, whereas γ type nano-crystallized structures are pointed out for films deposited at 800 °C. A dielectric constant of ∼ 9 is obtained for films deposited at room temperature and 11-13 for films deposited at 800 °C. Young modulus and hardness are in the range 116-254 GPa and 6.4-28.8 GPa respectively. In both cases, the results show that the deposited films have very interesting properties opening applications in mechanical, dielectric and optical fields.