Preferred growth of nanocrystalline silicon in boron-doped nc-Si:H Films

Preferred growth of nanocrystalline silicon (nc-Si) was first found in boron-doped hydrogenated nanocrystalline (nc-Si:H) films prepared using plasma-enhanced chemical vapor deposition system. The films were characterized by high-resolution transmission electron microscope, X-ray diffraction (XRD) spectrum and Raman Scattering spectrum. The results showed that the diffraction peaks in XRD spectrum were at 2θ≈47° and the exponent of crystalline plane of nc-Si in the film was (2 2 0). A considerable reason was electric field derived from dc bias made the bonds of Si-Si array according to a certain orient. The size and crystalline volume fraction of nc-Si in boron-doped films were intensively depended on the deposited parameters: diborane (B₂H₆) doping ratio in silane (SiH₄), silane dilution ratio in hydrogen (H₂), rf power density, substrate's temperature and reactive pressure, respectively. But preferred growth of nc-Si in the boron-doped nc-Si:H films cannot be obtained by changing these parameters.     

Hot wire configuration for depositing device grade nano-crystalline silicon at high deposition rate

The University of Barcelona is developing a pilot-scale hot wire chemical vapor deposition (HW-CVD) set up for the deposition of nano-crystalline silicon (nc-Si:H) on 10 cm × 10 cm glass substrate at high deposition rate. The system manages 12 thin wires of 0.15-0.2 mm diameter in a very dense configuration. This permits depositing very uniform films, with inhomogeneities lower than 2.5%, at high deposition rate (1.5-3 nm/s), and maintaining the substrate temperature relatively low (250 °C). The wire configuration design, based on radicals’ diffusion simulation, is exposed and the predicted homogeneity is validated with optical transmission scanning measurements of the deposited samples. Different deposition series were carried out by varying the substrate temperature, the silane to hydrogen dilution and the deposition pressure. By means of Fourier transform infrared spectroscopy (FTIR), the evolution in time of the nc-Si:H vibrational modes was monitored. Particular importance has been given to the study of the material stability against post-deposition oxidation.     

Effect of hydrogen plasma treatment on the surface morphology, microstructure and electronic transport properties of nc-Si:H

Hydrogenated nanocrystalline silicon (nc-Si:H) films, deposited by reactive radio-frequency sputtering with 33% hydrogen dilution in argon at 200 °C, were treated with low-power hydrogen plasma at room temperature at various power densities (0.1-0.5 W/cm²) and durations (10 s-10 min). Plasma treatment reduced the surface root mean square roughness and increased the average grain size. This was attributed to the mass transport of Si atoms on the surface by surface and grain boundary diffusion. Plasma treatment under low power density (0.1 W/cm²) for short duration (10 s) caused a significant enhancement of crystalline volume fraction and electrical conductivity, compared to as-deposited film. While higher power (0.5 W/cm²) hydrogen plasma treatment for longer durations (up to 10 min) caused moderate improvement in crystalline fraction and electrical properties; however, the magnitude of improvement is not significant compared to low-power (0.1 W/cm²)/short-duration (10 s) plasma exposure. The results indicate that low-power hydrogen plasma treatment at room temperature can be an effective tool to improve the structural and electrical properties of nc-Si:H.     

Cold deposition of large-area amorphous hydrogenated silicon films by dielectric barrier discharge chemical vapor deposition

Amorphous hydrogenated silicon films were deposited on glass substrates at room temperature. This cold deposition process was operated in a dielectric barrier discharge CVD reactor with a fixed strip-shaped plasma matched with a moving substrate holder. The maximum film area was 300 × 600 mm². The film deposition rate as a function of applied peak voltage of DBD power was investigated under different hydrogen-diluted silane concentrations, and the film surface smoothness, continuity, and film/glass adherence were also studied. The maximum deposition rate was 12.2 Å/s, which was performed under the applied peak voltage of 16 kV and a hydrogen-diluted silane concentration of 50%. IR measurements reveal that the silane concentration plays a key role in determining the hydrogen-silicon bonding configurations. With increasing hydrogen-diluted silane concentration, the H-Si bonding configurations shift gradually from Si-H₃ to Si-H. The variation of photo/dark conductivity ratio and optical bandgap versus hydrogen-diluted silane concentration were investigated. The use of DBD-CVD for deposition of a-Si:H films offers certain advantages, such as colder substrate, faster film growth rate, and larger deposition area. However, the consumption of silane for the DBD-PECVD procedure is much greater than for the RF-PECVD process.     

Flash-lamp-crystallized polycrystalline silicon films with high hydrogen concentration formed from Cat-CVD a-Si films

We investigate residual forms of hydrogen (H) atoms such as bonding configuration in poly-crystalline silicon (poly-Si) films formed by the flash-lamp-induced crystallization of catalytic chemical vapor deposited (Cat-CVD) a-Si films. Raman spectroscopy reveals that at least part of H atoms in flash-lamp-crystallized (FLC) poly-Si films form Si-H₂ bonds as well as Si-H bonds with Si atoms even using Si-H-rich Cat-CVD a-Si films, which indicates the rearrangement of H atoms during crystallization. The peak desorption temperature during thermal desorption spectroscopy (TDS) is as high as 900 °C, similar to the reported value for bulk poly-Si.     

Highly reflective nc-Si:H/a-CNx:H multilayer films prepared by r.f. PECVD technique

Multilayer thin films consisting of a-CN_x:H/nc-Si:H layers prepared by radio-frequency plasma enhanced chemical vapour (r.f. PECVD) deposition technique were studied. High optical reflectivity at a specific wavelength is one of major concern for its application. By using this technique, a-CN_x:H/nc-Si:H multilayered thin films (3-11 periods) were deposited on substrates of p-type (111) crystal silicon and quartz. These films were characterized using ultra-violet-visible-near infrared (UV-Vis-NIR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, field effect scanning electron microscopy (FESEM) and AUGER electron spectroscopy (AES). The multilayered films show high reflectivity and wide stop band width at a wavelength of approximately 650 ± 60 nm. The FTIR spectrum of this multilayered structure showed the formation of Si-H and Si-H₂ bonds in the nc-Si:H layer and CC and N-H bonds in a-CN_x:H layer. SEM image and AES reveal distinct formation of a-CN_x:H and nc-Si:H layers in the cross section image with a decrease in interlayer cross contamination with increasing number of periods.     

Variation of microstructure and transport properties with filament temperature of HWCVD prepared silicon thin films

Thin films of hydrogenated silicon are prepared by varying the filament temperature (T_F) (1600-1900 °C) at a deposition rate of 8-12 Å/s without using any hydrogen dilution. While the films deposited at low T_F are amorphous in nature, those deposited at higher T_F (≥ 1800 °C) contain nanocrystallites embedded in the amorphous network. The optical band gap (E₀₄) of the films (~ 1.89-1.99 eV) is slightly higher compared to the regular films, which is attributed to the improved short and medium range order as well as the presence of low density amorphous tissues in the grain boundary regions. The films show improved stability under long term light exposure due to more ordered structure and presence of hydrogen mostly as strong Si-H bonds.     

Optical and structural characterization of inhomogeneities in a-Si:H TO μc-Si transition

The a-Si:H films with different thickness and microstructure have been deposited with rf-PECVD using a plasma of silane diluted with hydrogen. The structure and optical analysis were carried out by X-ray diffraction, UV-VIS and Raman spectroscopy. Spectral refractive indices, optical energy band gaps, extinction coefficients, phases ratio and grain size were determined as a function of the hydrogen dilution (R = H₂/SiH₄). Hydrogen dilution of silane results in an inhomogeneous growth during which the material evolves from amorphous hydrogenated silicon (a-Si:H) to micro-crystalline hydrogenated silicon (μc-Si:H). XRD analysis indicated that films with R = 0 and R = 20 were amorphous and homogeneous, while films with R = 40 and higher were micro-crystalline consisting medium range ordered silicon hydride (Si₄H) and μc-Si phases with different size of crystallites, which was confirmed also by Raman spectroscopy.     

Comparative study of annealing and oxidation effects in a-SiC:H and a-SiC thin films deposited by radio-frequency magnetron sputtering

Thermal annealing and oxidation effects in hydrogenated (a-SiC:H) and nonhydrogenated (a-SiC) amorphous silicon-carbon alloy films deposited by radio-frequency magnetron sputtering have been studied. The a-SiC:H and a-SiC films were thermally treated in dry Ar, wet Ar, and dry O₂ atmospheres at temperatures up to 1150 °C. The principal effects of thermal annealing in an inert atmosphere on a-SiC:H films were found to be redistribution of hydrogen bonds and formation of amorphous graphitic carbon clusters. Strong oxidation of a-SiC:H was observed after thermal treatment in oxygen at 700 °C while annealing in wet argon caused partial oxidation. Oxidation of the carbon clusters in porous a-SiC:H structures is suggested to be responsible for the higher oxidation efficiency of a-SiC:H in oxygen. In contrast, the structure of a-SiC films remained almost unchanged after annealing in dry argon up to 1000 °C. No oxidation of a-SiC was detected until 1000 °C. Water vapor was found to be more effective at oxidizing a-SiC at 1000 °C than dry oxygen, which is similar to the oxidation behavior of crystalline SiC. The high thermal and oxidation stabilities of a-SiC layers were attributed to the dense and nanovoid-free amorphous SiC network.     

Size modulation of nanocrystalline silicon embedded in amorphous silicon oxide by Cat-CVD

Different issues related to controlling size of nanocrystalline silicon (nc-Si) embedded in hydrogenated amorphous silicon oxide (a-SiO_x:H) deposited by catalytic chemical vapor deposition (Cat-CVD) have been reported. Films were deposited using tantalum (Ta) and tungsten (W) filaments and it is observed that films deposited using tantalum filament resulted in good control on the properties. The parameters which can affect the size of nc-Si domains have been studied which include hydrogen flow rate, catalyst and substrate temperatures. The deposited samples are characterized by X-ray diffraction, HRTEM and micro-Raman spectroscopy, for determining the size of the deposited nc-Si. The crystallite formation starts for Ta-catalyst around the temperature of 1700 °C.     

High growth rate of a-SiC:H films using ethane carbon source by HW-CVD method

Hydrogenated amorphous silicon carbide (a-SiC:H) thin films were prepared using pure silane (SiH₄) and ethane (C₂H₆), a novel carbon source, without hydrogen dilution using hot wire chemical vapour deposition (HW-CVD) method at low substrate temperature (200 °C) and at reasonably higher deposition rate (19·5 Å/s < r _d < 3·2 Å/s). Formation of a-SiC:H films has been confirmed from FTIR, Raman and XPS analysis. Influence of deposition pressure on compositional, structural, optical and electrical properties has been investigated. FTIR spectroscopy analysis revealed that there is decrease in C–H and Si–H bond densities while, Si–C bond density increases with increase in deposition pressure. Total hydrogen content drops from 22·6 to 14·4 at.% when deposition pressure is increased. Raman spectra show increase in structural disorder with increase in deposition pressure. It also confirms the formation of nearly stoichiometric a-SiC:H films. Bandgap calculated using both Tauc’s formulation and absorption at 10⁴ cm^?1 shows decreasing trend with increase in deposition pressure. Decrease in refractive index and increase in Urbach energy suggests increase in structural disorder and microvoid density in the films. Finally, it has been concluded that C₂H₆ can be used as an effective carbon source in HW-CVD method to prepare stoichiometric a-SiC:H films.     

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.     

Synthesis of carbon coatings employing a plasma torch from an argon-acetylene gas mixture at reduced pressure

Amorphous hydrogenated carbon films (a-C:H) were formed on Si (1 1 1) wafers from an argon-acetylene gas mixture at a reduced pressure of 1000 Pa using a direct current (DC) plasma torch discharge. The Ar/C₂H₂ gas volume ratio varied from 1:1 to 8:1, the distance between plasma torch exit and the samples 0.04-0.095 m. The DC plasma torch technique allows the production of thick (∼90 μm) coatings at 0.3 μm/s growth rates. Raman spectra shape, D and G peak positions and the intensity ratio (I_D/I_G) show an increase of sp³ bond fraction with decreasing acetylene flow in argon plasma. Reflectance of the coatings deposited at Ar/C₂H₂=8:1 is high (∼97%) and slightly increases with increasing distance between samples and plasma torch exit.     

Physical properties of hydrogenated Al-doped ZnO thin layer treated by atmospheric plasma with oxygen gas

Hydrogenated Al-doped ZnO (H:AZO) thin films were deposited on glass substrates at room temperature by radio-frequency magnetron sputtering at various hydrogen flow rates. The addition of hydrogen improved the resistivity of the H:AZO films significantly. A thin insulating layer was produced on H:AZO films by atmospheric pressure plasma with Ar/O₂ reactive gas. The resistivity degenerated and the optical band gap of the oxygen plasma-treated H:AZO films decreased from 3.7 eV to 3.4 eV. This was attributed to a decrease in the hydrogen concentration at the film surface according to elemental depth analysis.     

Device-quality polycrystalline silicon films deposited at low process temperatures by hot-wire chemical vapor deposition

Device-grade undoped hydrogenated polycrystalline silicon thin films have been developed from a gas mixture of silane and hydrogen using a hot-wire chemical vapor deposition (HW-CVD) method, optimizing the deposition parameters. Proper design of the HW-CVD reactor helps to deposit a uniform quality of film over a large area (100 cm²) with a two filament configuration. Extensive studies have been made of the effects of hydrogen dilution (4–60), substrate temperature (180–400°C) and filament temperature (1500–1700°C) on the film growth. Atomic force micrographs give a quantitative estimate of roughness for these films. UV-visible ellipsometry analyses confirm their compactness and crystallinity while X-ray diffraction patterns allow for the determination of the crystallite sizes (up to 400 Å). Using a hydrogen dilution of 60, a substrate temperature of 300°C and a filament temperature of 1500°C, a dark conductivity of 2.5×10⁻⁵ S/cm and its activation energy of 0.45 eV have been obtained. For these films, the Hall mobility attains 10 cm²/V s. With these deposition parameters, the intrinsic layer of complete p–i–n HW-CVD solar cells has been realized. These cells, deposited on TCO coated Corning glass substrates, exhibit 1.8% conversion efficiency under 100 mW/cm² irradiation.     

Effects of hydrogen gas on properties of tin-doped indium oxide films deposited by radio frequency magnetron sputtering method

Tin-doped indium oxide (ITO) films were deposited at ∼ 70 °C of substrate temperature by radio frequency magnetron sputtering method using an In₂O₃-10% SnO₂ target. The effect of hydrogen gas ratio [H₂ / (H₂ + Ar)] on the electrical, optical and mechanical properties was investigated. With increasing the amount of hydrogen gas, the resistivity of the samples showed the lowest value of 3.5 × 10^− 4 Ω·cm at the range of 0.8-1.7% of hydrogen gas ratio, while the resistivity increases over than 2.5% of hydrogen gas ratio. Hall effect measurements explained that carrier concentration and its mobility are strongly related with the resistivity of ITO films. The supplement of hydrogen gas also reduced the residual stress of ITO films up to the stress level of 110 MPa. The surface roughness and the crystallinity of the samples were investigated by using atomic force microscopy and x-ray diffraction, respectively.     

Effect of composition on mechanical behaviour of diamond-like carbon coatings modified with titanium

In this study, diamond-like carbon (DLC) films modified with titanium were deposited by plasma decomposition of metallorganic precursor, titanium isopropoxide in CH₄/H₂/Ar gas atmosphere. The obtained films were composed of amorphous titanium oxide and nanocrystalline titanium carbide, embedded in an amorphous hydrogenated (a-C:H) matrix. The TiC/TiO₂ ratio in the DLC matrix was found to be dependent on the deposition parameters. The dependence of the films chemical composition on gas mixture and substrate temperature was investigated by X-ray photoelectron spectroscopy, whereas the crystallinity of TiC nanoparticles and their dimension were evaluated by X-ray diffraction. The size of TiC crystallites varied from 10 to 35 nm, depending on the process parameters. The intrinsic hardness of 10-13 GPa, elastic modulus of 170-200 GPa and hardness-to-modulus ratio of obtained coatings were measured by the nanoindentation technique. Obtained results demonstrated a correlation of mechanical properties with the chemical composition and the ratio of amorphous/crystalline phases in the films. In particular, the formation of nanocrystalline TiC with atomic concentration not exceeding 10% and with grain size between 10 nm and 15 nm resulted in significantly enhanced mechanical properties of composite material in comparison with ordinary DLC films.     

Optimization of n nc-Si:H and a-SiNx:H layers for their application in nc-Si:H TFT

The n-type doped silicon thin films were deposited by plasma enhanced chemical vapor deposition (PECVD) technique at high and low H₂ dilutions. High H₂ dilution resulted in n⁺ nanocrystalline silicon films (n⁺ nc-Si:H) with the lower resistivity (ρ ∼0.7 Ω cm) compared to that of doped amorphous silicon films (∼900 Ω cm) grown at low H₂ dilution. The change of the lateral ρ of n⁺ nc-Si:H films was measured by reducing the film thickness via gradual reactive ion etching. The ρ values rise below a critical film thickness, indicating the presence of the disordered and less conductive incubation layer. The 45 nm thick n⁺ nc-Si:H films were deposited in the nc-Si:H thin film transistor (TFT) at different RF powers, and the optimum RF power for the lowest resistivity (∼92 Ω cm) and incubation layer was determined. On the other hand, several deposition parameters of PECVD grown amorphous silicon nitride (a-SiN_x:H) thin films were changed to optimize low leakage current through the TFT gate dielectric. Increase in NH₃/SiH₄ gas flow ratio was found to improve the insulating property and to change the optical/structural characteristics of a-SiN_x:H film. Having lowest leakage currents, two a-SiN_x:H films with NH₃/SiH₄ ratios of ∼19 and ∼28 were used as a gate dielectric in nc-Si:H TFTs. The TFT deposited with the NH₃/SiH₄∼19 ratio showed higher device performance than the TFT containing a-SiN_x:H with the NH₃/SiH₄∼28 ratio. This was correlated with the N−H/Si−H bond concentration ratio optimized for the TFT application.     

Influence of hydrogen introduction on structure and properties of ZnO thin films during sputtering and post-annealing

ZnO thin films were prepared in Ar and Ar + H₂ atmospheres by rf magnetron sputtering, and then they were annealed in vacuum and Ar + H₂ atmosphere, respectively. The structure and optical-electrical properties of the films were investigated by X-ray diffraction, transmittance spectra, and resistivity measurement, and their dependences on deposition atmosphere, annealing treatment, and aging were studied. The results showed that adding H₂ in deposition atmosphere improved the crystallinity of the films, decreased lattice constant, increased band gap, decreased the resistivity by the order of 10⁴ Ω cm, but exhibited poor conductive stability with aging. After Ar + H₂ and vacuum annealing, crystallinity of the films deposited in Ar and Ar + H₂ was further improved; their resistivity was decreased by the order of 10⁵ and 10¹ Ω cm, respectively, and exhibited high conductive stability with aging. We suggest that the formed main defect is V_O and H_i when H₂ is introduced during deposition, which decreases the resistivity but cannot improve the conductive stability; hydrogen would remove negatively charged oxygen species near grain boundaries during Ar + H₂ annealing to decrease the resistivity, and grain boundaries are passivated by formation of a number of V_O-H complex (H_O) to improve the conductive stability at the same time. Under vacuum annealing, the hydrogen that is introduced non-intentionally from deposition chamber maybe plays an important role; it exists as H_O in the films to improve the conductive stability of the films.     

Properties of atomic layer deposited HfO2 thin films

The growth, composition and morphology of HfO₂ films that have been deposited by atomic layer deposition (ALD) are examined in this article. The films are deposited using two different ALD chemistries: i) tetrakis ethylmethyl amino hafnium and H₂O at 250° and ii) tetrakis dimethyl amino hafnium and H₂O at 275 °C. The growth rates are 1.2 Å/cycle and 1.0 Å/cycle respectively. The main impurities detected both by X-ray Photoelectron Spectroscopy and Fourier transform infrared spectroscopy (FTIR) are bonded carbon (~ 3 at.%) and both bulk and terminal OH species that are partially desorbed after high temperature inert anneals up to 900 °C. Atomic Force Microscopy reveals increasing surface roughness as a function of increasing film thickness. X-ray diffraction shows that the morphology of the as-deposited films is thickness dependent; films with thickness around 30 nm for both processes are amorphous while ~ 70 nm films show the existence of crystallites. These results are correlated with FTIR measurements in the far IR region where the HfO₂ peaks are found to provide an easy and reliable technique for the determination of the crystallinity of relatively thick HfO₂ films. The index of refraction for all films is very close to that for bulk crystalline HfO₂.