Investigation of optical and compositional properties of thin SiNx:H films with an enhanced growth rate by high frequency PECVD method

Hydrogenated thin silicon nitride (SiN_x:H) films were deposited by high frequency plasma enhanced chemical vapor deposition techniques at various NH₃ and SiH₄ gas flow ratios [R = NH₃/(SiH₄ + NH₃)], where the flow rate of NH₃ was varied by keeping the constant flow (150 sccm) of SiH₄. The deposition rate of the films was found to be 7.1, 7.3, 9 and 11 Å/s for the variation of R as 0.5, 0.67, 0.75 and 0.83, respectively. The films were optically and compositionally characterized by reflectance, photoluminescence, infrared absorption and X-ray photoelectron spectroscopy. The films were amorphous in nature and the refractive indices of the films were varied between 2.46 and 1.90 by changing the gas flow ratio during the deposition. The PL peak energy was increased and the linear band tails become broad with the increase in R. The incorporation of nitrogen takes place with the increase in R.     

Mechanical properties of a-C:H thin films deposited by r.f. PECVD method

Internal stress, hardness and deposition rate were evaluated for hydrogenated amorphous carbon (a-C:H) films prepared by conventional r.f. plasma-enhanced chemical vapour deposition. The internal stress, hardness and deposition rate of 0.9, 18 and 58 nm/min, respectively, achieved at 40 Pa gas pressure for negative self-bias voltages (V_b) window (from −370 to −550 V). It was found that the negative self-bias voltage window was associated with the existence of two turning points, which shift to higher wavenumber of G band peak position of Raman spectroscopy (Raman) at different V_b in relation to the internal stress and hardness, and rapid decreasing of the relative total peak areas of Fourier Transform Infra-red absorption spectroscopy (FT-IR).The internal stress relaxed from approximately 35 eV ion energy when the energy is increased and rapidly decreased in comparison with the stress relaxation equation.     

Crosslinking of copolymer thin films by initiated chemical vapor deposition for hydrogel applications

The ability of initiated chemical vapor deposition to finely tune crosslinking densities in copolymer thin films has been used to develop a functional, reactive hydrogel system. The system consists of poly[maleic anhydride-co-dimethyl acrylamide-co-di(ethylene glycol) divinyl ether] films covalently attached to silicon substrates using the coupling agent 3-aminopropylethoxydimethylsilane. The swelling of the films in water is pH-dependent, with a maximum swelling ratio of 11 at pH = 8. The hydrogel was also functionalized with 0.1 M cysteamine solutions in 2-propanol for 30 min to convert 97% of the anhydride functional groups to carboxylic acid and amide functionalities, confirmed by XPS and Fourier transform infrared spectroscopy. The functionalization yielded free thiol groups at the surface, which were used to attach CdSe/ZnS core-shell semiconductor nanoparticles to the hydrogels.     

BiFeO3 thin films prepared using metalorganic chemical vapor deposition

BiFeO₃ thin films were grown on (001) SrTiO₃ and (001) ZrO₂(Y₂O₃) substrates by single source metalorganic chemical vapor deposition in the temperature range T = 500 ÷ 800 °C using Fe(thd)₃ and Bi(C₆H₅)₃ as volatile precursors. X-ray diffraction analysis shows cube-on-cube epitaxial growth of BiFeO₃ on (001) SrTiO₃. The strongly reduced bismuth transfer into the film due to the high thermal stability of Bi(C₆H₅)₃ was counterbalanced by the increase of the total pressure as well as of the residence time of the precursor flow in the reactor; the Bi/Fe ratio in the film thus becomes close to that in the precursor mixture. Optical second harmonic generation measurements have evidenced the ferroelectric ordering in BiFeO₃ films and the apparent decrease of the Curie temperature of the strained films as compared to BiFeO₃ single crystal.     

Microstructure developments of F-doped SiO2 thin films prepared by liquid phase deposition

This study presents a systematic investigation of the microstructure dependence of liquid phase deposition (LPD) of SiO₂ films on solution parameters and deposition temperature. The corresponding deposition rate and film roughness were also evaluated under various deposition conditions. Smooth and sufficiently dense SiO₂ films, which are the prerequisite for reliable low-k dielectric applications, were deposited on both silicon and fluorine-doped tin oxide coated glass substrates from supersaturated hydrofluorosilicic acid (H₂SiF₆) solution with the addition of boric acid (H₃BO₃). It is shown that H₂SiF₆ acid controls the surface morphology and grain structure through surface reaction while H₃BO₃ acid prompts bulk precipitation in solution. For the 208-nm thick SiO₂ film, the breakdown field exceeded 1.9 MV/cm and the leakage current density was on the order of 10^− 9 A/cm² at 4 V, indicating excellent insulating properties of LPD SiO₂ films. The strong presence of Si-O-Si and some Si-F with little Si-OH bond as shown in FT-IR spectra indicate that the LPD SiO₂ films have mostly a silica network with some fluorine (F) content. F-doping was self-incorporated into the silica films from the H₂SiF₆ solution during deposition process.     

Some physical properties of Sn-doped CdO thin films prepared by chemical bath deposition

Undoped and Sn-doped CdO thin films were prepared by the chemical bath deposition method by means of a procedure that improves the deposition efficiency. All as-grown films were crystallized in the cubic structure of cadmium peroxide (CdO₂) and transformed into CdO with a cubic structure after an annealing process. The as-grown films have a high resistivity (> 10⁶ Ω cm) and an optical bandgap around 3.6 eV. Undoped CdO displays an optical bandgap around 2.32–2.54 eV and has an electrical conductivity of 8 × 10^− 4 Ω cm. The Sn incorporation into CdO produces a blue shift in the optical bandgap (from 2.55 to 2.84 eV) and a decrease in the electrical conductivity.The deposition procedure described here gives colloid-free surface thin films as indicated by the surface morphology analysis.     

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.     

Effect of HCl addition on the crystalline fraction in silicon thin films prepared by hot-wire chemical vapor deposition

In an effort to increase the crystalline fraction of silicon films directly deposited on a glass substrate by hot-wire chemical vapor deposition, the effect of HCl addition was studied. The silicon film was deposited on a glass substrate at 320 °C under a reactor pressure of 1333 Pa at the wire temperature of 1600 °C with 10%SiH₄–90%He at a fixed flow rate 100 standard cubic centimeter per minute (sccm) and HCl varied at 0, 10, 16 and 28 sccm. With increasing HCl, the crystalline fraction of silicon was increased as revealed by Raman spectra but the growth rate was decreased.     

Growth and characterization of indium oxide thin films prepared by spray pyrolysis

Highly transparent and conducting indium oxide thin films are prepared on glass substrates from precursor solution of indium chloride. These films are characterized by X-ray diffraction, scanning electron microscopy and optical transmission. The preferential orientation of these films is found to be sensitive to deposition parameters. A comparative study has been made on the dependence on the thickness of the film on substrate temperatures with aqueous solution and 1:1 C₂H₅OH and H₂O as precursors. Films deposited at optimum conditions have 167 nm thickness and exhibited a resistivity of 2.94 × 10⁻⁴ Ω m along with transmittance better than 82% at 550 nm. The analytical expressions enabling the derivation of the optical constants of these films from their transmission spectrum only have successfully been applied. Finally, the refractive index dispersion is discussed in terms of the single-oscillator Wemple and Didomenico model.     

Manganese oxide thin films prepared by pulsed laser deposition for thin film microbatteries

Manganese oxide thin films with various oxidation states (MnO, Mn₃O₄ and Mn₂O₃) have been prepared by pulsed laser deposition using a Mn target at different oxygen partial pressures. The structural and morphological features of the as-deposited thin films are characterized by X-ray diffraction, Raman, field emission scanning electron microscopy (FESEM). The oxidation states of Mn in different thin films are investigated by X-ray photoelectron spectroscopy for both Mn 2p and 3s levels. It is found that the structure, surface morphology, and Mn oxidation state of the thin films can be tuned by oxygen partial pressure during the deposition. As anode for thin film lithium-ion microbatteries, the Mn₃O₄ thin film electrode exhibits the largest reversible capacity up to 800 mAh g⁻¹ with good cycling stability and excellent rate capability. The promising electrochemical performance of the Mn₃O₄ thin film electrode indicates the potential application of Mn₃O₄ thin film anode in all solid-state thin film microbatteries.     

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.     

PECVD生长nc-Si∶H膜的沉积机理分析

nc-Si∶H膜具有显著不同于α-Si∶H与μc-Si∶H膜的新颖结构与物性。从热力学反应的基元过程出发，定性地分析了本征nc-Si∶H与掺磷nc-Si(P)∶H膜的沉积机理，并提出了进一步改善膜层质量的新途径     

Low temperature chemical vapor deposition of nanocrystalline V2O5 thin films

Spatially uniform, carbon-free thin films of V₂O₅ were deposited on silicon by chemical vapor deposition using vanadium oxide triisopropoxide and water as gaseous precursors, in the temperature range of 100-300 °C. Films with substantial crystallinity were obtained for deposition temperatures as low as 180 °C. The “neat” chemistry that nominally leaves no fragments of ligand or water in the solid promotes film purity and reduces the deposition temperature needed for crystallization. Such deposition temperatures also open up additional possibilities for using crystalline vanadia on fragile substrates such as polymers for electronics and optical applications.     

Microstructure and optical properties of chromium containing amorphous hydrogenated carbon thin films (a-C:H/Cr)

Chromium containing amorphous hydrogenated carbon thin films was deposited using a dc sputter deposition technique under various mixtures of methane and Ar. The microstructure, composition, and optical properties of the resulting films were investigated. We show that a-C:H/Cr thin films exhibiting absorptance in certain wavelengths are greater than 95% and the average absorptance was 86% in the 0.3 to 2.5 µm wavelength can be obtained by using appropriate methane/Ar ratios and deposition times.     

Structure and properties of nitrogen-doped titanium dioxide thin films grown by atmospheric pressure chemical vapor deposition

Using TiCl₄, O₂, and N₂O as precursors, N-doped titanium dioxide thin films with large area and continuous surface were obtained by atmospheric pressure chemical vapor deposition. Measurements of X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscope, transmission electron microscope and ultravoilet-Visible transmission spectra were performed. Using N₂O as N-doped source, anatase-rutile transformation is accelerated through oxygen vacancies formation, and the mean grain size of rutile crystallites decreases with the increase of N₂O flow rate. Compared to the pure TiO₂, N-doped TiO₂ films give a relative narrow optical band-gap, and their visible-light induced photocatalysis is much enhanced. Visible-light-induced hydrophilicity of the TiO₂ thin films enhances with the increase of N₂O flow rate, which might be due to the dentritic islands structure on the surface of the N-doped TiO₂ thin films.     

Supermagnetron plasma CVD of highly effective a-CNx:H electron-transport and hole-blocking films suited to Au/a-CNx:H/p-Si photovoltaic cells

Hydrogenated carbon nitride (a-CN_x:H) films (0-500 nm) were deposited on p-Si wafers to make Au/a-CN_x:H/p-Si photovoltaic cells using i-C₄H₁₀/N₂ supermagnetron plasma chemical vapor deposition. At a lower electrode RF power (LORF) of 50 W and an upper electrode RF power (UPRF) of 50-800 W, hard a-CN_x:H films with optical band gaps of 0.7-1.0 eV were formed. At a film thickness of 25 nm (UPRF of 500 W), the open circuit voltage and short circuit current density were 247 mV and 2.62 mA/cm², respectively. The highest energy conversion efficiency was 0.29%. The appearance of the photovoltaic phenomenon was found to be due to the electron-transport and hole-blocking effect of thin a-CN_x:H film.     

ECR-CVD方法生长a-SiNx:H薄膜的研究

使用微波电子回旋共振等离子体化学气相沉积(ECR-CVD)方法室温生长了非晶氢化的氮化硅薄膜,通过改变前驱气体(SiH4 80%Ar和NH3)的流量比,研究了薄膜的生长速率、等离子体的发射光谱和薄膜的红外特性.结果表明:随着NH3流量的增加,氮化硅薄膜的生长速率呈下降趋势,这主要是由于等离子体中的气相前驱成分之一硅基团浓度的不断下降所导致的;随着NH3流量的增加,薄膜中键合了较多的具有较高电负性的N原子是Si-N和Si-H伸缩振动发生蓝移的主要原因.红外光谱的定量计算表明所制备的氮化硅薄膜具有相对较低的H浓度,约15%左右.文中对氮化硅薄膜的生长机制也进行了讨论.     

Optical properties of SnO2:F films deposited by atmospheric pressure CVD

Atmospheric pressure chemical vapor deposition (APCVD) system, designed for the deposition of F-doped SnO₂ thin films, is compatible with industrial requirements such as high process speed, scaling to wide substrate widths and low costs. Precise method for measuring the optical absorptance in the spectral range 300–1700 nm combines transmittance, reflectance and photothermal deflection (PDS) spectra measured on the same spot of the sample immersed in the transparent liquid with a relatively high index of refraction. The effects of the film thickness, doping gas addition and the susceptor temperature on the optical absorptance and electrical resistivity of the TCO films are assessed. We show that the doping gas concentration and the susceptor temperature influence both the incorporation ratio of dopants into SnO₂ film as well as the defect concentration. The SnO₂ films growth at optimum APCVD conditions have thickness 0.7 µm, average surface roughness about 40 nm, sheet electrical resistance 10 Ω/sq and the optical absorption 1% at 500 nm and about 5% at 1000 nm.     

Deposition kinetics of silicon dioxide from tetraethylorthosilicate by PECVD

Tetraethylorthosilicate (TEOS)-based SiO₂ films were prepared in an RF reactor at various discharge powers and two substrate temperatures, and infra-red absorption spectra were taken for each deposited film using an FTIR spectrometer. Based on the FTIR observations, a model for the plasma and surface kinetics was developed. Using a proposed three-step reaction mechanism at the surface of a two-dimensional lattice, the growth rate of the films and the incorporation rate of Si---O---Si bridges into the films were derived as functions of the densities of the film precursors, oxygen atoms and molecular oxygen ions. The densities are further given by the uniform discharge model of our previous work as a function of the discharge power. According to the model, in the regime of high ratio of oxygen to TEOS flow the growth rate is governed by the film precursors generated from TEOS, and the incorporation rate is additionally determined by oxygen radicals and molecular oxygen ions and by the dehydration process. The growth rate was measured in μm/min and the relative incorporation rate was obtained from the absorption intensity of Si---O---Si rocking mode in FTIR spectra. The formulation of the model was compared with the experimental results, and on the validity of the model was discussed.     

Phase separated AlSi thin films prepared by filtered cathodic arc deposition

Phase separated AlSi films composed of Al cylinders embedded in an amorphous Si matrix were prepared on conducting Si substrates by filtered cathodic arc deposition. The compositional dependence of AlSi films on a negative substrate bias showed a different trend depending on the cathode composition because of the self-sputtering process during the deposition. The porous structure was obtained from the phase separated AlSi film after removal of Al cylinders by wet etching in an ammonia solution. Scanning electron microscope images of the etched AlSi films showed that the average diameter of pores was increased from 3 nm to 7 nm by applying a negative substrate bias voltage during the deposition. The honeycomb ordered arrangement of pores was observed at 0 V and − 25 V substrate bias. The substrate temperature during the depositions had almost the same effect on the film morphologies as the negative substrate bias.