Detection of deposition rate of plasma-polymerized acrylate and methacrylate derivatives using quartz crystal microbalance

The deposition rates of plasma-polymerized (pp-)films of 12 acrylate derivatives (CH₂CHCOOR: substitution R is H, CH₃, CHCH₂, CH₂CH₃, CH₂CH₂CH₃, (CH₂)₃CH₃, C(CH₃)₃, CH₂CH(CH₃)₂, CH₂(CH₂)₄CH₃, CH₂CF₃, CH₂CF₂CF₃, CH₂(CF₂)₂CF₃), and 12 methacrylate derivatives (CH₂CCH₃COOR′: substitution R′ is H, CH₃, CHCH₂, CH₂CH₃, CH₂CH₂CH₃, (CH₂)₃CH₃, C(CH₃)₃, CH₂CH(CH₃)₂, CH₂(CH₂)₄CH₃, CH₂CF₃, CH₂CF₂CF₃, CH₂(CF₂)₂CF₃) are determined by the quartz crystal microbalance technique. Using the same polymerization conditions (100 W RF and 100 Pa vapor pressure) for the various monomers, it is found that the deposition rates were proportional to the polymerization time. The average deposition rate of pp-acrylate derivatives is larger than that of pp-methacrylate derivatives without pp-hexylacrylate. The average deposition rate of pp-fluoroalkylacrylates was higher than 7-25 times that of pp-alkylacrylate, and the average deposition rate of pp-fluoroalkylmethacrylates was higher than 10-31 times that of pp-alkylmethacrylates, respectively. The average deposition rate of pp-film depends on the chemical structure of the monomer suggesting different mechanisms under plasma-polymerization.     

Optical spectroscopic characterization of plasma-polymerized thin films

We report optical spectroscopic measurements of plasma-polymerized thin films coated on aluminum (Al) substrates over a spectral range from 0.01 to 6 eV. While the reflectance spectra, R(ω), remain almost unchanged in the infrared range as compared with the bare Al, R(ω) starts to decrease significantly in the higher energy above 2.5 eV. This decrease in R(ω) arises from electronic absorptions characteristic of the polymer films. Moreover, the details of R(ω) in the energy above 3 eV depend on the fabrication conditions of the polymer films. Our results, therefore, demonstrate that this optical measurement can be an excellent method to characterize the quality of polymer films deposited by the plasma polymerization process.     

Dielectric properties of plasma-polymerized diphenyl thin films

Thin polymeric films of diphenyl were prepared by a plasma polymerization technique using a capacitively-coupled reactor. The dielectric relaxation spectroscopy was employed to investigate the behaviour of the as-deposited and heat-treated plasma-polymerized diphenyl (PPDP) thin films in a aluminium/PPDP/aluminium configuration over the frequency range from 10⁻¹ to 10⁶ Hz and temperature range from 223 to 423 K. The ac conductivity is more dependent on temperature in the low frequency region than in the high frequency region. In these materials the conduction may be dominated by hopping of carriers between the localized states at low temperatures and thermally excited carriers from energy levels within the band gap in the vicinity of high temperature. Dielectric constant is dependent on frequency above 303 and 343 K in the as-deposited and heat-treated PPDP, respectively. The as-deposited PPDP shows superposed and β relaxation processes. For different relaxation processes, the activation energies are estimated to be about 0.45 and 0.67 eV for the as-deposited and 1.35 eV for heat-treated PPDP. The dielectric data analyses show the existence of distribution of relaxation time in these materials.     

Study of the effect of process parameters for n-heptylamine plasma polymerization on final layer properties

Plasma polymerization processes are widely used to chemically functionalize surfaces, which properties can be tuned by different operating variables. In this study, thin amine-containing polymer layers were produced on solid substrates in a custom-made cylindrical plasma polymerization reactor by radio frequency glow discharges of n-heptylamine vapours. Carefully planned experiments were conducted to evaluate the importance of four different process parameters on the chemical composition and thickness of the resulting films. The parameters investigated were: 1) deposition time, 2) power of the glow discharge, 3) distance between the electrodes, and 4) monomer pressure. Possible interactions between these variables were investigated through the use of statistical analyses (i.e., factorial design). This study reveals that n-heptylamine plasma polymer (HApp) layer thickness is influenced by the power of the glow discharge and the deposition time, as assessed by surface plasmon resonance and atomic force microscopy step height measurements. Also, the atomic ratio of nitrogen to carbon atoms on the treated surfaces is mainly influenced by the power of the glow discharge, as revealed by X-ray photoelectron spectroscopy. Quartz crystal microbalance analysis also confirmed that HApp layers are stable when immersed in aqueous solution.     

An investigation of the optical properties of plasma-polymerized diphenyl thin films

Highly adhering plasma-polymerized diphenyl (PPDP) thin films were grown by a dry and flawless process in glow discharge. The structural analyses of as-deposited and heat treated PPDP samples (unaged and aged) were performed by infrared (IR) spectroscopy. The PPDP thin films were transparent and light yellow in colour. Optical properties were evaluated from ultraviolet–visible (UV–Vis) spectroscopic measurements of as-deposited, heat treated and aged (as-deposited and heat treated) PPDP thin films. From the optical absorption data band gaps, allowed direct and indirect transition energy gaps were determined. The results are discussed in the light of possible structural modification in PPDP thin films on heat treatment and aging.     

Synthesis and characterization of polyaniline-camphorsulphonic acid nanotube film

Polyaniline (PANI) nanotubes were prepared in the bulk solution and as films using the aniline oxidation with ammonium peroxydisulfate in aqueous solutions of camphorsulfonic acid (CSA). The in situ PANI films produced during the oxidation of aniline in CSA and also in hydrochloric acid solutions were followed by monitoring the frequency changes of quartz crystal microbalance (QCM). The kinetics of the film formation were discussed. The scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM) showed PANI nanotubes. In addition, nanorods and nanoflowers composed from nanofibers and nanoflakes are also present to some extent. The nanotubes were characterized using UV-Vis spectroscopy.     

Growth studies and characterization of silicon nitride thin films deposited by alternating exposures to Si2Cl6 and NH3

We deposited silicon nitride films by alternating exposures to Si₂Cl₆ and NH₃ in a cold-wall reactor, and the growth rate and characteristics were studied with varying process temperature and reactant exposures. The physical and electrical properties of the films were also investigated in comparison with other silicon nitride films. The deposition reaction was self-limiting at process temperature of 515 and 557 °C, and the growth rates were 0.24 and 0.28 nm/cycle with Si₂Cl₆ exposure over 2 × 10⁸ L. These growth rates with Si₂Cl₆ are higher than that with SiH₂Cl₂, and are obtained with reactant exposures lower than those of the SiH₂Cl₂ case. At process temperature of 573 °C where the wafer temperature during Si₂Cl₆ pulse is 513 °C, the growth rate increased with Si₂Cl₆ exposure owing to thermal deposition of Si₂Cl₆. The deposited films are nonstoichiometric SiN, and were easily oxidized by air exposure to contain 7-8 at.% of oxygen in the bulk film. The deposition by using Si₂Cl₆ exhibited a higher deposition rate with lower reactant exposures as compared with the deposition by using SiH₂Cl₂, and exhibited good physical and electrical properties that were equivalent or superior to those of the film deposited by using SiH₂Cl₂.     

Sputter-assisted plasma CVD of polymer-like amorphous CNx:H films using supermagnetron plasma

By using a sputter-assisted chemical vapor deposition (CVD) of supermagnetron plasma, amorphous CN_x:H films were deposited on the lower part of two parallel electrodes. By applying rf power to the upper electrode (UPRF) at 5 W to 800 W, polymer-like a-CN_x:H films were deposited on substrates placed on the lower electrode with an rf power (LORF) of 10 W. The deposition rate increased as UPRF increased. The hardness was as low as about 6.5 GPa, which is less than that of glass (13.1 GPa). The refractive index changed only slightly as UPRF changed from 1.6 to 1.75. The FT-IR spectrum showed strong absorption bands of NH and CH bonds at high and low UPRFs, respectively. The optical band gap was as large as 2.1 to 2.5, and it decreased as UPRF increased. These a-CN_x:H films showed white photoluminescence (PL) with broadband. With the increase of UPRF from 5 W to 800 W, the PL peak energy shifted down from 2.3 eV to 1.9 eV.     

静电自组装制备含苝衍生物的纳米层状复合膜

采用静电自组装方法制备了稳定的含苝衍生物纳米层状复合膜．用石英晶体微天平(QCM)对静电自组装过程进行了原位监控，发现组装次数与QCM频率变化呈线性关系，通过静电吸附得到的多层累积薄膜具有层状结构，X射线光电子能谱图上出现苝衍生物的特征峰表明组装的薄膜中含有苝衍生物．原子力显微镜表征结果表明，复合膜在一定程度上规整并且均匀的覆盖在电极表面，但存在分子团聚现象，将苝衍生物小分子溶解在聚电解质溶液中作混合浸渍液，提高了组装薄膜的稳定性．     

Chemomechanical bending behaviors of ionizable thin films with gradient network-size

An ionizable thin film with gradient network size in direction of thickness was prepared using 10-undecenoic acid(UA) by plasma polymerization. Gradient structure in the network size was estimated by values of relative diffusion coefficient of ferocian ions through the film. The obtained film was found to show chemomechanical behavior. The film bent in alkaline solution due to anisotropic swelling in direction of thickness and recovered to the original shape in acid solution.     

Poly(N-methyl aniline) thin films on copper: Synthesis, characterization and corrosion protection

Poly(N-methyl aniline) (PNMA) coatings were synthesized on copper by electrochemical polymerization of N-methyl aniline in aqueous oxalic acid solution by using cyclic voltammetry. The optimum electrodeposition conditions (e.g. upper potential limit, scan rate and cycle number) were determined in order to obtain PNMA coatings to have the best corrosion performance. PNMA coatings were characterized by cyclic voltammetry, Fourier Transform Infrared-Attenuated Total Reflectance spectroscopy and scanning electron microscopy. Redox parameters found after electrochemical tests indicate a thin film character and diffusion controlled electroactive behavior of PNMA. Corrosion test results revealed that PNMA coating appears to enhance protection of copper in 0.1 M H₂SO₄ solution.     

Electron emission characterization of diamond thin films grown from a solid carbon source

Diamond films of various morphologies and compositions have been deposited on silicon substrates by a plasma-enhanced chemical transport (PECT) process from a solid carbon source. Electron emission efficiency of these diamond films is related to their morphology and composition. The electric field required to excite emission in a boron-doped polycrystalline diamond film ranged between 20 to 50 MV m⁻¹. In an undoped conducting nanocrystalline diamond composite film, the field was as low as 5–11 MV m⁻¹. The cold field electron emission of these films is confirmed from the Fowler-Nordhelm plots of the data. Enhancement of electron emission by band-bending and by the nanocrystalline microstructure are discussed. New diamond emitters made of nanocrystalline boron-doped diamond composite are proposed.     

Physical and tribological properties of diamond films grown in argoncarbon plasmas

Nanocrystalline diamond films have been deposited using a microwave plasma consisting of argon, 2–10% hydrogen and a carbon precursor such as C₆₀ or CH₄. It was found that it is possible to grow the diamond phase with both carbon precursors, although the hydrogen concentration in the plasma was 1–2 orders of magnitude lower than normally required in the absence of the argon. Auger electron spectroscopy, X-ray diffraction measurements and transmission electron microscopy indicate the films are predominantly composed of diamond. Surface roughness, as determined by atomic force microscopy and scanning electron microscopy indicate the nanocrystalline films grown in low hydrogen content plasmas are exceptionally smooth (30–50 nm rms) to thicknesses of 10 m. The smooth nanocrystalline films result in low friction coefficients (μ = 0.04–0.06) and low average wear rates as determined by ball-on-disk measurements.     

Deposition of BaTiO3 thin films by plasma MOCVD

Barium titanium trioxide (BaTiO₃) thin films were deposited on fused silica or silicon wafer substrate from barium dipivaloylmethanate (II) (Ba(dpm)₂) and titanium tetraisopropoxide (IV) (TTIP) used as precursors in an oxygen microwave plasma. The substrates were dielectrically heated and the substrate temperatures were around 900 K during the film deposition. The deposition was performed for 15 min and the deposits were identified as BaTiO₃ by means of X-ray diffraction, X-ray photoelectron spectroscopy, infrared spectroscopy, and ellipsometry. Oxygen and barium atoms and TiO and CO molecules were identified in the plasma. These species would produce higher deposition rates at lower substrate temperatures than those did in the usual thermal metalorganic chemical vapor deposition (MOCVD). The dielectric constant of the BaTiO₃ thin film that was directly deposited on the silicon wafer substrate was as low as 10¹ order of magnitude. Because the deposit reacted with the substrate and an interdiffusional layer was formed, the platinum layer was coated on the silicon wafer substrate in order to prevent the formation of an interdiffusional layer. The dielectric constant then increased to 10³ order of magnitude.     

Chemical and electrical characteristics of low temperature plasma enhanced CVD silicon oxide films using Si2H6 and N2O

Silicon oxide films have been deposited at low temperatures in the range of 30–250 °C using Si₂H₆ and N₂O by conventional plasma enhanced chemical vapor deposition technique. The dependencies of deposition temperatures on the film properties are studied. The leakage current and the etch rate of these low temperature films compare favorably to films deposited by silane and TEOS at higher temperatures, respectively.     

Mechanical properties of a-C:H and a-C:H/SiOx nanocomposite thin films prepared by ion-assisted plasma-enhanced chemical vapor deposition

a-C:H and a-C:H/SiO_x nanocomposite thin films were deposited on silicon, aluminum and polyimide substrates at 25 °C in an asymmetric 13.56 MHz r.f.-driven plasma reactor under heavy ion bombardment. Fourier transform infrared spectra of the films indicate that the nanocomposite filmsappears to consist of an atomic scale random network of a-C:H and SiO_x. Raman spectroscopy revealed that the sp² carbon fraction in the nanocomposite film was reduced compared with the a-C:H film. The intrinsic stress of both films increased with increasing negative bias voltage (−V_dc) at the substrate. However, the nanocomposite films exhibited lower intrinsic stress compared w with a-C:H-only films. Especially, a thin SiO_x-rich interlayer was very effective in reducing the film stress and enhancing the bonding strength at the interface. The interlayer allowed deposition of thick films of up to 5 μm. Also, the nanocomposite films were stable in 0.1 M NaOH solution and showed good microhardness.     

Characterization of the chemical bath deposited In(OH)xSy films: Effect of the growth conditions

The In(OH)_xS_y thin films were deposited by chemical bath deposition (CBD) using three different deposition procedures: ‘hot’: starting the deposition at 70 °C, ‘cold’: starting the deposition at room temperature and pre-treatment with In³⁺ ions prior the ‘hot’ deposition. The analysis of the deposited In(OH)_xS_y layers on glass revealed that modifications in the chemical bath deposition procedure provoked significant changes in the nucleation process, the growth rate, the layer elemental composition and the layer morphology. With an additional In³⁺ pre-treatment or starting from a cold solution, the formation of a dense bottom layer has been observed, resulting in In(OH)_xS_y films with more compact structure with refractive index values of 2.6. The comparison of the measured In/S ratio with a thicker layer suggests, that the In(OH)_xS_y deposition starts with an OH-rich layer. Assuming the indirect allowed band gap transition type, an E_g of 2.2 eV was found independent of the procedure type or deposition time.     

Growth and characterization of CuInSe2 thin films prepared by successive ionic layer adsorption and reaction method with different deposition temperatures

CuInSe₂ films were prepared at different deposition temperatures (T_D) by successive ionic layer adsorption and reaction method with chelating solutions. Influence of T_D on film growth, morphology, crystal structure, and band gap energy was investigated. Results showed that elevation of T_D mainly enhanced reaction kinetics and ionic diffusion velocity, resulting in fast growth rate of CuInSe₂ films, and maximum 20-30 nm/cycle depended upon T_D were acquired. Films with 60 dip-cycles could grow from 180 nm to 1000 nm by elevating T_D from 30 °C to 90 °C. Surface roughness of CuInSe₂ films was closely related to dip-cycle times and T_D. Accelerated growth rate by T_D could reduce the dip-cycle times for a required film thickness, which improved quality of film morphology.     

Preparation of (Ti1−xAlx)N films from mixed alkoxide solutions by plasma CVD

(Ti_1−xAl_x)N films were prepared on a Si wafer at 700°C from toluene solution of alkoxides (titanium tetraetoxide and aluminum tri-butoxide) in an Ar/N₂/H₂ plasma by the thermal plasma chemical vapor deposition (CVD) method. The films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, electrical resistivity, and Vickers micro-hardness. Single phase TiN formed at an Al atomic fraction of 0–0.2, with a mixed TiN and AlN phase occurring up to 0.6 and single phase AlN forming above 0.8. The films had relatively sooth surfaces, 0.4 μm thick at an Al atomic fraction of 0.2, and thickened with increasing Al fraction. The atomic concentration of Ti, Al, N, O, and C determined from their respective XPS areas showed that the Ti and Al contents of the films changes with the solution composition in a complementary way. The impurities were about 10 at.% oxygen and carbon. The electrical resistivity was almost unchanged from the value of 10³ μΩ cm at 0–0.6 Al but then suddenly increased to 10⁴ μΩ cm at higher Al contents. The hardness showed a synergic maximum of about 20 GPa at an Al fraction of 0.6–0.8.     

Structures and vapor-sorption characteristics of sputtered polychlorotrifluoroethylene films treated by hydrogen-plasma

Hydrogen-plasma treatment of the polychlorotrifluoroethylene (PCTFE) film produced by radio-frequency sputtering induces considerable elimination of halogen (fluorine and chlorine) atoms. This dehalogenation produces some noteworthy structural features: surface densification (crosslinks), trapped radicals, and incorporation of oxygen in the carbon networks. These structural changes modify the vapor-sorption properties of the sputtered PCTFE film, producing a molecular-sieving effect and enhancing the polar character of solubility properties of organic vapors.