Ellipsometric examination of electrically conductive films of poly(2,5-thiophenediyl)

A polymer film formed by anodic oxidation of thiophene in acetonitrile on platinum at 2.08 V was examined by ellipsometry. The refraction index and absorption index were determined as a function of the wavelengths. The optical thickness was determined and compared with the electrical charge. Stoichiometric film growth by a two-electron reaction followed this comparison. The film properties studied were almost independent of the potential between −0.1 and +2.08 V. The time dependence of the ellipsometric parameter showed the film growth to be approximately linear with square root of time, typical for a diffusion controlled reaction.     

In situ surface plasmon study of the electropolymerization of Fe(vbpy)3 onto a gold surface

Sequential multilayer electropolymerization of Fe(vbpy)₃²⁺ (vbpy=4-vinyl-4′-methyl-2,2′-bipyridine) onto a thin gold electrode was followed in situ with surface plasmon spectroscopy (SPS) using a 1 mW HeNe laser at 6328 Å. The robustness of the gold film electrode necessary for electrochemical deposition in 0.10 M tetraethylammonium perchlorate+acetonitrile is imparted by use of a thin film of 3-mercaptopropyl-trimethoxysilane attached to a SF10 slide to which the metal is covalently bonded. As each polymer layer is deposited by cycling a potentiostat from 0.0 to −1.75 and back to 0.0 V, a plasmon spectrum (reflectivity versus prism angle) is obtained. SP analysis of the angular shift of the spectrum, which increases as the polymer layer thickens, yields an estimate of both the thickness and index of refraction of the polymer film. We found that the plasmon spectrum shifts to higher angles as the polymer layer thickens, along with a progressive decrease in the depth of the resonance minimum. Our modeling shows this unusual spectral behavior involving the resonance minimum is consistent with a Fe(vbpy)₃²⁺ chromophore absorption at 6328 Å, along with thickening of the polymer film. This work demonstrates that SPS is a viable in situ technique for obtaining thickness measurements of electrodeposited thin films.     

Effect of Showerhead Configuration on Coherent Raman Spectroscopically Monitored Pulsed Radio Frequency Plasma Enhanced Chemical Vapor Deposited Silicon Nitride Thin Films

The effect of showerhead design, number of holes and geometry, in a parallel plate reactor was studied by measuring the concentration of silane reactant by coherent anti-Stokes Raman scattering (CARS) spectroscopy as a function of radio frequency (rf) pulse width and peak power during pulsed power plasma enhanced chemical vapor deposition (PECVD) of silicon nitride thin films. Film deposition rate, stress, SiH/NH ratio, and thickness and index of refraction homogeneity were correlated with the change in silane concentration for each of the three head geometries: radial, square, and asymmetrical. The asymmetrical head caused plasma quality problems which affected the films' qualities. The square pattern showed good mixing qualities, but produced a film with high compressive stress. The radial head provided the most homogenous film, with respect to index of refraction and film thickness. With a 10 ms pulse width, however, the radial head plasma acted as a continuous plasma for depletion and stress data. The showerhead geometry affects plasma qualities, like stability and intensity, and reactant gas velocities, which in turn affect the nitride film thickness, nitride composition, and stress.     

Sol–gel preparation of antireflective coatings at 351 nm with different thickness and improved moisture-resistance

Antireflective (AR) coatings at 351 nm with different thickness were designed and prepared by sol–gel process using tetraethylorthosilicate as precursor and ammonia as catalyst. The parameters of these coatings, including film thickness and refractive index, were calculated by optical formula and the coatings were prepared accordingly. Sol dilution method was used to adjust the film thickness. The wavelengths of maximum transmission measured by UV–Vis spectrophotometer, were used to monitor the film thickness. It was found that AR coatings with higher thickness possess better abrasion-resistance. Hydroxyl terminated polydimethylsiloxane (PDMS) was added into pure silica sol to improve both the abrasion-resistance and moisture-resistance of AR coating.     

Plasma Polymerization on Metals

An ellipsometric technique is described for accurately measuring the film thickness of plasma-polymerized polymers on metallic substrates. The index of refraction n and absorption index Kof the plasma polymer film can also be studied by ellipsometry. Films of plasma polystyrene and polyepichlorohydrin were deposited on evaporated aluminum substrates and their thickness and optical constants determined. Plasma polystyrene films from 20 to 1600 Å thick have optical constants n = 1.63 and K =0 independent of film thickness. Plasma polyepichlorohydrin films over the same range of thickness give n ? 1.70 and K? 0.01. By utilizing the ellipsometric method the effect of plasma polymer film thickness on surface energy properties was determined. Advancing contact angle measurements and surface energy analysis detail the polar γSV^P dispersion γSV^Pcontributions to the solid-vapor surface tension γSV = γSV^d + γSV^P Polystyrene and polyepichlorohydrin films on etched aluminum. For thin plasma polystyrene films (600 Å), anomalies in the calculated surface energy are discussed and related to possible surface nonuniformity caused by film growth. Thicker films of plasma polystyrene are shown to have normal surface energy properties as does plasma poly-epichlorohydrin over the entire range of film thickness measured. The adhesive and cohesive properties of plasma polystyrene and polyepichlorohydrin films are discussed as estimated from a lap-shear bond strength study. Etched aluminum coated with various thicknesses of these two polymers and bonded with an epoxy-phenolic adhesive shows a decreasing shear strength with increasing plasma film thickness but begins to level off at ～1600 psi for films >1600 Å thick.     

Characterisation of boron nitride fibre coatings with different crystalline order by TEM and XPS

Reinforcement effects in composites are widely influenced by fibre coatings. A detailed understanding of their microstructure and chemical composition is of great interest. Boron nitride films were deposited continuously on fibre rovings of various ceramics in CVD reactors of vertical as well as horizontal position. XPS depth profilings show that the film compositions are close to stoichiometric BN with carbon and oxygen impurities in the range of 10 at%. Cross-sections of separated fibres were investigated by HREM and TEM diffraction. All BN films are hexagonal turbostratic. The (002) layers with an increased distance (about 0.36 nm) showed a mean stacking sequence near to graphite and a characteristic orientation to the fibre in the interface region. We assume the gas flow type and hence the exchange rate of matter and energy determines the film structure in this region. With increasing film thickness the (002) layers fold randomly in all directions or form nanocrystals at elevated temperatures. Received: 7 September 1998 / Revised: 13 January 1999 / Accepted: 5 February 1999     

Determination of thickness distribution and composition of thin coatings by EPMA: Application in the field of steel sheet production

A new method for the investigation of surface coatings by EPMA is presented. It is based on a physical model which takes into account the X-ray intensity depth distribution, the absorption and the electron backscattering effects at the interface between film and substrate. When combined with the concentration mapping (CM) technique, a two-dimensional film thickness distribution and the film composition can be determined simultaneously. Only bulk standards are required for this method.With some examples in the field of steel sheet production and electrogalvanizing the versatility of the method as well as its high sensitivity are pointed out. Particularly important for practical work is the applicability to almost any combinations of film and substrate materials as well as the wide thickness range from almost the total X-ray emergence depth down to the monolayer range.Dedicated to Professor Günther Tölg on the occasion of his 60th birthday     

Determination of optical constants and thickness of passivating films on nickel from multiple-angle-of-incidence reflectivity measurements

A method is proposed which allows to determine without non-optical assumptions the complex refractive index and the thickness of thin surface films from measurements of the relative changes of reflectivity due to the formation or removal of the film at different angles of incidence with monochromatic light polarized perpendicular or parallel to the plane of incidence. The exact equations for the reflectivity change are used, since the linear approximation introduces systematic errors which are too large in view of the experimental accuracy. The method is applied to the passivating film formed on nickel in 1 M sulphuric acid after 1 h at U_HSS=0.85 V. A complex refractive index n₂=2.10 (±0.05)–0.46 (±0.02) i and a film thickness d=2.1 (±0.1) nm were found. In the spectrum of the optical constants in the range 1.4≤hv/e V≤4.8 a characteristic peak of the absorption coefficient was observed at 3.1 e V. Both the values at γ=500 nm and the spectra of the optical constants are explained by a partly hydrated nickel oxide film.     

Mean thickness measurement of distributed fine particles by using alpha-ray absorption curves (author's transl)

The mean superficial density of fine particles, such as polystyrene latex particles or ion exchange resin particles, dispersed on a thin supporting film was measured by means of the thickness gauge which used the absorption curves of alpha-rays. The measured absorption curves coincided with the ones calculated from the particle diameter, density, number of particles per unit area and equivalent film thickness to an absorption gas of 1 mmHg. On the other hand, when the particle diameter exceeded a certain limit, the measured mean superficial density which was derived from the pressure displacement of absorption curve considerably differed from the true mean superficial density. This limit can be calculated from the shape of absorption curve, which depends on the alpha-ray spectrum emitted from the source. In the case of the 241Am source used in this study, the limit was about 450 microgram/cm2 for polystyrene latex particles. The mean superficial density of a sample can easily be obtained by measuring the pressure displacement of absorption curve when the maximum thickness difference is below the limit. However, when the maximum thickness difference exceeds the limit, it is necessary to estimate the whole shape of absorption curves.     

A method to measure the mean thickness and non-uniformity of non-uniform thin film by alpha-ray thickness gauge (author's transl)

The alpha-ray thickness gauge is used to measure non-destructively the thicknesses of thin films, and up to the present day, a thin film with uniform thickness is only taken up as the object of alpha-ray thickness gauge. When the thickness is determined from the displacement between the absorption curves in the presence and absence of thin film, the absorption curve must be displaced in parallel. When many uniform particles were dispersed as sample, the shape of the absorption curve was calculated as the sum of many absorption curves corresponding to the thin films with different thicknesses. By the comparison of the calculated and measured absorption curves, the number of particles, or the mean superficial density can be determined. This means the extension of thickness measurement from uniform to non-uniform films. Furthermore, these particle models being applied to non-uniform thin film, the possibility of measuring the mean thickness and non-uniformity was discussed. As the result, if the maximum difference of the thickness was more than 0.2 mg/cm2, the non-uniformity was considered to distinguish by the usual equipment. In this paper, an alpha-ray thickness gauge using the absorption curve method was treated, but one can apply this easily to an alpha-ray thickness gauge using alpha-ray energy spectra before and after the penetration of thin film.     

Analytical application of 2f-wavelength modulation for isotope selective diode laser graphite furnace atomic absorption spectroscopy

Experiences in the analytical application of the 2f-wavelength modulation technique for isotope selective atomic absorption spectroscopy in a graphite furnace are reported. Experimental as well as calculated results are presented, mainly for the natural lithium isotopes. Sensitivity, linearity, and (isotope) selectivity are studied by intensity modulation and wavelength modulation. High selectivities can be attained, however, on the cost of detection power. It is shown that the method enables the measurement of lithium isotope ratios larger than 2000 by absorption in a low-pressure graphite tube atomizer. Received: 26 April 1999 / Revised: 25 June 1999 / Accepted: 30 June 1999     

The reaction of thiourea to dicyandiamidine sulfate on silver surfaces investigated by reflection-absorption infrared spectroscopy

The reaction pathway of thiourea degradation on silver surfaces was investigated with reflection-absorption infrared spectroscopy. Adsorption of thiourea from aqueous solution produces a thin stable thiourea film that is not removed by rinsing. Aging at elevated temperature results in conversion to dicyandiamidine sulfate. The same reaction product is observed on daguerreotypes that were treated with commercial thiourea based silver cleaner. Received: 26 April 1999 / Revised: 7 June 1999 / /Accepted: 11 June 1999     

Development of Methods to Determine the Infrared-Optical Properties of Polymer Films

Summary: In this paper, two methods for the determination of infrared optical properties of thick polymer films, based on FTIR spectroscopy, were implemented and used. Complex index of refraction data were generated for various ethylene copolymer films. Transmittance and reflectance spectra were measured in the mid infrared range using a gold-coated 100 mm-diameter integrating sphere. For the investigated films n and k values ranging from 1.3 to 1.6 and from 10⁻⁴ to 0.25 were determined, respectively. Regarding n, a good agreement was obtained for both methods, the transmittance/reflectance procedure (T/R method) used for transparent and semitransparent regions, and Single Substractive Kramers-Kronig (SSKK) algorithm applied for non-transparent regions. The highest k values were determined for the CH₂ stretching vibration. The k values are dependent on comonomer content and film thickness. The combination of both methods allows for an accurate determination of n and k in the entire IR region relevant for solar application.     

Highly sensitive detection of transient absorption in dye-doped ultrathin polymer films by the TiO(2)/K(+) composite optical waveguide method upon pulsed laser excitation

A composite optical waveguide (OWG) composed of a 10–18 nm thick titanium dioxide (TiO₂) film sputtered on a conventional K⁺-doped optical waveguide was first applied to detect transient absorption of organic dyes in ultrathin polymer films upon excitation with ns laser. The thickness of the TiO₂ film considerably affected the relative sensitivity of the composite OWG. The composite OWG with 10 nm thick TiO₂ gave much stronger transient absorption for 30–415 nm thick polymer films containing organic dyes than that with 18 nm TiO₂. Transient absorption of phthalocyanine and spiropyran in 20–135 nm thick polymer films was detected 3–20 times more sensitively by the composite OWG with 10 nm TiO₂ than the conventional K⁺-doped OWG which showed a 150-fold sensitivity as compared with the usual normal incidence method. The relative sensitivity of the composite waveguide was also affected by the thickness and refractive index of polymers.     

溶液电沉积法制备苝酰亚胺类化合物薄膜

溶液电沉积法是一种具有沉积时间短,可以常温沉积以及沉积物在基底上附着力高等优点的薄膜制备方法.本文用水合肼增溶苝酰亚胺类化合物(PTCDI)的方法制备了可用于溶液电沉积的苝酰亚胺类化合物溶液.用紫外-可见分光光度法(UV-Vis)对溶解的过程进行了表征,并用顺磁共振(ESR)验证了水合肼对PTCDI的增溶过程实质上是化学反应过程.在制备苝酰亚胺类化合物溶液的基础上,采用阳极电沉积法在ITO导电玻璃上沉积出了薄膜.采用UV-Vis,扫描电镜(SEM)和X射线衍射仪(XRD)对薄膜进行了表征,证实得到了表面较为平整、具有可控结晶结构和形貌的PTCDI薄膜以及具有较宽光谱吸收范围的复合薄膜.     

不同厚度三倍频SiO2增透膜的设计、制备与改性

本文通过光学计算设计了具有不同厚度的三倍频增透膜。以氨水为催化剂、正硅酸乙酯(TEOS)为前驱体,通过溶胶-凝胶(Sol-Gel)技术制得SiO2溶胶;采用浸渍提拉法镀膜得到符合设计要求的三倍频增透膜。研究结果表明,增透膜的耐磨擦性能随着膜层厚度的增大而增大,本文制得的厚度达到200 nm以上的三倍频增透膜耐磨擦性能显著优于传统的1/4波长三倍频增透膜。此外,本文以甲基含氢硅油为膜表面修饰剂,提出一种全新的超快的表面疏水性改性的方法。经该方法处理后,增透膜由亲水膜转变为疏水膜,对水的接触角从23.4°增大至95°,增透膜的耐环境性显著提高。     

The effect of molecular weight on the topography of thin films of blends of poly(4-bromostyrene) and polystyrene

Blends of polystyrene and poly(4-bromostyrene) phase-separate during spin-casting onto silicon wafers to give a thin film with islands of poly(4-bromostyrene) in a sea of polystyrene. Variation of the molecular weights of the blend components shows that the poly- (4-bromostyrene) and polystyrene influence the film structure in different ways. For poly(4-bromostyrene) of a given molecular weight, the ratio of the observed feature height to the overall film thickness remained constant as the film thickness increased. Moreover, the mean height of the topographical features was independent of the polystyrene but decreased with the molecular weight of the brominated polymer. It is concluded that the substrate–poly(4-bromostyrene) interaction dominates the formation of topography and consequently, though the islands are poly(4-bromostyrene), the mean height of the topographical features is greater the lower the molecular weight of the brominated polymer. The polystyrene has a secondary role, altering the thermodynamics or viscosity of the blend, thereby controlling the number of islands formed: the higher the molecular weight of the polystyrene the greater the number of islands. Received: 2 December 1999 Accepted: 7 April 2000     

Interface effects on moisture absorption in ultrathin polyimide films

Water absorption in thin films (<1000 Å) of a commercial polyimide was evaluated by monitoring dimensional changes induced by a humid environment. Film thickness was measured using x-ray reflectivity, which is a nondestructive technique offering angstrom resolution in the measurements of thin film or multilayer thickness. The effect of several variables on the absorption of moisture were monitored in polyimide films adhered to polished silicon substrates, including total dry film thickness, exposure time, and the contribution of a coupling agent. The percentage increase in film thickness due to moisture uptake is found to be a weak function of dry film thickness, decreasing as dry film thickness increases, and to be somewhat affected by the use of an interfacial coupling agent. The observed behavior points to the polymer/substrate interface as a strong factor controlling the absorption of moisture in the polyimide/silicon system, and is believed to reflect the presence of a highly moisture-saturated interfacial layer. A bilayer model is proposed, and the feasibility of using this model to describe the observed behavior is considered. Published 1998 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

J Polym Sci B: Polym Phys 36 : 155–162, 1998     

THz reflection spectroscopy of liquid water

We report an investigation of the temperature-dependent far-infrared spectrum of liquid water. We have employed a new experimental technique based on ultrashort electromagnetic pulses (THz pulses). This technique allows for fast and reliable data of both index of refraction and absorption coefficient for highly absorbing liquids. The temperature dependence reveals an enthalpy of activation corresponding to 2.5 kcal/mol, in agreement with recent Raman experiments, but lower than the enthalpy observed in dielectric relaxation experiments. This demonstrates that part of the orientational relaxation in liquid water takes place without breaking of hydrogen bonds with bonding energy of 5 kcal/mol, as suggested in recent theoretical model.