The properties of free polymer surfaces and their influence on the glass transition temperature of thin polystyrene films

We present a detailed study of free polymer surfaces and their effects on the measured glass transition temperature (T_g) of thin polystyrene (PS) films. Direct measurements of the near-surface properties of PS films are made by monitoring the embedding of 10 and 20 nm diameter gold spheres into the surface of spin-cast PS films. At a temperature T = 378K( > T_g), the embedding of the spheres is driven by geometrical considerations arising from the wetting of the gold spheres by the PS. At temperatures below T_g ( 363K < T < 370K), both sets of spheres embed 3-4 nm into the PS films and stop. These studies suggest that a liquid-like surface layer exists in glassy PS films and also provide an estimate for the lower bound of the thickness of this layer of 3-4 nm. This qualitative idea is supported by a series of calculations based upon a previously developed theoretical model for the indentation of nanoscale spheres into linear viscoelastic materials. Comparing data with simulations shows that this surface layer has properties similar to those of a bulk sample of PS having a temperature of 374 K. Ellipsometric measurements of the T_g are also performed on thin spin-cast PS films with thicknesses in the range 8nm < h < 290nm. Measurements are performed on thin PS films that have been capped by thermally evaporating 5 nm thick metal (Au and Al) capping layers on top of the polymer. The measured T_g values (as well as polymer metal interface structure) in such samples depend on the metal used as the capping layer, and cast doubt on the general validity of using evaporative deposition to cover the free surface. We also prepared films that were capped by a new non-evaporative procedure. These films were shown to have a T_g that is the same as that of bulk PS (370±1 K) for all film thicknesses measured (> 7 nm). The subsequent removal of the metal layer from these films was shown to restore a thickness-dependent T_g in these samples that was essentially the same as that observed for uncapped PS films. An estimate of the thickness of the liquid-like surface layer was also extracted from the ellipsometry measurements and was found to be 5±1 nm. The combined ellipsometry and embedding studies provide strong evidence for the existence of a liquid-like surface layer in thin glassy PS films. They show that the presence of the free surface is an important parameter in determining the existence of T_g reductions in thin PS films.     

多晶薄膜表面粗化与生长方式转变

采用原子力显微镜研究了磁控溅射多晶薄膜表面粗化行为对归一化沉积温度T_s/T_m(T_s是沉积温度，T_m是材料熔点)的依赖性与薄膜生长方式转变行为.随着T_s/T_m增加，薄膜表面粗糙度增加，而表征粗糙度随时间演化特征的生长指数β历经了先减小再增加的过程.β对T_s/T_m的依赖关系反映了薄膜生长方式的转变行为，即薄膜生长依次由随机生长方式向表面扩散驱动生长方式与异常标度行为生长方式转变.在低于体扩散控制薄膜生长的温度时，晶界扩散机理导致多晶薄膜的表面粗化的异常标度行为. 关键词： 多晶薄膜 表面粗化 温度 生长     

椭偏透射法测量氢化非晶硅薄膜厚度和光学参数

针对多角度椭偏测量透明基片上薄膜厚度和光学参数时基片背面非相干反射光的影响问题,报道了利用椭偏透射谱测量等离子增强化学气相沉积法(PECVD)制备的a-Si:H薄膜厚度和光学参数的方法,分析了基片温度T_s和辉光放电前气体温度T_g的影响.研究表明,用椭偏透射法测量的a-Si:H薄膜厚度值与扫描电镜(SEM)测得的值相当,推导得到的光学参数与其他研究者得到的结果一致.该方法可用于生长在透明基片上的其他非晶或多晶薄膜. 关键词： 椭偏测量 透射法 光学参数 氢化非晶硅薄膜     

Vacancies ordered in screw form (VOSF) and layered indium selenide thin film deposition by laser back ablation

Indium selenide thin films are important due to their applications in non-volatile memory and solar cells. In this work, we present an initial study of a new application of deposition-site selective laser back ablation (LBA) for making thin films of In₂Se₃. Invacuo annealing and subsequent characterization of the films by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) indicate that control of substrate temperature during deposition and post-deposition annealing temperature is critical in determining the phase and composition of the films. The initial laser fluence and target film thickness determine the amount of material deposited onto the substrate.     

Growth and melting behaviour of thin in films on Ge(100)

Growth and melting behaviour of thin indium films on Ge(100) have been investigated by Auger-electron spectroscopy (AES), atomic force microscopy (AFM) and perturbed angular correlation (PAC) spectroscopy, respectively. At room temperature inidium is found to grow in three-dimensional islands even at submonolayer coverages. A very rough film surface is observed for thicknesses up to 230 ML. The melting behaviour of such films has been studied by PAC. A reduction of the melting temperature T _m as well as a strong supercooling of the films is observed. The electric field gradient for ¹¹¹In(¹¹¹Cd) in the indium islands is determined as a function of temperature and is used to monitor the local crystalline order of the films up to temperatures just below the melting point.     

Confinement and processing effects on glass transition temperature and physical aging in ultrathin polymer films: Novel fluorescence measurements

Fluorescence intensity measurements of chromophore-doped or -labeled polymers have been used for the first time to determine the effects of decreasing film thickness on glass transition temperature, T _g, the relative strength of the glass transition, and the relative rate of physical aging below T _g in supported, ultrathin polymer films. The temperature dependence of fluorescence intensity measured in the glassy state of thin and ultrathin films of pyrene-doped polystyrene (PS), poly(isobutyl methacrylate) (PiBMA), and poly(2-vinylpyridine) (P2VP) differs from that in the rubbery state with a transition at T _g. Positive deviations from bulk T _g are observed in ultrathin PiBMA and P2VP films on silica substrates while substantial negative deviations from bulk T _g are observed in ultrathin PS films on silica substrates. The relative difference in the temperature dependences of fluorescence intensity in the rubbery and glassy states is usually reduced with decreasing film thickness, indicating that the strength of the glass transition is reduced in thinner films. The temperature dependence of fluorescence intensity also provides useful information on effects of processing history as well as on the degree of polymer-substrate interaction. In addition, when used as a polymer label, a mobility-sensitive rotor chromophore is demonstrated to be useful in measuring relative rates of physical aging in films as thin as 10 nm. Received 21 August 2001     

Atomic dynamics of explosive boiling of liquid-argon films

Using molecular-dynamics simulation, we study the explosive boiling of thin liquid-argon films adsorbed on a metal surface. This process might be induced by heating the metal substrate by an ultra-fast laser. Upon sudden heating of the metal to temperatures well beyond the critical temperature of Ar, the film starts boiling. While thin films, with thickness below seven monolayers, fragment completely, in larger films only the near-surface Ar layers vaporize. The resulting vapor pressure drives the expansion of the remaining liquid overlayers. By monitoring the space and time dependence of the hydrodynamic variables density, pressure, and temperature, as well as the local thermodynamic state in the Ar sample, we obtain a detailed microscopic picture of the explosive boiling process. Finally, as a result of the fragmentation process, the abundance distribution of the clusters formed in the expansion follows a power-law distribution for cluster sizes m ≲ 10.     

Kinetic Monte Carlo simulation of thin film growth

A three-dimensional kinetic Monte Carlo technique has been developed for simulating growth of thin Cu films. The model involves incident atom attachment, diffusion of the atoms on the growing surface, and detachment of the atoms from the growing surface. The related effect by surface atom diffusion was taken into account. A great improvement was made on calculation of the activation energy for atom diffusion based on a reasonable assumtion of interaction potential between atoms. The surface roughness and the relative density of the films were simulated as the functions of growth substrate temperature and film thickness. The results showed that there exists an optimum growth temperatureT _opt at a given deposition rate. When the substrate temperature approaches toT _opt, the growing surface becomes smoothing and the relative density of the films increases. The surface roughness minimizes and the relative density saturates atT _opt. The surface roughness increases with an increment of substrate, temperature when the temperature is higher thanT _opt.T _opt is a function of the deposition rate and the influence of the deposition rate on the surface roughness depends on the substrate temperatures. The simulation results also showed that the relative density decreases with the increasing of the deposition rate and the average thickness of the film.     

Effect of substrate temperature and annealing temperature on the structural, electrical and microstructural properties of thin Pt films by rf magnetron sputtering

Influence of both substrate temperature, T_s, and annealing temperature, T_a, on the structural, electrical and microstructural properties of sputtered deposited Pt thin films have been investigated. X-ray diffraction results show that as deposited Pt films (T_s = 300, 400 °C) are preferentially oriented along (1 1 1) direction. A little growth both along (2 0 0) and (3 1 1) directions are also noticed in the as deposited Pt films. After annealing in air (T_a = 500-700 °C), films become strongly oriented along (1 1 1) plane. With annealing temperature, average crystallite size, D, of the Pt films increases and micro-strain, e, and lattice constant, a₀, decreases. Residual strain observed in the as deposited Pt films is found to be compressive in nature while that in the annealed films is tensile. This change in the strain from compressive to tensile upon annealing is explained in the light of mismatch between the thermal expansion coefficients of the film material and substrate. Room temperature resistivity of Pt films is dependant on both the T_s and T_a of the films. Observed decrease in the film resistivity with T_a is discussed in terms of annihilation of film defects and grain-boundary. Scanning electron microscopic study reveals that as the annealing temperature increases film densification improves. But at an annealing temperature of ∼600 °C, pinholes appear on the film surface and the size of pinhole increases with further increase in the annealing temperature. From X-ray photoelectron spectroscopic analysis, existence of a thin layer of chemisorbed atomic oxygen is detected on the surfaces of the as deposited Pt films. Upon annealing, coverage of this surface oxygen increases.     

The influence of substrate temperature variation on tungsten oxide thin film growth in an HFCVD system

Tungsten oxide (WO₃) thin films were deposited by a modified hot filament chemical vapor deposition (HFCVD) technique using Si (1 0 0) substrates. The substrate temperature was varied from room temperature to 430 °C at an interval of 100 °C. The influence of the substrate temperature on the structural and optical properties of the WO₃ films was studied. X-ray diffraction and Raman spectra show that as substrate temperature increases the film tends to crystallize from the amorphous state and the surface roughness decreases sharply after 230 °C as confirmed from AFM image analysis. Also from the X-ray analysis it is evident that the substrate orientation plays a key role in growth. There is a sharp peak for samples on Si substrate due to texturing. The film thickness also decreases as substrate temperature increases. UV-vis spectra show that as substrate temperature increases the film property changes from metallic to insulating behavior due to changing stoichiometry, which was confirmed by XPS analysis.     

Magnetic and optical properties of epitaxial n-type Cu-doped ZnO thin films deposited on sapphire substrates

In this paper, we report on pulsed laser deposition of n-type Cu-doped ZnO thin films on c-plane sapphire substrates at 700°C. XRD and HRTEM were employed to study the epitaxial growth relationship between the Zn_1−x Cu _x O film and sapphire substrate. Absorption measurements showed excitonic nature of the thin films and a decrease in the bandgap energy with increased Cu concentration was observed. Such as-deposited films showed room temperature ferromagnetism with Curie temperature (T _c ) at around 320 K. The moment per Cu atom decreases as the Cu concentration increases. The largest magnetic moment about 0.81μ _B /Cu atom was observed for Zn_0.95Cu_0.05O thin films. The presence of any magnetic second phase was ruled out and the ferromagnetism was attributed to Cu ions substituted directly into the ZnO lattice.     

Effect of process parameters on surface morphology and characterization of PE-ALD SnO2 thin films for gas sensing

Tin dioxide (SnO₂) thin films were deposited by plasma enhanced-atomic layer deposition (PE-ALD) on Si(1 0 0) substrate using dibutyl tin diacetate (DBTA) ((CH₃CO₂)₂Sn[(CH₂)₃-CH₃]₂) as precursor. The process parameters were optimized as a function of substrate temperature, source temperature and purging time. It is observed that the surface phenomenon of the thin films was changed with film thickness. Atomic force microscopy (AFM) images and X-ray diffraction (XRD) pattern were used to observe the texture and crystallanity of the films. The films deposited for 100, 200 and 400 cycles were characterized by XPS to determine the chemical bonding properties. XPS results reveal that the surface dominant oxygen species for 100, 200 and 400 cycles deposited films are O₂⁻, O⁻ and O²⁻, respectively. The 200 cycles film has exhibited highest concentration of oxygen (O⁻) species before and after annealing. Conductivity studies revel that this film has best adsorption strength to the oxygen ions forming on the surface. The sensor with 200 cycles SnO₂ thin film has shown highest sensitivity to CO gas than other films. A correlation between the characteristics of Sn3d_5/2 and O1s XPS spectra before and after annealing and the electrical behavior of the SnO₂ thin films is established.     

Thermodynamic approach to the size dependence of the melting temperatures of films

The size dependence of melting temperature T _m of metallic films (tin and copper) on different substrates, including amorphous carbon and another refractory metal (i.e., the dependence of T _m on film thickness h) is investigated. It is found that the effect of the interfacial boundary can result in the growth of T _m for thin metallic films on carbon substrates with a reduction in film thickness h. For a system with a metallic film on a metallic substrate, the size dependence of T _m is less pronounced and T _m falls with a reduction in h.     

Role of surface Cooper pair interactions on critical temperature of ultra thin film superconductors

The superconductivity mechanism of Pb thin film on a Si substrate in the weak interaction regime is investigated. A discrete Fermi surface is constructed depend on the film thickness and electron density and crystallographic orientation. We consider two types of Cooper pair interactions, Cooper pair interaction at thin film surfaces and Cooper pair in the thin film volume. We have chosen the surface Cooper pair interaction, of ultra thin films superconductor proportional to the inverse of thin film thickness, while the volume Cooper pair interaction has been considered as a constant. By these assumptions, we have found oscillation feature of critical temperature Tc and energy gap Δ in terms of thin film thickness similar to the experimental results for Pb/Si(111) thin film superconductor. However, by increasing number of Pb layers, the thin film Tc goes to bulk Tc. In contrast to the previous claimed constant value for the Δb(T=0)/kBTc in bulk, we have found oscillation of this parameter in terms of thin film thickness similar to the Tc oscillation.     

Effect of atmosphere on reductions in the glass transition of thin polystyrene films

We have used nulling ellipsometry to measure the glass transition temperature, T _g , of thin films of polystyrene in ambient, dry nitrogen, and vacuum environments. For all environments, the measured T _g values decrease with decreasing film thickness in a way that is quantitatively similar to previously reported studies in ambient conditions. These results provide strong reinforcement of previous conclusions that such reduced T _g values are an intrinsic property of the confined material. Furthermore, the results are in contrast to recent reports which suggest that the T _g reductions measured by many researchers are the results of artifacts (i.e. degradation of the polymer due to annealing in ambient conditions, or moisture content).     

不同氮流量制备Mn3CuNx薄膜及其电、磁输运性质的研究

采用对靶磁控溅射方法在单晶Si(100)基片上制备了反钙钛矿结构的Mn₃CuN_x薄膜.通过控制制备过程中的反应气体氮气(N₂) 流量(N₂/Ar+N₂), 研究了氮含量对Mn₃CuN_x薄膜结构及物理性能的影响.分别利用X射线衍射仪、俄歇电子能谱、 原子力显微镜、X射线光电子能谱、物理性能测试系统和超导量子干涉仪, 对所制备薄膜的晶体结构、成分、表面形貌和电、磁输运性质进行了测试.结果表明:制备的薄膜均为反钙钛矿立方结构,且沿 (200) 晶面择优生长.随着氮含量的增大,薄膜表面粗糙度和颗粒度尺寸逐渐增大, 导致电阻率增加.氮含量对薄膜的电输运性质没有影响,所有薄膜电阻率均随着温度的降低逐渐增大, 呈现半导体型导电行为,这与对应的块体材料结果相反.Mn₃CuN_x薄膜随着测试温度的增大发生了 亚铁磁到顺磁的磁转变,且N含量的增大降低了磁有序转变温度,主要是由于N缺陷对Mn₆N八面体结构中 磁交换作用的影响所致.     

Preparation of Pb2CrO5 thin films by an electron-beam evaporation technique

Pb₂CrO₅ thin films have been prepared by an electron-beam evaporation deposition technique on glass substrates using ceramic disks. The thin film fabrication conditions are studied by x-ray diffraction, replica electron micrography and scanning electron microscopy as parameters of substrate temperature, annealing temperature and annealing time. As-deposited Pb₂CrO₅ thin films in the amorphous state are crystallized by heat treatment. Annealed thin films are structurally classified into three types according to the preferred orientations which depend on substrate temperatures (T _s:

1. (i)

   (020) atT _s=room temperature

2. (ii)

   mainly (310) atT _s=100 ‡C, and

3. (iii)

   (200) atT _s=350 ‡C.

The substrate temperature contributes to film orientations; annealing temperature and time-enhance film crystallinity. The annealing temperature is fixed between 400 and 500 ‡C in making appropriate Pb₂CrO₅ thin films. These thin films, ranging between 0.3 and 2.0 Μm in thickness, are prepared at a deposition rate of 1500 å/m.

     

The electrical, optical properties of AlSb polycrystalline thin films deposited by magnetron co-sputtering without annealing

In order to fabricate AlSb polycrystalline thin films without post annealing, this paper studies a technology of magnetron co-sputtering onto intentionally heated substrate. It compares the structural characteristics and electrical properties of AlSb films which are deposited at different substrate temperatures. It finds that the films prepared at a substrate temperature of 450 oC exhibit an enhanced grain growth with an average grain size of 21 nm and the lattice constant is 0.61562 nm that goes well with unstained lattice constant (0.61355 nm). The ln(σ_dark) ～1/T curves show that the conductivity activation energy is about 0.38 eV when the film is deposited at 450 oC without an annealing. The transmittance and reflectance spectra show that the film deposited at 450 oC has an optical band gap of 1.6 eV. These results indicate that we have prepared AlSb polycrystalline films which do not need a post annealing.     

Molecular dynamics in thin films of isotactic poly(methyl methacrylate)

The molecular dynamics in thin films (18 nm-137 nm) of isotactic poly(methyl methacrylate) (i-PMMA) of two molecular weights embedded between aluminium electrodes are measured by means of dielectric spectroscopy in the frequency range from 50 mHz to 10 MHz at temperatures between 273 K and 392 K. The observed dynamics is characterized by two relaxation processes: the dynamic glass transition (α-relaxation) and a (local) secondary β-relaxation. While the latter does not depend on the dimensions of the sample, the dynamic glass transition becomes faster (≤2 decades) with decreasing film thickness. This results in a shift of the glass transition temperature T _g to lower values compared to the bulk. With decreasing film thickness a broadening of the relaxation time distribution and a decrease of the dielectric strength is observed for the α-relaxation. This enables to deduce a model based on immobilized boundary layers and on a region displaying a dynamics faster than in the bulk. Additionally, T _g was determined by temperature-dependent ellipsometric measurements of the thickness of films prepared on silica. These measurements yield a gradual increase of T _g with decreasing film thickness. The findings concerning the different thickness dependences of T _g are explained by changes of the interaction between the polymer and the substrates. A quantitative analysis of the T _g shifts incorporates recently developed models to describe the glass transition in thin polymer films. Received 12 August 2001 and Received in final form 16 November 2001     

Surface morphology of sputter deposited low melting point metallic thin films

This paper describes the development of surface morphology of thin InSn(90/10), In, Sn and Cr films, deposited on unheated glass substrates by d.c. magnetron sputtering, with the film thickness. The experiments show that the surface morphology of metallic films with low melting pointsT _m[InSn(90/10)–150°C, In–156.6°C, Sn–231.8°C] and that with high melting pointT _m [Cr–1875°C] strongly differ. InSn(90/10) and Sn films with thickness greater than about 30 nm and also In films with even lower thickness of about 20 nm have a rough surface, milky color and matt appearance. On the contrary, Cr films of the same thickness have a smooth and shiny surface. It is due to a large difference in normalized temperaturesT/T _m for low-T _m films [Sn–0.59, In–0.70, InSn(90/10) –0.71] and for high-T _m films [Cr–0.14] deposited at low temperatures close to room temperature (RT). High values of the ratioT/T _m>0.5 clearly indicate that just the low melting point materials can crystallize at low temperatures close to RT. A crystallization of lowT _m films results in rough surface, milky color and matt appearance of these films.This work was supported in part by the Grant Agency of Czech Republic under Grant No. 202/93/0508.