Crystallization Kinetics of Lamellar Crystals Confined in Polymer Thin Films

We used dynamic Monte Carlo simulations to investigate the crystallization kinetics of flat-on lamellar polymer crystals in variable thickness films. We found that the growth rates linearly reduced with decreasing film thickness for the films thinner than a transition thickness d_t , while they were constant for the films thicker than d_t . Moreover, the mean stem lengths (crystal thickness) we calculated decreased with film thickness in a similar way to the growth rates, and the intramolecular crystallinities we calculated confirmed the film thickness dependence of the crytsal thickness. Besides, the crystal melting rates in thin films were calculated and increased with decreasing film thickness. We proposed a new interpretation on the film thickness dependence of the crystal growth rate in thin films, suggesting that it is dominated by the crystal thickness in terms of the driving force term (l–l _min) expressed by Sadler, rather than the chain mobility based on experiments. The crystal thickness can determine whether a crystal grows or melts in a thin film at a fixed temperature, indicating the reversibility between the crystal growth and melting.     

Crystal growth rates of diblock copolymers in thin films: Influence of film thickness

Using optical and atomic force microscopy we determined the growth rate of polymer crystals in thin films of low molecular weight poly(styrene-ethyleneoxid) block copolymers. We focused in particular on films either thinner or slightly thicker than the thickness of a crystalline lamella (L). At a given temperature, three distinctly different growth rates were observed for i) crystals grown from adsorbed monolayers thinner than L, ii) primary compact lamellar crystals in films thicker than L and iii) secondary crystals formed from molecules remaining on top of ii). The growth rate of primary crystals did not indicate a dependence on film thickness. Crystals from monolayers grew by a factor of 30 more slowly than primary crystals. Secondary crystals grew faster than crystals from monolayers but slower than primary crystals and the degree of deviation from the growth rate of primary crystals was found to depend on the value of L, which varied with temperature. The mechanisms responsible for the differences in growth rate are discussed in terms of the amount of available polymers and the controlling influence of diffusion towards the crystal front.Received: 9 September 2003PACS: 61.41. + e Polymers, elastomers, and plastics - 68.47.Mn Polymer surfaces 68.55.-a Thin film structure and morphology - 81.10.Aj Theory and models of crystal growth; physics of crystal growth, crystal morphology and orientation     

CRYSTAL GROWTH OF ISOTACTIC POLYSTYRENE IN ULTRATHIN FILMS: FILM THICKNESS DEPENDENCE

The film thickness dependence of crystal growth is investigated for isotactic polystyrene (it-PS) in thin films for thicknesses from 20 down to 4 nm. The single crystals of it-PS grown at 180°C in the ultrathin films show a morphology typical of diffusion-controlled growth: dense branching morphology and fractal seaweed. The characteristic length of the morphology, i.e., the width of the branch, increases with decreasing film thickness. The thickness dependence of the crystal growth rate shows a crossover around the lamellar thickness of 8 nm. The thickness dependences of the growth rate and morphology are discussed in terms of the diffusion of chain molecules in thin films.     

Morphological Changes in Flat-on and Edge-on Lamellae of Poly(Ethylene Succinate) Crystallized from Molten Thin Films

Corrugated crystal morphologies of poly(ethylene succinate) (PESU) with a bird-wing shape grew from the thin-film melt with the film thickness less than 1 μm. The center of the bird-wing-shaped crystal consisted of a lozenge crystal. Corrugated steps were observed in the direction of the short axis of the lozenge crystal (b-axis). Fibrous textures extended in the direction of the long axis of the lozenge crystal (a-axis), and they wrapped around the corrugated crystals. The corrugated crystals and the fibrous textures consisted of flat-on and edge-on lamellae, respectively. The wing-shaped morphology was constructed by combining the crystal growth with the flat-on and edge-on lamellae.     

生长初期Ta膜的表面动态演化行为

用磁控溅射方法在单晶Si衬底上沉积膜厚为15—250nm的Ta膜.基于原子力显微镜获得的薄膜表面形貌，用动力学标度理论量化表征薄膜表面动态演化行为.结果表明：当膜厚d<50nm时，薄膜生长指数β≈0.17，而d>50nm后β≈0.45；随着d增加，粗糙度指数α由0.24逐渐增加到0.69，且在d>50nm后趋于稳定.Ta膜的表面动态演化行为揭示了其由小岛聚合结构向连续膜演化的生长过程.与自阴影等非局域效应引起的非稳定行为不同的是，当d<50nm时，薄膜表面动态演化的非稳定行为来源于生长初期的小岛聚合，表面小岛沿膜面切向的生长优于沿法向的生长.随着d继续增加，薄膜以连续膜形式生长，表面动态演化趋于稳定.     

Crystal Growth of Isotactic Polystyrene in Ultrathin Films: Thickness and Temperature Dependence

The growth rate and morphology of isotactic polystyrene crystals grown in ultrathin films have been examined experimentally in terms of the dependences both on the film thickness and on the crystallization temperature. We have found that the thickness dependence of growth rate, G, shows a crossover change when the film thickness becomes comparable with the lamellar thickness of the polymer crystals, irrespective of the temperatures. The morphology of crystals grown in ultrathin films shows a branching typical of dendrites, the growth of which is supposed to be controlled by a diffusion field. The change in the tip width of the dendrites with crystallization temperature follows the expected dependence of the Mullins–Sekerka stability length, ?_MS ∝ (D/G)^1/2, determined by the diffusion coefficient, D, and the growth rate. The results confirm that a diffusion field plays an essential role in the evolution of the structure.     

Thickness dependent magnetic and ferroelectric properties of LaNiO3 buffered BiFeO3 thin films

BiFeO₃ (BFO) thin films with thickness increasing from 40 to 480 nm were successfully grown on LaNiO₃ (LNO) buffered Pt/Ti/SiO₂/Si(100) substrate and the effects of thickness evolution on magnetic and ferroelectric properties are investigated. The LNO buffer layer promotes the growth and crystallization of BFO thin films. Highly (100) orientation is induced for all BFO films regardless of the film thickness together with the dense microstructure. All BFO films exhibited weak ferromagnetic response at room temperature and saturation magnetization is found to decrease with increase in film thickness. Well saturated ferroelectric hysteresis loops were obtained for thicker films; however, the leakage current dominated the ferroelectric properties in thinner films. The leakage current density decreased by three orders of magnitude for 335 nm film compared to 40 nm film, giving rise to enhanced ferroelectric properties for thicker films. The mechanisms for the evolution of ferromagnetic and ferroelectric characteristics are discussed.     

Mass density and dielectric constants of quench condensed AuSn-and AgSn-films

The mass density and dielectric constants at λ=632.8 nm of quench condensed AuSn and AgSn films are determined by ellipsometric measurements combined with quartz microbalances. The measurements, which were carried out continuously during the condensation process indicate that the properties of these films are thickness dependent for films thinner than about 30 nm. There is strong evidence that the films have a porous structure which decreases with increasing films have a porous structure which decreases with increasing film thickness asymptotically. The mass density of the films thicker than 30 nm is in the whole concentration range lower than the interpolations of the densities of the pure solid elements assuming a constant atomic volume but it is higher than a corresponding interpolation of the densities of the pure liquid elements. An evaluation of the complex dielectric constant (DC) of the thicker films according to the Drude theory yields a relaxation time of the disordered films, which is distinctly smaller than that of bulk metals. In the case of the thicker films no annealing effects are observed.     

Thickness effect on stress,structural, electrical and sensing properties of (0 0 2) preferentially oriented undoped ZnO thin films

Preferentially oriented (0 0 2) ZnO thin films with c-axis-oriented wurtzite structure have been grown on Si (1 0 0) and glass substrates using radio frequency magnetron sputtering. The residual stresses have been determined and calculated via the Stoney formalism. The ZnO thin films have been also characterised by X-ray diffraction and scanning electron microscope, and their stoichiometry was verified by Rutherford backscattering spectroscopy. The evolution of the residual stress was studied as a function of film thickness in the 10–1200 nm range. A growth scenario is proposed and a possible correlation between the residual stress, film’s texture and crystallographic orientation is highlighted. The crystalline quality was found to improve, while the stress values decreased with increasing thickness, and as a ramification the thicker films developed better sensing response to gases. The mechanical (stress) and electrical properties of the films were also investigated as a function of the film thickness, which tended to manifestly improve in dependence on thickness as well. We attribute this to the fact that the thinner films are under vehement misfit stress that declines with increasing the film thickness further.     

Crystallization of Poly(Ethylene Oxide) in Thin Films

Crystallization of poly(ethylene oxide) (PEO) in thin films was studied using hot-stage polarized optical microscopy. Isothermal linear crystal growth rates were measured for various film thicknesses at various degrees of undercooling. At a given crystallization temperature, the linear crystal growth rate decreased exponentially with decreasing film thickness below a film thickness of 80 nm. Films showed similar spherulitic morphology down to a film thickness of 30 nm. Control experiments on hydrophilic and hydrophobic surfaces showed that surface chemistry affects stability of the polymer films and causes a competition between crystallization and dewetting.     

Two hardening mechanisms in single crystal thin films studied by discrete dislocation plasticity

Two-dimensional discrete dislocation plasticity simulations of the evolution of thermal stress in single crystal thin films on a rigid substrate are used to study size effects. The relation between the residual stress and the dislocation structure in the films after cooling is analyzed using dislocation dynamics. A boundary layer characterized by a high stress gradient and a high dislocation density is found close to the impenetrable film-substrate interface. There is a material-dependent threshold film thickness above which the dislocation density together with the boundary layer thickness and stress state are independent of film thickness. In such films the stress outside the boundary layer is on average very low, so that the film-thickness-independent boundary layer is responsible for the size effect. A larger size effect is found for films thinner than the threshold thickness. The origin of this size effect stems from nucleation activity being hindered by the geometrical constraint of the small film thickness, so that by decreasing film thickness, the dislocation density decreases while the stress in the film increases. The size dependence is only described by a Hall–Petch type relation for films thicker than the threshold value.     

Size-Frustrated Thickening Growth of Extended-Chain Crystals in a Poly (Ethylene Terephthalate)/Bisphenol A Polycarbonate Blend Under High Pressure

High-pressure crystallized blend samples of poly (ethylene terephthalate)/bisphenol A polycarbonate (PET/BAPC) were investigated with scanning electron microscopy (SEM), confocal laser micro-Raman spectroscopy, and a standard general area detector diffraction system (GADDS) X-ray micro-diffraction system. The results showed that long time annealing at high pressure could result in extended-chain polymer single crystals with thicker lamellae. However, the large size of such crystals was also found to frustrate their thickening growth along the c-axis thickness, as demonstrated by the observation of a novel wrinkled crystal. The winkled crystals with different morphologies were thought to be formed as the compromise between the kinetic pathway and the thermodynamic driving force during the size-frustrated thickening growth of the large polymer crystals. Further observations revealed that environmental confinement was the main factor responsible for the creation of the wrinkled structures in polymer extended-chain crystals. The present study may promote understanding of the fundamental nature of the crystal thickening in these binary polyester blends.     

Hydrophilicity of amorphous TiO2 ultra-thin films

The UV-light-induced hydrophilicity of amorphous titanium dioxide thin films obtained by radio frequency magnetron sputtering deposition was studied in relation with film thickness. The effect of UV light irradiation on the film hydrophilicity was fast, strong and did not depend on substrate or thickness for films thicker than a threshold value of about 12 nm, while for thinner films it was weak and dependent on substrate or thickness. The weak effect of UV light irradiation observed for the ultra-thin films (with thickness less than 12 nm) is explained based on results of measurements of surface topography, UV-light absorption and photocurrent decay in vacuum. Comparing to thicker films, the ultra-thin films have a smoother surface, which diminish their real surface area and density of defects, absorb partially the incident UV light radiation, and exhibit a longer decay time of the photocurrent in vacuum, which proves a spatial charge separation. All these effects may contribute to a low UV light irradiation effect on the ultra-thin film hydrophilicity.     

金属诱导生长与超高真空化学气相沉积方法相结合制备多晶锗硅薄膜

采用金属Ni诱导与超高真空化学气相沉积(UHVCVD)相结合的方法，在热氧化硅衬底上生长了多晶锗硅薄膜.利用X射线衍射(XRD)、场发射扫描电镜(SEM)等对多晶锗硅薄膜的质量、表面形貌进行了测试分析，并就生长参数以及金属Ni对薄膜性能的影响进行了研究.结果表明：1)在420—500℃范围内，金属Ni具有明显的诱导作用；2)Ni层厚度对薄膜质量及形貌的影响使得晶粒尺寸随Ni厚度增加存在一极大值.在Ni层厚度为60nm时，能够获得晶粒尺寸均匀，晶粒大小为500—600nm，结晶质量良好的多晶锗硅薄膜. 关键词： 超高真空化学气相沉积 金属诱导 镍 多晶锗硅     

应力对La0.83Sr0.17MnO3薄膜输运性能的影响

采用溶胶-凝胶方法在Si(111)上制备了LSMO(x=0.17)薄膜.研究了块体材料和不同厚度薄膜R -T曲线、红外光谱和X射线衍射.结果表明，LSMO薄膜属于正交晶体结构，薄膜取向与膜厚度 有关，当膜厚度为450nm或680nm时，主要取向〈200〉，而膜厚度为900nm时取向为〈020〉 ：根据离子对相互作用能和谐振子模型，得到了红外吸收与Mn—O—Mn键长和键角关系式，6 00cm^-1附近红外吸收与晶格常数b的变化有关；块体与薄膜的金属—绝缘体转变 温度(T_MI)存在较大差别，薄膜转变温度显著低于块体，并与厚度有一定关系. 认为是LSMO薄膜中的应力诱导了晶格常数变化，引起键角改变及JT效应是转变温度变化的主 要原因. 关键词： 单晶硅 晶格常数 金属—绝缘体转变温度 应力诱导     

Magnetic anisotropy axis reorientation at ultrathin FePt films

Ultrathin FePt films (thickness between 1 nm and 5 nm) were studied for non‐volatile memories applications. The films were magnetron sputtered on monocrystalline MgO?001? substrates at 500 °C. The films are polycrystalline, except the 1 nm thick film which is not continuous. It is shown that films with thickness higher than 2.7 nm have L1₀ structure and perpendicular magnetic anisotropy, while a transition to in‐plane anisotropy occurs for thinner films. The out‐of‐plane coercivity drops from 16 kOe at the thicker film to 0.5 kOe at the thinner one.

Hysteresis cycles of FePt films as a function of film thickness.     

Optical transmittance and microgravimetric studies of the oxidation of 〈100〉 single crystal films of copper

Thin single crystal copper films have been grown and oxidized on (100) faces of cleaved sodium chloride discs suspended from a vacuum ultramicrobalance. Optical transmittance measurements between 400–800 nm and electron microscopic investigations were also used to characterize the oxidation process. Polycrystalline copper films grown at room temperature are substantially the same as those grown previously on glass substrates. Single crystalline growth at 325 ° C on rock salt produces a characteristic transmittance curve due to the “island” nature of the films. These curves compare favorably with other previously published results. Single crystal copper films oxidized to CuO_0.67 at temperatures of 117–159°C in 100 Torr of oxygen for films less than 500 A thick. For films 378 to 1000 Å thick, compositions of CuO_0.52 to CuO_0.62 were obtained between 123–176°C. The oxidation to less than CuO_0.67 is attributed to the existence of islands in these films which are thicker than the average film thickness, and require higher temperatures or thinner films to permit oxidation to CuO_0.67 before the nucleation of CuO sets in.     

薄膜厚度对La1.85Sr0.15CuO4薄膜结构和超导电性的影响

使用直流同轴磁控溅射法,在SrTiO₃(STO)衬底上成功制备出c取向的La_1.85Sr_0.15CuO₄(LSCO)超导薄膜.通过电输运测量系统和X射线衍射仪研究了薄膜厚度对LSCO(x＝0.15)薄膜电学性质和晶体结构的影响.实验证明随着膜厚增加,(006)衍射峰的半高宽(Full Width at Half Maximum,FWHM)逐渐减小,薄膜的取向性增强,与此同时,薄膜的超导转变温 关键词： 1.85Sr_0.15CuO₄薄膜')" href="#">La_1.85Sr_0.15CuO₄薄膜 超导电性 晶体结构     

Switching layer stability in a polymer bilayer by thickness variation

We use optical and scanning force microscopy to explore the possibility of switching the stability of a bilayer of poly(methyl methacrylate) (PMMA) on polystyrene by simply changing the film thickness. We show that for thin PMMA layers on thicker polystyrene films the PMMA layer is unstable to thickness fluctuations. However, polystyrene layers are unstable when they are substantially thinner than the now stable PMMA film. Dewetting morphologies are cataloged as a function of the thickness of individual polymer layers by identifying which layer is unstable by which mechanism, be it spinodal dewetting or heterogeneous thermal nucleation. Our results are in good agreement with a linear stability analysis of the influence of long-range dispersion forces, but also indicate the influence of film preparation and small variations of material properties.     

Surface structure and composition of flat titanium thin films as a function of film thickness and evaporation rate

To correlate flat titanium film surface properties with deposition parameters, titanium flat thin films were systematically deposited on glass substrates with various thicknesses and evaporation rates by electron-beam evaporation. The chemical compositions, crystal structure, surface topographies as well as wettability were investigated by using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), atomic force microscopy (AFM) and water contact angle measurement, respectively. The films consisted mainly of TiO₂. Small percentages of Ti₂O₃ and metallic Ti were also found at the film surface using high-resolution XPS analysis. Quantitative XPS showed little differences regarding elemental compositions among different groups of films. The films were obtained by varying the deposition rate and the film thickness, respectively. XRD data showed consistent reflection patterns of the different titanium samples deposited using different film thicknesses. Without exception measurements of all samples exhibited contact angles of 80° ± 5°. Quantitative AFM characterization demonstrated good correlation tendency between surface roughness and film thickness or evaporation rate, respectively. It is important to notice that titanium films with different sizes of grains on their surfaces but having the same chemistry and film bulk structure can be obtained in a controllable way. By increasing the film thickness and evaporation rate, the surface roughness increased. The surface morphology and grain size growth displayed a corresponding trend. Therefore, the control of these parameters allows us to prepare titanium films with desired surface properties in a controllable and reproducible way for further biological investigations of these materials.