Thermal change of organic light-emitting ALQ3 thin films

A series of Alq3 thin films with the thicknesses of 50, 100, and 200 nm was deposited on Si substrates at room temperature using the thermal evaporation method. The thermal crystallization process of Alq3 thin films, especially 50 nm thick films, was successfully examined using high-temperature X-ray diffraction (HT-XRD) with the in-plane scan mode. Film thickness, density, and changes in surface roughness while heating were determined using X-ray reflectometry (XRR). The decreased density and increased surface roughness, which were accompanied by sublimation, indicate the instability of the Alq3 film. Thus, thermal instability is a major factor for device failure.     

Study of Thin Polymeric Film Deposited by the PECVD Process for use at 193 nm

A plasma enhanced chemical vapor deposition (PECVD) reactor was used to deposit thin polymeric films with high absorption at 193 nm. The reactor is suitable to deposit uniform and pinhole free thin polymeric films with conformality over 95%. Conformal films with thickness as low as 200 Å have been deposited on silicon, glass, and quartz substrates, as well as silicon oxide, silicon nitrate, and aluminum films. Deposited films had variations in thickness of 3 to 5% over an area of 8 inches in diameter. Thin films deposited on silicon substrates under varying levels of RF power were scanned using the AFM technique. The measurements show increasing surface roughness of the scanned samples as the RF power increases.     

Thickness dependence of the structural,mechanical and electrical properties of Ni films deposited on polyimide by ion beam‐assisted deposition (IBAD)

Ni thin films with different thicknesses were deposited on pre‐treated polyimide substrates by ion beam‐assisted deposition. Dependence of structural, mechanical and electrical properties of the Ni films on their thickness was investigated. The results showed a clear correlation between film properties and film thickness. The inter‐diffusion at the interface regions of the films with different deposition time were demonstrated by transmission electron microscopy and X‐ray photoelectron spectroscopy. With increasing film thickness, surface roughness of the Ni films firstly decreased and then increased, while the grain size gradually increased. Residual stress of the Ni thin films decreased with increasing Ni film thickness up to 202 nm and then slightly increased as the film thickness further increased. Resistivity decreased, and temperature coefficient of resistivity (TCR) increased with increasing film thickness due to the enhancement of crystallization degree and the increase in grain size. The decrease in surface roughness and residual stress also contributed to the decrease of resistivity and the increase of TCR of the films. An optimal film thickness is suggested, which yielded a relatively high TCR value and low levels of both surface roughness and residual stress. Copyright © 2012 John Wiley & Sons, Ltd.     

Ultrathin film deposition by liquid CO2 free meniscus coating-uniformity and morphology

Ultrathin organic films of sucrose octaacetate (SOA) were deposited on 12.5 cm diameter silicon wafer substrates using high-pressure free meniscus coating (hFMC) with liquid CO2 (l-CO2) as a coating solvent. The dry film thickness across the wafer and the morphology of deposited films were characterized as a function of coating conditions-withdrawal velocity, solution concentration, and evaporation driving force (deltaP). When no evaporation driving force was applied (deltaP = 0), highly uniform films were deposited with thickness in the range of 8-105 angstroms over the entire concentration range (3-11 wt%). Uniform films were also obtained at low concentrations (3-5 wt%) with a low evaporation driving force (deltaP = 0.0138 MPa). However, films deposited at medium to high concentrations (7-11 wt%) were thicker (110-570 angstroms) and less uniform, with larger nonuniformities at higher applied evaporation driving forces. Optical microscopy and atomic force microscopy (AFM) were used to characterize film morphology including drying defects and film roughness. Films deposited without evaporation had no apparent drying defects and very low root-mean-square (RMS) roughness (1.4-3.8 angstroms). Spinodal-like dewetting morphologies including holes with diameters in the range of 100-300 nm, and surface undulations were observed in films deposited at medium concentration (7 wt%) and low deltaP (0.0138-0.0276 MPa). At higher concentrations and higher evaporative driving forces, spinodal-like dewetting morphologies disappeared but concentric ring defect structures were observed with diameters in the range 20-125 microm. The film thickness and morphology of SOA films deposited from 1-CO2 hFMC were compared to those deposited from toluene and acetone under normal dip coating. Films deposited from l-CO2 hFMC were much thinner, more uniform, and exhibited much fewer drying defects and lower RMS roughness.     

Partial dewetting of polyethylene thin films on rough silicon dioxide surfaces

The effect of roughness on the dewetting behavior of polyethylene thin films on silicon dioxide substrates is presented. Smooth and rough silicon dioxide substrates of 0.3 and 3.2-3.9 nm root-mean-square roughness were prepared by thermal oxidation of silicon wafers and plasma-enhanced chemical vapor deposition on silicon wafers, respectively. Polymer thin films of approximately 80 nm thickness were deposited by spin-coating on these substrates. Subsequent dewetting and crystallization of the polyethylene were observed by hot-stage optical microscopy in reflection mode. During heating, the polymer films melt and dewet on both substrates. Further observations after cooling indicate that, whereas complete dewetting occurs on the smooth substrate surface, partial dewetting occurs for the polymer film on the rough surface. The average thickness of the residual film on the rough surface was determined by ellipsometry to be a few nanometers, and the spatial distribution of the polymer in the cavities of the rough surface could be obtained by X-ray reflectometry. The residual film originates from the impregnation of the porous surface by the polymer fluid, leading to the observed partial dewetting behavior. This new type of partial dewetting should have important practical consequences, as most real surfaces exhibit significant roughness.     

Deposition of small organic molecules by the displacement of two immiscible supercritical phases

A new coating process is described (deposition from two immiscible supercritical phases, or DISP) in which a solution of supercritical carbon dioxide (scCO2) with a desired solute is displaced by supercritical helium (scHe). After depressurization, the solute is deposited on substrates initially submerged in the coating solvent. Micron-sized particles and thin films of sucrose octaacetate (SOA) were formed on silicon wafer substrate coupons from DISP at relatively low temperatures and pressures (< or = 6500 psi and < or = 60 degrees C). The particle size, film thickness, and morphology of SOA were characterized as a function of coating conditions-solution concentrations, withdrawal velocities, and pressures. Particles in the range of 1-14 microm in diameter were deposited at low solute concentrations (< or = 0.2 wt % at 4500 psi), whereas films in the range of 0.1-0.5 microm in thickness were deposited at higher solute concentrations (> or = 1.5 wt % at 4500 psi). Particle sizes decreased with increasing displacement velocity and increasing pressure. Estimates of characteristic times for diffusion and nucleation indicate that DISP is a diffusion-limited process. Optical microscopy and atomic force microscopy (AFM) were used to characterize film morphology, including defect formations and film roughness. Highly uniform films with low root-mean-square (RMS) roughness (approximately 10 angstroms) were obtained at a low displacement velocity of 0.0035 cm/s, while ring-like defect structures were observed in films deposited at a higher displacement velocity of 0.035 cm/s. The film thickness and morphology of the films deposited from DISP were compared with films from normal dip coating with typical organic solvents (acetone and toluene). Films deposited from scCO2 by DISP were much thicker, more uniform, and exhibited much fewer drying defects and lower RMS roughness compared with films from the organic solvents.     

Roughness correlation and interdiffusion in thin films of polymer chains

The surface morphology of thin bilayer polymer films on top of glass substrates was investigated. The bilayer consists of a blend film of protonated and deuterated polystyrene and an underlying deuterated polystyrene film. Choosing the thickness of the top film larger than 8 times and smaller than 2 times the radius of gyration of the chains enables the determination of film thickness and confinement effects. With diffuse neutron scattering at grazing incidence in the region of total external reflection, a depth sensitivity and a contrast even at the internal polymer–polymer interface was achieved. The underlying film is conformal to the substrate, and depending on the thickness of the top film two different types of roughness correlations are observed. Thin confined films nestle to the underlying polymer films, while the stiffness of thicker bulky films provides an independent morphology. In both cases, annealing above the glass-transition temperature yields an interdiffusion at the internal polymer–polymer interface, and the polymer–air surface remains essentially unchanged with respect to roughness correlations. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2862–2874, 1999     

高光学质量氮化碳薄膜的制备和表征

氮化碳(graphitic carbon nitride,g-CN)作为一种非金属半导体材料已被广泛应用于多种能源相关领域研究中。目前由于制备高质量g-CN薄膜的困难,大大限制了其在实际器件上的应用。本文中,我们报道了一种可制备高光学质量gCN薄膜的方法:即由三聚氰胺先通过热聚合制备本体g-CN粉末,再由本体g-CN粉末经过气相沉积在ITO导电玻璃或钠钙玻璃基底上制备g-CN薄膜。扫描电子显微镜和原子力显微镜的测量结果表明在ITO玻璃基底上形成的g-CN薄膜形貌结构均一且致密,厚度约为300nm。扫描电镜能量色散能谱和X射线光电子能谱测量结果表明在ITO玻璃基底上制备的g-CN薄膜的化学组成与本体g-CN粉末的化学组成基本一致。同时,我们发现制备的g-CN薄膜和本体g-CN粉末一样在光照射下可以有效降解亚甲基蓝染料。此外,我们还测量了制备的g-CN薄膜的稳态吸收光谱、稳态荧光光谱、荧光寿命和价带谱,并运用吸收光谱和价带谱数据确定了其能带结构。     

基底界面效应对聚苯乙烯薄膜分子运动行为的影响

本文研究了Si／Si02、Si／Si—H基底与聚苯乙烯（Ps）之间的界面相互作用对Ps薄膜的玻璃化转变及相关力学性能的影响．结果显示,无论何种基底,Ps薄膜的玻璃化转变温度（L）都随其厚度降低而降低．但相同厚度（〈110nm）下,以Si／Si-H为基底时Ps薄膜的瓦比以Si／Si02为基底的PS薄膜高．Si／Si02表面Ps薄膜疋开始下降的临界厚度为110nm,远高于以Si／Si—H为基底时的40nm．对Ps薄膜的膨胀系数和弹性模量进行研究,也得到相似的临界厚度．另外,与Si／Si02基底相比,在Si／Si-H上的Ps薄膜具有更低的膨胀系数以及较高弹性模量．可能原因是Si／Si-H与Ps具有较强的相互作用,限制了该界面分子的运动能力,导致基底／PS界面效应对薄膜分子运动的影响力增强,造成该薄膜瓦的厚度依赖性下降,并呈现出相对较硬的力学特征．     

Superhydrophilic/superhydrophobic surfaces fabricated by spark‐coating

In this study, the authors researched the preparations of superhydrophilic/superhydrophobic surfaces on commercial cup stock polyethylene coated papers by using sparked aluminum nanoparticles deposited on substrates through a sparking process. In this stage, the surface was porous and showed superhydrophilic properties. The samples were then annealed in air at various temperatures and some transformed to superhydrophobicity. It is well known that a suitable roughness in combination with low surface energy has been required to obtain superhydrophobic surfaces. Therefore, it is believed that during annealing process, when polyethylene is diffused from the substrate through the nanoparticle films and the superhydrophobic characteristics were created. The scanning electron microscope images showed that the film surfaces had a fluffy structure for both the as‐deposited and the annealed samples. However, the atomic force microscopy phase images showed completely different surface properties. Moreover, the X‐ray photoelectron spectroscopy spectra showed different surface chemical compositions. The experimental results revealed that the working temperature to produce superhydrophobic surfaces depended on the sparked film thickness. Furthermore, in order to prove the assumption explained above, glass and poly (methyl methacrylate) were also used as substrates.     

Glass transition behavior of spin-coated thin films of a hydrophilic polymer on supported substrates

Using ellipsometry, it is found the glass transition temperature of the spin-coated polyacrylamide(PAL) thin films on the supported silicon(Si) substrates with an oxide layer decreases with decreasing the film thickness. But Tgs of the asprepared thin films are much higher than that of the bulk sample. Such observations can be attributed to the combined result of the "surface effect" and increased hydrogen bonding interaction between PAL chains due to spin coating/thin film confinement.     

Influence of the substrate type on the microstructural,optical and electrical properties of sol–gel ITO films

Indium tin oxide (ITO) is recognized as the best transparent and conductive material [transparent conducting oxide (TCO)] until now and its properties are dependent on the preparation method. In the present work ITO films with In:Sn atomic ratio 9:1 were prepared by a sol–gel route on different substrates (microscope glass slides, microscope glass covered with one layer of SiO₂ and Si wafers) for TCO applications. The multilayer ITO films were obtained by successive deposition by the dip-coating method and the films were characterized from the structural, morphological, optical, and electrical points of view using X-ray diffraction, scanning electron microscopy, atomic force microscopy, spectroscopic ellipsometry and by Hall effect measurements, respectively. The results showed that the thickness, optical constants and carrier numbers depend strongly on the type of substrate, number of deposited layers and sol concentration. The optical properties of ITO films are closely related to their electrical properties. The enhancement of the conductivity was possible with the increase of crystallite size (which occurred after thermal treatment) and with the reduction of surface roughness.     

Surface structure and photoluminescence properties of AZO thin films on polymer substrates

Al‐doped zinc oxide (AZO) thin films were deposited on indium tin oxide (ITO) coated polyethylene terephthalate (PET) substrates by radio frequency (RF) magnetron sputtering method at room temperature. The effects of film thickness on the surface structure and the photoluminescence properties of the films were investigated by atomic force microscopy (AFM), secondary ion mass spectroscopy (SIMS) and room temperature photoluminescence (PL). AFM analysis showed that the surface of all films was extremely flat and uniform at nanoscale. Root mean square (RMS) value of the surface roughness which scanned the surface area of 3 µm by 3 µm and grain size increased with increasing the film thickness. Thus, the surface morphology of the films became rough because of the coarse grains. The depth profile of AZO layers was analyzed by SIMS. It was found that the thickness of the AZO layer is almost same with the desired film thickness. The PL intensity of the dominant peak decreased and shifted slightly towards the shorter wavelengths with increasing the film thickness. According to the relationships between luminescence intensity and crystalline characteristics, it was observed that the intensity of the peak decreased by the increased surface area of the grains. Copyright © 2014 John Wiley & Sons, Ltd.     

Measuring thickness changes in thin films due to chemical reaction by monitoring the surface roughness with in situ atomic force microscopy.

Measuring the changing thickness of a thin film, without a reference, using an atomic force microscope (AFM) is problematic. Here, we report a method for measuring film thickness based on in situ monitoring of surface roughness of films as their thickness changes. For example, in situ AFM roughness measurements have been performed on alloy film electrodes on rigid substrates as they react with lithium electrochemically. The addition (or removal) of lithium to (or from) the alloy causes the latter to expand (or contract) reversibly in the direction perpendicular to the substrate and, in principle, the change in the overall height of these materials is directly proportional to the change in roughness. If the substrate on which the film is deposited is not perfectly smooth, a correction to the direct proportionality is needed and this is also discussed.     

Effect of continuous magnetic field on the growth mechanism of nanoporous anodic alumina films on different substrates

The effects induced by an external homogeneous magnetic field on the oxide film growth on aluminum in aqueous solutions of oxalic and sulfuric acid and on surface morphology of the alumina films were studied. Aluminum films of 100 nm thickness were prepared by thermal evaporation on SiO₂/Si and glass-ceramic substrates. The pore diameter for oxalic acid alumina films on the SiO₂/Si substrate decreased by 0.8 nm, the interpore distance by 5.9 nm, and cell diameter by 6.9 nm if a magnetic field of 0.5 T was applied. When aluminum was anodized in sulfuric acid on the same substrate, the significant changes in parameters of porous structure of alumina, which were similar to the ones in oxalic acid, are firstly observed in stronger magnetic fields (of 0.7 T). On the basis of data obtained in this study and of previous investigation on the negative space charge and thermally activated defects in anodic alumina, we concluded that the intensity of the magnetic field is associated with energy of electron traps and that the changes of cell diameter characterize the trap concentration. The energy of electron traps in oxalic acid alumina films was proved to be smaller than the one in films formed in sulfuric acid, but the concentration of traps was of the same order of magnitude. When the substrate was replaced with the glass-ceramic one, the pore diameter in oxalic acid alumina films increased to ca. 17.6 nm.     

Effect of deposition parameters on the wettability and microstructure of superhydrophobic films with hierarchical micro-nano structures

Superhydrophobic films with hierarchical micro-nano structures were deposited on glass substrates by solution immersion method from a solution containing cobalt chloride, urea and cetyl trimethyl ammonium bromide (CTAB). Subsequently the films were hydrophobized with a low surface energy material like octadecanoic acid under ambient conditions resulting in superhydrophobic surfaces with water contact angle (WCA) of about 168° and contact angle hysteresis of 1°. The effect of deposition parameters such as solution composition, temperature, deposition time and alkanoic acid treatment on surface morphology and wettability of the films was studied. Mechanism of formation of cobalt chloride carbonate hydroxide film is discussed. Addition of CTAB to the solution resulted in a change in the surface morphology of the deposited films with flower-like structures. The wettability of films obtained under different process conditions was correlated to surface roughness using Wenzel and Cassie models.     

Structural and optical properties of TiO2 thin films prepared by spin coating

Transparent semiconducting thin films of titanium oxide (TiO₂) were deposited on glass substrates by the sol–gel method and spin-coating technique. The physical properties of the prepared films were studied as a function of the number of spun-cast layers. The microstructure and surface morphology of the TiO₂ films were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM), with respect to the film thickness. The XRD analysis reveals that the films are polycrystalline with an anatase crystal structure and a preferred grain orientation in the (101) direction. The morphological properties were investigated by AFM, which shows a porous morphology structure for the films. The optical properties of the films were characterized by UV–Visible spectrophotometry, which shows that the films are highly transparent in the visible region and their transparency is slightly influenced by the film thickness, with an average value above 80 %. The dependence of the refractive index (n), extinction coefficient (k), and absorption coefficient (α) of the films on the wavelength was investigated. A shift in the optical band gap energy of the films from 3.75 to 3.54 eV, as a function of the film thickness, has been observed.     

Characteristics of SnO2 thin films prepared by SILAR

SnO₂ thin films were deposited on glass substrates by using Successive Ionic Layer Adsorption and Reaction (SILAR) method at room temperature. The film thickness effect on characteristic parameters such as structural, morphological, optical and electrical properties of the films was studied. Also, the films were annealed in oxygen atmosphere (400 °C, 30 min) and characteristic parameters of the films were investigated. The X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) studies showed that all the films exhibited polycrystalline nature with tetragonal structure and were covered well on glass substrates. After the investigation of the crystalline and surface properties of the films, it was found that they were improving with increasing film thickness. Optical band gap decreased from 3.90 eV to 3.54 eV and electrical conductivity changed between 0.015–0.815 (Ω-cm)⁻¹ as the film thickness increased from 215 to 490 nm. The refractive index (n), optical static and high frequency dielectric constants (ɛ_o, ɛ_∞) values were calculated by using the optical band gap values as a function of the film thickness.     

Electrochemical modification of surface morphology of Au/Ti bilayer films deposited on a Si prism for in situ surface-enhanced infrared absorption (SEIRA) spectroscopy

Surface-enhanced infrared absorption (SEIRA)-active Au/Ti bilayer films sputter deposited on Si substrates have been prepared by an electrochemical annealing (ECA) treatment for the first time. The application of Au/Ti bilayer films on Si substrates to the spectroscopic technique is a promising alternative to the conventional technique using directly deposited Au films on Si substrates, offering excellent adhesive durability of the deposited metal films. However, Au/Ti bilayer films have never been selected for the spectroscopy technique because the films in the as-prepared state exhibit relatively smooth surface morphology: the excitation of the localized surface plasmon is vital to achieving SEIRA enhancements but could hardly be observed on the smooth morphology. It is shown by ex situ scanning tunneling microscopy measurements that the unfavorable smooth morphology of the as-prepared Au/Ti bilayer films can be modified by the ECA treatment to a reasonably rough, island-structure morphology similar to that of the conventional SEIRA-active Au films. In situ infrared absorption spectroscopy of adsorbed sulfate anions has been conducted on the Au/Ti bilayer film both before and after ECA treatment. The spectroscopy measurements demonstrate that the SEIRA activity of the film after being subjected to the treatment is significantly improved so that the technique could detect adsorbates on the film electrodes even with the submonolayer coverage. As an additional benefit, the ECA treatment has brought about a substantial increase in the fraction of Au(111) domains on the polycrystalline Au film surfaces. Accordingly, this approach enables us to prepare SEIRA-active Au films having sufficient adhesion to the Si substrates as well as the highly preferred (111) orientation.     

Thickness dependent physical properties of close space evaporated In2S3 films

In recent years, In₂S₃ is considered as a promising buffer layer in the fabrication of heterojunction solar cells. Film thickness is one of the important parameters that alters the physical characteristics of the grown layers significantly. The effect of film thickness on the structural, morphological, optical and electrical properties of close space evaporated In₂S₃ layers has been studied. In₂S₃ thin films with different thicknesses in the range, 100–700 nm were deposited on Corning glass substrates at a constant substrate temperature of 300 °C. The films were polycrystalline exhibiting strong crystallographic orientation along the (103) plane. The deposited films showed mixed phases of both cubic and tetragonal structures up to a thickness of 300 nm. On further increasing the film thickness, the layers showed only tetragonal phase. With increase of film thickness, both the crystallite size and surface roughness in the films were found to be increased. The optical constants such as refractive index and extinction coefficient of the as-grown layers have been calculated from the optical transmittance data in the wavelength range, 300–2500 nm. The optical transmittance of the films was decreased from 82% to 64% and the band gap varied in the range, 2.65–2.31 eV with increase of film thickness. The electrical resistivity as well as the activation energy was evaluated and found to decrease with film thickness. The detailed study of these results was presented and discussed.