Grain boundary potential and charge density at grain boundaries of chemically prepared thin silver sulfide films

The grain boundary potential and interface state charge density at the grain boundaries of silver sulfide (Ag₂S) thin films prepared by chemical conversion of cadmium sulfide (CdS) films have been determined from the dc resistance of the material and are found to be sensitive to annealing. A reduction in the grain boundary potential and the grain boundary charge density of the film has been noticed when the source CdS film is annealed at different temperatures prior to chemical conversion. The variation in the grain boundary charge density of the grown Ag₂S film with source annealing temperature has been found to be similar to that of thin cadmium sulfide film, reported earlier. An additional low temperature heat treatment of the sample results in an enhancement in the charge density at the grain boundaries. The change in the silver vacancy and/or oxygen and sulfur content of the films as revealed from the energy dispersive spectra of the films suggests possible role of film composition on the grain boundary charge density.     

Optimization of the optical and electrical properties of electron beam evaporated aluminum-doped zinc oxide films for opto-electronic applications

Aluminum-doped zinc oxide (AZO) thin films have been deposited by electron beam evaporation technique on glass substrates. The structural, electrical and optical properties of AZO films have been investigated as a function of annealing temperature. It was observed that the optical properties such as transmittance, reflectance, optical band gap and refractive index of AZO films were strongly affected by annealing temperature. The transmittance values of 84% in the visible region and 97% in the NIR region were obtained for AZO film annealed at 475 °C. The room temperature electrical resistivity of 4.6×10⁻³ Ω cm has been obtained at the same temperature of annealing. It was found that the calculated refractive index has been affected by the packing density of the thin films, whereas, the high annealing temperature gave rise to improve the homogeneity of the films. The single-oscillator model was used to analyze the optical parameters such as the oscillator and dispersion energies.     

Influence of surface properties on the structure of granular silver films and excitation of localized plasmons

Granular silver films deposited on a thin insulating film of amorphous hydrogenated carbon (a-C:H) and transparent conducting electrode (polycrystalline indium tin oxide (ITO) layer) have been investigated by spectroscopy and microscopy methods. The extinction spectra of silver films on the surface of these materials are found to be significantly different. An annealing of silver films causes a blue shift of the peak of plasmon resonance band in the spectrum of silver nanoparticles: by 16 nm on the a-C:H surface and by 94 nm on the ITO surface. Silver films on the surface of a-C:H films are characterized by a narrower band in the extinction spectrum, which is peaked at 446 nm. The changes observed in the optical density of Ag films are related to the change in size and area of nanoparticles. The results of spectral studies of Ag films are in agreement with the data on the nanostructure obtained by scanning electron microscopy and statistical image processing. The spectra of granular silver films are shown to correlate well with the nanoparticle distribution function over the film area.     

Asymmetric distribution of surface second harmonic generation for thin silver films deposited on Si(111)

The asymmetric distributions of surface optical second harmonic generation (SHG) through azimuthally angular scans of (111) silicon wafers on which thin silver films were deposited, have been detected with different polarizations of output beams. On account of the inversion symmetry of silicon crystals, the SHG for the Ag/Si system is mainly contributed by the silver film and the silicon surface. In this work, we found that the interface strain implies an asymmetric intensity variation of SHG with respect to the surface azimuthal angles as an ultra thin Ag film is deposited on silicon wafers. This asymmetric behavior is prominent as the deposited silver layer is heated so that the continuous film aggregates to become granular nanoparticles. Similar changes of the surface asymmetric SHG are observed for a bare Si wafer imposed upon by an external force.     

Second harmonic generation by cold-deposited silver films

The second harmonic generation (SHG) of light diffusely scattered by cold-deposited silver films is negligible with respect to the specular intensities. Therefore, a cold-deposited silver film is well approximated by a homogeneous effective medium. The intensities of SHG at 1.06 μm and the optical absorption at 0.53 μm depend on both the square of the internal effective field at 0.53 μm and a change in the same way when annealing the film. This can be understood by the assumption that SHG is also mainly following the electric field within the metal phase and surface contributions to SHG interfere destructively. This is corroborated by the observation that the SHG intensity does not show the ‘chemical first layer effects’ seen by surface-enhanced Raman scattering (SERS).     

纳米结构表面形貌成型机理及其对石墨烯拉曼光谱的影响

通过真空热蒸镀和高温退火法制备的金属纳米复结构SERS基底因其具有良好的灵敏度,稳定性和均匀性而广泛应用于各种检测领域。石墨烯具有优良的光学特性,化学惰性以及荧光猝灭效应,自被发现以后一直是光学微纳器件中的一大热门材料。石墨烯还可以有效分离探针分子与基底,优化拉曼光谱质量,因此广泛应用于SERS研究领域。同时石墨烯可以有效隔绝金属纳米结构与空气的直接接触防止金属纳米结构被氧化而失效,也可以催化氧化银的脱氧反应提升SERS基底的稳定性。在石墨烯/金属纳米复合结构SERS基底在制备过程中,受到金属膜的种类、厚度参数、气体种类、退火时间、温度和气压等因素的影响,制备的金属纳米结构形貌存在很大差异。石墨烯的拉曼光谱会因为应力和掺杂导致其拉曼特征峰出现不同程度的增强,移动以及展宽。（1）采用真空热蒸镀法和高温退火法制备石墨烯/银纳米复合结构SERS基底,建立了金属纳米颗粒成型机理的模型,从孔洞形成、孔洞生长、金属纳米岛形成三个阶段分析了金属纳米粒子的成型过程,实验沉积5,10,15以及20 nm的银薄膜,退火后银纳米结构的覆盖率分别为~35.1%,~24.4%,~30%以及~96.0%,在沉积银薄膜样品上使用湿法转移石墨烯,退火处理后发现石墨烯阻止了银纳米岛的形成过程;（2）理论分析了银薄膜厚度、石墨烯覆盖对复合结构的几何形貌、拉曼增强特性的影响,石墨烯由于其具有较高的杨氏模量和表面张力,可以有效抑制退火过程中银薄膜向纳米粒子转变的过程,从而实现对复合结构表面形貌的调控;（3）实验研究了银纳米粒结构形貌对石墨烯拉曼光谱的影响,并理论分析了蒸镀不同银薄膜厚度的样品对石墨烯的拉曼光谱增强,移动以及展宽影响的具体原因。     

Preparation and characterization of thermally evaporated titanium phthalocyanine dichloride thin films

Titanium phthalocyanine dichloride (TiPcCl₂) thin films are prepared on glass substrates by vacuum-sublimation technique. The optical constants of thin films are obtained by means of thin film spectrophotometry. Planar structures for the study of electrical properties are fabricated with TiPcCl₂ as active layer and silver as the contact electrodes. The effects of post-deposition annealing on the optical band gap have been studied. The optical transition is found to be direct allowed in nature. The invariance in the optical band gap shows the thermal stability of the material. The activation energies are determined using the Arrhenius plots between electrical conductivity and inverse temperature. The variation in activation energy with post-deposition annealing is investigated. The unit cell dimensions of TiPcCl₂ thin films are also determined by indexing the powder diffraction data. The variations of the surface morphology and grain size with annealing have also been studied.     

Regrowth of ZnO thin film with high surface flatness and enhanced optical properties on annealed buffer layers by rf sputtering deposition

We report a study on improving the surface flatness, optical properties, and crystallinity of ZnO thin films by rf sputtering deposition. ZnO thin films grown on sapphire substrate were first exposed to post-growth annealing, and then used to regrow high-quality ZnO thin films on top. Under the same deposition conditions, the regrown ZnO layers showed much improved crystallinity, surface flatness and enhanced optical properties. The effect of the annealed layer in improving the quality of the ZnO thin film is discussed in terms of characterization results from crystal orientation, surface morphology, and photoluminescence. It was clearly observed that, during the annealing process, the ZnO grains coalesced to form larger grains and smoother surfaces, with better crystallinity and fewer defects, which resulted in the much improved quality of the regrown ZnO thin films.     

Reactive Solid State Dewetting: Interfacial Cavitation in the System Ag-Ni-O

Micron thick silver films, vapour deposited onto high purity polycrystalline nickel substrates, dewet the substrate after high temperature annealing in oxygen rich atmospheres, while the films remain stable after annealing at the same temperature in a nitrogen atmosphere. Dewetting occurs when a nickel oxide layer is formed at the silver-nickel interface as a consequence of oxygen diffusion through the silver film.The sensitivity of the dewetting process on various parameters such as the annealing: temperature, time and oxygen partial pressure has been determined.Scanning Electron Microscopy (SEM) of cross-sections reveal that the main mechanism of dewetting at short annealing time is the nucleation of cavities at the Ag-NiO interface which grow towards the free surface of the Ag film. They are formed not only at Ag grain boundaries and triple junctions but also in the core of Ag grains. Such cavities do not occur when the Ag film is deposited onto a NiO single crystal. We propose a simple model for the cavitation: a vacancy supersaturation is sustained in Ag, at the Ag-NiO interface, as a result of oxygen consumption by the oxidation reaction. In regions of fast oxidation, the vacancy supersaturation is large enough to promote the nucleation and growth of interfacial cavities. The model qualitatively accounts for all the observed trends; quantitatively, on top of the vacancy supersaturation, extra-contributions to the driving force for cavitation must be invoked.     

Thermal stability of Ag films in air prepared by thermal evaporation

The thermal stability of silver films in air has been studied. Pure Ag films, 250 nm in thickness, were prepared on glass substrates by thermal evaporation process, and subsequently annealed in air for 1 h at temperatures between 200 and 400 °C. The structure and morphology of the samples were investigated by X-ray diffraction, Raman spectra and atomic force microscopy. It is found that the crystallization enhances for the annealed films, and film surface becomes oxidized when annealing temperature is higher than 350 °C. The electrical and optical properties of the films were studied by van der Pauw method and spectrophotometer, respectively. Reflectance drops sharply as Ag films are annealed at temperatures above 250 °C. Film annealed at 250 °C has the maximum surface roughness and the minimum reflectance at 600 nm optical wavelength. Film annealed at 200 °C has the minimum resistivity, and resistivity increases with the increasing of the annealing temperature when temperature is above 200 °C. The results show that both oxidization on film surface and agglomeration of silver film result in infinite of electrical resistivity as the annealing temperature is above 350 °C.     

基于铝浸润层的超薄银透明导电薄膜研究北大核心CSCD

超薄银薄膜具有高柔韧性和优良的光电性能,是用于透明导电电极的潜在材料。通过电阻热蒸发技术以金属铝作为浸润层制备超薄银透明导电薄膜。引入铝浸润层降低银薄膜的阈值厚度,使银薄膜在K9玻璃基底上以尽可能低的厚度达到连续。对不同厚度铝浸润层上银薄膜方块电阻进行测试,经SEM图像验证后得出,1 nm铝浸润层对银薄膜具有较好的浸润效果。随后采用相同的工艺在1 nm铝浸润层上制备了不同厚度的银薄膜,透过率和方阻测试结果表明,1 nm铝浸润层上制备的10 nm银薄膜方阻值可达到13Ω/,其在0.4μm~2.5μm波段内透过率可达到50%以上。     

Effect of Near Ultraviolet Irradiation on Changes in Island Metallic Films during Thermal Annealing

Optics and Spectroscopy - The effect of low-intensity near ultraviolet irradiation and subsequent thermal annealing on the surface morphology of gold and silver granular films was investigated. It...     

银表面光学二次谐波参数的研究

本文测量了几种玻璃-银膜界面反射二次谐波随入射光偏振角的变化,测量了超高真空中多晶银基底上冷凝银膜表面退火前后的反射二次谐波,以及超高真空中纯度为99.99%多晶银表面的反射二次谐波,计算了垂直和平行表面谐波电流参数a、b,得到对棱镜-银界面b=-0.97;α=2.1,多晶银表面α=-9,冷凝银膜退火前后α分别为7和-5.结果表明.α对表面状况极为敏感.     

相变记录介质GaSb薄膜的光学性质、微观结构及其记录性质

本文系统地研究了热致相变对射频磁控溅射的GaSb薄膜光学性质和微观结构的影响.发现在270℃左右具有连续无序网络结构的非晶GaSb薄膜发生相变,转变为具有立方晶系的多晶薄膜,其晶格常数为α_0=0.6095nm,相变后薄膜的吸收减小,GaSb薄膜的光能隙由0.7eV升高为0.94eV.用精密四探针法测量了GaSb薄膜电阻随温度变化的过程.给出了GaSb薄膜的一次写入记录特性,研究了光致晶化记录畴的微结构.     

Fine structures and switching of electrical conductivity in labyrinth silver films on sapphire

Changes in electrical resistance of silver films were measured in the range from 10¹³ to 10³ Ω during thermal deposition on sapphire in a high vacuum, after the deposition over time, and under an applied voltage. The dependences of the electrical resistance of the films on their thickness and deposition rate were determined. It was established that, with an increase in the film thickness from 2 to 10 nm during the deposition at rates of 0.6 and 0.1 Å/s, the resistance decreases by 7.5 and 4 orders of magnitude, respectively. The measured dependences of the resistance on the deposition time were found to be close to exponential. The room-temperature resistance of 10-nm-thick films deposited at different rates changed spontaneously by 3–4 orders of magnitude in different ways: the resistance of the slowly deposited films spontaneously increased, whereas in the rapidly deposited films, it spontaneously decreased. After fine annealing, the steady-state resistance changed also differently: it increased by 2 orders of magnitude in the former case and by 9 orders of magnitude in the latter case. Under voltages above 5 V, the resistance of the rapidly deposited films abruptly decreased from ～10¹² to ～10⁶ Ω, and these films became ohmic. After fine annealing, they became again high-ohmic. Under voltages above 5 V, the high-ohmic films thus obtained became again low-ohmic. This cycle of electrical conductivity switching was reproduced many times. The observed phenomena were explained in the framework of the hypothesis of the formation of fine metastable structures in channels of labyrinth films, namely, protrusions and bridges that bring together the boundaries of islands and connect them into conducting clusters, respectively.     

Mechanical and optoelectric properties of post-annealed fluorine-doped tin oxide films by ultraviolet laser irradiation

The fluorine-doped tin oxide (FTO) thin film deposited on a soda-lime glass substrate was annealed by a defocus ultraviolet (UV) laser irradiation at ambient temperature. The mechanical and optoelectric properties of FTO films annealed by using the various laser processing parameters were reported. After the FTO films were subjected to laser post-annealing, the microhardness were slightly less but the reduced modulus values were larger than that of unannealed FTO films, respectively. The average optical transmittance in the visible waveband slightly increased with increasing the laser annealing energy and scan speed. Moreover, all the sheet resistance of laser annealed films was less than that of the unannealed ones. We found that the sheet resistance decrease was obviously influenced by annealing. The suitable annealing conditions could maintain the film thickness and relief the internal stress generated in the film preparation process to improve the electrical conductivity via decreasing laser energy or increasing scan speed.     

激光辐照对热退火金属/掺氟二氧化锡透明导电薄膜光电性能的影响

采用532 nm纳秒脉冲激光对热退火的铝(Al)/掺氟二氧化锡(FTO)、铜(Cu)/FTO和银(Ag)/FTO三种双层复合薄膜表面分别进行处理, 结果显示薄膜样品的光电性能都得到提高.其中, 热退火Ag/FTO薄膜的平均透光率(400–800 nm)增幅最大, 从72.6%提高到80.5%, 主要是由于其表面产生了具有减反增透作用的光栅结构.激光辐照后热退火Ag/FTO薄膜的导电性也略有提高, 其方块电阻从5.6 Ω/sq下降到5.3 Ω/sq, 原因主要是激光辐照的热效应造成的退火作用使薄膜的晶粒尺寸增大, 减少了晶界散射而使载流子迁移率提高.计算结果显示, 激光辐照后热退火Ag/FTO薄膜的品质因子从0.73×10^-2Ω^-1增大为2.16×10^-2Ω^-1, 表明其综合光电性能得到显著提高.激光辐照可同步实现薄膜表面光栅结构的制备和附加退火作用, 这为金属层复合透明导电薄膜光电性能的综合优化提供了新的思路.     

基片温度和退火对CdIn2O4薄膜光学性质和载流子浓度的影响

对射频反应性溅射Cd In合金靶制备的透明导电CdIn2 O4薄膜 ,研究了基片温度及沉积后在氩气流中退火对薄膜的透射、反射和吸收光谱 ,光学常数和载流子浓度的影响。结果表明 :提高基片温度减少了薄膜的载流子浓度 ,退火增加了薄膜的载流子浓度。随着基片温度提高 ,薄膜折射率n和消光系数κ的短波峰将逐渐蓝移 ,而退火使其出现红移。基片温度和退火对薄膜光学常数的影响与其对薄膜载流子浓度的影响是一致的。在制备CdIn2 O4这样一种对于沉积方法和沉积条件极为敏感的透明导电薄膜的沉积过程中 ,这一现象对于实时监控具有极为重要的意义。     

Electrical properties, structure, and surface morphology of poly(p-xylylene)–silver nanocomposites synthesized by low-temperature vapor deposition polymerization

The crystalline structure, surface morphology, electrical, and optical properties of thin films of nanocomposites consisting of silver nanoparticles embedded in poly(p-xylylene) matrix prepared by low-temperature vapor deposition polymerization were studied. Depending on the filler content, the average size of silver nanoparticles varied from 2 to 5 nm for nanocomposites with 2 and 12 vol.% of silver, correspondingly. The optical adsorption in the visible region due to surface plasmon resonance also exhibited a clear correlation from silver content, revealing a red shift of the adsorption peak with the increase of the metal concentration. The temperature dependences of the dc resistance of pure p-xylylene condensate and p-xylylene–silver cocondensates during polymerization as well as temperature dependences of the formed poly(p-xylylene)–silver nanocomposites were examined. The observed variation of the temperature dependences of electrical resistance as a function of silver concentration are attributed to different conduction mechanisms and correlated with the structure of the composites. The wide-angle X-ray scattering and AFM measurements consistently show a strong effect of silver content on the nanocomposite structure. The evolution of the size of silver nanoparticles by thermal annealing was demonstrated.     

Plasma resonance absorption in interfacial photoemission from very thin silver films on Cu(111)

Very thin silver films deposited on a Cu(111) substrate were studied with the photoemission-into-electrolyte technique. The optical resonance absorption at the silver bulk plasma frequency was observed for films thicker than two monolayers. The correlation between optical absorption and photoemission intensities depends in a complicated fashion on the photon energy as well as the film thickness.