基底温度对直流磁控溅射制备氮化铜薄膜的影响研究

采用反应直流磁控溅射镀膜法,在氮气分压为0.9Pa、不同基底温度下、玻璃基底上制备了纳米多晶Cu3N薄膜,并研究了基底温度对薄膜结构和性能的影响。结果表明,当基底温度为100℃及以下时,薄膜以[111]方向择优生长为主;在150℃及200℃时,薄膜以[100]方向择优生长为主;250℃时开始出现Cu的[111]方向生长,300℃时已完全不能形成Cu3N晶体,只有明显的Cu晶体。随基底温度的升高,薄膜的沉积速率在13～28nm/min呈U型变化,低温和高温时较高,150℃时最低;薄膜的电阻率显著降低;薄膜的显微硬度先升后降,100℃时显微硬度最大。     

氧化物La-Ca-Mn-O巨磁电阻薄膜的制备及其结构特性的研究

采用磁控溅射方法在ＺｒＯ２（００１）、Ｓｉ（００１）和玻璃衬底上成功地制备了ＬａＣａＭｎＯ（以下简称为ＬＣＭＯ）巨磁电阻薄膜。Ｘ－射线分析表明，ＺｒＯ２的晶格常数与ＬＣＭＯ的晶格常数失配虽然较大，仍可得到较好的ＬＣＭＯ薄膜。在Ｓｉ片上难以制备出致密完整的ＬＣＭＯ薄膜，其原因有待查明。玻璃衬底上可以获得纯相的ＬＣＭＯ巨磁电阻薄膜，在ＺｒＯ２衬底上制备的ＬＣＭＯ薄膜，其巨磁电阻效应在１５０Ｋ，３０００Ｇａｕｓ下达１３％左右。     

Initiated Chemical Vapor Deposition: A Versatile Tool for Various Device Applications

Advances in device technology have been accompanied by the development of new types of materials and device fabrication methods. Considering device design, initiated chemical vapor deposition (iCVD) inspires innovation as a platform technology that extends the application range of a material or device. iCVD serves as a versatile tool for surface modification using functional thin film. The building of polymeric thin films from vapor phase monomers is highly desirable for the surface modification of thermally sensitive substrates. The precise control of thin film thicknesses can be achieved using iCVD, creating a conformal coating on nano‐, and micro‐structured substrates such as membranes and microfluidics. iCVD allows for the deposition of polymer thin films of high chemical functionality, and thus, substrate surfaces can be functionalized directly from the iCVD polymer film or can selectively gain functionality through chemical reactions between functional groups on the substrate and other reactive molecules. These beneficial aspects of iCVD can spur breakthroughs in device fabrication based on the deposition of robust and functional polymer thin films. This review describes significant implications of and recent progress made in iCVD‐based technologies in three fields: electronic devices, surface engineering, and biomedical applications.

     

Electrochemical characterization of carbon nanotube forests grown on copper foil using transition metal catalysts

Growth of vertical, multiwalled carbon nanotubes (CNTs) on bulk copper foil substrates can be achieved by sputtering either Ni or Inconel thin films on Cu substrates followed by thermal chemical vapor deposition using a xylene and ferrocene mixture. During CVD growth, Fe nanoparticles from the ferrocene act as a vapor phase delivered catalyst in addition to the transition metal thin film, which breaks up into islands. Both the thin film and iron are needed for dense and uniform growth of CNTs on the copper substrates. The benefits of this relatively simple and cost effective method of directly integrating CNTs with highly conductive copper substrates are the resulting high density of nanotubes that do not require the use of additional binders and the potential for low contact resistance between the nanotubes and the substrate. This method is therefore of interest for charge storage applications such as double layer capacitors. Inconel thin films in conjunction with Fe from ferrocene appear to work better in comparison to Ni thin films in terms of CNT density and charge storage capability. We report here the power density and specific capacitance values of the double layer capacitors developed from the CNTs grown directly on copper substrates.     

Composition controlling of KNbO3 thin films prepared by pulsed laser deposition

The composition of KNbO₃ thin films prepared by pulsed laser deposition is crucially influenced by the deposition configuration. In the present study, the composition of KNbO₃ thin films grown on Si (100) substrates by pulsed laser ablation was tried to be controlled by adjusting the target-substrate distance and the oblique angle of substrate from the plume axial direction. It was found that the K deficiency in the films can be effectively avoided by setting the substrate at an appropriate oblique angle from the plume axial direction. The stoichiometric KNbO₃ thin films with a K/Nb molar ratio of 0.98 were successfully obtained, where the substrates were set at an oblique angle of 3-12° from the plume axis while the target-substrate distance was kept at 40 mm.     

Heating of polymer substrate by discharge plasma in radiofrequency magnetron sputtering deposition

The substrate used for the thin film deposition in a radiofrequency magnetron sputtering deposition system is heated by the deposition plasma. This may change drastically the surface properties of the polymer substrates. Deposition of titanium dioxide thin films on polymethyl methacrylate and polycarbonate substrates resulted in buckling of the substrate surfaces. This effect was evaluated by analysis of atomic force microscopy topography images of the deposited films. The amount of energy received by the substrate surface during the film deposition was determined by a thermal probe. Then, the results of the thermal probe measurements were used to compute the surface temperature of the polymer substrate. The computation revealed that the substrate surface temperature depends on the substrate thickness, discharge power and substrate holder temperature. For the case of the TiO₂ film depositions in the radiofrequency magnetron plasma, the computation indicated substrate surface temperature values under the polymer melting temperature. Therefore, the buckling of polymer substrate surface in the deposition plasma may not be regarded as a temperature driven surface instability, but more as an effect of argon ion bombardment.     

电流密度和衬底处理方式对CaMoO4薄膜电化学制备的影响

主要研究了利用恒电流电化学技术制备CaMoO4薄膜的工艺中,电流密度和衬底处理方式对薄膜制备的影响.研究发现,增大阳极氧化电流密度会加快薄膜的生长速度,但会加剧晶粒团簇生长的趋势、减弱薄膜与衬底的附着力和薄膜的均匀性;衬底的不同处理方式对薄膜晶粒的生长速度、沉积方式、均匀性等有较大的影响,在抛光衬底上薄膜的沉积速度比酸腐蚀和粗磨的衬底要快,且不易造成晶粒的团簇生长.结果表明,CaMoO4薄膜的电化学沉积,应在抛光衬底上进行;电流密度控制在0.5mA/cm2附近比较好.     

Substrate dependent structural and magnetic properties of pulsed laser deposited Fe3O4 thin films

Nanocrystalline iron oxide thin films have been deposited on various substrates such as quartz, MgO(100), and Si(100) by pulsed laser deposition technique using excimer KrF laser (248 nm). The orientations, crystallite size and lattice parameters were studied using X-ray diffraction. The XRD results show that the films deposited on MgO and Si substrates are highly oriented and show only (400) and (311) reflections respectively. On the other hand, the orientation of the films deposited on quarts substrate changed from (311) to (400) with an increase in the substrate temperature from 400 degrees C to 600 degrees C, indicating thereby that the film growth direction is highly affected with nature of substrate and substrate temperature. The surface morphology of the deposited films was studied using Atomic Force Microscopy (AFM) and spherical ball like regular features of nanometer size grains were obtained. The magnetic properties were studied by Superconducting Quantum Interference Device (SQUID) magnetometer in the magnetic field +/- 6 Tesla. The magnetic field dependent magnetization (M-H) curves of all the Fe3O4 thin films measured at 5 K and 300 K show the ferrimagnetic nature. The electrochemical sensing of dopamine studied for these films shows that the film deposited on MgO substrate can be used as a sensing electrode.     

X-ray and transmission electron microscopy structural characterization of multifunctional Perovskite thin films

Different multifunctional (PbTiO₃, Sm_0.6Nd_0.4NiO₃, NdMnO₃) thin films were grown by metalorganic chemical vapor deposition (MOCVD) technique on SrTiO₃ and LaAlO₃ substrates. Transmission electron microscopy (TEM) and X-ray diffraction measurements reveal that almost single crystalline thin films can be epitaxially grown on the top of substrates. The relationship between the crystallographic orientation of the films and those of the substrates were determined by reciprocal space mapping and TEM analyses. PbTi03 thin films appear to be under tensile or compressive strain according to the different mismatch of their cell parameter with those of the substrate. Relaxation mechanism as a function of the film thickness arises from coexistence of different type of domains and size and strain effect are analyzed. SmNiO₃ thin films present diffuse scattering strikes and are less well organized when compared to PbTi0₃ thin films. Different domains are observed as well as an additional parasitic phase close to NiO. Its regular distribution can be associated to reduced transport properties. Preliminary observations on NdMnO₃ thin films shows that an amorphous phase is obtained during MOCVD that can be transformed in a single crystalline film by annealing. The films are under tensile or compressive strain according to the different mismatch of their cell parameter with those of the substrate. Magnetic properties are investigated.     

Surface-enhanced Raman spectroscopy of the growth of ultra-thin organosilicon plasma polymers on nanoporous Ag/SiO2-bilayer films

A new method for the synthesis of thin bilayer films as surface-enhanced Raman spectroscopy (SERS) active substrates was developed which is based on the combination of plasma polymerization, plasma calcination and Ag-film deposition by means of physical vapor deposition. The surface morphology of prepared substrates was characterized by field emission scanning electron microscopy, atomic force microscopy and electrochemical impedance spectroscopy. These substrates lead to high surface enhancement factors proven by the spectroscopic analysis of adsorbed Trans-1,2 bis-(4-pyridyl) ethylene molecules. By this preparation technique, SERS-active films can be deposited on any substrate. The new SERS substrates were successfully applied to study the growth of ultra-thin hexamethyldisiloxane plasma polymer films. The Raman intensity of the CH-stretching vibration was studied as a function of the film thickness. The surface enhancement decreased sharply at about 20 nm. The resulting increase in the intensity of Raman peaks for thin adsorbed plasma polymer films was observed to be a combination of the electromagnetic enhancement mechanism and the high surface area increase of the rough Ag-surface.     

Dünne Schichten durch Deposition unter streifenden Einfall

Micro‐ and nanostructured thin films by Glancing angle deposition Physical vapour deposition under conditions of obliquely incident flux and limited adatom diffusion results in films with a columnar microstructure. These columns will be oriented toward the vapour source. An additional substrate rotation can be used to sculpt the columns into various morphologies (slanted and vertical posts, chevrons, screws or spirals). With this glancing angle deposition (GLAD) technique can prepared porous thin films with engineered structures from a variety of dielectric, semiconducting and metallic materials. The paper presents the In this paper the physical fundamentals of the GLAD technique are introduced, the production of micro‐ and nanostructures of different morphology on non‐patterned and patterned substrates is demonstrated and some possible applications of this new deposition technique are introduced.     

Magnetic properties of oxidized iron thin films grown by sputtering at very low temperatures

Iron thin films have been grown by DC magnetron sputtering using Si(100) wafers as substrates, and then oxidized in a well-controlled oxygen atmosphere in the vacuum chamber. Film thickness is about 50 nm, and grains forming these samples do not exceed 20 nm. In order to control structural properties such as size and shape of these grains, growth conditions can be modified, like deposition rate or substrate temperature, varying from 150 to 300 K. Two sets of samples have been prepared considering deposition rate: (i) films grown at 0.6 nm/min and (ii) at 1.2 nm/min. In order to prevent iron films from natural oxidation, all the sample series were covered with a gold layer. Analysis of their magnetic behaviour shows a strong dependence on grain size and temperature, resulting in a more effective oxidation for samples prepared at higher deposition rates and lower substrate temperatures, which behaves as a Fe/Fe oxide granular system.     

Epitaxy of cubic boron nitride on (001)-oriented diamond

Cubic boron nitride (c-BN), although offering a number of highly attractive properties comparable to diamond, like hardness, chemical inertness and a large electronic bandgap, up to now has not found the attention it deserves. This mostly has to do with preparational problems, with easy chemical routes not available and, instead, the necessity to apply ion-bombardment-assisted methods. Hence, most of the c-BN samples prepared as thin films have been nanocrystalline, making the prospect of using this material for high-temperature electronic applications an illusion. Although heteroepitaxial nucleation of c-BN on diamond substrates has been demonstrated using the high-pressure-high-temperature technique, none of the low-pressure methods ever succeeded in the epitaxial growth of c-BN on any substrate. Here, we demonstrate that heteroepitaxial c-BN films can be prepared at 900 degrees C on highly (001)-oriented diamond films, formed by chemical vapour deposition, using ion-beam-assisted deposition as a low-pressure technique. The orientation relationship was found to be c-BN(001)[100]||diamond(001)[100]. High-resolution transmission electron microscopy additionally proved that epitaxy can be achieved without an intermediate hexagonal BN layer that is commonly observed on various substrates.     

Study of adhesion of carbon nitride thin films on medical alloy substrates

The adhesion improvement of biocompatible thin films on medical metal alloy substrates commonly used for joint replacement implants is studied. Diamond-like carbon (DLC) and carbon nitride (CN) thin films are, because of their unique properties such as high hardness, wear resistance and low friction coefficient, candidates for coating of medical implants. However, poor adhesion on substrates with high thermal expansion coefficient limits their application. We deposited CN films by pulsed DC discharge vacuum sputtering of graphite target on CoCrMo and Ti6Al4V substrates. Surface nitridation of the substrate, changing the deposition parameters and use of interlayer led to improved adhesion properties of the films. Argon and nitrogen gas flow, thickness of the film and frequency of the deposition pulses had significant influence on the adhesion to the substrate. Properties of deposited films were analyzed using Scanning Electron Microscopy, Raman spectroscopy and tribology tests.     

Oxygen-ion-assisted deposition of thin gold films

Thin gold films have been deposited on glass and silicon substrates using ion-assisted deposition techniques. The adhesion of the films to the substrates is assessed by a scratch test. Deposition assisted by 100 eV-1 keV oxygen ions yields highly adhesive films that can only be removed by damaging the substrate. Argon and hydrogen ions produce films with relatively poor adhesion. The results show that the reflectance of oxygen-assisted films is reduced by trapping of the oxygen in the gold but no bulk chemical or structural changes are detected. It is proposed that a thin stable layer of gold oxide is formed during film growth and diffuses into the substrate, providing a strong bond for subsequent film deposition. Highly adhesive films with bulk optical properties are deposited on glass and silicon using oxygen-ion assistance only to the point of continuous film formation.     

Dependence of the electrical and optical properties on the bias voltage for ZnO:Al films deposited by r.f. magnetron sputtering

Aluminum-doped zinc oxide (ZnO:Al) thin films were deposited on glass, polycarbonate (PC), and polyethylene terephthalate (PET) substrates by r.f. magnetron sputtering. The substrate dc bias voltage varied from 0 V to 50 V. Structural, electrical and optical properties of the films were investigated. The deposition rate of ZnO:Al films on glass substrate initially increased with the bias voltage, and then decreased with further increasing bias voltage. It was found that the best films on glass substrate with a low as 6.2 × 10^− 4 Ω cm and an average transmittance over 80% at the wavelength range of 500-900 nm can be obtained by applying the bias voltage of 30 V. The properties of the films deposited on polymer substrate, such as PC and PET, have a similar tendency, with slightly inferior values to those on glass substrate.     

不锈钢衬底两面同时液相电沉积类金刚石薄膜及其沉积机理研究

为了利用液相电沉积技术实现在金属衬底表面全方位电沉积类金刚石(DLC)薄膜,采用不同尺度的不锈钢片作为衬底,在表面电沉积了DLC薄膜,利用X射线光电子能谱、Raman光谱和扫描电子显微镜分别对衬底两面薄膜的化学成分、微观结构和表面形貌进行了分析。结果显示:对于尺度大于石墨阳极的不锈钢衬底,仅在衬底正对着阳极的一面实现了DLC薄膜的沉积;而对于尺度小于阳极的不锈钢衬底,在衬底两面都有DLC薄膜沉积,且两面薄膜结构相似,形貌相近。利用准静态电场理论对实验结果进行了解释,提出在金属衬底表面实现液相电沉积DLC薄膜的前提条件是存在垂直于衬底表面的电场分量,为进一步实现在复杂形状的导电性衬底表面沉积DLC薄膜提供了理论依据。     

Effect of target properties on transparent conducting impurity-doped ZnO thin films deposited by DC magnetron sputtering

For the purpose of using transparent conducting impurity-doped ZnO thin films in liquid crystal display (LCD) applications, the relationship between the properties of dc magnetron sputtering (dc-MS) deposited thin films and the properties of the oxide targets used to produce them is investigated. Both Al-doped and Ga-doped ZnO (AZO and GZO) thin films were deposited on glass substrates using a dc-MS apparatus with various high-density sintered AZO or GZO disk targets (diameter of about 150 mm); the target and substrate were both fixed during the depositions. Using targets with a lower resistivity results in attaining more highly stable dc-MS depositions with higher deposition rates and lower arcing. In addition, dc-MS depositions using targets with a lower resistivity produced improvements in resistivity distribution on the substrate surface. It was found that the oxygen content in deposited thin films decreased as the oxygen content of the target used in the deposition was decreased. As a result, the dc-MS deposition of transparent conducting impurity-doped ZnO thin films suitable for LCD applications requires the preparation of significantly reduced AZO and GZO targets with low oxygen content.     

Effects of sapphire substrates surface treatment on epitaxial ZnO thin films grown by MOCVD

The surface treatment effects of sapphire substrate on the quality of epitaxial ZnO thin films grown by metal-organic chemical vapor deposition (MOCVD) were studied. The sapphire substrates have been investigated by means of atomic force microscopy (AFM) and X-ray diffraction rocking curves (XRCs). The results show that sapphire substrate surfaces have the best-quality by CMP with subsequent chemical etching. The surface treatment effects of sapphire substrate on the ZnO thin films were examined by X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL) measurements. Results show that the intensity of (002) diffraction peak of ZnO thin films on sapphire substrates treated by CMP with subsequent chemical etching is strongest. FWHM of (002) diffraction peak is narrowest and the intensity of UV peak of PL spectrum is strongest, indicating surface treatment on sapphire substrate preparation may improve ZnO thin films crystal quality and photoluminescent property.     

Deposition of conductive materials on textile and polymeric flexible substrates

This paper describes the study, analysis and selection of textile and similar materials to be used as flexible substrates for thin conductive film deposition, in the context of integrating electronics into textiles. Kapton^® polyimide was chosen as reference substrate material, was characterized regarding mechanical and electrical properties and was used as a basis for a comparison with several textile substrates. Samples were fabricated using physical vapour deposition (thermal evaporation) to deposit a thin layer of aluminium on top of Kapton and textile substrates. The measurement of electrical resistance of the thin aluminum films was carried out using the Kelvin method. To characterize the mechanical behaviour of the substrate and aluminum film, several mechanical tests were performed and results were compared between Kapton and these textile materials. The chemical composition of the textile substrates and aluminum films as well as the continuity of the films was characterized. This selection process identified the material that was closer to the behaviour of polyimide, a flexible, but non-elastic woven textile coated on both sides with PVC.