Polyelectrolyte-mediated assembly of copper-phthalocyanine tetrasulfonate multilayers and the subsequent production of nanoparticulate copper oxide thin films

An approach to producing films of nanometer-sized copper oxide particulates, based on polyelectrolyte-mediated assembly of the precursor, copper(II)phthalocyanine tetrasulfonate (CPTS), is described. Multilayered CPTS and polydiallyldimethylammonium chloride (PDADMAC) were alternately assembled on different planar substrates via the layer-by-layer (LbL) procedure. The growth of CPTS multilayers was monitored by UV-visible spectrometry and quartz crystal microbalance (QCM) measurements. Both the UV-visible spectra and the QCM data showed that a fixed amount of CPTS could be attached to the substrate surface for a given adsorption cycle. Cyclic voltammograms at the CPTS/PDADMAC-covered gold electrode exhibited a decrease in peak currents with the layer number, indicating that the permeability of CPTS multilayers on the electrodes had diminished. When these CPTS multilayered films were calcined at elevated temperatures, uniform thin films composed of nanoparticulate copper oxide could be produced. Ellipsometry showed that the thickness of copper oxide nanoparticulate films could be precisely tailored by varying the thickness of CPTS multilayer films. The morphology and roughness of CPTS multilayer and copper oxide thin films were characterized by atomic force microscopy. X-ray diffraction (XRD) measurements indicated that these thin films contained both CuO and Cu2O nanoparticles. The preparation of such copper oxide thin films with the use of metal complex precursors represents a new route for the synthesis of inorganic oxide films with a controlled thickness.     

Preparation of nanocrystalline Cu<Subscript>2</Subscript>O thin film by pulsed laser deposition

In this paper, the synthesis of nanocrystalline copper oxides Cu₂O and CuO thin films on glass substrates using a pulsed 532 nm Nd:YAG laser is presented. Deposition of films is achieved at two different substrate temperatures. The influence of substrate temperature on the structural and optical properties of copper oxide films are discussed and analyzed. The X-ray diffraction (XRD) results show that the deposited films are crystalline in nature. Films prepared at 300 °C substrate temperature were Cu₂O and has (111) and (200) diffracted peaks, while films grown at 500 °C were CuO and has (111) and (020) planes. The morphology of deposited films were characterized by scanning electron microscope (SEM) and atomic force microscope (AFM). The optical energy gap of Cu₂O and CuO films have been determined and found to be 2.04 and 1.35 eV respectively.     

Copper carboxylate with different carbon chain lengths as metal–organic decomposition ink

The copper carboxylates with different carbon chain length (glycolate, lactate and oleate) were used to prepare the metal–organic decomposition ink. TG–MS showed that copper carboxylates underwent a two-step thermal decomposition for the conversion to elemental copper, and the organic residues after decomposition is relevant with the carbon chain length. Conductive copper films were obtained by drop coating of a copper carboxylate solution onto a glass slide followed by sintering at different temperatures. Copper carboxylates with shorter carbon chain give better conductive films. Both copper glycolate and copper lactate films begin to show conductivity after sintered at 150 °C for 60 min under nitrogen. The resistivity of the copper features with 2 μm thickness of copper glycolate and copper lactate was 23.0 ± 2 and 44.0 ± 6 μΩ cm after sintering at 250 °C for 60 min under nitrogen, respectively, with the former being about 7.4 % of the conductivity of bulk copper. X-ray photoelectron spectroscopy results showed slight surface oxidation in the sintered copper feature from these copper carboxylates. Although the conductivity of the obtained copper film needs to be improved further, the method shows some advantages over the copper nanoparticles ink, such as avoiding tedious synthesis and protection of nanoparticles, low cost, etc.     

The Role of Cuprous Oxide Seeds in the One‐Pot and Seeded Syntheses of Copper Nanowires

This paper demonstrates that Cu₂O nanoparticles form in the early stages of a solution‐phase synthesis of copper nanowires, and aggregate to form the seeds from which copper nanowires grow. Removal of ethylenediamine from the synthesis leads to the rapid formation of Cu₂O octahedra. These octahedra are introduced as seeds in the same copper nanowire synthesis to improve the yield of copper nanowires from 12% to >55%, and to enable independent control over the length of the nanowires. Transparent conducting films are made from nanowires with different lengths to examine the effect of nanowire aspect ratio on the film performance.     

Controlled Synthesis of Graphene on Copper Using the Method of Implantation of Carbon Recoil Atoms

Technical Physics Letters - A method of graphene synthesis on the surface of copper foil by cold implantation of carbon recoil atoms is considered. It is established that monolayer graphene films...     

Semi-conductive properties of passive films formed on copper in chromate solutions

The semi-conductive properties of passive films formed on copper in chromate solutions were investigated by means of capacitance measurements. The effects of the formation potential and temperature, chloride and chromate concentration in electrolyte solution, as well as measured frequency on the semi-conductive properties of passive films were studied. The results show that the passive films formed on copper display n-type semi-conductive characteristics. The slopes of the straight lines in Mott-Schottky plots decrease with moving the formation potential toward positive, increasing the chloride ion concentration, decreasing the formation temperature and the chromate solutions concentration. Moreover, the initial grain size of copper surface impacts remarkably on the semi-conductive properties. The donor density of the passive films formed on ultra-fine grained (UFG) copper is higher than that of the passive films on coarse-grained (CG) copper.     

铜基体上CVD金刚石厚膜的制备

用MWCVD方法在无预处理铜基体上获得了金刚石薄膜和厚膜。所得金刚石膜从基体上自动脱落,但形貌分析和Ramman分析表明,所得金刚石膜具有较好的质量。因此铜是制备金刚石厚膜的理想基体材料。     

Formation of small volatile complexes during copper film growth by the combined synthesis-transport method

Stable heterogeneous synthesis products in combined synthesis-transport processes for the growth of thin copper films have been studied by ESR, X-ray photoelectron, and IR spectroscopies. The results demonstrate that the synthesized volatile compounds condensed on solid surfaces have the form of formate-like metal complexes of copper(I). We have identified the mechanisms underlying the formation of volatile monomeric metal complexes on the surface of copper-containing precursor particles and the mechanism of the thermal decomposition of metal complexes on a heated substrate.     

Nanostructured copper and copper oxide thin films fabricated by hydrothermal treatment of copper hydroxide nitrate

Metallic copper and copper oxide thin films were fabricated on surface of glass slide substrates. Copper oxide thin films were prepared by a hydrothermal method using an α-phase layered hydroxide, copper hydroxide nitrate as a precursor. Morphology, thickness and crystallite size of the obtained copper oxide thin films changed by changing the time of hydrothermal treatment. Accordingly, the copper oxide thin films showed various water contact angles and optical band gaps. As, the optical band gap of the nanostructured copper oxide thin films increased with an increase in hydrothermal time from 1.85 to 2.95 eV. Moreover, the water contact angles changed from 16.4 to 38.8° by changing the hydrothermal time. By a reductive hydrothermal-treatment route, the copper oxide thin film was reduced to metallic copper thin film without any particle growth.     

Irreversible hydrogen effects on resistivity of sputtered copper films

Can hydrogen trapped within the lattice of copper film produce irreversible effects on the electrical resistivities of copper film at room temperature? In order to answer this question, copper films were sputtered in the presence of hydrogen and resistivities were measured in vacuum at room temperature. A series of sputtering depositions were carried out at different hydrogen partial pressures to confirm irreversible hydrogen effects. Films sputtered in argon only, were used as controls. The electrical resistivities of copper films were measured as a function of hydrogen partial pressure. Saturation is reached for the electrical resistivity in high hydrogen partial pressures. The saturation is at around 5.0% hydrogen partial pressure of total sputtering pressure. The electrical resistivities of copper films are lowered irreversibly by hydrogen, because the films were sputtered in the gas mixtures of argon and hydrogen and the electrical resistivities of films were measured in the air. The sputtering rate decreases as the hydrogen partial pressure increases. The sputtering rate is found to be proportional to the average mass of the incident ion.     

磁控溅射工艺参数对涤纶织物表面沉积铜膜性能的影响

在室温条件下采用射频磁控溅射法在涤纶平纹机织物表面沉积纳米Cu薄膜,借助原子力显微镜(AFM)观察镀膜前后样品表面变化。通过分别改变镀膜时间、溅射功率和气体压强,研究其对样品透光性和导电性的影响。实验结果表明,经Cu镀层处理的涤纶平纹织物对紫外光和可见光的吸收能力明显优于原样。溅射压强增加,透光性能增强,铜膜方块电阻增加,导电性能减弱;镀膜时间延长和溅射功率增加,样品透射率降低,屏蔽紫外线和可见光效果明显,在溅射时间接近15min和溅射功率增加到120W后,样品屏蔽效果不明显,铜膜方块电阻随溅射功率增加而减小,导电性能增强。     

电沉积铜薄膜中的内应力与织构特征

利用X射线衍射方法分析了电沉积铜薄膜的内应力及其织构特征.结果表明,随薄膜厚度的增加,薄膜内应力增大.电沉积铜薄膜具有较强的(220)丝织构,随着铜薄膜内应力的增加,(220)丝织构增强,同时叠加有板织构的特征.     

Structural studies of copper sulfide films: effect of ambient atmosphere

We examined the structural properties of copper sulfide films as a function of the sulfurization time of 70-nm-thick Cu films. Copper sulfide films with various phases such as mixed metallic Cu-chalcocite, chalcocite, roxbyite, and covellite phases were formed with increasing sulfurization time. To evaluate the structural stability of various films, all the films were exposed to the ambient atmosphere for the same amount of time. Although the phase structure and stoichiometry of the films were maintained at a greater depth, the near-surface region of the films was oxidized and covered with overlayers of oxide, hydroxide, and/or sulfate species due to the exposure and reaction with the ambient atmosphere. The oxygen uptake and its reactivity with the copper sulfide film surfaces were enhanced with increasing sulfur content of the films. In addition, the type of divalent state of copper formed on the film surfaces depended on the phase structure, composition, and stoichiometry of the films.     

表面沉积铜纳米颗粒的细菌纤维素/壳聚糖交联复合膜的制备及其抗菌性能研究

通过戊二醛交联制备了细菌纤维素/壳聚糖复合材料,并采用磁控溅射技术在交联复合膜表面沉积铜(Cu)纳米颗粒。利用扫描电子显微镜观察纳米纤维膜表面形貌,采用傅里叶红外光谱仪、热重分析仪和X射线衍射仪比较交联复合前后以及镀铜前后复合膜基本化学结构、热稳定性和晶面结构的变化。通过能量色散X射线光谱对壳聚糖和铜在复合膜表面的分布情况进行表征。同时借助抗菌实验探究复合膜对金黄色葡萄球菌和大肠杆菌的抗菌能力。结果表明:壳聚糖与细菌纤维素发生了有效交联,改变了细菌纤维素的基本形貌、化学结构、晶体形态以及热学性能,并且镀铜后交联复合膜的抗菌性能得到了明显的提升(膜与细菌接触20min,对金黄色葡萄球菌和大肠杆菌的抗菌效果均达到了99.999%)。     

磁控溅射制备紧固件防咬死涂层的厚度均匀性研究

为了研究磁约束聚变装置支撑装置紧固件的螺母和螺栓表面防咬死涂层的均匀性,利用磁控溅射技术在管形器件的内表面和外表面制备了铜膜,应用台阶仪进行薄膜厚度测试.采用矩形铜板作为磁控溅射靶,采用单自转和公转加自转两种方式进行沉积,分析了铜膜在管形器件的内表面和外表面的膜厚分布规律.结果表明:无论螺母还是螺栓,公转加自转相对于单...     

铜在甲胺-铁氰化钾化学机械抛光液中的腐蚀与钝化

用电化学测试技术研究了腐蚀介质和成膜剂浓度对铜表面的腐蚀与钝化成膜的影响,分析了钝化膜的成分,探讨了钝化膜在抛光压力和转速作用下的磨损与表面再钝化的行为,测量了铜在化学机械抛光过程中的极化曲线。结果表明铜在甲胺溶液介质铁氰化钾抛光液中易钝化,钝化膜的主要成分为Cu4[Fe(CN)6],有少量Cu20存在。钝化膜的磨损特性随成分浓度不同而不同。钝化膜的磨损难易程度与钝化膜的本身特性、抛光压力及转速有关。抛光过程中因钝化膜被磨损,腐蚀加快,腐蚀电流密度大幅增加。配方0．1％甲胺溶液 0．5％K3Fe(CN)6 5％Al2O3可行。     

Electrical resistivity and thermoelectric power of copper-germanium films

CuGe films over the whole composition range were prepared by the vapour quenching of the alloys onto glass substrates held at 300 K. The electrical resistivity, thermoelectric power and temperature dependence of the films were studied in the temperature range 100–500 K. The observed behaviour of the electrical resistivity and thermoelectric power is understandable on the basis of transmission electron microscopy and electron diffraction observations which indicate three structural regions. Up to 5 at.% Ge in copper the films are single phase with a structure similar to that of pure copper; in the range 5–80 at.% Ge in copper the films consist of a mixture of Cu₃Ge, copper and germanium; beyond 80 at.% the CuGe films are single-phase amorphous.     

Galvanostatic electrodeposition and microstructure of copper (I) oxide film

 Polycrystalline copper (I) oxide films were deposited on stainless steel substrate by galvanostatic electrodeposition method and were characterized by X-ray diffraction and scanning electron microscopy. The effect of bath temperature, bath pH and current density on the compositon, grain size, surface texture and surface morphology of the electrodeposited films were investigated. The films deposited at low bath pH (≤7) consisted of copper (I) oxide and metallic copper; while the films deposited at bath pH between 8 and 12 and bath temperature of 60°C were pure copper (I) oxide. The preferred orientation of the copper (I) oxide films depended on the relative growth rate of {111} and {200} faces and could be controlled by adjusting the bath pH and/or the cathodic current density. (100)-oriented copper (I) oxide films could be deposited at pH=9 and current densities in the range of 0.25–1 mA/cm², while (111)-oriented films could be prepared at pH=12 or at pH=9 using the current densities between 1.5–2.5 mA/cm². Computer simulated crystallite shapes showed that the crystal shape changed from octahedral for (100)-oriented film to trucated pyramids and cubs for (111)-oriented film. And they were approved by scanning electron microscopy. Received: 1 December 1997 / Accepted: 13 December 1997     

铜上采用镍过渡层化学气相沉积金刚石薄膜的研究

采用镍过渡层研究了铜基片上金刚石薄膜的化学气相沉积．镍过渡层与铜基底间在高温退火条件下形成的铜镍共晶体明显地增强了金刚石薄膜与铜基片之间的结合力．用扫描电子显微镜和激光Ｒａｍａｎ谱研究了薄膜的形貌和质量;采用高温氢等离子体退火工艺在基片表面形成的铜镍碳氢共晶体上抑制了无定形碳和石墨的形成,有利于金刚石薄膜的生长．金刚石薄膜的均匀性受到共晶体的均匀性的影响．     

Structural studies of copper sulfide films: effect of ambient atmosphere

Abstract

We examined the structural properties of copper sulfide films as a function of the sulfurization time of 70-nm-thick Cu films. Copper sulfide films with various phases such as mixed metallic Cu-chalcocite, chalcocite, roxbyite, and covellite phases were formed with increasing sulfurization time. To evaluate the structural stability of various films, all the films were exposed to the ambient atmosphere for the same amount of time. Although the phase structure and stoichiometry of the films were maintained at a greater depth, the near-surface region of the films was oxidized and covered with overlayers of oxide, hydroxide, and/or sulfate species due to the exposure and reaction with the ambient atmosphere. The oxygen uptake and its reactivity with the copper sulfide film surfaces were enhanced with increasing sulfur content of the films. In addition, the type of divalent state of copper formed on the film surfaces depended on the phase structure, composition, and stoichiometry of the films.