Using Electrodeposition of Carboxylated Chitosan for Green Preparation of Copper Nanoclusters and Nanocomposite Films

On the basis of coordinated electrodeposition of carboxylated chitosan(CCS),we presented a green method to prepare Cu NCs and Cu NCs/CCS nanocomposite films.The method shows a range of benefits,such as the convenient and eco-friendly process,mild conditions,and simple post-treatment.The experimental results reveal that a homogeneous deposited film(Cu NCs/CCS nanocomposite film)is generated on the Cu plate(the anode)after electrodeposition,which exhibits an obvious red florescence.The results from TEM observation suggest there are nanoparticles(with the average particle size of 2.3 nm)in the deposited film.Spectral analysis results both demonstrate the existence of Cu NCs in the deposited film.Moreover,the Cu NCs/CCS film modified electrode is directly created through electrodeposition of CCS,which enables promising application in the electrochemical sensing.By means of fluorescence properties of Cu NCs,the Cu NCs/CCS film also owns the potential in fluorescence detection.Therefore,this work builds a novel method for the green synthesis of Cu NCs,meanwhile it offers a convenient and new electrodeposition strategy to prepare polysaccharide-based Cu NCs nanocomposites for uses in functional nanocomposites and bioelectronic devices.

Activator-assisted electroless deposition of copper nanostructured films

This paper showed simple and effective synthesis of copper nanoparticles within controlled diameter using direct electroless deposition on glass substrates, following the sensitization and activation steps. Electroless-deposited metals, such as Cu, Co, Ni, and Ag, and their alloys had many advantages in micro- and nanotechnologies. The structural, morphological, and optical properties of copper deposits were characterized using X-ray diffraction （XRD）, atomic force microscopy （AFM）, and UV-Vis spectroscopy. The structural data was further analyzed using the Rietveld refinement program. Structural studies reveal that the deposited copper prefers a （111） orientation. AFM studies suggest the deposited materials form compact, uniform, and nanocrystalline phases with a high tendency to self-organize. The data show that the particle size can be controlled by controlling the activator concentration. The absorption spectra of the as-deposited copper nanoparticles reveal that the plasmonic peak broadens and exhibits a blue shift with decreasing particle size.

Thickness dependence of the optical constants of oxidized copper thin films based on ellipsometry and transmittance

Thin oxidized copper films in various thickness values are deposited onto quartz glass substrates by electron beam evaporation. The ellipsometry parameters and transmittance in a wavelength range of 300 nm-1000 nm are collected by a spectroscopic ellipsometer and a spectrophotometer respectively. The effective thickness and optical constants, i.e., refractive index n and extinction coefficient k, are accurately determined by using newly developed ellipsometry combined with transmittance iteration method. It is found that the effective thickness determined by this method is close to the physical thickness and has obvious difference from the mass thickness for very thin film due to variable density of film. Furthermore, the thickness dependence of optical constants of thin oxidized Cu films is analyzed.

Controllable fabrication of self-organized nano-multilayers in copper–carbon films

In order to clarify the influence of methane concentration and deposition time on self-organized nano-multilayers,three serial copper-carbon films have been prepared at various methane concentrations with different deposition times using a facile magnetron sputtering deposition system. The ratios of methane concentration(CH4/Ar+CH4) used in the experiments are 20%, 40%, and 60%, and the deposition times are 5 minutes, 20 minutes, and 40 minutes, respectively.Despite the difference in the growth conditions, self-organizing multilayered copper-carbon films are prepared at different deposition times by changing methane concentration. The film composition and microstructure are investigated by x-ray photoelectron spectroscopy(XPS), x-ray diffraction(XRD), field emission scanning electron microscopy(FESEM), and high-resolution transmission electron microscopy(HRTEM). By comparing the composition and microstructure of three serial films, the optimal growth conditions and compositions for self-organizing nano-multilayers in copper-carbon film are acquired. The results demonstrate that the self-organized nano-multilayered structure prefers to form in two conditions during the deposition process. One is that the methane should be curbed at low concentration for long deposition time,and the other condition is that the methane should be controlled at high concentration for short deposition time. In particular, nano-multilayered structure is self-organized in the copper-carbon film with copper concentration of 10-25 at.%.Furthermore, an interesting microstructure transition phenomenon is observed in copper-carbon films, that is, the nanomultilayered structure is gradually replaced by a nano-composite structure with deposition time and finally covered by amorphous carbon.

Effects of Annealing Temperature on the Properties of Copper Films Prepared by Magnetron Sputtering

Copper oxide thin films were prepared by a direct-current magnetron sputtering method followed by a thermal annealing treatment at 100-500 ℃. The obtained films were characterized by X-ray diffraction, UV-vis absorption spectroscopy, scanning electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. With the increase of the annealing temperature, it was found that the films transformed sequentially from amorphous to single-phase Cu （100℃）, mixed-phase of Cu and Cu2O （150 ℃）, single-phase Cu2O （200 ℃）, then to mixed-phase of Cu2O and CuO （300 ℃）, and finally to single-phase CuO （400 - 500 ℃）. Further analyses indicated that the Cu/Cu2O thin films and the Cu：O thin films presented no further oxidation even on the surface in air atmosphere. Additionally, the visible-light photocatalytic behavior of the copper oxide thin films on the degradation of methylene blue （MB） was also investigated, indicating that the films with pure Cu2O phase or Cu/Cu2O mixed phases have excellent photocatalytic efficiencies.

Computer simulation of the bombardment of a copper film on graphene with argon clusters

The process of graphene cleaning of a copper film by bombarding it with Ar_（13） clusters is investigated by the molecular dynamics method.The kinetic energies of the clusters are 5,10,20,and 30 eV and the incident angles are θ= 90°,75°,60°,45°,and 0°.It is obtained that the cluster energy should be in the interval 20 eV-30 eV for effective graphene cleaning.There is no cleaning effect at vertical incidence（θ =0°） of Ar_（13） clusters.The bombardments at 45° and 90° incident angles are the most effective on a moderate and large amount of deposited copper,respectively.

In Situ Studies of Deformation and Fracture in Sputtering Copper Film

Nanocrystalline copper films were prepared by sputtering and then in situ straining experiments were performed using a trans- mission electron microscope. Macroscopically, these copper films exhibited very low ductility (<l%). Dislocation activity was limited in regions far from propagating cracks. Near stable growing cracks, considerable local plasticity was observed. The evidence of slip ac- tivity both within grain interiors and in grain boundaries was also observed. Although some dislocation; moved very fast, others showed rates much lower than those typically measured for bulk copper. Fracture was intergranular, but not brittle. It occurred by linking of microcracks. Microcracks formed within a micrometer or so ahead of the main crack tip, usually within a grain boundary. Linking then took place by the easiest available path.

Preparation and Properties of Copper Fine Wire on Polyimide Film in Air by Laser Irradiation and Mixed-Copper-Complex Solution Containing Glyoxylic Acid Copper Complex and Methylamine Copper Complex

Formation of copper wiring on a polyimide film by laser irradiation to a stable copper-complex film consisting of glyoxylic acid copper complex and methylamine copper complex in air has been investigated. A stable metallic copper on the polyimide film was precipitated even in air. Since this copper was generated only in the laser-irradiated parts, direct patterning of copper wiring was possible. It was also found that copper was precipitated by electroless copper plating on the laser-deposited copper wiring and it was possible to thicken the copper wiring by this precipitation. The resistivity of the copper wiring was almost the same as that of the bulk of metallic copper. The developed method—combining laser irradiation to a copper-complex-coated film and electroless copper plating—enables the high-speed deposition of fine copper wiring on a polyimide film in air by a printing process, indicating an inexpensive and useful process for fabricating copper wiring without high vacuum facility and heat-treatment under inert gas.

Preparation and operation characteristics of organic semiconductor transistor using thin film Al gate and copper phthalocyanine

The organic static induction transistors (OSITs) are fabricated by the method of evaporating and plating in a vacuum with copper phthalocyanine (CuPc) dye, and has a five layered structure of Au/CuPc/Al/CuPc/Au. The experiment reveals that OSITs have obtained a low driving voltage, high current density and high switch speed such as I_ DS = 1.2×10 -6 A/mm2, and the degree of 1 000 Hz. The OSITs have excellent operation characteristics of typical static induction transistors.

Chemical Vapor Deposition Mechanism of Copper Films on Silicon Substrates

A versatile metal-organic chemical vapor deposition （MOCVD） system was designed and constructed. Copper films were deposited on silicon （100） substrates by chemical vapor deposition （CVD） using Cu（hfac）2 as a precursor. The growth of Cu nucleus on silicon substrates by H2 reduction of Cu（hfac）2 was studied by atomic force microscopy and scanning electron microscopy. The growth mode of Cu nucleus is initially Volmer-Weber mode （island）, and then transforms to Stranski-Rastanov mode （layer-by-layer plus island）. The mechanism of Cu nucleation on silicon （100） substrates was further investigated by X-ray photoelectron spectroscopy. From Cu2p, O1s, F1s, Si2p patterns, the observed C=O, OH and CF3/CF2 should belong to Cu（hfac） formed by the thermal dissociation of Cu（hfac）2. H2 reacts with hfac on the surface, producing OH. With its accumulation, OH reacts with hfac, forming HO-hfac, and desorbs, meanwhile, the copper oxide is reduced, and thus the redox reaction between Cu（hafc）2 and H2 occurs.

Electrochemical performance of organic film on copper surface by polymer plating of 6-mercapto-1,3,5-triazine-2,4-dithiol monosodium

The 6-mercapto-1,3,5-triazine-2,4-dithiol monosodium(TTN) compound was used to fabricate an organic film on pure copper. The polymer plating process of TTN on pure copper in Na2CO3 aqueous solution and the growth mechanism of poly(6-mercapto-1,3,5-triazine-2,4-dithiol)(PTT) film were studied by means of cyclic voltammetry. The polymer plating under galvanostatic mode at 0.05 mA/cm2 was conducted to generate PTT film on pure copper in the same electrolyte with different polymer-plating time. The film mass was determined by electronic balance and the insoluble fraction in tetrahydrofuran(THF) Is tested. The performance of organic film formed on copper surface was investigated preliminarily by potentiodynamic polarization and electrochemical impedance spectroscopy(EIS). It is found that a slight peak measured at 0 V vs SCE attributes to the oxidation of copper and generated Cu+ or/and Cu2+ to produce Cu-TTN complex,then a strong oxide peak is observed at 0.311 V vs SCE due to the polymerization of TTN for the increase of the film thickness. Electrochemical measurement results reveal that 10 min is an optimum polymer-plated time to obtain high quality film. The results of potentiodynamic polarization show that current density decreases from 1.85 μA/cm2 for bare copper to 0.168 μA/cm2 for polymer-plated copper while polymer-plated time is 10 min. The charge transfer resistances of bare copper and polymer-plated copper are 937 Ω·cm2 and 11.12 kΩ·cm2,respectively. The film capacitor for polymer-plated copper is as low as 1.82 μF·cm2. The EIS results confirm the results of potentiodynamic polarization and reveal that a homogenous and compact film is obtained by polymer plating technique.

La-doped Copper Nitride Films Prepared by Reactive Magnetron Sputtering

Copper nitride film （Cu3N） and La-doped copper nitride films （LaxCu3N） were prepared on glass substrates by reactive magnetron sputtering of a pure Cu and a pure La targets under N2 atmosphere. The results show that La-free film was composed of Cu3N crystallites with anti-ReO3 structure with （111） texture. The formation of the LaxCu3N films is affected strongly by La, and the peak intensity of the preferred crystalline [111]-orientation decreases with increasing the concentration of La. High concentration of La may prevent the formation of the Cu3N from crystallization. Compared with the Cu3N films, the resistivity of the LaxCu3N films have been decreased.

Properties of Al-doped Copper Nitride Films Prepared by Reactive Magnetron Sputtering

Cu3N and Al Cu3N films were prepared with reactive magnetron sputtering method. The two films were deposited on glass substrates at 0.8 Pa N2 partial pressure and 100 ℃ substrate temperature by using a pure Cu and AI target, respectively. X-ray diffraction （XRD） measurements show that the un-doped film was composed of Cu3N crystallites with anti-ReO3 structure and adopted [111] preferred orientation. XRD shows that the growth of Al-doped copper nitride films （AlxCu3N） was affected strongly by doping AI, the intensity of [111] peak decreases with increasing the concentration of Al and the high concentration of Al could prevent the Cu3N from crystallization. AFM shows that the surface of AlCu3N film is smoother than that of Cu3N film. Compared with the Cu3N films, the resistivities of the Al-doped copper nitride films （AlxCu3N） have been reduced, and the microhardness has been enhanced.

Reactive DC Magnetron Sputtering Deposition of Copper Nitride Thin Film

Copper nitride thin film was deposited on glass substrates by reactive DC （direct current） magnetron sputtering at a 0.5 Pa N2 partial pressure and different substrate temperatures. The as-prepared film, characterized with X-Ray diffraction, atomic force microscopy, and X-ray photoelectron spectroscopy measurements, showed a composed structure of Cu3N crystallites with anti-ReO3 structure and a slight oxidation of the resulted film.The crystal structure and growth rate of Cu3N films were affected strongly by substrate temperature. The preferred crystalline orientation of Cu3N films were （111） and （200） at RT, 100℃. These peaks decayed at 200℃ and 300℃ only Cu （111） peak was noticed. Growth of Cu3N films at 100℃ is the optimum substrate temperature for producing high-quality （111） Cu3N films. The deposition rate of Cu3N films estimated to be in range of 18-30 nm/min increased while the resistivity and the microhardness of Cu3N films decreased when the temperature of glass substrate increased.

X-Ray Photoelectron Spectroscopic Study on the Synthesis of Copper Sulphide in LB Films( Ⅱ )

The present paper covers the formation process of copper sulphide in copper stearate Langmuir-Blodgett films studied carefully by XPS. The further identification of sulfur species and the examination of its change in the reaction have been made. Also the formation mechanism of sulfur species in the special microenvironment-LB films is discussed.

Yield strength of attached copper film

Variation of stress in attached copper film with an applied strain is measured by X-ray diffraction combined with a four-point bending method. A lower slope of the initial elastic segment of the curve of X-ray measured stress versus applied strain results from incomplete elastic strain transferred from the substrate to the film due to insufficiently strong interface cohesion. So the slope of the initial elastic segment of the X-ray stress （or X-ray strain directly） of the film against the substrate applied strain may be used to measure the film-substrate cohesive strength. The yield strength of the attached copper film is much higher than that of the bulk material and varies linearly with the inverse of the film thickness.

EFFECT OF FABRICATION ON HIGH CYCLE FATIGUE PROPERTIES OF COPPER THIN FILMS

The influence of fabrication on the tensile and fatigue behavior of copper films manufactured by 3 kinds of fabrication methods was investigated. The tensile and high cycle fatigue tests were performed using the test machine developed by authors. Young＇s moduli （72, 71 and 69 GPa, respectively） are lower than the literature values （108-145 GPa）, while the yield strengths were as high as 358, 350 and 346 MPa, respectively and the ultimate strengths as 462, 456 and 446 MPa, respectively. There is not much difference in the tensile properties of the 3 kinds of films. There is little difference in the fatigue properties of the 3 kinds of films but one of them has shorter fatigue life than others in high cycle region and longer fatigue life than others in low cycle region.

Evolution of copper nanowires through coalescing of copper nanoparticles induced by aliphatic amines and their electrical conductivities in polyester films

Copper nanowires were synthesized by the wet chemical reduction method using copper sulfate as the copper precursor,aliphatic amines(methylamine,ethanediamine,1,2-propanediamine)as the inducing reagents,and hydrazine hydrate as the reductant through the aging and reduction processes.The high-resolution transmission electron microscopy(HRTEM)images reveal that the copper nanowires were synthesized by coalescing extremely small-sized copper nanoparticles with the particle sizes of1–6 nm in copper complex micelles.A longer aging time period favored the coalescing of the copper nanoparticles to form thinner copper nanowires in the following reduction process.The coalescing extent of copper nanoparticles in copper nanowires was highly enhanced by ethanediamine and 1,2-propanediamine as compared with that by methylamine.The copper nanowire-filled polyester films had higher electrical conductivity than the copper nanoparticle-filled ones.

Highly effective electrochemical water oxidation by copper oxide film generated in situ from Cu(Ⅱ) tricine complex

Developing highly efficient and stable water oxidation catalysts based on abundant metallic elements is a challenge that must be met to fulfill the promise of water splitting for clean energy production.In this work,we developed an oxygen evolution reaction catalyst consisting of a nanostructured film electrodeposited from a phosphate buffer solution(0.2mol/L,pH=12.0)containing Cu‐tricine complex.A Tafel plot showed that the required overpotential for a current densityof1.0mA/cm2was only395mV and the Tafel slope was46.7mV/decade.In addition,the Cu‐tricine film maintained a stable current density of7.5mA/cm2for the oxygen evolution reaction in phosphate buffer solution for10h,and a Faradaic efficiency of99%was obtained.

Gas sensor using gold doped copper oxide nanostructured thin films as modified cladding fiber

We investigate the spectral response of nanostructured copper oxides thin film. Gold was doped in two different concentrations(2% and 4%) using the spray method. A novel ammonia gas sensor at various concentrations(0–500 ppm)was fabricated by replacing CuO films with a clad region. In addition, the effect of gold doping on structural, optical,and morphological properties has been demonstrated. The study shows that the spectral intensity increases linearly with ammonia concentration. The 4% Au doped CuO presents higher sensitivity compared with 2% doped and pure copper oxides. Time response characteristics of the sensor are also reported.