Magnetron sputtering deposition of silicon nitride on polyimide separator for high-temperature lithium-ion batteries

To date,lithium-ion batteries are becoming increasingly significant in the application of portable devices and electrical vehicles,and revolutionary progress in theoretical research and industrial application has been achieved.However,the commercial polyolefin separators with unsatisfying electrolytes affinity and poor thermal stability have extremely restricted the further application of lithium-ion batteries,especially in the high-temperature fields.In this work,magnetron sputtering deposition technique is employed to modify the commercial polyimide separator by coating silicon nitride on both sides.Magnetron sputtering deposition modified polyimide(MSD-PI)composite separator shows high thermal stability and ionic conductivity.More importantly,compared with the cells using Celgard separator,the cells with MSD-PI separator exhibit superior electrochemical performance,especially long-term cycle performance under high temperature environment,owing to the high thermal conductivity of surface Si3 N4 particles.Hence,lithium-ion batteries with MSD-PI separator are capable of improving thermal safety and capacity retention,which demonstrates that magnetron sputtering deposition technique could be regarded as a promising strategy to develop advanced organic/inorganic composite separators for high-temperature lithium-ion batteries.

Preparation and Corrosion Resistance of Magnesium Coatings by Magnetron Sputtering Deposition

Magnesium coatings were fabricated on stainless steel substrates (1Cr11Ni2W2MoV) by a plane magnetron sputtering technique. The argon pressure and the substrate condition (including temperature and the substrate was rotated or fixed) were varied in order to evaluate the influence of the parameters on the crystal orientation and morphology of the coating. The corrosion behavior of the coatings in 1 wt pct NaCI solution was studied by electrochemical methods. The results showed that all coatings exhibited preferred orientation (002) as the argon pressure increased from 0.2 to 0.4 Pa. The morphologies of the coatings varied with the argon pressure and with whether the substrate was rotated or fixed. The open circuit potential of the coatings was more positive than that of cast AZ91D magnesium alloy. However, the immersion test in 1 wt pct NaCI solution showed that the corrosion rates of the coatings were higher than that of cast AZ91D magnesium alloy.

Effects of the ion-beam voltage on the properties of the diamond-like carbon thin film prepared by ion-beam sputtering deposition

Diamond-like carbon （DLC） thin film is one of the most widely used optical thin films. The fraction of chemical bondings has a great influence on the properties of the DLC film. In this work, DLC thin films are prepared by ion-beam sputtering deposition in Ar and CH4 mixtures with graphite as the target. The influences of the ion-beam voltage on the surface morphology, chemical structure, mechanical and infrared optical properties of the DLC films are investigated by atomic force microscopy （AFM）, Raman spectroscopy, nanoindentation, and Fourier transform infrared （FTIR） spec- troscopy, respectively. The results show that the surface of the film is uniform and smooth. The film contains sp2 and sp3 hybridized carbon bondings. The film prepared by lower ion beam voltage has a higher sp3 bonding content. It is found that the hardness of DLC films increases with reducing ion-beam voltage, which can be attributed to an increase in the fraction of sp3 carbon bondings in the DLC film. The optical constants can be obtained by the whole infrared optical spectrum fitting with the transmittance spectrum. The refractive index increases with the decrease of the ion-beam voltage, while the extinction coefficient decreases.

Density behaviors of Ge nanodots self-assembled by ion beam sputtering deposition

Self-assembled Ge nanodots with areal number density up to 2.33× 1010 cm-2 and aspect ratio larger than 0.12 are prepared by ion beam sputtering deposition. The dot density, a function of deposition rate and Ge coverage, is observed to be limited mainly by the transformation from two-dimensional precursors to three-dimensional islands, and to be associated with the adatom behaviors of attachment and detachment from the islands. An unusual increasing temperature dependence of nanodot density is also revealed when a high ion energy is employed in sputtering deposition, and is shown to be related to the breaking down of the superstrained wetting layer. This result is attributed to the interaction between energetic atoms and the growth surface, which mediates the island nucleation.

PHASE TRANSFORMATION BEHAVIOR IN THE SPUTTER DEPOSITED Ti-Pd-Ni THIN FILMS

Ti-Pd-Ni thin films were prepared by sputter deposition at room temperature. The as-deposited thin films were crystallized at 750°C followed by various cooling conditions, and the structural change emerging in the films was characterized by means of both X-ray diffraction (XRD) and differential scanning calorimetry (DSC). It was found that the phase transformation temperatures of Ti50.6Pd30Ni19.4 ingot we much higher than those of its thin film. The B19' and B19 phases coexisted, together with the Ti2Ni type and Ti2Pd type of precipitates at the room temperature. Both the B19-B2 one-stage and the B19'-B19-B2 two-stage phase transformations took place when the films experienced thermal change across the region of phase transformation temperatures.

EFFECT OF Ar PRESSURE ON STRUCTURAL AND ELECTRICAL PROPERTIES OF Cu FILMS DEPOSITED ON GLASS BY DC MAGNETRON SPUTTERING

Cu films with thickness of 630-1300nm were deposited on glass substrates without heating by DC magnetron sputtering in pure Ar gas. Ar pressure was controlled to 0.5, 1.0 and 1.5Pa respectively. The target voltage was fixed at 500V but the target current increased from 200 to 1150mA with Ar pressure increasing. X-ray diffraction, scanning electron microscopy and atomic force microscopy were used to observe the structural characterization of the films. The resistivity of the films was measured using four-point probe technique. At all the Ar pressures, the Cu films have mixture crystalline orientations of [111], [200] and [220] in the direction of the film growth. The film deposited at lower pressure shows more [111] orientation while that deposited at higher pressure has more [220] orientation. The amount of larger grains in the film prepared at 0.5Pa Ar pressure is slightly less than that prepared at 1.0Pa and 1.5Pa Ar pressures. The resistivities of the films prepared at three different Ar pressures represent few differences, about 3-4 times of that of bulk material. Besides the deposition rate increases with Ar pressure because of the increase in target current. The contribution of the bombardment of energetic reflected Argon atoms to these phenomena is discussed.

Characterization of La-doped xBiInO_3(1-x)PbTiO_3 Piezoelectric Films Deposited by the Radio-Frequency Magnetron Sputtering Method

La-doped and undoped xBiIn03-（1 - x）PbTi03 （BI-PT） thin films are deposited on （101）SrRuO3/（lOO）Pt/（lO0） MgO substrates by the rf-magnetron sputtering method. The structures of the films are characterized by XRD and SEM, and the results indicate that the thin films are grown with mainly （100） oriented and columnar structures. The ferroelectricity and piezoelectricity of the BI-PT films are also measured, and the measured results illustrate that both performances are effectively improved by the La-doping with suitable concentrations. These results will open up wide potential applications of the films in electronic devices.

Effects of Sputtering Parameters on the Performance of Sputtered Cathodes for Direct Methanol Fuel Cells

Plasma sputtering deposition techniques are good candidates for the fabrication of electrodes used for direct methanol fuel cells （DMFCs）. A house-made plasma sputtering system was used to deposit platinum of 0.1 mg/cm^2 onto un-catalyzed gas diffusion layers （GDLs） to form a Pt catalyzed cathode at different radio frequency （RF） powers and sputtering-gas pressures. The sputtered cathodes were assembled in custom-made membrane electrode assemblies （MEAs） with a commercial anode and tested for the electrical performance of the single cell. A custommade MEA with a sputtering prepared cathode was compared with that of a reference membrane electrode assembly made of commercial JM （Johnson Mattey） catalysts （Pt loading per electrode of 0.5 mg/cm^2） under passive methanol supply, ambient temperature and air-breathing conditions. The results showed that the cathode prepared at an input power of 110 W and sputtering-gas pressure of 5.3 Pa exhibited the best cell performance and highest Pt utilization efficiency, which was due to the miniaturization of the Pt particles and formation of the porous catalyst layer. Although the single cell performance of the commercial cathode was better than all the sputtering fabricated cathodes, the Pt utilization efficiency of all the sputtered cathodes was higher than that of the commercial cathode.

Preparation of Anodes for DMFC by Co-Sputtering of Platinum and Ruthenium

Anodes used for direct methanol fuel cells （DMFCs） were fabricated by magnetron sputtering process. A house-made plasma sputtering system was used to deposit Pt and PtRu onto un-catalyzed gas diffusion layers （GDLs） at different radio frequency （RF） powers and sputtering- gas pressures. The thin film catalyst layers were characterized by X-ray diffraction, energy dis- persive X-ray analysis, and X-ray photoelectron spectroscopy. The sputtered anodes were assem- bled in custom-made membrane electrode assemblies （MEAs） with a commercial cathode and the electrical performance of the single cell were tested under passive methanol supply, ambient tern- perature and air-breathing conditions. The electrochemical performance of the anodes prepared with PtRu alloy was compared with a reference anode sputtered with Pt only. X-ray diffraction and X-ray photoelectron spectroscopy revealed that platinum and ruthenium existed as a form of alloy. The cell polarization measurements showed that all the PtRu alloy catalysts had better electrochemical performance than the Ptl catalyst, and the Pto.n3Ruo.57 catalyst achieved the best performance.

Nano-sized Thin Films Fabricated by Ion Beam Sputtering and Its Properties

Nanoscale thick amorphous Ni-Cr alloy thin films were fabricated by low-energy ion beam sputtering technology; then the as-deposited samples experienced rapid thermal process to realize the transformation from amorphous to crystalline state. The film thickness was measured with a-stylus surface profiler, the structure and the compositions of the films were confirmed by low angle X-ray diffraction and scanning auger electron microprobe respectively, and the surface topography was characterized by scanning electron microscope and scanning probe microscope. Electrical property of the films was measured by fourpoint probe. The experimental results illustrate that the combined processes of ion beam sputtering and rajid thermal process are effective for fabrication nanoscale Ni-Cr alloy thin film with good properties.

Composition and Microstructure of Magnetron Sputtering Deposited Ti-containing Amorphous Carbon Films

Ti-containing carbon films were deposited by using magnetron sputtering deposition. The composition and microstructure of the carbon films were characterized in detail by combining the techniques of Rutherford backscattering spectrometry （RBS）, X-ray photoelectron spectroscopy （XPS）, X-ray diffraction （XRD） and transmission electron microscopy （TEM）. It is found that carbon films contain Ti 18 at pct; after Ti incorporation, the films consist of titanium carbide; C1s peak appears at 283.4 eV and it could be divided into 283.29 and 284.55 eV, representing sp2 and sp3, respectively, and sp2 is superior to sp3. This Ti-containing film with dominating sp2 bonds is nanocomposites with nanocrystalline TiC clusters embedded in an amorphous carbon matrix, which could be proved by XRD and TEM.

Discharge Properties of High-Power Pulsed Unbalanced Magnetron Sputtering

High-power pulsed magnetron sputtering （HPPMS or HiPIMS） is an emerging coating technology that produces very dense plasmas and highly ionized sputtering atoms. This paper is focused on discharge properties, unbalanced features and temporal evolution of pulse current of the HPPMS discharge. A hollow cathode was used to suppress the scattering of charges. A coaxial coil surrounding the target was used to control the breakdownvoltage and pulse repetition frequency by varying the coil current. A Langmuir probe and an oscilloscope were used to simultaneously measure the floating potential, pulse voltage and pulse current signMs. The pulse power density in the discharge reached 10 kW/cm2 with frequencies as high as N40 Hz and a pulse width about 1~5 ms. The characteristics of the discharge evolution were analyzed using magnetron discharge dynamics.

High Ferroelectricities and High Curie Temperature of BiInO3PbTiO3Thin Films Deposited by RF Magnetron Sputtering Method

Properties of ferroelectric xBiInO3-（1-x）PbTiO3（xBI-（1-x）PT） thin films deposited on（101） SrRuO3/（200）Pt/（200） MgO substrates by rf magnetron sputtering method and effects of deposition conditions are investigated.The structures of the xBI-（1-x）PT films are characterized by x-ray diffraction and scanning electron microscopy.The results indicate that the thin films are grown with mainly（001） orientation. The chemical compositions of the films are analyzed by scanning electron probe and the results indicate that the loss phenomena of Pb and Bi elements depend on the pressure and temperature during the sputtering process.The sputtering parameters including target composition, substrate temperature, and gas pressure are adjusted to obtain optimum sputtering conditions. To decrease leakage currents,2 mol% La2 O3 is doped in the targets. The P-E hysteresis loops show that the optimized xBI-（1-x）PT（x = 0.24） film has high ferroelectricities with remnant polarization2 Pr = 80μC/cm2 and coercive electric field 2 EC = 300 kV/cm. The Curie temperature is about 640℃. The results show that the films have optimum performance and will have wide applications.

Effects of Substrate Temperature on Properties of Transparent Conductive Ta-Doped TiO_2 Films Deposited by Radio-Frequency Magnetron Sputtering

Ta-doped titanium dioxide films are deposited on fused quartz substrates using the rf magnetron sputtering technique at different substrate temperatures. After post-annealing at 550℃ in a vacuum, all the films are crystallized into the polycrystalline anatase TiO2 structure. The effects of substrate temperature from room temperature up to 350℃ on the structure, morphology, and photoelectric properties of Ta-doped titanium dioxide films are analyzed. The average transmittance in the visible region（400-800 nm） of all films is more than 73%.The resistivity decreases firstly and then increases moderately with the increasing substrate temperature. The polycrystalline film deposited at 150℃ exhibits a lowest resistivity of 7.7 × 10^-4Ω·cm with the highest carrier density of 1.1×10^21 cm^-3 and the Hall mobility of 7.4 cm^2·V^-1s^-1.

Development of aperiodic multilayer mirrors operated at W-Lβline for plasma diagnostics application

Multilayer interference mirrors play a pivotal role in spectroscopic diagnostic systems,which probe electron temperature and density during inertial confinement fusion processes.In this study,aperiodic Mo/B_(4)C multilayer mirrors of varied thick-nesses were investigated for X-ray plasma diagnostics at the 9.67-keV W-Lβline.The thickness distribution of the aperiodic multilayers was designed using the first Bragg diffraction condition and then optimized through a simplex algorithm to realize a narrow bandwidth and consistent spectral response.To enhance spectral accuracy,further refinements were undertaken by matching the grazing incidence X-ray reflectivity data with actual structural parameters.X-ray reflectivity measurements from the SSRF synchrotron radiation facility on the optimized sample showed a reflectivity of 29.7±2.6%,flat-band range of 1.3 keV,and bandwidth of 1.7 keV,making it suitable for high-temperature plasma diagnostics.The study explored the potential of predicting the 9.67 keV reflectivity spectrum using the fitting data from the grazing incidence X-ray reflectivity curves at 8.05 keV.Additionally,the short-term thermal stability of an aperiodic multilayer was assessed using temperature-dependent in situ X-ray measurements.Shifts in the reflectivity spectrum during annealing were attributed to interdiffusion and interfacial relaxation.The research team recommends the aperiodic Mo/B_(4)C multilayer mirror for operations below 300℃.

Oxidation Behavior of Micro-Crystalline Coatings of 310S Stainless Steel

Micro-crystalline coatings of 310S stainless steels were produced by unbalanced magnetron sputter deposition. Isothermal oxidation behavior of the coated and uncoated specimens has been studied using a thermogravimetric analysis (TGA) station. The oxidation time was 50h and the temperature was 1 000℃. The oxidation rates of thecoated specimens was found to be much lower than the uncoated specimens after 50 h of oxidation. The oxidationkinetic curves of the coated specimens consisted of three stages : approximately parabolic at the first stage, speedingup at the second stage, and slow down at the third stage. The increase of the oxidation rate at the second stage nasattributed to the fast diffuison of Fe though the fine grained Cr2O3 layer formed on the micro-crystalline coatings.The top view and cross-section microstructures of the oxides formed on the coated and the uncoated specimens werestudied with SEM and EDS. It was observed that the nucleation of oxide on the coated specimens was muchenhanced at the initial oxidation stage. This was explained as the result of reduction in the critical free energychange and increase in the supply of chromium ions.

Sputtering Deposition of Ultra-thin α-Fe_2O_3 Films for Solar Water Splitting

Ultra-thin α-Fe2O3（hematite） films have been deposited by radio frequency（RF） sputtering technique and photoelectrochemically investigated towards their ability to oxidize water.By varying the deposition power and time as well as the sputter gas flow（argon）,the microstructure and morphology of the film were optimized.It was found that the increment in the film thickness resulted in the loss of efficiency for solar water oxidation.The film with a thickness of 27 nm exhibited the best result with a maximum photocurrent of 0.25 mA cm-2at 1.23 VRHE.Addition of small amounts of O2to the sputter gas improved the photoactivity significantly.

The 50 nm-thick yttrium iron garnet films with perpendicular magnetic anisotropy

Yttrium iron garnet(YIG) films possessing both perpendicular magnetic anisotropy(PMA) and low damping would serve as ideal candidates for high-speed energy-efficient spintronic and magnonic devices.However,it is still challenging to achieve PMA in YIG films thicker than 20 nm,which is a major bottleneck for their development.In this work,we demonstrate that this problem can be solved by using substrates with moderate lattice mismatch with YIG so as to suppress the excessive strain-induced stress release as increasing the YIG thickness.After carefully optimizing the growth and annealing conditions,we have achieved out-of-plane spontaneous magnetization in YIG films grown on sGGG substrates,even when they are as thick as 50 nm.Furthermore,ferromagnetic resonance and spin pumping induced inverse spin Hall effect measurements further verify the good spin transparency at the surface of our YIG films.

Films surface temperature calculation during growth by sputtering technique

A calculation of film surface temperature during thin films growth by sputtering technique is proposed. The calculation procedure is based on the conversion into heat of the total flux energy of species impinging the film surface during growth. The results indicate that the film＇s surface temperature depends drastically on material substrate thermal conductivity and thickness on one hand, and the plasma conditions namely the discharge power on the other. The predicted film surface temperatures were used to explain the microstructure evolution of hydro- genated amorphous silicon （a-Si：H） thin films deposited by reactive radio frequency （RF） sputtering on different substrates.

Influence of sputtering pressure on optical constants of a-GaAs_(1-x)N_x thin films

Amorphous GaAsl-xNx （a-GaAsl-xNx） thin films have been deposited at room temperature by a reactive magnetron sputtering technique on glass substrates with different sputtering pressures. The thickness, nitrogen content, carrier concentration and transmittance of the aseposited films were determined experimentally. The influence of sputtering pressure on the optical band gap, refractive index and dispersion parameters （Eo, Ed） has been investigated. An analysis of the absorption coefficient revealed a direct optical transition characterizing the asdeposited films. The refractive index dispersions of the as-deposited a-GaAsl-xNx films fitted well to the Cauchy dispersion relation and the Wemple model.