Because of their low electrical conductivity,sluggish ion diffusion,and poor stability,conventional electrode materials are not able to meet the growing demands of energy storage and portable devices.Graphene assemble...Because of their low electrical conductivity,sluggish ion diffusion,and poor stability,conventional electrode materials are not able to meet the growing demands of energy storage and portable devices.Graphene assembled films(GAFs)formed from graphene nanosheets have an ultrahigh conductivity,a unique 2D network structure,and exceptional mechanical strength,which give them the potential to solve these problems.However,a systematic understanding of GAFs as an advanced electrode material is lacking.This review focuses on the use of GAFs in electrochemistry,providing a comprehensive analysis of their synthesis methods,surface/structural characteristics,and physical properties,and thus understand their structure-property relationships.Their advantages in batteries,supercapacitors,and electrochemical sensors are systematically evaluated,with an emphasis on their excellent electrical conductivity,ion transport kinetics,and interfacial stability.The existing problems in these devices,such as chemical inertness and mechanical brittleness,are discussed and potential solutions are proposed,including defect engineering and hybrid structures.This review should deepen our mechanistic understanding of the use of GAFs in electrochemical systems and provide actionable strategies for developing stable,high-performance electrode materials.展开更多
[Background and purposes]Proton exchange membrane fuel cells(PEMFCs),which convert hydrogen energy directly into electrical energy and water,have received overwhelming attention,owing to their potential to significant...[Background and purposes]Proton exchange membrane fuel cells(PEMFCs),which convert hydrogen energy directly into electrical energy and water,have received overwhelming attention,owing to their potential to significantly reduce energy consumption,pollution emissions and reliance on fossil fuels.Bipolar plates are the major part and key component of PEMFCs stack,which provide mechanical strength,collect and conduct current segregate oxidants and reduce agents.They contribute 70-80%weight and 20-30%cost of a whole stack,while significantly affecting the power density.There are three types plates,including metal bipolar plate,graphite bipolar plate and composite bipolar plate.Stainless steel bipolar plates,as one of metal bipolar plate,exhibit promising manufacturability,competitive cost and durability among various metal materials.However,stainless steel would be corroded in the harsh acid(pH 2-5)and humid PEMFCs environment,whereas the leached ions will contaminate the membrane.In addition,the passivated film formed on the surface will increase the interfacial contact resistance(ICR).In order to improve the corrosion resistance and electrical conductivity of steel bipolar plates,surface coatings are essential.Metal nitride coatings,metal carbide coatings,polymer coatings and carbon-based coatings have been introduced in recent years.Carbon-based coatings,mainly including a-C(amorphous Carbon),Ta-C(Tetrahedral amorphous carbon)and DLC(diamond-like carbon),have attracted considerable attention from both academia and industry,owing to their superior performance,such as chemical inertness,mechanical hardness and electrical conductivity.However,Ta-C films as protective coating of PEMFCs have been rarely reported,due to the difficulty in production for industrial application.In this paper,multi-layer Ta-C composite films were produced by using customized industrial-scale vacuum equipment to address those issues.[Methods]Multiple layered Ta-C coatings were prepared by using PIS624 equipment,which assembled filtered cathodic arc evaporation,ion beam and magnetron sputtering into one equipment,while SS304 and silicon specimens were used as substrate for testing and analysis.Adhesion layer and intermediate layer were deposited by using magnetron sputtering at deposition temperature of 150℃and pressure of 3×10^(−1) Pa,while the sputtering current was set to be 5 A and bias power to be 300 V.The Ta-C layer was coated at arc current of 80-100 A,bias voltage of 1500 V and gas flow of 75 sccm.A scanning electron microscope(CIQTEK SEM3200)was used to characterize surface morphology,coating structure and cross-section profile of the coatings.Raman spectrometer(LabRam HR Evolution,HORIBA JOBIN YVON)was used to identify the bonding valence states.Electrochemical tests were performed by using an electrochemical work station(CHI760,Shanghai Chenhua Instrument Co.,Ltd.),with the traditional three electrode system,where saturated Ag/AgCl and platinum mesh were used as the reference electrode and counter electrode,respectively.All samples were mounted in plastic tube and sealed with epoxy resin,with an exposure area of 2.25 cm^(2),serving as the working electrode.Electrochemical measurements were carried out in simulated PEMFCs cathode environment in 0.5 mol·L^(−1) H_(2)SO_(4)+5 ppm F−solution,at operating temperature of 70℃.As the cathode environment was harsher than the anode environment,all the samples are stabilized at the open-circuit potential(OCP)for approximately 30 min before the EIS measurements.ICR between bipolar plates and GDL was a key parameter affecting performance of the PEMFCs stack.The test sample sandwiched between 2 pieces of carbon paper(simulate gas diffusion layer,GDL)was placed between 2 gold-plated copper electrodes at a compaction pressure of 1.4 MPa,which was considered to be the conventional compaction pressure in the PEMFCs.Under the same conditions,the resistance of a single carbon paper was measured as well.The ICR was calculated according to the formula ICR=1/2(R2−R1)×S,where S was the contact area between GDL and coated stainless steel BPPs.All data of ICR were measured three times for averaging.[Results]The coatings deposited by filtered cathodic arc technology were compact and smooth,which reduced coating porosity and favorable to corrosion resistance.The coating thickness of adhesion and intermediate layers were 180 nm,while the protective Ta-C coating thickness was about 300 nm,forming multiple coating to provide stronger protection for metal bipolar plates.Cr,Ti,Nb and Ta coatings were selected as adhesion layers for comparison.According to electrochemical test,Ta and Nb coatings have higher corrosion resistance.However,Ta and Nb materials would be costly when they are used for mass production.Relatively,Cr and Ti materials were cost effective.Hence,a comprehensive assessment was indispensable to decide the materials to be selected as adhesion layer.Ta-TiN and Ti-TiN combined adhesion and intermediate layer exhibited stronger corrosion resistance,with the corrosion current to be less than 10^(−6) A·cm^(−2).Ta-C protective coating deposited by using filtered cathodic arc technology indicated displayed higher corrosion resistance,with the average corrosion density to be about 1.26×10^(−7) A·cm^(−2).Ta-C coating also shown larger contact angle,with the highest hydrophobicity,which was one of the important advantages for Ta-C,in terms of corrosion resistance.According to Raman spectroscopy,the I(D)/I(G)=549.8/1126.7=0.487,with the estimated fraction of sp^(3) bonding to be in the range of 5154%.The intermediate layer TiN has higher conductivity than the CrN layer.Considering cost,corrosion performance and ICR result,the Ti-TiN layer combination is recommended for industrial scale application.[Conclusions]Multiple layer coating structure of Ta-C film had stronger corrosion resistance;with more than 50%sp^(3) content,while it also had larger water contact angle and higher corrosion resistance than DLC film.The filtered arcing deposition technology was able to make the film to be more consistent and stable than normal arcing technology in terms of the preparation of Ta-C.The coating displayed corrosion density of 1.26×10^(−7) A·cm^(−2) and ICR of less than 5 mΩ·cm^(2),far beyond technical target of 2025 DOE(US Department of Energy).This indicated that the mass-production scale coating technology for PEMFC bipolar plates is highly possible.展开更多
High-quality antiferromagnetic(AFM)θ-phase manganese nitride(MnN)films were successfully grown on MgO(001)substrates by plasma-assisted molecular beam epitaxy.Structural analysis confirms the high-quality MnN film ha...High-quality antiferromagnetic(AFM)θ-phase manganese nitride(MnN)films were successfully grown on MgO(001)substrates by plasma-assisted molecular beam epitaxy.Structural analysis confirms the high-quality MnN film has a tetragonal distortion with a c/a ratio of~0.98.The film exhibits exceptional stability in both aqueous and ambient conditions,which is a crucial factor for practical applications.Electrical transport reveals its metallic behavior with an upturn at low temperatures,which could be attributed to the Kondo effect originated from nitrogen vacancy-induced magnetic impurities.Room temperature exchange bias has been demonstrated in a MnN/CoFeB heterostructure,verifying the AFM ordering of MnN.Considering its high Néel temperature~650 K,superior stability,and low-cost,this work highlights the epitaxial MnN films as a promising candidate for AFM spintronic applications.展开更多
Developing lightweight and flexible thin films for electromagnetic interference(EMI)shielding is of great importance.Porous thin films of reduced graphene oxide containing SiC whiskers(SiC@RGO)for EMI shielding were p...Developing lightweight and flexible thin films for electromagnetic interference(EMI)shielding is of great importance.Porous thin films of reduced graphene oxide containing SiC whiskers(SiC@RGO)for EMI shielding were prepared by a two-step reduction of graphene oxide(GO),in which the two steps were chemical reduction by HI and the solid phase microwave irradiation.A significant increase of the film thickness from around 20 to 200μm was achieved due to the formation of a porous structure by gases released during the 3 s of solid phase microwave irradiation.The total shielding effectiveness(SET)and the reflective SE(SE_(R))of the SiC@RGO porous thin films depended on the GO/SiC mass ratio.The highest SET achieved was 35.6 dB while the SE_(R) was only 2.8 dB,when the GO/SiC mass ratio was 4∶1.The addition of SiC whiskers was critical for the multi-reflection,interfacial po-larization and dielectric attenuation of EM waves.A multilayer film with a gradient change of SE values was constructed using SiC@RGO porous films and multi-walled carbon nanotubes buckypapers.The highest SET of the multilayer films reached 75.1 dB with a SE_(R) of 2.7 dB for a film thickness of about 1.5 mm.These porous SiC@RGO thin films should find use in multilayer or sand-wich structures for EMI absorption in packaging or lining.展开更多
Energetic Semiconductor bridge(ESCB)based on reactive multilayered films(RMFs)has a promising application in the miniature and intelligence of initiator and pyrotechnics device.Understanding the ignition enhancement m...Energetic Semiconductor bridge(ESCB)based on reactive multilayered films(RMFs)has a promising application in the miniature and intelligence of initiator and pyrotechnics device.Understanding the ignition enhancement mechanism of RMFs on semiconductor bridge(SCB)during the ignition process is crucial for the engineering and practical application of advanced initiator and pyrotechnics devices.In this study,a one-dimensional(1D)gas-solid two-phase flow ignition model was established to study the ignition process of ESCB to charge particles based on the reactivity of Al/MoO_(3) RMFs.In order to fully consider the coupled exothermic between the RMFs and the SCB plasma during the ignition process,the heat release of chemical reaction in RMFs was used as an internal heat source in this model.It is found that the exothermal reaction in RMFs improved the ignition performance of SCB.In the process of plasma rapid condensation with heat release,the product of RMFs enhanced the heat transfer process between the gas phase and the solid charge particle,which accelerated the expansion of hot plasma,and heated the solid charge particle as well as gas phase region with low temperature.In addition,it made up for pressure loss in the gas phase.During the plasma dissipation process,the exothermal chemical reaction in RMFs acted as the main heating source to heat the charge particle,making the surface temperature of the charge particle,gas pressure,and gas temperature rise continuously.This result may yield significant advantages in providing a universal ignition model for miniaturized ignition devices.展开更多
The influence of oxygen vacancy-dominated carrier mobility on the performance of memristors has attractedconsiderable attention.The device’s carrier mobility can be significantly improved by forming a nano-multilayer...The influence of oxygen vacancy-dominated carrier mobility on the performance of memristors has attractedconsiderable attention.The device’s carrier mobility can be significantly improved by forming a nano-multilayeredheterostructure when the individual layer thickness is below a critical value.In this work,Pt/[ZrO_(2):Y_(2)O_(3)(YSZ)/SrTiO_(3)(STO)]n/Nb:SrTiO_(3)(NSTO)memristive devices were configurated through laser pulse deposited YSZ/STO nanomultilayeredactive layer with both Pt and NSTO acting as top and counter electrodes.Specifically,the Pt/[YSZ/STO]5/NSTO device with five consecutive layers of YSZ/STO thin film shows superior memristor performance,and itscorresponding carrier mobility presents a significantly enhanced value compared to that of other periodic numbers ofYSZ/STO composed memristive devices.This can be attributed to the increase of oxygen vacancy concentration in thedevice,as evidenced by both experimental results and theoretical analysis.This work provides a significant approach inimproving the performance of memristor dominated by oxygen vacancy transporting mechanism.展开更多
Nanostructured BN and BN-Co films with Cu,Co,Au as the top electrodes,and Pt as the bottom electrodes were grown by magnetron sputtering.Both BN samples and BN-Co ones show bipolar resistive switching behaviors.For th...Nanostructured BN and BN-Co films with Cu,Co,Au as the top electrodes,and Pt as the bottom electrodes were grown by magnetron sputtering.Both BN samples and BN-Co ones show bipolar resistive switching behaviors.For the sample with active Cu as the top electrode,the formation and rupture of metallic Cu conductive filaments can explain the resistive switching behavior;for the other samples,the generation and annihilation of nitrogen vacancies under the electric stimuli may contribute to the occurrence of resistive switching.Taking advantage of the formed and broken Co-N bonds during resistive switching,the saturation magnetization of the BN-Co films can be modulated.Thus,it investigated the resistive switching behavior of BN and BN-Co materials in this work.Similar to that of oxide materials,the resistive switching behaviors of the nitrides may be attributed to the movement of cations or anions within the dielectric or electrodes during the application of voltage.Additionally,ion migration may lead to the formation or breaking of Co-N bonds,which can effectively regulate the magnetism of BN-Co materials.This study extends resistive switching materials to nitrides,enabling the regulation of magnetism along with resistance changes,thus providing insights for the design of novel voltage-controlled magnetic devices and achieving multi-functionality.展开更多
Porous anodic oxide films were fabricated galvanostatically on titanium alloy Ti-10V-2Fe-3Al in ammonium tartrate solution with different anodizing time.Scanning electron microscopy(SEM) and field emission scanning el...Porous anodic oxide films were fabricated galvanostatically on titanium alloy Ti-10V-2Fe-3Al in ammonium tartrate solution with different anodizing time.Scanning electron microscopy(SEM) and field emission scanning electron microscopy(FE-SEM) were used to investigate the morphology evolution of the anodic oxide film.It is shown that above the breakdown voltage,oxygen is generated with the occurrence of drums morphology.These drums grow and extrude,which yields the compression stress.Subsequently,microcracks are generated.With continuous anodizing,porous oxides form at the microcracks.Those oxides grow and connect to each other,finally replace the microcrack morphology.The depth profile of the anodic oxide film formed at 1 800 s was examined by Auger electron spectroscopy(AES).It is found that the film is divided into three layers according to the molar fractions of elements.The outer layer is incorporated by carbon,which may come from electrolyte solution.The thickness of the outer layer is approximately 0.2-0.3 μm.The molar fractions of elements in the intermediate layer are extraordinarily stable,while those in the inner layer vary significantly with sputtering depth.The thicknesses of the intermediate layer and the inner layer are 2 μm and 1.0-1.5 μm,respectively.Moreover,the growth mechanism of porous anodic oxide films in neutral tartrate solution was proposed.展开更多
ZnO thin films were prepared by direct current(DC)reactive magnetron sputtering under different oxygen partial pressures.And then the samples were annealed in vacuum at 450℃.The effects of the oxygen partial pressure...ZnO thin films were prepared by direct current(DC)reactive magnetron sputtering under different oxygen partial pressures.And then the samples were annealed in vacuum at 450℃.The effects of the oxygen partial pressures and the treatment of annealing in vacuum on the photoluminescence and the concentration of six intrinsic defects in ZnO thin films such as oxygen vacancy(VO),zinc vacancy(VZn),antisite oxygen(OZn),antisite zinc(ZnO),interstitial oxygen(Oi)and interstitial zinc(Zni)were studied.The results show that a green photoluminescence peak at 520 nm can be observed in all the samples,whose intensity increases with increasing oxygen partial pressure;for the sample annealed in vacuum,the intensity of the green peak increases as well.The green photoluminescence peak observed in ZnO may be attributed to zinc vacancy,which probably originates from transitions between electrons in the conduction band and zinc vacancy levels,or from transitions between electrons in zinc vacancy levels and up valence band.展开更多
Preparation of TiO<sub>2</sub> thin films by MOCVD method is presented in this paper. A MOCVD system has been designed and built. A wide range of processing conditions are investigated to deposit TiO<su...Preparation of TiO<sub>2</sub> thin films by MOCVD method is presented in this paper. A MOCVD system has been designed and built. A wide range of processing conditions are investigated to deposit TiO<sub>2</sub> films on Si wafers starting from metal-organic precursor tetrabutyl titanate. Activation energy of the film formation （E） is obtained to be 23.6 kJ/mol. Structure of films is pure anatase when deposit temperatures are low, rutile forms at 700℃. The films also exhibit preferred crystallographic orientations which strongly depend on deposit conditions. Refractive index increases with increasing of film thickness and decreasing of deposit temperature.展开更多
[SiO2/FePt]5/Ag thin films were deposited by RF magnetron sputtering on the glass substrates and post annealing at 550 ℃ for 30 min in vacuum. Vibrating sample magnetometer and X-ray diffraction analyser were applied...[SiO2/FePt]5/Ag thin films were deposited by RF magnetron sputtering on the glass substrates and post annealing at 550 ℃ for 30 min in vacuum. Vibrating sample magnetometer and X-ray diffraction analyser were applied to study the magnetic properties and microstructures of the films. The results show that without Ag underlayer [SiO2/FePt]5 films deposited onto the glass are FCC disordered; with the addition of Ag underlayer [SiO]FePt]5/Ag films are changed into L10 and （111） mixed texture. The variation of the SiO2 nonmagnetic layer thickness in [SiO2/FePt]5/Ag films indicates that SiO2-doping plays an important role in improving the order parameter and the perpendicular magnetic anisotropy, and reducing the grain size and intergrain interactions. By controlling SiO2 thickness the highly perpendicular magnetic anisotropy can be obtained in the [SiO2 （0.6 nm）/FePt （3 nm）]5/Ag （50 nm） films and highly （001）-oriented films can be obtained in the [SiO2 （2 nm）/FePt （3 nm）]5/Ag （50 nm） films.展开更多
The crystalline structure and surface morphology of TiO2 semiconductor coating play an important role in the conversion efficiency of dye-sensitized solar cells. In order to obtain TiO2 coating with controllable morph...The crystalline structure and surface morphology of TiO2 semiconductor coating play an important role in the conversion efficiency of dye-sensitized solar cells. In order to obtain TiO2 coating with controllable morphology and high porosity, nanoporous TiO2 films were fabricated on conducting glass （FTO） substrates, Ti thin films （1.5-2 gin） were deposited on conducting glass （FTO） substrates via the DC sputtering method, and then electrochemically anodized in NH4F/ethylene glycol solution. The crystalline structure and surface morphology of the samples were characterized by X-ray diffraction （XRD） and field emission scanning electron microscopy （FESEM）, respectively. The influences of anodizing potential, electrolyte composition, and pH value on the surface morphology of nanoporous TiO2 films were extensively studied. The growth mechanism of nanoporous TiO2 films was discussed by current density variations with anodizing time. The results demonstrate that nanoporous TiO2 films with high porosity and three-dimensional （3D） networks are observed at 30 V, when the NH4F concentration in ethylene glycol solution is 0.3% （mass fraction） and the electrolyte pH value is 5.0.展开更多
Recently,with the rapid development of chemical vapor deposition(CVD)technology,large area free-standing CVD diamond films have been produced successfully.However,the coarse grain size on the surface and the non-unifo...Recently,with the rapid development of chemical vapor deposition(CVD)technology,large area free-standing CVD diamond films have been produced successfully.However,the coarse grain size on the surface and the non-uniform thickness of unprocessed CVD diamond films make it difficult to meet the application requirement.The current study evaluates several existing polishing methods for CVD diamond films,including mechanical polishing,chemical mechanical polishing and tribochemical polishing technology.展开更多
Vanadium pentoxide xerogel films used for lithium rechargeable batteries were prepared from crystalline c-V2O5 by melt quenching method,then the electrochemical process of lithium intercalation into vanadium pentoxide...Vanadium pentoxide xerogel films used for lithium rechargeable batteries were prepared from crystalline c-V2O5 by melt quenching method,then the electrochemical process of lithium intercalation into vanadium pentoxide xerogel films was simulated with an equivalent circuit model, which was derived from the mechanism of electrode reactions. Measured electrochemical impedance spectra at various electrode potentials were analyzed by using the complex non-linear least-squares fitting method. The results show that impedance spectra consist of 2 high-to- medium frequency depressed arcs and a low frequency straight line. The high frequency arc is attributed to the absorption reaction of lithium ions into the oxide film, the medium frequency arc is attributed to the charge transfer reaction at the vanadium oxide/electrolyte interface and the low frequency is characterized by a straight line with a phase angle of 45° corresponding to the diffusion of lithium ion through vanadium oxide phase. The experimental and calculated results are compared and discussed focusing on the electrochemical performance and the state of charge of the electrode. Moreover, the high consistence of the fitted values of the model to the experimental data indicates that this mathematical model does give a satisfying description of the intercalation process of vanadium pentoxide xerogel films.展开更多
Thin films of PrCoO3 were deposited on LaAlO3 substrates by pulsed laser deposition technique.X-ray diffraction result indicates that films are single phase and c-axis textured.To investigate the spin state transition...Thin films of PrCoO3 were deposited on LaAlO3 substrates by pulsed laser deposition technique.X-ray diffraction result indicates that films are single phase and c-axis textured.To investigate the spin state transition,Raman spectroscopy measurements were performed at different temperatures.The position of the Raman modes is found to increase while full width at half maximum(FWHM) of these modes is found to decrease with the decrease of temperature across spin state transition temperature(220 K) of PrCoO3.展开更多
Hydrogenated microcrystalline silicon(μc-Si:H)films were prepared on glass and silicon substrates by radio frequency magnetron sputtering at 100°C using a mixture of argon(Ar)and hydrogen(H2)gasses as precursor ...Hydrogenated microcrystalline silicon(μc-Si:H)films were prepared on glass and silicon substrates by radio frequency magnetron sputtering at 100°C using a mixture of argon(Ar)and hydrogen(H2)gasses as precursor gas.The effects of the ratio of hydrogen flow(H2/(Ar+H2)%)on the microstructure were evaluated.Results show that the microstructure,bonding structure,and surface morphology of theμc-Si:H films can be tailored based on the ratio of hydrogen flow.An amorphous to crystalline phase transition occurred when the ratio of hydrogen flow increased up to 50%.The crystallinity increased and tended to stabilize with the increase in ratio of hydrogen flow from 40%to 70%.The surface roughness of thin films increased,and total hydrogen content decreased as the ratio of hydrogen flow increased.Allμc-Si:H films have a preferred(111)orientation,independent of the ratio of hydrogen flow.And theμc-Si:H films had a dense structure,which shows their excellent resistance to post-oxidation.展开更多
Epitaxy is usually used to produce high quality crystals with ato-mic perfection. Up to now, many semiconductor crystals of functional materials could be obtained by epitaxial growth techniques, such as molecular beam...Epitaxy is usually used to produce high quality crystals with ato-mic perfection. Up to now, many semiconductor crystals of functional materials could be obtained by epitaxial growth techniques, such as molecular beam epitaxy, chemical vapor deposition, and liquid-phase epitaxy. However, these techniques are expensive, sophisticated, and not compatible with large area production. For solution-based deposition of epitaxial films such as hydrothermal processing [1], chemical bath deposition [2-3], and electrodeposition [4-5], specific conditions such as high temperature and pressure, or conducting substrates are commonly needed. Since single crystal epitaxial films have superior electronic and optical properties compared to amorphous and polycrystalline films due to absence of high-angle grain boundaries, searching for simple, rapid and inexpensive technique to grow epitaxial films is highly desired.展开更多
Platinum-Iridium alloy films were prepared by MOCVD on Mo substrate using metal-acetylacetonate precursors. Effects of deposition conditions on composition, microstructure and mechanical properties were determined. In...Platinum-Iridium alloy films were prepared by MOCVD on Mo substrate using metal-acetylacetonate precursors. Effects of deposition conditions on composition, microstructure and mechanical properties were determined. In these experimental conditions, the purities of films are high and more than 99.0%. The films are homogeneous and monophase solid solution of Pt and Ir. Weight percentage of platinum are much higher than iridium in the alloy. Lattice constant of the alloy changes with the platinum composition. Iridium composition showing an up-down-up trend at the precursor temperature of 190~230℃ and the deposition temperature at 400~ 550℃. The hardness of Pt-Ir alloys prepared by MOCVD is three times more than the alloys prepared by casting.展开更多
Titanium dioxide(TiO2) films were prepared by cone - jet mode electrospraying a titanium ethoxideprecursor solution onto a silicon substrate.The effects of spraying time,substrate temperature and aging on thesurface m...Titanium dioxide(TiO2) films were prepared by cone - jet mode electrospraying a titanium ethoxideprecursor solution onto a silicon substrate.The effects of spraying time,substrate temperature and aging on thesurface morphology of the films prepared were studied.Thin films obtained after spraying for 600 s were aged atroom temperature to form a porous TiO2 network with pores in the size range of 100 - 500 nm.Thicker filmswere prepared by spraying for 3 000 s,but these cracked on drying although it can be concluded that films pre-pared using a higher substrate temperature were denser.By this method,SiC coating was also prepared on anAl2O3 substrate using polysilane as a precursor.The result implies the potential of an industrial production ofdye sensitized solar cells by electrospraying technique.展开更多
基金the National Natural Science Foundation of China(22279097)the Key R&D Program of Hubei Province(2023BAB103)the PhD Scientific Research and Innovation Foundation of The Education Department of Hainan Province Joint Project of Sanya Yazhou Bay Science and Technology City(HSPHDSRF-2024-03-022)。
文摘Because of their low electrical conductivity,sluggish ion diffusion,and poor stability,conventional electrode materials are not able to meet the growing demands of energy storage and portable devices.Graphene assembled films(GAFs)formed from graphene nanosheets have an ultrahigh conductivity,a unique 2D network structure,and exceptional mechanical strength,which give them the potential to solve these problems.However,a systematic understanding of GAFs as an advanced electrode material is lacking.This review focuses on the use of GAFs in electrochemistry,providing a comprehensive analysis of their synthesis methods,surface/structural characteristics,and physical properties,and thus understand their structure-property relationships.Their advantages in batteries,supercapacitors,and electrochemical sensors are systematically evaluated,with an emphasis on their excellent electrical conductivity,ion transport kinetics,and interfacial stability.The existing problems in these devices,such as chemical inertness and mechanical brittleness,are discussed and potential solutions are proposed,including defect engineering and hybrid structures.This review should deepen our mechanistic understanding of the use of GAFs in electrochemical systems and provide actionable strategies for developing stable,high-performance electrode materials.
基金Major Science and technology projects of Anhui Province (202103a05020003)。
文摘[Background and purposes]Proton exchange membrane fuel cells(PEMFCs),which convert hydrogen energy directly into electrical energy and water,have received overwhelming attention,owing to their potential to significantly reduce energy consumption,pollution emissions and reliance on fossil fuels.Bipolar plates are the major part and key component of PEMFCs stack,which provide mechanical strength,collect and conduct current segregate oxidants and reduce agents.They contribute 70-80%weight and 20-30%cost of a whole stack,while significantly affecting the power density.There are three types plates,including metal bipolar plate,graphite bipolar plate and composite bipolar plate.Stainless steel bipolar plates,as one of metal bipolar plate,exhibit promising manufacturability,competitive cost and durability among various metal materials.However,stainless steel would be corroded in the harsh acid(pH 2-5)and humid PEMFCs environment,whereas the leached ions will contaminate the membrane.In addition,the passivated film formed on the surface will increase the interfacial contact resistance(ICR).In order to improve the corrosion resistance and electrical conductivity of steel bipolar plates,surface coatings are essential.Metal nitride coatings,metal carbide coatings,polymer coatings and carbon-based coatings have been introduced in recent years.Carbon-based coatings,mainly including a-C(amorphous Carbon),Ta-C(Tetrahedral amorphous carbon)and DLC(diamond-like carbon),have attracted considerable attention from both academia and industry,owing to their superior performance,such as chemical inertness,mechanical hardness and electrical conductivity.However,Ta-C films as protective coating of PEMFCs have been rarely reported,due to the difficulty in production for industrial application.In this paper,multi-layer Ta-C composite films were produced by using customized industrial-scale vacuum equipment to address those issues.[Methods]Multiple layered Ta-C coatings were prepared by using PIS624 equipment,which assembled filtered cathodic arc evaporation,ion beam and magnetron sputtering into one equipment,while SS304 and silicon specimens were used as substrate for testing and analysis.Adhesion layer and intermediate layer were deposited by using magnetron sputtering at deposition temperature of 150℃and pressure of 3×10^(−1) Pa,while the sputtering current was set to be 5 A and bias power to be 300 V.The Ta-C layer was coated at arc current of 80-100 A,bias voltage of 1500 V and gas flow of 75 sccm.A scanning electron microscope(CIQTEK SEM3200)was used to characterize surface morphology,coating structure and cross-section profile of the coatings.Raman spectrometer(LabRam HR Evolution,HORIBA JOBIN YVON)was used to identify the bonding valence states.Electrochemical tests were performed by using an electrochemical work station(CHI760,Shanghai Chenhua Instrument Co.,Ltd.),with the traditional three electrode system,where saturated Ag/AgCl and platinum mesh were used as the reference electrode and counter electrode,respectively.All samples were mounted in plastic tube and sealed with epoxy resin,with an exposure area of 2.25 cm^(2),serving as the working electrode.Electrochemical measurements were carried out in simulated PEMFCs cathode environment in 0.5 mol·L^(−1) H_(2)SO_(4)+5 ppm F−solution,at operating temperature of 70℃.As the cathode environment was harsher than the anode environment,all the samples are stabilized at the open-circuit potential(OCP)for approximately 30 min before the EIS measurements.ICR between bipolar plates and GDL was a key parameter affecting performance of the PEMFCs stack.The test sample sandwiched between 2 pieces of carbon paper(simulate gas diffusion layer,GDL)was placed between 2 gold-plated copper electrodes at a compaction pressure of 1.4 MPa,which was considered to be the conventional compaction pressure in the PEMFCs.Under the same conditions,the resistance of a single carbon paper was measured as well.The ICR was calculated according to the formula ICR=1/2(R2−R1)×S,where S was the contact area between GDL and coated stainless steel BPPs.All data of ICR were measured three times for averaging.[Results]The coatings deposited by filtered cathodic arc technology were compact and smooth,which reduced coating porosity and favorable to corrosion resistance.The coating thickness of adhesion and intermediate layers were 180 nm,while the protective Ta-C coating thickness was about 300 nm,forming multiple coating to provide stronger protection for metal bipolar plates.Cr,Ti,Nb and Ta coatings were selected as adhesion layers for comparison.According to electrochemical test,Ta and Nb coatings have higher corrosion resistance.However,Ta and Nb materials would be costly when they are used for mass production.Relatively,Cr and Ti materials were cost effective.Hence,a comprehensive assessment was indispensable to decide the materials to be selected as adhesion layer.Ta-TiN and Ti-TiN combined adhesion and intermediate layer exhibited stronger corrosion resistance,with the corrosion current to be less than 10^(−6) A·cm^(−2).Ta-C protective coating deposited by using filtered cathodic arc technology indicated displayed higher corrosion resistance,with the average corrosion density to be about 1.26×10^(−7) A·cm^(−2).Ta-C coating also shown larger contact angle,with the highest hydrophobicity,which was one of the important advantages for Ta-C,in terms of corrosion resistance.According to Raman spectroscopy,the I(D)/I(G)=549.8/1126.7=0.487,with the estimated fraction of sp^(3) bonding to be in the range of 5154%.The intermediate layer TiN has higher conductivity than the CrN layer.Considering cost,corrosion performance and ICR result,the Ti-TiN layer combination is recommended for industrial scale application.[Conclusions]Multiple layer coating structure of Ta-C film had stronger corrosion resistance;with more than 50%sp^(3) content,while it also had larger water contact angle and higher corrosion resistance than DLC film.The filtered arcing deposition technology was able to make the film to be more consistent and stable than normal arcing technology in terms of the preparation of Ta-C.The coating displayed corrosion density of 1.26×10^(−7) A·cm^(−2) and ICR of less than 5 mΩ·cm^(2),far beyond technical target of 2025 DOE(US Department of Energy).This indicated that the mass-production scale coating technology for PEMFC bipolar plates is highly possible.
文摘High-quality antiferromagnetic(AFM)θ-phase manganese nitride(MnN)films were successfully grown on MgO(001)substrates by plasma-assisted molecular beam epitaxy.Structural analysis confirms the high-quality MnN film has a tetragonal distortion with a c/a ratio of~0.98.The film exhibits exceptional stability in both aqueous and ambient conditions,which is a crucial factor for practical applications.Electrical transport reveals its metallic behavior with an upturn at low temperatures,which could be attributed to the Kondo effect originated from nitrogen vacancy-induced magnetic impurities.Room temperature exchange bias has been demonstrated in a MnN/CoFeB heterostructure,verifying the AFM ordering of MnN.Considering its high Néel temperature~650 K,superior stability,and low-cost,this work highlights the epitaxial MnN films as a promising candidate for AFM spintronic applications.
文摘Developing lightweight and flexible thin films for electromagnetic interference(EMI)shielding is of great importance.Porous thin films of reduced graphene oxide containing SiC whiskers(SiC@RGO)for EMI shielding were prepared by a two-step reduction of graphene oxide(GO),in which the two steps were chemical reduction by HI and the solid phase microwave irradiation.A significant increase of the film thickness from around 20 to 200μm was achieved due to the formation of a porous structure by gases released during the 3 s of solid phase microwave irradiation.The total shielding effectiveness(SET)and the reflective SE(SE_(R))of the SiC@RGO porous thin films depended on the GO/SiC mass ratio.The highest SET achieved was 35.6 dB while the SE_(R) was only 2.8 dB,when the GO/SiC mass ratio was 4∶1.The addition of SiC whiskers was critical for the multi-reflection,interfacial po-larization and dielectric attenuation of EM waves.A multilayer film with a gradient change of SE values was constructed using SiC@RGO porous films and multi-walled carbon nanotubes buckypapers.The highest SET of the multilayer films reached 75.1 dB with a SE_(R) of 2.7 dB for a film thickness of about 1.5 mm.These porous SiC@RGO thin films should find use in multilayer or sand-wich structures for EMI absorption in packaging or lining.
基金supported by the National Natural Science Foundation of China(Grant Nos.22275092,52102107 and 52372084)the Fundamental Research Funds for the Central Universities(Grant No.30923010920)。
文摘Energetic Semiconductor bridge(ESCB)based on reactive multilayered films(RMFs)has a promising application in the miniature and intelligence of initiator and pyrotechnics device.Understanding the ignition enhancement mechanism of RMFs on semiconductor bridge(SCB)during the ignition process is crucial for the engineering and practical application of advanced initiator and pyrotechnics devices.In this study,a one-dimensional(1D)gas-solid two-phase flow ignition model was established to study the ignition process of ESCB to charge particles based on the reactivity of Al/MoO_(3) RMFs.In order to fully consider the coupled exothermic between the RMFs and the SCB plasma during the ignition process,the heat release of chemical reaction in RMFs was used as an internal heat source in this model.It is found that the exothermal reaction in RMFs improved the ignition performance of SCB.In the process of plasma rapid condensation with heat release,the product of RMFs enhanced the heat transfer process between the gas phase and the solid charge particle,which accelerated the expansion of hot plasma,and heated the solid charge particle as well as gas phase region with low temperature.In addition,it made up for pressure loss in the gas phase.During the plasma dissipation process,the exothermal chemical reaction in RMFs acted as the main heating source to heat the charge particle,making the surface temperature of the charge particle,gas pressure,and gas temperature rise continuously.This result may yield significant advantages in providing a universal ignition model for miniaturized ignition devices.
基金Projects(2023JJ30690,2022JJ30722)supported by the Natural Science Foundation of Hunan Province,ChinaProject(kq2202093)supported by the Natural Science Foundation of Changsha,ChinaProject(SKL202202SIC)supported by the Opening Project of State Key Laboratory of High Performance Ceramics and Superfine Microstructure,China。
文摘The influence of oxygen vacancy-dominated carrier mobility on the performance of memristors has attractedconsiderable attention.The device’s carrier mobility can be significantly improved by forming a nano-multilayeredheterostructure when the individual layer thickness is below a critical value.In this work,Pt/[ZrO_(2):Y_(2)O_(3)(YSZ)/SrTiO_(3)(STO)]n/Nb:SrTiO_(3)(NSTO)memristive devices were configurated through laser pulse deposited YSZ/STO nanomultilayeredactive layer with both Pt and NSTO acting as top and counter electrodes.Specifically,the Pt/[YSZ/STO]5/NSTO device with five consecutive layers of YSZ/STO thin film shows superior memristor performance,and itscorresponding carrier mobility presents a significantly enhanced value compared to that of other periodic numbers ofYSZ/STO composed memristive devices.This can be attributed to the increase of oxygen vacancy concentration in thedevice,as evidenced by both experimental results and theoretical analysis.This work provides a significant approach inimproving the performance of memristor dominated by oxygen vacancy transporting mechanism.
文摘Nanostructured BN and BN-Co films with Cu,Co,Au as the top electrodes,and Pt as the bottom electrodes were grown by magnetron sputtering.Both BN samples and BN-Co ones show bipolar resistive switching behaviors.For the sample with active Cu as the top electrode,the formation and rupture of metallic Cu conductive filaments can explain the resistive switching behavior;for the other samples,the generation and annihilation of nitrogen vacancies under the electric stimuli may contribute to the occurrence of resistive switching.Taking advantage of the formed and broken Co-N bonds during resistive switching,the saturation magnetization of the BN-Co films can be modulated.Thus,it investigated the resistive switching behavior of BN and BN-Co materials in this work.Similar to that of oxide materials,the resistive switching behaviors of the nitrides may be attributed to the movement of cations or anions within the dielectric or electrodes during the application of voltage.Additionally,ion migration may lead to the formation or breaking of Co-N bonds,which can effectively regulate the magnetism of BN-Co materials.This study extends resistive switching materials to nitrides,enabling the regulation of magnetism along with resistance changes,thus providing insights for the design of novel voltage-controlled magnetic devices and achieving multi-functionality.
基金Project(50571003) supported by the National Natural Science Foundation of China
文摘Porous anodic oxide films were fabricated galvanostatically on titanium alloy Ti-10V-2Fe-3Al in ammonium tartrate solution with different anodizing time.Scanning electron microscopy(SEM) and field emission scanning electron microscopy(FE-SEM) were used to investigate the morphology evolution of the anodic oxide film.It is shown that above the breakdown voltage,oxygen is generated with the occurrence of drums morphology.These drums grow and extrude,which yields the compression stress.Subsequently,microcracks are generated.With continuous anodizing,porous oxides form at the microcracks.Those oxides grow and connect to each other,finally replace the microcrack morphology.The depth profile of the anodic oxide film formed at 1 800 s was examined by Auger electron spectroscopy(AES).It is found that the film is divided into three layers according to the molar fractions of elements.The outer layer is incorporated by carbon,which may come from electrolyte solution.The thickness of the outer layer is approximately 0.2-0.3 μm.The molar fractions of elements in the intermediate layer are extraordinarily stable,while those in the inner layer vary significantly with sputtering depth.The thicknesses of the intermediate layer and the inner layer are 2 μm and 1.0-1.5 μm,respectively.Moreover,the growth mechanism of porous anodic oxide films in neutral tartrate solution was proposed.
基金Project(60571043)supported by the National Natural Science Foundation of China
文摘ZnO thin films were prepared by direct current(DC)reactive magnetron sputtering under different oxygen partial pressures.And then the samples were annealed in vacuum at 450℃.The effects of the oxygen partial pressures and the treatment of annealing in vacuum on the photoluminescence and the concentration of six intrinsic defects in ZnO thin films such as oxygen vacancy(VO),zinc vacancy(VZn),antisite oxygen(OZn),antisite zinc(ZnO),interstitial oxygen(Oi)and interstitial zinc(Zni)were studied.The results show that a green photoluminescence peak at 520 nm can be observed in all the samples,whose intensity increases with increasing oxygen partial pressure;for the sample annealed in vacuum,the intensity of the green peak increases as well.The green photoluminescence peak observed in ZnO may be attributed to zinc vacancy,which probably originates from transitions between electrons in the conduction band and zinc vacancy levels,or from transitions between electrons in zinc vacancy levels and up valence band.
文摘Preparation of TiO<sub>2</sub> thin films by MOCVD method is presented in this paper. A MOCVD system has been designed and built. A wide range of processing conditions are investigated to deposit TiO<sub>2</sub> films on Si wafers starting from metal-organic precursor tetrabutyl titanate. Activation energy of the film formation （E） is obtained to be 23.6 kJ/mol. Structure of films is pure anatase when deposit temperatures are low, rutile forms at 700℃. The films also exhibit preferred crystallographic orientations which strongly depend on deposit conditions. Refractive index increases with increasing of film thickness and decreasing of deposit temperature.
基金Project(10574085) supported by the National Natural Science Foundation of ChinaProject(207020) supported by the Science Technology Key Project of the Ministry of Education, China
文摘[SiO2/FePt]5/Ag thin films were deposited by RF magnetron sputtering on the glass substrates and post annealing at 550 ℃ for 30 min in vacuum. Vibrating sample magnetometer and X-ray diffraction analyser were applied to study the magnetic properties and microstructures of the films. The results show that without Ag underlayer [SiO2/FePt]5 films deposited onto the glass are FCC disordered; with the addition of Ag underlayer [SiO]FePt]5/Ag films are changed into L10 and （111） mixed texture. The variation of the SiO2 nonmagnetic layer thickness in [SiO2/FePt]5/Ag films indicates that SiO2-doping plays an important role in improving the order parameter and the perpendicular magnetic anisotropy, and reducing the grain size and intergrain interactions. By controlling SiO2 thickness the highly perpendicular magnetic anisotropy can be obtained in the [SiO2 （0.6 nm）/FePt （3 nm）]5/Ag （50 nm） films and highly （001）-oriented films can be obtained in the [SiO2 （2 nm）/FePt （3 nm）]5/Ag （50 nm） films.
基金Projects(21171027,50872014) supported by the National Natural Science Foundation of ChinaProject(K1001020-11)supported by the Science and Technology Key Project of Changsha City,China
文摘The crystalline structure and surface morphology of TiO2 semiconductor coating play an important role in the conversion efficiency of dye-sensitized solar cells. In order to obtain TiO2 coating with controllable morphology and high porosity, nanoporous TiO2 films were fabricated on conducting glass （FTO） substrates, Ti thin films （1.5-2 gin） were deposited on conducting glass （FTO） substrates via the DC sputtering method, and then electrochemically anodized in NH4F/ethylene glycol solution. The crystalline structure and surface morphology of the samples were characterized by X-ray diffraction （XRD） and field emission scanning electron microscopy （FESEM）, respectively. The influences of anodizing potential, electrolyte composition, and pH value on the surface morphology of nanoporous TiO2 films were extensively studied. The growth mechanism of nanoporous TiO2 films was discussed by current density variations with anodizing time. The results demonstrate that nanoporous TiO2 films with high porosity and three-dimensional （3D） networks are observed at 30 V, when the NH4F concentration in ethylene glycol solution is 0.3% （mass fraction） and the electrolyte pH value is 5.0.
基金Science and technology plan project of Hebei Academy of Sciences(No.191408)Natural Science Foundation of Hebei Province(E2019302005)
文摘Recently,with the rapid development of chemical vapor deposition(CVD)technology,large area free-standing CVD diamond films have been produced successfully.However,the coarse grain size on the surface and the non-uniform thickness of unprocessed CVD diamond films make it difficult to meet the application requirement.The current study evaluates several existing polishing methods for CVD diamond films,including mechanical polishing,chemical mechanical polishing and tribochemical polishing technology.
文摘Vanadium pentoxide xerogel films used for lithium rechargeable batteries were prepared from crystalline c-V2O5 by melt quenching method,then the electrochemical process of lithium intercalation into vanadium pentoxide xerogel films was simulated with an equivalent circuit model, which was derived from the mechanism of electrode reactions. Measured electrochemical impedance spectra at various electrode potentials were analyzed by using the complex non-linear least-squares fitting method. The results show that impedance spectra consist of 2 high-to- medium frequency depressed arcs and a low frequency straight line. The high frequency arc is attributed to the absorption reaction of lithium ions into the oxide film, the medium frequency arc is attributed to the charge transfer reaction at the vanadium oxide/electrolyte interface and the low frequency is characterized by a straight line with a phase angle of 45° corresponding to the diffusion of lithium ion through vanadium oxide phase. The experimental and calculated results are compared and discussed focusing on the electrochemical performance and the state of charge of the electrode. Moreover, the high consistence of the fitted values of the model to the experimental data indicates that this mathematical model does give a satisfying description of the intercalation process of vanadium pentoxide xerogel films.
基金Project supported by the Second Stage of Brain Korea 21 Project
文摘Thin films of PrCoO3 were deposited on LaAlO3 substrates by pulsed laser deposition technique.X-ray diffraction result indicates that films are single phase and c-axis textured.To investigate the spin state transition,Raman spectroscopy measurements were performed at different temperatures.The position of the Raman modes is found to increase while full width at half maximum(FWHM) of these modes is found to decrease with the decrease of temperature across spin state transition temperature(220 K) of PrCoO3.
基金Projects(51505050,51805063) supported by the National Natural Science Foundation of China for Young ScholarsProjects(KJ1500942,KJQN201801134) supported by the Scientific and Technological Research Program of Chongqing Education Commission of ChinaProjects(cstc2017jcyjAX0075,cstc2015jcyj A50033) supported by the Chongqing Research Program of Basic Research and Frontier Technology,China
文摘Hydrogenated microcrystalline silicon(μc-Si:H)films were prepared on glass and silicon substrates by radio frequency magnetron sputtering at 100°C using a mixture of argon(Ar)and hydrogen(H2)gasses as precursor gas.The effects of the ratio of hydrogen flow(H2/(Ar+H2)%)on the microstructure were evaluated.Results show that the microstructure,bonding structure,and surface morphology of theμc-Si:H films can be tailored based on the ratio of hydrogen flow.An amorphous to crystalline phase transition occurred when the ratio of hydrogen flow increased up to 50%.The crystallinity increased and tended to stabilize with the increase in ratio of hydrogen flow from 40%to 70%.The surface roughness of thin films increased,and total hydrogen content decreased as the ratio of hydrogen flow increased.Allμc-Si:H films have a preferred(111)orientation,independent of the ratio of hydrogen flow.And theμc-Si:H films had a dense structure,which shows their excellent resistance to post-oxidation.
文摘Epitaxy is usually used to produce high quality crystals with ato-mic perfection. Up to now, many semiconductor crystals of functional materials could be obtained by epitaxial growth techniques, such as molecular beam epitaxy, chemical vapor deposition, and liquid-phase epitaxy. However, these techniques are expensive, sophisticated, and not compatible with large area production. For solution-based deposition of epitaxial films such as hydrothermal processing [1], chemical bath deposition [2-3], and electrodeposition [4-5], specific conditions such as high temperature and pressure, or conducting substrates are commonly needed. Since single crystal epitaxial films have superior electronic and optical properties compared to amorphous and polycrystalline films due to absence of high-angle grain boundaries, searching for simple, rapid and inexpensive technique to grow epitaxial films is highly desired.
基金supported by National Natural Science Foundation of China(Grant No.50771051)the Natural Science Foundation of Yunnan,China(Program No2003PY10and No2011FZ220)
文摘Platinum-Iridium alloy films were prepared by MOCVD on Mo substrate using metal-acetylacetonate precursors. Effects of deposition conditions on composition, microstructure and mechanical properties were determined. In these experimental conditions, the purities of films are high and more than 99.0%. The films are homogeneous and monophase solid solution of Pt and Ir. Weight percentage of platinum are much higher than iridium in the alloy. Lattice constant of the alloy changes with the platinum composition. Iridium composition showing an up-down-up trend at the precursor temperature of 190~230℃ and the deposition temperature at 400~ 550℃. The hardness of Pt-Ir alloys prepared by MOCVD is three times more than the alloys prepared by casting.
基金supported by the Science Foun-dation of Educational Commission and Provincial Key Laboratory Program of Liaoning Province of China(Grant No.2008593 and CL-200902)~~
文摘Titanium dioxide(TiO2) films were prepared by cone - jet mode electrospraying a titanium ethoxideprecursor solution onto a silicon substrate.The effects of spraying time,substrate temperature and aging on thesurface morphology of the films prepared were studied.Thin films obtained after spraying for 600 s were aged atroom temperature to form a porous TiO2 network with pores in the size range of 100 - 500 nm.Thicker filmswere prepared by spraying for 3 000 s,but these cracked on drying although it can be concluded that films pre-pared using a higher substrate temperature were denser.By this method,SiC coating was also prepared on anAl2O3 substrate using polysilane as a precursor.The result implies the potential of an industrial production ofdye sensitized solar cells by electrospraying technique.
