Microstructure evolution and mechanical properties of Ti-B-N coatings deposited by plasma-enhanced chemical vapor deposition

Ternary Ti-B-N coatings were synthesized on AISI 304 and Si wafer by plasma-enhanced chemical vapor deposition (PECVD) technique using a gaseous mixture of TiCl4,BCl3,H2,N2,and Ar.By virtue of X-ray diffraction analysis,X-ray photoelectron spectroscopy,scanning electron microscope,and high-resolution transmission electron microscope,the influences of B content on the microstructure and properties of Ti B N coatings were investigated systematically.The results indicated that the microstructure and mechanical properties of Ti-B-N coatings largely depend on the transformation from FCC-TiN phase to HCP-TiB2 phase.With increasing B content and decreasing N content in the coatings,the coating microstructure evolves gradually from FCC-TiN/a-BN to HCP-TiB2 /a-BN via FCC-TiN+HCP-TiB2/a-BN.The highest microhardness of about 34 GPa is achieved,which corresponds to the nanocomposite Ti-63%B-N (mole fraction) coating consisting of the HCP-TiB2 nano-crystallites and amorphous BN phase.The lowest friction-coefficient was observed for the nanocomposite Ti-41%B-N (mole fraction) coating consisting of the FCC-TiN nanocrystallites and amorphous BN

Direct low-temperature synthesis of graphene on various glasses by plasma-enhanced chemical vapor deposition for versatile, cost-effective electrodes

Catalyst-free and scalable synthesis of graphene on various glass substrates at low temperatures is of paramount significance to numerous applications such as low-cost transparent electronics and state-of-the-art displays. However, systematic study within this promising research field has remained scarce thus far. Herein, we report the direct growth of graphene on various glasses using a low-temperature plasma-enhanced chemical vapor deposition method. Such a facile and scalable approach guarantees the growth of uniform, transfer-free graphene films on various glass substrates at a growth temperature range of 400-600 ℃. The morphological, surface wetting, optical, and electrical properties of the obtained graphene can be tailored by controlling the growth parameters. Our uniform and high-quality graphene films directly integrated with low-cost, commonly used glasses show great potential in the fabrication of multi-functional electrodes for versatile applications in solar cells, transparent electronics, and smart windows.

Effects of various substrate materials on structural and optical properties of amorphous silicon nitride thin films deposited by plasma-enhanced chemical vapor deposition

The plasma-enhanced chemical vapor deposition(PECVD)technique is well suited for fabricating optical filters with continuously variable refractive index profiles;however,it is not clear how the optical and structural properties of thin films differ when deposited on different substrates.Herein,silicon nitride films were deposited on silicon,fused silica,and glass substrates by PECVD,using silane and ammonia,to investigate the effects of the substrate used on the optical properties and structures of the films.All of the deposited films were amorphous.Further,the types and amounts of Si-centered tetrahedral Si–SivN4-v bonds formed were based upon the substrates used;Si–N4 bonds with higher elemental nitrogen content were formed on Si substrates,which lead to obtaining higher refractive indices,and the Si–SiN3 bonds were mainly formed on glass and fused silica substrates.The refractive indices of the films formed on the different substrates had a maximum difference of0.05(at 550 nm),the refractive index of SiNx films formed on silicon substrates was 1.83,and the refractive indices of films formed on glass were very close to those formed on fused silica.The deposition rates of these SiNx films are similar,and the extinction coefficients of all the films were lower than 10-4.

Hydrophobic Ti_xO_y-C_mH_n Nanoparticle Film Prepared by Plasma Enhanced Chemical Vapor Deposition

The hydrophobic films of TixOy-CmHn. deposited from mixture gases of titanium isopropoxide （TTIP） and oxygen by plasma enhanced chemical vapor deposition （PECVD） were investigated. The films were investigated by scanning electron microscope （ SEM ）, transmission electron microscope （ TEM ）, Fourier transform infrared spectrometer （ FTIR）, X-Ray diffraction （ XRD ）, element analysis （ EA ）, ultraviolet visible spectrometer （ UV-Vis）, and water contact angle （WCA）. The results reveal that the surface of the films is formed by mierosized papillaes aggregated by inorganic and organic phases of complex nanoparticles with size from 50 nm to 200 nm when the discharge power is increased from 40 W to 150 W. All fdms demonstrate the strong broad of Ti-O-Ti stretching vibration at 400 -800cm-1, -CH bending vibration at 1 388 cm -1, and broadening -OH stretching vibration at 3 000-3500 cm-1 With the increase of the discharge power, the asdeposited film changes from amorphous to crystallization. The WCA of the film can be as high as 160°, indicating the hydrophobicity. The films show a similar ultraviolet absorption property as the bulk TiO2 film. The composition of the composition of film deposited at 150 W can be formulated as Tio.302-C1.5H3. Therefore, the composition formula of this hydrophobic film could be expressed as TiO2-C5H10O4.7. It is believed that the complex micro/nano structures of TiO2 and C5H10O4.7 residues are responsible for the observed hydrophobicity and the ultraviolet absorption property of the film.

Effect of trace oxygen on plasma nitriding of titanium foil

Titanium nitride films are prepared by plasma enhanced chemical vapor deposition method on titanium foil using N_(2) as precursor. In order to evaluate the effect of oxygen on the growth of titanium nitride films, a small amount of O_(2) is introduced into the preparation process. The study indicates that trace O_(2) addition into the reaction chamber gives rise to significant changes on the color and micro-morphology of the foil, featuring dense and long nano-wires. The as-synthesized nanostructures are characterized by various methods and identified as TiN, Ti_(2) N, and TiO_(2) respectively. Moreover, the experiment results show that oxide nanowire has a high degree of crystallinity and the nitrides present specific orientation relationships with the titanium matrix.

铂族金属化学气相沉积

化学气相沉积 (ChemicalVaporDeposition ,CVD)技术可用在高熔点金属如Mo、Re、W等表面制备结合力好的铂族金属涂层。用CVD法可得到具有微细晶粒的致密金属 (无针孔 )涂层 ,可制成大形状和形状复杂的制品 ,也可用于合金涂层的制备。本文介绍了该项技术的国外发展概况 ,并以高温抗氧化铱涂层 (可耐受 2 0 0 0℃高温 )为代表 ,叙述了铂族金属涂层的特点以及该项技术在制备涂层过程中的基本步骤 ,并对工艺参数等各项技术特点进行了系统评述。

Simple method to rapidly fabricate chain-like carbon nanotube films and its field emission properties

A simple process to fabricate chain-like carbon nanotube （CNT） films by microwave plasma-enhanced chemical vapor deposition （MPCVD） was developed successfully. Prior to deposition, the Ti/Al2O3 substrates were ground with Fe-doped SiO2 powder. The nano-structure of the deposited films was analyzed by scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, and Raman spectroscopy. The field electron emission characteristics of the chain-like carbon nanotube films were measured under the vacuum of 10-5 Pa. The low turn-on field of 0.80 V/μm and the emission current density of 8.5 mA/cm2 at the electric field of 3.0 V/μm are obtained. Based on the above results, chain-like carbon nanotube films probably have important applications in cold cathode materials and electrode materials.

Preparation of H-terminated and aminated diamond like carbon surfaces

H-terminated DLC layers were synthesized on SiO 2 substrate by radio frequency (RF) magnetron plasma-enhanced chemical vapor deposition (PECVD) in a conventional reactor using C 4 H 10 as carbon source. As-deposited DLC films were characterized by Raman spectroscopy, scanning electron microscopy (SEM) as well as atomic force microscopy (AFM). The chemical reactivity of the obtained DLC surface was further investigated by exposing the photochemically oxidized DLC surface to a silane reagent. The course of the reaction was followed using water contact angle and X-ray photoelectron spectroscopy.

Roll-to-roll fabrication of large-scale polyorgansiloxane thin film with high flexibility and ultra-efficient atomic oxygen resistance

One of the most widely used and well-established atomic oxygen(AO)protection solutions for low Earth orbit(LEO)satellites is the deposition of protective coatings on polymeric materials.However,manufacturing extensive expanses of these coating materials with good transparency,flexibility,smoothness,ultra-thinness,and exceptional AO resistance remains a critical issue.Herein,we successfully deposited a 400 nm thick polyorgansiloxane(SiO_(x)C_(y)H_(z))coating with high optical transparency and uniform good adherence on to a 1.2 m wide polyimide surface,by optimizing the distribution of hexamethyldisiloxane and oxygen as precursors in the roll-to-roll compatible plasmaenhanced chemical vapor deposition process.After AO irradiation with the fluence of 7.9×10^(20)atoms·cm^(–2),the erosion yield of the SiO_(x)C_(y)H_(z)-coated Kapton was less than 2.30×10^(–26)cm^3·atom^(–1),which was less than 0.77%of that of the Kapton.It indicates that the SiO_(x)C_(y)H_(z)coating can well prevent the erosion of Kapton by AO.In addition,it was also clarified that a SiO_(2) passivation layer was formed on the surface of the SiO_(x)C_(y)H_(z)coating during AO irradiation,which exhibited a‘self-reinforcing’defense mechanism.The entire preparation process of the SiO_(x)C_(y)H_(z)coating was highly efficient and low-cost,and it has shown great potential for applications in LEO.

微晶硅薄膜表面粗糙度的演化过程分析

采用射频等离子体化学气相沉积(RF-PECVD)方法制备了沉积时间系列的微晶硅薄膜。采用椭圆偏振光谱仪(SE)和原子力显微镜(AFM)表征薄膜表面粗糙度,分析了表面粗糙度随沉积时间的演化行为。讨论了这两种测量手段在分析薄膜表面粗糙度时的差异。结果表明,采用SE拟合得到的表面粗糙度数值要大于采用AFM直接测量得到的结果。产生差异的原因,一是由于两种测量手段的测量机制不同;二是由于薄膜的结构不均匀导致薄膜表面形貌差异。另外,还发现这两种测量手段得到的表面粗糙度数值之间存在线性关系。

Effects of the Fabrication Processes of NC-Si:H Films on Their Mechanical Properties

Studies of nanoindentation were performed on nc-Si：H films to evaluate the effects of the fabrication processes on their mechanical properties. It is observed that with the decrease of the SiH4 contents, the grain size of the films increases gradually, and as does the crystalline volume fraction. The smaller the grains become, the more homogeneous the films, and the more even the hardness as well as the modulus will be. The hardness and the modulus will increase with the substrate＇s temperature rising. The hardness and the modulus of the nc-Si：H films on the Si substrate prove to be higher than those on the glass substrate given the same technology parameters. How- ever, the films on the glass substrate appear to be more homogeneous.

SUBSTRATE EFFECT ON HYDROGENATED MICROCRYSTALLINE SILICON FILMS DEPOSITED WITH VHF-PECVD TECHNIQUE

Raman spectra and scanning electron microscope （SEM） techniques were used to determine the structural properties of microcrb＇stalline silicon （μc-Si：H） films deposited on different substrates with the very high frequency plasma-enhanced chemical vapor deposition （VHF-PECVD） technique. Using the Raman spectra, the values of crystalline volume fraction Xc and average grain size d are 86%, 12.3nm; 65%, 5.45nm; and 38%, 4.05nm, for single crystalline silicon wafer, coming 7059 glass, and general optical glass substrates, respectively. The SEM images further demonstrate the substrate effect on the film surface roughness. For the single crystalline silicon wafer and Coming 7059 glass, the surfaces of the μc-Si：H films are fairly smooth because of the homogenous growth or h＇ttle lattice mismatch. But for general optical glass, the surface of the μ-Si： H film is very rough, thus the growing surface roughness affects the crystallization process and determines the average grain size of the deposited material. Moreover, with the measurements of thickness, photo and dark conductivity, photosensitivity and activation energy, the substrate effect on the deposition rate, optical and electrical properties of the μc-Si：H thin films have also been investigated. On the basis of the above results, it can be concluded that the substrates affect the initial growing layers acting as a seed for the formation of a crystalline-like material and then the deposition rates, optical and electrical properties are also strongly influenced, hence, deposition parameter optimization is the key method that can be used to obtain a good initial growing layer, to realize the deposition of μc-Si：H films with device-grade quality on cheap substrates such as general glass.

利用等离子增强化学汽相沉积生长初期快速结晶的纳米晶硅(英文)

成功地利用传统的等离子增强化学汽相沉积技术制备了纳米晶硅。为了提高生长初期的结晶速度,在PECVD设备和干法刻蚀设备中,利用H2/SF6等离子体对Si Nx薄膜表面进行处理。在制备纳米/微米晶粒结晶硅时常用的氢气稀释条件下,沉积得到了纳米晶硅。利用XRD和TEM观察了氢化纳米晶硅(nc-Si∶H)的微结构,发现实验成功得到了小于10 nm的晶体硅。为了检测结构和电学特性,测试了纳米晶硅薄膜的亮态和暗态电导率。室温下,电导率从非晶硅的10-10S/cm增加到10-5S/cm。

Global optimization of process parameters for low-temperature SiN_(x) based on orthogonal experiments

Low-temperature silicon nitride(SiNx)films deposited by plasma-enhanced chemical vapor deposition(PECVD)have huge application potential in the flexible display.However,the applicability of SiNx largely depends on the film’s general properties,including flexibility,deposition rate,residual stress,elastic modulus,fracture strain,dielectric constant,refraction index,etc.Process optimization towards specific application by conventional experiment design needs lots of work due to the interaction of muti quality and process parameters.Therefore,an efficient global optimization approach for the process technology was proposed based on the Taguchi orthogonal experiment method considering muti-factor muti-responses.First of all,the Taguchi orthogonal experiment design and analysis was used to rank the influences of main process parameters on the quality characteristics,including radio frequency(RF)power,pressure,silane flow rate,ammonia flow rate and nitrogen flow rate.Then,the global optimization approach was carried out utilizing the multi-response optimizer considering the combination target of film formation rate,residual stress,dielectric constant,elastic modulus,fracture strain,refractive index.Finally,the optimal solution of the SiNx film was finally obtained and verified.

Property mapping of polycrystalline diamond coatings over large area

Large-area polycrystalline diamond(PCD)coatings are important for fields such as thermal management,optical windows,tribological moving mechanical assemblies,harsh chemical environments,biological sensors,etc.Microwave plasma chemical vapor deposition(MPCVD)is a standard technique to grow high-quality PCD films over large area due to the absence of contact between the reactive species and the filament or the chamber wall.However,the existence of temperature gradients during growth may compromise the desired uniformity of the final diamond coatings.In the present work,a thick PCD coating was deposited on a 100-mm silicon substrate inside a 915-MHz reactor;the temperature gradient resulted in a non-uniform diamond coating.An attempt was made to relate the local temperature variation during deposition and the different properties of the final coating.It was found that there was large instability inside the system,in terms of substrate temperature(as high asΔT=212℃),that resulted in a large dispersion of the diamond coating’s final properties:residual stress(-15.8 GPa to+6.2 GPa),surface morphology(octahedral pyramids with(111)planes to cubo-octahedrals with(100)flat top surfaces),thickness(190μm to 245μm),columnar growth of diamond(with appearance of variety of nanostructures),nucleation side hardness(17 GPa to 48 GPa),quality(Raman peak FWHM varying from 5.1 cm^(-1) to 12.4 cm^(-1) with occasional splitting).This random variation in properties over large-area PCD coating may hamper reproducible diamond growth for any meaningful technological application.

In situ separator modification via CVD-derived N-doped carbon for highly reversible Zn metal anodes

Attention toward aqueous zinc-ion battery has soared recently due to its operation safety and environmental benignity.Nonetheless,dendrite formation and side reactions occurred at the anode side greatly hinder its practical application.Herein,we adopt direct plasma-enhanced chemical vapor deposition strategy to in situ grow N-doped carbon(NC)over commercial glass fiber separator targeting a highly stabilized Zn anode.The strong zincophilicity of such a new separator would reduce the nucleation overpotential of Zn and enhance the Zn-ion transference number,thereby alleviating side reactions.Symmetric cells equipped with NC-modified separator harvest a stable cycling for more than 1,100 h under 1 mA·cm^(−2)/1 mAh·cm^(−2).With the assistance of NC,the depth of discharge of Zn anode reaches as high as 42.7%.When assembled into full cells,the zinc-ion battery based on NC-modified separator could maintain 79%of its initial capacity(251 mAh·g^(−1))at 5 A·g^(−1) after 1,000 cycles.

Cost-effective,environmentally-sustainable and scale-up synthesis of vertically oriented graphenes from waste oil and its supercapacitor applications

Vertically oriented graphenes(VGs)have attracted tremendous attention in a variety of energy storage-related applications.However,the high cost of preparing VGs significantly hinders their practical applications.Herein we introduce the Ar-plasma-enhanced chemical vapor deposition to demonstrate the cost-effective,environmentally-sustainable,and scale-up synthesis of VGs from waste oil.In our system,Ar gas can improve the electron energy and ionization rate of plasma,which breaks down the chemical bonding of waste oil into essential species to etch the amorphous carbon,yielding large-area VGs(12×3.5 cm^(2))with highly-oriented structure and superior growth efficiency beyond VGs from hydrocarbon precursors.In the supercapacitor applications,the VG-based electrode exhibits significantly enhanced capacitance(~4 times that from conventional hydrocarbon gases)and efficient AC(alternating current)filtering capability RC(resistor-capacitor)(time constant of of 163μs at 120 Hz),which is obviously superior to the non-oriented counterpart.Besides,MnO_(2)/VGs composite electrode is prepared to deliver a maximum energy density of~33.2 Wh/kg at 1.0 kW/kg and a power density of 10.2 kW/kg at 22.9 Wh/kg.In the end,the economic analysis suggests that the total cost of VGs can be reduced by~32%.This work provides an environment-friendly and low-cost avenue for preparing VGs for advanced energy storage applications.

The role of ions in plasma catalytic carbon nanotube growth： A review

While it is well-known that the plasma- enhanced catalytic chemical vapor deposition （PECVD） of carbon nanotubes （CNTs） offers a number of advantages over thermal CVD, the influence of the various individual contributing factors is not well understood. Especially the role of ions is unclear, since ions in plasmas are generally associated with sputtering rather than with growing a material. Even so, various studies have demonstrated the beneficial effects of ion bombardment during the growth of CNTs. This review looks at the role of the ions in plasma- enhanced CNT growth as deduced from both experimental and simulation studies. Specific attention is paid to the beneficial effects of ion bombardment. Based on the available literature, it can be concluded that ions can be either beneficial or detrimental for carbon nanotube growth, depending on the exact conditions and the control over the growth process.

Vertical graphene-coated Cu wire for enhanced tolerance to high current density in power transmission

Cu wires(CuWs)are widely used as electric transmission lines.However,their limited thermal and chemical stabilities become challenges under the high-power and harsh environment.Graphene is regarded as an ideal protective barrier for CuW benefiting from its impermeability to all atoms and molecules.Particularly,the excellent hydrophobicity of vertical graphene(VG)will strengthen its protective capability as a corrosion and oxidation barrier.Herein,VG is directly synthesized on CuW by plasmaenhanced chemical vapor deposition method.The hydrophobic VG coating with a high water contact angle can effectively exclude the corrosive liquid and moisture from CuW surface and prevent their further penetration.Consequently,the electrochemical corrosion rate of VG-CuW is reduced by~13,8,and 2 times,compared with bare CuW,VG-CuW with hydrophilic treatment,and CuW coated with thick horizontal graphene layers,respectively.Negligible oxidation occurs on VGCuW after the long-time exposure to humid air at~200℃ along with the largely enhanced tolerance under high-current operating condition.This study reveals the impressive potentials of hydrophobic VG as a robust corrosion and oxidation barrier for metal wires used in high-power cables and electronic devices in harsh environment.

Confining MOF-derived SnSe nanoplatelets in nitrogen-doped graphene cages via direct CVD for durable sodium ion storage

Tin-based compounds are deemed as suitable anode candidates affording promising sodium-ion storages for rechargeable batteries andhybrid capacitors.However,synergistically tailoring the electrical conductivity and structural stability of tin-based anodes to attain durablesodium-ion storages remains challenging to date for its practical applications.Herein,metal-organic framework(MOF)derived SnSe/C wrappedwithin nitrogen-doped graphene(NG@SnSe/C)is designed targeting durable sodium-ion storage.NG@SnSe/C possesses favorable electricalconductivity and structure stability due to the"inner"carbon framework from the MOF thermal treatment and"outer"graphitic cage from thedirect chemical vapor deposition synthesis.Consequently,NG@SnSe/C electrode can obtain a high reversible capacity of 650 mAh·g^-1 at 0.05 A·g^1,a favorable rate performance of 287.8 mAh·g^1 at 5 A·g^1 and a superior cycle stability with a negligible capacity decay of 0.016%percycle over 3,200 cycles at 0.4 A·g^1.Theoretical calculations reveal that the nitrogen-doping in graphene can stabilize the NG@SnSe/Cstructure and improve the electrical conductivity.The reversible Na-ion storage mechanism of SnSe is further investigated by in-situ X-raydiffraction/ex-s/tu transmission electron microscopy.Furthermore,assembled sodium-ion hybrid capacitor full-cells comprising our NG@SnSe/Canode and an active carbon cathode harvest a high energy/power density of 115.5 Wh·kg^-1/5,742 W·kg^-1,holding promise for next-generationen ergy storages.