四苯基卟啉锌-单壁碳纳米管复合薄膜的制备与光电特性研究

使用喷涂法制备了四苯基卟啉锌(ZnTPP)薄膜及ZnTPP-单壁碳纳米管复合薄膜。采用金相显微镜、扫描电子显微镜、台阶仪、四探针测试仪、紫外-可见光分光光度计、傅里叶红外光谱仪对薄膜的形貌、电学及光学性能等进行了系统的测量,研究了ZnTPP薄膜及ZnTPP-碳纳米管复合薄膜的太赫兹响应特性。结果表明,ZnTPP的太赫兹指纹谱峰为44,57,77,88,95和102 cm-1,与文献[3]报道的棕树叶中叶绿素的指纹谱峰基本一致。重要的是,通过与碳纳米管相复合的方法,不仅使ZnTPP有机薄膜的均匀性及致密性得到了改善,还使后者的导电性及在紫外到太赫兹波段的光吸收性能获得明显增强。此外,还发现了复合薄膜在47及66 cm-1处出现新的太赫兹吸收峰,证明了碳纳米管和ZnTPP之间存在的相互作用。这种作用使复合薄膜的综合性能得到提高。结果表明,通过加入碳纳米管,能够对ZnTPP的薄膜质量以及电学和光学性能等进行有效的改善,使之具有综合优良的物理性能、具备光电器件的应用前景。研究成果对促进有机物的太赫兹光谱研究以及寻找新型太赫兹有机敏感材料等具有重要意义。     

氟-氧化物复合薄膜的特性研究

以SiO_2、TiO_2、YF_3为单组分材料分别制备了SiO_2/YF_3、TiO_2/YF_3复合薄膜,探究复合后膜层的光学、力学以及抗激光损伤性能的变化情况.采用双源共蒸技术,通过控制膜料蒸发时的沉积速率制备了混合摩尔比为1∶1的两种氟氧化物复合薄膜,对复合膜层的折射率、消光系数、透射特性、表面形貌、粗糙度进行了测量,并研究了其抗激光损伤性能.结果表明:SiO_2/YF_3、TiO_2/YF_3复合膜层的折射率分别为1.478 7和1.864 6(波长550 nm),介于单组分材料之间(YF_3为1.493 6、SiO_2为1.465 1、TiO_2为2.048 3),且均呈现正常色散分布;ZYGO干涉测量的结果显示,SiO_2/YF_3膜层的应力值为1.9 GPa,比单组分材料SiO_2和YF_3的0.4 GPa大但粗糙度小;TiO_2/YF_3膜层的应力值为0.8 GPa,比TiO_2的3.9 GPa应力小但较YF_3大,表现出较明显的应力调节效果;SiO_2/YF_3复合薄膜的激光损伤阈值为9.2 J/cm~2,相比于单组分的SiO_2提高了2.2%,较YF_3提高了39.2%;TiO_2/YF_3的激光损伤阈值为7.8 J/cm~2,相比于单组分的TiO_2薄膜而言提高了85.6%,较YF_3提高了17.4%.通过双源共蒸技术沉积得到的氟氧化物复合薄膜,吸收小、膜层折射率可调;SiO_2/YF_3、TiO_2/YF_3复合膜层的抗激光损伤性能均优于单组分材料;YF_3的掺杂能够明显降低单一TiO_2材料的应力,但SiO_2/YF_3的应力大于单组分的SiO_2、YF_3薄膜.     

光学薄膜的等离子体离子镀的研究

根据薄膜沉积过程等离子体对光学薄膜膜蒸气分子或原子的作用，建立低压等离子体离子镀设备，并对常规光学薄膜、如硫化物、氧化物薄膜以及多层膜器件进行了系统的研究，对所制备薄膜样品的透射光谱、吸收、散射以及膜层的聚集密度等进行了全面的测试分析。实验研究表明，低压等离子体离子镀可大大提高常规光学薄膜的光机性能。     

基底微缺陷对介质薄膜光学性能影响的理论研究

基于非均匀膜理论提出一种存在微缺陷的介质基底的折射率分层模型，将基底依次分为表面层、亚表面层和体材料层，其中表面层和亚面层分别等效为折射率服从统计分布的非均匀膜，将它们分别再次细分为N₁和N₂个子层，每一子层均视为均匀介质 膜.应用光学薄膜特征矩阵法对其进行理论分析，并对单层介质膜的光学性能进行数值计算. 研究结果表明：基底的表面和亚表面微缺陷改变了薄膜和基底的等效折射率，导致了准Brew ster角和组合反射率与理想情形的偏离.同时这些微缺陷也改变了光在薄膜和基底中的传播 特性，因此反射相移和相位差均偏离理想情形.在研究基底的微缺陷对多层介质膜光学性能 影响的分析和计算时，该模型同样适用. 关键词： 微缺陷 介质薄膜 非均匀膜 光学性能     

非晶粉/硅橡胶复合薄膜应力阻抗性能

选用硅橡胶为基材,Fe73.5Cu1Nb3Si13.5B9非晶纳米晶软磁合金粉体为磁性功能填料,采用机械共混的方法制备非晶粉/硅橡胶力敏复合材料。采用自制测试夹具测试非晶粉/硅橡胶复合材料的阻抗值,采用扫描电镜分析非晶粉颗粒形貌及其在硅橡胶基材中分散情况,在此基础上研究了复合材料界面绝缘性、单层与多层叠加复合薄膜、加入导电层及其层数对复合应力阻抗性能的影响。研究结果表明:铜箔作为界面强化导电层的加入是提高复合薄膜力敏特性的有效途径之一,设计实验中的复合薄膜/铜箔/复合薄膜结构相当于聚合物/金属/聚合物三明治多层膜结构,对敏感性具有增强效应。     

C60-甲苯衍生物对酞菁铜/C60薄膜光电性能的影响

从光电导－时间关系，瞬态光电导能谱和光诱导放电曲线（PIDC）等方面研究C60－甲苯衍生物对酞菁铜（CuPc)/C60薄膜光电性能的影响，并对其机理进行了探讨，C60－甲苯衍生物对C60－甲苯衍生物／CuPc/C60多层膜的光电性能具有明显的增强效应。     

DLC/Ag/DLC复合多层薄膜光学性能

采用等离子体增强化学气相沉积类金刚石(DLC)薄膜、高真空磁控溅射镀膜设备溅射Ag靶的方法制备了不同厚度Ag、DLC层的DLC/Ag/DLC多层膜,分别用紫外可见分光光度计、四探针测试仪对样品的光学性能、电学性能进行了测试.结果表明,随着Ag层厚度的增加,DLC/Ag/DLC多层膜透射率先增后减,外层DLC薄膜和内层DLC薄膜对透射率影响基本一致,随着厚度增加透射率先增后减,在内外层厚度为40 nm,Ag夹层厚度为16 nm时,DLC(30 nm)/Ag(16 nm)/DLC(40 nm)膜在550 nm处的透射率高达94.4%,电气指数高达112.4 ×10-3Ω-1,远远超过现有透明导电膜的电气指数(FTC≈20×10-3Ω-1).     

Ag:ZnO/SiO_2复合薄膜的制备与光学性能

采用溶胶-凝胶法在玻璃衬底上制备Ag掺杂于ZnO层的Ag:ZnO/SiO2(AZSO)复合薄膜,采用XRD、SEM、UV-Vis和PL谱等手段对样品的晶体结构、微观形貌、透过率、吸收率及光致发光性能等进行表征,并观察了掺Ag量对复合薄膜光学性能的影响。XRD结果表明:样品经300℃退火处理后出现ZnO及单质Ag衍射峰;由SEM结果可观察到AZSO复合薄膜颗粒分散均匀,表面致密,其断面照片显示了薄膜的双层结构。UV-Vis吸收光谱结果表明:随着复合薄膜中Ag含量的增加,Ag与ZnO之间的电子转移及Ag颗粒的变大促使Ag的特征吸收峰呈现红移和宽化,样品的透过率也随之降低,吸收边向短波长方向移动,禁带宽度减小。PL谱结果表明:由于Ag的掺入减少了ZnO内空穴浓度并对复合薄膜的结构缺陷进行补偿,以及Ag在440nm附近的特征吸收,降低了复合薄膜的发光强度。     

Pb(Mg_(1/3)Nb_(2/3))O_3-PbTiO_3/CoFe_2O_4复合薄膜电学、磁学性能的研究

利用射频磁控溅射技术在LaNiO_3/SiO_2/Si基底上制备了Pb(Mg_(1/3)Nb_(2/3))O_3-PbTiO_3/CoFe_2O_4和Pb(Mg_(1/3)Nb_(2/3))O_3-Pb TiO_3/Co Fe_2O_4/Pb(Mg_(1/3)Nb_(2/3))O_3-PbTiO_3两种复合薄膜.我们采取了三种退火条件对复合薄膜进行退火处理,研究两种复合薄膜的晶体结构、电学和磁学性能.通过对两种复合薄膜的结构的分析,发现两步法退火后得到复合薄膜同时存在纯钙钛矿相和尖晶石相两种结构.铁电性能测试表明,两种复合薄膜均具有较好的铁电性能,其中三层复合薄膜的剩余极化强度Pr最大可以达到14.9μC/cm2,这要归因于多层复合薄膜内部的应力-应变效应和界面耦合效应.在电场强度为80 k V/cm的漏电流密度数量级仅10-5A/cm2,其导电机制在高电场区满足Schottky机制.介频性能测试表明:复合薄膜的介频特性较差,双层复合薄膜的介电性能较好,其介电常数εr为1078,其介电损耗tgδ较大,约为0.43.此外,对复合薄膜的磁滞回线测试表明:两种复合薄膜中均存在磁学性能,且双层结构复合薄膜的铁磁性能较大,其饱和磁化强度Ms为119 emu/cm3,剩余磁化强度Mr达到31.6 emu/cm3,矫顽场Hc为1360 Oe.以上测试结果表明,铁电有序和磁有序可以存在于钙钛矿-尖晶石结构当中,通过多层复合和合适退火方式可以增强其铁电和介电性能.     

Pb(Mg1/3Nb2/3)O3-PbTiO3/CoFe2O4复合薄膜 电学、磁学性能的研究

利用射频磁控溅射技术在LaNiO3/SiO2/Si基底上制备了Pb(Mg1/3Nb2/3)O3-PbTiO3/CoFe2O4和Pb(Mg1/3Nb2/3)O3-PbTiO3/CoFe2O4/Pb(Mg1/3Nb2/3)O3-PbTiO3两种复合薄膜.我们采取了三种退火条件对复合薄膜进行退火处理,研究两种复合薄膜的晶体结构、电学和磁学性能.通过对两种复合薄膜的结构的分析,发现两步法退火后得到复合薄膜同时存在纯钙钛矿相和尖晶石相两种结构.铁电性能测试表明:两种复合薄膜均具有较好的铁电性能,其中三层复合薄膜的剩余极化强度Pr最大可以达到14.9 μC/cm2,这要归因于多层复合薄膜内部的应力-应变效应和界面耦合效应.在电场强度为80kV/cm的漏电流密度数量级仅10-5A/cm2,其导电机制在高电场区满足Schottky机制.介频性能测试表明:复合薄膜的介频特性较差,双层复合薄膜的介电性能较好,其介电常数εr为1078,其介电损耗tgδ较大,约为0.43.此外,对复合薄膜的磁滞回线测试表明:两种复合薄膜中均存在磁学性能,且双层结构复合薄膜的铁磁性能较大,其饱和磁化强度Ms为119 emu/cm3,剩余磁化强度Mr达到31.6 emu/cm3,矫顽场Hc为1360 Oe. 以上测试结果表明,铁电有序和磁有序可以存在于钙钛矿-尖晶石结构当中,通过多层复合和合适退火方式可以增强其铁电和介电性能.     

Synthesis of anodizing composite films containing superfine Al2O3 and PTFE particles on Al alloys

Anodized composite films containing superfine Al₂O₃ and PTFE particles were prepared on 2024 Al alloy using an anodizing method. The microstructures and properties of the films were studied by scanning electron microscopy, optical microscopy and X-ray diffraction. Friction wear tests were performed to evaluate the mechanical properties of the composites. Results indicate that the composite films with reinforced Al₂O₃ and PTFE two-particles have reduced friction coefficients and relatively high microhardness. The friction coefficient can be as small as 0.15, which is much smaller than that of an oxide film prepared under the same conditions but without adding any particles (0.25), while the microhardness can reach as high as 404 HV. When rubbed at room temperature for 20 min during dry sliding friction tests, the wear loss of the film was about 16 mg, which is about the half of that of the samples without added particles. The synthesized composite films that have good anti-wear and self-lubricating properties are desirable for oil-free industrial machinery applications.     

Research on adhesion strength and optical properties of SiC films obtained via RF magnetron sputtering

SiC is widely used in various mechanical applications as a protective film because of its strength, thermal stability and good mechanical hardness. Here, amorphous SiC thin films with AlN as a buffer layer were deposited on glass and Si substrates through RF magnetron sputtering at different RF powers. The influence of the AlN buffer layer thickness on the morphological and the mechanical properties of the composite films was investigated. Results demonstrate that the AlN buffer layer can effectively improve the adhesion strength of SiC thin films, which has increased gradually from 26.78 N to 37.66 N. The transmittance of SiC thin films was measured using a UV–Vis–NIR spectrophotometer over a spectral range of 300–1200 nm. The average transmittance of SiC films decreases with increasing RF power, and their optical band gap values have varied from 3.31 eV to 3.50 eV.     

Flexible and ultrathin dopamine modified MXene and cellulose nanofiber composite films with alternating multilayer structure for superior electromagnetic interference shielding performance

With the development of modern electronics, especially the next generation of wearable electromagnetic interference (EMI) shielding materials requires flexibility, ultrathin, lightweight and robustness to protect electronic devices from radiation pollution. In this work, the flexible and ultrathin dopamine modified MXene@cellulose nanofiber (DM@CNF) composite films with alternate multilayer structure have been developed by a facile vacuum filtration induced self-assembly approach. The multilayered DM@CNF composite films exhibit improved mechanical properties compared with the homogeneous DM/CNF film. By adjusting the layer number, the multilayered DM3@CNF2 composite film exhibits a tensile strength of 48.14 MPa and a toughness of 5.28 MJ·m⁻³ with a thickness about 19 μm. Interestingly that, the DM@CNF film with annealing treatment achieves significant improvement in conductivity (up to 17264 S·m⁻¹) and EMI properties (SE of 41.90 dB and SSE/t of 10169 dB·cm²·g⁻¹), which still maintains relatively high mechanical properties. It is highlighted that the ultrathin multilayered DM@CNF film exhibits superior EMI shielding performance compared with most of the metal-based, carbon-based and MXene-based shielding materials reported in the literature. These results will offer an appealing strategy to develop the ultrathin and flexible MXene-based materials with excellent EMI shielding performance for the next generation intelligent protection devices.     

Synthesis of modified multi-walled carbon nanotube poly(benzimidazole-imide) composites: assessment of morphological and thermo-mechanical properties

A fully aromatic poly(benzimidazole-imide) (PBI) containing triazole side units and amine-modified multi-wall carbon nanotube (MWCNT)/PBI composites were fabricated via a polymerization process of monomer reactants and solution mixing with ultrasonication excitation. The polymer and composites were characterized by field emission scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction. According to the microscopic characterizations, the MWCNTs homogeneously dispersed in the composites. The mechanical properties of the composite films were also measured by tensile test. The test results evidently indicated that the Young’s modulus increased by about 60.0% at 1 wt% CNT loading, and further modulus growth was observed at higher filler loading. The composite films hold preferable thermal stability the same as the pure PBI. The improvement of the mechanical and thermal properties was attributed to the incorporation of the surface modified CNTs. For CNT-reinforced polymer composites, strong interfacial adhesion and uniform dispersion of CNTs are more crucial factors for improving such properties.     

Supermolecular structure and orientation of blown cellulosic films

N-Methylmorpholine-N-oxide (NMMO) technology provides new possibilities for shaping fibers and films from cellulose. We discuss a blow-extrusion technique can be applied to a cellulose-amine oxide dope, yielding blown cellulosie films. Process parameters, such as the draw down ratio and the blow ratio, can be used to control the mechanical film properties in both the machine and transverse directions. In this way, a wide range of properties is covered, and a completely balanced film can be manufactured. The film thickness can be made as small as 5 μm, and the membrane properties can be varied by the conditions of precipitation. The blown cellulosic films exhibit a partially crystalline supermolecular structure and, depending on the coagulation conditions, a symmetrical or asymmetrical homogeneous morphology and pore structure. Generally, a uniplanar orientation type was found, the chains being parallel to the film surface. Around the surface normal, the chain orientation can be varied from nearly random to strongly uniaxial, in this way determining the mechanical properties in the machine and transverse directions. As compared with the conventional viscose processing route of cellophane, the blown film's NMMO processing route is less complicated and friendlier to the environment. Blown films can be made much thinner, and the mechanical properties are superior to viscose films. Possible application fields of blown cellulose films are food casings, particularly small sausage casings, packaging, and membranes.     

Influence of silicon on the microstructure and mechanical properties of Zr-Si-N composite films

A series of Zr-Si-N composite films with different Si contents were synthesized in an Ar and N₂ mixture atmosphere by the bi-target reactive magnetron sputtering method. These films’ composition, microstructure and mechanical properties were characterized by energy dispersive spectroscopy, X-ray diffraction, scanning electron microscopy, atomic force microscopy and nanoindentation. Experimental results revealed that after the addition of silicon, Si₃N₄ interfacial phase formed on the surface of ZrN grains and prevented them from growing up. Zr-Si-N composite films were strengthened at low Si content with the hardness and elastic modulus reaching their maximum values of 29.8 and 352 GPa at 6.2 at% Si, respectively. With a further increase of Si content, the crystalline Zr-Si-N films gradually transformed into amorphous, accompanied with a remarkable fall of films’ mechanical properties. This limited enhancement of mechanical properties in the Zr-Si-N films may be due to the low wettability of Si₃N₄ on the surface of ZrN grains.     

Multiferroic and magnetoelectric properties of MnFe2O4/(Pb0.8Sr0.2)TiO3 composite films

Abstract

MnFe₂O₄/(Pb_0.8Sr_0.2)TiO₃ (MFO/PST20) heterostructured composite films with three different structures have been grown on Pt/TiO₂/SiO₂/Si substrates by metal–organic decomposition processing via spin coating technique. The structural analysis revealed that the crystal axes of the MnFe₂O₄ are aligned with those of the PST20 ferroelectric matrix with obvious interfaces and no diffusions exist in all the three composite films. These composite films exhibit simultaneously multiferroic and magnetoelectric responses at room temperature. The growth structure of MFO and PST20 layers has an effect on multiferroic and magnetoelectric coupling behaviours of the composite films. The bi- and four-layered MFO/PST20 composite films exhibit superior ferroelectric properties compared to the tri-layered film. The increasing MFO and PST20 layers in the composite films enhance ferromagnetic properties and are closely related to the strain release in MnFe₂O₄ phase. The MFO/PST20 bi-layered composite film shows a high magnetoelectric voltage co-efficient α_E ~ 194 mVcm^?1Oe^?1 at a dc magnetic field H_dc ~ 2.5 kOe. A significant decrease in α_E value has been observed for tri- and four- layered composite films. A close correlation between phase selective residual stress and magnetoelectric properties has been emerged. The results are reasonably encouraging for employing MnFe₂O₄ for growing multiferroic–magnetoelectric composite films.     

沉积温度对钛硅共掺杂类金刚石薄膜生长、结构和力学性能的影响

采用中频磁控溅射Ti80Si20复合靶在单晶硅表面制备了共掺杂的类金刚石薄膜.研究了沉积温度对薄膜生长速率、化学成分、结构、表面性质和力学性能的影响.结果表明:随沉积温度升高,薄膜生长速率降低,薄膜Ti和Si原子浓度增加,C原子浓度降低;在高温下沉积的薄膜具有低sp3C含量、低表面接触角、低内应力和高的硬度与弹性模量.基于亚表层注入生长模型分析了沉积温度对薄膜生长和键合结构的影响,从薄膜生长机制和微观结构解释了表面性质和力学性能的变化.     

The microstructure, mechanical and friction properties of protective diamond like carbon films on magnesium alloy

Protective hard coatings deposited on magnesium alloys are believed to be effective for overcoming their poor wear properties. In this work, diamond-like carbon (DLC) films as hard protective films were deposited on AZ91 magnesium alloy by arc ion plating under negative pulse bias voltages ranging from 0 to −200 V. The microstructure, composition and mechanical properties of the DLC films were analyzed by scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and nanoindentation. The tribological behavior of uncoated and coated AZ91 magnesium alloy was investigated using a ball-on-disk tribotester. The results show that the negative pulse bias voltage used for film deposition has a significant effect on the sp³ carbon content and mechanical properties of the deposited DLC films. A maximum sp³ content of 33.3% was obtained at −100 V, resulting in a high hardness of 28.6 GPa and elastic modulus of 300.0 GPa. The DLC films showed very good adhesion to the AZ91 magnesium alloy with no observable cracks and delamination even during friction testing. Compared with the uncoated AZ91 magnesium alloy, the magnesium alloy coated with DLC films exhibits a low friction coefficient and a narrow, shallow wear track. The wear resistance and surface hardness of AZ91 magnesium alloy can be significantly improved by coating a layer of DLC protective film due to its high hardness and low friction coefficient.