电沉积制备ZnSe薄膜材料的研究进展

综述了国外电沉积制备ZnSe薄膜的研究进展,尤其是在酸性电解液溶液中电沉积制备ZnSe薄膜、电沉积掺杂制备p型和n型ZnSe薄膜,且阐述了电沉积ZnSe薄膜材料的特性和机理,对其前景进行展望,提出了今后的重点研究方向.     

氧离子注人对金刚石薄膜微结构和力学性能的影响

采用扫描电镜（SEM）、Raman光谱和纳米压痕法研究了氧离子注入对低硼掺杂金刚石薄膜微结构和力学性能的影响。结果表明,薄膜中注入较高剂量的氧离子并退火后,晶粒尺寸减小。氧离子注入导致薄膜中金刚石含量减小;1000℃退火后,薄膜中金刚石含量增加为99．8％。氧离子注入后,薄膜中的内应力由拉应力转变为压应力;退火后,薄膜内应力再转变为柱应力。氧离子注入后的金刚石薄膜的硬度较注入前的薄膜硬度有所降低,但其硬度仍然大于40GPa并具有良好的弹性恢复率。薄膜的力学性能与薄膜中的金刚石含量、晶粒尺寸和应力值有直接关系。     

温度对n-ZnO/p-diamond薄膜异质结器件制备和电学性质的影响

采用反应磁控溅射法在p型硼掺杂金刚石(BDD)薄膜衬底上制备了非有意掺杂n型氧化锌(ZnO)薄膜。利用XRD、SEM、I-V特性曲线对n-ZnO/p-BDD薄膜复合结构进行表征分析。n-ZnO多晶膜沉积在p-BDD膜上形成了具有良好整流特性的异质结。在空气中对异质结进行退火处理,研究了退火(400℃,700℃)对异质结性质的影响。实验表明,较高退火温度处理,可获得多取向的ZnO膜,晶粒尺寸增大,n-ZnO/p-BDD异质结开启电压减小。不同温度下的电学性质测量结果证明该异质结适合在高温环境下工作。     

Mg-Co共掺杂对ZnO-TCO薄膜光学特性及微观结构的影响

研究了Sol-Gel法制备不同掺杂浓度的Mg-Co共掺杂对ZnO-TCO(transparent conductive oxide,TCO)薄膜的微观结构及光学特性的影响。样品的光学、成分结构及表面形貌特性表征分别利用荧光光谱仪、紫外-可见-近红外光谱仪、XPS、X射线衍射仪、扫描电子显微镜。结果发现:Mg、Co均以离子态对ZnO进行了替位掺杂,薄膜的生长特性均呈现(002)峰择优取向;掺杂前,ZnO薄膜晶粒尺寸较小,表面平整、颗粒疏松;共掺杂后,薄膜表面团簇增加。Mg-Co掺杂比例为2∶2时,薄膜的内部缺陷增多,结晶质量明显下降。由光透过率谱发现薄膜在可见-近红外区域的光透过率基本保持在95%左右,由于掺杂Co,薄膜的禁带宽度变窄,在波长500~650 nm之间出现了特征吸收峰,蓝色发光增强,并且紫外发光峰发生红移。     

热处理对锡/镍共掺杂二氧化钛相变及晶粒尺寸的影响

采用溶胶凝胶法制备了纯TiO_2以及锡掺杂、镍掺杂、锡/镍共掺杂TiO_2并对其进行了480℃和680℃保温1 h热处理,研究了掺杂对锐钛矿/金红石相变,以及对TiO_2晶粒尺寸的影响。结果表明纯TiO_2在480℃为锐钛矿,680℃为金红石,在这个温度区间内完成了锐钛矿向金红石相变。镍掺杂阻碍了相变,锡掺杂促进了相变。当锡/镍摩尔比为1∶3,1∶1时整体表现为抑制作用,3∶1时,锡的促进与镍的抑制作用几乎抵消,对相变无明显影响。掺杂后样品的晶粒尺寸都明显减小。SEM测试结果表明掺杂对颗粒形貌影响不大,温度升高,颗粒团聚程度增加。     

La1-xCaxMnO3稀土氧化物多晶材料的制备与性能

采用碳酸铵化学共沉淀法在1200℃保温24小时的条件下,制备了x组分为0.2、0.33和0.9的La1-xCaMnO3多晶靶材,通过R-T和XRD测试分析,结果表明化学共沉淀法获得了阻温特性良好(Tm-1为253K、TCR为3.2%)、物相较纯的各组分LCMO多晶材料.随着x组分的增加,Ca掺杂量越大,TCR越大、对应Tp温度越低,LCMO的晶格常数abc线性减小、晶粒尺寸增大.     

锑掺杂量对ATO薄膜结构及光、电性能的影响

以四氯化锡和三氯化锑为主要原料,采用溶胶-凝胶法制备了不同锑掺杂量的纳米锑掺杂二氧化锡（ATO）薄膜。分别利用XRD、FESEM、紫外可见分光光度计和四探针电阻仪对晶体结构、薄膜形貌、光透过率和薄膜方块电阻进行表征,考察锑掺杂量对ATO薄膜晶体结构、晶粒尺寸、光透过率和导电性能的影响。结果表明：所制备的ATO薄膜为（110）面择优取向的四方相锡石结构,晶粒尺寸小于26 nm,当锑掺杂量为10%（物质的量分数）时,ATO薄膜具有最小的方块电阻（60.1 Ω/□）,可见光透过率大于85%。     

Nd掺杂钛酸钡基陶瓷的制备及性能研究

采用溶胶-凝胶一步法制备了Nd掺杂锆钛酸钡基陶瓷,通过XRD、SEM等分析检测手段对样品进行表征。研究了Nd掺杂量的不同对其微观形貌及介电性能的影响。研究表明:随着Nd掺杂量的增大,钛酸钡基陶瓷的晶粒尺寸增大,介电常数呈现出先增大后减小的变化趋势,介电损耗逐渐减小;当Nd掺杂量为摩尔分数0.07%时,陶瓷较为致密,其室温介电常数达到最大值16032,介电损耗较小为0.0046。     

稀土掺杂混晶TiO2薄膜的制备和性能

利用溶胶-凝胶法在瓷片表面制备了纯的和少量Eu3 掺杂的TiO2薄膜,并用X-射线衍射技术对样品进行了表征。研究了少量Eu3 掺杂对样品相结构、晶粒尺寸和光催化降解亚甲基蓝活性的影响。利用相结构与TiO2薄膜光催化活性关系,探讨了少量Eu3 掺杂对TiO2薄膜的光催化活性的影响。结果表明,与纯TiO2薄膜相比,适量掺杂Eu3 可以显著提高其光催化活性。当Eu3 的质量分数为0.02%,TiO2薄膜的光催化活性最佳,降解率为62%,金红石相质量分数为17.2%,平均晶粒粒径为20 nm;Eu3 掺杂强烈地抑制TiO2由锐钛矿相向金红石相的转变并减小了晶粒尺寸,有利于提高光催化活性。     

溶胶-凝胶自燃烧法制备纳米CoYxFe2-xO4铁氧体的特性

采用溶胶-凝胶自燃烧法制备了CoYxFe2-xO4(x=0.0,0.1,0.2,0.3)铁氧体纳米粉末,并在不同温度下对样品进行了热处理.利用热重/差热综合分析仪及Fourier变换红外光谱仪研究样品的热反应过程.利用X射线衍射仪和振动样品磁强计对样品的结构、晶粒尺寸和磁性进行了测量和分析.结果表明:经自燃烧和不同温度热处理后粉末样品都具有尖晶石结构,晶粒尺寸为10～22 nm之间,存在亚铁磁性.随着稀土钇掺杂量的增加,晶格常数呈现变小趋势,晶粒尺寸减小,矫顽力增大,比饱和磁化强度减小,样品形成单相尖晶石结构能力变弱.经过热处理后,样品的晶格常数、晶粒尺寸、比饱和磁化强度增加,而矫顽力先增后减.     

Sol–Gel and Thermally Evaporated Nanostructured Thin ZnO Films for Photocatalytic Degradation of Trichlorophenol

In the present work, thermal evaporation and sol–gel coating techniques were applied to fabricate nanostructured thin ZnO films. The phase structure and surface morphology of the obtained films were investigated by X-ray diffractometer (XRD) and scanning electron microscope (SEM), respectively. The topography and 2D profile of the thin ZnO films prepared by both techniques were studied by optical profiler. The results revealed that the thermally evaporated thin film has a comparatively smoother surface of hexagonal wurtzite structure with grain size 12 nm and 51 m²/g. On the other hand, sol–gel films exhibited rough surface with a strong preferred orientation of 25 nm grain size and 27 m²/g surface area. Following deposition process, the obtained films were applied for the photodegradation of 2,4,6-trichlorophenol (TCP) in water in presence of UV irradiation. The concentrations of TCP and its intermediates produced in the solution during the photodegradation were determined by high performance liquid chromatography (HPLC) at defined irradiation times. Complete decay of TCP and its intermediates was observed after 60 min when the thermal evaporated photocatalyst was applied. However, by operating sol–gel catalyst, the concentration of intermediates initially increased and then remained constant with irradiation time. Although the degradation of TCP followed first-order kinetic for both catalysts, higher photocatalytic activity was exhibited by the thermally evaporated ZnO thin film in comparison with sol–gel one.     

Room temperature preparation of c axis oriented ZnO films on Si(100), SiO2, and ZnO substrates by rf magnetron sputtering

Abstract

Growth of ZnO thin films with c axis (002) orientation has been demonstrated at room temperature on Si(100), SiO₂, and amorphous ZnO substrates by the rf magnetron sputtering method. The structural properties of the ZnO thin films were investigated with varying rf power. X-ray diffraction analysis revealed that increasing rf power helped to increase the c axis lattice constant and grain size, regardless of substrate material. Scanning electron microscopy indicated that the structural morphology of the ZnO films was not dependent on the substrate material.     

Thickness-Dependent Mechanical Behaviour of Aluminium-Coated Polyethylene Terephthalate (PET) Films

Mechanical behaviour of aluminium-coated PET films has been investigated through Dynamic Mechanical Analyser. Aluminium is coated on PET substrate by vacuum thermal evaporation method. As thickness of aluminium coating increases from 150 nm to 350 nm, tensile strength decreases from 108.88 MPa to 99.25 MPa. This mechanical behaviour is correlated with microstructure and its evolution with the thickness of aluminium coating. Al-PET film consists of fine globular grains and average grain size increases monotonically with the film thickness. The relative contribution of the grain size to the strength of aluminium thin films is in good agreement with Hall-Patch equation.     

Influence of strain on the dielectric properties of Bi–Zn–Ti–Nb–O solid solution thin films

Bi–Zn–Ti–Nb–O (BZTN) solid solution thin films with various compositions were prepared by metalorganic decomposition (MOD) process on the platinized Si substrates. BZTN thin films showed a wide solid solubility since the thin films maintained the single phase of cubic pyrochlore structure in a broad range of composition. Crystal structure and dielectric properties of BZTN thin films were compared to those of BZTN bulk ceramics and the difference in dielectric properties such as dielectric constant, dielectric loss and tunability between thin films and bulk ceramics were understood to originate from the strain in the thin films since there was no apparent difference in the other factors such as microstructure and preferred orientation. The existence of strain in the thin films was confirmed by two ways. One is the rate of lattice shrinking. Shrinkage in the lattice parameter of thin films was depressed compared to that of bulk ceramics, which might introduce the internal strain in the thin films. Another is the thermal expansion coefficient (α, TEC) of BZTN solid solutions. TEC measured from the bulk ceramics varied with composition and the difference in the TEC between the polycrystalline thin film and underlying substrate would result in the thermal strain of thin films. Thin films with various compositions were under different degree of tensile stress state and the BZTN thin films with optimal composition demonstrated the high tunability of 30% under 1100 kV/cm with dielectric constant of 242 and dielectric loss of 0.004.     

Preparation and tunability properties of Ba(ZrxTi1−x)O3 thin films grown by a sol–gel process

Ba(Zr_xTi_1−x)O₃ (BZT) thin films were deposited via sol–gel process on LaNiO₃, as buffer layer, and Pt-coated silicon substrates. The BZT films were perovskite phase and showed a (1 0 0) preferred orientation dependent upon zirconium content. The grain size decreased and the microstructure became dense with increasing zirconium content. The addition of Zr to the BaTiO₃ lattice decreased the grain size of the crystallized films. The temperature dependent dielectric constant revealed that the thin films have relaxor behavior and diffuse phase transition characteristics that depend on the substitution of Zr for Ti in BaTiO₃. The dependence of electrical properties on film thickness has been studied, with the emphasis placed on dielectric nonlinear characteristics. Ba(Zr_0.35Ti₆₅)O₃ thin films with weak temperature dependence of tunability in the temperature range from 0 to 130 °C could be attractive materials for situations in which precise control of temperature would be either impossible or too expensive.     

The dielectric properties and optical propagation loss of c-axis oriented ZnO thin films deposited by sol–gel process

The c-axis oriented ZnO thin films were prepared on various substrates by sol–gel processes. The stability of solution was examined through solvent and stabilizer. The c-axis orientation and grain size of films were increased with increasing of heat treatment temperature. The optical propogation losses of ZnO films deposited SiO₂/Si(111) substrates were measured using end-coupling method. The losses result in the scattering of the interface of ZnO/SiO₂, and the ZnO grain. Dielectric constant and resistivity of thin films deposited on Pt/SiO₂/Si(111) substrates are, respectively, in the range of 7–13 and 1.7×10⁴9.8×10⁵Ω cm.     

Polymorphic Behavior of Thin Evaporated Films of Zirconium and Hafnium Oxides

Polymorphism in thin evaporated films of zirconium and hafnium oxides was investigated from 100° to 1500°C by electron diffraction and transmission electron microscopy. The films have metastable cubic structures at room temperature and at moderate temperatures. Zirconium oxide, depending on temperature, exists in cubic, tetragonal, and monoclinic forms, whereas hafnium oxide transforms directly from the cubic to the monoclinic structure. The transformation temperatures depend on the oxygen partial pressure. Air annealing of thin films of ZrO₂ and HfO₂ lowered the temperature of transformation of the tetragonal and the cubic structure into the monoclinic structure by about 150° and 100°C, respectively. The cubic/tetragonal transformation of ZrO₂ is monotropic, whereas the tetragonal monoclinic transformation occurs by the typical nucleation and growth mechanism. Determination of grain size in ZrO₂ at the tetragonal/monoclinic transformation temperature showed that the transformation occurs when a constant grain size of about 800 Å is reached. The oxygen partial pressure, grain size, and temperatures at which the metastable phases exist were correlated. The rate of grain growth is enhanced by increase in oxygen partial pressure. The accelerated transformation in air is attributed to rapid attainment of the critical size; grain boundary energy is an important controlling factor in transformation.     

Multiferroic behavior of heterostructures composed of lanthanum and bismuth ferrite

Heterostructured thin films of lanthanum ferrite (LFO) and bismuth ferrite (BFO) with different thicknesses were successfully obtained by a soft chemical method. The films were deposited by spin-coating and annealed at 500 °C for 2 h. The XRD pattern confirmed the purity of the thin films, where no additional peaks associated with impurity phases were present. The morphology analysis showed spherical grains with a random size distribution. The grain sizes increased with the number of BFO layers. The average grain size varied from 43 nm to 68 nm. The best dielectric results were obtained for the film with 6 LFO sublayers and 4 BFO top layers, in which the dielectric constant showed low dispersion. Since the capacitance-voltage curve for the film 6-LFO/4-BFO is symmetrical around null voltage, it can be inferred that this heterostructure has few mobile ions and accumulated charges on the film-substrate interface. In this film, polarization remains almost constant during 10¹² cycles before the onset of degradation, which shows the very high resistance of the films to fatigue. Magnetoelectric coefficient measurements of the films revealed the formation of hysteresis loops, and a maximum value of 12 V/cmOe was obtained for the magnetoelectric coefficient in the longitudinal direction; this value is much higher than that previously reported for pure BFO thin films.     

Effect of Internal Stress on Physical Temperature Characteristics of Cerium-Doped and Gadolinium-Doped Barium Titanate Ceramics

The effect of internal stress on the physical properties (the temperature dependence of the dielectric constant and the lattice constant, and the diffuseness (gamma)) of solid solutions of 0.97BaTiO₃-0.03Gd₂O₃:1.5TiO₂ and 0.97BaTiO₃-0.03CeO₂:1.5TiO₂ was investigated using various particle sizes of the starting BaTiO₃, pressure-dielectric spectroscopy, and high-pressure X-ray analysis. The grain size was almost proportional to the particle size of the starting BaTiO₃ and was inversely proportional to the internal stress. A sudden change in internal stress occurred at grain sizes of ∼2 µm for cerium-doped BaTiO₃ and ∼3 µm for gadolinium-doped BaTiO₃. With an increase in external pressure and a decrease in grain size, the lattice anomalies of the cubic-to-tetragonal transformation and two other factors (the tetragonal-to-orthorhombic and orthorhombic-to-rhombohedral transformations) shifted to lower and higher temperatures, respectively. The temperature dependencies of the dielectric constant and the lattice constant were less sensitive to external pressure in cerium-doped core-shell-grained BaTiO₃ than in gadolinium-doped homogeneous-grained BaTiO₃; this difference was attributable to internal stress. In cerium-doped BaTiO₃, gamma was related to internal stress.     

Structural,electrical and optical properties of stoichiometric In2Te3 thin films

In₂Te₃ thin films were grown by thermal evaporation technique. The annealing of films played a major role to obtain stoichiometry, regardless of substrate temperature. Annealing at 300 ⁰C resulted in well oriented, mono-phased and nearly stoichiometric In₂Te₃ thin films. The variation in grain size of In₂Te₃ films associated with the substrate temperatures provides a significant control over the resistivity of the films, and the resistivity decreased with an increase in the grain size. The activation energy and optical band gap of stoichiometric In₂Te₃ films were found to be 0.01±0.005 eV and 0.99±0.02 eV, respectively. The absorption co-efficient of these films was found to be of the order of 10⁵ cm⁻¹.