HOPG上ALD沉积Al2O3介电薄膜的生长行为研究

本文采用原子层沉积(ALD)的方法,选择三甲基铝(TMA)和H₂O₂作为反应前驱体,在高定向热解石墨(HOPG)基体上沉积Al₂O₃。系统研究了反应温度和生长周次对Al₂O₃生长行为的影响。研究表明：受HOPG表面饱和成键的影响,Al₂O₃在衬底表面处形核困难,在生长初期主要表现为台阶处择优生长,其形态为线状结构。当沉积100周次Al₂O₃时,其中在沉积温度为50 °C、150 °C和200 °C时呈现为纳米线状结构,而在100 °C时呈现为非连续薄膜。随着生长周次的增加,不同温度下沉积态Al₂O₃都趋于形成连续薄膜,表明其生长行为发生了由三维岛状生长模式向二维平面生长模式的转变。分析认为,生长模式的转变是由纳米线状结构横向生长造成的;横向生长速率主要受生长温度影响。拉曼结果表明：沉积后的石墨烯层结构未受影响,可保留其原有的优越性能。     

退火对TiO2薄膜的结构及电学性能的影响

以硅为衬底,采用射频磁控溅射技术制备了TiO₂薄膜,利用扫描电镜及拉曼光谱对退火前后的TiO₂进行分析。退火后的TiO₂具有良好的结晶特性,且呈锐钛矿结构。在此薄膜工艺条件下,以TiO₂为半导体层在玻璃基底上制备了Al/TiO₂/Pt肖特基二极管,并在153⁴33K范围内对其进行I-V测试。结果表明:在所有温度下,Al/TiO₂/Pt肖特基二极管均表现出良好的整流效应;其理想因子随温度升高而降低,势垒高度随温度升高而升高;在433K下,理想因子为1.31,势垒高度0.73,表明此肖特基二极管已接近理想的肖特基二极管。     

Fe2O3-CaO-TiO2 体系下铁酸钙的合成过程及TiO2 和CaTiO3 的影响

为了确定高钛型钒钛磁铁矿烧结过程中铁酸钙的生成是受TiO₂还是TiO₂和CaO形成的CaTiO₃影响,首先利用Fe₂O₃和CaO的纯试剂合成了铁酸钙,并研究了TiO₂和CaTiO₃对钛铁酸钙 （FCT） 形成的影响。在Factsage 7.0软件进行热力学计算的基础上,通过在空气气氛下进行烧结,获得了在1023~1423 K温度范围内、不同烧结时间的不同样品。通过X射线衍射和扫描电镜-能谱分析等表征手段,对烧结样品的物相转变和微观结构变化进行了表征。发现FCT的形成过程主要分为2个阶段：前一阶段为1023~1223 K温度范围内Fe₂O₃与CaO之间的反应,合成产物为Ca₂Fe₂O₅,反应方程式为“Fe₂O₃(s)+ 2CaO(s)= Ca₂Fe₂O₅(s)”;后一阶段为1223~1423 K温度范围内Ca₂Fe₂O₅和Fe₂O₃的反应,主要产物为CaFe₂O₄,反应为“Ca₂Fe₂O₅(s)+ Fe₂O₃(s)= 2CaFe₂O₄(s)”,该阶段尤其是温度为1423 K时,反应速率显著加快,随温度的升高CaTiO₃显著增加。然而,Ti元素在铁酸钙中的固溶很难实现,TiO₂与铁酸钙之间的反应不是形成FCT的有效途径。随着保温时间的延长,CaTiO₃和FCT相界中Fe元素含量增加。FCT主要是通过Fe组分在CaTiO₃中固溶形成的,主要反应是“Fe₂O₃+CaTiO₃(s)=FCT(s)”。     

氮氧比对AlOxNy薄膜结构和光学性能的影响

以单晶硅(111)和载玻片为基体,采用离子束辅助沉积技术沉积AlO_xN_y薄膜,使用XPS、XRD和椭偏仪研究了氮氧比对AlO_xN_y薄膜的成分、相结构和光学常数的影响。结果表明,随着氮氧比减小,薄膜中氮含量减小,氧含量增加;薄膜由非晶态转变为结晶态,结晶相为AlO_xN_y。沉积薄膜的消光系数为零,呈现电介质特性。随着氮氧比减小,沉积薄膜的折射率减小。随着氮氧比的减小,薄膜中的Al-O键增多是导致AlO_xN_y薄膜折射率减小的主要原因。     

纳米柱状多孔WO3- x /TiO2 薄膜的电致变色性能

采用反应磁控溅射在掠射角度α=0°和α=80°的条件下制备氧化钨（WO_3-x）薄膜,然后在其表面沉积二氧化钛（TiO₂）。利用X射线衍射仪（XRD）、场发射扫描电镜（FE-SEM）和X射线光电子能谱仪（XPS）对WO_3-x/TiO₂薄膜的晶体结构、表面/断面形貌以及表面化学成分进行表征。在三电极体系1 mol/L LiClO₄/PC溶液中,采用电化学工作站和紫外-可见分光光度计测试了WO_3-x/TiO₂薄膜的电致变色性能。XRD结果表明,WO_3-x/TiO₂薄膜为非晶态结构,与掠射角度无关。当掠射角度为80°时,获得了纳米柱状多孔薄膜。从 W 4f和Ti 2p的XPS谱图确认氧化钨为亚化学计量比的WO_3-x,而氧化钛为满足化学计量比的TiO₂。与致密薄膜相比,纳米柱状多孔薄膜需要较低的驱动电压且具有较快的响应速度。纳米柱状多孔薄膜的电荷容量为83.78 mC,是致密薄膜电荷容量30.83 mC的2倍以上。在±1.2 V驱动电压下,注入和脱出离子扩散速率分别为D_in=5.69×10^-10 cm²/s和D_de= 5.08×10^-10 cm²/s。与纯WO₃薄膜相比,WO_3-x/TiO₂薄膜的电致变色循环稳定性更好。纳米柱状多孔薄膜在可见光范围内具有较大的光调制幅度,因此其光密度变化（ΔOD）大于致密薄膜。     

SnO2 增强相对AgCuOIn2O3 电触头材料显微组织与性能的影响

采用反应合成法结合塑性变形工艺制备了不同SnO₂含量的AgCuOIn₂O₃SnO₂电触头材料,利用扫描电镜和金相显微镜表征了材料的微观形貌及显微组织,分析对比了不同SnO₂含量的材料金相组织及其增强相的分布均匀性,并利用X射线衍射分析了材料的物相结构。测量了材料的抗拉伸强度、硬度、电阻等性能。结果表明：添加适量的SnO₂能使组织中的孔隙尺寸缩小、其他缺陷明显减少。氧化物弥散分布在银基体中,极大地改善了AgCuOIn₂O₃电触头材料的显微组织均匀性。在SnO₂含量不变时,材料的电阻率随塑性变形程度增加而有所降低;随着SnO₂含量增多,电阻率呈现先降低后升高的趋势,最后趋于定值,约为2.4 μΩ·cm。添加SnO₂后各试样材料的硬度均显著升高,SnO₂含量为1%（质量分数）的材料具有最优的抗拉伸强度和延伸率。     

MSM结构TiO2基紫外探测器的制备及光电特性研究

采用RF磁控溅射技术在石英衬底上生长了厚度可调的锐钛矿相TiO₂薄膜,继而采用光刻技术在薄膜上生长了Ag叉指电极,获得了MSM结构TiO₂基紫外探测器。I-V特性测试结果表明Ag与TiO₂之间表现出优良的欧姆接触特性,所制备探测器为欧姆接触。此外,TiO₂薄膜厚度对探测器的光电性能影响显著,当薄膜厚度达到197 nm时,光电性能达到最高。此时,光电流高出暗电流近2.5个数量级,紫外光区的响应度高出可见光区近2个数量级。所制备Ag/TiO₂MSM紫外探测器表现出高灵敏度和可见盲特性。     

锆盐原料不同对LiZr2(PO4)3锂离子固体电解质结构及性能的影响

以不同的锆盐为原料,采用固相法及液相法制备LiZr_2(PO_4)_3锂离子固体电解质,通过无压烧结的方式制备得到固体电解质片,并通过X射线衍射(XRD),扫描电子显微镜(SEM),电化学交流阻抗(EIS)对LiZr_2(PO_4)_3锂离子固态电解质进行表征,通过测试结果对比分析,研究锆盐原料的不同对LiZr_2(PO_4)_3锂离子固态电解质结构及性能的影响。结果表明:当以醋酸锆为锆盐原料时,合成的LiZr_2(PO_4)_3以高电导率的菱方相于室温下稳定存在,而其他3种锆盐作原料时合成的LiZr_2(PO_4)_3室温下以三斜相存在。制备的菱方相LiZr_2(PO_4)_3电解质样品片室温锂离子总电导率最大,为2.25×10~(-5) S/cm,且激活能值最小,为0.28 eV。     

Fe3O4/SiO2/Bi2WO6磁性复合光催化剂的制备及其光催化性能

钨酸铋(Bi₂WO₆),结构最简单的Aurivillius相化合物,是近期受到研究者关注的新型光催化材料。然而,光催化剂粉末在反应介质中难被回收,工业化应用成本较高。本文用三步方法合成了可回收的Fe₃O₄/SiO₂/Bi₂WO₆磁性复合光催化剂,通过溶剂热法合成具有磁性的Fe₃O₄,用溶胶凝胶法在Fe₃O₄表面覆盖SiO₂层,后将磁性颗粒与Bi₂WO₆纳米片相结合。光催化剂的形貌结构及性能通过XRD、SEM、PL、UV-vis进行表征测试。结果表明,直径约500 nm的Fe₃O₄微球附着在边长约500 nm的Bi₂WO₆纳米片的表面,SiO₂在两者之间起到了粘连作用。光催化剂Fe₃O₄/SiO₂/Bi₂WO₆对于罗丹明B的光降解活性较好,且有一定磁性,可以通过外加磁场将其从溶液中分离,有较大的应用潜力。     

Bi2Sn2O7含量对改性Ag/SnO2电接触复合材料性能的影响研究

以SnO2、Bi2Sn2O7为增强相粉体,化学银粉为基体相,采用高能球磨辅助常压烧结工艺制备出系列Bi2Sn2O7改性SnO2增强银基复合材料。考察了Bi2Sn2O7含量、球磨时间、烧结制度对Ag/SnO2-Bi2Sn2O7复合材料物理性能的影响规律。结果表明：随着球磨时间从1h延长至12h,Ag/SnO2-(6 wt.%) Bi2Sn2O7复合粉体从颗粒态向片状结构发生转变,Ag/SnO2-(6 wt.%) Bi2Sn2O7复合材料的电阻率呈逐渐上升趋势而密度呈不断下降趋势。烧结温度的提升和Bi2Sn2O7掺杂量的增加均有助于降低Ag/SnO2-Bi2Sn2O7复合材料的电阻率,且当Bi2Sn2O7掺杂量为12 wt.%、烧结温度900℃时,样品Ag/ (12 wt.%) Bi2Sn2O7的电阻率达到最佳值2.24 μΩ·cm。循环50次的初期电弧烧蚀试验分析可知,相比于纯Ag/SnO2而言,Bi2Sn2O7改性样品表面的烧损面积并未快速扩展至整个表面,且当Bi2Sn2O7含量为6 wt%时,Ag/SnO2-(6 wt.%) Bi2Sn2O7样品表面的烧损面积最小。而当Bi2Sn2O7含量为12 wt.%时, Ag/ (12 wt.%) Bi2Sn2O7表面烧蚀区出现了飞溅现象,这可能归因于其较低的表面硬度(82.38HV0.3)。     

Effects of sputtering pressure and post-metallization annealing on the physical properties of rf-sputtered Y2O3 films

Y₂O₃ thin films were prepared by rf-sputtering under various sputtering pressures at room temperature. Spectroscopic ellipsometer, X-ray diffraction and semiconductor parameter analyzer were used to characterize the studied films. The results show the crystallinity and leakage current density of the films improved with decreasing sputtering pressure. The effects of post-metallization annealing (PMA) on optical, structural and electrical properties of the films were also evaluated. It is found that PMA can significantly enhance the electrical performance of Y₂O₃ film, and the lowest leakage current is found to be 1.54 × 10⁻⁸ A/cm² at 1 MV/cm for the samples treated at 350 °C for 30 min. The leakage current mechanisms were discussed as well, which reveals that space charge limited current dominates the as-deposited films while Schottky mechanism describes the PMA treated ones well.     

Effects of Mg substitution on the structural, optical, and electrical properties of CuAlO2 thin films

Mg-doped CuAlO₂ thin films are prepared by the chemical solution method. The XRD results show that the solid solubility of Mg species on Al sites in CuAlO₂ lattice is lower than 2 at.%. When less than 2 at.% of Mg is added to the CuAlO₂ film, the surface roughness of the films was reduced with Mg substitution. Moreover, the c-axis orientation of the films improves because the in-plane fusion between CuAlO₂ crystallites is hindered. Optical and electrical measurements show that substituting Al³⁺ in the films with Mg²⁺ increases both their transmittance in the visible region and their optical band gaps. As well, their electrical conductivity is enhanced. At 300 K, the conductivity of the 1 at.% Mg-doped sample is up to 5.2 × 10⁻³ S/cm. Thus, Mg-doped CuAlO₂ films may have potential applications as transparent conductive oxides.     

First-principles calculations of electronic and optical properties of Ti-doped monoclinic HfO2

Based on the first-principles density-functional theory, the electronic structures and optical properties of monoclinic HfO₂ and Ti-doped m-HfO₂ are comparatively investigated. The calculated lattice parameters of m-HfO₂ are in good agreement with the experimental values and the previous works, and the incorporation of Ti into HfO₂ induces a decrease in the lattice parameters. Electronic structures of m-HfO₂ and Ti-doped HfO₂ are studied through the densities of states (DOS) and band structures. The results indicate that the Ti substitution of Hf sites modifies the conduction band structure of HfO₂, which leads to a reduction of the band gap of HfO₂. The complex dielectric function and refractive index are calculated and the peak position distributions of imaginary parts of the complex dielectric function have been explained. The calculated optical properties are consistent with the experimental measurements for m-HfO₂.     

Effect of Nb doping on the phase transition and optical properties of sol-gel TiO2 thin films

Various content Nb-doped TiO₂ thin films were prepared by sol-gel process. XRD analysis shows that the existence of crystalline TiO₂ in anatase and rutile form depends on the Nb content in the examined samples. It is observed that Nb promotes the anatase to rutile phase transition but has a depression effect on the anatase grain growth. It is found that incorporation of about 4 at.% of Nb completely transforms anatase TiO₂ to the rutile form at a calcination temperature as high as 900 °C. The mechanism is proposed. Optical analyses show that the films have an average of 60% transmission in visible region. The energy gap values using Tauc's formula have also been estimated. The band gap of rutile Ti_1−xNb_xO₂ solid solutions increases with increasing x.     

Structural, optical and electrical properties of Mg-doped CuCrO2 thin films by sol-gel processing

CuCr_1−xMg_xO₂ (x = 0, 0.03, 0.05, 0.07) thin films were prepared on sapphire substrates by sol-gel processing. The effect of Mg concentrations on the structural, morphological, electrical and optical properties was investigated. Highly transparent ≧70% Mg-doped CuCrO₂ thin films with p-type conduction and semiconductor behavior were obtained. The microstructure of the systems was characterized by scanning electron microscopy and the roughness increased as the content of Mg increased. The photoluminescence spectra results indicated that it had a green luminescent emission peak at the 530 nm. In this paper, CuCr_0.95Mg_0.05O₂ film has the lowest resistivity of 7.34 Ω cm with direct band gap of 3.11 eV. In order to investigate the conduction mechanism, the energy band of the CuCrO₂ films is constructed based on the grain-boundary scattering.     

Laser annealing of flash-evaporated CuInSe2 thin films

In this paper, the impact of laser annealing on the structural, electrical, and optical properties of CuInSe₂ (CIS) thin films has been investigated. The films were deposited using a modified flash evaporation system onto glass substrates. Structural analysis using x-ray diffraction (XRD) showed that the films have a strong preferred growth direction in the 〈112〉 plane. After laser annealing with a diffused beam of 20 ns width, the structure was relaxed and an increase in the intensity of 〈112〉 diffraction line was observed. A gas-microphone-type, high-resolution, near-infared (IR) photoacoustic spectrometer was used for the analysis of nonradiative defect states in as-grown and laser-annealed CIS thin film samples at room temperature. The absorption coefficient has been derived from photoacoustic spectra to establish activation energies for several defect-related energy levels. The calculated intrinsic defect ionization energies were also compared with the existing data available in the literature. The changes in the optical properties of the films have been explained in terms of the variations in the structural characteristics within the material. This paper was presented at the fourth International Surface Engineering Congress and Exposition held August 1–3, 2005 in St. Paul, MN.     

Growth of HT-LiCoO2 thin films on Pt-metalized silicon substrates

Layered LiCoO2 （HT-LiCoO2） films were grown on Pt-metalized silicon （PMS） substrates and polished bulk nickel （PBN） substrates by pulsed laser deposition. The effects of substrate temperature, oxygen pressure, and substrate surface roughness on the microstructure of LiCoO2 films were investigated. It has been found that a higher substrate temperature and a higher oxygen pressure favor the formation of better crystallized and less lithium-deficient HT-LiCoO2 films. The HT-LiCoO2 film deposited on PBN substrates consists of large randomly orientated equiaxial grains, whereas on PMS substrate, it is made up of loosely packed highly [001] preferential orientated triangular shaped grains with the average grain size less than 100 nm. Electrochemical measurements show that the highly [001] preferentially orientated nanostructured HT-LiCoO2 thin film grown on PMS substrate has good structural stability upon lithium insertion/extraction and can deliver an initial discharge capacity of approximately 45μA·h·cm^-2·μm^-1 with a cycling efficiency of above 99% at the charge/discharge rate of 0.5 C.     

Effect of annealing temperature on the structure and optical properties of sputtered TiO2 films

TiO₂ thin films were deposited by DC reactive magnetron sputtering. Some TiO₂ thin films samples were annealed for 5 min at different temperatures from 300 to 900 °C. The structure and optical properties of the films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (SEM) and ultraviolet-visible (UV-vis) spectrophotometry, respectively. The influence of the annealing temperature on the structure and optical properties of the films was investigated. The results show that the as-deposited TiO₂ thin films are mixtures of anatase and rutile phases, and possess the column-like crystallite texture. With the annealing temperature increasing, the refractive index and extinction coefficient increase. When the annealing temperature is lower than 900 °C, the anatase phase is the dominant crystalline phase; the weight fraction of the rutile phase does not increase significantly during annealing process. As the annealing temperature rises to 900 °C, the rutile phase with the large extinction coefficient becomes the dominant crystalline phase, and the columnar structure disappears. The films annealed at 300 °C have the best optical properties for the antireflection coatings, whose refractive index and extinction coefficient are 2.42 and 8 × 10⁻⁴ (at 550 nm), respectively.     

退火温度对ZnTe薄膜结构和性能的影响

采用脉冲激光沉积法(PLD)在玻璃衬底上通过室温溅射和原位退火制备了ZnTe薄膜。通过X射线衍射(XRD)、原子力显微镜(AFM)、紫外-可见分光光度计和荧光分光光度计等研究了退火温度对薄膜结构和性能的影响。结果表明:薄膜具有明显的<110>择优生长特征。随着退火温度的升高,薄膜结晶质量逐渐提高,晶粒长大,透过率增加;但过高的退火温度降低了晶体的结晶质量和透过率。当退火温度为280℃时,ZnTe薄膜具有最好的结晶质量,平均透过率达到90%左右。     

Influence of O2/Ar flow ratio on the structure and optical properties of sputtered hafnium dioxide thin films

Hafnium dioxide (HfO₂) thin films were deposited on a quartz substrate by RF reactive magnetron sputtering. The influence of O₂/Ar flow ratio on the deposition rate, structure and optical properties of HfO₂ thin films were systematically studied using X-ray diffraction (XRD), scan electron microscopy (SEM) and UV-visible spectroscopy. The results show that the deposition rate decreases obviously when the O₂/Ar flow ratio increases from 0 to 0.25 and then, decreases little as the O₂/Ar flow ratio further increases to 0.50. The HfO₂ thin films prepared are all polycrystalline with a monoclinic phase. The thin film deposited with pure argon shows a preferential growth and has considerably improved crystallinity and much larger crystallite size. Meanwhile, after oxygen is introduced into the deposition, the thin films prepared have random orientation, weakened crystallinity and smaller crystallite size. The refractive index is higher for the thin film deposited without oxygen and increases as the O₂/Ar flow ratio increases from 0.25 to 0.50. The band gap energy of the thin film increases with an increasing O₂/Ar flow ratio.