Analysis of precursor residues in lithium aluminosilicate gels using XPS and RGA

Lithium aluminosilicate gels of composition 15 mol% lithia-2 mol% alumina-83 mol% silica were prepared by adding nitrates to tetraethyl-orthosilicate (TEOS) and going through the sol-gel process. Samples were prepared in thin film and bulk form. Dried and outgassed samples were studied with X-ray photoelectron spectroscopy (XPS) d residual gas analysis (RGA). XPS spectra show similar species in both thin film and bulk samples, but different relative quantities of each species. Some oxidation of organic groups by nitrate is evident in bulk samples which were heated to 70°C during the drying process. In both thin film and bulk samples, the O 1s spectra indicate oxygens associated with a silicate network and higher binding energy species such as - -O-. The C 1s spectra of bulk gels heated to 140° and 350°C in vacuum show some organics are vaporized at low temperature, while the oxidized-organic residues are decomposed to CO₂ at high temperature. These species are also observed with residual gas analysis at the corresponding temperatures.     

Temperature dependence of growth orientation and surface morphology of Li‐doped ZnO thin films on SiO2/Si substrates

ZnO thin films doped with Li (ZnO:Li) were deposited onto SiO₂/Si (100) substrates by direct‐current sputtering technique in the temperature range from room temperature to 500 °C. The crystalline structure, surface morphology and composition, and optical reflectivity of the deposited films were studied by X‐ray diffraction (XRD), Scanning Electron Microscopy (SEM), X‐ray Photoelectron Spectroscopy (XPS) and optical reflection measurements. Rough surface p‐type ZnO thin film deposition was confirmed. The results indicated that the ZnO:Li films growed at low temperatures show c‐axis orientation, while a‐axis growth direction is preferable at high temperatures. Moreover, the optical reflectivity from the surface of the films matched very well with the obtained results. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

真空蒸发法制备ZnSe薄膜的X射线光电子能谱研究

本文用真空蒸发法制备了CIS太阳能电池中做缓冲材料的ZnSe薄膜,利用X射线光电子能谱(XPS)对制备薄膜的表面化学状态及沉积质量进行了研究,并用氩离子溅射进行剥蚀,逐层分析薄膜的化合态随深度的变化关系.XPS分析表明,ZnSe薄膜含有Zn、Se、O、C等元素,其中O、C为样品置于空气中所致,含量随剥蚀深度的加大而逐渐降低.Zn的光电子峰为Zn2p1/2和Zn2p3/2,Zn2p3/2的电子结合能为1021.90eV,对应着Zn2+的化合态,表明薄膜中zn以形式电荷为Zn2+的化合态形式存在;Se的光电子峰为Se3d,其电子结合能为54.30eV,对应着Se2-的化合态,表明薄膜中Se以形式电荷Se2-的化合态形式存在.分别经过1min、3min、7min、11min的剥蚀后,Zn和Se的光电子峰几乎没有改变,表明沉积的ZnSe薄膜表面和内部化学状态稳定一致.     

氩氧流量比对CeOx-SnOx膜微观结构及光学性能的影响

采用磁控反应共溅射的方法,以金属Ce和Sn为金属源,成功地制备出CeOx-SnOx薄膜.利用扫描电子显微镜(SEM)、X射线衍射(XRD)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)等测试手段对薄膜的结构、表面形貌及成分进行了分析和表征.结果表明薄膜以岛状模式生长,随氩氧比降低,结晶性增强,出现CeO2和SnO相.此外,利用紫外-可见分光光度计对薄膜的光学性能进行了研究,测试结果表明薄膜对紫外光有极强的吸收作用.当氩氧流量比为3∶1时,紫外光平均透过率仅为5.80;,而可见光平均透过率为81.48;.     

Synthesis of type-I textured tungsten disulfide thin films on quartz substrate

Tungsten disulfide (WS₂) films were obtained by solid state reaction of spray deposited WO₃ with gaseous sulfur i.e. solid gas phase reaction (SGP). The XRD and SEM studies revealed the formation of WS₂ thin films on quartz substrate with a mixed type-I and type-II texture. The WS₂ thin films prepared with a controlled heating/cooling rate of 323 K/h. during the sulfurization were free from cracks while those prepared with higher heating/cooling rate during the sulfurization suffer from cracks. The former WS₂ thin film comprises well defined hexagonal crystallites with larger size (2 μm) and thickness. The complete conversion of WO₃ into WS₂ was observed when sulfurization carried out in evacuated quartz ampoule containing sulfur. A low oxygen and carbon content was observed in XPS spectrum due to air exposure of the sample which is removed by in-situ Ar cleaning. XPS and EDS studies showed that the films are stoichiometric.     

类石墨氮化碳薄膜的电化学沉积

用1:1.5的三聚氯氰和三聚氰胺的饱和乙腈溶液为沉积液,在Si(100)衬底上室温常压下电化学沉积了CNx薄膜.用X射线光电子能谱(XPS)、傅立叶转换红外光谱(FTIR)、X射线衍射图谱(XRD)对沉积的CNx薄膜进行了测试和分析.XRD的衍射峰的结构数据与文献计算的类石墨相氮化碳的结构数据较为吻合.XPS结果表明沉积的薄膜中主要元素为C、N,且N/C=0.81,C1s和N1s的结合能谱中287.84eV的碳和400.00eV的氮是样品中碳氮的主体,以C3N3杂环的形式存在.FTIR光谱中在800cm-1、1310cm-1和1610cm-1的吸收峰也表明薄膜中存在C3N3环,和XPS能谱的分析结果一致.Teter和Hemley预言的g-C3N4在结构形式上和三聚氰胺的完美脱胺缩聚物是一样的,红外光谱和X射线光电子能谱表明在样品中存在三嗪环(C3N3),支持XRD的实验结果.这说明CNx薄膜中有类石墨相的C3N4晶体存在.     

A solvothermal route to tellurium based thin films

Tellurium thin film was prepared via a solvothermal route on glass substrates modified by exchaning the positive charge with high charge. It was characterized by SEM and XRD. The possible growth of tellurium thin film was proposed. It is expected that this method would be extended to other functional thin films. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A new photoluminescent supramolecular inorganic‐organic hybrid zincophosphate complex pillared by carboxylate ligand through hydrogen bonding interactions

A new inorganic‐organic hybrid zincophosphate, [Zn(H₂O)₂(H₂PO₄)₂]·2PABA ( 1 ) (PABA = p‐aminobenzoic acid), pillared by PABA ligands through hydrogen bonding interactions, has been synthesized and characterized. Single‐crystal X‐ray diffraction reveals that 1 crystallizes in the monoclinic P 2₁/c space group. The geometric feature in 1 is the 3D supramolecular structure constructed from alternately arranged organic and inorganic layers that consist of infinite parallel inorganic chains. These chains are extended to a 2D inorganic layer through intermolecule hydrogen bonding interactions between N atoms (from PABA ligand) and two O atoms (from adjacent inorganic chains). 1 was characterized by IR spectroscopy, XRD, DSC/TGA. The fluorescent property for 1 in solid state was also investigated at room temperature. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

衬底温度对直流反应磁控溅射法制备的N掺杂p型ZnO薄膜性能的影响

利用直流反应磁控溅射法(纯金属锌作为靶材,Ar-N2-O2混合气体作为溅射气体)在石英玻璃衬底上制备了N掺杂p型ZnO薄膜.通过XRD、Hall和紫外可见透射谱分别研究了衬底温度对ZnO薄膜结构性能、电学性能和光学性能的影响.XRD结果显示所有制备的薄膜都具有垂直于衬底的c轴择优取向,并且随着衬底温度的增加,薄膜的晶体质量得到了提高.Hall测试表明衬底温度对p型ZnO薄膜的电阻率具有较大影响,400℃下生长的p型ZnO薄膜由于具有较高的迁移率(1.32 cm2/Vs)和载流子浓度(5.58×1017cm-3),因此表现出了最小的电阻率(8.44Ω·cm).     

磁控溅射（TiO2-ZnO）/TiO2梯度复合薄膜的制备及光致亲水性研究

采用磁控溅射离子镀设备制备了(TiO2-ZnO)/TiO2梯度复合薄膜,通过TEM、AFM、Raman、XPS分析了复合薄膜的结构、形貌和表面羟基含量,以甲基橙作为有机降解物,研究了(TiO2-ZnO)/TiO2梯度复合薄膜与普通TiO2-ZnO复合薄膜和TiO2薄膜在光催化性能和光致亲水性能上的差异。结果表明:(TiO2-ZnO)/TiO2梯度复合薄膜具有以主体为TiO2-ZnO层、顶层为TiO2的梯度结构,且薄膜表面致密、粒径均匀(10～14 nm),光催化性和亲水性均优于普通TiO2-ZnO复合薄膜和TiO2薄膜,且其光波响应范围红移至450 nm、表面羟基含量高达12.53%,同时梯度复合薄膜的抗光腐蚀性能良好,4 h以后其润湿角仍保持不变。     

PEM控制合成碳掺杂钛氧薄膜的成分结构研究

采用等离子体发射监测(PEM)系统实现闭环控制反应气体流量,使反应溅射稳定在滞回曲线过渡区,并以气相CO2和O2为碳源和氧源制备了碳掺杂钛氧(C∶Ti-O)薄膜.采用原子力显微镜、掠入射X射线衍射和X射线光电子能谱表征薄膜的表面形貌、结构、成分,紫外-可见分光光度计测试薄膜透射率并用Tauc作图法计算薄膜的带隙宽度.结果表明,随着辉光强度设定点(SP)的增大,沉积速率增大,薄膜中Ti-C键含量增多,带隙宽度降低,薄膜的结晶性增强且有利于金红石相的形成.     

Surface Chemical Bonding States and Ferroelectricity of Pb(Zr0.52Ti0.48)O3 Thin Films

The surface chemical bonding states and the ferroelectric properties of sol‐gel deposited lead zirconate titanate [Pb(Zr_0.52Ti_0.48)O₃, PZT] thin films coated on (111)Pt/Ti/SiO₂/Si substrates were investigated. X‐ray photoelectron spectroscopy (XPS) was used to determine the oxidation state of the surface and the chemical composition as a function of depth in ferroelectric PZT thin layers. Values for the dielectric constant and dissipation factor at 1 kHz for the 300 nm‐thick film were 1214 and 0.014 for the film annealed at 520 °C, and 881 and 0.015 for a film annealed at 670 °C. Measured values for the remanent polarization (P_r) and coercive field (E_c), from polarization‐electric field (P‐E) hysteresis loops biased at 10 V at a frequency of 100 Hz, were 16.7, 14.4 μC/cm² and 60, 41.7 kV/cm for 520 °C and 670 °C. The leakage current density (J) was 72 and 96 nA/cm² at an applied field of 100 kV/cm. It was found that the bonding states of lead and oxygen in the surface regions could be correlated with the ferroelectric properties of the integrated thin layers.     

New TiO2 precursor for TiO2:poly(N-vinylcarbazole) (PVK) thin film: Synthesis and reactivity to hydrolysis of titanium tetrakis (9H-carbazole-9-yl-ethyl-oxy)

The chemical reactivity of the ligand initially coordinated on the TiO₂ precursor plays a decisive role in the morphology of TiO₂:poly(N-vinylcarbazole) (PVK) thin film elaborated by in situ generation of the inorganic phase in the polymer matrix. The final aim of this study is to prepare a new nanocomposite TiO₂:poly(N-vinylcarbazole) (PVK) thin film from hydrolysis-condensation of titanium alkoxide in polymer thin film. In this context, we synthesized a new TiO₂ precursor, the tetrakis (9H-carbazole-9-yl-ethyl-oxy) [Ti(OeCarb)₄], bearing ligands close to the repetitive unit structure of the PVK to improve the interaction between both materials. In this study, the synthesis and reactivity to hydrolysis of Ti(OeCarb)₄ is presented. Ti(OeCarb)₄ was elaborated from alcoholysis reaction between titanium isopropoxide [Ti(ⁱOPr)₄] and 9H-carbazole-9-ethanol (ECOH) and identified by ¹H and ¹³C NMR spectroscopy. The reactivity to hydrolysis-oxolation of Ti(OeCarb)₄ was evaluated first in aqueous media by in situ ¹H NMR spectroscopy analysis. Moreover, reactivity of Ti(OeCarb)₄ to surrounding humidity was evaluated in thin film by X-ray photoelectron spectroscopy (XPS). Results show that steric hindrance of 9H-carbazole-9-yl-ethyl-oxide ligands do not influence the hydrolysis-condensation process in aqueous media in our experimental conditions when compared to [Ti(ⁱOPr)₄] but decrease the reactivity when the precursor is simply exposed to air humidity.     

退火效应对MOCVD生长的ZnO薄膜的影响

我们利用MOCVD设备在α-Al2O3衬底上生长了c轴取向的ZnO薄膜,通过X射线衍射(XRD)、光致发光谱(PL)对ZnO薄膜进行表征,研究了退火对ZnO薄膜光电特性影响.通过退火优化, ZnO薄膜的结晶性得到提高,晶粒尺寸变大,紫外光发射峰的强度相对变强.     

On the Chemical Mechanism of the Zinc Diffusion into GaAs from SiO2 Spin-on Films

The chemical processes which take place during annealing were studied in both model substances and thin films deposited onto GaAs wafers by thermal analysis, X-ray powder diffraction, IR spectroscopy, XPS and TEM. It was found that at 600°C only about 45% of the film was changed to SiO₂ glass. At 700 °C begins the formation of zinc silicates. In this form the zinc seems to be scarcely able to diffuse into GaAs. Obviously, the exothermic DTA effect at 800 °C arises from this zinc silicate formation connected with a recrystallization of the amorphous film.     

基于Si衬底的CdSe薄膜蒸镀工艺研究

采用真空蒸发技术在Si(100)基底上制备了CdSe纳米晶薄膜,利用X射线衍射仪(XRD)、膜厚测试仪、原子力显微镜(AFM)方法对不同蒸发电流下制备的薄膜的结晶情况、表面形貌进行分析表征.结果表明:蒸发电流对CdSe薄膜的结晶性能和表面形貌有显著影响.当蒸发电流为75 A时,CdSe薄膜沿(002)方向的衍射峰相对较强,沿c轴取向择优生长优势明显,薄膜厚度约为160 nm,晶粒尺寸约为40 nm,颗粒均匀;薄膜表面平整光滑,表面粗糙表面粗糙度(5.63 nm)相对较低,薄膜结晶质量较好.     

制备参数对钙钛氧化物薄膜的微结构和性能影响

利用钛酸丁酯-氯化钙-无水乙醇体系通过溶胶-浸渍提拉法制备了钙钛氧化物薄膜.采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)及能谱分析仪(EDS),荧光光谱仪和紫外-可见分光光度计等技术对薄膜的结构,形貌及元素成分和光学性能进行了分析.结果表明:当n(钛酸丁酯)/n(乙醇)为1∶15时,制备得到了光学性质良好(价带较宽)的钙钛氧化物薄膜.随着焙烧温度升高到550℃,薄膜的结晶强度不断增加,薄膜主晶相由CaTiO3相转化为层状结构CaTi2O4(OH)2主晶相,该薄膜呈现多孔结构,从而使光学特性进一步增强.     

Separation of 4-aminobenzoic acid by cocrystallization: Crystal structure of the complex of 4-aminobenzoic acid with (2R,3R)-tartaric acid

4-Aminobenzoic acid (PABA) has been successfully separated from a mixture containing 2-aminobenzoic acid and (2R,3R)-tartaric acid. X-ray structure analysis confirms the separating result. The molecular complex formed by PABA and tartaric acid in 1:1 molar ratio crystallizes in the orthorhombic space group P2₁2₁2₁ with cell dimensions of a = 7.329(1) Å, b = 12.095(2) Å, c = 15.231(3) Å, V = 1350.1(4) ų, Z = 4. The crystal structure comprises protonated PABA, monoanion of tartaric acid, and crystalline water. The extensive H-bonding network exists in the crystal structure. H bonding between tartaric acid and both terminal groups on para position of PABA is considered as a possible reason for the successful separation.     

结晶β-C3N4薄膜的制备和特性研究

用电子回旋共振等离子体化学汽相沉积(ECR CVD)法, 在单晶硅(100)衬底上沉积生长出了具有{221}结构特性的连续的结晶态β-C3N4薄膜.使用扫描电镜(SEM)观测了沉积薄膜的形态;采用X射线光电子光谱(XPS),X射线衍射(XRD)和拉曼散射表征薄膜的结构.研究表明,沉积结晶态β- C3N4薄膜具有{221}结构特性.     

Effect of plasma carrier gas on the moisture barrier properties of plasma-enhanced chemical vapor deposited (PECVD) polyorganosiloxane thin film

Abstract

A polyorganosiloxane thin film was deposited on an optically transparent poly(ethylene 2,6-naphthalate) (PEN) film using plasma-enhanced chemical vapor deposition (PECVD) at room temperature to improve the moisture barrier property of the PEN film. In the PECVD process, hexamethyldisiloxane (HMDSO) was used as the monomer. Argon or oxygen and their mixture gases were used as the plasma carrier gas. Poly(HMDSO) thin film was successfully deposited through plasma-induced radical polymerization reaction on the surface of PEN film. It was observed that the mixture ratio of argon-oxygen carrier gas significantly affected the surface and the moisture barrier properties of the resulting poly(HMDSO) film. Chemical structures of the poly(HMDSO) were confirmed using FT-IR analysis. Surface properties of the poly(HMDSO) thin film were investigated by water contact angle measurement and atomic force microscopy (AFM). Water vapor transmission rate (WVTR) value was obtained by an electrical calcium test (Ca test) at 85?°C and 85% relative humidity condition. It was confirmed that the poly(HMDSO) thin film exhibited excellent water vapor barrier capability. WVTR value of the PEN film coated with poly(HMDSO) deposited with a mixture of argon and oxygen (Ar: O₂ = 2: 8) was 5.09?g/m²-day, which is much lower than 18.4?g/m²-day of a bare PEN film.