Preparation,characterization and electronic properties of fluorine-doped tin oxide films

Tin oxide(SnO_2) and fluorine doped tin oxide(FTO) films were prepared on glass substrates by sol-gel spin-coating using SnCl_4 and NH_4F precursors.Fluorine doping concentration was fixed at 4 at%and 20 at%by controlling precursor sol composition.Films exhibited the tetragonal rutile-type crystal structure regardless of fluorine concentration.Uniform and highly transparent FTO films,with more than 85%of optical transmittance,were obtained by annealing at 600℃.Florine doping of films was verified by analyzing the valence band region obtained by XPS.It was found that the fluorine doping affects the shape of valence band of SnO_2 films.In addition,it was observed that the band gap of SnO_2 is reduced as well as the Fermi level is upward shifted by the effect of fluorine doping.     

Solvothermal preparation and characteristics of Sn-doped In2O3

Sn-doped In2O3 （ITO） nanopowders were prepared in ethanol solvent by solvothermal process. The effects of the solvothermal temperature, coprecipitation pH value and SnO2 content on the products phase and microwave absorption were investigated by X-ray diffractometry and microwave reflectance. ITO nanopowders with cubic structure can be respectively prepared at 250 and 270 ℃ for 6 h. The prepared product is InOOH or the mixture of InOOH and In3Sn4O12 when the solvothermal temperature is below 250℃. With rising solvothermal temperature and prolonging time, the absorption of the ITO powders gradually decreases. The products are ITO nanopowders by coprecipitating at pH=9 or 11, but ITO powders with Sn3O4 at pH=6. The absorption of powders prepared at pH=6 is better than that at any other pH value. The products are all ITO nanopowders and crystal size reduces with increasing SnO2 content. The microwave absorption of ITO nanopowders with SnO2 content of 8% （mass fraction） is the best among samples with different SnO2 contents.     

第一性原理研究:Mg2+掺杂尖晶石型LiMn2O4的电子结构

尖晶石 LiMn₂O₄ 正极材料是在原有锂电池正极材料 LiCoO₂ 、LiNiO₂ 、LiMnO₂ 的基础上研发出来的优选 正极材料, 它相较于 LiCoO₂ 材料价格更加低廉热稳定性加强且安全性能有所提高。采用 Mg²⁺ 掺杂 LiMn₂O₄正极 材料, 利用基于密度泛函理论的第一性原理对 LiMg_0.5Mn_1.5O₄ 晶格常数与能带结构、态密度进行计算与分析。结 果表明: 新材料 LiMg_0.5Mn_1.5O₄ 的空间群为 F4332, 掺杂后晶胞参数 a 明显减小, 晶胞体积收缩; 掺杂量为 0.5 时明 显比掺杂量 0.125 时 Fermi 能量和能量密度高。Mg ²⁺ 掺杂能影响 LiMn₂O₄ 的晶体结构, 形成更加稳定的共价键。 掺杂量会改变 LiMn₂O₄ 的空间群影响到结构稳定性, 所以掺杂量不宜过大。     

Preparation and characterization of CeO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript>/SnO<Subscript>2</Subscript>:Sb films deposited on glass substrates by R.F. sputtering

CeO2-TiO2 films and CeO2-TiO/SnO2：Sb （6 mol%） double films were deposited on glass substrates by radio-frequency magnetron sputtering （R.F. Sputtering）, using SnO2：Sb（6 mol%） target, and CeO2- TiO2 targets with different molar ratio of CeO2 to TiO2 （CeO2：TiO2-0：1.0; 0.1：0.9; 0.2：0.8; 0.3：0.7; 0.4：0.6; 0.5：0.5; 0.6：0.4; 0.7：0.3; 0.8：0.2; 0.9：0.1; 1.0：0）. The films are characterized by UV-visible transmission and infrared reflection spectra, scanning electron microscopy （SEM）, Raman spectroscopy, X-ray photoelectron spectroscopy （XPS） and X-ray diffraction （XRD）, respectively. The obtained results show that the amorphous phases composed of CeO2-TiO2 play an important role in absorbing UV, there are Ce^3-, Ce^4- and Ti^4- on the surface of the films; the glass substrates coated with CeO2-TiO2 （Ce/Ti=0.5：0.5; 0.6：0.4）/SnO2：Sb（6 mol%） double films show high absorbing UV（〉99）, high visible light transmission （75%） and good infrared reflection （〉70%）. The sheet resistance of the films is 30-50 Ω/□. The glass substrates coated with the double functional films can be used as window glass of buildings, automobile and so on.     

Self-cleaning glass coated with Fe^3＋ -TiO2 thin film

The self-cleaning glass coated with Fe^3 -TiO2 photocatalytic thin film was prepared by sol-gel process from the system Ti(OC4H9),-NH(C2H4OH)2-C2H5OH-H2O containing FeCl3. The microstructure and properties of the film were studied using differential thermal analysis-thermogravimetry(DTA-TG), X-ray diffration (XRD) and scanning electron microscope(SEM). The transmittance of the self-cleaning glass was measured by using UV-Vis spectrometer. The effects of content of Fe^3 and the thickness of Fe^3 -TiO2 thin film on the photocatalytic ac-tivity were examined. The results show that the photocatalytic thin films are mainly composed of Fe3O4 and TiO2 particles within 10-100 nm. The appropriate amount of Fe^3 is effective for improving the photocatalytic activities of TiO2. The best photocatalytic activity is obtained when the molar ratio of Fe^3 to TiO2 is 0. 005 and the glass is coated with 9 layers.     

Preparation of AgSnO2 composite powders by hydrothermal process

Silver-tin oxide powders were synthesized by the hydrothermal method with Ag（NH3）2^＋ solution and Na2SnO3 solution as raw materials and Na2SO3 as reductant. The precipitation conditions of Na2SnO3 solution and the reduction conditions of Ag（NH3）2^＋ were also investigated. The powders prepared were characterized by differential thermal analysis （DTA）, X-ray diffraction analysis （XRD）, scanning electron microscope （SEM） and energy spectrum analysis, The results show that pH value of the solution is a key parameter in the formation of Sn（OH）4 precipitate and the reduction reaction of Ag（NH3）2^＋ can release H^＋ ions, which results in synchronous precipitation of Sn（OH）6^2- as Sn（OH）4. The reduction of Ag（NH3）2^＋ and precipitation of Na2SnO3 occur simultaneously and the coprecipitation of silver and tin oxide is reached by the hydrothermal method. The silver-tin oxide composite powders have mainly flake shape of about 0.3 μm in thickness and there exists homogeneous distribution of tin oxide and silver in the powder synthesized.     

Mechanism and behaviors of Cr3+-doped TiO2

TiO₂ powder and TiO₂ thin film on the surface of glazed ceramic tile were prepared by sol-gel method. The influences of different doping Cr³⁺ concentration on the photocatalytic activity of TiO₂ were discussed, UV-visible and X-ray diffraction analysis were used to test the performance of TiO₂ powder and film. The results indicate that photocatalytic activity of doping Cr³⁺-TiO₂ thin film is higher than that of powder, and the interaction between Cr³⁺-doped and substrate can greatly enhance the photocatalytic activity. The results of X-ray diffraction and photoabsorption show that the Cr³⁺-doped energy level in TiO₂ is 0.62 eV high from the top of valence band, which belongs to the type of deep energy level doping. On the basis of the semiconductor energy level theory and Cr³⁺ dopant energy level, the semiconductor energy level model of Cr³⁺ in TiO₂ powder and thin film were established, and the doping mechanisms of Cr³⁺-doped in TiO₂ powder and thin film were analyzed. Foundation item: Project (20466001) supported by the National Natural Science Foundation of China     

Effects of In2O3 doping and sintering temperature on the electrical properties of ZnO varistors

ZnO varistors are prepared using the 0.1–0.3 mm ZnO powders. The effects of the sintering temperature, contents of In₂O₃ doping on the non-linear properties of ZnO varistors have been investigated. The results show that this kind of ZnO powder has a high sintering activity. It is suitable for making the low voltage varistors. The V _c decreases with the increase of sintered temperature, when the In₂O₃ content is fixed (0.98%, mass fraction), and increases with the increase of In₂O₃ contents when the temperature is steady. Project supported by the Nonferrous Metals Industry Corporation of China Synopsis of the first anthor Zhao Ruirong, born in Jan. 1935, majoring in nonferrous metal metallurgy and products exploition.     

Kinetic study of LiMn2O4 in process of lithium intercalation

Exchange current density of spinel LiMn₂O₄ was studied by linear polarization. The relationship of the kinetic property with the structure of spinel LiMn₂O₄ was investigated by studying the effect of the doping and surface coating on the kinetic properties of electrode material. The results show that the exchange current density of spinel LiMn₂O₄ electrode increases with the increase of the amount for lithium intercalation at first, and then decreases. The maximal exchange current density appeares at the 80%–90% lithium intercalation. The similar phenomenon was observed on the doped spinel LiMn₂O₄ electrode. Doping can enhance the exchange current density of spinel LiMn₂O₄ material. However, the degree of the doping effect varies with the doped element varying. Surface coating can also enhance the exchange current density of spinel material, and the increment of value is higher than that of doped ones. Foundation item: Project(50302016) supported by the National Natural Science Foundation of China     

Synthesis and characterization of triclinic structural LiVPO4F as possible 4.2 V cathode materials for lithium ion batteries

A potential 4.2 V cathode material LiVPO4F for lithium batteries was prepared by two-step reaction method based on a carbon-thermal reduction （CTR） process. Firstly, V2O5, NH4H2PO4 and acetylene black are reacted under an Ar atmosphere to yield VPO4. The transition-metal reduction is facilitated by the CTR based on C→CO transition. These CTR conditions favor stabilization of the vanadium as V^3＋ as well as leaving residual carbon, which is useful in the subsequent electrode processing. Secondly, VPO4 reacts with ElF to yield LiVPO4F product. The property of the LiVPO4F was investigated by X-ray diffractometry （XRD）, scanning electron microscopy （SEM） and electrochemical measurement. XRD studies show that LiVPO4F synthesized has triclinic structure（space group p I ）, isostructural with the naturally occurring mineral tavorite, EiFePO4-OH. SEM image exhibits that the particle size is about 2μm together with homogenous distribution. Electrochemical test shows that the initial discharge capacity of LiVPO4F powder is 119 mA·h/g at the rate of 0.2C with an average discharge voltage of 4.2V （vs Ei/Li^＋）, and the capacity retains 89 mA·h/g after 30 cycles.     

Studies of key technologies for CdTe solar modules

In this paper, CdS thin films, which act as the window layer and n-type partner to the p-type CdTe layer, were prepared by chemical bath deposition (CBD). CdTe thin films were deposited by the close-spaced sublimation (CSS) method. To obtain high-quality back contacts, a Te-rich layer was created with chemical etching and back contact materials were applied after CdTe annealing. The results indicate that the ZnTe/ZnTe:Cu complex layers show superior performance over other back contacts. Finally, by using laser scribing and mechanical scribing, the CdTe mini-modules were fabricated, in which a glass/SnO₂:F/CdS/CdTe/ZnTe/ZnTe:Cu/Ni solar module with a PWQC-confirmed total-area efficiency of 7.03% (54 cm²) was achieved. Supported by the Hi-Tech Research and Development Program of China (Grant No. 2003AA513010), and the Science and Technology Program of Sichuan Province, China (Grant No. 05GG021-003-3)     

Magnetostrictive distortion in Pr0.15Tbx Dy0.85-xFe2 polycrystals by X-ray diffraction

The ingots of Pr0.15 Tbx Dy0.85-x Fe2 (x=0.10-0.85) series compounds with a single phase were prepared by a arc melting method. The X-ray diffraction patterns were measured using a Philips X‘pert MPD X-ray diffractometer with a non-ambient sample stage at different temperatures, the magnetostfictive distortion in Pr0.15 Tbx Dy0.85-x Fe2 polycrystals was investigated by X-ray diffraction patterns and the magnetostfiction coefficient λ111 was calculated. The results show when the temperature is raised above the spin reorientation temperature region, a splitting appears in the reflection (440); the λ111 increase with the increasing of Tb content for Pr0.15 Tbx Dy0.85-x Fe2 polycrystals and thefull width at half maximum (FWHM) of the reflection (440) increases gradually with the increasing of Tb content.Moreover, as the FWHM of the reflection (440) decreases gradually with the increasing of temperature, the λ111 decreases slightly with the increasing of temperature at the temperature region of 223 -373 K for Pr0.15 Tb0.3 Dy0.55 Fe2 alloy.     

Ferroelectric properties of Bi3.4Ho0.6Ti3O12 thin films prepared by sol-gel method

We have prepared the Ho-substituted bismuth titanate (Bi_3.4Ho_0.6Ti₃O₁₂, BHT) thin films on Pt/Ti/SiO₂/Si substrates using sol-gel method. The crystal structure and morphology of the films were characterized using X-ray diffraction and atomic force microscopy. The BHT film shows a single phase of Bi-layered Aurivillius structure and dense microstructure. The 2Pr and 2Ec of the 600-nm-thick BHT film were 38.4 μC/cm² and 376.1 kV/cm, respectively at applied electric field 500 kV/cm. The dielectric constant and dielectric loss are about 310 and 0.015 at a frequency of 1 MHz, respectively. The Pr value decreased to 93% of its pre-fatigue values after 4.46×10⁹ switching cycles at 1 MHz frenquency, and the BHT film shows good insulating behavior according to the test of leakage current. Supported by the Hubei Province Natural Science Foundation (Grant No. 2007ABA309)     

Preparation and Properties of CdTe Polycrystalline Films for Solar Cells

The structure and characteristics of CdTe thin filrns are closely dependent on the whole deposition process in close-space sublimation （CSS）. The physical mechanism of CSS was analyzed aud the temperature distribution in CSS system was measured, and the influences of the increasing-temperature process and pressure on the preliminary nucleus creation were studied. The resuits indicate ： tire samples deposited at different pressures hare a cubical structure of CdTe and the diffraction peaks of CdS and SnO2 ： F. As the atmosphere pressure increases, the crystal size of CdTe decreases, the rate of the transparency of the thin film decreases and the absorption side moves towards the short-wave direction. After a 4-minute depositing process with a substrate teraw.rature of 500℃ and a source temperature of 620 ℃, the polycostallinc thin films can be mmade , so the production of high-quality integrated cell with StrO2： F/ CdS/ CdTe/ Au structure is hopeful.     

Antibiotic properties of Al2O3 doping silver

The preparation technique and properties of Ag-type inorganic antibiotic material carried by Al₂O₃ were studied. The results show that the material has good antibiotic and safety properties, the acute toxicity taken by stomata is LD ₅₀>8 000 mg/kg (little and big white rats), and the normal quantity in subacute toxicity test is 80 mg/(kg · d). The better mass fraction of doping Ag₂O in antibiotic material carried by Al₂O₃ is 4%–8%, and the optimal sintering temperature is from 1 000 °C to 1 100 °C. Foundation item: Project (2002AA327090) supported by National High Technology Research and Development Program of China     

Preparation and properties of 4.25Cu-0.75Ni／NiFe2O4 cermet

4.25Cu-0.75Ni/NiFe₂O₄ cermets were prepared by doping NiFe₂O₄ ceramic matrix with the mixed powders of Cu and Ni or Cu-Ni alloy powder as the electrical conducting metallic elements. The effects of technological parameters, such as the adding modes of metallic elements, the ball milling time, the sintering time and the sintering temperature, on the relative density and resistivity of the cermets were studied. The results show that the resistivity of 4.25Cu-0.75Ni/NiFe₂O₄ cermets decreases with increasing temperature, and has a turning point at 590 °C, which is similar to that of NiFe₂O₄ ceramic. The sintering temperature and adding modes of metallic elements have a great influence on the properties of 4.25Cu-0.75Ni/NiFe₂O₄ cermets. When the sintering temperature increases from 1200 °C to 1300 °C, the relative density increases from 89.86% to 95.33%, and the resistivity at 960 °C decreases from 0.11 Ω · cm to 0.03 Ω · cm, respectively. When the metallic elements are added with the mixed powders of Cu and Ni, the cermets of finely and uniformly dispersed metallic phase, high density and electric conductivity are obtained. The relative density and resistivity at 960 °C are 90.23% and 0.04 Ω · cm respectively for the cermet samples sintered at 1200 °C for 2 h, which are both better than those of the cermets prepared under the same technique conditions but with the metallic elements added as 85Cu-15Ni alloy powders. Foundation item: Project (G1999064903) supported by the National Key Fundamental Research and Development Program of China; project(2001AA335013) supported by the National High Technology Research and Development Program of China; project (50204014) supported by the National Natural Science Foundation of China     

Influence on performance and structure of spinel LiMn2O4 for lithium-ion batteries by doping rare-earth Sm

The spinel LiMn₂O₄ used as cathode materials for lithium-ion batteries was synthesized by mechano-chemistry fluid activation process, and modified by doping rare-earth Sm. Thesting of X-ray diffraction, cyclic voltammograms, charge-discharge and SEM was carried out for LiMn₂O₄ cathode materials and the modified materials. The results show that the cathode materials doped rare earth Li _x Mn_2−y Sm _z O₄ (0.95⩽x⩽1.2, 0⩽y⩽0.3, 0⩽z⩽0.2) exhibit standard spinel structure, high reversibility of electrochemistry and excellent properties of charge-discharge. In EC: DMC(1 : 1)+1 mol/L LiPF₆ electrolyte with discharge capacity more than 130 mA · h/g, and its capacity is deteriorated less than 15% after 300 cycles at room temperature and less than 20% after 200 cycles at 55°C. At the same time, Crystal Field Theory was applied to explain the function and mechanism of doped rare earth element. Foundation item: Project (02JJY2081) supported by the Natural Science Foundation of Hunan Province     

Morphology and conductivity of in-situ PEO-LiClO4-TiO2 composite polymer electrolyte

PEO-LiClO4-TiO2 composite polymer electrolyte films were prepared. TiO2 was formed directly in matrix by hydrolysis and condensation reaction of tetrabutyl titanate. The crystallinity, morphology and ionic conductivity of composite polymer electrolyte films were examined by differential scanning calorimetry, scanning electron microscopy, atom force microscopy and alternating current impedance spectroscopy, respectively. The glass transition temperature and the crystallinity of composite polymer electrolytes are decreased compared with those of PEO-LiClO4 polymer electrolyte film. The results show that TiO2 particles are uniformly dispersed in PEO-LiClO4-5%TiO2 composite polymer electrolyte film. The maximal conductivity of 5.5×10^-5 S/cm at 20℃ of PEO-LiClO4-TiO2 film is obtained at 5% mass fraction of TiO2.     

ZrO2 与TiO2 介孔薄膜对碳基介孔型钙钛矿太阳能电池的 性能影响

通过旋涂ZrO_2与TiO_2混合浆料,制备钙钛矿太阳能电池介孔层。以孔径较大的ZrO_2/TiO_2混合介孔薄膜(MIX)为基底制备了晶粒较大的甲胺铅碘(MAPbI3)钙钛矿光吸收层。以致密TiO_2薄膜为电子传输层,石墨/碳黑为对电极,制备了钙钛矿太阳能电池。比较了ZrO_2单层介孔、Ti O2单层薄膜、TiO_2+ZrO_2双层介孔与ZrO_2/TiO_2单层混合介孔的钙钛矿太阳能电池的性能。结果表明,用MIX制备的钙钛矿太阳能电池表现出最高的光电转换效率(PCE)和良好的长期稳定性。     

不同掺Al3+浓度的ZnO:Al薄膜性能研究

采用溶胶-凝胶法制备ZnO:Al (ZAO)薄膜,得到了不同掺Al3+浓度的ZAO薄膜;利用X射线衍射仪分析、原子力显微镜、紫外-可见分光光度计及四探针法等仪器与方法对其性能进行了测试。通过分析比较,得出所制备的ZAO薄膜为多晶纤锌矿结构,薄膜表面平整、晶粒致密均匀;Al3+掺杂能提高其导电性能:低掺杂时,薄膜在紫外-可见光范围的透过率超过80%,并伴有蓝移现象产生;高掺杂时,其透过率无明显增加,但蓝移现象加剧,最大蓝移量达340 nm。