非水解溶胶-凝胶法制备硅酸锆薄膜及抗碱腐蚀性能

以正丙醇锆和正硅酸乙酯分别为锆源和硅源,结合非水解溶胶-凝胶法和提拉镀膜工艺制备出硅酸锆(ZrSiO_4)薄膜。采用XRD、FTIR、SEM、AFM等分析测试手段研究了前驱体浓度、提拉速度对ZrSiO_4合成、ZrSiO_4薄膜形貌及显微结构的影响,并研究薄膜的抗碱液腐蚀性能。结果表明:当前驱体浓度为0.1 mol/L、提拉速度为1mm/s时可以在单晶硅片获得表面光滑、平整致密、无开裂的ZrSiO_4薄膜。镀有ZrSiO_4薄膜的单晶硅片在浓度为40%NaOH溶液中40℃条件下浸泡42 h,表面只发现有较小的坑蚀,且质量随腐蚀时间延长变化很小,质量损失仅为0.17%,表明该ZrSiO_4薄膜具有较好的抗碱液腐蚀性能。     

以氟化锆为生长助剂制备硅酸锆晶须的研究

以无水四氯化锆为锆源,正硅酸乙酯(TEOS)为硅源,氟化锂为矿化剂,乙醇为溶剂,氟化锆为生长助剂,采用非水解溶胶-凝胶法于800℃制备出硅酸锆晶须,借助XRD、SEM和TEM等测试手段研究了热处理气氛、氟化锂用量、氟化锆的引入方式等工艺因素对硅酸锆晶须形成的影响。结果表明:与空气气氛相比,氮气气氛更加有利于硅酸锆晶体的一维择优生长;矿化剂用量过多或过少均不利于晶须的形成;氟化锆以外置的方式引入能获得直径为0.2~0.4μm,长径比达15~30,沿c轴方向择优生长的硅酸锆晶须。     

正硅酸乙酯为碳源制备C@ZrSiO_4色料的研究

采用正硅酸乙酯为碳源和硅源,四氯化锆为锆源,Li F为矿化剂,通过非水解溶胶-凝胶法(NHSG)制备了硅酸锆包裹炭黑(C@ZrSiO_4)色料。通过XRD和SEM研究了前驱体和矿化剂浓度对硅酸锆合成及显微形貌的影响,同时采用CIE-L~*a~*b~*色度仪考察了该色料的色度。实验结果表明,正硅酸乙酯中的乙氧基原位炭化成细小的碳粒作为发色基团,同时与氯化锆通过非水解溶胶-凝胶反应生成硅酸锆均匀包裹于炭黑颗粒表面。随着前驱体浓度的增大原位碳含量增加,C@ZrSiO_4色料黑度提高;前驱体浓度高于3 mol·L~(-1)时样品颗粒团聚严重,同时过厚的包裹层不利于色料发色。经氮气气氛900℃热处理2 h,空气气氛800℃热处理2 h后制备出的C@ZrSiO_4黑色包裹色料具有良好的色度值,L~*=44.54,a~*=0.82,b~*=2.84,施于透明基础釉中经1200℃煅烧仍能保持优异的呈色能力。     

非水解溶胶-凝胶法制备硅酸锆晶须初探

以无水四氯化锆为锆源,正硅酸乙酯(TEOS)为硅源,氟化锂为矿化剂,乙醇为溶剂,炭黑为还原剂,采用非水解溶胶-凝胶法制备硅酸锆晶须,研究了炭黑种类与坩埚密封程度对硅酸锆晶须生长的影响。结果表明:相对于比表面积过小的炭黑8001或比表面积过大的超级活性炭,竹炭更利于硅酸锆晶须的生长;采用敞开坩埚方式热处理时能获得直径为30~90 nm,长径比为6~15,沿[001]方向择优生长的硅酸锆晶须,半敞开或密封的反应体系均不能形成硅酸锆晶须。     

非晶前驱体碳热还原法制备超细硼化锆粉体

利用Zr O2-B2O3-C反应体系碳热还原的基本原理,分别选用八水合氧氯化锆(Zr OCl2·8H2O)、硼酸(H3BO3)和蔗糖(C11H22O11)作为Zr O2、B2O3和C的来源,柠檬酸(C6H8O7)为络合剂,采用溶胶-凝胶法制得硼化锆的非晶前驱体,经过碳热还原反应热解制备出超细硼化锆粉体。分别研究了硼酸、蔗糖用量和热解温度对产物的物相组成的影响。采用红外光谱仪、热重-差热分析仪、X射线衍射仪、比表面积分析仪和扫描电镜对硼化锆前驱体及热解产物进行表征和分析。结果表明:初始原料中八水合氧氯化锆:硼酸:裂解碳(物质的量比)=1∶4∶10时,可在相对较低温度下(1300℃)热解得到硼化锆粉体,且随着热解温度的升高硼化锆粉体的纯度也越高。当热解温度为1600℃、热解时间为2 h时碳热还原反应完成,产物中只有硼化锆;硼化锆颗粒呈球形或类球形,粒径分布在0.2~0.6μm之间、比表面积为74 m2/g。     

溶胶-凝胶法制备钛酸铝薄膜及其抗熔盐腐蚀性能

以钛酸四丁酯和硝酸铝为原料,乙醇为溶剂,通过溶胶-凝胶法在碳化硅基片上制备钛酸铝薄膜。借助DSC-TG、XRD、FE-SEM和SEM研究了钛酸铝干凝胶在热处理过程中的热重效应与相变化、薄膜的晶相组成、显微结构及其抗硝酸钠熔体腐蚀性能。结果表明:制备的钛酸铝薄膜表面均匀、致密,晶粒尺寸在100nm左右,具有良好的抗硝酸钠熔体腐蚀性能。     

热丝CVD法沉积固态扩散源制备晶硅太阳电池p~+/n~+发射极研究

为进一步提高晶硅太阳能电池发射极的性能,本文提出了一种新的发射极制备技术-低温CVD法沉积固态薄膜扩散源并进行高温扩散。采用热丝化学气相沉积法(HWCVD)在单晶硅片上沉积重掺杂硅基薄膜作为固态扩散源,然后在空气氛围下的管式炉中进行高温扩散,最后用稀HF溶液去除表面的BSG/PSG。通过掺磷薄膜扩散在P型单晶硅片上制备了方阻在50~250Ω/□范围内可控的n+型发射极;通过掺硼薄膜扩散在N型硅片上制备了方阻在150~600Ω/□范围内可控的p+型发射极。并且通过在源气体中加入CO2作为氧源,实现了扩散后硅片表面残留扩散源层的彻底去除。     

SDC/YSZ双层电解质薄膜的制备与特性

利用脉冲激光沉积技术(PLD)在MgO单晶片基底上制备Ce_(0.8)Sm_(0.2)O_(2-δ)/ZrO_2∶Y_2O_3(SDC/YSZ)双层电解质薄膜。X射线衍射仪(XRD)和扫描电子显微镜(SEM)的结果显示SDC/YSZ双层电解质薄膜沿(111)方向择优生长,随着退火温度的升高,薄膜变得均匀致密,结晶度得到改善,(111)衍射峰强度变大,择优生长取向明显;电化学测量表明,SDC/YSZ双层电解质薄膜的离子电导率比单层YSZ薄膜的离子电导率高。     

熔盐中镁热还原合成碳化锆粉体

以炭黑、不同锆源(二氧化锆、钙稳定氧化锆、氧氯化锆)为原料,金属镁粉为还原剂,在NaCl/KCl熔盐、氩气气氛中发生还原反应及锆碳反应,开展了碳化锆粉体的合成研究.通过X射线衍射仪、场发射扫描电镜、激光粒度仪及比表面积分析仪等测试手段对合成的碳化锆粉体进行了分析表征.结果表明:碳化锆合成过程先后经历ZrO2被还原和锆碳反应.调节反应原料的活性、熔盐种类及反应温度,可以在900～ 1100℃实现碳化锆粉体的合成.以NaCl为熔盐、氧氯化锆为锆源,在1000℃可以制取D50为18.599 μm、比表面积15.27 m2/g的高纯碳化锆粉体.     

衬底温度对直流磁控溅射法制备掺锆氧化锌透明导电薄膜性能的影响(英文)

利用直流磁控溅射法在石英衬底上制备出了高透明导电的掺锆氧化锌(ZnO:Zr)薄膜。研究了衬底温度对ZnO:Zr薄膜结构、形貌及光电性能的影响。XRD表明实验中制备的ZnO:Zr为六方纤锌矿结构的多晶薄膜,具有垂直于衬底方向的c轴择优取向。实验所制备ZnO:Zr薄膜的晶化程度和导电性能对衬底温度有很强的依赖性。当衬底温度为300℃时,ZnO:Zr薄膜具有最小电阻率7.58×10-4Ω.cm,其可见光平均透过率超过了91%。     

Structural and optical properties of thin films prepared from surface modified ZrO2

This paper describes the preparation and characterization of ZrO₂ thin films deposited on silicon wafer by spin coating method. Nanocrystalline ZrO₂ was synthesized by hydrothermal method using zirconium (IV)-n-propoxide as a precursor material. Surface of the ZrO₂ particles was then modified with 2-acetoacetoxyethyl methacrylate used as a copolymer for coatings. The optical properties, nanostructure and surface morphology of the thin films prepared from surface modified ZrO₂ nanoparticles were examined by optical spectroscopy, X-ray diffraction and scanning electron microscopy, respectively. It was found that the films deposited on silicon wafer have crystalline structure of monoclinic (111) at temperature of 150 °C. It was observed that films depict very dense material that does not present any granular or columnar structure. It was found that optical transparency of thin ZrO₂ films distributed in the range of 30-40 percent in the spectral range 400-800 nm. Refractive index of ZrO₂ films were determined as functions of ZrO₂ content and it was found that the refractive index increases from 1.547 to 1.643 with increased ZrO₂ content.     

Improvement of photoconductivity in Silicon Tin (SiSn) thin films

Hydrogenated-amorphous silicon tin alloy (a-SiSn (C:H)) films have been prepared by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD) technique. We present investigations of the absorption and photoconductivity characteristics of a-SiSn(C:H) thin films as a function of the tin concentration, which could be a pivotal feature for the bottom solar cell development. We demonstrate that the photoconductivity is significantly improved by the film growth under enhanced hydrogen dilution. The results suggest that the hydrogen dilution plays an important role in development of high quality a-SiSn(C:H) photosensitive thin films.     

Structure and optical properties of amorphous silicon oxide thin films with different porosities

Amorphous silicon oxide thin films were prepared by evaporation of a silicon oxide powder. Samples were prepared under ultrahigh vacuum, under a flow of hydrogen ions or under a molecular hydrogen atmosphere. Two others sets of samples were prepared using deuterium instead of hydrogen. These five groups of samples were then annealed to different temperatures up to 950 °C and were exposed to the ambient air. The samples present different densities and microstructures. The sample prepared under ultrahigh vacuum is dense, hydrogen free and OH-bond free. Samples prepared under atomic hydrogen and deuterium flows contain Si–H and Si–D bonds, respectively, and are OH-bond free. The sample prepared under a molecular hydrogen atmosphere is very similar to that prepared under a molecular deuterium atmosphere. Both samples are porous and contain Si–H bonds and OH-groups coming from the exposure to the air. All the samples show visible photoluminescence attributed to isolated silicon clusters. The photoluminescence intensity increases with thermal annealing post-treatments up to an optimal annealing temperature. This maximum value is equal to 650 °C for the unhydrogenated sample and the sample prepared under an atomic hydrogen flow and to 800 °C for the sample prepared under a molecular hydrogen atmosphere. This difference is correlated to the different microstructures of the samples. Moreover the strongest photoluminescence intensity is obtained for the porous sample.     

基于原子层沉积的氧化锆薄膜工艺优化研究

利用原子层沉积技术(Atomic layer deposition,ALD)进行ZrO_2薄膜工艺研究,获得了低温下ZrO_2薄膜ALD的最佳工艺条件。分析了在低温下前驱体脉冲时间,吹扫时间生长工艺条件对薄膜性能的影响。以四(二甲基氨)基锆(TDMAZ)和H_2O为前驱体,制备了均匀性良好,表面粗糙度低,可见光透过率高,水汽阻挡效果良好的ZrO_2薄膜。     

影响化学机械抛光4H导电SiC晶片表面质量的关键参数研究

选用二氧化硅抛光液抛光4H导电SiC晶片表面,探究影响SiC晶片表面质量的关键参数,获得更高的去除效率和表面质量。实验结果表明,SiC表面的氧化是氢氧根离子和双氧水共同作用的结果。保持压力不变并增加氢氧根离子或双氧水的含量,SiC表面去除速率先增加后保持不变。在更大的压力下增加氢氧根离子的含量,SiC表面的抛光去除速率进一步增加。通过优化的抛光参数,SiC表面的抛光去除速率达到142 nm/h。进一步研究结果表明,保持化学机械抛光过程中氧化作用与机械作用相匹配,是获得高抛光效率和良好的表面质量的关键。表面缺陷检测仪(Candela)和原子力显微镜(AFM)的测试结果表明,SiC抛光片表面无划痕,粗糙度达到0.06 nm。外延后总缺陷密度小于1个/cm2,粗糙度达到0.16 nm。     

Ca0.6Mg0.4Zr4(PO4)6涂层改善堇青石陶瓷

本文采用溶胶-凝胶法和浸渍涂覆技术在致密堇青石陶瓷表面制备了Ca0.6Mg0.4Zr4(PO4)6(C0.6M0.4ZP)涂层,采用XRD、SEM等分析手段研究了涂层的相组成和微观结构,并通过分别测定涂覆和未涂覆涂层试样在1000℃下受腐蚀后的质量损失和强度变化,对涂层的耐碱腐蚀性能进行了表征。结果表明,在堇青石表面制备的涂层均匀致密,由单相的C0.6M0.4ZP组成。SEM分析表明涂层与堇青石基体间结合良好。C0.6M0.4ZP涂层具有较好的耐碱腐蚀性能,可显著提高堇青石陶瓷的高温耐碱腐蚀性能。     

石墨烯/钛酸锶钡/聚偏氟乙烯复合薄膜介电性能研究

首先制备了硅烷偶联剂改性后的石墨烯和钛酸锶钡粉体,然后采用溶液混合法制备了石墨烯/钛酸锶钡/聚偏氟乙烯薄膜,并且对复合薄膜的微观结构、介电性能和热稳定性进行测定和分析。结果表明:硅烷偶联剂成功接枝到石墨烯和钛酸锶钡粉体表面,石墨烯和钛酸锶钡粉体能够较好的分散在聚偏氟乙烯基体中,石墨烯的加入可以大幅度提高材料的介电性能。在石墨烯质量分数为4.06%时,复合薄膜的介电常数达到515,介电损耗为0.6。在质量分数4.14%时发生了渗流现象,介电常数达到1500,介电损耗也达到了5左右。石墨烯的加入大幅度提升了复合材料的介电性能,并且在常用温度范围内具有良好的温度稳定性。     

Hydrogenated amorphous silicon with substrate-dependent structure

Hydrogenated amorphous silicon (a-Si:H) thin films grown at 250°C on (1 0 0) crystalline substrate using plasma-enhanced chemical vapor deposition (PECVD) with SiH₄/H₂ gas flow ratio equal to 5/1 (sccm) are investigated by transmission electron microscopy. It is found that the thin film is totally amorphous when grown on a glass substrate. But when the substrate is changed to crystalline silicon, some crystalline grains are found embedded in the amorphous structure in certain regions even if the thickness of the film reaches 600 nm. It is suggested that the amorphous silicon film grown on a crystalline silicon substrate at a temperature of 250°C without heavy H₂ dilution is a mixed network of a small amount of crystalline silicon and the major portion of amorphous silicon.     

表面补偿的高雾度ZnO∶Al及其在硅薄膜太阳电池中的应用

采用稀盐酸对磁控溅射法制备的平面掺铝氧化锌(ZnO∶Al,AZO)薄膜表面进行湿法刻蚀制绒,分析了盐酸浓度和刻蚀时间对AZO薄膜表面的形貌特征和光电特性的影响。研究发现,湿法刻蚀导致AZO薄膜表面呈现大尺度的陨石坑形貌特征,随刻蚀时间增加,薄膜在大于500 nm的长波范围内光学透过率可维持在70%~75%,且800nm处雾度值可高达48%,陷光能力快速增加,而面电阻率呈现逐渐增加趋势。高的盐酸浓度可以导致薄膜表面呈现较快凹型形貌特征,并可给出较高的雾度值。为了在保持高雾度值的条件下改善薄膜导电性,在2%盐酸刻蚀30 s所制备绒面沉积300 nm AZO薄膜进行厚度补偿,所获得薄膜的表面方块电阻小于10Ω/sq,以其作为前电极所制成的单结薄膜电池转换效率达到9.24%。结果表明,采用酸性刻蚀+厚度补偿方法所制备的绒面AZO薄膜可兼顾高雾度和低电阻的性能要求,是用作硅基薄膜太阳电池前电极的理想材料。     

Effect of hydrogen peroxide on hydrofluoric acid etching of high-k materials: ESR investigations

Oxides and silicates of zirconium and hafnium are being actively considered for use as gate dielectrics in MOS devices. Because of their higher dielectric constant (k ∼ 16-22), they permit the use of thicker layers without sacrificing the capacitance value. Wet chemical etching is the method of choice for patterning these oxides. The etching process has to be selective to zirconium/hafnium oxides over silicon dioxide, which may be present in other areas. In this paper, work done on HF etching of ZrO₂ and HfO₂ in presence of hydrogen peroxide is presented and discussed. It was found that addition of hydrogen peroxide to HF solutions lower the etch rate of ZrO₂ and HfO₂ films. Electron spin resonance (ESR) spectroscopy was used to probe the reasons for the decrease in etch rates in this solution.