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(ZrSiO4)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ZrSiO4合成、ZrSiO4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1 mm/s时可以在单晶硅片获得表面光滑、平整致密、无开裂的ZrSiO4薄膜.镀有ZrSiO4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ZrSiO4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。     

低温固相反应法制备钠快离子导体NaZr2(PO4)3粉体

为了进一步促进钠快离子导体磷酸锆钠(NaZr2(PO4)3)粉体的实际应用,本文提出了一种以氧氯化锆(ZrOCl2·8H2O)和二水磷酸二氢钠(NaH2PO4·2H2O)为原料的低温固相反应法制备NaZr2(PO4)3粉体.通过XRD,SEM和Raman等测试手段系统研究了磷酸盐用量对制备磷酸锆钠粉体的影响.结果 表明:采用超量的磷酸盐有利于纯相磷酸锆钠粉体的合成.同时当锆盐与磷酸盐的摩尔比为2∶5.4时,能够合成平均粒径1μm,尺寸均匀,分散性良好的磷酸锆钠粉体.研究发现研磨时发生的固相反应对磷酸锆钠粉体的制备有重要作用,一方面促进了无定型磷酸锆钠的产生,有利于磷酸锆钠晶体形成;另一方面原位生成的氯化钠为晶体的生长提供了良好的液相环境,促进了磷酸锆钠粉体的低温合成.该工作为磷酸锆钠粉体的大规模生产提供了一条简单有效的方法.     

非晶前驱体碳热还原法制备超细硼化锆粉体

利用ZrO2-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(ZrOCl2·8H2O)、硼酸(H3BO3)和蔗糖(C11H22OH)作为ZrO2、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2h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0.2～0.6 μm之间、比表面积为74 m2/g.     

正硅酸乙酯为碳源制备C@ZrSiO4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,LiF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@ZrSiO4)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@ZrSiO4色料黑度提高;前驱体浓度高于3mol·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2h,空气气氛800℃热处理2h后制备出的C@ZrSiO4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.     

PECVD提高SiO2薄膜致密性的研究

为了在高功率980 nm激光器工艺中制备高质量、均匀性好、致密性高的SiO2薄膜,本文研究了PECVD的反应压强、射频功率、SiH4与N2O流量比对SiO2薄膜的沉积速率和BOE腐蚀速率的影响.实验采用BOE腐蚀速率来反映SiO2薄膜的致密性,采用傅里叶红外光谱仪得到SiO2薄膜的红外吸收特性,采用原子力显微镜(AFM)观察SiO2薄膜的表面形貌.通过优化各工艺参数最终获得了BOE腐蚀速率为9.18 nm/s的SiO2薄膜.     

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.     

还原氮化对ZrO2薄膜SERS性能的影响研究

以八水氧氯化锆(ZrOCl2·8H2 O)为原料制备前驱体溶液,采用旋涂工艺制备ZrO2薄膜,并对其进行还原氮化.利用XRD、FE-SEM、UV-Vis-Nir和Raman测试薄膜结构、光学性能及SERS效应.结果表明,还原氮化后薄膜中出现了氮氧化合物,颗粒明显,薄膜厚度约为0.77μm.薄膜的紫外可见近红外光谱在350～650 nm附近展现出较强的吸收.利用R6G作为探针分子研究了薄膜的SERS效应,结果表明,还原氮化后的氧化锆薄膜拉曼增强效应显著提升,拉曼增强因子为2.479×102.     

锆钛酸铅薄膜的溶胶-凝胶制备工艺及结构与物性的研究

采用溶胶-凝胶匀胶法制备锆钛酸铅铁电薄膜,研究了前驱体影响因素(如有机溶剂、前驱单体加入顺序、添加剂)、溶胶影响因素(如溶胶浓度、pH值)、匀胶速度和退火温度对成膜质量及薄膜微结构、铁电性的影响.结果表明:采用乙二醇甲醚为溶剂对pb2+、Zr4+和Ti4+金属盐进行溶解优于乙醇和乙二醇,但由于乙二醇甲醚对硝酸锆的溶解性差,对硝酸锆应先用乙醇溶解再加入乙二醇甲醚的方法来进行溶解;以硝酸锆为Zr源配制溶胶时,只有先将Pb前驱液滴加到Ti前驱液中,然后再滴入Zr前驱液的方式才能得到澄清前驱体.将锆钛酸铅溶胶浓度和pH值分别控制在0.2～0.3 mol/L和2～3较为适宜,与此溶胶相适应的匀胶参数:转速为4000 r/min,时间为60 s.随退火温度升高,薄膜的晶化程度增加,且逐渐表现出(100)晶面择优取向,晶格常数c和四方率c/a逐渐增加,而晶格常数a逐渐减小;随退火温度升高,晶粒尺寸逐渐增大,使得剩余极化强度逐渐增加,矫顽场强逐渐减小.当退火温度为850 ℃时制备的锆钛酸铅薄膜具有均匀的晶粒、较低的表面粗糙度和最为优异的铁电性.     

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100 nm左右,具有良好的抗硝酸钠熔体腐蚀性能.     

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ZrO2薄膜工艺研究,获得了低温下ZrO2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H2O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ZrO2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.     

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.     

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.石墨烯的加人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.     

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。