新型模板法制备ZnO纳米结构薄膜及其光学性能研究

通过电化学阳极氧化-化学溶蚀技术制备了一种由无数纳米凸点和凹点所构成的新型铝基纳米点阵模板.采用直流反应磁控溅射法在这种新型模板上沉积得到氧化锌纳米结构薄膜.在室温下观察了氧化锌纳米结构薄膜的形貌,测定材料的晶体结构和光致发光(PL)性能,并讨论了不同溅射时间下制备的氧化锌纳米阵列结构以及其对氧化锌PL谱的性能影响.结果表明,采用直流反应磁控溅射-铝基纳米点阵模板可以制备ZnO纳米结构薄膜;PL谱表明溅射时间为10 min得到的氧化锌薄膜在396.5 nm和506.4 nm处分别出现紫外发射峰和蓝绿色荧光发射峰;随着溅射时间延长,氧化锌薄膜PL谱伴有红移现象且强度逐渐增强.这可能是由于改善了晶粒结构导致不能观测到ZnO薄膜的深能级发射峰所致.     

高定向ZnO纳米棒阵列膜的制备及其光学性能

采用阴极恒电位沉积方法,在Zn(NO3)2溶液中,用六亚甲基四胺作为形貌控制试剂,直接在氧化铟锡玻璃衬底上制备出透明致密的ZnO纳米棒阵列膜。通过X射线衍射、扫描电镜和能量色散谱表征了薄膜的形貌和结构,测量了ZnO纳米棒阵列膜的光学透射谱和光致发光谱。结果表明:所制备的具有c轴高度择优取向的ZnO纳米棒为高纯单晶纤锌矿结构,粒径约为200nm,膜的结晶度和表面平整度明显提高。ZnO薄膜在可见光区具有高透射率(80%)和陡峭的吸收边缘,室温光致发光谱显示,在380nm处存在一个尖锐的强紫外发射峰和在510nm处存在一宽带弱绿光发射峰。     

PVA/CaF_2纳米复合薄膜的合成、表征及光学性质

利用共沉淀法合成了CaF2纳米颗粒(CaF2NPS),并利用不同量的CaF2NPS制备一系列的聚乙烯醇(PVA)/CaF2纳米复合薄膜。采用X射线衍射法(XRD)、扫描电子显微镜(SEM)对材料进行表征,并利用紫外-可见光谱(UV)和荧光光谱(PL)对材料的光学性质进行了研究。结果表明:CaF2纳米颗粒的形成与立方相有关,晶粒尺寸大约在20~27 nm;CaF2纳米颗粒均匀的分散在PVA膜表面;CaF2纳米颗粒在约300 nm的边缘有强烈的吸收,复合薄膜在200 nm和300 nm左右出现吸收带;CaF2纳米颗粒的PL谱在394 nm和790 nm附近有一系列的发射峰,复合薄膜的PL谱带表明PVA的这3种(间规、无规、等规)分子构象的游离羟基中氧原子的2p2非键电子会发生n←π*电子跃迁。     

超声辅助均匀沉淀法由前躯体ZnS制备ZnO纳米颗粒及其表征

前躯体ZnS在超声辅助60℃的低温条件下,采用醋酸锌为锌源、硫代乙酰胺为硫源来制备,然后采用在空气中热处理前躯体ZnS的方法制备了直径约为20~40 nm的ZnO纳米颗粒。所得产物分别采用红外光谱(FTIR)、热重-差热分析(TGA-DTA)、X射线衍射(XRD)、场发射扫描电镜(FE-SEM)、透射电镜(TEM)、电子能谱(EDS)和荧光光谱(PL)进行表征。实验结果表明,所得产物ZnO为六方纤锌矿结构,且结晶性很好,并且随着超声时间的延长其粒径有所降低。室温PL光谱表明,样品在400~550 nm内有3个较强的荧光发射峰。     

水热法制备In掺杂ZnO薄膜的表面形貌及其光学性质

采用水热法在ZnO籽晶层上制备了不同In掺杂量的ZnO薄膜,用X射线衍射仪(XRD)、原子力显微镜(AFM)、紫外可见分光光度计和荧光光谱仪等测试分析薄膜的微结构、表面形貌、透射谱和室温光致发光谱.结果表明,In离子的掺入未改变薄膜的晶相结构,但抑制了ZnO晶粒的生长,使得ZnO的结晶度明显下降.随着In含量的增加,薄膜表面rms粗糙度和平均颗粒尺寸均逐渐减小,光学带隙Eg先增大后减小.所有薄膜的PL谱中均观察到405 nm左右的紫光发光带,研究了In掺杂量对紫光发光带的强度和峰位的影响,并对其紫光发射机理进行了探讨.     

ZnO纳米棒水热法生长与表征

采用两步法在FTO导电玻璃衬底上制备ZnO纳米棒,首先利用浸渍-提拉法在FTO导电玻璃衬底上制备ZnO晶种层,然后把有ZnO晶种层的FTO衬底放入盛有生长溶液的反应釜中利用水热法制备ZnO纳米棒.研究了生长溶液的浓度、生长温度和生长时间对所制备的对ZnO纳米棒阵列的微结构和光致发光性能的影响,利用X射线衍射(XRD)、扫描电子显微镜(SEM)和光致发光谱(PL)研究了ZnO样品的结构、形貌和光学性质.实验结果表明:所制备的ZnO纳米棒呈现六方纤锌矿结构,沿(002)晶面择优取向生长,纳米棒的平均直径约为100 nm,长度约为2.5 μm.所制备的ZnO纳米棒在390 nm附近具有很强的紫外发光峰和在550 nm附近有较弱的宽绿光发光峰.     

CBD方法制备的Zn(O,S)薄膜的微结构表征及性能

对低温化学浴沉积方法制备的Zn(O,S)薄膜进行了研究,通过XPS、SEM、XRD、拉曼光谱、PL谱、紫外-可见吸收光谱等手段对薄膜的形貌、结构及组成进行系统表征,探究了其作为钙钛矿电池电子传输层的可能性。研究表明:化学浴沉积(CBD)方法制备的Zn(O,S)薄膜为ZnO、Zn S和ZnOS合金的复合膜;该薄膜对CH_3NH_3Pb I3光吸收层具有与TiO_2相当的电子抽提能力,是一种可供选择的高效柔性钙钛矿电池电子传输层材料。     

纳米氧化锌阵列的制备及发光机理研究

首先采用溶胶-凝胶法获得了Zn O晶种层薄膜,基于Zn O种子层的基础上,通过水热法制备出取向度高、分散性良好的纳米Zn O阵列。利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)和紫外可见分光光度计(PL)等对样品的形貌、结构、光学性质进行了表征。结果表明:制备的样品为六方纤锌矿结构,沿(002)晶面择优生长。样品在371.5 nm处有着较强的特征吸收及紫外吸收能力,PL图谱显示样品在387 nm处有一个较高的紫外发光峰,并在468 nm处出现了比较微弱的蓝光发射峰。最后解释了纳米Zn O阵列的微观发光机理。     

TiO_2/ZnO双层电子传输层的制备及光电化学性能

首先在氟掺杂的氧化锡导电玻璃(FTO)上水热生长一层TiO_2纳米棒阵列薄膜,然后通过旋涂法旋涂ZnO籽晶层后水热法生长ZnO纳米棒得到TiO_2/ZnO纳米棒阵列薄膜。通过XRD、SEM、PL、UV-Vis和电化学工作站等对单层TiO_2纳米棒和TiO_2/ZnO纳米棒的结构、表面形貌、荧光性能、光吸收强度以及光电化学性质进行表征。结果表明,随着水热生长ZnO时间的增长,ZnO纳米棒密度增加; ZnO纳米棒的生长时间不同使其荧光强度不同,TiO_2/Zn O纳米棒的荧光强度与单层TiO_2纳米棒相比有着微小的减弱,没有明显的衍射峰; TiO_2/ZnO纳米棒复合材料比单层TiO_2的光吸收强度高,提高其光学性能,但是吸光区域都在紫外光区域;在标准模拟太阳光照射下,TiO_2/Zn O纳米棒的光电流为0. 002 m A,单层TiO_2纳米棒的光电流为0. 006 m A,复合薄膜的电流有着明显的变化。     

形貌可控纳米/微米ZnO的绿色合成及光致发光性能研究

以[Bmim]Cl、[Bmim]BF_4、[C_2OH]mimCl和[C_2OHmim]BF_4四种室温离子液体为模板,采用微波加热前驱体Zn(OH)_4~(2-)溶液的方法制备了多形貌纳米/微米ZnO.采用XRD、SEM、TEM对实验样品进行了结构和形貌表征,通过SEM照片分析了不同合成条件对产物形貌的影响.结果表明:合成产物为结晶良好,具有六方纤锌矿结构的ZnO;不同离子液体中合成了鳞状、片状、棒状、锥状纳米ZnO晶体单元,大量ZnO晶体聚集成微米球、花簇;随着前驱体原料配比增大,[0001]方向择优生长明显;随温度从80 ℃增加到95 ℃,ZnO纳米锥生长趋势总体趋于明显, 长径比增大,同时产物形貌的规整性也明显变好;探讨了多形貌纳米/微米ZnO的生长机理;采用室温下光致发光(PL)光谱对多形貌纳米ZnO的光学性能研究表明,多形貌纳米ZnO具有较强的紫外发射和相对较弱的蓝绿发射,离子液体[Bmim]Cl中合成的ZnO纳米锥在387 nm处紫外发射峰强度最大,离子液体[C_2OHmim]Cl 中合成的ZnO纳米片在497 nm处有较强的绿光发射峰.     

针状ZnO的纳米纤维素诱导制备及光催化性能

以纳米纤维素（NCC）为形貌诱导剂,乙酸锌为反应前驱物,采用水热法合成针状ZnO。通过X射线衍射仪（XRD）、扫描电子显微镜（SEM）和能量色散X射线光谱仪（EDS）对ZnO的形貌、微观结构、结晶特性进行了表征,并探讨了其形成机理及光催化降解性能。结果表明水热条件下,NCC能诱导ZnO在其表面沉积和生长,可形成直径260nm、长度10μm的针状结构,诱导制备的针状ZnO室温下2h内对孔雀绿的紫外光降解效率为88.5%。针状ZnO在光催化剂等领域具有潜在应用价值。     

低温固相法制备纳米氧化锌及其在脱硫中的应用

以乙酸锌和草酸为原料,采用低温固相法制备了纳米氧化锌,考察了表面活性剂和焙烧温度对氧化锌晶粒的影响,采用XRD、TG-DTA、IR和TEM等技术进行表征。以不同晶粒的氧化锌为锌源,采用等体积浸渍法制备一系列NiO/ZnO吸附荆;以噻吩/正庚烷为模型化合物,在固定床微反装置考察氧化锌晶粒对吸附剂脱硫性能的影响。结果表明,表面活性剂以十二烷基硫酸钠效果最好,合适的焙烧温度为400℃;制备的氧化锌呈球形,为六方晶系纤锌矿结构,具有较好的分散性,平均粒径约15 nm。活性评价表明,NiO/ZnO吸附剂对噻吩类硫化物具有较高的活性。可以实现超深度脱硫;氧化锌晶粒越小,相应NiO/ZnO吸附剂的脱硫活性越高;脱硫前后吸附剂的XRD谱图对比表明,脱硫过程中S以ZnS的形式固定在吸附剂上。     

炭吸附纳米氧化锌的制备及其光催化性能研究

以粗氧化锌和冰乙酸为原料,采用炭吸附水热法制备纳米氧化锌粉体。通过热重/差热仪（TG-DTA）、X射线衍射仪（XRD）、透射电镜（TEM）和紫外可见光谱仪（UV-Vis）等对所得催化剂的焙烧温度、物相、微粒尺寸及光吸收性能进行表征。结果表明：炭黑的吸附有效阻止了纳米氧化锌在制备、干燥以及焙烧过程的团聚和烧结,600 ℃焙烧制备的催化剂颗粒均匀,分散性好,团聚较少,平均晶粒尺寸为20 nm,比表面积约为85.25 m2/g。纳米氧化锌作光催化剂对甲基橙进行光催化降解,在60 min内降解率为97%。     

纳米氧化锌的室温合成及表征

文章以醋酸锌、氯化锌和氢氧化钠为原料,在室温下成功制备了氧化锌纳米晶。制备的氧化锌样品用x射线衍射仪、透射电镜、荧光光谱仪等进行表征。XRD结果表明,制备的氧化锌样品为六方纤锌矿结构且具有好的结晶度;从透射电镜照片可以看出,氧化锌颗粒分散性较好,平均粒径在6～10nm;从紫外吸收光谱可以看到,在200-380nm具有很强的紫外吸收,在400-800／lm的可见光区吸收则比较弱;在340nm的激发光下,氧化锌呈现出较好的蓝光和绿光发光效应。     

Designing zinc oxide nanostructures (nanoworms,nanoflowers, nanowalls,and nanorods) by pulsed laser ablation technique for gas-sensing application

In this study, pulsed laser ablation technique, also known as pulsed laser deposition (PLD), is used to design and grow zinc oxide (ZnO) nanostructures (nanoworms, nanowalls, and nanorods) by template/seeding approach for gas-sensing applications. Conventionally, ZnO nanostructures used for gas-sensing have been usually prepared via chemical route, where the 3D/2D nanostructures are chemically synthesized and subsequently plated on an appropriate substrate. However, using pulsed laser ablation technique, the ZnO nanostructures are structurally designed and grown directly on a substrate using a two-step temperature-pressure seeding approach. This approach has been optimized to design various ZnO nanostructures by understanding the effect of substrate temperature in the 300-750°C range under O₂ gas pressure from 10-mTorr to 10 Torr. Using a thin ZnO seed layer as template that is deposited first at substrate temperature of ~300°C at background oxygen pressure of 10 mTorr on Si(100), ZnO nanostructures, such as nanoworms, nanowalls, and nanorods (with secondary flower-like growth) were grown at substrate temperatures and oxygen background pressures of (550°C and 2 Torr), (550°C and 0.5 Torr), and (650°C and 2 Torr), respectively. The morphology and the optical properties of ZnO nanostructures were examined by Scanning Electron Microscope (SEM-EDX), X-ray Diffraction (XRD), and photoluminescence (PL). The PLD-grown ZnO nanostructures are single-crystals and are highly oriented in the c-axis. The vapor-solid (VS) model is proposed to be responsible for the growth of ZnO nanostructures by PLD process. Furthermore, the ZnO nanowall structure is a very promising nanostructure due to its very high surface-to-volume ratio. Although ZnO nanowalls have been grown by other methods for sensor application, to this date, only a very few ZnO nanowalls have been grown by PLD for this purpose. In this regard, ZnO nanowall structures are deposited by PLD on an Al₂O₃ test sensor and assessed for their responses to CO and ethanol gases at 50 ppm, where good responses were observed at 350 and 400°C, respectively. The PLD-grown ZnO nanostructures are very excellent materials for potential applications such as in dye-sensitized solar cells, perovskite solar cells and biological and gas sensors.     

Sm掺杂ZnO QDs的制备及其荧光性能研究

通过研究不同碱/锌、钐/锌物质的量比制备了分散性良好的Sm掺杂氧化锌量子点（ZnO QDs）。通过紫外可见光谱（UV-vis）、X射线衍射（XRD）、场致发射透射电子显微镜（TEM）、能量色散X射线谱（EDS）、X射线光电子能谱（XPS）对样品做了表征。研究结果表明,n（Zn）∶n（OH^-）=1∶1、Sm掺杂量为4%（物质的量分数）时制备的ZnO QDs在383 nm紫外光激发下的荧光发射强度最强。并发现稀土钐离子的掺杂与ZnO QDs的氧空位（OV）形成有关。Sm掺杂后的ZnO QDs的氧空位浓度比未掺杂的高,且ZnO QDs氧空位的浓度越大,其荧光发射强度越强。     

A simple route to vertical array of quasi-1D ZnO nanofilms on FTO surfaces: 1D-crystal growth of nanoseeds under ammonia-assisted hydrolysis process

A simple method for the synthesis of ZnO nanofilms composed of vertical array of quasi-1D ZnO nanostructures (quasi-NRs) on the surface was demonstrated via a 1D crystal growth of the attached nanoseeds under a rapid hydrolysis process of zinc salts in the presence of ammonia at room temperature. In a typical procedure, by simply controlling the concentration of zinc acetate and ammonia in the reaction, a high density of vertically oriented nanorod-like morphology could be successfully obtained in a relatively short growth period (approximately 4 to 5 min) and at a room-temperature process. The average diameter and the length of the nanostructures are approximately 30 and 110 nm, respectively. The as-prepared quasi-NRs products were pure ZnO phase in nature without the presence of any zinc complexes as confirmed by the XRD characterisation. Room-temperature optical absorption spectroscopy exhibits the presence of two separate excitonic characters inferring that the as-prepared ZnO quasi-NRs are high-crystallinity properties in nature. The mechanism of growth for the ZnO quasi-NRs will be proposed. Due to their simplicity, the method should become a potential alternative for a rapid and cost-effective preparation of high-quality ZnO quasi-NRs nanofilms for use in photovoltaic or photocatalytics applications.PACS: 81.07.Bc; 81.16.-c; 81.07.Gf.     

Zinc oxide thin films prepared by thermal evaporation deposition and its photocatalytic activity

Thin zinc oxide (ZnO) films have been grown on silicon substrates by thermal physical vapor deposition approach. X-ray diffraction (XRD) analyses reveal that the deposited films are polycrystalline ZnO phase. Atomic force microscopy images (AFM) show needle-like shape highly oriented ZnO crystals. Thin film thickness ranges from 10 to 80 nm. X-ray photoelectron spectroscopy (XPS) results declare that the films compose mainly of Zn and O. Nevertheless, Si is not detected in the films and consequently no possibility of any silicide formation as is confirmed by XRD analysis. Photocatalytic decomposition of azo-reactive dye on ZnO films is tested. The results show that the dye decomposition efficiency increases with decreasing pH. Maximum photodecomposition, 99.6% is obtained at pH 2 with 10 mg/l dye concentration.     

Nanocrystalline ZnO Thin Film Synthesis Using Glycerol in Aqueous Polymeric Precursor Processing

Synthesis of high-quality ZnO thin films via simple and cost effective processing technique is a major challenge. In this work, the preparation of nanocrystalline ZnO thin films by a novel polymeric precursor processing using glycerol as chelating agent is presented. The process has advantages of being cost-effective and environment friendly. ZnO thin films were prepared by a single spin-coating deposition of aqueous polymeric precursor prepared with zinc nitrate [Zn(NO₃)₂] and glycerol as chelating agent. The thermal decomposition of polymeric precursors was studied by thermogravimetric analysis and Fourier transform infrared (FTIR) spectroscopy. Annealing of these films were performed over the range of 300°–600°C, and the effect of annealing on the degree of crystallization, surface morphology, crystallite size, and optical properties was investigated. X-ray diffraction analysis shows that the thin films are polycrystalline with wurtzite structure. The thin films are 80% dense, have crack free microstructure, and transparency of >85% in the visible region. These films exhibit absorption edge at 375 nm. On measuring at room temperature, the optical band gap energy of ZnO thin films, annealed at 450° and 600°C, was determined to be 3.295 and 3.267 eV. Room temperature photoluminescence spectra of these films show strong UV emission and a broad yellow-green emission in the range 525–600 nm. The intensity of UV emission peak increases with increase in annealing temperature that is attributed to an improvement in crystallinity.