柔性有序ZnO纳米棒/TiO2纳米粒子复合薄膜的制备及其光电转换性能研究

采用电沉积法,在柔性不锈钢网基底上制备了ZnO纳米棒阵列,随后旋涂P25浆料,最终经退火后得到了ZnO纳米棒阵列/TiO2纳米粒子的复合结构薄膜,详细探讨了TiO2纳米粒子的填充,初级ZnO纳米棒阵列的形貌,P25浆料的旋涂次数以及表面活性剂PEG添加量等制备条件对复合结构光阳极形貌及光电性能的影响.研究表明:TiO2纳米粒子的引入能有效提高光阳极的比表面积,增强半导体与染料的耦合能力,ZnO纳米棒阵列能够为电子提供快速传输的通道.最佳制备条件为:初级ZnO纳米棒沉积次数为两次,浆料浓度为1 g/50 mL,旋涂浆料次数为三次,PEG添加量为4g/100 mL,制备的复合结构DSSC的光电转换效率较单一纳米棒阵列有一定的提高.     

籽晶辅助化学水浴沉积法制备ZnO纳米棒阵列

采用籽晶辅助化学水浴沉积法,即先用磁控溅射法在硅片上制备c轴取向的ZnO薄膜,以此作为籽晶层,利用化学水浴沉积法制备ZnO纳米棒阵列.利用扫描电子显微镜(SEM)和X射线衍射(XRD),研究了ZnO薄膜籽晶层的沉积温度、水浴温度和前驱体溶液中Zn源的初始浓度等对ZnO纳米棒阵列生长的影响,由此得到了结晶性好且几乎垂直于衬底方向的ZnO纳米棒阵列的生长条件,为制备基于ZnO纳米棒阵列的器件提供了条件.     

基于直流磁控溅射晶种层的ZnO纳米阵列的制备及性能研究

采用直流反应磁控溅射法制备品种层薄膜,研究O2/Ar气体分压比和退火温度对品种层结构和微观形貌的影响.通过化学水浴沉积,在预制有晶种层的薄膜上制备ZnO纳米阵列结构,研究不同前驱体浓度和预制晶种层对纳米阵列生长的影响.结果表明,当O2/Ar中O2分压减少,薄膜均匀性较差,当Ar分压增加薄膜由于扩散而趋于平整.退火温度增加,晶粒尺寸增大,内应力降低.磁控溅射法预制的晶种层上生长的纳米棒垂直于衬底生长,(002)晶面的衍射峰强最高,说明纳米棒沿c轴择优取向.生长液的浓度对纳米棒的形貌影响显著,随着生长液浓度的升高,ZnO纳米阵列直径增大,顶端趋于平整的六棱柱结构.     

PLD制备的籽晶层对ZnO纳米棒形貌及性能的影响

本文研究了脉冲激光沉积法(PLD)制备的不同籽晶层对水热生长ZnO纳米棒的形貌及发光性能的影响,通过比较得出,籽晶层是获得高度取向,排列有序的ZnO纳米棒的基础.电子回旋共振(ECR)氧等离子体参与沉积,有利于获得表面均匀且光滑平整的籽晶层,进而得到形貌及结晶质量较好的ZnO纳米棒.籽晶层的厚度不仅能够改变纳米棒的疏密程度,而且还能够改善纳米棒的取向性.通过调节籽晶层的退火温度可以调节纳米棒直径的大小,恰当的籽晶层退火温度也是获得形貌优良的ZnO纳米棒的一个关键因素.     

衬底放置方式对ZnO阵列形貌的影响

ZnO纳米棒阵列通过两步化学法制备,首先通过水热法在ITO衬底上制备ZnO晶种,然后把有ZnO晶种的ITO衬底垂直放入以氯化锌和氨水为溶剂的pH值为11的溶液,在85℃恒温条件下生长2h,然后在600 ℃对其进行退火处理,就得到了在ITO衬底上生长的ZnO纳米棒阵列.利用X射线衍射(XRD)、扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)、紫外可见分光光度计和光致发光谱仪(PL)对样品的晶体结构、形貌和光学性能进行了表征.结果表明制备的高密度棒状ZnO纳米阵列是垂直生长在ITO衬底上,纳米棒的直径大约为150nm,长约1μm,纤锌矿ZnO纳米棒沿着[0002]方向一致生长;ZnO纳米棒阵列在波长为300 ～400 nm处出现了很强的紫外吸收峰;ZnO纳米棒阵列的光致发光光谱在380 nm左右有一个极强的紫外发光峰.研究了衬底放置方式对ZnO晶种形貌和光学性能的影响.最后通过对棒状ZnO纳米阵列形成过程中可能涉及到的化学反应以及形成机理做了简单的分析.     

钇掺杂多孔结构氧化锌纳米棒的制备与性能研究

采用两步法在二氧化锡掺氟(SnO2:F,FTO)导电玻璃基板上制备出钇(Y)掺杂多孔结构氧化锌(ZnO)纳米棒,首先利用浸渍-提拉法在FTO导电玻璃基板上制备ZnO晶种层,然后利用水热法在ZnO晶种层上生长Y掺杂ZnO纳米棒.研究了不同浓度Y掺杂ZnO纳米棒的晶相结构、微观形貌、化学组成及光学性能.实验结果表明:所制备的Y掺杂ZnO纳米棒为沿c轴择优取向生长的六方纤锌矿结构,随着Y掺杂浓度的增加,ZnO纳米棒(002)衍射峰强度先增大后减小,纳米棒的平均长度由1.3μm增加到2.6μm.ZnO纳米棒的形貌由锥状结构向柱状结构演化,纳米棒侧面的孔洞分布密度增加.所制备的Y掺杂ZnO纳米棒具有一个较弱的紫外发光峰和一个较强的宽可见发光峰.所制备样品的光学带隙随着Y掺杂浓度的增加而减小,其光学带隙在3.29～3.21 eV之间变化.利用Y掺杂ZnO纳米棒作为量子点敏化太阳能电池的光阳极可极大提高太阳电池的光电转换效率.     

枝状ZnO-TiO2复合纳米棒阵列的制备及表征

采用化学水浴沉积法,在预制晶种层的基底上得到垂直底面生长的有序ZnO纳米棒阵列,再用反应磁控溅射方法,沉积制备ZnO-TiO2复合结构的纳米棒阵列.利用X射线衍射(XRD)和扫描电子显微镜(SEM)对制备得到的样品进行结构和形貌表征,研究了晶种层、水浴生长液浓度和磁控溅射氧氩比对复合纳米阵列的影响.制备得到了具有TiO2分枝的复合纳米棒阵列,并初步探讨了TiO2分枝的形成机理,为制备基于复合纳米棒阵列的器件提供了条件.     

化学溶液沉积法制备超疏水氧化锌薄膜

采用化学溶液沉积法在涂覆ZnO缓冲层的玻璃衬底上制备超疏水ZnO薄膜。利用SEM、XRD和水接触角测量表征薄膜的微观结构和润湿性。结果表明:在涂覆ZnO的玻璃衬底上所沉积的ZnO膜为单分散的ZnO纳米棒阵列膜。ZnO纳米棒的形状和尺寸与氢氧化钠浓度、化学反应速度和沉积时间有关。氢氧化钠浓度较高时所获得的是细长浓密的纳米棒阵列膜,提高反应速度会降低ZnO纳米棒的均匀性和形状规则性。经硅烷偶联剂处理后所得薄膜与水的接触角达到165°。     

Ni2+掺杂氧化锌阵列膜的水热合成及性能表征

采用低温水热法制备了Ni2+掺杂的ZnO阵列膜,研究了Ni2+掺杂对样品形貌、晶相结构和光谱特性的影响,并对可能的影响机理进行探讨.结果表明:Ni2浓度增加不会改变ZnO的纤锌矿结构,但在一定程度上可以起到控制其形貌及均匀度的作用.Ni2+掺杂量x≤0.007 mol/L时,有助于ZnO纳米棒沿c轴方向生长,提高结晶度,但ZnO的生长机理保持不变.Ni2+掺杂量较多时(x ＞0.007 mol/L),ZnO纳米棒的生长习性发生变化,其六方结构被破坏,水热膜由垂直于基片表面排列的纳米棒阵列转变为由结构不规则的多边形晶粒组成的密堆积排列.由于Ni2+固溶入ZnO晶格产生晶格畸变,引起薄膜内应力以及载流子浓度的变化,使得ZnO拉曼光谱的特征峰出现明显的降低和移动.光致发光谱表明,Ni2掺杂使ZnO纳米棒的紫外发光峰强度IUV与绿光发光峰强度IGR之比值IUV/IGR增大.     

Co掺杂浓度对ZnO纳米棒结构和光学性能影响研究

采用水热法以不同浓度Co掺杂合成了具有六方纤锌矿结构的ZnO纳米粉体,通过X-射线衍射(XRD)、扫描电镜(SEM)、拉曼光谱、X射线光电子光能谱分析法(XPS)、(光致发光)PL谱等分别对样品的形貌、结构、光学性能进行了测试和表征.结果 表明:随着Co掺杂浓度的增大,纤锌矿ZnO的晶体结构没有改变,且Co以二价离子Co2+的形式掺杂进入ZnO晶格;同时花状ZnO纳米棒的均匀性变差,不同浓度Co掺杂ZnO纳米棒中均出现了少量且尺寸较小的单根纳米棒.PL光谱显示:随着Co掺杂浓度增大,样品的紫外发光峰没有明显地变化,而可见发光峰的强度先减小再增大,说明样品的缺陷先降低再提高.当Co掺杂的浓度为2.0;时,所制备的ZnO花状纳米棒可见发光峰相对最低,其具有较小的缺陷.     

Fabrication and photocatalytic property of ZnO/SrTiO3 core/shell nanorod arrays

ZnO/SrTiO₃ core/shell nanorod arrays were fabricated by a facile two‐step method. ZnO nanorod arrays were first hydrothermally grown on Si substrate. Then, using liquid phase deposition method, SrTiO₃ were deposited onto the ZnO nanorods to form core/shell nanorod structures. The morphologies and structures of the products were characterized by scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction. The photocatalytic behavior of the nanorod arrays was also examined through the photodegradation of methylene blue solution under UV irradiation. It was found that the core/shell nanorod arrays with deposition time of 10 min showed higher photocatalytic activity than bare ZnO nanorod arrays. This enhancement was attributed to the efficient charge separation at the ZnO/SrTiO₃ interface.     

Decisive role of Au layer on the oriented growth of ZnO nanorod arrays via a simple aqueous solution method

Vertically aligned arrays of ZnO nanorod were synthesized on the Au/SiO₂/Si(1 0 0) substrate by a simple aqueous solution growth process, without pre-prepared ZnO seed layer. For comparison, glass and SiO₂/Si were also used as substrates, and the results show that the Au layer plays a decisive role in orienting the growth of the ZnO nanorod. The effects of other growth parameters, including Zn²⁺ concentration and growth time, on morphology, density, and orientation of the ZnO nanostructure were also studied and with longer reaction time, a new structure namely ZnO nanotip was obtained. Moreover, the growth mechanism of ZnO nanorod arrays grown on the Au/SiO₂/Si substrate was proposed.     

Effect of growth temperature on the structure and optical properties of ZnO nanorod arrays grown on ITO substrate

ZnO nanorod arrays have been successfully prepared on ITO substrate by a chemical‐bath deposition method at different growth temperatures. The influence of the growth temperature on the morphology and microstructure of the ZnO nanorods was investigated by scanning electron microscopy (SEM) and X‐ray diffraction (XRD). The results showed that the diameter of the ZnO nanorods decreased and the size of the nanocrystals increased with increasing growth temperature. Optical absorption measurements showed the absorption band edge has shifted to a lower‐energy region due to the quantum size effect. Green emission and UV emission bands were observed and they are found to be temperature dependent, which indicates that the deep‐level emission and band‐edge emission of ZnO nanorods is closely related to the rod diameter, and the related mechanism is discussed.     

Improving the property of ZnO nanorods using hydrogen peroxide solution

Zinc oxide (ZnO) nanorod arrays made by the hydrothermal method were treated with hydrogen peroxide (H₂O₂) solution through two different approaches. One is to immerse ZnO nanorod sample into H₂O₂ solution. The other is a pre-treatment of spin-coating H₂O₂ solution on the seed layer before the growth of the ZnO nanorods. In the first approach, we found that the ultraviolet (UV) emission peak of the ZnO nanorod photoluminescence (PL) spectra was strongly dependent on the immersion time. In the second approach, the H₂O₂ solution influences not only the quality of the seed layer, but also the amount of the oxygen interstitial defects in the ZnO nanorods grown thereon. As a result, the UV emission intensity from the ZnO nanorods is enhanced almost five times. The ZnO nanorod arrays with few oxygen interstitial defects are prepared by the hydrogen peroxide treatment and expected to enable the fabrication of optoelectronic device with excellent performance.     

Growth and conductivity enhancement of N-doped ZnO nanorod arrays

A simple two-step process was developed for growing the nitrogen-doped ZnO (NZO) nanorod arrays on glass substrates. ZnO particles serve as a seed layer deposited by the electrostatic spray deposition method for the growth of NZO nanorods in aqueous solution. FE-SEM images revealed that nanorods have approximately uniform length distribution with hexagon end planes and grow vertically along the c-axis, which was also confirmed by X-rays diffraction. In addition, NZO nanorods had an average diameter of 140±20 nm and an average length of 1.2 to 2.7 μm with a wurtzite-type structure of ZnO. N doping had no prominent effect on the structure and crystal orientation, but it helps to increase the length and reduction in the diameter of nanorods. Moreover, electrical resistivity was found to decrease first and then increase with further nitrogen doping due to the decrease of mobility and increase of carrier concentration. Also the transmittance increased initially, but at higher nitrogen contents it decreased. Annealing the nanorods imparts no effect on the morphology, but there was a significant decrease in electrical resistivity due to the formation of oxygen vacancies. The realization of p-type ZnO nanorod arrays with durable and controlled transport properties is important for the fabrication of nanoscale electronic and optoelectronic devices.     

氨水浓度对化学浴沉积的Zn(O,S)薄膜形貌、结构和性能的影响

采用化学浴法,以ZnSO4·7H2O和SC( NH2)2作为反应前驱物,C6H5O7 Na3·2H2O作为络合剂,NH3·H2O 作为辅助络合剂和缓冲剂制备Zn(O,S)薄膜.采用SEM、EDS、XPS、XRD和透射光谱分析方法,研究氨水浓度对化学浴法制备的Zn(O,S)薄膜形貌、成分、结构和光学性能的影响以及Zn(O,S)薄膜的形成机理.结果表明:Zn(O,S)薄膜是由ZnO和ZnS纳米颗粒混合组成的,ZnO具有纤锌矿结构,ZnS是以非晶相存在.随着反应溶液中氨水浓度的降低,薄膜中所包含的ZnO逐渐减少,ZnS逐渐增加,S/Zn原子比逐渐增加,透射率和光学带隙也逐渐增大.     

载气流量对氧化锌纳米棒阵列的影响

本文研究了在金属有机化学气相沉积法(MOCVD)生长过程中,锌(Zn)源和氧(O)源载气流量的改变对ZnO纳米棒阵列的影响.通过改变源材料载气的流量,得到了直径从150 nm到20 nm范围、均一性明显改善的ZnO纳米棒.采用扫描电子显微镜(SEM),X射线衍射图谱(XRD),拉曼光谱(Raman)和光致荧光光谱(PL)等测试手段对样品的形貌结构和光学特性进行了表征.SEM和XRD结果表明当Zn源和O源的载气流量均为1 SLM时,所得的纳米棒直径最均匀,排列整齐,垂直于衬底生长,且结晶度最好.PL谱显示纳米棒的紫外带边峰发生了蓝移,可能与表面效应的增加有关.     

Structure and optical property of BexZn1‐xO nanorod arrays

Be_xZn_1‐xO nanorod arrays with high crystalline quality were fabricated on Si substrate by a simple, low‐cost hydrothermal method. The effect of Be‐corporation on the structure, morphology and optical property of ZnO nanorod arrays was investigated. The diameter of Be_xZn_1‐xO nanorods gradually decreased and the length of them increased with increasing Be concentration. Edge emissions of the Be_xZn_1‐xO nanorods show a obvious blue shift upon the increase of the Be content.