ZnO能带及态密度的密度泛函理论研究

本文采用基于密度泛函理论框架下第一性原理的平面波赝势方法,并采用局域密度近似(LDA)理论和ABINIT软件对ZnO电子结构进行了计算.得到了ZnO的能带和态密度曲线.研究表明,ZnO的价带基本上可以分为三个区域,即下价带区、上价带区和位于-18.1 eV处的宽度为1.1 eV的价带;导带部分主要是由Zn的4s态贡献的,O的2p态在该区域内具有微弱的贡献;ZnO是一种直接宽禁带半导体,导带底和价带顶位于布里渊区中心处,带隙为0.9 eV,相对比较该结果优于一些文献给出的计算值.     

CZTSe/Cd1-xZnxS界面能带结构研究

严重的开路电压损耗是限制铜锌锡硫(硒)薄膜太阳电池性能提升的关键问题,其吸收层和缓冲层界面的能带结构有待进一步优化.针对此问题,本文对CZTSe/Cd1-xZnxS界面的能带结构进行了研究.首先,模拟计算了化学水浴法制备Cd1-xZnxS薄膜所需的溶液体系条件,通过椭偏仪和SEM测试结果分析了不同Cd/Zn比例的Cd1-xZnxS缓冲层形貌、光学特性以及禁带宽度.然后,对CZTSe/Cd1-xZnxS界面进行了XPS测试分析,发现CZTSe/Cd0.9Zn01S界面最为匹配,其导带失调值约为0.3 eV.最后对电池器件进行了制备与测试,得到的CZTSe/Cd0.9Zn0.1S结构的太阳电池比CZTSe/CdS结构具有更高的开路电压,达到了394 mV,转换效率达到了5.78;.     

Mg/Cd共掺杂ZnO电子结构与光学性质的第一性原理研究

采用基于密度泛函理论的第一性原理平面波超软赝势法,研究了Mg/Cd(不同的Cd浓度)共掺杂ZnO的电子结构和光学性质.研究表明:Mg/Cd共掺杂ZnO,体系的晶胞尺寸变大,但结构稳定.当Mg/Cd为1:1时,吸收边略微发生蓝移.随Cd的掺杂浓度增加,导带部分逐渐下移,禁带宽度变窄,出现红移现象.除此之外体系的吸收率和反射率也减小.说明Mg/Cd共掺杂ZnO,不仅使得体系光学谱丰富,而且透射性增强.这对实验中制备出高透射率的材料具有一定的指导意义.     

第一性原理研究Cd掺杂对ZnO电子结构与光学性质的影响

采用第一性原理平面波超软赝势方法超软赝势方法,研究了Cd掺杂前后ZnO的电子结构以及光学性质.计算结果发现:Cd的掺入使得ZnO的电子结构发生了改变,晶胞变大,禁带宽度变窄.Cd掺杂使ZnO的光学性质也发生了变化,4.3 eV处的介电峰增强并发生红移,12.9 eV处的介电峰减弱,对紫外光吸收作用增强.     

Fe/Cu掺杂ZnO纳米粉体的结构及光学性能研究

采用络合物溶胶-凝胶法分别制备了不同掺杂浓度的Zn1-xFexO(0≤x≤0.20)、Zn1-xCuxO(0≤x≤0.20)及Zn0.095 Cu0.05-yFeyO(0.01≤y≤0.04)的粉体样品,研究掺杂浓度对ZnO晶体结构及光学性能的影响,利用X射线衍射仪、红外光谱仪、紫外-可见光分光光度计、荧光光谱仪对样品的物相和光学性能进行表征.结果表明,掺杂量小于5;时的Zn1-xFexO、Znl-xCuxO及Zn0.095 Cu0.05-yFeyO样品均为六方纤锌矿型ZnO晶体;掺杂后可见光波段的吸收率与纯ZnO相比明显提高,掺杂ZnO的光学带隙变窄;PL峰位略微蓝移;Fe3+/Cu2+共掺杂ZnO的PL峰发光强度比单掺Cu2+的强,比单掺Fe3+的弱.     

Al掺杂ZnO多晶的热电输运性质研究

采用固相反应法制备了六方纤锌矿结构Zn1-xAlxO(0≤x≤0.03)系列多晶,探究了Al掺杂对ZnO多晶的微观形貌和热电输运性质的影响.结果表明,Al掺杂促使ZnO晶粒长大联结,晶界减少,x＞0.003时出现在晶界分布的ZnAl2O4尖晶石相.掺杂后样品由ZnO的半导体行为转变为电阻率显著下降的金属行为,且x=0.003有最小的室温电阻率～1.7 mΩ·cm,主要由于掺杂使样品载流子浓度和迁移率显著提高,x=0.003时载流子浓度和迁移率为最高,分别为1.05×1021 cm-3和20 cm2/V·s;300 ～900 K下掺杂样品热电势的绝对值和功率因子均随温度升高而增大,x =0.003时有最大的室温功率因子～0.4mW/m·K2.综合得到ZnO中Al掺杂的饱和固溶度x≈0.003.     

磁控溅射Cd1-xZnxTe多晶薄膜组分的可控生长

采用双靶位共溅射方法制备出组分可控的Cd1-xZnxTe薄膜样品,组分偏离小于0.13.采用XRD对不同生长温度制备的样品进行了结晶性分析,研究了薄膜结晶与生长温度的关系.采用AFM、SEM对样品进行了表面和界面分析,表明薄膜表面平整,界面清晰.对不同组分的Cd1-xZnxTe样品进行了透射光谱测量,得到了光学性质随组分的变化规律,并拟合得出了这些样品的带隙和组分.     

ZnO晶体Al杂质与Zn间隙共存的复合缺陷研究

利用第一性原理,研究了ZnO晶体Al杂质与Zn间隙共存的复合缺陷(AlZnZni)电子结构和光学性质.计算结果显示,AlZnZni复合缺陷的形成能为-3.180 eV,较低的形成能表明这种缺陷容易形成;复合缺陷使ZnO晶体的能带整体下移,带隙减小,价带区域展宽;电子能带结构的变化对ZnO的光学性质在低能产生了重要影响,主要表现在:介电函数虚部往低能方向移动且强度显著增强,使得ZnO表现出简并半导体的特性;复合缺陷导致ZnO晶体光学吸收边缘产生了红移,可见光区的吸收系数增大,透过率降低.     

掺Cd对ZnO薄膜光学性能的影响

采用溶胶-凝胶法在石英玻璃上制备了不同掺Cd浓度的ZnO薄膜.X射线衍射(XRD)结果表明,所制备的薄膜具有c抽择优取向,随着Cd掺杂浓度的升高,(002)峰向低角度方向移动.UV透射曲线表明,薄膜具有明显的紫外吸收边,通过改变Cd的掺入浓度,可以使吸收边向长波方向移动并被控制在一定范围内,从而使薄膜的禁带宽度连续可调;薄膜的光致发光(PL)谱显示,ZnO薄膜的PL谱是由紫外激子发光峰和蓝光发光带组成,通过掺入Cd可使紫外带边发射的峰位向低能端方向红移,这与透射谱中吸收带边的红移相吻合,由紫外发光峰得到的光禁带宽度和由透射谱拟合得到的光禁带基本一致.对不同掺杂浓度的薄膜进行了比较,发现Cd掺入量为8;摩尔分数时ZnO薄膜具有最佳的结构性能和发光性能.     

高浓度Co掺杂ZnO晶体的水热法制备及磁性

采用水热法以CoO、ZnO混合为前驱物制备了ZnO晶体,矿化剂为6 mol/L KOH,填充度70;,温度430℃,两种样品CoO、ZnO组分物质的量百分比分别为0.5∶1和1∶1.当前驱物为nCo∶nZn=0.5∶1时,合成出Zn1-xCoxO晶体,Co元素掺杂量分别为6.83 at;和9.30 at;.当前驱物中nCo∶nZn=1∶1时,Zn1-xCoxO晶体中Co掺杂比例达到9.31 at;,同时伴有Co3O4生成,其中Zn掺杂比例达到14.59 at;,SEM显示,所制备的Zn1-xCoxO具有明显的ZnO晶体特征,形态完整,最大尺度约为50 μm.SQUID测量显示,生成物中Zn1-xCoxO晶体具有顺磁性,Zn1-xCoxO和Co3-xZnxO混合晶体也显示为顺磁性.     

The effect of ZnO buffer layer on structural and optical properties of ZnO nanorods

A low‐temperature synthetic route was used to prepare oriented arrays of ZnO nanorods on ITO conducting glass substrate coated with buffer layer of ZnO seeds in an aqueous solution. The corresponding growth behavior and optical properties of ZnO nanorod arrays were studied. It was found that the nature of the buffer layer had effect on the microstructures and optical properties of the resultant ZnO nanorod arrays. X‐ray diffraction (XRD) results showed the nanorods were preferentially grown along (002) direction, but the diameter of the nanorods prepared with the buffer layer was much smaller than the without one, which can be clearly seen from the scanning electron microscopy (SEM) results. And it also found that the buffer layer was not only enhanced the density of overall coverage but also beneficial to grown the oriented arrays. Photoluminescence spectroscopy (PL) results indicated that the all the samples had the better optical behaviors. By computation, the relative PL intensity ratio of ultraviolet emission (I_UV) to deep level emission (I_DLE) of ZnO nanorods grown with the pure substrate was much higher than that of the sample with the buffer layer. The defects on the surface increased with the size reduction of nanorods caused by the buffer layer may be the main reason for it. And the small shift in the UV emission was caused by the rapid reduction in crystal size and compressive stress from Raman spectra results. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

ZnO纳米棒的电致发光研究

采用化学浴沉积法在ITO导电玻璃衬底上制备了ZnO纳米棒膜层,构建了无绝缘层和添加Alq3为绝缘层的两类ZnO发光器件,测试和比较了两类器件的光致发光与电致发光特性.结果表明,在ZnO和Alq3混合体系的PL谱中,观察到ZnO的380nm发光减弱而Alq3的520 nm发光增强,这表明在ZnO的激子态和Alq3分子之间发生了能量转移.ZnO纳米棒的EL谱表现为随机激光,这主要是由于光在纳米棒内谐振,及纳米棒长短不一、阵列不整齐所致.加入Alq3后,器件的Ⅰ-Ⅴ曲线上出现了约为1.6V的阈值电压,工作电压由30 V降为18 V,且器件的发光颜色由黄绿区移到蓝紫区.     

ZnO growth on Si with low-temperature ZnO buffer layers by ECR-assisted MBE

High-quality ZnO films were grown on Si(1 0 0) substrates with low-temperature (LT) ZnO buffer layers by an electron cyclotron resonance (ECR)-assisted molecular-beam epitaxy (MBE). In order to investigate the optimized buffer layer temperature, ZnO buffer layers of about 1.1 μm were grown at different growth temperatures of 350, 450 and 550 °C, followed by identical high-temperature (HT) ZnO films with the thickness of 0.7 μm at 550 °C. A ZnO buffer layer with a growth temperature of 450 °C (450 °C-buffer sample) was found to greatly enhance the crystalline quality of the top ZnO film compared to others. The root mean square (RMS) roughness (3.3 nm) of its surface is the smallest, compared to the 350 °C-buffer sample (6.7 nm), the 550 °C-buffer sample (7.4 nm), and the sample without a buffer layer (6.8 nm). X-ray diffraction (XRD), photoluminescence (PL) and Raman scattering measurements were carried out on these samples at room temperature (RT) in order to characterize the crystalline quality of ZnO films. The preferential c-axis orientations of (0 0 2) ZnO were observed in the XRD spectra. The full-width at half-maximum (FWHM) value of the 450 °C-buffer sample was the narrowest as 0.209°, which indicated that the ZnO film with a buffer layer grown at this temperature was better for the subsequent ZnO growth at elevated temperature of 550 °C. Consistent with these results, the 450 °C-buffer sample exhibits the highest intensity and the smallest FWHM (130 meV) of the ultraviolet (UV) emission at 375 nm in the PL spectrum. The ZnO characteristic peak at 438.6 cm⁻¹ was found in Raman scattering spectra for all films with buffers, which is corresponding to the E₂ mode.     

基底温度对ZnO/Cu/ZnO透明导电膜性能的影响

采用射频磁控溅射ZnO陶瓷靶、直流磁控溅射Cu靶的方法在不同基底温度下制备了ZnO/Cu/ZnO多层膜.用X射线衍射仪、原子力显微镜、紫外可见分光光度计和四探针测试仪对样品的性能进行了表征.结果表明,随着基底温度的升高,ZnO层c轴择优取向明显,结晶程度变好,Cu层的结晶性先变好后逐渐变差;多层膜表面均方根粗糙度随基底温度的升高而增加;光学透过率随基底温度的升高逐渐增大,基底温度为300 ℃时最大透过率接近90;;面电阻随基底温度的升高逐渐增加,最小面电阻为12.4 Ω/□.     

氧化锌微米棱棒的水热法制备和稀土掺杂

本文采用水热法,通过改变溶剂制备了不同形貌的氧化锌微米棱棒,并尝试对其进行稀土Er3+的掺杂.通过X射线衍射(XRD)、扫描电镜(SEM)、荧光光谱(PL)及分光光度计对所得产物的组成、形貌、发光性能和光学特性进行了研究.实验表明:醇-水的环境有利于得到形态均匀的微米棱棒,醇水比例为1∶2.5,激子辐射复合发光与缺陷发光的比例最高,缺陷浓度最低,晶体质量最高.随着Er3+掺杂浓度的增加吸收强度增强,Er3+掺杂浓度达4mol;时吸收度不再变化.     

In-situ and ex-situ ZnO nanorod growth on ZnO homo-buffer layers

Vertically well-aligned ZnO nanorods were fabricated in-situ and ex-situ on ZnO homo-buffer layers using catalyst-free metal-organic chemical vapor deposition. Field-emission electron microscopy measurements demonstrated that the nanorods were well aligned and had a uniform diameter of 70–100 nm depending on the growth temperature, irrespective of growth conditions, in-situ and ex-situ. X-ray diffraction measurements demonstrated that the ZnO nanorods and the ZnO buffer layers had a wurtzite structure, and that the crystal quality of the nanorods grown on a smooth surface was better than that of the nanorods grown on a rough surface. Field-emission transmission electron microscopy measurements revealed the presence of a disordered layer at the interface of the nanorod and the buffer layer.     

本征缺陷对Ag掺杂ZnO的影响

采用基于密度泛函理论的第一性原理赝势法对Ag掺杂ZnO体系中Ag缺陷和本征缺陷复合体的几何结构、形成能和电子结构进行了比较研究.研究表明,Ag代替Zn位(AgZn)可以在ZnO中形成受主能级.同时,研究发现, Zni-AgZn和Oi-AgZn的形成能较小,存在的可能性较大.其中,Zni-AgZn 呈现明显的n型导电特性,而Oi-AgZn具有p型导电的趋势.因此Oi-AgZn有利于p型ZnO的形成.     

纳米氧化锌电致发光的研究进展

本文就当前纳米ZnO的电致发光研究进展作出综述,评论的重点在于ZnO缺陷态的无p-n结结构的电致发光,部分工作也涉及到激子态发光。文中所列研究结果和数据,除注明外均为本组工作,其中某些是首次报告。     

Al-N共掺杂ZnO的第一性原理研究

为了研究p型ZnO的掺杂改性,本文运用第一性原理密度泛函理论研究了未掺杂,Al、N单掺杂和Al-N共掺杂ZnO晶体的几何结构、能带结构、电子态密度.计算结果表明:未掺杂,Al、N单掺杂和Al-N共掺杂ZnO的超晶胞体积分别为0.2043 nm3、0.2034 nm3、0.2027 nm3、0.1990 nm3,带隙分别为0.72 eV、0.71 eV、0.60 eV、0.55 eV;N是比较理想的p型掺杂受主,若在禁带中再引入激活施主Al后,可填充的电子数由原来的19个增加到24个,N原子接受从价带跃迁的电子使价带产生非局域化空穴载流子,从而提高了晶体的导电性.与未掺杂,Al、N单掺杂相比,Al-N共掺杂ZnO具有更稳定的结构,更窄的带隙,更好的导电性,更有利于实现p型化.