Bi掺杂ZnO籽晶层生长纳米ZnO薄膜性能研究

采用溶胶 凝胶法制备得到不同浓度Bi3+掺杂ZnO籽晶层,又进一步采用水热法合成了六方纤锌矿结构的ZnO纳米棒。通过X线衍射（XRD）、场发射扫描电子显微镜（FESEM）、光致发光（PL）谱等测试手段对样品结构、形貌和光学性能进行测试和表征。结果表明,在不同浓度Bi掺杂ZnO籽晶层上生长纳米ZnO薄膜,ZnO的晶体结构没有改变,均为六方纤锌矿结构,且(002)晶面的峰强明显高于其他晶面的峰强值;在FESEM电镜观察下发现,不同掺杂浓度Bi掺杂ZnO籽晶层上水热生长的纳米ZnO薄膜均为纳米棒状。PL光谱显示随着Bi掺杂量增加,样品的近紫外发射峰和晶格缺陷峰等峰值明显增大,且有红移现象产生。其中禁带宽度随着Bi掺杂量的增大而减小,说明Bi3+可以有效地调节ZnO的禁带宽度。     

掺杂浓度对Co掺杂ZnO纳米棒的铁磁性的影响

采用化学气相沉积(CVD)方法制备出3种掺杂浓度的Co掺杂ZnO纳米棒。使用EDX(en-ergy dispersive X-ray)能谱,测得3种ZnO纳米棒中Co元素的掺杂浓度分别为0.4、1.4和2.4%。X射线衍射(XRD)分析表明,三个样品均为ZnO的六方铅锌矿结构,并沿着c轴取向择优生长。磁化曲线显示,掺杂浓度为0.4%的Co掺杂ZnO纳米棒为顺磁性,随着掺杂浓度的增大,Co掺杂ZnO纳米棒转变为铁磁性。扩展X射线吸收精细结构谱表明,Co掺杂ZnO纳米棒的铁磁性源于ZnO纳米棒中的Co金属团簇。     

Al掺杂对ZnO纳米结构阵列的影响

采用脉冲电磁场辅助水热合成法制备了高比表面积、高能面暴露的ZnO纳米片阵列,通过场发射扫描电镜(FESEM)、X线衍射(XRD)及X线光电子能谱(XPS)等手段测试纳米结构阵列的性能。结果表明,经过Al掺杂后的ZnO纳米结构由棒状转变为六边形的片状结构,当Al的摩尔分数为1%时,纳米片彼此交错,组织均匀,垂直于衬底,与传统纳米棒相比,纳米片具有更大的比表面积及更多暴露的高能晶面,并对纳米棒向纳米片的转变机理进行了详细的分析和探讨。     

ZnO:Al/n-ZnO/p-GaN异质结电致发光特性研究

利用ZnO和GaN材料制备了ZnO:Al/n-ZnO/p-GaN透明电极异质结发光二极管。通过SEM、TEM和荧光光谱对ZnO纳米棒进行了结构表征和发光特性表征。通过半导体特性分析系统和光谱测试技术对ZnO:Al/n-ZnO/p-GaN异质结进行了电致发光性能测试和机理分析。结果表明该器件能产生有效的蓝紫色电致发光,其发光分别来自于n型ZnO、p型GaN以及界面辐射;并且采用ZnO:Al作为透明电极可以提高该器件的出光效率。该异质结可应用于高效率短波发光器件。     

本征和Al3+掺杂ZnO薄膜的特性研究

采用溶胶-凝胶方法在载玻片衬底上制备了本征及不同Al3+掺杂浓度的ZnO:Al薄膜,利用X射线衍射(XRD)、原子力显微镜,紫外-可见光吸收光谱及霍尔效应研究了Al3+掺杂浓度对ZnO:Al薄膜结构和光电性能的影响。结果显示,ZnO:Al薄膜为六角纤锌矿晶体结构,具有很高的沿c轴的(002)择优取向,Al3+掺杂并没有改变ZnO的晶体结构,只是Al取代了Zn;掺杂前后薄膜样品均在ZnO带边吸收的位置有较强的吸收而在可见光范围吸收较小;并且当Al3+掺杂浓度为1.5%(摩尔百分比)时所获得的ZnO:Al薄膜具有最小的电阻率,为26Ωcm。     

Alq基有机发光二极管中Liq的“n型掺杂”机理研究

通过将Liq(8-hydroxyquinolinato-lithium)掺入电子传输层Alq(tris(8-hydroxyquinolinato)aluminum)中,制备了具有不同结构的仅传输电子的单载流子器件。实验结果表明,掺杂器件的电性能劣于含Liq/Al复合阴极的非掺杂器件,优于含Al阴极的非掺杂器件,这表明掺入Alq的Liq没有产生明显的“n型掺杂”效应,其具有双重作用:掺杂后分散在Alq/Al阴极界面上的Liq以电子注入层的形式出现,通过增强电子注入来提高器件电流;掺杂后存在于Alq体相中的Liq由于自身的导电性差,对电子传输具有不利影响,从而降低了器件的电流。在电致发光器件的测试中,Liq的掺杂表现出类似的现象,掺入Liq的器件性能介于非掺杂具有Liq/Al阴极和Al阴极结构器件之间,三种器件的最大电流效率分别为3.96,4.27和2.27cd/A,并且在吸收光谱和光致发光光谱中观察不到电荷转移所带来的额外变化。     

多孔ZnO纳米花电子传输层对有机太阳能电池性能的优化

通过水热法制备了多孔、单晶结构的三维ZnO纳米花材料。研究了不同生长时间下(6h、9h和12h)的ZnO材料的形貌及光电性能。结果表明,反应9h的多孔ZnO纳米花材料具有较高透光率、低缺陷密度以及高载流子迁移率等优点,是较为理想的电子传输层材料。将这些材料应用于有机太阳能电池的制备,性能测试结果表明,以生长时间为9h的多孔ZnO纳米花材料作为电子传输层的器件性能最佳,与无ZnO修饰层的参比器件相比,其短路电流密度Jsc和光电转化效率(PCE)明显提高,分别达到了5.68mA/cm2和1.24%。     

石墨烯基柔性衬底铬掺杂氧化锌的生长及催化性能研究

采用低温水热法,在石墨烯涂覆的聚对苯二甲酸乙二醇酯(PET-GR)柔性衬底上制备了不同浓度Cr掺杂的氧化锌纳米复合材料(Cr-ZnO/PET-GR)。通过X射线衍射仪(XRD)、场发射扫描电镜(FE-SEM)和X射线光电子能谱(XPS)对氧化锌的晶体结构、微观形貌及表面化学状态进行了表征,采用电化学阻抗(EIS)、光致发光光谱(PL光谱)研究了氧化锌的光、电性能,并计算了Cr³⁺、Cr²⁺掺杂前后的分子最高占据轨道(HOMO)和最低未占据轨道(LUMO),评价光电子产生的难易程度。结果表明,Cr掺杂前后,氧化锌薄膜均为六方纤锌矿结构。Cr-ZnO/PET-GR和未掺杂的氧化锌(ZnO/PET-GR)纳米薄膜均为棒状,微量Cr的掺入使得ZnO纳米棒垂直度和致密度增大,纳米棒的直径减小。Cr元素主要以Cr³⁺的形式存在。理论计算和试验均表明,Cr³⁺掺杂使得载流子的复合效率显著降低,显著提高了其光催化效率。     

ZnO基紫外光电探测材料研究

ZnO作为II-VI族直接宽禁带半导体材料,在室温下的禁带宽度约为3.37 eV,对应紫外波段的光子能量,且ZnO具有较高的化学和热稳定性,较强的抗辐射损伤能力,来源丰富,电子诱生缺陷较低等特点,适用于制备高性能的紫外探测器。而ZnO在掺杂后形成的合金可调节其禁带宽度,并与ZnO的晶格失配度及热膨胀系数差别较小,可构成量子阱或超晶格结构被广泛地应用于光电器件中,提高光电性能,所以相关的带隙工程的开展有利于推进实用的高性能的ZnO基光电器件的开发。尤其是对于ZnO基紫外探测器件,ZnO基三元合金具有可调控其探测波段到日盲区的特点,在此基础上所实现的紫外探测器在军事和民用领域具有广泛应用。基于此,笔者采用掺杂的方式调制ZnO的禁带宽度,使ZnO基三元合金材料的光学禁带宽度达到4.4 eV以上,获得可用于日盲紫外光波段探测的ZnO基光电探测器;同时,通过控制掺杂技术开发ZnO基异质复合结构,可应用于高性能的紫外光电发射探测器件。主要内容和创新性结果如下:1.采用溶胶–凝胶方法制备了Mg、Cd、Al掺杂的ZnO基三元合金薄膜,并对其微结构和光电性能进行研究,分析其掺杂效率和光学禁带调制效应,获得掺杂对ZnO薄膜禁带宽度调制的规律,并从不同元素掺杂引起Zn3d电子结合能变化的角度探讨了其禁带调制的机理。2.采用射频磁控溅射法制备AlxZn1-xO(AZO)合金薄膜,研究不同掺Al浓度对其微结构和光电性质的影响规律,研究表明:Al粒子数分数增大到20%会导致ZnO纤锌矿结构的消失,表明掺Al的固溶度在20%以内,而当掺Al粒子数分数达到30%则出现新的晶相;且随掺Al粒子数分数增加,薄膜中晶粒细化,电阻率大幅上升;通过改变Al组分可较大地展宽光学带隙,在Al粒子数分数为30%时带隙被展宽至4.43 eV。3.探讨氧气氛对AZO合金薄膜导电性的影响,并通过对其微结构和光电特性的研究发现:溅射过程中通入少量氧气有利于获得结晶质量较好的c轴择优取向薄膜;而纯氩气氛下溅射的薄膜具有很低的电阻率,拉曼测试和SEM分析表明其存在特殊的内建电场和c轴取向平行于膜面的晶粒;溅射过程中氧分压的增加会导致薄膜的绝缘性能增强;其透光谱显示光学吸收边发生明显蓝移。4.研究AZO合金薄膜的光电响应性能,结果表明:掺入Al可抑制ZnO薄膜中氧空位缺陷的形成,Al粒子数分数的增大使得薄膜的绝缘性能增强,有利于实现暗电流低的光电探测器件,提高其光暗电流比,尤其是可以抑制慢速的氧气吸附和解吸附反应,从而提高器件的响应速度。获得的快速响应的AZO探测器在紫外光照下显示出对称的非线性特征,即采用元件替代方法将光敏电阻应用于蔡氏电路时,在变型蔡氏电路中可产生三涡旋光电混沌吸引子。5.研究掺Al对AZO薄膜表面势垒和功函数的影响,通过对不同Al浓度AZO合金薄膜的C-V测试,获得其表面接触势垒高度随Al浓度增加而减小的规律;分别从理论计算和I-V-T测试拟合研究了5%粒子数分数掺Al对ZnO薄膜表面功函数的影响,两种方式获得的表面功函数值分别下降了0.090 eV和0.098 eV。以上研究结果表明掺Al使得AZO薄膜的费米能级上移至导带,从而形成较小的表面势垒,有利于电子从表面逸出。6.研究将AlxZn1-xO薄膜用于实现NEA紫外光电阴极,制作AZO阴极真空光电管,其光暗电流相差两个数量级以上。采用高导电AZO薄膜作为透明导电底电极,在其上诱导生长阳离子空位为主导的AZO纳米晶表面层,由以上掺杂调制技术获得的AZO异质复合结构阴极材料,因为底电极和阴极膜同属AZO材料体系,界面间结合紧密,并能有效实现能带调制,具有良好的紫外光电发射性能。在铯激活条件下的测试结果为:暗电流为0.2 nA,在254 nm波长的紫外光照射下产生220 nA光电发射电流,光暗电流比达到103数量级。     

溶胶-凝胶法制备Al3+掺杂ZnO薄膜的结构和光学性能

采用无机盐溶胶-凝胶方法在载玻片衬底上制备了ZnO:Al薄膜,利用X射线衍射(XRD)、紫外-可见光透射光谱(UV-Vis transmittance spectrum)和扫描电镜(SEM)研究了退火温度和Al3+掺杂浓度对ZnO:Al薄膜结构和光学性能的影响.结果表明,随退火温度的升高或进行适当浓度的Al3+掺杂,可...     

Preparation of Al-doped ZnO nanostructures and their application in acrylic resin-based heat insulation coatings

Al-doped ZnO (AZO) nanoflowers and nanorods were successfully synthesized by a simple precipitation method in the presence of polyethylene glycol as the surfactant. The effect of Al dosage on the morphology and structure of AZO was investigated. The AZO was characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, energy dispersive spectrometry and transmission electron microscopy. It has been found that the morphology of as-prepared AZO nanostructures varies with varying Al dosage. AZO nanoflowers are assembled by nanorods with a diameter of 80–100 nm and a length of 1 μm. In the AZO nanoflowers and nanorods, Al³⁺ substitutes Zn²⁺ but does not change the hexagonal wurtzite structure of ZnO. Moreover, the products were mixed into acrylic resin to generate AZO/acrylic resin composite coatings; and the heat insulation performance of the coatings was evaluated in relation to the function of the AZO fillers. The result shows that the coatings possess a certain degree of heat insulation performance.     

sol-gel法制备ZAO薄膜的结构与光学性能研究

采用溶胶—凝胶法在普通玻璃衬底上制备了ZAO(ZnO:A1)薄膜,利用XRD、SEM、紫外—可见光谱和光致发光光谱对所制备的AZO薄膜进行了表征,研究了ZAO薄膜的结构和光学性能.结果表明:ZAO薄膜的微晶晶相与ZnO一致,且具有c轴择优取向;ZAO薄膜在可见光区的透过率超过了88％,在350～575 nm范围内有强的...     

反应磁控溅射直接生长绒面结构ZnO:Al-TCO薄膜及其特性研究

利用反应磁控溅射技术,在玻璃衬底上直接生长获得了"弹坑状"绒面结构的ZnO:Al-TCO薄膜。通过梯度O2生长(GOG,gradual oxygen growth)方法改善ZnO薄膜的透过率和绒度特性,并且具有较好的电学性能。通过优化实验,GOG方法生长ZnO:Al薄膜(薄膜结构:11.0sccm/10R+9.5sccm/15R)的"弹坑状"特征尺寸为300～500nm,可见光范围透过率达到90%,方块电阻约为4.0Ω/□,电子迁移率为17.4cm2/V-1.s-1。大面积镀制的ZnO:Al具有良好的绒面结构和电学均匀性,可应用于光伏(PV)产业化推广应用。     

Al掺杂对ZnO薄膜形貌和光学性能的影响

采用溶胶-凝胶旋涂法在FTO玻璃衬底上制备得到了不同Al掺杂浓度的ZnO薄膜(AZO)。利用XRD、FESEM、UV-vis和PL等测试手段对样品结构、形貌和光学性能进行了表征。结果表明,合成的AZO薄膜均为六方纤锌矿结构且峰强随掺杂浓度的升高而减弱;同时,颗粒形貌由不规则向规则球形转变且尺寸逐渐减小;PL谱中的近紫外发射峰和晶格缺陷峰值随掺杂浓度的升高先增大后降低;由UV-vis吸收光谱可知,AZO薄膜在设定波长内的光吸收处于波动状态,且当Al掺杂浓度为3%时,光吸收强度最高,禁带宽度减小到3.12eV。     

AZO种子层朝向对ZnO纳米棒形貌和发光特性的影响

在水平管式炉中,采用热蒸发锌粉的方法,在镀有掺铝氧化锌(AZO)薄膜的石英基片上制备了大量高密度的ZnO纳米棒,AZO膜面分别正对和背对锌源。利用扫描电子显微镜、X射线衍射仪以及荧光光谱仪分析AZO膜面朝向对ZnO纳米棒的形貌、微结构及光学性能的影响。结果表明,不同朝向的AZO膜面上所生长的纳米棒具有相似的形貌和微结构。保温时间10min样品的氧空位的缺陷态发光为绿光,强度较强;保温时间15min样品的纳米棒长度较长、相对垂直衬底,其近带边发光较强,氧间隙的缺陷态发光较弱。正对锌源衬底上且保温时间15min样品的近带边发光最强,且缺陷态发光最弱。     

First-Principles Study of the Electronic Structure and Thermoelectric Properties of Al-Doped ZnO

ZnO materials doped with elements such as Al, Ga, etc. are of great interest for high-temperature thermoelectric applications. In this work, the effects of Al doping on the electronic structure and thermoelectric properties of the ZnO system are presented. The energy band structure and density of states of Al-doped ZnO were investigated using the projector-augmented plane wave pseudopotential method within the local density approximation. The calculated energy band structure was then used in combination with the Boltzmann transport equation to calculate the thermoelectric parameters of Al-doped ZnO. The electronic structure calculation showed that the position of the Fermi level of the doped sample was shifted to a higher energy level compared with the undoped material. The conduction band near the Fermi energy was a combination of hybridized Zn sp-orbitals and Al s-orbital. The calculated thermoelectric properties were compared with the experimental results, showing some agreement. For the Al-doped ZnO system, the Seebeck coefficient was shown to be negative and its absolute value increased with temperature. The electrical conductivity and electronic thermal conductivity followed the trend of the experimental results.     

The effects of Al doping and post-annealing via intrinsic defects on photoluminescence properties of ZnO:Eu nanosheets

Europium (Eu) and Aluminum (Al) co-doped ZnO nanosheets were synthesized by a hydrothermal method. The effects of Al concentration as a dopant and post-annealing of ZnO:Eu nanosheets on its structural, electrical and optical properties were investigated in detail. Prepared samples were characterized structurally using X-ray diffraction (XRD), morphologically using scanning electron microscopy (SEM) and optically using photoluminescence (PL) spectroscopy analyses. No diffraction peak related to dopants in XRD spectrum along with shift in peaks angles relevant to ZnO proved that Al and Eu ions were doped successfully into ZnO nanosheets. This study recommends that extrinsic doping and intrinsic defects have impressive roles on transferring energy to Eu ions at indirect excitations. Based on photoluminescence observations, intra-4f transitions of Eu³⁺ ions at an excitation wavelength of 390 nm allow a sharp red luminescence. Also the results showed that optical properties of ZnO can be tuned by varying the amount of Al concentration. In comparison with annealed Al doped ZnO:Eu nanostructures, as-grown samples showed the stronger PL peaks which indicated the effective role of intrinsic defects beside of extrinsic doping on energy transfer from ZnO host to Eu³⁺ ions which consequently led to producing the strong red emission from these sites.     

Structural and optical properties of (Al,K)-co-doped ZnO thin films deposited by a sol–gel technique

Thin films of Al-doped ZnO (AZO) and (Al, K)-co-doped ZnO (AKZO) were synthesized by sol–gel spin coating and their structural and optical properties were investigated. All the films had a preferential orientation in which the c-axis was perpendicular to the substrate. The optical bandgap increased after Al doping, but decreased after K doping at a given Al doping concentration. UV emission and a broad visible emission band were observed in photoluminescence (PL) spectra. The intensity of both emission bands decreased after Al and K co-doping. PL excitation (PLE) spectra of the blue emission band indicate that the initial state is possibly the same for all the samples and a similar case occurs for the orange–red emission band. The green emission can be attributed to electronic transitions involving oxygen vacancies. A possible process for the orange–red emission of the thin films is radiative recombination of an electron trapped in a zinc interstitial defect with a hole deeply trapped in interstitial oxygen.     

Thermoelectric properties of Al-doped ZnO: experiment and simulation

Advancement in doping other elements, such as Ce, Dy, Ni, Sb, In and Ga in ZnO^[1], have stimulated great interest for high-temperature thermoelectric application. In this work, the effects of Al-doping in a ZnO system on the electronic structure and thermoelectric properties are presented, by experiment and calculation.Nanosized powders of Zn_1-xAl_xO (x=0, 0.01, 0.02, 0.03 and 0.06) were synthesized by hydrothermal method. From XRD results, all samples contain ZnO as the main phase and ZnAl₂O₄ (spinel phase) peaks were visible when Al additive concentrations were just 6 at%. The shape of the samples changed and the particle size decreased with increasing Al concentration. Seebeck coefficients, on the other hand, did not vary significantly. They were negative and the absolute values increased with temperature. However, the electrical resistivity decreased significantly for higher Al content.The electronic structure calculations were carried out using the open-source software package ABINIT^[2], which is based on DFT. The energy band gap, density of states of Al-doped ZnO were investigated using PAW pseudopotential method within the LDA+U. The calculated density of states was then used in combination with the Boltzmann transport equation^[3] to calculate the thermoelectric parameters of Al-doped ZnO. The electronic band structures showed that the position of the Fermi level of the doped sample was shifted upwards in comparison to the undoped one. After doping Al in ZnO, the energy band gap was decreased, Seebeck coefficient and electrical conductivity were increased.Finally, the calculated results were compared with the experimental results. The good agreement of thermoelectric properties between the calculation and the experimental results were obtained.