水热法制备ZnO晶体及纳米材料研究进展

纳米ZnO材料是新型宽禁带半导体材料,具有优良的光学及电学性能,在太阳能电池电极及窗口材料、声表面波材料、光电材料、敏感材料等方面得到广泛应用.纳米ZnO材料性能与制备技术有很大关系,本文综合评述了水热法制备纳米ZnO材料研究现状,研究了其制备特点及制备机理,从纳米ZnO晶体、阵列或薄膜、粉体三个方面制备实例研究了水热制备方法,最后探讨了纳米ZnO材料发展前景.     

直流溅射缓冲层生长ZnO/Si薄膜

ZnO是一种新兴的的宽禁带半导体材料,相对于传统的宽禁带材料有很多的优势.在相对成本低廉的Si衬底上生长ZnO薄膜是现在攻关的热门课题.目前用缓冲层方法生长ZnO薄膜取得了一些突破.本文利用直流溅射,先在Si衬底上溅射一层ZnO多晶薄膜,通过对直流溅射时间的控制,可以得到不同厚度的ZnO缓冲层.再利用MOCVD设备生长高质量的ZnO薄膜.通过研究发现,直流溅射ZnO薄膜的厚度对于最终的薄膜质量有很大的影响.随着缓冲层的引入,双晶衍射XRD的摇摆半宽有显著下降,并且随着最终ZnO薄膜质量上升,光致发光也有显著的提升.可见缓冲层的引入对ZnO/Si薄膜的质量和发光强度有很大的贡献.     

绒面ZnO/Si异质结太阳能电池的初步研究

以p型单晶硅<100>作为衬底材料,通过化学腐蚀法得到硅绒面表面结构,采用喷雾热解法沉积掺Al的ZnO薄膜于绒面硅上,结合微电子光刻、磁控溅射和真空蒸镀等工艺制作上、下表面电极,于400 ℃氮气氛围下快速退火合金,得到Ag/Ti/n-ZnO/p-Si/Al异质结太阳能电池.对电池样品进行了原子力显微镜、霍尔效应测试、X射线衍射谱、电流电压特性等分析.得到电池最佳性能为:开路电压V_(oc)=355 mV,短路电流I_(sc)=36 mA,填充因子FF=0.41,电池效率达到5.2;.绒面异质结构有效降低了电池表面的光反射,相对增加了p-n结的有效面积,电池效率得到一定程度的提高.ZnO与Si界面之间SiO_2层的存在是目前影响电池效率的主要因素.     

衬底温度对直流磁控溅射法制备掺锆氧化锌透明导电薄膜性能的影响

利用直流磁控溅射法在石英衬底上制备出了高透明导电的掺锆氧化锌(ZnO:Zr)薄膜.研究了衬底温度对ZnO:Zr薄膜结构、形貌及光电性能的影响.XRD表明实验中制备的ZnO:Zr为六方纤锌矿结构的多晶薄膜,具有垂直于衬底方向的c轴择优取向.实验所制备ZnO:Zr薄膜的晶化程度和导电性能对衬底温度有很强的依赖性.当衬底温度为300 ℃时, ZnO:Zr薄膜具有最小电阻率7.58×10-4 Ω·cm,其可见光平均透过率超过了91;.     

镓掺杂氧化锌透明导电薄膜的制备及其性能研究

采用射频磁控溅射方法在玻璃基片上制备了镓掺杂氧化锌(Ga∶ ZnO)透明导电薄膜,通过XRD、XPS、四探针仪和分光光度计等表征技术,研究了衬底温度对Ga∶ ZnO薄膜结构、组分、光学和电学性质的影响.结果表明:所有样品均为具有(002)择优取向的高质量透明导电薄膜,其晶体结构和光电性能与衬底温度密切相关.当衬底温度为673 K时,所制备的Ga∶ ZnO薄膜具有最大的晶粒尺寸(72.6 nm)、最低的电阻率(1.3×10-3Ω·cm)、较高的可见∶ZnO薄膜的光学能隙,结果显示随着衬底温度的升高,薄膜的光学能隙单调增加.     

超声喷雾热解法制备稀磁掺杂ZnO薄膜的研究

近年来,基于ZnO稀磁半导体在自旋电子器件方面的潜在应用价值,过渡金属掺杂的ZnO材料被广泛研究.但由于p型ZnO材料的制备非常困难,获得具有室温以上居里温度的Mn掺杂p型ZnO基稀磁半导体仍然是个难题.在N-In共掺杂成功实现ZnO薄膜p型掺杂的前期研究基础上,本研究采用超声喷雾热解(USP)法在Si基底上制备了Zn1-x,MnxO系列薄膜样品.X射线衍射表明所有ZnO薄膜样品都具有纤锌矿结构,没有发现其他物相的衍射峰存在.薄膜形貌研究发现,样品中的颗粒分布均匀.磁性测量表明N-Mn-In掺杂的样品显示出室温铁磁性.对N-Mn共掺杂和N-Mn-In掺杂的样品进行热处理后,发现薄膜的铁磁性能与薄膜中的空穴载流子具有直接的关联,这一现象与Mn掺杂的p型ZnO会显示室温铁磁性的理论预测是一致的,并用束缚磁性极化子模型解释了ZnO薄膜的铁磁性来源.     

基于CVD自组装生长氧化锌半导体纳米结构的光电导紫外探测器研究

报道了一种基于自组装生长ZnO纳米结构的光电导型紫外探测器.首先,在石英衬底上制备银叉指电极,然后溅射ZnO纳米薄膜形成一种共面光电导型金属-半导体-金属(MSM)结构,再利用低压CVD生长方法进行ZnO纳米线的原位生长,从而在器件顶部形成了ZnO纳米线垂直阵列和其上交错排列ZnO纳米线所构成的双层ZnO纳米线结构.这种器件底部的ZnO薄膜既是MSM光电导器件的电荷传输层,也同时作为上层ZnO纳米结构自组装生长的籽晶层,顶部的ZnO纳米结构层作为紫外光敏感层,测试结果表明该器件具有光响应速度快、光响应电流大和良好的紫外响应可分辨特性.研究表明,相比于单根ZnO纳米线光电导紫外器件而言,基于ZnO纳米结构膜层的光电导紫外探测器能够大幅度提高可测光响应电流.     

Si(111)衬底上ZnO薄膜的磁控溅射法制备及表征

采用磁控溅射法在(111)单晶硅衬底上沉积了ZnO薄膜,并研究了退火温度对ZnO薄膜晶体质量、晶粒度大小、应力和光致发光谱的影响.X射线衍射(XRD)表明薄膜为高度c轴择优取向.不同退火温度下的ZnO薄膜应力有明显变化,应力分布最为均匀的退火温度为500℃.室温下对ZnO薄膜进行了光谱分析,可观测到明显的紫光发射(波长为380nm左右).实验结果表明,用磁控溅射法在单晶硅衬底上能获得高质量的ZnO薄膜.     

采用MOCVD法在p型Si衬底上生长Zn0薄膜

采用金属有机物化学气相沉积(MOCVD)法在p型Si(100)衬底上生长未掺杂的n型ZnO薄膜.在不同的生长温度下,c轴取向ZnO薄膜被生长在Si衬底上,生长所采用的锌源为二乙基锌(DEZn),氧源为氧气(O2).通过X射线衍射(XRD)、光电子能谱(XPS)和荧光光(PL)谱研究了薄膜的结构和光学特性.研究表明温度为610℃时生长的ZnO薄膜显示最好的结构和光学特性.此外,所生长n-ZnO/p-Si异质结的I-V特性曲线都表现明显的整流特性,且反向漏电流很小.在620℃生长的异质结的漏电流相对最大,大于在其它温度下生长的异质结的漏电流.     

薄膜厚度对MOCVD法沉积ZnO透明导电薄膜的影响

本文研究了薄膜厚度对MOCVD技术制备未掺杂ZnO薄膜的微观结构和电学特性影响.XRD和SEM的研究结果表明,随着薄膜厚度的增加,ZnO薄膜(110)峰趋于择优取向,且晶粒逐渐长大,薄膜从球状和细长棒状演变为具有类金字塔绒面结构特征的ZnO薄膜;Hall测量表明,较厚的ZnO薄膜有助于提高薄膜电学特性,可归于晶粒长大和晶体质量提高.40min沉积时间(膜厚为1250nm)制备出的ZnO薄膜具有明显绒面结构,其晶粒尺寸为300～500nm,电阻率为7.9×10-3Ω·cm,迁移率为26.8cm2/Vs.     

制作压电器件氧化锌单晶的评述

氧化锌材料制作压电器件已经有很长的研究历史,自从Robert F.Service在1997年报道氧化锌可以在短波长范围实现蓝光输出后,氧化锌单晶在质量和体积方面取得了很大的研究进展。通过对比分析20世纪60年代以来氧化锌单晶压电特性的研究结果,指出迄今为止制作压电器件的氧化锌单晶仍然需要继续优化。     

不同位置Mg掺杂ZnO电荷转移和光学性质的第一性原理研究

基于密度泛函理论计算了本征氧化锌、6.25%Mg以及同位、邻位、间位12.5%Mg原子掺杂氧化锌晶体的几何结构、原子轨道电子布居、静电势和电子结构特征;探究了Mg原子掺杂对氧化锌能带结构、态密度以及对应的光学性质和电学性质的影响。结果表明Mg掺杂会导致氧化锌晶体的晶格体积变大,载流子迁移率降低和吸收边蓝移;邻位双原子掺杂(ZnO+2Mg-ac、ZnO+2Mg-ad)可以显著降低氧化锌的光吸收系数和反射率,提升对太阳光的透过率;Mg掺杂氧化锌晶体适用于制作高质量光学透射膜。     

ZnO晶体研究的统计分析

ZnO晶体是近年来材料科学的研究热点.本文采用科学计量学方法对1997～2005年间发表的ZnO材料相关研究文章进行了分析.目前ZnO研究论文增长迅速,表明该材料其受到很高的关注程度,主要集中在薄膜和纳米两个研究方向.其中,纳米ZnO研究论文增长更快,成为热点中的热点.ZnO体单晶也呈增长趋势,主要集中在水热生长研究.     

A ZnO/TiO2 composite nanorods photoanode with improved performance for dye‐sensitized solar cells

A dye‐sensitized solar cell (DSSC) based on ZnO/TiO₂ composite nanorods (NRs) photoanode is fabricated. The power conversion efficiency (PCE) of the ZnO/TiO₂ composite NRs film DSSC is 4.36%, which is obviously higher than that of DSSCs based on pure TiO₂ NRs (0.6%) and ZnO NRs (3.10%). The enhanced performance of ZnO/TiO₂ composite NRs film DSSC can be attributed to the combined effects of ZnO and TiO₂ NRs. In this architecture, the thick ZnO NRs overlayer offers a large surface area for enough dye absorption, while the thin TiO₂ NRs underlayer not only offers a direct and quick pathway for photoinjected electron transfer along the photoanode but also acts as a blocking layer, which effectively hinders the direct contact between the substrate and the electrolyte resulting in lower carrier recombination.     

水热法ZnO单晶的缺陷和光学特性研究

运用电感耦合等离子体原子发射光谱仪(ICP-AES)分析了比较了水热法ZnO晶体+c及-c部分的杂质,用四探针法比较了两部分的电阻率.结果表明, 晶体+c部分杂质含量少于-c部分,且前者电阻率明显高于后者.比较了Xe灯激发下两部分的光学性质,用氧气和氢气分别对+c部分ZnO进行处理,并进一步用He-Cd激光器对晶体的光学性能进行了研究,分析表明ZnO晶体416 nm左右的蓝光发射来自导带到锌空位(VZn)浅受主能级的跃迁,490 nm的蓝绿光发射与锌填隙(Zni)有关,540 nm附近的黄绿光发射与氧填隙(Oi)形成的能级有关.     

Surface‐morphology evolution of ZnO nanostructures grown by hydrothermal method

Surface‐morphology evolution of ZnO nanocrystals has been observed by the hydrothermal process. The effects of stirring time and ammonia content on the morphology evolution have been discussed, respectively. Extension of stirring time of the precursor results in morphology transformation from star‐like to wire‐like ZnO nanocrystals. ZnO nuclei aggregation and uniform Zn(OH)₂ precipitation can readily explain these two morphologies, respectively. By increasing the ammonia content in the solution, the morphology of ZnO crystals is transformed from an irregular shape to hexagon sheets to nanorods, and the side length of ZnO crystals is decreased accordingly. Hollow structures are realized at the subsequent solution aging process. Variation of zinc ammonic complex and minimum surface energy can well explain the morphology evolution of ZnO nanostructures.     

氧化锌单晶生长、载流子调控与应用研究进展

氧化锌(ZnO)是一种历史悠久的材料,由于其微观结构非中心对称,最初被预测可以应用于压电和非线性光学领域,又因为它在室温下具有宽的禁带和高的激子束缚能,是一类重要的第三代宽禁带半导体材料,在半导体领域受到了广泛关注。然而,在实际应用中,ZnO在上述各个领域都遇到了一些瓶颈问题:在压电领域,原本被认为是绝缘的ZnO出现了意外的导电性;在非线性光学领域,ZnO的折射率差很小,难以获得好的相位匹配;在半导体领域,难以同时获得高载流子浓度、高迁移率、高热稳定性的p型ZnO。本文主要针对以上ZnO的应用前景及相关瓶颈问题进行了总结,并提出了适用于离子型化合物半导体的载流子调控普适性理论,即:载流子类型完全由材料的精细化学组分完整表达式来决定。这一规则将原本被认为是无关的材料精细化学组分完整表达式和载流子类型两个概念联系起来,在认识上具有很大的突破,并形成了材料科学研究的新范式。该范式成功指导了高绝缘和高热稳定性的n型ZnO单晶以及高迁移率掺Al∶ZnO薄膜的生长,并为高载流子浓度、高迁移率、高热稳定性p型ZnO的制备提供了新思路。近来,除了上述应用领域外,ZnO还被发现在超快闪烁体和中红外(MIR)透明导电窗口领域具有较大的应用贡献,并推测这些领域很可能领先于ZnO原本受到重视的研究领域而取得真正的应用进展。     

Template effects on the morphology of ZnO via colloidal crystals with different functional groups

ZnO is an important wide bandgap compound semiconducting material and exhibits a wide range of novel structures that can be grown by tuning the growth rates along its fast growth directions. Highly ordered macroporous materials by using colloidal crystal template method are of great interest in many fields including photonic crystals and catalysts. In this study, ZnO with highly ordered porous structure was deposited by different electrochemical method. Nanomeshes, inverse opal structures, and spherical/ellipsoidal particles with pore arrays are fabricated by the colloidal crystals with different functional groups. The template effects on the morphology of the macroporous structures for different surface groups are studied. All the nanomeshes grows along the {111} plane family by colloidal crystals without functional groups. Disordered arrangements of the nanomeshes are induced by colloidal crystals with hydroxyl groups. The inverse opal structures fabricated by template with carboxyl groups are smoother in surface.     

Characteristics of sputtered zinc-oxide films prepared by UBM sputtering for thin film transistors

In this work, we describe the characteristics of zinc-oxide (ZnO) thin films synthesized on Si (001) and Corning (7059) glass substrates by unbalanced magnetron (UBM) sputtering under various ZnO film thicknesses and RF powers. We investigated the characteristics of ZnO films' structural, optical, and electrical properties with various film thicknesses and RF powers for the active channel in a thin film transistor (TFT). We used the UBM sputtering system for high rate deposition of ZnO films. The ZnO film surface was rough and the grain size of the film increased with increasing RF power and film thickness. The electrical properties improved with the increase of RF power and film thickness. These results can be explained by the improvement of the crystallinity in the ZnO film related to the grain size increase with increasing RF power and ZnO film thickness.     

Optical properties of ZnO nano fiber thin films grown by spray pyrolysis of zinc acetate precursor

Good homogeneous and stoichiometric ZnO nanofiber thin films have been deposited onto cleaned glass substrate by a simple spray pyrolysis technique under atmospheric pressure using zinc acetate precursor at temperature 200 °C. Films of various thicknesses have been obtained by varying the deposition time, while all other deposition parameters such as spray rate, carrier gas pressure and distance between spray nozzle to substrate were kept constant. Surface morphology and optical properties of the as deposited thin films have been studied by Scanning Electron Microscopy (SEM) attached with an EDX and UV visible spectroscopy. From EDX data, atomic weight% of Zinc and Oxygen were found to be 49.22% and 49.62% respectively. The SEM micrograph of the film shows uniform deposition and scattered nano fiber around the nucleation centers. The optical band gap of the ZnO thin films was found to be in the range 3.3 to 3.4 eV and the band gap decreases with thickness of the film. Optical constants such as refractive index, extinction coefficient, real and imaginary parts of dielelectric constants were evaluated from reflectance and absorbance spectra. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)