Er3+掺杂对ZnO/GaN发光二极管电致发光性能的调控

采用水热法制备了Er~(3+)掺杂的ZnO纳米棒阵列,通过场发射扫描电镜、X单晶衍射谱仪、透射电镜、微区显微光谱仪等对其形貌结构和发光性能进行了表征。结果表明,掺杂前后ZnO纳米棒的形貌及晶型结构未发生改变,Er~(3+)被均匀地掺杂至ZnO纳米棒中,并未发现形成Er_2O_3;掺杂Er~(3+)后样品的光致发光光谱显示400 nm左右蓝光部分占比先提高后减少,其可见光占比减少归因于Er~(3+)填补了一部分锌空位缺陷,同时抑制了一部分氧空位缺陷。结合荧光寿命光谱分析也可发现其辐射发光部分寿命延长,表明荧光辐射效率提高。最终选取掺杂浓度为30%的单根ZnO纳米棒制备ZnO/GaN异质结发光二极管,与未掺杂Er~(3+)的样品相比,其电致发光强度提高了5倍。本研究可为ZnO基电致发光器件的性能改善提供一种简便可行的方法。     

Er^(3+)掺杂对ZnO/GaN发光二极管电致发光性能的调控EI北大核心CSCD

采用水热法制备了Er^(3+)掺杂的ZnO纳米棒阵列,通过场发射扫描电镜、X单晶衍射谱仪、透射电镜、微区显微光谱仪等对其形貌结构和发光性能进行了表征。结果表明,掺杂前后ZnO纳米棒的形貌及晶型结构未发生改变,Er^(3+)被均匀地掺杂至ZnO纳米棒中,并未发现形成Er_(2)O_(3);掺杂Er^(3+)后样品的光致发光光谱显示400 nm左右蓝光部分占比先提高后减少,其可见光占比减少归因于Er^(3+)填补了一部分锌空位缺陷,同时抑制了一部分氧空位缺陷。结合荧光寿命光谱分析也可发现其辐射发光部分寿命延长,表明荧光辐射效率提高。最终选取掺杂浓度为30%的单根ZnO纳米棒制备ZnO/GaN异质结发光二极管,与未掺杂Er^(3+)的样品相比,其电致发光强度提高了5倍。本研究可为ZnO基电致发光器件的性能改善提供一种简便可行的方法。     

SiC衬底上异质外延GaN薄膜XPS谱和PL谱研究

利用X射线光电子能谱,对在SiC衬底上采用MOCVD异质外延的未故意掺杂的GaN进行N、Ga组份测试,同时用光致发光技术对样品进行发光特性的研究.结果表明,随着GaN薄膜中Ga百分含量逐渐减小,室温下黄光输出峰值强度却逐渐增加.因此,在Ga含量相对低的GaN薄膜中容易形成Ga空位(即Ga空位浓度较高),而此时,黄光辐射强度单调递增证明,黄光辐射与VGa密切相关.     

Mg掺杂ZnO纳米晶的低温共沉淀法制备及光学性质

采用共沉淀(co-precipitation)法制备了Mg掺杂ZnO纳米晶,分别用X射线衍射(XRD)、傅立叶变换红外光谱(FTIR)、紫外可见吸收(UV-Vis)光谱、光致发光(PL)光谱、透射电镜(TEM)、电子顺磁共振(EPR)等分析手段对样品进行了表征。探究了Mg离子在ZnO纳米晶中的存在状态,ZnO纳米晶颗粒尺寸和发射光谱随Mg掺杂浓度的变化,并对其发光机理进行了分析。结果表明:Mg离子在ZnO晶格中以部分晶格位,部分间隙位的方式存在,没有形成MgO表面壳层结构;随Mg掺杂浓度的增大,ZnO纳米晶的颗粒尺寸变小,发射光的光强增大。发射光的最佳激发波长为342nm,中心波长为500nm,荧光量子产率为22.8%。实验分析表明:Mg离子的掺杂在ZnO纳米晶中引入了锌空位(VZn),间隙位的镁离子(IMg),提供了新的复合中心,从而增强了ZnO纳米晶的光致发光。     

运用第一性原理研究氧化锌电阻阀片中氧空位与掺杂条件下ZnO晶体电学性质

为了比较Nb_2O_5、MnO_2、MgO三种添加剂对氧化锌电阻阀片电学性能影响,在微观层面模拟Nb、Mn、Mg三种元素分别掺杂ZnO完整超晶胞和带有氧空位缺陷的ZnO超晶胞,并运用第一性原理分析掺杂晶胞的特性.本文计算了晶体结构、掺杂形成能、氧空位形成能、能带结构、态密度、载流子迁移率、电导率等.结果表明,掺入Nb原子的掺杂体系晶格体积最大,Mg掺杂体系的形成能最大,稳定性最弱,Nb掺杂氧空位形成能最低,更容易引入氧空位.Nb掺杂的ZnO超晶胞禁带宽度最小,氧空位缺陷增大掺杂晶体的禁带宽度.在相同掺杂浓度和同等条件下,Mn掺杂的晶体电导率最高.     

La、Ce掺杂ZnO纳米晶的发光特性

共沉淀法制备了稀土镧、铈掺杂的ZnO半导体纳米晶。X射线衍射(XRD)结果表明:掺杂的ZnO纳米晶为六方纤锌矿结构,随掺杂浓度增加ZnO粒径减小。对铈掺杂纳米ZnO,以波长380nm激发,在443nm处出现了半峰宽较窄的强的蓝光发射峰;镧掺杂ZnO纳米晶则为从418~610nm的多峰宽带发射。     

纳米晶ZnO可见发射机制的研究

利用化学沉淀法制备了纳米ZnO粉体,室温下测量了样品的光致发光谱(PL)、X射线衍射谱(XRD),给出了样品的透射电子显微照片(TEM).X射线衍射(XRD)的结果表明:纳米晶ZnO具有六角纤锌矿晶体结构,颗粒呈球形或椭球形.观察到二个荧光发射带,中心波长分别位于398 nm的紫带和510 nm的绿光带.发现随退火温度升高,粒径增大,紫带的峰值减弱、绿带的峰值增强.证实了纳米晶ZnO绿光可见发射带来自氧空位形成的施主和锌空位形成的受主之间的复合.     

过渡金属元素X(X=Mn,Fe,Co,Ni)掺杂对ZnO基阻变存储器性能的影响

实验表明掺杂是一种改善阻变存储器性能的有效手段,但其物理机理鲜有研究.本文采用第一性原理方法系统研究了过渡金属元素X(X=Mn,Fe,Co,Ni)掺杂对ZnO基阻变存储器中氧空位迁移势垒和形成能的影响.计算结果表明Ni掺杂可同时有效降低+1和+2价氧空位在掺杂原子附近的迁移势垒,X掺杂均减小了氧空位的形成能,特别是掺杂Ni时氧空位的形成能减小最为显著(比未掺杂时减少了64%).基于该结果制备了未掺杂和Ni掺杂ZnO阻变存储器,研究表明通过掺杂控制体系中氧空位的迁移势垒和形成能,可以有效改善器件的初始化过程、操作电压、保持性等阻变性能.研究结果有助于理解探究影响阻变的微观机制,并可为掺杂提高阻变存储器性能提供一定的理论指导.     

低能质子辐照对ZnO白漆光学性能退化的影响

 通过光致荧光光谱解谱和X射线光电子能谱（XPS）分析,研究了ZnO白漆经受能量低于200 keV低能质子辐照过程中氧空位缺陷的形成与演化过程。XPS解析表明质子辐照后晶格氧减少,光致荧光光谱解析表明锌空位减少,说明ZnO白漆中氧空位数量增加,且双电离氧空位能够捕获价带中的电子转变为单电离氧空位,使单电离氧空位逐渐成为辐照产生的主要缺陷。质子辐照使ZnO白漆中氧空位数量增加,而氧空位易捕获电子形成色心,从而导致光学性能下降。     

掺Sb纳米ZnO的光致发光的研究

用柠檬酸盐法合成了不同掺杂浓度的纳米ZnO,粒径约为15nm。探讨了Sb掺杂对ZnO光致发光峰的影响。随着掺杂量的提高,样品的发射峰从428nm移至444nm。未掺杂ZnO的发光主要是源于电子从锌填隙形成的缺陷能级到价带顶的跃迁;随着掺杂量的提高,体系的氧空位增加,从而使得电子从氧空位所形成的缺陷能级到价带顶的跃迁占据主导,光致发射峰向长波方向移动。     

生长条件对Ga掺杂ZnO薄膜微观结构及光致发光性能的影响

利用热氧化法在不同参数条件下生长了Ga掺杂范围较宽的ZnO薄膜, 研究了ZnO薄膜的表面微观结构和光致发光性能. 研究表明: Ga以Ga³⁺存在并掺入ZnO晶格取代Zn²⁺, Ga的掺入改变了ZnO薄膜中的缺陷类型及浓度、化学计量比、薄膜表面结晶质量, 进而影响了薄膜的光致发光性能. 随着热氧化温度升高, Ga掺杂量增大, ZnO薄膜的晶粒尺寸增大, 尺寸更均一, 紫外光与可见光强度比增大. 随着热氧化时间延长, Ga掺杂量降低, ZnO薄膜的晶粒尺寸均一性变差, 紫外光与可见光强度比减小.     

Effect of synthesis conditions on microstructures and photoluminescence properties of Ga doped ZnO nanorod arrays

Ga doped ZnO nanorod arrays were prepared on silicon substrates in a mixture solution of zinc nitrate hexahydrate, methenamine, and gallium nitrate hydrate. Effect of synthesis conditions on crystal structures, morphologies, surface compositions, and optical properties was analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and photoluminescence techniques (PL). Experimental results reveal that Ga doping amount can reach 1.67 at% with the increase of gallium nitrate concentration. Ga doping greatly affects the morphologies of ZnO nanorod arrays. The photoluminescence spectra show a sharp UV emission and a broad visible emission. With Ga doping, UV emission has an apparent broadening effect and its peak shifts from 3.27 eV to 3.31 eV. The intensity ratio of UV emission to visible emission demonstrates that appropriate Ga doping amount is beneficial for the improvement of ZnO crystalline quality.     

掺Ga对ZnO电子态密度和光学性质的影响

采用密度泛函理论下的第一性原理平面波赝势方法,研究了掺Ga对纤锌矿ZnO电子态密度和光学性质的影响.从晶体配位场理论分析了掺Ga前后ZnO的成键情况及态密度的变化.计算得到掺Ga后电子浓度为2.42×10²¹ cm^-3,ZnO的载流子浓度提高了10⁴倍.比较分析掺Ga前后ZnO的介电函数、复折射率、吸收光谱和反射光谱可得,ZnO光吸收边向高能端移动,光学带隙增大.在可见光区,ZnO光吸收系数与反射率减小,光透过率显著提高,使ZnO:Ga成为 关键词： 密度泛函理论 态密度 光学性质 ZnO:Ga     

Study on the defects of ZnO nanowire

The room-temperature photoluminescence property of ZnO nanowires was studied. It showed an ultraviolet peak and a visible light band in the PL spectrum. Through Gaussian fitting, it was found that the visible light band can be divided into two peaks at 2.37 eV and 2.53 eV, which was originated from oxygen antisite and oxygen vacancy defects, respectively. After being exposed to air or post-annealed in oxygen ambience, aging effect was observed and the peak at 2.53 eV disappeared due to the removal of oxygen vacancy defects. Therefore, it is suggested that oxygen antisite and oxygen vacancy coexist in ZnO and induce visible light emission.     

High UV absorption efficiency of nanocrystalline ZnO synthesized by ultrasound assisted wet chemical method

Ultrasound assisted wet-chemical method has been carried out to incorporate different metal and non-metal ions such as; Li, S and Ag into ZnO. Characteristic studies on the structural and optical properties of the samples especially; the ultra-violet (UV) light absorption have been carried out. X-ray diffraction (XRD) analysis shows the formation of hexagonal crystal structure of ZnO along with changes in crystallinity and micro-strain with impurity doping. The morphology of the doped samples changes from particle like structure to flower and rod like structures showing the influence of dopant ions on nano ZnO growth. Infra-red (IR) transmittance spectra give information about the presence of metal–oxygen bond along with other stretching and bending modes. UV–visible absorption studies show the narrowing and sharpening of UV absorption band along with a blue shift for the doped samples. This shows the intensification in the excitonic absorption in ZnO after doping specific elements which will find application in UV blocking agents. Photoluminescence (PL) measurement shows the presence of excitonic emission and emissions due to intrinsic defects and external impurities in UV and visible regions respectively. These emission bands show a change in their position and intensity which has been explained on the basis of the existence of impurity levels in the band gap of ZnO.     

Recent progress of the native defects and p-type doping of zinc oxide

Zinc oxide(ZnO) is a compound semiconductor with a direct band gap and high exciton binding energy.The unique property,i.e.,high efficient light emission at ultraviolet band,makes ZnO potentially applied to the short-wavelength light emitting devices.However,efficient p-type doping is extremely hard for ZnO.Due to the wide band gap and low valence band energy,the self-compensation from donors and high ionization energy of acceptors are the two main problems hindering the enhancement of free hole concentration.Native defects in ZnO can be divided into donor-like and acceptorlike ones.The self-compensation has been found mainly to originate from zinc interstitial and oxygen vacancy related donors.While the acceptor-like defect,zinc vacancy,is thought to be linked to complex shallow acceptors in group-VA doped ZnO.Therefore,the understanding of the behaviors of the native defects is critical to the realization of high-efficient p-type conduction.Meanwhile,some novel ideas have been extensively proposed,like double-acceptor co-doping,acceptor doping in iso-valent element alloyed ZnO,etc.,and have opened new directions for p-type doping.Some of the approaches have been positively judged.In this article,we thus review the recent(2011-now) research progress of the native defects and p-type doping approaches globally.We hope to provide a comprehensive overview and describe a complete picture of the research status of the p-type doping in ZnO for the reference of the researchers in a similar area.     

电化学沉积高c轴取向ZnO薄膜及其光学性能分析

采用阴极还原方法，在透明导电玻璃(ITO)上制备了高c轴择优取向的ZnO薄膜.通过X射线衍射、扫描电子显微镜等表征技术，研究了沉积电流对ZnO薄膜的结构、应力状态及表面形貌的影响；利用光致荧光光谱及透射光谱等分析方法，探讨了沉积电流变化对ZnO薄膜的光学性能的影响.研究结果显示：各沉积电流下均可制得高c轴取向的ZnO薄膜；薄膜表面形貌受电流的影响较大；从透射谱可以看出，薄膜在可见光波段有较高透射率，且薄膜厚度随沉积电流的增大而增大.光致荧光测量表明，电化学沉积的ZnO薄膜具有明显的带隙展宽.而且，随着沉积电流的增加，带隙发光强度逐渐减弱，缺陷发光逐渐增强.     

Photoluminescence study of pure and Li-doped ZnO thin films grown by sol-gel technique

The effect of annealing atmosphere, temperature and aging on the photoluminescence of pure and Li-doped ZnO thin films has been investigated. Annealing the pure ZnO in N₂ and He above 800 °C results in green emission centered at ca. 500 nm; however annealing in air red-shifts the green emission to 527 nm. The visible emission of the Li-doped ZnO is found to be largely dependent on the annealing atmosphere. Warm-white photoluminescence with a broad emission band covering nearly the whole visible spectrum is obtained for the Li-doped ZnO films annealed in helium. The substitutional and interstitial extrinsic point defects created by lithium doping may mediate the relative concentration of the intrinsic defects and thereby tune the intrinsic-defect-related visible emission. The enhanced intensity ratio of near-band-edge ultraviolet emission to deep-level visible emission with aging time may be ascribed to both in-diffusion of oxygen from air and self-diffusion of oxygen interstitials to heal the oxygen vacancies during the aging process.     

Modulation of electrical and optical properties of gallium-doped ZnO films by radio frequency magnetron sputtering

Ga-doped ZnO(GZO) films are prepared on amorphous glass substrates at room temperature by radio frequency magnetron sputtering.The results reveal that the gallium doping efficiency,which will have an important influence on the electrical and optical properties of the film,can be governed greatly by the deposition pressure and film thickness.The position shifts of the ZnO(002) peaks in X-ray diffraction(XRD) measurements and the varied Hall mobility and carrier concentration confirms this result.The low Hall mobility is attributed to the grain boundary barrier scattering.The estimated height of barrier decreases with the increase of carrier concentration,and the trapping state density is nearly constant.According to defect formation energies and relevant chemical reactions,the photoluminescence(PL) peaks at 2.46 eV and 3.07 eV are attributed to oxygen vacancies and zinc vacancies,respectively.The substitution of more Ga atoms for Zn vacancies with the increase in film thickness is also confirmed by the PL spectrum.The obvious blueshift of the optical bandgap with an increase of carrier concentration is explained well by the Burstein-Moss(BM) effect.The bandgap difference between 3.18 eV and 3.37 eV,about 0.2 eV,is attributed to the metal-semiconductor transition.     

Ga高掺杂对ZnO的最小光学带隙和吸收带边影响的第一性原理研究

采用基于密度泛函理论框架下的第一性原理平面波超软赝势方法, 建立了纯的和四种不同Ga掺杂量的ZnO超胞模型, 分别对模型进行了几何结构优化、能带结构分布、态密度分布和吸收光谱的计算. 结果表明, 在本文限定的Ga掺杂量2.08 at%–6.25 at%的范围内, 随着Ga掺杂量的增加, 掺杂后的ZnO体系体积变化不是很大, 但是, 掺杂体系ZnO的能量增加, 掺杂体系变得越来越不稳定, 同时, 掺杂体系ZnO的Burstein-Moss 效应越显著, 最小光学带隙变得越宽, 吸收带边越向高能方向移动. 计算结果和实验结果相一致. 关键词： Ga高掺杂ZnO 电子结构 吸收光谱 第一性原理