Interplay of native defect-related photoluminescence response of ZnO nanosticks subjected to 80 keV Ar ion irradiation

We report on the effect of 80 keV Ar⁺ ion irradiation on the luminescence response of zinc oxide (ZnO) nanosticks synthesized using a simple microemulsion route. The formation of nanoscale rods was confirmed from the transmission electron microscopy, whereas the hexagonal wurtzite phase of the nanorods was detected in an X-ray diffraction pattern. The photoluminescence pattern of the nanorods was dominated by various native defect states of ZnO, which are responsible for the quenching of the typical band edge emission of ZnO. Under Ar⁺ ion irradiation at a fluence of 1×10¹³ ions/cm², the band edge emission was recovered owing to the suppression of oxygen vacancy defects. In addition, the formation of new zinc vacancy and ionized zinc interstitial defects were also evident. Conversely, the band edge emission was found to be quenched as a result of the creation of more oxygen vacancy (V_O) defects due to ion irradiation (fluence: 1×10¹⁵ ions/cm²). The nuclear energy loss of the Ar⁺ ions in ZnO is responsible for the formation of point (vacancy-related) defects, while relatively small amount of electronic energy loss of the Ar⁺ ion results in the ionization of the neutral zinc interstitial (Zn_i) defects. The energy deposition scheme of the energetic ions has been elaborated with the help of theoretical modeling that explains the observed features quite satisfactorily.     

非掺杂ZnO薄膜中紫外与绿色发光中心

用直流反应溅射方法在硅衬底上淀积了ZnO薄膜,测量它们的光致发光(PL)光谱,观察到两个发光峰,峰值能量分别为3.18(紫外峰,UV)和2.38eV(绿峰).样品用不同温度分别在氧气、氮气和空气中热处理后,测量了PL光谱中绿峰和紫外峰强度随热处理温度和气氛的变化,同时比较了用FP-LMT方法计算的ZnO中几种本征缺陷的能级位置.根据实验和能级计算的结果,推测出ZnO薄膜中的紫外峰与ZnO带边激子跃迁有关,而绿色发光主要来源于导带底到氧错位缺陷(O_Zn)能级的跃迁,而不是通常认为的氧空 关键词： ZnO薄膜 热处理 光致发光光谱 缺陷能级     

The Formation of Defect Complexes in a ZnO Grain Boundary

The microscopic properties a ZnO grain boundary containing extrinsic point defects are studied using a density functional computational approach. The results show that the grain boundary acts as a sink for native defects, such as the zinc vacancy and the oxygen interstitial, and also for bismuth substitutional impurities. The defects tend to accumulate at under-coordinated sites in the boundary core and prefer to form small clusters. In particular the segregation of Bi promotes the formation of the other native defects by lowering their formation energies in the boundary. Individually, the native defects and the Bi impurity do not produce deep interface states in the band gap which are electrically active. However, when the defects cluster to form a Bi_Zn-V_Zn-O_i complex, new gap states are created of acceptor type. It is suggested that these new states are caused by defect interactions which compensate one another resulting in the depletion of an occupied impurity state and new bond formation. The results are discussed in terms of the Schottky barrier model commonly used to describe the electrical characteristics of ZnO varistors.     

Evidence for native-defect donors in n-type ZnO

Recent theory has found that native defects such as the O vacancy V(O) and Zn interstitial Zn(I) have high formation energies in n-type ZnO and, thus, are not important donors, especially in comparison to impurities such as H. In contrast, we use both theory and experiment to show that, under N ambient, the complex Zn(I)-N(O) is a stronger candidate than H or any other known impurity for a 30 meV donor commonly found in bulk ZnO grown from the vapor phase. Since the Zn vacancy is also the dominant acceptor in such material, we must conclude that native defects are important donors and acceptors in 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.     

Fast synthesize ZnO quantum dots via ultrasonic method

Green emission ZnO quantum dots were synthesized by an ultrasonic sol–gel method. The ZnO quantum dots were synthesized in various ultrasonic temperature and time. Photoluminescence properties of these ZnO quantum dots were measured. Time-resolved photoluminescence decay spectra were also taken to discover the change of defects amount during the reaction. Both ultrasonic temperature and time could affect the type and amount of defects in ZnO quantum dots. Total defects of ZnO quantum dots decreased with the increasing of ultrasonic temperature and time. The dangling bonds defects disappeared faster than the optical defects. Types of optical defects first changed from oxygen interstitial defects to oxygen vacancy and zinc interstitial defects. Then transformed back to oxygen interstitial defects again. The sizes of ZnO quantum dots would be controlled by both ultrasonic temperature and time as well. That is, with the increasing of ultrasonic temperature and time, the sizes of ZnO quantum dots first decreased then increased. Moreover, concentrated raw materials solution brought larger sizes and more optical defects of ZnO quantum dots.     

纳米ZnO薄膜的光致发光性质

利用溶胶－凝胶法制备了纳米ZnO薄膜,室温下测量了样品的光致发光谱(PL)、吸收谱(ABS)、X射线衍射谱(XRD)．X射线衍射(XRD)的结果表明：纳米ZnO薄膜呈多晶状态,具有六角纤锌矿晶体结构和良好的C轴取向．观察到二个荧光发射带,中心波长分别位于395 nm的紫带、524 nm的绿带和450 nm附近的蓝带．证实了纳米ZnO薄膜绿光可见发射带来自氧空位(VO)形成的浅施主能级和锌空位(VZn)形成的浅受主能级之间的复合;450 nm附近的蓝带来自电子从VO的浅施主能级到价带顶或锌填隙(Zni) 到价带顶或导带底到VZn的浅受主能级的复合．     

通过交替生长气氛调控N掺杂ZnO薄膜电学特性

使用分子束外延方法在c面蓝宝石衬底上生长了系列氮掺杂ZnO薄膜样品。在连续的富锌气氛环境中生长的样品,由于存在大量的施主缺陷,呈现n型电导。为了抑制施主缺陷带来的补偿效应,在生长过程中,通过周期性补充氧气,形成周期性的富氧气氛,缓解了氮掺杂浓度和施主缺陷浓度之间的矛盾。光致发光测量表明,通过交替生长气氛,氧空位和锌间隙等缺陷在薄膜中得到了显著抑制。通过交替生长气氛生长的外延薄膜的结晶质量也有所提高。样品显示出重复性较高的p型电导,载流子浓度可达到10¹⁶ cm^-3。周期性补氧调节生长气氛的生长方式是一种有效实现p型掺杂ZnO的方法。     

Nature of native defects in ZnO

This study revealed the nature of native defects and their roles in ZnO through positron annihilation and optical transmission measurements. It showed oxygen vacancies are the origin for the shift in the optical absorption band that causes the red or orange coloration. It also revealed experimental evidence that the donor nature of oxygen vacancy is approximately 0.7 eV. In addition, this work showed the Zn interstitial was not the donor in the as-grown ZnO and supported recent calculations that predicted hydrogen in an oxygen vacancy forms multicenter bonds and acts as a shallow donor.     

Metal-insulator electronic phase transitions in wide-gap ZnO semiconductors

Metal-insulator electronic phase transitions in wide-gap ZnO semiconductors have been studied. The influence of defect complex caused by oxygen vacancy and interstitial zinc atom on the metal-insulator transition is considered. The peculiarities of this transition in ZnO films doped with donor or acceptor impurity and the influence of mentioned defect complex on the charge carrier transfer mechanism were investigated.     

First-principles study of single intrinsic vacancy formation and its effect on the electronic density states and magnetic moment of V-doped ZnO

We calculated the formation energy of single vacancy in V-doped ZnO in different conditions (oxygen or zinc rich) by first principles. Effect of an intrinsic vacancy on the electronic density of states and magnetic moment of V-doped ZnO (Zn₁₅VO₁₆) with and without single vacancy was also calculated. Our calculation was performed by the CASTEP program within spin-polarized GGA approximation implemented in materials studio software. The formation energy showed that oxygen vacancy inclined to stay far from vanadium (V) and zinc vacancy preferred to stay at a position near V. The calculated formation energy also showed that a zinc vacancy may automatically occur but an oxygen vacancy may not appear automatically. Vanadium doping introduced spin-polarization around Fermi level. For an energy favorable vacancy, an oxygen vacancy had little effect on the electronic density of states. A zinc vacancy made the spin-polarization peaks around Fermi level broaden and decreased their magnitude. For the magnetic moment in energy favorable configurations, an oxygen vacancy had little effect on the magnetic moment; a zinc vacancy significantly decreased the magnetic moment (as high as 63.7%). Changes in magnetic moments were consistent with electronic density of states. Our calculation may interpret various experimental magnetic moment values. Our work also provided a reference for preparing V-doped ZnO-based dilute magnetic semiconductors.     

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.     

Single violet luminescence emitted from ZnO films obtained by oxidation of Zn film on quartz glass

The photoluminescence (PL) emission properties of ZnO films obtained on quartz glass substrate by the oxidation of Zn films were studied. The strong single violet emission centering about 413-424 nm was observed in the room temperature PL spectra of the ZnO films. The intensity of violet emission increased and the peak position shift from 424 to 413 nm with increasing oxygen pressures. The violet emission was attributed to the electron transition from the valence band to interstitial zinc (Zn_i) level under low oxygen pressure conditions (50-500 Pa). Under high oxygen pressure conditions (5000-23,000 Pa), both interstitial zinc (Zn_i) and zinc Vacancy (V_Zn) were thought to be responsible for the violet emission.     

p型K:ZnO导电机理的第一性原理研究

基于密度泛函理论,利用局域密度近似的第一性原理平面波赝势方法,对掺K以及含有氢填隙(H_i)、氧空位(V_O)、锌填隙(Zn_i)和锌空位(V_Zn)的K:ZnO电子结构分别进行了研究.结果表明,1) 单独掺K可引入浅受主,但系统总能增高;2) K与H共掺可降低系统总能,提升稳定性;3) V_O在K+H:ZnO中的形成比Zn_i困难得多,二者都是 关键词： 氧化锌 p型 第一性原理 电子结构     

Emission properties of Mn doped ZnO nanoparticles prepared by mechanochemical processing

Mechanochemical processing was reported to introduce lot of crystal defects which can significantly influence emission properties. Nevertheless, to the best of our knowledge, there are no reports on effect of mechanochemical processing on emission properties of transition metal ion doped ZnO. In this study, Zn_1?xMn_xO nanoparticles with different Mn content (x=0, 0.02, 0.04, 0.06, 0.08, and 0.1) were prepared by mechanochemical processing to study the effect of Mn doping and processing on emission properties. Confirmation of nanoparticles size and nanocrystalline nature of hexagonal wurtzite ZnO structure is carried out using transmission electron microscopy (TEM) and selected area electron diffraction (SAED), respectively. The samples were also characterized using Fluorescence Spectroscope before and after heat-treatment. The emission studies revealed that blue emission intensity is stronger compared to UV and green emission in contrast to the earlier reports, where other synthesis routes were employed for the ZnO nanoparticles' preparation. The blue emission originates from the zinc interstitial (Zn_i) and oxygen interstitial (O_i) defects, which indicate that the mechanochemical route resulted in more interstitial defects compared to oxygen substitution (O_Zn) and oxygen vacancy (V_o) defects which otherwise would give green emission. Mn doping resulted in shifting of near-band-edge (NBE) emission and the reduction in the intensities of NBE, blue and green emissions. The initial red shift at lower Mn content could be due to s–d and p–d exchange interactions as well as band tailing effect where as the blue shift at higher Mn content can be attributed to the Burstein-Moss shift. The reduction in emission intensity could be due to non-radiative recombination processes promoted by Mn ions with increasing Mn content.     

Microstructure and optical properties of ZnO nanoparticles prepared by a simple method

In this investigation, ZnO nanoparticles were prepared by a simple and rapid method. This method is based on the short time solid state milling and calcinations of zinc acetate and citric acid powders. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, photoluminescence and UV-vis spectroscopy. It was shown that the calcination temperature significantly affected the particle size and optical properties of the synthesized ZnO nanoparticles. Calculation based on the XRD data shows that the average sizes of ZnO particles are in agreement with those from TEM images and the size of the particles increases on increasing the calcination temperature. Also the band gap of samples decreased from 3.29 to 3.23 eV on increasing the calcination temperature from 350 to 600 °C. Photoluminescence analyses show that many defects such as interstitial zinc, zinc vacancy and oxygen vacancy are responsible for the observed optical properties.     

沉淀剂对ZnO压敏陶瓷缺陷结构和电气性能的影响

研究了不同沉淀剂(NH₄HCO₃和NaOH)对共沉淀法制备的ZnO压敏陶瓷性能的影响. 结果表明: 不同的沉淀剂对ZnO压敏陶瓷的微观结构及电气性能有明显的影响. 其中陶瓷微观结构的变化主要由沉淀剂本身的性质引起; 而电气性能的改变除了与微观结构相关外, 主要受不同沉淀剂对陶瓷晶界势垒参数的影响; 此外, 沉淀剂NaOH引入的Na⁺作为施主杂质离子掺杂ZnO压敏陶瓷, 增加晶粒中的自由电子浓度, 因此本征缺陷(锌填隙和氧空位)浓度受到抑制, 而锌填隙浓度相对于氧空位而言对施主离子掺杂更为敏感. 由此, 采用共沉淀法制备ZnO压敏陶瓷粉体时, 沉淀剂种类的选择很重要, 即使微量的杂质也会引起压敏陶瓷性能的较大改变, 应尽可能避免杂质离子的引入. 关键词： ZnO压敏陶瓷 缺陷结构 沉淀剂 介电性能     

氧空位浓度对ZnO电子结构和吸收光谱影响的研究

目前,氧空位对ZnO形成杂质能级的研究结果存在相反的结论,深杂质能级和浅杂质能级两种实验结果均有文献报道,并且,在实验中高温加热的条件下,氧空位体系ZnO中导带自由电子增加的来源认识不足.为了解决此问题,本文采用密度泛函理论框架下的第一性原理平面波超软赝势方法,建立了纯的与两种不同氧空位浓度ZnO超胞模型,分别对模型进行了几何结构优化、态密度分布、能带分布、布居值和差分电荷密度的计算.结果表明,氧空位浓度越大,系统能量越上升、稳定性越下降、形成能越高、氧空位越难、导带越向低能方向移动、电子跃迁宽度越减小、吸收光谱越红移.这对设计制备新型氧空位ZnO体系光学器件有一定的理论指导作用.     

Role of point defects on conductivity, magnetism and optical properties in In2O3

In order to assess the effects of point defects including transition metal doping on its electronic structure, the self-consistent band structure of the transparent oxide In₂O₃ (in the Ia₃ structure) has been calculated with oxygen vacancies, oxygen and indium interstitial atoms and several transition metal dopants using density functional theory based first principles calculations. An oxygen vacancy alone does not act as a strong native donor but when combined with interstitial indium and (substitutional) transition metal doping, shallow donor levels close to the conduction band are formed. Spin polarized calculations show measurable magnetism in some of the transition metal doped systems while the dielectric functions indicate whether such systems remain transparent among other things.     

Nanostructure growth-induced defect formation and band bending at ZnO surfaces

Morphological, electrostatic, and optical techniques reveal spontaneous growth of nano-“mounds” on ZnO polar surfaces in air creating native point defects at and under the surface that increase work function locally by hundreds of meV. Nanoscale surface photovoltage spectroscopy reveals Zn vacancies with gap states whose density grows with nano-mound proximity over hundreds of nanometers. The low activation energy for ZnO nano-mound growth with oxygen indicates interstitial Zn diffusion that feeds nanostructure growth, generating deep level acceptors that increase n-type band bending and impact Schottky barrier formation.