ZnO氧缺陷的电子结构和光学性质

采用基于密度泛函理论的平面波超软赝势方法对ZnO_0.875的电子结构和光学性质进行了计算. 用第一性原理对含氧空位的ZnO晶体进行了结构优化处理, 计算了完整的和含氧空位的ZnO晶体的电子态密度. 结合精确计算的电子态密度分析了带间跃迁占主导地位的ZnO_0.875 材料的介电函数、吸收系数、折射系数、湮灭系数和反射系数, 并对光学性质和极化之间的联系做了详细讨论. 结果表明ZnO_0.875晶体是单轴晶体, 并且在低能区域存在因氧缺陷而造成的一些特性. 我们的研究结果为ZnO的发光特性提供新的视野, 同时为ZnO的光电子材料的设计和应用提供理论基础.     

Prediction of vibrational frequencies of possible intermediates and side products of the methanol synthesis on ZnO(0001) by ab initio calculations

We used ab initio density functional theory in combination with an embedded cluster approach to calculate vibrational spectra and formation enthalpies of possible intermediates and side products (spectator species) in the synthesis of methanol out of syngas on the ZnO(0001) surface. Our investigations are based upon our previous work on possible reaction pathways and activation barriers for this reaction at oxygen vacancies on ZnO(0001). We present and discuss calculated vibrational frequencies of short-living formyl, hydroxymethylene, formaldehyde, acetale, and hydroxymethyl intermediates and compare the calculated frequencies of formate and methoxy species as well as CO and CO(2) species, at the defect free surface and at oxygen vacancies, with recent experimental findings. All investigated species show characteristic features in their spectra. Therefore, the analysis of their vibrational frequencies is a suitable mean to distinguish them and gain new insights in this reaction which is of recent experimental interest. We are able to identify the structure and characteristics of different surface species, such as monodentate and polydentate carbonate and formate species, in agreement with experimental results.     

Ab initio cluster calculations for the absorption energies of F and F+ centers in bulk ZnO

We present the results of a series of ab initio calculations on the ground states and the low lying excited states of the F and F+ centers in bulk ZnO. Both types of F centers are oxygen vacancies, causing rather strong distortions of the local geometries. The calculations were performed by means of wave function based methods, mostly at the CASSCF level. Dynamic correlation was included for the first two coordination shells of the F centers. The calculated absorption energy for the F+ center (3.19 eV) is in excellent agreement with the experimental value of 3.03 eV. For the emission from the 3T2 state of the F center to the 1A1 ground state we obtained a transition energy of 2.73 eV. Experimentally, a green photoluminescence is observed at 2.38-2.45 eV. We estimated that the errors in our calculation should be even smaller in the latter case than for the F+ state, where the calculated transition energy differs by less than 0.2 eV from the experimental value. Therefore, we assume that the 3T2 to 1A1 transition is not the origin of the green luminescence.     

Modulation of the morphology of ZnO nanostructures via aminolytic reaction: from nanorods to nanosquamas

Various diversified morphology-modulated ZnO nanostructures including nanorods, nanotetrahedrons, nanofans, nanodumbbells, and nanosquamas have been successfully prepared via an effective aminolytic reaction of zinc carboxylates with oleylamine in noncoordinating and coordinating solvents. Their shape- and structural defect-dependent optical properties have been investigated as well. Highly crystalline defect-free nanotetrahedrons/nanorods have a sharp band-edge emission, and highly defective nanodumbbells/nanosquamas show a very broad deep-trap emission, resulting from the radiative recombination of electrons with holes in singly ionized oxygen vacancies.     

Preparation and optical properties of high-quality oriented of Al and Er co-doped ZnO thin films

High-quality c-axis oriented Al and Er co-doped ZnO films were prepared on the quartz glasses by sol?Cgel method. In order to obtain the optimal processing parameters for the growth of the oriented film, an L₁₆ (4⁵) orthogonal experimental design was chosen. The experimental results show the rank of 5-factors as follows: Er at.%?>?the number of coating layer?>?annealing temperature?>?Al at.%?>?the concentration of the sol. The Al and Er co-doped film prepared using the optimal parameters exhibits the preferential orientation along the c-axis perpendicular to the substrate surface. In addition, the structural, morphological and optical properties of the films were studied by X-ray diffraction, scanning electron microscopy, and UV?Cvisible spectrophotometer, respectively. The photoluminescence spectra were also used to characterize the luminescence properties of the samples. It is found that when ZnO was co-doped with 7?% Al and 1.5?% Er, the blue emission centered at 465?nm disappears and the green emission centered at 547?nm increases with a blue shift, resulted from the rapid reducing of the interstitial Zn defect, and increasing of the oxygen defects and vacancies caused by Al³⁺ and Er³⁺ dopants.     

Growth and optical properties of faceted hexagonal ZnO nanotubes

Well-faceted hexagonal ZnO nanotubes were synthesized by a simple hydrothermal method and the subsequent aging process without any catalysts or templates. The formation of the tubular structure is closely linked to the polarity of ZnO and the selective adsorption behavior of Zn2+ amino complexes. The surface-related optical properties were studied with use of Raman and photoluminescence spectra. It was found that the oxygen vacancy-related visible emission intensity decreased while surface defect-related visible emission intensity increased when the nanotubes were annealed in oxygen ambient. The anomalous enhancement of PL integrated intensity with the temperature shows fairly high surface state density existing in ZnO nanotubes.     

Synthesis, characterization and photoluminescence properties of Ce3+-doped ZnO-nanophosphors

The present study involves the synthesis of Ce³⁺ doped ZnO nanophosphors by the zinc nitrate and cerium nitrate co-precipitation method. The synthesized nanophosphors were characterized with respect to their crystal structure, crystal morphology, particle size and photoluminescence (PL) properties using X-ray diffraction (XRD), scanning electron microscopy (SEM)/energy dispersive X-ray (EDX), transmission electron microscopy (TEM)/Energy-dispersive X-ray spectroscopy (EDS) and PL-spectroscopy respectively. XRD results revealed that ZnO nanophosphors are single phase and cubic type structures. Further, PL spectra of ZnO:Ce³⁺ nanophosphors showed green emission because of the charge transfer at single occupied oxygen vacancies with ZnO holes and red emission due to the cerium ion transitions. Intensity and fine structure of the Ce³⁺ luminescence and its temperature dependence are strongly influenced by the doping conditions. The formation of ZnO:Ce³⁺ nanophosphors was confirmed by Fourier transform infrared (FTIR) and XRD spectra.     

Tailoring the charge carrier dynamics in ZnO nanowires: the role of surface hole/electron traps

Post-fabrication thermal-annealed ZnO nanowires (NWs) in an oxidizing (or a reducing) ambient were investigated using transient photoluminescence and X-ray photoelectron spectroscopy. Our findings reveal an ultrafast hole-transfer process to the surface adsorbed oxygen species (e.g., O(2)(-)) occurring within a few hundred picoseconds (ps) in the air-annealed samples; and an ultrafast electron-transfer process to charged oxygen vacancies (i.e., V(O)(2+)) occurring within tens of ps in the H(2)-annealed samples. Contrary to the common perception that the band edge emission (BE) dynamics are strongly influenced by the carrier trapping to the green emission related defect states (i.e., V(Zn)), these above processes compete effectively with the ZnO BE. Hole trapping by ionized V(Zn), which occurs in an ultrashort sub-ps-to-ps timescale (and hence limits its effective hole capture radius), however, has less influence on the BE dynamics. Importantly, our findings shed new light on the photoinduced charge transfer processes that underpins the novel properties of enhanced photocatalytic activity, photovoltaic performance, and photoconductivity response of ZnO NWs, thereby suggesting a strategy for tailoring the ultrafast carrier dynamics in ZnO NW-based devices.     

ZnO-based hollow microspheres: biopolymer-assisted assemblies from ZnO nanorods

Many efforts have been made in fabricating three-dimensional (3D) ordered zinc oxide (ZnO) nanostructures due to their growing applications in separations, sensors, catalysis, bioscience, and photonics. Here, we developed a new synthetic route to 3D ZnO-based hollow microspheres by a facile solution-based method through a water-soluble biopolymer (sodium alginate) assisted assembly from ZnO nanorods. The products were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, and X-ray photoelectron spectroscopy. Raman and photoluminescence spectra of the ZnO-based hollow microspheres were obtained at room temperature to investigate their optical properties. The hollow microspheres exhibit exciting emission features with a wide band covering nearly all the visible region. The calculated CIE (Commission Internationale d'Eclairage) coordinates are 0.24 and 0.31, which fall at the edge of the white region (the 1931 CIE diagram). A possible growth mechanism of the 3D ZnO superstructures based on typical biopolymer-crystal interactions in aqueous solution is tentatively proposed, which might be really interesting because of the participation of the biopolymer. The results show that this biopolymer-directed crystal growth and mediated self-assembly of nanocrystals may provide promising routes to rational synthesis of various ordered inorganic and inorganic-organic hybrid materials with complex form and structural specialization.     

The study of electronic and optical properties of ZnO/MoS2 and its vacancy heterostructures by first principles

Based on the first principles calculation, the effects of vacancies on the structural, electronic and optical properties of ZnO/MoS₂ heterostructure are investigated in this work. The results show that vacancies could exist stably in the heterojunctions and cause a significant decrease in bandgap. ZnO/MoS₂ with an O vacancy maintains semiconductor property with a bandgap of 0.119 eV, while heterostructure with a Zn vacancy exhibits metallic characteristic. Furthermore, the absorption capability of defective heterojunctions has been extended to infrared light region with obvious redshift. To sum up, vacancy engineering effectively changes the electronic and optical properties of ZnO/MoS₂ heterostructure, which provides a feasible approach for adjusting the optoelectronic properties of two-dimensional heterostructures and broadening their application in functional nanoelectronic and optoelectronic devices.     

Optical properties of sol-gel synthesized calcium doped ZnO nanostructures

Optical properties of Ca doped ZnO nanoparticles prepared at room temperature through wet chemical method have been investigated. X-ray diffraction studies show that particles are crystalline in nature and doping did not induce impurity phases. Optical absorption measurements show an absorption peak at ∼372 nm which is due to excitonic absorption of the ZnO. Photoluminescence studies reveal a broad emission at an excitation wavelength of 335 nm and the bands are attributed to near band edge emission, oxygen vacancies, surface dangling bonds and zinc interstitials. Incorporating Ca²⁺ induces reduction in near band edge emission and there is an enhancement in the oxygen vacancy peaks which are attributed to the shape changes in the nanoparticles.     

Preparation of ZnO nanoparticles in a reverse micellar system and their photoluminescence properties

ZnO nanoparticles with spherical morphology and narrow size distribution were obtained by calcination of Zn(OH)2 nanoparticles, which were prepared in a polyethylene glycol mono-4-nonylphenyl ether (NP-5)/cyclohexane reverse micellar system and incorporated into polyurea (PUA) via an in situ polymerization of hexamethylene diisocyanate (HDI). The resulting ZnO nanoparticles demonstrated a near-UV emission and a green emission, the intensity ratio of which depended on calcination conditions. For the nanoparticles studied, the calcination atmosphere influenced remarkably the photoluminescence properties such as intensity ratio of the near-UV emission to green emission, rather than the size, morphology, and crystallinity of the ZnO nanoparticles. The green emission decreased by calcination in O2 flow but increased by calcination in N2 flow, as compared with the case calcined in air flow. This finding suggests that the green emission is enhanced with the increase of the number of oxygen vacancies of the ZnO nanoparticles and thus the photoluminescence properties of the nanoparticles were successfully controlled by the calcination condition, without changing the size and morphology.     

富表面氧空位Fe2O3/ZnO催化剂在光催化合成氨中的应用

光催化合成氨是一种绿色节能的合成氨技术,设计制造丰富的表面氧空位和异质结构是促进氮分子活化和抑制电子-空穴复合的重要方法。我们以乙二醇作为还原剂,采用溶剂热法制备合成了Fe2O3/ZnO光催化剂,利用X射线衍射(XRD)、透射电镜(TEM)、电子顺磁共振(EPR)、紫外-可见漫反射(UV-Vis DRS)、荧光光谱(PL)及光电流(PC)对Fe2O3/ZnO催化剂进行表征,并考察了Fe2O3/ZnO催化剂在常温、常压下的光催化合成氨的性能。4%Fe2O3/ZnO催化剂在无牺牲剂下用于光催化合成氨,有较好的光催化效率和稳定性,其合成氨效率达到2059μmol·L-1·g-1·h-1。其高催化效率归因于:可见光区域吸收的提高、氮分子在表面氧空位与Fe3+活性中心上的协同活化及光生电子与空穴的高分离效率。     

Preparation and Photoluminescence of ZnO Nanorods Arrays

A high-density well-aligned Zinc Oxide nanorod array was synthesized on Si (100) substrate by a simplevapor deposition under normal pressure using neither a catalyst and nor pre-deposition of ZnO film. Various different morphologies were obtained in different deposition regions. Si substrate put over the Zn source was the key factor in getting a well-aligned sample. Field emission scanning electron microscope (FESEM) observations and X-ray diffraction were carried out to characterize the surface morphology and crystalline quality of the samples. The growth mechanism is discussed. The photoluminescence properties of the ZnO samples were also investigated. It is suggested that the green band is related to oxygen vacancies and thekinetic process involving transition from shallow donor to deep acceptor level.     

Some clues about the interphase reaction between ZnO and MnO2 oxides

Raman spectroscopy is used to evidence both the nature of the interphase reaction between ZnO and MnO₂ particles and its kinetic evolution. Zn cations migrate from the ZnO grains during oxygen vacancies formation process and diffuse into the MnO₂ particles leading to an interphase region with an intermediate valence Mn⁺³-O-Mn⁺⁴. Large amounts of desorbed Zn cations promote the formation of ZnMn₂O₄ structure, in addition to the intermediate valence state. The system evolves towards complete formation of the spinel phase at higher thermal treatment times. The reactivity of the ZnO plays an important role in the formation of this interphase. Low-reactivity ZnO powder, in which the oxygen vacancies are previously produced, shows a stabilization of the intermediate valence state with very limited formation of the spinel phase. A clear correlation between the amount of the intermediate state interphase and the magnetic properties has been established.     

Photoluminescence of ZnO nanoparticles prepared by laser ablation in different surfactant solutions

ZnO nanoparticles were prepared by laser ablation of a zinc metal plate in a liquid environment using different surfactant (cationic, anionic, amphoteric, and nonionic) solutions. The nanoparticles were obtained in deionized water and in all surfactant solutions except the anionic surfactant solution. The average particle size and the standard deviation of particle size decreased with increasing amphoteric and nonionic surfactant concentrations. With the increase of the amphoteric surfactant concentration, the intensity of the defect emission caused by oxygen vacancies of ZnO rapidly decreased, while the exciton emission intensity increased. This indicates that anionic oxygen in the amphoteric surfactant molecules effectively occupied the oxygen vacancy sites at the ZnO nanoparticle surface due to charge matching with the positively charged ZnO nanoparticles.     

Ab initio calculations of the O1s XPS spectra of ZnO and Zn oxo compounds

O1s core level binding energies of oxygen atoms in bulk ZnO, at different ZnO surfaces, and in some Zn oxo compounds were calculated by means of wave function based quantum chemical ab initio methods. Initial and final state effects were obtained by Koopmans' theorem and at the DeltaSCF level, respectively. After correction for scalar relativistic effects and electron correlation, the calculated XPS peak positions are in excellent agreement with the available experimental data for all systems included in the present study. The O1s core level shifts between an isolated H2O molecule and the Zn oxo compounds or ZnO, as well as between oxygen atoms in bulk ZnO and at various ZnO surfaces, can be understood by means of Madelung potentials and electronic relaxation or screening. XPS spectra were calculated for various cluster models which are designed to describe different possibilities of stabilizing the polar O-terminated ZnO(0001) surface by the adsorption of H atoms. The experimental spectra are only compatible with the theoretical results for the fully hydroxylated H-ZnO(0001) surface exhibiting a (1x1) surface structure.     

Transition levels of defect centers in ZnO by hybrid functionals and localized basis set approach

A hybrid density functional study based on a periodic approach with localized atomic orbital basis functions has been performed in order to compute the optical and thermodynamic transition levels between different charge states of defect impurities in bulk ZnO. The theoretical approach presented allows the accurate computation of transition levels starting from single particle Kohn-Sham eigenvalues. The results are compared to previous theoretical findings and with available experimental data for a variety of defects ranging from oxygen vacancies, zinc interstitials, and hydrogen and nitrogen impurities. We find that H and Zn impurities give rise to shallow levels; the oxygen vacancy is stable only in the neutral V(O) and doubly charged V(O) (2+) variants, while N-dopants act as deep acceptor levels.     

The synthesis and optical properties of different zinc oxide nanostructures

The tetrapod-like whiskers (T-ZnO), nanoaeroplanes, nanocombs, nanobelts, bead-like nanoforms and many other forms of hexagonal zinc oxide were synthesized by the chemical deposition process (CVD). From the experimental results it can be seen that the composition of source gases and the speed of oxidation are essential to the growth of each of these morphologies of zinc oxide. By controlling the growth conditions, one novel morphology of ZnO (bead-like nanoform) has been obtained. The ZnO tetrapod-like whiskers were grown without catalysts on the walls of quartz tube. The structure and morphology of the T-ZnO was characterized. All four legs of as-grown ZnO nanotetrapods are needle-like and hexagonal shaped and grow in the ±[0001] direction. The effect of synthesis conditions on the morphology and size T-ZnO was observed. Possible mechanisms of growth were investigated. The lengths of the legs of the tetrapods range from 1 to 15 μm and diameter varying from 0.03 to 1 μm during the synthesis. In the photoluminescence spectra T-ZnO clearly shows two maxima at UV and visible regions. The oxygen impurity, particularly, oxygen flow rates mainly influences on increasing (decreasing) at PL peaks. The maximum near of 590–610 nm (～2 eV), confirming the influence of native defects (oxygen vacancies and interstitials) on the PL intensity and optical quenching exciton peak.     

ZnO纳米线阵列的电沉积法制备及表征(英文)

利用直流电沉积方法在多孔氧化铝模板的孔洞中生成锌纳米线,在氧气氛围中,于800°C下氧化2h,将氧化铝中的锌氧化成氧化锌.本研究利用氧气氛围进行锌的氧化,大大提高了传统方法的氧化锌纳米线的制备效率.用场发射扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)和X射线衍射仪(XRD)对其形貌及成分进行表征和分析,结果表明,氧化铝模板的有序孔洞中填充了大尺寸、均匀连续的多晶态氧化锌纳米线.纳米线具有约1000:1的高纵横比,其长度等于氧化铝模板的厚度,直径约为80nm.光致发光(PL)光谱表明,氧化锌纳米线在504nm处有由于氧空位引起的较强蓝绿光发射.这为进一步研究ZnO/AAO组装体发学性质和开发新型功能器件提供了基础.