Large-scale synthesis of ZnO nanowires using a low-temperature chemical route and their photoluminescence properties

Single-crystalline zinc oxide (ZnO) nanowires were synthesized from zinc powder and H₂O through a simple chemical route at 730 °C in Ar atmosphere. The potential exists for bulk synthesis of ZnO nanowires at temperatures significantly less than the 200–300 °C of thermal evaporation methods reported formerly. Scanning electron microscopy and transmission electron microscopy observations reveal that the ZnO nanowires are structurally uniform, have lengths up to several hundreds of micrometers and diameters of about 40–60 nm and crystallize in a hexagonal structure. The growth of ZnO nanowires is controlled by the vapor–solid crystal-growth mechanism. Photoluminescence measurements show that the ZnO nanowires have a strong near-band ultraviolet emission at 380 nm and a green light emission at 520 nm caused by oxygen vacancies. PACS 81.05.Ys; 78.55.Et     

Preparation and photoluminescence of Sc-doped ZnO nanowires

We demonstrate bulk synthesis of single-crystal Sc-doped ZnO nanowires by using (Sc+Zn) powders at . These mass nanowires are characterized through X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy (TEM), selected area electron diffraction, and high-resolution TEM, which have uniform diameters of about 40 nm and microns of several decades in length. The growth of ZnScO nanowires is suggested for self-catalyzed vapor–liquid–solid. In particular, PL spectra of these nanowires show emission peaks that intensely shift to long wavelength with increasing Sc and the doping quantity is found responsible for the different characteristics, in which PL mechanism is explained in detail.     

Synthesis and red-shifted photoluminescence of single-crystalline ZnO nanowires

Local-oriented single-crystalline ZnO nanowires have been synthesized in large scale by a simple microemulsion method in the presence of sulfonate-polystyrene (S-PS) and dodecyl benzene sulfonic acid sodium salt (DBS). The as-prepared product is characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), infrared (IR) spectra and photoluminescence (PL) spectrum. The nanowires exhibit a local congregation and preferentially grow along the [0 0 2] facet. FT-IR spectrum indicates that S-PS is adsorbed on the surface of ZnO nanowires. The PL spectrum shows evidently red-shifted ultraviolet (UV) emission.     

Mn掺杂ZnO纳米线磁性质的第一性原理研究

本文采用第一性原理方法系统研究了Mn原子单掺杂和双掺杂ZnO纳米线的稳定性和磁性质.所有掺杂纳米线的束缚能都为负值,表明掺杂增强了纳米线的稳定性.表面掺杂纳米线显示了直接带隙半导体特性,而中间掺杂纳米线显示了间接带隙半导体特性.纳米线的总磁矩主要来源于Mn原子3d轨道的贡献.由于杂化,相邻的O原子和Zn原子也产生了少量自旋.在超原胞内,Mn原子和O原子磁矩平行排列,表明它们之间是铁磁耦合.     

Excitonic polaron and phonon assisted photoluminescence of ZnO nanowires

The coupling strength of the radiative transition of hexagonal ZnO nanowires to the longitudinal optic (LO) phonon polarization field is deduced from temperature dependent photoluminescence spectra. An excitonic polaron formation is discussed to explain why the interaction of free excitons with LO phonons in ZnO nanowires is much stronger than that of bound excitons with LO phonons. The strong exciton-phonon coupling in ZnO nanowires affects not only the Haung-Ray S factor but also the FXA-1LO phonon energy spacing, which can be explained by the excitonic polaron formation.     

Surface effects on photoluminescence of single ZnO nanowires

The influence of surface effects on the temperature dependent photoluminescence (PL) spectra from individual ZnO nanowires has been studied. It is found that the surface effects of the nanowire are very important in both ultraviolet (UV) and visible emission. We propose a new luminescence mechanism based on the recombination related to oxygen vacancies to explain the temperature dependent visible emission, which is significantly influenced by the carrier depletion and band bending caused by surface effects. In addition, the observed attenuation of UV emission with increasing temperature is ascribed to the decreasing depletion region and the increasing surface states related nonradiative recombination.     

ZnO纳米线紫外探测器的制备和快速响应性能的研究

一维ZnO纳米结构由于具有比表面积大、室温下具有大激子结合能等特点而受到广泛关注. 但是如何实现纳米结构的器件一直是目前研究的一个挑战. 文章通过水热方法, 在玻璃衬底上实现了ZnO纳米线横向生长, 并制备出基于ZnO纳米线的金属-半导体-金属紫外探测器. 测量结果显示器件在365 nm处探测器的响应度达到5 A/W, 并且制备的探测器在空气中对紫外光照具有快速的响应, 其上升时间约4 s, 下降时间约5 s, 这与ZnO纳米线中的氧空位吸附和脱附水分子相关.     

Fabrication and temperature-dependent photoluminescence spectra of Zn–Cu–In–S quaternary nanocrystals

A series of Zn-Cu-In-S nanocrystals （ZCIS NCs） are prepared and the optical properties of the ZCIS NCs are tuned by adjusting the reaction time. It is interesting to observe that the temperature-dependent photoluminescence （PL） spectra of the ZCIS NCs show a redshift with decreasing intensity at low temperature （50-280 K） and a blueshift at high temperature （318--403 K）. The blueshift can be explained by the thermally active phonon-assisted tunneling from the excited states of the low-energy emission band to the excited states of the high-energy emission band.     

Influence of metallic coatings on the photoluminescence properties of ZnO nanowires

We report on low‐temperature photoluminescence studies of ZnO nanowires coated with thin metallic films. For all analyzed metals (Al, In, Au, Ni, Cu), we find an increased relative intensity of the green deep‐level emission. This is accompanied by a significant reduction of the relative intensity of the surface exciton band. The observed effects are most likely related to the formation of metal induced gap states in the surface region of the ZnO nanowires. A model for the band structure in the surface region of the metal‐coated nanowires is proposed that successfully explains the changes in the photoluminescence spectra after the coating process. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Manifestation of oxygen desorption in photoluminescence spectra of ZnO

The influence of oxygen desorption on the photoluminescence of zinc oxide has been investigated. Photodesorption and thermal desorption of oxygen have been controlled using mass spectrometry. It has been found that the removal of oxygen from the ZnO surface leads to a manifold increase in the exciton photoluminescence intensity. The process has a reversible character. The mechanism of increase in the exciton luminescence intensity of ZnO during the oxygen desorption has been discussed.     

Auger and photoluminescence analysis of ZnO nanowires grown on AlN thin film

ZnO nanowires were grown on AlN thin film deposited on the glass substrates using a physical vapor deposition method in a conventional tube furnace without introducing any catalysts. The temperature of the substrates was maintained between 500 and 600 °C during the growth process. The typical average diameters of the obtained nanowires on substrate at 600 and 500 °C were about 57 and 22 nm respectively with several micrometers in length. X-ray diffraction and Auger spectroscopy results showed Al diffused from AlN thin film into the ZnO nanowires for the sample grown at 600 °C. Photoluminescence of the nanowires exhibits appearance of two emission bands, one related to ultraviolet emission with a strong peak at 380-382 nm, and the other related to deep level emission with a weak peak at 503-505 nm. The ultraviolet peak of the nanowires grown at 500 °C was blue shifted by 2 nm compared to those grown at 600 °C. This shift could be attributed to surface effect.     

Structural, Raman, and photoluminescence characteristics of ZnO nanowires coated with Al-doped ZnO shell layers

Al-doped ZnO (AZO) shell layers were coated on core ZnO nanowires to fabricate ZnO/AZO core–shell nanowires. The energy-dispersive X-ray spectra confirmed the presence of Al element in the shell layers, and the lattice resolved transmission electron microscopy image revealed that these layers corresponded to the hexagonal ZnO structure. The X-ray diffraction pattern exhibited a shift of the ZnO peaks, suggesting the substitutive incorporation of Al into the ZnO lattice. The A₁(LO) mode line in the Raman spectra was enhanced by the AZO coating. In the photoluminescence measurements, the AZO coating enhanced the intensity ratio of the UV to green emission.     

Fabrication of Co-doped ZnO nanowires and their temperature-dependent ultraviolet emission properties

Co-doped ZnO nanowires have been fabricated through a high temperature vapor–solid deposition process. The temperature-dependent ultraviolet emission properties of Co-doped ZnO nanowires under 10–300 K were reported. The results show that there are multipeak emissions situated at the ultraviolet region. The investigation of the excitonic transition in Co-doped ZnO nanowires shows that there is an intensive ultraviolet periodic emission of Co-doped ZnO nanowires under low temperature. The oscillatory structure has an energy periodicity about 70 meV. The oscillatory structure is mainly attributed to the longitudinal optical phonon replicas of the free exciton. The ultraviolet emission shows an obvious redshift with the increasing temperature.     

Ferromagnetism in Mn-doped GaN nanowires

Using density functional theory we show that the magnetic coupling of Mn atoms in the nanowires, unlike that in the thin film, is ferromagnetic. This ferromagnetic coupling, brought about due to the confinement of electrons in the radial direction and the curvature of the Mn-doped GaN nanowires' surface, is mediated by N as is evidenced from the overlap between Mn 3d and N 2p states. Calculations of the anisotropic energy further show that the magnetic moment orients preferably along the [1010] direction while the wire axis points along the [0001] direction.     

Fabrication and photoluminescence of P doped ZnO nanobelts by thermal evaporation method

Uniform and flat single crystal ZnO:P nanobelts (NBs) were fabricated on Si (1 0 0) substrates by the thermal evaporation method. The growth process, free-catalyst self-assembly vapor-solid (V-S) mechanism, was described and investigated deeply in terms of thermodynamics and kinetics. Then, the photoluminescence (PL) properties of ZnO NBs were studied in a temperature range from 10 to 270 K. At 10 K the recombination of acceptor-bound exciton (A⁰X) was predominant in the PL spectrum, and was attributed to the transition of P_Zn−2V_Zn complex bound exciton. The active energy of A⁰X and acceptor binding energy were calculated to be 17.2 and 172 meV, respectively. The calculated acceptor binding energy of P doped ZnO nanostructure is in good agreement with that of P doped ZnO film.     

微流控技术制备ZnO纳米线阵列及其气敏特性

利用微流控技术在微通道中制备了Zn O纳米线阵列,通过X射线衍射和扫描电子显微镜分别对纳米线的物相和表面形貌进行了表征.结果发现,合成的Zn O纳米线具有良好的c轴择优取向性和结晶度.同时,对Zn O纳米线阵列在丙酮、甲醇和乙醇气体中的气敏特性进行了研究,测试结果表明:在最佳工作温度(475?C)下,纳米线阵列对200 ppm(1 ppm=10-6)丙酮气体的最大灵敏度可达8.26,响应恢复时间分别为9和5 s;通过与传统水热法制备的Zn O纳米线的气敏性能相比较发现,基于微流控技术制备的纳米线阵列具有更高的灵敏度和更快的响应恢复速度.最后,从材料表面氧气分子得失电子的角度对Zn O纳米线气敏机理进行了讨论.     

Properties of Mn-doped ZnO nanopowder

The structural and magnetic properties of Mn-doped ZnO nanopowder are investigated and compared to undoped ZnO crystals. Mn incorporation leads to an increase in the lattice constants as revealed by X-ray diffraction measurements. An inhomogeneous distribution of the Mn atoms within the nanopowder was detected by energy-dispersive X-ray and electron-energy-loss spectroscopy measurements. Magnetic features are investigated by means of SQUID magnetometry on ensembles of powder particles as well as by magnetic force microscopy to study the behavior of single grains. PACS 75.50.Pp; 75.75.+a; 78.55.Et     

Surface chemistry study of Mn-doped germanium nanowires

Single crystal germanium nanowires have been grown by vapour-liquid-solid deposition onto silicon oxide substrates with Au catalyst nanoparticles. They have been doped by two different techniques: Ge and Mn co-evaporation during growth and post-growth Mn implantation. Scanning electron microscopy images show that Mn-implanted nanowires have a lower surface density and a smaller average diameter (18.8 nm) than the un-doped ones and those Mn doped by co-deposition. The effectiveness of Mn doping has been verified by X-ray photoemission spectroscopy and by energy-dispersive X-ray measurements, indicating in the two cases significant Mn atomic concentration in the nanowire. X-ray diffraction indicates that the nanowires are single crystals and that they do not contain precipitates of Mn extrinsic phases. Both SEM and XPS experimental evidences are in line to indicate that the Mn doping by ion implantation is preferable with respect to that one performed by co-evaporation as it reduces the thickness of the outer oxide sheath of the nanowires and their diameter.     

Synthesis and photoluminescence of water-soluble Mn-doped ZnS quantum dots

The water-soluble Mn²⁺-doped ZnS quantum dots (Mn:ZnS d-dots) were synthesized by using thioglycolic acid (TGA) as stabilizer in aqueous solutions in air, and characterized by X-ray powder diffraction (XRD), UV-vis absorption spectra and photoluminescence (PL) emission spectroscopy. The sizes of Mn:ZnS d-dots were determined to be about 2 nm using XRD measurements and the UV-vis absorption spectra. It was found that the Mn²⁺⁴T₁ → ⁶A₁ emission intensity of Mn:ZnS d-dots significantly increased with the increase of Mn²⁺ concentration, and showed a maximum when Mn²⁺ doping content was 1.5%. If Mn²⁺ concentration continued to increase, namely more than 1.5%, the Mn²⁺⁴T₁ → ⁶A₁ emission intensity would decrease. In addition, the effects of TGA/(Zn + Mn) molar ratio on PL were investigated. It was found that the peak intensity ratio of Mn²⁺⁴T₁ → ⁶A₁ emission to defect-states emission showed a maximum when the TGA/(Zn + Mn) molar ratio was equal to 1.8.     

Mn掺杂ZnSe量子点变温发光性质研究

量子点(QD)照明器件中电流导致的焦耳热会使其工作温度高于室温,因此研究量子点的发光热稳定性十分重要。本文利用稳态光谱和时间分辨光谱研究了具有不同壳层厚度的Mn掺杂ZnSe(Mn: ZnSe)量子点的变温发光性质,温度范围是80～500 K。实验结果表明,厚壳层(6.5单层(MLs))Mn: ZnSe量子点的发光热稳定性要优于薄壳层(2.6 MLs)的量子点。从80 K升温到400 K的过程中,厚壳层Mn: ZnSe量子点的发光几乎没有发生热猝灭,发光量子效率在400 K高温下依然可以达到60%。通过对比Mn: ZnSe量子点的变温发光强度与荧光寿命,对Mn: ZnSe量子点发光热猝灭机制进行了讨论。最后,为了研究Mn: ZnSe量子点的发光热猝灭是否为本征猝灭,对具有不同壳层厚度的Mn: ZnSe量子点进行了加热-冷却循环(300-500-300 K)测试,发现厚壳层的Mn: ZnSe量子点的发光在循环中基本可逆。因此,Mn: ZnSe量子点可以适用于照明器件,即使器件中会出现不可避免的较强热效应。