Mg掺杂GaN纳米线的结构及其特性

利用类似Delta掺杂技术在硅衬底上沉积Mg:Ga2O3薄膜, 然后在850 ℃下对薄膜进行氨化, 反应后制备出大量Mg掺杂GaN纳米线. 采用扫描电子显微镜(SEM)、X射线衍射(XRD)、傅里叶变换红外(FTIR)光谱和高分辨透射电子显微镜(HRTEM)对样品进行分析.结果表明, Mg掺杂GaN纳米线具有六方纤锌矿单晶结构, 纳米线的直径在30-50 nm范围内, 长度为几十微米.     

Optical and field emission properties of thin single-crystalline GaN nanowires

Thin high-quality gallium nitride (GaN) nanowires were synthesized by a catalytic chemical vapor deposition method. The synthesized GaN nanowires with hexagonal single-crystalline structure had thin diameters of 10-50 nm and lengths of tens of micrometers. The thin GaN nanowires revealed UV bands at 3.481 and 3.285 eV in low-temperature PL measurements due to the recombination of donor-bound excitons and donor-acceptor pairs, respectively. The blue shifts of UV bands in the low-temperature PL measurement were observed, indicating quantum confinement effects in the thin GaN nanowires which have smaller diameters than the exciton Bohr radius, 11 nm. For field emission properties of GaN nanowires, the turn-on field of GaN nanowires was 8.5 V/microm and the current density was about 0.2 mA/cm(2) at 17.5 V/microm, which is sufficient for the applications of field emission displays and vacuum microelectronic devices. Moreover, the GaN nanowires indicated stronger emission stability compared with carbon nanotubes.     

Catalytic growth and characterization of gallium nitride nanowires.

The preparation of high-purity and -quality gallium nitride nanowires is accomplished by a catalytic growth using gallium and ammonium. A series of catalysts and different reaction parameters were applied to systematically optimize and control the vapor-liquid-solid (VLS) growth of the nanowires. The resulting nanowires show predominantly wurtzite phase; they were up to several micrometers in length, typically with diameters of 10-50 nm. A minimum nanowire diameter of 6 nm has been achieved. Temperature dependence of photoluminescence spectra of the nanowires revealed that the emission mainly comes from wurtzite GaN with little contribution from the cubic phase. Moreover, the thermal quenching of photoluminescence was much reduced in the GaN nanowires. The Raman spectra showed five first-order phonon modes. The frequencies of these peaks were close to those of the bulk GaN, but the modes were significantly broadened, which is indicative of the phonon confinement effects associated with the nanoscale dimensions of the system. Additional Raman modes, not observed in the bulk GaN, were found in the nanowires. The field emission study showing notable emission current with low turn-on field suggests potential of the GaN nanowires in field emission applications. This work opens a wide route toward detailed studies of the fundamental properties and potential applications of semiconductor nanowires.     

利用Pd催化合成单晶GaN纳米线的光学特性(英文)

基于金属元素钯具有的催化特性,采用射频磁控溅射方法,在Si(111)衬底上沉积Pd:Ga2O3薄膜,然后在950℃下对薄膜进行氨化,制备出大量GaN纳米线.采用扫描电子显微镜(SEM)、X射线衍射(XRD)、透射电子显微镜(TEM)和高分辨透射电子显微镜(HRTEM)等技术手段对样品的结构、形貌和成分进行分析.结果表明,制备的样品为具有六方纤锌矿结构的单晶GaN纳米线,直径在20-60nm范围内,长度为几十微米,表面光滑无杂质,结晶质量较高.用光致发光光谱对样品的发光特性进行测试,分别在361.1、388.6和426.3nm处出现三个发光峰,且与GaN体材料相比近带边紫外发光峰发生了较弱的蓝移.对GaN纳米线的生长机制也进行了简单的讨论.     

Time-dependent density functional theory study on optical properties of GaN doped with alkaline-earth atom

The absorption and the emission spectra of GaN and (Ga,AE)N (AE = Be, Mg, Ca) were calculated by using TDDFT method with cluster model. The calculation results show that Ga₂₆N₂₆H₅₀ cluster only has very weak absorption but has some emission bands in visible region. The band-to-band emission appears around 3.56 eV. If alkaline-earth atoms (Be, Mg and Ca) are doped into GaN, the blue emission band around 3.0 eV appears. Thereinto, Ga₂₅Ca₁N₂₆H₅₀ cluster shows a weaker yellow emission band and a stronger blue one (2.92 eV), which make (Ga,Ca)N material a promising candidate to emit blue light.     

Synthesis, characterization, and optical properties of In2O3 semiconductor nanowires

In2O3 semiconductor nanowires were synthesized by the chemical vapor deposition method through carbon thermal reduction at 900 degrees C with 95% Ar and 5% O2 gas flow. The In2O3 nanowires were characterized by field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), and photoluminescence spectroscopy (PL). For the first time, we observed the formation of corundum-type h-In2O3 nanowires and branched In2O3 nanowires. The PL spectra of In2O3 nanowires show strong visible red emission at 1.85 eV (670 nm) at low temperature, possibly caused by a small amount of oxygen vacancies in the nanowire crystal structure.     

N2流量对GaN的形貌及光学和电学性能的影响

采用化学气相沉积法(CVD)在Si(100)衬底上以Ni为催化剂, 金属Ga和NH₃为原料合成了GaN微纳米结构, 并研究了N₂流量对产物GaN的形貌及光学和电学性能的影响。利用场发射扫描电子显微镜(SEM)、透射电镜(TEM)、X射线衍射仪(XRD)、X-ray能谱仪(EDS)、光致发光谱(PL)和霍尔效应测试仪(HMS-3000)等测试手段对样品的形貌、结构、成分、光学和电学性能进行了分析。结果表明, 随着N₂流量的增加, 产物GaN的形貌发生了由微米棒到蠕虫状线再到光滑纳米线的转变;生成的GaN均为六方纤锌矿结构;样品均表现出383 nm的近带边紫外发射峰和470 nm左右的蓝光发射峰;所有样品均为n型;并对产物GaN的形貌转变机理进行了分析。     

Formation of arrays of gallium nitride nanorods within mesoporous silica SBA-15

We report the first formation of arrays of GaN nanorods inside the nanoscale channels of mesoporous silica SBA-15. GaCl3 dissolved in toluene was incorporated into the methyl group-functionalized SBA-15 powder. The pore surfaces functionalized with methyl groups should facilitate the impregnation with GaCl3. Formation of GaN nanorod arrays within SBA-15 was carried out by heating the powder to 700 degrees C for 3 h under nitrogen atmosphere, followed by ammonolysis at 900 degrees C for 5 h. epsilon-Ga2O3, an unusual phase for Ga2O3, formed after the first thermal process and was converted into wurtzite GaN during ammonolysis. The final products have been characterized by FT-IR spectra, powder XRD patterns, TEM images and SAED patterns, EDS analysis, and nitrogen adsorption-desorption isotherm measurements to confirm the presence of GaN nanostructures. The nanorods are 6-7.5 nm in diameter, and can be a few hundreds of a nanometer in length to exhibit nanowire structure. Free-standing GaN nanorod arrays were revealed upon removal of the silica framework with HF solution. Optical characterization of the isolated GaN nanorod arrays shows a strong and sharp near band-edge emission at 375 nm, and two phonon-assisted donor-acceptor peaks at 395 and 415 nm. A broad but weak emission in the region of 335-360 nm due to the quantum confinement effect of short nanorods was observed.     

Density Functional Theory Study on the Optical Properties of Mn-doped GaN

The absorption and emission spectra of the wurtzite Mn-doped GaN were calculated with cluster models.The predicted lattice parameters become slightly larger than those of undoped cluster.The average bond length of Mn-N is longer than that of Ga-N.Spin density shows that one Mn atom in these clusters has four single electrons with the same direction of the spin polarity.The new energy level with light Mn-doping appears at 1.37 eV above the valance band.The absorption spectra of Mn-doped GaN cover the visible light region.The calculated emission spectra show that the green luminescence of GaN material in experiment did not result from Mn dopant.With the increase of Mn doping,the emission intensity of yellow or blue band increases to different extent and the band-to-band emission band shows red shift from peak at 3.34 to 3.24 eV.     

Fabrication and optical property of silicon oxide layer coated semiconductor gallium nitride nanowires

Quasi one-dimensional GaN-SiO(2) nanostructures, with a silicon oxide layer coated on semiconductor GaN nanowires, were successfully synthesized through as-synthesized SiO(2) nanoparticles-assisted reaction. The experimental results indicate that the nanostructure consists of single-crystalline wurtzite GaN nanowire core, an amorphous SiO(2) outer shell separated in the radial direction. These quasi one-dimensional nanowires have the diameters of a few tens of nanometers and lengths up to several hundreds of micrometers. The photoluminescence spectrum of the GaN-SiO(2) nanostructures consists of one broad blue-light emission peak at 480 nm and another weak UV emission peak at 345 nm. The novel method, which may results in high yield and high reproducibility, is demonstrated to be a unique technique for producing nanostructures with controlled morphology.     

Formation of well-aligned ZnGa(2)O(4) nanowires from Ga(2)O(3)/ZnO core-shell nanowires via a Ga(2)O(3)/ZnGa(2)O(4) epitaxial relationship

Formation of well-aligned and single-crystalline ZnGa(2)O(4) nanowires on sapphire (0001) substrates has been achieved via annealing of the Ga(2)O(3)/ZnO core-shell nanowires. Ga(2)O(3)/ZnO core-shell nanowires were prepared using a two-step method. The thickness of the original ZnO shell and the thermal budget of the annealing process play crucial roles for preparing single-crystalline ZnGa(2)O(4) nanowires. Structural analyses of the annealed nanowires reveal the existence of an epitaxial relationship between ZnGa(2)O(4) and Ga(2)O(3) phases during the solid-state reaction. A strong CL emission band centered at 360 nm and a small tail at 680 nm are obtained at room temperature from the single-crystalline ZnGa(2)O(4) nanowires.     

砷掺杂的ZnO纳米线的发光特性

在GaAs基底上制备了高质量的直径为10～100 nm、长度约几个微米的As掺杂ZnO纳米线. 扫描电镜、EDX分析及透射电镜分析显示, ZnO纳米线具有较好的晶态结构. 对As掺杂前后的ZnO纳米线进行光学特性测量, 结果表明, ZnO纳米线在385 nm处有较强的紫外发光峰, 在505 nm左右有较弱的蓝绿发光峰; As掺杂较大地改变了ZnO纳米线的发光性质, 使本征发光峰移到393 nm处, 蓝绿发光强度有了很大程度的提高.     

Needlelike bicrystalline GaN nanowires with excellent field emission properties

Large-yield and crystalline GaN nanowires have been synthesized on a Si substrate via a simple thermal evaporation process. The majority of the GaN nanowires has bicrystalline structures with a needlelike shape, a triangular prism morphology, and a uniform diameter of approximately 100 nm. Field-emission measurements show that the bicrystalline GaN nanowires with sharp tips have a lower turn-on field of approximately 7.5 V/microm and are good candidates for low-cost and large-area electron emitters. It is believed that the excellent filed emission property is attributed to the bicrystalline structure defects and sharp tips.     

Synthesis of europium-doped zinc oxide micro- and nanowires

Single crystalline Eu³⁺-doped wurtzite ZnO micro- and nanowires were synthesized by a chemical vapor deposition method (CVD). The nanostructures were grown by autocatalytic mechanism at walls of an alumina boat. The structure and properties of the doped ZnO is fully characterized by X-ray diffraction (XRD), energy-dispersive X-ray spectrometry (EDX), scanning and transmission electron microscopy (SEM and TEM), and photoluminescence (PL) methods. The synthesis was carried out for 10 min giving vertically aligned nanowires with mean diameter of 50–400 nm and with length of up to several microns. The nanowires were grown along ±[0001] direction. The concentration of Eu³⁺ dopant in the synthesized nanowires was varied from 0.7 to 0.9 at %. The crystal structure and microstructures of the doped nanomaterials were discussed and compared with undoped ZnO. The photoluminescence spectra show that emission of doped samples were shifted towards orange-red region (2.02 eV) relative to undoped zinc oxide nanostructures (2.37 eV) due to Eu³⁺ intraionic transitions from ZnO/Eu.     

The electron affinity of gallium nitride (GaN) and digallium nitride (GaNGa): the importance of the basis set superposition error in strongly bound systems

The electron affinity of GaN and Ga2N as well as the geometries and the dissociation energies of the ground states of gallium nitrides GaN, GaN(-), Ga2N, and Ga2N(-) were systematically studied by employing the coupled cluster method, RCCSD(T), in conjunction with a series of basis sets, (aug-)cc-pVxZ(-PP), x=D, T, Q, and 5 and cc-pwCVxZ(-PP), x=D, T, and Q. The calculated dissociation energy and the electron affinity of GaN are 2.12 and 1.84 eV, respectively, and those of Ga2N are 6.31 and 2.53 eV. The last value is in excellent agreement with a recent experimental value for the electron affinity of Ga2N of 2.506+/-0.008 eV. For such quality in the results to be achieved, the Ga 3d electrons had to be included in the correlation space. Moreover, when a basis set is used, which has not been developed for the number of the electrons which are correlated in a calculation, the quantities calculated need to be corrected for the basis set superposition error.     

Fabrication of lead titanate single crystalline nanowires by hydrothermal method and their characterization

Single crystalline nanowires of lead titanate (PbTiO₃) were fabricated by hydrothermal method at 200°C using lead acetate and n-tetrabutyl titanate as starting materials, where sodium hydroxide was served as a mineralizer. Crystalline phases, microstructure and optical properties of PbTiO₃ nanowires were investigated. The PbTiO₃ nanowires were uniform and continuous along the long axis, and were composed of single crystalline PbTiO₃ with a tetragonal perovskite structure. The diameter of a single nanowire was around 12 nm and the length reached up to 3 μm. The chemical composition of the samples and the valence states of elements were determined by X-ray photoelectron spectroscopy (XPS). The ultraviolet/visible absorption spectroscopic investigation suggested that the absorption edge of optical transition of the first excitonic state occurred at around 320 nm. A blue-green light emission peaking at about 471 nm (2.63 eV) is observed at room temperature, and the intensity of this emission increased with increasing excitation wavelength. Oxygen vacancies are responsible for the light emission of PbTiO₃ nanowires.     

N2流量对GaN的形貌及光学和电学性能的影响

采用化学气相沉积法(CVD)在Si(100)衬底上以Ni为催化剂,金属Ga和NH3为原料合成了GaN微纳米结构,并研究了N2流量对产物GaN的形貌及光学和电学性能的影响。利用场发射扫描电子显微镜(SEM)、透射电镜(TEM)、X射线衍射仪(XRD)、Xray能谱仪(EDS)、光致发光谱(PL)和霍尔效应测试仪(HMS-3000)等测试手段对样品的形貌、结构、成分、光学和电学性能进行了分析。结果表明,随着N2流量的增加,产物GaN的形貌发生了由微米棒到蠕虫状线再到光滑纳米线的转变;生成的GaN均为六方纤锌矿结构;样品均表现出383 nm的近带边紫外发射峰和470 nm左右的蓝光发射峰;所有样品均为p型;并对产物GaN的形貌转变机理进行了分析。     

Defect-pit-assisted growth of GaN nanostructures: nanowires, nanorods and nanobelts

A new method using defect-pit-assisted growth technology to successfully synthesize the high-quality single crystalline GaN nanostructures by ammoniating Ga(2)O(3) films was proposed in this paper. During the ammoniating process, the amorphous middle buffer layer may unavoidably produce some defects and dislocations. Some defect pits come out, which have the lowest surface energy and can subsequently be used as a mask/template or act as potential nucleation sites to fabricate the GaN actinomorphic nanostructures. The as-prepared products are characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). The results indicate that all the reflections of the samples can be indexed to the hexagonal GaN phase and the clear lattice fringes in HRTEM further confirm the growth of high-quality single-crystal GaN nanostructures. The SEM images show that the nanostructures have been realized under different experimental conditions exhibiting different shapes: nanowires, nanorods, and nanobelts. No particles or other nanostructures are found in the SEM study, demonstrating that the product possesses pure nanostructures. These nanostructures show a very good emission peak at 366 nm, which will have a good advantage for applications in laser devices using one-dimensional structures. Finally, the growth mechanism is also briefly discussed.     

Sol-gel template synthesis and photoluminescence of n- and p-type semiconductor oxide nanowires.

A sol-gel template technique has been put forward to synthesize single-crystalline semiconductor oxide nanowires, such as n-type SnO2 and p-type NiO. Scanning electron microscopy and transmission electron microscopy observations show that the oxide nanowires are single-crystal with average diameters in the range of 100-300 nm and lengths of over 10 microm. Photoluminescence (PL) spectra show a PL emission peak at 401 nm for n-type semiconductor SnO2, and a PL emission at 407 nm for p-type semiconductor NiO nanowires, respectively. Correspondingly, the observed violet-light emission at room temperature is attributed to near-band-edge emission for SnO2 nanowires and the 3d(7)4s-->3d8 transition of Ni2+ for NiO nanowires.     

A simple solution route to single-crystalline Sb2O3 nanowires with rectangular cross sections

We report a simple solution route to large-scale synthesis of uniform, single-crystalline, and well-faceted orthorhombic antimony trioxide (Sb(2)O(3)) nanowires with rectangular cross sections by direct air oxidation of bulk metal antimony (Sb) in a mixed solution made of ethylenediamine (EDA) and deionized water (DIW). The as-synthesized products were analyzed by range of methods, such as XRD, SEM, EDX, TEM, SAED, HRTEM, FTIR, Raman, UV-vis absorption, and photoluminescence (PL) spectra. The as-synthesized Sb(2)O(3) nanowires with rectangular cross sections are usually hundreds of micrometers in length, typically 80-100 nm in width, and 60-80 nm in thickness. The novel room temperature photoluminescence properties of Sb(2)O(3) nanowires with rectangular cross sections displayed a significant UV luminescence with a strong emission band at 374 nm, which was reported for the first time, indicating the as-synthesized products with an optical band gap E(g) = 3.3 eV. It is expected that as-synthesized Sb(2)O(3) nanowires would be a new member of functional materials and used in the manufacture of advanced nanodevices.