ZnO以及Fe掺杂ZnO的光学性质和室温铁磁性研究

采用共沉淀法制备出不同掺杂浓度的Zn1-xFexO(0.00≤x≤0.10)粉末样品,研究掺杂浓度的不同对其结构、光学性质以及室温铁磁性的影响。采用X射线衍射仪、红外光谱仪、紫外-可见分光光度计、荧光光谱仪、振动样品磁强计对样品的结构、光学性质和磁性进行测试分析。结果表明:所有Zn1-xFexO样品都具有单一六方纤锌矿结构,没有出现第二相杂质。对紫外波段吸收率高达95%,掺Fe后可见光波段的吸收率与纯ZnO相比有明显提高,掺杂使得带隙宽度Eg由纯ZnO的3.20eV减小到3.11eV。样品光致发光主要有397nm的紫外发射和450,466nm处的蓝光发射,Fe的掺入降低了ZnO的发光强度,但并不影响其发光峰位。样品显示明显的室温铁磁性,磁性随掺杂浓度升高而减弱。     

Cu掺杂ZnO纳米粒子的光学性能及铁磁性

利用溶胶凝胶法制备了纳米结构的Cu掺杂ZnO基稀磁半导体,通过X射线衍射分析表明,样品为纯相ZnO纤锌矿结构,磁性测量表明样品在室温下呈室温铁磁性,铁磁性来源为氧化锌晶格中的缺陷与Cu2+离子之间的交换作用。室温光致发光(PL)谱观察到紫外带边和可见光区两个发射峰,且随着Cu掺杂量增加,紫外峰淬灭,可见峰发射增强。     

Ce3+、Mn2+掺杂Zn3（BO3）2的制备及其发光性能

采用共沉淀法在700℃和较短的烧结时间下制备了Zn3(BO3)2和不同浓度的Ce3+、Mn2+离子掺杂的Zn3(BO3)2纳米晶粉末,对合成产物的发光性质及发光机理进行了研究。利用荧光分光光度计、X射线粉末衍射仪以及透射电镜对其光学性能和纳米晶形貌进行了表征。结果表明Ce3+离子掺杂的Zn3(BO3)2样品在340～400nm之间有强的荧光发射,其最高发射峰峰位为365nm,在Ce3+掺量为0.5%(摩尔分数,下同)时发光强度达到最高值。Ce3+取代Zn2+离子作为发光中心,Mn2+离子作为激活剂加入,并不影响荧光发射峰的位置,但能够有效增强其发光强度。当Mn2+离子掺量为0.7%(摩尔分数)时,Ce3+、Mn2+共掺杂的Zn3(BO3)2纳米晶发光强度达到最高值。     

溶胶-凝胶法制备ZnO基稀释磁性半导体薄膜

用溶胶－凝胶法制备了具有良好光学性质和C轴取向的ZnO:Fe薄膜。ZnO:Fe薄膜具有尖锐的带边发光，禁带宽度约为3.3eV，半高宽13nm。磁性测量表明，ZnO：Fe薄膜在室温下具有铁磁性，饱和磁化强度约为10^-3emu量级，矫顽力为30奥斯特（Oe)。     

Eu2+、Dy3+、Li+共掺杂CaSi2O2N2荧光粉的发光性能

采用高温固相反应法制备了一系列白光LED用CaSi2O2N2:0.05Eu2+,xDy3+,xLi+(0≤x≤0.03)荧光粉.利用X射线衍射仪对样品的物相结构进行了分析,结果表明:Dy3+和Li+离子的掺入没有改变CaSi2O2N2:Eu2+荧光粉的主晶相.利用荧光光谱仪对样品的发光性能进行了测试,发现所有样品的激发光谱均覆盖了从近紫外到蓝光的较宽范围,400 nm激发下得到的发射光谱为宽波段的单峰,峰值位于545 nm左右,是Eu2+离子5d-4f电子跃迁引起的.Dy3+离子掺杂可以提高CaSi2O2N2:Eu2+荧光粉的发光强度,Dy3+与Li+共掺杂可进一步提高荧光粉的发光强度,当Dy3+和Li+的掺杂量为1mol%时,荧光粉的发光强度达到最大值,是单掺杂Eu2+的荧光粉发光强度的157%.     

掺杂Ni2+的六方相ZnTiO3的光致发光性能研究

钛酸锌(ZnTiO3)作为一种有应用潜力的光致发光材料,近年来得到了研究者的广泛关注。但目前的相关报道都是围绕立方相ZnTiO3的发光性能展开论述,没有关于六方相ZnTiO3发光性能的研究。以去离子水作溶剂,采用溶胶-凝胶法制备出掺杂Ni 2+的六方相ZnTiO3粉体,利用X射线衍射仪对其物相结构做了分析,使用荧光分光光度计对其激发光谱和发射光谱进行了表征,并将其与纯六方相ZnTiO3的发光性能做了对比分析。结果表明,在600℃制备出的样品主晶相均为纯六方相ZnTiO3,Ni 2+的引入并没有改变ZnTiO3的物相结构。Ni 2+掺杂量在3.0%以下的样品发射峰强度增大,原因是Ni 2+作为能量传递介质,提高了样品的发光效率;但Ni 2+掺杂量达到4.0%时,发生了浓度猝灭现象。Ni 2+在ZnTiO3中位于原Zn2+的格点位置。     

Yb3+、Er3+和Eu3+共掺杂TiO2纳米带的制备与表征

通过离子交换和水热两步合成过程简单制备了Yb3+、Er3+和Eu3+共掺杂锐钛矿型TiO2纳米带。该3种离子共掺杂未导致TiO2结构和形貌发生变化。光学特性测试结果表明,由于稀土离子掺杂浓度低,Eu3+掺杂未改变由Yb3+和Er3+产生的上转换发射峰位,但可观察到因上转换发光激发的Eu3+荧光发射峰;Eu3+荧光光谱也未受到Yb3+和Er3+掺杂的影响。通过对掺杂样品上转换发光机理的考察证实,上转换发光过程是双光子过程,但TiO2和Eu3+掺杂对此发光过程有明显影响。     

溶胶-凝胶法制备Cu/ZnO的室温铁磁性

为研究稀磁性半导体的室温铁磁性来源,采用溶胶-凝胶法制备了Cu掺杂ZnO半导体粉末。X射线衍射光谱显示Cu在ZnO中的固溶度小于0.08 (摩尔比);透射电子显微镜分析显示颗粒尺寸较为均匀,呈单结晶态;振动样品磁强计测试表明,Cu/ZnO具有室温铁磁性。由于Cu本身不具有任何磁性,样品的铁磁性来源为氧化锌晶格中的缺陷与Cu2+离子之间的交换作用。     

Cu掺杂对Fe/Mo双钙钛矿居里温度的影响

研究了双钙钛矿结构化合物Sr2FeMoO6中Fe位的Cu2+离子替代效应,样品中Cu2+离子替代Fe3+离子没有引起结构变化,但导致样品B位离子有序度降低.并且随Cu2+离子的掺入,室温下样品的磁化强度迅速下降.而居里温度TC随Cu2+的掺入有所上升,因此认为Cu2+离子的掺入破坏了Fe3+-Mo5+反铁磁耦合,抑制了样品的原有铁磁性,促使Mo5+向Mo6+的转变和Fe3+向Fe2+的转变引起Fe/Mo反位无序的增加,形成了Fe3+-Fe2+反铁磁耦合团簇.     

Cu掺杂ZnO的光致发光光谱

ZnO是宽禁带半导体,室温下禁带宽度为3.37eV,激子束缚能高达60meV,是制备光电器件的优选材料。然而,p型掺杂仍是亟待解决的问题。ⅠB元素Cu被认为在ZnO中产生受主能级,可以实现ZnO的p型掺杂。综述了各种制备方法、制备条件和激发条件下得到的Cu掺杂ZnO薄膜、纳米线和纳米棒的光致发光谱和机理,总结出Cu掺杂ZnO光致发光谱的带边发射会因为Cu的掺杂强度降低,或出现发射中心红移等现象。可见光区域由于Cu掺杂会产生新的蓝光、绿光和橙光发射峰,蓝光发射峰可能与Cu2+-Cu+跃迁或VZn和Zni有关;绿光发射峰可能与Cu杂质或VO-VZn跃迁有关,Cu掺杂还可能引入非辐射复合的点缺陷中心;橙光发射峰则可能由于Cu杂质受主能级向深施主能级跃迁而产生。     

Magnetic and optical properties of Mn doped ZnO nanocrystalline films

We have investigated the properties of Mn-doped ZnO nanocrystalline film growing on zinc foil by the hydrothermal method. X-ray photoelectron spectroscopy shows that the manganese ions exist as Mn2+ in the film. From UV-vis spectra, we observe a red shift in wavelength of absorption and greater reflectivity due to the Mn ion incorporation in ZnO lattices. The photoluminescence spectrum of the Mn-doped ZnO film shows two strong new blue peaks centered at 424 nm and 443 nm, besides the UV emission peak owing to the band gap of ZnO semiconductor. The magnetic property of the Mn-doped ZnO exhibits a room temperature ferromagnetic characteristic with a saturation magnetization (Ms) of 0.3902 x 10(-3) emu/cm3 and a coercive field of 47 Oe. We suggest that the blue emission of the Mn-doped ZnO film corresponds to the electron transition from the level of interstitial Zn and Mn to the valence band. The defects brought about by Mn ion incorporation are the main cause of the room temperature ferromagnetic property.     

Enhanced ferromagnetic and photocatalytic properties in Mn or Fe doped p-CuO/n-ZnO nanocomposites

Mn doped CuO/ZnO heterostructure exhibited significant room temperature ferromagnetism and visible light photocatalytic properties. Phase analysis for the pure, Mn and Fe doped CuO/ZnO nanocomposites evidently confirmed the formation of CuO and ZnO phases in each composite without any impurities. Based on Rietveld refinement analysis, the inclusion of Mn ions into CuO/ZnO nanocomposite decreased the unit cell volume of both oxides while Fe ions lead to lattice expansion. Mn ions induced the formation of ZnO hexagonal nanorods in CuO/ZnO nanocomposite. Nano-flakes and spherical nanoparticles shapes were seen for Fe doped CuO/ZnO nanocomposites. The characteristics IR absorption bands of CuO and ZnO overlapped together in their nanocomposites structure. From Kubelka-Munk plots, the incorporation of Mn ions enabled the ZnO band gap to absorb in the visible light region. Pure CuO/ZnO nanocomposite exhibited room temperature ferromagnetism with saturation magnetization (M_s) of 0.042 emu/g and coercivity (H_c) of 547 Oe. The ferromagnetic properties of the pure CuO/ZnO nanocomposite were greatly improved by Mn and Fe doping and the saturation magnetization extremely jumped to 0.86 and 0.85 emu/g, respectively. High photocatalytic activity, 98%, with good reusability for methyl orange (MO) degradation under visible light irradiation was achieved by 4 wt% Mn doped CuO/ZnO nanocomposite. A relation between the crystallinity, band gap and photocatalytic activity with dopant type (Mn or Fe) incorporated into CuO/ZnO nanocomposites was noticed. In contrary to Fe dopant, Mn as dopant played successful roles in improving the crystallinity, band gap and photocatalytic properties of CuO/ZnO nanocomposite. Multifunctional properties can be realized by combining different oxides in heterostructure form and using doping technique.     

[100]取向Al-Ti共掺杂ZnO薄膜的制备与光电性能研究

采用常压固相烧结法制备了Al-Ti共掺ZnO靶材, 采用射频磁控溅射技术及真空退火工艺, 在普通玻璃衬底上制备了具有[100]取向Al-Ti共掺杂ZnO薄膜(ZATO). 采用X射线衍射(XRD)、扫描电子显微镜(SEM)对ZATO薄膜的生长机理、显微结构、形貌进行了测试分析, 用四探针测试仪、紫外-可见分光光度计及荧光光谱仪对ZATO薄膜的光电性能进行了测试分析. 结果表明, ZATO薄膜经500℃保温3h退火后, 择优取向由(002)向(100)方向转变; 此时, 衍射谱上还观察到超点阵衍射线条. [100]取向ZATO薄膜的光学带隙从退火前的3.29降至2.86, 平均可见光透过率从90%降至70%, 表现为一般的透过性; 而电阻率则从1.89×10^-2Ω·cm降至1.25×10^-3Ω·cm, 呈现较好的导电性. 薄膜中均出现了380nm附近的带边发射(NBE)峰以及410、564nm的深能级发射峰, 且经500℃保温3h退火后, 这些峰的位置并未改变, 但峰强均明显减弱. 对上述实验机理进行了分析讨论.     

Optical and magnetic properties of Cu-doped ZnO nanoparticles

Cu-doped ZnO nanoparticles were synthesized by a simple chemical method at low temperature with Cu:Zn atomic ratio from 0 to 5 %. The synthesis process was based on the hydrolysis of zinc acetate dehydrate and copper acetate tetrahydrate heated under reflux to 65 °C using methanol as a solvent. X-ray diffraction (XRD) analysis reveals that the Cu-doped ZnO crystallize in a wurtzite structure with a change of crystal size from 12 nm for undoped ZnO to 5 nm for Cu-doped ZnO. These nano size crystallites of Cu doped ZnO self-organized into microspheres. The XRD patterns, Scanning electron microscopy and transmission electron microscopy micrographs of doping of Cu in ZnO confirmed the formation of microspheres and indicated that the Cu²⁺ is successfully substituted into the ZnO host structure of the Zn²⁺ site. Cu doping shifts the absorption onset to blue from 373 to 350 nm, indicating an increase in the band gap from 3.33 to 3.55 eV. A relative increase in the intensity of the deep trap emission of Cu-doped ZnO is observed when increasing the concentration of Cu. Magnetic measurements indicate that Cu-doped ZnO samples are ferromagnetic at room temperature except pure ZnO.     

Structural, Morphological and Optical Properties of ZnO Thin Films Grown on γ-LiAlO2 Substrate by Pulsed Laser Deposition

ZnO thin films were deposited on the substrates of (100) γ-LiAlO2 at 400, 550 and 700℃ using pulsed laser deposition (PLD) with the fixed oxygen pressure of 20 Pa, respectively. When the substrate temperature is 400℃, the grain size of the film is less than 1 μm observed by Leitz microscope and measured by X-ray diffraction (XRD). As the substrate temperature increases to 550℃, highly-preferred c-orientation and high-quality ZnO film can be attained.While the substrate temperature rises to 700℃, more defects appears on the surface of film and the ZnO films become polycrystalline again possibly because more Li of the substrate diffused into the ZnO film at high substrate temperature. The photoluminescence (PL) spectra of ZnO films at room temperature show the blue emission peaks centered at 430 nm. We suggest that the blue emission corresponds to the electron transition from the level of interstitial Zn to the valence band. Meanwhile, the films grown on γ-LiAlO2 (LAO) exhibit green emission centered at 540 nm, which seemed to be ascribed to excess zinc and/or oxygen vacancy in the ZnO films caused by diffusion of Li from the substrates into the films during the deposition.     

[101]取向Li掺杂ZnO薄膜光学性能的研究

采用射频磁控溅射法在玻璃衬底上制备了[101]取向的Li:ZnO薄膜, 研究了该薄膜的光学性能随热处理温度变化的规律. 结果表明, 399nm的发光峰是由Li的杂质能级引起; 与[002]取向的薄膜相比, 未经热处理的[101]薄膜其光学带隙大, 且出现了380nm附近的带边发射(NBE) 峰; 在560～580℃热处理下, 其晶胞变小、光学带隙变窄、360nm 左右的带间发光峰红移; 当热处理温度升至610℃时, 薄膜中再次出现380nm的NBE峰.     

电沉积ZnO纳米柱的光学带隙与非辐射复合EI北大核心CSCD

为实现ZnO纳米柱阵列材料在新型纳米结构化太阳能电池中的应用,需要对纳米柱的几何形貌与光电特性进行调控。ZnO纳米柱阵列材料的制备方法为电化学沉积方法。通过在生长溶液中使用In(NO_(3))_(3)和NH_(4)NO_(3),实现了对纳米柱的直径、阵列密度、柱间距、光学带隙、近带边发射、斯托克斯位移等物理性质的调控。采用扫描电子显微镜、X射线衍射仪、分光光度计、光致发光测试仪对样品的形貌、晶体性质、透射反射性质、光致发光性质进行测试与表征。结果表明,使用NH_(4)NO_(3)将紧密排列的ZnO纳米柱阵列密度降低了51%,导致柱间距增大至超过100 nm,同时可将纳米柱的直径降低至22 nm。使用In(NO_(3))_(3)使ZnO纳米柱的光学带隙展宽100 meV。通过NH_(4)NO_(3)的使用可在3.41 eV至3.55 eV范围内调控带隙。由于NH_(4)NO_(3)的引入,ZnO纳米柱的斯托克斯位移可降低至19 meV,表明NH_(4)NO_(3)的引入能够有效地抑制纳米柱阵列中的非辐射复合。     

Structural,electrical and photoluminescence properties of ZnO:Al network films grown on nanochannel Al2O3 substrates by direct current magnetron sputtering with an oblique target

ZnO:Al network films were grown on nanochannel Al₂O₃ substrates at 300 K by direct current magnetron sputtering with an oblique target. The film thicknesses are 60 nm, 160 nm and 190 nm. The holes of the network films diminish with increasing film thickness. For the 60-nm thick film, the network is formed by connecting grains. For the 160-nm and 190-nm thick films, however, the network is formed by connecting granules. The granules consist of many small grains. All the network films have a wurtzite structure. The 60-nm and 160-nm thick network films mainly have a [1 0 1] orientation in the film growth direction while the 190-nm thick network film grows with a random crystallographic orientation. A temperature dependence of the resistance within 160–300 K reveals that the network films exhibit a semiconducting behavior and their carrier transport mechanism is thermally activated band conduction. Room temperature photoluminescence spectra for wavelengths between 300 nm and 700 nm reveal a violet emission centered at 405 nm for the 60-nm thick network film and a blue emission centered at 470 nm for both the 160-nm and the 190-nm thick network films. Annealing decreases the resistivity of the network film.     

Blue fluorescence of decorated nano zinc oxide/polystyrene hybrid thin film prepared by pulsed laser ablation

Decorated nano ZnO/PS organic sol was successively produced by pulsed laser ablation at the interface of ZnO ZnO target submerged in the flowing liquid of butyl acetate solution of PS which contained salicylic acid, then decorated nano ZnO/PS hybrid thin film was obtained. It is found that decorated nano ZnO/PS hybrid thin film radiates intense blue light under ultraviolet radiation and has a broad emission band centered at 448 nm in the emission fluorescence spectrum. TEM shows that the size of the nano ZnO particles distributes between 10 nm and 15 nm. TG-DSC reveals that the heat resistance of decorated nano ZnO/PS hybrid thin film increases.