Mn掺杂ZnO稀磁半导体材料的制备和磁性研究

采用共沉淀方法制备了名义组分为Zn_1-xMn_xO(x=0.001,0.005,0.007,0.01)的Mn掺杂的ZnO基稀磁半导体材料,并研究了在大气气氛下经过不同温度退火后样品的结构和磁性的变化.结果表明：样品在600℃的大气条件下退火后, 仍为单一的六方纤锌矿结构的ZnO颗粒材料;当样品经过800℃退火后,Mn掺杂量为0.007,0.01的样品中除了ZnO纤锌矿结构外还观察到ZnMnO₃第二相的存在.磁性测量表明,大气条件下600℃退火后的样品,呈现出室温铁磁性;而800℃退火后的样品,其室温铁磁性显著减弱,并表现为明显的顺磁性.结合对样品的光致发光谱的分析,认为合成样品的室温铁磁性是由于Mn离子对ZnO中的Zn离子的替代形成的. 关键词： ZnO 掺杂 稀磁半导体 铁磁性     

Co掺杂的ZnO室温铁磁半导体材料制备与磁性和光学特性研究

采用溶胶-凝胶法制备出具有室温铁磁性的Co掺杂的ZnO稀磁半导体材料. 通过对样品的结构、磁性和发光特性的研究发现,样品具有室温铁磁性,并发现其铁磁性源于磁性离子对ZnO中Zn离子的取代. 对不同温度制备的样品的磁性以及其发光特性的变化研究发现,样品的铁磁性与样品中锌间隙位（Zn_i）缺陷的密度有关. 关键词： ZnO 稀磁半导体 铁磁性     

Growth temperature dependent evolutions of microstructural, optical and magnetic properties of Zn0.75Co0.25O films

Zn0.75Co0.25O films are fabricated via reactive electron beam evaporation. The influence of growth temperature on the microstructural, optical and magnetic properties of Zn0.75Co0.25O films is investigated by using x-ray diffraction, selected area electron diffraction, field emission scanning electron microscope, high resolution transmitting electron microscope, photoluminescence （PL）, field dependent and temperature dependent DC magnetization, and x-ray photoelectron spectroscopy （XPS）. It is shown that Zn0.75Co0.25O films grown at low temperatures （250-350℃） are of single-phase wurtzite structure. Films synthesized at 300 or 350℃ reveal room temperature （RT） ferromagnetism （FM）, while su for 250℃ fabricated films is found above 56 K. PL and XPS investigations show favour towards the perspective that the O-vacancy induced spin-split impurity band mechanism is responsible for the formation of RT FM of Zn0.75Co0.25O film, while the superparamagnetism of 250℃ fabricated film is attributed to the small size effect of nanoparticles in Zn0.75Co0.25O film.     

Comparative studies on Zn0.95Co0.05O thin films on C- and R-sapphire substrates

Zn0.95Co0.05 O precipitate-free single crystal thin films were synthesized by a dual beam pulsed laser deposition method.The films form a wurtzite structure whose hexagonal axis is perpendicular or parallel to the plane of the surface depending on the C-plane (0001) or R-plane (11 ˉ 20) sapphire substrate.Based on the results of high-resolution transmission electron microscopy and x-ray diffraction,C-plane films show larger lattice mismatch.The films exhibit magnetic and semiconductor properties at room temperature.The coercivity of the film is about 8000 A/m at room temperature.They are soft magnetic materials with small remanent squareness S for both crystal orientations.There is no evidence to show that the anisotropy is fixed to the hexagonal axis (C-axis) for the wurtzite structure.     

Dependence of substrate temperature of Zn0.8Co0.2O films deposited by pulsed DC magnetron sputtering

We have investigated the microstructure, electrical and magnetic properties of the ZnCoO thin films, which were prepared by the asymmetrical bipolar-pulsed DC magnetron sputtering as a function of substrate temperature. The structural properties of ZnCoO films were characterized with a high resolution XRD. The XRD patterns of the ZnCoO films showed a strong (0 0 2) preferential orientation. The average crystallite size was 23–35 nm, which was estimated from full width at half maximum of XRD results. The electrical resistivity of the films were measured by the van der Pauw method through Hall measurement and showed below 10⁻¹ Ω cm above 300 °C. The magnetic properties of the ZnCoO films were analyzed by the alternating gradient magnetometer at room temperature. All of the films were exhibited the ferromagnetic nature. The high conductivity and room temperature ferromagnetism of the ZnCoO films above 300 °C suggested that the possibility for the application to diluted magnetic semiconductors.     

Effect of annealing temperature on structure, magnetic properties and optical characteristics in Zn0.97Cr0.03O nanoparticles

The Cr-doped zinc oxide (Zn_0.97Cr_0.03O) nanoparticles were successfully synthesized by sol-gel method. The relationship between the annealing temperature (400 °C, 450 °C, 500 °C and 600 °C) and the structure, magnetic properties and the optical characteristics of the produced samples was studied. The results indicate that Cr (Cr³⁺) ions at least partially substitute Zn (Zn²⁺) ions successfully. Energy dispersive spectroscopy (EDS) measurement showed the existence of Cr ion in the Cr-doped ZnO. The samples sintered in air under the temperature of 450 °C had single wurtzite ZnO structure with prominent ferromagnetism at room temperature, while in samples sintered in air at 500 °C, a second phase-ZnCr₂O₄ was observed and the samples were not saturated in the field of 10000 Oe. This indicated that they were mixtures of ferromagnetic materials and paramagnetic materials. Compared with the results of the photoluminescence (PL) spectra, it was reasonably concluded that the ferromagnetism observed in the studied samples was originated from the doping of Cr in the lattice of ZnO crystallites.     

Mössbauer study of Na0.82Co0.99Fe0.01O2

We studied by Mössbauer spectroscopy the Na_0.82CoO₂ compound using 1% ⁵⁷Fe as a local probe which substitutes for the Co ions. Mössbauer spectra at T=300 K revealed two sites which correspond to Fe³⁺ and Fe⁴⁺. The existence of two distinct values of the quadrupole splitting instead of a continuous distribution should be related with the charge ordering of Co⁺³, Co⁺⁴ ions and ion ordering of Na(1) and Na(2). Below T=10 K part of the spectrum area, corresponding to Fe⁴⁺ and all of Fe³⁺, displays broad magnetically split spectra arising either from short-range magnetic correlations or from slow electronic spin relaxation.     

Al和Ni共掺ZnO光学性质的第一性原理研究

利用第一性原理方法研究了纯ZnO以及掺杂Al,Ni和（Al,Ni）共掺的ZnO材料,对掺杂前后晶体的几何结构、能带结构和电子态密度,特别是光学性质进行了比较分析. 计算结果表明,纯ZnO与Al-ZnO,Ni-ZnO和（Al,Ni）-ZnO的介电函数虚部在低能区有明显的差异,但在高能区则较为相似. 在光学性质上,Al-ZnO较之Ni-ZnO在可见光区的吸收系数和反射率都非常低,反映其在可见光区有高透过率. 而两原子共掺后的（Al,Ni）-ZnO,其光学性质较之单原子掺杂的情况有非常显著的变化. 关键词： ZnO 掺杂 第一性原理 光学性质     

Dopant distribution, oxygen stoichiometry and magnetism of nanoscale Sn0.99Co0.01O2

In recent work, we have shown that chemically synthesized Sn_1−xCo_xO₂ nanoscale powders with x≤0.01 are ferromagnetic at room temperature when prepared by annealing the reaction precipitate in the narrow temperature window of 350-600 ^°C. Combined high resolution x-ray photoelectron spectroscopy (on as-prepared and Ar⁺ ion sputtered samples), x-ray diffraction and magnetometry measurements showed that the Co distribution is more uniform throughout the individual Sn_0.99Co_0.01O₂ particles when prepared at lower annealing temperatures of 350-600 ^°C and this uniform dopant distribution is essential to produce stable high temperature ferromagnetism. However, surface segregation of the dopant atoms in samples annealed at >600 ^°C destroys the room-temperature ferromagnetic behavior and reduces the Curie temperature to <300 K.     

First-principles study of electronic and optical properties in wurtzite Zn1-xCuxO

We perform a first-principles simulation to study the electronic and optical properties of wurtzite Zn1 xCuxO.The simulations are based upon the Perdew-Burke-Ernzerhof form of generalised gradient approximation within the density functional theory.Calculations are carried out in different concentrations.With increasing Cu concentration,the band gap of Zn1 xCuxO decreases due to the shift of valence band.The imaginary part of the dielectric function indicates that the optical transition between O 2p states in the highest valence band and Zn 4s states in the lowest conduction band shifts to the low energy range as the Cu concentration increases.Besides,it is shown that the insertion of Cu atom leads to redshift of the optical absorption edge.Meanwhile,the optical constants of pure ZnO and Zn0.75Cu0.25O,such as loss function,refractive index and reflectivity,are discussed.     

Optical properties of oxide magnetic ZnO, Zn0.95Mn0.05O and Cu2O nanopowders

ZnO, Zn_0.95Mn_0.05O and Cu₂O nanocrystals are synthesized. Excitonic lines in absorption spectra of these materials are detected. In photoluminescence and photoluminescence excitation spectra of Zn_0.95Mn_0.05O the dangling bond hybrid (DBH) state is found. It has splitted out from the top of the valence band due to the hybridization between d-states of the Mn impurity and the p-states of oxygen.     

Optical properties of bulk Zn1−xCoxO magnetic semiconductors

Polycrystalline Zn_1−xCo_xO (x=0, 0.02, 0.05, 0.10 and 0.15) oxides have been synthesized by solid state reaction via sintering ZnO and Co powders in open air. X-ray diffraction analyses using Rietveld refinement indicate that a stoichiometric single phase with a wurtzite-like structure was found in Zn_1−xCo_xO samples with x up to 0.10. The elemental mapping using energy dispersive X-ray spectroscopic analyses presents a uniform distribution of Co. Optical transmittance measurements show that several extra absorption bands appear in the Co-doped ZnO, which is due to the transitions between the crystal-field-split 3d levels of tetrahedral Co²⁺ substituting Zn²⁺ ions. Raman measurements show that limited host lattice defects are induced by Co doping. Magnetization measurements reveal that the Co-doped ZnO samples are paramagnetic due to the absence of free carriers and in low temperature the dominant magnetic interaction is nearest-neighbor antiferromagnetic.     

Microstructures, surface bonding states and room temperature ferromagnetisms of Zn0.95Co0.05O thin films doped with copper

Zn_0.95−xCo_0.05Cu_xO (ZCCO, where x = 0, 0.005, 0.01 and 0.015) thin films were deposited on Si (1 0 0) substrates by pulsed laser deposition technique. Crystal structures, surface morphologies, chemical compositions, bonding states and chemical valences of the corresponding elements for ZCCO films were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM) and X-ray photoelectron spectroscopy (XPS). XRD and FESEM results indicate that crystallite sizes of the highly (0 0 2)-oriented ZCCO films slightly decrease with increasing Cu content. When the Cu content increases from 0 to 0.015, Zn 2p_3/2, Co 2p, Cu 2p_3/2 and O 1s peaks of the ZCCO film shift towards higher or lower binding energy regions, and the reasons for these chemical shifts are investigated by fitting the corresponding XPS narrow-scan spectra. Both in-plane and out-of-plane magnetization-magnetic field hysteresis loops of the ZCCO films reveal that all the films have room temperature ferromagnetisms (RTFMs). The conceivable origin of the RTFM is ascribed to the combined effects of the local structural disorder resulted from (Co²⁺, Cu²⁺, Cu¹⁺)-cations which substitute Zn²⁺ ions in the ZnO matrices, ferromagnetic coupling between coupled dopant atoms caused by Co²⁺ (3d⁷4s⁰) and Cu²⁺ (3d⁹4s⁰) spin states, and exchange interactions between the unpaired electron spins originating from lattice defects induced by Cu doping in the Zn_0.95Co_0.05O matrices.     

退火对Mn和N共掺杂的Zn0.88Mn0.12O:N薄膜特性的影响

以NH₃为掺N源,采用电子束反应蒸发技术生长了Mn和N共掺杂的Zn_1-xMn_xO:N薄膜,生长温度为300℃,然后在O₂气氛中400℃退火0.5 h.X射线衍射测量表明,Zn_0.88Mn_0.12O(Mn掺杂)薄膜或Zn_0.88Mn_0.12O:N(Mn和N共掺杂)薄膜仍具有单一晶相纤锌矿结构,未检测到杂质相 关键词： ZnO薄膜 Mn和N共掺杂 电学特性 磁特性     

溶剂热合成法制备的Zn1-xMnxO和Zn1-2xMnxLixO纳米材料的磁学性质

用溶剂热合成法在160oC制备出Zn_1-xMn_xO纳米棒和Zn_1-2xMn_xLi_xO纳米颗粒. XRD和拉曼测试结果表明Mn离子已很好地掺入ZnO母体中. M-H图中未观察到磁回滞,ESR谱中的精细结构说明掺杂的Mn离子间没有铁磁相互作用. 共掺Li仅仅改变了产物的形貌,并不能改变其磁学性质.     

A first-principles study of the magnetic properties in boron-doped ZnO

First-principles calculations based on density functional theory are performed to study the origin of ferromagnetism in boron-doped ZnO. It is found that boron atoms tend to reside at Zn sites. The induced Zn vacancy is a key factor for ferromagnetism in Zn1-xBxO (0相似文献   

Asymmetric electrical properties in Pt/Ba0.5Sr0.5Ti0.99Co0.01O3/Nb-doped SrTiO3 capacitors

Ba_0.5Sr_0.5Ti_0.99Co_0.01O₃ (BSTC) thin films have been fabricated with pulsed laser deposition on Nb-doped SrTiO₃ (STN) substrate. In Pt/BSTC/STN capacitor, we systematically investigated the capacitance, leakage current and polarization versus bias voltage characteristics, and found that curves of capacitance versus voltage and leakage current versus voltage were not symmetric, and polarization hysteresis loop exhibited large relaxation of the remnant polarization at negatively poled state. A detailed analysis of capacitance data demonstrated a difference of the built-in voltage between top Pt/BSTC interface (V_b,t=2.5 V) and bottom BSTC/STN interface (V_b,b=1.1 V). Such different built-in voltages lead to the presence of an internal electric field, which results in asymmetric electric characteristics in Pt/BSTC/STN capacitor.     

Al，Ga掺杂ZnO电子结构和光电特性的第一性原理计算

采用基于密度泛函理论(DFT)框架下广义梯度近似(GGA)的PBE平面波超软赝势方法,计算了本征ZnO,Al掺杂ZnO(ZnAlO)和Ga掺杂ZnO(ZnGaO)的能带结构、态密度、复介电函数和复电导率. 其中Al或Ga是以替位杂质的形式进入ZnO晶格. 计算结果表明纤锌矿型ZnO,ZnAlO和ZnGaO都是直接带隙半导体材料,掺杂后ZnO的带隙变小,且ZnAlO的带隙略大于ZnGaO. 掺杂后ZnO的电子结构发生变化,费米能级由本征态时位于价带顶上移进入导带,ZnO表现为n型掺杂半导体材料,掺杂后在导带底出现大量由掺杂原子贡献的自由载流子—电子,明显提高了电导率和介电函数,改善了ZnO的导电性能,并且ZnAlO的导电性能要略好于ZnGaO.     

Al，Ga掺杂ZnO电子结构和光电特性的第一性原理计算

采用基于密度泛函理论(DFT)框架下广义梯度近似(GGA)的PBE平面波超软赝势方法,计算了本征ZnO,Al掺杂ZnO(ZnAlO)和Ga掺杂ZnO(ZnGaO)的能带结构、态密度、复介电函数和复电导率. 其中Al或Ga是以替位杂质的形式进入ZnO晶格. 计算结果表明纤锌矿型ZnO,ZnAlO和ZnGaO都是直接带隙半导体材料,掺杂后ZnO的带隙变小,且ZnAlO的带隙略大于ZnGaO. 掺杂后ZnO的电子结构发生变化,费米能级由本征态时位于价带顶上移进入导带,ZnO表现为n型掺杂半导体材料,掺杂后在导带底出现大量由掺杂原子贡献的自由载流子—电子,明显提高了电导率和介电函数,改善了ZnO的导电性能,并且ZnAlO的导电性能要略好于ZnGaO.