An alternative approach to investigate the origin of p-type conductivity in arsenic doped ZnO

P-type conductivity in MOCVD grown ZnO was obtained by directional thermal diffusion of arsenic from semi-insulating GaAs substrate. The films were single crystalline in nature and oriented along (002) direction. Ab initio calculations in the framework of density functional theory have been carried out with different chemical states of arsenic in ZnO. Present calculations suggested As_Zn–2V_Zn defect is a shallow acceptor and results in ferromagnetism in ZnO. The magnetic measurements of the samples indeed showed ferromagnetic ordering at room temperature. X-ray photoelectron spectra confirmed the presence of As_Zn and V_Zn. The core level chemical shift in binding energy of As_Zn indicated the formation of As_Zn–2V_Zn. Diffused arsenic substitutes zinc atom and creates additional zinc vacancies. The zinc vacancies, surrounding the oxygen atoms, result in unpaired O 2p electrons which in turn induce ferromagnetism in the samples.     

Highly enhanced luminescence of ZnO green phosphors by calcining ZnS with NH4Br as additive

Zinc oxide (ZnO) phosphors with highly efficient green emission have been prepared by calcining ZnS with NH₄Br as additive in air atmosphere. The luminescent properties of as-prepared ZnO phosphors were characterized by X-ray photoelectron spectroscopy and photoluminescence. Our results reveal that the green emission is ascribed to a transition of a photo-generated electron from the localized defect centers (V_o⁺) to a deeply trapped hole (V_Zn⁻) within the band gap. The addition of NH₄Br enhances the luminescent emission of ZnO by promoting the formation of vacancies of both oxygen and zinc.     

Theoretical study of the magnetic interaction of Cr-doped ZnO with and without vacancies

First-principles density-functional theory (DFT) calculations have been performed to study the magnetic properties of ZnO:Cr with and without vacancies. The results indicate that the doping of Cr in ZnO induces obvious spin polarization around the Fermi level and a total magnetic moment of 3.77μ_B. The ferromagnetism (FM) exchange interaction between Cr atoms is short-ranged and decreases with increasing Cr separation distance. It is suggested that the FM state is not stable with low concentration of Cr. The presence of O vacancies can make the half-metallic FM state of the system more stable, so that higher Curie temperature ferromagnetism may be expected. Nevertheless, Zn vacancies can result in the FM stability decreasing slightly. The calculated formation energy shows that V_Zn+Cr_Zn complex forms spontaneously under O-rich conditions. However, under Zn-rich conditions, the complex of V_O+Cr_Zn forms more easily. Thus, ZnO doped with Cr may exhibit a concentration of vacancies that influence the magnetic properties.     

Sauerstofflücken als Donatoren in Zinkoxid

Then-conductivity of zinc oxide single crystals is discussed in terms of the formation of oxygen ion vacancies,V ₀, instead of interstitial zinc ions, Zn _i ⁺ . The oxygen vacancies act as donors and may have one or two electrons depending on the degree of ionization. Zinc ion vacanciesV _Zn ^{- –} act as acceptors in the crystals.     

p型K:ZnO导电机理的第一性原理研究

基于密度泛函理论,利用局域密度近似的第一性原理平面波赝势方法,对掺K以及含有氢填隙(H_i)、氧空位(V_O)、锌填隙(Zn_i)和锌空位(V_Zn)的K:ZnO电子结构分别进行了研究.结果表明,1) 单独掺K可引入浅受主,但系统总能增高;2) K与H共掺可降低系统总能,提升稳定性;3) V_O在K+H:ZnO中的形成比Zn_i困难得多,二者都是 关键词： 氧化锌 p型 第一性原理 电子结构     

The electronic and magnetic properties with intrinsic defects in ZnO nanosheets: First-principles prediction

Using full-potential linearized augmented plane wave (FLAPW) method, we investigated the effects of intrinsic vacancies on electronic and magnetic properties in graphene-like ZnO nanosheets. The results show that the oxygen vacancy (V_O) has no influence on magnetism in ZnO nanosheet, whereas the Zn vacancy (V_Zn) lead to spin polarization of the nanostructures with a total magnetic moment of 2.0μ_B due to O-2p and Zn-3d hybridization. When the distance of two V_Zn defects increases to 6.499 Å, the system shows an intriguing half-metallic character with 100% spin-polarized carriers due to O(2p)–Zn(3d)–O(2p) coupling chain between two V_Zn defects.     

Growth,electronic and magnetic properties of doped ZnO epitaxial and nanocrystalline films

We have used oxygen plasma assisted metal organic chemical vapor deposition along with wet chemical synthesis and spin coating to prepare Co_xZn_1-xO and Mn_xZn_1-xO epitaxial and nanoparticle films. Co(II) and Mn(II) substitute for Zn(II) in the wurtzite lattice in materials synthesized by both methods. Room-temperature ferromagnetism in epitaxial Co:ZnO films can be reversibly activated by diffusing in Zn, which occupies interstitial sites and makes the material n-type. O-capped Co:ZnO nanoparticles, which are paramagnetic as grown, become ferromagnetic upon being spin coated in air at elevated temperature. Likewise, spin-coated N-capped Mn:ZnO nanoparticle films also exhibit room-temperature ferromagnetism. However, the inverse systems, N-capped Co:ZnO and O-capped Mn:ZnO, are entirely paramagnetic when spin coated into films in the same way. Analysis of optical absorption spectra reveals that the resonances Co(I)↔Co(II)+e^- _CB and Mn(III)↔Mn(II)+h⁺ _VB are energetically favorable, consistent with strong hybridization of Co (Mn) with the conduction (valence) band of ZnO. In contrast, the resonances Mn(I)↔Mn(II)+e^- _CB and Co(III)↔Co(II)+h⁺ _VB are not energetically favorable. These results strongly suggest that the observed ferromagnetism in Co:ZnO (Mn:ZnO) is mediated by electrons (holes). PACS 75.50.Pp     

Structure and magnetism of Zn0.9Co0.1O DMS films prepared by chemical solution deposition method

The Zn_0.9Co_0.1O films are fabricated by chemical solution deposition method. All the films have the ZnO wurtzite structure with a preferential orientation along the c-axis. The analysis of X-ray near-edge absorption spectroscopy and X-ray photoelectron spectroscopy indicates that the valence of Co is +2, and there are oxygen vacancies in Zn_0.9Co_0.1O films annealed in Ar atmosphere. Extended X-ray absorption fine structure results reveal that Co²⁺ ions have dissolved into ZnO and substituted for Zn²⁺ ions. Magnetization measurements show that the film annealed in Ar exhibits ferromagnetism which can be explained by the formation of bound magnetic polarons.     

Microstructural and magnetic properties of Ax:Zn1-xO (A=Mn,Gd and Mn/Gd) nanocrystals

We report the microstructural and magnetic properties of transition (3d) and rare earth (4f) metal substituted into the A_x:Zn_1?xO (A=Mn, Gd and Mn/Gd) nanocrystal samples synthesized by solgel method. The structural properties and morphology of all samples have been analysed using X-ray diffraction (XRD) method and scanning electron microscopy. The impurity phase in the XRD patterns for all samples is not seen, except (Mn/Gd):ZnO sample where a very weak secondary phase of Gd₂O₃ is observed. Due to the large mismatch of the ionic radii between Mn²⁺ and Gd³⁺ ions, the strain inside the matrix increases, unlike the crystallite size decreases with the substitution of Mn and Gd into ZnO system. A couple of additional vibration modes due to the dopant have been observed in Raman spectrum. The magnetic properties have been studied by vibrating sample magnetometer. The magnetic hysteresis shows that Mn:ZnO and Gd:ZnO have soft ferromagnetic (FM) behaviour, whereas (Mn/Gd):ZnO has strong FM behaviour at room temperature (RT). The enhancement of ferromagnetism (FM) in (Mn/Gd):ZnO sample might be related to short-range FM coupling between Mn²⁺ and Gd³⁺ ions via defects potential and/or strain-induced FM coupling due to the expansion lattice by doping. The experimental results indicate that RTFM can be achieved by co-substitution of 3d and 4f metals in ZnO which can be used in spintronics applications.     

Comparative analysis of emission and absorption spectra of zinc oxide powders

Photoluminescence and optical absorption spectra induced by proton and electron irradiation in zinc oxide powders have been investigated. It has been found that the emission band in a visible region with a maximum of about 2.3 eV is a superposition of three bands with 2.55, 2.34, 2.12 eV, respectively, caused by oxygen vacancies V _O⁺, interstitial oxygen O _i ⁻, and zinc vacancies V _Zn⁻ absorbing in the 3.03-, 2.83-, and 2.64-eV bands.     

Ferromagnetism induced by oxygen-vacancy complex in (Mn,in) codoped ZnO

Mn doped Zinc oxide (ZnO) thin films were prepared by metal organic chemical vapor deposition (MOCVD) technique. Structural characterizations by X-ray diffraction technique (XRD) and photoluminescence (PL) indicate the crystal quality of ZnO films. PL and Raman show a large fraction of oxygen vacancies (V_O²⁺) are generated by vacuum annealed the film. The enhancement of ferromagnetism in post-annealed (Mn, In) codoped ZnO could result from V_O²⁺ incorporation. The effect of V_O²⁺ on the magnetic properties of (Mn, In) codoped ZnO has been studied by first-principles calculations. It is found that only In donor cannot induce ferromagnetism (FM) in Mn-doped ZnO. Besides, the presence of V_O²⁺ makes the Mn empty 3d-t_2g minority state broadened, and a t_2g-V_O²⁺ hybrid level at the conduction band minimum forms. The presence of V_O²⁺ can lead to strong ferromagnetic coupling with the nearest neighboring Mn cation by BMP model based on defects reveal that the ferromagnetic exchange is mediated by the donor impurity state, which mainly consists of Mn 3d electrons trapped in oxygen vacancies.     

氧空位对钴掺杂氧化锌半导体磁性能的影响

从实验和理论上阐述了氧空位对Co掺杂ZnO半导体磁性能的影响.采用磁控溅射法在不同的氧分压下制备了Zn_095Co_005O薄膜,研究了氧分压对薄膜磁性能的影响.实验结果表明,高真空条件下制备的Zn_095Co_005O薄膜具有室温铁磁性,提高氧分压后制备的薄膜铁磁性逐渐消失.第一性原理计算表明,在Co掺杂ZnO体系中引入氧空位有利于降低铁磁态的能量,铁磁态的稳定性与氧空位和Co之间的距离密切相关. 关键词： Co掺杂ZnO 稀磁半导体 第一性原理计算 氧空位缺陷     

Structure and energy level of native defects in as-grown and electron-irradiated zinc germanium diphosphide studied by EPR and photo-EPR

The properties of defects in as-grown p-type zinc germanium disphosphide (ZnGeP₂) and the influence of electron irradiation and annealing on the defect behavior were studied by means of electron paramagnetic resonance (EPR) and photo-EPR. Besides the well-known three native defects (V_Zn, V_P, Ge_Zn), an S=1/2 EPR spectrum with an isotropic g=2.0123 and resolved hyperfine splitting from four equivalent I=1/2 neighbors is observed in electron-irradiated ZnGeP₂. This spectrum is tentatively assigned to the isolated Ge vacancy. Photo-EPR and annealing treatments show that the high-energy electron irradiation-induced changes in the EPR intensities of the zinc and phosphorus vacancies are caused by the Fermi level shift towards the conduction band. Annealing of the electron-irradiated samples induces a shift of the Fermi level back to its original position, accompanied by an increase of the EPR signal associated with the V_Zn⁻ and a proportional increase of the EPR signal assigned to the V_P⁰ under illumination (λ<1 eV) as well as generation of a new defect. The results indicate that the EPR spectra originally assigned to the isolated V_Zn⁻ and V_P⁰ are in fact associated defects and the new defect is probably the isolated phosphorus vacancy V_Pi.     

Photoluminescence of zinc oxide modified by nanopowders

The modifying effect of Al₂O₃, Al₂O₃ · CeO₂, ZrO₂, ZrO₂ · Y₂O₃ nanopowders on the photoluminescence spectra of ZnO powder in the 360–660 nm range is investigated. It is found that the introduction of nanoparticles causes a decrease in the ultraviolet band intensity and an increase in the visual spectral band intensity. The change in the intensity of elementary components of the visible range band during modification seems to be explained by the emergence of oxygen and zinc vacancies (V _O⁺ and V _Zn⁻) and interstitial oxygen ions (O _i ⁻).     

共沉淀法制备Co掺杂ZnO的室温铁磁性的研究

利用共沉淀法并在5vol.%H₂/Ar气流中于300 ℃退火3 h,制备了Zn_1-xCo_xO稀磁半导体. 扫描电子微探针分析表明,对Co的名义组分分别为0.05,0.10,0.15的样品,其实际组分分别为x＝0.054, 0.100和0.159. X射线衍射表明, 主相为纤锌矿结构, x=0.100和 0.159的样品中含有CoO杂相. X射线光电子谱显示出Co有３种状态: 替代进入Z 关键词： 稀磁半导体 ZnO 共沉淀法 磁性来源     

Investigation of n-type donor defects in Co-doped ZnO

We investigate using density functional theory (DFT) the electronic structure of (∼3%) Co-doped ZnO in the presence of native n-type donor defects such as V_O and Zn_I. In particular, we apply a pseudopotential-based self-interaction correction (pseudo-SIC) scheme as an improvement to the local spin-density approximation (LSDA). This overcomes major short comings of the LSDA in describing Co-doped ZnO. Donor+dopant pair complexes such as Co–V_O and Co–Zn_I are studied as relevant magnetic centres for long-range magnetic interactions at low-dopant concentrations. We find that complex formation is energetically favourable but the inter-complex magnetic coupling is too weak to account for room temperature ferromagnetism in ZnO:Co     

Effects of copper and oxygen vacancies on the ferromagnetism of Mn- and Co-doped Cu2O

The ferromagnetic properties of Mn- and Co-doped Cu₂O with copper and oxygen vacancies (V_Cu and V_O) are studied by first-principles calculations. The results indicate that Mn-doped Cu₂O has an antiferromagnetic state in the near configuration, while it has a ferromagnetic state for the far configuration. On the contrary, Co-doped Cu₂O possess a ferromagnetic state regardless of the distance between the two Co atoms. The observed ferromagnetism can be attributed to the 90° ferromagnetic super-exchange mechanism. The presence of V_O can enhance the ferromagnetism, whereas V_Cudepresses it.     

Effect of doping with 3d elements (Co, Ni, Cu) on the intrinsic defect structure and photocatalytic properties of nanostructured ZnO with tubular morphology of aggregates

The precursor-derived nanostructured solid solutions Zn_0.95 M _0.05O (M = Co, Ni, Cu) with tubular aggregates have been investigated using optical absorption spectroscopy and electron paramagnetic resonance. The dependences of the concentration of intrinsic defects V _o ⁺ and the effective band gap on the dopant type have been determined. It has been shown using the oxidation reaction of hydroquinone dissolved in water as an example that an increase in the photocatalytic activity in the series ZnO → Zn_0.95Ni_0.05O → Zn_0.95Co_0.05O Zn_0.95Cu_0.05O in the ultraviolet and visible spectral regions correlates with a decrease in the band gap and with an increase in the concentration of oxygen vacancies V _O ⁺ .     

Ga<Subscript>Zn</Subscript>-V<Subscript>Zn</Subscript> acceptor complex defect in Ga-doped ZnO

Gallium (Ga)-doped ZnO is regarded as a promising plasmonic material with a wide range of applications in plasmonics. In this study, zinc self-diffusion experiments are adopted to disclose the nature of the dominant compensating defect in Ga-doped ZnO isotopic heterostructures. The (Ga_Zn-V_Zn)^? complex defect, instead of the isolated V_Zn^2?, is identified as the predominant compensating acceptor center responsible for the low donor doping efficiency. The comparative diffusion experiments operated by the secondary ion mass spectrometry reveal a ~0.78 eV binding energy of this complex defect, which well matches the electrical activation energy derived from the temperature-dependent Hall effect measurements (~(0.82±0.02) eV). These findings contribute to an essential understanding of the (Ga_Zn-V_Zn)^? complex defect and the potential engineering routes of heavily Ga-doped ZnO.     

Evolutions of defects and blue–green emissions in ZnO microwhiskers fabricated by vapor-phase transport

The corresponding evolutions of morphologies, defect-states and the PL properties have been employed to explore the defect-origins of visible emissions and growth mechanisms of microstructured ZnO. ZnO microtube and microrod whiskers were fabricated by non-catalytic vapor-phase transport using ZnO and graphite powders in air. The microstructures of the samples were studied in detail based on scanning electron microscopy (SEM), x-ray diffraction (XRD), energy-dispersive x-ray spectroscopy (EDX), and electron paramagnetic resonance (EPR). The main PL emission bands evolve from blue to green, which corresponds to that the main defect-states change from Zn interstitials (Zn_i) to O vacancies (V_O). The formation of Zn_i under the high temperature zinc-rich vapor environment is crucial both for the blue emission and for the formation of the microtubes.