Emission and excitation spectra of ZnO:Ga and ZnO:Ga,N ceramics

The spectral characteristics of ZnO:Ga and ZnO:Ga,N ceramics prepared by uniaxial hot pressing have been investigated. At room temperature, the edge (exciton) band at 3.12 eV dominates in the luminescence spectra of ZnO:Ga, while a wide luminescence band at 2.37 eV, which is likely to be due to zinc vacancies, is observed in the spectra of ZnO:Ga,N. Upon heating, the edge band maximum shifts to lower energies and the bandwidth increases. The extrapolated position of the edge-band maximum at zero temperature, E _m (0) = 3.367 ± 0.005 eV, is in agreement with the data for thin zinc oxide films. The luminescence excitation spectra in the range from 3 to 6.5 eV are reported and the mechanism of energy transfer to excitons and luminescence centers is considered.     

纳米ZnO薄膜的光致发光性质

利用溶胶－凝胶法制备了纳米ZnO薄膜,室温下测量了样品的光致发光谱(PL)、吸收谱(ABS)、X射线衍射谱(XRD)．X射线衍射(XRD)的结果表明：纳米ZnO薄膜呈多晶状态,具有六角纤锌矿晶体结构和良好的C轴取向．观察到二个荧光发射带,中心波长分别位于395 nm的紫带、524 nm的绿带和450 nm附近的蓝带．证实了纳米ZnO薄膜绿光可见发射带来自氧空位(VO)形成的浅施主能级和锌空位(VZn)形成的浅受主能级之间的复合;450 nm附近的蓝带来自电子从VO的浅施主能级到价带顶或锌填隙(Zni) 到价带顶或导带底到VZn的浅受主能级的复合．     

两步溶液法制备亚微米ZnO棒阵列及其退火后的发光

通过改变溶液浓度、酸碱度等生长条件,用两步化学溶液沉积法在玻璃衬底上制备出有序排列的亚微米级ZnO棒阵列,棒的截面呈正六边形,直径约为200~500nm。测量了样品的XRD谱和扫描电镜像,证明这些样品都是六方纤锌矿结构的ZnO单晶,且以[002]方向择优生长。将样品退火前后的PL光谱进行比较分析,发现退火后样品的发射光谱中紫外峰消失而长波段的红色发光峰红移并且增强(峰位由630nm左右移到720nm),而其激发光谱中的室温激子激发峰也增强。当退火时间增加到6h后,出现了由430nm的蓝峰和505nm绿峰组成的宽谱带蓝绿色发射。并对发光机理进行了讨论。     

纳米ZnO薄膜可见发射机制研究

利用溶胶－凝胶法 （Sol-Gel）制备了纳米ZnO薄膜,获得了高强的近紫外发射室温下测量了样品的光致发光谱(PL )、吸收谱(ABS)、X射线衍射谱(XRD).X射线衍射(XRD)的结果表明：纳米ZnO薄膜呈多晶态,具有六角纤锌矿结构和良好的C轴取向;发现随退火温度升高,（002）衍射峰强度显著增强,衍射峰的半高宽（FWHM）减小、纳米颗粒的粒径增大.由吸收谱(ABS)给出了样品室温下带隙宽度为3.30 eV.在PL谱中观察到二个荧光发射带,一个是中心波长位于392 nm附近强而尖的紫带,另一个是519 nm附近弱而宽的绿带研究了不同退火温度样品的光致发光峰值强度的变化关系,发现随退火温度升高,紫带峰值强度增强、绿带峰值强度减弱,均近似呈线性变化.证实了纳米ZnO薄膜绿光发射主要来自氧空位(Vo)形成的浅施主能级与锌空位(VZn)形成的浅受主能级之间的复合,或氧空位(Vo)形成的深施主能级上的电子至价带顶的跃迁;紫带来自于导带中的电子与价带中的空位形成的激子复合.     

Luminescence of a ZnO:Ga crystal upon excitation in vacuum UV region

The spectral-kinetic characteristics of a ZnO:Ga single crystal upon excitation in the vacuum UV region have been studied. At a temperature of 8 K, the exciton luminescence line peaking at 3.356 eV has an extremely small half-width (7.2 meV) and a short decay time (360 ps). In the visible range, a wide luminescence band peaking at ～2.1 eV with a long luminescence time at 8 K and a decay time in the nanosecond range at 300 K is observed. The luminescence excitation spectra of ZnO:Ga have been measured in the range of 4–12.5 eV.     

The charge states’ conversion of the activator ions in CaF2:Eu nanophosphors

According to stationary X-ray-excited luminescence spectra and thermally stimulated luminescence spectra of CaF₂:Eu nanophosphors, it was found that Eu³⁺?→?Eu²⁺ conversion can occur during thermal annealing of fine-grained (d?=?25?nm) nanoparticles in the 200–800°C range, which is accompanied by an increase in their size within 40–189?nm. An important role of the exciton mechanism of Eu²⁺ luminescence excitation was revealed according to the temperature dependence of X-ray-excited luminescence spectra of CaF₂:Eu nanoparticles of 114?nm size. The maximum of the X-ray-excited luminescence light output of CaF₂:Eu nanophosphors in the Eu²⁺ ions’ emission band was traced out at 400–500°C annealing temperature and at the size of nanoparticles of 114–180?nm. The subsequent growth of the annealing temperatures, particularly in the 800–1000°C range, causes the reduction of X-ray-excited luminescence light output because of the increment of lattice defects’ concentration due to a sharp increase in the size of nanoparticles and their agglomeration.     

Luminescence properties of transparent ceramics Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Yb

We present the results of studying the luminescence properties of transparent ceramics Y₃Al₅O₁₂:Yb obtained by the vacuum sintering and nanocrystalline technology. In the course of research, we measured the luminescence and luminescence excitation spectra, as well as the temperature and kinetic behavior of luminescence. Our results are analyzed in comparison with the characteristics of corresponding single crystals. We revealed that processes of generation and relaxation of electronic excitations that occur in ceramics, in particular, in the charge transfer state, are similar to processes occurring in crystals. The behavior of two charge-transfer luminescence bands at 340 and 490 nm is studied. In the range 300–600 nm, we revealed a broad emission band of radiation of other type, which is also observed in spectra of undoped ceramics. This broad band is attributed to F⁺ centers. Emission and excitation spectra of charge transfer luminescence at a maximum of the temperature dependence of 100 K are measured for the first time. We found that, upon excitation in the charge transfer band, luminescence in ceramics is more intense than in single crystals with similar concentrations of Yb and has a higher quenching temperature.     

Energy Levels in the Forbidden Band of the Bi4Ge3O12 Ceramics

Thermally stimulated luminescence in the Bi₄Ge₃O₁₂ ceramics and also in the ceramics of the parent components Bi₂O₃ and GeO₂ is investigated. The similarity of the curves of the thermally stimulated luminescence in bismuth germanate with the structure of eulytine Bi₄Ge₃O₁₂ and sillenite Bi₁₂GeO₂₀ is explained. The relation of the thermally stimulated luminescence band in Bi₄Ge₃O₁₂ (with a maximum at 143 K) to the disruptions in the germanium sublattice and of the thermally stimulated band (with a maximum at 187 K) to the recombination processes in the bismuth sublattice is shown. It has been established that the light sum in the Bi₄Ge₃O₁₂ ceramics is stored most effectively upon excitation by light in an energy region of 4.4 eV.     

Structural and optical properties of Au-implanted ZnO films

The structural and luminescence related optical behaviours of Au ion implanted ZnO films grown by magnetic sputtering and their post implantation annealing behaviours in the temperature range of 100-700 °C have been investigated. Optical absorption and transmittance spectra of the films indicate that band edge of Au-implanted ZnO has shifted to high energy range and optical band gap has increased, because the sharp difference of thermal expansion induces the lattice mismatch between ZnO and SiO₂. PL spectra reveal that UV and visible luminescence bands of ZnO films can be improved after thermal annealing due to recovery of defects and Au ions incorporation. Importantly, green luminescence band of 530 nm has been only observed in the Au-implanted and subsequently annealed ZnO films and it enhances with the increasing annealing temperature, which can be related to Au atoms or clusters in ZnO films. Furthermore, X-ray photoelectron spectroscopy measurements reveal that the Au⁰ is dominant state in Au implanted and annealed ZnO films. Possible mechanisms, such as optical transitions of Au atoms or clusters and deep level luminescence of ZnO, have been proposed for green emission.     

Thermally stimulated generation–recombination processes in zinc oxide single crystals and nanocrystals

We present an analysis of the theory of thermally stimulated generation×recombination processes occurring in semiconductors with participation of trapping and recombination centers, based on which we develop algorithms for a program for computer processing of experimental data and simulation of the thermally stimulated conductivity and thermally stimulated luminescence spectra. We determine the characteristic parameters of the trapping centers. We compare the results of computer simulation with experimentally observed thermally stimulated luminescence spectra of ZnO single crystals and nanocrystals.     

Tunneling recombination luminescence under excitation of PbWO4:Mo crystals in the defect-related absorption region

Time-resolved emission and excitation spectra and luminescence decay kinetics were studied at 150-300 K for the green emission of PbWO₄:Mo crystals. It was found that the slow (μs-ms) decay component observed under excitation in the defect-related absorption region (around 3.8-3.9 eV) arises from the G(II) emission which appears at the tunneling recombination of optically created electron and hole centers. The study of the emission decay kinetics at different temperatures and excitation intensities allowed concluding that both the monomolecular and the bimolecular tunneling recombination process can be stimulated in the mentioned energy range. The monomolecular process takes place in the isolated spatially correlated pairs of electron and hole centers produced without release of electrons into the conduction band. The bimolecular process takes place in the pairs of randomly distributed centers created at the trapping of free electrons from the conduction band. The formation of electron centers under irradiation in the defect-related absorption region was investigated by the electron spin resonance (ESR) and thermally stimulated luminescence (TSL) methods. The possibility of various photo-thermally stimulated defects creation processes, which take place with and without release of free electrons into the conduction band, was confirmed.     

Luminescence and thermally stimulated recombination processes in Li<Subscript>6</Subscript>Gd(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>:Ce<Superscript>3+</Superscript> crystals

The luminescence and thermally stimulated recombination processes in lithium borate crystals Li₆Gd(BO₃)₃ and Li₆Gd(BO₃)₃:Ce have been studied. The steady-state luminescence spectra under X-ray excitation (X-ray luminescence), temperature dependences of the intensity of steady-state X-ray luminescence (XL), and thermally stimulated luminescence (TSL) spectra of these compounds have been investigated in the temperature range of 90–500 K. The intrinsic-luminescence 312-nm band, which is due to the ⁶ P _J → ⁸ S _7/2 transitions in Gd³⁺ matrix ions, dominates in the X-ray luminescence spectra of these crystals; in addition, there is a wide complex band at 400–420 nm, which is due to the d → f transitions in Ce³⁺ impurity ions. It is found that the steady-state XL intensity in these bands increases several times upon heating from 100 to 400 K. The possible mechanisms of the observed temperature dependence of the steady-state XL intensity and their correlation with the features of electronic-excitation energy transfer in these crystals are discussed. The main complex TSL peak at 110–160 K and a number of minor peaks, whose composition and structure depend on the crystal type, have been found in all crystals studied. The nature of the shallow traps that are responsible for TSL at temperatures below room temperature and their relation with defects in the lithium cation sublattice are discussed.     

Photoluminescence of the ZnSe single crystals doped by thermal diffusion of nitrogen

Photoluminescence (PL) spectra of ZnSe single crystals annealed in different ambients containing molecular nitrogen are investigated. The compensating activity of N impurity in n-ZnSe crystals is shown. It is caused by the formation of N_Se acceptor centers, having 101-108 meV activation energy. The intensity of amplification of both long-wave luminescence spectra bands and the edge luminescence spectra bands caused by the presence of nitrogen in annealing medium is investigated. The presented results allow one to assign the long-wave luminescence to deep acceptors caused by uncontrollable impurities, and the relevant bands of the edge luminescence spectra to the excitons bound with the same deep acceptors. The model explaining the transformations of the luminescent properties of ZnSe crystals by means of nitrogen impurity doping is proposed. The model considers the presence of donors having 75 meV activation energy, acceptors having 220-720 meV activation energy and centers having levels localized near the middle of the band gap.     

Photoluminescence and Raman spectra of SnO<Subscript>x</Subscript> nanostructures doped with Sm ions

The photoluminescence (PL) and Raman scattering of SnO_x nanoparticles deposited from vapor phase have been studied. The PL spectra are characterized by a two-band structure. The high-energy band in the range from 300 to 350 nm is due to the exciton pair annihilation and may characterize the band gap of SnO_x nanocrystals as a function of their diameter. In the red spectral region (from 600 to 700 nm), a luminescence band due to defects in nanocrystals manifests itself. The existence of defects in SnO_x nanostructures is confirmed by Raman spectroscopy. Doping of SnO_x nanoparticles with rare earth (samarium) atoms leads to the appearance of strong luminescence lines in the red region of the PL spectrum.     

纳米ZnO薄膜的激子光致发光特性

报道了纳米ZnO薄膜激子光致发光(PL)与温度的关系。首先利用低压金属有机化学气相沉积(LPMOCVD)技术生长ZnS薄膜,然后将ZnS薄膜在氧气中于800℃下热氧化2h获得纳米ZnO薄膜。X射线衍射(XRD)结果表明,纳米ZnO薄膜具有六角纤锌矿多晶结构且具有择优(002)取向。室温下观察到一束强的紫外(326eV)光致发光(PL)和很弱的深能级(DL)发射。根据激子峰的半高宽(FWHM)与温度的关系,确定了激子纵向光学声子(LO)的耦合强度(ГLO)。     

Intrinsic ultraviolet luminescence from Lu2O3, Lu2SiO5 and Lu2SiO5:Ce

Radioluminescence and thermally stimulated luminescence measurements on Lu₂O₃, Lu₂SiO₅ (LSO) and Lu₂SiO₅:Ce³⁺ (LSO:Ce) reveal the presence of intrinsic ultraviolet luminescence bands. Characteristic emission with maximum at 256 nm occurs in each specimen and is attributed to radiative recombination of self-trapped excitons. Thermal quenching of this band obeys the Mott-Seitz relation yielding quenching energies 24, 38 and 13 meV for Lu₂O₃, LSO and LSO:Ce, respectively. A second intrinsic band appears at 315 nm in LSO and LSO:Ce, and at 368 nm in Lu₂O₃. Quenching curves for these bands show an initial increase in peak intensity followed by a decrease. Similarity in spectral peak position and quenching behavior indicate that this band has a common origin in each of the samples and is attributed to radiative recombination of self-trapped holes, in agreement with previous work on similar specimens. Comparison of glow curves and emission spectra show that the lowest temperature glow peaks in each specimen are associated with thermal decay of self-trapped excitons and self-trapped holes. Interplay between the intrinsic defects and extrinsic Ce³⁺ emission in LSO:Ce is strongly indicated.     

Thermally stimulated recombination processes and luminescence in Li<Subscript>6</Subscript>(Y,Gd,Eu)(BO<Subscript>3</Subscript>)<Subscript>3</Subscript> crystals

The thermally stimulated recombination processes and luminescence in crystals of the lithium borate family Li₆(Y,Gd,Eu)(BO₃)₃ have been investigated. The steady-state luminescence spectra under X-ray excitation (X-ray luminescence spectra), the temperature dependences of the X-ray luminescence intensity, and the glow curves for the Li₆Gd(BO₃)₃, Li₆Eu(BO₃)₃, Li₆Y_0.5Gd_0.5(BO₃)₃: Eu, and Li₆Gd(BO₃)₃: Eu compounds have been measured in the temperature range 90–500 K. In the X-ray luminescence spectra, the band at 312 nm corresponding to the ⁶ P _J → ⁸ S _7/2 transitions in the Gd³⁺ ion and the group of lines at 580–700 nm due to the ⁵ D ₀ → ⁷ F _J transitions (J = 0–4) in the Eu³⁺ ion are dominant. For undoped crystals, the X-ray luminescence intensity of these bands increases by a factor of 15 with a change in the temperature from 100 to 400 K. The possible mechanisms providing the observed temperature dependence of the intensity and their relation to the specific features of energy transfer of electronic excitations in these crystals have been discussed. It has been revealed that the glow curves for all the crystals under investigation exhibit the main complex peak with the maximum at a temperature of 110–160 K and a number of weaker peaks with the composition and structure dependent on the crystal type. The nature of shallow trapping centers responsible for the thermally stimulated luminescence in the range below room temperature and their relation to defects in the lithium cation sublattice have been analyzed.     

ZnO压敏陶瓷介电损耗的温度谱研究

利用Novocontrol宽频介电谱仪在-100—20 ℃温度范围内测量了ZnO-Bi₂O₃系压敏陶瓷的介电频谱,其频率范围为10^-2—10⁶ Hz. 研究表明： ZnO压敏陶瓷特征损耗峰的活化能分别为0.26和0.36 eV,结合实验条件、理论计算结果及其他现象的分析排除了特征损耗峰源于阴极电子注入、夹层极化和偶极子转向极化的可能.热刺激电流（TSC）谱共出现三个峰,其中高温峰对应于TSC实验加压过程引入的热离子极化,而中温峰和低温峰对应于介电损耗峰. 在分析的基础上,提出了ZnO压敏陶瓷的特征损耗峰起源于耗尽层内本征缺陷的电子弛豫过程. 关键词： ZnO压敏陶瓷 本征缺陷 介电谱 热刺激电流     

The nature of the predominant acceptors in high quality zinc telluride

We report very sharp bound exciton luminescence spectra in high quality melt-grown very lightly compensated ZnTe, p-type with N_A-N_D in the low 10⁺¹⁵ cm^-3. Bound exciton localisation energies at seven shallow neutral acceptors with E_A between ~55 and ~150 meV are very insensitive to E_A. Optical absorption and dye laser luminescence excitation spectroscopy were necessary to obtain a full separation of the transitions due to different acceptors, together with a study of certain ‘two-hole’ luminescence satellites in which the acceptor is left in a series of orbital states after bound exciton decay. Two shallow acceptors are P_Te and As_Te, a third possibly Li_Zn while a fourth, relatively prominent in our best undoped crystals, may be a complex. A deeper, 150 meV acceptor, frequently reported in the ZnTe literature and electrically dominant in most of our undoped crystals has the Zeeman character of a point defect. We present clear evidence from our spectra that this energy does not represent the binding of a single hole at a doubly ionized cation vacancy, a popular attribution since 1963. This acceptor may be covered by another impurity, possibly Cu_Zn. We also report bound phonon effects, lifetime broadening of excited bound exciton states and observe a single unidentified donor with E_D ~18.5 meV. This energy is determined using selective dye laser excitation at the weak neutral donor bound exciton line and from the onset of valence band to ionized donor photo-absorption.