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.     

Thermal Annealing Effects on the Absorption and Structural Properties of Regioregular Poly(3-Hexylthiophene) Films

Regioregular poly(3-hexylthiophene) (P3HT) was synthesized by a Grignard metathesis method. The annealed and fast cooled P3HT films were studied by UV-vis absorption spectroscopy, atomic force microscopy, and grazing incidence X-ray diffraction (GIXRD) measurements. It is demonstrated that thermal annealing at around the onset temperature of the melting point of the polymer results in the annealed film having the highest interchain and intrachain orders while preserving the original morphological features. However, the film that has the highest or lowest crystallinity does not have the strongest or weakest absorption. The lack of clear correlation between the absorption spectra and GIXRD data is explained by a quasi-ordered phase model, in which crystalline, amorphous, and quasi-ordered chains interconvert into each other depending on annealing temperature.     

Transformation of the microstructure and luminescence characteristics of LiF films during annealing

The microstructure of lithium fluoride thin films deposited on a glass substrate by thermal vacuum evaporation was investigated. An additional annealing of the films in air at temperatures of 400, 500, and 600°C resulted in an increase in the size of grains forming the film, as well as in the transformation of luminescence spectra of the initial and annealed samples before and after their X-ray irradiation used to generate in the films color centers that played the role of luminescent probes. It was found that an increase in the annealing temperature with an increase in the size of grains leads to a decrease in the intensity of the characteristic photoluminescence bands of color centers in lithium fluoride and to the appearance of new luminescence bands that are not characteristic of this material. Based on the results of the X-ray powder diffraction analysis, it was concluded that the increase in the grain size is caused by the change in the chemical composition of the films primarily due to the interaction of lithium fluoride with the substrate material.     

不同退火条件对纳米多孔氧化铝薄膜光致发光的影响

以草酸为电解液,采用二次阳极氧化法制备出了纳米多孔氧化铝薄膜,经不同退火温度和退火气氛处理氧化铝薄膜后,通过分析其光致发光光谱得出：相同的退火气氛中, 退火温度T≤600 ℃ 时,T=500 ℃具有最大的光致发光强度;退火温度T≥700 ℃时,随着退火温度的升高,样品的发光强度增大。在不同的退火气氛中,多孔氧化铝薄膜随着退火温度的升高,发光峰位改变不同,即在空气中退火处理后,随着退火温度的升高,发光峰位蓝移,而在真空中退火处理后,发光峰位并不随退火温度的升高而变化;通过对1 100 ℃高温退火处理后的氧化铝薄膜的光致发光曲线的高斯拟合,可以看出,经退火处理后的多孔氧化铝,主要存在三个发光中心,发光曲线在350～600 nm范围内对应三个发射峰, 发射波长分别为387,410,439 nm。相同的退火温度下,空气中退火得到的氧化铝薄膜的光致发光强度大于真空中退火处理后的氧化铝薄膜。基于实验结果,结合X射线色散能谱(EDS)、红外反射光谱等表征手段,探讨了多孔氧化铝薄膜的发光机制,并对经过不同退火条件得到的多孔氧化铝薄膜的光致发光特性的改变做出了合理的解释。     

Absorption and photoluminescence properties of silver clusters in SiO<Subscript>2</Subscript> matrix

Absorption and luminescence properties of silver nanoclusters embedded in SiO₂ matrixes were studied experimentally. Thin SiO₂ films with different amount of silver were produced by co-deposition of Ag and SiO₂ onto the silica substrates in vacuum. The thus obtained films possess three peaks in absorption spectra at 297, 329 and 401 nm and two peaks in luminescence spectra at about 500 and 650 nm. We ascribed these spectral features to silver nanoclusters of different sizes that present in the film. Thermal annealing transforms both absorption and emission spectra of the films. Lager clusters that are formed after annealing possess one absorption band at 350–450 nm and one luminescence band at 510 nm. The luminescence was observed only in samples with the silver content of less than 2.2%. Quenching of the luminescence in samples with higher concentration of silver is due to the presence of larger particles with plasmonic properties.     

Amorphous/microcrystalline transition of thick silicon film deposited by PECVD

Thick silicon films were deposited by plasma-enhanced chemical vapor deposition at different plasma power densities. Annealing treatment was performed on these deposited films. As-deposited and annealed films were characterized by X-ray diffraction, Raman scattering spectroscopy and reflectance spectroscopy. Before annealing, only the film deposited at the plasma power density of 500 mW/cm² exhibits a diffraction peak corresponding to the (111) plane orientation. Raman spectrum of this film confirms the presence of crystalline phase. After annealing, a transition from amorphous phase to crystalline one occurs for all samples. This transition is accompanied by an increase of the crystalline fraction volume deduced from Raman spectra analysis and by a reduction of optical gap energy.     

Influence of post-deposition annealing on the structural,optical and electrical properties of Li and Mg co-doped ZnO thin films deposited by sol–gel technique

Lithium (Li) and magnesium (Mg) co-doped zinc oxide (ZnO) thin films were deposited by sol–gel method using spin coating technique. The films were deposited on glass substrates and annealed at different temperatures. The effects of annealing temperature on the structural, optical and electrical properties of the deposited films were investigated using X-ray diffraction (XRD), Ultraviolet–Visible absorption spectra (UV–VIS), photoluminescence spectra (PL), X-ray photo electron spectroscopy (XPS) and Hall measurements. XRD patterns indicated that the deposited films had a polycrystalline hexagonal wurtzite structure with preferred (0 0 0 2) orientation. All films were found to exhibit a good transparency in the visible range. Analysis of the absorption edge revealed that the optical band gap energies of the films annealed at different temperatures varies between 3.49 eV and 3.69 eV. Room temperature PL spectra of the deposited films annealed at various temperatures consist of a near band edge emission and visible emission due to the electronic defects, which are related to deep level emissions, such as oxide antisite (O_Zn), interstitial zinc (Zn_i), interstitial oxygen (O_i) and zinc vacancy (V_Zn) which are generated during annealing process. The influence of annealing temperature on the chemical state of the dopants in the film was analysed by XPS spectra. Ion beam analysis (Rutherford back scattering) experiments were performed to evaluate the content of Li and Mg in the films. Hall measurements confirmed the p-type nature of the deposited films.     

不同衬底和CdCl2退火对磁控溅射CdS薄膜性能的影响

在科宁7059玻璃, FTO, ITO, AZO四种衬底上磁控溅射CdS薄膜, 并在CdCl₂+干燥空气380 ℃退火, 分别研究了不同衬底和退火工艺对CdS薄膜形貌、结构和光学性能的影响. 扫描电子显微镜形貌表明: 不同衬底原位溅射CdS薄膜的形貌不同, 退火后相应CdS薄膜的晶粒度和表面粗糙度明显增大. XRD衍射图谱表明: 不同衬底原位溅射和退火CdS薄膜均为六角相和立方相的混相结构, 退火前后科宁7059玻璃, FTO, AZO衬底上CdS薄膜有 H(002)/C(111) 最强衍射峰, ITO衬底原位溅射CdS薄膜没有明显的最强衍射峰, 退火后出现 H(002)/(111) 最强衍射峰. 紫外-可见分光光度计分析表明: AZO, FTO, ITO, 科宁7059玻璃衬底CdS薄膜的可见光平均透过率依次减小, 退火后相应衬底CdS薄膜的可见光平均透过率增大, 光学吸收系数降低; 退火显著增大了不同衬底CdS薄膜的光学带隙. 分析得出: 上述结果是由于不同衬底类型和退火工艺对CdS多晶薄膜的形貌、结构和带尾态掺杂浓度改变的结果. 关键词： CdS薄膜 磁控溅射 退火再结晶 带尾态     

退火气压对于P3HT∶PCBM微观形貌及光伏性能的影响

通过精确设定不同的退火环境气压,实现对P3HT(Poly(3-hexylthiophene -2,5-diyl)与PCBM([6,6]-Phenyl C₆₁ butyric acid methyl ester)体系中聚噻吩结晶度以及共混相分离程度的控制,并在此基础上制备了结构为ITO/PEDOT∶PSS/P3HT∶PCBM/Al的正型光伏器件。在允许的压强设定范围内,器件各项性能参数均随退火环境压强的增大表现出先升高后下降的变化规律,并统一于气压设定为1 500 mTorr时获得最大值。从活性层的紫外-可见(UV-Vis)吸收光谱中发现P3HT在510 nm吸收峰以及550和600 nm肩峰附近的吸收强度随退火气压升高而增大,在气压为1 500 mTorr时达到最高,吸收强度的提升源于聚合物分子π—π堆叠的增加。原子力显微镜(AFM)进一步分析结果表明,高气压环境(>1 000 mTorr)能够促进P3HT∶PCBM共混组分在退火过程中形成较大程度的相分离,而当环境压强合适时(1 500 mTorr)适度的相分离利于聚合物形成良好有序结晶,从而能够提升活性层内部载流子传输能力,保证较高的短路电流与填充因子,制备的器件也因此表现出良好的光伏性能,光电转化效率达到3.56%。     

Simulation of the influence of the polymer conformation,orientation, crystallinity,and stretching on its IR absorption spectrum

Using cis-1,4-polyisoprene as an example, the influence of the conformation and orientation of the polymer chain on its polarization absorption spectra has been simulated. It has been shown that if a change in the orientation of the polymer chain leads to a monotonic change in the intensities of the absorption bands with their maxima positions remaining unchanged, then changes in the polymer chain conformation additionally cause a shift and the appearance of new absorption bands. According to the results of the calculation of the vibrational spectra, the inversion of the IR dichroism of the absorption bands of polymers is associated with the conformation transition. We simulate the influence on the IR absorption spectrum of the degree of crystallinity of cis-1,4-polyisoprene, in which the amorphous and amorphous-crystalline states are considered as a mixture of noninteracting polymer chains, where each state is characterized by a certain ratio of conformers. Likewise, the changes in the IR absorption spectrum of cis-1,4-polyisoprene under its stretching have been investigated. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 727–733, November–December, 2005.     

Photoluminescence of sodium-implanted zinc selenide

Luminescence measurements indicate that Na acceptors implanted into ZnSe become optically active after annealing at 500°C. The spectra show a strong Na dependence for both the R series band and the I^Y₁ exciton line. In this work Ne-implanted and unimplanted samples were annealed and measured with the Na-implanted material to isolate defect-induced spectral features. Several new bands resulting from radiation damage are reported, along with annealing properties of the defect bands and Na-related luminescence.     

Anodization of aluminium thin films on pSi and annihilation of strong luminescence from Al2O3

Photoluminescence (PL) of Al₂O₃ films obtained by anodization of thermally evaporated and annealed thin Al films on p⁺⁺Si in 0.3 M oxalic acid has been investigated. Thermal annealing at 200–950 °C under the dry nitrogen atmosphere was used for deactivation of luminescence centres. Luminescence from as grown films was broad and located at 425 nm. This luminescence reached to highest level after annealing at 600 °C. Maximum 10 min was required for full optical activation and prolonged annealing up to 4 h did not change the luminescence intensity. Because of deep levels, absorption band edge of as grown films was shifted to the lower energy which is 3.25 eV. Annealing above 800 °C reduced the PL intensity and this observation was correlated with the blue shift of band edge as the defects annealed out. Disappearing PL intensity and blue shift of band edge absorption after annealing at 950 °C was mainly attributed to the oxygen-related defects and partly to impurities that may be originated from oxalic acid. AFM results did not show any hexagonally ordered holes but uniformly distributed nanosized Al₂O₃ clusters that were clearly seen. XRD measurements on as grown Al₂O₃ showed only [1 1 0] direction of α phase. Debye–Scherer calculation for this line indicates that cluster size is 35.7 nm. XRD and AFM pictures suggest that nanocrystalline Al₂O₃ are embedded in amorphous Al₂O₃.     

The influence of the preparation conditions on the energy disorder in poly(methylphenyl)silane films

The photoluminescence (T=5 K) and absorption (T=295 K) spectra and thermostimulated luminescence (T=5–300 K) curves of poly(methylphenyl)silane (PMPS) films are investigated as functions of the film thickness, annealing temperature, and oxygen content in air. It is revealed that the optical spectra and thermostimulated luminescence curves of PMPS films prepared in air at room temperature undergo changes after annealing at T=370–450 K. The assumption is made that the observed changes are associated with the formation of long polymer chain segments with a closer packing. This leads to an increase in the density of low-energy states of excitons and charge carriers. It is demonstrated that atmospheric oxygen substantially affects the formation processes and the energy disorder in the films prepared. The PMPS films are found to degrade after heating to T≥500 K.     

Spectral features of impurity luminescence in uniaxial polymer films and nematic glasses

A study is conducted of the static shift and the splitting of the photoluminescence and electroluminescence polarized bands of uniaxial impurity molecules, embedded into uniaxial polymer films with axial or in-plane orientation of the impurity subsystem or into the vitreous phase of a nematic liquid crystal. Dependences of the band shift and the splitting on the type of alignment of impurity molecules, the polarization of transition moments in absorption and emission, and the host-impurity anisotropic interactions of different ranks are established. For both types of host matrices, characteristic features of orientational statistics of impurity molecules at a high degree of orientation ordering are studied. These features are revealed in a qualitative difference between the dependences of positions and splittings of polarized impurity fluorescence bands on the order parameter of the impurity molecules axially ordered in stretched polymer films and relevant dependences in nematic glasses. Specific features of the polarized impurity-related photoluminescence and electroluminescence in the matrices under study, observed experimentally, are interpreted.     

Photoluminescence studies of nitrogen-doped TiO2 powders prepared by annealing with urea

Photoluminescence and excitation spectra have been investigated for undoped and nitrogen-doped TiO₂ powders at low temperatures. A broad luminescence band peaking at 2.25?eV is observed in the undoped TiO₂ powders. The 2.25?eV luminescence band exhibits a sharp rise from 3.34?eV in the excitation spectrum reflecting the fundamental absorption edge of anatase TiO₂. On the other hand, the N-doped TiO₂ powders obtained by annealing with urea at 350 and 500°C exhibit broad luminescence bands around 2.89 and 2.63?eV, respectively. The excitation spectra for these luminescence bands rise from the lower energy side of the fundamental absorption edge of anatase TiO₂. The origin of the luminescence bands and N-related energy levels formed in the band-gap of TiO₂ 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.     

Specific features of luminescence properties of nanostructured aluminum oxide

Aluminum oxide nanopowders are prepared by the gas phase method and characterized according to the particle sizes and the phase composition. Samples of the nanostructured ceramic material are produced by pressing and annealing in air. The photoluminescence and cathodoluminescence spectra of the Al₂O₃ nanostructured ceramic material and α-Al₂O₃ anion-defect single crystals are investigated under comparable conditions. The luminescence bands of centers formed by oxygen vacancies are revealed in the spectra of two types of samples. The nanostructured ceramic material is characterized by the appearance of a new luminescence band at 3.4 eV and a decrease in the luminescence decay time. The inference is made that the characteristic features of the luminescence of the nanostructured ceramic material can be associated with the presence of non-equilibrium phases and the specific features of relaxation processes.     

Annealing effect on the structural and optical properties of a Cd1−xZnxS thin film for photovoltaic applications

Herein is a report of a study on a Cd_1−xZn_xS thin film grown on an ITO substrate using a chemical bath deposition technique. The as-deposited films were annealed in air at 400 °C for 30 min. The composition, surface morphology and structural properties of the as-deposited and annealed Cd_1−xZn_xS thin films were studied using EDX, SEM and X-ray diffraction techniques. The annealed films have been observed to possess a crystalline nature with a hexagonal structure. The optical absorption spectra were recorded within the range of 350-800 nm. The band gap of the as-deposited thin films varied from 2.46 to 2.62 eV, whereas in the annealed film these varied from 2.42 to 2.59 eV. The decreased band gap of the films after annealing was due to the improved crystalline nature of the material.     

Temperature-induced transformations in hydrogenated and fluorinated single-wall carbon nanotubes studied by Raman scattering

Raman spectra of hydrogenated and fluorinated single-wall carbon nanotubes (SWCNTs) are measured at ambient temperature before and after heat treatment. The spectra of the as-prepared hydrogenated SWCNTs show a giant structureless band in the visible region that screens the Raman peaks related to the carbon atom vibrations. The onset of this strong band follows the excitation laser line, which is typical of hot luminescence. The intensity of the luminescence background decreases exponentially with the annealing time, while the dependence of the luminescence decay time constant on the annealing temperature is of the Arrhenius type with the activation energy E _a = 465 ± 44 meV. The luminescence background in the Raman spectra of the fluorinated SWCNTs is comparable with the Raman peak intensity and decreases exponentially with the annealing time. The dependence of the decay time constant on the temperature is again of the Arrhenius type with the activation energy E _a = 90 ± 8 meV. The appearance of hot luminescence is related to the upshift of the fundamental energy gap in functionalized SWCNTs and the structural disorder induced by random binding of hydrogen or fluorine atoms. The luminescence background disappears upon annealing in vacuum or in air after removal of hydrogen (fluorine), while the annealed samples still demonstrate large structural disorder.     

CVD两步法生长ZnO薄膜及其光致发光特性

用CVD两步法在常压下于p型Si(100)衬底上沉积出具有较好择优取向的多晶ZnO薄膜。在325nm波长的光激发下,室温下可观察到显著的紫外光发射(峰值波长381nm)。高温退火后氧空位缺陷浓度增加,出现了一个450~600nm的绿光发光带,发光峰值在510nm。作为比较,用一步法生长的ZnO薄膜结晶质量稍差。在其PL谱中不仅有峰值波长389nm的紫外发射而且还出现了一个很强的蓝光发光中心(峰值波长437nm),退火后同样产生绿光发光带。对这两种绿光发光带的发光机制进行了研究,认为前者源于VO,而后者与O_Zn有密切的关系。