高性能氧温双传感材料的研究

本文研究了荧光纳米材料与有机染料结合在多传感领域的应用:将荧光纳米材料CdSe/ZnS与有机染料铂(Ⅱ)四(五氟苯基)卟啉包埋于聚氨酯水凝胶D4,经过水解、缩合获得固体薄膜,来实现氧气浓度和温度的同时检测.利用发射峰在524nm的CdSe/ZnS荧光纳米材料提供温度传感,氧气传感则是基于发射峰为650nm的铂(Ⅱ)四(五氟苯基)卟啉的动态猝灭.所制得的薄膜具有良好的光学稳定性,由405nm的紫外光激发,得到两发射峰互不重叠的光谱.实验结果表明,在氧气浓度(0~30%)和温度(15~67℃)下传感膜能很好地应用于氧气和温度双传感系统,且氧气传感的灵敏系数为9.69×10-4,温度传感系数为-0.0035(误差在±0.0002),该技术为新型便携式多传感器提供了可能.     

Effect of substrate temperature on the growth and luminescence properties of ZnO nanostructures

ZnO nanowires, nanorods and nanoribbons have been prepared by heating a mixture of ZnO/graphite powders using the thermal evaporation and vapor transport on Si(1 0 0) substrates without any catalyst. The nanostructures are grown as a function of substrate temperature ranging from 900 to 1300 K. These nanostructures are of the size 100–300 nm in diameter or width and several tens of micrometers in length. We studied the influence of the substrate temperature on the luminescent properties of these nanostructures. We observed a strong relationship between the substrate temperature and the green emission band in ZnO, i.e., the photoluminescence study revealed that the green emission peak of the ZnO nanostructures is suppressed relative to the band edge emission when the substrate temperature is decreased from 1300 to 900 K.     

Exciton emission from forward-biased zinc selenide Schottky diodes

Exciton emission has been observed in the forward-biased electroluminesence of ZnSe Schottky diodes free of intentionally added luminescent centres. The emission has been studied from ≈ 95° K to room temperature and is attributed to the recombination of free excitons (zero-LO phonon line). No LO phonon side bands were observed. As with exciton photoluminescence in CdS the half-width of the emission line, although a linear function of temperature, is greater than that predicted by theory. At temperatures below ≈150°K pair emission was also observed.     

Properties of 397 nm luminescent band of Hg2Cl2 single crystal

Measurement of emission and excitation spectra of the luminescent band peaked at 397 nm of the mercurous chloride single crystals has been performed. This emission has been observed below the phase transition temperature. From the observed azimuthal dependence of the degree of polarization of the luminescence it was concluded that the luminescent centres are oriented in [001] direction. It is assumed that the luminescent centres are formed by Hg⁰ atoms, which interact strongly in the excited state with the surrounding ions of chlorine.The authors are much indebted to Dr. A.Bohun for his interest in this work and for many useful discussions.     

Photoluminescence from surface-oxidized Ge nanoclusters

Photoluminescence from gas-evaporated Ge nanoclusters consisting of a crystalline core encased in an oxide shell are presented. An as-grown sample shows room temperature luminescence with separate peaks around 357 and 580 nm. Prolonged air exposure of the clusters reduces the Ge core dimensions, and the emission initially at 580 nm shifts to 420 nm; however, the violet luminescence at 357 nm displays no difference. These results indicate that there are two mechanisms involved with light emission from Ge nanoclusters, visible light emission associated with the quantum confinement effect, and violet light emission correlated to luminescent centers.     

Multipeak-structured photoluminescence mechanisms of as-prepared and oxidized Si nanoporous pillar arrays

Silicon dominates the electronic industry, but its poor optical properties mean that it is not preferred for photonic applications. Visible photoluminescence (PL) was observed from porous Si at room temperature in 1990, but the origin of these light emissions is still not fully understood. This paper reports that an Si nanocrystal, silicon nanoporous pillar array (Si-NPA) with strong visible PL has been prepared on a Si wafer substrate by the hydrothermal etching method. After annealing in O₂ atmosphere, the hydride coverage of the Si pillar internal surface is replaced by an oxide layer, which comprises of a great quantity of Si nanocrystal (nc-Si) particles and each of them are encapsulated by an Si oxide layer. Meanwhile a transition from efficient triple-peak PL bands from blue to red before annealing to strong double-peak blue PL bands after annealing is observed. Comparison of the structural, absorption and luminescence characteristics of the as-prepared and oxidized samples provides evidence for two competitive transition processes, the band-to-band recombination of the quantum confinement effect of nc-Si and the radiative recombination of excitons from the luminescent centres located at the surface of nc-Si units or in the Si oxide layers that cover the nc-Si units because of the different oxidation degrees. The sizes of nc-Si and the quality of the Si oxide surface are two major factors affecting two competitive processes. The smaller the size of nc-Si is and the stronger the oxidation degree of Si oxide layer is, the more beneficial for the luminescent centre recombination process to surpass the quantum confinement process is. The clarification on the origin of the photons may be important for the Si nanoporous pillar array to control both the PL band positions and the relative intensities according to future device requirements and further fabrication of optoelectronic nanodevices.     

核/壳结构的ZnS:Mn/SiO_2纳米粒子的制备及发光性质研究

采用溶剂热法制备了Mn离子掺杂的ZnS纳米粒子(ZnS∶Mn),然后利用正硅酸乙酯(TEOS)的水解反应对其进行了不同厚度的SiO2无机壳层包覆。采用X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)及荧光发射光谱(PL)对样品的结构及光学性质进行了表征和研究。包覆SiO2壳层后,粒子的粒径明显增大并且在ZnS∶Mn纳米粒子表面可以观察到明显的SiO2壳层。XPS测试印证了ZnS∶Mn/SiO2的核壳结构。随着SiO2壳层的增厚,ZnS∶Mn/SiO2的Mn离子的发光先增强后减弱,这是因为SiO2壳层同时具有表面修饰和降低发光中心浓度这两种相反的作用。当壳层厚度(壳与核的物质的量的比)达到5时,发光效果达到最好,其强度达到未包覆样品的7.5倍。     

Luminescence with Local Distribution and Its Possible Mechanism in Zinc Oxide Micro-Crystallites

The spatial luminescence distribution hi the ZnO micro-crystallite fihns deposited on silicon substrates by CVD at room tempezature is investigated by the cathedolumineseence （CL） image. It has been observed that the CL image of the samples constitutes a certain pattern. The UV emission pattern projective to the （0001） face of ZnO grains consists of a series of lines nearby the grain boundaries . The included angles between any two adjacent lines are almost 120°. What is more, some luminescent lines form a close hexagon similar to ZnO crystalline structure. Such a local distribution propety shows that the UV emission on as-grown ZnO crystallite should be due to some local defects congregated to {1010} facets of ZnO grain rather than free exciton recombination.     

Synthesis of Light-emitting Silicon Nanoparticles by Intense Pulsed ion-beam Esvaporation

Synthesis of photoluminescent Si nanoparticles has been successfully prepared using an intense pulsed ion-beam evaporation (IBE) technique in vacuum. Si nanoparticles are produced by the IBE method without any post-annealings. Photoluminescence (PL) mainly in blue range with a peak of 455 nm and a shoulder near 510 nm is observed in as-deposited Si nanoparticles at room temperature. The blue light emission is relatively stable with no noticeable change, as the samples have already stored in air more than 4 months. The observed PL does not fit the quantum confinement model, since a majority of particle size is around ~20 nm, estimated by SEM and XRD measurements. Moreover, hydrofluoric acid (HF) corrosion tests on the Si nanoparticles also indicate a correlation between the presence of the surface oxide layers and the PL. Oxide-related luminescence is likely the source of this blue light emission.     

Luminescence of Bi3+-activated LaOBr,a system with emission from different states

The luminescence properties of LaOBr-Bi³⁺ are reported. Two luminescent centres are observed. These are ascribed to isolated Bi³⁺ ions and to a second BiOBr-rich phase. The emission of the isolated Bi³⁺ ion shows a remarkable temperature dependence. At low temperatures the emission is in the UV region. At higher temperatures the UV emission disappears and an emission in the visible region appears. At still higher temperatures the visible emission disappears and the UV emission reappears. The emission in the visible region is ascribed to a charge-transfer transition.     

镧系氧化物光子晶体自组装与自发辐射调制

光子晶体是介电常数(折射率)随光波长大小周期性巨大变化的人工晶体。光子晶体的诞生使人类操控光子由梦想成为现实。光子晶体结构对置于光子晶体中的荧光客体自发辐射速率和荧光强度具有重要的调制作用。与半导体晶格对电子波函数的调制相类似,光子带隙材料能够调制具有相应波长的电磁波——当电磁波在光子带隙材料中传播时,由于存在布拉格散射而受到调制,电磁波能量形成能带结构。能带与能带之间出现带隙,即光子带隙。所具能量处在光子带隙内的光子,不能进入该晶体。本文将在综述这一领域国际上的重要研究进展基础上,重点介绍本课题组在镧系氧化物三维晶体的自组装与光子带隙对稀土离子自发辐射调制方面的研究成果。     

A comparative study on determination of uranium and thorium in their mixed oxides by EDXRF using tube and radioisotope X‐ray sources

Studies on the matrix effects of uranium and thorium on the determinations of each other in their mixed oxides using energy dispersive X‐ray fluorescence (EDXRF) spectrometry with tube and radioisotope excitations of U Lα and Th Lα are reported. An internal standard method for the determination of uranium and thorium in these mixed oxides is found suitable. Comparison of the analytical results of EDXRF determinations of uranium and thorium using tube and radioisotope excitation sources has been made. The analytical methodology involves preparation of mixed oxide calibration/sample mixtures of uranium and thorium oxides, mixing of internal standard yttrium in these mixtures, pelletizing the mixtures after thorough mixing and grinding using boric acid binder and measuring EDXRF spectra of the specimens thus prepared using Rh X‐ray tube as well as ¹⁰⁹Cd radioisotope source. The samples were analyzed for uranium and thorium on the basis of the calibration plots obtained by plotting the intensity ratios of the analyte and internal standard characteristic X‐ray lines and their corresponding amount ratios. An average precision of 1.2% (1 s RSD) was observed for the determination of U and Th and the results deviated from the corresponding expected values by 3% on average. Due to the refractory nature of thorium oxide, comparatively more grinding time was required for thorium determinations. Copyright © 2011 John Wiley & Sons, Ltd.     

Photoluminescence characteristics of Pr3+ in ThO2: interplay of defects in a photo-induced charge transfer

Photo-luminescence studies of Pr³⁺ activated thorium oxide phosphor have revealed that mainly ³P→³H₄ and ¹D₂→³H₄ transitions with life-time of 30 and 600 μs are observed in this sample. An exponential reduction in the emission intensity of Pr³⁺ ions was observed on following continuous excitation with 275 nm corresponding to the f–d transition band of Pr³⁺ ions. Such a reduction in emission intensity was observed at all temperatures investigated in the range 90–330 K. The emission intensity recovered partially on dark storage only above 180 K. The recovery of emission intensity was also observed on the illumination of pre-exposed sample to light in the wavelength region 300–430 nm. Following illumination with 275 nm, Pr³⁺ activated thorium oxide phosphor has displayed a weak thermally stimulated luminescence. These results thus suggest that the optical excitation dynamically changes the state of the system under observation, and that changes are occurring in the valence state of Pr ions due to e/h transfer process on 275-nm exposure. On dark storage and also on 365-nm illumination of the pre-exposed sample, e/h traps recombine to cause emission signal recovery. The analysis of data on reduction in intensity obtained with exposure to 275 nm suggests the likelihood of the of Pr³⁺ ions existing at three different sites. The activation energies associated with the release of electrons from excited Pr³⁺ ions at different sites were determined from the temperature dependence of the photo-induced charge transfer process.     

Growth and field emission of tungsten oxide nanotip arrays on ITO glass substrate

High-density and uniformly aligned tungsten oxide nanotip arrays have been deposited by a conventional thermal evaporation on ITO glass substrates without any catalysts or additives. The temperature of substrate was 450-500 °C. It was shown that the tungsten oxide nanotips are single-crystal grown along [0 1 0] direction. For commercial applications, field emission of the tungsten oxide nanotip arrays was characterized in a poor vacuum at room temperature. The field emission behaviors are in agreement with Fowler-Nordheim theory. The turn-on field is 2.8 V μm⁻¹ as d is 0.3 mm. The excellent field emission performances indicated that the tungsten oxide nanotip arrays grown by the present approach are a good candidate for application in vacuum microelectronic devices.     

Field electron emission changes by face specific adsorption of aluminum oxide and corresponding decomposition products on tungsten {110} and {100} planes

After deposition of aluminum oxide on a tungsten field emission microscope (FEM) tip and stepwise heating, three stages of emission changes were observed on {100}. Stages I and II cause work function decreases of 0.28 and 0.07 eV, respectively. Stage III is characterized by a large increase (Δ??+3 eV). The changes are discussed in terms of interaction of decomposition products (oxygen and aluminum) and adsorption of aluminum oxide. On {110} only a single aluminum oxide layer growth, which results in a work function decrease to ?=4.69 eV, is observed. The field electron emission from this layer was measured between 1400°K and room temperature. The experimental values were compared with those determined from Christov's unified theory of field and thermionic emission. The {110} layer values coincide with those obtained earlier from an aluminum oxide covered tungsten {112}.     

Surface-structure-assisted chaotic mode lasing in vertical cavity surface emitting lasers

We demonstrate chaotic mode lasing in vertical cavity surface emitting lasers at room temperature, with an open cavity confined laterally by the native oxide layer. Instead of introducing any defect mode, we show that suppression of lower-order cavity modes can be achieved by destroying vertical reflectors with a surface microstructure. Lasing on chaotic modes is observed directly through collecting near-field radiation patterns. Various vertical emission transverse modes are identified by the spectrum in experiments as well as numerical simulations in real and phase spaces.     

Excitation characteristics of the IR luminescence in CU2O

Detailed luminescence excitation characteristics of the long-wave (0.93 μm), medium-wave (0.82 μm), and short-wave (0.72 μm) emission peaks in cuprous oxide were studied under pulsed dye laser excitation. The results show that the emission spectrum at 193 K contains only two peaks at 0.93 and 0.72 μm for excitation wavelenghts less than 5800 Å, and that for excitation wavelengths 5800 Å and longer an emission peak also appears at 0.82 μm. This medium wave band increases relatively faster with increase in wavelength until it becomes the dominant luminescent peak at an excitation wavelength of 6350 Å. All three emission peaks have much narrower excitation curves at 300 K than at 77 K, with the peak excitation wavelength shifting to longer wavelengths at higher temperature.     

与掺杂浓度相关的ZnS∶Mn纳米粒子的发光性质

采用溶胶法制备了Mn掺杂的ZnS纳米粒子,探讨了掺杂离子浓度对ZnS∶Mn纳米粒子的晶体结构和发光性质的影响。通过X射线衍射（XRD）对样品的结构进行了表征,结果表明：所制备的ZnS∶Mn纳米粒子为立方闪锌矿结构,其在Mn离子的掺杂浓度达到6%时不发生分相,但随着掺杂浓度的增加,纳米粒子的平均粒径会减小。光致发光光谱和荧光光谱的结果表明：通过改变掺杂离子的浓度可实现对ZnS∶Mn纳米粒子590 nm附近荧光发射波长的调节。此外,研究了温度对纳米粒子形貌和发光性质的影响。高分辨透射电子显微镜（HRTEM）观察发现,经过50℃陈化1 h后的ZnS∶Mn样品的平均粒径增大约为20 nm,且加热陈化有利于ZnS∶Mn纳米粒子中Mn2＋在590 nm处产生荧光。     

SrAl2O4∶Eu2+,Dy3+长余辉发光材料的喷雾热解制备及其表征

采用喷雾热解两段法制备了SrAl₂O₄∶Eu²⁺ ,Dy³⁺长余辉发光材料,并利用XRD、SEM、荧光长余辉亮度测试等方法分析了不同制备工艺条件下SrAl₂O₄∶Eu²⁺ ,Dy³⁺发光材料的结构、形貌以及发光性能的变化。结果表明:采用喷雾热解两段法可制备出球形SrAl₂O₄∶Eu²⁺ ,Dy³⁺长余辉发光材料,SrAl₂O₄∶Eu²⁺ ,Dy³⁺的晶体结构与α-SrAl₂O₄磷石英晶体结构相同。热解温度、还原温度、添加剂对产物的形貌、粒度分布、发光性能有较大影响。较之高温固相法,喷雾热解法制备的SrAl₂O₄∶Eu²⁺ ,Dy³⁺具有发光性能好、形貌好、粒度分布窄等优点。     

高低温条件下氟化锂材料的离子激发发光光谱分析

在北京师范大学GIC4117串列加速器原有离子激发发光(ion beam induced luminescence,IBIL)分析靶室基础上,安装了可实现80—900 K温度范围内精确控温的冷热样品台,实现高低温条件下IBIL光谱的测量.添加金硅面垒探测器,在离子辐照材料样品过程中同步采集背散射离子的计数,实现束流的在线监测.在不同温度下,利用2 MeV H~+束轰击氟化锂样品,获得的IBIL光谱中可明显观察到温度对不同发光中心发光效果的影响:激子峰和杂质峰发光在低温条件下更为清晰;高温时各类型F色心的发光强度在较小的注量下即可达到饱和值或开始衰减.辐照初期受扰激子峰(296 nm)发光强度的上升过程表明不能排除受扰激子峰与点缺陷发光中心相关的可能性,激子峰强度的上升源自低注量时核弹性碰撞产生的应变键;温度对空位迁徙速率及非辐射复合的影响是造成发光强度随注量演变差异的重要原因.