基于荧光猝灭原理的光纤溶解氧传感器研制

采用锁相放大技术研制了基于荧光猝灭原理的光纤溶解氧传感器,并组装了其测试系统。该系统采用高亮度蓝色LED作为光源,光电倍增管作为探测器,光栅光谱仪作为分光仪器,并使用SR830锁相放大器来检测荧光与激发光之间的相移。测定了相移差与调制信号频率、占空比之间的关系。实验结果表明,频率为60kHz、占空比为10%的矩形调制信号能使传感器的检测精度达到最大,对光纤溶解氧传感器的进一步研究具有参考意义。     

Oxygen Sensors Based on a Quenching of Tris-(4,7-diphenyl-1,10-phenanthroline)ruthenium(II) in Fluorinated Polymers

Luminescence quenching of Ru(II) complexes by oxygen has proved a powerful method of quantitative oxygen analysis. It has become clear that the polymer support for the sensor molecule plays a pivotal role in the sensor performance. The current work is devoted to understanding how the physical and photophysical properties of a sensor respond to changes in polymer composition. An oxygen quenching study was conducted on [Ru(Ph₂phen)₃]Cl₂(Ph₂phen=4,7-diphenyl-1,10-phenanthroline), in copolymer supports consisting of GP-163 (a polydimethylsiloxane (PDMS) with varying amounts of pendant acrylate groups) combined with a number of alkyl methacrylates with long chain alkyl or fluorinated alkyl esters. Increasing the chain length or the degree of fluorination on the hydrocarbon chains enhances performance. However, there is an optimal chain length for the fluorinated hydrocarbons for sensitivity, linearity, and physical properties. Too long a chain yields reduced quenching sensitivity and yields cloudy polymers. All systems showed some degree of heterogeneity as indicated by nonlinear Stern-Volmer quenching plots, but their intensity quenching data could be successfully fit with a two-site model.     

一种基于荧光猝灭原理的光纤氧气传感器

用钌 (Ⅱ ) 邻菲咯啉配合物作为指示剂 ,研制成功一种基于荧光猝灭原理的光纤氧气传感器。采用锁相放大技术 ,实现了对弱荧光信号的检测。该传感器的检测下限为 5× 10 -6,检测精度为 5× 10 -7,响应时间T≤ 10s,并具有较强的抗干扰能力、较好的重复性和稳定性。     

Gas Phase Oxygen Quenching Studies of Ketone Tracers for Laser-Induced Fluorescence Applications in Nitrogen Bath Gas

In this paper we report the quantitative oxygen quenching effect on laser-induced fluorescence of acetone, methyl ethyl ketone, and 3-pentanone at low pressures (～700 torr) with oxygen partial pressures up to 450 torr. Nitrogen was used as a bath gas in which these molecular tracers were added in different quantities according to their vapor pressure at room temperature. These tracers were excited by using a frequency-quadrupled, Q-switched, Nd:YAG laser (266 nm). Stern–Volmer plots were found to be linear for all the tracers, suggesting that quenching is collisional in nature. Stern–Volmer coefficients (k_sv) and quenching rate constants (k_q) were calculated from Stern–Volmer plots. The effects of oxygen on the laser-induced fluorescence of acetone, methyl ethyl ketone, and 3-pentanone were compared with each other. Further, the Smoluchowski theory was used to calculate the quenching parameters and compared with the experimental results.     

Eu2+在Ba2Ca(BO3)2中的发光特性及浓度猝灭

采用高温固相法,以CaCO₃ (A.R)、BaCO₃ (A.R)、H₃BO₃ (A.R)和Eu₂O₃ (99.99%)为原料制备了Ba₂Ca(BO₃)₂∶Eu²⁺绿色发光材料,测量了材料的晶体结构、发光特性及色坐标等。Ba₂Ca(BO₃)₂∶Eu²⁺材料的激发光谱覆盖200~500 nm的紫外-可见光区。在400 nm近紫外光激发下,材料的发射光谱为一主峰位于537 nm的非对称宽谱,对应于Eu²⁺的4f⁶5d¹→4f⁷特征跃迁。研究发现,随Eu²⁺掺杂浓度的增大,Ba₂Ca-(BO₃)₂∶Eu²⁺材料的发射强度呈现先增大、后减小的变化趋势,最大发射强度对应的Eu²⁺掺杂摩尔分数为2%。造成发射强度下降的原因为浓度猝灭,其机理为电偶极-电偶极相互作用。依据晶格常数及实验光谱数据,得出临界距离R_c分别为2.64 nm和2.11 nm。随Eu²⁺掺杂浓度的增大,Ba₂Ca(BO₃)₂∶Eu²⁺材料的色坐标变化微小。计算得到Ba₂Ca(BO₃)₂∶2%Eu²⁺的转换效率约为72%。     

Influence of Oxygen Vacancies on the Luminescence Spectra of Y2O3 Thin Films

Luminescence spectra of Y₂O₃ thin films annealed in air and in vacuum are investigated. It is established that the presence of oxygen vacancies leads to a decrease in the intensity of the luminescence band with a maximum at 3.4 eV (related to emission of selflocalized Frenkel excitons describing the excited state of a molecular ion (YO₆)^9–) and of the luminescence band with a maximum at 2.9 eV (related to the anion sublattice). It is revealed that the oxygen vacancies also lead to a decrease in the luminescence intensity in the 2.60, 2.35, 2.10. 1.90, and 1.70 eV bands that are related to radiative recombination in the donor–acceptor Y³⁺–O^2– pairs. The donor–acceptor distances are calculated.     

Eu~(3+)掺杂浓度及基质氧空位对Ca~(2-x)Eu_xSnO_4发光性能的影响

采用高温固相法制备Ca_(2-x)SnO_4:xEu~(3+)(x=0,0.001,0.005,0.01,0.015,0.02)发光材料,分别在空气和真空氛围中进行烧结,研究Eu3+掺杂浓度及基质中氧空位对样品发光性能的影响。随着Eu~(3+)离子浓度的增加,发射强度呈逐渐增大的趋势,主发射峰由两个分别位于614 nm和618 nm的峰逐步合为一个位于616nm的发射峰。在Ca_(2-x)SnO_4∶xEu~(3+)样品的激发光谱中,存在着200~295 nm的Eu~(3+)-O~(2-)电荷迁移带,随着Eu~(3+)离子浓度的增加,电荷迁移带的峰位由271 nm红移到286 nm。此外,在Eu~(3+)离子掺杂浓度相同的情况下,真空中烧结得到样品的发光强度是空气中烧结得到样品的2倍。这是由于在真空氛围中烧结产生的氧空位增加使得传导电子密度升高,导致发光强度增加。而且,氧空位的增加导致电子陷阱的增多,这使得Ca_(2-x)SnO_4∶xEu~(3+)样品的余辉性能得到了很大程度的提高。     

Influence of Oxygen Vacancies on the Luminescence Spectra of Thin Bi4Ge3O12 Films

Luminescence spectra of thin Bi₄Ge₃O₁₂ films annealed in air and in vacuum have been investigated. It has been established that the luminescence spectra for different forms of excitation consist of three bands with maxima at 2.70, 2.40, and 2.05 eV. The relation of the bands with maxima at 2.40 and 2.05 eV to the centers that incorporate an oxygen vacancy has been shown. The separated emission bands have been interpreted.     

Concentration self-quenching in solid solutions of complex organic molecules under intense excitation

A theoretical study was carried out to investigate concentration self-quenching which is nonlinear in intensity in a molecular system caused by nonradiative electronic excitation energy transfer to relatively long-lived acceptors that are formed in a solution and whose function is performed by molecules that have acquired the triplet state. It is shown that at ratios of constants of radiative and nonradiative transitions typical of complex molecules at concentrations of ∼10⁻³–10⁻² mole/liter substantial (2- to 10-fold) fluorescence takes place at intensities of excitation of ∼10⁴–10³ of the intensity of saturation for a singlet subsystem. Polarization characteristics of the system are analyzed. Belarusian State University, 4, F. Skorina Ave., 220050, Minsk, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 729–733, November–December, 1997.     

基于单光源频域荧光寿命的水体溶解氧浓度检测方法

现有的光学溶解氧浓度检测方法中光路及电路结构复杂,本文提出了一种单路光源的频域荧光寿命的溶解氧检测方法.采用单路光源的光学结构实现水体溶解氧浓度的检测,简化了光路及电路结构,改进了溶解氧浓度检测算法,降低了整体检测过程的计算量.设计对比实验对方法进行验证,实验结果表明:单光源的频域荧光寿命的检测方法与DOP1光学溶解氧分析仪相比,在0~9mg/L范围内,实际检测误差降低至0.04mg/L;衡量稳定性的检测标准偏差为0.007mg/L,同比降低了36%;采用快速傅里叶变换以及改进的溶解氧浓度计算方法,配合优化的电路及光路结构,在达到90%稳态时响应时间平均缩短了12s,浓度上升和下降时的响应速度分别提升为40%和28%.该方法具有较好的检测精度、稳定性以及响应速度.     

氧等离子体处理对GaAs表面单层自组装SiO2纳米球薄膜的影响

二维纳米阵列结构因其重要的光学性能被广泛应用于各类光电子器件。本文对自组装单层SiO2纳米球掩模刻蚀法制备GaAs纳米柱二维阵列结构的关键工艺技术进行了研究。采用旋涂法在GaAs表面制备自组装单层SiO2纳米球,重点研究了GaAs表面氧等离子体亲水处理工艺对纳米球排列特性的影响,获得最佳工艺条件为功率配比100 W+80 W、腔室压力4 Pa、氧气流量20 mL/min、处理时间1200 s,并最终得到排列紧密的大面积单层纳米球薄膜。以单层纳米球为掩模,采用感应耦合等离子体刻蚀技术在GaAs表面制备了纳米柱阵列并测试了其表面光反射谱。测试结果表明,GaAs纳米柱阵列在特定波段的反射率降低至5%,远低于表面无纳米结构的薄膜材料表面高达40%的光反射。分析表明纳米柱可以激发米氏散射共振效应,从而有效降低反射率并提升光吸收。     

Influence of Temperature on the Concentration Quenching of Sensitized Phosphorescence of Organic Molecules in n-Paraffin Solutions

The sensitized phosphorescence of naphthalene and acenaphthene in frozen n-paraffin solutions (n-octane and n-decane) before and after their heating has been investigated. It has been established that heating of the frozen solution leads to an increase in the sensitized phosphorescence intensity. The influence of the solvent concentration on the above phenomenon has been analyzed. On the basis of the results obtained it has been concluded that the nonmonotone character of the temperature dependence of the sensitized phosphorescence intensity and its increase upon the sample heating are due to the removal of the concentration quenching in the process of solution annealing. It has been shown that in this case the intensity increases owing to the increase in the number of acceptor molecules participating in the radiation. The possible mechanisms of this phenomenon are discussed.     

ZnO薄膜的特殊光谱性质及其机理

以同步辐射真空紫外光(195nm)为激发源,在低温下观察到Si基衬底上ZnO薄膜的发光有三种紫外发射,其峰值波长分别为380,369．5,290nm。它们各自具有不同的衰减时间和不同的温度依赖关系,但其激发谱相同。强激发带不在近紫外区,而在真空紫外区(100～200nm),可能源于ZnO的下价带(Zn3d组态)电子的激发。对三种紫外发射的来源作了分析讨论。     

Luminescence-Based Oxygen Sensors: ReL(CO)3Cl and ReL(CO)3CN Complexes on Copolymer Supports

A new class of luminescent rhenium complexes has been tested as oxygen sensors based on luminescent quenching. ReL(CO)₃Cl and ReL(CO)₃CN (L = 2,2-bipyridine or 1,10-phenanthroline and substituted analogues) have several features that seem to indicate suitability as oxygen sensors. These include simple synthesis, long excited-state lifetimes, and high luminescence quantum yields. Intensity and lifetime oxygen quenching measurements were used to study the complexes in various polymer supports including homopolymers of PDMS (polydimethylsiloxane), a methacryloxy containing PDMS (Gp-163), and trimethylsilylmethylmethacrylate (T3642), and copolymers containing Gp-163 and T3642. In contrast to previous studies utilizing [Ru(4,7-diphenyl-1,10-phenanthroline)₃]²⁺ as an oxygen sensor, quenching of the Re complexes proved much more sensitive to the polymer support. With suitable supports, the rhenium chloro complexes demonstrated significant quenching; but the cyano complexes, in spite of being robust in solution, exhibited severe photochemical instability in polymers. The potential of this class of complexes as oxygen sensors and as molecular probes as well as the ramifications in the design of new and different types of sensors is discussed.     

血清浓度变化对血清荧光光谱的影响

光谱分析技术应用于血液的某些疾病诊断具有方便、快速的特点.文章采用日本岛津荧光光度计RF5301,研究了血清荧光光谱随血清浓度变化的规律,为通过血液分析进行疾病诊断提供了实验依据.实验结果表明:在不同波长的激发光激励下产生的荧光光谱不同,当用220,230,310～420 nm波长的光激发时,血清的荧光强度随着血清浓度的增加越来越大;而采用240～300 nm波长的光激发时,血清的荧光强度随着血清浓度的增加变得越来越小.实验还发现:当采用220,230,310～420 nrn波长的光激发时,血清的浓度猝灭和吸收作用不明显,主要是激发出的荧光起作用;采用240～300 nm波长的光激发时,血清浓度猝灭和吸收作用明显,导致荧光强度随着血清浓度的增加变得越来越弱.这对研究血清荧光光谱时血清浓度的选择具有参考价值.     

Analysis of Energy Transfer and Concentration Quenching in Sm3+-Activated Borate GdB3O6 Phosphors by Means of Fluorescence Dynamics

This article reports on the optical properties of Sm³⁺-activated GdB₃O₆ phosphors based on the measurement of their photoluminescence spectra and luminescence decay curves. Energy transfer from Gd³⁺ to Sm³⁺ and the concentration quenching of the Sm³⁺ ion emission are investigated. From the photoluminescence spectra and decay curves, the energy transfer from Gd³⁺ to Sm³⁺ is confirmed. The concentration quenching of the Sm³⁺ ion emission can be ascribed to resonant cross-relaxation. The interaction between the Sm³⁺ ions is derived of the electric dipole–dipole type through fitting the data with the Inokuti-Hirayama model. The critical distances and energy transfer microparameter for the transfer processes are given. The decay curves of Sm³⁺⁴G_5/2 level exhibiting a buildup and decay process also confirm the energy transfer from Gd³⁺ to Sm³⁺ and between Sm³⁺ ions.     

Effect of surface fields on luminescence of ZnS and ZnO crystals

It is shown that changes in luminescence characteristics of zinc sulfide and oxide in the presence of external effects that alter the surface charge are associated with a change in the parameters of surface barriers and can be explained within the framework of a model that takes into account separation of recombining partners in the Schottky barriers. We suggest a barrier mechanism for the effect of the surface region of a crystal on experimentally measured luminescence parameters and show that errors occuring in the measurement of these parameters can reach 10% and greater, depending on the depth of penetration of light. Moscow State University of Railways, 15 Obraztsov Str., Moscow, 103055, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 6, pp. 804–808, November–December, 1999.     

Thermal Behavior of Amorphous Silicon Thin Film Transistor and Its Application to Micromachined Uncooled Infrared Sensors

This work reports a new uncooled infrared sensor based on amorphous silicon thin film transistors (a-Si TFTs). The temperature coefficient of channel current (TCC) of the a-Si TFT is given. Analysis shows that the a-Si TFT working in the saturation region is preferred for the sensitive element with a TCC value of 3.8-6.0 %/K. The a-Si TFT is placed on a suspended microbridge to reduce the thermal conductance by using micro-electro-mechanical system (MEMS) technology. The a-Si TFT-based IR sensor with a monolithic architecture is fabricated. Preliminary experimental results show that a responsivity of 40.8 kV/W, a thermal response time of 5.5 ms and a NETD of 90 mK are achieved.     

钯和铂金属在石墨烯表面不同生长机理第一性原理研究

本文采用密度泛函计算方法,研究了钯和铂金属在石墨烯表面不同的生长机理.几何结构和电子结构分析表明,钯金属的d2z轨道电子通过石墨烯的π电子为中介,转移电子至钯金属的dxz+dyz轨道,并保持石墨烯的π电子不变.该电荷转移机理增强了钯金属与石墨烯衬底之间的相互作用,是钯在石墨烯表面生长的主要原因.反之,铂金属不存在该生长机理,而铂原子的自发团聚是铂金属无法在石墨烯表面生长的另一主要原因.     

Dependence of photoluminescent properties of cubic Y2O3:Tb nanocrystals on particle size and temperature

Temperature-dependent spectral properties in the cubic Y₂O₃:Tb³⁺ nanocrystals (NCs, 10-70 nm) under 488 nm excitation were studied and compared to that in the bulk. In NCs, emission lines assigned to the ⁵D₄-⁷F_J (J=1-6) transitions of Tb³⁺ ions and a broad band originated from oxygen defects were observed. As a function of temperature, two intensity maximums of the ⁵D₄-Σ⁷F_J transitions appeared in the NCs, at ∼250 and ∼500 K, while in the bulk only one maximum appeared at ∼250 K. The relative intensity of the maximum at ∼500 K to that at ∼250 K increased with decreasing particle size. The intensity maximum of the band emissions that came from the oxygen defects appeared in the range of 500-600 K. The appearance of intensity maximum as a function of temperature was attributed to the rivalry between thermal quenching process and phonon-assisted excitation. The appearance of two maxima in the NCs was attributed to the luminescence contributed by different Tb³⁺ centers, the internal and the surface. The emission for the surface Eu³⁺ centers has higher quenching temperature in contrast to that for the internal centers.