光纤化学传感技术研究近况

光纤化学传感器作为传感器的一个重要分支,结合了化学和光学的相关技术,将化学制膜、光纤技术以及化学分析中的分光光度法、拉曼光谱、荧光光谱、折射率检测等方法相融合,以其微型化,抗电磁干扰,传输信息量大,拥有自身参比等特点不断向前发展。简要综述了光纤化学传感技术研究近况和未来的发展趋势。重点对光纤pH化学传感器、光纤离子化学传感器和光纤气体化学传感器进行了介绍。简要分析了常见的敏感膜制备方法如化学键合法和溶胶凝胶(sol-gel)等方法。新型光纤——微结构光纤的出现为光纤化学传感器开辟了新的发展方向。由于其具有大的内表面积,结构设计灵活多样,光纤内部提供感应场所等特点,快速度成为光纤化学传感器的重要发展方向和研究热点。对微结构光纤衍生而来的新型光纤化学传感器进行了详细评述, 最后对光纤化学传感器的未来进行展望。     

Measurements of spectral responses for developing fiber-optic pH sensor

In this study, we have fabricated a fiber-optic pH sensor, which is composed of a light source, a pH-sensing probe, plastic optical fibers and a spectrometer, for determining the degree of infection by Helicobacter pylori in the stomach. As pH indicators, phenol red and m-cresol purple are used, and pH liquid solutions are prepared by mixing phenol red or m-cresol purple solutions and various kinds of pH buffer solutions. The light emitted by a light source is guided by plastic optical fibers to the pH liquid solution, and the optical characteristic of a reflected light is changed according to the color variations of the pH indicator in the pH-sensing probe. Therefore, we have measured the intensities and wavelength shifts of the reflected lights, which change according to the color variations of indicators at different pH values, by using a spectrometer for spectral analysis. Also, the relationships between the pH values of liquid solutions and the optical properties of the modulated lights are obtained on the basis of the changes of the colors of indicators.     

Fiber-Optic Ammonia Sensors Utilizing Rectangular-Cladding Eccentric-Core Fiber

A new fiber-optic ammonia sensor utilizing rectangular-cladding eccentric-core fiber and a sensitive film containing an indicator dye is demonstrated. The sensitive film is a SiO₂-GeO₂ gel film including an indicator dye of bromocresol purple or bromocresol green, which is dip-coated by a sol-gel technique. The attenuation of this sensor changes depending on the concentration of ammonia at the wavelength range of 500–700 nm. This sensor can detect several ppm of gaseous ammonia. Various factors determining the sensitivity to detect the ammonia gas and time response of the sensor are also studied.     

Second-harmonic laser-coupled optical fiber sensor for pH measurement and corrosion detection based on evanescent field absorption

In the present paper, a laser-coupled optical fiber is introduced for pH sensing of Methyl red solution in the Ethanol solvent. Then it is modified for corrosion detection when it was placed inside a corrosive solution. Second-harmonic (SH) radiation of a microchip Q-switched pulsed Nd:YAG laser operating at λ=532 nm is generated via KTP nonlinear crystal, and it is launched into the fabricated fiber sensor. The provided evanescent field is absorbed by the surrounding environment in the sensing region, and the output intensity of the absorbed laser beam is monitored and recorded in the presence of the different kind of solvents and corrosive solutions. To increase the sensitivity of the pH sensor the fiber-optic probe is coiled and fixed on a Poly Propylene (PP) mount with 6 cm diameter and 10 cm long. The fabricated sensor is then calibrated for pH measurement of unknown media. For corrosion detection, a spin motor is used to uniformly coat a small portion of the fiber designed as U-shaped after its clad was removed by a simple chemical method. It is then electroplated by a very thin Fe–C film to form a corrosion sensor. It is observed that while the concentration of the NH₄Cl solution is changed from 0.068 to 0.125 mol/l and its pH from zero to 14, the output intensity of the launched laser is increased due to the Fe–C film corrosion.     

Fabrication and comparison of thermochromic material-based fiber-optic sensors for monitoring the temperature of water

In this study, we explored the feasibility of developing two types of fiber-optic temperature sensors that can measure the temperature of water. One uses a thermochromic material such as Lophine, whose optical absorbance changes according to the thermal variation. The other uses a thermochromic pigment that gradually loses its own color through heat absorption. We measured the change in the intensity of the reflected light, which was due to the variation of the optical property of Lophine and pigments, with thermal variation. The relationship between the temperature of water and the output signal of the fiber-optic sensors was also determined. The fiber-optic temperature sensor using Lophine provided a relatively broad range of temperature measurement with low sensitivity, whereas the fiber-optic temperature sensor using a thermochromic pigment offered a high sensitivity in a narrow range of temperature measurement.     

Effect of the Pd-Au thin film thickness uniformity on the performance of an optical fiber hydrogen sensor

Thin alloy film of Pd and Au, formed by simultaneous electron-beam and thermal evaporation techniques, respectively, is used in the design of an optical fiber hydrogen sensor. The sensor consists of a multimode fiber (MMF) in which a short section of single mode fiber (SMF), coated with the Pd-Au thin film, is inserted. Due to core diameter mismatch, the SMF cladding guides light, allowing the interaction between the sensing layer and the guided light. When the sensor is exposed to hydrogen, the Pd-Au layer refractive index diminishes and causes attenuation changes on the transmitted light. Several samples with different layer thickness uniformity were fabricated and tested in a very simple experimental set-up. We have observed that the sensor signal change is dependant on layer thickness uniformity, since the effective interaction length between the evanescent field and the sensing layer is increased. By contrast, such uniformity practically has no influence on the time response of the sensor. The resulting Pd-Au film can detect 4% hydrogen with a response time of 15 s.     

Sol-gel matrix modified microstructured optical fibre towards a fluoride sensitive optical probe

In this article, we report an optical fluoride probe based on microstructured polymer optical fibers (MPOFs) which is modified with morin-Al complex doped silica gel film. This probe is fabricated by sol-gel fluxion coating process. Sol solution doped with morin-Al is directly inhaled into array holes of MPOF and then forms morin-Al-gel matrix film in them. The sensing probe shows different fluorescence intensity to different fluoride ion concentrations in the aqueous solution. The range of response is 5-50 mmol/L, under the condition of pH 4.6.     

Development of optical fiber-based respiration sensor for noninvasive respiratory monitoring

In this study, two types of nasal-cavity-attached fiber-optic respiration sensors have been fabricated for noninvasive respiratory monitoring. One is a silver halide optical-fiber-based respiration sensor that can measure the variations of infrared radiation generated by the respiratory airflow from a nasal cavity. The other is a thermochromic-pigment-based fiber-optic respiration sensor that can measure the intensity of reflected light which changes owing to color variations of the temperature-sensing film according to the temperature difference between inspiratory and expiratory air. We have demonstrated the similarities of the respiratory signals using the fiber-optic respiration sensors and the temperature transducer of the BIOPAC? system. In addition, we verified that respiratory signals without the deterioration of the MR image can be obtained using the fiber-optic respiration sensors. It is anticipated that the proposed noninvasive fiberoptic respiration sensors will be highly effective for respiratory monitoring of a patient during MRI procedures.     

长周期光纤光栅气敏薄膜传感器结构优化

基于三包层长周期光纤光栅模型,研究了包层表面涂覆一层溶胶凝胶气敏薄膜的长周期光纤光栅化学传感器的灵敏度Sn与薄膜光学参量(折射率n3和厚度h3)和光纤光栅结构参量(光栅周期、折变量和光栅长度)之间的关系。采用最优化数值方法,找到了获得高灵敏度所需的最佳膜层光学参量和光栅结构参量。理论计算表明,该类型传感器对膜层折射率的测量分辨率高达10-8。实验上制作了对乙醇气体敏感的传感器,并证实了传感器结构优化的必要性。     

Flow Injection Small-volume Fiber-optic pH Sensor Based on Evanescent Wave Excitation and Fluorescence Determination

A small-volume fiber-optic pH sensor (FOEWS) based on evanescent wave excitation is developed and evaluated. The sensor is simply fabricated by inserting a decladded optical fiber into a transparent capillary tube. A microchannel between the optical fiber and the capillary inner wall was formed and acted as flow cell for solution flowing through. The pH-sensitive fluorophore of fluorescein can be excited by the evanescent wave field produced on the fiber core surface to produce emission fluorescence. pH value was then sensed by its enhancing effect on the emission fluorescence intensity. The response range of the sensor is from pH 2.09 to pH 8.85 and the linear range is from pH 3.25 to 8.85. The proposed sensor has a small detection volume of 2.5 μL and a short response time of 8 s. It has been applied to measure pH values of real water samples and was in good agreement with the results obtained by commercial pH meter.     

Optical CO<Subscript>2</Subscript> Sensing with Ionic Liquid Doped Electrospun Nanofibers

The first use of electrospun nanofibrous materials as highly responsive fluorescence quenching-based optical CO₂ sensors is reported. Poly(methyl methacrylate) and ethyl cellulose were used as polymeric materials. Sensing slides were fabricated by electrospinning technique. A fiber-optic bundle was used for the gas detection. CO₂ sensors based on the change in the fluorescence signal intensity of ion pair form of 8-hydroxypyrene-1,3,6-trisulfonic acid (HPTS). The sensor slides showed high sensitivities due to the high surface area-to-volume ratio of the nanofibrous membrane structures. The preliminary results of Stern-Volmer analysis show that the sensitivities of electrospun nanofibrous membranes to detect CO₂ are 24 to 120 fold higher than those of the thin film based sensors. The response times of the sensing reagents were short and the signal changes were fully reversible. The stability of ion pair form of HPTS in the employed matrix materials was excellent and when stored in the ambient air of the laboratory there was no significant drift in signal intensity after 7 months. Our stability tests are still in progress.     

Feasibility study on fiber-optic goniometer for measuring knee joint angle

In this study, we fabricated a fiber-optic goniometer using a plastic optical fiber, a light-emitting diode, and a photodiode. The cladding of the plastic optical fiber was removed at 0.5–3mm intervals regularly to increase the bending loss of the plastic optical fiber. Also, the output voltages of the photodiode based on light intensity that measured using the fiber-optic goniometer were measured light intensities using the fiber-optic goniometer were measured to evaluate the linearity of the fiber-optic goniometer. Finally, we measured the responses of the fiber-optic goniometer for gait speeds of 3, 5, and 10 km/h using a data acquisition board and a LabVIEW program.     

Fabrication of Si-based waveguide splitters using photosensitive sol-gel method

In this paper, a photosensitive sol-gel method for 1 × 8 Y-branch optical splitter is reported. The poly (methyl methacrylate) (PMMA) cladding films with different thicknesses (above 10 μm) on Si substrates are prepared on Si substrates by dip-coating, the root-mean-square roughness (Rrms) of which is less than 0.7 nm. The UV photosensitive organic-inorganic composite SiO₂/ZrO₂/H core films are then coated on these PMMA cladding films using photosensitive sol-gel method. The refractive indexes of PMMA cladding films examined by spectroscopic ellipsometer are 1.4854, 1.4815 and 1.4806 at 0.85, 1.31 and 1.55 μm, while that of the SiO₂/ZrO₂/H gel films are 1.5569, 1.5489 and 1.5472 μm, respectively, which is larger than that of PMMA cladding films. Therefore, the composite structure of SiO₂/ZrO₂/H gel films on PMMA-on-Si substrates could be used to fabricate waveguide splitter. Based on the inherent photosensitivity of the SiO₂/ZrO₂/H gel film, 1 × 8 Y-branch optical power splitters with a thickness of 5 μm are fabricated by irradiating the gel film with UV light through a mask followed by dissolving the non-irradiated area in a suitable solvent. The line-width and output spacing of this splitter are 25 and 110 μm, respectively. The observed near-field pattern indicates that the light with a wavelength of 1.53-1.56 μm can be transmitted and split into eight branches in the optical splitter, which is fabricated by using the above technique.     

Infrared radiation thermometer using a silver halide optical fiber for thermal ablation

In this study, we have fabricated non-contact temperature sensor using an infrared optical fiber for measuring temperature distributions during radiofrequency ablation. We have measured an infrared radiation, which is transferred by a silver halide optical fiber from the multi-points on the water around inserted electrode, using a thermopile sensor and the output voltages of a thermopile sensor are compared with those of the thermocouple recorder. Also, the relationship between the temperatures and the output voltages of a thermopile sensor at the measuring points is determined to obtain the temperature distribution. The measurable temperature range of a fiber-optic non-contact temperature sensor is from 37 to 80 °C.     

Determination of the absorption for incident light propagating parallel through the guest–host polymer film waveguide

Guest–host polymer thin films of polymethyl methacrylate (PMMA) incorporated with (4′-nitrobenzene)-3-azo-9-ethylcarbazole (NAEC) were fabricated by spin coating and then poled by the method of corona-onset poling at elevated temperature. The absorption mechanism of the polymeric film, which is very important for the optical transmission losses and directly relates to the orientation of chromophore NAEC in polymer PMMA, was investigated in detail. From the UV–visible absorption spectra for NAEC/PMMA film before and after being poled, we determined the change of absorption coefficient κ with the wavelength and approximately calculated the maximum absorption A_max as 3.46 for incident light propagating parallel through the film, i.e. the ordinary polarized light, which cannot be directly measured in the spectrophotometer.     

Fiber-optic humidity sensor based on an air-gap long period fiber grating

In this paper, we propose a novel high-sensitivity fiber-optic humidity sensor based on a calcium chloride thin film to be coated on an air-gap long-period grating fabricated (AG-LPG) by combining the fiber side-polishing and fiber etching methods. When the surrounding refractive index of the air-gap long-period grating is changed by a change in humidity, the grating resonant wavelength is considered varied. Experimental results indicate that humidity can be detected by this sensing mechanism and has a high sensitivity of about 1.36 nm/1%RH.     

Fiber-optic surface plasmon resonant sensor with low-index anti-oxidation coating

A multimode fiber-optic surface plasmon resonance(SPR) sensor with a MgF2 film as a modulated layer is studied.The fiber-optic SPR sensor is investigated theoretically,specifically the influence of the dielectric protecting layer,using a four-layer model.The sensor is then fabricated with the optimal parameters suggested by the theoretical simulation.The sensor has a high sensitivity in the analyte refractive index(RI) range of 1.33-1.40.The best sensitivity of 4 464 nm/RIU is achieved in the experiment.The use of dielectric film(MgF2) can not only modulate the resonance wavelength of the sensor,but also protect the silver film from oxidation.     

Minimizing optical losses in bulk heterojunction polymer solar cells

The efficiency that a solar cell can reach is ultimately limited by the number of photons absorbed in its active layer. Bulk heterojunction polymer solar cells are fabricated from a stack of thin film layers, each of which is thinner than a single wavelength from an incident photon within its absorption band. One consequence of this thin film layer stack is a strong optical interference between the various layers that can change the quantity of light dissipated in the active layer by 50%. Here we use optical modeling to quantitatively calculate the dissipation in each of the various layers as functions of wavelength and layer thickness. Using this information the loss free short circuit current density can be calculated (J_scmax). Optimization of J_scmax leads to direct improvements in the efficiency of the solar cell through improved light dissipation in the active layer. The optical properties for a P3HT:PCBM active layer and a model Lorentzian low band gap spectrum are optimized and ideal fabrication conditions are reported for these materials. PACS 72.40.+w; 72.80.Le     

Influence of pH in La-doped SnO2 nanoparticles towards sensor applications

The present investigation has been carried out to optimize the pH level of lanthanum (La)-doped tin dioxide (SnO₂) nanoparticles towards the potential application in gas sensor. The La-doped SnO₂ nanoparticles were synthesized by sol-gel method in different pH values varying from acidic to base nature. The synthesized nanoparticles were characterized by X-ray diffraction (XRD), ultraviolet (UV), photoluminescence (PL), and scanning electron microscopy (SEM) techniques. The XRD, UV, and PL analyses show the pH influences on the crystallite size of La-doped SnO₂ nanoparticles. The SEM images show the formation of porous structure at pH 11. Also, the electrical conductivity of 1 mol% La-doped SnO₂ at pH 3 and pH 11 were measured by impedance analyzer. In addition, we have fabricated and demonstrated device performance of synthesized La-doped SnO₂ nanoparticles for gas-sensing application. Real-time current response and long-time response to the gas sensing were also studied for the fabricated device.

     

固体电解质ZrO2薄膜气敏光学特性的研究

本文采用溶胶凝胶法制备了ZrO₂薄膜,并研究它在乙醇蒸汽和氨蒸汽中的透射光谱,发现当掺入适量的稳定剂后,其光学特性显著增大,光学透过率随乙醇蒸汽和氨蒸汽的浓度增大而单调上升,敏感波段扩展至整个可见光区域.其气敏光学特性的灵敏度、单调性、可重复性表明了该材料是一种有实用价值的气敏光纤传感器新材料.本文亦讨论了ZrO₂薄膜的气敏光学机理.