Advances in fluxgate sensors

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基于隧道磁阻传感器的三维电子罗盘设计

基于隧道磁阻传感器的三维电子罗盘设计∗王琪;李孟委;王增跃;蒋孝勇;李锡广【摘要】Existing electronic compass is vulnerable to be distracted by the Magnetic Field in external environment, which leads to low accuracy. To solve this problem,a three-dimensional electronic compass is designed based on Tunneling Magneto Resistance sensor and a prototype is made. The error characteristics of compass in a real envi-ronment is studied,and ellipse hypothesis are carried out to compensate the azimuth error after ellipsoid-fitting cor-rection. Through experimental tests,the compensation effect of the ellipse hypothesis method,which compensated az-imuth accuracy of up to 0.85° and effectively reducing 94.81% of the azimuth error. Experimental results show that applying TMR sensor to electronic compass is feasible.%针对现有电子罗盘在地磁场检测时易受到外界磁场干扰而导致测量精度不高的问题，设计了基于隧道磁阻传感器( TMR)的三维电子罗盘并完成样机制作。

Bartington Instruments Mag-13三轴磁场传感器操作手册说明书

Operation Manual for Mag-13 Three-Axis Magnetic Field Sensors1. About this Manual 31.1. Symbols Glossary 32 Safe Use 33. Introduction 34. General Description 45. Enclosures 46. Compatible Power Supply and Data Acquisition Units 47. Cables and Connectors 57.1. Cables 57.2. Mating Connectors 58. Mounting 58.1. Mag-13MC 68.2. Mag-13MS 69. Operation 79.1. Connector Pin Allocation 79.2. Interface 79.3. Power Supplies 79.4. Signal/Power Ground 79.5. Test Coil 89.6. Temperature Sensor 99.7. Connecting Power 99.8. Electromagnetic Compatibility 910. Performance 910.1. Noise 910.2 Excitation Frequency 1011. Troubleshooting, Care and Maintenance 1011.1. Troubleshooting 1011.2. Care and Maintenance 1012. Storage & Transport 1013. Disposal 1113.1. Waste Electrical and Electronic Equipment (WEEE) Regulations 111.This manual describes the installation, operation and maintenance of the Mag-13 range of three axis magnetic field sensors. It should be read in conjunction with the product brochure DS3143 and the outline drawings which can be found on the Mag-13 product page on the Bartington Instruments website at: .See Application Note AN0045: ‘Magnetic Units and Measurements’, available from Bartington Instruments, for important information about magnetic field measurement units.The following symbols used within this manual call your attention to specific types of information: WARNING: Indicates a situation in which serious bodily injury or death could result if thewarning is ignored.Caution: Indicates a situation in which bodily injury or damage to your instrument, or both,could result if the caution is ignored.Identifies items that must be disposed of safely to prevent unnecessary damage to theenvironment.Note: Provides useful supporting information on how to make better use of your purchase. 2WARNING: These products are not qualified for use in explosive atmospheres or life supportsystems. Consult Bartington Instruments for advice.These compact, high performance sensors with integral electronics provide measurementsof static and alternating magnetic fields in three axes. The sensors, also described as magnetometers, convert magnetic flux density, measured in three axes, into a bipolar analogue voltage. Analogue output voltages Vx, Vy and Vz vary linearly with magnetic flux density.The Mag-13 series are an evolution of the Mag-03 range of sensors and feature a number of improvements. These include improved orthogonality error of the sensing coils, and an inbuilt test coil and temperature sensor. There have also been other refinements in the design.The analogue output is positive for conventional flux direction, South to North, in the direction of the arrow shown on the label for each axis; i.e. the maximum positive output will be obtained from any axiswhen the arrow points towards magnetic north along the total field vector. The measurement axes are designated X, Y and Z in the Cartesian co-ordinate system, when viewed from the top or non-connector end of the sensor.The analogue outputs may require external filters if not used with a Bartington Instruments data acquisition unit, to achieve the noise specification of the sensor (see Noise).4.The Mag-13 contains three fluxgate sensing elements mounted orthogonally in a block at one end of an enclosure, which also contains the electronic circuitry. The connector is mounted at the opposite end of the enclosure. The position and direction of each sensing element is indicated by arrows on the outside of the sensor, together with the product code, measuring range and serial number. The sensor elements are precisely aligned along the centre lines of the package, directly beneath the diagram on the label.Details of the enclosures, mounting, connector dimensions, connector pin allocation and the position of the sensing elements relative to the enclosure are given in outline drawings on the Mag-13 product page.The sensors provide three high precision analogue outputs, proportional to the magnetic field along each axis. The relationship between the magnetic field and the analogue output is extremely linear. An additional output is provided in order to take temperature measurements or activate the internal test coil.The low output impedance of the sensor ensures it can be operated over long cables when interfaced with Bartington Instruments’ high impedance data acquisition systems. The zero field offset error, scale factor, orthogonality and frequency response are individually calibrated.The sensors are available in a variety of enclosures. All enclosures are environmentally sealed and electrically shielded. A full list of sensors with specifications is provided in the product brochure.Note: Using your sensor in an environment that exceeds its rating may result in the need for repair at the customer’s expense.6.A number of other Bartington Instruments products will work with the Mag-13 as power supply and/or data acquisition units. These are listed in the product brochure and can be found at www. /data-acquisition-and-conditioning-units.html.Note: Outputs for the test coil and temperature sensor are presently only available with the DecaPSU Power Supply Unit. See Test Coil for information on test coil operation.For further information on power supplies see Power Supplies.For information on using your own power supply or data acquisition unit see AN0042: ‘Connecting your own Power Supply to a Bartington Magnetic Field Sensor’, available from Bartington Instruments.Although the Mag-13 is singled-ended, the cable connecting it to the power supply has a signal ground for each axis. The configuration of the cable pin out for the Mag-13 on the power supply side will require the power supply/signal conditioning unit to be set to the balanced mode to operate the Mag-13 correctly.For the Spectramag and Mag-03DAM data acquisition units, an adaptor cable will be required. This cable must be used despite the connector of the original cable being compatible with the power supplies.Caution: The Mag-13 sensor will not function correctly if plugged directly into aSpectramag-6 or Mag-03DAM without the use of an adaptor cable.7.Cables are available to connect the range of Mag-13 sensors to the range of suitable Bartington Instruments power supply and data acquisition units. Specifications for each of the cables are given in the product brochure.Note: Cables must be ordered separately.Note: Customers manufacturing their own cables must ensure the cables are shielded to prevent them picking up EM (electromagnetic) interference.7.2.For information on suitable mating connectors refer to the product datasheet.The range of compatible mounting accessories are shown in the product brochure.The method of mounting will depend on the application and the enclosure. For details of the mounting arrangements for each sensor, refer to the product brochure and the relevant outline drawing on the Mag-13 product page.Note: The use of magnetic materials in the mounting arrangement must be avoided. Check all mounting components before installation by placing the component within the immediate vicinity of the sensing elements of a working magnetometer and observing any variation in the background field.Caution: Do not place the sensor head of the unpackaged sensor in the immediate vicinity ofelectrically conductive materials.Caution: The absolute maximum screw penetration depth within the body, as shown in therelevant outline drawing on the product page, must not be exceeded.The analogue output is positive for conventional flux direction, south to north, in the direction of the arrow shown on the label for each axis; i.e. the maximum positive output will be obtained from any axis when the arrow points towards magnetic north along the total field vector.8.1.This sensor can be supported by the Mag-TA Tripod Adaptor described in the product brochure.The end of the Mag-13MC has a threaded hole for fixing the sensor in place, and three conical indentations that can be used to achieve a more precise alignment of the axes when setting up the sensor.Caution: The label area of the sensor is recessed and should not be used for clamping.8.2.This sensor can be supported by the Mag-TA Tripod Adaptor described in the product brochure. This sensor has threaded holes tapped in the base which is also the datum face. The sensor can be mounted on any flat, non-magnetic surface, including the Tripod Adaptor, using the two brass screws supplied.Caution: The absolute maximum screw penetration depth within the body is 8 mm and thismust not be exceeded.9.The connector pin or cable colour allocation for the connection to each package type is shown on the appropriate outline drawing on the Mag-13 product page.The analogue outputs for the X, Y and Z axes are buffered to give a low output impedance, enabling the unit to be operated over long cables and interfaced with high impedance data acquisition systems.The normal power supply of the sensors is specified in the product brochure. The ideal power supply units are those referenced in Compatible Power Supply and Data Acquisition Units. Alternatively, users may wish to provide their own supply. This should provide a voltage within the specification found in the product brochure. For the low noise applications, any ripple in the power supply should not exceed a few mV.Note: Adequate performance of the sensor cannot be guaranteed if used with non-Bartington Instruments products. Bartington Instruments cannot advise on the operation of third party products.See the product brochure for nominal current requirements. There is an additional current in proportion to the measured field, which is drawn from the positive or negative supply depending on the direction of the field.Note: The two signal/power ground conductors are connected to a common point within the sensor and the power supply common (power 0V) should be connected to only one of them.The other signal/power ground conductor should be used as the signal output common (0V).Each signal is then measured between the signal output conductor and the signal output common. In this way, the signal output common carries no power supply currents.Note: In long cables, the minimum current in the power ground conductor will give rise to an appreciable potential difference between the power supply end and the sensor end of the power ground conductor. The use of separate power and signal ground conductors will ensure thatthis voltage is not included in the voltage measured between the signal output and the signal common.Wiring for the Mag-13 is shown in the diagram below.Mag-13 outline wiring diagramTest CoilThe Mag-13 features a test coil which applies a magnetic field to all axes when activated. The corresponding changes in X, Y and Z output voltages confirm that all axes of the sensor are operational.The test coil can be activated by grounding the relevant pin of the Mag-13 output connector, i.e. connecting it to 0V. In this way it can be seen that the sensor is measuring correctly when the corresponding change in field is detected in each of the three axes. Refer to the test record for the field values generated for each individual sensor.Note: Of the available Bartington power supplies, only the Decaport and the DecaPSU will allow operation of the test coil.The Mag-13 features an inbuilt temperature sensor that can be used to measure temperature changes inside the sensor over time while taking measurements.The temperature can be read from the same pin as the test coil as an analogue voltage output. Measure the output between the relevant pin and signal ground. Refer to the product brochure for the voltage output and temperature scaling parameters.Caution: Check that the polarity of the supply is correct. Incorrect polarity can be preventedby using the power supply and cables provided by Bartington Instruments.Caution: The power supply should be connected to the sensor before the supply isenergised, as this prevents high surge currents which could cause damage. Apply thepositive and negative supplies simultaneously and avoid leaving the sensor connected to one polarity only.9.8.The Mag-13 range of sensors are electrically shielded from external, and emission of internal, electromagnetic fields. Any emissions generated are at a low level with a primary frequency corresponding to the frequency of the energising field of the sensor. The sensor is required to respond to magnetic fields within the specified frequency band.Caution: Do not operate the sensor in very strong electromagnetic fields as it may develop apermanent offset, or damage could occur to the sensing coils.Note: Do not place the sensor near to any equipment which may be affected by the verysmall local field produced by the sensor excitation.10. PFor detailed figures on the performance of the Mag-13 range of sensors, refer to the product brochure.N oiseThe Mag-13 range includes different noise versions that are specified in the product brochure. These versions correspond to the internal noise of the sensor, which can only be achieved in a shielded environment where no external fields are present.10.2The output signal for each axis will also contain breakthrough, which is a residual signal associated with the excitation frequency. (See the product brochure for frequency and level of breakthrough.) All Bartington Instruments power supply and signal conditioning units have a filter to remove the breakthrough.Note: When using a non-Bartington Instruments power supply, it will be necessary to providea filter to remove the breakthrough. Not doing so will lead to a higher noise level than thatspecified. See application note ‘AN0042: Connecting your own Power Supply to a BartingtonMagnetic Field Sensor’ from Bartington Instruments for further information.11.Special equipment is required for the diagnosis of faults within the unit. Much of this equipment is beyond the scope of normal service facilities. Therefore, in the event of any apparent malfunction, email service@ or telephone the Bartington Instruments service team on +44 (0)1993 706565.Caution: Attempted repair or opening of the casing by users may invalidate the warranty.A calibration service is available from Bartington Instruments which is traceable to international standards.Surface or dirt contamination should be removed using a mild detergent solution only. If the connector pins become contaminated then they should be lightly cleaned with a swab of isopropyl alcohol.Note: Dirt on the connectors may lead to increased noise in the output.12. SYour sensor is a precision electronic instrument and should be treated as such.Caution: Avoid exposing this intrument to shocks or continuous vibration.Caution: Store only within the temperature range specified in the product brochure.Caution: Do not expose this instrument to strong magnetic fields while being stored.BARTINGTON INSTRUMENTSPage 11 of 12 OM3143/313.This product should not be disposed of in domestic or municipal waste. For information about disposing of your sensor safely, check local regulations for disposal of electrical / electronic products.Bartington Instruments Mag-13 sensors comply fully with Restriction of the Use ofCertain Hazardous Substances in Electrical and Electronic Equipment (RoHS) and WEEERegulations current at the time of printing.O M 3143/3The copyright of this document is the property of Bartington Instruments Ltd.Bartington® is a registered trade mark of Bartington Instruments Limited in the following countries: United Kingdom, Australia, Brazil, Canada, China, European Union, India, Japan, Norway and the United States of America.Bartington Instruments Limited 5 Thorney Leys Business Park,Witney, Oxford, OX28 4GE, England. T: +44 (0)1993 706565F: +44 (0)1993 774813E: sales @。

地理探测器英文文献

地理探测器英文文献和专利文献1.Balmer, Manuel, Maurice Gonseth, and Domenico Giardini. "Seismic array technology for regional Structural Geology Research and practical seismological applications." Bulletin of the Seismological Society of America 99.6 (2009): 2924-2945.2.Bayer, Joachim, and Sirak Habtemariam. "GPR time lapse monitoring and geo-electric array technology to assess changes in shallow subsurface." Near Surface Geophysics 6.6 (2008): 501-506.3.Civco, Daniel L., et al. "Imaging snow depth changes using a low-cost, wide-swath, scanning laser altimeter." IEEE Geoscience and Remote Sensing Letters 7.2 (2010): 270-274.4.Ehlers, Jürgen, et al. "Remote sensing technologies for geologic and hydrogeologic mapping and characterization." Hydrogeology Journal 10.4 (2002): 410-419.5.Farquharson, Colin G., et al. "Terrasar-X: advanced radar imaging in a new digital age." Remote sensing of environment 91.4 (2004): 445-455.专利1.Huang, Chien-Chung, et al. "Isotopic georadar for ground structure exploration." US Patent 7,635,081, 2009.2.Batina, John, and Jeffrey McAllister. "Method and apparatus for subsurface imaging using stray electromagnetic fields." US Patent 6,502,692, 2003.3.Lerner, DavidA, et al. "System and method for rapid detection and automatic classification of carbon dioxide leakage." US Patent 8,939,605, 2015.4.Westcott, Darius, and Richard B. Meulenberg. "Method and apparatus for subsurface rock characterization using nuclear magnetic resonance." US Patent 5,337,763, 1994.5.Dugdale, Mark, and Richard Wilson-Clingen. "Sub-surface georadar apparatus and method of operating same." US Patent 8,864,890, 2014.。

NETWORK OF REMOTE SENSORS FOR MAGNETIC DETECTION

NETWORK OF REMOTE SENSORS FOR MAGNETIC DETECTION
A. Sheinker1, N. Salomonski1, B. Ginzburg1, A. Shkalim1, L. Frumkis2, B. Z. Kaplan2
1
R&D Integrated Systems Section, Propulsion Division, Soreq NRC, Yavne 81800, Israel Department of Electrical and Computer Engineering, Ben-Gurion University of the Negev P.O. Box 653, Beer-Sheva 84105, Israel
r
r
r
r
magnetic field, B E , as is given by:
r r r Bm = B + B E
(2)
3. The Remote Magnetic Sensing Unit The Remote Magnetic Sensing Unit (RMSU) consists of a single-axis fluxgate magnetometer, an interface to the magnetometer with a 50 Hz/ 60 Hz digital notch filter, RF communication controller and an energy source. The architecture of the RMSU is depicted in figure 2.
Figure 2 The inside structure of the RMSU Due to power saving considerations we preferred to use a single-axis magnetometer rather than a three-axis magnetometer, although the latter one provides more information about the target. The singleaxis magnetometer has been installed in the direction of Earth magnetic field in order to reduce magnetic interferences caused by orientation instability. When installed in the

德国Magsys公司介绍

Presentation MAGSYSRohwedderstr. 7 44369 Dortmund Germany www.magsys.de sales@magsys.deMAGSYS magnet systemeMAGSYS magnet systemePresentation MAGSYSContents• Company Profile • Products • Basics • Examples of Use • Abstract ReferencesMAGSYS magnet systemeContentsPresentation MAGSYS2Company Profile• Founded in 1997by Michael Kopka former Technical Head at TechnoPhysikMAGSYS magnet systeme• 17 EmployeesPhysicists, Engineers, Technicians... General Manager: Technical Manager: Sales Manager: Dipl. Ing. Michael Kopka Dipl. Ing. Volker Grebe Dipl. Phys. Hartmut Pagel• Approx. $ 3 Mio. € business volume • Subsidiary MAGSYS LLC, USA • Office in Singapore covering Asia except Japan • Commercial representatives in other industrialized countriesCompany ProfilePresentation MAGSYS3MAGSYS LocationMAGSYS magnet systemeHeadquarters in Dortmund, Germany– Complete production – Engineering – Sales Management; contact to sales partnersCompany ProfilePresentation MAGSYS4TeamMAGSYS magnet systemeCompany ProfilePresentation MAGSYS5Engineering and ProductionMAGSYS magnet systemeEngineeringProductionCompany ProfilePresentation MAGSYS6Engineering ...MAGSYS magnet systemeCompany ProfilePresentation MAGSYS7... Production ...MAGSYS magnet systemeCompany ProfilePresentation MAGSYS8..and TestingMAGSYS magnet systemeCompany ProfilePresentation MAGSYS9MagnetizersMAGSYS magnet systeme100 Ws / 500 V …Cycle time 1 secondProductsPresentation MAGSYS10Products11MAGSYS magnet systemePresentation MAGSYSMagnetizers…>100 kWs / 5000 VCurrent up to 50 kAPresentation MAGSYSProducts12Presentation MAGSYSProducts13Products14MAGSYS magnet systemePresentation MAGSYSFluxmeter•Built in calibrator •Low drift•Automatic probe detection •Probe plug with extra low thermo voltage•Frequency range 0..30 kHz •PC controllableProducts15MAGSYS magnet systemePresentation MAGSYS3D Scanning System•Messbereich: 50*50*50cm³•Genauigkeit:10 µm0.002° rotatorisch •PC-gesteuert•Verschiedene Sensoren einsetzbar3D VCM ScanProducts16MAGSYS magnet systemePresentation MAGSYSFurther Measuring Equipment•Gaussmeter for production line withHall sensor or Fluxgate; incl. interface •Handheld Gaussmeter•Material detection (Steel/stainless steel)•Tripping characteristic circuit-breakers or earth-leakage trips •Angle stop-, synchronized speed-and noise measurement on stepper motors •Pull-off force measurement on brake assist systems •Bemf measurement •… SoftwareBasics17MAGSYS magnet systemePresentation MAGSYSSaturation CurveSimplified CurveMagnetizing Field Strength HI n d u c t i o n BBasics18MAGSYS magnet systemePresentation MAGSYSMagnet Material Energy ConsumptionValues referenced to Cylinder10 mm x 10 mmE l e c t r i c a l E n e r g y [W s ] o r [J ]Magnetizing Field Strength HBasics19MAGSYS magnet systemePresentation MAGSYSEnergiebedarf MagnetmaterialienPole Pattern throughthe heightaxialmultipole in sectors axial double side multipole in sectors axial single sideradial diametricalatcircumferenceat inner diameterin stripes single side in stripes double side segment radial segment diametricalBasics20MAGSYS magnet systemePresentation MAGSYSExample Pole Pattern•10-pole at the circumference•4-pole at the inner diameter•4-pole in sectors at the head sideBasics21Presentation MAGSYSMultipole magnetization is stray field magnetizationMain fieldStray fieldB maxB minExample cylindrical coilExample 10 pole Magnetization(Extract)•Field strength decreases with distance to conductor ⇒Field strength decreases in the depth of the magnet⇒Risk of incomplete saturation in the depth of the magnet⇒Field strength on the surface of the magnet much higher than therequired saturation field strengthPresentation MAGSYSBasics22Blau is magnet surfaceRot is inside the magnetPresentation MAGSYSBasics23Basics24Presentation MAGSYS•Principle•Magnetizer: modular design, specified by–Energy–Max. charging voltage –Max. current–Min. charging time (cycle time)–Shape of current pulse –Input power•Magnetizing fixture: usually specialized based on the product •FEM analysis defines the specs aboveMagnetizer Capacitors Electric energyMagnetizing fixture InductivityMagnetic energy•Actual standard (axial): Bitter coilPrinciple Photo Bitter coil under constructionPresentation MAGSYSBasics25•Actual standard: Bitter coil–Mechanical fixing of conductorsÆhigh field strength (forces)possible, long lifetime–No epoxy Ægood heat-transfervia copper Æshort cycle timewith air cooling–Higher costs–R und L not very variablePresentation MAGSYSBasics26Examples27MAGSYS magnet systemePresentation MAGSYSExample I•Magnetization andmeasurement of ABS Sensors •Energy: 2.4 kWs •Voltage:2 kV •Cycle time:10 s•Measurement: magnetic flux with fluxmeter; test of built-in coil with LCR-meter •Handling by MAGSYS•Magnetization ofVCM magnets•Energy:6kWs•Voltage:2kV•Current:35 kA•Cycle time: 1.7 s / part•Handling by MAGSYSPresentation MAGSYSExamples28•Magnetization ofStepper motors•Energy: 2.4 kWs•Voltage: 2.0 kV•Cycle time: 5 s / fixture0.8 s / part300 000 parts / dayIn 7 production lines•Measurement:–Angle stop–Synchronized speed–Noise•Handling by customerPresentation MAGSYSExamples29•Magnetization ofCircuit-breakers•Energy:5kWs•Voltage:2kV•Cycle time:30 sMagnetization and calibration•Measurement: Tripping current•Handling by MAGSYSPresentation MAGSYSExamples30Examples31MAGSYS magnet systemePresentation MAGSYSSolutions for•Sensors / Actuators (especially Automotive Industry)•ABS-system, seat positioning sensor, float switch, brake assistant, tirepressure control, angle sensor, roll bar sensor, positioning sensor in hydraulic cylinder, direct shift gearbox, balance, flow measurement,…•Electro-technics•Drilling machine, chainsaw, cell phone,…•Audio•Loudspeaker, microphone•Motors•Bicycle, wheelchair, stepper-, pumps-, window lift-, wiper-, blower-, elevator-motor, generator,…•Hard-disc drivesReferences 32MAGSYS magnet systemePresentation MAGSYSExcerpt Reference List Sensors/Actuators•Allegro MicroSystems, Inc. USA •Balda AG, Germany •Bourns, Inc. USA•Delphi Corporation Automotive, Portugal/ USA•Dichtungstechnik G. BRUSS GmbH & CO. KG, Germany •HOERBIGER HYDRAULIK GmbH, Germany •Kiekert AG, Germany •LUXALP S.A., France•Continental, Germany / Spain/ Malaysia/ India •SONCEBOZ SA, Switzerland •TI Automotive, USA•TRW Automotive Germany / USA •Visteon Corporation, Hungary/ USA •AB Elektronik GmbH, Germany•AKG Acoustics GmbH, Austria•Blaupunkt GmbH, Germany•Bose Corporation, USA•Morel Acoustic Inc., USA•Panasonic -Matsushita, USA•Robert Bosch GmbH, Malaysia/ Tunesia•Shabani Industries Ltd., Israel•Song Am Than, Vietnam•Harman/Becker Automotive Systems Ltd., Great Britain•Shure Inc., USAPresentation MAGSYSReferences33•Berger Lahr GmbH & Co. KG, Germany•ETEL S.A., Switzerland•Dr. Fritz Faulhaber GmbH & Co. KG, Germany•maxon motor AG, Switzerland•Bosch Rexroth GmbH, Germany•Robert Bosch GmbH, Germany / USA•Rockwell Automation Inc., USA•Rosenberg Ventilatoren GmbH, Germany•Siemens AG, Germany•Temic Automotive, Germany•Valeo, France•Volkswagen, GermanyPresentation MAGSYSReferences34References35MAGSYS magnet systemePresentation MAGSYSExcerpt Reference ListExcerpt Reference List Magnet Manufacturers •BT Magnet Technologie GmbH, Germany•Magnetfabrik Schramberg GmbH & Co. KG, Germany •Magneti Ljubljana, d.d., Slovenia •Max Baermann GmbH, Germany •ThyssenKrupp Magnettechnik, Germany•VACUUMSCHMELZE GmbH & Co. KG, Germany •Precision Magnetics, Singapore •Magnetfabrik Bonn GmbH, Germany •Arnold Magnetics, USA / SwitzerlandReferences36MAGSYS magnet systemePresentation MAGSYSExcerpt Reference List VCM•Precision Magnetics Singapore Pte Ltd, Singapore •Magnetronics Technology Pte Ltd, Singapore •Min Aik Technology Co., Ltd, Taiwan•MMI Holdings Ltd., Singapore/ Malaysia/ China •Shin-Etsu Chemical Co., Ltd., Malaysia •Vacuumschmelze, MalaysiaMAGSYS magnet systemePresentation MAGSYS Presentation MAGSYSMAGSYS magnet systemeRohwedderstr . 744369 Dortmund Germanywww.magsys.de sales@magsys.deThank you!。

SCI_期刊最新分区表-JCR-中科院-2015最新版

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TECHNOL1876-1070J TAIWAN INST CHEM E0263-4368INT J REFRACT MET H1943-068X IEEE T COMP INTEL AI0021-891X J APPL ELECTROCHEM0169-023X DATA KNOWL ENG0168-7433J AUTOM REASONING0272-8842CERAM INT0266-8254LETT APPL MICROBIOL0272-1716IEEE COMPUT GRAPH1049-8923INT J ROBUST NONLIN0142-1123INT J FATIGUE0340-1200BIOL CYBERN1558-7916IEEE T AUDIO SPEECH0003-7028APPL SPECTROSC0885-3010IEEE T ULTRASON FERR。

基于荧光猝灭效应的光纤传感器研究进展

第４１卷㊀第１０期２０２０年１０月发㊀光㊀学㊀报ＣＨＩＮＥＳＥＪＯＵＲＮＡＬＯＦＬＵＭＩＮＥＳＣＥＮＣＥＶｏｌ４１Ｎｏ１０Ｏｃｔ.ꎬ２０２０文章编号:１０００￣７０３２(２０２０)１０￣１２６９￣１０基于荧光猝灭效应的光纤传感器研究进展陈㊀静ꎬ杨㊀曌ꎬ黄宇豪ꎬ周明辉ꎬ赵奔阳ꎬ夏㊀历∗ꎬ李㊀微(华中科技大学光学与电子信息学院ꎬ湖北武汉㊀４３００７４)摘要:光纤荧光传感器结合了荧光检测灵敏度高㊁鉴别性强和光纤体积小㊁抗干扰能力强等优点ꎬ由于部分荧光检测物质对荧光强度有猝灭作用ꎬ所以基于猝灭效应的光纤荧光传感器具有重要的研究意义ꎮ本文对基于荧光猝灭效应光纤传感器的研究进展进行综述ꎬ简要描述了荧光猝灭效应的检测机理ꎬ并根据传感光纤结构的不同ꎬ对光纤与荧光检测的结合机理进行了分类总结ꎮ在此基础上阐述了基于荧光猝灭效应的光纤荧光传感器在重金属离子检测㊁爆炸物检测等领域的应用ꎬ分析了猝灭剂㊁荧光材料的相互作用和传感器的性能指标ꎬ最后对其发展方向进行了展望ꎮ关㊀键㊀词:光谱检测ꎻ光纤传感ꎻ发光机理ꎻ荧光猝灭中图分类号:Ｏ４３３㊀㊀㊀文献标识码:Ａ㊀㊀㊀ＤＯＩ:１０.３７１８８/ＣＪＬ.２０２００２０６ＲｅｓｅａｒｃｈＰｒｏｇｒｅｓｓｏｆＯｐｔｉｃａｌＦｉｂｅｒＳｅｎｓｏｒｓＢａｓｅｄｏｎＦｌｕｏｒｅｓｃｅｎｃｅＱｕｅｎｃｈｉｎｇＥｆｆｅｃｔＣＨＥＮＪｉｎｇꎬＹＡＮＧＺｈａｏꎬＨＵＡＮＧＹｕ￣ｈａｏꎬＺＨＯＵＭｉｎｇ￣ｈｕｉꎬＺＨＡＯＢｅｎ￣ｙａｎｇꎬＸＩＡＬｉ∗ꎬＬＩＷｅｉ(ＳｃｈｏｏｌｏｆＯｐｔｉｃｓａｎｄＥｌｅｃｔｒｏｎｉｃＩｎｆｏｒｍａｔｉｏｎꎬＨｕａｚｈｏｎｇＵｎｉｖｅｒｓｉｔｙｏｆＳｃｉｅｎｃｅａｎｄＴｅｃｈｎｏｌｏｇｙꎬＷｕｈａｎ４３００７４ꎬＣｈｉｎａ)∗ＣｏｒｒｅｓｐｏｎｄｉｎｇＡｕｔｈｏｒꎬＥ￣ｍａｉｌ:ｘｉａｌｉ＠ｈｕｓｔ.ｅｄｕ.ｃｎＡｂｓｔｒａｃｔ:Ｏｐｔｉｃａｌｆｉｂｅｒｆｌｕｏｒｅｓｃｅｎｃｅｓｅｎｓｏｒｃｏｍｂｉｎｅｓｔｈｅａｄｖａｎｔａｇｅｓｏｆｈｉｇｈｓｅｎｓｉｔｉｖｉｔｙꎬｓｔｒｏｎｇｄｉｓ￣ｃｒｉｍｉｎａｔｉｏｎｏｆｔｈｅｆｌｕｏｒｅｓｃｅｎｃｅｄｅｔｅｃｔｉｏｎａｎｄｓｍａｌｌｓｉｚｅꎬｓｔｒｏｎｇａｎｔｉ￣ｉｎｔｅｒｆｅｒｅｎｃｅａｂｉｌｉｔｙｏｆｆｉｂｅｒ.Ｂｅ￣ｃａｕｓｅｓｏｍｅｏｆｔｈｅｆｌｕｏｒｅｓｃｅｎｔｄｅｔｅｃｔｉｏｎｓｕｂｓｔａｎｃｅｓｈａｖｅａｑｕｅｎｃｈｉｎｇｅｆｆｅｃｔｏｎｔｈｅｆｌｕｏｒｅｓｃｅｎｃｅｉｎｔｅｎ￣ｓｉｔｙꎬｔｈｅｏｐｔｉｃａｌｆｉｂｅｒｆｌｕｏｒｅｓｃｅｎｃｅｓｅｎｓｏｒｂａｓｅｄｏｎｔｈｅｑｕｅｎｃｈｉｎｇｅｆｆｅｃｔｈａｓｉｍｐｏｒｔａｎｔｒｅｓｅａｒｃｈｓｉｇ￣ｎｉｆｉｃａｎｃｅ.Ｉｎｔｈｉｓｐａｐｅｒꎬｔｈｅｒｅｓｅａｒｃｈｐｒｏｇｒｅｓｓｏｆｔｈｅｏｐｔｉｃａｌｆｉｂｅｒｓｅｎｓｏｒｂａｓｅｄｏｎｔｈｅｆｌｕｏｒｅｓｃｅｎｃｅｑｕｅｎｃｈｉｎｇｅｆｆｅｃｔｉｓｒｅｖｉｅｗｅｄ.Ｔｈｅｄｅｔｅｃｔｉｏｎｍｅｃｈａｎｉｓｍｏｆｔｈｅｆｌｕｏｒｅｓｃｅｎｃｅｑｕｅｎｃｈｉｎｇｅｆｆｅｃｔｉｓｂｒｉｅｆ￣ｌｙｄｅｓｃｒｉｂｅｄ.Ｔｈｅｃｏｍｂｉｎａｔｉｏｎｍｅｃｈａｎｉｓｍｏｆｔｈｅｏｐｔｉｃａｌｆｉｂｅｒａｎｄｔｈｅｆｌｕｏｒｅｓｃｅｎｃｅｄｅｔｅｃｔｉｏｎｉｓｃｌａｓ￣ｓｉｆｉｅｄａｎｄｓｕｍｍａｒｉｚｅｄａｃｃｏｒｄｉｎｇｔｏｔｈｅｓｔｒｕｃｔｕｒｅｏｆｔｈｅｓｅｎｓｉｎｇｏｐｔｉｃａｌｆｉｂｅｒ.Ｏｎｔｈｉｓｂａｓｉｓꎬｔｈｅａｐ￣ｐｌｉｃａｔｉｏｎｓｏｆｔｈｅｏｐｔｉｃａｌｆｉｂｅｒｆｌｕｏｒｅｓｃｅｎｔｓｅｎｓｏｒｂａｓｅｄｏｎｔｈｅｆｌｕｏｒｅｓｃｅｎｃｅｑｕｅｎｃｈｉｎｇｅｆｆｅｃｔｉｎｔｈｅｆｉｅｌｄｓｏｆｈｅａｖｙｍｅｔａｌｉｏｎｄｅｔｅｃｔｉｏｎꎬｅｘｐｌｏｓｉｖｅｄｅｔｅｃｔｉｏｎａｎｄｏｔｈｅｒｆｉｅｌｄｓａｒｅｄｅｓｃｒｉｂｅｄ.Ｔｈｅｉｎｔｅｒａｃ￣ｔｉｏｎｂｅｔｗｅｅｎｔｈｅｑｕｅｎｃｈｅｒａｎｄｆｌｕｏｒｅｓｃｅｎｔｍａｔｅｒｉａｌꎬａｎｄｔｈｅｐｅｒｆｏｒｍａｎｃｅｉｎｄｅｘｏｆｔｈｅｓｅｎｓｏｒａｒｅａｎ￣ａｌｙｚｅｄ.Ｆｉｎａｌｌｙꎬｔｈｅｄｅｖｅｌｏｐｍｅｎｔｄｉｒｅｃｔｉｏｎｏｆｔｈｅｏｐｔｉｃａｌｆｉｂｅｒｓｅｎｓｏｒｓｂａｓｅｄｏｎｆｌｕｏｒｅｓｃｅｎｃｅｑｕｅｎｃｈ￣ｉｎｇｅｆｆｅｃｔｉｓｐｒｏｓｐｅｃｔｅｄ.Ｋｅｙｗｏｒｄｓ:ｓｐｅｃｔｒａｌｄｅｔｅｃｔｉｏｎꎻｏｐｔｉｃａｌｆｉｂｅｒｓｅｎｓｉｎｇꎻｌｕｍｉｎｅｓｃｅｎｃｅｍｅｃｈａｎｉｓｍꎻｆｌｕｏｒｅｓｃｅｎｃｅｑｕｅｎｃｈｉｎｇ㊀㊀收稿日期:２０２０￣０７￣１４ꎻ修订日期:２０２０￣０８￣０４㊀㊀基金项目:国家自然科学基金(６１７７５０６５)资助项目ＳｕｐｐｏｒｔｅｄｂｙＮａｔｉｏｎａｌＮａｔｕｒａｌＳｃｉｅｎｃｅＦｏｕｎｄａｔｉｏｎｏｆＣｈｉｎａ(６１７７５０６５)１２７０㊀发㊀㊀光㊀㊀学㊀㊀报第４１卷１㊀引㊀㊀言荧光检测法具有极高的灵敏度㊁良好的鉴别性和实时监测性ꎬ可以很好地将化学问题物理化处理[１]ꎮ２０２０年１月ꎬ新型冠状病毒肺炎疫情(简称新冠肺炎)全面爆发ꎮ荧光聚合酶链式反应(ＰＣＲ)检测仪在病毒确诊中起着关键作用[２]ꎻ但荧光ＰＣＲ检测仪仍在一些缺点ꎬ例如对操作人员及操作技术要求高㊁检测时间长㊁仪器体积庞大不易携带等[３]ꎮ而光纤具有体积小㊁价格便宜等优势ꎬ如果将光纤与荧光检测技术相结合ꎬ可以避免上述缺点ꎮ荧光猝灭是指溶剂分子使荧光分子发生猝灭的现象[４]ꎮ１９３１年ꎬＫａｕｔｓｋｙ在叶绿素荧光诱导实验[５￣６]中发现氧分子可以猝灭荧光ꎬ于是提出荧光猝灭原理[７]ꎮ氧分子㊁重金属离子㊁温度等都可以作为荧光猝灭剂 ꎬ对荧光强度产生猝灭作用ꎬ基于荧光猝灭效应的传感器有效地利用了这一特点ꎬ具有重大的研究意义和应用价值ꎮ本文以基于荧光猝灭效应的光纤传感器为主题ꎬ通过对传感光纤结构进行分类的方式ꎬ详细地阐述了光纤与荧光检测的有机结合ꎬ综述了基于荧光猝灭效应的光纤传感器的应用领域ꎬ最后对其未来发展进行了展望ꎮ２㊀荧光猝灭原理２.１㊀荧光检测机理当光照射到某物质上时ꎬ其原子核周围的电子吸收光能量ꎬ从基态跃迁到高能级激发态ꎮ由于单线态的不稳定性ꎬ电子会恢复到基态自发辐射产生荧光ꎬ该现象称为弛豫[８]ꎬ荧光光谱较吸收光谱波长的红移称为斯托克斯位移[９]ꎮ根据待测物的不同ꎬ可以通过解调发射光谱[１０￣１１]㊁荧光强度[１２￣１３]和荧光寿命[１４￣１５]等参数来定量分析待测物ꎮ荧光检测法主要是基于具有荧光效应的物质进行直接检测或利用荧光染料标记法进行间接检测ꎮ２.２㊀荧光猝灭效应荧光猝灭可以简单地描述为通过荧光分子和猝灭分子的相互作用来减少荧光分子的荧光强度[１６]ꎮ荧光猝灭可以分为两个类别ꎬ分别是静态猝灭和动态猝灭ꎮ静态猝灭指两分子弱结合形成的复合物使荧光完全消失ꎻ动态猝灭则是一种电子转移或能量转移的过程ꎬ荧光的猝灭程度和猝灭剂有关[１７￣１８]ꎮ动态猝灭主要包括:浓度猝灭㊁杂质猝灭㊁温度猝灭等ꎬ其过程通常遵循Ｓｔｅｒｎ￣Ｖｏｌｍｅｒ方程:τ０τ＝Ｉ０Ｉ＝１＋ＫＳＶＣＱꎬ(１)其中ꎬＩ０㊁τ０㊁Ｉ和τ分别是浓度为ＣＱ的指示剂染料在不存在和存在猝灭剂时的荧光强度和荧光寿命ꎻＫＳＶ是Ｓｔｅｒｎ￣Ｖｏｌｍｅｒ猝灭常数ꎬ单位通常为浓度单位的倒数ꎬ与猝灭剂的猝灭效率有关ꎮ荧光信号取决于猝灭剂浓度ꎬ所以在包含或添加了荧光化合物的样品中ꎬ可以通过猝灭作用来确定其信息ꎮ３㊀传感光纤结构３.１㊀空间光耦合型光纤在荧光检测中最简单的应用是将其用于激发光和接收光的传输ꎬ荧光检测过程则在光纤外的空间中进行ꎮ由于激发光纤和接收光纤的分离式结构会导致大部分的荧光信号丢失ꎬ所以经典的结构是由１根激发光纤和６根接收光纤构成的组合光纤[１９]ꎮ但是在该光纤模式中ꎬ大量的入射光会被耦合进入低阶模式ꎬ并且被噪声信号干扰的接收光纤存在阈值饱和问题ꎬ影响荧光信号的解调ꎮ为解决上述问题ꎬＳａｎｄｒａ等[２０]将两根标准多模光纤组成一个直径约为１５０μｍ的光纤探针ꎬ如图１所示ꎮ该结构的传输功率损耗小于０.２ｄＢꎬ由于波导纤芯不耦合ꎬ不会造成无关干扰ꎮＭｏｒａｄｉ等[２１]则利用微流控芯片的高度集成化㊁低消耗等优势ꎬ提出如图２所示的蛇形通道微流控结构ꎬ同样可以有效地减少信号干扰ꎮ60滋m（a）PVC tube(2mm/1mm)Catheter21G(0.8mm/0.55mm)Dual fiber tip（b）（c）图１㊀双光纤探针的端面(ａ)㊁组成材料(ｂ)㊁传感探头(ｃ)ꎮＦｉｇ.１㊀(ａ)Ｅｎｄｆａｃｅｏｆｔｈｅｄｕａｌ￣ｆｉｂｅｒｐｒｏｂｅ.(ｂ)Ｃｏｎｓｔｉｔｕｔｅｓｍａｔｅｒｉａｌ.(ｃ)Ｓｅｎｓｉｎｇｐｒｏｂｅ.㊀第１０期陈㊀静ꎬ等:基于荧光猝灭效应的光纤传感器研究进展１２７１㊀0.60i n c h2.40inchMixing channelsHPTS injection portSample injection portOutlet图２㊀蛇形结构微流控芯片Ｆｉｇ.２㊀Ｓｅｒｐｅｎｔｉｎｅｓｔｒｕｃｔｕｒｅｍｉｃｒｏｆｌｕｉｄｉｃｃｈｉｐ３.２㊀微结构光纤型光在纤芯中以驻波形式传输ꎬ传输过程中光波会部分透射进入光纤包层大约一个波长深度ꎬ而后反射回到纤芯ꎮ如图３所示ꎬ该透射光波的振幅随穿透深度的增加呈指数衰减ꎬ故称为倏逝波[２２]ꎮ拉锥光纤㊁裸芯光纤等微结构光纤可以有效地使倏逝波泄露ꎬ光纤泄露的倏逝波则可以激发荧光物质产生荧光ꎮn 2n 1波传播方向x倏逝场区驻波场强度zn 1＞n 2图３㊀光纤倏逝波原理图Ｆｉｇ.３㊀ＳｃｈｅｍａｔｉｃｄｉａｇｒａｍｏｆｏｐｔｉｃａｌｆｉｂｅｒｅｖａｎｅｓｃｅｎｔｗａｖｅＬｉ等利用拉锥光纤结构搭建了如图４(ａ)所示的荧光传感系统[２３]ꎬ激光光源在光纤拉锥区泄露倏逝波ꎬ从而激发荧光染料罗丹明６Ｇ产生荧光ꎮ荧光信号在拉锥区域产生并且耦合进入光纤ꎬ图４(ｂ)~(ｄ)分别表示自然状态㊁激光入射时和激发荧光时锥形光纤的扫描电子显微镜图像ꎮ（a ）（b ）（c ）FilterLaserSlot vial array Biconical taper Moving directionMicrochannel Capillary Syringe（d ）Filter SpectrographH OS 3H OS 2S 1H OS l o t v i a l图４㊀拉锥光纤荧光传感系统的实验装置ꎮ(ａ)显微镜下的自然状态ꎻ(ｂ)激光入射ꎻ(ｃ)荧光激发ꎻ(ｄ)图像ꎮＦｉｇ.４㊀Ｅｘｐｅｒｉｍｅｎｔａｌｄｅｖｉｃｅｏｆｔａｐｅｒｅｄｆｉｂｅｒｆｌｕｏｒｅｓｃｅｎｃｅｓｅｎｓｉｎｇｓｙｓｔｅｍ.(ａ)Ｎａｔｕｒａｌｓｔａｔｅｕｎｄｅｒｔｈｅｍｉｃｒｏ￣ｓｃｏｐｅ.(ｂ)Ｌａｓｅｒｉｎｃｉｄｅｎｃｅ.(ｃ)Ｆｌｕｏｒｅｓｃｅｎｃｅｅｘｃｉ￣ｔａｔｉｏｎ.(ｄ)Ｉｍａｇｅ.上述实验中需要将拉锥光纤嵌入检测皿中ꎬ无法实现方便快速地进行检测ꎬＺｈａｎｇ等[２４]提出裸芯结构的光纤探针ꎬ直接将制备好的光纤探针伸入大肠杆菌溶液中进行快速检测ꎮ图５(ａ)为FC connector Inlet Fiber probe OutletFC adaptorFC connectorFiber couplerLaserCollimator FilterPCR 1R 2n con cl 兹i兹i 1（z ）茁1琢1（z ）琢2（z ）茁2n mL 1L 2Taper 2Taper 1（a ）（b ）Sample cellFluorescent signalExcitation light R 3n clzPMTClad section图５㊀裸芯光纤探针荧光传感系统的实验装置(ａ)与裸芯结构(ｂ)Ｆｉｇ.５㊀Ｅｘｐｅｒｉｍｅｎｔａｌｄｅｖｉｃｅｏｆｂａｒｅ￣ｃｏｒｅｆｉｂｅｒｐｒｏｂｅｆｌｕｏｒｅｓｃｅｎｔｓｅｎｓｉｎｇｓｙｓｔｅｍ(ａ)ａｎｄｂａｒｅ￣ｃｏｒｅｓｔｒｕｃｔｕｒｅ(ｂ)活菌死菌碘化丙啶抗体激光荧光图６㊀功能化处理光纤探针原理图Ｆｉｇ.６㊀Ｓｃｈｅｍａｔｉｃｄｉａｇｒａｍｏｆｆｕｎｃｔｉｏｎａｌｉｚｅｄｏｐｔｉｃａｌｆｉｂｅｒｐｒｏｂｅ光纤荧光传感系统ꎬ图５(ｂ)为裸芯锥形光纤结构ꎬ利用管腐蚀法来去除光纤包层ꎮ而上述光纤探针不具有特异性检测能力ꎬＺｈａｎｇ等[２５]在原有结构的基础上用化学手段功能化处理光纤探针ꎬ使光纤探针表面交联抗体ꎬ抗体能够与大肠杆菌特异性结合ꎮ如图５所示ꎬ实验用荧光染料碘化丙啶标记了大肠杆菌死菌ꎬ倏逝波激发碘化丙啶１２７２㊀发㊀㊀光㊀㊀学㊀㊀报第４１卷产生荧光ꎬ实现了对死菌的检测ꎮ３.３㊀空心光纤荧光检测过程都需要在暗室中进行ꎬ避免外界环境因素对检测结果产生较大影响ꎮ如果将荧光检测过程置于空心光子晶体光纤(ＨＣ￣ＰＣＦ)中进行ꎬ则可以有效地抵抗环境的干扰ꎮ并且ＨＣ￣ＰＣＦ通过纤芯空气孔导光提供基模传输ꎬ能够将９９％的光都限制在纤芯内传输ꎬ实现低损耗传输[２６]ꎮ为估算ＨＣ￣ＰＣＦ纤芯传播模式数ꎬＣｒｅｇａｎ等[２７]推导了近似估算公式如下:ＮＰＢＧ＝(β２Ｈ－β２Ｌ)ｒ２ｃｏｒｅ４ꎬ(２)ＮＰＢＧ＝(ｋ２ｎ２１－β２Ｌ)ｒ２ｃｏｒｅ４ꎬ(３)其中ꎬＮＰＢＧ为传播的导模数ꎬｎ１为纤芯折射率ꎬβＨ㊁βＬ分别为定波长下传播常数最大值和最小值ꎮ由公式可知ꎬＨＣ￣ＰＣＦ纤芯半径必须适中ꎬ以接近理想传输模式ꎮ在该原理基础上ꎬＣｈｅｎ等[２８]提出如图７所示的ＨＣＰＣＦ结构ꎬ空心孔尺寸为４.８μｍꎮ包层孔用融合拼接技术密封ꎬ中心孔保持开放ꎬ并允许通过聚合诱导发射(ＡＩＥ)分子溶液ꎮ在基于该结构的ＡＩＥ分子检测中ꎬ仅需０.３６ｎＬ样本就可以完成实验ꎮＨＣ￣ＰＣＦ结构设计多样ꎬＹｕ等[２９]设计并制造了如图８所示的ＨＣ￣ＰＣＦ结构ꎬ将花青素Ｃｙ３㊁Ｃｙ５的混合溶液作为荧光染料注入到中空纤芯中ꎬ成功实现了激光的荧光共振能量转移ꎮAlE moleculeOutputFilled coreHollow core photonics crystal fiberCore 4.8滋mCladding 81滋m 图７㊀基于ＡＩＥ诱导分子的ＨＣ￣ＰＣＦ传感原理图Ｆｉｇ.７㊀ＨＣ￣ＰＣＦｓｅｎｓｉｎｇｐｒｉｎｃｉｐｌｅｄｉａｇｒａｍｂａｓｅｄｏｎＡＩＥｉｎ￣ｄｕｃｉｎｇｍｏｌｅｃｕｌｅ图８㊀基于花青素染料的ＨＣ￣ＰＣＦ结构Ｆｉｇ.８㊀ＨＣ￣ＰＣＦｓｔｒｕｃｔｕｒｅｂａｓｅｄｏｎａｎｔｈｏｃｙａｎｉｎｄｙｅｓ４㊀基于荧光猝灭效应的光纤传感器应用４.１㊀重金属离子检测工业排出的污水中还有大量的Ｃｕ２＋㊁Ｆｅ３＋㊁Ｈｇ２＋等重金属离子ꎬ重金属离子对人体危害极大ꎬ痕量重金属离子的检测也是研究热点[３０￣３１]ꎮ利用重金属离子对荧光的猝灭效应ꎬ基于荧光猝灭效应的光纤传感器也广泛应用于重金属离子检测中ꎮＺｈｏｕ等[３２]在裸芯光纤探针结构表面交联碲化镉(ＣｄＴｅ)量子点(ＱＤｓ)ꎬ并掺杂水凝胶ꎮＱＤｓ是把激子在三维空间方向上束缚住的半导体纳米结构作为一种特殊的纳米材料ꎬ具有特殊的光学㊁电学性质[３３￣３４]ꎮ在该结构中ꎬＱＤｓ可以被扩散到水凝胶基质ꎬ待测液中的Ｆｅ３＋对其进行选择性猝灭ꎬ可用于实时现场检测ꎮ传感器浓度响应在０~３.５μｍｏｌ/Ｌ范围内呈线性ꎬ检测限为１４ｎｍｏｌ/ＬꎮＬｉｕ等[３５]利用聚乙烯醇将ＡｇＩｎＺｎＳ￣ＱＤｓ沉积在光纤尖端制成光纤探针检测Ｃｕ２＋含量ꎬ如图９所示为检测过程中的光谱图和其浓度响应ꎮ随着浓度的增加ꎬ荧光强度逐渐减小ꎬ在２.５~８００ｎｍｏｌ/Ｌ浓度范围传感器呈线性响应ꎮ5k 500800姿/nmI n t e n s i t y /a .u .6k 4k 3k 2k 1k0nmol/L07517535050060070080025100250425550650750800nmol/L600700（a ）5k 0800[Cu 2+]/(nmol ·L -1)I n t e n s i t y /a .u .6k 4k 3k 2k 1k 0400600（b ）I =5438.63-4.97×109[Q ]R 2=0.997200Measured data Fitting curve图９㊀用于Ｃｕ２＋检测的ＡｇＩｎＺｎＳ￣ＱＤｓ光纤探针光谱(ａ)与浓度响应(ｂ)Ｆｉｇ.９㊀(ａ)ＡｇＩｎＺｎＳ￣ＱＤｓｆｉｂｅｒｐｒｏｂｅｓｐｅｃｔｒａｆｏｒＣｕ２＋ｄｅｔｅｃ￣ｔｉｏｎ.(ｂ)Ｃｏｎｃｅｎｔｒａｔｉｏｎｒｅｓｐｏｎｓｅ.㊀第１０期陈㊀静ꎬ等:基于荧光猝灭效应的光纤传感器研究进展１２７３㊀Ｈｅｌｅｎａ等[３６]提出一种基于碳点纳米颗粒的Ｈｇ２＋浓度传感系统ꎬ该纳米颗粒利用溶胶￣凝胶方法在光纤探针表面生成一层薄膜ꎮ实验可检测亚微米级浓度的Ｈｇ２＋水溶液ꎬ在ｐＨ＝６.８环境下ꎬ其Ｓｔｅｒｎ￣Ｖｏｌｍｅｒ常数ＫＳＶ达到５.３ˑ１０５Ｌ/ｍｏｌꎮ为寻求更加便捷的实验装置ꎬＬｉｕ等[３７]用智能手机取代光谱仪ꎬ利用硒化镉/硫化锌(ＣｄＳｅ/ＺｎＳ)ＱＤｓ改性后的光纤探针进行Ｈｇ２＋检测ꎮ如图１０所示为ＱＤｓ改性原理图ꎬＱＤｓ通过键合的方式与光纤探针表面交联ꎮ荧光信号由智能手机收集和处理ꎬ最终得到检测范围为１~１０００ｎｍｏｌ/Ｌꎬ检测限可以达到１ｎｍｏｌ/ＬꎮOH OH OH OHOH OH OHAPTESSiOC2H5NH2OC2H5C2H5OOHOHOHOOOO SiSiSiSiOC2H5OOONH2NH2NH2NH2OC2H5COOHHOOCOHOHOHOOOO SiSiSiSiOC2H5OOOOC2H5EDC/NHSCOOHCOOHCOOHCOOHOOOOQDsQDsQDsQDsQDsQDsQDs QDsHOOC COOHNCNNHOOCCNNNHOOOOOCOOHCOONOONHNHNHNHNH图１０㊀ＣｄＳｅ/ＺｎＳ￣ＱＤｓＱＤｓ改性原理Ｆｉｇ.１０㊀ＣｄＳｅ/ＺｎＳ￣ＱＤｓｍｏｄｉｆｉｃａｔｉｏｎｐｒｉｎｃｉｐｌｅ４.２㊀爆炸物检测微量炸药的准确测量与国际安全和日常生活安全息息相关ꎬ光纤荧光传感技术因其方便㊁快捷㊁灵敏度高等优点成为炸药检测领域的关键技术之一ꎮ中国科学院上海微系统与信息技术研究所从２００５年开始研制的ＳＩＭ系列痕量爆炸物探测器[３８]ꎬ采用了荧光聚合物猝灭传感技术ꎮ通过擦拭采样或吸气采样ꎬ可以快速检测三硝基甲苯(ＴＮＴ)㊁二硝基甲苯(ＤＮＴ)㊁硝化甘油(ＮＧ)㊁硝酸铵(ＡＮ)㊁黑火药(ＢＰ)㊁塑性炸药(Ｃ４)等爆炸物ꎮＣｈｕ等[３９]基于荧光猝灭原理对硝基芳香族炸药ＴＮＴ进行检测ꎬ将光纤绕棒缠绕构成的螺旋结构作为传感部位ꎬ荧光猝灭剂为聚[２￣甲氧基￣５￣(２￣乙基己氧基)￣１ꎬ４￣苯乙炔](ＭＥＨ￣ＰＰＶ)ꎬ测定荧光强度和寿命来确定ＴＮＴ浓度ꎬ传感器灵敏度达到了５ｎｇ/ｍＬꎮ中国科学院软物质化学重点实验室Ｌｉｕ等[４０]制作了锥形光纤探针ꎬ并交联荧光多孔聚合物膜结合在其表面ꎬ其存在的多面体低聚硅倍半氧烷(ＰＯＳＳ)使膜呈现出有序的多孔结构ꎬ同时该膜存在具有聚集诱导发射特性的四苯基乙烯(ＴＰＥ)以产生强烈的荧光ꎮ利用激光光源激发荧光对ＴＮＴ和ＤＮＴ浓度进行检测ꎬ图１１为ＴＮＴ检测的光谱和浓度响应ꎻＴＮＴ浓度在１００ˑ１０－９情况下ꎬ荧光猝灭在３０ｓ时达到２５.２％ꎬ在１２０ｓ时达到５１.８％ꎬ在５ｍｉｎ内达到了７３.５％ꎮＴＰＥ及其衍生物具有聚集诱导发光特性ꎬ在光电材料领域应用前景广阔ꎮＹａｎｇ等[４１]提出了基于荧光猝灭效应的ＨＣ￣ＰＣＦ挥发性痕量炸药传感器ꎬ该传感器是将烯丙基四苯乙烯(ＡＬ￣ＴＰＥ)荧光纳米薄膜涂覆在ＨＣ￣ＰＣＦ芯空气孔内ꎮ如图１２所示为ＡＬ￣ＴＰＥ膜与ＴＮＴ之间的电子转移过程ꎬ激发态ＡＬ￣ＴＰＥ分子与处于基态的爆炸分子之间发生电子转移ꎬ导致荧光强度降低ꎬ产生猝灭效应ꎮ当膜厚为１５５ｎｍ时ꎬ对ＴＮＴ的检测灵敏度达到了０.３０９ˑ１０９ꎬ最小检测限０.３４０ˑ１０－９ꎻ膜厚为１１０ｎｍ时ꎬＤＮＴ的响应时间达到１２０ｓꎮ１２７４㊀发㊀㊀光㊀㊀学㊀㊀报第４１卷30000500700姿/nmF l i n t e n s i t y /a .u .40000（a ）0s720s 6002000010000100700t /s（I 0-I ）/I 00.8（b ）400NO 3NO 3CH 3O 3N0.702003005006008000.60.50.40.30.20.10图１１㊀用于ＴＮＴ检测的光纤锥形探针光谱(ａ)与浓度响应(ｂ)Ｆｉｇ.１１㊀(ａ)ＦｉｂｅｒｔａｐｅｒｐｒｏｂｅｓｐｅｃｔｒａｆｏｒＴＮＴｄｅｔｅｃｔｉｏｎ.(ｂ)Ｃｏｎｃｅｎｔｒａｔｉｏｎｒｅｓｐｏｎｓｅ.Electron transferFluorescent bright stateQuenchers(TNT)Non 鄄fluorescent dark stateh 淄eee图１２㊀ＡＬ￣ＴＰＥ膜和ＴＮＴ之间的电子转移过程Ｆｉｇ.１２㊀ＥｌｅｃｔｒｏｎｔｒａｎｓｆｅｒｐｒｏｃｅｓｓｂｅｔｗｅｅｎＡＬ￣ＴＰＥｆｉｌｍａｎｄｅｘｐｌｏｓｉｖｅ㊀４.３㊀溶解气体检测溶解气体的精准检测在环境㊁生物㊁工业领域都具有重要意义ꎬ例如一氧化氮(ＮＯ)溶液的浓度检测可以诊断高血压㊁心衰㊁糖尿病等疾病ꎬ氧溶液的检测可以应用于污水处理厂㊁自来水厂水质的诊断ꎮ许多气体分子对荧光存在猝灭效应ꎬ因此也开拓了基于荧光猝灭效应的光纤传感器在溶解气体检测领域的应用ꎮＤｉｎｇ等[４２]搭建了荧光探针结构传感系统ꎬ将ＣｄＳｅ￣ＱＤｓ和醋酸纤维素(ＣＡ)作为敏感膜来检测水溶液中的ＮＯꎬ其中ＣｄＳｅ￣ＱＤ通过简单的杂交方法嵌入ＣＡ中ꎮＮＯ自由基可以很容易地与水中的溶解氧发生反应并与Ｃｄ２＋发生配位ꎬ对敏感膜中ＣｄＳｅ￣ＱＤｓ的荧光有明显的猝灭作用ꎮ使用这种新型的光纤传感器ꎬ通过相位调制荧光法确定了ＮＯ浓度ꎮ如图１３所示ꎬ在最佳条件下ꎬ１.０ˑ１０－７~１.０ˑ１０－６ｍｏｌ/Ｌ检测范围中的线性拟合系数为０.９９０８ꎬ最低检测限达到了１.０ˑ１０－８ｍｏｌ/Ｌꎮ邓辉等[４３]利用动态化学腐蚀法制备锥尖型光纤端面ꎬ以提拉法镀溶胶凝胶敏感膜组装了基于荧光猝灭的直径仅１.５μｍ的光纤氧溶液传感探头ꎮ探头锥面的长径比可通过调控腐蚀参数调控ꎬ构建相移测量系统ꎬ优化参数后进行０~２１％范围内的氧含量测定ꎬ工作曲线呈现良好的线性特征ꎬ拟合系数为０.９９９６ꎬ偏差小于测量值的５％ꎮ此外ꎬ德国Ｅ＋Ｈ公司研制的溶解氧传感器ＯｘｙｍａｘＣＯＳ６１Ｄ[４４]ꎬ同样基于荧光猝灭原理进行传感ꎮ该传感器检测范围０~２０ｍｇ/Ｌꎬ在<１２ｍｇ/Ｌ范围内ꎬ最大测量误差为ʃ１％ꎻ在１２~２０ｍｇ/Ｌ范围内ꎬ最大测量误差为ʃ２％ꎮ-78.46004800t /sP h a s e s h i f t 准/a .u .1200-79.2180024003000[NO]:滋mol/L0.10.20.30.40.50.60.70.80.91.03600420054006000图１３㊀不同浓度ＮＯ溶液的相位变化Ｆｉｇ.１３㊀ＰｈａｓｅｃｈａｎｇｅｉｎＮＯｓｏｌｕｔｉｏｎｗｉｔｈｄｉｆｆｅｒｅｎｔｃｏｎｃｅｎ￣ｔｒａｔｉｏｎ４.４㊀温度检测温度会使荧光强度降低产生荧光猝灭现象ꎬ基于荧光猝灭效应的光纤传感技术也可以对温度进行检测ꎮ这种基于荧光猝灭效应的光纤传感技术不受传感器外部变形的影响ꎬ是一种能够消除周围环境和背景噪声干扰的温度选择性传感器ꎮＺｈａｏ等[４５]利用微结构双拉锥结构光纤作为探针进行温度的检测ꎬ将Ｍｇ６Ａｓ２Ｏ１１ʒＭｎ４＋作为荧光材料ꎮ通过对荧光强度的解调ꎬ得到该温度传感器的精度为２ħꎬ温度范围３０~２１０ħꎬ该微传感器的响应时间比传统传感器快５０~１００倍ꎮ而日本安立(Ａｎｒｉｔｓｕ)公司研制的荧光式光纤温度计[４６￣４７]已经完全商业化ꎬ达到了－１９５.０~４５０.０ħ的检测范围ꎬ精度为０.１ħꎮ其产品由ＦＸ系㊀第１０期陈㊀静ꎬ等:基于荧光猝灭效应的光纤传感器研究进展１２７５㊀列发展到ＦＬ系列[４８]ꎬ如图１４所示为ＦＬ￣２０００型号产品探头结构ꎮ基于荧光猝灭原理ꎬ利用光纤前端表面存在的荧光物质进行温度检测ꎬ从接收激励光到衰减的寿命作为温度传感信息ꎮin sensorIndentation the connector of the instrument(×2)Protrusion of the sensor(×2)Key ring图１４㊀ＦＬ￣４０００型号光纤探头Ｆｉｇ.１４㊀ＦＬ￣４０００ｔｙｐｅｆｉｂｅｒｏｐｔｉｃｐｒｏｂｅ４.５㊀其他领域应用除了上述参量的检测ꎬ基于荧光猝灭效应的光纤荧光传感器也在其他领域检测中得到了应用ꎮＴｏｎ等[４９]在光纤波导上涂覆含有荧光信号基团的ＭＩＰꎬＭＩＰ由萘基荧光单体组成ꎬ用于检测除草剂中的２ꎬ４￣二氯苯氧乙酸和桔霉素ꎮ萘基单体与分析物的羧酸基分子结合后荧光增强ꎬ从而降低了氮给电子的能力ꎬ阻止负责荧光猝灭的光诱导电子转移ꎬ使ＭＩＰ的荧光强度增强具有浓度依赖性ꎮ中国科学院软物质化学重点实验室Ｚｈｕ等[５０]利用三烯丙基异氰脲酸酯㊁烷烃二硫醇和酸碱Ｄ￣天冬氨酸复合(ＰＢＩＭ/Ｄ￣Ａｓｐ)在光纤探针末端形成ＭＩＰ膜用于Ｄ￣Ａｓｐ含量检测ꎬ当ｐＨ值达到碱性条件时ꎬＰＢＩＭ结构会发生变化从而导致荧光猝灭ꎮＮｇｕｙｅｎ等[５１]制备了光纤探针ꎬ选择吖啶作为荧光染料ꎬ利用Ｃｌ－的荧光猝灭效应对其进行检测ꎬ检测限达到０.１ｍｏｌ/Ｌꎮ美国国家基础科学研究中心Ｐｏｌｌｅｙ等[５２]在光纤探头表面交联乙锭染料ꎬ实现对ＤＮＡ的检测ꎮ５㊀未来发展２０１７年ꎬ清华大学杨昌喜研究团队提出一种由有机硅聚合物制成的可穿戴式光纤传感器[５３]ꎬ该传感器能够承受和检测伸长率达１００％的形变ꎬ可以实时㊁有效地感测人体运动ꎮ该有机硅聚合物为聚二甲基硅氧烷(ＰＤＭＳ)ꎬ制造出的ＰＤＭＳ光纤表现出很好的机械柔韧性ꎮ为了辅助传感ꎬ研究人员将荧光染料罗丹明Ｂ混入光纤中ꎬ当光通过光纤时ꎬ部分光被荧光染料吸收ꎻ光纤拉伸越大ꎬ染料吸收的光就越多ꎬ因此由分光镜检测投射光就可以测量光纤的拉伸和弯曲程度ꎮ相较于一般的电子传感器ꎬ光纤型传感器具有体积小㊁弹性强㊁不受电磁干扰的优点ꎮ基于荧光猝灭效应的光纤传感技术同样有望与可穿戴式传感相结合ꎬ光纤可作为类纤维嵌入衣物中ꎬ可以实时监测温度㊁湿度等环境情况ꎬ也可以监测呼吸㊁心跳等人类生理特征ꎮ这些特点都可以在医疗行业㊁特种部队㊁工业养殖等领域得到广泛应用ꎮ荧光材料选择的多样性决定了其应用领域的广泛性ꎬ基于荧光猝灭效应的光纤传感器结合了荧光和光纤的优点ꎬ应用前景可观ꎬ但是目前光纤荧光传感技术仍面临一些挑战ꎮ５.１㊀增强集光能力上述提及的空间光耦合型㊁微结构光纤型等多样的光纤结构ꎬ目的都是为了使光纤能够最大程度地收集产生的荧光ꎬ提高传感器灵敏度的同时ꎬ减少杂散光的干扰ꎮ荧光猝灭材料中的共轭聚合物消光系数可达１０６Ｌｍｏｌ－１ｃｍ－１ꎬ具有较强的集光能力[５４]ꎻ在ＨＣ￣ＰＣＦ空气孔内进行荧光反应ꎬ能够极大地接收荧光ꎬ但是其实验要求高难以实用化ꎮ用多种方式增强光纤收集荧光的能力ꎬ仍然是目前的研究热点ꎮ５.２㊀提高荧光产率荧光产率是指发射荧光的光子数ｎ２与被激活物质从泵浦源吸收的光子数ｎ１之比ꎬ是评价荧光材料性能最直观的参考数据ꎮ目前的研究除了寻求和制备高荧光产率的荧光分子外ꎬ也会通过在原有荧光材料基础上掺入杂质物质来提高ꎮ例如ꎬ钇掺杂的碳量子点荧光产率达到４１％[５５]ꎬ相较于未掺杂情况提升了１７.３％ꎮ但目前荧光材料的荧光产率仍有待提高ꎮ而且通过从材料入手来提高荧光产率的方式ꎬ可以避免改变传感系统性能来提高灵敏度ꎬ可靠性更强ꎮ５.３㊀便携实时原位检测原位检测是不破坏待测物自身结构㊁状态而进行的无损伤检测方式ꎬ对于荧光猝灭光纤传感来说至关重要ꎮ荧光检测环境不能够仅仅局限于在实验室进行ꎬ最终目标仍然是实现便捷实时原位的现场检测ꎮ目前荧光猝灭光纤传感器产品已涉及爆炸物㊁水质等领域ꎬ但是设计紧凑便捷传感系统结构㊁开拓更多应用领域㊁实时地实地快速检１２７６㊀发㊀㊀光㊀㊀学㊀㊀报第４１卷测ꎬ仍然是研发工作人员的研究目标ꎮ６㊀结㊀㊀论基于荧光猝灭效应的光纤传感技术能够有效地利用光纤体积小㊁抗干扰能力强等优点ꎬ实现快速㊁便捷地特异性检测ꎮ本文以荧光猝灭原理为基础ꎬ从传感光纤结构㊁基于荧光猝灭效应的光纤传感器应用两个方面简要叙述了光纤与荧光检测的结合机理及传感器相关应用ꎮ基于荧光猝灭的光纤传感器有望作为类纤维嵌入衣物中ꎬ从而实现实时的智能传感ꎮ而基于荧光猝灭效应的光纤传感技术也面临挑战ꎬ未来将朝着集光能力更强㊁荧光产率更高㊁便携实时原位检测方向发展ꎮ参㊀考㊀文㊀献:[１]史慧超.基于神经网络的光纤荧光海藻测量理论及应用研究[Ｄ].秦皇岛:燕山大学ꎬ２０１０:１０￣１７.ＳＨＩＨＣ.ＳｔｕｄｙｏｎＴｈｅｏｒｙａｎｄＡｐｐｌｉｃａｔｉｏｎｏｆＯｐｔｉｃａｌＦｉｂｅｒＦｌｕｏｒｅｓｃｅｎｃｅＭｅａｓｕｒｅｍｅｎｔｆｏｒＡｌｇａｅＢａｓｅｄｏｎＮｅｒｖｅＮｅｔｗｏｒｋ[Ｄ].Ｑｉｎｈｕａｎｇｄａｏ:ＹａｎｓｈａｎＵｎｉｖｅｒｓｉｔｙｏｆＣｈｉｎａꎬ２０１０:１０￣１７.(ｉｎＣｈｉｎｅｓｅ)[２]ＮÖＲＺＤꎬＦＩＳＣＨＥＲＮꎬＳＣＨＵＬＴＺＥＡꎬｅｔａｌ..ＣｌｉｎｉｃａｌｅｖａｌｕａｔｉｏｎｏｆａＳＡＲＳ￣ＣｏＶ￣２ＲＴ￣ＰＣＲａｓｓａｙｏｎａｆｕｌｌｙａｕｔｏｍａｔｅｄｓｙｓｔｅｍｆｏｒｒａｐｉｄｏｎ￣ｄｅｍａｎｄｔｅｓｔｉｎｇｉｎｔｈｅｈｏｓｐｉｔａｌｓｅｔｔｉｎｇ[Ｊ].Ｊ.Ｃｌｉｎ.Ｖｉｒｏｌ.ꎬ２０２０ꎬ１２８:１０４３９０￣１￣３. [３]何关金.基于微流控技术的数字ＰＣＲ检测仪设计与实现[Ｊ].天津科技ꎬ２０２０ꎬ４７(１):３５￣４０.ＨＥＧＪ.ＤｅｓｉｇｎａｎｄｉｍｐｌｅｍｅｎｔａｔｉｏｎｏｆｄｉｇｉｔａｌＰＣＲｄｅｔｅｃｔｏｒｂａｓｅｄｏｎｍｉｃｒｏｆｌｕｉｄｉｃｔｅｃｈｎｏｌｏｇｙ[Ｊ].ＴｉａｎｊｉｎＳｃｉ.Ｔｅｃｈｎｏｌ.ꎬ２０２０ꎬ４７(１):３５￣４０.(ｉｎＣｈｉｎｅｓｅ)[４]ＭＣＥＶＯＹＡＫꎬＭＣＤＯＮＡＧＨＣＭꎬＭＡＣＣＲＡＩＴＨＢＤ.Ｄｉｓｓｏｌｖｅｄｏｘｙｇｅｎｓｅｎｓｏｒｂａｓｅｄｏｎｆｌｕｏｒｅｓｃｅｎｃｅｑｕｅｎｃｈｉｎｇｏｆｏｘｙ￣ｇｅｎ￣ｓｅｎｓｉｔｉｖｅｒｕｔｈｅｎｉｕｍｃｏｍｐｌｅｘｅｓｉｍｍｏｂｉｌｉｚｅｄｉｎｓｏｌ￣ｇｅｌ￣ｄｅｒｉｖｅｄｐｏｒｏｕｓｓｉｌｉｃａｃｏａｔｉｎｇｓ[Ｊ].Ａｎａｌｙｓｔꎬ１９９６ꎬ１２１(６):７８５￣７８８.[５]ＫＡＵＴＳＫＹＨꎬＤＥＢＲＵＩＪＮＨ.ＤｉｅＡｕｆｋｌäｒｕｎｇｄｅｒＰｈｏｔｏｌｕｍｉｎｅｓｃｅｎｚｔｉｌｇｕｎｇｆｌｕｏｒｅｓｃｉｅｒｅｎｄｅｒＳｙｓｔｅｍｅｄｕｒｃｈＳａｕｅｒｓｔｏｆｆ:ｄｉｅＢｉｌｄｕｎｇａｋｔｉｖｅｒꎬｄｉｆｆｕｓｉｏｎｓｆäｈｉｇｅｒＳａｕｅｒｓｔｏｆｆｍｏｌｅｋüｌｅｄｕｒｃｈＳｅｎｓｉｂｉｌｉｓｉｅｒｕｎｇ[Ｊ].Ｎａｔｕｒｗｉｓｓｅｎｓｃｈａｆｔｅｎꎬ１９３１ꎬ１９(５２):１０４３￣１０４３.[６]ＫＡＵＴＳＫＹＨ.Ｅｎｅｒｇｉｅ￣ＵｍｗａｎｄｌｕｎｇａｎＧｒｅｎｚｆｌäｃｈｅｎꎬＶＩＩ.Ｍｉｔｔｅｉｌ.:Ｈ.ＫａｕｔｓｋｙꎬＨ.ｄｅＢｒｕｉｊｎꎬＲ.ＮｅｕｗｉｒｔｈｕｎｄＷ.Ｂａｕｍｅｉｓｔｅｒ:ｐｈｏｔｏ￣ｓｅｎｓｉｂｉｌｉｓｉｅｒｔｅｏｘｙｄａｔｉｏｎａｌｓｗｉｒｋｕｎｇｅｉｎｅｓａｋｔｉｖｅｎꎬｍｅｔａｓｔａｂｉｌｅｎｚｕｓｔａｎｄｅｓｄｅｓｓａｕｅｒｓｔｏｆｆ￣ｍｏｌｅｋüｌｓ[Ｊ].Ｅｕｒ.Ｊ.Ｉｎｏｒｇ.Ｃｈｅｍ.ꎬ１９３３ꎬ６６(１０):１５８８￣１６００.[７]ＫＡＵＴＳＫＹＨ.Ｑｕｅｎｃｈｉｎｇｏｆｌｕｍｉｎｅｓｃｅｎｃｅｂｙｏｘｙｇｅｎ[Ｊ].Ｔｒａｎｓ.ＦａｒａｄａｙＳｏｃ.ꎬ１９３９ꎬ３５:２１６￣２１９.[８]ＫＵＺＭＩＮＡＶꎬＰＬＥＫＨＡＮＯＶМＳꎬＬＥＳＮＩＣＨＹＯＶＡＡＳ.Ｉｎｆｌｕｅｎｃｅｏｆｉｍｐｕｒｉｔｉｅｓｏｎｔｈｅｂｕｌｋａｎｄｇｒａｉｎ￣ｂｏｕｎｄａｒｙｃｏｎｄｕｃ￣ｔｉｖｉｔｙｏｆＣａＺｒＯ３￣ｂａｓｅｄｐｒｏｔｏｎ￣ｃｏｎｄｕｃｔｉｎｇｅｌｅｃｔｒｏｌｙｔｅ:ａｄｉｓｔｒｉｂｕｔｉｏｎｏｆｒｅｌａｘａｔｉｏｎｔｉｍｅｓｔｕｄｙ[Ｊ].Ｅｌｅｃｔｒｏｃｈｉｍ.Ａｃｔａꎬ２０２０ꎬ３４８:１３６３２７.[９]ＨＯＮＧＪＸꎬＸＩＡＱＦꎬＺＨＯＵＥＢꎬｅｔａｌ..ＮＩＲｆｌｕｏｒｅｓｃｅｎｔｐｒｏｂｅｂａｓｅｄｏｎａｍｏｄｉｆｉｅｄｒｈｏｄｏｌ￣ｄｙｅｗｉｔｈｇｏｏｄｗａｔｅｒｓｏｌｕｂｉｌｉｔｙａｎｄｌａｒｇｅＳｔｏｋｅｓｓｈｉｆｔｆｏｒｍｏｎｉｔｏｒｉｎｇＣＯｉｎｌｉｖｉｎｇｓｙｓｔｅｍｓ[Ｊ].Ｔａｌａｎｔａꎬ２０２０ꎬ２１５:１２０９１４.[１０]ＰＩＥＲＣＥＭＥꎬＧＲＡＮＴＳＡ.ＤｅｖｅｌｏｐｍｅｎｔｏｆａＦＲＥＴｂａｓｅｄｆｉｂｅｒ￣ｏｐｔｉｃｂｉｏｓｅｎｓｏｒｆｏｒｅａｒｌｙｄｅｔｅｃｔｉｏｎｏｆｍｙｏｃａｒｄｉａｌｉｎｆａｒｃｔｉｏｎ[Ｃ].ＰｒｏｃｅｅｄｉｎｇｓｏｆＴｈｅ２６ｔｈＡｎｎｕａｌＩｎｔｅｒｎａｔｉｏｎａｌＣｏｎｆｅｒｅｎｃｅｏｆＴｈｅＩＥＥＥＥｎｇｉｎｅｅｒｉｎｇｉｎＭｅｄｉｃｉｎｅａｎｄＢｉｏｌｏｇｙＳｏｃｉｅｔｙꎬＳａｎＦｒａｎｃｉｓｃｏꎬ２００４:２０９８￣２１０１.[１１]ＺＨＡＯＪＷꎬＺＨＥＮＧＹＹꎬＰＡＮＧＹＹꎬｅｔａｌ..Ｇｒａｐｈｅｎｅｑｕａｎｔｕｍｄｏｔｓａｓｆｕｌｌ￣ｃｏｌｏｒａｎｄｓｔｉｍｕｌｕｓｒｅｓｐｏｎｓｉｖｅｆｌｕｏｒｅｓｃｅｎｃｅｉｎｋｆｏｒｉｎｆｏｒｍａｔｉｏｎｅｎｃｒｙｐｔｉｏｎ[Ｊ].Ｊ.ＣｏｌｌｏｉｄＩｎｔｅｒｆａｃｅＳｃｉ.ꎬ２０２０ꎬ５７９:３０７￣３１４.[１２]ＬＩＡＯＫＣꎬＨＯＧＥＮ￣ＥＳＣＨＴꎬＲＩＣＨＭＯＮＤＦＪꎬｅｔａｌ..Ｐｅｒｃｕｔａｎｅｏｕｓｆｉｂｅｒ￣ｏｐｔｉｃｓｅｎｓｏｒｆｏｒｃｈｒｏｎｉｃｇｌｕｃｏｓｅｍｏｎｉｔｏｒｉｎｇｉｎｖｉ￣ｖｏ[Ｊ].Ｂｉｏｓｅｎｓ.Ｂｉｏｅｌｅｃｔｒｏｎ.ꎬ２００８ꎬ２３(１０):１４５８￣１４６５.[１３]ＨＥＷＹꎬＬＩＵＲＱꎬＬＩＡＯＹＨꎬｅｔａｌ..Ａｎｅｗ１ꎬ２ꎬ３￣ｔｒｉａｚｏｌｅａｎｄｉｔｓｒｈｏｄａｍｉｎｅＢｄｅｒｉｖａｔｉｖｅｓａｓａｆｌｕｏｒｅｓｃｅｎｃｅｐｒｏｂｅｆｏｒｍｅｒｃｕｒｙｉｏｎｓ[Ｊ].Ａｎａｌ.Ｂｉｏｃｈｅｍ.ꎬ２０２０ꎬ５９８:１１３６９０.[１４]ＪＩＮＣＺꎬＬＩＡＮＧＦＹꎬＷＡＮＧＪＱꎬｅｔａｌ..Ｒａｔｉｏｎａｌｄｅｓｉｇｎｏｆｃｙｃｌｏｍｅｔａｌａｔｅｄｉｒｉｄｉｕｍ(Ⅲ)ｃｏｍｐｌｅｘｅｓｆｏｒｔｈｒｅｅ￣ｐｈｏｔｏｎｐｈｏｓ￣ｐｈｏｒｅｓｃｅｎｃｅｂｉｏｉｍａｇｉｎｇ[Ｊ].Ａｎｇｅｗ.Ｃｈｅｍ.ꎬ２０２０ꎬ１３２(３７):１６１２１￣１６１２５[１５]ＰＥＮＪＷＥＩＮＩＲꎬＲＯＡＲＫＥＢꎬＡＬＳＰＡＵＧＨＧꎬｅｔａｌ..Ｓｉｎｇｌｅｃｅｌｌ￣ｂａｓｅｄｆｌｕｏｒｅｓｃｅｎｃｅｌｉｆｅｔｉｍｅｉｍａｇｉｎｇｏｆｉｎｔｒａｃｅｌｌｕｌａｒｏｘｙｇｅｎ￣ａｔｉｏｎａｎｄｍｅｔａｂｏｌｉｓｍ[Ｊ].ＲｅｄｏｘＢｉｏｌ.ꎬ２０２０ꎬ３４:１０１５４９￣１￣２５.㊀第１０期陈㊀静ꎬ等:基于荧光猝灭效应的光纤传感器研究进展１２７７㊀[１６]ＢＥＮＩＴＯ￣ＰＥÑＡＥꎬＶＡＬＤÉＳＭＧꎬＧＬＡＨＮ￣ＭＡＲＴÍＮＥＺＢꎬｅｔａｌ..Ｆｌｕｏｒｅｓｃｅｎｃｅｂａｓｅｄｆｉｂｅｒｏｐｔｉｃａｎｄｐｌａｎａｒｗａｖｅｇｕｉｄｅｂｉｏ￣ｓｅｎｓｏｒｓ.Ａｒｅｖｉｅｗ[Ｊ].Ａｎａｌ.Ｃｈｉｍ.Ａｃｔａꎬ２０１６ꎬ９４３:１７￣４０.[１７]ＳＴＥＮＫＥＮＪＡ.Ｉｎｔｒｏｄｕｃｔｉｏｎｔｏｆｌｕｏｒｅｓｃｅｎｃｅｓｅｎｓｉｎｇ[Ｊ].Ｊ.Ａｍ.Ｃｈｅｍ.Ｓｏｃ.ꎬ２００９ꎬ１３１(３０):１０７９１.[１８]ＶＡＬＥＵＲＢꎬＢＥＲＢＥＲＡＮ￣ＳＡＮＴＯＳＭＮ.ＭｏｌｅｃｕｌａｒＦｌｕｏｒｅｓｃｅｎｃｅ:ＰｒｉｎｃｉｐｌｅｓａｎｄＡｐｐｌｉｃａｔｉｏｎｓ[Ｍ].２ｎｄｅｄ.Ｗｅｉｎｈｅｉｍ:Ｗｉｌｅｙ￣ＶＣＨꎬ２０１２.[１９]ＵＴＺＩＮＧＥＲＵꎬＲＩＣＨＡＲＤＳ￣ＫＯＲＴＵＭＲＲ.Ｆｉｂｅｒｏｐｔｉｃｐｒｏｂｅｓｆｏｒｂｉｏｍｅｄｉｃａｌｏｐｔｉｃａｌｓｐｅｃｔｒｏｓｃｏｐｙ[Ｊ].Ｊ.Ｂｉｏｍｅｄ.Ｏｐｔ.ꎬ２００３ꎬ８(１):１２１￣１４７.[２０]ＳÁＮＣＨＥＺ￣ＥＳＣＯＢＡＲＳꎬＨＥＲＮÁＮＤＥＺ￣ＣＯＲＤＥＲＯＪ.Ｆｉｂｅｒｏｐｔｉｃｆｌｕｏｒｅｓｃｅｎｃｅｔｅｍｐｅｒａｔｕｒｅｓｅｎｓｏｒｓｕｓｉｎｇｕｐ￣ｃｏｎｖｅｒｓｉｏｎｆｒｏｍｒａｒｅ￣ｅａｒｔｈｐｏｌｙｍｅｒｃｏｍｐｏｓｉｔｅｓ[Ｊ].Ｏｐｔ.Ｌｅｔｔ.ꎬ２０１９ꎬ４４(５):１１９４￣１１９７.[２１]ＭＯＲＡＤＩＶꎬＡＫＢＡＲＩＭꎬＷＩＬＤＰ.Ａｆｌｕｏｒｅｓｃｅｎｃｅ￣ｂａｓｅｄｐＨｓｅｎｓｏｒｗｉｔｈｍｉｃｒｏｆｌｕｉｄｉｃｍｉｘｉｎｇａｎｄｆｉｂｅｒｏｐｔｉｃｄｅｔｅｃｔｉｏｎｆｏｒｗｉｄｅｒａｎｇｅｐＨｍｅａｓｕｒｅｍｅｎｔｓ[Ｊ].Ｓｅｎｓ.ＡｃｔｕａｔｏｒｓＡ:Ｐｈｙｓ.ꎬ２０１９ꎬ２９７:１１１５０７.[２２]帅彬彬.光子晶体光纤表面等离子体共振传感机理及其技术研究[Ｄ].武汉:华中科技大学ꎬ２０１３.ＳＨＵＡＩＢＢ.ＲｅｓｅａｒｃｈｏｎＴｈｅＰｈｏｔｏｎｉｃＣｒｙｓｔａｌＦｉｂｅｒＢａｓｅｄＰｌａｓｍｏｎｉｃＳｅｎｓｉｎｇＭｅｃｈａｎｉｓｍａｎｄＩｔｓＴｅｃｈｎｉｑｕｅ[Ｄ].Ｗｕｈａｎ:ＨｕａｚｈｏｎｇＵｎｉｖｅｒｓｉｔｙｏｆＳｃｉｅｎｃｅａｎｄＴｅｃｈｎｏｌｏｇｙꎬ２０１３.(ｉｎＣｈｉｎｅｓｅ)[２３]ＬＩＺＹꎬＸＵＹＸꎬＦＡＮＧＷꎬｅｔａｌ..Ｕｌｔｒａ￣ｓｅｎｓｉｔｉｖｅｎａｎｏｆｉｂｅｒｆｌｕｏｒｅｓｃｅｎｃｅｄｅｔｅｃｔｉｏｎｉｎａｍｉｃｒｏｆｌｕｉｄｉｃｃｈｉｐ[Ｊ].Ｓｅｎｓｏｒｓꎬ２０１５ꎬ１５(３):４８９０￣４８９８.[２４]ＺＨＡＮＧＺＨꎬＨＵＡＦꎬＬＩＵＴꎬｅｔａｌ..Ａｄｏｕｂｌｅ￣ｔａｐｅｒｏｐｔｉｃａｌｆｉｂｅｒ￣ｂａｓｅｄｒａｄｉａｔｉｏｎｗａｖｅｏｔｈｅｒｔｈａｎｅｖａｎｅｓｃｅｎｔｗａｖｅｉｎａｌｌ￣ｆｉ￣ｂｅｒｉｍｍｕｎｏｆｌｕｏｒｅｓｃｅｎｃｅｂｉｏｓｅｎｓｏｒｆｏｒｑｕａｎｔｉｔａｔｉｖｅｄｅｔｅｃｔｉｏｎｏｆＥｓｃｈｅｒｉｃｈｉａｃｏｌｉＯ１５７:Ｈ７[Ｊ].ＰＬｏＳＯｎｅꎬ２０１４ꎬ９(５):ｅ９５４２９.[２５]刘婷.基于荧光与表面增强拉曼光谱的光纤生化传感器[Ｄ].北京:清华大学ꎬ２０１４:２６￣２７.ＬＩＵＴ.ＯｐｔｉｃａｌＦｉｂｅｒＢｉｏｃｈｅｍｉｃａｌＳｅｎｓｏｒＢａｓｅｄｏｎＦｌｕｏｒｅｓｃｅｎｃｅａｎｄｓｕｒｆａｃｅｅｎｈａｎｃｅｄＲａｍａｎＳｐｅｃｔｒａ[Ｄ].Ｂｅｉｊｉｎｇ:Ｔｓｉｎｇ￣ｈｕａＵｎｉｖｅｒｓｉｔｙꎬ２０１４:２６￣２７.(ｉｎＣｈｉｎｅｓｅ)[２６]邸志刚ꎬ贾春荣ꎬ姚建铨ꎬ等.基于银纳米颗粒的ＨＣＰＣＦＳＥＲＳ传感系统优化设计[Ｊ].红外与激光工程ꎬ２０１５ꎬ４４(４):１３１７￣１３２２.ＤＩＺＧꎬＪＩＡＣＲꎬＹＡＯＪＱꎬｅｔａｌ..ＯｐｔｉｍｉｚａｔｉｏｎｏｎＨＣＰＣＦＳＥＲＳｓｅｎｓｏｒｂａｓｅｄｏｎｓｉｌｖｅｒｎａｎｏｐａｒｔｉｃｌｅｓ[Ｊ].ＩｎｆｒａｒｅｄＬａｓｅｒＥｎｇ.ꎬ２０１５ꎬ４４(４):１３１７￣１３２２.(ｉｎＣｈｉｎｅｓｅ)[２７]ＣＲＥＧＡＮＲＦꎬＭＡＮＧＡＮＢＪꎬＫＮＩＧＨＴＪＣꎬｅｔａｌ..Ｓｉｎｇｌｅ￣ｍｏｄｅｐｈｏｔｏｎｉｃｂａｎｄｇａｐｇｕｉｄａｎｃｅｏｆｌｉｇｈｔｉｎａｉｒ[Ｊ].Ｓｃｉｅｎｃｅꎬ１９９９ꎬ２８５(５４３３):１５３７￣１５３９.[２８]ＣＨＥＮＨＦꎬＪＩＡＮＧＱＪꎬＱＩＵＹＱꎬｅｔａｌ..Ｈｏｌｌｏｗ￣ｃｏｒｅ￣ｐｈｏｔｏｎｉｃ￣ｃｒｙｓｔａｌ￣ｆｉｂｅｒ￣ｂａｓｅｄｍｉｎｉａｔｕｒｉｚｅｄｓｅｎｓｏｒｆｏｒｔｈｅｄｅｔｅｃｔｉｏｎｏｆａｇｇｒｅｇａｔｉｏｎ￣ｉｎｄｕｃｅｄ￣ｅｍｉｓｓｉｏｎｍｏｌｅｃｕｌｅｓ[Ｊ].Ａｎａｌ.Ｃｈｅｍ.ꎬ２０１９ꎬ９１(１):７８０￣７８４.[２９]ＹＵＪꎬＺＨＡＯＸＭꎬＬＩＵＢＨꎬｅｔａｌ..Ｒｅｄｕｃｔｉｏｎｉｎｌａｓｉｎｇｔｈｒｅｓｈｏｌｄｏｆｈｏｌｌｏｗ￣ｃｏｒｅｍｉｃｒｏｓｔｒｕｃｔｕｒｅｄｏｐｔｉｃａｌｆｉｂｅｒｏｐｔｏｆｌｕｉｄｉｃｌａｓｅｒｂａｓｅｄｏｎｆｌｕｏｒｅｓｃｅｎｃｅｒｅｓｏｎａｎｔｅｎｅｒｇｙｔｒａｎｓｆｅｒ[Ｊ].Ｏｐｔ.ＦｉｂｅｒＴｅｃｈｎｏｌ.ꎬ２０２０ꎬ５８:１０２２８１.[３０]ＢＯＤＯＭꎬＢＡＬＬＯＮＩＳꎬＬＵＭＡＲＥＥꎬｅｔａｌ..Ｅｆｆｅｃｔｓｏｆｓｕｂ￣ｔｏｘｉｃｃａｄｍｉｕｍｃｏｎｃｅｎｔｒａｔｉｏｎｓｏｎｂｏｎｅｇｅｎｅｅｘｐｒｅｓｓｉｏｎｐｒｏｇｒａｍ:ｒｅｓｕｌｔｓｏｆａｎｉｎｖｉｔｒｏｓｔｕｄｙ[Ｊ].Ｔｏｘｉｃｏｌ.Ｖｉｔｒｏꎬ２０１０ꎬ２４(６):１６７０￣１６８０.[３１]ＦＡＴＴＡ￣ＫＡＳＳＩＮＯＳＤꎬＫＡＬＡＶＲＯＵＺＩＯＴＩＳＩＫꎬＫＯＵＫＯＵＬＡＫＩＳＰＨꎬｅｔａｌ..Ｔｈｅｒｉｓｋｓａｓｓｏｃｉａｔｅｄｗｉｔｈｗａｓｔｅｗａｔｅｒｒｅｕｓｅａｎｄｘｅｎｏｂｉｏｔｉｃｓｉｎｔｈｅａｇｒｏｅｃｏｌｏｇｉｃａｌｅｎｖｉｒｏｎｍｅｎｔ[Ｊ].Ｓｃｉ.ＴｏｔａｌＥｎｖｉｒｏｎ.ꎬ２０１１ꎬ４０９(１９):３５５５￣３５６３.[３２]ＺＨＯＵＭＪꎬＧＵＯＪＪꎬＹＡＮＧＣＸ.ＲａｔｉｏｍｅｔｒｉｃｆｌｕｏｒｅｓｃｅｎｃｅｓｅｎｓｏｒｆｏｒＦｅ３＋ｉｏｎｓｄｅｔｅｃｔｉｏｎｂａｓｅｄｏｎｑｕａｎｔｕｍｄｏｔ￣ｄｏｐｅｄｈｙ￣ｄｒｏｇｅｌｏｐｔｉｃａｌｆｉｂｅｒ[Ｊ].Ｓｅｎｓ.ＡｃｔｕａｔｏｒｓＢ:Ｃｈｅｍ.ꎬ２０１８ꎬ２６４:５２￣５８.[３３]ＺＨＡＯＬＸꎬＤＩＦꎬＷＡＮＧＤＢꎬｅｔａｌ..Ｃｈｅｍｉｌｕｍｉｎｅｓｃｅｎｃｅｏｆｃａｒｂｏｎｄｏｔｓｕｎｄｅｒｓｔｒｏｎｇａｌｋａｌｉｎｅｓｏｌｕｔｉｏｎｓ:ａｎｏｖｅｌｉｎｓｉｇｈｔｉｎ￣ｔｏｃａｒｂｏｎｄｏｔｏｐｔｉｃａｌｐｒｏｐｅｒｔｉｅｓ[Ｊ].Ｎａｎｏｓｃａｌｅꎬ２０１３ꎬ５(７):２６５５￣２６５８.[３４]ＭＵＲＲＡＹＣＢꎬＮＯＲＲＩＳＤＪꎬＢＡＷＥＮＤＩＭＧ.ＳｙｎｔｈｅｓｉｓａｎｄｃｈａｒａｃｔｅｒｉｚａｔｉｏｎｏｆｎｅａｒｌｙｍｏｎｏｄｉｓｐｅｒｓｅＣｄＥ(Ｅ＝ｓｕｌｆｕｒꎬｓｅ￣ｌｅｎｉｕｍꎬｔｅｌｌｕｒｉｕｍ)ｓｅｍｉｃｏｎｄｕｃｔｏｒｎａｎｏｃｒｙｓｔａｌｌｉｔｅｓ[Ｊ].Ｊ.Ａｍ.Ｃｈｅｍ.Ｓｏｃ.ꎬ１９９３ꎬ１１５(１９):８７０６￣８７１５.[３５]ＬＩＵＹＦꎬＴＡＮＧＸＳꎬＨＵＡＮＧＷꎬｅｔａｌ..Ａｆｌｕｏｒｏｍｅｔｒｉｃｏｐｔｉｃａｌｆｉｂｅｒｎａｎｏｐｒｏｂｅｆｏｒｃｏｐｐｅｒ(Ⅱ)ｂｙｕｓｉｎｇＡｇＩｎＺｎＳｑｕａｎｔｕｍｄｏｔｓ[Ｊ].Ｍｉｃｒｏｃｈｉｍ.Ａｃｔａꎬ２０２０ꎬ１８７(２):１４６.[３６]ＧＯＮÇＡＬＶＥＳＨＭＲꎬＤＵＡＲＴＥＡＪꎬＥＳＴＥＶＥＳＤＡＳＩＬＶＡＪＣＧ.ＯｐｔｉｃａｌｆｉｂｅｒｓｅｎｓｏｒｆｏｒＨｇ(Ⅱ)ｂａｓｅｄｏｎｃａｒｂｏｎｄｏｔｓ[Ｊ].Ｂｉｏｓｅｎｓ.Ｂｉｏｅｌｅｃｔｒｏｎ.ꎬ２０１０ꎬ２６(４):１３０２￣１３０６.[３７]ＬＩＵＴꎬＷＡＮＧＷＱꎬＪＩＡＮＤꎬｅｔａｌ..Ｑｕａｎｔｉｔａｔｉｖｅｒｅｍｏｔｅａｎｄｏｎ￣ｓｉｔｅＨｇ２＋ｄｅｔｅｃｔｉｏｎｕｓｉｎｇｔｈｅｈａｎｄｈｅｌｄｓｍａｒｔｐｈｏｎｅｂａｓｅｄ１２７８㊀发㊀㊀光㊀㊀学㊀㊀报第４１卷ｏｐｔｉｃａｌｆｉｂｅｒｆｌｕｏｒｅｓｃｅｎｃｅｓｅｎｓｏｒ(ＳＯＦＦＳ)[Ｊ].Ｓｅｎｓ.ＡｃｔｕａｔｏｒｓＢ:Ｃｈｅｍ.ꎬ２０１９ꎬ３０１:１２７１６８.[３８]创新.ＳＩＭ系列痕量爆炸物探测器[Ｊ].军民两用技术与产品ꎬ２００７(１２):３１.ＣＨＵＡＮＧＸ.ＳＩＭｓｅｒｉｅｓｔｒａｃｅｅｘｐｌｏｓｉｖｅｄｅｔｅｃｔｏｒ[Ｊ].Ｕｎｉｖｅｒｓ.Ｔｅｃｈｎｏｌ.Ｐｒｏｄ.ꎬ２００７(１２):３１.(ｉｎＣｈｉｎｅｓｅ)[３９]ＣＨＵＦＨꎬＹＡＮＧＪＪ.Ｃｏｉｌ￣ｓｈａｐｅｄｐｌａｓｔｉｃｏｐｔｉｃａｌｆｉｂｅｒｓｅｎｓｏｒｈｅａｄｓｆｏｒｆｌｕｏｒｅｓｃｅｎｃｅｑｕｅｎｃｈｉｎｇｂａｓｅｄＴＮＴｓｅｎｓｉｎｇ[Ｊ].Ｓｅｎｓ.ＡｃｔｕａｔｏｒｓＡ:Ｐｈｙｓ.ꎬ２０１２ꎬ１７５:４３￣４６.[４０]ＬＩＵＦＫꎬＣＵＩＭＸꎬＭＡＪＪꎬｅｔａｌ..Ａｎｏｐｔｉｃａｌｆｉｂｅｒｔａｐｅｒｆｌｕｏｒｅｓｃｅｎｔｐｒｏｂｅｆｏｒｄｅｔｅｃｔｉｏｎｏｆｎｉｔｒｏ￣ｅｘｐｌｏｓｉｖｅｓｂａｓｅｄｏｎｔｅｔｒａ￣ｐｈｅｎｙｌｅｔｈｙｌｅｎｅｗｉｔｈａｇｇｒｅｇａｔｉｏｎ￣ｉｎｄｕｃｅｄｅｍｉｓｓｉｏｎ[Ｊ].Ｏｐｔ.ＦｉｂｅｒＴｅｃｈｎｏｌ.ꎬ２０１７ꎬ３６:９８￣１０４.[４１]ＹＡＮＧＪＣꎬＳＨＥＮＲꎬＹＡＮＰＸꎬｅｔａｌ..Ｆｌｕｏｒｅｓｃｅｎｃｅｓｅｎｓｏｒｆｏｒｖｏｌａｔｉｌｅｔｒａｃｅｅｘｐｌｏｓｉｖｅｓｂａｓｅｄｏｎａｈｏｌｌｏｗｃｏｒｅｐｈｏｔｏｎｉｃｃｒｙｓｔａｌｆｉｂｅｒ[Ｊ].Ｓｅｎｓ.ＡｃｔｕａｔｏｒｓＢ:Ｃｈｅｍ.ꎬ２０２０ꎬ３０６:１２７５８５.[４２]ＤＩＮＧＬＹꎬＦＡＮＣꎬＺＨＯＮＧＹＭꎬｅｔａｌ..ＡｓｅｎｓｉｔｉｖｅｏｐｔｉｃｆｉｂｅｒｓｅｎｓｏｒｂａｓｅｄｏｎＣｄＳｅＱＤｓｆｌｕｏｒｏｐｈｏｒｅｆｏｒｎｉｔｒｉｃｏｘｉｄｅｄｅ￣ｔｅｃｔｉｏｎ[Ｊ].Ｓｅｎｓ.ＡｃｔｕａｔｏｒｓＢ:Ｃｈｅｍ.ꎬ２０１３ꎬ１８５:７０￣７６.[４３]邓辉ꎬ王晓英ꎬ肖吉群ꎬ等.基于荧光猝灭的锥尖型光纤氧传感探头[Ｊ].仪表技术与传感器ꎬ２０１５(７):１４￣１７.ＤＥＮＧＨꎬＷＡＮＧＸＹꎬＸＩＡＯＪＱꎬｅｔａｌ..Ｃｏｎｉｃａｌｔａｐｅｒｅｄｔｉｐｆｉｂｅｒｏｐｔｉｃａｌｏｘｙｇｅｎｓｅｎｓｏｒｐｒｏｂｅｂａｓｅｄｏｎｆｌｕｏｒｅｓｃｅｎｃｅｑｕｅｎｃｈｉｎｇ[Ｊ].Ｉｎｓｔｒｕｍ.Ｔｅｃｈ.Ｓｅｎｓ.ꎬ２０１５(７):１４￣１７.(ｉｎＣｈｉｎｅｓｅ)[４４]ＥＮＤＲＥＳＳ＋ＨＡＵＳＥＲ.ＴｅｃｈｎｉｃａｌｉｎｆｏｒｍａｔｉｏｎｏｘｙｍａｘＣＯＳ６１Ｄ/ＣＯＳ６１[ＥＢ/ＯＬ].(２０１８￣０７￣１７)[２０２０￣０５￣２９].ｈｔ￣ｔｐｓ://ｐｏｒｔａｌ.ｅｎｄｒｅｓｓ.ｃｏｍ/ｗａ００１/ｄｌａ/５０００５４３/５８９４/０００/０４/ＴＩ００３８７ＣＥＮ＿１３１２.ｐｄｆ.[４５]ＺＨＡＯＹＴꎬＰＡＮＧＣＬꎬＷＥＮＺꎬｅｔａｌ..Ａｍｉｃｒｏｆｉｂｅｒｔｅｍｐｅｒａｔｕｒｅｓｅｎｓｏｒｂａｓｅｄｏｎｆｌｕｏｒｅｓｃｅｎｃｅｌｉｆｅｔｉｍｅ[Ｊ].Ｏｐｔ.Ｃｏｍ￣ｍｕｎ.ꎬ２０１８ꎬ４２６:２３１￣２３６.[４６]ＡＮＲＩＴＳＵＭＥＴＥＲＣＯ.ꎬＬＴＤ.ＦｉｂｅｒＯｐｔｉｃｔｈｅｒｍｏｍｅｔｅｒＦＬ￣２０００ｕｓｅｒｓｍａｎｕａｌ[ＥＢ/ＯＬ].(２０１９￣０１￣２１)[２０２０￣０５￣２９].ｈｔｔｐ://ｗｗｗ.ａｎｒｉｔｓｕ￣ｍｅｔｅｒ.ｃｏｍ.ｃｎ.[４７]ＡＮＲＩＴＳＵＭＥＴＥＲＣＯ.ꎬＬＴＤ.４￣ｃｈａｎｎｅｌＦｉｂｅｒＯｐｔｉｃｔｈｅｒｍｏｍｅｔｅｒＡＭＯＴＨＦＬ￣２４００ｕｓｅｒｓｍａｎｕａｌ[ＥＢ/ＯＬ].(２０１９￣０１￣２１)[２０２０￣０５￣２９].ｈｔｔｐ://ｗｗｗ.ａｎｒｉｔｓｕ￣ｍｅｔｅｒ.ｃｏｍ.ｃｎ.[４８]萩原康二ꎬ郝文杰.荧光式光纤温度计[Ｊ].传感器技术ꎬ１９９３(６):５６￣５８.ＫＯＪＩＨꎬＨＡＯＷＪ.Ｆｌｕｏｒｅｓｃｅｎｔｆｉｂｅｒｏｐｔｉｃｔｈｅｒｍｏｍｅｔｅｒ[Ｊ].Ｊ.Ｔｒａｎｓ.Ｔｅｃｈｎｏｌ.ꎬ１９９３(６):５６￣５８.(ｉｎＣｈｉｎｅｓｅ)[４９]ＴＯＮＸＡꎬＡＣＨＡＶꎬＢＯＮＯＭＩＰꎬｅｔａｌ..Ａｄｉｓｐｏｓａｂｌｅｅｖａｎｅｓｃｅｎｔｗａｖｅｆｉｂｅｒｏｐｔｉｃｓｅｎｓｏｒｃｏａｔｅｄｗｉｔｈａｍｏｌｅｃｕｌａｒｌｙｉｍｐｒｉｎ￣ｔｅｄｐｏｌｙｍｅｒａｓａｓｅｌｅｃｔｉｖｅｆｌｕｏｒｅｓｃｅｎｃｅｐｒｏｂｅ[Ｊ].Ｂｉｏｓｅｎｓ.Ｂｉｏｅｌｅｃｔｒｏｎ.ꎬ２０１５ꎬ６４:３５９￣３６６.[５０]ＺＨＵＹＹꎬＣＵＩＭＸꎬＭＡＪＪꎬｅｔａｌ..Ｆｌｕｏｒｅｓｃｅｎｃｅｄｅｔｅｃｔｉｏｎｏｆｄ￣ａｓｐａｒｔｉｃａｃｉｄｂａｓｅｄｏｎｔｈｉｏｌ￣ｅｎｅｃｒｏｓｓ￣ｌｉｎｋｅｄｍｏｌｅｃｕｌａｒｌｙｉｍｐｒｉｎｔｅｄｏｐｔｉｃａｌｆｉｂｅｒｐｒｏｂｅ[Ｊ].Ｓｅｎｓ.ＡｃｔｕａｔｏｒｓＢ:Ｃｈｅｍ.ꎬ２０２０ꎬ３０５:１２７３２３.[５１]ＮＧＵＹＥＮＴＨꎬＬＩＮＹＣꎬＣＨＥＮＣＴꎬｅｔａｌ..Ｆｉｂｒｅｏｐｔｉｃｃｈｌｏｒｉｄｅｓｅｎｓｏｒｂａｓｅｄｏｎｆｌｕｏｒｅｓｃｅｎｃｅｑｕｅｎｃｈｉｎｇｏｆａｎａｃｒｉｄｉｎｉｕｍｄｙｅ[Ｃ].ＰｒｏｃｅｅｄｉｎｇｓｏｆＴｈｅ２０ｔｈＩｎｔｅｒｎａｔｉｏｎａｌＣｏｎｆｅｒｅｎｃｅｏｎＯｐｔｉｃａｌＦｉｂｒｅＳｅｎｓｏｒｓꎬＥｄｉｎｂｕｒｇｈꎬ２００９:７５０３１４￣１￣５.[５２]ＰＯＬＬＥＹＮꎬＳＩＮＧＨＳꎬＧＩＲＩＡꎬｅｔａｌ..ＵｌｔｒａｆａｓｔＦＲＥＴａｔｆｉｂｅｒｔｉｐｓ:ｐｏｔｅｎｔｉａｌａｐｐｌｉｃａｔｉｏｎｓｉｎｓｅｎｓｉｔｉｖｅｒｅｍｏｔｅｓｅｎｓｉｎｇｏｆｍｏ￣ｌｅｃｕｌａｒｉｎｔｅｒａｃｔｉｏｎ[Ｊ].Ｓｅｎｓ.ＡｃｔｕａｔｏｒｓＢ:Ｃｈｅｍ.ꎬ２０１５ꎬ２１０:３８１￣３８８.[５３]ＧＵＯＪＪꎬＮＩＵＭＸꎬＹＡＮＧＣＸ.Ｈｉｇｈｌｙｆｌｅｘｉｂｌｅａｎｄｓｔｒｅｔｃｈａｂｌｅｏｐｔｉｃａｌｓｔｒａｉｎｓｅｎｓｉｎｇｆｏｒｈｕｍａｎｍｏｔｉｏｎｄｅｔｅｃｔｉｏｎ[Ｊ].Ｏｐ￣ｔｉｃａꎬ２０１７ꎬ４(１０):１２８５￣１２８８.[５４]崔红.胆甾修饰ＯＰＥ衍生物薄膜的创制及其荧光传感性能研究[Ｄ].西安:陕西师范大学ꎬ２０１３:３１￣３７.ＣＵＩＨ.ＣｒｅａｔｉｏｎｏｆＣｈｏｌｅｓｔｅｒｉｃＭｏｄｉｆｉｅｄＯＰＥＤｅｒｉｖａｔｉｖｅＦｉｌｍａｎｄＩｔｓＦｌｕｏｒｅｓｃｅｎｃｅＳｅｎｓｉｎｇＰｅｒｆｏｒｍａｎｃｅ[Ｄ].Ｘｉａｎ:ＳｈａａｎｘｉＮｏｒｍａｌＵｎｉｖｅｒｓｉｔｙꎬ２０１３:２６￣２７.(ｉｎＣｈｉｎｅｓｅ)[５５]李晓峰.稀土掺杂碳量子点的制备及其荧光性能的研究[Ｄ].济南:济南大学ꎬ２０１９:１７￣２０.ＬＩＸＦ.ＰｒｅｐａｒａｔｉｏｎａｎｄＦｌｕｏｒｅｓｃｅｎｃｅＰｒｏｐｅｒｔｉｅｓｏｆＲａｒｅＥａｒｔｈＤｏｐｅｄＣａｒｂｏｎＱｕａｎｔｕｍＤｏｔｓ[Ｄ].Ｊｉｎａｎ:ＵｎｉｖｅｒｓｉｔｙｏｆＪｉ￣ｎａｎꎬ２０１４:１７￣２０.(ｉｎＣｈｉｎｅｓｅ)陈静(１９９７－)ꎬ女ꎬ重庆人ꎬ硕士研究生ꎬ２０１５年于重庆邮电大学获得学士学位ꎬ主要从事光纤荧光传感的研究ꎮＥ￣ｍａｉｌ:ｍ２０１９７２４５８＠ｈｕｓｔ.ｅｄｕ.ｃｎ夏历(１９７６－)ꎬ男ꎬ湖北武汉人ꎬ博士ꎬ教授ꎬ博士研究生导师ꎬ２００４年于清华大学获得博士学位ꎬ主要从事光纤通信与光纤传感的研究ꎮＥ￣ｍａｉｌ:ｘｉａｌｉ＠ｈｕｓｔ.ｅｄｕ.ｃｎ。

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SensorsandActuatorsA106(2003)8–14AdvancesinﬂuxgatesensorsPavelRipka∗DepartmentofMeasurement,FacultyofElectricalEngineering,CzechTechnicalUniversity,Technicka2,16627Praha6,CzechRepublic

AbstractThispaperreviewsrecentachievementsinthetechnologyanddesignofﬂuxgatesensorsandmagnetometers.Themajorrecenttrendsweredecreasingofthesensorsize,powerconsumptionandprice,and,ontheotherhand,increasingoftheprecisioninthelargerangeofthemeasuredﬁelds.ThepotentialfrequencyrangewasincreaseduptounitsofkHz.Presentﬂuxgatesensorshavearesolutioncomparablewithhigh-temperaturesuperconductingquantuminterferencedevices(SQUIDs),whiletheirprecisionisthebestofvectorialﬁeldsensors.©2003ElsevierScienceB.V.Allrightsreserved.

Keywords:Fluxgatesensor;Fluxgatemagnetometer

1.IntroductionFluxgatesensorsmeasuredcorlow-frequencyacmag-neticﬁelds.Theyarevectordevices,i.e.sensitivetotheﬁelddirectionintherangeofupto1mTwithachievableresolu-tiondownto10pT.Althoughﬁrstﬂuxgatesensorsappearedinearly1930s,thesesensorsarestillbeingusedinmanyapplications.Recentdevelopmentofmagnetoresistors,es-peciallyanisotropicmagnetoresistancesensors(AMR),limitthemarketforclassicalﬂuxgatetoapplicationsrequir-inghighprecisionandresolution.Thispaperreviewsrecentadvancesanddevelopmentintheﬂuxgatetechnologysincethelastreview[1].Somerecenttrendswerealreadycom-mentedin[2].Broaderoverviewofapplicationsofﬂuxgatesandothermagneticﬁeldsensorsandmagnetometersismadein[3].Recentcomparativestudyofuncooledmagne-tometersandsuperconductingquantuminterferencedevices(SQUIDs)withproposedhybridsystemscanbefoundin[4].Fluxgateprinciplewasﬁrstusedinmagneticmodulators.TheexcitationcurrentIexcthroughtheexcitationcoilpro-

ducesﬁeldthatperiodicallysaturates(inbothdirections)thesoftmagneticmaterialofthesensorcore(Fig.1).Insatura-tionthecorepermeabilitydropsdownandthedcﬂuxasso-ciatedwiththemeasureddcmagneticﬁeldB0isdecreased.

Thenameofthedevicecomesfromthis“gating”oftheﬂuxthatoccurswhenthecoreissaturated.Whenthemeasuredﬁeldispresent,thevoltageViisinducedintothesensing(pick-up)coilatthesecond(andalsohighereven)harmonicsoftheexcitationfrequency.Thisvoltage,proportionaltothe

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measuredﬁeld,isusuallythesensoroutput,butsomeﬂux-gatesalsoworkintheshort-circuitedmode(current-output).Althoughtheﬂuxgateeffectisknownfordecades,itstillattractsinterestoftheoreticalwork.KaplanandSuissahadshownadualitybetweenelectricantennaandgappedﬂux-gate[5,6].Theyalsonewlyderivedthesensorresponsetonon-uniformﬁelds.Althoughtheirresultsarenotdirectlyapplicableforcommonlyused“short”ﬂuxgates,theyhelptounderstandﬂuxgateeffect.Trujilloetal.analyzeﬂuxgateusingsimplespicemodel[7].ThistoolallowstoevaluatetheinﬂuenceofthecoreBHloopshapeandexcitationwaveformontheopen-loopperformanceofthesensor.Fluxgatemagnetometersareusedingeophysicsandforspaceapplications.SpaceapplicationsofﬂuxgatesensorswererecentlyreviewedbyAcuna[8].Fluxgatecompassesareexploitedforaircraftandvehiclenavigation.Theﬂux-gateprincipleisalsoemployedincurrentsensorsandpre-cisecurrentcomparatorsandforremotemeasurementofdccurrents.Forreadingmagneticmarksandlabelsandforde-tectionofferromagneticobjects,compactﬂuxgatemagne-tometersareused.Fluxgatesensorsarereliablesolid-statedevices,work-inginawidetemperaturerange.Resolutionof100pTand10nTabsoluteprecisionisstandardincommerciallypro-duceddevices,buttheycanreach10pTresolutionand1nTlong-termstability.Manydcﬂuxgatemagnetometershaveacut-offfrequencyofseveralHertz,butwhennecessary,theycanworkuptokilohertzfrequencies[9].Thetemperaturestabilityisthefollowing:theoffsetdriftmaybewellbe-low0.1nT/◦C,andthesensitivitytempcoisusuallyaround

50–30ppm/◦C,butsomeﬂuxgatesarecompensatedupto

0924-4247/$–seefrontmatter©2003ElsevierScienceB.V.Allrightsreserved.doi:10.1016/S0924-4247(03)00094-3P.Ripka/SensorsandActuatorsA106(2003)8–149Fig.1.Fluxgateprinciple.1ppm/◦C.Iftheyworkinthefeedbackmode,theresult-ingmagnetometerlinearityerrormaybeaslowas10−5

[10].Ifresolutioninthenanoteslarangeisrequired,ﬂuxgatesarethebestselection.Comparedtohigh-temperaturesu-perconductingquantuminterferencedevicetheymayhavesimilarnoiselevel,butthemeasurementrangeofﬂuxgateismuchlarger.IfpTorevensmallerﬁeldsaremeasured,alow-temperatureSQUIDshouldbeused.Magnetoresis-tors,mainlyanisotropicmagnetoresistancesensors,arethemaincompetitorsofﬂuxgatesensors.Commerciallyavail-ableAMRmagnetoresistorssuchasPhilipsKMZhaveares-olutionworsethan10nT,buttheyaresmallerandcheaperandmayconsumelessenergy.LinearityofthebestpresentcompensatedAMRsensorsis0.05%[11,12].Themostlyusedmodernlow-noiseﬂuxgatesensoristhe“parallel”typewithring-core.“Parallel”typemeansthattheexcitationandthemeasuredﬁeldhavethesamedirection.Orthogonaltypeisrarelyused,mostlyinthin-ﬁlmdevices.Thesecondharmonicintheinducedvoltageisextractedbyaphase-sensitivedetector,andthepick-upcoiloftenservesalsoforthefeedback.Current-outputisalsousedinsomedesigns.Otherdesignsareusedforspecialpurposes,suchasrod-typesensorsfornon-destructivetestingorpositionsensing[13].