CN108051422A - A kind of trace explosive and drug detector and its application method - Google Patents
A kind of trace explosive and drug detector and its application method Download PDFInfo
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- CN108051422A CN108051422A CN201711164525.9A CN201711164525A CN108051422A CN 108051422 A CN108051422 A CN 108051422A CN 201711164525 A CN201711164525 A CN 201711164525A CN 108051422 A CN108051422 A CN 108051422A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
Abstract
The invention discloses a kind of trace explosives and drug detector and its application method.It includes minipump, vacuum box, warm table, laser Raman spectrometer and gas sensor；Gas sensor is made of what the nano-metal particle on substrate and substrate was modified from curling micron tube；Nano-metal particle modification is to prepare plural layers first with vacuum coating equipment from curling micron tube, and then annealing curls into certainly at a suitable temperature.When carrying out trace explosive and drugs detection using detector, gas sensor is placed on vacuum box warm table；Minipump is evacuated vacuum box, and the trace gaseous molecular in the environment such as sucking explosive, drugs detects gaseous state characterization of molecules Raman peaks using laser Raman spectrometer, realizes the detection to explosive, drugs etc.；Thereafter, vacuumized by heating, exclude residual gas, Xun Huan measurement or idle spare.The detection device of the present invention is exquisite, ultra-high sensitive, is particularly suitable for the public safety fields such as anti-terrorism, scouting.
Description
Technical field
The invention belongs to trace explosives and drugs detection application technical field, specifically, are related to a kind of trace explosive
With drug detector and application method.
Background technology
With China's rapid economic development, public safety field is increasingly looked after extensively, from airport, station to wide
Field, big assembly etc. be both needed to check suspicious packages and personage, detects bomb, drugs and the dangerous goods that may be hidden.
Method typically now is using police dog smelling and utilizes the detection of ion mobility spectrometry technology and other methods.Wherein, police dog
Detection is to utilize the fabulous nasal cavity sensitivity of police dog, the remaining trace of the dangers such as smelling bomb or drugs or the gas given out
Molecule.For wrapping up tight dangerous material, the trace gaseous molecular concentration given out is extremely low, and police dog is also difficult to smelling and goes out.Ion moves
It is then the method by vacuum suction or wiping to move spectral technique, and the explosive component of denier is collected entering for explosive detector
It in mouthful, after heated gasification, is combined with special chemical reagent, the effect through micro radioactive source, generates chemistry-ionization reaction.Electricity
Sample charged molecule from after enters ionization door, by ionizing the electric field in face behind the door, its acceleration is made to drift to sample divider
On the target of pole, and record the flight time of ion in the electric field.According to the record to each ion flight time, judge the substance into
Point.This method equally exists certain shortcoming, it is necessary first to which radioactive source, environment are unfriendly；Secondly, equipment is heavy, and precision is not yet
It is very high, frequently results in mistake.Other methods further include capture ion detection technology, chemical method etc., but have precision
It is not very high, it is difficult to the shortcomings that accurately judging danger package.
Also have a kind of detection method at present, i.e., measured using Raman scattering spectrometer the Characteristic Raman scattering spectra of object to be detected come
Determine ingredient, this method is usually directly the scratch powder of explosive or drugs to be detected or is added to liquid to form solution
It is detected, it is very difficult to which the trace gaseous molecular distributed to wrapping up close article surface is accurately responded, thus cannot
It is detected applied to package.For this purpose, if the method that raman characteristic peak need to be detected by Raman scattering spectrometer detect danger,
The sensitivity of Raman scattering spectrometer need to be improved.A kind of method is to form surface using nano-metal particle excitating surface plasma
Enhance Raman scattering effect to improve the detectivity of Raman scattering instrument.This method basic principle be in semiconductor chip or
Nano-metal particle or coating nanometer colloidal solid are prepared on glass substrate, then trace object to be measured dissolve in liquid formed it is molten
Liquid drips to nano-metal particle surface, detects raman characteristic peak, and this method can cause detectivity to enhance 104It is left again
It is right.It is directly visited however, this method is still difficult the trace gaseous molecular gas distributed to wrapping up close article surface
It surveys；Also, another question is difficult to recycle problem, the reason is that, nano-metal particle surface is once exposed to gas
In (including air), it is easy to adsorb several layers of gas molecules, surface is wrapped up by gas molecule, it is difficult to discharge again, thus can only one
Secondary property uses.For this purpose, to overcome difficult point described above, it need to solve two problems, i.e., 1) further enhance detectivity；2）
It solves the problems, such as that the adsorption gas molecule of nano particle discharges again, forms detector and recycle.
The content of the invention
For above-mentioned technical problem, the object of the present invention is to provide a kind of lossless, quick, ultra-high sensitive based on nanogold
The trace explosive and drug detector and its application method from curling micron tube of metal particles modification, the present invention is based on surface etc. from
Daughter improves detector sensitivity with the dual enhancing Raman scattering effect of Echo Wall resonant check, and utilizes the method for heating degasification
Formation recycles.
Technical scheme is specifically described as follows.
A kind of trace explosive and drug detector, including gas sensor, vacuum box, warm table, minipump and
Laser Raman spectrometer；Warm table is set in the vacuum box, gas sensor is placed on warm table, vacuum box front opening,
It is opened or closed by switchable door and window, gas introduction port and gas export mouth is set respectively on vacuum box, gas introduction port is set
It puts in switchable front window, is provided with valve and imports gas or closed gas, gas export mouth is arranged on vacuum box rear end, by leading
Pipe is connected with minipump, sets valve on conduit at gas export mouth, and the top of vacuum box sets closed transparent glass
Glass window, window top set laser Raman spectrometer；Wherein：The gas sensor is by the nano metal on substrate and substrate
Particle modification is formed from curling micron tube, and the micron tube of curling certainly of nano-metal particle modification is to be set first by vacuum coating
Standby plural layers are prepared, then anneals and obtains at a temperature of 300-800 DEG C；The nano-particle modified multilayer micron tube of curling certainly
The material of inside and outside tunic is separately selected from aluminium oxide, titanium oxide, zirconium oxide, silica, hafnium oxide, zinc oxide, oxidation
One kind in gallium, magnesia, yttrium oxide, silicon nitride, aluminium nitride or gallium nitride, nano particle be gold, silver, copper, platinum, palladium, nickel and
One or more of chromium.
In the present invention, the internal diameter from curling micron tube of nano-metal particle modification is 1-20 μm, pipe thickness 5-
500nm, 10-200 μm of pipe range, the particle diameter 3-500nm of nano particle.
In the present invention, the internal diameter from curling micron tube of nano-metal particle modification is 8 ~ 14 μm, pipe thickness 200-
400nm, 50-150 μm of pipe range, the particle diameter 150-300nm of nano particle.
In the present invention, the nano particle in the micron tube of curling certainly of nano-metal particle modification is in discontinuous island structure.
In the present invention, vacuum box and warm table are rectangle.Warm table effect is to provide to bonding nano metal thereon
Particle modification is heated from curling micron tube, to exclude adsorption residual gas.
In the present invention, the speed of exhaust of minipump is 0.1-50 liters/second, ultimate pressure 0.1Pa；It is to use electric power
Driving, effect are that vacuum box is evacuated；Conduit is bellows or leather hose.
In the present invention, the vacuum coating equipment can be that magnetron sputtering, thermal evaporation, electron beam evaporation, pulse laser sink
The typical thin films Preparation equipment such as product, ion plating is known to professional.
In the present invention, laser Raman spectrometer optical maser wavelength is 488-632nm；It is 50-2000cm to detect spectral region-1。
In the present invention, the substrate elargol heat conduction gluing knot of warm table and the gas sensor being placed on it, heating temperature
For 50-200 DEG C.
In the present invention, the junction of switchable front window and vacuum box sets rubber ring.
The present invention also provides a kind of above-mentioned trace explosives and the application method of drug detector, are as follows：
(1) gas introduction port of trace explosive and drug detector is directed at object to be detected；
(2) start minipump, open valve at gas export mouth, open valve at gas introduction port, pass through micro vacuum
Pump is evacuated vacuum box, imports object surface to be detected and distributes gaseous molecular, adsorbs micro- from crimping in nano-metal particle modification
Nanotube surface；
(3) laser Raman spectrometer, detection sucking gas molecule raman scattering spectrum are opened；
(4) raman scattering spectrum of institute's probe gas molecule is contrasted with the Characteristic Raman scattering spectrum of drugs and explosive component, is sentenced
It is disconnected whether to there is explosive or drugs gas molecule to import, judge whether object to be detected is interior containing the danger such as explosive or drugs accordingly
Object；
(5) warm table power supply, the curling micron tube certainly of heating nano-metal particle modification are opened；
(6) the gas introduction port valve of vacuum box is closed, vacuum box is vacuumized, excludes residual gas；Open the gas of vacuum box
Body introducing port valve is simultaneously directed at new object loop detection to be detected or alignment nitrogen pot is passed through nitrogen protective gas, first closes gas
Export mouth valve turns off gas introduction port valve, turns off minipump, the closed nitrogen protective gas in vacuum box,
Idle protection detector, prepares to use next time.
The principle that the present invention solves the non-disposable application of detector is to use to heat nano-particle modified micron tube, and one
The method of side pumping, reaches adsorbed gas and discharges again.In general, gas absorption is τ=τ in the sticking probability of the surface of solids0 exp
(E d /RT), in formula,τIt is gas absorption probability,τ 0 It is constant,E d It is activation energy, R is gas constant,TFor absolute temperature；Pass through
Formula can see, and gas absorption probability can be reduced by improving temperature, i.e., residual on nano particle if necessary to exclude absorption
Gas is stayed, can be excluded by heating raising temperature to be evacuated, reach recycling for nano-particle modified micron tube.
In the present invention, detected mainly for danger package, more specifically detected to wrapping up distributed gaseous molecular,
Detection is gaseous molecular that solid explosive or drugs give out, wherein the explosive be main component for trinitrotoluene, sulphur,
The one or more combinations of pentaerythritol tetranitrate, hexogen, three peroxidating tri acetylacetonates；The drugs main component methylbenzene third
Amine, diamorphine hydrochloride, benzyl ecgonine.
More than, compared to the prior art, advantageous effect of the present invention is：
1) using the curling micron tube surface plasma certainly of nano-metal particle modification and Echo Wall resonant check Raman scattering
Intensity increases detectivity；
2）Make Gas desorption using nano-particle modified micron tube is heated, formation recycles mechanism.
3) panel detector structure is simple, and lightly, sensitivity superelevation is of low cost；Suitable for carrying out lossless spy to suspicious packages
It surveys, possible explosive, drugs etc. is detected for public safety fields such as airport, station, square rallies.
Description of the drawings
Fig. 1 is light in annular tube wall Echo Wall resonance schematic diagram.
Fig. 2 is the structure diagram that multilayer film is prepared in implementation process of the present invention.
Fig. 3 is the curling micron tube structure diagram certainly that nano-metal particle modification is prepared in implementation process of the present invention.
Fig. 4 is the structure diagram of explosive drug detector in implementation process of the present invention.
Figure label：1- annular resonance lumen walls, 2- Echo Wall harmonic lights, 3- substrates, 4- photoetching glue victim layers, 5- outer layers
Oxide or nitride film, 6- internal layers oxide or nitride film, 7- metallic films, 8- nano-metal particles, 9- heating
Platform, 10- vacuum boxs, the curling micron tube certainly of 11- nano-metal particles modification, 12- front windows, 13- gas introduction ports, 14- gases
Export mouth, 15- minipumps, 16- laser Raman spectrometers, 17- top layer glass windows, 18- incidences and shoot laser.
Specific embodiment
The term used in the present invention unless otherwise indicated, there is general professional domain those of ordinary skill to understand meaning.
With reference to specific embodiments and the drawings, the present invention is described in detail.
Fig. 1 is light in annular tube wall Echo Wall resonance schematic diagram.
The principle that the present invention increases detector sensitivity includes two aspects.On the one hand, gaseous molecular absorption is in nano metal
Particle surface when Raman scattering instrument incident laser is incided on molecule, can generate Raman scattering laser with molecular action, when
Nano-metal particle species and radius are optimized, and Raman scattering laser can be in nano-metal particle surface excitation plasma
Body electromagnetic wave resonates, and generates Raman scattering intensities increase effect, enhancer is up to 104；On the other hand, surface of excitation etc. from
Daughter electromagnetic wave（A kind of just electromagnetic wave）It can be coupled into from the tube wall for crimping micron tube, be limited in its tube wall；If
It is optimized from curling micron tube caliber, surface roughness, material, total reflection can be recurred in annular interface, along pipe
The annular interface interference of wall, forms loop light path, generates optical resonance, light intensity is amplified, schematic diagram is as shown in Figure 1.This
The light path resonance amplification of effect laser-like, generates laser.The light of Echo Wall resonance enhancing can be coupled by evanescent wave, be returned
To tube wall nano-metal particle surface, resonate with plasma oscillation electromagnetic wave, greatly enhance surface of metal particles local electromagnetism
Ripple electric vector；If at this point, being adsorbed with molecule in surface of metal particles, Raman scattering of molecule swears the local electromagnetism enhanced at this
Under amount excitation, greatly enhance.Dual increase mechanism in this way enhances detectivity, can be to adsorbing on nano particle
Trace molecules carry out characterization detection.
In the present invention, the preparation of explosive drug detector, key step includes two stages：I. gas sensor is made
Explosive drug detector is assembled with II.；It is specific as follows：
I. gas sensor is made
Specific preparation process is as follows：
1st, substrate 3 is cleaned.2 to 5 inch substrates 3 are taken, are carried out being cleaned by ultrasonic ten minutes successively with acetone, ethyl alcohol, deionized water,
Dry in nitrogen stream, substrate 3 can be silicon chip, quartz plate, sheet glass, and preferred substrate 3 is silicon chip.
2nd, photoetching process.Using the KW-5 types sol evenning machine of Chinese Academy of Sciences Microelectronics Institute in 3 surface spin coating one of substrate
Layer photoresist, used photoresist are positive photoetching rubber.First to be rotated with the 600-1000 rpm slow-speed of revolution, the time is coating technique
6-20 seconds；Then rotated at a high speed with 3000-5000 rpm, the time is 30-60 seconds.Substrate 3 is removed, is positioned over 100-150 DEG C of electricity
30-90 s are toasted on hot plate.Take out substrate 3, photoetching carried out to substrate 3 using ultraviolet photolithographic machine, the overall size of photolithography plate for 5 ×
5cm quadrate arrays, photoetching plate material are the quartz glass plate for being coated with square Cr metallic films array, each square Cr
The size of film is 10 × 10 to 200 × 200 μm.Substrate after photoetching is immersed in developer for positive photoresist, time 20-50 s；
Thereafter cleaned with deionized water, the photoetching glue victim layer 4 of square is obtained after nitrogen stream is dried.Specific photoetching process is special
Common processes known to industry technical staff.
3rd, multilayer membrane process is deposited.Photoresist array substrate obtained by above-mentioned photoetching is put into vacuum coating cavity, Vacuum Deposition
Film device electron beam evaporation plating, carries out successively electron-beam evaporation plated film, and evaporation process is professional's well-known processes.By base
The inclination of piece 3 is fixed on vacuum cavity specimen holder so that for evaporation material inclined deposition on substrate 3, angle of inclination is 60 °.It steams
Plating process is：One layer of oxide or nitride film, i.e. outer oxide object or nitride are evaporated first on photoetching glue victim layer 4
Film 5：Sedimentation rate is 1/s, and substrate temperature is 100-300 DEG C, and evaporation air pressure is 1-10 × 10-2Pa, thickness 2.5-
250nm, material is aluminium oxide, titanium oxide, zirconium oxide, silica, hafnium oxide, zinc oxide, gallium oxide, magnesia, yttrium oxide, nitrogen
One kind in SiClx, aluminium nitride, gallium nitride.Then redeposited one layer of internal layer oxide on outer layer oxide or nitride layer 5
Or nitride film 6；Sedimentation rate is 1/s, and substrate temperature is 100-300 DEG C, and evaporation air pressure is 1-10 × 10-2Pa, thickness
2.5-250nm.Finally, redeposited one layer of metallic film 7 on internal layer oxide or nitride layer 6；Sedimentation rate is 1/s,
Substrate temperature is 100-300 DEG C, and deposition pressure is 1-10 × 10-2Pa, thickness 2.5-100nm, material for gold, silver, copper, platinum, palladium,
One kind or wherein several combinations in nickel and chromium.The electron beam evaporation, it is also possible to sputtering coating equipment.
4th, annealing prepares nano-metal particle modification micron tube technique.Prepared by technique 3 gained plural layers to be put into quickly
It anneals in thermal annealing stove.Annealing temperature is 300-800 DEG C, annealing time 10-60s, annealing atmosphere N2, pressure of annealing
0.1-1 atmospheric pressure.This technique removes photoetching glue victim layer, exerts oneself in release film, obtains curling micrometer tube array structure, sees figure
3, the interior caliber of micron pipe diameter is 1-20 μm, pipe thickness 5-200nm, 10-200 μm of pipe range.In annealing process, metal foil
Film layer forms discrete island nano particle under surface tension effects, is attached to a micron tube wall inner wall, particle diameter 5-
500nm.By this technique, obtain seeing Fig. 3 from the gas sensor for crimping micron tube based on nano-metal particle modification.
II. explosive drug detector is assembled, assembling schematic diagram is shown in Fig. 4, and process is as follows：
(1) the preposition door and window 12 of vacuum box 10 is opened, warm table 9 is put into and is fixed in vacuum box 10, position face
Vacuum box top layer glass window 17；Vacuum box feature is as follows：The preferably interior polishing stainless steel of vacuum box material, stainless steel thickness 1-
5mm, preferably 2mm；Shape is cuboid, the outer length 5-30cm of box body, box body outer width 3-20cm, box high ira vitro 3-15cm；Very
Sylphon has gas export mouth 14；Vacuum box has a preposition switchable front window 12, and front window 12 and vacuum box are by the use of rubber ring as padding
Piece keeps air-tightness；Front window has gas introduction port 13；There is the circular light-permeable top layer glass window 17 of sealing at the top of vacuum box,
A diameter of 1-2cm, to import laser and export scattering laser 18.
(2) it is put into what is modified based on nano-metal particle from the gas sensor for crimping micron tube 11 in vacuum box 10
On warm table 9, it is fixed on elargol or heat-conducting glue on vacuum box warm table.
(3) electrified regulation warm table 9 is kept for heating time 20-60 minute so that nano metal in 80-120 DEG C of heating
Grain modification micrometer tube array substrate is tightly combined with warm table 9.
(4) front window 12 of vacuum box is closed, with screw means, the front window 12 of vacuum box is connect with vacuum box wall by rubber ring
It touches, keeps air-tightness.
(5) vacuum box 10 is made to be connected with minipump 15；Connection mode is plastic cement leather hose；Leather hose and vacuum box 10 connect
Locating gas export mouth 14 has valve, can close and be closed.Available commercially put of minipump can also make by oneself.
(6) the alignment probe top layer glass window 17 of laser Raman spectrometer 16, and it is fixedly clamped；The LR laser raman
Spectrometer can be made by oneself, can also be purchased from market；Its excitation laser wavelength is 488-632nm；Detecting Raman spectrum scope is
50-2000cm-1。
(7) valve at gas introduction port 13 is closed, valve at gas export mouth 14 is opened, vacuum box 10 is evacuated, pumping 2
Hour, valve at gas introduction port 13 is opened thereafter, and being filled with nitrogen by gas introduction port 13 protects, until 1 atmospheric pressure of pressure.
(8) so far, explosive drug detector assembling finishes, you can waits to be used.
In the present invention, the specifically used method of drugs and explosive detector is as follows：
(1) gas introduction port 13 of detector is directed at object to be detected；
(2) start minipump 15, open valve at gas export mouth 14, the valve of gas introduction port 13 is opened, by micro-
Type vacuum pump is evacuated, and is imported object surface to be detected emission gases and is entered vacuum box 10, object surface emission gases molecule to be detected is
It can be adsorbed onto the surfaces externally and internally of nano-metal particle modification micron tube 11.Pumpdown time is 20-60 seconds.
(3) laser Raman spectrometer 16, detection sucking gas molecule raman scattering spectrum are opened.
(4) judged with the Characteristic Raman scattering spectrum of drugs and explosive component according to institute's probe gas raman scattering spectrum
Whether there are explosive or drugs gas molecule to import, judge whether object to be monitored is interior containing explosive or drugs.Typical explosive ingredient-three
The Characteristic Raman scattering peak series of nitrotoleune is：240 cm-1, 693 cm-1, 840 cm-1, 1005 cm-1, 1210 cm-1,
1380 cm-1, wherein, highest peak is 1380 cm-1Peak, secondary strong peak are 1210 cm-1Peak, different scattering peaks correspond to different
Intramolecules vibration pattern, and intensity is different, and peak position slightly moves in different environment, forms characteristic peak, professional
It may determine that whether detection object contains trinitrotoluene accordingly.The Characteristic Raman scattering peak of typical methamphetamine ingredient-crystal methamphetamine
Series is：236 cm-1, 620 cm-1, 836 cm-1, 1001 cm-1, 1018 cm-1, 1209 cm-1, wherein, highest peak 1001
cm-1Peak, secondary strong peak are 836 cm-1Peak, different scattering peaks corresponds to different intramolecules vibration patterns, and intensity differs
Sample, peak position slightly moves in different environment, and professional may determine that whether detection object contains crystal methamphetamine accordingly.Its
He equally has characteristic spectral line in dangerous material Raman scattering of molecule peak, is known to professional.
(5) power supply of warm table 9, the curling micron tube 11 certainly of heating nano-metal particle modification are opened；
(6) valve of 10 preposition gas introduction port 13 of vacuum box is closed；Vacuum box 10 is vacuumized 1-5 minutes, in pumping process
Warm table 9 is kept to heat, excludes residual gas.
(7) (1)-(6) are cycled, physical prospecting to be measured is surveyed.
(8) nitrogen protective gas is passed through to standard atmospheric pressure, and leave unused protection detector, prepares to use next time.
Specific process parameter is determined as known to those skilled in the art or according to the prior art in present embodiment.
Further to get across based on the explosive for enhancing Ramam effect from curling micron tube surface plasma body resonant vibration
Drug detector and application with reference to the accompanying drawings and examples describe to the technical solution of present aspect in detail.
Embodiment 1
1st, substrate 3 is cleaned.2 inch silicon wafers are taken, are carried out being cleaned by ultrasonic ten minutes successively with acetone, ethyl alcohol, deionized water, in nitrogen
Dry in stream, silicon chip schematic diagram is as shown in Figure 2.
2nd, photoetching process.Using the KW-5 types sol evenning machine of Chinese Academy of Sciences Microelectronics Institute in one layer of 3 face spin coating of substrate
Photoresist, the AR-P3510T positive photoresists of used Allresist companies of photoresist model Germany.Coating technique is
It is first rotated with the 800 rpm slow-speed of revolution, the time is 10 seconds；Then rotated with 3000 rpm high rotating speeds, the time is 50 seconds.Remove base
Piece is positioned on 120 DEG C of electric hot plates and toasts 60 s.Substrate 3 is taken out, using the MA6 ultraviolet photolithographic machines of German SUSS companies to base
Piece 3 carries out photoetching, and photolithography plate overall size is 5cm × 5cm quadrate arrays, and photoetching plate material is to be coated with square Cr metallic films
The quartz glass plate of array, the size of each square Cr film is 50 × 50 μm.It is auspicious that substrate 3 after photoetching is immersed in Suzhou
In red electronic chemical product Co., Ltd developer for positive photoresist, positive photoresist model RZX-3038,30 s of Immersion time；Thereafter deionization is used
Water cleans, and the photoetching glue victim layer array 4 of square is obtained after nitrogen stream is dried.Specific photoetching process is professional technique people
Technique known to member.
3rd, multilayer membrane process is deposited.Photoresist array substrate obtained by above-mentioned photoetching process is put into vacuum coating cavity, very
Empty filming equipment reaches company's T SV700 type electron beam evaporation deposition machines for Shenzhen TianXing, carries out successively electron-beam evaporation and plates
Film, evaporation process are professional's well-known processes.The inclination of photoresist array substrate is fixed on vacuum cavity specimen holder so that
Material inclined deposition is evaporated on substrate 3, and angle of inclination is 60 °.One layer of SiO film is evaporated first on photoetching glue victim layer 4,
As 5 is signified in Fig. 2；Sedimentation rate is 1/s, and substrate temperature is 150 DEG C, and evaporation air pressure is 5 × 10-2Pa, thickness 10nm.Then
One layer of TiO of redeposition on SiO2Film；Sedimentation rate is 1/s, and substrate temperature is 150 DEG C, and evaporation air pressure is 5 × 10-2Pa,
Thickness 10nm.Finally, in TiO2Redeposited one layer of Ag film 7, is shown in Fig. 2 on film；Sedimentation rate is 1/s, and substrate temperature is
150 DEG C, deposition pressure is 5 × 10-2Pa, thickness 2.5nm.
4th, annealing process.Prepared by technique 3 gained plural layers to be put into rapid thermal anneler and anneal.Annealing device
Model：ULVAC ACS-4000-C4, annealing temperature are 500 DEG C, annealing time 30s, annealing atmosphere N2, annealing pressure 0.5 is greatly
Air pressure.With discontinuous island nano particle, as shown in Fig. 38, particle diameter point in curling micron tube, tube wall
Cloth is 5-30nm.In this way, obtaining gas sensor, Fig. 3 is seen.
5th, detector assembly combination assembly technology.Assembling schematic diagram is shown in Fig. 4, and process is as follows：
(1) homemade vacuum box 10.The material of vacuum box 10 be interior polishing stainless steel, stainless steel thickness 2mm；Shape is cuboid,
The outer length 20cm of box body, box body outer width 15cm, box high ira vitro 8cm；Vacuum box 10 has gas export mouth 14 and preposition opens
Front window 12 is closed, front window 12 keeps air-tightness with vacuum box 10 by the use of rubber ring as gasket；Front window 12 has gas introduction port 13, and
It is equipped with valve；10 top of vacuum box has sealing circular non-opaque top layer glass window 17, a diameter of 1.5cm.
(2) block furnace silk warm table 9 is fixed in vacuum box 10, position face vacuum box top layer glass window
17；9 maximum power 100W of warm table.
(3) the silicon chip from curling micron tube 11 modified with nano-metal particle（Gas sensor）It is put into vacuum
On warm table 9 in box 10, it is fixed on elargol on vacuum box warm table；Elargol is excellent Ni Weier (Uninwell) company BQ-
6770 model elargol.
(4) electrified regulation warm table 9 is kept for 30 minutes heating times, with nano-metal particle modification micron tube 11
Silicon chip is tightly combined with warm table.
(5) front window 12 of vacuum box is closed, and with screw means, the front window 12 and vacuum box wall for making vacuum box pass through rubber
Circle contact, keeps air-tightness.
(6) vacuum box 10 is connected with minipump 15；Connection mode is plastic cement leather hose；Leather hose diameter 1cm.Micro vacuum
It pumps to purchase the PK5008 type minipumps in Dandong Hai Hao Electronic Science and Technology Co., Ltd.s, the speed of exhaust is 20 liters/min.
(7) the 1 top layer glass window of alignment probe top layer glass window of laser Raman spectrometer 16 and it is fixedly clamped；This
It is selected in embodiment and enjoys optics K-sens-532 miniature laser Raman spectrometers, excitation wavelength 532nm, detection range 200- again
2000cm-1。
(8) valve at gas introduction port 13 is closed, starts minipump 15, opens valve at gas export mouth 14, it is right
Vacuum box 10 is evacuated, when pumping 2 is small；Thereafter valve at gas introduction port 13 is opened, is directed at nitrogen pot, closes gas export mouth 14
Locate valve, close minipump 15, being filled with nitrogen by gas introduction port 13 protects, until 1 atmospheric pressure of pressure, closes gas and lead
Valve at entrance 13.
(9) detector assembling finishes, you can waits to be used.
Embodiment 2
1st, substrate 3 is cleaned.2 inches of quartz plates are taken, are carried out being cleaned by ultrasonic ten minutes successively with acetone, ethyl alcohol, deionized water, in nitrogen
It is dry in air-flow.
2nd, photoetching process.Using the KW-5 types sol evenning machine of Chinese Academy of Sciences Microelectronics Institute in 3 surface spin coating one of substrate
Layer photoresist, the AR-P3510T positive photoresists of used Allresist companies of photoresist model Germany.Coating technique
It is rotated for elder generation with the 800 rpm slow-speed of revolution, the time is 10 seconds；Then rotated with 3000 rpm high rotating speeds, the time is 50 seconds.Remove base
Piece 3 is positioned on 120 DEG C of electric hot plates and toasts 60 s.Substrate 3 is taken out, using the MA6 ultraviolet photolithographic machines of German Suss companies to base
Piece 3 carries out photoetching, and photolithography plate overall size is 5cm × 5cm quadrate arrays, and photoetching plate material is to be coated with square Cr metallic films
The quartz glass plate of array, the size of each square figure is 50 × 50 μm.It is auspicious red that substrate 3 after photoetching is immersed in Suzhou
In electronic chemical product Co., Ltd developer for positive photoresist, positive photoresist model RZX-3038,30 s of Immersion time；Thereafter deionized water is used
Cleaning, square photoetching glue victim layer array is obtained after nitrogen stream is dried, sees photoetching glue victim layer array 4 in Fig. 2.Specifically
Photoetching process is technique known to professional technician.
3rd, multilayer membrane process is deposited.2 gained photoresist array substrate of photoetching process is put into vacuum coating cavity, Vacuum Deposition
Film device reaches company's T SV700 type electron beam evaporation deposition machines for Shenzhen TianXing, carries out successively electron-beam evaporation plated film, steams
Depositing process is professional's well-known processes.The inclination of photoresist array substrate is fixed on vacuum cavity specimen holder so that evaporation
For material inclined deposition on photoresist array substrate, angle of inclination is 60 °.One layer is evaporated first on Fig. 2 photoetching glue victim layers 4
Y2O3Film, as 5 is signified in Fig. 2；Sedimentation rate is 1/s, and substrate temperature is 150 DEG C, and evaporation air pressure is 5 × 10-2Pa, thickness
10nm.Then in Y2O3One layer of ZrO of redeposition on film2Film；Sedimentation rate is 1/s, and substrate temperature is 150 DEG C, boil-off gas
It presses as 5 × 10-2Pa, thickness 10nm.Finally, in ZrO2Redeposited layer of Au film 7, is shown in Fig. 2 on film；Sedimentation rate for 1/
S, substrate temperature are 150 DEG C, and deposition pressure is 5 × 10-2Pa, thickness 2.5nm.
4th, annealing process.Prepared by technique 3 gained plural layers to be put into rapid thermal anneler and anneal.Annealing device
Model：ULVAC ACS-4000-C4, annealing temperature are 700 DEG C, annealing time 50s, annealing atmosphere N2, annealing pressure 0.5 is greatly
Air pressure.Curling micrometer tube array structure is obtained, has discontinuous island nano particle in tube wall, indicated by Fig. 38,
Grain diameter is distributed as 3-20nm.In this way, it obtains seeing Fig. 3 from the gas sensor for crimping micron tube based on nano-particle modified.5、
Detector assembly combines assembly technology.1 kind of step 5 of assembly technology and embodiment is identical.
Claims (10)
1. a kind of trace explosive and drug detector, which is characterized in that it includes gas sensor, vacuum box, warm table, micro-
Type vacuum pump and laser Raman spectrometer；Warm table is set in the vacuum box, and gas sensor is placed on warm table, very
Gas introduction port and gas export mouth are set respectively on the opposite face on sylphon, and gas introduction port is arranged on switchable front window
On, and valve is set, it is imported by the switch of valve or closed gas, gas export mouth is connected by conduit and minipump
It connects, valve is set on conduit at gas export mouth, the top of vacuum box sets window, LR laser raman light is set above window
Spectrometer；Wherein：The gas sensor is made of what the nano-metal particle on substrate and substrate was modified from curling micron tube, is received
Rice metallic particles modification is to prepare plural layers by vacuum coating equipment first from micron tube is crimped, then 300-800 DEG C
At a temperature of anneal and obtain；The choosing of the material of the inside and outside tunic from curling micron tube of nano-metal particle modification independently
Self-alumina, titanium oxide, zirconium oxide, silica, hafnium oxide, zinc oxide, gallium oxide, magnesia, yttrium oxide, silicon nitride, nitridation
One kind in aluminium or gallium nitride, nano particle are one or more of gold, silver, copper, platinum, palladium, nickel and chromium.
2. trace explosive according to claim 1 and drug detector, which is characterized in that nano-particle modified crimps certainly
The internal diameter of micron tube is 1-20 μm, and pipe thickness is 5-500nm, and pipe range is 10-200 μm, the particle diameter of nano particle
It is 3-500nm.
3. trace explosive according to claim 1 and drug detector, which is characterized in that nano-particle modified crimps certainly
The internal diameter of micron tube is 8 ~ 14 μm, and pipe thickness is 200-400nm, and pipe range is 50-150 μm, and the particle of nano particle is straight
Footpath is 150-300nm.
4. trace explosive according to claim 1 and drug detector, which is characterized in that nano-metal particle modification from
It is in discontinuous island structure to crimp the nano particle in micron tube.
5. trace explosive according to claim 1 and drug detector, which is characterized in that vacuum box and warm table are length
It is square.
6. trace explosive according to claim 1 and drug detector, which is characterized in that the speed of exhaust of minipump
For 0.1-50 liters/second.
7. trace explosive according to claim 1 and drug detector, which is characterized in that the laser of laser Raman spectrometer
Wavelength is 488-632nm；It is 50-2000cm to detect spectral region-1。
8. trace explosive according to claim 1 and drug detector, which is characterized in that warm table and gas sensor
Substrate elargol heat conduction gluing knot, heating temperature are 50-200 DEG C.
9. trace explosive according to claim 1 and drug detector, which is characterized in that switchable front window and vacuum box
Junction sets rubber ring.
10. the application method of a kind of trace explosive according to claim 1 and drug detector, which is characterized in that specific
Step is as follows：
(1) gas introduction port of trace explosive and drug detector is directed at object to be detected；
(2) start minipump, open valve at gas export mouth, open valve at gas introduction port, pass through micro vacuum
Pump is evacuated vacuum box, imports object surface to be detected and distributes gaseous molecular, adsorbs micro- from crimping in nano-metal particle modification
Nanotube surface；
(3) laser Raman spectrometer, detection sucking gas molecule raman scattering spectrum are opened；
(4) raman scattering spectrum of institute's probe gas molecule is contrasted with the Characteristic Raman scattering spectrum of drugs and explosive component, is sentenced
It is disconnected whether to there is explosive or drugs gas molecule to import, judge whether object to be detected is interior containing the danger such as explosive or drugs accordingly
Object；
(5) warm table power supply, the curling micron tube certainly of heating nano-metal particle modification are opened；
(6) the gas introduction port valve of vacuum box is closed, vacuum box is vacuumized, excludes residual gas；Open the gas of vacuum box
Body introducing port valve is simultaneously directed at new object loop detection to be detected or alignment nitrogen pot is passed through nitrogen protective gas, first closes gas
Export mouth valve turns off gas introduction port valve, turns off minipump, the closed nitrogen protective gas in vacuum box,
Idle protection detector, prepares to use next time.
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| CN113970534A (en) * | 2021-12-27 | 2022-01-25 | 中国工程物理研究院流体物理研究所 | Vacuum cavity for carrying out in-situ diagnosis on toxic materials based on laser device and application method |
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| IT202000023584A1 (en) * | 2020-10-07 | 2022-04-07 | Velp Scient Srl | BASIC METHOD AND ANALYZER FOR ORGANIC AND INORGANIC SAMPLES |
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