CN108051422B - Trace explosive and drug detector and using method thereof - Google Patents
Trace explosive and drug detector and using method thereof Download PDFInfo
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Abstract
The invention discloses a trace explosive and drug detector and a using method thereof. The device comprises a micro vacuum pump, a vacuum box, a heating table, a laser Raman spectrometer and a gas sensor; the gas sensor consists of a substrate and a self-curling micron tube modified by nano metal particles on the substrate; the self-curling micron tube modified by the nano metal particles is formed by preparing a multilayer film by utilizing vacuum coating equipment and then annealing and self-curling at a proper temperature. When a detector is used for detecting trace explosives and drugs, the gas sensor is arranged on a vacuum box heating table; the micro vacuum pump is used for pumping the vacuum box, sucking trace gaseous molecules in the environments of explosives, drugs and the like, and detecting the characteristic Raman peak of the gaseous molecules by using a laser Raman spectrometer to realize the detection of the explosives, the drugs and the like; and then, heating and vacuumizing to remove residual gas, and performing cyclic measurement or standing for later use. The detection device is exquisite and ultrahigh in sensitivity, and is particularly suitable for the public safety fields of anti-terrorism, reconnaissance and the like.
Description
Technical Field
The invention belongs to the technical field of trace explosive and drug detection application, and particularly relates to a trace explosive and drug detector and a using method thereof.
Background
With the rapid development of economy in China, the public safety field is more and more widely concerned, and suspicious parcels and people need to be checked from airports, stations to squares, large-scale gatherings and the like to detect possibly hidden bombs, drugs and dangerous goods. The current common methods are sniffing by police dogs and detection by ion mobility spectroscopy and other methods. The police dog detection method is characterized in that the police dog detects residual traces of dangerous objects such as bombs or drugs or emitted gas molecules by using the excellent nasal cavity sensitivity of the police dog. For strictly wrapped dangerous goods, the concentration of emitted trace gaseous molecules is extremely low, and police dogs are difficult to smell. The ion migration spectrum technology is that by means of vacuum adsorption or wiping, the trace explosive components are collected into the inlet of explosive detector, heated and gasified, combined with special chemical reagent and acted by trace radioactive source to produce chemical-ionizing reaction. The ionized charged molecules of the sample enter the ionization gate, are accelerated to drift to the pole target of the sample collector by the electric field behind the ionization gate, and the flight time of the ions in the electric field is recorded. The composition of the material is determined from the recording of the time of flight of each ion. The method also has certain disadvantages, firstly, a radioactive source is needed, and the method is not environment-friendly; secondly, the equipment is heavy and the precision is not very high, often resulting in errors. Other methods also comprise a trapped ion detection technology, a chemical method and the like, but all have the defects of not very high precision and difficulty in accurately judging dangerous packages.
At present, a detection method is also provided, namely a Raman scattering spectrometer is used for measuring a characteristic Raman scattering spectrum of an object to be detected to determine components, the method generally directly detects scratch powder of explosives or drugs or dissolves the scratch powder into liquid to form solution for detection, and the method is difficult to accurately respond to trace gaseous molecules emitted from the surface of an object tightly wrapped, so that the method cannot be applied to parcel detection. Therefore, if the method of detecting the raman characteristic peak by the raman scattering spectrometer is required to detect the dangerous object, the sensitivity of the raman scattering spectrometer needs to be improved. One method is to improve the detection sensitivity of the Raman scattering instrument by using nano metal particles to excite surface plasmas to form a surface enhanced Raman scattering effect. The method is based on the principle that nano metal particles or coated nano colloidal particles are prepared on a semiconductor substrate or a glass substrate, then a trace substance to be detected is dissolved in liquid to form a solution, the solution is dripped on the surface of the nano metal particles to detect Raman characteristic peaks, and the method can enhance the detection sensitivity by 104About twice as much. However, this method still has difficulty in directly detecting the trace amount of gaseous molecular gas emitted from the surface of the tightly packed article; and, another problem, that is, a problem of difficult recycling, is that the nano metal particlesOnce the particle surface is exposed to gas (including atmosphere), a plurality of layers of gas molecules are easily adsorbed, and the surface is wrapped by the gas molecules and is difficult to release again, so that the particle can only be used once. To overcome the above difficulties, two problems need to be solved, namely 1) further enhancing the detection sensitivity; 2) the problem of re-release of adsorbed gas molecules of the nano particles is solved, and the detector is recycled.
Disclosure of Invention
Aiming at the technical problems, the invention aims to provide a trace explosive and drug detector which is lossless, rapid and ultra-high in sensitivity and is based on a self-curling micron tube modified by nano metal particles and a using method thereof.
The technical scheme of the invention is specifically introduced as follows.
A trace explosive and drug detector comprises a gas sensor, a vacuum box, a heating table, a micro vacuum pump and a laser Raman spectrometer; the vacuum box is internally provided with a heating table, the gas sensor is arranged on the heating table, the front end of the vacuum box is opened and can be opened or closed through a switchable door and window, the vacuum box is respectively provided with a gas inlet and a gas outlet, the gas inlet is arranged on the switchable front window and is provided with a valve for introducing gas or closed gas, the gas outlet is arranged at the rear end of the vacuum box and is connected with the micro vacuum pump through a guide pipe, the guide pipe is provided with a valve close to the gas outlet, the top of the vacuum box is provided with a closed transparent glass window, and a laser Raman spectrometer is arranged above the window; wherein: the gas sensor consists of a substrate and a self-curling micro-tube decorated by nano metal particles on the substrate, wherein the self-curling micro-tube decorated by the nano metal particles is obtained by firstly preparing a multilayer film through vacuum coating equipment and then annealing at the temperature of 300-; the material of the inner layer film and the outer layer film of the self-curling multilayer micro-tube modified by the nano-particles is respectively and independently selected from one of aluminum oxide, titanium oxide, zirconium oxide, silicon oxide, hafnium oxide, zinc oxide, gallium oxide, magnesium oxide, yttrium oxide, silicon nitride, aluminum nitride or gallium nitride, and the nano-particles are one or more of gold, silver, copper, platinum, palladium, nickel and chromium.
In the invention, the inner diameter of the self-curling micron tube modified by the nano metal particles is 1-20 μm, the thickness of the tube wall is 5-500nm, the length of the tube is 10-200 μm, and the particle diameter of the nano particles is 3-500 nm.
In the invention, the inner diameter of the self-curling micron tube modified by the nano metal particles is 8-14 μm, the wall thickness of the tube is 200-400nm, the length of the tube is 50-150 μm, and the particle diameter of the nano particles is 150-300 nm.
In the invention, the nanoparticles in the self-curling nanotube modified by the metal nanoparticles are in a discontinuous island-shaped structure.
In the invention, the vacuum box and the heating platform are rectangular. The heating stage is used for providing heating for the self-curling microtube which is bonded with the nano metal particle modification, so as to eliminate the residual gas adsorbed on the surface.
In the invention, the air exhaust rate of the micro vacuum pump is 0.1-50L/s, and the limiting pressure is 0.1 Pa; the vacuum box is driven by electric power and has the function of exhausting air to the vacuum box; the conduit is a corrugated pipe or a leather hose.
In the invention, the vacuum coating equipment can be common film preparation equipment such as magnetron sputtering, thermal evaporation, electron beam evaporation, pulsed laser deposition, ion plating and the like, and is well known by professionals.
In the invention, the laser wavelength of the laser Raman spectrometer is 488-632 nm; the detection spectral range is 50-2000cm-1。
In the invention, the heating table is bonded with the substrate of the gas sensor arranged on the heating table by using the silver colloid heat conducting adhesive, and the heating temperature is 50-200 ℃.
In the invention, a rubber ring is arranged at the joint of the switchable front window and the vacuum box.
The invention also provides a use method of the trace explosive and drug detector, which comprises the following specific steps:
(1) a gas inlet of the trace explosive and drug detector is aligned with an object to be detected;
(2) starting a micro vacuum pump, opening a valve at a gas leading-out port, opening a valve at a gas leading-in port, pumping air to the vacuum box through the micro vacuum pump, leading in a substance to be detected, emitting gaseous molecules on the surface of the substance to be detected, and adsorbing the molecules on the surface of the self-curling micro-tube modified by the nano metal particles;
(3) opening the laser Raman spectrometer, and detecting a Raman scattering spectrum of the inhaled gas molecules;
(4) comparing the characteristic Raman scattering spectra of the drugs and the explosive components with the Raman scattering spectrum of the detected gas molecules to judge whether the explosives or the drug gas molecules are introduced, and judging whether the object to be detected contains dangerous objects such as the explosives or the drugs according to the judgment;
(5) turning on a heating table power supply, and heating the self-curling micron tube modified by the nano metal particles;
(6) closing a gas inlet valve of the vacuum box, vacuumizing the vacuum box and removing residual gas; opening the gas inlet valve of the vacuum box and aiming at a new object to be detected for circular detection or aiming at a nitrogen tank to introduce nitrogen protective gas, closing the gas outlet valve, closing the gas inlet valve, closing the micro vacuum pump, sealing the nitrogen protective gas in the vacuum box, and leaving the detector to be protected for next use.
The invention solves the problem of non-disposable application of the detector by adopting a method of heating a nanoparticle modified microtube and exhausting air at the same time to achieve the purpose of releasing adsorbed gas. In general, the adsorption probability of a gas on a solid surface is τ = τ0exp(E d /RT) In the formula (I), wherein,τit is the probability of gas adsorption,τ 0 is a constant number of times that the number of the first,E d is the activation energy, R is the gas constant,Tis the absolute temperature; according to the formula, the gas adsorption probability can be reduced by increasing the temperature, namely if residual gas adsorbed on the nano particles needs to be removed, the residual gas can be removed by heating and increasing the temperature to exhaust, so that the recycling of the nano particle modified micron tube is realized.
In the invention, detection is mainly carried out aiming at dangerous packages, more specifically, detection is carried out on gaseous molecules emitted by the packages, and the gaseous molecules emitted by solid explosives or drugs are detected, wherein the explosives mainly comprise one or more of trinitrotoluene, sulfur, pentaerythritol tetranitrate, hexogen and tripropionic acid peroxide; the main components of the drug are methamphetamine, diacetylmorphine hydrochloride and benzyl ecgonine.
Compared with the prior art, the invention has the beneficial effects that:
1) the resonance of the surface plasma of the self-curling microtube modified by the nano metal particles and the echo wall is adopted to enhance the Raman scattering intensity, so that the detection sensitivity is increased;
2) the heating nano particles are used for modifying the micro-tube to desorb gas, so that a recycling mechanism is formed.
3) The detector has simple structure, light weight, ultrahigh sensitivity and low cost; the method is suitable for nondestructive detection of suspicious packages, and is used for detecting possible explosives, drugs and the like in public safety fields such as airports, stations, square gatherings and the like.
Drawings
Fig. 1 is a schematic diagram of light resonating at the echo wall of the ring-shaped pipe wall.
FIG. 2 is a schematic diagram of the structure of a multilayer film made in the practice of the present invention.
Fig. 3 is a schematic diagram of a self-curling microstructure modified by nano-metal particles prepared in the implementation process of the invention.
FIG. 4 is a schematic diagram of the configuration of an explosive drug detector in the practice of the present invention.
Reference numbers in the figures: the laser comprises a 1-ring resonator wall, a 2-echo wall resonant light, a 3-substrate, a 4-photoresist sacrificial layer, a 5-outer layer oxide or nitride film, a 6-inner layer oxide or nitride film, a 7-metal film, 8-nano metal particles, a 9-heating table, a 10-vacuum box, a 11-nano metal particle modified self-curling micro-tube, a 12-front window, a 13-gas inlet, a 14-gas outlet, a 15-micro vacuum pump, a 16-laser Raman spectrometer, a 17-top glass window, and 18-incident and emergent laser.
Detailed Description
Terms used in the present invention have meanings as understood by those of ordinary skill in the art unless otherwise specified.
The present invention will be described in detail below with reference to specific embodiments and the accompanying drawings.
Fig. 1 is a schematic diagram of light resonating at the echo wall of the ring-shaped pipe wall.
The principle of the invention to increase the sensitivity of the detector consists of two aspects. On one hand, gaseous molecules are adsorbed on the surface of the nano metal particles, when incident laser of a Raman scattering instrument is incident on the molecules, the gaseous molecules can act with the molecules to generate Raman scattering laser, when the types and the radiuses of the nano metal particles are optimized, the Raman scattering laser can excite plasma electromagnetic wave resonance on the surface of the nano metal particles to generate a Raman scattering intensity increasing effect, and the enhancement factor can reach 104(ii) a On the other hand, the excited surface plasma electromagnetic wave (light is an electromagnetic wave) can be coupled into the tube wall of the self-curling micro-tube and limited in the tube wall; if the diameter, surface roughness and material of the self-curling micro-tube are optimized, total reflection can be continuously generated on the annular interface, interference is carried out along the annular interface of the tube wall to form a loop light path, optical resonance is generated, and the light intensity is amplified, wherein the schematic diagram is shown in figure 1. This effect is analogous to resonant amplification of the optical path of a laser, producing laser light. The light with enhanced echo wall resonance can be coupled by evanescent waves, returns to the surface of the metal nanoparticles on the tube wall, and resonates with the plasma oscillation electromagnetic waves, so that the electric vector of the local electromagnetic waves on the surface of the metal particles is greatly enhanced; at this time, if molecules are adsorbed on the surface of the metal particles, the molecular raman scattering will be greatly enhanced under this enhanced local electromagnetic vector excitation. By the double increasing mechanism, the detection sensitivity is enhanced, and trace molecules adsorbed on the nano particles can be characterized and detected.
In the invention, the preparation of the explosive drug detector mainly comprises two stages: I. manufacturing a gas sensor and II, assembling an explosive drug detector; the method comprises the following specific steps:
I. making a gas sensor
The preparation method comprises the following specific steps:
1. the substrate 3 is cleaned. Taking a 2-to 5-inch substrate 3, carrying out ultrasonic cleaning for ten minutes by using acetone, ethanol and deionized water in sequence, and drying in a nitrogen flow, wherein the substrate 3 can be a silicon wafer, a quartz wafer or a glass wafer, and preferably the substrate 3 is a silicon wafer.
2. And (5) carrying out a photoetching process. A layer of photoresist is coated on the surface of the substrate 3 in a spin coating manner by using a KW-5 type spin coater of the micro-electronic research institute of Chinese academy of sciences, and the photoresist is a positive photoresist. The gluing process is that the glue is firstly rotated at the low rotating speed of 600 plus 1000 rpm for 6 to 20 seconds; then rotating at 3000-. Taking down the substrate 3, and placing the substrate on an electric hot plate at the temperature of 100 ℃ and 150 ℃ for baking for 30-90 s. Taking out the substrate 3, and photoetching the substrate 3 by using an ultraviolet photoetching machine, wherein the total size of a photoetching plate is a square array of 5 multiplied by 5cm, the photoetching plate material is a quartz glass plate plated with a square Cr metal thin film array, and the size of each square Cr film is 10 multiplied by 10 to 200 multiplied by 200 mu m. Immersing the substrate after photoetching in positive photoresist developing solution for 20-50 s; and then washing with deionized water, and drying by nitrogen flow to obtain the square photoresist sacrificial layer 4. The specific photolithographic process is a general process well known to those skilled in the art.
3. Putting the photo-resist array substrate obtained by the photo-etching into a vacuum coating cavity, and performing electron beam evaporation and deposition coating layer by using a vacuum coating device by using electron beams, wherein the evaporation process is a process well known by professional personnel, the substrate 3 is obliquely fixed on a sample rack of the vacuum cavity, so that an evaporation material is obliquely deposited on the substrate 3 at an inclination angle of 60 degrees, and the evaporation process comprises the steps of firstly evaporating a layer of oxide or nitride film on a photo-resist sacrificial layer 4, namely an outer layer oxide or nitride film 5, wherein the deposition rate is 1 Å/s, the substrate temperature is 100 DEG, the temperature is 300 DEG, and the evaporation pressure is 1-10 × 10 DEG-2Pa, thickness of 2.5-250nm, material selected from one of aluminum oxide, titanium oxide, zirconium oxide, silicon oxide, hafnium oxide, zinc oxide, gallium oxide, magnesium oxide, yttrium oxide, silicon nitride, aluminum nitride and gallium nitride, and then depositing an inner oxide or nitride film 6 on the outer oxide or nitride layer 5 at a deposition rate of 1 Å/s, a substrate temperature of 100℃ and 300℃, and an evaporation pressure of 1-10 × 10-2Pa, thickness of 2.5-250nm, and depositing a metal film 7 on the inner oxide or nitride layer 6 at a deposition rate of 1 Å/s, a substrate temperature of 100 ℃ and 300 ℃ and a deposition pressure of 1-10 × 10-2Pa, the thickness is 2.5-100nm, the material is one or the combination of several of gold, silver, copper, platinum, palladium, nickel and chromium. The electron beam evaporation can also be carried out by using sputtering coating equipment.
4. Annealing to prepare nanometer metal particle modified micron tube. And (3) putting the multilayer film prepared by the process 3 into a rapid thermal annealing furnace for annealing. The annealing temperature is 300-800 ℃, the annealing time is 10-60s, and the annealing atmosphere is N2And the annealing pressure is 0.1-1 atm. The process removes the photoresist sacrificial layer, releases the internal force of the film, and obtains a curled microtube array structure, as shown in figure 3, wherein the internal tube diameter of the microtube is 1-20 μm, the tube wall thickness is 5-200nm, and the tube length is 10-200 μm. In the annealing process, the metal film layer forms discontinuous island-shaped nano particles under the action of surface tension, the island-shaped nano particles are attached to the inner wall of the micron tube, and the particle diameter of the island-shaped nano particles is 5-500 nm. Through the process, the gas sensor based on the self-curling micron tube modified by the nano metal particles is obtained, and the figure is shown in figure 3.
Assembling the explosive drug detector, wherein the assembly schematic diagram is shown in figure 4, and the process is as follows:
(1) opening a front door and window 12 of the vacuum box 10, and putting and fixing the heating table 9 in the vacuum box 10 at a position opposite to a top glass window 17 of the vacuum box; the vacuum box is characterized as follows: the vacuum box is preferably made of inner polished stainless steel, and the thickness of the stainless steel is 1-5mm, preferably 2 mm; the shape is a cuboid, the external length of the box body is 5-30cm, the external width of the box body is 3-20cm, and the external height of the box body is 3-15 cm; the vacuum box has a gas outlet 14; the vacuum box is provided with a front openable front window 12, and the front window 12 and the vacuum box are kept airtight by using a rubber ring as a gasket; the front window has a gas inlet 13; the vacuum box has a sealed circular light permeable top glass window 17 with a diameter of 1-2cm at the top for introducing laser light and for discharging scattered laser light 18.
(2) A gas sensor based on a self-curling nanotube 11 modified by nano metal particles is placed on a heating table 9 in a vacuum box 10 and fixed on the heating table of the vacuum box by silver adhesive or heat-conducting adhesive.
(3) And electrifying to heat the heating table 9, heating at 80-120 ℃ for 20-60 minutes, and tightly bonding the nano metal particle modified micro-tube array substrate with the heating table 9.
(4) The front window 12 of the vacuum box is closed and screwed tightly, and the front window 12 of the vacuum box is contacted with the wall of the vacuum box through a rubber ring to keep air tightness.
(5) Connecting the vacuum box 10 with a micro vacuum pump 15; the connection mode is a plastic rubber tube; the gas outlet 14 at the connection of the bellows and the vacuum box 10 is provided with a valve which can be closed and opened. The micro vacuum pump can be purchased commercially or manufactured by self.
(6) Aligning a probe of the laser Raman spectrometer 16 to the top glass window 17, and clamping and fixing; the laser Raman spectrometer can be manufactured by self or purchased from the market; the excitation laser wavelength is 488-632 nm; the detection Raman spectrum range is 50-2000cm-1。
(7) And closing the valve at the gas inlet 13, opening the valve at the gas outlet 14, exhausting the vacuum box 10 for 2 hours, then opening the valve at the gas inlet 13, and filling nitrogen for protection through the gas inlet 13 until the pressure is 1 atmosphere.
(8) And the explosive drug detector can wait for use after being assembled.
In the invention, the specific use method of the drug and explosive detector is as follows:
(1) aligning a gas inlet 13 of the detector with an object to be detected;
(2) and starting the micro vacuum pump 15, opening a valve at the gas outlet 14, opening a valve of the gas inlet 13, pumping air through the micro vacuum pump, introducing the diffused gas on the surface of the object to be detected into the vacuum box 10, and adsorbing the diffused gas molecules on the surface of the object to be detected to the inner surface and the outer surface of the nano metal particle modified micron tube 11. The air suction time is 20-60 seconds.
(3) The laser raman spectrometer 16 is turned on and the molecular raman scattering spectrum of the inspired gas is detected.
(4) And comparing the characteristic Raman scattering spectra of the drugs and the explosive components with the Raman scattering spectrum of the detected gas to judge whether the explosives or drug gas molecules are introduced, and judging whether the object to be monitored contains the explosives or the drugs. The characteristic Raman scattering peak series of a typical explosive component trinitrotoluene is as follows: 240 cm-1，693 cm-1，840 cm-1，1005 cm-1，1210 cm-1，1380 cm-1Wherein the strongest peak is 1380 cm-1Peak, secondary strong peak 1210 cm-1The peak and different scattering peaks correspond to different intramolecular vibration modes, the intensities are different, the peak positions slightly move in different environments to form characteristic peaks, and a professional can judge whether the detected object contains trinitrotoluene or not according to the characteristic peaks. The characteristic Raman scattering peak series of the typical methamphetamine serving as an ingredient of the methamphetamine is as follows: 236 cm-1，620 cm-1，836 cm-1，1001 cm-1，1018 cm-1，1209 cm-1Wherein the strongest peak is 1001cm-1Peak, second intense peak 836 cm-1The peak and different scattering peaks correspond to different intramolecular vibration modes, the intensities are different, the peak positions slightly move in different environments, and a professional can judge whether the detected object contains methamphetamine or not. Other hazardous material molecular raman scattering peaks also have characteristic spectral lines and are well known to those skilled in the art.
(5) Turning on a power supply of the heating table 9, and heating the self-curling micro-tube 11 modified by the nano metal particles;
(6) a valve for closing the front gas inlet 13 of the vacuum box 10; and vacuumizing the vacuum box 10 for 1-5 minutes, keeping the heating table 9 heated in the air exhaust process, and removing residual gas.
(7) And (5) circulating the steps (1) to (6) and detecting the object to be detected.
(8) And introducing nitrogen protective gas to the standard atmospheric pressure, and idling to protect the detector and prepare for next use.
The specific process parameters in this embodiment are known to those skilled in the art or determined in accordance with the prior art.
For further explanation, the technical solution of the present invention will be described in detail with reference to the accompanying drawings and examples, wherein the explosive drug detector based on the self-curling microtube surface plasmon resonance enhanced raman effect and its application are explained in detail.
Example 1
1. The substrate 3 is cleaned. A 2-inch silicon wafer was taken, ultrasonically cleaned with acetone, ethanol, and deionized water in sequence for ten minutes, and dried in a nitrogen stream, and the schematic diagram of the silicon wafer is shown in fig. 2.
2. And (5) carrying out a photoetching process. A layer of photoresist is spin-coated on the 3 surface of the substrate by using a KW-5 type spin coater of the micro-electronic research institute of Chinese academy of sciences, and the type of the photoresist is AR-P3510T positive photoresist of Allresist company of Germany. The gluing process is that the glue is firstly rotated at a low rotating speed of 800 rpm for 10 seconds; then rotated at 3000 rpm for 50 seconds. Taking off the substrate, and baking the substrate on an electric hot plate at 120 ℃ for 60 s. Taking out the substrate 3, and photoetching the substrate 3 by using a MA6 ultraviolet photoetching machine of SUSS company of Germany, wherein the total size of a photoetching plate is a square array of 5cm multiplied by 5cm, the photoetching plate material is a quartz glass plate plated with a square Cr metal thin film array, and the size of each square Cr film is 50 multiplied by 50 mu m. Immersing the photoetched substrate 3 in a positive photoresist developer of Suzhou Rehong electronic chemical Co., Ltd, wherein the type of the positive photoresist is RZX-3038, and the immersion time is 30 s; and then washing with deionized water, and drying by nitrogen flow to obtain the square photoresist sacrificial layer array 4. Specific lithographic processes are well known to those skilled in the art.
3. Putting the photoresist array substrate obtained by the photoetching process into a vacuum coating cavity, wherein the vacuum coating equipment is a TSV700 type electron beam evaporation coating machine of Shenzhen Tianxinda company, performing electron beam evaporation deposition coating layer by layer, and the evaporation process is a process well known by professionals, fixing the photoresist array substrate on a sample rack of the vacuum cavity in an inclined manner to ensure that an evaporation material is obliquely deposited on the substrate 3 at an inclination angle of 60 degrees, firstly evaporating a SiO thin film on a photoresist sacrificial layer 4 as indicated by 5 in figure 2, wherein the deposition rate is 1 Å/s, the substrate temperature is 150 ℃, and the evaporation pressure is 5 × 10-2Pa, thickness 10 nm. Then depositing a layer of TiO on the SiO2The film deposition rate is 1 Å/s, the substrate temperature is 150 ℃, and the evaporation pressure is 5 × 10-2Pa, thickness 10 nm. Finally, in TiO2Depositing an Ag film 7 on the film at a deposition rate of 1 Å/s, a substrate temperature of 150 deg.C and a deposition pressure of 5 × 10-2Pa, thickness 2.5 nm.
4. And (5) annealing process. Placing the multilayer film prepared by the process 3And putting the mixture into a rapid thermal annealing furnace for annealing. The model of annealing equipment is as follows: ULVAC ACS-4000-C4, annealing temperature 500 deg.C, annealing time 30s, and annealing atmosphere N2And the annealing pressure is 0.5 atmosphere. The obtained self-curled micron tube has discontinuous island-shaped nanoparticles attached to the wall, as shown in 8 in FIG. 3, and has particle diameter distribution of 5-30 nm. Thus, a gas sensor was obtained, see fig. 3.
5. A detector device combination assembly process. The assembly is schematically shown in fig. 4, and the process is as follows:
(1) a self-made vacuum box 10. The vacuum box 10 is made of internally polished stainless steel, and the thickness of the stainless steel is 2 mm; the shape is a cuboid, the outer length of the box body is 20cm, the outer width of the box body is 15cm, and the outer height of the box body is 8 cm; the vacuum box 10 has a gas outlet 14 and a front openable front window 12, and the front window 12 and the vacuum box 10 use a rubber ring as a gasket to keep air tightness; the front window 12 has a gas introduction port 13 and is equipped with a valve; the vacuum box 10 has a sealed circular transparent top glass window 17 at the top, 1.5cm in diameter.
(2) A square electric furnace wire heating table 9 is installed and fixed in a vacuum box 10, and the position of the square electric furnace wire heating table is opposite to a top glass window 17 of the vacuum box; the heating stage 9 has a maximum power of 100W.
(3) Putting a silicon substrate (gas sensor) with a self-curling micro-tube 11 modified by nano metal particles on a heating table 9 in a vacuum box 10, and fixing the silicon substrate on the heating table of the vacuum box by using silver adhesive; the silver colloid is BQ-6770 model silver colloid of Uninwell company.
(4) And electrifying to heat the heating table 9, keeping the heating time for 30 minutes, and tightly combining the silicon substrate with the nano metal particle modified microtube 11 with the heating table.
(5) The front window 12 of the vacuum box is closed and screwed tightly, so that the front window 12 of the vacuum box is contacted with the wall of the vacuum box through a rubber ring to keep airtightness.
(6) The vacuum box 10 is connected with a micro vacuum pump 15; the connection mode is a plastic rubber tube; the diameter of the leather hose is 1 cm. The micro vacuum pump is a PK5008 type micro vacuum pump purchased from the electronic technology limited of Haoyao, Donghai, and the air suction rate is 20 liters/minute.
(7) Aligning the probe of the laser Raman spectrometer 16 with the top layerThe top layer of the glass window 1 is clamped and fixed; in this embodiment, a shared optical K-sens-532 micro laser Raman spectrometer is selected, the excitation wavelength is 532nm, and the detection range is 200-2000cm-1。
(8) Closing the valve at the gas inlet 13, starting the micro vacuum pump 15, opening the valve at the gas outlet 14, and pumping the vacuum box 10 for 2 hours; then, a valve at the gas inlet 13 is opened to align with the nitrogen tank, a valve at the gas outlet 14 is closed, the micro vacuum pump 15 is closed, nitrogen protection is filled through the gas inlet 13 to reach the pressure of 1 atmosphere, and the valve at the gas inlet 13 is closed.
(9) And after the detector is assembled, the detector can wait for use.
Example 2
1. The substrate 3 is cleaned. A 2 inch quartz plate was ultrasonically cleaned with acetone, ethanol, and deionized water for ten minutes in sequence, and dried in a nitrogen stream.
2. And (5) carrying out a photoetching process. A layer of photoresist is coated on the surface of the substrate 3 in a spin coating manner by using a KW-5 type spin coater of the micro-electronic research institute of Chinese academy of sciences, and the type of the photoresist is AR-P3510T positive photoresist of Allresist company of Germany. The gluing process is that the glue is firstly rotated at a low rotating speed of 800 rpm for 10 seconds; then rotated at 3000 rpm for 50 seconds. Taking off the substrate 3, and placing on an electric hot plate at 120 ℃ for baking for 60 s. Taking out the substrate 3, and photoetching the substrate 3 by using a MA6 ultraviolet photoetching machine of Suss company of Germany, wherein the total size of a photoetching plate is a square array of 5cm multiplied by 5cm, the photoetching plate material is a quartz glass plate plated with a square Cr metal thin film array, and the size of each square figure is 50 multiplied by 50 mu m. Immersing the photoetched substrate 3 in a positive photoresist developer of Suzhou Rehong electronic chemical Co., Ltd, wherein the type of the positive photoresist is RZX-3038, and the immersion time is 30 s; and then, washing with deionized water, and drying by nitrogen flow to obtain a square photoresist sacrificial layer array, which is shown as a photoresist sacrificial layer array 4 in FIG. 2. Specific lithographic processes are well known to those skilled in the art.
3. And (5) evaporating a multilayer film. Placing the photoresist array substrate obtained by the photoetching process 2 into a vacuum coating cavity, wherein the vacuum coating equipment is a TSV700 type electron of Shenzhen Tian Dy companyThe beam evaporation coating machine carries out electron beam evaporation deposition coating layer by layer, and the evaporation coating process is a process well known by professionals. And obliquely fixing the photoresist array substrate on a sample rack of the vacuum cavity, so that the evaporation material is obliquely deposited on the photoresist array substrate at an inclination angle of 60 degrees. First, a layer of Y is evaporated on the sacrificial photoresist layer 4 of FIG. 22O3The film, as indicated at 5 in FIG. 2, was deposited at a rate of 1 Å/s, at a substrate temperature of 150 ℃ and an evaporation pressure of 5 × 10-2Pa, thickness 10 nm. Then at Y2O3Depositing a layer of ZrO on the film2The film deposition rate is 1 Å/s, the substrate temperature is 150 ℃, and the evaporation pressure is 5 × 10-2Pa, thickness 10 nm. Finally, in ZrO2An Au thin film 7 is deposited on the thin film, as shown in figure 2, with the deposition rate of 1 Å/s, the substrate temperature of 150 ℃, and the deposition pressure of 5 × 10-2Pa, thickness 2.5 nm.
4. And (5) annealing process. And (3) putting the multilayer film prepared by the process 3 into a rapid thermal annealing furnace for annealing. The model of annealing equipment is as follows: ULVAC ACS-4000-C4, annealing temperature of 700 ℃, annealing time of 50s, and annealing atmosphere of N2And the annealing pressure is 0.5 atmosphere. A coiled micro-tube array structure is obtained, and discontinuous island-shaped nanoparticles are attached to the tube wall, and the particle diameter distribution is 3-20nm as indicated by 8 in figure 3. Thus, a gas sensor based on nanoparticle-modified self-curled microtubes was obtained, see fig. 3. 5. A detector device combination assembly process. The assembly process is the same as step 5 in example 1.
Claims (10)
1. A trace explosive and drug detector is characterized by comprising a gas sensor, a vacuum box, a heating table and a micro-scale
A vacuum pump and a laser Raman spectrometer; the vacuum box is internally provided with a heating table, the gas sensor is arranged on the heating table, a gas inlet and a gas outlet are respectively arranged on opposite surfaces of the vacuum box, the gas inlet is arranged on the switchable front window and is provided with a valve, gas is introduced or sealed through the switch of the valve, the gas outlet is connected with the micro vacuum pump through a guide pipe, the guide pipe is provided with a valve close to the gas outlet, the top of the vacuum box is provided with a window, and a laser Raman spectrometer is arranged above the window; wherein: the gas sensor consists of a substrate and a self-curling micro-tube decorated by nano metal particles on the substrate, wherein the self-curling micro-tube decorated by the nano metal particles is obtained by firstly preparing a multilayer film through vacuum coating equipment and then annealing at the temperature of 300-; the material of the inner layer film and the outer layer film of the self-curling micro-tube modified by the nano metal particles is respectively and independently selected from one of aluminum oxide, titanium oxide, zirconium oxide, silicon oxide, hafnium oxide, zinc oxide, gallium oxide, magnesium oxide, yttrium oxide, silicon nitride, aluminum nitride or gallium nitride, and the nano particles are one or more of gold, silver, copper, platinum, palladium, nickel and chromium.
2. The trace explosive and drug detector of claim 1, wherein the nanoparticle modified self-curling is
The inner diameter of the micron tube is 1-20 μm, the wall thickness of the tube is 5-500nm, the length of the tube is 10-200 μm, and the particle diameter of the nano-particles is 3-500 nm.
3. The trace explosive and drug detector of claim 1, wherein the nanoparticle modified self-curling is
The inner diameter of the micron tube is 8-14 μm, the wall thickness of the tube is 400nm, the tube length is 50-150 μm, and the particle diameter of the nano particles is 150 nm and 300 nm.
4. The trace explosive and drug detector according to claim 1, wherein the nanoparticles in the self-curled nanotubes modified by the metal nanoparticles are in a discontinuous island structure.
5. The trace explosive and drug detector of claim 1, wherein the vacuum box and the heating station are both long
And (4) square.
6. The trace explosive and drug detector of claim 1, wherein the micro vacuum pump has a pumping rate
Is 0.1-50L/s.
7. The trace explosive and drug detector of claim 1, wherein the laser of the laser raman spectrometer
Wavelength 488-632 nm; the detection spectral range is 50-2000cm-1。
8. The trace explosive and drug detector of claim 1, wherein the heating station is associated with a gas sensor
The substrate is bonded by silver colloid heat conducting glue, and the heating temperature is 50-200 ℃.
9. The trace explosive and drug detector of claim 1, wherein the front window and vacuum box are switchable
The joint is provided with a rubber ring.
10. The use method of the trace explosive and drug detector according to claim 1, characterized by comprising the following steps:
(1) a gas inlet of the trace explosive and drug detector is aligned with an object to be detected;
(2) starting a micro vacuum pump, opening a valve at a gas leading-out port, opening a valve at a gas leading-in port, pumping air to the vacuum box through the micro vacuum pump, leading in a substance to be detected, emitting gaseous molecules on the surface of the substance to be detected, and adsorbing the molecules on the surface of the self-curling micro-tube modified by the nano metal particles;
(3) opening the laser Raman spectrometer, and detecting a Raman scattering spectrum of the inhaled gas molecules;
(4) comparing the characteristic Raman scattering spectra of the drugs and the explosive components with the Raman scattering spectrum of the detected gas molecules to judge whether the explosives or the drug gas molecules are introduced, and judging whether the object to be detected contains dangerous objects such as the explosives or the drugs according to the judgment;
(5) turning on a heating table power supply, and heating the self-curling micron tube modified by the nano metal particles;
(6) closing a gas inlet valve of the vacuum box, vacuumizing the vacuum box and removing residual gas; opening the gas inlet valve of the vacuum box and aiming at a new object to be detected for circular detection or aiming at a nitrogen tank to introduce nitrogen protective gas, closing the gas outlet valve, closing the gas inlet valve, closing the micro vacuum pump, sealing the nitrogen protective gas in the vacuum box, and leaving the detector to be protected for next use.
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| CN108088837A (en) * | 2017-11-24 | 2018-05-29 | 复旦大学 | A kind of trace explosive and drug detector and its application method |
| CN112304666B (en) * | 2020-11-27 | 2023-07-25 | 北京华泰诺安探测技术有限公司 | Trace explosive detector |
| CN113970534B (en) * | 2021-12-27 | 2022-03-11 | 中国工程物理研究院流体物理研究所 | Application method of vacuum cavity for carrying out toxic material in-situ diagnosis based on laser device |
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