CN101504360A - Organic gas sensing method - Google Patents

Organic gas sensing method Download PDF

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Publication number
CN101504360A
CN101504360A CNA2009100788038A CN200910078803A CN101504360A CN 101504360 A CN101504360 A CN 101504360A CN A2009100788038 A CNA2009100788038 A CN A2009100788038A CN 200910078803 A CN200910078803 A CN 200910078803A CN 101504360 A CN101504360 A CN 101504360A
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China
Prior art keywords
organic gas
gas
sensing chip
sensing
substrate
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CNA2009100788038A
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Chinese (zh)
Inventor
马文英
杨欢
刘娟意
姚军
李飞
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Institute of Optics and Electronics of CAS
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Institute of Optics and Electronics of CAS
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Priority to CNA2009100788038A priority Critical patent/CN101504360A/en
Publication of CN101504360A publication Critical patent/CN101504360A/en
Pending legal-status Critical Current

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Abstract

The invention discloses a method for sensing organic gas, which is characterized by comprising the following steps: selecting a sensing chip substrate with an appropriate model according to the need of the transmission wavelength, and cleaning and drying the substrate; producing a metal nanometer structure array on the substrate to obtain a sensing chip; combining a layer of gas sensitive film on the metal nanometer structure array according to the variety of gas to be detected; utilizing a light source to irradiate the sensing chip after certain organic gas is absorbed, and then using a spectrum tester to probe transmitted light to obtain an extinction spectrum; and analyzing the extinction spectrum to obtain concentration information of the gas. The method for sensing the organic gas has the advantages of convenience, easiness, quick response speed, low cost and the like, and can be used in aspects such as environmental detection, explosive detection, food security and the like.

Description

A kind of organic gas sensing method
Technical field
The present invention relates to the optical sensor technology field, particularly a kind of gas sensor that is applicable to the environmental monitoring field.
Background technology
Along with the develop rapidly of society and advancing by leaps and bounds of science and technology, environmental pollution is on the rise, and often uses and produce some toxic and harmfuls in Chemical Manufacture and the decoration material, serious threat people's life and health.Therefore study these and be used for the gas sensor of environmental monitoring and explore new gas sensing method, become the problem that people are concerned about day by day.
Surface plasma body resonant vibration (SPR) is a kind of surface physics optical phenomena.When incident light wave produces total reflection at the interface at metal film, and the incident light wave frequency just produces surface plasma resonance when identical with metallic film surface free electron resonant frequency.Resonance angle or resonant wavelength are very responsive to the medium refraction index attached to the metallic film surface, thereby can be used for the detection to the biological or chemical molecule.But utilize the method for existing sensing organic gas based on surface plasma body resonant vibration (SPR) to expose a series of problem.At first, the organic gas molecule is chemical micromolecule, and the sensitivity of existing SPR sensing organic gas method is lower; Secondly, surface plasma body resonant vibration detects based on angular modulation, and accurately controlling incident angle is an operational difficult point; Once more, surface plasma body resonant vibration has the complicated vibrating system that rises, and it comprises light-source system, excitation light path system, coupled system etc.; At last, surface plasma body resonant vibration method detected gas device complexity is unfavorable for portability.In a word, just because of the difficulty that realizes, the method cost of surface plasma body resonant vibration detected gas is higher, is unfavorable for commercialization.
Along with the progress that deeply reaches the nanostructured process technology of plasma optics research, the local surface plasma resonance of metal Nano structure (LSPR) had obtained application in recent years.To be metal nanoparticle or structure absorb and scattering phenomenon the local surface plasma resonance of light its principle, different with the surface plasma body resonant vibration of metallic film.The LSPR spectrum is very responsive to surrounding medium, and main application generally shows detection and the aspects such as analysis, surface plasma resonance image-forming to biomolecule.Utilizing metal nanoparticle local surface plasma resonance (LSPR) to aspect the chemical gas micromolecule sensing, the metal nano ball that just has the people tentatively to propose to utilize chemical synthesis to make carries out sensing, but sensitivity is very low, can't satisfy present needs to gas sensing fully.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, proposed a kind of method of new detection organic gas.
The technical solution adopted for the present invention to solve the technical problems is: a kind of organic gas sensing method, and it is as follows to it is characterized in that comprising step:
(1) select the sensing chip substrate of suitable types according to the needs of transmission peak wavelength, to substrate clean, drying;
(2) in substrate, make metal Nano structure array, promptly obtain sensing chip;
(3) according to the gaseous species that will detect, on the metal Nano structure array of above-mentioned sensing chip in conjunction with one deck gas sensitization film;
(4) sensing chip with step (3) gained places the air that contains organic gas to be measured, utilizes the light source irradiation sensing chip then, surveys transmitted light with spectral investigator again and obtains extinction spectra;
(5) analyze extinction spectra, obtain the concentration information of organic gas to be measured.
The base material of the sensing chip of selecting in the described step (1) is visible light material glass or quartz, perhaps infra-red material silicon.
Metal is gold or silver or aluminium or copper in the metal Nano structure array in the described step (2); Nano particle be shaped as triangle or rhombus or cube shaped or clavate or spherical or linear, characteristic dimension at 20nm between the 500nm; Method for making comprises metal Nano structure self assembly, nanosphere photoetching, focused ion beam lithography, beamwriter lithography, nano impression.
Gas in the described step (3) comprises a certain organic gas in alkanes, alcohols, the benzene class.
Light source in the described step (4) is deuterium lamp, halogen tungsten lamp, xenon lamp.
Spectral investigator in the described step (4) is visible spectrophotometer or infrared spectrometer.
The present invention has the following advantages compared with prior art:
(1) the present invention adopts the local surface plasma resonance effect of metal Nano structure, need not to control the incident angle of light in realization, also need not light path coupling, only need measure and analyze and to draw gas concentration information the spectrum of the delustring before and after the gas absorption; Therefore it is convenient to realize, cost is low;
Therefore (2) the present invention can utilize the delustring information of spectral investigator real time record transmitted light, and its response speed only depends on light path system, real time record gas concentration information fast;
(3) the present invention adopts the metal Nano structure that can compare favourably with the micromolecule size, is therefore detecting aspect the micromolecule, and especially organic gas molecule aspect has special advantages.
Description of drawings
Fig. 1 is the process synoptic diagram of gas absorption on sensing chip;
Fig. 2 is the stereoscan photograph of the triangle metal nanostructured of utilization in the example 1.
Fig. 3 is the spectral measurement system synoptic diagram;
Fig. 4 utilizes spectral measurement system shown in Figure 2 to measure the graph of a relation of variable concentrations resulting flatting efficiency of butanols gas and wavelength in the example 1;
Fig. 5 is example 1 gas concentration and delustring peak wavelength graph of a relation;
Fig. 6 utilizes spectral measurement system shown in Figure 2 to measure the graph of a relation of variable concentrations resulting flatting efficiency of dimethylbenzene gas and wavelength in the example 2;
Fig. 7 is example 2 gas concentrations and delustring peak wavelength graph of a relation.
Embodiment
Introduce the present invention in detail below in conjunction with the drawings and the specific embodiments.But protection scope of the present invention is not limited in following example, should comprise the full content in claims.
Embodiment 1, utilizes method for sensing of the present invention to finish detection to butanols gas.
(1) the K9 glass of selecting to be of a size of 10mm * 20mm * 2mm is as sensing chip substrate, to substrate clean, drying;
(2) utilize the nanosphere photoetching process to make one deck triangle silver nano-array on the substrate of glass of above-mentioned selection, as first structure among Fig. 1 (A), the triangle length of side is 127nm, and the cycle is 400nm, and Fig. 2 is corresponding stereoscan photograph;
(3) to be immersed in concentration be 2.5 * 10 to the silver nanostructured sensing chip of triangle that contains that will be obtained by step (2) -4In the mycophenolic acid of M (MPA) solution (solvent is an ethanol) three minutes, form one deck molecular film comparatively responsive, shown in Fig. 1 (B) to butanols gas;
(4) step (3) resulting structures is placed the air that contains butanol molecules, the molecular film on structure top layer absorbs airborne butanol molecules, shown in Fig. 1 (C);
(5) as shown in Figure 3, be butanols gas detecting system block diagram.Sensing system is made up of visible light source halogen tungsten lamp 1, biography light optical fiber 2, collimation lens 3, air chamber 4, sensing chip 5, condenser lens 6, biography light optical fiber 7, spectrometer 8, data line 9, computing machine 10.The light that halogen tungsten lamp 1 sends shines on the sensing chip of placing in the air chamber 45 through collimation lens 3 by passing 2 transmission of light optical fiber; Transmitted light is coupled into optical fiber 7 by condenser lens 6, enters spectrometer 8 and surveys.The spectrum that spectrometer detects is linked to each other with computing machine 10 by data line 9, and wherein computing machine is equipped with relevant messaging software, carries out data processing;
(6) by after step (5) data processing, can obtain the relation of flatting efficiency and wavelength, as shown in Figure 4; When airborne butanols gas concentration is respectively 0, when 1000ppm, 2000ppm and 4000ppm, measure the delustring spectrum of sensing chip, peak value is in 619nm, 642nm, 667nm, 718nmnm place respectively;
(7) by the resultant data of step (6), the relation that can learn butanols gas concentration and peak wavelength position as shown in Figure 5; Known sensing chip delustring spectrum wavelength information just can be learnt butanols gas concentration information.
Embodiment 2, utilize method for sensing of the present invention to finish the detection of P-xylene gas.
(1) the K9 glass of selecting to be of a size of 10mm * 20mm * 2mm is as sensing chip substrate, to substrate clean, drying;
(2) utilize the beamwriter lithography method to make rhombus gold nano structure in the substrate of above-mentioned selection, as the 4th structure among Fig. 1 (A), the base length of side is 120nm, 60 ° of both sides angles, vertical high 50nm, cycle 400nm;
(3) will obtaining rhombus gold nano structure by step (2), to be immersed in concentration be 5 * 10 -4In the benzenethiol of M (BT) solution (solvent is an ethanol) three minutes, form the comparatively responsive molecular film of one deck P-xylene gas, shown in Fig. 1 (B);
(4) step (3) resulting structures is placed the air that contains dimethylbenzene, the molecular film on structure top layer absorbs airborne dimethylbenzene molecule, illustrates as Fig. 1 (C);
(5) as shown in Figure 3, be dimethylbenzene gas detecting system block diagram.Sensing system is made up of visible light source halogen tungsten lamp 1, biography light optical fiber 2, collimation lens 3, air chamber 4, sensing chip 5, condenser lens 6, biography light optical fiber 7, spectrometer 8, data line 9, computing machine 10.The light that halogen tungsten lamp 1 sends is shone on the sensing chip of placing in the air chamber 45 through collimation lens by optical fiber 2 transmission.Transmitted light is coupled into optical fiber 7 by condenser lens 6, enters spectrometer 8 and surveys; The spectrum that spectrometer detects is linked to each other with computing machine 10 by data line 9, and wherein computing machine is equipped with relevant messaging software, carries out data processing;
(6) by after step (5) data processing, can obtain the relation of flatting efficiency and wavelength, as shown in Figure 6; When airborne dimethylbenzene gas concentration is respectively 0, when 1000ppm, 2000ppm and 4000ppm, measure the delustring spectrum of sensing chip, peak value is in 569nm, 601nm, 619nm, 678nm place respectively;
(7) by the resultant data of step (6), the relation that can learn dimethylbenzene gas concentration and peak wavelength position as shown in Figure 7, known sensing chip delustring spectrum wavelength information just can be learnt dimethylbenzene gas concentration information.

Claims (6)

1, a kind of organic gas sensing method, it is as follows to it is characterized in that comprising step:
(1) select the sensing chip substrate of suitable types according to the needs of transmission peak wavelength, to substrate clean, drying;
(2) in substrate, make metal Nano structure array, promptly obtain sensing chip;
(3) according to the gaseous species that will detect, on the metal Nano structure array of above-mentioned sensing chip in conjunction with one deck gas sensitization film;
(4) sensing chip with step (3) gained places the air that contains organic gas to be measured, utilizes the light source irradiation sensing chip then, surveys transmitted light with spectral investigator again and obtains extinction spectra;
(5) analyze extinction spectra, obtain the concentration information of organic gas to be measured.
2, a kind of organic gas sensing method according to claim 1 is characterized in that: the base material of the sensing chip of selecting in the described step (1) is visible light material glass or quartz, perhaps infra-red material silicon.
3, a kind of organic gas sensing method according to claim 1 is characterized in that: metal is gold or silver or aluminium or copper in the metal Nano structure array in the described step (2); Nanostructured be shaped as triangle or rhombus or cube shaped or clavate or spherical or linear, characteristic dimension at 20nm between the 500nm; Method for making comprises metal Nano structure self assembly, nanosphere photoetching, focused ion beam lithography, beamwriter lithography, nano impression.
4, a kind of organic gas sensing method according to claim 1 is characterized in that: the gas in the described step (3) comprises a certain organic gas in alkanes, alcohols, the benzene class.
5, a kind of organic gas sensing method according to claim 1 is characterized in that: the light source in the described step (4) is deuterium lamp, halogen tungsten lamp, xenon lamp.
6, a kind of organic gas sensing method according to claim 1 is characterized in that: the spectral investigator in the described step (4) is visible spectrophotometer or infrared spectrometer.
CNA2009100788038A 2009-03-03 2009-03-03 Organic gas sensing method Pending CN101504360A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102412805A (en) * 2011-08-12 2012-04-11 应达利电子(深圳)有限公司 Quarts crystal resonator, detector as well as detection method for benzene gas detection
CN103940712A (en) * 2014-04-24 2014-07-23 张利胜 Haze particulate matter detection chip and manufacturing method thereof
CN103998918A (en) * 2012-01-13 2014-08-20 国立大学法人东京大学 Gas sensor
CN108169185A (en) * 2017-12-20 2018-06-15 中国科学院微电子研究所 A kind of optics hydrogen gas sensor and its preparation method and application system

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102412805A (en) * 2011-08-12 2012-04-11 应达利电子(深圳)有限公司 Quarts crystal resonator, detector as well as detection method for benzene gas detection
CN102412805B (en) * 2011-08-12 2017-06-16 应达利电子股份有限公司 A kind of quartz-crystal resonator, detector and detection method detected for benzene hydrocarbon gase
CN103998918A (en) * 2012-01-13 2014-08-20 国立大学法人东京大学 Gas sensor
CN103940712A (en) * 2014-04-24 2014-07-23 张利胜 Haze particulate matter detection chip and manufacturing method thereof
CN103940712B (en) * 2014-04-24 2016-02-03 首都师范大学 Haze particle detection chip and manufacture method thereof
CN108169185A (en) * 2017-12-20 2018-06-15 中国科学院微电子研究所 A kind of optics hydrogen gas sensor and its preparation method and application system

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Open date: 20090812