CN108709905A - The enhanced gas sensor of light based on inhomogeneous illumination - Google Patents
The enhanced gas sensor of light based on inhomogeneous illumination Download PDFInfo
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- CN108709905A CN108709905A CN201810658361.3A CN201810658361A CN108709905A CN 108709905 A CN108709905 A CN 108709905A CN 201810658361 A CN201810658361 A CN 201810658361A CN 108709905 A CN108709905 A CN 108709905A
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- 238000005286 illumination Methods 0.000 title claims abstract description 32
- 206010070834 Sensitisation Diseases 0.000 claims abstract description 35
- 230000008313 sensitization Effects 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000010409 thin film Substances 0.000 claims abstract description 14
- 230000035945 sensitivity Effects 0.000 claims abstract description 13
- 239000004065 semiconductor Substances 0.000 claims abstract description 11
- 230000008859 change Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 16
- 238000009792 diffusion process Methods 0.000 claims description 3
- 230000002269 spontaneous effect Effects 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims description 2
- 230000003760 hair shine Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 230000003319 supportive effect Effects 0.000 claims description 2
- 230000007423 decrease Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 73
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000002207 thermal evaporation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention belongs to gas sensor technical field, the enhanced gas sensor of specially a kind of light based on inhomogeneous illumination.Gas sensor of the present invention includes：Sensing unit, light shield layer and light source；Sensing unit includes substrate, gas sensitization layer, thin film electrode layer；Gas sensitization layer is semi-conducting material, for inhaling, being desorbed under test gas, is concurrently born from the change of body electrical properties；The change of electrical properties includes the resistance of gas sensitization layer, current or voltage variation.Its working method is applied voltage source and detects the curent change of output, to reflect the concentration for being tested gas.Under given illumination, electrode both ends generate photovoltage, at this time if additional voltage with photovoltage direction on the contrary, so output current, that is, base current can decline；Particularly, when additional bias and photoelectric current not only direction on the contrary, but also size it is identical when, then the base current of gas sensor can be greatly reduced, to increase considerably the sensitivity of the gas sensor.
Description
Technical field
The invention belongs to gas sensor technical fields, and in particular to a kind of enhanced air-sensitive of light based on inhomogeneous illumination
Element.
Background technology
Semiconductor gas sensor is using semi-conducting material as the gas sensor of air-sensitive responsive materials, is most common
Gas sensor, be widely used in family and industrial fuel gas leak detection apparatus.Since gas is in semiconductor table
Face is adsorbed and needs to overcome certain energy barrier when being desorbed, therefore commercial semiconductor-type gas sensor is needed in height mostly
The lower work of temperature, additional heater circuit make sensor structure become complicated, and energy consumption increases, and when detecting flammable explosive gas
There is certain security risk.
The response characteristic of gas sensitive can be enhanced with the method for illumination.Usually, light excitation can be semiconductor material
The intrinsic transition of material provides energy, generates electron hole pair in the semiconductors, accelerates gas de- in the suction of semiconductor material surface
Attached process, to improve sensitivity and the adsorption desorption time of gas sensor.But it when using up irradiation semi-conducting material, generates
Extra electron hole to the resistance of material can be made to reduce, cause the base current of gas sensor to increase.Therefore, for detection
The variation of the increased gas of gas sensor electric current after absorption, electric current increases relative to base current unobvious so as to cause sensitivity
Adding seldom even reduces, in terms of the response characteristic for enhancing gas sensitive using illumination, limit such gas sensor
Extensive use.
Invention content
The purpose of the present invention is to provide a kind of enhanced gas sensors of the light based on inhomogeneous illumination, to solve part gas
Sensitivity when using illumination of quick material enhances bad problem.
The enhanced gas sensor of light provided by the invention based on inhomogeneous illumination, structure include from bottom to top：Sensing
Unit 10, light shield layer 20 and light source 30；The sensing unit 10 includes：Substrate 11, gas sensitization layer 12, thin film electrode layer 13；
The substrate 11 is connect with gas sensitization layer 12, and substrate mainly plays a supportive role；
The gas sensitization layer 12 is semi-conducting material, can inhale, under test gas is desorbed, concurrently be born from changing for body electrical properties
Become.The change of the electrical properties includes the resistance of gas sensitization layer, current or voltage variation；
There are two independent parts for the thin film electrode layer 13, and material is metal or alloy, is connect respectively with gas sensitization layer 12
It touches, the change in electrical properties of gas sensitization layer is output to element-external；
The light shield layer 20 is lighttight material, and it acts as a part of light 31 for blocking light source 30 and irradiating, and make
Gas sensitization layer 12 receives irradiation heterogeneous.The irradiation heterogeneous refers to, using two electrodes as the two of direction
End, the light of varying strength is received in gas sensitization layer respectively close to the region at electrode both ends；
The thin film electrode layer 13 is above or below gas sensitization layer 12；
There are a fixed gap between the light shield layer 20 and gas sensitization layer 12, can allow to contact with gas；It can not also
It interspaces, is not contacted with gas；
The light source 30 is fixed on 20 top of light shield layer, and the optical wavelength range launched is 300 ~ 1100nm.
The enhanced gas sensor of light based on inhomogeneous illumination, production method pass through following key step reality
It is existing：
Step 1 makes sensing unit 10.Gas sensitization layer 12 is first made in substrate 11, is then made on gas sensitization layer 12
Make thin film electrode layer 13；Or thin film electrode layer 13 is first made in substrate 11, then gas sensitization layer 12 above；
Step 2 makes light shield layer 20 above sensing unit 10；
Step 3, the fixed light source 30 above light shield layer 20.
The working method of gas sensor of the present invention is applied voltage source（Current source）And detect the electric current of output（Voltage, electricity
The electrical properties such as resistance）Variation, to reflect the concentration for being tested gas.
When light source 30 works and shines, 12 material of gas sensitization layer by light uneven irradiation when, generate volume in material
Outer electron hole pair can at 13 both ends of electrode since electrons and holes are from high concentration region to the spontaneous diffusion of low concentration region
To detect the photovoltage or photoelectric current of generation, and significantly change the resistance of gas sensitization layer.
Further, under given illumination, when 13 both ends of electrode generate photovoltage, if additional voltage and photoelectricity
Press direction on the contrary, so output current, that is, base current can decline.Particularly, when additional bias and photoelectric current not only direction phase
Instead, when and size is identical, then the base current of gas sensor can be greatly reduced, to increase considerably the gas sensor
Sensitivity.The operation principle of the illumination enhancing is also applied for impressed current source, detects electric current or resistance variations.
The beneficial effects of the invention are as follows：Under given illumination, when electrode both ends generate photovoltage, if additional electricity
Pressure is with photovoltage direction on the contrary, so output current, that is, base current can decline.Particularly, when additional bias and photoelectric current not
Only direction on the contrary, and size it is identical when, then the base current of gas sensor can be greatly reduced, to increase considerably this
The sensitivity of gas sensor.
Description of the drawings
Fig. 1 is the sectional structure chart of the enhanced gas sensor of the light based on inhomogeneous illumination described in the embodiment of the present invention 1.
Fig. 2 is the decomposition chart of the enhanced gas sensor of the light based on inhomogeneous illumination described in the embodiment of the present invention 1.
Fig. 3 is the enhanced gas sensor of the light based on inhomogeneous illumination described in the embodiment of the present invention 1 open in light source and
VA characteristic curve under closed state compares.
Fig. 4 is the enhanced gas sensor of the light based on inhomogeneous illumination described in the embodiment of the present invention 1 open in light source and
The quick continuous dynamic response characteristic of 50 ppm ammonia under closed state compares.
Fig. 5 is the sectional structure chart of the enhanced gas sensor of the light based on inhomogeneous illumination described in the embodiment of the present invention 2.
Fig. 6 is the sectional structure chart of the enhanced gas sensor of the light based on inhomogeneous illumination described in the embodiment of the present invention 3.
Figure label：10 be sensing unit；11 be substrate；12 be gas sensitization layer；13 be thin film electrode layer；20 be shading
Layer；30 non-light sources；31 be light.
Specific implementation mode
The preferred embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings, so that advantages and features of the invention energy
It is easier to be readily appreciated by one skilled in the art, so as to make a clearer definition of the protection scope of the present invention.
Embodiment 1
In conjunction with Fig. 1 ~ Fig. 4, illustrate the gas sensor specific make step and work characteristics of the present embodiment.
The gas sensor step of the present embodiment is specially combined with Figure 1 and Figure 2,：
Step 1 makes sensing unit 10.In the present embodiment, using the preferable N-shaped monocrystalline silicon of light absorptive as substrate 11, thickness
250 μm, 3 ~ 5 k Ω cm of resistivity.Substrate is carried out after thoroughly cleaning, thickness is deposited in one side with the method for thermal evaporation plated film
Spend the selenium film of 70 nm.It is subsequently placed in the protective gas nitrogen that pressure is 70 kPa, high energy femtosecond laser is focused into substrate
On, 60 μm of spot diameter.Continuous moving substrate makes femtosecond laser go out micro-structure and doped layer as gas in substrate surface ablation
Body sensitive layer 12.With the method for thermal evaporation plated film, two thin film electrode layers 13 of area deposition in microstructured area, target material is aluminium, two
0.25 mm of electrode spacing, 400 nm of film thickness；
Step 2 after being drawn electrode with conducting wire, uses insulating black adhesive tape as light shield layer 20, is attached to the side of sensing unit 10, cruelly
Expose other side；
Step 3 makes said elements be relatively fixed for the LED white light sources 30 of 2 W with rated power.LED light source is driven to irradiate gas
Body sensitive layer.
It was former between output current-applied voltage as shown in figure 3, in the C-V characteristic of unglazed lower test gas sensor
The linear relationship of point.After LED light source is opened and is irradiated, electric current-voltage curve without origin, illustrate gas sensitization layer by
Additional electron hole pair is generated when uneven irradiation, in material, due to the spontaneous diffusion of electrons and holes, is generated at electrode both ends
Photovoltage or photoelectric current；In addition straight slope becomes larger, and illustrates that illumination reduces the internal resistance of gas sensor.
At this point, if voltage additional on two electrodes 13 is opposite with the photovoltage direction of gas sensor itself, size is identical
When, most of output current can be offset.As shown in figure 4, it is -4.5 mV this time to test added voltage swing.It can be seen that in light
According to rear, base current is reduced to about 0.1 nA by about 0.9 nA, and base current reduces 88.9%.Gas sensor is placed in concentration
After in the ammonia of 50 ppm, since the current-responsive that illumination is brought also greatly increases.If definition sensitivity is gas sensor
Electric current in ammonia divided by aerial electric current, sensitivity increase to about 50 by about 1.2, due to the enhancing of inhomogeneous illumination
Bring the promotion of about 42 times of sensitivity.Experiment shows that the enhanced gas sensor of light prepared by embodiment 1 can substantially reduce
Base current improves sensitivity.
Embodiment 2
The present embodiment is further limiting to the enhanced gas sensor of the light based on inhomogeneous illumination described in embodiment 1.Knot
Close Fig. 5 uses monocrystalline silicon as substrate 11 in the present embodiment, the method for first using thermal evaporation plated film, is deposited in substrate two thin
Membrane electrode layer 13.Then after being drawn electrode with conducting wire, drop-coating is used to deposit one layer of oxidation graphene film as gas
Sensitive layer 12.Remaining step is the same as embodiment 1.
It is found that the gas sensitization layer 12 is not limited to a certain certain material described in embodiment 1 and embodiment 2, but
It is to belong to semi-conducting material, under test gas can be adsorbed, plays the role of experiencing gas.
Embodiment 3
The present embodiment is further limiting to the enhanced gas sensor of the light based on inhomogeneous illumination described in embodiment 1.Knot
Fig. 6 is closed, in the present embodiment, insulating black adhesive tape is fixed on 10 top of sensing unit as light shield layer 20 and there are certain skies
Gap allows gas to circulate, remaining step is the same as embodiment 2.
Embodiment 4
The present embodiment is further limiting to the enhanced gas sensor of the light based on inhomogeneous illumination described in embodiment 1.
In the present embodiment, when additional electric current is opposite with the photoelectric current direction of gas sensor itself, size is identical, major part can be offset
Output voltage or baseline voltage.Remaining step is the same as embodiment 1.If it is output electricity of the gas sensor in ammonia to define sensitivity
Pressure divided by aerial output voltage, can similarly obtain the promotion of sensitivity.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification and accompanying drawing content is applied directly or indirectly in other relevant skills
Art field, is included within the scope of the present invention.
Claims (5)
1. the enhanced gas sensor of light based on inhomogeneous illumination, which is characterized in that structure includes from bottom to top：Sensing unit
（10）, light shield layer（20）And light source（30）；The sensing unit（10）Including：Substrate（11）, gas sensitization layer（12）, thin-film electro
Pole layer（13）；Wherein：
The substrate（11）With gas sensitization layer（12）Connection, substrate mainly play a supportive role；
The gas sensitization layer（12）It is semi-conducting material, for inhaling, being desorbed under test gas, is concurrently born from changing for body electrical properties
Become；The change of the electrical properties includes the resistance of gas sensitization layer, current or voltage variation；
The thin film electrode layer（13）There are two, independently of each other, material is metal or alloy, respectively with gas sensitization layer（12）It connects
It touches, for the change in electrical properties of gas sensitization layer to be output to element-external；
The thin film electrode layer（13）In gas sensitization layer（12）Above or below；
The light shield layer（20）Using lighttight material, for blocking light source（30）A part of light irradiated（31）, and
Make gas sensitization layer（12）Receive irradiation heterogeneous；
The light source（30）It is fixed on light shield layer（20）Top, the optical wavelength range launched are 300 ~ 1100nm.
2. the enhanced gas sensor of the light according to claim 1 based on inhomogeneous illumination, which is characterized in that described is non-
Uniform irradiation refers to, using two electrodes as the both ends in direction, in gas sensitization layer（12）Region point close to electrode both ends
The light of varying strength is not received.
3. the enhanced gas sensor of the light according to claim 1 based on inhomogeneous illumination, which is characterized in that the shading
Layer（20）With gas sensitization layer（12）Between there are a fixed gap, permission is contacted with gas；Or the light shield layer（20）With gas
Body sensitive layer（12）Between do not interspace, do not contacted with gas.
4. the enhanced gas sensor of the light according to claim 1 based on inhomogeneous illumination, which is characterized in that working method
It is：Applied voltage source or current source, and the variation of the current or voltage of output is detected, to reflect the concentration for being tested gas；
Work as light source（30）It works and shines, gas sensitization layer（12）Material is generated in material additional by the uneven irradiation of light
Electron hole pair, since electrons and holes are from high concentration region to the spontaneous diffusion of low concentration region, in electrode（13）It both ends can
To detect the photovoltage or photoelectric current of generation, and significantly change the resistance of gas sensitization layer；
Under given illumination, thin film electrode layer（13）Both ends generate photovoltage, if additional voltage and photovoltage direction
On the contrary, so output current, that is, base current declines；Particularly, make additional bias and photoelectric current not only direction on the contrary, but also
When size is identical, then the base current of gas sensor is greatly reduced, to increase considerably the sensitivity of the gas sensor.
5. the production method of the enhanced gas sensor of the light based on inhomogeneous illumination as described in one of claim 1-3, special
Sign is, the specific steps are：
Step 1 makes sensing unit（10）：First in substrate（11）Upper making gas sensitization layer（12）, then in gas sensitization layer
（12）Upper making thin film electrode layer（13）；Or first in substrate（11）Upper making thin film electrode layer（13）, then gas above
Sensitive layer（12）；
Step 2, in sensing unit（10）Top makes light shield layer（20）；
Step 3, in light shield layer（20）Top fixed light source（30）.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810658361.3A CN108709905B (en) | 2018-06-25 | 2018-06-25 | Light enhancement type gas sensitive element based on non-uniform illumination |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810658361.3A CN108709905B (en) | 2018-06-25 | 2018-06-25 | Light enhancement type gas sensitive element based on non-uniform illumination |
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| CN108709905A true CN108709905A (en) | 2018-10-26 |
| CN108709905B CN108709905B (en) | 2020-10-30 |
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Cited By (2)
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|---|---|---|---|---|
| CN110987880A (en) * | 2019-12-20 | 2020-04-10 | 华中科技大学鄂州工业技术研究院 | Light excitation gas sensor structure |
| CN111257393A (en) * | 2018-11-30 | 2020-06-09 | 北京纳米能源与系统研究所 | Gas sensing device and sensing method |
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| CN108709905B (en) | 2020-10-30 |
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