CN101825511A - Minitype capacitance type gas sensor and preparation method thereof - Google Patents
Minitype capacitance type gas sensor and preparation method thereof Download PDFInfo
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- CN101825511A CN101825511A CN 201010161765 CN201010161765A CN101825511A CN 101825511 A CN101825511 A CN 101825511A CN 201010161765 CN201010161765 CN 201010161765 CN 201010161765 A CN201010161765 A CN 201010161765A CN 101825511 A CN101825511 A CN 101825511A
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Abstract
The invention discloses a minitype capacitance type gas sensor, which comprises an upper electrode flat plate, a lower electrode flat plate, a plurality of struts and medium films, wherein the struts are arranged between the upper electrode flat plate and the lower electrode flat plate, so that a cavity is formed between the upper electrode flat plate and the lower electrode flat plate; and the medium films are coated on the struts and the inner surfaces of an upper electrode and a lower electrode. The minitype capacitance type gas sensor is characterized in that: (1) the medium films on adjacent struts are not in contact to each other and a reserved cavity structure forms a gas diffusion channel; and (2) an air hole is not formed on the upper electrode flat plate and side walls between the upper electrode flat plate and the lower electrode flat plate are open, so that gas enters from the side walls. The minitype capacitance type gas sensor can detect various gases to be detected with extremely-low density and has the characteristics of quick response, high sensitivity and wide detection object.
Description
Technical field
The present invention relates to the gas sensor technical field, be specifically related to a kind of capacitance type gas sensor and preparation method thereof.
Background technology
Gas sensor has polytype, and capacitance type gas sensor is wherein a kind of.It is that dielectric layer is set between positive and negative electrode, comes measure gas concentrations by measuring because dielectric layer adsorbs the capacitance variation that gas to be measured produces, have highly sensitive, characteristics such as volume is little, and noise is low, and the gaseous species of detection is many.
A lot of researchs have been done to minitype capacitance type gas sensor by U.S. Seacoast company.Fig. 1 is the mini type gas sensor of a kind of plate condenser structure of the said firm's development, between upper and lower plate electrode layer, form cavity by MEMS technology, filled polymer medium in cavity is characterized in being provided with diffusion and the absorption of air hole to carry out gas on top crown again.In this sensor, electric pole plate is equivalent to a unsettled diaphragm, and diaphragm also is provided with many pillars to reinforce top crown in the centre of diaphragm except supporting around carrying out, and support all around forms closed sensor sidewall.On top crown or sidewall, be provided with perforate with the injection of polymer medium.Document [1] Sensors and Actuators B, 2003,96:541-553; [2] Sensors and ActuatorsB, 2005,107:892-903; [3] Proc.of SPIE, 2005,5986,59860M; [4] Sensors andActuators B, 2006,116:192-201; [5] U.S. Pat 7115969; [6] U.S. Pat 7393740; [7] Talanta, 2008, describe the structure of this capacitance type gas sensor among the 76:872-877 in detail, and they are applied to survey organic volatile compound (VOCs), explosive, chemical warfare agent (CWAs) and poisonous industrial chemical gases such as (TICs).
The gas sensor of this kind capacity plate antenna type has very high sensitivity, has reached 2ppb and 0.1ppb respectively as the detection lower limit to DMMP and nitrobenzene explosive.But they all have a common ground, and gas to be measured exactly all is by the electric pole plate of porous or open top electrode, enter in the gas sensor, and through the absorption of medium sensitive material, thus the electric capacity of change specific inductive capacity and sensor.The shortcoming of this structure is:
Gas to be measured enters sensor by the pore on the electric pole plate, and by the fully absorption of medium sensitive material institute, need the long time, thereby the response time of whole capacitor formula gas sensor is longer, as the response time t to DMMP
90Up to 138s, this has a significant impact for the application that needs fast detecting and response, as the context of detection at explosion gas and poison gas.And because the area of pore is limited, the adsorption area that dielectric film comes out is very little, is unfavorable for fully contacting with gas.
Summary of the invention
Problem to be solved by this invention is: how a kind of minitype capacitance type gas sensor and preparation method thereof is provided, and this sensor can significantly shorten the diffusion time of gas to be measured, has improved the response speed of capacitance type gas sensor.
Technical matters proposed by the invention is to solve like this: a kind of minitype capacitance type gas sensor is provided, comprise top electrode flat board, bottom electrode flat board, some pillars and dielectric film, pillar is arranged between top electrode flat board and the bottom electrode flat board, make and form cavity between the two, described dielectric film be coated on the pillar and the inside surface of upper/lower electrode on, it is characterized in that:
1. the dielectric film on the adjacent struts does not contact each other, and the cavity structure of reservation forms gas diffusion paths;
2. on the top electrode flat board pore is not set, the sidewall between top electrode flat board and the bottom electrode flat board is open, and gas is entered from sidewall.
According to minitype capacitance type gas sensor provided by the present invention, it is characterized in that described dielectric film is organic dielectric thin film or inorganic oxide media film.
A kind of preparation method of minitype capacitance type gas sensor is characterized in that, may further comprise the steps:
1. on silicon substrate, prepare the bottom electrode film, and graphically form the bottom electrode flat board;
2. adopt chemical vapour deposition technique to prepare silicon nitride or nitrogen-oxygen-silicon film on the bottom electrode flat board, and etched film forms pillar, the shape of position, edge pillar can be inconsistent with the pillar in centre, and size is comparable centre bigger also;
3. spin-coating glass, its thickness is consistent with the height of pillar;
4. the polysilicon that adopts chemical vapour deposition technique to prepare on the glass sacrifice layer to mix forms plate condenser as the top electrode flat board;
5. adopt HF acid to remove the glass sacrifice layer, discharge cavity structure, form plate condenser with cavity structure;
6. adopt infusion process at coated media film on the pillar of plate condenser and on the inside surface of upper and lower electrode plate, form the miniature plate capacitance type gas sensor with cavity structure.
Preparation method according to minitype capacitance type gas sensor provided by the present invention, it is characterized in that, described dielectric film is organic dielectric thin film or inorganic oxide media film, the inorganic oxide media film adopts metallorganics as precursor aqueous solution, and immersion coating is after thermal treatment forms inorganic oxide film.
Preparation method according to minitype capacitance type gas sensor provided by the present invention, it is characterized in that, the bottom electrode flat board is the doped polycrystalline silicon film of chemical vapour deposition technique preparation or the metallic film of evaporation or sputtering method preparation, and metallic film comprises gold, copper, aluminium, nickel chromium triangle, platinum, titanium, tungsten.
The present invention is based on the improvement of the capacity plate antenna formula gas sensor of U.S. Seacoast company, and main innovative approach is:
(1) dielectric layer of the capacity plate antenna formula gas sensor of U.S. Seacoast company all fills up the cavity between the upper/lower electrode; And in the present invention, the dielectric layer that is coated on the pillar is thinner, still remains with the gap between the pillar, and gas can flow freely;
(2) sidewall of the capacity plate antenna formula gas sensor of U.S. Seacoast company seals, and gas is entered by the pore on the top electrode flat board; And on the top electrode flat board pore is not set in the present invention, and gas is that the sidewall by sensor enters, gapped between pillar and the pillar because the sidewall of sensor is surrounded by pillar, these gaps have constituted pore;
(3) dielectric layer of the capacity plate antenna formula gas sensor of U.S. Seacoast company is to be in the enclosed cavity, therefore adopts perfusion filled media layer; And in the present invention because cavity structure is open, perfusion is no longer suitable, and adopts infusion process coated media layer.Infusion process has also guaranteed only can apply the last layer dielectric film at the inwall of cavity, and whole cavity can not filled up;
(4) though the capacity plate antenna formula gas sensor of U.S. Seacoast company also has pillar between upper and lower battery lead plate, the effect of these pillars only is in order to strengthen the support to the top electrode flat board.And in the present invention, these characteristics of internal surface area have been increased after also having utilized pillar to form.And after the sensor of Seacoast company filled up whole space with dielectric film, the internal surface area that pillar provided had just disappeared.
Essence of the present invention is that the solid dielectric layer with the capacity plate antenna formula gas sensor of U.S. Seacoast company changes porous medium layer into, makes adsorption area bigger, and the path of absorption is longer, adsorbs more fully, helps improving the sensitivity of sensor; And the porous structure of dielectric layer is connected as a single entity, and communicates with the pore of outer wall, thereby helps the response time of the diffusion shortening sensor of gas.
The present invention is based on the improvement of existing miniature plate capacitance type gas sensor structure, and this improvement is simple, can continue to use original processing step fully, and the reticle that only needs to change entablature and upper electrode layer can realize.
Description of drawings
Fig. 1 is the capacity plate antenna formula gas sensor configuration synoptic diagram of U.S. Seacoast company, (a) sectional view (referring to Talanta, 2008,76:872-877); (b) top view (referring to Sensors and ActuatorsB, 2006,116:192-201);
Fig. 2 is the sectional view of miniature plate capacitance type gas sensor of the present invention;
Fig. 3 is the vertical view of first kind of structure sensor of the present invention;
Fig. 4 is the vertical view of second kind of structure sensor of the present invention;
Fig. 5 is the vertical view of the third structure sensor of the present invention;
Fig. 6 is the vertical view of the 4th kind of structure sensor of the present invention;
Fig. 7 is the vertical view of the 5th kind of structure sensor of the present invention;
Fig. 8 is the vertical view of the 6th kind of structure sensor of the present invention.
Wherein, 1 is silicon chip; 2 is lower electrode plate; 3 is electric pole plate; 4 is the medium sensitive thin film; 5 is top electrode pore/filling orifice; 6 is sidewall; 7 is pillar; 8 is side pore/filling orifice; 9 is gas channel.
Embodiment
Below in conjunction with accompanying drawing the present invention is further described:
This minitype capacitance type gas sensor, as shown in Figure 2, comprise top electrode flat board, bottom electrode flat board, some pillars and dielectric film, pillar is arranged between top electrode flat board and the bottom electrode flat board, make and form cavity between the two, described dielectric film be coated on the pillar and the inside surface of upper/lower electrode on, dielectric film on the adjacent struts does not contact each other, the cavity structure that keeps forms gas diffusion paths, pore is not set on the top electrode flat board, sidewall between top electrode flat board and the bottom electrode flat board is open, and gas is entered from sidewall.Dielectric film is organic dielectric thin film or inorganic oxide media film.
The preparation method may further comprise the steps:
1. on silicon substrate, prepare the bottom electrode film, and graphically form the bottom electrode flat board;
2. adopt chemical vapour deposition technique to prepare silicon nitride or nitrogen-oxygen-silicon film on the bottom electrode flat board, and etched film forms pillar, the shape of position, edge pillar can be inconsistent with the pillar in centre, and size is comparable centre bigger also;
3. spin-coating glass, its thickness is consistent with the height of pillar;
4. the polysilicon that adopts chemical vapour deposition technique to prepare on the glass sacrifice layer to mix forms plate condenser as the top electrode flat board;
5. adopt HF acid to remove the glass sacrifice layer, discharge cavity structure, form plate condenser with cavity structure;
6. adopt infusion process at coated media film on the pillar of plate condenser and on the inside surface of upper and lower electrode plate, form the miniature plate capacitance type gas sensor with cavity structure.
Dielectric film is organic dielectric thin film or inorganic oxide media film, and the inorganic oxide media film adopts metallorganics as precursor aqueous solution, and immersion coating is after thermal treatment forms inorganic oxide film.
The bottom electrode flat board is the doped polycrystalline silicon film of chemical vapour deposition technique preparation or the metallic film of evaporation or sputtering method preparation, and metallic film comprises gold, copper, aluminium, nickel chromium triangle, platinum, titanium, tungsten.
Below be specific embodiments of the invention:
As shown in Figure 3, the profile of sensor is circular, and pillar is a square.The gas sensor of this structure comprises lower electrode plate 2, electric pole plate 3, pillar 7, medium sensitive thin film 4, be arranged on the pore 5 of sidewall, have the sidewall 6 of perforate.Be the metallic aluminium film of 500nm by evaporation technology deposit one layer thickness on silicon chip 1, it is the circle of 1mm that the graphical back of thin film photolithography is formed diameter, as the lower electrode plate 2 of capacity plate antenna.Sidewall 6 and pillar 7 adopt silicon nitride, and film thickness is 2um, and using plasma strengthens the preparation of chemical vapor deposition (PECVD) technology and adopts dry etching to form pattern shown in Figure 3.The fan-shaped pillar of sidewall 6 for being separated from each other, dutycycle is 1: 1, the central angle of fan-shaped pillar and pore 5 correspondences all is 4.5 °; Inner leg 7 is that the length of side is the square of 50um, horizontal interval 150um, and perpendicular separation 50um is staggered on lower electrode plate 2.By spin-coating glass, make its thickness highly consistent with pillar 7 subsequently, adopting the PECVD method to deposit a layer thickness on the glass sacrifice layer is the doped polycrystalline silicon film of 500nm, forms electric pole plate 3, re-uses BOE buffering etching solution (HF: NH
4F: H
2O=3ml: 6g: 10ml), remove the glass sacrifice layer, form plate condenser with cavity structure.Medium sensitive thin film 4 is dissolved in PMPS in the chloroform soln for poly-methyl [3-(2-hydroxyl) phenyl] propyl-siloxane (PMPS), and being made into concentration is the PMPS solution of 1wt%.The miniature plate capacitance type gas sensor is impregnated in the PMPS solution pulls out after half a minute, put into baking oven, 90 ℃ of bakings of constant temperature 60min volatilizees the solvent methenyl choloride fully.This gas sensor can be used to survey DMMP gas, and the response time of sensor is 20-30s.
This routine sensor profile is circular, and pillar also is circular, as shown in Figure 4.Compare with example 1, the lower electrode plate 2 of sensor, sidewall 6, medium sensitive thin film 4 are identical with electric pole plate 3, and just dielectric layer pillar 7 is designed to circle.Circular pillar 7 highly is 2um, and diameter is 50um, horizontal interval 150um each other, and perpendicular separation 50um, and be staggered on lower electrode plate 2.
Compare with example 2 with embodiment 1, the lower electrode plate 2 of the sensor that this is routine, sidewall 6, medium sensitive thin film 4 and electric pole plate 3 are all identical, and just dielectric layer pillar 7 is designed to rectangle, as shown in Figure 5.Rectangle pillar 7 highly is 2um, and long is 75um, and wide is 37.5um, and horizontal interval and perpendicular separation all are 37.5um, perpendicular array between the adjacent struts.
Embodiment 4-embodiment 6
On the basis of embodiment 1-3, the profile of sensor is designed to rectangle, all the other do not change, and can obtain the sensor construction of the embodiment 4-6 shown in Fig. 6-8 respectively.Wherein, lower electrode plate 2 is the long 1100um that are, wide is the rectangle of 850um.Sidewall 6 is by long 60um, and the rectangle of wide 35um is arranged in order and forms, and dutycycle is 1: 1, and wherein place, four summits is the square of length of side 60um.
Claims (5)
1. minitype capacitance type gas sensor, comprise top electrode flat board, bottom electrode flat board, some pillars and dielectric film, pillar is arranged between top electrode flat board and the bottom electrode flat board, make and form cavity between the two, described dielectric film be coated on the pillar and the inside surface of upper/lower electrode on, it is characterized in that:
1. the dielectric film on the adjacent struts does not contact each other, and the cavity structure of reservation forms gas diffusion paths;
2. on the top electrode flat board pore is not set, the sidewall between top electrode flat board and the bottom electrode flat board is open, and gas is entered from sidewall.
2. minitype capacitance type gas sensor according to claim 1 is characterized in that, described dielectric film is organic dielectric thin film or inorganic oxide media film.
3. the preparation method of a minitype capacitance type gas sensor is characterized in that, may further comprise the steps:
1. on silicon substrate, prepare the bottom electrode film, and graphically form the bottom electrode flat board;
2. adopt chemical vapour deposition technique on the bottom electrode flat board, to prepare silicon nitride or nitrogen-oxygen-silicon film, and etched film form pillar;
3. spin-coating glass, its thickness is consistent with the height of pillar;
4. the polysilicon that adopts chemical vapour deposition technique to prepare on the glass sacrifice layer to mix forms plate condenser as the top electrode flat board;
5. adopt HF acid to remove the glass sacrifice layer, discharge cavity structure, form plate condenser with cavity structure;
6. adopt infusion process at coated media film on the pillar of plate condenser and on the inside surface of upper and lower electrode plate, form the miniature plate capacitance type gas sensor with cavity structure.
4. the preparation method of minitype capacitance type gas sensor according to claim 3, it is characterized in that, described dielectric film is organic dielectric thin film or inorganic oxide media film, the inorganic oxide media film adopts metallorganics as precursor aqueous solution, and immersion coating is after thermal treatment forms inorganic oxide film.
5. the preparation method of minitype capacitance type gas sensor according to claim 3, it is characterized in that, the bottom electrode flat board is the doped polycrystalline silicon film of chemical vapour deposition technique preparation or the metallic film of evaporation or sputtering method preparation, and metallic film comprises gold, copper, aluminium, nickel chromium triangle, platinum, titanium, tungsten.
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| CN102759551A (en) * | 2012-08-09 | 2012-10-31 | 电子科技大学 | Perforated plate capacitor type gas sensor and preparation method |
| CN105158305A (en) * | 2015-10-23 | 2015-12-16 | 上海集成电路研发中心有限公司 | Method for manufacturing humidity sensor compatible with CMOS process |
| CN105181764A (en) * | 2015-09-25 | 2015-12-23 | 上海集成电路研发中心有限公司 | Humidity sensor and manufacturing method |
| CN107960008A (en) * | 2017-12-25 | 2018-04-24 | 佛山市车品匠汽车用品有限公司 | A kind of integrated circuit plate |
| CN108037183A (en) * | 2017-12-12 | 2018-05-15 | 杭州电子科技大学 | A kind of supersonic array gas sensor based on condenser type bridge structure |
| CN108088877A (en) * | 2017-12-25 | 2018-05-29 | 佛山市车品匠汽车用品有限公司 | A kind of multifunctional semiconductor device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102759551A (en) * | 2012-08-09 | 2012-10-31 | 电子科技大学 | Perforated plate capacitor type gas sensor and preparation method |
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| CN108037183A (en) * | 2017-12-12 | 2018-05-15 | 杭州电子科技大学 | A kind of supersonic array gas sensor based on condenser type bridge structure |
| CN108037183B (en) * | 2017-12-12 | 2020-06-05 | 杭州电子科技大学 | Ultrasonic array gas sensor based on capacitance type bridge structure |
| CN107960008A (en) * | 2017-12-25 | 2018-04-24 | 佛山市车品匠汽车用品有限公司 | A kind of integrated circuit plate |
| CN108088877A (en) * | 2017-12-25 | 2018-05-29 | 佛山市车品匠汽车用品有限公司 | A kind of multifunctional semiconductor device |
| CN108088877B (en) * | 2017-12-25 | 2020-05-01 | 江西省吉晶微电子有限公司 | Multifunctional semiconductor device |
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