CN1274084A - Process for preparing moisture sensitive sensor - Google Patents
Process for preparing moisture sensitive sensor Download PDFInfo
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- CN1274084A CN1274084A CN 99113697 CN99113697A CN1274084A CN 1274084 A CN1274084 A CN 1274084A CN 99113697 CN99113697 CN 99113697 CN 99113697 A CN99113697 A CN 99113697A CN 1274084 A CN1274084 A CN 1274084A
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- technology
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- humidity
- film
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- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 238000005516 engineering process Methods 0.000 claims abstract description 30
- 239000011521 glass Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000000919 ceramic Substances 0.000 claims abstract description 4
- 239000000470 constituent Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000007669 thermal treatment Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000000352 supercritical drying Methods 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 239000000146 host glass Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 26
- 239000010408 film Substances 0.000 description 13
- 239000006193 liquid solution Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000002114 nanocomposite Substances 0.000 description 6
- 230000001953 sensory effect Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000007791 dehumidification Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 238000012804 iterative process Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
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- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
A process for preparing moisture-sensitive sensor for measuring humidity features use of sol-gel technology and includes preparing moisture-sensitive solution, coating film on the ceramic substrate with interdigital electrode by pull-up method, and heat treatment to obtain moisture-sensitive LiCl/glass substrate sensor. Said sensor has the advantages of wide humidity range, moderate electric resistance, good linearity of resistance to humidity and simple process.
Description
The present invention relates to a kind of manufacture method that is used for the moisture sensor of moisture measurement.
Hair hygrometer and psychrometer etc. are adopted in the monitoring of humidity the earliest, and their principle all is the physical quantity that humidity is changed into non-electrical signal, so incompatible to the accurate measurement of humidity and control automatically.The humidity-sensitive material that humidity is converted to electric parameter (as resistance, electric capacity, curtage etc.) mainly contains electrolyte and macromolecular compound wet sensory material now; The pottery wet sensory material; Porous metal oxide and semiconductor wet sensory material etc.
More than the development and the production application of the humidity sensitive device made of all kinds of humidity-sensitive materials, it also is relatively backward comparing with other Sensitive Apparatuses.Its main cause is the wet sensory material that is difficult to obtain to have ideal performance on the one hand, is that condition of work is complicated and abominable because humidity sensitive device when work must be exposed in the environment to be measured on the other hand.Subject matter for electrolyte and macromolecular material is to be difficult to adapt to bad working environment.For stupalith, its complicated process of preparation, poor repeatability, resistance is higher.For the semiconductor humidity-sensitive material, its manufacturing equipment costliness, the cost height, performance is also unsatisfactory.Therefore explore new technology, the research new material is the direction of humidity-sensitive material long-run development.
Dunmore's cell is traditional electrolyte moisture sensor, present preparation technology is dissolved in lithium chloride in the polyvinyl alcohol (PVA) (PVA), because the moisture absorption swelling of PVA, make its hygrometric scope become very narrow, usually to make the element of six kinds of different lithium chloride content, be stitched together then and just can finish measurement, its complex process complete wet scope.
It is simple to the purpose of this invention is to provide a kind of technology of preparing, and cost is low, is convenient to practicality, and can finish the moisture sensor manufacturing technology that complete wet scope is measured with an element.
The present invention is that to utilize nanometer composite technology to make wet sensing performance good, stable performance, the simple moisture sensor of manufacturing process.Because wet sensory material is often under middle and high humidity, unstable properties, pass through nanometer composite technology, one side utilizes the stability of matrix material to improve the stability of nano composite material, utilize the susceptibility of nanometer materials to improve the sensitivity of material on the other hand, utilize sol-gel technology to obtain the characteristics of porous matrix material easily simultaneously, make matrix material also possess wet quick characteristic, performance of composites be can regulate and control and optimize like this, thereby a kind of new preparation method and technology started for preparing wet quick new material.
Adopt the technology of preparing of nano composite material, the nanoscale wet sensory material is dispersed in the porous matrix material, the advantage that forms nano composite material is: at first, the wet quick constituent element of nanometer has huge surface area, and therefore traditional micron and block materials can improve greatly to the susceptibility of humidity.Secondly, because of the anti-environmental attack performance of matrix material is good, thereby improve the whole anti-environmental attack ability of compound substance.The 3rd, porous humidity sensing characteristic and nanometer wet quick constituent element compound of nano composite material by matrix material can reach the purpose of improving wet quick constituent element characteristic and enlarging the hygrometric scope.
Nanometer composite technology, it is brand-new humidity sensitive thin film material preparation technology, utilize this technology to prepare the humidity sensitive thin film sensor and yet there are no report, the prominent feature of this technology is to use sol-gel technology, and the quick constituent element that will wet (chlorination reason) is compound in the host glass colloidal sol based on silicon dioxide.Secondly, this technology adopts czochralski method being printed on plated film on the ceramic substrate of golden interdigital electrode.The 3rd, film drying is a natural drying at room temperature, or supercritical drying.The 4th, this technology is with film thermal treatment at high temperature (400～650 ℃) 0.5～2 hour.
Fig. 1, Fig. 2 are process chart.Fig. 3 is the ceramic substrate synoptic diagram that has interdigital electrode.Fig. 4 is the typical relation figure of such film impedance and relative humidity.Fig. 5 is the typical moisture absorption dehumidification of such a film response curve.
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail.
In Fig. 1, metal alkoxide is meant that those can form the metal alkoxide of the glass constituent element that is suitable as the humidity-sensitive material matrix, and the present invention adopts ethyl orthosilicate, aluminium isopropoxide, butyl borate etc.Solvent is meant deionized water, ethanol and ethylene glycol, adds an amount of hydrochloric acid or nitric acid in case of necessity.Glass elder generation liquid solution is meant and can forms silica glass, sial glass, the first liquid solution of silicon boron glass or sial boron glass.
The wet quick constituent element that the present invention adopts is meant lithium chloride, wet sensitization compound or oxide that tri-iron tetroxide etc. are common.Solvent refers to deionized water and ethanol.The first body of wet quick constituent element refers to the ethanol water of lithium chloride or tri-iron tetroxide etc.Tri-iron tetroxide colloidal sol adopts the preparation of Marsart method, sees IEEE Transaction on magnetics for details, Vol.mag-17, No.2, (1981). and the ferroferric oxide gel particle that utilizes this method to make is about 12 nanometers.
The compound first liquid solution of glass-base nanometer refers to the transparent colloidal sol that evenly has certain stoichiometric proportion that obtains after above two kinds of solution mix.
Fig. 2 has provided the compound humidity-sensitive material device preparing process of two kinds of glass-base nanometers that the present invention adopts, (1) is that the substrate that will be printed on interdigital electrode is immersed in by describing among Fig. 1 in the first liquid solution that obtains among the figure, slowly promote, on substrate surface, obtain colloidal sol-gel film, obtain the glass-base nanometer composite film material by dry and high-temperature heat treatment, can use after wearing out, testing, this is a step Technology for Heating Processing.Figure (two) is a two-step thermal treatment process, concrete technology is, at first substrate is immersed in glass elder generation body, system film step in the iterative process (), on substrate, obtain the fritted glass film, and then immerse in the wet quick constituent element elder generation liquid solution, finish thermal treatment at low temperatures behind the filming technology, obtain having the nano compound film of wet quick performance, behind burn-in test, can use.
Two kinds of technologies of the present invention are suitable for high temperature resistant respectively and quick constituent element of DIFFERENT WET non-refractory and the compound situation of glass, if wet quick constituent element maximum heat treatment temperature is lower than the formation temperature of nanoporous glass, then adopt a kind of technology in back, otherwise a kind of technology before adopting.
The preparation of elder generation's liquid solution is prerequisite and the basis that obtains nano combined humidity-sensitive material, and the molar content of the wet quick constituent element of the present invention is 10～50%, looks the requirement of wet sensitive device measurement range and the requirement of other characteristics and can suitably adjust the wet content of quick constituent element in glass.Also will look the ratio that concrete condition is adjusted various oxides for the glass composition, the glass that the present invention adopts consists of: SiO
2: 50～100%, Al
2O
3: 0～50%, B
2O
3: 0～50%.Requiring for first liquid solution is that first body is uniform and stable, meets predetermined stoichiometric proportion, satisfies the film forming requirement simultaneously.
Film drying is at room temperature dry 24 hours, also can adopt supercritical drying.
Thermal treatment is the key that obtains nano composite structure, and for first kind of technology, key is the wet quick constituent element of separating out nano-grade size by thermal treatment original position in having the noncrystal membrane of porous structure.For second kind of technology, key is that the first step at first will obtain the fritted glass film, is that the wet quick constituent element of nanometer enters in the porosint then, obtains nano composite structure.
The heat treatment temperature that the present invention adopts is 400～650 ℃, and thermal treatment is carried out under air atmosphere, for the tri-iron tetroxide glass based composite material, adopts two-step thermal treatment process, and the second step heat treatment temperature will be lower than 300 ℃, to avoid forming too much γ-Fe
2O
3
The aging method that the present invention adopts is that material is placed temperature is 50～80 ℃, and relative humidity is to place one to fortnight in 80～85% the environment.Fig. 3 provides the structural representation of the moisture sensor of the present invention's employing, and a is corundum or glass-ceramic substrate among the figure, and b is the golden interdigital electrode of printing, and c is the compound humidity sensitive thin film of glass-base nanometer.
Exemplary embodiments that makes according to the present invention:
Fig. 4 forms (mole percentage) to be LiCl:20%, Al
2O
3: 20%, SiO
2: 60%.At the impedance of 500 ℃ of following thermal treatments moisture sensor after hour and the relation curve of relative humidity, Fig. 5 is moisture absorption and the dehumidification response curve of this sensor after 550 ℃ of following thermal treatment.
Claims (2)
- The prominent feature of this technology is to use sol-gel technology, and the quick constituent element that will wet (chlorination reason) is compound in the host glass colloidal sol based on silicon dioxide.Secondly, this technology adopts czochralski method being printed on plated film on the ceramic substrate of golden interdigital electrode.The 3rd, film drying is a natural drying at room temperature, or supercritical drying.The 4th, this technology is with film thermal treatment at high temperature (400～650 ℃) 0.5～2 hour.Claimed scope: 1. utilize sol-gel technology, wet quick constituent element such as lithium chloride or tri-iron tetroxide is compound to (glass consists of: SiO in the silica based glasses 2: 50～100%, Al 2O 3: 0～50%, B 2O 3: 0～50%; The content of active component in glass is: 10～50%).
- 2. utilize czochralski method being printed on plated film on the substrate of golden interdigital electrode, (a step process heat treatment temperature is 400～650 ℃ to such moisture sensor that obtains through bakingout process then; Two step process are 200～300 ℃, and heat treatment time is 0.5～2 hour).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99113697 CN1274084A (en) | 1999-05-13 | 1999-05-13 | Process for preparing moisture sensitive sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99113697 CN1274084A (en) | 1999-05-13 | 1999-05-13 | Process for preparing moisture sensitive sensor |
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| Publication Number | Publication Date |
|---|---|
| CN1274084A true CN1274084A (en) | 2000-11-22 |
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ID=5276859
Family Applications (1)
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|---|---|---|---|
| CN 99113697 Pending CN1274084A (en) | 1999-05-13 | 1999-05-13 | Process for preparing moisture sensitive sensor |
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| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104483453A (en) * | 2014-12-23 | 2015-04-01 | 安徽助成信息科技有限公司 | Manufacturing technology of lithium chloride humidity sensitive element |
| CN108169295A (en) * | 2017-10-30 | 2018-06-15 | 上海幂方电子科技有限公司 | Flexible humidity sensor and preparation method thereof |
| CN109444235A (en) * | 2018-10-23 | 2019-03-08 | 中国科学院微电子研究所 | Integrated humidity sensor and method of manufacturing the same |
-
1999
- 1999-05-13 CN CN 99113697 patent/CN1274084A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104483453A (en) * | 2014-12-23 | 2015-04-01 | 安徽助成信息科技有限公司 | Manufacturing technology of lithium chloride humidity sensitive element |
| CN108169295A (en) * | 2017-10-30 | 2018-06-15 | 上海幂方电子科技有限公司 | Flexible humidity sensor and preparation method thereof |
| CN109444235A (en) * | 2018-10-23 | 2019-03-08 | 中国科学院微电子研究所 | Integrated humidity sensor and method of manufacturing the same |
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| Date | Code | Title | Description |
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| C06 | Publication | ||
| PB01 | Publication | ||
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| ASS | Succession or assignment of patent right |
Free format text: FORMER OWNER: ZHAO PENG; ZHAI JIWEI Effective date: 20021114 Owner name: TONGJI UNIVERSITY Free format text: FORMER OWNER: YAO XI |
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| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20021114 Address after: 1239 Institute of functional materials, Tongji University, Siping Road, 200092, Shanghai Applicant after: Tongji University Address before: 200092 Functional Materials Research Institute, Siping Road, Shanghai 1239 Applicant before: Yao Xi Co-applicant before: Zhao Peng Co-applicant before: Di Jiwei |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |