JPH01293501A - Porous tin oxide moisture-sensitive thin film and manufacture thereof - Google Patents
Porous tin oxide moisture-sensitive thin film and manufacture thereofInfo
- Publication number
- JPH01293501A JPH01293501A JP63124631A JP12463188A JPH01293501A JP H01293501 A JPH01293501 A JP H01293501A JP 63124631 A JP63124631 A JP 63124631A JP 12463188 A JP12463188 A JP 12463188A JP H01293501 A JPH01293501 A JP H01293501A
- Authority
- JP
- Japan
- Prior art keywords
- moisture
- thin film
- tin oxide
- sensitive
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 44
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 15
- 150000003606 tin compounds Chemical class 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 10
- 230000035945 sensitivity Effects 0.000 abstract description 10
- 238000010438 heat treatment Methods 0.000 abstract description 9
- 235000019441 ethanol Nutrition 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- KRZQYDMOEZDDGE-UHFFFAOYSA-N sodium;octan-1-olate Chemical compound [Na+].CCCCCCCC[O-] KRZQYDMOEZDDGE-UHFFFAOYSA-N 0.000 abstract description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 abstract description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 abstract description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 abstract description 2
- PYKSLEHEVAWOTJ-UHFFFAOYSA-N tetrabutoxystannane Chemical compound CCCCO[Sn](OCCCC)(OCCCC)OCCCC PYKSLEHEVAWOTJ-UHFFFAOYSA-N 0.000 abstract description 2
- 229940071676 hydroxypropylcellulose Drugs 0.000 abstract 1
- 230000000630 rising effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 19
- 238000000034 method Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- -1 tin alkoxides Chemical class 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- OYHQOLUKZRVURQ-HZJYTTRNSA-M 9-cis,12-cis-Octadecadienoate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O OYHQOLUKZRVURQ-HZJYTTRNSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 229940049918 linoleate Drugs 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BOBNBKILGZJTTM-UHFFFAOYSA-N propan-1-olate;tin(2+) Chemical compound [Sn+2].CCC[O-].CCC[O-] BOBNBKILGZJTTM-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- UMBFGWVRZIHXCK-FDGPNNRMSA-L strontium;(z)-4-oxopent-2-en-2-olate Chemical compound [Sr+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O UMBFGWVRZIHXCK-FDGPNNRMSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- YXTDAZMTQFUZHK-ZVGUSBNCSA-L (2r,3r)-2,3-dihydroxybutanedioate;tin(2+) Chemical compound [Sn+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O YXTDAZMTQFUZHK-ZVGUSBNCSA-L 0.000 description 1
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- UDOPITICNQWATG-UHFFFAOYSA-N 2-[1-(4-chlorophenyl)-2,5-dioxoimidazolidin-4-yl]acetic acid Chemical compound O=C1C(CC(=O)O)NC(=O)N1C1=CC=C(Cl)C=C1 UDOPITICNQWATG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 description 1
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920001612 Hydroxyethyl starch Polymers 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DJHZYHWLGNJISM-FDGPNNRMSA-L barium(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ba+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O DJHZYHWLGNJISM-FDGPNNRMSA-L 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- YBGHFLPNIGPGHX-UHFFFAOYSA-N calcium;octan-1-olate Chemical compound [Ca+2].CCCCCCCC[O-].CCCCCCCC[O-] YBGHFLPNIGPGHX-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- GFBPUGNCPRHXJM-UHFFFAOYSA-L dibenzyltin(2+);dihydroxide Chemical compound [OH-].[OH-].C=1C=CC=CC=1C[Sn+2]CC1=CC=CC=C1 GFBPUGNCPRHXJM-UHFFFAOYSA-L 0.000 description 1
- UHPZGYUGTLLMFS-UHFFFAOYSA-N dibutyl(dipropoxy)stannane Chemical compound CCCC[Sn](CCCC)(OCCC)OCCC UHPZGYUGTLLMFS-UHFFFAOYSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- ISXUHJXWYNONDI-UHFFFAOYSA-L dichloro(diphenyl)stannane Chemical compound C=1C=CC=CC=1[Sn](Cl)(Cl)C1=CC=CC=C1 ISXUHJXWYNONDI-UHFFFAOYSA-L 0.000 description 1
- LWHKXKZPLXYXRO-UHFFFAOYSA-L dichloro-bis(ethenyl)stannane Chemical compound C=C[Sn](Cl)(Cl)C=C LWHKXKZPLXYXRO-UHFFFAOYSA-L 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- PCYQGFDMDMYXAY-UHFFFAOYSA-N ethyl(hexoxy)tin Chemical compound C(C)[Sn]OCCCCCC PCYQGFDMDMYXAY-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229940050526 hydroxyethylstarch Drugs 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- HPBJPFJVNDHMEG-UHFFFAOYSA-L magnesium;octanoate Chemical compound [Mg+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HPBJPFJVNDHMEG-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- CYCFYXLDTSNTGP-UHFFFAOYSA-L octadecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CYCFYXLDTSNTGP-UHFFFAOYSA-L 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-M oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC([O-])=O ZQPPMHVWECSIRJ-KTKRTIGZSA-M 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- CCTFOFUMSKSGRK-UHFFFAOYSA-N propan-2-olate;tin(4+) Chemical compound [Sn+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] CCTFOFUMSKSGRK-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920006268 silicone film Polymers 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229940007163 stannous tartrate Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BXCONTUBAJHQLF-UHFFFAOYSA-N strontium octan-1-olate Chemical compound [Sr++].CCCCCCCC[O-].CCCCCCCC[O-] BXCONTUBAJHQLF-UHFFFAOYSA-N 0.000 description 1
- RWWNQEOPUOCKGR-UHFFFAOYSA-N tetraethyltin Chemical compound CC[Sn](CC)(CC)CC RWWNQEOPUOCKGR-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 1
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- HFFZSMFXOBHQLV-UHFFFAOYSA-M tributylstannyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)CCCC HFFZSMFXOBHQLV-UHFFFAOYSA-M 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は湿度センナ用の多孔性酸化スズ感湿体薄膜およ
びその製法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a porous tin oxide moisture sensitive thin film for a humidity sensor and a method for producing the same.
［従来の技術・発明が解決しようとする課題］これまで
湿度センサ用感湿体として、毛髪などの吸湿による膨張
を利用したもの、多孔性セラミックス焼結体や高分子系
薄膜のように吸湿による交流インピーダンス（以下、イ
ンピーダンスという）変化、容量変化を利用したものな
どが知られている。[Conventional technology/problems to be solved by the invention] Up until now, humidity sensors for humidity sensors have been made using the expansion caused by moisture absorption, such as hair, while porous ceramic sintered bodies and polymeric thin films have been used as humidity sensors. There are known methods that utilize alternating current impedance (hereinafter referred to as impedance) changes and capacitance changes.
しかし、毛髪などの膨張を利用したものでは応答速度が
遅く、精度的にも信頼性が低いなど。However, devices that utilize the expansion of hair and other materials have slow response times and low accuracy and reliability.
の問題がある。There is a problem.
また、多孔性セラミックス焼結体では、セラミックスと
いう材料の特性から耐環境性には優れているものの、応
答速度が遅い、吸着水の化学吸着による素子のインピー
ダンスの増加に起因する劣化がおこる、他のセンサと組
合わせた小型複合化あるいは多機能化が不可能であるな
どの問題がある。さらに相対湿度に対するインピーダン
スの変化が、対数目盛で直線的でないために、出力変換
回路が複雑になり、コスト高になるなどの欠点がある。In addition, although porous ceramic sintered bodies have excellent environmental resistance due to the characteristics of the ceramic material, they have slow response times, deterioration due to increased element impedance due to chemical adsorption of adsorbed water, etc. There are problems such as the impossibility of miniaturization or multifunctionalization by combining with other sensors. Furthermore, since the change in impedance with respect to relative humidity is not linear on a logarithmic scale, there are drawbacks such as a complicated output conversion circuit and increased cost.
さらに、高分子系薄膜では応答速度は比較的速く、感度
の優れた感湿体も市販され始めているが、有機物である
ことの欠点である耐環境性がよくない、使用温度範囲が
狭いなどの問題がある。Furthermore, the response speed of polymeric thin films is relatively fast, and moisture-sensitive materials with excellent sensitivity are beginning to be commercially available, but they have the disadvantages of being organic, such as poor environmental resistance and a narrow operating temperature range. There's a problem.
本発明者らはこれらの問題を解決するために酸化物薄膜
の研究を進めている中で、有機スズ化合物を含む溶液の
塗布加熱分解法による酸化スズ薄膜が良好な感湿特性を
有することを見出し、これまで応答速度が速いとされて
きたセラミックス厚膜感湿体あるいは有機物薄膜感湿体
よりも応答速度が速く、さらに有機物ではありえない高
耐熱性などを有する高性能な感湿体素子の開発をすでに
行なっている。しかし、相対湿度に対するインピーダン
ス変化、すなわち感湿特性が、対数目盛で直線性を有す
る感湿体かえられていないため、複雑な出力変換回路が
必要であるという問題がある。While conducting research on oxide thin films to solve these problems, the present inventors discovered that tin oxide thin films produced by applying and thermally decomposing a solution containing an organic tin compound have good moisture sensitivity characteristics. Headline: Development of a high-performance moisture-sensing element that has a faster response time than ceramic thick-film moisture-sensing elements or organic thin-film moisture-sensing elements, which have been thought to have a faster response time, and also has high heat resistance that cannot be achieved with organic materials. has already been done. However, there is a problem in that a complicated output conversion circuit is required because the impedance change with respect to relative humidity, that is, the humidity-sensitive characteristic is not changed to a moisture-sensitive material that has linearity on a logarithmic scale.
［課題を解決するための手段〕
本発明者らはこのような実情に鑑み、出力変換回路をよ
り低コストにするために必要な感湿特性、すなわち相対
湿度に対するインピーダンス変化が対数目盛で直線的で
あるという性質をも有する感湿体を開発するため鋭意研
究を重ねた結果、本発明を完成するに至った。[Means for Solving the Problems] In view of the above circumstances, the present inventors have developed a moisture-sensitive characteristic necessary for lowering the cost of the output conversion circuit, that is, impedance change with respect to relative humidity is linear on a logarithmic scale. As a result of intensive research to develop a moisture-sensitive body that also has the following properties, the present invention has been completed.
すなわち本発明は、基板上に設けられた直径ｌＯ虜以下
の細孔を有する多孔性酸化スズ感湿体薄膜および有機ス
ズ化合物と多官能性有機化合物とを含む溶液を基板上に
塗布し、乾燥後、加熱処理して前記多孔性酸化スズ感湿
体薄膜を製造する方法に関する。That is, the present invention provides a porous tin oxide moisture sensitive thin film having pores with a diameter of 10 mm or less provided on a substrate, and a solution containing an organotin compound and a polyfunctional organic compound, coated on the substrate, and dried. The present invention also relates to a method for producing the porous tin oxide moisture-sensitive thin film by heat treatment.
本発明においては、有機スズ化合物と多官能性有機化合
物とを含む溶液、さらに要すればアルカリ金属もしくは
アルカリ土類金属を含む溶液を基板上に塗布乾燥後、加
熱処理することにより直径】０虜以下の細孔を有する多
孔性酸化スズ薄膜を形成させると、低湿度から高湿度ま
で高感度で、かつ相対湿度に対するインピーダンス変化
が直線性を有する酸化スズ感湿体薄膜かえられる。この
酸化スズ感湿体薄膜は、感湿体として高感度であるだけ
でなく、応答速度が非常に速く、耐環境性にも優れ、小
型インテリジェント化が可能であり、直線的な感湿特性
を示すため、出力変換回路が低コストとなるという特徴
を有している。In the present invention, a solution containing an organotin compound and a polyfunctional organic compound, and if necessary, an alkali metal or an alkaline earth metal, is coated on a substrate, dried, and then heat-treated. By forming a porous tin oxide thin film having the following pores, a tin oxide moisture-sensitive thin film having high sensitivity from low humidity to high humidity and linear impedance change with respect to relative humidity can be obtained. This tin oxide moisture sensitive thin film not only has high sensitivity as a moisture sensitive body, but also has an extremely fast response speed, excellent environmental resistance, can be made compact and intelligent, and has linear moisture sensitive characteristics. Therefore, the output conversion circuit has a feature that the cost is low.
［実施例］
一般に、相対湿度の変化に伴ないインピーダンスが変化
するセラミックス湿度センサでは、水分の物理吸着を利
用している。それゆえ、水分が充分吸着できるように、
表面が多孔性であることが必要である。その際のある相
対湿度での水分吸着は、下記のケルビン式：
％式％）
（式中、ｒ、は細孔半径、γは水の表面張力、ρは水の
密度、Ｍは水の分子量、Ｐｓは飽和水蒸気圧、Ｐは水蒸
気圧を示す）にしたがい、細孔に吸着、凝縮する。この
凝縮水量が相対湿度変化に伴なって変化すると考えられ
ている。したかって、出力変換回路が低コストとなるよ
うな感湿特性、すなわち素子インピーダンス（Ｚ）と相
対湿度（ＲＨ）との間に、１ｏｇＺとＲＨとが直線とな
るような感湿体素子が作製されればよく、このような感
湿体素子を作製するためには、その感湿体の多孔性を制
御すればよいことになる。[Example] Generally, a ceramic humidity sensor whose impedance changes with changes in relative humidity utilizes physical adsorption of moisture. Therefore, so that moisture can be absorbed sufficiently,
It is necessary that the surface be porous. The water adsorption at a certain relative humidity is determined by the following Kelvin formula: % formula %) (where r is the pore radius, γ is the surface tension of water, ρ is the density of water, and M is the molecular weight of water. , Ps is saturated water vapor pressure, P is water vapor pressure), it is adsorbed and condensed in the pores. It is believed that the amount of condensed water changes with changes in relative humidity. Therefore, it is necessary to fabricate a moisture-sensitive element that has moisture-sensitive characteristics such that the output conversion circuit can be made at a low cost, that is, between the element impedance (Z) and the relative humidity (RH), 1ogZ and RH are a straight line. In order to produce such a moisture-sensitive element, it is sufficient to control the porosity of the moisture-sensitive element.
本発明者らは、有機スズ化合物を含む溶液を基板上に塗
布乾燥後、加熱分解することにより、えられる酸化スズ
薄膜が相対湿度の変化に対してインピーダンス変化が生
じることを見出しており、さらに有機金属化合物を含む
溶液を基板上に塗布乾燥後、加熱分解することによって
金属酸化物薄膜をうる際に、塗布溶液中に多官能性有機
化合物を添加することにより、孔径１０項以下の細孔を
有する金属酸化物薄膜かえられることを見出しているが
、酸化スズ薄膜を感湿体として用いるばあい、薄膜を多
孔化することで良好な感湿特性を示すことを見出した。The present inventors have discovered that by coating a solution containing an organic tin compound on a substrate, drying it, and then thermally decomposing the resulting tin oxide thin film, the impedance changes in response to changes in relative humidity. When obtaining a metal oxide thin film by coating a solution containing an organometallic compound on a substrate, drying it, and then thermally decomposing it, by adding a polyfunctional organic compound to the coating solution, pores with a pore size of 10 items or less can be formed. However, when a tin oxide thin film is used as a moisture sensitive material, it has been found that by making the thin film porous, it exhibits good moisture sensitive properties.
水分吸着によるインピーダンス変化を利用したセラミッ
クス湿度センサでは、表面の多孔性は、その感湿体の感
湿特性を左右する重要な因子であり、細孔径分布が重要
な因子となるが、この細孔径分布を調整することで、低
湿度側で高感度になったり、高湿度側で高感度となる感
湿体かえられる。In ceramic humidity sensors that utilize impedance changes due to moisture adsorption, the porosity of the surface is an important factor that influences the moisture-sensing characteristics of the sensor, and the pore size distribution is an important factor. By adjusting the distribution, you can change the humidity sensor to have high sensitivity on the low humidity side or high sensitivity on the high humidity side.
清白らの報告（表面、第２４巻、第３号、１５４頁（１
９８６年））によれば、直線的な感湿特性を示す感湿体
とするには、孔径１０Å以下の細孔から１０１ｓ程度の
細孔まで適度に分布していることが必要とされている。Report by Seihaku et al. (Surface, Vol. 24, No. 3, p. 154 (1)
According to 986)), in order to produce a moisture sensitive material that exhibits linear moisture sensitive characteristics, it is necessary to have a moderate distribution of pores ranging from pore diameters of 10 Å or less to pores of about 101 s. .
本発明の多孔性酸化スズ感湿体薄膜は、このように表面
の多孔性を適宜調整することで良好な感湿特性を示す感
湿体となる。The porous tin oxide moisture-sensitive thin film of the present invention becomes a moisture-sensitive body that exhibits good moisture-sensing characteristics by appropriately adjusting the porosity of the surface.
また、酸化スズは半導体であるために感湿体素子自身の
インピーダンスが比較的小さくなるため、水分吸着は生
じてもインピーダンス変化として検出しにくくなってし
まうが、これは酸化スズにアルカリ金属もしくはアルカ
リ土類金属を添加することで解決できる。In addition, since tin oxide is a semiconductor, the impedance of the moisture-sensitive element itself is relatively small, so even if moisture adsorption occurs, it is difficult to detect it as an impedance change. This can be solved by adding earth metals.
本発明におけるアルカリ金属およびアルカリ土類金属と
しては、リチウム、ナトリウム、カリウム、ルビジウム
、セシウム、ベリリウム、マグネシウム、カルシウム、
ストロンチウム、バリウムから選ばれた１種もしくは２
種以上を用いることができるが、このうちリチウム、ナ
トリウム、カリウム、マグネシウム、カルシウム、スト
ロンチウム、バリウムがとくに好ましい。The alkali metals and alkaline earth metals in the present invention include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium,
One or two selected from strontium and barium
More than one species can be used, but among these, lithium, sodium, potassium, magnesium, calcium, strontium, and barium are particularly preferred.
アルカリ金属もしくはアルカリ土類金属の添加量として
は、スズに対して０．１モル％以上であればよいが、良
好な感湿特性を有する酸化スズ薄膜感湿体を再現よくう
るためには、０．５モル％以上が好ましい。The amount of the alkali metal or alkaline earth metal to be added may be 0.1 mol % or more based on tin, but in order to reproducibly obtain a tin oxide thin film moisture sensitive material having good moisture sensitive characteristics, The content is preferably 0.5 mol% or more.
また、本発明の酸化スズ感湿体薄膜では、感湿体として
の性能に悪影響を与えない範囲であれば、スズに対して
１０モル％以下の濃度で他の金属が含まれていてもよい
が、添加する金属により表面での水分子の解離度が変化
するため、その都度細孔径分布を調整するのが好ましい
。Further, the tin oxide moisture sensitive thin film of the present invention may contain other metals at a concentration of 10 mol% or less based on tin, as long as it does not adversely affect the performance as a moisture sensitive body. However, since the degree of dissociation of water molecules on the surface changes depending on the metal added, it is preferable to adjust the pore size distribution each time.
具体的に、この多孔性酸化スズ感湿体薄膜をうる方法と
しては、有機スズ化合物を含む溶液の塗布加熱分解法も
しくは金属化合物溶液を高温の基板上に噴霧して熱分解
させるスプレー法があるが、より簡単に、かつ再現性の
よい酸化スズ感湿体薄膜をうる方法としては、塗布加熱
分解法が優れている。Specifically, methods for obtaining this porous tin oxide moisture-sensitive thin film include a method of applying and thermally decomposing a solution containing an organic tin compound, or a spray method of spraying a metal compound solution onto a high-temperature substrate and thermally decomposing it. However, the coating thermal decomposition method is an excellent method for obtaining a tin oxide moisture-sensitive thin film more easily and with good reproducibility.
本発明に用いる有機スズ化合物としては、たとえば一般
式（Ｉ）：
８口（ＯＲ’ ）２
（ＩＩ（式中、Ｒ１は炭素数１〜２０の炭化
水素基である）で表わされる２価のスズのアルコキシド
類、一般式（■）＝
Ｓｎ （ＯＲ’ ）４ ［１［）
（式中、Ｒ１は前記と同じ）で表わされる４価のスズの
アルコキシド類、
一般式ＣＤＩ） 。Examples of the organic tin compound used in the present invention include general formula (I): 8-unit (OR')2
Divalent tin alkoxides represented by (II (in the formula, R1 is a hydrocarbon group having 1 to 20 carbon atoms), general formula (■) = Sn (OR')4 [1[)
Tetravalent tin alkoxides represented by (wherein R1 is the same as above), general formula CDI).
５ｎ（ＯＲ１） Ｙ ｆｌ［Ｄ−ａ
ａ
（式中、Ｒ１は前記と同じ、Ｙはキレート能を有する官
能基またはハロゲン原子、ａは１〜３の整数である）で
表わされる４価のスズの部分アルコキシド類、
一般式（１）、一般式（１）、一般式ｌで表わされる化
合物の縮合多量体、
一般式■：
Ｓｎ （ＯＣＯＲ２）２ （ｔＶ）（式
中、Ｒ２は水素原子または炭素数１〜３０の炭化水素基
である）で表わされる２価のスズのカルボン酸塩類、
一般弐Ｍ：
Ｓｎ （ＯＣＯＲ２）４ （Ｖｌ（式中
、Ｒ２は前記と同じ）で表わされる４価のスズのカルボ
ン酸塩類、
２価または４価のスズとアセチルアセトン、ベンゾイル
アセトンなどとの反応物であるβ −ジケトン錯体類、
スズオキシβ−ジケトン錯体類、テトラメチルスズ、テ
トラエチルスズなどのアルキルスズ類、テトラフェニル
スズなどの有機スズ化合物類、一般式■；
５ｎＸ
ａ ４−ａ （ＶＤ（式中、Ｒは
水素原子または炭素数１〜２０の炭化水素基、Ｘは塩素
原子、フッ素原子などのハロゲン原子、アルコキシ基、
カルボン酸残基、ａは前記と同じ）で表わされる化合物
、一般式■：
Ｒ２ＳｎＯ■
（式中、Ｒは前記と同じ）で表わされる化合物などがあ
げられるが、これらに限定されるものではない。5n(OR1) Y fl[D-a
Tetravalent tin partial alkoxides represented by a (wherein R1 is the same as above, Y is a functional group having chelating ability or a halogen atom, and a is an integer of 1 to 3), general formula (1) , general formula (1), a condensation polymer of a compound represented by general formula l, general formula ■: Sn (OCOR2)2 (tV) (wherein R2 is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms) General 2M: Tetravalent tin carboxylates represented by Sn (OCOR2)4 (Vl (in the formula, R2 is the same as above), divalent or β-diketone complexes that are reaction products of tetravalent tin and acetylacetone, benzoylacetone, etc., tinoxyβ-diketone complexes, alkyltins such as tetramethyltin and tetraethyltin, organic tin compounds such as tetraphenyltin, General formula ■; 5nX a 4-a (VD (in the formula, R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
Examples include, but are not limited to, compounds represented by a carboxylic acid residue (a is the same as above), compounds represented by the general formula: R2SnO (wherein R is the same as above), etc. .
前記一般式（１）で示される化合物の具体例としては、
ジェトキシスズ、ジプロポキシスズ、ジー２−エチルヘ
キソキシスズ、ジプロポキシスズなど、
一般式（１）で示される化合物の具体例としては、テト
ラエトキシスズ、テトラプロポキシスズ、テトラブトキ
シスズ、テトラキス（２−エチルヘキソキシ）スズ、テ
トラステアロキシスズなど、一般式ｌで示される化合物
の具体例としては、スズブトキシジクロライド、トリス
テアロキシスズモノクロライドなど、
一般式■で示される化合物の具体例としては、酢酸第１
スズ、シュウ酸第１スズ、酒石酸第１スズ、オクチル酸
第１スズ、オレイン酸第１スズ、リノール酸第１スズ、
ステアリン酸第１スズなど、
一般式Ｍで示される化合物の具体例としては、酢酸第２
スズ、乳酸第２スズ、酪酸第２スズ、オクチル酸第２ス
ズ、リノール酸第２スズなど、一般式■で示される化合
物の具体例としては、ジオクチルスズジアセテート、ジ
エチルスズオキサイド、ジブチルスズマレエート、ジフ
ェニルスズジクロライド、ジベンジルスズジヒドロキシ
ド、トリブチルスズラウレート、ジブチルスズラウレー
ト、ジブチルスズプロポキシド、ジビニルスズジクロラ
イドなど、
一般式■で示される化合物としては、酸化ジ−ｎ−ブチ
ルスズなど
があげられる。これらの化合物は単独で用いてもよく、
２８１以上混合して用いてもよいが、有機溶媒に可溶で
、３５０℃以下の加熱で無機スズ化合物に分解するもの
がとくに好ましい。Specific examples of the compound represented by the general formula (1) include:
Specific examples of the compound represented by the general formula (1) include jetoxytin, dipropoxytin, di-2-ethylhexoxytin, dipropoxytin, tetraethoxytin, tetrapropoxytin, tetrabutoxytin, tetrakis(2- Specific examples of compounds represented by the general formula 1, such as ethylhexoxytin, tetrastearoxytin, etc., include tin butoxy dichloride, tristearoxytin monochloride, etc. Specific examples of compounds represented by the general formula
tin, stannous oxalate, stannous tartrate, stannous octylate, stannous oleate, stannous linoleate,
Specific examples of compounds represented by the general formula M, such as stannous stearate, include stannous acetate.
Specific examples of compounds represented by the general formula (■), such as tin, stannic lactate, stannic butyrate, stannic octylate, and stannic linoleate, include dioctyltin diacetate, diethyltin oxide, and dibutyltin maleate. , diphenyltin dichloride, dibenzyltin dihydroxide, tributyltin laurate, dibutyltin laurate, dibutyltin propoxide, divinyltin dichloride, etc. Examples of the compound represented by the general formula (2) include di-n-butyltin oxide. These compounds may be used alone,
Although a mixture of 281 or more compounds may be used, it is particularly preferable to use a compound that is soluble in an organic solvent and decomposes into an inorganic tin compound when heated at 350° C. or lower.
本発明に聴いて、多孔性酸化スズ薄膜をつるばあい、塗
布溶液中に多官能性有機化合物を添加するが、その多官
能性有機化合物としては、たとえばハロゲン原子、アミ
ノ基、イミド基、カルボキシル基、カルボニル基、水酸
基、エポキシ基などの同種または異種の官能基を分子内
に２個以上含む化合物があげられ、これらのうちでも分
子内に水酸基を２個以上含む有機化合物がとくに好まし
い。According to the present invention, when a porous tin oxide thin film is coated, a polyfunctional organic compound is added to the coating solution. Examples of the polyfunctional organic compound include halogen atoms, amino groups, imide groups, carboxyl Among these, organic compounds containing two or more hydroxyl groups in the molecule are particularly preferred.
分子内に水酸基を２個以上含む有機化合物としては、と
くにアルコール性水酸基を含むものが好ましく、多価ア
ルコール類、デンプン、セルロースなどがあげられる。As the organic compound containing two or more hydroxyl groups in the molecule, those containing alcoholic hydroxyl groups are particularly preferred, and include polyhydric alcohols, starch, cellulose, and the like.
これらの具体例としては、たとえばグリセリン、１，４
−ブタンジオール、ペンタエリスリトール、デキストリ
ン、アルギン酸、メチルセルロース、ヒドロキシエチル
セルロース、カルボキシメチルセルロース、カルボキシ
メチルデンプン、ヒドロキシエチルデンプン、ポリビニ
ルアルコールなどの１種または２種以上の混合物があげ
られる。Specific examples of these include glycerin, 1,4
- One or a mixture of two or more of butanediol, pentaerythritol, dextrin, alginic acid, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carboxymethyl starch, hydroxyethyl starch, polyvinyl alcohol, and the like.
アルカリ金属やアルカリ土類金属を与えるために用いる
アルカリ金属化合物およびアルカリ土類金属化合物とし
ては、有機溶媒に可溶な無機、有機化合物を用いること
ができるが、具体的には酢酸塩、オクチル酸塩などのカ
ルボン酸塩、ナトリウムエチラートなどのアルコキシド
、アセチルアセトナートなどの金属錯体などが用いられ
る。As the alkali metal compounds and alkaline earth metal compounds used to provide alkali metals and alkaline earth metals, inorganic and organic compounds that are soluble in organic solvents can be used, but specifically acetate, octylic acid, etc. Carboxylate salts such as salts, alkoxides such as sodium ethylate, metal complexes such as acetylacetonate, etc. are used.
カルボン酸塩としては、たとえば酢酸カリウム、酢酸ナ
トリウム、オクチル酸ナトリウム、オクチル酸リチウム
、オクチル酸マグネシウム、オクチル酸カルシウム、オ
クチル酸ストロンチウム、オクチル酸バリウムなど、ア
ルコキシドとしては、たとえばナトリウムメチラート、
ナトリウムエチラート、マグネシウムエトキシドなど、
金属錯体としては、たとえばストロンチウムアセチルア
セトナート、バリウムアセチルアセトナートなどがあげ
られる。Examples of carboxylates include potassium acetate, sodium acetate, sodium octylate, lithium octylate, magnesium octylate, calcium octylate, strontium octylate, and barium octylate; examples of alkoxides include sodium methylate,
Sodium ethylate, magnesium ethoxide, etc.
Examples of the metal complex include strontium acetylacetonate and barium acetylacetonate.
また、上記化合物以外にも、水酸化ナトリウム、水酸化
カリウムなどの無機化合物を用いてもよい。In addition to the above compounds, inorganic compounds such as sodium hydroxide and potassium hydroxide may also be used.
本発明に用いる有機溶液は、有機スズ化合物と多官能性
有機化合物とを、たとえば共通溶媒に溶解してえられる
。The organic solution used in the present invention can be obtained by dissolving an organotin compound and a polyfunctional organic compound in, for example, a common solvent.
共通溶媒としては、たとえばメチルアルコール、エチル
アルコール、イソプロピルアルコール、ブチルアルコー
ル、ペンタノールなどの１価アルコール類；エチレング
リコール、グリセリン、■、４−ブタンジオールなどの
多価アルコール類；酢酸エチル、酢酸プロピル、酢酸イ
ソアミル、蟻酸プロピルなどのカルボン酸エステル類；
アセトン、アセチルアセトン、ジエチルケトン、メチル
エチルケトンなどのケトン類；ベンゼン、トルエン、キ
シレンなどの芳香族溶媒類；ジオキサン、テトラヒドロ
フランなどのエーテル類；メチルセロソルブ、エチルセ
ロソルブなどのグリコールエーテル類−Ｎ−メチル−２
−ビロリドン、ジメチルホルムアミド、ジメチルアセト
アミドなどのチッ素含有有機溶媒類などがあげられるが
、これらに限定されるものではない。これらの有機溶媒
は単独で用いてもよく、２種以上混合して用いてもよい
。これらの溶媒は、用いる有機スズ化合物と多官能性有
機化合物の種類や組合わせによって、適宜選ばれる。Examples of common solvents include monohydric alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and pentanol; polyhydric alcohols such as ethylene glycol, glycerin, and 4-butanediol; ethyl acetate and propyl acetate. , carboxylic acid esters such as isoamyl acetate and propyl formate;
Ketones such as acetone, acetylacetone, diethyl ketone, and methyl ethyl ketone; Aromatic solvents such as benzene, toluene, and xylene; Ethers such as dioxane and tetrahydrofuran; Glycol ethers such as methyl cellosolve and ethyl cellosolve - N-methyl-2
Examples include, but are not limited to, nitrogen-containing organic solvents such as pyrrolidone, dimethylformamide, and dimethylacetamide. These organic solvents may be used alone or in combination of two or more. These solvents are appropriately selected depending on the type and combination of the organotin compound and polyfunctional organic compound used.
本発明の方法の好ましい実施態様としては、たとえば、
有機スズ化合物と多官能性有機化合物とを共通溶媒に溶
解させ、好ましくは熱処理により反応せしめた溶液を基
板上に塗布後、加熱して熱分解させる方法があげられる
。共通溶媒に溶解させたのちの熱処理は、有機スズ化合
物と多官能性有機化合物との反応を促進させるために行
なうものであり、溶媒の沸点以下で還流させるのが好ま
しい。Preferred embodiments of the method of the invention include, for example:
An example of this method is to dissolve an organic tin compound and a polyfunctional organic compound in a common solvent, preferably to cause a reaction by heat treatment, apply a solution onto a substrate, and then heat the solution to thermally decompose it. The heat treatment after dissolving in the common solvent is carried out to promote the reaction between the organotin compound and the polyfunctional organic compound, and is preferably refluxed at a temperature below the boiling point of the solvent.
有機スズ化合物を含む溶液を基板上に塗布する方法とし
ては、通常行なわれている方法、すなわち、浸漬塗布法
、スプレー法、スピンコーティング法などのどの方法で
もよい。The solution containing the organic tin compound may be applied onto the substrate by any of the commonly used methods, such as dip coating, spray coating, and spin coating.
本発明に用いる基板材料とじ−では、通常用いられる基
板材料が使用できるが、具体的にはソーダガラス、石英
ガラスなどのガラス基板、アルミナなどのセラミックス
基板、あるいはステンレス、シリコン、ポリイミドフィ
ルムなどがあげられる。For the substrate material binding used in the present invention, commonly used substrate materials can be used, but specific examples include glass substrates such as soda glass and quartz glass, ceramic substrates such as alumina, stainless steel, silicon, and polyimide films. It will be done.
基板上に塗布したのち乾燥するばあいの温度にもとくに
限定はなく、溶媒が揮発する温度であればよい。従って
使用する溶媒によっても異なるが、通常５０〜３００℃
が適している。There is no particular limitation on the temperature at which the solvent is dried after being applied onto the substrate, as long as the temperature is such that the solvent evaporates. Therefore, although it varies depending on the solvent used, it is usually 50 to 300℃.
is suitable.
乾燥後の加熱処理温度としては、有機スズ化合物が熱分
解により酸化スズに変る温度以上であればよく、通常３
５０℃程度以上を要するが、再現性に優れた感湿体薄膜
をうるためには４００℃程度以上で焼成するのが望まし
い。焼成温度が高すぎると薄膜の緻密化が促進されるた
め良好な感湿特性かえられにくくなってしまう。そのた
め基板材料にもよるが、■０００℃程度以下、さらには
８００℃程度以下であるのが好ましい。The heat treatment temperature after drying should be at least the temperature at which the organic tin compound turns into tin oxide through thermal decomposition, and is usually 3.
The firing temperature is approximately 50° C. or higher, but it is desirable to bake at approximately 400° C. or higher in order to obtain a moisture-sensitive thin film with excellent reproducibility. If the firing temperature is too high, the densification of the thin film will be promoted, making it difficult to obtain good moisture sensitivity characteristics. Therefore, although it depends on the substrate material, the temperature is preferably about 000°C or less, more preferably about 800°C or less.
酸化スズに分解する焼成時の雰囲気としては、チッ素な
どの不活性ガス雰囲気もしくは酸素を含む雰囲気下で行
なうのが好ましい。The firing atmosphere for decomposition into tin oxide is preferably an atmosphere of an inert gas such as nitrogen or an atmosphere containing oxygen.
本発明においてアルカリ金属やアルカリ土類金属を酸化
スズに添加する方法として、塗布溶液中にアルカリ金属
やアルカリ土類金属を添加することなしに、アルカリ金
属やアルカリ土類金属を含む基板上に製膜し、加熱処理
することで、酸化スズ薄膜中に基板から拡散によってア
ルカリ金属やアルカリ土類金属を含有させることも可能
である。In the present invention, as a method for adding an alkali metal or an alkaline earth metal to tin oxide, the method of adding an alkali metal or an alkaline earth metal to tin oxide is to produce a product on a substrate containing an alkali metal or an alkaline earth metal without adding the alkali metal or alkaline earth metal to the coating solution. By forming a film and subjecting it to heat treatment, it is also possible to contain alkali metals and alkaline earth metals by diffusion from the substrate into the tin oxide thin film.
溶液中の金属含有量は、塗布時の加水分解速度が適切に
なるべく、また膜厚の調整のために適宜選択する必要が
あるが、通常０．５〜２０重量％、とくに３〜１０重量
％が好ましく、多官能性有機化合物の比率は、その種類
や有機スズ化合物の種類や量によって変わるが、通常有
機スズ化合物に対して０．５〜１００％、とくに５〜３
０％の範囲でよい結果かえられる。The metal content in the solution needs to be selected appropriately to achieve an appropriate hydrolysis rate during coating and to adjust the film thickness, but it is usually 0.5 to 20% by weight, particularly 3 to 10% by weight. is preferable, and the ratio of the polyfunctional organic compound varies depending on the type and amount of the organic tin compound, but is usually 0.5 to 100%, particularly 5 to 3%, based on the organic tin compound.
Good results can be obtained within the range of 0%.
また、本発明においては、本発明の目的を妨げない無機
または有機金属塩、増粘剤、安定剤などを添加してもよ
い。In addition, in the present invention, inorganic or organic metal salts, thickeners, stabilizers, etc. may be added that do not interfere with the purpose of the present invention.
なお、本発明によってえられる酸化スズ感湿体薄膜は、
湿度センサとして使用する上で充分な長期安定性を有し
ている。Note that the tin oxide moisture sensitive thin film obtained by the present invention is
It has sufficient long-term stability for use as a humidity sensor.
つぎに、実施例に基づき本発明を説明するが、本発明は
かかる実施例によって限定されるものではない。Next, the present invention will be explained based on Examples, but the present invention is not limited by these Examples.
実施例１
スズテトラブトキシド１０ｇを１００ｇのｎ−プロピル
アルコールに溶解させたのち、オクチル酸ナトリウムを
０．３ｇ添加し、さらに３％ヒドロキシプロピルセルロ
ースを含むエチルアルコール溶液を１０ｇ加え、充分撹
拌して透明な均一溶液をえた。えられた溶液を、アルミ
ナ基板上に１５ｃｏ＋／分の引上げ速度で浸漬塗布し、
８０℃の空気中で乾燥後、マツフル炉にて１０℃／分の
昇温速度で６００℃まで昇温し、１時間保持したのち放
冷して、均質な酸化スズ薄膜をえた。Example 1 After dissolving 10 g of tin tetrabutoxide in 100 g of n-propyl alcohol, 0.3 g of sodium octylate was added, and then 10 g of an ethyl alcohol solution containing 3% hydroxypropyl cellulose was added, and the mixture was thoroughly stirred to form a transparent solution. A homogeneous solution was obtained. The obtained solution was dip coated onto an alumina substrate at a pulling rate of 15 co+/min,
After drying in air at 80°C, the temperature was raised to 600°C at a heating rate of 10°C/min in a Matsufuru furnace, maintained for 1 hour, and then allowed to cool to obtain a homogeneous tin oxide thin film.
えられた酸化スズ薄膜は透明性を有しており、走査型電
子顕微鏡による観察の結果、膜厚約０．３−で０．２
Ｊ１以下の孔径の細孔を有する均一性のある多孔性酸化
スズ薄膜であった。The obtained tin oxide thin film has transparency, and as a result of observation with a scanning electron microscope, the film thickness is about 0.3-0.2
It was a uniform porous tin oxide thin film having pores with a pore diameter of J1 or less.
この膜表面上に金の櫛形電極（電極間隔０．２■、電極
総長２０ｈａ）を真空蒸着法により設置し、感湿体素子
を作製した。この感湿体の感湿特性を測定したところ、
相対湿度に対するインピーダンス変化が、対数目盛で直
線的であり１０〜９５％Ｉ？Ｈの間で約３桁の変化があ
った。また、応答速度も速く良好な感湿体膜であった。Gold comb-shaped electrodes (electrode spacing: 0.2 square meters, electrode total length: 20 ha) were placed on the surface of this film by vacuum evaporation to produce a moisture-sensitive element. When we measured the moisture-sensing characteristics of this moisture-sensitive body, we found that
The impedance change with respect to relative humidity is linear on a logarithmic scale and is 10 to 95% I? There was a change of about 3 orders of magnitude between H. Moreover, the response speed was fast and the moisture sensitive film was good.
さらに、インピーダンスの経時変化もほとんどなかった
。Furthermore, there was almost no change in impedance over time.
実施例２
スズテトライソプロポキシドｌｏｇを１００ｇの無水イ
ソプロピルアルコールに溶解させ、さらに５％のグリセ
リンを含むエチルアルコール溶液を２０ｇ撹拌しながら
、加えて、均一溶液とした。Example 2 Log tin tetraisopropoxide was dissolved in 100 g of anhydrous isopropyl alcohol, and 20 g of an ethyl alcohol solution containing 5% glycerin was added with stirring to form a homogeneous solution.
えられた溶液を、実施例１と同様、金の櫛型電極を真空
蒸着法により設置したソーダライムガラス基板上に１５
０１１／分の引上げ速度で浸漬塗布し、実施例１と同様
にして、マツフル炉中５００℃で焼成することにより、
マグネシウムを含有した透明な酸化スズ薄膜をえた。こ
の酸化スズ膜の膜厚は、走査型電子顕微鏡観察の結果約
０．４虜であり、０．５」以下の孔径の細孔を有する多
孔性酸化スズ薄膜であった。As in Example 1, the obtained solution was placed on a soda lime glass substrate on which a gold comb-shaped electrode was placed by vacuum evaporation.
By dip coating at a pulling rate of 0.011/min and baking at 500°C in a Matsufuru furnace in the same manner as in Example 1,
A transparent tin oxide thin film containing magnesium was obtained. The thickness of this tin oxide film was found to be about 0.4 mm as a result of observation using a scanning electron microscope, and it was a porous tin oxide thin film having pores with a pore diameter of 0.5'' or less.
この酸化スズ薄膜の感湿体素子の感湿特性を測定したと
ころ、１０〜９５％ＲＨの相対湿度変化に対して、イン
ピーダンスが対数目盛で直線的に変化し、その変化量は
約３桁であり、湿度センサとして充分な感湿特性を示し
た。When we measured the moisture-sensing characteristics of this tin oxide thin film moisture-sensitive element, we found that the impedance changed linearly on a logarithmic scale in response to changes in relative humidity from 10 to 95% RH, and the amount of change was about 3 orders of magnitude. It showed sufficient moisture sensitivity characteristics as a humidity sensor.
実施例３
オクチル酸スズ（Ｉｌ溶液（石油エーテル系溶媒）２０
ｇをｎ−ブチルアルコール１００ｇに溶解させ、ストロ
ンチウムアセチルアセトナートを２．０ｇ添加し、さら
にジエチレングリコールを５０％含むエチルアルコール
溶液を３０ｇ添加して加熱しながら充分撹拌して、均一
な透明溶液をえた。この溶液を実施例１と同様にして、
金の櫛形電極を設置した石英ガラス基板上に塗布し、空
気中１２０℃で乾燥したのち、マツフル炉中、８００℃
で２０分間加熱することにより、透明な酸化スズ感湿体
薄膜素子をえた。 ２この感湿
体薄膜素子の感湿特性を測定したところ、相対湿度１０
％ＲＨから９５％ＲＨにかけてインピーダンスが直線的
に約４桁変化した。Example 3 Tin octylate (Il solution (petroleum ether solvent) 20
g was dissolved in 100 g of n-butyl alcohol, 2.0 g of strontium acetylacetonate was added, and 30 g of an ethyl alcohol solution containing 50% diethylene glycol was added and thoroughly stirred while heating to obtain a uniform transparent solution. . This solution was prepared in the same manner as in Example 1,
It was coated on a quartz glass substrate equipped with gold comb-shaped electrodes, dried in air at 120°C, and then heated in a Matsufuru furnace at 800°C.
By heating for 20 minutes, a transparent tin oxide moisture-sensitive thin film element was obtained. 2 When we measured the moisture sensitivity characteristics of this moisture sensitive thin film element, we found that the relative humidity was 10
The impedance changed linearly by about 4 orders of magnitude from %RH to 95%RH.
上記実施例における相対湿度とインピーダンス値との関
係は第１図のグラフ（１）に示すように直線的な関係に
あった。The relationship between the relative humidity and the impedance value in the above example was a linear relationship as shown in graph (1) of FIG.
比較例１
従来のセラミックス湿度センサーの相対湿度とインピー
ダンス値との関係を第１図のグラフ（′２Ｊに示す。Comparative Example 1 The relationship between relative humidity and impedance value of a conventional ceramic humidity sensor is shown in the graph of FIG. 1 ('2J).
［発明の効果］
本発明による効果としては、従来の感湿体と比較して、
相対湿度に対するインピーダンス変化が直線的であり、
出力変換回路が低コストになること、高速応答性である
こと、薄膜素子であることによる小型インテリジェント
化が可能なこと、安価な原料から容易に製造できるため
、製造コストが安易になることなどがあげられる。[Effects of the Invention] The effects of the present invention are as follows compared to conventional moisture sensitive bodies:
Impedance change with relative humidity is linear,
The output conversion circuit is low-cost, has high-speed response, can be made compact and intelligent because it is a thin film element, and can be easily manufactured from inexpensive raw materials, so manufacturing costs are low. can give.
第１図は、本発明の方法によりえられた本発明の多孔性
酸化スズ感湿体薄膜を有する湿度センサおよび従来のセ
ラミックス湿度センサを用いて測定した相対湿度とイン
ピーダンス値との関係を示すグラフである。
特許出願人 鐘淵化学工業株式会社FIG. 1 is a graph showing the relationship between relative humidity and impedance values measured using a humidity sensor having a porous tin oxide moisture-sensitive thin film of the present invention obtained by the method of the present invention and a conventional ceramic humidity sensor. It is. Patent applicant Kanebuchi Chemical Industry Co., Ltd.
Claims (1)
る多孔性酸化スズ感湿体薄膜。 ２ 酸化スズ薄膜が、アルカリ金属およびアルカリ土類
金属から選ばれた少なくとも１種の金属をスズに対して
０．１モル％以上含有するものからなる請求項１記載の
多孔性酸化スズ感湿体薄膜。 ３ 有機スズ化合物と多官能性有機化合物とを含む溶液
を基板上に塗布し、乾燥後、加熱処理して請求項１記載
の多孔性酸化スズ感湿体薄膜を製造する方法。[Scope of Claims] 1. A porous tin oxide moisture-sensitive thin film having pores with a diameter of 10 μm or less provided on a substrate. 2. The porous tin oxide moisture sensitive material according to claim 1, wherein the tin oxide thin film contains at least 0.1 mol% of at least one metal selected from alkali metals and alkaline earth metals based on tin. Thin film. 3. A method for producing a porous tin oxide moisture-sensitive thin film according to claim 1, by applying a solution containing an organic tin compound and a polyfunctional organic compound onto a substrate, drying, and then heat-treating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63124631A JPH01293501A (en) | 1988-05-20 | 1988-05-20 | Porous tin oxide moisture-sensitive thin film and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63124631A JPH01293501A (en) | 1988-05-20 | 1988-05-20 | Porous tin oxide moisture-sensitive thin film and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01293501A true JPH01293501A (en) | 1989-11-27 |
Family
ID=14890194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63124631A Pending JPH01293501A (en) | 1988-05-20 | 1988-05-20 | Porous tin oxide moisture-sensitive thin film and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01293501A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03238349A (en) * | 1990-02-16 | 1991-10-24 | Koroido Res:Kk | Humidity sensor |
| JPH06120003A (en) * | 1992-09-30 | 1994-04-28 | Taiyo Yuden Co Ltd | Tin oxide thin film resistor and manufacture thereof |
| JP2011112359A (en) * | 2009-11-24 | 2011-06-09 | Figaro Engineerign Inc | METHOD OF MANUFACTURING SnO2 GAS SENSOR |
-
1988
- 1988-05-20 JP JP63124631A patent/JPH01293501A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03238349A (en) * | 1990-02-16 | 1991-10-24 | Koroido Res:Kk | Humidity sensor |
| JPH06120003A (en) * | 1992-09-30 | 1994-04-28 | Taiyo Yuden Co Ltd | Tin oxide thin film resistor and manufacture thereof |
| JP2011112359A (en) * | 2009-11-24 | 2011-06-09 | Figaro Engineerign Inc | METHOD OF MANUFACTURING SnO2 GAS SENSOR |
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