JPS63243260A - Production of nitrogen oxide detecting element - Google Patents
Production of nitrogen oxide detecting elementInfo
- Publication number
- JPS63243260A JPS63243260A JP7890987A JP7890987A JPS63243260A JP S63243260 A JPS63243260 A JP S63243260A JP 7890987 A JP7890987 A JP 7890987A JP 7890987 A JP7890987 A JP 7890987A JP S63243260 A JPS63243260 A JP S63243260A
- Authority
- JP
- Japan
- Prior art keywords
- nitrogen oxide
- phthalocyanine
- film
- vapor
- insulating 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.)
- Granted
Links
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 238000000151 deposition Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- WSQYJDCCFQPFJC-UHFFFAOYSA-N ac1lcry1 Chemical compound [Pb+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 WSQYJDCCFQPFJC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001514 detection method Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 239000010408 film Substances 0.000 description 19
- 239000010409 thin film Substances 0.000 description 9
- 238000007740 vapor deposition Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005092 sublimation method Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、窒素酸化物検出素子の製造法に関する。更に
詳しくは、フタロシアニン−金属錯体系の薄膜を用いた
窒素酸化物検出素子に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for manufacturing a nitrogen oxide detection element. More specifically, the present invention relates to a nitrogen oxide detection element using a phthalocyanine-metal complex thin film.
フタロシアニンまたはその金属錯体の薄膜についてのガ
ス感応性が検討されており、この場合の薄膜の形成は、
フタロシアニンまたはその金属錯体を溶解させる適当な
溶媒がないため、真空下に加熱する昇華法を利用する製
膜法がとられている（Ｊ、Ｐｈｙｓ、Ｃｈｅｍ、５ｏ１
ｉｄｓ第１ｉｄｓ８３３〜８３８頁、１９８３）。The gas sensitivity of thin films of phthalocyanine or its metal complexes has been investigated, and the formation of thin films in this case is
Since there is no suitable solvent for dissolving phthalocyanine or its metal complex, a film forming method using a sublimation method using heating under vacuum has been adopted (J, Phys, Chem, 5o1
ids 1 ids pp. 833-838, 1983).
しかしながら、このような昇華法によって製膜されたフ
タロシアニン−金属錯体系の薄膜は、その膜強度が弱く
、検出素子などとして用いる場合に、その耐久性に問題
がみられた。However, the phthalocyanine-metal complex thin film formed by such a sublimation method has a weak film strength, and there have been problems with its durability when used as a detection element or the like.
そこで本発明者らは、フタロシアニン−金属錯体系の薄
膜の膜強度を向上せしめる方法を求めて検討を重ねた結
果、この薄膜をプラズマ状態にして蒸着させると、フタ
ロシアニンの一部がポリマー化して膜強度を増加させる
ことを見出し、更にこの蒸着膜を加熱処理して結晶性を
増加させることにより、窒素酸化物ガスが膜中に吸着さ
れることなく１表面に接触するのみで抵抗を変化させる
ようになると考えられる結果として、応答速度の向上が
図られることも同時に見出した。Therefore, the present inventors conducted repeated studies in search of a method to improve the film strength of phthalocyanine-metal complex thin films, and found that when this thin film is vapor-deposited in a plasma state, part of the phthalocyanine becomes polymerized and forms a film. By heat-treating this vapor-deposited film to increase its crystallinity, the nitrogen oxide gas was not adsorbed into the film, but was able to change its resistance just by contacting one surface. At the same time, we have also found that the response speed can be improved as a result of this.
従って、本発明は窒素酸化物検出素子の製造法に係り、
窒素酸化物検出素子の製造は、絶縁性基板上にフタロシ
アニン−金属錯体を高周波電力により空中でプラズマ状
態にして蒸着させた後、形成された蒸着膜を加熱処理す
ることにより行われる。Therefore, the present invention relates to a method for manufacturing a nitrogen oxide detection element,
The nitrogen oxide detection element is manufactured by depositing a phthalocyanine-metal complex on an insulating substrate in a plasma state in the air using high-frequency power, and then heat-treating the deposited film.
この蒸着膜の絶縁性基板上への形成は、絶縁性基板上へ
直接行なってその後くし形電極などの電極を蒸着膜上に
形成させる方法あるいは絶縁性基板上にくし形電極など
の電極を形成させた後その上に蒸着膜を形成させる方法
のいずれでも行なうことができる。This vapor deposited film can be formed on an insulating substrate by directly forming an electrode such as a comb-shaped electrode on the vapor-deposited film after directly forming it on the insulating substrate, or by forming an electrode such as a comb-shaped electrode on an insulating substrate. Any method may be used in which a vapor-deposited film is formed thereon.
図面の第２図に示される態様は、上記前者の場合であり
、ガラス板などの絶縁性基板１１上に蒸着膜１２を形成
させた後、くシ形電極１３．１３ ’をその上に形成さ
せている。The embodiment shown in FIG. 2 of the drawings is the former case, in which a vapor deposited film 12 is formed on an insulating substrate 11 such as a glass plate, and then a comb-shaped electrode 13, 13' is formed thereon. I'm letting you do it.
フタロシアニン−金属錯体としては、例えば鉛錯体、鉄
錯体、コバルト錯体、ニッケル錯体、銅錯体、亜鉛錯体
などが用いられ、それの高周波電力による空中プラズマ
状態での蒸着は、第１図に示されるような装置を用いて
次のようにして行われる。Examples of phthalocyanine-metal complexes used include lead complexes, iron complexes, cobalt complexes, nickel complexes, copper complexes, and zinc complexes. It is carried out as follows using a suitable device.
蒸着装置の本体容器１内には、高周波電源２に接続され
た基板台電極３および直流型ｇ４に接続されたタングス
テン製またはモリブデン製の蒸着ボート５がそれぞれ設
置されており、基板台電極には必要なマスキングを施し
た絶縁性基板６が取り付けられ、また蒸着ボート内には
フタロシアニン−金属錯体７が収容されている。A substrate stand electrode 3 connected to a high frequency power source 2 and a tungsten or molybdenum vapor deposition boat 5 connected to a DC type g4 are installed in the main body container 1 of the vapor deposition apparatus. An insulating substrate 6 that has undergone necessary masking is attached, and a phthalocyanine-metal complex 7 is accommodated in the deposition boat.
蒸着に際しては、まずディフュージョンポンプ８および
ロータリーポンプ９を作動させることにより、本体容器
内を５ Ｘ １０−’ Ｔｏｒｒの圧力迄排気した後、
アルゴンガスをボンベ１０より導入し、圧力を約５ Ｘ
ｌｏ−４〜Ｉ Ｘ １０−’Ｔｏｒｒの範囲内に調整
し、高周波電源により基板台電極に高周波を印加して放
電させる。このときの出力は、約１０〜１００１ｊであ
る。その後、直流電源により蒸着ボートを加熱し、フタ
ロシアニン−金属錯体を放電下で蒸発させ、絶縁性基板
上に薄膜として形成させる。For vapor deposition, first, by operating the diffusion pump 8 and the rotary pump 9, the inside of the main container is evacuated to a pressure of 5 x 10-' Torr, and then
Introduce argon gas from cylinder 10 and increase the pressure to approximately 5
The voltage is adjusted within the range of lo-4 to I.times.10-' Torr, and high frequency is applied to the substrate stage electrode using a high frequency power source to cause discharge. The output at this time is about 10 to 1001j. Thereafter, the evaporation boat is heated by a DC power source, and the phthalocyanine-metal complex is evaporated under discharge to form a thin film on the insulating substrate.
このようにして形成された蒸着膜は不安定で、検出に適
すると思われる１２０〜２００℃の温度条件下では結晶
化が進み、素子抵抗が減少する方向に遷移する。そこで
、予め適当な条件下での熱処理により、膜を安定化して
おくことが必要となる。その処理温度については、４０
０℃付近でフタロシアニン−金属錯体が昇華するのでそ
の上限は約３５０℃程度であり、また下限温度は時間を
長くすることによって約１５０℃程度迄下げることがで
きる。The deposited film thus formed is unstable, and under temperature conditions of 120 to 200° C., which are considered suitable for detection, crystallization progresses and the element resistance shifts to decrease. Therefore, it is necessary to stabilize the film in advance by heat treatment under appropriate conditions. Regarding the processing temperature, 40
Since the phthalocyanine-metal complex sublimates at around 0°C, its upper limit is about 350°C, and the lower limit temperature can be lowered to about 150°C by increasing the time.
その後、蒸着膜上にくし形電極が形成される。Thereafter, comb-shaped electrodes are formed on the deposited film.
〔作用〕および〔発明の効果〕
本発明にかかる窒素酸化物検出素子は、素子表面に吸着
する窒素酸化物ガスおよび脱離するこのガスが平衡に達
したときの抵抗値と検量線より濃度を知ることができ、
サンプリングすることなく、実時間で計測が可能である
。[Function] and [Effects of the Invention] The nitrogen oxide detection element according to the present invention can calculate the concentration from the resistance value and the calibration curve when nitrogen oxide gas adsorbed on the element surface and this gas desorbed reach equilibrium. can know,
Measurement can be performed in real time without sampling.
また、その検出は薄膜によって行われるため。Also, because the detection is done by a thin film.
応答時間の短縮化が図れるが、このように作用する薄膜
が本発明方法で製造されると、普通の蒸着膜はセロハン
テープ剥離試験に耐えないが、それに耐え得るようにな
るなどその膜強度の点での問題はなく、検出素子などと
して用いた場合耐久性の点ですぐれている。Although the response time can be shortened, if a thin film that acts in this way is produced by the method of the present invention, the strength of the film will be improved, such as being able to withstand the cellophane tape peeling test, whereas ordinary vapor-deposited films cannot withstand the cellophane tape peeling test. There are no problems with this, and it has excellent durability when used as a detection element.
この窒素酸化物検出素子は、数ＩＩＩＩＩ＋角程度の大
きさで作製することができ、また表示部も小型化できる
ので、ポータプルな計測器として構成することができ、
他のセンサとの複合化も容易である。This nitrogen oxide detection element can be manufactured with a size of about several III+ squares, and the display part can also be made smaller, so it can be configured as a portable measuring instrument.
It is also easy to combine with other sensors.
次に、実施例について本発明を説明する。 Next, the present invention will be explained with reference to examples.
実施例
ガラス基板（２０Ｘ２０Ｘ０．８ｍｍ）上に、フタロシ
アニン−鉛錯体の蒸着膜を、第１図に図示された蒸着装
置を用いて形成させた。蒸着条件は、アルゴンガス圧力
５ Ｘ １０−’Ｔｏｒｒ、有効電力５０１である。そ
の後、蒸着膜形成ガラス基板を、２００℃の加熱雰囲気
に１０時間放置して加熱処理し、更にその上に蒸着法に
よりくし彫金電極を形成させた。EXAMPLE A vapor deposition film of a phthalocyanine-lead complex was formed on a glass substrate (20×20×0.8 mm) using the vapor deposition apparatus shown in FIG. The deposition conditions were argon gas pressure of 5 x 10-'Torr and effective power of 501. Thereafter, the glass substrate on which the vapor-deposited film had been formed was left in a heated atmosphere at 200° C. for 10 hours for heat treatment, and furthermore, a comb-engraved electrode was formed thereon by a vapor deposition method.
このようにして形成された素子を、空気希釈二酸化窒素
について、流通系雰囲気温度１２０℃で、二酸化窒素濃
度と抵抗値との関係を測定した・得られた結果は、第３
図のグラフに示される。The relationship between the nitrogen dioxide concentration and the resistance value of the element thus formed was measured using air-diluted nitrogen dioxide at a flow system ambient temperature of 120°C.
As shown in the graph of figure.
第１図は１本発明方法で用いられる蒸着装置の一態様の
概略図である。第２図は、本発明に係る窒素酸化物検出
素子の一態様の平面図である。また、第３図は、この検
出素子を用いて測定した二酸化窒素濃度と抵抗値との関
係を示すグラフである。
（符号の説明）
２・・・・・高周波電源
３・・・・・基板台電極
４・・・・・直流電源
５・・・・・蒸着ボート
６・・・・・絶縁性基板
７・・・・・フタロシアニン−金、ａｉｌｌｌｔ体１１
・・・・・絶縁性基板
１２・・・・・蒸着膜
１３・・・・・くし形電極
第１図FIG. 1 is a schematic diagram of one embodiment of a vapor deposition apparatus used in the method of the present invention. FIG. 2 is a plan view of one embodiment of the nitrogen oxide detection element according to the present invention. Moreover, FIG. 3 is a graph showing the relationship between nitrogen dioxide concentration and resistance value measured using this detection element. (Explanation of symbols) 2... High frequency power supply 3... Substrate stand electrode 4... DC power supply 5... Vapor deposition boat 6... Insulating substrate 7... ...phthalocyanine-gold, ailllt body 11
... Insulating substrate 12 ... Deposited film 13 ... Comb-shaped electrode Fig. 1
Claims (1)
波電力により空中でプラズマ状態にして蒸着させた後、
形成された蒸着膜を加熱処理することを特徴とする窒素
酸化物検出素子の製造法。 ２、フタロシアニン−金属錯体がフタロシアニン−鉛錯
体である特許請求の範囲第１項記載の窒素酸化物検出素
子の製造法。 ３、加熱処理が約１５０〜３５０℃で行われる特許請求
の範囲第１項記載の窒素酸化物検出素子の製造法。[Claims] 1. After depositing a phthalocyanine-metal complex on an insulating substrate in a plasma state in the air using high-frequency power,
A method for manufacturing a nitrogen oxide detection element, which comprises heat-treating a deposited film. 2. The method for producing a nitrogen oxide detection element according to claim 1, wherein the phthalocyanine-metal complex is a phthalocyanine-lead complex. 3. The method for manufacturing a nitrogen oxide detection element according to claim 1, wherein the heat treatment is performed at about 150 to 350°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62078909A JP2521948B2 (en) | 1987-03-31 | 1987-03-31 | Manufacturing method of nitrogen oxide detection element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62078909A JP2521948B2 (en) | 1987-03-31 | 1987-03-31 | Manufacturing method of nitrogen oxide detection element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63243260A true JPS63243260A (en) | 1988-10-11 |
| JP2521948B2 JP2521948B2 (en) | 1996-08-07 |
Family
ID=13674967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62078909A Expired - Lifetime JP2521948B2 (en) | 1987-03-31 | 1987-03-31 | Manufacturing method of nitrogen oxide detection element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2521948B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5348797A (en) * | 1976-10-12 | 1978-05-02 | Cerberus Ag | Gas sensor containing metal oxide and method of preparating and using the sensor |
| JPS59123766A (en) * | 1982-12-16 | 1984-07-17 | Fujitsu Ltd | Formation of metallic film |
| JPS61183471A (en) * | 1985-02-07 | 1986-08-16 | Fujitsu Ltd | Method and device for forming thin film |
-
1987
- 1987-03-31 JP JP62078909A patent/JP2521948B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5348797A (en) * | 1976-10-12 | 1978-05-02 | Cerberus Ag | Gas sensor containing metal oxide and method of preparating and using the sensor |
| JPS59123766A (en) * | 1982-12-16 | 1984-07-17 | Fujitsu Ltd | Formation of metallic film |
| JPS61183471A (en) * | 1985-02-07 | 1986-08-16 | Fujitsu Ltd | Method and device for forming thin film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2521948B2 (en) | 1996-08-07 |
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