JPH04170003A - Thin-film thermistor and its manufacture - Google Patents
Thin-film thermistor and its manufactureInfo
- Publication number
- JPH04170003A JPH04170003A JP27162490A JP27162490A JPH04170003A JP H04170003 A JPH04170003 A JP H04170003A JP 27162490 A JP27162490 A JP 27162490A JP 27162490 A JP27162490 A JP 27162490A JP H04170003 A JPH04170003 A JP H04170003A
- Authority
- JP
- Japan
- Prior art keywords
- thermistor
- heat
- thin film
- film
- temperature
- 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 36
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010408 film Substances 0.000 claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011572 manganese Substances 0.000 claims abstract description 9
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000004544 sputter deposition Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000007740 vapor deposition Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 229910016955 Fe1-xMnx Inorganic materials 0.000 abstract 1
- 238000010292 electrical insulation Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910021332 silicide Inorganic materials 0.000 description 4
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 229910015136 FeMn Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- 206010057040 Temperature intolerance Diseases 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000008543 heat sensitivity Effects 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- XEOCKQIQXJNTER-UHFFFAOYSA-N gold palladium platinum Chemical compound [Pd].[Pd].[Pd].[Pd].[Pd].[Pt].[Pt].[Pt].[Pt].[Pt].[Pt].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au] XEOCKQIQXJNTER-UHFFFAOYSA-N 0.000 description 1
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical group [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
Landscapes
- Thermistors And Varistors (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は感熱性抵抗膜が鉄とマンガンとけい素からなる
薄膜サーミスタ及びその製造方法に関する。特に高温用
に好適な薄膜サーミスタ及びその製造方法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thin film thermistor whose heat-sensitive resistive film is made of iron, manganese, and silicon, and a method for manufacturing the same. The present invention particularly relates to a thin film thermistor suitable for high temperature applications and a method for manufacturing the same.
［従来の技術］
従来、薄膜サーミスタの感熱性抵抗膜は酸化物材料又は
非酸化物材料により構成される。前者の酸化物材料とし
ては、Ｍｎ、Ｃ０．Ｎｉの金属複合酸化物又はＭｎ、Ｃ
０．ＮｉＯ中の２〜３成分にＡ交、Ｃｒ、Ｃｕ、Ｆｅ等
の中の１つ以上の成分を加えた金属複合酸化物が知られ
ている（例えば、特開昭６２−２９１００２．特開昭６
２−２９３７０１ 、特開平１−５０５０１）。また後
者の非酸化物材料としては、炭化けい素が知られている
（例えば、特公昭５６−２６９６５ 、特開昭６１−２
４５５０２．特開平１−１３０５０３）。[Prior Art] Conventionally, a heat-sensitive resistance film of a thin film thermistor is made of an oxide material or a non-oxide material. The former oxide materials include Mn, C0. Ni metal composite oxide or Mn, C
0. Metal composite oxides are known in which two to three components of NiO are added with one or more components of A, Cr, Cu, Fe, etc. 6
2-293701, JP-A-1-50501). Silicon carbide is known as the latter non-oxide material (for example, Japanese Patent Publication No. 56-26965, Japanese Patent Application Laid-open No. 61-2
45502. JP 1-130503).
［発明が解決しようとする課題］
一般にサーミスタ用の材料では、温度係数であるＢ定数
は少なくとも１００ＯＫ以上が必要である。[Problems to be Solved by the Invention] Generally, materials for thermistors require a B constant, which is a temperature coefficient, of at least 100 OK.
しかし、前者の酸化物材料の場合に上記Ｂ定数でその抵
抗率が２５℃においては数Ω・ｃｍ以上の値となる。例
えば、電気絶縁性基板上に少なくとも１対の基底電極を
備え、これに薄膜を形成したサーミスタではその膜厚が
約２μｍ以下であることから２５℃においてその抵抗値
は数にΩ〜ＬｏｏｋΩ以上となり゛、高抵抗のサーミス
タしか作れない問題点があった。またこの高抵抗を利用
して、前者の酸化物材料で高温用サーミスタを作ると、
その組成が酸化物であることから高温時において酸化状
態が変化しサーミスタとしての特性が安定しなくなる問
題点があった。However, in the case of the former oxide material, the resistivity at 25° C. is a value of several Ω·cm or more based on the above-mentioned B constant. For example, in a thermistor that has at least one pair of base electrodes on an electrically insulating substrate and a thin film formed thereon, the film thickness is about 2 μm or less, so the resistance value at 25°C is several Ω to LookΩ or more.゛There was a problem that only high-resistance thermistors could be made. Also, if you make use of this high resistance and make a high-temperature thermistor using the former oxide material,
Since its composition is an oxide, there is a problem in that the oxidation state changes at high temperatures, making the characteristics as a thermistor unstable.
後者の炭化けい素の場合には、この材料は熱的安定性が
高いため高温に耐える特長がある反面、その抵抗率が比
較的高く、膜厚を数μｍとしても２５℃で抵抗値が数１
００にΩ以上となり、やはり高抵抗のサーミスタしか作
れない問題点があった。また炭化けい素はＢ定数が２５
℃付近において２５００に程度と低いため、酸化物材料
と異なり程々の温度係数をもつ薄膜サーミスタを作るこ
とができない問題点があった。更に炭化けい素をサーミ
スタ用の材料とする場合、その構造上けい素と炭素の組
成比の変更は難しいため、成膜条件によってのみサーミ
スタの特性を変えられるに過ぎず、各種用途にきめ細か
に対応し幅広い特性を具備したサーミスタが得がたい不
具合があった。In the case of the latter, silicon carbide, this material has high thermal stability and can withstand high temperatures, but on the other hand, its resistivity is relatively high, and even if the film thickness is several micrometers, the resistance value at 25 degrees Celsius is several micrometers. 1
However, there was a problem that only high-resistance thermistors could be made. Also, silicon carbide has a B constant of 25
Since the temperature coefficient is as low as 2,500° C., there is a problem in that unlike oxide materials, it is not possible to create a thin film thermistor with a moderate temperature coefficient. Furthermore, when using silicon carbide as a material for a thermistor, it is difficult to change the composition ratio of silicon and carbon due to its structure, so the characteristics of the thermistor can only be changed by changing the film formation conditions, making it possible to fine-tune the characteristics of the thermistor. However, there was a problem that made it difficult to obtain a thermistor with a wide range of characteristics.
本発明の目的は、上記問題点を解決するもので電気絶縁
性基板上に少なくとも１対の基底電極を備え、これに薄
膜を形成したサーミスタにおいて、少なくとも１００Ｏ
Ｋ以上のＢ定数を有し、膜厚が０．１〜２μｍ程度で数
Ω〜数１００にΩの抵抗値を有し、幅広い特性を具備す
ることができ、しかも少なくとも３００℃以上の温度で
安定性の良い薄膜サーミスタ及びその製造方法を提供す
ることにある。An object of the present invention is to solve the above-mentioned problems, and to provide a thermistor comprising at least one pair of base electrodes on an electrically insulating substrate and a thin film formed on the base electrodes.
It has a B constant of K or more, a film thickness of about 0.1 to 2 μm, a resistance value of several Ω to several 100 Ω, and can have a wide range of characteristics, and can be used at temperatures of at least 300°C or higher. An object of the present invention is to provide a thin film thermistor with good stability and a method for manufacturing the same.
［課題を解決するための手段］
本発明者らは耐熱材料として開発されたＦｅ５ｉｓ系の
バルク材料が耐酸化性にも優れ、しかも大気中で利用で
きる高温用熱電材料であること（Ｒ。[Means for Solving the Problems] The present inventors have discovered that the Fe5is-based bulk material, which was developed as a heat-resistant material, has excellent oxidation resistance and is a high-temperature thermoelectric material that can be used in the atmosphere (R.
Ｋｉｅｆｆｅｒ、 Ｆ、Ｂｅｎｅｓｏｖｓｋｙ ａｎｄ
Ｃ，Ｋｏｎｏｐｉｃｋｙ： Ｂｅｒ。Kieffer, F., Benesovsky and
C, Konopicky: Ber.
Ｄｅｕｎｔ、 Ｋｅｒａｍ、 Ｇｅｓ、、３１ （１９
５４） ２２３など）、また９８６℃までは状態図上安
定な材料であって（Ｊ。Deunt, Keram, Ges, 31 (19
54) 223, etc.), and is a stable material on the phase diagram up to 986°C (J.
Ｐ、Ｐｉｔｏｎ ａｎｄ ＭＪ：、Ｆａｙ： Ｃ，Ｒ，
Ａｃａｄ、 Ｓｃｉ、、Ｃ２６６（１９６８） １５４
） 、Ｌかもこの材料が半導体材料としても用いられて
いることに着目し、この材料を薄膜化することにより、
上記目的を達成できることを見出し、本発明に到達した
。P, Piton and MJ:, Fay: C,R,
Acad, Sci., C266 (1968) 154
), L.Komo focused on the fact that this material is also used as a semiconductor material, and by making this material into a thin film,
The inventors have discovered that the above object can be achieved and have arrived at the present invention.
第１図に示すように、本発明の薄膜サーミスタ１は、電
気絶縁性基板２上に１対の電極３．３が設けられ、これ
らの電極３．３の上面及び電極が設けられていない基板
２の上面に感熱性抵抗膜４が設けられる。そしてこの感
熱性抵抗膜４が鉄、マンガン及びけい素からなり、その
組成が（Ｆ ｅ １−１Ｍ ｎ ｘ）１−ｙ Ｓ ｉ
ｙであって、０＜ｘ≦０．３０，０．６３≦ｙ≦０．７
１であることを特徴とする。電極３．３は２対以上あっ
てもよく、また電極３．３は感熱性抵抗膜４の上面に設
けてもよい。As shown in FIG. 1, the thin film thermistor 1 of the present invention includes a pair of electrodes 3.3 provided on an electrically insulating substrate 2, and a top surface of these electrodes 3.3 and a substrate on which no electrodes are provided. A heat-sensitive resistive film 4 is provided on the upper surface of 2. This heat-sensitive resistive film 4 is made of iron, manganese, and silicon, and has a composition of (F e 1-1M n x )1-y Si
y, 0<x≦0.30, 0.63≦y≦0.7
It is characterized by being 1. There may be two or more pairs of electrodes 3.3, and the electrodes 3.3 may be provided on the upper surface of the heat-sensitive resistive film 4.
この薄膜サーミスタを製造するには、不活性ガス雰囲気
中において、鉄とマンガンとけい素からなるターゲット
を用いて電気絶縁性基板上にスパッタリング蒸着により
、その組成が
（Ｆ ｅ １−ｘＭ ｎ Ｘ）ｌ−）Ｉ Ｓ ｉ ｙで
あって、０＜ｘ≦０．３０，０．６３≦ｙ≦０，７１で
ある感熱性抵抗膜を形成する。In order to manufacture this thin film thermistor, the composition is (F e 1-xM n -) A heat-sensitive resistive film is formed where I S i y and 0<x≦0.30, 0.63≦y≦0,71.
本発明の電気絶縁性基板は、耐熱性を有し、鉄けい化物
の熱膨張率（１０ｘ １０−’ｄｅｇ−”）に近い熱膨
張率を有し、鉄けい化物の付着性の大きいものであれば
よい。例示すればアルミナ、フォルスライト、ステアラ
イト、ベリリア、Ｍｇ−ＡＵスピネル等のいずれかの材
料からなる基板が好ましい。The electrically insulating substrate of the present invention has heat resistance, has a coefficient of thermal expansion close to that of iron silicide (10 x 10-'deg-''), and has a high adhesion of iron silicide. For example, a substrate made of any material such as alumina, forsrite, stearite, beryllia, or Mg-AU spinel is preferable.
また電極は、耐熱性と耐蝕性に優れた導電性材料により
作られる。例えば銀、金、白金、白金−金、金−パラジ
ウム−白金等が挙げられる。この電極は上記金属ペース
トを基板端部に印刷して焼付けて形成される。Further, the electrodes are made of a conductive material with excellent heat resistance and corrosion resistance. Examples include silver, gold, platinum, platinum-gold, gold-palladium-platinum, and the like. This electrode is formed by printing and baking the metal paste on the edge of the substrate.
更に感熱性抵抗膜は、気相成長法、電子ビーム蒸着法、
イオンビーム蒸着法、真空蒸着法、スパッタリング蒸着
法等により形成される。スパッタリング蒸着法が量産に
適しているため好ましい。Furthermore, heat-sensitive resistive films can be produced using vapor phase growth method, electron beam evaporation method,
It is formed by ion beam evaporation, vacuum evaporation, sputtering evaporation, or the like. Sputtering deposition is preferred because it is suitable for mass production.
スパッタリング蒸着は、Ａｒガスのような不活性ガス雰
囲気中で行われ、ターゲットには鉄とマンガンとけい素
の各粉末を所定の比率で配合し、円盤状に粉末冶金した
ものを使用する。蒸着した抵抗膜は結晶構造上、（Ｆｅ
Ｍｎ）Ｓｉ＊化合物を形成している必要があるため、基
板を３００〜９５０℃の温度で加熱した状態で蒸着する
ことが望ましい。Sputtering vapor deposition is performed in an inert gas atmosphere such as Ar gas, and a target containing powders of iron, manganese, and silicon in a predetermined ratio and powder metallurgized into a disk shape is used. Due to the crystal structure of the vapor-deposited resistive film, (Fe
Since it is necessary to form a Mn)Si* compound, it is desirable to perform the vapor deposition while heating the substrate at a temperature of 300 to 950°C.
しかし室温で蒸着した後に、次に述べる熱処理により（
ＦｅＭｎ）Ｓｉｔ化合物を得てもよい。However, after vapor deposition at room temperature, the following heat treatment (
FeMn)Sit compounds may also be obtained.
本発明の感熱性抵抗膜は、その組成が
（Ｆ ｅ １−ＸＭ ｎ ｘ）ｂｙ Ｓ ｉ ｙであっ
て、０＜ｘ≦０．３０，０．６３≦ｙ≦０７１であるこ
とを特徴とする。Ｍｎの含有率Ｘが０７３０を越えるか
又はＳｉの含有率ｙが０．６３〜０７１の範囲を外れる
組成になると、Ｂ定数が１０００に以下となりサーミス
タの特性上好ましくない。The heat-sensitive resistive film of the present invention is characterized in that its composition is (F e 1-XM n x) by Si y, and 0<x≦0.30, 0.63≦y≦071. do. If the Mn content x exceeds 0730 or the Si content y falls outside the range of 0.63 to 071, the B constant will be less than 1000, which is unfavorable in terms of the characteristics of the thermistor.
この抵抗膜の厚さは０１〜２μｍの範囲からサーミスタ
の用途に応じて作られる。０．１μｍ未満の場合、電極
に接続されるリード線の電気的抵抗の影響を受は易く、
また２μｍを越えると基板との熱膨張率の違いにより膜
が剥離し易くなるため、上記範囲内で作られる。The thickness of this resistive film is made in the range of 0.1 to 2 μm depending on the purpose of the thermistor. If it is less than 0.1 μm, it is easily affected by the electrical resistance of the lead wire connected to the electrode.
Furthermore, if the thickness exceeds 2 μm, the film is likely to peel off due to the difference in coefficient of thermal expansion from the substrate, so it is made within the above range.
スパッタリング蒸着した後、感熱性抵抗膜を形成した電
気絶縁性基板を４００〜９８５℃の温度範囲で熱処理す
ると、サーミスタとしての感熱性の再現性がよく、かつ
熱的安定性に優れるため好ましい。この熱処理は不活性
ガス雰囲気中又は真空中がより安定した特性を得るため
に好ましいが、大気中でも特性が安定しているためよい
。また熱処理は４００℃未満であるとその効果が乏しく
、９８５℃を越えると抵抗膜が熱的損傷を受は易くなる
。After sputtering and vapor deposition, it is preferable to heat-treat the electrically insulating substrate on which the heat-sensitive resistive film is formed at a temperature in the range of 400 to 985° C., since this results in good reproducibility of heat sensitivity as a thermistor and excellent thermal stability. This heat treatment is preferably performed in an inert gas atmosphere or in vacuum in order to obtain more stable characteristics, but it is also preferable to perform this heat treatment in the air because the characteristics are stable. Further, if the heat treatment temperature is less than 400°C, the effect will be poor, and if the temperature exceeds 985°C, the resistive film will be easily damaged by heat.
［作 用コ
基板上に感熱性抵抗膜を鉄とマンガンとけい素の組成比
を所定の範囲内で変えてスパッタリング蒸着することに
より、一般にサーミスタに要求されるＢ定数及び抵抗値
の中から所望の特性を具備することができる。また、基
板上に形成された鉄けい化物薄膜は耐熱性にも耐酸化性
にも優れ、しかも大気中で利用できる高温用熱電材料で
あるため、３００℃以上の温度でも感熱性の再現性が良
好になる。[Operation] By sputtering and depositing a heat-sensitive resistive film on a co-substrate while changing the composition ratio of iron, manganese, and silicon within a predetermined range, a desired value can be obtained from among the B constant and resistance value generally required for a thermistor. characteristics. In addition, the iron silicide thin film formed on the substrate has excellent heat resistance and oxidation resistance, and is a high-temperature thermoelectric material that can be used in the atmosphere, so it has excellent heat sensitivity reproducibility even at temperatures of 300°C or higher. Become good.
［発明の効果］
以上述べたように、本発明の（ＦｅＭｎ）ＳＬ薄膜サー
ミスタは鉄とマ：／ガソとけい素の組成比に応じてＢ定
数が少なくとも１００ＯＫ以Ｆの、サーミスタとして好
ましい値を有し、しかも室温での抵抗率が数１０ｍΩ・
Ｃｍ〜数Ω・ｃｍと広範囲でかつ従来のサーミスタと比
べて極めて小さいため、薄膜サーミスタ素子として従来
不可能であった数１０Ω〜数１０００Ωの低い抵抗値を
容易に得ることができる。[Effects of the Invention] As described above, the (FeMn)SL thin film thermistor of the present invention has a B constant of at least 100 OK or more, which is a preferable value as a thermistor, depending on the composition ratio of iron and magnesium/gaso and silicon. Moreover, the resistivity at room temperature is several tens of mΩ.
Since it has a wide range of Cm to several Ω·cm and is extremely small compared to conventional thermistors, it is possible to easily obtain a low resistance value of several tens of Ω to several thousand Ω, which was conventionally impossible as a thin film thermistor element.
特に薄膜に対してトリミング等を行えば、更に高抵抗化
することができ、高温における特性がより向上する。ま
た鉄けい化物は耐熱性に優れているため、本発明の薄膜
サーミスタは高温用に好適である。In particular, if the thin film is trimmed, the resistance can be further increased, and the characteristics at high temperatures can be further improved. Further, since iron silicide has excellent heat resistance, the thin film thermistor of the present invention is suitable for use at high temperatures.
［実施例］ 次に本発明の実施例を比較例とともに説明する。[Example] Next, examples of the present invention will be described together with comparative examples.
〈実施例１〉
電気絶縁性基板として、この例ではアルミナ基板を選定
した。ガラス粉末が混入された、所謂ガラスフリット入
り白金ペーストを基板の上面にスクリーン印刷法により
印刷し大気中にて１０００℃の温度で１時間焼付けて１
対の電極を形成した。。<Example 1> In this example, an alumina substrate was selected as the electrically insulating substrate. A so-called glass frit-containing platinum paste mixed with glass powder was printed on the top surface of the substrate by screen printing and baked in the air at a temperature of 1000°C for 1 hour.
A counter electrode was formed. .
この基板を９枚用意した後、各基板の上面に高周波スパ
ッタリング法により（ＦｅＭｎ）Ｓｉ薄膜を形成し、９
種類の薄膜サーミスタを作製した。即ち、鉄とマンガン
とけい素の原子比を変えた９種類のターゲットを用意し
て、各ターゲットを高周波スパッタリング装置の陰極に
各別に設け、数ｍＴｏｒｒ程度のＡｒガス雰囲気中で、
高周波電力ａｏｏｗ、成膜速度３μｍ／時の条件でスパ
ッタリシグし基板の上面に薄膜を形成した。After preparing nine of these substrates, a (FeMn)Si thin film was formed on the top surface of each substrate by high frequency sputtering method.
We fabricated various types of thin film thermistors. That is, nine types of targets with different atomic ratios of iron, manganese, and silicon were prepared, and each target was separately placed on the cathode of a high-frequency sputtering device in an Ar gas atmosphere of about several mTorr.
A thin film was formed on the upper surface of the substrate by sputtering under the conditions of high frequency power AOOW and film formation rate of 3 μm/hour.
蒸着後、薄膜を形成した基板を６００℃の温度で熱処理
した。After the vapor deposition, the substrate on which the thin film was formed was heat-treated at a temperature of 600°C.
〈比較例１〉
実施例１の９種類のターゲットの中で、Ｍｎの含有率が
最大のものより更にＭｎの含有率の大きいターゲット、
Ｓｉの含有率が最小のものより更にＳｉの含有率の小さ
いターゲット及びＳｉの含有率が最大のものより更にＳ
ｉの含有率の大きいターゲットを用いた以外は、実施例
１と同様にして３種類の薄膜サーミスタを作製した。<Comparative Example 1> Among the nine types of targets in Example 1, a target with a higher Mn content than the one with the highest Mn content,
Targets with a lower Si content than those with a minimum Si content and targets with a lower Si content than those with a maximum Si content
Three types of thin film thermistors were produced in the same manner as in Example 1, except that a target with a high content of i was used.
実施例１及び比較例１で作製したサーミスタの特性を第
１表に示す。１１種類の薄膜サーミスタはいずれも膜厚
約１μｍ１電極間距離１ｍｍ、薄膜の幅１ｍｍであった
。Table 1 shows the characteristics of the thermistors manufactured in Example 1 and Comparative Example 1. All of the 11 types of thin film thermistors had a film thickness of approximately 1 μm, a distance between electrodes of 1 mm, and a thin film width of 1 mm.
（以下、本頁余白）
第 １ 表
第１表の結果から、Ｍｎの含有率Ｘが０．３０を越える
か、又はＳｉの含有率ｙが０．６３〜０４７１の範囲を
外れる組成になると、Ｂ定数が１０００に以下となりサ
ーミスタの特性上好ましくないことが判った。(Hereinafter, this page margin) Table 1 From the results in Table 1, when the Mn content X exceeds 0.30 or the Si content y falls outside the range of 0.63 to 0471, It was found that the B constant was less than 1000, which was unfavorable in terms of the characteristics of the thermistor.
また実施例１の９種類の薄膜サーミスタはいずれも３０
０〜５００℃付近の温度まではＢ定数がほぼ一定で、５
００℃までの高温でも熱的に安定していた。５００℃を
上回ると、Ｂ定数が大きくなる傾向を示し、これらの特
性は高温用サーミスタとして極めて好ましい結果であっ
た。Furthermore, each of the nine types of thin film thermistors in Example 1 had a
The B constant is almost constant from 0 to 500℃, and 5
It was thermally stable even at high temperatures up to 00°C. When the temperature exceeds 500° C., the B constant tends to increase, and these characteristics are extremely favorable results for a high temperature thermistor.
一方比較例１の３種類の薄膜サーミスタはＢ定数が１０
００に以下と温度係数が小さいため、温度センサ或いは
温度補償用のサーミスタとしては不向きであった。On the other hand, the three types of thin film thermistors of Comparative Example 1 have a B constant of 10.
Since the temperature coefficient was small, less than 0.00, it was not suitable as a temperature sensor or a thermistor for temperature compensation.
〈実施例２〉
実施例１のサーミスタの電極間距離を０．１ｍｍにした
以外は、実施例１と同様にして薄膜サーミスタを作製し
た。この結果、実施例２のサーミスタの抵抗値は実施例
１の抵抗値の約１０分の１になった。<Example 2> A thin film thermistor was produced in the same manner as in Example 1 except that the distance between the electrodes of the thermistor in Example 1 was set to 0.1 mm. As a result, the resistance value of the thermistor of Example 2 was approximately one tenth of the resistance value of Example 1.
〈実施例３〉
実施例１のサーミスタの膜厚を０．１μｍにした以外は
、実施例１と同様にして薄膜サーミスタを作製した。こ
の結果、実施例３のサーミスタの抵抗値は実施例１の抵
抗値の約１０倍になった。<Example 3> A thin film thermistor was produced in the same manner as in Example 1 except that the film thickness of the thermistor in Example 1 was changed to 0.1 μm. As a result, the resistance value of the thermistor of Example 3 was approximately 10 times that of Example 1.
第１図は本発明の方法により製造した薄膜サーミスタの
断面図。
１：薄膜サーミスタ、
２：電気絶縁性基板、
３：電極、
４：感熱性抵抗膜。
特許出願人 三菱鉱業セメント株式会社１ 簿膜サーミ
スタ
第１図
手続補正書０．え）
平成３年８月５日
２、発明の名称 薄膜サーミスタ及びその製造方法３、
補正をする者
事件との関係 特許出願人
住所（居所）東京都千代田区大手町−丁目６番１号氏名
（名称） 三菱マテリアル株式会社４、代理人
８、補正の内容
（１）明細書第３頁第５行目
「・・・１００ＯＫ以上・・・」を
「・・・５００に以上・・・」と訂正する。
（２）明細書第４頁第５行目
「・・・２５００に程度と低いため、・・・」を「・・
・２５００に程度であり、・・・」と訂正する。
（３）明細書第４頁第１６行目
「・・・１００ＯＫ以上・・・」を
［・・・５００に以上・・・」と訂正する。
（４）明細書第８頁第４行目〜同頁第５行目「・・・１
００ＯＫ以下・・・」を
「・・・５００に以下・・・」と訂正する。
（５）明細書第９頁第１５行目
「・・・１００ＯＫ以上・・・」を
「・・・５００に以上・・・」と訂正する。
（以下、本頁余白）
（３）明細書第１２頁第１表
第 １ 表
を
（以下、本頁余白）
第 １ 表
と訂正する。
（４）明細書第１２頁下から第２行目
ｒｌｏｏＯＫ以下」を
ｒ５００に以下Ｊと訂正する。
（５）明細書第１３頁第８行目
「・・・１００ＯＫ以下・・・」を
「・・・５００に以下・・・」と訂正する。FIG. 1 is a sectional view of a thin film thermistor manufactured by the method of the present invention. 1: thin film thermistor, 2: electrically insulating substrate, 3: electrode, 4: heat-sensitive resistance film. Patent Applicant Mitsubishi Mining Cement Co., Ltd. 1 Book Membrane Thermistor Diagram 1 Procedural Amendment 0. e) August 5, 1991 2. Title of invention: Thin film thermistor and method for manufacturing the same 3.
Relationship with the case of the person making the amendment Patent applicant address (residence) 6-1 Otemachi-chome, Chiyoda-ku, Tokyo Name: Mitsubishi Materials Corporation 4, Agent 8, Contents of amendment (1) Specification No. On page 3, line 5, "...more than 100 OK..." is corrected to "...more than 500...". (2) On page 4, line 5 of the specification, "...because it is as low as 2,500..." is replaced with "...
・It is about 2,500, and...'' I corrected it. (3) On page 4, line 16 of the specification, "...more than 100 OK..." is corrected to "...more than 500...". (4) Specification page 8, line 4 to line 5 of the same page “...1
00OK or less..." is corrected to "...500 or less...". (5) On page 9, line 15 of the specification, "...more than 100 OKs..." is corrected to "...more than 500...". (hereinafter referred to as "this page margin") (3) Table 1 of Table 1 on page 12 of the specification is corrected to (hereinafter referred to as "this page margin") Table 1. (4) ``rlooOK and below'' on page 12 of the specification, line 2 from the bottom, is corrected to r500 and below as J. (5) On page 13, line 8 of the specification, "...100 OK or less..." is corrected to "...500 or less...".
Claims (1)
の抵抗膜（４）の上面又は下面に少なくとも１対の電極
（３，３）がそれぞれ設けられた薄膜サーミスタ（１）
において、前記感熱性抵抗膜（４）が鉄、マンガン及び
けい素からなり、 その組成が（Ｆｅ＿１＿−＿ｘＭｎ＿ｘ）＿１＿−＿ｘ
Ｓｉ＿ｙであって、０＜ｘ≦０．３０，０．６３≦ｙ≦
０．７１であることを特徴とする薄膜サーミスタ。 ２）不活性ガス雰囲気中において、鉄とマンガンとけい
素からなるターゲットを用いて電気絶縁性基板上にスパ
ッタリング蒸着により その組成が（Ｆｅ＿１＿−＿ｘＭｎ＿ｘ）＿１＿−＿ｙ
Ｓｉ＿ｙであって、０＜ｘ≦０．３０，０．６３≦ｙ≦
０．７１である感熱性抵抗膜を形成する薄膜サーミスタ
の製造方法。 ３）スパッタリング蒸着した後、感熱性抵抗膜を形成し
た電気絶縁性基板を不活性ガス雰囲気中又は真空中で４
００〜９８５℃の温度範囲で熱処理する請求項２記載の
薄膜サーミスタの製造方法。[Claims] 1) A heat-sensitive resistive film (4) on an electrically insulating substrate (2), and at least one pair of electrodes (3, 3) provided on the upper or lower surface of this resistive film (4), respectively. Thin film thermistor (1)
, the heat-sensitive resistive film (4) is made of iron, manganese and silicon, and its composition is (Fe_1_-_xMn_x)_1_-_x
Si_y, 0<x≦0.30, 0.63≦y≦
A thin film thermistor characterized in that the temperature is 0.71. 2) In an inert gas atmosphere, the composition is (Fe_1_-_xMn_x)_1_-_y by sputtering deposition on an electrically insulating substrate using a target consisting of iron, manganese, and silicon.
Si_y, 0<x≦0.30, 0.63≦y≦
A method for manufacturing a thin film thermistor forming a heat-sensitive resistance film having a temperature of 0.71. 3) After sputtering and vapor deposition, the electrically insulating substrate on which the heat-sensitive resistive film has been formed is heated in an inert gas atmosphere or in a vacuum.
3. The method for manufacturing a thin film thermistor according to claim 2, wherein the heat treatment is carried out at a temperature range of 00 to 985°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27162490A JPH04170003A (en) | 1990-10-09 | 1990-10-09 | Thin-film thermistor and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27162490A JPH04170003A (en) | 1990-10-09 | 1990-10-09 | Thin-film thermistor and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04170003A true JPH04170003A (en) | 1992-06-17 |
Family
ID=17502670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27162490A Pending JPH04170003A (en) | 1990-10-09 | 1990-10-09 | Thin-film thermistor and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04170003A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5916104B2 (en) * | 1977-02-21 | 1984-04-13 | 極東開発工業株式会社 | Hydraulic actuation device for piston pump for fluid pumping |
| JPS62291003A (en) * | 1986-06-10 | 1987-12-17 | 日本鋼管株式会社 | Manufacture of thin film thermistor |
| JPS62293701A (en) * | 1986-06-13 | 1987-12-21 | 日本鋼管株式会社 | Thin film temperature sensor and manufacture of the same |
-
1990
- 1990-10-09 JP JP27162490A patent/JPH04170003A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5916104B2 (en) * | 1977-02-21 | 1984-04-13 | 極東開発工業株式会社 | Hydraulic actuation device for piston pump for fluid pumping |
| JPS62291003A (en) * | 1986-06-10 | 1987-12-17 | 日本鋼管株式会社 | Manufacture of thin film thermistor |
| JPS62293701A (en) * | 1986-06-13 | 1987-12-21 | 日本鋼管株式会社 | Thin film temperature sensor and manufacture of the same |
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