JPH04192302A - Thin film thermistor element - Google Patents
Thin film thermistor elementInfo
- Publication number
- JPH04192302A JPH04192302A JP2302058A JP30205890A JPH04192302A JP H04192302 A JPH04192302 A JP H04192302A JP 2302058 A JP2302058 A JP 2302058A JP 30205890 A JP30205890 A JP 30205890A JP H04192302 A JPH04192302 A JP H04192302A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- heat
- film
- electrodes
- iron silicide
- 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 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000010408 film Substances 0.000 claims abstract description 50
- 229910052742 iron Inorganic materials 0.000 claims abstract description 41
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 229910021332 silicide Inorganic materials 0.000 claims abstract description 23
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims description 12
- 230000000737 periodic effect Effects 0.000 claims description 2
- 230000004044 response Effects 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 229910052697 platinum Inorganic materials 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000004544 sputter deposition Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 229910005347 FeSi Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 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
- 239000011261 inert gas Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- -1 Si2 compound Chemical class 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Thermistors And Varistors (AREA)
- Ceramic Products (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は感熱性抵抗膜か鉄けい化物からなる薄膜サーミ
スタ素子に関する。特に高温用センサに好適な薄膜サー
ミスタ素子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 element made of a heat-sensitive resistive film or iron silicide. In particular, the present invention relates to a thin film thermistor element suitable for high temperature sensors.
［従来の技術］
従来、この種のサーミスタ素子としては、■アルミナを
主成分とする金属酸化物の焼結体に白金なとのリード線
を埋込みガラスコートして外気と遮断・保護したビード
型素子、■上記■と同一材料のチップ状素子の両側に電
極を付け、これをガラス封入したＤ ＨＴ （ｄｏｕｂ
ｌｅ ｈｅａｔ−ｓｉｎｋ ｔｈｅｒｍｉｓ−ｔｏｒ）
型素子、■電極にリード線を付はガラスコートしたガラ
スモールドチップ型素子、或いは■電気絶練性基板上に
炭化けい素からなる感熱性薄膜を形成してリード線を付
与した薄膜サーミスタ素子（例えば、特開昭５３−６３
５５２）が知られている。[Conventional technology] Conventionally, this type of thermistor element is a bead type in which lead wires such as platinum are embedded in a sintered body of metal oxide whose main component is alumina and coated with glass to isolate and protect it from the outside air. The device is a DHT (double
heat-sink thermistor)
type element, ■Glass-molded chip type element with a glass coated electrode with lead wires, or ■Thin film thermistor element with lead wires formed by forming a heat-sensitive thin film made of silicon carbide on an electrically refractory substrate. For example, JP-A-53-63
552) is known.
［発明が解決しようとする課題］
上記■〜■のサーミスタ素子は高温において安定性がな
く、構造上から熱的応答性が劣るという問題点があった
。[Problems to be Solved by the Invention] The thermistor elements of (1) to (4) above have problems in that they are not stable at high temperatures and have poor thermal responsiveness due to their structure.
また上記■の薄膜サーミスタ素子は熱的安定性に優れて
いるため高温に耐える特長がある反面、その構造上けい
素と炭素の組成比の変更は難しいため、スパッタリング
時の成膜条件によってのみＢ定数や抵抗値等のサーミス
タ特性を変えられるに過ぎず、材料特性が限定され、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
スタ素子が得がたい不具合があった。In addition, although the thin film thermistor element mentioned above has excellent thermal stability and can withstand high temperatures, it is difficult to change the composition ratio of silicon and carbon due to its structure. Only the thermistor characteristics such as constants and resistance values can be changed, and the material properties are limited, making it difficult to create a thermistor element with a wide range of characteristics that can be tailored to various applications.
本発明の目的は、上記問題点を解決するもので熱的安定
性が高く、熱的応答性に優れ、かつ任意のＢ定数と抵抗
値とを組合せて各種用途にきめ細かに対応し得る幅広い
特性を具備した薄膜サーミスタ素子を提供することにあ
る。The purpose of the present invention is to solve the above-mentioned problems, and has high thermal stability, excellent thermal responsiveness, and a wide range of characteristics that can be finely adapted to various uses by combining arbitrary B constants and resistance values. An object of the present invention is to provide a thin film thermistor element having the following.
［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ＦｅＳｉ□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（ＲＫｉｅｆｆｅｒ、
Ｆ、Ｂｅｎｅｓｏｖｓｋｙ ａｎｄ Ｃ，Ｋｏｎｏｐｉ
ｃｋｙ： Ｂｅｒ。[Means for Solving the Problems] The present inventors discovered that the FeSi□-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. Konopi
cky: 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（ＪＰ、Ｐｉｔｏｎ ａｎｄ Ｍ、Ｆ
、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。Deunt, Keram, Ges, 31 (19
54) 223, etc.), and is a stable material on the phase diagram up to 986°C (JP, Piton and M, F
, Fay: C,R,Acad,Sci,C266
(1968) 154) focused on the fact that this material is also used as a semiconductor material, and found that the above object could be achieved by making this material into a thin film, thereby achieving the present invention.
第１図に示すように、本発明の薄膜サーミスタ素子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。電極３，
３に′はリード線５゜５が接着される。As shown in FIG. 1, the thin film thermistor element 1 of the present invention includes a pair of electrodes 3.3 provided on an electrically insulating substrate 2.
A heat-sensitive resistive film 4 is provided on the upper surface of these electrodes 3.3 and on the upper surface of the substrate 2 where no electrodes are provided. electrode 3,
A lead wire 5.5 is glued to 3'.
本発明の特徴あるところは、感熱性抵抗膜４か鉄けい化
物であることにある。特に、鉄けい化物の組成がＦｅ１
−ｙＳｉｙであって、０．６３≦ｙ≦０７１であること
が好ましい。また鉄けい化物はＦｅ及びＳｉを主成分と
し、この一部を金属元素Ｍで置換してもよい。この場合
、鉄けい化物の組成は（Ｆ ｅ４−ｘＭ’ｘ）１−ｙ
Ｓ ｉ ｙであって、金属元素Ｍは元素周期表の３Ａ族
、４Ａ族、５Ａ族。A feature of the present invention is that the heat-sensitive resistive film 4 is made of iron silicide. In particular, the composition of iron silicide is Fe1
-ySiy, and preferably 0.63≦y≦071. Moreover, iron silicide has Fe and Si as main components, and a part of this may be replaced with metal element M. In this case, the composition of iron silicide is (Fe4-xM'x)1-y
S i y, and the metal element M is a group 3A, 4A, or 5A of the periodic table of elements.
６Ａ族、７Ａ族、８族及び１Ｂ族の元素から選ばれた少
なくとも１つの元素であり、Ｘ及びｙがそれぞれＯ＜ｘ
≦０．３０，０．６３≦ｙ≦０．７１であることが好ま
しい。特に好ましい元素は遷移金属元素（Ｓｃ、Ｔｉ、
Ｖ、Ｃｒ、Ｍｎ、Ｆｅ。At least one element selected from the elements of Group 6A, Group 7A, Group 8, and Group 1B, and X and y are each O<x
It is preferable that ≦0.30, 0.63≦y≦0.71. Particularly preferred elements are transition metal elements (Sc, Ti,
V, Cr, Mn, Fe.
Ｃｏ、Ｎｉ、Ｃｕ）又は白金属元素（Ｒｕ、Ｒｈ。Co, Ni, Cu) or platinum metal elements (Ru, Rh.
Ｐｄ、Ｏｓ、Ｉ ｒ、Ｐｔ）である。金属元素Ｍの含有
率Ｘが０．１５を越えるか又はＳｉの含有率ｙが０．６
３〜０７１の範囲を外れる組成になると、Ｂ定数が１０
００に以下となりサーミスタの特性上好ましくない。Pd, Os, Ir, Pt). The content x of the metal element M exceeds 0.15 or the content y of Si is 0.6
When the composition falls outside the range of 3 to 071, the B constant becomes 10.
00 or less, which is unfavorable in terms of the characteristics of the thermistor.
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。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.
また第２図に示すように、感熱性抵抗膜４の上面に電気
絶縁用保護膜６を形成してもよい。Furthermore, as shown in FIG. 2, an electrically insulating protective film 6 may be formed on the upper surface of the heat-sensitive resistive film 4.
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（ＩＯＸ １０−’ｄｅｇ−１）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−Ａ文スピネル等のいずれかの材
料からなる基板か好ましい。The electrically insulating substrate of the present invention has heat resistance, has a coefficient of thermal expansion close to that of iron silicide (IOX 10-'deg-1), and has a high adhesion of iron silicide. Good to have. For example, a substrate made of any one of materials such as alumina, forsrite, stearite, beryllia, and Mg-A 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。この電極は薄膜もしくは上記金属
ペーストを基板端部に印刷して焼付けた厚膜により形成
される。Furthermore, the electrodes are made of a conductive material with excellent heat resistance and corrosion resistance. For example, platinum, platinum-gold, gold-palladium-
Examples include platinum. This electrode is formed by a thin film or a thick film obtained 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けい素の各粉末又
は鉄とけい素と前述した金属元素Ｍ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、ＦｅＳｉ＊化合物又は（Ｆ
ｅｌＪ）Ｓｉ２化合物を形成している必要かあるため、
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 the target is a mixture of iron and silicon powders or iron, silicon, and metal element M powders in a predetermined ratio, and a disk-shaped Use powder metallurgy. Due to its crystal structure, the vapor-deposited resistive film is made of FeSi* compound or (F
elJ) Since it is necessary to form a Si2 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Ｆ
ｅＳｉ２化合物又は（ＦｅＭ）Ｓｉｚ化合物を得てもよ
い。However, after vapor deposition at room temperature, F
An eSi2 compound or a (FeM)Siz compound may be obtained.
本発明の感熱性抵抗膜は、膜厚が０．０１〜２μｍの範
囲からサーミスタの用途に応じて作られる。００１μｍ
未満の場合、抵抗膜が基板と反応したり、また基板の凹
凸により膜が形成しにくいなどの基板からの影響を受は
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 heat-sensitive resistance film of the present invention is made to have a film thickness in the range of 0.01 to 2 μm depending on the purpose of the thermistor. 001μm
If it is less than 2 μm, the resistive film may react with the substrate, or it may be difficult to form a film due to the irregularities of the substrate, and if it exceeds 2 μm, the film may be difficult to form due to the difference in thermal expansion coefficient with the substrate. Since it becomes easy to peel off, it is made within the above range.
感熱性抵抗膜を形成した後、その電気絶縁性基板を４０
０〜９８５℃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か、大気
中でも特性か安定しているためよい。また熱処理は４０
０℃未満であるとその効果か乏しく、９８５℃を越える
と抵抗膜が熱的損傷を受は易くなる。After forming the heat-sensitive resistive film, the electrically insulating substrate was heated for 40 minutes.
Heat treatment in the temperature range of 0 to 985° C. is preferable because it provides good reproducibility of heat sensitivity as a thermistor and excellent thermal stability. This heat treatment is preferably carried out in an inert gas atmosphere or vacuum in order to obtain more stable characteristics, or in the air because the characteristics are stable. Also, heat treatment is 40
If the temperature is less than 0°C, the effect will be poor, and if it exceeds 985°C, the resistive film will be susceptible to thermal damage.
電気絶縁用保護膜はイオン性のある湿気や水分が感熱性
抵抗膜に直接付着してサーミスタ特性か変化するのを防
止するもので、０１〜１０μｍの膜厚に形成される。０
１μｍ未満であると保護機能に劣り、１０μｍを越える
と熱膨張率の違いにより剥離し易くなるため、上記範囲
に形成される。この保護膜としては、熱膨張率か感熱性
抵抗膜のそれに近くて、耐蝕性に優れた材料か選ばれる
。例示すれば鉄けい化物の酸化物、高純度けい素、二酸
化けい素、窒化けい素等が挙げられる。The electrical insulating protective film prevents ionic moisture or moisture from directly adhering to the heat-sensitive resistive film and changing the thermistor characteristics, and is formed to a thickness of 01 to 10 μm. 0
If it is less than 1 μm, the protective function will be inferior, and if it exceeds 10 μm, it will be easy to peel off due to the difference in coefficient of thermal expansion, so it is formed within the above range. For this protective film, a material with a coefficient of thermal expansion close to that of the heat-sensitive resistive film and excellent corrosion resistance is selected. Examples include iron silicide oxides, high purity silicon, silicon dioxide, and silicon nitride.
この保護膜は前述した感熱性抵抗膜を形成した後の熱処
理によって形成されることもあるか、この熱処理後、更
に保護膜形成のために特別に熱処理することが好ましい
。This protective film may be formed by heat treatment after forming the above-mentioned heat-sensitive resistive film, or it is preferable that after this heat treatment, a special heat treatment is further performed for forming the protective film.
例えば、二酸化けい素の保護膜を作るには、熱処理した
電気絶縁性基板を大気中又は酸化性雰囲気中で５００〜
１０００℃の温度で更に熱処理すると、鉄けい化物の膜
表面の一部が分離し、抵抗膜上に５ｉＯｚの保護膜が形
成される。この熱処理は鉄けい化物の膜表面の一部を分
離させる必要かあることから前述の熱処理と比べて、短
時間で若干高い温度で行われる。絶縁性を高めるために
、５ｉｎ２のターゲットを用いてスパッタリングして５
ｉ０２の保護膜を形成してもよい。For example, to make a silicon dioxide protective film, a heat-treated electrically insulating substrate is heated to
When further heat-treated at a temperature of 1000° C., part of the surface of the iron silicide film separates, and a protective film of 5 iOz is formed on the resistive film. This heat treatment is performed in a shorter time and at a slightly higher temperature than the above-mentioned heat treatment because it is necessary to separate a part of the surface of the iron silicide film. To improve the insulation, sputtering is performed using a 5in2 target.
A protective film of i02 may be formed.
別の保護膜の成膜法としては、鉄けい化物の薄膜を形成
するときに、アルゴンガスの雰囲気を一部酸素で置換し
、活性スパッタリングを行って形成する方法もある。Another method for forming a protective film is to replace part of the argon gas atmosphere with oxygen and perform active sputtering when forming a thin film of iron silicide.
最後にリード線を電極に接着することにより、薄膜サー
ミスタ素子が得られる。このリード線の電極への接着方
法は、例えば白金細線をボンディングし、これを太い耐
熱性導線に溶接する方法、或いは電極焼付けに用いた白
金ペーストを用いて白金リード線を電極に焼付は固定す
る方法がある。Finally, by bonding the lead wires to the electrodes, a thin film thermistor element is obtained. The method of adhering this lead wire to the electrode is, for example, by bonding a thin platinum wire and welding it to a thick heat-resistant conductor wire, or by baking and fixing the platinum lead wire to the electrode using the platinum paste used for baking the electrode. There is a way.
リード線を電極に接着した後、耐熱性が高く絶縁性の高
い無機充填剤を用いて薄膜サーミスタ素子全体を金属性
パイプ内に埋め込むと、温度センサか得られる。After bonding the lead wires to the electrodes, a temperature sensor is obtained by embedding the entire thin-film thermistor element in a metal pipe using an inorganic filler that has high heat resistance and high insulation properties.
［作 用］
本発明の薄膜サーミスタ素子は、鉄とけい素の組成比又
は鉄とけい素の組成比を所定の範囲内で変えたり、鉄の
一部を金属元素Ｍで置換して感熱性抵抗膜を形成できる
ため、種々の温度特性を有し、Ｂ定数が１０００〜５０
００に、膜厚か００１〜２μｍで室温におい′て数Ω〜
数ＭΩ以上の幅広い範囲の抵抗値を有し、少なくとも３
００℃以上の温度で安定性の良いサーミスタ特性を備え
る。[Function] The thin film thermistor element of the present invention can be made into a heat-sensitive resistive film by changing the composition ratio of iron and silicon or the composition ratio of iron and silicon within a predetermined range, or by replacing a part of iron with metal element M. It has various temperature characteristics and has a B constant of 1000 to 50.
00, the film thickness is 001 to 2 μm, and the resistance is several Ω at room temperature.
It has a wide range of resistance values of several MΩ or more, and at least 3
Equipped with thermistor characteristics that are stable at temperatures above 00°C.
電気絶縁基板上に形成された鉄けい化物薄膜はバルクと
して耐熱性にも耐酸化性にも優れているため、薄膜サー
ミスタの状態でも高温用サーミスタとして極めて安定で
ある。Since the iron silicide thin film formed on the electrically insulating substrate has excellent heat resistance and oxidation resistance as a bulk, it is extremely stable as a high-temperature thermistor even in the form of a thin film thermistor.
また感熱性抵抗膜は成膜時の形状寸法の自由度が比較的
高＜、シかも形成された薄膜のトリミングも可能である
ため、一般にサーミスタ素子に要求される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。In addition, heat-sensitive resistive films have a relatively high degree of freedom in shape and size during film formation, and trimming of the formed thin film is also possible. It can have desired properties.
［発明の効果］
以上述べたように、本発明の薄膜サーミスタ素子は、感
熱性抵抗膜がＦｅＳｉ、系材料であるため、耐熱性及び
耐酸化性に優れ、しかも薄膜であるため、熱的応答性が
良好で、高温用に好適である。[Effects of the Invention] As described above, the thin film thermistor element of the present invention has excellent heat resistance and oxidation resistance because the heat-sensitive resistive film is made of FeSi, and because it is a thin film, it has excellent thermal response. It has good properties and is suitable for high temperature applications.
また鉄とけい素の組成比又は鉄とけい素の組成比を所定
の範囲内で変えたり、鉄の一部を金属元素Ｍで置換して
感熱性抵抗膜を形成できるため、種々のＢ定数と抵抗値
の組合せが可能になり、所望の特性のサーミスタ素子が
得られる。In addition, it is possible to form a heat-sensitive resistive film by changing the composition ratio of iron and silicon or the composition ratio of iron and silicon within a predetermined range, or by replacing a part of iron with the metal element M. Combinations of values become possible and a thermistor element with desired characteristics can be obtained.
特に感熱性抵抗膜の上面に電気絶縁用保護膜を形成すれ
ば、外界の影響を受けにくくなり、かつ耐酸化性も高ま
るため、より特性が安定し、高温用サーミスタにより一
層適したものになる。In particular, if an electrically insulating protective film is formed on the top surface of the heat-sensitive resistive film, it will be less susceptible to external influences and will also have higher oxidation resistance, making the characteristics more stable and making it more suitable for high-temperature thermistors. .
［実施例コ 次に本発明の実施例を比較例とともに説明する。[Example code] 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１８枚用意し、そのうち４枚は鉄とけい素か
らなる鉄けい化物、残りの１３枚は鉄の一部を金属元素
Ｍ （Ｍ＝Ｍｎ、Ｃｒ、Ｎ ｉ、ｖ。Eighteen of these substrates were prepared, four of which were made of iron silicide made of iron and silicon, and the remaining 13 were made of metal elements M (M=Mn, Cr, Ni, v).
Ｐｔ、Ｐｄ）で置換した鉄けい化物からなる薄膜を作る
ために用いた。各基板の上面に高周波スパッタリング法
により鉄けい化物薄膜を形成し、１８種類の薄膜サーミ
スタを作製した。即ち、鉄とけい素の原子比及び鉄とけ
い素と金属元素Ｍ（Ｍ＝Ｍｎ、Ｃｒ、Ｎｉ、Ｖ、Ｐｔ、
Ｐｄ）の原子比を変えた１８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３００Ｗ、成膜速度３μｍ ／ ｈ ｒの条件で
スパッタリングし基板の上面に薄膜を形成した。It was used to make a thin film made of iron silicide substituted with Pt, Pd). An iron silicide thin film was formed on the upper surface of each substrate by high frequency sputtering, and 18 types of thin film thermistors were manufactured. That is, the atomic ratio of iron and silicon, iron, silicon, and metal element M (M=Mn, Cr, Ni, V, Pt,
Eighteen types of targets with different atomic ratios of Pd) were prepared, and each target was separately placed on the cathode of a high-frequency sputtering device. A thin film was formed on the upper surface of the substrate by sputtering under the following conditions.
蒸着後、薄膜を形成した基板を６００℃の温度で熱処理
した。続いて薄膜の一部をエツチングし、電極部分を露
出させ、この部分に直径０１５ｍｍの白金細線をパラレ
ルギャップ法により接続し、高温用センサに適した薄膜
サーミスタ素子を作製した。After the vapor deposition, the substrate on which the thin film was formed was heat-treated at a temperature of 600°C. Subsequently, a part of the thin film was etched to expose an electrode part, and a thin platinum wire with a diameter of 015 mm was connected to this part by the parallel gap method to produce a thin film thermistor element suitable for a high temperature sensor.
く比較例１〉
実施例１の１８種類のターゲットの中で、金属元素Ｍを
含有しない４種類のもののうち、鉄の原子比が最低のも
のより更に低いターゲット及び鉄の原子比が最高のもの
より更に高いターゲットを用いた以外は、実施例１と同
様にして２種類の薄膜サーミスタ素子を作製した。Comparative Example 1> Among the 18 types of targets in Example 1, among the four types that do not contain the metal element M, a target with an iron atomic ratio lower than the lowest one and a target with the highest iron atomic ratio Two types of thin film thermistor elements were produced in the same manner as in Example 1, except that a higher target was used.
〈比較例２〉
実施例１の１８種類のターゲットの中で、金属元素Ｍを
含有する１４種類のもののうち、金属元素Ｍの含有率が
最大のものより更にＭの含有率の大きいターゲット、Ｓ
ｉの含有率が最小のものより更にＳｔ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Ｓｉ
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素子を作製した。<Comparative Example 2> Among the 18 types of targets in Example 1, among the 14 types containing the metal element M, a target with a higher content of M than the target with the highest content of the metal element M, S
Targets with a smaller St content than those with a minimum i content and even more Si than those with a maximum Si content
Example 1 except that a target with a large content of
Three types of thin film thermistor elements were fabricated in the same manner as above.
実施例１．比較例１及び比較例２で作製した２３種類の
サーミスタ素子の特性を第１表に示す。Example 1. Table 1 shows the characteristics of the 23 types of thermistor elements manufactured in Comparative Example 1 and Comparative Example 2.
第３図にそのうちの１種類の鉄とけい素からなる鉄けい
化物でｙ＝０．６７６のトリミング処理した抵抗値が７
２００にΩのサーミスタ素子の温度特性を示す。２３種
類の薄膜サーミスタ素子は膜厚が０．１μｍ又は１．０
μｍであって、いずれも電極間距離１ｍｍ、薄膜の幅１
ｍｍであった。Figure 3 shows that one type of iron silicide made of iron and silicon has a resistance value of 7 after trimming at y=0.676.
200 Ω shows the temperature characteristics of the thermistor element. The 23 types of thin film thermistor elements have a film thickness of 0.1 μm or 1.0 μm.
μm, the distance between the electrodes is 1 mm, and the width of the thin film is 1 mm.
It was mm.
Ｂ定数は２５℃と１００℃の抵抗値より算出した。The B constant was calculated from the resistance values at 25°C and 100°C.
抵抗値は２５℃における値である。また高抵抗化にする
ために、２３種類の薄膜サーミスタ素子のうち１９種類
について薄膜の表面の一部をレーザーにてトリミング処
理した。The resistance value is the value at 25°C. Furthermore, in order to increase the resistance, a portion of the surface of the thin film of 19 out of 23 types of thin film thermistor elements was trimmed using a laser.
（以下、本頁余白）
第１表
第１表の結果から金属元素Ｍ （Ｍ＝Ｍ ｎ 、 Ｃ
ｒ。(Hereinafter, this page margin) Table 1 From the results in Table 1, the metal element M (M=M n , C
r.
Ｎｉ、Ｖ、Ｐｔ、Ｐｄ）の含有率Ｘが０．１５以下であ
るか、又はＳｉの含有率ｙか０６３〜０７１の範囲内に
あると、Ｂ定数が１００ＯＫを上回り、温度センサ或い
は温度補償用のサーミスタに好適なサーミスタ素子であ
ることか判った。If the content (X) of Ni, V, Pt, Pd) is 0.15 or less, or if the Si content (y) is within the range of 063 to 071, the B constant will exceed 100OK and the temperature sensor or temperature compensation It was found that this thermistor element is suitable for use in commercial thermistors.
また第３図に示すように、本実施例の薄膜サーミスタ素
子は２５℃〜５００℃の温度範囲において極めて安定し
た特性を示すことか判った。Furthermore, as shown in FIG. 3, it was found that the thin film thermistor element of this example exhibited extremely stable characteristics in the temperature range of 25 DEG C. to 500 DEG C.
第１図は本発明の薄膜サーミスタ素子の断面図。
第２図は本発明の別の薄膜サーミスタ素子の断面図。
第３図は本発明一実施例薄膜サーミスタ素子の特性図。
１：薄膜サーミスタ素子、
２：電気絶縁性基板、
３：電極、
４：感熱性抵抗膜、
５：リード線、
６：電気絶縁用保護膜。
特許出願人 三菱鉱業セメント株式会社Ｔ （”Ｃ）
手続補正書６．え、
平成３年８月５日
特許庁長官 深 沢 亘 殿
２、発明の名称 薄膜サーミスタ素子
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５頁第１６行目
「・・・１０００に以下・・・」を
「・・・５００に以下・・・」と訂正する。
（２）明細書第１０頁第８行目
ｒ・・・１０００〜５０００ Ｋ・Ｊを「・・・５００
に以上・・・」と訂正する。
（３）明細書第１５頁第１表
（以下、本頁余白）
第１表
第１表
と訂正する。
（４）明細書第１６頁第４行目
「・・・１０００Ｋｊを
ｒ、５００ＫＪと訂正する。FIG. 1 is a sectional view of a thin film thermistor element of the present invention. FIG. 2 is a sectional view of another thin film thermistor element of the present invention. FIG. 3 is a characteristic diagram of a thin film thermistor element according to an embodiment of the present invention. DESCRIPTION OF SYMBOLS 1: Thin film thermistor element, 2: Electrically insulating substrate, 3: Electrode, 4: Heat-sensitive resistance film, 5: Lead wire, 6: Protective film for electrical insulation. Patent applicant: Mitsubishi Mining and Cement Co., Ltd. T (“C) Procedural amendment 6. August 5, 1991 Commissioner of the Japan Patent Office Mr. Wataru Fukazawa 2, Title of invention: Thin film thermistor element 3 Amendment case Related Patent applicant address (residence) 6-1 Otemachi-chome, Chiyoda-ku, Tokyo Name: Mitsubishi Materials Corporation 4, Agent 8 Contents of amendment (1) Page 5, line 16 of the specification " ...1000 or less..." is corrected to "...500 or less...". (2) Page 10, line 8 of the specification r...1000-5000 K.J....500
More than that…” I corrected myself. (3) Table 1, page 15 of the specification (hereinafter referred to as the margin of this page) is corrected to Table 1, Table 1. (4) Page 16, line 4 of the specification: ``...1000Kj is corrected to r, 500KJ.
Claims (1)
面又は下面に少なくとも１対の電極がそれぞれ設けられ
た薄膜サーミスタにおいて、 前記電極にリード線が接着され、かつ 前記感熱性抵抗膜が鉄けい化物であることを特徴とする
薄膜サーミスタ素子。 ２）鉄けい化物の組成が Ｆｅ＿１＿−＿ｙＳｉ＿ｙであって、 ０．６３≦ｙ≦０．７１である請求項１記載の薄膜サー
ミスタ素子。 ３）鉄けい化物はＦｅ及びＳｉを主成分とし、この一部
を金属元素Ｍで置換し、その組成が （Ｆｅ＿１＿−＿ｘＭ＿ｘ）＿１＿−＿ｙＳｉ＿ｙであ
って、金属元素Ｍは元素周期表の３Ａ族，４Ａ族，５Ａ
族，６Ａ族，７Ａ族，８族及び１Ｂ族の元素から選ばれ
た少なくとも１つの元素であり、ｘ及びｙがそれぞれ０
＜ｘ≦０．３０，０．６３≦ｙ≦０．７１である請求項
１記載の薄膜サーミスタ素子。 ４）感熱性抵抗膜の上面に電気絶縁用保護膜が形成され
た請求項１記載の薄膜サーミスタ素子。[Scope of Claims] 1) A thin film thermistor comprising a heat-sensitive resistive film on an electrically insulating substrate and at least one pair of electrodes on the upper or lower surface of the resistive film, the lead wires being bonded to the electrodes, A thin film thermistor element characterized in that the heat-sensitive resistive film is made of iron silicide. 2) The thin film thermistor element according to claim 1, wherein the composition of the iron silicide is Fe_1_-_ySi_y, and 0.63≦y≦0.71. 3) Iron silicide has Fe and Si as main components, some of which are replaced with metal element M, and its composition is (Fe_1_-_xM_x)_1_-_ySi_y, where metal element M belongs to Group 3A of the periodic table of elements. , 4A group, 5A
at least one element selected from the elements of Group 6A, Group 7A, Group 8 and Group 1B, and x and y are each 0.
The thin film thermistor element according to claim 1, wherein <x≦0.30, 0.63≦y≦0.71. 4) The thin film thermistor element according to claim 1, wherein an electrically insulating protective film is formed on the upper surface of the heat-sensitive resistance film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2302058A JPH04192302A (en) | 1990-11-07 | 1990-11-07 | Thin film thermistor element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2302058A JPH04192302A (en) | 1990-11-07 | 1990-11-07 | Thin film thermistor element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04192302A true JPH04192302A (en) | 1992-07-10 |
Family
ID=17904411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2302058A Pending JPH04192302A (en) | 1990-11-07 | 1990-11-07 | Thin film thermistor element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04192302A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100227490B1 (en) * | 1995-05-11 | 1999-11-01 | 모리시타 요이찌 | Temperature sensor element, temperature sensor having the same and method for producing the same temperature sensor element |
| JP2007027541A (en) * | 2005-07-20 | 2007-02-01 | Tateyama Kagaku Kogyo Kk | Ntc thermistor element and its manufacturing method |
-
1990
- 1990-11-07 JP JP2302058A patent/JPH04192302A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100227490B1 (en) * | 1995-05-11 | 1999-11-01 | 모리시타 요이찌 | Temperature sensor element, temperature sensor having the same and method for producing the same temperature sensor element |
| JP2007027541A (en) * | 2005-07-20 | 2007-02-01 | Tateyama Kagaku Kogyo Kk | Ntc thermistor element and its manufacturing method |
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