JP6308364B2 - Metal nitride material for thermistor, manufacturing method thereof, and film type thermistor sensor - Google Patents
Metal nitride material for thermistor, manufacturing method thereof, and film type thermistor sensor Download PDFInfo
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- 239000000463 material Substances 0.000 title claims description 137
- 229910052751 metal Inorganic materials 0.000 title claims description 82
- 239000002184 metal Substances 0.000 title claims description 82
- 150000004767 nitrides Chemical class 0.000 title claims description 78
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 239000010408 film Substances 0.000 claims description 149
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 70
- 239000013078 crystal Substances 0.000 claims description 55
- 239000010409 thin film Substances 0.000 claims description 50
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 42
- 229910052719 titanium Inorganic materials 0.000 claims description 41
- 229910052804 chromium Inorganic materials 0.000 claims description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 21
- 238000005546 reactive sputtering Methods 0.000 claims description 17
- 238000004544 sputter deposition Methods 0.000 claims description 17
- 229910000838 Al alloy Inorganic materials 0.000 claims description 12
- 238000005477 sputtering target Methods 0.000 claims description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 22
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- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
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- 229910019590 Cr-N Inorganic materials 0.000 description 1
- 229910019588 Cr—N Inorganic materials 0.000 description 1
- 229910004491 TaAlN Inorganic materials 0.000 description 1
- 229910004688 Ti-V Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
- H01C17/075—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thin film techniques
- H01C17/12—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thin film techniques by sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/06—Epitaxial-layer growth by reactive sputtering
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/38—Nitrides
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
- G01K7/16—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements
- G01K7/22—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements the element being a non-linear resistance, e.g. thermistor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/04—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient
- H01C7/042—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient mainly consisting of inorganic non-metallic substances
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- Chemical & Material Sciences (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Electromagnetism (AREA)
- Inorganic Chemistry (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Thermistors And Varistors (AREA)
- Measuring Temperature Or Quantity Of Heat (AREA)
- Apparatuses And Processes For Manufacturing Resistors (AREA)
Description
本発明は、フィルム等に非焼成で直接成膜可能なサーミスタ用金属窒化物材料及びその製造方法並びにフィルム型サーミスタセンサに関する。 The present invention relates to a metal nitride material for a thermistor that can be directly formed on a film or the like without firing, a method for manufacturing the material, and a film type thermistor sensor.
温度センサ等に使用されるサーミスタ材料は、高精度、高感度のために、高いＢ定数が求められている。従来、このようなサーミスタ材料には、Ｍｎ，Ｃｏ，Ｆｅ等の遷移金属酸化物が一般的である（特許文献１〜３参照）。また、これらのサーミスタ材料では、安定なサーミスタ特性を得るために、５５０℃以上の焼成等の熱処理が必要である。 A thermistor material used for a temperature sensor or the like is required to have a high B constant for high accuracy and high sensitivity. Conventionally, transition metal oxides such as Mn, Co, and Fe are generally used for such thermistor materials (see Patent Documents 1 to 3). In addition, these thermistor materials require heat treatment such as firing at 550 ° C. or higher in order to obtain stable thermistor characteristics.
また、上記のような金属酸化物からなるサーミスタ材料の他に、例えば特許文献４では、一般式：ＭｘＡｙＮｚ（但し、ＭはＴａ，Ｎｂ，Ｃｒ，Ｔｉ及びＺｒの少なくとも１種、ＡはＡｌ，Ｓｉ及びＢの少なくとも１種を示す。０．１≦ｘ≦０．８、０＜ｙ≦０．６、０．１≦ｚ≦０．８、ｘ＋ｙ＋ｚ＝１）で示される窒化物からなるサーミスタ用材料が提案されている。また、この特許文献４では、Ｔａ−Ａｌ−Ｎ系材料で、０．５≦ｘ≦０．８、０．１≦ｙ≦０．５、０．２≦ｚ≦０．７、ｘ＋ｙ＋ｚ＝１としたものだけが実施例として記載されている。このＴａ−Ａｌ−Ｎ系材料では、上記元素を含む材料をターゲットとして用い、窒素ガス含有雰囲気中でスパッタリングを行って作製されている。また、必要に応じて、得られた薄膜を３５０〜６００℃で熱処理を行っている。 In addition to the thermistor material composed of the metal oxide as described above, for example, in Patent Document 4, the general formula: MxAyNz (where M is at least one of Ta, Nb, Cr, Ti and Zr, and A is Al, It represents at least one of Si and B. 0.1 ≦ x ≦ 0.8, 0 <y ≦ 0.6, 0.1 ≦ z ≦ 0.8, x + y + z = 1) Thermistor made of nitride Materials have been proposed. Moreover, in this patent document 4, it is Ta-Al-N type material, 0.5 <= x <= 0.8, 0.1 <= y <= 0.5, 0.2 <= z <= 0.7, x + y + z = 1. Only those described above are described as examples. This Ta—Al—N-based material is produced by performing sputtering in a nitrogen gas-containing atmosphere using a material containing the above elements as a target. Moreover, the obtained thin film is heat-processed at 350-600 degreeC as needed.
また、サーミスタ材料とは異なる例として、例えば特許文献５では、一般式：Ｃｒ１００−ｘ−ｙＮｘＭｙ（但し、ＭはＴｉ、Ｖ、Ｎｂ、Ｔａ、Ｎｉ、Ｚｒ、Ｈｆ、Ｓｉ、Ｇｅ、Ｃ、Ｏ、Ｐ、Ｓｅ、Ｔｅ、Ｚｎ、Ｃｕ、Ｂｉ、Ｆｅ、Ｍｏ、Ｗ、Ａｓ、Ｓｎ、Ｓｂ、Ｐｂ、Ｂ、Ｇａ、Ｉｎ、Ｔｌ、Ｒｕ、Ｒｈ、Ｒｅ、Ｏｓ、Ｉｒ、Ｐｔ、Ｐｄ、Ａｇ、Ａｕ、Ｃｏ、Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｍｎ、Ａｌおよび希土類元素から選択される１種または２種以上の元素であり、結晶構造が主としてｂｃｃ構造または主としてｂｃｃ構造とＡ１５型構造との混合組織である。０．０００１≦ｘ≦３０、０≦ｙ≦３０、０．０００１≦ｘ＋ｙ≦５０）で示される窒化物からなる歪センサ用抵抗膜材料が提案されている。この歪センサ用抵抗膜材料は、窒素量ｘ、副成分元素Ｍ量ｙをともに３０原子％以下の組成において、Ｃｒ− Ｎ基歪抵抗膜のセンサの抵抗変化から、歪や応力の計測ならびに変換に用いられる。また、このＣｒ−Ｎ−Ｍ系材料では、上記元素を含む材料等のターゲットとして用い、上記副成分ガスを含む成膜雰囲気中で反応性スパッタリングを行って作製されている。また、必要に応じて、得られた薄膜を２００〜１０００℃で熱処理を行っている。 As an example different from the thermistor material, for example, in Patent Document 5, the general formula: Cr100-x-yNxMy (where M is Ti, V, Nb, Ta, Ni, Zr, Hf, Si, Ge, C, O , P, Se, Te, Zn, Cu, Bi, Fe, Mo, W, As, Sn, Sb, Pb, B, Ga, In, Tl, Ru, Rh, Re, Os, Ir, Pt, Pd, Ag , Au, Co, Be, Mg, Ca, Sr, Ba, Mn, Al and one or more elements selected from rare earth elements, and the crystal structure is mainly bcc structure or mainly bcc structure and A15 type structure A resistance film material for a strain sensor made of a nitride represented by 0.0001 ≦ x ≦ 30, 0 ≦ y ≦ 30, 0.0001 ≦ x + y ≦ 50) has been proposed. This resistance film material for strain sensors measures and converts strains and stresses from changes in the resistance of the Cr-N-based strain resistance film in a composition where both the nitrogen content x and the subcomponent element M content y are 30 atomic% or less. Used for. In addition, this Cr—N—M-based material is produced by performing reactive sputtering in a film-forming atmosphere containing the subcomponent gas, using it as a target such as a material containing the element. Moreover, the obtained thin film is heat-processed at 200-1000 degreeC as needed.
上記従来の技術には、以下の課題が残されている。
近年、樹脂フィルム上にサーミスタ材料を形成したフィルム型サーミスタセンサの開発が検討されており、フィルムに直接成膜できるサーミスタ材料の開発が望まれている。すなわち、フィルムを用いることで、フレキシブルなサーミスタセンサが得られることが期待される。さらに、０．１ｍｍ程度の厚さを持つ非常に薄いサーミスタセンサの開発が望まれているが、従来はアルミナ等のセラミックスを用いた基板材料がしばしば用いられ、例えば、厚さ０．１ｍｍへと薄くすると非常に脆く壊れやすい等の問題があったが、フィルムを用いることで非常に薄いサーミスタセンサが得られることが期待される。
しかしながら、樹脂材料で構成されるフィルムは、一般的に耐熱温度が１５０℃以下と低く、比較的耐熱温度の高い材料として知られるポリイミドでも２００℃程度の耐熱性しかないため、サーミスタ材料の形成工程において熱処理が加わる場合は、適用が困難であった。上記従来の酸化物サーミスタ材料では、所望のサーミスタ特性を実現するために５５０℃以上の焼成が必要であり、フィルムに直接成膜したフィルム型サーミスタセンサを実現できないという問題点があった。そのため、非焼成で直接成膜できるサーミスタ材料の開発が望まれているが、上記特許文献４に記載のサーミスタ材料でも、所望のサーミスタ特性を得るために、必要に応じて、得られた薄膜を３５０〜６００℃で熱処理する必要があった。また、このサーミスタ材料では、Ｔａ−Ａｌ−Ｎ系材料の実施例において、Ｂ定数：５００〜３０００Ｋ程度の材料が得られているが、耐熱性に関する記述がなく、窒化物系材料の熱的信頼性が不明であった。
また、特許文献５のＣｒ−Ｎ−Ｍ系材料は、Ｂ定数が５００以下と小さい材料であり、また、２００℃以上１０００℃以下の熱処理を実施しないと、２００℃以内の耐熱性が確保できないことから、フィルムに直接成膜したフィルム型サーミスタセンサが実現できないという問題点があった。そのため、非焼成で直接成膜できるサーミスタ材料の開発が望まれている。
The following problems remain in the conventional technology.
In recent years, development of a film type thermistor sensor in which a thermistor material is formed on a resin film has been studied, and development of a thermistor material that can be directly formed on a film is desired. That is, it is expected that a flexible thermistor sensor can be obtained by using a film. Furthermore, although development of a very thin thermistor sensor having a thickness of about 0.1 mm is desired, conventionally, a substrate material using ceramics such as alumina is often used. When thinned, there were problems such as being very brittle and fragile, but it is expected that a very thin thermistor sensor can be obtained by using a film.
However, since a film made of a resin material generally has a heat resistant temperature as low as 150 ° C. or less, and polyimide known as a material having a relatively high heat resistant temperature has only a heat resistance of about 200 ° C., a thermistor material forming process In the case where heat treatment is applied, application is difficult. The conventional oxide thermistor material requires firing at 550 ° C. or higher in order to realize desired thermistor characteristics, and there is a problem that a film type thermistor sensor directly formed on a film cannot be realized. Therefore, it is desired to develop a thermistor material that can be directly film-formed without firing, but even with the thermistor material described in Patent Document 4, the obtained thin film can be obtained as necessary in order to obtain desired thermistor characteristics. It was necessary to perform heat treatment at 350 to 600 ° C. Further, in this example of the thermistor material, a material having a B constant of about 500 to 3000 K is obtained in the example of the Ta-Al-N material, but there is no description regarding heat resistance, and the thermal reliability of the nitride material. Sex was unknown.
Further, the Cr—N—M material of Patent Document 5 is a material having a B constant as small as 500 or less, and heat resistance within 200 ° C. cannot be ensured unless heat treatment at 200 ° C. or more and 1000 ° C. or less is performed. Therefore, there has been a problem that a film type thermistor sensor formed directly on a film cannot be realized. Therefore, it is desired to develop a thermistor material that can be directly formed without firing.
本発明は、前述の課題に鑑みてなされたもので、フィルム等に非焼成で直接成膜することができ、高い耐熱性を有して信頼性が高いサーミスタ用金属窒化物材料及びその製造方法並びにフィルム型サーミスタセンサを提供することを目的とする。 The present invention has been made in view of the above-described problems. The metal nitride material for a thermistor, which can be directly formed on a film or the like without being baked, has high heat resistance, and has high reliability, and a method for manufacturing the same. It is another object of the present invention to provide a film type thermistor sensor.
本発明者らは、窒化物材料の中でもＡｌＮ系に着目し、鋭意、研究を進めたところ、絶縁体であるＡｌＮは、最適なサーミスタ特性（Ｂ定数：１０００〜６０００Ｋ程度）を得ることが難しいが、Ａｌサイトを電気伝導を向上させる特定の金属元素で置換すると共に、特定の結晶構造とすることで、非焼成で良好なＢ定数と耐熱性とが得られることを見出した。
したがって、本発明は、上記知見から得られたものであり、前記課題を解決するために以下の構成を採用した。
The inventors of the present invention focused on the AlN system among the nitride materials and made extensive research. As a result, it is difficult for AlN as an insulator to obtain optimum thermistor characteristics (B constant: about 1000 to 6000 K). However, it has been found that by replacing the Al site with a specific metal element that improves electrical conduction and having a specific crystal structure, a good B constant and heat resistance can be obtained without firing.
Therefore, the present invention has been obtained from the above findings, and the following configuration has been adopted in order to solve the above problems.
すなわち、第１の発明に係るサーミスタ用金属窒化物材料は、サーミスタに用いられる金属窒化物材料であって、一般式：（Ｍ１−ｗＶｗ）ｘＡｌｙＮｚ（０．０＜ｗ＜１．０、０．７０≦ｙ／（ｘ＋ｙ）≦０．９８、０．４≦ｚ≦０．５、ｘ＋ｙ＋ｚ＝１）で示される金属窒化物からなり、その結晶構造が、六方晶系のウルツ鉱型の単相であり、前記Ｍが、Ｔｉ，Ｃｒの内の１種又は２種であることを特徴とする。
したがって、ＭがＴｉの場合、一般式は（Ｔｉ１−ｗＶｗ）ｘＡｌｙＮｚ（０．０＜ｗ＜１．０、０．７０≦ｙ／（ｘ＋ｙ）≦０．９８、０．４≦ｚ≦０．５、ｘ＋ｙ＋ｚ＝１）となる。また、ＭがＣｒの場合、一般式は（Ｃｒ１−ｗＶｗ）ｘＡｌｙＮｚ（０．０＜ｗ＜１．０、０．７０≦ｙ／（ｘ＋ｙ）≦０．９８、０．４≦ｚ≦０．５、ｘ＋ｙ＋ｚ＝１）となる。さらに、ＭがＴｉ，Ｃｒの場合、（ＴｉａＶｂＣｒｃ）ｘＡｌｙＮｚ（０．０＜ａ＜１．０、０．０＜ｂ＜１．０、０．０＜ｃ＜１．０、ａ＋ｂ＋ｃ＝１、０．７０≦ｙ／（ｘ＋ｙ）≦０．９８、０．４≦ｚ≦０．５、ｘ＋ｙ＋ｚ＝１）となる。
このサーミスタ用金属窒化物材料では、一般式：（Ｍ１−ｗＶｗ）ｘＡｌｙＮｚ（０．０＜ｗ＜１．０、０．７０≦ｙ／（ｘ＋ｙ）≦０．９８、０．４≦ｚ≦０．５、ｘ＋ｙ＋ｚ＝１）で示される金属窒化物からなり、その結晶構造が、六方晶系のウルツ鉱型の単相であり、前記Ｍが、Ｔｉ，Ｃｒの内の１種又は２種であるので、非焼成で良好なＢ定数が得られると共に高い耐熱性を有している。
That is, the metal nitride material for a thermistor according to the first invention is a metal nitride material used for the thermistor, and has a general formula: (M1-wVw) × AlyNz (0.0 <w <1.0, 0. 70 ≦ y / (x + y) ≦ 0.98, 0.4 ≦ z ≦ 0.5, x + y + z = 1), the crystal structure of which is a hexagonal wurtzite single phase The M is one or two of Ti and Cr.
Accordingly, when M is Ti, the general formula is (Ti1−wVw) × AlyNz (0.0 <w <1.0, 0.70 ≦ y / (x + y) ≦ 0.98, 0.4 ≦ z ≦ 0. 5, x + y + z = 1). When M is Cr, the general formula is (Cr1-wVw) xAlyNz (0.0 <w <1.0, 0.70 ≦ y / (x + y) ≦ 0.98, 0.4 ≦ z ≦ 0. 5, x + y + z = 1). Further, when M is Ti or Cr, (TiaVbCrc) xAlyNz (0.0 <a <1.0, 0.0 <b <1.0, 0.0 <c <1.0, a + b + c = 1, 0 .70 ≦ y / (x + y) ≦ 0.98, 0.4 ≦ z ≦ 0.5, x + y + z = 1).
In the metal nitride material for the thermistor, the general formula: (M1-wVw) xAlyNz (0.0 <w <1.0, 0.70 ≦ y / (x + y) ≦ 0.98, 0.4 ≦ z ≦ 0 .5, x + y + z = 1), the crystal structure of which is a hexagonal wurtzite single phase, and the M is one or two of Ti and Cr. Therefore, a good B constant can be obtained without firing and high heat resistance is obtained.
なお、上記「ｙ／（ｘ＋ｙ）」（すなわち、Ａｌ／（Ｍ＋Ｖ＋Ａｌ））が０．７０未満であると、ウルツ鉱型の単相が得られず、ＮａＣｌ型相との共存相又はＮａＣｌ型のみの結晶相となってしまい、十分な高抵抗と高Ｂ定数とが得られない。
また、上記「ｙ／（ｘ＋ｙ）」（すなわち、Ａｌ／（Ｍ＋Ｖ＋Ａｌ））が０．９８を超えると、抵抗率が非常に高く、きわめて高い絶縁性を示すため、サーミスタ材料として適用できない。
また、上記「ｚ」（すなわち、Ｎ／（Ｍ＋Ｖ＋Ａｌ＋Ｎ））が０．４未満であると、金属の窒化量が少ないため、ウルツ鉱型の単相が得られず、十分な高抵抗と高Ｂ定数とが得られない。
さらに、上記「ｚ」（すなわち、Ｎ／（Ｍ＋Ｖ＋Ａｌ＋Ｎ））が０．５を超えると、ウルツ鉱型の単相を得ることができない。このことは、ウルツ鉱型の単相において、窒素サイトにおける欠陥がない場合の化学量論比が０．５（すなわち、Ｎ／（Ｍ＋Ｖ＋Ａｌ＋Ｎ）＝０．５）であることに起因する。
When the above “y / (x + y)” (ie, Al / (M + V + Al)) is less than 0.70, a wurtzite single phase cannot be obtained, and only a coexisting phase with NaCl type phase or NaCl type Thus, a sufficiently high resistance and a high B constant cannot be obtained.
Further, if the above “y / (x + y)” (that is, Al / (M + V + Al)) exceeds 0.98, the resistivity is very high and the insulating property is extremely high, so that it cannot be applied as a thermistor material.
Further, when the “z” (that is, N / (M + V + Al + N)) is less than 0.4, since the amount of nitriding of the metal is small, a wurtzite type single phase cannot be obtained, and sufficient high resistance and high B A constant cannot be obtained.
Furthermore, when the “z” (that is, N / (M + V + Al + N)) exceeds 0.5, a wurtzite single phase cannot be obtained. This is due to the fact that in the wurtzite type single phase, the stoichiometric ratio when there is no defect at the nitrogen site is 0.5 (that is, N / (M + V + Al + N) = 0.5).
第２の発明に係るサーミスタ用金属窒化物材料は、第１の発明において、膜状に形成され、前記膜の表面に対して垂直方向に延在している柱状結晶であることを特徴とする。
すなわち、このサーミスタ用金属窒化物材料では、膜の表面に対して垂直方向に延在している柱状結晶であるので、膜の結晶性が高く、高い耐熱性が得られる。
The metal nitride material for a thermistor according to the second invention is a columnar crystal formed in a film shape and extending in a direction perpendicular to the surface of the film in the first invention. .
That is, the metal nitride material for thermistor is a columnar crystal extending in a direction perpendicular to the surface of the film, so that the film has high crystallinity and high heat resistance.
第３の発明に係るサーミスタ用金属窒化物材料は、第１又は第２の発明において、膜状に形成され、前記膜の表面に対して垂直方向にａ軸よりｃ軸が強く配向していることを特徴とする。
すなわち、このサーミスタ用金属窒化物材料では、膜の表面に対して垂直方向にａ軸よりｃ軸が強く配向しているので、ａ軸配向が強い場合に比べて高いＢ定数が得られ、さらに耐熱性に対する信頼性も優れている。
The metal nitride material for thermistors according to the third invention is formed in a film shape in the first or second invention, and the c-axis is oriented more strongly than the a-axis in the direction perpendicular to the surface of the film. It is characterized by that.
That is, in this metal nitride material for the thermistor, the c-axis is oriented more strongly than the a-axis in the direction perpendicular to the film surface, so that a higher B constant can be obtained than when the a-axis orientation is strong, Excellent reliability for heat resistance.
第４の発明に係るフィルム型サーミスタセンサは、絶縁性フィルムと、該絶縁性フィルム上に第１から第３のいずれかの発明のサーミスタ用金属窒化物材料で形成された薄膜サーミスタ部と、少なくとも前記薄膜サーミスタ部の上又は下に形成された一対のパターン電極とを備えていることを特徴とする。
すなわち、このフィルム型サーミスタセンサでは、絶縁性フィルム上に第１から第３のいずれかの発明のサーミスタ用金属窒化物材料で薄膜サーミスタ部が形成されているので、非焼成で形成され高Ｂ定数で耐熱性の高い薄膜サーミスタ部により、樹脂フィルム等の耐熱性の低い絶縁性フィルムを用いることができると共に、良好なサーミスタ特性を有した薄型でフレキシブルなサーミスタセンサが得られる。
また、従来、アルミナ等のセラミックスを用いた基板材料がしばしば用いられ、例えば、厚さ０．１ｍｍへと薄くすると非常に脆く壊れやすい等の問題があったが、本発明においてはフィルムを用いることができるので、例えば、厚さ０．１ｍｍの非常に薄いフィルム型サーミスタセンサを得ることができる。
A film type thermistor sensor according to a fourth invention comprises an insulating film, a thin film thermistor portion formed of the metal nitride material for a thermistor of any one of the first to third inventions on the insulating film, and at least And a pair of pattern electrodes formed above or below the thin film thermistor portion.
That is, in this film type thermistor sensor, since the thin film thermistor portion is formed of the metal nitride material for a thermistor according to any one of the first to third inventions on the insulating film, it is formed without firing and has a high B constant. In addition, an insulating film having low heat resistance such as a resin film can be used by the thin film thermistor portion having high heat resistance, and a thin and flexible thermistor sensor having good thermistor characteristics can be obtained.
Conventionally, substrate materials using ceramics such as alumina are often used. For example, when the thickness is reduced to 0.1 mm, the substrate material is very brittle and easily broken. Therefore, for example, a very thin film type thermistor sensor having a thickness of 0.1 mm can be obtained.
第５の発明に係るフィルム型サーミスタセンサは、第４の発明において、前記Ｍが、Ｔｉ，Ｃｒの内の少なくともＣｒを含む１種又は２種であり、前記パターン電極の少なくとも前記薄膜サーミスタ部に接合する部分がＣｒで形成されていることを特徴とする。
すなわち、このフィルム型サーミスタセンサでは、パターン電極の少なくとも薄膜サーミスタ部に接合する部分がＣｒで形成されているので、ＭＶＡｌＮ（Ｍが、Ｔｉ，Ｃｒの内の少なくともＣｒを含む１種又は２種）の薄膜サーミスタ部とパターン電極のＣｒとの高い接合性が得られる。すなわち、薄膜サーミスタ部を構成する元素の一つであるＣｒをパターン電極の接合部材料とすることで、両者の高い接合性が得られ、高い信頼性を得ることができる。
The film type thermistor sensor according to a fifth aspect of the present invention is the film type thermistor sensor according to the fourth aspect of the present invention, wherein the M is one or two of at least Cr out of Ti and Cr, The part to be joined is made of Cr.
That is, in this film type thermistor sensor, at least a portion of the pattern electrode joined to the thin film thermistor portion is formed of Cr, so MVAlN (M is one or two of at least Cr out of Ti and Cr). High bondability between the thin film thermistor portion and the pattern electrode Cr can be obtained. That is, by using Cr, which is one of the elements constituting the thin film thermistor portion, as the joint material of the pattern electrode, high jointability between them can be obtained, and high reliability can be obtained.
第６の発明に係るサーミスタ用金属窒化物材料の製造方法は、第１から第３のいずれかの発明のサーミスタ用金属窒化物材料を製造する方法であって、Ｍ−Ｖ−Ａｌ合金スパッタリングターゲットを用いて窒素含有雰囲気中で反応性スパッタを行って成膜する成膜工程を有しており、前記Ｍが、Ｔｉ，Ｃｒの内の１種又は２種であることを特徴とする。
すなわち、このサーミスタ用金属窒化物材料の製造方法では、Ｍ−Ｖ−Ａｌ合金スパッタリングターゲットを用いて窒素含有雰囲気中で反応性スパッタを行って成膜し、前記Ｍが、Ｔｉ，Ｃｒの内の１種又は２種であるので、上記ＭＶＡｌＮ（Ｍは、Ｔｉ，Ｃｒの内の１種又は２種）からなる本発明のサーミスタ用金属窒化物材料を非焼成で成膜することができる。
A method for producing a metal nitride material for a thermistor according to a sixth invention is a method for producing the metal nitride material for a thermistor according to any one of the first to third inventions, and comprises an MV-Al alloy sputtering target. A film forming step of forming a film by reactive sputtering in a nitrogen-containing atmosphere, wherein M is one or two of Ti and Cr.
That is, in this method for producing the metal nitride material for thermistor, a film is formed by performing reactive sputtering in a nitrogen-containing atmosphere using an MV-Al alloy sputtering target, where M is Ti or Cr. Since it is 1 type or 2 types, the metal nitride material for the thermistors of this invention which consists of said MVAlN (M is 1 type or 2 types in Ti and Cr) can be formed into a film without baking.
第７の発明に係るサーミスタ用金属窒化物材料の製造方法は、第６の発明において、前記反応性スパッタにおけるスパッタガス圧を、０．７Ｐａ未満に設定することを特徴とする。
すなわち、このサーミスタ用金属窒化物材料の製造方法では、反応性スパッタにおけるスパッタガス圧を、０．７Ｐａ未満に設定するので、膜の表面に対して垂直方向にａ軸よりｃ軸が強く配向している第３の発明に係るサーミスタ用金属窒化物材料の膜を形成することができる。
A method for producing a metal nitride material for a thermistor according to a seventh aspect is characterized in that, in the sixth aspect, a sputtering gas pressure in the reactive sputtering is set to less than 0.7 Pa.
That is, in this method for producing the thermistor metal nitride material, since the sputtering gas pressure in reactive sputtering is set to less than 0.7 Pa, the c axis is oriented more strongly than the a axis in the direction perpendicular to the film surface. A film of the metal nitride material for a thermistor according to the third invention can be formed.
第８の発明に係るサーミスタ用金属窒化物材料の製造方法は、第６又は第７の発明において、前記成膜工程後に、形成された膜に窒素プラズマを照射する工程を有していることを特徴とする。
すなわち、このサーミスタ用金属窒化物材料の製造方法では、成膜工程後に、形成された膜に窒素プラズマを照射するので、膜の窒素欠陥が少なくなって耐熱性がさらに向上する。
The method for producing a metal nitride material for a thermistor according to an eighth aspect of the present invention includes the step of irradiating the formed film with nitrogen plasma after the film formation step in the sixth or seventh aspect of the invention. Features.
That is, in this method for producing the metal nitride material for the thermistor, the formed film is irradiated with nitrogen plasma after the film forming step, so that nitrogen defects in the film are reduced and the heat resistance is further improved.
本発明によれば、以下の効果を奏する。
すなわち、本発明に係るサーミスタ用金属窒化物材料によれば、一般式：（Ｍ１−ｗＶｗ）ｘＡｌｙＮｚ（０．０＜ｗ＜１．０、０．７０≦ｙ／（ｘ＋ｙ）≦０．９８、０．４≦ｚ≦０．５、ｘ＋ｙ＋ｚ＝１）で示される金属窒化物からなり、その結晶構造が、六方晶系のウルツ鉱型の単相であり、前記Ｍが、Ｔｉ，Ｃｒの内の１種又は２種であるので、非焼成で良好なＢ定数が得られると共に高い耐熱性を有している。また、本発明に係るサーミスタ用金属窒化物材料の製造方法によれば、Ｍ−Ｖ−Ａｌ合金スパッタリングターゲットを用いて窒素含有雰囲気中で反応性スパッタを行って成膜するので、上記ＭＶＡｌＮからなる本発明のサーミスタ用金属窒化物材料を非焼成で成膜することができる。さらに、本発明に係るフィルム型サーミスタセンサによれば、絶縁性フィルム上に本発明のサーミスタ用金属窒化物材料で薄膜サーミスタ部が形成されているので、樹脂フィルム等の耐熱性の低い絶縁性フィルムを用いて良好なサーミスタ特性を有した薄型でフレキシブルなサーミスタセンサが得られる。さらに、基板材料が、薄くすると非常に脆く壊れやすいセラミックスでなく、樹脂フィルムであることから、厚さ０．１ｍｍの非常に薄いフィルム型サーミスタセンサが得られる。
The present invention has the following effects.
That is, according to the metal nitride material for a thermistor according to the present invention, the general formula: (M1-wVw) × AlyNz (0.0 <w <1.0, 0.70 ≦ y / (x + y) ≦ 0.98, 0.4 ≦ z ≦ 0.5, x + y + z = 1), the crystal structure of which is a hexagonal wurtzite single phase, and the M is an element of Ti and Cr. Therefore, a good B constant can be obtained without firing, and high heat resistance can be obtained. In addition, according to the method for manufacturing a metal nitride material for thermistor according to the present invention, a film is formed by performing reactive sputtering in a nitrogen-containing atmosphere using an MV-Al alloy sputtering target, and thus the above-described MVAlN is used. The metal nitride material for a thermistor of the present invention can be formed without firing. Furthermore, according to the film type thermistor sensor according to the present invention, since the thin film thermistor portion is formed of the metal nitride material for thermistor of the present invention on the insulating film, the insulating film having low heat resistance such as a resin film. Can be used to obtain a thin and flexible thermistor sensor having good thermistor characteristics. Furthermore, since the substrate material is not a ceramic that is very brittle and fragile when thin, but a resin film, a very thin film type thermistor sensor having a thickness of 0.1 mm can be obtained.
以下、本発明に係るサーミスタ用金属窒化物材料及びその製造方法並びにフィルム型サーミスタセンサにおける一実施形態を、図１から図５を参照しながら説明する。なお、以下の説明に用いる図面では、各部を認識可能又は認識容易な大きさとするために必要に応じて縮尺を適宜変更している。 Hereinafter, an embodiment of a metal nitride material for a thermistor according to the present invention, a manufacturing method thereof, and a film type thermistor sensor will be described with reference to FIGS. In the drawings used for the following description, the scale is appropriately changed as necessary to make each part recognizable or easily recognizable.
本実施形態のサーミスタ用金属窒化物材料は、サーミスタに用いられる金属窒化物材料であって、一般式：（Ｍ１−ｗＶｗ）ｘＡｌｙＮｚ（０．０＜ｗ＜１．０、０．７０≦ｙ／（ｘ＋ｙ）≦０．９８、０．４≦ｚ≦０．５、ｘ＋ｙ＋ｚ＝１）で示される金属窒化物からなり、その結晶構造が、六方晶系のウルツ鉱型（空間群Ｐ６３ｍｃ（Ｎｏ．１８６））の単相であり、前記Ｍが、Ｔｉ，Ｃｒの内の１種又は２種である。 The metal nitride material for a thermistor of the present embodiment is a metal nitride material used for the thermistor, and has a general formula: (M1-wVw) × AlyNz (0.0 <w <1.0, 0.70 ≦ y / (X + y) ≦ 0.98, 0.4 ≦ z ≦ 0.5, x + y + z = 1), the crystal structure of which is a hexagonal wurtzite type (space group P63mc (No. 186)) and the M is one or two of Ti and Cr.
すなわち、ＭがＴｉの場合、このサーミスタ用金属窒化物材料は、図１に示すように、Ｔｉ−Ｖ（バナジウム）−Ａｌ−Ｎ系３元系相図における点Ａ，Ｂ，Ｃ，Ｄで囲まれる領域内の組成を有し、結晶相がウルツ鉱型である金属窒化物である。
また、ＭがＣｒの場合、このサーミスタ用金属窒化物材料は、図２に示すように、Ｃｒ−Ｖ（バナジウム）−Ａｌ−Ｎ系３元系相図における点Ａ，Ｂ，Ｃ，Ｄで囲まれる領域内の組成を有し、結晶相がウルツ鉱型である金属窒化物である。
さらに、ＭがＴｉ，Ｃｒの場合、このサーミスタ用金属窒化物材料は、図３に示すように、Ｔｉ−Ｃｒ−Ｖ（バナジウム）−Ａｌ−Ｎ系３元系相図における点Ａ，Ｂ，Ｃ，Ｄで囲まれる領域内の組成を有し、結晶相がウルツ鉱型である金属窒化物である。
なお、上記点Ａ，Ｂ，Ｃ，Ｄの各組成比（ｘ，ｙ，ｚ）（ａｔｍ％）は、Ａ（１５．０，３５．０，５０．０），Ｂ（１．０，４９．０，５０．０），Ｃ（１．２，５８．８，４０．０），Ｄ（１８．０，４２．０，４０．０）である。
That is, when M is Ti, the metal nitride material for the thermistor is represented by points A, B, C, and D in the Ti-V (vanadium) -Al-N ternary phase diagram as shown in FIG. It is a metal nitride having a composition in the enclosed region and having a crystalline phase of wurtzite type.
When M is Cr, the metal nitride material for the thermistor is represented by points A, B, C, and D in the Cr-V (vanadium) -Al-N ternary phase diagram as shown in FIG. It is a metal nitride having a composition in the enclosed region and having a crystalline phase of wurtzite type.
Furthermore, when M is Ti or Cr, the metal nitride material for the thermistor has points A, B, and B in the Ti—Cr—V (vanadium) -Al—N ternary phase diagram as shown in FIG. It is a metal nitride having a composition in a region surrounded by C and D and having a crystal phase of wurtzite type.
The composition ratios (x, y, z) (atm%) of the points A, B, C, and D are A (15.0, 35.0, 50.0), B (1.0, 49). .0, 50.0), C (1.2, 58.8, 40.0), D (18.0, 42.0, 40.0).
また、このサーミスタ用金属窒化物材料は、膜状に形成され、前記膜の表面に対して垂直方向に延在している柱状結晶である。さらに、膜の表面に対して垂直方向にａ軸よりｃ軸が強く配向していることが好ましい。
なお、膜の表面に対して垂直方向（膜厚方向）にａ軸配向（１００）が強いかｃ軸配向（００２）が強いかの判断は、Ｘ線回折（ＸＲＤ）を用いて結晶軸の配向性を調べ、（１００）（ａ軸配向を示すｈｋｌ指数）と（００２）（ｃ軸配向を示すｈｋｌ指数）とのピーク強度比から、「（１００）のピーク強度」／「（００２）のピーク強度」が１未満である場合、ｃ軸配向が強いものとする。
The metal nitride material for the thermistor is a columnar crystal formed in a film shape and extending in a direction perpendicular to the surface of the film. Further, it is preferable that the c-axis is oriented more strongly than the a-axis in the direction perpendicular to the film surface.
Whether the a-axis orientation (100) is strong or the c-axis orientation (002) is strong in the direction perpendicular to the film surface (film thickness direction) is determined using X-ray diffraction (XRD). The orientation was investigated, and the peak intensity ratio of (100) (hkl index indicating a-axis orientation) and (002) (hkl index indicating c-axis orientation) was calculated as “(100) peak intensity” / “(002) When the “peak intensity of” is less than 1, the c-axis orientation is strong.
次に、本実施形態のサーミスタ用金属窒化物材料を用いたフィルム型サーミスタセンサについて説明する。このフィルム型サーミスタセンサ１は、図４に示すように、絶縁性フィルム２と、該絶縁性フィルム２上に上記サーミスタ用金属窒化物材料で形成された薄膜サーミスタ部３と、少なくとも薄膜サーミスタ部３上に形成された一対のパターン電極４とを備えている。 Next, a film type thermistor sensor using the metal nitride material for the thermistor of this embodiment will be described. As shown in FIG. 4, the film type thermistor sensor 1 includes an insulating film 2, a thin film thermistor portion 3 formed of the metal nitride material for the thermistor on the insulating film 2, and at least the thin film thermistor portion 3. And a pair of pattern electrodes 4 formed thereon.
上記絶縁性フィルム２は、例えばポリイミド樹脂シートで帯状に形成されている。なお、絶縁性フィルム２としては、他にＰＥＴ：ポリエチレンテレフタレート，ＰＥＮ：ポリエチレンナフタレート等でも構わない。
上記一対のパターン電極４は、例えばＣｒ膜とＡｕ膜との積層金属膜でパターン形成され、薄膜サーミスタ部３上で互いに対向状態に配した櫛形パターンの一対の櫛形電極部４ａと、これら櫛形電極部４ａに先端部が接続され基端部が絶縁性フィルム２の端部に配されて延在した一対の直線延在部４ｂとを有している。
The insulating film 2 is formed in a band shape with, for example, a polyimide resin sheet. In addition, as the insulating film 2, PET: polyethylene terephthalate, PEN: polyethylene naphthalate, or the like may be used.
The pair of pattern electrodes 4 is formed by patterning a laminated metal film of, for example, a Cr film and an Au film, and a pair of comb-shaped electrode portions 4a having a comb-shaped pattern arranged on the thin film thermistor portion 3 so as to face each other, and these comb-shaped electrodes A tip end portion is connected to the portion 4a, and a base end portion is disposed at an end portion of the insulating film 2 and has a pair of linear extending portions 4b extending.
また、一対の直線延在部４ｂの基端部上には、リード線の引き出し部としてＡｕめっき等のめっき部４ｃが形成されている。このめっき部４ｃには、リード線の一端が半田材等で接合される。さらに、めっき部４ｃを含む絶縁性フィルム２の端部を除いて該絶縁性フィルム２上にポリイミドカバーレイフィルム５が加圧接着されている。なお、ポリイミドカバーレイフィルム５の代わりに、ポリイミドやエポキシ系の樹脂材料層を印刷で絶縁性フィルム２上に形成しても構わない。 On the base end portion of the pair of linearly extending portions 4b, a plating portion 4c such as Au plating is formed as a lead wire lead-out portion. One end of a lead wire is joined to the plating portion 4c with a solder material or the like. Further, the polyimide coverlay film 5 is pressure-bonded on the insulating film 2 except for the end of the insulating film 2 including the plated portion 4c. In place of the polyimide coverlay film 5, a polyimide or epoxy resin material layer may be formed on the insulating film 2 by printing.
このサーミスタ用金属窒化物材料の製造方法及びこれを用いたフィルム型サーミスタセンサ１の製造方法について、図５を参照して以下に説明する。 A manufacturing method of the metal nitride material for the thermistor and a manufacturing method of the film type thermistor sensor 1 using the same will be described below with reference to FIG.
まず、本実施形態のサーミスタ用金属窒化物材料の製造方法は、Ｍ−Ｖ−Ａｌ合金スパッタリングターゲットを用いて窒素含有雰囲気中で反応性スパッタを行って成膜する成膜工程を有している。ここで、前記Ｍは、Ｔｉ，Ｃｒの内の１種又は２種である。
すなわち、ＭがＴｉの場合、Ｔｉ−Ｖ−Ａｌ合金スパッタリングターゲットを用い、またＭがＣｒの場合、Ｃｒ−Ｖ−Ａｌ合金スパッタリングターゲットを用い、さらにＭがＴｉ，Ｃｒの場合、Ｔｉ−Ｃｒ−Ｖ−Ａｌ合金スパッタリングターゲットを用いる。
また、上記反応性スパッタにおけるスパッタガス圧を、０．７Ｐａ未満に設定することが好ましい。
さらに、上記成膜工程後に、形成された膜に窒素プラズマを照射することが好ましい。
First, the method for producing a metal nitride material for a thermistor according to the present embodiment includes a film forming process for forming a film by performing reactive sputtering in a nitrogen-containing atmosphere using an MV-Al alloy sputtering target. . Here, the M is one or two of Ti and Cr.
That is, when M is Ti, a Ti-V-Al alloy sputtering target is used. When M is Cr, a Cr-V-Al alloy sputtering target is used. When M is Ti or Cr, Ti-Cr- A V-Al alloy sputtering target is used.
Moreover, it is preferable to set the sputtering gas pressure in the reactive sputtering to less than 0.7 Pa.
Furthermore, it is preferable to irradiate the formed film with nitrogen plasma after the film formation step.
より具体的には、例えば図５の（ａ）に示す厚さ５０μｍのポリイミドフィルムの絶縁性フィルム２上に、図５の（ｂ）に示すように、反応性スパッタ法にて上記本実施形態のサーミスタ用金属窒化物材料で形成された薄膜サーミスタ部３を２００ｎｍ成膜する。
ＭがＴｉの場合、その時のスパッタ条件は、例えば到達真空度：５×１０−６Ｐａ、スパッタガス圧：０．４Ｐａ、ターゲット投入電力（出力）：３００Ｗで、Ａｒガス＋窒素ガスの混合ガス雰囲気下において窒素ガス分圧：２０％とする。
ＭがＣｒの場合、その時のスパッタ条件は、例えば到達真空度：５×１０−６Ｐａ、スパッタガス圧：０．６７Ｐａ、ターゲット投入電力（出力）：３００Ｗで、Ａｒガス＋窒素ガスの混合ガス雰囲気下において窒素ガス分圧：８０％とする。
ＭがＴｉ，Ｃｒの場合、その時のスパッタ条件は、例えば到達真空度：５×１０−６Ｐａ、スパッタガス圧：０．４Ｐａ、ターゲット投入電力（出力）：３００Ｗで、Ａｒガス＋窒素ガスの混合ガス雰囲気下において窒素ガス分圧：３０％とする。
More specifically, for example, the present embodiment is formed on the insulating film 2 of a polyimide film having a thickness of 50 μm shown in FIG. 5A by reactive sputtering as shown in FIG. 5B. A thin film thermistor portion 3 made of the metal nitride material for thermistor is formed to a thickness of 200 nm.
When M is Ti, sputtering conditions at that time are, for example, ultimate vacuum: 5 × 10 −6 Pa, sputtering gas pressure: 0.4 Pa, target input power (output): 300 W, mixed gas of Ar gas + nitrogen gas In the atmosphere, the partial pressure of nitrogen gas is set to 20%.
When M is Cr, sputtering conditions at that time are, for example, ultimate vacuum: 5 × 10 −6 Pa, sputtering gas pressure: 0.67 Pa, target input power (output): 300 W, mixed gas of Ar gas + nitrogen gas Nitrogen gas partial pressure is set to 80% under the atmosphere.
When M is Ti or Cr, sputtering conditions at that time are, for example, ultimate vacuum: 5 × 10 −6 Pa, sputtering gas pressure: 0.4 Pa, target input power (output): 300 W, Ar gas + nitrogen gas In a mixed gas atmosphere, the nitrogen gas partial pressure is set to 30%.
また、メタルマスクを用いて所望のサイズにサーミスタ用金属窒化物材料を成膜して薄膜サーミスタ部３を形成する。なお、形成された薄膜サーミスタ部３に窒素プラズマを照射することが望ましい。例えば、真空度：６．７Ｐａ、出力：２００Ｗ及びＮ２ガス雰囲気下で、窒素プラズマを薄膜サーミスタ部３に照射させる。 The thin film thermistor portion 3 is formed by forming a metal nitride material for the thermistor into a desired size using a metal mask. Note that it is desirable to irradiate the formed thin film thermistor portion 3 with nitrogen plasma. For example, the thin film thermistor section 3 is irradiated with nitrogen plasma under a degree of vacuum of 6.7 Pa, an output of 200 W, and an N 2 gas atmosphere.
次に、スパッタ法にて、例えばＣｒ膜を２０ｎｍ形成し、さらにＡｕ膜を２００ｎｍ形成する。さらに、その上にレジスト液をバーコーターで塗布した後、１１０℃で１分３０秒のプリベークを行い、露光装置で感光後、現像液で不要部分を除去し、１５０℃で５分のポストベークにてパターニングを行う。その後、不要な電極部分を市販のＡｕエッチャント及びＣｒエッチャントによりウェットエッチングを行い、図５の（ｃ）に示すように、レジスト剥離にて所望の櫛形電極部４ａを有したパターン電極４を形成する。なお、絶縁性フィルム２上に先にパターン電極４を形成しておき、その櫛形電極部４ａ上に薄膜サーミスタ部３を成膜しても構わない。この場合、薄膜サーミスタ部３の下にパターン電極４の櫛形電極部４ａが形成されている。 Next, by sputtering, for example, a Cr film is formed to 20 nm, and an Au film is further formed to 200 nm. Further, after applying a resist solution thereon with a bar coater, prebaking is performed at 110 ° C. for 1 minute 30 seconds, and after exposure with an exposure apparatus, unnecessary portions are removed with a developer, and post baking is performed at 150 ° C. for 5 minutes. Patterning is performed at. Thereafter, unnecessary electrode portions are wet-etched with a commercially available Au etchant and Cr etchant, and as shown in FIG. 5C, pattern electrodes 4 having desired comb-shaped electrode portions 4a are formed by resist stripping. . Alternatively, the pattern electrode 4 may be formed on the insulating film 2 first, and the thin film thermistor portion 3 may be formed on the comb electrode portion 4a. In this case, the comb electrode portion 4 a of the pattern electrode 4 is formed under the thin film thermistor portion 3.
次に、図５の（ｄ）に示すように、例えば厚さ５０μｍの接着剤付きのポリイミドカバーレイフィルム５を絶縁性フィルム２上に載せ、プレス機にて１５０℃，２ＭＰａで１０分間加圧し接着させる。さらに、図５の（ｅ）に示すように、直線延在部４ｂの端部を、例えばＡｕめっき液によりＡｕ薄膜を２μｍ形成してめっき部４ｃを形成する。 Next, as shown in FIG. 5 (d), for example, a polyimide coverlay film 5 with an adhesive having a thickness of 50 μm is placed on the insulating film 2, and pressed by a press at 150 ° C. and 2 MPa for 10 minutes. Adhere. Further, as shown in FIG. 5E, an end portion of the linearly extending portion 4b is formed with a 2 μm Au thin film by using, for example, an Au plating solution to form a plated portion 4c.
なお、複数のフィルム型サーミスタセンサ１を同時に作製する場合、絶縁性フィルム２の大判シートに複数の薄膜サーミスタ部３及びパターン電極４を上述のように形成した後に、大判シートから各フィルム型サーミスタセンサ１に切断する。
このようにして、例えばサイズを２５×３．６ｍｍとし、厚さを０．１ｍｍとした薄いフィルム型サーミスタセンサ１が得られる。
When a plurality of film type thermistor sensors 1 are manufactured simultaneously, after forming the plurality of thin film thermistor portions 3 and the pattern electrodes 4 on the large sheet of the insulating film 2 as described above, each film type thermistor sensor is formed from the large sheet. Cut to 1.
In this way, for example, a thin film thermistor sensor 1 having a size of 25 × 3.6 mm and a thickness of 0.1 mm is obtained.
このように本実施形態のサーミスタ用金属窒化物材料では、一般式：（Ｍ１−ｗＶｗ）ｘＡｌｙＮｚ（０．０＜ｗ＜１．０、０．７０≦ｙ／（ｘ＋ｙ）≦０．９８、０．４≦ｚ≦０．５、ｘ＋ｙ＋ｚ＝１）で示される金属窒化物からなり、その結晶構造が、六方晶系のウルツ鉱型（空間群Ｐ６３ｍｃ（Ｎｏ．１８６））の単相であり、前記Ｍが、Ｔｉ，Ｃｒの内の１種又は２種であるので、非焼成で良好なＢ定数が得られると共に高い耐熱性を有している。
また、このサーミスタ用金属窒化物材料では、膜の表面に対して垂直方向に延在している柱状結晶であるので、膜の結晶性が高く、高い耐熱性が得られる。
さらに、このサーミスタ用金属窒化物材料では、膜の表面に対して垂直方向にａ軸よりｃ軸を強く配向させることで、ａ軸配向が強い場合に比べて高いＢ定数が得られる。
Thus, in the metal nitride material for the thermistor of the present embodiment, the general formula: (M1−wVw) × AlyNz (0.0 <w <1.0, 0.70 ≦ y / (x + y) ≦ 0.98, 0 .4 ≦ z ≦ 0.5, x + y + z = 1), the crystal structure of which is a single phase of a hexagonal wurtzite type (space group P6 3 mc (No. 186)) In addition, since the M is one or two of Ti and Cr, a good B constant can be obtained without firing, and it has high heat resistance.
In addition, since the metal nitride material for the thermistor is a columnar crystal extending in a direction perpendicular to the surface of the film, the film has high crystallinity and high heat resistance.
Furthermore, in this metal nitride material for the thermistor, a B constant higher than that when the a-axis orientation is strong can be obtained by orienting the c-axis more strongly than the a-axis in the direction perpendicular to the film surface.
本実施形態のサーミスタ用金属窒化物材料の製造方法では、Ｍ−Ｖ−Ａｌ合金スパッタリングターゲットを用いて窒素含有雰囲気中で反応性スパッタを行って成膜し、前記Ｍが、Ｔｉ，Ｃｒの内の１種又は２種であるので、上記ＭＶＡｌＮ（Ｍは、Ｔｉ，Ｃｒの内の１種又は２種）からなる上記サーミスタ用金属窒化物材料を非焼成で成膜することができる。
また、反応性スパッタにおけるスパッタガス圧を、０．７Ｐａ未満に設定することで、膜の表面に対して垂直方向にａ軸よりｃ軸が強く配向しているサーミスタ用金属窒化物材料の膜を形成することができる。
さらに、成膜工程後に、形成された膜に窒素プラズマを照射するので、膜の窒素欠陥が少なくなって耐熱性がさらに向上する。
In the manufacturing method of the metal nitride material for thermistor according to the present embodiment, a film is formed by performing reactive sputtering in a nitrogen-containing atmosphere using an MV-Al alloy sputtering target, where M is Ti, Cr. Therefore, the metal nitride material for the thermistor made of the above-mentioned MVAlN (M is one or two of Ti and Cr) can be formed without firing.
Also, by setting the sputtering gas pressure in reactive sputtering to less than 0.7 Pa, a metal nitride material film for thermistor in which the c-axis is oriented more strongly than the a-axis in the direction perpendicular to the surface of the film. Can be formed.
Furthermore, since the formed film is irradiated with nitrogen plasma after the film formation step, the number of nitrogen defects in the film is reduced and the heat resistance is further improved.
したがって、本実施形態のサーミスタ用金属窒化物材料を用いたフィルム型サーミスタセンサ１では、絶縁性フィルム２上に上記サーミスタ用金属窒化物材料で薄膜サーミスタ部３が形成されているので、非焼成で形成され高Ｂ定数で耐熱性の高い薄膜サーミスタ部３により、樹脂フィルム等の耐熱性の低い絶縁性フィルム２を用いることができると共に、良好なサーミスタ特性を有した薄型でフレキシブルなサーミスタセンサが得られる。
また、従来、アルミナ等のセラミックスを用いた基板材料がしばしば用いられ、例えば、厚さ０．１ｍｍへと薄くすると非常に脆く壊れやすい等の問題があったが、本実施形態においてはフィルムを用いることができるので、例えば、厚さ０．１ｍｍの非常に薄いフィルム型サーミスタセンサを得ることができる。
Therefore, in the film thermistor sensor 1 using the thermistor metal nitride material of the present embodiment, the thin film thermistor portion 3 is formed on the insulating film 2 from the thermistor metal nitride material. The formed thin film thermistor portion 3 having a high B constant and high heat resistance allows the use of an insulating film 2 having low heat resistance such as a resin film, and a thin and flexible thermistor sensor having good thermistor characteristics. It is done.
Conventionally, substrate materials using ceramics such as alumina are often used. For example, when the thickness is reduced to 0.1 mm, there is a problem that the substrate material is very brittle and easily broken. In this embodiment, a film is used. Therefore, for example, a very thin film type thermistor sensor having a thickness of 0.1 mm can be obtained.
さらに、パターン電極４の少なくとも薄膜サーミスタ部３に接合する部分がＣｒ膜で形成されているので、ＭＶＡｌＮ（Ｍが、Ｔｉ，Ｃｒの内の少なくともＣｒを含む１種又は２種）の薄膜サーミスタ部３とパターン電極４のＣｒ膜との高い接合性が得られる。すなわち、薄膜サーミスタ部３を構成する元素の一つであるＣｒをパターン電極４の接合部材料とすることで、両者の高い接合性が得られ、高い信頼性を得ることができる。 Further, since at least a portion of the pattern electrode 4 to be bonded to the thin film thermistor portion 3 is formed of a Cr film, a thin film thermistor portion of MVAlN (M is one or two of at least Cr of Ti and Cr). 3 and the Cr film of the pattern electrode 4 are obtained with high bondability. That is, by using Cr, which is one of the elements constituting the thin film thermistor section 3, as the joint material of the pattern electrode 4, high jointability between them can be obtained, and high reliability can be obtained.
次に、本発明に係るサーミスタ用金属窒化物材料及びその製造方法並びにフィルム型サーミスタセンサについて、上記実施形態に基づいて作製した実施例により評価した結果を、図６から図３１を参照して具体的に説明する。 Next, with respect to the metal nitride material for thermistor, the manufacturing method thereof, and the film type thermistor sensor according to the present invention, the results of evaluation based on the example manufactured based on the above embodiment will be specifically described with reference to FIGS. I will explain it.
＜膜評価用素子の作製＞
本発明の実施例及び比較例として、図６に示す膜評価用素子１２１を次のように作製した。
まず、反応性スパッタ法にて、様々な組成比のＴｉ−Ｖ−Ａｌ合金ターゲット、Ｃｒ−Ｖ−Ａｌ合金ターゲットおよびＴｉ−Ｃｒ−Ｖ−Ａｌ合金ターゲットを用いて、Ｓｉ基板Ｓとなる熱酸化膜付きＳｉウエハ上に、厚さ５００ｎｍの表１から表３に示す様々な組成比で形成されたサーミスタ用金属窒化物材料の薄膜サーミスタ部３を形成した。
<Production of film evaluation element>
As examples and comparative examples of the present invention, a film evaluation element 121 shown in FIG. 6 was produced as follows.
First, thermal oxidation to become a Si substrate S by using a Ti-V-Al alloy target, a Cr-V-Al alloy target, and a Ti-Cr-V-Al alloy target having various composition ratios by reactive sputtering. A thin film thermistor portion 3 of the metal nitride material for thermistor formed with various composition ratios shown in Tables 1 to 3 having a thickness of 500 nm was formed on the Si wafer with a film.
次に、上記薄膜サーミスタ部３の上に、スパッタ法でＣｒ膜を２０ｎｍ形成し、さらにＡｕ膜を２００ｎｍ形成した。さらに、その上にレジスト液をスピンコーターで塗布した後、１１０℃で１分３０秒のプリベークを行い、露光装置で感光後、現像液で不要部分を除去し、１５０℃で５分のポストベークにてパターニングを行った。その後、不要な電極部分を市販のＡｕエッチャント及びＣｒエッチャントによりウェットエッチングを行い、レジスト剥離にて所望の櫛形電極部１２４ａを有するパターン電極１２４を形成した。そして、これをチップ状にダイシングして、Ｂ定数評価及び耐熱性試験用の膜評価用素子１２１とした。
なお、比較として（Ｍ１−ｗＶｗ）ｘＡｌｙＮｚ（Ｍが、Ｔｉ，Ｃｒの内の１種又は２種）の組成比が本発明の範囲外であって結晶系が異なる比較例についても同様に作製して評価を行った。
Next, a 20 nm Cr film was formed on the thin film thermistor portion 3 by sputtering, and a 200 nm Au film was further formed. Further, after applying a resist solution thereon with a spin coater, pre-baking is performed at 110 ° C. for 1 minute 30 seconds. After exposure with an exposure apparatus, unnecessary portions are removed with a developing solution, and post-baking is performed at 150 ° C. for 5 minutes. Then, patterning was performed. Thereafter, unnecessary electrode portions were wet-etched with a commercially available Au etchant and Cr etchant, and a patterned electrode 124 having a desired comb-shaped electrode portion 124a was formed by resist stripping. Then, this was diced into chips to obtain a film evaluation element 121 for B constant evaluation and heat resistance test.
For comparison, a comparative example in which the composition ratio of (M1-wVw) xAlyNz (M is one or two of Ti and Cr) is outside the scope of the present invention and has a different crystal system was prepared in the same manner. And evaluated.
＜膜の評価＞
（１）組成分析
反応性スパッタ法にて得られた薄膜サーミスタ部３について、Ｘ線光電子分光法（ＸＰＳ）にて元素分析を行った。このＸＰＳでは、Ａｒスパッタにより、最表面から深さ２０ｎｍのスパッタ面において、定量分析を実施した。その結果を表１から表３に示す。なお、以下の表中の組成比は「原子％」で示している。一部のサンプルに対して、最表面から深さ１００ｎｍのスパッタ面における定量分析を実施し、深さ２０ｎｍのスパッタ面と定量精度の範囲内で同じ組成であることを確認している。
<Evaluation of membrane>
(1) Composition analysis About the thin film thermistor part 3 obtained by the reactive sputtering method, the elemental analysis was conducted by X-ray photoelectron spectroscopy (XPS). In this XPS, quantitative analysis was performed on the sputtered surface having a depth of 20 nm from the outermost surface by Ar sputtering. The results are shown in Tables 1 to 3. In addition, the composition ratio in the following table | surface is shown by "atomic%". Quantitative analysis was performed on a sputter surface having a depth of 100 nm from the outermost surface of some samples, and it was confirmed that the composition was the same as that of the sputter surface having a depth of 20 nm within the range of quantitative accuracy.
なお、上記Ｘ線光電子分光法（ＸＰＳ）は、Ｘ線源をＭｇＫα（３５０Ｗ）とし、パスエネルギー：５８．５ｅＶ、測定間隔：０．１２５ｅＶ、試料面に対する光電子取り出し角：４５ｄｅｇ、分析エリアを約８００μｍφの条件下で定量分析を実施した。なお、定量精度について、Ｎ／（Ｍ＋Ｖ＋Ａｌ＋Ｎ）の定量精度は±２％、Ａｌ／（Ｍ＋Ｖ＋Ａｌ）の定量精度は±１％である（Ｍは、Ｔｉ，Ｃｒの内の１種又は２種）。 In the X-ray photoelectron spectroscopy (XPS), the X-ray source is MgKα (350 W), the path energy is 58.5 eV, the measurement interval is 0.125 eV, the photoelectron extraction angle with respect to the sample surface is 45 deg, and the analysis area is about Quantitative analysis was performed under the condition of 800 μmφ. The quantitative accuracy of N / (M + V + Al + N) is ± 2% and the quantitative accuracy of Al / (M + V + Al) is ± 1% (M is one or two of Ti and Cr).
（２）比抵抗測定
反応性スパッタ法にて得られた薄膜サーミスタ部３について、４端子法にて２５℃での比抵抗を測定した。その結果を表１から表３に示す。
（３）Ｂ定数測定
膜評価用素子１２１の２５℃及び５０℃の抵抗値を恒温槽内で測定し、２５℃と５０℃との抵抗値よりＢ定数を算出した。その結果を表１から表３に示す。また、２５℃と５０℃との抵抗値より負の温度特性をもつサーミスタであることを確認している。
(2) Specific resistance measurement About the thin film thermistor part 3 obtained by the reactive sputtering method, the specific resistance in 25 degreeC was measured by the 4 terminal method. The results are shown in Tables 1 to 3.
(3) B constant measurement The resistance value of 25 degreeC and 50 degreeC of the element 121 for film | membrane evaluation was measured within the thermostat, and B constant was computed from the resistance value of 25 degreeC and 50 degreeC. The results are shown in Tables 1 to 3. Further, it has been confirmed that the thermistor has a negative temperature characteristic from resistance values of 25 ° C. and 50 ° C.
なお、本発明におけるＢ定数算出方法は、上述したように２５℃と５０℃とのそれぞれの抵抗値から以下の式によって求めている。
Ｂ定数（Ｋ）＝ｌｎ（Ｒ２５／Ｒ５０）／（１／Ｔ２５−１／Ｔ５０）
Ｒ２５（Ω）：２５℃における抵抗値
Ｒ５０（Ω）：５０℃における抵抗値
Ｔ２５（Ｋ）：２９８．１５Ｋ ２５℃を絶対温度表示
Ｔ５０（Ｋ）：３２３．１５Ｋ ５０℃を絶対温度表示
In addition, the B constant calculation method in this invention is calculated | required by the following formula | equation from each resistance value of 25 degreeC and 50 degreeC as mentioned above.
B constant (K) = ln (R25 / R50) / (1 / T25-1 / T50)
R25 (Ω): resistance value at 25 ° C. R50 (Ω): resistance value at 50 ° C. T25 (K): 298.15K 25 ° C. is displayed as an absolute temperature T50 (K): 323.15K 50 ° C. is displayed as an absolute temperature
これらの結果からわかるように、（Ｍ１−ｗＶｗ）ｘＡｌｙＮｚ（Ｍが、Ｔｉ，Ｃｒの内の１種又は２種）の組成比が図１から図３に示す３元系の三角図において、点Ａ，Ｂ，Ｃ，Ｄで囲まれる領域内、すなわち、「０．０＜ｗ＜１．０、０．７０≦ｙ／（ｘ＋ｙ）≦０．９８、０．４≦ｚ≦０．５、ｘ＋ｙ＋ｚ＝１」となる領域内の実施例全てで、抵抗率：１００Ωｃｍ以上、Ｂ定数：１５００Ｋ以上のサーミスタ特性が達成されている。 As can be seen from these results, the composition ratio of (M1-wVw) × AlyNz (M is one or two of Ti and Cr) is shown in the triangular diagram of the ternary system shown in FIGS. In the region surrounded by A, B, C, D, that is, “0.0 <w <1.0, 0.70 ≦ y / (x + y) ≦ 0.98, 0.4 ≦ z ≦ 0.5, In all examples in the region where “x + y + z = 1”, thermistor characteristics of resistivity: 100 Ωcm or more and B constant: 1500 K or more are achieved.
上記結果から２５℃での抵抗率とＢ定数との関係を示したグラフを、図７から図９に示す。また、Ａｌ／（Ｔｉ＋Ｖ＋Ａｌ）比とＢ定数との関係を示したグラフを、図１０に示すと共に、Ａｌ／（Ｃｒ＋Ｖ＋Ａｌ）比とＢ定数との関係を示したグラフを、図１１に示す。また、Ａｌ／（Ｔｉ＋Ｃｒ＋Ｖ＋Ａｌ）比とＢ定数との関係を示したグラフを、図１２に示す。
さらに、Ｖ／（Ｔｉ＋Ｖ）比とＢ定数との関係を示したグラフを、図１３に示す。また、Ｖ／（Ｃｒ＋Ｖ）比とＢ定数との関係を示したグラフを、図１４に示す。
Graphs showing the relationship between the resistivity at 25 ° C. and the B constant based on the above results are shown in FIGS. A graph showing the relationship between the Al / (Ti + V + Al) ratio and the B constant is shown in FIG. 10, and a graph showing the relationship between the Al / (Cr + V + Al) ratio and the B constant is shown in FIG. FIG. 12 is a graph showing the relationship between the Al / (Ti + Cr + V + Al) ratio and the B constant.
Further, a graph showing the relationship between the V / (Ti + V) ratio and the B constant is shown in FIG. FIG. 14 is a graph showing the relationship between the V / (Cr + V) ratio and the B constant.
これらのグラフから、Ａｌ／（Ｔｉ＋Ｖ＋Ａｌ）＝０．７〜０．９８、かつ、Ｎ／（Ｔｉ＋Ｖ＋Ａｌ＋Ｎ）＝０．４〜０．５の領域で、結晶系が六方晶のウルツ鉱型の単一相であるものは、２５℃における比抵抗値が１００Ωｃｍ以上、Ｂ定数が１５００Ｋ以上の高抵抗かつ高Ｂ定数の領域が実現できている。
また、Ａｌ／（Ｃｒ＋Ｖ＋Ａｌ）＝０．７〜０．９８、かつ、Ｎ／（Ｃｒ＋Ｖ＋Ａｌ＋Ｎ）＝０．４〜０．５の領域で、結晶系が六方晶のウルツ鉱型の単一相であるものは、２５℃における比抵抗値が１００Ωｃｍ以上、Ｂ定数が１５００Ｋ以上の高抵抗かつ高Ｂ定数の領域が実現できている。さらに、Ａｌ／（Ｔｉ＋Ｃｒ＋Ｖ＋Ａｌ）＝０．７〜０．９８、かつ、Ｎ／（Ｔｉ＋Ｃｒ＋Ｖ＋Ａｌ＋Ｎ）＝０．４〜０．５の領域で、結晶系が六方晶のウルツ鉱型の単一相であるものは、２５℃における比抵抗値が１００Ωｃｍ以上、Ｂ定数が１５００Ｋ以上の高抵抗かつ高Ｂ定数の領域が実現できている。
なお、図７及び図１４のデータにおいて、同じＡｌ／（Ｔｉ＋Ｖ＋Ａｌ）比又はＶ／（Ｔｉ＋Ｖ）比、同じＡｌ／（Ｃｒ＋Ｖ＋Ａｌ）比又はＶ／（Ｃｒ＋Ｖ）比、または同じＡｌ／（Ｔｉ＋Ｃｒ＋Ｖ＋Ａｌ）比に対して、Ｂ定数がばらついているのは、結晶中の窒素量が異なる、もしくは窒素欠陥等の格子欠陥量が異なるためである。
From these graphs, the wurtzite single crystal system is hexagonal in the region of Al / (Ti + V + Al) = 0.7 to 0.98 and N / (Ti + V + Al + N) = 0.4 to 0.5. As a phase, a high resistance and high B constant region having a specific resistance value at 25 ° C. of 100 Ωcm or more and a B constant of 1500 K or more can be realized.
Further, it is a wurtzite single phase in which the crystal system is hexagonal in the region of Al / (Cr + V + Al) = 0.7 to 0.98 and N / (Cr + V + Al + N) = 0.4 to 0.5. A high resistance and high B constant region having a specific resistance value at 25 ° C. of 100 Ωcm or more and a B constant of 1500 K or more can be realized. Furthermore, in the region of Al / (Ti + Cr + V + Al) = 0.7 to 0.98 and N / (Ti + Cr + V + Al + N) = 0.4 to 0.5, the crystal system is a wurtzite single phase with a hexagonal system. A high resistance and high B constant region having a specific resistance value at 25 ° C. of 100 Ωcm or more and a B constant of 1500 K or more can be realized.
7 and 14, the same Al / (Ti + V + Al) ratio or V / (Ti + V) ratio, the same Al / (Cr + V + Al) ratio or V / (Cr + V) ratio, or the same Al / (Ti + Cr + V + Al) ratio. On the other hand, the B constant varies because the amount of nitrogen in the crystal is different or the amount of lattice defects such as nitrogen defects is different.
ＭがＴｉの場合である表１に示す比較例２，３は、Ａｌ／（Ｔｉ＋Ｖ＋Ａｌ）＜０．７の領域であり、結晶系は立方晶のＮａＣｌ型となっている。
このように、Ａｌ／（Ｔｉ＋Ｖ＋Ａｌ）＜０．７の領域では、２５℃における比抵抗値が１００Ωｃｍ未満、Ｂ定数が１５００Ｋ未満であり、低抵抗かつ低Ｂ定数の領域であった。
表１に示す比較例１は、Ｎ／（Ｔｉ＋Ｖ＋Ａｌ＋Ｎ）が４０％に満たない領域であり、金属が窒化不足の結晶状態になっている。この比較例１は、ＮａＣｌ型でも、ウルツ鉱型でもない、非常に結晶性の劣る状態であった。また、これら比較例では、Ｂ定数及び抵抗値が共に非常に小さく、金属的振舞いに近いことがわかった。
Comparative Examples 2 and 3 shown in Table 1 where M is Ti are regions of Al / (Ti + V + Al) <0.7, and the crystal system is cubic NaCl type.
Thus, in the region of Al / (Ti + V + Al) <0.7, the specific resistance value at 25 ° C. was less than 100 Ωcm, the B constant was less than 1500 K, and the region was low resistance and low B constant.
Comparative Example 1 shown in Table 1 is a region where N / (Ti + V + Al + N) is less than 40%, and the metal is in a crystalline state with insufficient nitriding. This Comparative Example 1 was neither in the NaCl type nor in the wurtzite type, but in a state of very poor crystallinity. Further, in these comparative examples, it was found that both the B constant and the resistance value were very small and close to the metallic behavior.
ＭがＣｒの場合である表２に示す比較例２は、Ａｌ／（Ｃｒ＋Ｖ＋Ａｌ）＜０．７の領域であり、結晶系は立方晶のＮａＣｌ型となっている。
このように、Ａｌ／（Ｃｒ＋Ｖ＋Ａｌ）＜０．７の領域では、２５℃における比抵抗値が１００Ωｃｍ未満、Ｂ定数が１５００Ｋ未満であり、低抵抗かつ低Ｂ定数の領域であった。
表２に示す比較例１は、Ｎ／（Ｃｒ＋Ｖ＋Ａｌ＋Ｎ）が４０％に満たない領域であり、金属が窒化不足の結晶状態になっている。この比較例１は、ＮａＣｌ型でも、ウルツ鉱型でもない、非常に結晶性の劣る状態であった。また、これら比較例では、Ｂ定数及び抵抗値が共に非常に小さく、金属的振舞いに近いことがわかった。
Comparative Example 2 shown in Table 2 where M is Cr is a region of Al / (Cr + V + Al) <0.7, and the crystal system is cubic NaCl type.
Thus, in the region of Al / (Cr + V + Al) <0.7, the specific resistance value at 25 ° C. was less than 100 Ωcm, the B constant was less than 1500 K, and the region was low resistance and low B constant.
Comparative Example 1 shown in Table 2 is a region where N / (Cr + V + Al + N) is less than 40%, and the metal is in a crystalline state that is insufficiently nitrided. This Comparative Example 1 was neither in the NaCl type nor in the wurtzite type, but in a state of very poor crystallinity. Further, in these comparative examples, it was found that both the B constant and the resistance value were very small and close to the metallic behavior.
ＭがＴｉ，Ｃｒの場合である表３に示す比較例２は、Ａｌ／（Ｔｉ＋Ｃｒ＋Ｖ＋Ａｌ）＜０．７の領域であり、結晶系は立方晶のＮａＣｌ型となっている。
このように、Ａｌ／（Ｔｉ＋Ｃｒ＋Ｖ＋Ａｌ）＜０．７の領域では、２５℃における比抵抗値が１００Ωｃｍ未満、Ｂ定数が１５００Ｋ未満であり、低抵抗かつ低Ｂ定数の領域であった。
表３に示す比較例１は、Ｎ／（Ｔｉ＋Ｃｒ＋Ｖ＋Ａｌ＋Ｎ）が４０％に満たない領域であり、金属が窒化不足の結晶状態になっている。この比較例１は、ＮａＣｌ型でも、ウルツ鉱型でもない、非常に結晶性の劣る状態であった。また、これら比較例では、Ｂ定数及び抵抗値が共に非常に小さく、金属的振舞いに近いことがわかった。
Comparative Example 2 shown in Table 3 where M is Ti and Cr is a region of Al / (Ti + Cr + V + Al) <0.7, and the crystal system is cubic NaCl type.
Thus, in the region of Al / (Ti + Cr + V + Al) <0.7, the specific resistance value at 25 ° C. was less than 100 Ωcm, the B constant was less than 1500 K, and the region was low resistance and low B constant.
Comparative Example 1 shown in Table 3 is a region where N / (Ti + Cr + V + Al + N) is less than 40%, and the metal is in a crystal state that is insufficiently nitrided. This Comparative Example 1 was neither in the NaCl type nor in the wurtzite type, but in a state of very poor crystallinity. Further, in these comparative examples, it was found that both the B constant and the resistance value were very small and close to the metallic behavior.
（４）薄膜Ｘ線回折（結晶相の同定）
反応性スパッタ法にて得られた薄膜サーミスタ部３を、視斜角入射Ｘ線回折（Grazing Incidence X-ray Diffraction）により、結晶相を同定した。この薄膜Ｘ線回折は、微小角Ｘ線回折実験であり、管球をＣｕとし、入射角を１度とすると共に２θ＝２０〜１３０度の範囲で測定した。一部のサンプルについては、入射角を０度とし、２θ＝２０〜１００度の範囲で測定した。
(4) Thin film X-ray diffraction (identification of crystal phase)
The crystal phase of the thin film thermistor part 3 obtained by the reactive sputtering method was identified by grazing incidence X-ray diffraction (Grazing Incidence X-ray Diffraction). This thin film X-ray diffraction was a small angle X-ray diffraction experiment, and the measurement was performed in the range of 2θ = 20 to 130 degrees with Cu as the tube, the incident angle of 1 degree. Some samples were measured in the range of 2θ = 20 to 100 degrees with an incident angle of 0 degrees.
その結果、Ａｌ／（Ｍ＋Ｖ＋Ａｌ）≧０．７の領域（Ｍは、Ｔｉ，Ｃｒの内の１種又は２種）においては、ウルツ鉱型相（六方晶、ＡｌＮと同じ相）であり、Ａｌ／（Ｍ＋Ｖ＋Ａｌ）＜０．６６の領域においては、ＮａＣｌ型相（立方晶、ＴｉＮ、ＣｒＮ、ＶＮと同じ相）であった。また、０．６６＜Ａｌ／（Ｍ＋Ｖ＋Ａｌ）＜０．７においては、ウルツ鉱型相とＮａＣｌ型相との共存する結晶相であると考えられる。 As a result, in the region of Al / (M + V + Al) ≧ 0.7 (M is one or two of Ti and Cr), it is a wurtzite phase (hexagonal crystal, same phase as AlN), Al In the region of /(M+V+Al)<0.66, it was a NaCl type phase (the same phase as cubic, TiN, CrN, VN). Further, when 0.66 <Al / (M + V + Al) <0.7, it is considered that the wurtzite type phase and the NaCl type phase coexist.
このようにＭＶＡｌＮ（Ｍは、Ｔｉ，Ｃｒの内の１種又は２種）系においては、高抵抗かつ高Ｂ定数の領域は、Ａｌ／（Ｍ＋Ｖ＋Ａｌ）≧０．７のウルツ鉱型相に存在している。なお、本発明の実施例では、不純物相は確認されておらず、ウルツ鉱型の単一相である。
なお、表１から表３に示す比較例１は、上述したように結晶相がウルツ鉱型相でもＮａＣｌ型相でもなく、本試験においては同定できなかった。また、これらの比較例は、ＸＲＤのピーク幅が非常に広いことから、非常に結晶性の劣る材料であった。これは、電気特性により金属的振舞いに近いことから、窒化不足の金属相になっていると考えられる。
Thus, in the MVAlN (M is one or two of Ti and Cr) system, the region of high resistance and high B constant exists in the wurtzite phase of Al / (M + V + Al) ≧ 0.7. doing. In the examples of the present invention, the impurity phase is not confirmed, and is a wurtzite type single phase.
In Comparative Example 1 shown in Tables 1 to 3, the crystal phase was neither a wurtzite type phase nor an NaCl type phase as described above, and could not be identified in this test. Further, these comparative examples were materials with very poor crystallinity because the peak width of XRD was very wide. This is considered to be a metal phase with insufficient nitriding because it is close to a metallic behavior due to electrical characteristics.
次に、本発明の実施例は全てウルツ鉱型相の膜であり、配向性が強いことから、Ｓｉ基板Ｓ上に垂直な方向（膜厚方向）の結晶軸においてａ軸配向性とｃ軸配向性のどちらが強いか、ＸＲＤを用いて調査した。この際、結晶軸の配向性を調べるために、（１００）（ａ軸配向を示すｈｋｌ指数）と（００２）（ｃ軸配向を示すｈｋｌ指数）とのピーク強度比を測定した。 Next, all the examples of the present invention are films of wurtzite type phase, and since the orientation is strong, the a-axis orientation and the c-axis in the crystal axis in the direction perpendicular to the Si substrate S (film thickness direction). Which of the orientations is stronger was investigated using XRD. At this time, the peak intensity ratio of (100) (hkl index indicating a-axis orientation) and (002) (hkl index indicating c-axis orientation) was measured in order to investigate the orientation of crystal axes.
その結果、スパッタガス圧が０．７Ｐａ未満で成膜された実施例は、（１００）よりも（００２）の強度が非常に強く、ａ軸配向性よりｃ軸配向性が強い膜であった。一方、スパッタガス圧が０．７Ｐａ以上で成膜された実施例は、（００２）よりも（１００）の強度が非常に強く、ｃ軸配向よりａ軸配向が強い材料であった。
なお、同じ成膜条件でポリイミドフィルムに成膜しても、同様にウルツ鉱型の単一相が形成されていることを確認している。また、同じ成膜条件でポリイミドフィルムに成膜しても、配向性は変わらないことを確認している。
As a result, the example in which the film was formed at a sputtering gas pressure of less than 0.7 Pa was a film having a stronger (002) strength than (100) and a stronger c-axis orientation than a-axis orientation. . On the other hand, the example in which the film was formed at a sputtering gas pressure of 0.7 Pa or higher was a material having a (100) strength much stronger than (002) and a stronger a-axis orientation than c-axis orientation.
In addition, even if it formed into a film on the polyimide film on the same film-forming conditions, it confirmed that the wurtzite type single phase was formed similarly. Moreover, even if it forms into a film on a polyimide film on the same film-forming conditions, it has confirmed that orientation does not change.
ｃ軸配向が強い実施例のＸＲＤプロファイルの一例を、図１５から図１７に示す。図１５の実施例は、Ａｌ／（Ｔｉ＋Ｖ＋Ａｌ）＝０．８８（ウルツ鉱型、六方晶）であり、入射角を１度として測定した。また、図１６の実施例は、Ａｌ／（Ｃｒ＋Ｖ＋Ａｌ）＝０．９５（ウルツ鉱型、六方晶）であり、入射角を１度として測定した。さらに、図１７の実施例は、Ａｌ／（Ｔｉ＋Ｃｒ＋Ｖ＋Ａｌ）＝０．８５（ウルツ鉱型、六方晶）であり、入射角を１度として測定した。
これらの結果からわかるように、これらの実施例では、（１００）よりも（００２）の強度が非常に強くなっている。
An example of the XRD profile of the embodiment having a strong c-axis orientation is shown in FIGS. In the example of FIG. 15, Al / (Ti + V + Al) = 0.88 (wurtzite type, hexagonal crystal), and the incident angle was measured as 1 degree. In the example of FIG. 16, Al / (Cr + V + Al) = 0.95 (wurtzite type, hexagonal crystal), and the incident angle was 1 degree. Further, in the example of FIG. 17, Al / (Ti + Cr + V + Al) = 0.85 (wurtzite type, hexagonal crystal), and the incident angle was measured as 1 degree.
As can be seen from these results, in these examples, the intensity of (002) is much stronger than (100).
また、ａ軸配向が強い実施例のＸＲＤプロファイルの一例を、図１８から図２０に示す。図１８の実施例は、Ａｌ／（Ｔｉ＋Ｖ＋Ａｌ）＝０．８６（ウルツ鉱型、六方晶）であり、入射角を１度として測定した。また、図１９の実施例は、Ａｌ／（Ｃｒ＋Ｖ＋Ａｌ）＝０．８９（ウルツ鉱型、六方晶）であり、入射角を１度として測定した。さらに、図２０の実施例は、Ａｌ／（Ｔｉ＋Ｃｒ＋Ｖ＋Ａｌ）＝０．８３（ウルツ鉱型、六方晶）であり、入射角を１度として測定した。
これらの結果からわかるように、これらの実施例では、（００２）よりも（１００）の強度が非常に強くなっている。
Moreover, an example of the XRD profile of an Example with a strong a-axis orientation is shown in FIGS. In the example of FIG. 18, Al / (Ti + V + Al) = 0.86 (wurtzite type, hexagonal crystal), and the incident angle was measured as 1 degree. In the example of FIG. 19, Al / (Cr + V + Al) = 0.89 (wurtzite type, hexagonal crystal), and the incident angle was 1 degree. Further, in the example of FIG. 20, Al / (Ti + Cr + V + Al) = 0.83 (wurtzite type, hexagonal crystal), and the incident angle was measured as 1 degree.
As can be seen from these results, in these examples, the intensity of (100) is much stronger than (002).
なお、グラフ中（＊）は装置由来および熱酸化膜付きＳｉ基板由来のピークであり、サンプル本体のピーク、もしくは、不純物相のピークではないことを確認している。また、入射角を０度として、対称測定を実施し、そのピークが消失していることを確認し、装置由来および熱酸化膜付きＳｉ基板由来のピークであることを確認した。 In the graph, (*) is a peak derived from the apparatus and from the Si substrate with a thermal oxide film, and it is confirmed that it is not the peak of the sample body or the peak of the impurity phase. Moreover, the incident angle was set to 0 degree, the symmetry measurement was implemented, it confirmed that the peak had disappeared, and it was checked that it is a peak derived from a device and a Si substrate with a thermal oxide film.
次に、ウルツ鉱型材料である本発明の実施例に関して、さらに結晶構造と電気特性との相関を詳細に比較した。
図２１から図２３に示すように、Ａｌ／（Ｍ＋Ｖ＋Ａｌ）比、すなわちＡｌ／（Ｔｉ＋Ｖ＋Ａｌ）比、Ａｌ／（Ｃｒ＋Ｖ＋Ａｌ）比又はＡｌ／（Ｔｉ＋Ｃｒ＋Ｖ＋Ａｌ）比が近い比率のものに対し、基板面に垂直方向の配向度の強い結晶軸がｃ軸である実施例の材料とａ軸である実施例の材料とがある。なお、図２３には、Ａｌ／（Ｔｉ＋Ｃｒ＋Ｖ＋Ａｌ）比が０．７５〜０．８５の材料が、プロットされている。
Next, the correlation between the crystal structure and the electrical characteristics was further compared in detail for the example of the present invention which is a wurtzite type material.
As shown in FIGS. 21 to 23, the Al / (M + V + Al) ratio, that is, the Al / (Ti + V + Al) ratio, Al / (Cr + V + Al) ratio, or Al / (Ti + Cr + V + Al) ratio is close to the substrate surface. There are an example material in which the crystal axis having a strong degree of orientation in the direction is the c axis and an example material in which the crystal axis is the a axis. In FIG. 23, materials having an Al / (Ti + Cr + V + Al) ratio of 0.75 to 0.85 are plotted.
これら両者を比較すると、Ａｌ／（Ｍ＋Ｖ＋Ａｌ）比がほぼ同じであると、ａ軸配向が強い材料よりもｃ軸配向が強い材料の方が、Ｂ定数が大きいことがわかる。また、Ｎ量（Ｎ／（Ｍ＋Ｖ＋Ａｌ＋Ｎ））に着目すると、ａ軸配向が強い材料よりもｃ軸配向が強い材料の方が、窒素量がわずかに大きいことがわかる。窒素欠陥がない場合の化学量論比が０．５（すなわち、Ｎ／（Ｍ＋Ｖ＋Ａｌ＋Ｎ）＝０．５）であることから、ｃ軸配向が強い材料のほうが、窒素欠陥量が少なく理想的な材料であることがわかる。 Comparing these two, it can be seen that when the Al / (M + V + Al) ratio is substantially the same, a material having a strong c-axis orientation has a larger B constant than a material having a strong a-axis orientation. Further, focusing on the N amount (N / (M + V + Al + N)), it can be seen that the material having a strong c-axis orientation has a slightly larger amount of nitrogen than the material having a strong a-axis orientation. Since the stoichiometric ratio when there is no nitrogen defect is 0.5 (that is, N / (M + V + Al + N) = 0.5), a material with strong c-axis orientation has less nitrogen defect and is an ideal material. It can be seen that it is.
なお、ａ軸配向の強い実施例とｃ軸配向の強い実施例とを比較したＶ／（Ｔｉ＋Ｖ）比とＢ定数との関係を示すグラフを、図２４とに示す。なお、図２４には、Ａｌ／（Ｔｉ＋Ｖ＋Ａｌ）比がほとんど同じ材料が、プロットされている。Ａｌ／（Ｔｉ＋Ｖ＋Ａｌ）比が同じで、かつ、Ｖ／（Ｔｉ＋Ｖ）比が同じであると、ａ軸配向が強い材料よりもｃ軸配向が強い材料の方が、Ｂ定数が大きくなることを見出している。
また、ａ軸配向の強い実施例とｃ軸配向の強い実施例とを比較したＶ／（Ｃｒ＋Ｖ）比とＢ定数との関係を示すグラフを、図２５に示す。なお、図２５には、Ａｌ／（Ｃｒ＋Ｖ＋Ａｌ）比が０．９５〜０．９８の材料が、プロットされている。Ａｌ／（Ｃｒ＋Ｖ＋Ａｌ）比が同程度量で、かつ、Ｖ／（Ｃｒ＋Ｖ）比が同程度量であると、ａ軸配向が強い材料よりもｃ軸配向が強い材料の方が、Ｂ定数が大きいことがわかる。
FIG. 24 is a graph showing the relationship between the V / (Ti + V) ratio and the B constant, which compares an example with strong a-axis orientation and an example with strong c-axis orientation. In FIG. 24, materials having almost the same Al / (Ti + V + Al) ratio are plotted. It has been found that when the Al / (Ti + V + Al) ratio is the same and the V / (Ti + V) ratio is the same, a material having a strong c-axis orientation has a higher B constant than a material having a strong a-axis orientation. ing.
In addition, FIG. 25 shows a graph showing the relationship between the V / (Cr + V) ratio and the B constant, comparing an example with strong a-axis orientation and an example with strong c-axis orientation. In FIG. 25, materials having an Al / (Cr + V + Al) ratio of 0.95 to 0.98 are plotted. When the Al / (Cr + V + Al) ratio is about the same amount and the V / (Cr + V) ratio is about the same amount, a material having a strong c-axis orientation has a larger B constant than a material having a strong a-axis orientation. I understand that.
＜結晶形態の評価＞
次に、薄膜サーミスタ部３の断面における結晶形態を示す一例として、ＭがＴｉの場合として、熱酸化膜付きＳｉ基板Ｓ上に４４０ｎｍ程度成膜された実施例（Ａｌ／（Ｔｉ＋Ｖ＋Ａｌ）＝０．８８，ウルツ鉱型六方晶、ｃ軸配向性が強い）の薄膜サーミスタ部３における断面ＳＥＭ写真を、図２６に示す。
また、ＭがＣｒの場合として、熱酸化膜付きＳｉ基板Ｓ上に４５０ｎｍ程度成膜された実施例（Ａｌ／（Ｃｒ＋Ｖ＋Ａｌ）＝０．９０，ウルツ鉱型六方晶、ｃ軸配向性が強い）の薄膜サーミスタ部３における断面ＳＥＭ写真を、図２７に示す。
さらに、ＭがＴｉ，Ｃｒの場合として、熱酸化膜付きＳｉ基板Ｓ上に４５０ｎｍ程度成膜された実施例（Ａｌ／（Ｔｉ＋Ｃｒ＋Ｖ＋Ａｌ）＝０．８５，ウルツ鉱型六方晶、ｃ軸配向性が強い）の薄膜サーミスタ部３における断面ＳＥＭ写真を、図２８に示す。
<Evaluation of crystal form>
Next, as an example showing the crystal form in the cross section of the thin film thermistor section 3, when M is Ti, an embodiment (Al / (Ti + V + Al) = 0. FIG. 26 shows a cross-sectional SEM photograph of the thin film thermistor portion 3 of (88, wurtzite hexagonal crystal, strong c-axis orientation).
Further, in the case where M is Cr, an example in which about 450 nm is formed on a Si substrate S with a thermal oxide film (Al / (Cr + V + Al) = 0.90, wurtzite type hexagonal crystal, strong c-axis orientation) A cross-sectional SEM photograph of the thin film thermistor section 3 is shown in FIG.
Further, in the case where M is Ti, Cr, an example (Al / (Ti + Cr + V + Al) = 0.85, a wurtzite hexagonal crystal with c-axis orientation is formed on a Si substrate S with a thermal oxide film. FIG. 28 shows a cross-sectional SEM photograph of the (strong) thin film thermistor section 3.
次に、ＭがＴｉの場合として、別の実施例（Ａｌ／（Ｔｉ＋Ｖ＋Ａｌ）＝０．８６，ウルツ鉱型六方晶、ａ軸配向性が強い）の薄膜サーミスタ部３における断面ＳＥＭ写真を、図２９に示す。
また、ＭがＣｒの場合として、別の実施例（Ａｌ／（Ｃｒ＋Ｖ＋Ａｌ）＝０．８９，ウルツ鉱型六方晶、ａ軸配向性が強い）の薄膜サーミスタ部３における断面ＳＥＭ写真を、図３０に示す。
さらに、ＭがＴｉ，Ｃｒの場合として、別の実施例（Ａｌ／（Ｔｉ＋Ｃｒ＋Ｖ＋Ａｌ）＝０．８３，ウルツ鉱型六方晶、ａ軸配向性が強い）の薄膜サーミスタ部３における断面ＳＥＭ写真を、図３２に示す。
これら実施例のサンプルは、Ｓｉ基板Ｓをへき開破断したものを用いている。また、４５°の角度で傾斜観察した写真である。
Next, as a case where M is Ti, a cross-sectional SEM photograph in the thin film thermistor part 3 of another example (Al / (Ti + V + Al) = 0.86, wurtzite hexagonal crystal, strong a-axis orientation) is shown in FIG. 29.
Further, in the case where M is Cr, a cross-sectional SEM photograph in the thin film thermistor portion 3 of another example (Al / (Cr + V + Al) = 0.89, wurtzite hexagonal crystal, strong a-axis orientation) is shown in FIG. Shown in
Furthermore, as a case where M is Ti, Cr, a cross-sectional SEM photograph in the thin film thermistor portion 3 of another example (Al / (Ti + Cr + V + Al) = 0.83, wurtzite hexagonal crystal, strong a-axis orientation) As shown in FIG.
The samples of these examples are those obtained by cleaving the Si substrate S. Moreover, it is the photograph which observed the inclination at an angle of 45 degrees.
これらの写真からわかるように、いずれの実施例も緻密な柱状結晶で形成されている。すなわち、ｃ軸配向が強い実施例及びａ軸配向が強い実施例の共に基板面に垂直な方向に柱状の結晶が成長している様子が観測されている。なお、柱状結晶の破断は、Ｓｉ基板Ｓをへき開破断した際に生じたものである。 As can be seen from these photographs, all the examples are formed of dense columnar crystals. That is, it has been observed that columnar crystals grow in a direction perpendicular to the substrate surface in both the embodiment with strong c-axis orientation and the embodiment with strong a-axis orientation. Note that the breakage of the columnar crystal occurred when the Si substrate S was cleaved.
なお、図中の柱状結晶サイズについて、ＭがＴｉの場合である図２６のｃ軸配向が強い実施例は、粒径が１０ｎｍφ（±５ｎｍφ）、長さ４４０ｎｍ程度であり、図２９のａ軸配向が強い実施例は、粒径が１５ｎｍφ（±１０ｎｍφ）、長さ４３０ｎｍ程度であった。
また、ＭがＣｒの場合である図２７のｃ軸配向が強い実施例は、粒径が１０ｎｍφ（±５ｎｍφ）、長さ４５０ｎｍ程度であり、図３０のａ軸配向が強い実施例は、粒径が１５ｎｍφ（±１０ｎｍφ）、長さ４２５ｎｍ程度であった。
さらに、ＭがＴｉ，Ｃｒの場合である図２８のｃ軸配向が強い実施例は、粒径が１０ｎｍφ（±５ｎｍφ）、長さ４５０ｎｍ程度であり、図３１のａ軸配向が強い実施例は、粒径が１５ｎｍφ（±１０ｎｍφ）、長さ４７０ｎｍ程度であった。
In addition, as for the columnar crystal size in the figure, the embodiment with strong c-axis orientation in FIG. 26 where M is Ti has a grain size of about 10 nmφ (± 5 nmφ) and a length of about 440 nm, and the a-axis in FIG. In the example with strong orientation, the particle size was about 15 nmφ (± 10 nmφ) and the length was about 430 nm.
Further, in the embodiment with strong c-axis orientation in FIG. 27 where M is Cr, the embodiment has a grain size of about 10 nmφ (± 5 nmφ) and a length of about 450 nm, and the embodiment with strong a-axis orientation in FIG. The diameter was 15 nmφ (± 10 nmφ) and the length was about 425 nm.
Further, in the embodiment having a strong c-axis orientation in FIG. 28 where M is Ti and Cr, the embodiment has a particle diameter of about 10 nmφ (± 5 nmφ) and a length of about 450 nm, and the embodiment having a strong a-axis orientation in FIG. The particle diameter was about 15 nmφ (± 10 nmφ) and the length was about 470 nm.
なお、ここでの粒径は、基板面内における柱状結晶の直径であり、長さは、基板面に垂直な方向の柱状結晶の長さ（膜厚）である。
柱状結晶のアスペクト比を（長さ）÷（粒径）として定義すると、ｃ軸配向が強い実施例およびａ軸配向が強い実施例の両実施例とも１０以上の大きいアスペクト比をもっている。柱状結晶の粒径が小さいことにより、膜が緻密となっていると考えられる。
なお、熱酸化膜付きＳｉ基板Ｓ上に２００ｎｍ、５００ｎｍ、１０００ｎｍの厚さでそれぞれ成膜された場合にも、上記同様、緻密な柱状結晶で形成されていることを確認している。
Here, the particle diameter is the diameter of the columnar crystal in the substrate surface, and the length is the length (film thickness) of the columnar crystal in the direction perpendicular to the substrate surface.
When the aspect ratio of the columnar crystal is defined as (length) / (grain size), both the embodiment with a strong c-axis orientation and the embodiment with a strong a-axis orientation have a large aspect ratio of 10 or more. It is considered that the film is dense due to the small grain size of the columnar crystals.
In addition, even when each film is formed with a thickness of 200 nm, 500 nm, and 1000 nm on the Si substrate S with a thermal oxide film, it is confirmed that the film is formed with dense columnar crystals as described above.
＜耐熱試験評価＞
表１から表３に示す実施例及び比較例の一部において、大気中，１２５℃，１０００ｈの耐熱試験前後における抵抗値及びＢ定数を評価した。その結果を表４から表６に示す。なお、比較として従来のＴａ−Ａｌ−Ｎ系材料による比較例も同様に評価した。
これらの結果からわかるように、Ａｌ濃度及び窒素濃度は異なるものの、Ｔａ−Ａｌ−Ｎ系である比較例と同程度量のＢ定数をもつ実施例で比較したとき、Ｍ−Ｖ−Ａｌ−Ｎ（Ｍは、Ｔｉ，Ｃｒの内の１種又は２種）系のほうが抵抗値上昇率、Ｂ定数上昇率がともに小さく、耐熱試験前後における電気特性変化でみたときの耐熱性は、Ｍ−Ｖ−Ａｌ−Ｎ（Ｍは、Ｔｉ，Ｃｒの内の１種又は２種）系のほうが優れている。
<Evaluation of heat resistance test>
In some examples and comparative examples shown in Tables 1 to 3, resistance values and B constants before and after a heat resistance test at 125 ° C. and 1000 h in the air were evaluated. The results are shown in Tables 4 to 6. For comparison, comparative examples using conventional Ta—Al—N materials were also evaluated in the same manner.
As can be seen from these results, although the Al concentration and the nitrogen concentration are different, when compared with an example having the same amount of B constant as that of the comparative example which is a Ta-Al-N system, MV-Al-N (M is one or two of Ti and Cr) The resistance increase rate and B constant increase rate are both smaller in the system, and the heat resistance when viewed from the change in electrical characteristics before and after the heat test is MV The -Al-N (M is one or two of Ti and Cr) system is superior.
なお、ＭがＴｉの場合、表１の実施例５，６はｃ軸配向が強い材料であり、実施例９，１０はａ軸配向が強い材料である。両者を比較すると、ｃ軸配向が強い実施例の方がａ軸配向が強い実施例に比べて、抵抗値上昇率が小さく、僅かに耐熱性が向上している。
また、ＭがＣｒの場合、表２の実施例６，７はｃ軸配向が強い材料であり、実施例９はａ軸配向が強い材料である。両者を比較すると、ｃ軸配向が強い実施例の方がａ軸配向が強い実施例に比べて、抵抗値上昇率が小さく、僅かに耐熱性が向上している。
さらに、ＭがＴｉ，Ｃｒの場合、表３の実施例６はｃ軸配向が強い材料であり、実施例１０はａ軸配向が強い材料である。両者を比較すると、ｃ軸配向が強い実施例の方がａ軸配向が強い実施例に比べて、抵抗値上昇率が小さく、僅かに耐熱性が向上している。
When M is Ti, Examples 5 and 6 in Table 1 are materials with strong c-axis orientation, and Examples 9 and 10 are materials with strong a-axis orientation. When both are compared, the resistance value increase rate is smaller and the heat resistance is slightly improved in the example in which the c-axis orientation is stronger than in the example in which the a-axis orientation is strong.
When M is Cr, Examples 6 and 7 in Table 2 are materials with strong c-axis orientation, and Example 9 is a material with strong a-axis orientation. When both are compared, the resistance value increase rate is smaller and the heat resistance is slightly improved in the example in which the c-axis orientation is stronger than in the example in which the a-axis orientation is strong.
Further, when M is Ti or Cr, Example 6 in Table 3 is a material with strong c-axis orientation, and Example 10 is a material with strong a-axis orientation. When both are compared, the resistance value increase rate is smaller and the heat resistance is slightly improved in the example in which the c-axis orientation is stronger than in the example in which the a-axis orientation is strong.
なお、Ｔａ−Ａｌ−Ｎ系材料では、Ｔａのイオン半径がＴｉ，Ｃｒ，ＶやＡｌに比べて非常に大きいため、高濃度Ａｌ領域でウルツ鉱型相を作製することができない。ＴａＡｌＮ系がウルツ鉱型相でないがゆえ、ウルツ鉱型のＭ−Ｖ−Ａｌ−Ｎ（Ｍは、Ｔｉ，Ｃｒの内の１種又は２種）系の方が耐熱性が良好であると考えられる。 In the Ta—Al—N-based material, the ionic radius of Ta is much larger than that of Ti, Cr, V, and Al, and thus a wurtzite type phase cannot be produced in a high concentration Al region. Since the TaAlN system is not a wurtzite type phase, the wurtzite type M-V-Al-N (M is one or two of Ti and Cr) systems are considered to have better heat resistance. It is done.
＜窒素プラズマ照射による耐熱性評価＞
ＭがＴｉの場合、表１に示す実施例５の薄膜サーミスタ部３を成膜後に、真空度：６．７Ｐａ、出力：２００ＷでＮ２ガス雰囲気下で、窒素プラズマを照射させた。また、ＭがＣｒの場合、表２に示す実施例６の薄膜サーミスタ部３を成膜後に、真空度：６．７Ｐａ、出力：２００ＷでＮ２ガス雰囲気下で、窒素プラズマを照射させた。さらに、ＭがＴｉ，Ｃｒの場合、表３に示す実施例６の薄膜サーミスタ部３を成膜後に、真空度：６．７Ｐａ、出力：２００ＷでＮ２ガス雰囲気下で、窒素プラズマを照射させた。
<Evaluation of heat resistance by nitrogen plasma irradiation>
When M was Ti, after forming the thin film thermistor part 3 of Example 5 shown in Table 1, nitrogen plasma was irradiated in a N2 gas atmosphere at a vacuum degree of 6.7 Pa and an output of 200 W. Further, when M is Cr, after forming the thin film thermistor portion 3 of Example 6 shown in Table 2, nitrogen plasma was irradiated in a N 2 gas atmosphere at a vacuum degree of 6.7 Pa and an output of 200 W. Further, when M is Ti or Cr, after forming the thin film thermistor portion 3 of Example 6 shown in Table 3, the plasma was irradiated with nitrogen plasma in a N 2 gas atmosphere at a vacuum degree of 6.7 Pa and an output of 200 W. .
この窒素プラズマを実施した膜評価用素子１２１と実施しない膜評価用素子１２１とで耐熱試験を行った結果を、表７から表９に示す。この結果からわかるように、窒素プラズマを行った実施例では、比抵抗の上昇率が小さく、膜の耐熱性が向上している。これは、窒素プラズマによって膜の窒素欠陥が低減され、結晶性が向上したためである。なお、窒素プラズマはラジカル窒素を照射するとさらに良い。 Tables 7 to 9 show the results of the heat resistance test performed on the film evaluation element 121 that performed this nitrogen plasma and the film evaluation element 121 that did not. As can be seen from this result, in the example in which nitrogen plasma is used, the rate of increase in specific resistance is small, and the heat resistance of the film is improved. This is because the nitrogen plasma of the film is reduced by the nitrogen plasma and the crystallinity is improved. Nitrogen plasma is better irradiated with radical nitrogen.
このように上記評価において、Ｎ／（Ｍ＋Ｖ＋Ａｌ＋Ｎ）：０．４〜０．５の範囲で作製すれば、良好なサーミスタ特性を示すことができることがわかる。しかしながら、窒素欠陥のない場合の化学量論比は０．５（すなわち、Ｎ／（Ｍ＋Ｖ＋Ａｌ＋Ｎ）＝０．５）であり、今回の試験においては、窒素量が０．５より小さく、材料中に窒素欠陥があることがわかる。このため、窒素欠陥を補うプロセスを加えることが望ましく、その一つとして上記窒素プラズマ照射などが好ましい。 Thus, in the above evaluation, it can be seen that if the N / (M + V + Al + N) is made in the range of 0.4 to 0.5, good thermistor characteristics can be exhibited. However, the stoichiometric ratio when there is no nitrogen defect is 0.5 (that is, N / (M + V + Al + N) = 0.5). In this test, the nitrogen amount is smaller than 0.5, It can be seen that there is a nitrogen defect. For this reason, it is desirable to add a process for compensating for nitrogen defects, and as one of them, the nitrogen plasma irradiation or the like is preferable.
なお、本発明の技術範囲は上記実施形態及び実施例に限定されるものではなく、本発明の趣旨を逸脱しない範囲において種々の変更を加えることが可能である。 The technical scope of the present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the spirit of the present invention.
１…フィルム型サーミスタセンサ、２…絶縁性フィルム、３…薄膜サーミスタ部、４，１２４…パターン電極 DESCRIPTION OF SYMBOLS 1 ... Film type thermistor sensor, 2 ... Insulating film, 3 ... Thin film thermistor part, 4,124 ... Pattern electrode
Claims (8)
一般式：（Ｍ１−ｗＶｗ）ｘＡｌｙＮｚ（０．０＜ｗ＜１．０、０．７０≦ｙ／（ｘ＋ｙ）≦０．９８、０．４≦ｚ≦０．５、ｘ＋ｙ＋ｚ＝１）で示される金属窒化物からなり、
その結晶構造が、六方晶系のウルツ鉱型の単相であり、
前記Ｍが、Ｔｉ，Ｃｒの内の１種又は２種であることを特徴とするサーミスタ用金属窒化物材料。 A metal nitride material used for the thermistor,
General formula: (M1-wVw) xAlyNz (0.0 <w <1.0, 0.70 ≦ y / (x + y) ≦ 0.98, 0.4 ≦ z ≦ 0.5, x + y + z = 1) Made of metal nitride,
The crystal structure is a hexagonal wurtzite single phase,
The metal nitride material for a thermistor, wherein M is one or two of Ti and Cr.
膜状に形成され、
前記膜の表面に対して垂直方向に延在している柱状結晶であることを特徴とするサーミスタ用金属窒化物材料。 The thermistor metal nitride material according to claim 1,
Formed into a film,
A metal nitride material for a thermistor, wherein the metal nitride material is a columnar crystal extending in a direction perpendicular to the surface of the film.
膜状に形成され、
前記膜の表面に対して垂直方向にａ軸よりｃ軸が強く配向していることを特徴とするサーミスタ用金属窒化物材料。 The metal nitride material for a thermistor according to claim 1 or 2,
Formed into a film,
A metal nitride material for a thermistor, wherein the c-axis is oriented more strongly than the a-axis in a direction perpendicular to the surface of the film.
該絶縁性フィルム上に請求項１から３のいずれか一項に記載のサーミスタ用金属窒化物材料で形成された薄膜サーミスタ部と、
少なくとも前記薄膜サーミスタ部の上又は下に形成された一対のパターン電極とを備えていることを特徴とするフィルム型サーミスタセンサ。 An insulating film;
A thin film thermistor portion formed of the metal nitride material for a thermistor according to any one of claims 1 to 3 on the insulating film,
A film type thermistor sensor comprising at least a pair of pattern electrodes formed above or below the thin film thermistor section.
前記Ｍが、Ｔｉ，Ｃｒの内の少なくともＣｒを含む１種又は２種であり、
前記パターン電極の少なくとも前記薄膜サーミスタ部に接合する部分がＣｒで形成されていることを特徴とするフィルム型サーミスタセンサ。 In the film type thermistor sensor according to claim 4,
The M is one or two of at least Cr of Ti and Cr;
A film type thermistor sensor, wherein at least a portion of the pattern electrode joined to the thin film thermistor portion is formed of Cr.
Ｍ−Ｖ−Ａｌ合金スパッタリングターゲットを用いて窒素含有雰囲気中で反応性スパッタを行って成膜する成膜工程を有しており、
前記Ｍが、Ｔｉ，Ｃｒの内の１種又は２種であることを特徴とするサーミスタ用金属窒化物材料の製造方法。 A method for producing the thermistor metal nitride material according to any one of claims 1 to 3,
A film forming step of forming a film by performing reactive sputtering in a nitrogen-containing atmosphere using an MV-Al alloy sputtering target;
The method for producing a metal nitride material for a thermistor, wherein M is one or two of Ti and Cr.
前記反応性スパッタにおけるスパッタガス圧を、０．７Ｐａ未満に設定することを特徴とするサーミスタ用金属窒化物材料の製造方法。 In the manufacturing method of the metal nitride material for thermistors according to claim 6,
A method for producing a metal nitride material for a thermistor, wherein a sputtering gas pressure in the reactive sputtering is set to less than 0.7 Pa.
前記成膜工程後に、形成された膜に窒素プラズマを照射する工程を有していることを特徴とするサーミスタ用金属窒化物材料の製造方法。 In the manufacturing method of the metal nitride material for thermistors according to claim 6 or 7,
A method for producing a metal nitride material for a thermistor, comprising a step of irradiating the formed film with nitrogen plasma after the film forming step.
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