WO2014196649A1 - Matériau à base de nitrure métallique pour thermistors, son procédé de production et capteur à thermistor de type film - Google Patents

Matériau à base de nitrure métallique pour thermistors, son procédé de production et capteur à thermistor de type film Download PDF

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WO2014196649A1
WO2014196649A1 PCT/JP2014/065168 JP2014065168W WO2014196649A1 WO 2014196649 A1 WO2014196649 A1 WO 2014196649A1 JP 2014065168 W JP2014065168 W JP 2014065168W WO 2014196649 A1 WO2014196649 A1 WO 2014196649A1
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film
thermistor
metal nitride
nitride material
strong
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PCT/JP2014/065168
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English (en)
Japanese (ja)
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利晃 藤田
寛 田中
長友　憲昭
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三菱マテリアル株式会社
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Priority to CN201480022247.1A priority Critical patent/CN105144311A/zh
Publication of WO2014196649A1 publication Critical patent/WO2014196649A1/fr

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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
    • 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

Definitions

  • 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 manufacturing method thereof, and a film type thermistor sensor.
  • 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.
  • transition metal oxides such as Mn, Co, and Fe are generally used for such thermistor materials (see Patent Documents 1 to 3).
  • these thermistor materials require heat treatment such as firing at 550 ° C. or higher in order to obtain stable thermistor characteristics.
  • 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.
  • 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. Further, the obtained thin film is heat-treated at 350 to 600 ° C. as necessary.
  • 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 sensor in a composition where both the nitrogen content x and the subcomponent element M content y are 30 atomic% or less. Used for.
  • 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. Further, the obtained thin film is heat-treated at 200 to 1000 ° C. as necessary.
  • 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.
  • 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-based material, but there is no description regarding heat resistance, and the thermal reliability of the nitride-based 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.
  • 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.
  • 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.
  • the M is one or two of Ti and Cr.
  • M Cr
  • 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.
  • 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.
  • a film type thermistor sensor 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.
  • 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.
  • 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.
  • 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 of Ti and Cr, and at least the thin film thermistor portion of the pattern electrode.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 1 is a (Ti + V) -Al—N ternary phase diagram showing a composition range of a thermistor metal nitride material in an embodiment of a metal nitride material for a thermistor, a method for manufacturing the same, and a film type thermistor sensor according to the present invention. is there.
  • 1 is a (Cr + V) -Al—N-based ternary phase diagram showing a composition range of a thermistor metal nitride material in an embodiment of a metal nitride material for a thermistor, a manufacturing method thereof, and a film type thermistor sensor according to the present invention. is there.
  • FIG. 1 is a (Ti + Cr + V) -Al—N-based ternary phase diagram showing a composition range of a thermistor metal nitride material in an embodiment of a thermistor metal nitride material, a manufacturing method thereof, and a film type thermistor sensor according to the present invention. is there.
  • it is a perspective view which shows a film type thermistor sensor.
  • it is a perspective view which shows the manufacturing method of a film type thermistor sensor in order of a process.
  • Example of the metal nitride material for thermistors which concerns on this invention, its manufacturing method, and a film type thermistor sensor it is the front view and top view which show the element
  • it is a graph which shows the relationship between 25 degreeC resistivity and B constant about the case where M is Ti.
  • Example and comparative example which concern on this invention it is a graph which shows the relationship between Al / (Ti + V + Al) ratio and B constant.
  • it is a graph which shows the relationship between Al / (Cr + V + Al) ratio and B constant.
  • it is a graph which shows the relationship between V / (Ti + V) ratio and B constant.
  • Example and comparative example which concern on this invention it is a graph which shows the relationship between V / (Cr + V) ratio and B constant.
  • XRD X-ray diffraction
  • it is a graph which shows the relationship between Al / (Ti + V + Al) ratio and B constant which compared the Example with strong a-axis orientation, and the Example with strong c-axis orientation.
  • it is a graph which shows the relationship between Al / (Cr + V + Al) ratio and B constant which compared the Example with strong a-axis orientation, and the Example with strong c-axis orientation.
  • Example which concerns on this invention it is a graph which shows the relationship between Al / (Ti + Cr + V + Al) ratio and B constant which compared the Example with strong a-axis orientation, and the Example with strong c-axis orientation.
  • it is a graph which shows the relationship of V / (Ti + V) ratio and B constant which compared the Example with strong a-axis orientation, and the Example with strong c-axis orientation.
  • it is a graph which shows the relationship between V / (Cr + V) ratio and B constant which compared the Example with strong a-axis orientation, and the Example with strong c-axis orientation.
  • Example which concerns on this invention it is a cross-sectional SEM photograph which shows an Example with strong c-axis orientation about the case where M is Ti. In the Example which concerns on this invention, it is a cross-sectional SEM photograph which shows an Example with strong c-axis orientation about the case where M is Cr. In the Example which concerns on this invention, it is a cross-sectional SEM photograph which shows an Example with strong c-axis orientation about the case where M is Ti and Cr. In the Example which concerns on this invention, it is a cross-sectional SEM photograph which shows an Example with strong a-axis orientation about the case where M is Ti.
  • Example which concerns on this invention it is a cross-sectional SEM photograph which shows an Example with strong a-axis orientation about the case where M is Cr.
  • FIGS. 1 to 5 an embodiment of a metal nitride material for a thermistor, a manufacturing method thereof, and a film type thermistor sensor according to the present invention will be described with reference to FIGS. 1 to 5.
  • the scale is appropriately changed as necessary to make each part recognizable or easily recognizable.
  • 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.
  • M 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.
  • 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).
  • 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).
  • XRD X-ray diffraction
  • 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.
  • 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.
  • the insulating film 2 is formed in a band shape with, for example, a polyimide resin sheet.
  • 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.
  • a plating portion 4c such as Au plating is formed as a lead wire drawing portion on the base end portion of the pair of linear extending portions 4b. One end of a lead wire is joined to the plating portion 4c with a solder material or the like.
  • 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.
  • the method for producing a metal nitride material for a thermistor 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.
  • 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.
  • 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.
  • the present embodiment is formed on the insulating film 2 of a polyimide film having a thickness of 50 ⁇ m 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.
  • 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%.
  • 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.
  • 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%.
  • a 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.
  • a Cr film is formed to 20 nm, and an Au film is further formed to 200 nm.
  • 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. .
  • 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.
  • the comb electrode portion 4 a of the pattern electrode 4 is formed under the thin film thermistor portion 3.
  • a polyimide coverlay film 5 with an adhesive having a thickness of 50 ⁇ m 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 ⁇ m Au thin film by using, for example, an Au plating solution to form a plated portion 4c.
  • 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.
  • 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))
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the X-ray source is MgK ⁇ (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
  • the analysis area is about Quantitative analysis was performed under the condition of 800 ⁇ m ⁇ .
  • 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).
  • B constant (K) In (R25 / R50) / (1 / T25-1 / T50)
  • T25 (K): 298.15K 25 ° C. is displayed as an absolute temperature
  • T50 (K): 323.15K 50 ° C. is displayed as an absolute temperature
  • 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.
  • A, B, C, D that is, “0.0 ⁇ w ⁇ 1.0, 0.70 ⁇ y / (x + y) ⁇ 0.98, 0.4 ⁇ z ⁇ 0.5
  • thermistor characteristics of resistivity 100 ⁇ cm or more and B constant: 1500 K or more are achieved.
  • FIGS. 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.
  • FIG. 14 is a graph showing the relationship between the V / (Cr + V) ratio and the B constant.
  • a high resistance and high B constant region having a specific resistance value at 25 ° C. of 100 ⁇ cm or more and a B constant of 1500 K or more can be realized.
  • the crystal system is a hexagonal wurtzite single phase.
  • a high resistance and high B constant region having a specific resistance value at 25 ° C.
  • the crystal system is a wurtzite single phase having a hexagonal system.
  • a high resistance and high B constant region having a specific resistance value at 25 ° C. of 100 ⁇ cm or more and a B constant of 1500 K or more can be realized.
  • 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.
  • 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.
  • the specific resistance value at 25 ° C. was less than 100 ⁇ cm
  • the B constant was less than 1500 K
  • 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.
  • Thin film X-ray diffraction (identification of crystal phase)
  • the crystal phase of the thin film thermistor portion 3 obtained by the reactive sputtering method was identified by grazing incidence X-ray diffraction (Grazing Incidence X-ray Diffraction).
  • the region of high resistance and high B constant exists in the wurtzite phase of Al / (M + V + Al) ⁇ 0.7. is doing.
  • the impurity phase is not confirmed, and is a wurtzite type single phase.
  • 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.
  • 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 perpendicular to the Si substrate S (film thickness direction) Which of the orientations is stronger was investigated using XRD.
  • 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.
  • 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.
  • 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.
  • 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.
  • orientation does not change.
  • Al / (Ti + V + Al) 0.88 (wurtzite type, hexagonal crystal), and the incident angle was measured as 1 degree.
  • Al / (Cr + V + Al) 0.95 (wurtzite type, hexagonal crystal), and the incident angle was 1 degree.
  • Al / (Ti + Cr + V + Al) 0.85 (wurtzite type, hexagonal crystal), and the incident angle was measured as 1 degree.
  • the intensity of (002) is much stronger than (100).
  • FIGS. an example of the XRD profile of an Example with a strong a-axis orientation is shown in FIGS.
  • Al / (Ti + V + Al) 0.86 (wurtzite type, hexagonal crystal), and the incident angle was measured as 1 degree.
  • Al / (Cr + V + Al) 0.89 (wurtzite type, hexagonal crystal), and the incident angle was 1 degree.
  • Al / (Ti + Cr + V + Al) 0.83 (wurtzite type, hexagonal crystal), and the incident angle was measured as 1 degree.
  • the intensity of (100) is much stronger than (002).
  • (*) in the graph is a peak derived from the apparatus and a Si substrate with a thermal oxide film, and it is confirmed that it is not a peak of the sample body or a 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.
  • 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.
  • 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.
  • 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.
  • materials having an Al / (Ti + Cr + V + Al) ratio of 0.75 to 0.85 are plotted.
  • 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.
  • 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.
  • 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.
  • 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.
  • materials having an Al / (Cr + V + Al) ratio of 0.95 to 0.98 are plotted.
  • 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.
  • FIG. 26 shows a cross-sectional SEM photograph of the thin film thermistor portion 3 of (88, wurtzite hexagonal crystal, strong c-axis orientation).
  • M Cr
  • Al / (Cr + V + Al) 0.90, wurtzite type hexagonal crystal, strong c-axis orientation
  • FIG. 28 shows a cross-sectional SEM photograph of the (strong) thin film thermistor section 3.
  • the embodiment with strong c-axis orientation in FIG. 26 where M is Ti has a grain size of about 10 nm ⁇ ( ⁇ 5 nm ⁇ ) 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 nm ⁇ ( ⁇ 10 nm ⁇ ) and the length was about 430 nm.
  • the embodiment with strong c-axis orientation in FIG. 27 where M is Cr the embodiment has a grain size of about 10 nm ⁇ ( ⁇ 5 nm ⁇ ) and a length of about 450 nm, and the embodiment with strong a-axis orientation in FIG.
  • the diameter was 15 nm ⁇ ( ⁇ 10 nm ⁇ ) 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 nm ⁇ ( ⁇ 5 nm ⁇ ) and a length of about 450 nm, and the embodiment having a strong a-axis orientation in FIG. The particle diameter was about 15 nm ⁇ ( ⁇ 10 nm ⁇ ) and the length was about 470 nm.
  • the particle diameter is the diameter of the columnar crystal in the substrate surface
  • the length is the length (film thickness) of the columnar crystal in the direction perpendicular to the substrate surface.
  • 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.
  • the film is dense due to the small grain size of the columnar crystals.
  • 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.
  • 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.
  • Examples 5 and 6 in Table 1 are materials with strong c-axis orientation
  • Examples 9 and 10 are materials with strong a-axis orientation.
  • 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.
  • M Cr
  • Examples 6 and 7 in Table 2 are materials with strong c-axis orientation
  • Example 9 is a material with strong a-axis orientation.
  • 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.
  • Example 6 in Table 3 is a material with strong c-axis orientation
  • Example 10 is a material with strong a-axis orientation.
  • 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.
  • a Ta-Al-N-based material has an extremely large Ta ion radius compared to Ti, Cr, V, and Al, and thus cannot produce a wurtzite type phase 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.
  • Tables 7 to 9 show the results of the heat resistance test performed on the film evaluation element 121 subjected to the nitrogen plasma and the film evaluation element 121 not performed.
  • 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.

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Abstract

L'invention concerne un matériau à base de nitrure métallique pour thermistors qui possède une grande résistance à la chaleur, qui est d'une grande stabilité et qui peut être mis sous forme de film, par exemple directement sur un film sans combustion, ainsi qu'un procédé de fabrication de ce matériau à base de nitrure métallique, et un capteur à thermistor de type film. Ce matériau à base de nitrure métallique pour thermistors est fait d'un nitrure métallique correspondant à la formule générale (M1-wVw)xAlyNz où 0,0 < w < 1,0, 0,70 ≤ y/(x+y) ≤ 0,98, 0,4 ≤ z ≤ 0,5, et x+y+z = 1), et posséde une structure cristalline hexagonale de wurtzite à phase unique, M représentant Ti et/ou Cr. Ce procédé de production du matériau à base de nitrure métallique pour thermistors comprend une étape de formation de film afin de former un film en effectuant une pulvérisation réactive dans une atmosphère contenant de l'azote en utilisant une cible de pulvérisation en alliage M-V-Al, M représentant Ti et/ou Cr.
PCT/JP2014/065168 2013-06-05 2014-06-02 Matériau à base de nitrure métallique pour thermistors, son procédé de production et capteur à thermistor de type film WO2014196649A1 (fr)

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JPS6396262A (ja) * 1986-10-14 1988-04-27 Fujitsu General Ltd 窒化物の薄膜抵抗体製造方法
JPH0590011A (ja) * 1991-09-26 1993-04-09 Anritsu Corp 感温抵抗体及びその製造方法
JPH06158272A (ja) * 1992-11-17 1994-06-07 Ulvac Japan Ltd 抵抗膜および抵抗膜の製造方法
JPH10270201A (ja) * 1997-03-21 1998-10-09 Res Inst Electric Magnetic Alloys Ｃｒ−Ｎ基歪抵抗膜およびその製造法ならびに歪センサ
JP2008251611A (ja) * 2007-03-29 2008-10-16 Mitsubishi Materials Corp 薄型複合素子及びその製造方法

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JP4436064B2 (ja) * 2003-04-16 2010-03-24 大阪府 サーミスタ用材料及びその製造方法

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Publication number Priority date Publication date Assignee Title
JPS6396262A (ja) * 1986-10-14 1988-04-27 Fujitsu General Ltd 窒化物の薄膜抵抗体製造方法
JPH0590011A (ja) * 1991-09-26 1993-04-09 Anritsu Corp 感温抵抗体及びその製造方法
JPH06158272A (ja) * 1992-11-17 1994-06-07 Ulvac Japan Ltd 抵抗膜および抵抗膜の製造方法
JPH10270201A (ja) * 1997-03-21 1998-10-09 Res Inst Electric Magnetic Alloys Ｃｒ−Ｎ基歪抵抗膜およびその製造法ならびに歪センサ
JP2008251611A (ja) * 2007-03-29 2008-10-16 Mitsubishi Materials Corp 薄型複合素子及びその製造方法

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