WO2014097891A1 - 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 - Google Patents
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 Download PDFInfo
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- WO2014097891A1 WO2014097891A1 PCT/JP2013/082653 JP2013082653W WO2014097891A1 WO 2014097891 A1 WO2014097891 A1 WO 2014097891A1 JP 2013082653 W JP2013082653 W JP 2013082653W WO 2014097891 A1 WO2014097891 A1 WO 2014097891A1
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- 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
- H01C7/008—Thermistors
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- 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
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
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- 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
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- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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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
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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
- H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
- H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
- H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
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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
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- 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 and 2).
- these thermistor materials require firing at 600 ° C. or higher in order to obtain stable thermistor characteristics.
- 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.
- Patent Document 4 the general formula: Cr 100-x-y N x M y (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, It is one or more elements selected from Pt, Pd, Ag, Au, Co, Be, Mg, Ca, Sr, Ba, Mn, Al and rare earth elements, and the crystal structure is mainly bcc structure or mainly bcc A strain film resistance film material made of a nitride represented by 0.0001 ⁇ x ⁇ 30, 0 ⁇ y ⁇ 30, 0.0001 ⁇ x + y ⁇ 50) is 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 very thin thermistor sensor can be obtained by using a film.
- 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 600 ° 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.
- the Cr—NM material of Patent Document 4 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.
- An object of the present invention is 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 “z” that is, N / (Cr + Al + N)
- the “z” ie, N / (Cr + Al + N)
- 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 in the past. 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 is characterized in that, in the fourth aspect, at least a portion of the pattern electrode joined to the thin film thermistor portion is formed of Cr. That is, in this film type thermistor sensor, since at least a portion of the pattern electrode to be bonded to the thin film thermistor portion is formed of Cr, high bondability between the CrAlN 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 a metal nitride material for a thermistor according to any one of the first to third inventions, wherein a Cr—Al alloy sputtering target is used. And a film forming step of forming a film by reactive sputtering in a nitrogen-containing atmosphere. That is, in this method for producing a thermistor metal nitride material, a film is formed by reactive sputtering in a nitrogen-containing atmosphere using a Cr—Al alloy sputtering target. A physical material can be deposited without firing.
- 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 0.67 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 0.67 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.
- the present invention comprising the above CrAlN.
- the metal nitride material for thermistor 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. Can be used to obtain a thin and flexible thermistor sensor having good thermistor characteristics.
- the substrate material is not a ceramic material 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.
- FIG. 1 is a Cr—Al—N-based ternary phase diagram showing a composition range of a thermistor metal nitride material in one embodiment of the metal thermistor material for thermistor, the manufacturing method thereof, and the film type thermistor sensor according to the present invention.
- 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.
- it is a graph which shows the relationship between Al / (Cr + Al) ratio and B constant.
- Example which concerns on this invention it is a graph which shows the relationship between Al / (Cr + 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 cross-sectional SEM photograph which shows an Example with strong c-axis orientation.
- it is a cross-sectional SEM photograph which shows an Example with a strong a-axis orientation.
- FIGS. 1 to 3 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. 1 to 3.
- the scale is appropriately changed as necessary to make each part recognizable or easily recognizable.
- each composition ratio (x, y, z) of the points A, B, C, and D is A (15, 35, 50), B (2.5, 47.5, 50), C (3, 57, 40), D (18, 42, 40) It is.
- 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 film type thermistor sensor 1 includes an insulating film 2, a thin film thermistor portion 3 formed on the insulating film 2 from the metal nitride material for the thermistor, 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.
- 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, polyimide or epoxy resin material may be formed on the insulating film 2 by printing.
- the manufacturing method of the metal nitride material for thermistors of this embodiment includes a film forming step of performing film formation by reactive sputtering in a nitrogen-containing atmosphere using a Cr—Al alloy sputtering target. Moreover, it is preferable to set the sputtering gas pressure in the reactive sputtering to less than 0.67 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. 3A by reactive sputtering as shown in FIG.
- a thin film thermistor portion 3 made of the metal nitride material for thermistor is formed to a thickness of 200 nm.
- the sputtering conditions at that time are, for example, ultimate vacuum: 5 ⁇ 10 ⁇ 6 Pa, sputtering gas pressure: 0.4 Pa, target input power (output): 200 W, and nitrogen gas content in a mixed gas atmosphere of Ar gas + nitrogen gas Pressure: 80%.
- 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 vacuum degree: 6.7 Pa, an output: 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. 3C, 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. 3E, an end portion of the linearly extending portion 4b is formed with an Au thin film of 2 ⁇ m 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: Cr x Al y N z (0.70 ⁇ y / (x + y) ⁇ 0.95, 0.4 ⁇ z ⁇ 0.5, x + y + z 1), and its crystal structure is a hexagonal crystal system and a wurtzite single phase, so that a good B constant can be obtained without firing and a 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.
- the c-axis is oriented stronger than the a-axis in the direction perpendicular to the film surface, and a higher B constant can be obtained than when the a-axis orientation is strong.
- the film is formed by performing reactive sputtering in a nitrogen-containing atmosphere using a Cr—Al alloy sputtering target, so that the metal nitride for thermistors made of CrAlN is used.
- the material can be deposited without firing.
- a thermistor metal nitride material film 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.
- 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 in the past. 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 pattern electrode 4 to be bonded to the thin film thermistor portion 3 is formed of a Cr film, high bondability between the CrAlN thin film thermistor portion 3 and the pattern electrode 4 is obtained. 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. 4 was produced as follows. First, by reactive sputtering, Cr—Al alloy targets with various composition ratios are used to form Si substrates with Si oxides with thermal oxide films at various composition ratios shown in Table 1 having a thickness of 500 nm. The formed thin film thermistor portion 3 of the thermistor metal nitride material was formed.
- the sputtering conditions at that time were: ultimate vacuum: 5 ⁇ 10 ⁇ 6 Pa, sputtering gas pressure: 0.1 to 1 Pa, target input power (output): 100 to 500 W, and in a mixed gas atmosphere of Ar gas + nitrogen gas The nitrogen gas partial pressure was changed from 10 to 100%.
- 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 the quantitative accuracy of N / (Cr + Al + N) is ⁇ 2%
- the quantitative accuracy of Al / (Cr + Al) is ⁇ 1%.
- 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
- FIG. 5 shows a graph showing the relationship between the resistivity at 25 ° C. and the B constant from the above results.
- a high resistance and high B constant region having a specific resistance value at 25 ° C. of 20 ⁇ cm or more and a B constant of 1500 K or more can be realized.
- the B constant varies for the same Al / (Cr + Al) ratio 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 to 5 shown in Table 1 are regions of Al / (Cr + Al) ⁇ 0.7, and the crystal system is a cubic NaCl type.
- the NaCl type and the wurtzite type coexist.
- the specific resistance value at 25 ° C. was less than 20 ⁇ 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 / (Cr + 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.
- Thin film X-ray diffraction (identification of crystal phase)
- the thin film thermistor portion 3 obtained by the reactive sputtering method is subjected to oblique incidence X-ray diffraction (Grazing Incidence).
- the crystal phase was identified by X-ray Diffraction).
- all the examples of the present invention are films of wurtzite type phase, and since the orientation is strong, is the a-axis orientation strong in the crystal axis in the direction perpendicular to the Si substrate S (film thickness direction)? Whether the c-axis orientation is strong 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.
- the example in which the film was formed at a sputtering gas pressure of less than 0.67 Pa was a film having a (002) strength much stronger 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 0.67 Pa or higher was a material having a (100) strength much stronger than (002) and a a-axis orientation stronger than the c-axis orientation.
- it formed into a film on the polyimide film on the same film-forming conditions it confirmed that the single phase of the wurtzite type phase was formed similarly.
- orientation does not change.
- FIG. 1 An example of an XRD profile of an example with strong c-axis orientation is shown in FIG.
- Al / (Cr + Al) 0.84 (wurtzite type, hexagonal crystal), and the incident angle was 1 degree.
- the intensity of (002) is much stronger than (100).
- FIG. 1 An example of the XRD profile of an Example with a strong a-axis orientation is shown in FIG.
- Al / (Cr + Al) 0.85 (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. Symmetric measurement was performed with the incident angle set to 0 degree, and it was confirmed that the peak had disappeared, and it was confirmed that the peak was derived from the apparatus and from the Si substrate with a thermal oxide film.
- FIG. 1 An example of the XRD profile of the comparative example is shown in FIG.
- Al / (Cr + Al) 0.61 (NaCl type, cubic crystal), and the incident angle was 1 degree.
- a peak that could be indexed as a wurtzite type (space group P6 3 mc (No. 186)) was not detected, and it was confirmed to be a NaCl type single phase.
- 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.
- materials having substantially the same Al / (Cr + Al) ratio but a crystal axis having a strong degree of orientation perpendicular to the substrate surface is the c-axis (Examples 4, 6 and 6). 7, 8, 9) and a material which is a-axis (Examples 12 and 13).
- FIG. 11 shows a cross-sectional SEM photograph of the thin film thermistor portion 3 having a strong crystal and c-axis orientation.
- 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.
- the ionic radius of Ta is much larger than that of Cr or Al, so that 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 Cr—Al—N system is considered to have better heat resistance.
- the N / (Cr + Al + N) is made in the range of 0.4 to 0.5, good thermistor characteristics can be exhibited.
- the amount of nitrogen is smaller than 0.5, and it can be seen that there are nitrogen defects in the material. 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.
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Abstract
Description
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材料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600℃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3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4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。
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。
このサーミスタ用金属窒化物材料では、一般式:CrxAlyNz(0.70≦y/(x+y)≦0.95、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、上記「y/(x+y)」(すなわち、Al/(Cr+Al))が0.95をこえると、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/(Cr+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/(Cr+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、N/(Cr+Al+N)=0.5であることに起因する。
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。
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。
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。
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、CrAlN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。
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、Cr−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CrAlN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。
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、0.67Pa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。
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。
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:CrxAlyNz(0.70≦y/(x+y)≦0.95、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、Cr−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CrAlN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材料でなく、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。
なお、上記点A,B,C,Dの各組成比(x、y、z)は、A(15、35、50),B(2.5、47.5、50),C(3、57、40),D(18、42、40)
である。
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ることで、(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未満であることで決定する。
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。
また、上記反応性スパッタにおけるスパッタガス圧を、0.67Pa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。
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。
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、a軸配向が強い場合に比べて高いB定数が得られる。
また、反応性スパッタにおけるスパッタガス圧を、0.67Pa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。
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。
本発明の実施例及び比較例として、図4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Cr−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。その時のスパッタ条件は、到達真空度:5×10−6Pa、スパッタガス圧:0.1~1Pa、ターゲット投入電力(出力):100~500Wで、Arガス+窒素ガスの混合ガス雰囲気下において、窒素ガス分圧を10~100%と変えて作製した。
なお、比較としてCrxAlyNz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。
(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。
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に示す。
B定数(K)=In(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
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。
なお、表1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。
なお、同じ成膜条件でポリイミドフィルムに成膜しても、同様にウルツ鉱型相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。
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8に示す。この実施例は、Al/(Cr+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。この結果からわかるように、この実施例では、(002)よりも(100)の強度が非常に強くなっている。
表2及び図10に示すように、Al/(Cr+Al)比がほぼ同じ比率のものに対し、基板面に垂直方向の配向度の強い結晶軸がc軸である材料(実施例4,6,7,8,9)とa軸である材料(実施例12,13)とがある。
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、熱酸化膜付きSi基板S上に250nm程度成膜された実施例(Al/(Cr+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11に示す。また、別の実施例(Al/(Cr+Al)=0.85,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12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。
表3に示す実施例及び比較例において、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3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じB定数で比較したとき、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、Cr−Al−N系のほうが優れている。なお、実施例4,6はc軸配向が強い材料であり、実施例12,13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僅かに耐熱性が向上している。
表1に示す実施例4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。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4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、比抵抗及びB定数の変化が小さく、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。
Claims (8)
- 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:CrxAlyNz(0.70≦y/(x+y)≦0.95、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ることを特徴とするサーミスタ用金属窒化物材料。 - 請求項1に記載のサーミスタ用金属窒化物材料において、
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サーミスタ用金属窒化物材料。 - 請求項1に記載のサーミスタ用金属窒化物材料において、
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サーミスタ用金属窒化物材料。 - 絶縁性フィルムと、
該絶縁性フィルム上に請求項1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。 - 請求項4に記載のフィルム型サーミスタセンサにおいて、
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。 - 請求項1に記載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、
Cr−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。 - 請求項6に記載のサーミスタ用金属窒化物材料の製造方法において、
前記反応性スパッタにおけるスパッタガス圧を、0.67Pa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。 - 請求項6に記載のサーミスタ用金属窒化物材料の製造方法において、
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サーミスタ用金属窒化物材料の製造方法。
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CN201380060807.8A CN104838453B (zh) | 2012-12-21 | 2013-11-28 | 热敏电阻用金属氮化物材料及其制造方法以及薄膜型热敏电阻传感器 |
KR1020157016314A KR20150097537A (ko) | 2012-12-21 | 2013-11-28 | 서미스터용 금속 질화물 재료 및 그 제조 방법 그리고 필름형 서미스터 센서 |
US14/652,720 US9905342B2 (en) | 2012-12-21 | 2013-11-28 | Thermistor method made of metal nitride material, method for producing same, and film type thermistor sensor |
EP13864889.4A EP2937874A1 (en) | 2012-12-21 | 2013-11-28 | Metal-nitride thermistor material, manufacturing method therefor, and film-type thermistor sensor |
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JP2012279146A JP6015423B2 (ja) | 2012-12-21 | 2012-12-21 | 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 |
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JP (1) | JP6015423B2 (ja) |
KR (1) | KR20150097537A (ja) |
CN (1) | CN104838453B (ja) |
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JP6680995B2 (ja) * | 2015-03-26 | 2020-04-15 | 三菱マテリアル株式会社 | 窒化物熱電変換材料及びその製造方法並びに熱電変換素子 |
DE102017108582A1 (de) * | 2017-04-21 | 2018-10-25 | Epcos Ag | Schichtwiderstand und Dünnfilmsensor |
DE102017113401A1 (de) * | 2017-06-19 | 2018-12-20 | Epcos Ag | Schichtwiderstand und Dünnfilmsensor |
JP7234573B2 (ja) | 2017-12-25 | 2023-03-08 | 三菱マテリアル株式会社 | サーミスタ及びその製造方法並びにサーミスタセンサ |
WO2019131570A1 (ja) | 2017-12-25 | 2019-07-04 | 三菱マテリアル株式会社 | サーミスタ及びその製造方法並びにサーミスタセンサ |
JP2019129185A (ja) | 2018-01-22 | 2019-08-01 | 三菱マテリアル株式会社 | サーミスタ及びその製造方法並びにサーミスタセンサ |
CN111826621A (zh) * | 2019-04-17 | 2020-10-27 | 中国兵器工业第五九研究所 | 玻璃模压模具涂层及其制备方法和应用 |
JP2022157019A (ja) * | 2021-03-31 | 2022-10-14 | Tdk株式会社 | 歪抵抗膜および圧力センサ |
CN114381690B (zh) * | 2022-01-11 | 2024-03-01 | 厦门钨业股份有限公司 | 一种CrAlMeN-CrAlN纳米多层结构涂层及其制备方法与用途 |
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- 2013-11-28 KR KR1020157016314A patent/KR20150097537A/ko not_active Application Discontinuation
- 2013-11-28 US US14/652,720 patent/US9905342B2/en active Active
- 2013-11-28 EP EP13864889.4A patent/EP2937874A1/en not_active Withdrawn
- 2013-11-28 CN CN201380060807.8A patent/CN104838453B/zh not_active Expired - Fee Related
- 2013-11-28 WO PCT/JP2013/082653 patent/WO2014097891A1/ja active Application Filing
- 2013-12-09 TW TW102145124A patent/TW201443256A/zh unknown
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CN104838453B (zh) | 2017-07-04 |
EP2937874A1 (en) | 2015-10-28 |
US9905342B2 (en) | 2018-02-27 |
JP2014123646A (ja) | 2014-07-03 |
KR20150097537A (ko) | 2015-08-26 |
TW201443256A (zh) | 2014-11-16 |
US20150325345A1 (en) | 2015-11-12 |
JP6015423B2 (ja) | 2016-10-26 |
CN104838453A (zh) | 2015-08-12 |
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