JP5939397B2 - Temperature sensor - Google Patents

Description

  The present invention relates to a temperature sensor that is a film type thermistor temperature sensor having excellent bending resistance.

  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 and 2). In addition, these thermistor materials require firing at 600 ° C. or higher in order to obtain stable thermistor characteristics.

In addition to the thermistor material composed of the metal oxide as described above, for example, in Patent Document 3, the general formula: M _x A _y N _z (where M is at least one of Ta, Nb, Cr, Ti, and Zr) , A represents at least one of Al, Si, and B. 0.1 ≦ x ≦ 0.8, 0 <y ≦ 0.6, 0.1 ≦ z ≦ 0.8, x + y + z = 1) A thermistor material made of nitride has been proposed. Moreover, in this patent document 3, 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.

JP 2003-226573 A JP 2006-324520 A JP 2004-319737 A

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 a ceramic material such as alumina is often used. For example, to a thickness of 0.1 mm However, if the film is made thin, there is a problem that it is very brittle and easily broken. However, it is expected that a very thin thermistor sensor can be obtained by using a film.
Conventionally, in a temperature sensor in which a nitride thermistor made of TiAlN is formed, when a thermistor material layer made of TiAlN and an electrode are laminated on a film, an electrode layer such as Au is formed on the thermistor material layer. And patterning into a comb shape having a plurality of comb portions. However, this thermistor material layer has a large radius of curvature and is not easily cracked and there is no change in electrical properties such as resistance, but cracks are generated when the radius of curvature is small and tight. The resistance value and the like are greatly changed, and the reliability of the electrical characteristics is lowered. In particular, when the film is bent with a small radius of curvature in a direction perpendicular to the extending direction of the comb portion, the electrode edge is caused by the difference in stress between the comb-shaped electrode and the thermistor material layer compared to the case where the film is bent in the extending direction of the comb portion. There is a disadvantage that cracks are likely to occur in the vicinity and the reliability of the electrical characteristics is lowered.
In addition, a film made of a resin material generally has a heat resistant temperature as low as 150 ° C. or lower, and even a polyimide known as a material having a relatively high heat resistant temperature has only a heat resistance of about 300 ° C. 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. 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 3, 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.

  The present invention has been made in view of the above-mentioned problems. Even when bent, the TiAlN thermistor material layer is hardly cracked, and can be directly formed on a film or the like without firing, and has high heat resistance. An object of the present invention is to provide a temperature sensor having a highly reliable thermistor material layer.

  The present invention employs the following configuration in order to solve the above problems. That is, the temperature sensor according to the first invention includes an insulating film, a thin film thermistor portion patterned with a TiAlN thermistor material on the surface of the insulating film, and at least one above and below the thin film thermistor portion. A pair of comb-shaped electrodes having a plurality of comb portions and formed in patterns facing each other; and a pair of pattern electrodes connected to the pair of comb-shaped electrodes and patterned on the surface of the insulating film; A reinforcing resin material harder than the insulating film is installed on at least one of the front and back surfaces of the insulating film directly or via another film, and the reinforcing resin material extends in the extending direction of the comb portion. The thin film thermistor portion extends in a direction orthogonal to the thin film thermistor portion in the extending direction and is longer than the width of the thin film thermistor portion.

  In this temperature sensor, since the reinforcing resin material extends in a direction orthogonal to the extending direction of the comb portion and is longer than the width of the thin film thermistor portion in the extending direction, the direction is weak in bending. A rigid reinforcing resin material extends in a direction perpendicular to the extending direction of the comb portion, and the thin film thermistor portion is reinforced to ensure rigidity. Thereby, a bending is suppressed and the reliability of an electrical property improves.

The temperature sensor according to a second invention is characterized in that, in the first invention, the pair of reinforcing resin materials are disposed with the thin film thermistor portion interposed therebetween.
That is, in this temperature sensor, since the pair of reinforcing resin materials are installed with the thin film thermistor portion sandwiched therebetween, by reinforcing on both sides of the thin film thermistor portion, a stable rigidity with a good balance can be obtained.

A temperature sensor according to a third invention is the temperature sensor according to the first or second invention, wherein the reinforcing resin material is installed on a surface of the insulating film, and a protective film covering the thin film thermistor portion is at least the reinforcing material. The insulating film is formed on the surface of the insulating film except for a portion where the resin material is installed, and the surface of the reinforcing resin material and the surface of the protective film are flush with each other.
That is, in this temperature sensor, a protective film that covers the thin film thermistor portion is formed on the surface of the insulating film except at least a portion where the reinforcing resin material is installed, and the surface of the reinforcing resin material and the surface of the protective film are face to face. Therefore, when the surface side of the insulating film is used as a mounting surface, it can be in close contact with the object to be measured without being uneven due to the flat surface. Therefore, loss due to thermal resistance is reduced, and high-accuracy measurement is possible due to high thermal conductivity.

The temperature sensor according to a fourth aspect of the present invention is characterized in that, in the first or second aspect, the reinforcing resin material is installed on the back surface of the insulating film.
That is, in this temperature sensor, since the reinforcing resin material is installed on the back surface of the insulating film, the reinforcing resin material does not hinder the thermal conductivity of the surface, and more accurate measurement is possible. become.

Temperature sensor according to the fifth invention, in any one of the first to fourth invention, the thin film thermistor portion has the general _{formula: Ti x Al y N z (} 0.70 ≦ y / (x + y) ≦ 0. 95, 0.4 ≦ z ≦ 0.5, x + y + z = 1), and the crystal structure thereof is a hexagonal wurtzite single phase.

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). For this reason, it was 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 thin film thermistor portion has a general formula: Ti _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 wurtzite single phase, so that a good B constant can be obtained without firing and a high heat resistance. It has sex.

When the above “y / (x + y)” (ie, Al / (Ti + Al)) is less than 0.70, a wurtzite type single phase cannot be obtained, and a coexisting phase with an NaCl type phase or an NaCl type phase Therefore, a sufficiently high resistance and a high B constant cannot be obtained.
Further, if the above “y / (x + y)” (that is, Al / (Ti + Al)) exceeds 0.95, 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 / (Ti + Al + N)) is less than 0.4, since the amount of metal nitriding is small, a wurtzite type single phase cannot be obtained, and a sufficiently high resistance and high B A constant cannot be obtained.
Furthermore, when the “z” (that is, N / (Ti + Al + N)) exceeds 0.5, a wurtzite single phase cannot be obtained. This is because in the wurtzite type single phase, the correct stoichiometric ratio when there is no defect at the nitrogen site is N / (Ti + Al + N) = 0.5.

The present invention has the following effects.
That is, according to the temperature sensor of the present invention, the reinforcing resin material extends in a direction orthogonal to the extending direction of the comb portion and is longer than the width of the thin film thermistor portion in the extending direction. The reinforcing resin material extends in the direction perpendicular to the extending direction of the comb portion, which is a weak direction to bend, and the thin film thermistor portion is reinforced to ensure rigidity. Reliability is improved.
Furthermore, the thin film thermistor portion is formed by metal nitriding represented by the general formula: Ti _x Al _y N _z (0.70 ≦ y / (x + y) ≦ 0.95, 0.4 ≦ z ≦ 0.5, x + y + z = 1). By using a material that has a hexagonal wurtzite type single phase and has a crystal structure, a good B constant can be obtained without firing, and high heat resistance can be obtained.
Therefore, according to the temperature sensor of the present invention, it is difficult to generate a crack with respect to bending, is flexible and has little unevenness, and is installed by being inserted into a gap such as a substrate of an electronic device, a narrow gap such as a non-contact power feeding device or a battery. It can also be installed on a curved surface.

It is a top view which shows 1st Embodiment of the temperature sensor which concerns on this invention. In 1st Embodiment, it is sectional drawing cut | disconnected along the comb-shaped electrode and the pattern electrode. In 1st Embodiment, it is a Ti-Al-N type | system | group ternary phase diagram which shows the composition range of the metal nitride material for thermistors. In 1st Embodiment, it is a top view which shows the manufacturing process of a temperature sensor in order of a process. It is sectional drawing cut | disconnected along the comb-shaped electrode and pattern electrode which show 2nd Embodiment of the temperature sensor which concerns on this invention. It is sectional drawing cut | disconnected along the comb-shaped electrode and pattern electrode which show 3rd Embodiment of the temperature sensor which concerns on this invention. In the Example of the temperature sensor which concerns on this invention, it is the front view and top view which show the element for film | membrane evaluation of the metal nitride material for thermistors. In the Example and comparative example which concern on this invention, it is a graph which shows the relationship between 25 degreeC resistivity and B constant. In the Example and comparative example which concern on this invention, it is a graph which shows the relationship between Al / (Ti + Al) ratio and B constant. In the Example which concerns on this invention, it is a graph which shows the result of X-ray diffraction (XRD) in case c / axis orientation with Al / (Ti + Al) = 0.84 is strong. In the Example which concerns on this invention, it is a graph which shows the result of X-ray diffraction (XRD) in case a-axis orientation is strong made into Al / (Ti + Al) = 0.83. In the comparative example which concerns on this invention, it is a graph which shows the result of X-ray diffraction (XRD) in the case of Al / (Ti + Al) = 0.60. In the Example which concerns on this invention, it is a graph which shows the relationship between Al / (Ti + Al) ratio and B constant which compared the Example with strong a-axis orientation, and the Example with strong c-axis orientation. In the Example which concerns on this invention, it is a cross-sectional SEM photograph which shows an Example with strong c-axis orientation. In the Example which concerns on this invention, it is a cross-sectional SEM photograph which shows an Example with a strong a-axis orientation.

  Hereinafter, a temperature sensor according to a first embodiment of the present invention will be described with reference to FIGS. Note that in some of the drawings used for the following description, the scale is appropriately changed as necessary to make each part recognizable or easily recognizable.

  The temperature sensor 1 of this embodiment is a film type thermistor sensor, and as shown in FIGS. 1 and 2, the insulating film 2 and the surface of the insulating film 2 are patterned with a TiAlN thermistor material. The thin film thermistor section 3, the pair of comb electrodes 4 having a plurality of comb sections 4 a on the thin film thermistor section 3 and patterned to face each other, and the insulating film 2 connected to the pair of comb electrodes 4 And a pair of pattern electrodes 5 patterned on the surface.

A terminal portion 5 a on which a plating film 8 is formed is provided at the base end portion of the pair of pattern electrodes 5.
A protective film 7 is formed on the surface of the insulating film 2 so as to cover at least the surface of the thin film thermistor portion 3 except for the pair of terminal portions 5a. In the present embodiment, a protective film 7 is formed on the entire surface of the insulating film 2 except for the terminal portion 5 a and covers the thin film thermistor portion 3, the comb electrode 4, and the pattern electrode 5.

  On the surface of the insulating film 2, a pair of reinforcing resin materials 6 harder than the insulating film 2 are provided on the protective film 7. These reinforcing resin materials 6 extend in a direction orthogonal to the extending direction of the comb portion 4a and are set longer than the width of the thin film thermistor portion 3 in the extending direction. In the present embodiment, the reinforcing resin material 6 extends over the entire width of the insulating film 2. The pair of reinforcing resin materials 6 are installed with the thin film thermistor portion 3 interposed therebetween.

The insulating film 2 is formed in a band shape with, for example, a polyimide resin sheet having a thickness of 7.5 to 125 μm. In addition, as the insulating film 2, PET: polyethylene terephthalate, PEN: polyethylene naphthalate, or the like may be used.
The thin film thermistor portion 3 is formed of a TiAlN thermistor material. In particular, the thin film thermistor portion 3 is a metal represented by the general formula: Ti _x Al _y N _z (0.70 ≦ y / (x + y) ≦ 0.95, 0.4 ≦ z ≦ 0.5, x + y + z = 1). It consists of nitride and its crystal structure is a hexagonal wurtzite single phase.

The pattern electrode 5 and the comb-shaped electrode 4 are formed on the thin film thermistor portion 3 with a thickness of 5 to 100 nm of a Cr or NiCr bonding layer and a noble metal such as Au on the bonding layer with a thickness of 50 to 1000 nm. And an electrode layer formed.
The pair of comb-shaped electrodes 4 has a comb-shaped pattern in which comb portions 4a are arranged alternately and arranged in opposition to each other.

The pair of pattern electrodes 5 is a terminal portion 5 a having a distal end portion connected to the comb-shaped electrode 4 and a proximal end portion disposed on the proximal end portion of the insulating film 2.
The protective film 7 is an insulating resin film or the like, for example, a polyimide film having a thickness of 20 μm is employed.
The reinforcing resin material 6 is formed of, for example, an epoxy resin, but the material is not particularly limited as long as the resin film is harder than the insulating film 2.

As described above, the thin film thermistor portion 3 is a metal nitride material, and has a general formula: Ti _x Al _y N _z (0.70 ≦ y / (x + y) ≦ 0.95, 0.4 ≦ z ≦ 0.5, x + y + z = 1), the crystal structure of which is a hexagonal crystal system with a single phase of wurtzite type (space group P6 ₃ mc (No. 186)) is there. That is, this metal nitride material has a composition in a region surrounded by points A, B, C, and D in the Ti—Al—N ternary phase diagram as shown in FIG. It is a metal nitride that is a wurtzite type.
In addition, each composition ratio (x, y, z) (atomic%) 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).

The thin film thermistor portion 3 is a columnar crystal that is formed in a film shape of, for example, a film thickness of 100 to 1000 nm and extends 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). By examining the orientation, from the peak intensity ratio of (100) (Miller index indicating a-axis orientation) and (002) (Miller index indicating c-axis alignment), “(100) peak intensity” / “(( 002) peak intensity ”is less than 1.

A method for manufacturing the temperature sensor 1 will be described below with reference to FIG.
The manufacturing method of the temperature sensor 1 of the present embodiment includes a thin film thermistor portion forming step of patterning the thin film thermistor portion 3 on the insulating film 2 and a pair of comb-shaped electrodes 4 facing each other on the thin film thermistor portion 3. Then, an electrode forming step of forming a pair of pattern electrodes 5 on the insulating film 2, a protective film forming step of forming the protective film 7 on the surface of the insulating film 2, and a reinforcing resin material on the protective film 7 6 for forming a reinforcing resin material.

As a more specific example of the manufacturing method, Ti _x Al _y is used by reactive sputtering in a nitrogen-containing atmosphere using a Ti—Al alloy sputtering target on a 40 μm-thick polyimide insulating film 2. A thermistor film of N _z (x = 9, y = 43, z = 48) is formed with a film thickness of 200 nm. The sputtering conditions at that time were an ultimate vacuum of 5 × 10 ⁻⁶ Pa, a sputtering gas pressure of 0.4 Pa, a target input power (output) of 200 W, and a nitrogen gas fraction of 20 in a mixed gas atmosphere of Ar gas + nitrogen gas. %.

A resist solution is applied onto the deposited thermistor film with a bar coater, pre-baked at 110 ° C. for 1 minute and 30 seconds, exposed to light with an exposure device, and unnecessary portions are removed with a developer, and further at 150 ° C. for 5 minutes. Patterning is performed by post-baking. Thereafter, an unnecessary Ti _x Al _y N _z thermistor film was wet-etched with a commercially available Ti etchant to form a 300 × 400 μm thin film thermistor portion 3 by resist stripping as shown in FIG.

Next, a 20 nm-thick Cr film bonding layer is formed on the thin film thermistor portion 3 and the insulating film 2 by sputtering. Further, an Au film electrode layer is formed to a thickness of 200 nm on this bonding layer by sputtering.
Next, after applying a resist solution on the electrode layer formed with a bar coater, pre-baking is performed at 110 ° C. for 1 minute 30 seconds, and after exposure with an exposure apparatus, unnecessary portions are removed with a developing solution, Patterning is performed by post-baking for 5 minutes. Thereafter, unnecessary electrode portions are wet-etched in the order of a commercially available Au etchant and a Cr etchant, and as shown in FIG. 4B, desired comb electrodes 4 and pattern electrodes 5 are formed by resist stripping. .
At this time, the pair of comb-shaped electrodes 4 is formed by six pairs of comb portions 4a having a width of 30 μm and a distance of 30 μm.

Further, a polyimide varnish is applied thereon by a printing method and cured at 250 ° C. for 30 minutes to form a 20 μm thick polyimide protective film 7 as shown in FIG.
Next, a hard epoxy resin film which is harder to bend than the insulating film 2 is applied by a printing method and cured at 150 ° C. for 30 minutes, and as shown in FIG. The resin material 6 is patterned. Further, as shown in FIG. 1, a plating layer 8 by thick plating of electroless Au for solder connection is formed to a thickness of 0.3 μm on the portion to be the terminal portion 5 a.

In addition, when producing the several temperature sensor 1 simultaneously, several thin film thermistor part 3, the comb-shaped electrode 4, the pattern electrode 5, the protective film 7, and the reinforcing resin material 6 are formed on the large sheet | seat of the insulating film 2 as mentioned above. After forming, the large sheet is cut into each temperature sensor 1.
In this way, the temperature sensor 1 of a thin film type thermistor sensor having a size of 16 × 4 mm and a thickness of 0.08 mm, for example, is obtained.

As described above, in the temperature sensor 1 of the present embodiment, the reinforcing resin material 6 extends in a direction orthogonal to the extending direction of the comb portion 4a and is equal to or larger than the width of the thin film thermistor portion 3 in the extending direction. Therefore, the rigid reinforcing resin material 6 extends in the direction perpendicular to the extending direction of the comb portion 4a, which is a weak direction to bend, and the thin film thermistor portion 3 is reinforced to ensure rigidity. Thereby, a bending is suppressed and the reliability of an electrical property improves.
In addition, since the pair of reinforcing resin materials 6 are disposed with the thin film thermistor portion 3 interposed therebetween, reinforcement with reinforcement on both sides of the thin film thermistor portion 3 provides a balanced and stable rigidity.

The thin-film thermistor portion 3 has the general _formula: metal represented by _{Ti x Al y N z (0.70} ≦ y / (x + y) ≦ 0.95,0.4 ≦ z ≦ 0.5, x + y + z = 1) Since it is made of nitride and its crystal structure is a hexagonal crystal system and is a wurtzite single phase, it has a good B constant without firing and has high heat resistance.
In addition, since this metal nitride material is a columnar crystal extending in a direction perpendicular to the surface of the film, the film has high crystallinity and high heat resistance can be obtained.
Further, in this metal nitride material, by aligning the c-axis more strongly than the a-axis in the direction perpendicular to the film surface, a higher B constant can be obtained than when the a-axis alignment is strong.

In the method for manufacturing the thermistor material layer (thin film thermistor portion 3) of the present embodiment, since the film is formed by reactive sputtering in a nitrogen-containing atmosphere using a Ti—Al alloy sputtering target, the above-mentioned TiAlN is used. The metal nitride material can be formed without firing.
Further, by setting the sputtering gas pressure in reactive sputtering to less than 0.67 Pa, a metal nitride material film in which the c-axis is oriented more strongly than the a-axis in the direction perpendicular to the film surface is formed. be able to.

Therefore, in the temperature sensor 1 of the present embodiment, since the thin film thermistor portion 3 is formed of the thermistor material layer on the insulating film 2, the thin film thermistor portion 3 is formed without firing and has a high B constant and high heat resistance. Thus, an insulating film 2 having low heat resistance such as a resin film can be used, and a thin and flexible thermistor sensor having good thermistor characteristics can be obtained.
In addition, 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, as described above, for example, a very thin film type thermistor sensor having a thickness of 0.1 mm can be obtained.

  Next, 2nd Embodiment and 3rd Embodiment of the temperature sensor which concerns on this invention are described below with reference to FIG.5 and FIG.6. In the following description of each embodiment, the same constituent elements described in the above embodiment are denoted by the same reference numerals, and the description thereof is omitted.

  The difference between the second embodiment and the first embodiment is that, in the first embodiment, the pair of reinforcing resin materials 6 are formed on the protective film 7, whereas the temperature sensor of the second embodiment. 5, as shown in FIG. 5, a pair of reinforcing resin materials 6 are directly installed on the surface of the insulating film 2, and a protective film 7 covering the thin film thermistor portion 3 is composed of the terminal portion 5a and the reinforcing resin material. 6 is formed on the surface of the insulating film 2 except for the installation portion 6. Furthermore, in the second embodiment, the surface of the reinforcing resin material 6 and the surface of the protective film 7 are flush with each other.

When the temperature sensor 21 of the second embodiment is manufactured, when the protective film 7 is formed by a printing method, the protective resin 7 is formed by leaving a portion where the reinforcing resin material 6 is installed. The reinforcing resin material 6 is formed by a printing method on the unexposed portion. If it does in this way, the protective film 7 and the resin material 6 for reinforcement will become flush | level, and the surface side of the insulating film 2 will become a flat surface.
Therefore, in the temperature sensor 21 of the second embodiment, since the surface of the reinforcing resin material 6 and the surface of the protective film 7 are flush with each other, when the surface side of the insulating film 2 is a mounting surface, By being a flat surface, it can be made to adhere to an object to be measured without unevenness. Therefore, loss due to thermal resistance is reduced, and high-accuracy measurement is possible due to high thermal conductivity.

  Next, the difference between the third embodiment and the first embodiment is that, in the first embodiment, the pair of reinforcing resin materials 6 are on the surface side of the insulating film 2 on which the thin film thermistor portion 3 is formed. In contrast, the temperature sensor 31 of the third embodiment is provided on the back surface of the insulating film 2 as shown in FIG.

  Thus, in the temperature sensor 31 of the third embodiment, since the reinforcing resin material 6 is installed on the back surface of the insulating film 2, the reinforcing resin material 6 may hinder the thermal conductivity of the surface. In addition, more accurate measurement is possible. That is, also in the case of this 3rd Embodiment, when making the surface side of the insulating film 2 into a mounting surface, it can be made to contact | adhere with a measurement object without an unevenness | corrugation because it is a flat surface.

  Next, the results of evaluating the temperature sensor according to the present invention by the example produced based on the above embodiment will be described in detail with reference to FIGS.

<Production of film evaluation element>
As examples and comparative examples for evaluating the thermistor material layer (thin film thermistor portion 3) of the present invention, a film evaluation element 121 shown in FIG. 7 was produced as follows.
First, by reactive sputtering, Ti—Al alloy targets having various composition ratios are used to form Si substrates S on a Si wafer with a thermal oxide film at various composition ratios shown in Table 1 having a thickness of 500 nm. A thin film thermistor portion 3 of the formed 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, in a mixed gas atmosphere of Ar gas + nitrogen gas The nitrogen gas fraction was changed to 10 to 100%.

Next, a 20 nm Cr film was formed on the thin film thermistor portion 3 by sputtering, and a 100 nm Au film was further formed. Furthermore, after applying a resist solution thereon with a spin coater, pre-baking is performed at 110 ° C. for 1 minute 30 seconds, and 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. Patterning. 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, comparative examples in which the composition ratio of Ti _x Al _y N _z is out of the scope of the present invention and the crystal system is different were similarly prepared and evaluated.

<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 Table 1. In addition, the composition ratio in the following table | surface is shown by "atomic%".

  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. As for the quantitative accuracy, the quantitative accuracy of N / (Ti + Al + N) is ± 2%, and the quantitative accuracy of Al / (Ti + Al) is ± 1%.

(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 Table 1.
(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 Table 1.

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

As can be seen from these results, the composition ratio of Ti _x Al _y N _z is within the region surrounded by the points A, B, C, and D in the ternary triangular diagram shown in FIG. ≦ y / (x + y) ≦ 0.95, 0.4 ≦ z ≦ 0.5, x + y + z = 1 ”, thermistor characteristics of resistivity: 100 Ωcm or more, B constant: 1500 K or more Has been achieved.

  FIG. 8 shows a graph showing the relationship between the resistivity at 25 ° C. and the B constant based on the above results. A graph showing the relationship between the Al / (Ti + Al) ratio and the B constant is shown in FIG. From these graphs, in the region of Al / (Ti + Al) = 0.7 to 0.95 and N / (Ti + Al + N) = 0.4 to 0.5, the wurtzite single crystal system is hexagonal. 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. In the data of FIG. 9, the B constant varies for the same Al / (Ti + Al) ratio because the amount of nitrogen in the crystal is different.

  Comparative Examples 3 to 12 shown in Table 1 are regions of Al / (Ti + Al) <0.7, and the crystal system is a cubic NaCl type. In Comparative Example 12 (Al / (Ti + Al) = 0.67), the NaCl type and the wurtzite type coexist. Thus, in the region of Al / (Ti + 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 Examples 1 and 2 shown in Table 1 are regions where N / (Ti + Al + N) is less than 40%, and the metal is in a crystalline state with insufficient nitriding. In Comparative Examples 1 and 2, neither the NaCl type nor the wurtzite type was 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) 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.

  As a result, in the region of Al / (Ti + Al) ≧ 0.7, it is a wurtzite type phase (hexagonal crystal, the same phase as AlN), and in the region of Al / (Ti + Al) <0.65, the NaCl type phase. (Cubic, same phase as TiN). Further, in the case of 0.65 <Al / (Ti + Al) <0.7, it was a crystal phase in which the wurtzite type phase and the NaCl type phase coexist.

Thus, in the TiAlN system, a region having a high resistance and a high B constant exists in the wurtzite phase of Al / (Ti + Al) ≧ 0.7. In the examples of the present invention, the impurity phase is not confirmed, and is a wurtzite type single phase.
In Comparative Examples 1 and 2 shown in Table 1, the crystal phase was neither the wurtzite type phase nor the 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.

  Next, 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, in order to investigate the orientation of the crystal axis, the peak intensity ratio between (100) (Miller index indicating a-axis orientation) and (002) (Miller index indicating c-axis orientation) was measured.

As a result, 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. . On the other hand, 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.
In addition, even if 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. 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.

An example of an XRD profile of an example with strong c-axis orientation is shown in FIG. In this example, Al / (Ti + Al) = 0.84 (wurtzite type, hexagonal crystal), and the incident angle was 1 degree. As can be seen from this result, in this example, the intensity of (002) is much stronger than (100).
Moreover, an example of the XRD profile of an Example with a strong a-axis orientation is shown in FIG. In this example, Al / (Ti + Al) = 0.83 (wurtzite type, hexagonal crystal), and the incident angle was measured as 1 degree. As can be seen from this result, in this example, the intensity of (100) is much stronger than (002).

  Further, for this example, the symmetric reflection measurement was performed with the incident angle set to 0 degree. In the graph, (*) is a peak derived from the device, and it is confirmed that it is not the peak of the sample body or the peak of the impurity phase (in addition, the peak disappears in the symmetric reflection measurement). It can be seen that the peak is derived from the apparatus.)

An example of the XRD profile of the comparative example is shown in FIG. In this comparative example, Al / (Ti + Al) = 0.6 (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.

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 Table 2 and FIG. 13, a material in which the crystal axis having a strong degree of orientation in the direction perpendicular to the substrate surface is the c-axis with respect to the Al / (Ti + Al) ratio being substantially the same ratio (Examples 5, 7, 8, 9) and a material which is a-axis (Examples 19, 20, 21).

  Comparing the two, it can be seen that when the Al / (Ti + Al) ratio is the same, the material having a strong c-axis orientation has a larger B constant by about 100K than the material having a strong a-axis orientation. Further, when focusing attention on the N amount (N / (Ti + 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 ideal stoichiometric ratio: N / (Ti + Al + N) = 0.5, it can be seen that a material with a strong c-axis orientation is an ideal material with a small amount of nitrogen defects.

<Evaluation of crystal form>
Next, as an example showing the crystal form in the cross section of the thin film thermistor part 3, an example (Al / (Ti + Al) = 0.84 wurtzite type, hexagonal crystal formed on the Si substrate S with a thermal oxide film, FIG. 14 shows a cross-sectional SEM photograph of the thin film thermistor portion 3 having a strong c-axis orientation. Moreover, the cross-sectional SEM photograph in the thin film thermistor part 3 of another Example (Al / (Ti + Al) = 0.83, a wurtzite type hexagonal crystal and strong a-axis orientation) is 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.

  As can be seen from these photographs, all the examples are formed of high-density 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.

<Evaluation of heat resistance test of membrane>
In Examples and Comparative Examples shown in Table 1, resistance values and B constants before and after a heat resistance test at 125 ° C. and 1000 h in the atmosphere were evaluated. The results are shown in Table 3. 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 the same B constant as that of the comparative example which is a Ta-Al-N system, the heat resistance when viewed in terms of changes in electrical characteristics before and after the heat resistance test is The Ti-Al-N system is superior. Examples 5 and 8 are materials with strong c-axis orientation, and Examples 21 and 24 are materials with strong a-axis orientation. When both are compared, the heat resistance of the example with a strong c-axis orientation is slightly improved as compared with the example with a strong a-axis orientation.

  Note that, in the Ta—Al—N-based material, the ionic radius of Ta is much larger than that of Ti or 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 Ti-Al-N system of the wurtzite type phase is considered to have better heat resistance.

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.
For example, in the second embodiment, the reinforcing resin material is provided in the portion without the protective film and the surface side is made flat. However, the reinforcing resin material is provided directly on the surface of the insulating film, and the reinforcing resin material is provided. The surface of the insulating film may be flattened by forming a thick protective film on the insulating film so as to cover and fill the surface.

  Further, in each of the above embodiments, the reinforcing resin material is provided only on one of the front surface and the back surface of the insulating film directly or through a protective film, but the reinforcing resin material is provided on each of the front and back surfaces of the insulating film. It doesn't matter. Although two reinforcing resin materials are provided, one or three or more resin materials may be provided. Further, a reinforcing resin material extending along the extending direction of the comb portion may be additionally provided.

  DESCRIPTION OF SYMBOLS 1, 21, 31 ... Temperature sensor, 2 ... Insulating film, 3 ... Thin film thermistor part, 4a ... Comb part, 4 ... Comb-shaped electrode, 5 ... Pattern electrode, 6 ... Reinforcing resin material, 7 ... Protective film

Claims (5)

An insulating film;
A thin film thermistor portion patterned with a TiAlN thermistor material on the surface of the insulating film;
A pair of comb-shaped electrodes that have a plurality of comb portions on at least one of the upper and lower sides of the thin film thermistor portion and are patterned to face each other;
A pair of pattern electrodes connected to the pair of comb electrodes and patterned on the surface of the insulating film;
A reinforcing resin material harder than the insulating film is installed directly or through another film on at least one of the front and back surfaces of the insulating film,
The reinforcing resin material extends in a direction orthogonal to the extending direction of the comb portion and is longer than the width of the thin film thermistor portion in the extending direction ,
A temperature sensor , wherein the pair of reinforcing resin materials are disposed with the thin film thermistor portion interposed therebetween . The temperature sensor according to claim 1 ,
The reinforcing resin material is installed on the surface of the insulating film,
A protective film covering the thin film thermistor portion is formed on the surface of the insulating film except at least a portion where the reinforcing resin material is installed, and the surface of the reinforcing resin material is flush with the surface of the protective film. Temperature sensor. The temperature sensor according to claim 1 ,
The temperature sensor, wherein the reinforcing resin material is installed on the back surface of the insulating film. The temperature sensor according to any one of claims 1 to 3 ,
The thin film thermistor portion is a metal nitride represented by the general formula: Ti _x Al _y N _z (0.70 ≦ y / (x + y) ≦ 0.95, 0.4 ≦ z ≦ 0.5, x + y + z = 1) A temperature sensor characterized in that its crystal structure is a hexagonal wurtzite single phase. An insulating film;
A thin film thermistor portion patterned with a TiAlN thermistor material on the surface of the insulating film;
A pair of comb-shaped electrodes that have a plurality of comb portions on at least one of the upper and lower sides of the thin film thermistor portion and are patterned to face each other;
A pair of pattern electrodes connected to the pair of comb electrodes and patterned on the surface of the insulating film;
A reinforcing resin material harder than the insulating film is installed directly or through another film on at least one of the front and back surfaces of the insulating film,
The reinforcing resin material extends in a direction orthogonal to the extending direction of the comb portion and is longer than the width of the thin film thermistor portion in the extending direction ,
The reinforcing resin material is installed on the surface of the insulating film,
A protective film covering the thin film thermistor portion is formed on the surface of the insulating film except at least a portion where the reinforcing resin material is installed, and the surface of the reinforcing resin material is flush with the surface of the protective film. temperature sensor, characterized in that it is.