JP6115823B2 - Metal nitride material for thermistor, manufacturing method thereof, and film type thermistor sensor - Google Patents

Description

  The present invention relates to a metal nitride material for a thermistor that can be directly formed on a film or the like, 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. Conventionally, transition metal oxides such as Mn, Co, and Fe are generally used for such thermistor materials (see Patent Documents 1 to 3). In addition, these thermistor materials require heat treatment such as firing at 550 ° C. or higher in order to obtain stable thermistor characteristics.

In addition to the thermistor material composed of the metal oxide as described above, for example, in Patent Document 4, 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 4, it is Ta-Al-N type material, 0.5 <= x <= 0.8, 0.1 <= y <= 0.5, 0.2 <= z <= 0.7, x + y + z = 1. Only those described above are described as examples. This Ta—Al—N-based material is produced by performing sputtering in a nitrogen gas-containing atmosphere using a material containing the above elements as a target. Moreover, the obtained thin film is heat-processed at 350-600 degreeC as needed.

As examples different from the thermistor material, for example, Patent Document 5, 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. ing. This resistance film material for strain sensors measures and converts strains and stresses from changes in the resistance of the Cr-N-based strain resistance film in a composition where both the nitrogen content x and the subcomponent element M content y are 30 atomic% or less. Used for. In addition, this Cr—N—M-based material is produced by performing reactive sputtering in a film-forming atmosphere containing the subcomponent gas, using it as a target such as a material containing the element. Moreover, the obtained thin film is heat-processed at 200-1000 degreeC as needed.

JP 2000-068110 A JP 2000-348903 A JP 2006-324520 A JP 2004-319737 A Japanese Patent Laid-Open No. 10-270201

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, development of a very thin thermistor sensor having a thickness of about 0.1 mm is desired. Conventionally, however, a substrate using ceramics such as alumina is often used. For example, the thickness is reduced to 0.1 mm. Then, although there existed problems, such as being very brittle and fragile, it is anticipated that a very thin thermistor sensor will be obtained by using a film.
However, since a film made of a resin material generally has a heat resistant temperature as low as 150 ° C. or less, and polyimide known as a material having a relatively high heat resistant temperature has only a heat resistance of about 200 ° C., a thermistor material forming process In the case where heat treatment is applied, application is difficult. The conventional oxide thermistor material requires firing at 550 ° C. or higher in order to realize desired thermistor characteristics, and there is a problem that a film type thermistor sensor directly formed on a film cannot be realized. Therefore, it is desired to develop a thermistor material that can be directly formed on a film or the like, but even with the thermistor material described in Patent Document 4, the obtained thin film is obtained as necessary in order to obtain desired thermistor characteristics. It was necessary to perform heat treatment at 350 to 600 ° C. Further, in this example of the thermistor material, a material having a B constant of about 500 to 3000 K is obtained in the example of the Ta-Al-N material, but there is no description regarding heat resistance, and the thermal reliability of the nitride material. Sex was unknown.
Further, the Cr—N—M material of Patent Document 5 is a material having a B constant as small as 500 or less, and heat resistance within 200 ° C. cannot be ensured unless heat treatment at 200 ° C. or more and 1000 ° C. or less is performed. Therefore, there has been a problem that a film type thermistor sensor formed directly on a film cannot be realized. Therefore, it is desired to develop a thermistor material that can be directly formed on a film or the like.
Further, as described in Patent Document 5, Ga is sometimes used as a nitride material. However, Ga has a very low melting point of about 30 ° C. For example, when attempting to form a film by reactive sputtering, if Ga is used as a sputtering target, the temperature of the thermistor material does not melt at the time of film formation. Manufacturing is very difficult to manufacture.

  The present invention has been made in view of the above-mentioned problems, and can be directly formed on a film or the like, and has high heat resistance and high reliability, a metal nitride material for a thermistor, a manufacturing method thereof, and a film mold An object is to provide a thermistor sensor.

The inventors of the present invention have paid attention to the GaN system among the nitride materials and have made extensive studies. However, it is difficult for GaN, which is a semiconductor, to obtain optimum thermistor characteristics (B constant: about 1000 to 6000 K). The present inventors have found that a favorable B constant and heat resistance can be obtained by replacing the Ga site with a specific metal element that improves electrical conduction and a specific crystal structure.
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.

That is, the metal nitride material for a thermistor according to the first invention is a metal nitride material used for the thermistor, and has the general formula: Ti _x Ga _y (N _1-w O _w ) _z (0.0 ≦ w ≦ 0.85, 0.70 ≦ y / (x + y) ≦ 0.99, 0.45 ≦ z ≦ 0.55, x + y + z = 1), the crystal structure of which is hexagonal The wurtzite type single phase.
This metal nitride material for a thermistor is a metal nitride material used for the thermistor, and has a general formula: Ti _x Ga _y (N _1-w O _w ) _z (0.0 ≦ w ≦ 0.85,. 70 ≦ y / (x + y) ≦ 0.99, 0.45 ≦ z ≦ 0.55, x + y + z = 1), the crystal structure of which is a hexagonal wurtzite single phase Therefore, a good B constant can be obtained and high heat resistance can be obtained. In particular, when oxygen (O) is contained, the heat resistance is further improved by the effect of filling the nitrogen defects in the crystal with oxygen or introducing interstitial oxygen.

When the above “y / (x + y)” (ie, Ga / (Ti + Ga)) is less than 0.70, a wurtzite type single phase cannot be obtained, and only a coexisting phase with NaCl type phase or NaCl type Thus, a sufficiently high resistance and a high B constant cannot be obtained.
Further, if the above “y / (x + y)” (that is, Ga / (Ti + Ga)) exceeds 0.99, 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 + O) / (Ti + Ga + N + O)) is less than 0.45, since the amount of metal nitriding is small, a wurtzite type single phase cannot be obtained, and sufficient resistance is obtained. A high B constant cannot be obtained.
Further, when the above “z” (that is, (N + O) / (Ti + Ga + N + O)) exceeds 0.55, a wurtzite single phase cannot be obtained. This means that the stoichiometric ratio when there is no defect at the nitrogen site in the wurtzite type single phase is N / (Ti + Ga + N) = 0.5, and when all the defects at the nitrogen site are supplemented by oxygen. This results from the fact that the stoichiometric ratio of (N + O) / (Ti + Ga + N + O) = 0.5. The z amount exceeding 0.5 is due to the introduction of interstitial oxygen and the accuracy of quantitative determination of light elements (nitrogen, oxygen) in XPS analysis.
On the other hand, if the “w” (that is, O / (N + O)) exceeds 0.85, a wurtzite single phase cannot be obtained. This means that when w = 1 and y / (x + y) = 0, it is a rutile TiO ₂ phase, and when w = 1 and y / (x + y) = 1, it is a corundum Ga ₂ O ₃ phase. Can be understood by considering

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.

A film-type thermistor sensor according to a third aspect of the invention includes an insulating film, a thin film thermistor portion formed on the insulating film with the metal nitride material for the thermistor of the first or second aspect, and at least the thin film thermistor. And a pair of pattern electrodes formed above or below the portion.
That is, in this film type thermistor sensor, the thin film thermistor portion is formed of the metal nitride material for the thermistor of the first or second invention on the insulating film. The thin film thermistor portion having a high B-constant and high heat resistance allows the use of an insulating film having a low heat resistance such as a resin film, and a thin and flexible thermistor sensor having good thermistor characteristics.
Conventionally, substrates 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 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.

A method for manufacturing a metal nitride material for a thermistor according to a fourth invention is a method for manufacturing a metal nitride material for a thermistor according to the first or second invention, wherein a Ga evaporation source, a Ti evaporation source, It has the film-forming process which forms into a film by the reactive plasma vapor deposition method in nitrogen and oxygen containing atmosphere.
That is, in this method for producing a metal nitride material for a thermistor, a reactive plasma deposition (RPD) method is used in a nitrogen and oxygen containing atmosphere using a Ga evaporation source and a Ti evaporation source. Therefore, the metal nitride material for the thermistor of the present invention made of TiGaNO can be formed. In particular, this manufacturing method enables film formation at a relatively low temperature of 200 ° C. or lower. In addition, if this reactive plasma vapor deposition method is used, even if the form of Ga is granular or liquid, it is possible to form a film without being limited to the form. Therefore, the reactive plasma deposition method is more suitable for forming a nitride material containing Ga than reactive sputtering.

The present invention has the following effects.
That is, according to the metal nitride material for a thermistor according to the present invention, the general formula: Ti _x Ga _y (N _1-w O _w ) _z (0.0 ≦ w ≦ 0.85, 0.70 ≦ y / ( x + y) ≦ 0.99, 0.45 ≦ z ≦ 0.55, x + y + z = 1), and its crystal structure is a hexagonal wurtzite type single phase, which is good B constant can be obtained, and it has high heat resistance. In addition, according to the method for manufacturing a metal nitride material for thermistor according to the present invention, a film is formed by a reactive plasma deposition method in a nitrogen and oxygen containing atmosphere using a Ga evaporation source and a Ti evaporation source. The metal nitride material for thermistors of the present invention made of TiGaNO can be formed. Furthermore, according to the film type thermistor sensor according to the present invention, since the thin film thermistor portion is formed of the metal nitride material for thermistor of the present invention on the insulating film, the insulating film having low heat resistance such as a resin film. Can be used to obtain a thin and flexible thermistor sensor having good thermistor characteristics. Further, since the substrate 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—Ga— (N + O) -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. In this embodiment, it is a perspective view which shows a film type thermistor sensor. In this embodiment, it is a perspective view which shows the manufacturing method of a film type thermistor sensor in order of a process. It is simple front sectional drawing which shows the internal structure of a reactive plasma vapor deposition (RPD) apparatus. In the 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 | device 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 Ga / (Ti + Ga) ratio and B constant. In the Example which concerns on this invention, it is a graph which shows the relationship between N / (Ti + Ga + N) ratio and O / (N + O) ratio. In the Example which concerns on this invention, it is a graph which shows the result of X-ray diffraction (XRD) in the case where Ga / (Ti + Ga) = 0.91. It is a cross-sectional SEM photograph of the Example which concerns on this invention.

  Hereinafter, an embodiment of a metal nitride material for a thermistor according to the present invention, a manufacturing method thereof, and a film type thermistor sensor will be described with reference to FIGS. In the drawings used for the following description, the scale is appropriately changed as necessary to make each part recognizable or easily recognizable.

The metal nitride material for the thermistor of this embodiment is a metal nitride material used for the thermistor, and has the general formula: Ti _x Ga _y (N _1-w O _w ) _z (0.0 ≦ w ≦ 0.85) 0.70 ≦ y / (x + y) ≦ 0.99, 0.45 ≦ z ≦ 0.55, x + y + z = 1), the crystal structure of which is a hexagonal wurtzite type It is a single phase of (space group P6 ₃ mc (No. 186)).

As shown in FIG. 1, this metal nitride material for the thermistor has a composition in a region surrounded by points A, B, C, and D in the Ti—Ga— (N + O) ternary phase diagram, It is a metal nitride whose phase is wurtzite.
The composition ratios (x, y, z) (atm%) of the points A, B, C, and D are A (13.50, 31.50, 55.00), B (0.45, 44). .55, 55.00), C (0.45, 54.45, 45.00), D (16.50, 38.50, 45.00).

As described above, the crystal structure of the wurtzite type is a hexagonal space group P6 ₃ mc (No. 186), and Ti and Ga belong to the same atomic site and are in a so-called solid solution state (for example, In the case of Ti _0.1 Ga _0.9 N, Ti and Ga are present at the same atomic site with a probability of 10% and 90%.) The wurtzite type has a (Ti, Ga) (N, O) tetrahedral apex-connected structure, and the closest site of the (Ti, Ga) site is N (nitrogen) or O (oxygen). , Ga) is tetracoordinate with nitrogen or oxygen.

The metal nitride material for a thermistor of this embodiment is a columnar crystal that is formed in a film shape and extends in a direction perpendicular to the surface of the film. Furthermore, in the metal nitride material for thermistors of this embodiment, the a axis is oriented more strongly than the c 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) (hkl index indicating a-axis orientation) and (002) (hkl index indicating c-axis orientation), “(100) peak intensity” / “(( 002) peak intensity ”is less than 1, and the c-axis orientation is strong.

  Next, a film type thermistor sensor using the metal nitride material for the thermistor of this embodiment will be described. As shown in FIG. 2, the film type thermistor sensor 1 includes an insulating film 2, a thin film thermistor section 3 formed on the insulating film 2 from the metal nitride material for the thermistor, and at least the thin film thermistor section 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. In addition, as the insulating film 2, PET: polyethylene terephthalate, PEN: polyethylene naphthalate, or the like may be used. Moreover, as the insulating film 2, the film which has 200 degreeC or more heat resistance, such as a polyimide, is suitable.
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.

  On the base end portion of the pair of linearly extending portions 4b, a plating portion 4c such as Au plating is formed as a lead wire lead-out portion. One end of a lead wire is joined to the plating portion 4c with a solder material or the like. Further, the polyimide coverlay film 5 is pressure-bonded on the insulating film 2 except for the end of the insulating film 2 including the plated portion 4c. In place of the polyimide coverlay film 5, a polyimide or epoxy resin material layer may be formed on the insulating film 2 by printing.

  A manufacturing method of the metal nitride material for the thermistor and a manufacturing method of the film type thermistor sensor 1 using the same will be described below with reference to FIG.

  First, in the method for producing a metal nitride material for a thermistor of this embodiment, a film is formed by a reactive plasma deposition (RPD) method in a nitrogen and oxygen-containing atmosphere using a Ga evaporation source and a Ti evaporation source. It has a film forming process. In the RPD method of this film forming process, nitrogen gas and oxygen gas are introduced into the apparatus as reaction gases, and Ar plasma 14 is transferred from the plasma gun 11 to the Ga evaporation source 12 and Ti evaporation source 13 as shown in FIG. Is a physical vapor deposition method in which a thin film of an oxynitride film is deposited on a substrate (insulating film 2) placed on the top by melting, sublimating and ionizing the substrate. The RPD apparatus 10 used for this film formation is an ion plating apparatus using a pressure gradient type Ar plasma gun, which is equipped with two plasma guns 11 and vapor-deposits Ga and Ti independently controlled. be able to.

More specifically, first, for example, the insulating film 2 of a polyimide film having a thickness of 50 μm shown in FIG. 3A is mounted on the substrate rotation support portion 15 in the RPD device 10. The substrate rotation support unit 15 is rotationally driven around the axis during film formation.
In FIG. 4, 16A is a crucible containing metal Ga, 16B is a crucible containing metal Ti, and 17 is a reaction gas inlet.

Furthermore, after heating the inside of the furnace to a predetermined temperature with the heater 18 while evacuating the inside of the apparatus and maintaining a vacuum,
-Furnace atmosphere temperature: 180-200 ° C
Evaporation source 12: metallic Ga
-Plasma gun discharge power for the evaporation source 12: 2 kW
Evaporation source 13: metal Ti
-Plasma gun discharge power to the evaporation source 13: 5 to 11 kW
-Discharge gas flow rate: Argon (Ar) gas 80sccm
Reaction gas flow rate: nitrogen _{(N 2)} gas 50~100sccm
Oxygen (O ₂ ) gas 0-70sccm
For the thermistor, a composite oxynitride layer comprising a (Ti, Ga) (N, O) layer having a predetermined composition and a target average layer thickness is formed on the surface of the insulating film 2 by vapor deposition. A thin film thermistor portion 3 made of a metal nitride material is formed.
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.

  Next, by sputtering, for example, a Cr film is formed to 20 nm, and an Au film is further formed to 200 nm. Further, after applying a resist solution thereon with a bar coater, prebaking is performed at 110 ° C. for 1 minute 30 seconds, and after exposure with an exposure apparatus, unnecessary portions are removed with a developer, and post baking is performed at 150 ° C. for 5 minutes. Patterning is performed at. Thereafter, unnecessary electrode portions are wet-etched with a commercially available Au etchant and Cr etchant, and as shown in FIG. 3C, pattern electrodes 4 having desired comb-shaped electrode portions 4a are formed by resist stripping. . Alternatively, the pattern electrode 4 may be formed on the insulating film 2 first, and the thin film thermistor portion 3 may be formed on the comb electrode portion 4a. In this case, the comb electrode portion 4 a of the pattern electrode 4 is formed under the thin film thermistor portion 3.

  Next, as shown in FIG. 3 (d), for example, a polyimide coverlay film 5 with an adhesive having a thickness of 50 μm is placed on the insulating film 2 and pressed by a press at 150 ° C. and 2 MPa for 10 minutes. Adhere. Further, as shown in FIG. 3E, an end portion of the linearly extending portion 4b is formed with a 2 μm Au thin film by using, for example, an Au plating solution to form a plated portion 4c.

When a plurality of film type thermistor sensors 1 are manufactured simultaneously, after forming the plurality of thin film thermistor portions 3 and the pattern electrodes 4 on the large sheet of the insulating film 2 as described above, each film type thermistor sensor is formed from the large sheet. Cut to 1.
In this way, for example, a thin film thermistor sensor 1 having a size of 25 × 3.6 mm and a thickness of 0.1 mm is obtained.

Thus, in the metal nitride material for the thermistor of this embodiment, the general formula: Ti _x Ga _y (N _1-w O _w ) _z (0.0 ≦ w ≦ 0.85, 0.70 ≦ y / (x + y) ) ≦ 0.99, 0.45 ≦ z ≦ 0.55, x + y + z = 1), and the crystal structure is a hexagonal wurtzite single phase, A B constant is obtained and high heat resistance is obtained. In particular, when oxygen (O) is contained, heat resistance is improved by an effect such as oxygen filling nitrogen defects in the crystal or introducing interstitial oxygen.
In addition, since the metal nitride material for the thermistor is a columnar crystal extending in a direction perpendicular to the surface of the film, the film has high crystallinity and high heat resistance.

  In the manufacturing method of the metal nitride material for the thermistor of the present embodiment, a film forming step is performed by a reactive plasma deposition method in an atmosphere containing nitrogen and oxygen using a Ga evaporation source and a Ti evaporation source. Therefore, the metal nitride material for thermistors of the present invention made of TiGaNO can be formed. In particular, this manufacturing method enables film formation at a relatively low temperature of 200 ° C. or lower.

Therefore, in the film type thermistor sensor 1 using the thermistor metal nitride material of the present embodiment, the thin film thermistor portion 3 is formed on the insulating film 2 from the thermistor metal nitride material. The thin film thermistor portion 3 that can be formed with a high B constant and has high heat resistance allows the use of an insulating film 2 with low heat resistance such as a resin film, and is thin and flexible with good thermistor characteristics. A thermistor sensor can be obtained.
Conventionally, substrates 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 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.

  Next, with respect to the metal nitride material for thermistor according to the present invention, the manufacturing method thereof, and the film type thermistor sensor, the results of the evaluation made by the example manufactured based on the above embodiment will be specifically described with reference to FIGS. I will explain it.

<Production of film evaluation element>
As an example of the present invention and a comparative example, a film evaluation element 121 shown in FIG. 5 was produced as follows. In each of the following examples of the present invention, _one using a metal nitride for the thermistor which was Ti _x Ga _y (N _1-w O _w ) _z was produced.
First, a metal nitride material for a thermistor formed with various composition ratios shown in Table 1 having a thickness of 500 nm on a Si wafer with a thermal oxide film to be a Si substrate S with various composition ratios by the RPD method described above. The thin film thermistor part 3 was formed.

Next, a 20 nm Cr film was formed on the thin film thermistor portion 3 by sputtering, and a 200 nm Au film was further formed. Further, after applying a resist solution thereon with a spin coater, pre-baking is performed at 110 ° C. for 1 minute 30 seconds. After exposure with an exposure apparatus, unnecessary portions are removed with a developing solution, and post-baking is performed at 150 ° C. for 5 minutes. Then, patterning was performed. Thereafter, unnecessary electrode portions were wet-etched with a commercially available Au etchant and Cr etchant, and a patterned electrode 124 having a desired comb-shaped electrode portion 124a was formed by resist stripping. Then, this was diced into chips to obtain a film evaluation element 121 for B constant evaluation and heat resistance test.
For comparison, comparative examples in which the composition ratio of Ti _x Ga _y (N _1-w O _w ) _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
The thin film thermistor portion 3 obtained by the RPD method was subjected to elemental analysis 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 2. In addition, the composition ratio in the following table | surface is shown by "atomic%". Quantitative analysis was performed on a sputter surface having a depth of 100 nm from the outermost surface of some samples, and it was confirmed that the composition was the same as that of the sputter surface having a depth of 20 nm within the range of quantitative accuracy.

  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 + O) / (Ti + Ga + N + O) is ± 2%, and the quantitative accuracy of Ga / (Ti + Ga) is ± 1%.

(2) Specific resistance measurement
About the thin film thermistor part 3 obtained by RPD method, the specific resistance in 25 degreeC was measured by the 4 terminal method. The results are shown in Table 2.
(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 2. Further, it has been confirmed that the thermistor has a negative temperature characteristic from resistance values of 25 ° C. and 50 ° C.

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 Ga _y (N _1-w O _w ) _z is within the region surrounded by points A, B, C, and D in the ternary triangular diagram shown in FIG. That is, all examples in the region where “0.0 ≦ w ≦ 0.85, 0.70 ≦ y / (x + y) ≦ 0.99, 0.45 ≦ z ≦ 0.55, x + y + z = 1” are satisfied. Thus, thermistor characteristics of resistivity: 1000 Ωcm or more and B constant: 1000 K or more are achieved.

  FIG. 6 shows a graph showing the relationship between the resistivity at 25 ° C. and the B constant from the above results. A graph showing the relationship between the Ga / (Ti + Ga) ratio and the B constant is shown in FIG. From these graphs, in the region of Ga / (Ti + Ga) = 0.7 to 0.98 and (N + O) / (Ti + Ga + N + O) = 0.4 to 0.5, the wurtzite type crystal system is hexagonal. In the case of a single phase, a high resistance and high B constant region having a specific resistance value at 25 ° C. of 1000 Ωcm or more and a B constant of 1000 K or more can be realized. In the data of FIG. 7, the B constant varies with the same Ga / (Ti + Ga) ratio because the amount of nitrogen and oxygen in the crystal are different, or the amount of lattice defects such as nitrogen defects and oxygen defects. This is because they are different.

Comparative Example 1 shown in Table 1 is a region where (N + O) / (Ti + Ga + N + O) is less than 40%, and the metal is in a crystal state in which nitriding is insufficient. 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.
Comparative Examples 2 and 3 shown in Table 1 are regions of Ga / (Ti + Ga) ≦ 0.66, and the crystal system is a cubic NaCl type.
Comparative Example 4 shown in Table 1 is a region of 0.66 <Ga / (Ti + Ga) <0.70, and the crystal system coexists with a hexagonal wurtzite type and a cubic NaCl type.
Thus, in the region of Ga / (Ti + Ga) <0.7, the specific resistance value at 25 ° C. was less than 1000 Ωcm, the B constant was less than 1000 K, and the region was low resistance and low B constant.

(4) Thin film X-ray diffraction (identification of crystal phase)
The crystal phase of the thin film thermistor portion 3 obtained by the RPD method was identified by grazing incidence X-ray diffraction (Grazing Incidence X-ray Diffraction). This thin film X-ray diffraction was a small angle X-ray diffraction experiment, and the measurement was performed in the range of 2θ = 20 to 130 degrees with Cu as the tube, the incident angle of 1 degree. Some samples were measured in the range of 2θ = 20 to 100 degrees with an incident angle of 0 degrees.

  As a result, in the region of Ga / (Ti + Ga) ≧ 0.7, it is a wurtzite type phase (hexagonal crystal, the same phase as GaN), and in the region of Ga / (Ti + Ga) ≦ 0.66, the NaCl type phase. (Cubic, same phase as TiN). Moreover, in 0.66 <Ga / (Ti + Ga) <0.7, it was a crystal phase in which the wurtzite type phase and the NaCl type phase coexist.

Thus, in the TiGaNO system, a region having a high resistance and a high B constant exists in the wurtzite phase of Ga / (Ti + Ga) ≧ 0.7. In the examples of the present invention, the impurity phase is not confirmed, and is a wurtzite type single phase.
In Comparative Example 1 shown in Table 1, as described above, the crystal phase was neither the wurtzite type phase nor the NaCl type phase, 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 that is deficient in nitriding and deficient in oxidation 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, 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.
As a result, the examples of the present invention had strong a-axis orientation.

  In addition, even if it formed into a film on the polyimide film on the same film-forming conditions, it confirmed that the wurtzite type single phase was formed similarly. Moreover, even if it forms into a film on a polyimide film on the same film-forming conditions, it has confirmed that orientation does not change.

An example of an XRD profile of an example with strong a-axis orientation is shown in FIG. In this example, Ga / (Ti + Ga) = 0.91 (wurtzite type, hexagonal crystal), and the incident angle was 1 degree. As can be seen from this result, in this example, the intensity of (100) is stronger than (002).
In the graph, (*) is a peak derived from the apparatus and from the Si substrate with a thermal oxide film, and it is confirmed that it is not the peak of the sample body or the peak of the impurity phase. Moreover, the incident angle was set to 0 degree, the symmetry measurement was implemented, it confirmed that the peak had disappeared, and it was checked that it is a peak derived from a device and a Si substrate with a thermal oxide film.

  Regarding the wurtzite material of the example of the present invention, the correlation between the nitrogen amount and the oxygen amount was further examined. FIG. 8 shows the results of examining the relationship between the N / (Ti + Ga + N) ratio and the O / (N + O) ratio. As can be seen from this result, the sample with less N / (Ti + Ga + N) tends to have a larger amount of O / (N + O). In other words, it is shown that a material with a smaller amount of atomic defects at the nitrogen site requires less oxygen.

<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 (Ga / (Ti + Ga) = 0.91, wurtzite type, hexagonal type formed on a Si substrate S with a thermal oxide film about 140 nm. FIG. 9 shows a cross-sectional SEM photograph of the thin film thermistor portion 3 having a strong crystal and a-axis orientation.
A sample obtained by cleaving and cleaving the Si substrate S is used as the sample of this example. Moreover, it is the photograph which observed the inclination at an angle of 45 degrees.

  As can be seen from this photograph, the examples of the present invention are formed of dense columnar crystals. That is, it has been observed that columnar crystals grow in a direction perpendicular to the substrate surface. Note that the breakage of the columnar crystal occurred when the Si substrate S was cleaved. In addition, even when each film is formed with a thickness of 200 nm, 500 nm, and 1000 nm on the Si substrate S with a thermal oxide film, it is confirmed that the film is formed with dense columnar crystals as described above.

For the columnar crystal size in the figure, the example in which the a-axis orientation was strong in FIG. 8 had a particle size of about 15 nmφ (± 5 nmφ) and a length of about 140 nm. Here, the particle diameter is the diameter of the columnar crystal in the substrate surface, and the length is the length (film thickness) of the columnar crystal in the direction perpendicular to the substrate surface.
When the aspect ratio of the columnar crystal is defined as (length) / (grain size), this embodiment has a large aspect ratio of 7 or more. It is considered that the film is dense due to the small grain size of the columnar crystals.

<Evaluation of heat resistance test>
In some of the 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 2. For comparison, comparative examples using conventional Ta—Al—N materials were also evaluated in the same manner.
As can be seen from these results, the resistance increase rate of the Ti-Ga- (N + O) system is higher when compared with an example having the same amount of B constant as the comparative example of the Ta-Al-N system. Both the B constant increase rate is small, and the Ti—Ga— (N + O) system is superior in heat resistance when viewed in terms of changes in electrical characteristics before and after the heat resistance test.

  Note that it is considered that a wurtzite phase cannot be produced in a high concentration Al region because the Ta ion radii of Ta—Al—N materials are much larger than those of Ti and Al. Since the TaAlN system is not a wurtzite type phase, the wurtzite type Ti—Ga— (N + O) system is considered to have better heat resistance.

Thus, in the said evaluation, if it produces in the range of (N + O) / (Ti + Ga + N + O): 0.45-0.55, it turns out that a favorable thermistor characteristic can be shown.
Note that the ideal stoichiometric ratio without nitrogen and oxygen defects is (N + O) / (Ti + Ga + N + O) = 0.5. In this test, there is a sample with an amount of (N + O) / (Ti + Ga + N + O) exceeding 0.5, but due to the introduction of interstitial oxygen and the quantitative accuracy of light elements (nitrogen, oxygen) in XPS analysis. It is thought to be caused. On the other hand, there are (N + O) / (Ti + Ga + N + O) amount samples smaller than 0.5, and it can be seen that there are atomic defects in the nitrogen and oxygen sites in the thermistor material of these samples. Furthermore, in order to compensate for defects, it is particularly desirable to add a process for compensating for nitrogen defects, and as one of them, nitrogen plasma irradiation or the like is preferably performed.

  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.

  DESCRIPTION OF SYMBOLS 1 ... Film type thermistor sensor, 2 ... Insulating film, 3 ... Thin film thermistor part, 4,124 ... Pattern electrode

Claims (4)

A metal nitride material used for the thermistor,
General formula: Ti _x Ga _y (N _1-w O _w ) _z (0.0 ≦ w ≦ 0.85, 0.70 ≦ y / (x + y) ≦ 0.99, 0.45 ≦ z ≦ 0.55 X + y + z = 1), and a metal nitride represented by
A metal nitride material for a thermistor characterized in that its crystal structure is a hexagonal wurtzite type single phase. The thermistor metal nitride material according to claim 1,
Formed into a film,
A metal nitride material for a thermistor, wherein the metal nitride material is a columnar crystal extending in a direction perpendicular to the surface of the film. An insulating film;
A thin film thermistor portion formed of the metal nitride material for a thermistor according to claim 1 or 2 on the insulating film;
A film type thermistor sensor comprising at least a pair of pattern electrodes formed above or below the thin film thermistor section. A method for producing a metal nitride material for a thermistor according to claim 1 or 2,
A metal nitride material for a thermistor comprising a film forming step of forming a film by a reactive plasma deposition method in a nitrogen and oxygen containing atmosphere using a Ga evaporation source and a Ti evaporation source Production method.