Temperature sensor

Abstract

The temperature sensor is provided with a pair of lead frames, a sensor portion connected to the pair of lead frames, and an insulating holding portion which is fixed to the pair of lead frames and holds the lead frames. The sensor portion is provided with an insulating film; a thin film thermistor portion formed as a pattern on the surface of the insulating film with a thermistor material; a pair of interdigitated electrodes formed as patterns having multiple comb portions and facing each other on the thin film thermistor portion; and a pair of pattern electrodes connected to the pair of interdigitated electrodes and formed as patterns on the surface of the insulating film. The pair of lead frames is extended and adhered to the surface of the insulating film disposing the thin film thermistor portion therebetween and is connected to the pair of pattern electrodes.

Claims

1. A temperature sensor comprising: a pair of lead frames; a sensor portion connected to the pair of lead frames; and an insulating holding portion which is fixed to the pair of lead frames and holds the lead frames, wherein the sensor portion further comprises: an insulating film; a thin film thermistor portion formed as a pattern on the surface of the insulating film with a thermistor material; a pair of interdigitated electrodes formed as patterns having multiple comb portions and facing each other on at least one of the top or the bottom of the thin film thermistor portion; and a pair of pattern electrodes that respectively have ends connected to the pair of interdigitated electrodes and other ends connected to the pair of lead frames, and are formed as patterns on the surface of the insulating film, and wherein the pair of lead frames is extended on both sides of the thin film thermistor portion at a certain interval in the surface of the insulating film.

2. The temperature sensor according to claim 1, wherein the insulating film is generally rectangular, the pair of lead frames extends across substantially the entire length in the extending direction of the insulating film, the thin film thermistor portion is arranged at one end of the insulating film, and the pattern electrodes are formed extending from one end to the other end of the insulating film and are connected to the lead frames at the other end of the insulating film, respectively.

3. The temperature sensor according to claim 2, wherein the pair of pattern electrodes is formed in a meander shape.

4. The temperature sensor according to claim 1, wherein an insulating protective sheet covering at least the lead frames is adhered to the surface of the insulating film.

5. The temperature sensor according to claim 1, wherein the thin film thermistor portion consists of a metal nitride represented by the general formula: Ti.sub.xAl.sub.yN.sub.z (where 0.70≦y/(x+y)≦0.95, 0.4≦z ≦0.5, and x+y+z=1), and the crystal structure thereof is a hexagonal wurtzite-type single phase.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is an example of a plan view and a front view illustrating a temperature sensor according to a first embodiment of the present invention.

(2) FIG. 2 is an example of a plan view and a cross-sectional view illustrating a sensor portion according to the first embodiment.

(3) FIG. 3 is a Ti—Al—N-based ternary phase diagram illustrating the composition range of a metal nitride material for a thermistor according to the first embodiment.

(4) FIG. 4 is an example of a plan view and a cross-sectional view illustrating a step of forming a thin film thermistor portion according to the first embodiment.

(5) FIG. 5 is an example of a plan view and a cross-sectional view illustrating electrode forming step according to the first embodiment.

(6) FIG. 6 is an example of a plan view and a front view illustrating a lead frame adhering step according to the first embodiment.

(7) FIG. 7 is an example of a plan view and a cross-sectional view illustrating a sensor portion of a temperature sensor according to a second embodiment of the present invention.

(8) FIG. 8 is an example of a plan view and a front view illustrating the temperature sensor according to the second embodiment.

(9) FIG. 9 is an example of a plan view and a cross-sectional view illustrating a sensor portion of a temperature sensor according to a third embodiment of the present invention.

(10) FIG. 10 is an example of a plan view and a front view illustrating the temperature sensor according to the third embodiment.

(11) FIG. 11 is a front view and a plan view illustrating a film evaluation element for a metal nitride material for a thermistor according to Example of a temperature sensor of the present invention.

(12) FIG. 12 is a graph illustrating the relationship between a resistivity at 25° C. and a B constant according to Examples and Comparative Example of the present invention.

(13) FIG. 13 is a graph illustrating the relationship between the Al/(Ti+Al) ratio and the B constant according to Examples and Comparative Example of the present invention.

(14) FIG. 14 is a graph illustrating the result of X-ray diffraction (XRD) in the case of a strong c-axis orientation where Al/(Ti+Al)=0.84 according to Example of the present invention.

(15) FIG. 15 is a graph illustrating the result of X-ray diffraction (XBD) in the case of a strong a-axis orientation where Al/(Ti+Al)=0.83 according to Example of the present invention.

(16) FIG. 16 is a graph illustrating the result of X-ray diffraction (XRD) in the case where Al/(Ti+Al)=0.60 according to Comparative Example of the present invention.

(17) FIG. 17 is a graph illustrating the relationship between the Al/(Ti+Al) ratio and the B constant obtained by comparing Example revealing a strong a-axis orientation and Example revealing a strong c-axis orientation according to Examples of the present invention.

(18) FIG. 18 is a cross-sectional SEM photograph illustrating Example revealing a strong c-axis orientation according to Example of the present invention.

(19) FIG. 19 is a cross-sectional SEM photograph illustrating Example revealing a strong a-axis orientation according to Example of the present invention.

BEST MODES FOR CARRYING OUT THE INVENTION

(20) Hereinafter, a description will be given of a film-type thermistor sensor according to a first embodiment of the present invention with reference to FIGS. 1 to 6. In a part of the drawings used in the following description, the scale of each component is changed as appropriate so that each component is recognizable or is readily recognized.

(21) As shown in FIGS. 1 and 2, a temperature sensor (1) of the present embodiment includes a pair of lead frames (2), a sensor portion (3) connected to the pair of lead frames (2), and an insulating holding portion (4) which is fixed to the pair of lead frames (2) and holds the lead frames (2).

(22) The pair of lead frames (2) is formed of an alloy such as a copper based alloy, an iron based alloy, stainless, or the like, and is supported by the resin holding portion (4) with the lead frames (2) being held at regular intervals. Note that the pair of lead frames (2) is connected to a pair of lead wires (5) in the holding portion (4). The holding portion (4) has an opening (4a) for attachment.

(23) The sensor portion (3) is a film-type thermistor sensor that includes an insulating film (6); a thin film thermistor portion (7) formed as a pattern on the surface of the insulating film (6) with a thermistor material; a pair of interdigitated electrodes (8) formed as patterns having multiple comb portions (8a) and facing each other on at least one of the top or the bottom of the thin film thermistor portion (7); a pair of pattern electrodes (9) connected to the pair of interdigitated electrodes (8) and formed as patterns on the surface of the insulating film (6); and an insulating protective film (10) for covering the thin film thermistor portion (7) and the interdigitated electrodes (8). An insulating protective sheet (11) covering the thin film thermistor portion (7), the pattern electrodes (9), and the lead frames (2) is adhered to the surface of the insulating film (6).

(24) The pair of lead frames (2) is extended and adhered to the surface of the insulating film (6) disposing the thin film thermistor portion (7) therebetween by an adhesive (not shown) such as a conductive resin adhesive and is connected to the pair of the pattern electrodes (9).

(25) The insulating film (6) is substantially rectangular and is, for example, a polyimide resin sheet formed in a band shape having a thickness from 7.5 to 125 μm. Although the insulating film (6) may also be produced by polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or the like, a polyimide film is preferably used for measuring the temperature of a heating roller because the maximum working temperature thereof is as high as 230° C.

(26) The pair of lead frames (2) extends across substantially the entire length in the extending direction of the insulating film (6) and is adhered to the insulating film (6).

(27) Terminal portions (9a) are provided at the proximal end of the pair of the pattern electrodes (9), and the lead frames (2) are connected to the terminal portions (9a) by a conductive resin adhesive or the like.

(28) The thin film thermistor portion (7) is arranged at one end of the insulating film (6) and is formed of a thermistor material of TiAlN. In particular, the thin film thermistor portion (7) consists of a metal nitride represented by the general formula: Ti.sub.xAl.sub.yN.sub.z (where 0.70≦y/(x+y)≦0.95, 0.4≦z≦0.5, and x+y+z=1), and the crystal structure thereof is a hexagonal wurtzite-type single phase.

(29) Each of the pattern electrodes (9) and the interdigitated electrodes (8) has a bonding layer of Cr or NiCr having a film thickness from 5 to 100 nm formed on the thin film thermistor portion (7) and an electrode layer of a noble metal such as Au having a film thickness from 50 to 1000 nm formed on the bonding layer.

(30) The pair of the interdigitated electrodes (8) is arranged in opposing relation to each other such that the comb portions (8a) are interlocked with one another in an alternating comb-like pattern.

(31) Note that the comb portions (8a) extend along the extending direction (the extending direction of the lead frames (2)) of the insulating film (6). Specifically, temperature measurement is performed with the backside of the insulating film (6) being brought into abutment with the heating roller in rotation. Since the insulating film (6) is bent to a curvature along its extending direction, the bending stresses are also applied to the thin film thermistor portion (7) in the same direction. At this time, the comb portions (8a) extend in the same direction as the insulating film (6), which reinforces the thin film thermistor portion (7), resulting in suppression of occurrence of cracks.

(32) The distal ends of the pair of pattern electrodes (9) are respectively connected to the interdigitated electrodes (8), and the proximal ends thereof are the terminal portions (9a) which are arranged on the both side sections of the insulating film (6).

(33) The protective film (10) is an insulating resin film or the like, and a polyimide film having a thickness of 20 μm is employed as the protective film (10).

(34) As described above, the thin film thermistor portion (7) is a metal nitride material consisting of a metal nitride represented by the general formula: Ti.sub.xAl.sub.yN.sub.z (where 0.70≦y/(x+y)≦0.95, 0.4≦z≦0.5, and x+y+z=1), wherein the crystal structure thereof is a wurtzite-type (space group P6.sub.3mc (No. 186)) single phase having a hexagonal crystal system. Specifically, the metal nitride material has a composition within the region enclosed by the points A, B, C, and D in the Ti—Al—N-based ternary phase diagram as shown in FIG. 3, wherein the crystal phase thereof is a wurtzite-type metal nitride.

(35) Note that the composition ratios (x, y, z) (at %) at the points A, B, C, and D are A (15, 35, 50), B (2.5, 47.5, 50), C (3, 57, 40), and D (18, 42, 40), respectively.

(36) Also, the thin film thermistor portion (7) is formed into the shape of a film having a film thickness from 100 to 1000 nm and is a columnar crystal extending in a vertical direction to the surface of the film. Furthermore, it is preferable that the thin film thermistor portion (7) is strongly oriented along the c-axis more than the a-axis in a vertical direction to the surface of the film.

(37) Note that the decision on whether the thin film thermistor portion (7) has a strong a-axis orientation (100) or a strong c-axis orientation (002) in a vertical direction (film thickness direction) to the surface of the film is determined whether the peak intensity ratio of “the peak intensity of (100)”/“the peak intensity of (002)” is less than 1 by examining the orientation of crystal axis using X-ray diffraction (XRD), where (100) is the Miller index indicating a-axis orientation and (002) is the Miller index indicating c-axis orientation.

(38) A description will be given below of a method for producing the temperature sensor (1) with reference to FIGS. 4 to 6.

(39) The method for producing the temperature sensor (1) of the present embodiment includes a thin film thermistor portion forming step of patterning a thin film thermistor portion (7) on an insulating film (6); an electrode forming step of patterning a pair of pattern electrodes (9) on the insulating film (6) with a pair of the interdigitated electrodes (8) facing each other being disposed on the thin film thermistor portion (7); a protective film forming step of forming a protective film (10) on the surface of the insulating film (6); and a sheet adhering step of adhering a protective sheet (11) for covering the thin film thermistor portion (7), the interdigitated electrodes (8), the pattern electrodes (9), the protective film (10), and the lead frames (2) to the surface of the insulating film (6).

(40) As a more specific example of such a production method, a thermistor film of Ti.sub.xAl.sub.yN.sub.z (x=9, y=43, z=48) having a film thickness of 200 nm is deposited on the insulating film (6) made of a polyimide film having a thickness of 50 μm using a Ti—Al alloy sputtering target in the reactive sputtering method in a nitrogen-containing atmosphere. The thermistor film is produced under the sputtering conditions of an ultimate degree of vacuum of 5×10.sup.−6 Pa, a sputtering gas pressure of 0.4 Pa, a target input power (output) of 200 W, and a nitrogen gas fraction under a mixed gas (Ar gas+nitrogen gas) atmosphere of 20%.

(41) A resist solution is coated on the formed thermistor film using a bar coater, and then prebaking is performed for 1.5 minutes at a temperature of 110° C. After being exposed by an exposure device, an unnecessary portion is removed by a developing solution, and then patterning is performed by post baking for 5 minutes at a temperature of 150° C. Then, an unnecessary thermistor film of Ti.sub.xAl.sub.yN.sub.z is subject to wet etching using commercially available Ti etchant, and then the resist is stripped so as to form the thin film thermistor portion (7) in a desired shape as shown in FIG. 4.

(42) Next, a Cr film bonding layer having a film thickness of 20 nm is formed on the thin film thermistor portion (7) and the insulating film (6) in the sputtering method. Furthermore, an Au film electrode layer having a film thickness of 200 nm is formed on the bonding layer in the sputtering method.

(43) Next, a resist solution is coated on the laminated electrode layer using a bar coater, and then prebaking is performed for 1.5 minutes at a temperature of 110° C. After being exposed by an exposure device, an unnecessary portion is removed by a developing solution, and then patterning is performed by post baking for 5 minutes at a temperature of 150° C. Then, an unnecessary electrode portion is subject to wet etching sequentially using commercially available Au etchant and Cr etchant, and then the resist is stripped so as to form desired interdigitated electrodes (8) and pattern electrodes (9) as shown in FIG. 5.

(44) Furthermore, a polyimide varnish is coated on the resulting interdigitated electrodes (8) and pattern electrodes (9) and then is cured for 30 minutes at a temperature of 250° C. to thereby form a polyimide protective film (10) having a thickness of 20 μm as shown in FIG. 6.

(45) Next, as the protective sheet (11), a polyimide film with adhesive agent is adhered to the surface of the insulating film (6) from the lead frames (2) side to thereby produce the temperature sensor (1).

(46) When a plurality of sensor portions (3) is simultaneously produced, the thin film thermistor portion (7), the interdigitated electrodes (8), the pattern electrodes (9), and the protective film (10) are formed in plural on a large sized sheet of the insulating film (6) as described above, and then the resulting laminated large film is cut into a plurality of sensor portions (3).

(47) Since, in the temperature sensor (1) of the present embodiment, the pair of lead frames (2) is extended and adhered to the surface of the insulating film (6) disposing the thin film thermistor portion (7) therebetween, the sensor portion (3) may be supported by the insulating film (6) while ensuring the rigidity thereof. The entire thickness of the temperature sensor (1) may be thinned by the presence of the thin film thermistor portion (7) directly formed on the insulating film (6) supported by the lead frames (2), so that the temperature sensor (1) may exhibit excellent responsiveness in a small volume thereof.

(48) Since the pair of lead frames (2) is connected to the pair of pattern electrodes (9), the thin film thermistor portion (7) and the lead frames (2) are connected to each other via the pattern electrodes (9) directly formed on the insulating film (6), so that the influence of thermal conductivity with the lead frames (2) is suppressed by a patterned thin wiring as compared with the case where the thin film thermistor portion (7) and the lead frames (2) are connected to each other via lead wires or the like. Since the temperature sensor (1) has high flatness over the contact area against a measurement object and thus is brought into surface contact therewith, accurate temperature detection may be achieved and the surface of the measurement object such as a heating roller or the like in rotation is less prone to be damaged.

(49) Furthermore, since the insulating protective sheet (11) covering at least the lead frames (2) is adhered to the surface of the insulating film (6), the lead frames (2) may be stably held by sandwiching it between the insulating film (6) and the protective sheet (11) and the rigidity of the insulating film (6) may improve.

(50) Since the thin film thermistor portion (7) consists of a metal nitride represented by the general formula: Ti.sub.xAl.sub.yN.sub.z (where 0.70≦y/(x+y)≦0.95, 0.4≦z≦0.5, and x+y+z=1), wherein the crystal structure thereof is a wurtzite-type single phase having a hexagonal crystal system, the metal nitride material having a good B constant and exhibiting excellent heat resistance may be obtained without baking.

(51) Since the metal nitride material is a columnar crystal extending in a vertical direction to the surface of the film, the crystallinity of the film is high, resulting in obtaining high heat resistance.

(52) Furthermore, since the metal nitride material is strongly oriented along the c-axis more than the a-axis in a vertical direction to the surface of the film, the metal nitride material having a high B constant as compared with the case of a strong a-axis orientation is obtained.

(53) Since, in the method for producing the thermistor material layer (the thin film thermistor portion (7)) of the present embodiment, film deposition is performed by the reactive sputtering in a nitrogen-containing atmosphere using a Ti—Al alloy sputtering target, so that the metal nitride material consisting of the above TiAlN can be deposited on a film without baking.

(54) Since a sputtering gas pressure during the reactive sputtering is set to be less than 0.67 Pa, the film made of the metal nitride material, which is strongly oriented along the c-axis more than the a-axis in a vertical direction to the surface of the film, can be formed.

(55) Thus, since, in the temperature sensor (1) of the present embodiment, the thin film thermistor portion (7) is formed in the form of the thermistor material layer on the insulating film (6), the insulating film (6) having low heat resistance, such as a resin film, can be used by the presence of the thin film thermistor portion (7) which is formed without baking and has a high B constant and high heat resistance, so that a thin and flexible thermistor sensor having an excellent thermistor characteristic is obtained.

(56) Conventionally, a substrate material using a ceramics material such as alumina has often been used. For example, if the substrate material is thinned to a thickness of 0.1 mm, the substrate material is very fragile and easily breakable. In the present invention, a film can be used, so that a very thin film-type thermistor sensor (the sensor portion (3)) having a thickness of 0.1 mm can be obtained.

(57) Next, a description will be given below of a temperature sensor according to second and third embodiments of the present invention with reference to FIGS. 7 to 10. In the following embodiments, the same components as those described in the above embodiment are denoted by the same reference numerals, and description thereof is omitted.

(58) While, in the first embodiment, the terminal portions (9a) of the pattern electrodes (9) are arranged at one end of the insulating film (6), the second embodiment is different from the first embodiment in that, in a temperature sensor (21) according to the second embodiment, the pattern electrodes (29) are formed extending from one end to the other end of the insulating film (6) and are connected to the lead frames (2) at the other end of the insulating film (6) as shown in FIGS. 7 and 8.

(59) Specifically, in the second embodiment, the pattern electrodes (29) of the sensor portion (23) are patterned on the inside of the pair of lead frames (2) so as to extend along the same, and are connected to the lead frames (2) by the terminal portions (9a) which are arranged at the other end of the insulating film (6).

(60) Thus, since, in the temperature sensor (21) in the second embodiment, the pattern electrodes (29) are formed extending from one end to the other end of the insulating film (6) and are connected to the lead frames (2) at the other end of the insulating film (6), respectively, the thin pattern electrodes (29) extend in an elongated manner and the connection between the pattern electrodes (29) and the lead frames (2) is set to be away from the thin film thermistor portion, heat transfer to the lead frames (2) may further be suppressed, resulting in highly accurate temperature measurement with excellent responsiveness.

(61) Next, while the pattern electrodes (29) extend linearly in the second embodiment, the third embodiment is different from the second embodiment in that, a temperature sensor (31) according to the third embodiment has a sensor portion (33) in which pattern electrodes (39) extends in a meander shape as shown in FIGS. 9 and 10.

(62) Specifically, in the third embodiment, the pattern electrodes (39) are repeatedly folded back in a zigzag pattern extending from one end to the other end of the insulating film (6), so that the pattern electrodes (39) are longer than the linear pattern electrodes (9).

(63) Thus, since, in the temperature sensor (31) in the third embodiment, the pair of pattern electrodes (39) is formed in a meander shape, the length of the pattern electrodes (39) increases, resulting in suppression of thermal conductivity to the lead frames (2).

EXAMPLES

(64) Next, the evaluation results of Examples produced based on the above embodiment with regard to the temperature sensor according to the present invention will be specifically described with reference to FIGS. 11 to 19.

(65) <Production of Film Evaluation Element>

(66) Film evaluation elements (121) shown in FIG. 11 were produced as follows as Examples and Comparative Examples for evaluating the thermistor material layer (the thin film thermistor portion (7)) of the present invention.

(67) Firstly, each of the thin film thermistor portions (7) having a thickness of 500 nm, which were made of metal nitride materials formed with various composition ratios as shown in Table 1, was formed on a Si wafer with a thermal oxidation film as a Si substrate S by using Ti—Al alloy targets formed with various composition ratios in the reactive sputtering method. The thin film thermistor portions (7) were produced under the sputtering conditions of an ultimate degree of vacuum of 5×10.sup.−6 Pa, a sputtering gas pressure of from 0.1 to 1 Pa, a target input power (output) of from 100 to 500 W, and a nitrogen gas fraction under a mixed gas (Ar gas+nitrogen gas) atmosphere of from 10 to 100%.

(68) Next, a Cr film having a thickness of 20 nm was formed on the thin film thermistor portion (7) and an Au film having a thickness of 100 nm was further formed thereon by the sputtering method. Furthermore, a resist solution was coated on the laminated metal films using a spin coater, and then prebaking was performed for 1.5 minutes at a temperature of 110° C. After being exposed by an exposure device, an unnecessary portion was removed by a developing solution, and then patterning was performed by post baking for 5 minutes at a temperature of 150° C. Then, an unnecessary electrode portion was subject to wet etching using commercially available Au etchant and Cr etchant, and then the resist was stripped so as to form a pair of the pattern electrodes (124) each having a desired interdigitated electrode portion (124a). Then, the resulting elements were diced into chip elements so as to obtain film evaluation elements (121) for evaluating a B constant and for testing heat resistance.

(69) Note that Comparative Examples in which the film evaluation elements (121) respectively have the composition ratios of Ti.sub.xAl.sub.yN.sub.z outside the range of the present invention and have different crystal systems were similarly produced for comparative evaluation.

(70) <Film Evaluation>

(71) (1) Composition Analysis

(72) The elemental analysis for the thin film thermistor portion (7) obtained by the reactive sputtering method was performed by X-ray photoelectron spectroscopy (XPS). In the XPS, a quantitative analysis was performed for a sputtering surface up to a depth of 20 nm from the outermost surface by Ar sputtering. The results are shown in Table 1. In the following tables, the composition ratio is represented by “at %”.

(73) In the X-ray photoelectron spectroscopy (XPS), a quantitative analysis was performed under the conditions of an X-ray source of MgKα (350 W), a path energy of 58.5 eV, a measurement interval of 0.125 eV, a photo-electron take-off angle with respect to a sample surface of 45 deg, and an analysis area of about 800 μmφ. For the quantification accuracy, the quantification accuracy of N/(Ti+Al+N) was ±2%, and the quantification accuracy of Al/(Ti+Al) was ±1%.

(74) (2) Specific Resistance Measurement

(75) The specific resistance of each of the thin film thermistor portions (7) obtained by the reactive sputtering method was measured by the four-probe method at a temperature of 25° C. The results are shown in Table 1.

(76) (3) Measurement of B Constant

(77) The resistance value for each of the film evaluation elements (121) at temperatures of 25° C. and 50° C. was measured in a constant temperature bath, and a B constant was calculated based on the resistance values at temperatures of 25° C. and 50° C. The results are shown in Table 1.

(78) In the B constant calculating method of the present invention, the B constant is calculated by the following formula using the resistance values at temperatures of 25° C. and 50° C.
B constant (K)=ln(R25/R50)/(1/T25−1/T50)

(79) R25 (Ω): resistance value at 25° C.

(80) R50 (Ω): resistance value at 50° C.

(81) T25 (K): 298.15 K which is absolute temperature of 25° C. expressed in Kelvin

(82) T50 (K): 323.15 K which is absolute temperature of 50° C. expressed in Kelvin

(83) As can be seen from these results, a thermistor characteristic having a resistivity of 100 Ωcm or greater and a B constant of 1500 K or greater is achieved in all Examples in which the composition ratio of Ti.sub.xAl.sub.yN.sub.z falls within the region enclosed by the points A, B, C, and D in the Ti—Al—N-based ternary phase diagram as shown in FIG. 3, i.e., the region where “0.70≦y/(x+y)≦0.95, 0.4≦z≦0.5, and x+y+z=1”.

(84) From the above results, a graph illustrating the relationship between a resistivity at 25° C. and a B constant is shown in FIG. 12. Also, a graph illustrating the relationship between the Al/(Ti+Al) ratio and the B constant is shown in FIG. 13. From these graphs, the film evaluation elements (121) which fall within the region where Al/(Ti+Al) is from 0.7 to 0.95 and N/(Ti+Al+N) is from 0.4 to 0.5 and the crystal system thereof is a hexagonal wurtzite-type single phase have a specific resistance value at a temperature of 25° C. of 100 Ωcm or greater and a B constant of 1500 K or greater, and thus, fall within the region of high resistance and high B constant. In data shown in FIG. 13, the reason why the B constant varies with respect to the same Al/(Ti+Al) ratio is because the film evaluation elements (121) have different amounts of nitrogen in their crystals.

(85) Comparative Examples 3 to 12 shown in Table 1 fall within the region where Al/(Ti+Al)<0.7, and the crystal system thereof is a cubic NaCl-type phase. In Comparative Example 12 (Al/(Ti+Al)=0.67), a NaCl-type phase and a wurtzite-type phase coexist. Thus, the region where Al/(Ti+Al)<0.7 exhibits a specific resistance value at a temperature of 25° C. of less than 100 Ωcm and a B constant of less than 1500 K, and thus, is a region of low resistance and low B constant.

(86) Comparative Examples 1 and 2 shown in Table 1 fall within the region where N/(Ti+Al+N) is less than 40%, and thus, are in a crystal state where nitridation of metals contained therein is insufficient. Comparative Examples 1 and 2 were neither a NaCl-type nor a wurtzite-type and had very poor crystallinity. In addition, it was found that Comparative Examples 1 and 2 exhibited near-metallic behavior because both the B constant and the resistance value were very small.

(87) (4) Thin Film X-Ray Diffraction (Identification of Crystal Phase)

(88) The crystal phases of the thin film thermistor portions (7) obtained by the reactive sputtering method were identified by Grazing Incidence X-ray Diffraction. The thin film X-ray diffraction is a small angle X-ray diffraction experiment. Measurement was performed under the condition of a Cu X-ray tube, the angle of incidence of 1 degree, and 2θ of from 20 to 130 degrees.

(89) As a result of measurement, a wurtzite-type phase (hexagonal, the same phase as that of AlN) was obtained in the region where Al/(Ti+Al)≧0.7, whereas a NaCl-type phase (cubic, the same phase as that of TiN) was obtained in the region where Al/(Ti+Al)<0.65. A crystal phase in which a wurtzite-type phase and a NaCl-type phase coexist was obtained in the region where 0.65<Al/(Ti+Al)<0.7.

(90) Thus, in the Ti—Al—N-based metal nitride material, the region of high resistance and high B constant exists in the wurtzite-type phase where Al/(Ti+Al)≧0.7. In Examples of the present invention, no impurity phase was confirmed and the crystal structure thereof was a wurtzite-type single phase.

(91) In Comparative Examples 1 and 2 shown in Table 1, the crystal phase thereof was neither a wurtzite-type phase nor a NaCl-type phase as described above, and thus, could not be identified in the testing. In these Comparative Examples, the peak width of XRD was very large, resulting in obtaining materials exhibiting very poor crystallinity. It is contemplated that the crystal phase thereof was a metal phase with insufficient nitridation because Comparative Examples 1 and 2 exhibited near-metallic behavior from the viewpoint of electric properties.

(92) TABLE-US-00001 TABLE 1 CRYSTAL AXIS EXHIBITING STRONG DEGREE OF ORIEN- TATION IN VERTICAL DIRECTION XRD PEAK TO INTENSITY SUBSTRATE RATIO OF SURFACE RESULT OF (100)/(002) WHEN ELECTRIC WHEN CRYSTAL SPUT- PROPERTIES CRYSTAL PHASE IS TERING SPECIFIC PHASE IS WURTZITE GAS COMPOSITION RATIO B RESISTANCE WURTZITE TYPE PHASE PRES- Al/ CON- VALUE CRYSTAL TYPE (a-AXIS OR SURE (Ti + Al) STANT AT 25° C. SYSTEM PHASE c-AXIS) (Pa) Ti (%) Al (%) N (%) (%) (K) (Ω cm) COMPARATIVE UNKNOWN — — 29 43 28 60 <0 2.E−04 EXAMPLE 1 INSUFFICIENT NITRIDATION COMPARATIVE UNKNOWN — — 16 54 30 77 25 4.E−04 EXAMPLE 2 INSUFFICIENT NITRIDATION COMPARATIVE NaCl TYPE — — 50 0 50 0 <0 2.E−05 EXAMPLE 3 COMPARATIVE NaCl TYPE — — 47 1 52 3 30 2.E−04 EXAMPLE 4 COMPARATIVE NaCl TYPE — — 51 3 48 6 248 1.E−03 EXAMPLE 5 COMPARATIVE NaCl TYPE — — 50 5 45 9 69 1.E−03 EXAMPLE 6 COMPARATIVE NaCl TYPE — — 23 30 47 57 622 3.E−01 EXAMPLE 7 COMPARATIVE NaCl TYPE — — 22 33 45 80 477 2.E−01 EXAMPLE 8 COMPARATIVE NaCl TYPE — — 21 32 47 61 724 4.E+00 EXAMPLE 9 COMPARATIVE NaCl TYPE — — 20 34 46 83 564 5.E−01 EXAMPLE 10 COMPARATIVE NaCl TYPE — — 19 35 46 85 402 5.E−02 EXAMPLE 11 COMPARATIVE NaCl TYPE + — — 18 37 45 67 665 2.E+00 EXAMPLE 12 WURTZITE TYPE EXAMPLE 1 WURTZITE 0.05 c-AXIS <0.67 15 38 47 72 1980 4.E+02 TYPE EXAMPLE 2 WURTZITE 0.07 c-AXIS <0.67 12 38 50 76 2798 5.E+04 TYPE EXAMPLE 3 WURTZITE 0.45 c-AXIS <0.67 11 42 47 79 3385 1.E+05 TYPE EXAMPLE 4 WURTZITE <0.01 c-AXIS <0.67 11 41 48 79 2437 4.E+02 TYPE EXAMPLE 5 WURTZITE 0.34 c-AXIS <0.67 9 43 48 83 2727 2.E+04 TYPE EXAMPLE 6 WURTZITE <0.01 c-AXIS <0.67 8 42 50 84 3057 2.E+05 TYPE EXAMPLE 7 WURTZITE 0.08 c-AXIS <0.67 8 44 48 84 2665 3.E+03 TYPE EXAMPLE 8 WURTZITE 0.05 c-AXIS <0.67 8 44 48 85 2527 1.E+03 TYPE EXAMPLE 9 WURTZITE <0.01 c-AXIS <0.67 8 45 47 86 2557 8.E+02 TYPE EXAMPLE 10 WURTZITE 0.04 c-AXIS <0.67 7 46 46 86 2449 1.E+03 TYPE EXAMPLE 11 WURTZITE 0.24 c-AXIS <0.67 7 48 65 88 3729 4.E+05 TYPE EXAMPLE 12 WURTZITE 0.73 c-AXIS <0.67 5 49 46 90 2798 5.E+05 TYPE EXAMPLE 13 WURTZITE <0.01 c-AXIS <0.67 5 45 50 90 4449 3.E+06 TYPE EXAMPLE 14 WURTZITE 0.38 c-AXIS <0.67 5 50 45 91 1821 1.E+02 TYPE EXAMPLE 15 WURTZITE 0.13 c-AXIS <0.67 4 50 46 93 3439 6.E+05 TYPE EXAMPLE 16 WURTZITE 3.54 a-AXIS ≧0.67 15 43 42 74 1507 3.E+02 TYPE EXAMPLE 17 WURTZITE 2.94 a-AXIS ≧0.67 10 49 41 83 1794 3.E+02 TYPE EXAMPLE 18 WURTZITE 1.05 a-AXIS ≧0.67 6 52 42 90 2164 1.E+02 TYPE EXAMPLE 19 WURTZITE 2.50 a-AXIS ≧0.67 9 44 47 83 2571 5.E+03 TYPE EXAMPLE 20 WURTZITE 9.09 a-AXIS ≧0.67 8 46 46 84 2501 6.E+03 TYPE EXAMPLE 21 WURTZITE 6.67 a-AXIS ≧0.67 8 45 47 84 2408 7.E+03 TYPE EXAMPLE 22 WURTZITE 2.22 a-AXIS ≧0.67 8 46 46 86 2364 3.E+04 TYPE EXAMPLE 23 WURTZITE 1.21 a-AXIS ≧0.67 7 46 47 87 3317 2.E+06 TYPE EXAMPLE 24 WURTZITE 3.33 a-AXIS ≧0.67 6 51 43 89 2599 7.E+04 TYPE

(93) Next, all of Examples in the present invention were wurtzite-type phase films having strong orientation. Thus, whether the films have strong a-axis orientation or c-axis orientation to the crystal axis in a vertical direction (film thickness direction) to the Si substrate S was examined by XRD. At this time, in order to examine the orientation of crystal axis, the peak intensity ratio of (100)/(002) was measured, where (100) is the Miller index indicating a-axis orientation and (002) is the Miller index indicating c-axis orientation.

(94) Consequently, in Examples in which film deposition was performed at a sputtering gas pressure of less than 0.67 Pa, the intensity of (002) was much stronger than that of (100), so that the films exhibited stronger c-axis orientation than a-axis orientation. On the other hand, in Examples in which film deposition was performed at a sputtering gas pressure of 0.67 Pa or greater, the intensity of (100) was much stronger than that of (002), so that the films exhibited stronger a-axis orientation than c-axis orientation.

(95) Note that it was confirmed that a wurtzite-type single phase was formed in the same manner even when the thin film thermistor portion (7) was deposited on a polyimide film under the same deposition condition. In addition, it was confirmed that the crystal orientation did not change even when the thin film thermistor portion (7) was deposited on a polyimide film under the same deposition condition.

(96) An exemplary XRD profile in Example exhibiting strong c-axis orientation is shown in FIG. 14. In this Example, Al/(Ti+Al) was equal to 0.84 (wurtzite-type, hexagonal), and measurement was performed at the angle of incidence of 1 degree. As can be seen from the result in this Example, the intensity of (002) was much stronger than that of (100).

(97) An exemplary XRD profile in Example exhibiting strong a-axis orientation is shown in FIG. 15. In this Example, Al/(Ti+Al) was equal to 0.83 (wurtzite-type, hexagonal), measurement was performed at the angle of incidence of 1 degree. As can be seen from the result in this Example, the intensity of (100) was much stronger than that of (002).

(98) Furthermore, in this Example, symmetrical reflective measurement was performed at the angle of incidence of 0 degrees. The asterisk (*) in the graph was a peak derived from the device, and thus, it was confirmed that the asterisk (*) in the graph is neither a peak derived from the sample itself nor a peak derived from the impurity phase (it can be seen from the fact that the peak indicated by (*) is lost in the symmetrical reflective measurement, and thus, it is a peak derived from the device).

(99) An exemplary XRD profile in Comparative Example is shown in FIG. 16. In this Comparative Example, Al/(Ti+Al) was equal to 0.6 (NaCl type, cubic), and measurement was performed at the angle of incidence of 1 degree. No peak which could be indexed as a wurtzite-type (space group P6.sub.3mc (No. 186)) was detected, and thus, this Comparative Example was confirmed as a NaCl-type single phase.

(100) Next, the correlation between a crystal structure and its electric properties was compared in detail with each other with regard to Examples of the present invention in which the wurtzite-type materials were employed.

(101) As shown in Table 2 and FIG. 17, there were materials (Examples 5, 7, 8, and 9) of which the crystal axis is strongly oriented along a c-axis in a vertical direction to the surface of the substrate and materials (Examples 19, 20, and 21) of which the crystal axis is strongly oriented along an a-axis in a vertical direction to the surface of the substrate despite the fact that they have substantially the same Al/(Ti+Al) ratio.

(102) When both groups were compared to each other, it was found that the materials having a strong c-axis orientation had a greater B constant by about 100 K than that of the materials having a strong a-axis orientation upon the same Al/(Ti+Al) ratio. When focus was placed on the amount of N (N/(Ti+Al+N)), it was found that the materials having a strong c-axis orientation had a slightly larger amount of nitrogen than that of the materials having a strong a-axis orientation. Since the ideal stoichiometric ratio of N/(Ti+Al+N) is 0.5, it was found that the materials having a strong c-axis orientation were ideal materials due to a small amount of nitrogen defects.

(103) TABLE-US-00002 TABLE 2 CRYSTAL AXIS EXHIBITING STRONG DEGREE OF ORIEN- TATION IN VERTICAL DIRECTION XRD PEAK TO INTENSITY SUBSTRATE RATIO OF SURFACE RESULT OF (100)/(002) WHEN ELECTRIC WHEN CRYSTAL SPUT- PROPERTIES CRYSTAL PHASE IS TERING SPECIFIC PHASE IS WURTZITE GAS COMPOSITION RATIO B RESISTANCE WURTZITE TYPE PHASE PRES- Al/ CON- VALUE CRYSTAL TYPE (a-AXIS OR SURE (Ti + Al) STANT AT 25° C. SYSTEM PHASE c-AXIS) (Pa) Ti (%) Al (%) N (%) (%) (K) (Ω cm) EXAMPLE 5 WURTZITE 0.34 c-AXIS <0.67 9 43 48 83 2727 2.E+04 TYPE EXAMPLE 7 WURTZITE 0.09 c-AXIS <0.67 8 44 48 84 2665 3.E+03 TYPE EXAMPLE 8 WURTZITE 0.05 c-AXIS <0.67 8 44 48 85 2527 1.E+03 TYPE EXAMPLE 9 WURTZITE <0.01 c-AXIS <0.67 8 45 47 86 2557 8.E+02 TYPE EXAMPLE 19 WURTZITE 2.50 a-AXIS ≧0.67 9 44 47 83 2571 5.E+03 TYPE EXAMPLE 20 WURTZITE 9.09 a-AXIS ≧0.67 8 46 46 84 2501 6.E+03 TYPE EXAMPLE 21 WURTZITE 6.67 a-AXIS ≧0.67 8 45 47 84 2408 7.E+03 TYPE
<Crystal Form Evaluation>

(104) Next, as an exemplary crystal form in the cross-section of the thin film thermistor portion (7), a cross-sectional SEM photograph of the thin film thermistor portion (7) in Example (Al/(Ti+Al)=0.84, wurtzite-type, hexagonal, and strong c-axis orientation) in which the thin film thermistor portion (7) was deposited on the Si substrate S with a thermal oxidation film is shown in FIG. 18. Also, a cross-sectional SEM photograph of the thin film thermistor portion (7) in another Example (Al/(Ti+Al)=0.83, wurtzite-type, hexagonal, and strong a-axis orientation) is shown in FIG. 19.

(105) The samples in these Examples were obtained by breaking the Si substrates S by cleaving them. The photographs were taken by tilt observation at the angle of 45 degrees.

(106) As can be seen from these photographs, samples were formed of a high-density columnar crystal in both Examples. Specifically, the growth of columnar crystal in a direction perpendicular to the surface of the substrate was observed in Example revealing a strong c-axis orientation and another Example revealing a strong a-axis orientation. Note that the break of the columnar crystal was generated upon breaking the Si substrate S by cleaving it.

(107) <Film Heat Resistance Test Evaluation>

(108) In Examples and Comparative Example shown in Table 1, a resistance value and a B constant before and after the heat resistance test at a temperature of 125° C. for 1000 hours in air were evaluated. The results are shown in Table 3. Comparative Example made by a conventional Ta—Al—N-based material was also evaluated in the same manner for comparison.

(109) As can be seen from these results, although the Al concentration and the nitrogen concentration vary, the heat resistance of the Ti—Al—N-based material based on the electric properties change before and after the heat resistance test is better than the Ta—Al—N-based material in Comparative Example when comparison is made by using the same B constant. Note that the materials used in Examples 5 and 8 have a strong c-axis orientation and the materials used in Examples 21 and 24 have a strong a-axis orientation. When both groups were compared to each other, the heat resistance of Examples revealing a strong c-axis orientation is slightly improved as compared with that of Examples revealing a strong a-axis orientation.

(110) Note that, in the Ta—Al—N-based material, ionic radius of Ta is very large compared to that of Ti and Al, and thus, a wurtzite-type phase cannot be produced in the high-concentration Al region. It is contemplated that the Ti—Al—N-based material having the wurtzite-type phase has better heat resistance than the Ta—Al—N-based material because the Ta—Al—N-based material is not the wurtzite-type phase.

(111) TABLE-US-00003 TABLE 3 RISING RATE OF SPECIFIC RESISTANCE RISING RATE OF SPECIFIC AT 25° C. AFTER CONSTANT B AFTER RESISTANCE HEAT RESISTANCE HEAT RESISTANCE VALUE TEST AT 125° C. TEST AT 125° C. M Al/(M + Al) B25-50 AT 25° C. FOR 1,000 HOURS FOR 1,000 HOURS ELEMENT M (%) Al (%) N (%) (%) (K) (Ω cm) (%) (%) COMPARATIVE Ta 60 1 39 2 2671 5.E+02 25 16 EXAMPLE EXAMPLE 5 Ti 9 43 48 83 2727 2.E+04 <4 <1 EXAMPLE 8 Ti 8 44 48 85 2527 1.E+03 <4 <1 EXAMPLE 21 Ti 8 45 47 84 2408 7.E+03 <5 <1 EXAMPLE 24 Ti 6 51 43 89 2599 7.E+04 <5 <1

(112) The technical scope of the present invention is not limited to the aforementioned embodiments and Examples, but the present invention may be modified in various ways without departing from the scope or teaching of the present invention.

REFERENCE NUMERALS

(113) 1, 21, and 31: temperature sensor, 2: lead frame, 3, 23, and 33: sensor portion, 6: insulating film, 7: thin film thermistor portion, 8: interdigitated electrode, 8a: comb portion, 9, 29, and 39: pattern electrode, 10: protective film, 11: protective sheet