JP2007243173A - Laminate, thin film sensor, and thin film sensor module - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate suitable for a thin film sensor because of its high sensitivity and its temperature-sensitive resistor that is hard to be peeled off; a thin film sensor (for example, a temperature sensor) consisting of the laminate; and a thin film sensor module (for example, a temperature sensor module) comprising the thin film sensor. <P>SOLUTION: A laminate comprises: an insulating substrate; a silicon compound layer that is formed on the insulating substrate and is made of a compound consisting of silicon and an element selected from the group consisting of carbon, nitrogen, fluorine, and oxygen; an adhesion layer that is formed on the silicon compound layer and is made of a material consisting primarily of a transition metal; and a temperature-sensitive resistor that is formed on the adhesion layer and is made of metal crystals consisting primarily of a platinum group element. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a laminate, a thin film sensor (for example, a temperature sensor) comprising the laminate, and a thin film sensor module (for example, a temperature sensor module) having the thin film sensor.

  Conventionally, as a thin film sensor module that is used to demonstrate the temperature sensor function of measuring the temperature of various objects or fluids, a thin film sensor module that uses a temperature sensitive resistor that detects the temperature by converting the amount of heat into an electrical signal is used. Widely used. Among them, thin film sensor modules (temperature sensor modules) using platinum group elements with a large absolute value of resistance temperature coefficient in terms of sensitivity are widely used, but the current situation is that higher sensitivity is required. It is.

  In general, it is known that the temperature coefficient of resistance of a resistor is affected by the presence form of crystals constituting the resistor (Non-Patent Document 1). For example, Non-Patent Document 2 discloses a technique for increasing the sensitivity by increasing the grain size of a crystal constituting a resistor.

  As a method of enlarging the grain size of the crystal constituting the temperature-sensitive resistor, first, a temperature-sensitive resistor material such as platinum is deposited on the substrate by forming a pattern by a lamination technique such as plating or vapor deposition, Examples thereof include a method of producing a crystal having a large particle size by, for example, growing a crystal by heat treatment at about several hundred to 1,000 ° C.

  However, when such a method is used, a large amount of heat is required to grow the crystal. In addition, accompanying this, a facility capable of withstanding this amount of heat is required, which is disadvantageous in terms of cost. Furthermore, the present situation is that improvement is also required in terms of the sensitivity of the temperature sensor.

  Japanese Patent Application Laid-Open No. 11-354302 (Patent Document 1) describes a layer (for example) a titanium layer for improving the adhesion between a platinum thin film and a substrate during the production of a platinum thin film resistor. Is described.

  Furthermore, JP 2001-291607 A (Patent Document 2) discloses an improvement in the adhesion of a platinum thin film to a substrate by interposing a titanium layer between the platinum thin film and the substrate in a method for producing a platinum thin film resistor. It is described that the resistance temperature coefficient of the platinum thin film can be sufficiently improved by high-temperature annealing by mixing oxygen in the sputtering gas for forming the platinum thin film or the titanium layer. .

However, there is room for further improvement in the adhesion between the platinum thin film and the substrate.
JP 11-354302 A JP 2001-291607 A “Structure and Physical Properties of Thin Films / Fine Particles”, Maruzen, pp. 139-156 (1974) “Development of high TCR platinum thin film”, IEEE Trans. SM. , 124, 7, 242-247 (2004)

The present invention has been made in view of the above-mentioned problems, and has a high sensitivity and is difficult to peel off a temperature-sensitive resistor, and is suitable as a thin film sensor, and a thin film sensor (for example, a temperature sensor) made of the multilayer material. Sensor) and a thin film sensor module (for example, a temperature sensor module) having the thin film sensor.

  The present invention also provides a thin film sensor (for example, a temperature sensor) that achieves high sensitivity without using a technique for enlarging crystal grains, and a thin film sensor module (for example, a temperature sensor module) having the thin film sensor. This is a further purpose.

The laminate of the present invention is
An insulating substrate;
A silicon compound layer made of a compound of silicon and an element selected from the group consisting of carbon, nitrogen, fluorine and oxygen, laminated on the insulating substrate;
An adhesion layer made of a material mainly composed of a transition metal, laminated on the silicon compound layer;
And a temperature-sensitive resistor made of a metal crystal composed mainly of a platinum group element, which is laminated on the adhesion layer.

It is preferable that the ratio of the (111) plane of the crystal oriented within 10 ° with respect to the surface perpendicular direction (ND direction) of the layer of the temperature sensitive resistor is 90% or more.
It is preferable that the crystal has a fibrous oriented structure, and in the fibrous oriented structure, the (111) plane of the crystal has a rotational axis in the direction perpendicular to the surface of the layer of the temperature sensitive resistor.

The crystal grain size is preferably 0.2 μm or more.
The platinum group element is preferably platinum.
The thin film sensor of this invention consists of the said laminated body.

  Examples of the thin film sensor include a sensor selected from the group consisting of a temperature sensor, a flow rate sensor, a specific heat sensor, a thermal conductivity sensor, a concentration sensor, a liquid type identification sensor, a strain sensor, a stress sensor, and a humidity sensor.

The temperature sensor of the present invention comprises the thin film sensor.
The thin film sensor module of the present invention includes the thin film sensor.
The temperature sensor module of the present invention includes the temperature sensor.

  ADVANTAGE OF THE INVENTION According to this invention, it is highly sensitive and a temperature sensitive resistor does not peel easily, The laminated body suitable as a thin film sensor, the thin film sensor which consists of this laminated body, and the thin film sensor module which has this thin film sensor are provided.

  According to one embodiment of the present invention, the sensitivity of the thin film sensor is increased by controlling the orientation of the crystals constituting the temperature sensitive resistor.

<Laminated body and thin film sensor>
FIG. 1 is a schematic view of a laminate or a thin film sensor (for example, a temperature sensor) (thin film chip) of the present invention. The laminate of the present invention and the thin film sensor 10 made of the laminate include an insulating substrate 11, a silicon compound layer 12 laminated on the insulating substrate 11, and an adhesion layer 13 laminated on the silicon compound layer 12. And a temperature sensitive resistor 14 laminated on the adhesion layer 13.

In the present invention, the direction from the insulating substrate toward the temperature sensitive resistor may be referred to as “upper” for convenience.
The material of the insulating substrate 11 is not particularly limited as long as it is an insulating material, and examples thereof include silicon and alumina. The shape of the insulating substrate 11 can be various shapes. For example, the insulating substrate 11 may have a rectangular shape as shown in FIG. 1, an elliptical shape, or a circular shape. The film thickness of the insulating substrate 11 may be about 300 to 1,000 μm.

  The material of the temperature sensitive resistor 14 is not particularly limited as long as it has a large temperature coefficient of resistance and is thermally stable, and is at least one of platinum group elements (ruthenium, rhodium, palladium, osmium, iridium, platinum). A metal or an alloy mainly containing more than one kind of element is used. In particular, platinum is preferable from the viewpoints of film formation, stability of characteristics, and cost. The temperature sensitive resistor 14 may be formed into a desired film thickness or a desired pattern using such a material. For example, the film thickness may be about 0.1 to 1 μm.

  The laminated body and thin film sensor (for example, temperature sensor) of the present invention are in close contact between the insulating substrate 11 and the temperature sensitive resistor 14 for the purpose of further improving the adhesion between the insulating substrate and the temperature sensitive resistor. It has a layer 13.

The material of the adhesion layer 13 may be variously selected within the range and the material that does not affect the temperature-resistance characteristics of the insulating substrate 11, and examples thereof include a material mainly composed of a transition metal. May contain a metal other than a transition metal as a metal. Specific examples of the material mainly composed of this transition metal include titanium (Ti), chromium (Cr), TiO ₂ ,
TiBaO and the like can be mentioned, among which titanium and chromium are preferable from the viewpoint of adhesion. In the material mainly composed of transition metal, transition metal is usually contained in an amount of 10 to 100% by weight, preferably 60 to 100% by weight. The thickness of the adhesion layer is, for example, preferably 0.002 to 0.1 μm, and more preferably 0.005 to 0.05 μm.

The laminated body and thin film sensor (for example, temperature sensor) of the present invention have a silicon compound layer 12 between the insulating substrate 11 and the adhesive layer 13 for the purpose of further improving the adhesion between the insulating substrate and the adhesive layer. Have. The silicon compound layer 12 is made of a compound of silicon and an element selected from the group consisting of carbon, nitrogen, fluorine and oxygen. Examples of such a compound include SiO ₂ , SiN, SiON, SiC, SiOC, and SiOF. Of these, SiO ₂ is preferable from the viewpoint of film formation.

The thickness of the silicon compound layer 12 is preferably 50 to 5,000 nm, more preferably 100 to 1,000 nm.
Since the temperature sensitive resistor 14 is laminated on the insulating substrate 11 via the adhesion layer 13 and further the silicon compound layer 12, the temperature sensitive resistor 14 is firmly adhered to the insulating substrate 11 and hardly peeled off.

  The laminated body and thin film sensor (for example, temperature sensor) of the present invention may be provided with a protective film 16 for the purpose of preventing physical damage. The material of the protective film 16 is not particularly limited as long as it can achieve this purpose, and examples thereof include resin and glass. Further, the thickness of the protective film 16 may be about 1 μm.

  The laminate and thin film sensor (eg, temperature sensor) of the present invention may have a bonding pad 18 that is electrically connected. The material of the bonding pad 18 is not particularly limited as long as it has good conductivity, and examples thereof include gold (Au) and platinum. Further, the bonding pad 18 may have various shapes depending on an applied form, for example, a shape of about 0.2 × 0.15 mm in length and width and about 0.1 μm in thickness.

The resistance temperature coefficient of the thin film sensor of the present invention is preferably 3,000 ppm / K or more, more preferably 3,300 ppm / K or more, and the upper limit is about 3,900 ppm / K.

  In addition, the thin film sensor of this invention can be used for the apparatus which measures the parameter | index which influences resistance values, such as not only a temperature sensor but flow volume. More specifically, the thin film sensor of the present invention having the thin film sensor can be used in an apparatus for measuring an index that affects the resistance value of the temperature sensitive resistor. , Flow rate sensor, specific heat sensor, thermal conductivity sensor, concentration sensor, liquid type identification sensor, strain sensor, stress sensor, humidity sensor and the like.

<Manufacturing method of laminated body and thin film sensor (for example, temperature sensor)>
The manufacturing method of the laminated body and thin film sensor (for example, temperature sensor) of this invention is demonstrated.

In the production of the laminate and the thin film sensor (for example, temperature sensor) of the present invention, first, a silicon compound layer is laminated on one surface of the above-described insulating substrate.
The silicon compound layer can be formed by means such as a sol-gel method, a spin coating method, a CVD method, or a sputtering method. Specifically, for example, it can be produced under the following conditions.

Lamination means: Spin coating method Equipment: Spin coater Raw material: Coating type SiO ₂ film forming material (SOG)
Rotation speed: 1,000-6,000 rpm
Temperature: 450-1,000 ° C.

  Next, an adhesion layer is formed on the surface of the silicon compound layer (the surface opposite to the insulating substrate side). The adhesion layer may be laminated using various vapor deposition means such as sputtering. The deposition conditions are not particularly limited as long as the adhesion is ensured and the resistance temperature characteristics of the temperature sensitive resistor are not adversely affected. If a titanium (Ti) layer is formed as the adhesion layer, for example, vapor deposition can be performed under the following conditions.

Vapor deposition means: Sputtering method Apparatus: Magnetron sputtering apparatus Ultimate vacuum: 6.0 × 10 ⁻⁵ Pa or less Film forming pressure: 0.1 to 2 Pa
Gas flow rate: 10-180 SCCM
Deposition power: 400-1400W.

Next, a temperature-sensitive resistor is laminated on the surface of the adhesion layer (surface opposite to the silicon compound layer side) by vapor deposition means such as sputtering.
Conditions such as the degree of vacuum and pressure at the time of sputtering are not particularly limited, but when an adhesion layer is used, after the adhesion layer is formed, a resistor is continuously formed without touching air, oxygen, moisture, or the like. There is a need to. During sputtering, an oxygen gas may be mixed with an inert gas such as argon as an introduction gas. The amount of oxygen mixed with the inert gas can be, for example, in the range of 0.5 to 30% by volume in the standard state, and preferably in the range of 2 to 20% by volume. If it is less than 0.5% by volume, a part of the metal atoms constituting the adhesion layer diffuses into the temperature sensitive resistor, and its resistance temperature coefficient (TCR) is lowered. When it is 30% by volume or more, oxygen is dissolved in the crystal constituting the temperature-sensitive resistor, and thus its TCR is lowered.

If a platinum thin film is formed as the temperature sensitive resistor, for example, vapor deposition can be performed under the following conditions.
Vapor deposition means: Sputtering method Apparatus: Magnetron sputtering apparatus Ultimate vacuum: 6.0 × 10 ⁻⁵ Pa or less Film forming pressure: 0.1 to 0.8 Pa
Gas flow rate: 10-180 SCCM
Deposition power: 400-1400W
Deposition temperature: room temperature to 250 ° C.

  Next, annealing is performed within a range of 900 ° C. to 1100 ° C., for example, with respect to the obtained laminate (that is, a laminate including an insulating base material, a silicon compound layer, an adhesion layer, and a temperature-sensitive resistor). A thin film sensor (for example, a temperature sensor) is obtained.

  If the annealing temperature is lower than 900 ° C., the resistance temperature coefficient of the thin film sensor (eg, temperature sensor) tends to decrease. Moreover, when it exceeds 1100 degreeC, it exists in the tendency for the surface state of a thin film sensor (for example, temperature sensor) to deteriorate. The annealing time can be, for example, 4 hours or longer. When the annealing time is less than 4 hours, that is, too short, the rate of change with time of the resistance value of the temperature-sensitive resistor tends to increase.

  The temperature sensitive resistor may be formed into various patterns by means such as etching. For example, the temperature sensitive resistor may be processed into a meandering pattern shape having a width of, for example, 5 to 25 μm and a total length of, for example, 4 to 23 cm by an etching method or the like.

<Presence form of crystal of temperature-sensitive resistor in the present invention>
In the thin film sensor (for example, temperature sensor) of the present invention, the crystals constituting the temperature sensitive resistor exist in a form having a specific orientation. In the present invention, this orientation state is defined by “orientation” described below. In the present invention, “orientation” refers to a crystal (that is, a crystal constituting the temperature-sensitive resistor) that is oriented within 10 ° from the surface perpendicular direction (ND direction) of the layer of the temperature-sensitive resistor. 111) The ratio of the surface. In the thin film sensor (for example, temperature sensor) of the present invention, this ratio is preferably 90% or more. The “orientation” value is a value obtained by the method described in the column of Examples described later.

  In general, it is known that the crystalline state of the temperature-sensitive resistor affects the change in resistance value accompanying the temperature rise in the temperature-sensitive resistor. It is known that the gradient of the resistance temperature coefficient increases as the crystal state, particularly the crystal grain size increases, and the increase in the grain size is a technique for increasing the sensitivity of a thin film sensor (for example, a temperature sensor). It is widely used as one.

  On the other hand, in the present invention, attention is paid to the existence form of crystals constituting the temperature sensitive resistor. That is, the present inventors have found that the temperature coefficient of resistance of the temperature-sensitive resistor is improved by controlling the crystal form, particularly the crystal orientation. Although the mechanism for improving the temperature coefficient of resistance by controlling the orientation as in the present invention is not clear, it is considered that the electrical characteristics of the crystal can be improved by aligning the crystal orientation in a specific direction.

Examples of the orientation control method include film formation on a single crystal substrate and promotion of grain growth by heat treatment.
Further, the crystal constituting the temperature sensitive resistor has a fibrous oriented structure, and in the fibrous oriented structure, the (111) plane of the crystal is set with the plane perpendicular to the layer of the temperature sensitive resistor as the rotation axis. Preferably it is. By having such a structure, the electrical characteristics are further improved. In addition, what is necessary is just to observe for the observation of this fibrous orientation structure | tissue using the various methods used for structure | tissue observation, for example, you may observe using the following EBSP evaluation apparatus.

  In the present invention, the crystal orientation was evaluated using the EBSD (Backscattered Electron Diffraction Pattern) method. An X-ray diffractometer (XRD) is generally used to evaluate the crystal structure of inorganic materials, but this device can only obtain average information of the entire crystal structure, It is not possible to evaluate the existence form of the individual crystal grains constituting. On the other hand, in order to evaluate the orientation of individual crystal grains, a transmission electron microscope (TEM) is generally used. However, statistical evaluation of crystal grains included in a crystal structure is performed. Really impossible.

On the other hand, if an EBSD evaluation apparatus is used, it is possible to quickly evaluate the existence form of individual crystal grains, and it is possible to evaluate crystal grain size, grain size distribution, crystal orientation, strain calculation, and the like.
The grain size of the crystals constituting the temperature sensitive resistor is preferably 0.2 μm or more, more preferably 0.4 μm or more, and the upper limit is not particularly limited, but is usually about 5.0 μm. In addition, the value of this “crystal grain size” is a value obtained by the method described in the column of Examples described later.

<Thin film sensor module>
Next, the thin film sensor module (for example, temperature sensor module) of this invention is demonstrated. The temperature sensor module of the present invention includes a member that is thermally connected to an object or fluid to be measured, the above-described temperature sensor that is thermally connected to the member, and an electrical connection to the temperature sensor. Member. This configuration is illustrated in FIGS.

  FIG. 2 is a schematic view illustrating a thin film sensor module (for example, a temperature sensor module) of the present invention, and FIG. 3 is a schematic cross-sectional view illustrating a thin film sensor module (for example, a temperature sensor module) of the present invention. (A) is a plan longitudinal sectional view, and (b) is a lateral longitudinal sectional view. The thin film sensor module (for example, temperature sensor module) 20 of the present invention has a thin film sensor (for example, temperature sensor) 10 in which a fin plate 24 and an output terminal 26 are fixed inside a housing 22.

  Various materials can be used as the material of the housing 22 as long as the material has low thermal conductivity. In addition, materials imparted with chemical resistance and oil resistance can be used according to the object or fluid to be measured. Examples having these characteristics include epoxy resin, polybutylene terephthalate (PBT), polyphenylene sulfide (PPS), and the like. Further, the shape of the thin film sensor module (for example, the temperature sensor module) may be various forms depending on the mode of application of the thin film sensor module (for example, the temperature sensor module). For example, as shown in FIGS. 2 and 3B, the housing 22 includes a first large diameter portion 34 from which the output terminal 26 protrudes, and a second large position located below the first large diameter portion 34 with a space therebetween. It may have a diameter portion 36, and a notch portion 38 for forming a heat insulating space may be provided between the first large diameter portion 34 and the second large diameter portion 36. The housing 22 is not limited to this form.

  The fin plate 24 is not particularly limited as long as it is made of a material having good thermal conductivity, and is made of, for example, copper, aluminum, tungsten, duralumin, a copper-tungsten alloy, or the like. Further, the fin plate 24 may have various shapes as appropriate according to the application of a thin film sensor module (for example, a temperature sensor module), and may be a thin plate having a thickness of about 200 μm, for example. In addition, as a material for adhering the fin plate 24 and the thin film sensor (for example, the temperature sensor) 10, any material can be used as long as it has a thermal conductivity, for example, a silver paste.

  The output terminal 26 is not particularly limited as long as it is made of a conductive material, and examples of this material include copper and aluminum. The output terminal 26 is electrically connected to the thin film sensor (for example, temperature sensor) 10 through the bonding wire 32. In FIG. 2, the shape of the output terminal 26 protrudes from the resin housing 2 in such a manner that it is juxtaposed in a straight line on the outside of the resin housing 2 and extends from one end to the other end of the straight line. Although the length is shown as gradually increasing (gradually decreasing), it may be formed into various shapes depending on the form to be applied. 2, the sensor pressing plate that presses the thin film sensor module (for example, the temperature sensor module) 20 from above, and the mounting of the flow rate detection circuit board that is connected to the output terminal 26 to form a circuit, It can be done easily. Further, the risk of damaging the thin film sensor module (for example, the temperature sensor module) 20 is reduced when the sensor pressing plate and the flow rate detection circuit board are mounted.

[Example]
(Example a1)
A 300 nm-thick SiO ₂ layer was formed on an alumina substrate (size: disk with a diameter of 100 mm, thickness: 385 μm) by the spin coating method under the following conditions.

Equipment: Spin coater Ingredients: Coating type SiO ₂ film forming material
(Manufactured by Tokyo Ohka Kogyo Co., Ltd., raw material: OCD (trade name), siloxane-based material)
Rotational speed: 1,000 rpm x 5 s → 5,000 rpm x 30 s
Temperature: 695 ° C.

Next, sputtering was performed on the SiO ₂ layer thus formed using metal titanium (purity: 99.99%) as a target under the following conditions to form a titanium layer having a thickness of 30 nm.

Apparatus: Magnetron sputtering apparatus Ultimate vacuum: less than 6.0 × 10 ⁻⁵ Pa Deposition pressure: 0.86 Pa
Gas flow rate: 180 SCCM [Ar: O ₂ = 10: 0 (volume ratio in the standard state)]
Deposition power: 1,000 W (DC)
Deposition temperature: 250 ° C.

  Next, sputtering was performed on the titanium layer thus formed using platinum (purity 99.9%) as a target under the following conditions to form a 400 nm-thick temperature sensitive resistor.

Apparatus: Magnetron sputtering apparatus Ultimate vacuum: less than 6.0 × 10 ⁻⁵ Pa Deposition pressure: 0.18 Pa
Gas flow rate: 10 SCCM [Ar: O ₂ = 9: 1 (volume ratio in standard state)]
Deposition power: 500W (RF)
Deposition temperature: 250 ° C.

The laminated body 1 thus produced was measured for the temperature coefficient of resistance (TCR), the crystal grain size, the orientation and the adhesion as described below. The results are shown in Table 1.
(Comparative Example a1)
A laminate 2 was produced in the same manner as in Example a1, except that the SiO ₂ layer was not formed.

(Example b1)
The laminated body 1 was heat-treated at 1,000 ° C. for 4 hours in an air atmosphere to obtain a temperature sensor 1. With respect to this temperature sensor 1, the following resistance temperature coefficient (TCR), crystal grain size, orientation, pole figure regarding (111) plane and adhesion were measured. The results are shown in Table 1.

(Example b2)
The laminated body 1 was heat-treated at 900 ° C. for 4 hours in an air atmosphere to obtain a temperature sensor 2. With respect to this temperature sensor 2, the following resistance temperature coefficient (TCR), crystal grain size, orientation and adhesion were measured. The results are shown in Table 1.

(Example b3)
The laminated body 1 was heat-treated at 1,000 ° C. for 4 hours under an argon atmosphere to obtain a temperature sensor 3. The temperature sensor 3 was measured for the temperature coefficient of resistance (TCR), the crystal grain size, the orientation, the pole figure relating to the (111) plane and the adhesion as described below. The results are shown in Table 1.

(Comparative Example b1)
The laminated body 2 was heat-treated at 800 ° C. for 4 hours in an air atmosphere to obtain a temperature sensor 4. The temperature sensor 4 was measured for the temperature coefficient of resistance (TCR), crystal grain size, orientation, and adhesion as described below. The results are shown in Table 1.

<Crystal grain size>
The longitudinal section of the target laminate and temperature sensor was polished and smoothed using a focused ion beam (FIB). About this smoothed longitudinal section, an FE gun type scanning electron microscope (JSM-6700F or JSM-7000F, manufactured by JEOL Ltd.) equipped with an EBSD evaluation apparatus (OIM Analysis, manufactured by TSL Solutions Co., Ltd.) and Using the attached EBSD analyzer, image data of a crystal state pattern was obtained according to the EBSD method. With respect to this image data, an analysis menu “Grain Size” of the EBSD analysis program (OIM Analysis, same as above) was selected, crystal grains having a crystal rotation angle of 5 ° or more were observed, and crystal grain size (μm) was calculated. The crystal grain size was calculated considering the Σ3 grain boundary indicating the twin grain boundary as an intragranular defect.

<Measurement of resistance temperature coefficient (TCR)>
About the laminated body and temperature sensor used as object, the resistance temperature coefficient TCR was measured from the measurement of specific electrical resistance ρ-T characteristic.

In the present invention, the temperature coefficient of resistance refers to a value represented by the following (Equation 1).
(Formula 1): α = (1 / R) × (dR / dT) × 10 ⁶
α: Temperature coefficient of resistance (ppm / ° C)
T: Any absolute temperature (K)
R: Zero load resistance value (Ω) at T (K).

<Orientation>
The longitudinal sections of the laminate and the temperature sensor manufactured as described above were smoothed using polishing and a focused ion beam (FIB). Using an FE gun type scanning electron microscope (JSM-6700F or JSM-7000F, manufactured by JEOL Ltd.) equipped with an EBSD evaluation device (OIM Analysis, manufactured by TSL Solutions, Inc.) and an attached EBSD analysis device, With respect to this smoothed longitudinal section, image data of a crystal state pattern was obtained according to the EBSD method. This image data is selected from the analysis menu “Crystal Direction” of the EBSD analysis program (OIM Analysis, same as above), the “ND direction” of the laminated body or the temperature sensor, and the (111) plane orientation of the platinum crystal of the temperature sensitive resistor. Analysis was performed under the condition of calculating the ratio of crystal grains with respect to all crystal grains within 10 degrees, and this ratio was defined as “orientation”. Note that a grain rotation angle of 5 ° or more was regarded as a crystal grain boundary, and an aggregate within 5 ° was recognized as one crystal grain.

<Pole figure about (111) plane>
Similarly to the above “orientation”, the (111) plane of the temperature sensitive resistor platinum crystal is selected by selecting the analysis menu “Pole figure” of the EBSP analysis program (OIM Analysis, same as above) and A pole figure was obtained.

<Adhesion>
About each of the laminated body and temperature sensor which were manufactured as mentioned above, the adhesiveness of an insulated substrate and a temperature sensitive resistor was evaluated with the following wire pull test methods.
* Wire Pull Test Method A gold wire (25 μmφ) was bonded (bonded) on a gold electrode pad (18) of a thin film chip (thin film sensor). Thereafter, the gold wire was pulled with a force of about 10 g in the vertical direction of the thin film chip at room temperature. The evaluation criteria are as follows.

AA: The gold electrode pad and the temperature sensitive resistor did not peel from the gold wire, and the gold wire was broken.
CC: The gold electrode pad and the temperature sensitive resistor were peeled from the gold wire.

1 is a schematic view of a thin film sensor (eg, temperature sensor) (thin film chip) according to the present invention. It is the schematic which illustrated the thin film sensor module (for example, temperature sensor module) by this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is the schematic sectional drawing which illustrated the thin film sensor module (for example, temperature sensor module) by this invention, Comprising: (a) is a plane longitudinal cross-sectional view, (b) is a side longitudinal cross-sectional view. The pole figure regarding the (111) plane in the temperature sensitive resistor of the laminated body 1 obtained in Example a1 is shown. The pole figure regarding the (111) plane in the temperature sensitive resistor of the temperature sensor 1 obtained in Example b1 is shown. The pole figure regarding the (111) plane in the temperature sensitive resistor of the temperature sensor 3 obtained in Example b3 is shown.

Explanation of symbols

10 Thin film sensor (thin film chip) (for example, temperature sensor)
DESCRIPTION OF SYMBOLS 11 Insulating substrate 12 Silicon compound layer 13 Adhesion layer 14 Temperature sensitive resistor 16 Protective film 18 Bonding pad 20 Thin film sensor module (for example, temperature sensor module)
22 Housing 24 Fin plate 26 Output terminal 32 Bonding wire 34 First large diameter portion 36 Second large diameter portion 38 Notch

Claims (10)

An insulating substrate;
A silicon compound layer made of a compound of silicon and an element selected from the group consisting of carbon, nitrogen, fluorine and oxygen, laminated on the insulating substrate;
An adhesion layer made of a material mainly composed of a transition metal, laminated on the silicon compound layer;
A laminate having a temperature-sensitive resistor made of a metal crystal containing a platinum group element as a main component and laminated on the adhesion layer.   The ratio of the (111) plane of the crystal that is oriented within 10 ° with respect to the surface perpendicular direction (ND direction) of the layer of the temperature sensitive resistor is 90% or more. The laminated body as described in.   2. The crystal according to claim 1, wherein the crystal has a fibrous orientation structure, and in the fibrous orientation structure, a (111) plane of the crystal has a rotational axis in a plane perpendicular to the layer of the temperature sensitive resistor. Or the laminated body of 2.   The laminate according to any one of claims 1 to 3, wherein the crystal has a grain size of 0.2 µm or more.   The laminate according to any one of claims 1 to 4, wherein the platinum group element is platinum.   A thin film sensor comprising the laminate according to any one of claims 1 to 5.   7. The sensor according to claim 6, wherein the sensor is selected from the group consisting of a temperature sensor, a flow rate sensor, a specific heat sensor, a thermal conductivity sensor, a concentration sensor, a liquid type identification sensor, a strain sensor, a stress sensor, and a humidity sensor. Thin film sensor.   A temperature sensor comprising the thin film sensor according to claim 6.   A thin film sensor module comprising the thin film sensor according to claim 6.   A temperature sensor module comprising the temperature sensor according to claim 8.

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