KR20110047145A

KR20110047145A - Material for a resistor, a sputtering target for forming resistance thin film, a resistance thin film, a thin film resistor, and manufacturing method thereof

Info

Publication number: KR20110047145A
Application number: KR1020100105202A
Authority: KR
Inventors: 사다유키 요코바야시; 마사히로 수기하라
Original assignee: 스미토모 긴조쿠 고잔 가부시키가이샤
Priority date: 2009-10-29
Filing date: 2010-10-27
Publication date: 2011-05-06

Abstract

PURPOSE: Resistor materials, a sputtering target for forming a resistance thin film, the resistive thin film, a thin film resistor with high corrosion resistance and manufacturing methods thereof are provided to reduce the manufacturing costs of the thin film resistor through a thermal process of a low temperature. CONSTITUTION: A thin film resistor includes an insulation material substrate(1), a resistive thin film(2), and an electrode(3). The resistive thin film is formed on the insulation material substrate. An electrode is formed on both sides of the resistive thin film on the insulation material substrate. The electrode is made of one of Au, Al, Ag, Cu, Ni, and Cr.

Description

Resistor material, sputtering target for forming a resistive thin film, resistive thin film, thin film resistor and a method for manufacturing the same {Material for a resistor, a sputtering target for forming resistance thin film, a resistance thin film, a thin film resistor, and manufacturing method

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin film resistor and a resistive thin film used to obtain the thin film resistor as an electronic component, a sputtering target for forming the resistive thin film, the sputtering target resistor material, and a manufacturing method thereof.

Thin film resistors using resistive thin films are used for electronic components such as chip resistors, precision resistors, network resistors, resistors such as high voltage resistors, temperature sensors such as RTDs, and thermocouples, and hybrid ICs and composite module products.

Thin film resistors include (1) resistance temperature characteristics where the absolute value of the resistance temperature coefficient (TCR) is close to zero, (2) high temperature stability at which the resistance change rate is low over time, and (3) human sweat or seawater. Four characteristics are required, such as corrosion resistance (saline resistance) and (4) high specific resistance.

Although miniaturization of thin film resistors is required with the miniaturization of electrical and electronic products, it is necessary to further increase the specific resistance of the resistor material constituting the resistive thin film while maintaining the above characteristics.

For thin film resistors, Ta alloys, TaN compounds, and Ni-Cr based alloys are mainly used as resistor materials that often form resistive thin films.

Among these, resistive thin films using Ni-Cr based alloys are commonly used in thin film resistors because they have Omiku characteristics, which are the characteristics of metals, have a small change in resistance value and high thermal stability with respect to changes in ambient temperature. have. However, Ni-Cr alloy has a problem that the specific resistance is low as a resistor material.

Therefore, a resistive thin film has been proposed to increase the specific resistance by adding Ta, Al, and Mo to a Ni-Cr alloy (see Patent Document 1). The resistive thin film according to the Ni-Cr based alloy to which Ta, Al, and Mo were added is superior to the resistive thin film using the Ni-Cr based alloy, but the corrosion test using an acidic artificial sweat solution (JIS L0848) is performed. In this regard, a resistive thin film having a melting start voltage of less than 6 V and more excellent in corrosion resistance is desired.

In addition, the Ni-Cr-based alloy is heat-treated in order to obtain a predetermined characteristic, but heat treatment is required at a high temperature of 500 ℃ or more in accordance with the required properties. Therefore, it is required to be able to lower such heat treatment temperature further.

Patent Document: Japanese Patent Publication No. 2008-10604

Therefore, the present invention maintains high resistivity, excellent resistance temperature characteristics, and high temperature stability, such as Ni-Cr-based alloys to which Ta, Al, and Mo are added even when the heat treatment of the resist thin film is performed at a relatively low temperature. It is an object of the present invention to provide a thin film resistor having corrosion resistance.

The resistor material of the present invention is a Ni alloy containing 10 to 60% by mass of at least one additional element selected from Cr, Al, and Y, the balance being made of Ni and an unavoidable impurity, and SiO ₂ (silica) mainly as a component. And 3 to 20% by mass of a silicate-based glass containing 0 to 90% by mass of at least one selected from B, Mg, Ca, Ba, Al, Zr and oxides thereof.

The sputtering target for forming a resistive thin film of the present invention comprises silicate-based glass powder containing SiO 2 as a main component, and 0 to 90% by mass of at least one selected from B, Mg, Ca, Ba, Al, Zr and oxides thereof; Ni alloy powder containing 10 to 60% by mass of at least one additional element selected from Cr, Al, and Y, and the balance of Ni and inevitable impurities to be 3 to 20% by mass of the silicate glass powder The molded product obtained by molding the mixed powder obtained in the desired shape is obtained by sintering at 500 to 1400 ° C. under pressure of 50 kg / cm 2 or higher in a vacuum or inert atmosphere.

The composition of this sputtering target is almost the same as that of the resistor material.

The resistive thin film of the present invention is obtained by heat-treating a thin film obtained by forming a thin film on an insulating material substrate by the sputtering method using the sputtering target at 200 to 500 ° C. in an air or an inert gas atmosphere for 1 to 10 hours. .

The composition of such a resistive thin film is also substantially the same as the resistive material constituting the sputtering target.

The resistive thin film of the present invention has a specific resistance of 300 to 1500 µΩ · cm and a resistance temperature coefficient of −25 to +25 ppm / ° C., resulting in a change in resistance over time due to the high temperature holding at 155 ° C. for 1000 hours. It becomes less than% and has the characteristic that the initiation voltage of dissolution according to the corrosion test using the acidic artificial sweat liquid (JIS L0848) is 9V or more.

The thin film resistor of the present invention comprises an insulating material substrate, a resistive thin film formed on the insulating material substrate, and an electrode formed on both sides of the resistive thin film on the insulating material substrate, wherein the electrical resistive thin film has the resistive thin film characteristics. It features.

Using the resistive thin film material of the present invention as a sputtering target A thin film resistor using a resistive thin film obtained by film formation by the sputtering method has a high specific resistance of 300 to 1500 µΩ · cm and an absolute value of the resistance temperature coefficient of ± 25 ppm / ° C. Excellent resistance temperature characteristics, high temperature stability with a change rate of resistance of 0.1% or less with 1000 hours of high temperature at 155 ° C, and furthermore, the initiation voltage of the corrosion test using acidic artificial sweat (JIS L0848) is 9V or more. It is possible to satisfy high corrosion resistance (salt water resistance) at the same time.

That is, according to the present invention, it is possible to use an electronic component having excellent high temperature stability at high resistance in an extreme environment requiring better corrosion resistance than before, and at the same time, the above characteristics can be obtained by heat treatment at a lower temperature than before. The present invention also contributes to reducing the manufacturing cost of the thin film resistor.

1 is a schematic diagram of a thin film resistor to which the present invention is applied.
2 is a diagram illustrating an outline of a corrosion test.

Thin film resistors require four characteristics: high resistance, stable resistance temperature characteristics, excellent high temperature stability, and high corrosion resistance (salt water resistance), and various attempts have been made to improve the Ni-Cr based alloys.

Among Ni-Cr alloys, Ni-Cr alloys having Ta, Al, and Mo added thereto have been tried to improve resistance and corrosion resistance while maintaining resistance temperature characteristics and high temperature stability as compared with the conventional one. However, as mentioned above, in order to obtain such characteristics, in particular, to make the resistance temperature coefficient within a predetermined range, the thin film deposited using the resistor material is subjected to heat treatment for 1 to 10 hours at a temperature of 200 to 600 ° C. It is necessary to carry out, and according to a desired characteristic, heat processing is required at the temperature which becomes high temperature, and the resistor material which enables heat processing at lower temperature is desired, maintaining or improving said characteristic.

As a result of intensive studies, the present inventors have conducted a heat treatment temperature for obtaining desired characteristics by adding only a predetermined amount of silicate-based glass to a Ni alloy, which is not used as a resistor material used in a thin film resistor of a conventional electronic component. The present invention was completed by recognizing that it is possible to relatively reduce and to improve the above characteristics, particularly corrosion resistance.

The resistive material of the present invention contains 10 to 60% by mass of at least one additional element selected from Cr, Al, and Y, and the balance of Ni and inevitable impurities is SiO ₂ (silica) as a main component. And 3 to 20% by mass of a silicate-based glass containing 0 to 90% by mass of at least one selected from B, Mg, Ca, Ba, Al, Zr and oxides thereof.

In addition, such a resistor material is characterized by the above-mentioned composition, and as long as it has substantially the same composition, it is not limited to the form. Therefore, the terminology of the resistor material is a general term for all forms from the raw material to the resistive thin film in the process of forming the resistive thin film.

It is Ni alloy which comprises the resistor material of this invention as a basis. Such Ni alloy contains 10-60 mass% of 1 or more additive elements selected from Cr, Al, and Y, and remainder consists of Ni and an unavoidable impurity.

The added elements have respective effects, Cr contributes to the reduction of the absolute value of the resistance temperature coefficient, Al improves the corrosion resistance, and Y contributes to the improvement of adhesion between the Ni alloy and the glass powder. Although such an additional element is added only a necessary amount according to the required characteristic, in order to have the characteristic in the thin film resistor of this invention, it is preferable to contain all the additional element. In order to exhibit each characteristic, Cr must contain 10 mass% or more, Al 10 mass% or more, Y must contain 0.3 mass% or more, and it is necessary to be 10 mass% or more in total. When the addition amount of the additional element is less than 10% by mass in total, the specific resistance of the obtained resistive thin film does not become large enough. On the other hand, when such an additional element becomes excessive, since the stability after film-forming and heating will worsen, and reproducibility will worsen, it is necessary to be 60 mass% or less in total amount. Preferably, the total amount of the additional elements is in the range of 40 to 50 mass% in terms of decreasing the absolute value of the resistance temperature coefficient. Although the resistance temperature coefficient changes the composition of glass mentioned later, the composition of Ni alloy also changes. In view of this point, the total amount of the additional elements to the Ni alloy is preferably 40 to 50% by mass.

The resistor material of the present invention is a silicate system containing 0 to 90% by mass of at least one selected from B, Mg, Ca, Ba, Al, Zr, and oxides thereof, based on such Ni alloy and SiO ₂ (silica). It is characteristic that 3-20 mass% of glass is added.

The silicate-based glass mainly has an effect of increasing the resistance value of the resistive thin film. It also has the effect of improving the corrosion resistance of the resistive thin film. Moreover, in order to obtain a desired characteristic by containing a silicate type glass, the heat processing temperature with respect to the thin film after film formation can be relatively reduced.

Since the silicate-based glass is an insulator, the effect can be obtained even by adding a small amount of 3% by mass or more. On the contrary, when the added amount exceeds 20% by mass, the insulation is insulated, so that film formation by DC sputtering cannot be performed, which causes problems in terms of cost. In addition, the addition amount of the silicate-based glass is preferably in the range of 5 to 10% by mass.

The silicate-based glass contains, as an additive, one or more selected from B, Mg, Ca, Ba, Al, Zr, and oxides thereof. However, the content of such additives is 90 mass% or less. When the content of such additives exceeds 90% by mass, the absolute value of the resistance temperature coefficient cannot be in the range of ± 25 ppm / ° C.

By adding such B, Mg, Ca, Ba, Al, Zr or these oxides, fine adjustment of the fusion temperature and water resistance of a resistive thin film can be performed. Further, the case where the phase separation of the thin film resistance caused by the addition of Al or alumina (Al ₂ O ₃₎ is suppressed. However, the present invention is not affected by these additives, but the above merely illustrates additives that can be contained in the silicate glass, and silicate glass which does not contain any of these additives can also be applied to the present invention. . In addition, when adding such an additive from the viewpoint of the crystallinity of a silicate glass, it is preferable that all of B, Mg, Ca, Ba, Al, Zr is contained. In addition, it is preferable to make the total amount into the range of 30-70 mass% including the case where these are oxides for the same reason.

As needed, after performing sintering in the hot press mentioned later, it may be desirable to adjust such additives and addition amount so that a silicate-type glass may not crystallize. This is because when the silicate glass is crystallized, the density of the resistor material does not increase, the strength decreases, and it may interfere with the film formation by sputtering.

Next, preparation of the sputtering target for forming a resistance thin film of this invention is demonstrated. The raw material of such a sputtering target is a silicate-based glass powder in which 0 to 90 mass% of one or more selected from B, Mg, Ca, Ba, Al, Zr, and oxides thereof are added, mainly with SiO ₂ , and Cr, Al And Ni alloy powder containing 30 to 60 mass% (preferably 40 to 50 mass%) of at least one additional element selected from Y, the balance being made of Ni and an unavoidable impurity.

As Ni alloy powder which becomes a raw material powder, an average particle diameter exists in the range of 10-200 micrometers, Preferably it is 30-150 micrometers, More preferably, it is about 100 micrometers, It is preferable to use spherical atomized powder. In addition, the silicate-based glass powder has an average particle diameter of 0.5 to 50 µm, preferably 1 to 30 µm, more preferably about 10 µm, and it is preferable to use a powder.

The raw material powder is sintered, and in general, the particle size of the raw material powder is preferably fine. However, there is no limitation in the case of sintering by hot press. When hot pressing is carried out, the raw powder is filled in carbon form, and since there is a gap in the carbon form, when the raw powder is minute, raw powder may leak from the gap and workability may be deteriorated.

On the other hand, when the average particle diameter of Ni alloy powder exceeds 200 micrometers or the average particle diameter of a silicate-type glass powder exceeds 50 micrometers, the problem of the density of a target will fall.

Such a raw material is dry mixed so that the silicate-based glass powder is 3 to 20% by mass (preferably 5 to 10% by mass), a mixed powder is obtained from the raw material powder, and a molded product obtained by molding the obtained mixed powder into a desired shape, Preferably, the said sputtering target can be obtained by sintering by a hot press method. As specific sintering conditions, it is preferable to sinter by baking for 1 to 5 hours at 500-1400 degreeC under pressure of 50 kg / cm <2> or more in a vacuum or inert atmosphere. In addition, the hot press method in this specification also includes the HIP (hot hydrostatic press) method. When less than 50 kg / cm <2> and baking time is less than 1 hour, a high density target is not obtained. On the other hand, even if the hot press for more than 5 hours is executed, the effect of improving the density cannot be obtained.

The sintering temperature is preferably higher than the softening point of the glass powder and lower than the melting point of the Ni alloy. The sintered compact thus obtained can be prepared in size, bonded, and the like, to obtain a sputtering target.

Next, the production of the resistive thin film of the present invention will be described. When the film is formed by the sputtering method using the sputtering target obtained as described above, a thin film having a composition substantially the same as that of the resistor material can be obtained. In this case the substrate, the insulating substrate such as Al ₂ O _3, SiO ₂ is preferable. In addition to the sputtering method, it is also possible to process the resistor material of the present invention into a deposition tablet and to form a resistive thin film by a vapor deposition method such as vacuum deposition.

Although there is no restriction | limiting according to the kind about sputtering method, It is preferable to use DC sputtering from a cost point and mass productivity viewpoint. Sputtering conditions vary depending on the sputtering device, but, for example, when using a sputtering target with a target size of φ75 mm × 3 mm and output: 200 W (fixed), voltage: 400 to 600 V, current: 0.3 to 0.5 A, Ar flow rate: 15 ~ 25SCCM, voltage force: 0.4 ~ 0.6Pa, TS distance (target-to-substrate distance): 85mm.

Only the thin film which sputtered film formation performed has a negative resistance temperature coefficient, and its resistance stability at high temperature is inadequate. Therefore, it is necessary to heat-process for 1 to 10 hours at 200-500 degreeC in air | atmosphere or inert gas according to the composition of a thin film after film-forming. By such heat treatment, a resistive thin film having an absolute value of the resistive temperature coefficient of less than ± 25 ppm / 占 폚 can be obtained.

If the temperature of the heat treatment is less than 200 ° C, the resistance temperature coefficient of the obtained resistive thin film is not stable. On the other hand, if it exceeds 500 ° C, the resistive temperature coefficient of the resistive thin film becomes positive. In addition, when the heat treatment time is less than 1 hour, the resistance temperature coefficient of the obtained resistive thin film is not stabilized, whereas even if it exceeds 10 hours, an additional increase in stability improvement effect of the resistance temperature coefficient is not seen, so that only the cost increases.

In addition, in the composition of the resistor material of the present invention, this heat treatment temperature is relatively lower than that of the resist thin film using a Ni—Cr based alloy to which Ta, Al, and Mo are added. In particular, such Ni-Cr alloys may require heat treatment at a high temperature exceeding 500 ° C. in order to obtain desired properties depending on the composition. However, in the composition of the resistor material of the present invention, the Ni-Cr alloy is 500 ° C. or less. Even in the composition range, the heat treatment temperature can be shifted toward the lower temperature.

In addition, the resistive thin film of the present invention maintains the same characteristics as the conventional ones, and particularly, in corrosion resistance (salt resistance), a superior effect of dissolution starting voltage of corrosion test using an acidic artificial sweat solution (JIS L0848) is 9 V or more. You can get it.

As shown in FIG. 1, the thin film resistor according to the present invention includes an insulating material substrate 1, a resistive thin film 2 formed thereon, and an electrode formed on both sides of the resistive thin film 2 on the insulating material substrate 1. 3) consists of. As the electrode 3, an electrode such as Al, Ag, Cu, Ni, Cr, etc. may be used in addition to the Au electrode. Such a thin film resistor will have the characteristics according to the resistive thin film of the present invention.

Example

Example 1

Ni alloy powder with an average particle diameter of 100 µm was prepared by adding 40 mass% (Cr: Al: Y = 29.5: 10.0: 0.5 (mass ratio)) of Cr, Al, and Y in total amounts as the Ni alloy powder. On the other hand, as the silicate-based glass powder, 50 mass% of B, Mg, Ca, Ba, Al, and Zr are added in total (B: Mg: Ca: Ba: Zr: Al = 2: 5: 18: 18: 5: 2 ( mass ratio)) by, the average particle diameter was prepared as a SiO ₂ powder of 10μm.

These two types of powder were mixed so that the addition amount of the silicate-based glass powder became 5% by mass to obtain a raw material powder.

This raw material powder was loaded in the carbon form of desired shape, and the hot press was performed using the atmospheric hot press furnace (AHP) of the optical axis products. In the inert atmosphere which flows Ar at 2 L / min, this molded object was sintered under the conditions of the pressure of 200 kg / cm <2>, the baking temperature of 1100 degreeC, and the baking time for 3 hours, and the sintered compact was obtained.

The resultant sintered body was processed to a thickness of 3.0 mm in a plane grinding machine (PSG-105DX manufactured by Okamoto Machine Tool Co., Ltd.), and then processed into a diameter of 75.0 mm in a wire cut (AQ750L manufactured by Sodick Co., Ltd.), and then packed using an indium wax material. The plate and the sintered body were bonded to obtain a sputtering target.

The sputtering target thus obtained is mounted on a DC sputtering equipment (CFS-4ES manufactured by Shibaura Mechatronics Co., Ltd.) so that the TS distance (distance from the target to the substrate) is 85 mm and exhausted to 5 × 10 ^-4 Pa, followed by purity of 99.999% or more. Ar gas was introduced to maintain a pressure of 0.5 Pa, and sputtering was performed at a sputtering power of 200 W, a voltage of 500 V, and a current of 0.4 A so as to have a thickness of 100 nm, thereby forming a 20 mm x 25 mm thin film on the substrate. Al ₂ O ₃ was used for the substrate at this time.

An Au electrode having a thickness of 500 nm was formed by the DC sputtering method of the same form at both ends of the obtained thin film. Then, heat treatment was performed for 3 hours at a temperature of 300 ° C. in an air atmosphere to obtain a thin film resistor using the resistive thin film of the present invention.

Specific resistance, resistance temperature characteristic, high temperature stability, and corrosion resistance (saline resistance) were evaluated about the obtained thin film resistor as follows.

Resistivity was measured by a four probe method at room temperature using a resistivity meter (manufactured by Mitsubishi Chemical's Anarikku Co., Ltd., Loresta GP MCP-T610). In this invention, it was judged that having a specific resistance in 300 micro ohm * cm or more was defective.

The resistance temperature characteristics were evaluated by calculating the resistance temperature coefficient from the resistance value obtained by measuring the resistance value (unit: Ω) at 25 ° C and 125 ° C by using the obtained thin film resistor in a thermostat. In the present invention, those lower than ± 25 ppm / ° C were judged as defective.

Regarding high temperature stability, the obtained thin film resistor was kept in a thermostatic chamber at 155 ° C for 1000 hours, and the resistance change rate (155 ° C, 1000 hours) was measured from the resistance value obtained by measuring the resistance value (unit: Ω) before and after the measurement using the resistivity meter. Was calculated and evaluated. In the present invention, it was determined that the ratio of the resistance value after the introduction was 0.1% or less based on the resistance value before the introduction into the thermostat.

The salt resistance was evaluated by performing the following corrosion test on the obtained thin film resistor and measuring the melt start voltage.

First, the initial resistance value of the resistive thin film 2 was measured by the four-terminal method using the digital multimeter (The VOAC7521A by a cancer measurement company, Inc.). As shown in FIG. 2, 30 μL of an acidic artificial sweat (JIS L0848) is dropped in the center of the resistance thin film 2 in the microcylinder, and the water droplets are separated from the diameter of the water droplet 4 and the length between the Au electrodes 3. The voltage Vp between the Au electrodes 3 was prepared such that the voltage Vd loaded at both ends of (4) was 1V. After the voltage Vp between the Au electrodes 3 was kept constant, the voltage was loaded for 3 minutes, washed with water and dried, the resistance value was measured by the four-terminal method, and the resistance change rate before and after the voltage load was measured.

This measurement is repeated to adjust the voltage Vp between the Au electrodes 3 so that the voltage Vd loaded across the water drop 4 rises from 1V to 0.2V, and when the resistance change rate exceeds 0.2%, (4) The voltage Vd loaded at both ends was obtained, and it was set as the melting start voltage of the resistive thin film 2.

Therefore, the obtained melt start voltage was loaded with acidic artificial sweat (JIS L0848), loaded with a voltage for 3 minutes at a constant voltage between Au electrodes at both ends, and subjected to water washing and drying, and the resistance change rate measured was greater than 0.2%. The minimum value of the voltages across the drop measured when In the present invention, it was determined that the melting start voltage was 9.0 V or more.

Example 2

A thin film resistor was obtained in the same manner as in Example 1 except that the amount of the silicate glass powder added was 3% by mass, and the properties thereof were measured.

Example 3

A thin film resistor was obtained in the same manner as in Example 1 except that the amount of the silicate glass powder added was 10 mass%, and the properties thereof were measured.

Example 4

A thin film resistor was obtained in the same manner as in Example 1 except that the amount of the silicate glass powder added was 20% by mass, and the properties thereof were measured.

Example 5

A thin film resistor was obtained in the same manner as in Example 1 except that no additive was added to the silicate-based glass powder (the additive content of the silicate-based glass powder was 0% by weight).

Example 6

In the silicate-based glass powder, a thin film resistor was obtained in the same manner as in Example 1 except that the content of the additive was 30% by mass, and the characteristics thereof were measured.

Example 7

In the silicate-based glass powder, a thin film resistor was obtained in the same manner as in Example 1 except that the content of the additive was 70% by mass, and the properties thereof were measured.

Example 8

In the silicate-based glass powder, a thin film resistor was obtained in the same manner as in Example 1 except that the content of the added amount was 90% by mass, and the characteristics thereof were measured.

Example 9

A thin film resistor was obtained in the same manner as in Example 1 except that the content of the additional element of the Ni alloy was set to 10% by mass, and the properties thereof were measured.

Example 10

A thin film resistor was obtained in the same manner as in Example 1 except that the content of the additional element of the Ni alloy was 30% by mass, and the properties thereof were measured.

Example 11

A thin film resistor was obtained in the same manner as in Example 1 except that the content of the additional element of the Ni alloy was set to 50% by mass, and the characteristics thereof were measured.

Example 12

A thin film resistor was obtained in the same manner as in Example 1 except that the content of the additional element of the Ni alloy was set to 60 mass%, and the properties thereof were measured.

Comparative Example 1

A thin film resistor was obtained in the same manner as in Example 1 except that the silicate-based glass powder was not added, and the properties thereof were measured. The thin film resistor of Comparative Example 1 had a specific resistance of less than 300 µΩ · cm, a resistance change rate of more than 0.1%, and a very low melt start voltage. As described above, it is understood that a thin film resistor having sufficient characteristics cannot be obtained when the heat treatment temperature at the time of obtaining the resistive thin film is relatively low.

Comparative Example 2

A sputtering target was obtained like Example 1 except having made the addition amount of the silicate glass powder into 30 mass%. However, an attempt was made to form a resistive thin film in the same manner as in Example 1 using this sputtering target, but the film could not be formed because the target lacked conductivity.

Comparative Example 3

A thin film resistor was obtained in the same manner as in Example 1 except that the additive content of the silicate glass powder was set to 95% by mass and the addition amount of the silicate glass powder was set to 10% by mass, and the characteristics thereof were measured. It is understood that the thin film resistor of Comparative Example 3 has a resistance temperature coefficient of more than ± 25 ppm · ° C, a melting initiation voltage of less than 9 V, and cannot achieve the resistance temperature characteristics and the corrosion resistance required in the present invention.

Comparative Example 4

A thin film resistor was obtained in the same manner as in Example 1 except that the content of the added element of the Ni alloy was 0% by mass, and the properties thereof were measured. The thin film resistor of Comparative Example 4 also has a specific resistance of less than 300 μΩ · cm, a resistance temperature coefficient of ± 25 ppm / ° C., and a melting start voltage of less than 9 V, which does not achieve the resistance, resistance temperature characteristics, and corrosion resistance required by the present invention. It is understood that you do not.

Comparative Example 5

A thin film resistor was obtained in the same manner as in Example 1 except that the content of the additional element of the Ni alloy was 70 mass%, and the properties thereof were measured. It is understood that the thin film resistor of Comparative Example 5 has a resistance temperature coefficient of more than ± 25 ppm / 占 폚 and a melting initiation voltage of less than 9 v, so that resistance temperature characteristics and corrosion resistance required in the present invention cannot be achieved.

The composition of each Example, whether or not DC sputtering, the heat treatment temperature of the thin film after film formation, and the characteristic measurement result of the obtained thin film resistor are shown in Table 1, respectively.

Element added to Ni (total amount added)
(mass%) Glass powder
Addition amount
(mass%) Additives to Glass (Total Additives)
(mass%) DC sputtering Heat treatment temperature
(℃ / hr) Resistivity
(μΩcm) Resistance temperature coefficient
(ppm / ℃) Resistance change rate
(155 ℃, 1000hr)
(%) Melting start pressure
(V) Example 1 Cr, Al, Y (40) 5 B, Ba, Mg, Ca, Zr, Al (50) possible 300/3 510 One 0.03 9.2 Example 2 Cr, Al, Y (40) 3 B, Ba, Mg, Ca, Zr, Al (50) possible 300/3 498 -3 0.04 9.1 Example 3 Cr, Al, Y (40) 10 B, Ba, Mg, Ca, Zr, Al (50) possible 300/3 939 0 0.02 10.0 Example 4 Cr, Al, Y (40) 20 B, Ba, Mg, Ca, Zr, Al (50) possible 300/3 1056 3 0.01 11.6 Example 5 Cr, Al, Y (40) 5 - possible 300/3 520 -16 0.02 9.5 Example 6 Cr, Al, Y (40) 5 B, Ba, Mg, Ca, Zr, Al (30) possible 300/3 516 One 0.03 9.4 Example 7 Cr, Al, Y (40) 5 B, Ba, Mg, Ca, Zr, Al (70) possible 300/3 518 One 0.04 9.1 Example 8 Cr, Al, Y (40) 5 B, Ba, Mg, Ca, Zr, Al (90) possible 300/3 511 16 0.04 9.0 Example 9 Cr, Al, Y (10) 5 B, Ba, Mg, Ca, Zr, Al (50) possible 300/3 499 -15 0.04 9.1 Example 10 Cr, Al, Y (30) 5 B, Ba, Mg, Ca, Zr, Al (50) possible 300/3 501 -2 0.03 9.2 Example 11 Cr, Al, Y (50) 5 B, Ba, Mg, Ca, Zr, Al (50) possible 300/3 514 0 0.03 9.1 Example 12 Cr, Al, Y (60) 5 B, Ba, Mg, Ca, Zr, Al (50) possible 300/3 522 10 0.03 9.2 Comparative Example 1 Cr, Al, Y (40) 0 - possible 300/3 189 7 0.21 1.6 Comparative Example 2 Cr, Al, Y (40) 30 B, Ba, Mg, Ca, Zr, Al (50) Impossible - - - - - Comparative Example 3 Cr, Al, Y (40) 10 B, Ba, Mg, Ca, Zr, Al (50) possible 300/3 946 31 0.07 8.4 Comparative Example 4 - 5 B, Ba, Mg, Ca, Zr, Al (50) possible 300/3 282 -27 0.06 8.2 Comparative Example 5 Cr, Al, Y (70) 5 B, Ba, Mg, Ca, Zr, Al (50) possible 300/3 952 29 0.05 9.4

Example 13

A silicate-based glass powder in the raw material powder, in which 50% by mass of Mg, Ca, Ba, Al, and Zr were added (Mg: Ca: Ba: Zr: Al = 5: 20: 18: 5: 2 (mass ratio)). A thin film resistor was obtained in the same manner as in Example 1 except that the SiO ₂ powder having an average particle diameter of 10 μm was used, and the characteristics thereof were measured.

Example 14

A thin film resistor was obtained in the same manner as in Example 13 except that the addition amount of the silicate-based glass powder was 7% by mass, and the properties thereof were measured.

Example 15

A thin film resistor was obtained in the same manner as in Example 13 except that the addition amount of the silicate glass powder was 10 mass%, and the properties thereof were measured.

Example 16

A thin film resistor was obtained in the same manner as in Example 13 except that no additive was added to the silicate glass powder (addition content of the silicate glass powder was 0% by mass), and the properties thereof were measured.

Example 17

A thin film resistor was obtained in the same manner as in Example 13 except that the additive content of the silicate-based glass powder was 90% by mass, and the properties thereof were measured.

Example 18

A thin film resistor was obtained in the same manner as in Example 13 except that the content of the additional elements of the Ni alloy was set to 50% by mass, and the properties thereof were measured.

Comparative Example 6

A thin film resistor was obtained in the same manner as in Example 13 except that the silicate-based glass powder was not added, and the properties thereof were measured.

Comparative Example 7

A thin film resistor was obtained in the same manner as in Example 13 except that the amount of the silicate glass powder added was 30% by mass, and the properties thereof were measured.

Comparative Example 8

A thin film resistor was obtained in the same manner as in Example 13 except that the content of the additive of the silicate glass powder was set to 95% by weight and the addition amount of the silicate glass powder was set to 10% by mass, and the characteristics thereof were measured.

Comparative Example 9

A thin film resistor was obtained in the same manner as in Example 13 except that the content of the additional element of the Ni alloy was 0% by mass, and the properties thereof were measured.

Comparative Example 10

A thin film resistor was obtained in the same manner as in Example 13 except that the content of the additional elements of the Ni alloy was 70 mass%, and the properties thereof were measured.

It is understood that the same trends as Comparative Examples 1 to 5 can be seen also in Comparative Examples 6 to 10.

The composition of each Example, the presence or absence of DC sputtering, the heat treatment temperature of the thin film after film formation, and the characteristic measurement result of the obtained thin film resistor are shown in Table 2, respectively.

Element added to Ni (total amount added)
(mass%) Glass powder
Addition amount
(mass%) Additives to Glass (Total Additives)
(mass%) DC sputtering Heat treatment temperature
(℃ / hr) Resistivity
(μΩcm) Resistance temperature coefficient
(ppm / ℃) Resistance change rate
(155 ℃, 1000hr)
(%) Melting start pressure
(V) Example 13 Cr, Al, Y (40) 5 Ba, Mg, Ca, Zr, Al (50) possible 300/3 510 5 0.05 9.2 Example 14 Cr, Al, Y (40) 7 Ba, Mg, Ca, Zr, Al (50) possible 300/3 678 4 0.04 9.6 Example 15 Cr, Al, Y (40) 10 Ba, Mg, Ca, Zr, Al (50) possible 300/3 939 3 0.02 10.0 Example 16 Cr, Al, Y (40) 5 - possible 300/3 504 -11 0.03 9.4 Example 17 Cr, Al, Y (40) 5 Ba, Mg, Ca, Zr, Al (90) possible 300/3 563 23 0.04 9.0 Example 18 Cr, Al, Y (50) 5 Ba, Mg, Ca, Zr, Al (50) possible 300/3 521 6 0.08 9.2 Comparative Example 6 Cr, Al, Y (40) 0 - possible 300/3 189 7 0.41 1.6 Comparative Example 7 Cr, Al, Y (40) 30 Ba, Mg, Ca, Zr, Al (50) Impossible - - - - - Comparative Example 8 Cr, Al, Y (40) 10 Ba, Mg, Ca, Zr, Al (95) possible 300/3 946 31 0.33 8.4 Comparative Example 9 - 5 Ba, Mg, Ca, Zr, Al (50) possible 300/3 282 -55 0.29 8.2 Comparative Example 10 Cr, Al, Y (70) 5 Ba, Mg, Ca, Zr, Al (50) possible 300/3 952 57 0.27 9.4

1 --- insulating substrate (alumina substrate)
2 --- resistive thin film
3 --- electrode (Au electrode)
4 --- Droplets

Claims

B, Mg, Ca, Ba, Al containing 10 to 60% by mass of at least one additional element selected from Cr, Al and Y, and the balance of SiO ₂ as a main component in a Ni alloy composed of Ni and an unavoidable impurity And 3 to 20 mass% of a silicate glass containing 0 to 90 mass% of one or more selected from Zr and oxides thereof.

B, Mg, Ca, Ba, Al containing 10 to 60% by mass of at least one additional element selected from Cr, Al and Y, and the balance of SiO ₂ as a main component in a Ni alloy composed of Ni and an unavoidable impurity And a sputtering target for forming a resistor thin film, wherein a silicate-based glass containing 0 to 90 mass% of at least one selected from Zr and oxides thereof is added.

B, Mg, Ca, Ba, Al containing 10 to 60% by mass of at least one additional element selected from Cr, Al and Y, and the balance of SiO ₂ as a main component in a Ni alloy composed of Ni and an unavoidable impurity 3 to 20 mass% of silicate glass containing 0 to 90 mass% of at least one selected from Zr and oxides thereof, and has a specific resistance of 300 to 1500 µΩ · cm and a resistance temperature coefficient of -25 to + It is in the range of 25 ppm / ° C, the resistance change rate with time of 1000 hours at 155 ° C is maintained at 0.1% or less, and the dissolution start voltage of the corrosion test using an acidic artificial sweat solution (JIS L0848) is 9V or more. Resistive thin film.

A thin film resistor comprising an insulating substrate, a resistive thin film according to claim 3 formed on the insulating material substrate, and electrodes formed on both sides of the resistive thin film on the insulating material substrate.

Silicate-based glass powder containing SiO ₂ as a main component, 0 to 90% by mass of at least one selected from B, Mg, Ca, Ba, Al, Zr, and oxides thereof, and Cr, Al, and Y Mixing the Ni alloy powder containing 10 to 60 mass% of one or more additional elements and the balance consisting of Ni and inevitable impurities so that the silicate-based glass powder is 3 to 20 mass%, molding the obtained mixed powder into a desired shape The molded article obtained by sintering at 500-1400 degreeC under pressure of 50 kg / cm <2> or more in a vacuum or inert atmosphere, The manufacturing method of the sputtering target for resistance thin film formation characterized by the above-mentioned.

A thin film obtained by forming a thin film on an insulating material substrate by a sputtering method using the sputtering target according to claim 5 is subjected to a heat treatment for 1 to 10 hours at 200 to 500 ° C. in an air or an inert gas atmosphere. Method of manufacturing a resistive thin film.

The method of manufacturing a resistive thin film according to claim 6, wherein a DC sputtering method is used as the sputtering method.