JP7087741B2 - A method for manufacturing a resistor material, a sputtering target for forming a resistance thin film, a resistance thin film and a thin film resistor, and a method for manufacturing a sputtering target for forming a resistance thin film and a method for manufacturing a resistance thin film. - Google Patents

Description

The present invention relates to a thin film resistor as an electronic component, a resistance thin film used to obtain a thin film resistor, a sputtering target for forming a resistance thin film, a resistor material as a sputtering target for forming a resistance thin film, and a sputtering target for forming a resistance thin film. And a method for manufacturing a resistance thin film.

Resistors such as chip resistors, precision resistors, network resistors, high-voltage resistors, temperature sensors such as side temperature resistors and temperature-sensitive resistors, and electronic components such as hybrid ICs and their composite module products have resistance thin films. A thin film resistor using is used.

In recent years, with the miniaturization and high integration of electrical and electronic products, it has been required to reduce the size of thin film resistors. With the miniaturization and higher functionality of electronic components, the environment in which electronic components are used has become hotter than before. Further, high temperature stability is strongly required, in which the rate of change in resistance with time is small in a state of being held at a high temperature.

In thin film resistors, Ta alloys, TaN compounds, and Ni—Cr alloys are often used as resistor materials for forming resistance thin films.

This resistance thin film using a Ni—Cr alloy has the characteristics of ohmic characteristics, which are the characteristics of metals, and has the characteristics that the resistance value does not change much with changes in the ambient temperature and the thermal stability is high. Commonly used for thin film resistors.

However, the Ni—Cr based alloy has a problem that the specific resistance is low as a resistor material. To solve this problem, for example, the following Patent Document 1 proposes a resistance thin film in which Ta, Al, and Mo are added to a Ni—Cr based alloy to increase the specific resistance. Furthermore, as a method for increasing the specific resistance of the thin film resistivity even if the heat treatment is performed at a temperature lower than the conventional one, for example, in the following Patent Document 2, one or more additive elements selected from Cr, Al and Y are added. A silicate film containing 0 to 90% by mass of B, Mg, Ca, Ba, Al, Zr and one or more selected from these oxides in the Ni alloy powder contained, with SiO ₂ (silica) as the main component. A method for manufacturing a sputtering target for forming a resistivity thin film having a step of adding glass powder has been proposed.

Japanese Unexamined Patent Publication No. 2008-01604 Japanese Unexamined Patent Publication No. 2011-119234

A resistance film obtained by adding Ta, Al, and Mo to the Ni—Cr alloy proposed in Patent Document 1 and one or more additive elements selected from Cr, Al, and Y proposed in Patent Document 2. To the Ni alloy powder contained, a silicate-based glass powder containing SiO ₂ (silica) as a main component and containing B, Mg, Ca, Ba, Al, Zr and one or more selected from these oxides is added. The resistance thin film formed by using the sputtering target for forming the resistance thin film produced in the above can obtain a higher specific resistance than the resistance thin film made of the conventional Ni—Cr alloy.

By the way, the resistance thin film in which Ta, Al, and Mo are added to the Ni—Cr based alloy proposed in Patent Document 1 is heat-treated at a high temperature exceeding 500 ° C. in order to obtain a predetermined specific resistance and resistance change rate. You will need it.
However, in recent years, it has been required to lower the heat treatment temperature in order to obtain a predetermined resistivity and high temperature stability.

However, the resistance thin film proposed in Patent Document 2 is a Ni—Cr system proposed in Patent Document 1 even if it is heat-treated at a lower temperature than the resistance thin film proposed in Patent Document 1. High specific resistance and excellent high temperature stability similar to those of a resistance thin film obtained by adding Ta, Al, and Mo to an alloy can be obtained.
However, in recent years, with the miniaturization of electronic components, when heat treatment is performed at a relatively low temperature similar to the resistance thin film proposed in Patent Document 2, compared with the resistance thin film proposed in Patent Document 2. There is a demand for a resistance thin film that satisfies further high resistance and further high temperature stability.

The present invention has been made in view of such problems, and even if the resistance thin film is heat-treated at a relatively low temperature, the resistance thin film has higher specific resistance and high-temperature stability than the conventional resistance thin film. It is an object of the present invention to provide a thin-film resistor provided with a resistance thin film, a thin-film resistor material for manufacturing a resistance thin film, a sputtering target for forming a resistance thin film, and a sputtering target for forming a resistance thin film and a method for manufacturing the resistance thin film. ..

Similar to the resistance thin film proposed in Patent Document 2, the present inventors have compared with the resistance thin film proposed in Patent Document 2 when the resistance thin film is heat-treated at a relatively lower temperature than before. Further, a resistance thin film using a Ni—Cr alloy having further high resistance and further high temperature stability was enthusiastically examined and evaluated. As a result, the present inventors have found that the Ni—Cr alloy powder does not contain B, Mg, Ca, Ba, Al, Zr and oxides thereof, and has a pure SiO ₂ (silica) having an average particle size within a predetermined range. ) Only glass powder is used as a resistivity thin film formed by using a Ni—Cr alloy material, which contains SiO ₂ (silica) as a main component, and B, Mg, Ca, Ba, Al, Zr and these. It has been found that it has higher resistivity and high temperature stability than Ni—Cr alloys containing silicate-based glass containing the oxide of.

That is, the resistor material according to the present invention contains 10% by mass or more and 60% by mass or less of one or more additive elements selected from Cr, Al and Y, and the balance is a Ni alloy powder composed of Ni and unavoidable impurities. A resistor material made of a sintered body of a mixed powder containing 3% by mass or more and 20% by mass or less of a glass powder made of pure SiO ₂ having an average particle size of 30 μm or more and 200 μm or less. It is characterized by having a specific resistance of 525 μΩ · cm or more and 1700 μΩ · cm or less when a thin film is formed, and a resistivity change rate of 0.1% or less over time when the temperature of 155 ° C. is maintained for 1000 hours. do.

Further, the sputtering target for forming a resistance thin film, which is one form of the resistor material according to the present invention, contains 10% by mass or more and 60% by mass or less of one or more additive elements selected from Cr, Al and Y, and the balance. A resistance thin film formed of a sintered body of a mixed powder containing 3% by mass or more and 20% by mass or less of a glass powder made of pure SiO ₂ having an average particle size of 30 μm or more and 200 μm or less in a Ni alloy powder composed of Ni and unavoidable impurities. Sputtering target for forming a resistance thin film with a specific resistance of 525 μΩ · cm or more and 1700 μΩ · cm or less when a resistance thin film is formed using the sputtering target for forming a resistance thin film over time when the temperature of 155 ° C. is maintained for 1000 hours. It is characterized by having a characteristic that the resistance change rate is 0.1% or less .

Further, the resistivity thin film according to the present invention contains 10% by mass or more and 60% by mass or less of one or more additive elements selected from Cr, Al and Y, and the balance is a Ni alloy powder composed of Ni and unavoidable impurities on average. A thin film formed from a sintered body of a mixed powder containing 3% by mass or more and 20% by mass or less of a glass powder made of pure SiO ₂ having a particle size of 30 μm or more and 200 μm or less, and having a specific resistance of 525 μΩ · cm or more. It is characterized by having a resistance change rate of 1700 μΩ · cm or less and 0.1% or less over time when the temperature of 155 ° C. is maintained for 1000 hours.

Further, the thin film resistor according to the present invention is composed of an insulating material substrate, the above-mentioned resistance thin film of the present invention formed on the insulating material substrate, and electrodes formed on both sides of the resistance thin film on the insulating material substrate. It is characterized by becoming.

Further, in the method for manufacturing a sputtering target for forming a resistance thin film according to the present invention, a glass powder made of pure SiO ₂ having an average particle size of 30 μm or more and 200 μm or less and one or more additive elements selected from Cr, Al and Y are used. A Ni alloy powder having an average particle size of 10 μm or more and 200 μm or less, which contains 10% by mass or more and 60% by mass or less and the balance is composed of Ni and unavoidable impurities, so that the glass powder has an average particle size of 3% by mass or more and 20% by mass or less. After mixing, the obtained mixed powder is molded into a desired shape, and the obtained molded product is subjected to a pressure of 50 kg / cm ² or more in a vacuum or an inert atmosphere at a temperature of 1100 ° C. or higher and 1400 ° C. or lower. When a sintered body was produced by firing in 1 and a resistance thin film was formed using the sintered body as a material, the specific resistance became 525 μΩ · cm or more and 1700 μΩ · cm or less, and the time elapsed when the temperature of 155 ° C. was maintained for 1000 hours. It is characterized by having a characteristic that the target resistance change rate is 0.1% or less .

Further, in the method for producing a resistance thin film according to the present invention, a thin film is formed on an insulating material substrate by a sputtering method using the sputtering target of the present invention, and the obtained thin film is placed in the atmosphere or an inert gas atmosphere. The present invention is characterized in that the heat treatment is performed at a temperature of 200 ° C. or higher and 500 ° C. or lower for 1 hour or longer and 10 hours or shorter.

The "average particle size" in the present invention means that the abundance ratio (volume basis) of both the glass powder and the Ni alloy powder is integrated from the small diameter side in the particle size distribution of each powder measured by the laser diffraction method. This is the particle size (D50) whose value is half the integrated value of the abundance ratio over the entire particle size.

Further, the composition of the resistance thin film formed by the sputtering method can be considered to be substantially the same as the composition of the sputtering target because the composition of the sputtering target, which is the resistor material, is formed on the target substrate by sputtering.

According to the present invention, a thin film resistor having a resistance thin film and a resistance thin film having a higher specific resistance and high temperature stability than a conventional resistance thin film even when a heat treatment is applied to the resistance thin film at a relatively low temperature. A thin-film resistor material for manufacturing a resistance thin film, a sputtering target for forming a resistance thin film, a sputtering target for forming a resistance thin film, and a method for manufacturing a resistance thin film can be obtained. For example, a thin-film resistor configured by using the resistance thin film material of the present invention as a sputtering target for forming a resistance thin film and using the resistance thin film obtained by the sputtering method is subjected to heat treatment on the resistance thin film at a relatively low temperature. However, it has higher specific resistance and high temperature stability than conventional resistance thin films, and has a high specific resistance of 525 μΩ · cm or more and 1700 μΩ · cm or less, and the rate of change in resistance over time when held at a temperature of 155 ° C for 1000 hours. High high temperature stability of 0.1% or less can be obtained.

It is a schematic diagram of the thin film resistor to which this invention is applied. It is sectional drawing which shows typically the state of the structure in the sintered body which forms the resistor material by this invention. It is sectional drawing which shows typically the state of the structure in the sintered body which makes a conventional resistor material.

Hereinafter, embodiments of the present invention will be specifically described.

Thin-film resistors are required to have various characteristics, but among them, the characteristics for miniaturization of electronic components in recent years are particularly required to have high resistance and excellent high-temperature stability, mainly Ni-Cr alloys. As a result, various attempts have been made to improve it.
The resistance thin film in which Ta, Al and Mo are added to the Ni—Cr based alloy proposed in Patent Document 1 maintains high temperature stability as compared with the resistance thin film using the conventional Ni—Cr based alloy. , Resistance and corrosion resistance are improved.
Further, the resistance thin film proposed in Patent Document 2 is obtained by adding a predetermined amount of silicate-based glass to a Ni alloy, which has not been conventionally used as a resistor material used for a thin film resistor for electronic parts. The heat treatment temperature for obtaining the desired properties is relatively lowered.
However, with the recent miniaturization of electronic components, when the heat treatment temperature for obtaining predetermined resistivity and high temperature stability is relatively lowered, the improvement effect in the resistance thin film proposed in Patent Document 2 is exceeded. However, sufficient high resistance and high temperature stability are required.

The resistor material of the embodiment of the present invention contains 10% by mass or more and 60% by mass or less of one or more additive elements selected from Cr, Al and Y, and the balance is a Ni alloy powder composed of Ni and unavoidable impurities. It is composed of a sintered body of a mixed powder containing 3% by mass or more and 20% by mass or less of a glass powder made of pure SiO ₂ having an average particle size of 30 μm or more and 200 μm or less.
The "resistor material" in the present invention refers to a material for forming the resistance thin film of the present invention, and is particularly suitable for the form as long as it is made of a sintered body of a mixed powder having the above composition. Not limited. For example, tablets and sputtering targets are one of the forms of such resistor materials. Hereinafter, embodiments of the present invention will be described in detail.

(Resistance material)
The resistor material of the embodiment of the present invention is constructed by using a Ni alloy powder based on Ni. This Ni alloy powder contains 10% by mass or more and 60% by mass or less of one or more additive elements selected from Cr, Al and Y, and the balance is Ni and unavoidable impurities.
By containing each additive element in a predetermined amount, the composition has characteristics as a resistor material. The content of Cr is particularly effective in reducing the absolute value of the temperature coefficient of resistance. Further, the inclusion of Al is particularly effective in improving the corrosion resistance. Further, the content of Y is particularly effective in improving the adhesion between the Ni alloy and the glass powder. These additive elements are added in a required amount according to the required characteristics, but in order to have the characteristics in the resistance thin film and the thin film resistor of the present invention, all the additive elements are contained in a fixed amount. In order to exert the effect of each additive element, it is necessary to contain 10% by mass or more in total. In order to more effectively exhibit each characteristic, Cr is preferably contained in an amount of 20% by mass or more, Al is preferably contained in an amount of 10% by mass or more, and Y is preferably contained in an amount of 0.3% by mass or more. preferable. On the other hand, if the amount of these additive elements is excessive, the stability after film formation and heating is deteriorated, various characteristics such as resistance value are greatly varied, and the reproducibility may be deteriorated. Therefore, the total content of these additive elements needs to be 60% by mass or less. The total content of the added elements is more preferably in the range of 40% by mass or more and 50% by mass or less.
The resistor material of the embodiment of the present invention is a mixed powder containing 3% by mass or more and 20% by mass or less of glass made of pure SiO ₂ having an average particle size of 30 μm or more and 200 μm or less in a Ni alloy powder having such a composition. It consists of a sintered body.

The present inventors have described in Patent Document 2 a Ni alloy powder containing one or more additive elements selected from Cr, Al and Y, containing SiO ₂ (silica) as a main component, and B, Mg, and the like. The texture of the cross section of the sintered body of the mixed powder forming the resistor material formed by adding a silicate-based glass powder containing Ca, Ba, Al, Zr and one or more selected from these oxides was investigated. rice field. As a result, as shown in FIG. 3, the silicate-based glass powder is in a molten and agglomerated state, whereas the Ni alloy powder hardly melts and maintains the shape of the powder (spherical in FIG. 3). It was confirmed that the Ni alloy powder and the silicate-based glass powder were not mixed with each other because they were pushed and collected by the silicate-based glass that had been melted and aggregated.
Regarding this cause, the present inventors considered that the softening point of the silicate-based glass powder was too low compared to the melting point of the Ni alloy powder.
Therefore, instead of the silicate-based glass powder containing the additive element such as B, the present inventors use a glass powder made of pure SiO ₂ containing no additive element having a higher softening point than the silicate-based glass as a Ni alloy. The mixed powder added to the powder was prepared, and the prepared mixed powder was fired to prepare a sintered body of the mixed powder, and the structure of the cross section of the sintered body of the prepared mixed powder was examined.
However, when the average particle size of the glass powder made of pure SiO ₂ added to the Ni alloy powder is about 10 μm described in Patent Document 2, it is fired to prepare a sintered body of the mixed powder, and the prepared mixture is prepared. As shown in FIG. 3, the structure of the cross section of the sintered body of the powder is such that the glass powder is melted and aggregated, and the Ni alloy powder and the glass powder made of pure SiO ₂ are not mixed. Was confirmed.
Regarding this cause, the present inventors considered that the average particle size of the glass powder made of pure SiO ₂ is too small and melts quickly.
Therefore, the present inventors next prepare several kinds of mixed powders in which glass powders made of pure SiO ₂ having different average particle sizes are added to Ni alloy powders, and each mixed powder is fired to form a mixed powder. The sintered body of the above was prepared, and the structure of the cross section of the sintered body of each of the prepared mixed powders was examined.
As a result, the present inventors have obtained a sintered body of the mixed powder produced by firing a mixed powder obtained by adding a glass powder composed of pure SiO ₂ having an average particle size of 30 μm or more and 200 μm or less to a Ni alloy powder. As shown in 2, there is no agglomeration of the glass powder made of pure SiO ₂ , the Ni alloy powder is melted and deformed, and the Ni alloy powder and the glass powder made of pure SiO ₂ are appropriately mixed. I found that it would be.

Further, the present inventors have made a resistance thin film by using a resistor material made of a sintered body of a mixed powder in which a glass powder made of pure SiO ₂ having an average particle size of 30 μm or more and 200 μm or less is contained in a Ni alloy powder. It has been found that the resistance value of the resistance thin film can be increased by forming the resistance thin film, and the rate of change of the resistance value at high temperature can be suppressed to a low level. Further, it was confirmed that the resistance thin film of the embodiment of the present invention has not only the effect of improving electrical characteristics such as resistance value but also the effect of improving corrosion resistance.
Further, the present inventors have found that a glass powder made of pure SiO ₂ having an average particle size of 30 μm or more and 200 μm or less is an insulator, and the effect can be obtained with a content of 3% by mass or more. If the content exceeds 20% by mass, the conductivity of the Ni alloy will not be sufficiently exhibited and it will become an insulator. Even if the resistor material is in the form of a sputtering target, film formation by DC sputtering using the sputtering target It is not preferable because it may not be possible. The content of the glass powder made of pure SiO ₂ having an average particle size of 30 μm or more and 200 μm or less is more preferably 5% by mass or more and 10% by mass or less.

(Preparation of sputtering target for forming resistance thin film)
The raw materials of the sputtering target for forming a resistance thin film according to the embodiment of the present invention include a glass powder made of pure SiO ₂ having an average particle size of 30 μm or more and 200 μm or less, and one or more additive elements selected from Cr, Al and Y. Is contained in an amount of 10% by mass or more and 60% by mass or less, and a Ni alloy powder having an average particle size of 10 μm or more and 200 μm or less, the balance of which is Ni and unavoidable impurities, is used. The total content of the additive elements in the Ni alloy powder is more preferably 40% by mass or more and 50% by mass or less.

As described above, the average particle size of the glass powder made of pure SiO ₂ used as the raw material of the sputtering target for forming a resistance thin film according to the embodiment of the present invention is 30 μm or more and 200 μm or less, but it is possible to use a powder of about 100 μm. More preferred. When the average particle size of the glass powder made of pure SiO ₂ is less than 30 μm, the state shown in FIG. 3 is obtained when the mixed powder mixed with the Ni alloy powder is fired to prepare a sintered body of the mixed powder. Similarly, if the SiO ₂ glass powder aggregates, composition segregation occurs, the sintering density does not increase, and the resistance thin film obtained by sputtering using the produced sputtering target for forming a resistance thin film can obtain the desired characteristics. , It is not preferable because sputtering itself may not be possible.

As the Ni alloy powder, a spherical powder having an average particle size of 10 μm or more and 200 μm or less is used. Such spherical Ni alloy powder can be obtained, for example, by atomization. When sintering, it is usually desirable that the particle size of the raw material powder is fine. However, this is not the case when sintering is performed by hot pressing. When hot-pressing, the carbon mold is filled with the raw material powder, but since the carbon mold has gaps at the joints, if the raw material powder is too fine, the raw material powder will leak from the gaps and workability will deteriorate. be. In addition, if the raw material powder is too fine, the frictional force between the raw material powders also increases, the raw material powder does not move sufficiently when pressed, and the density of the resistor material (sintered body) after sintering is sufficiently high. It is not preferable because it may not be possible to do so.

These raw materials are added to a predetermined amount in the range of 3% by mass or more and 20% by mass or less (more preferably 5% by mass or more and 10% by mass or less) of a glass powder made of pure SiO ₂ having an average particle size of 30 μm or more and 200 μm or less. To obtain a mixed powder as a raw material powder. A sintered body of the mixed powder can be obtained by filling the obtained mixed powder into a carbon mold or the like to form a desired shape, and sintering the obtained molded body by a hot press method. .. As specific sintering conditions, it is sintered in a vacuum or in an inert atmosphere under pressure of 50 kg / cm ² or more at a temperature of 1100 ° C. or higher and 1400 ° C. or lower by firing for 1 hour or longer and 5 hours or shorter. .. The hot pressing method in the present invention also includes a HIP (hot hydrostatic pressure pressing) method.

The sintering temperature is preferably set according to the sintering temperature of the Ni alloy of about 1000 ° C. or higher and 1300 ° C. or lower. Since the softening point of the glass made of pure SiO ₂ is about 1600 ° C., the mixed powder forming the resistor material of the embodiment of the present invention is obtained by sintering at a temperature within the above range (1100 ° C. or higher and 1400 ° C. or lower). As shown in FIG. 2, the structure of the sintered body of the above can be brought into a state where there is no agglomeration of glass powder and no composition segregation.

By adjusting the dimensions of the sintered body of the mixed powder thus obtained as necessary, the sputtering target for forming a resistance thin film according to the embodiment of the present invention can be obtained. When sputtering is performed, it is used by attaching it to a sputtering device or the like by bonding it to a copper plate called a backing plate, which is a member for attaching to the sputtering device.

(Preparation of resistance thin film)
The resistance thin film of the embodiment of the present invention can be obtained, for example, by forming a film by a sputtering method using the sputtering target for forming a resistance thin film of the embodiment of the present invention obtained as described above. The resistance thin film formed by such a method such as sputtering can obtain substantially the same composition as the resistor material. As a substrate for a thin film resistor having such a resistance thin film, it is desirable to use an insulating material substrate such as Al ₂ O ₃ or SiO ₂ . In addition to the above sputtering method, the resistance thin film can also be formed by processing the resistor material of the embodiment of the present invention into a thin-film deposition tablet and forming a resistance thin film by a vapor deposition method such as vacuum deposition. ..

There are various methods in the sputtering method, and the application to the embodiment of the present invention is not particularly limited by the type of the method, but it is preferable to use the DC sputtering method from the viewpoint of cost and mass productivity. The sputtering conditions depend on the sputtering device, but for example, when a sputtering target having a target size of φ75 mm × 3 mm is used and a sputtering device having an output of 200 W (fixed) is used, the voltage is 400 to 600 V and the current is 0. The film can be formed under the conditions of .3 to 0.5 A, Ar flow rate: 15 to 25 SCCM, total pressure: 0.4 to 0.6 Pa, and TS distance (distance from the target to the substrate): 85 mm.

The thin film immediately after the sputtering film formation has a negative temperature coefficient of resistance and may have insufficient resistance stability at high temperatures. The temperature coefficient of resistance of the thin film immediately after film formation is subjected to heat treatment in the air or in an inert gas at a temperature of 200 ° C. or higher and 500 ° C. or lower for 1 hour or longer and 10 hours or lower, depending on the composition of the thin film. Can be completed as a resistance thin film with improved resistance stability at high temperatures.

As shown in FIG. 1, the thin film resistor of the embodiment of the present invention is insulated from the insulating material substrate 1 and the resistance thin film 2 of the embodiment of the present invention formed on the insulating material substrate 1 as described above. It is composed of electrodes 3 formed on both sides of the resistance thin film 2 on the material substrate 1. As the electrode 3, in addition to the Au electrode, electrodes such as Al, Ag, Cu, Ni, and Cr can be used. Since the thin film resistor configured as described above has characteristics based on the resistance thin film of the embodiment of the present invention, it can be an electronic component having high resistance and a low resistance change rate at high temperature.

Hereinafter, the present invention will be described in detail based on more specific examples. The scope of the present invention is not limited to the examples.

(Example 1)
1. 1. Preparation of sintered body for evaluation
As a Ni alloy powder, 40% by mass of Cr, Al, and Y are added in total (Cr: Al: Y = 29.5: 10.0: 0.5 (mass ratio)), and a Ni alloy powder having an average particle size of 50 μm is added. Prepared. On the other hand, as a pure SiO ₂ glass powder, a SiO ₂ glass powder having an average particle size of 100 μm with an impurity content of 10 ppm or less was prepared.
These two types of powders were mixed so that the amount of SiO ₂ glass powder added was 5% by mass to obtain a raw material powder.
This raw material powder was loaded into a carbon mold having a predetermined shape and hot-pressed using an atmospheric hot press furnace to obtain a molded product having a predetermined shape. Then, the molded body was fired in an inert atmosphere in which Ar was flown at 2 L / min under the conditions of a pressure of 200 kg / cm ² , a firing temperature of 1100 ° C., and a firing time of 3 hours to obtain a sintered body of the mixed powder. Obtained. The obtained sintered body of the mixed powder was processed into a thickness of 3.0 mm by a surface grinding machine, and then processed into a disk-shaped sputtering target for forming a resistance thin film having a diameter of 75.0 mm by using a wire cut. The obtained sputtering target was bonded to a copper backing plate using an indium wax material to prepare a sample for sputtering.

2. 2. Evaluation of Sintered Body The density and agglomeration of glass powder were evaluated for the obtained mixed powder sintered body as follows.
The density was evaluated by obtaining the density from the weight and volume of the obtained sintered body of the mixed powder (sputtering target for forming a resistance thin film) and calculating the ratio with the theoretical density.
The evaluation of the agglomeration of the glass powder was carried out by observing the cross section of the sintered body of the obtained mixed powder and confirming the presence or absence of the agglomeration of the glass powder.
The evaluation results of the sintered body of the mixed powder are shown in Table 1 together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

3. 3. Fabrication of Thin Film Resistor for Evaluation The sputtering target for forming a resistance thin film thus obtained is mounted on a sputtering device so that the distance from the substrate is 85 mm, and after exhausting to 5 × 10 ^-4 Pa, the purity is 99. .999% or more of Ar gas is introduced and maintained at a pressure of 0.5 Pa, and sputtering is performed at a sputtering power of 200 W, a voltage of 500 V, and a current of 0.4 A so that the film thickness becomes 100 nm, and the film is placed on the substrate. A resistance thin film having a size of 20 mm × 25 mm was formed. At this time, Al ₂ O ₃ was used for the substrate.
Next, the sputtering target for forming a resistance thin film is removed from the sputtering device, and the separately prepared sputtering target for forming an Au electrode is attached to the sputtering device. An Au electrode having a film thickness of 500 nm was formed by the same DC sputtering method as in the case of forming a resistance thin film. Then, the heat treatment was carried out in an air atmosphere at a temperature of 300 ° C. for 3 hours to obtain a thin film resistor using the resistance thin film of Example 1 of the present invention.

4. Evaluation of thin-film resistors The obtained thin-film resistors were evaluated for specific resistance and high-temperature stability as follows.
The specific resistance was obtained by measurement by the four-probe method at room temperature.
The high temperature stability was evaluated by holding the obtained thin film resistor in a constant temperature bath at 155 ° C. for 1000 hours and calculating the resistance change rate (155 ° C., 1000 hours) from the resistance values measured before and after that. ..
The evaluation results of the thin film resistor are shown in Table 1 together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Example 2)
A sintered body of the mixed powder and a thin film resistor were obtained in the same manner as in Example 1 except that the amount of the SiO ₂ glass powder added was 3% by mass, and the characteristics thereof were measured. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Example 3)
A sintered body of the mixed powder and a thin film resistor were obtained in the same manner as in Example 1 except that the average particle size of the SiO ₂ glass powder was 30 μm, and the characteristics thereof were measured. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Example 4)
A sintered body of the mixed powder and a thin film resistor were obtained and their characteristics were measured in the same manner as in Example 1 except that the average particle size of the SiO ₂ glass powder was set to 200 μm. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Example 5)
A sintered body of the mixed powder and a thin film resistor were obtained in the same manner as in Example 1 except that the amount of the SiO ₂ glass powder added was 7% by mass, and the characteristics thereof were measured. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Example 6)
A sintered body of the mixed powder and a thin film resistor were obtained in the same manner as in Example 1 except that the amount of the SiO ₂ glass powder added was 10% by mass, and the characteristics thereof were measured. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Example 7)
A sintered body of the mixed powder and a thin film resistor were obtained in the same manner as in Example 1 except that the amount of the SiO ₂ glass powder added was 15% by mass, and the characteristics thereof were measured. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Example 8)
A sintered body of the mixed powder and a thin film resistor were obtained in the same manner as in Example 1 except that the amount of the SiO ₂ glass powder added was 20% by mass, and the characteristics thereof were measured. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Example 9)
A sintered body of the mixed powder and a thin film resistor were obtained and their characteristics were measured in the same manner as in Example 8 except that the average particle size of the SiO ₂ glass powder was set to 200 μm. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Comparative Example 1)
As a glass powder, 50% by mass of B, Ba, Mg, Ca, Zr, and Al are added to SiO ₂ glass in a total amount (B: Ba: Mg: Ca: Zr: Al = 2: 18: 5: 18: 5). : 2 (mass ratio)) The same as in Example 1 except that the SiO ₂ glass powder having an average particle size of 3 μm was used for mixing with the Ni alloy powder so that the addition amount was 20% by mass. A sintered body of mixed powder and a thin film resistor were obtained, and their characteristics were measured. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Comparative Example 2)
A sintered body of the mixed powder and a thin film resistor were obtained in the same manner as in Comparative Example 1 except that the average particle size of the SiO ₂ glass powder was set to 30 μm, and the characteristics thereof were measured. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Comparative Example 3)
A sintered body of the mixed powder and a thin film resistor were obtained and their characteristics were measured in the same manner as in Comparative Example 1 except that the average particle size of the SiO ₂ glass powder was 100 μm. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Comparative Example 4)
A sintered body of the mixed powder and a thin film resistor were obtained and their characteristics were measured in the same manner as in Comparative Example 1 except that the average particle size of the SiO ₂ glass powder was set to 200 μm. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Comparative Example 5)
A sintered body of the mixed powder and a thin film resistor were obtained and their characteristics were measured in the same manner as in Example 1 except that the average particle size of the SiO ₂ glass powder was 3 μm. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Comparative Example 6)
A sintered body of the mixed powder and a thin film resistor were obtained in the same manner as in Comparative Example 5, except that the amount of the SiO ₂ glass powder added was 3% by mass, and the characteristics thereof were measured. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Comparative Example 7)
A sintered body of the mixed powder and a thin film resistor were obtained in the same manner as in Comparative Example 5, except that the amount of the SiO ₂ glass powder added was 7% by mass, and the characteristics thereof were measured. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Comparative Example 8)
A sintered body of the mixed powder and a thin film resistor were obtained in the same manner as in Comparative Example 5, except that the amount of the SiO ₂ glass powder added was 10% by mass, and the characteristics thereof were measured. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Comparative Example 9)
A sintered body of the mixed powder and a thin film resistor were obtained in the same manner as in Comparative Example 5, except that the amount of the SiO ₂ glass powder added was 15% by mass, and the characteristics thereof were measured. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Comparative Example 10)
A sintered body of the mixed powder and a thin film resistor were obtained in the same manner as in Comparative Example 5, except that the amount of the SiO ₂ glass powder added was 20% by mass, and the characteristics thereof were measured. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size).

(Comparative Example 11)
A sintered body (sputtering target) of the mixed powder was obtained in the same manner as in Example 1 except that the amount of the SiO ₂ glass powder added was 30% by mass. However, when an attempt was made to form a resistance thin film using this sputtering target in the same manner as in Example 1, the film could not be formed because the conductivity of the target was insufficient. Table 1 shows the evaluation results together with the conditions of the glass powder (content, presence / absence of additives, average particle size). Since the thin film resistor could not be manufactured, the evaluation is indicated by "-".

As shown in Table 1, in the samples of Examples 1, 2, 4 to 9 having the constituent requirements of the present invention, the density ratio of the sintered body of the mixed powder was as high as 95.4% or more, and the glass powder was aggregated. It is recognized that the specific resistance of 525 μΩ · cm or more can be easily exhibited, and the resistance change rate is 0.09% or less, which is very stable even in high temperature storage at 155 ° C. for 1000 hours. The result was.
Further, the sample of Example 3 using the SiO ₂ glass powder whose average particle size is the lower limit of the range of the present invention, which is a sample satisfying the constituent requirements of the present invention, is a sintered body of a mixed powder. Although the density ratio was 94.5%, which was a relatively low value, there was no agglomeration of glass powder, the specific resistance was 530 μΩ · cm, and the resistivity change rate was 0.07%, which are the characteristics (ratio) required by the present invention. Resistance: 525 μΩ · cm or more, resistivity change rate: 0.1% or less) was confirmed to be satisfied.

On the other hand, the sample of Comparative Example 1 using a SiO ₂ -based glass containing an additive element such as B and having an average particle size of the glass powder smaller than the lower limit of the range of the present invention is a glass powder. The resistance change rate was 0.09%, which satisfied the characteristics required in the present invention (0.1% or less), but the density ratio increased only to 93.7%, and the specific resistance was 386 μΩ. The result was that it could not be made sufficiently high as cm.
Further, although the average particle size of the glass powder is within the range of the present invention, the samples of Comparative Examples 2 to 4 using the conventional SiO ₂ -based glass containing an additive element such as B do not aggregate the glass powder. However, the density ratio does not increase to 94.5% or less, the specific resistance cannot be sufficiently increased to 407 μΩ · cm, and the resistance change rate is required to be 0.11% or more in the present invention. As a result, it was confirmed that the specified characteristics (0.1% or less) were not satisfied.
Further, even when SiO ₂ glass containing no additive element is used, the samples of Comparative Examples 5 to 10 in which the average particle size of the glass powder is smaller than the lower limit of the range of the present invention have a density ratio of 92. Results showing a low value of 7% or less, agglomeration of glass powder, and a resistance change rate of 0.22% or more, indicating that the characteristics (0.1% or less) required by the present invention cannot be obtained. It became. In the samples of Comparative Examples 5 to 10, it is possible to increase the specific resistance by increasing the glass content, but the resistance change rate during high temperature storage also increases accordingly, which is preferable as a thin film resistor. do not have.
Further, in the sample of Comparative Example 11 in which only the content of the glass powder was contained more than the range of the present invention, the content of the Ni alloy powder was too small to obtain the conductivity required for sputtering, and the resistance was increased. The result was that it was not possible to form a thin film.

INDUSTRIAL APPLICABILITY The present invention is useful in a field where it is required to manufacture a thin film resistor used for an electronic component in a high temperature usage environment.

1 Alumina substrate 2 Resistance thin film 3 (Au) Electrode

Claims (6)

A pure Ni alloy powder containing 10% by mass or more and 60% by mass or less of one or more additive elements selected from Cr, Al and Y, and the balance consisting of Ni and unavoidable impurities, with an average particle size of 30 μm or more and 200 μm or less. It is a resistor material made of a sintered body of a mixed powder containing 3% by mass or more and 20% by mass or less of a glass powder made of SiO ₂ , and has a specific resistance of 525 μΩ when a resistance thin film is formed using the resistor material as a material. A resistor material having a characteristic of having a resistivity of cm or more and 1700 μΩ · cm or less and a resistivity change rate of 0.1% or less over time when the temperature of 155 ° C. is maintained for 1000 hours . A pure Ni alloy powder containing 10% by mass or more and 60% by mass or less of one or more additive elements selected from Cr, Al and Y, and the balance consisting of Ni and unavoidable impurities, with an average particle size of 30 μm or more and 200 μm or less. It is a sputtering target for forming a resistance thin film made of a sintered body of a mixed powder containing 3% by mass or more and 20% by mass or less of a glass powder made of SiO ₂ , and a resistance thin film is formed by using the sputtering target for forming a resistance thin film as a material. The resistivity thin film is characterized in that the specific resistance at the time is 525 μΩ · cm or more and 1700 μΩ · cm or less, and the resistance change rate with time when the temperature of 155 ° C. is maintained for 1000 hours is 0.1% or less. A sputtering target for forming. A pure Ni alloy powder containing 10% by mass or more and 60% by mass or less of one or more additive elements selected from Cr, Al and Y, and the balance consisting of Ni and unavoidable impurities, with an average particle size of 30 μm or more and 200 μm or less. A thin film formed from a sintered body of a mixed powder containing 3% by mass or more and 20% by mass or less of glass powder composed of SiO ₂ , having a specific resistance of 525 μΩ · cm or more and 1700 μΩ · cm or less, and 155 ° C. A resistance thin film having a resistivity change rate of 0.1% or less over time when the temperature is maintained for 1000 hours. A thin film resistor comprising an insulating material substrate, a resistance thin film formed on the insulating material substrate according to claim 3, and electrodes formed on both sides of the resistance thin film on the insulating material substrate. Glass powder consisting of pure SiO ₂ with an average particle size of 30 μm or more and 200 μm or less,
A Ni alloy powder having an average particle size of 10 μm or more and 200 μm or less, which contains 10% by mass or more and 60% by mass or less of one or more additive elements selected from Cr, Al and Y, and the balance is Ni and unavoidable impurities.
The glass powder is mixed so as to be 3% by mass or more and 20% by mass or less, the obtained mixed powder is molded into a desired shape, and the obtained molded product is 50 kg / cm in a vacuum or an inert atmosphere. A sintered body is produced by firing at a temperature of 1100 ° C. or higher and 1400 ° C. or lower under a pressure of ² or more, and the specific resistance when a resistance thin film is formed using the sintered body as a material is 525 μΩ · cm or more and 1700 μΩ · cm. The following is a method for manufacturing a sputtering target for forming a resistance thin film, which has a characteristic that the rate of change in resistance with time when the temperature of 155 ° C. is maintained for 1000 hours is 0.1% or less . Using the sputtering target according to claim 5, a thin film is formed on an insulating material substrate by a sputtering method, and the obtained thin film is subjected to a temperature of 200 ° C. or higher and 500 ° C. or lower in an atmosphere or an inert gas atmosphere. A method for producing a resistance thin film, which comprises performing a heat treatment for 1 hour or more and 10 hours or less.

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