TW201441399A - Manufacturing method of molybdenum alloy sputtering target materials and molybdenum alloy sputtering target materials - Google Patents

Abstract

A manufacturing method which stably and inexpensively provides molybdenum alloy sputtering target materials and a novel molybdenum alloy sputtering target material are provided. The molybdenum alloy sputtering target material has low resistance, and has excellent thermal resistance, moist resistance and adhesion to a substrate, and has high density and purity suitable for an electrode and a wiring film, and is nonmagnetic. The method is to mix a molybdenum powder with one kind or two kinds or more of nickel alloy powder in a manner of satisfying a composition containing 10 to 49 atom% of nickel and 1 to 30 atom% of titanium, wherein the total amount of nickel and titanium is 50 atom% or less, and the residues contain molybdenum and inevitable impurities and then pressure sintering. The molybdenum alloy sputtering target material has an organization in which the alloy phase of nickel is dispersed in the matrix of molybdenum, and is composed of 10 to 49 atom% of nickel and 1 to 30 atom% of titanium, wherein the total amount of nickel and titanium is 50 atom% or less, and the residues contain molybdenum and inevitable impurities.

Description

Method for manufacturing molybdenum alloy sputtering target and molybdenum alloy sputtering target

The present invention relates to a method for producing a molybdenum alloy sputtering target for forming an electrode for an electronic component and a wiring film, and a molybdenum alloy sputtering target.

A flat display device such as a liquid crystal display (Liquid Crystal Display: hereinafter referred to as LCD), a plasma display panel (hereinafter referred to as PDP), or an electrophoretic display used for electronic paper on a glass substrate ( In the thin-film electronic parts such as the FPD) and various semiconductor elements, thin film sensors, and magnetic heads, a low-resistance wiring film is required. For example, FPDs such as LCDs, PDPs, and organic EL displays require a low-impedance wiring film due to large screen, high detail, and high-speed reaction. In addition, in recent years, new products such as a touch panel that imparts maneuverability to an FPD and a flexible FPD that uses a resin substrate have been developed.

In recent years, thin film wiring (Thin Film Transistor: hereinafter referred to as TFT) used as a driving unit of an FPD has been required to be low-impedance, and research has been conducted to change the main wiring material from the past aluminum to the low-impedance copper.

At present, an amorphous germanium semiconductor film is used in the TFT, and copper as a main wiring film is used. Direct contact with ruthenium causes thermal diffusion due to a heating step in TFT fabrication, thereby deteriorating the characteristics of the TFT. Therefore, a laminated wiring film in which molybdenum or a molybdenum alloy excellent in heat resistance is used as a barrier film is used as a cover film between copper and tantalum.

In addition, the touch panel substrate screen that is directly operability while viewing the FPD screen is also being enlarged, and low-resistance copper is being used as a main wiring material.

Indium Tin Oxide (hereinafter referred to as ITO) which is a transparent conductive film is generally used for a position detecting electrode of a touch panel used in a pixel electrode, a portable terminal, or a tablet computer that is connected to a TFT. Although copper of the main wiring film can obtain contact with ITO, but has low adhesion to the substrate, in order to ensure adhesion, a laminated wiring film in which a base as a base film is covered with molybdenum or a molybdenum alloy is required.

Furthermore, the application of a transparent semiconductor film using an oxide capable of realizing a higher-speed reaction is being carried out from the amorphous germanium semiconductor film, and the copper of the main wiring film is also used in the wiring film of these oxide semiconductors. A molybdenum or molybdenum alloy is used as a laminate wiring film of a base film or a cover film. Therefore, the demand for thin film wiring composed of molybdenum or molybdenum alloy for forming these laminated wiring films is increasing.

As a low-resistance molybdenum alloy film excellent in heat resistance, corrosion resistance, and substrate adhesion, the present applicant has proposed to add 3 atom% to 50 atom% of vanadium to molybdenum, and further add nickel and copper to bismuth. Thin film wiring; an example of a thin film wiring formed of a composition of Mo-15 Nb-10 Ni (atomic %) is specifically disclosed in the examples (Patent Document 1). Further, the possibility of being a molybdenum alloy film of a novel Mo-Nb-Ti alloy having high moisture resistance was confirmed.

On the other hand, as a method of forming the above-described thin film wiring, a sputtering method using a sputtering target is most suitable. The sputtering method is one of physical vapor deposition methods, and is a method for stably forming a thin film wiring over a large area as compared with other vacuum evaporation or ion plating, and even if the alloy is added as described above, An effective method for obtaining an excellent film having a small composition variation can be obtained.

As a method of obtaining such a sputtering target, for example, as disclosed in Patent Document 2, there is proposed a method in which a raw material molybdenum powder, nickel powder, and a powder containing other additive elements (for example, cerium) are mixed. The mixed powder or the molybdenum alloy powder obtained by the atomization method is pressure-sintered, and the obtained sintered body is subjected to mechanical processing.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-140319

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-132974

In order to stably obtain a high-quality molybdenum alloy thin film, a sputtering target which is a base material of a molybdenum alloy thin film requires a uniform structure of high density, high purity, low gas composition, and segregation-free. In order to form such a structure, as proposed in Patent Document 2, it is desirable to use a molybdenum alloy powder obtained by alloying all component elements in advance.

However, since molybdenum is a high-melting-point metal, the molybdenum alloy containing molybdenum as a main component has a high melting point, and it is difficult to melt the molybdenum alloy powder produced by a general-purpose induction heating device and produced by a high-yield atomization method. In addition, since the melting point of the molybdenum alloy is high, There is a problem that if the particle size of the alloy powder is large, it is not easy to obtain a sintered body of high density; if the alloy powder is to be refined, impurities in the obtained sputtering target will increase.

In addition, if molybdenum is oxidized, its oxide is easily sublimated and vaporized before reaching the melting point of molybdenum. Therefore, in order to suppress oxidation of molybdenum in the process, it is necessary to melt a large and expensive apparatus controlled by the environment, thereby obtaining the obtained molybdenum alloy. Powder has also become an expensive product.

Further, when the molybdenum powder, the nickel powder, and the titanium powder are simply mixed as a raw material powder to obtain a mixed powder and subjected to pressure sintering, there is a problem that the alloying is insufficient and the sputtering target is insufficient. The residual nickel magnetic phase that is easily magnetic is reduced, the sputtering rate is lowered, or the life of the sputtering target is shortened.

An object of the present invention is to provide a method for producing a molybdenum alloy sputtering target which can stably and inexpensively, and a novel molybdenum alloy sputtering target which has low resistance, heat resistance and moisture resistance. It is also a high-density, high-purity, non-magnetic target suitable for the formation of electrodes and wiring films, which is also excellent in adhesion to substrates.

In view of the above problems, the inventors of the present invention have conducted intensive studies on a molybdenum alloy sputtering target having a high melting point molybdenum as a main component. As a result, by optimizing the properties of the powder of the main component molybdenum, it has been found that a method of producing a high-density and high-purity molybdenum alloy sputtering target can be stably and inexpensively manufactured, and the present invention has been completed. The molybdenum alloy sputtering target is used for a high-quality film excellent in low electric resistance, heat resistance, moisture resistance, and substrate adhesion.

That is, the present invention is a method for producing a molybdenum alloy sputtering target, which contains 10 atom% to 49 atom% of nickel, 1 atom% to 30 atom% of titanium, and the total amount of nickel and titanium is 50 atom%. Hereinafter, the remaining portion is a method for producing a molybdenum alloy sputtering target comprising molybdenum and unavoidable impurities, wherein the molybdenum powder is mixed with at least one or two or more kinds of nickel alloy powders to satisfy the above composition, and then carried out Pressure sintering.

The above nickel alloy powder preferably contains a Ni-Mo alloy and is further added by adding titanium powder. Further, the above Ni-Mo alloy powder preferably contains 8 atom% to 40 atom% of molybdenum.

Further, the present invention is a molybdenum alloy sputtering target which contains 10 atom% to 49 atom% of nickel, 1 atom% to 30 atom% of titanium, and the total amount of nickel and titanium is 50 atom% or less, and the remainder Part of the molybdenum alloy sputtering target consisting of molybdenum and unavoidable impurities, and having a structure in which a nickel alloy phase is dispersed in a matrix of molybdenum.

In the molybdenum alloy sputtering target of the present invention, preferably, the nickel alloy phase comprises one or more selected from the Ni-Mo alloy phase and the Ni-Ti alloy phase, more preferably an interface between the nickel alloy phase and the molybdenum substrate. Has a diffusion layer.

The present invention can stably and inexpensively produce a high-density, high-purity, non-magnetic molybdenum alloy sputtering target, and can provide low resistance, heat resistance, moisture resistance, and excellent adhesion to a substrate, and is suitable for an electrode and a wiring film. The formation of a molybdenum alloy sputter target. Therefore, the present invention is a technique useful for improving the manufacturing and reliability of electronic components.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of a photograph of a microstructure of a molybdenum alloy sputtering target observed by an optical microscope of the present invention.

Fig. 2 is another example of a photograph of the microstructure of a molybdenum alloy sputtering target observed by an optical microscope of the present invention.

Fig. 3 is another example of a photograph of the microstructure of a molybdenum alloy sputtering target observed by an optical microscope of the present invention.

4 is an example of a photograph of FIG. 3 observed at a high magnification.

As described above, the alloy having molybdenum as a main component has a high melting point, and it is difficult to form a powder by alloying by the atomization method used in the prior art, and various problems are obtained when the sputtering target is stably and inexpensively obtained. .

An important feature of the production method of the present invention is that the high-melting-point molybdenum alloy is not melted, and the molybdenum powder is mixed with a specific nickel alloy powder, followed by pressure sintering.

First, the powder used in the production method of the present invention will be described. As the molybdenum powder used in the present invention, a commercially available molybdenum powder which is easily available can be used. When the average particle diameter of the molybdenum powder is less than 1 μm, impurities in the obtained sputtering target increase, and if it exceeds 50 μm, it is difficult to obtain a sintered body having a high density. Therefore, the range of the average particle diameter of the molybdenum powder is preferably 1 μm to 50 μm. Further, in order to form a matrix of molybdenum in the sputtering target, it is preferable to mix 50 atom% or more of molybdenum powder in total.

As the nickel alloy powder used in the production method of the present invention, for example, a powder of Ni-Mo alloy powder, Ni-Ti alloy powder or Ni-Mo-Ti alloy can be used. As a result, since the melting point of each of the nickel alloy powders is lower than the melting point of the molybdenum, the production of the alloy powder and the sintering of the mixed powder can easily improve the fineness of the sintered body. These nickel alloy powders can be easily obtained by an atomization method to form an alloy having a predetermined composition ratio. Further, it is also possible to produce a nickel alloy powder by performing melt-pulverization. Further, when a nickel alloy powder not containing titanium is used, titanium powder is added and mixed to form a component of the present invention.

If the average particle diameter of the nickel alloy powder is less than 5 μm, impurities in the obtained sputtering target increase. On the other hand, when the nickel alloy powder exceeds 300 μm, it is difficult to obtain a sintered body having a high density. Therefore, the range of the average particle diameter of the nickel alloy powder is preferably 5 μm to 300 μm.

Further, the average particle diameter described in the present invention is defined by JIS Z 8901, and is represented by a Sphere-equivalent diameter obtained by a light scattering method using laser light.

Further, the nickel alloy powder used in the production method of the present invention is non-magnetic and does not impair the sinterability, and it is preferred to select the above-mentioned elements and the added amount. Therefore, since nickel is a magnetic substance as described above, if the amount of nickel added is increased, a nickel ferromagnetic phase which is easily magnetically retained in the sputtering target remains, and magnetron sputtering which is commonly used for the production of FPD is used. In plating, the speed of sputtering may be lowered, and the life of the sputtering target may be shortened. In the present invention, a nickel alloy powder is used in order to disperse the structure of the nonmagnetic nickel alloy phase in the matrix of molybdenum. According to the present invention, a sputtering target having excellent sputtering properties can be obtained.

The nickel alloy powder used in the production method of the present invention is preferably a Ni-Mo alloy powder which is alloyed with nickel and molybdenum, and preferably has a molybdenum content of 8 atom% to 40 atom%. Ni-Mo in this composition range has a lower melting point than nickel and can be easily obtained by atomization. The reason for setting this composition range is as follows: if the molybdenum content of the nickel alloy powder is less than 8 atom%, it is very difficult to be non-magnetized; on the other hand, if the content of molybdenum exceeds 40 atom%, many nickel molybdenum which is easily embrittled is found. The compound phase is likely to contain cracks in the compound phase, and defects are likely to remain in the sputtering target. The nickel alloy powder used in the production method of the present invention has a molybdenum content of preferably 30 atom% or less, and the nickel molybdenum compound phase is hardly found.

Further, a Ni-Ti alloy may be used as the nickel alloy powder used in the production method of the present invention. At this time, the titanium content of the Ni-Ti alloy powder is preferably 10 atom% or more. Thereby, a non-magnetic molybdenum alloy sputtering target can be obtained. On the other hand, when the amount of titanium added to the Ni-Ti alloy powder exceeds 50 atom%, a phase having a melting point of 1000 ° C or less is easily found. Since the liquid phase is found, it is necessary to lower the sintering temperature. In this case, in order to increase the relative density of the sputtering target, it is necessary to lengthen the sintering time to lower the productivity. Therefore, the Ni content of the Ni-Ti alloy powder used in the production method of the present invention is preferably 50 atom% or less. Further, in order to increase the relative density of the sputtering target and to increase the sintering time, the Ti content of the Ni-Ti alloy powder is more preferably 25 atom% or less.

In the method for producing a molybdenum alloy sputtering target of the present invention, the molybdenum powder is mixed with one or two or more kinds of nickel alloy powders in accordance with a target composition, and then subjected to pressure sintering to obtain high density and high purity. Molybdenum alloy sputtering target.

The pressure sintering can be performed by hot isostatic pressing (hereinafter referred to as HIP) and hot pressing (Hot press), preferably at 1000 to 2000 ° C, 10 to 200 MPa, and 1 to 10 hours. The choice of these conditions depends on the device for pressure sintering. For example, HIP is easy to apply to low temperature and high pressure conditions, and hot pressing is easy to apply to high temperature and low pressure conditions. In the production method of the present invention, at the time of pressure sintering, the diffusion of the nickel alloy and the titanium can be suppressed by sintering at a low temperature, and it is preferable to use a HIP which can obtain a sintered body having a high density by high-pressure sintering.

When the sintering temperature is less than 1000 ° C, sintering is difficult to proceed, and a sintered body having a high density cannot be obtained. On the other hand, when the sintering temperature exceeds 1500 ° C, the liquid phase is found, the crystal growth of the sintered body is not remarkable, and it is difficult to obtain a uniform fine structure. Further, since the melting point of the Ni-Mo alloy having the above composition range is 1300 ° C or higher and sintered in the range of 1000 to 1300 ° C, a high-density molybdenum alloy sputtering target can be easily obtained.

Further, when the pressure is 10 MPa or less, sintering is difficult and it is difficult to obtain a sintered body having a high density. On the other hand, if the pressure exceeds 200 MPa, there is a problem that the durable device is limited.

Further, it is difficult to sufficiently perform sintering for a sintering time of 1 hour or less, and it is difficult to obtain a sintered body having a high density. On the other hand, if the sintering time exceeds 10 hours, it is still better to avoid the manufacturing efficiency.

When pressure-sintering is performed by HIP and hot pressing, it is preferred to fill the mixed powder into a pressurizing vessel or a press-molding die for pressurization, and then depressurize the gas while heating. The degassing under reduced pressure is preferably carried out at a heating temperature of from 100 to 600 ° C under a reduced pressure of less than atmospheric pressure (101.3 kPa). This is because the oxygen of the obtained sintered body can be further reduced Gas, and can obtain high purity molybdenum alloy sputtering target.

Next, the molybdenum alloy sputtering target of the present invention will be described. The molybdenum alloy sputtering target of the present invention has 10 atom% to 49 atom% of nickel and 1 atom% to 30 atom% of titanium, and the total amount of nickel and titanium is 50 atom% or less, and the remaining portion contains molybdenum and is not Impurities avoided, and having a structure in which a nickel alloy phase is dispersed in a matrix of molybdenum. Here, the nickel alloy phase means a Ni-Mo alloy phase, a Ni-Ti alloy phase, and a Ni-Ti-Mo alloy phase.

In the molybdenum alloy sputtering target of the present invention, the nickel alloy phase preferably includes one or more selected from the group consisting of a Ni-Mo alloy phase and a Ni-Ti alloy phase. When nickel is present alone in the molybdenum alloy sputtering target, nickel is a magnetic material, which causes the problem of stability at the time of the above sputtering and short life of the sputtering target. The molybdenum alloy sputtering target of the present invention is stably dispersed by forming a structure in which nickel is used as a so-called non-magnetic Ni-Mo alloy phase or a nickel-phase phase of a Ni-Ti alloy phase in a matrix of molybdenum. At the same time as plating, a uniform Mo alloy film can be formed on the substrate.

Further, the molybdenum alloy sputtering target of the present invention preferably has a diffusion layer on the interface between the nickel alloy and the molybdenum substrate. Thereby, a high-density molybdenum alloy sputtering target having few defects is formed, and the height of the unevenness generated in the eroded area formed by the surface erosion of the sputtering target at the time of sputtering can be reduced. This result has an effect of suppressing abnormal discharge, sputtering, and the like, and stably forming a molybdenum alloy film having no defects.

In the molybdenum alloy sputtering target of the present invention, the reason for adding nickel or titanium to the molybdenum is to improve the heat resistance and the moisture resistance when forming a film which is laminated with copper or aluminum of the main wiring film. And the adhesion when forming a film as a base film.

When the amount of nickel added is less than 10 atom%, the oxidation inhibiting effect is insufficient. On the other hand, compared with molybdenum, nickel is an element which is easily diffused into copper or aluminum, and if it is a nickel-rich alloy, it tends to diffuse to copper or aluminum of the main wiring film, and in order to increase the resistance value, nickel The amount of addition is set to 49 atom% or less.

Further, when the amount of titanium added is less than 1 atom%, the effect of improving moisture resistance cannot be obtained. On the other hand, when the amount of addition of titanium exceeds 30 atom%, the effect of improving the moisture resistance is saturated, and the etching property is lowered, and it is desirable that the amount of addition is as small as possible. Therefore, the amount of titanium added to the molybdenum alloy sputtering target of the present invention is set to be 1 atom% to 30 atom%. Further, compared with molybdenum, since titanium is also an element which is easily diffused toward copper or aluminum of the main wiring film, the amount of nickel added in the present invention is set to 10 atom% to 49 atom%, and the total amount of nickel and titanium is 50. Below atomic %.

Further, copper of the main wiring film is inferior in oxidation resistance and moisture resistance as compared with aluminum. When the molybdenum alloy film formed by the molybdenum alloy sputtering target of the present invention is used as a cover film, in order to sufficiently ensure oxidation resistance and moisture resistance, the amount of nickel added is preferably 20 atom% or more. The amount of titanium added is set to 10 atom% or more. Therefore, the molybdenum alloy sputtering target of the present invention has a more preferable range of 20 atom% to 35 atom% of nickel and 10 atom% to 20 atom% of titanium. In addition, the aluminum of the main wiring film is excellent in oxidation resistance and moisture resistance, and since nickel and titanium are more likely to be thermally diffused than copper, the amount of nickel added is preferably 25 atom% or less, and the amount of titanium added is set. It is 15 atom% or less. Therefore, the molybdenum alloy sputtering target of the present invention is preferably added in the range of 10 atom% to 25 atom% of nickel and 3 atom% to 15 atom% of titanium.

In addition, the molybdenum alloy sputtering target of the present invention preferably has a main component of molybdenum and There are as few elements as possible other than nickel and titanium. When there are many impurities other than the main component, the electric resistance of the film increases, or the other laminated film reacts depending on the type of the element, and the properties such as adhesion, moisture resistance, and oxidation resistance are deteriorated. In particular, oxygen or nitrogen of the gas component is easily introduced into the film to lower the adhesion or cause defects in the film. Therefore, the molybdenum alloy sputtering target of the present invention has a purity of 99.9% or more, and preferably has an impurity such as oxygen of 1000 ppm by mass or less, more preferably 400 ppm by mass or less of impurities such as oxygen.

[Example 1]

In order to produce a molybdenum alloy sputtering target having an atomic ratio of 20% nickel to 15% titanium and the remainder being molybdenum and unavoidable impurities, a molybdenum powder having a purity of 99.99% and an average particle diameter of 6 μm is prepared, and A Ni-30 atomic% molybdenum alloy powder having a purity of 99.9%, an average particle diameter of 70 μm, and a titanium powder having a purity of 99.8% and an average particle diameter of 30 μm were produced by an atomization method.

The powder was weighed in such a manner as to be a composition of the molybdenum alloy sputtering target described above, and mixed by a cross-rotating mixer to obtain a mixed powder. Thereafter, the container was filled in a mild steel container having an inner diameter of 133 mm, a height of 30 mm, and a thickness of 3 mm, and heated at 450 ° C for 10 hours, and then subjected to degassing treatment, and then the soft steel container was sealed, and then HIP device was used. Sintering was carried out at 1000 ° C and 148 MPa for 5 hours. After cooling, it was taken out from the HIP apparatus, and the soft steel container was removed by mechanical processing to obtain a molybdenum alloy sputtering target having a diameter of 100 mm and a thickness of 5 mm, and the test piece was cut out from the remaining portion.

Further, for comparison, an atomic ratio was prepared by a dissolution method. 20% nickel-15% titanium - the remaining part is a molybdenum alloy composed of molybdenum and unavoidable impurities, but the molybdenum is dissolved and cannot be used to make a normal alloy ingot.

The relative density of the obtained test piece was measured by the Archimedes method, and as a result, it was 99.9%. It was confirmed that the high-density molybdenum alloy sputtering target can be obtained according to the production method of the present invention. The relative density referred to herein refers to a value obtained by multiplying the total density divided by the theoretical density by 100 by the Archimedes method, which is obtained as a composition for sputtering a target from a molybdenum alloy. The theoretical density obtained by the weighted average of the calculated elemental masses than the obtained mass.

In addition, the inductively coupled plasma (ICP) (model number: ICPV-1017) manufactured by Shimadzu Corporation was used for quantitative analysis of the metal elements of the obtained test piece, and by non-dispersion When the amount of oxygen was determined by the infrared absorption method, the total purity of the analysis values of molybdenum, nickel, and titanium was 99.9%, and the oxygen concentration was 350 ppm by mass. It was confirmed that the high-purity molybdenum alloy can be obtained by the production method of the present invention. Sputter target.

The test piece obtained above was subjected to mirror polishing, and then etched by a nitric acid etching solution (nital), and the results of observation by a light microscope were shown in Fig. 1. As shown in FIG. 1, the molybdenum alloy sputtering target of the present invention has a spherical Ni-Mo alloy phase dispersed in a matrix of fine recrystallized molybdenum, and is in the vicinity of a matrix of molybdenum. The interface having the diffusion layer was not confirmed to have large defects such as segregation or voids, and it was confirmed that it was a sputtering target suitable for sputtering film formation.

In addition, the above-obtained molybdenum alloy sputtering target having a diameter of 100 mm and a thickness of 5 mm was welded to a copper backing plate and mounted on the back plate. It was sprayed on a sputtering apparatus manufactured by Canon Anelva Co., Ltd. (model number: SPF-440HL), and then sputtered in an Ar environment at a pressure of 0.5 Pa and a power of 500 W. It has been confirmed that if the molybdenum alloy sputtering target of the present invention is used for sputtering, no abnormal discharge is caused, and stable sputtering can be performed.

A sample of a molybdenum alloy film having a film thickness of 200 nm was formed on a 25 mm × 50 mm glass substrate manufactured by Corning Co., Ltd. (product number: Eagle XG) under the above-described sputtering conditions, and adhesion and resistance were evaluated. Humidity and heat resistance.

The evaluation of the adhesion was carried out by the method specified in JIS K5400. First, a transparent adhesive tape (product name: transparent beauty) manufactured by Sumitomo 3M Co., Ltd. was attached to the above-mentioned molybdenum alloy film, and a square of 2 mm square was processed with a utility knife, and then the transparent adhesive tape was peeled off. The evaluation was carried out with or without the presence of a film. It was confirmed that the film formed by using the molybdenum alloy sputtering target of the present invention was not peeled off, and had high adhesion.

The moisture resistance was evaluated by allowing the above-mentioned molybdenum alloy film to stand in an environment of a temperature of 85 ° C and a humidity of 85% for 300 hours, and visually confirming the presence or absence of discoloration on the surface of the molybdenum alloy film. It was confirmed that the film formed by using the molybdenum alloy sputtering target of the present invention does not discolor even when exposed to a high-temperature and high-humidity environment, and has high moisture resistance.

The heat resistance was evaluated by heating the above-mentioned molybdenum alloy film in an atmosphere at 350 ° C for 30 minutes in the air, and visually confirming the presence or absence of discoloration of the molybdenum alloy film. It was confirmed that the film formed by using the molybdenum alloy sputtering target of the present invention does not discolor even when heated at a high temperature, and has high heat resistance.

[Example 2]

In order to produce a molybdenum alloy sputtering target having an atomic ratio of 15% nickel to 15% titanium and the remainder being molybdenum and unavoidable impurities, molybdenum powder having a purity of 99.99% and an average particle diameter of 6 μm is prepared, and A titanium alloy powder of Ni-50 atom% having a purity of 99.9% and an average particle diameter of 60 μm produced by an atomization method.

The powder was weighed in such a manner as to be a composition of the molybdenum alloy sputtering target described above, and mixed by a cross-rotating mixer to obtain a mixed powder. Thereafter, the container was filled in a mild steel container having an inner diameter of 133 mm, a height of 30 mm, and a thickness of 3 mm, and heated at 450 ° C for 10 hours, and then subjected to degassing treatment, and then the soft steel container was sealed, and then HIP device was used. Sintering was carried out at 1000 ° C and 148 MPa for 5 hours. After cooling, it was taken out from the HIP apparatus, and the soft steel container was removed by mechanical processing to obtain a molybdenum alloy sputtering target having a diameter of 100 mm and a thickness of 5 mm, and the test piece was cut out from the remaining portion.

The relative density of the obtained test piece was measured by the Archimedes method and found to be 98.7%. It was confirmed that the high-density molybdenum alloy sputtering target can be obtained by the production method according to the present invention.

Further, quantitative analysis of the metal element of the obtained test piece was carried out under the same conditions as in Example 1, and the amount of oxygen was measured by a non-dispersive infrared absorption method, and as a result, the total of the analysis values of molybdenum, nickel, and titanium was obtained. The purity was 99.9%, and the oxygen concentration was 400 ppm by mass. It was confirmed that the high-purity molybdenum alloy sputtering target can be obtained by the production method of the present invention.

After the mirror piece obtained by the above-mentioned test piece was mirror-polished, it was etched by the nitric acid etching agent (nital), and the result of the structure observation by the optical microscope was shown. In Figure 2. As shown in FIG. 2, the molybdenum alloy sputtering target of the present invention has a substantially spherical Ni-Mo alloy phase having a dispersion of about 10 μm in a matrix of fine recrystallized molybdenum, and is in a matrix with molybdenum. The interface was only the structure of the diffusion layer, and large defects such as segregation or voids were not confirmed, and it was confirmed that it was a sputtering target suitable for sputtering film formation.

Further, in the same manner as in Example 1, the above-obtained molybdenum alloy sputtering target having a diameter of 100 mm and a thickness of 5 mm was welded to a copper backing plate, and then mounted on Canon Anelva. The sputtering apparatus manufactured by Co., Ltd. (model number: SPF-440HL) was then sputtered in an Ar environment at a pressure of 0.5 Pa and a power of 500 W. It has been confirmed that if the molybdenum alloy sputtering target of the present invention is used for sputtering, no abnormal discharge is caused, and stable sputtering can be performed.

A sample of a molybdenum alloy film having a film thickness of 200 nm was formed on a 25 mm × 50 mm glass substrate manufactured by Corning Co., Ltd. (product number: Eagle XG) under the above-described sputtering conditions, and adhesion and resistance were evaluated. Humidity and heat resistance.

The evaluation of the adhesion was carried out by the same method as in Example 1. It was confirmed that the film formed by using the molybdenum alloy sputtering target of the present invention was not peeled off, and had high adhesion.

The evaluation of moisture resistance was carried out by the same method as in Example 1. It was confirmed that the film formed by using the molybdenum alloy sputtering target of the present invention does not discolor even when exposed to a high-temperature and high-humidity environment, and has high moisture resistance.

The evaluation of heat resistance was carried out by the same method as in Example 1. It was confirmed that the film formed by using the molybdenum alloy sputtering target of the present invention does not discolor even when heated at a high temperature, and has high heat resistance.

[Example 3]

In order to prepare a molybdenum alloy sputtering target having an atomic ratio of 40% nickel-10% titanium and the remainder being molybdenum and unavoidable impurities, a molybdenum powder having a purity of 99.99% and an average particle diameter of 6 μm is prepared, and borrowed. A titanium alloy powder of Ni-40 atom% having a purity of 99.9% and an average particle diameter of 55 μm and a Ni-20 atom% of a molybdenum alloy powder having an average particle diameter of 65 μm were produced by an atomization method.

The powder was weighed in such a manner as to be a composition of the molybdenum alloy sputtering target described above, and mixed by a cross-rotating mixer to obtain a mixed powder. Thereafter, the container was filled in a mild steel container having an inner diameter of 133 mm, a height of 30 mm, and a thickness of 3 mm, and heated at 450 ° C for 10 hours, and then subjected to degassing treatment, and then the soft steel container was sealed, and then HIP device was used. Sintering was carried out at 1000 ° C and 148 MPa for 5 hours. After cooling, it was taken out from the HIP apparatus, and the soft steel container was removed by mechanical processing to obtain a molybdenum alloy sputtering target having a diameter of 100 mm and a thickness of 5 mm, and the test piece was cut out from the remaining portion.

The relative density of the obtained test piece was measured by the Archimedes method, and as a result, it was 99.9%. It was confirmed that the high-density molybdenum alloy sputtering target can be obtained according to the production method of the present invention.

Further, quantitative analysis of the metal element of the obtained test piece was carried out under the same conditions as in Example 1, and the amount of oxygen was measured by a non-dispersive infrared absorption method, and as a result, the total of the analysis values of molybdenum, nickel, and titanium was obtained. The purity was 99.9%, and the oxygen concentration was 350 ppm by mass. It was confirmed that the high-purity molybdenum alloy sputtering target can be obtained by the production method of the present invention.

The test piece obtained above was subjected to mirror polishing, and then etched by a nitric acid etching solution (nital), and the results of observation by a light microscope were shown in Fig. 3 and Fig. 4 at a high magnification. As shown in FIG. 3 and FIG. 4, the molybdenum alloy sputtering target of the present invention has a Ni-Mo alloy phase and a substantially spherical Ni-Ti dispersed in a matrix of fine recrystallized molybdenum. The alloy phase had a structure in which a diffusion layer was formed on the interface with the matrix of molybdenum, and no large defects such as segregation or voids were observed, and it was confirmed that this was a sputtering target suitable for sputtering film formation.

Further, in Example 3, as compared with Example 1 and Example 2, it is understood that the amount of molybdenum diffusion is increased because the amount of molybdenum and titanium added in the nickel alloy is small.

Next, the above-obtained molybdenum alloy sputtering target having a diameter of 100 mm and a thickness of 5 mm was welded to a copper backing plate, and then mounted on a Canon Anelva Co., Ltd. (model No. SPF-440HL) was sputtered on a sputtering apparatus, and then subjected to sputtering in an Ar environment at a pressure of 0.5 Pa and a power of 500 W. It has been confirmed that if the molybdenum alloy sputtering target of the present invention is used for sputtering, no abnormal discharge is caused, and stable sputtering can be performed.

A sample of a molybdenum alloy film having a film thickness of 200 nm was formed on a 25 mm × 50 mm glass substrate manufactured by Corning Co., Ltd. (product number: Eagle XG) under the above-described sputtering conditions, and adhesion and resistance were evaluated. Humidity and heat resistance.

The evaluation of the adhesion was carried out by the same method as in Example 1. It was confirmed that the film formed by using the molybdenum alloy sputtering target of the present invention was not peeled off, and had high adhesion.

The evaluation of moisture resistance was carried out by the same method as in Example 1. Can be sure It is considered that a film formed by using the molybdenum alloy sputtering target of the present invention does not discolor even when exposed to a high-temperature and high-humidity environment, and has high moisture resistance.

The evaluation of heat resistance was carried out by the same method as in Example 1. It was confirmed that the film formed by using the molybdenum alloy sputtering target of the present invention does not discolor even when heated at a high temperature, and has high heat resistance.

Claims (6)

A method for producing a molybdenum alloy sputtering target, characterized in that the composition of the molybdenum alloy sputtering target contains 10 atom% to 49 atom% of nickel, 1 atom% to 30 atom% of titanium, and nickel and titanium The total amount is 50 atom% or less, and the remainder contains molybdenum and unavoidable impurities. The molybdenum powder is mixed with at least one or two or more kinds of nickel alloy powders to satisfy the above composition, followed by pressure sintering. A method for producing a molybdenum alloy sputtering target, characterized in that the composition of the molybdenum alloy sputtering target contains 10 atom% to 49 atom% of nickel, 1 atom% to 30 atom% of titanium, and nickel and titanium The total amount is 50 atom% or less, and the remainder contains molybdenum and unavoidable impurities; the molybdenum powder, the nickel-molybdenum alloy powder and the titanium powder are mixed in such a manner as to satisfy the above composition, followed by pressure sintering. The method for producing a molybdenum alloy sputtering target according to claim 2, wherein the nickel-molybdenum alloy powder contains 8 atom% to 40 atom% of molybdenum. A molybdenum alloy sputtering target characterized in that: the composition of the molybdenum alloy sputtering target contains 10 atom% to 49 atom% of nickel, 1 atom% to 30 atom% of titanium, and the total amount of nickel and titanium The content is 50 atom% or less, and the remainder contains molybdenum and unavoidable impurities; and has a structure in which a nickel alloy phase is dispersed in a matrix of molybdenum. The molybdenum alloy sputtering target according to claim 4, wherein the nickel alloy phase is at least one selected from the group consisting of a nickel-molybdenum alloy phase and a nickel-titanium alloy phase. The molybdenum alloy sputtering target according to claim 4, wherein the diffusion layer is provided in an interface between the nickel alloy phase and the matrix of the molybdenum.