TW201513744A - Laminated wiring film and method for producing the same and nickel alloy sputtering target - Google Patents

Abstract

The invention provides a novel laminated wiring film which executes stable wet etching, and meets the requirement of low reflection of an electrode or a wiring film for improving display quality of a high-definition planar display device. Besides, the invention provides a nickel alloy sputtering target for forming a nickel alloy film. The nickel alloy film functions as a low-reflective intermediate film. A laminated wiring film is provided, which has a laminated structure. In the laminated structure, the intermediate film including a nickel alloy having a film thickness of 20 nm to 100 nm is formed on a transparent substrate or a transparent substrate having a transparent film formed thereon, and a conductive film having a specific resistance of 150 [mu] [Omega] cm or less is formed right above the intermediate film. A reflectance of visible light measured from a side of the transparent substrate is 20% or less.

Description

Laminated wiring film, manufacturing method thereof and nickel alloy sputtering target

The present invention relates to a laminated wiring film used for an electrode film or a wiring film for a flat display device, which is required to have low reflection characteristics, a method for producing the same, and a nickel for forming a low reflection film (hereinafter referred to as "Ni"). Alloy sputtering target.

A liquid crystal display (hereinafter referred to as "LCD"), a plasma display panel (hereinafter referred to as "PDP"), an electronic paper, or the like which forms a thin film element on a transparent glass substrate or the like is used. A flat panel display device (hereinafter referred to as "FPD") such as an electrophoretic display device requires a low resistance value for a wiring film in accordance with a large screen, high definition, and high speed response. Further, in recent years, new types of products such as a touch panel that adds operability to an FPD or a flexible FPD that uses a transparent resin substrate or an extremely thin glass substrate have been developed.

In recent years, a wiring film of a thin film transistor (hereinafter referred to as "TFT") used as a driving element of an FPD requires a low resistance value in order to achieve the above-described high performance, and Al or Cu is used as a main wiring film. s material.

When a Si semiconductor film is used for a TFT, when Al or Cu as a main wiring material is in direct contact with Si, heat is diffused due to a heating step in the production of the TFT, and the characteristics of the TFT are deteriorated. Therefore, a laminated wiring film in which pure Mo or a Mo alloy having excellent heat resistance is used as a barrier film is provided between the main wiring film of Al or Cu and Si of the semiconductor film. Further, as the pixel electrode to be connected to the wiring film, a film of Indium-Tin Oxide (hereinafter referred to as "ITO") as a transparent conductive film is generally used.

Moreover, the touch panel substrate screen which gives direct operability while viewing the FPD screen is also enlarged, and is used in a smart phone, a personal computer (PC), a desktop PC, or the like. Products that perform touch panel operations are also becoming popular. The position detecting electrode of the touch panel generally uses an ITO film of a transparent conductive film.

In recent years, in the capacitive touch panel capable of multi-point detection, a general-purpose diamond arrangement in which a quadrangular ITO film is disposed is used, and a metal film is also used in an electrode or a wiring film that connects the quadrilateral ITO film. A Mo alloy or a laminated film of Mo alloy and Al which is easy to obtain contact with an ITO film is used for the metal film.

The present applicant has proposed a metal film containing 3 to 50 atom% of V or Nb in Mo, and further adding a metal film of Ni or Cu as a low-resistance metal film excellent in heat resistance, corrosion resistance, or adhesion to a substrate. (Patent Document 1)

On the other hand, in order to protect the surface of the low-resistance Cu main wiring film, a laminated wiring film coated with a Ni-Cu alloy has been proposed. (for example, Patent Document 2 and Patent Document 3)

[Prior Art Literature] [Patent Literature]

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

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-52304

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2006-310814

It is a high-definition mobile phone that replaces the full-size high-fidelity (Full Hi-Vision) with 4x pixels in recent years or a smart phone with a close-up operation display of about 10cm from the viewpoint. Chemical. With this high definition, new problems such as deterioration of display quality due to reflection of incident light by the metal film become remarkable. Therefore, the demand for a new characteristic (hereinafter referred to as "low reflection") such as a low reflectance of the metal film is rapidly increased.

Further, the Al film used in the wiring film of the flat display element is a metal having a high reflectance of 90% or more in the visible light region. Further, the Cu film used in the wiring film of the flat display element has a reflectance of 70% in the visible light region and a high reflectance of 95% or more in the long wavelength region of 600 nm or more.

On the other hand, the Mo film or the Mo alloy film laminated to protect the wiring films has a reflectance of about 60%. Since these metal films do not substantially change in reflectance even after passing through the manufacturing process of the flat display device, reflection of the metal film is a factor which causes deterioration in display quality particularly in a high-definition display device. As above In the high-definition display device described above, an electrode or a wiring film having a lower reflection of about 30% or less of about half of a Mo film or the like is required.

As described above, a wiring film or a laminated wiring film using various materials has been developed so far. However, these patent documents have been studied as a barrier property or a protective property of a wiring film or a coating layer. Further, in these patent documents, no new research has been conducted on new characteristics such as low reflection required to cope with future high-definition display devices.

In addition, in the case of the wet etching of the laminated wiring film in which the coating layer containing the Ni alloy disclosed in the above-mentioned Patent Document 2 or Patent Document 3 is wet-etched, the following is also the case. Problem: In the surface of the substrate, the etching of the coating layer containing the Ni alloy is uneven, and unevenness is likely to occur, and the wiring width is uneven.

It is an object of the present invention to provide a novel laminated wiring film which is capable of performing stable wet etching and which is required to have low reflection of an electrode or a wiring film required for improving display quality of a high-definition flat display element, and A Ni alloy sputtering target for forming a Ni alloy film which functions as a low reflection intermediate film is provided.

In view of the above-described problems, the present inventors have studied various alloy films and laminated films in order to obtain new characteristics such as low reflection in addition to stable wet etching properties in the production steps of a flat display device or a touch panel. As a result, it was found that an interlayer film containing a Ni alloy and a conductive film were laminated on a transparent substrate or formed transparent. On the transparent substrate of the film, a low-reflection laminated wiring film can be obtained, thereby completing the present invention.

That is, the present invention is an invention of a laminated wiring film having a laminated structure in which an intermediate film including a Ni alloy and having a film thickness of 20 nm to 100 nm is formed on a transparent substrate or a transparent substrate on which a transparent film is formed. A conductive film having a specific resistance of 150 μΩcm or less is formed directly above the intermediate film, and the visible light reflectance measured from the transparent substrate side is 20% or less.

Preferably, the conductive film is mainly composed of an element selected from the group consisting of Al, Cu, Mo, Ni, and Ag, and has a film thickness of 10 nm to 500 nm.

It is preferable that the intermediate film contains a total of 15 atom% to 60 atom% of one or more elements selected from the group consisting of Cu, Mn, Mo, and Fe, and the remainder contains Ni and unavoidable impurities.

Further, it is preferable that the intermediate film contains 10 atom% to 40 atom% of Cu, and 3 atom% to 20 atom% of Mo, and the total amount of Cu and Mo is 15 atom% to 50 atom%, and the remainder includes Ni and inevitable impurities.

Further, it is more preferable that the intermediate film contains 1 atom% to 25 atom% of Mn, and 3 atom% to 30 atom% of Mo, and the total amount of Mn and Mo is 15 atom% to 50 atom%, and the remainder includes Ni and inevitable impurities.

Further, it is more preferable that the intermediate film contains 1 atom% to 25 atom% of Mn, 10 atom% to 40 atom% of Cu, 3 atom% to 20 atom% of Mo, and 0 atom% to 5 atom%. Fe, the remainder contains Ni and unavoidable impurities.

Moreover, the present invention is an invention of a Ni alloy sputtering target, which is used a Ni alloy sputtering target for forming the intermediate film, which contains a total of 15 atom% to 60 atom% of one or more elements selected from the group consisting of Cu, Mn, Mo, and Fe, and the balance containing Ni and inevitable impurities The Curie point is below normal temperature.

Preferably, the Ni alloy sputtering target contains 10 atom% to 40 atom% of Cu, and 3 atom% to 20 atom% of Mo, and the total amount of Cu and Mo is 15 atom% to 50 atom%.

Further, it is more preferable that the Ni alloy sputtering target contains 1 atom% to 25 atom% of Mn, 3 atom% to 30 atom% of Mo, and the total amount of Mn and Mo is 15 atom% to 50 atom%. .

Further, it is still more preferable that the Ni alloy sputtering target contains 1 atom% to 25 atom% of Mn, 10 atom% to 40 atom% of Cu, 3 atom% to 20 atom% of Mo, and 0 atom%. 5 atom% Fe.

The intermediate film is formed by sputtering using the Ni alloy sputtering target in an environment containing at least one of oxygen and nitrogen in an amount of 20% by volume to 60% by volume.

In the step of manufacturing a flat display device or a touch panel, the laminated wiring film of the present invention can achieve a low reflectance which cannot be obtained by a conventional electrode or wiring film in addition to stable wet etching properties. The display quality such as FPD is improved. Therefore, it is a useful technique for a next-generation information terminal such as a 4K-TV, a smart phone, or a tablet PC, or a flexible FPD using a transparent resin substrate, which is attracting attention as a higher-definition FPD. The reason for this is that in these products, especially the low reflection of the metal film is very important.

1‧‧‧Transparent substrate

2‧‧‧ interlayer film

3‧‧‧Electrical film

Fig. 1 is a schematic cross-sectional view showing an application example of a laminated wiring film of the present invention.

An application example of the laminated wiring film of the present invention is shown in Fig. 1 . The build-up wiring film of the present invention can be obtained, for example, by forming an intermediate film 2 on the transparent substrate 1 and forming a conductive film 3 on the intermediate film 2. Further, in FIG. 1, the conductive film 3 is made of a single material, but it may be laminated according to the required resistance value or the heating temperature or environment in the manufacturing step, and may be appropriately selected.

One of the important features of the present invention is that, as a transparent substrate such as a glass substrate or an intermediate film formed on a transparent substrate on which a transparent film such as a transparent resin film is formed, a Ni alloy is used, and the film thickness is set. It is 20nm~100nm. Further, in the present invention, a conductive film having a specific resistance of 150 μΩcm or less is formed directly above the intermediate film to form a laminated structure. Further, another important feature of the present invention is that the visible light reflectance measured from the transparent substrate side is 20% or less. Hereinafter, each feature of the present invention will be described in detail.

In the following description, the "reflectance" means an average reflectance in a range of a wavelength in the visible light region of 360 nm to 740 nm.

The interlayer film of the Ni alloy in the laminated wiring film of the present invention contains, for example, one or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, and Cu. Thereby, a low-reflection semi-transmissive colored intermediate film can be obtained.

Further, in the laminated wiring film of the present invention, the film thickness of the interlayer film is set to 20 nm or more, whereby light transmission can be suppressed, and reflection of light can be prevented by the upper conductive film, whereby low reflection characteristics can be obtained. Moreover, by setting the film thickness of the interlayer film to 100 nm or less, the film formation time can be shortened, which contributes to an improvement in productivity. Further, in order to obtain a reflectance of 10% or less, it is preferred to set the film thickness of the interlayer film to 40 nm to 70 nm.

It is preferable that the intermediate film in the build-up wiring film of the present invention contains at least one selected from the group consisting of oxygen and nitrogen in the Ni alloy in an amount of 20 at% to 60 at%. The reason for this is that the intermediate film is a semi-transmissive colored film that easily absorbs light, and the visible light reflectance is reduced. In the present invention, by setting the content of oxygen or nitrogen contained in the intermediate film to 20 atom% or more, a semi-transmissive colored film in which metallic luster is suppressed can be obtained, thereby contributing to reduction in visible light reflectance. . Furthermore, in the present invention, by setting the content of oxygen or nitrogen contained in the intermediate film to 60 atom% or less, it is helpful to maintain adhesion to a transparent substrate or a conductive film.

The specific resistance of the conductive film formed directly above the intermediate film in the laminated wiring film of the present invention is desirably as low as possible, and can be made 150 μΩ cm or less equivalent to that of the ITO film.

In the present invention, by laminating the intermediate film and the conductive film in an optimum film thickness, a laminated wiring film having lower reflection characteristics can be obtained. The conductive film is preferably, for example, an element selected from the group consisting of Al, Cu, Mo, Ni, and Ag as a main component. It can be suitably selected in consideration of the required electric resistance value, the temperature or environment of the heating step in the manufacturing step, the adhesion to other oxide film or protective film, the barrier property, and the like. In addition, the present invention The term "main component" as used herein means an element selected from the group consisting of Al, Cu, Mo, Ni, and Ag in an amount of 50 atom% or more in the conductive film.

In particular, it is preferable that the electric resistance of Al is low, and if it is laminated with an ITO film as a transparent conductive film and a heating step is performed, an oxide of Al is formed at the interface, and electrical contact property may be lowered. Therefore, a coating film having excellent contact with the ITO film and containing Mo as a main component can be formed between the conductive film containing Al and the ITO film.

Further, Cu has a low resistance value and is suitable. However, since Cu has low oxidation resistance, it can be coated on a conductive film containing Cu by a coating film containing Ni as a main component.

When Al or Cu which is useful as the above-mentioned low-resistance conductive film is used, the problem of oxidation resistance can be solved by laminating a conductive film and a coating film containing Mo or Ni as a main component. On the other hand, in the case where the required resistance value is also relatively high, a conductive film having high heat resistance and containing Mo as a main component, and a conductive film having excellent weather resistance and containing Ni as a main component may be used in a single layer. Further, the conductive film containing Ag as a main component has a low electrical resistance value similar to that of Cu, and is excellent in oxidation resistance and moisture resistance as compared with Cu. Therefore, for these requirements, a single layer may be used. A conductive film containing Ag as a main component is used.

The film thickness of the conductive film is preferably from 10 nm to 500 nm. In the present invention, by setting the film thickness of the conductive film to 10 nm or more, the continuity of the conductive film can be maintained, and low reflection can be easily obtained, and the influence of electron scattering becomes proportionally small on the surface of the conductive film. Helps to suppress the increase in resistance. Further, in the present invention, by setting the film thickness of the conductive film to 500 nm or less, the film formation time can be shortened, and warpage due to film stress can be suppressed when applied to a transparent film substrate or the like.

Further, the light transmittance of the conductive film varies depending on the material selected, and in order to obtain stable low reflection characteristics, it is more preferable that the film thickness of the conductive film is 50 nm or more in which the transmitted light is reduced. Further, in order to make the influence of electron scattering on the surface of the film of the conductive film proportionally smaller, the resistance value is increased to obtain a stable resistance value, and it is more preferable to set the film thickness of the conductive film to 100 nm or more.

Further, it is preferable that the intermediate film contains one or more elements selected from the group consisting of Cu, Mn, Mo, and Fe in a total amount of 15 atom% to 60 atom%, and the balance is a Ni alloy containing Ni and unavoidable impurities.

Ni is excellent in weather resistance. On the other hand, it is difficult to perform etching by using an etchant or the like which is generally used for FPD, which is a chemical solution for using Al or Cu, and is also resistant to dry etching, so that it is difficult to process into a wiring film. Elements. Cu, Mn, Mo, and Fe are elements having an effect of improving the wet etching property of the chemical solution by being contained in Ni. This effect increases with the amount of addition. In the FPD, etching of a conductive film mainly composed of Mo, Ni, and Ag is mainly performed using an etchant for Al or Cu as a host. Therefore, in consideration of the etchability of the etchant of Al or Cu, the content of Cu, Mn, Mo, and Fe is preferably 15 atom% or more in total.

On the other hand, when the total content of Cu, Mn, Mo, and Fe exceeds 60 atom%, the weather resistance originally possessed by Ni is largely lowered. Therefore, in the present invention, the content of Cu, Mn, Mo, and Fe is preferably 15 atom% to 60 atom% in total.

Further, the effect of improving the etching property by Cu contained in the interlayer film becomes clear at 10 atom% or more. On the other hand, if the content of Cu exceeds 40 atoms When % is introduced, the low reflection characteristics, particularly the reflectance on the short wavelength side, are hard to be lowered. Therefore, in the present invention, it is preferred that the content of Cu in the interlayer film be 10 atom% to 40 atom%. More preferably, it is 10 atom% to 25 atom%.

Further, Mn contained in the intermediate film is an element having the highest etching effect improvement effect among Cu, Mn, Mo, and Fe, and is easily bonded to oxygen or nitrogen, so that the intermediate film can be easily made semi-transmissive. The element of the colored film. The effect of improving etching by Mn is exhibited at 1 atom% or more, and the effect of producing a semi-transmissive colored film which contributes to low reflection characteristics becomes clear at 6 atom% or more.

On the other hand, when Mn exceeds 25 atom%, for example, when nitrogen is contained in the interlayer film, the adhesion of the interlayer film is lowered. Therefore, in the present invention, it is preferred that the content of Mn in the interlayer film be 1 atom% to 25 atom%. More preferably, it is 6 atom% to 20 atom%.

The effect of improving the etching property by Mo contained in the interlayer film is exhibited at 3 atom% or more. Further, the effect of improving the low reflection property by Mo is the highest among Cu, Mn, Mo, and Fe, and the effect is clear at 5 atom% or more, and the effect is increased as the content is increased. However, when the content of Mo exceeds 30 atom%, the moisture resistance which is one of the weather resistance is lowered, and therefore it is preferably 30 atom% or less.

In addition, when Mo and Cu are contained at the same time, when the content of Mo exceeds 20 atomic%, the reflectance greatly fluctuates with respect to the wavelength in the light-receiving region due to the film thickness of the interlayer film. It is difficult to obtain stable low reflection characteristics. The reason is not clear, but consider the following effects: since Cu and Mo are on the equilibrium state diagram A combination of elements that are easy to phase separate, so if they are contained in a large amount at the same time, the intermediate film becomes irregular.

In the case where Mo and Cu are contained in the same manner, when Mo is contained in an amount of more than 20 atomic%, when Cu is used as a conductive film and is laminated with the intermediate film, it is easy to cause etching by etching with Cu. Uneven etching.

According to the above, in the present invention, it is preferable that the content of Mo in the case where Cu is contained in the intermediate film is 3 atom% to 20 atom%, and the total amount of Cu and Mo is 15 atoms. %~50 atom%. More preferably, Mo is 5 atom% to 15 atom%.

Further, when Mn and Mo are contained in the intermediate film, the content of Mo is preferably 30 atom% or less. The reason for this is that if the content of Mo exceeds 30 atom%, the moisture resistance may be lowered as described above.

In the present invention, in order to perform etching by an etchant of Cu or Al, it is preferable that the content of Mn and Mo in the interlayer film is 15 atom% or more in total. In addition, when the total amount of Mn and Mo in the interlayer film exceeds 50 atom%, oxidation resistance or moisture resistance may be lowered.

According to the above, in the present invention, the total amount of Mn and Mo in the intermediate film is more preferably in the range of 15 atom% to 50 atom%.

Further, in order to stably obtain low reflection characteristics together with the etching property, it is more preferable that the Ni alloy of the interlayer film contains 1 atom% to 25 atom% of Mn, and 10 atom% to 40 atom% of Cu, 3 Atom%~20 atom% of Mo, 0 atom%~5 atom% of Fe.

Further, there is a case where etchability is satisfied by Mn or Cu depending on the material of the conductive film laminated with the intermediate film. In this case, Mo may be substituted by Ti, Zr, Hf, V, Nb, Ta, Cr, W, Co or the like as another transition metal.

Moreover, Fe is an element which can improve etching property. When the amount of Fe contained in the interlayer film exceeds 5 atom%, the reflectance increases due to the film thickness of the interlayer film, and is affected by magnetic properties or the like. When the laminated wiring film such as FPD has magnetic characteristics, there is a case where noise is generated by electromagnetic induction or the like when a current flows, and it is preferable that the intermediate film is as nonmagnetic as possible. Therefore, in the present invention, Fe contained in the interlayer film is preferably contained in a range of 5 atom% or less, in the case where the effect of improving the etching property of the element is insufficient. More preferably, it is 3 atom% or less.

As a method of forming the above intermediate film, a sputtering method using a Ni alloy sputtering target is most suitable. The sputtering method is one of the physical vapor deposition methods, and is a method for stably forming a large-area film as compared with other vacuum vapor deposition or ion plating, and is an effective method for obtaining an excellent thin film layer having little composition variation. .

The formation of the interlayer film can be obtained by a reactive sputtering method using a Ni alloy sputtering target. In this case, the environment in which the sputtering is performed may be in the environment of at least one selected from the group consisting of oxygen and nitrogen, in addition to the inert gas Ar generally used in the sputtering gas, by sputtering. Formed by plating.

In order to form the intermediate film, the Ni alloy sputtering target of the present invention contains a total of 15 atom% to 60 atom% of one or more elements selected from the group consisting of Cu, Mn, Mo, and Fe, and the remainder contains Ni and unavoidable impurities. And the Curie point is set to be below normal temperature.

Further, since the Ni contained in the interlayer film is a magnetic body at normal temperature, the magnetron sputtering apparatus generally used in FPD applications has a problem that the magnetic flux of the magnetic circuit is absorbed by the sputtering target, and it is difficult to be efficient. Stable sputtering is performed well. Therefore, in the present invention, in the normal temperature using the Ni alloy sputtering target, the non-magnetic, that is, the Curie point is set to be normal temperature or lower. In addition, the "Curie point is below normal temperature" in the present invention means 0 when the saturation magnetization is measured at normal temperature (25 ° C).

When Mn is added to Ni, the addition amount of the Curie point in the region where Mn is solid-solved is reduced to about 15 at%. On the other hand, when the addition amount of Mn in Ni exceeds about 20 atom%, the Curie point becomes high, and if it exceeds 25 atom%, the following problem also becomes remarkable: a compound phase is exhibited due to a phase transition, Curie The dots become higher than pure Ni, and the Ni alloy sputtering target becomes brittle, making it difficult to perform stable machining.

Further, Mn is an element which is more easily oxidized than Ni. When Mn is added to Ni, it is easy to form an oxide at the interface with a glass substrate or a transparent conductive film, and the effect of further improving the adhesion. Therefore, in the case where Mn is added in the present invention, it is preferred to set the amount thereof to be 1 atom% to 25 atom%. More preferably, the amount of Mn added is from 6 atom% to 20 atom%.

When Cu is added to Ni, the Curie point is lowered. On the other hand, when the amount of Cu added exceeds 40 atom% as described above, when oxygen is introduced into the interlayer film, low reflection characteristics, particularly on the short wavelength side, are obtained. The reflectance becomes difficult to reduce. Therefore, in the present invention, it is preferred to set the addition amount of Cu to 10 atom% to 40 atom%. More preferably, it is 10 atom% to 25 atom%. Further, the total amount of Cu and Mo is preferably 15 atom% to 50 atom%.

The Mo which is a non-magnetic element is the most effective in reducing the Curie point of Ni as a magnetic material. When Mo is added in an amount of about 8 at% or more to Ni, the Curie point is at most normal temperature. In addition, when the amount of addition of Mo having a high non-magnetic effect is increased, the adhesion to the glass substrate or the transparent conductive film is improved, and the weather resistance and the like are lowered. Therefore, in the present invention, it is preferred to set the amount of Mo to be 3 atom% to 20 atom%. More preferably, it is 5 atom% to 15 atom%. Further, the total amount of Mn and Mo is preferably 15 atom% to 50 atom%.

The effect of improving the etching property of Mn or Fe is high. Therefore, when Fe as a magnetic substance is added to Ni, the Curie point rises to a large extent. Further, Fe and Cu have a small solid solution domain and are easily expressed as a compound with Mo. When excessively added, the sputtering target is embrittled. Therefore, in the present invention, it is preferable that the sputtering target is added with Fe in a range satisfying non-magnetic properties and etching properties and not embrittlement, and the addition amount thereof is 5 atom% or less. More preferably, it is 3 atom% or less.

According to the above, it is more preferable that the Ni alloy sputtering target of the present invention contains 1 atom% to 25 atom% of Mn, 10 atom% to 40 atom% of Cu, 3 atom% to 20 atom% of Mo, 0 atom. %~5 atom% of Fe.

In the Ni alloy sputtering target of the present invention, an element having a Curie point or less is an element below normal temperature as an element added to the magnetic material Ni. For example, a molten ingot can be produced, and a plate shape can be formed by plastic working, and then machined. Cut out to obtain the specified size.

Among them, in the composition in which the amount of addition of Mn is large or the composition containing both of Mo and Fe, it is difficult to exhibit a compound phase and plastic working in the Ni alloy sputtering target. In this case, it is preferably selected from the magnetic body Ni. The element to be added is subjected to pressure sintering of a Ni alloy powder having a Curie point below normal temperature. In particular, the laminated wiring film of the present invention is used in the field of FPD using a large transparent substrate. Therefore, in order to stably produce the Ni alloy sputtering target of the present invention, it is preferable to press-sinter the Ni alloy powder.

The Ni alloy powder having a Curie point below normal temperature can be easily obtained by an atomization method using a Ni alloy adjusted to a final composition. Further, the melted ingot may be pulverized to produce a Ni alloy powder. Further, a method of producing various Ni alloy powders and mixing them in a final composition can also be applied.

Further, in the present invention, by using a Ni alloy powder having an average particle diameter of 5 μm or more, an increase in impurities in the obtained Ni alloy sputtering target can be suppressed. Further, in the present invention, a sintered body having a high density can be obtained by using a Ni alloy powder having an average particle diameter of 300 μm or less.

In addition, the average particle diameter in the present invention is represented by the equivalent spherical diameter of the light scattering method using laser light prescribed in JIS Z 8901, and is represented by D50 of the cumulative particle size distribution.

The pressure sintering applied to obtain the Ni alloy sputtering target of the present invention may be applied by hot press pressing (hereinafter referred to as "HIP (Hot Isostatic Press)") or hot pressing, preferably at 800 ° C to 1250 ° C. It is carried out under the conditions of 10 MPa to 200 MPa and 1 hour to 10 hours. The choice of these conditions depends on the means for performing pressure sintering. For example, HIP is easy to apply conditions of low temperature and high pressure, and hot pressing is easy to apply conditions of high temperature and low pressure. In the present invention, it is preferred to use a HIP which can be sintered at a low temperature to suppress diffusion of the Ni alloy and which is sintered under high pressure to obtain a sintered body having a high density.

When the sintering temperature is less than 800 ° C, sintering is difficult, and it is difficult to obtain a sintered body having a high density. On the other hand, when the sintering temperature exceeds 1,250 ° C, the liquid phase is exhibited, or the crystal growth of the sintered body becomes remarkable, and it becomes difficult to obtain a uniform fine structure. By sintering in the range of 800 ° C to 1250 ° C, a high-density Ni alloy sputtering target can be easily obtained.

Further, when the pressing force at the time of sintering is less than 10 MPa, sintering is difficult, and a sintered body having a high density cannot be obtained. On the other hand, if the pressure exceeds 200 MPa, there is a problem that the device capable of withstanding this pressure is limited.

Further, when the sintering time is less than 1 hour, it is difficult to sufficiently perform sintering, and it is difficult to obtain a sintered body having a high density. On the other hand, from the viewpoint of production efficiency, it is preferred to avoid the sintering time of more than 10 hours.

When pressure sintering is performed by HIP or hot pressing, it is preferable to fill the Ni alloy powder in a pressurizing vessel or a pressurizing mold, and then perform degassing under reduced pressure while heating. Deaeration under reduced pressure is preferably carried out at a lower pressure than atmospheric pressure (101.3 kPa) at a heating temperature of from 100 ° C to 600 ° C. This is because the oxygen of the obtained sintered body can be further reduced, and the formation of a coarse oxide which inhibits machinability can be suppressed, and a high-purity sputtering target can be obtained.

Further, in the Ni alloy sputtering target of the present invention, it is preferable that elements other than Ni and Mn, Cu, Mo, and Fe are as small as possible. When there are many impurities other than these elements, the electric resistance value of the laminated wiring film obtained is increased, and it reacts with other laminated film by the kind of element, and the characteristics, such as adhesiveness and weather resistance, are deteriorated. Especially the oxygen or nitrogen of the gas component is easy to generate coarse oxidation in the sputtering target. Object or nitride, thereby impeding machinability. Therefore, the purity of the Ni alloy sputtering target of the present invention is 99.9% by mass or more, and the impurity is preferably 1000 ppm by mass or less, more preferably 300 ppm by mass or less.

[Example 1]

First, in order to form a Ni-Cu-Mo alloy film as an intermediate film, the atomic ratio was measured so that Ni-15% Cu-8% Mo was weighed, and in the vacuum melting furnace, an ingot was produced by a melt-casting method. A Ni alloy sputtering target having a diameter of 100 mm and a thickness of 5 mm was produced by machining the ingot.

The obtained Ni alloy sputtering target was brought close to the SmCo magnet, and it was confirmed that it was not attached to the magnet. Furthermore, a part of the obtained ingot was placed in a magnetic property measuring cartridge, and a vibrating sample magnetometer (model: VSM-5) manufactured by Riken Electronics Co., Ltd. was used and measured at room temperature (25 ° C). The magnetic properties were confirmed to be non-magnetic.

Further, in order to form an Al film, an Ag film, a Cu film, and a Mo film as a conductive film laminated on the intermediate film, a sputtering target of Al, Ag, Cu, and Mo having a diameter of 100 mm and a thickness of 5 mm was prepared. The Al sputter target was manufactured by Sumitomo Chemical Co., Ltd., and the Ag sputter target was manufactured by Guwu Metal Co., Ltd. Further, a Cu sputtering target for forming a Cu film as a conductive film can be produced by cutting out an oxygen-free copper (OFC) raw material manufactured by Hitachi Cable Co., Ltd. (currently: Hitachi Metals Co., Ltd.). Further, a Mo sputtering target for forming a Mo film as a conductive film can be produced by cutting out a material obtained by pressure-sintering a Mo powder having a purity of 4N.

Each of the prepared sputtering targets was welded to a copper backing plate and mounted on a sputtering apparatus (Model: CS-200) manufactured by ULVAC. Then, a film having a film thickness shown in Table 1 was formed on a 25 mm × 50 mm glass substrate (product number: Eagle XG) to prepare each sample. In addition, the sputtering gas composition [Ar+O ₂ ] shown in Table 1 was formed in an environment containing 50% by volume of oxygen in Ar. Further, the conductive film is formed directly above the intermediate film using Ar gas.

The results of measuring the reflectance and specific resistance of each of the obtained samples are shown in Table 1. In addition, the reflectance was measured by using a spectrophotometer (model: CM2500d) manufactured by Konica Minolta Co., Ltd., and the reflectance from the glass substrate side and the reflectance from the conductive film side were measured. Further, the specific resistance was measured by using a thin film resistivity meter (model: MCP-T400) manufactured by Mitsubishi Oil Chemical Co., Ltd. (currently: Daia Instruments Co., Ltd.), and the specific resistance from the side of the conductive film was measured. .

As shown in Table 1, it can be confirmed by the sputtering gas containing Ar and oxygen. A laminated wiring film which is an example of the present invention in which a conductive film is formed on an intermediate film containing a Ni alloy, and a reflectance measured from the side of the transparent glass substrate has a low reflectance of 10% or less. In addition, a laminated wiring film which is an example of the present invention using Cu, Al, Ag, Mo, or Ni alloy in the conductive film was confirmed, and the specific resistance of the conductive film was 150 μΩcm or less, which was low resistance.

Further, regarding a sample for forming an intermediate film in the multilayer wiring film of the present invention of 50 nm, an X-ray photoelectron spectroscope (ESCA) (model: AXIS-HS) manufactured by KRATOS ANALYTICAL Co., Ltd. was used to measure the middle. The concentration of oxygen in the membrane. As a result, it was found that 46 atom% of oxygen was contained, and Cu ₂ O and MoO ₃ were confirmed by an analysis chart, and it was confirmed that a part of the additive element was an oxide and was present in the intermediate film.

[Embodiment 2]

Next, in order to produce a Ni alloy sputtering target containing an atomic ratio of Ni-10%Mn-25%Cu-10%Mo-3%Fe, the purity of the composition was first prepared by gas atomization method to be 99.9%. A Ni alloy powder having an average particle diameter of 65 μm.

The obtained Ni alloy powder was brought close to the SmCo magnet, and as a result, it was confirmed that it did not adhere to the magnet. Furthermore, a part of the obtained Ni alloy powder was placed in a powder box for measuring magnetic properties, and a vibrating sample type magnetometer (model: VSM-5) manufactured by Riken Electronics Co., Ltd. was used at normal temperature (25 ° C). The magnetic properties were measured and found to be non-magnetic.

Next, the Ni alloy powder obtained above was filled to an inner diameter of 133. In a mild steel container having a height of 30 mm and a thickness of 3 mm, the mixture was heated at 450 ° C for 10 hours to perform a degassing treatment, and then the soft steel container was sealed, and at 1000 ° C, 148 MPa, 5 by a HIP device. Sintering was carried out under an hour condition.

After cooling the soft steel container, it was taken out from the HIP apparatus, and the soft steel container was removed by mechanical processing to obtain a Ni alloy sputtering target having a diameter of 100 mm and a thickness of 5 mm. Moreover, the test piece is cut out by the remaining portion.

The relative density of the obtained test piece was measured by Archimedes' law, and it was confirmed that it was 99.9%. In addition, the "relative density" in the present invention means a value obtained by dividing a volume density by a value of a theoretical density by 100, which can be measured by Archimedes' law, which can be used as The mass ratio obtained by forming the composition ratio of the sputtering target according to the present invention is obtained by weighted average of the calculated elemental monomers.

Next, the quantitative analysis of the metal elements of the obtained test piece was carried out by an inductively coupled plasma luminescence analyzer (ICP) (Model: ICPV-1017) manufactured by Shimadzu Corporation, and determined by a non-dispersive infrared absorption method. As a result of quantification of oxygen, it was confirmed that the total purity of the analysis values of Ni, Mn, Cu, Mo, and Fe was 99.9%, and the oxygen concentration was 500 ppm by mass.

The obtained Ni alloy sputtering target material was welded to a copper backing plate in the same manner as in Example 1, and then mounted on a sputtering apparatus (Model: CS-200) manufactured by Ubeck Co., Ltd. Then, on a 25 mm × 50 mm glass substrate (product number: Eagle XG), 50% by volume of oxygen is contained in Ar. A Ni alloy film to be an interlayer film is formed under the environment. Further, a conductive film formed directly above the intermediate film was formed by using Ar gas, and each sample was produced by the configuration shown in Table 2. Further, the Ni alloys of the conductive films of Sample No. 39 to Sample No. 43, Sample No. 45, and Sample No. 48 shown in Table 2 were used to contain an atomic ratio of Ni - 10% Mn - 25%. Ni alloy of Cu-10%Mo-3%Fe.

The evaluation of each sample was carried out by measuring the reflectance and specific resistance in the same manner as in Example 1. The results are shown in Table 2.

As shown in the sample No. 11, the sample No. 12, and the sample No. 19 which are comparative examples shown in Table 2, it was confirmed that the film thickness of the intermediate film containing the Ni alloy contained in the oxygen ratio was larger than When 20 nm is thin, a low reflectance of 20% or less is not obtained.

On the other hand, it is confirmed that the multilayer wiring film in which the interlayer film and the conductive film are laminated in the range of the present invention has a reflectance of 20% or less and is excellent in low reflection characteristics. In addition, it is confirmed that the specific resistance of the conductive film which is a laminated wiring film of the present invention using Mo, Cu, Al, or Ni alloy in the conductive film is 150 μΩcm or less, and is low resistance.

It is understood that the film thickness of the intermediate film having the most reduced reflectance varies depending on the material of the conductive film, but the film thickness is in the vicinity of 50 nm. Here, when the film thickness of the interlayer film containing the Ni alloy is fixed to 50 nm, when the film thickness of the conductive film is 10 nm or more, low reflection characteristics of 15% or less are obtained.

Next, the evaluation of the etching property was performed. The samples of sample No. 44 and sample No. 45 were etched using an etchant for Al manufactured by Kanto Chemical Co., Ltd., and as a result, etching was performed without unevenness. In addition, the sample of sample No. 48 was etched using an etchant for Cu manufactured by Kanto Chemicals Co., Ltd., and as a result, etching was performed satisfactorily without causing residue.

[Example 3]

Forming an intermediate film on the substrate shown in Table 3, followed by the intermediate film A conductive film was formed to obtain a sample of the laminated wiring film. Further, when an intermediate film is formed, a sputtering gas having oxygen or nitrogen is mixed by Ar/or Ar in a predetermined gas concentration so as to have a predetermined gas concentration, and is formed on the substrate. Further, the conductive film is formed by using an Ar gas directly above the intermediate film.

The results of measuring the reflectance and the specific resistance of each of the obtained samples are shown in Table 3. In addition, the reflectance was measured in the same manner as in the first embodiment and the second embodiment using a spectrophotometer (model: CM2500d) manufactured by Konica Minolta Co., Ltd., from both the glass substrate side and the self-conductive film side. The reflectance was measured. Further, the specific resistance was measured using a film resistivity meter (model: MCP-T400) manufactured by Mitsubishi Petrochemical Co., Ltd. (currently: Daya Instruments Co., Ltd.).

The transparent wiring side of the laminated wiring film of Sample No. 51 to Sample No. 55, Sample No. 57 to Sample No. 59, and Sample No. 61 to Sample No. 64 which are examples of the present invention was confirmed. The measured visible light reflectance was 20% or less, and a low reflectance was obtained.

In addition, it was confirmed that an intermediate film was formed on the transparent substrate on which the ITO film of sample No. 55 was formed, and a laminated wiring film having a conductive film having a specific resistance of 3.7 μΩcm was formed directly above the intermediate film. Underneath, a low reflectance is also obtained.

In addition, as shown in the sample No. 62 of the other example of the present invention, it was confirmed that an intermediate film was formed on the film transparent substrate on which the ITO film was formed on the transparent film of PET as a resin, and a ratio was formed directly above the intermediate film. In the case of a laminated wiring film of a conductive film having a resistance of 2.4 μΩcm or less, a low reflectance is also obtained.

The amount of oxygen in the intermediate film of sample No. 56 formed by using Ar + 10 vol% of oxygen in the sputtering gas was measured in the same manner as in Example 1. As a result, the amount of oxygen in the interlayer film was 15 atom%. Further, the amount of oxygen in the intermediate film of sample No. 57 in which the sputtering gas was formed using Ar + 20% by volume of oxygen was 24 atom%.

Test of laminated wiring film of sample No. 51, sample No. 52, sample No. 53, sample No. 54, and sample No. 55 using an etchant for Al manufactured by Kanto Chemical Co., Ltd. The etching test was performed. As a result, in any of the samples which are examples of the present invention, etching can be performed uniformly without residue.

An etching test was performed on a sample of the laminated wiring film of sample No. 55, sample No. 59, sample No. 62, and sample No. 63 using an etchant for Cu manufactured by Kanto Chemical Co., Ltd. As a result, it is possible to have no unevenness in any sample. The etching is performed uniformly in time.

1‧‧‧Transparent substrate

2‧‧‧ interlayer film

3‧‧‧Electrical film

Claims (11)

A laminated wiring film having a laminated structure in which an intermediate film having a thickness of 20 nm to 100 nm including a nickel alloy is formed on a transparent substrate or a transparent substrate on which a transparent film is formed, and A conductive film having a specific resistance of 150 μΩcm or less is formed directly above the intermediate film, and the visible light reflectance measured from the transparent substrate side is 20% or less. The laminated wiring film according to claim 1, wherein the conductive film is mainly composed of an element selected from the group consisting of Al, Cu, Mo, Ni, and Ag, and has a film thickness of 10 nm to 500 nm. The laminated wiring film according to claim 1 or 2, wherein the intermediate film contains a total of 15 atom% to 60 atom% of one or more elements selected from the group consisting of Cu, Mn, Mo, and Fe, and the remainder Part contains Ni and unavoidable impurities. The laminated wiring film according to claim 1 or 2, wherein the intermediate film contains 10 atom% to 40 atom% of Cu, 3 atom% to 20 atom% of Mo, and a total of Cu and Mo The amount is 15 atom% to 50 atom%, and the remainder contains Ni and unavoidable impurities. The laminated wiring film according to claim 1 or 2, wherein the intermediate film contains 1 atom% to 25 atom% of Mn, 3 atom% to 30 atom% of Mo, and the total of Mn and Mo The amount is 15 atom% to 50 atom%, and the remainder contains Ni and unavoidable impurities. The laminated wiring film according to claim 1 or 2, wherein the intermediate film contains 1 atom% to 25 atom% of Mn, and 10 atom% to 40 atom% Cu, 3 atom% to 20 atom% of Mo, 0 atom% to 5 atom% of Fe, and the remainder contains Ni and unavoidable impurities. A nickel alloy sputtering target which is a nickel alloy sputtering target for forming an intermediate film according to claim 1, wherein the nickel alloy sputtering target is characterized by containing a total of 15 atoms %~60 atom% of one or more elements selected from the group consisting of Cu, Mn, Mo, and Fe, and the remainder contains Ni and unavoidable impurities, and the Curie point is below normal temperature. The nickel alloy sputtering target according to claim 7, which contains 10 atom% to 40 atom% of Cu, 3 atom% to 20 atom% of Mo, and the total amount of Cu and Mo is 15 atom%. ~50 atomic %. The nickel alloy sputtering target according to claim 7, which contains 1 atom% to 25 atom% of Mn, 3 atom% to 30 atom% of Mo, and the total amount of Mn and Mo is 15 atom%. ~50 atomic %. The nickel alloy sputtering target according to claim 7, which contains 1 atom% to 25 atom% of Mn, 10 atom% to 40 atom% of Cu, 3 atom% to 20 atom% of Mo, 0. Atomic % to 5 atomic % Fe. A method for producing a laminated wiring film, characterized in that the intermediate film is used in an environment containing at least one of oxygen and nitrogen in an amount of 20% by volume to 60% by volume, as in the seventh to the fourth The nickel alloy sputtering target described in item 10 is formed by a sputtering method.