KR20150021891A - Sputtering target material for forming coating layer and manufacturing method thereof - Google Patents

Abstract

The purpose of the present invention is to provide a sputtering target material to form a new coating layer, and a manufacturing method for the same to secure an adhesion, weather resistance, and oxidation resistance of a low resistance copper thin film layer; to stably carry out wet etching; and to stably form a new coating layer. The sputtering target material to form a coating layer of a thin film layer made of copper or a copper alloy is composed of 5-25 at% of manganese; 60 at% or less of one or more elements selected from molybdenum, copper, and iron; the remaining amount of nickel and impurities; and has a curie point lower than a room temperature.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sputtering target material for forming a coating layer,

The present invention relates to a sputtering target material for forming a coating layer used for forming a coating layer on a thin film layer made of, for example, Cu or a Cu alloy serving as a main wiring of an electronic component, and a manufacturing method thereof.

(Hereinafter referred to as " PDP ") used for forming a thin film device on a glass substrate, a liquid crystal display (hereinafter referred to as " LCD "), a plasma display panel In a thin film electronic device such as various semiconductor devices, thin film sensors, magnetic heads, etc., in addition to a flat display device (flat panel display, hereinafter referred to as "FPD") such as a display, Do. For example, FPDs such as LCDs, PDPs, organic EL displays and the like are required to have low resistances in their wiring films due to their large screen, high resolution, and high-speed response. Recently, new products such as a flexible FPD using a touch panel or a resin substrate that adds operability to the FPD have been developed.

In recent years, a wiring film of a thin film transistor (hereinafter referred to as " TFT ") which is used as a driving element of an FPD is required to have a low resistance and the material of the main wiring thin film layer is changed from a conventional Al to a low resistance Cu Has been reviewed.

In addition, a touch panel substrate screen that gives direct operability while viewing the screen of the FPD is also becoming larger, and a thin film layer made of Cu or a Cu alloy (hereinafter referred to as a " Cu thin film layer " The use is under review.

Indium Tin Oxide (hereinafter referred to as " ITO "), which is a transparent conductive film, is generally used for a position detection electrode of a touch panel used in a portable terminal or a tablet PC. Cu has a problem that contact property with ITO is obtained, but adhesion with a substrate is low and weather resistance is poor. For this reason, in order to secure the adhesion of the Cu thin film layer and to improve the weather resistance, it is necessary to form a laminated wiring film in which the Cu thin film layer is covered with a coating layer of Ni alloy or the like.

On the other hand, as a method for forming the above-described thin film wiring, a sputtering method using a sputtering target material is most suitable. The sputtering method is one of the physical vapor deposition methods, and is an effective method that can stably form a large area in comparison with other vacuum deposition or ion plating, and is also an excellent thin film layer with less composition fluctuation.

Ni, which is the main component of the coating layer, is a magnetic substance at room temperature, and therefore, in the magnetron sputtering apparatus generally used for FPD applications, the magnetic flux of the magnetic circuit is absorbed by the sputtering target material, so that it is difficult to efficiently perform stable sputtering.

The inventors of the present invention have found that when the element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W is used as a coating layer of Ag or Cu thin film layer, To 25 atomic%, and the total amount of addition is not more than 35 atomic%. (Patent Document 1)

The coating layer proposed in Patent Document 1 is a useful technique in that it is abbreviated as a Ni alloy to which a predetermined amount of a transition metal such as Ti, V, Cr or the like is added and thereby film formation by sputtering is stable and can be performed for a long time.

For the purpose of improving the etching property against Cu etchant of the Ni alloy coating layer, a Ni-Cu alloy containing 25 to 45 wt% of Cu and an alloy containing 5 wt% or less of Mo or Co, A Ni-Cu alloy in which 5 wt% or less of Fe or Mn is added to a Ni-Cu alloy added with? 25 wt% is proposed. (Patent Document 2)

Also, for the purpose of improving the etching property to Cu etchant and improving the weather resistance and adhesion, it is preferable to use a Ni-Cu alloy containing 15 to 55 wt% of Cu and a Ni-Cu alloy containing 10 wt% or less of Cr or Ti Alloy has been proposed (Patent Document 3)

These Ni-Cu alloys disclosed in Patent Document 2 and Patent Document 3 are useful techniques because they can improve etchability.

Japanese Patent Application Laid-Open No. 2006-310814 Japanese Patent Application Laid-Open No. 2011-052304 Japanese Patent Application Laid-Open No. 2012-193444

In recent FPDs, since high resolution is rapidly proceeding, it is desired to etch the FPD with high accuracy with narrower wiring width. However, Cu is not easy to perform dry etching, which is an etching method with high precision, and therefore, wet etching is mainly used in FPD applications.

However, there is a problem that when a wet etching is performed on the laminated wiring film made of the Cu thin film layer and the coating layer, residues tend to be generated. As a result, it is clear that there is a problem that it is difficult to stably obtain a wiring film with a narrow width, which is expected to increase in the side etching amount because the residue is suppressed by performing over etching using an etchant containing hydrogen peroxide with high volatility, It has come.

According to the study by the present inventors, when the Cu thin film layer and the laminated wiring film formed of the coating layer made of the Ni alloy described in the above-mentioned Patent Document 1 are wet-etched, the etching of the covering layer made of the Ni alloy in the substrate surface becomes uneven, And it is confirmed that there is a new problem in that a deviation occurs in the wiring width.

In addition, in the case of the Ni-Cu alloy proposed in Patent Documents 2 and 3, if the amount of Cu to be added is increased in order to improve the etching property, the oxidation resistance is lowered and a film substrate such as a glass substrate, Or adhesion to ITO which is a transparent conductive film is lowered, and oxidation resistance is significantly lowered.

It is an object of the present invention to provide a new coating layer forming sputtering capable of stably forming a new coating layer which is capable of ensuring adhesion, weather resistance, and oxidation resistance to a low-resistance Cu thin film layer, And a method of manufacturing the same.

In view of the above-described problems, the inventors of the present invention have studied the sputtering target material for forming the coating layer on the Cu thin film layer. As a result, it has been found that a new coating layer, which is less prone to unevenness during etching, can be formed while securing adhesion, weather resistance, and oxidation resistance by adding a specific amount of Ni-specific elements.

That is, the present invention is a sputtering target material for forming a coating layer of a thin film layer made of Cu or a Cu alloy, which comprises 5 to 25 atomic percent of Mn and at least one element selected from Mn, By mass or less and 60% by atom or less in terms of mass, the balance being Ni and inevitable impurities, and having a Curie point of room temperature or less.

In the sputtering target for forming a coating layer of the present invention, it is preferable that the Mn content is 5 to 25 atomic%, the Mo content is 5 to 40 atomic%, and the total amount of Mn and Mo is 15 to 50 atomic%.

The sputtering target for forming a coating layer of the present invention preferably contains 5 to 25 atomic% of Mn, 5 to 30 atomic% of Mo, 10 to 40 atomic% of Cu and 0 to 5 atomic% of Fe Do.

The sputtering target material for forming a coating layer of the present invention is a sputtering target material for forming a coating layer, wherein the Mn is 7 to 20 atomic%, the Mo is 10 to 25 atomic%, the Cu is 10 to 25 atomic%, the Fe is 0 to 3 atomic% And the total amount of Mn, Mo, Cu and Fe is 27 to 50 atomic%.

The present invention also provides a method for producing a sputtering target material for forming a coating layer of a thin film layer made of Cu or a Cu alloy, which comprises 5 to 25 atomic percent of Mn and at least one element selected from the group consisting of Cu, Mo and Fe Of a total amount of 60 atomic% or less, and the balance amount of Ni and inevitable impurities, and pressurizing and sintering an alloy powder having a Curie point at room temperature or lower.

In the present invention, it is preferable that the alloy powder contains Mn in an amount of 5 to 25 atomic%, Mo in an amount of 5 to 40 atomic%, and the total amount of Mn and Mo in an amount of 15 to 50 atomic%.

It is preferable that the alloy powder contains 5 to 25 atom% of Mn, 5 to 30 atom% of Mo, 10 to 40 atom% of Cu, and 0 to 5 atom% of Fe.

The alloy powder preferably contains 7 to 20 atomic% of Mn, 10 to 30 atomic% of Mo, 10 to 25 atomic% of Cu, 0 to 3 atomic% of Fe, The total amount of Cu and Fe is preferably 27 to 50 atomic%.

INDUSTRIAL APPLICABILITY The present invention can stably provide a sputtering target material capable of securing the adhesion with the Cu thin film layer, weather resistance, oxidation resistance, and also capable of forming a coating layer which is unlikely to cause unevenness during wet etching, This is a technique useful for improving the reliability of electronic components.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an example of a photograph of a cross-section microstructure of a sputtering target material for forming a coating layer of the present invention observed with an optical microscope. Fig.

A sputtering target material for forming a coating layer used for forming a coating layer covering a Cu thin film layer, the sputtering target material containing 5 to 25 atomic% of Mn and containing at least one element selected from the group consisting of Mo, Cu, and Fe By atom in total, and the remainder being composed of Ni and unavoidable impurities, and having a Curie point of not more than room temperature.

Ni is an element which is superior to Cu in terms of improving adhesion with a substrate, a Cu thin film layer, or a transparent conductive film, and also improving weather resistance. In the coating layer formed using the sputtering target material for forming a coating layer of the present invention, Cu or Cu It is possible to obtain an effect of improving the adhesion and weather resistance by coating the thin film layer made of the alloy.

In the present invention, Mn, Mo, Cu, and Fe to be added to Ni are elements having an effect of improving the etchability to a catalyst for a multilayer wiring film composed of a thin film layer made of Cu or a Cu alloy and a coating layer. As for the improvement effect, Mn is the highest, followed by Fe, Cu, and Mo. This improvement effect can be improved when the total of these added elements is 15 atomic% or more. When the total amount of the added elements exceeds 60 atomic%, the inherent weather resistance of Ni is significantly lowered. Therefore, the total of these added elements is 60 atom% or less.

In the sputtering target material for forming a coating layer of the present invention, the Curie point is set to room temperature or lower. As described above, Ni is a magnetic substance. In the present invention, in order to perform efficient stable sputtering, it is necessary to set the non-magnetic property, that is, the Curie point at room temperature or lower, at room temperature using a sputtering target material. In the present invention, the term " Curie point at room temperature or below " means zero when the saturation magnetization is measured at room temperature (25 DEG C).

When Mn is added to Ni, the Curie point is lowered to about 15 atomic%, which is a region where Mn is solved. On the other hand, when the addition amount of Mn to Ni exceeds about 20 atomic%, the Curie point becomes high. When the addition amount exceeds 25 atomic%, the compound phase is expressed by the phase transformation and the Curie point becomes higher than pure Ni, And it becomes difficult to perform stable machining. In addition, it is not possible to make the Curie point at room temperature or lower simply by adding Mn. In order to perform stable sputtering, it is necessary to reduce the thickness of the sputtering target material, and the production efficiency is lowered. Therefore, in the present invention, in order to keep the Curie point at room temperature or lower, it is added in combination with other elements effective for non-magnetization.

Mn is an element which is more easily oxidized than Ni. When Mn is added to Mn in an amount of 5 atomic% or more, oxides are easily formed at the interface of the film with respect to the substrate, the Cu thin film layer or the transparent conductive film, , Whereas if it exceeds 25 atomic%, the oxidation resistance may be lowered. For this reason, in the present invention, the addition amount of Mn is 5 to 25 atomic%. Preferably, the addition amount of Mn is 7 to 20 atomic%.

When Cu is added to Ni, the Curie point is lowered. On the other hand, when the laminated wiring film coated with the Cu thin film layer is heated, the oxidation resistance is lowered and the effect of protecting the thin film layer made of Cu or Cu alloy is lowered, And the adhesiveness with the substrate, the Cu thin film layer, the transparent conductive film or the like is deteriorated. Therefore, in the present invention, it is preferable that the addition amount of Cu is 10 to 40 atomic%. And more preferably 10 to 25 atomic%.

The effect of lowering the Curie point of Ni, which is a magnetic substance, is highest for Mo, which is a non-magnetic element, and the Curie point is below room temperature when Mo is added to Ni in an amount of about 8 atomic%. Further, Ni solves about 30 atom% of Mo in the high temperature region and lowers the high capacity in the low temperature region. When the addition amount of Mo exceeds 30 atomic%, the compound phase is expressed. When the addition amount of Mo exceeds about 40 atomic%, the compound phase is increased to make the sputtering target material weak and it becomes difficult to perform stable machining.

Increasing the amount of Mo, which has a high effect of nonmagnetization, has an effect of improving the adhesiveness with the substrate, the Cu thin film layer, or the transparent conductive film, while the weather resistance is easily lowered and etching with Cu etchant Etching unevenness is likely to occur. Therefore, in the present invention, the amount of Mo added is preferably 5 to 40 atomic%. More preferably 5 to 30 atomic%, and still more preferably 10 to 25 atomic%.

Mn and Fe have a high effect of improving the etching property. However, the addition of Fe, which is a magnetic substance, to Ni increases the Curie point significantly. In addition, Fe has a low solubilization area with Cu and is easy to express a compound with Mo, and when added too much, the sputtering target becomes brittle. Therefore, in the present invention, it is preferable to add Fe in a range in which the sputtering target material satisfies the non-magnetic property and the etching property and is not brittle, and the addition amount thereof is 5 atomic% or less. More preferably, it is 3 atom% or less.

From the above, the sputtering target material for forming a coating layer of the present invention, which has a Curie point at room temperature or lower, which is capable of stably sputtering a coating layer which can achieve the adhesion, weather resistance, oxidation resistance and etching properties required for the coating layer of the Cu thin film layer, Is 5 to 25 atomic%, and the total amount of Mn and at least one element selected from Mo, Cu and Fe is 60 atomic% or less.

In addition, the greater the type and amount of the element added to Ni, the more the amount of the compound phase present in the sputtering target material increases, and the cracking tends to occur in machining or bonding when manufacturing a large sputtering target material required for FPD applications Loses. Therefore, in the present invention, it is preferable that Mn is 5 to 25 atomic%, Mo is 5 to 40 atomic%, and the total amount of Mn and Mo is 15 to 50 atomic%.

It is also preferable that Mn is 5 to 25 atomic%, Mo is 5 to 30 atomic%, Cu is 10 to 40 atomic%, and Fe is 0 to 5 atomic%.

Further, it is preferable that the total amount of Mn, Mo, Cu, and Fe is 27 to 20 atomic%, Mn is 10 to 25 atomic%, Cu is 10 to 25 atomic%, and Fe is 0 to 3 atomic% To 50 atomic%.

Next, a method for producing a sputtering target material for forming a coating layer of the present invention will be described.

An important feature of the method for producing a sputtering target material for forming a coating layer of the present invention is to select an element to be added to Ni which is a magnetic substance and to pressurize and sinter the alloy powder whose Curie point is not higher than room temperature. This is because Ni is a magnetic substance as described above. When the amount of Ni is increased, a Ni ferromagnetic phase, which easily tends to magnetize, remains in the sputtering target material. In the magnetron sputtering generally used in the production of FPD, Or the life of the sputtering target material may be shortened.

Conventionally, an ingot prepared by dissolving a raw material adjusted in a predetermined composition is subjected to plastic working to obtain a plate shape, and machining is performed to produce a sputtering target material. On the other hand, in the present invention, as described above, the addition amount of Mn or Mo is large and the plastic workability is deteriorated. Therefore, in order to stably produce the large sputtering target material for FPD, the manufacturing method of pressure- desirable.

In the present invention, it is preferable that the alloy powder contains Mn in an amount of 5 to 25 atomic% and contains at least 60 atomic% of Mn and at least one element selected from Mo, Cu and Fe in total, An alloy powder made of unavoidable impurities and having a Curie point of room temperature or lower is used.

In the present invention, the alloy powder preferably contains an alloy powder containing 5 to 25 atomic% of Mn, 5 to 40 atomic% of Mo, 15 to 50 atomic% of total of Mn and Mo, and the balance Ni and inevitable impurities Is preferably used.

The alloy powder preferably contains 5 to 25 atomic% of Mn, 5 to 30 atomic% of Mo, 10 to 40 atomic% of Cu, and 0 to 5 atomic% of Fe, with the balance being Ni and inevitable impurities .

The alloy powder preferably contains 7 to 20 atomic% of Mn, 10 to 30 atomic% of Mo, 10 to 25 atomic% of Cu, and 0 to 3 atomic% of Fe, with the balance being Ni and inevitable impurities , And the total amount of Mn, Mo, Cu and Fe is preferably 27 to 50 atomic%.

The alloy powder whose Curie point is not higher than room temperature can be easily obtained by the atomization method using an alloy adjusted to the final composition. It is also possible to produce an alloy powder by pulverizing the molten ingot. Also, a method of preparing various alloy powders and mixing them so as to have a final composition can be applied.

If the average particle size of the alloy powder is less than 5 占 퐉, impurities in the resulting sputtering target material are increased. On the other hand, when the average particle diameter of the alloy powder exceeds 300 탆, it becomes difficult to obtain a high-density sintered body. Therefore, the average particle diameter of the alloy powder is preferably 5 to 300 mu m.

The average particle diameter referred to in the present invention is represented by D50 of the cumulative particle size distribution using the spherical equivalent diameter by the light scattering method specified by JIS Z 8901 using laser light.

The pressure sintering used in the method for producing a sputtering target material for forming a coating layer of the present invention can be applied to a hot isostatic press (hereinafter referred to as " HIP ") or a hot press, 10 hours. The selection of these conditions depends on the apparatus for pressure sintering. For example, in the case of HIP, conditions of low temperature and high pressure are easily applied, and conditions of high temperature and low pressure are easily applied to hot press. In the production method of the present invention, it is preferable to use a hot isostatic press capable of suppressing diffusion of an alloy by sintering at a low temperature and sintering at a high pressure to obtain a high-density sintered body.

When the sintering temperature is less than 800 ° C, sintering is difficult to proceed and it is difficult to obtain a high-density sintered body. On the other hand, when the sintering temperature exceeds 1250 deg. C, a liquid phase is developed or the crystal growth of the sintered body becomes remarkable, making it difficult to obtain a uniform fine structure. By sintering in the range of 800 to 1250 占 폚, it becomes possible to easily obtain a sputtering target material for forming a high density coating layer.

When the pressing force at sintering is less than 10 MPa, sintering is difficult to proceed and a high-density sintered body can not be obtained. On the other hand, when the pressure exceeds 200 MPa, there is a problem that a device which can endure is limited.

If the sintering time is less than 1 hour, it is difficult to sufficiently advance sintering, and it is difficult to obtain a high-density sintered body. On the other hand, a sintering time exceeding 10 hours is preferably avoided from the viewpoint of production efficiency.

In the case of pressurizing and sintering by HIP or hot press, it is preferable that the alloy powder is filled in a pressure vessel or a pressure die, and then subjected to vacuum degassing while heating. The vacuum degassing is preferably carried out under a reduced pressure lower than the atmospheric pressure (101.3 kPa) in the heating temperature range of 100 to 600 ° C. This is because oxygen of the obtained sintered body can be further reduced and a sputtering target material for forming a coating layer of high purity can be obtained.

In the sputtering target material for forming a coating layer of the present invention, the elements other than Ni and Mn, Cu, Mo and Fe as main components are preferably as small as possible. If the amount of impurities other than the main component is large, the electrical resistance of the resultant laminated wiring film may increase, or the laminated thin film may react with other laminated thin films depending on the kind of the element to deteriorate properties such as adhesion and weather resistance. Particularly, oxygen and nitrogen of the gas component are easily introduced into the thin film, and the adhesiveness is lowered or defects are generated in the thin film. Therefore, the purity of the sputtering target material for forming a coating layer according to the present invention is preferably 99.9% by mass or more, more preferably 1000 ppm by mass or less, and more preferably 300 ppm by mass or less.

[Example 1]

10% Mn-25% Cu-10% Mo-3% in terms of atomic ratio In order to prepare a sputtering target material for forming a coating layer composed of Ni and inevitable impurities in the remaining amount of Fe, the purity of the composition was 99.9% The alloy powder having a thickness of 65 mu m was prepared by the gas atomization method.

When the obtained alloy powder was brought close to the SmCo magnet, it was confirmed that it did not adhere to the magnet. The obtained alloy powder was placed in a powder case for magnetic property measurement, and magnetic properties were measured at room temperature (25 ° C) using a vibrating sample type magnetometer VSM-5 manufactured by Rikudenshi Kabushiki Kaisha In other words, I confirmed that I was a visa adult.

Next, the alloy powder obtained above was filled in a container made of soft-drawn steel having an inner diameter of 133 mm, a height of 30 mm and a thickness of 3 mm and heated at 450 캜 for 10 hours for degassing treatment. Thereafter, , And sintered under the conditions of 1000 占 폚 and 148 MPa for 5 hours by a HIP apparatus.

The cooled soft container was cooled and taken out from the HIP apparatus, and the soft container was removed by machining to obtain a sputtering target material for forming a coating layer having a diameter of 100 mm and a thickness of 5 mm. Further, the test piece was cut out from the remaining portion.

The relative density of the obtained test pieces was measured by the Archimedes method. The relative density referred to in the present invention refers to the density obtained by dividing the bulk density measured by the Archimedes method by the theoretical density obtained as a weighted average of the elemental organisms calculated by the mass ratio obtained from the composition ratio of the sputtering target material for forming a coating layer of the present invention The value obtained by multiplying the value by 100.

As a result, it was confirmed that the relative density was 99.9%. According to the manufacturing method of the present invention, it was confirmed that a sputtering target material for forming a coating layer of high density can be obtained.

Next, the quantitative analysis of the metal element of the obtained test piece was carried out using an inductively coupled plasma emission spectrometer (ICP) (model number: ICPV-1017) manufactured by Shimadzu Corporation of Shibaisha Seisakusho Co., , The total purity of the analysis values of Ni, Mn, Cu, Mo, and Fe was 99.9% and the oxygen concentration was 500 mass ppm. According to the production method of the present invention, It was confirmed that a sputtering target material for forming a coating layer was obtained.

The specimens obtained above were mirror-polished, corroded with a bombardment reagent, and observed under an optical microscope. The results are shown in Fig. As shown in Fig. 1, the sputtering target for forming a coating layer of the present invention had a fine recrystallized structure in spherical alloy powder obtained by the gas atomization method, and the average crystal grain diameter was 35 탆. Further, it was confirmed that the sputtering target material for forming a coating layer of the present invention is a sputtering target material suitable for sputtering deposition without any large defects such as segregation or vacancy.

Next, the sputtering target material for forming a coating layer obtained above was brazed to a backing plate made of copper, and then mounted on a sputtering machine (Model No. CS-200) manufactured by ULVAC CO., LTD. A sputter test was performed under the condition of 500 W of electric power. It was confirmed that sputtering using the sputtering target for forming a coating layer of the present invention enabled sputtering with no abnormal discharge and stable sputtering.

[Example 2]

Next, a Cu sputtering target material cut out from a sheet of oxygen-free copper made by Hitachi Densen Co., Ltd. (currently Hitachi Metal Corporation) (Hitachi Metal Corporation) Using a sputtering target material for forming a coating layer of the present invention, a glass substrate (product number: EagleXG) of 25 mm x 50 mm made by Corning Incorporated was subjected to the same sputtering conditions as in Example 1, A 50 nm thick coating layer, a 200 nm thick Cu thin film layer, and a 50 nm thick coating layer were sequentially formed, and the moisture resistance and heat resistance were evaluated as adhesion and weather resistance.

The adhesion was evaluated by the method prescribed in JIS K5400. First, a transparent pressure-sensitive adhesive tape (trade name: transparent clear color) made by Sumitomo 3M Ltd. was attached to the surface of the coating layer formed above, and a grid pattern having a side of 2 mm was cut with a cutter knife And a transparent adhesive tape was peeled off, and evaluation was made as to whether or not the coating layer remained. It was confirmed that the coating layer formed by using the sputtering target material for forming a coating layer of the present invention did not peel off even one space and had high adhesion.

In the evaluation of the moisture resistance, the sample prepared above was allowed to stand in an atmosphere having a temperature of 85 캜 and a humidity of 85% for 300 hours, and the presence or absence of discoloration of the surface of the coating layer was visually confirmed. It was confirmed that the coating layer formed by using the sputtering target material for forming a coating layer of the present invention did not discolor even when exposed to a high temperature and high humidity atmosphere and had high moisture resistance.

In the evaluation of the heat resistance, the sample prepared above was heated for 30 minutes in an atmosphere at 350 캜 in the atmosphere, and the presence or absence of discoloration of the surface of the coating layer was visually confirmed. It was confirmed that the coating layer formed by using the sputtering target material for forming a coating layer of the present invention did not change color even when heated at a high temperature and was a coating layer having high heat resistance.

[Example 3]

First, a sputtering target material for forming a coating layer of the present invention prepared in Example 1 and a Cu sputtering target material prepared in Example 2 were prepared. As a comparison, an ingot of each alloy consisting of Ni-18% Mo and Ni-30% Cu-3% Ti in atomic ratio was cast by a vacuum melting method and machined to have a diameter of 100 mm and a thickness of 5 mm Thereby preparing a sputtering target material. Next, each of the sputtering target materials was brazed to a copper backing plate, and the sputtering target material was mounted on the same sputtering apparatus as in Example 2. Then, a sample for evaluation of etching, in which a coating layer having a thickness of 100 nm was formed on a 25 mm x 50 mm glass substrate (product number: EagleXG) manufactured by Corning Incorporated under the same conditions as in Example 2, was obtained.

Using a sputtering target material for forming a coating layer of the present invention and a Cu sputtering target material prepared above, a glass substrate (product number: EagleXG) of 25 mm x 50 mm made by Corning Incorporated under the same sputter conditions as in Example 1 , A coating layer having a film thickness of 50 nm, a Cu thin film layer having a film thickness of 200 nm, and a coating layer having a film thickness of 50 nm were sequentially formed.

Each of the samples obtained above was immersed in CU-02 manufactured by Kanto Chemical Co., Ltd., an etchant of Cu, to perform etching, and the sample was visually observed until the coating layer on the glass substrate was completely observed. The time was measured, and the unevenness at the time of etching was also checked.

As a result, in the sample of the single layer film of 100 nm, Cu was uniformly etched in about 25 seconds. On the other hand, the coating layer made of the Ni-18 atomic% Mo alloy required 90 seconds to complete the etching, and it was confirmed that irregularities were caused by etching in a region where the etching is fast and the region where the etching is fast and the island portion.

In addition, it was confirmed that a coating layer composed of a Ni-30 atomic% Cu-3 atomic% Ti alloy requires a time of 100 seconds until the etching is finished, and that a portion with a high etching speed and a portion with a slow etching rate are etched in a stripe shape.

On the contrary, it was confirmed that the coating layer formed by the sputtering target material for forming a coating layer of the present invention was uniformly etched in about 40 seconds.

Further, the sample for etching evaluation, in which the laminated wiring film was formed using the sputtering target material for forming a coating layer of the present invention, required about 90 seconds until completion of etching, and it was possible to etch uniformly without stains.

From the above, it is presumable that the coating layer formed of the sputtering target material for forming a coating layer of the present invention can etch uniformly at a narrow pitch by using an etchant of Cu, even when the layer is laminated with a Cu thin film layer.

[Example 4]

In order to produce a sputtering target material having the composition shown in Table 1, raw materials of Ni, Mn, Cu, and Mo having a purity of 3N or more were prepared, weighed so as to have a predetermined composition, and an ingot was produced by a molten casting method in a vacuum melting furnace. The adhesion of the produced ingot to the magnet, machinability, and sputtering resistance were evaluated. The evaluation of the machinability of the sputtering target material was evaluated as & cir &, where cracking occurred during machining, and & cir & The evaluation of the spatter dischargeability was evaluated as & cir &, in which no abnormal discharge was observed and good sputtering was possible. The results are shown in Table 1.

The SmCo magnet was brought close to the ingot, and the sample No. 3 as a comparative example was attached to the magnet, confirming that it was a magnetic body. On the other hand, samples made of other alloys were found not to be attached to SmCo magnets but viscous.

Sample No. 2 and Sample No. 4 had cracks when the ingot was taken out of the ingot case. Then, the sample No. 2 stopped its evaluation.

Using each ingot described above, an alloy powder was produced by the atomization method as in Example 1, and a sintered body was produced by HIP. Each of the sintered bodies was cut with a wire cut to produce a sputtering target material having a diameter of 100 mm and a thickness of 5 mm. As a result, Sample No. 3 and Sample No. 10 were cracked during processing. Sample No. 4 was cracked, and a sputtering target could not be produced.

Next, sputtering targets of sample No. 1, sample No. 3, and samples No. 5 to No. 10, which were producible, were brazed to a copper backing plate. Thereafter, the resultant was mounted on a sputtering apparatus (model number: CS-200) manufactured by ULVAC CO., LTD. And subjected to a sputter test under the conditions of an Ar atmosphere, a pressure of 0.5 Pa, and a power of 500 W.

It was confirmed that sputtering using the sputtering target for forming a coating layer of the present invention enabled sputtering with no abnormal discharge and stable sputtering.

[Example 5]

After the discharge test in Example 4, a coating layer having a film thickness shown in Table 2 was formed on a glass substrate having a size of 25 mm x 50 mm to prepare a sample for evaluation of etching. The evaluation of the etchability was carried out by using an etchant for Cu (CU-02) made by Kanto Kagaku Co., Ltd. in the same manner as in Example 3. It is necessary to suppress the unevenness of the etching time, to reduce the over-etching time, and to appropriately suppress the wettability to the etchant.

The etching unevenness was visually confirmed as in Example 3. To make a clearer difference, each sample was immersed in an etchant solution, and a time difference between the time when a part of the film was permeated and the time when the entire surface was permeated was measured. This means that the smaller the time difference is, the smaller the etching unevenness is. Further, 20 占 퐇 of an etchant was dripped onto the surface of the film, and an enlarged diameter after 2 minutes was measured. This means that as the enlarged diameter is smaller, side etching can be suppressed and etching with high precision can be performed. The evaluation results are shown in Table 2.

As shown in Table 2, the coating layer formed of a sputtering target material for forming a coating layer containing an appropriate amount of Mn of the present invention had a small time lag between initiation and termination of membrane permeation at the time of etching, an enlarged diameter of the etchant was small, It was confirmed that it is possible to carry out etching with a high degree of accuracy, which is almost equivalent and has less etching unevenness and less side etching.

[Example 6]

Next, in the same manner as in Example 2, a sample of a laminated wiring film in which a coating layer having a film thickness of 50 nm, a Cu thin film layer having a film thickness of 300 nm, and a coating layer having a film thickness of 50 nm were sequentially formed was formed on a glass substrate. Then, the adhesion and oxidation resistance of each sample were evaluated. The evaluation of the adhesion was carried out in the same manner as in Example 2. The coating layer having no peeled off was evaluated as?, The peeled one with?, And the peeled with two or more peelings.

In the evaluation of the oxidation resistance, each sample was subjected to heat treatment at a temperature of 200 ° C to 300 ° C in an air atmosphere for 30 minutes, and the reflectance was measured. The reflectance was measured using a spectrocolorimeter (model number: CM2500d) manufactured by Konica Minolta Co., Ltd. The evaluation results are shown in Table 3.

As shown in Table 3, Sample No. 1 and Sample No. 11 had poor adhesion. In Sample No. 5, the adhesion was improved by containing 4% of Mn, but it was found that the sample No. 5 was not yet sufficient.

On the other hand, it was confirmed that the laminated film in which the coating film was formed by using the sputtering target material for forming a coating layer of the present invention was greatly improved in adhesion.

In sample No. 1, the reflectance was significantly lowered at a high temperature and the oxidation resistance was low.

On the other hand, it was confirmed that even when the laminated film formed with the coating film using the sputtering target material for forming a coating layer was heated to a high temperature of 350 캜, the decrease in reflectance was suppressed and sufficient oxidation resistance was obtained.

[Example 7]

Next, using the sample prepared in Example 6, the moisture resistance, which is one of the weather resistance, was evaluated. The moisture resistance was evaluated in the same manner as in Example 2, and the reflectance was measured in the same manner as in Example 6. [ The evaluation results are shown in Table 4.

As shown in Table 4, it was confirmed that the laminated film in which the coating layer was formed by using the sputtering target material for forming a coating layer of the present invention had a small decrease in reflectance due to discoloration even after being left in a high temperature and high humidity atmosphere for a long time, I could.

From the above, it was confirmed that by using the sputtering target material for forming a coating layer of the present invention, it is possible to stably form a coating layer capable of stable wet etching while ensuring the adhesion of the Cu thin film layer, weather resistance, and oxidation resistance.

Claims (8)

A sputtering target material for forming a coating layer of a thin film layer made of Cu or a Cu alloy, which contains 5 to 25 atom% of Mn and at least one element selected from Mn, Mo, Cu and Fe in a total amount of 60 atomic% And the balance being Ni and inevitable impurities, and having a Curie point of not more than room temperature. The sputtering target material for forming a coating layer according to claim 1, wherein the Mo content is 5 to 40 atomic%, and the total amount of Mn and Mo is 15 to 50 atomic%. The sputtering target material for forming a coating layer according to claim 1, wherein the Mo is from 5 to 30 atomic%, the Cu is from 10 to 40 atomic%, and the Fe is from 0 to 5 atomic%. The nonaqueous electrolyte secondary battery according to claim 1, wherein the Mn is 7 to 20 atomic%, the Mo is 10 to 25 atomic%, the Cu is 10 to 25 atomic%, the Fe is 0 to 3 atomic% Wherein the total amount of Cu and Fe is 27 to 50 atomic%. A method for producing a sputtering target material for forming a coating layer of a thin film layer made of Cu or a Cu alloy, which comprises 5 to 25 atomic percent of Mn and at least one element selected from Mn, Mo, Cu and Fe, By mass or less, and the remainder being Ni and inevitable impurities, and the alloy powder having a Curie point of not more than room temperature is pressed and sintered to obtain a sputtering target material for forming a coating layer. The method for producing a sputtering target material for forming a coating layer according to claim 5, wherein the alloy powder contains 5 to 40 atom% of Mo and 15 to 50 atom% of the total amount of Mn and Mo. The sputtering target material for forming a coating layer according to claim 5, wherein the alloy powder contains 5 to 30 atomic% of Mo, 10 to 40 atomic% of Cu, and 0 to 5 atomic% of Fe Way. The alloy powder according to claim 5, wherein the alloy powder contains 7 to 20 atomic% of Mn, 10 to 30 atomic% of Mo, 10 to 25 atomic% of Cu, 0 to 3 atomic% of Fe, Wherein the total amount of Mn, Mo, Cu and Fe is 27 to 50 atomic%.

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