KR20060119735A - Sputtering target and manufacturing method thereof - Google Patents

Abstract

A sputtering target and a manufacturing method thereof are provided to acquire a black matrix thin film without Cr and to reduce an environmental pollution. A sputtering target is made of tungsten of 5 to 30 weight%, a predetermined material, oxygen, and nickel. The predetermined material is made of at least one selected from a group consisting of aluminium and titanium. The weight% of the predetermined material is in a predetermined range of 0.1 to 10. The weight% of the oxygen is in a predetermined range of 0.05 or less. The mean grain size of the sputtering target is in a predetermined range of 100 mum or less. The surface roughness of the sputtering target is in a predetermined range of 10 mum or less.

Description

Sputtering target and manufacturing method

Patent Document 1: Japanese Patent Publication No. 2001-342561

Patent Document 2: Japanese Patent Publication No. 2000-121824

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to sputtering targets used in forming thin films using the sputtering method, and methods of manufacturing the same. More particularly, the present invention relates to sputtering targets suitable for forming a black matrix film and a method of manufacturing the same. .

In the field of optics and microelectronics, various thin film members obtained by forming a thin film on a substrate such as sputtering are used. One of these members is a black matrix for color filters used in display devices such as liquid crystal display devices and plasma displays.

In liquid crystal displays and plasma displays, color filters are used that enable color display in accordance with transmission of light from a light source. This color filter is formed by forming a colored layer, a transparent protective layer, and the like on a transparent glass substrate, and a light shielding film called a black matrix is provided in the color filter in order to improve contrast and prevent color mixing.

As a typical method for producing this black matrix, the method of forming a predetermined pattern using the photolithography method is common. In the photolithography method, a metal thin film is formed by sputtering a metal on a glass substrate, then a photoresist is applied on the metal thin film, followed by exposure and development to etch the metal thin film.

This black matrix requires not only a light shielding that blocks unwanted portions of light from the light source, and a low reflectance to maintain a good contrast of the display image, but also no film defects that can cause color defects on the display. Is required. In particular, in recent years, advances have been made in realizing these displays having high resolution and high field of view, and also progressed in making the pitch of the black matrix narrower and higher apertured, so that there is no black defect. Formation of the matrix film is required. In other words, the black matrix is required to be free from disconnection or defects in the black matrix line due to pin holes or the like. Moreover, in recent years, with the improvement of display performance, the high resolution of the black matrix and the improvement of an aperture ratio are needed, and the pitch of a line width narrows in progress. Therefore, in the production of the black matrix, it is required to further reduce the film defect and to make it smaller.

Since this kind of performance is required in the black matrix, chromium (Cr) is commonly used as the black matrix thin film.

Chromium has low reflectance and excellent light shielding properties and has good optical properties for use as a black matrix. However, a film defect easily occurs when the film of chromium is formed by the sputtering method.

In addition, when chromium is used for a thin film member such as a black matrix, hexavalent chromium ions are generated during an etching process in a patterning process, thereby causing environmental pollution.

Therefore, in recent years, nickel (Ni) -based alloy (see, for example, Patent Document 1 (Japanese Patent Laid-Open No. 2001-342561)) and indium (In) -based alloy or zinc (Zn) -based alloy as a substitute material for chromium An alloy (for example, refer patent document 2 (Japanese Patent Laid-Open No. 2000-121824)) is proposed.

However, although the black matrix film of patent document 1 is excellent in the aspect of an optical characteristic, a film defect generate | occur | produces when manufactured using the sputtering method.

In addition, when manufacturing the black matrix film of patent document 2, sputtering is performed using the target containing indium or zinc, but when oxygen mixes with argon gas, a nodule generate | occur | produces on the target surface, and abnormal discharge is prevented. There is a problem that is easy to occur. In addition, film defects easily occur.

The present invention has been made in view of these problems, and an object of the present invention is to provide a sputtering target capable of forming a thin film containing little chromium which causes environmental pollution.

The sputtering target according to the present invention contains 5 to 30% by weight of tungsten (W), 0.1 to 10% by weight of at least one of aluminum (Al) and titanium (Ti), and the amount of oxygen contained is 0.05% by weight or less. And the balance is substantially nickel (Ni).

In the sputtering target, the average grain size is preferably 100 µm or less, and the surface roughness Ra is preferably 10 µm or less. Here, the average grain size is the average value of the grain sizes measured by the quadrature method described in JIS H051, and the surface roughness Ra is the arithmetic mean roughness of the roughness curve (measured according to JIS B0601 (1994)).

The thin film obtained by performing sputtering using the sputtering target has a particle number of 3 µm or more in the film of less than 2 / cm 2.

Method for producing a sputtering target according to the present invention contains 5 to 30% by weight of tungsten (W), 0.1 to 10% by weight of at least one of aluminum (Al) and titanium (Ti) in total, the amount of oxygen contained 0.05 weight Step 1 and the castings obtained in step 1 are obtained by measuring and mixing the raw material metal so that the remainder is% or less, and the balance is substantially nickel (Ni), dissolving and casting the sugar raw material metal in a vacuum or in an inert atmosphere. Process 2 to obtain a forging material or a rolled material by hot forging and / or hot rolling in a vacuum or in an inert atmosphere, and processing the forging material or rolled material obtained in step 2 to a predetermined shape to obtain a sputtering target It is characterized by having a step 3. In the said process 2, it is preferable to perform heat processing after performing hot forging and / or hot rolling. Or after performing hot forging and / or hot rolling in the said process 2, it is preferable to cold-process and then to heat-treat.

It is preferable that the size of the average crystal grain size of the forging material or the rolling material produced in step 2 is 100 µm or less.

Moreover, it is preferable that the surface roughness Ra of the sputtering target obtained by the said process 3 becomes 10 micrometers or less.

The present inventor has made a thorough research and investigation into the defects of the black matrix film in order to identify the cause of the defects of the black matrix film. As a result, particles of 3 to 80 µm in size that are believed to adhere to the film during sputtering are present at the defect site of the film. It was found that these particles contributed to defects in the black matrix film. As a result of analysis of these particles, it was confirmed that there existed the same metal as the target and that the amount of oxygen was larger than that of the black matrix film.

In addition, as a result of intensive research on the cause of the generation of these particles, the following four facts were found.

The first case is as follows. When the oxygen concentration in the sputtering target of the Ni-based alloy is high, a part of Al and / or Ti, which is an active metal added to the Ni-based alloy, becomes an oxide and exists in the sputtering target as a inclusion. This inclusion is a starting point for abnormal discharge during sputtering because its resistance is significantly higher than that of other parts. Thus, it has been found that particles are formed because the abnormal discharge causes the inclusions to be destroyed or scattered or the micro parts around the inclusions melted and scattered.

The second case is as follows. Some of the sputtered particles sputtered once are returned to the target direction by scattering between the particles during the sputtering process, or when the unevenness of the target surface is severe, the sputtered particles accumulate in the fine part (groove). In the case of forming a black matrix film, reactive sputtering is performed by introducing oxygen or nitrogen into argon, which is a sputtering gas, in order to lower the optical transmittance. For this reason, the sputtered particles returned to the target become oxide or nitride particles having high resistance, and the accumulated particles remain on the target without sputtering again. On the other hand, the usual metal parts around the deposits are sputtered and shaved off. For this reason, it was found that the accumulated portion of the returned particles forms a projection on the target surface, and this site is a starting point of abnormal discharge and generates particles. In addition, the average crystal grains and the surface roughness Ra cause the particles of the sputtering target surface to scatter during sputtering, thereby affecting the unevenness of the sputtering target surface.

The third case is as follows. When the chromium film is formed by the sputtering method, since the stress of the film is increased, the chromium film adhered to the protective plate in the sputtering apparatus or the like tends to be torn and scattered due to the stress of the film. When the scattered pieces of film adhere to the film on the substrate, they tend to become particles in the film defect. Furthermore, since the Cr target is produced by the powder metallurgy method, a large amount of fine space is generated in the Cr target and at the same time, the amount of oxygen also increases. For this reason, when Cr target was used, it turned out that particle | grains generate | occur | produce easily in the film | membrane on a board | substrate by abnormal discharge during sputtering.

The fourth case is as follows. As described in Patent Literature 2, it has been found that sputtering using a target containing indium or zinc, which is a low melting point metal, tends to cause large molten particles likely to occur in the film due to abnormal discharge.

Based on the above facts, the present inventors have 5 to 30% by weight of W, and 0.1 to 10% by weight of at least one of Al and Ti in total, and the balance is made of Ni-based alloy with substantially Ni. By using a sputtering target having an oxygen content of 0.05% by weight or less, the particles in the film obtained by sputtering can be reduced, thereby completing the present invention. In particular, in the present invention, it has been found that the particles in the film obtained can be further reduced by setting the average grain size of the sputtering target to 100 µm or less and the surface roughness Ra of the target to 10 µm or less.

EMBODIMENT OF THE INVENTION Hereinafter, the sputtering target by this invention is demonstrated in detail.

The sputtering target according to the present invention is a Ni-based alloy based on nickel (Ni) and containing tungsten (W) and aluminum (Al) and / or titanium (Ti) and containing no chromium (Cr) at all.

In the production of the sputtering target according to the present invention, the metal, which is a raw material, is heated to a high temperature in a vacuum to be melted, and then flowed into a mold and cast, followed by hot forging and / or hot rolling in a vacuum. Thereafter, heat treatment may be performed in a vacuum at a predetermined temperature or after cold working. Thereafter, lathe machining and surface grinding are performed to a predetermined shape and metal bonded to a backing plate to obtain a sputtering target according to the present invention.

Ni is a black matrix used for color filters and is an element necessary to attain the required optical properties and at the same time to ensure corrosion resistance.

W acts to improve the corrosion resistance of the thin film. In the sputtering target by this invention, it is necessary to contain W by 5-30 weight%. When W is lower than 5 weight%, corrosion resistance is inadequate, and when W exceeds 30 weight%, workability as an alloy worsens.

Al and Ti serve to improve the resist wettability of the obtained thin film. In the sputtering target by this invention, it is necessary to contain 0.1-10 weight% in total of at least 1 sort (s) of Al and Ti. When the total content of Al and Ti is lower than 0.1% by weight, the resist wettability of the obtained thin film is insufficient, making it difficult to form a predetermined shape pattern on the thin film by the photolithography method. If the content exceeds 10% by weight, workability as an alloy is deteriorated, so that cracking occurs in processing steps such as hot forging and cold rolling, and machining as a sputtering target becomes difficult.

In addition, the amount of oxygen in the target needs to be 0.05% by weight or less. As described above, in the sputtering target according to the present invention, at least one of Al and Ti is contained in the target, and since Al and Ti are active metals, they are easily oxidized in the steps of dissolution, forging, hot forging and rolling, and sputtering target. It becomes an oxide in the inside, and it becomes easy to become an inclusion. When these inclusions exist in a target, it becomes a cause of the particle | grains which generate | occur | produce by abnormal discharge etc. at the time of sputtering. Therefore, in the sputtering target by this invention, it is necessary to make oxygen amount into 0.05 weight% or less. For this reason, in manufacture of the sputtering target by this invention, when melt | dissolution, forging, hot forging, and rolling are performed, it is preferable to carry out in inert atmosphere or in vacuum.

In addition, the sputtering target according to the present invention may be manufactured by a method of powder metallurgy such as hot pressing or HIP, or by sintering by sintering molten metal liquid droplets without dissolving and forging. In any of the above methods, it is preferable to sinter in an inert atmosphere or in vacuum using a raw material having a small oxygen content.

Next, preferable surface roughness Ra and average grain size in the sputtering target by this invention are demonstrated.

If the surface of the sputtering target has irregularities exceeding 10 μm, the sputtered particles once sputtered back to the target and accumulate in the grooves on the target surface. When manufacturing a thin film for black matrix, a film having particles accumulated in grooves on the target surface to form reactive sputtering by injecting oxygen or nitrogen into argon, a sputtering gas, in order to reduce optical transmittance, forms a high resistance film of an oxide film or a nitride film. Done. For this reason, as mentioned above, since abnormal discharge is easy to generate | occur | produce and particle generation may increase, it is preferable to make surface roughness Ra of a sputtering target into 10 micrometers or less, and it is more preferable to set it as 5 micrometers or less. However, in order to make surface roughness Ra into 1 micrometer or less, since grinding | polishing process cost is high, it is industrially difficult to make surface roughness Ra into 1 micrometer or less.

The average grain size affects the flatness (unevenness) of the sputtering target surface caused by corrosion by sputtering. If the average grain size is larger than 100 µm, large irregularities occur in the sputtered corrosion surface. In this recessed portion, sputtered particles returned are likely to accumulate and are likely to cause abnormal discharge. In addition, when the average grain size is large, inclusions tend to be ubiquitous at the grain boundary, and the size of the inclusions also increases, so that abnormal discharge easily occurs, and particles are easily generated. Therefore, the size of the average grain size of the sputtering target according to the present invention is preferably set to 100 µm or less.

As described above, the sputtering target according to the present invention contains 5 to 30% by weight of W, 0.1 to 10% by weight of at least one of Al and Ti in total, the amount of oxygen contained is 0.05% by weight or less, Since the balance is substantially Ni, by using the sputtering target according to the present invention, abnormal discharge can be reduced during sputtering, and a thin film for black matrix having a number of particles of 3 µm or more in the film of less than 2 / cm 2 can be formed. . When the number of particles having a thickness of 3 µm or more in the film is less than 2 / cm 2, the defect as the film used for the black matrix can be said to be a level where there is no problem in practical use.

Furthermore, in the sputtering target according to the present invention, the average crystal grain size is 100 µm or less and the surface roughness Ra is 10 µm or less, so that abnormal discharge can be reduced during sputtering, and the black matrix has fewer particles. A thin film can be formed.

In addition, since the sputtering target according to the present invention does not contain Cr, hexavalent chromium ions are not generated during etching for patterning the formed thin film, and there is no fear of contaminating the environment.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example  One

The total amount of metal Ni (electrolytic nickel, purity 99.99% by weight), metal W (purity 99.9% by weight), metal Al (Al bare metal, purity 99% or more) is about 30 kg, and the composition is W 15% by weight, 2% by weight of Al and the balance were weighed to be Ni.

Each raw material blended to the above composition was melted in vacuum using a high frequency vacuum melting furnace and cast using a mold, followed by hot forging and hot rolling at 1100 ° C. in a vacuum to press the sheet to have a thickness of 8 mm. Then, a heat treatment at 750 ° C. was performed in vacuum. Thereafter, lathe and planar grinding were performed to cut each into a shape of 152 mm in diameter and 5 mm in thickness, and metal bonded to a steel backing plate to obtain a sputtering target having the above composition. In the planar grinding, abrasive grains were used with a grain size of # 60, the polishing depth was 6 to 8 µm, and the polishing rate was 25 m / min.

The amount of oxygen of the obtained target was measured by the high frequency combustion infrared absorption method. The average crystal grain size of the obtained target was measured by the quadrature method described in Japanese Industrial Standard JIS H0501 (1986). The surface roughness Ra of the obtained target was measured using the arithmetic mean roughness (measured according to JIS B0601 (1994)) of the roughness curve. The oxygen amount, average grain size, and surface roughness Ra of the measured target are shown in Table 1.

Next, sputtering was performed using the obtained sputtering target, and the thin film of thickness 0.1micrometer was formed on the glass substrate of 100 mm x 100 mm x 5 mm.

In sputtering conditions, the inside of the sputtering apparatus was evacuated to high vacuum, and then Ar gas was introduced to perform preliminary sputtering for 30 minutes to exclude the influence of oxidation of the target surface. Subsequently, a gas in which 15% by volume of oxygen was mixed with Ar gas was introduced to about 300 pa, and sputtered at an input power of 510W.

About the obtained film | membrane, 20 particle | grains were measured about 100 mm x 100 mm area | region by the particle counter using the particle counter, and the average value was computed. The results are shown in Table 1.

In addition, the resist wettability of the obtained film was evaluated. Specifically, the contact angle between the film and the photoresist obtained by the projection method by dropping a novolac resin photoresist on the surface of the sample and using the Kyowa contact angle system CA-P type manufactured by Kyoyo Kagaku Co., Ltd. Was measured. Table 1 shows the result of measuring the contact angle between the obtained film and resist.

In addition, scattering of debris due to detachment of the film adhered in the sputtering device and tearing of the film after sputtering was not observed.

Example  2

In order to investigate the influence of the surface roughness, except that the surface roughness Ra of the target is 12 µm, plane grinding is performed by using the abrasive grain of abrasive stone as # 40, the polishing depth as 15 µm and the polishing speed as 25 m / min. A sputtering target was produced in the same manner as in Example 1. Furthermore, sputtering was carried out in the same manner as in Example 1 to form a film. The particle number measurement of the obtained film | membrane was performed like Example 1. Furthermore, the contact angle measurement of the obtained film and resist was carried out as in Example 1.

Table 1 shows the measurement results of the number of particles of 3 µm or more in the film obtained by the amount of oxygen, average grain size, surface roughness Ra, and sputtering of the obtained target. Moreover, the measurement result of the contact angle of the obtained film | membrane and a resist was shown in Table 1 together.

In addition, scattering of debris due to detachment of the film adhered in the sputtering device and tearing of the film after sputtering was not observed.

Example  3

As in Example 1, except that the metal Ni was made of high purity Ni (99.995 weight%, oxygen amount 0.001% or less), the metal Al was made of high purity Al (purity 99.999%, oxygen content 0.002% or less), and the amount of oxygen contained was used as a raw material. Sputtering targets were prepared. In addition, sputtering was carried out as in Example 1 to form a film. The particle number was measured in the same manner as in Example 1. In addition, the contact angle of the obtained film | membrane and resist was measured like Example 1.

Table 1 shows the particle number measurement results of 3 µm or more in the film obtained by the amount of oxygen, average grain size, surface roughness Ra, and sputtering of the obtained target. Moreover, the measurement result of the contact angle of the obtained film | membrane and a resist was shown in Table 1 together.

In addition, scattering of debris due to detachment of the film adhered in the sputtering device and tearing of the film after sputtering was not observed.

Example  4

In order to reduce the average crystal grains of the alloy constituting the target, the hot rolled sheet obtained in the same manner as in Example 1 was cold rolled sequentially from 8 mm to 5.5 mm in thickness, and then at a relatively low temperature of 550 ° C. in vacuum. Heat treatment was performed. The obtained plate material was then made into a sputtering target in the same manner as in Example 1, and further sputtered as in Example 1 to form a film. The particle number was measured in the same manner as in Example 1. In addition, the contact angle of the obtained film | membrane and resist was measured like Example 1.

Table 1 shows the particle number measurement results of 3 µm or more in the film obtained by the amount of oxygen, average grain size, surface roughness Ra, and sputtering of the obtained target. Moreover, the measurement result of the contact angle of the obtained film | membrane and a resist was shown in Table 1 together.

In addition, scattering of debris due to detachment of the film adhered in the sputtering device and tearing of the film after sputtering was not observed.

Example  5

In order to increase the average crystal grains of the alloy constituting the target, the hot rolled sheet obtained in the same manner as in Example 1 was cold rolled sequentially from 8 mm to 5.5 mm in thickness, and then at a relatively high temperature of 980 ° C. in vacuum. Heat treatment was performed. The obtained plate material was then made into a sputtering target in the same manner as in Example 1, and further sputtered as in Example 1 to form a film. The particle number was measured in the same manner as in Example 1. In addition, the contact angle of the obtained film | membrane and resist was measured like Example 1.

Table 1 shows the particle number measurement results of 3 µm or more in the film obtained by the amount of oxygen, average grain size, surface roughness Ra, and sputtering of the obtained target. Moreover, the measurement result of the contact angle of the obtained film | membrane and a resist was shown in Table 1 together.

In addition, scattering of debris due to detachment of the film adhered in the sputtering device and tearing of the film after sputtering was not observed.

Example  6

A sputtering target was prepared in the same manner as in Example 5 except that the surface roughness Ra of the target was changed to 12 µm using abrasive grains having coarse abrasive grains for planar grinding. Then, as in Example 1, sputtering was performed to form a film. The particle number was measured in the same manner as in Example 1. In addition, the contact angle of the obtained film | membrane and resist was measured like Example 1.

Table 1 shows the particle number measurement results of 3 µm or more in the film obtained by the amount of oxygen, average grain size, surface roughness Ra, and sputtering of the obtained target. Moreover, the measurement result of the contact angle of the obtained film | membrane and resist is shown in Table 1.

In addition, scattering of debris due to detachment of the film adhered in the sputtering device and tearing of the film after sputtering was not observed.

Example  7

Using the same metal as in Example 1, the composition was weighed so as to have a composition of 17% by weight of W, 7% by weight of Al, and the remaining amount of Ni, and was dissolved in vacuum in the same manner as in Example 1 except that it was blended, and cast using a mold. . The resulting cast material was cut into a plate of 6 mm thickness with a wire cutter, cut in a diameter of 152 mm with a wire cutter in the same manner, and then subjected to lathe and surface grinding under the same conditions as in Example 1, followed by a sputtering target. Was prepared. And sputtering was carried out as in Example 1 to form a film. The particle number was measured in the same manner as in Example 1, and the contact angle between the obtained film and the resist was measured in the same manner as in Example 1.

Table 1 shows the particle number measurement results of 3 µm or more in the film obtained by the amount of oxygen, average grain size, surface roughness Ra, and sputtering of the obtained target. Moreover, the measurement result of the contact angle of the obtained film | membrane and a resist was shown in Table 1 together.

In addition, scattering of debris due to detachment of the film adhered in the sputtering device and tearing of the film after sputtering was not observed.

Example  8

The total amount of metal Ni (electrolytic nickel, purity 99.99% by weight), metal W (purity 99.99% by weight), metal Al (Al now, purity 99% or more) and metal Ti (Ti ore, JIS grade 1) It became about 30 kg, and it weighed and mix | blended so that the composition might be 15 weight% of W, 3.5 weight% of Al, 3.5 weight% of Ti, and remainder to Ni. Thereafter, the sputtering target was manufactured by casting and processing in the same manner as in Example 7. Then, sputtering was carried out in the same manner as in Example 1 to form a film. The particle number was measured in the same manner as in Example 1, and the contact angle between the obtained film and the resist was measured in the same manner as in Example 1.

Table 1 shows the particle number measurement results of 3 µm or more in the film obtained by the amount of oxygen, average grain size, surface roughness Ra, and sputtering of the obtained target. Moreover, the measurement result of the contact angle of the obtained film | membrane and a resist was shown in Table 1 together.

In addition, scattering of debris due to detachment of the film adhered in the sputtering device and tearing of the film after sputtering was not observed.

Example  9

The total amount of metal Ni (electrolytic nickel, purity 99.99% by weight), metal W (purity 99.99% by weight), and metal Ti (Ti ,, JIS grade 1) is about 30 kg, and the composition is 15% by weight W , Ti 6% by weight and the balance was weighed to blend Ni. Otherwise, the sputtering target was manufactured by casting and processing in the same manner as in Example 7. And sputtering was carried out in the same manner as in Example 1 to form a film. The particle number was measured in the same manner as in Example 1, and the contact angle between the obtained film and the resist was measured in the same manner as in Example 1.

Table 1 shows the particle number measurement results of 3 µm or more in the film obtained by the amount of oxygen, average grain size, surface roughness Ra, and sputtering of the obtained target. Moreover, the measurement result of the contact angle of the obtained film | membrane and a resist was shown in Table 1 together.

In addition, scattering of debris due to detachment of the film adhered in the sputtering device and tearing of the film after sputtering was not observed.

Comparative example  One

In order to determine the effect of the amount of oxygen in the target, using the same metal raw material as in Example 1, the same composition was measured and blended, dissolved and subjected to gas atomization to prepare a Ni-W-Al alloy powder , And separated by sieving to less than 150 mesh 200 mesh or more. Oxygen amount of the obtained alloy powder was 0.08 weight%. Next, the alloy powder was put into a graphite mold having a diameter of 154 mm and hot-pressed to sinter. The hot press was heated up to 1000 degreeC in a vacuum atmosphere, and the pressure was 200 kg / cm <2>. The sintered compact of 160 mm in diameter and 6 mm in thickness was subjected to lathe processing and plane grinding under the same conditions as in Example 1 to produce a target having a diameter of 152 mm and a thickness of 5 mm. The amount of oxygen in the obtained target was 0.08% by weight. Thus, sputtering was carried out in the same manner as in Example 1 to form a film. The particle number was measured in the same manner as in Example 1, and the contact angle between the obtained film and the resist was measured in the same manner as in Example 1.

Table 1 shows the particle number measurement results of 3 µm or more in the film obtained by the amount of oxygen, average grain size, surface roughness Ra, and sputtering of the obtained target. Moreover, the measurement result of the contact angle of the obtained film | membrane and a resist was shown in Table 1 together.

In addition, scattering of debris due to detachment of the film adhered in the sputtering device and tearing of the film after sputtering was not observed.

Comparative example  2

In order to determine the effect of the amount of oxygen, using the same raw material as in Example 1, the same composition was measured and dissolved, and then dissolved, followed by water atomization to prepare Ni-W-Al alloy powder, This was separated by sieving to 80 mesh or more and 120 mesh or less. Oxygen amount of the obtained alloy powder was 0.11 weight%. Next, the alloy powder was put into a graphite mold having a diameter of 154 mm and hot-pressed to sinter. The hot press was heated up to 1000 degreeC in a vacuum atmosphere, and the pressure was 200 kg / cm <2>. Only the lathe processing was performed with respect to the obtained sintered compact of 160 mm diameter x 6 mm, and the target of diameter 152 mm x thickness 5 mm was produced. The amount of oxygen in the obtained target was 0.11% by weight. Then, sputtering was carried out in the same manner as in Example 1 to form a film. The particle number was measured in the same manner as in Example 1, and the contact angle between the obtained film and the resist was measured in the same manner as in Example 1.

Table 1 shows the particle number measurement results of 3 µm or more in the film obtained by the amount of oxygen, average grain size, surface roughness Ra, and sputtering of the obtained target. Moreover, the measurement result of the contact angle of the obtained film | membrane and a resist was shown in Table 1 together.

In addition, scattering of debris due to detachment of the film adhered in the sputtering device and tearing of the film after sputtering was not observed.

Comparative example  3

A Ni-W-Al-Ti alloy powder was prepared in the same manner as in Comparative Example 1 except that the raw materials were weighed and blended so as to have the same composition as in Example 8, and the target was manufactured by hot pressing. The amount of oxygen in the obtained target was 0.10% by weight. Then, sputtering was carried out in the same manner as in Example 1 to form a film. The particle number was measured in the same manner as in Example 1, and the contact angle between the obtained film and the resist was measured in the same manner as in Example 1.

Table 1 shows the particle number measurement results of 3 µm or more in the film obtained by the amount of oxygen, average grain size, surface roughness Ra, and sputtering of the obtained target. Moreover, the measurement result of the contact angle of the obtained film | membrane and a resist was shown in Table 1 together.

In addition, scattering of debris due to detachment of the film adhered in the sputtering device and tearing of the film after sputtering was not observed.

Comparative example  4

A film was formed by sputtering in the same manner as in Example 1 using a target of high purity Cr (purity 99.9 wt% and oxygen amount 0.1 wt%). The particle number was measured in the same manner as in Example 1, and the contact angle between the obtained film and the resist was measured in the same manner as in Example 1.

Table 1 shows the particle number measurement results of 3 µm or more in the film obtained by the amount of oxygen, average grain size, surface roughness Ra, and sputtering of the obtained target. Moreover, the measurement result of the contact angle of the obtained film | membrane and a resist was shown in Table 1 together.

In addition, after the sputtering test, the Cr film attached in the sputtering apparatus was partially detached and was scattered in powder form.

Composition of target (% by weight) Average grain size (㎛) Surface Roughness Ra (㎛) Particle Number (pcs / ㎠) Contact angle (°) Ni W Al Ti Cr Oxygen Example 1 Remaining amount 15 2 - - 0.05 60 5 1.5 11.5 Example 2 Remaining amount 15 2 - - 0.05 60 12 1.7 14 Example 3 Remaining amount 15 2 - - 0.002 64 5 0.7 11.5 Example 4 Remaining amount 15 2 - - 0.04 14 5 1.2 11.5 Example 5 Remaining amount 15 2 - - 0.05 106 5 1.7 11.5 Example 6 Remaining amount 15 2 - - 0.05 106 12 1.9 14.4 Example 7 Remaining amount 17 7 - - 0.01 100 5 1.4 12.5 Example 8 Remaining amount 15 3.5 3.5 - 0.05 60 5 1.5 13 Example 9 Remaining amount 15 - 6 - 0.01 100 3 1.1 13 Comparative Example 1 Remaining amount 15 2 - - 0.08 80 5 3.0 18.5 Comparative Example 2 Remaining amount 15 2 - - 0.11 150 6 4.2 19 Comparative Example 3 Remaining amount 15 3.5 3.5 - 0.10 110 6 3.2 20 Comparative Example 4 - - - - 99.9 0.10 100 6 3.8 25.5

Passage or disqualification of the number of particles of 3 µm or more in the obtained film is judged from the viewpoint of whether or not there is no problem level when using it as a film for black matrix, in other words, it is judged by whether the number is less than 2 particles / cm 2. .

As can be seen from Table 1, in Examples 1 to 9 within the scope of the present invention, a good film having a particle number of 3 µm or more and less than 2 / cm 2 and a small particle number was obtained in the obtained films. Moreover, in Example 3 where the amount of oxygen in the target was less than 0.002% by weight, the number of particles having a particle size of 3 µm or more was 0.7 pieces / cm 2, and thus a good film having a very small particle number was obtained. In Examples 7 and 9 where the amount of oxygen in the target was 0.01% by weight, the number of particles having a particle size of 3 µm or more in the membrane was 1.4 / cm 2 and 1.1 / cm 2, respectively. It becomes less than the number of particles in the film | membrane obtained by 2, 5, and 6. Therefore, it is preferable that the amount of oxygen in the target is small.

Further, Examples 1, 3, 4, 7 to 9 in which the average grain size in the sputtering target was 100 µm or less and the surface roughness Ra were 10 µm or less were 0.7 to 1.5 particles / 3 or more in the obtained film. In Example 2, in which the surface roughness Ra was 12 µm and exceeded 10 µm, the particle size was 1.7 cm / cm 2 and the average grain size was 106 µm and exceeded 100 µm, while In Example 5, the particle number of 3 micrometers or more was 1.7 / cm <2> in the obtained film | membrane, and the average grain size of 106 micrometers exceeded 100 micrometers, and surface roughness Ra exceeded 10 micrometers by 12 micrometers in Example 6. The number of particles of 3 micrometers or more is 1.9 piece / cm <2> in the obtained film | membrane. As described above, in Examples 2, 5, and 6 in which the average grain size is more than 100 µm or the surface roughness Ra is more than 10 µm, the number of particles of 3 µm or more in the obtained film is 2.0 particles / cm 2 or less, but 2.0 particles / cm2. The value close to cm <2> is shown. Therefore, in the sputtering target which concerns on this invention, it is preferable that average grain size is 100 micrometers or less, and surface roughness Ra is 10 micrometers or less.

In Comparative Example 1, the amount of oxygen in the sputtering target is 0.08% by weight, exceeding 0.05% by weight, which is the upper limit of the amount of oxygen contained in the sputtering target according to the present invention. For this reason, the average grain size of the sputtering target is 80 µm and does not exceed 100 µm, and in particular, the surface roughness Ra is 5 µm and does not exceed 10 µm, but the number of particles of 3 µm or more in the obtained film is 3.0 particles / cm 2 and 2.0 particles / cm 2. Is over.

In Comparative Example 2, the amount of oxygen in the sputtering target is 0.11% by weight, more than that of Comparative Example 1. In addition, the average grain size of a sputtering target is 150 micrometers and exceeds 100 micrometers. Therefore, the particle number of 3 micrometers or more in the obtained film | membrane is 4.2 number / cm <2>, and greatly exceeds 2.0 number / cm <2>.

In Comparative Example 3, the amount of oxygen in the sputtering target is 0.10 wt%, which is higher than that of Comparative Example 1. Moreover, the average grain size of a sputtering target is 110 micrometers, and exceeds 100 micrometers. Therefore, the particle number of 3 micrometers or more in the obtained film | membrane is 3.2 piece / cm <2>, and exceeds 2.0 piece / cm <2>.

In Comparative Example 4, the composition of the sputtering target is 99.9% by weight of Cr and 0.10% by weight of oxygen, and is a target for black mattresses that has been conventionally used. The number of particles of 3 micrometers or more in the obtained film | membrane is largely exceeding 2.0 piece / cm <2> at 3.8 piece / cm <2>.

In addition, about the contact angle of the film | membrane obtained with the resist, it is 18.5-25.5 degrees in the comparative examples 1-4 which are out of the scope of this invention, and is 11.5-14.4 degrees in Examples 1-9 which are within the scope of the present invention. The film produced using the sputtering target according to the present invention has good resist wettability.

The sputtering target according to the present invention contains 5 to 30% by weight of tungsten (W), 0.1 to 10% by weight of at least one of aluminum (Al) and titanium (Ti), and the amount of oxygen contained is 0.05% by weight or less. Since the remainder is substantially nickel (Ni), it is possible to form a thin film that does not contain chromium (Cr), which is a cause of environmental pollution, and has few film defects due to particles. In addition, when using the sputtering target according to the present invention, abnormal discharge during sputtering is reduced. By using the sputtering target which concerns on this invention, the thin film for black matrices with few film defects can be obtained.

Claims (8)

5 to 30% by weight of tungsten (W), 0.1 to 10% by weight of at least one of aluminum (Al) and titanium (Ti) in total, the amount of oxygen contained is 0.05% by weight or less, and the balance is substantially nickel ( Ni) sputtering target, characterized in that. The sputtering target according to claim 1, wherein the average grain size is 100 µm or less, and the surface roughness Ra is 10 µm or less. The sputtering target according to claim 1 or 2, wherein the number of particles having a particle diameter of 3 µm or more is 2 / cm 2 or less in the film obtained by sputtering using the sputtering target. 5 to 30% by weight of tungsten (W), 0.1 to 10% by weight of at least one of aluminum (Al) and titanium (Ti) in total, the amount of oxygen contained is 0.05% by weight or less, and the balance is substantially nickel ( Ni) weighing and mixing the raw metal to be Ni, dissolving and casting the raw metal in a vacuum or in an inert atmosphere to obtain a casting; Hot forging and / or hot rolling the casting in a vacuum or in an inert atmosphere to obtain a forging or rolling material; And And machining the forged or rolled material into a predetermined shape to obtain a sputtering target. The method for producing a sputtering target according to claim 4, wherein heat treatment is performed after the hot forging and / or hot rolling. The method for producing a sputtering target according to claim 4, wherein the hot working is performed after the hot forging and / or hot rolling, and then heat treatment is performed. The method for producing a sputtering target according to any one of claims 4 to 6, wherein the size of the average grain size of the forging material or the rolling material is set to 100 µm or less. The surface roughness Ra of the said sputtering target is 10 micrometers or less, The manufacturing method of the sputtering target in any one of Claims 4-7 characterized by the above-mentioned.