JP2013023745A - Titanium nitride sputtering target and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable industrial deposition of continuous and uniform titanium nitride film on a large-area resin film.SOLUTION: TiN powder having an average particle diameter of 0.4-1.5 μm is added with 0.5-2.0 pts.mass dispersant per 100 pts.mass TiN powder, wet milled, spray dried, formed under a pressure of 98-294 MPa, reduced at 400-1,000°C in an atmospheric pressure reducing atmosphere, burnt at 1,800-2,100°C in an atmospheric pressure nitrogen atmosphere, and processed, thereby obtaining a titanium nitride sputtering target achieving 0.8≤x≤1.0 in a general formula: TiNx, a relative density of 93-100%, and an average vacancy diameter of 0.1-1.5 μm.

Description

  The present invention relates to a sputtering target for forming a titanium nitride film applied to a wide field including surface modification of a resin film and a method for manufacturing the same.

  The titanium nitride film is used as a hard film formed on the surface of a tool or the like that requires durability, and is also used as a conductive film in IC / semiconductor applications because of its conductivity. In recent years, it is also desired to form a titanium nitride film on a resin film for the purpose of surface modification for improving conductivity and corrosion resistance. In accordance with such applications and the accompanying increase in demand, it is required to form a uniform film over a large area in the titanium nitride film.

  Conventionally, a reactive sputtering technique in a nitrogen atmosphere using a titanium target is generally used for forming a titanium nitride film. However, when reactive sputtering is performed, the specific resistance, crystallinity, deposition rate, etc. of the resulting film are likely to change depending on the partial pressure of nitrogen and input power, and the characteristics of the film remain in the apparatus. There is a technical problem that it will change greatly depending on the situation. In particular, when titanium nitride is formed on a resin film by reactive sputtering, oxygen is taken into the resulting titanium nitride film due to moisture and oxygen generated from the resin film, and the characteristics of the film change, There is a problem that a titanium nitride film having uniform film characteristics cannot be obtained. Further, in reactive sputtering, there is also a problem that the deposition rate is rapidly reduced due to the formation of a titanium nitride film on the target surface.

  Under these circumstances, in order to solve the problem of reactive sputtering with a titanium target, a titanium nitride sputtering target is strongly desired as a film forming material that can be substituted for the titanium target.

  The titanium nitride sputtering target can also be obtained by a powder sintering method using titanium nitride powder as a starting material. As the powder sintering method, a hot press, a HIP (hot isostatic press) or the like is usually used. Yes.

  However, titanium nitride is a material that is difficult to sinter, and even if a titanium nitride sputtering target is produced by the above powder sintering method, since many coarse pores exist between the sintered particles, It becomes low density. Due to the presence of the large number of holes, nodules (protruding foreign matter) are generated on the surface of the target during the sputtering film formation, which causes a significant decrease in the film formation rate. In addition, there is also a problem that nodules are more likely to be generated on the target surface due to foreign matters generated from the resin film during film formation on the resin film. Therefore, in order to solve such a problem, there is an urgent need to make the titanium nitride sputtering target dense.

  To increase the density of the titanium nitride sputtering target, use titanium nitride powder mixed with titanium hydride as the raw material powder, and adjust the N / Ti molar ratio of the raw material powder when hot pressing this powder. Is disclosed (see Patent Document 1). However, in this technique, in order to realize a high density of the titanium nitride sputtering target, it is necessary to greatly reduce the N / Ti molar ratio of the target composition, and as a result, to supplement the nitrogen quality of the titanium nitride film. In addition, it is necessary to increase the amount of nitrogen in the gas introduced at the time of sputtering film formation in large quantities. Since introduction of nitrogen gas causes a significant decrease in the deposition rate, it is difficult to use such a target for the formation of an industrial titanium nitride film.

  Further, it is disclosed that a titanium nitride sputtering target with less generation of particles is obtained by a method in which titanium powder is sintered and then nitrided (see Patent Documents 2 and 3). However, in the titanium nitride sputtering target manufactured by this method, since the average pore size becomes large, as described above, the occurrence frequency of nodules due to foreign matters generated from the resin film during film formation is high. Therefore, the film forming speed cannot be improved.

  Furthermore, in the hot press method and HIP employed for increasing the density of the target, mass production is difficult and the cost is high, so these manufacturing methods cannot be employed as industrial means. .

Japanese Unexamined Patent Publication No. 63-259075 JP-A-6-212417 JP-A-6-212418

  An object of the present invention is to provide a high-density titanium nitride sputtering target capable of forming a continuous and uniform titanium nitride film on a large-area resin film. Another object of the present invention is to enable the high-density titanium nitride sputtering target to be supplied stably and at low cost by industrial means.

  The present invention relates to a titanium nitride sputtering target for forming a titanium nitride film on a resin film.

In particular, the titanium nitride sputtering target of the present invention is composed of titanium, nitrogen, and inevitable components, and the composition ratio is 0.8 ≦ x ≦ 1.0 in the general formula: TiN _x . The sintered body density is in the range of 93% to 100% in terms of the theoretical density ratio, and the average pore diameter is in the range of 0.1 μm to 1.5 μm. Inevitable components include oxygen and carbon, and the maximum content of oxygen and carbon in the titanium nitride sputtering target is allowed up to 10 at%.

  In addition, it is preferable that the average particle diameter of the titanium nitride grain which comprises a titanium nitride sputtering target exists in the range of 5 micrometers-20 micrometers.

The titanium nitride sputtering target of the present invention is
(1) Using a titanium nitride powder having an average particle size in the range of 0.4 μm to 1.5 μm as a starting material,
(2) In a water solvent, the titanium nitride powder is added to 100 parts by mass of the titanium nitride powder together with a dispersant selected from an acrylic acid-methacrylic acid copolymer neutralized ammonia and an acrylic acid-based copolymer amine salt. On the other hand, the dispersant is added so as to be in the range of 0.5 parts by mass to 2.0 parts by mass, wet pulverized,
(3) The obtained pulverized product is spray-dried,
(4) The resulting granulated powder is molded at a pressure in the range of 98 MPa to 294 MPa using a cold isostatic press,
(5) The obtained molded body was reduced at a temperature in the range of 400 ° C. to 1000 ° C. in a reducing atmosphere, and then fired at a temperature of 1800 ° C. to 2100 ° C. in a nitrogen atmosphere.
(6) processing the obtained sintered body;
It can obtain by a manufacturing method provided with the process of.

  It is preferable to use a nitrogen-hydrogen mixed atmosphere or a hydrogen atmosphere containing 1% by volume or more of hydrogen as the reducing atmosphere.

  Further, it is preferable that the reduction treatment is performed in an atmospheric pressure or pressurized reducing atmosphere, and the baking treatment is performed in an atmospheric pressure or pressurized nitrogen atmosphere.

  In the wet pulverization step, it is preferable to further add 1.0 to 2.0 parts by mass of polyvinyl alcohol as a binder with respect to 100 parts by mass of the titanium nitride powder.

  In the spray drying step, it is preferable to obtain spherical granulated powder using a spray dryer.

  Furthermore, it is preferable to use a carbon heater furnace in the firing step.

  In the titanium nitride sputtering target of the present invention, generation of coarse vacancies is suppressed, and coarsening of the vacancies itself is also suppressed. Therefore, by using the titanium nitride sputtering target of the present invention, generation of nodules on the target surface due to coarse vacancies during film formation is suppressed, and further, a remarkable decrease in film formation rate is suppressed. Further, there is an advantage that the variation in the thickness of the titanium nitride film is reduced even during continuous film formation on the resin film.

  In addition, by adjusting the average particle size of the titanium nitride grains to a predetermined range, the strength of the sintered body can be further improved, and even when high sputtering power is applied, the target is not cracked during film formation, A titanium nitride sputtering target that can be used efficiently is provided. Furthermore, since the film formation by the direct current sputtering method can be performed using the titanium nitride sputtering target of the present invention, the film formation rate can be improved as compared with the conventional reactive sputtering method.

  On the other hand, even when performing film formation with low power with little damage to the resin film, the use of the titanium nitride sputtering target of the present invention brings about the effect that a titanium nitride film with high crystallinity and low resistance can be obtained. It is.

  As described above, the titanium nitride sputtering target of the present invention is a high-density titanium nitride sputtering target suitable for continuous film formation of a uniform titanium nitride film on a large-area resin film, and its value is It can be said that it is very expensive.

  Further, unlike the hot press or the like in which the amount of processing at one time is limited in the firing step by the method for producing the titanium nitride sputtering target of the present invention, the molded body is arranged in multiple stages in the firing furnace, and the atmospheric pressure atmosphere. Since it can be fired in the inside, the processing amount can be increased and mass production becomes possible. Therefore, according to the present invention, it is possible to provide a sputtering target, that is, a titanium nitride film, which is a material for forming a titanium nitride film, stably and at low cost, and it can be said that the industrial significance of the present invention is great.

FIG. 1 is a graph showing the XRD (X-ray diffraction) measurement results of the titanium nitride sintered body obtained in the example of the present invention. FIG. 2 is an SEM image of a fracture surface of the titanium nitride sputtering target of the present invention obtained by firing after performing a reduction treatment in a nitrogen atmosphere containing hydrogen. FIG. 3 is an SEM image of a fracture surface of a titanium nitride sputtering target obtained by firing without performing a reduction treatment.

The components constituting the titanium nitride sputtering target of the present invention are titanium, nitrogen, and unavoidable components, particularly oxygen and carbon. The composition ratio of titanium and nitrogen is 0.8 ≦ x ≦ 1.0 in the general formula: TiN _x . Further, the theoretical density ratio is in the range of 93% to 100%, and the average pore diameter is in the range of 0.1 μm to 1.5 μm.

  The titanium nitride sputtering target of the present invention uses titanium nitride powder as a starting material, but components inevitably contained in the raw material titanium nitride powder are contained in addition to titanium and nitrogen. In addition, oxygen and carbon are inevitably mixed in the manufacturing process of the sputtering target. Therefore, in addition to titanium and nitrogen, inevitable components including oxygen, carbon, and other components are included as the components.

The oxygen and carbon contents can be allowed up to 10 at%. If each of these exceeds the maximum allowable amount, the composition ratio of titanium and nitrogen in the titanium nitride sputtering target becomes less than 0.8 in the general formula: TiN _x , and the conductivity of the titanium nitride film obtained by the direct current sputtering method. It becomes inadequate and cannot be used for a conductive film. The oxygen and carbon contents are regulated by controlling the atmosphere in the manufacturing process. On the other hand, the content of impurities other than oxygen and carbon is about 0.1% by mass at maximum. These impurities are controlled by adjusting the purity of the raw material powder, pulverization adjustment, and the like.

Even when the composition ratio of titanium and nitrogen is less than 0.8 in the general formula: TiN _x , titanium nitride having conductivity and corrosion resistance according to its application by supplementing nitrogen quality during sputter deposition Although a film can be obtained, in the present invention, from the viewpoint of enabling an industrial titanium nitride film to be formed, the composition ratio is regulated to be 0.8 or more in the general formula: TiN _x .

  The sintered body density (relative density) of the titanium nitride sputtering target of the present invention is in the range of 93% to 100% of the theoretical density ratio. Furthermore, since it can suppress that a nodule generate | occur | produces on the target surface at the time of sputtering, continuous film-forming on a resin film is attained. From the viewpoint of long and stable film formation, the theoretical density ratio is more preferably in the range of 95% to 100%.

  In order to increase the density of the sintered body, various conditions in the manufacturing process, specifically selection of starting materials, molding by cold isostatic pressing (CIP), molding conditions thereof, conditions for reduction treatment and firing, etc. are appropriately selected. In particular, controlling the firing conditions so that the average pore diameter is 1.5 μm or less greatly contributes to the achievement of high density as described above.

  In the titanium nitride sputtering target of the present invention, the average pore diameter is in the range of 0.1 μm to 1.5 μm. If the average pore diameter exceeds 1.5 μm, generation of nodules on the target surface during film formation cannot be sufficiently suppressed. On the other hand, the lower limit of the average pore diameter is preferably small, but in order to make it lower than 0.1 μm, it is necessary to further increase the molding pressure during molding and the firing temperature during firing. Such conditions are not suitable for mass production, and it is impossible to suppress the formation of coarse vacancies due to the decomposition of titanium nitride. It can be said that it is difficult from the viewpoint of production.

  In this way, by using the titanium nitride sputtering target of the present invention having a high density, a remarkable decrease in the film formation rate is suppressed, and uniform film formation with little film thickness fluctuation even during continuous film formation on a film. Is possible. Therefore, it can be said that the titanium nitride sputtering target of the present invention is extremely suitable for forming a titanium nitride film on a large area resin film. The sintered body density here refers to a volume ratio and a mass of the obtained test piece of the sintered body, and a theoretical density ratio of the obtained density to the theoretical density is calculated.

In addition, since the composition ratio of titanium and nitrogen in the titanium nitride sputtering target of the present invention is 0.8 ≦ x ≦ 1.0 in the general formula: TiN _x , the film forming gas atmosphere during sputtering is only Ar. Even under the film forming conditions using the above atmosphere, a titanium nitride film with high nitrogen quality can be obtained. Therefore, it is possible to obtain a titanium nitride film excellent in both conductivity and corrosion resistance without introducing nitrogen gas that impedes sputtering efficiency.

As described above, when _{x in} the general formula: TiN _x indicating nitrogen quality is less than 0.8, it is necessary to add nitrogen gas at the time of film formation, which significantly reduces the film formation speed. Thus, it is extremely important to set the nitrogen quality to 0.8 ≦ x ≦ 1.0. Thus, it can be said that the present invention is extremely useful in realizing a titanium nitride sputtering target having a high nitrogen quality. In view of the characteristics of the obtained titanium nitride film, the nitrogen quality is preferably 0.9 or more.

  In addition, the crystal grains of the titanium nitride sputtering target of the present invention preferably have an average particle diameter in the range of 5 μm to 20 μm from the viewpoint of the strength of the sintered body and the remaining pore size. When the average particle size is smaller than 5 μm, the bonding between the particles becomes poor and the target becomes low in strength, which is not preferable. On the other hand, when the average particle size is larger than 20 μm, the particle size varies greatly, and a large number of coarse particles are present. If the target has such a low strength, the target is likely to break due to the thermal load during film formation, which is not preferable. Furthermore, when the crystal grains are increased, the pore size is increased, which is not preferable from the viewpoint that nodules are easily generated. From the viewpoint of the crystallinity of such a titanium nitride sintered body, the average particle size is more preferably in the range of 10 μm to 15 μm.

  Next, the manufacturing method of the titanium nitride sputtering target of this invention is demonstrated.

(1) Starting material First, titanium nitride powder is used as a starting material. As the titanium nitride powder, a powder having an average particle diameter in the range of 0.4 μm to 1.5 μm is used. In general, it is expected to improve the sinterability of the target by making the raw material powder of the sputtering target fine. However, if the average particle diameter is made finer than 0.4 μm, the powder tends to aggregate and the powder is oxidized. However, the sinterability is hindered. On the other hand, when the average particle size is larger than 1.5 μm, coarse particles increase, and the sinterability of the powder is significantly inhibited. From the viewpoint of sinterability of the powder and handleability during mass production of the target, it is more preferable to use a powder in the range of 0.5 μm to 1.1 μm. Even when the pulverization of the powder in the solvent is considered, it is necessary to set the average particle diameter of the starting material within the above range.

Further, BET value as an index of the primary particle diameter is preferably in the range of 1m ² / g~15m ² / g. When the BET value is less than 1 m ² / g, the sinterability is significantly deteriorated and it is difficult to improve the target density. On the other hand, when the BET value is greater than 15 m ² / g, the aggregation is increased. In addition to being difficult to handle, it becomes easy to take in oxygen, so that the sinterability is hindered. The BET value is more preferably in the range of 5m ² / g~10m ² / g.

(2) Wet grinding process Next, the raw material titanium nitride powder is wet ground and atomized. The wet pulverization of the titanium nitride powder needs to be carried out in an aqueous solvent using an acrylic acid / methacrylic acid copolymer neutralized ammonia or an acrylic acid copolymer amine salt as a dispersant. Although the wet pulverization using water alone as a solvent is easy to mass-produce as a process, there is a problem that the oxidation of the powder and the dispersion of the titanium nitride powder in the aqueous solvent are poor.

  Therefore, in the present invention, by using an acrylic acid / methacrylic acid copolymer neutralized ammonia or an acrylic acid copolymer amine salt as a dispersant, titanium nitride powder close to water repellency can be obtained in an aqueous solvent. It is possible to achieve high dispersion. That is, since the slurry concentration of the titanium nitride powder in the aqueous solvent can be increased to 50% or more, preferably about 70%, the production efficiency can be increased. Even when the slurry concentration is 50% or more, the slurry viscosity can be less than 100 cps.

  The acrylic acid / methacrylic acid copolymer ammonia neutralized product has a composition represented by the following formula.

  In addition, examples of the acrylic acid copolymer amine salt include those having a composition represented by the following formula.

  Specific examples of the acrylic acid copolymer amine salt include polyacrylic acid amine salts.

  The dispersant should be added in an amount of 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the raw material titanium nitride powder. It is desirable to treat with a smaller amount of 0 parts by weight. If the amount is less than 0.5 parts by mass, the effect of addition cannot be obtained.

  In this pulverization process, which is a wet process, the titanium nitride powder is surface-oxidized. However, the problem with the oxidation of the titanium nitride powder is that the raw material powder has an average particle size of 0.4 μm to 1.5 μm Thus, in the subsequent firing step, it is possible to solve the problem caused by oxidation by adjusting the firing temperature and the atmosphere.

In addition to the additive, it is desirable to add polyvinyl alcohol (PVA: — [CH ₂ CH (OH)] _n —) as an organic binder. By adding PVA, a high-strength molded body can be obtained during molding, and PVA can be easily volatilized during sintering. PVA having a saponification degree in the range of 90 mol% to 100 mol% and a polymerization degree in the range of 500 to 1000 is preferably used. The amount of PVA added is preferably in the range of 1.0 to 2.0 parts by mass with respect to 100 parts by mass of the raw material titanium nitride powder, more preferably 1.0 to 1.5 parts by mass. It is desirable to process with a small amount of addition. When the amount is less than 1.0 part by mass, the effect of addition cannot be obtained. The organic binder may be added at the same time as the dispersant before the wet pulverization step. Alternatively, the organic binder may be added to the pulverized slurry after the wet pulverization and used for the spray drying step.

  In the wet pulverization, a mixing means such as a ball mill or a bead mill can be used. It is preferable to use a plastic bottle, a urethane-lined stainless steel container or the like for the container, and a zirconia ball or the like for the media from the viewpoints of stability and wear resistance. The pulverization and mixing time is preferably about 5 to 20 hours for ball milling. The ball mill condition is desirably performed at a peripheral speed of 30 m / min to 40 m / min using a medium about three times the mass of the processed powder. On the other hand, in the case of a bead mill, it is desirable to pulverize using φ0.5 mm beads at about 1000 rpm to 1500 rpm for about 1 hour to 5 hours.

(3) Spray drying process About the obtained slurry containing the ground material, spray drying is performed to obtain granulated powder. In particular, it is preferable to obtain a spherical granulated powder by using a spray dryer. As described above, in the present invention, a methacrylic acid copolymer ammonia neutralized product or an acrylic acid copolymer amine salt is used as a dispersant, and more preferably, PVA is used as an organic binder. As a result, aggregation of the titanium nitride powder is prevented, and generation of pores in the obtained granulated powder is also prevented.

  In addition, it is preferable to make the drying temperature at the time of spray-drying into the range of 140 to 200 degreeC. Moreover, according to an apparatus, a drying rate is suitably adjusted with the amount of exhaust air etc. so that spherical granulated powder may be obtained. For spray drying, it is preferable to use a spray dryer using a disk with excellent mass productivity. By setting the disk rotation speed to 10000 rpm to 15000 rpm and a slurry concentration of 50% or more, a granulated powder having excellent spherical formability is obtained. can get. By lowering the drying temperature, the binder does not become hard, and the grains close to each other at the time of molding are deformed and adhered to each other, whereby a high-strength molded product is obtained. The particle size of the granulated powder is preferably 50 μm to 100 μm in terms of average particle size, and it is desirable that the maximum particle size be 150 μm to be sieved to stabilize the tap density.

(4) Molding step The granulated powder obtained through the spray-drying step is filled in a rubber mold and using a cold isostatic press (CIP) at a pressure of 98 MPa to 294 MPa, more preferably 196 MPa to 294 MPa. , Forming granulated powder. At this time, CIP may be performed after preforming by uniaxial pressing. By performing CIP at a high pressure in the range of 98 MPa to 294 MPa, unlike the case of hot pressing or HIP, the granulated powders are brought into close contact with each other and voids are eliminated, so that it is possible to improve the density in sintering. Become. CIP has an advantage in that it is excellent in production stability and shape stability. The maximum pressure holding time at the time of molding is preferably 1 minute to 10 minutes.

  By shaping | molding on the said conditions, a high intensity | strength molded object is obtained and a molded object density (relative density) can be 50% or more. The compact density here refers to the theoretical density ratio of the obtained density to the theoretical density by measuring the volume and mass of the test piece of the obtained compact. If the density of the molded body is lower than 50%, it becomes difficult to handle the molded body, and the shrinkage of the molded body increases during sintering, which increases the possibility of causing sintered cracks.

  In addition, although it is possible to mold at a molding pressure higher than 294 MPa in the molding process, it is not suitable for mass production considering the durability of the apparatus.

(5) Reduction treatment step The molded body obtained in the molding step is preferably heated in a reducing atmosphere at atmospheric pressure (0.1 MPa) for 1 hour to 15 at a temperature of 400 ° C to 1000 ° C. The reduction process is performed for about an hour.

After the molded body is placed in the furnace and evacuated until the pressure in the furnace reaches about 5 × 10 ⁻² Pa to 7 × 10 ⁻³ Pa, a nitrogen-hydrogen mixed gas or hydrogen gas is introduced into the furnace, Atmospheric pressure reducing atmosphere. As the reducing atmosphere, a nitrogen-hydrogen mixed atmosphere containing 1% by volume or more of hydrogen or a hydrogen atmosphere (hydrogen 100% by volume) can be used. When a nitrogen-hydrogen mixed atmosphere is used, a sufficient effect cannot be obtained when the hydrogen content is less than 1% by volume. From the viewpoint of the efficiency of the reduction treatment, the hydrogen content in the nitrogen-hydrogen mixed atmosphere is preferably 2% by volume or more. Further, the temperature during the reduction treatment is 400 ° C. to 1000 ° C., preferably 500 ° C. to 1000 ° C. If the temperature is less than 400 ° C., the reduction reaction does not proceed sufficiently. Titanium metal etc. will be generated. In order to uniformly reduce the molded body, the rate of temperature rise is 1.0 ° C./min to 7.0 ° C./min, preferably 2.0 ° C./min to 7.0 ° C./min. .

  By performing the reduction treatment in this manner, generation of oxides can be prevented, organic components can be removed, and generation of vacancies that hinders densification can be suppressed. As a result, the generation of vacancies is sufficiently suppressed during the subsequent firing step in an atmospheric pressure nitrogen atmosphere.

  In addition, as a heating furnace, although it can be used if it is a furnace which can be heated to said temperature range, it is desirable to use the carbon heater furnace which can implement | achieve a reducing atmosphere.

  In addition, the atmosphere during the reduction treatment can obtain the same effect even in a pressurized atmosphere up to about 0.9 MPa, but from the viewpoint of mass productivity, it is possible to employ an atmosphere of nitrogen-hydrogen mixture or hydrogen atmosphere at atmospheric pressure. preferable.

(6) Firing step The firing step is performed using the same heating furnace continuously with the reduction treatment step. In the firing step, firing is performed in a temperature range of 1800 ° C. to 2100 ° C., more preferably in a temperature range of 1900 ° C. to 2100 ° C., in a nitrogen atmosphere at atmospheric pressure (0.1 MPa). A temperature of 1800 ° C. or higher is necessary for sufficient grain growth. If the temperature is lower than 1800 ° C., the grain growth of titanium nitride is insufficient, coarse pores remain, and a high-density sintered body cannot be obtained. Therefore, the generation of nodules cannot be suppressed during film formation, and the film formation rate is significantly reduced, so that uniform film formation for a long time cannot be performed. Even if the temperature exceeds 2100 ° C., grain growth occurs and a sintered body having a high relative density can be obtained. However, since titanium nitride is easily decomposed, the formation of coarse pores cannot be suppressed, and nodules are not formed during film formation. It is necessary to fire at a temperature of 2100 ° C. or lower because it causes the generation.

  In order to cause grain growth, it is desirable that the holding time at the above baking temperature is 3 hours or more. In view of the efficiency of firing, the holding time is more preferably in the range of 3 hours to 10 hours. In order to perform grain growth uniformly, it is necessary to set the temperature increase rate to 20 ° C./min or less, and preferably to a temperature increase rate of 3 ° C./min to 10 ° C./min. In addition, after holding at the firing temperature for a predetermined time, it is preferable to cool to near room temperature at a cooling rate in the range of 2 ° C./min to 10 ° C./min.

  The firing atmosphere needs to be heated in nitrogen gas so that the titanium nitride is not easily decomposed. Oxidation in the wet treatment process can be removed by reduction treatment in the reduction treatment process and heat treatment in the baking process. Grain growth can be promoted by sintering in either a pressurized nitrogen atmosphere or an atmospheric nitrogen atmosphere up to about 0.9 MPa, and titanium nitride can be sintered. However, from the viewpoint of mass productivity, it is preferable to employ an atmospheric pressure nitrogen gas atmosphere.

(7) Processing Step The obtained sintered body is processed into an appropriate size such as a 6 inch (152 mm) diameter or a 150 × 150 mm square, polished, and then bonded to a backing plate to obtain a sputtering target. In addition, although this process is comprised by the wheel using a diamond abrasive grain, and the surface grinding and end surface process by a mill, a well-known process means can be used for each of these processes. The strength of the sputtering target thus obtained does not break the target during film formation even when high sputtering power is applied.

(8) Film-forming process About the sputtering method at the time of film-forming using the sputtering target of this invention, any well-known means can be used without being restrict | limited at all, but from a viewpoint of mass-productivity. It is preferable to adopt means using a direct current sputtering apparatus. In the sputtering target of the present invention, the density of the compact according to the theoretical density ratio is as high as 93% or more, and vacancies are not a problem. Therefore, the generation of nodules is suppressed even when direct current sputtering is used.

In addition, when sputtering was performed under normal sputtering conditions using the sputtering target of the present invention, the composition of the film after film formation was almost the same as the composition of the sputtering target, and when nitrogen analysis in the film was performed, TiN _x In this case, 0.8 ≦ x ≦ 1.0.

In film formation on a resin film, it is preferable to use a roll coater capable of continuous film formation. Using Ar gas, by a gas pressure 0.2Pa～0.3Pa, it is deposited at input power ^{3W / cm 2 ~22W / cm 2} . Taking into consideration the influence on the resin film, if it is 12 W / cm ² or less, the thermal load is small and good. Further, while reducing the damage to the film, in order to form a low-resistance titanium nitride film is preferably in the range of ^{7W / cm 2 ~12W / cm 2} .

  EXAMPLES Hereinafter, although an Example demonstrates further more concretely about this invention, this invention is not limited to an Example.

Example 1
Neutralizing ammonium methacrylic acid copolymer with 100 parts by mass of titanium nitride powder (manufactured by Nippon Shin Metal Co., Ltd.) having an average particle size of 1.1 μm and a BET value of about 3 m ² / g, as a dispersant. 1.5 parts by mass of a product (manufactured by Chubu Seiden Co., Ltd.), 1.5 parts by weight of polyvinyl alcohol (PVA: manufactured by Nippon Binbo Bhopal Co., Ltd.) having a saponification degree of 91 mol% and a polymerization degree of 500 as an organic binder. After weighing each part so that water (pure water) as a mass part and 100 parts by mass (slurry concentration: 50%) as a solvent, all of these were added together with φ5 mm zirconia balls (manufactured by Nikkato Co., Ltd.) (to titanium nitride powder) About 3 times) and put into a 10 L polybin, and ball milling was performed for 15 hours at a rotation speed of 60 rpm (peripheral speed of about 38 m / min). When the viscosity of the obtained slurry was measured with a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.), it was 50 cps.

  Thereafter, the obtained slurry was spray-dried at a hot air temperature of 150 ° C. using a spray dryer (manufactured by Okawara Chemical Co., Ltd.) to obtain granulated powder. When the shape of the granulated powder was confirmed by an optical microscope, it was spherical, and the average particle size was about 75 μm.

  The obtained granulated powder is filled into a rubber mold (25 cm width × 25 cm length × 1.4 cm height), and using a hydrostatic pressure molding apparatus (manufactured by Kobe Steel, Ltd.) at a molding pressure of 294 MPa for 6 minutes. CIP molding was performed.

Further, the obtained molded body was placed in a carbon furnace (manufactured by Noritake Engineering Co., Ltd.) and evacuated to 8 × 10 ⁻³ Pa, and then nitrogen gas containing 3% by volume of hydrogen was added to atmospheric pressure (0 .1 MPa) while maintaining the temperature at 800 ° C. at a rate of temperature increase of 4 ° C./min. The atmosphere was replaced with a nitrogen atmosphere at atmospheric pressure, and the temperature was raised to a firing temperature of 1800 ° C. at a rate of temperature increase of 2 ° C./min. The temperature was maintained for 10 hours. A sintered body was obtained.

The obtained sintered body was processed into a size of 150 × 150 × 6 mm. One of them as a sample, was measured sintered body density by the Archimedes method, was 5.05 g / cm ^3, the relative density is the ratio of the titanium nitride of the theoretical density (5.43g / cm ³⁾ is It was 94%, and the average pore diameter was 1.5 μm from the SEM image of the fracture surface of the sintered body.

Further, when nitrogen analysis of the sintered body was performed by an X-ray photoelectron spectroscopy (XPS) apparatus, x = 0.92 in TiN _x . Further, when the sintered body was measured by an X-ray diffraction (XRD) apparatus, as shown in FIG. 1, only the peak of titanium nitride (TiN _x ) appeared, and generation of titanium oxide (TiO ₂ ) was observed. There wasn't. Furthermore, when the average particle diameter of the titanium nitride particles was confirmed using an electron microscope, the average particle diameter was 10 μm.

  Thereafter, the sintered body after the surface polishing was bonded to a backing plate using a hot plate to obtain a sputtering target.

Next, using the obtained sputtering target, a DC sputtering apparatus (continuous film roll coater) is used to introduce 10 W / cm ² of input power and Ar gas, and perform DC sputtering in an atmosphere of 0.3 Pa pressure. As a result, abnormal discharge due to nodule generation did not occur until 10 hours after the start of discharge. Further, the rate of decrease in the film formation rate at the end of discharge (after about 24 hours) with respect to the film formation rate at the start of discharge was as good as 10%. Further, when the obtained film was subjected to nitrogen analysis, x = 0.92 in TiN _x .

(Example 2)
A sputtering target was manufactured under the same conditions as in Example 1 except that the firing temperature in the firing step was 1900 ° C. The sintered body density of the obtained sintered body was 95%, the average pore diameter was 1.2 μm from the SEM image of the fracture surface of the sintered body, x = 0.94 in TiN _x , and the average particle diameter of the titanium nitride grains was It was 12 μm. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, sputtering was performed and the target was evaluated. As a result, no nodules were produced and good results were obtained. Further, the rate of film formation rate reduction was as good as 9%.

(Example 3)
A sputtering target was manufactured under the same conditions as in Example 1 except that the firing temperature in the firing step was 2000 ° C. The sintered body density of the obtained sintered body was 96%, the average pore diameter was 0.9 μm from the SEM image of the fracture surface of the sintered body, x = 0.93 in TiN _x , and the average particle diameter of the titanium nitride grains was It was 15 μm. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, sputtering was performed and the target was evaluated. As a result, no nodules were produced and good results were obtained. Further, the rate of film formation rate reduction was as good as 7%.

Example 4
A sputtering target was manufactured under the same conditions as in Example 3 except that the reduction treatment conditions of the reduction treatment step were performed in a hydrogen atmosphere using 100 vol% hydrogen gas instead of nitrogen gas containing 3 vol% hydrogen. . The sintered body density of the obtained sintered body was 97%, the average pore diameter was 0.7 μm from the SEM image of the fracture surface of the sintered body, x = 0.93 in TiN _x , and the average particle diameter of the titanium nitride grains was It was 15 μm. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, sputtering was performed and the target was evaluated. As a result, no nodules were produced and good results were obtained. Further, the rate of decrease in the film formation rate was as good as 6%.

(Example 5)
A sputtering target was manufactured under the same conditions as in Example 3 except that nitrogen gas containing 1% hydrogen was used in place of nitrogen gas containing 3% by volume of hydrogen. The sintered body density of the obtained sintered body was 96%, the average pore diameter was 0.8 μm from the SEM image of the fracture surface of the sintered body, x = 0.93 in TiN _x , and the average particle diameter of the titanium nitride grains was It was 15 μm. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, sputtering was performed and the target was evaluated. As a result, no nodules were produced and good results were obtained. Further, the rate of film formation rate reduction was as good as 7%.

(Example 6)
A sputtering target was manufactured under the same conditions as in Example 3 except that the molding pressure in the molding process was 98 MPa. The sintered body density of the obtained sintered body was 94%, the average pore diameter was 1.3 μm from the SEM image of the fracture surface of the sintered body, x = 0.93 in TiN _x , and the average particle diameter of the titanium nitride grains was 14 μm. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, sputtering was performed and the target was evaluated. As a result, no nodules were produced and good results were obtained. Further, the rate of film formation rate reduction was as good as 10%.

(Example 7)
A sputtering target was manufactured under the same conditions as in Example 3 except that the titanium nitride powder as the raw material powder was pulverized and classified in advance to use a powder having an average particle size of 0.5 μm. The sintered body density of the obtained sintered body was 98%, the average pore diameter was 0.6 μm from the SEM image of the fracture surface of the sintered body, x = 0.93 in TiN _x , and the average particle diameter of the titanium nitride grains was It was 13 μm. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, sputtering was performed and the target was evaluated. As a result, no nodules were produced and good results were obtained. Further, the rate of film formation rate reduction was as good as 5%.

(Example 8)
A sputtering target was manufactured under the same conditions as in Example 3 except that the reduction treatment temperature in the reduction treatment was 1000 ° C. The sintered body density of the obtained sintered body was 97%, the average pore diameter was 0.7 μm from the SEM image of the fracture surface of the sintered body, x = 0.92 in TiN _x , and the average particle diameter of the titanium nitride grains was It was 15 μm. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, sputtering was performed and the target was evaluated. As a result, no nodules were produced and good results were obtained. Further, the rate of decrease in the film formation rate was as good as 6%.

Example 9
The same conditions as in Example 3 except that an acrylic acid-based copolymer amine salt (HIPLAAD, manufactured by Enomoto Kasei Co., Ltd.) was used in place of the neutralized acrylic acid / methacrylic acid copolymer as a dispersant. A sputtering target was manufactured. The sintered body density of the obtained sintered body was 97%, the average pore diameter was 0.9 μm from the SEM image of the fracture surface of the sintered body, x = 0.92 in TiN _x , and the average particle diameter of the titanium nitride grains was It was 15 μm. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, sputtering was performed and the target was evaluated. As a result, no nodules were produced and good results were obtained. Further, the rate of film formation rate reduction was as good as 8%.

(Example 10)
A sputtering target was manufactured under the same conditions as in Example 9 except that the molding pressure in the molding process was 98 MPa. The sintered body density of the obtained sintered body was 94%, the average pore diameter was 1.5 μm from the SEM image of the fracture surface of the sintered body, x = 0.94 in TiN _x , and the average particle diameter of the titanium nitride grains was 14 μm. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, sputtering was performed and the target was evaluated. As a result, no nodules were produced and good results were obtained. Further, the rate of film formation rate reduction was as good as 10%.

(Example 11)
A sputtering target was manufactured under the same conditions as in Example 3 except that the reduction treatment time was 10 hours and the sintering temperature was 2100 ° C. The sintered body density of the obtained sintered body was 99.5%, x = 0.94 in TiN _x , and the average particle diameter of the titanium nitride grains was 20 μm. Further, the average pore diameter was 0.1 μm from the SEM image of the fracture surface of the sintered body. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, sputtering was performed and the target was evaluated. As a result, no nodules were produced and good results were obtained. Further, the rate of decrease in the film formation rate was as good as 3%.

(Comparative Example 1)
In the firing step, a sputtering target was produced under the same conditions as in Example 3 except that the firing temperature in the atmospheric pressure nitrogen atmosphere was 1750 ° C. The sintered body density of the obtained sintered body was 92%, the average pore diameter was 3.0 μm from the SEM image of the fracture surface of the sintered body, x = 0.93 in TiN _x , and the average particle diameter of the titanium nitride grains was It was 3 μm. Thus, it was confirmed by carrying out an electron microscope observation of the fracture surface of the sintered body that the grain growth of titanium nitride was insufficient and that there were many coarse pores. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, when sputtering film formation was performed and the target was evaluated, the generation of nodules was large, and the rate of film formation rate reduction was 15%, indicating that it was not suitable for long-time uniform film formation.

(Comparative Example 2)
A sputtering target was manufactured under the same conditions as in Example 3 except that the reduction treatment temperature in the reduction treatment was 350 ° C. The sintered body density of the obtained sintered body was 95%, the average pore diameter was 2.0 μm from the SEM image of the fracture surface of the sintered body, x = 0.93 in TiN _x , and the average particle diameter of the titanium nitride grains was It was 15 μm. As described above, although the crystal grains were sufficiently grown, it was confirmed by performing an electron microscope observation of the fracture surface of the sintered body that a small number of coarse grains exist. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, when sputtering film formation was performed and the target was evaluated, the effect of suppressing abnormal discharge was recognized and no nodules were generated, but the rate of film formation rate reduction was 12%, and uniform film formation over a long period of time. It turned out that it is not suitable for.

(Comparative Example 3)
A sputtering target was manufactured under the same conditions as in Example 3 except that the reduction treatment temperature in the reduction treatment was 1100 ° C. The sintered body density of the obtained sintered body was 94%, the average pore diameter was 1.8 μm from the SEM image of the fracture surface of the sintered body, x = 0.91 for TiN _x , and the average particle diameter of the titanium nitride grains was It was 15 μm. As described above, although the crystal grains were sufficiently grown, it was confirmed by performing an electron microscope observation of the fracture surface of the sintered body that a small number of coarse grains exist. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, when sputtering film formation was performed and the target was evaluated, the effect of suppressing abnormal discharge was recognized and no nodules were generated. However, the film formation rate was reduced by 11%, and uniform film formation for a long time was achieved. Is not suitable.

(Comparative Example 4)
A sputtering target was manufactured under the same conditions as in Example 3 except that the titanium nitride powder as the raw material powder was pulverized and classified in advance to use a powder having an average particle size of 0.35 μm. The sintered body density of the obtained sintered body was 92%, the average pore diameter was 2.5 μm from the SEM image of the fracture surface of the sintered body, x = 0.90 in TiN _x , and the average particle diameter of the titanium nitride grains was It was 16 μm. Although the crystal grains were sufficiently grown as described above, it was confirmed by observation with an electron microscope of the fracture surface of the sintered body that there were many coarse pores. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, sputtering film formation was performed and the target was evaluated. As a result, nodules were frequently generated, and the film formation rate decreased by 14%, which was not suitable for uniform film formation for a long time.

(Comparative Example 5)
A sputtering target was produced under the same conditions as in Example 3 except that the titanium nitride powder as the raw material powder was classified in advance and a powder having an average particle size of 1.7 μm was used. The sintered body density of the obtained sintered body was 91%, the average pore diameter was 2.8 μm from the SEM image of the fracture surface of the sintered body, x = 0.93 in TiN _x , and the average particle diameter of the titanium nitride grains was It was 12 μm. Although the crystal grains were sufficiently grown as described above, it was confirmed by observation with an electron microscope of the fracture surface of the sintered body that there were many coarse pores. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, sputtering film formation was performed and the target was evaluated. As a result, nodules were frequently generated and the rate of film formation rate reduction was 16%, which was not suitable for long-time uniform film formation.

(Comparative Example 6)
A sputtering target was manufactured under the same conditions as in Example 3 except that the molding pressure in the molding process was 90 MPa. The sintered body density of the obtained sintered body was 92%, the average pore diameter was 2.4 μm from the SEM image of the fracture surface of the sintered body, x = 0.92 in TiN _x , and the average particle diameter of the titanium nitride grains was It was 12 μm. Although the crystal grains were sufficiently grown as described above, it was confirmed by observation with an electron microscope of the fracture surface of the sintered body that there were many coarse pores. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, sputtering was performed and the target was evaluated. As a result, nodules were frequently generated and the rate of film formation rate reduction was 14%, indicating that it was not suitable for long-time uniform film formation.

(Comparative Example 7)
A sputtering target was manufactured under the same conditions as in Example 3 except that the firing temperature in the firing step was 2150 ° C. The sintered body density of the obtained sintered body was 92%, the average pore diameter was 3.5 μm from the SEM image of the fracture surface of the sintered body, x = 0.89 in TiN _x , and the average particle diameter of the titanium nitride grains was It was 25 μm. Although the crystal grains were sufficiently grown as described above, it was confirmed by observation with an electron microscope of the fracture surface of the sintered body that there were many coarse pores. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, sputtering film formation was performed and the target was evaluated. As a result, nodules were frequently generated and the rate of film formation rate reduction was 16%, which was not suitable for long-time uniform film formation.

(Comparative Example 8)
As a starting material, except that a mixture of TiH ₂ powder (average particle size 3 μm) and TiN powder (average particle size 1.2 μm) was used, and sintering was performed at a sintering temperature of 1650 ° C. for 5 hours, A sputtering target was manufactured under the same conditions as in Example 3. The sintered body density of the obtained sintered body was 95%, the average pore diameter was 3.0 μm from the SEM image of the fracture surface of the sintered body, x = 0.75 in TiN _x , and the average particle diameter of the titanium nitride grains was It was 3 μm. Thus, it was confirmed by carrying out an electron microscope observation of the fracture surface of the sintered body that the grain growth of titanium nitride was not sufficient and there were many coarse pores. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. As a result of target evaluation by sputtering film formation on a film, it was found that nodules were generated and it was not suitable for long-time film formation. The obtained film was also subjected to nitrogen analysis, and as a result, the nitrogen quality of TiN _x was extremely low at x = 0.75. Therefore, nitrogen gas was added to the sputter introduction gas, and accordingly, the rate of film formation rate reduction was 20%.

(Example 12)
A sputtering target was produced under the same conditions as in Example 3 except that the amount of the dispersant added was 0.5 parts by mass. Although there was a tendency for the density of the compact to be low, cracks did not occur in the molding process, the density of the sintered body was 94%, and the average pore diameter from the SEM image of the fracture surface of the sintered body Was 1.3 μm, x = 0.94 in TiN _x , and the average particle size of the titanium nitride grains was 15 μm. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, sputtering was performed and the target was evaluated. As a result, no nodules were produced and good results were obtained. Further, the rate of film formation rate reduction was as good as 9%.

(Example 13)
A sputtering target was produced under the same conditions as in Example 3 except that the amount of the dispersant added was 1.8 parts by mass. Cracks in the firing step is not generated, the sintered body density is 93% of the obtained sintered body, the average pore size than the SEM image of the fracture surface of the sintered body 1.4 [mu] m, x = 0 in TiN _x. 93. The average particle diameter of the titanium nitride grains was 15 μm. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, sputtering was performed and the target was evaluated. As a result, no nodules were produced and good results were obtained. Further, the rate of film formation rate reduction was as good as 10%.

(Comparative Example 9)
A sputtering target was produced under the same conditions as in Example 3 until the molding step, except that the amount of dispersant added was 0.4 parts by mass. An increase in slurry viscosity (> 100 cps) was observed in the granulation step, spherical granulated powder was not obtained, and cracks occurred in the molded body in the molding step.

(Comparative Example 10)
A sputtering target was produced under the same conditions as in Example 3 up to the firing step except that the amount of the dispersant added was 2.2 parts by mass. Cracks occurred in the sintered body during the binder removal process in the firing step.

(Example 14)
A sputtering target was produced under the same conditions as in Example 3 except that the amount of polyvinyl alcohol (PVA) added was 1.1 parts by mass. Although the strength of the compact was reduced and chipping was apt to occur somewhat, cracks in the compact did not occur in the molding process, and the sintered compact density of the resulting sintered compact was 95%. From the SEM image of the fracture surface of the bonded body, the average pore diameter was 0.8 μm, in TiN _x , x = 0.93, and the average particle diameter of the titanium nitride grains was 16 μm. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, sputtering was performed and the target was evaluated. As a result, no nodules were produced and good results were obtained. Further, the rate of decrease in the film formation rate was as good as 6%.

(Example 15)
A sputtering target was produced under the same conditions as in Example 3 except that the amount of polyvinyl alcohol (PVA) added was 1.8 parts by mass. Cracking of the sintered body did not occur in the firing step, the sintered body density of the obtained sintered body was 93%, the average pore diameter was 1.3 μm from the SEM image of the fracture surface of the sintered body, _x in TiN x = 0.94, and the average particle diameter of the titanium nitride grains was 15 μm. Moreover, generation | occurrence | production of the titanium oxide was not seen by the X-ray-diffraction measurement. Similarly, sputtering was performed and the target was evaluated. As a result, no nodules were produced and good results were obtained. Further, the rate of film formation rate reduction was as good as 10%.

(Comparative Example 11)
A sputtering target was produced under the same conditions as in Example 1 until the molding step, except that the amount of polyvinyl alcohol (PVA) added was 0.8 parts by mass. A reduction in the strength of the compact was observed, and cracks occurred in the compact in the molding process.

(Comparative Example 12)
A sputtering target was produced under the same conditions as in Example 1 up to the firing step, except that the amount of polyvinyl alcohol (PVA) added was 2.2 parts by mass. Cracks occurred in the sintered body during the binder removal process in the firing step.

Claims (8)

A titanium nitride sputtering target for forming a titanium nitride film on a resin film, the constituents of which are titanium, nitrogen, and unavoidable components, the composition ratio of which is 0.00 in the general formula: TiN _x . 8 ≦ x ≦ 1.0, the sintered body density is in the range of 93% to 100% in terms of the theoretical density ratio, and the average pore diameter is in the range of 0.1 μm to 1.5 μm. A titanium nitride sputtering target characterized by that.   2. The titanium nitride sputtering target according to claim 1, wherein the average particle diameter of the titanium nitride grains is in the range of 5 μm to 20 μm. (1) Using a titanium nitride powder having an average particle size in the range of 0.4 μm to 1.5 μm as a starting material,
(2) In a water solvent, the titanium nitride powder is added to 100 parts by mass of the titanium nitride powder together with a dispersant selected from an acrylic acid-methacrylic acid copolymer neutralized ammonia and an acrylic acid-based copolymer amine salt. On the other hand, the dispersant is added so as to be in the range of 0.5 parts by mass to 2.0 parts by mass, wet pulverized,
(3) The obtained pulverized product is spray-dried,
(4) The resulting granulated powder is molded at a pressure in the range of 98 MPa to 294 MPa using a cold isostatic press,
(5) The obtained molded body was reduced at a temperature in the range of 400 ° C. to 1000 ° C. in a reducing atmosphere, and then fired at a temperature of 1800 ° C. to 2100 ° C. in a nitrogen atmosphere.
(6) processing the obtained sintered body;
The manufacturing method of a titanium nitride sputtering target provided with the process of.   The manufacturing method of the titanium nitride sputtering target of Claim 3 using the nitrogen hydrogen mixed atmosphere or hydrogen atmosphere containing 1 volume% or more of hydrogen as said reducing atmosphere.   The method for producing a titanium nitride sputtering target according to claim 3, wherein the reduction treatment is performed in a reducing atmosphere of atmospheric pressure or pressure, and the baking treatment is performed in an atmosphere of atmospheric pressure or pressure.   4. The titanium nitride sputtering target according to claim 3, wherein in the wet pulverization step, 1.0 part by mass to 2.0 parts by mass of polyvinyl alcohol is further added as a binder to 100 parts by mass of the titanium nitride powder. Production method.   The manufacturing method of the titanium nitride sputtering target of Claim 3 which obtains spherical granulated powder using a spray dryer in the said spray drying process.   The method for manufacturing a titanium nitride sputtering target according to claim 3, wherein a carbon heater furnace is used in the firing step.