JP2928907B2 - High purity precipitated titanium material and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-purity precipitated titanium material particularly suitable as a sputtering target material used for forming a thin film as a wiring material in the manufacture of semiconductor devices such as LSIs and ULSIs, and its production. About the method.

[0002]

2. Description of the Related Art Due to the rapid increase in the degree of integration of LSIs in recent years, electrode materials used for LSIs and ULSIs have been replaced by polysilicon which has been frequently used in order to solve signal delay caused by thinning of electrode wiring. Instead, there is a shift to lower resistance, high purity, high melting point metallic materials. LSI, ULS
Molybdenum, tungsten, titanium or their silicides are high-purity and high-melting metal materials used for I. Among them, titanium is particularly promising because it has excellent specific strength, workability and corrosion resistance. I have.

[0003] When a semiconductor electrode is formed of titanium, sputtering is used. Therefore, a sputtering target material made of high-purity titanium is required. A high-purity titanium target material is usually manufactured as follows.

[0004] A high-purity precipitated titanium material refined by an iodide pyrolysis method or an electrolytic method is dissolved, processed, and heat-treated to form a plate-like ingot target material. However, in these methods, melting, processing, and heat treatment are performed after purification, so that the number of steps is increased and the production cost is increased.

In order to solve these problems, a direct production method of a high-purity target material disclosed in Japanese Patent Application Laid-Open No. Sho 62-294175 has been proposed. In this method, a purified metal is deposited on the surface of a plate-like substrate by a halide pyrolysis method. Since the purified metal is deposited on the surface of the plate-like substrate, the deposited material can be used as it is as a sputtering target material. As a result, dissolution, processing, and heat treatment after purification become unnecessary, and the production cost is reduced. That is, the method disclosed in Japanese Patent Application Laid-Open No. 62-294175 proposes a method for producing a deposition target material with respect to a smelting target material.

[0006]

However, Japanese Patent Application Laid-Open No. Sho 62-62
In the method of manufacturing a deposition target material disclosed in Japanese Patent No. 294175, impurity contamination is considered as a problem, but the crystal grain size of the purified metal deposited on the substrate surface is not considered.

In the case of a high-purity titanium target material for sputtering, it is necessary to refine the crystal grains of high-purity titanium in order to make the thickness of a thin film formed by sputtering uniform. For this reason, in the production of a smelting target material, heat treatment is performed after melting and processing. However, in the method disclosed in Japanese Patent Application Laid-Open No. 62-294175, a method for making the crystal grains fine is not specified, and the crystal grains of high-purity titanium are made fine enough to make the sputtering film thickness uniform. I don't think it is. Therefore, it is difficult to use the produced deposition target material directly for sputtering.

In the method disclosed in Japanese Patent Application Laid-Open No. 62-294175, a halide pyrolysis method is used for purification of high-purity titanium. In this method, the following reaction proceeds in the reaction vessel. Crude Ti + 2I ₂ → TiI ₄ (synthesis reaction) TiI ₄ → high-purity Ti + 2I ₂ (pyrolysis reaction)

In the halide pyrolysis method, since the temperature of the synthesis reaction is as low as 200 to 400 ° C., low melting titanium iodide (TiI ₂ , TiI ₃ ) as a by-product is easily generated in a solid state. . Lower iodide titanium generated covers the rough titanium surfaces, the continuation of the reaction hinder. On the other hand, the temperature of the thermal decomposition reaction is as high as 1300 to 1500 ° C., which promotes the thermal decomposition of metal impurities contained in titanium tetraiodide as a titanium deposition gas source, and causes a limitation on the purification of the precipitated titanium. .

[0010] Therefore, it is also difficult to deposit high-purity, purified titanium having a sufficient thickness on the surface of the substrate.

An object of the present invention is to provide a high-purity precipitated titanium material which can be directly used as a target material for sputtering without any problem, and a method for producing the same. Another object of the present invention is to provide a method for producing a high-purity precipitated titanium material capable of giving purified titanium high purity and sufficient thickness.

[0012]

As a method for purifying high-purity titanium for depositing high-purity titanium having a sufficient thickness on the surface of a substrate, the present applicant has previously developed a method using a lower iodide pyrolysis method. (JP-A-3-215633). The method includes holding crude titanium and a substrate in a reaction vessel,
A method of reacting crude titanium with titanium tetraiodide to synthesize lower titanium iodide, and thermally decomposing the synthesized lower titanium iodide on the surface of a substrate to deposit purified titanium on the surface of the substrate. It is.

Here, lower titanium iodide is defined as TiI ₂ , T
iI is that _3. These lower titanium iodides have a higher synthesis reaction temperature and a lower thermal decomposition reaction temperature than titanium tetraiodide.

The lower iodide pyrolysis method developed by the present applicant utilizes this reaction temperature of lower titanium iodide.
In the reaction vessel, crude titanium is once reacted with titanium tetraiodide to synthesize lower titanium iodide, and high purity titanium is produced via the lower titanium iodide. The reaction formula in this case is as follows. Crude Ti + TiI ₄ → 2TiI ₂ (synthetic reaction) 2TiI ₂ → high-purity Ti + TiI ₄ (pyrolytic reaction)

The synthesis of lower titanium iodide by the reaction of crude titanium and titanium tetraiodide is carried out at about 700 to 900 ° C., which is higher than the synthesis of titanium tetraiodide, and the lower titanium iodide is directly gaseous. can get. At the synthesis temperature of lower titanium iodide, unreacted titanium tetraiodide produced by thermal decomposition is also maintained in a gaseous state. Therefore, there is no possibility that the iodide gas (lower titanium iodide and titanium tetraiodide) in the reaction vessel covers the rough titanium surface, and the synthesis reaction is stably continued.

The synthesized lower titanium iodide is easier to thermally decompose than titanium tetraiodide, and has a thermal decomposition temperature of 1100 to 13
It can be lowered to about 00 ° C. Therefore, thermal decomposition of metal impurities contained in the lower titanium iodide as a titanium deposition gas source is prevented, and there is no possibility that the metal impurities are mixed into the deposited titanium.

If titanium iodide (titanium tetraiodide and lower titanium iodide) is discharged from the reaction vessel while titanium tetraiodide is supplied into the reaction vessel during the reaction, crude iodide can be converted from crude titanium. The metal impurities released into the titanium gas are discharged one by one to the outside of the reaction vessel, so that there is no possibility that the metal impurities are concentrated in the titanium iodide gas in the reaction vessel.

[0018] Thus, the lower iodide pyrolysis method can continue to deposit purified titanium of higher purity on the surface of the substrate for a long time.

The present inventors have conducted various studies to use a high-purity precipitated titanium material produced by a lower iodide pyrolysis method as a sputtering target material, and have obtained the following findings. It was completed.

That is, if the average crystal grain size of the purified titanium deposited on the substrate surface is 500 μm or less, the sputtering film thickness becomes uniform when the high purity precipitated titanium material is directly used as a sputtering target material. When the average crystal grain size of the substrate is 500 μm or less, the average crystal grain size of the purified titanium deposited on the surface is 500 μm.
μm was knowledge that you become less.

Further, in order to make the thickness of the thin film formed by sputtering uniform, it is important to make the crystal grain size of the deposited titanium uniform and to make the crystal grain size uniform. Accordingly, the present inventors have further studied to develop a method for imparting uniform and fine crystal grains to purified titanium deposited on the surface of the substrate, and as a result, have used a mesh having a constant lattice spacing on the substrate or the substrate surface. It has been found that it is effective to further perform cold rolling and recrystallization heat treatment on the precipitated material.

The high-purity precipitated titanium material of the present invention has a low iodide content.
Is a high-purity precipitated titanium material in which purified titanium is deposited on the surface of a substrate by a lower iodide pyrolysis method using a synthesis reaction and a thermal decomposition reaction of a product, and the average crystal grain size of the purified titanium deposited on the surface of the substrate is It is set to 500 μm or less.

The method for producing a high-purity precipitated titanium material of the present invention comprises, first, a synthesis reaction and a thermal decomposition reaction of a lower iodide.
When precipitating the purified titanium on the surface of the substrate by a lower iodide pyrolysis method using an average crystal grain size by using the following substrate 500 [mu] m, purification deposited on the surface of the substrate
The average crystal grain size of titanium is set to 500 μm or less .

The second method involves a synthesis reaction of lower iodide and
When precipitating the purified titanium on the surface of the substrate by a lower iodide pyrolysis method using fine thermal decomposition reaction, the use of grid-like net average lattice spacing is 500μm or less in the substrate or substrate surface, the substrate Purified copper deposited on the surface of
The average crystal grain size of tan is set to 500 μm or less .

The third method involves the synthesis reaction of lower iodide and
And a total reduction ratio of not less than 0.5 at 400 ° C. or less and 1 pass to high-purity deposited titanium material obtained by depositing purified titanium on the surface of a substrate by a lower iodide pyrolysis method using thermal decomposition reaction .
Cold rolling with a distribution ratio of reduction ratio of 10% or more ,
Further particular performing recrystallization heat treatment at 400 to 600 ° C.
The average crystal grain size of purified titanium deposited on the surface of the substrate
Is set to 500 μm or less .

The lower iodide pyrolysis method is more specifically described as follows.
The crude titanium and the substrate are held as raw materials in a reaction vessel, and titanium tetraiodide is reacted with the crude titanium to synthesize lower titanium iodide, and the synthesized lower titanium iodide is thermally decomposed on the surface of the substrate. How to

[0027]

The high purity precipitated titanium material of the present invention can be directly used as a target material for sputtering because the average crystal grain size of the purified titanium is 500 μm or less while being a deposited material, and a thin film having a uniform thickness in the sputtering. Can be formed. In addition, lower iodide
Since the thermal decomposition method is used, there are few impurities and the thickness is
It is easy to maintain the sputtering target.
Suitable as

According to the first method of the present invention, the substrate is 500 μm
Since having an average grain size less can the average crystal grain size of the purified titanium is deposited on the surface to 500μm or less.

This is because the deposited titanium grows depending on the crystal structure of the substrate at the beginning of the reaction. Although the reaction mechanism is not clear, it is considered to be due to epitaxy growth in which one crystal grows in a certain orientation on the surface of another crystal. That is, when a substrate having a similar lattice spacing is used, a crystal plane layer that is structurally well associated with the crystal plane of the substrate is deposited.

The average crystal grain size of the purified titanium is set to 500 μm or less, preferably 100 μm or less, more preferably 50 μm or less for uniformizing the film thickness distribution during sputtering. Therefore, the average crystal grain size of the substrate is also set to 500 μm or less, preferably 100 μm or less, more preferably 50 μm or less.
μm or less.

A substrate having an average crystal grain size of 500 μm or less is
It can be manufactured by performing a heat treatment for recrystallization miniaturization after processing. If the heat treatment is insufficient, flat
Even when the average crystal grain size is 500 μm or less, a processed structure that has not been recrystallized (unrecrystallized grains) may remain. If unrecrystallized grains remain, the structure becomes non-uniform, and the purified titanium deposited also does not have a uniform structure, which adversely affects the film thickness distribution during sputtering. Therefore, the substrate needs to be sufficiently heat-treated so that unrecrystallized grains do not remain.

As a material for the substrate, tantalum, molybdenum, tungsten, silicon, etc. can be used in addition to titanium.

The shape of the substrate is preferably a flat plate or a rectangular tube formed by combining flat plates in view of direct use as a sputtering target material, but may be a circular tube and is not particularly limited.

In the second method of the present invention, the use of a lattice-like net having an average lattice spacing of 500 μm or less on the substrate or the surface of the substrate allows the crystal grains of purified titanium to be reduced to an average of 500 μm or less while being a precipitation material. It can be made finer and its crystal grain size can be made uniform.

Then, the high-purity precipitated titanium can be directly used as a sputtering target material, and a thin film having a uniform thickness can be formed by the sputtering.

The lattice spacing of the net is desirably constant in order to make the crystal grain size of the purified titanium uniform. The interval is 500 on average to reduce the crystal grain size.
μm or less is required, preferably 100 μm or less on average , particularly preferably 50 μm or less on average .

As a material of the net, molybdenum, tantalum or the like can be used in addition to titanium.

When a net is used as the base, the net itself becomes the base.

The shape of the substrate is desirably a flat plate or a rectangular tube formed by combining flat plates in view of direct use as a sputtering target material, but may be a cylinder, and is not particularly limited.

When a net is used on the surface of the substrate, a substrate obtained by attaching a net to the surface of the substrate is used as the substrate. In this case, the material of the base does not need to be the same as that of the net, and may be of a different kind. In addition to titanium, tantalum, molybdenum, tungsten, silicon, or the like can be used as appropriate.

Regarding the relationship between the crystal grain size of the substrate and the lattice spacing of the net, when the net is adhered to the surface of the base, the purified titanium precipitates on the net lattice, so And the crystal grain size of the purified titanium is determined by the lattice spacing of the net. Therefore, it is not necessary to make the crystal grain size of the substrate finer and uniform.

In the third method of the present invention, the total rolling ratio is 0.5 or more to 400 ° C. or less with respect to the precipitated material in one pass.
Cold rolling at a distribution ratio of the reduction ratio of 10% or more , followed by recrystallization heat treatment at 400 to 600 ° C., results in an average crystal grain size of 500 μm or less, and more preferably 10 to 1 μm.
A fine and uniform crystal structure of 00 μm can be given to purified titanium.

The reason for setting the rolling temperature in the cold rolling at 400 ° C. or lower is as follows. If cold rolling is performed at this temperature, deformation resistance is large, so that the crystal grains have a dense fibrous structure, and the stored energy of internal strain increases.
As a result, in the subsequent heat treatment, recrystallization easily occurs with the strain as a nucleus, so that the crystal grains can be made finer and uniform.

As for the rolling reduction ratio, the total reduction ratio was 0.5
As described above, the distribution ratio of the reduction ratio in one pass is set to 10% or more . This is because when the total reduction ratio is less than 0.5, the rolling structure exerted by the processing up to the center of the material thickness becomes non-uniform, and when the one-pass distribution ratio of the reduction ratio is less than 10%, the total reduction ratio is 0.5. This is because unrecrystallized grains remain in the subsequent heat treatment. A particularly desirable distribution ratio is 25% or more.

The reason why the heat treatment temperature is set to 400 to 600 ° C. is that if the temperature is lower than 400 ° C., unrecrystallized grains remain, and if the temperature exceeds 600 ° C., the crystal grains become coarse.

The average crystal grain size of the refined titanium before rolling is assumed to exceed 500 μm.
The average grain size is set to 500 μm by the method described above.
when controlled below m it is possible to further refine the average crystal grain size by rolling and the subsequent heat treatment <br/> and Do Ri which are also within the scope of the present invention.

In the direct production of a high-purity deposited titanium material by a lower iodide pyrolysis method, cracks are formed in the titanium during the deposition process, which also adversely affects the film thickness distribution during sputtering. This crack is eliminated by the subsequent rolling, and from this point, the sputtering film thickness can be made uniform.

[0048]

Embodiments of the present invention will be described below.

Example 1 A titanium plate having an average crystal grain size of 500 μm or less is obtained by hot forging, rolling at 400 ° C. or less, and further heat-treating at a temperature of 500 to 650 ° C. A substrate made of

Using the manufactured substrate, purification is performed by a lower iodide pyrolysis method. FIG. 1 shows a purification apparatus.

The reaction vessel 1 is a cylindrical airtight vessel made of stainless steel, Inconel, Hastelloy or the like, and is arranged in the heating furnace 2. Au, Pt, T
a, Mo, W, or quartz is coated to a thickness of 2 mm or less. The dimensions of the reaction vessel 1 are 250 in this case.
mm and a height of 600 mm.

A vacuum pump 4 is connected to the reaction vessel 1 via a collector 3, and a titanium tetraiodide vessel 5 housed in an electric furnace is connected via a valve.

The substrate 6 made of a titanium plate is a rectangular tube having a closed upper end, is arranged upright in the center of the reaction vessel 1, and is indirectly heated by a heater 8 arranged inside. Around the base 6, four pieces of coarse titanium 7 made of a titanium plate are set in a square cylindrical shape so as to take in the base. The crude titanium 7 is heated to a predetermined temperature by heating the inside of the reaction vessel 1 in the heating furnace 2.

To perform purification, the inside of the reaction vessel 1 is evacuated to 10 ^-1 to 10 ^-3 Torr by a vacuum pump.
The inside of the reaction vessel 1 is heated to 700 to 900 ° C. by the heating furnace 2. The substrate 6 is heated to 1100 to 1300 ° C. Titanium tetraiodide (TiI ₄ ) is supplied into the reaction vessel 1. At this time, the vacuum evacuation is continued, and the inside of the reaction vessel 1 is 10 ^-1 to 1.
To maintain a 0 ^-3 Torr.

The titanium tetraiodide introduced from below into the reaction vessel 1 reacts with the crude titanium 7 set around the base 6 to synthesize lower titanium iodide (TiI ₂ , TiI ₃ ). The synthesized lower titanium iodide reaches the center in the reaction vessel 1 by gas diffusion, and is thermally decomposed on the surface (here, the outer surface) of the substrate 6 to deposit high-purity purified titanium on the surface. Precipitate.

The iodine or titanium tetraiodide generated by the thermal decomposition reacts again with the crude titanium 13 to synthesize lower titanium iodide. While repeating this reaction, the titanium tetraiodide and the lower titanium iodide rise in the reaction vessel 1 to keep depositing high-purity purified titanium on the surface of the substrate 6, and eventually, excess tetraiodide Agglomeration and collection are performed in the collector 3 together with titanium. The collected lower titanium iodide is reacted with iodine to be regenerated and recycled as titanium tetraiodide.

Under the conditions shown in Table 1, thickness 11 mm × width 100
A high-purity precipitated titanium material having a size of 200 mm x 200 mm was produced. Substrate purity 5N (99.999%), thickness 1m
m and the purity of the purified titanium is 6N (99.99999).
%) And the thickness was 10 mm. Also, the average crystal of the substrate
The particle size is 20 μm, 50 μm, 100 μm
There were six types: 500 μm, 1000 μm, and 2000 μm. The average grain size of purified titanium is 20μ corresponding to the substrate.
m, 50 μm, 100 μm, 500 μm, 1000 μ
m, 2000 μm.

The six types of high purity precipitated titanium materials produced were used as sputtering target materials. Table 2 shows the thickness distribution of the thin films obtained in each case. The average film thickness is about 5000 angstroms, and the film thickness distribution is (tma
(x-tmin) / (tmax + tmin) × 100
(%). The average crystal grain size of purified titanium is 500
When the thickness is less than μm, the film thickness distribution becomes 10% or less, and it was confirmed that the high-purity precipitated titanium material can be directly used for sputtering. In particular, the average crystal grain size of the purified titanium is 5
When the thickness is 0 μm or less, the film thickness distribution is uniformed to 7%.

[0059]

[Table 1]

[0060]

[Table 2]

Example 2 A titanium plate having an average crystal grain size of 500 μm or less is obtained by hot forging, rolling at 400 ° C. or less, and further heat-treating at a temperature of 500 to 650 ° C. A substrate made of

[0062] attaching the Mo steel net of the produced same average grating period and the average <br/> crystal grain size of the substrate on one surface of the substrate, the purification by lower iodide pyrolysis method using the substrate . FIG. 2 shows a purification device.

The reaction vessel 1 is a cylindrical airtight vessel made of stainless steel, Inconel, Hastelloy or the like, and is disposed in the heating furnace 2. Au, Pt, T
a, Mo, W, or quartz is coated to a thickness of 2 mm or less. The dimensions of the reaction vessel 1 are 250 in this case.
mm and a height of 600 mm.

A vacuum pump 4 is connected to the reaction vessel 1 via a collector 3, and a titanium tetraiodide vessel 5 housed in an electric furnace is connected via a valve.

The substrate 6 made of a titanium plate is assembled in a rectangular tube shape with the upper end closed with the surface on which the net 9 is stuck facing outward, placed upright in the center of the reaction vessel 1, and placed inside. Heated indirectly by heater 8. Around the base body 6, four coarse titanium layers 7 made of a titanium plate are set in a square cylindrical shape so as to surround the base body. Crude titanium 7
Is heated to a predetermined temperature by heating the inside of the reaction vessel 1 with the heating furnace 2.

To perform the purification, the inside of the reaction vessel 1 is evacuated to 10 ^-1 to 10 ^-3 Torr by a vacuum pump.
The inside of the reaction vessel 1 is heated to 700 to 900 ° C. by the heating furnace 2. The substrate 6 is heated to 1100 to 1300 ° C. Titanium tetraiodide (TiI ₄ ) is supplied into the reaction vessel 1. At this time, the vacuum evacuation is continued, and the inside of the reaction vessel 1 is 10 ^-1 to 1.
To maintain a 0 ^-3 Torr.

The titanium tetraiodide introduced from below into the reaction vessel 1 reacts with the crude titanium 7 set around the substrate 6 to synthesize lower titanium iodide (TiI ₂ , TiI ₃ ). The synthesized lower titanium iodide reaches the center in the reaction vessel 1 by gas diffusion, and is thermally decomposed on the surface (here, the outer surface) of the substrate 6 to deposit high-purity purified titanium on the surface. Precipitate.

The iodine or titanium tetraiodide generated by the thermal decomposition reacts again with the crude titanium 7 to synthesize a lower titanium iodide. While repeating this reaction, the titanium tetraiodide and the lower titanium iodide rise in the reaction vessel 1 to keep depositing high-purity purified titanium on the surface of the substrate 6, and eventually, excess tetraiodide Agglomeration and collection are performed in the collector 3 together with titanium. The collected lower titanium iodide is reacted with iodine to be regenerated and recycled as titanium tetraiodide.

Under the conditions shown in Table 3, thickness 11 mm × width 100
A plate-shaped high-purity precipitated titanium material having a size of 200 mm x 200 mm was produced. The purity of the substrate was 5N (99.999%), the thickness was 1 mm, and the purity of the purified titanium was 6N (99.99%).
99%) and the thickness was 10 mm. The average crystal grain size of the substrate and the average lattice spacing of the Mo net were 500 μm,
Three types of 200 μm and 50 μm were used. The average crystal grain size of the purified titanium is 500 μm corresponding to the substrate and Mo net,
It was 200 μm and 50 μm.

The average crystal of purified titanium in the manufactured high-purity precipitated titanium material was determined for each case where three types of substrates having different average crystal grain diameters were used without attaching a net and when using the substrate with an attached net. Measurement results of the grain size (maximum average crystal grain size, minimum average crystal grain size), and the film thickness distribution of the thin film obtained when each high-purity precipitated titanium material was used as a sputtering target material Are shown in Table 4. The average crystal grain size was measured using a cutting method. The average thickness of the thin film was about 500 angstroms, and the thickness distribution was represented by (maximum thickness−minimum thickness) / average thickness × 100 (%).

[0071]

[Table 3]

[0072]

[Table 4]

By attaching a net made of Mo to the surface of the Ti substrate, it is possible to prevent the influence of the average crystal grain size of the Ti substrate.
The average crystal grain size of purified titanium can be reduced. Also, Ti
Even when the average crystal grain size is the same, the content is different between the case where only the substrate is used and the case where the Mo net is stuck on the surface of the Ti substrate, and the variation in the crystal grain size is the case where the Mo net is stuck. Is small and uniform, and the film thickness distribution of the thin film obtained by sputtering is also uniformed.

Example 3 A plate-like high-purity precipitated titanium material having an average crystal grain size of 200 μm [purity 6N (99.9999%)] produced in Example 2
Then, rolling and heat treatment were further performed. The temperature in rolling is room temperature 300 ° C, 400 ° C, 500 ° C, 600 ° C.
The total reduction ratio is 0.5, and the distribution ratio of the reduction ratio in one pass is 5.0%, 9.1%, 10.0%, and 12.5%.
%, 25.0%, and 100%. Allocation rate 10
0% means one-pass rolling, and 25.0% means four-pass rolling.

The crystal grain size (average and maximum) of the purified titanium part in the high-purity precipitated titanium material after the heat treatment was measured by a cutting method. Was measured. The average film thickness was about 500 Å, and the film thickness distribution was represented by (maximum film thickness−minimum film thickness) / average film thickness × 100 (%). The measurement results are shown in Tables 5 to 9 together with the processing conditions.

At 400 ° C. or less, the total reduction ratio is 0.5 or more,
A target having a uniform and fine grain structure with an average crystal grain size of 10 to 100 μm is formed by performing cold rolling in which the distribution ratio of the reduction ratio in the pass is 10% or more and then performing heat treatment at 400 to 600 ° C. By performing sputtering using this target, the film thickness distribution is suppressed to less than 10%.

[0077]

[Table 5]

[0078]

[Table 6]

[0079]

[Table 7]

[0080]

[Table 8]

[0081]

[Table 9]

[0083]

As described above, the high purity analysis of the present invention
Exits titanium material, yet precipitated titanium material, it is possible to obtain a uniform film thickness distribution when used in sputtering, moreover less impurity, since the thickness also ensures easy, directly used without any problem as a target material for sputtering it can.

Since the sputtering target material using the high-purity precipitated titanium material of the present invention is a precipitated titanium material, the production cost is low, the amount of impurities is small, and a thin film having a uniform film thickness distribution can be formed. Therefore, the thin film is of high quality at low cost.

[0085] manufacturing method of high purity precipitated titanium material of the present invention, a high-quality high-purity precipitated Chi <br/> Tan material capable of obtaining a uniform film thickness when used as a target material for sputtering, purified Can be manufactured more easily.

[0086] Moreover, because of the use of lower iodide pyrogenic as iodide pyrogenic, it can provide a particularly high purity and sufficient thickness to purification titanium.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of a refining apparatus suitable for producing a high-purity precipitated titanium material of the present invention.

FIG. 2 is a schematic configuration diagram of another refining apparatus suitable for producing a high-purity precipitated titanium material of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Reaction container 5 Titanium tetraiodide container 6 Substrate 7 Crude titanium 9 Net

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kazuo Kobayashi 1 in Higashihama-cho, Amagasaki City, Hyogo Prefecture Inside Sumitomo Citizens Co., Ltd. References JP-A-5-214520 (JP, A) JP-A-62-294175 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C23C 14/34 C23C 18/08 C22B 34 / 12 C22C 1/00

Claims (6)

(57) [Claims] 1. A synthesis reaction and a thermal decomposition reaction of a lower iodide.
A high purity precipitated titanium material to precipitate purified titanium on the surface of the substrate by a lower iodide pyrolysis method using the substrate of
The average crystal grain size of purified titanium deposited on the surface is 500 μm
A high purity precipitated titanium material characterized by the following. 2. A sputtering target material using the high-purity precipitated titanium material according to claim 1. 3. A thin film formed from the sputtering target material according to claim 2. 4. Synthesis reaction and thermal decomposition reaction of lower iodide
When the purified titanium is deposited on the surface of the substrate by a lower iodide pyrolysis method using, a substrate having an average crystal grain size of 500 μm or less is used, so that the refined titanium deposited on the surface of the substrate can be used.
A method for producing a high-purity precipitated titanium material, characterized in that the average crystal grain size of titanium production is 500 μm or less . 5. A synthesis reaction and a thermal decomposition reaction of a lower iodide.
When the purified titanium is deposited on the surface of the substrate by a lower iodide pyrolysis method using , a lattice network having an average lattice spacing of 500 μm or less is used on the substrate or the substrate surface.
As a result, the average amount of purified titanium deposited on the surface of the base
High purity characterized by a crystal grain size of 500 μm or less
Manufacturing method of deposited titanium material. 6. A synthesis reaction and a thermal decomposition reaction of a lower iodide.
400.degree. C. for a high-purity deposited titanium material obtained by depositing purified titanium on the surface of a substrate by a lower iodide pyrolysis method using
When the total reduction ratio is 0.5 or more, the reduction ratio in one pass
Perform cold rolling with a distribution ratio of 10% or more, and
By performing a recrystallization heat treatment at 600 ° C.,
The average crystal grain size of purified titanium deposited on the surface is 500 μm
A method for producing a high-purity precipitated titanium material, characterized in that :