Tungsten Sintered Compact Sputtering Target and Tungsten Film Formed Using Said Target

Abstract

A tungsten sintered compact sputtering target, wherein a molybdenum strength detected with a secondary ion mass spectrometer (D-SIMS) is equal to or less than 1/10000 of the tungsten strength. This target reduces the specific resistance of a tungsten film sputtered using the tungsten sintered compact target by reducing the molybdenum in the tungsten sintered compact sputtering target and adjusting the grain size distribution of the W powder that is used during sintering.

Claims

1. A method of producing a sputtering target consisting of tungsten, molybdenum, and unavoidable impurities, wherein a W powder having a grain size distribution in which a grain size ratio of tungsten grains of 10 m or less is 30% or more and less than 70%, and a content of molybdenum is 3 ppm or less, is sintered to obtain the sputtering target.

2. The method according to claim 1, wherein a molybdenum peak intensity of the sputtering target detected with a secondary ion mass spectrometer (D-SIMS) is equal to or less than 1/100000 of a tungsten peak intensity.

3. The method according to claim 1, wherein a molybdenum peak intensity of the sputtering target detected with a secondary ion mass spectrometer (D-SIMS) is equal to or less than 1/1000000 of a tungsten peak intensity.

4. The method according to claim 1, wherein a molybdenum peak intensity of the sputtering target detected with a secondary ion mass spectrometer (D-SIMS) is equal to or less than 1/10000 of a tungsten peak intensity of the sputtering target.

5. The method according to claim 1, wherein the content of molybdenum is 1 ppm or less.

6. The method according to claim 1, wherein the content of molybdenum is 0.1 ppm or less.

7. A method of producing a sputtering target, comprising the step of sintering a powder consisting of W of a purity of 99.999% in which a content of molybdenum is 3 ppm or less and having a grain size distribution in which a grain size ratio of tungsten grains of 10 m or less is 30% or more and less than 70% to produce a high-purity tungsten sputtering target.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0027] FIG. 1 is a diagram showing the data (sample A) of the grain size distribution of the W raw material powder of Example 1.

[0028] FIG. 2 is a diagram showing the data (sample C) of the grain size distribution of the W raw material powder of Comparative Example 1.

DETAILED DESCRIPTION

[0029] The tungsten sintered compact sputtering target of the present invention is characterized in that the molybdenum strength (i.e., (peak) intensity) detected with a secondary ion mass spectrometer (D-SIMS) is equal to or less than 1/10000 of the tungsten strength (i.e., (peak) intensity), the molybdenum strength detected with a secondary ion mass spectrometer (D-SIMS) is preferably equal to or less than 1/100000 of the tungsten strength, and the molybdenum strength detected with a secondary ion mass spectrometer (D-SIMS) is more preferably equal to or less than 1/1000000 of the tungsten strength. This is the basic invention of the present invention. Note that the molybdenum strength and the tungsten strength in the thin film also take on the same values as those of the target.

[0030] There is a problem in that a tungsten thin film has a high specific resistance that is double that of its theoretical specific resistance, and its inherent high conductivity is not being sufficiently yielded. Thus, there are cases where a tungsten thin film is used upon reducing its resistance by eliminating the dislocation in the thin film via heat treatment.

[0031] According to Japanese Patent Application Publication No. 2001-295036, up to roughly 100 ppm is tolerated as the molybdenum concentration in a target, but when this kind of large amount of molybdenum exists in the target, and consequently in the thin film, it has been discovered that the effect of being able to reduce the specific resistance of the film via heat treatment is impaired.

[0032] Thus, as a result of intense study, the present inventors discovered that, as a solution to the foregoing problem, the film resistance can be efficiently reduced when, in a tungsten sintered compact sputtering target, the molybdenum strength in the thin film detected with a secondary ion mass spectrometer (D-SIMS) is equal to or less than 1/10000 of the tungsten strength. The present invention discovered the requirements for realizing the above.

[0033] Moreover, the present invention additionally provides the foregoing tungsten sintered compact sputtering target, wherein the film resistance after subjecting the sputtered film to heating treatment (heat treatment) at 850 C. for 60 minutes is 95% or less, preferably 92% or less, and more preferably 90% or less, in comparison to a sputtered film that was not subject to heat treatment (non-heat treated sputtered film). This further describes the characteristics and features offered by the tungsten sintered compact sputtering target of the present invention.

[0034] Moreover, the heating treatment (heat treatment) at 850 C. for 60 minutes shows the conditions of standard heating treatment that is performed as needed in a tungsten sintered compact sputtering target, and while heating treatment may also be performed under conditions that are different from the foregoing temperature and time, the foregoing conditions represent an index capable of realizing the characteristics of the target of the present invention based on the foregoing temperature and time. Accordingly, conditions of this heating treatment (heat treatment) within the range of the film resistance are covered by the present invention.

[0035] The present invention additionally provides the foregoing tungsten sintered compact sputtering target, wherein the molybdenum content in the tungsten target used in sputtering is 3 ppm or less, preferably 1 ppm or less, and more preferably 0.1 ppm or less. This further describes the characteristics and features offered by the tungsten sintered compact sputtering target of the present invention.

[0036] As described above, reduction of the molybdenum content enables the stable reduction of the electrical resistivity of a tungsten sputtering film.

[0037] Moreover, the present invention additionally provides a sintered compact sputtering target, wherein, based on the grain size distribution measurement of a W powder used during sintering, sintering is performed using a W powder in which the grain size ratio of tungsten grains of 10 m or less is 30% or more and less than 70%, and further based on the grain size distribution measurement, sintering is performed using a W powder in which the grain size ratio of tungsten grains of 10 m or less is 50% or more and less than 70%.

[0038] These are the effective conditions upon realizing the foregoing tungsten sintered compact sputtering target of the present invention. This further describes the characteristics and features offered by the tungsten sintered compact sputtering target of the present invention.

[0039] When performing measurement based on the grain size distribution measurement, primary grains or secondary grains can be measured. The W powder to be used may be primary grains or secondary grains. The upper limit of 70% is set because, if the grains are too fine, the bulk density will decrease excessively when the grains are filled during hot press, and consequently deteriorate the productivity (number of targets that can be produced at once will decrease). The characteristic values in cases of changing the value of the grain size distribution of the W powder used during sintering will be in detail with reference to the Examples and Comparative Examples described later.

[0040] In addition, the present invention covers a tungsten thin film that is deposited using the foregoing tungsten sintered compact sputtering target. The tungsten sputtering film sputtered using a tungsten sintered compact sputtering target with a reduced molybdenum content reflects the foregoing reduction of molybdenum and enables the stable reduction of electrical resistance of the tungsten film.

[0041] Note that SIMS is preferably used for viewing the Mo distribution. SIMS is a preferred measurement means since it can perform measurement even in a micro area of a thin film.

[0042] During sintering, it is effective to perform hot press (HP) at a temperature exceeding 1500 C. After the hot press, HIP treatment can be performed at a temperature exceeding 1600 C. in order to further improve the density.

[0043] Moreover, it is possible to provide a tungsten sintered compact sputtering target having a relative density of 99% or higher, and even 99.5% or higher. Improvement of density is favorable since it can increase the strength of the target.

[0044] Since the improvement in the density will reduce holes and cause the crystal grains to become refined, and cause the sputtered surface of the target to become uniform and smooth, the present invention yields the effect of being able to reduce the generation of particles and nodules during the sputtering process and additionally extend the target life, and also yields the effect of being able to reduce the variation in quality and improve mass productivity.

[0045] Thus, simultaneously with being able to reduce the specific resistance of the tungsten film that is deposited by using a tungsten target, the target structure is uniformized in the diameter direction and the thickness direction of the target, the target strength is also sufficient, and there are no problems such as the target cracking during the operation or use thereof. Accordingly, it is possible to improve the production yield of the target.

EXAMPLES

[0046] The present invention is now explained based on the Examples and Comparative Examples. These Examples are merely illustrative, and the present invention shall in no way be limited thereby. In other words, various modifications and other embodiments based on the technical spirit claimed in the claims shall be included in the present invention as a matter of course.

Example 1

[0047] A raw material having a Mo concentration of 1 wt % in Na.sub.2WO.sub.4 was subject to sulfidization treatment once, the obtained ammonium tungstate was subject to calcination to obtain a tungsten oxide, and the obtained tungsten oxide was subject to hydrogen reduction to cause the molybdenum concentration in the high purity tungsten powder to be 3 wtppm. The Mo amount was measured with the wet process. Hydrogen reduction was performed based on the following methods 1) and 2) to obtain a tungsten raw material powder.

[0048] Hydrogen reduction is performed at a hydrogen flow rate of 10 L/min to obtain a raw material in which the grain size (secondary grain size) of tungsten powder of 10 m or less is 20%. As a specific example, when the size of the reducing furnace is 2 L, used is a raw material that is produced at a flow rate of replacing hydrogen in the reducing furnace five times in one minute.

[0049] Hydrogen reduction is performed at a hydrogen flow rate of 30 L/min to obtain a raw material in which the grain size (secondary grain size) of tungsten powder of 10 m or less is 80%. As a specific example, when the size of the reducing furnace is 2 L, used is a raw material that is produced at a flow rate of replacing hydrogen in the reducing furnace fifteen times in one minute.

[0050] The foregoing sulfidization treatment is performed based on the following method.

[0051] The starting raw material is a sodium tungstate aqueous solution. Sulfidized Na and sulfuric acid were added to the aqueous solution, and the sulfide of Mo was precipitated and separated. Subsequently, sodium hydroxide and calcium salt were added to recover calcium tungstate, hydrochloric acid was further added to the obtained calcium tungstate and decomposed to obtain tungstic acid (WO.sub.3). Subsequently, ammonia was added thereto to obtain an ammonium tungstate aqueous solution.

[0052] The calcination may be suitably performed within the following conditions of 600 to 900 C.30 minutes to 3 hours.

[0053] The sulfidization treatment described above is merely an example, and without limitation to such treatment, any other means may be adopted so as long an ammonium tungstate aqueous solution can be obtained.

[0054] Filled in a carbon die were a tungsten powder (48%) having a purity of 99.999% and in which a grain size (secondary grain size) of 10 m or less is 20%, and a tungsten powder (52%) having a purity of 99.999% and in which a grain size (secondary grain size) of 10 m or less is 80%.

[0055] Subsequently, after hermetically sealing the carbon die with an upper punch and a lower punch, a pressure of 210 kgf/cm.sup.2 was applied to the die, the die was heated at 1200 C. via external heating and held for 6 hours thereafter, and then hot press was performed. The maximum temperature was 1600 C.2 hours. The hot press shape was (diameter) 456 mm10 mmt (thickness).

[0056] After the HP, HIP treatment was performed at 1750 C. for 5 hours. The relative density of the obtained tungsten sintered compact was 99.0%, the Mo/W strength ratio was 1:34,000, the Mo concentration in the target was 3 ppm, the grain size distribution (ratio of 10 m or less) of the W powder as the sintering raw material was 51%, and the specific resistance after the heat treatment performed at 850 C. for 60 minutes was 94%. These results are shown in Table 1. All of these results satisfied the conditions of the present invention.

[0057] Note that the data (sample A) of the grain size distribution of the W raw material powder of Example 1 is shown in FIG. 1.

TABLE-US-00001 TABLE 1 Mo Grain size Specific resistance Mo/W concen- distribution after heat treatment strength tration (ratio % of 10 at 850 C. for 60 ratio in target m or less) minutes Example 1 1:34,000 3 ppm 51 94% Example 2 1:210,000 0.9 ppm 45 91% Example 3 1:1,700,000 0.07 ppm 38 89% Comparative 1:8,000 15 ppm 27 97% Example 1 Comparative 1:1,100 75 ppm 22 97% Example 2

Example 2

[0058] A raw material having a Mo concentration of 1 wt % in Na.sub.2WO.sub.4 was subject to sulfidization treatment twice, the obtained ammonium tungstate was subject to calcination to obtain a tungsten oxide, and the obtained tungsten oxide was subject to hydrogen reduction to cause the molybdenum concentration in the high purity tungsten powder to be 0.9 wtppm. The Mo amount was measured with the wet process. Hydrogen reduction was performed based on the following methods 1) and 2) to obtain a tungsten raw material powder.

[0059] Hydrogen reduction is performed at a hydrogen flow rate of 10 L/min to obtain a raw material in which the grain size (secondary grain size) of tungsten powder of 10 m or less is 20%. As a specific example, when the size of the reducing furnace is 2 L, used is a raw material that is produced at a flow rate of replacing hydrogen in the reducing furnace five times in one minute.

[0060] Hydrogen reduction is performed at a hydrogen flow rate of 30 L/min to obtain a raw material in which the grain size (secondary grain size) of tungsten powder of 10 m or less is 80%. As a specific example, when the size of the reducing furnace is 2 L, used is a raw material that is produced at a flow rate of replacing hydrogen in the reducing furnace fifteen times in one minute.

[0061] Filled in a carbon die were a tungsten powder (58%) having a purity of 99.999% and in which a grain size (secondary grain size) of 10 m or less is 20%, and a tungsten powder (42%) having a purity of 99.999% and in which a grain size (secondary grain size) of 10 m or less is 80%.

[0062] Subsequently, after hermetically sealing the carbon die with an upper punch and a lower punch, a pressure of 210 kgf/cm.sup.2 was applied to the die, the die was heated at 1200 C. via external heating and held for 4 hours thereafter, and then hot press was performed. The maximum temperature was 1570 C.2 hours. The hot press shape was (diameter) 456 mm10 mmt (thickness).

[0063] After the HP, HIP treatment was performed at 1850 C. for 5 hours. The relative density of the obtained tungsten sintered compact was 99.0%, the average grain size was 32.1 m, the Mo/W strength ratio was 1:210,000, the Mo concentration in the target was 0.9 ppm, the grain size distribution (ratio of 10 m or less) of the W powder as the sintering raw material was 45%, and the specific resistance after the heat treatment performed at 850 C. for 60 minutes was 91%. These results are shown in Table 1. All of these results satisfied the conditions of the present invention.

Example 3

[0064] A raw material having a Mo concentration of 0.1 wt % in Na.sub.2WO.sub.4 was subject to sulfidization treatment twice, the obtained ammonium tungstate was subject to calcination to obtain a tungsten oxide, and the obtained tungsten oxide was subject to hydrogen reduction to cause the molybdenum concentration in the high purity tungsten powder to be 0.07 wtppm. The Mo amount was measured with the wet process. Hydrogen reduction was performed based on the following methods 1) and 2) to obtain a tungsten raw material powder.

[0065] Hydrogen reduction is performed at a hydrogen flow rate of 10 L/min to obtain a raw material in which the grain size (secondary grain size) of tungsten powder of 10 m or less is 20%. As a specific example, when the size of the reducing furnace is 2 L, used is a raw material that is produced at a flow rate of replacing hydrogen in the reducing furnace five times in one minute.

[0066] Hydrogen reduction is performed at a hydrogen flow rate of 30 L/min to obtain a raw material in which the grain size (secondary grain size) of tungsten powder of 10 m or less is 80%. As a specific example, when the size of the reducing furnace is 2 L, used is a raw material that is produced at a flow rate of replacing hydrogen in the reducing furnace fifteen times in one minute.

[0067] Filled in a carbon die were a tungsten powder (70%) having a purity of 99.999% and in which a grain size (secondary grain size) of 10 m or less is 20%, and a tungsten powder (30%) having a purity of 99.999% and in which a grain size (secondary grain size) of 10 m or less is 80%.

[0068] Subsequently, after hermetically sealing the carbon die with an upper punch and a lower punch, a pressure of 210 kgf/cm.sup.2 was applied to the die, the die was heated at 1200 C. via external heating and held for 4 hours thereafter, and then hot press was performed. The maximum temperature was 1570 C.2 hours. The hot press shape was (diameter) 456 mm10 mmt (thickness).

[0069] After the HP, HIP treatment was performed at 1570 C. for 5 hours. The relative density of the obtained tungsten sintered compact was 99.0%, the average grain size was 39.7 m, the Mo/W strength ratio was 1:1,700,000, the Mo concentration in the target was 0.07 ppm, the grain size distribution (ratio of 10 m or less) of the W powder as the sintering raw material was 38%, and the specific resistance after the heat treatment performed at 850 C. for 60 minutes was 89%. These results are shown in Table 1. All of these results satisfied the conditions of the present invention.

Comparative Example 1

[0070] A raw material having a Mo concentration of 10 wt % in Na.sub.2WO.sub.4 was subject to sulfidization treatment once, the obtained ammonium tungstate was subject to calcination to obtain a tungsten oxide, and the obtained tungsten oxide was subject to hydrogen reduction to cause the molybdenum concentration in the high purity tungsten powder to be 15 wtppm.

[0071] The Mo amount was measured with the wet process. Hydrogen reduction was performed based on the following methods 1) and 2) to obtain a tungsten raw material powder.

[0072] Hydrogen reduction is performed at a hydrogen flow rate of 10 L/min to obtain a raw material in which the grain size (secondary grain size) of tungsten powder of 10 m or less is 20%. As a specific example, when the size of the reducing furnace is 2 L, used is a raw material that is produced at a flow rate of replacing hydrogen in the reducing furnace five times in one minute.

[0073] Hydrogen reduction is performed at a hydrogen flow rate of 30 L/min to obtain a raw material in which the grain size (secondary grain size) of tungsten powder of 10 m or less is 80%. As a specific example, when the size of the reducing furnace is 2 L, used is a raw material that is produced at a flow rate of replacing hydrogen in the reducing furnace fifteen times in one minute.

[0074] Filled in a carbon die were a tungsten powder (88%) having a purity of 99.999% and in which a grain size (secondary grain size) of 10 m or less is 20%, and a tungsten powder (12%) having a purity of 99.999% and in which a grain size (secondary grain size) of 10 m or less is 80%, and this was wrapped with a carbon sheet.

[0075] Subsequently, after hermetically sealing the carbon die with an upper punch and a lower punch, a pressure of 210 kgf/cm.sup.2 was applied to the die, the die was heated at 1200 C. via external heating and held for 2 hours thereafter, and then hot press was performed. The maximum temperature was 1800 C.2 hours. The hot press shape was (diameter) 456 mm10 mmt (thickness).

[0076] After the HP, HIP treatment was performed at 1850 C. for 5 hours. The relative density of the obtained tungsten sintered compact was 99.2%, the average grain size was 22.5 urn, the Mo/W strength ratio was 1:8,000, the Mo concentration in the target was 15 ppm, the grain size distribution (ratio of 10 m or less) of the W powder as the sintering raw material was 27%, and the specific resistance after the heat treatment performed at 850 C. for 60 minutes was 97%. These results are shown in Table 1. The data (sample C) of the grain size distribution of the W raw material powder of Comparative Example 1 is shown in FIG. 2.

[0077] Consequently, the Mo/W strength ratio, the Mo concentration in the target, the grain size distribution (ratio of 10 m or less) of the W powder, and the specific resistance after the heat treatment performed at 850 C. for 60 minutes all failed to satisfy the conditions of the present invention.

Comparative Example 2

[0078] A raw material having a Mo concentration of 1 wt % in Na.sub.2WO.sub.4 was subject to sulfidization treatment once, the obtained ammonium tungstate was subject to calcination to obtain a tungsten oxide, and the obtained tungsten oxide was subject to hydrogen reduction to cause the molybdenum concentration in the high purity tungsten powder to be 3 wtppm.

[0079] The Mo amount was measured with the wet process. Hydrogen reduction was performed based on the following method 1) to obtain a tungsten powder, and Mo was further added to obtain a tungsten raw material powder having a predetermined Mo concentration (75 wtppm).

[0080] Hydrogen reduction is performed at a hydrogen flow rate of 10 L/min to obtain a raw material in which the grain size (secondary grain size) of tungsten powder of 10 m or less is 20%. As a specific example, when the size of the reducing furnace is 2 L, used is a raw material that is produced at a flow rate of replacing hydrogen in the reducing furnace five times in one minute.

[0081] Filled in a carbon die was a tungsten powder (100%) having a purity of 99.999% and in which a grain size (secondary grain size) of 10 m or less is 20%.

[0082] Subsequently, after hermetically sealing the carbon die with an upper punch and a lower punch, a pressure of 210 kgf/cm.sup.2 was applied to the die, the die was heated at 1200 C. via external heating and held for 2 hours thereafter, and then hot press was performed. The maximum temperature was 1400 C.2 hours. The hot press shape was (diameter) 456 mm10 mmt (thickness).

[0083] After the HP, HIP treatment was performed at 1570 C. for 5 hours. The relative density of the obtained tungsten sintered compact was 99.0%, the average grain size was 69.7 m, the Mo/W strength ratio was 1:1,100, the Mo concentration in the target was 75 ppm, the grain size distribution (ratio of 10 m or less) of the W powder as the sintering raw material was 22%, and the specific resistance after the heat treatment performed at 850 C. for 60 minutes was 97%. These results are shown in Table 1. Consequently, the Mo/W strength ratio, the Mo concentration in the target, the grain size distribution (ratio of 10 m or less) of the W powder, and the specific resistance after the heat treatment performed at 850 C. for 60 minutes all failed to satisfy the conditions of the present invention.

[0084] The tungsten sintered compact targets prepared with Example 1 and Comparative Example 1 were used to form a tungsten film on a silicon substrate via sputtering, and the specific resistance of the film was measured. An FIB device was used to measure the film thickness and calculate the deposition rate of the film that was deposited so that the film thickness would be approximately 1000 . The sheet resistance was separately measured.

[0085] The specific resistance of the film was obtained from the foregoing values. Consequently, the specific resistance of Example 1 was 11.47 cm, and it was confirmed that the specific resistance decreased by 3% in comparison to the specific resistance of 11.83 cm of Comparative Example 1. Note that it is extremely difficult to reduce the specific resistance of a tungsten film, and in this respect, it could be said that the reduction of 3% is a significant effect.

[0086] The present invention mainly provides a tungsten sintered compact sputtering target, wherein the molybdenum strength detected with a secondary ion mass spectrometer (D-SIMS) is equal to or less than 1/10000 of the tungsten strength and yields a superior effect of being able to stably reduce the electrical resistivity in a tungsten film that is sputter-deposited using a tungsten sintered compact sputtering target. Accordingly, the tungsten sintered compact sputtering target of the present invention is effective for the usage in forming an electrode material or a wiring material for VLSI.