WO2014021139A1 - ルテニウムスパッタリングターゲット及びルテニウム合金スパッタリングターゲット - Google Patents
ルテニウムスパッタリングターゲット及びルテニウム合金スパッタリングターゲット Download PDFInfo
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- WO2014021139A1 WO2014021139A1 PCT/JP2013/069870 JP2013069870W WO2014021139A1 WO 2014021139 A1 WO2014021139 A1 WO 2014021139A1 JP 2013069870 W JP2013069870 W JP 2013069870W WO 2014021139 A1 WO2014021139 A1 WO 2014021139A1
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- sputtering target
- ruthenium
- wtppm
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- grain size
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- 238000005477 sputtering target Methods 0.000 title claims abstract description 68
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 36
- 229910000929 Ru alloy Inorganic materials 0.000 title claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 63
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 abstract description 35
- 238000004544 sputter deposition Methods 0.000 abstract description 19
- 238000005245 sintering Methods 0.000 description 14
- 239000000758 substrate Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 239000010703 silicon Substances 0.000 description 7
- 239000010955 niobium Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011863 silicon-based powder Substances 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- 230000002159 abnormal effect Effects 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
- H01J37/3411—Constructional aspects of the reactor
- H01J37/3414—Targets
- H01J37/3426—Material
- H01J37/3429—Plural materials
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
- H01J37/3411—Constructional aspects of the reactor
- H01J37/3414—Targets
- H01J37/3426—Material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
- H01J2237/32—Processing objects by plasma generation
- H01J2237/33—Processing objects by plasma generation characterised by the type of processing
- H01J2237/332—Coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28026—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor
- H01L21/28079—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor the final conductor layer next to the insulator being a single metal, e.g. Ta, W, Mo, Al
Definitions
- the present invention relates to a ruthenium sputtering target and a ruthenium alloy sputtering target, and more particularly to a sputtering target used for forming a ruthenium oxide film used as a lower electrode of a ferroelectric capacitor of a semiconductor memory.
- ruthenium or ruthenium alloys have been used as electronic materials such as ferroelectric capacitors for semiconductor memories.
- a sputtering method is often used to form a ruthenium thin film.
- the sputtering method itself is a well-known method in the electronics field, but a target made of ruthenium or a ruthenium alloy having uniform and stable characteristics suitable for this sputtering is required.
- commercially available ruthenium materials with relatively high purity are 3N level powders, but materials used in the recent electronics field are disclosed in the following patent documents for the purpose of preventing noise generation and improving characteristics. As described above, higher purity is required, and a high purity ruthenium sputtering target is required to have a purity level of 5N.
- Patent Document 1 discloses that each alkali metal element is less than 1 ppm, each alkaline earth metal element is less than 1 ppm, each transition metal element is less than 1 ppm, each radioactive element is less than 10 ppb, carbon and gas components (oxygen, hydrogen, nitrogen, chlorine).
- a high-purity ruthenium target is described in which the purity of ruthenium excluding gas component elements is less than 500 ppm in total and is 99.995% or more.
- any content of alkali metal elements is 0.1 ppm by weight or less, and any content of alkaline earth metal elements is 0.1 ppm by weight or less.
- Patent Document 3 describes a high-purity ruthenium target having a purity of oxygen of 10 wtppm or less and nitrogen of 10 wtppm or less and a purity of 5N level or more.
- Patent Document 4 describes a sputtering target having a composition containing 1 to 9 ppm of Si and the balance being made of Ru having a purity of 99.998% or more.
- the present invention suppresses crystal growth of ruthenium or a ruthenium alloy and reduces the generation of coarse crystal grains, thereby suppressing arcing generated during sputtering as much as possible and reducing the generation of particles, or a ruthenium sputtering target or ruthenium. It is an object to provide an alloy sputtering target.
- the present inventors have conducted intensive research. As a result, it is possible to suppress coarsening of crystal grains by containing a small amount of silicon (Si) in ruthenium or a ruthenium alloy. And gained knowledge.
- the ruthenium sputtering target or the ruthenium alloy sputtering target contains a small amount of silicon, it is possible to suppress the coarsening of crystal grains. Sputtering is possible, and it has the outstanding effect that the film
- the ruthenium sputtering target of the present invention is characterized in that the Si content is 10 to 100 wtppm, the total content of inevitable impurities excluding gas components is 50 wtppm or less, and the balance is Ru.
- the Si content is 10 to 100 wtppm
- the total content of inevitable impurities excluding gas components is 50 wtppm or less
- the balance is Ru.
- the silicon content is preferably 10-100 wtppm, more preferably 10-50 wtppm. If it is less than 10 wtppm, the coarsening of the crystal grains cannot be sufficiently suppressed. On the other hand, if it exceeds 100 wtppm, the performance of the semiconductor device becomes unstable, such being undesirable.
- the present invention is also a ruthenium alloy sputter target containing 3 to 35 atomic% of one or more alloy elements selected from the group of Ta, Nb, Mo, W, and Mn, and the balance being Ru. It is characterized by that.
- ruthenium alloys are excellent in thermal stability, low resistance, and excellent barrier properties, and thus are useful as film forming materials for semiconductor elements, particularly as gate electrode materials and various diffusion barrier materials.
- the ruthenium sputtering target or ruthenium alloy sputtering target of the present invention preferably has an average crystal grain size of 5 to 100 ⁇ m and a maximum crystal grain size of 500 ⁇ m or less. This is because if coarse crystal grains exceeding the above numerical range are present, abnormal discharge (arcing) is induced during sputtering, and the number of generated particles increases.
- the ruthenium sputtering target or ruthenium alloy sputtering target of the present invention can be produced by a powder metallurgy method. First, purified Ru powder having a purity of 99.995% or more and Si powder having a purity of 99.999% or more are prepared. Further, when producing a ruthenium alloy sputtering target, Ta, Nb, Mo, W, and Mn powders having a purity of 99.999% or more are prepared as alloy elements. At this time, it is preferable to use Ru powder having an average particle size of 10 to 150 ⁇ m.
- Si powder having an average particle size of 5 to 100 ⁇ m
- Ta, Nb, Mo, W, and Mn powders, which are alloy elements are preferably used having an average particle size of 5 to 100 ⁇ m. . If the particle size of the raw material powder is too small, the bulk density of the powder becomes high and the weight charged in the mold is limited, which is not preferable. This is not preferable since the density of the sintered body is lowered as a result.
- the mixed powder is filled in a carbon mold, and then the temperature is 1200 to 1600 ° C., the pressure is 200 to 500 kg / cm 2 ,
- a sintered body of ruthenium or a ruthenium alloy can be produced by hot pressing for 4 hours under conditions of Ar or a vacuum atmosphere.
- the present invention is not limited to the above sintering conditions, but if the sintering temperature or pressure is too low or the sintering time is too short, a sufficient sintered body density cannot be obtained. It is not preferable. Further, if the sintering temperature or the sintering time is too long, coarse particles are generated, which is not preferable.
- the sputtering target of the present invention can be produced by machining the sintered body thus obtained into a target shape. In sputtering, such a target is used in a form bonded to a backing plate.
- the ruthenium sputtering target and ruthenium alloy sputtering target obtained as described above can suppress the coarsening of crystal grains, it is possible to suppress abnormal discharge (arcing) at the time of sputtering and the effect that there are few particles. Can get.
- Example 1 Ruthenium powder (purity 99.995%) having an average particle diameter of 50 ⁇ m and silicon powder (purity 99.999%) having an average particle diameter of 10 ⁇ m were prepared, and these raw material powders were mixed so that the Si content was 12 wtppm. . Next, this was filled in a carbon mold and hot pressed.
- the hot press conditions were an Ar atmosphere, a sintering temperature of 1500 ° C., a sintering pressure of 200 kg / cm 2 , and a sintering time of 1 hour.
- the sintered body thus obtained was taken out from the hot press and machined into a target shape to produce a sputtering target.
- the surface of the target was polished, and the crystal grain size of the structure was measured with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- this target was bonded to the backing plate, it was attached to a sputtering apparatus and sputtering was performed.
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles with a particle size of 0.25 ⁇ m or more adhering to the substrate was measured with a particle counter. At this time, the number of particles was as small as 72.
- Example 2 A sputtering target was produced under the same conditions as in Example 1 except that the Si content was 35 wtppm. As a result of observing the surface of this sputtering target, the average crystal grain size was 48 ⁇ m and the maximum crystal grain size was 103 ⁇ m. Coarse crystal grains were not observed. Next, this sputtering target was bonded to a backing plate and sputtered under the same conditions as in Example 1. As a result, the number of particles adhering to the substrate was as small as 63 particles.
- Example 3 A sputtering target was produced under the same conditions as in Example 1 except that the Si content was 62 wtppm. As a result of observing the surface of this sputtering target, the average crystal grain size was 21 ⁇ m and the maximum crystal grain size was 65 ⁇ m. Coarse crystal grains were not observed. Next, this sputtering target was bonded to a backing plate and sputtered under the same conditions as in Example 1. As a result, the number of particles adhering to the substrate was as small as 58.
- Example 4 A sputtering target was produced under the same conditions as in Example 1 except that the Si content was 94 wtppm. As a result of observing the surface of this sputtering target, the average crystal grain size was 8 ⁇ m and the maximum crystal grain size was 18 ⁇ m. Coarse crystal grains were not observed. Next, this sputtering target was bonded to a backing plate and sputtered under the same conditions as in Example 1. As a result, the number of particles adhering to the substrate was as small as 42.
- Example 5 Ruthenium powder (purity 99.995%) having an average particle diameter of 50 ⁇ m, tantalum powder (purity 99.995%) having an average particle diameter of 10 ⁇ m, and silicon powder (purity 99.999%) having an average particle diameter of 10 ⁇ m are prepared. These raw material powders were mixed so that the tantalum content was 15 atomic%, the Si content was 10 wtppm, and the balance was Ru. Next, this was filled in a carbon mold and hot pressed. The hot press conditions were an Ar atmosphere, a sintering temperature of 1500 ° C., a sintering pressure of 200 kg / cm 2 , and a sintering time of 1 hour.
- the sintered body thus obtained was taken out from the hot press and machined into a target shape to produce a sputtering target.
- the surface of the target was polished, and the crystal grain size of the structure was measured with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- this target was bonded to the backing plate, it was attached to the sputtering apparatus and sputtering was performed.
- the sputtering conditions were an input power of 1 kW and an Ar gas pressure of 1.7 Pa.
- a film was formed on a 4-inch diameter silicon substrate for 20 seconds.
- the number of particles with a particle size of 0.25 ⁇ m or more adhering to the substrate was measured with a particle counter. At this time, the number of particles was as small as 78.
- Example 6 A sputtering target was produced under the same conditions as in Example 5 except that the tantalum (Ta) content was 15 atomic% and the Si content was 40 wtppm. As a result of observing the surface of this sputtering target, the average crystal grain size was 53 ⁇ m and the maximum crystal grain size was 123 ⁇ m. Coarse crystal grains were not observed. Next, this sputtering target was bonded to a backing plate and sputtered under the same conditions as in Example 1. As a result, the number of particles adhering to the substrate was as small as 60.
- Example 7 A sputtering target was produced under the same conditions as in Example 5 except that the niobium (Nb) content was 8 atomic% and the Si content was 40 wtppm. As a result of observing the surface of this sputtering target, the average crystal grain size was 55 ⁇ m and the maximum crystal grain size was 118 ⁇ m. Coarse crystal grains were not observed. Next, this sputtering target was bonded to a backing plate and sputtered under the same conditions as in Example 1. As a result, the number of particles adhering to the substrate was as small as 57.
- Example 8 A sputtering target was produced under the same conditions as in Example 5 except that the tungsten (W) content was 25 atomic% and the Si content was 90 wtppm. As a result of observing the surface of this sputtering target, the average crystal grain size was 15 ⁇ m and the maximum crystal grain size was 28 ⁇ m. Coarse crystal grains were not observed. Next, this sputtering target was bonded to a backing plate and sputtered under the same conditions as in Example 1. As a result, the number of particles adhering to the substrate was as small as 37.
- Example 1 A sputtering target was prepared under the same conditions as in Example 1 except that the Si content was 3 wtppm. As a result of observing the surface of this sputtering target, the average crystal grain size was 121 ⁇ m and the maximum crystal grain size was 520 ⁇ m. The crystal grains were coarsened. Next, this sputtering target was bonded to a backing plate and sputtered under the same conditions as in Example 1. As a result, the number of particles adhering to the substrate increased to 131.
- Example 2 A sputtering target was produced under the same conditions as in Example 1 except that the Si content was 109 wtppm. As a result of observing the surface of this sputtering target, the average crystal grain size was 9 ⁇ m and the maximum crystal grain size was 15 ⁇ m. Coarse crystal grains were not observed. Next, this sputtering target was bonded to a backing plate and sputtered under the same conditions as in Example 1. As a result, the number of particles adhering to the substrate was as small as 43. On the other hand, when the volume resistivity of the formed thin film was measured, the variation was large.
- Example 3 A sputtering target was produced under the same conditions as in Example 5 except that the tantalum (Ta) content was 15 atomic% and the Si content was 107 wtppm. As a result of observing the surface of this sputtering target, the average crystal grain size was 8 ⁇ m and the maximum crystal grain size was 18 ⁇ m. Coarse crystal grains were not observed. Next, this sputtering target was bonded to a backing plate and sputtered under the same conditions as in Example 1. As a result, the number of particles adhering to the substrate was as small as 41. On the other hand, when the volume resistivity of the formed thin film was measured, the variation was large.
- the ruthenium sputtering target containing a small amount of Si suppresses the coarsening of crystal grains and reduces the generation of particles.
- increasing the Si content is effective in increasing the crystal grain size, but may affect the operating performance of the semiconductor device.
- the ruthenium sputtering target or ruthenium alloy sputtering target of the present invention can suppress the coarsening of crystal grains, suppress arcing caused by the coarse grains, enable stable sputtering, and form a film with few particles. It has an extremely excellent effect that can be formed into a film.
- the sputtering target of the present invention is particularly useful for forming a ruthenium oxide film used as a lower electrode of a ferroelectric capacitor of a semiconductor memory.
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Abstract
Description
一般に、市販されている比較的純度の高いルテニウム材料は3Nレベルの粉末であるが、最近のエレクトロニクス分野で使用される材料はノイズ発生を防止し、特性を向上させる目的から、下記特許文献に開示されるように、さらに高純度化が要求されており、高純度ルテニウムスパッタリングターゲットとしても、純度5Nレベルが必要とされている。
特許文献2には、アルカリ金属元素のいずれの含有量も0.1重量ppm以下、アルカリ土類金属元素のいずれの含有量も0.1重量ppm以下で、白金族元素以外の遷移金属元素のいずれの含有量も0.1重量ppm以下、放射性同位体元素のいずれの含有量も1重量ppb以下、ガス成分元素の含有量の合計が30重量ppm以下である純度99.995重量%以上の高純度ルテニウムターゲットが記載されている。また、特許文献3には、酸素10wtppm以下、窒素10wtppm以下であり、純度が5Nレベル以上の純度を有する高純度ルテニウムターゲットが記載されている。さらに、特許文献4には、Siを1~9ppm含有し、残部が純度99.998%以上のRuからなる組成のスパッタリングターゲットが記載されている。
1)Si含有量が10~100wtppm、ガス成分を除く不可避的不純物の総含有量が50wtppm以下、残部がRuであることを特徴とするルテニウムスパッタリングターゲット。
2)Si含有量が10~50wtppm、ガス成分を除く不可避的不純物の総含有量が10wtppm以下、残部がRuであることを特徴とする上記1)記載のルテニウムスパッタリングターゲット。
3)平均結晶粒径が5~100μm、最大結晶粒径が500μm以下であることを特徴とする上記1)又は2)記載のルテニウムスパッタリングターゲット。
4)Ta、Nb、Mo、W、Mnの群から選択される1種以上の合金元素を3~35原子%含有し、Si含有量が10~100wtppm、ガス成分を除く不可避的不純物の総含有量が50wtppm以下、残部がRuであることを特徴とするルテニウム合金スパッタリングターゲット。
5)Si含有量が10~50wtppm、ガス成分を除く不可避的不純物の総含有量が10wtppm以下、残部がRuであることを特徴とする上記4)記載のルテニウム合金スパッタリングターゲット。
6)平均結晶粒径が5~100μm、最大結晶粒径が500μm以下であることを特徴とする上記4)又は5)記載のルテニウム合金スパッタリングターゲット。
シリコン含有量は10~100wtppmが好ましく、さらに好ましくは10~50wtppmとする。10wtppm未満では、結晶粒の粗大化を十分に抑制することができず、一方、100wtppmを超えると、半導体デバイスの性能を不安定にするため好ましくない。
また、ルテニウム合金は、熱的安定性に優れると共に、低抵抗性、バリヤ性に優れているので、半導体素子の成膜材料として、特にゲート電極材、各種拡散バリヤ材として有用である。
このとき、Ru粉末は平均粒径が10~150μmのものを用いるのが好ましい。また、Si粉末は平均粒径が5~100μmのものを用いるのが好ましく、合金元素であるTa、Nb、Mo、W、Mn粉末は平均粒径が5~100μmのものを使用することが好ましい。原料粉末の粒径が小さ過ぎると、粉体の嵩密度が高くなり、モールドに充填する重量に制限が生じるため好ましくなく、一方、粒径が大きすぎると、表面積の低下に伴い焼結性が低下し、結果として焼結体の密度が低くなるため、好ましくない。
本発明は、上記の焼結条件に限定されるものではないが、焼結温度や焼結圧力が低過ぎたり、焼結時間が短過ぎたりすると、十分な焼結体の密度が得られず、好ましくない。また、焼結温度や焼結時間が長過ぎると、粗大粒が発生するため、好ましくなく、焼結圧力が高過ぎると、焼結体に割れが発生するため、好ましくない。
このようにして得られた焼結体を機械加工してターゲット形状にすることで、本発明のスパッタリングターゲットを作製することができる。なお、スパッタリングに際して、このようなターゲットは、バッキングプレートに接合した形態で用いられる。
平均粒径が50μmのルテニウム粉末(純度99.995%)、平均粒径が10μmのシリコン粉末(純度99.999%)を用意し、Si含有量12wtppmからなるようにこれらの原料粉末を混合した。次に、これをカーボン製の型に充填し、ホットプレスした。ホットプレス条件は、Ar雰囲気、焼結温度1500℃、焼結圧力200kg/cm2、焼結時間1時間とした。
Si含有量を35wtppmとし、それ以外は実施例1と同様の条件でスパッタリングターゲットを作製した。このスパッタリングターゲットの表面を観察した結果、平均結晶粒径は48μmであり、最大結晶粒径は103μmであった。粗大結晶粒は観察されなかった。次に、このスパッタリングターゲットをバッキングプレートに接合し、実施例1と同様の条件でスパッタリングした結果、基板上へ付着したパーティクル数は63個と少なかった。
Si含有量を62wtppmとし、それ以外は実施例1と同様の条件でスパッタリングターゲットを作製した。このスパッタリングターゲットの表面を観察した結果、平均結晶粒径は21μmであり、最大結晶粒径は65μmであった。粗大結晶粒は観察されなかった。次に、このスパッタリングターゲットをバッキングプレートに接合し、実施例1と同様の条件でスパッタリングした結果、基板上へ付着したパーティクル数は58個と少なかった。
Si含有量を94wtppmとし、それ以外は実施例1と同様の条件でスパッタリングターゲットを作製した。このスパッタリングターゲットの表面を観察した結果、平均結晶粒径は8μmであり、最大結晶粒径は18μmであった。粗大結晶粒は観察されなかった。次に、このスパッタリングターゲットをバッキングプレートに接合し、実施例1と同様の条件でスパッタリングした結果、基板上へ付着したパーティクル数は42個と少なかった。
平均粒径が50μmのルテニウム粉末(純度99.995%)、平均粒径10μmのタンタル粉末(純度99.995%)、平均粒径が10μmのシリコン粉末(純度99.999%)を用意し、タンタル含有量15原子%、Si含有量10wtppm、残部Ruとなるようにこれらの原料粉末を混合した。次に、これをカーボン製の型に充填し、ホットプレスした。ホットプレス条件は、Ar雰囲気、焼結温度1500℃、焼結圧力200kg/cm2、焼結時間1時間とした。
タンタル(Ta)含有量15原子%、Si含有量を40wtppmとし、それ以外は実施例5と同様の条件でスパッタリングターゲットを作製した。このスパッタリングターゲットの表面を観察した結果、平均結晶粒径は53μmであり、最大結晶粒径は123μmであった。粗大結晶粒は観察されなかった。次に、このスパッタリングターゲットをバッキングプレートに接合し、実施例1と同様の条件でスパッタリングした結果、基板上へ付着したパーティクル数は60個と少なかった。
ニオブ(Nb)含有量8原子%、Si含有量を40wtppmとし、それ以外は実施例5と同様の条件でスパッタリングターゲットを作製した。このスパッタリングターゲットの表面を観察した結果、平均結晶粒径は55μmであり、最大結晶粒径は118μmであった。粗大結晶粒は観察されなかった。次に、このスパッタリングターゲットをバッキングプレートに接合し、実施例1と同様の条件でスパッタリングした結果、基板上へ付着したパーティクル数は57個と少なかった。
タングステン(W)含有量25原子%、Si含有量を90wtppmとし、それ以外は実施例5と同様の条件でスパッタリングターゲットを作製した。このスパッタリングターゲットの表面を観察した結果、平均結晶粒径は15μmであり、最大結晶粒径は28μmであった。粗大結晶粒は観察されなかった。次に、このスパッタリングターゲットをバッキングプレートに接合し、実施例1と同様の条件でスパッタリングした結果、基板上へ付着したパーティクル数は37個と少なかった。
Si含有量を3wtppmとし、それ以外は実施例1と同様の条件でスパッタリングターゲットを作製した。このスパッタリングターゲットの表面を観察した結果、平均結晶粒径は121μmであり、最大結晶粒径は520μmであった。結晶粒が粗大化していた。次に、このスパッタリングターゲットをバッキングプレートに接合し、実施例1と同様の条件でスパッタリングした結果、基板上へ付着したパーティクル数は131個と増加していた。
Si含有量を109wtppmとし、それ以外は実施例1と同様の条件でスパッタリングターゲットを作製した。このスパッタリングターゲットの表面を観察した結果、平均結晶粒径は9μmであり、最大結晶粒径は15μmであった。粗大な結晶粒は観察されなかった。次に、このスパッタリングターゲットをバッキングプレートに接合し、実施例1と同様の条件でスパッタリングした結果、基板上へ付着したパーティクル数は43個と少なかった。一方、形成した薄膜の体積抵抗率を測定したところ、そのバラツキが大きくなっていた。
タンタル(Ta)含有量15原子%、Si含有量を107wtppmとし、それ以外は実施例5と同様の条件でスパッタリングターゲットを作製した。このスパッタリングターゲットの表面を観察した結果、平均結晶粒径は8μmであり、最大結晶粒径は18μmであった。粗大な結晶粒は観察されなかった。次に、このスパッタリングターゲットをバッキングプレートに接合し、実施例1と同様の条件でスパッタリングした結果、基板上へ付着したパーティクル数は41個と少なかった。一方、形成した薄膜の体積抵抗率を測定したところ、そのバラツキが大きくなっていた。
Claims (6)
- Si含有量が10~100wtppm、ガス成分を除く不可避的不純物の総含有量が50wtppm以下、残部がRuであることを特徴とするルテニウムスパッタリングターゲット。
- Si含有量が10~50wtppm、ガス成分を除く不可避的不純物の総含有量が10wtppm以下、残部がRuであることを特徴とする請求項1記載のルテニウムスパッタリングターゲット。
- 平均結晶粒径が5~100μm、最大結晶粒径が500μm以下であることを特徴とする請求項1又は2記載のルテニウムスパッタリングターゲット。
- Ta、Nb、Mo、W、Mnの群から選択される1種以上の合金元素を3~35原子%含有し、Si含有量が10~100wtppm、ガス成分を除く不可避的不純物の総含有量が50wtppm以下、残部がRuであることを特徴とするルテニウム合金スパッタリングターゲット。
- Si含有量が10~50wtppm、ガス成分を除く不可避的不純物の総含有量が10wtppm以下、残部がRuであることを特徴とする請求項4記載のルテニウム合金スパッタリングターゲット。
- 平均結晶粒径が5~100μm、最大結晶粒径が500μm以下であることを特徴とする請求項4又は5記載のルテニウム合金スパッタリングターゲット。
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JPWO2016052371A1 (ja) | 2014-09-30 | 2017-06-08 | Jx金属株式会社 | スパッタリングターゲット用母合金及びスパッタリングターゲットの製造方法 |
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