WO2010113638A1 - スパッタリング用ランタンターゲット - Google Patents
スパッタリング用ランタンターゲット Download PDFInfo
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- WO2010113638A1 WO2010113638A1 PCT/JP2010/054494 JP2010054494W WO2010113638A1 WO 2010113638 A1 WO2010113638 A1 WO 2010113638A1 JP 2010054494 W JP2010054494 W JP 2010054494W WO 2010113638 A1 WO2010113638 A1 WO 2010113638A1
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- target
- lanthanum
- sputtering
- ingot
- temperature
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J1/00—Preparing metal stock or similar ancillary operations prior, during or post forging, e.g. heating or cooling
- B21J1/02—Preliminary treatment of metal stock without particular shaping, e.g. salvaging segregated zones, forging or pressing in the rough
- B21J1/025—Preliminary treatment of metal stock without particular shaping, e.g. salvaging segregated zones, forging or pressing in the rough affecting grain orientation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J1/00—Preparing metal stock or similar ancillary operations prior, during or post forging, e.g. heating or cooling
- B21J1/04—Shaping in the rough solely by forging or pressing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J5/00—Methods for forging, hammering, or pressing; Special equipment or accessories therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
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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
Definitions
- the present invention relates to a sputtering lantern target having no macro pattern unevenness on the surface and a method for producing the same.
- Lanthanum (La) is contained in rare earth elements, but is contained in the earth's crust as a mixed complex oxide as a mineral resource. Since rare earth elements were separated from relatively rare (rare) minerals, they were named as such, but they are not rare when viewed from the entire crust. Lanthanum is a white metal having an atomic number of 57 and an atomic weight of 138.9, and has a double hexagonal close-packed structure at room temperature.
- the melting point is 921 ° C.
- the boiling point is 3500 ° C.
- the density is 6.15 g / cm 3.
- the surface is oxidized in the air and gradually dissolved in water. Soluble in hot water and acid. There is no ductility, but there is slight malleability.
- the resistivity is 5.70 ⁇ 10 ⁇ 6 ⁇ cm. It burns at 445 ° C or higher to become oxide (La 2 O 3 ) (see Physics and Chemistry Dictionary).
- As for rare earth elements compounds having an oxidation number of 3 are generally stable, but lanthanum is also trivalent. Recently, lanthanum has been researched and developed as an electronic material such as a metal gate material and a high dielectric constant material (High-k), and is a metal that has attracted attention (see Non-Patent Document 1).
- lanthanum metal Since lanthanum metal has a problem that it is easily oxidized during purification, it is difficult to achieve high purity. In addition, when lanthanum metal is left in the air, it oxidizes in a short time and turns black, so that there is a problem that handling is not easy. Recently, thinning is required as a gate insulating film in next-generation MOSFETs, but in SiO 2 that has been used as a gate insulating film so far, leakage current due to a tunnel effect increases and normal operation has become difficult. .
- HfO 2 , ZrO 2 , Al 2 O 3 , La 2 O 3 having a high dielectric constant, high thermal stability, and a high energy barrier against holes and electrons in silicon are proposed.
- La 2 O 3 is highly evaluated, electrical characteristics have been investigated, and research reports as a gate insulating film in next-generation MOSFETs have been made (see Non-Patent Document 1).
- the subject of research is the La 2 O 3 film, and the characteristics and behavior of the La element are not particularly mentioned.
- Patent Document 1 Although there is a description that a target is manufactured with lanthanum regarding lanthanum (and its manufacturing method) which is mainly a target material, there is no description of a specific target manufacturing method (conditions). I could't refer to it.
- lanthanum lanthanum oxide
- the substrate It is possible to form a thin film of lanthanum on the top, and it is easy to investigate the behavior of the interface with the silicon substrate, and further the characteristics of a high dielectric constant gate insulating film by forming a lanthanum compound. It has the great advantage of increasing the degree of freedom as a product.
- FIG. 1 shows a photograph of a lanthanum target with macro pattern unevenness on the surface.
- macro pattern unevenness looks like a cloud
- this is a coarse structure and an unbalanced structure with other fabrics.
- An object of the present invention is to provide a technique capable of efficiently and stably providing a sputtering lantern target having no macro pattern unevenness on the surface and a method for producing the same.
- lanthanum is a material in which unevenness of a macro pattern is likely to occur on the surface in the process of manufacturing the target.
- the inventor of the present application increases the hardness of the lanthanum target and maintains a constant hardness. As a result, it was found that the occurrence of macro-pattern unevenness on the surface can be reduced. An application for this is planned as a novel invention. However, it has been confirmed by many tests that a sputtering lanthanum target without macro pattern unevenness can be provided even if the Vickers hardness is not 60 or more. That is, the structure of the sputtering lanthanum target is a recrystallized structure having an average crystal grain size of 100 ⁇ m or less.
- a sputtering lanthanum target having no macro pattern unevenness on the surface, to achieve uniformity of film formation during sputtering, and to effectively suppress generation of particles. became.
- a LaOx film is mainly formed.
- an arbitrary film is formed in order to increase the degree of freedom of film formation.
- Lanthanum metal is required.
- the present invention can provide a target material compatible therewith.
- the lanthanum raw material used in the present invention it is desirable to use a material having as high a purity as possible, but impurities usually contained are allowed.
- rare earth elements contained in lanthanum are Sc, Y, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
- Ce approximates La
- Ce it is not easy to reduce Ce.
- these rare earth elements have similar properties, if the total rare earth elements are less than 1000 wtppm, there is no particular problem when used as an electronic component material.
- the lanthanum target of the present invention is allowed to contain this level of rare earth element.
- the total amount of rare earth elements other than lanthanum is preferably 100 wtppm or less, more preferably 10 wtppm or less, and still more preferably the content of each rare earth element is 1 wtppm or less. It can be said.
- the present invention can achieve these and includes them.
- C, N, O, S, and H exist as gas components. These may exist as single elements, but many may exist in the form of compounds (CO, CO 2 , SO 2 etc.) or compounds with constituent elements. Since these gas component elements have a small atomic weight and atomic radius, even if they are present as impurities, they do not significantly affect the properties of the material unless they are contained in large amounts. Therefore, when displaying the purity, it is usual to use the purity excluding the gas component.
- the purity of the lanthanum of the present invention is such that the purity excluding gas components is 4N or more.
- Lanthanum refined to this level will also reduce the gas components accordingly.
- the oxygen contained in the lanthanum is 2000 wtppm or more, and in some cases 5000 wtppm or less, it may not be a big problem.
- the present invention is not intended for an oxygen content of around 5000 wtppm. That is, it is needless to say that it is desirable that oxygen be as low as possible. In the present invention, this is achieved with the aim of 1500 wtppm or less, and further less than 1000 wtppm.
- the lanthanum target of the present invention preferably has a purity of 4N or higher excluding rare earth elements and gas components.
- aluminum, iron and copper in lanthanum are each 100 wtppm or less, oxygen content is 1500 wtppm or less, each element of alkali metal and alkaline earth metal is 1 wtppm or less, each element of transition metal and refractory metal other than the above Are preferably 10 wtppm or less, and each of the radioactive elements is preferably 10 wtppb or less.
- an ingot is manufactured by melting and casting lanthanum as a raw material, and then the ingot is kneaded and forged at a temperature of 300 to 500 ° C, and then further set at 300 to 500 ° C.
- a target original shape by internal forging or warm rolling, then heat-treat it at a temperature of 150 to 300 ° C, recrystallize it, and machine it to produce a lanthanum target for sputtering as a target It is.
- the kneading forging is hot forging in which large strain is alternately applied from the vertical direction and the horizontal direction, thereby destroying the cast structure of the ingot.
- a sputtering lanthanum target having a recrystallized structure with an average crystal grain size of 100 ⁇ m or less and having no uneven macro pattern on the surface.
- the average crystal grain size of the recrystallized structure exceeds 100 ⁇ m, macro pattern unevenness is observed, so that the average crystal grain size of 100 ⁇ m or less is an essential requirement.
- This can be further cut into a predetermined size and made into a sputtering target through a polishing step.
- the present invention relates to a sputtering lanthanum target having a recrystallized structure having an average crystal grain size of 100 ⁇ m or less and having no macro-pattern unevenness on the machined surface.
- the lanthanum target thus obtained is used.
- sputtering is performed, uniform film formation is possible, and the generation of particles can be suppressed.
- FIG. It is a photograph which shows the nonuniformity of the macro pattern of the target surface after machining. It is a microscope picture of the target surface after the machining of Example 1 of the present invention ( ⁇ 200). 3 is a diagram showing a peak of crystal orientation by XRD of Example 1.
- FIG. It is a microscope picture of the target surface after the machining of Example 2 of the present invention ( ⁇ 200). It is a figure which shows the peak of the crystal orientation by XRD of the present Example 2.
- the average crystal grain size of the recrystallized structure of the target is refined, and macro pattern unevenness is removed from the lanthanum target.
- the manufacturing process is important.
- lanthanum is dissolved and cast (solidified) to produce an ingot.
- the ingot is kneaded and forged at a temperature of 300 to 500 ° C.
- the ingot is usually forged at a high temperature (about 800 ° C.) as it is, adjusted to a target shape, and then machined.
- a material produced under such forging conditions has a problem that “peeling” occurs during machining and remains on the surface of the lanthanum target.
- the conventional manufacturing method has a problem that unevenness of a macro pattern occurs on the machined lanthanum surface. When such macro pattern unevenness or “peeling” exists on the surface of the lanthanum target, particles are generated during sputtering, and a large problem arises that uniform film formation cannot be performed.
- lanthanum ingots are rich in workability, it has been difficult to increase the diameter of the target, that is, to produce a target having a diameter of 300 mm or more only under such forging conditions.
- the present inventor can devise the manufacturing conditions through a number of experiments and obtain a sputtering lanthanum target having no macro pattern unevenness on the surface. It was. After the lantern is melted and cast to produce an ingot, the ingot is kneaded and forged at a temperature of 300 to 500 ° C, then upset forged at 300 to 500 ° C to adjust the shape to the target shape, This is heat-treated at a temperature of 150 to 300 ° C. for recrystallization, and further machined to obtain a target.
- This process is a major feature of the present invention. Once the kneading forging is performed, the structure of the material is destroyed and work-hardened, and then the forged material in which the strain is stored is subjected to the heat treatment, thereby making it possible to obtain a fine crystal grain size.
- the process of adjusting the shape to the target shape by upsetting forging or warm rolling makes it possible to make the diameter of the target 300 mm or more, further expanding the use of the lanthanum target, and improving the work efficiency. .
- this ingot is kneaded and forged at a temperature of 300 to 500 ° C. It can be warm-rolled at a temperature of ⁇ 500 ° C. to adjust the shape of the target and recrystallize, and this can be further machined to obtain a target. Further, after melting and casting lanthanum to produce an ingot, this ingot is kneaded and forged at a temperature of 300 to 500 ° C, and then warm-rolled at a temperature of 300 to 500 ° C to form a target original shape.
- the present invention obtains a predetermined recrystallized structure using these methods, and includes these.
- This is further processed into a target. After this, finishing (polishing) can be performed as necessary. As a result, a sputtering lanthanum target having a recrystallized structure with an average crystal grain size of 100 ⁇ m or less can be obtained. Although the hardness of the lanthanum target produced in this way was lowered, no macro pattern unevenness was observed on the surface.
- the structure of the lanthanum target of the present invention is greatly different as described above, the structure was observed by crystal orientation by X-ray diffraction (XRD) in order to investigate the difference. However, no major difference was observed in this XRD. However, many of the lanthanum targets of the present invention have a result that the (100) peak intensity is stronger than the (101) peak intensity compared to the lanthanum target obtained by the conventional manufacturing method described later. Some were not. This result will be described again in Examples and Comparative Examples described later.
- the lanthanum target of the present invention is bonded to the backing plate after the production of the target, but is usually not brazed but diffusion bonded (DB) and bonded to a copper (usually: OFC “oxygen-free copper”) backing plate .
- DB diffusion bonded
- OFC oxygen-free copper
- the joining portion between the target and the backing plate does not peel or float during sputtering, and good joining is possible.
- This backing plate is also one of the unique features of the lantern target of the present invention.
- Example 1 As a lanthanum raw material, lanthanum having a purity of 99.9% was used. This raw material was melted in a 70 kW EB melting furnace at a vacuum degree of 6.0 ⁇ 10 ⁇ 5 to 7.0 ⁇ 10 ⁇ 4 mbar and a melting power of 10 kW. This was cast and cooled to make a lantern ingot. Next, this ingot is kneaded and forged at a temperature of 400 ° C. in the atmosphere, then upset forged at a temperature of 300 ° C. to increase the diameter and adjust the shape to the target shape, and then 180 ° C. for 1 hr. Heat treatment was performed to obtain a recrystallized structure.
- this was machined into a disk-shaped target of ⁇ 140 ⁇ 14t (the unit is mm, the same applies hereinafter).
- the weight of this target was 1.42 kg.
- This was further diffusion bonded to a copper-chromium alloy backing plate to obtain a sputtering lanthanum target. From this, it was confirmed that kneading forging and upset forging at a temperature of 300 to 500 ° C., and then recrystallizing it.
- tissue of the lanthanum target for sputtering obtained in this way, it etched using 1 wt% nitric acid aqueous solution.
- a micrograph ( ⁇ 200) of the result is shown in FIG.
- the target structure was a recrystallized structure.
- the crystal grain size was 20-30 ⁇ m.
- the average crystal grain size was 25 ⁇ m, which satisfied the conditions of the present invention.
- no macro pattern unevenness was observed on the surface of the sputtering lanthanum target.
- the Vickers hardness in this case was 49, but no macro pattern unevenness was observed despite the low hardness. This was considered that the fine recrystallized structure greatly influenced the prevention of macro pattern unevenness.
- the measurement results of the crystal orientation of the sputtering lanthanum target obtained in this example by X-ray diffraction (XRD) are shown in FIG. The result showed that the (101) peak intensity was stronger than the (100) peak intensity as compared with the lanthanum target of Comparative Example 1 described later, but there was no significant difference with respect to other points. As a result, it was considered that the difference in crystal orientation did not greatly affect the occurrence of unevenness of the macro pattern of the present invention.
- sputtering was performed using a lanthanum target for sputtering under conditions of a power of 100 W. As a result, no particles were generated and a uniform film on the substrate was formed. In addition, even when sputtering was performed for a long time, the target was not lifted off from the backing plate or peeled off between the target and the backing plate, and good sputtering was possible. As a result, it was confirmed that diffusion bonding was effective for the copper-chromium alloy backing plate.
- Example 2 As a lanthanum raw material, lanthanum having a purity of 99.9% was used. This raw material was melted in a 70 kW EB melting furnace at a vacuum degree of 6.0 ⁇ 10 ⁇ 5 to 7.0 ⁇ 10 ⁇ 4 mbar and a melting power of 10 kW. This was cast and cooled to make a lantern ingot. Next, the ingot is kneaded and forged at a temperature of 500 ° C. in the atmosphere, and then upset forged at a temperature of 400 ° C. to increase the diameter and adjust the shape to the target original shape, and then 290 ° C. for 1 hr. Heat treatment was performed to obtain a recrystallized structure.
- this was machined to obtain a disk-shaped target of ⁇ 140 ⁇ 14t.
- the weight of this target was 1.42 kg.
- This was further diffusion bonded to a copper-chromium alloy backing plate to obtain a sputtering lanthanum target.
- tissue of the lanthanum target for sputtering obtained in this way, it etched using 1 wt% nitric acid aqueous solution.
- a micrograph ( ⁇ 200) of the result is shown in FIG.
- the target structure was a recrystallized structure.
- the average particle size was 100 ⁇ m, which satisfied the conditions of the present invention.
- no macro pattern unevenness was observed on the surface of the sputtering lanthanum target. From this, it was confirmed that the heat treatment at 290 ° C. 1 hr after forging was good.
- the Vickers hardness in this case was 38, but no macro pattern unevenness was observed despite the low hardness. This was considered that the fine recrystallized structure greatly influenced the prevention of macro pattern unevenness.
- the measurement results of the crystal orientation of the sputtering lanthanum target obtained in this example by X-ray diffraction (XRD) are shown in FIG. The result showed that the (101) peak intensity was stronger than the (100) peak intensity as compared with the lanthanum target of Comparative Example 1 described later, but there was no significant difference with respect to other points. As a result, it was considered that the difference in crystal orientation did not greatly affect the occurrence of unevenness of the macro pattern of the present invention.
- sputtering was performed using a lanthanum target for sputtering under conditions of a power of 100 W. As a result, no particles were generated and a uniform film on the substrate was formed. In addition, even when sputtering was performed for a long time, the target was not lifted off from the backing plate or peeled off between the target and the backing plate, and good sputtering was possible. As a result, it was confirmed that diffusion bonding was effective for the copper-chromium alloy backing plate.
- Example 3 As a lanthanum raw material, lanthanum having a purity of 99.9% was used. This raw material was melted in a 70 kW EB melting furnace at a vacuum degree of 6.0 ⁇ 10 ⁇ 5 to 7.0 ⁇ 10 ⁇ 4 mbar and a melting power of 10 kW. This was cast and cooled to make a lantern ingot. Next, the ingot was kneaded and forged at a temperature of 300 ° C. in the atmosphere, and then warm-rolled at a temperature of 400 ° C. to increase the diameter, to adjust the shape to the target original shape, and to obtain a recrystallized structure. Further, this was machined to obtain a disk-shaped target of ⁇ 140 ⁇ 14t. The weight of this target was 1.42 kg. This was further diffusion bonded to a copper-chromium alloy backing plate to obtain a sputtering lanthanum target.
- tissue of the lanthanum target for sputtering obtained in this way, it etched using 1 wt% nitric acid aqueous solution.
- a micrograph ( ⁇ 200) of the result is shown in FIG.
- the target structure was a recrystallized structure.
- the average particle size was 40 to 60 ⁇ m, which satisfied the conditions of the present invention.
- no macro pattern unevenness was observed on the surface of the sputtering lanthanum target. From this, it was confirmed that kneading forging and subsequent warm rolling of the ingot at a temperature of 300 to 500 ° C. are good.
- the Vickers hardness in this case was 46, but the macro pattern unevenness was not observed despite the low hardness. This was considered that the fine recrystallized structure greatly influenced the prevention of macro pattern unevenness.
- the measurement results of the crystal orientation of the sputtering lanthanum target obtained in this example by X-ray diffraction (XRD) are shown in FIG. The result showed that the peak intensity of (100) was stronger than the (101) peak intensity as compared with the lanthanum target of Comparative Example 1 described later, but there was no significant difference with respect to other points. As a result, it was considered that the difference in crystal orientation did not greatly affect the occurrence of unevenness of the macro pattern of the present invention.
- sputtering was performed using a lanthanum target for sputtering under conditions of a power of 100 W. As a result, no particles were generated and a uniform film on the substrate was formed. In addition, even when sputtering was performed for a long time, the target was not lifted off from the backing plate or peeled off between the target and the backing plate, and good sputtering was possible. As a result, it was confirmed that diffusion bonding was effective for the copper-chromium alloy backing plate.
- Example 4 As a lanthanum raw material, lanthanum having a purity of 99.9% was used. This raw material was melted in a 70 kW EB melting furnace at a vacuum degree of 6.0 ⁇ 10 ⁇ 5 to 7.0 ⁇ 10 ⁇ 4 mbar and a melting power of 10 kW. This was cast and cooled to make a lantern ingot. Next, this ingot is kneaded and forged at a temperature of 400 ° C. in the atmosphere, and then warm-rolled at a temperature of 400 ° C. to increase the diameter, adjust the shape to the target shape, and further heat-treat at 300 ° C. A recrystallized structure was obtained.
- this was machined to obtain a disk-shaped target of ⁇ 140 ⁇ 14t.
- the weight of this target was 1.42 kg.
- This was further diffusion bonded to a copper-chromium alloy backing plate to obtain a sputtering lanthanum target.
- tissue of the lanthanum target for sputtering obtained in this way, it etched using 1 wt% nitric acid aqueous solution.
- a micrograph ( ⁇ 200) of the result is shown in FIG.
- the target structure was a recrystallized structure.
- the crystal grain size was 10 to 150 ⁇ m, which satisfied the conditions of the present invention.
- no macro pattern unevenness was observed on the surface of the sputtering lanthanum target. From this, it was confirmed that kneading forging of the ingot at a temperature of 300 to 500 ° C., followed by warm rolling and recrystallization by heat treatment at 300 ° C. were good.
- the Vickers hardness in this case was 42, but no macro pattern unevenness was observed despite the low hardness. This was considered that the fine recrystallized structure greatly influenced the prevention of macro pattern unevenness.
- the measurement results of the crystal orientation of the sputtering lanthanum target obtained in this example by X-ray diffraction (XRD) are shown in FIG. The result showed that the (101) peak intensity was stronger than the (100) peak intensity as compared with the lanthanum target of Comparative Example 1 described later, but there was no significant difference with respect to other points. As a result, it was considered that the difference in crystal orientation did not greatly affect the occurrence of unevenness of the macro pattern of the present invention.
- sputtering was performed using a lanthanum target for sputtering under conditions of a power of 100 W. As a result, no particles were generated and a uniform film on the substrate was formed. In addition, even when sputtering was performed for a long time, the target was not lifted off from the backing plate or peeled off between the target and the backing plate, and good sputtering was possible. As a result, it was confirmed that diffusion bonding was effective for the copper-chromium alloy backing plate.
- lanthanum raw material As a lanthanum raw material, lanthanum having a purity of 99.9% was used. This raw material was melted in a 70 kW EB melting furnace at a vacuum degree of 6.0 ⁇ 10 ⁇ 5 to 7.0 ⁇ 10 ⁇ 4 mbar and a melting power of 10 kW. This was cast and cooled to make a lantern ingot. Next, this ingot is hot-pressed (HP) in vacuum at a temperature of 800 ° C., thereby increasing the diameter and adjusting the shape of the target, and further machining it to obtain a disk shape of ⁇ 140 ⁇ 14t. Targeted. The weight of this target was 1.42 kg. This was further diffusion bonded to a copper backing plate to obtain a sputtering lanthanum target. Incidentally, the Vickers hardness in this case was 51.
- tissue of the lanthanum target for sputtering obtained in this way, it etched using 1 wt% nitric acid aqueous solution.
- a micrograph ( ⁇ 100) of the result is shown in FIG.
- the target structure was a coarse crystal structure with a crystal grain size of 200 to 300 ⁇ m, and macro-patterned unevenness was observed on the surface of the sputtering lanthanum target.
- lanthanum raw material As a lanthanum raw material, lanthanum having a purity of 99.9% was used. This raw material was melted in a 70 kW EB melting furnace at a vacuum degree of 6.0 ⁇ 10 ⁇ 5 to 7.0 ⁇ 10 ⁇ 4 mbar and a melting power of 10 kW. This was cast and cooled to make a lantern ingot. Next, the ingot is kneaded and forged at a temperature of 600 ° C. in the atmosphere, and then upset and forged at a temperature of 300 ° C. to increase the diameter and adjust the shape to the target shape. Heat treatment was performed to obtain a recrystallized structure. Further, this was machined into a disk-shaped target of ⁇ 140 ⁇ 14t. The weight of this target was 1.42 kg. This was further diffusion bonded to a copper backing plate to obtain a sputtering lanthanum target.
- tissue of the lanthanum target for sputtering obtained in this way, it etched using 1 wt% nitric acid aqueous solution.
- the target structure was a coarse crystal structure with a crystal grain size of 100 to 200 ⁇ m, and macro pattern irregularities were observed on the surface of the sputtering lanthanum target.
- the Vickers hardness in this case was 55.
- the crystal orientation of the lanthanum target for sputtering obtained in this comparative example was measured by X-ray diffraction (XRD). Similar to the lanthanum target of the above example, the (101) peak intensity was stronger than the (100) peak intensity. It was considered that this crystal orientation did not significantly affect the occurrence of macro pattern unevenness. Further, sputtering was performed under the condition of power 100 W using the sputtering lanthanum target obtained in this comparative example. As a result, the generation of particles increased compared to the example, and the film formation on the substrate became non-uniform.
- the lanthanum target for sputtering having a recrystallized structure with an average crystal grain size of 100 ⁇ m or less obtained by the present invention and having no uneven macro pattern on the surface does not generate particles during sputtering and enables uniform film formation. is there.
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Abstract
Description
ランタンの原子番号は57、原子量138.9の白色の金属であり、常温で複六方最密構造を備えている。
希土類元素は一般に酸化数3の化合物が安定であるが、ランタンも3価である。最近ではランタンをメタルゲート材料、高誘電率材料(High-k)等の、電子材料として研究開発が進められており、注目されている金属である(非特許文献1参照)。
最近、次世代のMOSFETにおけるゲート絶縁膜として薄膜化が要求されているが、これまでゲート絶縁膜として使用されてきたSiO2では、トンネル効果によるリーク電流が増加し、正常動作が難しくなってきた。
また、特許文献1に、主にターゲット材料となるランタン(及びその製造方法)に関し、ランタンでターゲットを製造するという記載があるものの、具体的なターゲットの製造方法(条件)の記載がないので、参考することはできなかった。
この図1では、ターゲットの中心からやや外れた位置とターゲットの周辺に、マクロ模様のムラ(雲のように見える)が発生しているのが観察できる。これは、後述する比較例に示すように、粗大化した組織で、他の生地とのアンバランスな組織となっている。
しかしながら、このようにビッカース硬度60以上としなくても、表面にマクロ模様のムラのないスパッタリング用ランタンターゲットを提供することができることを多くの試験により確認した。それは、スパッタリング用ランタンターゲットの組織を平均結晶粒径が100μm以下の再結晶組織とすることである。
MOSFETにおけるゲート絶縁膜として利用する場合に、形成するのは主としてLaOx膜であるが、このような膜を形成する場合には、任意の膜を形成するという、膜形成の自由度を増すために、ランタン金属が必要となる。本願発明は、これに適合するターゲット材料を提供することができる。
しかしながら、本願発明は、5000wtppm近傍の酸素含有量を目途とするものではないことは理解されるべきことである。すなわち、酸素もできるだけ少ない方が望ましいことは言うまでもない。本願発明においては、1500wtppm以下、さらには1000wtppm未満とすることを目途とし、これを達成するものである。
本願発明のスパッタリング用ランタンターゲットを製造するには、ランタンを溶解し、これを鋳造して(凝固させて)インゴットを製造する。そして、このインゴットを300~500°Cの温度でこねくり鍛造する。
また、従来の製法では、機械加工したランタン表面に、マクロ模様のムラが生ずるという問題がある。このような、ランタンターゲット表面のマクロ模様のムラや「むしれ」が存在する場合には、スパッタリング時にパーティクルが発生し、また均一な成膜ができないという大きな問題を生ずる。さらに、ランタンインゴットは加工性に富むとは言っても、このような鍛造条件だけでは、ターゲットの大径化、すなわち300mm以上の径のターゲットの製作は困難であった。
ランタンを溶解、鋳造してインゴットを製造した後、このインゴットを300~500°Cの温度でこねくり鍛造し、その後300~500°Cで、据え込み鍛造してターゲット原形に形状を整え、次にこれを150~300°Cの温度で熱処理を行って再結晶させ、さらに機械加工してターゲットとする。
また、据え込み鍛造又は温間圧延してターゲット原形に形状を整える工程により、ターゲットの直径を300mm以上とすることが可能となり、ランタンターゲットの利用をさらに拡大させ、作業能率を向上させることができる。
本願発明は、これらの方法を用いて所定の再結晶組織を得るものであり、これらを包含するものである。
この結果、平均結晶粒径が100μm以下の再結晶組織を有するスパッタリング用ランタンターゲットを得ることができる。このようにして作製したランタンターゲットの硬度は低下しているが、その表面には、マクロ模様のムラは一切見られなくなった。
しかし、本願発明のランタンターゲットでは、後述する従来の製造方法で得たランタンターゲットに比べ、(101)のピーク強度よりも(100)ピーク強度が強くなっているという結果があるものが多いが、そうでないものもあった。この結果については、後述する実施例及び比較例で、再度説明する。
しかし、接合部の剥がれや浮きが発生しないように、銅-クロム(Cu-1%Cr)合金製のバッキングプレートを使用するのが望ましい。このような銅-クロム合金製のバッキングプレートを使用した場合には、スパッタリング中に、ターゲットとバッキングプレートとの接合部の剥がれや浮きが発生せず、良好な接合が可能となる。このバッキングプレートの使用は、本願発明のランタンターゲットの固有の特徴の一つでもある。
ランタンの原料として、純度99.9%のランタンを使用した。この原料を70kWのEB溶解炉を用い、真空度6.0×10-5~7.0×10-4mbar、溶解出力10kWで溶解した。これを鋳造し、冷却してランタンインゴットを作成した。
次に、このインゴットを大気中、400°Cの温度でこねくり鍛造し、その後300°Cの温度で据え込み鍛造して径を大きくし、かつターゲット原形に形状を整え、次に180°C1hrの熱処理を行い、再結晶組織とした。
さらにこれを機械加工してφ140×14t(単位は、いずれもmmである。以下同様。)の円盤状ターゲットとした。このターゲットの重量は1.42kgであった。これをさらに銅-クロム合金バッキングプレートに拡散接合して、スパッタリング用ランタンターゲットとした。
このことから、インゴットを300~500°Cの温度でこねくり鍛造及び据え込み鍛造し、その後に再結晶させることが良いことが確認できた。
一方、この実施例で得たスパッタリング用ランタンターゲットをX線回折(XRD)による結晶方位の測定結果を図3に示す。後述する比較例1のランタンターゲットに比べ、(100)のピーク強度よりも(101)ピーク強度が強くなっているという結果が出たが、それ以外の点については、大きな差異はなかった。この結果、結晶方位の相違は、本願発明のマクロ模様のムラの発生には、大きく影響はしていないと考えられた。
ランタンの原料として、純度99.9%のランタンを使用した。この原料を70kWのEB溶解炉を用い、真空度6.0×10-5~7.0×10-4mbar、溶解出力10kWで溶解した。これを鋳造し、冷却してランタンインゴットを作成した。
次に、このインゴットを大気中、500°Cの温度でこねくり鍛造し、その後400°Cの温度で据え込み鍛造して径を大きくし、かつターゲット原形に形状を整え、次に290°C1hrの熱処理を行い、再結晶組織とした。
さらにこれを機械加工してφ140×14tの円盤状ターゲットとした。このターゲットの重量は1.42kgであった。これをさらに銅-クロム合金バッキングプレートに拡散接合して、スパッタリング用ランタンターゲットとした。
一方、この実施例で得たスパッタリング用ランタンターゲットをX線回折(XRD)による結晶方位の測定結果を図5に示す。後述する比較例1のランタンターゲットに比べ、(100)のピーク強度よりも(101)ピーク強度が強くなっているという結果が出たが、それ以外の点については、大きな差異はなかった。この結果、結晶方位の相違は、本願発明のマクロ模様のムラの発生には、大きく影響はしていないと考えられた。
ランタンの原料として、純度99.9%のランタンを使用した。この原料を70kWのEB溶解炉を用い、真空度6.0×10-5~7.0×10-4mbar、溶解出力10kWで溶解した。これを鋳造し、冷却してランタンインゴットを作成した。
次に、このインゴットを大気中、300°Cの温度でこねくり鍛造し、その後400°Cの温度で温間圧延して径を大きくし、ターゲット原形に形状を整え、かつ再結晶組織とした。
さらにこれを機械加工してφ140×14tの円盤状ターゲットとした。このターゲットの重量は1.42kgであった。これをさらに銅-クロム合金バッキングプレートに拡散接合して、スパッタリング用ランタンターゲットとした。
一方、この実施例で得たスパッタリング用ランタンターゲットをX線回折(XRD)による結晶方位の測定結果を図7に示す。後述する比較例1のランタンターゲットに比べ、(100)のピーク強度が(101)ピーク強度よりも強くなっているという結果が出たが、それ以外の点については、大きな差異はなかった。この結果、結晶方位の相違は、本願発明のマクロ模様のムラの発生には、大きく影響はしていないと考えられた。
ランタンの原料として、純度99.9%のランタンを使用した。この原料を70kWのEB溶解炉を用い、真空度6.0×10-5~7.0×10-4mbar、溶解出力10kWで溶解した。これを鋳造し、冷却してランタンインゴットを作成した。
次に、このインゴットを大気中、400°Cの温度でこねくり鍛造し、その後400°Cの温度で温間圧延して径を大きくし、ターゲット原形に形状を整え、さらに300°Cで熱処理し再結晶組織とした。
さらにこれを機械加工してφ140×14tの円盤状ターゲットとした。このターゲットの重量は1.42kgであった。これをさらに銅-クロム合金バッキングプレートに拡散接合して、スパッタリング用ランタンターゲットとした。
この図8に示すように、スパッタリング用ランタンターゲットの表面にはマクロ模様のムラは観察されなかった。このことから、インゴットを300~500°Cの温度でこねくり鍛造、その後の温間圧延及び300°Cの熱処理による再結晶化が良いことが確認できた。
一方、この実施例で得たスパッタリング用ランタンターゲットをX線回折(XRD)による結晶方位の測定結果を図9に示す。後述する比較例1のランタンターゲットに比べ、(100)のピーク強度よりも(101)ピーク強度が強くなっているという結果が出たが、それ以外の点については、大きな差異はなかった。この結果、結晶方位の相違は、本願発明のマクロ模様のムラの発生には、大きく影響はしていないと考えられた。
ランタンの原料として、純度99.9%のランタンを使用した。この原料を70kWのEB溶解炉を用い、真空度6.0×10-5~7.0×10-4mbar、溶解出力10kWで溶解した。これを鋳造し、冷却してランタンインゴットを作成した。
次に、このインゴットを真空中、800°Cの温度でホットプレス(HP)し、これによって、径を大きくすると共にターゲット原形に形状を整え、さらにこれを機械加工してφ140×14tの円盤状ターゲットとした。このターゲットの重量は1.42kgであった。これをさらに銅バッキングプレートに拡散接合して、スパッタリング用ランタンターゲットとした。因みに、この場合のビッカース硬度は51であった。
また、スパッタリング実施時に、ターゲットとバッキングプレートとの間の剥がれはなかったが、若干バッキングプレートからターゲットが浮き上がる傾向が見られた。これは、スパッタリング時間が短時間であったため、大きな影響がなかったと思われる。
しかし、これを長時間実施したところ、予想通りターゲットとバッキングプレートとの間の剥がれが発生した。これにより、実施例に示す銅-クロム合金製バッキングプレートが好ましいことが確認することができた。
ランタンの原料として、純度99.9%のランタンを使用した。この原料を70kWのEB溶解炉を用い、真空度6.0×10-5~7.0×10-4mbar、溶解出力10kWで溶解した。これを鋳造し、冷却してランタンインゴットを作成した。
次に、このインゴットを大気中、600°Cの温度でこねくり鍛造し、その後300°Cの温度で据え込み鍛造して径を大きくし、かつターゲット原形に形状を整え、次に180°C1hrの熱処理を行い、再結晶組織とした。
さらに、これを機械加工してφ140×14tの円盤状ターゲットとした。このターゲットの重量は1.42kgであった。これをさらに銅バッキングプレートに拡散接合して、スパッタリング用ランタンターゲットとした。
因みに、この場合のビッカース硬度は55であった。
さらに、この比較例で得たスパッタリング用ランタンターゲットを用いて、パワー100Wの条件でスパッタリングを実施した。この結果、パーティクルの発生が実施例に比べて多くなり、基板への成膜も不均一となった。
しかし、これを長時間実施したところ、予想通りターゲットとバッキングプレートとの間の剥がれが発生した。これにより、実施例に示す銅-クロム合金製バッキングプレートが好ましいことが確認することができた。
Claims (5)
- 平均結晶粒径が100μm以下の再結晶組織を有し、表面にマクロ模様のムラのないスパッタリング用ランタンターゲット。
- ターゲットの直径が300mm以上であることを特徴とする請求項1記載のスパッタリング用ランタンターゲット。
- ランタンを溶解、鋳造してインゴットを製造した後、このインゴットを300~500°Cの温度でこねくり鍛造し、その後さらに300~500°Cで、据え込み鍛造又は温間圧延してターゲット原形に形状を整え、次にこれを150~300°Cの温度で熱処理を行って再結晶させ、さらに機械加工してターゲットとすることを特徴とするスパッタリング用ランタンターゲットの製造方法。
- ランタンを溶解、鋳造してインゴットを製造した後、このインゴットを300~500°Cの温度でこねくり鍛造し、次に300~500°Cの温度で温間圧延してターゲット原形に形状を整えると共に再結晶させ、これをさらに機械加工してターゲットとすることを特徴とするスパッタリング用ランタンターゲットの製造方法。
- ランタンを溶解、鋳造してインゴットを製造した後、このインゴットを300~500°Cの温度でこねくり鍛造し、次に300~500°Cの温度で温間圧延してターゲット原形に形状を整え、これを300~500°Cの温度で熱処理して再結晶させ、さらに機械加工してターゲットとすることを特徴とするスパッタリング用ランタンターゲットの製造方法。
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JP2011507083A JP5456763B2 (ja) | 2009-03-31 | 2010-03-17 | スパッタリング用ランタンターゲット |
CN2010800123783A CN102378825B (zh) | 2009-03-31 | 2010-03-17 | 溅射用镧靶 |
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KR101412404B1 (ko) * | 2008-07-07 | 2014-06-25 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | 산화물 소결체, 산화물 소결체로 이루어지는 스퍼터링 타깃, 산화물 소결체의 제조 방법 및 산화물 소결체 스퍼터링 타깃 게이트의 제조 방법 |
JP5301541B2 (ja) * | 2008-07-07 | 2013-09-25 | Jx日鉱日石金属株式会社 | 酸化ランタン基焼結体、同焼結体からなるスパッタリングターゲット、酸化ランタン基焼結体の製造方法及び同製造方法によるスパッタリングターゲットの製造方法 |
CN102356180B (zh) | 2009-03-27 | 2013-11-06 | 吉坤日矿日石金属株式会社 | 溅射用镧靶 |
WO2011062003A1 (ja) | 2009-11-17 | 2011-05-26 | Jx日鉱日石金属株式会社 | ランタン酸化物ターゲットの保管方法及び真空密封したランタン酸化物ターゲット |
EP2641982B1 (en) | 2010-11-19 | 2019-07-24 | JX Nippon Mining & Metals Corporation | Production method for high-purity lanthanum, high-purity lanthanum, sputtering target composed of high-purity lanthanum, and metal gate film containing high-purity lanthanum as main component |
US9013009B2 (en) | 2011-01-21 | 2015-04-21 | Jx Nippon Mining & Metals Corporation | Method for producing high-purity lanthanum, high-purity lanthanum, sputtering target formed from high-purity lanthanum, and metal gate film having highy-purity lanthanum as main component |
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CN102378825A (zh) | 2012-03-14 |
TWI482869B (zh) | 2015-05-01 |
EP2415899B1 (en) | 2013-11-20 |
TW201040298A (en) | 2010-11-16 |
EP2415899A1 (en) | 2012-02-08 |
US20110308940A1 (en) | 2011-12-22 |
KR20110106925A (ko) | 2011-09-29 |
JPWO2010113638A1 (ja) | 2012-10-11 |
EP2415899A4 (en) | 2012-12-19 |
KR101376453B1 (ko) | 2014-03-19 |
JP2014095152A (ja) | 2014-05-22 |
JP5913259B2 (ja) | 2016-04-27 |
CN102378825B (zh) | 2013-10-23 |
JP5456763B2 (ja) | 2014-04-02 |
US9382612B2 (en) | 2016-07-05 |
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