WO2009107763A1 - Metallic sputtering target material - Google Patents

Metallic sputtering target material Download PDF

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Publication number
WO2009107763A1
WO2009107763A1 PCT/JP2009/053645 JP2009053645W WO2009107763A1 WO 2009107763 A1 WO2009107763 A1 WO 2009107763A1 JP 2009053645 W JP2009053645 W JP 2009053645W WO 2009107763 A1 WO2009107763 A1 WO 2009107763A1
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Prior art keywords
sputtering
rolling
target material
sputtering target
present
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PCT/JP2009/053645
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French (fr)
Japanese (ja)
Inventor
徹 稲熊
広明 坂本
彰朗 安藤
忠美 大石
真吾 泉
元 中村
Original Assignee
新日鉄マテリアルズ株式会社
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Application filed by 新日鉄マテリアルズ株式会社 filed Critical 新日鉄マテリアルズ株式会社
Priority to CN200980106669.6A priority Critical patent/CN101960042B/en
Priority to JP2010500759A priority patent/JPWO2009107763A1/en
Publication of WO2009107763A1 publication Critical patent/WO2009107763A1/en

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/18—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers

Definitions

  • the present invention relates to a metal-based sputtering target material.
  • Metal materials such as Cr, Mo, Mo alloy, Al, Al alloy, Ta, Ti, Ag alloy, and Ni alloy are used as electrode materials for flat panel displays such as liquid crystal displays.
  • a sputtering method (sputtering process) is applied to the formation of the electrode, and a sputtering target material used in the sputtering method is made of a metal that serves as an electrode.
  • the size of the sputtering target material has increased, and the quality of the sputtering target material has been studied. That is, a sputtering target material that has a high film formation rate and is unlikely to generate particles and arcing (abnormal discharge) has been studied.
  • Patent Document 1 relates to a sputter target material characterized in that the X-ray diffraction pattern on the sputter surface is the same as the X-ray diffraction pattern on the side surface substantially orthogonal to the sputter surface.
  • the film formation rate can be increased without changing the existing film formation conditions by making the crystal grains of the sputtering target material not oriented and having no crystallinity anisotropy.
  • Patent Document 2 in order to solve the problem of arcing, Mo (molybdenum) ingot obtained by sintering in hydrogen (in Patent Document 2, “ingot” was obtained by sintering). It is used to mean a lump of metal, and is usually also referred to as “block. Here, it is hereinafter referred to as“ block. ”) Is rolled at a temperature of 1300 ° C. or less, and this Mo rolled sheet is heat treated to randomly A Mo sputtering target material having a proper crystal orientation and an average recrystallized grain size of 100 ⁇ m or less is disclosed. If the crystal grain size of the Mo sputtering target material is uniform and the crystal orientation is random, the generation of particles and arcing during sputtering are suppressed.
  • the crystal grain size of the sputtering target is made fine and uniform, and the orientation is low, that is, non-oriented. Is preferred.
  • the orientation specifically, the relative intensity ratio R (110) of the Mo ( 110 ) plane and the relative intensity R (200) of the Mo (200) plane, normalized by five main peaks in X-ray diffraction, are used. Both are described as 10% or more and 30% or less.
  • Patent Document 4 discloses that the concentration of impurity elements other than the main constituent elements of the metal sputtering target is 500 ppm or more and 1000 ppm or less in order to suppress the occurrence of arcing in high power density sputtering. It is described that since the impurity element has a sputtering rate different from that of the metal element of the sputtering target, it is easy to form a protrusion from which arcing occurs when sputtering progresses.
  • Patent Document 5 discloses that in a sputtering target material containing zirconium and the remaining molybdenum, the amount of oxygen contained can be reduced to facilitate rolling and to improve the film formation characteristics during sputtering. . Specifically, the frequency of generation of particles is shown as the film forming characteristic. Further, the oxygen content is preferably reduced from 0.05% to 0.3%.
  • Patent Document 6 in manufacturing the Mo sputtering target material, by making the oxygen content of the Mo sintered body 500 ppm or less, plastic working becomes easy, and the sputtering target material is an oxide particle phase. It is said that the generation of particles can be suppressed because the formation is reduced. Furthermore, by increasing the relative intensity ratio of the (110) plane, which is the most dense surface of Mo having a BCC (body-centered cubic lattice) crystal structure, the sputtering rate (deposition rate) is increased and productivity is improved. I can do it. Specifically, it is desirable that the relative intensity ratio R (110) of the (110) plane normalized by four main peaks in X-ray diffraction is 40% or more. Here, it was shown that the preferable range of the rolling reduction per pass during rolling was 10% or less, and specifically, that the structure was obtained at a rolling reduction of about 4% per pass.
  • Patent Document 7 discloses a molybdenum target that is a pressure-sintered target material that has a fine structure with an average particle size of 10 ⁇ m or less and a relative density of 99% or more. By controlling to such a structure, the sputtering film becomes uniform and the number of particles in the film can be reduced.
  • An object of the present invention is to provide a metal-based sputtering target material that can obtain a high film formation rate without using high-density power, can reduce the occurrence of arcing, and can dramatically improve the throughput of the sputtering process. .
  • the present inventors have made it possible to release metal atoms from each crystal plane for a metal having a cubic crystal structure used as a sputtering target material.
  • the ⁇ 200 ⁇ plane and the ⁇ 222 ⁇ plane have a high metal atom releasing ability.
  • the ⁇ 200 ⁇ plane integration degree and ⁇ 222 ⁇ plane integration degree of the crystal phase with respect to the sputtered surface with a low oxygen content in a specific range are obtained.
  • the inventors have found that a high sputtering target material exhibits extremely excellent throughput performance, and reached the present invention. That is, the present invention has the following gist.
  • the sum of the ⁇ 200 ⁇ plane integration degree and ⁇ 222 ⁇ plane integration degree of the crystal phase with respect to the sputtering surface of the sputtering target material is 30% or more and 95% or less.
  • the metal or alloy constituting the sputtering target material has one or more of Cr, Mo, W, V, or Ta as a main element, and the crystal structure is a cubic system centered cubic lattice structure.
  • the throughput performance in the sputtering process is improved.
  • the obtained electrode film is of high quality, a high-performance product can be provided.
  • the inventors of the present invention have a remarkable throughput performance in the sputtering process by controlling the texture and the oxygen concentration of the sputtering target material composed of a metal or alloy having a cubic crystal structure as described above. I found that it can be improved.
  • the throughput performance is mainly represented by the relationship between the film formation rate and the number of arcing occurrences. For example, the throughput characteristics are better as the film forming speed is higher and as the number of arcing occurrences is smaller.
  • FIG. 1 shows the amount of atomic emission on the other crystal planes as relative values, with the amount of atomic emission on the ⁇ 200 ⁇ plane being 100.
  • the ⁇ 200 ⁇ plane has a higher atomic emission rate, and is particularly remarkable as the applied energy (acceleration voltage of the ion beam) is lower.
  • the number of atoms per unit area there are many ⁇ 110 ⁇ planes, but the atomic emission rates are larger on the ⁇ 200 ⁇ plane and ⁇ 222 ⁇ plane than the ⁇ 200 ⁇ plane and ⁇ 222 ⁇ plane. This is presumed to be due to the high atomic emission ability of the surface.
  • the atomic emission rate correlates with the deposition rate in sputtering, and it is considered that the deposition rate increases as the atomic emission rate increases.
  • the ⁇ 110 ⁇ plane has a particularly low atomic emission rate at a low acceleration voltage, that is, the ⁇ 110 ⁇ plane has a low atomic emission capability, or high energy is required for atomic emission.
  • the ⁇ 200 ⁇ plane integration degree and ⁇ 222 ⁇ plane integration degree of the crystal phase with respect to the sputter surface are low with a specific range of low oxygen content. It has been found that a sputtering target material having a high texture exhibits extremely excellent throughput performance. Specifically, it is as follows.
  • the range of the sum of the ⁇ 200 ⁇ plane integration degree and the ⁇ 222 ⁇ plane integration degree is 30% or more and 95% or less. If the range of the sum of the ⁇ 200 ⁇ plane integration degree and the ⁇ 222 ⁇ plane integration degree is less than 30%, it is within the range of the effects obtained by the present invention, but the film formation rate may be low. On the other hand, when the range of the sum of ⁇ 200 ⁇ plane integration and ⁇ 222 ⁇ plane integration exceeds 95%, the film formation rate becomes fast, but there is a grain boundary between ⁇ 200 ⁇ plane and ⁇ 222 ⁇ plane.
  • the ratio of the occupancy decreases, and it may be cleaved and easily broken like a single crystal, or may be cracked by heat during sputtering.
  • the range of the sum of the ⁇ 200 ⁇ plane integration degree and the ⁇ 222 ⁇ plane integration degree is more preferably 60% or more and 95% or less.
  • the ⁇ 110 ⁇ plane integration degree of the sputtering target material is preferably 0.01% or more and 8% or less. This is because a larger film deposition rate can be maintained when the surface integration degree of ⁇ 110 ⁇ having a smaller electron emission capability is lower. Therefore, if the ⁇ 110 ⁇ plane integration degree exceeds 8%, the film formation speed may not be dramatically improved. On the other hand, if the ⁇ 110 ⁇ plane integration degree is less than 0.01%, further improvement of the film formation rate may be saturated, or production may be time-consuming to reduce the crystal plane. . In particular, from the viewpoint of film formation speed and target manufacturing cost, a more preferable range of ⁇ 110 ⁇ plane integration is 0.01% or more and 3% or less.
  • the measurement of the degree of surface integration can be performed by an X-ray diffraction method, for example, using MoK ⁇ rays.
  • the ⁇ 200 ⁇ plane integration degree, ⁇ 222 ⁇ plane integration degree, and ⁇ 110 ⁇ plane integration degree of the crystal phase are obtained as follows. Cubic crystal 11 plane parallel to the sample surface ⁇ 110 ⁇ , ⁇ 200 ⁇ , ⁇ 211 ⁇ , ⁇ 310 ⁇ , ⁇ 222 ⁇ , ⁇ 321 ⁇ , ⁇ 411 ⁇ , ⁇ 420 ⁇ , ⁇ 332 ⁇ , ⁇ 521 ⁇ and ⁇ 442 ⁇ are measured, and each measured value is divided by the theoretical integrated intensity of the sample having a random orientation, and then the ratio of ⁇ 200 ⁇ or ⁇ 110 ⁇ intensity is obtained as a percentage. This is expressed, for example, by the following formula (1) in the ⁇ 200 ⁇ intensity ratio.
  • the symbols are as follows. i (hkl): Measured integrated intensity of ⁇ hkl ⁇ plane in the measured sample I (hkl): Theoretical integrated intensity of ⁇ hkl ⁇ plane in the sample with random orientation ⁇ : Sum of the cubic crystal 11 plane As a place to measure the texture in the material, the depth position in the thickness direction is within the range of 1 mm depth position from the outermost surface to half the target material thickness with respect to the surface of the unused sputtering target material. Choose. It is important to select the site used for sputtering.
  • the oxygen content contained in the sputtering target material of the present invention is 5 ppm or more and 500 ppm or less by mass.
  • the oxygen content is the plane integration degree of the crystal plane, the film formation rate is high, the number of arcing occurrences can be drastically reduced, and extremely excellent throughput performance can be obtained.
  • the oxygen content is less than 5 ppm, the number of occurrences of arcing can be reduced, but it is not practical because it takes a lot of time and labor during the reduction process during production.
  • the oxygen content exceeds 500 ppm, an oxide is formed inside the sputtering target material, and the number of occurrences of arcing increases due to the influence, resulting in a decrease in throughput performance.
  • a more preferable range of oxygen content is 10 ppm or more and 200 ppm or less, and in this range, higher throughput performance can be obtained. Furthermore, if the oxygen content is 10 ppm or more and less than 100 ppm, the occurrence of arcing can be almost eliminated, which is more desirable. As described above, the oxygen content greatly affects the occurrence of arcing, but there is a tendency that arcing tends to occur even if the degree of integration of the ⁇ 200 ⁇ plane and ⁇ 222 ⁇ plane decreases. That is, the degree of surface integration also affects the occurrence of arcing. The fact that the surface integration degree is reduced and the film formation rate is slow means that the metal atom releasing ability is lowered. When metal atoms are not released, abnormal discharge (arcing) occurs to compensate for the decrease in metal atom release ability.
  • the throughput performance is further improved.
  • the next factor affecting the throughput performance is the crystal grain size.
  • a desirable range is 1 ⁇ m or more and 50 ⁇ m or less. When the crystal grain size is 1 ⁇ m or less, it may be difficult to control the degree of ⁇ 200 ⁇ or ⁇ 222 ⁇ plane integration within the range of the present invention. Further, a more desirable range is more than 10 ⁇ m and 50 ⁇ m or less.
  • the metal sputtering target material of the present invention is composed of a metal or alloy having a cubic crystal structure.
  • the metal or alloy is not particularly limited as long as it has a cubic crystal structure.
  • a main metal element constituting the metal or alloy Cr, Mo, W, V, Nb, Ta, Fe, Pd, Pt, Ir, Au, Ag, Cu, Al, Ni etc. are mentioned.
  • the metal or alloy constituting the sputtering target material has one or more of Cr, Mo, W, V, or Ta as a main element, and the crystal structure thereof is a cubic body-centered cubic lattice (BCC) structure. It is more desirable to have
  • These may be single-component metals or alloys (multi-component metals) with other elements added.
  • the alloy include Cr—Mo, Mo—W, and Mo—Nb.
  • the metal or alloy is a cubic metal and may have a BCC structure. Moreover, even if it is not completely alloyed, it is only necessary that a substance having the largest volume ratio is a main phase, these are cubic metals, and have a BCC structure.
  • Cr, Mo, W, V, or Ta metal has a low electrical resistance, is suitable as an electrode material, and has a relatively high throughput performance in many cases.
  • the manufacturing method of the metal-based sputtering target material of the present invention can utilize a melting method, a powder metallurgy method, and the like, and is not particularly limited.
  • the step of manufacturing the block and the heated block are plastically deformed by rolling or the like.
  • a production method comprising a step of areaization is preferred. That is, the sputtering target material having the texture of the present invention can be easily obtained by controlling the oxygen concentration, average crystal grain size, and relative density contained in the block within a specific range and further plastically deforming within a specific temperature range. Therefore, the details of the manufacturing method will be described below.
  • the block preferably has the following conditions.
  • the oxygen concentration contained in the block material before rolling is preferably at least lower than 500 ppm by mass. If it exceeds 500 ppm by mass, the texture of the present invention may not be obtained, or ear cracks and cracks may occur during rolling, and the yield may be significantly reduced.
  • the oxygen concentration of the block depends on the oxygen concentration (oxygen content) of the metal powder as a raw material, and by selecting a raw metal powder having a different oxygen content, or by oxidizing or reducing the raw metal powder, It is possible to control the oxygen concentration of the block.
  • HIP hot isostatic pressing
  • the crystal grain size of the block before rolling is desirably more than 1 ⁇ m and 50 ⁇ m or less. Within this range, if the crystal grain size is more than 10 ⁇ m and not more than 50 ⁇ m, it is easy to control the texture within the range of the present invention. A block having a crystal grain size of less than 1 ⁇ m may be difficult to manufacture. If it exceeds 50 ⁇ m, the texture of the present invention may be difficult to obtain, or cracks may easily occur during rolling.
  • the crystal grain size of the block can be controlled from the grain size of the raw metal powder and the conditions under which the metal powder is sintered while growing the grains, as will be described later in the production method.
  • the relative density of the block before rolling has an important influence on the formation of a texture accompanying rolling, and the desirable range of the relative density is 90.0% or more and less than 99.0%.
  • the texture of the present invention can be easily obtained by rolling.
  • a more preferable range of relative density for easily obtaining the texture of the present invention is 94.0% or more and 98.0% or less. If it is this range, a higher texture will be obtained stably at the time of manufacture.
  • the relative density of the block can be controlled by the density of the temporary molded body, the particle size of the metal powder, and the pressure and temperature for sintering, as will be described in the production method described later.
  • the block before rolling can be manufactured by melting, but a method of pressure-sintering metal powder with HIP that can cope with Cr, Mo, W or the like having a high melting point is efficient.
  • the raw material metal powder used as the sputtering target material is vacuum-sealed in a capsule container made of SS400 steel plate having a thickness of about 3 mm, and is pressure-sintered by HIP under conditions of a temperature of 600 ° C. to 1300 ° C. and a pressure of 500 to 2000 atm. The optimum temperature is selected depending on the metal or alloy.
  • the relative density of the pressure sintered body (block) thus obtained is 90% or more and less than 99.0%.
  • the relative density can be controlled by the density of the temporary molded body, the particle size of the metal powder, and the pressure and temperature of the HIP.
  • the metal powder desirably has a size of about 0.1 ⁇ m to 50 ⁇ m. For example, a powder having an average particle diameter of 6 ⁇ m is used.
  • the crystal grain size of the block is determined in consideration of grain growth according to the grain size of the metal powder and the HIP temperature condition.
  • a block by flowing hydrogen under normal pressure or reduced pressure and sintering the green compact solidified with CIP while reducing it at a high temperature.
  • the average hydrogen concentration during the heat treatment is 0.5% or more and 20% or less, and the oxygen concentration can be controlled by the hydrogen flow rate.
  • Sintering is performed at about 500 to 1800 ° C., and a molded body having a relative density of 90% or more and less than 99.0% is obtained.
  • the optimum sintering temperature is selected depending on the metal or alloy. That is, the temperature can be set to a temperature at which the sintering phenomenon starts when diffusion above the Tamman temperature calculated from the melting point of each metal or alloy starts. Control of the relative density of the block and the crystal grain size can be performed in the same manner as in the case of the above HIP.
  • Plastic working can be carried out by rolling, and rolling temperature conditions and rolling conditions are important.
  • the rolling start temperature which is a rolling temperature condition, is usually in a temperature range in which a metal or alloy can be plastically deformed by the pressing capacity of the rolling equipment, but the desired rolling start temperature is the texture of the metal or alloy obtained after rolling. It is decided by.
  • a desirable rolling start temperature range is 600 ° C. or higher and 900 ° C. or lower. If the temperature is lower than 600 ° C., a desired texture can be obtained, but there are cases where rolling resistance cannot be achieved because the deformation resistance increases and the capacity of the rolling mill becomes insufficient. If it exceeds 900 ° C., the texture of the present invention cannot be obtained, and the effects of the present invention may not be obtained.
  • the reduction condition is to control the reduction rate per pass during rolling and the total reduction rate.
  • the control is performed as follows for any metal or alloy.
  • the rolling reduction per pass in rolling is preferably relatively high. Specifically, the rolling reduction per pass is preferably more than 10% and 50% or less. Within the above range, the texture of the present invention can be easily obtained. If the rolling reduction per pass is 10% or less, the texture of the present invention may be difficult to obtain. Moreover, since it may generate
  • a preferable range of the total rolling reduction is 20% or more and 95% or less. If it is less than 20%, the texture of the present invention may be difficult to obtain. If it exceeds 95%, not only the effect of obtaining a texture is saturated but also ear cracks or the like may occur, resulting in a decrease in yield.
  • the block may undergo work hardening during rolling, and deformation resistance may increase or toughness may decrease.
  • the block can be reheated and softened by recovery or recrystallization.
  • the phenomenon described on the left is likely to occur in the case of Mo-based blocks, and in the case of Mo, it can be reheated to over 900 ° C. and less than 1100 ° C. and held for 1 minute to 10 hours and softened.
  • the texture of the sputtering target material of the present invention can be obtained without problems if it is softened by reheating during rolling and then rolled again in a temperature range of 600 ° C. or more and 900 ° C. or less.
  • the texture of the present invention even if heat treatment is performed after rolling to improve the toughness of the target material. If the reheating temperature is more than 900 ° C. and less than 1100 ° C., the texture of the present invention can be obtained without any problem. When it is 1100 ° C. or higher, the crystal orientation tends to be randomized by reheating, and the target material of the present invention cannot be obtained.
  • the block may be directly rolled, but the sputtering target material of the present invention can be more easily produced by a method of rolling the block while covering it with a capsule metal plate to prevent oxidation.
  • the rolling conditions for the blocks placed in the capsule may be rolled under the same conditions as described above.
  • a gap may be created between the capsule plate and the block. Oxidation may not be suppressed if air is contained in the capsule. However, even if a gap is generated, the capsule plate and the block surface are in close contact during rolling, so the air in the capsule is pushed out and oxidation is suppressed.
  • the In order to suppress oxidation the air in the gap may be removed in advance by evacuation.
  • the welded portion such as the seam of the capsule plate should be free from pinholes and cracks.
  • a steel plate may be used, and a carbon steel plate such as SS400 can be used. Since the steel sheet is low in material cost and the joint welding of the capsule plate is relatively easy, reliable encapsulation is possible.
  • Example 1 Using a pure Mo powder (raw material powder) with an average particle size of 5 ⁇ m as a starting material, a Mo sputtering target material was manufactured by HIP and rolling.
  • the used raw material powder had 1500 mass ppm of oxygen attached, and the oxygen concentration was reduced by reducing heat treatment in hydrogen.
  • An SS400 HIP container was prepared, and the Mo raw material powder was filled in the container. The inside of the container was evacuated and then purged with hydrogen, and further heated to 300 ° C. for reduction.
  • the oxygen concentration was controlled by the reduction time (retention time) using the tendency that the oxygen concentration decreased as the retention time increased. Analysis of the oxygen concentration of the Mo block was performed on the block after HIP sintering.
  • the obtained Mo block was heated and stretched in the length direction by rolling.
  • the total rolling reduction was constant at 59%, and rolling was performed for 4 passes at a rolling reduction rate of 20% per pass.
  • Rolling was performed while changing various block temperatures when starting rolling, and the texture of the obtained Mo rolled sheet was examined.
  • the range of the rolling start temperature was 500 ° C to 1200 ° C.
  • the relative density of the obtained rolled sheet was 99.5 to 99.9%.
  • the ⁇ 200 ⁇ , ⁇ 222 ⁇ , ⁇ 110 ⁇ plane integration degree of the obtained rolled plate was measured by an X-ray diffraction method (MoK ⁇ ray).
  • the measurement surface was located at a depth of 1.5 mm in the thickness direction from the surface of the rolled plate, and a surface parallel to the rolled surface was cut out by machining.
  • the ⁇ 200 ⁇ plane integration degree, ⁇ 222 ⁇ plane integration degree, and ⁇ 110 ⁇ plane integration degree of the crystal phase are obtained by the method described above. For example, in the ⁇ 200 ⁇ intensity ratio, It was obtained as in 1).
  • the sum of the ⁇ 200 ⁇ plane integration degree and the ⁇ 222 ⁇ plane density exceeds 70% when the rolling start temperature is 850 ° C. or less, and very excellent characteristics are obtained. This excellent characteristic is almost maintained up to 600 ° C., and the rolling start temperature at which particularly excellent characteristics are obtained is 600 ° C. or higher and 850 ° C. or lower.
  • the rolled sheet obtained in this experiment was heat-treated at 1050 ° C. for 2 hours, and the texture was examined in the same manner as described above. According to this, it was confirmed that the ⁇ 200 ⁇ plane integration degree and the ⁇ 222 ⁇ plane integration degree satisfy the conditions of the present invention even after the heat treatment.
  • the rolled sheet obtained in this experiment was heat-treated at 1200 ° C. for 2 hours, and the texture was examined in the same manner as described above. According to this, the crystal orientation was randomized, and the ⁇ 200 ⁇ plane integration degree, the ⁇ 222 ⁇ plane integration degree, and the ⁇ 110 ⁇ plane integration degree before and after the heat treatment did not satisfy the conditions of the present invention.
  • the texture of the sputtering target material of the present invention can be controlled by setting the rolling start temperature to a specific condition.
  • a 127 mm ⁇ 191 mm ⁇ 6 mmt test material was cut out from a rolled plate produced at each rolling start temperature.
  • the sputtering surface of the cut out test material was set at a depth of 1.5 mm in the depth direction from the surface of the rolled surface (127 mm ⁇ 191 mm surface of the test material).
  • the test material was bonded to a Cu backing plate to prepare a sputtering target material. Using this target material, the throughput performance during sputtering was evaluated.
  • the sputtering target was mounted on a sputtering apparatus, and the arcing characteristics were evaluated.
  • the discharge conditions were sputtering gas: Ar, sputtering gas pressure: 2.0 mTorr (0.27 Pa), sputtering power: 2.0 kW, continuous discharge until the integrated sputtering power reached 5 kWh, and the number of arcing generated during that time was measured.
  • a coil was directly wound around a DC power supply cable, and arcing was observed with an oscilloscope.
  • the rolling start temperature is important for controlling the texture of the present invention, and in the same rolling start temperature range. It was confirmed that the sputtering target material was within the range of the present invention, and it was shown that arcing can be suppressed.
  • the Mo powder was hardened by the CIP method, vacuumed and then purged with hydrogen, and further heated and sintered while being reduced in a heat treatment furnace in which hydrogen was passed at atmospheric pressure.
  • the sintering temperature varied from block to block and the range was 1200-1800 ° C.
  • the obtained block dimensions were a constant value of 210 mm width and 810 mm length, and the thickness was 22.8 to 85 mm.
  • the average crystal grain size was 9.8 to 55 ⁇ m, and the relative density was 89.2% to 99.2%.
  • the oxygen concentration contained in the produced block decreased as the treatment time increased, and the oxygen concentration was controlled by the treatment time.
  • the analysis of oxygen concentration was performed on the block after sintering.
  • the Mo block plates having different oxygen concentrations and crystal grain sizes were rolled under various conditions shown in Table 1. As conditions, the rolling start temperature, the rolling reduction per pass, and the total rolling reduction were changed. Here, when the plate temperature during rolling decreased by 100 ° C. or more compared to the rolling start temperature, reheating was performed to return the plate temperature to the rolling start temperature.
  • the ⁇ 200 ⁇ , ⁇ 222 ⁇ and ⁇ 110 ⁇ plane integration degree of the obtained rolled sheet was measured by an X-ray diffraction method (MoK ⁇ ray).
  • the measurement surface was located at a depth of 1.5 mm in the thickness direction from the surface of the rolled plate, and a surface parallel to the rolled surface was cut out by machining.
  • the ⁇ 200 ⁇ plane integration degree, ⁇ 222 ⁇ plane integration degree, and ⁇ 110 ⁇ plane integration degree of the crystal phase are obtained by the method described above. For example, in the ⁇ 200 ⁇ intensity ratio, It was obtained as in 1).
  • the metal structure was observed from the normal direction of the rolled surface at a position 1.5 mm deep in the thickness direction from the surface of the rolled plate, and the crystal grain size in the direction perpendicular to the rolling was measured by the line segment method.
  • a 127 mm ⁇ 191 mm ⁇ 6 mmt test material was cut out from the obtained block plate.
  • the sputtering surface of the cut out test material was set at a depth of 1.5 mm in the depth direction from the surface of the rolled surface (127 mm ⁇ 191 mm surface of the test material).
  • the test material was bonded to a Cu backing plate to produce a sputtering target material. Using this target material, the throughput performance during sputtering was evaluated.
  • the sputtering target was mounted on a sputtering apparatus, and the arcing characteristics were evaluated.
  • the discharge conditions were sputtering gas: Ar, sputtering gas pressure: 2.0 mTorr (0.27 Pa), sputtering power: 2.0 kW, continuous discharge until the integrated sputtering power reached 5 kWh, and the number of arcing generated during that time was measured.
  • a coil was directly wound around a DC power supply cable, and arcing was observed with an oscilloscope.
  • No. Materials 1 to 8 are comparative examples in which the conditions of the target plate are not within the scope of the present invention.
  • No. 1 is a raw material block plate having an oxygen concentration of 600 ppm, a crystal grain size of 33 ⁇ m, a relative density of 97.6%, and a thickness of 44 mm, rolled at a rolling start temperature of 800 ° C., a rolling reduction per pass of 15%, and a total rolling reduction of 56%. It is what. Both ⁇ 200 ⁇ plane integration and ⁇ 222 ⁇ plane integration were within the scope of the present invention, but the oxygen concentration was outside the scope of the present invention. In this case, the film formation rate was similar to that of the other invention examples, but the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
  • No. 2 is a raw material block plate having an oxygen concentration of 50 ppm, a crystal grain size of 55 ⁇ m, a relative density of 97.8%, and a thickness of 67 mm, rolling at a rolling start temperature of 750 ° C., a rolling reduction per pass of 13%, and a total rolling reduction of 67%. It is what. Although the oxygen concentration was within the range of the present invention, the ⁇ 200 ⁇ plane integration level and the ⁇ 222 ⁇ plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
  • No. 3 is a raw material block plate having an oxygen concentration of 50 ppm, a crystal grain size of 9.8 ⁇ m, a relative density of 97.8%, a thickness of 67 mm, a rolling start temperature of 750 ° C., a rolling reduction per pass of 13%, and a total rolling reduction of 67%.
  • the oxygen concentration was within the range of the present invention, the ⁇ 200 ⁇ plane integration level and the ⁇ 222 ⁇ plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
  • No. 4 is a raw material block plate having an oxygen concentration of 100 ppm, a crystal grain size of 13 ⁇ m, a relative density of 89.2%, and a thickness of 55 mm, rolled at a rolling start temperature of 850 ° C., a reduction rate of 25% per pass, and a total reduction rate of 44%. It is what. Although the oxygen concentration was within the range of the present invention, the ⁇ 200 ⁇ plane integration level and the ⁇ 222 ⁇ plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
  • No. 5 is a raw material block plate having an oxygen concentration of 100 ppm, a crystal grain size of 13 ⁇ m, a relative density of 99.2%, and a thickness of 55 mm, rolled at a rolling start temperature of 850 ° C., a reduction rate of 25% per pass, and a total reduction rate of 44%. It is what. Although the oxygen concentration was within the range of the present invention, the ⁇ 200 ⁇ plane integration level and the ⁇ 222 ⁇ plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
  • No. 6 is a raw material block plate having an oxygen concentration of 200 ppm, a crystal grain size of 33 ⁇ m, a relative density of 96.5% and a thickness of 44 mm, rolled at a rolling start temperature of 800 ° C., a rolling reduction rate of 4%, and a total rolling reduction rate of 56%. It is a thing. Although the oxygen concentration was within the range of the present invention, the ⁇ 200 ⁇ plane integration level and the ⁇ 222 ⁇ plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
  • No. 8 is a raw material block plate having an oxygen concentration of 30 ppm, a crystal grain size of 23 ⁇ m, a relative density of 96.5%, and a thickness of 85 mm, rolling at a rolling start temperature of 950 ° C., a rolling reduction rate of 30%, and a total rolling reduction rate of 83%. It is what. Although the oxygen concentration was within the range of the present invention, the ⁇ 200 ⁇ plane integration level and the ⁇ 222 ⁇ plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
  • No. Nos. 9 to 13 are raw material block plates having an oxygen concentration of 5 to 500 ppm, a crystal grain size of 33 ⁇ m, a relative density of 97.3 to 98.2%, and a thickness of 44 mm, a rolling start temperature of 800 ° C., and a rolling reduction per pass of 15%. , Rolled at a total rolling reduction of 56%.
  • the oxygen concentration falls within the range of 5 ppm to 500 ppm of the present invention, and the ⁇ 200 ⁇ plane integration degree and the ⁇ 222 ⁇ plane integration degree both fall within the scope of the present invention.
  • the deposition rate was higher than that of the comparative example (excluding the comparative example of No. 1), and no arcing occurred. Therefore, the throughput performance was superior to the comparative example.
  • a raw material block plate having an oxygen concentration of 50 ppm, a crystal grain size of 10.5 to 50 ⁇ m, a relative density of 97.8%, and a thickness of 67 mm was set at a rolling start temperature of 750 ° C. and a reduction rate per pass of 13%. Rolled at a rolling reduction of 67%.
  • the oxygen concentration is within the scope of the present invention, and the ⁇ 200 ⁇ plane integration degree and the ⁇ 222 ⁇ plane integration degree are both within the scope of the present invention.
  • the crystal grain size of the raw material block plate is more than 10 ⁇ m and 50 ⁇ m or less, the target plate of the present invention was obtained.
  • the film formation rate was higher than that of the comparative example (excluding the comparative example of No. 1), and no arcing occurred.
  • the film formation rate was particularly high when the crystal grain size was 20 to 40 ⁇ m.
  • a raw material block plate having an oxygen concentration of 100 ppm, a crystal grain size of 13 ⁇ m, a relative density of 90.0 to 98.8%, and a thickness of 55 mm, a rolling start temperature of 850 ° C., a rolling reduction per pass of 25%, Rolled at a rolling reduction of 44%.
  • the oxygen concentration is within the scope of the present invention, and the ⁇ 200 ⁇ plane integration degree and the ⁇ 222 ⁇ plane integration degree are both within the scope of the present invention.
  • the relative density of the raw material block plate was 90.0% or more and less than 99.0%, the target plate of the present invention was obtained.
  • the film formation rate was higher than that of the comparative example (excluding the comparative example of No. 1), and no arcing occurred.
  • the relative density of the raw material block plate was 94.0% or more and 98.0% or less, a higher surface integration degree was obtained, and the film formation rate was high.
  • Example 3 Various sputtering target materials were manufactured by HIP and rolling using Cr, W, V, Ta, Mo, and Nb powder having an average particle diameter of 1 to 20 ⁇ m as starting materials. First, for Cr, W, V, Ta, and Nb, a pure metal target material was manufactured with a single powder. Moreover, the alloy target material was manufactured by mixing powder in the ratio of 50:50 by mass ratio with the combination of Cr and Mo, Mo and W, and Mo and Nb.
  • the raw material powders each had 1500 ppm by mass of oxygen attached thereto, and the oxygen concentration was reduced by reducing heat treatment in hydrogen.
  • An SS400 HIP container was prepared and filled with raw material powder. The inside of the container was evacuated and purged with hydrogen, and then heated to 300 ° C. for reduction. The oxygen concentration decreased as the retention time increased, and the oxygen concentration was controlled by the reduction time. Analysis of the oxygen concentration of the raw material block was performed on the block after HIP sintering.
  • the inside of the HIP container was evacuated with a rotary pump and an oil diffusion pump. After the degree of vacuum reached about 10 -2 Pa, the suction port and the like were sealed carefully so as not to leak due to pinholes. Thereafter, the HIP sintering process was performed under the conditions of 1150 to 1400 ° C. ⁇ 2 hours, 1200 atm (121.6 MPa). A raw material block having a width of 250 mm, a length of 1700 mm and a thickness of 20 to 80 mm was cut out from the obtained sintered body.
  • the obtained raw material block was heated and rolled at different rolling temperatures and total reduction ratios.
  • the raw material block conditions and rolling conditions are shown in Table 2.
  • the ⁇ 200 ⁇ , ⁇ 222 ⁇ , ⁇ 110 ⁇ plane integration degree of the obtained rolled plate was measured by an X-ray diffraction method (MoK ⁇ ray). It was confirmed by X-ray diffraction that all the measurement pieces were body-centered cubic crystals. The measurement surface was located at a depth of 3 mm from the surface of the rolled plate in the thickness direction, and a surface parallel to the rolled surface was cut out by machining.
  • the ⁇ 200 ⁇ plane integration degree, ⁇ 222 ⁇ plane integration degree, and ⁇ 110 ⁇ plane integration degree of the crystal phase are obtained by the method described above. For example, in the ⁇ 200 ⁇ intensity ratio, It was obtained as in 1).
  • a test material of 127 mm ⁇ 191 mm ⁇ 6 mmt was cut out from the obtained rolled plate. This was bonded to a Cu backing plate to prepare a sputtering target material. Using this target material, the throughput performance during sputtering was evaluated.
  • the produced sputtering target material was attached to a sputtering apparatus, and a film formation rate was measured by forming a thin film on a glass substrate.
  • the sputtering conditions were as follows. Sputtering gas: Ar, sputtering gas pressure: 2.0 mTorr (0.27 Pa), sputtering power: 2.0 kW, substrate: Corning # 7059 (50 ⁇ 50 mm 2 ).
  • pre-sputtering was performed in advance when measuring the film formation rate.
  • the pre-sputtering conditions were an Ar gas pressure of 5.0 mTorr (0.67 Pa), a sputtering power of 2.0 kW, and a time of 10 min.
  • the sputtering target was mounted on a sputtering apparatus, and the arcing characteristics were evaluated.
  • the discharge conditions were sputtering gas: Ar, sputtering gas pressure: 2.0 mTorr (0.27 Pa), sputtering power: 2.0 kW, continuous discharge until the integrated sputtering power reached 5 kWh, and the number of arcing generated during that time was measured.
  • a coil was directly wound around a DC power supply cable, and arcing was observed with an oscilloscope.
  • the deposition rate differs depending on the metal or alloy, but when compared in the same metal or alloy, in any case, the ⁇ 200 ⁇ and ⁇ 222 ⁇ plane integration levels are outside the scope of the present invention.
  • the film formation rate was high.
  • No. 28 to 30 are Cr target materials.
  • No. No. 28 had a rolling reduction per pass during rolling of 10% or less, and the ⁇ 200 ⁇ and ⁇ 222 ⁇ plane integration degrees were comparative examples outside the scope of the present invention.
  • no. 29 and 30 were invention examples within the scope of the present invention.
  • the inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
  • No. 31 to 33 are W target materials.
  • No. No. 31 had a rolling temperature exceeding 900 ° C., and the degree of ⁇ 200 ⁇ and ⁇ 222 ⁇ plane integration was a comparative example outside the scope of the present invention.
  • no. 32 and 33 were invention examples within the scope of the present invention.
  • the inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
  • No. 34 to 36 are V target materials.
  • the crystal grain size of the raw material block exceeded 50 ⁇ m, and the ⁇ 200 ⁇ and ⁇ 222 ⁇ plane integration degrees were comparative examples outside the scope of the present invention.
  • no. 35 and 36 were invention examples within the scope of the present invention.
  • the inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
  • No. Reference numerals 37 to 39 are Ta target materials.
  • No. No. 37 had a crystal grain size of the raw material block of 10 ⁇ m or less, and the ⁇ 200 ⁇ and ⁇ 222 ⁇ plane integration degrees were comparative examples outside the scope of the present invention.
  • no. 38 and 39 were invention examples within the scope of the present invention.
  • the invention example had a smaller number of arcing times than the comparative example.
  • No. Reference numerals 40 to 42 are Cr—Mo target materials.
  • No. No. 40 had a total rolling reduction of less than 20% during rolling, and the ⁇ 200 ⁇ and ⁇ 222 ⁇ plane integration degrees were comparative examples outside the scope of the present invention.
  • no. 41 and 42 were invention examples within the scope of the present invention.
  • the inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
  • No. 43 to 45 are Mo-W target materials.
  • No. No. 43 has an oxygen concentration exceeding 500 ppm, which is a comparative example outside the scope of the present invention.
  • no. 44 and 45 were invention examples within the scope of the present invention.
  • the invention example had a smaller number of arcing times than the comparative example.
  • No. Reference numerals 46 to 48 denote Mo—Nb target materials.
  • No. No. 46 had a relative density of raw material blocks of 99.0% or more, and the ⁇ 200 ⁇ and ⁇ 222 ⁇ plane integration degrees were comparative examples outside the scope of the present invention.
  • no. 47 and 48 were invention examples within the scope of the present invention.
  • the inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
  • No. Reference numerals 49 to 51 are Nb target materials.
  • the crystal grain size of the raw material block exceeded 50 ⁇ m, and the ⁇ 200 ⁇ and ⁇ 222 ⁇ plane integration degrees were comparative examples outside the scope of the present invention.
  • no. 50 and 51 were invention examples within the scope of the present invention.
  • the inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
  • the metal-based sputtering target plate of the present invention has better throughput performance than the conventional one.
  • Example 4 Various Mo sputtering target materials were manufactured by heat sintering and rolling using pure Mo powder having an average particle size of 4 ⁇ m as a starting material.
  • the raw material powder had 1200 mass ppm of oxygen attached thereto, and it was decided to produce a block in which the oxygen concentration was reduced by reducing and sintering in hydrogen.
  • the Mo powder was hardened by the CIP method, vacuumed and then purged with hydrogen, and further heated and sintered while being reduced in a heat treatment furnace in which hydrogen was passed at atmospheric pressure.
  • the sintering temperature varied from block to block and the range was 1100-1800 ° C.
  • the obtained block dimensions were constant values of 300 mm width and 950 mm length, and the thickness was 46 to 80 mm.
  • the average crystal grain size was 9.9 to 53 ⁇ m, and the relative density was 89.9% to 99.0%.
  • the oxygen concentration contained in the produced block decreased as the treatment time increased, and the oxygen concentration was controlled by the treatment time.
  • the analysis of oxygen concentration was performed on the block after sintering. Further, no texture was formed in the block, and the crystal orientation was random.
  • Table 3 shows the crystal grain size of each block obtained by observing the metal structure by the line segment method.
  • Each of the Mo block plates having different oxygen concentrations and crystal grain sizes was covered with a capsule of SS400 steel plate having a thickness of 12 mm. At this time, the gap between the block surface and the capsule plate was set to 1 mm or less.
  • the Mo block plate covered with the capsule was rolled under various conditions shown in Table 3. As conditions, the rolling start temperature, the rolling reduction per pass, and the total rolling reduction were changed. Here, when the plate temperature during rolling decreased by 100 ° C. or more compared to the rolling start temperature, reheating was performed at the same temperature in order to return the plate temperature to the rolling start temperature.
  • Each Mo plate was heat treated to restore toughness after completion of rolling. As shown in Table 3, the temperature of this heat treatment was in the range of 850 ° C. to 1100 ° C., respectively.
  • the ⁇ 200 ⁇ , ⁇ 222 ⁇ and ⁇ 110 ⁇ plane integration degree of the obtained rolled sheet was measured by an X-ray diffraction method (MoK ⁇ ray). The measurement surface was located at a depth of 2.0 mm in the thickness direction from the surface of the rolled plate, and a surface parallel to the rolled surface was cut out by machining.
  • the ⁇ 200 ⁇ plane integration degree, ⁇ 222 ⁇ plane integration degree, and ⁇ 110 ⁇ plane integration degree of the crystal phase are obtained by the method described above. For example, in the ⁇ 200 ⁇ intensity ratio, It was obtained as in 1).
  • the same surface integration degree was measured at the position of the thickness center, but the same level of surface integration degree was measured for each surface.
  • the metal structure was observed from the normal direction of the rolling surface at a position 2.0 mm deep from the surface of the rolled plate in the thickness direction, and the crystal grain size in the direction perpendicular to the rolling was measured by the line segment method.
  • a 127 mm ⁇ 191 mm ⁇ 5 mmt test material was cut out from the obtained block plate and processed into 100 mm ⁇ ⁇ 5 mmt.
  • the sputtering surface of the cut out test material was set at a depth of 2.0 mm in the depth direction from the surface of the rolled surface.
  • the test material was bonded to a Cu backing plate to prepare a sputtering target material. Using this target material, the throughput performance during sputtering was evaluated.
  • the produced sputtering target material was mounted on a sputtering apparatus, and a film formation rate was measured by forming a Mo thin film on a glass substrate.
  • the sputtering conditions were as follows. Sputtering gas: Ar, a sputtering gas pressure: 2.5mTorr (0.33Pa), sputtering power: 0.6 kW, substrate: Corning # 7059 (50 ⁇ 50mm 2).
  • pre-sputtering was performed in advance when measuring the film formation rate.
  • the pre-sputtering conditions are an Ar gas pressure of 5 mTorr (0.66 Pa), a sputtering power of 1.0 kW, and a time of 10 min.
  • the film thickness of the thin film formed by depositing for 11 min at an input power of 1.0 kW was measured.
  • the film thickness of the Mo thin film formed on the substrate under the above conditions was measured, and the value obtained by dividing this by the film formation time was defined as the film formation rate [nm / sec].
  • the sputtering target was mounted on a sputtering apparatus, and the arcing characteristics were evaluated.
  • the discharge conditions were sputtering gas: Ar, sputtering gas pressure: 2.5 mTorr (0.33 Pa), sputtering power: 1.0 kW, continuous discharge until the integrated sputtering power reached 3 kWh, and the number of arcing generated during that time was measured. .
  • the number of arcing times was measured by detecting electromagnetic waves generated by abnormal discharge with a waveguide sensor, which is a highly sensitive sensor, and analyzing with an oscilloscope.
  • No. No. 52 is a raw material block plate having an oxygen concentration of 550 ppm, a crystal grain size of 27 ⁇ m, a relative density of 97.4%, and a thickness of 46 mm, rolled at a rolling start temperature of 650 ° C., a rolling reduction per pass of 14%, and a total rolling reduction of 53%. It is a thing. After rolling, a heat treatment of 900 ° C. ⁇ 4 h was performed. Both ⁇ 200 ⁇ plane integration and ⁇ 222 ⁇ plane integration were within the scope of the present invention, but the oxygen concentration was outside the scope of the present invention. In this case, the deposition rate was similar to that of the other invention examples, but the number of arcing was extremely large. Therefore, the throughput performance was inferior compared to the other invention examples.
  • No. 53 is a material block plate having an oxygen concentration of 35 ppm, a crystal grain size of 53 ⁇ m, a relative density of 96.8%, and a thickness of 70 mm, rolled at a rolling start temperature of 820 ° C., a rolling reduction rate of 13%, and a total rolling reduction rate of 75%. It is a thing. After rolling, a heat treatment of 950 ° C. ⁇ 2 h was performed. Although the oxygen concentration was within the range of the present invention, the ⁇ 200 ⁇ plane integration level and the ⁇ 222 ⁇ plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
  • No. No. 54 is a raw material block plate having an oxygen concentration of 35 ppm, a crystal grain size of 9.9 ⁇ m, a relative density of 96.9% and a thickness of 70 mm, a rolling start temperature of 820 ° C., a rolling reduction per pass of 13%, and a total rolling reduction of 75%.
  • a heat treatment of 950 ° C. ⁇ 2 h was performed.
  • the oxygen concentration was within the range of the present invention, the ⁇ 200 ⁇ plane integration level and the ⁇ 222 ⁇ plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
  • No. No. 56 is a raw material block plate having an oxygen concentration of 95 ppm, a crystal grain size of 18 ⁇ m, a relative density of 99.0% and a thickness of 60 mm, rolled at a rolling start temperature of 870 ° C., a reduction rate of 23% per pass, and a total reduction rate of 41%. It is a thing. After rolling, a heat treatment of 1050 ° C. ⁇ 0.5 h was performed. Although the oxygen concentration was within the range of the present invention, the ⁇ 200 ⁇ plane integration level and the ⁇ 222 ⁇ plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
  • No. No. 57 is a raw material block plate having an oxygen concentration of 200 ppm, a crystal grain size of 27 ⁇ m, a relative density of 96.3%, and a thickness of 40 mm, rolled at a rolling start temperature of 650 ° C., a rolling reduction rate of 3%, and a total rolling reduction rate of 53%. It is a thing. After rolling, a heat treatment of 900 ° C. ⁇ 4 h was performed. Although the oxygen concentration was within the range of the present invention, the ⁇ 200 ⁇ plane integration level and the ⁇ 222 ⁇ plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
  • No. No. 58 is a raw material block plate having an oxygen concentration of 200 ppm, a crystal grain size of 27 ⁇ m, a relative density of 97.0% and a thickness of 40.0 mm, a rolling start temperature of 650 ° C., a rolling reduction per pass of 14%, and a total rolling reduction of 14%.
  • a heat treatment of 900 ° C. ⁇ 4 h was performed.
  • the oxygen concentration was within the range of the present invention, the ⁇ 200 ⁇ plane integration level and the ⁇ 222 ⁇ plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
  • No. 59 is a raw material block plate having an oxygen concentration of 25 ppm, a crystal grain size of 18 ⁇ m, a relative density of 95.9% and a thickness of 80 mm, rolled at a rolling start temperature of 950 ° C., a rolling reduction rate of 30%, and a total rolling reduction rate of 83%. It is a thing. After rolling, a heat treatment of 1000 ° C. ⁇ 2 h was performed. Although the oxygen concentration was within the range of the present invention, the ⁇ 200 ⁇ plane integration level and the ⁇ 222 ⁇ plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
  • No. 60 is a raw material block plate having an oxygen concentration of 10 ppm, a crystal grain size of 21 ⁇ m, a relative density of 97.5%, and a thickness of 75 mm, a rolling start temperature of 850 ° C., a rolling reduction per pass of 20%, and a total rolling reduction of 73.8%.
  • the oxygen concentration was within the range of the present invention, the ⁇ 200 ⁇ plane integration level and the ⁇ 222 ⁇ plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
  • the materials 61 to 85 are invention examples in which the conditions of the target plate are within the scope of the present invention.
  • No. Nos. 61 to 65 were prepared as raw material block plates in which the oxygen concentration was changed in the range of 5 to 500 ppm, the crystal grain size was 27 ⁇ m, the relative density was 97.3 to 98.0%, and the thickness was 46 mm.
  • the rolling reduction per pass is 14% and the rolling reduction is 53%.
  • a heat treatment of 900 ° C. ⁇ 4 h was performed.
  • the oxygen concentration falls within the range of 5 ppm to 500 ppm of the present invention, and the ⁇ 200 ⁇ plane integration degree and the ⁇ 222 ⁇ plane integration degree both fall within the scope of the present invention.
  • the film formation rate was higher than that of the comparative example (excluding the comparative example of No. 52), and in both cases exceeded 40 nm / min.
  • the oxygen concentration was 500 ppm. In 61, the number of arcing was slightly large, 9 times. When the oxygen concentration of the target material was 100 ppm or more and 200 ppm or less, it decreased to 2 to 6 times. Furthermore, if it was less than 100 ppm, no arcing occurred.
  • the raw material block plate having an oxygen concentration of 35 ppm, a relative density of 96.2 to 96.8%, and a thickness of 70 mm was prepared by changing the crystal grain size to 10.5 to 50 ⁇ m, and the rolling start temperature was 820 ° C. for 1 pass.
  • the rolling reduction is 13% and the rolling reduction is 75%.
  • heat treatments of 950 ° C. ⁇ 2 h, 930 ° C. ⁇ 0.5 h, and 920 ° C. ⁇ 0.5 h were performed.
  • the oxygen concentration is within the scope of the present invention, and at least one of the ⁇ 200 ⁇ plane integration degree and the ⁇ 222 ⁇ plane integration degree is within the scope of the present invention.
  • the film formation rate is larger than that of the comparative example (excluding the comparative example of No. 52). Except for 71 examples, no arcing occurred.
  • No. 72-77 is a raw material block plate having an oxygen concentration of 95 ppm, a crystal grain size of 18 ⁇ m, a relative density of 90.0 to 98.8%, and a thickness of 60 mm, a rolling start temperature of 870 ° C., a rolling reduction per pass of 23%, Rolled at a rolling reduction of 41%. After rolling, a heat treatment of 1050 ° C. ⁇ 0.5 h was performed.
  • the oxygen concentration is within the scope of the present invention, and at least one of the ⁇ 200 ⁇ plane integration degree and the ⁇ 222 ⁇ plane integration degree is within the scope of the present invention.
  • the film formation rate was higher than that of the comparative example (excluding the comparative example of No. 52), and no arcing occurred.
  • the relative density of the block plate was 94.0% or more and 98.0% or less, a higher surface integration degree was obtained, and the film formation rate was high.
  • No. Nos. 78 to 81 are raw material block plates having an oxygen concentration of 25 ppm, a crystal grain size of 18 ⁇ m, a relative density of 96.5%, and a thickness of 80 mm, a rolling start temperature of 600 to 900 ° C., a rolling reduction rate per pass of 30%, and a total rolling reduction rate Rolled at 83%. After rolling, a heat treatment of 1000 ° C. ⁇ 2 h was performed.
  • the oxygen concentration is within the scope of the present invention, and the ⁇ 200 ⁇ plane integration degree and the ⁇ 222 ⁇ plane integration degree are both within the scope of the present invention.
  • the film formation rate was higher than that of the comparative example (excluding the comparative example of No. 52), and no arcing occurred.
  • No. 82 to 87 are raw material block plates having an oxygen concentration of 10 ppm, a crystal grain size of 21 ⁇ m, a relative density of 97.5%, and a thickness of 75 mm, a rolling start temperature of 850 ° C., a rolling reduction per pass of 20%, and a total rolling reduction of 73.
  • heat treatment was performed at a temperature of 850 ° C. to 1090 ° C. for 2 hours.
  • the oxygen concentration is within the scope of the present invention, and at least one of the ⁇ 200 ⁇ plane integration degree and the ⁇ 222 ⁇ plane integration degree is within the scope of the present invention.
  • the target plate of the present invention was obtained at a heat treatment temperature after rolling of less than 1100 ° C.
  • the film formation rate was higher than that of the comparative example (excluding the comparative example of No. 52), and no arcing occurred.
  • the Mo sputtering target plate of the present invention has better throughput performance than the conventional one.
  • the film formation rate is larger than that of the comparative example (excluding the comparative example of No. 52).
  • the crystal grain size of the target plate exceeded 50 ⁇ m, and arcing occurred 10 times, but it was within the acceptable range.
  • the Mo sputtering target plate of the present invention has better throughput performance than the conventional one.
  • Example 5 Various sputtering target materials were manufactured by HIP and rolling using Cr, W, V, Ta, Mo, and Nb powder having an average particle diameter of 1 to 20 ⁇ m as starting materials.
  • Cr, W, V, Ta, and Nb a pure metal target material was manufactured with a single powder.
  • the alloy target material was manufactured by mixing powder in the ratio of 50:50 by mass ratio by the combination of Ta and Mo, Mo and W, and Mo and Nb.
  • the HIP temperature is Cr: 1150 ° C., W: 1400 ° C., V: 1150 ° C., Nb: 1200 ° C., Ta—Mo: 1300 ° C., Mo—W: 1350 ° C., Mo— Nb: 1200 ° C., which is equal to or higher than 1/3 (Taman temperature) of each melting point.
  • the relative density of these raw material blocks and the oxygen concentration contained in each raw material block are as shown in Table 4.
  • the raw material block obtained was encapsulated with a SS400 steel plate having a thickness of 12 mm. At this time, the gap between the block surface and the capsule plate was set to 1 mm or less. These were heated and rolled at different rolling temperatures and total rolling reductions.
  • the raw material block conditions and rolling conditions are shown in Table 4. Each rolled sheet was subjected to heat treatment to restore toughness after completion of rolling. As shown in Table 4, the temperature of this heat treatment was in the range of 850 ° C. to 1100 ° C., respectively.
  • the ⁇ 200 ⁇ , ⁇ 222 ⁇ , ⁇ 110 ⁇ plane integration degree of the obtained rolled plate was measured by an X-ray diffraction method (MoK ⁇ ray). It was confirmed by X-ray diffraction that all the measurement pieces were body-centered cubic crystals. The measurement surface was located at a depth of 3 mm from the surface of the rolled plate in the thickness direction, and a surface parallel to the rolled surface was cut out by machining.
  • the ⁇ 200 ⁇ plane integration degree, ⁇ 222 ⁇ plane integration degree, and ⁇ 110 ⁇ plane integration degree of the crystal phase are obtained by the method described above. For example, in the ⁇ 200 ⁇ intensity ratio, It was obtained as in 1).
  • test material of 100 mm ⁇ ⁇ 5 mmt was cut out from the obtained block plate.
  • the sputtering surface of the cut out test material was set at a depth of 2.0 mm in the depth direction from the surface of the rolled surface.
  • the test material was bonded to a Cu backing plate to prepare a sputtering target material. Using this target material, the throughput performance during sputtering was evaluated.
  • the film thickness of the thin film formed by depositing for 11 min at an input power of 1.0 kW was measured.
  • the film thickness of the metal or alloy thin film formed on the substrate under the above conditions was measured, and the value obtained by dividing this by the film formation time was defined as the film formation rate [nm / sec].
  • the sputtering target was mounted on a sputtering apparatus, and the arcing characteristics were evaluated.
  • the discharge conditions were sputtering gas: Ar, sputtering gas pressure: 2.5 mTorr (0.33 Pa), sputtering power: 1.0 kW, continuous discharge until the integrated sputtering power reached 3 kWh, and the number of arcing generated during that time was measured. .
  • the number of arcing times was measured by detecting electromagnetic waves generated by abnormal discharge with a highly sensitive waveguide sensor and analyzing with an oscilloscope.
  • No. Reference numerals 91 to 93 are Cr target materials.
  • No. No. 91 had a rolling reduction per pass of 10% or less, and the ⁇ 200 ⁇ and ⁇ 222 ⁇ plane integration degrees were comparative examples outside the scope of the present invention.
  • no. 92 and 93 were invention examples within the scope of the present invention.
  • the inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
  • No. 94 to 96 are W target materials.
  • No. No. 94 had a rolling temperature exceeding 900 ° C., and the ⁇ 200 ⁇ and ⁇ 222 ⁇ plane integration degrees were comparative examples outside the scope of the present invention.
  • no. 95 and 96 were invention examples within the scope of the present invention.
  • the inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
  • No. Reference numerals 97 to 99 are V target materials.
  • No. No. 97 used a raw material block having a crystal grain size exceeding 50 ⁇ m, and the ⁇ 200 ⁇ and ⁇ 222 ⁇ plane integration degrees of the obtained target material were comparative examples outside the scope of the present invention.
  • no. 98 and 99 were invention examples within the scope of the present invention.
  • the inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
  • No. 100 to 102 are Ta target materials.
  • No. No. 100 used a raw material block having a crystal grain size of 10 ⁇ m or less, and the ⁇ 200 ⁇ and ⁇ 222 ⁇ plane integration degrees of the obtained target material were comparative examples outside the scope of the present invention.
  • no. 101 and 102 were invention examples within the scope of the present invention.
  • the invention example had a smaller number of arcing times than the comparative example.
  • No. Reference numerals 103 to 105 are Ta—Mo target materials.
  • No. No. 103 had a total rolling reduction of less than 20%, and the ⁇ 200 ⁇ and ⁇ 222 ⁇ plane integration degrees were comparative examples outside the scope of the present invention.
  • no. 104 and 105 were invention examples within the scope of the present invention.
  • the inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
  • No. 106 to 108 are Mo-W target materials.
  • No. No. 106 the oxygen concentration of the target material exceeded 500 ppm, and was a comparative example outside the scope of the present invention.
  • no. 107 and 108 were invention examples within the scope of the present invention.
  • the invention example had a smaller number of arcing times than the comparative example.
  • No. Reference numerals 109 to 111 denote Mo—Nb target materials.
  • No. No. 109 has a relative density of the raw material block of 99.0% or more, and the ⁇ 200 ⁇ and ⁇ 222 ⁇ plane integration degrees are comparative examples outside the scope of the present invention.
  • no. 110 and 111 were invention examples within the scope of the present invention.
  • the inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
  • No. Reference numerals 112 to 114 are Nb target materials.
  • the heat treatment temperature after rolling was 1100 ° C. or higher, the crystal orientation was randomized, and the ⁇ 200 ⁇ and ⁇ 222 ⁇ plane integration degrees were comparative examples outside the scope of the present invention.
  • no. 113 and 114 were invention examples within the scope of the present invention.
  • the inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
  • the metal-based sputtering target plate of the present invention has better throughput performance than the conventional one.
  • FIB focused ion beam
  • Deposition rate of material whose surface integration is changed by rolling start temperature deposition rate of material in FIG. 2

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Abstract

Disclosed is a metallic sputtering target material that can provide a high film formation speed without use of a high-density power, can reduce the occurrence of arcing and can dramatically improve the throughput of a sputtering process. The metallic sputtering target material is formed of a metal or an alloy having a cubic crystal structure. The metallic sputtering target material is characterized in that the content of oxygen in the sputtering target material is not less than 10 ppm by mass and not more than 1000 ppm by mass, and the accumulation degree of {200} plane in a crystal phase to the sputtering surface is not less than 15% and not more than 80%, or the accumulation degree of {222} plane in a crystal phase to the sputtering surface is not less than 15% and not more than 80%.

Description

金属系スパッタリングターゲット材Metal-based sputtering target material
　本発明は、金属系スパッタリングターゲット材に関するものである。 The present invention relates to a metal-based sputtering target material.
　液晶ディスプレイ等のフラットパネルディスプレイの電極材料として、Ｃｒ、Ｍｏ、Ｍｏ合金、Ａｌ、Ａｌ合金、Ｔａ、Ｔｉ、Ａｇ合金、Ｎｉ合金等の金属系材料が使用されている。前記電極の形成にはスパッタ法（スパッタリングプロセス）が適用されおり、スパッタ法で使用されるスパッタリングターゲット材は、電極となる金属から構成される。液晶ディスプレイ等のフラットパネルディスプレイの大型化に伴って、前記スパッタリングターゲット材の大型化が進むとともに、スパッタリングターゲット材の高品質化も検討されている。すなわち、成膜速度が速く、パーティクル発生やアーキング（異常放電）が起こり難いスパッタリングターゲット材の検討がなされている。 Metal materials such as Cr, Mo, Mo alloy, Al, Al alloy, Ta, Ti, Ag alloy, and Ni alloy are used as electrode materials for flat panel displays such as liquid crystal displays. A sputtering method (sputtering process) is applied to the formation of the electrode, and a sputtering target material used in the sputtering method is made of a metal that serves as an electrode. With the increase in the size of flat panel displays such as liquid crystal displays, the size of the sputtering target material has increased, and the quality of the sputtering target material has been studied. That is, a sputtering target material that has a high film formation rate and is unlikely to generate particles and arcing (abnormal discharge) has been studied.
　例えば、特許文献１では、スパッタ面のＸ線回折パターンと該スパッタ面にほぼ直交する側面のＸ線回折パターンが同じであることを特徴とするスパッタターゲット材に関するものである。このように、スパッタリングターゲット材の結晶粒が配向せず、結晶性に異方性のないようにすることで、既存の成膜条件を変更することなく成膜速度を増大させることができるとしている。 For example, Patent Document 1 relates to a sputter target material characterized in that the X-ray diffraction pattern on the sputter surface is the same as the X-ray diffraction pattern on the side surface substantially orthogonal to the sputter surface. Thus, it is said that the film formation rate can be increased without changing the existing film formation conditions by making the crystal grains of the sputtering target material not oriented and having no crystallinity anisotropy. .
　また、特許文献２では、アーキングが起きるという問題を解消するために、水素中での焼結によって得られたＭｏ（モリブデン）インゴット（特許文献２では、「インゴット」を、焼結によって得られた金属塊を意味して使用されており、通常、「ブロック」とも言う。ここでは、以下「ブロック」という。）を１３００℃以下の温度で圧延し、このＭｏ圧延板を熱処理することによって、ランダムな結晶方位を備え、再結晶粒径の平均が１００μｍ以下であるＭｏスパッタリングターゲット材が開示されている。Ｍｏスパッタリングターゲット材の結晶粒径が均一で、結晶方位がランダムであると、スパッタ中のパーティクル発生やアーキングが抑制されるとしている。 Further, in Patent Document 2, in order to solve the problem of arcing, Mo (molybdenum) ingot obtained by sintering in hydrogen (in Patent Document 2, “ingot” was obtained by sintering). It is used to mean a lump of metal, and is usually also referred to as “block. Here, it is hereinafter referred to as“ block. ”) Is rolled at a temperature of 1300 ° C. or less, and this Mo rolled sheet is heat treated to randomly A Mo sputtering target material having a proper crystal orientation and an average recrystallized grain size of 100 μm or less is disclosed. If the crystal grain size of the Mo sputtering target material is uniform and the crystal orientation is random, the generation of particles and arcing during sputtering are suppressed.
　同様に、特許文献３には、パーティクル発生や異常放電（アーキング）発生を抑制するために、スパッタリングターゲットの結晶粒径を微細で均一にするとともに、配向性は低いこと、即ち無配向に近いことが望ましいとされている。前記配向性に関して、具体的には、Ｘ線回折における主ピーク５点で規格化した、Ｍｏ（１１０）面の相対強度比Ｒ（１１０）とＭｏ（２００）面の相対強度Ｒ（２００）が共に１０％以上、３０％以下とすることが記載されている。 Similarly, in Patent Document 3, in order to suppress generation of particles and abnormal discharge (arcing), the crystal grain size of the sputtering target is made fine and uniform, and the orientation is low, that is, non-oriented. Is preferred. Regarding the orientation, specifically, the relative intensity ratio R (110) of the Mo ( 110 ) plane and the relative intensity R (200) of the Mo (200) plane, normalized by five main peaks in X-ray diffraction, are used. Both are described as 10% or more and 30% or less.
　また、特許文献４には、高パワー密度のスパッタリングにおけるアーキング発生を抑制するために、金属スパッタリングターゲットの主要構成元素以外の不純物元素濃度を５００ｐｐｍ以上、１０００ｐｐｍ以下にすることが開示されている。不純物元素は、スパッタリングターゲットの金属元素とスパッタ率が異なるために、スパッタリングが進むと、アーキングが発生起点となる突起を形成し易いと記載されている。 Patent Document 4 discloses that the concentration of impurity elements other than the main constituent elements of the metal sputtering target is 500 ppm or more and 1000 ppm or less in order to suppress the occurrence of arcing in high power density sputtering. It is described that since the impurity element has a sputtering rate different from that of the metal element of the sputtering target, it is easy to form a protrusion from which arcing occurs when sputtering progresses.
　Ｍｏを主成分とするスパッタリングターゲット材に関して、含有酸素量を低減することで性能を改善することも検討されている。特許文献５には、ジルコニウムと残部モリブデンを含有するスパッタリングターゲット材において、含有酸素量を低減することで、圧延加工を容易にし、スパッタリング時の成膜特性を優れたものにできることが開示されている。成膜特性として、具体的にはパーティクルの発生頻度が示されている。また、酸素含有量としては、０．０５％から０．３％に低減することが好ましいとしている。 Regarding a sputtering target material containing Mo as a main component, it has been studied to improve performance by reducing the oxygen content. Patent Document 5 discloses that in a sputtering target material containing zirconium and the remaining molybdenum, the amount of oxygen contained can be reduced to facilitate rolling and to improve the film formation characteristics during sputtering. . Specifically, the frequency of generation of particles is shown as the film forming characteristic. Further, the oxygen content is preferably reduced from 0.05% to 0.3%.
　同様に、特許文献６では、Ｍｏスパッタリングターゲット材を製造するにあたり、Ｍｏ焼結体の酸素含有量を５００ｐｐｍ以下にすることで、塑性加工が容易になり、スパッタリングターゲット材としては酸化物粒子相の形成が少なくなるのでパーティクルの発生を抑制できるとされている。更に、ＢＣＣ（体心立方格子）結晶構造を有するＭｏの最稠密面である（１１０）面の相対強度比を高めることによって、スパッタリングレート（成膜速度）が高くなり、生産性を向上させることができるとしている。具体的には、Ｘ線回折における主ピーク４点で規格化した（１１０）面の相対強度比Ｒ（１１０）が４０％以上であることが望ましいとしている。ここでは、圧延時の１パス当たりの圧下率の好ましい範囲としては１０％以下とし、具体的には１パスあたり４％程度の圧下率で上記組織を得たことを示していた。 Similarly, in Patent Document 6, in manufacturing the Mo sputtering target material, by making the oxygen content of the Mo sintered body 500 ppm or less, plastic working becomes easy, and the sputtering target material is an oxide particle phase. It is said that the generation of particles can be suppressed because the formation is reduced. Furthermore, by increasing the relative intensity ratio of the (110) plane, which is the most dense surface of Mo having a BCC (body-centered cubic lattice) crystal structure, the sputtering rate (deposition rate) is increased and productivity is improved. I can do it. Specifically, it is desirable that the relative intensity ratio R (110) of the (110) plane normalized by four main peaks in X-ray diffraction is 40% or more. Here, it was shown that the preferable range of the rolling reduction per pass during rolling was 10% or less, and specifically, that the structure was obtained at a rolling reduction of about 4% per pass.
　特許文献７では、加圧焼結を施してなるターゲット材であって、平均粒径１０μｍ以下の微細組織を有し、かつ相対密度が９９％以上であるモリブデンターゲットが示されている。このような組織に制御することにより、スパッタリング膜が均一となり、膜中のパーティクル数が低減できるとしている。
特開２０００－０４５０６５号公報 特開２０００－２３４１６７号公報 特開２０００－０４５０６６号公報 特開２００５－１５４８１４号公報 特開２００２－３３９０３１号公報 特開２００７－１１３０３３号公報 特開平１０－１８３３４１号公報 Patent Document 7 discloses a molybdenum target that is a pressure-sintered target material that has a fine structure with an average particle size of 10 μm or less and a relative density of 99% or more. By controlling to such a structure, the sputtering film becomes uniform and the number of particles in the film can be reduced.
JP 2000-045065 A JP 2000-234167 A JP 2000-045066 A JP 2005-154814 A JP 2002-339031 A JP 2007-113033 A Japanese Patent Laid-Open No. 10-183341
　上述のように、種々の観点から、スパッタリングターゲット材の改善が進められている。一方、液晶ディスプレイ等のフラットパネルディスプレイの製造において、電極を形成するスパッタリング工程は、他の工程に比べてスループットが遅く、製造効率向上や最終製品のコスト低減の観点から、スパッタリング工程にはより高いスループットが求められるようになってきている。即ち、上述のようなこれまで行われてきた、成膜速度、パーティクル発生、アーキング（異常放電）発生等といったそれぞれの特性要素の改善といったものではなく、製造工程における高いスループットというトータルソリューションとしての性能向上がスパッタリングターゲット材に求められるようになってきた。 As described above, the sputtering target material is being improved from various viewpoints. On the other hand, in the production of flat panel displays such as liquid crystal displays, the sputtering process for forming electrodes has a slower throughput than other processes, and is higher in the sputtering process from the viewpoint of improving production efficiency and reducing the cost of the final product. Throughput has been demanded. In other words, it does not improve the respective characteristics such as film formation speed, particle generation, arcing (abnormal discharge) generation, etc., which have been performed so far, but the performance as a total solution of high throughput in the manufacturing process. Improvements have come to be sought for sputtering target materials.
　スパッタリング工程においてスループットを向上させる１つの方法としては、スパッタリングのパワーを上げて成膜速度を大きくすることが考えられる。しかしながら、高いパワー密度でスパッタリングするとアーキングの発生率が増加して、結局、スループットを向上できないという問題が起こる。また、特許文献６に記載のように、スパッタリングターゲットの金属結晶の最稠密面（ＢＣＣ結晶構造を有するＭｏの（１１０）面）の相対強度比を高めることによって、成膜速度を大きくするという考え方もできるが、実際には金属原子の平面密度が高い面ほど多くのスパッタ原子（スパッタ粒子）が放出されて成膜速度が向上するとは限らない。特に、スパッタリングのパワーによって、スパッタ原子の放出挙動が異なる。したがって、これまでは、スパッタリングターゲット材の結晶配向とスパッタ粒子の放出方向の因果関係は明らかになっておらず、スパッタ面にどのような組織または、結晶組織を持ったターゲットが成膜速度に対して有効であるかわからない状況であった。 As one method for improving the throughput in the sputtering process, it is conceivable to increase the sputtering power to increase the deposition rate. However, when sputtering is performed at a high power density, the rate of arcing increases, resulting in a problem that throughput cannot be improved. Further, as described in Patent Document 6, the idea of increasing the deposition rate by increasing the relative intensity ratio of the densest surface of the metal crystal of the sputtering target (the (110) surface of Mo having a BCC crystal structure). However, in practice, the higher the plane density of metal atoms, the more sputtered atoms (sputtered particles) are released and the film formation rate is not always improved. In particular, the emission behavior of sputtered atoms varies depending on the sputtering power. Thus, until now, the causal relationship between the crystal orientation of the sputtering target material and the emission direction of the sputtered particles has not been clarified. The situation is unknown.
　本発明では、高密度パワーを使用しなくても高い成膜速度が得られ、アーキング発生を低減でき、スパッタリング工程のスループットを飛躍的に向上できる金属系スパッタリングターゲット材を提供することを目的とする。 An object of the present invention is to provide a metal-based sputtering target material that can obtain a high film formation rate without using high-density power, can reduce the occurrence of arcing, and can dramatically improve the throughput of the sputtering process. .
　本発明者らは、スループット性能を向上させるスパッタリングターゲット材の好ましい集合組織とするために、スパッタリングターゲット材として使用される立方晶系の結晶構造である金属について、各結晶面からの金属原子放出能を調べた結果、{２００}面と｛２２２｝面が高い金属原子放出能をすることを見出した。前記知見に基づき、スパッタリングターゲット材を作製し、そのスループット性能を検討した結果、特定の範囲の低い酸素含有量で、スパッタ面に対する結晶相の{２００}面集積度と｛２２２｝面集積度が高いスパッタリングターゲット材が、極めて優れたスループット性能を示すこと見出し、本発明に到達した。即ち、本発明は、以下の要旨とするものである。 In order to obtain a preferred texture of a sputtering target material that improves throughput performance, the present inventors have made it possible to release metal atoms from each crystal plane for a metal having a cubic crystal structure used as a sputtering target material. As a result, it was found that the {200} plane and the {222} plane have a high metal atom releasing ability. As a result of producing a sputtering target material based on the above knowledge and examining its throughput performance, the {200} plane integration degree and {222} plane integration degree of the crystal phase with respect to the sputtered surface with a low oxygen content in a specific range are obtained. The inventors have found that a high sputtering target material exhibits extremely excellent throughput performance, and reached the present invention. That is, the present invention has the following gist.
（１）立方晶系の結晶構造である金属又は合金から構成されているスパッタリングターゲット材であって、前記スパッタリングターゲット材に含有する酸素含有量が質量で５ｐｐｍ以上５００ｐｐｍ以下であり、スパッタ面に対する結晶相の{２００}面集積度が１５％以上８０％以下、または、スパッタ面に対する結晶相の{２２２}面集積度が１５％以上８０％以下であることを特徴とする金属系スパッタリングターゲット材。
（２）前記スパッタリングターゲット材のスパッタ面に対する結晶相の{２００}面集積度と{２２２}面集積度の和が、３０％以上９５％以下であることを特徴とする上記（１）記載の金属系スパッタリングターゲット材。
（３）前記スパッタリングターゲット材のスパッタ面に対する{１１０}面集積度が、０．０１％以上８％以下であることを特徴とする上記（１）又は（２）記載の金属系スパッタリングターゲット材。
（４）前記スパッタリングターゲット材を構成する金属又は合金が、Ｃｒ、Ｍｏ、Ｗ、Ｖ、又はＴａのいずれか１つ以上を主元素とし、その結晶構造が立方晶系の体心立方格子構造を有することを特徴とする上記（１）～（３）のいずれかに記載の金属系スパッタリングターゲット材。
（５）前記スパッタリングターゲット材の結晶相の結晶粒径が、１μｍ以上５０μｍ以下であることを特徴とする上記（１）～（４）のいずれかに記載の金属系スパッタリングターゲット材。 (1) A sputtering target material composed of a metal or alloy having a cubic crystal structure, wherein the oxygen content contained in the sputtering target material is 5 ppm to 500 ppm in mass, A metal-based sputtering target material, wherein the {200} plane integration degree of the phase is 15% or more and 80% or less, or the {222} plane integration degree of the crystal phase with respect to the sputtering surface is 15% or more and 80% or less.
(2) The sum of the {200} plane integration degree and {222} plane integration degree of the crystal phase with respect to the sputtering surface of the sputtering target material is 30% or more and 95% or less. Metal sputtering target material.
(3) The metal-based sputtering target material according to (1) or (2) above, wherein the {110} plane integration degree with respect to the sputtering surface of the sputtering target material is 0.01% or more and 8% or less.
(4) The metal or alloy constituting the sputtering target material has one or more of Cr, Mo, W, V, or Ta as a main element, and the crystal structure is a cubic system centered cubic lattice structure. The metal-based sputtering target material as described in any one of (1) to (3) above,
(5) The metal-based sputtering target material according to any one of (1) to (4) above, wherein the crystal grain size of the crystal phase of the sputtering target material is 1 μm or more and 50 μm or less.
　本発明の金属系スパッタリングターゲット材によれば、スパッタリング工程におけるスループット性能が向上する。また、液晶ディスプレイ等のフラットパネルディスプレイ等の電極膜作製が効率的になる。また、得られる電極膜は高品位なため、高性能な製品が提供できるようになる。 According to the metal-based sputtering target material of the present invention, the throughput performance in the sputtering process is improved. In addition, it is possible to efficiently produce electrode films for flat panel displays such as liquid crystal displays. In addition, since the obtained electrode film is of high quality, a high-performance product can be provided.
　本発明者らは、立方晶系の結晶構造である金属又は合金から構成されているスパッタリングターゲット材について、上述のように集合組織と含有酸素濃度を制御することによって、スパッタリング工程におけるスループット性能が著しく向上できることを見出した。上述のように、スループット性能は、主に成膜速度とアーキング発生回数との関係によって表される。例えば、スループット特性は、成膜速度が大きいほど良く、アーキング発生回数は小さいほど良くなる。 The inventors of the present invention have a remarkable throughput performance in the sputtering process by controlling the texture and the oxygen concentration of the sputtering target material composed of a metal or alloy having a cubic crystal structure as described above. I found that it can be improved. As described above, the throughput performance is mainly represented by the relationship between the film formation rate and the number of arcing occurrences. For example, the throughput characteristics are better as the film forming speed is higher and as the number of arcing occurrences is smaller.
　発明者らは、成膜速度に関し、スパッタリングターゲット材として使用される立方晶系の結晶構造である金属について、各結晶面からの金属原子放出能を調べた結果、{２００}面が高い金属原子放出能を有することを見出した。具体的な例として、立方晶系の結晶構造であるＭｏを使用して、前記Ｍｏ結晶相の{２００}、{１１０}、{２１１}、{３１０}、及び{２２２}面のそれぞれに、加速電圧１０ｋＶと３０ｋＶの集束イオンビーム(FIB, Focused Ion Beam)をそれぞれ一定時間照射して、照射され加工された部位の体積を測定し、原子放出量を計算した。 As a result of investigating the metal atom releasing ability from each crystal face of a metal having a cubic crystal structure used as a sputtering target material with respect to the film formation rate, the inventors have found that a metal atom having a high {200} face. It has been found that it has a releasing ability. As a specific example, using Mo having a cubic crystal structure, each of the {200}, {110}, {211}, {310}, and {222} planes of the Mo crystal phase, A focused ion beam (FIB, Focused Ion Beam) with an acceleration voltage of 10 kV and 30 kV was respectively irradiated for a certain period of time, and the volume of the irradiated and processed part was measured to calculate the amount of atomic emission.
　図１は、{２００}面における原子放出量を１００として、その他の各結晶面の原子放出量を相対値で示したものである。{２００}面が、原子放出速度が大きく、特に、印加するエネルギー（イオンビームの加速電圧）が低いほど顕著である。単位面積当たりの原子数としては、{１１０}面が多いのであるが、原子放出速度は{２００}面と｛２２２｝面の方が大きくなっているのは、{２００}面と｛２２２｝面の原子放出能が高いためであると推測される。前記原子放出速度は、スパッタリングにおける成膜速度と相関し、原子放出速度が大きいほど成膜速度が大きくなるものと考えられる。一方、{１１０}面は、特に、低加速電圧で原子放出速度が低く、すなわち、{１１０}面では原子放出能が低い、或いは、原子放出には高いエネルギーが必要であると考えられる。 FIG. 1 shows the amount of atomic emission on the other crystal planes as relative values, with the amount of atomic emission on the {200} plane being 100. The {200} plane has a higher atomic emission rate, and is particularly remarkable as the applied energy (acceleration voltage of the ion beam) is lower. As for the number of atoms per unit area, there are many {110} planes, but the atomic emission rates are larger on the {200} plane and {222} plane than the {200} plane and {222} plane. This is presumed to be due to the high atomic emission ability of the surface. The atomic emission rate correlates with the deposition rate in sputtering, and it is considered that the deposition rate increases as the atomic emission rate increases. On the other hand, it is considered that the {110} plane has a particularly low atomic emission rate at a low acceleration voltage, that is, the {110} plane has a low atomic emission capability, or high energy is required for atomic emission.
　上記知見に基づき、スパッタリングターゲット材を作製し、そのスループット性能を検討した結果、特定の範囲の低い酸素含有量で、スパッタ面に対する結晶相の{２００}面集積度と｛２２２｝面集積度が高い集合組織としたスパッタリングターゲット材が、極めて優れたスループット性能を示すこと見出した。具体的には、以下のようである。 As a result of producing a sputtering target material based on the above knowledge and examining its throughput performance, the {200} plane integration degree and {222} plane integration degree of the crystal phase with respect to the sputter surface are low with a specific range of low oxygen content. It has been found that a sputtering target material having a high texture exhibits extremely excellent throughput performance. Specifically, it is as follows.
　本発明のスパッタリングターゲット材の集合組織は、スパッタ面に対する結晶相の｛２００｝面集積度が１５％以上８０％以下、または、スパッタ面に対する結晶相の{２２２}面集積度が１５％以上８０％以下である。{２００}面集積度と{２２２}面集積度の両方が１５％未満では、成膜速度の向上が見られない。一方、{２００}面集積度が８０％を超えると、成膜速度は向上するものの、結晶面をそろえるために製造に手間がかかったり、多結晶の集合組織としては実質的に製造できなかったりする。 In the texture of the sputtering target material of the present invention, the {200} plane integration degree of the crystal phase with respect to the sputtering surface is 15% or more and 80% or less, or the {222} plane integration degree of the crystal phase with respect to the sputtering surface is 15% or more and 80%. % Or less. When both the {200} plane integration degree and the {222} plane integration degree are less than 15%, the film formation rate is not improved. On the other hand, when the {200} plane integration degree exceeds 80%, the film formation rate is improved, but it takes time to manufacture because the crystal planes are aligned, or it cannot be manufactured substantially as a polycrystalline texture. To do.
　また、{２００}面集積度が高くなりすぎて８０％を超えると、結晶粒が粗大化し、粒界の無い単結晶となってしまうので、スパッタリングターゲット材として使用する場合、取り扱いの際に、へき開して割れたり、スパッタリング中の熱で割れたりする。同様に、{２２２}面集積度が８０％を超えると、成膜速度は向上するものの、結晶面をそろえるために製造に手間がかかったり、多結晶の集合組織としては実質的に製造できなかったりする。また、{２２２}面集積度が高くなりすぎて８０％を超えると結晶粒が粗大化し、粒界の無い単結晶に極めて近い組織になってしまうので、スパッタリングターゲット材として使用する場合、取り扱いの際に、へき開して割れたり、スパッタリング中の熱で割れたりする。 Also, if the {200} plane integration degree becomes too high and exceeds 80%, the crystal grains become coarse and become a single crystal without grain boundaries. Therefore, when used as a sputtering target material, It cleaves when cleaved or cracks due to heat during sputtering. Similarly, when the {222} plane integration degree exceeds 80%, the film formation rate is improved, but it takes time to manufacture because the crystal planes are aligned, and it cannot be substantially manufactured as a polycrystalline texture. Or In addition, if the {222} plane integration degree becomes too high and exceeds 80%, the crystal grains become coarse and become a structure very close to a single crystal having no grain boundary. In some cases, it is cleaved and cracked, or cracked by heat during sputtering.
　成膜速度と製造コストの観点から、{２００}面集積度と{２２２}面集積度の和の範囲は３０％以上９５％以下である方が、より好ましい。{２００}面集積度と{２２２}面集積度の和の範囲が、３０％未満では、本発明で得られる作用効果の範囲内であるが、成膜速度が低くなる場合がある。一方、{２００}面集積度と{２２２}面集積度の和の範囲が、９５％を超えると、成膜速度ははやくなるが、{２００}面と{２２２}面との粒界は存在するがその占める割合が少なくなって、単結晶のようにへき開して割れやすくなったり、スパッタリング中の熱で割れたりする場合がある。{２００}面集積度と{２２２}面集積度の和の範囲が、更により好ましいのは、６０％以上９５％以下である。 From the viewpoint of film formation speed and manufacturing cost, it is more preferable that the range of the sum of the {200} plane integration degree and the {222} plane integration degree is 30% or more and 95% or less. If the range of the sum of the {200} plane integration degree and the {222} plane integration degree is less than 30%, it is within the range of the effects obtained by the present invention, but the film formation rate may be low. On the other hand, when the range of the sum of {200} plane integration and {222} plane integration exceeds 95%, the film formation rate becomes fast, but there is a grain boundary between {200} plane and {222} plane. However, the ratio of the occupancy decreases, and it may be cleaved and easily broken like a single crystal, or may be cracked by heat during sputtering. The range of the sum of the {200} plane integration degree and the {222} plane integration degree is more preferably 60% or more and 95% or less.
　更に、本発明では、スパッタリングターゲット材の{１１０}面集積度が、０．０１％以上８％以下であるのが好ましい。これは、電子放出能が小さい{１１０}の面集積度が低い方が、大きな成膜速度が維持できるためである。よって、{１１０}面集積度が８％を超えると、成膜速度の飛躍的な向上が見られない場合がある。一方、{１１０}面集積度が、０．０１％未満とするには、成膜速度の更な向上が飽和したり、前記結晶面を低減するために製造に手間がかかったりする場合がある。特に、成膜速度及びターゲット製造コストの観点から、より好ましい{１１０}面集積度の範囲は、０．０１％以上３％以下である。 Furthermore, in the present invention, the {110} plane integration degree of the sputtering target material is preferably 0.01% or more and 8% or less. This is because a larger film deposition rate can be maintained when the surface integration degree of {110} having a smaller electron emission capability is lower. Therefore, if the {110} plane integration degree exceeds 8%, the film formation speed may not be dramatically improved. On the other hand, if the {110} plane integration degree is less than 0.01%, further improvement of the film formation rate may be saturated, or production may be time-consuming to reduce the crystal plane. . In particular, from the viewpoint of film formation speed and target manufacturing cost, a more preferable range of {110} plane integration is 0.01% or more and 3% or less.
　ここで、上記面集積度の測定は、Ｘ線回折法によって行うことができ、例えば、ＭｏＫα線を用いる。結晶相の｛２００｝面集積度、｛２２２｝面集積度、および、｛１１０｝面集積度は以下のように求める。試料表面に対して平行な立方晶の結晶１１面｛１１０｝、｛２００｝、｛２１１｝、｛３１０｝、｛２２２｝、｛３２１｝、｛４１１｝、｛４２０｝、｛３３２｝、｛５２１｝、｛４４２｝の積分強度を測定し、その測定値それぞれをランダム方位である試料の理論積分強度で除した後、｛２００｝あるいは｛１１０｝強度の比率を百分率で求める。これは、例えば、｛２００｝強度比率では、以下の式（１）で表される。 Here, the measurement of the degree of surface integration can be performed by an X-ray diffraction method, for example, using MoKα rays. The {200} plane integration degree, {222} plane integration degree, and {110} plane integration degree of the crystal phase are obtained as follows. Cubic crystal 11 plane parallel to the sample surface {110}, {200}, {211}, {310}, {222}, {321}, {411}, {420}, {332}, { 521} and {442} are measured, and each measured value is divided by the theoretical integrated intensity of the sample having a random orientation, and then the ratio of {200} or {110} intensity is obtained as a percentage. This is expressed, for example, by the following formula (1) in the {200} intensity ratio.
｛２００｝面集積度
Figure JPOXMLDOC01-appb-M000001
 {200} surface integration degree
Figure JPOXMLDOC01-appb-M000001
ただし、記号は以下の通りである。
　　ｉ（ｈｋｌ）：測定した試料における｛ｈｋｌ｝面の実測積分強度
　　Ｉ（ｈｋｌ）：ランダム方位をもつ試料における｛ｈｋｌ｝面の理論積分強度
　　Σ：立方晶結晶１１面についての和
　尚、スパッタリングターゲット材の中で集合組織を測定する場所としては、未使用のスパッタリングターゲット材表面に対して、最表面から１ｍｍ深さ位置～ターゲット材厚みの半分位置の範囲内で、厚み方向の深さ位置を選ぶ。スパッタリングで使用される部位を選ぶことが重要である。 However, the symbols are as follows.
i (hkl): Measured integrated intensity of {hkl} plane in the measured sample I (hkl): Theoretical integrated intensity of {hkl} plane in the sample with random orientation Σ: Sum of the cubic crystal 11 plane As a place to measure the texture in the material, the depth position in the thickness direction is within the range of 1 mm depth position from the outermost surface to half the target material thickness with respect to the surface of the unused sputtering target material. Choose. It is important to select the site used for sputtering.
　本発明のスパッタリングターゲット材に含有する酸素含有量は、質量で５ｐｐｍ以上５００ｐｐｍ以下である。前記酸素含有量で、上記結晶面の面集積度であると、大きな成膜速度であり、更にアーキング発生回数も飛躍的に低減でき、極めて優れたスループット性能が得られる。前記酸素含有量が５ｐｐｍ未満であると、アーキング発生回数は低くできるが、製造時の還元処理過程で著しく時間と手間がかかるので実用的でない。一方、前記酸素含有量が５００ｐｐｍを超えると、スパッタリングターゲット材の内部に酸化物が形成され、その影響で特にアーキング発生回数が増加し、その結果スループット性能が低下する。より好ましい酸素含有量の範囲は１０ｐｐｍ以上２００ｐｐｍ以下であり、この範囲では、より高いスループット性能が得られる。さらに、酸素含有量が１０ｐｐｍ以上１００ｐｐｍ未満ならば、アーキング発生をほとんど無くすことができるため、より望ましい。上記のように酸素含有量は、アーキング発生に大きく影響するものであるが、｛２００｝面と｛２２２｝面の面集積度が低くなってもアーキング発生が起こりやすくなる傾向にある。すなわち、前記面集積度もアーキング発生に影響する。前記面集積度が低下して成膜速度が遅くなるということは、金属原子放出能が低下するということを意味する。金属原子が放出されなくなると、金属原子放出能の低下を補うように異常放電（アーキング）が起こるのである。 The oxygen content contained in the sputtering target material of the present invention is 5 ppm or more and 500 ppm or less by mass. When the oxygen content is the plane integration degree of the crystal plane, the film formation rate is high, the number of arcing occurrences can be drastically reduced, and extremely excellent throughput performance can be obtained. If the oxygen content is less than 5 ppm, the number of occurrences of arcing can be reduced, but it is not practical because it takes a lot of time and labor during the reduction process during production. On the other hand, when the oxygen content exceeds 500 ppm, an oxide is formed inside the sputtering target material, and the number of occurrences of arcing increases due to the influence, resulting in a decrease in throughput performance. A more preferable range of oxygen content is 10 ppm or more and 200 ppm or less, and in this range, higher throughput performance can be obtained. Furthermore, if the oxygen content is 10 ppm or more and less than 100 ppm, the occurrence of arcing can be almost eliminated, which is more desirable. As described above, the oxygen content greatly affects the occurrence of arcing, but there is a tendency that arcing tends to occur even if the degree of integration of the {200} plane and {222} plane decreases. That is, the degree of surface integration also affects the occurrence of arcing. The fact that the surface integration degree is reduced and the film formation rate is slow means that the metal atom releasing ability is lowered. When metal atoms are not released, abnormal discharge (arcing) occurs to compensate for the decrease in metal atom release ability.
　本発明のスパッタリングターゲット材の結晶粒径が特定の範囲にあると、更にスループット性能が向上する。スループット性能に影響する次の因子としては結晶粒径が挙げられる。結晶粒径が大きくなるほど粒界の占める割合が小さくなり、スループット性能が向上する。望ましい範囲は１μｍ以上５０μｍ以下である。結晶粒径が１μｍ以下では、｛２００｝、または、｛２２２｝面集積度を本発明範囲に制御することが難しい場合がある。さらに、より望ましい範囲は１０μｍ超５０μｍ以下である。一方、結晶粒径が５０μｍ超であっても、アーキング発生回数が低減されない場合があり、スループット性能の更なる向上が望めない場合がある。ここで、結晶粒径は線分法で求めた平均値である。測定した箇所は表面から厚み方向へ最表面から１ｍｍ～ターゲット材厚みの半分の位置の範囲内で離れた位置で、圧延面に平行な面、圧延方向に平行で圧延面に垂直な面、圧延方向に垂直で圧延面に垂直な面のそれぞれで金属組織を観察し、線分法で測定した結晶粒径をさらに平均化する。 If the crystal grain size of the sputtering target material of the present invention is in a specific range, the throughput performance is further improved. The next factor affecting the throughput performance is the crystal grain size. The larger the crystal grain size, the smaller the proportion of grain boundaries, and the throughput performance is improved. A desirable range is 1 μm or more and 50 μm or less. When the crystal grain size is 1 μm or less, it may be difficult to control the degree of {200} or {222} plane integration within the range of the present invention. Further, a more desirable range is more than 10 μm and 50 μm or less. On the other hand, even if the crystal grain size exceeds 50 μm, the number of occurrences of arcing may not be reduced, and further improvement in throughput performance may not be expected. Here, the crystal grain size is an average value obtained by a line segment method. The measured location is from the surface to the thickness direction within a range of 1 mm from the outermost surface to half the target material thickness, parallel to the rolling surface, parallel to the rolling direction and perpendicular to the rolling surface, rolling The metal structure is observed on each of the surfaces perpendicular to the direction and perpendicular to the rolling surface, and the crystal grain size measured by the line segment method is further averaged.
　本発明の金属系スパッタリングターゲット材は、立方晶系の結晶構造である金属又は合金から構成されている。前記金属又は合金は、立方晶系の結晶構造を有していれば、特に限定されないが、例えば、前記金属又は合金を構成する主金属元素として、Ｃｒ、Ｍｏ、Ｗ、Ｖ、Ｎｂ、Ｔａ、Ｆｅ、Ｐｄ、Ｐｔ、Ｉｒ、Ａｕ、Ａｇ、Ｃｕ、Ａｌ、Ｎｉ等が挙げられる。中でも、スパッタリングターゲット材を構成する金属又は合金が、Ｃｒ、Ｍｏ、Ｗ、Ｖ、又はＴａのいずれか１つ以上を主元素とし、その結晶構造が立方晶系の体心立方格子（ＢＣＣ）構造を有するのがより望ましい。 The metal sputtering target material of the present invention is composed of a metal or alloy having a cubic crystal structure. The metal or alloy is not particularly limited as long as it has a cubic crystal structure. For example, as a main metal element constituting the metal or alloy, Cr, Mo, W, V, Nb, Ta, Fe, Pd, Pt, Ir, Au, Ag, Cu, Al, Ni etc. are mentioned. In particular, the metal or alloy constituting the sputtering target material has one or more of Cr, Mo, W, V, or Ta as a main element, and the crystal structure thereof is a cubic body-centered cubic lattice (BCC) structure. It is more desirable to have
　これらは、一元系金属であっても良いし、他の元素を加えた合金（多元系金属）であっても良い。合金の例としては、Ｃｒ－Ｍｏ、Ｍｏ－Ｗ、Ｍｏ－Ｎｂ等が挙げられる。前記金属又は合金は立方晶金属であり、ＢＣＣ構造を有していれば良い。また、完全に合金化していなくても、最も大きな体積比の物質を主相とし、これらが立方晶金属であり、ＢＣＣ構造を有していれば良い。ここで、Ｃｒ、Ｍｏ、Ｗ、Ｖ、又はＴａの金属は電気抵抗が低く、電極材として適しているとともに、スループット性能がよい場合が比較的多い。  These may be single-component metals or alloys (multi-component metals) with other elements added. Examples of the alloy include Cr—Mo, Mo—W, and Mo—Nb. The metal or alloy is a cubic metal and may have a BCC structure. Moreover, even if it is not completely alloyed, it is only necessary that a substance having the largest volume ratio is a main phase, these are cubic metals, and have a BCC structure. Here, Cr, Mo, W, V, or Ta metal has a low electrical resistance, is suitable as an electrode material, and has a relatively high throughput performance in many cases.
　本発明の金属系スパッタリングターゲット材の製造方法は、溶融法、粉末冶金法等を利用でき、特に限定されないが、例えば、ブロックを製造する工程と、加熱したブロックを圧延等で塑性変形させて大面積化する工程から構成される製造方法が好ましい。即ち、ブロックに含有する酸素濃度、平均結晶粒径、相対密度を特定範囲に制御し、さらに特定温度範囲で塑性変形させることによって、本発明の集合組織を有するスパッタリングターゲット材が容易に得られる。そこで、前記製造方法について、以下にその詳細を記載する。 The manufacturing method of the metal-based sputtering target material of the present invention can utilize a melting method, a powder metallurgy method, and the like, and is not particularly limited. For example, the step of manufacturing the block and the heated block are plastically deformed by rolling or the like. A production method comprising a step of areaization is preferred. That is, the sputtering target material having the texture of the present invention can be easily obtained by controlling the oxygen concentration, average crystal grain size, and relative density contained in the block within a specific range and further plastically deforming within a specific temperature range. Therefore, the details of the manufacturing method will be described below.
　本発明のスパッタリングターゲット材の集合組織を好適に得るためには、ブロックが以下の条件であると好ましい。 In order to suitably obtain the texture of the sputtering target material of the present invention, the block preferably has the following conditions.
　まず、圧延前のブロック材に含有される酸素濃度は少なくとも５００質量ｐｐｍよりも低くするのが好ましい。５００質量ｐｐｍ超であると本発明の集合組織が得られない場合があったり、圧延中に耳割れや亀裂が発生して歩留まりが著しく低下する場合があったりする。前記ブロックの酸素濃度は、原料となる金属粉末の酸素濃度（酸素含有量）に依存し、酸素含有量の異なる原料金属粉末を選んだり、原料金属粉末を酸化や還元処理したりすることで、前記ブロックの酸素濃度を制御ことが可能である。また、熱間静水圧プレス（以下「ＨＩＰ」という）によって原料金属粉末を高温・高圧下で焼結させる場合、原料金属粉末の酸素含有量が多い場合には、ＨＩＰ前の金属粉末を予め水素ガス等の還元雰囲気中で熱処理して含有する酸素濃度を減少させることもできる。また、粉末をＣＩＰ（冷間静水圧プレス）やプレス加工等で仮成形させた後に、仮成形体を同様に還元雰囲気中で熱処理して含有する酸素濃度を減少させることも可能である。 First, the oxygen concentration contained in the block material before rolling is preferably at least lower than 500 ppm by mass. If it exceeds 500 ppm by mass, the texture of the present invention may not be obtained, or ear cracks and cracks may occur during rolling, and the yield may be significantly reduced. The oxygen concentration of the block depends on the oxygen concentration (oxygen content) of the metal powder as a raw material, and by selecting a raw metal powder having a different oxygen content, or by oxidizing or reducing the raw metal powder, It is possible to control the oxygen concentration of the block. In addition, when the raw metal powder is sintered at high temperature and high pressure by hot isostatic pressing (hereinafter referred to as “HIP”), if the oxygen content of the raw metal powder is high, the metal powder before HIP is preliminarily hydrogenated. It is also possible to reduce the oxygen concentration contained by heat treatment in a reducing atmosphere such as gas. In addition, after the powder is temporarily formed by CIP (cold isostatic pressing), pressing, or the like, the temporary formed body is similarly heat-treated in a reducing atmosphere to reduce the oxygen concentration contained.
　圧延前のブロックの結晶粒径は１μｍ超５０μｍ以下であることが望ましい。この範囲の中でも結晶粒径が１０μｍ超５０μｍ以下であると、本発明範囲への集合組織の制御が容易である。結晶粒径が１μｍ未満のブロックは製造困難な場合がある。５０μｍを超えると本発明の集合組織が得られ難くなる場合があったり、圧延中に割れが発生しやすくなる場合があったりする。前記ブロックの結晶粒径は、後述の製造方法でも説明するように、原料の金属粉末の粒径と、前記金属粉末が粒成長しながら焼結する条件から制御することができる。 The crystal grain size of the block before rolling is desirably more than 1 μm and 50 μm or less. Within this range, if the crystal grain size is more than 10 μm and not more than 50 μm, it is easy to control the texture within the range of the present invention. A block having a crystal grain size of less than 1 μm may be difficult to manufacture. If it exceeds 50 μm, the texture of the present invention may be difficult to obtain, or cracks may easily occur during rolling. The crystal grain size of the block can be controlled from the grain size of the raw metal powder and the conditions under which the metal powder is sintered while growing the grains, as will be described later in the production method.
　圧延前のブロックの相対密度は、圧延に伴う集合組織形成に重要な影響を及ぼし、相対密度の望ましい範囲は９０．０％以上９９．０％未満である。相対密度がこの範囲であると、圧延によって本発明の集合組織が容易に得やすくなる。本発明の集合組織を容易に得られるさらに好ましい相対密度の範囲は、９４．０％以上９８．０％以下である。この範囲であれば、製造時に安定してより高い集合組織が得られる。前記ブロックの相対密度は、後述の製造方法でも説明するように、仮成形体の密度と金属粉末の粒径、及び、焼結させる圧力と温度によって制御できる。 The relative density of the block before rolling has an important influence on the formation of a texture accompanying rolling, and the desirable range of the relative density is 90.0% or more and less than 99.0%. When the relative density is within this range, the texture of the present invention can be easily obtained by rolling. A more preferable range of relative density for easily obtaining the texture of the present invention is 94.0% or more and 98.0% or less. If it is this range, a higher texture will be obtained stably at the time of manufacture. The relative density of the block can be controlled by the density of the temporary molded body, the particle size of the metal powder, and the pressure and temperature for sintering, as will be described in the production method described later.
　圧延前のブロックの製造は溶製による方法をとることもできるが、融点が高いＣｒ、Ｍｏ、Ｗ等の場合に対応できるＨＩＰで金属粉末を加圧焼結させる方法が効率的である。スパッタリングターゲット材となる原料金属粉末を厚み３ｍｍ程度のＳＳ４００鋼板からなるカプセル容器に真空封入して、温度６００℃以上１３００℃以下、５００気圧以上２０００気圧以下の条件でＨＩＰにより加圧焼結させる。前記温度は、金属や合金によって最適値が選定される。 The block before rolling can be manufactured by melting, but a method of pressure-sintering metal powder with HIP that can cope with Cr, Mo, W or the like having a high melting point is efficient. The raw material metal powder used as the sputtering target material is vacuum-sealed in a capsule container made of SS400 steel plate having a thickness of about 3 mm, and is pressure-sintered by HIP under conditions of a temperature of 600 ° C. to 1300 ° C. and a pressure of 500 to 2000 atm. The optimum temperature is selected depending on the metal or alloy.
　即ち、各金属や合金の融点から算出されるタンマン温度以上の拡散が始まって焼結現象が起こる温度とすることができる。こうして得られる加圧焼結体（ブロック）の相対密度は９０％以上９９．０％未満である。前記相対密度は、仮成形体の密度と金属粉末の粒径、更に、ＨＩＰの圧力と温度によって制御できる。ここで、金属粉末は０．１μｍから５０μｍ程度の大きさのものが望ましく、例えば平均粒径で６μｍの粉末が使用される。前記金属粉末の粒径とＨＩＰ温度条件により粒成長を加味して、ブロックの結晶粒径を決定する。これらの粉末をＨＩＰ用容器内に挿入するが、容器に挿入する前にプレス加工や冷間静水圧プレスによって仮成型してコンパクト化するとより効率的な作業が可能となる。 That is, it can be set to a temperature at which the sintering phenomenon starts when diffusion above the Tamman temperature calculated from the melting point of each metal or alloy starts. The relative density of the pressure sintered body (block) thus obtained is 90% or more and less than 99.0%. The relative density can be controlled by the density of the temporary molded body, the particle size of the metal powder, and the pressure and temperature of the HIP. Here, the metal powder desirably has a size of about 0.1 μm to 50 μm. For example, a powder having an average particle diameter of 6 μm is used. The crystal grain size of the block is determined in consideration of grain growth according to the grain size of the metal powder and the HIP temperature condition. These powders are inserted into the HIP container. However, if the powder is temporarily formed by pressing or cold isostatic pressing before being inserted into the container, more efficient work can be performed.
　ＨＩＰによるブロック製造方法とは別に、常圧もしくは減圧中に水素を流して、ＣＩＰで固めた圧粉体を高温化で還元しながら焼結させてもブロックを製造することは可能である。熱処理中の平均的な水素濃度は０．５％以上２０％以下であり、水素流量によって酸素濃度を制御できる。焼結は５００～１８００℃程度で行い、相対密度９０％以上９９．０％未満の成形体が得られる。この場合の焼結温度も、金属や合金によって最適値が選定される。即ち、各金属や合金の融点から算出されるタンマン温度以上の拡散が始まって焼結現象が起こる温度とすることができる。ブロックの相対密度と結晶粒径の制御は、上記のＨＩＰの場合と同様に行うことができる。 In addition to the block manufacturing method using HIP, it is possible to manufacture a block by flowing hydrogen under normal pressure or reduced pressure and sintering the green compact solidified with CIP while reducing it at a high temperature. The average hydrogen concentration during the heat treatment is 0.5% or more and 20% or less, and the oxygen concentration can be controlled by the hydrogen flow rate. Sintering is performed at about 500 to 1800 ° C., and a molded body having a relative density of 90% or more and less than 99.0% is obtained. The optimum sintering temperature is selected depending on the metal or alloy. That is, the temperature can be set to a temperature at which the sintering phenomenon starts when diffusion above the Tamman temperature calculated from the melting point of each metal or alloy starts. Control of the relative density of the block and the crystal grain size can be performed in the same manner as in the case of the above HIP.
　ここで、ＨＩＰや常圧焼結が行われる前に、粉末の状態、または、仮成型体の状態に対して酸素を減少させることは可能である。水素雰囲気の中で粉末、もしくは、仮成型体を２００℃から５００℃程度に加熱して酸素を還元脱離させればよい。 Here, before HIP or atmospheric pressure sintering is performed, it is possible to reduce oxygen with respect to the state of the powder or the state of the temporary molded body. What is necessary is just to heat-reducing a powder or a temporary molded object in a hydrogen atmosphere at about 200 to 500 degreeC, and to carry out reductive desorption of oxygen.
　次に、該ブロックに特定条件で塑性変形処理を施すことによって、本発明の集合組織が得られる。その条件について、詳細に述べる。 Next, the texture of the present invention is obtained by subjecting the block to plastic deformation under specific conditions. The conditions will be described in detail.
　塑性加工は圧延によって実施することができ、圧延温度条件と圧下条件が重要である。 Plastic working can be carried out by rolling, and rolling temperature conditions and rolling conditions are important.
　圧延温度条件となる圧延開始温度は、通常、圧延設備の加圧能力で金属や合金を塑性変形できる温度範囲であればよいが、望ましい圧延開始温度は、圧延後に得られる金属や合金の集合組織によって決められる。ブロックが純Ｍｏの場合には、望ましい圧延開始温度の範囲は６００℃以上９００℃以下である。６００℃未満であると所望の集合組織は得られるが、変形抵抗が大きくなり圧延機の能力が足りなくなって圧延できない場合がある。９００℃を超えると、本発明の集合組織が得られず、本発明の効果が得られなくなってしまう場合がある。 The rolling start temperature, which is a rolling temperature condition, is usually in a temperature range in which a metal or alloy can be plastically deformed by the pressing capacity of the rolling equipment, but the desired rolling start temperature is the texture of the metal or alloy obtained after rolling. It is decided by. When the block is pure Mo, a desirable rolling start temperature range is 600 ° C. or higher and 900 ° C. or lower. If the temperature is lower than 600 ° C., a desired texture can be obtained, but there are cases where rolling resistance cannot be achieved because the deformation resistance increases and the capacity of the rolling mill becomes insufficient. If it exceeds 900 ° C., the texture of the present invention cannot be obtained, and the effects of the present invention may not be obtained.
　圧下条件は、圧延時の１パス当たりの圧下率と、全圧下率を制御することである。圧下条件に関しては、どの金属や合金においても、次のように制御する。 The reduction condition is to control the reduction rate per pass during rolling and the total reduction rate. Regarding the reduction conditions, the control is performed as follows for any metal or alloy.
　圧下率に関しては、圧延における１パス当たりの圧下率は比較的高くすると好ましく、具体的には１パス当たりの圧下率は１０％超５０％以下が望ましい。前記範囲であると、本発明の集合組織が容易に得られるようになる。１パス当たりの圧下率が１０％以下になると、本発明の集合組織は得にくくなる場合がある。また、５０％を超えると耳割れや亀裂が発生する場合があるため、前記範囲が望ましい。 Regarding the rolling reduction, the rolling reduction per pass in rolling is preferably relatively high. Specifically, the rolling reduction per pass is preferably more than 10% and 50% or less. Within the above range, the texture of the present invention can be easily obtained. If the rolling reduction per pass is 10% or less, the texture of the present invention may be difficult to obtain. Moreover, since it may generate | occur | produce an ear crack and a crack when it exceeds 50%, the said range is desirable.
　全圧下率に関しては、全圧下率の好ましい範囲は２０％以上９５％以下である。２０％を下回ると本発明の集合組織は得られにくくなる場合がある。９５％を超えると、集合組織を得られる効果が飽和するばかりでなく、耳割れ等が発生して歩留まりが低下する場合がある。 Regarding the total rolling reduction, a preferable range of the total rolling reduction is 20% or more and 95% or less. If it is less than 20%, the texture of the present invention may be difficult to obtain. If it exceeds 95%, not only the effect of obtaining a texture is saturated but also ear cracks or the like may occur, resulting in a decrease in yield.
　さて、上記条件では、場合によっては圧延途中にブロックが加工硬化を起こして、変形抵抗が増加したり、靱性が低下することがある。その場合には、ブロックを再加熱して回復や再結晶によって軟化させることができる。例えば、Ｍｏ系ブロックの場合に左記現象が起こりやすく、Ｍｏの場合には９００℃超１１００℃未満に再加熱して１分以上１０時間以下保持して軟化させることが可能である。圧延途中に再加熱して軟化させたのち、再び６００℃以上９００℃以下の温度領域で圧延してやれば、本発明のスパッタリングターゲット材の集合組織は問題なく得られる。
　また、圧延後に熱処理を施してターゲット材の靭性を向上させても本発明の集合組織を得ることは可能である。再加熱温度が９００℃超１１００℃未満ならば、そのまま本発明の集合組織は問題なく得られる。１１００℃以上であると再加熱によって結晶方位はランダム化する傾向にあり、本発明のターゲット材が得られなくなる。 Now, under the above conditions, in some cases, the block may undergo work hardening during rolling, and deformation resistance may increase or toughness may decrease. In that case, the block can be reheated and softened by recovery or recrystallization. For example, the phenomenon described on the left is likely to occur in the case of Mo-based blocks, and in the case of Mo, it can be reheated to over 900 ° C. and less than 1100 ° C. and held for 1 minute to 10 hours and softened. The texture of the sputtering target material of the present invention can be obtained without problems if it is softened by reheating during rolling and then rolled again in a temperature range of 600 ° C. or more and 900 ° C. or less.
Further, it is possible to obtain the texture of the present invention even if heat treatment is performed after rolling to improve the toughness of the target material. If the reheating temperature is more than 900 ° C. and less than 1100 ° C., the texture of the present invention can be obtained without any problem. When it is 1100 ° C. or higher, the crystal orientation tends to be randomized by reheating, and the target material of the present invention cannot be obtained.
　上記圧延では、ブロックを直接圧延してもよいが、ブロックをカプセル金属板で覆って酸化を防ぎながら圧延する方法で本発明のスパッタリングターゲット材はより容易に製造できる。カプセルに入れたブロックの圧延条件に関しても、上記と同様の条件で圧延すればよい。カプセルを調製するに関し、カプセル板とブロックの間には隙間は生じてよい。カプセル内に空気が入っていると酸化を抑制できない場合あるが、通常、隙間が生じても、圧延時にはカプセル板とブロック表面が密着するために、カプセル内の空気が押し出され、酸化が抑制される。また、酸化を抑制するために、隙間の空気を予め真空引きによって除去しておいても良い。この際には、加熱時はもとより、圧延時にカプセル板が破れて空気が入らないように、カプセル板の継ぎ目等の溶接部にはピンホールや亀裂が無いようにする。
　カプセルを構成する金属板としては、鋼板を用いれば良く、ＳＳ４００等の炭素鋼板が使用できる。前記鋼板は、材料コストが安い上に、カプセル板の継ぎ手溶接が比較的容易であるため、確実なカプセル化が可能となる。なお、ＨＩＰする際に使用した容器をそのまま圧延時のカプセルに流用して、容器を除去する作業を省略するとより効率的である。 In the above rolling, the block may be directly rolled, but the sputtering target material of the present invention can be more easily produced by a method of rolling the block while covering it with a capsule metal plate to prevent oxidation. The rolling conditions for the blocks placed in the capsule may be rolled under the same conditions as described above. In preparing the capsule, a gap may be created between the capsule plate and the block. Oxidation may not be suppressed if air is contained in the capsule. However, even if a gap is generated, the capsule plate and the block surface are in close contact during rolling, so the air in the capsule is pushed out and oxidation is suppressed. The In order to suppress oxidation, the air in the gap may be removed in advance by evacuation. At this time, in order to prevent the capsule plate from being broken and air from entering at the time of rolling as well as during heating, the welded portion such as the seam of the capsule plate should be free from pinholes and cracks.
As the metal plate constituting the capsule, a steel plate may be used, and a carbon steel plate such as SS400 can be used. Since the steel sheet is low in material cost and the joint welding of the capsule plate is relatively easy, reliable encapsulation is possible. In addition, it is more efficient if the container used at the time of HIP is diverted as it is to the capsule at the time of rolling and the operation | work which removes a container is abbreviate | omitted.
　カプセル材でブロックを覆って製造した場合には、圧延後にスパッタリングターゲット材を取り出すためにカプセル材を除去しなければならない。この際、カプセルの端部は鋸法やウォータージェット法によって切断でき、歩留まりを向上させるためにはできるだけスパッタリングターゲット材を避けて端部を切断除去する。 When the block is covered with a capsule material, the capsule material must be removed to take out the sputtering target material after rolling. At this time, the end portion of the capsule can be cut by a saw method or a water jet method. In order to improve the yield, the end portion is cut and removed while avoiding the sputtering target material as much as possible.
　以下、実施例により、本発明をさらに詳しく説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
　　(実施例１)
　平均粒径が５μｍの純Ｍｏ粉末（原料粉末）を出発材料として、ＨＩＰと圧延によってＭｏスパッタリングターゲット材の製造を行った。 (Example 1)
Using a pure Mo powder (raw material powder) with an average particle size of 5 μm as a starting material, a Mo sputtering target material was manufactured by HIP and rolling.
　使用した原料粉末には１５００質量ｐｐｍの酸素が付着しており、水素中で還元熱処理することによって酸素濃度を減少させることにした。ＳＳ４００製のＨＩＰ用容器を用意して、前記容器の中にＭｏ原料粉末を充填した。容器内部を真空引きした後に水素をパージし、さらに３００℃に加熱して還元させた。保定時間が長くなるほど酸素濃度が減少する傾向を利用して、還元時間（保定時間）で酸素濃度の制御を行った。Ｍｏブロックの酸素濃度の分析はＨＩＰ焼結させた後のブロックで行った。 The used raw material powder had 1500 mass ppm of oxygen attached, and the oxygen concentration was reduced by reducing heat treatment in hydrogen. An SS400 HIP container was prepared, and the Mo raw material powder was filled in the container. The inside of the container was evacuated and then purged with hydrogen, and further heated to 300 ° C. for reduction. The oxygen concentration was controlled by the reduction time (retention time) using the tendency that the oxygen concentration decreased as the retention time increased. Analysis of the oxygen concentration of the Mo block was performed on the block after HIP sintering.
　酸素濃度を制御する上記還元熱処理後、ロータリーポンプと油拡散ポンプでＨＩＰ用容器の内部を真空引きした。真空度が１０-2Ｐa程度に到達した後、吸引口等をピンホールが発生してリークしないように注意して封印した。この後、温度：１２５０℃、保定時間：４ｈ、圧力：１２００気圧の条件でＨＩＰ処理を施した。得られた焼結体から幅２５０ｍｍ×長さ１７００ｍｍ×厚み４０ｍｍのＭｏブロックを切り出した。それぞれのブロックに含有する酸素濃度は２００ｐｐｍであり、平均結晶粒径は１８μｍ、相対密度は９７．８％であった。また、ブロックには集合組織は形成されておらず、等方的であった。前記ブロックは、下記の各手順でスパッタリングターゲット材とした後も、各試料の酸素濃度は、ブロックと同じ２００ｐｐｍであった。 After the reduction heat treatment for controlling the oxygen concentration, the inside of the HIP container was evacuated with a rotary pump and an oil diffusion pump. After the degree of vacuum reached about 10 -2 Pa, the suction port and the like were sealed carefully so as not to leak due to pinholes. Thereafter, the HIP treatment was performed under the conditions of temperature: 1250 ° C., holding time: 4 h, pressure: 1200 atm. A Mo block having a width of 250 mm, a length of 1700 mm, and a thickness of 40 mm was cut out from the obtained sintered body. The oxygen concentration contained in each block was 200 ppm, the average crystal grain size was 18 μm, and the relative density was 97.8%. Also, no texture was formed in the block, and it was isotropic. Even after the block was used as a sputtering target material in the following procedures, the oxygen concentration of each sample was 200 ppm, the same as the block.
　得られたＭｏブロックを加熱して、圧延によって長さ方向へ引き伸ばした。全圧下率は全て５９％で一定とし、１パス当たり２０％の圧下率で４パスの圧下を施した。圧延を開始するときのブロック温度を各種変更して圧延を行い、得られたＭｏ圧延板の集合組織を調べた。圧延開始温度の範囲は、５００℃～１２００℃であった。ここで、得られた圧延板の相対密度は９９．５～９９．９％であった。 The obtained Mo block was heated and stretched in the length direction by rolling. The total rolling reduction was constant at 59%, and rolling was performed for 4 passes at a rolling reduction rate of 20% per pass. Rolling was performed while changing various block temperatures when starting rolling, and the texture of the obtained Mo rolled sheet was examined. The range of the rolling start temperature was 500 ° C to 1200 ° C. Here, the relative density of the obtained rolled sheet was 99.5 to 99.9%.
　得られた圧延板の｛２００｝、｛２２２｝、｛１１０｝面集積度は、Ｘ線回折法（ＭｏＫα線）で測定した。測定面は圧延板の表面から厚み方向へ１．５ｍｍ深さの位置にあり、圧延面に平行な面を機械加工で切り出して行った。結晶相の｛２００｝面集積度、｛２２２｝面集積度、および、｛１１０｝面集積度の測定は、先に述べた方法で求め、例えば、｛２００｝強度比率では、前述した式（１）のように求めた。 The {200}, {222}, {110} plane integration degree of the obtained rolled plate was measured by an X-ray diffraction method (MoKα ray). The measurement surface was located at a depth of 1.5 mm in the thickness direction from the surface of the rolled plate, and a surface parallel to the rolled surface was cut out by machining. The {200} plane integration degree, {222} plane integration degree, and {110} plane integration degree of the crystal phase are obtained by the method described above. For example, in the {200} intensity ratio, It was obtained as in 1).
　図２には、｛２００｝面集積度、｛２２２｝面集積度、および、｛１１０｝面集積度の圧延開始温度依存性を示した。圧延開始温度が６００℃未満の場合には、圧延に必要な圧下力が不足して圧延ができなかった。 FIG. 2 shows the rolling start temperature dependence of the {200} plane integration degree, the {222} plane integration degree, and the {110} plane integration degree. When the rolling start temperature was less than 600 ° C., the rolling force required for rolling was insufficient and rolling was not possible.
　圧延開始温度が１０００℃以上の場合には、集合組織は等方的でありいずれの面集積度も９％程度であった。１０００℃を下回ると｛２２２｝面集積度は増加し、｛１１０｝面集積度は減少する傾向にあった。｛２２２｝面集積度は６００℃以上９００℃以下で１５％を上回り、８００℃付近で最大となった。｛２００｝面密度は８５０℃以下で１５％を上回り、６００℃付近で最大値に達していた。｛２２２｝面集積度、または、｛２００｝面集積度が６００℃以上９００℃以下の場合に本発明の範囲に達することを確認した。 When the rolling start temperature was 1000 ° C. or higher, the texture was isotropic and the degree of surface integration was about 9%. Below 1000 ° C., the {222} plane integration degree increased and the {110} plane integration degree tended to decrease. The {222} plane integration degree exceeded 15% at 600 ° C. or more and 900 ° C. or less, and reached a maximum near 800 ° C. The {200} surface density exceeded 15% at 850 ° C. or less, and reached the maximum value at around 600 ° C. It was confirmed that the range of the present invention was reached when the {222} plane integration degree or {200} plane integration degree was 600 ° C or higher and 900 ° C or lower.
　｛２００｝面集積度と｛２２２｝面密度の和は圧延開始温度が８５０℃以下で７０％を超え、非常に優れた特性が得られる。この優れた特性は６００℃までほぼ維持され、特に優れた特性が得られる圧延開始温度は６００℃以上８５０℃以下である。 The sum of the {200} plane integration degree and the {222} plane density exceeds 70% when the rolling start temperature is 850 ° C. or less, and very excellent characteristics are obtained. This excellent characteristic is almost maintained up to 600 ° C., and the rolling start temperature at which particularly excellent characteristics are obtained is 600 ° C. or higher and 850 ° C. or lower.
　本実験で得られた圧延板を１０５０℃で２時間熱処理して、上記と同様に集合組織を調べた。それによると、熱処理後でも｛２００｝面集積度、および、｛２２２｝面集積度は本発明条件を満足していることを確認した。
　本実験で得られた圧延板を１２００℃で２時間熱処理して、上記と同様に集合組織を調べた。それによると、結晶方位はランダム化して、熱処理前後で｛２００｝面集積度、｛２２２｝面集積度、および、｛１１０｝面集積度は本発明条件を満足しなくなった。 The rolled sheet obtained in this experiment was heat-treated at 1050 ° C. for 2 hours, and the texture was examined in the same manner as described above. According to this, it was confirmed that the {200} plane integration degree and the {222} plane integration degree satisfy the conditions of the present invention even after the heat treatment.
The rolled sheet obtained in this experiment was heat-treated at 1200 ° C. for 2 hours, and the texture was examined in the same manner as described above. According to this, the crystal orientation was randomized, and the {200} plane integration degree, the {222} plane integration degree, and the {110} plane integration degree before and after the heat treatment did not satisfy the conditions of the present invention.
　以上示したように、Ｍｏブロック板を加熱して圧延する際に、圧延開始温度を特定の条件に設定することにより、本発明のスパッタリングターゲット材の集合組織に制御することができる。 As described above, when the Mo block plate is heated and rolled, the texture of the sputtering target material of the present invention can be controlled by setting the rolling start temperature to a specific condition.
　各圧延開始温度で作製した圧延板から１２７ｍｍ×１９１ｍｍ×６ｍｍｔの試験材を切り出した。ここで、前記切り出した試験材のスパッタリング面は、圧延面（前記試験材の１２７ｍｍ×１９１ｍｍ面）の表面から深さ方向に１．５ｍｍ深さの位置に設定した。前記試験材をＣｕ製のバッキングプレートにボンディングしてスパッタリングターゲット材を作成した。このターゲット材を用いて、スパッタリング時のスループット性能を評価した。 A 127 mm × 191 mm × 6 mmt test material was cut out from a rolled plate produced at each rolling start temperature. Here, the sputtering surface of the cut out test material was set at a depth of 1.5 mm in the depth direction from the surface of the rolled surface (127 mm × 191 mm surface of the test material). The test material was bonded to a Cu backing plate to prepare a sputtering target material. Using this target material, the throughput performance during sputtering was evaluated.
　作製されたスパッタリングターゲット材をスパッタ装置に装着し、ガラス基板上にＭｏ薄膜を成膜することにより成膜速度の測定を行った。スパッタリングにおける条件は次の通りとした。スパッタリングガス：Ａｒ、スパッタリングガス圧：２．０ｍＴｏｒｒ（０．２７Ｐａ）、スパッタリング電力：２．０ｋＷ、基板：Ｃｏｒｎｉｎｇ＃７０５９（５０×５０ｍｍ2）。また、成膜速度測定の際には、予めプレスパッタリングを行った。このプレスパッタリングの条件は、Ａｒガス圧５．０ｍＴｏｒｒ（０．６７Ｐａ）、スパッタリング電力２．０ｋＷ、時間１０ｍｉｎである。その後、投入電力２．０ｋＷにて１０ｍｉｎ成膜し、形成された薄膜の膜厚を測定した。上記条件で基板上に成膜したＭｏ薄膜の膜厚測定を行い、これを成膜時間で除した値を成膜速度［ｎｍ／ｓｅｃ］とした。 The produced sputtering target material was mounted on a sputtering apparatus, and a film formation rate was measured by forming a Mo thin film on a glass substrate. The sputtering conditions were as follows. Sputtering gas: Ar, sputtering gas pressure: 2.0 mTorr (0.27 Pa), sputtering power: 2.0 kW, substrate: Corning # 7059 (50 × 50 mm 2 ). In addition, pre-sputtering was performed in advance when measuring the film formation rate. The pre-sputtering conditions are an Ar gas pressure of 5.0 mTorr (0.67 Pa), a sputtering power of 2.0 kW, and a time of 10 min. Thereafter, a film was formed for 10 minutes at an input power of 2.0 kW, and the film thickness of the formed thin film was measured. The film thickness of the Mo thin film formed on the substrate under the above conditions was measured, and the value obtained by dividing this by the film formation time was defined as the film formation rate [nm / sec].
　スパッタリング中における放電安定性を評価するため、上記スパッタリングターゲットをスパッタ装置に装着し、アーキング特性を評価した。放電条件はスパッタリングガス：Ａｒ、スパッタリングガス圧：２．０ｍＴｏｒｒ（０．２７Ｐａ）、スパッタリング電力：２．０ｋＷで、積算スパッタリング電力が５ｋＷｈに達するまで連続放電し、その間に発生したアーキング回数を測定した。アーキングはＤＣ電源供給ケーブルに直接コイルを巻き、オシロスコープにてアーキングを観察した。 In order to evaluate the discharge stability during sputtering, the sputtering target was mounted on a sputtering apparatus, and the arcing characteristics were evaluated. The discharge conditions were sputtering gas: Ar, sputtering gas pressure: 2.0 mTorr (0.27 Pa), sputtering power: 2.0 kW, continuous discharge until the integrated sputtering power reached 5 kWh, and the number of arcing generated during that time was measured. . For arcing, a coil was directly wound around a DC power supply cable, and arcing was observed with an oscilloscope.
　図２で本発明の範囲内に入っている集合組織を有するターゲットは、アーキングが起こらず、図３に示しているように、良好な成膜速度となった。 In FIG. 2, the target having a texture that falls within the scope of the present invention did not cause arcing, and as shown in FIG.
　なお、ターゲット板を構成する主元素がＣｒ、Ｗ、Ｖ、Ｔａのいずれかである場合にも、圧延開始温度が本発明の集合組織に制御するために重要であり、同じ圧延開始温度範囲で本発明範囲のスパッタリングターゲット材に入ることが確認でき、アーキングを抑制できることが示された。 Even when the main element constituting the target plate is any one of Cr, W, V, and Ta, the rolling start temperature is important for controlling the texture of the present invention, and in the same rolling start temperature range. It was confirmed that the sputtering target material was within the range of the present invention, and it was shown that arcing can be suppressed.
　(実施例２)
　平均粒径が５μｍの純Ｍｏ粉末を出発材料として、加熱焼結と圧延によって各種のＭｏスパッタリングターゲット材の製造を行った。 (Example 2)
Using a pure Mo powder having an average particle size of 5 μm as a starting material, various Mo sputtering target materials were manufactured by heat sintering and rolling.
　原料粉末には１５００質量ｐｐｍの酸素が付着しており、水素中で還元焼結処理することによって酸素濃度を減少させたブロックを作製することにした。 The raw material powder had 1500 mass ppm of oxygen attached thereto, and it was decided to produce a block in which the oxygen concentration was reduced by reduction sintering treatment in hydrogen.
　まず、ＣＩＰ法によりＭｏ粉末を固め、真空引きした後に水素をパージし、さらに大気圧で水素を流した熱処理炉内で還元しながら同時に加熱焼結させた。焼結温度はブロックによって変え、その範囲は１２００～１８００℃であった。得られたブロック寸法は幅２１０ｍｍ、長さ８１０ｍｍの一定値とし、厚みは２２．８～８５ｍｍであった。平均結晶粒径は９．８～５５μｍ、相対密度は８９．２％～９９．２％であった。 First, the Mo powder was hardened by the CIP method, vacuumed and then purged with hydrogen, and further heated and sintered while being reduced in a heat treatment furnace in which hydrogen was passed at atmospheric pressure. The sintering temperature varied from block to block and the range was 1200-1800 ° C. The obtained block dimensions were a constant value of 210 mm width and 810 mm length, and the thickness was 22.8 to 85 mm. The average crystal grain size was 9.8 to 55 μm, and the relative density was 89.2% to 99.2%.
　作製したブロックに含有する酸素濃度は処理時間が長くなるほど減少し、酸素濃度の制御は処理時間で行った。酸素濃度の分析は焼結させた後のブロックで行った。 The oxygen concentration contained in the produced block decreased as the treatment time increased, and the oxygen concentration was controlled by the treatment time. The analysis of oxygen concentration was performed on the block after sintering.
　また、ブロックには集合組織は形成されておらず、結晶方位はランダムであった。金属組織を観察して線分法で求めた各ブロックの結晶粒径は表１に示した。 Also, no texture was formed in the block, and the crystal orientation was random. The crystal grain size of each block obtained by observing the metal structure by the line segment method is shown in Table 1.
　異なる酸素濃度と結晶粒径のＭｏブロック板に対して、表１に示した各種の条件で圧延を施した。条件としては、圧延開始温度、１パスあたりの圧下率、全圧下率を変えた。ここで、圧延中の板温度が圧延開始温度に比べて１００℃以上低下した際には、圧延開始温度に板温度を戻すために再加熱を行った。 The Mo block plates having different oxygen concentrations and crystal grain sizes were rolled under various conditions shown in Table 1. As conditions, the rolling start temperature, the rolling reduction per pass, and the total rolling reduction were changed. Here, when the plate temperature during rolling decreased by 100 ° C. or more compared to the rolling start temperature, reheating was performed to return the plate temperature to the rolling start temperature.
　得られた圧延板の｛２００｝、｛２２２｝、および、｛１１０｝面集積度は、Ｘ線回折法（ＭｏＫα線）で測定した。測定面は圧延板の表面から厚み方向へ１．５ｍｍ深さの位置にあり、圧延面に平行な面を機械加工で切り出して行った。結晶相の｛２００｝面集積度、｛２２２｝面集積度、および、｛１１０｝面集積度の測定は、先に述べた方法で求め、例えば、｛２００｝強度比率では、前述した式（１）のように求めた。 The {200}, {222} and {110} plane integration degree of the obtained rolled sheet was measured by an X-ray diffraction method (MoKα ray). The measurement surface was located at a depth of 1.5 mm in the thickness direction from the surface of the rolled plate, and a surface parallel to the rolled surface was cut out by machining. The {200} plane integration degree, {222} plane integration degree, and {110} plane integration degree of the crystal phase are obtained by the method described above. For example, in the {200} intensity ratio, It was obtained as in 1).
　圧延板の表面から厚み方向へ１．５ｍｍ深さの位置において圧延面の法線方向から金属組織を観察し、圧延に垂直方向の結晶粒径を線分法で測定した。 The metal structure was observed from the normal direction of the rolled surface at a position 1.5 mm deep in the thickness direction from the surface of the rolled plate, and the crystal grain size in the direction perpendicular to the rolling was measured by the line segment method.
　得られたブロック板から１２７ｍｍ×１９１ｍｍ×６ｍｍｔの試験材を切り出した。ここで、前記切り出した試験材のスパッタリング面は、圧延面（前記試験材の１２７ｍｍ×１９１ｍｍ面）の表面から深さ方向に１．５ｍｍ深さの位置に設定した。前記試験材をＣｕ製のバッキングプレートにボンディングしてスパッタリングターゲット材を作製した。このターゲット材を用いて、スパッタリング時のスループット性能を評価した。 A 127 mm × 191 mm × 6 mmt test material was cut out from the obtained block plate. Here, the sputtering surface of the cut out test material was set at a depth of 1.5 mm in the depth direction from the surface of the rolled surface (127 mm × 191 mm surface of the test material). The test material was bonded to a Cu backing plate to produce a sputtering target material. Using this target material, the throughput performance during sputtering was evaluated.
　作製されたスパッタリングターゲット材をスパッタ装置に装着し、ガラス基板上にＭｏ薄膜を成膜することにより成膜速度の測定を行った。スパッタリングにおける条件は次の通りとした。スパッタリングガス：Ａｒ、スパッタリングガス圧：２．０ｍＴｏｒｒ（０．２７Ｐａ）、スパッタリング電力：２．０ｋＷ、基板：Ｃｏｒｎｉｎｇ＃７０５９（５０×５０ｍｍ2）。また、成膜速度測定の際に、Ａｒガス圧５．０ｍＴｏｒｒ（０．６７Ｐａ）、スパッタリング電力２．０ｋＷの条件にて１０ｍｉｎプレスパッタリングを実施した。その後、投入電力２．０ｋＷにて１０ｍｉｎ成膜し形成された薄膜の膜厚を測定した。基板上に成膜したＭｏ薄膜の膜厚測定を行い、これを成膜時間で除した値を成膜速度［ｎｍ／ｓｅｃ］とした。  The produced sputtering target material was mounted on a sputtering apparatus, and a film formation rate was measured by forming a Mo thin film on a glass substrate. The sputtering conditions were as follows. Sputtering gas: Ar, sputtering gas pressure: 2.0 mTorr (0.27 Pa), sputtering power: 2.0 kW, substrate: Corning # 7059 (50 × 50 mm 2 ). Further, pre-sputtering was performed for 10 minutes under the conditions of Ar gas pressure of 5.0 mTorr (0.67 Pa) and sputtering power of 2.0 kW at the time of measuring the film formation rate. Then, the film thickness of the thin film formed by depositing for 10 min at an input power of 2.0 kW was measured. The film thickness of the Mo thin film formed on the substrate was measured, and the value obtained by dividing this by the film formation time was defined as the film formation rate [nm / sec].
　また、スパッタリング中における放電安定性を評価するため、上記スパッタリングターゲットをスパッタ装置に装着し、アーキング特性を評価した。放電条件はスパッタリングガス：Ａｒ、スパッタリングガス圧：２．０ｍＴｏｒｒ（０．２７Ｐａ）、スパッタリング電力：２．０ｋＷで、積算スパッタリング電力が５ｋＷｈに達するまで連続放電し、その間に発生したアーキング回数を測定した。アーキングはＤＣ電源供給ケーブルに直接コイルを巻き、オシロスコープにてアーキングを観察した。 Also, in order to evaluate the discharge stability during sputtering, the sputtering target was mounted on a sputtering apparatus, and the arcing characteristics were evaluated. The discharge conditions were sputtering gas: Ar, sputtering gas pressure: 2.0 mTorr (0.27 Pa), sputtering power: 2.0 kW, continuous discharge until the integrated sputtering power reached 5 kWh, and the number of arcing generated during that time was measured. . For arcing, a coil was directly wound around a DC power supply cable, and arcing was observed with an oscilloscope.
Figure JPOXMLDOC01-appb-T000002
 　 
Figure JPOXMLDOC01-appb-T000002
 　 
　表１において、成膜速度が２１．０（nm／min）以上であって、かつ、アーキング回数が０であった材料を合格として評価した。 In Table 1, a material having a deposition rate of 21.0 nm / min or more and an arcing count of 0 was evaluated as a pass.
　Ｎｏ．１～８の材料はターゲット板の条件が本発明範囲に入っていない比較例である。Ｎｏ．１は、酸素濃度６００ｐｐｍ、結晶粒径３３μｍ、相対密度９７．６％、厚み４４ｍｍの原料ブロック板を圧延開始温度８００℃、１パス当たりの圧下率を１５％とし、全圧下率５６％で圧延したものである。｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲に入っていたが、酸素濃度が本発明の範囲から外れていた。この場合には、成膜速度は他の発明例と同程度であったが、アーキング回数が多かった。したがって、スループット性能は他の発明例に比べて劣っていた。 No. Materials 1 to 8 are comparative examples in which the conditions of the target plate are not within the scope of the present invention. No. 1 is a raw material block plate having an oxygen concentration of 600 ppm, a crystal grain size of 33 μm, a relative density of 97.6%, and a thickness of 44 mm, rolled at a rolling start temperature of 800 ° C., a rolling reduction per pass of 15%, and a total rolling reduction of 56%. It is what. Both {200} plane integration and {222} plane integration were within the scope of the present invention, but the oxygen concentration was outside the scope of the present invention. In this case, the film formation rate was similar to that of the other invention examples, but the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
　Ｎｏ．２は、酸素濃度５０ｐｐｍ、結晶粒径５５μｍ、相対密度９７．８％、厚み６７ｍｍの原料ブロック板を圧延開始温度７５０℃、１パス当たりの圧下率を１３％とし、全圧下率６７％で圧延したものである。酸素濃度は本発明の範囲に入っていたが、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲を外れていた。この場合には、成膜速度はいずれの発明例に比べて小さく、アーキング回数が多かった。したがって、スループット性能は他の発明例に比べて劣っていた。 No. 2 is a raw material block plate having an oxygen concentration of 50 ppm, a crystal grain size of 55 μm, a relative density of 97.8%, and a thickness of 67 mm, rolling at a rolling start temperature of 750 ° C., a rolling reduction per pass of 13%, and a total rolling reduction of 67%. It is what. Although the oxygen concentration was within the range of the present invention, the {200} plane integration level and the {222} plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
　Ｎｏ．３は、酸素濃度５０ｐｐｍ、結晶粒径９．８μｍ、相対密度９７．８％、厚み６７ｍｍの原料ブロック板を圧延開始温度７５０℃、１パス当たりの圧下率を１３％とし、全圧下率６７％で圧延したものである。酸素濃度は本発明の範囲に入っていたが、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲を外れていた。この場合には、成膜速度はいずれの発明例に比べて小さく、アーキング回数が多かった。したがって、スループット性能は他の発明例に比べて劣っていた。 No. 3 is a raw material block plate having an oxygen concentration of 50 ppm, a crystal grain size of 9.8 μm, a relative density of 97.8%, a thickness of 67 mm, a rolling start temperature of 750 ° C., a rolling reduction per pass of 13%, and a total rolling reduction of 67%. Rolled with Although the oxygen concentration was within the range of the present invention, the {200} plane integration level and the {222} plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
　Ｎｏ．４は、酸素濃度１００ｐｐｍ、結晶粒径１３μｍ、相対密度８９．２％、厚み５５ｍｍの原料ブロック板を圧延開始温度８５０℃、１パス当たりの圧下率を２５％とし、全圧下率４４％で圧延したものである。酸素濃度は本発明の範囲に入っていたが、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲を外れていた。この場合には、成膜速度はいずれの発明例に比べて小さく、アーキング回数が多かった。したがって、スループット性能は他の発明例に比べて劣っていた。 No. 4 is a raw material block plate having an oxygen concentration of 100 ppm, a crystal grain size of 13 μm, a relative density of 89.2%, and a thickness of 55 mm, rolled at a rolling start temperature of 850 ° C., a reduction rate of 25% per pass, and a total reduction rate of 44%. It is what. Although the oxygen concentration was within the range of the present invention, the {200} plane integration level and the {222} plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
　Ｎｏ．５は、酸素濃度１００ｐｐｍ、結晶粒径１３μｍ、相対密度９９．２％、厚み５５ｍｍの原料ブロック板を圧延開始温度８５０℃、１パス当たりの圧下率を２５％とし、全圧下率４４％で圧延したものである。酸素濃度は本発明の範囲に入っていたが、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲を外れていた。この場合には、成膜速度はいずれの発明例に比べて小さく、アーキング回数が多かった。したがって、スループット性能は他の発明例に比べて劣っていた。 No. 5 is a raw material block plate having an oxygen concentration of 100 ppm, a crystal grain size of 13 μm, a relative density of 99.2%, and a thickness of 55 mm, rolled at a rolling start temperature of 850 ° C., a reduction rate of 25% per pass, and a total reduction rate of 44%. It is what. Although the oxygen concentration was within the range of the present invention, the {200} plane integration level and the {222} plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
　Ｎｏ．６は、酸素濃度２００ｐｐｍ、結晶粒径３３μｍ、相対密度９６．５％、厚み４４ｍｍの原料ブロック板を圧延開始温度８００℃、１パス当たりの圧下率を４％とし、全圧下率５６％で圧延したものである。酸素濃度は本発明の範囲に入っていたが、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲を外れていた。この場合には、成膜速度はいずれの発明例に比べて小さく、アーキング回数が多かった。したがって、スループット性能は他の発明例に比べて劣っていた。 No. 6 is a raw material block plate having an oxygen concentration of 200 ppm, a crystal grain size of 33 μm, a relative density of 96.5% and a thickness of 44 mm, rolled at a rolling start temperature of 800 ° C., a rolling reduction rate of 4%, and a total rolling reduction rate of 56%. It is a thing. Although the oxygen concentration was within the range of the present invention, the {200} plane integration level and the {222} plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
　Ｎｏ．７は、酸素濃度２００ｐｐｍ、結晶粒径３３μｍ、相対密度９７．６％、厚み２２．８ｍｍの原料ブロック板を圧延開始温度８００℃、１パス当たりの圧下率を１５％とし、全圧下率１５％で圧延したものである。酸素濃度は本発明の範囲に入っていたが、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲を外れていた。この場合には、成膜速度はいずれの発明例に比べて小さく、アーキング回数が多かった。したがって、スループット性能は他の発明例に比べて劣っていた。 No. 7 is a raw material block plate having an oxygen concentration of 200 ppm, a crystal grain size of 33 μm, a relative density of 97.6%, a thickness of 22.8 mm, a rolling start temperature of 800 ° C., a rolling reduction per pass of 15%, and a total rolling reduction of 15%. Rolled with Although the oxygen concentration was within the range of the present invention, the {200} plane integration level and the {222} plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
　Ｎｏ．８は、酸素濃度３０ｐｐｍ、結晶粒径２３μｍ、相対密度９６．５％、厚み８５ｍｍの原料ブロック板を圧延開始温度９５０℃、１パス当たりの圧下率を３０％とし、全圧下率８３％で圧延したものである。酸素濃度は本発明の範囲に入っていたが、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲を外れていた。この場合には、成膜速度はいずれの発明例に比べて小さく、アーキング回数が多かった。したがって、スループット性能は他の発明例に比べて劣っていた。 No. 8 is a raw material block plate having an oxygen concentration of 30 ppm, a crystal grain size of 23 μm, a relative density of 96.5%, and a thickness of 85 mm, rolling at a rolling start temperature of 950 ° C., a rolling reduction rate of 30%, and a total rolling reduction rate of 83%. It is what. Although the oxygen concentration was within the range of the present invention, the {200} plane integration level and the {222} plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
　以下のＮｏ．９～２７の材料はターゲット板の条件が本発明範囲に入っている発明例である。 The following No. Materials 9 to 27 are invention examples in which the conditions of the target plate are within the scope of the present invention.
　Ｎｏ．９～１３は、酸素濃度５～５００ｐｐｍ、結晶粒径３３μｍ、相対密度９７．３～９８．２％、厚み４４ｍｍの原料ブロック板を圧延開始温度８００℃、１パス当たりの圧下率を１５％とし、全圧下率５６％で圧延したものである。酸素濃度は本発明の範囲５ｐｐｍ以上５００ｐｐｍ以下に入っており、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲に入っていた。この場合には、成膜速度は比較例（Ｎｏ．１の比較例を除く）に比べて大きく、アーキングは全く起きなかった。したがって、スループット性能は比較例に比べて優れていた。 No. Nos. 9 to 13 are raw material block plates having an oxygen concentration of 5 to 500 ppm, a crystal grain size of 33 μm, a relative density of 97.3 to 98.2%, and a thickness of 44 mm, a rolling start temperature of 800 ° C., and a rolling reduction per pass of 15%. , Rolled at a total rolling reduction of 56%. The oxygen concentration falls within the range of 5 ppm to 500 ppm of the present invention, and the {200} plane integration degree and the {222} plane integration degree both fall within the scope of the present invention. In this case, the deposition rate was higher than that of the comparative example (excluding the comparative example of No. 1), and no arcing occurred. Therefore, the throughput performance was superior to the comparative example.
　Ｎｏ．１４～１７は、酸素濃度５０ｐｐｍ、結晶粒径１０．５～５０μｍ、相対密度９７．８％、厚み６７ｍｍの原料ブロック板を圧延開始温度７５０℃、１パス当たりの圧下率を１３％とし、全圧下率６７％で圧延したものである。酸素濃度は本発明の範囲に入っており、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲に入っていた。原料ブロック板の結晶粒径が１０μｍ超５０μｍ以下で、本発明のターゲット板が得られた。成膜速度は比較例（Ｎｏ．１の比較例を除く）に比べて大きく、アーキングは全く起きなかった。ここで、結晶粒径が２０～４０μｍで特に成膜速度は高かった。 No. 14 to 17, a raw material block plate having an oxygen concentration of 50 ppm, a crystal grain size of 10.5 to 50 μm, a relative density of 97.8%, and a thickness of 67 mm was set at a rolling start temperature of 750 ° C. and a reduction rate per pass of 13%. Rolled at a rolling reduction of 67%. The oxygen concentration is within the scope of the present invention, and the {200} plane integration degree and the {222} plane integration degree are both within the scope of the present invention. When the crystal grain size of the raw material block plate is more than 10 μm and 50 μm or less, the target plate of the present invention was obtained. The film formation rate was higher than that of the comparative example (excluding the comparative example of No. 1), and no arcing occurred. Here, the film formation rate was particularly high when the crystal grain size was 20 to 40 μm.
　Ｎｏ．１８～２３は、酸素濃度１００ｐｐｍ、結晶粒径１３μｍ、相対密度９０．０～９８．８％、厚み５５ｍｍの原料ブロック板を圧延開始温度８５０℃、１パス当たりの圧下率を２５％とし、全圧下率４４％で圧延したものである。酸素濃度は本発明の範囲に入っており、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲に入っていた。原料ブロック板の相対密度が９０．０％以上９９．０％未満で、本発明のターゲット板が得られた。成膜速度は比較例（Ｎｏ．１の比較例を除く）に比べて大きく、アーキングは全く起きなかった。ここで、原料ブロック板の相対密度が９４．０％以上９８．０％以下の場合により高い面集積度が得られ、成膜速度は高かった。 No. 18-23, a raw material block plate having an oxygen concentration of 100 ppm, a crystal grain size of 13 μm, a relative density of 90.0 to 98.8%, and a thickness of 55 mm, a rolling start temperature of 850 ° C., a rolling reduction per pass of 25%, Rolled at a rolling reduction of 44%. The oxygen concentration is within the scope of the present invention, and the {200} plane integration degree and the {222} plane integration degree are both within the scope of the present invention. When the relative density of the raw material block plate was 90.0% or more and less than 99.0%, the target plate of the present invention was obtained. The film formation rate was higher than that of the comparative example (excluding the comparative example of No. 1), and no arcing occurred. Here, when the relative density of the raw material block plate was 94.0% or more and 98.0% or less, a higher surface integration degree was obtained, and the film formation rate was high.
　Ｎｏ．２４～２７は、酸素濃度３０ｐｐｍ、結晶粒径２３μｍ、相対密度９６．５％、厚み８５ｍｍの原料ブロック板を圧延開始温度６００～９００℃、１パス当たりの圧下率を３０％とし、全圧下率８３％で圧延したものである。酸素濃度は本発明の範囲に入っており、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲に入っていた。圧延開始温度が６００℃以上９００℃以下で、本発明のターゲット板が得られた。成膜速度は比較例（Ｎｏ．１の比較例を除く）に比べて大きく、アーキングは全く起きなかった。 No. 24 to 27 are raw material block plates having an oxygen concentration of 30 ppm, a crystal grain size of 23 μm, a relative density of 96.5% and a thickness of 85 mm, a rolling start temperature of 600 to 900 ° C., a rolling reduction per pass of 30%, and a total rolling reduction Rolled at 83%. The oxygen concentration is within the scope of the present invention, and the {200} plane integration degree and the {222} plane integration degree are both within the scope of the present invention. The target plate of the present invention was obtained at a rolling start temperature of 600 ° C. or higher and 900 ° C. or lower. The film formation rate was higher than that of the comparative example (excluding the comparative example of No. 1), and no arcing occurred.
　以上示したように、本発明のＭｏスパッタリングターゲット板は従来に比べてより優れたスループット性能を有することを確認できた。
(実施例３)
　平均粒径が１～２０μｍのＣｒ、Ｗ、Ｖ、Ｔａ、Ｍｏ、Ｎｂ粉末を出発材料として、ＨＩＰと圧延によって各種スパッタリングターゲット材の製造を行った。まず、Ｃｒ、Ｗ、Ｖ、Ｔａ、Ｎｂについては単一粉末で純金属によるターゲット材を製造した。また、ＣｒとＭｏ、ＭｏとＷ、ＭｏとＮｂの組み合わせで粉末を質量比で５０：５０の割合で混合して、合金ターゲット材を製造した。 As shown above, it has been confirmed that the Mo sputtering target plate of the present invention has better throughput performance than the conventional one.
Example 3
Various sputtering target materials were manufactured by HIP and rolling using Cr, W, V, Ta, Mo, and Nb powder having an average particle diameter of 1 to 20 μm as starting materials. First, for Cr, W, V, Ta, and Nb, a pure metal target material was manufactured with a single powder. Moreover, the alloy target material was manufactured by mixing powder in the ratio of 50:50 by mass ratio with the combination of Cr and Mo, Mo and W, and Mo and Nb.
　原料粉末にはそれぞれ１５００質量ｐｐｍの酸素が付着しており、水素中で還元熱処理することによって酸素濃度を減少させることにした。ＳＳ４００製のＨＩＰ用容器を用意して、原料粉末を中に充填した。容器内部を真空引きした後に水素をパージした後３００℃に加熱して還元させた。酸素濃度は保定時間が長くなるほど減少し、酸素濃度の制御は還元時間で行った。原料ブロックの酸素濃度の分析はＨＩＰ焼結させた後のブロックで行った。 The raw material powders each had 1500 ppm by mass of oxygen attached thereto, and the oxygen concentration was reduced by reducing heat treatment in hydrogen. An SS400 HIP container was prepared and filled with raw material powder. The inside of the container was evacuated and purged with hydrogen, and then heated to 300 ° C. for reduction. The oxygen concentration decreased as the retention time increased, and the oxygen concentration was controlled by the reduction time. Analysis of the oxygen concentration of the raw material block was performed on the block after HIP sintering.
　酸素濃度制御の処理後、ロータリーポンプと油拡散ポンプでＨＩＰ用容器の内部を真空引きした。真空度が１０-2Ｐa程度に到達した後、吸引口等をピンホールが発生してリークしないように注意して封印した。この後、１１５０～１４００℃×２時間保定、１２００気圧（１２１．６ＭＰａ）の条件でＨＩＰ焼結処理を施した。得られた焼結体から幅２５０ｍｍ×長さ１７００ｍｍ×厚み２０～８０ｍｍの原料ブロックを切り出した。前記ＨＩＰ温度は、具体的には、各金属について、Ｃｒ：１１５０℃、Ｗ：１４００℃、Ｖ：１１５０℃、Ｎｂ：１２００℃、Ｃｒ－Ｍｏ：１２００℃、Ｍｏ－Ｗ：１３５０℃、Ｍｏ－Ｎｂ：１２００℃であり、それぞれの融点の１／３（タンマン温度）以上である。 After the oxygen concentration control process, the inside of the HIP container was evacuated with a rotary pump and an oil diffusion pump. After the degree of vacuum reached about 10 -2 Pa, the suction port and the like were sealed carefully so as not to leak due to pinholes. Thereafter, the HIP sintering process was performed under the conditions of 1150 to 1400 ° C. × 2 hours, 1200 atm (121.6 MPa). A raw material block having a width of 250 mm, a length of 1700 mm and a thickness of 20 to 80 mm was cut out from the obtained sintered body. Specifically, for each metal, the HIP temperature is Cr: 1150 ° C., W: 1400 ° C., V: 1150 ° C., Nb: 1200 ° C., Cr—Mo: 1200 ° C., Mo—W: 1350 ° C., Mo— Nb: 1200 ° C., which is equal to or higher than 1/3 (Taman temperature) of each melting point.
　これらの原料ブロックの相対密度、及び、それぞれの原料ブロックに含有する酸素濃度は表２に示したとおりである。  The relative density of these raw material blocks and the oxygen concentration contained in each raw material block are as shown in Table 2.
　得られた原料ブロックを加熱して、異なる圧延温度と全圧下率で圧延を施した。原料ブロックの条件と圧延条件に関しては、表２に記載した。 The obtained raw material block was heated and rolled at different rolling temperatures and total reduction ratios. The raw material block conditions and rolling conditions are shown in Table 2.
　得られた圧延板の｛２００｝、｛２２２｝、｛１１０｝面集積度は、Ｘ線回折法（ＭｏＫα線）で測定した。いずれの測定片においても体心立方結晶であることがＸ線回折法でも確認できた。測定面は圧延板の表面から厚み方向へ３ｍｍ深さの位置にあり、圧延面に平行な面を機械加工で切り出して行った。結晶相の｛２００｝面集積度、｛２２２｝面集積度、および、｛１１０｝面集積度の測定は、先に述べた方法で求め、例えば、｛２００｝強度比率では、前述した式（１）のように求めた。 The {200}, {222}, {110} plane integration degree of the obtained rolled plate was measured by an X-ray diffraction method (MoKα ray). It was confirmed by X-ray diffraction that all the measurement pieces were body-centered cubic crystals. The measurement surface was located at a depth of 3 mm from the surface of the rolled plate in the thickness direction, and a surface parallel to the rolled surface was cut out by machining. The {200} plane integration degree, {222} plane integration degree, and {110} plane integration degree of the crystal phase are obtained by the method described above. For example, in the {200} intensity ratio, It was obtained as in 1).
　得られた圧延板から１２７ｍｍ×１９１ｍｍ×６ｍｍｔの試験材を切り出した。これをＣｕ製のバッキングプレートにボンディングしてスパッタリングターゲット材を作成した。このターゲット材を用いて、スパッタリング時のスループット性能を評価した。 A test material of 127 mm × 191 mm × 6 mmt was cut out from the obtained rolled plate. This was bonded to a Cu backing plate to prepare a sputtering target material. Using this target material, the throughput performance during sputtering was evaluated.
　作製されたスパッタリングターゲット材をスパッタ装置に装着し、ガラス基板上に薄膜を成膜することにより成膜速度の測定を行った。スパッタリングにおける条件は次の通りとした。スパッタリングガス：Ａｒ、スパッタリングガス圧：２．０ｍＴｏｒｒ（０．２７Ｐａ）、スパッタリング電力：２．０ｋＷ、基板：Ｃｏｒｎｉｎｇ＃７０５９（５０×５０ｍｍ2）。また、成膜速度測定の際には、予めプレスパッタリングを行った。このプレスパッタリングの条件は、Ａｒガス圧５．０ｍＴｏｒｒ（０．６７Ｐａ）、スパッタリング電力２．０ｋＷ、時間１０ｍｉｎであった。その後、投入電力２．０ｋＷにて１０ｍｉｎ成膜し形成された薄膜の膜厚を測定した。上記条件で基板上に成膜した金属又は合金薄膜の膜厚測定を行い、これを成膜時間で除した値を成膜速度［ｎｍ／ｓｅｃ］とした。
  The produced sputtering target material was attached to a sputtering apparatus, and a film formation rate was measured by forming a thin film on a glass substrate. The sputtering conditions were as follows. Sputtering gas: Ar, sputtering gas pressure: 2.0 mTorr (0.27 Pa), sputtering power: 2.0 kW, substrate: Corning # 7059 (50 × 50 mm 2 ). In addition, pre-sputtering was performed in advance when measuring the film formation rate. The pre-sputtering conditions were an Ar gas pressure of 5.0 mTorr (0.67 Pa), a sputtering power of 2.0 kW, and a time of 10 min. Then, the film thickness of the thin film formed by depositing for 10 min at an input power of 2.0 kW was measured. The film thickness of the metal or alloy thin film formed on the substrate under the above conditions was measured, and the value obtained by dividing this by the film formation time was defined as the film formation rate [nm / sec].
　また、スパッタリング中における放電安定性を評価するため、上記スパッタリングターゲットをスパッタ装置に装着し、アーキング特性を評価した。放電条件はスパッタリングガス：Ａｒ、スパッタリングガス圧：２．０ｍＴｏｒｒ（０．２７Ｐａ）、スパッタリング電力：２．０ｋＷで、積算スパッタリング電力が５ｋＷｈに達するまで連続放電し、その間に発生したアーキング回数を測定した。アーキングはＤＣ電源供給ケーブルに直接コイルを巻き、オシロスコープにてアーキングを観察した。 Also, in order to evaluate the discharge stability during sputtering, the sputtering target was mounted on a sputtering apparatus, and the arcing characteristics were evaluated. The discharge conditions were sputtering gas: Ar, sputtering gas pressure: 2.0 mTorr (0.27 Pa), sputtering power: 2.0 kW, continuous discharge until the integrated sputtering power reached 5 kWh, and the number of arcing generated during that time was measured. . For arcing, a coil was directly wound around a DC power supply cable, and arcing was observed with an oscilloscope.
Figure JPOXMLDOC01-appb-T000003
 　 
Figure JPOXMLDOC01-appb-T000003
 　 
　表２において、金属又は合金によって成膜速度が異なってくるが、同じ金属又は合金の中で比較すると、いずれの場合においても｛２００｝と｛２２２｝面集積度が本発明範囲外の比較例に比べて本発明範囲内の発明例では成膜速度が大きいものとなった。
　Ｎｏ．２８～３０はＣｒのターゲット材である。Ｎｏ．２８は圧延時の１パス当たりの圧下率が１０％以下であり、｛２００｝と｛２２２｝面集積度が本発明範囲外の比較例となった。一方、Ｎｏ．２９、３０は本発明範囲内の発明例であった。発明例は比較例に比べて成膜速度が大きく、アーキング回数は小さくなっていた。 In Table 2, the deposition rate differs depending on the metal or alloy, but when compared in the same metal or alloy, in any case, the {200} and {222} plane integration levels are outside the scope of the present invention. In contrast, in the invention examples within the scope of the present invention, the film formation rate was high.
No. 28 to 30 are Cr target materials. No. No. 28 had a rolling reduction per pass during rolling of 10% or less, and the {200} and {222} plane integration degrees were comparative examples outside the scope of the present invention. On the other hand, no. 29 and 30 were invention examples within the scope of the present invention. The inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
　Ｎｏ．３１～３３はＷのターゲット材である。Ｎｏ．３１は圧延温度が９００℃を超えており、｛２００｝と｛２２２｝面集積度が本発明範囲外の比較例となった。一方、Ｎｏ．３２、３３は本発明範囲内の発明例であった。発明例は比較例に比べて成膜速度が大きく、アーキング回数は小さくなっていた。 No. 31 to 33 are W target materials. No. No. 31 had a rolling temperature exceeding 900 ° C., and the degree of {200} and {222} plane integration was a comparative example outside the scope of the present invention. On the other hand, no. 32 and 33 were invention examples within the scope of the present invention. The inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
　Ｎｏ．３４～３６はＶのターゲット材である。Ｎｏ．３４は原料ブロックの結晶粒径が５０μｍを超えており、｛２００｝と｛２２２｝面集積度が本発明範囲外の比較例となった。一方、Ｎｏ．３５、３６は本発明範囲内の発明例であった。発明例は比較例に比べて成膜速度が大きく、アーキング回数は小さくなっていた。 No. 34 to 36 are V target materials. No. In No. 34, the crystal grain size of the raw material block exceeded 50 μm, and the {200} and {222} plane integration degrees were comparative examples outside the scope of the present invention. On the other hand, no. 35 and 36 were invention examples within the scope of the present invention. The inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
　Ｎｏ．３７～３９はＴａのターゲット材である。Ｎｏ．３７は原料ブロックの結晶粒径が１０μｍ以下であり、｛２００｝と｛２２２｝面集積度が本発明範囲外の比較例となった。一方、Ｎｏ．３８、３９は本発明範囲内の発明例であった。発明例は比較例に比べてアーキング回数は小さくなっていた。 No. Reference numerals 37 to 39 are Ta target materials. No. No. 37 had a crystal grain size of the raw material block of 10 μm or less, and the {200} and {222} plane integration degrees were comparative examples outside the scope of the present invention. On the other hand, no. 38 and 39 were invention examples within the scope of the present invention. The invention example had a smaller number of arcing times than the comparative example.
　Ｎｏ．４０～４２はＣｒ－Ｍｏのターゲット材である。Ｎｏ．４０は圧延時の全圧下率が２０％未満であり、｛２００｝と｛２２２｝面集積度が本発明範囲外の比較例となった。一方、Ｎｏ．４１、４２は本発明範囲内の発明例であった。発明例は比較例に比べて成膜速度が大きく、アーキング回数は小さくなっていた。 No. Reference numerals 40 to 42 are Cr—Mo target materials. No. No. 40 had a total rolling reduction of less than 20% during rolling, and the {200} and {222} plane integration degrees were comparative examples outside the scope of the present invention. On the other hand, no. 41 and 42 were invention examples within the scope of the present invention. The inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
　Ｎｏ．４３～４５はＭｏ－Ｗのターゲット材である。Ｎｏ．４３は酸素濃度が５００ｐｐｍを超えており、本発明範囲外の比較例となった。一方、Ｎｏ．４４、４５は本発明範囲内の発明例であった。発明例は比較例に比べてアーキング回数は小さくなっていた。 No. 43 to 45 are Mo-W target materials. No. No. 43 has an oxygen concentration exceeding 500 ppm, which is a comparative example outside the scope of the present invention. On the other hand, no. 44 and 45 were invention examples within the scope of the present invention. The invention example had a smaller number of arcing times than the comparative example.
　Ｎｏ．４６～４８はＭｏ－Ｎｂのターゲット材である。Ｎｏ．４６は原料ブロックの相対密度が９９．０％以上でおり、｛２００｝と｛２２２｝面集積度が本発明範囲外の比較例となった。一方、Ｎｏ．４７、４８は本発明範囲内の発明例であった。発明例は比較例に比べて成膜速度が大きく、アーキング回数は小さくなっていた。 No. Reference numerals 46 to 48 denote Mo—Nb target materials. No. No. 46 had a relative density of raw material blocks of 99.0% or more, and the {200} and {222} plane integration degrees were comparative examples outside the scope of the present invention. On the other hand, no. 47 and 48 were invention examples within the scope of the present invention. The inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
　Ｎｏ．４９～５１はＮｂのターゲット材である。Ｎｏ．４９は原料ブロックの結晶粒径が５０μｍを超えており、｛２００｝と｛２２２｝面集積度が本発明範囲外の比較例となった。一方、Ｎｏ．５０、５１は本発明範囲内の発明例であった。発明例は比較例に比べて成膜速度が大きく、アーキング回数は小さくなっていた。 No. Reference numerals 49 to 51 are Nb target materials. No. In No. 49, the crystal grain size of the raw material block exceeded 50 μm, and the {200} and {222} plane integration degrees were comparative examples outside the scope of the present invention. On the other hand, no. 50 and 51 were invention examples within the scope of the present invention. The inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
　以上示したように、本発明の金属系スパッタリングターゲット板は従来に比べてより優れたスループット性能を有することを確認できた。 As described above, it was confirmed that the metal-based sputtering target plate of the present invention has better throughput performance than the conventional one.
　(実施例４)
　平均粒径が４μｍの純Ｍｏ粉末を出発材料として、加熱焼結と圧延によって各種のＭｏスパッタリングターゲット材の製造を行った。原料粉末には１２００質量ｐｐｍの酸素が付着しており、水素中で還元焼結処理することによって酸素濃度を減少させたブロックを作製することにした。 Example 4
Various Mo sputtering target materials were manufactured by heat sintering and rolling using pure Mo powder having an average particle size of 4 μm as a starting material. The raw material powder had 1200 mass ppm of oxygen attached thereto, and it was decided to produce a block in which the oxygen concentration was reduced by reducing and sintering in hydrogen.
　まず、ＣＩＰ法によりＭｏ粉末を固め、真空引きした後に水素をパージし、さらに大気圧で水素を流した熱処理炉内で還元しながら同時に加熱焼結させた。焼結温度はブロックによって変え、その範囲は１１００～１８００℃であった。得られたブロック寸法は幅３００ｍｍ、長さ９５０ｍｍの一定値とし、厚みは４６～８０ｍｍであった。平均結晶粒径は９．９～５３μｍ、相対密度は８９．９％～９９．０％であった。 First, the Mo powder was hardened by the CIP method, vacuumed and then purged with hydrogen, and further heated and sintered while being reduced in a heat treatment furnace in which hydrogen was passed at atmospheric pressure. The sintering temperature varied from block to block and the range was 1100-1800 ° C. The obtained block dimensions were constant values of 300 mm width and 950 mm length, and the thickness was 46 to 80 mm. The average crystal grain size was 9.9 to 53 μm, and the relative density was 89.9% to 99.0%.
　作製したブロックに含有する酸素濃度は処理時間が長くなるほど減少し、酸素濃度の制御は処理時間で行った。酸素濃度の分析は焼結させた後のブロックで行った。また、ブロックには集合組織は形成されておらず、結晶方位はランダムであった。金属組織を観察して線分法で求めた各ブロックの結晶粒径は表３に示した。異なる酸素濃度と結晶粒径のＭｏブロック板に対して、それぞれ、厚み１２ｍｍのＳＳ４００鋼板のカプセルで周りを覆った。この際、ブロック表面とカプセル板の間の隙間は１ｍｍ以下になるようにした。 The oxygen concentration contained in the produced block decreased as the treatment time increased, and the oxygen concentration was controlled by the treatment time. The analysis of oxygen concentration was performed on the block after sintering. Further, no texture was formed in the block, and the crystal orientation was random. Table 3 shows the crystal grain size of each block obtained by observing the metal structure by the line segment method. Each of the Mo block plates having different oxygen concentrations and crystal grain sizes was covered with a capsule of SS400 steel plate having a thickness of 12 mm. At this time, the gap between the block surface and the capsule plate was set to 1 mm or less.
　表３に示した各種の条件で、前記カプセルで覆ったＭｏブロック板に圧延を施した。条件としては、圧延開始温度、１パスあたりの圧下率、全圧下率を変えた。ここで、圧延中の板温度が圧延開始温度に比べて１００℃以上低下した際には、圧延開始温度に板温度を戻すために同じ温度で再加熱を行った。 The Mo block plate covered with the capsule was rolled under various conditions shown in Table 3. As conditions, the rolling start temperature, the rolling reduction per pass, and the total rolling reduction were changed. Here, when the plate temperature during rolling decreased by 100 ° C. or more compared to the rolling start temperature, reheating was performed at the same temperature in order to return the plate temperature to the rolling start temperature.
　圧延完了後に靱性を回復させるために各Ｍｏ板に熱処理を施した。表３に示したように、この熱処理の温度はそれぞれ８５０℃～１１００℃の範囲であった。得られた圧延板の｛２００｝、｛２２２｝、および、｛１１０｝面集積度は、Ｘ線回折法（ＭｏＫα線）で測定した。測定面は圧延板の表面から厚み方向へ２．０ｍｍ深さの位置にあり、圧延面に平行な面を機械加工で切り出して行った。結晶相の｛２００｝面集積度、｛２２２｝面集積度、および、｛１１０｝面集積度の測定は、先に述べた方法で求め、例えば、｛２００｝強度比率では、前述した式（１）のように求めた。ここで、厚み中心の位置で同じ面集積度の測定を行ったが、各面とも同等なレベルの面集積度が測定された。 Each Mo plate was heat treated to restore toughness after completion of rolling. As shown in Table 3, the temperature of this heat treatment was in the range of 850 ° C. to 1100 ° C., respectively. The {200}, {222} and {110} plane integration degree of the obtained rolled sheet was measured by an X-ray diffraction method (MoKα ray). The measurement surface was located at a depth of 2.0 mm in the thickness direction from the surface of the rolled plate, and a surface parallel to the rolled surface was cut out by machining. The {200} plane integration degree, {222} plane integration degree, and {110} plane integration degree of the crystal phase are obtained by the method described above. For example, in the {200} intensity ratio, It was obtained as in 1). Here, the same surface integration degree was measured at the position of the thickness center, but the same level of surface integration degree was measured for each surface.
　圧延板の表面から厚み方向へ２．０ｍｍ深さの位置において圧延面の法線方向から金属組織を観察し、圧延に垂直方向の結晶粒径を線分法で測定した。得られたブロック板から１２７ｍｍ×１９１ｍｍ×５ｍｍｔの試験材を切り出し、１００ｍｍφ×５ｍｍｔに加工した。ここで、前記切り出した試験材のスパッタリング面は、圧延面の表面から深さ方向に２．０ｍｍ深さの位置に設定した。前記試験材をＣｕ製のバッキングプレートにボンディングしてスパッタリングターゲット材を作成した。このターゲット材を用いて、スパッタリング時のスループット性能を評価した。 The metal structure was observed from the normal direction of the rolling surface at a position 2.0 mm deep from the surface of the rolled plate in the thickness direction, and the crystal grain size in the direction perpendicular to the rolling was measured by the line segment method. A 127 mm × 191 mm × 5 mmt test material was cut out from the obtained block plate and processed into 100 mmφ × 5 mmt. Here, the sputtering surface of the cut out test material was set at a depth of 2.0 mm in the depth direction from the surface of the rolled surface. The test material was bonded to a Cu backing plate to prepare a sputtering target material. Using this target material, the throughput performance during sputtering was evaluated.
　作製されたスパッタリングターゲット材をスパッタ装置に装着し、ガラス基板上にＭｏ薄膜を成膜することにより成膜速度の測定を行った。スパッタリングにおける条件は次の通りとした。スパッタリングガス：Ａｒ、スパッタリングガス圧：２．５ｍＴｏｒｒ（０．３３Ｐａ）、スパッタリング電力：０．６ｋＷ、基板：Ｃｏｒｎｉｎｇ＃７０５９（５０×５０ｍｍ2）。また、成膜速度測定の際には、予めプレスパッタリングを行った。このプレスパッタリングの条件は、Ａｒガス圧５ｍＴｏｒｒ（０．６６Ｐａ）、スパッタリング電力１．０ｋＷ、時間１０ｍｉｎである。その後、投入電力１．０ｋＷにて１１ｍｉｎ成膜し形成された薄膜の膜厚を測定した。上記条件で基板上に成膜したＭｏ薄膜の膜厚測定を行い、これを成膜時間で除した値を成膜速度［ｎｍ／ｓｅｃ］とした。  The produced sputtering target material was mounted on a sputtering apparatus, and a film formation rate was measured by forming a Mo thin film on a glass substrate. The sputtering conditions were as follows. Sputtering gas: Ar, a sputtering gas pressure: 2.5mTorr (0.33Pa), sputtering power: 0.6 kW, substrate: Corning # 7059 (50 × 50mm 2). In addition, pre-sputtering was performed in advance when measuring the film formation rate. The pre-sputtering conditions are an Ar gas pressure of 5 mTorr (0.66 Pa), a sputtering power of 1.0 kW, and a time of 10 min. Then, the film thickness of the thin film formed by depositing for 11 min at an input power of 1.0 kW was measured. The film thickness of the Mo thin film formed on the substrate under the above conditions was measured, and the value obtained by dividing this by the film formation time was defined as the film formation rate [nm / sec].
　また、スパッタリング中における放電安定性を評価するため、上記スパッタリングターゲットをスパッタ装置に装着し、アーキング特性を評価した。放電条件はスパッタリングガス：Ａｒ、スパッタリングガス圧：２．５ｍＴｏｒｒ（０．３３Ｐａ）、スパッタリング電力：１．０ｋＷで、積算スパッタリング電力が３ｋＷｈに達するまで連続放電し、その間に発生したアーキング回数を測定した。アーキング回数の測定は異常放電で発生する電磁波を、高感度センサである導波管センサで検出し、オシロスコープで分析する方法で行った。
Figure JPOXMLDOC01-appb-T000004
 Moreover, in order to evaluate the discharge stability during sputtering, the sputtering target was mounted on a sputtering apparatus, and the arcing characteristics were evaluated. The discharge conditions were sputtering gas: Ar, sputtering gas pressure: 2.5 mTorr (0.33 Pa), sputtering power: 1.0 kW, continuous discharge until the integrated sputtering power reached 3 kWh, and the number of arcing generated during that time was measured. . The number of arcing times was measured by detecting electromagnetic waves generated by abnormal discharge with a waveguide sensor, which is a highly sensitive sensor, and analyzing with an oscilloscope.
Figure JPOXMLDOC01-appb-T000004
　表３において、成膜速度が４０．０（nm／min）以上であって、かつ、アーキング回数が１０回以下であったＭｏ板を合格として評価した。ターゲットのサイズが大きいので成膜速度が全て大きくなっている。また、アーキング測定の感度が高いので、アーキングが発生するサンプルではその発生回数が多くなっている。Ｎｏ．５２～６０の材料はターゲット板の条件が本発明範囲に入っていない比較例である。 In Table 3, a Mo plate having a deposition rate of 40.0 (nm / min) or more and an arcing count of 10 or less was evaluated as acceptable. Since the target size is large, the film formation rate is all increased. In addition, since the sensitivity of arcing measurement is high, the number of occurrences of arcing increases in samples. No. The materials 52 to 60 are comparative examples in which the conditions of the target plate are not within the scope of the present invention.
　Ｎｏ．５２は、酸素濃度５５０ｐｐｍ、結晶粒径２７μｍ、相対密度９７．４％、厚み４６ｍｍの原料ブロック板を圧延開始温度６５０℃、１パス当たりの圧下率を１４％とし、全圧下率５３％で圧延したものである。圧延後には９００℃×４ｈの熱処理を施した。｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲に入っていたが、酸素濃度が本発明の範囲から外れていた。この場合には、成膜速度は他の発明例と同程度であったが、アーキング回数が極めて多かった。したがって、スループット性能は他の発明例に比べて劣っていた。 No. No. 52 is a raw material block plate having an oxygen concentration of 550 ppm, a crystal grain size of 27 μm, a relative density of 97.4%, and a thickness of 46 mm, rolled at a rolling start temperature of 650 ° C., a rolling reduction per pass of 14%, and a total rolling reduction of 53%. It is a thing. After rolling, a heat treatment of 900 ° C. × 4 h was performed. Both {200} plane integration and {222} plane integration were within the scope of the present invention, but the oxygen concentration was outside the scope of the present invention. In this case, the deposition rate was similar to that of the other invention examples, but the number of arcing was extremely large. Therefore, the throughput performance was inferior compared to the other invention examples.
　Ｎｏ．５３は、酸素濃度３５ｐｐｍ、結晶粒径５３μｍ、相対密度９６．８％、厚み７０ｍｍの原料ブロック板を圧延開始温度８２０℃、１パス当たりの圧下率を１３％とし、全圧下率７５％で圧延したものである。圧延後には９５０℃×２ｈの熱処理を施した。酸素濃度は本発明の範囲に入っていたが、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲を外れていた。この場合には、成膜速度はいずれの発明例に比べて小さく、アーキング回数が多かった。したがって、スループット性能は他の発明例に比べて劣っていた。 No. 53 is a material block plate having an oxygen concentration of 35 ppm, a crystal grain size of 53 μm, a relative density of 96.8%, and a thickness of 70 mm, rolled at a rolling start temperature of 820 ° C., a rolling reduction rate of 13%, and a total rolling reduction rate of 75%. It is a thing. After rolling, a heat treatment of 950 ° C. × 2 h was performed. Although the oxygen concentration was within the range of the present invention, the {200} plane integration level and the {222} plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
　Ｎｏ．５４は、酸素濃度３５ｐｐｍ、結晶粒径９．９μｍ、相対密度９６．９％、厚み７０ｍｍの原料ブロック板を圧延開始温度８２０℃、１パス当たりの圧下率を１３％とし、全圧下率７５％で圧延したものである。圧延後には９５０℃×２ｈの熱処理を施した。酸素濃度は本発明の範囲に入っていたが、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲を外れていた。この場合には、成膜速度はいずれの発明例に比べて小さく、アーキング回数が多かった。したがって、スループット性能は他の発明例に比べて劣っていた。 No. No. 54 is a raw material block plate having an oxygen concentration of 35 ppm, a crystal grain size of 9.9 μm, a relative density of 96.9% and a thickness of 70 mm, a rolling start temperature of 820 ° C., a rolling reduction per pass of 13%, and a total rolling reduction of 75%. Rolled with After rolling, a heat treatment of 950 ° C. × 2 h was performed. Although the oxygen concentration was within the range of the present invention, the {200} plane integration level and the {222} plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
　Ｎｏ．５５は、酸素濃度９５ｐｐｍ、結晶粒径１８μｍ、相対密度８９．９％、厚み６０ｍｍの原料ブロック板を圧延開始温度８７０℃、１パス当たりの圧下率を２３％とし、全圧下率４１％で圧延したものである。圧延後には１０５０℃×０．５ｈの熱処理を施した。酸素濃度は本発明の範囲に入っていたが、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲を外れていた。この場合には、成膜速度はいずれの発明例に比べて小さく、アーキング回数が多かった。したがって、スループット性能は他の発明例に比べて劣っていた。 No. 55 is a raw material block plate having an oxygen concentration of 95 ppm, a crystal grain size of 18 μm, a relative density of 89.9%, and a thickness of 60 mm, rolled at a rolling start temperature of 870 ° C., a reduction rate of 23% per pass, and a total reduction rate of 41%. It is a thing. After rolling, a heat treatment of 1050 ° C. × 0.5 h was performed. Although the oxygen concentration was within the range of the present invention, the {200} plane integration level and the {222} plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
　Ｎｏ．５６は、酸素濃度９５ｐｐｍ、結晶粒径１８μｍ、相対密度９９．０％、厚み６０ｍｍの原料ブロック板を圧延開始温度８７０℃、１パス当たりの圧下率を２３％とし、全圧下率４１％で圧延したものである。圧延後には１０５０℃×０．５ｈの熱処理を施した。酸素濃度は本発明の範囲に入っていたが、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲を外れていた。この場合には、成膜速度はいずれの発明例に比べて小さく、アーキング回数が多かった。したがって、スループット性能は他の発明例に比べて劣っていた。 No. No. 56 is a raw material block plate having an oxygen concentration of 95 ppm, a crystal grain size of 18 μm, a relative density of 99.0% and a thickness of 60 mm, rolled at a rolling start temperature of 870 ° C., a reduction rate of 23% per pass, and a total reduction rate of 41%. It is a thing. After rolling, a heat treatment of 1050 ° C. × 0.5 h was performed. Although the oxygen concentration was within the range of the present invention, the {200} plane integration level and the {222} plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
　Ｎｏ．５７は、酸素濃度２００ｐｐｍ、結晶粒径２７μｍ、相対密度９６．３％、厚み４０ｍｍの原料ブロック板を圧延開始温度６５０℃、１パス当たりの圧下率を３％とし、全圧下率５３％で圧延したものである。圧延後には９００℃×４ｈの熱処理を施した。酸素濃度は本発明の範囲に入っていたが、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲を外れていた。この場合には、成膜速度はいずれの発明例に比べて小さく、アーキング回数が多かった。したがって、スループット性能は他の発明例に比べて劣っていた。 No. No. 57 is a raw material block plate having an oxygen concentration of 200 ppm, a crystal grain size of 27 μm, a relative density of 96.3%, and a thickness of 40 mm, rolled at a rolling start temperature of 650 ° C., a rolling reduction rate of 3%, and a total rolling reduction rate of 53%. It is a thing. After rolling, a heat treatment of 900 ° C. × 4 h was performed. Although the oxygen concentration was within the range of the present invention, the {200} plane integration level and the {222} plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
　Ｎｏ．５８は、酸素濃度２００ｐｐｍ、結晶粒径２７μｍ、相対密度９７．０％、厚み４０．０ｍｍの原料ブロック板を圧延開始温度６５０℃、１パス当たりの圧下率を１４％とし、全圧下率１４％で圧延したものである。圧延後には９００℃×４ｈの熱処理を施した。酸素濃度は本発明の範囲に入っていたが、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲を外れていた。この場合には、成膜速度はいずれの発明例に比べて小さく、アーキング回数が多かった。したがって、スループット性能は他の発明例に比べて劣っていた。 No. No. 58 is a raw material block plate having an oxygen concentration of 200 ppm, a crystal grain size of 27 μm, a relative density of 97.0% and a thickness of 40.0 mm, a rolling start temperature of 650 ° C., a rolling reduction per pass of 14%, and a total rolling reduction of 14%. Rolled with After rolling, a heat treatment of 900 ° C. × 4 h was performed. Although the oxygen concentration was within the range of the present invention, the {200} plane integration level and the {222} plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
　Ｎｏ．５９は、酸素濃度２５ｐｐｍ、結晶粒径１８μｍ、相対密度９５．９％、厚み８０ｍｍの原料ブロック板を圧延開始温度９５０℃、１パス当たりの圧下率を３０％とし、全圧下率８３％で圧延したものである。圧延後には１０００℃×２ｈの熱処理を施した。酸素濃度は本発明の範囲に入っていたが、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲を外れていた。この場合には、成膜速度はいずれの発明例に比べて小さく、アーキング回数が多かった。したがって、スループット性能は他の発明例に比べて劣っていた。 No. 59 is a raw material block plate having an oxygen concentration of 25 ppm, a crystal grain size of 18 μm, a relative density of 95.9% and a thickness of 80 mm, rolled at a rolling start temperature of 950 ° C., a rolling reduction rate of 30%, and a total rolling reduction rate of 83%. It is a thing. After rolling, a heat treatment of 1000 ° C. × 2 h was performed. Although the oxygen concentration was within the range of the present invention, the {200} plane integration level and the {222} plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
　Ｎｏ．６０は、酸素濃度１０ｐｐｍ、結晶粒径２１μｍ、相対密度９７．５％、厚み７５ｍｍの原料ブロック板を圧延開始温度８５０℃、１パス当たりの圧下率を２０％とし、全圧下率７３．８％で圧延したものである。また、圧延後に１１００℃×２ｈ熱処理を施した。酸素濃度は本発明の範囲に入っていたが、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲を外れていた。この場合には、成膜速度はいずれの発明例に比べて小さく、アーキング回数が多かった。したがって、スループット性能は他の発明例に比べて劣っていた。 No. 60 is a raw material block plate having an oxygen concentration of 10 ppm, a crystal grain size of 21 μm, a relative density of 97.5%, and a thickness of 75 mm, a rolling start temperature of 850 ° C., a rolling reduction per pass of 20%, and a total rolling reduction of 73.8%. Rolled with Moreover, 1100 degreeC * 2 h heat processing was performed after rolling. Although the oxygen concentration was within the range of the present invention, the {200} plane integration level and the {222} plane integration level were both outside the range of the present invention. In this case, the film formation rate was smaller than that of any of the invention examples, and the number of arcing was large. Therefore, the throughput performance was inferior compared to the other invention examples.
　以下のＮｏ．６１～８５の材料はターゲット板の条件が本発明範囲に入っている発明例である。Ｎｏ．６１～６５は、酸素濃度を５～５００ｐｐｍの範囲で変え、結晶粒径２７μｍ、相対密度９７．３～９８．０％、厚み４６ｍｍにした原料ブロック板を用意し、圧延開始温度６５０℃、１パス当たりの圧下率を１４％とし、全圧下率５３％で圧延したものである。圧延後には９００℃×４ｈの熱処理を施した。酸素濃度は本発明の範囲５ｐｐｍ以上５００ｐｐｍ以下に入っており、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲に入っていた。ちなみに、酸素濃度が３ｐｐｍのブロック板の製造には、他のものに比べて１．５倍の時間がかかり、実用的でないと判断した。よって、前記ブロック板で、５ｐｐｍより低い酸素濃度ターゲット材を作製しなかった。 The following No. The materials 61 to 85 are invention examples in which the conditions of the target plate are within the scope of the present invention. No. Nos. 61 to 65 were prepared as raw material block plates in which the oxygen concentration was changed in the range of 5 to 500 ppm, the crystal grain size was 27 μm, the relative density was 97.3 to 98.0%, and the thickness was 46 mm. The rolling reduction per pass is 14% and the rolling reduction is 53%. After rolling, a heat treatment of 900 ° C. × 4 h was performed. The oxygen concentration falls within the range of 5 ppm to 500 ppm of the present invention, and the {200} plane integration degree and the {222} plane integration degree both fall within the scope of the present invention. By the way, it was determined that the production of a block plate having an oxygen concentration of 3 ppm took 1.5 times longer than the other, and was impractical. Therefore, an oxygen concentration target material lower than 5 ppm was not produced with the block plate.
　成膜速度は比較例（Ｎｏ．５２の比較例を除く）に比べて大きく、いずれの場合も４０ｎｍ／ｍｉｎを超えていた。酸素濃度が５００ｐｐｍであったＮｏ．６１では、アーキング回数は９回とやや大きかった。ターゲット材の酸素濃度が１００ｐｐｍ以上２００ｐｐｍ以下では２～６回と減少した。さらに、１００ｐｐｍ未満ならば、アーキングは全く起こらなかった。 The film formation rate was higher than that of the comparative example (excluding the comparative example of No. 52), and in both cases exceeded 40 nm / min. The oxygen concentration was 500 ppm. In 61, the number of arcing was slightly large, 9 times. When the oxygen concentration of the target material was 100 ppm or more and 200 ppm or less, it decreased to 2 to 6 times. Furthermore, if it was less than 100 ppm, no arcing occurred.
　Ｎｏ．６６～７１は結晶粒径を１０．５～５０μｍに変えて、酸素濃度３５ｐｐｍ、相対密度９６．２～９６．８％、厚み７０ｍｍの原料ブロック板を作製し、圧延開始温度８２０℃、１パス当たりの圧下率を１３％とし、全圧下率７５％で圧延したものである。圧延後には９５０℃×２ｈ、９３０℃×０．５ｈ、９２０℃×０．５ｈの熱処理を施した。酸素濃度は本発明の範囲に入っており、｛２００｝面集積度および｛２２２｝面集積度のうち少なくとも一方が本発明範囲に入っていた。 No. In Nos. 66 to 71, the raw material block plate having an oxygen concentration of 35 ppm, a relative density of 96.2 to 96.8%, and a thickness of 70 mm was prepared by changing the crystal grain size to 10.5 to 50 μm, and the rolling start temperature was 820 ° C. for 1 pass. The rolling reduction is 13% and the rolling reduction is 75%. After rolling, heat treatments of 950 ° C. × 2 h, 930 ° C. × 0.5 h, and 920 ° C. × 0.5 h were performed. The oxygen concentration is within the scope of the present invention, and at least one of the {200} plane integration degree and the {222} plane integration degree is within the scope of the present invention.
　成膜速度は比較例（Ｎｏ．５２の比較例を除く）に比べて大きく、Ｎｏ．７１の実施例を除いてアーキングは全く起きなかった。ここで、ターゲット板の結晶粒径が、１μｍ以上ではアーキングが起こらなくなり、更に１０μｍを超えると特に成膜速度は高かった。
　Ｎｏ．７２～７７は、酸素濃度９５ｐｐｍ、結晶粒径１８μｍ、相対密度９０．０～９８．８％、厚み６０ｍｍの原料ブロック板を圧延開始温度８７０℃、１パス当たりの圧下率を２３％とし、全圧下率４１％で圧延したものである。圧延後には１０５０℃×０．５ｈの熱処理を施した。酸素濃度は本発明の範囲に入っており、｛２００｝面集積度および｛２２２｝面集積度のうち少なくとも一方が本発明範囲に入っていた。 The film formation rate is larger than that of the comparative example (excluding the comparative example of No. 52). Except for 71 examples, no arcing occurred. Here, when the crystal grain size of the target plate is 1 μm or more, arcing does not occur, and when it exceeds 10 μm, the film formation rate is particularly high.
No. 72-77 is a raw material block plate having an oxygen concentration of 95 ppm, a crystal grain size of 18 μm, a relative density of 90.0 to 98.8%, and a thickness of 60 mm, a rolling start temperature of 870 ° C., a rolling reduction per pass of 23%, Rolled at a rolling reduction of 41%. After rolling, a heat treatment of 1050 ° C. × 0.5 h was performed. The oxygen concentration is within the scope of the present invention, and at least one of the {200} plane integration degree and the {222} plane integration degree is within the scope of the present invention.
　成膜速度は比較例（Ｎｏ．５２の比較例を除く）に比べて大きく、アーキングは全く起きなかった。ここで、ブロック板の相対密度が９４．０％以上９８．０％以下の場合により高い面集積度が得られ、成膜速度は高かった。 The film formation rate was higher than that of the comparative example (excluding the comparative example of No. 52), and no arcing occurred. Here, when the relative density of the block plate was 94.0% or more and 98.0% or less, a higher surface integration degree was obtained, and the film formation rate was high.
　Ｎｏ．７８～８１は、酸素濃度２５ｐｐｍ、結晶粒径１８μｍ、相対密度９６．５％、厚み８０ｍｍの原料ブロック板を圧延開始温度６００～９００℃、１パス当たりの圧下率を３０％とし、全圧下率８３％で圧延したものである。圧延後には１０００℃×２ｈの熱処理を施した。酸素濃度は本発明の範囲に入っており、｛２００｝面集積度および｛２２２｝面集積度はいずれも本発明範囲に入っていた。成膜速度は比較例（Ｎｏ．５２の比較例を除く）に比べて大きく、アーキングは全く起きなかった。 No. Nos. 78 to 81 are raw material block plates having an oxygen concentration of 25 ppm, a crystal grain size of 18 μm, a relative density of 96.5%, and a thickness of 80 mm, a rolling start temperature of 600 to 900 ° C., a rolling reduction rate per pass of 30%, and a total rolling reduction rate Rolled at 83%. After rolling, a heat treatment of 1000 ° C. × 2 h was performed. The oxygen concentration is within the scope of the present invention, and the {200} plane integration degree and the {222} plane integration degree are both within the scope of the present invention. The film formation rate was higher than that of the comparative example (excluding the comparative example of No. 52), and no arcing occurred.
　Ｎｏ．８２～８７は、酸素濃度１０ｐｐｍ、結晶粒径２１μｍ、相対密度９７．５％、厚み７５ｍｍの原料ブロック板を圧延開始温度８５０℃、１パス当たりの圧下率を２０％とし、全圧下率７３．８％で圧延したものである。圧延後には８５０℃から１０９０℃の温度で２ｈの熱処理を施した。酸素濃度は本発明の範囲に入っており、｛２００｝面集積度および｛２２２｝面集積度のうち少なくとも一方が本発明範囲に入っていた。圧延後の熱処理温度が１１００℃未満で本発明のターゲット板が得られた。成膜速度は比較例（Ｎｏ．５２の比較例を除く）に比べて大きく、アーキングは全く起きなかった。以上示したように、本発明のＭｏスパッタリングターゲット板は従来に比べてより優れたスループット性能を有することを確認できた。 No. 82 to 87 are raw material block plates having an oxygen concentration of 10 ppm, a crystal grain size of 21 μm, a relative density of 97.5%, and a thickness of 75 mm, a rolling start temperature of 850 ° C., a rolling reduction per pass of 20%, and a total rolling reduction of 73. Rolled at 8%. After rolling, heat treatment was performed at a temperature of 850 ° C. to 1090 ° C. for 2 hours. The oxygen concentration is within the scope of the present invention, and at least one of the {200} plane integration degree and the {222} plane integration degree is within the scope of the present invention. The target plate of the present invention was obtained at a heat treatment temperature after rolling of less than 1100 ° C. The film formation rate was higher than that of the comparative example (excluding the comparative example of No. 52), and no arcing occurred. As shown above, it has been confirmed that the Mo sputtering target plate of the present invention has better throughput performance than the conventional one.
　Ｎｏ．８８～９０は、酸素濃度３０ｐｐｍ、結晶粒径５０μｍ、相対密度９７．９％、厚み７５ｍｍの原料ブロック板を圧延開始温度８５０℃、１パス当たりの圧下率を２０％とし、全圧下率７３．８％で圧延したものである。圧延後には１０００℃から１０９０℃の温度で９ｈの熱処理を施した。酸素濃度は本発明の範囲に入っており、｛２００｝面集積度および｛２２２｝面集積度のうち少なくとも一方が本発明範囲に入っていた。圧延後の熱処理温度が１１００℃未満で本発明のターゲット板が得られた。成膜速度は比較例（Ｎｏ．５２の比較例を除く）に比べて大きく、Ｎｏ．８８、８９ではアーキングは全く起きなかった。Ｎｏ．９０ではターゲット板の結晶粒径が５０μｍを超えており、アーキングが１０回発生したが合格内に入っていた。以上示したように、本発明のＭｏスパッタリングターゲット板は従来に比べてより優れたスループット性能を有することを確認できた。 No. Nos. 88 to 90 are a raw material block plate having an oxygen concentration of 30 ppm, a crystal grain size of 50 μm, a relative density of 97.9%, and a thickness of 75 mm, a rolling start temperature of 850 ° C., a rolling reduction per pass of 20%, and a total rolling reduction of 73. Rolled at 8%. After rolling, heat treatment was performed for 9 hours at a temperature of 1000 ° C. to 1090 ° C. The oxygen concentration is within the scope of the present invention, and at least one of the {200} plane integration degree and the {222} plane integration degree is within the scope of the present invention. The target plate of the present invention was obtained at a heat treatment temperature after rolling of less than 1100 ° C. The film formation rate is larger than that of the comparative example (excluding the comparative example of No. 52). In 88 and 89, no arcing occurred. No. In 90, the crystal grain size of the target plate exceeded 50 μm, and arcing occurred 10 times, but it was within the acceptable range. As shown above, it has been confirmed that the Mo sputtering target plate of the present invention has better throughput performance than the conventional one.
　(実施例５)
　平均粒径が１～２０μｍのＣｒ、Ｗ、Ｖ、Ｔａ、Ｍｏ、Ｎｂ粉末を出発材料として、ＨＩＰと圧延によって各種スパッタリングターゲット材の製造を行った。まず、Ｃｒ、Ｗ、Ｖ、Ｔａ、Ｎｂについては単一粉末で純金属によるターゲット材を製造した。また、ＴａとＭｏ、ＭｏとＷ、ＭｏとＮｂの組み合わせで粉末を質量比で５０：５０の割合で混合して、合金ターゲット材を製造した。 (Example 5)
Various sputtering target materials were manufactured by HIP and rolling using Cr, W, V, Ta, Mo, and Nb powder having an average particle diameter of 1 to 20 μm as starting materials. First, for Cr, W, V, Ta, and Nb, a pure metal target material was manufactured with a single powder. Moreover, the alloy target material was manufactured by mixing powder in the ratio of 50:50 by mass ratio by the combination of Ta and Mo, Mo and W, and Mo and Nb.
　原料粉末にはそれぞれ１５００質量ｐｐｍの酸素が付着しており、水素中で還元熱処理することによって酸素濃度を減少させることにした。ＳＳ４００製のＨＩＰ用容器を用意して、原料粉末を中に充填した。容器内部を真空引きした後に水素をパージした後３００℃に加熱して還元させた。酸素濃度は保定時間が長くなるほど減少し、酸素濃度の制御は還元時間で行った。原料ブロックの酸素濃度の分析はＨＩＰ焼結させた後のブロックで行った。 The raw material powders each had 1500 ppm by mass of oxygen attached thereto, and the oxygen concentration was reduced by reducing heat treatment in hydrogen. An SS400 HIP container was prepared and filled with raw material powder. The inside of the container was evacuated and purged with hydrogen, and then heated to 300 ° C. for reduction. The oxygen concentration decreased as the retention time increased, and the oxygen concentration was controlled by the reduction time. Analysis of the oxygen concentration of the raw material block was performed on the block after HIP sintering.
　酸素濃度制御の処理後、ロータリーポンプと油拡散ポンプでＨＩＰ用容器の内部を真空引きした。真空度が１０-2Ｐa程度に到達した後、吸引口等をピンホールが発生してリークしないように注意して封印した。この後、１１５０～１４００℃×２時間保定、１２００気圧（１２１．６ＭＰａ）の条件でＨＩＰ焼結処理を施した。得られた焼結体から幅２５０ｍｍ×長さ１７００ｍｍ×厚み２０～９０ｍｍの原料ブロックを切り出した。前記ＨＩＰ温度は、具体的には、各金属について、Ｃｒ：１１５０℃、Ｗ：１４００℃、Ｖ：１１５０℃、Ｎｂ：１２００℃、Ｔａ－Ｍｏ：１３００℃、Ｍｏ－Ｗ：１３５０℃、Ｍｏ－Ｎｂ：１２００℃であり、それぞれの融点の１／３（タンマン温度）以上である。 After the oxygen concentration control process, the inside of the HIP container was evacuated with a rotary pump and an oil diffusion pump. After the degree of vacuum reached about 10 -2 Pa, the suction port and the like were sealed carefully so as not to leak due to pinholes. Thereafter, the HIP sintering process was performed under the conditions of 1150 to 1400 ° C. × 2 hours, 1200 atm (121.6 MPa). A raw material block having a width of 250 mm, a length of 1700 mm and a thickness of 20 to 90 mm was cut out from the obtained sintered body. Specifically, for each metal, the HIP temperature is Cr: 1150 ° C., W: 1400 ° C., V: 1150 ° C., Nb: 1200 ° C., Ta—Mo: 1300 ° C., Mo—W: 1350 ° C., Mo— Nb: 1200 ° C., which is equal to or higher than 1/3 (Taman temperature) of each melting point.
　これらの原料ブロックの相対密度、及び、それぞれの原料ブロックに含有する酸素濃度は表４に示したとおりである。 得られた原料ブロックは厚さ１２ｍｍのＳＳ４００鋼板でカプセル化した。この際、ブロック表面とカプセル板の隙間は１ｍｍ以下になるようにした。これらを加熱して、異なる圧延温度と全圧下率で圧延を施した。原料ブロックの条件と圧延条件に関しては、表４に記載した。圧延完了後に靱性を回復させるために各圧延板に熱処理を施した。表４に示したように、この熱処理の温度はそれぞれ８５０℃～１１００℃の範囲であった。 The relative density of these raw material blocks and the oxygen concentration contained in each raw material block are as shown in Table 4. The raw material block obtained was encapsulated with a SS400 steel plate having a thickness of 12 mm. At this time, the gap between the block surface and the capsule plate was set to 1 mm or less. These were heated and rolled at different rolling temperatures and total rolling reductions. The raw material block conditions and rolling conditions are shown in Table 4. Each rolled sheet was subjected to heat treatment to restore toughness after completion of rolling. As shown in Table 4, the temperature of this heat treatment was in the range of 850 ° C. to 1100 ° C., respectively.
　得られた圧延板の｛２００｝、｛２２２｝、｛１１０｝面集積度は、Ｘ線回折法（ＭｏＫα線）で測定した。いずれの測定片においても体心立方結晶であることがＸ線回折法でも確認できた。測定面は圧延板の表面から厚み方向へ３ｍｍ深さの位置にあり、圧延面に平行な面を機械加工で切り出して行った。結晶相の｛２００｝面集積度、｛２２２｝面集積度、および、｛１１０｝面集積度の測定は、先に述べた方法で求め、例えば、｛２００｝強度比率では、前述した式（１）のように求めた。 The {200}, {222}, {110} plane integration degree of the obtained rolled plate was measured by an X-ray diffraction method (MoKα ray). It was confirmed by X-ray diffraction that all the measurement pieces were body-centered cubic crystals. The measurement surface was located at a depth of 3 mm from the surface of the rolled plate in the thickness direction, and a surface parallel to the rolled surface was cut out by machining. The {200} plane integration degree, {222} plane integration degree, and {110} plane integration degree of the crystal phase are obtained by the method described above. For example, in the {200} intensity ratio, It was obtained as in 1).
　得られたブロック板から１００ｍｍφ×５ｍｍｔの試験材を切り出した。ここで、前記切り出した試験材のスパッタリング面は、圧延面の表面から深さ方向に２．０ｍｍ深さの位置に設定した。前記試験材をＣｕ製のバッキングプレートにボンディングしてスパッタリングターゲット材を作成した。このターゲット材を用いて、スパッタリング時のスループット性能を評価した。 A test material of 100 mmφ × 5 mmt was cut out from the obtained block plate. Here, the sputtering surface of the cut out test material was set at a depth of 2.0 mm in the depth direction from the surface of the rolled surface. The test material was bonded to a Cu backing plate to prepare a sputtering target material. Using this target material, the throughput performance during sputtering was evaluated.
　作製されたスパッタリングターゲット材をスパッタ装置に装着し、ガラス基板上にＭｏ薄膜を成膜することにより成膜速度の測定を行った。スパッタリングにおける条件は次の通りとした。スパッタリングガス：Ａｒ、スパッタリングガス圧：２．５ｍＴｏｒｒ（０．３３Ｐａ）、スパッタリング電力：０．６ｋＷ、基板：Ｃｏｒｎｉｎｇ＃７０５９（５０×５０ｍｍ2）。また、成膜速度測定の際には、予めプレスパッタリングを行った。このプレスパッタリングの条件は、Ａｒガス圧５ｍＴｏｒｒ（０．６６Ｐａ）、スパッタリング電力１．０ｋＷ、時間１０ｍｉｎである。その後、投入電力１．０ｋＷにて１１ｍｉｎ成膜し形成された薄膜の膜厚を測定した。上記条件で基板上に成膜した金属又は合金薄膜の膜厚測定を行い、これを成膜時間で除した値を成膜速度［ｎｍ／ｓｅｃ］とした。  The produced sputtering target material was mounted on a sputtering apparatus, and a film formation rate was measured by forming a Mo thin film on a glass substrate. The sputtering conditions were as follows. Sputtering gas: Ar, sputtering gas pressure: 2.5 mTorr (0.33 Pa), sputtering power: 0.6 kW, substrate: Corning # 7059 (50 × 50 mm 2 ). In addition, pre-sputtering was performed in advance when measuring the film formation rate. The pre-sputtering conditions are an Ar gas pressure of 5 mTorr (0.66 Pa), a sputtering power of 1.0 kW, and a time of 10 min. Then, the film thickness of the thin film formed by depositing for 11 min at an input power of 1.0 kW was measured. The film thickness of the metal or alloy thin film formed on the substrate under the above conditions was measured, and the value obtained by dividing this by the film formation time was defined as the film formation rate [nm / sec].
　また、スパッタリング中における放電安定性を評価するため、上記スパッタリングターゲットをスパッタ装置に装着し、アーキング特性を評価した。放電条件はスパッタリングガス：Ａｒ、スパッタリングガス圧：２．５ｍＴｏｒｒ（０．３３Ｐａ）、スパッタリング電力：１．０ｋＷで、積算スパッタリング電力が３ｋＷｈに達するまで連続放電し、その間に発生したアーキング回数を測定した。アーキング回数の測定は異常放電で発生する電磁波を、高感度である導波管センサで検出し、オシロスコープで分析する方法で行った。
Figure JPOXMLDOC01-appb-T000005
 Moreover, in order to evaluate the discharge stability during sputtering, the sputtering target was mounted on a sputtering apparatus, and the arcing characteristics were evaluated. The discharge conditions were sputtering gas: Ar, sputtering gas pressure: 2.5 mTorr (0.33 Pa), sputtering power: 1.0 kW, continuous discharge until the integrated sputtering power reached 3 kWh, and the number of arcing generated during that time was measured. . The number of arcing times was measured by detecting electromagnetic waves generated by abnormal discharge with a highly sensitive waveguide sensor and analyzing with an oscilloscope.
Figure JPOXMLDOC01-appb-T000005
　表４において、成膜速度が４０．０（nm／min）以上であって、かつ、アーキング回数が１０回以下であったターゲット材を合格として評価した。 In Table 4, a target material having a deposition rate of 40.0 (nm / min) or more and an arcing count of 10 or less was evaluated as acceptable.
　Ｎｏ．９１～９３はＣｒのターゲット材である。Ｎｏ．９１は１パス当たりの圧下率が１０％以下であり、｛２００｝と｛２２２｝面集積度が本発明範囲外の比較例となった。一方、Ｎｏ．９２、９３は本発明範囲内の発明例であった。発明例は比較例に比べて成膜速度が大きく、アーキング回数は小さくなっていた。 No. Reference numerals 91 to 93 are Cr target materials. No. No. 91 had a rolling reduction per pass of 10% or less, and the {200} and {222} plane integration degrees were comparative examples outside the scope of the present invention. On the other hand, no. 92 and 93 were invention examples within the scope of the present invention. The inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
　Ｎｏ．９４～９６はＷのターゲット材である。Ｎｏ．９４は圧延温度が９００℃を超えており、｛２００｝と｛２２２｝面集積度が本発明範囲外の比較例となった。一方、Ｎｏ．９５、９６は本発明範囲内の発明例であった。発明例は比較例に比べて成膜速度が大きく、アーキング回数は小さくなっていた。 No. 94 to 96 are W target materials. No. No. 94 had a rolling temperature exceeding 900 ° C., and the {200} and {222} plane integration degrees were comparative examples outside the scope of the present invention. On the other hand, no. 95 and 96 were invention examples within the scope of the present invention. The inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
　Ｎｏ．９７～９９はＶのターゲット材である。Ｎｏ．９７は、結晶粒径が５０μｍを超えた原料ブロックを使用し、得られたターゲット材の｛２００｝と｛２２２｝面集積度が本発明範囲外の比較例となった。一方、Ｎｏ．９８、９９は本発明範囲内の発明例であった。発明例は比較例に比べて成膜速度が大きく、アーキング回数は小さくなっていた。 No. Reference numerals 97 to 99 are V target materials. No. No. 97 used a raw material block having a crystal grain size exceeding 50 μm, and the {200} and {222} plane integration degrees of the obtained target material were comparative examples outside the scope of the present invention. On the other hand, no. 98 and 99 were invention examples within the scope of the present invention. The inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
　Ｎｏ．１００～１０２はＴａのターゲット材である。Ｎｏ．１００は、結晶粒径が１０μｍ以下の原料ブロックを使用し、得られたターゲット材の｛２００｝と｛２２２｝面集積度が本発明範囲外の比較例となった。一方、Ｎｏ．１０１、１０２は本発明範囲内の発明例であった。発明例は比較例に比べてアーキング回数は小さくなっていた。 No. 100 to 102 are Ta target materials. No. No. 100 used a raw material block having a crystal grain size of 10 μm or less, and the {200} and {222} plane integration degrees of the obtained target material were comparative examples outside the scope of the present invention. On the other hand, no. 101 and 102 were invention examples within the scope of the present invention. The invention example had a smaller number of arcing times than the comparative example.
　Ｎｏ．１０３～１０５はＴａ－Ｍｏのターゲット材である。Ｎｏ．１０３は全圧下率が２０％未満であり、｛２００｝と｛２２２｝面集積度が本発明範囲外の比較例となった。一方、Ｎｏ．１０４、１０５は本発明範囲内の発明例であった。発明例は比較例に比べて成膜速度が大きく、アーキング回数は小さくなっていた。 No. Reference numerals 103 to 105 are Ta—Mo target materials. No. No. 103 had a total rolling reduction of less than 20%, and the {200} and {222} plane integration degrees were comparative examples outside the scope of the present invention. On the other hand, no. 104 and 105 were invention examples within the scope of the present invention. The inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
　Ｎｏ．１０６～１０８はＭｏ－Ｗのターゲット材である。Ｎｏ．１０６は、ターゲット材の酸素濃度が５００ｐｐｍを超えており、本発明範囲外の比較例となった。一方、Ｎｏ．１０７、１０８は本発明範囲内の発明例であった。発明例は比較例に比べてアーキング回数は小さくなっていた。 No. 106 to 108 are Mo-W target materials. No. No. 106, the oxygen concentration of the target material exceeded 500 ppm, and was a comparative example outside the scope of the present invention. On the other hand, no. 107 and 108 were invention examples within the scope of the present invention. The invention example had a smaller number of arcing times than the comparative example.
　Ｎｏ．１０９～１１１はＭｏ－Ｎｂのターゲット材である。Ｎｏ．１０９は原料ブロックの相対密度が９９．０％以上であり、｛２００｝と｛２２２｝面集積度が本発明範囲外の比較例となった。一方、Ｎｏ．１１０、１１１は本発明範囲内の発明例であった。発明例は比較例に比べて成膜速度が大きく、アーキング回数は小さくなっていた。 No. Reference numerals 109 to 111 denote Mo—Nb target materials. No. No. 109 has a relative density of the raw material block of 99.0% or more, and the {200} and {222} plane integration degrees are comparative examples outside the scope of the present invention. On the other hand, no. 110 and 111 were invention examples within the scope of the present invention. The inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
　Ｎｏ．１１２～１１４はＮｂのターゲット材である。Ｎｏ．１１２は圧延後の熱処理温度が１１００℃以上であり、結晶方位がランダム化して｛２００｝と｛２２２｝面集積度が本発明範囲外の比較例となった。一方、Ｎｏ．１１３、１１４は本発明範囲内の発明例であった。発明例は比較例に比べて成膜速度が大きく、アーキング回数は小さくなっていた。 No. Reference numerals 112 to 114 are Nb target materials. No. In No. 112, the heat treatment temperature after rolling was 1100 ° C. or higher, the crystal orientation was randomized, and the {200} and {222} plane integration degrees were comparative examples outside the scope of the present invention. On the other hand, no. 113 and 114 were invention examples within the scope of the present invention. The inventive example had a higher deposition rate and a lower arcing frequency than the comparative example.
　以上示したように、本発明の金属系スパッタリングターゲット板は従来に比べてより優れたスループット性能を有することを確認できた。 As described above, it was confirmed that the metal-based sputtering target plate of the present invention has better throughput performance than the conventional one.
集束イオンビーム(FIB, Focused Ion Beam)をそれぞれ一定時間照射した場合の各結晶面における原子放出量Atom emission at each crystal plane when irradiated with focused ion beam (FIB, Focused Ion) Beam) for a certain period of time ｛２００｝面集積度、｛２２２｝面集積度、および、｛１１０｝面集積度の圧延開始温度依存性Rolling start temperature dependence of {200} plane integration, {222} plane integration, and {110} plane integration 圧延開始温度によって面集積度を変化させた材料の成膜速度（図２の材料の成膜速度）Deposition rate of material whose surface integration is changed by rolling start temperature (deposition rate of material in FIG. 2)

Claims (5)

  1.  立方晶系の結晶構造である金属又は合金から構成されているスパッタリングターゲット材であって、前記スパッタリングターゲット材に含有する酸素含有量が質量で５ｐｐｍ以上５００ｐｐｍ以下であり、スパッタ面に対する結晶相の{２００}面集積度が１５％以上８０％以下、または、スパッタ面に対する結晶相の{２２２}面集積度が１５％以上８０％以下であることを特徴とする金属系スパッタリングターゲット材。 A sputtering target material composed of a metal or alloy having a cubic crystal structure, wherein the oxygen content contained in the sputtering target material is 5 ppm or more and 500 ppm or less by mass, and the crystalline phase { 200} Surface integration degree is 15% or more and 80% or less, or {222} face integration degree of a crystal phase with respect to a sputtering surface is 15% or more and 80% or less.
  2.  前記スパッタリングターゲット材のスパッタ面に対する結晶相の{２００}面集積度と{２２２}面集積度の和が、３０％以上９５％以下であることを特徴とする請求項１記載の金属系スパッタリングターゲット材。 2. The metal-based sputtering target according to claim 1, wherein the sum of the {200} plane integration degree and {222} plane integration degree of the crystal phase with respect to the sputtering surface of the sputtering target material is 30% or more and 95% or less. Wood.
  3.  前記スパッタリングターゲット材のスパッタ面に対する{１１０}面集積度が、０．０１％以上８％以下であることを特徴とする請求項１又は２記載の金属系スパッタリングターゲット材。 The metal-based sputtering target material according to claim 1 or 2, wherein the {110} plane integration degree with respect to the sputtering surface of the sputtering target material is 0.01% or more and 8% or less.
  4.  前記スパッタリングターゲット材を構成する金属又は合金が、Ｃｒ、Ｍｏ、Ｗ、Ｖ、又はＴａのいずれか１つ以上を主元素とし、その結晶構造が立方晶系の体心立方格子構造を有することを特徴とする請求項１～３のいずれか１項に記載の金属系スパッタリングターゲット材。 The metal or alloy constituting the sputtering target material has one or more of Cr, Mo, W, V, or Ta as a main element, and the crystal structure thereof has a cubic body-centered cubic lattice structure. The metal sputtering target material according to any one of claims 1 to 3, wherein
  5. 　前記スパッタリングターゲット材の結晶相の結晶粒径が、１μｍ以上５０μｍ以下であることを特徴とする請求項１～４のいずれか１項に記載の金属系スパッタリングターゲット材。 5. The metal-based sputtering target material according to claim 1, wherein the crystal grain size of the crystal phase of the sputtering target material is 1 μm or more and 50 μm or less.
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US10570505B2 (en) 2015-05-22 2020-02-25 JX Nippon Mining & Materials Corporation Tantalum sputtering target, and production method therefor
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