TW593719B - Fine grain size material, sputtering target, methods of forming, and micro-arc reduction method - Google Patents

Abstract

A material may include grains of sizes such that at least 99% of a measured area contains grains that exhibit grain areas less than 10 times an area of a mean grain size of the measured area. As examples, at least 99% of the measured area may contain grains with grain areas less than 8, 6, or 3 times the area of the mean grain size. The grains may also have a mean grain size of less than 3 times a minimum statically recrystallized grain size, for example, a mean grain size of less than about 50 microns, 10 microns, or 1 micron. The material may be comprised by a sputtering target and a thin film may be deposited on a substrate from such a sputtering target. A micro-arc reduction method may include sputtering a film from a sputtering target comprising grains of sizes as described. A sputtering target forming method may include deforming a sputtering material. After the deforming, the sputtering material may be shaped into at least a portion of a sputtering target. The sputtering target may include grains of sizes as described. Also, the deforming may induce a strain level corresponding to epsilon of at least about 4. Further, the deforming may include equal channel angular extrusion.

Description

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 593719 A7 --_____ B7 V. Description of the Invention (1) iL Technical Field The present invention relates to fine-grained materials and sputtering targets, as well as methods for forming and reducing micro-melons. U Background Sputtering (also referred to as Physical Vapor Deposition (PVD)) is a technique that enables thin metal and / or ceramic magnetic layers to be deposited on a substrate by pure techniques. Money-emitting materials are used as cathodes in standard radio frequency (RF) and / or direct current (dc) base-radiation devices. For example, PVD is widely used in the semiconductor industry to produce integrated circuits. Extinction targets can be formed from a variety of metals and alloys. Some suitable materials are, in particular, A1'Ti'Cu'Ta'Ni'Mo, Au, Ag, and Pt, and alloys thereof, including alloys with & and 7G. Provided high resolution of sputter deposited films, as well as providing uniform and stage coverage, effective money shooting speed and other requirements. The target should have a homogeneous composition, a fine and uniform structure, controllable texture and no precipitation, particles and other contents. Thing. Like _, it should have high strength and simple selection for recycling. Therefore, important improvements in target metallurgy are expected. Some target sizes can be quite large. A typical target used to make liquid crystal displays (LCDs) is 860 X 910 X 19 cubic meters, which is expected to become larger in the future. These dimensions can pose additional challenges for making the right tools and methods. Various publications show that the main elements of the three targets can affect sputtering performance. The first element is the particle size of the material, which is the smallest component of a polycrystalline metal with a continuous lattice. The particle size range often ranges from a few millimeters to tens of micrometers 'depending on the nature of the metal' composition and processing. The letter is more compact and more -4- ^ The paper size applies the Chinese National Standard (CNS) ^^^ x 297 & Meal 1) ——rl · — 丨 #! (Please read the precautions on the back before filling this page} 、 π V. Description of the invention (Uniform particle size will improve the uniformity of the film, on the one hand, reduce the micro-arc. On the other hand, the yield and the deposition rate are the second factor. The second element is the target pattern. The specific way of each plane is determined by the "continued lattice" It is oriented relative to the stem surface of Geba. When the special = particle sum is not defined as the reorganization. Similar to the particle size, the knot: 0, 'grain is considered to be random structure, and the basis of the established metal ^ = It depends very much on the uniformity and sputtering speed of the predetermined thermomechanical location. The crystal grain can affect the size and structure of the two elements of the film, such as structural components, grains, and casting defects (such as precipitation, α 罘 phase precipitation, and Undesired, and " gap or 'hole). These structural components are often for the source of Γ and cold-dyeing of the film. Ma f. Geba Ba ·· {Report, production 0. Target production is difficult. I in Reduction of microisolation during sputtering and reduction of One grain, even # $ j material is enough to include p of a plurality of sizes so that at least 99% of the measurement area is based on the average ρ_ in the product, and the particle area is 10 times lower than the measurement surface J. For example, ^, Can contain particles with a larger particle area than Ping Qing |, soil shaojing measurement area. The particles can also have a small area that is 8, 6 or 3 times lower than the size of 3 pieces. Flat M 4 ^ smaller than the lowest recrystallization The average particle size of the particles can also be lower than the average energy A a 3 ^ ± size. For example, that chanting # sad recrystallized particles, particles can have an average particle size of less than 4 5QII about 1 to about 10 microns, or about 〇1 to about M, 万, 々, 々 _ ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, (-,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, ::::::: Ca, Sc, Ti, V, Cr, this paper rule New Zealand financial materials ^ ΤA4 · (21QX297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention Description (3 steal, ^, Co, Ni, c

Nb, Mo, Ru, pd, ~, n '~, Ge, Se, Sr, γ, Zr, w, ir, Pt, Au, Bi, =, In, Sn, Sb, Ba, La, Hf, ^, The sputtering target may include the above-mentioned " Nd'Sm, Eu, Gd, Tb, or Dy. A thin film is deposited on the substrate. Only expected. At the same time, from this sputtering target, particles of various sizes can be used in the micro-reduction method to shoot thin films. The thin film includes a complex product that is flat compared to the measured area. At least 99% of the measured area contains particles. The surface sputtering method includes 3 times lower recrystallized particle size. Can be shaped to at least-; two-shot material deformed. After deformation, the size of the sputtered material is so small that it shoots. Base shots can include multiple types, which are 9% lower than the average particle size in the measurement area. It is known that the particle area is 10 times lower than the average groove angle. For example, the deformation can be a cumulative strain of at least four. Temple ’s deformation can induce the equivalent of ε as a simple convergence of the world map. A preferred embodiment of the invention. The second figure shows the processing steps of ECAE embryo preparation. Figure A is a blueprint showing uneven microstructure.

FIG. 5B is a schematic diagram, and a cross-sectional view of the base metal structure of Table 亍 A has the micro-junction shown in FIG. 5A during the domain method. The optical microscopy of Xun alloy is used to illustrate the particle size distribution chart. Non-uniform microstructure of high purity prepared optical microscopy-6 This paper scale is applicable to China National Materials (CNS) 7 ^ :( 21GX297 Public meal — ——rl · 丨 丨 .1 — (Please read the precautions on the back before (Fill in this page)-Order V. Description of the invention (4) Figure. Figure 7 shows the optical micrograph of the high-purity record with the microstructure of the double uneven sentence. Figure 8A shows the particle area distribution of conventionally treated titanium Fig. 8B shows the area distribution of condensed particles treated with high strain technology. Fig. 9A shows the area distribution of copper treated with conventional treatment. Fig. 9B shows the area distribution of copper particles treated with high strain technology. Fig. 10A shows Optical micrograph of traditional microstructure of high-purity copper. Figure 10B shows the microscopic micrograph produced by the high-strain copper high-strain treatment technology. Figure ^ First figure, UA and 11B are used for target embryos. : Schematic diagram of the device. Figure 12 shows the preparation flow of the present invention Figure Π shows the flow chart of the particle area distribution evaluation method. The specific examples of the fish are detailed. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The size of the semiconducting ffH has decreased rapidly in the past ten years. The particles may become more important. The particles that were too small to cause problems may gradually appear to cause device damage or significantly affect the daily yield of the sundial. Studies indicate that the removal of base shots is becoming increasingly important in areas that cause micro-arcs. Type f9 also deducts more uniform and finer particle size sputtering target microstructures that can help reduce microfoxes. In particular, a novel method for imparting dryness characteristics may be required. Traditionally, sputtering leathers use The measurement of the average position from one or more positions in the leather is determined by the number of average particle sizes. Even. A target with a small average particle size can have particles in the particle size distribution, which can significantly affect sputtering performance. Therefore , With a narrow patellar -7-593719 V. Description of the invention (5)

A small distribution of money shot Geba can lead to the average particle size of each AA. ^ Beneficial. This ㈣ can still have a fine flat. Return to Figure 5A, and propose-insert + γ m kinds of non-uniform use of non-uniform microstructure 丨 produced by the conventional thermomechanical method. Five people, the main stand 4e h were distributed by reason. Fig. 5B shows the riding; j a wide range of particle sizes ... A *, shot, and material in the sputtering target 20. Due to the application of energy to the sputtering target 20, the micro-arc 26, «private», 土 & & 大 "big fruit, the right 24% of the combination occurred and generated ^ 22. The smooth sputtered surface of the fine particles 22 from the finer fine-grained area of the larger particles 24 is driven away. 2. The unproduced god, such as adultery, Ή Ή 5C indicates that the vanadium material 形成 formed by the traditional method is not used, and the possible particle size unevenness is shown. By deleting clusters of large particles and large particles within the ridge, you can target micro-arcs and generate particles. Large particles can be deleted ^ ./M, Guang Guang, j Chen Gang degrees can be set in the local microstructure to order 22 = ratio. Therefore, it is hardly enough to give spatter characteristics by deriving from distribution and / = heavy particle size, no additional characteristics-some materials 'such as copper' nickel 'nickel,' face and others, suffer from structural particle size irregularities. . There can be two types of dual; the right structure. The first type presents agglomeration of large particles in the parent material of small particles, whereas the second type presents a more continuous dispersion of particles with a small amount of scattering throughout the dry matrix, which is outside the desired normal particle size distribution. When the large particles in the family or the isolation point increase the tendency of micro-solitary, the second method is conducive to the low shot method. -Some materials, like convergence ... Ming alloy and others? It is not difficult for Yuma to suffer from double particle size distribution. However, the particle size distribution generated by conventional processing in such materials may be too broad for the above needs. -8 This paper size is in accordance with Chinese National Standard (CNS) A4 specifications (210 X297 printed and invented by the Consumers' Cooperative of the Central Economic and Technical Standards Bureau of the Ministry of Economic Affairs) (6 = 2 Figures 6 and 7 illustrate the dual particle structure. Figure 6 shows high Purity = uniform sentence microstructure, if it can be known by thermomechanical processing technology. A few: similar high-purity records of similar double uneven sentence microstructure, also produced by conventional thermomechanical processing technology. According to one invention The name of the granules, so that at least the measuring surface includes, the average size of the particles is 10 times lower than the average particle size area .: Two: the particle area in the product is lower than the average particle size area. Calculate.-An appropriate method is a method known to the measurement / artist. The center of t is approximately the same diameter as the circle. For the average particle size area, the average particle size can be m ,, and ", and the round door is approximately the same diameter: Wanfa It can be determined that the average area afterwards can be appropriately determined by the average particle size. The particle size distribution can be reduced by reducing the size of particles in extremely small areas. The base shot produces particles. The particles are two-hearted: the size of the particles is 3 times lower than the minimum static recrystallized particle size: the particles can have a flat static recrystallized particle size. For example, the weight of ten spoons is less than about 50 microns, about 1 to about 10 microcentre = meters. For many (but not all) traditional static recrystallized particles used for low-level shots, "materials", the lowest static recrystallized particles, about 1. Within micrometer range. At the same time, for this class In terms of materials, moving; about two crystal particles can fall within about G1 to about 1 micron. Again ~ the measured area can include at least four weeks of statistical representative area. Statistical representative surface 2 丨 Qx meal) ir- l · 丨 · — (Please read the notes on the back before filling in this page), π 593719 A7 B7 V. Description of the invention (The product can be calculated by any method known to the artist who is familiar with the present or future. Select to J / representative area The purpose of the four weeks is to include a large number of particles when measuring the average particle size and particle size distribution, and the data correctly reflects the overall microstructure of the material. Below a representative area may distort the data, so that the calculation (particle size distribution is more Measure the surface of the entire sample from a narrow or well-known producer. For example, the measurement area may include at least 1,000 particles of material condensing (joining together) particles. It may be possible to compare all surfaces of the sample on which the indicated measurement is made (that is, measurable) Even so, evaluation is more effective than representative area and is desirable. A suitable method is ASTM Test Method E112, Standard Test Method for Measuring Average Particle Size (Standard Test MethOdS fOr). Determining Average Grain Size)-At the same time, the rule of thumb or other methods are known in the art to select the representative area. Such other methods can include one or more of various martial arts methods cited by astm Em. In conjunction with the aspects of the invention described herein, FIG. 13 illustrates a method for evaluating particle area distribution. Materials that can have particles with the above properties may include one or more of the following: Be, B, C, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, co, Ni, with, &, with, with, heart, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs—r—K 丨 丨 #! (Please read the notes on the back before filling out this page) Y 'Zr, Nb, M. , RU, Pd, Ag, In, Sn, Sb, Ba, ^,

Hf, Ta, W, Ir, Pt, Au, Bi, Ce, and Sm, Eu, Gd, Chi or Dy. The material may basically consist of any one of the listed elements. The material also includes at least about 90 atomic percent parent elements, such as Ab η, cr,

Co ’Ni’ Cu ’Zr’ RU, Ag, In, Sn, Hf, Ta, ir, Pt

Au, and about 0 to about 10 atomic% of one or more alloying elements. The material ^ This paper size applies to the Chinese National Standard (CNS) A4 specification (2i × 297 mm 593719 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, and the invention description (8) may also include at least about 95 atoms. Kaibei Rensusu and .spoon ο · 1 to about 5 atomic% First listed: 丨 to 70 primes can include-one or more of the first genus, such as ... 22: primes can also include-one or more Transition gold Ta, 1 U '", Nb, Mo, pd, Ag, In, Sn, Sc, Sr, /, 7 and instead include reactive elements such as Mg, Ca,

Zr, Ba, LA, Hf, Ce or Nd. In Yiming <another point, the sputtering target may include the material. And in the dots, the thin film can be deposited on the substrate from this. : In view, the material can be composed of a plurality of particle groups. The measured surface area is composed of particles, and the current area is lower than the average particle size 2 in the measured surface area; 〇The above is expected to be used for sputtering leather The advantages of the material you include include shooting from a thin film—the film can be composed so that at least 99% of any measurement is made. ”It shows that the particle area is lower than the average of the measured surface area ==: 10 times. Sputtering target The particles can also be recrystallized by 3 times the size of the particles. The size is lower than the minimum static cost! Another point of view is that sputtering ... is composed of the lasing material and "Wanfa. After deformation, the occupational material can be empty], + Part of the sputtering target. The sputtering target can include a plurality of sizes of particle groups: 郅: less than 99% of any measured surface area is composed of two particles to two times the average particle size area of the measured surface area; times. = In order to include 鬲 strain treatment technology or severe plastic deformation. Under-form ^ In addition, the deformation can be -11-This paper size applies Chinese National Standard (CNS) M specification (210x297 public meal-—HrlK .—— # —— (Please first Read the precautions on the back and fill out this page) Order A7 ^^ ______ B7 V. Description of the invention (9) (Please read the precautions on the back before filling out this page) $ redundant equivalent to ε is a cumulative strain of at least 4. High strain Processing technology or strict = plastic deformation can include at least one kind of equal groove angle extrusion, high strain rate fire, or i method. The manufacturing method can also include rapid quenching and rapid thermal regression / ,. ~ A kind of rapid quenching technology can include die casting And rapid cooling to achieve small particle size and desired microstructures. The manufacturing method may also include a combination of thermomechanical processing and material alloys and / or Timura. Although alloys and / or supplemental additions are typically not used for refining microstructures, However, the addition of edge 2 to pure materials can stabilize the particle size and reduce the particle growth, so that a fine and uniform microstructure can be achieved without significantly affecting the properties of the stacked film. For example, with several different transition metals Supplementing high-purity aluminum can be successfully used to generate the particle size distribution according to the present invention, which can be difficult to obtain in pure aluminum. The powder metallurgy method is used to produce in a sputtering target. I hope the possible mechanism of the microstructure. The target with the desired microstructure can be produced by using the fine sieving material powder (preferably nanopowder), followed by the compaction and sintering steps. High strain techniques, such as those listed, and others, are suitable for forming microstructures according to the aspects of the invention described above. Traditional thermomechanical processing techniques, such as forging, rolling and annealing, sowing alloy additions and / or supplements are not helpful Fully uniform deformation can be obtained to remove large particles in the material. Such traditional methods typically include the generation of large gadolinium particles, the area of which is more than 10 times or more than 10 times larger than the area of the average particle size. Conversely, Some of the methods enumerated in this aspect of the invention impart south strain in a very uniform manner and / or ultra-high strain rates during rapid thermal processing. The desired microstructure control can also be achieved in materials with additives alloys, which control the stability and formation of highly strain-treated particles. -12- This paper size applies to the Chinese national standard ¥ 7cNS) A4 size (210 X297 mm) ) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 593719 V. Invention Description (10) Long. Figure 8A is a graph illustrating particle size distribution in the warp roots. This — when the middle of mechanical technology treatment occurs, this material can be improved when the two materials are mixed in the base, as indicated by the cumulative area: rate = slightly lonely tendency. … The measurement area referred to, this—; measuring knife / (A-F-㈣ 12 · 2 times the particles. About the picture: Γ two average particle size area), Π7 square microns. In the measurement area ^ 豕 the measurement area is rr which is calculated as the average particle size ====== on the contrary 1 according to various inventions === ?. After analysis to produce _ the material = 卞 9 weights of 5.9 microns, the average particle size and area under test was 27 3 2 miles: product / 2,192 square micrometers of internal production _ The measurement area is shown by the outside as shown in Figure 8B Generally, the area is composed of particles. The area is less than about 7.4 times the average particle size. Figures 9A and 9 show that the copper materials are similar to the data shown in Figure 8. In FIG. 9A ', the average particle size is 207 microns. Density: The area of the average particle size within a product of 692,481 square microns is Kappa: Unknown. At 99% of the measured area, the particles have a particle area 37 times lower than the average I small area. This proves the existence of larger particles, which can improve micro-direction. According to various viewpoints of the present invention, the particle size distribution of Figure VII is shown to be narrow. The copper material evaluated in Figure 9B clearly shows that the average particle size is: micron, and the average particle size is generated within the measurement area of 1,435,689 square microns. ——Rl · 丨 丨 #! (Please read the precautions on the back before filling this page }, Π -13-593719 A7 B7 V. Description of the invention (11) Master's is 28.9 5 square microns. At 99% of the measurement area, the particles have a particle surface

And the area below the average particle size is 4.75 times. FIG. 1GA shows an example of a high-purity copper material showing a W9A <particle area distribution pattern. Through comparison, Figures ~ OB show tf species in Figure 9B. High-purity copper materials with particle area distribution patterns. For example, Figure 10B is significantly easier than the particle size distribution difference in Figure 10A. More advantageous to use-a technology known as equal groove angle extrusion (ecae) &lt; special deformation technology. This technology was invented by ¥ M · sig (segai), and the United States Patent No. 5,400 633; 5,513 512; $, And states; and 5,590,39G, and co-suspended U.S. Patent No. 09 / 098,761, which was filed on June 17, 1998. The disclosure of the above patent application is incorporated herein by reference. ECAE -The general principle is to use two kinds of cross grooves of approximately equal cross-section, through which H embryos are caused to cause intra-embryo deformation. The best cross-sectional area of cross grooves is indeed equal to "exactly equal", which can be measured and manufactured in ECAE device. . However, "approximately equal" -words are used to indicate that the cross-sectional areas can be close to equal, rather than completely phase I, because, for example, they are used to form technical limitations. k Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs _ 丨 丨 rl · — ·! (Please read the precautions on the back before filling this page) «Set the thin areas of the cross section of the cross groove, one layer after another, and simply cut it to achieve. -A significant feature of the ECAE is that the shape and size of the embryo remain substantially unchanged during processing ("substantially unchanged"-the word indicates that the size has not been maintained ^ to the extent that the cross groove has a completely equal cross-section, and it also means that it must have exactly the same cross-section. Cross section). -14- Consumption cooperation by employees of the Central Bureau of Standards of the Ministry of Economic Affairs 593719 A7 ___B7_ V. Description of Invention (12) ECAE technology has many advantages. Such advantages can include: uniform and uniform strain in the whole cook; height deformation at each pass (ε = 117, ε has' traditional meaning, which is equivalent to reducing the natural logarithm of the proportion); high cumulative strain due to multiple passes (at N = 4 2 passes, ε = 4.64); different deformation paths, that is, the orientation changes of the embryos for ^ passes, allow for various paths and microstructures; and low loads and pressures. Compared to traditional practice, ECAE can reduce the particle size of high-purity alloys by at least a factor of 3. In terms of texture control, ECAE can also provide additional advantages over traditional practices. A preferred target has: a composition that is substantially uniform from beginning to end; almost no pores, inclusions, and any casting defects; a predetermined and smaller than about 50 microns; and a knot that is substantially uniform from beginning to end == grain. Very fine and uniform precipitates with an average particle diameter below 0.5 microns can also be present in the preferred palladium microstructure. The sputtering target of the present invention can be formed from an ingot made of any of the metals listed above. The bond block can be heat treated and treated by one or more of homogenization, hot forging, and maturation. It is extruded through two dies with equal cross sections separated from each other at a certain angle from the U groove. The key block material can also be annealed or / and processed by pass-by-dry methods, such as light pressing, cross-rolling or forging, and manufactured as an extinguishing target. In the final annealing, traditional processing and manufacturing steps can be repeated several extrusion steps through different deformation paths to produce a very extreme and uniform particle size in the treated material, and to control the texture strength and orientation in the material. -一-~ 15-——rl · — · —, (Please read the notes on the back before filling out this page) The standard is applicable ® ® Home Standard (CNS) Α4 Specification (210X 297mm) Central Ministry of Economic Affairs Printed by the Consumer Bureau of Standards Bureau 593719 V. Method of Invention (13) This method can be applied to a large target consisting of two or more parts. The sputtering target of the present invention can have the following characteristics: In: substantially uniform material composition at the location; = there are no holes, voids, inclusions and other casting defects in the quality; no deposits in the greed; particles Size is less than about 1 micron; Fine stable structure for sputtering applications; f. Substantially uniform structure and texture at any location; High-strength target without precision plate; Fork texture can be made from strong to medium, weak and close to random; Control the combined particle size and texture; large overall dry size; prolong the life of the sputtering target; and the optimal structural gradient across the target thickness. Targets with none of these characteristics can be produced by the methods described herein. Due to the back purity, the casting bond metallurgy method is: However, the constituent elements and additions that are cast across the ingot and large crystals: 1 results in a dendritic structure with a strong uneven hook. In addition, from 10,000 and two particles, high temperature and long-term homogenization cannot be applied to a specific embodiment of the present invention to use the homogenization time and temperature sufficient for redistribution and micro-condensation, followed by Equal channel angle extrusion (ECAE) with a sufficient number of passes (preferably soil solid) in order to solve this problem again. Refined granules from the plant and another-specific embodiments delete other casts that are not enough to completely remove by homogenization -16- This paper ruler (210χ 297 meals (please read the precautions on the back before filling this page)

593719 A7 B7__ 5. Description of the invention (14) Defects such as S-gap, porosity, cavities, gases, and inclusions, and use hot forging operations. Among the currently known methods, hot forging has limited applications, as reductions are limited and typically operate at low temperatures for pellet refining. When using slag ingots with the same thickness as the ECAE embryo, other methods cannot solve the problem. In the present invention, the cast-shaped key block has a large length-to-diameter ratio, preferably up to 2. During hot forging, the thickness of the ingot changed to the thickness of the ECAE embryo. This will provide substantial reductions sufficient to fully restore and remove casting defects. Another embodiment of the present invention relates to precipitates and particulate-free leather. In the currently known method, a precipitation-free material can be prepared by solubilizing in a final processing step. However, in this case, heating to the coagulation temperature produces very large particles. The present invention provides a method for manufacturing a precipitation-free and ultra-fine micronized target. According to this specific embodiment of the present invention, the solubilization is performed at the temperature and time required to dissolve all the precipitates and phase-bearing microparticles, followed by rapid quenching before ECAE. Subsequent ECAE and annealing are performed at temperatures below the maturation temperature of the corresponding material environment. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling out this page) A further specific embodiment of the present invention is a specific arrangement of homogenization, forging and solubilization operations. The cast ingot is heated and immersed at this temperature for the time required for homogenization, then cooled to the initial forging temperature, and then forged to the final thickness at the final forging temperature (which is higher than the melting temperature), and from Quenched at temperature. Through this specific embodiment, all processing steps are performed with one heating. This specific embodiment also includes another combination of non-homogenizing operation steps: forging at a temperature of about the solubilizing temperature and &gt; leveling after forging. According to the present invention, it is also possible to perform maturation after the time required for the temperature solubilization and the continuous production of fine sinkers with an average diameter of less than 0.5 microns. These Shen-17- This paper size applies Chinese National Standard (CNS) A4 specifications (210X 297 public envy 1 593719 A7 B7 V. Description of the invention (15) The sediment will promote the development of fine and uniform particles during the ECAE procedure. An additional specific embodiment of the invention is an ECAE embryo after forging. The diameter d. And length h. Of the cast cylindrical ingot (Figure 1) are forged into a disk with a diameter ^ and a thickness H (Figure 2). Thickness Η It is equivalent to the thickness of the ECAE embryo. Then, for example, by machining or cutting, the two parts are removed from the two opposite sides of the forged embryo (Figure 3), so as to improve the size of the square ECAE (Figure 4). ECAE is performed along the "C" in the direction shown in Figure 3. After the first pass, the embryo has a nearly square shape. If the ECAE embryo size (AxAXH), the forged disc size (DxH) and its prayer size (d. X h.) Is related by:

D = 1. 18A d〇2h0 2 1 · 39 · A2H The present invention is also related to the manufacture of targets with fine and uniform particle structure. ecaes are performed in multiple passes at temperatures below the electrostatic recrystallization temperature, and the processing path is adjusted to provide power for recrystallization during the ECAE. The processing temperature and speed are sufficiently low and sufficiently low, respectively, to provide macro- and micro-uniform plastic flow. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Also provides a method for manufacturing a fine and safe structure for sputtering applications: and provides high strength handles. The submicron structure after the ECAE was dynamically recrystallized, the embryo was annealed at a temperature equal to the target surface temperature during stable sputtering. Therefore, the 'target temperature cannot exceed the sputtering temperature of this structure, so that the target lifetime is equal to 疋. This structure is the finest stable structure possible at present, and provides excellent target performance. Therefore, the present invention particularly provides the following important advantages:-High-strength monolithic targets can be made from mild materials, such as pure: copper, gold, pins, nickel, titanium, and their alloys;-no need to use extra and complicated operations Scary &lt; phase plate, such as diffusion bonding or welding 18- A7 &quot; ~ — 一.--____B7____________ V. Description of the invention (16) Connection; (Please read the precautions on the back before filling this page}-Manufacturing large The target is not a problem; and-the stem can be easily recirculated after its low-shot life has expired. Examples of seeding and external gearing include a two-step ecae process. In the first step, the number of passes in different directions of the ECAE is (It is better to 丨 3 times.) The pre-treated embryos that have been pre-treated receive sufficient low temperature ripening annealing, but it is enough to produce very fine precipitates with an average diameter of less than about 0.1 micron. After annealing Ec ae is repeated with multiple passes to develop the recrystallized structure with the desired fine and equiaxed particles. The Central Consumers Bureau of the Ministry of Economic Affairs, the Consumer Cooperative, printed another specific example of this April. Device for green leather. The device (Figures 11, 11A and 11B) includes mold set j, mold base 2, slide 3, punching set 4, 6, hydraulic cylinder 5, sensor 7, and guide pin 11. Mold It also has a heating element 12. The mold set 丨 has a vertical groove 8. The horizontal groove 9 is formed between the mold set 1 and the slide 3. The mold is fixed on the pressure table ι〇, the punching group *, 6 is connected to the pressure air cylinder In the original position aa, the front end of the sliding blade 3 covers the slot 丨, the punch 4 is in the upper position, and the well-lubricated embryo is inserted into the vertical slot. During the punching phase, the punching benefit 4 moves downward and enters the slot 8, Contact the embryo and squeeze it in t 9. The alpha sheet 3 moves with the embryo c. At the end of the impact, the puncher reaches the upper edge of the slot 9, and then returns to the original position. The barrel 5 moves the slider to the position. b, release the embryo, move the slide to the center a, and push the treated embryo out of the mold. Note the following characteristics ... (a) During extrusion, the slide 3 is at the same speed as the material extruded in the groove 9. Moved via the hydraulic cylinder 5. In order to control the speed, the slider is equipped with an inductor 7. This causes a complete deletion in the lower pressurized load and the effective ECAE Friction and stick-slip-19- This paper size applies to Chinese National Standard (CNS) A4 (210X 297mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 593719 V. Description of the invention (17) Sheet material; made V Plate: 1: 1 is attached to the mold base 2 with the guide pin 11 and provides free operation 2% of the time, the mold set is placed on the base plate machine with the friction inside the groove 8 η ::: When the mold returns to the original position, the mold There is no force on the group and the slide, and it is easy to move the slide to the position ^, and then the embryo is pushed from the mold. The three embryonic walls in the 22 slot are formed by the slide (Figure M, which will The second is that the internal friction is minimized. (d) The side wall of the second groove in the sliding plate is provided with 5. To 12. Ventilation (…. During extrusion: It is kept inside the slide in this way, but can be removed from the slide after extrusion. At the same time, the thin flash formed in the gap between the slide and the mold can be used for the mold group Easily trim. (E) The mold set is equipped with a heater 12 and a spring 13. Before processing, there is a gap β between the mold set 丨 and the mold base 2. During the heating, this gap is raised between the mold set and the mold base. The thermal isolation results in short heating time, low heating power and high heating temperature. The device is quite simple, reliable, and can be used at normal pressure. Figure 12 shows a flowchart of an example method of the present invention. In the first step, the quality is The block is deformed at equal groove angle extrusion (ECAE). This deformation can be completed one or more times with the pass = ECAE device. The example ECAE device is described in US Patent Nos. 5,400,633; 5,513,512; 5,600,989, and 5,590,390. 0 Figure 12 In the second step, the deformed mass is formed into at least a part of the sputtering target. This forming can include, for example, rolling the mass to make it lighter 20- This paper size applies the Chinese National Standard (CNS) A4 regulations Grid (210x297 public meal) 丨 !! -1! — (Please read the precautions on the back before filling this page)

、 1T W719 V. Description of the invention (18 Press, hot forging and cutting — I — — I! — #! (Please read the notes on the back before filling this page) Including the entire _… :: 种 或多 #. The mass can be shaped into a dry shape.-An example application where mass can be shaped to include only-Partial sputtering, a two-form horse that includes only a single sputtering target shape application. Inlay ^ block is used to form —Some of the so-called inlaid 1 bar targets that define a single large punishment and cover many individual target blocks are joined by. ^ Soil targets. The use of inlaid targets in forming large targets is advantageous I: ^: 5 inlays The small independent part of the target is usually earlier than the manufacturing single-large size. If mass blocks are used for inlaying, it can be hoped that all the targets of the inlay bar are extruded and deformed at an equal groove angle before being mixed in the inlay target. In the first step of S, the frame of the formed mass is shot on the structure plate to mix the texture block with the Geba structure. The method of proper slab and setting the target frame to the slab is known in the art. Note that the present invention includes a mass that is used directly as a shooting target without A specific embodiment erected on the stern plate, and a specific embodiment erected on the slab. The method of the present invention printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs can be used to manufacture the mass with very fine and uniform particles. In the target of the structure, the predetermined size of the particles is less than about 50 microns. The present invention understands that the refinement of the particles can be provided by the ECAE technology on material processing. The ECAE is preferably performed at a temperature and speed sufficient to achieve the desired microstructure, and provides Uniform strain-stress states throughout the treated embryo. The number of times the ECAE device is passed, and the special ECAE deformation path selected to pass through the device can be selected to optimize the target microstructure. For example, particle refining during intense strain due to The result of the basic structural deformation of the simple cutting and shearing of the ECAE device. Various flaws, such as the translocation 'cut male belt' Fengge-21-This paper size applies to Chinese National Standard (CNS) A4 specification (21〇 &gt; &lt; 297 Male thin) 593719 A7 B7__ 5. The description of the invention (19) and the sub-particles were generated during the first pass of the ECAE on improving deformation, The original particles are subdivided into finer areas. Depending on the nature and composition of the materials used during the exposure to the ECAE method, different types of particle sizes can be obtained. For example, if the ECAE treatment is performed at a temperature below the static recrystallization, the The ECAE device can produce particles less than 1 micron in size after four or more times. The size of such particles is at least 100 times smaller than the structure produced by traditional methods. For example, it is relatively pure aluminum (that is, 99.99% aluminum) The static recrystallization temperature of the mass is typically known as a temperature lower than about 100 ° C, and can be about room temperature (ie, about 20 ° C to about 25 ° C). If the static recrystallization of the aluminum-containing mass is The crystallization temperature is about room temperature, and the mass of ECAE at room temperature without the occurrence of a heated ECAE device can provide a microstructure with particles of several microns. After ECAL ·, the fine area of the original particles is subdivided in the material structure to obtain a high-angle boundary to become a granular structure. This method can be cited as "the dynamic recrystallization of mechanical slander", and the main force of subdividing the recrystallization is to cut and deform plastic deformation alone. Conversely, if the ECAE is performed at a temperature higher than the static recrystallization, both the temperature effect and the shear effect will cause particle growth. Therefore, a particle size of a few micrometers can be debunked by passing three or more times through the ECAE device. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling this page) At least three different ECAE perspectives constitute a significant reduction in particle size, and the mass is processed according to the invention to achieve particle uniformity. These three perspectives are the deformation of plastics given by ECAE: the deformation path of ECAE, and the simple shearing force that occurs during ECAL ·. After the material is subjected to ECAE according to the method of the present invention, the material can be formed by the traditional forging method, cross-rolled and rolled to form the material into a stable shape, so that the national paper (CNS) A4 specification (210X297) is applicable at the -22-paper size. (Mm) 593719 Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs, and Description of Invention (20) Used as a target in the sputtering method. The ultra-fine particles produced between ECA_ were found to be stable and uniform, R, 隹 + size were determined by the maid and son, and the traditional processing showed limited growth; even during the processing including the material thickness was significantly reduced. -Right. The traditional forming operation used to shape the material after ECAE treatment is performed at the temperature and plastic deformation that will occur during sputtering. For example, the low-shot method is expected to be around 150. (: Occurs, then the traditional ^ 2 such as light pressing, cross light pressing, or forging that occurs after ECAE, preferably at a temperature below 15.0 ° C. By performing at a temperature below the sputtering temperature In the second operation, the possibility of increasing the particle size of the traditional method beyond the target of the sputtering target is reduced. 'The microstructures generated during the ECAE were found to exhibit the expected stability when annealing, compared to the microstructures produced by the traditional method. This proves that both sub-micron and micro-structures are formed in the material deformed by ecae. For example, after annealing for 1 hour at 150 ° C, the samples treated with ECAE appear to have a restricted particle size and increase from about 12 microns to asymptotic to 3 0 micron. The size of this particle did not change significantly after 16 hours of annealing. On the contrary, the thickness of the sample reduced by 85 ° / (received by rolling only), which was dramatic after i hour annealing, was dramatic. Particle growth up to a particle size greater than 250 microns. As discussed above, annealing can occur between ECAE devices or after ECAE. Note that annealing can occur between traditional methods such as rolling, crossing Annealing occurs after pressing and ecae, or can occur after the target forming step after gCAE. The target forming step preferably occurs at a temperature of less than or equal to about 20 (rc is better (less than or equal to about 50 C)) In order to maintain the target forming step at a temperature lower than the final target sputtering temperature. According to regulations, as far as the structure and method characteristics are concerned, the present invention is approximately -23. This paper size applies the Chinese National Standard (CNS) A4 specification ( 210X297 mm) —I—rl · —— · — (Please read the notes on the back before filling out this page) Order 593719 A7 B7 21 V. Description of the invention (Description of the language. However, you are aware of the invention and are limited to it The particular features shown and described, because the device disclosed herein includes a preferred form of practicing the invention. Therefore, the invention is claimed with any of its forms or adjustments within the appropriate scope of an additional application based on an equivalent theoretical description. Please read the notes on the back before filling out this page) Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economics -24 This paper size applies to China National Standard (CNS) A4 (210X 297 mm)

Claims (1)

1. A measurement area containing 99% of particles of a plurality of sizes is composed of particles: two ::, which is characterized by at least two times the measurement area of particles two: the product is lower than the average particle size 2. The area of item i is composed of particles having a particle area that is 8 times smaller than the average measurement volume of the mean and at least ㈣. Thousand average particle size measurement surface 3. According to the item i of the scope of patent application, the area is made of 6 kernels, M 4 with a measurement volume of at least 99% of the protection bamboo shoots, and M 4-"below the average particle size measurement The surface is composed of 6 times the particles. J is called 4. According to the application of the scope of the patent application 丨 * ^ ^., Wood material, at least 99% of the measured area is from the particle area is 3 times the product Particles ^ average particle size measurement surface 5. ==! The material surrounding item 1, wherein the particles have an average particle size of less than 6 according to Shen: Zhi'an recrystallized particle size 3 times. ^ Materials range The material of item 1, wherein the particles have an average particle size which is lower than the minimum static recrystallized particle size of the material. ^: For the material of item 1 of the patent scope, the particles have an average particle size of less than ⑻m. Size: 1 wherein the particles have a mean particle size from 1 to 10, wherein the particles have an average particle size from a material in which the measured area includes 8 according to the scope of the patent application item to 10 microns. 0.1 to 1 micron . ⑴ · The average particle size range of the material _ patenting of the i-th item, at least the materials statistics representative areas O:. \ 71 \ 7l547-93042l.doc 2- Application of patent scope According to the material of patent application scope W, the measurement area contains less than 1000 agglomerated particles. 12. According to the material of the erector in the scope of the patent application, the measurement area in the figure includes the entire measurable area of the material. : The material according to item i of the claimed M patent scope, including one or more of the following materials: Be, B, c, Mg, Ab Si, ca, Sc, Ding, V, Cr, Mn'Fe'C0, Ni, Cu, Zn, Ga, Ge, Se, Sr, Y, Nb M0 'Ru' Pd 'Ag' In, Sn, Sb, Ba, La, Ta 'W' Ir 'Pt' Au, Bi, Ce, Nd, Sm, Eu, Gd, Db or Dy. ] ―A kind of shot 1 bar, including the material according to item 1 of the patent scope. From the low-quality dry deposition according to item 14 of the scope of the applied patent 16 :: The material covered by the scope of the patent is composed of plural fruits and rights, and is characterized by having at least one private and common ^ v / 〇 and any The area measured by I is composed of particles with a surface area of less than the average particle size. 10 times the sentence According to the material in the patent claim No. 16, the minimum static recrystallized particles of this material are doubled, and the material in the patent scope No. ㈣, the average particle size at 50 microns. The grains have low Han material according to item 16 of the scope of patent application, where the hab contains at least a statistically representative area of the material. I area package O: \ 7l \ 7l547-93042l.doc 297 mm) 20.—A species composed of a plurality of particles and having a minimum static energy of <shooting target 'is characterized in that the particles are small and have an average particle mass product that is three times the size of the two particles. It has a particle area distribution, which is such that at least 99% of the measurement surface is 10 times smaller than the average particle size of the measurement area, and 8 to one volume of the particle is formed by a product that is below the average particle size. The area 22 'according to the patent application area is composed of 6 particles with at least 99% of the measurement volume, and 4 areas are 6 times the area of the measurement surface C which is less than the average particle size. = The range of profit of item 20 of the profit range is dry, at least &quot;% measurement 2 is composed of particles having a particle area that is three times smaller than the average particle size measurement surface. 24. According to the second of the scope of patent application The average particle size of the sputtering target of item 0 is less than 50 microns. 25. The sputtering target according to item 20 of the patent application scope includes at least a statistically representative area of the material. 26 'Sputtering according to item 20 of the patent application scope The target contains one or more of the following substances: Be, B, C, Mg, A1, ^, ^, sc, Ti'v'Cr, Mn'Fe, Co'Ni, Cu, &amp;, to, to, &amp;, Y, Zr 'Nb, Mo, Ru, Pd, Ag, ", &amp;, 讥, &amp;, La'Hf'Ta, W'lr, Pt, Au, Be, ^, then, Sm, Eu 'Gd, Tb or Dy o O: \ 7l \ 71547-930421.doc This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm). The size of the particle is bound. The measurement area is 593719 8 8 8 8 AB c D 6. Application scope 27. The sputtering target according to item 20 of the scope of patent application, which contains at least 90 atomic% A1, Ti, Cr, Co, Ni , Cu, Zr, Ru, Ag, In, Sn, Hf, Ta, Ir, Pt or Au, and one or more of the following substances: Be, B, C, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Sr Y, Zr, Nb, Mo, Ru, Pd, Ag, In, Sn 5, Sb, Ba La , Hf, Ta, W, Ir, Pt, Au, Bi, Ce, Nd, Sm Eu, Gd, Tb or Dy. 28. The sputtering target according to item 20 of the patent application scope, containing at least 90 atomic% Al, Ti , Cr, Co, Ni, Cu, Zr, Ru, Ag, In, Sn, Hf, Ta, Ir, Pt or Au, and one or more kinds of chin 1J from 0 to 01 to 10 atomic% Substances: Al, Si, Ti, Cu, Ga, Nb, Mo, Pd, Ag, In, Sn, Ta, W or Au o 29. Sputtering target according to item 20 of the patent application scope, containing at least 90 atomic% Al, Ti, Cr, Co, Ni , Cu, Zr, Ru, Ag, In, Sn, Hf, Ta, Ir, Pt or Au, and one or more kinds of ytterbium from 0.01 to 10 atomic% | J Substances · Mg, Ca, Sc, Sr, Y, Zr, Ba, La, Hf, Ce or Nd〇30. Sputtering according to item 20 of the scope of patent application Containing at least 95 atomic% of Al, Ti, Cr, Co, Ni, Cu, Zr, Ru, Ag, In, Sn, Hf, Ta, Ir, Pt or Au, and one or more of from 0.1 to 5 atomic% The following substances: Be, B, C, Mg, Abu Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Sr, Y, Zr, Nb , Mo, Ru, Pd, Ag, In, Sn, Sb, Ba, O: \ 71 \ 71547-930421.doc-4-This paper size applies to China National Standard (CNS) A4 (210X297 mm) La, Hf , Ta, w, Ir, Pt, Au, Bi, Ce, Nd, Sm, Eu 'Gd, Tb or Dy. 31. The sputtering target according to item 20 of the scope of patent application, which contains at least 95 atomic% of Ti, Cr, Co, Ni, Cu, Zr, Ru, Ag, In, Sn,, Ta, Ir, pt, or Au, And 0.1 to 5 atomic percent of europium or more of the following: Al, Si, Ti, Cu, Ga, Nb, Mo, Pd, In, 'Ta' W or Au. 32. The sputtering target according to item 20 of the patent application scope, comprising at least 95 atomic% Al, Ti, Cr, Co, Ni, Cu, Zr, Ru, Ag, In, Sn, Hi Ta 'Ir' Pt or Au, And 0.1 to 5 atoms 0/0, or more of the following substances: Mg, Ca, Sc, Sr, Y, Zr, Ba, La, Hf, Ce or Nd 〇33. According to the scope of the patent application No. 20 A sputtering target containing aluminum. 34. The sputtering target according to item 20 of the patent application scope, comprising titanium. 35. The sputtering target according to claim 20 of the scope of patent application, including tantalum. 36. A sputtering target according to item 20 of the scope of patent application, including copper. 37. A sputtering target according to item 20 of the scope of patent application, comprising niobium. 38. The sputtering target according to item 20 of the application, which includes nickel. 39. The sputtering target according to claim 20 of the scope of patent application, comprising molybdenum. 40. The sputtering handle according to item 20 of the scope of patent application, including gold. 41. The sputtering target according to item 20 of the patent application scope, comprising silver. 42. Sputtering target according to the scope of application for patent No. 20, package; platinum. 43 · -thin film deposited on a substrate from a sputtering target according to item 20 of the patent application. O: \ 71 \ 71547-930421 .doc -5- 'Applicable patent scope 44 · A method of reducing the micro-arc, a Sputtering target of the A-spray particle / sputtering—thin D from the area containing a plurality of sizes to measure Has grains: member grains <characterized by at least 99% of the area of the hoof cut structure is less than the size of the flat phase grains according to the scope of the patent application No. 44 system has a lower static energy renewal society 33; / 'where the base Shoot dry particle size. The average particle size is 3 times the particle size of 46 days. 46. A method for generating a sputtering target, including: deforming the sputtering material; and deforming the sputtering target material into W points, and forming the sputtering target into sputtering. At least a part of the target's measuring surface is characterized by at least 99% of the measurement area: the second product is less than the average particle size. 47 · = method of patent application range ㈣, at least 99% of which is measured by particles Particles with an area 8 times smaller than the measurement surface of the average particle size. 5 The method according to claim 46 of the patent, wherein at least 9 states of measurement are made up of particles having a particle area that is 6 times smaller than the measurement of the average particle size. 49 'The method according to item 46 of the patent application, wherein at least 99% of the measurement is made up of particles having a particle area which is three times smaller than the average particle size measurement. The method according to item 46 of the patent application, wherein the deformation includes a high strain treatment technology. Measuring surface area Measuring surface area includes O: \ 71 \ 7l547-930421.doc -6- This paper size is applicable to the gjg family standard (CNS) M specification (2_297 public policy) 593719 A8 B8 C8 D8 VI. The scope of patent application 51 The method according to item 46 of the patent application scope, wherein the deformation includes equal groove angle extrusion. 52. According to the method of claim 46 of the scope of patent application, after deformation, the sputtering target particles have an average particle size that is less than three times the minimum static recrystallization particle size. 53. The method according to item 46 of the application, wherein the degree of deformation-induced accumulated strain is equivalent to ε of at least 4. O: \ 71 \ 71547-930421.doc This paper size applies to China National Standard (CNS) Α4 (210X297 mm)