TWI278525B - Copper sputtering targets and methods of forming copper sputtering targets - Google Patents

Abstract

The invention includes a copper-comprising sputtering target. The target is monolithic or bonded and contains at least 99.99% copper by weight and has an average grain size of from 1 micron to 50 microns. The copper-comprising target has a yield strength of greater than or equal to about 15 ksi and a Brinell hardness (HB) of greater than about 40. The invention includes copper alloy monolithic and bonded sputtering targets consisting essentially of less than or equal to about 99.99% copper by weight and a total amount of alloying element(s) of at least 100 ppm and less than 10% by weight. The targets have an average grain size of from less than 1 micron to 50 microns and have a grain size non-uniformity of less than about 15% standard deviation (1-sigma) throughout the target. The invention additionally includes methods of producing bonded and monolithic copper and copper alloy targets.

Description

1278525 玖, DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a copper-containing monolithic sputtering target and a copper-containing bonded sputtering target. The invention additionally relates to a method of forming a copper-containing monolith and bonding a sputtering target. [Prior Art] High-purity copper sputtering targets and copper alloy sputtering targets are currently used in various applications (including, for example, fabrication of integrated circuits). The sputtering properties of the copper-containing structure (such as connectors and films) = quality target. The various factors of the sputtering target can be shadowed, and the sputtering performance of the target includes: the average grain size of the standard (four) material and the uniformity of the grain size, the crystal orientation/texture of the target material, and the structure of the target and Composition uniformity and strength of the target material. Typically, the smaller average crystal size is related to the strength of the material. In addition, the amount of alloying elements can affect the strength and hardness of the target material, and the increase in the alloying element typically results in an increase in the dry strength. Due to the low strength of high purity copper (more than 99.99% by weight copper), conventional high purity copper sputtering targets typically form a bonding target. The copper sputtering target can be combined with a high purity copper target bonded to a backing plate containing a relatively high strength material such as aluminum. However, the high temperatures utilized in combining copper targets to backing sheets often result in abnormal grain growth that results in a non-homogeneous structure and an increase in the overall average grain size. Conventional back-purity copper targets typically have an average grain size greater than 50 microns that results in lower repulsive strength. Traditionally formed high-purity copper sputter targets (grain size and structural heterogeneity adversely affect the quality of sputter deposited high-purity copper films and connectors. In addition to the large grain size and Regular grain growth &lt; External 'diffusion bonded copper targets are often subject to burnt-through or short target lifetimes. 1278525 t. In addition, the bonding process can be complex and time consuming. The grain size uniformity and the enhancement of the 'worm' method are to form copper with one or more alloying elements 八' because the existence of alloying elements affects the impedance of copper, limiting the combination;: Xin: The amount of not more than 1% by weight is suitable. For: σ to 兀素 <the amount should be limited to less than or equal to 3% by weight. The other is that the disadvantage is that it may become a potential defect, such as formation: two Separation. ^Children or traditional material treatments that reduce or remove defects in the sink or separation are feasible in some cases, but such treatments typically include a large crystal size of 1 (greater than 丨5 () microns). Temperature. Another - select as part There is little transmission (4) the second phase sink in the sputum; the temple or separation defects can be achieved in some cases by using pressure-transmitting milk and/or forging techniques in some cases At present, the conventional processing of forming a copper alloy having a weight of less than or equal to 3: alloy bismuth produces an average grain size of typically greater than 30 microns ("typically over 5 〇 microns") and has a second phase sink in it. #巴0 Development of a tool for the production of copper-based smear and copper alloys for the sputtering performance of Wenliang. [Invention] In one aspect, the invention includes a copper-containing sputtering target. Target. The target contains at least 99.99 liters/inch of copper and has an average grain size from 丨 micron to 5 〇 micron. The copper-containing standard 降 "four degrees" is greater than or equal to about 15 ksiJL and the hardness (hb) is greater than about 1278525 40 In one aspect the invention includes a copper alloy sputtering target having substantially less than or equal to about 99.99% by weight copper and at least one selected from the group consisting of *Cd,

Au' Ag, Be, Li, Mg, Al, Pd, Hg, Ni, In, Zn, B, Ga, μ

Sn ′ Ge, W, Cr, O, Sb, Ir, P, As, Co, Te, Fe, S, ΊΊ 7 丄i , Zr ,

An alloying element composition of a group consisting of Sc ' Si, Mo, pt, Nb, Re, and Hf. ^ The total amount of alloying elements of gram is at least 100 PPm and less than 10% by weight. The average grain size of the granules is also from 丨 micron to 50 micrometers and the grain size uniformity of one sigma which is less than about 15% in the entire target. In one aspect the invention includes a method of forming a monolithic sputtering target. The copper tantalum consisting essentially of copper and one or more of the eight gold elements in a total amount of less than or equal to 10% by weight is heated to at least about 900 T and maintained at this temperature to the center V for about 45 minutes. The billet is hot forged at a height reduction of at least about 50% to form a barrier and the forged block is cold rolled to a reduction rate of at least about 60% to form a bullseye. The leather is heated to cause recrystallization and to form a fine particle distribution having an average grain size of less than 1 Å. The bullseye then forms a monolithic target shape. In one aspect the invention includes a method of forming a copper-containing sputtering target from a copper having a purity of at least 99.9%. The billet is forged at a temperature of at least 40% above the temperature of 3 〇〇 °c to form a forged block. The forged block is quenched with water and is subjected to at least 4 passes through the equal-diameter corner extrusion process. The solubilization process can be performed in the forging, followed by water, fire and ECAE. The intermediate annealing is performed between at least some of the eCae passes. After the ECAE processing is completed, the forged block is cold rolled to a reduction of less than 9 〇q/q to form a bullseye. The target can be heat treated and subsequently formed into a sputtering target. 278525 Embodiments The present invention comprises a single high-purity copper sputtering standard dry, single-copper alloy handle, := human = high-purity method. 1 For the purpose of the present invention, high-purity copper can be used to refer to: Buzhongli red steel Neodymium steel material. The present invention includes a high-purity standard leather bar with a steel weight of up to 99.99999%. In addition, the 捃 太 ° ° Η Η Η Η 用作 用作 政 政 政 政 政 政 政 政 。 。 。 。 。 。 。 。 : : : : : : : : The combination of Erming or a single piece of high-purity dry can have a smaller average size of less than i microns or a temple of about gamma (preferably less than 50 microns), and may be averaged by V. The grain size is about a single piece or a combination of the meter. Monoliths and junctions according to the present invention:: in particular, an average particle size of from W meters to about 20 microns, such as from about 5 microns to about 10 microns. Or the dryness of the standard, the uniformity of the grain size makes the standard deviation (10) gamma less than about 15% (also known as W non-uniformity). In the case of gender, the sentence can reflect the standard deviation of less than or equal to 1〇% (1 Sigma).曰: The invention of the high-purity copper sputtering target can be compared with substantially the same element: a composition of an average granule size of 50 μm of the standard dryness of at least about 1%, and in the case of: - The grain size is 3 〇 microns: the gram is at least 10 〇 / 〇. For the purposes of the present invention, "substantially the same composition" means a material that has no compositional differences that can be made. The method of &lt;Desc/Clms Page number&gt; The high-purity copper balance of the present invention may have an ultimate tensile strength at least 15% greater than a target having an average elemental composition of I278525 and a particle size of 50 μm, and in some cases, an average of the same elemental composition. The target has a grain size of 30 microns and the target has an ultimate tensile strength of at least 15%. In addition, the hardness of the high-purity copper target is about 5% less than that of the target material having an average crystal grain size of 3 μm. In particular, the high purity target of the present invention has a Brinell hardness greater than 40 HB and, in particular, greater than about 6 Η Ηβ. In a particular aspect, the high purity copper sputter target of the present invention has a purity of 99.99% (4N) or higher. For the purposes of the present invention, all percentages and amounts included are by weight unless otherwise indicated. In some aspects, high purity targets comprising 99.999% (5N) of copper are preferred, and may include 99.9999% (6n) of copper preferably or may include 99.99995% (6N5) of copper.

The combined high purity copper target of the present invention may comprise diffusion bonding to the backing plate

咼 Purity copper standard leather bar. In a special case, the degree is greater than 10 ksi, and the combined high-purity copper target is bonded to the backing plate at a bonding strength greater than or equal to about 30, including, for example, one or more types of pressure, roll friction forging. The combination of ksi is preferred. It is better to combine the diffusion of the standard dryness with the 15 vsi, and in special cases ksi. Another option is to use cladding, soldering, explosive bonding, and no backing. Other bonding methods have a clocking strength of greater than or equal to about 1 Torr. The backing sheet used in the bonding target of the present invention is preferably an aluminum or CuCr backing sheet. If you know what this artist knows, use other backing materials x. For purposes of the present invention, a steel eighty-eight sputtering target comprising less than or equal to about 99.9% by weight of steel is included. The copper alloy sputtering target of the present invention consists essentially of: to, or equal to -10- 1278525, about 99.99 weight %. The copper and at least one selected from the group consisting of 〇 (1, €3, eight 11, eight §, :^,

Li,Mg,A1,Pd,Hd,Ni,In,zn,B,Ga,Μη,Sn,Ge,W, Ci*,O,Sb ' Ir ' P ' As 'Co,Te,Fe,S,Ti ,Zr,Sc,Si,pt,

The alloying element composition of the group consisting of Nb'Re, Mo and Hf is preferred. In particular, at least one alloying element is selected from the group consisting of Ag, A, In, Zn, B, ^, Mg, Sn, Ge, Ti and Zr. Preferably, the total amount of at least one alloying element in the target is at least about 100 卯 111 by weight, preferably at least about 1% by weight. In one case, at least one alloying element may be present at least 10 ppm by weight, preferably about 3%, more preferably less than 2% by weight. The copper alloy sputtering target according to the present invention has an average crystallite size of less than 1 micrometer in a particular viewpoint. Another option for copper alloy sputtering targets can include an average grain size of about 100 microns (preferably less than 50 microns). In some cases, the grain size of the ''copper alloy scale is better than i to the working meter. The application of the method of the present invention can produce, in some cases, an average grain size of less than or equal to plus microns, and in particular from about 5 microns to (four) microns. In addition, the copper alloy standard bag of the present invention has a uniform grain size throughout the standard leather bar or across the standard leather. In special accounts, the average grain size is less than 15% (#4^^&lt;_ is equal to about 15%) throughout the material. In the special case, the standard deviation is less than or equal to (non-uniformity is less than or equal to 1%). Root: The copper alloy of the present invention has a Brinell hardness of at least about 4 Å. In the case of the present invention, the hardness of the invention (4) is greater than about 60 Γ. The bismuth copper alloy has a cross-progressive surface and / or in the entire standard dryness, for example, in the special case, the standard deviation of the entire copper alloy standard bar hardness of 1278525 Ο Sigma) is less than about 5%, 5%). In special cases, the hardness is (::: two leather... ‘sex small sigma). / 勾午爰 is less than about 3.5% (1 the steel of the present invention is Δ-bonded. The second is a monolith or in other embodiments may be - or a plurality of = rr: alloy dry can be combined by diffusion or borrowing = and other suitable: = technology =, two: tin, explosive combination, frictionless forging combination, intrusion, 10,000 ~ to the back of the maple plate. In the copper alloy target ksi better ... <combined fall strength greater than about 10 - and greater than about 15 (: The near-method of processing copper material can be produced by a very weak core copper target, depending on the processing path utilized (in material: for the purposes of the present invention, "copper," ("copper standard dry", "copper invention two (four) use) - generally refers to high-purity copper or copper alloy. According to small; typical copper hiding crystal grain orientation distribution function _), έ: 5 temple at about 15 Any value. In special cases, the target can be extremely weak and reasonable, characterized by an ODF less than 5 times any value. The t target can include a major grain orientation, where ''primary,' One of the grain orientations in the private target is more Toyota than any other grain orientation. > Wang Yi "main" does not have to be large Part of the grains are present in this orientation. "There is no single other orientation in the main target, but a large amount of other orientations are present. In a particular view, the method of the present invention can be used to produce a grain boundary of significant grain orientation other than (22〇). ^ Another processing method according to the present invention can produce a copper-based leather bar having less than any texture. The present invention includes processing to cause strong texture in a copper-generating article, where 1278525 "strong texture word refers to (10) is higher than about 15 times arbitrary. Material of value. The standard of the present invention additionally: manufactures four extremely strong textures characterized by (10) any value higher than 2G times. In special cases, the present invention is dry and the main grain orientation other than (22G) is utilized. The size of the copper target produced according to the method of the present invention is not limited by a specific value. In addition, the target can be manufactured in various shapes such as a pattern or a rectangle. Since the material manufactured by the method is increased in strength compared with the conventional method, the manufacturing ratio can be made. The larger size of the copper standard is produced by conventional methodologies. As discussed above, conventional copper targets are bonded to the backing plate to provide sufficient strength. The high strength of the materials of the present invention is particularly advantageous because of the increase In addition, the strength can be reduced or avoided in the manufacturing and/or (d) process. This methodology allows for the use of monolithic (unbound) copper targets and allows for larger target sizes for binding and single target. Monolithic targets can be fabricated for a variety of sputtering applications, including but limited to 2°° mm wafer processing and 300 mm wafer processing. Although the standard and method of the present invention are described in terms of specific reference steels and copper alloys, it should be understood The invention includes other materials, including high purity metals and alloy materials. Typical other materials that are particularly advantageous for use in the methodology include aluminum, aluminum alloys, titanium, titanium alloys, knobs, niobium alloys, nickel, nickel alloys, molybdenum, Molybdenum alloys, gold, gold alloys, silver, silver alloys, platinum and platinum alloys. It is preferred that the alloys listed contain less than or equal to 1% by weight of alloying elements. As will be appreciated by those skilled in the art, the temperature and other values of the method-related copper materials described below can be adjusted based on the particular composition to which the methodology is applied. It is provided in the desired step 100 in a typical processing scheme. Initially, the methodology of the present invention is generally described with reference to FIG. The material that is processed to form the Tibetan standard dry is initially added! 278525 The material can be as shown in Figure 2. (4) The island 12 can include the lower surface Η, the upper surface 16 and can be packaged with each H. Referring to Figure 2, 16 is labeled as Tl material. thickness. (4) It may be as shown in Fig. 9 with the upper surface tr or another selected to contain a cylinder or other shape (not: two positive: f2 binding material is better, although other extension materials may be considered and the material may be Providing a very pure form * West is Blood Jing L Gan + Zhi Nai Wan, to the target of the housing estate, the soil is basically the same as the composition of the blank. S 1 AK here basically the same reference枓There is no detectable difference in composition. The texture of the material of Figure 12 can be changed, "heart sound," and/or achieve the desired final texture of 2 pieces according to the present invention. The initial texture of the desired texture within the label. It is advantageous to provide a strong texture of the blank 12, where the strong texture is required in the final object. However, it should be noted that the other side of the invention can be used to produce a weak texture from a strong textured blank. Or extremely weak texture. In addition, the interest of weak texture can be processed according to the methodology of the present invention to produce a target with strong or extremely strong texture. A blank with a particular primary or predetermined grain orientation can be processed to produce the same or different primary Oriented or not having a single predetermined grain orientation In particular, the blank 12 may comprise at least 99.99% by weight of a high purity copper material. In a particular application, 12 is substantially 99.99% by weight pure (4N), 99.999% pure (5N), 99.9999% by weight. Pure (6N) or more than 6N (e.g., 99.99995% pure) copper composition, the present invention also includes the process of burying 12 other high purity metals such as Ming, Jin, Silver '鈥, 4s, nickel, Gu or molybdenum. Another option for the blank 12 may include less than 99.99% copper or less than 99.99% of any other selectable metal shown above. For ease of description, the blank 12 will be referred to as a copper blank, although the invention includes other Selected metals and alloys thereof. In some aspects of the invention, the copper blank 12 is substantially less than 99.99% copper and at least one selected from the group consisting of Cd, Ca, Au, Ag, Be, Li, Mg, A1,

Pd, Hg, Ni, In, Zn, B, Ga, Mn, Sn, Ge, W, Cr, 〇, Sb,

The alloying element composition of the group consisting of Ir, P, As, Co, Te, Fe, S, Ti, Zr, Sc, Si, Pt, Nb, Re, Mo and Hf is preferred. The total amount of alloying elements in the copper billet is preferably at least 100 ppm by weight to less than or equal to about 10%. In particular, it is preferred that the copper comprises at least 1000 ppm by weight to less than or equal to about 3% of the alloying element, or less than or equal to about 2% by weight of the total alloying element. In a particular embodiment, the alloying elements may comprise one or more of Ag, Al, In, Zn, B, Ga, Mg, Sn, Ge, Ti and Zr. Referring again to FIG. 1, the copper blank provided in step 100 is subjected to preliminary processing 200. The preliminary treatment 200 can include at least one of homogenization, solubilization, and hot forging. As will be appreciated by those skilled in the art, the appropriate temperature for solubilization, homogenization or hot forging may depend on the particular composition of the blank 12. In a particular aspect, the invention preferably includes hot forging in the preliminary treatment 200 to form a forged block. Hot forging of the billet 12 is carried out at a temperature of at least about 300 ° C, preferably at a temperature of at least about 500 ° C. Hot forging reduces the initial thickness of the blank 12 (1 of Figure 2) by at least about 40%, and in particular, at least about 50% is preferred. At the time of initial processing, hot forging may be required before or after additional heat treatment comprising solubilizing and/or homogenizing the copper material. The heat treatment can be carried out at a temperature sufficient to cause solubilization and/or homogenization in the particular composition to be treated. This solubilization/homogenization temperature is preferably maintained for a time sufficient to maximize solubilization and/or homogenization of the composition. Pay attention to the temperature sufficient for solubilization or homogenization

-15 - Ϊ278525 degrees can cause the occurrence of grain size greater than, ^ crystal #士, and 10,000;, 'force 1 〇 〇 micron two questions, 曰 4 growth. Therefore, it is attempted to achieve a more targeted and minimized solution or homogenization treatment. ^...pass _ method tends. . In the afternoon, the grains are squashed/smelted and the grains are squashed and homogenized, and the sputum is reduced, and the shovel is reduced to achieve solution and/or both at the same time. In the preliminary processing step 200, the particles are all ::: ^ away. - reduce or remove the chemical components in the blank 12

:: Ming: The preliminary treatment process is not limited to homogenization, solutionization = rational order. In (4) view M, the initial sentence of the copper after the formation of the sentence and subsequent solubilization. In other; :' The solubilization is carried out after hot forging. Typical Preferred Preliminary Processing: A narrative statement of a typical preferred embodiment of the invention. In some cases when hot forging is carried out in the preliminary treatment, it may additionally include quenching after hot forging, and the forging is immediately after forging.

good. Μ Other alternative quenching techniques can be utilized to take advantage of the water. In a particular embodiment, hot forging can include a period of initial heating and a subsequent reheating event. The height reduction produced between the initial heating and each subsequent reheating in each forging event may vary with factors such as the particular composition and the forging temperature utilized. Any quenching that takes place is preferred only after the final reheating. Typical reheating may include one or more reheating of the forged mass to a temperature of 1400 Torr for at least about 1 minute followed by initial hot forming. -16 - 1278525 In addition to the process described above, the initial processing 2 can be visually processed as needed. When the preliminary treatment involves aging, it is preferred that Tan 12 is a forged block before aging. The aging is better in the final step in the pre-processing stage. In special cases, aging can be utilized to cause the formation of fine precipitates in the copper material. The resulting diameter of the sinks of this type is less than about Q5 microns. In special applications, it is advantageous to cause precipitation by aging because such precipitation promotes the development of fine and uniform grains in the subsequent two processes and stabilizes the crystal structure thus produced. The hot forged and/or melted block formed in the preliminary treatment 200 then undergoes other alternative processing as shown in FIG. In one aspect, the machined block $ is formed by an equal diameter corner extrusion (ECAE) process 310 to form the target's bullion. Referring to Figure 3, this depicts a typical ECAE device 20. Apparatus 2 includes a pair of intersecting channels 24 and 26 ι mold combination 22. The intersecting passages 24 and 26 are identical or substantially identical in cross-section, and the term "substantially identical" means that the passage is the same within a tolerance acceptable to the device. In operation, the blank 28 is extruded. For the forged block described above, it passes through channels 24 and 26. Such extrusion causes plastic deformation of the blank by a layer of men in the thin plane of the intersecting plane of the channel, although the channels Μ and 26 are at an angle of about 90. The crossover is better, it should be understood that other optional tool angles can be used (not shown tf). Approximately 90. The tool angle (channel crossing angle) is better because the best deformation (true shear strain) can be achieved. ECAE can be Severe plastic deformation is introduced into the forged block material, and its size is not changed. ECAE is a better method for causing severe strain in metal materials, in which ecae is used to cause strict uniformity and uniform strain under low load and pressure. In addition, the ECAE can achieve a high deformation per pass (true 1278525 strain 8J1·17), and multiple passes through the ECAE device (N=4 passes, ε = 4.64) can reach the convergence of the set-up Use in material Various textures/microstructures are created by utilizing different deformation paths (ie, by changing the orientation of the forged blocks between ECAE devices). ~ In the typical method of the present invention, the ECAE is sufficient to obtain the copper blank or forged block θ. Microstructures (such as weak texture and small grain size) and are carried out under the entire &amp;towel; the base strain-strain state strain rate and processing temperature. Copper = material in 11 夕 path and in accordance with cold or hot processed materials The temperature is passed through the ECAE device several times: the preferred path for multiple passes through the ECAE device 20 can be "path · D in each - continuous pass before the fixed 90 rotation. Because the ECAE path can be affected in dynamic recrystallization Structural orientation, one or more special paths may be selected for deformation to cause the desired orientation in the processed material. In a particular application, the forged block processed in step 2 is passed through process 31〇 - at least four ECAE passes Code f ±, ECAE processing 31 〇 contains 4 to 8 passes - and preferably contains 4 to 6 passes. It has been found that the typical number is generally sufficient to promote grain refinement by mechanically causing dynamic recrystallization. The size of the next micron (where the submicron refers to the average grain size is less than 丨 microns). Typically, ECAE produces defects (microstrip, 'man's belt, array') by successively producing defects from 1 to 3 times. Etc.) In these initial passes, the heat is rearranged to produce the grain boundaries of the primary and secondary grains and the initial unfavorable orientation. £(: The texture strength of the material before the eight can affect the initial 3 passes. The strength of a material with a strong initial texture is typically more messy than a material with a weak initial texture. Subsequent passes (ie, the 4th pass and any additional passes) cause an increase in the number of large-angle boundaries. The submicron crystals that produce dynamic recrystallization are large. In the re-crystallization, the newly formed grains gradually get a weaker texture and gradually become equiaxed. - In some applications, the heated ecae device mold can be used in the ECAE pass: plus the blank 2曰8. The cookware can be heated to a temperature less than the static of the processed copper material, &apos;the lowest day/dish of the day (the other is referred to as the minimum recrystallization temperature), and is heated to about 125t to about 350. (The temperature is better.) In ECAE processing 310, intermediate annealing may be performed between some or all of the ECAE passes. Intermediate annealing may be below the onset of static recrystallization, at or near the beginning of static recrystallization. The temperature (defined as the lowest temperature at which the recrystallization of the material to be processed begins to occur) or within the temperature range in which the composition is completely static recrystallized. The temperature at which the intermediate annealing is carried out can affect the size and orientation of the crystal grains and can therefore be utilized as a Specify the pattern required in the situation.

Intermediate annealing at temperatures that produce complete static recrystallization allows more texture weakening to occur in subsequent ECAE passes. Annealing at temperatures below the onset temperature of static recrystallization can also result in a change in texture strength and orientation (applied force release). The reorientation effect is greatest when the secondary crystallization temperature anneal is performed between one or more initial four passes, and becomes less significant when performed between passes after the fourth pass. Annealing at the onset temperature of static recrystallization can simultaneously cause texture (strength and/or orientation) and some changes in recrystallization. The intermediate annealing repeated between successive passes may have a reinforcing effect than the effect described by the individual annealing events. In the particular application of the invention it is preferred to carry out any intermediate annealing at temperatures and times which would result in static recrystallization of the material being processed. It is advantageous to perform an intermediate anneal at a temperature below -19-1278525 which causes static recrystallization to minimize surface cracking and enhance structural uniformity. When the forged block of ECAE comprises high purity copper, the intermediate annealing is preferably carried out at a temperature of from about 125 ° C to about 225 ° C and for a period of time of about one hour. This allows the ECAE process 3 10 to produce a directionally pure copper material having a very uniform and small grain size (e.g., an average submicron grain size to about 20 microns). In the view of the present invention, when the forged block material comprises a copper alloy, it is preferred to perform the sub-crystallization temperature intermediate annealing in the ECAE process 310 to include a temperature of from about 150 ° C to about 325 ° C, such that the temperature is maintained for at least 1 hour. good. This recrystallization temperature annealing process produces a copper alloy material having an average grain size of less than 1 micron. The high purity copper and copper alloy materials produced by the above ECAE process have improved hardness compared to materials produced by conventional processing techniques. A comparison of the final hardness of 6N copper and various copper alloys processed according to the methodology of the present invention with that of the same material before ECAE is shown in Table 1. Figure 4 compares the drop strength and ultimate tensile strength of high purity copper and various copper alloys processed in accordance with the methodology of the present invention, as well as 6N copper and various backing sheet materials having a grain size of 40 microns. Table 1: Effect of ECAE treatment on grain size and hardness of materials. Material before ECAE (grain size 30-50 μιη) Hardness (Vickers) Average grain size after ECAE Hardness after ECAE (Vickers) Hardness increase Rate 6 Ν copper 48.44 HV 5 μΐΉ 72.2 HV 49% 6Ν Cu+0.8% Ag 73.02 HV 4 μηι 89.88 HV 23% 6N Cu+0.8% Ag 73.02 HV 0.3 5 μιτι 172.4 HV 136% 6N Cu+0.5% Sn 75 HV 4 μιτι 104.56 HV 39.4% 6N Cu+0.5% Sn 75 HV 0.35 μηι 182 HV 142% -20 - 1278525 After preliminary treatment 200, the copper material may undergo another alternative path 330 including a rolling process to produce a target bullion (eg Figure 1). The embossing process 330 comprises forging the forged mass produced by the preliminary treatment 220 by a total of 60% reduction in cold milk, and at 60°/. Up to 85% is preferred. Cooling may include more than 4 passes, preferably more than 8 passes and preferably 8 to 16 passes. In the total squeezing process, the first four passes of each pass are preferably carried out at a reduction of from about 5% to about 6% of the thickness of the forged block. Further, the last four presses are preferably reduced by a thickness reduction of from about 10% to about 20% each time. Smaller reductions in the first 4 passes reduce or avoid cracks during the rolling process. Rolling produces small grain sizes in the resulting cold rolled high purity copper or copper alloy materials. Another option for the upper processing path is that the processing path 320 can be performed as shown in FIG. Path 320 utilizes a combination of cold rolling and equal diameter corner extrusion techniques. In the present invention, when the processing option 320 is utilized, it is preferred that the hot forged block produced by the preliminary process 200 is subjected to ECAE and subsequent cold rolling. However, it should be understood that the present invention contemplates performing cold rolling before or after ECAE before and after ECAE. The ECAE portion of process 320 can include the ECAE processing described above. The material extruded from the ECAE can then be cold rolled to a reduction of less than 90% to form the bullseye. In particular, the cold rolled portion of path 320 produces a reduction of at least about 60%, preferably. The cold rolling of the ECAE extruded material may include the above-described rolling process of the associated embossing process 330. In a particular aspect, path 320 can be combined with forging and rolling to produce at least 60% and less than 90°/. The total reduction rate. Another option is to use the forging process to produce a desired reduction of 60% to 90% without nip. Combining ECAE with subsequent nip and/or forging processes is advantageous because such processing of 1278525 can cause the desired grain orientation into the copper material. The resulting orientation may comprise a predominantly grain orientation or may comprise the most significant grain orientation. Pressurization and/or forging can be used to produce a strong or strong texture within the copper article of the present invention. In some views, the strong texture produced by post-ECAE embossing/forging will be a texture other than (220). The dry core comprising the copper or copper alloy may undergo a final target forming process 500 and may optionally undergo an additional heat treatment process 400 (as shown in Figure 1) prior to final target formation 500. The heat treatment process 400 as desired may include annealing at a temperature and time less than the onset of static recrystallization. Low temperature annealing (also known as recovery annealing) is carried out at a minimum temperature below static recrystallization. Re-annealing or annealing as needed is advantageous to maintain a very small grain size. Such low temperatures or no annealing can result in a bulls-eye having an average grain size of less than about 1 micron. Alternatively, the target may be subjected to a temperature equal to or greater than the lowest temperature at which recrystallization occurs for a period of time sufficient to form a final grain distribution within the target. Although static recrystallization increases the grain size, this increase can be minimized by the minimum time to produce the desired amount of recrystallization (partial or complete recrystallization) by annealing at a temperature close to the recrystallization minimum temperature. The recrystallization annealing of the copper alloy is preferably carried out at a temperature of from about 350 ° C to about 500 ° C for from about 1 hour to about 8 hours. The recrystallization annealing of the high purity copper is preferably carried out at a temperature of from about 225 ° C to about 300 ° C for from about 1 hour to about 4 hours.

Figures 5 and 6 show the grain size and distribution of 6N copper having an average grain size of about 6 microns produced using the ECAE according to the methodology of the present invention and subsequently annealed at 250 °C for 5 hours. Figure 7 shows the evolution of grain size as a function of heat treatment of copper alloyed with 0.53% Mg alloyed by ECAE of 6 passes D -22 - 1278525 before annealing. Figure 8 shows the grain size and distribution of the copper/0.53% Mg alloy of Figure 7 after annealing at 300 °C for 2 hours. Figures 9 and 10 show the grain size and distribution of the copper/0.53% Mg alloy of Figure 7 after annealing at 450 °C for 1.5 hours, using EBSD/SEM (Figure 9 and optical microscopy (Figure 10) analysis.

It should be noted that the optional target 310, 32 〇 or 33 靶 can be aged (not shown) after the heat treatment step 400 or after the heat treatment step 4 . When aging is utilized, the aging is performed at a temperature of less than about 5 Torr (rc). Performing the aging step as indicated above increases the strength of the copper or copper alloy bullseye by causing a fine precipitate having an average precipitate size of less than about 〇5 microns. The method produces a purity copper or copper alloy dry core which can be subjected to a final standard &amp; 500 to produce a monolithic standard or alternatively - to produce a bonded standard leather (here, the binding target) means to be bonded to, for example, a backing sheet. Supported sputtering target).

When the final crown is formed as a single piece of standard leather, the final standard of the leather can include, for example, the shape of the standard leather required for the mechanical work of the dry heart. When used in the semiconductor wafer addition step 500 generated by the method of the present invention, the method and the method can be applied to a wafer having a size of 00 mm, or a 300 mm wafer, and can be used for processing, for example, according to the present invention. A typical single piece of copper on a 200 mm semi-conductive silicon wafer: 丰导- 于力.... . The size of the wafer is about the thickness. · 89 leaves. The sputtering surface of the sputtering target can be used with a diameter of 20.7 吋 and the housing _! λ 丄 and 仏 is 17·5 pairs, and the 标 block target is a plane 俨 “The monolithic target formed by the method of the present invention is千面禚 target is preferred 'Although it can be tested / he can choose the size. 拎 target shape and its -23 - 1278525 According to the invention, the grain size of the monolithic stem of the ancient i, 刚屋生 is less than or equal to about 50 The micron is preferably so as to increase the size of the 微米f^. The submicron grain size &lt; The monolithic standard of the invention | The strength of the yak, the ultimate tensile strength (UTS) and the hardness are larger than the average grain size of 3 The micro-U is not substantially the same as the target composition of at least about 5%. According to the present invention, the size of the σ 生 卞叼 卞叼 为 大小 大小 大小 大小 大小 大小 大小 : : : : : : : : : : : : : : : : : : : : : 10%. For the application of the maximum standard (four degrees) for the monolithic block, the single block is better in the case of no heat treatment. Because of this, a single block is produced to maintain the front processing yield of 'half large'. When the sub-micron grain size is pulverized and/or produced, the sub-micron grain can be maintained in the final monolithic standard dry The target strength of the scorpion is maximized. In another 彳 彳 违 违 违 违 违 违 违 违 违 违 违 违 违 违 违 违 违 违 违 违 违 违 违 违 违 , , , , , , , , , , , , , The final grain distribution of 20 micrometers is a single piece of standard bar. When the step 500 is generated, the 巴 巴 巴 巴 纟 & & & & & & & & & 立 & & & 标 标 标 标 标 标 标 标 标 标 标 标 标 标 标 标 标 标 标 标 标 标In addition to any machining performed to form the desired target shape: a social integration step. The bonding process may include bonding the dry core formed by the prior processing method to a support such as a backing sheet. A typical backing sheet may include, for example, and/or Copper. The bloody board is made of (5), A1 chest and A1606 i T4. The combination process can include various types or kinds of strange pressure, pressing, coating, soldering, explosion combination, blood and forging, diffusion bonding or familiarity. Other alternative methods known to the artist: The process can produce a combination of a drop strength of at least about 10 ksi. In particular, the 'bonding process produces a bond strength greater than or equal to m5 ksi and in a particular application, the bond strength produced is equal to Or more than 3〇ksi. Available on Various processing methods produce a very uniform and small grain size of copper -24- Ϊ 278525 2. The average grain size is usually sub-micron to Longfu, #, and the size is extremely high. $ _ 1 〃, nearby The small grain gate has a strength of ~3, because the high (10) can be used to combine the standard dryness, and the β method. When the target is prepared, the heating (heat treatment 400) can be combined with the standard. The high-purity temperature of the process according to the method of the present invention is less than or equal to about 4 hours; = less than or equal to the minimum grain growth. Although in the high temperature society: the implementation of the standard grain growth Initially fine grain size;: = Some of the Α Α 姑 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 成长 成长 成长 成长 成长 成长 成长The strength of the crater of the 太 穴 τ 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在曰4 combined with the copper alloy standard I &gt; shape, recrystallization, the better, the degree and time is less than the full static 9 仃. The sample is combined with less than about 400t: production, good combination is better for 4 hours, and less than 4〇〇~ degrees for 々, JJU u for 1-4 hours. Another-choice for the combination can include a higher than a specific combination of Yue ~ Tuo from the earth, the 'mouth imitation / dish degree. In the combination of the temperature of the lowest temperature of the crystal, the combination of the temperature of 4 and the amount of f f f μ _ will be minimized to minimize the grain growth. In combination with the private & a $ ^ 丄 and ", then, the daily average grain size produced in the copper alloy is 1 soil is preferably 20 microns. The heat treatment of the full recrystallization is preferably carried out at a temperature of about 200 C for at least about 1 hour, and preferably between 350 ° C and 500 ° C for more than 1 hour. . Another option for heat treatment combined with heat and combined with &gt;&amp;&lt;&gt;&gt; is that the heat treatment can be carried out in the bonding step (i.e., heat treatment 4), or after the bonding step. The combined combination and heat treatment are beneficial to enhance the social bagua city d degree and re-bond the copper or copper alloy material to 1278525. According to the method of the present invention, the shape is formed by a conventional method: the combination of the mouth steel and the combined copper alloy target ratio In some aspects of the present invention, the binding strength is increased. It is preferred that the diffusion is combined with the grain size of the dry core. When the standard dry can produce a very high intensity diffusion bond. The enhanced diffusivity of fine grains from Q4 is 15 ksi or higher, and left-I 13. The combined diffusion and strength of the resulting diffusion combined with copper and copper alloys 2 or super-the present invention is resistant to bending of the standard leather, reducing electricity = gram-bar. Additional advantages include improved applications that provide improved quality. The use of the target of the present invention for sputtering provides a better uniformity: the factory: and the film: and = in the film of the particles therein, and the method according to the invention is used ====-. This improved film thickness and impedance of the wafer to crystal: conductor processing provides::, the invention of the monolithic high-purity copper and copper alloy formed by the traditional method of the formation of the traditional combination of copper and copper two , 0%. Typically 40% longer. The ability to achieve a single piece of copper standard can be avoided: in the traditional combination of the combination (separated from the backing plate). According to the present invention &lt;single block target additionally has increased resistance to target bending, reduced arcing, reduced uniformity of film produced by such target sputtered films, enhanced film thickness and impedance. In addition, the monolithic target according to the present invention improves wafer-to-wafer film thickness uniformity and impedance uniformity. The examples shown below are typical preferred embodiments of the invention. It is understood that the present invention contemplates additional specific embodiments and is not intended to be limited to the particular -26-1278525 examples shown. Example 1: Manufacture of a High Purity Copper Monolithic Sputtering Target A 6N purity 6 inch diameter and 1 inch long cast copper billet was heated in an air oven and maintained at a temperature of about 990 °F for about 60 minutes. The copper billet is then hot forged (using yttria or graphite foil in hot forging) to a final height reduction of 55-75% and engraved with water and ocean fire. Thereafter, the forged block was passed through cold rolling for 6 times, and quenched after the first 8 passes, and the total reduction rate was about 6 Torr. /() to about 80%. Cracking is avoided by cold rolling in each of the first four passes resulting in a reduction of about 5% to about 6% each time. A 13-16 pass is made to produce a reduction of about 10% to about 11% each time to achieve a small grain size. After cold rolling, the Baxin was recrystallized by heating to about 480 F for about 120 minutes. Machining the bullseye produces the final target. The resulting high purity copper monolithic target has an average grain size of less than 50 microns and a uniform grain distribution throughout the target. Figure 11 depicts a sampling location for analyzing the production of a monolithic target. The thickness of the standard is 0.89吋. The grain sizes measured at each point on the sputter surface and their average are listed in Table 2. The grain size measurement of the surface of the rabbit and the standard bar f 1 2 3 4 6 7 8 9 The average grain size 38 45 45 38 38 53 38 38 53 43 The internal plane of Figure 11 indicates the grain size measured and the The test value is average. Table 4 shows the measured texture of the same labeled target point in Figure 11. The crystals of the marked points in the target are measured to the depth of 2 4 5 7 _ average 0.250&quot; 53 38 ______ a 45 _ 45.3 0.460&quot; 45 38 45_„_ 45 __ 43.3 〇·7〇〇&quot; 45 45 ------ _^ 45 _, 45 -27- 1278525 Table 4: Texture depth position of the target microstructure on the marked point (111) (200) (220) (Π3) 0.00 丨, 2 24.0% 20.9% 25.0% 30.1% 4 23.9% 22.3% 23.7% 30.1% 5 21.5% 20.6% 26.2% 31.7% 7 23.5% 20.5% 24.2% 31.7% 0.250, ' 2 22.5% 16.9% 30.8% 29.7% 4 24.6% 16.7% 28.7% 30.2% 5 18.0% 15.2% 39.4% 27.5% 7 24.5% 15.2% 31.2% 28.0% 0.460&quot; 2 21.5% 17.6% 35.1% 25.8% 4 19.0% 17.6% 42.4% 21.0% 5 16.8% 15.9% 41.2% 26.2% 7 20.5% 17.2% 33.1% 29.3% 0.700&quot; 2 21.9% 20.5% 26.0% 31.6% 4 23.0% 20.8% 25.8% 30.4% 5 22.2% 20.8% 27.2% 29.8% 7 22.4% 22.4% 21.1% 34.0%

Additional examples of high purity targets were formed as shown in the previous examples except that ECAE was included in this process. The ECAE is performed prior to cold rolling to reduce the presence of grain size present in the pseudo-cast. The resulting targets were analyzed as shown in the previous examples. The average grain size of the target is less than 15 microns throughout the target. Example 2: Fabrication of a Copper Alloy Monolithic Sputtering Target A copper alloy billet of less than 10% Ag, Sn, Al or Ti was heated and maintained at a temperature of from about 900 °F to about 1500 °F for about 45 minutes. The billet is then hot forged to produce a final reduction of at least about 50°/〇. Some forgings (depending on the alloy) are heated in forging for at least 10 minutes. After the final forging, the forging is immediately quenched with water. The forged block is cold rolled to a reduction of at least 60% to form a bullion recrystallized by heating to about 750 °F to about 1 200 °F for 120 minutes. The recrystallized target core is mechanically processed to form a monolithic target. The average grain size of each target is from about 15 microns to -28 - 1278525 to about 50 microns. The specific target of copper alloyed with 原子.3 atom% of foot Α1 is formed by the diameter of 6 吋 long 丄i 吋. The bad was initially heated at 1400 T for 1 hour and initially forged to 6 吋 high. After the initial forging, the bad was heated at 1400 T for another 15 minutes and then forged to 3 Torr. After the final forging, the forged block is immediately quenched with water. After the cold rolling consisting of 7 passes, it was carried out according to the rolling plan shown in Table 5 to form a rolled dry core.

After rolling, the bulls were annealed at about 825 °F for about 120 minutes and formed the final monolithic target. The analysis target table (according to the surface points shown in Figure 11) shows the composition of the scoop and the average grain size of 37 microns. The grain size non-uniformity is 8 6% (丄 Sigma).

Table 5: 压11-0.3 atom% A1 nip plan pass direction (angle) △ high (吋) 鬲 (吋, %) 3⁄4 1 !/n 1 0 0.1 / υ //ρχ^ y -χ- _3. 3 :— 2 135 0.1 __2^δ _ 3.4 --- _: 3 270 0.1 2.7 --- -- 4 45 0.1 Z .0 5 180 0.1 -----__ 1 Q 6 315 0.1 ---- —————- --~~LJ . 〇__4.0 ~Γ —·—_ 7 90 0.1 - 2.3 —----- 4.2 8 225 0.1 - 丄2 9 0 0.13 2.07^^ -__ 4.3 CQ 10 135 0.13 1.94 _ J . y _ 6.2 C 7 _ 11 270 0.13 — — 12 45 0.13 __L68 _ 0./ _ 7.1 7 7 13 180 0.13 14 315 0.13 1.4? Q ^ —15 90 0.13 O . J 〇1 —16 225 0.13 _J^16 y . 1 in Π —17 One free passage -~-- - - -29- 1278525 Example 3: Copper alloy diffusion bonded sputtering target fabrication Copper alloy billet and processed as described in Example 2 Except for cold rolling to a reduction rate of at least about 50%. The cold rolled I bar was bonded to the CuCr backing plate at a bonding temperature of about 450 ° C for 120 minutes. Recrystallization of the alloy occurs in combination. The grain size of the bonded standard bar is less than about 30 micrometers and the bonding strength is up to about 30 ksi. Example 4: Fabrication of a High Purity Copper Sputtering Target Using ECAE Provides a copper run of at least 99.9999% pure cast copper. High purity copper is forged at a height reduction rate of at least about 40% at a temperature of at least about 500 ° C to form a forged block. The forged block is liquefied by heating to a temperature of at least about 500 ° C for at least about 1 hour. The liquefied forged block was quenched with water immediately after heat treatment and extruded 4 to 6 times to obtain a submicron structure by equal channel angular extrusion (ECAE) according to path D (in continuous passage 90. rotary forged block). An intermediate anneal at a temperature of from about 125 Torr to about 225 ° C for a period of at least about ten hours is performed between some or all of the ECAE passes. The extruded high-purity copper block is cold [to a reduction rate of at least 6〇0/〇 to form a monolith or a target target of the binding target. Machining a single block of dry | Ba Xin to produce the final mark. Direct mechanical processing dry ~ produce / people 彳 米 rice grain size of the standard. Recrystallization is performed to produce a monolithic target having an average grain size of from 1 micron to about 2 microns. The target core of the binding target is diffusion-bound to the backing plate. The diffusion bonding is carried out at a temperature lower than 350 ° C for less than 4 hours. The combined fall strength is greater than about 15 ksi. The size of the bound target is from submicron to about 2 microns. Sub-micron standard dry = traditional standard strength of the standard bar. The grain size is (1) the combination of glutinous rice and the strength of the traditional copper standard 1 bar is at least 1G%. The grain size of the entire 6N copper standard bag after 2 hours of diffusion at 250 C is shown in Table 6 1278525. The size of the sentence is 丨1.37 μm and the standard deviation is 6.97% (1 Sigma). Grain size (μιη)

The three-point hardness measurement obtained from the upper and lower planes of the target of Table 6 is used. The average hardness is 53.3% and the standard deviation is 218% (ι Sigma). Target hardness (hb)

Example 5: Copper alloy sputtered leather was produced using ECAE. A steel billet containing copper alloyed at 1000 ppm to less than or equal to about 10% Ag, A, In, Zn, B, %, Ge, Ti or Zr was used. The billet is hot forged at a reduced rate of at least about 4% of the C to form a forged block. The forging block is heated to forge a block to a temperature of at least about 5 Torr (arc and maintained for at least 1278525 for about 1 hour to form a solution block. The solubilized block is quenched with water immediately after solubilization. The solubilized block is carried out by 4 to 6 The second pass through the ECAE extrusion. The solubilized block is rotated 90 each time according to the passage of path D. The intermediate annealing is carried out in some of the ECAE for at least one hour between about 150 C and about 325 C. The ecae extrusion block Cold rolling to a reduction rate of at least about 60% to form a copper alloy dry core. The first monolithic copper alloy &amp; dry by mechanical processing of the resulting copper alloy bullseye to form a monolithic target. The first monolithic standard The average grain size of the target is less than 1 micron. In addition, the first piece of the monolith target has a maximum strength, ultimate tensile strength (UTS), and hardness of at least 30 mm of the average element size of the target component. The height of the first single copper alloy target is generated by heat treatment as described above to produce a copper alloy bullhead. The heat treatment is carried out at a temperature of 350 t for about 丨 hours. The average grain size of the second target is from 1 μm to about 2 〇 micron, basically no sink Precipitate (where essentially no precipitation means no detectable precipitation) and no detectable separation and the largest void size is less than 1 micron. The first piece is combined with a copper alloy target by diffusion bonding as described. The copper alloy target is produced to the backing plate. The diffusion bonding is carried out at a temperature of less than 35 〇t: 丨 to 々 hours. The average grain size of the first bonded alloy target is less than 丨 micron. The second bond is combined with the copper alloy target. Spreading at a bonding temperature of about 35 〇t: to about 5 〇〇τ for at least 1 hour, the copper alloy target core generated as described above is diffused to the backing plate. The second copper-bonded copper alloy target is completely recrystallized and the average grain size is It is about 1 micrometer to about 20 micrometers. ~ [Simple description of the scheme] 1278525 The following is a description of the processing method of the present invention with reference to the following. A general overview of the present invention is generally based on Figure 2 depicts a cross-section and a view of a material treated by an equal-diameter angle extrusion device in Figure 3 of Figure 3. The two types of copper and copper alloys are processed by 'turn-angle extrusion. Drop...and The tensile strength is compared with the grain size and compared with the various backing sheets. 铋卞6N copper Figure 5 is 99.9999% copper material (6N) in accordance with one aspect of the invention, equal-diameter angular extrusion and Subsequently, after annealing at 25 吖 for 5 hours, the grain size is divided into: EBSD/SEM image of the image of K. 曰 Figure 6 shows the grain area distribution of the material of the image of Figure 5. The average grain size of the material is about 6 μm. Figure 7 shows that the average grain size as measured by EBSD and optical microscopy is a function of the annealing process. The annealing process is performed on the I-corner extrusion of the six-pass path D. The copper material was performed on copper. Figure 8 shows the EBSD/SEM image of the Cu 0·53 weight of Figure 7 / 〇Mg of the ECAE material after annealing at 300 °C for 2 hours. Figure 9 is an EBSD/SEM image of the Cu 0.53 wt% Mg ECAE material of Figure 7 after annealing at 450 °C for 1.5 hours. Figure 10 shows an image of the material of Figure 9 obtained using an optical microscope. Figure 11 is a sampling diagram depicting the measurement of grain size and texture in accordance with one aspect of the present invention. [Illustration of symbolic representation] 1278525 10 Machining scheme 12 Square blank 14 Lower surface 16 Upper surface 20 Equal-diameter angle extrusion device 22 Mold combination 24, 26 Channel 28 100 Provide copper burial 200 Preliminary treatment 310 Equal-diameter angular extrusion 320 Pressure Rolling and Equal Channel Corner Extrusion 330 Rolling 400 Heat Treatment 500 Final Marker Formation • 34-

Claims (1)

127^)^19421 Patent Application Chinese Patent Application Range Replacement Monthly (8) Year/Month) Pickup, Patent Application Range: Copper &amp; Golden Age Shooter, which basically consists of: Less than or equal to about 99.99 Weight ❶/〇 copper; at least one selected from the group consisting of Cd, Ca, Au, Ag, Be, u, Mg, Al, Pd, g See In ' Zn ' B ' Ga ' Mn, Sn, Ge, W, Cr, 〇 , Sb, Ir, P, As, Co, Te, Fe, s, Ti, Zr, Sc, ^, external, can, ^, m 〇 group of alloying elements, there is a total of at least one alloying element in the standard dry The amount is at least 1 〇〇ppm to less than 1% by weight, the hardness of the target is at least 40 HB; and /, the sentence size is less than 1 micrometer, and the standard deviation of grain size uniformity is within the target. Less than or equal to about 15% (1 Sigma). 2. For example, please refer to the standard of item 1 of the patent scope, the standard deviation of grain size uniformity is less than or equal to about 10% (1 sigma) in the target. 3. If the standard of the first paragraph of the patent application is applied, the standard deviation of hardness uniformity is less than about 5% (1 Sigma) in the entire standard bar. 4. If the standard of the third paragraph of the patent application is applied, the standard deviation of hardness uniformity in the crucible is less than about 3.5% (1 Sigma). 5. If you apply for the standard of the i-th item of the patent park, the remainder is monolithic. 6. If you apply for a patent scope! The index of the item, which is diffused and bonded to the backing sheet, has a combined diffusion strength of greater than about 15 ksi. 7. The target distribution function (〇df) is less than about 15 times the value of the target in the scope of the patent application. 8. The target distribution function (〇df) is less than about 5 times any value as claimed in the scope of the patent application. 86830-951215.doc 1278525 I master's grain orientation is not 9 · Target of the first scope of the patent application (220). 10. The standard of claim 1 is selected from the group consisting of Ag, Al, In, Ζη, Β. a target, wherein the at least one alloying element, Ga'Mg' Sn, Ge, Ti, and Zr, wherein the total amount of the alloying elements is as specified in the scope of the ninth aspect of the invention is from 1000 ppm to less than about 2%. 12. A copper alloy sputtering target substantially consisting of less than or equal to about 99.99% by weight of copper; and at least one selected from the group consisting of Cd, Ca, Hg, Ni, In, Ζη, Β, Ga, Μη P, As, Co, Te, Fe, S, Ti, Au 'Ag ' Be, Li, Mg, A, Pd, , Sn, Ge, W, Cr, 0, Sb, Ir, Zr, Sc, Mo, Si An alloying element of a group consisting of Re, Pt, Nb and Hf, wherein the total amount of at least one alloying element in the standard dry is at least 1 〇〇 ppm to less than 1% by weight, and the target 1 grain size is From 1 micron to about 2 micron, and the uniformity of grain size uniformity is less than about 15% (1 sigma) throughout the target. $申: The target of item 12 of the hi patent scope, wherein the standard deviation of the grain size uniformity is less than about 1% (1 sigma). 14. The dryness of the 12th paragraph of the patent application has a hardness of at least about 40 HB. For example, in the case of the patent #12, the hardness uniformity is included in the hardness standard deviation of less than about 5% of the sigma in the entire target. 6_ The target of claim 12, wherein the target is monolithic. 7. The target of claim 12, which is diffusion-bonded to the backing sheet, has a combined strength of greater than about 15 ksi. 86830-951215.doc -2 - 1278525 18. The target of the object of claim 12 has an orientation distribution function (ODF) of less than about 15 times any value. 19. The target distribution function (ODF) of the target of claim 12 is less than about 5 times any value. 20. For the target of claim 12, the main grain orientation is not (220) 〇 21. The target of claim 12, wherein the at least one alloying element is selected from the group consisting of Ag, Al, In a group consisting of Zn, B, Ga, Mg, Sn, Ge, Ti and Zr. 22. The target of claim 12, wherein the total amount of the alloying elements is from 1000 ppm to less than about 2%. 23. A monolithic sputtering target consisting essentially of copper and a total of less than or equal to 10% by weight of alloying elements selected from the group consisting of Cd, Ca, Au, Ag, Be, Li, Mg , Al, Pd, Hg, Ni, In, Zn, B, Ga, Mn, Sn, Ge, W, Cr, O, Sb, Ir, P, As, Co, Te, Fe, S, Ti, Zr, Sc An element of a group consisting of Mo, Si, Re, Pt, Nb and Hf; the target having an average grain size of from about 15 microns to about 50 microns and a hardness of at least 40 HB. 24. The monolithic target of claim 23, wherein the total amount of the alloying elements is less than or equal to about 2% by weight. 25. A monolithic target according to claim 23, which comprises at least 99.99% by weight of copper. 26. A bonded sputtering target consisting essentially of copper and a total of less than or equal to 10% by weight of alloying elements selected from the group consisting of Cd, Ca, 86830-951215.doc 1278525 Au, Ag, Be, Li, Mg, A1, Pd, Hg, Ni, In, Zn, B, Ga, Mn, Sn, Ge, W, Cr, 0, Sb, Ir, P, As, Co, Te, Fe, S, An element of a group consisting of Ti, Zr, Sc, Mo, Si, Re, Pt, Nb, and Hf; the standard dry diffusion is bonded to the backing plate at a bond strength of at least about 15 ksi, and the average grain size of the target It is from about 15 microns to about 50 microns. 27. The binding target of claim 26, wherein the at least one element is selected from the group consisting of Ag, Al, Sn, and Ti. 28. The binding target of claim 26, wherein the total amount of the alloying elements is less than or equal to about 2% by weight. 29. A bonded target according to claim 26, which comprises at least 99.99% by weight of copper. 30. A method of forming a monolithic sputtering target, comprising: providing a copper substantially consisting of copper and a total amount of one or more alloying elements of less than or equal to 10% by weight, the alloying elements being selected from Cd, Ca, Au, Ag, Be, Li, Mg, Al, Pd, Hg, Ni, In, Zn, B, Ga, Mn, Sn, Ge, W, Cr, O, Sb, Ir, P, As, An element of a group consisting of Co, Te, Fe, S, Ti, Zr, Sc, Mo, Si, Re, Pt, Nb and Hf; heating the billet to a temperature of at least about 900 °F and maintaining the temperature for at least about 45 minutes Hot forging a copper billet to form a forged block with a height reduction rate of at least about 50%; cold rolling the forged block to a reduction rate of at least about 60% to form a bullseye; heating #巴心 to cause recrystallization and forming an average grain size less than Final grain orientation of about 100 microns; and 86830-951215.doc -4 - 1278525 The target core is formed into a monolithic target shape. 31. The method of claim 30, further comprising water quenching after hot forging. 32. A method of forming a monolithic sputtering target comprising: burying copper with at least 99.99% by weight copper; heating copper to a temperature of at least about 900 T and maintaining at this temperature for at least about 45 minutes The billet is hot forged at a height reduction rate of at least about 50% to form a forged block; the equal-diameter angular extrusion of the forged block is performed; the forged block is cold-rolled to at least about 60°/. The rate of reduction is such that a dry core is formed; the target is heated to cause recrystallization and a final grain distribution having an average grain size of less than about 100 microns is formed; and the &apos;heart is formed into a monolithic shape. 33. The method of claim 32, wherein the average grain size is less than or equal to about 50 microns. 34. The method of claim 32, wherein the average grain size is less than or equal to about 15 microns. 35. A method of forming a bonded yttrium mark, comprising: providing a copper chain comprising at least 99.99% by weight of copper; heating the copper blank to a temperature of at least about 900 T and maintaining the temperature at at least about 45 minutes; Approximately 50% of the height reduction rate is hot forged copper blank to form a forged block, 86830-951215.doc 1278525 for equal-diameter angular extrusion of the forged block; cold-rolled forged block to a reduction rate of at least about 50% to form a bull's eye; The bull's eye is bonded to the backing plate. 36. The method of claim 35, wherein the bonding is performed at a temperature that causes recrystallization and forms a final grain size having an average grain size of less than about 100 microns. 37. The method of claim 35, wherein the combination produces a combination of at least 15 ksi intensities. 38. A method of forming a combined dry shot, comprising: providing a copper blank consisting essentially of copper and one or more alloying elements less than or equal to 1% by weight, the alloying elements being selected from Cd, Ca, Au, Ag, Be, Li, Mg, Al, Pd, Hg, Ni, In, Zn, B, Ga, Mn, Sn, Ge, W, Cr, O, Sb, Ir, P, As, An element of a group consisting of Co, Te, Fe, S, Ti, Zr, Sc, Mo, Si, Re, Pt, Nb and Hf; heating the billet to a temperature of at least about 900 °F and maintaining the temperature for at least about 45 minutes The billet is hot forged at a height reduction rate of at least about 50% to produce a forged block, the cold forged block is cold cut to a reduction of at least about 50% to form a bullseye; and the target is bonded to the backing plate. 39. The method of claim 3, wherein the bonding is carried out at a temperature that causes recrystallization and forms a final grain size having an average grain size of less than about 100 microns. 40. The method of claim 38, wherein the hot forging comprises: 86830-951215.doc -6 - 1278525 initial heating; a reduction in the height of the sub-segment; and at least one reheating and an additional height reduction. 1. The method of claim 38, wherein the method further comprises performing an equal-diameter angular extrusion prior to the cold rolling. 42. A method of forming a copper-containing sputtering target, comprising: providing a Cu blank having a purity of at least 99.99%; hot forging at a temperature greater than 3 ° C with a height reduction rate of at least about 40% To form a forged block; a water-quenched forged block; to perform an extrusion process comprising the following items: passing the forged block through an equal-angle angular extrusion (ECAE) at least 4 times; and containing 1 or 2 times at least some at least 4 passes Heat treatment of the intermediate annealing, and the ECAE is molded to a temperature of about 125 ° C to about 225 ° C during the extrusion process; after the extrusion process, cold rolling to a reduction rate of less than 90% to form #巴心; The bullseye forms a target having an average grain size of from 1 micron to about 50 microns and a hardness of at least 40 HB. 43. The method of claim 42, further comprising solubilizing the forged block prior to water quenching, the solubilizing comprising heating the forged block to a temperature of at least about 500 ° C and maintaining the temperature for at least 60 minutes. 44. The method of claim 42, further comprising heating the leather core to recrystallize the copper and form a final grain distribution in the dry core, the maximum grain distribution of 86830-951215.doc 1278525 The average grain size is from about 1 to about 20 microns, wherein the core is formed into a monolithic standard to form a monolithic I bar. 45. The method of claim 42, wherein there is a uniform grain size distribution throughout the center of the grain, the standard deviation of the uniform grain size being less than 15% (1 sigma). 46. The method of claim 42, wherein the 〇:11 chain has a purity of up to about 99.999% copper. 47. A method of forming a copper alloy sputtering target, comprising: providing substantially less than 99.99% copper and at least one selected from the group consisting of Cd, Ca, Au, Ag, Be, Li, Mg, A, Pd, Hg , Ni, In, Zn, B, Ga ' Mn ' Sn, Ge, W, Cr, 0, Sb, Ir, P, As, Co, Te, Fe, S, Ti, Zr, Sc and Hf The element, wherein the total amount of the at least one alloying element is at least 100 ppm to less than 10% by weight; the hot forging of the Cu billet at a temperature of more than 300 ° C at a height reduction rate of at least about 40% for forging Block; performing an extrusion process comprising: subjecting the forged block to an equal diameter angular extrusion (ECAE) at least 4 times; and heat treating the heated ECAE mold once or simultaneously during extrusion, and at least some at least 4 Sub-annealing at a temperature of between about 120 ° C and about 325 ° C for at least one hour; after the extrusion process, cold rolling to a reduction of less than about 90% to form a plaque; and forming the target Target. 86. The method of claim 1, wherein the squeezing process comprises heating the ECAE mode to about 125. (: to a temperature of about 325 ° C. 49. The method of claim 47, further comprising heating to at least about 5 Torr (the temperature of TC and maintaining the temperature at least about 60 prior to the extrusion process) The method of claim 47, wherein the target has an average grain size of from 1 micrometer to about 20 micrometers. 51. The method of claim 47, wherein The average grain size of the target is less than 1 micrometer. 52. The method of claim 47, wherein there is a uniform grain size distribution in the entire target, and the standard deviation of the uniform grain size is less than 15% (1) Sigma. 86830-951215.doc -9 -