Copper Manganese Sputtering Target

Abstract

To provide a sputtering assembly comprising a copper manganese alloy sputtering target that has high-strength, high-thermal stability, and refined microstructures.SOLUTION: The invention provides a sputtering assembly 10 comprising a sputtering target 14 comprising: a copper alloy containing manganese present at a weight percentage from about 2 wt.% to about 20 wt.% with the balance comprising cupper and inevitable impurities. The sputtering target has substantially refined secondary phases, so that the secondary phases have a mean diameter that is at least about 1.5 times smaller than a mean diameter obtained by conventional thermo-mechanical processing methods.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to high-strength copper-manganese alloys. More specifically, the present disclosure relates to copper-manganese alloys containing at least 2 wt.% manganese. In some embodiments, the copper-manganese alloys can be used in sputtering target assemblies. Methods for forming the high-strength copper-manganese alloys are also described. [Background technology]

[0002] Physical vapor deposition ("PVD") is widely used to form thin films of materials on the surfaces of various substrates. In one PVD process, known as sputtering, atoms are ejected from the surface of a sputtering target by collision with gas ions, such as a plasma. The sputtering target is therefore the source of the material to be deposited on the substrate.

[0003] A diagram of a portion of an exemplary sputtering assembly is shown in FIG. 1. The sputtering assembly 10 includes a backing plate 12 having a sputtering target 14 bonded thereto. A semiconductor wafer 18 is disposed within the assembly and spaced apart from the sputtering surface 16 of the sputtering target 14. During operation, particles or sputtered material 22 are displaced from the surface 16 of the sputtering target 14 and deposited on the surface of the semiconductor wafer 18 to form a coating (or thin film) 20 on the wafer. It should be understood that the sputtering assembly 10 shown in FIG. 1 is an exemplary configuration, as, for example, both the target 14 and the backing plate 12 can be of any suitable size or shape. In some embodiments, the physical vapor deposition apparatus 10 can include the sputtering target 14 without the backing plate 12. This configuration is referred to as a monolithic configuration.

[0004] Various metals and alloys can be deposited using PVD techniques, including, for example, Al, Ti, Cu, Ta, Ni, Mo, Au, Ag, Pt, and alloys of these elements. One such alloy is copper manganese ("CuMn"), which is used in sputtering targets to form various metal interconnects used in the semiconductor industry, for example. Current CuMn alloy sputtering targets contain less than 1 wt. % Mn.

[0005] Additionally, advances in semiconductor wafer manufacturing technology have led to a demand for larger sputtering target configurations, such as 300 mm and 450 mm sputtering targets (i.e., targets for use in 300 mm or 450 mm silicon wafer deposition processes). Higher sputtering powers have also been used to improve throughput, film quality, and uniformity. However, high sputtering powers can increase the risk of deflection and warpage in conventional sputtering targets. Therefore, there is a desire in the semiconductor industry for sputtering targets with higher strength to limit deflection. Summary of the Invention

[0006] In one embodiment, a method of forming a high strength copper alloy includes heating a copper material containing manganese to a temperature above 400°C, wherein the copper material contains about 2% to about 20% by weight of manganese; cooling the copper material to a temperature of about 325°C to about 350°C to form a cooled copper material; and extruding the cooled copper material by equal channel angular extrusion (ECAE) to form a cooled copper material. and forming a manganese alloy.

[0007] In another embodiment, a sputtering assembly includes a sputtering target having a copper-based, manganese-containing copper alloy, the manganese being present in a weight percent of about 2 wt % to about 20 wt % by weight of the copper alloy. The sputtering target has a substantially refined secondary phase, such that the secondary phase has an average diameter at least about 1.5 times smaller than the average diameter obtained by conventional thermomechanical processing methods such as forging and rolling.

[0008] While multiple embodiments are disclosed, still other embodiments of the present invention will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments of the invention. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not restrictive. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a diagrammatic view of a portion of a physical vapor deposition apparatus. [Figure 2] FIG. 1 is a flow diagram of a method of forming a copper manganese alloy, according to some embodiments. [Figure 3] 1 is a graph comparing Brinell hardness and annealing temperature for certain exemplary copper alloys. [Figure 4] 1 is a graph comparing recrystallized grain size with annealing temperature for certain exemplary processing methods. [Figure 5A] 1 is a photomicrograph taken with an optical microscope comparing the grain size of copper manganese alloys subjected to specific processing conditions; [Figure 5B] 1 is a photomicrograph taken with an optical microscope comparing the grain size of copper manganese alloys subjected to specific processing conditions; [Figure 5C] 1 is a photomicrograph taken with an optical microscope comparing the grain size of copper manganese alloys subjected to specific processing conditions; [Figure 5D] 1 is a photomicrograph taken with an optical microscope comparing the grain size of copper manganese alloys subjected to specific processing conditions; [Figure 6]1 is a graph comparing yield strength and ultimate tensile strength for copper manganese alloys subjected to certain exemplary processing methods. [Figure 7] 1 is a graph comparing the yield strength of several existing backing plate materials with the yield strength of certain exemplary copper manganese alloys. [Figure 8] 1 is a graph comparing the Brinell hardness of several existing backing plate materials with the Brinell hardness of certain exemplary copper manganese alloys. DETAILED DESCRIPTION OF THE INVENTION

[0010] Disclosed herein are high-strength copper-manganese alloys for use in, for example, sputtering targets. More specifically, disclosed herein are copper-manganese alloys having high strength, high thermal stability, and refined microstructures. Also disclosed are methods of forming the copper-manganese alloys, including heat treatment steps and equal channel angular extrusion (ECAE).

[0011] High-strength copper-manganese alloys include copper as a major component and manganese as a minor component. The major component copper is present in a higher weight percent than the minor component manganese. For example, high-strength copper-manganese alloys may include about 80% to about 98%, about 88% to about 97%, or about 90% to about 92% copper by weight, and about 2% to about 20%, about 3% to about 12%, or about 8% to about 10% manganese by weight. In some embodiments, high-strength copper-manganese alloys may include copper, manganese, and one or more additional minor components. In other embodiments, high-strength copper-manganese alloys may include copper, manganese, and oxygen, carbon, or other metals. and other trace elements.

[0012] High-strength copper-manganese alloys have a refined microstructure. In some embodiments, the alloys have an average grain size of up to about 15 μm (e.g., about 0.2 μm to about 15 μm) in diameter. For example, the grain size can be about 0.2 μm to about 1 μm, about 1 μm to about 2.5 μm, about 2.5 μm to about 6.5 μm, about 6.5 μm to about 12.5 μm, or about 12.5 μm to about 15 μm.

[0013] The copper manganese alloy may be substantially free of porosity, such that fewer porosity occurs in the copper manganese alloy of the present disclosure compared to "cast" materials. In some embodiments, the alloy may be porosity-free, such that no porosity occurs. In other embodiments, the alloy may be substantially free of large porosity or pores, such as those greater than about 100 μm in diameter.

[0014] Copper-manganese alloys may also have refined secondary phases. Copper alloys with a high (i.e., 2 wt. % or greater) weight percent manganese may contain manganese precipitates and secondary phases or inclusions that are undesirable in sputtering targets. Secondary phases may include, for example, manganese oxides (MnO) and / or manganese sulfide (MnS), the formation of which depends on the presence of oxygen and / or sulfur during the alloying process. Current copper-manganese alloys contain limited amounts of secondary phases, and the secondary phases present have average diameters that are smaller than those of secondary phases present in alloys processed by conventional thermomechanical processing methods. For example, the secondary phases of current copper-manganese alloys may have average diameters that are at least about 1.5 times smaller than those of conventionally processed alloys. Examples of conventional thermomechanical processing methods, or alternatively referred to herein as conventional methods, include casting, forging, and rolling. Thus, copper manganese alloys processed with current processing methods may have secondary phases with average diameters that are at least about 1.5 times smaller than copper manganese alloys processed with conventional methods.

[0015] The copper manganese alloy may also have increased hardness properties. In some embodiments, the Brinell Hardness (HB or HBN) of the copper manganese alloy may be from about 155HB to about 200HB.

[0016] Copper-manganese alloys can also have high strength. Copper alloys with a high weight percent (i.e., 2 weight percent or more) of manganese typically have higher strength than copper alloys with a low weight percent (i.e., less than 2 weight percent) of manganese. For example, copper-manganese alloys can have an average yield strength of about 475 MPa to about 700 MPa.

[0017] In some embodiments, the copper manganese alloy can be a sputtering target for use in a physical vapor deposition apparatus, such as apparatus 10 shown in Figure 1. In some embodiments, the copper manganese alloy sputtering target can be connected or bonded to a backing plate. In other embodiments, the copper manganese alloy can be a monolithic target.

[0018] The copper manganese alloy sputtering target 14 may be formed by a method according to Figure 2. Figure 2 is a flow diagram of a method 100 of forming a copper manganese alloy, according to some embodiments. In one embodiment, the method 100 includes a first initial processing step 110. The first initial processing step 110 may include, for example, using powder, chips, flakes, cast master alloys, or granules to add alloying elements (i.e., manganese) to obtain a preferred material composition. The first initial processing step 110 may also include other processes known to those skilled in the art, such as casting. In some embodiments, the method 100 also includes a second initial processing step 111 involving an initial thermo-mechanical (TMP) treatment. One exemplary A suitable TMP processing method involves hot forging the copper-manganese material. During hot forging, the height of the copper-manganese billet is reduced so that the billet size is suitable for further processing. Hot forging can also further refine the casting grain size, increase homogenization or composition, and reduce casting defects such as voids and porosity. The hot forging temperature depends on the weight percentage of manganese. For example, for alloys with lower weight percent manganese, a suitable hot forging temperature range may be about 400 to 600°C for a period of at least one hour. For alloys with higher weight percent manganese, a suitable temperature range may be about 600 to about 950°C for a period of at least one hour. After hot forging, the copper material may be water quenched or cooled to room temperature in air. The second initial processing step 111 may also include other processes known to those skilled in the art.

[0019] The method 100 further includes a first processing sequence 104, which includes steps 112, 114, and 116. In step 112, the copper material is heated to a temperature above 400°C for a period of at least one hour. For example, the copper material may be heated to a temperature of about 425°C to about 450°C for a period of at least one hour. However, this temperature may vary depending on the weight percent of manganese present in the CuMn alloy. For example, the temperature may be higher for CuMn alloys with a higher weight percent of manganese to achieve better healing of porosity and homogenize the composition. This temperature can be determined by measuring the Brinell hardness. For example, the Brinell hardness should be about 90-130 after the heat treatment to limit cracking and reduce stress during subsequent ECAE processing. In some embodiments, the temperature may be about 10°C below the full recrystallization temperature of a copper-manganese alloy that has undergone three to four passes of ECAE. The full recrystallization temperature can be determined by heat treating the copper material at various temperatures for one hour and measuring the grain size and Brinell hardness. Full recrystallization is complete when all grains are recrystallized. The copper material is a mixture of copper and manganese, where copper is present as the primary component and manganese is present as a minor component. For example, the copper may be present in an amount of about 80% to about 98% by weight copper and about 2% to about 20% by weight manganese. The copper material may also contain other minor components or impurities. In some embodiments, step 112 can be performed by homogenization or annealing to provide a uniform microstructure.

[0020] In step 114, the copper material is cooled to a temperature of about 300° C. to about 350° C. to form a cooled copper material. For example, the copper material may be cooled to a temperature of about 325° C. to about 350° C. The copper material may be cooled rapidly, such as by quenching, or may be air-cooled at ambient temperature.

[0021] In step 115, the cooled copper material may undergo a first optional heat treatment step. For example, the cooled copper material may be heated to a temperature of about 425°C to about 750°C for a period of at least one hour. This optional heat treatment may be completed to recrystallize any variations in the microstructure resulting from annealing step 112 and / or cooling step 114, resulting in a more uniform and refined microstructure.

[0022] In step 116, the cooled copper material is extruded through ECAE to form an ECAE copper-manganese alloy. In some embodiments, step 116 includes one to four passes through ECAE. In other embodiments, step 116 may include more than four passes through ECAE. In some embodiments, the copper-manganese alloy may be rotated between ECAE passes. For example, step 116 may include four passes through ECAE, with the cooled copper material rotated 90 degrees between each pass.

[0023] The method 100 may further include a final processing step 124, which may include, for example, a multi-step heat treatment, stress relieving, or any other process that does not affect the properties of the copper manganese alloy. The alloy may then be subjected to further processing to be used as a monolithic target or may be bonded to a backing plate for use in sputtering applications.

[0024] In another embodiment, method 100 may include an initial processing step 110 as disclosed above, a first processing step 104 as disclosed above, and an optional second processing sequence 106 including steps 118, 120, and 122.

[0025] In step 118, the cooled copper manganese alloy is subjected to a first rolling step.

[0026] In step 120, the alloy may undergo a second optional heat treatment step in which it is heated to a temperature above 400°C for a period of at least 0.5 hours to form a cooled copper manganese alloy. For example, in one embodiment, the cooled copper manganese alloy may be heated to a temperature of about 400°C to about 575°C for a period of about 0.5 hours to about 4 hours. In another example, the alloy may be heated to a temperature of about 425°C to about 550°C, depending on the desired properties of the alloy, such as strength, grain size, and any other properties.

[0027] In step 122, the heated copper manganese alloy may be subjected to a second rolling step, or a forging, extrusion, or drawing step, to form a hardened copper manganese alloy. In some embodiments, the hardened copper manganese alloy has a substantially refined microstructure, whereby the grain structure is substantially uniform and equiaxed. Furthermore, in some embodiments, the hardened copper manganese alloy may have an average grain size of about 1.5 μm to about 15 μm. In other embodiments, the alloy may have an average grain size of about 1.5 μm to about 5 μm. Method 100 may further include a final processing step 124, as disclosed above.

[0028] CuMn alloys with a high percentage of manganese often exhibit increased strength and / or hardness properties compared to CuMn alloys with a lower percentage of manganese. However, because CuMn alloys with a higher percentage of manganese are harder, they are more prone to forming porosity and casting defects, and therefore often more prone to cracking due to the brittleness of the material. The ECAE process described herein results in manufacturable CuMn alloys.

[0029] Example 1: Effect of annealing temperature and Mn content on hardness The effect of annealing (i.e., heat treatment) temperature on hardness was observed for various copper-manganese alloys having weight percentages of Mn ranging from about 0.5 wt.% to about 10 wt.%. The copper-manganese alloys were heated to temperatures ranging from about 250°C to about 600°C, and the corresponding Brinell hardness (HB) values ​​were determined by performing standard Brinell hardness tests according to American Standard ASTM E10-14.

[0030] Figure 3 shows the relationship between HB value and annealing temperature for seven different copper manganese alloy compositions formed by combining high purity copper with manganese in the amounts listed in Table 1. For all CuMn alloys used in this example, 6N Cu (99.9999% purity) and 5N Mn (99.999% purity) were used. All alloys were processed by ECAE. All numbers in Table 1 are expressed on a weight percent basis.

[0031] [Table 1]

[0032] As shown in Figure 3, Compositions 2 and 6, which have weight percents of Mn of 7 wt% and 10 wt%, respectively, have higher HB values ​​than copper manganese alloys with lower weight percents of Mn, regardless of annealing temperature. For example, at 425°C, both Compositions 2 and 6 have HB values ​​of about 90, while Compositions 3 and 4, which have lower weight percents of Mn, have HB values ​​of only about 60. Composition 7, which has a weight percent of Mn of 2.6 wt%, provides a higher HB value than the copper manganese alloys with lower weight percents.

[0033] The relationship with grain size is also shown in Figure 3. In this example, grain size was measured for each sample by measuring the average size of several individual grains according to American Standard ASTM E112. The limit for obtaining a grain size less than 1 μm is indicated by a dashed line; points above the dashed line have grain sizes less than 1 μm, and points below the dashed line have grain sizes equal to or greater than 1 μm. Thus, the dashed line represents the hardness limit (i.e., the minimum hardness that can be obtained for each alloy) for grains less than 1 μm at a particular annealing temperature. For example, Compositions 2 and 6 require higher annealing temperatures to reach the same grain size as compositions with lower weight percent Mn. However, Compositions 2 and 6 also have higher HB values ​​at the same grain size than compositions with lower weight percent Mn. For example, Composition 6 had an HB value of approximately 120 at a grain size less than 1 μm, while Compositions 1, 3, 4, and 5 only had HB values ​​of approximately 100-110 at the same grain size. Figure 3 also shows that the maximum achievable hardness of CuMn alloys with a high weight percent of manganese and a grain size less than 1 μm increases. For example, at 250°C, compositions 2 and 6 have HB values ​​in the range of 180-190, while compositions 1, 3, 4, and 5 have HB values ​​below 150.

[0034] Example 2: Effect of annealing temperature and treatment method The effect of annealing temperature was observed for three different processing methods. The control process included a standard forging and rolling (forging + rolling) process without ECAE. This control process was compared to 1) a four-pass ECAE and rolling (ECAE + rolling) process, and 2) a four-pass ECAE without rolling (ECAE) process. Annealing was completed after the standard forging + rolling, ECAE + rolling, and ECAE steps, respectively. A copper-manganese alloy with approximately 10 wt.% Mn was used for all processes. The results are shown in Figure 4.

[0035] Figure 4 shows that both the ECAE + rolling process and the ECAE process resulted in a finer grain structure and smaller recrystallized grain size than the forged + rolling process at all tested annealing temperatures. On average, Figure 4 shows that the forged + rolling process had a grain size 3 to 4 times larger than each of the processes with ECAE. For example, at 500°C, When annealed, the forged+rolled process had an average grain size of about 20 μm compared to an average grain size of about 7 μm for both the ECAE+rolled and ECAE processes.

[0036] Example 3: Effect of Annealing Temperature on Recrystallized Grain Size The effect of annealing temperature on grain size was observed for copper-manganese alloys processed by ECAE. Copper-manganese alloys with 10 wt.% manganese were processed by ECAE in four passes and then annealed at various temperatures. After annealing, the grain sizes of the alloy samples were compared using an optical microscope.

[0037] Figures 5A, 5B, 5C, and 5D show the resulting grain sizes. In Figure 5A, the sample was annealed to a temperature of about 425°C. As shown, the average grain size was about 1.8 μm to about 2.3 μm. In Figure 5B, the sample was annealed to a temperature of about 450°C, resulting in an average grain size of about 3.75 μm. In Figure 5C, the sample was annealed to a temperature of about 500°C, resulting in an average grain size of about 6.5 μm. In Figure 5D, the sample was annealed to about 550°C, resulting in an average grain size of about 12.1 μm. Thus, in this example, annealing at lower temperatures (i.e., about 425°C to about 450°C) resulted in a more refined crystalline structure with a lower average grain size, while annealing at higher temperatures (i.e., about 500°C to about 550°C) resulted in a significantly larger average grain size. Annealing at temperatures below 425°C resulted in submicron grain sizes.

[0038] Example 4: Effect of treatment method on strength The effect of processing method on strength was observed for two copper alloys. The Cu10Mn alloy was formed by combining copper with 10 wt. % manganese. This Cu10Mn alloy was processed via 1) standard forging and rolling, 2) ECAE, and 3) ECAE with rolling (ECAE + rolling). Copper alloy C18000 (a copper-based alloy containing chromium, nickel, and silicon) was also tested. Cu C18000 is one alloy currently used for backing plates in sputtering targets. The Cu C18000 material was tested 1) "as received" (i.e., without additional processing) and 2) after a hot isostatic pressing (HIP) process, in which high temperature and pressure were applied to the material. Yield strength and ultimate tensile strength were determined for all samples by performing standard tensile tests according to ASTM E8 standards. Circular tensile specimens having a gauge length of 5.08 cm (2 inches) and a diameter of 1.27 cm (0.5 inches) were cut from each material and tested at room temperature according to the standard procedures referenced above.

[0039] Figure 6 compares the yield strength and ultimate tensile strength of each of the above processing methods. The results for the Cu10Mn alloy show greater yield strength and ultimate tensile strength for the ECAE and ECAE + rolling processes. For example, the ECAE and ECAE + rolling samples had yield strengths of approximately 600 MPa and 630 MPa, respectively, which were approximately 4.5 times higher than the standard forging and rolling process, which had a yield strength of approximately 150 MPa. Similarly, the ECAE and ECAE + rolling processes had ultimate tensile strengths of approximately 620 MPa and 650 MPa, respectively, which were approximately two times higher than the standard forging and rolling process, which had an ultimate tensile strength of approximately 320 MPa.

[0040] Figure 6 also compares the Cu10Mn alloy with the C18000 material. The results show that the Cu10Mn alloy, when processed by either ECAE or ECAE + rolling, has higher yield strength and ultimate tensile strength than the C18000 material when tested both "as received" and after HIP.

[0041] Additionally, the resulting average grain size of the CuMn alloy after both the ECAE and ECAE + rolling processes was less than 1 μm, which contributes to a more refined microstructure. The average grain size of the CuMn alloy after standard forging and rolling was approximately 30 μm.

[0042] Example 5: Effect of composition on yield strength The effect of composition on yield strength was observed for various copper manganese alloy compositions and various other backing plate materials, and the materials tested are shown in Table 2 below.

[0043] [Table 2]

[0044] Sample 1 contained approximately 10 wt% Mn and was processed by standard forging and rolling. Samples 2-4 contained amounts of manganese commonly used in sputtering applications. Samples 2-4 contained approximately 0.43 wt%, 0.69 wt%, and 0.87 wt% Mn, respectively. Sample 5 also contained approximately 10 wt% Mn. Samples 2-5 were each processed by four-pass ECAE. Between each ECAE pass, Samples 2-4 were heated to a temperature of approximately 325°C to approximately 350°C. Sample 5 was subjected to a heat treatment process between ECAE passes. This process included heat treating at a temperature of approximately 400-450°C for at least 30 minutes, air cooling at ambient temperature to reach a temperature of approximately 350°C, and heat treating at a temperature of approximately 325-350°C for at least 30 minutes. This process was performed to limit stress and provide better surface quality for the samples. Samples 6-10 include a variety of backing plate materials commonly used in sputtering applications.

[0045] Figure 7 compares the yield strengths of the above materials. As shown, all materials processed with ECAE (i.e., Samples 2-5) produced, on average, higher yield strengths than materials not processed with ECAE. Sample 5 (ECAE Cu10Mn) exhibited the highest yield strength of all samples tested, more than four times higher than the yield strength of Sample 1. For example, Sample 5 had a yield strength of approximately 640 MPa, while Sample 1 only had a yield strength of approximately 140 MPa. Sample 5 also had a higher yield strength than all of Samples 6-10.

[0046] Example 6: Effect of Composition on Brinell Hardness The effect of composition on Brinell hardness (HB) was observed for various copper manganese alloy compositions and various other backing plate materials. The materials tested are shown in Table 3 below.

[0047] [Table 3]

[0048] Samples 1-4 contain approximately 0.43 wt%, 0.43 wt%, 0.87 wt%, and 1.7 wt% Mn, respectively. Samples 5-6 contain approximately 7 wt% and 10 wt% Mn, respectively. Sample 1 was processed by standard forging and rolling, resulting in a grain size of approximately 35 μm. Samples 2-6 were processed by ECAE, resulting in a grain size of less than 1 μm. Samples 7-11 comprise various backing plate materials commonly used in sputtering applications.

[0049] Figure 8 compares the Brinell hardness (HB) of the above materials. Again, most materials treated with ECAE (Samples 2-5) yielded higher HB values ​​than materials not treated with ECAE, with the exception of Sample 10 (high-strength aluminum) and Sample 11 (C18000). However, Samples 5-6, with weight percents of 7 wt% and 10 wt%, respectively, had higher HB values ​​than all other materials tested. For example, Sample 5 had an HB of approximately 180, Sample 6 had an HB of approximately 190, Sample 10 had an HB of approximately 130, and Sample 11 had an HB of approximately 160. Thus, a weight percent of manganese greater than approximately 2 wt% (i.e., between approximately 7 wt% and approximately 10 wt%) and treatment with ECAE yielded the highest Brinell hardness values.

[0050] Example 7: Effect of treatment method on secondary phase The effect of processing method on the size of secondary phases was observed. The secondary phases were detected by an automated procedure using integrated SEM / EDX and include manganese sulfate (MnS). The integrated SEM / EDX system used in this example is sold by FEI under the name Aspex Explorer and provides data reporting at magnifications up to 50,000x. The average diameter of secondary phases in a copper manganese alloy with approximately 10% manganese by weight (Cu10Mn) was detected in the "cast" material after forging and rolling, and after ECAE and rolling. The results are compared in Table 4 below. All diameters are in micrometers (μm).

[0051] [Table 4]

[0052] The average area of ​​secondary phases in the Cu10Mn material was also detected in the "out-cast" material after forging and rolling, and after ECAE and rolling. The results are compared in Table 5 below. All area measurements are in square micrometers (μm 2 )

[0053] [Table 5]

[0054] As shown in Tables 4 and 5 above, the Cu10Mn alloy subjected to ECAE exhibited smaller secondary phases compared to both the "cast" material and the forged and rolled material. On average, the secondary phases in the material subjected to ECAE had approximately three times smaller diameters and seven times smaller areas than the secondary phases in the "cast" material. Thus, processing the copper manganese alloy with ECAE resulted in a more refined secondary phase (MnS) with smaller diameters and / or areas than without ECAE.

[0055] Various modifications and variations may be made to the exemplary embodiments described without departing from the scope of the present invention. For example, while the embodiments described above refer to particular features, the scope of this invention also includes embodiments having different combinations of features and embodiments that do not include all of the described features. The present specification includes the following aspects of the invention. [1] 1. A method of forming a high strength copper alloy, comprising: heating a copper material containing manganese to a temperature above 400°C, the copper material containing about 2% to about 20% by weight of manganese; cooling the copper material to a temperature of about 325°C to about 350°C to form a cooled copper material; and extruding the cooled copper material by equal channel angular extrusion (ECAE) to form a cooled copper manganese alloy. [2] 10. The method of claim 1, wherein extruding the copper alloy comprises at least four passes of equal channel angular extrusion. [3] The method according to [1], wherein the high strength copper alloy has an average grain size of up to about 2 μm in diameter after heating to a temperature of about 400° C. to about 450° C. for at least 1 hour. [4] The method according to [1], wherein the high-strength copper alloy has an average grain size of about 12 μm to about 15 μm in diameter after heating to a temperature of about 500° C. to about 550° C. for at least 1 hour. [5] The method comprises: subjecting the cooled copper-manganese alloy to a first rolling step; heating the cooled copper manganese alloy to a temperature of about 400°C to about 575°C for at least 0.5 hours to form a heated copper manganese alloy; 10. The method of claim 1, further comprising subjecting the heated copper manganese alloy to a second rolling step to form a hardened copper manganese alloy. [6] The method according to [5], wherein the hardened copper manganese alloy has an average grain size of about 1.5 μm to about 15 μm in diameter. [7] 1. A sputtering assembly comprising a sputtering target, 1. A sputtering assembly comprising a copper alloy having a copper base and containing manganese, the manganese being present in a weight percent of about 2 wt. % to about 20 wt. % by weight of the copper alloy, the sputtering target having a substantially refined secondary phase, such that the secondary phase has an average diameter at least about 1.5 times smaller than the average diameter obtained by conventional thermomechanical processing methods. [8] The sputtering assembly according to [7], wherein the copper alloy contains about 3% to about 12% by weight of manganese. [9] [7] The sputtering assembly of [7], wherein the copper alloy has an average grain size of up to about 15 μm in diameter.

[10] The sputtering assembly according to [7], wherein the copper alloy has an average yield strength of about 475 MPa to about 700 MPa.

Claims

1. 1. A sputtering assembly comprising a sputtering target made of a copper alloy having a weight percent of manganese between 2% and 20% by weight, the balance being copper and unavoidable impurities, A sputtering assembly, wherein the copper alloy is processed by equal channel angular extrusion (ECAE) to have a Brinell hardness of 155 HB to 200 HB and an average yield strength of 475 MPa to 700 MPa.

2. The sputtering assembly of claim 1, wherein the copper alloy has an average grain size of 0.2 μm to 15 μm in diameter.

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