CN1681960A - 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

The method of copper sputtering target and formation copper sputtering target

Technical field

The present invention relates to copper bearing monolithic sputtering target and the copper bearing sputtering target that is connected.The invention still further relates to and form copper bearing monolithic and the method that is connected sputtering target.

Background of invention

At present, in the many application that comprise in for example unicircuit is manufactured on, use high purity copper sputtering targets and copper alloy sputtering target.Contain steel structure depends on target as the quality of interconnection (interconnect) and film sputtering performance.Many factors of sputtering target can influence the sputtering performance of target, and these factors comprise: your homogeneity of the median size of target and particle diameter; Crystalline orientation/the texture of target; The homogeneity of target inner structure and composition and the intensity of target.Typically, less median size is relevant with the high strength of material.In addition, the amount of alloying can influence the intensity and the hardness of target, and the alloying that is typically raising causes target strength to increase.

Because the intensity of high purity copper (greater than 99.99 weight % copper) is low, so typically, the high purity copper sputtering targets of routine is made for the connection target.Connect copper sputtering target and have the high purity copper target that connects with the supporting plate that contains relative high-strength material such as aluminium.Yet, usually causing unusual grain growth at the high temperature that will use in copper target and the process that supporting plate is connected, this causes the inhomogeneous and total median size of microstructure to increase.Typically, conventional high purity copper target has the median size greater than 50 microns, and this can cause low relatively yield strength.The particle diameter and the structural inhomogeneity that obtain in the conventional high purity copper sputtering targets that forms can influence the high-purity copper film of sputtering sedimentation and the quality of interconnector nocuously.

Big particle diameter that in connection procedure, produces except meeting and the unusual grain growing, make troubles such as burning the copper target of also usually being connected for diffusion with the short such problem of target lifetime.In addition, connection procedure is complicated and time-consuming.

A kind of sputtering target that increases is to make copper become alloy with one or more " alloying " elements with the particle size uniformity of copper product and the method that improves its intensity.Yet,, be restricted to and be not more than 10 weight % so it is desirable to total amount with alloy element in the target because the existence of alloy element influences the resistivity of copper.For specific application such as copper film and interconnector, wherein need the resistivity that can compare with high purity copper resistivity, the amount of alloying should be restricted to and be less than or equal to 3 weight %.Another shortcoming of alloying is that the potential defective is as forming second phase precipitate or the segregation.

Although handle conventional material to reduce or to remove precipitate or the segregation defective is being possible in some cases, typically, this processing comprises the high temperature that can cause extremely big particle diameter (greater than 150 microns).Perhaps, conventional rolling and/or forging method can obtain to be present in the second phase precipitate in the conventional material or the part of segregation defective reduces using in some cases.Yet remaining defective still can influence the quality of sputtered film.At present, form the conventional processing that alloy element is less than or equal to the copper alloy of 3 weight % and cause target typically to have,, and the second phase precipitate is arranged wherein usually greater than 50 microns median size greater than 30 microns.

It is desirable to develop make and have the copper sputtering target that improves sputtering performance and the method for copper alloy sputtering target.

Summary of the invention

On the one hand, the present invention includes a kind of copper bearing sputtering target.This target contains at least 99.99 weight % copper, and median size is the 1-50 micron.The yield strength of this cupric target is more than or equal to about 15ksi, and Brinell hardness (HB) is greater than about 40.

On the one hand, the present invention includes a kind of copper alloy sputtering target, this sputtering target is formed by being less than or equal to about 99.99 weight % copper and at least a alloy element that is selected from the following element substantially: 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, Si, Mo, Pt, Nb, Re and Hf.The total amount of this palladium alloy element is at least 100ppm, but is less than 10 weight %.This target also have the median size of 1-50 micron and in entire target 1-σ standard deviation less than about 15% particle size uniformity.

In one aspect, the present invention includes a kind of method that forms the monolithic sputtering target.Be heated to temperature with substantially being less than or equal to copper base that one or more alloy elements of 10 weight % form at least about 900 by copper and total amount, and under this temperature maintenance at least about 45 minutes.This copper base of heat forged is about 50% to highly dropping to less, forges piece thereby form, cold rolling this piece to reduction at least about 60%, thereby form slab.Heating this slab distributes less than about 100 microns close grain to bring out recrystallize and to form median size.Subsequently this slab is configured as the monolithic target shape.

On the one hand, the present invention includes a kind of method that is at least the copper base formation copper-comprising sputtering target of 99.99% bronze medal with purity.Be higher than this base of forge hot under 300 ℃ of temperature, making highly to descend at least 40%, forging piece thereby form.This forging piece of shrend also carries out extrusion process to forging piece, and this processing comprises making forges piece by equal channel angular extruding (ECAE) at least 4 times.After forging, can select to carry out solutionizing and handle, follow by shrend and ECAE.Between at least some ECAE times, carry out process annealing, and cold rolling this piece reduces less than 90% extremely after ECAE finishes dealing with, thereby form slab.But this slab of thermal treatment is configured as sputtering target subsequently.

The accompanying drawing summary

With reference to following accompanying drawing the preferred embodiment of the invention is described below.

Fig. 1 is the schema of describing according to the working method general survey of one aspect of the invention.

Fig. 2 has illustrated at the square billet during the initial manufacture step according to the present invention.

Fig. 3 is the schematic sectional view of the material just handled with equal channel angular extrusion device.

Fig. 4 has illustrated that the various copper and copper alloy that adopt the equal channel angular extrusion process are 40 microns standard 6N copper and with respect to yield strength and the ultimate tensile strength of various supporting plates with respect to particle diameter.

Fig. 5 is after also annealing 5 hours under 250 ℃ subsequently according to the equal channel angular extruding of one aspect of the invention, the size distribution of 99.9999% copper product (6N) and the imaging EBSD/SEM of texture figure.

Fig. 6 has illustrated that the chip area of the material of imaging in Fig. 5 distributes.The median size of this material is about 6 microns.

Fig. 7 has illustrated when measuring by EBSD and optical microscopy, the median size relevant with anneal that obtains.The copper product that contains with the copper of 0.53 weight %Mg alloying has been carried out anneal, and this copper product has stood 6 times equal channel angulars extruding by passage D.

Fig. 8 has illustrated that annealing is after 2 hours down at 300 ℃, and the EBSD/SEM of Cu-0.53wt%MgECAE material schemes among Fig. 7.

Fig. 9 is that annealing is after 1.5 hours down at 450 ℃, and the EBSD/SEM of the crystalline-granular texture of Cu-0.53wt%Mg material schemes among Fig. 7.

Figure 10 has illustrated the picture of Fig. 9 material that adopts the optical microscopy acquisition.

Figure 11 describes according to the particle diameter of the target of one aspect of the invention and the figure of texture measurement sampling.

DESCRIPTION OF THE PREFERRED

The present invention includes monolithic high purity copper sputtering targets, connection high purity copper sputtering targets, monolithic copper alloy sputtering target, connection copper alloy sputtering target and make the method for these targets.Concerning this specification sheets, high purity copper refers to copper or the copper product with at least 99.99 weight % copper.The present invention includes and have high-purity target of 99.99%-99.99995 weight % copper at least.In addition, use term " monolithic " to refer to not to be connected and be used for the target of sputter with supporting plate.

Have less than 1 micron to being less than or equal to about 100 microns, preferably less than 50 microns median size according to connection of the present invention or the high-purity target of monolithic.In some cases, can use method of the present invention to make median size and be 1-about 30 microns monolithic or connection target.Under specific situation, according to the monolithic of high purity copper of the present invention be connected target and preferably have about 20 microns of 1-, the about 10 microns median size of for example about 5-.

High-purity target of the present invention is along having particle size uniformity in the sputtering surface of target and/or the entire target, and the homogeneity of this particle diameter is to be less than or equal to about 15% standard deviation (1-σ) (being also referred to as less than 15% ununiformity).Under specific situation, homogeneity can show as and be less than or equal to 10% standard deviation (1-σ).

The yield strength ratio median size that high purity copper sputtering targets of the present invention has is 50 microns, has basic identical elementary composition target height at least about 10%, in some cases, be 30 microns, have basic identical elementary composition target height than median size at least about 10%.Concerning this specification sheets, phrase " basic identical elementary composition " refer to do not have can detected composition difference material.Typically, give the yield strength of target more than or equal to about 15ksi by method as described below.

The ultimate tensile strength that high purity copper sputtering targets of the present invention has is 50 microns, has basic identical elementary composition target height at least about 15% than median size, in some cases, this ultimate tensile strength is 30 microns, has basic identical elementary composition target greatly at least about 15% than median size.In addition, the hardness ratio median size of this high purity copper target is 30 microns, has a basic identical elementary composition target height at least 15%.Under specific situation, the Brinell hardness of the high-purity target of the present invention is greater than about 40HB, under specific situation, greater than about 60HB.

In aspect specific, high purity copper sputtering targets of the present invention has 99.99% (4N) or higher purity.Concerning this specification sheets, unless specify in addition, all per-cents and the amount that comprises are all by weight.In certain aspects, this high-purity target can preferably comprise 99.999% (5N) copper, can preferably comprise 99.9999% (6N) copper or can preferably comprise 99.99995% (6N5) copper.

Connection high purity copper target of the present invention comprises the high purity copper target that is connected with the supporting plate diffusion.Under specific situation, this diffusion that connects target connects yield strength greater than 10ksi, is preferably greater than or equals about 15ksi, and under special situation, diffusion connection yield strength is more than or equal to about 30ksi.Perhaps, can adopt another kind of method of attachment that target is connected with supporting plate, for example, comprise etc. that static pressure, rolling coating, welding, blast connect and do not have friction one or more in forging.Preferably, another kind of method of attachment can be connected the high purity copper target to produce the connection of yield strength more than or equal to about 10ksi with supporting plate.

The present invention connects the supporting plate that uses in the target and is preferably aluminium or CuCr supporting plate.As what understand, also can use other supporting plate material as one sees fit for those of ordinary skills.

The present invention includes and contain the copper alloy sputtering target that is less than or equal to about 99.99 weight % copper.Preferably, copper alloy sputtering target of the present invention is formed by being less than or equal to about 99.99 weight % copper and at least a alloy element that is selected from the following element substantially: 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, Si, Pt, Nb, Re, Mo and Hf.Under specific situation, this at least a alloy element is preferably selected from Ag, Al, In, Zn, B, Ga, Mg, Sn, Ge, Ti and Zr.The total amount of at least a alloy element of this that exists in the target is preferably at least about 100ppm weight-less than about 10 weight %.In some cases, this at least a alloy element is preferably so that 1000ppm weight-less than about 3 weight %, the amount that is more preferably less than about 2 weight % exists at least.

In aspect specific, according to the median size of copper alloy sputtering target of the present invention less than 1 micron.Perhaps, the median size of copper alloy sputtering target is about 100 microns of 1-, preferably less than 50 microns.In certain aspects, the particle diameter of copper alloy target is preferably the 1-30 micron.In some cases, use method of the present invention and target is had be less than or equal to 20 microns median size, and in aspect specific, be about 10 microns of about 5-.In addition, copper alloy target of the present invention has particle size uniformity in entire target and/or along the sputtering surface of target.In aspect specific, median size in the entire target has particle diameter ununiformity less than 15% (with respect to standard deviation (1-σ), be less than or equal to about 15% particle diameter), under specific situation, have and be less than or equal to about 10% standard deviation (1-σ) (being less than or equal to 10% ununiformity).

Copper alloy sputtering target of the present invention has the Brinell hardness at least about 40HB.In some cases, target of the present invention has the hardness more than or equal to about 60HB.In addition, this copper alloy target has uniformity of hardness along sputtering surface and/or in entire target.For example, under specific situation, the hardness in the whole copper alloy target has the standard deviation (1-σ) (in other words, this target has the ununiformity less than 5%) less than about 5%.Under specific situation, uniformity of hardness has the standard deviation (1-σ) less than about 3.5%.

Copper alloy target of the present invention can be a monolithic, or in another embodiment, can connect.Can connection copper alloy target of the present invention be connected with supporting plate by one or more the method that diffusion connects or connects, do not have in the forging of rubbing and other suitable linking method by static pressure such as applications, rolling coating, welding, blast.Under the situation that connects the copper alloy target, this connection has greater than about 10ksi, is preferably greater than the connection yield strength of about 15ksi.

The copper product of handling according to the inventive method can be made texture, and to extremely strong copper target, this depends on the operational path (following argumentation) of use from extremely weak (approaching at random).Concerning this specification sheets, term " copper " (as using in term " copper target ", " copper product ", " the copper base " etc.) general reference high purity copper or copper alloy.The exemplary copper target that the present invention has weak texture has and is less than or equal to about 15 times (times) unordered grain orientation distribution function (ODF).Under specific situation, this target has extremely weak texture, be characterised in that ODF less than about 5 times unordered.

This copper target can comprise main grain orientation, and wherein term " mainly " refers to the grain orientation that exists in this target, Duo than any single other grain orientation.It is to be noted that term " mainly " needn't mean that most of particle all is orientated with this and exist.On the contrary, term " mainly " means do not have more another single orientation in target.In aspect specific, can use method manufacturing of the present invention to have the main grain-oriented target of non-(220).

Another kind of processing according to the present invention can be made the copper target with less texture at random.The present invention includes the processing that can bring out strong-texture in the brass work of making, wherein term " strong-texture " refers to ODF above about 15 materials at random.In addition, target of the present invention can have extremely strong texture, is characterised in that ODF surpasses 20 times at random.Under specific situation, target of the present invention preferably has the main grain orientation of non-(220).

Adopt the size of the copper target of the inventive method manufacturing to be not limited to particular value.In addition, target can be made many shapes, for example circular or orthogonal.Owing to the intensity of the material of making by described method with respect to the material of ordinary method manufacturing increases, so can make the big copper target of making than by ordinary method of copper target size.As mentioned above, the copper target with routine is connected with supporting plate so that enough intensity to be provided.The high strength of material of the present invention is useful especially, because the intensity that increases can reduce or prevent the distortion of target in the process of manufacturing and/or sputtering technology.This method makes can use monolithic (disconnected) copper target, and bigger target size can be used to connect target and monolithic target.Can make connection of the present invention or monolithic target and be used for many sputter applications, include but not limited to 200 millimeters processing of wafers and 300 millimeters processing of wafers.

Although specifically described target of the present invention and method with reference to copper and copper alloy, it being understood that to the present invention includes other material, comprise high pure metal and alloy material.It is useful especially that described method is used for following other exemplary material, and these materials comprise aluminium, aluminium alloy, titanium, titanium alloy, tantalum, tantalum alloy, nickel, nickelalloy, molybdenum, molybdenum alloy, gold, au-alloy, silver, silver alloys, platinum and platinum alloy.The alloy of enumerating preferably comprises and is less than or equal to 10 weight % alloy elements.As what understand for those of ordinary skills, the temperature of the method for describing with respect to copper product and other value can be adjusted the specific composition that is used based on this method below.

With reference to figure 1 method of the present invention is described briefly.In an exemplary processing scheme 10, in initial manufacture step 100, provide pending to form the material of sputtering target.Can provide original material with the form of the exemplary base 12 described among base such as Fig. 2.With reference to figure 2, base 12 comprises bottom surface 14, end face 16, and comprises the thickness of material between bottom surface 14 and the end face 16, is designated as T ₁Base 12 can be square or rectangular shape as shown in Figure 2, perhaps can comprise cylindrical or other shape (not shown).Base 12 preferably includes cast material, although also can be other base material.In the embodiment of the high-purity target of needs, base 12 is particularly preferred for cast material, because cast material can provide with very pure form.Typically the composition of the composition of the target of the inventive method manufacturing and base is basic identical; Wherein basic identical refer to that material do not have can detected composition difference.

The texture of base 12 materials can influence the texture of goods constructed in accordance and/or obtain the difficulty of the required final texture of these goods.Therefore, can provide and have the base 12 that helps the initial texture of required texture in the manufactured copper target.Need in end article under the situation of strong-texture, useful providing has the base 12 of strong-texture.Yet, it is to be noted, can adopt the another kind of method among the present invention, make weak or extremely weak texture with base with strong-texture.In addition, can the method according to this invention handle that the base with weak texture has by force with manufacturing or the target of strong-texture extremely.Can handle and have specific base main or the principal crystal grain orientation and have identical or different main or principal crystal grain orientation, or not have the target of single principal crystal grain orientation with manufacturing.

In aspect specific, base 12 comprises the high purity copper material with at least 99.99 weight % copper.In specific application, base 12 is that 99.99% (4N), purity are that 99.999% (5N), purity are that 99.9999% (6N) or purity surpass 6N by purity basically, and for example the copper of 99.99995 weight % is formed.The present invention comprises that also base 12 contains the method for another kind of high pure metal such as aluminium, gold and silver, titanium, tantalum, nickel, platinum or molybdenum.

Perhaps, base 12 comprises and is less than 99.99% bronze medal or is less than other aforesaid metal of 99.99%.For convenience of explanation, after this base 12 is called the copper base,, the present invention includes other metal and their alloy although should be appreciated that.In aspect more of the present invention, copper base 12 preferably is made up of copper that is less than 99.99 weight % and at least a alloy element that is selected from the following element substantially: 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, Si, Pt, Nb, Re, Mo and Hf.The total amount of copper base interalloy element is preferably at least 100ppm weight-be less than or equals about 10 weight %.In aspect specific, the copper base preferably contains the alloy element that 1000ppm-at least is less than or equals about 3 weight %, more preferably less than or equal the alloy element of about 2 weight %.In specific embodiment, alloy element preferably includes one or more among Ag, Al, In, Zn, B, Ga, Mg, Sn, Ge, Ti and the Zr.

With reference to figure 1, the copper base that provides in the step 100 is subjected to pre-treatment 200 again.Pre-treatment 200 comprises at least a in homogenizing, solutionizing and the forge hot.Just as one of ordinary skill understood, the suitable temp that carries out solutionizing, homogenizing or forge hot depends on the concrete composition of base 12.In aspect specific, the present invention is preferably included in the process of pre-treatment 200 and carries out forge hot, forges piece thereby form.Carry out the forge hot of copper base 12 under at least about 300 ℃ temperature, preferably under at least about 500 ℃ temperature, carry out.Preferably, forge hot is with the original depth (T among Fig. 2 of base 12 ₁) reduce at least about 40%, and under specific situation, preferably at least about 50%.

In pretreated process, forge hot is optional to be positioned at after the additional heat treatment that comprises solutionizing and/or homogenizing copper product or before.Heat-treat under the temperature that solutionizing and/or homogenizing are occurred in processed specific composition being enough to.This solutionizing/homogenization temperature preferably keeps being enough to make the time of the solutionizing/homogenizing maximum of composition.It is to be noted that the temperature that is enough to solutionizing or homogenizing can cause grain growing, produce particle diameter and surpass less than about 100 microns required scopes.Therefore, attempting to obtain ordinary method than small particle size, to be easy to make solutionizing or homogenizing to handle minimum.Yet particle diameter reduced after method of the present invention can make homogenizing/solutionizing, thereby obtained the benefit of solutionizing/homogenizing processing and small particle size simultaneously.Useful is solutionizing and/or homogenizing in the process of pre-treatment step 200, thereby makes any precipitate and/or particle dissolving that is present in the copper base.Homogenizing also reduces or eliminates chemical segregation in the base 12.

Pretreatment technology of the present invention is not limited to the particular order that homogenizing, solutionizing and/or forge hot are handled.In aspect specific, pre-treatment 200 comprises homogenizing copper base, then forge hot, solutionizing subsequently.After solutionizing, carry out forge hot in other cases.Below set forth exemplary preferred pretreatment in the mode of the exemplary preferred embodiment of the present invention.

Carry out in the process of pre-treatment 200 under the certain situation of forge hot, pre-treatment comprises in addition follows, and preferably follows the quenching of forge hot immediately.Although can use other method of quenching, preferably adopt shrend.

In specific embodiment, forge hot can comprise initial heating, and can carry out one or many reheat situation subsequently.The height decline that produces in each forging situation between initial heating and each reheat subsequently can change, and this depends on such as the such factor of the forging temperature of specific composition and use.Preferably, the quenching of just carrying out later at final reheat.Exemplary reheat is included in after the initial forge hot, and one or many will be forged piece reheat to 1400 °F at least about 10 minutes.

Except that above-mentioned technology, pre-treatment 200 randomly comprises ageing treatment.Comprise in pre-treatment and preferably before timeliness, base 12 is processed into the forging piece under the situation of timeliness.More preferably, timeliness is embodied as finally processing in the pretreatment stage.Under specific situation, Use Limitation brings out the tiny precipitate of formation in copper material.This precipitate that brings out has less than about 0.5 micron mean diameter.In specific application, useful is to bring out precipitate by timeliness, because this precipitate can impel the development of tiny and even grained in the process of following process, and can make the crystalline-granular texture of such manufacturing stable.

Subsequently, the piece of forge hot that forms in pre-treatment 200 and/or solutionizing stands another kind processing as shown in Figure 1.In one aspect, the piece of this processing stands equal channel angular extruding (ECAE) processing 310, thereby forms the target work in-process.With reference to figure 3, it has illustrated exemplary ECAE equipment 20.Equipment 20 comprises the die assembly 22 that limits pair of intersecting passage 24 and 26.Intersecting passage 24 is identical or essentially identical at least with 26 cross section, and it is identical within the acceptable tolerance of ECAE device that term " essentially identical " refers to passage.In the operation, base 28 (can be above-mentioned forging piece) is by passage 24 and 26 extruding.Thisly be pressed through pure shear and successively cause base being arranged in the thin zone viscous deformation at channel cross-section place.Although preferably passage 24 and 26 is with about 90 ° angle of intersection, it being understood that and to use another kind of tool angle (not shown).About 90 ° tool angle (passage intersects angle) is preferred, because can obtain best deformation (real shear strain).

ECAE can introduce serious viscous deformation and forge in the block of material, simultaneously the maintainance block size constancy.For bring out violent strain in metallic substance, ECAE is a preferable methods, because can use ECAE to introduce very consistent under low load and pressure and uniform strain.In addition, every time ECAE can obtain high distortion (true strain ε=1.17); Can obtain high accumulation strain (N=4 all over time, ε=4.64) by ECAE equipment multipass; And by use different distortion approach (that is, by change by ECAE equipment all between the direction of forging piece) can be used for the various texture/microstructures of formation in material.

In an exemplary method of the present invention, be enough at the copper base or forge the strain rate that obtains required microstructure (for example Ruo texture and little particle diameter) in the piece and in whole base, produce uniform stress-state of strain and processing temperature under carry out ECAE.Make copper product by ECAE device some times with multiple route with under cold working that is equivalent to material or hot worked temperature.Use is " route D " by the preferred routes of ECAE device 20 multipass, this be equivalent to subsequently each all over before 90 ° of constant rotation bases.Because the ECAE route can influence the structural approach that produces in the process of dynamic recrystallization, so select one or more specific routes to be used for being out of shape all over to bring out required orientation in material processed.

In specific application, the forging piece of processing experiences 4 times ECAE at least in technology 310 in step 200.Typically, ECAE technology 310 comprises 4-8 time, preferably includes 4-6 time.Owing to bring out dynamic recrystallization with mechanical means, so find that usually it is submicron-scale (wherein, submicron refers to the median size less than 1 micron) that this exemplary pass is enough to impel grain refining.

Typically, 1-3 time ECAE forms defective (little band separately continuously; Shear zone, dislocation array etc.).In these processes of initial several times, can the development of heat reset generation born of the same parents and subgrain, and cause the crystal boundary misorientation.Before ECAE, the intensity that the texture intensity of material influence produces in 3 times process, typically, and with respect to material with weak initial texture, the randomization that after more pass, becomes of strong initial texture.Subsequently several times (the 4th times and any more time) increase the submicron particle diameter that forms dynamic recrystallization by bringing out high angle number of boundary purpose.In the process of dynamic recrystallization, the new crystal grain that forms obtains more weak texture and becomes more approaching to wait spool gradually.

In some applications, in ECAE time process, can use the mould of heating ECAE device to heat base 28.Preferably, mold heated to being lower than the minimum temperature (perhaps, being called minimum recrystallization temperature) that processed copper product produces static recrystallize, more preferably is heated to about 350 ℃ of about 125-.

In the process of ECAE processing 310, randomly, between some or all of ECAE time, carry out process annealing.Can below the beginning temperature of static recrystallize, static recrystallize begin under the temperature (being defined as the minimum temperature that begins to bring out processed material recrystallize) or near or forming in the temperature range of complete static recrystallize and carrying out process annealing.Carry out the size and the orientation of the temperature effect crystal grain of process annealing, and therefore be used in the required texture of promotion under the given situation.

In ECAE time process subsequently, make texture that reduction take place to increase in the process annealing of carrying out under the temperature that produces complete static recrystallize.Annealing can produce answers (stress relief) under the temperature that static recrystallize begins temperature being lower than, and answer also can cause texture intensity and orientation to change.When carrying out inferior Tc annealing between one time in 4 times or the multipass, can make reorientation effect maximum, when the 4th time after time between when carrying out, this effect becomes more not obvious.Carrying out process annealing under the beginning temperature of static recrystallize causes texture (intensity and/or orientation) and some recrystallize all to change.Repeating process annealing between continuous time has the effect of raising than the independent annealing case effect of describing.

In application-specific of the present invention, preferably carry out any process annealing being lower than under the temperature and time that causes the static recrystallize of machined material.Useful is carries out process annealing under the temperature that can bring out static recrystallize so that the uniform microstructure minimum of skin breakage and raising being lower than.Contain under the situation of high purity copper at the forging piece that is subjected to ECAE, preferably under the about 225 ℃ temperature of about 125-, carry out process annealing above about 1 hour.This produces ECAE processing 310 to have extremely evenly and small particle size, for example average from the submicron particle diameter to about 20 microns high purity copper material.

In aspect of the present invention, under the situation of forging the block of material copper-bearing alloy, process the inferior Tc process annealing of carrying out in 310 processes at ECAE and preferably include the about 325 ℃ temperature of about 150-, preferably kept this temperature at least 1 hour.This inferior recrystallization temperature anneal produces median size and is lower than 1 micron Cu alloy material.

High purity copper and Cu alloy material by the manufacturing of above-mentioned ECAE method have the hardness of raising with respect to the material by the conventional treatment method manufacturing.Shown in the table 1 with respect to respective material before ECAE, according to the 6N copper of the inventive method processing and the generation hardness of each Albatra metal-.It is 40 microns 6N copper and various supporting plate material that Fig. 4 has compared with respect to particle diameter, according to the high purity copper of the inventive method processing and the yield strength and the ultimate tensile strength of each Albatra metal-.

Table 1:ECAE handles the effect to material particle size and hardness

Material (particle diameter 30-50 micron) before the ECAE	Hardness (Vickers)	Median size behind the ECAE	Hardness behind the ECAE (Vickers)	Hardness increases
					6N copper	??48.44HV	5 microns	??72.2HV	?49％
??6N?Cu+0.8％Ag	??73.02HV	4 microns	??89.88HV	?23％
					??6N?Cu+0.8％Ag	??73.02HV	0.35 micron	??172.4HV	?136％
??6N?Cu+0.5％Sn	??75HV	4 microns	??104.56HV	?39.4％
					??6N?Cu+0.5％Sn	??75HV	0.35 micron	??182HV	?142％

As shown in Figure 1, after pre-treatment 200, copper product stands to comprise the another kind of operational path of rolling technology, thereby makes the target work in-process.Rolling processing 330 preferably includes the forging piece that pre-treatment 220 is made and carries out cold rollingly, makes total reduction be at least 60%, preferred 60-85%.Be preferably greater than 8 roads cold rolling comprising greater than 4 roads, more preferably the 8-16 road.In the whole operation of rolling, preferably, each road in initial 4 roads is used for the thickness of piece is reduced about 5%-about 6%.In addition, the rolling thickness decline about 10-about 20% that makes separately in preferably final 4 roads.Relatively little draught in the initial 4 road processes can alleviate or prevent the crackle in the rolling technology process.Rollingly can in cold rolling high purity copper that obtains or Cu alloy material, produce little particle diameter.

As shown in Figure 1, operational path above replacing can carry out operational path 320.The combination that route 320 is used cold rolling and equal channel angular extrusion technique.Under the situation of using another processing route 320, preferably the forge hot piece that pre-treatment 200 is made carries out ECAE and cold-rolling treatment subsequently.Yet, it being understood that invention attempts carrying out cold rolling before the ECAE or before ECAE and all carry out cold rolling afterwards.

The ECAE of process 320 partly comprises above-mentioned ECAE working method.Subsequently, the material of cold rolling ECAE extruding to draught less than about 90%, thereby form work in-process.Under specific situation, the cold rolling part of route 320 preferably produces the draught at least about 60%.The cold rolling processing of ECAE extruded material comprises the rolling process with respect to the operation of rolling 330.In aspect specific, route 320 combination rolling with forge to produce at least 60% but less than total decline of 90%.Perhaps, can be in the decline that does not have to use forging processing to produce required 60-90% under the rolling situation.

Useful is with ECAE and the rolling and/or forging process of combination subsequently, because this processing can be brought out required grain orientation in copper product.The orientation of bringing out comprises main grain orientation or comprises the principal crystal grain orientation.Use rolling and/or forge in brass work of the present invention and form by force or extremely strong texture.In certain aspects, by rolling behind the ECAE/to forge the strong-texture form can not be (220) texture.

As shown in Figure 1, the cupric that obtains or the work in-process of Cu alloy material stand final target and form processing 500, and choose wantonly before final target forms 500 and standing additional heat treatment 400.Optional thermal treatment process 400 is included in to be lower than to bring out under the temperature and time that static recrystallize begins carries out anneal.Below the minimum temperature of static recrystallize, carry out low-temperature annealing, be also referred to as recovery annealing.For keeping extremely little particle diameter, recovery annealing or optional unannealed be useful.This low-temperature annealing or unannealed generation median size are less than about 1 micron work in-process.

Perhaps, these work in-process stand to equal or exceed the minimum temperature for some time of bringing out recrystallize, and this time is enough to form final size-grade distribution in work in-process.Although static recrystallize can increase particle diameter, can make this increase minimum to produce required recrystallize amount (partially or completely recrystallize) by the time that is annealed to the minimum temperature minimum that approaches recrystallize.For copper alloy, preferably under about 500 ℃ of about 350-, carried out the about 1-of recrystallization annealing about 8 hours.For high purity copper, preferably under about 300 ℃ of about 225-, carried out the about 1-of recrystallization annealing about 4 hours.

Fig. 5 and 6 explanation the method according to this invention are used ECAE and the median size that produced in 5 hours of annealing under 250 ℃ subsequently is the particle diameter and the distribution of about 6 microns 6N copper.Fig. 7 illustrated for before annealing pass course D stand the copper alloy of 6 times ECAE with 0.53%Mg, the particle diameter relevant with anneal develops.Fig. 8 illustrated in annealing under 300 ℃ after 2 hours, the particle diameter and the distribution of copper among Fig. 7/0.53%Mg alloy.Fig. 9 and 10 has illustrated that annealing is after 1.5 hours down at 450 ℃, and the particle diameter and the distribution of copper among Fig. 7/0.53%Mg alloy use EBSD/SEM (Fig. 9) and optical microscopy (Figure 10) to analyze.

It is to be noted that the work in-process of making are not having under the situation of heat treatment stages 400 or stand the ageing treatment (not shown) after thermal treatment 400 in optional step 310,320 or 330.In use under the situation of Xiaoing, preferably carry out timeliness under about 500 ℃ temperature being lower than.As what point out above, useful is to carry out the timeliness step to improve copper or the half-finished intensity of copper alloy by bringing out average precipitate size less than about 0.5 micron tiny precipitate.

High purity copper or copper alloy work in-process by the inventive method manufacturing stand final target shaping 500, connect target (wherein, " connection target " refers to the sputtering target that is connected with upholder such as supporting plate) thereby make monolithic target or make.

Handling the final target that forms in 500 is under the situation of monolithic target, and final target is shaped and comprises that for example, thereby these work in-process of machining form required target shape.To be used for by the target of the inventive method manufacturing under the situation of semiconductor wafer processing, final forming step 500 comprises making to have and is suitable for the target handling the 200mm wafer or be suitable for handling the size of 300mm wafer.For example, be used to handle the exemplary monolithic copper of the present invention of 200mm semiconductor wafer or the sputtering surface diameter of copper or copper alloy target is 13.7 inches, apparent surface (back side) diameter is 16.6 inches, and thickness is about 0.89 inch.The sputtering surface diameter that is used to handle the respective target of 300 millimeters wafers is 17.5 inches, and back side diameter is 20.7 inches, and thickness is about 1.0 inches.The monolithic target that the inventive method forms is flat plate target preferably, although also comprise other target shape and other size.

In order to make the target strength maximum, preferably have according to the monolithic target of the inventive method manufacturing and to be less than or equal to about 50 microns particle diameter.Having yield strength, ultimate tensile strength (UTS) and hardness ratio that the monolithic target of the present invention of submicron particle diameter has, to have basic identical composition, median size be that 30 microns target is greatly at least about 50%.Median size constructed in accordance is that 1-improves at least 10% less than the conventional copper target of strength ratio that about 20 microns monolithic copper target has.For extremely big monolithic target or in the application of the maximum target strength of needs, preferably under the condition that does not have heat treatment step 400, make monolithic target.Therefore, the monolithic target that obtains can remain on the little particle diameter that produces in the previous processed.For example, under the situation of using rolling and/or ECAE generation submicron particle diameter, the submicron particle diameter can be remained in the final monolithic target, thereby make the target strength maximum.In one aspect of the method, use heat treatment step 400 to make such monolithic target in the process of handling, it is about 20 microns of about 1-that the final size distribution that this target can produce in the monolithic target that obtains can make median size.

The target of making in step 500 is to connect under the situation of target, and except any machining of carrying out in order to form required target shape, target forms and also comprises Connection Step.Connect technology and comprise that the work in-process that will be formed by above-mentioned working method are connected with upholder such as supporting plate.For example, exemplary supporting plate comprises aluminium and/or copper.Exemplary supporting plate material is CuCr, Al 2024 and Al 6061 T4.Connect technology comprise wait static pressure (hipping), rolling, coat, welding, blast connect, do not have that friction is forged, in the diffusion bonding one or more or be other method known to those of ordinary skills.This connection produces the connection that yield strength is at least about 10ksi.Under specific situation, this connects the strength of joint that produces more than or equal to about 15ksi, and in application-specific, produces the strength of joint that equals or exceeds 30ksi.

Can use above-mentioned various working method manufacturing to have the brass work of extremely even and little particle diameter.Usually, the particle diameter of generation on average from sub-micron grain near.Because can use the high temperature method of attachment, so this little particle diameter makes it possible to obtain very high strength of joint.Making under the situation that connects target, heating (thermal treatment 400) and target can formed and combine being connected in the technology.

Preferably be less than or equal to about 325 ℃ temperature, be less than or equal to carry out under about 4 hours time connection, so that grain growth minimum in the target according to the high purity copper target of the inventive method.Although some grain growings can occur in high temperature binding process, initial ultrafine particle diameter makes and some grain growings to occur and do not cause observed greater particle size in using the target that conventional treatment method forms.The present invention who obtains finally connects the particle diameter that 1-is about 20 microns in the target makes the copper target of strength ratio routine improve at least 10%.

Preferably be lower than the formation that connects the copper alloy target under the temperature and time that produces complete static recrystallize.This connection is preferably included in to be lower than and connects 4 hours under about 400 ℃ temperature, more preferably carries out under 350 ℃ 1-4 hour being lower than.Adopt these condition of contacts can form median size less than 1 micron copper alloy target.

Perhaps, connection comprises the temperature that can cause the copper alloy recrystallize.In a kind of like this process of connection, i.e. this connection comprises the temperature of the static recrystallize minimum temperature that is higher than concrete alloy, it is desirable to make the temperature and time minimum of connection, thereby makes the grain growing minimum.The recrystallize that occurs in connection procedure is preferably such, and the median size that promptly produces in copper alloy is about 20 microns of 1-.Preferably carry out about at least 1 hour of this thermal treatment that is used for perfect recrystallization under about 200 ℃ temperature, be preferably 350-500 ℃, the time was greater than 1 hour.

As the another kind of method of combined heated and connection procedure, heat-treat before or after the Connection Step at Connection Step (being thermal treatment 400).Useful is be connected and thermal treatment to improve strength of connection and to make copper or the Cu alloy material recrystallize.

The connection copper that forms according to the inventive method and is connected the copper alloy target has raising with respect to the connection target of application ordinary method formation strength of joint.In aspect more of the present invention, for target is connected with supporting plate, it is preferred that diffusion connects.At the half-finished particle diameter of target is under the situation of submicron, because the diffusibility that superfine crystal particle improves connects so can produce the diffusion of very high strength.The diffusion connection that obtains has 15ksi or higher yield strength, and in some cases, yield strength can equal or exceed 30ksi.With respect to the target of routine, the additional advantage that the present invention connects copper target and copper alloy target comprises the distortion drag that improves target and reduces change curved.Target of the present invention is used for the sputter purposes can be provided and wherein have the less film that improves in conjunction with the particulate quality, and film thickness homogeneity preferably can be provided and therefore improve the homogeneity of resistance.In addition, will be used for semiconductor machining according to the target that the inventive method forms the inhomogeneity wafer that film thickness and resistance improve between wafer and the wafer will be provided.

The high-purity copper and copper alloy target of monolithic that forms according to the inventive method have with respect to the routine that adopts other method to form connect the copper and copper alloy target grow to few 30%, typical case long 40% life-span.Can obtain the feasible routine of can avoiding of monolithic copper target and connect peeling off (separating) of target appearance with supporting plate.In addition, monolithic target according to the present invention have increase target distortion drag, become particle produces, improves in the film of the curved this target sputter of usefulness that reduces, reduces the film thickness and the homogeneity of resistivity.In addition, monolithic target according to the present invention has film thickness consistence and resistivity evenness between the wafer of raising and the wafer.

The embodiment that below provides is the exemplary preferred embodiment of the present invention.It being understood that to the present invention includes extra embodiment, and the specific embodiment that is not limited to provide.

Embodiment 1: make high purity copper monolithic sputtering target

The heating diameter is that 6 inches, length are that 11 inches, purity are the casting copper base of 6N in air furnace, is heated under about 990 temperature and keeps about 60 minutes.Then, this base of heat forged carries out shrend immediately to finally highly reducing 55-75%, uses silicon-dioxide or graphite foil in forged process.Then, cold rolling forging piece 16 roads quench after initial 8 roads, and making total reduction is about 60-about 80%.By being about 6% crackle that prevents in the cold-rolled process of about 5-carrying out 4 road draught that per pass produces when cold rolling.Carry out the 13-16 road with about 11% draught of the generation about 10-of per pass, thereby obtain little particle diameter.After cold rolling, made the work in-process recrystallize in about 120 minutes by being heated to about 480 °F.These work in-process of machining are to make final target.The high purity copper monolithic target that obtains has the median size less than 50 microns, has homogeneous granules simultaneously and distribute in entire target.

The sample position that the monolithic target that Figure 11 obtains is used to analyze.The thickness of target is 0.89 inch.Particle diameter and the mean value thereof measured at the place of each point shown in the sputtering surface provide in table 2.

Table 2: the grain diameter measurement data of target surface

The position	??1	??2	??3	??4	??5	??6	??7	??8	??9	On average
											Particle diameter	??38	??45	??45	??38	??38	??53	??38	??38	??53	?43

Provided a little the particle diameter indicated of depth plane among the Figure 11 that measures in the table 3, and the mean value of these observed values.Table 4 has illustrated the texture that object point is determined of indicating of target definite in Figure 11.

Table 3: the grain diameter measurement data of indicating a place in the target

The degree of depth	????2	????4	????5	????7	On average
						??0.250”	????53	????38	????45	????45	????45.3
??0.460”	????45	????38	????45	????45	????43.3
						??0.700”	????45	????45	????45	????45	????45

A table 4: indicate and locate the microstructural texture of target

The degree of depth	The position	????(111)	????(200)	????(220)	????(113)
						??0.00”	????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”	????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”		????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％

By another embodiment of the high-purity target of formation that illustrates among the embodiment of front, difference is ECAE is introduced in the technology.Before cold rolling, carry out ECAE to reduce to cast the particle diameter that exists in the base.With point out above be used for the same target that obtains of analyzing of the foregoing description.This target has the median size less than 15 microns in entire target.

Embodiment 2: make the copper alloy monolithic sputtering target

Heating has the copper alloy base that is less than 10% Ag, Sn, Al or Ti, and holds it under about 1500 temperature of about 900-about 45 minutes.Then, this base of heat forged is to produce the final reduction at least about 50%.Some forging bases (depending on alloy) at least 10 minutes of reheat in forged process.After final forging, shrend immediately should be forged base.It is about 60% that cold rolling forging piece to draught is at least, thereby form work in-process, made this work in-process recrystallize in 120 minutes by being heated to about 1200 temperature of about 750-.The work in-process of this recrystallize of machining are to form monolithic target.Each target all has the about 50 microns median size of about 15-.

Form the particular target of copper alloy with 0.3 atom %Al with the base of 6 inches of diameters, 11 inches of length.At first, heated this base 1 hour down, and at first this base being forged is 6 inches highly extremely at 1400 °F.After initial the forging,, subsequently this base is forged to being 3 inches highly this base of 1400 following reheat 15 minutes.After final forging, piece is forged in shrend immediately.Then, according to rolling scaduled shown in the table 5 carry out by 17 roads form cold rolling, thereby form rolling work in-process.

Annealed about 120 minutes down at about 825 °F at rolling work in-process afterwards, and form final monolithic target.The analysis on target surface (according to surface point shown in Figure 11) shows forms all even 37 microns median size.The particle diameter ununiformity is 8.6% (1-σ).

Table 5:Cu-0.3 atom %Al's is rolling scaduled

The road	Direction (degree)	Δ height (inch)	Highly (inch)	The % draught
					????1	????0	????0.1	????2.9	????3.3
????2	????135	????0.1	????2.8	????3.4
					????3	????270	????0.1	????2.7	????2.6
????4	????45	????0.1	????2.6	????3.7
					????5	????180	????0.1	????2.5	????3.8
????6	????315	????0.1	????2.4	????4.0
					????7	????90	????0.1	????2.3	????4.2
????8	????225	????0.1	????2.2	????4.3
					????9	????0	????0.13	????2.07	????5.9
????10	????135	????0.13	????1.94	????6.2
					????11	????270	????0.13	????1.81	????6.7
????12	????45	????0.13	????1.68	????7.1
					????13	????180	????0.13	????1.55	????7.7
????14	????315	????0.13	????1.42	????8.3
					????15	????90	????0.13	????1.29	????9.1
????16	????225	????0.13	????1.16	????10.0
					????17	Free road (One free pass)

Embodiment 3: the manufactured copper alloy diffusion connects sputtering target

By providing and the worked copper alloy preform of describing among the embodiment 2, difference is to be cold-rolled to draught and is at least about 50%.Under about 450 ℃ connection temperature, cold rolling work in-process are connected about 120 minutes with the CuCr supporting plate.The recrystallize that alloy in the process that connects, occurs.The target that connects has less than about 30 microns particle diameter with up to the strength of joint of about 30ksi.

Embodiment 4: adopt ECAE to make high purity copper sputtering targets

Provide purity to be at least 99.9999% cast copper copper base.This high purity copper base of heat forged under minimum about 500 ℃ temperature, simultaneous altitude descends at least about 40%, forges piece thereby form.Be heated at least about 500 ℃ and make this piece solutionizing by forging piece, keep this temperature at least about 1 hour.The piece of this solutionizing of shrend immediately after thermal treatment, and according to route D (piece rotates 90 degree between continuous time), adopt 4-6 time equal channel angular to push (ECAE) and push this piece, thereby generate the submicron microstructure.Process annealing under the temperature that about 125-is about 225 ℃ between some or all of ECAE time was at least about 1 hour.High-purity copper billet to the draught of cold rolling extruding is at least 60%, thereby forms the target work in-process, and these work in-process are formed monolithic target or connect target.

Machining monolithic target work in-process, thus final target made.Directly this work in-process manufacturing of machining has the target of submicron particle diameter.Carry out recrystallize and have the monolithic target of the about 20 microns median sizes of 1-with manufacturing.

The work in-process diffusion that will be used to connect target is connected to supporting plate.Spread connection less than 4 hours being lower than under 350 ℃ the temperature.Connect yield strength greater than about 15ksi.This connection target has from submicron to about 20 microns particle diameter.This submicron target improves about 50% with respect to conventional target strength.Particle diameter is that the about 20 microns connection target of 1-improves at least 10% with respect to conventional copper target strength.Spreading connection under 250 ℃ after 2 hours, the particle diameter (seeing sample intelligence Figure 11) at different positions place is shown in Table 6 in the whole 6N copper target.Median size is 11.37 microns, and standard deviation is 6.97% (1-σ).

Table 6:6N diffusion connects the particle diameter (micron) of target

The position	End face	Middle face	The bottom surface
				????1	????13	????11	????11
????2	????11	????13	????11
				????3	????11	????11	????11
????4	????13	????11	????11
				????5	????11	????11	????11
????6	????11	????11	????13
				????7	????11	????11	????13
????8	????11	????11	????11
				????9	????11	????11	????11

Table 7 has provided the three point hardness observed values that obtain the end face that hits from table 6 and the bottom surface.Average hardness is 53.3HB, and standard deviation is 2.18% (1-σ).

Table 7:6N diffusion connects the hardness (HB) of target

The position	End face	The bottom surface
			????1	????53.4/55.1/53.4	????51.8/51.8/50.3
????2	????50.3/51.8/51.8	????53.4/53.4/51.8
			????3	????53.4/55.1/51.8	????53.4/53.4/53.4
????4	????53.4/55.1/53.4	????50.3/51.8/51.8
			????5	????55.1/55.1/53.4	????51.8/51.8/51.8
????6	????53.4/55.1/53.4	????51.8/53.4/50.3
			????7	????55.1/55.1/53.4	????53.4/53.4/51.8
????8	????53.4/53.4/51.8	????51.8/53.4/51.8
			????9	????53.4/53.4/51.8	????53.4/53.4/51.8

Embodiment 5: adopt ECAE manufactured copper alloy sputtering targets

Provide with 1000ppm to the copper base that is less than or equals the copper-bearing alloy of about 10% Ag, Al, In, Zn, B, Ga, Mg, Sn, Ge, Ti or Zr alloying.This base of heat forged under at least about 500 ℃ temperature, simultaneous altitude descends at least about 40%, forges piece thereby form.Be heated at least about 500 ℃ and make this piece solutionizing by forging piece, keep this temperature at least about 1 hour, thereby form the piece of solutionizing.The piece of this solutionizing of shrend immediately after solutionizing.

Push the piece of this solutionizing by carrying out 4-6 all over ECAE.According to route D, piece 90 degree of this solutionizing of rotation between each time.Some ECAE all between, under the about 325 ℃ temperature of about 150-, carry out process annealing at least 1 hour.It is about 60% that cold rolling ECAE crushing block to draught is at least, thereby form the copper alloy work in-process.

Made first piece monolithic copper alloy target according to the copper alloy work in-process of described manufacturing to form monolithic target by machining.The median size of first monolithic target is less than 1 micron.In addition, to have basic identical elementary composition, median size be that 30 microns the height of target is at least about 50% for the yield strength of this first monolithic copper alloy target, ultimate tensile strength (UTS) and hardness ratio.

Make second monolithic copper alloy target by the copper alloy work in-process that thermal treatment is made as mentioned above.Under 350 ℃ temperature, heat-treated about 1 hour.The median size of second target is about 20 microns of 1-, does not have precipitate (do not have precipitate to refer to substantially do not have can detected precipitate) substantially, and not having can detected segregation, and the maximum interspace size is less than 1 micron.

Make first connection copper alloy target by being connected with the supporting plate diffusion according to the copper alloy work in-process of describing manufacturing.Connect 1-4 hour being lower than to spread under 350 ℃ the temperature.First median size that connects alloys target is less than 1 micron.

Be connected at least 1 hour by the copper alloy work in-process that under the about 500 ℃ connection temperature of about 350-, will make as mentioned above with the supporting plate diffusion and make second connection copper alloy target.Second connects the copper alloy target is abundant recrystallize, and the median size of this target is about 20 microns of about 1-.

Claims (109)

1. copper-comprising sputtering target comprises:

At least 99.99 weight % copper;

At least 1 micron to being less than or equal to about 50 microns median size; With

The yield strength of this target is more than or equal to about 15ksi.

2. the target of claim 1, wherein the hardness of this target is 40HB at least.

3. the target of claim 1, the ultimate tensile strength of this target is 50 microns, has a basic identical elementary composition target height at least 15% than median size.

4. the sputtering target of claim 1, the hardness ratio median size of this target be 50 microns, have basic identical elementary composition target height at least 15%.

5. the sputtering target of claim 1, the yield strength ratio median size of this target be 50 microns, have basic identical elementary composition target height at least 10%.

6. the sputtering target of claim 1, wherein this target is a monolithic, sputter life is 50 microns, has basic identical elementary composition another kind and connect target and grow to and lack 30% than median size.

7. the target of claim 1, wherein this target contains at least 99.999 weight % copper.

8. the target of claim 1, wherein this target contains at least 99.9999 weight % copper.

9. the target of claim 1, wherein this target contains at least 99.99995 weight % copper.

10. the target of claim 1, wherein this target contains and has the particle size uniformity that is less than or equal to 20% ununiformity.

11. the target of claim 10, wherein this ununiformity is less than 15% (1-σ).

12. the target of claim 1, wherein this target has the particle size uniformity that standard deviation is less than or equal to 10% (1-σ).

13. the target of claim 1 wherein is connected to this target diffusion on the supporting plate, this diffusion connects the connection yield strength that has greater than 10ksi.

14. the target of claim 13 wherein should connect yield strength more than or equal to about 15ksi.

15. the target of claim 1, wherein this median size is about 20 microns of about 5-.

16. copper alloy sputtering target composed of the following components substantially:

Be less than or equal about 99.99 weight % copper;

At least a alloy element that is selected from the following element: 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, Si, Pt, Nb, Re, Mo and Hf, the total amount of at least a alloy element that exists in the target for 100ppm-at least less than 10 weight %; The hardness of this target is 40HB at least.

17. the target of claim 16, its median size is less than 1 micron.

18. the particle size uniformity standard deviation is less than or equal to about 15% (1-σ) in the target of claim 17, entire target.

19. the particle size uniformity standard deviation is less than or equal to about 10% (1-σ) in the target of claim 17, entire target.

20. the uniformity of hardness standard deviation is less than about 5% (1-σ) in the target of claim 16, entire target.

21. the target of claim 20, wherein the uniformity of hardness standard deviation is less than about 3.5% (1-σ).

22. the target of claim 16, wherein this target is a monolithic.

23. the target of claim 16, its diffusion is connected on the supporting plate, and this diffusion connects the connection yield strength that has greater than about 15ksi.

24. the target of claim 16, its orientation distribution function (ODF) less than about 15 times unordered.

25. the target of claim 16, its orientation distribution function (ODF) less than about 5 times unordered.

26. the target of claim 16, its main grain orientation is not (220).

27. the target of claim 16, at least a alloy element wherein is selected from Ag, Al, In, Zn, B, Ga, Mg, Sn, Ge, Ti and Zr.

28. the target of claim 16, wherein the total amount of alloy element is less than about 2% for about 1000ppm-.

29. copper alloy sputtering target composed of the following components substantially:

Be less than or equal to about 99.99 weight % copper;

At least a alloy element that is selected from the following element: 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, Mo, Si, Re, Pt, Nb and Hf, the total amount of at least a alloy element that exists in the target for 100ppm-at least less than 10 weight %; The median size of target is about 20 microns of 1-, and the standard deviation of particle size uniformity is less than about 15% (1-σ) in the entire target.

30. the target of claim 29, wherein the particle size uniformity standard deviation is less than about 10% (1-σ).

31. the target of claim 29, wherein the hardness of this target is at least about 40HB.

32. the target of claim 29, its uniformity of hardness that has are included in the entire target hardness standard deviation less than about 5% 1-σ.

33. the target of claim 29, wherein this target is a monolithic.

34. the target of claim 29, its diffusion is connected on the supporting plate, and this diffusion connects the connection yield strength that has greater than about 15ksi.

35. the target of claim 29, its orientation distribution function (ODF) less than about 15 times unordered.

36. the target of claim 29, its orientation distribution function (ODF) less than about 5 times unordered.

37. the target of claim 29, its main grain orientation is not (220).

38. the target of claim 29, wherein this at least a alloy element is selected from Ag, Al, In, Zn, B, Ga, Mg, Sn, Ge, Ti and Zr.

39. the target of claim 29, wherein the total amount of alloy element is less than about 2% for about 1000ppm-.

40. a monolithic sputtering target substantially is made up of the alloy element that copper and total amount are less than or equal to 10 weight %.

41. the monolithic target of claim 40, wherein the total amount of alloy element comprises at least a element that is selected from the following element: 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, Mo, Si, Re, Pt, Nb and Hf.

42. the monolithic target of claim 41, wherein this at least a element is selected from Ag, Al, Sn and Ti.

43. the monolithic target of claim 40, wherein the total amount of alloy element is less than or equals about 2 weight %.

44. the monolithic target of claim 40, it contains at least 99.99 weight % copper.

45. the monolithic target of claim 40, wherein this target comprises that thickness is about 1 inch round-shaped.

46. the monolithic target of claim 40, median size is about 50 microns of about 15-.

47. one kind connects sputtering target, it is less than by copper and total amount substantially or the alloy element that equals 10 weight % is formed.

48. the connection target of claim 47, wherein the total amount of alloy element comprises at least a element that is selected from the following element: 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, Mo, Si, Re, Pt, Nb and Hf.

49. the connection target of claim 48, wherein this at least a element is selected from Ag, Al, Sn and Ti.

50. the connection target of claim 47, wherein the total amount of alloy element is less than or equals about 2 weight %.

51. the connection target of claim 47, it contains at least 99.99 weight % copper.

52. the connection target of claim 47, wherein this target comprises round-shaped.

53. the connection target of claim 47, its median size is less than about 100 microns.

54. the connection target of claim 53, wherein this median size is about 50 microns of about 15-.

55. the connection target of claim 53, wherein this median size is less than about 30 microns.

56. the connection target of claim 47 wherein is connected to the target diffusion on the supporting plate, strength of joint is at least about 15ksi.

57. the connection target of claim 56, wherein this strength of joint is at least about 30ksi.

58. the connection target of claim 56, wherein this supporting plate is the CuCr supporting plate.

59. a method that forms the monolithic sputtering target comprises:

Provide and substantially be less than or equal the copper base that one or more alloy elements of 10 weight % are formed by copper and total amount;

This base is heated at least about 900 °F, keeps this temperature at least about 45 minutes;

This base of forge hot makes highly to descend at least about 50%, forges piece thereby form;

It is about 60% that cold rolling this forging piece to draught is at least, thereby form work in-process;

Heat these work in-process bringing out recrystallize, and form median size and distribute less than about 100 microns final size; With

These work in-process are configured as the monolithic target shape.

60. the method for claim 59 also is included in forge hot and carries out shrend afterwards.

61. the method for claim 59, wherein these one or more alloy elements comprise one or more elements that are selected from the following element: 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, Mo, Si, Re, Pt, Nb and Hf.

62. the method for claim 61, wherein these one or more alloy elements are selected from Ag, Al, Sn and Ti.

63. a method that forms the monolithic sputtering target comprises:

The copper base that contains at least 99.99 weight % copper is provided;

This base is heated to temperature at least about 900, and keeps this temperature at least about 45 minutes;

This base of forge hot makes highly to descend at least about 50%, forges piece thereby form;

It is about 60% that cold rolling this forging piece to draught is at least, thereby form work in-process;

Heat these work in-process bringing out recrystallize, and form median size and distribute less than about 100 microns final size; With

These work in-process are configured as the monolithic target shape.

64. the method for claim 63, wherein median size is less than or equal to about 50 microns.

65. the method for claim 57, wherein median size is less than or equal to about 15 microns.

66. the method for claim 57 also is included in the cold rolling equal channel angular extruding of carrying out before.

67. one kind forms the method that connects sputtering target, comprising:

The copper base that contains at least 99.99 weight % copper is provided;

This base is heated at least about 900 °F, and keeps this temperature at least about 45 minutes;

This base of forge hot makes highly to descend at least about 50%, forges piece thereby form;

It is about 50% that cold rolling this forging piece to draught is at least, thereby form work in-process; With

Work in-process are connected on the supporting plate.

68. the method for claim 67 wherein carries out this connection and forms median size distributing less than about 100 microns final size bringing out under the temperature of recrystallize.

69. the method for claim 67, wherein this connection produces the connection that intensity is at least 15ksi.

70. the method for claim 67, wherein forge hot comprises:

Preheating;

Part highly descends; With

At least reheat and additional height reduce.

71. the method for claim 67 also is included in forge hot and carries out shrend afterwards.

72. one kind forms the method that connects sputtering target, comprising:

Provide and substantially be less than or equal the copper base that one or more alloy elements of 10 weight % are formed by copper and total amount;

This base is heated to temperature at least about 900, and keeps this temperature at least about 45 minutes;

This base of forge hot makes highly to descend at least about 50%, forges piece thereby form;

It is about 50% that cold rolling this forging piece to draught is at least, thereby form work in-process; With

Work in-process are connected on the supporting plate.

73. the method for claim 72 wherein carries out this connection and forms median size distributing less than about 100 microns final size bringing out under the temperature of recrystallize.

74. the method for claim 72, wherein these one or more alloy elements comprise one or more elements that are selected from the following element: 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, Mo, Si, Re, Pt, Nb and Hf.

75. the method for claim 74, wherein these one or more alloy elements are selected from Ag, Al, Sn and Ti.

76. the method for claim 72, wherein this connection comprises that generation intensity connects for the diffusion of the connection of 15ksi at least.

77. the method for claim 72, wherein this forge hot comprises:

Preheating;

Part highly reduces; With

At least reheat and additional height reduce.

78. the method for claim 72 also is included in the cold rolling equal channel angular extruding of carrying out before.

79. a method that forms copper-comprising sputtering target comprises:

It is the Cu base of at least 99.99% copper that purity is provided;

Be higher than this copper base of forge hot under 300 ℃ the temperature, making highly to descend, forging piece thereby form at least about 40%;

Shrend should be forged piece;

Carry out extrusion process, comprising:

Make and forge piece by equal channel angular extruding (ECAE) at least 4 times; With

Thermal treatment, its be included in these at least 4 times at least some all between process annealing once or twice, and in the process of extrusion process with the ECAE mold heated to about 225 ℃ of about 125-;

After extrusion process, be cold-rolled to draught less than 90%, thereby form work in-process; With

These work in-process are configured as target.

80. the method for claim 79 also is included in this forging piece of solutionizing before the shrend, solutionizing comprises and is heated to this forging piece at least about 500 ℃ and keeps this temperature at least about 60 minutes.

81. the method for claim 79, wherein extrusion process is included in and carries out process annealing under the about 225 ℃ temperature of about 125-greater than about 1 hour.

82. the method for claim 79 comprises also these work in-process are heated to making the copper recrystallize and form final size-grade distribution in these work in-process that the median size that final size distributes is about 20 microns of about 1-; Wherein work in-process are configured as target and comprise the formation monolithic target.

83. the method for claim 79 wherein forms work in-process target and comprises that formation connects target.

84. the method for claim 83, wherein form connecting target comprises target is connected on the supporting plate, connect under about 325 ℃ temperature less than about 4 hours being less than or equal to, this connection static pressure, rolling coating, welding such as comprises and at least a during diffusion is connected.

85. the method for claim 84, wherein this connection comprises that diffusion connects to form the connection that yield strength is at least about the about 15ksi of 10-.

86. the method for claim 79, wherein this median size is about 50 microns of 1-.

87. the method for claim 86, wherein this median size is about 20 microns of 5-.

88. the method for claim 79, wherein at whole half-finished overall memory in uniform size distribution, uniformly particle diameter has the standard deviation less than 15% (1-σ).

89. the method for claim 88, wherein this particle size uniformity standard deviation is less than about 10% (1-σ).

90. the method for claim 79, wherein the purity of this copper base is at least about 99.999% bronze medal.

91. the method for claim 79, wherein the purity of this copper base is at least about 99.9999% bronze medal.

92. the method for claim 79, wherein the purity of this copper base is at least about 99.99995% bronze medal.

93. the method for claim 79, wherein these at least 4 times by 4-6 all over forming.

94. a method that forms copper alloy sputtering target comprises:

Provide substantially by being less than 99.99% bronze medal and being selected from the Cu base that at least a alloy element in the following element is formed: 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 and Hf, the total amount of at least a alloy element that exists in the Cu base is less than 10 weight % for 100ppm-at least;

Be higher than this copper base of forge hot under 300 ℃ the temperature, making highly to descend, forging piece thereby form at least about 40%;

Carry out extrusion process, comprising:

Make this forging piece by equal channel angular extruding (ECAE) at least 4 times; With

Thermal treatment, it is included in the process of extrusion process heating ECAE mould once or twice, and in these at least 4 times at least some all between, under about 325 ℃ of about 120-, carry out at least 1 hour time of process annealing;

After extrusion process, be cold-rolled to draught less than about 90%, thereby form work in-process; With

These work in-process are configured as target.

95. the method for claim 94, wherein extrusion process comprises the ECAE mold heated to about 325 ℃ of about 125-.

96. the method for claim 94 also is included in before the extrusion process by being heated at least about 500 ℃, and keep this temperature at least about 60 minutes this forging piece of solutionizing.

97. the method for claim 94, wherein these at least 4 times by 4-6 all over forming.

98. the method for claim 94, wherein in the process of extrusion process and after extrusion process, this method only adopts the temperature of being less than or equal to 350 ℃, and wherein work in-process is configured as target and comprises the formation monolithic target.

99. the method for claim 94 wherein is configured as work in-process target and comprises that formation connects target.

100. the method for claim 99 also is included in formation connection target and carried out the about 1-of complete static recrystallize processing before about 8 hours under the about 500 ℃ of temperature of about 250-.

101. the method for claim 99 also is included in formation connection target and carried out the about 1-of complete static recrystallize processing afterwards about 8 hours under the about 500 ℃ of temperature of about 250-.

102. the method for claim 99, wherein form connecting target comprises target is connected on the supporting plate, be less than or equal to about 4 hours connection under about 500 ℃ temperature being less than or equal to, this connection comprises etc. that static pressure, rolling coating, welding, blast connect, do not have that friction is forged and at least a in being connected of diffusion.

103. the method for claim 99, wherein this connection comprises that diffusion connects to form the connection that yield strength is at least about the about 15ksi of 10-.

104. the method for claim 94, wherein this median size is about 20 microns of 1-.

105. the method for claim 104, wherein this median size is about 10 microns of about 5-.

106. the method for claim 94, wherein this median size is less than 1 micron.

107. the method for claim 94, wherein at whole half-finished overall memory in uniform size distribution, uniformly particle diameter has the standard deviation less than 15% (1-σ).

108. the method for claim 107, wherein this particle size uniformity standard deviation is less than about 10% (1-σ).

109. the method for claim 94 also is included in before the extrusion process, carries out ageing treatment under less than about 500 ℃ temperature, on average separates out size and is less than or equal to about 0.5 micron precipitate thereby form.

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