The present invention generally relates to sputtering targets and methods for fabricating sputtering targets and, in particular, relates to sputter targets comprising a plurality of materials including at least a first material and a second material, the first material comprised of cobalt (Co), chromium (Cr), ruthenium (Ru), nickel (Ni), or iron (Fe) and the second material comprised of carbon (C), a carbon (C)-containing material, a carbide, a nitrogen (N)-containing material, a nitride, silicon (Si), a silicon (Si)-containing material, a silicide, an oxygen (O)-containing material, an oxide, boron (B), a boron (B)-containing material, or a boride, and further relates to methods for fabricating such sputter targets, and products produced thereby.
Cathodic sputtering processes are widely used for the deposition of thin films of material onto desired substrates. A typical sputtering system includes a plasma source for generating an electron or ion beam, a target that comprises a material to be atomized and a substrate onto which the sputtered material is deposited. The process involves bombarding the target material with an electron or ion beam at an angle that causes the target material to be sputtered or eroded. The sputtered target material is deposited as a thin film or layer on the substrate.
According to one embodiment, the present invention relates to a novel method of fabricating sputtering targets that include non-metals such as boron, carbon, nitrogen, oxygen, silicon, a boride, a carbide, a nitride, an oxide, a silicide, a boron (B)-containing material, a carbon (C)-containing material, a nitrogen (N)-containing material, an oxygen (O)-containing material, or a silicon (Si)-containing material, including mixtures of non-metals, compounds of non-metals, master alloys containing boron, carbon or silicon and products produced by these processes. According to one embodiment, a process comprises preparation of pre-alloyed powder(s) or master alloy powder(s) or selection of ultra fine compound powder(s) of about 0.01 to 50 microns, preferably 0.1 to 10 microns, more preferably 1.0 to 5.0 microns average particle size and most preferably less than 2 microns. It has been discovered that spitting will not occur when the above phases are in form of ultra fine particles of less than 50 microns, preferably less than 10 microns in size. After the ultra fine powders are blended together, the powder blend is canned, followed by a hot isostatic press (HIP) consolidation. Powder processing as above is employed to make the target materials because of unique advantages over the prior art's melting process, both technically and economically.
According to one embodiment of the present invention, a sputter target comprises a plurality of materials. The plurality of materials includes at least a first material and a second material. The first material is comprised of cobalt (Co), chromium (Cr), ruthenium (Ru), nickel (Ni), or iron (Fe). The second material is comprised of carbon (C), a carbon (C)-containing material, a carbide, a nitrogen (N)-containing material, a nitride, a silicon (Si)-containing material, or a silicide. The second material constitutes a phase. The phase of the second material has an average size between greater than 0 micron and 50 microns. The first material comprises at least 15 atomic percent or greater.
According to one embodiment of the present invention, a sputter target comprises a plurality of materials. The plurality of materials includes at least a first material and a second material. The first material is comprised of cobalt (Co), ruthenium (Ru), nickel (Ni), or iron (Fe). The second material is comprised of an oxygen (O)-containing material or an oxide. The second material constitutes a phase. The phase of the second material has an average size between greater than 0 micron and 50 microns.
According to one embodiment of the present invention, a sputter target comprises a plurality of materials. The plurality of materials includes at least a first material and a second material. The first material is comprised of cobalt (Co), chromium (Cr), ruthenium (Ru), nickel (Ni), or iron (Fe). The second material is comprised of an oxygen (O)-containing material or an oxide. The second material constitutes a phase. The phase of the second material has an average size between greater than 0 micron and 50 microns. If the sputter target consists of chromium (Cr) and the oxygen (O)-containing material only, the oxygen (O)-containing material is an oxygen (O)-containing material other than simply chromium oxide. If the sputter target consists of chromium (Cr) and the oxide only, the oxide is an oxide other than simply chromium oxide.
According to one embodiment of the present invention, a sputter target comprises a plurality of materials. The plurality of materials includes at least a first material and a second material. The first material is comprised of cobalt (Co), chromium (Cr), ruthenium (Ru), nickel (Ni), or iron (Fe). The second material is comprised of boron (B), a boron (B)-containing material or a boride. The second material constitutes a phase. The phase of the second material has an average size between greater than 0 micron and less than 10 microns.
According to one embodiment of the present invention, a sputter target comprises a plurality of materials. The plurality of materials includes at least a first material and a second material. The first material is comprised of ruthenium (Ru), nickel (Ni), or iron (Fe). The second material is comprised of boron (B), a boron (B)-containing material or a boride. The second material constitutes a phase. The phase of the second material has an average size between greater than 0 micron and 50 microns.
According to one aspect of the present invention, a method of fabricating a sputter target comprises the steps of: blending a plurality of materials; canning; and pressing. The plurality of materials includes at least a first material and a second material. The first material is comprised of cobalt (Co), chromium (Cr), ruthenium (Ru), nickel (Ni), or iron (Fe). The second material is comprised of carbon (C), a carbon (C)-containing material, a carbide, a nitrogen (N)-containing material, a nitride, a silicon (Si)-containing material, or a silicide. The second material has an average particle size between greater than 0 micron and 50 microns. The first material comprises at least 15 atomic percent or greater. The plurality of materials is comprised of multiple powders, one or more master alloy or compound powders, or a mixture of one or more powders with one or more master alloy or compound powders.
According to one aspect of the present invention, a method of fabricating a sputter target comprises the steps of: blending a plurality of materials; canning; and pressing. The plurality of materials includes at least a first material and a second material. The first material is comprised of cobalt (Co), ruthenium (Ru), nickel (Ni), or iron (Fe). The second material is comprised of an oxygen (O)-containing material or an oxide. The second material has an average particle size between greater than 0 micron and 50 microns. The plurality of materials is comprised of multiple powders, one or more master alloy or compound powders, or a mixture of one or more powders with one or more master alloy or compound powders.
According to one aspect of the present invention, a method of fabricating a sputter target comprises the steps of: blending a plurality of materials; canning; and pressing. The plurality of materials includes at least a first material and a second material. The first material is comprised of cobalt (Co), chromium (Cr), ruthenium (Ru), nickel (Ni), or iron (Fe). The second material is comprised of an oxygen (O)-containing material or an oxide. The second material has an average particle size between greater than 0 micron and 50 microns. The plurality of materials is comprised of multiple powders, one or more master alloy or compound powders, or a mixture of one or more powders with one or more master alloy or compound powders. If the plurality of materials consists of chromium (Cr) and the oxygen (O)-containing material only, the oxygen (O)-containing material is an oxygen (O)-containing material other than simply chromium oxide. If the plurality of materials consists of chromium (Cr) and the oxide only, the oxide is an oxide other than simply chromium oxide.
According to one aspect of the present invention, a method of fabricating a sputter target comprises the steps of: blending a plurality of materials; canning; and pressing. The plurality of materials includes at least a first material and a second material. The first material is comprised of cobalt (Co), chromium (Cr), ruthenium (Ru), nickel (Ni), or iron (Fe). The second material is comprised of boron (B), a boron (B)-containing material or a boride. The second material has an average particle size between greater than 0 micron and less than 10 microns. The plurality of materials is comprised of multiple powders, one or more master alloy or compound powders, or a mixture of one or more powders with one or more master alloy or compound powders.
According to one aspect of the present invention, a method of fabricating a sputter target comprises the steps of: blending a plurality of materials; canning; and pressing. The plurality of materials includes at least a first material and a second material. The first material is comprised of ruthenium (Ru), nickel (Ni), or iron (Fe). The second material is comprised of boron (B), a boron (B)-containing material or a boride. The second material has an average particle size between greater than 0 micron and less than 50 microns. The plurality of materials is comprised of multiple powders, one or more master alloy or compound powders, or a mixture of one or more powders with one or more master alloy or compound powders.
Reference is now made to the accompanying drawing wherein:
Appendix 1 shows a Periodic Table of elements.
Sputtering target materials for sputtering process range from pure metals to ever more complicated alloys. Complex 3 to 6 element alloys may be utilized for sputtering targets. Alloying additions such as boron, carbon, nitrogen, oxygen, silicon and so on are added to Cr—, Co—, Fe-based alloys to modify characteristics such as deposited film grain-size, surface energy and magnetic properties.
According to one embodiment, the presence of non-metal additions like boron, carbon, nitrogen, oxygen and silicon to target materials is either in the form of pure elements, e.g. boron and carbon, or in the form of compounds like boride, carbide, nitride and oxide. The pure element phases such as boron and carbon and the compound phases like boride, carbide, nitride, oxide, and silicide, however cause spitting problems during sputtering. The present invention provides a solution to this problem.
The powders of the present invention include elemental powders, pre-alloyed powders, powders of master alloys and/or intermetallic compound powders composed of 2 to 6 elements, including but not limited to Cr—, Co—, Ru—, Ni—, and/or Fe-based alloys. According to one aspect of the present invention, examples of master alloys include pre-alloyed powders, and pre-alloyed powders may be atomized master alloys.
The powders of the present invention contain pure Cr, Co, Ru, Ni, Fe, Pt and/or Ta and/or (optionally) pre-alloyed or master alloy powders of said pure elements, and include at least a boride, a boron (B)-containing material (e.g., boron based inorganic compound or master alloy), a carbide, a carbon (C)-containing material (e.g., carbon based inorganic compound or master alloy), a nitride, a nitrogen (N)-containing material, a silicide, a silicon (Si)-containing material (e.g., silicon based master alloy), an oxide, or an oxygen (O)-containing material of one or more elements from the Periodic Table of elements shown in Roman numeral column number IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB or IVB (see Appendix 1). These Roman numeral column numbers correspond to column numbers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 and 14.
Examples of a boron (B)-containing material include a boride; examples of a carbon (C)-containing material include a carbide; examples of a nitrogen (N)-containing material include a nitride; examples of a silicon (Si)-containing material include a silicide; and examples of an oxygen (O)-containing material includes an oxide.
In preferred embodiments, the non-metallic additive is in combined form such as an inorganic compound or a master alloy of a non-metal although elemental additions may be used if desired. Preferred doping non-metals are compounds of boron, carbon and nitrogen. In still other embodiments compounds of oxygen or silica are included as dopants. Preferred doping compounds are borides or boron (B)-containing materials, carbides, or carbon (C)-containing materials and nitrides, as well as oxides and suicides or silicon (Si)-containing master alloys. Especially preferred compounds are MoB, AlN (Aluminum Nitride), and B4C, as well as Al2O3, Cr2O3, SiO2, and mixtures thereof. The amount of dopant may range from about 1 to 15 atomic percent (at. %), and preferably from 1 to 12 at. %.
In further embodiments, the step of forming the doped elemental powders or alloys is carried out by mechanical mixing to achieve substantially uniform blending of the materials. In further embodiments, the canning step is carried out so as to avoid segregation of the doped element or alloy.
Proper canning techniques are needed to avoid segregation during canning. Hot pressing in a graphite die could be used as well to consolidate the powder. The powders are canned in preparation for consolidation. In canning for example, a container is filled with the powder, evacuated under heat to ensure the removal of any moisture or trapped gasses present, and then sealed. In vacuum hot pressing, the chamber is continuously evacuated prior to and during load application. Although the geometry of the container is not limited in any manner, the container can possess a near-net shape geometry with respect to the final material configuration.
The encapsulate material from the canning step is then consolidated preferably via Hot-Isostatic-Pressing (HIP), a procedure known in the art. A HIP unit is typically a cylindrical pressure vessel large enough to house one or more containers. The inner walls of the vessel can be lined with resistance heating elements, and the pressure can be controlled by the introduction of inert gas within the container. HIP parameters including temperature, pressure and hold time will be minimized to prevent the growth of compound phases and grain size, as well as to save energy and to protect the environment. Pressures of about 5 to about 60 ksi (preferably 10-20 ksi) at temperatures between about 500° C. to about 1500° C., are typically employed to achieve appropriate densities. Depending upon the complexity of the cycle, total hold times during isostatic pressing typically vary from about 0.5 to about 12 hours. Pressure during vacuum hot pressing is varied from 0.5 to 5 ksi (preferably 1.5 to 2.5 ksi) at temperatures ranging from about 500° C. to 1500° C. (preferably 800-1000° C.). It is noteworthy that other powder consolidation techniques such as hot pressing and cold pressing can also be employed independently or in conjunction with HIP processing.
After consolidation, the solid material form (billet) is removed from the encapsulation can, and a slice of the billet can then be sent to be tested as to various properties of the billet. If desired, the billet can be subjected to optional thermo-mechanical processing to further manipulate the microstructural and macro-magnetic properties of the target. Also, the final shape and size of the sputter targets can be formed, for example, by processes such as wire EDM, saw, waterjet, lathe, grinder, mill, etc. In these steps, the target can be cleaned and subjected to a final inspection.
Table 1 shows examples of sputter target materials and their exemplary chemistry in accordance with one aspect of the present invention.
Table 2 shows examples of sputter target materials and their exemplary phases in accordance with one aspect of the present invention. The sputter target materials set forth in each row may include some or all of the exemplary phases described in the row, and they may include other additional phases.
Table 3 shows examples of sputter target materials and their exemplary powders that may be used to fabricate the sputter targets. The sputter target materials set forth in each row may be fabricated using some of all of the powders set forth in the row and optionally using other additional powders.
The following examples demonstrate the present invention further, but should not be construed as a limitation of the present invention. The processes for all materials are similar with each other as shown in
The above alloy is made with the following powder blends: (1) Cr powder, Mo powder and ultra fine MoB compound powder, or (2) Cr powder, Mo powder and pre-alloyed Cr-3.1 wt % B powder (i.e., Cr-3.1 wt % B master alloy powder) that is made with a vacuum induction melter at 1730° C. and mechanically crushing cast ingots into powder at room temperature. The pre-alloyed Cr-3.1 wt. % B powder can also be made by gas atomization. Special attention must be paid to mixing all powders together when ultra fine compound powder like MoB is used, otherwise segregation may occur. Herewith an attritor mill or a ball mill must be used for blending from 2 to 24 hours. The HIP parameters for this kind of alloy include the temperature ranging from about 1000-1400° C., at a pressure from about 5-40 ksi and a hold time from about 1-12 hours. The cooling rate must be controlled too, otherwise the HIPed billet may crack during cooling down. A cooling rate of 3° C./min and a hold plateau at 800° C. for 6 hours is introduced to cooling phase.
Two different combinations of starting powders are employed herein. A first alternative is the combination of Co powder, Cr powder, Pt powder and ultra fine Sio2 compound powder. A second alternative is the combination of Co powder, Cr powder, Pt powder, atomized Co—Si pre-alloy powder (i.e., Co—Si master alloy powder) and ultra fine Cr2O3 compound powder. The silicides are ultra fine and well dispersed in Co matrix of original gas-atomized Co—Si particles. Special mixing methods using an attritor mill or a ball mill for 2 to 24 hours must be employed here to mix all powders together homogeneously when ultra fine compound powders like SiO2 and Cr2O3 are used, otherwise segregation may occur. The HIP parameters for this kind of alloy include the temperature ranging from about 600-1400° C., at a pressure from about 5-40 ksi and a hold time from about 1-12 hours.
One example of Cr—Mo—X: Cr80 at %-Mo20 at % doped with oxygen of 1-4 atomic % (at. %).
Regular Cr powder, Mo powder and partly oxidized Cr compound powder of oxygen level 15000 ppm are used to make the targets. The Cr powder of high oxygen is produced by oxidizing Cr flakes at high temperature and then subjected to mechanical crushing. In this case, only a part of the surface area of Cr powder is covered with oxides. Special attention must be paid to Cr powder of high oxygen level and mixing all powders together in this case, otherwise segregation may occur. Herewith an attritor mill or a ball mill may be used for blending from 2 to 24 hours. The HIP parameters for this kind of alloy include the temperature ranging from about 800-1400° C., at a pressure from about 5-40 ksi and a hold time from about 1-12 hours. The cooling rate must be controlled too, otherwise the HIPed billet may crack during cooling down. A cooling rate of 3° C./min and a hold plateau at 800° C. for 6 hours is introduced to cooling phase.
Gas-atomized NiAl intermetallic compound powder and ultra fine Al2O3 compound powder and AlN compound powder of less than 5 microns in average particle diameter size were taken for making NiAl sputtering targets doped with oxygen or nitrogen. Besides gas-atomized NiAl powder, boron-doped gas-atomized NiAl powder was also taken for making NiAl sputtering targets doped with boron and borides are ultra fine and well dispersed in the matrix. Conventional gas atomization methods are used to manufacture the powders. Special attention must be paid to mixing all powders together when ultra fine compound powders like Al2O3 and AlN are used, otherwise segregation may occur. Herewith an attritor mill or a ball mill may be used for blending from 2 to 24 hours. The HIP parameters for this kind of alloy include the temperature ranging from about 900-1400° C., at a pressure from about 5-40 ksi, and a hold time from about 1-12 hours. The cooling rate must be controlled too, otherwise the HIPed billet may crack during cooling down. A power-off furnace cooling and a hold plateau at 700° C. for 4 hours is introduced to cooling phase.
The sputter target includes dark Co phases, dark Co—Cr master alloy phases, light Pt phases, and dark SiO2 compound phases. In this example, the SiO2 compound phases have an average size between greater than 0 and 10 microns (e.g., between greater than 0 and 5 microns).
The sputter target includes dark Co phases, dark Co—Cr master alloy phases, light Pt phases, and dark CoSi2 compound phases. In this example, the CoSi2 compound phases have an average size between greater than 0 and 5 microns. The Co phases have an average size between greater than 0 and 150 microns.
According to one embodiment of the present invention, a sputter target comprises a plurality of materials. The plurality of materials includes at least a first material and a second material. The first material is comprised of cobalt (Co), chromium (Cr), ruthenium (Ru), nickel (Ni), or iron (Fe). For example, the first material is comprised of one or more of the following according to one aspect: a cobalt (Co) element, a chromium (Cr) element, a ruthenium (Ru) element, a nickel (Ni) element, an iron (Fe) element, a cobalt (Co) based master alloy, a chromium (Cr) based master alloy, a ruthenium (Ru) based master alloy, a nickel (Ni) based master alloy, an iron (Fe) based master alloy, a cobalt (Co) based compound, a chromium (Cr) based compound, a ruthenium (Ru) based compound, a nickel (Ni) based compound, and an iron (Fe) based compound. According to one aspect, the first material comprises at least 15 atomic percent or greater. According to one aspect, the first material constitutes a first phase, and the first phase has an average size between greater than 0 micron and 50 microns (i.e., 0<phase size≦50 microns). The present invention is not limited to these ranges, and in another embodiment, the first phase has an average size greater than 50 microns.
The second material is comprised of carbon (C), a carbon (C)-containing material, a carbide, a nitrogen (N)-containing material, a nitride, a silicon (Si)-containing material, a silicide, an oxygen (O)-containing material, an oxide, boron (B), a boron (B)-containing material, or a boride. For example, the second material is comprised of one or more of the following according to one aspect: MoB compound, Co—Cr—B master alloy, Co—B master alloy, Co—B compound, Cr—B master alloy, Cr—B compound (e.g., Cr2B), Ti—B compound (e.g., TiB2), Ti—O compound, Ni—B master alloy, Ni—B compound, Al—B compound (e.g., AlB2), Co—Si master alloy, Fe—Si master alloy, Cr—Si compound, silicon oxide compound (e.g., SiO2), Co—Si compound (e.g., CoSi2, CO2Si), titanium oxide (e.g., TiO2), chromium oxide (e.g., Cr2O3), molybdenum oxide, aluminum oxide (e.g., Al2O3), ruthenium oxide, C (e.g., graphite), Ta—C compound, Fe—C master alloy, Fe—C compound, aluminum nitride, cobalt nitride, chromium nitride, and iron nitride.
According to one aspect, the second material constitutes a second phase, and the second phase of the second material has an average size between greater than 0 micron and 50 microns (e.g., between greater than 0 micron and 20 microns, between greater than 0 micron and 10 microns, between 0.1 microns and 10 microns, between greater than 0 micron and 5 microns, between 1 micron and 5 microns, between greater than 0 micron and 2 microns, or less than 2 microns, etc.).
According to one aspect, the plurality of materials further includes a third material. According to one aspect, the third material is comprised of one or more of the following: a transition element, a refractory element, a cobalt-transition element based master alloy, a cobalt-refractory element based master alloy, a transition element based compound, and a refractory element based compound. In another aspect, the third material is comprised of platinum (Pt) or tantalum (Ta). According to one aspect, the third material constitutes a third phase, and the third phase has an average size between greater than 0 micron and 50 microns (i.e., 0<phase size≦50 microns). The present invention is not limited to these ranges, and in another embodiment, the third phase has an average size greater than 50 microns.
According to one aspect of the present invention, a sputter target is fabricated by blending a plurality of materials, canning and pressing. The plurality of materials includes at least the first material and the second material described above. The plurality of materials may also include the third material described above. The plurality of materials may further include other materials. When the plurality of materials are blended, each of the plurality of materials (e.g., each of the first, second and third materials) is in powder form, for example, elemental powders, one or more master alloy or compound powders, or a mixture of one or more powders with one or more master alloy or compound powders. Each of the first material, second material and third materials described above is in powder form for blending. According to one aspect, the particle size of the first material, the particle size of the second material, and particle size of the third material are the same as the size of the first phase, the size of the second phase, and the size of the third phase described above, respectively.
Some examples of a transition element include elements from the Periodic Table of elements shown in Roman numeral column number IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB according to one aspect of the present invention. Some examples of a refractory element include elements from the Periodic Table of elements shown in Roman numeral column number IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB that have a melting point greater than or about equal to the melting point of iron (Fe) according to one aspect of the present invention.
Some examples of a cobalt-transition element based master alloy include a Co—Cr master alloy, a Co—Mn master alloy, a Co—Fe master alloy, a Co—Cr—B master alloy, and a Co—Ni master alloy according to one aspect of the present invention. Some examples of a cobalt-refractory element based master alloy include a Co—Ta master alloy, a Co—Pt master alloy and a Co—Zr master alloy according to one aspect of the present invention.
Some examples of a transition element based compound include CoSi2, CrSi2, Fe3C, and Ni3Al according to one aspect of the present invention. Some examples of a refractory element based compound include TaC, Ta2C, TaB2, TaB, Mo2C, MoSi2, Mo2B and Mo2C according to one aspect of the present invention.
According to one aspect of the present invention, a master alloy is a combination of two or more elements consisting of a single or a multi-phase material, either as a simple solid solution (single-phase) of a minor element in a matrix of the major element or a combination of a solid solution and one or more secondary phases (multi-phase) having at least two constituents among the alloying elements. Compounds of two or three different elements are substances containing a defined number of each atom species and having specific physical and chemical properties, on the whole, different from those which their constituents had as elementary substances.
According to one aspect of the present invention, a sputter target includes chromium and an oxide that is not a simple chromium oxide or Cr2O3. For example, such sputter target includes: chromium; chromium oxide or Cr2O3; and other element(s), alloy(s) and/or compound(s). In another example, such sputter target includes: chromium; and a compound(s) based on a chromium oxide (as opposed to a particular chromium oxide such as Cr2O3).
According to one aspect of the present invention, a sputter target includes chromium and an oxide that is not a simple silicon dioxide (SiO2). For example, such sputter target includes: chromium; silicon dioxide; and other element(s), alloy(s) and/or compound(s). In another example, such sputter target includes: chromium; and a compound(s) based on a silicon oxide (as opposed to a particular silicon oxide such as siO2).
While this invention has been described with reference to several preferred embodiments, it is contemplated that various alterations and modifications thereof will become apparent to those skilled in the art upon a reading of the detailed description contained herein. It is therefore intended that the following claims are interpreted as including all such alterations and modifications as fall within the true spirit and scope of this invention.
This application is a continuation-in-part of U.S. patent application Ser. No. 10/739,401, filed Dec. 19, 2003, which is a continuation-in-part of U.S. patent application Ser. No. 10/200,590, filed Jul. 23, 2002, all of which are hereby incorporated by reference in their entirety for all purposes.
Number | Date | Country | |
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Parent | 10739401 | Dec 2003 | US |
Child | 11650515 | Jan 2007 | US |
Parent | 10200590 | Jul 2002 | US |
Child | 10739401 | Dec 2003 | US |