EP2277191A1 - Alliages de molybdene-niobium, cibles de pulverisation contenant de tels alliages, procedes de fabrication de telles cibles, films minces prepares a partir de celles-ci et leurs utilisations - Google Patents

Alliages de molybdene-niobium, cibles de pulverisation contenant de tels alliages, procedes de fabrication de telles cibles, films minces prepares a partir de celles-ci et leurs utilisations

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Publication number
EP2277191A1
EP2277191A1 EP09739573A EP09739573A EP2277191A1 EP 2277191 A1 EP2277191 A1 EP 2277191A1 EP 09739573 A EP09739573 A EP 09739573A EP 09739573 A EP09739573 A EP 09739573A EP 2277191 A1 EP2277191 A1 EP 2277191A1
Authority
EP
European Patent Office
Prior art keywords
present
thin film
substrate
target
film device
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09739573A
Other languages
German (de)
English (en)
Inventor
Shuwei Sun
Prabhat Kumar
Olaf Schmidt-Park
Rong-Chein Richard Wu
Gary Rozak
Mark Gaydos
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Materion Newton Inc
Original Assignee
HC Starck Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by HC Starck Inc filed Critical HC Starck Inc
Publication of EP2277191A1 publication Critical patent/EP2277191A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • C03C17/09—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals by deposition from the vapour phase
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/045—Alloys based on refractory metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/25—Metals
    • C03C2217/27—Mixtures of metals, alloys
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/154—Deposition methods from the vapour phase by sputtering

Definitions

  • Sputtering is a technique used to produce a metallic layer in various manufacturing processes used in the semiconductor and the photoelectric industries.
  • the properties of films formed during sputtering are related to the properties of the sputtering target itself, such as the size of the respective crystal grain and the formation of secondary phase with distribution characteristics. It is desirable to produce a sputter target that will provide film uniformity, minimal particle generation during sputtering, and the desired electrical and physical properties in the resultant film.
  • Various sputtering techniques are used in order to effect the deposition of a film over the surface of a substrate.
  • Deposited metal films can be formed by a magnetron sputtering apparatus or other sputtering techniques.
  • the magnetron sputtering apparatus induces plasma ions of a gas to bombard a target, causing surface atoms of the target material to be ejected and deposited as a film or layer on the surface of a substrate.
  • a sputtering source in the form of a planar disc or rectangle is used as the target, and ejected atoms travel along a ljne-of-sight trajectory to deposit on top of a wafer whose deposition face is parallel to the erosion face of the target.
  • Tubular-shaped sputtering targets can also be used, such as described in U.S. Patent Application Publication No. 2007/0042728, the entire contents of which are incorporated herein by reference.
  • Sputtering targets may be desired which comprise materials or combinations of materials that cannot be fabricated by conventional means such as rolling. In such cases, targets are made by hot isostatic pressing (HIP) powders. Ideally, the target is made in a single step. However, physical limitations of powder packing density and size of HIP equipment make it necessary to join smaller segments in order to produce large sputtering targets. For single-phase targets, conventional processing such as welding may be used; for multi-phase materials or where alloy formation is to be avoided for any reason, solid-state edge to edge bonding is preferred.
  • HIP hot isostatic pressing
  • Interconnects in semiconductors and TFT-LCDs are evolving from aluminum and toward copper, thus new diffusion barriers are needed. Titanium provides excellent adhesion properties while the molybdenum contributes its dense barrier stability.
  • Integrated circuits for semiconductors and flat panel displays) use Mo-Ti as an underlayer or capping layer for aluminum, copper, and aluminum alloys to minimize hillocks formation, to control the reflectivity and provide protection from physical and chemical attack during photolithography.
  • the present invention relates, in general, to molybdenum alloys, their use in preparing sputtering targets, methods of preparing thin films using such sputtering targets and thin films prepared thereby. More specifically, the present invention relates to molybdenum alloys comprising a majority portion of molybdenum, an alloying amount of niobium and a doping amount of a third metal selected from the group consisting of nickel, chromium, titanium, zirconium, hafnium and/or vanadium. [0006] One embodiment of the present invention includes alloys which comprise
  • Another embodiment of the present invention includes alloys which comprise (a) molybdenum present in a majority portion; (b) niobium present in an alloying amount; and (c) a third metal selected from the group consisting of nickel, chromium, titanium, hafnium, vanadium and mixtures thereof, wherein the third metal is present in a doping amount.
  • Another embodiment of the present invention includes sputtering targets comprising a densified alloy comprising: (a) molybdenum present in a majority portion; (b) niobium present in an alloying amount; and (c) a third metal selected from the group consisting of nickel, chromium, titanium, zirconium, hafnium, vanadium and mixtures thereof, wherein the third metal is present in a doping amount.
  • the invention includes sputtering targets comprising a densified alloy comprising: (a) molybdenum present in a majority portion; (b) niobium present in an alloying amount; and (c) a third metal selected from the group consisting of nickel, chromium, titanium, zirconium, hafnium, vanadium and mixtures thereof, wherein the third metal is present in a doping amount; with the proviso that when the third metal is zirconium, the doping amount is less than 0.01% by weight or greater than 1% by weight.
  • Still another embodiment of the present invention includes methods comprising providing a blend of a molybdenum powder present in a majority portion, a niobium powder present in an alloying amount and a third metal powder selected from the group consisting of nickel, chromium, titanium, zirconium, hafnium, vanadium and mixtures thereof, wherein the third metal is present in a doping amount, with the proviso that when the third metal powder is zirconium, the doping amount is less than 0.01% by weight or greater than 1% by weight; and (b) subjecting the blend to heat and pressure to form a densified sputtering target.
  • Yet another embodiment of the present invention includes methods comprising: (a) providing a sputtering target comprising a densified alloy comprising: (i) molybdenum present in a majority portion; (ii) niobium present in an alloying amount; and (iii) a third metal selected from the group consisting of nickel, chromium, titanium, zirconium, hafnium, vanadium and mixtures thereof, wherein the third metal is present in a doping amount; (b) providing a substrate; and (c) subjecting the target to sputtering conditions to form a coating comprised of the target material on the substrate.
  • Another embodiment of the present invention includes thin film devices comprising a substrate and a thin film disposed above the substrate, the thin film prepared according to any of the sputtering method embodiments of the present invention.
  • Various embodiments of the present invention can provide sputtering targets which can be used in accordance with other method embodiments of the present invention to provide thin films for use in various devices also embodied by the present invention in which the performance properties of the thin film device are at least comparable to, and in some cases an improvement over, thin film devices known in the art, and wherein the thin films exhibit superior adhesion to the substrate.
  • Thin films according to the present invention and devices containing a thin film in accordance with the invention can also provide advantageous photolithography characteristics which can improve manufacturing productivity.
  • thin films in accordance with the present invention are uniform, rapid and controllable etch rates, which in combination with improved adhesion (both between the substrate and the thin films of the invention, but also between the thin films of the invention and later deposited metallic films, e.g., copper) can greatly improve photolithographic operations.
  • Fig. Ia is a secondary electron image of a comparative Mo-Ti target at a magnification of 100OX;
  • Fig. Ib is a backscattering electron image of the comparative Mo-Ti target in Fig. Ia at a magnification of 100OX;
  • Fig. 2a is a secondary electron image of the comparative Mo-Ti target in
  • Fig. 2b is a backscattering electron image of the comparative Mo-Ti target in Fig. Ia at a magnification of IOOOX ;
  • (0019J Fig. 3a is a secondary electron image of a MoNbZr target in accordance with one embodiment of the present invention at a magnification of 200X;
  • Fig. 3b is a backscattering electron image of the MoNbZr target in Fig. 3a at a magnification of 200X;
  • Fig. 4a is a secondary electron image of the MoNbZr target in Fig. 3a at a magnification of IOOOX;
  • Fig. 4b is a backscattering electron image of the MoNbZr target in Fig. 3a at a magnification of IOOOX;
  • Fig. 5a is a secondary electron image of a film prepared using a comparative Mo-Ti target on an Si substrate at a magnification of IOOOX;
  • Fig. 5b is a backscattering electron image of the film in Fig. 5a at a magnification of IOOOX;
  • Fig. 6a is a secondary electron image of another film prepared using a comparative Mo-Ti target on an Si substrate at a magnification of 20000X;
  • Fig. 6b is a backscattering electron image of the film in Fig. 6a at a magnification of 20000X;
  • Fig. 7 is a backscattering electron image of the film in Fig. 7a at a magnification of IOOOX;
  • Fig. 8a is a secondary electron image of a film prepared using a comparative Mo-Ti target on a Corning 1737 glass substrate at a magnification of
  • Fig. 8b is a secondary electron image of the film in Fig. 8a at a magnification of 5000X;
  • Fig. 9a is a secondary electron image of another film prepared using a comparative Mo-Ti target on a Corning 1737 glass substrate at a magnification of
  • Fig. 9b is a secondary electron image of the film in Fig. 9a at a magnification of 5000X;
  • Fig. 10a is a secondary electron image of another film prepared using a comparative Mo-Ti target on a Corning 1737 glass substrate at a magnification of
  • Fig. 10b is a secondary electron image of the film in Fig. 10a at a magnification of 5000X;
  • Fig. 1 Ia is a secondary electron image of another film prepared using a comparative Mo-Ti target on a Corning 1737 glass substrate at a magnification of
  • Fig. 1 Ib is a secondary electron image of the film in Fig. 1 Ia at a magnification of 5000X;
  • Fig. 12a is a secondary electron image of another film prepared using a comparative Mo-Ti target on a Corning 1737 glass substrate at a magnification of
  • Fig. 12b is a secondary electron image of the film in Fig. 12a at a magnification of 5000X;
  • Fig. 13a is a secondary electron image of a film prepared using a comparative Mo-Ti target on an Si substrate at a magnification of 10000X;
  • FIG. 13b is a secondary electron image of the film in Fig. 13a at a magnification of 5000X;
  • Fig. 14a is a secondary electron image of another film prepared using a comparative Mo-Ti target on an Si substrate at a magnification of 10000X;
  • Fig. 14b is a secondary electron image of the film in Fig. 14a at a magnification of 5000X;
  • Fig. 15a is a secondary electron image of another film prepared using a comparative Mo-Ti target on an Si substrate at a magnification of 10000X;
  • Fig. 15b is a secondary electron image of the film in Fig. 15a at a magnification of 5000X;
  • Fig. 16a is a secondary electron image of another film prepared using a comparative Mo-Ti target on an Si substrate at a magnification of 10000X;
  • Fig. 16b is a secondary electron image of the film in Fig. 16a at a magnification of 5000X;
  • Fig. 17a is a secondary electron image of a film prepared using a MoNbZr target according to one embodiment of the present invention on a Corning 1737 glass substrate at a magnification of 10000X;
  • Fig, 17b is a secondary electron image of the film in Fig. 17a at a magnification of 5000X;
  • Fig. 18a is a secondary electron image of another film prepared using a
  • MoNbZr target according to one embodiment of the present invention on a Corning 1737 glass substrate at a magnification of 10000X;
  • Fig. 18b is a secondary electron image of the film in Fig. 18a at a magnification of 5000X;
  • Fig. 19a is a secondary electron image of another film prepared using a
  • MoNbZr target according to one embodiment of the present invention on a Corning 1737 glass substrate at a magnification of 10000X;
  • Fig. 19b is a secondary electron image of the film in Fig. 19a at a magnification of 5000X;
  • Fig. 20a is a secondary electron image of a film prepared using a MoNbZr target according to one embodiment of the present invention on an Si substrate at a magnification of 10000X;
  • Fig. 20b is a secondary electron image of the film in Fig. 20a at a magnification of 5000X;
  • Fig. 21a is a secondary electron image of another film prepared using a
  • MoNbZr target according to one embodiment of the present invention on an Si substrate at a magnification of 10000X;
  • Fig. 23 b is a secondary electron image of the film in Fig. 21 a at a magnification of 5000X;
  • Fig. 22a is a secondary electron image of another film prepared using a
  • MoNbZr target according to one embodiment of the present invention on an Si substrate at a magnification of 10000X;
  • Fig. 22b is a secondary electron image of the film in Fig. 22a at a magnification of 5000X;
  • Fig. 23a is a secondary electron image of another film prepared using a
  • MoNbZr target according to one embodiment of the present invention on an Si substrate at a magnification of 10000X;
  • Fig. 23b is a secondary electron image of the film in Fig. 23a at a magnification of 5000X;
  • Fig. 24a is a secondary electron image of another film prepared using a
  • MoNbZr target according to one embodiment of the present invention on an Si substrate at a magnification of 10000X;
  • Fig. 24b is a secondary electron image of the film in Fig. 24a at a magnification of 5000X;
  • Fig. 25 is a schematic representation of sheet resistance measurement point locations on a wafer
  • Fig. 26a is a schematic representation of sheet resistance measurements at the locations identified in Fig. 25 on an Si wafer coated with a thin film prepared using a comparative MoTi target;
  • Fig. 26b is a schematic representation of sheet resistance measurements at the locations identified in Fig. 25 on an Si wafer coated with a thin film prepared using a
  • Alloys in accordance with the various embodiments of the present invention include molybdenum in a majority portion.
  • majority portion refers to a percent by weight content of greater than 50%.
  • a majority portion is 75% or more, and even more preferably, a majority portion is 94 to 99%.
  • alloys of the present invention are present in a majority portion of 95 to 98%, and most preferably 95 to 97%.
  • Alloys in accordance with the various embodiments of the present invention include niobium in an alloying amount.
  • alloying amount refers to a percent by weight content of about 0.5 to 6%.
  • an alloying amount is 1 to 5%, even more preferably, 2 to 4%, and most preferably 3 to 4%.
  • Alloys in accordance with the various embodiments of the present invention include a third metal in a doping amount.
  • the term "doping amount" refers to a percent by weight content generally less than an alloying amount.
  • a eloping amount is up to about 2%.
  • a doping amount can be up to about 1%.
  • a doping amount can be from 100 ppm to 1%.
  • a doping amount can be up to 100 ppm.
  • a doping amount can be any amount greater than 1% up to an amount less than an alloying amount.
  • a third metal which is present in alloys in accordance with the various embodiments of the present invention can be selected from the group consisting of nickel, chromium, titanium, zirconium, hafnium, vanadium and mixtures thereof.
  • the third metal comprises zirconium.
  • One embodiment according to the present invention includes alloys which comprise (a) molybdenum present in a majority portion; (b) niobium present in an alloying amount; and (c) zirconium in an amount less than 100 ppm.
  • Another embodiment according to the present invention includes alloys which comprise (a) molybdenum present in a majority portion; (b) niobium present in an alloying amount; and (c) zirconium in an amount greater than 1% by weight.
  • Alloys according to the various embodiments of the present invention can be characterized in that the niobium and the third metal are predominantly bound with the molybdenum in a substitutional solid solution, or as a mixture without alloying of the various metals in the crystal structure, or as a mixture with partial alloying.
  • Alloys according to the various embodiments of the present invention can be prepared by any appropriate melt metallurgical process. Alloys according to the present invention can be further milled and/or ground to produce powders for forming sputtering targets according to the present invention. Powders can also be prepared using an atomization process, e.g., a rotating elctrode process.
  • a suitable melt metallurgy process for preparing an alloy according to the present invention is described in U.S. Patent Application Publication No. US2006/0172454, the entire contents of which are incorporated herein by reference.
  • appropriate amounts of a molybdenum powder, a niobium powder and a third metal powder can be blended, vacuum sintered, vacuum hot pressed or hot isostatically pressed (HIP).
  • Such billets can then subsequently be consolidated by hot deformation processes such as extrusion, forging and/or rolling.
  • the present invention also includes sputtering targets comprising a densified alloy according to any of the various alloy embodiments of the invention.
  • Finished sputtering targets of the present invention have a density of greater than about 90% theoretical density, preferably at least 95% of theoretical density, more preferably at least 98% of theoretical density, and most preferably at least 99.5% of theoretical density.
  • Sputtering targets according to the present invention can be provided through suitable conventional techniques such as a melting process or a powder metallurgy process.
  • suitable conventional techniques such as a melting process or a powder metallurgy process.
  • Various ingot metallurgy methods are known in the art, including, but not limited to, methods such as electron beam melting process, arc melting, plasma melting and the like.
  • melting can be performed at a condition of ultimate vacuum equal to or lower than 4 x 10 "5 torr.
  • melting can be done under an atmosphere between 8 x 10 "4 and 4 x lO- 3 torr.
  • molybdenum powder, niobium powder and third metal powder are blended in lhe proportions described earlier, (or a previously milled and ground alloy powder as described above), and compacted and sintered by various means known in the art. Furthermore, a powdered alloy produced with a predetermined composition through an atomization method or the like may be used in place of or along with elemental powders.
  • the average particle size for the molybdenum powder is preferably between 0.1-25 microns, more preferably less than 5 microns.
  • the desired average particle size is preferably 5-50 microns, more preferably 20-35 microns.
  • the powders can be blended in accordance with powder blending techniques that are well known in the art. For example, mixing may occur by placing the molybdenum, niobium and third metal powders in a dry container and rotating the closed container about its central axis. Mixing is continued for a period of time sufficient to result in a completely blended and uniformly distributed powder. A ball mill or similar apparatus may also be used to accomplish the blending step. The invention is not limited to any particular mixing technique, and other mixing techniques may be chosen if they will sufficiently blend the constituent starting powders.
  • the powder blend is optionally then consolidated in a preliminary compacting step to a density that is from 60-85% of theoretical density. Consolidation can be accomplished by any means known to one skilled in the art of powder metallurgy, e.g., cold isostatic pressing, rolling or die compaction. The length of time and amount of pressure used will vary depending on the desire degree of consolidation to be achieved in this step. For some types of targets, such as tubular, this step may not be necessary. [0078] Following the preliminary consolidation step, the consolidated powder is encapsulated, e.g., in a mild steel can.
  • Encapsulation can also be accomplished by any method that will provide a compact workpiece that is free of an interconnected surface porosity, such as by sintering, thermal spraying, and the like.
  • the term "encapsulation” will refer to any method known to one skilled in the art for providing the compact piece free of interconnected surface porosity. A preferred method of encapsulation is by use of the steel can.
  • the encapsulated piece is compacted under heat and pressure.
  • Various compacting methods are known in the art, including, but not limited to, methods such as inert gas uniaxial hot pressing, vacuum hot pressing, and hot isostatic pressing, and rapid omnidirectional compaction, the CeraconTM process.
  • the encapsulated piece is hot isostatically pressed into the desired target shape, as that method is known in the art, under pressure of 75-300 MPa, more preferably 100-175 MPa, at temperatures of 1000°-1500°C, more preferably 1150"-135O 0 C, for a period of 2- 16 hours, more preferably 4-8 hours.
  • Sputtering targets in accordance with the various embodiments of the present invention can be prepared as rectangular plates or other appropriate shapes using the compaction and sintering methods described above, or as tubular sputtering targets. Larger targets can be prepared by bonding multiple plates such as described in U.S. Patent Application Publication No. US2007/0089984, the entire contents of which are incorporated herein by reference. A suitable method for the preparation of tubular targets is described in U.S. Patent Application Publication No. US2006/0172454, which has been incorporated by reference in its entirety. Methods of making tubular sputtering targets which can also be used to prepare targets according to the present invention are disclosed in U.S. Patent Application Publication No. US2006/0042728, the entire contents of which are incorporated herein by reference.
  • the present invention also includes thin films prepared by sputtering the targets according to the various embodiments of targets according to the invention described herein.
  • Thin films according to the present invention can be prepared by sputtering a target according to the present invention comprising an alloy of molybdenum, niobium and a third metal.
  • Sputtering a target of the present invention includes subjecting the target to sputtering conditions. Any suitable means of sputtering can be employed. DC magnetron sputtering is preferred.
  • Suitable sputtering conditions which can be used in accordance with the methods of the present invention can include a preliminary burn in procedure which can comprise power application to a target, with ramping of the wattage, e.g., from 0 to 100 W, and maintaining a constant power for 10 minutes, ramping to 1000 W over a period of 50 minutes and then maintaining constant power at 1000 W for 2 hours.
  • a burn in procedure e.g., from 0 to 100 W
  • sputtering can be carried out.
  • a substrate Prior to deposition, a substrate can be subjected to chemical cleaning by successive rinsing in ultrasonic baths of acetone and ethyl alcohol. The substrates can then be blown dry in nitrogen and loaded into the deposition chamber for sputtering.
  • Deposition in the sputtering chamber can be carried under various parameters or power applied to the target and gas pressure in the chamber. Suitable power levels applied to the target can be 500 to 2000W and are preferably about 100OW.
  • the substrate is preferably grounded at OV, and a substrate source spacing (SSS) is maintained at about 5 inches.
  • the gas pressure is generally about 1 to 10 mTorr, and more preferably 1 to 5 mTorr.
  • the present invention also includes thin film devices incorporating a thin film made in accordance with the above-described methods of sputtering targets according to the present invention.
  • thin film devices include electronic components such as semiconductor devices, thin film transistors, TFT-LCD devices, black matrix devices that enhance image contrast in Flat Panel Displays, solar cells, sensors, and gate devices for CMOS (complementary metal oxide semiconductor) with tunable work functions.
  • CMOS complementary metal oxide semiconductor
  • Thin films prepared in accordance with the methods of the present invention by sputtering a target according to the invention can be used in any of the aforementioned thin film devices in any suitable manner. Accordingly, for example, a Mo x Nb x M 3 Z ; thin film (M 3 represents a third metal and x+y+z preferably equals 100%) prepared from a target of the present invention can serve as a barrier layer, a conductive wiring after etching, a gate, source and/or drain electrode, etc. Thin films according to the various embodiments of the present invention are preferably used in flat panel displays and solar cells.
  • a thin film in accordance with the various embodiments of the present invention can serve as a diffusion barrier layer (e.g., between an Si substrate and a metallic layer disposed above), or as a protective layer disposed above an underlying layer within a device, or both.
  • a diffusion barrier layer e.g., between an Si substrate and a metallic layer disposed above
  • a protective layer disposed above an underlying layer within a device, or both.
  • Thin films of the present invention can be deposited on any suitable substrate upon which materials can be sputtered.
  • a substrate upon which a thin film according to the present invention is sputtered comprises glass, silicon, steel or a polymeric material.
  • a thin film according to the invention can be deposited onto other thin film silicon/silicon alloy layers.
  • the substrate can comprise glass, silicon and/or stainless steel.
  • the substrate can comprise low sodium glass, other non-alkaline LCD substrates glasses (e.g., Coming® 1737), or combinations thereof.
  • MoNbM 3 thin films prepared in accordance with the present invention can be advantageously used in various thin film devices, particularly preferably in flat panel displays as wiring.
  • the MoNbM 3 thin films exhibit minimal particle generation, good substrate adhesion and low resistivity.
  • uniformity of the MoNbM 3 thin films is comparable to, or even better than, known Mo and MoTi films.
  • Comparative sputtering targets 1, 2, 3 A and 3B were prepared based on known high purity molybdenum alloys where molybdenum comprises substantially the entire target. An additional comparative target based on a known molybdenum-titanium alloy was also prepared. Finally, a target comprising molybdenum, niobium and zirconium was prepared for preparation of a thin films in accordance with an embodiment of the invention. Thin films were then deposited on various substrates under various conditions and evaluated for morphology, particle generation, accumulation rate, microstructure, adhesion, etch rate, resistivity, and uniformity. [0090] Target preparation:
  • Each of the targets were prepared by combining the appropriate metals and conventional melting with electron beam radiation, annealing, extrusion, annealing, forging and annealing. All annealing steps were carried out under a protective atmosphere or in vacuum. Each of the targets used were circular with a thickness of 0.25 inches.
  • each of the silicon, stainless steel (AlSI 304), soda lime glass, and Corning 1737 glass substrates were subjected to chemical cleaning by successive rinsing in ultrasonic baths of acetone and ethyl alcohol, Each of the substrates were then dried with nitrogen and loaded into the deposition chamber.
  • the chamber was then evacuated to a pressure below 5 x 10 ⁇ 6 Torr, and subsequently filled with argon to a pressure of 65 x 10 "3 Torr.
  • the substrates were then sputter etched by applying a negative voltage of 400 V, pulsing at 100 kHz for 30 minutes, and accelerating argon ions to the substrate. After the substrates were sputter cleaned, the argon gas flow was reduced to 2 mTorr and the target was sputter cleaned at
  • the substrate source spacing was maintained at 5".
  • the power applied to the target was 1000 W and the substrate was maintained at 0 V.
  • the deposition chamber employed was a cylindrical vessel with a base pressure of 1 x 10 "6 Torr, manufactured by ACSEL powered by an Advanced Energy-manufactured, Pinnacle power supply having dual channel DC 6 kW power.
  • pores can be discerned in the MoTi target, particularly at 500Ox magnification, such as shown in Fig. 2a.
  • Backscattering electron imaging of the MoTi target at 500x magnification shows that most of the pores were between Mo grains.
  • no pores are discernible in the MoNbZr targets.
  • Particle Generation [00102] Referring to Figs. 5a, 5b, 6a, 6b, and 7, macroparticles were also observed in the thin films produced with the comparative MoTi target. The particles encountered had measurements between 2 and 5 ⁇ m in diameter.
  • Adhesion (Tape Test):
  • 1737 glass having a thickness around 200 nm demonstrated much better adhesion than the coatings prepared on stainless steel and soda lime glass substrates with thicknesses of about 5 ⁇ m.
  • the results are shown below in Table 3a and Table 3b.
  • Ta e test Mo-Ti and Mo-NbZr coatin s; thickness ⁇ 200 nm on Cornin 1737
  • Ta e test Mo-Ti and Mo-NbZr coatin s; thickness ⁇ 5 m.
  • the etch rate of the coatings on silicon substrates prepared using the MoTi sputtering targets were measured by immersing the coatings in a ferricyanide solution at 25 0 C for 30 minutes.
  • the etch rate of the coatings prepared using the MoNbZr target on silicon substrates were measured by immersing the coatings in a ferricyanide solution at 25 0 C for 5 minutes.
  • the etch rates of the coatings prepared using the MoTi target were much lower than those of the coatings prepared using the MoNbZr targets and the coatings prepared from pure molybdenum targets. The results are shown below in Table 4.
  • the uniformity of the thin films was determined through sheet resistance measurements of 37 points of a coating produced on a 4" wafer positioned at 5" from the target. The uniformity of the coatings prepared using each of the targets are comparable. The uniformity evaluation results are shown below in Table 6 and graphically with reference to Figs. 25, 26a and 26b.

Abstract

L'invention porte sur des alliages comprenant : (a) du molybdène présent en quantité majoritaire ; (b) du niobium présent dans une quantité d'alliage ; et (c) un troisième métal choisi dans le groupe constitué par le nickel, le chrome, le titane, le zirconium, l'hafnium, le vanadium et des mélanges de ceux-ci, le troisième métal étant présent dans une quantité de dopage. L'invention porte également sur des cibles de pulvérisation préparées avec ceux-ci, sur des films pulvérisés à l'aide de telles cibles et sur des dispositifs à couches minces contenant de tels films.
EP09739573A 2008-04-28 2009-04-28 Alliages de molybdene-niobium, cibles de pulverisation contenant de tels alliages, procedes de fabrication de telles cibles, films minces prepares a partir de celles-ci et leurs utilisations Withdrawn EP2277191A1 (fr)

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US7837929B2 (en) 2005-10-20 2010-11-23 H.C. Starck Inc. Methods of making molybdenum titanium sputtering plates and targets
US8449817B2 (en) * 2010-06-30 2013-05-28 H.C. Stark, Inc. Molybdenum-containing targets comprising three metal elements
US8449818B2 (en) 2010-06-30 2013-05-28 H. C. Starck, Inc. Molybdenum containing targets
KR20160021299A (ko) 2011-05-10 2016-02-24 에이치. 씨. 스타아크 아이앤씨 멀티-블록 스퍼터링 타겟 및 이에 관한 제조방법 및 물품
JP5958822B2 (ja) * 2011-12-22 2016-08-02 日立金属株式会社 Ｍｏ合金スパッタリングターゲット材の製造方法およびＭｏ合金スパッタリングターゲット材
US9334565B2 (en) 2012-05-09 2016-05-10 H.C. Starck Inc. Multi-block sputtering target with interface portions and associated methods and articles
CN102922225B (zh) * 2012-08-16 2015-05-06 宁夏东方钽业股份有限公司 一种钼靶材的制备方法
JP6284004B2 (ja) * 2013-02-15 2018-02-28 日立金属株式会社 Ｍｏ合金スパッタリングターゲット材の製造方法およびＭｏ合金スパッタリングターゲット材
JP6292466B2 (ja) * 2013-02-20 2018-03-14 日立金属株式会社 金属薄膜および金属薄膜形成用Ｍｏ合金スパッタリングターゲット材
JP6361957B2 (ja) * 2013-03-22 2018-07-25 日立金属株式会社 電子部品用積層配線膜および被覆層形成用スパッタリングターゲット材
AU2015251477A1 (en) * 2014-04-24 2016-11-03 Triumf Target system for irradiation of molybdenum with particle beams

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US20060042728A1 (en) * 2004-08-31 2006-03-02 Brad Lemon Molybdenum sputtering targets
AT8697U1 (de) * 2005-10-14 2006-11-15 Plansee Se Rohrtarget
US7837929B2 (en) * 2005-10-20 2010-11-23 H.C. Starck Inc. Methods of making molybdenum titanium sputtering plates and targets

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