JP2011523978A - Molybdenum-niobium alloy, sputtering target containing such alloy, method for producing such target, thin film produced therefrom, and use thereof - Google Patents

Abstract

  (B) niobium present in an amount of alloy; and (c) a third metal selected from the group consisting of nickel, chromium, titanium, zirconium, hafnium, vanadium and mixtures thereof. An alloy in which the third metal is present in a doping amount; a sputtering target produced using it; a film sputtered using such a target; and a thin film device containing such a film.

Description

BACKGROUND OF THE INVENTION Sputtering is a technique used to produce metal layers in various production processes used in the semiconductor and photoelectric industries. The properties of the film formed during sputtering are related to the properties of the sputtering target itself, such as the size of each crystal grain, and the formation of secondary layers with varying properties. It is desirable to produce a sputter target that provides film homogeneity, minimal particle production during sputtering, and provides the desired electrical and physical properties in the resulting film.

  Various sputtering techniques are used to perform film deposition on the substrate surface. Deposited metal films, such as metal films on flat panel display elements, are formed by magnetron sputtering equipment or other sputtering techniques. A magnetron sputtering apparatus induces gaseous plasma ions, impacts the target, causes surface atoms of the target material to jump out, and deposits on the substrate surface as a film or layer. Conventionally, a planar disk or a sputtering source in the form of a rectangle is used as a target, and the ejected atoms travel along the line of sight line and are deposited on the top surface of the wafer. The plane is parallel to the erosion plane of the target. Tubular shaped sputtering targets are also used and are described, for example, in US Patent Application Publication No. 2007/0042728, the entire text of which is hereby incorporated by reference.

  It may be desirable for the sputtering target to include a material or combination of materials that cannot be manufactured by conventional means such as rolling. In such a case, the target is manufactured by hot isostatic pressing (HIP) powder. Ideally, the target is manufactured in a single process. However, physical limitations in powder packing density and the size of the HIP device require that smaller parts be joined to produce a larger sputtering target. For single-phase targets, conventional methods, such as welding, may be used, multi-phase materials, or edges in the solid state if alloy formation should be avoided for any reason. Bonding to the edge is preferred.

  Interconnects in semiconductors and TFT-LCDs have evolved from aluminum to copper and therefore new diffusion barriers are needed. Titanium provides excellent adhesion properties, while molybdenum contributes to dense barrier stability. Integrated circuits (for semiconductor and flat panel displays) use Mo-Ti as an underlayer or cap layer for aluminum, copper, and aluminum alloys to minimize hillock formation, adjust reflectivity, and Provides protection from physical and chemical corrosion during photolithography.

SUMMARY OF THE INVENTION The present invention generally relates to molybdenum alloys, their use in the production of sputtering targets, methods for producing thin films using such sputtering targets, and thin films produced thereby. More specifically, the present invention comprises a molybdenum comprising a third metal selected from the group consisting of a majority of molybdenum, an alloy amount of niobium, and a doping amount of nickel, chromium, titanium, zirconium, hafnium and / or vanadium. Regarding alloys.

  One embodiment of the present invention consists of (a) molybdenum present in the majority; (b) niobium present in the alloy amount; and (c) nickel, chromium, titanium, zirconium, hafnium, vanadium and mixtures thereof. Including a third metal selected from the group, wherein the third metal is present in a doping amount; provided that when the third metal is zirconium, the doping amount is less than 0.01% by weight or 1 More than mass%.

  Other embodiments of the invention include: (a) Molybdenum present; (b) Niobium present in an alloy amount; and (c) Nickel, Chromium, Titanium, Hafnium, Vanadium, and mixtures thereof. A third metal selected, including an alloy in which the third metal is present in a doping amount.

  Other embodiments of the present invention consist of (a) molybdenum present in the majority; (b) niobium present in the amount of alloy; and (c) nickel, chromium, titanium, zirconium, hafnium, vanadium and mixtures thereof. A sputtering target comprising a densified alloy comprising a third metal selected from the group, the third metal being present in a doping amount. In various preferred embodiments, the present invention comprises (a) molybdenum present predominantly; (b) niobium present in an alloy amount; and (c) nickel, chromium, titanium, zirconium, hafnium, vanadium and mixtures thereof. Including a densified alloy including a third metal selected from the group, wherein the third metal is present in a doping amount; provided that when the third metal is zirconium, the doping amount is 0.01 Includes sputtering targets less than or greater than 1% by weight.

  Yet another embodiment of the present invention is a first selected from the group consisting of molybdenum powder present in the majority, niobium powder present in the amount of alloy, and nickel, chromium, titanium, zirconium, hafnium, vanadium and mixtures thereof. A blend of three metal powders, wherein the third metal is present in a doping amount, provided that the third metal powder is zirconium, the doping amount is less than 0.01% by weight or less than 1% by weight. Providing a bulk formulation; and (b) heating and pressurizing the blend to form a densified sputtering target.

  Still other embodiments of the present invention include: (a) (i) Molybdenum present; (ii) Niobium present in an alloy amount; and (iii) Nickel, Chromium, Titanium, Zirconium, Hafnium, Vanadium and the like Providing a sputtering target comprising a densified alloy comprising a third metal selected from the group consisting of: a third metal present in a doping amount; (b) providing a substrate; And (c) subjecting the target to sputtering conditions to form a coating composed of the target material on the substrate.

  Another embodiment of the present invention includes a thin film device comprising a substrate and a thin film disposed on the substrate, wherein the thin film is produced by any of the embodiments of the sputtering method of the present invention.

  Various embodiments of the present invention can be used by other method embodiments of the present invention to provide thin films for use in various devices that are also embodied by the present invention, in which case the performance of the thin film devices. The properties can provide a sputtering target that is at least comparable to known state-of-the-art thin film devices, is improved in some cases, and the thin film exhibits excellent adhesion to the substrate. Thin films according to the present invention and devices containing thin films according to the present invention can also provide advantageous photolithography properties, thereby improving productivity during manufacture. Among others, the advantage provided by the thin film according to the present invention is a uniform, rapid and controllable etch rate, and improved adhesion (between the substrate and the thin film of the present invention, and later deposition of the thin film of the present invention. Lithographic operations can be significantly improved in combination with a metal film (for example, between copper).

BRIEF DESCRIPTION OF THE DRAWINGS The following summary, as well as the following detailed description of the invention, may be better understood when read in conjunction with the appended drawings. For the purpose of assisting in the description of the invention, representative embodiments that are considered exemplary are shown in the drawings. However, it should be understood that the invention is in no way limited to the precise arrangements and instrumentalities shown.

  In the figure:

FIG. 1a is a secondary electron image of the comparative Mo—Ti target at 1000 × magnification; FIG. 1b is a backscattered electron image of the comparative Mo—Ti target of FIG. 1a at 1000 × magnification. . FIG. 2a is a secondary electron image of the comparative Mo—Ti target of FIG. 1a at 1000 × magnification; FIG. 2b is the backscattered electron of the comparative Mo—Ti target of FIG. 1a at 1000 × magnification. It is a statue. FIG. 3a is a secondary electron image at 200 × magnification of a MoNbZr target according to one embodiment of the present invention; FIG. 3b is a backscattered electron image at 200 × magnification of the MoNbZr target of FIG. 3a. . FIG. 4a is a secondary electron image of the MoNbZr target of FIG. 3a at a magnification of 1000; FIG. 4b is a backscattered electron image of the MoNbZr target of FIG. FIG. 5a is a secondary electron image at 1000 × magnification of a film produced on a Si substrate using a comparative Mo—Ti target; FIG. 5b is at 1000 × magnification of the film of FIG. 5a. It is a backscattered electron image. FIG. 6a is a secondary electron image at a magnification of 20000x for another film produced on a Si substrate using a comparative Mo-Ti target; FIG. 6b is a magnification of 20000x for the film of FIG. 6a. It is a backscattered electron image at. FIG. 7 is a backscattered electron image at 1000 × magnification of the film of FIG. 7a. FIG. 8a is a secondary electron image at a magnification of 10,000 times for a film produced using a comparative Mo—Ti target on a Corning 1737 glass substrate; FIG. 8b is a magnification of 5000 times for the film of FIG. 8a. Is a secondary electron image at. FIG. 9a is a secondary electron image at a magnification of 10,000 times of another film produced on a Corning 1737 glass substrate using a comparative Mo—Ti target; FIG. 9b is a magnification of the film of FIG. 9a. It is a secondary electron image at 5000 times. FIG. 10a is a secondary electron image at a magnification of 10,000 times for another film produced on a Corning 1737 glass substrate using a comparative Mo—Ti target; FIG. 10b is a magnification of the film of FIG. It is a secondary electron image at 5000 times. FIG. 11 a is a secondary electron image at a magnification of 10,000 times of another film produced on a Corning 1737 glass substrate using a comparative Mo—Ti target; FIG. 11 b is a magnification of the film of FIG. It is a secondary electron image at 5000 times. FIG. 12a is a secondary electron image at a magnification of 10,000 times of another film produced on a Corning 1737 glass substrate using a comparative Mo—Ti target; FIG. 12b is a magnification of the film of FIG. It is a secondary electron image at 5000 times. FIG. 13a is a secondary electron image at a magnification of 10,000 times for a film produced using a comparative Mo—Ti target on a Si substrate; FIG. 13b is a magnification of 5000 times for the film of FIG. 13a. It is a secondary electron image. FIG. 14a is a secondary electron image at a magnification of 10,000 times of another film produced on a Si substrate using a comparative Mo—Ti target; FIG. 14b is a magnification of 5000 times that of the film of FIG. 14a. Is a secondary electron image at. FIG. 15a is a secondary electron image at a magnification of 10,000 times of another film produced using a comparative Mo—Ti target on a Si substrate; FIG. 15b is a magnification of 5000 times that of the film of FIG. 15a. Is a secondary electron image at. FIG. 16a is a secondary electron image at a magnification of 10,000 times of another film produced on a Si substrate using a comparative Mo—Ti target; FIG. 16b is a magnification of 5000 times that of the film of FIG. 16a. Is a secondary electron image at. FIG. 17a is a secondary electron image at a magnification of 10,000 times of a film produced using a MoNbZr target according to one embodiment of the present invention on a Corning 1737 glass substrate; FIG. , A secondary electron image at a magnification of 5000 times. FIG. 18a is a secondary electron image at 10000 × magnification of another film produced on a Corning 1737 glass substrate using a MoNbZr target according to one embodiment of the present invention; FIG. 2 is a secondary electron image of a film at a magnification of 5000 times. FIG. 19a is a secondary electron image at 10000 × magnification of another film fabricated on a Corning 1737 glass substrate using a MoNbZr target according to one embodiment of the present invention; FIG. 2 is a secondary electron image of a film at a magnification of 5000 times. FIG. 20a is a secondary electron image at a magnification of 10,000 times of a film produced using a MoNbZr target according to one embodiment of the present invention on a Si substrate; FIG. 20b is a magnification of the film of FIG. It is a secondary electron image at 5000 times. FIG. 21a is a secondary electron image at a magnification of 10000 times of another film produced using a MoNbZr target according to one embodiment of the present invention on a Si substrate; FIG. , A secondary electron image at a magnification of 5000 times. FIG. 22a is a secondary electron image at a magnification of 10,000 times of another film produced using a MoNbZr target according to one embodiment of the present invention on a Si substrate; FIG. , A secondary electron image at a magnification of 5000 times. FIG. 23a is a secondary electron image at a magnification of 10,000 times of another film produced using a MoNbZr target according to one embodiment of the present invention on a Si substrate; FIG. , A secondary electron image at a magnification of 5000 times. FIG. 24a is a secondary electron image at a magnification of 10,000 times of another film produced using a MoNbZr target according to one embodiment of the present invention on a Si substrate; FIG. 24b is a diagram of the film of FIG. , A secondary electron image at a magnification of 5000 times. FIG. 25 is a schematic view of the position of the sheet resistance measurement point on the wafer. FIG. 26a is a schematic diagram of sheet resistance measurements at the locations specified in FIG. 25 on a thin film coated Si wafer produced using a comparative MoTi target; and FIG. FIG. 26 is a schematic diagram of sheet resistance measurements at the locations specified in FIG. 25 on a thin film coated Si wafer manufactured using a MoNbZr target according to an embodiment.

DETAILED DESCRIPTION OF THE INVENTION As used herein, the singular terms “a” and “the” are synonymous, and together with “one or more” and “at least one” are language and Unless otherwise explicitly stated in the context, they are used interchangeably. Thus, for example, reference to “metal” herein or in the appended claims may refer to a single metal or more than one metal. Unless otherwise specified or otherwise indicated, all numbers or expressions used in the specification with respect to amounts of ingredients, reaction conditions, etc. are understood to be modified in all cases by the term “about”. Shall be. Various numerical ranges are disclosed herein. Since these ranges are continuous, they include all values between the minimum and maximum values. Further, all ranges disclosed herein include all narrower ranges disclosed for the same attribute, and any higher or lower range value is disclosed for the same attribute. Can work as an alternative higher or lower value for any other range. Thus, for example, with respect to the range of 1 to 10 and 4 to 6 for the same attribute, the range of 1 to 4, 4 to 10, 1 to 6, and 6 to 10 is also included in the attribute.

  Alloys according to various embodiments of the present invention include a majority of molybdenum. As used herein, the term “major” refers to a content of greater than 50% by weight percent. Preferably, the majority is 75% or more, and even more preferably, the majority is 94-99%. In an even more preferred embodiment of the alloy of the present invention, molybdenum is present in the majority 95-98%, and more preferably 95-97%.

  Alloys according to various embodiments of the invention include an alloy amount of niobium. As used herein, the term “alloy amount” refers to a content of about 0.5-6% by weight percent. Preferably, the alloy amount is 1-5%, even more preferably 2-4%, and most preferably 3-4%.

  Alloys according to various embodiments of the invention include a doping amount of a third metal. As used herein, the term “doping amount” refers to a percent content, generally less than the amount of alloy. Preferably, the doping amount is about 2% or less. In various embodiments, the doping amount may be about 1% or less. In various embodiments, the doping amount may be 100 ppm to 1% or less. In various embodiments, the doping amount may be 100 ppm or less. In various embodiments, the doping amount can be any amount greater than 1% and less than the alloy amount.

  The third metal present in the alloy according to various embodiments of the present invention may be selected from the group consisting of nickel, chromium, titanium, zirconium, hafnium, vanadium, and combinations thereof. In various preferred embodiments of the invention, the third metal comprises zirconium.

  One embodiment according to the present invention comprises an alloy comprising (a) a majority of molybdenum present; (b) niobium present in an alloy amount; and (c) zirconium in an amount of less than 100 ppm. Other embodiments according to the present invention include (a) molybdenum present in the majority; (b) niobium present in the amount of alloy; and (c) alloys containing zirconium in an amount greater than 1% by weight.

  Alloys according to various embodiments of the present invention include niobium and a third metal bonded primarily to molybdenum in a substitutional solid solution, or as a mixture free of alloys of various metals in the crystal structure, or with a partial alloy. Characterized as a mixture.

  Alloys according to various embodiments of the present invention can be made by any suitable metallurgical method. The alloy according to the invention can be further pulverized and / or ground to produce a powder for forming a sputtering target according to the invention. The powder may be produced using an atomization method, such as a rotating electrode method. A suitable metallurgical process for producing the alloys according to the invention is described in US Patent Application Publication No. US 2006/0172454, which is hereby incorporated by reference in its entirety. Optionally, for example, blending appropriate amounts of molybdenum powder, niobium powder, and third metal powder, sintering in vacuum, hot pressing in vacuum, or hot isostatic pressing (HIP) be able to. Such billets are then subsequently consolidated by thermal deformation methods such as extrusion, forging and / or rolling.

  The present invention also includes a sputtering target comprising a densified alloy according to any of the various alloy embodiments of the present invention. The finished sputtering target of the present invention is greater than about 90% of 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. % Density.

The sputtering target according to the present invention can be provided by any suitable conventional technique, such as melting or powder metallurgy. Various ingot metallurgy methods are known in the art and include, but are not limited to, for example, electron beam melting, arc melting, plasma melting and the like. In a suitable electron beam melting method, the melting can be carried out under ultra vacuum conditions of 4 × 10 ⁻⁵ torr or less. In a suitable plasma melting method, the melting may be performed in an atmosphere of 8 × 10 ⁻⁴ to 4 × 10 ⁻³ torr.

  In various suitable powder metallurgy processes, the component powders (ie, molybdenum powder, niobium powder, and third metal powder) are blended in the proportions previously described (or previously ground and ground alloy as described above. Powder) and compacted and sintered by various means known in the art. Furthermore, powdered alloys made with a predetermined composition can be used in place of or in conjunction with elemental powders through an atomization process or the like. The average particle size of the molybdenum powder is preferably 0.1 to 25 microns, more preferably less than 5 microns. For niobium powder and third metal powder, the desired average particle size is preferably 5-50 microns, more preferably 20-35 microns.

  The powder can be blended by powder blending techniques well known in the art. For example, mixing may be performed 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 time sufficient to obtain a complete blend and a homogeneously distributed powder. The compounding process can be accomplished using a ball mill or similar equipment. The present invention is not limited to any particular mixing technique, and other mixing techniques may be selected provided that the ingredients of the starting powder are well blended.

  The powder blend is optionally subsequently consolidated in a pre-compression process to a density of 60-85% of theoretical density. Solidification can be accomplished by any means known to those skilled in the art of powder metallurgy, such as cold isostatic pressing, rolling or die compression. The length of time and the amount of pressure used will vary depending on the desired degree of solidification to be achieved in this process. For some types of targets, for example tubular, this step may not be necessary.

  Following the pre-hardening step, the hardened powder is enclosed, for example, in a mild steel can. Encapsulation may be accomplished by any method that provides a compressed workpiece without interconnected surface porosity, such as sintering, thermal spraying and the like. As used herein, the term “encapsulation” refers to any method known to those skilled in the art to provide interconnected compressed pieces without surface porosity. A preferred method of encapsulation is by use of a steel can.

  After encapsulation, the enclosed piece is compressed under heat and pressure. Various compression methods are known in the art and include, but are not limited to, for example, inert gas uniaxial hot press, vacuum hot press, and hot isostatic press, and rapid omnidirectional compression and Ceracon ™ method Including methods. Preferably, the encapsulated piece is in the desired target shape at a temperature of 1000 ° -1500 ° C., preferably 1150 ° -1350 ° C., under a pressure of 75-300 MPa, more preferably 100-175 MPa, 2-16 Methods for hot isostatic pressing in time, more preferably 4-8 hours, are known in the art. As long as the proper temperature, pressure, and time conditions are maintained, other methods of hot pressing can be used to produce the Mo—Nb—Zr sputtering target of the present invention.

  Sputtering targets according to various embodiments of the present invention can be manufactured as rectangular plates or other suitable shapes, using the compression and sintering methods described above, or as tubular sputtering targets. For example, as described in US Patent Application Publication No. US2007 / 0089984, larger targets can be manufactured by combining multiple targets, the entire text of which is hereby incorporated by reference. A suitable method for the manufacture of the tubular target is described in US Patent Application Publication No. US2006 / 0172454, which is hereby incorporated by reference in its entirety. A method of manufacturing a tubular sputtering target that can also be used to manufacture a target according to the present invention is disclosed in US Patent Application Publication No. US 2006/0042728, the entire text of which is hereby incorporated by reference.

  The invention also includes thin films produced by sputtering targets according to various embodiments of the targets according to the invention described herein. A thin film according to the present invention can be produced by a sputtering target according to the present invention comprising an alloy of molybdenum, niobium and a third metal. Sputtering of the target of the present invention includes subjecting the target to sputtering conditions. Any suitable means of sputtering can be used. DC magnetron sputtering is preferred.

  Suitable sputtering conditions that can be used by the method of the present invention are to increase the wattage, for example from 0 to 100 W, maintain a constant power for 10 minutes, increase to 1000 W over 50 minutes, and then 1000 W The procedure may include pre-combustion, which may include applying power to the target, maintaining a constant power for 2 hours. Subsequent to burning in the procedure and optional substrate cleaning, sputtering may be performed. Prior to deposition, the substrate may be subjected to chemical cleaning of acetone and ethyl alcohol in an ultrasonic bath, a continuous rinse. The substrate can then be dried with a nitrogen blow and introduced into the deposition chamber for sputtering.

  Deposition in the sputtering chamber may be performed under various parameters or power applied to the target and gas pressure in the chamber. A suitable power level applied to the target may be 500-2000W and is preferably about 1000W. The substrate is preferably installed at 0V, and the substrate-to-source spacing (SSS) is maintained at about 5 inches. The gas pressure is generally about 1-10 mTorr, and more preferably 1-5 mTorr.

  The present invention also includes a thin film device comprising a thin film produced by the above-described method of a sputtering target according to the present invention. As used herein, “thin film elements” are electronic components such as semiconductor elements, thin film transistors, TFT-LCD elements, black matrix elements that enhance image contrast in flat panel displays, solar cells, sensors, and adjustable. A gate element for CMOS (complementary metal oxide semiconductor) having a work function is included.

A thin film according to the method of the present invention by sputtering a target according to the present invention can be used in any suitable manner in the thin film element described above. Thus, for example, Mo _x Nb _y M ³ _z thin film prepared from a target of the present invention (M ³ represents a third metal, and x + y + z is preferably equal to 100%), the barrier layer, the conductive after etching Can serve as a wiring, gate, source and / or drain electrode. Thin films according to various embodiments of the present invention are preferably used in flat panel displays and solar cells. Any suitable method for the manufacture of etching, photolithography, and other electronic device structures can be used to form appropriate wiring, electrodes, transistor components from thin films deposited according to the present invention. As a barrier layer, a thin film according to various embodiments of the present invention is disposed as a diffusion barrier layer (eg, between a Si substrate and a metal layer disposed thereon) or over a layer underlying the device. It can act as a protective layer or both. The use of a molybdenum layer as a barrier layer is described, for example, in US Pat. No. 7,352,417, the full text of which is hereby incorporated by reference.

  The thin films of the present invention can be deposited on any suitable substrate on which materials can be sputtered. In various preferred embodiments of the present invention, the substrate on which the thin film according to the present invention is sputtered comprises glass, silicon, steel or a polymer material. Furthermore, thin films according to the present invention can be deposited on other thin film silicon / silicon alloy layers. In various preferred embodiments, the substrate may comprise glass, silicon and / or stainless steel. In various particularly preferred embodiments, the substrate may comprise low sodium glass, other alkali-free LCD substrate glass (eg, Corning® 1737), or combinations thereof.

The MoNbM ³ thin film produced according to the present invention can be advantageously used as wiring in various thin film devices, particularly preferably in flat panel displays. The MoNbM ³ thin film exhibits minimal particle formation, good substrate adhesion and low resistance. As discussed below, the homogeneity of MoNbM ³ thin films is comparable to or better than known Mo and MoTi films.

  The invention will now be described in more detail with reference to the following non-limiting examples.

Examples Comparative sputtering targets 1, 2, 3A and 3B were manufactured based on known high purity molybdenum alloys in which molybdenum substantially constitutes the entire target. Additional comparative targets based on known molybdenum-titanium alloys were also produced. Finally, a target comprising molybdenum, niobium and zirconium was produced for the production of thin films according to embodiments of the present invention. Thin films were then deposited on various substrates under various conditions and evaluated for morphology, particle formation, accumulation rate, microstructure, adhesion, etching rate, resistivity, and homogeneity.

Target manufacturing:
Individual targets were produced by combining the appropriate metals with conventional melting using electron beam irradiation, annealing, extrusion, annealing, casting and annealing. All annealing steps were performed in a protective atmosphere or in vacuum. The individual targets used were circular with a thickness of 0.25 inches.

Board and board manufacturing:
Prior to thin film deposition on the substrate, individual silicon, stainless steel (AISI 304) soda lime glass, and Corning 1737 glass substrates were subjected to chemical cleaning of acetone and ethyl alcohol in an ultrasonic bath and subsequently rinsed. Thereafter, the individual substrates were dried with nitrogen and introduced into the deposition chamber.

The chamber was then evacuated to a pressure below 5 × 10 ⁻⁶ Torr and subsequently filled with argon to a pressure of 65 × 10 ⁻³ Torr. Thereafter, the substrate was sputter etched by applying a negative voltage of 400 V, applying a pulse at 100 kHz for 30 minutes, and accelerating argon ions on the substrate. After cleaning the substrate by sputtering, the flow of argon gas was reduced to 2 mTorr, and the target was cleaned by sputtering at 500 W (DC) for 5 minutes. While the target was cleaned by sputtering, a shutter was placed in front of the target to prevent deposition on the substrate.

  Deposition on the substrate was performed using a fixed power application to the target and under various conditions of gas pressure and time. The conditions are shown in Table 1 below.

The substrate / source spacing was maintained at 5 ″. The voltage applied to the target was 1000 W, and the substrate was held at 0V. The deposition chamber used was a cylindrical vessel with a base pressure of 1 × 10 ⁻⁶ Torr, powered by Advanced Energy supplied by Advanced Energy, manufactured by ACSEL and having a power of 2 channels DC 6 kW. .

Thin film evaluation:
Individual different substrates were supplied with thin films using individual manufactured sputtering targets. The coated substrate was then evaluated as follows.

Target morphology:
Several pores were observed in the erosion track of the comparative molybdenum-titanium film. Based on the backscattered electron image, it is clear that some molybdenum and titanium grains are separated and most of the pores are in brighter regions (consisting of molybdenum grains with a higher number of atoms). In contrast, in the film produced from the MoNbZr sputtering target, no separation of pores or molybdenum, niobium and zirconium grains was observed. Furthermore, the grain size in the MoNbZr sputtering target was much larger than in the comparative target. Referring to FIGS. Ia, Ib, 2a and 2b, pores are identified in the MoTi target, in particular at a magnification of 5000 times as shown in FIG. 2a. The backscattered electron image of the MoTi target at 500x magnification shows that most of the pores are between Mo grains. Referring to FIGS. 3a, 3b, 4a and 4b, no pores are observed in the MoNbZr target.

Particle generation:
Referring to FIGS. 5a, 5b, 6a, 6b and 7, macroparticles are also observed in thin films produced using a comparative MoTi target. The particles encountered were measured to have a size of 2-5 μm in diameter. The macroparticle density estimate is about 4 macroparticles in a 50 μm × 50 μm region. In contrast, no macroparticles were observed in films fabricated using a MoNbZr target at 5 mTorr, 3 mTorr, or 1 mTorr on a silicon substrate.

Accumulation speed:
The accumulation rate of coatings produced using individual targets, both on silicon and on Corning 1737 glass substrates, was measured using a scanning electron microscope (SEM). The data is shown in Table 2 below.

Fine structure:
The microstructure of films produced using MoTi and MoNbZr sputtering targets on silicon and Corning 1737 glass substrates was also observed using SEM. As the deposition pressure decreased, the films produced using both targets became denser. The coating on the 1737 glass substrate was denser than the coating on the silicon substrate. With reference to FIGS. 8a to 24b, films of similar density are shown.

Adhesion (tape test):
The adhesion of coatings produced using MoTi and MoNbZr sputtering targets was measured using a tape test. A coating made on Corning 1737 glass having a thickness of about 200 nm demonstrated much better adhesion than a coating made on stainless steel and soda lime glass having a thickness of about 5 μm. . The results are shown in Table 3a and Table 3b below.

Etching rate:
The etch rate of coatings produced using a MoTi sputtering target on a silicon substrate was measured by immersing the coating in a ferricyanide solution at 25 ° C. for 30 minutes. The etch rate of coatings produced using a MoTiZr target on a silicon substrate was measured by immersing the coating in a ferricyanide solution at 25 ° C. for 5 minutes. The etch rate of coatings made using MoTi targets was much lower than that of coatings made using MoNbZr targets and coatings made from pure molybdenum targets. The results are shown in Table 4 below.

Resistivity:
The sheet resistance of the selected molybdenum film was measured using the four probe method. The results are shown in Table 5 below. As shown in Table 5, the resistivity of the coating produced using the MoTi target was much higher than that of the coating produced using the MoNbZr sputtering target.

Homogeneity:
Thin film homogeneity was measured by 37 sheet resistance measurements of coatings produced on 4 ″ wafers placed 5 ″ from the target. The homogeneity of coatings produced using individual targets is comparable. The homogeneity assessment results are shown in Table 6 below and illustrated with respect to FIGS. 25, 26a and 26b.

  It will be appreciated by those skilled in the art that the embodiments described above can be modified without departing from the broad inventive concept. Accordingly, it is to be understood that the invention is not limited to the particular implementations disclosed, but is intended to encompass modifications within the spirit and scope of the invention as defined by the appended claims.

Claims (24)

  (B) niobium present in an amount of alloy; and (c) a third metal selected from the group consisting of nickel, chromium, titanium, zirconium, hafnium, vanadium and mixtures thereof. An alloy in which the third metal is present in a doping amount, provided that when the third metal is zirconium, the doping amount is less than 0.01 mass% or greater than 1 mass%.   The alloy of claim 1, wherein the third metal is selected from the group consisting of nickel, chromium, titanium, hafnium, vanadium, and combinations thereof.   The alloy according to claim 1, wherein the doping amount is less than 0.01% by mass.   The alloy according to claim 1, wherein the doping amount is greater than 1% by weight.   The alloy according to claim 2, wherein the doping amount is less than 0.01% by mass.   The alloy according to claim 2, wherein the doping amount is greater than 1% by weight.   The alloy according to claim 2, wherein the doping amount is 0.01 to 1% by mass.   The alloy according to claim 1, wherein the alloy amount is 0.5 to 10% by mass.   The alloy according to claim 2, wherein the alloy amount is 0.5 to 10% by mass.   A sputtering target comprising the densified alloy according to claim 1.   A sputtering target comprising the densified alloy according to claim 2.   (A) a blend of molybdenum powder present in the majority, niobium powder present in the amount of alloy, and a third metal powder selected from the group consisting of nickel, chromium, titanium, zirconium, hafnium, vanadium and mixtures thereof. Providing a formulation in which the third metal is present in a doping amount, provided that the doping amount is less than 0.01% by weight or less than 1% by weight when the third metal is zirconium. And (b) heating and pressing the formulation to form a densified sputtering target.   (Ii) selected from the group consisting of (i) molybdenum present in the majority; (ii) niobium present in the alloy amount; and (iii) nickel, chromium, titanium, zirconium, hafnium, vanadium and combinations thereof. Providing a sputtering target comprising a densified alloy comprising three metals and a third metal present in a doping amount, (b) providing a substrate, and (c) subjecting the target to sputtering conditions Providing a coating comprised of the target material on the substrate.   (A) providing a sputtering target according to claim 10; (b) providing a substrate; and (c) subjecting the target to sputtering conditions to form a coating composed of the target material on the substrate. Method.   14. A thin film device comprising a substrate and a thin film disposed on the substrate and produced by the method of claim 13.   15. A thin film device comprising a substrate and a thin film disposed on the substrate and produced by the method of claim 14.   The thin film element according to claim 15, wherein the substrate is transparent.   The thin film element according to claim 17, wherein the transparent substrate comprises glass and the thin film element is a flat panel display.   The thin film element of claim 15, wherein the substrate comprises one or more selected from the group consisting of glass, steel, polymer, and combinations thereof, and the thin film element is a solar cell.   The thin film element according to claim 16, wherein the substrate is transparent.   The thin film element according to claim 20, wherein the transparent substrate comprises glass and the thin film element is a flat panel display.   The thin film element of claim 16, wherein the substrate comprises one or more selected from the group consisting of glass, steel, polymer, and combinations thereof, and the thin film element is a solar cell.   The thin film element of claim 15, wherein the substrate comprises silicon.   The thin film device according to claim 16, wherein the substrate comprises silicon.

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