TWI438295B - Fine grained, non banded, refractory metal sputtering targets with a uniformly random crystallographic orientation, method for making such film, and thin film based devices and products made therefrom - Google Patents

Description

Fine particle non-ribbon refractory metal splash target with uniform random crystal orientation, method for manufacturing the film, and film device and product manufactured thereby

The present application claims priority to the following patent applications: U.S. Patent Application Serial No. 60/915,967, filed on May 4, 2007, and U.S. Patent Application Serial No. 11/937,164, filed on November 8, 2007, The entire contents of the documents are hereby incorporated by reference for all utility purposes.

The physical properties of the splash target for physical gas deposition (PVD) in the conventional electronics industry greatly influence the final properties of the film being produced, and in fact, contribute to the goal of enhancing the manufacture of high quality thin film devices and circuit structures. The characteristics are: fine and uniform fine-grained structure; random and uniform random crystal orientation of the individual particles; a microstructure that is substantially constant throughout the entire body of the target when viewed on a macroscopic scale; can be copied from one target to another a microstructure of the target; and a microstructure that is substantially 100% dense and provides high strength bonding between the particles.

Especially in the targets of tantalum (Ta) and niobium (Nb), it is extremely difficult to obtain such characteristics, which are caused by the fact that high-purity niobium and tantalum are refined and purified by electron beam melting and casting into a cold water cooling mold. The resulting casting mold has a number of extremely large particles whose length and width are measured in centimeters by centimeters. These very large particles require extensive and expensive heat treatment to reduce particle size and reduce the crystal alignment of individual particles (reduced texture). Thermal treatment is limited in the reduction of particle size, the resulting random crystallization and the uniformity of the resulting microstructure, usually from mold casting The target material still contains a large degree of non-uniformity in the particle size and texture band, with a common particle size and texture that is not characteristic of the overall particle size and texture of the entire target.

The importance and size of this problem is raised in U.S. Patent No. 6,193,821, in which the first side is forged or side-pressed by several molds, followed by tipping forging or tipping. U.S. Patent Publication No. 2002/0112789 A1 describes a process which utilizes tip forging, then pull back forging, then side forging, and finally a cross-twisting process to provide a particle having {100} and {111} orientations. mixing. In U.S. Patent Nos. 6,331,233 and 7,101,447, the inventors clearly indicate a complex three-step process comprising a plurality of deformed and annealed parts. Although this complex processing route successfully refines the particle size, the process still creates a dominant {111} texture.

U.S. Patent Publication No. 2005/0155856 A1 describes a splash target having a preferential (222) orientation over a limited portion of the target thickness, the patent publication claiming to improve the uniformity of the thickness of the splash film.

Other patents understand the inherent advantages of starting with tantalum metal powder rather than solid tantalum molds. U.S. Patent Nos. 5,580,516 and 6,521,173 illustrate the cold compression of tantalum powder into several short metal strips which can then be processed in a wide range of thermal/mechanical process techniques. To create a number of fully dense short metal strips that can produce a splash target. U.S. Patent No. 6,770,154 teaches that a short strip of powder is strengthened to full density, followed by rolling and annealing to provide a uniform but non-random particle structure. U.S. Patent No. 7,081,148 is extended over such processes of U.S. Patent No. 6,770,154 to include a resulting splatter target which is at least 99.99% pure ruthenium.

U.S. Patent No. 7,067,197 describes a powder metallurgy process which first surface tantalum nitride powder prior to compaction. The surface nitrided powder can then be compacted by a succession of at least 23 different processing steps which must retain the high nitrogen content of the powder. One of the least appreciated steps is spray deposition, but there is no mention of any type of spray deposition technique, namely plasma spray, low pressure plasma deposition, flame spray, high velocity oxygen fuel, etc., which are among the many processes currently used. Some processes.

World Patent Nos. WO 2006/117145 and WO 2006/117144 describe several cold spray processes for producing a ruthenium coating, which are incorporated herein by reference for use in the disclosure of such cold spray processes.

Due to the fact that the process of combining the 钽 and 支持 into the support board is extremely expensive, there is also an economic interest in the recovery or reprocessing or repair of the used target, plus only the need to replace the entire target before splashing. The fact that about 25 to 30% of a planar target and about 60 to 70% of a rotating target. Therefore, the recovery of the cockroaches that have never been used is of great interest.

U.S. Patent Publication No. 2004/0065546 A1 discloses a method of hydrogenating the target to make the crucible brittle to allow the crucible to be separated from the support sheet, ground into a powder, and reused as a powder material in the manufacture of the mold. U.S. Patent Publication No. 2006/0032735 discusses the use of laser beams and other focused energy sources for simultaneous melting and welding of powders that feed a worn area of the target to fill the space created by the splash. Of course all of these techniques generate a large amount of heat and require the support plate to be removed from the target prior to repair. Furthermore, as is well known to those skilled in the art, when melting occurs, the powder solidifies in a targeted manner and the resulting microstructure is sturdy. Texture composition.

A target must be machined to a final set size before being used, and then welded, brazed or spread bonded to a high heat transfer support plate for installation in a splash machine.

Splash targets are used to make a wide range of films, including reflections for window glass and low emissivity coatings, photovoltaics (molybdenum), narrow-pass filters (钽-铌). However, their most well-known use may be in integrated circuits in which a layered splash film is used to fabricate basic switching devices, and circuit structures for connecting the switching devices to fabricate functional electronic components (integrated circuits) , flat panel display, etc.). As mentioned above, the quality of the films produced, and thus the quality of the products produced using the film technology, are highly dependent on the quality of the target that splashes them out.

Cold spray or power spray (see U.S. Patent Nos. 5,302,414, 6,502,767 and 6,759,085; "Analysis of Tantalum Coatings Produced by the Kinetic Spray Process" by Van Steenkiste et al.", Thermal Spray Journal of Science and Technology, Vol. 13 (2), June 2004, pages 265 to 273; US Patent No. 6,139,913 and U.S. Patent Publication Nos. 2005/0120957 and 2005/0252450) are emerging industrial technologies that are being used to solve many Industrial manufacturing challenges (see also U.S. Patent Nos. 6,924,974; 6,444,259; 6,491,208 and 6,905,728). All of the above references are incorporated herein by reference for their disclosure of cold spray or power spray.

Cold spray utilizes a high velocity gas jet to rapidly accelerate a powder having a size generally less than about 44 microns to a high speed so that the powder adheres to the surface upon impact of a surface to form a complete, well bonded and dense coating. Floor. It has been suggested to spray the tantalum powder onto a variety of substrates (including steel) (see, for example, "Analysis of Tantalum Coaitngs Produced by the Kinetic Spray Process" by Van Steenkiste et al." , Journal of Thermal Spray Technology, Vol. 13, No. 2, June 2004, pp. 265-273; "Cold spraying-innovative layers for new applications" by Marx et al. (Cold Spray - Innovation Layer for New Applications) "", Thermal Spray Technology Journal, Vol. 15, No. 2, June 2006, pp. 177-183; and "The Cold Spray Process and its Potential for Industrial Applications" by Gartner et al. Potential for industrial applications)", Journal of Thermal Spray Technology, Vol. 15, No. 2, June 2006, pp. 223-232). This cold spray does not have to be fully heated by heating the powder to a temperature near or above its melting point, as is the case with conventional thermal spray processes. The fact that a dense coating can be formed at a low temperature raises many advantages. Such advantageous points include no oxidation, high density deposits, solid compaction, no heat induced stress, in which case in particular no substantial substrate heating.

Achieving the power spray can be carried out, for example, by injecting a powder having a particle diameter of more than 65 μm into a lava-type de laval-type nozzle, carried away by a supersonic flow, and accelerated to a high speed due to a resistance effect. The kinetic energy of the particles is converted into tension and heat upon impact with the surface of the substrate via plastic deformation. The particles melt in the process.

In the case of manufacturing a cathode or electron splash target bullion for the field of physical gas deposition (PVD), it is preferred that the substrate be heated to a limited extent. The target material is often a high melting temperature ("TM") refractory metal (钽TM is 2998 degrees Celsius), while The support plate for the target is selected for its high thermal conductivity, and is usually copper or aluminum (the aluminum TM is 660 degrees Celsius), both of which are low melting temperatures. Therefore, it is not possible to deposit a refractory metal on a low-melting-temperature support plate using other thermal spray processes that require the powder to be heated to or near its melting point. The current implementation method is to completely separate the target from the support plate, and then use welding, brazing, diffusion bonding or explosion bonding techniques to combine the target with the support plate. Since the cold spray or power spray does not substantially heat the powder, it can be used to make several targets directly on the support plate and to repair the used target without removing the target from the support plate.

It is an object of the present invention to create a splash target having a uniform fine and randomly crystallized microstructure throughout the body of the target.

It is yet another object of the present invention to provide a process that can cost-effectively produce such a microstructure and replicate the structure from one object to another. Preferably, the process does not require melting. Several examples of such processes include cold spray or power spray processes.

It is a further object of the present invention to provide a cost effective repair or recovery process that provides the same or preferred microstructure of the repair target as the original.

Yet another object of the present invention is to develop a target recovery process by a method that does not require melting, such as a cold spray or a power spray.

We have discovered a technique and several parameters that allow direct fabrication of a fine-grained structure having a randomly oriented shape to pass the entire thickness of the target without the above-described complicated process, and one that allows for the fabrication of several desired micros directly on the support plate. The goal of the structure and the technology that allows for the simple repair of used targets. The technique No melting process is used. Several examples of such processes include cold spray or powered spray of fine metal powder such as, but not limited to, tantalum powder.

Moreover, the present invention provides a method of splashing whereby any of the above-described splash targets are treated in a plurality of splash conditions and thereby subjected to splashing. Any suitable splash method can be used in the present invention. Suitable methods of splashing include, but are not limited to, magnetron splash, pulsed laser splash, ion beam splash, triode splash, and combinations thereof.

Moreover, the present invention provides a splash target comprising a uniform fine grain structure substantially less than 44 microns, the splash target having no preferred texture orientation when measured by an electron backscatter diffractometer ("EBSD") ( That is, it contains substantially a plurality of randomly oriented particles, comprising a plurality of particles substantially less than 44 microns, and the body throughout the target exhibits no particle size or texture band.

Furthermore, the present invention provides an object which, in an annealed state, comprises a large particle size of equal parties, the particle size being smaller than the starting powder particle size.

Furthermore, the present invention provides a splash target having a crystalline particle structure characterized by substantially no interparticle diffusion, without a preferred texture orientation as measured by an electron backscatter diffractometer ("EBSD"), and throughout The ontology of the target shows no particle size or texture banding.

In addition, the present invention provides a process for manufacturing a splash target assembly in an additive manner by depositing the target materials directly on a support plate for the target assembly via a powder spray in a single step. The deposits and substrates are machined to the final target assembly size.

The invention also provides a method of manufacturing a film comprising the steps of: (a) splashing the above-mentioned splash target; (b) removing a plurality of metal atoms from the target; (c) forming a film comprising the above metal on a substrate.

We have found a technique and several parameters that allow for the direct fabrication of several targets without the complex processing described above, and allow for the fabrication of several targets having the desired microstructure directly on the support board, with or without prior use. A technique in which the target is removed from the support board to simply repair the used target. This technique does not use a melting process, and several examples of such processes include cold spray or power spray of fine metal powder such as, but not limited to, tantalum powder.

This technique can also be used for recovery or repair of a splash target.

As the gas which forms a gas powder mixture with the metal powder, an inert gas is usually used. The inert gas according to the present invention includes, but is not limited to, argon, helium or less reactive nitrogen, or a mixture of two or more thereof. In special cases, air can also be used. If safety regulations are met, hydrogen or a mixture of hydrogen and other gases may also be considered, and it may be advantageously used due to the extremely high sonic speed of hydrogen. In fact, the speed of sound of hydrogen is 30% greater than the speed of sound of 氦, and the speed of sound of 氦 is about three times that of nitrogen. The sound velocity of air at 20 degrees Celsius and 1 atmosphere (atm) is 344 meters per second, compared to the atomic weight of air 28.96, hydrogen with an atomic weight of 2.016 is the lightest element, and its density is about 14 times smaller than air and has The speed of sound at 1308 meters per second.

In a preferred version of the process, the spray comprises the steps of: providing a spray aperture adjacent a surface to be coated by splashing; providing a particulate material powder to the spray aperture, the particulate material being selected from the group consisting of Group of 铌, 钽, tungsten, molybdenum, titanium, zirconium, at least a mixture of the two a compound or alloy thereof with another or other metal having a particle size of from 0.5 to 150 micrometers (μm), preferably from 5 to 80 micrometers, and most preferably from 10 to 44 micrometers, the powder being under pressure Providing an inert gas to the spray hole at an elevated non-flow pressure, and providing a spray of the particulate material and gas onto a surface of a substrate to be coated; placing the spray hole in a low ambient pressure region; The ambient pressure is substantially less than the no-flow pressure in front of the spray orifice to provide a substantial acceleration of the spray of particulate material and gas onto the surface to be coated; and thereby the substrate is coated with a hard coat when the coating is annealed Floor. Note that the hardened coating can be removed from the substrate before or after annealing.

In another preferred version of the process, the spray is performed using a cold spray gun and the target to be coated and the cold spray gun are at a pressure below 80 kPa or above 0.1 MPa ( MPa) an inert chamber.

The term cold spray is used throughout the application and it should be understood that a power spray process can be used in place of the cold spray process in the example of only the cold spray process.

In another preferred version of the process, a power unit is utilized to perform the spray. Using a particle diameter of less than 50 microns with a higher particle velocity and generally lower particle temperature than a cold spray process, the power process uses a larger particle size distribution between 65 and 200 microns and a higher particle temperature to produce a coating. . Since kinetic energy is proportional to the cube of the particle diameter and the square of the particle velocity, the total kinetic energy available for plastic deformation is typically greater than that of the cold spray process. Performing the power spray is to use a longer spray behind the throat area The length of the mouth (eg 280 mm (mm) versus standard 80 mm) and higher gas temperatures (eg above 200 degrees Celsius, but well below the melting point of the material). Higher particle velocities improve the coating characteristics compared to coatings produced with shorter nozzles, resulting in high levels of plastic deformation, increased adhesion, lower porosity, and higher work hardening.

Typically, the refractory metal has a purity of at least 99%, such as 99.5% or 99.7%, 99.9%, based on metal impurities, advantageously having a purity of at least 99.95%, in particular at least 99.995% or at least 99.999%, especially at least 99.9995% purity.

Typically, if an alloy is used in place of a single refractory metal, then at least the refractory metal (but preferably the alloy as a whole) has this purity so that a corresponding high purity coating can be produced.

In one of several embodiments according to the present invention, the total content of non-metallic impurities such as oxygen, carbon, gas or hydrogen in the powder should advantageously be less than 1,000 ppm, preferably less than 500 ppm, and more preferably less than 150 ppm.

In one of several embodiments according to the present invention, the oxygen content is 50 ppm or less, the nitrogen content is 25 ppm or less, and the carbon content is 25 ppm or less.

The metal impurity content is advantageously 500 ppm or less, preferably 100 ppm or less, and most preferably 50 ppm or less, especially 10 ppm or less.

Such metal powders can be purchased commercially or can be formulated using a reducing agent to reduce refractory metal compounds and preferably subsequent deoxidation. For example, tungsten oxide or molybdenum oxide is reduced in a hydrogen stream at elevated temperature. This formulation is disclosed, for example, in the book "Tungsten (Tungsten)" by Schubert, Lassner (Kluwer Academic / Charging Press, New York, 1999), or Brauer, "Handbuch der Praparativen Anorganischen Chemie" (Ferdinand Enke Verlag Stuttgart, 1981, p. 1530).

In the examples of ruthenium and osmium, the formulation is carried out in most of the examples by reducing an alkali heptane fluoro-antimonate and an alkaline earth metal heptane fluoro-antimonate by an alkali metal or an alkaline earth metal. Or an oxide such as sodium heptane citrate, potassium heptane citrate, sodium heptane fluoroantimonate or potassium heptanofluoride. The reduction can be carried out, for example, in a salt which is melted by the addition of sodium, or in a gas phase in which calcium or magnesium vapor is advantageously used. The refractory metal compound may be mixed with an alkali or alkaline earth metal and the mixture may be heated. Hydrogen environments can be advantageous, and many suitable processes are known to those skilled in the art, and process parameters that select suitable reaction conditions are also known. Several suitable processes are described, for example, in U.S. Patent No. 4,483,819 and World Patent No. 98/37,249.

For example, as disclosed in the World Patent No. WO 01/12364 and the European Patent No. EP-A-1200218, if a low oxygen content is desired, a further process for formulating a pure powder having a low oxygen content includes the use of an alkaline earth metal. As a reducing agent to reduce a refractory metal hydride.

Furthermore, the present invention relates to a process for reprocessing a splash target (a metal source in a metal cathode splash), wherein a gas flow rate forms a gas/powder mixture with a material powder selected from the following: a group consisting of ruthenium, rhodium, tungsten, molybdenum, titanium, zirconium, or a mixture of two or more thereof, or an alloy thereof with at least two or with other metals, the powder having a particle size of from 0.5 to 150 microns, wherein The gas flow is given a supersonic velocity and the supersonic jet is directed to the surface of the article to be reprocessed or fabricated.

A splash target is a source of metal in a metal cathode splash. These splash targets are used in the manufacture of integrated circuits, semiconductors, and other electrical, magnetic, and optical products. During the splash process, the metal surface of the splash target is typically unevenly worn, resulting in a groove on the surface. In order to avoid the material contamination of the support plate or even the unfavorable penetration of the coolant, the splash target will not be used up until the refractory metal target is used up, but it is quickly stopped in advance, so when a new splash must be used Only a small amount of expensive refractory metal is used when hitting the target. Due to the need to remove the support plate and connect to the new refractory metal plate, most splash targets can only be sold as scrap or recycled. However, the support board is here a part of the lower value of the splash target.

There is therefore a need for a technique for providing reprocessing of a splash target or the possibility of recovering a splash target without having to disassemble the support plate, or providing direct deposition of splash material to the support plate or for a rotating target support tube. possibility.

For this purpose, the use of a groove in the splash target to refill the particular refractory metal, preferably without the use of melting, can be accomplished, for example, by the cold spray or power process described above. For this purpose, the supersonic jet of the gas/powder mixture is directed onto the groove and moved over the entire length and shape of the groove. This action is repeated as needed to refill the groove so that the surface of the splash target re-forms an almost completely flat area and/or the fill material is slightly above the surface of the splash target. Preferably, the supersonic jet of the gas/powder mixture is then directed onto the remaining surface of the splash target and directed over the entire length, width and shape of the splash target surface until complete A uniform thickness planar layer covering the surface of the splash target. The resulting rough surface can then be polished by conventional processing to obtain the desired smooth surface.

We note that if the original target is made by conventional mold metallurgy or powder metallurgy techniques, the cold spray repair will have a finer particle size and a more random structure than the original target. If the original target is made of a cold spray, the repair will have a microstructure that is similar to the original target if it is difficult to distinguish. However, there will be a clear dividing line between the original target and the repair zone, which can be seen in the profile of the target.

The target is applied directly to a support plate during the manufacture of a new splash target. Depending on the configuration of the target, the supersonic jet of the gas/powder mixture is directed onto the entire surface of the support plate of the splash target and the entire length, width and shape of the splash target surface is directed Above, it results in considerable material savings until a uniform and thick enough planar layer that completely covers the splash target surface, or only the contact area of the plasma is applied.

Preferably, the target has a thickness of between 2 and 20 mm, more preferably between 3.0 and 15 mm, still more preferably between 5 and 12 mm, still more preferably between 8 and 10 mm.

The purity and oxygen content of the resulting target should be less than 5%, and preferably no more than 1%, of the powder.

This can be advantageously achieved if the target to be retreated is applied under an inert gas. Argon is advantageously used as the inert gas because of its higher density than air. Especially if the target of the splash is in a container that prevents argon from leaking or flowing out and continuously filling argon, argon tends to cover the object to be coated and still exists. . Other inert gases that operate in accordance with the present invention have been discussed above.

The process according to the invention is particularly suitable for the treatment or manufacture of several splash targets On the one hand, because of the preferred crystal orientation which can be changed at different intervals during the manufacturing process of the thermal mechanism, no uniform texture is obtained, but instead a so-called strip shape, that is, several regions with different preferred orientations occur. In the thermal mechanism, only very complicated and expensive processes can be used to avoid this situation. In contrast, a uniform random texture can be obtained by the process according to the invention, wherein no detectable preferred orientation occurs above the thickness of the refractory metal target.

Similarly, a uniform and random particle size distribution and particle size distribution are obtained in these targets so that, if not desired, ribbons of different particle sizes or particle sizes are not obtained. The particle size or texture band in the splash target is particularly bad because of the splash rate and uniform film variation.

In the process of applying powder to the splash target and melting the powder, it is known from experience that bubble and particle growth occur. This situation will not be seen in the process according to the invention.

After application of the target, the surface of the splash target is typically ground and polished to provide a suitable smooth surface, which may be performed by conventional processes in accordance with prior art techniques.

In the manufacture of a new splash target, the target is applied to a support member, such as a support plate, typically a copper or aluminum, or a plate made of an alloy of at least one of the metals and the hinge. . This support board can contain several channels with a cooling medium.

The support plate and thus the splash target may be in the form of a plane, rod, cylinder, block or any other desired shape, plus additional structural components, liquid cooling coils and/or larger coolant reservoirs and/or Complex flange or Other mechanical or electrical structures.

Objects made in accordance with the present invention, or targets produced during manufacture or reprocessing of a splash target, may have high purity and low oxygen content.

The resulting target has a gaseous impurity content that deviates from the starting powder content at which this target is made by no more than 50%, or no more than 20%, or no more than 10%, or no more than 5%, or no more than 1%. In this context, it should be understood that the term deviation is specifically meant to increase; the object of the invention should therefore advantageously have a gaseous impurity content which exceeds the starting powder content by no more than 50%.

The powder hardened on the surface preferably has an oxygen content which deviates from the starting powder by an oxygen content of not more than 5%, especially not more than 1%.

In an advantageous embodiment, the targets also have a density of at least 97%, preferably greater than 98%, especially greater than 99% or 99.5%. The density of the target is here a measure of the containment nature and porosity of the target. A 97% density of a target indicates that the target has a density of 97% of the bulk material. A closed, almost completely pore-free target typically has a density of more than 99.5%. The density can be determined by image analysis of a cross-sectional image (profile) of the target, or by helium pyknometry, which is less advantageous because in the case of extremely dense targets, no detection is detected. Pore that exists in the target and is removed from the surface, so that it has a lower porosity than the actual one. The density can be determined by image analysis by first determining the total area of the object to be investigated in the image profile of the photomicrograph, and then correlating this area with the area of the pores. By this method, the pores removed from the surface and close to the substrate interface are also recorded. At least 97% of the high density is particularly important in the manufacture and reprocessing of splash targets, preferably greater than 98%, especially It is 99% or 99.5% larger.

These targets show high mechanical strength due to their high density and high deformation of the particles. In the case of ruthenium, if the gas forming a gas/powder mixture with the metal powder is nitrogen, the strength is therefore at least 80. Million Pascals (MPa), more preferably at least 100 MPa, and most preferably at least 140 MPa. This mechanical strength and plasticity of the spray powder can be further increased by providing an annealing or diffusion bonding heat treatment after spraying.

If hydrazine is used, the strength is typically at least 150 megapascals, preferably at least 170 megapascals, more preferably at least 200 megapascals, and most preferably greater than 250 megapascals.

The present invention also provides a method of making a film comprising the steps of: (a) fabricating the desired splash target by cold spray or power spray; (b) splashing the splash target; (c) moving from the target Dividing a plurality of metal atoms; and (d) forming a film comprising a plurality of metal atoms on a substrate.

The metal atoms according to the present invention include, but are not limited to, ruthenium, rhenium, tungsten, molybdenum, titanium, zirconium, chromium, vanadium, magnesium, tin, lead, aluminum, zinc, copper, ruthenium, silver, gold, cobalt, Iron, bismuth, antimony, gallium, indium, antimony, a mixture of two or more thereof, or an alloy of two or more thereof, or an alloy with other metals having the above characteristics. Depending on the application of the film, a combination of metals or metal atoms in the manufacture of the splash target would be required.

In another embodiment of the invention, a step may be added after step (c) comprising supplying a reactive gas to the metal atoms. A reactive gas is a gas comprising a component which reacts with the metal atoms in a gaseous state or once deposited on a substrate to form a metal or alloy compound Things. As a non-limiting example, the reactive gas can be oxygen, nitrogen, and/or a helium containing gas.

The film applied by the method can have any desired thickness, the thickness of which will depend on the desired end use application. Typically, the film may have a thickness of at least 0.5 nanometers (nm), in some cases at least 1 nanometer, in some examples at least 5 nanometers, in other examples at least 10 nanometers, in some cases It is at least 25 nanometers, in other cases at least 50 nanometers, in some environments at least 75 nanometers, and in other environments at least 100 nanometers. Moreover, the film thickness can reach 10 microns, in some examples up to 5 microns, in other examples up to 2 microns, in some cases up to 1 micron, and in other cases up to 0.5 microns. The film thickness can be any of the stated values or can be between any of the above values. The film according to the invention is advantageous in that the film can have an excellent uniformity and minimal surface roughness. Surprisingly, under similar magnetron sputtering conditions, the film made by the target of cold spray is less than 4.3% to 15.4% compared to the conventional mold compacting target. The unevenness is between 1.5% and 4% (as shown in Table 1). The improved film uniformity is the result of a cold spray target exhibiting a random uniform texture and a fine particle size substantially less than 44 microns.

The use of the film according to the invention includes products used in a variety of different applications. In one embodiment, a film made in accordance with the present invention can be used in thin film transistor (TFT)-liquid crystal display (LCD) applications. Moreover, in another embodiment, the invention includes a film for solar cell applications, inductor applications, semiconductor devices, and CMOS (Complementary Metal Oxygen) technology metal gates. In one embodiment, the invention is directed to a TFT-LCD device comprising a plurality of molybdenum films as a gate having an excellent uniformity. Another embodiment is directed to a number of thin film solar cell applications, wherein the invention includes several solar cells, with a molybdenum (Mo) film acting as a back contact and a barrier layer. The film can be used in ink jet print head applications (eg, ruthenium as a heating element (a highly corrosion resistant metal material), a cavitation barrier and a purification layer (such as Ta ₂ O ₅ ) to provide a higher electrical breakdown), Or architectural glass coating, the film may be part of a flat panel display or a flat panel display, or a magnetic thin film material as a disk drive storage, and an optical coating. The film according to the invention can replace the conventional film according to the prior art.

Due to the uniform fine grain size and texture throughout the thickness of the metal splash target, since the cold spray target is a fine particle non-belt having a random particle orientation, the film obtained from such a target has excellent uniformity.

Solar devices are well known for this art. For example, the following patents and references for solar cell devices are incorporated herein by reference for the disclosure of several solar cell devices (molybdenum film as barrier layer and backside contact): US Patent No. 7,053,294 (in flexibility) Thin film solar cells fabricated on metal substrates), US Patent No. 4,915,745 (thin film solar cells and manufacturing methods), The Fabrication and Physics of High-efficiency CdTe Thin Film Solar Cells (manufacturing and physics of high efficiency cadmium-tellurium thin film solar cells) (published by Alvin, Compaan and Victor Karpov, National Renewable Energy Laboratory, 2003), and Development of Cu(In,Ga)Se ₂ Superstrate Thin Film Solar Cells (Cu(In,Ga)Se ₂ super-substrate thin film solar Development of the battery) (published by Franz-Josef Haug, 2001, Ph.D., Swiss Federal Institute of Science and Technology, Zurich).

Generally, a solar cell may include: A) a cover glass; B) a top electrical contact layer; C) a transparent contact; D) a top bonding layer; E) an absorbing layer; F) a back surface electrical contact; And G) a substrate.

In accordance with the present invention, a film is produced by using a plurality of splash targets made by a power or cold spray process as described above. Preferably, the splash target is a powder mixture from at least one of the following metals: cerium, lanthanum, molybdenum, aluminum, zinc, cerium, copper or gold. The film according to the invention can be used as a backside electrical contact as well as a barrier layer.

In accordance with the present invention, to create a semiconductor device, a splash target is created by the power or cold spray process described above. The splash target is produced by cold spray, preferably using a powder mixture from at least one of the following metals: ruthenium, rhodium, molybdenum, tungsten, chromium, titanium, cerium and zirconium. Films made from such targets are used as barrier layers. The use of such barrier layers is well known in the art. For example, the following patents relating to barrier layers are incorporated herein by reference for the disclosure of several barrier layers: Semiconductor Carrier Film, and Semiconductor Device and Liquid Crystal Module Using The Same, and semiconductor devices using the same. And liquid crystal module) (US Patent No. 7,164,205), Methods of forming an interconnect on a Semiconductor substrate (a method of forming an interconnection on a semiconductor substrate) (U.S. Patent No. 5,612,254), Fabrication of Semiconductor device (tungsten, chromium or molybdenum, and barrier layer) (semiconductor device (tungsten, chromium or molybdenum, and barrier layer) (Manufacturing) (U.S. Patent No. 7,183,206), the entire disclosure of which is incorporated herein.

A semiconductor device having a thin film produced using a cold spray or power process in accordance with the present invention comprises titanium, tantalum, niobium, tungsten, chromium, hafnium and zirconium, and films made of the nitride, telluride or tantalum oxide. These membranes can be used as barrier layers and can replace conventional diaphragms. For example, the following patent describes a Ta (Ta) barrier layer and the disclosure of a barrier layer for inclusion herein: Tantalum Barrier Layer for Copper Metallization (U.S. Patent No. 6,953,742) , Method of Preventing Diffusion of Copper through a Tantalum-comprising Barrier Layer (Method for preventing copper from diffusing through a barrier layer containing barriers) (U.S. Patent No. 6,919,275), and Method of Depositing a TaN seed Layer (TaN) Method of seed layer) (US Patent No. 6,911,124).

The magnetic film material according to the present invention is manufactured by using a splash target manufactured by the above-described power or cold spray process. Preferably, the splash target is produced by cold spray having a synthetic powder mixture, at least two of which are derived from at least the following metals: platinum, cobalt, nickel, chromium, iron, cerium, zirconium, natural elements. The magnetic film material can be used in a hard disk storage device and a magnetic random access memory (MRAM) to replace the conventional magnetic film material. Such conventional magnetic thin film materials are known in the art: for example, the following patents are incorporated herein by reference. Magnetic film materials for use in hard disk storage devices: Magnetic Materials Structures, Devices and Methods (US Patent No. 7,128,988), Method and Apparatus to Control the Formation of Layers useful in Integrated Circuits (Method and apparatus for controlling the formation of useful layers in an integrated circuit) (U.S. Patent No. 6,669,782), Magnetic Recording Medium and Method for Its Production (U.S. Patent No. 5,679,473), Magnetic Recording Medium (Magnetic Recording Medium) Recording media) (US Patent No. 4,202,932). Hard disk drives are well known for this art.

Optical coatings are known in the art: for example, the following patents which disclose optical coatings are incorporated herein by reference for disclosure of several optical coatings: Optical Reflector for Reducing Radiation Heat Transfer to Hot Engine Parts (for Optical Reflector for Reducing Radiation Heat Transfer to Hot Engine Parts) Reduced radiant heat transfer to the optical reflective layer of the heat engine parts) (US Patent No. 7,208,230), Thin Layer of Hafnium Oxide and Deposit Process (US Patent No. 7,192,623), Anti-reflective (AR) Coating For High Index Gain Media (anti-reflective (AR) coating for high coefficient gain media) (US Patent No. 7,170,915). According to the invention, several optical coatings are produced by using a film according to the invention. The splash target is manufactured by the above-described power or cold spray process. The splash target is made of tantalum, titanium or zirconium. The oxide material is hard pressed onto the splash target. The oxide film can be produced by reactive magnetron sputtering of the above target, instead of the conventional oxide film splashed by a target made by vacuum hot pressing or hot isostatic pressing.

Inkjet print heads (including ruthenium) are known to the art: according to the present invention, by making The film according to the present invention is used to fabricate an ink jet print head by the above-described power or cold spray process to produce the splash target. The splash target is made of 钽 or 铌. The film is produced by splashing with a reaction of decane and/or oxygen, which can replace the ruthenium-iridium-oxygen anti-corrosion film as described in U.S. Patent No. 6,962,407. For example, the following disclosure of an inkjet printhead is incorporated herein by reference for the disclosure of several inkjet printheads: Inkjet recording head, method of manufacturing the same, and inkjet printer. Method, and inkjet printer (U.S. Patent No. 6,962,407), Print head for Ink-Jet Printing A method for Making Print Heads (Method for manufacturing a print head) (US Patent No. 5,859,654).

A TFT-OLED (Thin Film Transistor Organic Light Emitting Diode) device structure for a flat panel display is known in the art. According to the present invention, a film is produced by using a splash target manufactured by the above-described power or cold spray process. The splash target is made of tungsten, chromium, copper or molybdenum. A film that is splattered by the cold spray target to serve as a gate layer can replace the conventional film layer in the TFT-OLED. For example, a TFT-OLED is disclosed in U.S. Patent No. 6,773,969.

In a TFT-LCD (thin film transistor liquid crystal display for a flat panel display), the liquid crystal display comprises: A) a glass substrate; B) a source; C) a drain; D) a gate insulator; pole; F) an amorphous germanium, polycrystalline or single crystal germanium layer; G) an n-doped germanium layer; H) a passivation layer; I) a pixel transparent electrode; J) a common electrode; An amine alignment layer; and L) a storage capacitor electrode.

The gate is extremely metal such as molybdenum, tungsten or aluminum.

In another outline diagram for TFT-LCD, an aluminum gate completely covered with molybdenum is used to avoid hillocks formed by aluminum diffusion. Typically, the molybdenum coating is used to prevent the formation of hillocks to a thickness of approximately 300 angstroms ( ). The molybdenum full-cover aluminum film with low impedance (about 4.08 micro ohm-cm) was successfully integrated into the fabrication of high performance amorphous Si:H TFT. Other patents illustrating TFTs in the field of semiconductors are as follows: U.S. Patent Nos. 6,992,234, 6, 489, 222, 6, 613, 697, incorporated herein by reference in its entirety for all purposes for the use in the field of the s. According to the present invention, a film is produced by using the above-described power or cold spray process to produce a splash target. The splash target is made of molybdenum, tungsten or aluminum. The film made by the splash target can replace the conventional aluminum and/or molybdenum layer in the TFT-LCD.

Films derived from such targets have excellent uniformity due to uniform particle size and texture throughout the thickness of the metal splash target. The cold spray target is a fine-grained non-belt with random particle orientation.

In a particular embodiment of the invention an extreme film is provided. In this embodiment, the film is at least 100 angstroms, in some examples at least 250 angstroms, and in other examples at least 500 angstroms. In this embodiment, the film can It reaches 5,000 angstroms, reaching 3,000 angstroms in some cases, 2,500 angstroms in other examples, and 2,000 angstroms in some cases.

In addition to metal films on a variety of different substrates, it is also possible to generate MO _x (oxidation), MN _x (nitride), MSi _x (deuterated), and any combination thereof (such as MO _x ) by reactive splashing or ion implantation. Si _y, etc., where M is a metal. Metal atoms according to the present invention include, but are not limited to, ruthenium, rhenium, tungsten, molybdenum, titanium, zirconium, chromium, vanadium, magnesium, tin, lead, aluminum, zinc, copper, ruthenium, silver, gold, cobalt, iron,钌, 铼, gallium, indium, bismuth, a mixture of two or more thereof.

For many applications, glass is not perfect, especially for architectural purposes. On the one hand, in colder climates, the low reflection of glass in far infrared (room temperature radiation) causes a poor loss of heat energy required to heat the building. On the other hand, in areas with hot climates, the high transmission of glass in near infrared (solar radiation) increases the energy required to cool a building.

Glass coatings for construction are known in the art: for example, the following disclosure of glass coatings for construction is incorporated herein by reference for disclosure of several architectural glass coatings: DCreactively sputtered antireflection coatings Splashing anti-reflective coating) (U.S. Patent No. 5,270,858), Multilayer antireflection coating using zinc oxide to provide ultraviolet blocking (U.S. Patent No. 5,147,125) using Coated Architectural Glass System And method (coated glass system and method for construction (U.S. Patent No. 3,990,784), Electrically-conductive, light-attenuating antireflection coating (U.S. Patent No. 5,091,244). According to the present invention, a film is produced by using the above-described power or cold spray process to produce a splash target. The splash target is made of zinc. During the splashing of the zinc target, oxygen is introduced into the chamber (such as air or oxygen), thereby forming a zinc oxide film. The film made from the splash target can replace the conventional zinc oxide layer in the glass coating.

Carefully designed coatings on glass today overcome all of these shortcomings. The purpose of such coatings is to control the delivery of energy through the glass for more efficient heating or air conditioning. These coatings are multilayer metals and ceramics, the exact composition of which is tailored to specific needs. The heat reflection (so-called low emissivity) coating allows the maximum amount of daylight to pass, but then blocks the heat (greenhouse effect) generated when light strikes an object.

The most important metal compounds for large area glass coatings are, but are not limited to, SiO ₂ , SiN ₄ , SnO ₂ , ZnO, Ta ₂ O ₅ , Nb ₂ O ₅ and TiO ₂ . These thin film coatings are obtained by reactive splashing of yttrium (Si), zinc (Sn), yttrium (Ta), niobium (Nb) and titanium (Ti) metal targets. The splash targets are manufactured by the above-described power or cold spray process.

Other areas of film that can be used in accordance with the present invention are coatings such as optical coatings. Optical coatings include reflective and anti-reflective materials, selective transmission coatings (ie, filters), and nonlinear optical applications. Examples such as TiO ₂ film and Nb ₂ O ₅ film are splashed by sputum and sputum splash targets.

For automotive applications, it is required to transmit 70% visible light and reflect 100% (or near) infrared (IR) and ultraviolet (UV) coatings to meet the goals set by the car manufacturer.

The above areas for film applications include magnetic film materials. Film material The impact of science on disk storage technology is a major revolution, shifting from ferrite read-write heads and particle disks to thin-film disks and read/write heads. Future generations of thin film disks require high coercivity and high inductance. The film media must also be smooth and thinner than current particle surfaces to achieve higher recording densities. Vertical recording is clearly the most promising technology for achieving extremely high recording densities. Several examples of magnetic thin film materials are used, for example, for alloys of cobalt, chromium, nickel, iron, cerium, zirconium, boron, and platinum for storage applications. According to the present invention, a film is produced by using a splash target manufactured by the above-described power or cold spray process. The splash target is made from a composition of at least two of the following metals: cobalt, chromium, nickel, iron, cerium, zirconium, boron, and platinum.

As also mentioned above, the film also includes semiconductor applications. Splashing ruthenium in an Ar-N ₂ environment to form a tantalum nitride (TaN) layer, which is used as a diffusion barrier layer between a copper layer and a germanium substrate for a semiconductor wafer to ensure high use. Interconnection of conductive copper.

Therefore, the present invention is also related to several splash targets, including refractory metal bismuth, antimony, tungsten, molybdenum, titanium, zirconium, chromium, vanadium and niobium, and metallic magnesium, tin, lead, aluminum, zinc, copper, antimony. , silver, gold, cobalt, iron, bismuth, gallium, indium, antimony, a mixture of two or more thereof, or an alloy of two or more thereof, or an alloy with other metals having the above characteristics.

Preferably, the target formed by tungsten, molybdenum, titanium, zirconium or a mixture of two or more thereof, or an alloy of two or more thereof, or an alloy with other metals is excellently a target of ruthenium or osmium formation. Apply to the surface of a substrate to be coated by a cold spray or a power spray. In such cold spray targets, the oxygen content of the metal is substantially constant compared to the oxygen content of the powders. With plasma spray Such cold spray or powered spray targets exhibit a relatively high density compared to targets made by vacuum spray. In addition, depending on the powder characteristics and coating parameters, these cold spray or power spray targets can be made without any texture or with a small texture.

Surprisingly, it has been found that reducing the oxygen content of the cold spray or power spray target, the density and other properties of the splash film layers are improved. The oxygen in the splash target affects the splash rate and therefore the uniformity of the film. For metal films, oxygen is poor at high concentrations due to the effect of oxygen on the resistivity of the film.

We have invented a splatter target and a method of fabricating the target having a uniform fine grain structure substantially less than 44 microns, which is not preferred when measured by an electron backscatter diffractometer ("EBSD"). The texture orientation, and the body throughout the target, show no particle size or texture band, and also has a microstructure that can be copied from one target to another. In addition, we have invented a process for repairing such targets as well as certain hot isostatically pressed (HIP) targets that completely replicate the microstructure of the target prior to repair. When used to repair other targets of poor microstructures, the repair section has an improved microstructure, just like this technique to make the entire target. This technology is not limited by shape or material and has been used to make planar, profiled and cylindrical targets and spray a range of target compositions.

Improvements in the present invention include heat treatment to improve the interparticle bonding and stress reduction of the target, as well as designing the material of the target assembly to minimize the effects of the same spray stress, and allowing heat treatment of the entire assembly to eliminate the need for conventional support sheet materials. Disassembly steps.

Thermal management materials by cold spray technology

The goal of such metal matrix compositions is to produce a composite material that maintains the high thermal conductivity of the metal elements while increasing the low thermal expansion coefficient of molybdenum or tungsten to reduce differential expansion and contraction of the heating bath relative to the tantalum wafer.

Traditionally, the industry has developed tungsten-copper (WCu) or molybdenum-copper (MoCu) metal matrix composites by sintering molybdenum or tungsten (referred to as "skeletons") followed by melting copper at temperature and pressure. Infiltrate to produce a metal matrix composition. The difficulties associated with this technology are an expensive operation in this technology. The permeation temperature is usually in the range of 800 degrees Celsius or higher.

In addition, current WCu or MoCu composite heating bath fabrication requires the fabrication of tungsten blocks, which are sliced to an appropriate size, followed by copper infiltration. The end user then needs to further slice it into the appropriate thickness and set the size. Cold sprays directly produce extremely thin, homogeneously distributed compositions.

Cold sprays are a less expensive operation than "sintering and infiltration" operations because cold sprays are a direct way to make parts from powder at temperatures well below the melting point of the materials.

Here are a few examples: Example 1 is a flat splatter target manufacturing, testing, and film evaluation.

Powdered 15 to 38 micron bismuth powder (Amperit #151, special grade, commercial purity (>99.95 钽), manufactured by HCSTarch), cold spray rated thickness 1/8", diameter 3.1" two-plane circular plate to provide The total thickness of .300 inches. The gas, in one example nitrogen, in another example is ruthenium, preheated to 600 degrees Celsius and used at a flow pressure of 3 million Pascals (MPa). Commercially available Kinetiks gun spray using Cold Gas Technology (Ampfing, Germany) The powder and gas. After spraying, the disc is machined to a nominal 1/4" thickness and the splash surface is polished prior to splashing (see Figure 1). These targets are burned by a standard in the program and then used in several standards. The condition is to use a constant current (DC) magnetron splash unit to make several films.

Figure 2 shows the target surface after splashing. For comparison purposes, a standard compact disc target was also splashed under the same conditions. The measured properties of the films produced are shown in Table 1 below. Table 1 shows that the films made from the cold spray targets have a preferred uniformity, which is a very attractive integrated circuit because it allows a lower film thickness in the process and etches less circuitry in less time to produce less waste. ("IC") A feature of the manufacturer. It is extremely important to improve the uniformity for both electrical and physical properties and to reduce the size of the circuit structure on the wafer. Compared to a conventional target, the extremely fine and random particle structure of a cold spray target directly causes this uniform improvement.

The used target surface shown in Figure 4 directly illustrates this uniform improvement. Figure 4 shows a close-up of a stamping mold metallurgy target (top) and a He (氦) cold spray target (bottom). The stamped target has a mottled and irregular surface after splashing compared to the surface of the cold spray target. The smoother non-moire surface that causes the cold spray target is due to the more uniform non-textured microstructure, which in turn produces a more uniform splash rate and the resulting film (see Figure 3). Table 1 also shows that the resistivity and surface morphology of all three films are similar. Therefore, it can be considered that the splash film made of the cold spray target is as good as or better than the conventional target of the rolling mold. Figure 3 also shows that the membranes made from these targets have different internal morphology, the 氦 spray target creates a columnar internal structure (Figure 3A), the nitrogen spray target creates a large internal structure (Figure 3B), and Compressed target Into a less graphical internal structure (Figure 3C).

Example 2 Manufacturing and Microstructure Analysis of Tubular Concrete Target Preforms

The same operating parameters of Example 1 were used to make several tubular tantalum preforms (see Figure 5). Several samples were cut from the preforms and annealed at different temperatures. Several metallurgical pedestals are then prepared and microstructure analysis is performed on the same sprayed and annealed samples. Table 2 shows a summary of these characteristics. All samples were from a preform using a powder having a starting intermediate size of 15.9 microns (particle count distribution) and approximately 26 microns (integral distribution).

Table 2. Summary of microstructure characteristics of cold spray crucibles for the same spray and subsequent annealing

Table 2 and Figure 6 show the characteristics of the cold spray enthalpy in the same spray, annealing and hot isostatic pressing (HIP) conditions. The process temperature is shown in the figure. All annealing was maintained at a temperature of 1.5 hours, and a hot isostatic flattening (HIP) cycle was maintained for 3 hours. Starting the powder size seems to control the resulting particle size, even after high temperature annealing. Thus, in particular, the cold spray material has a particle size of less than 44 microns, and even large scale working mold materials will typically have a particle size of 60 to 100 microns, or even larger. This finer particle size is an important feature of the target to result in a more uniform film, however, in order to produce a result, it must be combined with a completely textureless microstructure.

Figure 6 illustrates a flat or elongated or crystalline structure of the same spray material which recrystallizes into several large particles during annealing, has a very fine grain structure before and after annealing, and even after extensive annealing, the particle size is still equal to or less than the original size. Powder particle size.

Four cold spray samples and one plasma spray sample were examined by an electron backscatter diffractometer (EBSD) to determine the nature of the crystal texture presented. All Both are through the thickness of the sample, and all oriented for the electron backscatter diffraction (EBSD), so the spray direction is vertically downward.

In the context of materials science, "texture" means "crystallized preferred orientation." These orientations are completely random in a sample, and the sample is said to have no texture. If the crystallographic orientation is not random, but has some preferred orientation, the sample has a weak, strong, or intermediate texture. An electron backscatter diffractometer (EBSD) obtains orientation information for a sample by applying a Kikuchi diffraction pattern formed when the sample tiling is about 70 degrees Celsius.

The samples were mounted, polished, and etched using the step size shown in Table 3, with an electronic backscatter diffractometer (EBSD) at high resolution (2 and 4 micron step size) or lower resolution ( 50 micrometers) characterizes it. The step size is selected based on the particle size of the sample to ensure that small features are not missed when performing an electronic backscatter diffraction (EBSD) scan at a reasonable time.

Results - Cold spray, annealed at 1450 degrees Celsius Figure 7A shows a texture map of the relevant 3 orthogonal directions. Particles oriented within 20 turns of the {100} direction are shown in blue, in yellow in 20 ∘ in the {111} direction, and in red in 20 { in the {110} direction, in colors when the orientation error is reduced. Getting darker. Gray indicates particles that are oriented between the three orientations. The random distribution of colors in the figure is caused by the random distribution of the individual particles. If the particles exhibit any particular texture, one of the colors has an advantage, meaning that if most of the particles are oriented in the {100} direction, yellow will be the dominant color.

The polar map (Fig. 7B) also shows complete lack of symmetry, indicating that the texture is missing in the microstructure. From the texture maps and polar maps, the sample can be considered to have a random texture with no texture bands, and the particles are randomly oriented, have small particle sizes and have no system characteristics.

Result - Cold spray, annealed at 1150 degrees Celsius As shown in the texture map and polar map in Figure 8, the texture is random. The particle structure is finer than the sample annealed at 1450 degrees Celsius.

Results - Cold spray, annealing at 942 degrees Celsius As shown in Figure 9, this sample also has a random texture. However, this indexation ratio is much lower than in previous samples, indicating that the material retains a high tension - the material does not recrystallize at lower annealing temperatures.

Results - Again cold spray (no annealing) Similarly, as shown in the texture map and polar map (see Figures 10 and 11), the texture was found to be random and uniformly random through the thickness. In this example, the following three texture maps represent three inspection zones, the first being the first material deposited (the bottom of the spray layer) and the last one being the last material deposited (the top of the spray layer): all The figures show that the texture associated with this vertical direction (through the thickness direction) is random.

Results - Plasma Spray The substrate or support plate (the lower portion of the texture map of Figures 12 through 13) has extremely large particles of equal width, which have a textured feature of the rolled and overannealed disks. The particles in the texture map are mainly blue and yellow, and a number of polar maps H3, which only include the lower third of the texture grain map, at {100}//ND and {111}/ /ND displays several peaks (although it is a weaker peak), where ND is perpendicular to the sample surface. The triple symmetry of these H3 pole maps is evidence of pressure.

The plasma deposition material shows several columnar particles with many low angle boundaries (shown in red in the particle map). As shown in the polar map H1 (the upper third of the texture grain map) and by the blue color in the figure, the texture is mainly {100}//ND. The polar map H1 is effectively axisymmetric.

The origin and cause of the rougher sides of the columnar particles are unknown.

Since the number of points included is extremely small, both the H1 and H3 polar maps are 15 ∘ smooth angle half width (compared to the usual 10 ∘) to avoid the introduction of unnecessary peaks.

Briefly, the above electron backscatter diffraction (EBSD) analysis showed a completely random non-textured microstructure in the same cold spray and annealed cold spray target, regardless of the annealing temperature. The plasma spray target shows a significant texture.

Example 3 N-铌 (TaNb) cold spray target

A 50/50 volume percent 铌-钽 (NbTa) rectangular target was directly cold sprayed onto a copper support plate. Figure 14 shows a 3 mm (mm) bend in the copper support plate due to the same spray stress in the deposit. The support plate must be flat to seal against its mating flange. Because of these stresses in the machine During processing, it will only redistribute and cause continuous deformation, so the bending cannot be removed by machining. Since the same spray enthalpy, Ta-b and cold spray deposits typically have very limited plasticity (Fig. 15), the bend cannot be mechanically pressed.

However, experiments have shown that plasticity can be greatly improved by annealing. Figure 16 shows that a tantalum deposit is plastically deformed to give a permanent deformation after annealing at 950 °C for 1.5 hours. The copper support plate was removed from the target; the target was then annealed, flattened and machined (Fig. 17).

It is also apparent from this example that conventional copper and aluminum support plate materials are not ideal for refractory metal targets by cold spray. Although traditional copper and aluminum support plates have high thermal conductivity, their elastic modulus tends to be low (promoting deformation), and a large coefficient of thermal expansion ("CTE") cannot match these refractory metals (promoting deformation and annealing to increase the target and The possibility of failure of the bond between the support plates), and the low melting point (which hinders the annealing process when bonding the support plates). Table 4 shows that materials such as molybdenum, titanium or 316 stainless steel have a better combination of properties to resist bending during cold spray processes (high modulus of elasticity) or to allow for high temperature annealing ("CTE") required for refractory metals. ) similar to those of the refractory metal and high melting point).

Cold spray can be used to create a multi-layer target that overcomes the thermal expansion coefficient ("CTE") mismatch and the above-mentioned problems that cause undesirable results. Spraying a splashable target material directly on the support plate, but first spraying a thin coating or a plurality of coatings having a coefficient of thermal expansion ("CTE") between the support plate and the target material between. These intermediate layers may have a thickness of 0.25 to 2.0 millimeters (mm). One way to spray this layer is to use a powder mixture that is packaged The support plate material and the target material are included.

Example 4 Splash of cold spray 铌-钽 (NbTa) target

The pseudo-alloy (the bismuth and bismuth powders are still chemically distinct) targets are placed in a 18"x5" planar magnetron cathode splatter. The target setting size is 4"x17"x approximately 0.125".

Three tests were performed: straight metal deposition, oxide deposition, and nitride deposition. The conditions used and the results obtained are explained below.

Straight metal deposition Splashing was performed using argon at 100 sccm with a splash pressure of 1.0 x 10-3 Torr (basic pressure 4 x 10-5 Torr), 5.0 kW, 550 volts, approximately 73 watts per square foot. The target is excellently splashed from the beginning, no arc is formed, and there is no real "burning" time required for stability.

A final film thickness of 1401 angstroms was deposited on a glass substrate (as measured by a Dektak 2A microsection meter). This is a rate of deposition time of 1 angstrom / (Watt / square inch) / second, slightly higher than the individual rates for helium and neon. The film resistance was 3.7 ohms/square (as measured on a glass slide using a 4 pt probe). Calculated this result is 51.8 - Ohm centimeters.

The calculated result is higher than about 28 - The desired resistivity of ohm centimeters. This material is sensitive to background pressure (impurities) and needs to be pumped to a low -5 to -6 Torr range for proper resistivity values. The film has a solar absorption of 0.41 (as measured and calculated according to ASTM 5903 and E490).

Oxide deposition Splashing was performed using argon at 100 sccm and oxygen at 90 sccm (lower oxygen levels caused a gradual switch to metal mode), at 1.2 to 3 Torr, 3.0 kW (44 watts per square foot) at 680 volts. This is one of the few materials that have a higher splash voltage in oxide mode than in metal mode. An additive was supplied on the 20 kHz operated Sparc-le unit using the MDX D.C. A one-pole stable splash process is obtained, no arc is formed and no problem occurs. Splash yield is 40% of the metal ratio. This process provides a very beautiful and transparent film with a slight pink color in the transmission, a slight green color in the reflection, and a final film thickness of 4282 angstroms. The calculated refractive index is 2.8, which is higher than the refractive index of individual tantalum and niobium oxides (about 2.2 to 2.3).

Nitride deposition Splashing was performed using argon at 100 sccm and nitrogen at 200 sccm, with a splash pressure of approximately 2.0 x 10-3 Torr. This nitride splash is satisfactory and very stable. However, a transparent nitride coating cannot be produced even after many process parameters have been tried. The 3.0 kW using the MDX and Sparc-le units worked well. Splash yield is 51% of the metal ratio. Final film thickness At 69 ohms/square is 1828 angstroms (1260 micro ohm centimeters). The daylight absorption was measured to be 0.59.

Some observations are: splashing is satisfactory in metal mode; splashing is excellent in oxide mode.

The arc is not noted, which means that the oxide content in the target is stable, and the target does not constitute a dielectric layer during deposition. Very high index oxides, which will be quantified and used for measurement of changes as a chemical function due to position and time.

Excellent clear runway with no discoloration points in the runway.

The entire target is deposited at a good rate.

At a maximum power of 5 kilowatts (kW), the target is 5 kW converted to 75 watts per square foot - reference titanium (Ti) or nickel-chromium (Ni-Cr) is splashed at 35 watts per square foot.

The target power ramped up in the 1 kW increase and no problems were noticed.

At high power, there is no problem in terms of target expansion and overheating.

Good dimensional stability is achieved, no problem occurs at these chucks or edges.

Example 5. Annealing and smoothing of a cold spray 钽-铌 (TaNb) target on a copper support plate

A 17" xl.5" x 0.300 钽-铌 (TaNb) deposit was cold sprayed onto a 0.500 thick copper support plate. A layer of approximately 50% copper 50% (TaNb) approximately 0.030" thick is sprayed onto the copper prior to spraying the pure tantalum-tantalum (TaNb) to provide an intermediate compliance coefficient of thermal expansion (CTE) layer. The same spray assembly has A midpoint bend of about 0.2 。. The target assembly is then vacuum annealed at 825 degrees Celsius for 1.5 hours - just enough to introduce recovery in the crucible and make it malleable. After cooling, the target assembly was placed in a flattening machine, successfully flattened to within 0.010 Torr, and machined.

Example 6. A molybdenum-titanium (MoTi) splash target of approximately 50/50 percent composition, produced by hot isostatic pressing (HIP) and by cold spray. The MoTi alloy system does not exhibit 100% solids solubility and contains several harmful fragile mesophases. When molybdenum (Mo) and titanium (Ti) are alloyed in a liquid state, such phases are unavoidable. The goal of developing HIP parameters is to minimize the formation of such phases. However, due to the mutual diffusion of the two elements, if the full density is to be achieved, the formation of such phases cannot be avoided. Figure 19 clearly shows that these harmful phases occur in powders that are hot isostatically pressed (HIP) for 7 hours at 825 degrees Celsius and 15,000 ksi. A third phase material having a thickness of about 15 to 20 microns surrounds both titanium powder and molybdenum powder (Fig. 19), however, it shows that molybdenum and titanium do not diffuse, and only molybdenum and titanium are present in the target produced by cold spray. Pure elemental phase. Figure 20 shows that even after annealing for 1.5 hours at 700 degrees Celsius, there is substantially no interdiffusion, and at this magnification, no visible harmful phase is formed.

The cold spray conditions used to make the tungsten-copper (WCu) composite thermal management materials are listed below: Equipment: Cold Gas Technology (Germany) Kinetiks 3000 or Kinetiks 4000 cold spray conditions: nitrogen at 600 to 900 degrees Celsius, pressure at 2.0 to 4.0 MPa, powder feed rate of 30 to 90 grams, and spray distance of 10 to 80 mm.

Preferred conditions are: 800 to 900 degrees Celsius and a pressure of 3 to 3.8 MPa, a power feed rate of 30 to 50 grams per minute, and a spray distance of 20 to 40 millimeters.

Use powder: Tungsten (W): AMPERIT 140, 25/10 micron particle slicing, sintering; and copper (Cu): AMPERIT 190, 35/15 micron, gas atomization.

Both materials are manufactured by H. C. Starck. The cold spray WCu sample was fabricated by mixing about 50 volume percent W with 50 volume percent copper, and fed through a powder feeder of a CGS cold spray system to make a WCu composite. The substrates can be stainless steel or titanium. The combination between the composite structure and the substrate is excellent. The microstructure of W-Cu (50/50 volume percent) is shown in Figures 21A and 21B.

The table below shows that the same spray WCu has a thermal conductivity of 193 W/m-K and a coefficient of thermal expansion of 13.49 ppm/°C. Annealing at 1600 degrees Fahrenheit (871 degrees Celsius) over 2 hours and 4 hours showed a significant improvement in both thermal conductivity and coefficient of thermal expansion. Annealing is clearly an important step to significantly enhance thermal conductivity and to reduce the coefficient of thermal expansion for cold spray thermal management materials.

The thermal management products manufactured by cold spray technology have the following composition: tungsten-copper (WCu) compound: having a tungsten (W) content ranging from 10% to 85%, a molybdenum-copper (MoCu) compound: having molybdenum ( Mo) content varies from 10% to 85%.

For thermal management applications, the main features of compounds made by cold spray processes are: (a) Copper flat microstructure, other metals such as silver, aluminum or gold may also be used. (b) Molybdenum or tungsten will generally maintain its particulate form or agglomerated particles. Other materials such as aluminum nitride (AlN), tantalum carbide (SiC), and the like can also be used. The microstructure of W-Cu (50/50 volume percent) is shown in Figures 21A and B.

All of the above references are hereby incorporated by reference in their entirety for all utility purposes.

While the present invention has been shown and described with respect to the specific embodiments of the present invention, it is understood that various modifications and arrangements of the various components can be made without departing from the spirit and scope of the basic inventive concept. The components are not limited to the specific forms shown and described herein.

Figure 1 (A) illustrates several planar crucible targets produced by cold spray using helium; Figure 1 (B) illustrates several planar crucible targets produced by cold spray using nitrogen; Figure 2 illustrates Several planar crucible targets made by cold spray after splashing; Figure 3 is prepared by scanning electron microscopy ("SEM") photomicrographs prepared by cold spray, nitrogen cold spray and rolled short metal strips. Several target films are splashed out by several targets; Figure 4A shows the smashing target after splashing in close-up, showing the variegated and irregular surface of the pressing target; Figure 4B shows the splashing in close-up a subsequent cold spray target showing a smoother, non-mosquito surface of the cold spray target; Figure 5 illustrates several tubular preforms in accordance with the present invention; Figure 6 is a photomicrograph showing several identical sprayed and annealed structures taken perpendicular to the spray direction; Figures 7A and B illustrate several results using a cold spray and annealing at 1450 degrees Celsius; Figure 8 illustrates the use of a cold spray and Several results of annealing at 1150 degrees Celsius; Figure 9 illustrates several results using cold spray and annealing at 942 degrees Celsius; Figure 10 illustrates that the substrate has several extremely large particles of equal width, with over-pressure and over-annealing a texture unique to the panel; Figure 11 illustrates a number of polar maps in accordance with the present invention; and Figure 12 illustrates the plasma sprayed helium sample having a plurality of maximal particles of equal width and the like, having a rolled and overannealed sheet A unique texture; Figure 13 illustrates several polar maps in accordance with the present invention; Figure 14 illustrates a cold spray tantalum-tantalum (TaNb) target with deposits over 440 mm long, 110 mm wide and 7 mm thick, note the copper The center of the support plate causes a 3 mm bend; Figure 15 illustrates the load pair deflection for the same spray ,, please note that the deposit failure due to fragile cracks does not exhibit any plastic deformation; Figure 16 illustrates the deflection during the bending test 0.08吋Afterwards, the permanent deformation obtained in the tantalum deposit; Figure 17 illustrates a target after annealing and straightening, the straight edge rule proves that the bend has been successfully removed; Figure 18 illustrates the microstructure of a molybdenum-titanium (MoTi) target and The harmful phases, and the hot isostatic pressing ("HIP") period are interdiffusion zones produced by combining the powders; Figure 19 illustrates a microstructure of a similar spray molybdenum-titanium target produced by a cold spray comprising only elemental molybdenum and elemental titanium, and no harmful phase formation; Figure 20 illustrates cold sprayed molybdenum after annealing at 700 degrees Celsius and 1.5 hours - Titanium, which shows substantially no harmful phase formation compared to a hot isostatic flattening ("HIP") target (Figure 19); Figure 21A illustrates tungsten-copper (W-Cu) (50/50 volume percent) Microstructure; Figure 21B illustrates copper (Cu) having a flat structure.

Claims (31)

A splash target includes: a support plate comprising: a support plate material; an intermediate layer on the support plate; and a target material on the intermediate layer, wherein the intermediate layer has a coefficient of thermal expansion (" CTE") between the thermal expansion coefficient ("CTE") of the support plate and the thermal expansion coefficient ("CTE") of the target material, and the intermediate layer comprising the support plate material and a powder mixture of the target material. The splash target of claim 1, wherein the target material consists essentially of non-melted metal powder. The splash target of claim 2, wherein the metal powder is selected from the group consisting of ruthenium, osmium, tungsten, molybdenum, zirconium, titanium, and alloys thereof. The splash target of claim 1, wherein the target material has substantially no preferred lens texture. The splash target of claim 1, wherein the support sheet material comprises copper, aluminum, or a tantalum alloy having at least copper or aluminum. The splash target of claim 1, wherein the target material is substantially free of fine-grained size bands and textured bands. The splash target of claim 1, wherein the target material has a substantially uniform fine-grained structure and a level of less than 44 micrometers. Average fine particle size. The splash target of claim 7, wherein the average fine particle size is less than 10 microns. A method of forming a splash target, the method comprising: providing a structure comprising: a support plate comprising: a support plate material, and an intermediate layer on the support plate; and coating a target material in the middle a layer, wherein the intermediate layer has a coefficient of thermal expansion ("CTE") between the thermal expansion coefficient ("CTE") of the support plate and a thermal expansion coefficient ("CTE") of the target material, and the intermediate layer A powder mixture of the support sheet material and the target material is included. The method of claim 9, wherein the support sheet material comprises copper, aluminum, or a tantalum alloy having at least copper or aluminum. The method of claim 9, wherein the target material is selected from the group consisting of ruthenium, rhodium, tungsten, molybdenum, zirconium, titanium, and alloys thereof. The method of claim 9, wherein applying the target material comprises spray deposition. The method of claim 12, wherein applying the target material comprises cold spraying. The method of claim 9, wherein when the target material is coated on the intermediate layer, the target material and any portion of the support sheet are not melted. The method of claim 9, wherein the target material has substantially no preferred lens texture after application to the intermediate layer. The method of claim 9, further comprising annealing the structure after applying the target material. A method of restoring a splash target, the method comprising: providing a splash target, initially formed by mold metallurgy or powder metallurgy, and including a splash target material, the splash target material (1) comprising a refractory metal (2) defining a groove therein, and (3) having a particle size and a crystalline microstructure of the original target; and spraying the powder in the groove to form a layer, the layer (1) including the metal, and (2) having The particle size of the planar layer, which is finer than the original target particle size, and (3) the crystalline microstructure of the planar layer, which is more random than the original target crystalline microstructure, wherein the powder is sprayed in the trench for A distinct boundary is formed between the layer and the splash target material. The method of claim 17, wherein the splash target comprises a support plate on which the splash target material is disposed. The method of claim 18, wherein the powder spray does not disassemble the support sheet from the splash target material. The method of claim 17, wherein the spray of the powder comprises a cold spray. The method of claim 17, wherein the refractory material is selected from the group consisting of ruthenium, osmium, tungsten, molybdenum, zirconium, titanium, and alloys thereof. The method of claim 17, wherein the layer has a uniform random texture. The method of claim 17, wherein the planar layer has a particle size of less than 44 microns. The method of claim 17, wherein the planar layer has a particle size of less than 10 microns. The method of claim 17, wherein the layer is substantially free of particle size bands and texture bands. The method of claim 17, further comprising annealing the splash target after spraying the powder. The method of claim 17, further comprising grinding and/or polishing the surface of the layer after spraying the powder. The method of claim 17, wherein spraying the powder comprises spraying the powder only in the grooves. The method of claim 17, wherein spraying the powder comprises spraying the powder in a groove and spraying the powder on a splash target material outside the groove. For the method described in claim 17, the target material for splashing includes different preferences. The region of the crystal orientation, and the layer has substantially no preferred crystallographic orientation. The method of claim 17, further comprising diffusing the layer to spray the target material after spraying the powder.