TW200902741A - 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

Abstract

The invention relates to a sputtering target which has a fine uniform equiaxed grain structure of less than 44 microns, no preferred texture orientation as measured by electron back scattered diffraction ("EBSD") and that displays no grain size banding or texture banding throughout the body of the target. The invention relates a sputtering target with a lenticular or flattened grain structure, no preferred texture orientation as measured by EBSD and that displays no grain size or texture banding throughout the body of the target and where the target has a layered structure incorporating a layer of the sputtering material and at least one additional layer at the backing plate interface, said layer has a coefficient of thermal expansion ("CTE") value between the CTE of the backing plate and the CTE of the layer of sputtering material.; The invention also relates to thin films and their use of using the sputtering target and other applications, such as coatings, solar devices, semiconductor devices etc. The invention further relates to a process to repair or rejuvenate a sputtering target.

Description

200902741 IX. Description of invention: [Technical field to which the invention belongs] ... the priority of the application for the singer (4) The priority of the lion's request: the US patent provisional application number 60/915,967' application 曰 2〇〇7 May*曰, and U.S. Patent Application Serial No. 11/937,164, filed on Jan. 28, the entire contents of each of which is hereby incorporated by reference. [Prior Art] The physical properties of the slamming target for physical gas deposition (pvD) in the conventional electronics industry greatly influence the final characteristics of the film produced, in fact 'helping to enhance high quality thin film devices and circuits The target characteristics of structural fabrication are: a fine and uniform fine-grained structure; a 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 at a viewing scale; A microstructure that is replicated to another target; and a microstructure that is substantially 100% coherent and provides high intensity bonding between the particles. Especially in button (Ta) and niobium (Nb) targets, it is extremely difficult to obtain such characteristics, which are caused by the fact that the high-purity knob and crucible are refined and purified by electron beam melting and casting into a cold water cooling mold. The resulting mold has many extremely large particles whose length and width are measured in centimeters by centimeters. These very large particles require large heat and ep shell heat treatment to reduce particle size and reduce the crystal alignment of individual particles (reduced texture). The heat treatment is limited in reducing the particle size, the random crystallization generated, and the uniformity of the resulting microstructure. Usually, the target material from the mold production 200902741 still contains the large-scale X of the particle size and the texture band. Among them, the common particle size and texture are not the characteristics of the entire particle size and texture of the entire target. * U.S. Patent No. 6,193,821 addresses the importance of this problem and the size gauge =', where the first side is forged or side-punched by several molds, followed by tipping forging or tipping. U.S. Patent Publication No. 9 A1 describes a clothing process 'which utilizes tipping forging, then pulls back forging, then side forging, and finally the father and the squeezing process to provide orientation with mouth (8) 丨 and 丨丨丨丨} - particle mixing. In U.S. Patent Nos. 6,331,233 and 7, iqi, 447, the inventors have explicitly pointed out that the complicated three-step process comprises a plurality of deformation and anneal parts. Although this complex processing route successfully refines the particle size, the process still produces a dominant {111} texture. U.S. Patent Publication No. 2005/0155856 A1 describes a button splash target having a -priority (222) orientation above the -finite 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 a button metal powder rather than a solid tantalum mold. U.S. Patent Nos. 5,58G,516 and 6,521,173 illustrate the cold compression of a group of powder into several short metal strips which can then be used for a wide range of heats. / Mechanical process ^ to process a number of fully dense short metal strips that produce a splash target. U.S. Patent No. 6,770,154 teaches a powdered short metal strip reinforced to full density' followed by a hardening anneal to provide a __ but non-random Z-grain structure. U.S. Patent No. 7,081,148 is extended over the processes of U.S. Patent No. 6,77, 154 to include a resulting splatter target which is at least 99.99% pure ruthenium. 200902741 U.S. Patent No. 7,067,197 describes a powder metallurgy process for surface nitriding short powder prior to compaction. The surface nitrided powder can then be compacted by a series of at least 23 different processing steps which must retain the high nitrogen content of the powder. The least appreciated step is spray deposition, but there is no mention of what type of spray deposition technology is used, namely plasma spray, low pressure paddle deposition, fire spray, high velocity oxygen fuel, etc., which are currently used in many processes. Some of the processes. World Patent Nos. WO 2006/117145 and WO 2006/117144 describe several cold spray processes for producing button coatings, which are incorporated herein by reference for use in the disclosure of such cold spray processes. The fact that the process of integrating the support board into the support board is extremely expensive is also economically interesting for the recovery or reprocessing or repair of the used target. In addition, it is only used in the splash before the entire target has to be replaced. The fact that a plane target is about 30% and a rotating target is about 6〇 to 7〇%. Therefore, the retraction of buttons that have never been used is of great interest. U.S. Patent Publication No. 2004/0065546 A1 discloses a method of hydrogenating the button to make the button brittle to allow the button to be separated from the support sheet, ground into a powder, and used as a powder material in the manufacture of the mold. U.S. Patent Publication No. 2006/0032735 discusses the use of laser beam and other focused energy sources for simultaneous refining and welding of powders that feed a used area of wear to fill the space created by splashing. 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. 200902741 A target must be machined to the 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 variety of films. Applications range from reflective glass for window glass to low emissivity coatings, photovoltaics (molybdenum), and 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.) ;, Journal of Thermal Spray Technology, Vol. 13(2), June 2004, pp. 265-273; US Patent No. 6,139,913 and US Patent Publication No. 2005/0120957 and 2005/0252450) is a new industrial technology To solve many of the industrial manufacturing challenges (see also, for example, U.S. Patent Nos. 6,924,974; 6,444,259; 6,491, 2, 8 and 6, 9, 5, 728), the entireties of each of Or the disclosure of a power spray. The cold spray utilizes a high velocity gas jet to rapidly accelerate a powder having a size of typically less than about 44 microns to a high speed so that the powder bonds to a surface upon impacting a surface to form a complete, bonded Good and dense coating of 200902741 layer. It has been suggested to spray the button powder on various substrates (including steel) (see, for example, Van Steenkiste, etc.) Published "Anaiysis 〇f Tantaium Coaitngs Produced by the Kinetic Spray Process", Journal of Thermal Spray Technology, Vol. 13, No. 2, June 2004, p. 265 To 273 pages; Marx et al., "Cold spraying - innovative layers for new applications" " Thermal Spray Technology Journal, Vol. 15 'No. 2, 2006 June pp. 177-183; and "The Cold Spray Process and its Potential for Industrial Applications by Gartner et al., Journal of Thermal Spray Technology, 15th Vol. 2, June 2006, pp. 223-232). This cold spray does not have to be fully heated by heating the powder to a temperature close to or above its melting point, as 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 this case in particular no substantial substrate heating. The achievement of the power spray can be carried out, for example, by injecting a powder having a particle diameter of more than 65 μm into a de Laval-type nozzle, carrying it away in a supersonic flow, and accelerating to a high speed due to a resistance effect. The kinetic energy of the particles is transformed by plastic deformation into tension and heat when striking the surface of the substrate. The particles melt during the process. In the case of manufacturing a cathode or electron splatter target body 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 (the button's TM is 2,998 degrees Celsius), while the support plate of the 200902741 support target is selected for its high thermal conductivity, and is usually copper or (named TM 660 660 ° C), both are low melting temperature materials. Therefore, 'to use*' to heat the powder to or near the other thermal spray process deposits the resistant material on the low temperature support plate. The current implementation method is to separate the target completely 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 repair the used target directly on the support plate by a number of targets; ^ ' and without removing the target from the support plate. SUMMARY OF THE INVENTION The object of the present invention is to create a splash target having a fine-grained and randomly crystallized microstructure throughout the body of the object. It is a further object of the present invention to provide a process that can cost-effectively generate the microstructure and replicate the structure from the target to the other. Preferably, the process does not require melting. Several examples of such processes include cold spray or power spray processes. The present invention is also directed to providing a cost effective repair or recovery process which provides the same or preferred microstructure of the repair target as the original. Still another object of the present invention is a development-target recovery process by a method that does not require melting, such as a cold spray or a power spray. We have found that it is possible to directly manufacture a fine-grained structure having an Ik machine orientation to pass the entire thickness of the target and a plurality of parameters & 4 each directly on the support plate without using a complicated process. The target of the desired microstructure and the technique of simply modifying the target ^ This technique 200902741 does not use the - smashing process. Several examples of such processes include cold spray or power spray of fine metal powders such as (d) limited to group powders. Further, the present invention provides a method of splashing whereby any of the above-mentioned mitigation targets are subjected to a plurality of money-stroke conditions and thereby subjected to slamming. Any suitable splash method can be used in the present invention. Suitable transfer methods include, but are not limited to, magnetron shock, pulsed laser turn, ion beam splash, triode, and combinations thereof. In addition, the present invention provides a splash target that includes a uniform fine grain structure that is substantially smaller than A* microns, which is not preferred when measured by an electron backscatter diffractometer ("EBSD"). The texture orientation (i.e., substantially comprising a plurality of particles along the distraction) comprises a plurality of particles substantially less than 44 microns, and the body throughout the target exhibits no particle size or texture band. Further, the present invention provides a target, It includes a large particle size 'particle size' in the annealed state that is 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, by electrons The Backscatter Burner ("EBSD") does not have a good texture orientation when measured, and the body throughout the target shows no grain size or texture banding. In addition, the present invention provides a process for manufacturing a _ snip target component by depositing the smear target directly on a support plate for the target component via a _ powder nozzle. The target material, the deposit and the substrate are machined to the final target assembly size. The present invention also provides a method of manufacturing a film comprising the steps of: (a) splashing the above-mentioned money target; 12 200902741 (b) removing a plurality of metal atoms from the target; forming a metal including the above on a substrate a thin film. [Embodiment]

We have found that the technology and several parameters that allow the direct manufacture of several targets without the above complicated processing, and the production of several targets having the desired microstructure directly on the support board, may or may not be used first. The purpose of the self-support board removal is to simply repair the used technology. The 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, short 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: or more. Air can also be used in special situations. If safety regulations are met, hydrogen or a mixture of hydrogen and other gases will also be considered and advantageously used due to the extremely high sonic speed of hydrogen. In fact, the speed of sound of hydrogen is higher than the speed of sound of A3G%, and the speed of sound of 氦 is: three times the speed of sound of nitrogen. The air is at 344 meters per second in the Celsius temperature and the idling speed of the (4) (_), compared to 28% of the atomic weight of air. Hydrogen with an atomic weight of 2.016 is the lightest element, and its density is about 14 times smaller than air. Has a speed of sound of 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 The group: 铌, knob, tungsten, molybdenum, titanium, zirconium, at least two of them mixed 13 200902741 or its other or other 150 material 4 ^ am. An alloy of the genus, the powder having a particle size of 0.5 to 150 未 (μΓη), 芏10 to 44 η 兮 兮 疋 5 to 80 μm and the best is Chuanzhi 44 secret, the powder is under pressure Providing an inert gas to the spray hole at an elevated non-flowing force, spraying the particulate material and the gas to the surface to be coated, so that the spray hole is located in the low-period force region; ; = Μ Μ force is substantially smaller than the front of the spray hole is not for the particulate material - read a large number of accelerated service coating surface and thereby annealing the coating, the substrate is coated with a hard coating . 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 and the target to be coated and the cold spray are subjected to a pressure of less than 80 kPa or higher (U million). Mpa - Inert chamber. This application uses a cold spray from beginning to end. It should be understood that in the example of the cold spray process only, a power spray process can be used instead of the cold spray. Process. In another preferred version of the process, a power device is utilized to perform the spray. A particle diameter of less than 5 microns is used to have a higher particle velocity and generally a lower particle temperature than a cold spray process. The power process uses a larger particle size distribution between Μ 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, it can be used for total plastic deformation. The kinetic energy is usually greater than the cold spray process. The power spray is applied using a longer spray 14 behind the throat area. 200902741 mouth length (eg 280 mm (mm) versus standard 80 mm) and higher gas temperature (eg higher than 200 degrees Celsius , but much lower than the melting point of the material. Compared to coatings produced with shorter nozzles, higher particle velocities improve the coating properties, resulting in high levels of plastic deformation, increased adhesion, and 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 % purity, especially at least 99.9995% purity. Generally, if an alloy is used instead of a single refractory metal, at least the refractory metal (but preferably the alloy as a whole) has this purity so that a corresponding high purity can be produced. In one of several embodiments according to the present invention, the total content of non-metallic impurities such as oxygen, carbon, nitrogen 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 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 a reducing agent can be used to reduce refractory metal compounds and It is preferably formulated for subsequent deoxidation, for example, reduction of tungsten oxide or oxidized key in a hydrogen stream at elevated temperature. This formulation is disclosed, for example, in Schubert, Lassner's "Tungsten" (Kluwer Academic / 15 200902741). Charging Press, New York, 1999) 'or Brauer's Handbuch der Praparativen Anorganischen Chemie" (Ferdinand Enke Verlag Stuttgart, 1981, p. 1530). In the examples of ruthenium and osmium, the preparation is carried out in most of the examples by reducing an alkali heptane fluoromonitate and an alkaline earth metal heptane fluoro-monate 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 hexanoate. 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. An argon atmosphere can be advantageous. Many suitable processes are known to those skilled in the art, and process parameters for selecting 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. Further, 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 rolled body/powder mixture with a material powder. The material is selected from the following a group consisting of: ruthenium, osmium, 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 〇5 to 15 〇 micron particles Dimensions in which the gas flow is given a supersonic velocity and the supersonic jet is directed to the surface of the article to be reprocessed or manufactured. 16 200902741

κ... — The target of splashing is a source of metal in the splash of metal cathode. These mitigation targets are used in the manufacture of integrated circuits, semiconductors, and other electrical, magnetic, and optical products. During the splashing process, the metal surface of the splash target is usually rubbed off unevenly, 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 to provide re-processing of a splash target or the possibility of recovering a splash target without having to disassemble the support plate, or to provide direct/spray material to the support plate or for a rotating target support. The possibility of tube. For this purpose, the groove in the target of the rescue is filled with the special refractory metal, which can be accomplished by, for example, the above-mentioned cold spray or power process. For this purpose, the supersonic jet of the gas/powder mixture is guided to the top and moved over the entire length and shape of the grooving. If necessary, the action is to refill _ so that the surface of the slamming target is reformed - almost completely flat area and / or the filling material is slightly "(4) the surface of the target. Preferably, the gas is then applied / Powdered-kneaded supersonic jet material (4) _ the remaining surface of the target, and guided over the entire length, width and shape of the target surface of the target, until the full thickness of the target surface is covered Plane layer 17 200902741 The rough surface obtained by conventional polishing can be polished to obtain the desired smooth surface. We noticed that if the original target is made by traditional mold metallurgy or powder metallurgy technology, the target is _ target Finer (four) grain size and more random structure. If the original target is made of cold spray, the repair will have similar microstructures that are similar to the original target, but there will be a clear dividing line between the original target and the secret zone. It can be seen in the profile of the target during the manufacturing-new_target period, which is directly applied to a support plate. Depending on the construction of the target, the gas/powder is thus mixed. The supersonic jet of the object is superimposed on the entire surface of the cutting board of the Ogaki target and guided over the entire length, width and shape of the surface of the splash target until it is completely uniform and sufficient to cover the surface of the target a thick planar layer, or only the contact area of the plasma, which results in considerable material savings. Preferably, the target has a thickness of between 2 and 20 mm, more preferably between 3 and 15 mm, More preferably between 5 and 12 milliliters, and even more preferably between 8 and 10 millimeters. The purity and oxygen content of the target to be obtained should not deviate from the powder by no more than 5%, and preferably not more than 1%. This can be advantageously achieved by applying the to-be-processed target under inert gas. Argon is advantageously used as the inert gas because of its higher density than air. Especially if the target of splashing is to prevent argon from leaking or flowing out In the continuous tank-container, 'argon tends to cover the object to be coated and still exists. Other identifiable gases according to the present day have been discussed. The process according to the invention is particularly suitable for the treatment of several slamming targets. Or system 18 200902741 made, one side Since the preferred crystal orientation which can be changed at different intervals during the manufacturing process of the thermal mechanism often occurs, a uniform texture is not obtained, but rather a so-called strip shape, that is, several regions in which different preferred orientations occur. This can be avoided only by extremely complicated and expensive processes. A uniform random texture can be obtained by the process according to the invention, wherein no detectable is found above the thickness of the target of the metal Preferred orientations to 0 Similarly, a uniform and random particle size distribution and particle size distribution are obtained in the targets so that, if not desired, ribbons of different particle sizes or particle sizes are not obtained. The size or texture is particularly bad. The reason is that it will cause the splash rate and the change of the film. In the process of applying the powder to the splash target and melting the powder, it is known from experience that bubbles will occur and it is difficult to grow. This situation will not be seen in the process of the invention. After application of the edge target, the surface of the splash target is typically ground and polished to provide a suitable smooth surface, which can 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, which is typically copper or aluminum, or a plate of such metal and hinged alloy. 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 19 200902741 Other mechanical or electrical structures. The object produced in accordance with the present invention, or the target produced during the manufacture or reprocessing of a splash target, may have a high purity and a 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 2%, 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 beginning of the beginning by an oxygen content of not more than 5%, especially not more than 1 Torr. In an advantageous embodiment, the targets 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 the closed nature and porosity of the target. Measure. - 97/ of the target. The degree indicates that the target has a density of the bulk material. A closed, almost non-porous target usually has a density of more than 99.5%. The image can be analyzed by a cross-sectional image (profile) of the target or by tamping. (helium pykn〇metry), the latter method is less advantageous because in the case of extremely dense targets, the pores that are present in the target and removed from the surface are not detected. Therefore, a hole lower than the actual one is detected. (Determination. The density can be determined by image analysis, first in the image of the photomicrograph), and the total area of the object to be investigated is determined, and then the area is correlated with the area of the pores. 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 the splash target, preferably greater than _, especially 20 200902741 which is a large 99 % or 99.5%. These targets show high mechanical strength, resulting in their high density and high deformation of the particles. In the giant case, if the gas forming a gas/powder mixture with the metal powder is nitrogen, Equal strength is therefore at least 8 million (MPa) 'More preferably at least 1 MPa, preferably at least 14 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 usually at least 15 MPa, preferably at least 17 MPa, more preferably at least 200 MPa, and most preferably greater than 250 MPa. The method of film comprising the steps of: (4) manufacturing the desired target by cold spray or power spray; (b) splashing the splash target; (c) removing a plurality of metal atoms from the target; (d) forming a thin film comprising a plurality of metal atoms on the substrate. The metal atoms according to the invention include, but are not limited to, sharp, group 'cranes, = titanium, tantalum, chromium, vanadium, magnesium, tin, lead , aluminum, zinc, copper, antimony, silver, di-, cobalt, iron, antimony, bismuth, gallium, indium, antimony, a mixture of two or more thereof, or an alloy of two or more thereof, or with the above characteristics The combination of other metals, depending on the application of the film, will require the use of the target in the manufacture of the target. a combination of a metal or a metal atom. In addition, after the step (4), a step -4 can be added, which includes supplying a reaction gas to the metal atoms. The reaction gas 疋 includes a component-containing gas enthalpy. In a state or a state, deposited on a substrate and reacted with the metal atoms to form a metal or alloy compound 21 200902741 as a non-limiting example, the reaction gas can be a gas, a gas, and/or a The film comprising the film applied by the method may have any desired thickness which will eventually be used to make the film of the desired film. Typically, the second is at least .5 nanometers (four), in some cases at least The dryness is at least 5 nanometers in some cases, 2: in other examples; Leica: meters, in some cases at least 25 not 5. Nano, in a _ environment... In other cases, at least ^ 75 at least 75 nm in the environment, and 疋乂 100 nm in other environments. Moreover, the film thickness can be as large as 10 micrometers, and in some cases, up to 5 micrometers, in other examples up to 2 micrometers, in a trait, up to 1 micro-finish, and in other cases up to 5 micrometers. The ^ 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 a very small surface roughness. Surprisingly, under the similar magnetrons, the film made by the target of the traditional mold-pressing button is uneven. 4. It is caught between 15.4%. The resulting film is not uniform but is between 1.5% and 4% (as shown in Table j). 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 metal gates for CMOS (Complementary Metal Oxygen) technology. 22 200902741 In one embodiment, the invention is directed to a tft-lcd device comprising a plurality of molybdenum thin ruthenium as a gate having an excellent uniformity. Another embodiment is directed to a number of thin film solar cell applications in which the invention includes a plurality of solar cells' wherein a molybdenum (M〇) film serves as a back contact and a barrier layer. The film is used in ink jet print head applications (for example, as a heating element (a highly corrosion-resistant metal material), a cavitation barrier and a purification layer (such as TkO5) to provide a higher electrical breakdown), or The building is coated with glass, which 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 present invention can be substituted for a conventional film according to the prior art. Due to the uniform fine particle size and texture throughout the thickness of the metal splash target, since the cold spray target is a fine particle non-band shape with 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 'disclosure for several solar cell devices (molybdenum film as barrier layer and backside contact). US Patent No. 7,053,294 Thin film solar cells fabricated on a metal substrate), 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 (Manufacture and physics of high-efficiency cadmium-tantalum thin film solar cells) (published by Alvin, Compaan and Victor Karpov, 2003 National Renewable Energy Laboratory), and Development of Cu(In, Ga) Se2 Superstrate Thin Film Solar Cells (Cu(In,Ga)Se2 super-substrate thin film solar cells) Development) (published by Franz-Josef Haug, 2001 23 200902741, Ph.D. the Swiss Federal Institute of Science and Technology, Zurich). Typically, a solar cell can include: A) - a cover glass; B) a top electrical contact layer; C) a transparent contact; D) a top bond layer; E) an absorber layer; F) a backside electrical contact; And G) - 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: group, sharp, enamel, indium, zinc, bismuth, copper or gold. The film according to the present invention can be used as a back surface electrical contact and a barrier layer. According to the present invention, in order to fabricate a semiconductor device, a splash target is produced by the above-described power or cold spray process. The splash target is produced by cold spray, preferably using a powder mixture from at least one of the following metals: group, bismuth, molybdenum, tungsten, chromium, titanium, niobium and hammer. 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 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 a liquid crystal module) (U.S. Patent No. 7,164,205), Methods of forming an interconnect on a 24 200902741 semiconductor substrate (Method for 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) (manufacture of semiconductor devices (tungsten, chromium or molybdenum, and barrier layers)) (U.S. Patent No. 7,183,206), the entire disclosure of which is incorporated herein. A semiconductor device having a film produced by using a cold spray or a power process according to the present invention comprises titanium, tantalum, niobium, tungsten, chromium, hafnium and zirconium, and a film thereof made of a nitride, a telluride or a tantalum oxide. These films can be used as a barrier layer and can replace conventional button films. 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 layers) (U.S. Patent No. 6,919,275), and Methodof 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 produced by using a splash target manufactured by the above-described power or cold spray process. Preferably, the 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, ruthenium, osmium, a natural element. This magnetic film material can be used in hard disk storage devices and magnetic random access memories (MRAM) to replace conventional magnetic film materials. Such conventional magnetic thin film materials are known in the art. For example, the following patents are incorporated herein by reference. 25 200902741 The disclosure of magnetic thin film materials for hard disk storage devices: Magnetic Materials Structures, Devices and Methods Material Structure, Apparatus, and Method) (U.S. Patent No. 7,128,988), Method and Apparatus to Control the Formation of Layers useful in Integrated Circuits (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 (U.S. 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 disclosure of optical coatings is incorporated herein by reference for the disclosure of several optical coatings: Optical Reflector for Reducing Radiation Heat Transfer to Hot Engine Parts (for 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-Reflection for High Coefficient Gain Media (AR Wide Coating) (U.S. Patent No. 7,170,915) according to the invention, by using a film according to the invention to make several optical coatings. a power or cold spray process to produce the splash target. The splash target is made of tantalum, titanium or tantalum. The oxide material is hard pressed onto the splash target. The reactive magnetron can be splashed by the above target The oxide film is fabricated to replace the conventional oxide film which is splashed by a target made by vacuum hot pressing or hot isostatic pressing. The ink jet printing head (including ruthenium) is known to the art: according to the present According to the invention, the splash target is manufactured by using the film according to the present invention to make an ink jet print head by using the above-described power or cold spray process. The splash target is made of a button or a cymbal. The film is made by splashing with a reaction of decane and/or oxygen, which can replace the button-矽-oxygen anti-corrosion film as described in U.S. Patent No. 6,962,407. For example, the disclosure of the ink jet print head is hereby incorporated by reference. Used in this paper for several inkjet print heads Inkjet recording head, method of manufacturing the same, and inkjet printer (inkjet recording head, method of manufacturing the same, and inkjet printer (U.S. Patent No. 6,962,407), Print head for Ink-Jet Printing A method for Making Print Heads (printing head for ink jet printing, method of manufacturing a printing head (U.S. Patent No. 5,859,654). TFT-OLED (Thin Film Transistor Organic Light Emitting Diode) device structure for flat panel display Conventionally, 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 formed as a gate layer can be substituted for a conventional film layer in a TFT-OLED. For example, a TFT-OLED is disclosed in US Pat. No. 6,773,969. A TFT-LCD (Thin Film Transistor Liquid Crystal Display for Flat Panel Display) Afro include: A) - glass substrate; B) - source; C) a drain; D) - gate insulator; E) a gate; 27 200902741 F) - amorphous germanium, polycrystalline or single crystal矽 layer; G) — η doping矽 layer; Η) — passivation layer; I) one pixel transparent electrode; J) a common electrode; Κ) a polyimide aligning layer; and L) a storage capacitor electrode. The gate is extremely metal such as molybdenum, tungsten or aluminum. In the other outline of the TFT LCD, the gates that are completely covered by the eye are used to avoid the hills formed by the diffusion of |g. Usually, the thickness required to turn over the cover layer to prevent the J-opening/forming is about a fan (human). The molybdenum-coated aluminum film with low impedance (about Ο8 micro Λ Λ) was successfully integrated into the high-performance non-lanthanide Si'H TFT fabrication. Other patents describing tft in the field of semiconductors are as follows: U.S. Patent No. 6,992,234, 6, 489, 222, 6, 613, 697, incorporated herein by reference in its entirety for the use in the the the the the the the the The splashed eye & is made to make a film. The scale target is made of a turn, a crane or a charm. The film made by the target of the reduction can replace the conventional and/or key layer in the TFT丄CD. Since the average (four) grain size and texture of the entire thickness of the metallographic targets are excellent, the film obtained from such a target has a fine particle non-band shape with random particle orientation. Provided in a particular embodiment of the invention - <RTIgt; </ RTI> <RTIgt; </ RTI> In this embodiment, the film is at least 1 angstrom, in some examples at least angstroms, and in the eight examples it is at least 5 〇〇. Gentry. In this embodiment, the film can reach 5,000 angstroms in 28 200902741, 3,000 angstroms in some instances, 2,500 angstroms in other instances, and 2,000 angstroms in some cases. In addition to metal films on a variety of different substrates, it is also possible to generate MOx (oxidation), MNX (nitride), MSix (deuterated), and any combination thereof (such as MOxSiy, etc.) by reactive sputtering or ion implantation. M is a metal. The metal atoms according to the present invention include, but are not limited to, sharp, bismuth, tungsten, molybdenum, chin, wrong, collateral, hunger, town, tin, wrong, inscription, recital, copper, recorded, silver, gold, aunt, iron, A mixture of two or more of ruthenium, osmium, gallium, indium, and yttrium. Regarding many applications, glass is not perfect, especially for architectural purposes. On one side, 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 penetration 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: DC reactively 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 zinc oxide to provide ultraviolet blocking. Coated architectural glass system and method (US Patent No. 3,990,784), Electrically-conductive, light-attenuating antireflection coating (US Patent No. 5,091,244) 29 200902741 俨虞: "Ming, hunting is made by using the above-mentioned power or cold spray process to create a film with a splash target. The target of the reduction! ^ 墼射射... I know it is made of zinc I. In the zinc target Splashing n, in the chamber (such as air or oxygen) bow into the oxygen, thereby taking the zinc film. By the splash target Broken glass film system may be substituted zinc oxide layer. * Now on glass coating may be carefully designed to overcome all these drawbacks. The purpose of this coating and the like to control the energy delivery is by adding more effective for the glass

Hot or air conditioning. These coatings are multi-layered 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 sunlight to pass through, but then blocks the heat generated by the impact of the object (greenhouse effect). The most important metal compounds for large-area glass coatings are (but are not limited to) Si〇2, SiN4, Sn〇2, Zno, Ta205, Nb205, and Ti〇2. These thin film coatings can be transmitted by reactive sputtering of yttrium (Si), zinc (Sn), button (Ta), niobium (Nb) and titanium (Ti) metal targets. The slamming 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 that provide selective transmission of coatings (i.e., filters)&apos; and nonlinear optical applications. Examples such as Ti〇2 film and Nb205 film are splashed by sputum and sputum splash targets. For automotive applications, it is required to transmit 70% visible light and reflect 100% (or close) infrared (IR) and ultraviolet (UV) coatings to meet the automotive manufacturer's goals. The above areas for film applications include magnetic film materials. Thin Film Materials 30 200902741 The impact of science on disk storage technology is a major revolution, shifting from ferrite read and write heads and particle disks to thin film disks and read/write heads. The future generation of thin film disks requires high coercivity and high inductance. The film media must also be smooth and thinner than the current (iv) surface to achieve a higher score. Vertical recording is clearly the most promising way to achieve extremely high-tech. Several examples of magnetic thin film materials are used, for example, for the storage of alloys of application, chromium, recording, iron, sharp, offset, deletion and turning. Geno County invented the manufacture of a film by sputtering targets made by the above-mentioned power or cold process. The splash target is made from a composition of at least two of the following metals: cobalt, chromium, nickel, iron, ruthenium, osmium, boron, and platinum. ^ The film as described above also includes semiconductor applications. The shock group is formed in the surrounding environment of -Ar_N2 to form a nitride layer (TaN) layer, which is used as a diffusion barrier layer between the copper layer and the -shixi substrate for the semiconductor wafer to ensure that the use is still conductive. Copper interconnection. Therefore, the present invention is also related to several splash targets, including metal-resistant fine sets, cranes, turns, titanium, aluminum, chrome, niobium and tantalum, and metal towns, tin, antimony, aluminum, zinc, copper, antimony, Silver, gold, cobalt, iron, ruthenium, gallium, indium, antimony, a mixture of one or more thereof, or an alloy of two or more thereof, or an alloy with other metals having the above characteristics. Preferably 'by tungsten, molybdenum, titanium, niobium or a mixture of two or more thereof, or an alloy of two or more thereof, or an alloy with other metals, the target of excellent bismuth or bismuth formation' Apply to the surface of a substrate to be coated by a cold spray or a power spray. In these cold spray targets, the oxygen content of the metal is almost constant compared to the oxygen containing enthalpy of the powders. Compared with the target made by vacuum spray 31 200902741, the target shows a considerable degree of reading of the older & In addition, depending on the characteristics of the powder and the sound of the coating;: 'There can be any such cold and fine power fog target without any (4) or with a small texture. 1", and buried 7 people with horror 'have been found to reduce the cold spray or movement: the amount: the density and other characteristics of the slamming film layer are improved ^ Gold::: the milk strike rate' Affect the uniformity of the film. For the Jade 4 film, oxygen is poorly affected by the oxygen resistance of the film. "We have invented - a method of hitting a target and making a touch target, the button target has a uniform fine grain structure of substantially less than 44 microns, measured by electrons; when measured by a scattering diffractometer (&quot;EBSD") There is no better texture orientation, and the present invention shows no age or (4) strips throughout the target, and also has a microstructure that can be copied to another target. In addition, we have invented a process for repairing such targets and certain hot isostatically pressed (HIP-type) targets, which completely replicate the target before repair. When used to repair other targets of poor microstructures, the recovery section has an improved microstructure, just like this technique. This technique is not limited by shape or material 'has been used to make planar, longitudinal and cylindrical targets and spray a range of target compositions. 'The improvements made by the present invention include heat treatment to improve the interparticle bonding and stress reduction of the target, and 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 conventional support sheet materials. Required removal steps. 32 200902741 Thermal management materials by cold spray technology The goal of these metal matrix compositions is to produce a synthetic material, ... with a low thermal expansion coefficient of indium or crane to reduce the difference between the heating bath and the wafer: another expansion and contraction 'Maintain the high thermal conductivity of these metal elements. Traditionally, the tungsten-copper (WCu) or molybdenum-copper (MoCu) metal matrix sigma has been developed by sintering tantalum or tungsten (referred to as "skeleton"), followed by temperature and dust (four) The copper penetrates to produce a metal-composite. "The difficulty associated with this technology is an expensive operation in this technology. The permeation temperature is usually in the range of Celsius or higher. / The manufacturing of the heating tank of the WCu or MoCu composition requires the first fabrication of the town block - sliced into - appropriate The size 'follows the copper infiltration. Then, the end user needs to step in and slice it «in thickness and mosquito size. Cold spray can directly produce a very thin, homogeneously distributed composition. Compared to 'sintering and infiltration&quot; Operation, cold spray is a less expensive operation, because cold spray is 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 button splash Target manufacturing, testing and film evaluation. 纽 New size powder of 15 to 38 microns (Amperit # 151, premium grade, commercial purity (&gt;99.95钽), manufactured by HC STarch) Cold spray rated thickness 1/8, diameter 3 · 1 &quot; two-plane circular plate 'to provide a total thickness of 3 。. § Hai gas, in one case is nitrogen, in another example is 氦, preheated to 6 degrees Celsius, and at 3 One million kPa (MPa) Flow pressure used. Commercially available Kinetiks rush spray 33 using cold gas technology company (Ampfing, Germany) 200902741 The powder and gas. After spraying, the disc is machined to a nominal ι/4" thickness and polished before splashing. Splash the surface (see Figure 1). These targets are incinerated by a standard in the program and then used in several standard conditions to fabricate several films using a direct current (DC) magnetron splash unit. Figure 2 shows the target surface after the sniper. For comparison purposes, a standard 辗 disc target is also struck under the same conditions. The measurement characteristics of the produced 4th film are shown in the following Table i. We show that the film made from these cold spray targets - good uniformity - is extremely attractive because it allows the process towel to use a lower film thickness and a smaller number of scraps generated by a smaller circuit. ''1C') The characteristics of the manufacturer. For both electrical and physical properties and the pursuit of reducing the size of the circuit structure, the improvement of the hook is extremely important for a traditional target, a cold spray target The extremely fine and random particle structure directly causes this uniform change. The target surface used in Figure 4 can directly explain this uniform improvement. Figure 4 义明. 儿明-辗压式模模金属冶金 target (above) and out (nitrogen) Cold spray Ding (below) only looks at the surface of the cold spray target. After splashing, the rolling, 'U motley and irregular surface. A smoother non-color table that causes the cold spray target Φ It is a more uniform mitigation microstructure, which in turn produces a more uniform attack rate and the resulting film (see Figure 3). Table i also shows that all three films have similar resistivity and surface morphology. Identify the sniper film and μ made of cold spray target The traditional goal of mold-casting is better or better. Figure 3 also shows that the membranes made from these targets have different internal forms of evil, 11 spray targets create - columnar internal structure (Figure 3Α), nitrogen spray The target causes - the internal structure of the parties (Fig. 3Β), and the construction of the target 34 200902741 into a relatively unpatterned internal structure (Fig. 3C). Table 1. Characteristics of several splash films Film characteristics Film number Process thickness ( Nano) Average thickness (nano) Uneven film thickness Rs (European marriage sq) Resistivity coefficient (Omtical) Microstructure surface morphology 106 CSHe 230,168,197 198 1.50% 8.642±2.4°/〇1.71E-04 Smoothing 107 CSHe 157,170,170 166 3.40% 10.281±3.6% 1.71E-04 City smoothing 109 csn2 288^88^27 268 3.50% 8.713±3.6°/〇2.33E-04 Smoothing 110 csn2 288^04^06 233 4.00% 7.867i4.0% 1.83E -04 All parties and other large smooth 111 prototype 4.30% 8.42U4.4% 112 prototype 244 244 5.00% 7.87 &amp; M.2% 1.92E-04 no graphic smoothing 113 prototype 15.40% 4.120*12% 114 275^48^30 251 7.40% 6.76U7.9% 1.70E-04 No graphic smoothing example 2 Tubular button target prefabrication Model Manufacturing and Microstructure Analysis 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 mounts 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 mid-size of 15.9 microns (particle count distribution) and approximately 26 microns (integral distribution). Table 2. Microstructure characteristics of cold spray crucibles for the same spray and subsequent annealing. Abstract 35 200902741 Conditions also deposited annealing Celsius 942 degrees Annealing 1150 degrees Annealing 1450 degrees Celsius hot isostatic pressing (HIP) 1300 degrees Celsius powder size (4) 15.9 15.9 15.9 15.9 15.9 Particle size (m) 12 12 6.7 10.6 5.5 Particle shape Long and long, all sides, equal parties, large parties, etc., large recrystallization, whether it is crystallographically oriented random random random random list 2 and 6 shows the characteristics of the cold spray button in the same spray, annealing and hot isostatic pressing (HIP) conditions. The process temperature is shown in the figure. All annealing was maintained for a temperature of 1.5 hours, and the hot isostatic flattening (HIP) cycle was maintained for 3 hours. Starting the powder size appears 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 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 36 200902741 are all samples of thickness, and are all oriented for use in an electron backscatter scatterer (EBSD), so the spray direction is vertically downward. In the context of materials science, "texture" means "crystal orientation is preferred". These orientations are completely random in a sample, and the sample is said to have no texture. If the crystalline orientation is not random, but has some preferred orientation, the sample has a weak, strong, or intermediate texture. Electronic Backscattering Diffraction (EBSD) The orientation information of the sample is obtained 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 chosen based on the particle size of the sample to ensure that the small features are not missed when the electronic backscatter diffraction (EBSD) scan is completed in a reasonable amount of time. Table 3 Process EBSD Stepping EBSD Area Index% CS, 1450〇c 2μπι 330μιηχ300 94 CS, 1150°C 2μπι 330μιηχ300 95 CS, 942〇C 2μπι 280μηιχ250 66 CS, No Annealing 4μηι 3 Area '330μηιχ150 71 to 73 Plasma Spray 50μιη 2.95 mm&gt;&lt;9&gt; 96 Results A cold spray, annealed at 1450 degrees Celsius Figure 7A shows a texture map of the relevant three orthogonal directions. Particles oriented within 20° of the {100} direction are shown in blue, 20 in the {111} direction. The inside is indicated by yellow, and is indicated by red in 20° in the {110} direction. When the orientation error 37 200902741 is reduced, the color is darkened. Gray (four) aligns the particles between the three orientations. The random distribution of colors in the graph is caused by the random distribution of the individual wheels. If the particles exhibit any particular texture, the one in the color of the material will have the advantage that if the majority of the particles are oriented in the {100} direction, yellow will be the dominant color.曰 The polar map (Fig. 7B) also shows a complete lack of symmetry, indicating that there is no texture in the microstructure. From the pattern, the sample can be considered to have a texture-free _ random texture, and the material particles are randomly oriented, have small particle sizes and have no system characteristics. Celsius 1150 疳 ' 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 Celsius. Celsius 942 grinding silver is small as shown in Figure 9. This sample also has a random texture. However, the indexation ratio is much lower than the previous sample, indicating that the material remains—high tension—the material is not recrystallized at lower annealing temperatures, as well as the texture map and polar map shown in Figure ( (see Figure 1 〇 And 11), it is found that the 3H texture is random, and the thickness is uniform and random. In this example, 'the following three texture maps represent three inspection areas, the first one is the first material deposited (the bottom of the spray layer), and the last one is the last material deposited (3 Heha fog layer Top): All graphs show that the texture associated with this vertical direction (through the thickness direction) is random. The result is a plasma. 38 200902741 • The substrate or support plate (the lower part of the texture map of Figures 12 to 13) has extremely large particles of equal width, which have a texture characteristic of the rolled and overannealed disk. 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 {1 〇〇}//ND and .{ 11丨}//ND shows 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 half of the texture grain map) and by the blue color in the figure, the texture is mainly 疋{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 Η1 and H3 polar maps are 15° smooth angle half width (compared to the usual one 〇.) to avoid the introduction of unnecessary peaks. In short, the above electron backscatter diffraction (EBSD) analysis shows 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: 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 that a 3 mm (mm) bend is produced in the copper support plate due to the same nozzle fog stress in the deposit. The support plate must be flat to seal against its mating flange. Because of these stresses, the machine is crying 39 200902741 During processing, it will only redistribute and cause continuous deformation, so the bending cannot be removed by machining. Since the same spray button, 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 Μ shows that a button deposit is plastically deformed to a permanent deformation after annealing for 15 hours at 95 °C. The copper support plate was removed from the target; the target was then annealed, bent and machined (Fig. 17). It is also apparent from this example that conventional copper and IS support plate materials are not ideal for refractory metal targets by cold spray. M traditional copper and Ming support plates have high thermal conductivity, but their elastic modulus is low (promoting deformation), and a large thermal expansion coefficient ("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 (thermal expansion coefficient) required for refractory metals. CTE&quot;) is similar to these refractory metals and has a high melting point). Cold spray can be used to make 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 〇 25 to 2 mm. One way to spray this layer is to use a powder mixture, which includes 200902741 including the support plate material and the target material __. Target and support plate material wins, 14 , .,, ~ ' π~~~--- material heat conduction Sex '--- Partial coefficient thermal expansion coefficient melting point ------ card cm / cm 2 seconds it X10'6PSI cm / cm °c °C copper ------ --------- - —_ 0.94 -----—__ 1 17 16.5 1083 Aluminum 0.53 10 23.6 660 铌0.12 17 7.3 2468 New 0.13 27 6.5 2996 Molybdenum.34 47 4.9 2610 Titanium 0.22 16.8 8.4 1668 316 Unrecorded steel 28 14 ～1350 KNbTal The sprinkling of the Japanese standard targets the pseudo-alloy (the bismuth and bismuth powders are still chemically different) in a 18&quot;x5&quot; planar magnetron cathode splatter. The target setting size is 4"xl7&quot;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 for splashing is used in 100 seem of argon, using a splash pressure of ι·〇x 1〇_3 Torr (basic pressure 4x 1〇_5 Torr), 5 〇 kW, 55 〇, approximate 73 watts per square foot. The target is excellently splashed from the beginning, no arc formation, no realism required for stability, burnout, time. A final film thickness of 1401 angstroms was deposited on a glass substrate (as measured by a Dektak 2A micro-section measuring instrument), which is a deposition time of the upper angstrom 41 200902741 watts squared shift - the rate is slightly higher than that used for 铌And the individual rate of the button is 3.7 ohms/square (as measured by the 4 ρί• probe on the glass plate). The result is calculated to be 51·8 〇 _ ohm centimeters. The expected resistivity of approximately 28 _ ohm centimeters. This material is sensitive to background house forces (impurities) and needs to be pumped to a low _5 to -6 Torr range for proper resistivity values. The absorption is 〇_4U as measured and calculated according to ASTM 5903 and Ε490). Oxide deposition# is performed using argon at (10)_ and oxygen at 90 sccm (lower oxygen levels cause gradual switching to metal mode), at 12 to 3 Torr, 3 〇 kW (44 watts/square) In the secondary volts. This is the _ of a few materials that have a higher erbium voltage in the oxide mode than in the metal mode. This Μ〇χ D.C. supplies an additive on the Sparc_le unit operating at 20 Hz. Once again, the - extremely stable splash process, no arc formation and no problem. The reduction rate is 40% of the ratio. This process provides a very aesthetically pleasing transparent film with a slight pink color in the reflection. The reflection has a slight green color and the final film thickness is 4282 angstroms. The refractive index is calculated to be 2·8, which is higher than the refractive index of individual lanthanum oxides (about 2.2 to 2.3). Nitride Deposition The attack is performed using a gas of 100 coffee and a gas of 2 coffee, approximately 2·0 X 1G-3 Torr. The nitride is freshly satisfactory and very stable. n A transparent nitride coating cannot be produced even after many process parameters have been tried. Using 3D kW of the MDX and Sparc_le units works well 1 shot yield is the metal ratio of m final film thickness 42 200902741 = ohms/square is ED (126G micro ohm centimeters). The daylight absorption was measured to be 0.59. Some observations are: Splatter is satisfactory in metal mode; sniper is excellent in oxide mode. The electrical isolation 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' No discoloration point in the runway. The entire target is deposited at a good rate. At a maximum power of 5 kW (kW) operating target, 5 kW converted to 75 watts/square 吋 a reference titanium (Ti) or nickel-chromium (Ni_Cr) is splashed at 35 watts per square foot. The target power is increased by 1 kW, and the towel is not inclined. At high power, there is no problem in terms of target expansion and overheating. Good 疋 dimensional stability, no problem at these chucks or edges. Fe Example 5. — A cold spray button on a copper support plate—Annealed and smoothed a TaNb target. A 17”xl.5”x〇.3〇〇-铌(TaNb) deposit On a 5 inch thick copper support plate. A layer of approximately 50% copper 50% (TaNb) thick was sprayed onto the copper prior to spraying the pure button (TaNb) to provide an intermediate coefficient of thermal expansion (CTE). The same spray assembly has a midpoint bend of approximately 〇·2吋. The target assembly is then vacuum annealed at 825 degrees Celsius for 1.5 hours to be sufficient to introduce recovery in the crucible and to make it ductile. Once 43 200902741 is cooled, the target assembly is placed in a flattening machine, successfully flattened to within 0.010 Torr, and machined. Example 6. Approximately 50/50 percent composition of the ^^(M〇Ti) splash target, which was produced by hot isostatic pressing (HIP) and by cold spray. The M〇Ti alloy system does not exhibit 100% solid solubility and contains several harmful brittle intermediate phases. When molybdenum (Mo) and titanium (Τι) 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 at 825 ° C and 15,000 ksi for 7 hours. 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 that only molybdenum is present in the target produced by cold spray. The pure elemental phase of titanium. Figure 20 shows that even after annealing for 15 hours at 700 degrees Celsius, there is substantially no interdiffusion, and at this magnification, no visible harmful phase is formed. The following is a list of the following materials: Equipment Cold Air Technology (Germany) Kinetiks 3000 or Kinetiks 4000 Cold Spray Condition: Nitrogen at 600 to 900 Celsius Degrees, pressures from 2 〇 to 4 〇 MPa (MPa) 'Powder feed rate from 3 〇 to 9 〇, and spray distance from 10 to 80 mm. Preferred conditions are 8 Torr to 900 ° C and a pressure of 3 to 3.8 MPa, a power feed rate of 30 to 50 g per minute, and a spray distance of 20 to 4 mm. Powder used: 44 200902741 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 of W with 50 volume percent copper, and fed through a powder feeder of a CGS cold spray system to make a WCu composition. 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 Figs. 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) for 2 hours and 4 hours showed a significant improvement in both thermal conductivity and coefficient of thermal expansion. Annealing is clearly demonstrated as an important step to significantly enhance thermal conductivity and to reduce thermal expansion coefficients for use in cold spray thermal management materials. Sample identification Thermal conductivity W/mK Thermal expansion coefficient ppm/C as it is 193 13.49 2 hours X 1600F 281 11.8 4 hours X 1600F 276 11.82 These thermal management products manufactured by cold spray technology have the following composition: Tungsten-copper ( WCu) compound: a molybdenum-copper (MoCu) compound having a tungsten (W) content ranging from 10% to 85%: having a molybdenum (Mo) content ranging from 10% to 85%. For thermal management applications, the main features of compounds produced by cold spray processes are: 45 200902741 (4) Copper flat microstructures, which can also be used with other metals such as silver, gold or gold. () Molybdenum or tungsten will generally maintain its particulate morphology or agglomerated particles. Eight materials such as Niobium (A1N), Carbonized Sith (Sic), etc. can also be used. The microstructure of the 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 purposes for all 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. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1(A) illustrates several planar representations made by using a cold gas of helium; Fig. 1(B) illustrates several planes produced by cold spray using nitrogen gas. Figure 2; Figure 2 illustrates several planar group targets made by cold spray after killing; Figure 3 shows the scanning electron microscope ("SEM") photomicrograph by means of a cold spray, Nitrogen cooling « and several sputum films that are turned out by several targets prepared by rolling short money; Figure 4A shows the smashing target after the smashing in close-up, showing the variegated and irregular of the light-pressing target Figure 4B is a close-up illustration of a squirting spray target after splashing, showing a smoother, non-mosquito surface of the chilled spray target; Figure 5 illustrates a plurality of button tubular preforms in accordance with the present invention; 46 200902741 Figure 6 shows a number of identical sprayed and annealed structures taken perpendicular to the spray direction in a photomicrograph; ', Figure 7AU illustrates several fruits treated with cold spray and annealed at Celsius; ° Figure 8 illustrates several results using a cold spray and annealing at 115 degrees Celsius Figure 9 illustrates several results using a cold spray and annealing at 942 degrees Celsius; Figure 10 illustrates that the substrate has a plurality of maximal particles of equal width and the like, which have a texture unique to the stamped and overannealed sheets; A number of polar maps in accordance with the present invention are illustrated; FIG. 12 illustrates a sample of the plasma spray button having a plurality of maximal particles of equal width and the like, having a texture unique to the stamped and overannealed sheet; FIG. Figure 1 illustrates a cold spray button-tank (TaNb) target with deposits over 44 mm long, 110 mm wide and 7 mm thick. Please note that in the center of the copper support plate 3 Millimeter bending; Figure 15 illustrates the load pair deflection for the same spray button, please note that the deposit failure due to fragile cracks does not exhibit any plastic deformation; Figure 16 illustrates the skew after 弯曲 8吋 during the bending test , permanent deformation obtained in tantalum deposits; 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 (M〇Ti) target And such harmful phases, and Isobaric flattening (&quot;HIP&quot;) period is the interdiffusion zone produced by combining the powder; 47 200902741 Figure 19 illustrates a similar sprayed molybdenum-titanium structure produced by cold spray, which contains only elemental elements and elements钬, and the no-harm diagram of the micro-junction shows that the cold spray shouting after annealing at 700 °C and L5 hours is not comparable to the hot-press equalization (&quot;HIP" target (Figure 19). ), substantially the formation of the sacred phase; ... Figure 21A illustrates the microstructure of tungsten-copper (w_Cu) (5 〇 / 5 〇 volume percent); Figure 21B illustrates copper (Cu) with a flat structure. [Main components Explanation of symbols] r /- k 48

Claims (1)

200902741 X. Patent application scope: 1. A splash target, including large uniform fine-grained structures such as those of less than 44 microns. No better texture when measured by an electron backscatter diffractometer (&quot;EBSD") The orientation, and the body throughout the target, exhibits a particle-free ribbon or textured ribbon. 2. The object of claim 2, wherein the average particle size is less than 20 microns, preferably less than 1 μm. 3. The object of claim 2, wherein the object has a layered structure incorporating a layer of the desired splash material and at least one additional layer on the support plate interface, the layer having a coefficient of thermal expansion ("cte") value between: the thermal expansion coefficient of the support plate (, CTE) and the thermal expansion coefficient (&quot;CTE" of the layer of splash material. 4. A lens or flat particle The splash target of the structure is measured by an electron backscatter diffractometer ("EBSD" without a better texture orientation, and the body of the target exhibits no grain size or texture band, and the target has a layered structure incorporating a layer of the splash material and at least an additional layer in the interface of the board having a thermal expansion coefficient (CTE) value which is between the thermal expansion coefficients of the support sheet ( , π.) is between the layer's slamming material's thermal expansion coefficient (&quot;CTE&quot;). 5. The object of any one of claims 1 to 4, wherein there is substantially no diffusion between the particles. The process of splattering the target component, including the deposition of a target powder material directly on the support plate or support tube, and manufacturing the target component in a single-Hungary, and subsequent 49 200902741 , Support board or support ★ Machined to the final target set size I, where the target includes - a large uniform fine particle structure of less than 44 microns / by an electron backscatter diffractometer (&quot; EBSD") has substantially no diffusion between particles and no good texture orientation, and exhibits no particle size or texture band throughout the body of the target. 7) The process described in claim 6 of the patent application, wherein The spraying is carried out by a cold, fog or power spray process. 8. The process of claim 6, wherein the target has a crystalline or flat grain structure characterized by no interparticle diffusion. The object 'is not measured by the electron backscatter diffractometer (&quot;EBSD&quot;), and the body of the target does not have a grain size or a texture band. a target component comprising a target and a support plate material, wherein the support plate material closely matches a thermal expansion coefficient of the target, and (4) of the support plate material is at least Celsius, which exceeds a temperature at which the target material can be annealed The target component of claim 9 wherein the target has been annealed to serve as a component for relaxing any of the same spray stresses. 11. The process of claim 6 of the patent scope, wherein The process is a cold spray process that includes a m-to-target, wherein the gas stream forms a gas powder mixture with a material powder selected from the group consisting of: 铌, knob, tungsten, molybdenum, Titanium, zirconium, and at least two of them, or alloys thereof with at least two or with other metals, the powder having a particle size of from 0.5 to 15 microns, wherein a supersonic 50 200902741 is provided to the Airflow, and directing the supersonic jet onto the target surface, thereby cold spraying a target having a completely random and uniformly random (in the entire thickness) fine particle size and crystallization U. The process of claim 11, wherein the spray is performed with a cold spray, and the target to be coated and the cold spray are placed at a pressure greater than 0.1 MPa. The environment controls the small room. a process for producing a plurality of multiple metal powder targets, comprising applying a metal powder mixture to a support plate to provide compliance between the target and the support plate, without detectable interdiffusion of the metal, Mutual diffusion can cause the formation of undesirable phases. 14. The process of claim 13, wherein the metal powder comprises a mixture of at least two metals, the metal being selected from the group consisting of tungsten, molybdenum, niobium, tantalum, titanium, and wrong. 15. A method of mitigation, which involves processing a plurality of silk conditions as described in the Scope of the Scope of the Patent or the 6 items, and thereby transferring the target. K. The method of claim 15, wherein the splattering method is selected from the group consisting of: magnetron splash, pulsed laser splash, ion Shusaki, tripolar splashing 'and its combination. A method of claim 16, wherein a method is used to complete the killing, the slamming method is selected from the group consisting of: magnetron splash, pulse laser, ion 'splashing Hit, and its combination. A method for manufacturing a film, comprising the following steps: 51 200902741 (4) The manufacture of a cold spray or a power nozzle mist - a difficult target; (b) / slamming the patent range 1 And (b) removing a plurality of metal atoms from the target; and (d) forming a film comprising the metal atoms on the substrate. 19. The method of claim 18, wherein the step of adding after (9) further comprises the step of supplying a reactive gas to the metal atoms. The method of claim 19, wherein the reaction gas is oxygen, nitrogen and/or a helium containing gas. The method of claim 2, wherein the film has a thickness ranging from 0.5 nm to 1 μm. 22. A film produced by the method of any one of claims 18 to 21 of the patent application. A film produced as described in claim 22, wherein the film has a non-uniformity of less than 4%. A flat panel display device comprising a film as described in claim 22 or 23. The flat panel display device of claim 24, wherein the device is selected from the group consisting of a thin film transistor _ liquid crystal display, a plasma display panel, an organic light emitting diode, and an inorganic light emitting diode Body display' and electroluminescent display. 26_ The film of claim 22 or 23, in a solar cell device, a semiconductor device, a coated glass for architectural use, an ink jet print head, 52 200902741 - an optical coating, or a diffusion barrier Use in the layer. 27. The objective of claim 1, wherein the target is a disc-shaped, tubular or contoured target. Twisting the target and - (4) hitting the target component, which has previously been destroyed to its available end of life, and then has been repaired by filling a hard (four) end in the rot (four) product to cause the entire volume of the target to have The microstructure of any one of claims 1 to 5 is claimed. 29. A sniper target and a slamming target component that has previously been destroyed to the end of its useful life, and then has been repaired by filling a hardened powder in the rot (four) product to cause the new material - The large microstructures of the parties are relatively finer than the raw materials. 30. A thermal management material produced by a process comprising: a cold spray or a power spray-powder mixture to form a composite structure on a substrate, the powder mixture consisting of a solvent-resistant powder and a high heat conductive metal powder . 31. The process of claim 30, wherein the thermally conductive metal powder is copper, aluminum 'silver, gold, and the substrate is a stainless steel substrate. 32. The process of claim 31, wherein the stainless steel substrate is removed by machine processing. 53