TWI229698B - A gas-spraying powder manufacture method of aluminum alloy sputtering target - Google Patents

Abstract

A gas-spraying powder forming method of aluminum alloy sputtering target applicable in forming various kinds of aluminum alloy sputtering target (aluminum-chromium, aluminum-silicon-copper, aluminum-titanium) provides a better procedure as following: melting metallic raw materials for producing the aluminum alloy sputtering target into a metallic solution; gas-spraying the metallic solution into metallic powders; vacuum hot pressing the metallic powders into aluminum alloy sputtering target while adding inert gas as protection gas. The hot pressing means adding pressure onto the metallic powders by a hot press oven at a certain temperature for a certain period of time to purge gap among metallic powders to form a product of expected density and shape.

Description

1229698 V. Description of the invention (1) (I) Field of invention: The present invention is related to: a kind of raw material for making Ming alloy quenching target material by air spray powder. 曰: 5: spray method to make money keys according to the alloy distribution ratio The i, μ + ^ δ gold powder without material is sieved to obtain the appropriate powder granules: Finally, vacuum hot pressing is performed at the end of this description to make a description of the conventional technology of Qianqiangan (2): During the process of reading and writing multiple-time optical discs (CD-Rflf, DVD-ram, etc.), it is necessary to use aluminum alloy (such as aluminum-titanium, aluminum-chromium alloy) thin reflective layers; while flat-panel displays (such as TFT- For LCD, PDP, and 0LED, it is also necessary to use aluminum alloys (such as aluminum-tantalum and aluminum) to make conductive films, and then to make electrodes (electrode). Because the alloy splashes dry materials, it becomes an optical disc. It is an indispensable material in the manufacturing process of the flat panel display industry. Among the major sputtering target manufacturers in the world, there are two different processes for the aluminum alloy sputtering dry manufacturing, one is to make the casting key by casting method. 'Follow the forging process to make it, and the other one is Spray F〇rmin Made by g method, Japan ’s Kobe is the only company to produce aluminum alloy sputter targets using the Spray Farming process. Please refer to US Patent Nos. 9 and 6096438, which are based on molten alloys that use high pressure gas to: After that, hot isostatic pressing (HIP) or forging process is used to make it. In the conventional casting / forging process, when making aluminum alloys / base materials, aluminum alloys are often spattered by the addition of alloying elements. Wood production

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Segregation, which makes the quality of the thin film obtained by sputtering worse, and the particles on the surface of the sputter handle are prone to produce particles, which will also affect the uniformity of the film properties; and if the conventional Spray F0rming method is used, the formula 0 Although the above-mentioned related defects can be avoided when making Shao alloy sputtering targets, > it will greatly increase the production cost of sputtering targets, especially when making some sputtering targets that are not easy to forge and must use hot equal pressure, Its cost will increase due to the use of hot equalizing pressure. Obviously, the use of custom-made aluminum alloys without sputtering is not easy to cause segregation, which in turn makes the quality of the thin film obtained by sputtering, or easy to produce micro particles (particie) on the dry surface of money deposits, or the production cost is too high. , The process is too complicated, and the production yield is not easy to control. (3) Brief description of the invention: An object of the present invention is to provide a method for manufacturing aluminum alloy sputtering shoes * material by air spray powder, which can avoid the phenomenon of material segregation. Another object of the present invention is to provide a method for making aluminum alloy sputtering material by using air spray powder, and the raw material powder of sputtering target material can be produced according to the alloy composition distribution ratio. Yet another object of the present invention is to provide an air spray material. The method for making aluminum alloy money key dry material by powder has simple process and low cost. In order to achieve the above-mentioned object, the present invention proposes a method for making an aluminum two-gold sputtering target by using an air-spraying powder. For the production of various different aluminum alloy sputtering targets, the inscription r—chrome, aluminum—silicon—copper, and aluminum _ Titanium, etc.) can be applied, and its preferred implementation is' township: providing metal raw materials for making aluminum alloy sputtering targets to melt into one

5. Description of the invention on page 5 (3) Straight, "The metal spray is made into a metal powder by air spraying; r and: the metal powder is made by hot pressing forming Inert gas is used as a protective gas. To 1301 ', the metal aluminum and aluminum-titanium master alloy are heated to 1100 at the same time. Titanium molten metal is used to melt it into an aluminum-titanium molten liquid; -To 65 (T (Λ into anaerobic titanium powder; using vacuum hot pressing forming, at a temperature of 500 yi a titanium powder tif 20MP3 to 50MP3, for 80 to 100 minutes, the aluminum body, hydrogen gas Λ combined money) The remaining material, and chlorine gas is introduced as a protective gas, wind milk is used as a reducing gas. The steps 3 and 3 provide a more in-depth description of the present invention, which is illustrated by the following diagrams: Gongming and the detailed description of the invention. $ Helpful when working. Goods (5) Detailed description of the present invention: :: In the manufacturing of optical discs and LCD flat displays, it has accounted for a certain amount in the world, so it is also used in the sputtering target of related films. ^ 制 # 古 、 ± _ 罝. However, the imported sputtering target form generally used in the industrial market ⑴The casting and forging process and ⑺Spray free scale after the / 1 p process; the innovation of this patent is to avoid catching and: the appropriate process to make high-quality light-plated light-reducing materials. Implementation :: to !:嗔 The method for making target alloy sputtering target with 嗔 powder, its 耳 ear steps are shown in Figure 1. ⑷The raw material standard m, different ming alloy minified handles can be made according to the desire, example 1229698

、, Ming 'Shi Xi—Steel ϋ and other alloys with different ming alloys are recorded in the dry pit 2 ”! Different metal raw materials, when #, can also be used to destroy the ore alloy (splash ore material to the remaining- (Replacement and replacement) After recycling and confirming the composition, collect the inscription; after the gold sputtering target is crushed, it is used as the different metal raw material required. (B) Air-spraying method to make powder 2. The metal prepared in step (a) The raw materials are placed in a heating furnace of an air jet furnace, and the metal raw materials are melted into a metal melt, and then an aluminum alloy powder is produced by a gas injection method using a gas generated to avoid oxidation of the alloy powder. (C) Powder, collection , Sieving 3, after collecting the aluminum alloy powder obtained in step (b), sieving to leave a powder that meets the required particle size, the total material yield (γ ie 1 d) is 8 5 (D) Powder sintering and forming 4, put the aluminum alloy powder sieved in step (c) into the hot pressing furnace, and apply hot pressing at different time, temperature and pressure according to different requirements. And inert gas is used as a protective gas. (E) Finish the aluminum alloy sputtering target 5 and go through the vacuum hot pressing of step (d). The gap between the aluminum alloy powders has disappeared, and the required aluminum alloy sputtering target has been obtained. The air spray method, as the name implies, uses the gas as the spray medium to break up the molten metal melt into small droplets. Or use centrifugal force to break it into small droplets, and then cool and solidify it into a metal powder. The commonly used gases are air and inert gas, such as nitrogen and argon, and the required gas injection furnace can be divided into levels There are two types: vertical and vertical. The following uses vertical gas jet furnace as an example.

Fifth, the description of the invention. ⑸ Refer to the schematic diagram in Figure 2. The required metal 60 heater uses the inlet and outlet, and due to the effect of I swell, the intermediate superheated band is formed in 62, followed by 63. The formula is as follows: The gas spray furnace used in the gas spray method of the present Λ is a direct spray furnace δ, which is used to put the aluminum material into a crucible 600 of the heating furnace 60, and use ^ 埶 6 〇1 heating to melt the metal raw materials into an aluminum alloy melt? ,,,, and :: Gas 8 'Make the aluminum alloy melt 7 from the nozzle "quickly close:" 7 at the outlet of the nozzle 61 under the inert gas 8 quickly, so that the aluminum alloy melt 7 is at the outlet of the nozzle 61, that is, empty The cone 70 diverges outward if the #alloy solution 7 has the effects of shear stress and acceleration force. First, it forms a tough :: sphere-shaped Ming alloy powder 71 concentrated on the particle size and spray of the powder collection chamber system. Experiment of the relationship between conditions D = |-[r / pm] 0-22 [Um / pm] 0.57 D: Powder particle size C: Nozzle geometric constant V: Spray gas velocity Um: Viscosity of metal melt pm: Metal Density of the melt 9 " •• The surface tension of the metal melt is known from the formula 'the size of the powder particles produced is inversely proportional to the speed of the spray gas', that is, the faster the speed of the spray gas, the larger the particle size of the powder The “smaller” can also use different control parameters to control the particle size of the powder. 1229698 5. Description of the invention (6) and the chemical composition of the powder. The invention uses the air spray method to make aluminum alloy powder, which can accurately grasp the particle size and chemical composition of the Shao alloy, and uses an inert gas to rapidly spray the powder to make sure that no segregation caused by alloy elements occurs.

“Hot pressing” as the name implies is to use a hot pressing furnace to apply pressure to the metal powder to be press-formed, and maintain it at a certain temperature for a period of time to make the gap between the metal powder disappear, and obtain the required density and shape. It can be roughly divided into two steps: (1) in the initial sintering stage, the metal powder undergoes a rapid necking growth through diffusion process or plastic deformation, resulting in an increase in the particle contact area ', so that the gap between the metal powder becomes a cylindrical hole; (2) Medium-term sintering stage 'In this stage, these cylindrical holes will shrink into smaller cylindrical holes' and any gas will be squeezed out and trapped in the holes, and then the' small cylindrical holes become extremely unstable and subject to Under the action of surface and grain boundary energy, closed and rough spherical pores are formed; (3) in the final sintering stage, the 'independent spherical pores' disappear and reach full density to obtain the required density and shape. As shown in Fig. 3 ', it is a schematic diagram of a hot-pressing furnace used in the hot-press forming of the present invention. The sieved aluminum alloy powder 71 (shown in Figure 2) is placed in the graphite mold 90 of the autoclave 9, and the graphite mold 90 is formed by the shell base 9!

The hydraulic pressure device 92 applies pressure to the aluminum alloy powder 71, and the heater 93 heats the alloy powder 71. In this way, after a period of time, the required aluminum alloy sputtering target can be obtained. The hydraulic device 92 includes a base 920, a hydraulic rod 921, a pad 922, and a punch 923. When the oil pressure device 92 is activated, the oil pressure rod 921 is displaced by pressure and drives its front end.

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: Connect the pad 922 and the punch 923 'Apply pressure to Ming alloy powder 7i as shown in Figure 4 #, which is a flow chart of the invention using air spray gold sputtering target, the steps are as follows: (a) For aluminum and aluminum-titanium master alloy 13, a composite example of pure aluminum and aluminum-titanium master (Ab 2.3wt% Ti) is prepared. Knife ratio (b) Aluminum and aluminum-titanium master alloy are melted into aluminum-titanium melt, and powder is produced by air-jet method 2 =. The raw materials prepared in step (a) are placed in an air-jet furnace for air-jetting. The nozzle material used in this gas injection furnace is made of ceramic material. The caliber is 2 · 5 ~ 4 · 0mm, and the crucible is made of zirconia. The metal boat and the non-titanium master alloy are placed in a crucible and heated to 11000 ~ 13 (C) to melt the metal aluminum and the aluminum-titanium master alloy into an aluminum-titanium alloy melt, and the nozzle is performed by water circulation. Cool and spray with ordinary argon (Ar) 'The atomization process of the aluminum-titanium alloy powder produced by this gas spray method takes a total of about 2 to 4 minutes, and due to the use of a protective atmosphere-argon rapid spray powdering' Therefore, the produced aluminum-titanium alloy powder does not segregate. (c) Collecting and sieving aluminum-titanium powder 3a. Then, the aluminum-titanium powder is collected and sieved. The total material yield (Yield) is 90.5%, and the particle size distribution is 40%. ~ 100. Analysis of the composition of some aluminum-titanium powder shows that its composition is the same as that of the prepared raw material, that is, A1-2 · 3wt0 / 〇Ti 〇 (d) Ming-titanium powder sintering, forming 4a, and sieving in step (c) is completed The aluminum-rhenium powder is placed in a graphite mold of a hot-pressing furnace.

Page 10 V. Description of the invention (8) ':: $ 体' in which argon is used as the protective gas for the lice milk in the hot press forming process as the reducing gas, and the sintering temperature is 5500c ~ 6 > and the junction pressure is 20MPa ~ 50MPa The sintering time is 80 ~ 10q. After the firing example is sintered for 90 minutes, the Ming_iridium coin plating: Zhong'ben (e) completes the Ming-titanium alloy sputtering target 53, after step (d) Winding into a community shape. After 2, the Al-2.3wt% Ti was sputter-dried and taken out of the hot-pressing furnace, the amount; Gan Cheng ~ degree value of 2. 71 g / cm3 (the density of aluminum is 2.7, dense ". 5_, can be known The obtained A " .3 has very good density. Fig. 5 shows the flow chart of the dried ore, which is the flow chart of the invention using air spray powder to make the material; as shown in Fig. 6, it is the invention of the two: In the end, the process of the sputtering target for aluminum-silicon-copper alloy sputtering is similar to the previous step, but the splash ore produced by the step of using the raw materials is not eye-catching; it also shows that the invention uses a gas nozzle = And the method of alloy sputtering target can be applied to the production of various aluminum alloys, and can avoid the use of conventional casting and forging: making ::: target plating target will cause material segregation; and It not only produces: °° Gold Spattering: sPray Formin "type production of alloy sputtering target y is earlier and many more, it can be said that all the disadvantages of the conventional technology are completely improved. The cost of the material is low. 1 The description uses the preferred embodiment to explain the above, and I understand that such as: using other air spray powder to make easy coupling or using horizontal air spray Carry out the air-jet method, etc .; 丨 plating the target material; The description of the preferred embodiment of the present invention is only used to help "::: application: application: 1229698 V. Description of the invention (9) 1 2 0 0 ° C -The titanium alloy is melted into a melt, and the nozzle is cooled by water flow, and sprayed with argon (Ar) pressure of 25 Kgf / cm2. The atomization process of the aluminum-titanium alloy powder produced by this air spray method takes about a total of about 4 minutes, and because the protective atmosphere-argon is used for rapid spray powdering, the aluminum-titanium alloy powder produced does not have segregation. (B) collection, the aluminum-titanium powder is collected and sieved Action, the total material yield (Yie 1 d) is 93%, the particle size distribution of its powder is shown in Table 1 below, and the SEM measurement chart of its powder is shown in Figure 7. Table 1: Al_2.3wt% Ti Powder particle size distribution (μτη) > 149 149-104 104-61 6144 < 44% 10.27 11.58 43.57 25.6 8.97 (c) Collect the above-mentioned aluminum-titanium spray powder and place it in a graphite mold of a hot press furnace A mixed gas of argon and hydrogen is passed in, wherein argon is used as a protective gas in the hot-press forming process, and hydrogen is used as a reduction Gas, sintering temperature is 600 ° C, sintering pressure is 3 5 M pa, and sintering time is 90 minutes, forming the Ming-titanium alloy sputtering target. (D) Finishing the aluminum-titanium alloy sputtering target, amount The density value was measured as 2. · 7 1 g / cm3 (the density of Ming was 2.7 g / cm3; the density of titanium was 4.5 g / cm3), and the density of the obtained Al-2. 3wt% Ti sputtering target was known. Very good, as shown

Page 121229698 V. Description of the invention (ί) The difference between the product shown in this article and the product difference of Mitsubishi is shown, but the product manufacturing process is simple and allows the invention to be obtained. Jiashi has limited the spirit and scope of the invention. In summary, it is revealed that there are novel problems, and the patents of inventions whose method effectiveness has already been detailed should be prayed for. The comparison between the Al-2.3wt% Ti alloy target sputtered film produced by Ming and Japan shows that the effect of the sputtered film of the present invention is better than that of the commercial product of Kate 1 c 〇, which is only higher than that of High Purity Chemical. There are many businesses, so the cost is cheap. The drawings and descriptions are explained in the preferred embodiment as above. It is easy to connect: using other air-spraying powder to make aluminum alloy sputtering targets, air-blasting furnace for air-spraying powder, etc., familiar with the spirit of the invention in this field, all It is conceivable to implement the changes, so the description of the embodiments is only used to help understand the present invention, not for the spirit. Without departing from the spirit of the present invention, when it can be replaced with equivalent changes, it will not depart from the present invention. The present invention has no related technical disclosure in the field of conventional technology; the technical content of the present invention can definitely solve the principles in this field. Those who are not easy to complete based on the conventional skills, and their achievements are progressive and sincere. In accordance with the provisions of the Patent Law, I would like to ask your reviewing committee to review and give permission to «

Page 13 1229698 Brief description of the drawings (4) Brief description of the drawings: Figure 1 is a flow chart of the present invention for making an aluminum alloy sputtering target by using air spray powder. FIG. 2 is a schematic diagram of an air jet furnace used in the air jet method of the present invention. Fig. 3 is a schematic view of a hot-pressing furnace used in hot-press forming of the present invention. FIG. 4 is a flowchart of manufacturing an aluminum-titanium alloy sputtering target by using air spray powder according to the present invention. Fig. 5 is a flow chart of manufacturing an aluminum-chromium alloy sputtering target by using air spray powder according to the present invention. Fig. 6 is a flow chart of manufacturing an aluminum-silicon-copper alloy sputtering target by using an air spray powder according to the present invention. FIG. 7 is a SEM image of Al-2.3wt% powder according to an example of the present invention. FIG. 8 is a comparison diagram of the difference in wiping rate between A 1-2.3 w t% alloy palladium sputtered film and Japanese products according to the embodiment of the present invention. Description of drawing number: 1 ~ Raw material preparation «1 a ~ Ming and Ming-titanium master alloy lb ~ Ming and Shao-chrome master alloy lc ~ Ming and Ming-ί Xi master alloy and Ming-copper master alloy 2 ~ Air-jet powder 2 a ~ Melting aluminum and aluminum-titanium master alloy into aluminum-titanium melt, and making powder by air spray method 2b ~ Melting aluminum and aluminum-chromium master alloy into aluminum-chromium melt, and making powder by air spray method

Page 141229698 Brief description of the drawing 2 c ~ 纟 g and 纟 g-broken master alloy and Ming-copper master alloy are melted into Ming-s-copper melt, air-pulverized 3 ~ powder collection, sieving Divide 3a ~ collection, sieving aluminum-titanium powder 3 b ~ collection, sieving aluminum-chromium powder 3c ~ collection, sieving Ming-shixi-copper powder 4 ~ powder sintering, forming 4a ~: is- Qin powder sintering, forming 4b ~ Ming · Luo powder sintering, forming 4c ~ Shao-crushed-copper powder sintering, forming 5 ~ Complete aluminum alloy sputtering target 5a ~ Complete Ming-titanium alloy demineralization dry material 5b ~ Complete aluminum- Chromium alloy sputtering target 5c ~ Complete aluminum-silicon-copper alloy sputtering target 6 ~ Vertical gas spray furnace 6 0 ~ Heating furnace 6 0 0 ~ Hanging pan Θ01 ~ Heating device 6 1 ~ Nozzle 62 ~ Spray chamber 6 3 ~ Powder collection bin 7 ~ Ming alloy solution 70 ~ Hollow cone 7 1 ~ Aluminum alloy powder

Page 15 1229698 Brief description of drawings 8 ~ Inert gas 9 ~ Hot press furnace 9 0 ~ Graphite mold 9 1 ~ Housing base 9 2 ~ Hydraulic device 9 2 0 ~ Base 9 2 1 ~ Hydraulic rod 9 2 2 ~ Pad 9 2 3 ~ Punch 9 3 ~ Heater

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Claims (1)

1229698 6. Applying for a patent for snake enclosure 7. As described in item 6 of the scope of the patent application, a method for producing an aluminum alloy sputtering target by using air spray powder, wherein step (c) the aluminum alloy sputtering target is aluminum-titanium Alloy minus: dry mineral. 8. The method for making an aluminum alloy sputtering target by using air spray powder as described in item 1 of the scope of the patent application, wherein the hot-press forming system described in step (c) can pass an inert gas as a protective gas. 9. The method for producing an aluminum alloy sputtering target by using an air spray powder as described in item 1 of the scope of the patent application, wherein the inert gas system may be argon. 1 0. — A method for making an aluminum-titanium alloy sputtering target with an aluminum content of 50-100 wt% by using an air spray powder, the steps include: (a) aluminum alloy sputtering according to the desire Prepare the metal inscription and the inscription-titanium master alloy raw material in the proportion of the target to be plated, and heat it to melt into the inscription-titanium mixed melt; (b) Pass in an inert gas with a pressure of 40_60Kgi / cm2, and apply the Aluminum-titanium mixed melt is used to make aluminum-titanium alloy powder; (c) Pass the alloy powder into inert gas and hydrogen, apply a pressure of 20_50Mpa, and sinter at a temperature of 550-600 ° C for 80-100 minutes. The aluminum-titanium alloy powder is made into an aluminum-titanium alloy key bond dry material by compression molding. 1 1. The method for producing an aluminum alloy sputtering target by using air spray powder as described in item 10 of the scope of patent application, wherein the step (a) is a heating temperature of 1 1 0 0 ° C to 1 300 ° C. between. 1 2. The method for producing an aluminum alloy sputtering target by using an air spray powder as described in item 10 of the scope of the patent application, wherein the required time is 90 minutes. Page 18 1229698 Page 19