阅读说明：本技术 一种高纯无氧铜溅射镀膜靶材的制备方法 (Preparation method of high-purity oxygen-free copper sputtering coating target material ) 是由 张灵杰 于 2021-05-31 设计创作，主要内容包括：本发明提供了一种高纯无氧铜溅射镀膜靶材的制备方法,包括选取高纯无氧铜铜锭步骤、清洗步骤、真空熔炼提纯步骤、铸造步骤、预热处理及挤压、退火处理步骤、冷焊步骤、缺陷探伤和结晶扫描检测、清洁处理步骤,制得无氧铜溅射镀膜靶材,本发明采用真空熔炼提纯工艺和金属挤压工艺相配合的方法,通过低温真空冷焊工艺和低温锻造工艺,得到纯度≥99.9995%,平均晶粒尺寸≤100um,且晶粒均匀、晶粒取向一致的高纯度、高镀膜率的溅射铜管靶,为平面显示器行业的发展和应用奠定了坚实的基础。(The invention provides a preparation method of a high-purity oxygen-free copper sputtering coating target material, which comprises the steps of selecting a high-purity oxygen-free copper ingot, cleaning, vacuum smelting and purifying, casting, preheating, extruding, annealing, cold welding, defect detection, crystal scanning and detection and cleaning to prepare the oxygen-free copper sputtering coating target material.)

1. A preparation method of a high-purity oxygen-free copper sputtering coating target material is characterized by comprising the following steps: the preparation method comprises the following preparation steps:

selecting a high-purity oxygen-free copper ingot as a raw material of an oxygen-free copper sputtering coating target, and sieving the high-purity oxygen-free copper ingot for later use;

step two, cleaning the surface of the copper ingot selected in the step one, drying and then cleaning the surface of the copper ingot with acetone for later use;

step three, carrying out heat treatment on the copper ingot treated in the step two, wherein the temperature of the baked copper ingot is 150-250 ℃, and then putting the baked copper ingot into a vacuum smelting furnace to purify the copper ingot;

casting a corresponding mold according to the size specification of the product, wherein the casting mold is connected with the interior of a vacuum smelting furnace, and a copper bar blank with a corresponding specification is obtained through a casting process;

step five, carrying out preheating treatment on the copper bar blank obtained in the step four, wherein the preheating temperature is 700-950 ℃, and then carrying out extrusion and low-temperature annealing treatment on the copper bar blank to obtain a tube blank with uniform crystal grains;

step six, welding the two ends of the tube blank in the step five to prepare a tube target blank body with flange plates at the two ends;

step seven, performing primary detection and cleaning on the tube target blank obtained in the step six, and then performing defect detection and crystal scanning detection;

and step eight, after nondestructive inspection is qualified, washing the target, drying and carrying out vacuum packaging to obtain the oxygen-free copper sputtering coating target material with the purity of more than or equal to 99.9995% and the average grain size of less than or equal to 50 um.

2. The method for preparing a high-purity oxygen-free copper sputtering coating target material according to claim 1, which is characterized by comprising the following steps: and step two, a high-pressure water gun is adopted to spray water on the surface of the copper ingot for cleaning, and the pressure of the high-pressure water gun is 0.2-1 MPa.

3. The method for preparing a high-purity oxygen-free copper sputtering coating target material according to claim 1, which is characterized by comprising the following steps: and step three, the purity of the copper bar billet after vacuum melting and purification is more than or equal to 99.99%.

4. The method for preparing a high-purity oxygen-free copper sputtering coating target material according to claim 1, which is characterized by comprising the following steps: and step four, introducing argon as protective gas in the casting process, wherein the purity of the argon is more than or equal to 99.99 percent.

5. The method for preparing a high-purity oxygen-free copper sputtering coating target material according to claim 1, which is characterized by comprising the following steps: and fifthly, the low-temperature treatment temperature is 600-750 ℃.

6. The method for preparing a high-purity oxygen-free copper sputtering coating target material according to claim 1, which is characterized by comprising the following steps: and welding the tube blank in the sixth step by adopting a vacuum cold welding mode, controlling the welding temperature during welding, and controlling the temperature of a welding affected zone to be less than or equal to 200 ℃.

7. The method for preparing a high-purity oxygen-free copper sputtering coating target material according to claim 1, which is characterized by comprising the following steps: and seventhly, detecting the flaw of the welding seam by using an ultrasonic nondestructive flaw detector, detecting whether the welding part has a defect, simultaneously performing C scanning by using water immersion type ultrasonic waves, wherein no pore defect with the average diameter larger than 0.3mm exists in the machined pipe blank, the wave intensity of the bottom surface of the crystal scanning is not smaller than 80%, and the average grain diameter is smaller than 30 mu m.

Technical Field

The invention belongs to the technical field of thin film liquid crystal displays, and particularly relates to a preparation method of a high-purity oxygen-free copper sputtering coating target material.

Background

With the rapid development of new devices and new materials in the microelectronics industry and the application of electronic, magnetic, optical, photoelectric and superconducting films in high-tech and industrial fields, the market scale of sputtering targets is increasingly enlarged, and targets throughout the world are mainly produced in japan, the united states and germany.

The utilization rate of the copper tube target is as high as 70-80%, the utilization rate of the plate target is only 30%, and the copper purity in the copper tube target for sputtering is low, the coating film is not uniform, and the like, so that the future use is in an increasing trend. However, due to the reasons of high cost, complex process, high technical and quality requirements, long purchase period and the like, a large number of imports are needed, and become a key factor for limiting the development of the liquid crystal panel field in China for a long time. Therefore, the development of the high-purity oxygen-free copper tube target material for sputtering becomes the key for promoting the rapid development of the flat panel display industry in China at present.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a preparation method of a high-purity oxygen-free copper sputtering coating target material, which adopts a method of matching a vacuum melting purification process with a metal extrusion process and adopts a low-temperature vacuum cold welding process and a low-temperature forging process to obtain a high-purity high-coating-rate sputtering copper tube target with the purity of more than or equal to 99.9995 percent, the average grain size of less than or equal to 100um (the average grain size of less than or equal to 50um in a conventional state), uniform grains and consistent grain orientation.

The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a high-purity oxygen-free copper sputtering coating target material comprises the following preparation steps:

selecting a high-purity oxygen-free copper ingot as a raw material of an oxygen-free copper sputtering coating target, and sieving the high-purity oxygen-free copper ingot for later use;

step two, cleaning the surface of the copper ingot selected in the step one, drying and then cleaning the surface of the copper ingot with acetone for later use;

step three, carrying out heat treatment on the copper ingot treated in the step two, wherein the temperature of the baked copper ingot is 150-250 ℃, and then putting the baked copper ingot into a vacuum smelting furnace to purify the copper ingot;

casting a corresponding mold according to the size specification of the product, wherein the casting mold is connected with the interior of a vacuum smelting furnace, and a copper bar blank with a corresponding specification is obtained through a casting process;

step five, carrying out preheating treatment on the copper bar blank obtained in the step four, wherein the preheating temperature is 700-950 ℃, and then carrying out extrusion and low-temperature annealing treatment on the copper bar blank to obtain a tube blank with uniform crystal grains;

step six, welding the two ends of the tube blank in the step five to prepare a tube target blank body with flange plates at the two ends;

step seven, performing primary detection and cleaning on the tube target blank obtained in the step six, and then performing defect detection and crystal scanning detection;

and step eight, after nondestructive inspection is qualified, washing the target, drying and carrying out vacuum packaging to obtain the oxygen-free copper sputtering coating target material with the purity of more than or equal to 99.9995% and the average grain size of less than or equal to 50 um.

And further, in the step two, a high-pressure water gun is adopted to spray water on the surface of the copper ingot for cleaning, and the pressure of the high-pressure water gun is 0.2-1 MPa.

Further, the purity of the copper bar billet after vacuum melting and purification in the third step is more than or equal to 99.99%.

Furthermore, in the fourth step, argon is introduced as protective gas in the casting process, and the purity of the argon is more than or equal to 99.99 percent.

Further, the low-temperature treatment temperature in the fifth step is 600-750 ℃.

Further, the tube blank in the sixth step is welded in a vacuum cold welding mode, the welding temperature is controlled during welding, and the temperature of a welding affected area is controlled to be less than or equal to 200 ℃.

And step seven, detecting the flaw of the welding seam by using an ultrasonic nondestructive flaw detector, detecting whether the welding part has a defect, simultaneously scanning by using water immersion type ultrasonic C, wherein no pore defect with the average diameter of more than 0.3mm exists in the machined pipe blank, the wave intensity of the bottom surface of the crystal scanning is not less than 80%, and the average grain diameter is less than 30 mu m.

The invention has the beneficial effects that: the invention adopts the method of matching the vacuum melting purification process with the metal extrusion process, and obtains the sputtering copper tube target with the purity of more than or equal to 99.9995 percent, the average grain size of less than or equal to 100um (the average grain size of less than or equal to 50um in the conventional state), uniform grains, consistent grain orientation, high purity and high coating rate by the low-temperature vacuum cold welding process and the low-temperature forging process, overcomes the limitations of low purity, large and uneven grains and the like of the copper tube target prepared by the traditional process, and lays a solid foundation for the development and application of the flat panel display industry.

Detailed Description

The embodiments of the present invention are described in detail with reference to specific embodiments, and the embodiments and specific operations are provided in the present embodiment on the premise of the technical solution of the present invention, but the scope of the present invention is not limited to the following embodiments.

A preparation method of a high-purity oxygen-free copper sputtering coating target material comprises the following preparation steps:

selecting a high-purity oxygen-free copper ingot as a raw material of an oxygen-free copper sputtering coating target, wherein the raw material copper ingot prepared from the high-purity oxygen-free copper sputtering coating target is selected, and the preparation modes of the copper ingot comprise two modes: the method comprises the steps of (1) a vacuum melting method and a powder metallurgy method, wherein the copper ingot prepared by the powder metallurgy method is low in density and purity, so that an oxygen-free copper ingot prepared by the vacuum melting method is selected as a raw material; sieving for later use;

step two, cleaning the surface of the copper ingot selected in the step one, drying and then cleaning the surface of the copper ingot with acetone, wherein the purity of the acetone is more than or equal to 99 percent for later use;

step three, carrying out heat treatment on the copper ingot treated in the step two, wherein a copper baking furnace is selected as the furnace during the heat treatment, the temperature of the baked copper ingot is more than or equal to 200 ℃, but the temperature cannot be too high, the oxidation of the copper ingot is avoided, the temperature of the baked copper ingot is controlled to be 150-250 ℃, and then the baked copper ingot is put into a vacuum smelting furnace to purify the copper ingot;

casting a corresponding mold according to the size specification of a product, wherein the casting mold is connected with the interior of a vacuum smelting furnace, impurities and oxygen are not introduced from the outside in the whole process, after the casting is finished, rough machining is needed to be carried out on the mold, burrs or bulges at the end part are cut off, meanwhile, high-purity argon is needed to be introduced in the casting process to protect others, new gas impurities are prevented from being introduced into the copper bar in the casting process, the purity of the high-purity argon is more than or equal to 99.99%, and a copper bar blank with the corresponding specification is obtained through the casting process;

preheating before forging, extruding or rolling, wherein the preheating temperature is 700-950 ℃, and the machining allowance is reserved, carrying out low-temperature annealing treatment after extruding to obtain a tube blank with uniform crystal grains, and the low-temperature treatment temperature is 600-750 ℃;

step six, welding the two ends of the tube blank in the step five to prepare a tube target blank body with flange plates at the two ends; the cold welding machine adopts a sub-laser instant melting cold welding machine, and the whole welding process needs to be in a vacuum environment, so as to avoidFree of introduction of O into the weld₂Impurities such as gas; meanwhile, the cold welding power of the sub-laser instant fusion cold welding machine is taken as follows: p is more than or equal to 2000W and less than or equal to 3200W, and t is more than or equal to 0.1s and less than or equal to 1s in single-time repair time;

step seven, performing primary detection and cleaning on the tube target blank obtained in the step six, and then performing defect detection and crystal scanning detection; detecting the flaw of a welding seam by using an ultrasonic nondestructive flaw detector, detecting whether a welding part has a defect or not, simultaneously performing submerged ultrasonic C scanning, wherein no pore defect with the average diameter of more than 0.3mm exists in the machined pipe blank, the wave intensity of the bottom surface of crystal scanning is not less than 80%, and the average grain diameter is less than 100 mu m;

and step eight, after nondestructive inspection is qualified, washing the target, drying and carrying out vacuum packaging to obtain the oxygen-free copper sputtering coating target material with the purity of more than or equal to 99.9995%, the average grain size of less than or equal to 100um (the average grain size of less than or equal to 50um in a conventional state), uniform grains, consistent grain orientation, high purity and high coating rate.

And further, in the step two, a high-pressure water gun is adopted to spray water on the surface of the copper ingot for cleaning, and the pressure of the high-pressure water gun is 0.2-1 MPa.

Furthermore, in the fourth step, argon is introduced as protective gas in the casting process, and the purity of the argon is more than or equal to 99.99 percent.

Further, the low-temperature treatment temperature in the fifth step is 600-750 ℃.

Further, the tube blank in the sixth step is welded in a vacuum cold welding mode, the welding temperature is controlled during welding, and the temperature of a welding affected area is controlled to be less than or equal to 200 ℃.

And step seven, detecting the flaw of the welding seam by using an ultrasonic nondestructive flaw detector, detecting whether the welding part has a defect, simultaneously scanning by using water immersion type ultrasonic C, wherein no pore defect with the average diameter of more than 0.3mm exists in the machined pipe blank, the wave intensity of the bottom surface of the crystal scanning is not less than 80%, and the average grain diameter is less than 30 mu m.

Example 1

A preparation method of a high-purity oxygen-free copper sputtering coating target material comprises the following steps:

step one, calculating the consumption of a copper ingot according to the product specification phi 167 multiplied by phi 125 multiplied by 2940mm, and then selecting a proper amount of raw material copper ingot prepared from a high-purity oxygen-free copper sputtering coating target material, wherein the copper ingot is prepared by a vacuum melting method, and the purity is more than or equal to 99.95%;

step two, selecting a high-pressure water gun to clean the raw material copper ingot, wherein the pressure of the high-pressure water gun is 0.3Mpa, distilled water is selected as a water source in the cleaning process, after cleaning and drying, the copper ingot is cleaned by acetone with the purity of more than or equal to 99%, and the cleaned copper ingot is reserved; meanwhile, a copper baking furnace is selected to bake the copper ingot, and the temperature of the baked copper ingot is 210 ℃;

step three, putting the preheated copper ingot into a vacuum smelting furnace, wherein the vacuum degree needs to be controlled at 10^-3The purity of the purified copper bar blank is more than or equal to 99.99 percent;

and step four, the casting mold is connected with the interior of the vacuum smelting furnace, and no external impurities or oxygen are introduced in the whole process. In the casting process, high-purity argon is required to be introduced for protecting other parts, the purity of the argon is more than or equal to 99.99 percent, rough machining is required to be carried out on the argon after casting is finished, and burrs or bulges at the end part are cut off;

and step five, extruding the casting part according to the specification of the product, preheating the casting part in advance before extrusion at the preheating temperature of 700 ℃, obtaining the specification of phi 175 multiplied by phi 115 multiplied by 3150mm after extrusion, and performing low-temperature annealing treatment after extrusion to obtain the copper pipe with uniform crystal grains, wherein the low-temperature treatment temperature is 650 ℃.

Step six, adopting a sub-laser instant melting and cooling welding machine as the cooling welding machine, wherein the whole welding process needs to be in a vacuum environment, so as to avoid introducing O into the welding line₂Impurities such as gas; meanwhile, the cold welding power of the sub-laser instant fusion cold welding machine is 2200W, and the single repair time is 0.3 s;

step seven, flaw detection is carried out on the welding seam by using an ultrasonic nondestructive flaw detector, whether a welding part has a defect is detected, meanwhile, water immersion type ultrasonic C scanning is used, no pore defect with the average diameter larger than 0.3mm exists in the machined pipe blank, the wave intensity of the bottom surface of crystal scanning is not smaller than 80%, and the average grain diameter is smaller than 100 um;

and step eight, washing the machined target body with clean water, drying and then carrying out vacuum packaging to obtain the oxygen-free copper sputtering coating tube target with the purity of more than or equal to 99.9995 percent, the average grain size of 42 mu m, uniform grains and consistent grain orientation.

Example 2

A preparation method of a high-purity oxygen-free copper sputtering coating target material comprises the following steps:

step one, calculating the consumption of a copper ingot according to the product specification phi 171 phi 135 phi 2692mm, and then selecting a proper amount of raw material copper ingot prepared from a high-purity oxygen-free copper sputtering coating target material, wherein the copper ingot is prepared by a vacuum melting method, and the purity is more than or equal to 99.95%;

step two, selecting a high-pressure water gun to clean the raw material copper ingot, wherein the pressure of the high-pressure water gun is 0.5Mpa, selecting distilled water as a water source in the cleaning process, cleaning the copper ingot by using acetone with the purity of more than or equal to 99% after cleaning and drying, and cleaning for later use; meanwhile, a copper baking furnace is selected to bake the copper ingot, and the temperature of the baked copper ingot is 220 ℃;

step three, putting the preheated copper ingot into a vacuum smelting furnace, wherein the vacuum degree needs to be controlled at 10^-3The purity of the purified copper bar blank is more than or equal to 99.99 percent;

and step four, the casting mold is connected with the interior of the vacuum smelting furnace, and no external impurities or oxygen are introduced in the whole process. In the casting process, high-purity argon is required to be introduced for protecting other parts, the purity of the argon is more than or equal to 99.99 percent, rough machining is required to be carried out on the argon after casting is finished, and burrs or bulges at the end part are cut off;

and step five, extruding the casting part according to the product specification, preheating the casting part in advance before extrusion at the preheating temperature of 850 ℃, obtaining a copper pipe with uniform crystal grains after extrusion at the specification of phi 185 multiplied by phi 126 multiplied by 2900mm, and performing low-temperature annealing treatment after extrusion to obtain the copper pipe with uniform crystal grains, wherein the low-temperature treatment temperature is 700 ℃.

Step six, adopting a sub-laser instant melting and cooling welding machine as the cooling welding machine, wherein the whole welding process needs to be in a vacuum environment, so as to avoid introducing O into the welding line₂Impurities such as gas; meanwhile, the cold welding power of the sub-laser instant fusion cold welding machine is 2600W, and the single repair time is 0.5 s;

step seven, flaw detection is carried out on the welding seam by using an ultrasonic nondestructive flaw detector, whether a welding part has a defect is detected, meanwhile, water immersion type ultrasonic C scanning is used, no pore defect with the average diameter larger than 0.3mm exists in the machined pipe blank, the wave intensity of the bottom surface of crystal scanning is not smaller than 80%, and the average grain diameter is smaller than 100 um;

and step eight, washing the machined target body with clean water, drying and then carrying out vacuum packaging to obtain the oxygen-free copper sputtering coating tube target with the purity of more than or equal to 99.9995 percent, the average grain size of 45 mu m, uniform grains and consistent grain orientation.

Example 3

A preparation method of a high-purity oxygen-free copper sputtering coating target material comprises the following steps:

step one, calculating the consumption of a copper ingot according to the specification of a product, namely 19 multiplied by 180 multiplied by 2650mm, and then selecting a proper amount of raw material copper ingot prepared from a high-purity oxygen-free copper sputtering coating target material, wherein the copper ingot is prepared by a vacuum melting method, and the purity is more than or equal to 99.95%;

step two, selecting a high-pressure water gun to clean the raw material copper ingot, wherein the pressure of the high-pressure water gun is 0.6Mpa, selecting distilled water as a water source in the cleaning process, cleaning the copper ingot by using acetone with the purity of more than or equal to 99% after cleaning and drying, and cleaning for later use; meanwhile, a copper baking furnace is selected to bake the copper ingot, and the temperature of the baked copper ingot is 235 ℃;

step three, putting the preheated copper ingot into a vacuum smelting furnace, wherein the vacuum degree needs to be controlled at 10^-3The purity of the purified copper bar blank is more than or equal to 99.99 percent;

and step four, the casting mold is connected with the interior of the vacuum smelting furnace, and no external impurities or oxygen are introduced in the whole process. In the casting process, high-purity argon is required to be introduced for protecting other parts, the purity of the argon is more than or equal to 99.99 percent, rough machining is required to be carried out on the cast plate blank, and burrs or bulges at the end part are cut off;

and step five, rolling the casting at low temperature according to the specification of the product, preheating the casting in advance before rolling at the preheating temperature of 710 ℃, extruding to obtain the copper plate blank with the specification of 26 multiplied by 200 multiplied by 2780mm, and performing low-temperature annealing treatment after rolling to obtain the copper plate blank with uniform crystal grains, wherein the low-temperature treatment temperature is 620 ℃.

Step six, using water immersion type ultrasonic C scanning, wherein no pore defect with the average diameter larger than 0.3mm exists in the machined copper plate blank, the wave intensity of the bottom surface of crystal scanning is not less than 80%, and the average grain diameter is less than 100 um;

and seventhly, washing the machined target body with clean water, drying and then carrying out vacuum packaging to obtain the oxygen-free copper sputtering coating tube target with the purity of more than or equal to 99.9995 percent, the average grain size of 38 mu m, uniform grains and consistent grain orientation.

The invention adopts the method of matching the vacuum melting purification process with the metal extrusion process, and obtains the sputtering copper tube target with the purity of more than or equal to 99.9995 percent, the average grain size of less than or equal to 50um in the conventional state, uniform grains and consistent grain orientation, high purity and high coating rate by the low-temperature vacuum cold welding process and the low-temperature forging process, overcomes the limitations of low purity, large and uneven grains and the like of the copper tube target prepared by the traditional process, and lays a solid foundation for the development and application of the flat panel display industry.

The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

It should be noted that while the invention has been described in terms of the above-mentioned embodiments, other embodiments are also possible. It will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention, and it is intended that all such changes and modifications be covered by the appended claims and their equivalents.