Method for preparing high-purity irregular copper phosphorus anode from regenerated high-purity copper / copper phosphorus and high-purity irregular copper phosphorus anode

Abstract

The present application relates to non-ferrous metal regeneration technical field, specifically to a kind of method for preparing high-purity special-shaped copper phosphorus anode of high-purity copper / copper phosphorus and high-purity special-shaped copper phosphorus anode, high-purity copper phosphorus residual anode and high-purity copper residual target are directly ultrasonic cleaned, purity test is carried out to high-purity copper phosphorus residual anode and high-purity copper residual target after pretreatment.Purity qualified high-purity copper phosphorus residual anode and high-purity copper residual target are vacuum induction smelting, casting is carried out using multi-cavity gradient cooling mold and crucible bottom leakage casting mode, and high-purity special-shaped copper phosphorus casting blank is obtained;High-purity special-shaped copper phosphorus casting blank is machined, cleaned and packaged, and high-purity special-shaped copper phosphorus anode product is obtained.The purity of high-purity special-shaped copper phosphorus anode is ≥99.99wt%, the content of P is 525-650ppm, O≤2ppm, S≤8ppm, and the average grain size of high-purity special-shaped copper phosphorus anode is 310-450μm.The present application uses copper residual target / copper phosphorus residual anode recovery material for vacuum induction smelting again, and the composition and internal grain structure of the product are kept uniform by controlling fluid velocity and temperature.

Description

Technical Field

[0001] This invention relates to the field of non-ferrous metal recycling technology, specifically to a method for preparing high-purity shaped copper-phosphorus anodes by regenerating high-purity copper / copper-phosphorus, and the high-purity shaped copper-phosphorus anodes themselves. Background Technology

[0002] With the continuous iteration and upgrading of integrated circuit manufacturing technology, the performance of interconnect materials directly determines the integration density, reliability, and operating efficiency of chips. In this technological evolution, copper interconnects have completely replaced traditional aluminum and aluminum alloy interconnects due to their significant performance advantages, becoming the core interconnect material in the modern integrated circuit manufacturing field. Copper interconnects not only possess excellent conductivity due to low resistivity and good reliability due to high electromigration resistance, but also offer cost advantages, higher wiring density, and finer wiring capabilities, making them a key foundational material supporting the development of integrated circuits towards higher integration and higher performance.

[0003] The widespread application of copper interconnect technology has directly driven the continuous rise in demand for core thin-film materials. Among them, high-purity copper targets and copper-phosphorus anodes, as key consumables in the copper interconnect manufacturing process, have seen their market demand grow year by year. However, the integrated circuit manufacturing process generates a large amount of high-value solid waste, mainly including two categories: first, copper residue targets remaining after the use of high-purity copper targets, whose remaining mass accounts for about 70% of the total mass of the finished product; and second, copper-phosphorus residue anodes remaining after the electrolysis process, whose remaining mass can reach 50% of the total mass of the finished product. Although these waste materials differ in physical form, they are all rich in high-grade copper and other valuable metals, possessing extremely high resource recycling value.

[0004] Currently, treating such high-value scrap materials as ordinary industrial waste would not only result in a serious waste of precious high-purity metal resources, but the phosphorus they contain could also pose a potential pollution risk to the ecological environment, contradicting the concept of sustainable development in the integrated circuit industry. Therefore, how to achieve efficient recycling and high-value utilization of recycled raw materials such as copper target scraps and copper-phosphorus anode scraps has become a crucial issue restricting the green development of the integrated circuit industry.

[0005] From a performance suitability perspective, the purity requirements for high-purity copper targets used in integrated circuits are extremely stringent (≥99.999wt%). Directly using recycled high-purity copper targets to re-prepare high-purity copper targets presents a very high quality control risk and is unlikely to pass the rigorous verification of integrated circuit chip manufacturers. In contrast to the stringent requirements of high-purity copper targets, the performance specifications for copper-phosphorus anodes used in integrated circuits are more lenient, specifically: a purity requirement of ≥99.95wt%, a phosphorus content controlled within the range of 400~650ppm, and an average grain size of 100~450μm. This performance difference makes recycled raw materials such as high-purity copper targets and copper-phosphorus anodes fully capable of being used to prepare copper-phosphorus anodes, providing a feasible path for the high-value utilization of recycled raw materials.

[0006] However, existing traditional manufacturing processes for copper-phosphorus anodes have many drawbacks, making it difficult to achieve efficient conversion of recycled raw materials. Traditional methods typically use high-purity virgin materials as raw materials. After smelting to obtain high-purity copper-phosphorus ingots, the finished product requires multiple processes including forging, rolling, heat treatment, machining, and cleaning. This process route suffers from lengthy processing steps, low production efficiency, low material utilization, and high production costs. Taking the copper-phosphorus alloy anode manufacturing method disclosed in patent CN102517622B as an example, it requires complex processes such as forging, cold rolling, multiple rounds of heat treatment, and recrystallization annealing, significantly increasing the production cycle due to the time consumed in each process alone.

[0007] The shortcomings of traditional processes are even more pronounced in the fabrication of irregularly shaped copper-phosphorus anodes: the irregular structure requires multiple cutting processes in subsequent processing, further extending the process route; at the same time, a large amount of cutting is required during processing to remove the surface oxide layer, resulting in a material utilization rate of less than 60%. This inefficient and high-loss fabrication mode can neither fully utilize the resource value of recycled raw materials nor meet the demand of the integrated circuit industry for large-scale, low-cost supply of copper-phosphorus anodes. Summary of the Invention

[0008] To address the problems existing in the prior art, the present invention provides a method for preparing high-purity irregularly shaped copper-phosphorus anodes by regenerating high-purity copper / copper-phosphorus, and the high-purity irregularly shaped copper-phosphorus anodes themselves.

[0009] To achieve the above objectives, the technical solution of the present invention is as follows:

[0010] A method for preparing high-purity shaped copper-phosphorus anodes by regenerating high-purity copper / copper-phosphorus, comprising the following steps:

[0011] (1) Pretreatment of recycled raw materials: The high-purity copper-phosphorus residual anode and the single high-purity copper residual target are directly ultrasonically cleaned, and the copper target surface after the composite high-purity copper residual target is unbound is ultrasonically cleaned.

[0012] (2) Purity test of recycled raw materials: The purity of the pretreated high-purity copper-phosphorus residual anode and high-purity copper residual target is tested;

[0013] (3) Melt refining: Select high-purity copper residual targets with a purity ≥99.999wt% or high-purity copper residual targets with a purity ≥99.999wt% and high-purity copper-phosphorus residual anodes with a purity ≥99.999wt% for vacuum induction melting, and add copper-phosphorus intermediate alloy to obtain high-purity copper-phosphorus melt;

[0014] (4) Irregular casting: The high-purity copper-phosphorus melt is cast using a multi-cavity gradient cooling mold and a bottom-casting method. The fluid velocity in the first third of the casting process is 0.5-0.6 kg / s, the fluid velocity in the middle third of the casting process is 1.0-1.2 kg / s, and the fluid velocity in the last third of the casting process is 0.7-0.8 kg / s, to obtain a high-purity irregular copper-phosphorus billet.

[0015] (5) Precision machining: The high-purity irregular copper-phosphorus billet is machined to obtain a high-purity irregular copper-phosphorus anode;

[0016] (6) Cleaning and packaging: The high-purity irregular copper-phosphorus anode is cleaned and vacuum-packed using automated cleaning and packaging equipment.

[0017] Further, the cleaning medium in step (1) is an ultrasonic cleaning solution containing 0.1-0.5% sodium dodecyl sulfonate, the ultrasonic vibration frequency is 50-100 kHz, and the cleaning time is 10-20 min; the unbinding method of the composite high-purity copper residual target is electrical discharge cutting.

[0018] Further, in step (2), purity is detected by glow discharge mass spectrometry or inductively coupled plasma mass spectrometry.

[0019] Furthermore, the vacuum degree of vacuum induction melting in step (3) is ≤5.0×10 -4 Pa, melting temperature is 1250-1280℃, refining time is 7-8 min.

[0020] Furthermore, the material of the multi-cavity gradient cooling mold in step (4) is high-purity graphite, and the bottom of the multi-cavity gradient cooling mold is equipped with a vibration device with a vibration frequency of 75-95 Hz.

[0021] Furthermore, the casting temperature in step (4) is 1220-1250℃, the cooling rate in the gating zone is 80-100℃ / s, and the cooling rate in the end zone is 15-20℃ / s.

[0022] This invention also includes the following technical solutions:

[0023] A high-purity irregularly shaped copper-phosphorus anode prepared by the above method, wherein the purity of the high-purity irregularly shaped copper-phosphorus anode is ≥99.99wt%, wherein the content of P is 525-650ppm, Ag≤1ppm, Fe≤1ppm, Si≤1ppm, O≤2ppm, and S≤8ppm, and the average grain size of the high-purity irregularly shaped copper-phosphorus anode is 310-450 μm.

[0024] Furthermore, the high-purity irregular copper-phosphorus anode can be in the shape of a disc, a 1 / 3 circular fan-shaped part, a 1 / 4 circular fan-shaped part, a ring, or a 1 / 4 ring.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0026] (1) The present invention uses high-purity copper residual target and copper-phosphorus residual anode as raw materials to prepare high-purity irregular copper-phosphorus anode with a purity ≥99.99 wt%, which is higher than that of traditional anodes made of electrolytic copper (99.95 wt%-99.99 wt%). Its impurity element content is extremely low, Ag≤1ppm, Fe≤1ppm, Si≤1ppm, O≤2ppm, S≤8ppm, which is conducive to uniform dissolution of the anode during electroplating and improves the coating quality;

[0027] (2) The present invention adopts a multi-cavity gradient cooling mold and a crucible bottom casting method. By controlling the fluid speed and temperature, the product composition and internal grain structure are kept uniform, which can not only meet the high requirements of integrated circuit electroplating process, but also significantly reduce production energy consumption by about 50%.

[0028] (3) This invention utilizes recycled copper target / copper-phosphorus anode material for vacuum induction melting again. Compared with the production of electrolytic copper plates, the exhaust volume is significantly reduced, the melting time is shortened, and the production energy consumption is reduced by about 20%. In addition, this invention eliminates the traditional lengthy processes such as forging, rolling, and multiple annealing, significantly reducing the machining time, shortening the production cycle by 66%, and increasing the material utilization rate to over 90%. At the same time, it realizes resource recycling and has significant economic, environmental, and social benefits. Attached Figure Description

[0029] The embodiments of the present invention will be further described below with reference to the accompanying drawings, wherein:

[0030] Figure 1 A process flow diagram of the present invention is shown;

[0031] Figure 2 A schematic diagram of an embodiment of the present invention using a casting mold is shown;

[0032] Figure 3 A 50X microstructure of the copper-phosphorus anode in Example 1 is shown;

[0033] Figure 4 A 50X micrograph of the copper-phosphorus anode in Example 2 is shown;

[0034] Figure 5 A 50X micrograph of the copper-phosphorus anode in Example 3 is shown;

[0035] Figure 6 A 50X microstructure of the copper-phosphorus anode in Comparative Example 2 is shown. Detailed Implementation

[0036] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0037] Example 1

[0038] The process of manufacturing a high-purity, irregularly shaped copper-phosphorus anode of type SE with a purity of 4N8 using a single high-purity copper residual target and CuP master alloy includes the following steps:

[0039] Pretreatment of recycled raw materials: The high-purity copper target residue was ultrasonically cleaned in an ultrasonic cleaning solution containing 0.1% sodium dodecyl sulfonate. The ultrasonic vibration frequency was 80 kHz and the cleaning time was 15 min.

[0040] Purity testing of recycled raw materials: A 5×5×20mm sample was cut from the cleaned high-purity copper residue target, cleaned again, and then its purity was determined by glow discharge mass spectrometry.

[0041] (3) Melt refining: Select high-purity copper residue with a purity ≥ 99.999 wt% and place it in a vacuum induction furnace for melting. At the same time, add copper-phosphorus master alloy, of which 160 kg of high-purity copper residue and 7 kg of CuP master alloy are added. The melting vacuum degree is maintained at 5.0 × 10⁻⁶. -4 Below Pa, the melting temperature is 1250℃, the refining time is 8 min, and the refining time starts from when the raw material is completely melted to obtain high-purity copper-phosphorus melt;

[0042] (4) Irregular shape casting: High-purity copper-phosphorus melt is cast using a 6-cavity gradient cooling mold and a crucible bottom casting method. The multi-cavity gradient cooling mold is placed on a vibration device with a vibration frequency of 75 Hz. The casting temperature is 1220℃. The fluid velocity in the first third of the casting process is 0.5 kg / s, which fills the narrow cavity at the bottom of the mold. The fluid velocity in the middle third of the casting process is 1.0 kg / s, which fills the main body of the mold. The fluid velocity in the last third of the casting process is 0.7 kg / s to reduce impact and obtain a high-purity irregular shape copper-phosphorus billet.

[0043] (5) Precision machining: High-purity irregular copper-phosphorus billets are machined using a high-precision, low-damage CNC milling machine to obtain high-purity irregular copper-phosphorus anodes;

[0044] (6) Cleaning and packaging: Use an automatic cleaning machine to remove dirt from the surface of the high-purity irregular copper-phosphorus anode, then place it in a vacuum oven to dry, and after cooling, use an automatic packaging machine to perform three-layer vacuum sealing packaging to prevent oxidation.

[0045] The high-purity irregularly shaped copper-phosphorus anode prepared in this embodiment is disc-shaped, with a purity of 4N8 and an average grain size of 335 μm. The compositional analysis of the high-purity irregularly shaped copper-phosphorus anode is shown in Table 1, and the 50X microstructure image is shown in [Table 1]. Figure 3 .

[0046] Table 1

[0047]

[0048] Example 2

[0049] The process of manufacturing a high-purity, irregularly shaped copper-phosphorus anode of EXT type with a purity of 4N5 using a composite high-purity copper residual target and CuP master alloy includes the following steps:

[0050] (1) Pretreatment of recycled raw materials: First, use electrical discharge machining to separate the copper target surface of the composite high-purity copper residual target from the back plate (containing elements other than Cu and P). Then, the unbound copper target surface is ultrasonically cleaned in an ultrasonic cleaning solution containing 0.5% sodium dodecyl sulfonate. The ultrasonic vibration frequency is 50 kHz and the cleaning time is 20 min.

[0051] (2) Purity test of recycled raw materials: A 5×5×20mm sample was cut from the cleaned copper target surface, cleaned again, and then its purity was determined by glow discharge mass spectrometry.

[0052] (3) Melt refining: Select copper target surfaces with a purity ≥ 99.999 wt% and place them in a vacuum induction furnace for melting. At the same time, copper-phosphorus master alloy is added, including 150 kg of high-purity copper target residue and 5.4 kg of CuP master alloy. The melting vacuum degree is maintained at 5.0 × 10⁻⁶. -4 Below Pa, the melting temperature is 1280℃, the refining time is 7 min, and the refining time starts from when the raw material is completely melted to obtain high-purity copper-phosphorus melt;

[0053] (4) Irregular shape casting: High-purity copper-phosphorus melt is cast using an 8-cavity gradient cooling mold and a crucible bottom casting method. The multi-cavity gradient cooling mold is placed on a vibration device with a vibration frequency of 80 Hz. The casting temperature is 1250℃. The fluid velocity in the first third of the casting process is 0.6 kg / s, which fills the narrow cavity at the bottom of the mold. The fluid velocity in the middle third of the casting process is 1.2 kg / s, which fills the main body of the mold. The fluid velocity in the last third of the casting process is 0.8 kg / s to reduce impact and obtain a high-purity irregular shape copper-phosphorus billet.

[0054] (5) Precision machining: High-purity irregular copper-phosphorus billets are machined using a high-precision, low-damage CNC milling machine to obtain high-purity irregular copper-phosphorus anodes;

[0055] (6) Cleaning and packaging: Use an automatic cleaning machine to remove dirt from the surface of the high-purity irregular copper-phosphorus anode, then place it in a vacuum oven to dry, and after cooling, use an automatic packaging machine to perform three-layer vacuum sealing packaging to prevent oxidation.

[0056] The high-purity irregularly shaped copper-phosphorus anode prepared in this embodiment is a 1 / 3 circular fan-shaped part with a purity of 4N5 and an average grain size of 424 μm. The compositional analysis of the high-purity irregularly shaped copper-phosphorus anode is shown in Table 2, and the 50X microstructure image is shown in Table 2. Figure 4 .

[0057] Table 2

[0058]

[0059] Example 3

[0060] The process of manufacturing a 4N purity SNL-type high-purity irregularly shaped copper-phosphorus anode using a single high-purity copper target residue, CuP master alloy, and copper-phosphorus anode residue includes the following steps:

[0061] (1) Pretreatment of recycled raw materials: The high-purity copper target recovery material and copper-phosphorus anode recovery material were ultrasonically cleaned in an ultrasonic cleaning solution containing 0.3% sodium dodecyl sulfonate. The ultrasonic vibration frequency was 100 kHz and the cleaning time was 10 min.

[0062] (2) Purity test of recycled raw materials: A 5×5×20mm sample was cut from the cleaned high-purity copper residue target and cleaned again. Then, its purity was determined by glow discharge mass spectrometry. A 5g chip sample was drilled from the cleaned copper-phosphorus residue anode and its purity and P content were determined by inductively coupled plasma mass spectrometry.

[0063] (3) Melt refining: Select high-purity copper residual targets with a purity ≥99.999wt% and copper-phosphorus residual anodes with a purity ≥99.999wt% and place them in a vacuum induction furnace for melting. At the same time, copper-phosphorus master alloy is added. The amount of high-purity copper residual targets is 100 kg, copper-phosphorus residual anodes are 65 kg, and CuP master alloy is 3 kg. The melting vacuum degree is maintained at 5.0×10 -4 Below Pa, the melting temperature is 1260℃, the refining time is 7 min, and the refining time starts from when the raw material is completely melted to obtain high-purity copper-phosphorus melt;

[0064] (4) Irregular shape casting: High-purity copper-phosphorus melt is cast using a 6-cavity gradient cooling mold and a crucible bottom casting method. The multi-cavity gradient cooling mold is placed on a vibration device with a vibration frequency of 95 Hz. The casting temperature is 1240℃. The fluid velocity in the first third of the casting process is 0.5 kg / s, which fills the narrow cavity at the bottom of the mold. The fluid velocity in the middle third of the casting process is 1.1 kg / s, which fills the main body of the mold. The fluid velocity in the last third of the casting process is 0.7 kg / s to reduce impact and obtain a high-purity irregular shape copper-phosphorus billet.

[0065] (5) Precision machining: High-purity irregular copper-phosphorus billets are machined using a high-precision, low-damage CNC milling machine to obtain high-purity irregular copper-phosphorus anodes;

[0066] (6) Cleaning and packaging: Use an automatic cleaning machine to remove dirt from the surface of the high-purity irregular copper-phosphorus anode, then place it in a vacuum oven to dry, and after cooling, use an automatic packaging machine to perform three-layer vacuum sealing packaging to prevent oxidation.

[0067] The high-purity irregularly shaped copper-phosphorus anode prepared in this embodiment is a ring with a purity of 4N and an average grain size of 380 μm. The compositional analysis of the high-purity irregularly shaped copper-phosphorus anode is shown in Table 3, and the 50X microstructure image is shown in Table 3. Figure 5 .

[0068] Table 3

[0069]

[0070] Comparative Example 1

[0071] The manufacturing of SE-type high-purity irregularly shaped copper-phosphorus anodes using electrolytic copper and CuP master alloy includes the following steps:

[0072] (1) Pretreatment of recycled raw materials: Electrolytic copper is ultrasonically cleaned in an ultrasonic cleaning solution containing 0.1% sodium dodecyl sulfonate. The ultrasonic vibration frequency is 80 kHz and the cleaning time is 15 min.

[0073] (2) Purity test of recycled raw materials: A 5×5×20mm sample was cut from the cleaned electrolytic copper, cleaned again, and then its purity was determined by glow discharge mass spectrometry.

[0074] (3) Melt refining: Select electrolytic copper with a purity ≥ 99.99 wt% and place it in a vacuum induction furnace for smelting. At the same time, add copper-phosphorus master alloy, of which 160 kg of electrolytic copper and 7 kg of CuP master alloy are added. The smelting vacuum degree is maintained at 5.0 × 10⁻⁶. - 4 Below Pa, the melting temperature is 1250℃, the refining time is 8 min, and the refining time starts from when the raw material is completely melted to obtain high-purity copper-phosphorus melt;

[0075] (4) Irregular shape casting: High-purity copper-phosphorus melt is cast using a 6-cavity gradient cooling mold and a crucible bottom casting method. The multi-cavity gradient cooling mold is placed on a vibration device with a vibration frequency of 75 Hz. The casting temperature is 1220℃. The fluid velocity in the first third of the casting process is 0.5 kg / s, which fills the narrow cavity at the bottom of the mold. The fluid velocity in the middle third of the casting process is 1.0 kg / s, which fills the main body of the mold. The fluid velocity in the last third of the casting process is 0.7 kg / s to reduce impact and obtain a high-purity irregular shape copper-phosphorus billet.

[0076] (5) Precision machining: High-purity irregular copper-phosphorus billets are machined using a high-precision, low-damage CNC milling machine to obtain high-purity irregular copper-phosphorus anodes;

[0077] (6) Cleaning and packaging: Use an automatic cleaning machine to remove dirt from the surface of the high-purity irregular copper-phosphorus anode, then place it in a vacuum oven to dry, and after cooling, use an automatic packaging machine to perform three-layer vacuum sealing packaging to prevent oxidation.

[0078] The high-purity irregularly shaped copper-phosphorus anode prepared in this comparative example is disc-shaped with a purity of 3N5 and an average grain size of 350 μm. The compositional analysis of the high-purity irregularly shaped copper-phosphorus anode is shown in Table 4.

[0079] Table 4

[0080]

[0081] Comparative Example 2

[0082] The process of manufacturing a high-purity, irregularly shaped copper-phosphorus anode of type SE with a purity of 4N8 using a single high-purity copper residual target and CuP master alloy includes the following steps:

[0083] (1) Pretreatment of recycled raw materials: The high-purity copper target residue of monomer was ultrasonically cleaned in an ultrasonic cleaning solution containing 0.1% sodium dodecyl sulfonate. The ultrasonic vibration frequency was 80 kHz and the cleaning time was 15 min.

[0084] (2) Purity test of recycled raw materials: A 5×5×20mm sample was cut from the cleaned high-purity copper residue target, cleaned again, and then its purity was determined by glow discharge mass spectrometry.

[0085] (3) Melt refining: Select high-purity copper residue with a purity ≥ 99.999 wt% and place it in a vacuum induction furnace for melting. At the same time, add copper-phosphorus master alloy, of which 160 kg of high-purity copper residue and 7 kg of CuP master alloy are added. The melting vacuum degree is maintained at 5.0 × 10⁻⁶. -4 Below Pa, the melting temperature is 1250℃, the refining time is 8 min, and the refining time starts from when the raw material is completely melted to obtain high-purity copper-phosphorus melt;

[0086] (4) Irregular casting: High-purity copper-phosphorus melt is cast using a 6-cavity gradient cooling mold and crucible bottom casting method. The casting temperature is 1300℃ and the fluid velocity is 0.7 kg / s to obtain high-purity irregular copper-phosphorus billet.

[0087] (5) Precision machining: High-purity irregular copper-phosphorus billets are machined using a high-precision, low-damage CNC milling machine to obtain high-purity irregular copper-phosphorus anodes;

[0088] (6) Cleaning and packaging: Use an automatic cleaning machine to remove dirt from the surface of the high-purity irregular copper-phosphorus anode, then place it in a vacuum oven to dry, and after cooling, use an automatic packaging machine to perform three-layer vacuum sealing packaging to prevent oxidation.

[0089] The high-purity irregularly shaped copper-phosphorus anode prepared in this comparative example is disc-shaped, with a purity of 4N8 and an average grain size of 480 μm. The compositional analysis of the high-purity irregularly shaped copper-phosphorus anode is shown in Table 5, and the 50X microstructure is shown in […]. Figure 6 .

[0090] Table 5

[0091]

[0092] The beneficial effects of this invention are as follows:

[0093] (1) The present invention uses high-purity copper residual target and copper-phosphorus residual anode as raw materials to prepare high-purity irregular copper-phosphorus anode with a purity ≥99.99 wt%, which is higher than that of traditional anodes made of electrolytic copper (99.95 wt%-99.99 wt%). Its impurity element content is extremely low, Ag≤1ppm, Fe≤1ppm, Si≤1ppm, O≤2ppm, S≤8ppm, which is conducive to uniform dissolution of the anode during electroplating and improves the coating quality;

[0094] (2) The present invention adopts a multi-cavity gradient cooling mold and a crucible bottom casting method. By controlling the fluid speed and temperature, the product composition and internal grain structure are kept uniform, which can not only meet the high requirements of integrated circuit electroplating process, but also significantly reduce production energy consumption by about 50%.

[0095] (3) This invention utilizes recycled copper target / copper-phosphorus anode material for vacuum induction melting again. Compared with the production of electrolytic copper plates, the exhaust volume is significantly reduced, the melting time is shortened, and the production energy consumption is reduced by about 20%. In addition, this invention eliminates the traditional lengthy processes such as forging, rolling, and multiple annealing, significantly reducing the machining time, shortening the production cycle by 66%, and increasing the material utilization rate to over 90%. At the same time, it realizes resource recycling and has significant economic, environmental, and social benefits.

[0096] The foregoing descriptions have outlined some exemplary embodiments of the present invention. It is understood that these embodiments are merely illustrative and do not constitute a limitation on the scope of protection of the present invention. Features in these embodiments can be rearranged in suitable ways, and the resulting solutions remain within the scope of protection claimed by the present invention. All other embodiments obtained by those skilled in the art based on the foregoing embodiments without inventive effort, i.e., all modifications, equivalent substitutions, and improvements made within the spirit and principles of this application, fall within the scope of protection claimed by the present invention.

Claims

1. A method for preparing high-purity irregularly shaped copper-phosphorus anodes by regenerating high-purity copper / copper-phosphorus, characterized in that, Includes the following steps: Pretreatment of recycled raw materials: High-purity copper-phosphorus residual anodes and monomeric high-purity copper residual targets are directly ultrasonically cleaned, and the copper target surface after unbinding the composite high-purity copper residual target is ultrasonically cleaned. Purity testing of recycled raw materials: The purity of the pretreated high-purity copper-phosphorus residual anode and high-purity copper residual target is tested; Melt refining: Select high-purity copper residual targets with a purity ≥99.999wt% or high-purity copper residual targets with a purity ≥99.999wt% and high-purity copper-phosphorus residual anodes with a purity ≥99.999wt% for vacuum induction melting, and add copper-phosphorus master alloy to obtain high-purity copper-phosphorus melt; Irregular shape casting: The high-purity copper-phosphorus melt is cast using a multi-cavity gradient cooling mold and a bottom-casting method. The casting temperature is 1220-1250℃, the cooling rate in the gating zone is 80-100℃ / s, the cooling rate in the end zone is 15-20℃ / s, the fluid velocity in the first third of the casting process is 0.5-0.6 kg / s, the fluid velocity in the middle third of the casting process is 1.0-1.2 kg / s, and the fluid velocity in the last third of the casting process is 0.7-0.8 kg / s, to obtain a high-purity irregular shape copper-phosphorus billet. Precision machining: The high-purity irregular-shaped copper-phosphorus billet is machined to obtain a high-purity irregular-shaped copper-phosphorus anode; Cleaning and Packaging: The high-purity irregularly shaped copper-phosphorus anodes are cleaned and vacuum-packed using automated cleaning and packaging equipment.

2. The method for preparing high-purity irregularly shaped copper-phosphorus anodes by regenerating high-purity copper / copper-phosphorus according to claim 1, characterized in that, The cleaning medium in step (1) is an ultrasonic cleaning solution containing 0.1-0.5% sodium dodecyl sulfonate, the ultrasonic vibration frequency is 50-100 kHz, and the cleaning time is 10-20 min; the unbinding method of the composite high-purity copper residual target is electrical discharge cutting.

3. The method for preparing high-purity shaped copper-phosphorus anodes by regenerating high-purity copper / copper-phosphorus according to claim 1, characterized in that, Step (2) Purity is determined by glow discharge mass spectrometry or inductively coupled plasma mass spectrometry.

4. The method for preparing high-purity shaped copper-phosphorus anodes by regenerating high-purity copper / copper-phosphorus according to claim 1, characterized in that, Step (3) Vacuum degree of vacuum induction melting ≤ 5.0 × 10 -4 Pa, melting temperature is 1250-1280℃, refining time is 7-8 min.

5. The method for preparing high-purity shaped copper-phosphorus anodes by regenerating high-purity copper / copper-phosphorus according to claim 1, characterized in that, The material of the multi-cavity gradient cooling mold in step (4) is high-purity graphite. The bottom of the multi-cavity gradient cooling mold is equipped with a vibration device with a vibration frequency of 75-95 Hz.

6. A high-purity irregularly shaped copper-phosphorus anode prepared by the method according to any one of claims 1-5, characterized in that, The purity of the high-purity irregularly shaped copper-phosphorus anode is ≥99.99wt%, wherein the content of P is 525-650ppm, Ag≤1ppm, Fe≤1ppm, Si≤1ppm, O≤2ppm, and S≤8ppm, and the average grain size of the high-purity irregularly shaped copper-phosphorus anode is 310-450 μm.

7. The high-purity irregularly shaped copper-phosphorus anode according to claim 6, characterized in that, The high-purity irregular copper-phosphorus anode is in the shape of a disc, a 1 / 3 circular fan-shaped part, a 1 / 4 circular fan-shaped part, a ring, or a 1 / 4 ring.

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