CN116752104A - Manufacturing method of high-purity low-oxygen fine-grain Ag rotary tube target for semiconductor - Google Patents

Abstract

The invention discloses a method for making a high-purity low-oxygen fine-grained Ag rotating tube target for semiconductors. The key points of the technical solution are: including the following steps: S1. Material preparation: prepare Ag raw materials with a purity greater than 99.999% for later use; S2. smelting : Place the Ag raw material in the smelting furnace and smelt it to obtain the Ag ingot; S3. Deoxidation: Before the ingot is cast, perform a deoxidation process of burning and biting oxygen; S4. Water quenching: Water-cool the ingot; S5. Remove the skin of the stomatal layer: Cart off the skin of the stomatal layer; S6, extrusion: heat the ingot to 300-800℃, keep it warm, the holding time is 10-60min, and then extrud it once, and the dosage form ratio is 80-95% to obtain Ag. Rotating tube embryo; S7, processing: Process the Ag rotating tube embryo to the required size to obtain the Ag rotating tube target. The process method is simple and the cost is low.

Description

A method for manufacturing a high-purity low-oxygen fine-grained Ag rotating tube target for semiconductors

Technical field

The present invention relates to the technical field of target manufacturing, and in particular to a method for manufacturing a high-purity low-oxygen fine-grained Ag rotating tube target for semiconductors.

Background technique

Currently, many Ag rotating tube targets are prepared by spraying process, and most of them are used in the Low-E industry. This is due to the limitations of the spraying process, resulting in lower quality, such as low target purity, low density, uneven grains, and high gas content, especially oxygen content >1000ppm, which makes it unable to meet the semiconductor industry standards.

For example, the existing Chinese patent with publication number CN105483691A discloses a process for preparing a silver rotating tube by cold spraying. The silver rotating tube is composed of a base tube and a spray coating. The cold spraying process is: 1) Cold spray nozzle The working gas pressure at the inlet is 2-3Mpa, and the temperature is 300-500℃; 2) The working gas is heated to 400-850℃ and pressurized to 3.0-3.5Mpa; 3) N2 is used as the working gas, and the N2 flow rate is 28-60m3 /h. .

Another example is the existing Chinese patent with publication number CN114395749A, which discloses a large-size, multi-component Ag-based alloy sputtering target, which is characterized in that: the sputtering target is used to make anode materials in AMOLED panels. , to meet the large-size integrated wide-width targets required for G4.5G6 AMOLED production line production. The sputtering target material includes Ag ingot, In or Cu ingot, and any one of Sn, Sb, Ca, Mg, Ce, Eu, Ga, and Pd.

The above patents use different processes for production, each with some advantages; of course, smelting metallurgical methods can be used, and then high-quality flat targets can be obtained through forging, rolling, annealing and other processes, but the utilization rate of flat targets is low, usually less than 40 %, which is far lower than the 70-80% usage rate of the rotating tube target. Therefore, the use cost of the flat target is much higher than that of the rotating tube target, thus increasing the cost of use and not conducive to the development of the enterprise. Rotating tube targets are a future development trend due to their high usage rate.

Contents of the invention

In view of the problems mentioned in the background art, the purpose of the present invention is to provide a method for manufacturing a high-purity low-oxygen fine-grained Ag rotating tube target for semiconductors, so as to solve the problems mentioned in the background art.

The above technical objectives of the present invention are achieved through the following technical solutions:

A method for manufacturing a high-purity low-oxygen fine-grained Ag rotating tube target for semiconductors, including the following steps:

S1. Material preparation: Prepare Ag raw materials with a purity greater than 99.999% for later use;

S2. Smelting: Place the Ag raw material in the smelting furnace and smelt it to obtain Ag ingot;

S3. Deoxidation: Before the ingot is cast, a deoxidation process of burning and biting oxygen is carried out;

S4. Water quenching: water-cool the ingot;

S5. Remove the outer skin of the stomatal layer: Carry off the outer skin of the stomatal layer;

S6. Extrusion: Heat the ingot to 300-800°C, keep it warm for 10-60 minutes, and then extrud it once to obtain the Ag rotating tube embryo;

S7. Processing: Process the Ag rotating tube blank to the required size to obtain the Ag rotating tube target.

Preferably, the S3 is deoxidizing, and before the ingot is cast, the deoxidizing process is to use lathe processing to remove the leather with pores on the surface of the ingot.

Preferably, when S2 is smelted, the furnace selected is an intermediate frequency furnace. The Ag raw material is first preheated, and then the temperature of the intermediate frequency furnace is heated to 980-990°C for insulation, and then the melting aid is added to the intermediate frequency furnace. Carry out smelting.

Preferably, the additives added in the intermediate frequency furnace are potassium permanganate and borax. After the smelting is completed, the smelting slag is separated from the molten liquid and the smelting slag is taken out with furnace tongs.

Preferably, during water quenching in S4, the ingot is pickled before water cooling. During pickling, citric acid water is used for pickling. The mass concentration of citric acid is 3%, and after water cooling, Remove flash burrs and foreign inclusions.

Preferably, during extrusion of S6, the extrusion pressure is controlled to be greater than 15 tons/cm2.

Preferably, when the silver blank is extruded, it is heated to a recrystallization temperature of 580-590°C for extrusion.

Preferably, during the processing of S7, a lathe is used to process the Ag rotating tube embryo to the required size, and it is stored after passing the inspection.

To sum up, the present invention mainly has the following beneficial effects:

The production method of the new high-purity low-oxygen fine-grained Ag rotating tube target is to smelt high-purity elemental Ag according to the required weight, perform the necessary deoxidation process before casting, and cool it after casting to obtain an Ag ingot. The outer skin of the ingot is then turned to remove the pore layer. Then the peeled ingot undergoes an extrusion process to obtain a rotating tube embryo with an oxygen content of less than 30ppm and an average grain size of less than 20um. The tube embryo can be processed to the required size, and the process method is simple.

Description of the drawings

Figure 1 is a flow chart of the present invention.

Detailed ways

The present invention will be described in detail below with reference to the drawings and examples.

Example 1

Referring to Figure 1, a method for manufacturing a high-purity low-oxygen fine-grained Ag rotating tube target for semiconductors includes the following steps:

S1. Material preparation: Prepare Ag raw materials with a purity greater than 99.999% for later use;

S2. Smelting: Place the Ag raw material in the smelting furnace and smelt it to obtain Ag ingot;

S3. Deoxidation: Before the ingot is cast, a deoxidation process is carried out;

S4. Water quenching: water-cool the ingot;

S5. Remove the outer skin of the stomatal layer: Carry off the outer skin of the stomatal layer;

S6. Extrusion: Heat the ingot to 300°C, keep it warm for 60 minutes, and then extrud it once to obtain the Ag rotating tube embryo;

S7. Processing: Process the Ag rotating tube blank to the required size to obtain the Ag rotating tube target.

Among them, the S3 is in deoxidation. Before the ingot is cast, the deoxidation process is to use lathe processing to remove the leather with pores on the surface of the ingot.

Among them, when S2 is smelted, the selected furnace is an intermediate frequency furnace. The Ag raw material is first preheated, and then the temperature of the intermediate frequency furnace is heated to 980°C for heat preservation, and then smelting aids are added to the intermediate frequency furnace for smelting.

Among them, the additives added in the intermediate frequency furnace are potassium permanganate and borax. After the smelting is completed, the smelting slag is separated from the molten liquid and the smelting slag is taken out with furnace tongs.

Among them, during water quenching in S4, the ingot is pickled before water cooling. During pickling, citric acid water is used for pickling. The mass concentration of citric acid is 3%, and the fly ash is removed after water cooling. Edge burrs and foreign inclusions.

Among them, during extrusion of S6, the extrusion pressure is controlled to be greater than 15 tons/cm².

Wherein, during extrusion molding, the silver billet is heated to a recrystallization temperature of 580°C for extrusion.

Preferably, during the processing of S7, a lathe is used to process the Ag rotating tube embryo to the required size, and it is stored after passing the inspection.

Among them, the new high-purity low-oxygen fine-grained Ag rotating tube target is made by melting high-purity elemental Ag according to the required weight, performing the necessary deoxidation process before casting, and cooling after casting to obtain an Ag ingot. The outer skin of the ingot is then turned to remove the pore layer. Then the peeled ingot undergoes an extrusion process to obtain a rotating tube embryo with an oxygen content of less than 30ppm and an average grain size of less than 20um. Just process the tube blank to the required size.

Example 2

Referring to Figure 1, a method for manufacturing a high-purity low-oxygen fine-grained Ag rotating tube target for semiconductors includes the following steps:

S1. Material preparation: Prepare Ag raw materials with a purity greater than 99.999% for later use;

S2. Smelting: Place the Ag raw material in the smelting furnace and smelt it to obtain Ag ingot;

S3. Deoxidation: Before the ingot is cast, a deoxidation process is carried out;

S4. Water quenching: water-cool the ingot;

S5. Remove the outer skin of the stomatal layer: Carry off the outer skin of the stomatal layer;

S6. Extrusion: Heat the ingot to 800°C, keep it warm for 50 minutes, and then extrud it once to obtain the Ag rotating tube embryo;

S7. Processing: Process the Ag rotating tube blank to the required size to obtain the Ag rotating tube target.

Among them, the S3 is in deoxidation. Before the ingot is cast, the deoxidation process is to use lathe processing to remove the leather with pores on the surface of the ingot.

Among them, when S2 is smelted, the selected furnace is an intermediate frequency furnace. The Ag raw material is first preheated, and then the temperature of the intermediate frequency furnace is heated to 980-990°C for heat preservation, and then smelting aids are added to the intermediate frequency furnace for smelting. .

Among them, the additives added in the intermediate frequency furnace are potassium permanganate and borax. After the smelting is completed, the smelting slag is separated from the molten liquid and the smelting slag is taken out with furnace tongs.

Among them, during water quenching in S4, the ingot is pickled before water cooling. During pickling, citric acid water is used for pickling. The mass concentration of citric acid is 3%, and the fly ash is removed after water cooling. Edge burrs and foreign inclusions.

Among them, during extrusion of S6, the extrusion pressure is controlled to be greater than 15 tons/cm².

When the silver billet is extruded, it is heated to a recrystallization temperature of 585°C for extrusion.

Preferably, during the processing of S7, a lathe is used to process the Ag rotating tube embryo to the required size, and it is stored after passing the inspection.

Among them, the new high-purity low-oxygen fine-grained Ag rotating tube target is made by melting high-purity elemental Ag according to the required weight, performing the necessary deoxidation process before casting, and cooling after casting to obtain an Ag ingot. The outer skin of the ingot is then turned to remove the pore layer. Then the peeled ingot undergoes an extrusion process to obtain a rotating tube embryo with an oxygen content of less than 30ppm and an average grain size of less than 20um. Just process the tube blank to the required size.

Example 3

Referring to Figure 1, a method for manufacturing a high-purity low-oxygen fine-grained Ag rotating tube target for semiconductors includes the following steps:

S1. Material preparation: Prepare Ag raw materials with a purity greater than 99.999% for later use;

S2. Smelting: Place the Ag raw material in the smelting furnace and smelt it to obtain Ag ingot;

S3. Deoxidation: Before the ingot is cast, a deoxidation process is carried out;

S4. Water quenching: water-cool the ingot;

S5. Remove the outer skin of the stomatal layer: Carry off the outer skin of the stomatal layer;

S6. Extrusion: Heat the ingot to 500°C, keep it warm for 40 minutes, and then extrud it once to obtain the Ag rotating tube embryo;

S7. Processing: Process the Ag rotating tube blank to the required size to obtain the Ag rotating tube target.

Among them, the S3 is in deoxidation. Before the ingot is cast, the deoxidation process is to use lathe processing to remove the leather with pores on the surface of the ingot.

When S2 is smelted, the selected melting furnace is an intermediate frequency furnace. The Ag raw material is first preheated, and then the temperature of the intermediate frequency furnace is heated to 990°C for heat preservation, and then melting aids are added to the intermediate frequency furnace for smelting.

Among them, the additives added in the intermediate frequency furnace are potassium permanganate and borax. After the smelting is completed, the smelting slag is separated from the molten liquid and the smelting slag is taken out with furnace tongs.

Among them, during water quenching in S4, the ingot is pickled before water cooling. During pickling, citric acid water is used for pickling. The mass concentration of citric acid is 3%, and the fly ash is removed after water cooling. Edge burrs and foreign inclusions.

Among them, during extrusion of S6, the extrusion pressure is controlled to be greater than 15 tons/cm2.

Wherein, during extrusion molding, the silver billet is heated to a recrystallization temperature of 90°C for extrusion.

Preferably, during the processing of S7, a lathe is used to process the Ag rotating tube embryo to the required size, and it is stored after passing the inspection.

Among them, the new high-purity low-oxygen fine-grained Ag rotating tube target is made by melting high-purity elemental Ag according to the required weight, performing the necessary deoxidation process before casting, and cooling after casting to obtain an Ag ingot. The outer skin of the ingot is then turned to remove the pore layer. Then the peeled ingot undergoes an extrusion process to obtain a rotating tube embryo with an oxygen content of less than 30ppm and an average grain size of less than 20um. Just process the tube blank to the required size.

Example 4

Referring to Figure 1, a method for manufacturing a high-purity low-oxygen fine-grained Ag rotating tube target for semiconductors includes the following steps:

S1. Material preparation: Prepare Ag raw materials with a purity greater than 99.999% for later use;

S2. Smelting: Place the Ag raw material in the smelting furnace and smelt it to obtain Ag ingot;

S3. Deoxidation: Before the ingot is cast, a deoxidation process is carried out;

S4. Water quenching: water-cool the ingot;

S5. Remove the outer skin of the stomatal layer: Carry off the outer skin of the stomatal layer;

S6. Extrusion: Heat the ingot to 800°C, keep it warm for 45 minutes, and then extrud it once to obtain the Ag rotating tube embryo;

S7. Processing: Process the Ag rotating tube blank to the required size to obtain the Ag rotating tube target.

Among them, the S3 is in deoxidation. Before the ingot is cast, the deoxidation process is to use lathe processing to remove the leather with pores on the surface of the ingot.

Among them, when S2 is smelted, the selected furnace is an intermediate frequency furnace. The Ag raw material is first preheated, and then the temperature of the intermediate frequency furnace is heated to 985°C for heat preservation, and then smelting aids are added to the intermediate frequency furnace for smelting.

Among them, the additives added in the intermediate frequency furnace are potassium permanganate and borax. After the smelting is completed, the smelting slag is separated from the molten liquid and the smelting slag is taken out with furnace tongs.

Among them, during water quenching in S4, the ingot is pickled before water cooling. During pickling, citric acid water is used for pickling. The mass concentration of citric acid is 3%, and the fly ash is removed after water cooling. Edge burrs and foreign inclusions.

Among them, during extrusion of S6, the extrusion pressure is controlled to be greater than 15 tons/cm2.

Wherein, during extrusion molding, the silver billet is heated to a recrystallization temperature of 582°C for extrusion.

Preferably, during the processing of S7, a lathe is used to process the Ag rotating tube embryo to the required size, and it is stored after passing the inspection.

Among them, the new high-purity low-oxygen fine-grained Ag rotating tube target is made by melting high-purity elemental Ag according to the required weight, performing the necessary deoxidation process before casting, and cooling after casting to obtain an Ag ingot. The outer skin of the ingot is then turned to remove the pore layer. Then the peeled ingot undergoes an extrusion process to obtain a rotating tube embryo with an oxygen content of less than 30ppm and an average grain size of less than 20um. Just process the tube blank to the required size.

In order to verify the excellence of the present invention, the following experiments were carried out:

First, select the comparison document and Example 1, Example 2, Example 3 and Example 4 for comparison. The experimental content and results are as follows:

Through various experiments, it can be found that the targets prepared in Example 1, Example 2, Example 3, and Example 4 have better impurity content, average grain size, and structural uniformity. The lower the total impurity content, the better. , the higher the purity, the better the effect in subsequent applications. In addition, the sputtering rate of targets with fine grains is faster than that of targets with coarse grains, and the thickness distribution of films deposited by sputtering from targets with smaller grain size differences is more uniform. In addition, usually the target material has a polycrystalline structure, and the grain size can range from microns to millimeters. The better the structural uniformity, the better its performance.

In addition, based on actual production statistics, the following results are obtained:

The experimental contents and results are as follows:

Through various experiments, it can be found that the production processes of Example 1, Example 2, Example 3, and Example 4 have lower various cost consumption and lower carbon emissions.

The above are only preferred embodiments of the present invention. The protection scope of the present invention is not limited to the above-mentioned embodiments. All technical solutions that fall under the idea of the present invention belong to the protection scope of the present invention. It should be pointed out that for those of ordinary skill in the art, several improvements and modifications may be made without departing from the principles of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims (8)

1. A method for manufacturing a high-purity low-oxygen fine-grained Ag rotating tube target for semiconductors, which is characterized by: including the following steps: S1. Material preparation: Prepare Ag raw materials with a purity greater than 99.999% for later use; S2. Smelting: Place the Ag raw material in the smelting furnace and smelt it to obtain Ag ingot; S3. Deoxidation: Before the ingot is cast, a deoxidation process of burning and biting oxygen is carried out; S4. Water quenching: water-cool the ingot; S5. Remove the outer skin of the stomatal layer: Carry off the outer skin of the stomatal layer; S6. Extrusion: Heat the ingot to 300-800°C, keep it warm for 10-60 minutes, and then extrud it once to obtain the Ag rotating tube embryo; S7. Processing: Process the Ag rotating tube blank to the required size to obtain the Ag rotating tube target. 2. A method for manufacturing a high-purity low-oxygen fine-grained Ag rotating tube target for semiconductors according to claim 1, characterized in that: the S3 is deoxidized before the ingot is cast. The process is to use lathe processing to remove the leather with pores on the surface of the ingot. 3. A method for manufacturing a high-purity low-oxygen fine-grained Ag rotating tube target for semiconductors according to claim 1, characterized in that: when S2 is smelted, the furnace selected is an intermediate frequency furnace, and the Ag raw material is first Preheat, then heat the intermediate frequency furnace to 980-990°C for heat preservation, and then add melting aids to the intermediate frequency furnace for smelting. 4. The manufacturing method of a high-purity low-oxygen fine-grained Ag rotating tube target for semiconductors according to claim 3, characterized in that: the additives added in the intermediate frequency furnace are potassium permanganate and borax, After the smelting is completed, separate the slag from the molten liquid and take out the slag with furnace tongs. 5. A method for manufacturing a high-purity low-oxygen fine-grained Ag rotating tube target for semiconductors according to claim 1, characterized in that: during water quenching in S4, the ingot is cooled before being water-cooled. Carry out pickling, use citric acid water for pickling, the mass concentration of citric acid is 3%, and remove flash burrs and foreign inclusions after water cooling. 6. A method for manufacturing a high-purity low-oxygen fine-grained Ag rotating tube target for semiconductors according to claim 1, characterized in that: when the S6 is extruded, the extrusion molding pressure is controlled to be greater than 15 tons/ square centimeters. 7. A method for manufacturing a high-purity low-oxygen fine-grained Ag rotating tube target for semiconductor use according to claim 6, characterized in that: the silver blank is heated to 580-590°C during extrusion molding. Extrusion is performed at a recrystallization temperature of ℃. 8. A method for manufacturing a high-purity low-oxygen fine-grained Ag rotating tube target for semiconductors according to claim 1, characterized in that: during processing of S7, a lathe is used to process the Ag rotating tube blank to the required level. Size, stored after passing the inspection.