CN115595539A - A kind of zinc magnesium target material and preparation method thereof - Google Patents

Abstract

The invention discloses a zinc-magnesium target material and a preparation method thereof, and belongs to the technical field of target material preparation. The preparation method of the zinc-magnesium target material comprises the following steps: uniformly mixing a zinc source and a magnesium source, placing the mixture into a vacuum induction furnace for vacuumizing treatment, and introducing protective atmosphere until the pressure in the furnace is 2-10 Pa; starting a vacuum induction furnace at the speed of 20-30 ℃/min for magnetic induction heating to 520-560 ℃, preserving heat for 20-35 min, then cooling to 430-450 ℃, and continuing preserving heat for 3-5 h; casting the mixture obtained after heat preservation into a mold and cooling to obtain a zinc-magnesium alloy material; preheating a zinc-magnesium alloy material to 300-320 ℃, rolling, and processing the shape and the size of the obtained blank target to obtain the zinc-magnesium target material. According to the method, zinc and magnesium are rapidly fused by magnetic induction high-temperature heating, then the temperature is reduced and the temperature is kept, so that material loss and component segregation are avoided, and finally the target obtained by preheating and rolling is defect-free in the interior, high in component uniformity and capable of achieving a relative density of more than 99.5%.

Description

A kind of zinc magnesium target material and preparation method thereof

technical field

The invention relates to the technical field of target preparation, in particular to a zinc-magnesium target and a preparation method thereof.

Background technique

Recently, the output and usage of solar cells are increasing year by year, and the development prospect is good. In solar cells, ZnMgO film not only has the characteristics of TCO film, but also has a larger band gap than ZnO film and AZO film, and is more High visible light transmittance and structural stability. At the same time, ZnMgO thin films are green, non-toxic, rich in sources, and have broad development space.

At present, most of the methods for preparing ZnMgO thin films use ZnMgO powder as raw material to directly prepare them, or use zinc-magnesium targets to sputter in an oxygen atmosphere. However, the target products prepared by these current methods have certain defects, resulting in poor component uniformity, and the relative density has not always reached the ideal level.

Contents of the invention

Based on the defects existing in the prior art, the object of the present invention is to provide a method for preparing a zinc-magnesium target. In this method, zinc and magnesium are rapidly fused by magnetic induction heating treatment, and then multi-stage temperature zone treatment is used to avoid zinc vapor pressure. Due to material loss and component segregation, the target material obtained after rolling has no internal defects, high component uniformity, and relative density can be greater than 99.5%.

In order to achieve the above object, the technical scheme that the present invention takes is:

A method for preparing a zinc-magnesium target, comprising the following steps:

(1) Mix the zinc source and the magnesium source evenly, put them into a vacuum induction furnace for vacuum treatment, and then introduce a protective atmosphere until the pressure in the furnace is 2-10Pa;

(2) The vacuum induction furnace turns on the magnetic induction heating at a rate of 20-30 °C/min to 520-560 °C, keeps the temperature for 20-35 minutes, then cools down to 430-450 °C and continues the heat preservation for 3-5 hours;

(3) casting the mixed material obtained after step (2) heat preservation to the mold for cooling to obtain the zinc-magnesium alloy material;

(4) The zinc-magnesium alloy material is preheated to 300-320° C. and then rolled, and the obtained blank target is processed in shape and size to obtain the zinc-magnesium target material.

In the preparation method of the zinc-magnesium target material described in the present invention, the temperature is raised to a relatively high degree by magnetic induction heating to make the raw material zinc and raw material magnesium mixed quickly and uniformly, so as to ensure the component uniformity of the product, and then rapidly cooled to a lower temperature zone for Two-stage heat preservation, this step can avoid material loss and composition segregation caused by zinc vapor pressure, casting to the mold and finally rolling with the preheating process, not only can make the internal defects of the final prepared zinc-magnesium target disappear, but also the surface of the target The appearance is good, there will be no cracking, etc., the relative density is high, and the quality of the finished product is good.

Preferably, the mass ratio of the zinc source to the magnesium source in the step (1) is (90-99.9): (0.1-10).

According to the actual needs and the appropriate range of the processing temperature rise interval, the addition ratio of the zinc source and the magnesium source within the above range can effectively control the uniformity of the setting conditions during the preparation of the zinc-magnesium target material of the present invention, and ensure the uniform quality of batches of products.

Preferably, the step of vacuuming treatment in the step (1) is: vacuuming the vacuum induction furnace until the pressure in the furnace is lower than 3×10 ^-3 Pa, then injecting a protective atmosphere until the pressure in the furnace becomes normal pressure, and then Vacuumize until the pressure in the furnace is lower than 3×10 ^{- 2} Pa.

More preferably, the protective atmosphere is argon.

Preferably, the number of times of rolling in the step (4) is 8-10 times, and the thickness of a single rolling is 0.1-0.3 mm.

When the zinc-magnesium alloy material is heated to 300-320°C, its machinability is significantly improved. After multiple rolling with a thinner rolling thickness, the internal defect degree in the obtained rough target can be effectively reduced, thereby significantly improving the product quality. Density, and at the same time, it will not cause cracking and other undesirable phenomena due to excessive rolling.

Another object of the present invention is to provide a zinc-magnesium target prepared by the method for preparing the zinc-magnesium target.

The zinc-magnesium target prepared by the preparation method of the present invention can achieve a relative density of up to 99.7% under the optimal process, has high component uniformity, has no internal defect structure, and has no cracks on the appearance, and has high relative quality.

Another object of the present invention is to provide the application of the zinc-magnesium target in preparing ZnMgO thin films for solar cells.

The beneficial effect of the present invention is that the present invention provides a method for preparing a zinc-magnesium target. In this method, the temperature is raised to a higher temperature by magnetic induction heating to quickly fuse zinc and magnesium, and then the temperature is lowered to a specific temperature for heat preservation treatment to avoid Material loss and component segregation caused by zinc vapor pressure, and finally the target obtained after special preheating rolling process has no defects inside, high component uniformity, and relative density can be greater than 99.5%.

detailed description

In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific examples/comparative examples, the purpose of which is to understand the contents of the present invention in detail, rather than limiting the present invention. All other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention. The experimental reagents, raw materials and instruments designed in the implementation of the present invention and comparative examples are common common reagents, raw materials and instruments unless otherwise specified.

Example 1

An embodiment of the zinc-magnesium target material and its preparation method described in the present invention comprises the following steps:

(1) Mix zinc powder and magnesium powder evenly according to the mass ratio of 90:10, put them into a vacuum induction furnace, evacuate the vacuum induction furnace until the pressure in the furnace is lower than 3×10 ^-3 Pa, and then inject argon into the furnace The internal pressure becomes normal pressure, then vacuumize until the pressure in the furnace is lower than 3×10 ^-2 Pa, and finally introduce argon until the pressure in the furnace is 10Pa;

(2) The vacuum induction furnace turns on the magnetic induction heating at a rate of 30°C/min to 560°C, keeps the temperature for 20 minutes and then cools down to 450°C for 3 hours;

(3) casting the mixed material obtained after the heat preservation in step (2) into a mold, cooling to a temperature lower than 40° C., and then discharging to obtain a zinc-magnesium alloy material;

(4) Preheat the zinc-magnesium alloy material to 310°C and put it into a rolling machine for rolling. The thickness of each rolling is 0.2mm, and rolling back and forth 10 times. After the obtained rough target is processed according to the shape and size requirements, it is Obtain the zinc-magnesium target.

Example 2

An embodiment of the zinc-magnesium target material and its preparation method described in the present invention comprises the following steps:

(1) Mix zinc powder and magnesium powder evenly according to the mass ratio of 99.9:0.1, put them into a vacuum induction furnace, evacuate the vacuum induction furnace until the pressure in the furnace is lower than 3×10 ^-3 Pa, and then inject argon into the furnace The internal pressure becomes normal pressure, then vacuumize until the pressure in the furnace is lower than 3×10 ^-2 Pa, and finally introduce argon until the pressure in the furnace is 10Pa;

(2) The vacuum induction furnace turns on the magnetic induction heating at a rate of 25°C/min to 530°C, keeps the temperature for 25 minutes and then cools down to 430°C for 4 hours;

(3) casting the mixed material obtained after the heat preservation in step (2) into a mold, cooling to a temperature lower than 40° C., and then discharging to obtain a zinc-magnesium alloy material;

(4) Preheat the zinc-magnesium alloy material to 300°C and put it into a rolling mill for rolling. Each rolling thickness is 0.3mm, rolling back and forth 8 times, and the obtained rough target is processed according to the shape and size requirements, that is, Obtain the zinc-magnesium target.

Example 3

An embodiment of the zinc-magnesium target material and its preparation method described in the present invention comprises the following steps:

(1) Mix zinc powder and magnesium powder evenly according to the mass ratio of 94:6, put them into a vacuum induction furnace, evacuate the vacuum induction furnace until the pressure in the furnace is lower than 3×10 ^-3 Pa, and then inject argon into the furnace The internal pressure becomes normal pressure, then vacuumize until the pressure in the furnace is lower than 3×10 ^-2 Pa, and finally introduce argon until the pressure in the furnace is 10Pa;

(2) The vacuum induction furnace turns on the magnetic induction heating at a rate of 25°C/min to 520°C, keeps the temperature for 25 minutes and then cools down to 440°C for 4 hours;

(3) casting the mixed material obtained after the heat preservation in step (2) into a mold, cooling to a temperature lower than 40° C., and then discharging to obtain a zinc-magnesium alloy material;

(4) Preheat the zinc-magnesium alloy material to 320°C and put it into a rolling mill for rolling. The thickness of each rolling is 0.2mm, rolling back and forth 9 times, and the obtained rough target is processed according to the shape and size requirements, that is, Obtain the zinc-magnesium target.

Comparative example 1

A method for preparing a zinc-magnesium target, comprising the following steps:

(1) Mix zinc powder and magnesium powder evenly according to the mass ratio of 90:10, put them into a vacuum induction furnace, evacuate the vacuum induction furnace until the pressure in the furnace is lower than 3×10 ^-3 Pa, and then inject argon into the furnace The internal pressure becomes normal pressure, then vacuumize until the pressure in the furnace is lower than 3×10 ^-2 Pa, and finally introduce argon until the pressure in the furnace is 10Pa;

(2) Turn on the magnetic induction heating at a rate of 30°C/min in the vacuum induction furnace to 450°C for 3 hours;

(3) casting the mixed material obtained after the heat preservation in step (2) into a mold, cooling to a temperature lower than 40° C., and then discharging to obtain a zinc-magnesium alloy material;

(4) Preheat the zinc-magnesium alloy material to 310°C and put it into a rolling machine for rolling. The thickness of each rolling is 0.2mm, and rolling back and forth 10 times. After the obtained rough target is processed according to the shape and size requirements, it is Obtain the zinc-magnesium target.

Comparative example 2

A method for preparing a zinc-magnesium target, comprising the following steps:

(1) Mix zinc powder and magnesium powder evenly according to the mass ratio of 90:10, put them into a vacuum induction furnace, evacuate the vacuum induction furnace until the pressure in the furnace is lower than 3×10 ^-3 Pa, and then inject argon into the furnace The internal pressure becomes normal pressure, then vacuumize until the pressure in the furnace is lower than 3×10 ^-2 Pa, and finally introduce argon until the pressure in the furnace is 10Pa;

(2) The vacuum induction furnace starts magnetic induction heating at a rate of 30°C/min to 560°C for 20 minutes;

(3) casting the mixed material obtained after the heat preservation in step (2) into a mold, cooling to a temperature lower than 40° C., and then discharging to obtain a zinc-magnesium alloy material;

(4) Preheat the zinc-magnesium alloy material to 310°C and put it into a rolling machine for rolling. The thickness of each rolling is 0.2mm, and rolling back and forth 10 times. After the obtained rough target is processed according to the shape and size requirements, it is Obtain the zinc-magnesium target.

Comparative example 3

A method for preparing a zinc-magnesium target, comprising the following steps:

(1) Mix zinc powder and magnesium powder evenly according to the mass ratio of 90:10, put them into a vacuum induction furnace, evacuate the vacuum induction furnace until the pressure in the furnace is lower than 3×10 ^-3 Pa, and then inject argon into the furnace The internal pressure becomes normal pressure, then vacuumize until the pressure in the furnace is lower than 3×10 ^-2 Pa, and finally introduce argon until the pressure in the furnace is 10Pa;

(2) The vacuum induction furnace turns on the magnetic induction heating at a rate of 30°C/min to 560°C, keeps the temperature for 20 minutes and then cools down to 450°C for 3 hours;

(3) casting the mixed material obtained after the heat preservation in step (2) into a mold, cooling to a temperature lower than 40° C., and then discharging to obtain a zinc-magnesium alloy material;

(4) Put the zinc-magnesium alloy material directly into a rolling machine for rolling, each rolling thickness is 0.2mm, rolling back and forth 10 times, after the obtained blank target is processed according to the shape and size requirements, the zinc-magnesium alloy can be obtained target.

Comparative example 4

A method for preparing a zinc-magnesium target, comprising the following steps:

(1) Mix zinc powder and magnesium powder evenly according to the mass ratio of 90:10, put them into a vacuum induction furnace, evacuate the vacuum induction furnace until the pressure in the furnace is lower than 3×10 ^-3 Pa, and then inject argon into the furnace The internal pressure becomes normal pressure, then vacuumize until the pressure in the furnace is lower than 3×10 ^-2 Pa, and finally introduce argon until the pressure in the furnace is 10Pa;

(2) The vacuum induction furnace starts magnetic induction heating at a rate of 30°C/min to 560°C for 3h+20min;

(3) casting the mixed material obtained after the heat preservation in step (2) into a mold, cooling to a temperature lower than 40° C., and then discharging to obtain a zinc-magnesium alloy material;

(4) Preheat the zinc-magnesium alloy material to 310°C and put it into a rolling machine for rolling. The thickness of each rolling is 0.2mm, and rolling back and forth 10 times. After the obtained rough target is processed according to the shape and size requirements, it is Obtain the zinc-magnesium target.

Comparative example 5

(1) Mix zinc powder and magnesium powder evenly according to the mass ratio of 90:10, put them into a vacuum induction furnace, evacuate the vacuum induction furnace until the pressure in the furnace is lower than 3×10 ^-3 Pa, and then inject argon into the furnace The internal pressure becomes normal pressure, then vacuumize until the pressure in the furnace is lower than 3×10 ^-2 Pa, and finally introduce argon until the pressure in the furnace is 10Pa;

(2) The vacuum induction furnace turns on the magnetic induction heating at a rate of 30°C/min to 450°C, and keeps warm for 3h+20min;

(3) casting the mixed material obtained after the heat preservation in step (2) into a mold, cooling to a temperature lower than 40° C., and then discharging to obtain a zinc-magnesium alloy material;

(4) Preheat the zinc-magnesium alloy material to 310°C and put it into a rolling machine for rolling. The thickness of each rolling is 0.2mm, and rolling back and forth 10 times. After the obtained rough target is processed according to the shape and size requirements, it is Obtain the zinc-magnesium target.

Comparative example 6

(1) Mix zinc powder and magnesium powder evenly according to the mass ratio of 90:10, put them into a vacuum induction furnace, evacuate the vacuum induction furnace until the pressure in the furnace is lower than 3×10 ^-3 Pa, and then inject argon into the furnace The internal pressure becomes normal pressure, then vacuumize until the pressure in the furnace is lower than 3×10 ^-2 Pa, and finally introduce argon until the pressure in the furnace is 10Pa;

(2) The vacuum induction furnace is heated to 560°C by magnetic induction at a rate of 30°C/min, and then cooled to 480°C for 2 hours after holding for 20 minutes;

(3) casting the mixed material obtained after the heat preservation in step (2) into a mold, cooling to a temperature lower than 40° C., and then discharging to obtain a zinc-magnesium alloy material;

(4) Preheat the zinc-magnesium alloy material to 310°C and put it into a rolling machine for rolling. The thickness of each rolling is 0.2mm, and rolling back and forth 10 times. After the obtained rough target is processed according to the shape and size requirements, it is Obtain the zinc-magnesium target.

Effect Example 1

In order to verify the performance superiority of the products prepared by the preparation method of the zinc-magnesium target material of the present invention, the internal defect test, component uniformity test and relative density test of the products of each embodiment and comparative example, wherein the internal defect test directly adopts Ultrasonic scanning C-Scan confirmation; component uniformity is mainly to take points from the head, middle and tail of the prepared zinc-magnesium target and use the elemental analysis method to test the magnesium content, and take the average value; the relative density directly adopts the traditional Akimi The test is carried out in Germany and France; if the target is cracked or has no complete shape, the above test will not be carried out. The test results are shown in Table 1.

Table 1

It can be seen from Table 1 that the zinc-magnesium target prepared by the method for preparing the zinc-magnesium target according to the present invention has a relatively high relative density, no obvious internal defects, and high component uniformity. The impurity amounts were all as expected. In contrast, the process described in Comparative Example 1 lacks the high-temperature zinc-magnesium fusion step, although the prepared product has a high relative density, but the magnesium element is unevenly distributed; the product of Comparative Example 2 is not subjected to the second-stage heat preservation process because the temperature is not lowered. process, the product has material loss and component segregation, and small hole defects appear inside, and the relative density of the target is also low, only 99%. Therefore, cracking occurred after rolling, which failed to meet the requirements for use; the products of Comparative Example 4 and Comparative Example 5 did not undergo the second-stage heat preservation treatment. Although they were all heat-preserved for the same time, the component uniformity of the products was difficult to reach expectations. At the same time, the relative density of the product of Comparative Example 5 is insufficient; although the product of Comparative Example 6 has undergone two stages of heat preservation treatment in the preparation process, the time is relatively short, and the product has a relatively high density, but the component uniformity is insufficient; In addition, the inventor It has been found through experiments that if the high-temperature section is used for a long time during the second-stage heat preservation process, the zinc and magnesium in the raw materials will volatilize to varying degrees, causing the ratio of zinc and magnesium in the final product to deviate from the expected one. The second stage of heat preservation treatment is carried out at a certain time.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that The technical solution of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solution of the present invention.

Claims (6)

1. The preparation method of the zinc-magnesium target is characterized by comprising the following steps:

(1) Uniformly mixing a zinc source and a magnesium source, putting the mixture into a vacuum induction furnace for vacuumizing treatment, and introducing protective atmosphere until the pressure in the furnace is 2-10 Pa;

(2) Starting a vacuum induction furnace at the speed of 20-30 ℃/min for magnetic induction heating to 520-560 ℃, preserving heat for 20-35 min, then cooling to 430-450 ℃, and continuously preserving heat for 3-5 h;

(3) Casting the mixed material obtained after heat preservation in the step (2) into a mould, and cooling to obtain a zinc-magnesium alloy material;

(4) Preheating the zinc-magnesium alloy material to 300-320 ℃, rolling, and processing the shape and the size of the obtained blank target to obtain the zinc-magnesium target material.

2. The method for preparing the zinc-magnesium target material according to claim 1, wherein the mass ratio of the zinc source to the magnesium source in the step (1) is (90-99.9): (0.1-10).

3. The method for preparing the zinc-magnesium target material according to claim 1, wherein the step of performing vacuum pumping in the step (1) comprises the following steps: vacuumizing the vacuum induction furnace until the pressure in the furnace is lower than 3 x 10 ^-3 Pa, then injecting protective atmosphere until the pressure in the furnace is changed to normal pressure, and vacuumizing until the pressure in the furnace is lower than 3X 10 ^-2 Pa; preferably, the protective atmosphere is argon.

4. The method for preparing the zinc-magnesium target material according to claim 1, wherein the rolling in the step (4) is performed for 8 to 10 times, and the thickness of each rolling is 0.1 to 0.3mm.

5. The zinc-magnesium target material prepared by the preparation method of the zinc-magnesium target material according to any one of claims 1 to 4.

6. The use of the zinc-magnesium target material of claim 5 in the preparation of a ZnMgO thin film for a solar cell.