JP5192990B2 - Copper-gallium alloy sputtering target, method for producing the sputtering target, and related applications - Google Patents

Copper-gallium alloy sputtering target, method for producing the sputtering target, and related applications Download PDF

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JP5192990B2
JP5192990B2 JP2008288573A JP2008288573A JP5192990B2 JP 5192990 B2 JP5192990 B2 JP 5192990B2 JP 2008288573 A JP2008288573 A JP 2008288573A JP 2008288573 A JP2008288573 A JP 2008288573A JP 5192990 B2 JP5192990 B2 JP 5192990B2
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copper
sputtering target
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JP2010116580A (en
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威智 黄
承▲シン▼ 杜
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光洋應用材料科技股▲分▼有限公司
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Description

  The present invention relates to a method for manufacturing a sputtering target, and more particularly, to a method for manufacturing a copper-gallium alloy sputtering target mainly having a solid solution phase.

  As non-renewable fuels are being exhausted, the development of renewable energy is becoming increasingly important. Since CIGS is a direct band gap material having high photoelectric conversion efficiency, it is suitable for use as an absorption layer for solar cells.

  CIGS thin films are most commonly manufactured by physical vapor deposition (PVD). PVD can use sputtering to form thin films on CIGS solar cells. Sputtering requires formation of a target and a substrate, and a CIGS thin film can be formed by sputtering a target material such as CIG on the substrate and then performing selenizing.

  The sputtering target can be manufactured by powder metallurgy or casting. When casting is used, the melting points of copper, indium, gallium and selenium are very different. Therefore, since these materials do not precipitate, a non-uniform thin film is formed. The eutectic microstructure of the copper alloy target has a solid solution phase and a compound phase, and the compound phase generally occupies about 30 to 40% of the metal microstructure of the copper alloy target.

However, the microstructure of such a copper alloy target has the following disadvantages.
(1) Since the material distribution of the copper alloy target is not uniform, macro segregation or micro segregation occurs.
(2) The two phases of the copper alloy target are non-uniform thin films with inferior characteristics (such as photoelectric conversion efficiency).
(3) Since the two phases of the copper alloy target cause a micro arc during sputtering, the thin film has poor properties.

  Therefore, the manufacturing cost and efficiency of CIGS solar cells depend on the sputtering target.

  In order to eliminate the drawbacks, the present invention provides a method for producing a copper-gallium alloy sputtering target for suppressing or eliminating the above disadvantages.

  The main object of the present invention is to provide a method for producing a copper-gallium alloy sputtering target mainly having a solid solution phase.

Means to solve the problem

  In order to achieve the above object, a method for producing a copper-gallium alloy sputtering target according to the present invention includes a step of forming a raw material target and a step of subjecting the raw material target to a heat treatment at a temperature range of 500 ° C. to 850 ° C. at least once. In order to obtain a copper-gallium alloy sputtering target consisting of 71 atomic% to 78 atomic% Cu and 22 atomic% to 29 atomic% Ga, and having a compound phase of 25% or less in the metal microstructure, And cooling the target thus treated to room temperature.

  Therefore, the copper-gallium alloy sputtering target does not produce micro arcs during sputtering and can maintain a consistent sputtering rate, thus forming a uniform copper-gallium thin film. Therefore, the characteristics of the copper-gallium thin film are improved.

FIG. 1 is a phase diagram of a general copper-gallium (Cu—Ga) alloy. FIG. 2 is a metal microstructure of a general copper-gallium alloy target according to the prior art. FIG. 3 is a metal microstructure of a copper-gallium alloy target according to Example 1 of the present invention. FIG. 4 is a metal microstructure of a copper-gallium alloy target according to Example 2 of the present invention.

  The method of manufacturing a copper-gallium alloy sputtering target according to the present invention includes a step of forming a raw material target and a heat treatment at a temperature range of 500 ° C. to 850 ° C. at least once to form the treated target. To obtain a copper-gallium alloy sputtering target consisting of 71 atomic% to 78 atomic% Cu and 22 atomic% to 29 atomic% Ga, and having a compound phase of 25% or less in the metal microstructure And a step of cooling the target processed as described above to room temperature.

  In the process of forming the raw material target, the raw material target is formed using powder metallurgy, or casting such as vacuum melting, continuous casting, centrifugal casting, hot press sintering, high temperature isostatic pressing (HIP), high temperature plastic deformation, etc. can do.

  At least one heat treatment is at least one mechanical treatment in a temperature range of 500 ° C. to 850 ° C., 0.5 to 0.5 in a temperature range of 500 ° C. to 850 ° C. to form a treated target. 5 hours of at least one annealing treatment or a combination of these treatments.

  In one embodiment, the at least one heat treatment comprises subjecting the raw material target to a mechanical treatment with at least one heat.

  In another form, the at least one heat treatment comprises subjecting the raw material target to at least one annealing treatment.

  In another form, the at least one heat treatment comprises subjecting the raw material target to at least one mechanical treatment with heat and then subjecting the raw material target to at least one annealing treatment.

  In another embodiment, the at least one heat treatment comprises subjecting the raw material target to at least one annealing treatment and then subjecting the raw material target to at least one mechanical treatment with heat.

  In another embodiment, the at least one heat treatment includes subjecting the raw material target to at least one mechanical treatment, then subjecting the raw material target to at least one annealing treatment, and further subjecting the raw material target to a plurality of times. It consists of repeatedly performing mechanical treatment with heat.

  Combinations of the above forms can be varied to achieve a balance between processing costs and preferred sputtering targets.

  Preferably, the mechanical treatment with heat is forging, rolling or hot pressing. Preferably, the reduction in area by mechanical treatment with heat is 0 to 90%.

  More preferably, the area reduction rate by mechanical treatment with heat is 0 to 50%.

  Most preferably, to obtain a solid solution phase with a high ratio to the compound phase, the heat treatment is at least once rolled at 800 ° C. with a reduction in area of 25% and annealed at least once at 700 ° C. for 1 hour. Including processing.

  The treated target can be cooled using air, water or oil.

  The copper-gallium alloy sputtering target according to the present invention is composed of 71 atomic% to 78 atomic% Cu and 22 atomic% to 29 atomic% Ga, and has a compound phase of 25% or less in the metal microstructure. Includes alloys.

  The invention further relates to a solar cell comprising a copper alloy.

  Since the compound phase of the copper-gallium alloy sputtering target is 25% or less of the metal microstructure, the microstructure is substantially a single phase. Therefore, the copper-gallium alloy sputtering target does not produce micro arcs during sputtering and can maintain a consistent sputtering rate, thus forming a uniform copper-gallium thin film. Therefore, the characteristics of the copper-gallium thin film are improved.

  In the following examples, the sputtering target is analyzed using an etching solution containing nitric acid, hydrogen peroxide, and water in a 3 to 1 to 1 ratio to calculate the ratio of the compound phase to the solid solution phase. It was. The microstructure was obtained using an Olympus BH microscope manufactured by Olympus. In the microstructure, the solid solution phase is shown in light gray and the compound phase is shown in dark gray. The ratio of the solid solution phase to the compound phase can be calculated by MediaCybernetics image measurement software, Image-Pro Plus Version 6.3, using the image measurement software, Image-Pro Plus Version 6.3, according to Equation 1 below. Was calculated.

(Compound phase [B]) / (Solid solution phase [A] + Compound phase [B]) Formula 1
FIG. 1 shows a phase diagram of a Cu—Ga alloy that is a eutectic system containing a solid solution phase (β phase) and a compound phase (γ phase).

  The theoretical ratio of the compound phase and the solid solution phase is calculated by Equation 1 and gives 30-40%. A is the β phase, B is the γ phase, and the compound phase generally occupies about 30 to 40% of the metal microstructure of the Cu—Ga alloy sputtering target.

  Another conventional Cu-Ga alloy sputtering target contains 75% by weight copper and 25% by weight gallium, produced by casting.

  In FIG. 2, the solid solution phase is shown in light gray and the compound phase is shown in dark gray. The empirical ratio calculated by Equation 1 is 30.4%. Therefore, the empirical ratio is consistent with the theoretical ratio.

  The method of the present invention relates to solid solution phase transformation and atomic diffusion of Cu-Ga alloy, which affects the ratio of compound phase to solid solution phase in the microstructure of the copper-gallium alloy sputtering target. Therefore, regardless of whether the raw material target is produced by powder metallurgy or casting, according to the method of the present invention, a copper-gallium alloy sputtering target having a substantially solid solution phase is shown in FIG. Is obtained as follows.

  The following examples present the heat treatment methods of the present invention for producing Cu-Ga alloy sputtering targets and compare these Cu-Ga alloy sputtering targets. Each target before treatment was shown to have an empirical ratio of about 35%. The examples are illustrative only and are not meant to limit the invention thereby.

Example 1
The raw material target was formed by vacuum melting. The raw material target was rolled at 800 ° C. with a reduction in area of 25%. Then, after annealing at 700 ° C. for 1 hour, it was cooled to room temperature. As a result, a Cu—Ga alloy sputtering target was formed.

Example 2
The raw material target was formed by air dissolution. The raw material target was annealed at 800 ° C. for 1 hour. Then, after rolling at 800 ° C. with a reduction in area of 25%, it was cooled to room temperature. As a result, a Cu—Ga alloy sputtering target was formed.

Example 3
The raw material target was formed by vacuum melting. The raw material target was hot-press sintered at 600 ° C. Then, it was annealed at 800 ° C. for 1 hour and then cooled to room temperature. As a result, a Cu—Ga alloy sputtering target was formed.

Example 4
The raw material target was formed by vacuum melting. The raw material target was rolled at 700 ° C. with a reduction in area of 40% and then cooled to room temperature. As a result, a Cu—Ga alloy sputtering target was formed.

Example 5
The raw material target was formed by vacuum melting. The raw material target was annealed at 700 ° C. for 3 hours and then cooled to room temperature. As a result, a Cu—Ga alloy sputtering target was formed.

Example 6 (comparative example)
The raw material target was formed by vacuum melting. The raw material target was rolled at 400 ° C. with a reduction in area of 25%, and then cooled to room temperature. As a result, a Cu—Ga alloy sputtering target was formed.

  In Table 1, TA indicates annealing treatment, and TMT indicates mechanical treatment with heat. In Table 1, all raw materials targets had 35% compound phase before being processed. After the method of the present invention was applied as shown in Examples 1 to 5, the compound phase of each Cu-Ga alloy sputtering target was clearly reduced. However, since the Cu—Ga alloy sputtering target of Example 6 was only treated at 400 ° C. not belonging to the scope of the present invention, the empirical ratio between the solid solution phase and the compound phase did not decrease. . Therefore, a eutectic system containing two phases still exists in the Cu—Ga alloy sputtering target of Example 6.

  FIG. 3 shows the metal microstructure of Example 1 showing the preferred state of the method of the present invention. The compound phase is only 5% of the metal microstructure of the Cu—Ga alloy sputtering target. Therefore, the Cu—Ga alloy sputtering target is substantially single phase.

  FIG. 4 shows the metal microstructure of Example 2. The compound phase is 25% of the metal microstructure of the Cu—Ga alloy sputtering target. Although the result of Example 2 is not as good as Example 1, it is an improvement over Example 6.

Claims (2)

  1.   A copper-gallium alloy sputtering target comprising an alloy composed of 71 atomic% to 78 atomic% Cu and 22 atomic% to 29 atomic% Ga, and having a compound phase of 25% or less in the metal microstructure.
  2. Forming a raw material target;
    In order to form a treated target, the raw material target is mechanically treated with at least one heat in a temperature range of 500 ° C. to 850 ° C., 0.5 to 0.5 in a temperature range of 500 ° C. to 850 ° C. Applying at least one annealing treatment for 5 hours, or a combination thereof;
    In order to obtain a copper-gallium alloy sputtering target composed of 71 atomic% to 78 atomic% Cu and 22 atomic% to 29 atomic% Ga and having a compound phase of 25% or less in the metal microstructure, as described above. Cooling the target processed to room temperature to a room temperature, a method for producing a copper-gallium alloy sputtering target.
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CN102358027B (en) * 2011-07-25 2014-07-09 天津市宏程伟业塑料制品厂 Single mold one-step forming system and single mold one-step forming method

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JP5818139B2 (en) * 2010-06-28 2015-11-18 日立金属株式会社 Cu-Ga alloy target material and method for producing the same
JP2012017481A (en) * 2010-07-06 2012-01-26 Mitsui Mining & Smelting Co Ltd Cu-Ga ALLOY AND Cu-Ga ALLOY SPUTTERING TARGET
JP5153911B2 (en) * 2011-04-22 2013-02-27 三菱マテリアル株式会社 Sputtering target and manufacturing method thereof
JP5769004B2 (en) * 2011-04-22 2015-08-26 三菱マテリアル株式会社 Sputtering target and manufacturing method thereof
EP2684978A4 (en) * 2011-08-29 2015-01-14 Jx Nippon Mining & Metals Corp Cu-Ga ALLOY SPUTTERING TARGET AND METHOD FOR PRODUCING SAME
JP5165100B1 (en) * 2011-11-01 2013-03-21 三菱マテリアル株式会社 Sputtering target and manufacturing method thereof
WO2014077110A1 (en) * 2012-11-13 2014-05-22 Jx日鉱日石金属株式会社 Cu-Ga ALLOY SPUTTERING TARGET, AND METHOD FOR PRODUCING SAME
JP5882248B2 (en) * 2013-03-21 2016-03-09 Jx金属株式会社 Cu-Ga alloy sputtering target, casting product for the sputtering target, and production method thereof
JP5622012B2 (en) * 2013-03-29 2014-11-12 三菱マテリアル株式会社 Cylindrical sputtering target and manufacturing method thereof

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JP3249408B2 (en) * 1996-10-25 2002-01-21 昭和シェル石油株式会社 Method and apparatus for manufacturing a thin-film light absorbing layer of the thin-film solar cell
JPH11260724A (en) * 1998-03-16 1999-09-24 Matsushita Electric Ind Co Ltd Method and device for manufacturing compound semiconductor thin film
JP2000073163A (en) * 1998-08-28 2000-03-07 Vacuum Metallurgical Co Ltd Copper-gallium alloy sputtering target and its production
US20040072009A1 (en) * 1999-12-16 2004-04-15 Segal Vladimir M. Copper sputtering targets and methods of forming copper sputtering targets
EP1992010A2 (en) * 2006-02-23 2008-11-19 Van Duren, Jeroen K.J. High-throughput printing of chalcogen layer and the use of an inter-metallic material
JP4811660B2 (en) * 2006-11-30 2011-11-09 三菱マテリアル株式会社 High Ga-containing Cu-Ga binary alloy sputtering target and method for producing the same

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CN102358027B (en) * 2011-07-25 2014-07-09 天津市宏程伟业塑料制品厂 Single mold one-step forming system and single mold one-step forming method

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