JP2012031508A - Cu-Ga ALLOY TARGET MATERIAL AND METHOD FOR MANUFACTURING THE SAME - Google Patents
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本発明は、例えば、カルコパイライト系薄膜太陽電池の光吸収層を形成するためのＣｕ（ＩｎＧａ）Ｓｅ２合金膜を形成するのに使用されるＣｕ−Ｇａ合金ターゲット材およびその製造方法に関するものである。 The present invention relates to a Cu—Ga alloy target material used for forming a Cu (InGa) Se 2 alloy film for forming a light absorption layer of a chalcopyrite thin film solar cell, for example, and a method for producing the same. is there.
現在、シリコン太陽電池、薄膜太陽電池、化合物太陽電池等の様々な太陽電池の開発が進んでおり、その中でも、薄膜太陽電池は薄膜技術を応用した光デバイスとして製造プロセスが簡易かつ低エネルギーで可能となる利点から商品化が進んでいる。また、薄膜太陽電池の中でも、カルコパイライト化合物であるＣｕ（ＩｎＧａ）Ｓｅ２（以下ＣＩＧＳという。）を光吸収層として備えた薄膜太陽電池が有望視されている。
ＣＩＧＳ薄膜太陽電池は、一般的に、ソーダライムガラス基板、Ｍｏ金属からなる背面電極層、ＣＩＧＳ層からなる光吸収層、透明導電膜からなる前面電極で構成される多層積層構造である。
Currently, various solar cells such as silicon solar cells, thin film solar cells, and compound solar cells are being developed. Among them, thin film solar cells can be manufactured easily and with low energy as optical devices applying thin film technology. Commercialization is progressing because of the advantages. Among thin-film solar cells, a thin-film solar cell including Cu (InGa) Se 2 (hereinafter referred to as CIGS), which is a chalcopyrite compound, as a light absorption layer is promising.
A CIGS thin film solar cell generally has a multilayer laminated structure including a soda lime glass substrate, a back electrode layer made of Mo metal, a light absorption layer made of a CIGS layer, and a front electrode made of a transparent conductive film.
このＣＩＧＳ層を形成する方法としては、例えば、Ｉｎターゲットを用いてスパッタリング法によりＩｎ薄膜を成膜した上に、Ｃｕ−Ｇａ合金ターゲット材を用いてＣｕ−Ｇａ合金薄膜を形成し、その後この積層膜をＳｅ雰囲気中で熱処理を施して四元系合金膜であるＣＩＧＳ層とする方法が用いられている。その際のＣｕ−Ｇａ合金ターゲット材としては、例えば、所望のＣｕ−Ｇａ組成の合金を真空溶解し鋳造する溶解鋳造法で作製したものが使用されている（例えば、特許文献１参照）。 As a method for forming this CIGS layer, for example, an In thin film is formed by sputtering using an In target, a Cu—Ga alloy thin film is formed using a Cu—Ga alloy target material, and then this lamination is performed. A method is used in which the film is heat treated in an Se atmosphere to form a CIGS layer that is a quaternary alloy film. As the Cu—Ga alloy target material at that time, for example, a material prepared by a melting casting method in which an alloy having a desired Cu—Ga composition is vacuum-melted and cast is used (for example, see Patent Document 1).
また、Ｃｕ−Ｇａ系合金は、脆弱で成分の偏析を生じやすいため、粉末焼結法による製造も試みられている。具体的には、高Ｇａ含有のＣｕ−Ｇａ合金組成においては、脆弱なＣｕ−Ｇａ合金相が形成されやすく、ターゲット材としての形状に機械加工する際に、欠け等の加工不具合が発生する場合がある。このため、高Ｇａ含有のＣｕ−Ｇａ合金相を低Ｇａ含有のＣｕ−Ｇａ合金相で包囲した二相共存組織に制御された焼結組織とすることで、機械加工時の問題を抑制可能なＣｕ−Ｇａ合金ターゲット材が提案されている（例えば、特許文献２参照）。 Moreover, since Cu-Ga type alloys are brittle and easily cause segregation of components, production by a powder sintering method has also been attempted. Specifically, in a Cu-Ga alloy composition containing a high Ga content, a fragile Cu-Ga alloy phase is likely to be formed, and processing defects such as chipping occur when machining into a shape as a target material. There is. For this reason, the problem at the time of machining can be suppressed by making the sintered structure controlled by the two-phase coexistence structure surrounded by the Cu-Ga alloy phase containing low Ga content the Cu-Ga alloy phase containing high Ga. A Cu—Ga alloy target material has been proposed (see, for example, Patent Document 2).
上述した特許文献２に開示されるＣｕ−Ｇａ二元系合金ターゲット材は、より脆弱な高Ｇａ含有のＣｕ−Ｇａ合金相を低Ｇａ含有のＣｕ−Ｇａ合金相を覆うように形成される二相共存組織とすることで、良好な機械加工が実現できるので有効である。
しかしながら、本発明者の検討によれば、このような二相共存組織の場合には、Ｇａ含有の濃淡を積極的に形成する方法であるため、スパッタリングに際して、レートの差が生じるために安定して所望のＣｕ−Ｇａ合金層が形成しづらいという問題が生じることを確認した。
本発明の目的は、上記課題を解決し、スパッタリングの際に安定した成膜が可能なＣｕ−Ｇａ合金ターゲット材およびその製造方法を提供することである。
The Cu—Ga binary alloy target material disclosed in Patent Document 2 described above is formed so that a more fragile high Ga-containing Cu—Ga alloy phase is covered with a low Ga-containing Cu—Ga alloy phase. A phase-coexisting structure is effective because good machining can be realized.
However, according to the study of the present inventors, in the case of such a two-phase coexisting structure, since it is a method of positively forming Ga-containing shades, a difference in rate occurs during sputtering, so that it is stable. Thus, it was confirmed that a problem that it was difficult to form a desired Cu—Ga alloy layer occurred.
An object of the present invention is to provide a Cu—Ga alloy target material that can solve the above-described problems and can stably form a film during sputtering, and a method for producing the same.
本発明者は、上記の課題を検討した結果、組成変動のない均一なＣｕ−Ｇａ合金相で一定の粒径以下の組織とし、ターゲット材全体でＧａ含有量のばらつきのないターゲット材とすることで、スパッタリングの際に安定した成膜が可能なＣｕ−Ｇａ合金ターゲット材を実現できることを見いだし本発明に到達した。 As a result of examining the above-mentioned problems, the present inventor has a uniform Cu-Ga alloy phase having no composition variation and a structure having a certain particle size or less, and a target material having no variation in Ga content in the entire target material. Thus, it has been found that a Cu—Ga alloy target material capable of stable film formation during sputtering can be realized, and the present invention has been achieved.
すなわち本発明は、Ｇａを１０〜９５質量％含有し、残部Ｃｕおよび不可避的不純物からなるＣｕ−Ｇａ合金ターゲット材であって、組織が平均粒径３００μｍ以下のＣｕ−Ｇａ合金相からなり、且つターゲット材中の各部位のＧａ含有量がターゲット材全体のＧａ含有量の平均値に対する変動量が±３％以下であるＣｕ−Ｇａ合金ターゲット材である。
また、本発明のＣｕ−Ｇａ合金ターゲット材は、ターゲット材の各部位の相対密度がターゲット材全体の相対密度の平均値に対する変動量が±２％以内であり、且つ相対密度が１００％以上である。
また、本発明のＣｕ−Ｇａ合金ターゲット材は、ターゲット材の各部位の酸素含有量がターゲット材全体の酸素含有量の平均値に対する変動量が±２０％以内の範囲にあり、且つターゲット材全体の酸素含有量の平均値が３００質量ｐｐｍ以下である。
また、本発明のＣｕ−Ｇａ合金ターゲット材は、前記酸素含有量が２００質量ｐｐｍ以下であることが好ましい。
また、本発明のＣｕ−Ｇａ合金ターゲット材の前記平均粒径は、４０μｍ以上であることが好ましい。
また、本発明のＣｕ−Ｇａ合金ターゲット材は、Ｇａを１０〜９５質量％含有し、残部Ｃｕおよび不可避的不純物からなるＣｕ−Ｇａ合金粉を温度７００〜９００℃、圧力１０〜２００ＭＰａで１〜１０時間の加圧焼結を行うことで得ることができる。
That is, the present invention is a Cu-Ga alloy target material containing 10 to 95% by mass of Ga, the balance being Cu and unavoidable impurities, the structure comprising a Cu-Ga alloy phase having an average particle size of 300 μm or less, and The Ga content of each part in the target material is a Cu—Ga alloy target material whose variation with respect to the average value of the Ga content of the entire target material is ± 3% or less.
Further, in the Cu—Ga alloy target material of the present invention, the relative density of each part of the target material has a variation amount within ± 2% with respect to the average value of the relative density of the entire target material, and the relative density is 100% or more. is there.
Further, in the Cu—Ga alloy target material of the present invention, the oxygen content of each part of the target material is within a range of variation within ± 20% with respect to the average value of the oxygen content of the entire target material, and the entire target material The oxygen content average value is 300 mass ppm or less.
In the Cu—Ga alloy target material of the present invention, the oxygen content is preferably 200 mass ppm or less.
Moreover, it is preferable that the said average particle diameter of the Cu-Ga alloy target material of this invention is 40 micrometers or more.
Moreover, the Cu-Ga alloy target material of this invention contains 10-95 mass% of Ga, Cu-Ga alloy powder which consists of remainder Cu and an unavoidable impurity is 1-200 MPa at the temperature of 700-900 degreeC, and the pressure of 10-200 MPa. It can be obtained by performing pressure sintering for 10 hours.
本発明のＣｕ−Ｇａ合金ターゲット材によれば、スパッタの際のターゲット上でのノジュールの発生を抑制することができる。また、本発明のＣｕ−Ｇａ合金スパッタリングターゲット材を使用してスパッタ成膜することで、スパッタ成膜後の薄膜中で欠陥原因となる異常放電（アーキング）やパーティクルの発生が抑制され良好なＣｕ−Ｇａ層が形成できるため、太陽電池の製造において極めて有効である。 According to the Cu—Ga alloy target material of the present invention, generation of nodules on the target during sputtering can be suppressed. Also, by using the Cu—Ga alloy sputtering target material of the present invention to form a sputter film, the abnormal discharge (arcing) and the generation of particles that cause defects in the thin film after the sputter film formation are suppressed and good Cu is obtained. Since a -Ga layer can be formed, it is extremely effective in the production of solar cells.
本発明のＣｕ−Ｇａ合金ターゲット材は、Ｇａを１０〜９５質量％含有し、残部Ｃｕおよび不可避的不純物からなるものである。
Ｇａ含有量を上記の範囲とした理由は、Ｇａ含有量を１０〜９５質量％含有するＣｕ−Ｇａ合金では組成の偏在が起こりやすく、組成変動のない均一なＣｕ−Ｇａ合金相を得ることが望まれる組成であるためである。
また、特に、本発明のＣｕ−Ｇａ合金ターゲット材をＣＩＧＳ光吸収層の形成に適用する場合には、Ｇａ含有量が１０質量％に満たない場合ではＣＩＧＳ光吸収層中のＧａ濃度が低く変換効率が向上しない。一方、Ｇａ含有量が９５質量％を超えるとわずかな組成ズレで融点が大きく低下するため、製膜時のスプラッシュやバッキングプレートとのボンディング剥離を引き起こし、安定的なスパッタを行うターゲット材としては適さない。
なお、ＣＩＧＳ層形成時における５００℃前後の加熱により、Ｃｕ−Ｇａ層、Ｉｎ層及びＳｅ（Ｓ）の拡散処理が必要であり、このときＣｕ−Ｇａ合金層と背面電極層との密着性を確保するためにはＣｕ−Ｇａ合金層が溶融しないことが好ましいという理由から、ターゲット材の組成においてもＧａ含有量は、７０質量％以下であることが好ましい。
The Cu—Ga alloy target material of the present invention contains 10 to 95% by mass of Ga, and consists of the remainder Cu and inevitable impurities.
The reason why the Ga content is in the above range is that a Cu-Ga alloy containing 10 to 95% by mass of Ga content tends to have an uneven composition, and a uniform Cu-Ga alloy phase having no composition variation can be obtained. This is because the composition is desired.
In particular, when the Cu—Ga alloy target material of the present invention is applied to the formation of the CIGS light absorption layer, the Ga concentration in the CIGS light absorption layer is converted to be low when the Ga content is less than 10% by mass. Efficiency does not improve. On the other hand, if the Ga content exceeds 95% by mass, the melting point is greatly lowered with a slight compositional deviation, causing splashing during film formation and bonding peeling from the backing plate, making it suitable as a target material for stable sputtering. Absent.
In addition, the diffusion process of a Cu-Ga layer, In layer, and Se (S) is required by heating at around 500 ° C. when forming the CIGS layer. At this time, the adhesion between the Cu—Ga alloy layer and the back electrode layer is improved. In order to ensure, it is preferable that the Cu—Ga alloy layer does not melt, so that the Ga content is preferably 70% by mass or less even in the composition of the target material.
本発明のＣｕ−Ｇａ合金ターゲット材は、平均粒径３００μｍ以下のＣｕ−Ｇａ合金相からなり、且つターゲット材中の各部位のＧａ含有量がターゲット材全体のＧａ含有量の平均値に対する変動量が±３％以内である。以下、その理由を説明する。
まず、本発明のＣｕ−Ｇａ合金ターゲット材は、ターゲット材中の各部位の成分変動を抑制するために、Ｃｕ−Ｇａ合金相を平均粒径３００μｍ以下に限定する。本発明では、より顕著に成分変動をなくすためには、Ｃｕ−Ｇａ合金相の平均粒径を４０μｍ以上にすることが好ましい。これにより、本発明のＣｕ−Ｇａ合金ターゲット材は、スパッタの際に凹凸が小さい平滑なエロージョン面をターゲット材表面に実現することが可能となり、ターゲット上のノジュールの発生を抑制することができる。
また、本発明のＣｕ−Ｇａ合金ターゲット材は、組成変動のない均一なＣｕ−Ｇａ相からなるターゲット材とすることにより、組成変動におけるスパッタレート差を抑制し、局所的な凹凸のバラつきをなくすことで均一なエロージョン面を実現し、ターゲット上のノジュールの発生を抑制することが可能となるためである。また、ノジュールの発生の抑制は、スパッタ中の異常放電やスパッタ成膜後の薄膜中で欠陥原因となるパーティクルの発生を抑制することにも寄与する。
The Cu—Ga alloy target material of the present invention is composed of a Cu—Ga alloy phase having an average particle diameter of 300 μm or less, and the Ga content of each part in the target material is a variation with respect to the average value of the Ga content of the entire target material. Is within ± 3%. The reason will be described below.
First, the Cu—Ga alloy target material of the present invention limits the Cu—Ga alloy phase to an average particle size of 300 μm or less in order to suppress component fluctuations at each site in the target material. In the present invention, in order to eliminate the component fluctuation more remarkably, it is preferable that the average particle diameter of the Cu—Ga alloy phase is 40 μm or more. Thereby, the Cu—Ga alloy target material of the present invention can realize a smooth erosion surface with small irregularities on the surface of the target material during sputtering, and can suppress the generation of nodules on the target.
In addition, the Cu—Ga alloy target material of the present invention is a target material composed of a uniform Cu—Ga phase without composition variation, thereby suppressing the difference in sputtering rate in composition variation and eliminating local unevenness. This is because a uniform erosion surface can be realized and generation of nodules on the target can be suppressed. Further, the suppression of the generation of nodules also contributes to the suppression of abnormal discharge during sputtering and generation of particles that cause defects in the thin film after sputtering film formation.
また、Ｃｕ−Ｇａ合金は、組成によって非常に脆弱な相が現れるが、ターゲット材中の各部位のＧａ含有量をターゲット材全体のＧａ含有量の平均値に対する変動量を±３％以下とすることで不連続組織を抑制し、ノジュールの基点となる機械加工による表面肌荒れや脱落を防止することが可能である。 Moreover, although a very fragile phase appears depending on the composition of the Cu—Ga alloy, the variation of the Ga content of each part in the target material with respect to the average value of the Ga content of the entire target material is ± 3% or less. In this way, it is possible to suppress discontinuous structures and prevent surface roughening and falling off due to machining, which is the base point of nodules.
本発明のＣｕ−Ｇａ合金ターゲット材は、各部位の相対密度がターゲット材全体の相対密度の平均値に対する変動量が±２％以内であり、且つその相対密度が全て１００％以上である。
ターゲット材中の密度にばらつきが存在していると、各部位でスパッタレートがばらつくことから、膜厚、膜応力が影響を受け面内均一性が低下する。各部位の相対密度がターゲット材全体の相対密度の平均値に対する変動量が±２％を超えると面内ばらつきが著しく増加するため、本発明では相対密度の平均値に対する変動量を±２％以内にする。
また、相対密度が低くなるとターゲット材中に存在する空隙が増加し、空隙を基点としてスパッタリング工程中に、異常放電の原因となるノジュールの発生が起こりやすくなる。特に、相対密度が１００％に満たないとノジュールが発生する確率が高くなるため、相対密度は１００％以上にする。より好ましくは、１０７％以上である。
In the Cu—Ga alloy target material of the present invention, the relative density of each part has a variation amount within ± 2% with respect to the average value of the relative density of the entire target material, and the relative density is all 100% or more.
If there is a variation in the density in the target material, the sputtering rate varies at each site, so that the film thickness and film stress are affected and the in-plane uniformity is reduced. If the relative density of each part exceeds ± 2% relative to the average relative density of the entire target material, the in-plane variation increases significantly. Therefore, in the present invention, the fluctuation relative to the average relative density is within ± 2%. To.
Further, when the relative density is lowered, voids existing in the target material increase, and nodules that cause abnormal discharge are likely to occur during the sputtering process with the voids as a base point. In particular, if the relative density is less than 100%, the probability that nodules are generated increases, so the relative density is set to 100% or more. More preferably, it is 107% or more.
なお、本発明において「相対密度」とは、アルキメデス法により測定されたＣｕ−Ｇａ合金ターゲット材のかさ密度をその理論密度で割った値を百分率で表したものをいう。ここで、Ｃｕ−Ｇａ合金の理論密度としては、簡単のため、合金相を含まないＣｕ及びＧａのみからなるものと仮定して算出した理論密度を用いた。具体的には、Ｃｕ、Ｇａの密度として各々８．９６ｇ／ｃｍ３、５．９１ｇ／ｃｍ３の値を用い、組成比から得られる質量比で算出した加重平均として得られた値を理論密度の値として用いた。Ｃｕ−Ｇａ合金の密度の真の値は、本発明でいう理論密度に比べて一般に高くなるため、上記のようにして求めた相対密度の値は１００％を超える場合がある。 In the present invention, “relative density” refers to a value obtained by dividing the bulk density of a Cu—Ga alloy target material measured by the Archimedes method by its theoretical density, expressed as a percentage. Here, as the theoretical density of the Cu—Ga alloy, for the sake of simplicity, the theoretical density calculated on the assumption that the alloy is composed only of Cu and Ga not including an alloy phase was used. Specifically, values of 8.96 g / cm 3 and 5.91 g / cm 3 are used as the densities of Cu and Ga, respectively, and the value obtained as a weighted average calculated by the mass ratio obtained from the composition ratio is the theoretical density. Was used as the value of. Since the true value of the density of the Cu—Ga alloy is generally higher than the theoretical density in the present invention, the relative density value obtained as described above may exceed 100%.
本発明のＣｕ−Ｇａ合金ターゲット材は、各部位の酸素含有量がターゲット全体の酸素含有量の平均値に対する変動量が±２０％以内の範囲にあり、且つターゲット材全体の酸素量の平均値が３００質量ｐｐｍ以下である。
それは、ターゲット材中の酸素含有量にばらつきが存在していると、スパッタによって得られる膜の酸素量がばらつくことから、膜の抵抗値、熱伝導率、膜応力が影響を受けこれらの各種特性の面内均一性が低下するためである。このため、各部位の酸素量は、ターゲット材全体の酸素量の平均値に対する変動量を±２０％以内としている。
また、ターゲット材全体としての酸素含有量は、２００質量ｐｐｍ以下とすることが望ましい。ターゲット材全体としての酸素含有量は、３００質量ｐｐｍを超えるとそのばらつきの影響よりも酸素の絶対量の方がより大きく影響するようになる。ターゲット材中に存在する酸素が多いとスパッタリング中に酸素が膜中に取り込まれＣＩＧＳ層形成時のセレン化、硫化を阻害するため、Ｃｕ−Ｇａ合金ターゲット材中の酸素含有量を３００質量ｐｐｍ以下とすることは、良好なＣＩＧＳ層の形成に有効である。
また、特に、粉末焼結法による焼結ターゲット材においては、原料粉末を焼結する際に酸素を低減することが困難であり、Ｃｕ−Ｇａ合金組成においても酸素含有量３０質量ｐｐｍ以下とすることは困難である。そのため、酸素３０〜３００質量ｐｐｍを不可避的に含む焼結Ｃｕ−Ｇａ合金ターゲット材においては、各部位の酸素含有量がターゲット全体の酸素含有量の平均値に対して±２０％以内の範囲とすることは、均一な成膜の特性を得るために特によい。
In the Cu—Ga alloy target material of the present invention, the oxygen content of each part is within a range of variation within ± 20% with respect to the average value of the oxygen content of the entire target, and the average value of the oxygen content of the entire target material Is 300 ppm by mass or less.
This is because if the oxygen content in the target material varies, the amount of oxygen in the film obtained by sputtering varies, so the resistance value, thermal conductivity, and film stress of the film are affected. This is because the in-plane uniformity is reduced. For this reason, the amount of oxygen in each part is within ± 20% of the variation with respect to the average value of the amount of oxygen of the entire target material.
Further, the oxygen content of the target material as a whole is desirably 200 mass ppm or less. When the oxygen content of the target material as a whole exceeds 300 ppm by mass, the absolute amount of oxygen has a greater influence than the influence of the variation. If there is a lot of oxygen present in the target material, oxygen is taken into the film during sputtering and selenization and sulfidation during CIGS layer formation are inhibited, so the oxygen content in the Cu-Ga alloy target material is 300 mass ppm or less. It is effective to form a good CIGS layer.
In particular, in a sintering target material by a powder sintering method, it is difficult to reduce oxygen when sintering raw material powder, and the oxygen content is 30 mass ppm or less even in the Cu-Ga alloy composition. It is difficult. Therefore, in the sintered Cu-Ga alloy target material inevitably containing 30 to 300 ppm by mass of oxygen, the oxygen content of each part is within a range of ± 20% with respect to the average value of the oxygen content of the entire target. This is particularly good for obtaining uniform film formation characteristics.
本発明におけるターゲット材の各部位のＧａ含有量、相対密度、酸素含有量とは、図２に示すように、例えば円板状のターゲット材の場合には、中心部（部位１）と、中心部を通り円周を均等に分割した２本の直線上の外周近傍位置の４箇所（部位２〜５）、およびその１／２の距離の位置の４箇所（部位６〜９）の合計９箇所からそれぞれ採取した試料の分析値とする。
また、各試料の寸法は、１５×１５×６（ｍｍ）とし、Ｇａ含有量は原子吸光法、相対密度はアルキメデス法、酸素含有量は赤外線吸収法で分析した値とする。
As shown in FIG. 2, the Ga content, relative density, and oxygen content of each part of the target material in the present invention are, for example, in the case of a disk-shaped target material, the center (part 1) and the center 4 parts (parts 2 to 5) in the vicinity of the outer periphery on two straight lines that pass through the part and the circumference is equally divided, and a total of 9 parts (parts 6 to 9) at positions that are ½ the distance The analysis value of each sample collected from each location.
The dimensions of each sample are 15 × 15 × 6 (mm), the Ga content is an atomic absorption method, the relative density is an Archimedes method, and the oxygen content is a value analyzed by an infrared absorption method.
次に、本発明のＣｕ−Ｇａ合金ターゲット材を作製するための方法を以下に説明する。
本発明のＣｕ−Ｇａ合金ターゲット材は、単一組成のＣｕ−Ｇａ合金相を得るために、ターゲット材の所望組成のＣｕ−Ｇａ合金粉末を作製し、そのＣｕ−Ｇａ合金粉末を加圧焼結法によって焼結体を得る方法を適用する。Ｃｕ−Ｇａ合金粉末は、ターゲット材の所望組成のＣｕ−Ｇａ合金に調整できれば使用可能であり、所望組成に調整したＣｕ−Ｇａ合金を真空溶解後に鋳造した鋳塊を粉砕して得られる粉砕粉末、Ｃｕ−Ｇａ合金溶湯をガスアトマイズ法等のアトマイズ法に代表される溶湯急冷法によって得られる粉末、などを使用することができる。その中でも、粉末中の不純物を低減でき、粒径の揃った粉末を比較的得やすいガスアトマイズ粉末を用いることが好ましい。
Next, a method for producing the Cu—Ga alloy target material of the present invention will be described below.
In order to obtain a Cu—Ga alloy target material having a single composition, the Cu—Ga alloy target material of the present invention produces a Cu—Ga alloy powder having a desired composition of the target material, and pressurizes the Cu—Ga alloy powder. A method of obtaining a sintered body by a sintering method is applied. The Cu-Ga alloy powder can be used if it can be adjusted to a Cu-Ga alloy having a desired composition of the target material, and is a pulverized powder obtained by pulverizing an ingot obtained by casting a Cu-Ga alloy adjusted to a desired composition after vacuum melting The powder obtained by the molten metal quenching method represented by atomizing methods, such as a gas atomizing method, etc. can be used for a Cu-Ga alloy molten metal. Among them, it is preferable to use a gas atomized powder that can reduce impurities in the powder and relatively easily obtain a powder having a uniform particle diameter.
ガスアトマイズ法によるＣｕ−Ｇａ合金粉末を使用する場合には、アトマイズ出湯温度はＣｕ−Ｇａ合金の融点に対して５０℃から３００℃高い温度であることが好ましい。この理由は、合金融点から融点に対し５０℃高い温度範囲では溶湯ノズルが閉塞する可能性があり、合金融点に対し３００℃を超える温度では、アトマイズ粉末がアトマイズ装置のチャンバー内で凝集する可能性があるためである。また、より球状で酸素含有量を抑制したアトマイズ粉末を得るためにはアトマイズのガス圧力は１ＭＰａ以上１０ＭＰａ以下とすることが好ましい。
また、Ｃｕ−Ｇａ合金粉末は、平均粒径２０〜３００μｍであることが好ましい。平均粒径が２０μｍを下回る粉末では、単位体積当たりの比表面積が大きくなるため、粉末全体の酸素含有量が高くなり、焼結体の酸素含有量に影響を与えるためである。一方、平均粒径が３００μｍを超える粉末では、焼結性が低下し、高密度の焼結体を得ることが困難になる。
When using the Cu-Ga alloy powder by a gas atomization method, it is preferable that the atomization hot water temperature is 50 to 300 degreeC higher than melting | fusing point of Cu-Ga alloy. This is because the molten metal nozzle may clog in the temperature range higher than the melting point of the alloy by 50 ° C., and the atomized powder aggregates in the chamber of the atomizing device at a temperature exceeding 300 ° C. relative to the melting point of the alloy. This is because there is a possibility. In order to obtain atomized powder having a more spherical shape and a reduced oxygen content, the gas pressure of atomization is preferably 1 MPa or more and 10 MPa or less.
Moreover, it is preferable that Cu-Ga alloy powder is 20-300 micrometers in average particle diameter. This is because, in the powder having an average particle size of less than 20 μm, the specific surface area per unit volume is increased, so that the oxygen content of the entire powder is increased, which affects the oxygen content of the sintered body. On the other hand, when the average particle size exceeds 300 μm, the sinterability is lowered and it is difficult to obtain a high-density sintered body.
本発明の緻密化した焼結体のターゲット材を得るためには、上述したＣｕ−Ｇａ合金粉末を加圧焼結法によって作製する。加圧焼結法としては、ホットプレス、熱間静水圧プレス、通電加圧焼結、熱間押し出しなどの方法を適用することができる。中でも熱間静水圧プレスは加圧圧力が高く、緻密な焼結体が得られ易いため、特に好ましい。
なお、加圧焼結時の最高温度は、Ｃｕ−Ｇａ合金の融点に対して１０℃から３００℃低い温度に設定することが好ましい。この理由は、焼結温度がＣｕ−Ｇａ合金の融点に対し３００℃以上低い場合には、緻密な焼結体が得られ難く、Ｃｕ−Ｇａ合金の融点に対し１０℃低い温度を超えると粉末が溶融する可能性があるためである。本発明では、焼結温度を７００〜９００℃とする。
また、加圧焼結時の最高圧力は、１０ＭＰａ以上に設定することが好ましい。その理由は最高圧力が１０ＭＰａを下回ると緻密な焼結体が得にくいためである。一方、２００ＭＰａを超えると耐え得る装置が限られるという問題がある。本発明では、加圧力を１０〜２００ＭＰａとする。
また、焼結時間は、１時間未満では焼結を十分に進行させるのが難しく、１０時間を超えると製造効率において避ける方がよい。本発明では、焼結時間を１〜１０時間とする。
なお、熱間静水圧プレスやホットプレスで加圧焼結をする際には、混合粉末を加圧容器や加圧用ダイスに充填した後に、加熱しながら減圧脱気をすることが望ましい。減圧脱気は、加熱温度１００〜６００℃の範囲で、大気圧（１０１．３ｋＰａ）より低い減圧下で行うことが望ましい。それは、得られる焼結体の酸素をより低減することが可能となるためである。
In order to obtain the densified sintered compact target material of the present invention, the above-mentioned Cu-Ga alloy powder is produced by a pressure sintering method. As the pressure sintering method, methods such as hot pressing, hot isostatic pressing, energizing pressure sintering, hot extrusion, and the like can be applied. Among them, the hot isostatic press is particularly preferable because the pressurization pressure is high and a dense sintered body can be easily obtained.
In addition, it is preferable to set the maximum temperature at the time of pressure sintering to a temperature lower by 10 to 300 ° C. than the melting point of the Cu—Ga alloy. This is because if the sintering temperature is lower than the melting point of the Cu—Ga alloy by 300 ° C. or more, it is difficult to obtain a dense sintered body, and if the temperature exceeds 10 ° C. lower than the melting point of the Cu—Ga alloy, the powder This is because there is a possibility of melting. In the present invention, the sintering temperature is 700 to 900 ° C.
The maximum pressure during pressure sintering is preferably set to 10 MPa or more. The reason is that it is difficult to obtain a dense sintered body when the maximum pressure is less than 10 MPa. On the other hand, if it exceeds 200 MPa, there is a problem that the apparatus that can withstand is limited. In the present invention, the applied pressure is 10 to 200 MPa.
In addition, if the sintering time is less than 1 hour, it is difficult to sufficiently advance the sintering, and if it exceeds 10 hours, it is better to avoid the production efficiency. In the present invention, the sintering time is 1 to 10 hours.
In addition, when performing pressure sintering by hot isostatic pressing or hot pressing, it is desirable to deaerate under reduced pressure while heating after filling the mixed powder into a pressure vessel or a pressure die. The vacuum degassing is desirably performed under a reduced pressure lower than the atmospheric pressure (101.3 kPa) in the heating temperature range of 100 to 600 ° C. This is because oxygen in the obtained sintered body can be further reduced.
以下の実施例で本発明を更に詳しく説明する。
実施例１として先ず、Ｃｕ原料を６８質量％、Ｇａ原料を３２質量％の割合になるように秤量して溶解炉内に装填し真空溶解した後、出湯温度１０００℃、アトマイズガス圧４ＭＰａでガスアトマイズを行いＣｕ−Ｇａ合金粉末を得た。得られた粉末を目開き２５０μｍのふるいを用いて分級を実施し、平均粒径（Ｄ５０）が７５μｍの粉末を得た。この粉末をカーボン製の加圧容器に充填しホットプレス装置の炉体内部に設置して７５０℃、３０ＭＰａ、２時間の加圧焼結を実施した。加圧焼結後にカーボン製の加圧容器から取り出し焼結体を得た。得られた焼結体を、ダイヤモンド砥石を用いて平面研削による板厚加工を実施後、ウォータージェット切断機を用いて切断加工することによって、直径１８０ｍｍ×厚さ６ｍｍのＣｕ−Ｇａ合金ターゲット材を２枚製作した。２枚のＣｕ−Ｇａ合金ターゲット材は同一原料、同一条件で製作したものであり、同一の密度、Ｇａ含有量、酸素含有量を有しているものとみなすことができる。
The following examples further illustrate the present invention.
As Example 1, first, Cu raw material was weighed to a ratio of 68% by mass and Ga raw material to a ratio of 32% by mass, charged in a melting furnace and vacuum melted, and then gas atomized at a tapping temperature of 1000 ° C. and an atomizing gas pressure of 4 MPa. To obtain a Cu—Ga alloy powder. The obtained powder was classified using a sieve having an opening of 250 μm to obtain a powder having an average particle diameter (D50) of 75 μm. This powder was filled in a carbon pressure vessel and placed inside a furnace body of a hot press apparatus, and pressure sintering was performed at 750 ° C., 30 MPa for 2 hours. After pressure sintering, the sintered body was obtained from the carbon pressure vessel. The obtained sintered body is subjected to plate thickness processing by surface grinding using a diamond grindstone, and then cut using a water jet cutting machine to obtain a Cu-Ga alloy target material having a diameter of 180 mm and a thickness of 6 mm. Two pieces were produced. The two Cu—Ga alloy target materials are manufactured under the same raw material and under the same conditions, and can be regarded as having the same density, Ga content, and oxygen content.
このようにして得たＣｕ−Ｇａ合金ターゲット材の内、１枚は分析用として用い、図２に示す各測定位置からそれぞれ１５×１５×６（ｍｍ）の分析用試料を切り出し、各試料の相対密度、Ｇａ含有量、酸素含有量を測定した。表１に各部位における相対密度、Ｇａ含有量、酸素含有量とその平均値を示す。また表２に各部位における相対密度、Ｇａ含有量、酸素含有量のそれぞれの全体平均に対する変動率（％）を示す。 One of the Cu—Ga alloy target materials thus obtained was used for analysis, and 15 × 15 × 6 (mm) analysis samples were cut out from the respective measurement positions shown in FIG. Relative density, Ga content, and oxygen content were measured. Table 1 shows the relative density, the Ga content, the oxygen content and the average value in each part. Table 2 shows the rate of change (%) relative to the overall average of the relative density, Ga content, and oxygen content at each site.
比較例１として以下のようにＣｕ−Ｇａ合金ターゲット材を製作した。先ず、Ｃｕ原料を６８質量％、Ｇａ原料を３２質量％の割合になるように秤量して溶解炉内に装填し、真空溶解を行った後、出湯温度１０００℃で鋳型に流し込みＣｕ−Ｇａ合金鋼塊を得た。得られた鋼塊の押し湯部を、ワイヤー放電加工機を用いて切除した後、ダイヤモンド砥石を用いて平面研削による板厚加工を実施後、ウォータージェット切断機を用いて切断加工することによって、直径１８０ｍｍ×厚さ６ｍｍのＣｕ−Ｇａ合金ターゲット材を２枚製作した。２枚のＣｕ−Ｇａ合金ターゲット材は同一原料、同一条件で製作したものであり、同一の密度、Ｇａ含有量、酸素含有量を有しているものとみなすことができる。 As Comparative Example 1, a Cu—Ga alloy target material was manufactured as follows. First, the Cu raw material is weighed to a ratio of 68% by mass and the Ga raw material to a ratio of 32% by mass, charged in a melting furnace, vacuum melted, poured into a mold at a tapping temperature of 1000 ° C., and a Cu—Ga alloy. A steel ingot was obtained. After excising the hot metal part of the obtained steel ingot using a wire electric discharge machine, after carrying out plate thickness processing by surface grinding using a diamond grindstone, by cutting using a water jet cutting machine, Two Cu—Ga alloy target materials having a diameter of 180 mm and a thickness of 6 mm were produced. The two Cu—Ga alloy target materials are manufactured under the same raw material and under the same conditions, and can be regarded as having the same density, Ga content, and oxygen content.
このようにして得たＣｕ−Ｇａ合金ターゲット材の内、１枚は分析用として用い、前述した方法に従って各測定位置からそれぞれの分析用試料を切り出し、各試料の相対密度、Ｇａ含有量、酸素含有量を測定した。表３に各部位における相対密度、Ｇａ含有量、酸素含有量とその平均値を示す。また表４に各部位における相対密度、Ｇａ含有量、酸素含有量のそれぞれの全体平均に対する変動率（％）を示す。 One of the Cu—Ga alloy target materials thus obtained was used for analysis, and each analysis sample was cut out from each measurement position according to the method described above, and the relative density, Ga content, oxygen of each sample was cut out. The content was measured. Table 3 shows the relative density, Ga content, oxygen content and the average value in each part. Table 4 shows the fluctuation rate (%) with respect to the overall average of the relative density, Ga content, and oxygen content in each part.
また、実施例１及び比較例１のＣｕ−Ｇａ合金ターゲット材の平均結晶粒径を測定した。実施例１のＣｕ−Ｇａ合金ターゲット材では、図１に示す光学顕微鏡像で示すように平均粒径は、５０μｍであった。比較例１は場所により粒径は異なるが１ｍｍを超える大きな結晶粒であった。 Moreover, the average crystal grain size of the Cu—Ga alloy target material of Example 1 and Comparative Example 1 was measured. In the Cu—Ga alloy target material of Example 1, the average particle size was 50 μm as shown in the optical microscope image shown in FIG. Comparative Example 1 was a large crystal grain exceeding 1 mm, although the grain size was different depending on the location.
次に上記で製作した各ターゲット材のスパッタテストを実施した。スパッタはＡｒ圧力０．６Ｐａ、ＤＣ電力５００Ｗの条件で積算時間５時間実施した。比較例１はアーキングが発生していたのに対し、実施例１はアーキングが確認されなかった。また、スパッタ後のターゲット表面観察を行った比較例１のＣｕ−Ｇａ合金ターゲットでは目視で多数のノジュールが確認されたのに対し、実施例１のＣｕ−Ｇａ合金ターゲット材では目視ではノジュールが確認されなかった。 Next, the sputter test of each target material produced above was carried out. Sputtering was performed under the conditions of an Ar pressure of 0.6 Pa and a DC power of 500 W for an integrated time of 5 hours. In Comparative Example 1, arcing occurred, whereas in Example 1, no arcing was confirmed. In addition, a large number of nodules were visually confirmed in the Cu—Ga alloy target of Comparative Example 1 in which the target surface was observed after sputtering, whereas nodules were visually confirmed in the Cu—Ga alloy target material of Example 1. Was not.
次に実施例２として、Ｃｕ原料を７５質量％、Ｇａ原料を２５質量％の割合になるように秤量して溶解炉内に装填し真空溶解した後、出湯温度１０５０℃、アトマイズガス圧４ＭＰａでガスアトマイズを行いＣｕ−Ｇａ合金粉末を得た。得られた粉末を目開き２５０μｍのふるいを用いて分級を実施し、平均粒径（Ｄ５０）が９５μｍの粉末を得た。この粉末を鉄製の加圧容器に充填し熱間静水圧プレス装置の炉体内部に設置して８００℃、１２０ＭＰａ、５時間の加圧焼結を実施した。加圧焼結後に鉄製の加圧容器を切削により除去して焼結体を得た。得られた焼結体を、ダイヤモンド砥石を用いて平面研削による板厚加工を実施後、ウォータージェット切断機を用いて切断加工することによって、直径１８０ｍｍ×厚さ６ｍｍのＣｕ−Ｇａ合金ターゲット材を２枚製作した。２枚のＣｕ−Ｇａ合金ターゲット材は同一原料、同一条件で製作したものであり、同一の密度、Ｇａ含有量、酸素含有量を有しているものとみなすことができる。 Next, as Example 2, the Cu raw material was weighed to a ratio of 75 mass% and the Ga raw material to a ratio of 25 mass%, charged in a melting furnace and melted in a vacuum, and then the hot water temperature was 1050 ° C. and the atomizing gas pressure was 4 MPa. Gas atomization was performed to obtain a Cu-Ga alloy powder. The obtained powder was classified using a sieve having an opening of 250 μm to obtain a powder having an average particle diameter (D50) of 95 μm. This powder was filled in an iron pressure vessel and placed inside a furnace body of a hot isostatic press to perform pressure sintering at 800 ° C., 120 MPa for 5 hours. After pressure sintering, the iron pressure vessel was removed by cutting to obtain a sintered body. The obtained sintered body is subjected to plate thickness processing by surface grinding using a diamond grindstone, and then cut using a water jet cutting machine to obtain a Cu-Ga alloy target material having a diameter of 180 mm and a thickness of 6 mm. Two pieces were produced. The two Cu—Ga alloy target materials are manufactured under the same raw material and under the same conditions, and can be regarded as having the same density, Ga content, and oxygen content.
このようにして得たＣｕ−Ｇａ合金ターゲット材の内、１枚は分析用として用い、図２に示す各測定位置からそれぞれ１５×１５×６（ｍｍ）の分析用試料を切り出し、各試料の相対密度、Ｇａ含有量、酸素含有量を測定した。表５に各部位における相対密度、Ｇａ含有量、酸素含有量とその平均値を示す。また表６に各部位における相対密度、Ｇａ含有量、酸素含有量のそれぞれの全体平均に対する変動率（％）を示す。 One of the Cu—Ga alloy target materials thus obtained was used for analysis, and 15 × 15 × 6 (mm) analysis samples were cut out from the respective measurement positions shown in FIG. Relative density, Ga content, and oxygen content were measured. Table 5 shows the relative density, the Ga content, the oxygen content and the average value in each part. Table 6 shows the rate of change (%) relative to the overall average of the relative density, Ga content, and oxygen content in each part.
また、実施例２のＣｕ−Ｇａ合金ターゲット材の平均結晶粒径を測定した。実施例２のＣｕ−Ｇａ合金ターゲット材では、図３に示す光学顕微鏡像で示すように平均粒径は、１００μｍであった。 Moreover, the average crystal grain size of the Cu—Ga alloy target material of Example 2 was measured. In the Cu—Ga alloy target material of Example 2, the average particle diameter was 100 μm as shown in the optical microscope image shown in FIG.
次に上記で製作したターゲット材のスパッタテストを実施した。スパッタはＡｒ圧力０．６Ｐａ、ＤＣ電力５００Ｗの条件で積算時間５時間実施した。実施例２でもアーキングが確認されなかった。また、スパッタ後のターゲット表面観察を行った、実施例２のＣｕ−Ｇａ合金ターゲット材でも目視ではノジュールが確認されなかった。 Next, a sputter test was performed on the target material produced above. Sputtering was performed under the conditions of an Ar pressure of 0.6 Pa and a DC power of 500 W for an integrated time of 5 hours. In Example 2, arcing was not confirmed. Further, no nodules were visually confirmed even in the Cu—Ga alloy target material of Example 2 in which the target surface was observed after sputtering.
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