JP2022022959A - Method of manufacturing copper cylinder type target for thin film coating using sputtering method through hot extrusion technique - Google Patents
Method of manufacturing copper cylinder type target for thin film coating using sputtering method through hot extrusion technique Download PDFInfo
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- 229910052802 copper Inorganic materials 0.000 title claims abstract description 126
- 239000010949 copper Substances 0.000 title claims abstract description 126
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 238000001192 hot extrusion Methods 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000010409 thin film Substances 0.000 title abstract description 27
- 238000004544 sputter deposition Methods 0.000 title abstract description 23
- 238000009501 film coating Methods 0.000 title abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 55
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000001125 extrusion Methods 0.000 claims abstract description 14
- 238000010622 cold drawing Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000012080 ambient air Substances 0.000 claims 1
- 239000012535 impurity Substances 0.000 claims 1
- 239000013077 target material Substances 0.000 abstract description 32
- 238000001816 cooling Methods 0.000 abstract description 5
- 238000005266 casting Methods 0.000 abstract description 4
- 238000007598 dipping method Methods 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 6
- 238000005477 sputtering target Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000002159 abnormal effect Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000001771 vacuum deposition Methods 0.000 description 4
- 238000001311 chemical methods and process Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000005482 strain hardening Methods 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000002547 anomalous effect Effects 0.000 description 1
- 239000005328 architectural glass Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005596 ionic collisions Effects 0.000 description 1
- 238000001182 laser chemical vapour deposition Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
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Abstract
Description
本発明は、冶金学の分野に関し、特に、スパッタリング法を使用した薄膜コーティングのための銅円筒型ターゲットの熱間押出技術からの製造の分野に関する。 The present invention relates to the field of metallurgy, in particular to the field of manufacture from hot extrusion techniques for copper cylindrical targets for thin film coating using sputtering.
現在、大部分の表面めっきは、電気めっきなどの化学技術を好む。しかし、かかる技術には、完成した表面の品質が低いことや環境問題など、いくつかの問題がある。そのため、真空コーティングなどの新たな表面めっき技術が開発されてきた。真空コーティング技術は真空中で実施され、環境問題を生じ得る化学物質を必要としない。更に、真空コーティング技術は、「薄膜」と呼ばれる非常に薄いコーティング表面を作製できる。通常、膜は、その厚さが５μｍ以下の場合に「薄膜」と呼ばれる。 Currently, most surface plating prefers chemical techniques such as electroplating. However, such technology has some problems such as poor quality of the finished surface and environmental problems. Therefore, new surface plating technologies such as vacuum coating have been developed. Vacuum coating technology is performed in vacuum and does not require chemicals that can cause environmental problems. In addition, vacuum coating techniques can produce very thin coated surfaces called "thin films". Usually, a film is called a "thin film" when its thickness is 5 μm or less.
薄膜真空コーティングプロセスは、化学的プロセスと物理的プロセスの２種類に分類できる。
１）薄膜コーティングの化学的プロセスは、気相中での化学物質の分解及びコーティングしようとする表面上での新たな種の形成を利用する。このプロセスの例は、プラズマＣＶＤ及びレーザーＣＶＤである。
２）薄膜コーティングの物理的プロセスは、コーティング材の表面からコーティング材の原子をエッチングすることを利用する。遊離コーティング原子は拡散し、コーティングしようとする材料の表面に結合する。このプロセスの例は、蒸発及びスパッタリングである。
Thin film vacuum coating processes can be classified into two types: chemical processes and physical processes.
1) The chemical process of thin film coating utilizes the decomposition of chemicals in the gas phase and the formation of new species on the surface to be coated. Examples of this process are plasma CVD and laser CVD.
2) The physical process of thin film coating utilizes etching of the atoms of the coating material from the surface of the coating material. Free coating atoms diffuse and bond to the surface of the material to be coated. Examples of this process are evaporation and sputtering.
スパッタリング技術は、研究及び薄膜製品開発に好適な薄膜コーティング技術である。この技術の利点は、金属、ガラス、合金、セラミックス及び半導体などのいくつかの薄膜材料に応用できること、薄膜の厚さを精密に制御できること、及び薄膜の特性を様々に変更できることである。産業界がスパッタリング技術を活用している例は、マイクロエレクトロニクス、半導体、導電性フィルム、保護フィルム、ハードディスクドライブ、自動車、建築用ガラスパネル、光ファイバー、太陽電池、テレビ画面、及びモバイルデバイス画面である。 Sputtering technology is a thin film coating technology suitable for research and thin film product development. The advantages of this technique are that it can be applied to several thin film materials such as metals, glass, alloys, ceramics and semiconductors, that the thickness of the thin film can be precisely controlled, and that the properties of the thin film can be varied. Examples of industry utilization of sputtering technology are microelectronics, semiconductors, conductive films, protective films, hard disk drives, automobiles, architectural glass panels, optical fibers, solar cells, television screens, and mobile device screens.
真空スパッタリング技術の原理は、コーティングチャンバ内に１×１０－６ｍｂａｒ以下の圧力の真空を作ることから始まる。その後、アルゴンなどの不活性ガスを、所定の圧力までチャンバ内に充填する。スパッタリングは、磁場を用いてアルゴン分子のイオンを生成することで始まり、生成したイオンを、電場を用いて方向づけしてコーティング材（又はターゲット材）の表面に衝突させることで、コーティング材の表面上の原子がコーティング材の表面から除去されて基材の表面へと移動する。次いで、コーティング材の原子は、図１～４に示すように、基材の表面上に付着して、基材の表面上に薄膜を生じる。 The principle of vacuum sputtering technology begins with creating a vacuum with a pressure of 1 x 10-6 mbar or less in the coating chamber. The chamber is then filled with an inert gas such as argon to a predetermined pressure. Sputtering begins by generating ions of argon molecules using a magnetic field, and the generated ions are directed using an electric field to collide with the surface of the coating material (or target material) on the surface of the coating material. Atoms are removed from the surface of the coating material and migrate to the surface of the substrate. Then, as shown in FIGS. 1 to 4, the atoms of the coating material adhere to the surface of the base material to form a thin film on the surface of the base material.
１９８５年のスパッタリング技術では、半導体特性を有する薄膜の場合、アルミニウムの抵抗は最も低くはなかったが、ターゲット材としてアルミニウムを使用することが好まれた。これは、当時のこの技術の限界によるものである。しかし、１９８０年代のＩＢＭの開発後は、高速、精密かつ十分に開発された技術により、ターゲット材として銅及び銀の使用が増えて現在に至る。これは、これらの金属は両方ともアルミニウムよりも電気抵抗が低く、電子移動抵抗性に優れるためである。得られる薄膜の品質は、チャンバ内圧力、ターゲット材表面のガスイオン衝突数、ガスの種類などのスパッタリング装置の操作条件にも依存することが知られている。更に、薄膜の品質は、ターゲット材の特性にも依存し、これは品質又はスパッタリング工程中の欠陥の生成に直接影響する。かかる特性は：
１）ターゲット材の純度
２）ターゲット材に含まれる酸化物（例えば、アルミニウムターゲットの場合Ａｌ２Ｏ３、銅ターゲットの場合ＣｕＯ）などの誘電体の量。
３）気孔率、例えば、スパッタリング工程中にガスから発生した空隙の量。
４）ターゲット材の結晶粒径
５）ターゲット材の表面粗さ
６）ターゲット材の機械的強度又は硬度
In the 1985 sputtering technique, the resistance of aluminum was not the lowest for thin films with semiconductor properties, but it was preferred to use aluminum as the target material. This is due to the limitations of this technology at the time. However, after the development of IBM in the 1980s, the use of copper and silver as target materials has increased due to high-speed, precise and well-developed technology. This is because both of these metals have lower electrical resistance than aluminum and have excellent electron transfer resistance. It is known that the quality of the obtained thin film also depends on the operating conditions of the sputtering apparatus such as the pressure in the chamber, the number of gas ion collisions on the surface of the target material, and the type of gas. In addition, the quality of the thin film also depends on the properties of the target material, which directly affects the quality or the generation of defects during the sputtering process. Such characteristics are:
1) Purity of the target material 2) Amount of dielectric such as oxides contained in the target material (for example, Al 2 O 3 for an aluminum target and Cu O for a copper target).
3) Porosity, eg, the amount of voids generated from the gas during the sputtering process.
4) Crystal grain size of the target material 5) Surface roughness of the target material 6) Mechanical strength or hardness of the target material
オリエンタルカッパー社（Ｏｒｉｅｎｔａｌ Ｃｏｐｐｅｒ Ｃｏ．，Ｌｔｄ）は、２０１７年９月２９日以降、特許「Ｍｅｔｈｏｄ ｆｏｒ ｍａｎｕｆａｃｔｕｒｉｎｇ ｃｏｐｐｅｒ ｃｙｌｉｎｄｒｉｃａｌ ｔａｒｇｅｔ ｆｒｏｍ ｈｏｔ ｅｘｔｒｕｓｉｏｎ ｔｅｃｈｎｉｑｕｅ ｆｏｒ ｔｈｉｎ ｆｉｌｍ ｃｏａｔｉｎｇ ｕｓｉｎｇ ｓｐｕｔｔｅｒｉｎｇ ｍｅｔｈｏｄ」をタイ国知的財産局に出願している。この出願は、平板状ターゲット材の形態のスパッタリングターゲットを開示している。しかし、現在、別のスパッタリングターゲットが薄膜コーティングに使用され始めている。かかるターゲットは円筒型の形状を有し、「円筒型ターゲット材」と呼ばれる。円筒型ターゲット材の価格は平板状ターゲット材よりも高いが、円筒型ターゲット材は、材料利用率が高い（すなわち、ターゲット材１つ当たり約８０％であるが、平板状ターゲット材はわずか３５％）という利点を有する。更に円筒型ターゲット材の単位重量当たりの価格も、平板状ターゲット材より低い。表１は、クロム製の平板状ターゲット材と円筒型ターゲット材の比較を示す。上記の理由により、発明者らは、スパッタリング技術を使用した薄膜コーティングに好適な円筒型材料を作製するための研究をより多く行ってきた。 Oriental Copper Co., Ltd. (Oriental Copper Co., Ltd.) has been working on the patent "Manufacturing copper cylindrical corpper cylindrical cult is doing. This application discloses a sputtering target in the form of a flat plate target material. However, other sputtering targets are now beginning to be used for thin film coatings. Such a target has a cylindrical shape and is called a "cylindrical target material". The price of the cylindrical target material is higher than that of the flat plate target material, but the cylindrical target material has a high material utilization rate (that is, about 80% per target material, but the flat plate target material is only 35%. ). Furthermore, the price per unit weight of the cylindrical target material is also lower than that of the flat plate target material. Table 1 shows a comparison between a flat plate target material made of chrome and a cylindrical target material. For the above reasons, the inventors have conducted more research to produce cylindrical materials suitable for thin film coatings using sputtering techniques.
Ｃｒ平板状ターゲット材と円筒型ターゲット材の比較 Comparison of Cr flat plate target material and cylindrical target material
過去には、銅円筒型ターゲットの特性を研究し、要求を満たすように銅円筒型ターゲットの特性に影響する、又は特性を制御できる製造方法及び条件を見出そうとした研究が数件ある。 In the past, there have been several studies that have studied the properties of copper cylindrical targets and have sought to find manufacturing methods and conditions that affect or control the properties of copper cylindrical targets to meet their requirements.
例えば、特許文献１（古河電気工業株式会社）は、無酸素（ＯＦ）銅から製造した円筒状スパッタリングターゲット材を開示している。その製造工程は、以下のステップを有する：無酸素銅（Ｃｕ＝９９．９９５％）→熱間加工（圧延／押出工程）→焼鈍（温度＝７４０～８１０℃）→引抜（冷間加工％＝９．７～１７．０％）。得られたターゲット材の結晶粒径は、９０～１４０μｍの範囲であった。この特許は、１４０μｍ未満の結晶粒径は、過度のスパッタリングを起こさず、スパッタリングされた原子がより均一な拡散方向を有すると主張している。 For example, Patent Document 1 (Furukawa Electric Co., Ltd.) discloses a cylindrical sputtering target material manufactured from oxygen-free (OF) copper. The manufacturing process has the following steps: oxygen-free copper (Cu = 99.995%) → hot working (rolling / extrusion process) → annealing (temperature = 740 to 810 ° C) → drawing (cold working% =) 9.7 to 17.0%). The crystal grain size of the obtained target material was in the range of 90 to 140 μm. The patent claims that a crystal grain size of less than 140 μm does not cause excessive sputtering and that the sputtered atoms have a more uniform diffusion direction.
特許文献２（日立電線株式会社）及び特許文献３（株式会社ＳＨカッパープロダクツ）は、無酸素銅から製造した外径１６５ｍｍ、肉厚２５ｍｍの円筒型スパッタリングターゲット材の製造方法を開示している。この製造方法は、以下のステップを有する：無酸素銅（Ｃｕ＝９９．９又は９９．９９％）→熱間押出→拡管引抜→熱処理。いずれの研究も、拡管率を１０％に保ちながら熱処理温度を４００～６５０℃で変えること、及び熱処理温度を４００℃に保ちながら拡管率を３～２０％で変えることによって、熱処理温度及び拡管率の影響を研究した。その結果、低い熱処理温度（４００℃）はターゲット材の割れを引き起こし、高い熱処理温度（６００℃）は、銅の結晶粒が広く異なる粒径を有する原因となることが見出された。低い拡管率（３％）は、銅の結晶粒が広く異なる粒径を有する原因となるが、高い拡管率（２０％）はターゲット材の割れを引き起こす。したがって、両研究から、次の最適条件が画定された：熱処理温度＝４５０～６００℃で１８０分、及び拡管率５～１５％。得られた銅結晶粒径は５０～１００μｍで、ターゲット材に割れがなかった。更に、両研究から、１００μｍ未満の銅結晶粒径はスパッタリング工程中の異常放電の数が少ないという別の利点を有することも主張された。 Patent Document 2 (Hitachi Electric Wire Co., Ltd.) and Patent Document 3 (SH Copper Products Co., Ltd.) disclose a method for manufacturing a cylindrical sputtering target material having an outer diameter of 165 mm and a wall thickness of 25 mm, which is manufactured from oxygen-free copper. This manufacturing method has the following steps: oxygen-free copper (Cu = 99.9 or 99.99%) → hot extrusion → tube expansion drawing → heat treatment. In both studies, the heat treatment temperature and the tube expansion rate were changed by changing the heat treatment temperature at 400 to 650 ° C while keeping the tube expansion rate at 10%, and by changing the tube expansion rate at 3 to 20% while keeping the heat treatment temperature at 400 ° C. The effect of was studied. As a result, it was found that a low heat treatment temperature (400 ° C.) causes cracking of the target material, and a high heat treatment temperature (600 ° C.) causes the copper crystal grains to have widely different particle sizes. A low tube expansion rate (3%) causes copper grains to have widely different grain sizes, while a high tube expansion rate (20%) causes cracking of the target material. Therefore, from both studies, the following optimal conditions were defined: heat treatment temperature = 450-600 ° C. for 180 minutes, and tube expansion rate 5-15%. The obtained copper crystal grain size was 50 to 100 μm, and the target material was not cracked. Furthermore, both studies have also argued that copper crystal grain sizes less than 100 μm have the additional advantage of having a smaller number of anomalous discharges during the sputtering process.
特許文献４（三菱マテリアル株式会社）及び特許文献５（三菱マテリアル株式会社）は、外径１４０～１８０ｍｍ、内径１１０～１３５ｍｍ、長さ１，０００～４，０００ｍｍを有する円筒型スパッタリングターゲットの製造方法を開示している。この製造方法は以下のステップを有する：無酸素銅（連続鋳造工程からの円筒状鋳塊は、銅結晶粒径が２０ｍｍ以下である）→拡管引抜→熱処理（温度＝４００～９００℃、１５～１２０分）。拡管引抜ステップは、銅の結晶粒径を均一に分布させるために繰り返され得る。外径は０％～３０％拡がり、断面積は－１０％～＋１０％の範囲内で変化した。銅又は銅合金を出発材料として使用した場合、外表面周辺領域における銅の結晶粒径は、１０～１５０μｍの範囲であった。外表面領域における無酸素銅の銅結晶粒径は、１０５及び１４６μｍであった。平均粒径の２倍の粒径を有する結晶粒が占める面積割合が総面積の２５％未満の場合、スパッタリング工程中の異常放電の数が低減された。 Patent Document 4 (Mitsubishi Materials Corporation) and Patent Document 5 (Mitsubishi Materials Corporation) are methods for manufacturing a cylindrical sputtering target having an outer diameter of 140 to 180 mm, an inner diameter of 110 to 135 mm, and a length of 1,000 to 4,000 mm. Is disclosed. This manufacturing method has the following steps: oxygen-free copper (cylindrical ingots from continuous casting steps have a copper crystal grain size of 20 mm or less) → tube expansion drawing → heat treatment (temperature = 400-900 ° C, 15- 120 minutes). The expansion tube extraction step can be repeated to evenly distribute the crystal grain size of copper. The outer diameter expanded by 0% to 30%, and the cross-sectional area varied within the range of -10% to + 10%. When copper or a copper alloy was used as the starting material, the crystal grain size of copper in the outer surface peripheral region was in the range of 10 to 150 μm. The copper crystal grain size of oxygen-free copper in the outer surface region was 105 and 146 μm. When the area ratio occupied by the crystal grains having a particle size twice the average particle size was less than 25% of the total area, the number of abnormal discharges during the sputtering process was reduced.
特許文献６（三菱マテリアル株式会社）及び特許文献７（三菱マテリアル株式会社）は、外径１４０～１８０ｍｍ、内径１１０～１３５ｍｍ、長さ１，０００～４，０００ｍｍを有する円筒型スパッタリングターゲット材の製造方法を開示している。この製造方法は以下のステップを有する：無酸素銅（異常放電を防止するため、（Ｓｉ＋Ｃ）元素の量が１０ｐｐｍ未満の円柱状鋳塊）→熱間加工（圧延／押出加工により結晶粒径２０ｍｍ以下の銅を製造）→拡管引抜→熱処理（温度＝４００～９００℃、１５～１２０分）。拡管引抜ステップは、銅の結晶粒径を均一に分布させるために繰り返され得る。肉厚は１５％～２５％大きくなり、外径は０％～３０％拡がり、内径は０～２０％拡がった。銅又は銅合金を出発材料として使用した場合、外表面周辺領域における銅の結晶粒径は、１０～１５０μｍの範囲であった。外表面領域における無酸素銅の銅結晶粒径は、５９、８４及び１０３μｍであった。平均粒径の２倍の粒径を有する結晶粒が占める割合が総面積の２０％未満の場合、スパッタリング工程中の異常放電の数が低減された。 Patent Document 6 (Mitsubishi Materials Corporation) and Patent Document 7 (Mitsubishi Materials Corporation) manufacture cylindrical sputtering target materials having an outer diameter of 140 to 180 mm, an inner diameter of 110 to 135 mm, and a length of 1,000 to 4,000 mm. The method is disclosed. This manufacturing method has the following steps: oxygen-free copper (cylindrical ingot with (Si + C) element content less than 10 ppm to prevent abnormal discharge) → hot working (rolling / extrusion to crystal grain size 20 mm) Manufacture the following copper) → Rolling out tube → Heat treatment (temperature = 400-900 ° C, 15-120 minutes). The expansion tube extraction step can be repeated to evenly distribute the crystal grain size of copper. The wall thickness increased by 15% to 25%, the outer diameter increased by 0% to 30%, and the inner diameter increased by 0 to 20%. When copper or a copper alloy was used as the starting material, the crystal grain size of copper in the outer surface peripheral region was in the range of 10 to 150 μm. The copper crystal grain size of oxygen-free copper in the outer surface region was 59, 84 and 103 μm. When the proportion of crystal grains having a particle size twice the average particle size was less than 20% of the total area, the number of abnormal discharges during the sputtering process was reduced.
従先行技術調査から、銅円筒型ターゲット形成のための製造方法は、表２に示すように大部分が鋳造（Ｃｕ－ＯＦ）→熱間加工（圧延／押出）→冷間加工（引抜）→熱処理の工程を含むことがわかった。高品質のコーティング又は薄膜を高品質のターゲット材から作製するためには、スパッタリング工程中の異常放電の問題を低減するために、銅結晶粒の粒径が均一かつ１５０μｍ未満であることが必要である。しかし、従来技術は、常に、用途に適するように銅の微細構造を変えるための熱処理ステップを含んでいた。本発明は、鋳造（Ｃｕ－ＯＦ）→熱間加工（押出）→冷間加工（引抜）のステップにより、熱処理を必要とすることなく、スパッタリング法による薄膜コーティング塗布に適した微細構造を維持しながら銅円筒型ターゲットを作製することを目的とし、更には製造コストを削減する。 From the prior art search, most of the manufacturing methods for forming copper cylindrical targets are casting (Cu-OF) → hot working (rolling / extrusion) → cold working (drawing) → It was found to include a heat treatment step. In order to produce a high quality coating or thin film from a high quality target material, the grain size of the copper crystal grains must be uniform and less than 150 μm in order to reduce the problem of abnormal discharge during the sputtering process. be. However, prior art has always included a heat treatment step to alter the copper microstructure to suit the application. The present invention maintains a microstructure suitable for thin film coating application by the sputtering method without the need for heat treatment by the steps of casting (Cu-OF) → hot working (extrusion) → cold working (pulling). However, the purpose is to produce a copper cylindrical target, and further reduce the manufacturing cost.
過去の研究の円筒型ターゲットの銅結晶粒径 Copper crystal grain size of cylindrical targets in past studies
したがって、本発明者であるオリエンタルカッパー社のＶａｃｈａｋａｒｎ Ｔｅｃｈａｃｈｕｎｈａｋｉｔは、熱間押出技術を使用して、熱処理ステップを必要とすることなく、銅結晶粒径の均一性を維持するとともに、粒径をスパッタリング法による薄膜コーティング塗布に適した５０～１５０μｍの範囲としながら銅円筒型ターゲットを作製するための製造方法を開発した。 Therefore, the inventor, Vachakarn Techachunhakit of Oriental Copper Co., Ltd., uses a hot extrusion technique to maintain the uniformity of the copper crystal grain size and to sputter the grain size without the need for a heat treatment step. We have developed a manufacturing method for producing a copper cylindrical target with a range of 50 to 150 μm suitable for applying a thin film coating.
文献調査から、高品質の薄膜は、均一な結晶粒径を有する１５０μｍ未満のターゲットに依拠すると結論づけることができる。したがって、本発明の目的は、スパッタリング法による薄膜コーティング塗布のための銅円筒型ターゲットを、高品質の薄膜を製造するために銅結晶粒径を５０～１５０μｍの範囲に制御できる熱間押出から製造することである。調査した銅結晶粒の粒径及び均一性に影響を有する熱間押出工程のパラメータは：
１）熱間押出工程の前の鋳塊温度
２）押出速度（メインラム速度）
である。
From literature research, it can be concluded that high quality thin films rely on targets with uniform grain sizes of less than 150 μm. Therefore, an object of the present invention is to manufacture a copper cylindrical target for coating a thin film coating by a sputtering method from hot extrusion in which the copper crystal grain size can be controlled in the range of 50 to 150 μm in order to produce a high quality thin film. It is to be. The parameters of the hot extrusion process that affect the grain size and uniformity of the copper grains investigated are:
1) Ingot temperature before hot extrusion process 2) Extrusion speed (main ram speed)
Is.
熱間押出工程中の押出ダイ後方の銅の急速な冷却速度は、図５に示すように、押出した銅を直ちに水に通すこと（又は水中押出）によって達成される。これは、銅の結晶粒成長を防止するための重要な技術である。水の温度は４０℃を超えるべきではない。その後直ちに、図６の示すように、銅バーを冷間引抜工程に供して、５１～１００ビッカース硬さの範囲の硬度を有する銅ターゲットを作製する。 The rapid cooling rate of copper behind the extrusion die during the hot extrusion process is achieved by immediately passing the extruded copper through water (or underwater extrusion), as shown in FIG. This is an important technique for preventing the growth of copper grains. The temperature of the water should not exceed 40 ° C. Immediately thereafter, as shown in FIG. 6, the copper bar is subjected to a cold drawing step to produce a copper target having a hardness in the range of 51-100 Vickers hardness.
本発明の銅円筒型ターゲットを作製するための製造方法は、銅鋳塊（Ｃｕ純度９９．９９％以上及び酸素５ｐｐｍ未満）を鋳造して直径１２インチのロッドを形成するステップ、その後得られた銅ロッドを熱間押出（これは銅結晶粒の粒径及び均一性の制御において重要である）のステップを含む。調査するパラメータは：
１）熱間押出工程の前の鋳塊温度（８００、８５０、及び９００℃）
２）ダイを通した銅ロッドの押出に使用した油圧シリンダーの速度から測定した押出速度（５、１０、及び２０ｍｍ／秒）
である。
The manufacturing method for producing the copper cylindrical target of the present invention was obtained by casting a copper ingot (Cu purity of 99.99% or more and oxygen of less than 5 ppm) to form a rod having a diameter of 12 inches. The step of hot extrusion of the copper rod (which is important in controlling the particle size and uniformity of the copper crystal grains) is included. The parameters to investigate are:
1) Ingot temperature (800, 850, and 900 ° C.) before the hot extrusion process.
2) Extrusion speed (5, 10, and 20 mm / sec) measured from the speed of the hydraulic cylinder used to extrude the copper rod through the die.
Is.
制御されるパラメータは、銅の冷却速度である。通常、銅が熱間押出工程で処理された後、「動的再結晶」と呼ばれる現象から、銅結晶粒径が小さくなる。しかし、冷却速度を制御することなく、銅バーを周囲雰囲気中で自然冷却した場合、銅結晶粒径をより大きくし、結晶粒径の不均一性を生じる「結晶粒成長」と呼ばれる次のステップへと再結晶化が継続又は発展するには、わずか１０秒の時間で十分である。 The parameter to be controlled is the cooling rate of copper. Usually, after copper is processed in a hot extrusion process, the copper grain size becomes smaller due to a phenomenon called "dynamic recrystallization". However, when the copper bar is naturally cooled in the ambient atmosphere without controlling the cooling rate, the next step called "grain growth" is to increase the grain size of the copper and cause non-uniformity of the grain size. Only 10 seconds is sufficient for the recrystallization to continue or develop.
したがって、本発明は、銅バーの冷却速度を、４０℃以下の温度の冷却水を用いて制御する。押し出した銅ロッドを直ちに、ダイ後方に配置された冷却水浴に１０秒以内に浸漬して、銅の結晶粒成長を防止する。 Therefore, in the present invention, the cooling rate of the copper bar is controlled by using cooling water having a temperature of 40 ° C. or lower. Immediately immerse the extruded copper rod in a cooling water bath located behind the die within 10 seconds to prevent copper grain growth.
熱間押出ステップの後、銅ロッドを冷間引抜ステップに供して、決められた外径及び内径を有し、使用前の表面硬度が１００ビッカース硬さを超えない銅ターゲットを作製する。この研究の詳細を以下に示す。 After the hot extrusion step, the copper rod is subjected to a cold drawing step to produce a copper target having a determined outer diameter and inner diameter and having a surface hardness of no more than 100 Vickers hardness before use. Details of this study are shown below.
直径１２インチ、長さ５５０ｍｍの銅鋳塊を８００、８５０又は９００℃に加熱する。次いで、鋳塊を押出ダイに通して押出して、外径１５５ｍｍ、内径１００ｍｍを有する銅ロッドを形成する。高温の銅ロッドを、直ちに、ダイの後方に配置した水浴に浸漬する。押出速度を、表３に示すように、５、１０又は２０ｍｍ／秒に設定する。 A copper ingot 12 inches in diameter and 550 mm in length is heated to 800, 850 or 900 ° C. The ingot is then extruded through an extrusion die to form a copper rod with an outer diameter of 155 mm and an inner diameter of 100 mm. Immediately immerse the hot copper rod in a water bath located behind the die. The extrusion rate is set to 5, 10 or 20 mm / sec as shown in Table 3.
銅ロッドの温度及び押出速度 Copper rod temperature and extrusion speed
次いで、冷却した銅ロッドを、引抜ダイを使用した冷間引抜工程に供し、外径及び内径がそれぞれ１５０ｍｍ及び９５ｍｍの銅ロッドを作製する。冷間引抜工程から得られた銅ロッドを、図７に示すように、頭部、中央部、及び尾部で試験する。 Next, the cooled copper rod is subjected to a cold drawing step using a drawing die to prepare copper rods having an outer diameter and an inner diameter of 150 mm and 95 mm, respectively. Copper rods obtained from the cold drawing step are tested at the head, center and tail as shown in FIG.
銅結晶粒径の試験は、内径から外径まで測定した半径方向に５箇所の同じ位置で実施した。図８に示すように、位置１は、内表面に近い位置であり、位置２、３、４及び５はそれぞれ内表面から離れている。位置５は外表面に最も近い。 The copper crystal grain size test was carried out at five same positions in the radial direction measured from the inner diameter to the outer diameter. As shown in FIG. 8, position 1 is a position close to the inner surface, and positions 2, 3, 4 and 5 are separated from the inner surface, respectively. Position 5 is closest to the outer surface.
異なる押出条件を使用して得られた銅結晶粒径の試験を、表４～３０に報告し、表３１にまとめる。 Tests of copper crystal grain size obtained using different extrusion conditions are reported in Tables 4-30 and summarized in Table 31.
銅の結晶粒径、温度８００℃、熱間押出速度５ｍｍ／秒、頭部 Copper crystal grain size, temperature 800 ° C, hot extrusion speed 5 mm / sec, head
銅の結晶粒径、温度８００℃、熱間押出速度５ｍｍ／秒、中央部 Copper crystal grain size, temperature 800 ° C, hot extrusion speed 5 mm / sec, central part
銅の結晶粒径、温度８００℃、熱間押出速度５ｍｍ／秒、尾部 Copper crystal grain size, temperature 800 ° C, hot extrusion speed 5 mm / sec, tail
銅の結晶粒径、温度８００℃、熱間押出速度１０ｍｍ／秒、頭部 Copper crystal grain size, temperature 800 ° C, hot extrusion speed 10 mm / sec, head
銅の結晶粒径、温度８００℃、熱間押出速度１０ｍｍ／秒、中央部 Copper crystal grain size, temperature 800 ° C, hot extrusion speed 10 mm / sec, central part
銅の結晶粒径、温度８００℃、熱間押出速度１０ｍｍ／秒、尾部 Copper crystal grain size, temperature 800 ° C, hot extrusion speed 10 mm / sec, tail
銅の結晶粒径、温度８００℃、熱間押出速度２０ｍｍ／秒、頭部 Copper crystal grain size, temperature 800 ° C, hot extrusion speed 20 mm / sec, head
銅の結晶粒径、温度８００℃、熱間押出速度２０ｍｍ／秒、中央部 Copper crystal grain size, temperature 800 ° C, hot extrusion speed 20 mm / sec, central part
銅の結晶粒径、温度８００℃、熱間押出速度２０ｍｍ／秒、尾部 Copper crystal grain size, temperature 800 ° C, hot extrusion speed 20 mm / sec, tail
銅の結晶粒径、温度８５０℃、熱間押出速度５ｍｍ／秒、頭部 Copper crystal grain size, temperature 850 ° C, hot extrusion speed 5 mm / sec, head
銅の結晶粒径、温度８５０℃、熱間押出速度５ｍｍ／秒、中央部 Copper crystal grain size, temperature 850 ° C, hot extrusion speed 5 mm / sec, central part
銅の結晶粒径、温度８５０℃、熱間押出速度５ｍｍ／秒、尾部 Copper crystal grain size, temperature 850 ° C, hot extrusion speed 5 mm / sec, tail
銅の結晶粒径、温度８５０℃、熱間押出速度１０ｍｍ／秒、頭部 Copper crystal grain size, temperature 850 ° C, hot extrusion speed 10 mm / sec, head
銅の結晶粒径、温度８５０℃、熱間押出速度１０ｍｍ／秒、中央部 Copper crystal grain size, temperature 850 ° C, hot extrusion speed 10 mm / sec, central part
銅の結晶粒径、温度８５０℃、熱間押出速度１０ｍｍ／秒、尾部 Copper crystal grain size, temperature 850 ° C, hot extrusion speed 10 mm / sec, tail
銅の結晶粒径、温度８５０℃、熱間押出速度２０ｍｍ／秒、頭部 Copper crystal grain size, temperature 850 ° C, hot extrusion speed 20 mm / sec, head
銅の結晶粒径、温度８５０℃、熱間押出速度２０ｍｍ／秒、中央部 Copper crystal grain size, temperature 850 ° C, hot extrusion speed 20 mm / sec, central part
銅の結晶粒径、温度８５０℃、熱間押出速度２０ｍｍ／秒、尾部 Copper crystal grain size, temperature 850 ° C, hot extrusion speed 20 mm / sec, tail
銅の結晶粒径、温度９００℃、熱間押出速度５ｍｍ／秒、頭部 Copper crystal grain size, temperature 900 ° C, hot extrusion speed 5 mm / sec, head
銅の結晶粒径、温度９００℃、熱間押出速度５ｍｍ／秒、中央部 Copper crystal grain size, temperature 900 ° C, hot extrusion speed 5 mm / sec, central part
銅の結晶粒径、温度９００℃、熱間押出速度５ｍｍ／秒、尾部 Copper crystal grain size, temperature 900 ° C, hot extrusion speed 5 mm / sec, tail
銅の結晶粒径、温度９００℃、熱間押出速度１０ｍｍ／秒、頭部 Copper crystal grain size, temperature 900 ° C, hot extrusion speed 10 mm / sec, head
銅の結晶粒径、温度９００℃、熱間押出速度１０ｍｍ／秒、中央部 Copper crystal grain size, temperature 900 ° C, hot extrusion speed 10 mm / sec, central part
銅の結晶粒径、温度９００℃、熱間押出速度１０ｍｍ／秒、尾部 Copper crystal grain size, temperature 900 ° C, hot extrusion speed 10 mm / sec, tail
銅の結晶粒径、温度９００℃、熱間押出速度２０ｍｍ／秒、頭部 Copper crystal grain size, temperature 900 ° C, hot extrusion speed 20 mm / sec, head
銅の結晶粒径、温度９００℃、熱間押出速度２０ｍｍ／秒、中央部 Copper crystal grain size, temperature 900 ° C, hot extrusion speed 20 mm / sec, central part
銅の結晶粒径、温度９００℃、熱間押出速度２０ｍｍ／秒、尾部 Copper crystal grain size, temperature 900 ° C, hot extrusion speed 20 mm / sec, tail
銅円筒型ターゲットの結晶粒径 Crystal grain size of copper cylindrical target
本発明の最良の方法
「発明を実施するための形態」に詳細に記載したとおりである。
The best method of the present invention is as described in detail in "Modes for Carrying Out the Invention".
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| JP2012111994A (en) * | 2010-11-24 | 2012-06-14 | Furukawa Electric Co Ltd:The | Cylindrical target material, its manufacturing method and its sheet coating method |
| JP2013057112A (en) * | 2011-09-09 | 2013-03-28 | Hitachi Cable Ltd | Cylindrical sputtering target material, and wiring board and thin film transistor using the same |
| JP2016156097A (en) * | 2016-05-25 | 2016-09-01 | 古河電気工業株式会社 | Sputtering target |
| JP2017137558A (en) * | 2016-02-05 | 2017-08-10 | 住友化学株式会社 | Production method of cylindrical target |
| JP2018059171A (en) * | 2016-10-07 | 2018-04-12 | 三菱マテリアル株式会社 | Hot extrusion material for cylindrical sputtering target and manufacturing method of cylindrical sputtering target |
| JP2018135573A (en) * | 2017-02-23 | 2018-08-30 | 株式会社Ｕａｃｊ銅管 | Cylindrical sputtering target material and method for manufacturing the same |
| JP2020105563A (en) * | 2018-12-27 | 2020-07-09 | 三菱マテリアル株式会社 | Copper stock for sputtering target |
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| WO2011024909A1 (en) * | 2009-08-28 | 2011-03-03 | 古河電気工業株式会社 | Copper material for use in a sputtering target, and manufacturing method therefor |
| KR101515341B1 (en) * | 2009-09-18 | 2015-04-24 | 후루카와 덴키 고교 가부시키가이샤 | Method for producing copper material for use as sputtering target |
| CN103510055B (en) * | 2012-06-27 | 2015-10-21 | 宁波江丰电子材料股份有限公司 | The preparation method of high-purity copper target material |
| JP5783293B1 (en) * | 2014-04-22 | 2015-09-24 | 三菱マテリアル株式会社 | Material for cylindrical sputtering target |
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| JP2012111994A (en) * | 2010-11-24 | 2012-06-14 | Furukawa Electric Co Ltd:The | Cylindrical target material, its manufacturing method and its sheet coating method |
| JP2013057112A (en) * | 2011-09-09 | 2013-03-28 | Hitachi Cable Ltd | Cylindrical sputtering target material, and wiring board and thin film transistor using the same |
| JP2017137558A (en) * | 2016-02-05 | 2017-08-10 | 住友化学株式会社 | Production method of cylindrical target |
| JP2016156097A (en) * | 2016-05-25 | 2016-09-01 | 古河電気工業株式会社 | Sputtering target |
| JP2018059171A (en) * | 2016-10-07 | 2018-04-12 | 三菱マテリアル株式会社 | Hot extrusion material for cylindrical sputtering target and manufacturing method of cylindrical sputtering target |
| JP2018135573A (en) * | 2017-02-23 | 2018-08-30 | 株式会社Ｕａｃｊ銅管 | Cylindrical sputtering target material and method for manufacturing the same |
| JP2020105563A (en) * | 2018-12-27 | 2020-07-09 | 三菱マテリアル株式会社 | Copper stock for sputtering target |
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| TWI778503B (en) | 2022-09-21 |
| CN113846297A (en) | 2021-12-28 |
| TW202200799A (en) | 2022-01-01 |
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