JP2005000911A - Method for cleaning ceramic member - Google Patents
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- JP2005000911A JP2005000911A JP2004150123A JP2004150123A JP2005000911A JP 2005000911 A JP2005000911 A JP 2005000911A JP 2004150123 A JP2004150123 A JP 2004150123A JP 2004150123 A JP2004150123 A JP 2004150123A JP 2005000911 A JP2005000911 A JP 2005000911A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 97
- 238000004140 cleaning Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 70
- 230000002378 acidificating effect Effects 0.000 claims abstract description 27
- 238000011282 treatment Methods 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 abstract description 12
- 239000000243 solution Substances 0.000 description 37
- 238000004519 manufacturing process Methods 0.000 description 16
- 239000007795 chemical reaction product Substances 0.000 description 13
- 210000002381 plasma Anatomy 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000010980 sapphire Substances 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000008155 medical solution Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- CUPFNGOKRMWUOO-UHFFFAOYSA-N hydron;difluoride Chemical compound F.F CUPFNGOKRMWUOO-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Landscapes
- Cleaning By Liquid Or Steam (AREA)
- Detergent Compositions (AREA)
Abstract
Description
本発明は、セラミックス部材の洗浄方法に関する。 The present invention relates to a method for cleaning a ceramic member.
セラミックス部材は、製造工程の最終段階においてダイヤモンド工具等で加工されるのが一般的である。その際、セラミックス部材に加工屑やダイヤモンド砥粒等が付着してしまい、これらがセラミックス部材の使用時に種々の悪影響を及ぼすおそれがある。特に、半導体製造プロセスや液晶表示装置製造プロセスでセラミックス部材が使用される場合、セラミックス部材の付着物がパーティクルとして半導体ウエハや液晶基板に再付着すると欠陥の原因になるために、セラミックス部材からこのような付着物を予め完全に除去しておく必要がある。 The ceramic member is generally processed with a diamond tool or the like at the final stage of the manufacturing process. At that time, processing scraps, diamond abrasive grains, and the like adhere to the ceramic member, which may cause various adverse effects when the ceramic member is used. In particular, when a ceramic member is used in a semiconductor manufacturing process or a liquid crystal display device manufacturing process, if the deposit on the ceramic member reattaches to a semiconductor wafer or a liquid crystal substrate as particles, it causes a defect. It is necessary to completely remove the extraneous matter.
一方、半導体製造プロセスや液晶表示装置製造プロセスにおいては、近時、腐食性の高いフッ素系や塩素系のガスまたはプラズマを用いる工程が必須となっており、特に半導体製造プロセスにおいては、化学気相成長（ＣＶＤ）やドライエッチング、チャンバーのクリーニング等の工程にこれら腐食性ガスやプラズマが多用されている。そのため、このような工程で腐食性ガス雰囲気やプラズマ雰囲気に曝される部材には、腐食性ガスやプラズマに対する高い耐食性が要求されており、例えば最近では、アルミナ焼結体やサファイア、あるいは窒化アルミニウム焼結体などのセラミック材料が用いられている。 On the other hand, in the semiconductor manufacturing process and the liquid crystal display device manufacturing process, recently, a process using highly corrosive fluorine-based or chlorine-based gas or plasma is essential. These corrosive gases and plasmas are frequently used in processes such as growth (CVD), dry etching, and chamber cleaning. Therefore, a member exposed to a corrosive gas atmosphere or a plasma atmosphere in such a process is required to have high corrosion resistance against a corrosive gas or plasma. For example, recently, an alumina sintered body, sapphire, or aluminum nitride is required. Ceramic materials such as sintered bodies are used.
しかし、このようなセラミックス部材を上述した用途に使用した場合であっても、腐食性ガスやプラズマとセラミックス部材との間で化学反応が生じ、その反応生成物がセラミックス部材の表面を汚染する。この反応生成物はセラミックス部材の表面にパーティクルとして存在し、またはセラミックス部材の表面に直接に形成される。このような反応生成物は、プラズマの状態を不安定としたり、製造されている半導体装置等を汚染する原因となるために、適宜、このような反応生成物を除去することが必要である。 However, even when such a ceramic member is used in the above-described application, a chemical reaction occurs between the corrosive gas or plasma and the ceramic member, and the reaction product contaminates the surface of the ceramic member. This reaction product exists as particles on the surface of the ceramic member or is directly formed on the surface of the ceramic member. Such a reaction product may cause the plasma state to become unstable or cause contamination of a semiconductor device or the like that is manufactured. Therefore, it is necessary to appropriately remove such a reaction product.
前者のセラミックス部材の製造段階でセラミックス部材に付着した付着物を除去する方法としては、薬液を用いてこの付着物を溶解洗浄して除去する化学的な方法が用いられている。また、後者の装置製造プロセス中にセラミックス部材を汚染する反応生成物を除去する方法としては、セラミックス部材の表面を研削して物理的に除去する方法や、薬液を用いて反応生成物を溶解、洗浄して除去する化学的な方法が用いられている。このうち、付着物や反応生成物（以下「付着物等」という）の化学的な除去方法としては、付着物等で汚染されたセラミックス部材をアルカリ性薬液ならびに酸性薬液で処理し、その後さらに所定の熱処理を施す方法が知られている（例えば、特許文献１参照）。
しかしながら、近時、例えば半導体装置等ではその回路パターンの微細化や高集積化が急速に進んでいるために、従来は付着物等の残存量が製造される製品に悪影響を及ぼさないレベルにまで達していたセラミックス部材であっても、このような最新の半導体装置等の製造プロセスで使用した場合には、セラミックス部材の付着物等が原因となって、製造される製品の歩留まりが低下する等の障害が起こるようになってきている。このために、セラミックス部材の付着物等を高精度に除去して、その残存量をさらに低減することができる洗浄方法が求められている。 However, recently, for example, in semiconductor devices and the like, circuit patterns have been rapidly miniaturized and highly integrated, so that the remaining amount of deposits and the like has hitherto been reduced to a level that does not adversely affect the manufactured products. Even if the ceramic member has reached it, when used in the manufacturing process of such a latest semiconductor device, etc., the yield of manufactured products decreases due to the deposits of the ceramic member, etc. The obstacles are starting to happen. For this reason, there is a need for a cleaning method that can remove deposits and the like on ceramic members with high accuracy and further reduce the residual amount.
本発明はかかる事情に鑑みてなされたものであり、付着物等によって汚染されたセラミックス部材からその付着物等を高精度に除去することができるセラミックス部材の洗浄方法を提供することを目的とする。 This invention is made | formed in view of this situation, and it aims at providing the washing | cleaning method of the ceramic member which can remove the deposit | attachment etc. from the ceramic member contaminated by the deposit | attachment etc. with high precision. .
本発明によれば、表面が汚染されたセラミックス部材の洗浄方法であって、
前記セラミックス部材を超音波の存在下においてｐＨが１０以上のアルカリ性薬液で処理する工程と、
前記アルカリ性薬液処理で処理されたセラミックス部材を超音波の存在下において所定の酸性薬液で処理する工程と、
前記酸性薬液で処理されたセラミックス部材を１０００℃以上で加熱処理する工程と、
を有することを特徴とするセラミックス部材の洗浄方法、が提供される。
According to the present invention, a method for cleaning a ceramic member having a contaminated surface,
Treating the ceramic member with an alkaline chemical having a pH of 10 or higher in the presence of ultrasonic waves;
Treating the ceramic member treated with the alkaline chemical treatment with a predetermined acidic chemical in the presence of ultrasonic waves;
Heat-treating the ceramic member treated with the acidic chemical solution at 1000 ° C. or higher;
There is provided a method for cleaning a ceramic member, comprising:
このようなセラミックス部材の洗浄方法においては、アルカリ性薬液として、アルカリ金属と、有機酸と、グリコール系溶剤と、界面活性剤と、純水と、を含む薬液が好適に用いられる。また、セラミックス部材をアルカリ性薬液で処理した後、酸性薬液で処理する前にセラミックス部材を純水で洗浄することが好ましい。 In such a method for cleaning a ceramic member, a chemical solution containing an alkali metal, an organic acid, a glycol solvent, a surfactant, and pure water is preferably used as the alkaline chemical solution. Moreover, it is preferable to wash the ceramic member with pure water after treating the ceramic member with the alkaline chemical solution and before treating with the acidic chemical solution.
本発明によれば、セラミックス部材の製造工程でセラミックス部材に付着した付着物や、セラミックス部材を実際に所定の環境下で使用することによってセラミックス部材の表面に生成した反応生成物等を、極めて高精度にセラミックス部材から除去することができる。 According to the present invention, deposits attached to a ceramic member in the manufacturing process of the ceramic member, reaction products generated on the surface of the ceramic member by actually using the ceramic member in a predetermined environment, etc. are extremely high. It can be accurately removed from the ceramic member.
以下、本発明について具体的に説明する。本発明のセラミックス部材の洗浄方法では、大略的に、汚染されたセラミックス部材を超音波の存在下においてｐＨが１０以上のアルカリ性薬液で処理し、次いでアルカリ性薬液で処理されたセラミックス部材を超音波の存在下において所定の酸性薬液で処理し、さらに酸性薬液で処理されたセラミックス部材を１０００℃以上で加熱処理するものである。 Hereinafter, the present invention will be specifically described. In the method for cleaning a ceramic member of the present invention, generally, a contaminated ceramic member is treated with an alkaline chemical having a pH of 10 or more in the presence of ultrasonic waves, and then the ceramic member treated with the alkaline chemical is ultrasonically treated. A ceramic member treated with a predetermined acidic chemical in the presence and further treated with an acidic chemical is heat-treated at 1000 ° C. or higher.
本発明が適用されるセラミックス部材の材料および用途等には制限はない。例えば、セラミックス部材の具体例としては、半導体製造装置に用いられるフォーカスリング、静電チャック、ウエハ搬送ハンド、チャンバードーム、クランプリング等や、液晶表示装置製造装置に用いられるマスクプレート等、さらに絶縁碍子や真球ビーズ等が挙げられる。 There is no restriction | limiting in the material, use, etc. of the ceramic member to which this invention is applied. For example, specific examples of the ceramic member include a focus ring, an electrostatic chuck, a wafer transfer hand, a chamber dome, a clamp ring used in a semiconductor manufacturing apparatus, a mask plate used in a liquid crystal display manufacturing apparatus, and an insulator. And true spherical beads.
汚染されたセラミックス部材とは、その表面に異物が付着し、またはその表面の少なくとも一部が本来のセラミックス部材の組成とは異なる組成に変化しているものをいい、例えば、製造工程において切削屑や研磨砥粒等が表面に付着したものや、所定の環境下での使用によってその表面が化学的に変化して生成した反応生成物がその表面にパーティクルとして付着していたり、またはその表面に直接に形成されているもの、あるいは所定の環境下で使用されることによってその表面に物理的に異物が付着等しているもの等、をいう。 A contaminated ceramic member is a member in which foreign matter adheres to its surface, or at least a part of its surface changes to a composition different from the composition of the original ceramic member. Or abrasive particles, etc. attached to the surface, or reaction products produced by chemically changing the surface due to use in a predetermined environment are attached to the surface as particles, or on the surface It refers to those that are formed directly, or those that have foreign substances physically attached to their surfaces when used in a predetermined environment.
アルカリ性薬液でのセラミックス部材の洗浄処理は、主に、セラミックス部材の表面に存在する油脂汚れや有機物を溶解する処理である。アルカリ性薬液としては、アルカリ金属と、有機酸と、グリコール系溶剤と、界面活性剤と、純水（イオン交換水）と、を含む薬液が好適に用いられる。より具体的には、アルカリ金属としてカリウム（水酸化カリウムを純水に溶解することによって生成する）が、有機酸としてクエン酸、グルコン酸、エデト酸等が、それぞれ挙げられる。また、グリコール系溶剤としてはエチレングリコールが好適に用いられ、界面活性剤としては非イオン系界面活性剤が好適に用いられる。 The cleaning treatment of the ceramic member with the alkaline chemical solution is mainly a treatment for dissolving oily and dirt stains and organic substances present on the surface of the ceramic member. As the alkaline chemical solution, a chemical solution containing an alkali metal, an organic acid, a glycol solvent, a surfactant, and pure water (ion exchange water) is preferably used. More specifically, potassium (generated by dissolving potassium hydroxide in pure water) is used as the alkali metal, and citric acid, gluconic acid, edetic acid, and the like are listed as the organic acid. Further, ethylene glycol is preferably used as the glycol solvent, and a nonionic surfactant is preferably used as the surfactant.
アルカリ金属と有機酸とグリコール系溶剤と界面活性剤の合計量は２０重量％以下とすることが好ましい。これは、これらの合計量が２０重量％を超えると、洗浄効果は高まるものの、セラミックス素材そのものが化学的に腐食され、本来のセラミックス部材の表面状態を保持することができなくなるという問題が生ずるからである。また、工業的な面でも、薬液費用およびその処理費用が嵩むという問題が生ずるため、好ましくない。アルカリ性薬液は、油脂汚れ等に対して高い溶解能力を有するように、そのｐＨを１０以上とする。これはｐＨが１０未満では、油脂汚れや有機物を溶解する能力が著しく低下し、好ましくないからである。また、アルカリ性薬液での洗浄処理は超音波の存在下において行う。これにより洗浄能力が高められる。 The total amount of alkali metal, organic acid, glycol solvent and surfactant is preferably 20% by weight or less. This is because, if the total amount of these exceeds 20% by weight, the cleaning effect is enhanced, but the ceramic material itself is chemically corroded and the original surface state of the ceramic member cannot be maintained. It is. Also, from an industrial viewpoint, there is a problem in that the cost of the chemical solution and the processing cost increase, which is not preferable. The alkaline chemical solution has a pH of 10 or higher so as to have a high dissolving ability with respect to fat and oil stains and the like. This is because if the pH is less than 10, the ability to dissolve fat and oil stains and organic substances is remarkably lowered, which is not preferable. Further, the cleaning treatment with the alkaline chemical solution is performed in the presence of ultrasonic waves. This enhances the cleaning ability.
酸性薬液によるセラミックス部材の洗浄処理は、セラミックス部材の表面に存在する金属を除去する処理である。酸性薬液としては、セラミックス部材に付着している金属の種類（元素）に応じて、その金属を有効に除去することができるものを選択すればよく、例えば、硝酸、フッ化水素酸（フッ酸）、王水、硫酸、酢酸とフッ酸の混合物等を用いることができる。 The cleaning process of the ceramic member with the acidic chemical solution is a process of removing the metal present on the surface of the ceramic member. What is necessary is just to select what can remove the metal effectively as an acidic chemical | medical solution according to the kind (element) of the metal adhering to the ceramic member, for example, nitric acid, hydrofluoric acid (hydrofluoric acid) ), Aqua regia, sulfuric acid, a mixture of acetic acid and hydrofluoric acid, and the like.
酸性薬液の濃度は１０重量％以下とすることが好ましく、複数種の酸を含む場合にはその合計量が１０重量％以下であればよい。これは、酸性溶液の濃度が１０重量％超では、洗浄効果は高まるものの、セラミックス素材そのものが化学的に腐食され、本来のセラミックス部材の表面状態を保持することができなくなるという問題が生ずるからである。また、工業的な面でも、薬液費用およびその処理費用が嵩むという問題が生ずるため、好ましくない。この酸性薬液による洗浄処理もまた、洗浄能力を高めるために、超音波の存在下において行う。 The concentration of the acidic chemical solution is preferably 10% by weight or less, and when a plurality of acids are included, the total amount may be 10% by weight or less. This is because when the concentration of the acidic solution exceeds 10% by weight, the cleaning effect is enhanced, but the ceramic material itself is chemically corroded, and the original surface state of the ceramic member cannot be maintained. is there. Also, from an industrial viewpoint, there is a problem in that the cost of the chemical solution and the processing cost increase, which is not preferable. The cleaning treatment with the acidic chemical solution is also performed in the presence of ultrasonic waves in order to enhance the cleaning capability.
セラミックス部材の加熱処理は、主に、このような薬液による処理の後にセラミックス部材の表面に残存する付着物や反応生成物等を揮発（蒸発）または分解して除去する処理である。この加熱処理は、セラミックス部材を電気炉やガス炉、マイクロ波加熱炉等に収容し、セラミックス部材を１０００℃以上の所定温度で所定時間保持することによって行われる。１０００℃未満ではセラミックス部材の表面に残存している付着物や反応生成物の除去が不十分になるおそれがある。なお、この加熱処理の処理温度に上限はないが、セラミックス部材の変形や変質等を防止する観点から、事実上、セラミックス部材が焼結体の場合にはその製造時の焼結温度以下とし、セラミックス部材が単結晶体であればその融点以下に制限される。 The heat treatment of the ceramic member is mainly a treatment of removing deposits, reaction products and the like remaining on the surface of the ceramic member by volatilization (evaporation) or decomposition after the treatment with the chemical solution. This heat treatment is performed by housing the ceramic member in an electric furnace, a gas furnace, a microwave heating furnace or the like and holding the ceramic member at a predetermined temperature of 1000 ° C. or higher for a predetermined time. If it is less than 1000 degreeC, there exists a possibility that the removal of the deposit | attachment and reaction product which remain | survived on the surface of the ceramic member may become inadequate. In addition, although there is no upper limit to the processing temperature of this heat treatment, from the viewpoint of preventing deformation or alteration of the ceramic member, in fact, when the ceramic member is a sintered body, the sintering temperature is equal to or lower than the sintering temperature, If the ceramic member is a single crystal, it is limited to the melting point or less.
なお、加熱処理としてプラズマ処理を用いることもでき、セラミックス部材にプラズマを作用させて加熱することにより付着物や反応生成物を除去する。このとき、当然に、プラズマ雰囲気によってセラミックス部材が再汚染されないように、その雰囲気ガスを選択する必要がある。 Note that plasma treatment can also be used as the heat treatment, and deposits and reaction products are removed by heating the ceramic member by applying plasma. At this time, naturally, it is necessary to select the atmosphere gas so that the ceramic member is not recontaminated by the plasma atmosphere.
このようなセラミックス部材の洗浄方法において、アルカリ性薬液による洗浄処理回数に制限はなく、複数回行ってもよい。この場合には、例えば、汚染されたセラミックス部材を、最初に既に使用頻度の多いアルカリ性薬液で処理し、次に使用頻度の少ないアルカリ性薬液で処理し、最後に未使用のアルカリ性薬液で処理するという手法を用いてもよい。なお、酸性薬液による処理についても同様に行うことができる。また、アルカリ性薬液処理と酸性薬液処理とを交互に繰り返して行ってもよく、さらにアルカリ性薬液と酸性薬液による処理と加熱処理とを交互に繰り返して行ってもよい。 In such a method for cleaning a ceramic member, the number of cleaning treatments with an alkaline chemical solution is not limited and may be performed a plurality of times. In this case, for example, a contaminated ceramic member is first treated with an alkaline chemical that is already frequently used, then treated with an alkaline chemical that is less frequently used, and finally treated with an unused alkaline chemical. A technique may be used. In addition, it can carry out similarly about the process by an acidic chemical | medical solution. Further, the alkaline chemical solution treatment and the acidic chemical solution treatment may be alternately repeated, and the alkaline chemical solution and the acidic chemical solution treatment and the heat treatment may be alternately repeated.
さらにまたセラミックス部材をアルカリ性薬液処理で処理した後には純水による洗浄処理（水洗処理）を行い、セラミックス部材に付着したアルカリ性薬液を十分に洗い流した後に、酸性薬液による処理を行うことが好ましい。これは、セラミックス部材にアルカリ金属成分が残っていると、このセラミックス部材を半導体製造装置等に配置したときに、その処理環境をこのアルカリ成分が汚染するおそれがあるので、それを防止するためである。また、この水洗処理によって、アルカリ性薬液と酸性薬液との中和反応によって酸性薬液の洗浄能力が低下したり、酸性薬液が汚染されることが防止される。 Furthermore, after the ceramic member is treated with the alkaline chemical solution treatment, it is preferable to perform a washing treatment with pure water (water washing treatment), and after washing away the alkaline chemical solution adhering to the ceramic member sufficiently, the treatment with the acidic chemical solution is performed. This is to prevent the alkali metal component remaining in the ceramic member, because this alkali component may contaminate the processing environment when the ceramic member is placed in a semiconductor manufacturing apparatus or the like. is there. In addition, this washing treatment prevents the cleaning ability of the acidic chemical liquid from being reduced or the acidic chemical liquid from being contaminated by the neutralization reaction between the alkaline chemical liquid and the acidic chemical liquid.
さらに、酸性薬液による処理の後には純水による洗浄処理を行うことが好ましい。これによってセラミックス部材の表面に残存する酸成分が後に行われる加熱処理によって蒸発等し、加熱処理に用いる炉を汚染することが防止される。さらにまた、セラミックス部材を加熱処理した後にセラミックス部材を純水で洗浄することが好ましい。これにより炉の断熱材等に原因する付着物があった場合に、その付着物を除去することができる。 Furthermore, it is preferable to carry out a cleaning treatment with pure water after the treatment with the acidic chemical solution. As a result, the acid component remaining on the surface of the ceramic member is prevented from evaporating or the like by a heat treatment performed later and contaminating the furnace used for the heat treatment. Furthermore, it is preferable that the ceramic member is washed with pure water after the ceramic member is heat-treated. Thereby, when there is a deposit caused by the heat insulating material of the furnace, the deposit can be removed.
以上のような方法でセラミックス部材を洗浄すれば、そのセラミックス部材の製造工程における付着物またはセラミックス部材を実際に所定の環境下で使用することによって生成した反応生成物等を、極めて高精度に除去することができ、付着物等の残存量を著しく少なくすることができる。 If the ceramic member is washed by the above method, the deposits in the manufacturing process of the ceramic member or the reaction products generated by actually using the ceramic member in a predetermined environment are removed with extremely high accuracy. It is possible to significantly reduce the remaining amount of deposits and the like.
表１は、アルミナ焼結体（表１に「Ａｌ２Ｏ３」と記載）または単結晶アルミナ（表１に「サファイア」と記載）からなり、所定のプラズマ雰囲気で処理されたるセラミックス部材を準備し、これに所定の洗浄処理を行ったときの、そのプラズマ処理条件、アルカリ性薬液および酸性薬液による洗浄処理条件および加熱処理温度、洗浄処理結果を示している。 Table 1 is a ceramic member made of an alumina sintered body (described as “Al 2 O 3 ” in Table 1) or single crystal alumina (described as “Sapphire” in Table 1) and processed in a predetermined plasma atmosphere. The plasma processing conditions, the cleaning processing conditions with the alkaline chemical solution and the acidic chemical solution, the heat processing temperature, and the cleaning processing result when a predetermined cleaning processing is performed on the same are shown.
表１中、実施例１〜９は本発明の範囲内で洗浄処理を行ったものであり、比較例１〜５は本発明の範囲を外れる条件で洗浄処理を行ったものである。ここで、アルカリ性薬液としては、水酸化カリウムと、クエン酸（但し、実施例７、８では含まず）と、エチレングリコール（但し、実施例６、８では含まず）と、非イオン系界面活性剤とからなり、表１に示すｐＨに調整されたものを用いた。また、酸性薬液としては、硝酸とフッ化水素酸を主成分とする希酸薬液を使用した。アルカリ性薬液と酸性薬液の超音波洗浄は、ＢＲＡＮＳＯＮ社製のＳ８５４０型超音波洗浄器を用いて行った。また、酸性薬液処理後の加熱処理は、電気炉を用いて大気雰囲気で行った。 In Table 1, Examples 1 to 9 were subjected to cleaning treatment within the scope of the present invention, and Comparative Examples 1 to 5 were subjected to cleaning treatment under conditions outside the scope of the present invention. Here, as the alkaline chemical solution, potassium hydroxide, citric acid (but not included in Examples 7 and 8), ethylene glycol (but not included in Examples 6 and 8), and nonionic surface activity What was adjusted to pH shown in Table 1 was used. Further, as the acidic chemical solution, a dilute acid chemical solution mainly composed of nitric acid and hydrofluoric acid was used. The ultrasonic cleaning of the alkaline chemical solution and the acidic chemical solution was performed using an S8540 type ultrasonic cleaner manufactured by BRANSON. Moreover, the heat treatment after the acidic chemical solution treatment was performed in an air atmosphere using an electric furnace.
表１に示されるように、実施例１，２，６〜９および比較例１〜５の各セラミックス部材は、エッチング装置に用いられ、フッ素系ガスプラズマ雰囲気に所定時間さらされたアルミナ焼結体部材である。また、実施例５のセラミックス部材は、実施例２と同じ処理条件で処理されたサファイア部材である。実施例３，４のセラミックス部材はＣＶＤ装置に用いられ、塩素系ガスプラズマ雰囲気に所定時間さらされたアルミナ焼結体部材である。 As shown in Table 1, the ceramic members of Examples 1, 2, 6 to 9 and Comparative Examples 1 to 5 were used in an etching apparatus and were exposed to a fluorine gas plasma atmosphere for a predetermined time. It is a member. Moreover, the ceramic member of Example 5 is a sapphire member processed under the same processing conditions as Example 2. The ceramic members of Examples 3 and 4 are sintered alumina members used in a CVD apparatus and exposed to a chlorine-based gas plasma atmosphere for a predetermined time.
洗浄処理後のセラミックス部材の評価は、セラミックス部材の表面における付着物等の除去状態と有色斑点の発生の有無を光学顕微鏡を用いて目視判定し、Ｘ線光電子分光法（ＥＳＣＡ；パーキンエルマー社製 Ｍｏｄｅｌ ５４００ＭＣ）を用いてフッ素または塩素および金属成分（Ｆｅ，Ｎｉ，Ｃｒ，Ｃｕ，アルカリ金属）の成分量を表面分析することにより行った。なお、有色斑点は、微量に残存するＦｅ，Ｎｉ，Ｃｒ等によって発生する欠陥である。 The evaluation of the ceramic member after the cleaning treatment is carried out by visually determining the removal state of deposits and the presence of colored spots on the surface of the ceramic member using an optical microscope, and X-ray photoelectron spectroscopy (ESCA; manufactured by Perkin Elmer) Using Model 5400MC, surface analysis was performed on the component amounts of fluorine or chlorine and metal components (Fe, Ni, Cr, Cu, alkali metal). The colored spots are defects generated by Fe, Ni, Cr, etc. remaining in a minute amount.
表１から明らかなように、実施例１〜５では、セラミックス部材の目視観察において付着物等の除去状態が良好であり、また有色斑点も確認されず、しかもフッ素または塩素および金属成分も検出されなかったことから、最も良好な洗浄処理状態が得られた。また、実施例６〜８では、目視観察においては付着物は除去されていると判断されたが、この付着物が除去された跡の下地に、外観上、色調が変化している部分が観察された。しかし、この部分についてＥＳＣＡによる分析を行っても金属成分等は非検出であったことから、実用上はエッチング装置に再び使用することは差し支えない、つまり実用的な品質の上からは問題がないと判断された。 As is apparent from Table 1, in Examples 1 to 5, the state of removal of deposits and the like is good in visual observation of the ceramic member, no colored spots are confirmed, and fluorine or chlorine and metal components are also detected. As a result, the best cleaning condition was obtained. Further, in Examples 6 to 8, it was determined that the attached matter was removed by visual observation, but a portion where the color tone was changed in appearance was observed on the ground of the trace from which the attached matter was removed. It was done. However, even if this part was analyzed by ESCA, the metal components and the like were not detected, so that it could be reused in the etching apparatus in practice, that is, there was no problem in terms of practical quality. It was judged.
同様に実施例９でも、実施例６〜８よりは軽度であるが、付着物が除去された跡の下地に、外観上、色調が変化している部分が観察された。この実施例９についても、実用的に問題がないと判断された。これに対して、比較例１〜３では、セラミックス部材の目視観察において付着物が残存しており、かつ、フッ素成分が検出された。また比較例３では、金属成分の残留に起因する有色斑点も確認された。比較例４，５では、付着物とフッ素成分は除去されていたが、金属成分の残留による有色斑点が確認された。これら比較例１〜５は、エッチング装置に再び使用することは好ましくないと判断された。 Similarly, in Example 9, although it was milder than Examples 6 to 8, a portion where the color tone was changed in appearance was observed on the base of the trace from which the deposits were removed. This Example 9 was also judged to have no practical problem. On the other hand, in Comparative Examples 1-3, the deposit | attachment remained in visual observation of the ceramic member, and the fluorine component was detected. Moreover, in the comparative example 3, the colored spot resulting from the residue of a metal component was also confirmed. In Comparative Examples 4 and 5, the deposit and the fluorine component were removed, but colored spots due to the remaining metal component were confirmed. These Comparative Examples 1 to 5 were determined not to be used again in the etching apparatus.
本発明は、半導体製造装置用のセラミックス部材の製造および半導体製造装置に用いられているセラミックス部材の洗浄に好適である。 The present invention is suitable for manufacturing a ceramic member for a semiconductor manufacturing apparatus and cleaning a ceramic member used in the semiconductor manufacturing apparatus.
Claims (3)
前記セラミックス部材を超音波の存在下においてｐＨが１０以上のアルカリ性薬液で処理する工程と、
前記アルカリ性薬液処理で処理されたセラミックス部材を超音波の存在下において所定の酸性薬液で処理する工程と、
前記酸性薬液で処理されたセラミックス部材を１０００℃以上で加熱処理する工程と、
を有することを特徴とするセラミックス部材の洗浄方法。 A method for cleaning a ceramic member having a contaminated surface,
Treating the ceramic member with an alkaline chemical having a pH of 10 or higher in the presence of ultrasonic waves;
Treating the ceramic member treated with the alkaline chemical treatment with a predetermined acidic chemical in the presence of ultrasonic waves;
Heat-treating the ceramic member treated with the acidic chemical solution at 1000 ° C. or higher;
A method for cleaning a ceramic member, comprising:
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| JP2007197266A (en) * | 2006-01-27 | 2007-08-09 | Taiheiyo Cement Corp | Ceramic member and its producing method |
| JP2011105539A (en) * | 2009-11-17 | 2011-06-02 | Showa Denko Kk | Method for cleaning aluminum nitride sintered compact |
| WO2022242539A1 (en) * | 2021-05-20 | 2022-11-24 | 北京北方华创微电子装备有限公司 | Ceramic piece cleaning method |
| CN117602967A (en) * | 2023-11-28 | 2024-02-27 | 湖南德智新材料有限公司 | A method for purifying ceramic materials |
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| JP2003055070A (en) * | 2001-08-17 | 2003-02-26 | Nihon Ceratec Co Ltd | Method for cleaning ceramic member |
| JP2003088817A (en) * | 2001-05-22 | 2003-03-25 | Mitsubishi Chemicals Corp | Substrate surface cleaning method |
| JP2003126795A (en) * | 2001-10-26 | 2003-05-07 | Seika Son | Method for cleaning ceramic insulator |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003088817A (en) * | 2001-05-22 | 2003-03-25 | Mitsubishi Chemicals Corp | Substrate surface cleaning method |
| JP2003055070A (en) * | 2001-08-17 | 2003-02-26 | Nihon Ceratec Co Ltd | Method for cleaning ceramic member |
| JP2003126795A (en) * | 2001-10-26 | 2003-05-07 | Seika Son | Method for cleaning ceramic insulator |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007197266A (en) * | 2006-01-27 | 2007-08-09 | Taiheiyo Cement Corp | Ceramic member and its producing method |
| JP2011105539A (en) * | 2009-11-17 | 2011-06-02 | Showa Denko Kk | Method for cleaning aluminum nitride sintered compact |
| WO2022242539A1 (en) * | 2021-05-20 | 2022-11-24 | 北京北方华创微电子装备有限公司 | Ceramic piece cleaning method |
| CN117602967A (en) * | 2023-11-28 | 2024-02-27 | 湖南德智新材料有限公司 | A method for purifying ceramic materials |
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