JP2004244294A - Corrosion resistant member and method of manufacturing the same - Google Patents
Corrosion resistant member and method of manufacturing the same Download PDFInfo
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- JP2004244294A JP2004244294A JP2003038861A JP2003038861A JP2004244294A JP 2004244294 A JP2004244294 A JP 2004244294A JP 2003038861 A JP2003038861 A JP 2003038861A JP 2003038861 A JP2003038861 A JP 2003038861A JP 2004244294 A JP2004244294 A JP 2004244294A
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- 230000007797 corrosion Effects 0.000 title claims abstract description 25
- 238000005260 corrosion Methods 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims abstract description 45
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005530 etching Methods 0.000 claims abstract description 27
- 238000012545 processing Methods 0.000 claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000011260 aqueous acid Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 40
- 230000003746 surface roughness Effects 0.000 claims description 6
- CABDFQZZWFMZOD-UHFFFAOYSA-N hydrogen peroxide;hydrochloride Chemical compound Cl.OO CABDFQZZWFMZOD-UHFFFAOYSA-N 0.000 claims description 3
- 238000010586 diagram Methods 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000012805 post-processing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000003578 releasing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
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Abstract
【課題】イットリア焼結体を加工した後に塩酸、塩酸過水、ふっ酸、硝酸、ふっ硝酸から選ばれる１種以上の酸水溶液により表面酸エッチングされたイットリア焼結体からなる耐食性部材、及びその製造方法を提供する。
【解決手段】イットリア焼結体は、イットリア焼結体を加工した後に塩酸、塩酸過水、ふっ酸、硝酸、ふっ硝酸から選ばれる１種以上の酸水溶液に浸漬せしめ、イットリア焼結体の表面をエッチングして製造される。
【選択図】 図１A corrosion-resistant member made of a yttria sintered body that has been subjected to surface acid etching with at least one aqueous solution of an acid selected from hydrochloric acid, hydrogen peroxide, hydrofluoric acid, nitric acid, and hydrofluoric nitric acid after processing the yttria sintered body; A manufacturing method is provided.
The yttria sintered body is formed by processing a yttria sintered body, immersing the yttria sintered body in one or more aqueous acid solutions selected from hydrochloric acid, hydrogen peroxide, hydrofluoric acid, nitric acid, and hydrofluoric nitric acid. Is manufactured by etching.
[Selection diagram] Fig. 1
Description
【０００１】
【発明の属する技術分野】
本発明は耐食性部材、及びその製造方法に係わり、特に耐プラズマ部材などの各種部材に使用され耐食性部材、及びその製造法に関する。
【０００２】
【従来の技術】
イットリア部材は、その優れた耐プラズマ性、耐溶融塩性、耐ウラン性、耐Ｔｉ合金性などから、半導体用部材、各種溶融用坩堝などへの適用が期待されており、特に半導体デバイスの製造プロセスにおける半導体部材としての適用が期待されている。
【０００３】
イットリア焼結体も多種のセラミックス部材と同様に焼結後、加工され製品化される。坩堝形状では鋳込み成形における排泥方法により成形されるため、その焼結後の加工は必要としないが、半導体部材では孔明けや各種加工が必要となる。その際に加工面が円滑でないと使用時異物混入が生じ、あるいは部材寿命を縮めてしまう。
【０００４】
さらに、イットリア焼結体は、破壊靭性値が１．３〜１．５ＭＰａ・ｍ−１／２と小さいため、加工時に欠けや粒子脱落が発生し易い。特に孔明け加工時、欠けや粒子脱落が生じると、それを除去し円滑化するための後加工が必要となる。また、一部に比較的円滑な表面を有するイットリア焼結体を機械加工すると、その表面から欠けや粒子脱落が生じるが、これら部分を加工により微細な凹凸に修復するのは困難である。
【０００５】
なお、表面凹凸化したセラミックス部材の製造方法として、特許文献１に記載されているように、セラミックス部材を酸エッチングする製造方法が提案されている。しかしながら、この製造方法はエッチング時間短縮の課題を残す。
【０００６】
そこで、加工時生じた欠けや粒子脱落の除去のために後加工を必要とせず、かつエッチング時間を短縮して製造される耐食性部材、及びその製造方法が要望されていた。
【０００７】
また、加工時欠けた部分や粒子脱落跡を時間が短縮されたエッチングにより微細な凹凸に形成するよう耐食性部材、及びその製造方法が要望されていた。
【０００８】
【特許文献１】
特開２００２−３０８６８３号公報（段落番号［００１６］、［００２６］）
【０００９】
【発明が解決しようとする課題】
本発明は上述した事情を考慮してなされたもので、加工時生じた欠けや粒子脱落の除去のために後加工を必要とせず、かつエッチング時間を短縮して製造されるイットリア焼結体からなる耐食性部材、及びその製造方法を提供することを目的とする。
【００１０】
また、欠けた部分や粒子脱落跡を時間が短縮されたエッチングにより微細な凹凸に形成するイットリア焼結体からなる耐食性部材、及びその製造方法を提供することを目的とする。
【００１１】
【課題を解決するための手段】
上記目的を達成するため、本発明の１つの態様によれば、イットリア焼結体を加工した後に塩酸、塩酸過水、ふっ酸、硝酸、ふっ硝酸から選ばれる１種以上の酸水溶液により表面酸エッチングされたイットリア焼結体からなることを特徴とする耐食性部材が提供される。これにより、加工時生じた欠けや粒子脱落の除去のために後加工を必要とせず、かつエッチング時間を短縮して製造されるイットリア焼結体あるいは欠けた部分や粒子脱落跡を時間が短縮されたエッチングにより微細な凹凸に形成されるように耐食性部材が実現される。
【００１２】
好適な一例では、加工時に生じる算術平均粗さＲａ５．０ミクロン未満の面粗さを算術平均粗さＲａ０．８ミクロン未満の面粗さにしたことを特徴とする耐食性部材である。これにより、耐プラズマ性が向上し、半導体部材として用いても、プラズマクリーニング時における選択的なエッチングなどが回避され、耐プラズマ性が助長されるだけでなく、パーティクル問題を解消でき、半導体デバイスの信頼性向上や歩留向上を図ることができる。また、熱応力に対して高い耐性を呈するので、割れや破損など機械的な損傷問題も大幅に解消される。
【００１３】
また、他の好適な一例では、欠けや粒子脱落が生じた表面は、微細な凹凸に表面酸エッチングされたイットリア焼結体からなることを特徴とする耐食性部材である。これにより、ガス放出性も抑制されているので、蒸着やスパッタリングの処理室内部などの構造部材としての使用で、歩留よく、信頼性の高い加工が可能となり、また、真空系の構成部材、凹凸構造面（アンカー効果）を被接合体（積層体）の基材などとして有効であり、付着する粒子や形成する膜の離脱・剥離などの不都合・不具合が全面的に回避・解消される。
【００１４】
本発明の他の態様によれば、加工時算術平均粗さ５．０ミクロン未満面粗さが生じたイットリア焼結体を塩酸、塩酸過水、ふっ酸、硝酸、ふっ硝酸から選ばれる１種以上の酸水溶液により表面エッチングし、その表面を算術平均粗さＲａ０．８ミクロン未満にすることを特徴とする耐食性部材の製造方法が提供される。これにより、破壊靭性値が小いさく、加工時に欠けや粒子脱落が発生し易いイットリアであっても、低コストで加工面荒れを円滑化することができる。
【００１５】
また、本発明の他の態様によれば、欠けや粒子脱落が生じた表面を有するイットリア焼結体を塩酸、塩酸過水、ふっ酸、硝酸、ふっ硝酸から選ばれる１種以上の酸水溶液により表面エッチングし、その表面に微細な凹凸を形成することを特徴とする耐食性部材の製造方法が提供される。これにより、破壊靭性値が小いさく、加工時に欠けや粒子脱落が発生し易いイットリアであっても、低コストで加工面荒れを修復することができる。
【００１６】
【発明の実施の形態】
以下、本発明に係わるイットリア焼結体及びその製造方法の実施形態について添付図面を参照して説明する。
【００１７】
本発明者らは、イットリア焼結体は特定の酸により効果的に表面酸エッチングされるとの知見を得、本発明を完成させるに至った。
【００１８】
すなわち、本発明に係わるイットリア焼結体は、イットリア焼結体を加工した後に塩酸、塩酸過水、ふっ酸、硝酸、ふっ硝酸から選ばれる１種以上の酸水溶液に浸漬せしめ、イットリア焼結体の表面をエッチングして製造される。
【００１９】
具体的には、図１に示すように、加工時にイットリア焼結体１の表面２に生じる算術平均粗さＲａ５．０ミクロン未満面粗さを算術平均粗さＲａ０．８ミクロン未満にする。算術平均粗さＲａはＪＩＳ Ｂ０６０１（２００１）に準ずる方法にて測定し、以下単にＲａと記す。加工時に生じる面粗さが、Ｒａ５．０ミクロンを超えると、上記酸水溶液では効果的に円滑化できず、円滑化後の表面がＲａ０．８ミクロンを超えると、半導体装置用部材などとしてガス拡散工程に使用すると、異物混入が発生する。
【００２０】
上記イットリア焼結体は、純度が９５重量％以上で、平均粒径が１０〜７０μｍであるのが好ましい。その理由として、イットリア焼結体は、粒子同士が粒界を介して接合・一体化した微細構造をなしており、一般的に、結晶粒子（内部）に比べて、結晶粒子間に偏析する不純物の存在量が多い粒界部の方が侵食され易い。しかしながら、その理由は明確でないが、焼結体の構成成分の純度が、９５重量％以上、より好ましくは９９重量％以上で、かつ焼結体の平均粒径が１０〜７０μｍの場合、酸性エッチング液による粒子自体の侵食速度と粒子間（粒界）の侵食速度との差が小さくなって、ほとんど同時的な侵食が進行する。なお、上記平均粒径は１０〜７０μｍであるが、好ましくは１０〜５０μｍ、より好ましくは０〜４５μｍである。また、上記エッチング工程は、常温でもよいが、加湿あるいは加圧することにより反応速度を加速できる。
【００２１】
一般的にイットリア焼結体のプラズマによるエッチングは、表面の破砕層（マイクロクラック）を中心として選択的に行われる傾向があり、イットリア焼結体表面は、プラズマに曝されると徐々にエッチングされるが、このとき、先ず、表面に形成されているマイクロクラックが選択的に行われる。そして、このマイクロクラックは、プラズマクリーニング回数の増加に伴って広がり、半導体デバイスの製造プロセスにおける半導体部材として用いると、選択的なエッチングによって、パーティクル問題を助長する。
【００２２】
上記のようにして、Ｒａ５．０ミクロン未満面粗さのイットリア焼結体は、その表面粗さＲａ０．８ミクロン未満となり、円滑化されるとともに表面に形成されたマイクロクラックも除去され、耐プラズマ性が向上し、半導体部材として用いても、プラズマクリーニング時における選択的なエッチングなどが回避され、耐プラズマ性が助長されるだけでなく、パーティクル問題を解消でき、半導体デバイスの信頼性向上や歩留向上を図ることができる。また、熱応力に対して高い耐性を呈するので、割れや破損など機械的な損傷問題も大幅に解消される。さらに、上記イットリア焼結体を製造する方法を用いれば、低コストで加工面荒れを円滑化することができる。
【００２３】
また、他の具体例について説明する。
【００２４】
図２に示すように、イットリア焼結体１Ａは、欠けや粒子脱落が生じた表面をもったイットリア焼結体を、塩酸、塩酸過水、ふっ酸、硝酸、ふっ硝酸から選ばれる１種以上の酸水溶液に浸漬せしめ、その表面２Ａを表面エッチングして表面２Ａに微細な凹凸を形成して製造される。
【００２５】
欠けや粒子脱落が生じた表面を酸エッチングすることにより、表面層（平均粒径の５倍以内）は、深さ方向に径大部がある平均粒子サイズオーダーの微細孔を含む凹凸構造、換言すると、部分的に粒子が脱落したように見える凹凸構造に侵食される一方、ビッカース硬度も向上する。なお、粒子が脱落したような形状とは、エッチング後の形状がそのように見えると言うだけであり、実際に粒子が欠落するのは、主に粒界そのものが同時にエッチングされることによる。この酸エッチング処理において、表面に形成されたマイクロクラックが除去される。
【００２６】
上記イットリア焼結体の深さ方向に径大部がある凹凸構造は、実質的に平均粒径の５倍以内の表面層のみであり、基体部が緻密で、ガス吸着作用ないしガス放出作用もほとんど無視できる。従って、ガス放出性も抑制されているので、例えば蒸着やスパッタリングの処理室内部などの構造部材としての使用で、歩留よく、信頼性の高い加工が可能となる。また、上記ビッカース硬度の改善・構造と相俟って、例えば真空系の構成部材、凹凸構造面（アンカー効果）を被接合体（積層体）の基材などとして有効である。このアンカー効果により、付着する粒子や形成する膜の離脱・剥離などの不都合・不具合が全面的に回避・解消される。
【００２７】
また、上記本イットリア焼結体を製造する方法を用いれば、破壊靭性値が小いさく、加工時に欠けや粒子脱落が発生し易いイットリアであっても、低コストで加工面荒れを修復することができる。
【００２８】
【実施例】
試験方法：次のようにして作製した試料を用い、表面酸エッチングに用いる２０重量％濃度の酸と、エッチング時間を変え、欠け部の粗さを電子顕微鏡により観察した。
【００２９】
試料：純度９９．９９％以上、焼結体密度４．９８ｇ／ｃｍ３、縦２００ｍｍ×横２００ｍｍ×厚さ５ｍｍのイットリア焼結体に直径０．５ｍｍの貫通孔を２０個明けたところ、全ての孔の入口部に約４ミクロン程度の非定形な欠けが存在し、その表面は粗面であった。
【００３０】
結果：観察結果を表１に示す。
【表１】
表１からもわかるように、いずれの酸を用いた場合にも、面粗さをＲａ０．８ミクロン未満にできることがわかった。特にふっ硝酸を用いると、エッチングが２時間を超えれば、Ｒａ０．８ミクロン未満が達成できる。また、ふっ硝酸、硝酸、ふっ酸、塩酸、塩酸過水の順でエッチングが速いこともわかった。
【００３２】
【発明の効果】
本発明に係わる耐食性部材によれば、加工により生じた欠けや粒子脱落の除去のために後加工を必要とせず、かつエッチング時間を短縮して製造されイットリア焼結体からなる耐食性部材、及びその製造方法を提供することができる。
【００３３】
また、本発明に係わる耐食性部材によれば、欠けた部分や粒子脱落跡を時間が短縮されたエッチングにより微細な凹凸に形成されイットリア焼結体からなる耐食性部材、及びその製造方法を提供することができる。
【図面の簡単な説明】
【図１】本発明に係わる耐食性部材の一実施形態の断面を示す概念図。
【図２】本発明に係わる耐食性部材の他の実施形態の断面を示す概念図。
【符号の説明】
１ イットリア焼結体
２ 表面[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a corrosion-resistant member and a method of manufacturing the same, and more particularly to a corrosion-resistant member used for various members such as a plasma-resistant member and a method of manufacturing the same.
[0002]
[Prior art]
Yttria members are expected to be applied to semiconductor members, various melting crucibles, etc. due to their excellent plasma resistance, molten salt resistance, uranium resistance, Ti alloy resistance, etc. The application as a semiconductor member in a process is expected.
[0003]
The yttria sintered body is processed and commercialized after sintering like many kinds of ceramic members. In the case of a crucible shape, since it is formed by the method of drainage in cast molding, processing after sintering is not required, but in a semiconductor member, drilling and various processing are required. At that time, if the processed surface is not smooth, foreign matter is mixed in during use, or the life of the member is shortened.
[0004]
Further, since the yttria sintered body has a small fracture toughness value of 1.3 to 1.5 MPa · m −1/2 , chipping and particle falling easily occur during processing. In particular, when chipping or falling off of particles occurs during drilling, post-processing is required to remove and smooth the particles. Further, when a yttria sintered body having a relatively smooth surface is partially machined, chipping or particle dropout occurs from the surface, but it is difficult to repair these portions to fine irregularities by machining.
[0005]
As a method for manufacturing a ceramic member having an uneven surface, a manufacturing method in which a ceramic member is acid-etched has been proposed, as described in
[0006]
Therefore, there has been a demand for a corrosion-resistant member that does not require post-processing to remove chips and particles that have been generated during processing and that is manufactured with a reduced etching time, and a method of manufacturing the same.
[0007]
Further, there has been a demand for a corrosion-resistant member and a method of manufacturing the same so that a chipped portion or a trace of falling particles during processing is formed into fine irregularities by etching with a reduced time.
[0008]
[Patent Document 1]
JP-A-2002-308683 (paragraph numbers [0016] and [0026])
[0009]
[Problems to be solved by the invention]
The present invention has been made in consideration of the above-described circumstances, and does not require post-processing to remove chips or particles that have been generated during processing, and has been manufactured from an yttria sintered body manufactured with a reduced etching time. An object of the present invention is to provide a corrosion-resistant member and a method of manufacturing the same.
[0010]
It is another object of the present invention to provide a corrosion-resistant member made of a yttria sintered body in which a chipped portion or a trace of falling particles is formed into fine irregularities by etching with a reduced time, and a method of manufacturing the same.
[0011]
[Means for Solving the Problems]
In order to achieve the above object, according to one aspect of the present invention, after processing a yttria sintered body, surface yttria is treated with one or more aqueous acid solutions selected from hydrochloric acid, hydrogen peroxide, hydrofluoric acid, nitric acid, and hydrofluoric acid. There is provided a corrosion-resistant member comprising an etched yttria sintered body. As a result, it is not necessary to perform post-processing to remove chips and particles that have been generated during processing, and the yttria sintered body manufactured by shortening the etching time or the chipped portion or the trace of the particles falling off is reduced in time. Thus, a corrosion-resistant member is realized so as to be formed into fine irregularities by etching.
[0012]
In a preferred example, the corrosion-resistant member is characterized in that an arithmetic average roughness Ra less than 5.0 microns generated during processing is reduced to an arithmetic average roughness Ra less than 0.8 microns. As a result, plasma resistance is improved, and even when used as a semiconductor member, selective etching or the like during plasma cleaning is avoided, not only plasma resistance is promoted, but also particle problems can be solved, and Reliability and yield can be improved. In addition, since it exhibits high resistance to thermal stress, mechanical damage problems such as cracking and breakage are largely eliminated.
[0013]
In another preferred example, the surface on which chipping or particle detachment has occurred is a corrosion-resistant member characterized by being made of a yttria sintered body that has been subjected to surface acid etching with fine irregularities. As a result, the gas emission is also suppressed, so that it can be used as a structural member such as the inside of a processing chamber for vapor deposition or sputtering, and can be processed with good yield and high reliability. The uneven structure surface (anchor effect) is effective as a base material of a joined body (laminated body) and the like, and inconveniences and defects such as particles adhering and detachment / peeling of a film to be formed are completely avoided or eliminated.
[0014]
According to another aspect of the present invention, the yttria sintered body having an arithmetic mean roughness of less than 5.0 microns during processing is a member selected from the group consisting of hydrochloric acid, hydrogen peroxide, hydrofluoric acid, nitric acid, and hydrofluoric nitric acid. A method for producing a corrosion-resistant member, characterized in that the surface is etched with the above-mentioned acid aqueous solution and the surface thereof is made to have an arithmetic mean roughness Ra of less than 0.8 μm. Thereby, even if it is an yttria which has a small fracture toughness value and is liable to cause chipping or particle falling off during processing, it is possible to smooth the roughened surface at low cost.
[0015]
Further, according to another aspect of the present invention, the yttria sintered body having a surface in which chipping or particle detachment has occurred is prepared by using an aqueous solution of at least one acid selected from hydrochloric acid, hydrogen peroxide, hydrofluoric acid, nitric acid, and hydrofluoric nitric acid. A method for producing a corrosion-resistant member, characterized in that a surface is etched to form fine irregularities on the surface. Thereby, even if it is an yttria having a small fracture toughness value and easily causing chipping or falling off of particles during processing, it is possible to repair the roughened surface at low cost.
[0016]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of a yttria sintered body and a method for manufacturing the same according to the present invention will be described with reference to the accompanying drawings.
[0017]
The present inventors have found that the yttria sintered body is effectively surface acid-etched by a specific acid, and have completed the present invention.
[0018]
That is, the yttria sintered body according to the present invention is obtained by processing the yttria sintered body, then immersing the yttria sintered body in one or more kinds of aqueous acid solutions selected from hydrochloric acid, hydrogen peroxide, hydrofluoric acid, nitric acid and hydrofluoric nitric acid. Manufactured by etching the surface of
[0019]
Specifically, as shown in FIG. 1, the arithmetic mean roughness Ra of less than 5.0 microns generated on the
[0020]
The yttria sintered body preferably has a purity of 95% by weight or more and an average particle size of 10 to 70 μm. The reason for this is that the yttria sintered body has a fine structure in which the particles are joined and integrated via the grain boundaries, and in general, impurities segregated between the crystal particles as compared with the crystal particles (inside). Are more likely to be eroded in the grain boundary portion where the abundance of is present. However, although the reason is not clear, when the purity of the constituents of the sintered body is 95% by weight or more, more preferably 99% by weight or more, and the average particle diameter of the sintered body is 10 to 70 μm, the acid etching is performed. The difference between the erosion rate of the particles themselves due to the liquid and the erosion rate between the particles (grain boundaries) becomes small, and almost simultaneous erosion proceeds. The average particle size is 10 to 70 μm, preferably 10 to 50 μm, more preferably 0 to 45 μm. The etching step may be performed at room temperature, but the reaction rate can be accelerated by humidification or pressurization.
[0021]
Generally, the etching of the yttria sintered body by plasma tends to be selectively performed centering on a crushed layer (micro crack) on the surface, and the surface of the yttria sintered body is gradually etched when exposed to the plasma. However, at this time, first, microcracks formed on the surface are selectively performed. The microcracks spread as the number of times of plasma cleaning increases, and when used as a semiconductor member in a semiconductor device manufacturing process, the selective etching promotes the particle problem.
[0022]
As described above, the yttria sintered body having a surface roughness of less than Ra 5.0 micron has a surface roughness of less than 0.8 micron Ra, is smoothed, and the microcracks formed on the surface are also removed. When used as a semiconductor member, selective etching during plasma cleaning is avoided, not only promoting plasma resistance, but also eliminating particle problems, improving the reliability of semiconductor devices, and improving semiconductor device reliability. Can be improved. In addition, since it exhibits high resistance to thermal stress, mechanical damage problems such as cracking and breakage are largely eliminated. Further, by using the method for producing the yttria sintered body, it is possible to smooth the roughened surface at low cost.
[0023]
Another specific example will be described.
[0024]
As shown in FIG. 2, the yttria sintered
[0025]
The surface layer (within 5 times the average particle size) is subjected to acid etching on the surface where the chipped or dropped particles are formed, so that the surface layer has an uneven structure including fine pores having an average particle size order with a large diameter in the depth direction. Then, while the particles are partially eroded by the uneven structure that appears to have dropped, the Vickers hardness also increases. Note that the shape in which the particles are dropped merely means that the shape after etching looks like that. The reason that the particles are actually missing is mainly that the grain boundaries themselves are etched at the same time. In this acid etching treatment, microcracks formed on the surface are removed.
[0026]
The uneven structure having a large-diameter portion in the depth direction of the yttria sintered body is substantially only a surface layer having an average particle diameter of 5 times or less, the base portion is dense, and a gas adsorbing action or a gas releasing action is also obtained. Almost negligible. Therefore, since the gas release property is also suppressed, high-yield and highly reliable processing can be performed, for example, when used as a structural member in a processing chamber for vapor deposition or sputtering. Further, in combination with the improvement and the structure of the Vickers hardness described above, for example, a vacuum-based constituent member, a concave-convex structure surface (anchor effect) is effective as a base material of a bonded body (laminated body). Due to this anchor effect, inconveniences and inconveniences such as detachment and detachment of the adhered particles and the film to be formed are completely avoided or eliminated.
[0027]
Further, if the method for producing the present yttria sintered body is used, the fracture toughness value is small, and even in the case of yttria in which chipping or particle falling easily occurs during processing, it is possible to repair a roughened surface at a low cost. Can be.
[0028]
【Example】
Test method: Using a sample prepared as follows, an acid having a concentration of 20% by weight used for surface acid etching and the etching time were changed, and the roughness of the notch was observed with an electron microscope.
[0029]
Specimen: purity of 99.99% or more, sintered body density of 4.98 g / cm 3 , length of 200 mm × width of 200 mm × thickness of 5 mm. An irregular chip of about 4 microns was present at the entrance of the hole, and the surface was rough.
[0030]
Results: The observation results are shown in Table 1.
[Table 1]
As can be seen from Table 1, it was found that the surface roughness could be reduced to less than 0.8 micron Ra when any of the acids was used. In particular, when fluorinated nitric acid is used, Ra of less than 0.8 μm can be achieved if etching is performed for more than 2 hours. It was also found that the etching speed was faster in the order of hydrofluoric acid, nitric acid, hydrofluoric acid, hydrochloric acid, and hydrogen peroxide.
[0032]
【The invention's effect】
According to the corrosion-resistant member according to the present invention, a corrosion-resistant member made of a yttria sintered body which is manufactured without shortening the etching time and does not require post-processing for removing chips and particles falling off due to processing, and the same. A manufacturing method can be provided.
[0033]
Further, according to the corrosion-resistant member according to the present invention, it is possible to provide a corrosion-resistant member made of a yttria sintered body in which chipped portions and traces of falling particles are formed into fine irregularities by etching with a reduced time, and a method of manufacturing the same. Can be.
[Brief description of the drawings]
FIG. 1 is a conceptual diagram showing a cross section of an embodiment of a corrosion resistant member according to the present invention.
FIG. 2 is a conceptual diagram showing a cross section of another embodiment of the corrosion resistant member according to the present invention.
[Explanation of symbols]
1 Yttria sintered
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003038861A JP2004244294A (en) | 2003-02-17 | 2003-02-17 | Corrosion resistant member and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003038861A JP2004244294A (en) | 2003-02-17 | 2003-02-17 | Corrosion resistant member and method of manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004244294A true JP2004244294A (en) | 2004-09-02 |
| JP2004244294A5 JP2004244294A5 (en) | 2005-11-04 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003038861A Pending JP2004244294A (en) | 2003-02-17 | 2003-02-17 | Corrosion resistant member and method of manufacturing the same |
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| Country | Link |
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| JP (1) | JP2004244294A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007063070A (en) * | 2005-08-31 | 2007-03-15 | Toshiba Ceramics Co Ltd | Method for manufacturing plasma-resistant yttria sintered compact |
| US8158544B2 (en) | 2008-04-28 | 2012-04-17 | Ferrotec Ceramics Corporation | Yttria sintered body and component used for plasma processing apparatus |
| CN109196620A (en) * | 2016-04-01 | 2019-01-11 | 应用材料公司 | Precipitate the cleaning procedure of fluorine yttrium oxide |
-
2003
- 2003-02-17 JP JP2003038861A patent/JP2004244294A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007063070A (en) * | 2005-08-31 | 2007-03-15 | Toshiba Ceramics Co Ltd | Method for manufacturing plasma-resistant yttria sintered compact |
| US8158544B2 (en) | 2008-04-28 | 2012-04-17 | Ferrotec Ceramics Corporation | Yttria sintered body and component used for plasma processing apparatus |
| CN109196620A (en) * | 2016-04-01 | 2019-01-11 | 应用材料公司 | Precipitate the cleaning procedure of fluorine yttrium oxide |
| CN109196620B (en) * | 2016-04-01 | 2023-07-04 | 应用材料公司 | Cleaning process of precipitated yttrium oxyfluoride |
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