201016630 六、發明說明 【發明所屬之技術領域】 本發明之狀態’一般而言，係與耐蝕性構件及其製造 方法有關者，特別是有關由具有高的耐飽特性（ anticorrosion charasteristic )且體積電阻率（volume resistivity)低的陶瓷構件所成之耐鈾性構件。 φ 【先前技術】 在來，作爲半導體製造裝置用構件等所用之具有耐蝕 性與導電性（electro conductivity )的雙方之材料，一直 在硏究採用具有局的耐電獎特性 （antiplasma charasteristic)之氧化記（Yttrium Oxide)之陶瓷構件。 氧化釔係一種絕緣體（insulator )。一般周知，如對此氧 化釔添加顯示導電性之物質時，則其體積電阻率會降低之 事實。 ® 專利文獻1中，記載有如對氧化釔添加Sic (碳化矽 )2至30wt (重量）％，使用熱壓機（hot press )加以燒 成則可成爲1x1 〇9Ω · cm之事實。 又，專利文獻2中，記載有如對氧化釔添加Ti02-x ( 氧化鈦）（〇<x<2 ) 1至1 5wt%，在氧化氣氛燒成後使其 接觸以碳作爲主成分之物質，並實施惰性氣體或還原氣氛 燒成或者HIP (hot isostatic press’熱間等靜水壓成型） 處理，則可成爲1 ο5至1 〇 14 Ω · cm之事實。 專利文獻3中’記載有如對氧化釔添加金屬釔、碳、 -5- 201016630 氮化釔、碳化釔中的任一種0.5至10wt%，並實施惰性加 壓氣氛燒成，則可成爲至1〇1()Ω · cm之事實。 專利文獻4中，記載有對氧化釔添加鑭系氧化物（ Lanthanoid Oxide) 5質量％以下所成之耐飽性構件之製造 方法。 另一方面，本發明申請人曾經揭示如對氧化釔粉末， 作爲助燒結劑（sintering aide )而添加硼化合物，並在 1400至1 500°C下進行燒成，則可製得緻密體之事實（例 0 如，參考專利文獻5 )。 〔先前技術文獻〕 專利文獻1·'曰本專利特開2006-069843號公報 專利文獻2:日本專利特開2001-089229號公報 專利文獻3 :日本專利特開2005-206402號公報 專利文獻4:日本專利特開2005-335991號公報 專利文獻5:日本專利特開2007-45700號公報 〇 【發明內容】 〔發明所欲解決之課題] 專利文獻1至3的製法，雖可製得低電阻的氧化釔， 惟係一種添加金屬、碳材料、SiC或Ti〇2-X(〇<x<2)之製 法。如將碳等的難燒結物質作爲導電物質利用時，則需要 在高溫或高壓下的熱處理，而招致製作時間的增長及成本 增高。如添加金屬等的導電性物質時，則爲防止所添加之 -6 - 201016630 金屬成分氧化而失去導電性起見，需要煩雜的混合過程或 在特殊的氣氛下的燒成過程，而招致製作時間的增長及成 本增高。 藉由導電性物質之添加所得之低電阻陶瓷的微細構造 ，係在高電阻的絕緣相（insulator phase)中散佈低電阻 的導電相（conducting phase)或導體導電相（conductor conducting phase)之構造或形成網狀（net work)之構造 ❿ ，而此等導電相，在利用電獎照射（phasma exposure)之 腐蝕環境下，將在構件的局部發生電漿的集中，以致有選 擇性進行腐蝕之可能性。 本發明之要旨，係關於耐蝕性構件及其製造方法者， 其目的在於提供一種由具有高的耐蝕特性且體積電阻率低 的陶瓷構件所成之耐蝕性構件。 〔用以解決課題之手段〕 Φ 爲達成前述目的起見，本發明之一實施形態中，可製 得一種耐蝕性構件，其特徵爲：由以氧化釔作爲主成分， 含有鈽（Ce)的元素，利用非氧化氣氛中的燒成所得之陶 瓷構件所成。 本發明之較佳形態中，可製得耐蝕性構件，其係於陶 瓷構件中，釔氧化物中所含之铈元素如以氧化物換算計， 爲5重量％以上，6 0重量％以下者。 本發明之較佳形態中，可製得耐蝕性構件，其係於陶 瓷構件中，體積電阻率係在室溫下，爲1χ1〇7Ω · cm以上 201016630 ，未達 1χ1014Ω · cm 者。 本發明之較佳形態中，可製得耐蝕性構件，其係於陶 瓷構件中，於其燒成體表面之依X射線繞射所得之最強峰 値（peak)位置（20 )，係較下述參比（reference)的 粉末X射線繞射所得之最強峰値位置（2 Θ )爲往低角度 側位移（Shift )者。（在此，參比係將利用氧化氣氛燒成 而立方晶（cubic)氧化釔中固溶（solid dissolved)有立 方晶氧化铈之固溶體（solid solution )加以粉碎所得之粉 _ 末）。 本發明之其他實施形態中，如對氧化釔，按5重量％ 以上’ 60重量％以下的比例添加氧化鈽，並將此混合物成 型後，於非氧化氣氛下在1 3 00 °C以上1 8 00 °C以下進行燒 成，則可製造耐蝕性構件。 本發明之其他實施形態中，如對氧化釔，以铈的氧化 物換算計’按5重量％以上、60重量％以下的比例添加鈽 化合物，並將此混合物成型後，於氧化氣氛下在1 3 00 °C以 參 上1800 °C以下進行燒成後，於非氧化氣氛下在1300 Ό以 上1 800°C以下的溫度進行熱處理，則可製造耐蝕性構件。 本發明之其他實施形態中，如對氧化釔，按5重量％ 以上、60重量％以下的比例添加氧化铈、以氧化硼換算計 ，按0.02重量％以上' 10重量％以下的比例添加硼化合物 ，並將此混合物成型後，於非氧化氣氛下在1300 °C以上 160(TC以下進行燒成，則可製造耐蝕性構件。 本發明之其他實施形態中，如對氧化釔，以铈的氧化 -8 - 201016630 物換算計，按5重量°/β以上、60重量。/。以下的比例添加鈽 化合物、以氧化硼換算計’按0.02重量％以上、1〇重量％ 以下的比例添加硼化合物’並將此混合物成型後，於氧化 氣氛下在1 300 °C以上1 600°C以下進行燒成後，於非氧化 氣氛下在1 300 °C以上1600°C以下的溫度進行熱處理，則 可製造耐蝕性構件。 φ 〔發明之最佳實施形態〕 以下’在參考圖面以下，就本發明之實施形態加以說 明。 本說明書中所使用之語句之意義，爲如下之說明。 (密度） 本發明中所稱密度，乃係視密度（apparent density ) 之意。具體而言，係將試料質量除以從外容積排除開氣孔 ® 後之容積之値，而依阿基米德法（Archimedes method)進 行測定者。 (阿基米德法） 本發明中之阿基米德法，係指JIS規定（JIS R1634) 中所示之密度測定方法之意。水飽和方法（water saturating method)係採用真空法，爲媒液（vehicle)則 採用蒸餾水以進行測定。氣孔率（porosity )的算出方法 ，亦依照JI S R 1 6 3 4所實施者。 201016630 (低電阻） 氧化釔燒成體的體積電阻率，係在室溫（25 °C)下爲 1 Χ1 Ο14 Ω . cm以上。本發明中之低電阻，係將能企圖性改 變作爲絕緣材料之氧化釔的體積電阻率成爲未達1χ1014Ω • cm之性質，定義爲低電阻。 (體積電阻率） 本發明中之體積電阻率，係指將JIS規格（JIS C2142 )中所示之試驗材料的電阻換算爲每單位體積之値之意。 將室溫（25°C)下之體積電阻率，係依三端子法（triod method)加以測定者。 (氧化氣氛） 本發明中之氧化氣氛，係指含有氧氣之氣氛，而經控 制大氣氣氛或氧化濃度之氣氛之意。 (非氧化氣氛） 本發明中之非氧化氣氛，係指還原氣氛及惰性氣氛之 意。具體而言，還原氣氛，係指含有CO (—氧化碳）或 H2 (氫氣）般的還原氣體之氣氛之意，而惰性氣氛，係指 導入(氮氣）或Ar (氬氣）等惰性氣體後加熱時的氣 氛之意。 -10- 201016630 (χ射線繞射外形） 本發明中之X射線外形，係指對試料使用Cu (銅） 燈泡以照射CuK (銅鉀）α線的X射線，將經檢測所繞射 之繞射X射線之角度（20 )作爲橫軸，將繞射強度作爲 縱軸時的曲線圖（chart )之意。本發明中，係將該所檢測 之角度（2 0 )作爲峰値（peak )位置，並將所繞射之X 射線的檢測強度最高的峰値，作爲最強峰値。 (X射線繞射峰値位置往低角度側的位移） 本發明中之X射線繞射峰値位置往低角度側的位移， 係指以氧化釔作爲主成分，於因燒成所製得之陶瓷構件表 面之X射線繞射的20係較下述參比的粉末X射線繞射之 20爲往低角度側位移之意。（在此，上述參比係將因氧 化氣氛燒成而立方晶氧化釔：JCPDF卡00-041-1105中固 體溶解有立方晶氧化鈽：JCPDF卡01-071-4807之固溶體 # 加以粉碎所得之粉末）。 接著’就本發明之一實施形態加以記載。 (混合•原料粉末） 如作爲原料而採用氧化物時，則採用如球磨（ball mill )般的陶瓷製造過程中所利用之混合方法而將原料加 以混合。氧化釔原枓粉末的粒徑，並不特別加以限制，惟 較佳爲平均ΙΟμιη以下、更佳爲2μηι以下較宜。下限値並 無限制’惟可能有成型性的低落之故，較佳爲〇. ! μπι以上 -11 - 201016630 。氧化铈原料粉末的粒徑亦並無限制，惟較佳爲平均 1 Ομιη以下，更佳爲2μιη以下。下限値並無限制，惟可能 有成型性的低落之故’較佳爲〇.1 μπι以上。如球磨般之連 帶粉碎過程之混合方法，不僅能磨細粒徑，尙有粉碎粗大 粒子之效果之故，係—種製造均質且由微細的粒子所成之 陶瓷構件上很合適的方法。 如作爲氧化氣氛中成爲鈽的氧化物之原料粉末而採用 如硝酸鈽般的水溶性化合物時，如姉化合物的水溶液中置 入氧化原料，並將經濕式混合之料漿（slurry)在氧化 氣氛中進行燒成，需要時實施撕碎（shredding )，則可獲 得氧化铈經均質分散之氧化釔-氧化铈原料粉末，而可將 此作成原料粉末。 (成型） 本發明之實施形態中之成型方法，可將經造粒之粉粒 依壓機成型（press molding)或 CIP ( cold isostatic press ’冷間等靜水壓成型）等的乾式成型方法而製得成型體。 成型不僅限於乾式成型，可利用擠壓成型（extruding molding )、注射成型（inj ection molding )、片材成型（ sheet molding)、燒鑄成型（casting molding)、凝膠澆 鏡成型（gel casting molding)等的成型方法以製得成型 體。在乾式成型的情形，可添加黏合劑（binder )後利用 噴霧乾燥機（spray dryer )等，作成顆粒以供利用。 201016630 (燒成） 本發明之一實施形態中，燒成時能在氧化氣氛中進行 1 300°C以上1 800°C以下的燒成，亦能進行具有SiC (碳化 矽）或考塔爾（Kanthal )發熱體之電爐中的燒成。氧化氣 氛燒成後如在13〇〇°C以上1 800°C以下的溫度實施非氧化 氣氛下的熱處理，則可製得陶瓷構件。所得陶瓷構件，需 要時，亦可實施HIP處理。由此，氣孔率（porosity)將 φ 成爲〇%以上，0.1%以下，更佳爲0.05%以下，而可得緻 密質陶瓷構件。 本發明之一實施形態中，如將於前述氧化氣氛的燒成 後之非氧化氣氛的燒成過程，作成HIP處理，則能製得本 發明之陶瓷構件。即使省略非氧化氣氛燒成而實施HIP處 理，仍能製得與前述燒成體同樣的陶瓷構件。HIP處理後 的陶瓷構件將成爲氣孔率0 %以上、0.1 %以下，較佳爲 0_〇5 %以下，而可製得緻密質陶瓷構件。 • 本發明之一實施形態中，燒成時能在非氧化氣氛中進 行1 300°C以上1 800°C以下的燒成。藉由非氧化氣氛的燒 成，而可製得本發明之一實施形態的陶瓷構件。所得陶瓷 構件，需要時，可實施HIP處理。由此，氣孔率將成爲 0%以上、0.1以下，更佳爲0.05%以下，而可得緻密質陶 瓷構件。 添加於氧化釔之鈽化合物而言，能利用：三氧化二铈 (Ce203 )、氧化铈（Ce02 )、氯化鈽、硝酸铈的銨鹽、 三硝酸铈的水合物、氫氧化鈽、碳酸铈、硼化鈽、草酸铈 -13- 201016630 、醋酸鈽等在利用氧化氣氛之燒成的過程中成爲氧化物之 铈化合物，其中氧化鈽很適合利用。 爲提高燒結性起見，而於原料陶瓷中添加硼化合物時 ，則由於燒成中硼化合物容易蒸散之故，較佳爲施加塘瓷 (muffle )等後燒成。硼化合物將在燒成的過程中形成 Υ3Β06、在1100至1600 °C的溫度下形成液相以促進燒成 〇 如添加硼化合物時，則由於將在1 100至1600°c的溫 ❹ 度範圍生成液相之故，燒成溫度在1 300°C以上1600°C以 下，較佳爲在1400°C以上1 550°C以下的溫度領域進行燒 成較宜。燒成時間，可於0.5至8小時之間加以選擇。 在添加有硼化合物之情形，如在成型、脫脂後，利用 氧化氣氛燒成而製得燒成體後，實施N2或Air或CO、H2 等的非氧化氣氛中之熱處理，即可製得所希望的陶瓷構件 。又，成型後，如進行氮氣或氣、氫氣等的氣氛燒成或 真空中的燒成，即可製得所希望的陶瓷構件。 ® 所得陶瓷燒結體可實施HIP處理。由此，氣孔率將成 爲〇 %以上、〇. 1 %以下、更佳爲〇. 〇 5 %以下，而可得緻密 質陶瓷構件。 能生成前述y3bo6結晶之硼化合物而言，並不特別限 制於氧化硼，尙可利用硼酸、氮化硼、碳化硼、ybo3、 y3bo6等的硼化合物，其中氧化硼、硼酸、ybo3很適合 利用。 就利用此種製造方法所得之燒成體的特異性加以說明 -14- 201016630 如混合氧化釔與氧化鈽後進行大氣燒成時，經確認氧 化釔與氧化鋪會成爲1種結晶相之事實。此種結晶相係在 室溫下具有1χ1018Ω . cm以上的高的體積電阻率。但， 經確認如將由非氧化氣氛燒成所得燒成體或者由大氣燒成 所得燒結體加以非氧化氣氛處理，則由大氣燒成所得之結 晶相的峰値位置將往低角度側位移之事實。並發現經峰値 φ 位移之燒成體會顯現低電阻之事實。 從大氣燒成中所得結晶相的峰値位置算出晶格常數（ lattice constant )之結果，經確認其係按照氧化釔與氧化 铈的晶格常數的比例之晶格常數之事實。 另一方面，由非氧化氣氛所燒成之試料的晶格常數， 係經算出數由大氣燒成所得晶格常數爲大的値。此種事實 係可推測爲因該晶格變化成爲峰値位移而出現者。由於因 晶格的變化而顯現有峰値位移之故，本發明之峰値位移的 φ 現象，並不因最強峰値而有所限制。 由本發明所製得之耐蝕性構件，可利用爲：基板熱處 理用之爐室（chamber)、鐘狀真空容器（bell jar)、支 撐體（Suscepter )、壓緊環（champ ring )、聚焦環（ focusing ring )、捕捉環（Capture ring )、鹿蔽環（ shadow ring)、絕緣環（insulating ring)、襯板（liner )、仿真晶圓（dummy wafer )，爲發生高頻電榮（high froguency plasma)之用的軟管（tube)、爲發生高頻電獎 之用的圓頂（dome )、爲支撐半導體晶圓之用的升降銷（ -15- 201016630 lift pin)、淋浴式分散板（shower plate)、緩衝板（ buffie plate)、真空膜盒蓋（bellows cover)、上部電極 (upper electrode )、下部電極（lower electrode)、爐室 內部的構件固定用螺釘（screw)、螺帽 (screw cap ) 、 機器人手臂等將曝露於電漿氣氛中之半導體或者液晶製造 裝置用構件。例如，係爐室或鐘狀真空容器，則可利用爲 進行電漿照射之內壁面，如係聚焦環或捕捉環，則可利用 爲與電漿氣氛相接觸之面。又，其他構件亦可利用爲曝露 @ 於電漿氣氛之面。 再者，由於本發明之耐蝕性構件，具有1x1 07Ω · cm 以上，未達lx 1014 Ω · cm的體積電阻率之故，能利用爲 對半導體晶圓或石英晶圓實施微細加工之蝕刻（etching ) 裝置等的約翰森臘伯克（Johnsen-Rahbek)型靜電吸盤（ electrostatic chuck ) 。 又，本發明之耐蝕性構件，可利用爲輸運氟化氫等的 腐蝕溶液或腐蝕氣體等之用的輸送管等的防止腐蝕用構件 @ 、或實施採用腐蝕溶液之化學處理等時所使用之坩堝（ crucible) ° 有關本發明之一實施形態之耐蝕性構件，係由氧化釔 與铈元素所成之陶瓷構件，由於所添加之鈽元素並非單獨 存在於氧化釔的晶界（inter granule )或三相點（triple point )之故，可在不致於影響氧化釔的耐蝕性之下，製得 具有高的電漿耐性之陶瓷構件。 -16- 201016630 【實施方式】 (實施例1 ) 作爲原料，準備氧化釔粉末（Y2〇3:平均粒徑Ιμηι、 比表面積1 1至l5cm2/g )及氧化铈（Ce02 :平均粒徑 0.6μιη、比表面積約20cm2/g)，將氧化鈽添加量作成5重 量％ '氧化硼粉末（試藥）添加量作成1重量％，添加分 散劑1 ·黏合劑•脫模劑後實施利用球磨之粉碎攪拌混合。 # 混合後實施利用噴霧乾燥機（spray dryer )之造粒（ granulation)。所得造粒粉末，在實施壓機成型後，實施 C IP成型。如藉由利用噴霧乾燥機之造粒及CIP處理而使 成型體密度提升時，則可穩定製得燒成體。所得成型體， 係經脫脂後，在氧化氣氛中1 480°C下加以燒成。所得燒成 體’則在lOOMPa (兆帕）的氬氣氛中實施1 5 00 °C 2小時 的HIP處理。 Φ (實施例2 ) 作爲原料，準備氧化釔粉末（Y2〇3 :平均粒徑Ιμιη、 比表面積11至15cm2/g)及氧化鈽（Ce02:平均粒徑 〇·6μιη、比表面積約20cm2/g )，將氧化铈添加量作成1〇 重量％、氧化硼粉末（試藥）添加量作成1重量％，添加 分散劑•黏合劑•脫模劑後實施利用球磨之粉碎攪拌混合 。混合後實施利用噴霧乾燥機之造粒。所得造粒粉末，在 實施壓機成型後，實施CIP成型。如藉由利用噴霧乾燥機 之造粒及C IP處理而使成型體密度提升時，則可穩定製得 -17- 201016630 燒成體。所得成型體，係經脫脂後，在氧化氣氛中148 0 °C 下加以燒成。所得燒成體，則在lOOMPa氬氣氛中實施 1 500°C 2小時的HIP處理。 (實施例3) 作爲原料，準備氧化釔粉末（Y203 :平均粒徑Ιμπι、 比表面積 1 1至15cm2/g )及氧化铈（Ce〇2 :平均粒徑 〇.6μιη、比表面積約20cm2/g)，將氧化鈽添加量作成20 φ 重量％，添加分散劑•黏合劑•脫模劑後實施利用球磨之 粉碎攪拌混合。混合後實施利用噴霧乾燥機之造粒。所得 造粒粉未，在實施壓機成型後，實施C IP成型。如藉由利 用噴霧乾燥機之造粒及CIP處理而使成型體密度提升時， 則可穩定製得燒成體。所得成型體，係經脫脂後，在氧化 氣氛中1 650°C下加以燒成。所得燒成體，則在lOOMPa氬 氣氛中實施1 500°C 2小時的HIP處理。 (實施例4) 作爲原料，準備氧化釔粉末（Y2〇3 :平均粒徑Ιμιη、 比表面積 1 1至15cm2/g )及氧化鈽（Ce02 :平均粒徑 〇.6μιη、比表面積約20cm2/g )，並將氧化鈽添加量作成 40重量％，添加分散劑•黏合劑•脫模劑後實施利用球磨 之粉碎攪拌混合。混合後實施利用噴霧乾燥機之造粒。所 得造粒粉末，在實施壓機成型後，實施CIP成型。如藉由 利用噴霧乾燥機之造粒及CIP處理而使成型體密度提升時 -18- 201016630 ’則可穩定製得燒成體。所得成型體，係經脫脂後，在氧 化氣氛中1 650°C下加以燒成。所得燒成體，則在lOOMPa 氬氣氛中實施l5〇0°C2小時的HIP處理。 (實施例5) 作爲原料，準備氧化釔粉末（Y2〇3 :平均粒徑Ιμιη、 比表面積 1 1至 15cm2/g )及氧化姉（Ce02 :平均粒徑 φ 〇.6μηι、比表面積約20cm2/g )，並將氧化鈽添加量作成 60重量％，添加分散劑•黏合劑•脫模劑後實施利用球磨 之粉碎攪拌混合。混合後實施利用噴霧乾燥機之造粒。所 得造粒粉末，在實施壓機成型後，實施C IP成型。如藉由 利用噴霧乾燥機之造粒及CIP處理而使成型體密度提升時 ，則可穩定製得燒成體。所得成型體，係經脫脂後，在氧 化氣氛中165(TC下加以燒成。所得燒成體，則在lOOMPa 氬氣氛中實施1 500°C 2小時的HIP處理。 (實施例6) 作爲原料，準備氧化釔粉末（Y2〇3 :平均粒徑Ιμιη、 比表面積1 1至15cm2/g )及氧化铈（Ce02 :平均粒徑 0.6μπι、比表面積約20cm2/g )，並將氧化铈添加量作成5 重量％，添加分散劑•黏合劑•脫模劑後實施利用球磨之 粉碎攪拌混合。混合後實施利用噴霧乾燥機之造粒。所得 造粒粉末，在實施壓機成型後，實施C IP成型。如藉由利 用噴霧乾燥機之造粒及CIP處理而使成型體密度提升時， -19- 201016630 則可穩定製得燒成體。所得成型體，係經脫脂後，在氧化 氣氛中1 650°C下加以燒成。所得燒成體，則在ιοοΜΡa氬 氣氛中實施l5〇〇t： 2小時的HIP處理。 (實施例7) 作爲原料，準備氧化釔粉末（γ2〇3 :平均粒徑Ιμιη、 比表面積 11至 15cm2/g)及氧化铈（Ce02:平均粒徑 0.6μιη、比表面積約20cm2/g )，並將氧化鈽添加量作成 1 5重量％，添加分散劑•黏合劑•脫模劑後實施利用球磨 之粉碎攪拌混合。混合後實施利用噴霧乾燥機之造粒。所 得造粒粉末，在實施壓機成型後，實施C IP成型。如藉由 利用噴霧乾燥機之造粒及CIP處理而使成型體密度提升時 ’則可穩定製得燒成體。所得成型體，係經脫脂後，在氧 化氣氛中1 650°C下加以燒成。所得燒成體，則在lOOMPa 氬氣氛中實施1 500°C 2小時的HIP處理。 (實施例8) 作爲原料，準備氧化釔粉末（Y203 :平均粒徑Ιμπι、 比表面積11至15cm2/g )及氧化铈（Ce02 :平均粒徑 0.6μιη、比表面積約20cm2/g )，並將氧化鈽添加量作成 20重量％、將氧化硼粉末（試藥）添加量作成1重量％， 添加分散劑•黏合劑·脫模劑後實施利用球磨之粉碎攪拌 混合。混合後實施利用噴霧乾燥機之造粒。所得造粒粉末 ，在實施壓機成型後，實施C IP成型。如藉由利用噴霧乾 201016630 定 中 中 徑 80 之 得 型 添 裂 電 燥機之造粒及CIP處理而使成型體密度提升時，則可穩 製得燒成體。所得成型體，係經脫脂後，在氧化氣氛 1 480°C下加以燒成。所得燒成體，則在lOOMPa氬氣氛 實施1 500°C 2小時的HIP處理。 (比較例1 ) 作爲原料，準備氧化釔粉末（Y203 :平均粒徑Ιμπι φ 比表面積11至l5cm2/g)及氧化鈽（Ce〇2:平均粒 0.6μιη、比表面積約20cm2/g )，將氧化姉添加量作成 重量％ ’添加分散劑•黏合劑•脫模劑後實施利用球磨 粉碎攪拌混合。混合後實施利用噴霧乾燥機之造粒。所 造粒粉末’在實施壓機成型後，實施CIP成型。所得成 體’係經脫脂後，在氧化氣氛中1 6 5 0 r下加以燒成。經 加氧化铈80重量％之試料，在利用脫脂之熱處理而發生 紋以致難於進行燒成，結果未能從所得燒成體測定體積 ❹阻。 (比較例2 ) 比較例2爲高純度的氧化釔燒成體。 (比較例3 ) 比較例3爲純度99.7 %的高純度氧化鋁燒成體。 (比較例4 ) -21 - 201016630 作爲原料，準備氧化釔粉末（Υ2〇3 :平均粒徑1 μιη、 比表面積1 1至15cm2/g )及氧化姉（Ce02 :平均粒徑 0·6μπι、比表面積約20cm2/g )，將氧化鈽添加量作成20 重量％ ’添加分散劑•黏合劑.脫模劑後實施利用球磨之 粉碎攪拌混合。混合後實施利用噴霧乾燥機之造粒。所得 造粒粉末’在實施壓機成型後，實施CIP成型。如藉由利 用噴霧乾燥機之造粒及CIP處理而使成型體密度提升時， 則可穩定製得燒成體。所得成型體，係經脫脂後，在氧化 氣氛中1650°C下加以燒成。 (比較例5 ) 作爲原料，準備氧化釔粉末（Y2〇3 ··平均粒徑Ιμιη、 比表面積 1 1至 15cm2/g )及氧化铈（Ce02 :平均粒徑 0.6μιη、比表面積約20cm2/g )，並將氧化鈽添加量作成 40重量％ ’添加分散劑•黏合劑.脫模劑後實施利用球磨 之粉碎攪拌混合。混合後實施利用噴霧乾燥機之造粒。所 得造粒粉末，在實施壓機成型後，實施CIP成型。如藉由 利用噴霧乾燥機之造粒及CIP處理而使成型體密度提升時 ’則可穩定製得燒成體。所得成型體，係經脫脂後，在氧 化氣氛中1 650°c下加以燒成。 (比較例6) 作爲原料，準備氧化釔粉末（Y2〇3 :平均粒徑Ιμιη、 比表面積1 1至15cm2/g )及氧化铈（Ce02 :平均粒徑 -22- 201016630 0.6μηι、比表面積約20cm2/g )，並將氧化铈添加量作成 60重量％，添加分散劑•黏合劑•脫模劑後實施利用球磨 之粉碎攪拌混合。混合後實施利用噴霧乾燥機之造粒。所 得造粒粉末，在實施壓機成型後，實施CIP成型。如藉由 利用噴霧乾燥機之造粒及CIP處理而使成型體密度提升時 ，則可穩定製得燒成體。所得成型體，係經脫脂後，在氧 化氣氛中1 65 0°C下加以燒成。 (比較例7) 作爲原料，準備氧化釔粉末（Y2〇3 :平均粒徑Ιμιη、 比表面積 11至 15cm2/g )及氧化铈（Ce02 :平均粒徑 〇·6μιη、比表面積約2〇cm2/g)，並將氧化鈽添加量作成5 重量％ ’添加分散劑•黏合劑•脫模劑後實施利用球磨之 粉碎擾拌混合。混合後實施利用噴霧乾燥機之造粒。所得 造粒粉末’在實施壓機成型後，實施CIP成型。如藉由利 # 用噴霧乾燥機之造粒及CIP處理而使成型體密度提升時， 則可穩定製得燒成體。所得成型體，係經脫脂後，在氧化 氣氛中165〇°C下加以燒成。 (比較例8) 作爲原料，準備氧化釔粉末（γ2〇3 :平均粒徑1μιη、 比表面積1 1至15cm2/g )及氧化鈽（Ce02 :平均粒徑 〇.6μηι、比表面積約2〇cln2/g )，並將氧化鈽添加量作成 1 5重量％ ’添加分散劑•黏合劑•脫模劑後實施利用球磨 -23- 201016630 之粉碎攪拌混合。混合後實施利用噴霧乾燥機之造粒。所 得造粒粉末，在實施壓機成型後，實施CIP成型。如藉由 利用噴霧乾燥機之造粒及CIP處理而使成型體密度提升時 ，則可穩定製得燒成體。所得成型體，係經脫脂後，在氧 化氣氛中1 650°c下加以燒成。 將實施例1至8及比較例1中所得之陶瓷構件的密度 、體積電阻率表示於表1。實施例1至8的陶瓷構件的體 積電阻率，顯示1χ1〇7Ω . cm以上、未達 1χ1014Ω · cm _ 之値。 又，實施例1至8的陶瓷構件，係緻密質者。作爲代 表例，將實施例4的陶瓷構件的剖面的電子顯微鏡照片， 表示於第1圖。該陶瓷構件係由均質的組織所成’爲不存 在氣孔之緻密的組織。 由以上的結果可知，如釔氧化物中，以氧化物換算計 ，添加铈元素5重量％以上、60重量％以下，則可製得體 積電阻率在室溫下爲1χ1〇7Ω · cm以上、未達1><1〇14Ω · φ cm之陶瓷構件。 -24- 201016630 〔表1〕 組成(重量％) 燒成體密度 (g/cm3) 體積電阻率 (Ω · cm) Y2〇3 Ce〇2 B2〇3 實施例1 94 5 1 5.06 3-lxlO13 實施例2 89 10 1 5.11 3.0x 1011 實施例3 80 20 0 5.25 5.1χ ΙΟ9 實施例4 60 40 0 5.46 1.6χ ΙΟ7 實施例5 40 60 0 5.77 1.5χ ΙΟ7 實施例6 95 5 0 5.08 9Αχ ΙΟ11 實施例7 85 15 0 5.19 7.5χ ΙΟ10 實施例8 79 20 1 5.21 7.7χ ΙΟ9 比較例1 20 80 0 不能燒成 爲進行本發明之一實施形態的耐蝕性構件的耐電漿性 之評價起見，採用反射性離子蝕刻裝置（reachtive ino etching device)(阿內盧巴（股）製，DEA-506)，触'刻 氣體則使用CF4(四氟化碳）（4〇SCCm (每分鐘標準立方 厘米）+02(氧氣）（lOsccm)，對實施例1至8及比較 φ 例2、3進行1 000W (瓦特），30小時的電槳照射處理。 將其結果，表示於表2。 -25- 201016630 〔表2〕 誠(重量％) ___ 蝕刻速度 Y2〇3 Ce〇2 —— (nm/h) 實施例1 94 5 1 78-80 實施例2 89 10 1 54-62 實施例3 80 20 0 40-55 實施例4 60 40 0 ----- 57-76 實施例5 40 60 0 65-78 實施例6 95 5 0 44-52 實施例7 85 15 0 51-58 實施例8 79 20 1 43-60 比較例2 100 0 0 40-80 比較例3 Al2〇3---- 220-300 由表2可知，實施例1至8’具有與比較例2的筒純 度的氧化釔同樣以上的耐電漿性，並具有較比@例1 3 @胃 純度氧化鋁爲非常優異的耐電漿性之事實° 將實施例3至7及比較例4至8的氧化鈽添加量’燒 成氣氛以及最強峰値（2 0 /CuKot)之間的關係’表示於表 3 ° 由表3可知，非氧化氣氛燒成後的峰値位移係按照氧 化铈添加量而改變，有氧化鈽添加量愈多者，其位移量愈 大的傾向。又，經確認位移量愈大者，其電阻値愈低的傾 向。 -26- 201016630 〔表3〕 2 0,(CuKo〇 電阻(Ω · cm) 實施例3 Ce02 20 重量 ％ 還原氣氛燒成 28.91 5.1x10s 實施例4 Ce02 40 重量 ％ 還原氣氛燒成 28.70 1.6x107 實施例5 Ce02 60 雷量％ 還原氣氛燒成 28.43 1.5x107 實施例6 Ce02 5重量％ 還原氣氛燒成 29.07 9.4χ10η 實施例7 Ce02 15 重量 ％ 還原氣氛燒成 28.93 7.5χ1010 比較例4 Ce02 20 重量 ％ 氧化氣氛燒成 29.02 1χ1〇15以上 比較例5 Ce02 40 雷量 ％ 氧化氣氛燒成 28.98 ΙχΙΟ15以上 比較例ό Ce02 60 雷量％ 氧化氣氛燒成 28.94 lxl〇15以上 比較例7 Ce02 5重量％ 氧化氣氛燒成 29.08 lxlO15以上 比較例8 Ce02 15 雷量％ 氧化氣氛燒成 28.98 lxio15以上 將於實施例3至5的試料中，經整理成型體、大氣燒 成品、ΗIP品分別的X射線繞射外形中的最強峰値位置的 變化，表示於第2圖。 成型體中’氧化紀的（ 222)賦予（assignment)峰値 (圖中a)與氧化鈽的（111)賦予峰値，係互爲分離者。 因大氣燒成之結果，2個峰値成爲1個（圖中c)，而峰 値位置則位置於2個峰値之間。ΗIP後，觀察有從c的位 置往低角度側位移之情形（圖中d)。此種現象，不管鈽 添加量之多寡均因HIP處理而確認有往低角度位移的表現 (behavior)。 〔產業上之利用領域〕 如根據本發明之內容，其係關於耐蝕性構件及其製造 方法者，可提供一種由具有高的耐蝕特性且體積電阻率低 的陶瓷構件所成之耐蝕性構件。 -27- 201016630 【圖式簡單說明】 第1圖：表示依本發明之一實施例之耐蝕性構件的電 子顯微鏡照片之圖。 第2圖：表示依本發明之一實施例之耐蝕性構件於檢 測角度（detection angle ) 2 0 =28至30°C下之X射線繞射 外形（profile)之圖。201016630 VI. Description of the Invention [Technical Fields of the Invention] The state of the present invention is generally related to corrosion resistant members and methods of manufacturing the same, and particularly relates to having an anticorrosion charcastistic and volume resistance. A uranium-resistant member made of a ceramic member having a low volume resistivity. φ [Prior Art] As a material having both corrosion resistance and electro conductivity used as a member for a semiconductor manufacturing device, it has been studied to use an oxidation resistance with an antiplasma charasteristic property. (Yttrium Oxide) ceramic components. Cerium oxide is an insulator. It is generally known that when a substance exhibiting conductivity is added to the cerium oxide, the volume resistivity thereof is lowered. In Patent Document 1, there is described the fact that Sic (barium carbide) is added in an amount of 2 to 30 wt% to cerium oxide, and it can be 1 x 1 〇 9 Ω · cm by heating with a hot press. Further, in Patent Document 2, it is described that Ti02-x (titanium oxide) (〇<x<2) is added to cerium oxide from 1 to 15% by weight, and after being fired in an oxidizing atmosphere, it is brought into contact with a substance containing carbon as a main component. And the inert gas or reducing atmosphere firing or HIP (hot isostatic press) treatment can be 1 ο5 to 1 〇 14 Ω · cm. In Patent Document 3, it is described that if 0.5 to 10% by weight of any of metal ruthenium, carbon, -5-201016630 tantalum nitride, and tantalum carbide is added to ruthenium oxide, and it is baked in an inert pressurized atmosphere, it can be 1 〇. 1 () Ω · cm fact. Patent Document 4 describes a method for producing a saturable member formed by adding lanthanum oxide (55% by mass or less) to cerium oxide. On the other hand, the applicant of the present invention has revealed the fact that a dense body can be obtained by adding a boron compound as a sintering aide to a cerium oxide powder and firing it at 1400 to 1,500 ° C. (Example 0, for example, refer to Patent Document 5). [PRIOR ART DOCUMENT 1] 'Patent Document No. 2006-069843. Patent Document 2: Japanese Patent Laid-Open No. 2001-089229. Patent Document 3: Japanese Patent Laid-Open No. 2005-206402. [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. 2007-45700A SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The methods of Patent Documents 1 to 3 can be used to obtain low resistance. Cerium oxide is a method of adding a metal, a carbon material, SiC or Ti〇2-X (〇<x<2). When a hard-to-sinter material such as carbon is used as a conductive material, heat treatment at a high temperature or a high pressure is required, which leads to an increase in production time and an increase in cost. When a conductive material such as a metal is added, it is necessary to prevent the added -6 - 201016630 metal component from being oxidized and lose conductivity. It requires a complicated mixing process or a firing process in a special atmosphere, resulting in production time. Growth and cost increase. The fine structure of the low-resistance ceramic obtained by the addition of the conductive material is a structure in which a low-resistance conducting phase or a conductor conducting phase is dispersed in a high-resistance insulator phase or Forming a net work structure, and in such a conductive phase, in a corrosive environment using phasma exposure, plasma concentration occurs locally in the member, so that selective corrosion is possible. Sex. The gist of the present invention relates to a corrosion-resistant member and a method for producing the same, and an object thereof is to provide a corrosion-resistant member made of a ceramic member having high corrosion resistance and low volume resistivity. [Means for Solving the Problem] Φ In order to achieve the above object, in an embodiment of the present invention, a corrosion-resistant member characterized by containing cerium (Ce) as a main component The element is formed by using a ceramic member obtained by firing in a non-oxidizing atmosphere. In a preferred embodiment of the present invention, a corrosion-resistant member can be obtained, which is contained in a ceramic member, and the cerium element contained in the cerium oxide is 5% by weight or more and 60% by weight or less in terms of oxide. . In a preferred embodiment of the present invention, a corrosion-resistant member can be obtained which is attached to a ceramic member, and has a volume resistivity of 1 χ 1 〇 7 Ω · cm or more and 201016630 at a room temperature of less than 1 χ 1014 Ω · cm. In a preferred embodiment of the present invention, a corrosion-resistant member can be obtained which is attached to the ceramic member and has the strongest peak position (20) obtained by X-ray diffraction on the surface of the fired body. The strongest peak position (2 Θ ) obtained by the powder X-ray diffraction of the reference is the shift to the low angle side (Shift). (In this case, the reference is obtained by firing in an oxidizing atmosphere and solid-solving a solid solution of cubic cerium oxide in a cubic cerium oxide to pulverize the powder). In another embodiment of the present invention, the cerium oxide is added in an amount of 5% by weight or more to 60% by weight or less, and the mixture is molded, and the mixture is molded at a temperature of 1 300 00 ° C or higher in a non-oxidizing atmosphere. When fired at 00 ° C or lower, a corrosion-resistant member can be produced. In another embodiment of the present invention, the cerium compound is added in an amount of 5% by weight or more and 60% by weight or less in terms of cerium oxide, and the mixture is molded in an oxidizing atmosphere. After firing at 00 °C for 1800 °C or less, and then heat-treating at a temperature of 1,300 Å or more and 1,800 °C or less in a non-oxidizing atmosphere, a corrosion-resistant member can be produced. In another embodiment of the present invention, cerium oxide is added in an amount of 5% by weight or more and 60% by weight or less to cerium oxide, and boron compound is added in a ratio of 0.02% by weight or more to 10% by weight or less in terms of boron oxide. After the mixture is molded and fired at 1300 ° C or higher and 160 (TC or less) in a non-oxidizing atmosphere, a corrosion-resistant member can be produced. In another embodiment of the present invention, oxidation of ruthenium is carried out by ruthenium oxide. -8 - 201016630 The amount of boron compound added is 5% by weight or more and 5% by weight or less in terms of boron oxide, in the range of 5 weight % / β or more and 60 weight %. After the mixture is molded, it is fired at 1,300 ° C to 1,600 ° C in an oxidizing atmosphere, and then heat-treated at a temperature of 1,300 ° C to 1600 ° C in a non-oxidizing atmosphere. Manufacture of corrosion-resistant members φ [Best Embodiment of the Invention] Hereinafter, embodiments of the present invention will be described below with reference to the drawings. The meaning of the statements used in the present specification is as follows. (Density) The density referred to in the present invention is the apparent density. Specifically, the mass of the sample is divided by the volume after the open pores are excluded from the outer volume, and The Archimedes method is used for the measurement. (Archimeder method) The Archimedes method in the present invention means the method of density measurement shown in JIS Regulation (JIS R1634). The water saturation method ( The water saturating method is a vacuum method, and the vehicle is distilled water for measurement. The method for calculating the porosity is also carried out in accordance with JI SR 1 6 3 4. 201016630 (low resistance) bismuth oxide The volume resistivity of the fired body is 1 Χ1 Ο 14 Ω·cm or more at room temperature (25 ° C). The low resistance in the present invention is capable of attempting to change the volume resistivity of yttrium oxide as an insulating material. The property of the test material which is less than 1χ1014 Ω • cm is defined as low resistance. (Volume resistivity) The volume resistivity in the present invention means the resistance of the test material shown in JIS specification (JIS C2142) is converted to per unit volume. value The volume resistivity at room temperature (25 ° C) is determined by a three-terminal method (oxidizing atmosphere). The oxidizing atmosphere in the present invention means an atmosphere containing oxygen and is controlled. The atmosphere of the atmosphere or the oxidizing concentration means (non-oxidizing atmosphere) The non-oxidizing atmosphere in the present invention means a reducing atmosphere and an inert atmosphere. Specifically, the reducing atmosphere means CO (carbon monoxide) or The atmosphere of the reducing gas like H2 (hydrogen) is intended, and the inert atmosphere is intended to guide the atmosphere when heated by an inert gas such as (nitrogen) or Ar (argon). -10- 201016630 (X-ray diffraction profile) The X-ray profile in the present invention refers to the use of a Cu (copper) bulb for the sample to illuminate the X-ray of the CuK (copper-potassium) alpha line, and the diffraction of the detected diffraction. The angle (20) of the X-ray is taken as the horizontal axis, and the diffraction intensity is taken as the graph of the vertical axis. In the present invention, the detected angle (20) is taken as the peak position, and the peak of the detected X-ray diffraction intensity is the strongest peak. (The displacement of the X-ray diffraction peak position to the low angle side) The displacement of the X-ray diffraction peak position to the low angle side in the present invention means that yttrium oxide is used as a main component and is obtained by firing. The 20-ray diffraction of the surface of the ceramic member is 20 degrees lower than the following reference powder X-ray diffraction. (Here, the above reference system will be calcined by an oxidizing atmosphere and cubic yttrium oxide: JCPDF card 00-041-1105 solid dissolved in cubic cerium oxide: JCPDF card 01-071-4807 solid solution # 碎The resulting powder). Next, an embodiment of the present invention will be described. (Mixing/raw material powder) When an oxide is used as a raw material, the raw materials are mixed by a mixing method used in a ceramic manufacturing process such as a ball mill. The particle size of the cerium oxide cerium powder is not particularly limited, but is preferably an average ΙΟμηη or less, more preferably 2 μηι or less. The lower limit is not limited. However, there may be a decrease in formability, preferably 〇. ! μπι以上 -11 - 201016630. The particle size of the cerium oxide raw material powder is not limited, but is preferably 1 Ομηη or less, more preferably 2 μιη or less. The lower limit is not limited, but may be low in formability, preferably 〇.1 μπι or more. The mixing method of the pulverization process, such as ball milling, not only can grind the particle size, but also has the effect of pulverizing coarse particles, and is a suitable method for manufacturing a ceramic member which is homogeneous and made of fine particles. For example, when a water-soluble compound such as cerium nitrate is used as a raw material powder of cerium oxide in an oxidizing atmosphere, an oxidizing raw material is placed in an aqueous solution of a cerium compound, and a wet mixed slurry is oxidized. The firing is carried out in an atmosphere, and if necessary, shredding is carried out to obtain a cerium oxide-cerium oxide raw material powder which is uniformly dispersed in cerium oxide, and this can be used as a raw material powder. (Molding) In the molding method according to the embodiment of the present invention, the granulated powder may be subjected to a dry molding method such as press molding or CIP (cold isostatic press). A molded body is obtained. Molding is not limited to dry molding, and extrusion molding, injection molding, sheet molding, casting molding, gel casting molding, and the like can be utilized. A molding method such as to obtain a molded body. In the case of dry molding, a binder may be added and then sprayed with a spray dryer or the like to prepare pellets for use. 201016630 (baking) In one embodiment of the present invention, firing at a temperature of 1 300 ° C or higher and 1 800 ° C or lower in an oxidizing atmosphere can be performed in the case of firing, and SiC (tantalum carbide) or kotar can be performed ( Kanthal) The firing in the electric furnace of the heating element. After the oxidation gas atmosphere is fired, a heat treatment in a non-oxidizing atmosphere is carried out at a temperature of 13 ° C or more and 1 800 ° C or less to obtain a ceramic member. The obtained ceramic member can also be subjected to HIP treatment as needed. Thus, the porosity is φ% or more, 0.1% or less, more preferably 0.05% or less, and a dense ceramic member can be obtained. In one embodiment of the present invention, the ceramic member of the present invention can be obtained by subjecting the oxidizing atmosphere to a non-oxidizing atmosphere after the firing in the oxidizing atmosphere to form a HIP treatment. Even if the HIP treatment is performed by omitting the non-oxidizing atmosphere, the same ceramic member as the above-described fired body can be obtained. The ceramic member after the HIP treatment has a porosity of 0% or more and 0.1% or less, preferably 0_〇5 % or less, to obtain a dense ceramic member. In one embodiment of the present invention, firing at 1 300 ° C or higher and 1 800 ° C or lower can be carried out in a non-oxidizing atmosphere during firing. The ceramic member of one embodiment of the present invention can be obtained by firing in a non-oxidizing atmosphere. The obtained ceramic member can be subjected to HIP treatment as needed. Thereby, the porosity is 0% or more and 0.1 or less, more preferably 0.05% or less, and a dense ceramic member can be obtained. For the cerium oxide-added cerium compound, it can be used: cerium oxide (Ce203), cerium oxide (Ce02), cerium chloride, ammonium cerium nitrate, cerium trinitrate hydrate, cerium hydroxide, cerium carbonate , lanthanum boride, lanthanum oxalate-13-201016630, yttrium acetate, etc. become an oxide compound in the process of firing in an oxidizing atmosphere, wherein cerium oxide is suitable for use. In order to improve the sinterability, when a boron compound is added to the raw material ceramic, since the boron compound is easily evaporated during the firing, it is preferable to apply a muffle or the like and then fire it. The boron compound will form Υ3Β06 during firing, and form a liquid phase at a temperature of 1100 to 1600 °C to promote firing. For example, when a boron compound is added, it will be in a temperature range of 1 100 to 1600 ° C. The liquid phase is formed so that the firing temperature is preferably from 1,300 ° C to 1,600 ° C, preferably from 1400 ° C to 1,550 ° C. The firing time can be selected between 0.5 and 8 hours. When a boron compound is added, for example, after molding or degreasing, the sintered body is obtained by firing in an oxidizing atmosphere, and then heat treatment in a non-oxidizing atmosphere such as N2 or Air or CO or H2 is carried out to obtain a sintered body. Desirable ceramic components. Further, after molding, a desired ceramic member can be obtained by firing in an atmosphere of nitrogen, gas, hydrogen or the like or baking in a vacuum. ® The resulting ceramic sintered body can be subjected to HIP treatment. Thereby, the porosity is set to be 〇% or more, 〇.1% or less, more preferably 〇. 〇 5 % or less, and a dense ceramic member can be obtained. The boron compound capable of producing the y3bo6 crystal is not particularly limited to boron oxide, and a boron compound such as boric acid, boron nitride, boron carbide, ybo3 or y3bo6 can be used, and boron oxide, boric acid and ybo3 are suitably used. The specificity of the fired body obtained by the above-described production method is explained. -14 - 201016630 When the cerium oxide and the cerium oxide are mixed and then calcined in the air, it is confirmed that the cerium oxide and the oxidized layer become one crystal phase. This crystal phase has a high volume resistivity of 1 χ 1018 Ω·cm or more at room temperature. However, it has been confirmed that the sintered body obtained by firing in a non-oxidizing atmosphere or the sintered body obtained by firing in the atmosphere is treated in a non-oxidizing atmosphere, and the peak position of the crystal phase obtained by firing in the atmosphere is displaced to the low angle side. . It is also found that the sintered body with a peak 値 φ displacement exhibits a low resistance. The fact that the lattice constant was calculated from the peak position of the crystal phase obtained in the air calcination was confirmed to be a lattice constant in accordance with the ratio of the lattice constant of cerium oxide to cerium oxide. On the other hand, the lattice constant of the sample fired in the non-oxidizing atmosphere is a enthalpy in which the calculated lattice constant obtained by firing in the atmosphere is large. This fact can be presumed to occur as the lattice change becomes a peak-to-peak displacement. Since the existing peak-to-peak displacement due to the change of the crystal lattice, the φ phenomenon of the peak-to-peak displacement of the present invention is not limited by the strongest peak. The corrosion-resistant member obtained by the present invention can be used as a chamber for heat treatment of a substrate, a bell jar, a support (Suscepter), a clamp ring, and a focus ring ( Focusing ring ), capture ring, shadow ring, insulating ring, liner, and dummy wafer for high froguency plasma ), a tube for the high-frequency electric prize, a lift pin for supporting the semiconductor wafer ( -15- 201016630 lift pin), a shower type dispersion plate (shower) Plate), buffie plate, bellows cover, upper electrode, lower electrode, screw for component fixing inside the furnace, screw cap ), a robot arm or the like for exposing the semiconductor or liquid crystal manufacturing apparatus to a plasma atmosphere. For example, a furnace chamber or a bell-shaped vacuum vessel can be used as an inner wall surface for plasma irradiation, such as a focus ring or a capture ring, which can be used as a surface in contact with the plasma atmosphere. Also, other components may be utilized to expose the surface of the plasma atmosphere. Further, since the corrosion-resistant member of the present invention has a volume resistivity of 1×1 07 Ω·cm or more and less than 1×10 14 Ω·cm, it can be used for etching of a semiconductor wafer or a quartz wafer by etching (etching) ) Johnsen-Rahbek type electrostatic chuck for devices, etc. In addition, the corrosion-resistant member of the present invention can be used as a corrosion-preventing member such as a transporting tube for transporting an aqueous solution such as hydrogen fluoride or a corrosive gas, or a chemical treatment such as a chemical solution using a corrosive solution. (crucible) The corrosion-resistant member according to an embodiment of the present invention is a ceramic member made of yttrium oxide and yttrium element, since the added yttrium element is not present in the intergranular or intergranular layer of yttrium oxide alone. At the triple point, ceramic members having high plasma resistance can be produced without affecting the corrosion resistance of yttrium oxide. -16-201016630 [Embodiment 1] (Example 1) As a raw material, cerium oxide powder (Y2〇3: average particle diameter Ιμηι, specific surface area 1 1 to 15 cm 2 /g) and cerium oxide (Ce02 : average particle diameter 0.6 μm) were prepared. The specific surface area is about 20 cm 2 /g, and the amount of cerium oxide added is 5% by weight. 'The amount of boron oxide powder (reagent) is 1% by weight, and the dispersing agent 1 · binder and releasing agent are added, and then pulverized by ball milling. Stir and mix. # After mixing, granulation using a spray dryer was carried out. The obtained granulated powder was subjected to C IP molding after being subjected to press molding. When the density of the molded body is increased by granulation by a spray dryer and CIP treatment, the fired body can be stably produced. The obtained molded body was degreased and then fired at 1,480 ° C in an oxidizing atmosphere. The obtained fired body was subjected to HIP treatment at 1 500 ° C for 2 hours in an argon atmosphere of 100 MPa (MPa). Φ (Example 2) As a raw material, cerium oxide powder (Y2〇3: average particle diameter Ιμηη, specific surface area: 11 to 15 cm 2 /g) and cerium oxide (Ce02: average particle diameter 〇·6 μmη, specific surface area of about 20 cm 2 /g) were prepared. The amount of cerium oxide added is 1% by weight, and the amount of boron oxide powder (reagent) is 1% by weight. The dispersing agent, the binder, and the releasing agent are added, and then pulverized and stirred by ball milling. After mixing, granulation by a spray dryer was carried out. The obtained granulated powder was subjected to CIP molding after being subjected to press molding. When the density of the molded body is increased by granulation by a spray dryer and CIP treatment, the sintered body of -17-201016630 can be stably obtained. The obtained molded body was degreased and then fired at 148 ° C in an oxidizing atmosphere. The obtained fired body was subjected to HIP treatment at 1,500 ° C for 2 hours in an argon atmosphere of 100 MPa. (Example 3) As a raw material, cerium oxide powder (Y203: average particle diameter Ιμπι, specific surface area: 1 to 15 cm 2 /g) and cerium oxide (Ce 〇 2 : average particle diameter 〇.6 μιη, specific surface area of about 20 cm 2 /g) were prepared. The amount of cerium oxide added is 20 φ% by weight, and a dispersing agent, a binder, and a releasing agent are added, and then pulverized and stirred by a ball mill. After mixing, granulation by a spray dryer was carried out. The obtained granulated powder was not subjected to C IP molding after press molding. When the density of the molded body is increased by granulation by a spray dryer and CIP treatment, the fired body can be stably produced. The obtained molded body was degreased and then fired at 1,650 ° C in an oxidizing atmosphere. The obtained fired body was subjected to HIP treatment at 1,500 ° C for 2 hours in an argon atmosphere of 100 MPa. (Example 4) As a raw material, cerium oxide powder (Y2〇3: average particle diameter Ιμηη, specific surface area: 1 to 15 cm 2 /g) and cerium oxide (Ce02 : average particle diameter 〇.6 μιη, specific surface area of about 20 cm 2 /g) were prepared. And adding the amount of cerium oxide to 40% by weight, adding a dispersing agent, a binder, and a releasing agent, and then performing pulverization and stirring mixing by ball milling. After mixing, granulation by a spray dryer was carried out. The obtained granulated powder was subjected to CIP molding after being subjected to press molding. When the density of the molded body is increased by granulation by a spray dryer and CIP treatment, the sintered body can be stably produced by -18-201016630 '. The obtained molded body was degreased and then fired at 1,650 ° C in an oxidizing atmosphere. The obtained fired body was subjected to HIP treatment at 150 ° C for 2 hours in an argon atmosphere of 100 MPa. (Example 5) As a raw material, cerium oxide powder (Y2〇3: average particle diameter Ιμηη, specific surface area: 1 to 15 cm 2 /g) and cerium oxide (Ce02 : average particle diameter φ 6.6 μηι, specific surface area of about 20 cm 2 / were prepared) g), and the amount of cerium oxide added is 60% by weight, and a dispersing agent, a binder, and a releasing agent are added, and then pulverized and stirred by a ball mill. After mixing, granulation by a spray dryer was carried out. The obtained granulated powder was subjected to C IP molding after being subjected to press molding. When the density of the molded body is increased by granulation by a spray dryer and CIP treatment, the fired body can be stably produced. The obtained molded body was degreased, and then fired in an oxidizing atmosphere at 165 (TC). The obtained fired body was subjected to HIP treatment at 1,500 ° C for 2 hours in an argon atmosphere of 100 MPa. (Example 6) As a raw material Prepare cerium oxide powder (Y2〇3: average particle diameter Ιμιη, specific surface area 1 1 to 15 cm 2 /g) and cerium oxide (Ce02 : average particle diameter 0.6 μπι, specific surface area about 20 cm 2 /g), and the amount of cerium oxide added 5% by weight, adding a dispersing agent, a binder, and a releasing agent, and then performing pulverization and stirring mixing by ball milling. After mixing, granulation by a spray dryer is carried out. The obtained granulated powder is subjected to C IP molding after press molding. When the density of the molded body is increased by granulation and CIP treatment using a spray dryer, the sintered body can be stably produced by -19-201016630. The obtained molded body is degreased in an oxidizing atmosphere. The fired body was fired at 650 ° C. The obtained fired body was subjected to HIP treatment for 15 hours in an argon atmosphere of ιοοΜΡa. (Example 7) As a raw material, cerium oxide powder (γ 2 〇 3 : average granules) was prepared. Diameter ιμιη, specific surface area 11 to 15cm2 /g) and cerium oxide (Ce02: average particle diameter 0.6 μιη, specific surface area: about 20 cm 2 /g), and the amount of cerium oxide added is 15% by weight, and a dispersing agent, a binder, and a releasing agent are added, and then ball milling is performed. The mixture is pulverized and mixed, and then granulated by a spray dryer, and the obtained granulated powder is subjected to C IP molding after press molding, and the density of the molded body is obtained by granulation and CIP treatment using a spray dryer. When the film is lifted, the fired body can be stably obtained. The obtained molded body is degreased and then fired at 1,650 ° C in an oxidizing atmosphere. The obtained fired body is subjected to 1500 ° C in an argon atmosphere of 100 MPa. 2 hours of HIP treatment. (Example 8) As a raw material, cerium oxide powder (Y203: average particle diameter Ιμπι, specific surface area: 11 to 15 cm 2 /g) and cerium oxide (Ce02 : average particle diameter 0.6 μm, specific surface area of about 20 cm 2 ) were prepared. /g), the amount of cerium oxide added is 20% by weight, and the amount of boron oxide powder (reagent) is 1% by weight, and a dispersing agent, a binder, and a releasing agent are added, and then pulverized and stirred by a ball mill is mixed. Post-implementation using spray drying Granulation of the machine. The obtained granulated powder is subjected to C IP molding after being subjected to press molding, for example, by granulation and CIP treatment using a spray-dried 201016630 medium-diameter 80-type type cracking electric dryer. When the density of the molded body is increased, the fired body can be stabilized. The obtained molded body is degreased and then fired in an oxidizing atmosphere at 480 ° C. The obtained fired body is subjected to 1500 ° in an argon atmosphere of 100 MPa. C 2 hour HIP treatment. (Comparative Example 1) As a raw material, cerium oxide powder (Y203: average particle diameter Ιμπι φ specific surface area 11 to 15 cm 2 /g) and cerium oxide (Ce 〇 2: average particle 0.6 μmη, specific surface area: about 20 cm 2 /g) were prepared. The amount of cerium oxide added is made into a weight %. After adding a dispersing agent, a binder, and a releasing agent, the mixture is stirred and mixed by a ball mill. After mixing, granulation by a spray dryer was carried out. The granulated powder ' was subjected to CIP molding after being subjected to press molding. The obtained adult was degreased and then fired in an oxidizing atmosphere at 165 rpm. When the sample containing 80% by weight of cerium oxide was formed by heat treatment by degreasing, it was difficult to carry out baking, and as a result, the volume enthalpy was not measured from the obtained fired body. (Comparative Example 2) Comparative Example 2 is a high-purity yttrium oxide sintered body. (Comparative Example 3) Comparative Example 3 was a high-purity alumina fired body having a purity of 99.7 %. (Comparative Example 4) -21 - 201016630 As a raw material, cerium oxide powder (Υ2〇3: average particle diameter 1 μιη, specific surface area 1 1 to 15 cm 2 /g) and cerium oxide (Ce02 : average particle diameter 0·6 μπι, ratio) were prepared. The surface area is about 20 cm 2 /g), and the amount of cerium oxide added is 20% by weight. 'Adding a dispersing agent and a binder. After releasing the mold, the mixture is stirred and mixed by ball milling. After mixing, granulation by a spray dryer was carried out. The obtained granulated powder ' was subjected to CIP molding after being subjected to press molding. When the density of the molded body is increased by granulation by a spray dryer and CIP treatment, the fired body can be stably produced. The obtained molded body was degreased and then fired at 1,650 ° C in an oxidizing atmosphere. (Comparative Example 5) As a raw material, cerium oxide powder (Y2〇3 ··average particle diameter Ιμηη, specific surface area: 1 to 15 cm 2 /g) and cerium oxide (Ce02 : average particle diameter of 0.6 μm, specific surface area of about 20 cm 2 /g) were prepared. And adding the amount of cerium oxide to 40% by weight 'adding a dispersing agent, a binder, and a releasing agent, and then performing pulverization and stirring mixing by ball milling. After mixing, granulation by a spray dryer was carried out. The obtained granulated powder was subjected to CIP molding after being subjected to press molding. When the density of the molded body is increased by granulation by a spray dryer and CIP treatment, the sintered body can be stably produced. The obtained molded body was degreased and then fired at 1,650 ° C in an oxidizing atmosphere. (Comparative Example 6) As a raw material, cerium oxide powder (Y2〇3: average particle diameter Ιμηη, specific surface area: 1 to 15 cm 2 /g) and cerium oxide (Ce02 : average particle diameter -22 - 201016630 0.6 μηι, specific surface area) were prepared. 20 cm 2 /g ), and the amount of cerium oxide added was 60% by weight, and a dispersing agent, a binder, and a releasing agent were added, and then pulverized and stirred by a ball mill was carried out. After mixing, granulation by a spray dryer was carried out. The obtained granulated powder was subjected to CIP molding after being subjected to press molding. When the density of the molded body is increased by granulation by a spray dryer and CIP treatment, the fired body can be stably produced. The obtained molded body was degreased and then fired at 1,650 ° C in an oxidizing atmosphere. (Comparative Example 7) As a raw material, cerium oxide powder (Y2〇3: average particle diameter Ιμηη, specific surface area: 11 to 15 cm 2 /g) and cerium oxide (Ce02 : average particle diameter 〇·6 μmη, specific surface area of about 2 〇cm 2 /) were prepared. g), and the amount of cerium oxide added is 5% by weight. 'Adding a dispersing agent, a binder, and a releasing agent, and then mixing and mixing by ball milling. After mixing, granulation by a spray dryer was carried out. The obtained granulated powder ' was subjected to CIP molding after being subjected to press molding. When the density of the molded body is increased by granulation and CIP treatment using a spray dryer, the sintered body can be stably produced. The obtained molded body was degreased and then fired at 165 ° C in an oxidizing atmosphere. (Comparative Example 8) As a raw material, cerium oxide powder (γ 2 〇 3 : average particle diameter 1 μm, specific surface area 1 1 to 15 cm 2 /g) and cerium oxide (Ce02 : average particle diameter 〇.6 μηι, specific surface area about 2 〇 cln 2 ) were prepared. /g), and the amount of cerium oxide added is made into 15% by weight 'Adding a dispersing agent, a binder, and a releasing agent, and then mixing and pulverizing and mixing using a ball mill -23-201016630. After mixing, granulation by a spray dryer was carried out. The obtained granulated powder was subjected to CIP molding after being subjected to press molding. When the density of the molded body is increased by granulation by a spray dryer and CIP treatment, the fired body can be stably produced. The obtained molded body was degreased and then fired at 1,650 ° C in an oxidizing atmosphere. The density and volume resistivity of the ceramic members obtained in Examples 1 to 8 and Comparative Example 1 are shown in Table 1. The volume resistivity of the ceramic members of Examples 1 to 8 was χ1〇7 Ω·cm or more and less than 1χ1014 Ω·cm _. Further, the ceramic members of Examples 1 to 8 are dense. An electron micrograph of a cross section of the ceramic member of Example 4 is shown in Fig. 1 as an example. The ceramic member is formed of a homogeneous structure as a dense structure in which no pores exist. From the above results, it is found that, in the cerium oxide, when the cerium element is added in an amount of 5 wt% or more and 60 wt% or less in terms of an oxide, the volume resistivity can be made 1 χ 1 〇 7 Ω · cm or more at room temperature. A ceramic member of less than 1>1〇14 Ω · φ cm. -24- 201016630 [Table 1] Composition (% by weight) Density of sintered body (g/cm3) Volume resistivity (Ω · cm) Y2〇3 Ce〇2 B2〇3 Example 1 94 5 1 5.06 3-lxlO13 Implementation Example 2 89 10 1 5.11 3.0x 1011 Example 3 80 20 0 5.25 5.1χ ΙΟ9 Example 4 60 40 0 5.46 1.6χ ΙΟ7 Example 5 40 60 0 5.77 1.5χ ΙΟ7 Example 6 95 5 0 5.08 9Αχ ΙΟ11 Example 7 85 15 0 5.19 7.5 χ 10 Example 8 79 20 1 5.21 7.7 χ ΙΟ 9 Comparative Example 1 20 80 0 Failure to burn is evaluated by the evaluation of the plasma resistance of the corrosion-resistant member according to the embodiment of the present invention. A reachtive ino etching device (DEA-506, manufactured by Aneluba), using CF4 (carbon tetrafluoride) for touch gas (4〇SCCm (standard cubic centimeters per minute) +02 (Oxygen) (10 seccm), 1 000 W (Watt) of Example 1 to 8 and Comparative φ Examples 2 and 3, and 30 hours of electric paddle irradiation treatment. The results are shown in Table 2. -25 - 201016630 [Table 2] Honest (% by weight) ___ Etching speed Y2〇3 Ce〇2 ——(nm/h) Example 1 94 5 1 78-80 Example 2 8 9 10 1 54-62 Example 3 80 20 0 40-55 Example 4 60 40 0 ----- 57-76 Example 5 40 60 0 65-78 Example 6 95 5 0 44-52 Example 7 85 15 0 51-58 Example 8 79 20 1 43-60 Comparative Example 2 100 0 0 40-80 Comparative Example 3 Al2〇3---- 220-300 As can be seen from Table 2, Examples 1 to 8' have The pulverization of the tube purity of Comparative Example 2 was similar to the above-mentioned plasma resistance, and had a much superior plasma resistance than that of the Example 1 3 @gas purity alumina. Examples 3 to 7 and Comparative Example 4 were The amount of cerium oxide added in 8 'the relationship between the firing atmosphere and the strongest peak 2 (20 / CuKot)' is shown in Table 3 ° It can be seen from Table 3 that the peak enthalpy displacement after firing in a non-oxidizing atmosphere is added according to cerium oxide. The amount of cerium oxide added is larger, and the amount of displacement is larger. The larger the displacement is, the lower the resistance is. -26- 201016630 [Table 3] 2 0, (CuKo〇 resistance (Ω · cm) Example 3 Ce02 20% by weight Reduction atmosphere firing 28.91 5.1x10s Example 4 Ce02 40% by weight Reduction atmosphere firing 28.70 1.6x107 Example 5 Ce02 60 Amount % Reduction atmosphere calcination 28.43 1.5x107 Example 6 Ce02 5 wt% Reduction atmosphere calcination 29.07 9.4 χ 10η Example 7 Ce02 15 wt% Reduction atmosphere calcination 28.93 7.5 χ 1010 Comparative Example 4 Ce02 20 wt% Oxidation atmosphere calcined 29.02 1χ1 〇15 or more Comparative Example 5 Ce02 40 Thunder amount % Oxidation atmosphere firing 28.98 ΙχΙΟ15 or more Comparative example ό Ce02 60 Thunder amount % Oxidation atmosphere firing 28.94 lxl 〇 15 or more Comparative Example 7 Ce02 5 wt% Oxidation atmosphere firing 29.08 lxlO15 or more Example 8 Ce02 15 Light % % Oxidation atmosphere firing 28.98 lxio 15 or more In the samples of Examples 3 to 5, the strongest peak position in the X-ray diffraction profile of the finished molded body, the atmospheric fired product, and the ΗIP product was respectively The change is shown in Figure 2. In the molded body, the oxidative (222) assignment peak 値 (a in the figure) and the (111) yttrium oxide yttrium peak are separated from each other. As a result of the firing of the atmosphere, the two peaks become one (c in the figure), and the peak position is between the two peaks. After ΗIP, observe the case where the position from c is shifted to the low angle side (d in the figure). This phenomenon, regardless of the amount of 钸 added, is confirmed by the HIP process to have a low angle of displacement behavior (behavior). [Industrial Applicability] According to the present invention, it is possible to provide a corrosion-resistant member made of a ceramic member having high corrosion resistance and low volume resistivity, relating to the corrosion-resistant member and the method for producing the same. -27- 201016630 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an electron micrograph of a corrosion-resistant member according to an embodiment of the present invention. Fig. 2 is a view showing an X-ray diffraction profile of a corrosion-resistant member according to an embodiment of the present invention at a detection angle of 20 = 28 to 30 °C.
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