TW201943317A - 電漿處理裝置用構件及具備其之電漿處理裝置 - Google Patents

電漿處理裝置用構件及具備其之電漿處理裝置 Download PDF

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TW201943317A
TW201943317A TW108111705A TW108111705A TW201943317A TW 201943317 A TW201943317 A TW 201943317A TW 108111705 A TW108111705 A TW 108111705A TW 108111705 A TW108111705 A TW 108111705A TW 201943317 A TW201943317 A TW 201943317A
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film
plasma processing
pores
processing apparatus
plasma
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TW108111705A
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TWI704843B (zh
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石川和洋
日野高志
斎藤秀一
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日商京瓷股份有限公司
日商東芝高新材料公司
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    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32Gas-filled discharge tubes
    • H01J37/32431Constructional details of the reactor
    • H01J37/32458Vessel
    • H01J37/32477Vessel characterised by the means for protecting vessels or internal parts, e.g. coatings
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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Abstract

本發明之電漿處理裝置用構件具備基材及位於該基材上之至少一部分的稀土元素之氧化物、氟化物、氟氧化物或氮化物之膜。該膜之被暴露於電漿之表面之算術平均粗糙度Ra為0.01 μm以上0.1 μm以下,且於上述表面具有複數個氣孔,自相鄰之上述氣孔彼此之重心間距離之平均值減去上述氣孔之圓相當直徑之平均值所得之值為28 μm以上48 μm以下。本發明之電漿處理裝置具備上述所記載之電漿處理裝置用構件。

Description

電漿處理裝置用構件及具備其之電漿處理裝置
本發明係關於一種電漿處理裝置用構件及具備其之電漿處理裝置。
先前,作為要求較高之耐電漿性之構件,使用具備基材及位於該基材上之包含氧化釔之膜的電漿處理裝置用構件。
作為此種電漿處理裝置用構件,例如於專利文獻1中提出有基材之表面經純度為95質量%以上之Y2 O3 熔射皮膜被覆之電漿處理容器內構件。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本專利特開2005-217351號公報
[解決問題之技術手段]
本發明之電漿處理裝置用構件具備基材及位於該基材上之至少一部分的稀土元素之氧化物、氟化物、氟氧化物或氮化物之膜。該膜之被暴露於電漿之表面之算術平均粗糙度Ra為0.01 μm以上0.1 μm以下,並且於上述表面具有複數個氣孔,自相鄰之上述氣孔彼此之重心間距離之平均值減去上述氣孔之圓相當直徑之平均值所得之值為28 μm以上48 μm以下。
本發明之電漿處理裝置具備上述所記載之電漿處理裝置用構件。
以下,參照圖式,對本發明之電漿處理裝置用構件進行詳細說明。
如圖1B所示,本發明之電漿處理裝置用構件1具備基材2及位於基材2之至少一部分的稀土元素之氧化物、氟化物、氟氧化物或氮化物之膜3。而且,於圖1B中示有基材2之一個上表面2a經膜3被覆之例。
被暴露於電漿之膜3之表面(圖1B中之上表面,以下有時簡稱為表面)之算術平均粗糙度Ra為0.01 μm以上0.1 μm以下。又,於表面具有複數個氣孔4。圖1A中示有具有複數個氣孔4a、4b、…之例。再者,被暴露於電漿之膜3之表面包含被暴露於電漿,膜之厚度減少而新露出之面。
算術平均粗糙度Ra只要依據JIS B 0601-2013進行測定即可。具體而言,使用小坂研究所股份有限公司製造之表面粗糙度測定機(Surfcorder)SE500,將觸針之半徑設為5 μm、將測定長度設為2.5 mm、將臨界值設為0.8 mm即可。
再者,於圖1B中係為了使膜3之存在明確而進行記載,並非真實地表示基材2及膜3之厚度之相關關係。
而且,膜3係稀土元素之氧化物、氟化物、氟氧化物或氮化物(以下,將氧化物、氟化物、氟氧化物及氮化物統稱為化合物),作為稀土元素,可列舉釔(Y)、鈰(Ce)、釤(Sm)、釓(Gd)、鏑(Dy)、鉺(Er)及鐿(Yb)等。此處,於稀土元素為釔時,耐蝕性優異,並且價格較其他稀土元素便宜,因此成本效益較高。
釔之化合物之組成式例如可列舉Y2 O3-x (0≦x≦1)、YF3 、YOF、Y5 O4 F7 、Y5 O6 F7 、Y6 O5 F8 、Y7 O6 F9 、Y17 O14 F23 或YN。
再者,膜3並非僅包含稀土元素之化合物,根據膜3之形成時所使用之靶之純度及裝置構成等,有除稀土元素以外,亦包含氟(F)、鈉(Na)、鎂(Mg)、鋁(Al)、矽(Si)、磷(P)、硫(S)、氯(Cl)、鉀(K)、鈣(Ca)、鈦(Ti)、鉻(Cr)、錳(Mn)、鐵(Fe)、鈷(Co)、鎳(Ni)、銅(Cu)、鋅(Zn)、鍶(Sr)等之情形。構成膜3之成分之鑑定只要使用薄膜X射線繞射裝置進行即可。
基材2例如可列舉:石英、純度為99.999%(5N)以上之鋁、鋁6061合金等鋁合金、氮化鋁質陶瓷、氧化鋁質陶瓷等。所謂氮化鋁質陶瓷或氧化鋁質陶瓷,例如若為氧化鋁質陶瓷,則意指構成基材2之成分之合計100質量%中,將Al換算成Al2 O3 所得之值即氧化鋁之含量為90質量%以上的陶瓷。再者,氧化鋁質陶瓷有除氧化鋁以外,亦包含氧化鎂、氧化鈣及氧化矽等之情形。
而且,膜3具有複數個氣孔,自相鄰之氣孔彼此之重心間距離之平均值減去氣孔之圓相當直徑之平均值所得之值A為28 μm以上48 μm以下。
所謂值A為28 μm以上48 μm以下係指氣孔之數量較少,氣孔較小,且氣孔分散地存在。因此,滿足上述構成之電漿處理裝置用構件1之自氣孔之內部發生之微粒之個數較少。又,即便發生以氣孔為起點之微裂痕,亦以微裂痕之伸展可被附近之氣孔阻斷之程度分散地存在,因此伴隨著微裂痕之伸展發生之微粒之個數較少。
又,於本發明之電漿處理裝置用構件1中,膜3中之複數個氣孔之面積佔有率可為1.5面積%以上6面積%以下。於氣孔之面積佔有率為1.5面積%以上6面積%以下時,於被暴露於電漿之表面(包含被暴露於電漿,膜之厚度減少而新露出之面),即便發生微裂痕,微裂痕之伸展亦可被氣孔阻斷,因此伴隨著微裂痕之微粒之個數較少。又,由於被暴露於電漿之表面中之氣孔之面積率較低,故而自氣孔之內部發生之微粒之個數更少。
又,於本發明之電漿處理裝置用構件1中,膜3中之氣孔之球狀化率之平均值可為60%以上。於氣孔之球狀化率為該範圍時,變得不易於氣孔之周邊部蓄積殘留應力,因此於被暴露於電漿時變得不易自氣孔之周邊部發生微粒。
此處,所謂氣孔之球狀化率係指轉用由石墨面積法所規定之比率者,係由以下之數式(1)所規定者。
氣孔之球狀化率(%)=(氣孔之實際面積)/(氣孔之最小外接圓之面積)×100 (1)
尤其,氣孔之球狀化率之平均值為62%以上即可。
又,氣孔彼此之重心間距離之平均值、氣孔之圓相當直徑之平均值、面積佔有率及球狀化率可利用以下之方法求出。
首先,使用數位顯微鏡於100倍之倍率下對膜之表面進行觀察,例如將利用CCD(Charge Coupled Device,電荷耦合器件)相機於面積成為7.68 mm2 (橫向長度為3.2 mm,縱向長度為2.4 mm)之範圍內拍攝到之觀察像作為對象,使用圖像解析軟體「Azokun(ver2.52)」(註冊商標,Asahi Kasei Engineering股份有限公司製造,再者,於以下記載為圖像解析軟體「Azokun」之情形時,表示Asahi Kasei Engineering股份有限公司製造之圖像解析軟體),可利用分散度計測之重心間距離法之方法,而求出氣孔之重心間距離之平均值。
又,使用與上述觀察像相同之觀察像,藉由利用圖像解析軟體「Azokun」之粒子解析之方法進行解析,藉此可求出氣孔之圓相當直徑之平均值、面積佔有率及球狀化率。再者,於觀察像中符合於氣孔之區域看上去為較暗之區域,因此能夠識別。
作為重心間距離法及粒子解析之設定條件,例如將作為表示圖像之亮暗之指標的閾值設為140、將亮度設為暗、將小圖形去除面積設為1 μm2 、且設為有雜訊去除濾波器即可。再者,於進行上述測定時,閾值設為140,但只要根據觀察像之亮度調整閾值即可,於將亮度設為暗、將二值化之方法設為手動、將小圖形去除面積設為1 μm2 及設為有雜訊去除濾波器後,以於觀察像中大小隨閾值變化之標記與氣孔之形狀一致之方式調整閾值即可。
又,於本發明之電漿處理裝置用構件1中,膜3中之複數個氣孔之圓相當直徑之峰度Ku1可為0.5以上2以下。於氣孔之圓相當直徑之峰度Ku1為該範圍時,氣孔之圓相當直徑之分佈狹窄,並且異常大之圓相當直徑之氣孔較少,因此具有微裂痕之伸展抑制效果,並且自氣孔之內部發生之微粒之個數較少,耐電漿性優異。又,於在製膜後進行研磨之情形時,滿足上述構成之膜3由於偏磨耗較少,故而可以最小之研磨量形成所需之表面性狀。尤其,峰度Ku1為1.3以上1.9以下即可。
再者,於本發明之電漿處理裝置用構件1中,即便於已進行研磨之膜3中,氣孔之圓相當直徑之平均值等亦滿足上述範圍。
此處,所謂峰度Ku1係表示分佈之波峰及下擺與常態分佈相比有何種程度之不同的指標(統計量),於峰度Ku1>0之情形時,成為具有較尖之波峰及較長且較粗之下擺之分佈,於峰度Ku1=0之情形時,成為常態分佈,於峰度Ku1<0之情形時,分佈成為具有帶有弧度之波峰及較短且較細之尾部之分佈。再者,氣孔之圓相當直徑之峰度Ku1只要使用Excel(註冊商標,Microsoft Corporation)所具備之函數Kurt求出即可。
又,於本發明之電漿處理裝置用構件1中,膜3中之複數個氣孔之圓相當直徑之偏度Sk1可為3以上5.6以下。於氣孔之圓相當直徑之偏度Sk1為該範圍時,氣孔之圓相當直徑之平均值較小,並且異常大之圓相當直徑之氣孔較少,因此具有微裂痕之伸展抑制效果,並且自氣孔之內部發生之微粒之個數較少,耐電漿性優異。又,於在製膜後進行研磨之情形時,滿足上述構成之膜3由於偏磨耗較少,故而可以最小之研磨量形成所需之表面性狀。尤其,偏度Sk1為3.2以上5.3以下即可。
此處,所謂偏度Sk1係表示分佈自常態分佈偏斜何種程度即表示分佈之左右對稱性之指標(統計量),於偏度Sk1>0之情形時,分佈之下擺朝向右側,於偏度Sk1=0之情形時,分佈成為左右對稱,於偏度Sk1<0之情形時,分佈之下擺朝向左側。再者,氣孔之圓相當直徑之偏度Sk1只要使用Excel(註冊商標,Microsoft Corporation)所具備之函數SKEW求出即可。
又,於本發明之電漿處理裝置用構件1中,膜3中之氣孔彼此之重心間距離之峰度Ku2可為0.1以上0.5以下。於氣孔彼此之重心間距離之峰度Ku2為該範圍時,重心間距離之分佈狹窄,並且異常大之重心間距離較少,因此可具有微裂痕之伸展抑制效果,並且可抑制殘留應力之偏集存在。
又,於本發明之電漿處理裝置用構件1中,膜3中之氣孔彼此之重心間距離之偏度Sk2可為0.5以上1以下。
又,膜3之相對密度可為98%以上,尤其為99%以上即可。於相對密度為該範圍時,膜3為緻密質,因此即便暴露於電漿,膜3之厚度減少,亦可抑制微粒之發生。膜3之相對密度只要先使用薄膜X射線繞射裝置利用X射線反射率測定法(XRR)求出實測密度,求出實測密度相對於理論密度之比率即可。
如上所述,氣孔之佔有面積率較佳為1.5面積%以上6面積%以下。與此相對,膜3之相對密度較佳為98%以上。氣孔之佔有面積率與膜3之相對密度看上去無相關性。認為其原因在於,氣孔之佔有面積率係利用圖像解析,與此相對,膜之相對密度係使用XRR。XRR係使X射線透過膜3而進行測定。若於X射線之透過方向上,具有氣孔之部位與無氣孔之部位重疊,則亦有判定為「無氣孔」之情況。因此,利用XRR所獲得之膜3之相對密度係檢測出較高值。
如此,本發明之電漿處理裝置用構件1不易發生微粒,因此具備電漿處理裝置用構件1之電漿處理裝置之可靠性優異。
其次,對本發明之電漿處理裝置用構件之製造方法進行說明。
首先,對基材之製造方法進行說明。
準備平均粒徑為0.4~0.6 μm之氧化鋁(Al2 O3 )A粉末及平均粒徑為1.2~1.8 μm左右之氧化鋁B粉末。又,準備氧化矽(SiO2 )粉末作為Si源,準備碳酸鈣(CaCO3 )粉末作為Ca源。再者,氧化矽粉末係準備平均粒徑為0.5 μm以下之微粉者。又,為了獲得含有Mg之氧化鋁質陶瓷,使用氫氧化鎂粉末。再者,於以下之記載中,將氧化鋁A粉末及氧化鋁B粉末以外之粉末統稱為第1副成分粉末。
然後,分別稱量特定量之第1副成分粉末。其次,以質量比率成為40:60~60:40,且構成所獲得之氧化鋁質陶瓷之成分100質量%中將Al進行Al2 O3 換算所得之含量成為99.4質量%以上之方式稱量氧化鋁A粉末與氧化鋁B粉末,製成氧化鋁調合粉末。又,關於第1副成分粉末,較佳而言,首先把握氧化鋁調合粉末中之Na量,自製成氧化鋁質陶瓷之情形時之Na量換算成Na2 O,以該換算值與將構成第1副成分粉末之成分(於該例中為Si或Ca等)換算成氧化物所得之值的比成為1.1以下之方式稱量。
然後,將氧化鋁調合粉末、第1副成分粉末、相對於氧化鋁調合粉末與第1副成分粉末之合計100質量份為1~1.5質量份之PVA(聚乙烯醇)等黏合劑、100質量份之溶劑、及0.1~0.55質量份之分散劑加入至攪拌裝置中進行混合、攪拌,而獲得漿料。
其後,於將漿料進行噴霧造粒而獲得顆粒後,利用粉末加壓成形裝置、靜水壓加壓成形裝置等將該顆粒成形為特定形狀,並視需要實施切削加工而獲得基板狀之成形體。
其次,於將煅燒溫度設為1500℃以上1700℃以下、將保持時間設為4小時以上6小時以下而進行煅燒後,使用平均粒徑為1 μm以上5 μm以下之金剛石研磨粒與包含錫之研磨盤對形成膜3之側之表面進行研磨,藉此可獲得基材5。
其次,使用圖2對膜之形成方法進行說明。圖2係表示濺鍍裝置20之模式圖,濺鍍裝置20具備:腔室15、連結於腔室15內之氣體供給源13、位於腔室15內之陽極14及陰極12、以及連接於陰極12側之靶11。
作為膜之形成方法,將利用上述方法所獲得之基材5設置於腔室15內之陽極14側。又,於腔室15內之相反側,將以稀土元素、此處為以金屬釔作為主成分之靶11設置於陰極12側。於該狀態下,利用排氣泵將腔室15內設為減壓狀態,自氣體供給源13供給作為氣體G之氬氣及氧氣。
然後,利用電源對陽極14與陰極12之間施加電場,產生電漿P而進行濺鍍,藉此於基材5之表面形成金屬釔膜。再者,1次形成中之厚度為次奈米級。其次,進行金屬釔膜之氧化步驟。然後,以膜之厚度之合計成為10 μm以上200 μm以下之方式交替地進行金屬釔膜之形成與氧化步驟而進行積層,藉此可獲得具備釔之氧化物之膜的本發明之電漿處理裝置用構件。
又,為了獲得複數個氣孔之面積佔有率為1.5面積%以上6面積%以下的電漿處理裝置用構件,預先將與膜對向之基材之表面中之氣孔之面積佔有率設為1面積%以上5面積%以下即可。
又,為了獲得複數個氣孔之球狀化率之平均值為60%以上的電漿處理裝置用構件,預先將與膜對向之基材之表面中之氣孔之球狀化率之平均值設為62%以上即可。
又,為了獲得複數個氣孔之圓相當直徑之峰度Ku為0.5以上2以下的電漿處理裝置用構件,預先將與膜對向之基材之表面中之氣孔之圓相當直徑之峰度Ku設為0.6以上1.8以下即可。
又,為了獲得複數個氣孔之圓相當直徑之偏度Sk為3以上5.6以下的電漿處理裝置用構件,預先將與膜對向之基材之表面中之氣孔之圓相當直徑之偏度Sk設為3.1以上5.4以下即可。
又,為了形成釔之氟化物之膜,將氧化步驟變更為氟化步驟即可。
又,為了形成釔之氟氧化物之膜,依序交替地進行金屬釔膜之形成、氧化步驟及氟化步驟而進行積層即可。
又,為了形成釔之氮化物之膜,將氧化步驟變更為氮化步驟即可。
再者,自電源輸入之電力可為高頻電力及直流電力之任一者。
利用上述製造方法所獲得之本發明之電漿處理裝置用構件可使自氣孔之內部發生之微粒及伴隨著微裂痕之伸展而發生之微粒之個數均變少,因此例如亦可為讓用以產生電漿之高頻透過之高頻透過用窗構件、用以分配電漿生成用氣體之簇射板、用以載置半導體晶圓之基座等。
以下,參照圖式,對本發明之電漿處理裝置用構件進行詳細說明。
圖3A係利用光學顯微鏡對本發明之另一實施形態之電漿處理裝置用構件之被暴露於電漿之表面進行拍攝所獲得之照片,圖3B係模式性地表示本發明之另一實施形態之電漿處理裝置用構件之一例之剖視圖,圖3C係模式性地表示本發明之另一實施形態之電漿處理裝置用構件之另一例之剖視圖。
本發明之電漿處理裝置用構件30具備基材25及位於基材25上之至少一部分的稀土元素之氧化物之膜23。於被暴露於電漿之膜3之表面具有複數個開氣孔24的圖3A~圖3C中,示有具有複數個開氣孔24a、24b、…之例。又,示有於膜23之內部具有複數個閉氣孔26之例。
又,於圖3C中,示有膜3具備位於基材25上之第1層(下層)21及位於第1層(下層)21上之第2層(上層)22之例。第1層21之厚度t1 與第2層22之厚度t2 之比t1 :t2 例如為4~6:6~4。
基材25例如可列舉:石英、純度為99.999%(5N)以上之鋁、鋁6061合金等鋁合金、氮化鋁質陶瓷、氧化鋁質陶瓷等。所謂氮化鋁質陶瓷係指構成基材5之成分之合計100質量%中將Al換算成AlN所得之值即氮化鋁之含量為90質量%以上之陶瓷。又,所謂氧化鋁質陶瓷係指構成基材5之成分之合計100質量%中將Al換算成Al2 O3 所得之值即氧化鋁之含量為90質量%以上之陶瓷。再者,氧化鋁質陶瓷有除氧化鋁以外,亦包含氧化鎂、氧化鈣及氧化矽等之情形。
而且,膜23為稀土元素之氧化物,作為稀土元素,可列舉釔(Y)、鈰(Ce)、釤(Sm)、釓(Gd)、鏑(Dy)、鉺(Er)及鐿(Yb)等。此處,於稀土元素為釔時,耐蝕性優異,並且價格低於其他稀土元素,因此成本效益較高。
再者,膜23並非僅包含稀土元素之氧化物,根據膜3之形成時所使用之靶之純度及裝置構成等,有除稀土元素以外,亦包含氟(F)、鈉(Na)、鎂(Mg)、鋁(Al)、矽(Si)、磷(P)、硫(S)、氯(Cl)、鉀(K)、鈣(Ca)、鈦(Ti)、鉻(Cr)、錳(Mn)、鐵(Fe)、鈷(Co)、鎳(Ni)、銅(Cu)、鋅(Zn)、鍶(Sr)等之情形。
膜23之厚度為10 μm以上200 μm以下,膜23之微維氏硬度Hmv為7.5 GPa以上。又,關於膜23之主成分,例如於稀土元素為釔時,可為以缺失氧之Y2 O3-x (0≦x<1)表示之氧化釔,於氧化釔以該組成式表示之情形時,具有半導電性,因此可抑制膜23之表面之帶電。
此處,分別構成基材25及膜23之成分可藉由使用CuKα射線之X射線繞射裝置進行鑑定,各成分之含量例如可利用ICP(Inductively Coupled Plasma,感應耦合電漿)發光分光分析裝置或螢光X射線分析裝置求出。
關於本發明之電漿處理裝置用構件30,膜23之被暴露於電漿之表面之開氣孔24之面積佔有率為8面積%以下,並且開氣孔24之平均直徑為8 μm以下。
藉由為此種構成,於被暴露於電漿之表面,開氣孔24較少,且開氣孔24較小。因此,本發明之電漿處理裝置用構件30之耐電漿性優異。又,由於自開氣孔24之內部發生之微粒之個數較少,且所發生之微粒之大小較小,故而可持續長時間使用,並且具備本發明之電漿處理裝置用構件30之電漿處理裝置之可靠性優異。
此處,為了求出膜23之開氣孔24之平均直徑及面積佔有率,將被暴露於電漿之表面設為測定面。然後,使用數位顯微鏡(KEYENCE股份有限公司製造,VHX-5000),將落射照明設定為同軸落射,將照明強度設定為255,將符合於物鏡之ZS20透鏡設為100倍。其次,就面積成為7.223 mm2 (橫向長度為3.1 mm,縱向長度為2.33 mm)之範圍,於自動面積計測模式下選擇亮度,擷取較暗之區域(符合於開氣孔24之區域)後,將閾值設定為例如-20而進行測定,藉此可算出膜23之開氣孔24之平均直徑及面積佔有率。但,閾值只要對應於較暗區域之亮度適當設定即可。
被暴露於電漿之表面之開氣孔24之面積佔有率可為4面積%以下,開氣孔24之平均直徑可為4 μm以下。
又,關於膜23,亦可開氣孔24之平均直徑為8 μm以下,並且開氣孔24之面積佔有率為8面積%以下的區域相對於膜3之厚度,自表面起占5%以上。再者,所謂開氣孔24之面積佔有率,僅適用於被暴露於電漿之表面,但此處,於計算面積佔有率時,對表面進行研磨而於面上出現之氣孔亦設為開氣孔24。
於圖3C所示之例之電漿處理裝置用構件30中,該區域符合於第2層22。於開氣孔24之平均直徑為8 μm以下,並且開氣孔24之面積佔有率為8面積%以下者不僅存在於表面,而且自表面遍及內部時,即便於被暴露於電漿而出現之表面,自開氣孔24之內部發生之微粒之個數亦較少,且所發生之微粒之大小亦較小。因此,可持續長時間良好地進行電漿處理。
又,膜23具備自位於基材25之與膜23對向之面的凹部27向厚度方向延伸之空隙部28,空隙部28之前端亦可封閉於膜23內。此處,所謂凹部27係指基材25之與膜23對向之面中之開氣孔或空隙,於形成膜23之前為基材25之表面。
於膜23具備空隙部28時,即便重複進行升溫及降溫,亦可抑制殘留應力之蓄積,並且由於空隙部8未連通至外部,故而位於空隙部28內之微粒不會排出至膜23外。
又,沿膜23之厚度方向剖視之空隙部28之寬度亦可膜23之表面側窄於基材25之凹部27側。於為此種構成時,即便膜23被暴露於電漿,膜厚減少,空隙部8之前端開口,亦相較膜23之表面側之空隙部8之寬度大於基材25之凹部27側時,位於空隙部28內之微粒更不易排出至膜23外。
又,基材25包含以氧化鋁作為主成分之陶瓷,基材25亦可於與膜23對向之基材25之被覆面上含有釔鋁石榴石(YAG)、釔鋁單斜晶體(YAM)及釔鋁鈣鈦礦(YAP)之至少任一者。
於為此種構成時,膜23對基材25之化學鍵結力變高,因此可提高膜23對基材25之密接強度。
其次,對本發明之電漿處理裝置用構件之製造方法進行說明。
首先,對基材之製造方法進行說明。
準備平均粒徑為0.4~0.6 μm之氧化鋁(Al2 O3 )A粉末及平均粒徑為1.2~1.8 μm左右之氧化鋁B粉末。又,準備氧化矽(SiO2 )粉末作為Si源,準備碳酸鈣(CaCO3 )粉末作為Ca源。再者,氧化矽粉末係準備平均粒徑為0.5 μm以下之微粉者。又,為了獲得含有Mg之氧化鋁質陶瓷,使用氫氧化鎂粉末。再者,於以下之記載中,將氧化鋁A粉末及氧化鋁B粉末以外之粉末統稱為第1副成分粉末。
然後,分別稱量特定量之第1副成分粉末。其次,以質量比率成為40:60~60:40,且構成所獲得之氧化鋁質陶瓷之成分100質量%中將Al進行Al2 O3 換算所得之含量成為99.4質量%以上之方式稱量氧化鋁A粉末與氧化鋁B粉末,製成氧化鋁調合粉末。又,關於第1副成分粉末,較佳而言,首先把握氧化鋁調合粉末中之Na量,自製成氧化鋁質陶瓷之情形時之Na量換算成Na2 O,以該換算值與將構成第1副成分粉末之成分(於該例中為Si或Ca等)換算成氧化物所得之值的比成為1.1以下之方式稱量。
然後,將氧化鋁調合粉末、第1副成分粉末、相對於氧化鋁調合粉末與第1副成分粉末之合計100質量份為1~1.5質量份之PVA(聚乙烯醇)等黏合劑、100質量份之溶劑、及0.1~0.55質量份之分散劑加入至攪拌裝置中進行混合、攪拌,而獲得漿料。
其後,於將漿料進行噴霧造粒而獲得顆粒後,利用粉末加壓成形裝置、靜水壓加壓成形裝置等將該顆粒成形為特定形狀,並視需要實施切削加工而獲得基板狀之成形體。
其次,於將煅燒溫度設為1500℃以上1700℃以下、將保持時間設為4小時以上6小時以下而進行煅燒後,使用平均粒徑為1 μm以上5 μm以下之金剛石研磨粒與包含錫之研磨盤對形成膜之側之表面進行研磨,藉此可獲得基材25。
其次,使用圖4對膜之形成方法進行說明。圖4係表示濺鍍裝置40之模式圖,濺鍍裝置40具備:腔室35、連結於腔室35內之氣體供給源33、位於腔室35內之陽極34及陰極32、以及連接於陰極32側之靶11。
作為膜之形成方法,將利用上述方法所獲得之基材25設置於腔室35內之陽極34側。又,於腔室35內之相反側,將以稀土元素、此處為以金屬釔作為主成分之靶31設置於陰極32側。於該狀態下,利用排氣泵將腔室15內設為減壓狀態,自氣體供給源33供給作為氣體G之氬氣及氧氣。
然後,利用電源對陽極34與陰極32之間施加電場,產生電漿P而進行濺鍍,藉此於基材25之表面形成金屬釔膜。再者,1次形成中之厚度為次奈米級。其次,進行金屬釔膜之氧化步驟。然後,以膜之厚度之合計成為10 μm以上200 μm以下之方式交替地進行金屬釔膜之形成與氧化步驟而進行積層,藉此可獲得第1層21。
此處,為了獲得於基材25之相對於膜之對向面上含有釔鋁石榴石(YAG)、釔鋁單斜晶體(YAM)及釔鋁鈣鈦礦(YAP)之至少任一者的電漿處理裝置用構件,只要將濺鍍中之基材25之溫度設定為400℃以上即可。再者,自電源輸入之電力可為高頻電力及直流電力之任一者。
其次,將形成有第1層之基材25自腔室35取出,對第1層21之成膜面進行平滑化處理。此處,所謂平滑化處理,例如為研磨,使用平均粒徑為1 μm以上5 μm以下之金剛石研磨粒與包含錫之研磨盤,對第1層21之成膜面進行研磨而成為處理面(研磨面)即可。
再者,為了獲得具備自位於基材25之與膜對向之面的凹部27向厚度方向延伸之空隙部28,且空隙部28之前端封閉於膜23內的電漿處理裝置用構件,準備基材25之與膜對向之面中之開氣孔之平均直徑為1 μm以上8 μm以下者,以開氣孔之平均直徑成為0.1 μm以上5 μm以下之方式對第1層21之成膜面進行研磨即可。
又,若使用與膜對向之面中之開氣孔之平均直徑為1 μm以上8 μm以下者作為基材25,利用圖2所示之濺鍍裝置40形成膜,則沿膜23之厚度方向剖視之空隙部28之寬度係膜23之表面側變得窄於基材5之凹部27側,若以開氣孔之平均直徑成為0.1 μm以上5 μm以下之方式對第1層21之成膜面進行研磨,形成下述第2層22,則空隙部28被封閉於膜23內。
然後,利用與獲得第1層21之方法相同之方法,於第1層21之處理面上形成以氧化釔作為主成分之第2層22,藉此可獲得本發明之電漿處理裝置用構件30。
利用上述製造方法所獲得之本發明之電漿處理裝置用構件30可減少自開氣孔內部發生之微粒之個數,並且可減小所發生之微粒之大小,因此例如亦可為讓用以產生電漿之高頻透過之高頻透過用窗構件、用以分配電漿生成用氣體之簇射板、用以載置半導體晶圓之基座等。
本發明可於不脫離其精神或主要特徵之情況下,利用其他各種形態實施。因此,上述實施形態於所有方面僅為例示,本發明之範圍係申請專利範圍所揭示者,且不受說明書正文任何約束。進而,屬於申請專利範圍之變化或變更均為本發明之範圍內者。例如,由本發明之實施形態之組合所產生之發明亦為本發明之範圍內者。
1‧‧‧電漿處理裝置用構件
2‧‧‧基材
2a‧‧‧上表面
3‧‧‧膜
4‧‧‧氣孔
4a‧‧‧氣孔
4b‧‧‧氣孔
5‧‧‧基材
11‧‧‧靶
12‧‧‧陰極
13‧‧‧氣體供給源
14‧‧‧陽極
15‧‧‧腔室
20‧‧‧濺鍍裝置
21‧‧‧第1層
22‧‧‧第2層
23‧‧‧膜
24‧‧‧開氣孔
24a‧‧‧開氣孔
24b‧‧‧開氣孔
24c‧‧‧開氣孔
24d‧‧‧開氣孔
24e‧‧‧開氣孔
25‧‧‧基材
26‧‧‧閉氣孔
27‧‧‧凹部
28‧‧‧空隙部
30‧‧‧電漿處理裝置用構件
31‧‧‧靶
32‧‧‧陰極
33‧‧‧氣體供給源
34‧‧‧陽極
35‧‧‧腔室
40‧‧‧濺鍍裝置
P‧‧‧電漿
本發明之目的、特色及優點應根據下述詳細之說明及圖式而變得更明確。
圖1A係利用光學顯微鏡對本發明之一實施形態之電漿處理裝置用構件之被暴露於電漿之表面進行拍攝所獲得之照片。
圖1B係本發明之一實施形態之電漿處理裝置用構件之側視圖。
圖2係表示用以獲得本發明之一實施形態之電漿處理裝置用構件的濺鍍裝置之模式圖。
圖3A係利用光學顯微鏡對本發明之另一實施形態之電漿處理裝置用構件之被暴露於電漿之表面進行拍攝所獲得之照片。
圖3B係模式性地表示本發明之另一實施形態之電漿處理裝置用構件之剖視圖。
圖3C係模式性地表示本發明之另一實施形態之電漿處理裝置用構件之另一例之剖視圖。
圖4係表示用以獲得本發明之另一實施形態之電漿處理裝置用構件的濺鍍裝置之模式圖。

Claims (7)

  1. 一種電漿處理裝置用構件,其具備: 基材、及 位於該基材上之至少一部分的稀土元素之氧化物、氟化物、氟氧化物或氮化物之膜, 該膜之被暴露於電漿之表面之算術平均粗糙度Ra為0.01 μm以上0.1 μm以下,且於上述表面具有複數個氣孔,自相鄰之上述氣孔彼此之重心間距離之平均值減去上述氣孔之圓相當直徑之平均值所得之值為28 μm以上48 μm以下。
  2. 如請求項1之電漿處理裝置用構件,其中複數個上述氣孔之面積佔有率為1.5面積%以上6面積%以下。
  3. 如請求項1或2之電漿處理裝置用構件,其中複數個上述氣孔之球狀化率之平均值為60%以上。
  4. 如請求項1至3中任一項之電漿處理裝置用構件,其中複數個上述氣孔之圓相當直徑之峰度Ku1為0.5以上2以下。
  5. 如請求項1至4中任一項之電漿處理裝置用構件,其中複數個上述氣孔之圓相當直徑之偏度Sk1為3以上5.6以下。
  6. 如請求項1之電漿處理裝置用構件,其中上述氣孔彼此之重心間距離之峰度Ku2為0.1以上0.5以下。
  7. 一種電漿處理裝置,其具備如請求項1至6中任一項之電漿處理裝置用構件。
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