TW201623481A - 電漿處理檢測油墨組成物及使用其之電漿處理檢測指示劑 - Google Patents
電漿處理檢測油墨組成物及使用其之電漿處理檢測指示劑 Download PDFInfo
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Abstract
本發明係提供一種電漿處理檢測油墨組成物,其係為了形成藉由電漿處理而變色之變色層的油墨組成物;且可將因電漿處理所導致變色層氣體化或形成為微細碎屑而飛散之情形,抑制在不會影響電子設備特性之程度,並且,具有良好耐熱性。
本發明,具體而言,係提供一種電漿處理檢測油墨組成物,其特徵為其係為了形成藉由電漿處理而變色之變色層的油墨組成物;且該油墨組成物係含有金屬氧化物粒子及接著劑樹脂;前述金屬氧化物粒子係含有選自Mo、W、Sn、V、Ce、Te及Bi所成群中至少一種元素者。
Description
本發明係關於一種電漿處理檢測油墨組成物及使用其之電漿處理檢測指示劑,特別係關於一種作為電子設備製造裝置所使用之指示劑非常有效,且使用金屬氧化物粒子作為變色成分之電漿處理檢測油墨組成物及使用其之電漿處理檢測指示劑。
傳統上,電子設備的製造工程,係對於電子設備基板(被處理基板)進行各種處理者。例如,電子設備為半導體時,投入半導體晶圓(晶圓)後,經過形成絕緣膜或金屬膜的成膜步驟、形成光阻圖型之光蝕刻步驟、使用光阻圖型對於膜進行加工之蝕刻步驟、在半導體晶圓上形成導電層之雜質添加步驟(又稱為摻雜或擴散步驟)、研磨具有凹凸之膜的表面使其平坦之CMP步驟(化學機械性研磨)等,至確認圖型之完成結果或電特性而進行之半導體晶圓電特性檢查(有將至此之步驟總稱為前步驟的情形)。接著,開始進行形成半導體晶片的後步驟。如此之前步驟,不限於電子設備為半導體時進行,同樣亦應用在製造其他電子設備(發光二極體(LED)、太陽能電池、液晶顯示器、有機EL(Electro-Luminescence)顯示器等)之情形。
前步驟,係除了上述步驟,更包含其他使用電漿、臭氧、紫外線等的洗淨步驟;藉由電漿、含有自由基的氣體等進行之光阻圖型的除去步驟(又稱灰化或灰化去除);等之步驟。此外,上述成膜步驟,係在晶圓表面使反應性氣體發生化學反應而成膜之CVD、或形成金屬膜之濺射等,此外上述蝕刻步驟,可列舉出:藉由在電漿中的化學反應之乾式蝕刻、藉由離子束之蝕刻等。在此,電漿係指氣體呈電離狀態,離子、自由基及電子存在於其內部。
電子設備的製造步驟,為了確保電子設備的性能、信賴性等,必須適當地進行上述的各種處理。因此,例如,代表成膜步驟、蝕刻步驟、灰化步驟、雜質添加步驟、洗淨步驟等之電漿處理,為了確認電漿處理的完成,可實施:使用分光裝置分析電漿的發光、具有在電漿處理環境下會變色之變色層的電漿處理檢測指示劑等,從而確認是否完成。
作為電漿處理檢測指示劑的例子,專利文獻1揭示一種油墨組成物,其係含有1)蒽醌系色素、偶氮系色素及酞菁系色素中之至少1種,以及2)接著劑樹脂、陽離子系界面活性劑及增量劑中至少1種的電漿處理檢測用油墨組成物,其特徵為:前述電漿處理所使用的電漿產生用氣體含有氧氣及氮氣中至少1種;並且,揭示一種電漿處理檢測指示劑,其係於基材上形成有該油墨組成物所成之變色層。
此外,專利文獻2揭示一種油墨組成物,其係含有1)蒽醌系色素、偶氮系色素及次甲基系色素中至少1種,以及2)接著劑樹脂、陽離子系界面活性劑及增量劑中之至少1種的惰性氣體電漿處理檢測用油墨組成物,其特徵為:前述惰性氣體係含有選自氦、氖、氩、氪及氙所成群
中至少1種;並且,揭示一種電漿處理檢測指示劑,其係於基材上形成有該油墨組成物所成之變色層。
然而,使用發光分析或傳統之電漿處理檢測指示劑的確認方法,作為電子設備製造裝置所使用之指示劑會有性能不充分之情形。具體而言,使用發光分析的確認方法,限定為必須從設置於電子設備製造裝置上的窗口進行的測定及分析,因此電子設備製造裝置內若無法看清楚,容易使測定及分析難以有效進行。此外,使用傳統的電漿處理檢測指示劑時,藉由變色層的變色確認電漿處理是否完成雖然係簡便且優良的手段,但卻有作為變色材料的有機色素因電漿處理而氣體化或形成微細的碎屑飛散,而降低電子設備製造裝置的高清淨性或導致電子設備的汙染(交叉汙染)之疑慮。此外,亦有變色材料的氣體化對於電子設備製造裝置的真空性造成影響之疑慮。進一步,變色材料為有機色素的傳統之變色層,由於其耐熱性不充分,故在電子設備製造裝置為高溫時難以作為指示劑使用之問題。
因此,目前正期望開發一種具有藉由電漿處理而變色之變色層的指示劑,且可將因電漿處理所導致變色材料氣體化或形成為微細碎屑而飛散之情形,抑制在不會影響到電子設備特性的程度,並且,具有良好耐熱性的電漿處理檢測指示劑。
【專利文獻1】日本特開2013-98196號公報
【專利文獻2】日本特開2013-95764號公報
本發明之目的係提供一種形成藉由電漿處理而變色之變色層的油墨組成物,且可將因電漿處理所導致變色層氣體化或形成為微細碎屑而飛散之情形,抑制在不會影響到電子設備特性的程度,並且,具有良好耐熱性的電漿處理檢測油墨組成物。此外,另一目的係提供一種使用前述電漿處理檢測油墨組成物的電漿處理檢測指示劑。
本發明人為達到上述目的而深入研究的結果,發現作為電漿處理檢測油墨組成物所包含之變色材料使用特定的金屬氧化物粒子時可達成上述目的,從而完成本發明。
亦即,本發明係關於下述的電漿處理檢測油墨組成物及使用其之電漿處理檢測指示劑。
1.一種電漿處理檢測油墨組成物,其特徵為其係用以形成藉由電漿處理而變色之變色層的油墨組成物;且該油墨組成物係含有金屬氧化物粒子及接著劑樹脂;前述金屬氧化物粒子係含有選自Mo、W、Sn、V、Ce、Te及Bi所成群中至少一種元素者。
2.如上述項1所記載之電漿處理檢測油墨組成物,其中,前述金屬氧化
物粒子,係含有選自氧化鉬粒子(IV)、氧化鉬粒子(VI)、氧化鎢粒子(VI)、氧化錫粒子(IV)、氧化釩粒子(II)、氧化釩粒子(III)、氧化釩粒子(IV)、氧化釩粒子(V)、氧化鈰粒子(IV)、氧化碲粒子(IV)、氧化鉍粒子(III)、碳酸氧化鉍粒子(III)及氧化硫酸釩粒子(IV)所成群中至少一種者。
3.如上述項1或2所記載之電漿處理檢測油墨組成物,其中,前述金屬氧化物粒子,係含有選自氧化鉬粒子(Ⅵ)、氧化鎢粒子(Ⅵ)、氧化釩粒子(III)、氧化釩粒子(V)及氧化鉍粒子(III)所成群中至少一種者。
4.如上述項1~3中任一項所記載之電漿處理檢測油墨組成物,其中,前述金屬氧化物粒子之平均粒徑為50μm以下。
5.如上述項1~4中任一項所記載之電漿處理檢測油墨組成物,其中,前述接著劑樹脂,係含有選自石油烴系樹脂、乙烯基樹脂、丁醛樹脂、醇酸樹脂、丙烯酸樹脂、環氧樹脂、聚氨酯樹脂、丙烯腈樹脂、氟樹脂、矽樹脂、甲醛樹脂、聚酯樹脂、聚乙烯樹脂、酮樹脂、聚醯胺樹脂、馬來酸樹脂、古馬隆樹脂、聚醯亞胺樹脂、聚醚醚酮樹脂、脂環族樹脂所成群中至少一種者。
6.如上述項1~5中任一項所記載之電漿處理檢測油墨組成物,其中,前述接著劑樹脂之軟化點為70℃以上。
7.一種電漿處理檢測指示劑,其特徵為其之基材上,係具有由上述項1~6中任一項所記載之電漿處理檢測油墨組成物的硬化塗膜所形成之變色層。
8.如上述項7所記載之電漿處理檢測指示劑,其中,其係電子設備製造裝置所使用之指示劑。
9.如上述項8所記載之電漿處理檢測指示劑,其中,前述指示劑的形狀,係與前述電子設備製造裝置所使用之電子設備基板的形狀相同者。
10.如上述項8或9所記載之電漿處理檢測指示劑,其中,前述電子設備製造裝置,係進行有選自成膜步驟、蝕刻步驟、灰化步驟、雜質添加步驟及洗淨步驟所成群中至少一種的電漿處理者。
11.如上述項7~10中任一項所記載之電漿處理檢測指示劑,其中,其係具有藉由電漿處理而不變色之非變色層。
12.如上述項11所記載之電漿處理檢測指示劑,其中,前述非變色層,係含有選自氧化鈦(IV)、氧化鋯(IV)、氧化釔(III)、硫酸鋇、氧化鎂、二氧化矽、氧化鋁、鋁、銀、釔、鋯、鈦、白金所成群中至少一種者。
13.如上述項11或12所記載之電漿處理檢測指示劑,其中,前述基材上,係依序形成有前述非變色層及前述變色層;前述非變色層,係鄰接於前述基材的主面上而形成;前述變色層,係鄰接於前述非變色層的主面上而形成。
使用本發明之電漿處理檢測油墨組成物的電漿處理檢測指示劑,作為變色層所含變色材料係使用特定的金屬氧化物粒子,該變色層藉由電漿處理而導致金屬氧化物粒子的價數改變,從而發生化學性變色,因此藉由電漿處理使變色層氣體化或成為微細碎屑飛散之情形,可被抑制在不影響電子設備特性的程度。此外,因變色材料係由無機成分所構成,
故可具有耐受電子設備製造時的過程溫度之耐熱性。如此之本發明的指示劑,不僅為高清淨性更具有真空性,作為要求在高溫下進行處理的電子設備製造裝置所使用之電漿處理檢測指示劑係特別有用。又,作為電子設備電子,可列舉例如:半導體、發光二極體(LED)、半導體雷射、功率設備、太陽能電池、液晶顯示器、有機EL顯示器等。
【圖1】試驗例1所使用容量結合電漿(平行平板型;Capacitively Coupled Plasma)型之電漿蝕刻裝置(使用13.56MHz之高頻電源)的概略斷面圖。又,圖中之TMP係表示渦輪分子泵(Turbo-Molecular Pump)的簡稱。
【圖2】表示試驗例2中升溫與真空度的關係之圖表。
【圖3】試驗例2中升溫至200℃時的變色層的狀態之示意圖。(a)表示為實施例1、(b)表示為傳統例1的狀態。
以下,詳細說明本發明之電漿處理檢測油墨組成物及電漿處理檢測指示劑。
電漿處理檢測油墨組成物
本發明之電漿處理檢測油墨組成物(以下,亦稱為「本發明之油墨組成物」),係為了形成藉由電漿處理而變色之變色層的油墨組成物,其特徵為其係含有金屬氧化物粒子及接著劑樹脂;前述金屬氧化物粒子係含選自
Mo、W、Sn、V、Ce、Te及Bi所成群中至少一種元素者。
使用本發明之油墨組成物所得之電漿處理檢測指示劑(以下,亦稱為「本發明之指示劑」),其相當於油墨組成物之硬化塗膜的變色層所含變色材料係特定的金屬氧化物粒子,該變色層藉由電漿處理而導致金屬氧化物粒子的價數改變,從而發生化學性變色,因此藉由電漿處理使變色層氣體化或成為微細碎屑飛散之情形,可被抑制在不影響電子設備特性的程度。此外,因變色材料係由無機成分所構成,故可具有耐受電子設備製造時的過程溫度電子之耐熱性。
本發明之油墨組成物,係含有金屬氧化物粒子及接著劑樹脂;且前述金屬氧化物粒子係含選自Mo、W、Sn、V、Ce、Te及Bi所成群中至少一種元素。其他,亦含有為了溶解接著劑樹脂之溶劑,並可進一步在不影響本發明效果的範圍含有增黏劑等習知的添加劑作為任意成分更。以下,對於構成本發明之油墨組成物之各成分進行說明。
(金屬氧化物粒子)
金屬氧化物粒子,可列舉為選自氧化鉬粒子(IV)、氧化鉬粒子(VI)、氧化鎢粒子(VI)、氧化錫粒子(IV)、氧化釩粒子(II)、氧化釩粒子(III)、氧化釩粒子(IV)、氧化釩粒子(V)、氧化鈰粒子(IV)、氧化碲粒子(IV)、氧化鉍粒子(III)、碳酸氧化鉍粒子(III)及氧化硫酸釩粒子(IV)所成群中至少一種。又,金屬氧化物粒子,雖然亦容許分子中有若干之結晶水,但因有水分子(水分氣體)放出的可能性,故較佳係未含有結晶水者。
特別係,本發明係藉由電漿處理而使金屬氧化物粒子的價數改變,從而發生化學性變色。相關的金屬氧化物粒子與傳統之變色材料的
有機色素相異,不僅可將因電漿處理所導致變色材料氣體化或形成為微細碎屑而飛散之情形,抑制在不會影響電子設備特性的程度,更可具有耐受電子設備製造時的過程溫度之耐熱性。
金屬氧化物粒子,在上述之中,考慮到藉由電漿處理的變色性,較佳可列舉選自氧化鉬粒子(Ⅵ)、氧化鎢粒子(Ⅵ)、氧化釩粒子(III)、氧化釩粒子(V)及氧化鉍粒子(III)所成群中至少一種。
金屬氧化物粒子之平均粒徑雖無限定,但根據提高藉由電漿處理的變色性(感受性)之觀點而言,係以50μm以下為佳,約0.01~10μm更佳。又,本說明說中的平均粒徑,係以雷射衍射‧散射式粒徑分佈測定裝置(製品名:MICROTRACK MT3000、日機装製)之方法而測定之值。
本發明之油墨組成物中的金屬氧化物粒子之含量雖無限定,但以10~90重量%為佳,30~60重量%更佳。金屬氧化物粒子之含量若未達10重量%時,會有降低藉由電漿處理的變色性之疑慮。此外,金屬氧化物粒子之含量若超過90重量%,不僅成本較高,在形成相當於油墨組成物的乾燥塗膜之變色層時,會有變色層之對於基材的定著性下降之疑慮。
(接著劑樹脂)
接著劑樹脂,僅需係在基材上形成變色層時,可賦予變色層良好的定著性者即可。如此之接著劑樹脂,可列舉例如:選自石油烴樹脂、乙烯基樹脂、丁醛樹脂、醇酸樹脂、丙烯酸樹脂、環氧樹脂、聚氨酯樹脂、丙烯腈樹脂、氟樹脂、矽樹脂、甲醛樹脂、聚酯樹脂、聚乙烯樹脂、酮樹脂、聚醯胺樹脂、馬來酸樹脂、古馬隆樹脂、聚醯亞胺樹脂、聚醚醚酮樹脂、脂環族樹脂所成群中至少一種。此等接著劑樹脂,通常,可由後述的溶劑
溶解而包含於油墨組成物中。
此等接著劑樹脂中,較佳係軟化點為70℃以上之樹脂,其中,軟化點為130℃以上之聚醯亞胺樹脂、松香變性酮樹脂、矽樹脂、丁醛樹脂、聚醯胺樹脂、氟樹脂等更佳。特別係根據給予變色層的變色層較少影響,且進一步具有優異之耐熱性並同時可將電漿處理所發生之氣體化抑制在較低之觀點而言,以丁醛樹脂中之聚乙烯醇縮丁醛樹脂(PVB樹脂)為佳。
本發明中,接著劑樹脂除了上述例示以外,亦可使用熱硬化型樹脂、光硬化型樹脂等。使用此等樹脂時,因係藉由熱、光等的照射而重合硬化等使樹脂硬化,故在油墨組成物中可使用藉由重合硬化等而成為目標之接著劑樹脂的樹脂前軀體。又,熱、光等的照射,如後述僅對於油墨組成物的塗膜進行即可。
本發明之油墨組成物中的接著劑樹脂之含量可因應接著劑樹脂之種類等,並無限定,惟以0.5~30重量%為佳,5~10重量%更佳。接著劑樹脂之含量未達3重量%及超過15重量%任一者時,有變色層之對於基材的定著性下降之疑慮。
(溶劑)
溶劑,僅要可溶解接著劑樹脂,並賦予油墨組成物良好的塗佈性者即可,並無限定。例如,使用石油系溶劑等為佳,特別係乙二醇單丁基醚(丁基溶纖劑)、乙二醇單乙醚(乙基溶纖劑)等為更佳。
本發明之油墨組成物中的溶劑之含量雖可因應接著劑樹脂之種類等,並無限定,但以10~70重量%為佳,25~40重量%更佳。溶劑
之含量未達10重量%及超過70重量%任一者時,有降低油墨組成物的塗佈性之疑慮。此外,溶劑之含量為過量時,乾燥油墨組成物需耗費較多時間。
(增黏劑等添加劑)
本發明之油墨組成物,除了上述成分以外可含有增黏劑等習知的添加劑作為任意成分。增黏劑,較佳係可賦予油墨組成物增黏效果並抑制金屬氧化物粒子的沉澱同時提升塗佈性者。
增黏劑,例如,矽酸鹽礦物質及矽酸鹽化合物中至少一種為佳,其等中以二氧化矽為特佳。
本發明之油墨組成物中的增黏劑之含量雖無限定,惟若添加時以10重量%以下為佳,3~6重量%更佳。增黏劑之含量若超過10重量%,有油墨組成物高黏度化,導致塗佈性下降之虞。此外,含有二氧化矽作為增黏劑時,可賦予變色層下地隱蔽性,故基於下地隱蔽性,可得到提升變色層之變色性的效果。
調製本發明之油墨組成物時,可藉由習知的方法將上述成分混合、攪拌而調製。
電漿處理檢測指示劑
本發明之指示劑,其特徵係在基材上,具有由本發明之油墨組成物的硬化塗膜所形成之變色層。又,上述硬化塗膜,包含:藉由除去溶劑而形成之乾燥塗膜以外、藉由熱、光等之照射使樹脂前驅體重合硬化等從而形成硬化塗膜的兩種態樣。
變色層之形成方法,只要係在基材上形成油墨組成物之硬化塗膜之方法即可,並無限定,例如,可藉由將油墨組成物塗佈於基板上,
蒸餾溶劑後放置大氣中乾燥而形成變色層。此外,因應接著劑樹脂(及其樹脂前軀體)之種類,亦可以熱、光等之照射取代乾燥或乾燥並進一步進行熱、光等之照射。
(基材)
基材,只要係可形成及支持變色層者即可,並無特別限制。例如,可使用金屬或合金、陶瓷、石英、玻璃、混凝土、樹脂類、纖維類(不織布,織布、玻璃纖維濾紙、其他纖維片材)、此等之複合材料等。此外,一般作為電子設備基板而廣被習知的矽、砷化鎵、碳化矽、藍寶石、玻璃、氮化鎵、鍺等亦可採用作為本發明之指示劑的基材。基材的厚度可因應指示劑的種類進行適當設定。
上述樹脂類,可使用熱可塑性樹脂及熱硬化性樹脂中任一者,可列舉例如:PE(聚乙烯)樹脂、PP(聚丙烯)樹脂、PS(聚苯乙烯)樹脂、AS(丙烯腈苯乙烯)樹脂、ABS(丙烯腈-丁二烯-苯乙烯共聚物)樹脂、乙烯基樹脂、PMMA(丙烯酸-甲基丙烯酸)樹脂、PET(聚對苯二甲酸乙酯)樹脂、PA(尼龍)樹脂、POM(聚甲醛)樹脂、PC(聚碳酸酯)樹脂、PBT(聚對苯二甲酸乙二醇酯)樹脂、PPS(聚苯硫醚)樹脂、PI(聚醯亞胺)樹脂、PEI(聚醚醯亞胺)樹脂、PSF(聚碸)樹脂、PTFE(特氟隆(登録商標))樹脂、PCTFE(氟)樹脂、PAI(聚醯胺醯亞胺)樹脂、PF(酚醛)樹脂、UF(尿素)樹脂、MF(三聚氰胺)樹脂、UP(不飽和聚酯)樹脂、PU(聚氨酯)樹脂、PDAP(烯丙基)樹脂、EP(環氧)樹脂、SI(矽酮)樹脂、FF(呋喃)樹脂、PEEK(聚醚醚酮)樹脂等。此等樹脂之中,根據具有耐熱性及變色層的良好定著性的觀點而言,PI樹脂為佳。
(變色層)
基材上形成變色層時油墨組成物之塗佈方法並無限定,例如,可廣泛採用旋轉塗佈、狹縫塗佈、噴射、浸漬塗佈等習知的塗佈方法、絲網印刷、凹版印刷、膠版印印、凸版印刷、柔版印刷等習知的印刷方法等。本發明中,塗佈係包含塗佈以外之印刷、浸漬等之概念。
塗佈油墨組成物後,將塗膜乾燥。乾燥溫度雖無限定,但通常約80~200℃為佳,約100~150℃更佳。
本發明之指示劑中變色層的厚度雖無限定,但約500nm~2mm為佳,約1~100μm更佳。
(非變色層)
本發明之指示劑,亦可為了提高變色層的辨識性而設置電漿處理後不會變色之非變色層作為下地層。非變色層,需求係具有耐熱性且可抑制氣體化。非變色層,較佳係白色層、金屬層等。
白色層,可藉由例如:氧化鈦(IV)、氧化鋯(IV)、氧化釔(III)、硫酸鋇、氧化鎂、二氧化矽、氧化鋁等形成。
金屬層,可藉由例如:鋁、銀、釔、鋯、鈦、白金等形成。
形成非變色層之方法,例如,除了可藉由物理蒸著(PVD)、化学蒸著(CVD)、濺射,亦可藉由調製含有可成為非變色層之物質的漿料後,將該漿料塗佈於基板上蒸餾溶劑後在大氣中燒成而形成。將上述漿料塗佈、印刷之方法,例如,可廣泛採用旋轉塗佈、狹縫塗佈、噴霧塗佈、浸漬塗佈、絲網印刷、凹版印刷、膠版印刷、凸版印刷、柔版印刷等習知的塗佈方法、印刷方法等。非變色層之厚度可因應指示劑的種類進行適當
設定。
本發明,只要能確認電漿處理是否完成,變色層與非變色層不論如何組合皆可。例如,可將變色層及非變色層形成為藉由變色層的變色而開始導致變色層與非變色層具有色差從而可辨識,或將兩者形成為因變色而開始使變色層及非變色層之色差消失。本發明,特別係將變色層及非變色層形成為藉由變色而開始導致變色層與非變色層間有色差從而可辨識為佳。
可由色差進行辨識之情形,可例如將變色層及非變色層形成為因變色層之變色而開始顯現文字、圖案及記號中至少一種。本發明之文字、圖案及記號,係包含通知變色之所有資訊。此等文字等,可因應使用目的等而進行適當設計即可。
此外,變色前的變色層與非變色層相互係不同顏色亦可。例如,兩者實質上為同一顏色,而變色後開始使變色層與非變色層間之色差(對比度)可辨識亦可。
本發明中,層構成的較佳態樣,可列舉例如:(i)變色層鄰接在基材之至少一側的主面上而形成的指示劑;(ii)基材上,前述非變色層及前述變色層依序形成,且前記非變色層係鄰接在前述基材之主面上而形成,前述變色層係鄰接在前述非變色層之主面上而形成的指示劑。
(黏著層)
本發明之指示劑,可因應必要,而在基材裏面(與變色層形成面相逆之面)具有黏著層。藉由在基材裏面具有黏著層,本發明之指示劑可確實固定於電漿處理裝置內所望部位(例如供應電漿處理的對象物、裝置底面
等),故具有其較佳。
黏著層之成分,其本身可抑制電漿處理導致的氣體化為佳。如此之成分,例如,特殊黏著劑為佳,其中,矽酮系黏著劑較佳。
(本發明之指示劑的形狀)
本發明之指示劑的形狀並無特別限定,可廣泛採用習知之電漿處理檢測指示劑的形狀。其中,本發明之指示劑的形狀與電子設備製造裝置所使用之電子設備基板的形狀相同時,亦即作為虛擬基板,可簡便地檢測電漿處理對於電子設備基板全體是否均一的進行。
在此,「指示劑的形狀與電子設備製造裝置所使用之電子設備基板的形狀相同」係包含:(i)指示劑的形狀,與電子設備製造裝置所使用之電子設備基板的形狀完全相同,以及,(ii)指示劑的形狀,與電子設備製造裝置所使用之電子設備基板的形狀,及約可放置(嵌合)於進行電漿處理之電子設備裝置內之電子設備基板的設置位置係實質上相同中任一者。
例如,上述(ii)中,實質上相同包含:對於電子設備基板的主面之長度(基板的主面形狀為圓形時指直徑、基板的主面形狀為正方形、矩形等時則指縱及寬之長度),本發明之指示劑的主面之長度相差在約±5.0mm以內、對於電子設備基板,本發明之指示劑之厚度相差在約±1000μm以內。
本發明指示劑雖不限定使用在電子設備製造裝置,但使用在電子設備製造裝置時,較佳係使用在藉由選自成膜步驟、蝕刻步驟、灰化步驟、雜質添加步驟及洗浄步驟所成群中至少一種步驟而進行電漿處理之
電子設備製造裝置。
(電漿)
電漿,並無特別限定,可使用藉由電漿產生用氣體而產生之電漿。電漿之中,藉由選自氧、氮、氫、氯、氬、矽烷、氨、溴硫、三氯化硼、溴化氫、水蒸氣、一氧化二氮、四乙氧基矽烷、三氟化氮、四氟化碳、全氟環丁烷、二氟甲烷、三氟甲烷、四氯化碳、四氯化矽、六氟化硫、六氟乙烷、四氯化鈦、二氯矽烷、三甲基鎵、三甲基銦、及三甲基鋁所成群中至少一種的電漿產生用氣體而產生之電漿為佳。此等電將產生用氣體之中,特別係選自四氟化碳;全氟環丁烷;三氟甲烷;六氟化硫;氬與氧的混合氣體;所成群中至少一種為佳。
電漿,可藉由電漿處理裝置(藉由在含有電漿產生用氣體之環境下,施加交流電壓、直流電、脈衝電壓、高頻電、微波電等使電漿產生以實施電漿處理之裝置)而產生。特別係在電子設備製造裝置中,電漿處理,係在以下說明之成膜步驟、蝕刻步驟、灰化步驟、雜質添加步驟、洗浄步驟等中使用。
成膜步驟,例如,在電漿CVD(Chemical Vapor Depositon,化學氣相成長)中,可併用電漿及熱能、並以400℃以下之低温而由較快之成長速度在半導體晶圓上使膜成長。具體而言,將材料氣體導入減壓之反應室,藉由激發電漿使氣體自由基離子化而進行反應。電漿CVD,可列舉出容量結合型(陽極結合型、平行平板型)、誘導結合型、ECR(Electron Cyclotron Resonance:電子迴旋共振)型之電漿。
其他之成膜步驟,可列舉為藉由濺射而成之成膜步驟。具體
之例示為,在高頻放電濺射裝置內,導入1Torr~10-4Torr之不活性氣體(例如Ar),並在半導體晶圓與目標物之間施加數10V~數Kv之電壓,使離子化的Ar朝向目標物加速及衝撞,從而使目標物的物質濺射至半導體晶圓上並堆積。此時,同時從目標物產生高能量之γ-電子,與Ar原子衝撞時使Ar原子離子化(Ar+),從而使電漿持續。
此外,其他成膜步驟,可列舉為藉由離子鍍而成之成膜步驟。具體之例示為,使內部成為約10-5Torr~10-7Torr之高真空狀態,並注入不活性氣體(例如Ar)或反應性氣體(氮、烴等),從加工裝置之熱電子發生陰極(電子槍)將電子束朝向蒸著材進行放電,使離子與電子分離而產生電漿。接著,藉由電子束,將金屬加熱至高溫,蒸發後,藉由對於蒸發之金屬粒子施加正電壓,在電漿中使電子與金屬粒子衝撞,從而使金屬粒子成為陽離子,如此可朝向被加工物前進並同時可促進金屬粒子與反應性氣體結合之化學反應。被促進化學反應之粒子,將朝向增加負電子之被加工物加速,從而可高能量衝撞,使堆積在表面作為金屬化合物。又,與離子鍍類似之蒸著法亦可列舉為成膜步驟。
進一步,氧化、氮化步驟,可列舉藉由ECR電漿、表面波電漿等而電漿氧化,從而使半導體晶圓表面變換為氧化膜之方法;或導入氨氣,藉由電漿激起而使前述氨氣電離、分解、離子化,從而使半導體晶圓表面變換為氮化膜之方法等。
蝕刻步驟,例如,可有效利用:在反應性離子蝕刻裝置(RIE)中,將圓形平板電極平行對向,並導入反應氣體至減壓反應室(腔室),藉由電漿激起而使導入氣體自由基化或離子化而生成在電極間,藉由此等自
由基或離子與在半導體晶圓上的材料化學反應使其揮發物質化而蝕刻;及物理性濺射兩者。此外,電漿蝕刻裝置,除了上述平行平板型外,亦可列舉出桶型(圓筒型)。
其他之蝕刻步驟,可列舉為逆濺射。逆濺射,雖原理與前述濺射類似,但其係在電漿中之離子化的Ar與半導體晶圓衝撞之蝕刻的方法。此外,與逆濺射類似之離子束蝕刻亦可列舉作為蝕刻步驟。
灰化步驟,例如,使用氧電漿,在減壓下使氧化氣體電漿激起,從而分解及揮發光阻。
雜質添加步驟,例如,將含有摻雜有雜質原子之氣體導入置減壓腔室內,激起電漿使雜質離子化,對於半導體晶圓施加負電之偏置電壓,從而摻雜雜質離子。
洗浄步驟,係在進行半導體晶圓之各步驟前,對於半導體晶圓上附著之異物,在不使半導體晶圓受傷之情況下將其除去之步驟,可列舉例如,以氧氣電漿發生化學反應之電漿洗淨、或以不活性氣體(氬等)電漿而物理性的除去之電漿洗淨(逆濺射)等。
以下表示實施例及比較例從而具體說明本發明。惟,本發明並非限定為實施例。
實施例1~5及比較例1
準備下述表1所示組成的油墨組成物,藉由個別在聚醯亞胺薄膜上塗佈及乾燥,而在聚醯亞胺薄膜上形成20μm之變色層。
具體而言,對於基材之聚醯亞胺薄膜進行絲網印刷而印刷電漿處理檢測用油墨組成物,並將塗膜以170℃乾燥10分製作出指示劑。
試驗例1
圖1,係容量結合電漿(CCP;Capacitively Coupled Plasma)型之電漿蝕刻裝置的概略斷面圖。
本裝置,係在真空容器內設置平行平板型之電極,上部電極形成為淋浴構造,使反應氣體為淋浴狀供給至被處理物表面。
實際實施蝕刻時,係使真空容器內排氣後,從上部電極淋浴部導入反應性氣體,此外藉由上部電極供給之高頻電力,在平行平板電極內之空間產生電漿,並藉由產生之激起種使被處理物表面發生化學反應,
從而進行蝕刻。
試驗例1,在本裝置內載置實施例1~5及比較例1所製作之指示劑,導入四氟化碳氣體(CF4)作為反應性氣體時,評估各指示劑之變色層的變色性(處理前後之色差△E的測定)及剝離。
表2表示電漿處理之條件。
表1表示變色性之結果。變色性之評估基準如以下所示。
○:色差△E>15
×:色差△E<15
表1表示剝離之結果。剝離之評估基準如以下所示。
○:電漿處理後,觸摸變色層時變色層亦不會剝離
×:電漿處理後,觸摸變色層時變色層剝離
試驗例2
準備實施例1所製作之指示劑、與在變色層中含有有機色素之傳統例1的電漿處理檢測指示劑(wahl公司製、Wahl Instruments.Inc.Temp-plate(登錄商標)101-6-215C),比較升溫時的放出氣體特性。
具體而言,將實施例1之指示劑與傳統例1之指示劑載置於安裝在升溫可能之試料台上之真空裝置內,藉由真空排氣使其成為1.0E-6Pa
台之真空度後,藉由以30℃/分使試料台升溫時之真空装置內的真空度變化而調查放出氣體特性。放出氣體特性之結果以圖2表示。
由圖2之結果可明確得知,相對於傳統例1之指示劑在150℃~200℃時真空度將會有增大之變化,實施例1之指示劑,真空度變化較傳統例1之指示劑為少。因此,使用金屬氧化物粒子作為變色材料的本發明之指示劑,與在變色層中含有有機色素之傳統例1之指示劑比較,可發現在升溫時的放出氣體較少。
此外,由圖3之結果可明確得知,觀察升溫後之各樣品的顏色之結果,相對於傳統例之指示劑(圖3之(b))會因熱而變色,實施例1所製作之指示劑(圖3之(a))並未發現其因熱而變色之情形。
理由係,傳統例1之指示劑係在變色層中含有機色素,因此在200℃附近時,將發生有機物的分解,伴隨於此,會有放出氣體的發生及有機色素的變色,另一方面,實施例1所製作之指示劑,其係在變色層中含有金屬氧化物粒子(無機物),因此具有優異之放出氣體特性及耐熱性。
Claims (13)
- 一種電漿處理檢測油墨組成物,其特徵為其係用以形成藉由電漿處理而變色之變色層的油墨組成物;且該油墨組成物係含有金屬氧化物粒子及接著劑樹脂;前述金屬氧化物粒子係含選自Mo、W、Sn、V、Ce、Te及Bi所成群中至少一種元素者。
- 如申請專利範圍第1項所記載之電漿處理檢測油墨組成物,其中,前述金屬氧化物粒子,係含有選自氧化鉬粒子(IV)、氧化鉬粒子(VI)、氧化鎢粒子(VI)、氧化錫粒子(IV)、氧化釩粒子(II)、氧化釩粒子(III)、氧化釩粒子(IV)、氧化釩粒子(V)、氧化鈰粒子(IV)、氧化碲粒子(IV)、氧化鉍粒子(III)、碳酸氧化鉍粒子(III)及氧化硫酸釩粒子(IV)所成群中至少一種者。
- 如申請專利範圍第1或2項所記載之電漿處理檢測油墨組成物,其中,前述金屬氧化物粒子,係含有選自氧化鉬粒子(Ⅵ)、氧化鎢粒子(Ⅵ)、氧化釩粒子(III)、氧化釩粒子(V)及氧化鉍粒子(III)所成群中至少一種者。
- 如申請專利範圍第1~3項中任一項所記載之電漿處理檢測油墨組成物,其中,前述金屬氧化物粒子之平均粒徑為50μm以下。
- 如申請專利範圍第1~4項中任一項所記載之電漿處理檢測油墨組成物,其中,前述接著劑樹脂,係含有選自石油烴系樹脂、乙烯基樹脂、丁醛樹脂、醇酸樹脂、丙烯酸樹脂、環氧樹脂、聚氨酯樹脂、丙烯腈樹脂、氟樹脂、矽樹脂、甲醛樹脂、聚酯樹脂、聚乙烯樹脂、酮樹脂、聚醯胺 樹脂、馬來酸樹脂、古馬隆樹脂、聚醯亞胺樹脂、聚醚醚酮樹脂、脂環族樹脂所成群中至少一種者。
- 如申請專利範圍第1~5項中任一項所記載之電漿處理檢測油墨組成物,其中,前述接著劑樹脂之軟化點為70℃以上。
- 一種電漿處理檢測指示劑,其特徵為其之基材上,係具有由申請專利範圍第1~6項中任一項所記載之電漿處理檢測油墨組成物的硬化塗膜所形成之變色層。
- 如申請專利範圍第7項所記載之電漿處理檢測指示劑,其中,其係電子設備製造裝置所使用之指示劑。
- 如申請專利範圍第8項所記載之電漿處理檢測指示劑,其中,前述指示劑的形狀,係與前述電子設備製造裝置所使用之電子設備基板的形狀相同者。
- 如申請專利範圍第8或9項所記載之電漿處理檢測指示劑,其中,前述電子設備製造裝置,係進行有選自成膜步驟、蝕刻步驟、灰化步驟、雜質添加步驟及洗淨步驟所成群中至少一種的電漿處理者。
- 如申請專利範圍第7~10項中任一項所記載之電漿處理檢測指示劑,其中,其係具有藉由電漿處理而不變色之非變色層。
- 如申請專利範圍第11項所記載之電漿處理檢測指示劑,其中,前述非變色層,係含有選自氧化鈦(IV)、氧化鋯(IV)、氧化釔(III)、硫酸鋇、氧化鎂、二氧化矽、氧化鋁、鋁、銀、釔、鋯、鈦、鉑金所成群中至少一種者。
- 如申請專利範圍第11或12項所記載之電漿處理檢測指示劑,其中,前述 基材上,係依序形成有前述非變色層及前述變色層;前述非變色層,係鄰接於前述基材的主面上而形成;前述變色層,係鄰接於前述非變色層的主面上而形成。
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JP6143444B2 (ja) * | 2012-12-03 | 2017-06-07 | 株式会社サクラクレパス | 過酸化水素ガス検知用インキ組成物、過酸化水素ガス検知インジケーター、過酸化水素ガス滅菌用包装体、及び過酸化水素ガス滅菌処理方法 |
JP6126042B2 (ja) | 2013-06-04 | 2017-05-10 | 株式会社サクラクレパス | プラズマ処理検知用インキ組成物及びプラズマ処理検知インジケーター |
TWI624890B (zh) * | 2013-08-22 | 2018-05-21 | Sakura Color Prod Corp | Indicator for electronic component manufacturing apparatus, and design and/or management method of the same |
WO2015122425A1 (ja) | 2014-02-14 | 2015-08-20 | 株式会社サクラクレパス | プラズマ処理検知インジケータ |
JP2015205995A (ja) | 2014-04-21 | 2015-11-19 | 株式会社サクラクレパス | プラズマ処理検知用インキ組成物及びプラズマ処理検知インジケータ |
KR102296893B1 (ko) | 2014-05-09 | 2021-08-31 | 사쿠라 컬러 프로덕츠 코포레이션 | 무기 물질을 변색층으로 사용한 플라스마 처리 감지 표시기 |
JP6567863B2 (ja) | 2014-09-16 | 2019-08-28 | 株式会社サクラクレパス | プラズマ処理検知用インキ組成物及びプラズマ処理検知インジケータ |
JP6567817B2 (ja) | 2014-12-02 | 2019-08-28 | 株式会社サクラクレパス | プラズマ処理検知インキ組成物及びそれを用いたプラズマ処理検知インジケータ |
JP2016111063A (ja) | 2014-12-02 | 2016-06-20 | 株式会社サクラクレパス | 変色層として金属酸化物微粒子を使用したプラズマ処理検知インジケータ |
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KR20170091093A (ko) | 2017-08-08 |
CN107001837B (zh) | 2020-11-10 |
JP6567817B2 (ja) | 2019-08-28 |
US10180413B2 (en) | 2019-01-15 |
KR102471131B1 (ko) | 2022-11-24 |
CN107001837A (zh) | 2017-08-01 |
US20170261476A1 (en) | 2017-09-14 |
JP2016108371A (ja) | 2016-06-20 |
TWI672344B (zh) | 2019-09-21 |
WO2016088595A1 (ja) | 2016-06-09 |
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