TW202235551A - 去除犧牲層之上部的方法、使用於其之犧牲溶液及酸性水溶液 - Google Patents
去除犧牲層之上部的方法、使用於其之犧牲溶液及酸性水溶液 Download PDFInfo
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- TW202235551A TW202235551A TW110148154A TW110148154A TW202235551A TW 202235551 A TW202235551 A TW 202235551A TW 110148154 A TW110148154 A TW 110148154A TW 110148154 A TW110148154 A TW 110148154A TW 202235551 A TW202235551 A TW 202235551A
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- Prior art keywords
- sacrificial
- sacrificial layer
- solution
- substrate
- alkyl
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- 239000000243 solution Substances 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 66
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 48
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 116
- 229920000642 polymer Polymers 0.000 claims abstract description 53
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 125000006239 protecting group Chemical group 0.000 claims abstract description 23
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- 125000000217 alkyl group Chemical group 0.000 claims description 45
- 238000012545 processing Methods 0.000 claims description 31
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Abstract
本發明提供一種去除犧牲層之上部的方法。
本發明之去除犧牲層之上部的方法包含以下的步驟。
(1)將包含具有因酸而解離之保護基的聚合物(A)及溶劑(B)的犧牲溶液施用於基板上方;
(2)由所施用之犧牲溶液形成犧牲層;
(3)使酸性水溶液接觸犧牲層的表面;及
(4)將去除液施用於犧牲層。
Description
本發明係關於去除犧牲層之上部的方法、使用於其之犧牲溶液及酸性水溶液。本發明進一步關於加工基板的製造方法及裝置的製造方法。
在半導體等的裝置之製造過程中,為了避免在預期部分之外進行加工,會形成犧牲膜(或保護膜)以進行保護後再進行加工,之後再去除犧牲膜(例如專利文獻1)。近年來因為微細化的發展而要求以更高的精度來形成犧牲膜的膜厚。
為了使犧牲膜成為預期的膜厚,會在成膜後進行回蝕。回蝕可藉由乾式蝕刻或濕式蝕刻進行。為了提升回蝕後的膜厚精度,有人想到以耐蝕性高的膜作為犧牲膜,或是著重於蝕刻用的化學藥液種類及濃度,藉此降低蝕刻速度,但其處理時間變長。
非專利文獻1中,作為EUVL用的材料與製程開發,以抑制酸在非曝光部中擴散作為一觀點而進行了各種嘗試。該文獻中,將曝光後的光阻層剝離並集中而使其成型,設置於其他樹脂層上並加熱,得到下方樹脂層的減膜量ΔL。
[先前技術文獻]
[專利文獻]
[專利文獻1] 國際公開2003/015183號公報
[非專利文獻]
[非專利文獻1] 16nm半間距適用的EUVL用材料及製程開發(丸山研,JSR TECHNICAL REVIEW No.120/2013)
[發明欲解決之課題]
本案發明人針對去除犧牲層之上部的方法,認為目前仍存在1個以上需要改良的課題。此等可列舉如下:去除犧牲層之上部並使其成為預期的膜厚;控制去除之犧牲膜上部的厚度、深度;縮小去除之犧牲膜上部的厚度、深度的不均勻,提高對比;對於基板的既定高度、深度部分進行加工;去除犧牲膜的一部分時會對於基板造成損傷;優化犧牲溶液對於加工基板填入性;在將加工基板重合時開口部彼此會錯位;與所製造的裝置連接不良及電特性不均;製造良率低;裝置的製造步驟複雜;裝置的製造時間長。
本發明係根據上述技術背景而完成,其提供一種去除犧牲層之上部的方法、使用於其之犧牲溶液及酸性水溶液。
[用以解決課題之手段]
本發明之去除犧牲層之上部的方法包含以下步驟。
(1)將包含具有因酸而解離之保護基的聚合物(A)及溶劑(B)的犧牲溶液施用於基板的上方;
(2)由所施用之犧牲溶液形成犧牲層;
(3)使酸性水溶液接觸犧牲層的表面;及
(4)將去除液施用於犧牲層。
本發明之加工基板的製造方法包含以下步驟。
準備已藉由上述方法去除犧牲層之上部的基板;
(5)對於前述基板之犧牲層經去除的部分進行表面處理;
(6)去除剩餘的犧牲層;及
(7)對於前述基板實施進一步的加工。
本發明之裝置的製造方法包含上述方法。
本發明之犧牲溶液包含具有因酸而解離之保護基的聚合物(A)及溶劑(B),
此犧牲溶液形成犧牲層,犧牲層與酸性水溶液接觸,則犧牲層上部會被去除液所去除。
本發明之酸性水溶液,包含選自含有下式(ZA)、(ZB)及(ZC)所示之化合物的群組的酸及水,其係用以接觸犧牲層。
(此處,R
ZA為C
1-10氟取代烷基、C
1-10氟取代烷醚、C
6-20氟取代芳基、C
1-10氟取代醯基或C
6-20氟取代烷氧基芳基)
(此處,R
ZB各自獨立為C
1-10氟取代烷基、C
1-10氟取代烷醚、C
6-20氟取代芳基、C
1-10氟取代醯基或C
6-20氟取代烷氧基芳基,2個R
ZB亦可互相鍵結而形成經氟取代的雜環結構)
(此處,
R
ZC為氫、C
1-6烷基、C
1-6烷氧基或羥基;L
ZC為氧基或羰氧基;
X
ZC各自獨立為氫或氟;
n
ZC1為0~10,且
n
ZC2為0~21)
[發明之效果]
根據本發明,可期待以下的一個或多個效果。
去除犧牲層之上部而可成為預期的膜厚;可控制去除之犧牲膜的上部之厚度、深度;可縮小去除之犧牲膜上部的厚度、深度的不均勻並提高對比;可對於基板的既定高度、深度之部分進行加工;去除犧牲膜的一部分時可減少對於基板的損傷;加工基板中犧牲溶液的填入性高;可將在加工基板重合時錯位的開口部彼此連接;可抑制與所製造之裝置的連接不良及電特性不均;可改善製造的良率;可簡化裝置製造步驟;可縮短裝置製造時間。
[用以實施發明的形態]
[定義]
本說明書中,只要未特別限定或提及,則依照本段中所記載的定義及例子。
單數形包含複數形,「一個」或「其」表示「至少一個」。某一概念的要件亦可以多種呈現,記載其量(例如質量%或莫耳%)的情況,其量則表示此等多種的總和。
「及/或」包含要件的所有組合,又亦包含以單質使用。
使用「~」或「-」表示數值範圍時,此等包含兩邊的端點,單位則為共通。例如,5~25莫耳%表示5莫耳%以上25莫耳%以下。
「C
x-y」、「C
x~C
y」及「C
x」等的記載表示分子或取代基中的碳數。例如,C
1-6烷基表示具有1個以上6個以下的碳的烷基鏈(甲基、乙基、丙基、丁基、戊基、己基等)。
聚合物具有多種重複單元時,此等的重複單元進行共聚合。此等共聚合亦可為交互共聚合、無規共聚合、嵌段共聚合、接枝共聚合或此等混合的任一種。以結構式表示聚合物或樹脂時,一併記載於括弧中的n或m等表示重複數。
溫度單位使用攝氏(Celsius)。例如,20度表示攝氏20度。
添加劑係指具有該功能之化合物本身(例如,若為鹼產生劑則是會產生鹼的化合物本身)。該化合物亦可為溶解或分散於溶劑後添加至組成物的態樣。作為本發明的一型態,這樣的溶劑較佳係作為溶劑(B)或其他成分而含有於本發明之犧牲溶液中。
以下詳細說明本發明的實施型態。
<去除犧牲層之上部的方法>
本發明之去除犧牲層之上部的方法包含以下的步驟。
(1)將包含具有因酸而解離之保護基的聚合物(A)及溶劑(B)的犧牲溶液施用於基板的上方;
(2)由所施用之犧牲溶液形成犧牲層;
(3)使酸性水溶液接觸犧牲層的表面;及
(4)將去除液施用於犧牲層。
以下使用圖來說明各步驟。若為了明確性而記載,係在(3)的步驟之前進行(1)及(2)的步驟。顯示步驟的()之中的數字係表示順序。以下相同。
步驟(1)
步驟(1)中,將犧牲溶液施用於基板的上方。
作為基板,可列舉例如:矽/二氧化矽被覆基板、氮化矽基板、矽晶圓基板、玻璃基板及ITO基板。本發明中,即使施用於具有凹凸之圖案基板、例如具有高縱橫比之溝槽形狀的基板之情況,亦具有可以良好的精度去除犧牲層這樣的特徵,因此在使用圖案基板的情況中有效而較佳。
基板的較佳態樣之一為Si基板;更佳為多種含Si層積層而成者。更佳為絕緣性含Si層與導電性含Si層交互連續積層而成的結構。作為絕緣性含Si層,可列舉SiO
2層,作為導電性含Si層,可列舉SiN層。作為這樣的結構,宜為以絕緣性含Si層與導電性含Si層為一組而連續交互積層5~500次而成的結構;更宜為10~300次;再宜為50~300次。基板的最下層需要作為結構支撐的功能,這種最下層的較佳例可列舉Si基板。
基板整體厚度較佳為1~20μm;更佳為4~15μm;再佳為5~10μm。
作為圖案基板,可列舉具有接觸孔的基板。在接觸孔深度大幅超過直徑之處的條件嚴苛,例如若以異向性蝕刻設置接觸孔,則孔的直徑可能會隨著深度逐漸變小。作為本發明的態樣,在單一圖案基板中條件最嚴苛之處的接觸孔的直徑與深度的比較佳為0.5:1~400:1;更佳為0.5:1~300:1;再佳為0.5:1~250:1;再佳為0.5:1~200:1。
又,作為另一態樣,在溝槽圖案基板的圖案壁的縱橫比中,縱橫比最高(壁的高度大幅超過壁的寬度)之處,去除膜等的條件變得嚴苛。作為本發明的態樣,在單一圖案基板中條件最嚴苛之處的縱橫比較佳為0.5:1~400:1;更佳為0.5:1~300:1;再佳為0.5:1~250:1;再佳為0.5:1~200:1。
圖案基板可以習知的方法製作。作為將圖案基板加工的方法,宜為乾式蝕刻、濕式蝕刻、離子注入或金屬鍍覆方法;更宜為乾式蝕刻或濕式蝕刻;再宜為異向性乾式蝕刻或濕式蝕刻;再宜為異向性乾式蝕刻。亦可使用光阻圖案作為遮罩。作為異向性乾式蝕刻的氣體環境,可列舉N
2、NF
3、H
2、稀有氣體、氟碳化物;理想而言,可列舉:Ar、Ne、NF
3、H
2、CF
4、CHF
3、CH
2F
2、CH
3F、C
4F
6、C
4F
8等。此等的氣體亦可混合2種以上使用。可對於圖案基板進行加工而在接觸孔或溝槽的表面(宜排除此等的底部)形成導電層。
圖1(a)係圖案基板的例子,基板1具有壁寬度5的壁2,溝槽寬度6且從溝槽底部4起算的深度7之溝槽3部分係挖空的部分。
藉由適當的方法將後述犧牲溶液施用於基板的上方。此處,本發明中「基板的上方」包含形成於基板正上方的情況及隔著其他層而形成的情況。例如,亦可在基板的正上方形成平坦化膜或光阻底層膜,再於其正上方施用犧牲溶液。施用方法並未特別限定,可列舉例如:以旋轉器、塗布機進行塗布的方法。
[犧牲溶液]
本發明之犧牲溶液包含具有因酸而解離之保護基的聚合物(A)(以下有時稱為聚合物(A))及溶劑(B)。此犧牲溶液係用於本發明之去除犧牲層之上部的方法,亦即形成犧牲層後,犧牲層與酸性水溶液接觸而藉由去除液去除犧牲層之上部。又,作為另一態樣,本發明提供一種犧牲溶液,其包含具有因酸而解離之保護基的聚合物(A)及溶劑(B),其特徵為:犧牲溶液形成犧牲層,犧牲層與酸性水溶液接觸,則犧牲層上部被去除液所去除。
(A)具有因酸而解離之保護基的聚合物
聚合物(A),會因為與後述酸性水溶液接觸而保護基解離,對於去除液的溶解度增加。一般而言,可使用在化學增幅型光阻組成物中所使用的聚合物。聚合物(A)可以習知的方法合成及取得。
聚合物(A)的因酸而解離之保護基係選自包含-C(R
1)(R
2)(R
3)、-C(R
1)(R
2)(OR
4)及-C(R
5)(R
6)(OR
4)之群組中的至少一式所表示的基。
較佳為聚合物(A)的主鏈及/或側鏈具有因酸而解離之保護基;更佳為主鏈或側鏈具有因酸而解離之保護基;再佳為側鏈具有因酸而解離之保護基。
此處,
R
1~R
4各自獨立為烷基、環烷基、芳基、芳烷基或烯基、R
1與R
2亦可相互鍵結而形成環。
R
5及R
6各自獨立為氫、烷基、環烷基、芳基、芳烷基或烯基。
R
1~R
6的烷基較佳為C
1-8烷基,可列舉例如:甲基、乙基、丙基、正丁基、二級丁基、己基、辛基等。
R
1~R
6的環烷基可為單環型,亦可為多環型。作為單環型,較佳為C
3-8環烷基,可列舉例如:環丙基、環丁基、環戊基、環己基、環辛基等。作為多環型,較佳為C
6-20環烷基,可列舉例如:金剛烷基、降莰基、異莰基、莰基、二環戊基、α-蒎烯基(α-pinel)、三環癸基、四環十二基、雄固烷基(androstanyl)等。另外,環烷基中的至少1個碳原子亦可由氧原子等雜原子所取代。
R
1~R
6的芳基較佳為C
6-10芳基,可列舉例如:苯基、萘基、蒽基等。
R
1~R
6的芳烷基較佳為C
7-12芳烷基,可列舉例如:苄基、苯乙基、萘基甲基等。
R
1~R
6的烯基較佳為C
2-8烯基,可列舉例如:乙烯基、烯丙基、丁烯基、環己烯基(cyclohexenyl)等。
作為R
1與R
2鍵結所形成的環,較佳為環烷基(單環或多環)。作為環烷基,較佳為環戊基、環己基等單環的環烷基、降莰基、四環癸基、四環十二基、金剛烷基等多環的環烷基。更佳為C
5-6的單環之環烷基,再佳為C
5單環之環烷基。
聚合物(A)較佳為包含式(P-1)、(P-2)、及/或(Q)所示之重複單元。聚合物(A)更佳為包含式(P-1)及/或(P-2)所示之重複單元;再佳為包含式(P-1)所示之重複單元。作為聚合物(A)的例子,可列舉:聚羥基苯乙烯(PHS)系聚合物及聚甲基丙烯酸甲酯(PMMA)系聚合物。
此處,
R
p1及R
p3各自獨立為氫或C
1-4烷基;較佳為氫或甲基;再佳為氫。
R
p2、R
p4及R
q1各自獨立為直鏈、分支或環狀的C
3-15烷基(此處,烷基亦可由氟所取代,烷基中的-CH
2-亦可由-O-替換)。R
p2、R
p4及R
q1的C
3-15烷基宜為C
3-10;更宜為C
3-8;再宜為C
3-5;再更宜為C
4。此處,前述「經氟取代的烷基」係指存在於烷基上的H被取代成F。前述的取代成氟,表示存在於烷基上的H的全部或一部分被取代成F,亦可全部皆被取代。作為本發明的一態樣,R
p2、R
p4及R
q1的C
3-15烷基未被氟所取代。又,作為本發明的一態樣,R
p2、R
p4及R
q1的烷基中的-CH
2-未由-O-所替換。
作為本發明的一態樣,R
p2、R
p4及R
q1各自獨立為以-C(R
1)(R
2)(R
3)、-C(R
1)(R
2)(OR
4)或-C(R
5)(R
6)(OR
4)所表示的因酸而解離之保護基。
x1及y1各自獨立,其為1~3;較佳為1~3的整數;再佳為1。
T
1及T
2各自獨立地為單鍵或C
1-12的連結基;宜為單鍵。作為T
1或T
2的C
1-12的連結基,可各自獨立地列舉包含伸烷基、-COO-Rt-、-O-Rt-或此等任2種以上之組合的連結基;宜為-COO-Rt-。Rt為伸烷基或伸環烷基;更宜為C
1-5伸烷基;再宜為-CH
2-、-(CH
2)
2-或-(CH
2)
3-。
R
p5各自獨立為C
1-5烷基(此處,烷基中的-CH
2-亦可由-O-所替換)。R
p5宜為C
1-4烷基;更宜為甲基或三級丁基;再宜為甲基。作為本發明的一態樣,R
p5的C
1-5烷基中的-CH
2-未由-O-所替換。
R
q2各自獨立為羥基或C
1-5烷基(此處,烷基中的-CH
2-亦可由-O-所替換);宜為羥基。R
q2的C
1-5烷基為C
1-4烷基;更宜為甲基或三級丁基;再宜為甲基。作為本發明的一態樣,R
q2的C
1-5烷基中的-CH
2-未由-O-所替換。
x2及y2各自獨立為0~2;較佳為0~2的整數;更佳為0。
作為較佳的一型態,聚合物(A)含有由包含式(P-1)~(P-4)之群組所示的重複單元,更佳為含有由包含式(P-1)~(P-4)之群組所示的重複單元,且式(P-1)~(P-4)以外的重複單元的比例在20莫耳%以下,再佳為由包含式(P-1)~(P-4)之群組所示的重複單元所構成。
作為較佳的一型態,聚合物(A)包含(P-1)或(P-2)作為重複單元。作為本發明的一態樣,聚合物(A)包含式(P1)及/或(P2)任一者所表示的重複單元與式(P3)及/或(P4)任一者所表示的重複單元。此處,聚合物(A)中,式(P-1)~(P-4)以外的重複單元的比例較佳為20莫耳%以下,更佳為由包含式(P-1)~(P-4)之群組所示之重複單元所構成。
此處,
R
p6及R
p8各自獨立為氫或C
1-3烷基;較佳為氫或甲基;更佳為氫。
R
p7及R
p9各自獨立為C
1-5烷基(此處,烷基中的-CH
2-亦可由-O-所替換)。R
p7及R
p9宜為C
1-4烷基;更宜為甲基或三級丁基;再宜為甲基。作為本發明的一態樣,R
p7及R
p9的C
1-5烷基中的-CH
2-未由-O-所替換。
x3及x5各自獨立為0~2;較佳為0~2的整數;更佳為0。
x4為1~2;較佳為0~1的整數;更佳為1。
此等的重複單元,係以藉由與酸性水溶液接觸而使其對於去除液之溶解度增加的比例成為適當的方式摻合。以聚合物中的所有重複單元作為基準,(P-1)及(P-2)的重複單元的比例較佳為5~50莫耳%,更佳為10~40莫耳%。
聚合物(A)中,將式(P-1)、(P-2)、(P-3)及(P-4)的重複單元數分別設為n
p1、n
p2、n
p3及n
p4。
n
p1/(n
p1+n
p2+n
p3+n
p4)較佳為0~60%;更佳為1~60%;再佳為5~50%;再更佳為10~30%。
n
p2/(n
p1+n
p2+n
p3+n
p4)較佳為0~60%;更佳為0~50%;再佳為5~50%;再更佳為5~30%。作為本發明的一態樣,n
p2/(n
p1+n
p2+n
p3+n
p4)=0%亦為理想。
n
p3/(n
p1+n
p2+n
p3+n
p4)較佳為0~90%;更佳為5~80%;再佳為30~80%;再更佳為50~70%。
n
p4/(n
p1+n
p2+n
p3+n
p4)較佳為0~60%;更佳為1~50%;再佳為5~40%;再更佳為10~30%。
n
p1+n
p2>0%。n
p1與n
p2的至少一者大於0%;宜為n
p1大於0%。
n
p1、n
p2、n
p3及n
p4較佳係滿足下式:
0%≤n
p1/(n
p1+n
p2+n
p3+n
p4)≤60%;
0%≤n
p2/(n
p1+n
p2+n
p3+n
p4)≤60%;
0%≤n
p3/(n
p1+n
p2+n
p3+n
p4)≤90%;及
0%≤n
p4/(n
p1+n
p2+n
p3+n
p4)≤60%,且滿足n
p1+n
p2>0%。
聚合物(A)亦可含有(P-1)、(P-2)、(P-3)及(P-4)以外的重複單元。此處聚合物(A)所包含的所有重複單元的總數n
total較佳係滿足下式:
80%≤(n
p1+n
p2+n
p3+n
p4)/n
total≤100%。
(n
p1+n
p2+n
p3+n
p4)/n
total更佳為90~100%,再佳為95~100%。(n
p1+n
p2+n
p3+n
p4)/n
total=100%,亦即不含(P-1)、(P-2)、(P-3)、及(P-4)以外的重複單元,亦為本發明的較佳態樣之一。
聚合物(A)的含量,以犧牲溶液的總質量為基準,宜為5~50質量%;更宜為10~45質量%;再宜為20~40質量%;再更宜為30~35質量%。
聚合物(A)的質量平均分子量(Mw)較佳為2,000~200,000;更佳為4,000~200,000;再佳為8,000~20,000。此處,質量平均分子量係由凝膠滲透層析法而來的聚苯乙烯換算質量平均分子量。
(B)溶劑
溶劑(B)只要是可將摻合之各成分溶解者則未特別限定,可任意選自微影法中一般使用者。溶劑(B)較佳為水、烴溶劑、醚溶劑、酯溶劑、醇溶劑、酮溶劑或此等任一組合。
作為溶劑(B)的具體例,可列舉例如:水、正戊烷、異戊烷、正己烷、異己烷、正庚烷、異庚烷、2,2,4-三甲基戊烷、正辛烷、異辛烷、環己烷、甲基環己烷、苯、甲苯、二甲苯、乙苯、三甲苯、甲基乙基苯、正丙苯、異丙苯、二乙苯、異丁苯、三乙苯、二異丙苯、正戊基萘、三甲苯、甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、二級丁醇、三級丁醇、正戊醇、異戊醇、2-甲基丁醇、二級戊醇、三級戊醇、3-甲氧基丁醇、正己醇、2-甲基戊醇、二級己醇、2-乙基丁醇、二級庚醇、庚醇-3、正辛醇、2-乙基己醇、二級辛醇、正壬醇、2,6-二甲基庚醇-4、正癸醇、二級十一烷醇、三甲基壬醇、二級十四烷醇、二級十七烷醇、酚、環己醇、甲基環己醇、3,3,5-三甲基環己醇、苄醇、苯基甲基甲醇(phenylmethylcarbinol)、二丙酮醇、甲酚、乙二醇、丙二醇、1,3-丁二醇、戊二醇-2,4、2-甲基戊二醇-2,4、己二醇-2,5、庚二醇-2,4、2-乙基己二醇-1,3、二乙二醇、二丙二醇、三乙二醇、三丙二醇、甘油、丙酮、甲乙酮、甲基-正丙酮、甲基-正丁酮、二乙酮、甲基-異丁酮、甲基-正戊酮、乙基-正丁酮、甲基-正己酮、二異丁酮、三甲基壬酮、環己酮、環戊酮、甲基環己酮、2,4-戊二酮、丙酮基丙酮(acetonylacetone)、二丙酮醇、苯乙酮、葑酮(fenchone)、乙醚、異丙醚、正丁醚(二-正丁醚,DBE)、正己醚、2-乙基己醚、環氧乙烷、1,2-環氧丙烷、二㗁𠷬、4-甲基二㗁𠷬、二㗁烷、二甲基二㗁烷、乙二醇單甲醚、乙二醇單乙醚、乙二醇二乙醚、乙二醇單-正丁醚、乙二醇單-正己醚、乙二醇單苯醚、乙二醇單-2-乙基丁醚、乙二醇二丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇二乙醚、二乙二醇單-正丁醚、二乙二醇二-正丁醚、二乙二醇單-正己醚、乙氧基三二醇、四乙二醇二-正丁醚、丙二醇單甲醚(PGME)、丙二醇單乙醚、丙二醇單丙醚、丙二醇單丁醚、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單丙醚、二丙二醇單丁醚、三丙二醇單甲醚、四氫呋喃、2-甲基四氫呋喃、二乙基碳酸酯、乙酸甲酯、乙酸乙酯、γ-丁內酯、γ-戊內酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯(正丁基乙酸酯、nBA)、乙酸異丁酯、乙酸二級丁酯、乙酸正戊酯、乙酸二級戊酯、乙酸3-甲氧基丁酯、乙酸甲酯戊酯、乙酸2-乙基丁酯、乙酸2-乙基己酯、乙酸苄酯、乙酸環己酯、乙酸甲酯環己酯、乙酸正壬酯、乙醯乙酸甲酯、乙醯乙酸乙酯、乙酸乙二醇單甲醚、乙酸乙二醇單乙醚、乙酸二乙二醇單甲醚、乙酸二乙二醇單乙醚、乙酸二乙二醇單-正丁醚、乙酸丙二醇單甲醚、乙酸丙二醇單乙醚、乙酸丙二醇單丙醚、乙酸丙二醇單丁醚、乙酸二丙二醇單甲醚、乙酸二丙二醇單乙醚、二乙酸二醇、乙酸甲氧基三二醇、丙酸乙酯、丙酸正丁酯、丙酸異戊酯、乙二酸二乙酯、乙二酸二-正丁酯、乳酸甲酯、乳酸乙酯(EL)、乳酸正丁酯、乳酸正戊酯、丙二酸二乙酯、苯二甲酸二甲酯、苯二甲酸二乙酯、丙二醇1-單甲醚2-醋酸酯(PGMEA)、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、N-甲基甲醯胺、N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、乙醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基丙醯胺、N-甲基吡咯啶酮、硫化二甲酯、硫化二乙酯、噻吩、四氫噻吩、二甲基亞碸、環丁碸、及1,3-丙烷磺內酯(1,3-propanesultone)。此等的溶劑可單獨或混合2種以上使用。
溶劑(B)較佳為PGME、PGMEA、EL、nBA、DBE或此等任一者的混合物;更佳為PGMEA、PGME、EL、nBA、DBE或此等任一者的混合物;再佳為PGME及PGMEA的混合物。此處將舉出的較佳例、即PGME、PGMEA、EL、nBA、DBE或此等任一者的混合物作為溶劑(B-1)。
雖不拘泥於理論,本發明的犧牲溶液為了提升填入性,較佳係亦包含沸點高的第2溶劑。將第2溶劑記為(B-2)。(B-2)較佳係高沸點溶劑。沸點宜以標準沸點來測量。(B-2)的標準沸點較佳為170℃以上;更佳為180℃以上;再佳為200℃以上;再更佳為210℃以上。(B-2)的標準沸點較佳為250℃以下;更佳為240℃以下;再佳為230℃以下。
作為(B-2)的具體例,可列舉例如:γ-丁內酯(204℃)、γ-戊內酯(207℃)、1,3-丁二醇二乙酸酯(232℃)、苄醇(205℃)、1,3-丁二醇(208℃)、二丙二醇(230℃)、乙二醇單丁醚(171℃)、乙二醇單苯醚(244℃)、二乙二醇單丁醚(231℃)、三乙二醇單丁醚(271℃)、二乙二醇單苯基醚 (283℃)、乙二醇單苄醚(256℃)、二乙二醇單苄醚(302℃)、二丙二醇單甲醚(187℃)、及三丙二醇單甲醚(242℃)。此等溶劑(B-2)可單獨或混合2種以上使用。
作為本發明的一態樣,犧牲溶液所包含的溶劑(B)、(B-1)及(B-2)的質量比{(B-1)+(B-2)}/(B)較佳為90%以上;更佳為95%以上;再佳為98%以上;再更佳為100%。作為本發明的一態樣,犧牲溶液所包含的溶劑(B-1)與(B-2)的質量比(B-2)/(B-1)較佳為0~4/6;更佳為0~1/9;再佳為0~5/95;再更佳為0。
在與其他層或膜的關係中,溶劑(B)實質上不含水亦為一態樣。例如,以溶劑(B)的總質量為基準,水的含量較佳為0.1質量%以下,更佳為0.01質量%以下,再佳為0.001質量%以下。溶劑(B)不含水(0質量%)亦為較佳型態之一。
溶劑(B)的含量可根據塗布方法及目標膜厚等調整,例如,以犧牲溶液的總質量為基準,較佳為50~95質量%;更佳為50~80質量%;再佳為60~70質量%。
(C)酸產生劑
本發明之犧牲溶液可包含酸產生劑(C)。作為酸產生劑(C),可列舉因照光而產生酸的光酸產生劑(PAG)、及因熱而產生酸的熱酸產生劑(TAG)。另外,可從步驟(3)的酸性水溶液得到用以使聚合物(A)的因酸而解離之保護基解離的酸,因此本發明的犧牲溶液中未必要為了去除犧牲層之上部而含有酸產生劑。
酸產生劑(C)的含量,以犧牲溶液的總質量為基準,宜為0~5質量%;更宜為0~1質量%;再宜為0質量%。作為本發明的一態樣,宜不含酸產生劑(C)(0質量%)。
又,本發明的另一態樣,係使犧牲溶液含有PAG,在去除犧牲層之上部後,再進行曝光、顯影,藉此可使去除後的犧牲層圖案化。亦即,亦可以光阻組成物的態樣使用。
作為犧牲溶液中所使用的PAG,可選自以往已知的光阻組成物中所使用的PAG。亦可將2種以上的PAG組合。PAG較佳為鎓鹽,更佳為錪鹽或鋶鹽。
含TAG的情況,到犧牲層去除之前(步驟(4)以前)的製程中,需要控制以避免因加熱而產生酸,此點係為重要。因此,較佳為產生酸所需之溫度高於犧牲層去除為止之加熱溫度的TAG。
(D)添加劑
本發明之犧牲溶液可含有添加劑(D)。添加劑(D)為界面活性劑、鹼性化合物、對比增強劑、塑化劑或此等任一者的混合物。作為本發明的一態樣,添加劑(D)宜為界面活性劑、鹼性化合物、塑化劑或此等的混合物;更宜為界面活性劑或鹼性化合物;再宜為界面活性劑。
添加劑(D)的含量,以犧牲溶液的總質量為基準,宜為0~10質量%;更宜為0.01~10質量%;再宜為0.01~5質量;再更宜為0.01~3質量%。若為了明確性而記載,添加劑(D)為多種混合物的情況(例如界面活性劑與塑化劑),前述較佳含量係由此等的總和所算出。作為本發明的一態樣,不含添加劑(D)(0質量%)亦為理想。
作為含界面活性劑的效果,可期待塗布性的提升及/或對於圖案基板的填入性提升。作為可用於本發明的界面活性劑,可列舉:(I)陰離子界面活性劑、(II)陽離子界面活性劑或(III)非離子界面活性劑,更具體而言,可列舉:(I)烷基磺酸酯、烷基苯磺酸、及烷基苯磺酸酯;(II)月桂基吡啶鎓氯化物(laurylpyridinium chloride)、及月桂基甲基氯化銨、以及(III)聚氧基乙烯基辛醚、聚氧乙烯基月桂基醚、聚氧乙烯基乙炔二醇醚(polyoxyethylene acetylenic glycolether)、含氟界面活性劑(例如,FLUORAD(3M)、MEGAFAC(DIC)、SULFURON(旭硝子)及有機矽氧烷界面活性劑(例如,KF-53、KP341(信越化學工業))。
此等的界面活性劑可單獨或混合2種以上使用。界面活性劑的含量,以犧牲溶液的總質量為基準,較佳為0~2質量%;更佳為0.01~2質量%;再佳為0.1~1質量%。
作為含鹼性化合物的效果,可列舉:在本發明之犧牲溶液含光酸產生劑並進行曝光的情況中,抑制在曝光部產生的酸擴散。雖不拘泥於理論,但認為藉由包含鹼性化合物而可抑制去除犧牲膜的深度不均並提高對比。
作為鹼性化合物的具體例,可列舉:
(i)氨,
(ii)C
1-16第一級脂肪族胺及其衍生物,例如甲胺、乙胺、異丙胺、三級丁胺、環己胺、伸乙二胺、四伸乙二胺等,
(iii)C
2-32第二級脂肪族胺及其衍生物,例如二甲胺、二乙胺、甲基乙胺、二環己胺、N,N-二甲基亞甲基二胺等,
(iv)C
3-48第三級脂肪族胺及其衍生物,例如三甲胺、三乙胺、二甲基乙胺、三環己胺、N,N,N’,N’-四甲基伸乙二胺、N,N,N’,N”,N”-五甲基二伸乙三胺、參[2-(二甲胺基)乙基]胺、參[2-(2-甲氧基乙氧基)乙基]胺等,
(v)C
6-30芳香族胺及其衍生物,例如苯胺、苄胺、萘胺、N-甲基苯胺、2-甲基苯胺、4-胺基苯甲酸、苯基丙胺酸等,
(vi)C
5-30雜環胺及其衍生物,例如吡咯、㗁唑、噻唑、咪唑、4-甲基咪唑、吡啶、甲基吡啶、丁基吡啶等。
鹼性化合物的鹼解離常數pKb(H
2O)較佳為-12~5;更佳為1~4。
鹼性化合物的分子量較佳為17~500;更佳為60~400。
鹼性化合物的含量,以犧牲溶液的總質量為基準,較佳為0~1質量%;更佳為0.01~1質量%。為了減少擴散至犧牲層中之酸的量,不含鹼性化合物(0質量%)亦為較佳型態之一。
作為對比增強劑,可列舉例如:由鹼可溶性的酚性化合物或羥基環化合物所衍生的、包含對於酸不穩定之基(以下稱為脫離基)的低分子量化合物。此處,脫離基與源自酸產生劑(C)的酸反應而從化合物脫離,使化合物對於鹼性水溶液的溶解度增加,而使對比變大。這樣的脫離基為例如-R
r1、-COOR
r1或-R
r2-COOR
r1(此處,R
r1為亦可在碳-碳之間包含氧原子的C
1-10直鏈狀、分支鏈狀或環狀烷基,R
r2為C
1-10伸烷基),亦可取代與化合物鍵結之羥基中的氫。這樣的對比增強劑,較佳係在分子內含2個以上之脫離基者。又,質量平均分子量為3,000以下,較佳為100~2,000。作為在羥基中導入脫離基之前的化合物,較佳為下述者。
對比增強劑可單獨或混合2種以上使用。對比增強劑的含量,以犧牲溶液的總質量為基準,較佳為0~5質量%;更佳為0.1~5質量%。
作為含塑化劑的效果,可期待提升犧牲層的彈性。
作為塑化劑的例子,可列舉:鹼可溶性乙烯基聚合物或含酸解離性基的乙烯基聚合物。更具體而言,可列舉例如:聚氯乙烯、聚苯乙烯、聚羥基苯乙烯、聚乙酸乙烯酯、聚苯甲酸乙烯酯、聚乙烯醚、聚乙烯基丁醛、聚乙烯醇、聚醚酯、聚乙烯基吡咯啶酮,聚丙烯酸、聚甲基丙烯酸、聚丙烯酸酯、馬來酸聚醯亞胺、聚丙烯醯胺、聚丙烯腈、聚乙烯基酚、酚醛清漆及此等的共聚物等,更佳為聚乙烯醚、聚乙烯基丁醛、聚醚酯。
塑化劑的質量平均分子量較佳為1,000~50,000;更佳為1,500~30,000;再佳為2,000~21,000;再更佳為2,000~15,000。
塑化劑的含量,以犧牲溶液的總質量為基準,較佳為0~5質量%;更佳為0.1~5質量%。不含塑化劑(0質量%)亦為本發明的較佳態樣之一。
本發明之犧牲溶液可含有(A)~(D)成分以外的成分,(A)~(D)成分以外的成分,以犧牲溶液的總質量為基準,較佳為5質量%以下,更佳為3質量%以下,再佳為0.5質量%以下。不含(A)~(D)成分以外的成分(0質量%),亦為本發明之犧牲溶液的較佳型態之一。
步驟(2)
步驟(2)中,由犧牲溶液形成犧牲層。
已施用犧牲溶液之基板,較佳係藉由加熱而形成犧牲層。(2)的加熱,例如係藉由加熱板進行。加熱溫度較佳為100~250℃;更佳為100~200℃;再佳為100~160℃。此處的溫度為加熱環境、例如加熱板的加熱面溫度。加熱時間較佳為30~300秒;更佳為30~120秒;再佳為60~120秒。加熱較佳係在大氣或氮氣環境下進行;更佳係在大氣環境下進行。
圖1(b)係基板上形成有犧牲層8的狀態下,從底部起算的高度為膜厚(初始膜厚)9。犧牲層的膜厚可因應目的而選擇,較佳為1~30μm;更佳為2~20μm;再佳為3~15μm。
步驟(2)與(3)之間,較佳係更包含對於犧牲層進行化學機械研磨的步驟。
藉由進行化學機械研磨,可達成表面的平坦化。
步驟(3)
步驟(3)中,可使犧牲層的表面接觸後述酸性水溶液。
圖1(c)係顯示犧牲層與酸性水溶液10接觸的狀態。
作為酸性水溶液接觸犧牲層的方法,可列舉例如:覆液(paddle)法、浸漬法、噴霧(沖淋)法,較佳為覆液法或浸漬法,更佳為覆液法。覆液法係指從噴嘴對於基板滴下液體,保持固定時間後,以旋轉器等使基板旋轉而使液體飛濺,藉此進行處理的方法。浸漬法係指在充滿液體的槽中連同基板一起浸漬固定時間,藉此進行處理的方法。噴霧法係指從多個噴嘴對於基板吹附液體,藉此進行處理的方法。本發明中,前述接觸時間較佳為10~600秒;更佳為10~300秒;再佳為20~180秒。雖不拘泥於理論,但為了提升裝置的製造效率,前述的接觸時間宜不過長,據認為藉由提升酸的濃度、使用pKa小的酸可縮短接觸時間。
與酸性水溶液接觸後,較佳為使用水等的沖洗液進行沖洗,以取代酸性水溶液。在經過上述接觸時間後,較佳係立即去除酸性水溶液,使用沖洗液的情況可藉由取代來去除,未使用沖洗液的情況可以旋轉乾燥等來去除。在經過上述接觸時間之後,以0.5~180秒進行酸性水溶液的去除;更佳係以0.5~60秒進行;再佳係以1~60秒進行;再更佳係以5~30秒進行。雖不拘泥於理論,但認為若不控制該間隔,則酸會擴散而無法控制去除犧牲層的深度。使用沖洗液的情況,可以習知的方法(例如旋轉乾燥)去除取代了酸性水溶液後的沖洗液。
之後,較佳係將基板加熱。雖不拘泥於理論,藉由該(3)的加熱,從犧牲層的表面滲透的酸在犧牲層中擴散。(3)的加熱根據欲去除之膜厚而有所不同,加熱溫度較佳為100~250℃;更佳為110~210℃;再佳為110~170℃。加熱時間較佳為30~600秒;更佳為60~450秒;再佳為180~450秒。加熱較佳係在大氣或氮氣環境中進行;更佳係在大氣環境中進行。藉由此酸,具有因酸而解離之保護基的聚合物其保護基解離,聚合物的溶解性改變,而可藉由去除液將其去除。藉由調整(3)的加熱時間及加熱溫度,可控制酸在犧牲層中擴散的區域、更宜為其深度。
[酸性水溶液]
本發明之酸性水溶液包含酸及水,其係用於與犧牲層接觸。酸性水溶液可包含酸及水以外的成分。例如酸性水溶液可包含界面活性劑。酸性水溶液所包含的酸及水以外的成分(多種的情況中為此等的總和),以酸性水溶液的總質量為基準,較佳為10質量%以下;更佳為5質量%以下;再佳為1質量%以下;再更佳為0質量%。
酸,如上述所記載,只要是可使聚合物(A)的保護基解離者,則未特別限定。較佳為選自包含下式(ZA)、(ZB)及(ZC)所示之化合物的群組。酸亦可為此等任一者的混合物。
式(ZA)所示之化合物如下。
此處,R
ZA為C
1-10氟取代烷基、C
1-10氟取代烷醚、C
6-20氟取代芳基、C
1-10氟取代醯基或C
6-20氟取代烷氧基芳基。前述氟取代係指R
ZA之烷基部分的氫的一部分或全部由氟所取代。R
ZA較佳為C
1-10氟取代烷基;更佳為C
2-6氟取代烷基;再佳為C
2-4氟取代烷基。然後,再佳為所有的氫皆被氟取代的全氟烷基。
作為式(ZA)所示之化合物的具體例,可列舉:CF
3SO
3H、C
4F
9SO
3H或C
3F
7SO
3H;更佳為CF
3SO
3H。
式(ZB)所示之化合物如下。
此處,R
ZB各自獨立為C
1-10氟取代烷基、C
1-10氟取代烷醚、C
6-20氟取代芳基、C
1-10氟取代醯基或C
6-20氟取代烷氧基芳基、2個R
ZB亦可互相鍵結而形成經氟取代的雜環結構。R
ZB較佳為C
1-10氟取代烷基;更佳為C
2-6氟取代烷基。然後,再佳為所有的氫皆被氟取代的全氟烷基。
2個R
ZB互相鍵結而形成經氟取代的雜環結構時,雜環可為單環亦可為多環。前述雜環結構可為飽和環,亦可為不飽和環;更佳為飽和環。雜環的構成員數較佳為5~20;較佳為構成員數5~8的單環結構。此時,R
ZB一般係包含經氟取代的碳氫鏈,但較佳為全氟伸烷基。又,R
ZB亦可更包含雜原子。
前述酸的酸解離常數的pKa(H
2O)較佳為-20~2.5;更佳為-16~2.0;再佳為-16~1.5;再更佳為-16~1.2。
酸的含量,以酸性水溶液的總質量為基準,較佳為0.0001~20質量%;更佳為0.001~20質量%;再佳為0.01~10質量%;再佳為1~10質量%。
步驟(4)
步驟(4)中,對於犧牲層施用後述去除液。
圖1(d)係顯示對於犧牲層施用去除液11的狀態。
去除液的施用方法,可列舉例如:覆液法、浸漬法、噴霧法。去除液的溫度較佳為5~50℃;更佳為25~40℃,去除液施用時間較佳為30~180秒;更佳為60~120秒。去除液施用後,將去除液去除。藉由此處理,去除犧牲層的一部分。典型而言,以大致均勻的薄膜減少量,從施用去除液之前的犧牲層表面去除犧牲層。
去除液的去除較佳係使用水等沖洗液進行沖洗,以取代去除液。使水等沖洗液流至基板表面以進行沖洗,亦為本發明的較佳態樣之一。較佳係在經過去除液施用時間後,以0.5~180秒進行去除液的去除;更佳為以0.5~60秒進行;再佳為以1~60秒進行;再更佳為以5~30秒進行。
圖1(e)係顯示犧牲層上部經去除的狀態,犧牲層中,去除了薄膜減少量13,而成為去除後的膜厚12。
根據本發明,可以高精度控制犧牲層的薄膜減少量,而能夠以預期的深度減少犧牲層的膜厚。
[去除液]
去除液係對於保護基解離後的聚合物之溶解性高、對於保護基未解離的聚合物之溶解性低者。較佳為鹼水溶液。作為鹼水溶液,可列舉:包含氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉等無機鹼、氨、乙胺、丙胺、二乙胺、二乙胺基乙醇、三乙胺等有機胺、四甲基氫氧化銨(TMAH)等四級胺等的水溶液,更佳為TMAH水溶液,再佳為2.38質量%TMAH水溶液。
去除液中亦可更添加上述界面活性劑。
本發明提供一種加工基板的製造方法,其中藉由上述方法形成上部經去除的犧牲層,更包含以下的步驟:
(5)對於犧牲層經去除之部分的基板進行表面處理;
(6)去除剩餘的犧牲層;及
(7)對於基板實施進一步的加工。
步驟(5)
步驟(5)中,對於犧牲層經去除的部分之基板進行表面處理。經過表面處理的部分,在後續步驟中成為遮罩。表面處理方法並未特別限定,可列舉:HMDS處理等。
圖2(f),係在基板14上形成上部經去除之犧牲層15,再填充表面處理16。進一步經過表面處理16者為圖2(g),其中露出犧牲層。經表面處理的部分發揮作為非加工部分之保護膜的功用。
步驟(6)
步驟(6)中,去除剩餘之犧牲層的一部分或全部。將犧牲層全部去除的方法,一般而言,可使用將光阻剝離的方法,可列舉例如施用有機溶劑。
圖2(h)顯示犧牲層經去除的狀態。
步驟(7)
步驟(7)中,對於基板實施進一步的加工。此處,步驟(5)中經表面處理的部分作為遮罩,僅對於步驟(6)中所去除的犧牲層曾經存在之處的基板進行加工。加工方法較佳為乾式蝕刻或濕式蝕刻;更佳為濕式蝕刻。雖不拘泥於理論,但認為藉由此處理,可在直徑隨著深度逐漸變窄的接觸孔或溝槽中於底部附近擴展,使孔或溝槽整體接近矩形。
前述濕式蝕刻液可使用一般的蝕刻液,可列舉例如:鹽酸、硫酸、硝酸、氟酸、磷酸、乙酸、氨、氫氧化鉀、氫氧化鈉、四甲基氫化銨(tetramethylammonium hydride)、過氧化氫水或此等的混合物。
圖2(i)係顯示犧牲層經去除並且經過加工之基板17的狀態。
具有在步驟(6)中去除了剩餘犧牲層之一部分的狀態下進行步驟(7)之加工的態樣。藉此,可不對於底部而是對於深度方向之中心周邊進行加工。雖具有藉由將形成有孔或溝槽的基板與相同地形成有孔或溝槽的基板重合以使基板變厚的態樣,但此時可能在孔或溝槽發生錯位。雖不拘泥於理論,但藉由前述處理增加接合部分之孔或溝槽的寬度,藉此可確保電性接合。藉此應對CIS配線等的填入不良,而可抑制連接不良及電特性不均。
在步驟(6)中去除剩餘之犧牲層的一部分時,可在步驟(6)中重複上述步驟(2)與(3)記載的方法。藉此,可將犧牲層去除至預期的深度。前述重複宜為1~3次;更宜為1~2次;再宜為1次。
因應需求去除保護膜,可得到加工基板。
根據本發明,可輕易製造僅對於基板中的特定處實施加工而成的基板。
又,重複上述步驟2次以上,可製造具有複雜結構的基板。
本發明提供一種加工基板的製造方法,其中藉由上述方法形成上部經去除的犧牲層,更包含以下步驟:
(5)’以等向性蝕刻對於基板進行加工;及
(6)’去除剩餘犧牲層的一部分或全部。
此處,步驟(5)’及(6)’係分別以此順序僅進行1次,或交互重複進行。步驟(5)’係在上述步驟(1)~(4)之後進行。若為了明確性而記載,則步驟(5)以後與步驟(5)’以後為不同的態樣,步驟(5)’並非接續於步驟(5)之後。
再者,本發明提供一種在步驟(5)’及(6)’之後更包含以下步驟的加工基板的製造方法:
(7)’在去除了犧牲層之處填充導電性構件。
步驟(5)’
步驟(5)’中,以等向性蝕刻對於基板進行加工。藉由步驟(5)’,可對於已去除犧牲層之處的基板進行選擇性加工。等向性蝕刻宜為濕式蝕刻。
作為用以對於構成基板的導電性含Si層進行加工的選擇性濕式蝕刻液,可列舉例如:磷酸水溶液。
作為用以對於構成基板的絕緣性含Si層進行加工的選擇性濕式蝕刻液,可列舉例如:氫氟酸水溶液。
基板具有絕緣性含Si層與導電性含Si層交互連續積層而成之結構時,藉由使用上述選擇性濕式蝕刻液,可大量蝕刻其中的任一層。可藉由變更濕式蝕刻液來進行目的加工。
步驟(6)’
步驟(6)’中去除剩餘犧牲層的一部分或全部。步驟(6)’中去除剩餘犧牲層的一部分時,可在步驟(6)’中重複上述步驟(2)與(3)記載的方法。
藉由重複進行前述步驟(5)’與步驟(6)’,可在深度方向上較淺之處的基板進行較多的加工,而在較深之處的基板進行較少的加工。藉此,可形成在深度方向上逐漸變窄的孔或溝槽。最後以對於構成基板之絕緣性含Si層進行選擇性加工的濕式蝕刻液進行加工,亦為本發明的一態樣。
圖3係顯示重複進行步驟(5)’與步驟(6)’三次而形成階梯狀結構之製造方法的一例的概念圖。圖3(i)係具有導電性含Si層31與絕緣性含Si層32交互積層而成之結構的基板,使用光阻等而成為具有凹部之結構的狀態。圖3(ii)係顯示該凹部中形成有以本發明之方法去除上部之犧牲層33的狀態。圖3(iii)係顯示以犧牲層作為遮罩而對於導電性含Si層的一部分進行等向性蝕刻的狀態。圖3(iv)係顯示犧牲層的一部分進一步被去除的狀態。圖3(v)~(viii)係顯示重覆等向性蝕刻與去除犧牲層之步驟的態樣。圖3(ix)係顯示從(viii)的狀態對於絕緣性含Si層進行選擇性濕式蝕刻而形成階梯狀結構的狀態。
步驟(7)’
(7)’中在犧牲層經去除之處填充導電性構件。填充可以習知的方法進行,例如使因加熱而溶解的導電性構件流入其中。(7)’之前的步驟(6)’宜為將剩餘的犧牲層全部去除的態樣。導電性構件宜為金屬或氧化金屬;更宜為金屬。此處所述的金屬,可為合金亦可為純金屬。合金宜為包含多種金屬元素的金屬。藉由步驟(5)’可對於基板在深度方向上較淺之處進行加工而使其擴展,因此可形成上部在橫向上具有寬結構而在下部具有細長結構的導電構件。
圖4係顯示形成上部在橫向上具有寬結構的導電構件之方法的一例的概念圖。圖4(i)係顯示具有絕緣性含Si層的基板,圖4(ii)係顯示光阻圖案42形成於其上的狀態,圖4(iii)係顯示使用光阻圖案且絕緣性含Si層經過加工的狀態。作為圖4(i)的絕緣性含Si層的較佳例,可列舉SiO
2層。圖4(iv)係顯示藉由本發明之方法形成上部經去除之犧牲層43的狀態。圖4(v)係顯示將上部經去除的犧牲層作為遮罩且絕緣性含Si層的上部經過加工的狀態,之後犧牲層經去除的狀態則為圖4(vi)。圖4(vii)係顯示在犧牲層經去除之處填充有導電性構件44的狀態。
犧牲溶液包含酸產生劑的情況,亦可藉由曝光、顯影使其圖案化,而作為如所謂光阻的使用方法。曝光、顯影在例如步驟(4)之後或是步驟(5)之後進行為本發明的一態樣。
本發明提供一種裝置的製造方法,包含上述的犧牲層上部經去除之基板的製造方法或是加工基板的製造方法。可因應需求進一步對於基板加工,將基板裁切為晶片狀,與引線框架連接,然後以樹脂等封裝。較佳係以習知的方法在基板上形成配線。本發明中,將此經過封裝者稱為裝置。作為裝置,可列舉:半導體元件、液晶表示元件、有機EL顯示元件、電漿顯示器元件、太陽能電池元件。裝置較佳為半導體元件。
[實施例]
以下以各例說明本發明。另外,本發明的態樣不限於此等例子。
[犧牲溶液1的製備]
將聚合物A1(34.8質量%)與界面活性劑(0.2質量%)添加至PGME(45.5質量%)及PGMEA(19.5質量%)的混合溶劑。各質量%的值係以犧牲溶液的總質量為基準的含有率。在常溫下將所得之溶液攪拌60分鐘。以目視確認溶質完全溶解。以0.2μm的氟化樹脂過濾器過濾該溶液,得到犧牲溶液1。
[犧牲溶液2~6的製備]
將組成變更為表1記載的內容,除此之外,與犧牲溶液1相同地製備犧牲溶液2~6。表1中的數值係以犧牲溶液的總質量為基準的各成分之含量(質量%)。
[表1]
表中,
・聚合物A1:對羥基苯乙烯/苯乙烯/丙烯酸三級丁酯共聚物(聚合比分別60%:20%:20%,Mw12,000)
・聚合物A2:間甲酚/對甲酚共聚物(聚合比60:40,Mw12,000)
・光酸產生劑:三苯基鋶全氟-1-丁烷磺酸酯,(Sigma-Aldrich)
・界面活性劑:MEGAFACR-41(DIC)
・鹼性化合物:參[2-(2-甲氧基乙氧基)乙基]胺(東京化成工業,以下稱為TCI)
・對比增強劑:1,1,1-參(4-羥基苯基)乙烷(TCI)
・塑化劑:聚乙烯基甲醚(Mw57,000)
表1 | 聚合物(A) | 溶劑(B) | 酸產生劑(C) | 添加劑(D) | ||||||||
犧牲溶液1 | 聚合物A1 | 34.8 | PGME | 45.5 | PGMEA | 19.5 | - | 界面活性劑 | 0.2 | - | ||
犧牲溶液2 | 聚合物A1 | 34.7 | PGME | 45.5 | PGMEA | 19.5 | - | 界面活性劑 | 0.2 | 鹼性化合物 | 0.1 | |
犧牲溶液3 | 聚合物A1 | 32.8 | PGME | 45.5 | PGMEA | 19.5 | - | 界面活性劑 | 0.2 | 對比增強劑 | 2.0 | |
犧牲溶液4 | 聚合物A1 | 32.8 | PGME | 45.5 | PGMEA | 19.5 | - | 界面活性劑 | 0.2 | 塑化劑 | 2.0 | |
犧牲溶液5 | 聚合物A1 | 33.8 | PGME | 45.5 | PGMEA | 19.5 | 光酸產生劑 | 1.0 | 界面活性劑 | 0.2 | - | |
犧牲溶液6 | 聚合物A2 | 34.8 | PGME | 45.5 | PGMEA | 19.5 | - | 界面活性劑 | 0.2 | - | ||
[實施例1]
使用Coater Developer (「CLEAN TRACK Mark 8」,Tokyo Electron),以1,000rpm將犧牲溶液1旋塗於階差Si基板上。所使用之階差Si基板係1:1線距,溝槽寬度:10μm,壁寬度:10μm,深度:10μm,縱橫比1:1。在大氣條件下於120℃將此基板加熱90秒,形成犧牲層。
此處製作所得之犧牲層的切片,得到SEM(SU8230,Hitachi High-Tech Fielding)影像,觀察犧牲層埋入階差基板。所得之結果如表2所示。填入性良好係指填入其中且圖案附近無孔洞。再者,以階差基板的溝槽底部為起點,測量犧牲層的膜厚。所得之膜厚(初始膜厚)如表2所示。
與上述相同地形成犧牲層。在所形成之犧牲層的表面上澆注作為酸性水溶液的8質量%之三氟甲磺酸(TfOH)水溶液,並且保持(覆液)。此酸的接觸時間(覆液時間)如表2所示。之後,在犧牲層上澆注去離子水,沖洗20秒,以去離子水取代酸。以1,000rpm將基板旋轉乾燥2秒。之後,在大氣條件下於130℃將基板乾燥300秒。之後,在犧牲層上,於表2之去除液施用時間的期間內覆液作為去除液的2.38質量%TMAH水溶液。之後立即在該此犧牲層上澆注去離子水,沖洗20秒,以去離子水取代TMAH水溶液。以1,000rpm將基板旋轉乾燥2秒。藉此得到上部經去除的犧牲層(第1次)。
此處,與上述切片之製作相同地形成切片,與上述膜厚之測量相同地測量膜厚。實施例1中,初始膜厚為12μm,去除處理後的膜厚為5μm,可確認第一次的薄膜減少量(上部的去除量)為7μm。
與上述相同地形成上部經去除的犧牲層(第1次)。在該犧牲層上,於表2的去除液施用時間之期間,覆液作為去除液的2.38質量%TMAH水溶液。之後,在該犧牲層上澆注去離子水,沖洗20秒,以去離子水取代TMAH水溶液。以1,000rpm將基板旋轉乾燥2秒。藉此得到上部經去除的犧牲層(第2次)。
此處,與上述切片之製作相同地形成切片,與上述膜厚之測量相同地測量膜厚。實施例1中,第2次的薄膜減少量((上部經去除的犧牲層(第1次)的膜厚)-(上部經去除的犧牲層(第2次)的膜厚))為0。
[實施例2~7及比較例1及2]
使犧牲溶液、酸性水溶液、酸接觸時間及去除液施用時間為表2所記載之內容,除此之外,與實施例1相同地進行犧牲層上部的去除。與實施例1相同地進行填入性、膜厚及薄膜減少量的測量,所得之結果如表2所示。
另外,比較例1中未進行酸性水溶液之接觸。
[表2]
表中,
・TfOH:三氟甲烷磺酸(Sigma-Aldrich)
表2 | 犧牲溶液 | 填入性 | 膜厚 | 酸性水溶液 | 酸接觸時間 (秒) | 去除液適用 時間(秒) | 薄膜減少量(μm) | ||
(μm) | 第1次 | 第2次 | |||||||
實施例 | 1 | 犧牲溶液1 | 良好 | 12 | 8質量%TfOH | 60 | 90 | 7 | 0 |
2 | 犧牲溶液2 | 良好 | 12 | 8質量%TfOH | 60 | 90 | 7 | 0 | |
3 | 犧牲溶液3 | 良好 | 12 | 8質量%TfOH | 60 | 90 | 7 | 0 | |
4 | 犧牲溶液4 | 良好 | 12 | 8質量%TfOH | 60 | 90 | 7 | 0 | |
5 | 犧牲溶液1 | 良好 | 12 | 1質量%TfOH | 120 | 90 | 7 | 0 | |
6 | 犧牲溶液1 | 良好 | 12 | 0.1質量%TfOH | 300 | 90 | 7 | 0 | |
7 | 犧牲溶液1 | 良好 | 12 | 0.01質量%TfOH | 600 | 90 | 7 | 0 | |
比較例 | 1 | 犧牲溶液5 | 良好 | 12 | - | - | 600 | 0 | 0 |
2 | 犧牲溶液6 | 良好 | 12 | 8質量%TfOH | 60 | 600 | 3 | 3 |
在實施例1~7及比較例1中,確認在第2次施用去除液後,薄膜並未進一步減少。例如,實施例1中即使第2次施用去除液,膜厚仍為5μm,可確認從第1次的去除後薄膜即未減少。比較例2中,確認不僅是第1次施用去除液,在第2次施用去除液後薄膜亦減少。
1:基板
2:壁
3:溝槽
4:溝槽底部
5:壁寬度
6:溝槽寬度
7:溝槽深度
8:犧牲層
9:初始膜厚
10:酸性水溶液
11:去除液
12:去除後膜厚
13:薄膜減少量
14:基板
15:上部經去除的犧牲層
16:表面處理
17:經加工之基板
31:導電性含Si層
32:絕緣性含Si層
33:上部經去除的犧牲層
41:絕緣性含Si層
42:光阻圖案
43:上部經去除的犧牲層
44:導電性構件
圖1係顯示去除犧牲層之上部之方法的一型態的概念圖。
圖2係顯示加工基板的製造方法之一型態的概念圖。
圖3係顯示加工基板的製造方法之另一型態的概念圖。
圖4係顯示加工基板的製造方法之另一型態的概念圖。
1:基板
2:壁
3:溝槽
4:溝槽底部
5:壁寬度
6:溝槽寬度
7:溝槽深度
8:犧牲層
9:初始膜厚
10:酸性水溶液
11:去除液
12:去除後膜厚
13:薄膜減少量
Claims (15)
- 一種去除犧牲層之上部的方法,包含以下步驟: (1)將包含具有因酸而解離之保護基的聚合物(A)及溶劑(B)的犧牲溶液施用於基板(較佳為圖案基板)的上方; (2)從所施用之犧牲溶液(較佳係藉由加熱)形成犧牲層; (3)使酸性水溶液接觸犧牲層的表面(接觸較佳係以覆液法(paddle)或浸漬法進行,及/或較佳係在接觸後進行加熱);及 (4)將去除液施用於犧牲層。
- 如請求項1之方法,其中在(2)與(3)之間,更包含對於犧牲層進行化學機械研磨的步驟。
- 如請求項1或2之方法,其中聚合物(A)的因酸而解離之保護基係選自包含-C(R 1)(R 2)(R 3)、-C(R 1)(R 2)(OR 4)及-C(R 5)(R 6)(OR 4)之群組中的至少一式所表示的基; 此處, R 1~R 4各自獨立為烷基、環烷基、芳基、芳烷基或烯基,R 1與R 2亦可相互鍵結而形成環; R 5及R 6各自獨立為氫、環烷基、烷基、芳基、芳烷基或烯基; 較佳係聚合物(A)的主鏈及/或側鏈具有因酸而解離之保護基。
- 如請求項1至5中至少任一項之方法,其中聚合物(A)的含量,以犧牲溶液的總質量為基準,為5~50質量%; 溶劑(B)的含量,以犧牲溶液的總質量為基準,較佳為50~95質量%。
- 如請求項1至6中至少任一項之方法,其中犧牲溶液包含酸產生劑(C),酸產生劑(C)的含量,以犧牲溶液的總質量為基準,為0~5質量%; 酸產生劑(C)的含量,以犧牲溶液的總質量為基準,較佳為0質量%。
- 如請求項1至7中至少任一項之方法,其中犧牲溶液更包含添加劑(D),此處添加劑(D)為界面活性劑、鹼性化合物、對比增強劑、塑化劑或此等任一者的混合物。
- 如請求項1至8中至少任一項之方法,其中犧牲溶液中,以犧牲溶液的總質量為基準,包含: 0~2質量%的界面活性劑; 0~1質量%的鹼性化合物; 0~5質量%的對比增強劑;及/或 0~5質量%的塑化劑。
- 一種犧牲溶液,包含具有因酸而解離之保護基的聚合物(A)及溶劑(B), 前述犧牲溶液形成犧牲層,犧牲層與酸性水溶液接觸,而藉由去除液去除犧牲層之上部。
- 一種酸性水溶液,用以與犧牲層接觸,其含有選自包含下式(ZA)、(ZB)及(ZC)所示之化合物的群組中的酸及水: (此處,R ZA為C 1-10氟取代烷基、C 1-10氟取代烷醚、C 6-20氟取代芳基、C 1-10氟取代醯基或C 6-20氟取代烷氧基芳基); (此處,R ZB各自獨立為C 1-10氟取代烷基、C 1-10氟取代烷醚、C 6-20氟取代芳基、C 1-10氟取代醯基或C 6-20氟取代烷氧基芳基,2個R ZB亦可互相鍵結而形成經氟取代的雜環結構); (此處, R ZC為氫、C 1-6烷基、C 1-6烷氧基或羥基; L ZC為氧基或羰氧基; X ZC各自獨立為氫或氟; n ZC1為0~10;且 n ZC2為0~21)。
- 一種加工基板的製造方法,包含下述步驟: 準備已藉由如請求項1至9中至少任一項之方法去除犧牲層之上部的基板; (5)對於前述基板中去除了犧牲層的部分進行表面處理; (6)去除剩餘的犧牲層;及 (7)對於前述基板實施進一步的加工。
- 一種加工基板的製造方法,包含下述步驟: 準備已藉由如請求項1至9中至少任一項之方法去除犧牲層之上部的基板; (5)’以等向性蝕刻對於基板進行加工;及 (6)’去除剩餘犧牲層的一部分或全部: 此處,步驟(5)’及(6)’分別以此順序僅進行一次,或是交互重複進行。
- 如請求項13之加工基板的製造方法,其更包含以下步驟: (7)’在犧牲層經去除之處填充導電性構件。
- 一種裝置的製造方法,包含如請求項1至9及12至14中至少任一項之方法,其中, 較佳係更包含在前述基板上形成配線的步驟;或 前述裝置較佳為半導體元件。
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