TWI688580B - 器件形成方法及層狀製品 - Google Patents

器件形成方法及層狀製品 Download PDF

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TWI688580B
TWI688580B TW107103227A TW107103227A TWI688580B TW I688580 B TWI688580 B TW I688580B TW 107103227 A TW107103227 A TW 107103227A TW 107103227 A TW107103227 A TW 107103227A TW I688580 B TWI688580 B TW I688580B
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Taiwan
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methyl
monomer
meth
copolymer
substituted
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TW107103227A
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TW201819437A (zh
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詹姆士W 薩克雷
科 杜
彼得 Iii 特萊弗納斯
伊德里斯 布萊基
安德魯 凱斯 惠特克
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美商羅門哈斯電子材料有限公司
昆士蘭大學
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    • A24BMANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B1/00Preparation of tobacco on the plantation
    • A24B1/04Sifting, sorting, cleaning or removing impurities from tobacco
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    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • A24B13/00Tobacco for pipes, for cigars, e.g. cigar inserts, or for cigarettes; Chewing tobacco; Snuff
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract

藉由使包括紫外光吸收型單體以及鹼溶解度增強型單體的單體聚合來製備共聚物。所述共聚物適用於形成電子束以及遠紫外微影術用的面塗層。亦描述包括所述面塗層的層狀製品以及形成電子器件的相關方法。

Description

器件形成方法及層狀製品
本發明係關於共聚物、含有所述共聚物的光微影術面塗層、包含所述面塗層的層狀製品,以及形成電子器件的方法,其中所述方法利用所述面塗層。
遠紫外(Extreme ultraviolet;EUV)微影術及電子束微影術在20奈米及小於20奈米的等級下為有前景的圖案化技術。EUV輻射源亦產生較長波長的輻射,所謂的頻帶外(out-of-band;OOB)輻射,其能使成像效能顯著惡化。因此需要能減少頻帶外輻射之負面影響而不會過度降低其他光微影回應的組合物。共同提交的美國專利申請案第14/820647號描述一種光阻組合物,其包含自分層的OOB輻射吸收型嵌段聚合物。就希望避免或最小化修飾光阻組合物的情形而言,本申請描述一種適用於OOB輻射吸收型、顯影劑可溶性面塗層中的共聚物。
一個實施例為一種共聚物,其中所述共聚物包含單體聚合產物,所述單體包括:頻帶外吸收單體;及鹼溶解度增強型單體;其中由所述共聚物鑄成的膜在150奈米至400奈米範圍內的波長下具有0.1至0.5的消光係數k。
另一個實施例為形成聚合物層的方法,所述方法包含對聚合物溶液進行旋塗,所述聚合物溶液包含存在於溶劑中的0.1重量%至3重量%共聚物,所述溶劑選自由以下各者組成的群組:2-甲基-2-丁醇、2-甲基-2-戊醇、2-甲基-2-丁醇與2-甲基-2-戊醇的組合、二丙二醇單甲基醚與2-甲基-2-丁醇的組合(含有至少90重量%的2-甲基-2-丁醇)、二丙二醇單甲基醚與2-甲基-2-戊醇的組合(含有至少90重量%的2-甲基-2-戊醇),以及二丙二醇單甲基醚與2-甲基-2-丁醇與2-甲基-2-戊醇的組合(總計含有至少90重量%的2-甲基-2-丁醇以及2-甲基-2-戊醇)。
另一個實施例為一種層狀製品,其包含:基板;位於所述基板上的光阻層;以及包含所述共聚物、位於所述光阻層上並且與所述光阻層接觸的面塗層。
另一個實施例為一種形成電子器件的方法,所述方法包含:(a)在基板上塗覆光阻層;(b)在所述光阻層上塗覆包含共聚物的面塗層;(c)使光阻層直至面塗層逐圖案曝露於活化輻射;以及(d)使所曝露的光阻層顯影以提供抗蝕劑浮雕影像。
下文詳細描述此等及其他實施例。
第1圖為合成聚(PEGMA-共-BzMA-共-HFACHOH)的反應流程。
第2圖為移除聚(PEGMA-共-BzMA-共-HFACHOH)中的RAFT端基的反應流程。
第3圖提供聚(PEGMA-共-BzMA-共-HFACHOH)在RAFT端基裂解(移除)之前及之後的標準化紫外光-可見光光譜。
第4圖為面塗層聚合物聚(PEGMA-共-BzMA-共-HFACHOH)的1H NMR光譜。
第5A圖及第5B圖呈現:第5A圖CBP-4光阻層;以及第5B圖面塗層中的膜厚度(nm)相對於聚合物濃度(重量%(wt%))的圖。
第6圖為10奈米面塗層、30奈米面塗層、CBP-4+10nm面塗層、CBP-4+30nm面塗層以及CBP-4的接觸角(°)與顯影時間(1秒或60秒)關係的圖。
第7圖為具有10奈米以及30奈米厚度的面塗層的消光係數相對於波長(nm)的圖。
第8圖為具有10奈米以及30奈米厚度的面塗層的透射率(%)相對於波長(nm)的圖。
第9圖為(a)CBP-4光阻以及(b)CBP-4光阻+10nm面塗層的標準化膜厚度(%)與劑量(微庫侖/厘米2(μC/cm2))關係的圖。
第10A圖、第10B圖、第10C圖、第10D圖、第10E圖及第10F圖由以下各物的線圖案的掃描電子顯微照片(scanning electron micrographs;SEM)組成:第10A圖51μC/cm2的光阻CBP-4;第10B圖53μC/cm2的光阻CBP-4;第10C圖55μC/cm2的光阻CBP-4;第10D圖51μC/cm2的光阻CBP-4+面塗層;第10E圖57μC/cm2的光阻CBP-4+面塗層;第10F圖60μC/cm2的光阻CBP-4+面塗層。
本發明人已確定特定共聚物在電子束或遠紫外微影術中適用作面塗層的主要或唯一組分。所述共聚物吸收頻帶外(OOB)輻射並且容易溶解於鹼性顯影劑中。
如本文所用,術語「共聚物」包括無規共聚物(包括統計學共聚物)、嵌段共聚物以及接枝共聚物。無規共聚物可以包括兩、三、四種或超過四種不同類型的重複單元。嵌段共聚物可以為多嵌段共聚物並且可以包括例如二嵌段共聚物、三嵌段共聚物、四嵌段共聚物,或具有五個嵌段或超過五個嵌段的共聚物。嵌段可以為線性共聚物、分支鏈共聚物(其中分支鏈接枝至主鏈上)(此等共聚物有時也稱為「梳形共聚物」)、星形共聚物(有時稱為徑向嵌段共聚物)及其類似物的一部分。在接枝共聚物中,主鏈以及一或多個側鏈的組成就組成或重複單元的順序而言為不同的。
如本文所用,術語「(甲基)丙烯酸酯」意指丙烯酸酯或甲基丙烯酸酯。
如本文所用,術語「烴基」無論單獨地還是作為另一術語的前綴、後綴或片段使用,是指僅含有碳及氫的殘基,除非其特定地被標識為「經取代的烴基」。烴基殘基可以為脂族或芳族、直鏈、環狀、雙環、分支鏈、飽和或不飽和的。其亦可含有脂族、芳族、直鏈、環狀、雙環、分支鏈、飽和以及不飽和烴部分的組合。當烴基殘基被描述為經取代時,除碳及氫之外,其亦可以含有雜原子。
除非另有說明,否則術語「經取代」意指包含至少一個取代基,例如鹵素(即F、Cl、Br、I)、羥基、胺基、 硫醇、羧基、羧酸酯、酯(包括丙烯酸酯、甲基丙烯酸酯以及內酯)、醯胺、腈、硫化物、二硫化物、硝基、C1-18烷基、C1-18烯基(包括降冰片烯基以及金剛烷基)、C1-18烷氧基、C2-18烯氧基(包括乙烯基醚)、C6-18芳基、C6-18芳氧基、C7-18烷基芳基或C7-18烷基芳氧基。
如本文所用,術語「氟化」應理解為意指基團中併入一或多個氟原子。舉例而言,在指示C1-18氟烷基的情況下,氟烷基可以包含一或多個氟原子,例如單個氟原子、兩個氟原子(例如,如1,1-二氟乙基)、三個氟原子(例如,如2,2,2-三氟乙基)或位於碳的每個自由價上的氟原子(例如,如全氟化基團,例如-CF3、-C2F5、-C3F7或-C4F9)。
如本文所用,術語「烷基」包括直鏈烷基、分支鏈烷基、環狀烷基,以及合併直鏈、分支鏈以及環基的雙向組合以及三向組合的烷基。烷基可以為未經取代或經取代的。烷基的特定實例包括甲基、乙基、1-丙基、2-丙基、環丙基、1-丁基、2-丁基、2-甲基-1-丙基、第三丁基、環丁基、1-甲基環丙基、2-甲基環丙基、1-戊基、2-戊基、3-戊基、2-甲基-1-丁基、3-甲基-1-丁基、2-甲基-2-丁基、3-甲基-2-丁基、2,2-二甲基-1-丙基(新戊基)、環戊基、1-甲基環丁基、2-甲基環丁基、3-甲基環丁基、1,2-二甲基環丙基、2,2-二甲基環丙基、2,3-二甲基環丙基、1-己基、2-己基、3-己基、2-甲基-1-戊基、3-甲基-1-戊基、4-甲基-1-戊基、2-甲基-2-戊基、4-甲基-2-戊基、2-甲基-3-戊基、3-甲基-2-戊基、3-甲基-3-戊基、2,2-二甲基-1-丁基、3,3-二甲基-1-丁基、3,3-二甲基-2-丁基、2,3-二甲基-1-丁基、2,3-二甲基-2-丁基、1,2,2-三甲基環丙基、 2,2,3-三甲基環丙基、(1,2-二甲基環丙基)甲基、(2,2-二甲基環丙基)甲基、1,2,3-三甲基環丙基、(2,3-二甲基環丙基)甲基、2,2-二甲基環丁基、2,3-二甲基環丁基、(1-甲基環丁基)甲基、1,2-二甲基環丁基、2,3-二甲基環丁基、(2-甲基環丁基)甲基、1,3-二甲基環丁基、2,4-二甲基環丁基、(3-甲基環丁基)甲基、1-甲基環戊基、2-甲基環戊基、環戊基甲基、環己基、1-降冰片烷基、2-降冰片烷基、3-降冰片烷基、1-金剛烷基、2-金剛烷基、八氫-1-并環戊二烯基、八氫-2-并環戊二烯基、八氫-3-并環戊二烯基、八氫-1-苯基-1-并環戊二烯基、八氫-2-苯基-2-并環戊二烯基、八氫-1-苯基-3-并環戊二烯基、八氫-2-苯基-3-并環戊二烯基、十氫-1-萘基、十氫-2-萘基、十氫-3-萘基、十氫-1-苯基-1-萘基、十氫-2-苯基-2-萘基、十氫-1-苯基-3-萘基以及十氫-2-苯基-3-萘基。
一個實施例為一種共聚物,其中所述共聚物包含單體聚合產物,所述單體包括:頻帶外吸收單體;及鹼溶解度增強型單體;其中由所述共聚物鑄成的膜在150奈米至400奈米範圍內的波長下具有0.1至0.5的消光係數k。
如本文所用,術語「頻帶外吸收型單體」意指吸收輻射的波長比打算曝露光阻的輻射長的單體。舉例而言,若曝光器件使用13.5奈米波長的遠紫外線輻射,則吸收150奈米至400奈米(確切地說,190奈米至300奈米)波長範圍內的紫外輻射的單體將為頻帶外吸收型單體。「頻帶外吸收型單體」提供在150奈米至400奈米範圍內具有吸光度的共聚物。確切地說,由共聚物鑄成的膜在150奈米至400奈米範圍內的波長(即,至少一種波長)下具有0.1至0.5的消光係 數k。在一些實施例中,在150奈米至400奈米範圍內,消光係數k的最大值為0.1至0.5。應瞭解,消光係數k在150奈米至400奈米範圍內的一些波長下可以小於0.1並且甚至為零。頻帶外吸收型單體不包括氟取代的酯基。在一些實施例中,頻帶外吸收型單體包含未經取代或經取代的不含氟的C6-C18芳基、未經取代或經取代的C2-C17雜芳基、C5-C12二烯酮基團,或其組合。
在一些實施例中,頻帶外吸收型單體具有結構:
Figure 107103227-A0101-12-0007-2
其中R1為氫或甲基;n為0、1、2、3或4;並且Ar1為未經取代或經取代的C6-C18芳基,其條件為經取代的C6-C18芳基不含氟。
頻帶外吸收型單體的特定實例包括
Figure 107103227-A0101-12-0007-3
及其組合。
以共聚物中的100莫耳%總重複單元計,共聚物可以包含20莫耳%至60莫耳%的衍生自頻帶外吸收型單體的 重複單元。在20莫耳%至60莫耳%範圍內,衍生自頻帶外吸收型單體的重複單元的含量可以為30莫耳%至50莫耳%。
除衍生自頻帶外吸收型單體的重複單元之外,共聚物亦包含衍生自鹼溶解度增強型單體的重複單元。鹼溶解度增強型單體包括聚(氧化乙烯)的(甲基)丙烯酸酯、聚(氧化丙烯)的(甲基)丙烯酸酯、鹼不穩定性(甲基)丙烯酸酯、經具有2至12的pKa的基團取代的(甲基)丙烯酸酯,及其組合。
聚(氧化乙烯)以及聚(氧化丙烯)的(甲基)丙烯酸酯可以具有結構:
Figure 107103227-A0101-12-0008-4
其中R1為氫(對於丙烯酸酯)或甲基(對於甲基丙烯酸酯)、R2為氫(對於聚(氧化乙烯))或甲基(對於聚(氧化丙烯)),並且n為3至50,確切地說,5至30。
鹼不穩定(甲基)丙烯酸酯包括經內酯取代的單體,例如
Figure 107103227-A0101-12-0008-5
Figure 107103227-A0101-12-0009-6
及其組合。
經具有2至12的pKa的基團取代的(甲基)丙烯酸酯包括經羧酸、苯酚、芳基磺酸、鄰苯二甲醯亞胺、磺醯胺、磺醯亞胺以及醇取代的(甲基)丙烯酸酯。熟習此項技術者可容易確定包含此等酸性官能基之一的特定物質是否具有2至12範圍內的pKa值。經具有2至12的pKa的基團取代的(甲基)丙烯酸酯的特定實例包括例如
Figure 107103227-A0101-12-0009-7
Figure 107103227-A0101-12-0010-8
及其組合。
在一些實施例中,鹼溶解度增強型單體包含聚(氧化乙烯)的(甲基)丙烯酸酯,以及包含1,1,1,3,3,3-六氟-2-丙基的(甲基)丙烯酸酯。
以共聚物中的100莫耳%總重複單元計,共聚物可以包含40莫耳%至80莫耳%的衍生自鹼溶解度增強型單體的重複單元。在40莫耳%至80莫耳%範圍內,衍生自頻帶外吸收型單體的重複單元的含量可以為50莫耳%至70莫耳%。在非常特定的實施例中,共聚物包含30莫耳%至50莫耳%的聚(氧化乙烯)的(甲基)丙烯酸酯以及10莫耳%至30莫耳%的 經1,1,1,3,3,3-六氟-2-丙基取代的(甲基)丙烯酸酯。
在一些實施例中,共聚物由衍生自頻帶外吸收型單體以及鹼溶解度增強型單體的重複單元組成。
共聚物在193奈米波長下具有0.1至0.4的消光係數「k」。在此範圍內,在193奈米波長下,消光係數「k」可以為0.15至0.35。測定消光係數「k」的程序描述於實施例中。
對於共聚物的分子量不存在特定的限制。分子量特徵可以藉由尺寸排阻層析法、使用聚苯乙烯標準以及四氫呋喃溶劑來測定。在一些實施例中,共聚物具有2,000道爾頓至100,000道爾頓(Daltons)的數目平均分子量。在此範圍內,數目平均分子量可以為3,000道爾頓至60,000道爾頓,確切地說,4,000道爾頓至40,000道爾頓。具體而言,當使用本文所述的RAFT方法製備共聚物時,其可以具有窄分子量分佈。分子量分佈可以藉由分散度表徵,分散度為重量平均分子量相對於數目平均分子量的比率。在一些實施例中,共聚物具有1.05至1.2的分散度(Mw/Mn)。在此範圍內,分散度可以為1.05至1.15。然而,窄分子量分佈並非為共聚物發揮預定功能所必需的。舉例而言,在一些實施例中,共聚物具有1.05至2的分散度。
在一些實施例中,使用選自由以下各者組成的群組的方法提純共聚物:沈澱、過濾、溶劑交換、離心、傾析(包括多傾析)、離子交換及其組合。
在共聚物的一個非常特定的實施例中,頻帶外吸收型單體具有結構:
Figure 107103227-A0101-12-0012-10
其中R1為氫或甲基,n為0、1、2、3或4,並且Ar1為未經取代或經取代的不含氟的C6-C18芳基;鹼溶解度增強型單體包含聚(氧化乙烯)的(甲基)丙烯酸酯以及經1,1,1,3,3,3-六氟-2-丙基取代的(甲基)丙烯酸酯;以單體的總莫耳數計,單體包含30莫耳%至50莫耳%的頻帶外吸收型單體、30莫耳%至50莫耳%的聚(氧化乙烯)的(甲基)丙烯酸酯以及10莫耳%至30莫耳%的經1,1,1,3,3,3-六氟-2-丙基取代的(甲基)丙烯酸酯;並且共聚物具有1.05至1.2的分散度(Mw/Mn)。
共聚物特別適用於形成電子束微影術或遠紫外微影術中的面塗層。共聚物在面塗層中可以占50重量%至100重量%。面塗層中的可選組分包括疏水性添加劑以增強面塗層與下伏光阻層的實體分離。
面塗層可以具有5奈米至50奈米的厚度,確切地說,5奈米至40奈米的厚度。層厚度可以藉由改變用於旋塗的溶液中的共聚物濃度來控制。
一個實施例為形成聚合物層的方法,包含對共聚物溶液進行旋塗,所述共聚物溶液包含存在於溶劑中的0.1重量%至3重量%共聚物(其上述變型中的任一者),所述溶劑選自由以下各者組成的群組:2-甲基-2-丁醇、2-甲基-2-戊醇、2-甲基-2-丁醇與2-甲基-2-戊醇的組合、二丙二醇單甲基醚與2-甲基-2-丁醇的組合(含有至少90重量%的2-甲基-2-丁醇)、二丙二醇單甲基醚與2-甲基-2-戊醇的組合(含有至少 90重量%的2-甲基-2-戊醇),以及二丙二醇單甲基醚與2-甲基-2-丁醇與2-甲基-2-戊醇的組合(總計含有至少90重量%的2-甲基-2-丁醇以及2-甲基-2-戊醇)。
本發明另外包括一種層狀製品,其包含:基板;位於所述基板上的光阻層;以及包含所述共聚物(其上述變型中的任一者)、位於所述光阻層上並且與所述光阻層接觸的面塗層。在此實施例中,層狀製品可以任選地另外包含一或多個位於基板與光阻層之間的額外層。
本發明另外包括一種形成電子器件的方法,所述方法包含:(a)在基板上塗覆光阻;(b)在光阻層上塗覆面塗層(其上述變型中的任一者);(c)使光阻層直至面塗層逐圖案曝露於活化輻射;以及(d)使所曝露的光阻層顯影以提供抗蝕劑浮雕影像。方法可任選地另外包括(e)在下伏基板中蝕刻抗蝕劑浮雕圖案。在一些實施例中,活化輻射為電子束或遠紫外線輻射。
基板的材料可以為例如半導體,例如矽或化合物半導體(例如III-V或II-VI)、玻璃、石英、陶瓷、銅及其類似物。典型地,基板為半導體晶圓,例如單晶矽或化合物半導體晶圓,其具有一或多個層以及在其表面上形成的圖案化特徵。下伏基底基板材料本身可以視情況經圖案化,例如當需要在基底基板材料中形成溝槽時。在基底基板材料上形成的層可以包括例如一或多個導電層,例如鋁層、銅層、鉬層、鉭層、鈦層、鎢層以及合金層、此類金屬的氮化物層或矽化物層;摻雜非晶矽或摻雜多晶矽;一或多個電介質層,例如氧化矽層、氮化矽層、氮氧化矽層或金屬氧化物層;半導體 層,例如單晶矽;底層;抗反射層,例如底部抗反射層;及其組合。所述層可以藉由各種技術形成,例如化學氣相沈積(chemical vapor deposition;CVD),例如電漿增強型CVD、低壓CVD或磊晶生長;物理氣相沈積(physical vapor deposition;PVD),例如濺鍍或蒸鍍、電鍍或旋塗。
可以使用適於電子束或遠紫外微影術中的任何光阻組合物。
將光阻組合物塗覆至基板上可以藉由任何適合方法完成,包括旋塗、噴塗、浸塗以及刀片刮抹。在一些實施例中,塗覆光阻組合物層是如下完成:使用塗佈軌道旋塗溶劑中的光阻,其中將光阻組合物分配於旋轉晶圓上。在分配期間,晶圓的旋轉速度可以高達4,000轉/分鐘(rotations per minute;rpm),確切地說,500rpm至3,000rpm,且更確切地說,1,000rpm至2,500rpm。旋轉所塗佈的晶圓以移除溶劑,並且在加熱板上烘焙以自膜中移除殘餘溶劑及自由體積來使其密度均勻。
接著使用曝光工具(例如步進器)來進行逐圖案曝光,其中膜經由圖案遮罩照射並且借此逐圖案曝光。在一些實施例中,方法使用先進曝光工具,其在能夠實現高解析度的波長下產生活化輻射,包括遠紫外(EUV)或電子束(e束)輻射。此類曝光工具的解析度可以小於30奈米。
接著藉由用能夠均勻溶解面塗層的適合正型顯影劑處理曝光層並且覆蓋面塗層並且選擇性地移除光阻層的曝光部分來完成曝光光阻層的顯影。在一些實施例中,正型顯影劑為不含金屬離子的四烷基氫氧化銨溶液,例如0.26當 量濃度的四甲基氫氧化銨水溶液。
當用於一或多種此類圖案形成方法中時,光阻組合物可以用於製造電子以及光電器件,例如記憶體器件、處理器晶片(包括中央處理單元或CPU)、圖形晶片以及其他此類器件。
實例
表1提供用於合成面塗層共聚物以及光阻共聚物的單體的化學結構以及首字母縮寫詞。
藉由RAFT技術合成聚(PEGMA-共-BzMA-共-HFACHOH)統計學共聚物。RAFT合成聚(PEGMA-共-BzMA-共-HFACHOH)的反應流程呈現於第1圖中。將PEGMA(4.75公克,0.01莫耳)、甲基丙烯酸苯甲酯(BzMA,1.76公克,0.01 莫耳)、HFACHOH(1.67公克,0.005莫耳)、4-氰基-4-[(十二烷基硫基硫羰基)硫基戊酸(CDTPA,RAFT劑,221.8毫克(91%純),5×10-4莫耳)、偶氮異丁腈(AIBN,起始劑,8.2毫克,5×10-5莫耳)以及1,4-二噁烷(15毫升)引入裝備有電磁攪拌器的50毫升舒倫克瓶(Schlenk flask)中([M]0:[mCTA]0:[Init]0=50:1:0.1,[PEGMA]:[BzMA]:[HFACHOH]=2:2:1)。反應混合物在冰浴中用氬氣吹洗30分鐘以移除氧氣,且接著在70℃下加熱。根據1H NMR計算單體轉化率並且藉由在己烷中進行雙沈澱來回收聚合物。使用聚苯乙烯標準物以及四氫呋喃溶劑,藉由質子核磁共振譜(1H NMR)、紫外光-可見光光譜法(UV-VIS)以及尺寸排阻層析法(SEC)來表徵聚合物。SEC指示分散度(Mw/Mn)為1.12。聚合物表徵概述於表2中。
聚(PEGMA-共-BzMA-共-HFACHOH)的RAFT裂解。從RAFT聚合物中移除端基的反應流程呈現於第2圖中。統計學共聚物的端基裂解如下進行。將聚(PEGMA-共-BzMA-共-HFACHOH)(3公克,1.85×10-4莫耳)、AIBN(0.912 公克,5.6×10-3莫耳,30當量)以及1,4-二噁烷(25毫升)引入裝備有電磁攪拌器的100mL舒倫克瓶中。反應混合物在冰浴中用氬氣吹洗30分鐘以移除氧氣,且接著在70℃下加熱。8小時之後,藉由在甲醇中透析且接著移除溶劑來提純聚合物。藉由1H NMR、UV-VIS以及SEC來表徵聚合物。1H NMR譜顯示於第3圖中,並且端基移除之前及之後的共聚物的UV-VIS光譜呈現於第4圖中。
薄膜製備
測定膜厚度與聚合物濃度的關係。光阻聚合物CBP-4之結構顯示於表3中。以乳酸乙酯或丙二醇單甲基醚乙酸酯(propylene glycol monomethyl ether acetate;PGMEA)作為溶劑,以1重量%、2重量%、3重量%、4重量%以及5重量%的目標濃度,如同光阻聚合物CBP-4溶液來製備一系列光阻溶液。如下執行代表性旋塗製程。首先,用丙酮以及異丙醇沖洗矽晶圓。接著將矽晶圓在100℃加熱板上置放10分鐘。接著藉由O2電漿處理來進一步清潔矽晶圓。以3000轉/分鐘(rpm)的速度將光阻溶液在矽晶圓旋塗60秒。光阻溶液塗佈至晶圓上之後,光阻層藉由在100℃下加熱90秒來乾燥以移除溶劑,直至光阻層無黏性。在SCI Filmtek 4000光譜學反射計上量測膜厚度。膜厚度相對於聚合物濃度的線性曲線呈現於第5A圖中。根據曲線,使用2.5重量%至3重量%作為最終聚合物濃度,直至實現約50奈米的所要光阻層厚度。
由不同面塗層溶劑引起的光阻層厚度變化。此步驟的目的為選擇面塗層溶劑。一般而言,面塗層溶劑不應溶解光阻層。否則,在面塗層旋塗過程中,溶劑將部分地溶解抗蝕劑表面,形成互混層。評價抗蝕劑與面塗層之間的溶劑相容性的有效方法為藉由使不同面塗層溶劑暴露於抗蝕劑膜來量測抗蝕劑的厚度變化。典型製程如下。首先,將光阻溶液旋塗於矽晶圓上。塗覆後烘焙之後,量測光阻層的厚度。接著藉由旋塗於光阻層上來塗覆不同溶劑。再進行塗覆後烘焙之後,量測膜厚度。溶劑特性概述於表4中,其中「TMAH」表示四甲基氫氧化銨。不同溶劑引起的厚度變化呈現於表5中,其中「二(丙二醇)單甲基醚+2-甲基-2-丁醇」是指11:89重量比的二(丙二醇)單甲基醚及2-甲基-2-丁醇。
互混測試
用於互混測試的典型方法如下進行。首先,將光阻溶液旋塗於矽晶圓上以形成50奈米層。塗覆後烘焙之後,量測光阻層的厚度。接著將面塗層溶液(含有聚(PEGMA-共-BzMA-共-HFACHOH)的2-甲基-2-丁醇)旋塗於光阻層上。塗覆後烘焙之後,量測總層厚度。將面塗層溶解於顯影劑溶液(2.38重量%的TMAH溶液)中、隨後用去離子水沖洗之後,量測「暗損失」。「暗損失」為移除面塗層之前與之後的光阻層厚度之間的差異並且由於曝光不涉及量測而被稱為暗損失。
互混測試的結果顯示於表6中。將聚(PEGMA-共-BzMA-共-HFACHOH)/2-甲基-2-丁醇溶液塗佈於裸矽基板上,得到10奈米(0.3重量%溶液)或27奈米(0.7重量%溶液)的層厚度。光阻層厚度為約50奈米。面塗層塗佈於光阻層上之後,接著層厚度為約60奈米(對於0.3重量%面塗層溶液)或約80奈米(對於0.7重量%溶液)。使用2.38% TMAH溶液移除面塗層並且用去離子水沖洗之後,光阻層的最終厚度類似於其原始厚度。此等結果表明,本文所述的面塗層不與光阻層形成混合層並且可以使用顯影劑溶液移除。
量測接觸角
用於製備供量測接觸角用之樣品的典型程序如下。將CBP-4光阻溶液旋塗於潔淨的矽晶圓上。塗覆光阻層之前,在晶圓上不塗覆助黏塗層。將面塗層溶液旋塗於光阻層上,形成10奈米或30奈米厚度的面塗層。在室溫下,使用Dataphysics OCA20接觸角系統量測接觸角。在樣品表面上滴加去離子水滴(2微升)以便對濕潤行為進行量測。
第6圖中所呈現的結果顯示,裸面塗層(10奈米 或30奈米)具有相當的親水性。去離子水接觸角為約35°並且去離子水滴伸展極快。60秒之後,去離子水接觸角變成約11°。然而,在面塗層塗佈於光阻層上的情況下,水接觸角不同於直接塗佈於矽晶圓上的裸面塗層的水接觸角。對於30奈米厚度的面塗層而言,水接觸角(water contact angle;WCA)為55°並且在60秒之後變成25°。對於10奈米厚度的面塗層而言,WCA為72°並且在60秒之後變成46°。WCA在裸光阻層表面上為82°並且在60秒之後保持不變。已知矽在空氣中容易氧化而塗上氧化矽層,氧化矽層為親水性表面。雖然不希望被任何特定假設束縛,但本發明人推測,如第6圖中的示意性影像所示,晶圓表面上的親水性羥基氫原子可以與HFACHOH重複單元羥基中的氧原子形成氫鍵。因此,面塗層表面可傾向於具有更大親水性。然而,當面塗層旋塗於光阻層上時,由於在旋塗過程中表面能低,因此更多的HFACHOH重複單元可以移動至表面。此原因可能是,光阻層上所塗佈的面塗層的疏水性傾向於比直接塗佈於矽基板上的面塗層大。
VUV VASE橢偏儀表徵
為了檢查面塗層對頻帶外光的阻擋作用,藉由VUV VASE橢偏儀量測面塗層薄膜的光學特性。在J.A.WoollamTM VUV VASETM光譜學橢偏儀上量測光學常數n及k以及膜厚度。使用1.2電子伏特(electron-volts;eV)至8.3電子伏特的光譜範圍(對應於波長範圍λ 150奈米至1000奈米)以及65°至75°的入射角(以5°作為步長),進行VUV VASE量測。整個光學路徑圍封於乾燥氮氣吹掃環境內以消除環境 水蒸汽以及氧氣的吸收。此研究中的建模以及擬合程序由以下內容組成:首先使用柯西層(Cauchy layer)測定厚度以及300奈米至1000奈米透光光譜區間的光學常數,且接著使用逐點方法擬合150nm至300nm範圍內的曲線以便獲得光學常數消光係數‘k’以及折射率‘n’。面塗層的光學特性概述於表7中並且呈現於第7圖(消光係數與波長以及面塗層厚度的關係)以及第8圖(透射率百分比與波長以及面塗層厚度的關係)中。如表7以及第7圖以及第8圖中所示,對於13奈米以及30奈米厚度的面塗層而言,消光係數k分別為0.213以及0.215。193奈米下的透射率百分比分別計算為83.2%以及64%。吸收係數α為13.9μm-1以及14.0μm-1
微影效能
電子束微影術(electron beam lithography;EBL)用的樣品如下製備。將光阻聚合物CBP-4(25毫克)以及三異丙醇胺(0.20毫克,20莫耳%,相對於CBP-4共聚物中的光酸產生重複單元)引入20毫升小瓶中。添加乳酸乙酯(760微升,786毫克)以製備CBP-4聚合物濃度為3重量%的溶液。將面塗層聚合物聚(PEGMA-共-BzMA-共-HFACHOH)(10毫克)溶解於2-甲基-2-丁醇(5毫升,4.02公克)中以製備濃 度為0.25重量%的溶液。
如下執行代表性旋塗製程。首先,用丙酮以及異丙醇沖洗矽晶圓。接著將矽晶圓在100℃加熱板上置放10分鐘。接著藉由O2電漿處理來進一步清潔矽晶圓。以TI/HDMS塗漆獲自MicroChemicals的助黏劑以3000rpm的速度在潔淨矽晶圓上旋塗20秒,隨後在120℃加熱板上焙烤5分鐘以移除溶劑。光阻溶液以3000rpm的速度在底塗層上旋塗60秒。將光阻溶液塗佈於晶圓上之後,藉由在100℃下加熱90秒來乾燥晶圓以移除溶劑,直至光阻層無黏性。接著將面塗層溶液以3000rpm的速度在光阻層上旋塗60秒。在塗覆後烘焙步驟中,將所塗晶圓在100℃加熱板上置放90秒以移除殘餘溶劑。
接著將具有面塗層的光阻圖案化並且曝露於活化輻射,曝光能量典型地在約10μC/cm2至100μC/cm2範圍內。典型地,使用電子束微影技術作為產生圖案的曝光工具。
曝光之後,將具有面塗層的光阻在100℃的溫度下烘焙60秒。隨後,藉由用水性鹼性顯影劑(例如0.26N四甲基氫氧化銨(2.38重量% TMAH))處理20秒、隨後用水沖洗20秒來使樣品顯影。
使用7800場發射掃描電子顯微鏡(Field Emission Scanning Electron Microscope;FE-SEM)聯合熱(肖特基(Schottky))電子槍進行電子束微影分析,其在15kV下具有0.8nm的解析度(與樣品相關)並且在1kV下具有1.2nm的解析度。其裝備有電子束微影術用的RAITHTM系統。
第9圖顯示CBP-4光阻層以及CBP-4光阻層加 10奈米面塗層的對比度曲線。根據曲線可以看出,抗蝕劑敏感性在面塗層存在下不發生變化。兩個樣品的清除劑量值為約40μC/cm2。然而,CBP-4光阻層加10奈米面塗層的曲線的斜率較高。因此,對比度在添加面塗層的情況下改善。掃描電子顯微法
第10圖呈現以下線圖案的掃描電子顯微照片(SEM):(a)以51μC/cm2曝光的CBP-4光阻層;(b)以53μC/cm2曝光的CBP-4光阻層;(c)以55μC/cm2曝光的CBP-4光阻層;(d)以51μC/cm2曝光的CBP-4光阻層+10nm面塗層;(e)以57μC/cm2曝光的CBP-4光阻層+10nm面塗層;以及(f)以60μC/cm2曝光的CBP-4光阻層+10nm面塗層。
Figure 107103227-A0101-11-0002-1

Claims (8)

  1. 一種形成電子器件的方法,所述方法包含:(a)在基板上塗覆光阻層;(b)在所述光阻層上塗覆包含共聚物的面塗層;(c)使所述光阻層直至所述面塗層逐圖案曝露於活化輻射;以及(d)使所述的所曝光光阻層顯影以提供抗蝕劑浮雕影像,其中所述共聚物包含單體聚合產物,所述單體包含:頻帶外吸收型單體,其中所述頻帶外吸收型單體包含未經取代或經取代的不含氟的C6-C18芳基、未經取代或經取代的C2-C17雜芳基、C5-C12二烯酮基團,或其組合;以及鹼溶解度增強型單體,其中所述鹼溶解度增強型單體選自由以下各物組成的群組:聚(氧化乙烯)的(甲基)丙烯酸酯、聚(氧化丙烯)的(甲基)丙烯酸酯、鹼不穩定性(甲基)丙烯酸酯、經具有2至12的pKa的基團取代的(甲基)丙烯酸酯,及其組合;以及其中由所述共聚物鑄成的膜在150奈米至400奈米範圍內的波長下具有0.1至0.5的消光係數k。
  2. 如申請專利範圍第1項所述之方法,其中所述活化輻射包含電子束或遠紫外輻射。
  3. 如申請專利範圍第1項或第2項所述之方法,其中所述聚合物具有1.05至1.2的分散度(Mw/Mn)。
  4. 如申請專利範圍第1項或第2項所述之方法,其中所述頻 帶外吸收型單體具有結構:
    Figure 107103227-A0305-02-0028-3
    其中R1為氫或甲基,n為0、1、2、3或4,以及Ar1為未經取代或經取代的不含氟的C6-C18芳基。
  5. 如申請專利範圍第1項或第2項所述之方法,其中所述鹼溶解度增強型單體包含聚(氧化乙烯)的(甲基)丙烯酸酯以及經1,1,1,3,3,3-六氟-2-羥基-2-丙基取代的(甲基)丙烯酸酯。
  6. 如申請專利範圍第1項或第2項所述之方法,其中所述頻帶外吸收型單體具有結構:
    Figure 107103227-A0305-02-0028-2
    其中R1為氫或甲基,n為0、1、2、3或4,並且Ar1為未經取代或經取代的不含氟的C6-C18芳基;其中所述鹼溶解度增強型單體包含聚(氧化乙烯)的(甲基)丙烯酸酯以及經1,1,1,3,3,3-六氟-2-羥基-2-丙基取代的(甲基)丙烯酸酯;其中以單體的總莫耳數計,所述單體包含:30莫耳%至50莫耳%的所述頻帶外吸收型單體,30莫耳%至50莫耳%的聚(氧化乙烯)的(甲基)丙烯酸 酯,以及10莫耳%至30莫耳%的經1,1,1,3,3,3-六氟-2-羥基-2-丙基取代的(甲基)丙烯酸酯;以及其中所述共聚物具有1.05至1.2的分散度(Mw/Mn)。
  7. 如申請專利範圍第1項或第2項所述之方法,其中所述面塗層係藉由對聚合物溶液進行旋塗而形成,所述聚合物溶液包含存在於溶劑中的0.1重量%至3重量%之該共聚物,所述溶劑選自由以下各物組成的群組:2-甲基-2-丁醇、2-甲基-2-戊醇、2-甲基-2-丁醇與2-甲基-2-戊醇的組合、二丙二醇單甲基醚與2-甲基-2-丁醇的含有至少90重量%2-甲基-2-丁醇的組合、二丙二醇單甲基醚與2-甲基-2-戊醇的含有至少90重量%2-甲基-2-戊醇的組合,以及二丙二醇單甲基醚與2-甲基-2-丁醇與2-甲基-2-戊醇的含有總計至少90重量%2-甲基-2-丁醇以及2-甲基-2-戊醇的組合。
  8. 一種層狀製品,其包含:基板:位於所述基板的光阻層;以及包含共聚物、位於所述光阻層上並且與所述光阻層接觸的面塗層,其中所述共聚物包含單體聚合產物,所述單體包含:頻帶外吸收型單體,其中所述頻帶外吸收型單體包含未經取代或經取代的不含氟的C6-C18芳基、未經取代或經取代的C2-C17雜芳基、C5-C12二烯酮基團,或其組合;以及鹼溶解度增強型單體,其中所述鹼溶解度增強型單體 選自由以下各物組成的群組:聚(氧化乙烯)的(甲基)丙烯酸酯、聚(氧化丙烯)的(甲基)丙烯酸酯、鹼不穩定性(甲基)丙烯酸酯、經具有2至12的pKa的基團取代的(甲基)丙烯酸酯,及其組合;以及其中由所述共聚物鑄成的膜在150奈米至400奈米範圍內的波長下具有0.1至0.5的消光係數k。
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