TW201038595A - Polymer for forming photoresist pattern and method for forming pattern of semiconductor device using the same - Google Patents
Polymer for forming photoresist pattern and method for forming pattern of semiconductor device using the same Download PDFInfo
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- TW201038595A TW201038595A TW99105733A TW99105733A TW201038595A TW 201038595 A TW201038595 A TW 201038595A TW 99105733 A TW99105733 A TW 99105733A TW 99105733 A TW99105733 A TW 99105733A TW 201038595 A TW201038595 A TW 201038595A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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Abstract
Description
201038595 六、發明說明: 本申請案主張2009年2月27曰申請之韓國專利申請 案號10-2009-0016965的優先權。該韓國專利申請案全 文以引用方式將其併入本文。 【發明所屬之技術領域】 本發明係關於一種用於塗佈光阻圖案的聚合物,詳言 之,本發明係關於一種用於塗佈光阻圖案並藉此改善微 影製程解析度的聚合物,以及使用該聚合物形成半導體 元件圖案的方法。 【先前技術】 隨著半導體元件密集度提高,需進行光微影製程來形 成線寬小於或等於80奈米(nm)的極小光阻圖案。在習知 ◎ 光微影製程中,含感光聚合物和溶劑的光阻組成物塗佈 在基材(如矽晶圓)上以製造積體電路,所塗佈的光阻組 成物中的溶劑則經烘烤而揮發以形成光阻層薄膜。隨 後,光阻層曝照曝光源的光圖案’曝照之感光聚合物的 化性因而改變。諸如可見光、紫外(uv)光電子束、χ - 光等可做為曝光源。曝光後,使用顯影液選擇性溶解並 - 移除曝照之光阻層,以形成光阻圖案。 在光微影製程中,各種改善光阻圖案解析度的技術已 被開發。例如,PCT國際公開號w〇 2〇〇8/122884和Ep 4 201038595201038595 VI. Description of the Invention: This application claims priority to Korean Patent Application No. 10-2009-0016965, filed on Feb. 27, 2009. This Korean patent application is incorporated herein by reference in its entirety. BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a polymer for coating a photoresist pattern, and more particularly to an polymerization for coating a photoresist pattern and thereby improving the resolution of the lithography process. And a method of forming a pattern of a semiconductor element using the polymer. [Prior Art] As the density of semiconductor elements is increased, a photolithography process is required to form a very small photoresist pattern having a line width of less than or equal to 80 nanometers (nm). In a conventional ◎ photolithography process, a photoresist composition containing a photopolymer and a solvent is coated on a substrate such as a germanium wafer to fabricate an integrated circuit, a solvent in the applied photoresist composition. Then, it is baked and volatilized to form a photoresist layer film. Subsequently, the photopolymer layer exposed to the light pattern of the exposure source is exposed to a change in the photopolymer. For example, visible light, ultraviolet (uv) photoelectron beam, xenon-light, etc. can be used as an exposure source. After exposure, the developer is used to selectively dissolve and - remove the exposed photoresist layer to form a photoresist pattern. Various techniques for improving the resolution of photoresist patterns have been developed in the photolithography process. For example, PCT International Publication No. w〇 2〇〇8/122884 and Ep 4 201038595
1757989 A揭露之藉由聚合物塗佈光阻圖案以縮小圖案 間隔的方法,騎示於第。第1圖顯示用於形成細 小光阻圖案的習知方法之-實施例。如第!圖所示,形 成光阻圖案的習知方法包括形成光阻I 120至基材110 步驟(參見第!圖的A),藉由曝光及顯影光阻層12〇 成為所需影像而形成光阻圖帛122之步驟(參見第i圖的 B)’以及塗佈微縮材料13〇之聚合物至光阻圖帛122上 以縮減線寬之步驟(參見第!圖的〇。烘烤塗佈了微縮材 料130之聚合物的基材’藉以黏接光阻圖案122和微縮 材料30’並接著形成邊界層132(參見第丨圖的d”使用 溶液(如水)顯影微縮材料13〇未反應的部分,藉以縮小 光阻圖案122間的間隔(參見第i圖的E)。藉由上述方法 可形成具較小關鍵尺寸(critical dimension,CD)的光阻圖 案。第1圖所示之用於形成光阻圖案的方法縮減了先前 形成的接觸孔(contact hole, C/H)尺寸。 【發明内容】 因此’本發明之一目的在於提供一種用於塗佈光阻圖 案的聚合物,其可改善微影製程的解析度。 本發明之另一目的在於提供一種使用前述之聚合物塗 佈光阻圖案’以形成具高解析度之半導體元件圖案的方 法。 本發明之又一目的在於提供一種藉由圖案自我對準, 5 201038595 以於半導體元件圖案的線與線之間的間隔形成雙倍圖案 的方法。 為達上述目的,本發明提供一種用於塗佈光阻圖案的 聚合物,其以下列化學式1表示。 [化學式1] ,R* R* 卜 o r2 · 01757989 A discloses a method of coating a photoresist pattern by a polymer to reduce the pattern spacing, and riding is shown in the first. Figure 1 shows an embodiment of a conventional method for forming a fine photoresist pattern. As the first! As shown, a conventional method of forming a photoresist pattern includes the steps of forming a photoresist I 120 to a substrate 110 (see A of FIG. 3), and forming a photoresist by exposing and developing the photoresist layer 12 to a desired image. The step of Fig. 122 (see B of Fig. i) and the step of coating the polymer of the micronized material 13 to the photoresist pattern 122 to reduce the line width (see the figure of Fig. Fig. The substrate of the polymer of the micro-material 130 is used to bond the photoresist pattern 122 and the micro-material 30' and then form the boundary layer 132 (see d of the figure) using a solution (such as water) to develop the unreacted portion of the micro-material 13 In order to reduce the interval between the photoresist patterns 122 (see E of FIG. i), a photoresist pattern having a smaller critical dimension (CD) can be formed by the above method. The method of the photoresist pattern reduces the size of the previously formed contact hole (C/H). [Invention] It is therefore an object of the present invention to provide a polymer for coating a photoresist pattern which can be improved. Resolution of the lithography process. Another object of the present invention It is to provide a method of coating a photoresist pattern using the aforementioned polymer to form a high-resolution semiconductor element pattern. A further object of the present invention is to provide a pattern of semiconductor elements by pattern self-alignment, 5 201038595 The method of forming a double pattern with the line-to-line spacing. To achieve the above object, the present invention provides a polymer for coating a photoresist pattern, which is represented by the following Chemical Formula 1: [Chemical Formula 1], R* R * 卜o r2 · 0
II
Ri、 . 、nh2 在化學式1中,R*個別為氫原子或甲基(_CH3),尺1為 具1至18個碳原子的直鏈或環狀烴基,r2為羥基(_0H)、 緩基(_C00H),或具3至10個碳原子' i至3個氮原子 與1至3個氧原子的直鏈或環狀烴基,且X、y各自表示 化學式1所表示之聚合物的複數個重複單元佔總體重複 單元的莫耳/〇,且分別為5 i i 〇〇莫耳%以及。至9 耳%。 本發明尚提供—種用於塗佈光阻圖案的組成物其包 3以上述化學式1表示,用於塗佈光阻圖案的聚合物; =及溶解用於塗佈光阻圖案的聚合物之溶劑。本發明還 提供-種用於形成半導體元件圖案的方法,其包含下列 步驟·⑴塗佈做為第—光阻層的卜光阻至基材上,然 後曝光及顯影第—光阻層,以形成第—光阻圖案;( 塗佈含有用於塗佈第—光阻圖案且以化學式1表示之聚 物和办解該聚合物之溶劑的組成物,並接著揮發該溶 劑’以形成塗佈層至第—光阻圖案上;㈣使塗佈層^ 6 201038595 層邻八接^顯影方式移除未反應的塗佈 …以形成介面層覆蓋第一光阻圖 光阻來填充介面層間的間隔,以於第—光阻圖牵二第: 第-先阻圖案,接著以顯影方式移除介面層,致使第一 先阻圖案和第二光阻圖案仍留在基材上。藉此,雙倍圖 =第-和第二光阻圖案)可形成在半導體元件 與線之間。Ri, . , nh2 In Chemical Formula 1, R* is each a hydrogen atom or a methyl group (_CH3), the rule 1 is a linear or cyclic hydrocarbon group having 1 to 18 carbon atoms, and r2 is a hydroxyl group (_0H), a slow group. (_C00H), or a linear or cyclic hydrocarbon group having 3 to 10 carbon atoms 'i to 3 nitrogen atoms and 1 to 3 oxygen atoms, and each of X and y represents a plurality of polymers represented by Chemical Formula 1. The repeating unit accounts for the molar/〇 of the overall repeating unit and is 5 ii 〇〇 mol % and respectively. Up to 9 ears. The present invention further provides a composition for coating a photoresist pattern, wherein the package 3 is represented by the above Chemical Formula 1, a polymer for coating a photoresist pattern; and a polymer for dissolving a photoresist pattern. Solvent. The present invention also provides a method for forming a pattern of a semiconductor element, comprising the steps of: (1) coating a photoresist as a first photoresist layer onto a substrate, and then exposing and developing the first photoresist layer to form a first a photoresist pattern; (coating a composition containing a polymer for coating a first photoresist pattern and expressing a solvent of the polymer, and then volatilizing the solvent to form a coating layer to (4) applying a coating layer to remove the unreacted coating ... to form an interface layer covering the first photoresist pattern photoresist to fill the interval between the interface layers, In the first-resistance diagram, the first-first-resistance pattern is followed by development to remove the interface layer, so that the first first-resistance pattern and the second photoresist pattern remain on the substrate. The first and second photoresist patterns may be formed between the semiconductor element and the line.
簡口之’本發明之聚合物塗佈在第一光阻圖案上並經 過反應’接著使用去離子水顯影源自該聚合物之塗佈層 的未反應部分而形成介面層。如此將縮小第一光阻圖案 間的間隔。藉此介面層’第二光阻圖案能以自我對準方 式形成在第一光阻圖案之間。雙倍圖案即形成在半導體 儿件圖案的線與線之間。故可減少依據先前技術利用曝 光設備形成第二光阻圖案可能產生的對準誤差。 〇 【實施方式】 本發明及其優點在參閱以下詳細說明後當能更徹底了 解。 依據本發明預先形成之用於塗佈光阻圖案的聚合物以 下列化學式1表示,其與光阻圖案反應形成介面層包圍 光阻圖案。 ' [化學式1] 201038595The polymer of the present invention is coated on a first photoresist pattern and subjected to a reaction' followed by development of an unreacted portion of the coating layer derived from the polymer using deionized water to form an interface layer. This will reduce the interval between the first photoresist patterns. Thereby the interface layer 'the second photoresist pattern can be formed between the first photoresist patterns in a self-aligned manner. The double pattern is formed between the lines and lines of the semiconductor pattern. Therefore, the alignment error that may be generated by forming the second photoresist pattern using the exposure apparatus according to the prior art can be reduced. [Embodiment] The present invention and its advantages will be more fully understood from the following detailed description. The polymer previously formed for coating a photoresist pattern according to the present invention is represented by the following Chemical Formula 1, which reacts with the photoresist pattern to form an interface layer surrounding the photoresist pattern. '[Chemical Formula 1] 201038595
Rl、Rl,
t 、nh2 在化學式1中,R*個別為氫原子或曱基(-CH3),h為 具1至18個碳原子的直鏈或環狀烴基,R2為羥基(-OH)、 羧基(-COOH),或具3至10個碳原子' 1至3個氮原子 與1至3個氧原子的直鏈或環狀烴基。R】可為直鏈或環 狀院基或芳基,且可視需求含有雜原子,例如氧原子 (0)、氮原子(N)、硫原子(S)等。R,的詳細實例包括 —CH2—、'CH2CH2*~~、—CH2CH2CH2—、"""CHaCHaCHzCHa*~、—CH2CH2CH2CH2CH2~~·、 •CH2CH2CH2CH2CH2CH;r -CHCH2— CH3 、 -CHCH2—o»chch2-CH3 CH3 -CHCH2CH2— ch3 -ch2ch2-〇-ch2ch2- ch3 —ch2cch2— 、 ch3 CH2CH;t〇—CH2CH2-〇-CH2CHr ch2oh ch3 -CH2CCH2CH2 ch3 ch2cch2- ch2oh —CHCH2-0-CHCH2-O-CHCH2— ch3 I ch3 ch3t, nh2 In Chemical Formula 1, R* is each a hydrogen atom or a fluorenyl group (-CH3), h is a linear or cyclic hydrocarbon group having 1 to 18 carbon atoms, and R2 is a hydroxyl group (-OH) or a carboxyl group (- COOH), or a linear or cyclic hydrocarbon group having from 1 to 3 nitrogen atoms and from 1 to 3 oxygen atoms of 3 to 10 carbon atoms. R] may be a linear or cyclic compound or an aryl group, and may contain a hetero atom such as an oxygen atom (0), a nitrogen atom (N), a sulfur atom (S), or the like as the case requires. Detailed examples of R, include -CH2—, 'CH2CH2*~~, —CH2CH2CH2—, """CHaCHaCHzCHa*~, -CH2CH2CH2CH2CH2~~·, •CH2CH2CH2CH2CH2CH;r-CHCH2—CH3, -CHCH2—o» chch2-CH3 CH3 -CHCH2CH2—ch3 -ch2ch2-〇-ch2ch2-ch3 —ch2cch2— , ch3 CH2CH;t〇—CH2CH2-〇-CH2CHr ch2oh ch3 -CH2CCH2CH2 ch3 ch2cch2-ch2oh —CHCH2-0-CHCH2-O-CHCH2— Ch3 I ch3 ch3
CH2-* —CH2·CH2-* —CH2·
'尸 丫 、、 -ο-s—ο- 等。r2較佳 為雜環基,例如咪唑基、内醯胺基等,更佳為吡咯酮基。 在化學式1中,x、y各自表示化學式1之聚合物中的 重複單元佔總體重複單元的莫耳%,且X為5至100莫 201038595'corpse 、,, -ο-s-ο-, etc. R2 is preferably a heterocyclic group such as an imidazolyl group or an indolylamine group, more preferably a pyrrolidone group. In Chemical Formula 1, x and y each represent a molar unit of the repeating unit in the polymer of Chemical Formula 1 as a percentage of the total repeating unit, and X is 5 to 100%.
酸擴散供烤(acid-diffusing-baking)造成乙縮醛去保護, 以致減少聚合物的溶劑選擇性。若y含量太多則會降 0 低聚合物與光阻圖案間的附著性。 根據本發明之用於塗佈光阻圖案的聚合物之詳細實例 以下列化學式2a-2g表示。在化學式2a-2g中,X、y的 定義與化學式1相同。 [化學式2a]Acid-diffusing-baking causes the acetal to be deprotected, thereby reducing the solvent selectivity of the polymer. If the y content is too large, it will lower the adhesion between the polymer and the resist pattern. A detailed example of the polymer for coating a photoresist pattern according to the present invention is represented by the following Chemical Formula 2a-2g. In Chemical Formula 2a-2g, X and y have the same definitions as Chemical Formula 1. [Chemical Formula 2a]
〇 [化學式2b]〇 [Chemical Formula 2b]
[化學式2c] 201038595[Chemical Formula 2c] 201038595
[化學式2e][Chemical Formula 2e]
OH ΟOH Ο
ΟΟ
'ΝΗ2 [化學式2f] . [化學式2g] Ο 本發明用於塗佈光阻圖案的聚合物可藉由利用f知起 始劑(如偶氛二異丁猜以習^方法合成乙缚單體 - 來製造’該乙烯單體包括一L。—/ 1 、R_*、β竣 . ^ Κ·2等。在本 • 冑明之聚合物中’每-重複單元含量與單體用量成正 比。本發明用於塗佈絲圖案的聚合物可為團聯或雜亂 共聚物。本發明之聚合物的重量平均分子量(Mw)較佳為 201038595'ΝΗ2 [Chemical Formula 2f] . [Chemical Formula 2g] 聚合物 The polymer for coating a photoresist pattern of the present invention can be synthesized by using a known initiator (for example, an octagonal diisobutylene method) - To manufacture 'the ethylene monomer includes one L. —/ 1 , R_*, β竣. ^ Κ·2, etc. In the polymer of Benming Ming, the content of each repeat unit is proportional to the amount of monomer used. The polymer for coating the silk pattern may be agglomerated or a scrambled copolymer. The weight average molecular weight (Mw) of the polymer of the present invention is preferably 201038595.
Ο 5,000至100,000,更佳為5 〇〇〇至2〇,〇〇()。本發明之聚 合物的聚合度分佈性(p〇lydiSpersity, PD)較佳為1.0至 5.0’更佳為1.0至2.0。若該聚合物的重量平均分子量和 聚合物的聚合度分佈性超出上述範圍,則會減弱用於塗 佈光阻圖案的塗佈層之性質。因本發明之聚合物分子具 有胺基,故光阻圖案與本發明用於塗佈層之聚合物間容 易附著,且塗佈不會破壞光阻圖案。本發明之用於塗佈 光阻圖案的聚合物可藉曝光及烘烤產生的酸而引起去保 護作用。又,由於該聚合物分子中之乙縮醛基的去保護, 及顯影步驟的對比提高,導致第一光阻圖案與聚合物間 的附著性降低,使用去離子水等即可輕易顯影並移除本 發明用於塗佈光阻圖案的聚合物。 本發明之用於塗佈光阻圖案的聚合物可做為溶於溶劑 中的組成物。用於塗佈光阻圖案的組成物之溶劑可為 水,較佳為去離子水。若有必要,亦可採用水與醇之混 合溶劑。在用於塗佈光阻圖案的組成物中,化學式丨表 不之聚合物的含量為0.5至30重量%,較佳為3至1〇重 量%,其餘部分為溶劑。若聚合物含量太少,則形成塗 佈層後的聚合物層會太薄,以致無法形成預定厚度的塗 佈層;若聚合物含量太多,則會降低塗佈層的均勻度。 在本發明用於塗佈光阻圖案的組成中,可配合水使用的 醇實例包括具1至4個碳原子的低級醇,例如甲醇、乙 醇,且醇成分佔總體組成物的〇至5〇重量%,較佳佔1 至50重量更佳佔5至25重量%。若醇成分含量太少,1 11 201038595 則會降低塗佈層的均勻度;若醇成分含量太多,則第一 光阻圖案可能溶解,以致無法形成第二光阻圖案。再者, 若有必要,本發明用於塗佈光阻圖案的組成物更可包含 習知的光酸產生劑(photo acid generator, PAG)、熱酸產 生劑(thermal acid generator,TAG)、有機鹼做為淬滅體 (quencher)、界面活性劑等。pag照光時會產生酸成分, 並去保護(de-protect)用於塗佈光阻圖案之聚合物的保護 基。任何於光線照射下可產生酸成分的化合物皆可當作 PAG。較佳地,可使用銃鹽類化合物(如有機磺酸)、鑌鹽 類化合物(如鑌鹽)’或其混合物。PAG的非限定實例包 括醜酿亞胺三氟甲續酸鹽(phthalimidotrifluoro methane sulfonate)、二硝苯基曱苯續酸鹽(dinitrobenzyl tosylate)、正-癸烧基二颯(n-decyl disulfone)、萘酿亞胺 三氟甲續酸鹽(naphthylimido trifluorome thane sulfonate)、六氟填酸二苯基鎖鑌(diphenyl iodonium hexafluorophosphate)、六氟砰酸二苯基錤鏽(diphenyl iodonium hexafluoroarsenate)、六氟録酸二苯基鐄鑌 (diphenyl iodonium hexafluoroantimonate)、三氟曱續酸 二苯基對-甲氧苯基疏鹽(diphenyl p-methoxyphenyl sulfonium triflate)、 六氟録酸三苯基硫鹽 (triphenylsulfonium hexafluoroantimonate)、三氟甲磺酸 三苯基銃鹽(triphenylsulfonium triflate)、三氟甲續酸二 丁萘基锍鹽(dibutylnaphtylsulfonium triflate),及其混合 物。若使用PAG或TAG,則其用量按聚合物100重量部 201038595 分計’較佳佔0至20重量部分,更佳佔0.05至20重量 • 部分,最佳佔0·1至10重量部分。S PAG或TAG用量 '太^ W因t合物對光的感光性降低,導致保護基的去 保護不足;若PAG或TAG用量太多,則目pAG或TAG 產生過量的酸’以致塗佈層形狀不佳。可用於本發明的 界面活性劑較佳為水溶性界面活性劑,然也可採用陰離 子界面活性劑、陽離子界面活性劑和兩性界面活性劑。 〇 例如’可使用烷基苯磺酸鹽類、高級鹵化胺、四級銨鹽 類炫基比咬鹽類、氨基酸類、颯酿亞胺類、續酿胺類 界面活性劑,或其混合物。界面活性劑的含量按用於塗 佈光阻圖案之總體組成物1〇〇重量部分計,# 〇 〇1至2 重里部刀’較佳佔〇. i至丨重量部分。若界面活性劑含 量太少,則會降低塗佈的均勻度;若界面活性劑含量太 多’則因用水移除塗佈層的過程中大量失去膜層,而無 法於第一圖案上有效形成塗佈層。 接著,請參照第2圖,,第2圖說明用於形成半導體 元件圖案的方法。第-光阻層20形成在基材1〇(例如矽 晶圓、鋁等)上(參見第2圖的A)。以所需影像曝光及顯 影第一光阻層20,以形成第一光阻圖案22(參見第2圖 的B)。塗佈用於塗佈第一光阻圖案22的組成物,接著 揮發組成物中的溶劑,以形成塗佈層3〇(參見第2圖的 C)。利用諸如烘烤塗佈層30之方法,黏著第一光阻圖案 22和塗佈層30的聚合物,或使酸從第一光阻圖案擴 散到塗佈層30的聚合物,以使由覆蓋材料所形成之介面 201038595 層32圍繞第一光阻圖案22(參見第2圖的 ^ 1文用顯影 液(如水、醇、鹼性水溶液,及其混合物)顯影並移除未 反應的塗佈層30部分,藉以縮小第一光阻 禾間的 ΟΟ 5,000 to 100,000, more preferably 5 〇〇〇 to 2 〇, 〇〇 (). The polymerity distribution (p〇lydiSpersity, PD) of the polymer of the present invention is preferably from 1.0 to 5.0', more preferably from 1.0 to 2.0. If the weight average molecular weight of the polymer and the degree of polymerization of the polymer exceed the above range, the properties of the coating layer for coating the photoresist pattern are weakened. Since the polymer molecule of the present invention has an amine group, the photoresist pattern is easily adhered to the polymer for coating the layer of the present invention, and the coating does not damage the photoresist pattern. The polymer for coating a photoresist pattern of the present invention can be deprotected by the acid generated by exposure and baking. Moreover, since the deprotection of the acetal group in the polymer molecule and the contrast of the development step are improved, the adhesion between the first photoresist pattern and the polymer is lowered, and the development and migration can be easily performed using deionized water or the like. In addition to the polymer of the present invention for coating a photoresist pattern. The polymer for coating a photoresist pattern of the present invention can be used as a composition dissolved in a solvent. The solvent for coating the composition of the photoresist pattern may be water, preferably deionized water. If necessary, a mixed solvent of water and alcohol can also be used. In the composition for coating the photoresist pattern, the content of the polymer of the formula is 0.5 to 30% by weight, preferably 3 to 1% by weight, and the balance is a solvent. If the polymer content is too small, the polymer layer after the formation of the coating layer is too thin to form a coating layer of a predetermined thickness; if the polymer content is too large, the uniformity of the coating layer is lowered. In the composition for coating a photoresist pattern of the present invention, examples of the alcohol which can be used in combination with water include lower alcohols having 1 to 4 carbon atoms, such as methanol and ethanol, and the alcohol component accounts for 〇 to 5 总体 of the total composition. The weight %, preferably from 1 to 50 by weight, more preferably from 5 to 25% by weight. If the content of the alcohol component is too small, 1 11 201038595 will lower the uniformity of the coating layer; if the content of the alcohol component is too large, the first photoresist pattern may be dissolved, so that the second photoresist pattern cannot be formed. Furthermore, if necessary, the composition for coating a photoresist pattern of the present invention may further comprise a conventional photo acid generator (PAG), a thermal acid generator (TAG), or an organic The base is used as a quencher, a surfactant, and the like. The pag generates an acid component upon irradiation and de-protects the protecting group of the polymer used to coat the photoresist pattern. Any compound that produces an acid component when exposed to light can be used as a PAG. Preferably, an onium salt compound (e.g., an organic sulfonic acid), a phosphonium salt compound (e.g., a phosphonium salt) or a mixture thereof can be used. Non-limiting examples of PAG include phthalimidotrifluoro methane sulfonate, dinitrobenzyl tosylate, n-decyl disulfone, Naphthylimido trifluorome thane sulfonate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroarsenate, hexafluoride Diphenyl iodonium hexafluoroantimonate, diphenyl p-methoxyphenyl sulfonium triflate, triphenylsulfonium hexafluoroantimonate , triphenylsulfonium triflate, dibutylnaphtylsulfonium triflate, and mixtures thereof. If PAG or TAG is used, it is preferably used in an amount of from 0 to 20 parts by weight, more preferably from 0.05 to 20 parts by weight, based on the weight of the polymer 100 parts by weight of 201038595. It is preferably from 0.1 to 10 parts by weight. The amount of S PAG or TAG is too high. The photo-sensitivity of the t-form is reduced, resulting in insufficient deprotection of the protecting group. If the amount of PAG or TAG is too large, the target pAG or TAG generates an excess of acid' so that the coating layer The shape is not good. The surfactant which can be used in the present invention is preferably a water-soluble surfactant, but an anionic surfactant, a cationic surfactant and an amphoteric surfactant can also be used. 〇 For example, an alkylbenzenesulfonate, a higher halogenated amine, a quaternary ammonium salt, a snap salt, an amino acid, a brewed imine, a continuous amine surfactant, or a mixture thereof may be used. The content of the surfactant is based on the weight of the entire composition for coating the photoresist pattern, and the weight of the 里1 to 2 is preferably 〇. If the surfactant content is too small, the uniformity of coating will be reduced; if the surfactant content is too large, the film layer will be lost in a large amount during the process of removing the coating layer by water, and it cannot be effectively formed on the first pattern. Coating layer. Next, please refer to Fig. 2, which illustrates a method for forming a pattern of a semiconductor element. The first photoresist layer 20 is formed on a substrate 1 (e.g., a wafer, aluminum, etc.) (see A of Fig. 2). The first photoresist layer 20 is exposed and developed with the desired image to form a first photoresist pattern 22 (see B of Fig. 2). The composition for coating the first photoresist pattern 22 is coated, followed by volatilization of the solvent in the composition to form a coating layer 3 (see C of Fig. 2). The polymer of the first photoresist pattern 22 and the coating layer 30 is adhered by a method such as baking the coating layer 30, or the acid is diffused from the first photoresist pattern to the polymer of the coating layer 30 so as to be covered by the coating. Interface formed by the material 201038595 Layer 32 is developed around the first photoresist pattern 22 (see Figure 2 for developer (such as water, alcohol, aqueous alkaline solution, and mixtures thereof) and removes unreacted coating layer 30 parts, in order to reduce the gap between the first light barrier
間隔(開放區域)(參見第2圖的Ε)β塗佈第二光阻來填充 介面層32間的間隔,以形成第二光阻圖案42(參見第2 圖的F)。若有必要,利用曝光或烘烤第二光阻圖案々a, 使酸擴散到第二光阻圖案42,以增進第二光阻圖案42 的硬度。在此情況下,第二光阻較佳為光照射下可改變 性質的感光光阻。接著,使用已溶解〇1至1〇重量%之 鹼性化合物(如氫氧化鈉、氫氧化鉀、碳酸鈉和氫氧化 甲基錢(tetramethyl ammonium hydr〇xide, ΤΜαη ⑽驗 性水溶液,顯影移除介面層32,且第一光阻圖案U和 第二光阻圖案42仍留在基材上(參見第2圖的G)。如 此將形成間隔寬度比習知技術更小的光阻圖案。其中, 因第-光阻圖案22、第二光阻圖案42、塗佈層3〇和介 面層32對顯影液的溶解度視其材料性質、烘烤或曝光而 變得不同’控制顯影條件或顯影時間可選擇性顯影介面 層32。尤其是在本發明用於塗佈光阻圖案的聚合物實例 中’酸擴散製程是在形成第二光阻圖案42後進行曝光或 烘烤而施行’因此用於介面& 32、第一光阻圖案22及 :二光阻圖案42之塗佈光阻圖案的聚合物的性質會變 传更不相同’這是由於酸擴散製程將去保護用於塗佈光 _案的聚合物。利用以第—光阻圖案22和第二光阻圖 案42做為遮罩並利用㈣方式處理基材1(),或改變基 201038595 材ι〇之開放區域的性質’可形成半導體元件圖案。 • §知氟化氬(ArF)或氣化氪(KrF)光阻可當作用於形成 . 帛-光阻圖案22和第二光阻圖案42的光阻。例如,藉 由形成線性第二光阻圖案42於第一光阻圖案U間的間 隔,可形成接近30奈米(nm)的高解析度圖 、” 取仕此用於 形成半導體元件圖案的方法中,用於塗佈層3〇戈介面層 32的聚合物做為覆蓋材料來保留用於形成第二光阻圖案 Q 42的間隔,進而形成雙倍光阻圖案。 以下將詳述較佳實例來更清楚地說明本發明。然而, 本發明理應不限於下列實例。 [實例1-1]製備以化學式2a表示之聚合物 將11.1克((M莫耳)的1-乙烯吡咯酮 • (1-vinyl-PyrroUd〇ne)、13.2 克(0.1 莫耳)的丙烯酸氨基甲 氧基曱酯(acrylic acid aminomethoxymethyl ester)和 〇 7 克的偶 雙異 丁腈(azobis(isobutyronitrile), AIBN)加入 0 反應器内並溶於100克的乙腈。接著,利用冷凍方法以 安瓿移除氣體,去氣之反應物則在70。(:下聚合24小時。 聚合完成後’將反應物緩緩加到過量二乙鍵中而沉搬出 產物’接著將產物溶於乙腈。溶解之產物於二乙醚中再 沉澱而製備以化學式2a表示之聚合物。所得聚合物的重 量平均分子量(Mw)、數目平均分子量(Μη)和聚合度分佈 性(PD)由凝膠滲透層析儀(Gel Permeation Chromatography, G1)C)測量(GPC 分析:Mn=29,000 ; Mw=81,000 ; PD = 2.79)。 15 201038595 [實例1-2]製備以化學式2b表示之聚合物 ^ 除了使用14.5克(0.1莫耳)的丙烯酸氨基乙氧基甲酯 (acrylic acid aminoethoxymethyl ester)取代 13.2 克(〇·1 莫耳)的丙烯酸氨基甲氧基曱酯外,以與實例1 _ 1相同的 方式製備化學式2b表示之聚合物。所得聚合物的重量平 均分子量(Mw)、數目平均分子量(Μη)和聚合度分佈性 (PD)由 GPC 測量(GPC 分析:Mn = 26,500 ; Mw=69,800 ; PD = 2.63)。 [實例1-3]製備以化學式2c表示之聚合物 除了使用19.9克(0.1莫耳)的‘氨基環己氧基甲酯 (4-amino-cyclohexyloxymethyl ester)取代 13.2 克(〇· 1 莫 耳)的丙烯酸氨基f氧基甲酯外,以與實例1 -1相同的方 - 式製備化學式2c表示之聚合物。所得聚合物的重量平均 分子量(Mw)、數目平均分子量(Μη)和聚合度分佈性(PD) 由 GPC 測量(GPC 分析:Mn=24,800 ; Mw=78,500 ; 〇 PD=3.17)。 [實例1-4]製備以化學式2d表示之聚合物 除了使用 〇·1莫耳的 4-氨基苯氧基甲酯 (4-amino-phenoxymethyl ester)取代 13.2 克(0.1 莫耳)的 丙烯酸氨基曱氧基甲酯外,以與實例1-1相同的方式製 備化學式2d表示之聚合物。所得聚合物的重量平均分子 ' 量(Mw)、數目平均分子量(Μη)和聚合度分佈性(PD)由 GPC 測量(GPC 分析:Mn=26,900; Mw=77,000; PD=2.86)。 [實例1-5]製備以化學式2e表示之聚合物 16 201038595 除了使用8.6克(0.1莫耳)的卜乙酸乙烯酯(1_vinyi acetate)取代1M克((M莫耳)的丨乙烯吡咯酮外,以與 實例相同的方式製備化學式2e表示之聚合物。所得 聚合物的重量平均分子量(Mw)、數目平均分子量(_和 聚合度分佈性(PD)由GPC測量(GPC分析:Mn=19 〇〇〇 ;The spacer (open area) (see Ε of Fig. 2) is coated with a second photoresist to fill the space between the interface layers 32 to form a second photoresist pattern 42 (see F of Fig. 2). If necessary, the acid is diffused to the second photoresist pattern 42 by exposing or baking the second photoresist pattern 々a to enhance the hardness of the second photoresist pattern 42. In this case, the second photoresist is preferably a photosensitive photoresist which can change properties under light irradiation. Next, using an alkaline compound (such as sodium hydroxide, potassium hydroxide, sodium carbonate, and methyl hydrazide (10%), which has been dissolved in 〇1 to 1% by weight of an alkaline compound, is removed by development. The interface layer 32, and the first photoresist pattern U and the second photoresist pattern 42 remain on the substrate (see G of FIG. 2). Thus, a photoresist pattern having a smaller spacer width than the prior art will be formed. The solubility of the developing solution due to the first-resist pattern 22, the second photoresist pattern 42, the coating layer 3, and the interface layer 32 becomes different depending on the material properties, baking or exposure. 'Control development conditions or development time The interface layer 32 can be selectively developed. Especially in the polymer example for coating a photoresist pattern of the present invention, the 'acid diffusion process is performed by exposing or baking after forming the second photoresist pattern 42. The properties of the polymer of the interface & 32, the first photoresist pattern 22 and the photoresist pattern of the two photoresist patterns 42 may be changed more differently. This is because the acid diffusion process will be deprotected for coating light. _ the polymer of the case. 22 and the second photoresist pattern 42 are used as a mask and the substrate 1 () is treated by the method of (4), or the property of the open region of the substrate 201038595 is changed to form a semiconductor element pattern. Or a vaporized germanium (KrF) photoresist can be used as a photoresist for forming the germanium-resist pattern 22 and the second photoresist pattern 42. For example, by forming a linear second photoresist pattern 42 to the first photoresist The interval between the patterns U can form a high-resolution map close to 30 nanometers (nm), "in the method for forming a pattern of a semiconductor element, the polymer used for coating the layer 3 of the interface layer 32 The space for forming the second photoresist pattern Q 42 is reserved for the cover material, thereby forming a double photoresist pattern. The preferred embodiment will be described in more detail below to more clearly illustrate the present invention. However, the present invention is not limited to the following examples. [Example 1-1] Preparation of a polymer represented by Chemical Formula 2a 11.1 g ((M mole) of 1-vinylpyrrolidone (1-vinyl-Pyrro Ud〇ne), 13.2 g (0.1 mol) of acrylic acid Acrylic acid aminomethoxymethyl ester and 偶7 g of even double Isobutyronitrile (AIBN) was added to the 0 reactor and dissolved in 100 g of acetonitrile. Then, the gas was removed by ampoules using a freezing method, and the degassed reactant was at 70. (: Polymerization for 24 hours) After the completion of the polymerization, the reactant was gradually added to the excess of the diethyl bond to precipitate the product, and then the product was dissolved in acetonitrile. The dissolved product was reprecipitated in diethyl ether to prepare a polymer represented by the chemical formula 2a. The weight average molecular weight (Mw), number average molecular weight (?n) and degree of polymerization (PD) of the material were measured by Gel Permeation Chromatography (G1) C) (GPC analysis: Mn = 29,000; Mw = 81,000; PD = 2.79). 15 201038595 [Example 1-2] Preparation of a polymer represented by Chemical Formula 2b ^ In addition to using 14.5 g (0.1 mol) of acrylic acid aminoethoxymethyl ester in place of 13.2 g (〇·1 mol) A polymer represented by Chemical Formula 2b was prepared in the same manner as in Example 1-1 except for the methoxy methoxy acrylate. The weight average molecular weight (Mw), number average molecular weight (??) and degree of polymerization (PD) of the obtained polymer were measured by GPC (GPC analysis: Mn = 26,500; Mw = 69,800; PD = 2.63). [Example 1-3] Preparation of the polymer represented by Chemical Formula 2c except that 19.9 g (0.1 mol) of 'amino-cyclohexyloxymethyl ester' was used instead of 13.2 g (〇·1 mol) The polymer represented by Chemical Formula 2c was prepared in the same manner as in Example 1-1 except for the amino-f-oxymethyl acrylate. The weight average molecular weight (Mw), number average molecular weight (??) and degree of polymerization (PD) of the obtained polymer were measured by GPC (GPC analysis: Mn = 24,800; Mw = 78,500; 〇 PD = 3.17). [Example 1-4] Preparation of a polymer represented by Chemical Formula 2d In place of 13.2 g (0.1 mol) of aminoguanidine acrylate, except for 4-amino-phenoxymethyl ester of 〇·1 mole was used. A polymer represented by Chemical Formula 2d was prepared in the same manner as in Example 1-1 except for the oxymethyl ester. The weight average molecular weight (Mw), number average molecular weight (?n), and degree of polymerization distribution (PD) of the obtained polymer were measured by GPC (GPC analysis: Mn = 26,900; Mw = 77,000; PD = 2.86). [Example 1-5] Preparation of Polymer 16 represented by Chemical Formula 2e 201038595 In addition to the use of 8.6 g (0.1 mol) of vinyl acetate (1 vinyi acetate) in place of 1 M g ((M mole) of fluorenylpyrrolidone, The polymer represented by Chemical Formula 2e was prepared in the same manner as the Example. The weight average molecular weight (Mw), number average molecular weight (_ and degree of polymerization distribution (PD) of the obtained polymer were measured by GPC (GPC analysis: Mn = 19 〇〇) Oh ;
Mw=68,400 ; PD=3.60) 〇 [實例1-6]製備以化學式汀表示之聚合物 Ο 除了使用13.9克(0·1莫耳)的1-乙烯己内醯胺(l-vinyl caprolactame)取代克(0.1莫耳)的丨-乙烯吡咯酮外, 以與實例1-1相同的方式製備化學式2f表示之聚合物。 所得聚合物的重量平均分子量(Mw)、數目平均分子量 (Μη)和聚合度分佈性(PD)由gpC測量(Gpc分析: • Mn=30,200 ; Mw=75,600 ; PD=2.50) ° [實例1-7]製備以化學式2g表示之聚合物 除了使用7‘2克(0.1莫耳)的丙烯酸取代11_1克(0.1莫 耳)的1-乙烯吡咯蜩外,以與實例卜丨相同的方式製備化 學式2g表示之聚合物。所得聚合物的重量平均分子量 (Mw)、數目平均分子量(Mn)和聚合度分佈性(pD)由 測量(GPC 分析.Mn=29,500 ; Mw=78,600 ; PD = 2.66)。 [實例2-1至2-8]製備用於塗佈光阻圖案的組成 如下表1所示,將2.7克用於塗佈光阻圖案的聚合物(其 分別依實例1-1至丨―7(化學式2a至2g)製備)、〇 3克的 水溶性界面活性劑(磺醯胺類界面活性劑,tci有限公 ~ 〇.1克的TAG(二氣甲績酸錄(amm〇nium 17 201038595 trifluoromethane sulfonate,Aldrich 有限公司))和 〇_15 克 的PAG(三氟曱炫續酸三苯基銷·鹽(triPhenylsulfonium triflate))溶於17.0克的去離子水,或溶於去離子水與異 丙醇以6 : 4之比例混合的溶劑中’並以〇.2微米(Pm)之 盤濾機過濾,進而製備用於塗佈光阻圖案的組成物。 表1 聚合物 聚合物含量 界面活性劑 TAG PAG 去離子水 醇 實例2-1 化學式2a 2.7克 0.3克 0.1克 - 17克 實例2-2 化學式2b 2_7克 0.3克 0.1克 - 17克 - 實例2-3 化學式2c 2.7克 0.3克 0.1克 - 17克 - 實例2-4 化學式2d 2.7克 0.3克 0.1克 - 17克 - 實例2-5 化學式2e 2·7克 0.3克 0.1克 - Π克 - 實例2-6 化學式2f 2.7克 0.3克 0.1克 - 17克 - 實例2-7 化學式2g 2.7克 0.3克 0.1克 - 17克 - 實例2-8 化學式2g 2.7克 0.3克 0.1克 0.15 克 10.2 克 6.8克 [實例3-1至3-8]以用於塗佈光阻圖案的組成來形成 Q 半導體元件圖案 將2克的以下列化學式3表示之ArF光阻聚合物(分子 量(Mw) : 10,100 ;聚合度分佈性(PD) : 1·89 ; a : b : c(莫 耳%)=45 : 40 : 15)、0.02克的三氟酸三苯基硫鹽和〇.〇1 克的三乙醇胺溶於 10克的丙二酵單甲醚醋酸酯 . (propyleneglycolmonomethyletheracetate, PGMEA),並以 〇.2μηι之過滹器過濾,進而製備用於塗佈第一光阻圖案 的組成物。 [化學式3] 18 201038595Mw = 68,400; PD = 3.60) 〇 [Example 1-6] Preparation of polymer 表示 represented by chemical formula In addition to using 13.9 g (0.1 mol) of 1-vinyl caprolactame A polymer represented by Chemical Formula 2f was prepared in the same manner as in Example 1-1 except for gram (0.1 mol) of oxime-vinylpyrrolidone. The weight average molecular weight (Mw), number average molecular weight (?n), and degree of polymerization distribution (PD) of the obtained polymer were measured by gpC (Gpc analysis: • Mn = 30,200; Mw = 75,600; PD = 2.50) ° [Example 1 7] Preparation of polymer represented by Chemical Formula 2g Formula 2g was prepared in the same manner as in the example dip except that 7'2 g (0.1 mol) of acrylic acid was used instead of 11_1 g (0.1 mol) of 1-vinylpyrroleium. Represents the polymer. The weight average molecular weight (Mw), number average molecular weight (Mn) and degree of polymerization distribution (pD) of the obtained polymer were measured by GPC analysis. Mn = 29,500; Mw = 78,600; PD = 2.66. [Examples 2-1 to 2-8] Preparation of a composition for coating a photoresist pattern As shown in Table 1 below, 2.7 g of a polymer for coating a photoresist pattern (which is respectively according to Example 1-1 to 丨) 7 (chemical formula 2a to 2g)), 3 grams of water-soluble surfactant (sulfonamide surfactant), tci limited ~ 〇. 1 gram of TAG (two gas A acid 录 record (amm〇nium 17 201038595 trifluoromethane sulfonate, Aldrich Co., Ltd.)) and 〇15 grams of PAG (triPhenylsulfonium triflate) dissolved in 17.0 grams of deionized water, or dissolved in deionized water Isopropanol was filtered in a solvent mixed at a ratio of 6:4 and filtered through a 2 micrometer (Pm) disk filter to prepare a composition for coating a photoresist pattern. Table 1 Polymer polymer content interface Active agent TAG PAG Deionized water alcohol Example 2-1 Chemical formula 2a 2.7 g 0.3 g 0.1 g - 17 g Example 2-2 Chemical formula 2b 2_7 g 0.3 g 0.1 g - 17 g - Example 2-3 Chemical formula 2c 2.7 g 0.3 g 0.1克 - 17g - Example 2-4 Chemical Formula 2d 2.7g 0.3g 0.1g - 17g - Example 2-5 Chemical Formula 2e 2·7g 0.3g 0 .1 g - gram - Example 2-6 Chemical formula 2f 2.7 g 0.3 g 0.1 g - 17 g - Example 2-7 Chemical formula 2g 2.7 g 0.3 g 0.1 g - 17 g - Example 2-8 Chemical formula 2g 2.7 g 0.3 g 0.1克 0.15 g 10.2 g 6.8 g [Examples 3-1 to 3-8] to form a Q semiconductor element pattern for coating the composition of the photoresist pattern 2 g of an ArF photoresist polymer represented by the following Chemical Formula 3 (molecular weight (Mw) : 10,100 ; degree of polymerization distribution (PD): 1·89 ; a : b : c (mol %) = 45 : 40 : 15), 0.02 g of triphenylsulfate trifluorosulfate and 〇. 1 g of triethanolamine is dissolved in 10 g of propylene glycol monomethyl ether acetate (PGMEA) and filtered through a 〇.2μηι filter to prepare a first photoresist pattern. Composition. [Chemical Formula 3] 18 201038595
OH 利用上述光阻組成物形成線寬與間隔之比例為1 : 3之 50nm圖案(第一光阻圖案)。將依實例2-1至2-8製備之 光阻組成物旋塗在形成有第一光阻圖案的晶圓頂部,以 形成薄層,接著在烤箱中或在加熱板上,以1 50°C軟烤已 〇 旋塗之晶圓60秒。將經烘烤之晶圓沉浸於2.38重量%之 氩氧化四曱基銨(TMAH)水溶液或去離子水中60秒,以 進行顯影而覆蓋第一光阻圖案(形成介面層)。依上述方 法形成的塗覆圖案之線寬變化列於表2。 表2 第一光阻圖案的線寬; 關鍵尺寸(CD) 以介面層塗覆第一光阻圖案 後的線寬 實例3-1 50 nm 82 nm 實例3-2 50 nm 78 nm 實例3-3 50 nm 78 nm 實例3-4 50 run 65 nm 實例3-5 50 nm 86 nm 實例3-6 50 nm 85 nm 實例3-7 50 run 76 nm 實例3-8 50 nm 82 nmOH The above photoresist composition was used to form a 50 nm pattern (first photoresist pattern) having a line width to space ratio of 1:3. The photoresist composition prepared according to Examples 2-1 to 2-8 was spin-coated on top of the wafer on which the first photoresist pattern was formed to form a thin layer, followed by 1 50° in an oven or on a hot plate. C soft bake has been applied to the wafer for 60 seconds. The baked wafer was immersed in a 2.38 wt% aqueous solution of tetradecyl ammonium arsenate (TMAH) or deionized water for 60 seconds to develop to cover the first photoresist pattern (forming the interface layer). The line width variation of the coating pattern formed by the above method is shown in Table 2. Table 2 Line width of the first photoresist pattern; critical dimension (CD) Line width after coating the first photoresist pattern with the interface layer Example 3-1 50 nm 82 nm Example 3-2 50 nm 78 nm Example 3-3 50 nm 78 nm Example 3-4 50 run 65 nm Example 3-5 50 nm 86 nm Example 3-6 50 nm 85 nm Example 3-7 50 run 76 nm Example 3-8 50 nm 82 nm
接著,將2克的以下列化學式4表示之KrF光阻聚合 物(分子量(Mw) : 14,800 ;聚合度分佈性(PD) : 2.02 ; a : b(莫耳°/。)=65 : 35)和0.01克的三乙醇胺溶於10克的丙 19 201038595 二醇單曱醚醋酸酯(PGMEA),並以〇.2μιη之過濾器過 濾’進而製備用於塗佈光阻圖案的組成物。 [化學式4]Next, 2 g of a KrF photoresist polymer represented by the following Chemical Formula 4 (molecular weight (Mw): 14,800; degree of polymerization distribution (PD): 2.02; a: b (mole ° /.) = 65 : 35) And 0.01 g of triethanolamine was dissolved in 10 g of C19 201038595 diol monoterpene ether acetate (PGMEA) and filtered through a filter of 〇.2 μηη to prepare a composition for coating a photoresist pattern. [Chemical Formula 4]
0 為於第一光阻圖案間的間隔形成第二光阻圖案,將光 阻組成物(用於第二圖案的光阻)旋塗在晶圓上,且在烤 箱中或在加熱板上,以12(rc軟烤6〇秒。將經烘烤之晶 圓此浸於2·38重量%之氫氧化四甲基銨(TMAH)水溶液 中60秒,以顯影移除塗覆部分(介面層)。高度比第一光 阻圖案低的第二光阻圖案因此形成在第一光阻圖案間的 間隔。第3圖為由實例3_5之組成物所形成的光阻圖案 掃描式電子顯微圖。如第3圖所示,利用本發明之自我 〇 對準雙重圖案化製程(self_align_double-patterning process) ’可輕易在第一光阻圖案間形成線寬與間隔1 : 3之第一光阻圖案。故使用本發明用於塗佈光阻圖案的 聚合物來形成第二光阻圖帛時,採用諸如習头〇 i93nm、 248nm等光源之曝光設備不需進行遮罩對準製程,且該 自我對準雙重圖案化製程只需烘烤及曝光晶圓即可施 行0 【圖式簡單說明】 20 201038595 第1圖為用於形成細小光阻圖案之習知方法之—實施 例的示意圖。 第2圖為根據本發明之用於形成半導體元件圖案的方 法之一實施例的示意圖。 第3圖為由實例3-5之組成物所形成的光阻圖案之掃 描式電子顯微圖。 【主要元件符號說明】 〇 10 基材 20 光阻層 22 第一光阻圖案 42 第二光阻圖 30 塗佈層 32 介面層 110 基材 120 光阻層 122 光阻圖案 130 微縮材料 132 邊界層 210, a second photoresist pattern is formed at intervals between the first photoresist patterns, and a photoresist composition (resist for the second pattern) is spin-coated on the wafer, and in an oven or on a heating plate, Soft-bake at 12 rc for 6 sec. The immersed wafer was immersed in a 3.8 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds to remove the coated portion (interface layer). The second photoresist pattern having a lower height than the first photoresist pattern thus forms an interval between the first photoresist patterns. Fig. 3 is a scanning electron micrograph of the photoresist pattern formed by the composition of Example 3-5. As shown in FIG. 3, the first photoresist pattern having a line width and an interval of 1: 3 can be easily formed between the first photoresist patterns by using the self_align_double-patterning process of the present invention. Therefore, when the second resistive pattern is formed by using the polymer for coating a photoresist pattern of the present invention, an exposure apparatus using a light source such as a head 〇i93 nm, 248 nm does not need a mask alignment process, and the self Aligning the double patterning process requires baking and exposing the wafer to perform 0. BRIEF DESCRIPTION OF THE DRAWINGS 20 201038595 Fig. 1 is a schematic view of a conventional method for forming a fine photoresist pattern. Fig. 2 is a schematic view showing an embodiment of a method for forming a pattern of a semiconductor element according to the present invention. Fig. 3 is a scanning electron micrograph of the photoresist pattern formed by the composition of Examples 3-5. [Main element symbol description] 〇10 Substrate 20 Photoresist layer 22 First photoresist pattern 42 Second Photoresist pattern 30 coating layer 32 interface layer 110 substrate 120 photoresist layer 122 photoresist pattern 130 micro-material 132 boundary layer 21
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KR102656746B1 (en) * | 2017-02-03 | 2024-04-11 | 도오꾜오까고오교 가부시끼가이샤 | Resist composition and method of forming resist pattern |
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