TW201120578A - Aromatic ring-included polymer for underlayer of resist, underlayer composition of resist including same, and method of patterning device using same - Google Patents
Aromatic ring-included polymer for underlayer of resist, underlayer composition of resist including same, and method of patterning device using same Download PDFInfo
- Publication number
- TW201120578A TW201120578A TW099125591A TW99125591A TW201120578A TW 201120578 A TW201120578 A TW 201120578A TW 099125591 A TW099125591 A TW 099125591A TW 99125591 A TW99125591 A TW 99125591A TW 201120578 A TW201120578 A TW 201120578A
- Authority
- TW
- Taiwan
- Prior art keywords
- photoresist
- polymer
- group
- chemical formula
- underlayer
- Prior art date
Links
Classifications
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/127—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from carbon dioxide, carbonyl halide, carboxylic acids or their derivatives
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
- G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
Abstract
Description
201120578 六、發明說明： 【發明所屬之技術销域】 發明領域 本揭示係有關於用於光阻底層之包含芳香環的聚合 物、製備該聚合物之方法、包含該聚合物之光喊層挺戍 物，以及使用該組成物將材料圖案化的方法。 I[失*朝Γ治L冬好3 發明背景 於微電子工業以及其他相關的工業（包括微觀結構（諸 如’微機械和磁阻式磁頭）的製造）中，對於降低結構形狀的 尺寸有持續的需求。於微電子工業中’有需要降低微電子 裝置的尺寸俾以於-特定晶片尺寸上提供—些電路。有效 的微影技術對於要達到降低結構形狀的尺寸為必要的。> 典型的微影製程涉及下列的製程。首先，一光阻劑係 被塗覆於-底層材料之上’以及其接受曝露於照射來形成 一光阻層。隨後，該級層接受使用—顯影溶液之辟以 提供了 一圖案化的光阻層，以及該«化的光阻層内之暴 露的底層㈣倾似Ux將1_衫職層材敎 内。在轉移完成之後1轨層之剩餘部分係被移除。 然而，該光阻劑沒有對触刻步驟提供足以有效地轉移 所欲的圖案至-底層材料之阻力。於需要極薄的光㈣、 要被触刻的底㈣料是厚的、需要大_觀度，妓取 決於底層材料_類”要使用特定的軸劑的情況下， 使用一光阻底層。 201120578 中間層光^底層作用為介於該光M和該底層材料之間的 化。圖案化的光阻劑之轉移而予以圖案 圖案以及來自該經㈣化的光阻層的 刻。㈣抵㈣®_移至縣層材細需要的蚀 底層々多用於此—底層之材料，但是對於改良的 二，需求。既然習知的底層材料不容易施加至基 或高溫1:要使用化學和物理蒸氣沈積、特殊的溶劑，及/ 5门恤、共烤。然*，此等方法具有高成本。 t最近已㉘研究—種能藉由旋轉塗佈的技術予以 ^而不心溫供烤的底層組成物。-底層組成物，其能 以今易的方式使用—上覆光阻層作為遮罩而予以選擇性蚀 玄J同a寺對於使用—底層作為遮罩之圖案化一底層金屬層 所必須的⑽純抗‘_，《要被研究。 &層”且成物’其提供了令人滿意的儲存壽命性質以 及避免與-祕光阻層之不需要的交互作用（諸如 ，由硬式 遮罩之底層組成物之内的酸催化劑所造成的光阻劑或基材 污染），為進一步需要研究的。一底層組成物，其具有對抗 短波長(諸如：157 nm、193 nm，以及248 nm)的成像照射 之預定的光學性質’亦需要被研究。 總而言之，一抗反射組成物，其具有高蝕刻選擇性及 具有充分的阻抗對抗多重蝕刻，以及可最小化一光阻劑和 底層材料之間的反射性，需要一微影技術。此一微影技術 能生產非常精細的半導體裝置。 201120578 t發明内容3 發明概要 本發明的一個具體例提供了一種用於光阻底層之包含 芳香環的聚合物，其可以使用一旋轉塗佈技術予以塗佈， 以及具有優秀的光學性質、機械特性，和蝕刻選擇性的特 性。 本發明的另一個具體例提供了一種光阻底層組成物， 其不會有由於一酸催化劑之污染的問題。 本發明的再另一個具體例提供了 一種使用該光阻底層 組成物將裝置圖案化的方法。 依據本發明的一個具體例，提供了一種用於光阻底層 之包含芳香環的聚合物，其包括由下列化學式1表示的一單 元。 [化學式1]201120578 VI. Description of the Invention: [Technical Field of the Invention] Field of the Invention The present disclosure relates to a polymer comprising an aromatic ring for a photoresist underlayer, a method of preparing the polymer, and a light-emitting layer comprising the polymer A sputum, and a method of patterning a material using the composition. I [missing * 朝朝治 L冬好3] Background of the invention In the microelectronics industry and other related industries (including the fabrication of microstructures such as 'micromechanical and magnetoresistive heads), there is a continuation of the reduction in the size of the structural shape Demand. In the microelectronics industry, there is a need to reduce the size of microelectronic devices to provide - some circuits. Effective lithography is necessary to achieve a reduction in the size of the structure. > Typical lithography processes involve the following processes. First, a photoresist is applied over the underlying material and it is exposed to radiation to form a photoresist layer. Subsequently, the grade layer accepts the use of a developing solution to provide a patterned photoresist layer, and the underlying layer of the exposed photoresist layer (4) is like Ux. The remainder of the 1 track layer is removed after the transfer is completed. However, the photoresist does not provide sufficient resistance to the tracing step to effectively transfer the desired pattern to the underlying material. The need for extremely thin light (4), the bottom to be touched (four) is thick, requires a large degree of spectroscopy, and depends on the underlying material _ class. In the case of using a specific axillant, a photoresist underlayer is used. 201120578 The interlayer light acts as a layer between the light M and the underlying material. The patterning of the photoresist is transferred to pattern and the photoresist layer from the (four) photoresist layer. ®_ moved to the county layer to require the etched underlayer to be used for this - the underlying material, but for the improved second, the need. Since the conventional underlying material is not easy to apply to the base or high temperature 1: use chemical and physical vapors Deposition, special solvents, and / 5 door glasses, co-baked. However, these methods have high cost. t Recently, 28 studies have been carried out - a kind of bottom layer that can be baked by spin coating technology. Composition. - The underlying composition, which can be used in an easy-to-use manner - the overlying photoresist layer is used as a mask to selectively etch the sacred J and the a temple for use - the underlying layer is used as a mask to pattern an underlying metal layer Required (10) pure anti-'_, "to be studied. & layer And the article's which provide satisfactory shelf life properties and avoid unwanted interactions with the smectic photoresist layer (such as photoresists caused by acid catalysts within the underlying composition of the hard mask) Or substrate contamination) for further research. A bottom layer composition having predetermined optical properties for imaging illumination against short wavelengths (such as: 157 nm, 193 nm, and 248 nm) also needs to be investigated. In summary, an anti-reflective composition that has high etch selectivity and sufficient impedance against multiple etches, as well as minimizes reflectivity between a photoresist and the underlying material, requires a lithography technique. This lithography technology produces very fine semiconductor devices. 201120578 t SUMMARY OF INVENTION Summary of the Invention One embodiment of the present invention provides a polymer containing an aromatic ring for a photoresist underlayer which can be coated using a spin coating technique and has excellent optical properties and mechanical properties. , and etch selectivity characteristics. Another embodiment of the present invention provides a photoresist underlayer composition which does not have the problem of contamination by an acid catalyst. Still another embodiment of the present invention provides a method of patterning a device using the photoresist underlayer composition. According to a specific example of the present invention, there is provided a polymer comprising an aromatic ring for a photoresist underlayer comprising a unit represented by the following Chemical Formula 1. [Chemical Formula 1]
A R1I Si-I R2 η * 其中， R1和R2獨立地為氫、Cl至CIO烷基基團，或是一芳香 基團，且 A為一官能基，其係衍生自具有一雜原子或沒有一雜原 子之一芳香化合物，以及 η為一或更多數量的整數。η可以為1至100的整數。 201120578 該包含芳香環的聚合物可以具有2000至20,〇〇〇的重量 平均分子量(Mw)。 該芳香基團可以為C5至C20芳香基團。 雜原子可以為N、Ο、S，或P。 依據本發明的另一個具體例之一光阻的底層組成物包 括（a)—種包含芳香環的聚合物，其包括由以上化學式丨所表 示的一單元，以及(b)—有機溶劑。 依據本發明的另一個具體例，提供了一種用於圖案化 裝置的方法，該方法包括：（a)於一基材上提供一材料層； (b) 使用違光阻底層組成物於該材料層上形成一光阻底層； (c) 於該光阻底層上形成一光阻層；（…令該基材上的該光阻 層曝光；（e)令該曝光的基材顯影；以及(f)蝕刻該顯影的基 材。 本方法可進一步包括在形成該光阻層的步驟(ste〇) (c) 之前’形成一含矽光阻底層。 本方法可進一步包括在步驟(c)之前，於該含石夕光阻底 層上形成底部抗反射塗層（BARC)。 一光阻底層的聚合物具有優秀的光學性質、機械特 性，以及蝕刻選擇性特性。包括聚合物之光阻底層組成物 的’其可以使用一旋轉塗佈技術予以塗佈於一基材之上， 對於短波長的微影製程是有用的，以及不被一酸催化劑所 污染的’因為酸催化劑可以以小量來使用。 既然一光阻的底層組成物於D U V波長區域（例如a rF 193nm)中具有作為一抗反射層之折射指數和適當範圍的 201120578 吸收，所以其可以將介於該光阻劑和該底層之間的反射性 予以最小化。從而，一光阻的底層組成物可以提供就圖案 輪廓或者邊緣而論之優秀的微影結構。既然一光阻的底層 組成物在微影製程的期間具有高的蝕刻選擇性以及充分 的阻抗對抗多重的触刻，相較於習知的組成物，所以一光 阻底層的蝕刻輪廓（要被轉移至較低層的圖像）是非常好 的。 I：實施方式3 較佳實施例之詳細說明 在下文中將詳細地說明本發明之例示性具體例。然 而，此等具體例僅供舉例說明之用，且不會限制本發明。 依據本發明的一個具體例，提供了一種包含芳香環的 聚合物，其包括由下列化學式1表示的一單元。該包括由下 列化學式1表示的一單元之包含芳香環的聚合物包括一芳 香環於一聚合物主鏈内，該芳香環在短波長區域(特別地， 193nm、248nm，等等）具有強的吸收，以及因而可以使用 作為一抗反射塗層。 [化學式1] R1 Γ I Ί *--A——Si--*A R1I Si-I R2 η * wherein R1 and R2 are independently hydrogen, a Cl to CIO alkyl group, or an aromatic group, and A is a monofunctional group derived from having a hetero atom or not An aromatic compound of one of a hetero atom, and η is an integer of one or more. η may be an integer from 1 to 100. 201120578 The polymer containing an aromatic ring may have a weight average molecular weight (Mw) of from 2,000 to 20 Å. The aromatic group may be a C5 to C20 aromatic group. The hetero atom can be N, Ο, S, or P. According to another embodiment of the present invention, the underlayer composition of the photoresist comprises (a) a polymer comprising an aromatic ring comprising a unit represented by the above chemical formula, and (b) an organic solvent. According to another embodiment of the present invention, a method for patterning a device is provided, the method comprising: (a) providing a layer of material on a substrate; (b) using a composition of the photoresist underlying layer Forming a photoresist underlayer on the layer; (c) forming a photoresist layer on the photoresist underlayer; (...exposing the photoresist layer on the substrate; (e) developing the exposed substrate; and f) etching the developed substrate. The method may further comprise forming a germanium-containing photoresist under the step (ste) (c) of forming the photoresist layer. The method may further comprise prior to step (c) A bottom anti-reflective coating (BARC) is formed on the underlying photoresist layer. The polymer of the photoresist bottom layer has excellent optical properties, mechanical properties, and etch selectivity characteristics, including the photoresist underlayer composition of the polymer. 'It can be applied to a substrate using a spin coating technique, useful for short-wavelength lithography processes, and not contaminated with an acid catalyst' because the acid catalyst can be small Use. Since the bottom layer of a photoresist The material has a refractive index as an anti-reflective layer and an appropriate range of 201120578 absorption in the DUV wavelength region (e.g., a rF 193 nm), so it can minimize the reflectivity between the photoresist and the underlayer. Thus, a photoresist underlayer composition can provide excellent lithographic structure in terms of pattern outline or edge. Since a photoresist underlayer composition has high etch selectivity and sufficient impedance resistance during lithography processes. Multiple etches, the etch profile of a photoresist underlayer (the image to be transferred to the lower layer) is very good compared to conventional compositions. I: Embodiment 3 Details of the preferred embodiment The exemplified embodiments of the present invention will be described in detail below. However, these specific examples are for illustrative purposes only and are not intended to limit the invention. In accordance with one embodiment of the present invention, an aromatic ring is provided. a polymer comprising a unit represented by the following Chemical Formula 1. The polymer comprising an aromatic ring represented by a unit represented by the following Chemical Formula 1 includes an aromatic ring In a polymer main chain, the aromatic ring has strong absorption in a short wavelength region (particularly, 193 nm, 248 nm, etc.), and thus can be used as an anti-reflection coating. [Chemical Formula 1] R1 Γ I Ί * --A——Si--*
L I J R2 n 於以上的化學式ί中， R1和R2獨立地為氫、Cl至CIO烷基基團，或一芳香基L I J R2 n In the above formula, R1 and R2 are independently hydrogen, Cl to CIO alkyl group, or an aromatic group
S 7 201120578 團， A為一官能基，其係衍生自具有一雜原子或是沒有一雜 原子之一芳香化合物，以及 η為一或更多數量的整數，例如1至100。 該芳香基團可以為C5至C20芳香基圑，以及也可以為 C6至C40芳香基團。 雜原子可以為Ν、Ο、S，或是Ρ。 衍生自具有一雜原子或沒有一雜原子之芳香化合物的 官能基（Α)為一官能基，其係衍生自一 C6至C40芳香化合 物。Α可以為一官能基，其係衍生自用下列化學式la或lb 表示的芳香化合物。於下列化學式la和lb中，X*表示與以 上化學式1的Si結合之位址或是一末端位址。 [化學式la] R4S 7 201120578 A, A is a monofunctional group derived from an aromatic compound having one hetero atom or no one hetero atom, and η is an integer of one or more numbers, for example, 1 to 100. The aromatic group may be a C5 to C20 aromatic oxime, and may also be a C6 to C40 aromatic group. The hetero atom can be Ν, Ο, S, or Ρ. The functional group (Α) derived from an aromatic compound having one hetero atom or no one hetero atom is a monofunctional group derived from a C6 to C40 aromatic compound. The oxime may be a monofunctional group derived from an aromatic compound represented by the following chemical formula la or lb. In the following chemical formulas la and lb, X* represents an address or an end site which is bonded to Si of the above chemical formula 1. [chemical formula la] R4
於以上的化學式la中， R3和R4獨立地為氫、羥基基團、烷氧基基團，或C1-C4 低級烧基基團， R5和R6獨立地為氫、烷氧基基團、C1-C4低級烷基基 團，或羥基基團，以及 X為〇(氧）或S(硫），以及可以為Ο。 ⑧ 8 201120578 [化學式lb]In the above formula la, R3 and R4 are independently hydrogen, a hydroxyl group, an alkoxy group, or a C1-C4 lower alkyl group, and R5 and R6 are independently hydrogen, an alkoxy group, C1. a -C4 lower alkyl group, or a hydroxyl group, and X is deuterium (oxygen) or S (sulfur), and may be deuterium. 8 8 201120578 [Chemical Formula lb]
於化學式lb中， R7和R8獨立地為氫、烷氧基基團、羥基基團，或C1-C4 低級烧基基團， R9和R10獨立地為氫、烷氧基基團、C1-C4低級烷基基 團，或羥基基團，以及 X為〇(氧）或S(硫），且可以為Ο。 該烷氧基基團可以為C1-C10烷氧基基團。 該芳香化合物之實例包括：9,9'-雙酚苐、9,9-雙（1-萘酚) 第、二羥苯、二羥萘、二羥芘、二羥蒽，或是其等之組合， 但非囿限於此。 該包含芳香環的聚合物可以具有2000至20,000的重量 平均分子量(Mw)。當該包含芳香環的聚合物具有於以上的 範圍内之重量平均分子量時，可以獲得到令人滿意的塗層 厚度或是薄膜。 可以獲得到薄膜。 使用依據一具體例之包含芳香族的聚合物之光阻底層 可以為0.30至0.70之吸光度。具有該吸光度之光阻底層可以 充分地作用為底部抗折射塗覆層。 201120578 依據一具體例之包含芳香族的聚合物可以藉由以下方 式予以製備：於一溶劑中使一芳香化合物（為一官能基之A 可以由其所衍生的）與由下列化學式5表示的二氣矽烷化合 物，以及一弱鹼進行反應。製備為一個具體例以及非囿限 於本發明。 [化學式5] R1 I. c I —Si— ciIn the formula lb, R7 and R8 are independently hydrogen, an alkoxy group, a hydroxyl group, or a C1-C4 lower alkyl group, and R9 and R10 are independently hydrogen, an alkoxy group, C1-C4. Lower alkyl group, or hydroxyl group, and X is deuterium (oxygen) or S (sulfur), and may be deuterium. The alkoxy group can be a C1-C10 alkoxy group. Examples of the aromatic compound include: 9,9'-bisphenolphthalein, 9,9-bis(1-naphthol), dihydroxybenzene, dihydroxynaphthalene, dihydroxyindole, dihydroxyindole, or the like. Combination, but not limited to this. The aromatic ring-containing polymer may have a weight average molecular weight (Mw) of from 2,000 to 20,000. When the polymer containing the aromatic ring has a weight average molecular weight within the above range, a satisfactory coating thickness or film can be obtained. A film can be obtained. The photoresist underlayer using a polymer containing an aromatic polymer according to a specific example may have an absorbance of 0.30 to 0.70. The photoresist bottom layer having the absorbance can sufficiently function as the bottom anti-reflection coating layer. 201120578 According to a specific example, the aromatic-containing polymer can be prepared by subjecting an aromatic compound (which may be derived from a functional group A) to a compound represented by the following Chemical Formula 5 in a solvent. The gas decane compound, and a weak base, react. The preparation is a specific example and is not limited to the present invention. [Chemical Formula 5] R1 I. c I —Si—ci
I R2 於以上的化學式5中，R1和R2具有以上提供的意義。 該芳香化合物之實例包括：9,9’-雙酚苐、9,9-雙（1-萘酚) 苐、二羥苯、二羥萘、二羥芘、二羥蔥，或是其等之組合， 但非囿限於此。 由下列化學式la’，或化學式lb’表示的芳香化合物之說 明性（explanary)實施例： [化學式la’] R4I R2 In the above Chemical Formula 5, R1 and R2 have the meanings provided above. Examples of the aromatic compound include: 9,9'-bisphenolphthalein, 9,9-bis(1-naphthol) anthracene, dihydroxybenzene, dihydroxynaphthalene, dihydroxyindole, dihydroxy onion, or the like Combination, but not limited to this. An illustrative example of an aromatic compound represented by the following chemical formula la', or chemical formula lb': [Chemical formula la'] R4
於化學式la’中，R3至R6具有以上提供的意義，以及Y 為-OH或-SH。 10 201120578 [化學式lb’]In the formula la', R3 to R6 have the meanings given above, and Y is -OH or -SH. 10 201120578 [Chemical formula lb']
於化學式lb’中，R7至R10具有以上提供的意義，以及 Y為-OH或-SH。 該弱驗可以是係為被包括：三乙基胺、苯胺、σ比。定、 氫氧化鋁，等等，但非囿限於此。 該溶劑可以為任何的有機溶劑，以及可以為任何一 者，只要其可以溶解該芳香化合物、二氣矽烷化合物，以 及該弱鹼。該溶劑之實例包括：曱苯、二甲苯，等等，但 非囿限於此。 該反應可以在-20至100 °C的溫度予以執行歷時5至 15。該芳香化合物與二氣矽烷化合物的混合比率可以適當 地被控制。再者，反應的條件，例如溫度，可以適當地被 控制。 依據本發明的另一個具體例之光阻底層組成物包括（a) 一種包含芳香環的聚合物以及(b) —有機溶劑。 至於有機溶劑，可以使用對於該聚合物具有充分的溶 解度之任何的有機溶劑。有機溶劑之實例包括：丙二醇一 甲基醚乙酸酯（PGMEA)、丙二醇曱醚(PGME)、環己酮、乳 酸乙酯、γ -丁内酯（GBL)、丙酮乙醯，及類似物。 11 201120578 於依據一具體例之光阻底層組成物中，該包含芳香環 的聚合物可以以1至20 wt%的量予以含括，以及於另一個具 體例中，3至10 wt%。當該包含芳香環的聚合物係以以上的 範圍予以含括時，可以適當地調整一光阻底層之令人滿意 的塗層厚度。 該有機溶劑可以以差額量，或是80至99 wt%予以使 用。當該有機溶劑係以以上的範圍予以含括時，可以適當 地調整一光阻底層之令人滿意的塗層厚度。 依據一具體例之光阻底層組成物進一步包括一界面活 性劑，或是一交聯組分。並且，依據一具體例之光阻底層 組成物進一步包括一酸催化劑。 於本文中，以100份該光阻底層組成物的重量為基準， 該界面活性劑的含量可在0.01至1份以重量計的範圍内。以 100份該光阻底層組成物的重量為基準，該交聯組分的含量 可以在0.01至1份以重量計的範圍内。以100份該光阻底層 組成物的重量為基準，該酸催化劑的含量可以在0.01至1份 以重量計的範圍内。 當該交聯組分的含量落在以上範圍内時，可以獲得適 當的交聯特性同時不改變該形成的底層之光學特性。 至於界面活性劑，可以使用烧基苯續酸鹽、院基。比°定 鹽、聚乙二醇，以及四級銨鹽，但本發明非囿限於此。 該交聯組分可以包括任何的交聯劑，其可以藉著所產 生的酸予以催化而與一聚合物組成物的一經基反應。此一 交聯組分包括係選自於以下之一者：三聚氰胺樹脂、胺樹 12 201120578 脂、乙炔脲化合物化合物、雙環氧化合物，或是其等之組 合。 適合的交聯組分之實例包括：醚化胺樹脂、甲基化三 聚氰胺樹脂（諸如，N-曱氧基甲基-三聚氰胺樹脂）、丁基化 三聚氰胺樹脂（諸如，N-丁氧基曱基-三聚氰胺樹脂）、甲基 化脲樹脂或丁基化脲樹脂（諸如，Cymel U-65樹脂和UFR 80 樹脂）、由下列的化學式30表示的乙炔脲衍生物（諸如， Powderlink 1174)，以及2,6-雙（經曱基)-/?-甲驗。由下列化 學式31表示的雙環氧為主的化合物以及由下列的化學式32 表示的三聚氰胺為主的化合物亦可以使用作為一交聯組 分。 [化學式30]In the formula lb', R7 to R10 have the meanings given above, and Y is -OH or -SH. The weak test may be included to include: triethylamine, aniline, sigma ratio. Fixed, aluminum hydroxide, etc., but not limited to this. The solvent may be any organic solvent, and may be any one as long as it can dissolve the aromatic compound, the dioxane compound, and the weak base. Examples of the solvent include: toluene, xylene, and the like, but are not limited thereto. The reaction can be carried out at a temperature of from -20 to 100 ° C for a period of from 5 to 15. The mixing ratio of the aromatic compound to the dioxane compound can be appropriately controlled. Further, the conditions of the reaction, such as temperature, can be appropriately controlled. A photoresist underlayer composition according to another embodiment of the present invention comprises (a) a polymer comprising an aromatic ring and (b) an organic solvent. As the organic solvent, any organic solvent having a sufficient solubility for the polymer can be used. Examples of the organic solvent include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol oxime ether (PGME), cyclohexanone, ethyl lactate, γ-butyrolactone (GBL), acetone acetonide, and the like. 11 201120578 In the photoresist underlayer composition according to a specific example, the aromatic ring-containing polymer may be contained in an amount of from 1 to 20% by weight, and in another specific example, from 3 to 10% by weight. When the polymer containing the aromatic ring is included in the above range, a satisfactory coating thickness of a photoresist underlayer can be appropriately adjusted. The organic solvent can be used in a differential amount or in an amount of 80 to 99% by weight. When the organic solvent is included in the above range, a satisfactory coating thickness of a photoresist underlayer can be appropriately adjusted. The photoresist underlayer composition according to a specific example further comprises an interface active agent or a cross-linking component. Further, the photoresist base composition according to a specific example further includes an acid catalyst. Herein, the content of the surfactant may be in the range of 0.01 to 1 part by weight based on 100 parts by weight of the photoresist underlayer composition. The content of the crosslinking component may be in the range of 0.01 to 1 part by weight based on 100 parts by weight of the composition of the photoresist underlayer. The content of the acid catalyst may be in the range of 0.01 to 1 part by weight based on 100 parts by weight of the composition of the photoresist underlayer. When the content of the crosslinking component falls within the above range, appropriate crosslinking characteristics can be obtained without changing the optical characteristics of the formed underlayer. As the surfactant, a burnt-based benzoate or a hospital base can be used. Salts, polyethylene glycols, and quaternary ammonium salts are specified, but the invention is not limited thereto. The crosslinking component can include any crosslinking agent which can be catalyzed by the acid produced to react with a radical of a polymer composition. The cross-linking component comprises one selected from the group consisting of melamine resin, amine tree 12 201120578 lipid, acetylene urea compound compound, diepoxide, or combinations thereof. Examples of suitable crosslinking components include: etherified amine resins, methylated melamine resins (such as N-methoxymethyl-melamine resins), butylated melamine resins (such as N-butoxy fluorenyl) - melamine resin), methylated urea resin or butylated urea resin (such as Cymel U-65 resin and UFR 80 resin), acetylene urea derivative represented by the following Chemical Formula 30 (such as Powderlink 1174), and 2 , 6-double (via 曱基)-/?-A test. The diepoxy-based compound represented by the following Chemical Formula 31 and the melamine-based compound represented by the following Chemical Formula 32 can also be used as a cross-linking component. [Chemical Formula 30]
[化學式32] 13 201120578[Chemical Formula 32] 13 201120578
HOHO
OHOH
OH 該酸催化劑之實例可包括一有機酸（例如對曱苯績酸 一水合物），以及具有尚的儲存女定性之熱酸產生劑(tag)_ 為主的化合物。熱酸產生劑為酸產生化合物，其在熱處理 期間生產酸。熱酸產生劑之貫例包括：°比。定對曱苯續酸酿、 2,4,4,6-四溴環己二烯酮、二苯乙二酮甲苯磺酸酯 (benzointosylate)、2-硝基苯甲基甲笨續酸酯，以及有機續 酸之烷基酯。而且，可以使用光阻技術領域中廣為人知的 其他的光敏性酸催化劑，只要其等與該抗反射組成物的其 他組份為相容的。 依據本發明的另一個具體例，提供了—種用於圖案化 裝置的方法。該方法包括：（a)於一基材上提供一材料層； (b) 使用該光阻底層組成物於該材料層上形成—光阻底層； (c) 於該光阻底層上形成一光阻層；（d)令該基材上的該光阻 曰> (e)令该曝光的基材顯影，以及(f)餘刻該顯影的基 材。 在下文中，詳細地說明一種圖案化方法。 首先，於—基材上提供一材料層。 5玄基材可以為-絲材(諸如，晶圓），以及該材料層係 由傳導、半料性、磁性材制製成，或是絕緣材料， 201120578 例如：鋁、氮化矽（SiN)，以及類似物所製成。該材料層可 以使用任何的本技藝中已知的技術予以提供，以及因而未 提供其之詳細說明。 隨後，使用一種依據本發明的一個具體例之光阻底層 組成物來提供一光阻底層。該光阻底層組成物係以500至 4000A的厚度予以塗敷、接著烘烤以提供一光阻底層。塗敷 製程可以使用旋轉塗佈製程予以執行，以及烘烤製程可以 在100至500°C下執行歷時10秒至10分鐘。該光阻底層層的 厚度、烘烤溫度，以及烘烤時間非囿限於以上，以及該光 阻底層層係由熟習此藝者依據各種各樣的塗敷製程技術、 厚度、烘烤溫度，以及烘烤時間予以形成而不需特定的技 術特徵。 一光阻層（一照射敏感性成像層）係提供於該光阻底層 層之上。既然該光阻層可以經由普遍知曉之塗敷光敏性光 阻組成物的製程以及執行烘烤製程予以形成，其之進一步 的說明將不於本說明書中提供。 在形成該光阻層之前，可以進一步執行形成該含矽光 阻底層的製程，或可以進一步執行形成該底部抗折射塗覆 層之製程，或是進一步執行二個製程，其中可以在形成該 含矽光阻底層之後執行一底部抗折射塗覆層。 既然形成該含矽光阻底層以及形成該抗反射塗層為本 發明所屬之技藝之熟習此藝者所廣泛知道的，其等之進一 步的說明將不於本說明書中提供。 隨後，令一光阻層曝光。關於曝光製程，可以使用不 15 201120578 同的曝光光源，例如：ArF、KrF、極紫外線(EUV)，以及 電子束。當曝光完成時，執行烘烤製程以於該曝光區内誘 導化學反應。烘烤製程可以在大約90至12(TC的範圍内的溫 度下執行歷時大約60至90秒。 隨後，執行顯影製程。顯影製程可以使用鹼性水溶液 予以執行。鹼性水溶液顯影溶液之實例包括氫氧化四曱基 銨(TMAH)水溶液。當曝光光源為ArF準分子雷射時，使用5 至30 mJ/cm2的劑量可以獲得到80至i〇〇nm的線-及-間隔圖 案。 依據顯影製程’該光阻層與該光阻底層係被選擇性地 移除以及因而該材料層的一部分係被曝光。 隨後，執行蝕刻製程。經由蝕刻製程，該經曝光的材 料層係被蝕刻以藉此形成一圖案。該蝕刻製程可以使用一 體之電 留在該 以移除 蝕刻氣體予以執行。蝕刻氣體之實例包括：_素氣 漿、氟碳氣體之電漿，諸如，CHF3和CF4。隨後， 基材上的該光阻層與該光阻底層可以使用脫除劑予 以藉此形成所欲的圖案。 經由本製程，可以提供半導體積體電路裝置。 因而，依據本發明的一個具體例製備之組成物和微景, 結構可以被使用來依據半導體製造製程而製造 體電路裝置。舉例而言，依據本發明的一個具體例製備 組成物和微影結構可以用於形成經圖案化的材料層之= 構，例如：金屬線、用於接觸或者偏壓的孔、絕緣段，： 如：鑲嵌溝槽(DT)或者淺層溝槽隔離(STI)結構，以及用 16 201120578 =結構的溝槽。而且，熟習此藝者了解到本發明的概 心不限於肢的微影方法或錢置結構。 幹而1文中’本發明係更洋盡地參照實施例予以闡釋。 然而’其等為本發明的例稀具軸以及非限制性的。 合成實施例1 將35〇.4g(1.0mol)的9,9:雙料、⑼ ig(i 〇m〇i)的苯 ^甲基二氯錢，以及服4g⑽m叫的三乙基胺溶解於 :反應器⑽35G_甲苯中，該反應料有—機械授拌 為、：冷卻器，和l〇L燒瓶。該溶液係用攪拌器予以攪動。 在60°C 10小時之後，該反應完成。 繼而二乙基胺鹽g㈣係用水^>以移除。該曱苯溶劑 於降低的壓力下予以蒸顧’獲得到由下列化學式2表示的-聚合物(Mw = 4300，多分散性=ι·6 ,以及n = 8)。 [化學式2] CH,OH Examples of the acid catalyst may include an organic acid (e.g., p-benzoic acid monohydrate), and a compound having a thermal acid generator (tag) which is still stored as a female. The thermal acid generator is an acid generating compound which produces an acid during heat treatment. Examples of thermal acid generators include: ° ratio. Benzal benzoic acid, 2,4,4,6-tetrabromocyclohexadienone, benzointosylate, 2-nitrobenzylidene acid ester, And an alkyl acid ester of an organic acid. Moreover, other photosensitive acid catalysts well known in the art of photoresist technology can be used as long as they are compatible with other components of the antireflective composition. In accordance with another embodiment of the present invention, a method for patterning a device is provided. The method comprises: (a) providing a material layer on a substrate; (b) forming a light-resisting underlayer on the material layer using the photoresist underlayer composition; (c) forming a light on the photoresist underlayer a resist layer; (d) the photoresist on the substrate; (e) developing the exposed substrate, and (f) developing the developed substrate. Hereinafter, a patterning method will be described in detail. First, a layer of material is provided on the substrate. 5 Xuan substrate can be - wire (such as wafer), and the material layer is made of conductive, semi-material, magnetic material, or insulating material, 201120578 For example: aluminum, tantalum nitride (SiN) , as well as analogs made. The layer of material can be provided using any technique known in the art, and thus a detailed description thereof is not provided. Subsequently, a photoresist substrate is provided using a photoresist sublayer composition in accordance with one embodiment of the present invention. The photoresist underlayer composition is applied at a thickness of 500 to 4000 Å and then baked to provide a photoresist underlayer. The coating process can be performed using a spin coating process, and the baking process can be performed at 100 to 500 ° C for 10 seconds to 10 minutes. The thickness of the photoresist underlayer, the baking temperature, and the baking time are not limited to the above, and the photoresist underlayer is prepared by the artist according to various coating process technologies, thicknesses, baking temperatures, and The baking time is formed without specific technical features. A photoresist layer (an illumination sensitive imaging layer) is provided over the photoresist underlayer. Since the photoresist layer can be formed by a generally known process for applying a photosensitive photoresist composition and performing a baking process, further description thereof will not be provided in the present specification. Before the formation of the photoresist layer, the process of forming the germanium-containing photoresist underlayer may be further performed, or the process of forming the bottom anti-refractive coating layer may be further performed, or two processes may be further performed, wherein the formation may be performed A bottom anti-reflective coating is applied after the photoresist layer is applied. Since the formation of the ruthenium containing photoresist layer and the formation of the anti-reflective coating are well known to those skilled in the art, further description of these will not be provided in this specification. Subsequently, a photoresist layer is exposed. For the exposure process, you can use the same exposure light source as 15201120578, such as ArF, KrF, extreme ultraviolet (EUV), and electron beam. When the exposure is complete, a baking process is performed to induce a chemical reaction in the exposed area. The baking process can be carried out at a temperature in the range of about 90 to 12 (TC) for about 60 to 90 seconds. Subsequently, the developing process is performed. The developing process can be carried out using an alkaline aqueous solution. Examples of the alkaline aqueous developing solution include hydrogen. An aqueous solution of tetradecyl ammonium (TMAH) is oxidized. When the exposure source is an ArF excimer laser, a line-and-space pattern of 80 to i 〇〇 nm can be obtained using a dose of 5 to 30 mJ/cm 2 . The photoresist layer and the photoresist underlayer are selectively removed and thus a portion of the material layer is exposed. Subsequently, an etching process is performed. The exposed material layer is etched through the etching process. A pattern is formed. The etching process can be performed using an integrated electricity to remove the etching gas. Examples of the etching gas include: a gas slurry of a gas, a fluorocarbon gas such as CHF3 and CF4. The photoresist layer on the material and the photoresist underlayer can be formed into a desired pattern by using a removing agent. Through the process, a semiconductor integrated circuit device can be provided. A composition and a microscopic structure prepared by a specific example of the invention can be used to fabricate a bulk circuit device in accordance with a semiconductor fabrication process. For example, a composition and a lithography structure can be formed for formation according to a specific example of the present invention. The patterned material layer, such as a metal wire, a hole for contact or biasing, an insulating segment, such as: a damascene trench (DT) or a shallow trench isolation (STI) structure, and 16 201120578 = Structured grooves. Moreover, those skilled in the art understand that the present invention is not limited to the lithography method or the money structure of the limb. The present invention is more fully described with reference to the embodiments. However, 'they are the rare axis of the invention and are not limiting. Synthesis Example 1 35 〇.4 g (1.0 mol) of 9,9: double material, (9) ig (i 〇m〇i) benzene ^ Methyl dichlorohydrin, and 4 g (10) m of triethylamine are dissolved in: reactor (10) 35G_toluene, the reaction material is - mechanically mixed,: cooler, and l L flask. The solution is stirred. The device was agitated. After 10 hours at 60 ° C, the reaction was completed. The diethylamine salt g (tetra) is removed by water [>. The toluene solvent is distilled under reduced pressure to obtain a polymer represented by the following chemical formula 2 (Mw = 4300, polydispersity = ι·). 6 , and n = 8). [Chemical Formula 2] CH,
合成實施例2 將350.4g (1.0 mol)的 9,9，-雙酚第、253 2g (! 〇 m〇1)的二 苯基二氣矽烷，以及202.4g (2.0 mol)的三乙基胺溶解於〆 反應器内的3500g的甲苯中’該反應器具有一機械授掉器、 一冷卻器，和10L燒瓶。該溶液係用攪拌器予以攪動。在6〇 201120578 °C 10小時之後，該反應完成。 繼而，三乙基胺鹽酸鹽係使用水予以移除。該甲苯溶 劑於降低的壓力下予以蒸餾，獲得到由下列化學式3表示的 一聚合物（Mw = 3600，多分散性=1.4，以及η = 6)。 [化學式3]Synthesis Example 2 350.4 g (1.0 mol) of 9,9,-bisphenol, 253 2 g (! 〇m〇1) of diphenyldioxane, and 202.4 g (2.0 mol) of triethylamine Dissolved in 3500 g of toluene in a helium reactor. The reactor had a mechanical applicator, a cooler, and a 10 L flask. The solution was agitated with a stirrer. The reaction was completed after 10 hours at 6〇201120578 °C. Then, triethylamine hydrochloride was removed using water. The toluene solvent was distilled under a reduced pressure to obtain a polymer represented by the following Chemical Formula 3 (Mw = 3,600, polydispersity = 1.4, and η = 6). [Chemical Formula 3]
合成實施例3 將450.5g (1.0 mol)的9,9-雙（1-萘酚）苐、129.1g (1.0 mol) 的二曱基二氣矽烷，以及202.4g(2.0 mol)的三乙基胺溶解於 一反應器内的4000g的曱苯中，該反應器具有一機械攪拌 器、一冷卻器，和10L燒瓶。該溶液係用攪拌器予以攪動。 在60°C 12小時之後，該反應完成。 繼而，三乙基胺鹽酸鹽係使用水予以移除。該曱苯溶 劑於降低的壓力下予以蒸餾，獲得到由下列化學式4表示的 一聚合物(Mw = 5700，多分散性=1.7，以及η = 10)。 [化學式4] ⑧Synthesis Example 3 450.5 g (1.0 mol) of 9,9-bis(1-naphthol) anthracene, 129.1 g (1.0 mol) of dinonyl dioxane, and 202.4 g (2.0 mol) of triethyl group The amine was dissolved in 4000 g of toluene in a reactor having a mechanical stirrer, a cooler, and a 10 L flask. The solution was agitated with a stirrer. After 12 hours at 60 ° C, the reaction was completed. Then, triethylamine hydrochloride was removed using water. The terpene benzene solvent was distilled under a reduced pressure to obtain a polymer represented by the following Chemical Formula 4 (Mw = 5700, polydispersity = 1.7, and η = 10). [Chemical Formula 4] 8
18 201120578 合成實施例4 將450.5g (1.0 mol)的9,9-雙（1-萘盼）苐、253.2g (1·〇 mol) 的二苯基二氣矽烷，以及202.4g(2.0 mol)的三乙基胺邊解於 一反應器内的4000g的曱苯中，該反應器具有一機械攪拌 器、一冷卻器，和10L燒瓶。該溶液係用攪拌器予以攪動。 在60°C 12小時之後，該反應完成。 繼而’三乙基胺鹽酸鹽係使用水予以移除。該曱笨溶 劑於降低的壓力下予以蒸餾，獲得到由下列化學式5表示的 一聚合物（Mw = 5,600 ’多分散性=1.4，以及n = 8)。 [化學式5]18 201120578 Synthesis Example 4 450.5 g (1.0 mol) of 9,9-bis(1-naphthene) fluorene, 253.2 g (1·〇mol) of diphenyldioxane, and 202.4 g (2.0 mol) The triethylamine was decomposed into 4000 g of toluene in a reactor having a mechanical stirrer, a cooler, and a 10 L flask. The solution was agitated with a stirrer. After 12 hours at 60 ° C, the reaction was completed. The 'triethylamine hydrochloride salt is then removed using water. The hydrazine solvent was distilled under a reduced pressure to obtain a polymer represented by the following Chemical Formula 5 (Mw = 5,600 'polydispersity = 1.4, and n = 8). [Chemical Formula 5]
合成實施例5 將450.5g(1.0 mol)的9,9-雙（1-萘酚）苐、283 4g (1 〇 m〇1) 的二氣十二基曱基石夕烧，以及202.4g(2.〇 mol)的三乙基胺溶 解於一反應器内的4000g的曱苯中，該反應器具有一機械攪 拌器、一冷卻器，和10L燒瓶。該溶液係用攪拌器予以攪動。 在60°C 12小時之後，該反應完成。 繼而，三乙基胺鹽酸鹽係使用水予以移除β該甲苯溶 劑係於降壓蒸餾下予以蒸餾，獲得到由下列化學式6表示的 19 201120578 一聚合物(Mw = 5200，多分散性=1.5，以及n = 7) [化學式6]Synthesis Example 5 450.5 g (1.0 mol) of 9,9-bis(1-naphthol) anthracene, 283 4 g (1 〇m〇1) of dioxadodecyl fluorene, and 202.4 g (2) The 〇mol) triethylamine was dissolved in 4000 g of toluene in a reactor having a mechanical stirrer, a cooler, and a 10 L flask. The solution was agitated with a stirrer. After 12 hours at 60 ° C, the reaction was completed. Then, triethylamine hydrochloride was removed using water. The toluene solvent was distilled under reduced pressure distillation to obtain a polymer of 19 201120578 represented by the following Chemical Formula 6 (Mw = 5200, polydispersity = 1.5, and n = 7) [Chemical Formula 6]
〇.8g的依據合成實施例1至4之聚合物係各別地予以稱 重以及溶解於9g的丙二醇一甲基醚乙酸酯（在下文中稱為 PGMEA)之内。該溶液係予以過濾，各別地製備實施例卜2、 3 ’和4之各光阻底層組成物。 依據實施例1至4之光阻底層組成物係以旋轉塗佈的方 法塗佈於一石夕晶圓上以及在4〇〇 °c燒製歷時6〇秒，形成 2500A-厚的光阻底層。 測量該底磨之有關作為折射指數之η以及作為吸光度 之k。測量係使用一橢圓偏光計(j. a. Woollam Co.)予以執 行。下列表1中提供了結果。 比較實施例1 一光阻底層係依據實施例1至4之相同的方法予以形 成，除了使用合成實施例5的聚合物代替合成實施例1至4的 聚合物之外。測量該底層之有關η和k值。下列表1中提供了 結果。 20 ⑧ 201120578 表1 用於底層的聚合物 光學性質0^~ η (折射指數） k (吸光度） 實施例1 1.41 0.40 實施例2 1.39 ----- 0.66 實施例3 1.33 --- 0.38 實施例4 1.42 0.61 比較實施例1 1.43 ~~ _— 0.73 如表1中顯示出的，依據實施例1至4之組成物經鑑定為 具有可以於ArF(193 nm)波長中使用作為—抗反射層之折 射指數及吸收程度。 實施例5至8 依據實施例1至4之光阻底層組成物各別地以旋轉塗佈 的方法予以塗佈於SiN(silicon nitride)晶圓以及在4〇〇。匸燒 製歷時60秒，形成2500A-厚的底層。 然後，將一ArF光阻塗覆於該底層之上以及在丨⑴^燒 製歷時60秒。在燒製製程之後，所生成的產物係使用ArF 曝光設備（ASML1250(FN70 5.0活動，NA0.82))予以曝光以 及氫氧化四甲基銨（具有2.38 wt%濃度之水溶液）予以顯 影。繼而，使用FE(場發射）-SEM來檢查其等之80nm線和間 隔圖案。 取決於曝光變化之EL(曝光寬容度）邊緣以及取決於與 光的距離變化之DoF(焦距的深度）邊緣係被測量。下列表2 中提供了結果。 21 201120578 比較實施例2 一圖案化的樣品係依據實施例5至8之相同的方法予以 製備，除了使用比較實施例1的光阻底層組成物代替實施例 1至4之光阻底層組成物以外，以及各別地測量有關EL、 DoF，以及圖案的輪廓。下列表2中提供了結果。 表2 用於底層 的樣本 圖案性質 FT邊续 (△mJ/曝光能量mJ) DoF邊緣 (μηι) 輪廓 實施例5 4 0.25 立方的 實施例6 4 0.25 立方的 實施例7 4 0.25 立方的 實施例8 4 0.25 立方的 比較實施例2 4 0.25 立方的 如表2中顯示出的，圖案評估的結果顯示出實施例與比 較實施例均具有良好的EL邊緣、DoF邊緣，以及圖案的輪 廓，介於其間沒有多少差異。 實施例9至12 依據實施例5至8之圖案化的樣品係使用來乾式蝕 刻，其係使用CHF3和CF4的混合氣體，以及該氮化矽繼而 係使用不同選擇比之CHF3和CF4的氣體混合物予以乾式蝕 刻。 最後，所有剩餘的有機材料係使用氧(〇2)氣體予以移 除，以及接而用FE-SEM觀察橫截面。觀察結果係如表3中 顯示的。 22 201120578 比較實施例3 一底層係依據實施例9至12之相同的方法予以蝕刻，除 了使用比較實施例2之圖案化的樣品以外，以及檢查橫截 面。下列表3中提供了結果。 表3 在蝕刻後的底層的圖案 在蝕刻後的氮化矽的圖案 實施例9 垂直的(各向異性） 垂直的(各向異性） 實施例10 垂直的(各向異性） 垂直的(各向異性） 實施例11 垂直的(各向異性） 垂直的(各向異性） 實施例12 垂直的(各向異性） 垂直的(各向異性） 比較實施例3 彎曲的 逐漸變得尖細的 如表3中顯示出的，由實施例1至4之底層組成物形成之 實施例9至12的底層在底層姓刻以及氮化石夕触刻之後各別 地具有良好的圖案，以及因而結果是具有對抗敍刻的氣體 之充分的阻抗，由於触刻評估。於是，氮化石夕姓刻係被執 行良好。 另一方面，由比較實施例3該底層組成物形成之比較實 施例1的底層係鑑定為具有彎曲形狀之各向同性链刻，在底 層蝕刻之後。因此，其在氮化矽蝕刻的期間内逐漸變得央 細。 縱然本發明已經就目前認為為可實施的例示性具體例 予以說明’要了解到本發明非囿限於揭示的具體例，而是， 相反地，打算涵蓋附隨的申請專利範圍之精神和範嘴所包 括的各種各樣的修飾和等效配置。 23 201120578 L圖式簡單說明3 (無） 【主要元件符號說明】 (無） 24 ⑧8 g of the polymer according to Synthesis Examples 1 to 4 were each weighed and dissolved in 9 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA). This solution was filtered, and each of the photoresist underlayer compositions of Examples 2, 3' and 4 was separately prepared. The photoresist underlayer compositions according to Examples 1 to 4 were applied by spin coating on a lithographic wafer and fired at 4 ° C for 6 sec to form a 2500 Å thick photoresist underlayer. The bottom grinding is measured as η as a refractive index and as k in absorbance. The measurement was performed using an ellipsometer (j. a. Woollam Co.). The results are provided in Listing 1 below. Comparative Example 1 A photoresist underlayer was formed in the same manner as in Examples 1 to 4 except that the polymer of Synthesis Example 5 was used instead of the polymer of Synthesis Examples 1 to 4. The underlying η and k values of the underlayer are measured. The results are provided in Listing 1 below. 20 8 201120578 Table 1 Polymer optical properties for the underlayer 0^~ η (refractive index) k (absorbance) Example 1 1.41 0.40 Example 2 1.39 ----- 0.66 Example 3 1.33 --- 0.38 Example 4 1.42 0.61 Comparative Example 1 1.43 ~~ _- 0.73 As shown in Table 1, the compositions according to Examples 1 to 4 were identified as having an anti-reflective layer which can be used in the ArF (193 nm) wavelength. Refractive index and degree of absorption. Examples 5 to 8 The photoresist underlayer compositions according to Examples 1 to 4 were each applied by spin coating to a SiN (silicon nitride) wafer and at 4 Å. The crucible was fired for 60 seconds to form a 2500 A-thick bottom layer. Then, an ArF photoresist was applied over the underlayer and fired at 丨 (1) for 60 seconds. After the firing process, the resulting product was developed using an ArF exposure apparatus (ASML 1250 (FN70 5.0 Activity, NA 0.82)) and tetramethylammonium hydroxide (aqueous solution having a concentration of 2.38 wt%). Then, an FE (field emission)-SEM was used to examine the 80 nm line and the interval pattern thereof. The edge of the EL (exposure latitude) depending on the change in exposure and the edge of the DoF (depth of focal length) depending on the distance from the light are measured. The results are provided in Listing 2 below. 21 201120578 Comparative Example 2 A patterned sample was prepared in the same manner as in Examples 5 to 8, except that the photoresist underlayer composition of Comparative Example 1 was used instead of the photoresist underlayer compositions of Examples 1 to 4. And individually measure the outlines of the EL, DoF, and patterns. The results are provided in Listing 2 below. Table 2 Sample pattern properties for the bottom layer FT edge (ΔmJ / exposure energy mJ) DoF edge (μηι) Contour Example 5 4 0.25 cubic embodiment 6 4 0.25 cubic embodiment 7 4 0.25 cubic embodiment 8 4 0.25 Cubic Comparative Example 2 4 0.25 Cubic As shown in Table 2, the results of the pattern evaluation showed that the examples and the comparative examples both had good EL edges, DoF edges, and contours of the pattern. There are not many differences. Examples 9 to 12 The patterned samples according to Examples 5 to 8 were dry etched using a mixed gas of CHF3 and CF4, and the tantalum nitride was followed by a gas mixture of CHF3 and CF4 having different selectivity ratios. Dry etching is performed. Finally, all remaining organic material was removed using oxygen (〇2) gas and the cross section was observed by FE-SEM. The observation results are shown in Table 3. 22 201120578 Comparative Example 3 A primer layer was etched in the same manner as in Examples 9 to 12 except that the patterned sample of Comparative Example 2 was used, and the cross section was examined. The results are provided in Listing 3 below. Table 3 Pattern of the underlying pattern after etching of the tantalum nitride after etching Example 9 Vertical (anisotropic) Vertical (anisotropic) Example 10 Vertical (anisotropic) Vertical (direction) Heterogeneous) Example 11 Vertical (anisotropic) Vertical (anisotropic) Example 12 Vertical (anisotropic) Vertical (anisotropic) Comparative Example 3 Curved gradually tapered as shown The underlayers of Examples 9 to 12 formed by the underlayer compositions of Examples 1 to 4, as shown in 3, each have a good pattern after the underlying surname and the nitride etch, respectively, and thus the result is antagonistic. The full impedance of the gas engraved, due to the tactile evaluation. As a result, the name of the nitrite Xixia was executed well. On the other hand, the underlayer of Comparative Example 1 formed by the underlayer composition of Comparative Example 3 was identified as an isotropic chain having a curved shape after the underlayer etching. Therefore, it gradually becomes fine during the yttrium nitride etching. The present invention has been described with respect to the exemplary embodiments that are presently considered to be exemplified. It is to be understood that the invention is not limited to the specific examples disclosed, but rather, the invention is intended to cover the spirit and scope of the accompanying claims. A variety of modifications and equivalent configurations are included. 23 201120578 L mode simple description 3 (none) [Main component symbol description] (none) 24 8
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20090070937 | 2009-07-31 | ||
| KR1020100074307A KR101333703B1 (en) | 2009-07-31 | 2010-07-30 | Aromatic ring-included polymer for under-layer of resist, under-layer composition of resist including same, and method of patterning device using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201120578A true TW201120578A (en) | 2011-06-16 |
| TWI456351B TWI456351B (en) | 2014-10-11 |
Family
ID=43773005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW099125591A TWI456351B (en) | 2009-07-31 | 2010-08-02 | Aromatic ring-included polymer for underlayer of resist, underlayer composition of resist including same, and method of patterning device using same |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR101333703B1 (en) |
| TW (1) | TWI456351B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113311661A (en) * | 2020-02-27 | 2021-08-27 | 台湾积体电路制造股份有限公司 | Photoresist underlayer composition and method for manufacturing semiconductor device |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9971243B2 (en) | 2015-06-10 | 2018-05-15 | Samsung Sdi Co., Ltd. | Polymer, organic layer composition, organic layer, and method of forming patterns |
| KR102551719B1 (en) | 2021-07-20 | 2023-07-06 | 엠에이치디 주식회사 | Composition for forming silicon-containing resist underlayer film having star-shaped structure |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3767676B2 (en) * | 2000-09-12 | 2006-04-19 | 信越化学工業株式会社 | Organosiloxane polymer compound, photocurable resin composition, pattern forming method, and film for protecting substrate |
| WO2006126406A1 (en) * | 2005-05-24 | 2006-11-30 | Nissan Chemical Industries, Ltd. | Polysilane compound-containing lower layer film forming composition for lithography |
| KR100725793B1 (en) | 2005-12-26 | 2007-06-08 | 제일모직주식회사 | Hardmask composition coated under photoresist and process of producing integrated circuit devices using thereof |
| JP4718390B2 (en) * | 2006-08-01 | 2011-07-06 | 信越化学工業株式会社 | Resist underlayer film material, resist underlayer film substrate using the same, and pattern forming method |
| KR100760522B1 (en) | 2006-09-28 | 2007-10-04 | 제일모직주식회사 | Hardmask composition coated under photoresist and process of producing integrated circuit devices using thereof |
| JP5154957B2 (en) * | 2007-02-28 | 2013-02-27 | 国立大学法人東京工業大学 | New fluorene skeleton-containing polymer |
-
2010
- 2010-07-30 KR KR1020100074307A patent/KR101333703B1/en active IP Right Grant
- 2010-08-02 TW TW099125591A patent/TWI456351B/en active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113311661A (en) * | 2020-02-27 | 2021-08-27 | 台湾积体电路制造股份有限公司 | Photoresist underlayer composition and method for manufacturing semiconductor device |
| TWI777426B (en) * | 2020-02-27 | 2022-09-11 | 台灣積體電路製造股份有限公司 | Photoresist underlayer composition and method of manufacturing a semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20110013332A (en) | 2011-02-09 |
| KR101333703B1 (en) | 2013-11-27 |
| TWI456351B (en) | 2014-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI317854B (en) | Antireflective hardmask composition and methods for using same | |
| TWI389932B (en) | Hardmask composition having antireflective properties and method of patterning material using the same | |
| KR100655064B1 (en) | Hardmask composition having antireflective property | |
| TWI223128B (en) | Antireflective composition for a deep ultraviolet photoresist | |
| EP2399169B1 (en) | Acid-sensitive, developer-soluble bottom anti-reflective coatings | |
| KR100816735B1 (en) | Hardmask composition having antireflective property, process of producing patterned materials by using the same and integrated circuit devices | |
| US7989144B2 (en) | Antireflective coating composition | |
| KR100826104B1 (en) | High etch resistant hardmask composition having antireflective property and process of producing patterned materials by using the same | |
| KR100671115B1 (en) | Hardmask composition having antireflective property | |
| TW201011078A (en) | An antireflective coating composition | |
| TW200916539A (en) | An antireflective coating composition comprising fused aromatic rings | |
| KR100697979B1 (en) | Antireflective hardmask composition | |
| KR101824763B1 (en) | An underlayer composition and process thereof | |
| KR100671120B1 (en) | Novel fluorene polymer and hardmask composition having antireflective property prepared by using the same | |
| TW200936635A (en) | Hardmask composition having antireflective properties and method of patterning material using the same | |
| TW200819919A (en) | Antireflective coating compositions comprising siloxane polymer | |
| EP3686672B1 (en) | Process of coating a hard mask composition for pattern transfer into a silicon substrate | |
| TW201134799A (en) | Aromatic ring-containing compound for resist underlayer, and resist underlayer composition | |
| JP2008547045A (en) | Anti-reflective hard mask composition and method for using the same | |
| TW201018712A (en) | An antireflective coating composition comprising fused aromatic rings | |
| TW201018713A (en) | An antireflective coating composition comprising fused aromatic rings | |
| TW200933302A (en) | An antireflective coating composition and process thereof | |
| WO2010143054A1 (en) | Spin on organic antireflective coating composition comprising polymer with fused aromatic rings | |
| EP2516566A2 (en) | Antireflective coating composition and process thereof | |
| TW200304582A (en) | Negative deep ultraviolet photoresist |