1301632 A7 B7 五、發明説明（ 發明領域： 經濟部智慧財產局員工消費合作社印製 本發明係有關於積體電路中的微影製程，特別是有關 於利用水溶性負型光阻在微影製程中的製造方法。疋 發明背景： 目前的積體電路微影製程非常複雜，大多包含了數十 個以上的光罩步驟。一般微影製程中所使用的光阻係由樹 脂、感光劑、溶劑與其他添加物所混合而成，遇光之後會 產生鏈結使光阻結構加強而不溶於顯影劑時，稱為負光 P矣，反之，則稱為正光阻。光阻的優劣除了光阻的感光能 力之外，應該還具備良好的附著性、抗蝕刻性及解析度 (resolution)。因此，光阻的材料性質與性能與製程的良率 和精確度有極為密切的關係。 要成功完成微影製程，除了選擇光阻的材料外，還需 留意線寬、疊對、良率和元件特性，而評估微影製程中轉 移圖案品質的好壞，主要係依據解析度以及聚焦深度兩項 指標’解析度越高、聚焦深度越深代表圖案之轉移品質越 佳。隨著70件積集度的曰益提升，當線寬與線距愈趨細 微’對微影製程之解析度的要求也越來越高。在製作集積 度高、圖案細密的積體電路時，微影製程中光學的繞射效 應（diffraction effect)例如近接效應（pr〇ximity effect)，會 涞紙張尺度適财關家標準(CNS)A4規格⑽χ_297^) ............$: (請先閲讀背面之注意事項再填寫本頁) 訂· l3〇l632 A7 B7 i、發明説明（） 造成主體對比性及解析度不良，而產生不完全或錯誤的電 路圖案。為了要提南光學曝光系統之解析度’通常需使用 波長較短之光源來作為曝光光源。然而，光源波長的縮減 會導致聚焦深度（depth of focus ; DOF)縮小，對於〇·5微 米以下之線寬而言，其聚焦深度幾乎等於表面起伏之差 異’不易成功聚焦。一般係利用高數值孔徑的設備來改善 曝光寬容度與印刷程度，但是如此卻更導致聚焦深度的減 少。較淺之聚焦深度會導致顯影劑無法顯影至光阻底部… 而造成接觸金屬導線無法完全接觸到元件，甚至 <战接觸 金屬導線無法與元件接觸而形成斷路。因此，生一 •^風7L件的 電性穩定度降低，導致製程可靠度下降。 ..............t! (請先閲讀背面之注意事項再填寫本頁} 經濟部智慧財產局員工消費合作社印製 發明目的及概述： 上述之發明背景中，在線寬日趨縮小的積體電路微影 製程中，所使用之光罩仍有聚焦深度不足…豕，而無法 顯像至光阻層底部，進而造成接觸金屬導線盥 _ 叮不一 70件之間接 觸不完全，甚至導致接觸金屬導線與元件之間形成斷路， 嚴重影響半導體元件的電性穩定度。 ’ 因此，本發明的目的之一為提供一種積體電路製造方 法，形成較寬的接觸洞開口，由於接觸洞開口寬度越寬 其製程窗也越大，可以避免聚焦深度不足 ^見象。因此先 在原先光阻上定義較預定寬度為寬之開口，再 丹刊用水溶性1301632 A7 B7 V. INSTRUCTIONS (Invention Field: Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printing This invention is related to the lithography process in integrated circuits, especially regarding the use of water-soluble negative photoresist in lithography processes. The manufacturing method of the invention. Background of the invention: The current integrated circuit lithography process is very complicated, and most of them contain dozens of mask steps. The photoresist used in the general lithography process is made of resin, sensitizer, solvent. It is mixed with other additives. When it is light, it will form a chain to strengthen the photoresist structure and is not soluble in the developer. It is called negative light P矣, otherwise it is called positive light resistance. In addition to the photographic ability, it should have good adhesion, etch resistance and resolution. Therefore, the material properties and properties of the photoresist are closely related to the yield and accuracy of the process. The lithography process, in addition to selecting the material of the photoresist, also pay attention to line width, stacking, yield and component characteristics, and evaluate the quality of the transfer pattern in the lithography process, mainly According to the resolution and depth of focus, the higher the resolution and the deeper the depth of focus, the better the transfer quality of the pattern. With the increase of 70 pieces of accumulation, the line width and line spacing become more and more subtle. The resolution of the lithography process is also becoming higher and higher. In the fabrication of a high-accuracy, fine-patterned integrated circuit, the optical diffraction effect in the lithography process, such as the pr〇ximity effect. , will be the paper scale for the financial standards (CNS) A4 specifications (10) χ _ 297 ^) ............ $: (Please read the note on the back and then fill out this page) Order · l3 〇 l632 A7 B7 i, invention description () Causes poor contrast and resolution of the main body, resulting in incomplete or wrong circuit patterns. In order to get the resolution of the South Optical Exposure System, it is usually necessary to use a light source with a shorter wavelength as the exposure light source. However, the reduction in the wavelength of the light source causes a reduction in the depth of focus (DOF), and for a line width of less than 5 μm, the depth of focus is almost equal to the difference in surface undulations, which is difficult to focus successfully. Devices with high numerical aperture are generally used to improve exposure latitude and printing, but this leads to a reduction in depth of focus. A shallower depth of focus can result in the developer not being able to develop to the bottom of the photoresist... and the contact metal wire cannot be completely in contact with the component, and even the <combat contact metal wire cannot contact the component to form an open circuit. Therefore, the electrical stability of the 7L piece is reduced, resulting in a decrease in process reliability. ..............t! (Please read the notes on the back and then fill out this page.) Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printed Inventions and Overview: In the above-mentioned invention background, In the lithography process of the integrated circuit with reduced line width, the reticle used still has insufficient depth of focus... 豕, and cannot be imaged to the bottom of the photoresist layer, thereby causing contact between the metal wires 盥 叮 叮The contact is incomplete, and even causes an open circuit between the contact metal wire and the component, which seriously affects the electrical stability of the semiconductor component. Therefore, one of the objects of the present invention is to provide a method for manufacturing an integrated circuit to form a wide contact hole. The opening, because the width of the opening of the contact hole is wider, the process window is larger, and the depth of focus can be prevented from being insufficient. Therefore, an opening having a wider width than the predetermined width is defined on the original photoresist, and the water is used for water saving.
訂 1301632 A7 B7 五、發明説明（） 負型光阻會與原先光阻材料中酸成分作用的特性，形成薄 膜於原先光阻之暴露表面上，因為此薄膜並不會在後續顯 影步驟中去除，可藉以縮小前述已定義之接觸洞開口寬 度’而達成原先設計的線寬。 本發明的另一目的為提供一種積體電路製造方法，係 利用具有填充洞（Padding H〇le)圖案之光罩定義第—光阻 層，接著形成水溶性負型光阻於第一光阻層上，利用水溶 性負型光阻會與原先光阻材料中酸成分作用的特性，形成 薄膜於原先光阻之暴露表面上，並且保留上述之填充洞内 之水溶性負型光阻，如此可藉以提高聚焦深度以及縮小接 觸洞開口寬度。 根據以上所述之目的，本發明所提供之積體電路製造 方法包括：於基材上形成第一光阻層，此第一光阻層係具 有數個開口；形成第二光阻層覆蓋於第一光阻層與基材 上，並填滿上述之開口，其中此第二光阻層係與第一光阻 層之酸成份反應，而在其與第一光阻層之接觸介面間形成 薄膜；以及’進行一微影製程，藉以去除一部份的第二光 阻層而暴露出開口之一部分，且保留薄膜於第一光阻層 上。另外，更可在第一光阻層中加入例如上述之填充洞的 另些開口，而第二光阻層於微影製程後，會仍填滿這些開 口 ° 上述之第二光阻層係由水溶性負型光阻所構成，其成 分包括：可為水溶性，且佔水溶性負型光阻之重量百分比 象紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) ..............I I (請先閲讀背面之注意事項再填寫本頁) 訂· 經濟部智慧財產局員工消費合作社印製 1301632 A7 B7 五、發明説明（） 介於約 4°/◦至約 8%的一聚合物；可為水溶性光酸產生劑 (PhotoAcidGenerator; PAG)，且光活性化合物佔該水溶性 負型光阻之重量百分比介於約0.01%至約〇·1%的一光活性 化合物（Photo-Active Compound); 可為水溶性胺類 (Amine)，且佔水溶性負型光阻之濃度介於約百萬分之 1 (Parts Per Million ; ppm)至約 30ppm 之一抑制劑 (Quencher);可為水溶性，且佔水溶性負型光阻之重量百分 比介於約0.5%至約2〇/〇之一交鏈劑（Crosslinking Agent);以 及，包含去離子水（De-Ionized Water ; D.I.W)之一溶劑。或 者，上述溶劑可由去離子水與異丙醇（Isopropyl Alcohol ; IPA)所組成，其中異丙醇佔水溶性負型光阻之重量百分比 介於約4%至約7%之間。 利用本發明之積體電路製造方法，具有提高聚焦深度 並加大製程窗等優點，因此在可進而提升金屬連線的穩定 性。另外，由於在1 0 0奈米技術節點中，半導體結構中會 被拿來測試微影技術的能力將是接觸洞，而本發明具有所 小接觸洞線寬的優點，更具有較佳的積體電路製程競爭 力。 圈式簡單說明： 本發明的較佳實施例將於往後之說明文字中辅以下 列圖形做更詳細的闡述，其中： 沐紙張尺度適用中國國家標準(CNS)A4規格(210X 297公釐) ..............費： (請先閲讀背面之注意事項再填寫本頁) 訂_ 經濟部智慧財產局員工消費合作社印製 1301632 五、發明説明（Order 1301632 A7 B7 V. INSTRUCTIONS () The negative photoresist reacts with the acid component of the original photoresist material to form a film on the exposed surface of the original photoresist because the film is not removed in subsequent development steps. The line width of the original design can be achieved by narrowing the width of the previously defined contact opening. Another object of the present invention is to provide a method for fabricating an integrated circuit by defining a first photoresist layer using a photomask having a padding pattern, and then forming a water soluble negative photoresist on the first photoresist On the layer, the water-soluble negative photoresist is used to interact with the acid component of the original photoresist material to form a thin film on the exposed surface of the original photoresist, and to retain the water-soluble negative photoresist in the above-mentioned filled hole, It can increase the depth of focus and reduce the width of the contact hole opening. According to the above object, the integrated circuit manufacturing method provided by the present invention comprises: forming a first photoresist layer on a substrate, the first photoresist layer having a plurality of openings; forming a second photoresist layer covering the The first photoresist layer and the substrate are filled with the opening, wherein the second photoresist layer reacts with the acid component of the first photoresist layer and forms a contact interface with the first photoresist layer. And performing a lithography process to remove a portion of the second photoresist layer to expose a portion of the opening and leaving the film on the first photoresist layer. In addition, further openings such as the above-mentioned filling holes may be added to the first photoresist layer, and the second photoresist layer may still fill the openings after the lithography process. The second photoresist layer is The water-soluble negative photoresist is composed of components including: water-soluble, and the weight percentage of the water-soluble negative photoresist is as applicable to the Chinese National Standard (CNS) A4 specification (210×297 mm). ..........II (Please read the notes on the back and fill out this page) Order · Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1301632 A7 B7 V. Invention Description () Between about 4° /◦ to about 8% of a polymer; may be a water-soluble photoacid generator (PhotoAcidGenerator; PAG), and the photoactive compound accounts for about 0.01% by weight to about %·1 of the water-soluble negative photoresist % Photo-Active Compound; may be a water-soluble amine (Amine), and the concentration of the water-soluble negative photoresist is between about 1 part per million (Parts Per Million; ppm) to about 30 ppm one of the inhibitors (Quencher); can be water soluble and accounts for the weight percent of water soluble negative photoresist The ratio is from about 0.5% to about 2 〇 / 〇 one of the crosslinking agents (Crosslinking Agent); and, including one of deionized water (De-Ionized Water; D.I.W). Alternatively, the above solvent may be composed of deionized water and isopropanol (IPA), wherein the isopropanol comprises from about 4% to about 7% by weight of the water-soluble negative photoresist. The method for manufacturing an integrated circuit of the present invention has the advantages of increasing the depth of focus and increasing the process window, thereby further improving the stability of the metal wiring. In addition, since in the 100 nanometer technology node, the ability to be used in the semiconductor structure to test the lithography technique will be a contact hole, and the present invention has the advantage of a small contact hole line width, and has a better product. Body circuit process competitiveness. BRIEF DESCRIPTION OF THE PREFERRED EMBODIMENT: The preferred embodiment of the present invention will be explained in more detail in the following description with the following figures, wherein: The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm). .............. fee: (please read the note on the back and fill out this page) _ Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1301632 V. Invention description (
第 本…-較— 圈统對照說明： 100 基材 104 第二光阻材料 106 接觸洞 110 薄膜 Wi 寬度發明詳細說明： 本發明係揭露一種 102 第一光阻層 l〇4a第二光阻層 108 填充洞 W2 寬度 ............Mwi. (請先閲讀背面之注意事項再填寫本頁) 積 -訂· 經 濟 部 智 慧 財 產 局 員 工 消 費 合 社 印 製 體電路製造方法，係應用兩道光 罩與水溶性負型光a，並搭配填充洞以提高開口率而達到 提高聚焦深度的目白勺。本發明係利用一較佳實施例來進行 說明’請參照下列描述並配合第i圖至第3圖之圖示，其 中第1圖至第3圖係繪示依據本發明積體電路製造方法之 一較佳實施例的製程剖面圖。 請參照第1圖，其係緣示依據本發明之一較佳實施例 之積體電路製造方法的方法之製程剖面圖。首先，提供基 材100,此基材100上已覆蓋有利用例如旋轉塗蓋（sp= coating)法所形成的第一光阻材料，其中第一光阻材料係為 ㈢革紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐） 1301632 五、發明説明（） (請先閲讀背面之注意事項再填寫本頁} 正型光阻，且可由！'線（Μ — )光阻、氣化氮阶F)光阻、氟 化氬（ArF)光阻、氟（d光阻、極紫外光㈣ uUravic^et ; EUV)光阻與電子束（e beam)光阻等材料所構 成接著進行第微影製程步驟，經過曝光步驟與顯影 步驟後’在第一光阻材料中形成數個接觸洞1〇6以及數個 填充洞108，並暴露出部分之基材100,形成第一光阻層 102。由於在微影製程中，經由填充洞圖案投射至第一光阻 材料的光線，能增強經由填充洞圖案相鄰之接觸洞圖案投 射至第一光阻材料的光能量強度，因此可增加第一光阻材 料中接觸洞106區域之聚焦深度。 然後，請參照第2圖，形成第二光阻材料1〇4覆蓋在 第一光阻層102與基材100上，並填滿接觸洞1〇6以及填 充洞1 08。第二光阻層丨〇4係由水溶性負型光阻所構成， 水溶係負型光阻之成分包括聚合物、光活性化合物、抑制 劑、交鏈劑、以及溶劑等。 其中’聚合物可為水溶性聚舍物，佔水溶性負型光阻 之重量百分比介於約4%至約8%之間，其較佳之具體例子 如聚乙烯醇縮乙搭（polyvinylacetal)、聚乙烯基。比洛院嗣 經濟部智慧財產局員工消費合作社印製 (polyvinyl pyrrolidone ; PVP)、聚烯丙酸(polyaUylic Acid)、聚乙婦醇（polyvinyl alcohol ; PVA)、聚乙 '歸亞胺 (polyethyleneimine)、聚環氧乙烷（polyethylene 〇xide ; PEO)、以及聚乙烯基胺（polyvinylamine)等，更佳者為聚乙 烯醇縮乙醛，而聚乙烯醇縮乙醛之結構式（I )如下所示： 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐〉 1301632 A7 B7 五、發明説明（） + CH—CH2—CH—CH2^- OCH3The first ... - comparison - circle description: 100 substrate 104 second photoresist material 106 contact hole 110 film Wi width invention Detailed Description: The present invention discloses a 102 first photoresist layer 104a second photoresist layer 108 Filling hole W2 width............Mwi. (Please read the note on the back and fill out this page) 积-订· Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Co., Ltd. Printed circuit manufacturing The method uses two masks and a water-soluble negative light a, and is matched with a filling hole to increase the aperture ratio to achieve the purpose of increasing the depth of focus. The present invention is described with reference to a preferred embodiment. Please refer to the following description and the drawings of FIGS. 1 to 3, wherein FIG. 1 to FIG. 3 show the manufacturing method of the integrated circuit according to the present invention. A process cross-sectional view of a preferred embodiment. Referring to Fig. 1, there is shown a cross-sectional view showing a process of a method for fabricating an integrated circuit in accordance with a preferred embodiment of the present invention. First, a substrate 100 is provided, which is covered with a first photoresist material formed by, for example, a spin coating method, wherein the first photoresist material is (3) leather paper scale applicable to China Standard (CNS) A4 specification (210X297 mm) 1301632 V. Invention description () (Please read the note on the back and fill out this page) Positive photoresist, and can be made by ''Line (Μ)) photoresist, gasification Nitrogen order F) photoresist, argon fluoride (ArF) photoresist, fluorine (d photoresist, extreme ultraviolet (4) uUravic^et; EUV) photoresist and electron beam (e beam) photoresist and other materials The lithography process step, after the exposing step and the developing step, forming a plurality of contact holes 1 〇 6 and a plurality of filling holes 108 in the first photoresist material, and exposing a portion of the substrate 100 to form a first photoresist layer 102. Since the light projected onto the first photoresist material through the fill hole pattern in the lithography process enhances the intensity of the light energy projected onto the first photoresist material via the contact hole pattern adjacent to the fill hole pattern, the first The depth of focus of the area of the contact hole 106 in the photoresist material. Then, referring to Fig. 2, a second photoresist material 1〇4 is formed to cover the first photoresist layer 102 and the substrate 100, and fills the contact holes 1〇6 and fills the holes 108. The second photoresist layer 4 is composed of a water-soluble negative photoresist, and the components of the water-soluble negative photoresist include a polymer, a photoactive compound, an inhibitor, a crosslinking agent, a solvent, and the like. Wherein the polymer may be a water-soluble polymer, and the weight percentage of the water-soluble negative photoresist is between about 4% and about 8%, and preferred specific examples are polyvinylacetal, Polyethylene. Bilbao Institute of Economics, Intellectual Property Bureau, Staff Consumer Cooperatives (polyvinyl pyrrolidone; PVP), polya-Uylic acid, polyvinyl alcohol (PVA), polyethylene imine (polyethyleneimine) Polyethylene oxide (PEO), polyvinylamine, etc., more preferably polyvinyl acetal, and polyvinyl acetal structural formula (I) is as follows Show: This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm> 1301632 A7 B7 V. Invention description () + CH—CH2—CH—CH2^- OCH3
結構式（I ) 0 C/ h2 光活性化合物係為水溶性先酸產生劑（ph〇to acid generator ; PAG)，且此光活性化合物佔水溶性負型光阻之 重量百分比介於約0.01 %至約0.1 %之間，其較佳之具體例 子如翁鹽衍生物（onium salt derivative)與三氮苯衍生物 (triazine derivative)等，更佳者為嗡鹽衍生物Pag2087 與PAG-C，而PAG20 87之結構式（Π )與PAG-C之結構式 (皿）分別如下所示： 結構式（Π ) (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製The structural formula (I) 0 C / h2 photoactive compound is a water-soluble acid generator (PAG), and the photoactive compound accounts for about 0.01% by weight of the water-soluble negative photoresist. Between about 0.1%, preferred specific examples are onium salt derivative and triazine derivative, and more preferably sulfonium derivatives Pag2087 and PAG-C, and PAG20 The structural formula (Π) of 87 and the structural formula (dish) of PAG-C are as follows: Structural formula (Π) (Please read the notes on the back and fill out this page) Printed by the Intellectual Property Office of the Ministry of Economic Affairs
S CF3S〇3 結構式（πη #本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) 1301632 A7 B7 五、發明説明（） (請先閲讀背面之注意事項再填寫本頁) 抑制劑係為水溶性胺類（amine)，且此光活性化合物佔 水溶性負型光阻之濃度介於約百萬分之 l(parts per million ; ppm)至約 3Oppm之間，其較佳之具體例子如乙 胺（ethylamine)、二 曱 胺 (dimethylamine)、 二 乙 胺 (diethylamine)、 三 甲 胺 (trimethyl amine)、 三 乙 胺 (triethylamine)、 正 丙 胺 (n-propylamine)、 異 丙 胺 (isopropylamine)、第 二丁胺（s-butylamine)、第 三1 -胺（t· butylamine)、環 己 胺 (c yclohexylamine)、 乙 -一一 胺 (ethylenediamine)、六亞甲二胺（hexamethylenediamine)、 乙醇胺（mo no ethanol amine ； ME A)、二乙醇胺 (diethanolamine ; DEA)、三乙醇胺（triethanolamine ; TEA)、 正丁基二乙醇胺（n-butyldiethanolamine)、四甲基氫氧化銨 (tetra-methy 1 ammonium hydroxide ； TMAH)、四丁 基氫氧 化銨（tetra-butyl ammonium hydroxide ; TBAH)與膽驗 (choline)等，更佳者為四丁基氫氧化鈹。 經濟部智慧財產局員工消費合作社印製 交鏈劑係為水溶性交鍵劑，且此光活性化合物佔水溶 性負型光阻之重量百分比介於約0.5%至約2°/。之間，其較 佳之具體例子如尿素衍生物（urea derivative)與三聚氛胺 衍生物（melamine derivative)，例如為環氧乙基尿素 (ethyleneurea)，其中環氧乙基尿素之結構式（IV )如下所 不 · 23¾紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) 1301632 A7 B7 五、發明説明（） R1— CH-CH— R2 結構式（IV ) (請先閲讀背面之注意事項再填寫本頁) R3—N N—R4 0 上述之官能基Ri、R2、R3以及R4係選自於由氫與烷 基（alkyl gr0Up)所組成之一族群，其中更佳者為甲氧基羥曱 基尿素（methoxy-methylol-urea)。 溶劑至少包括去離子水（de-ionized water ; D.I.W)，其 中去離子水佔水溶性負型光阻之重量百分比介於約8 5 %至 約90%之間。根據本發明之水溶性負型光阻，溶劑更可以 由去離子水與異丙醇所組成，其中異丙醇佔水溶性負型光 阻之重量百分比介於約4%至約7%之間。 由於本發明的水溶性負型光阻會和上述第一光阻層 102中的酸成分作用，因此會在第二光阻材料1〇4與第一 光阻層1 02的接觸界面，包含表面和接觸洞1 〇6和填充洞 1 0 8中，形成一層固化的薄膜1丨〇，此薄膜丨丨〇在後續的曝 先顯^^步驟中’並不會被去除。 經濟部智慧財產局員工消費合作社印製 之後’請參照第3圖，進行第二微影製程以定義第二 光阻材料1 〇 4，藉以開啟第一光阻層丨〇 2中之接觸洞1 〇 6， 並選擇性地保留填滿填充洞i 08之第二光阻材料1〇4。先 進行曝光步驟，其係利用波長365奈米（Nan〇meter; nm)、 248nm、193nm、157nm之光源、極紫外光或電子束對此水 溶性負型光阻曝光，以將光罩之圖案轉移至此水溶性負型 、本紙張尺度適用中國國家標準(CNs)A4規格(210X297公釐) 1301632S CF3S〇3 Structure (πη #本纸标准Applicable to China National Standard (CNS) A4 Specification (210X297 mm) 1301632 A7 B7 V. Invention Description () (Please read the back note before completing this page) Inhibitor It is a water-soluble amine, and the photoactive compound accounts for a concentration of a water-soluble negative photoresist of between about 1 part per million (ppm) and about 3Oppm, and a preferred specific example thereof. Such as ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, n-propylamine, isopropylamine, S-butylamine, third 1-amine (t-butylamine), c-yclohexylamine, ethylenediamine, hexamethylenediamine, ethanolamine (mo no) ME A), diethanolamine (DEA), triethanolamine (TEA), n-butyldiethanolamine, tetra-methy 1 ammonium hydro Xide; TMAH), tetra-butyl ammonium hydroxide (TBAH) and choline, etc., more preferably tetrabutylphosphonium hydroxide. Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed The chain agent is a water-soluble crosslinking agent, and the photoactive compound accounts for between about 0.5% and about 2% by weight of the water-soluble negative photoresist, and a preferred specific example thereof is a urea derivative (urea derivative). And a melamine derivative, such as ethylene ethyl urea (ethyleneurea), wherein the structural formula (IV) of the epoxy ethyl urea is as follows: 233⁄4 paper scale applies to the Chinese National Standard (CNS) A4 size (210X297 mm) 1301632 A7 B7 V. Description of invention () R1—CH-CH— R2 Structural formula (IV) (Please read the notes on the back and fill out this page) R3—NN—R4 0 The radicals Ri, R2, R3 and R4 are selected from the group consisting of hydrogen and alkyl gr0Up, and more preferably methoxy-methylol-urea. The solvent includes at least de-ionized water (D.I.W), wherein the deionized water accounts for between about 85 % and about 90% by weight of the water-soluble negative photoresist. According to the water-soluble negative photoresist of the present invention, the solvent may be further composed of deionized water and isopropyl alcohol, wherein the isopropyl alcohol accounts for between about 4% and about 7% by weight of the water-soluble negative photoresist. . Since the water-soluble negative photoresist of the present invention acts on the acid component in the first photoresist layer 102, the surface is included at the contact interface between the second photoresist material 1〇4 and the first photoresist layer 102. And in the contact hole 1 〇 6 and the filling hole 1 0 8 , a cured film 1 形成 is formed, and the film ' is not removed in the subsequent exposure step. After printing by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperatives, please refer to Figure 3 for the second lithography process to define the second photoresist material 1 〇4 to open the contact hole 1 in the first photoresist layer 丨〇2. 〇6, and selectively retaining the second photoresist material 1〇4 filled with the filled holes i 08. First, an exposure step is performed by exposing the water-soluble negative photoresist to a light-emitting negative photoresist using a light source of 365 nm (nm), 248 nm, 193 nm, 157 nm, an extreme ultraviolet light or an electron beam to pattern the photomask. Transfer to this water-soluble negative type, this paper scale applies to China National Standard (CNs) A4 specification (210X297 mm) 1301632
、發明説明( 光阻上。接著，進行顯影步驟，其係利用去離子水或者包 含去離子水的水溶液，例如去離子水和醇類的混合液，將 第二光阻材料104中所轉移之潛在圖案顯現出來，而形成 第一光阻層104a。 其中，由於薄膜110並不會被上述微影製程所去除， 因此而保留在第一光阻層的表面上，如此一來，會使得第土 圖中原本接觸洞106的寬度Wi，變成第3圖中的寬度W2， 而達到減少接觸洞線寬的目的。或者，可利用開口較大製 程窗較廣的光罩，並搭配利用本發明所提供之方法，而達 到原先預期開口寬度的目的。因此值得注意的是，本發明 上述搭配具有填充洞之光罩的方法僅為舉例，更可與不具 填充洞的一般光罩搭配使用，本發明不限於此。 另外’當本發明之水溶性負型光阻，作為第二光阻層 i〇4覆蓋於第一光阻層102與基材1〇〇上時，更可進行軟 烤（soft bake ; SB)步驟，例如利用約85°c之溫度軟烤此水 溶性負型光阻約70秒。或者，在第二光阻材料1〇4進行曝 光後，可進行曝光後烘烤（Post ExP〇sure Bake; pEB)的+ 驟’例如利用約1 3 0 °C之溫度烘烤此水溶性負型光阻約9 〇 秒。值得注意的是’上述之軟烤步驟係用已將光阻層的部 分容易由光阻中驅除的步驟，而曝光後烘烤步驟係進一牛 將光阻内所殘留的溶劑含量，藉著蒸發而達到最低。此兩 烘烤步驟並不影響本發明之方法與水溶性負型光阻Description of the Invention (Photoresist. Next, a development step is carried out by transferring the second photoresist material 104 using deionized water or an aqueous solution containing deionized water, such as a mixture of deionized water and an alcohol. The potential pattern is formed to form the first photoresist layer 104a. Since the film 110 is not removed by the lithography process, it remains on the surface of the first photoresist layer, so that the first In the soil map, the width Wi of the original contact hole 106 becomes the width W2 in the third figure, and the purpose of reducing the line width of the contact hole is achieved. Alternatively, a mask having a wider opening process window can be used, and the present invention can be used in combination. The method provided provides the purpose of the original expected opening width. Therefore, it is worth noting that the method of the present invention with the filling of the reticle is only an example, and can be used together with a general reticle without a filling hole. The invention is not limited to this. In addition, when the water-soluble negative photoresist of the present invention is applied as the second photoresist layer i〇4 on the first photoresist layer 102 and the substrate 1 , soft baking is possible ( Sof t bake ; SB) step, for example, softly baking the water-soluble negative photoresist for about 70 seconds with a temperature of about 85 ° C. Alternatively, after exposure of the second photoresist material 1 〇 4, post-exposure baking may be performed ( Post ExP〇sure Bake; pEB) + step 'for example, baking the water-soluble negative photoresist with a temperature of about 130 ° C for about 9 〇 seconds. It is worth noting that the above soft-bake step has been used The portion of the photoresist layer is easily removed by the photoresist, and the post-exposure baking step is incorporated into a cow to minimize the amount of solvent remaining in the photoresist by evaporation. The two baking steps do not affect the present invention. Method and water soluble negative photoresist
/V 效，因此並不限制本發明之範圍。 11 Θ本紙張尺度適用中國國家標準(CNS)A4規格(210χ297公釐） ..............I · (請先閲讀背面之注意事項再填寫本頁} -、一叮_ 經 濟 部 智 慧 財 產 局 員 工 消 費 合 社 印 製 1301632 A7 五、發明説明（ 另外本發明所採用 .. 尤卓’係視實際需求及所採用夕 光阻的種類，而選擇且木用之 迸擇具不冋背景的光罩。舉例而言，當第 一光阻層為正光阻時，所選 ^ ^ ^ ^ 之第一光罩應具暗背景且所 需之圖案應為透明，而备第-止 所 叩田第一先阻層為水溶性負光阻時， 所選用之第二光罩應具透 明 ^边月者景且所需之圖案應為不透 系示合上述’本發明之^__ /5 ψ, 知5之優點就是由於水溶性負型光阻 與原先形成於基材上之光阻材料之酸成分反應後，會在兩 者介面間形成薄膜"〇,而達到縮小線寬的…另外， 本發明的另一優點在於更搭配利用具有填充洞圖案之光罩 後’更達到提高聚焦深度的目的。 如熟悉此技術之人員所瞭解的，以上所述僅為本發明 之較佳實施例而已，並非用以限定本發明之申請專利範 圍，凡其它未脫離本發明所揭示之精神下所完成之等效改 憂或修飾’均應包括在下述之申請專利範圍内。 (請先閲讀背面之注意事項再填寫本頁} 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210x 297公爱)/V effect, and therefore does not limit the scope of the invention. 11 Θ本纸标准Applicable to China National Standard (CNS) A4 specification (210χ297 mm) ..............I (Please read the note on the back and fill out this page) -,一叮 _ Ministry of Economic Affairs Intellectual Property Bureau employee consumption company printing 1301632 A7 V. Invention description (In addition to the invention adopted. For example, when the first photoresist layer is a positive photoresist, the first mask of the selected ^ ^ ^ ^ should have a dark background and the desired pattern should be transparent, and When the first barrier layer of the first-stop field is water-soluble negative photoresist, the second mask used should be transparent and the desired pattern should be the same as the above-mentioned Inventive ^__ /5 ψ, the advantage of knowing 5 is that since the water-soluble negative photoresist reacts with the acid component of the photoresist material originally formed on the substrate, a thin film is formed between the two interfaces. Achieving a reduction in line width... In addition, another advantage of the present invention is that it is more versatile after using a mask with a filled hole pattern. The purpose of the present invention is to improve the depth of focus. It is to be understood by those skilled in the art that the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Equivalent changes or modifications made under the spirit of the company shall be included in the scope of the patent application below. (Please read the notes on the back and fill out this page.) Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printed Paper Scale Applicable to China National Standard (CNS) A4 specification (210x 297 public)