TW565745B - Compositions of matter, resist structures including a layer of electrically conductive polymer having controlled pH and methods of fabrication thereof - Google Patents

Abstract

The present invention is an electrically conductive polymeric composition of matter having a controlled pH and structures fabricated therewith and methods of fabrication thereof having: a surface; a plurality of layer on the surface; at least one of the plurality of layers is formed from an energy sensitive material; at least another layer is formed from an electrically conductive polymer; the electrically conductive polymer contains acid functionality; and the electrically conductive polymer has a predetermined pH. The pH is controlled by additives mixed in with the electrically conductive polymer or by constituents on the electrically conductive polymer. The electrically conductive polymer is preferably a top layer. The structures are useful for lithography in microelectronic fabrication to avoid the effects of charging on resist from electron beams. The compositions are also useful in applications as static dissipation, electromagnetic interference shielding, corrosion protection, electroplating, and wiring.

Description

565745565745

I部中—伞If作社印欠 發明範圍 本發明係針對具有經控制pH値之導電性物質組合物 其製成I結構，此結構具有—層能量敏感性材料 具有經控制阳値之導電性聚合物，及其製造方法。更2 K，根據本發明之結構可用於製造電子裝置， ^ 敏感性材料爲光阻。 ，、中把量 發明背t 在許夕工業應用中，係在所製造物體表面之一声 :樣特在微電子工業中，必須形成各種複雜圖 ㈣：如矽在晶片或其互連體上之各種經摻雜區域，或： 封裝上之各種互連體，彳？莽石£卩姑if- # & nih 卩°^印術係倚賴 ，馬先阻之能量敏感性材料。能量敏感性材料係配£ 於表面上。使此能量敏感性材料層曝露至 k 層之經曝光區域中之性質，因此可二經 Μ或者未經曝光區域’以在能量敏隸層中形成圖樣。 在真性作用光阻中’經曝光區域變成可溶性，然而在自性 阻中’經曝光區域變成不溶性。於任—情況中:、、圖 樣係在光阻或能量敏感性層中產生'然後可藉各種蚀刻機 制’使此圖樣向下轉移至其下方層。 在能量之圖樣會造成電荷產生或帶有電荷之情況中，電 荷可因而蓄積在能量敏感性層處或在其下方層中，這可能 會造成能量敏感性層中產生圖樣之變形。此二變形會產生 巨大影像安置偏差與錯誤。此係發生在介電能量敏感性材 (請先閱讀背面之注意事項再填寫本頁} 訂 J0 4-Part I-Umbrella If the company owes the scope of the invention The present invention is directed to a conductive material composition having a controlled pH 値, which is made into an I structure. This structure has-a layer of energy-sensitive material with controlled impotence. Polymers and methods of making same. More than 2 K, the structure according to the present invention can be used to manufacture electronic devices, and the sensitive material is photoresist. In the industrial application of Xu Xi, it is a sound on the surface of the manufactured object: In the microelectronics industry, various complex patterns must be formed. For example, silicon is on the wafer or its interconnects. Various doped regions, or: various interconnects on the package, 彳? Mang Stone £ 卩 姑 if- # & nih 卩 ° ^ Sitting is dependent on the energy-sensitive material of Ma Xianzhe. Energy-sensitive materials are formulated on the surface. The nature of exposing this energy-sensitive material layer to the exposed areas of the k-layer can therefore be subjected to M or unexposed areas' to form a pattern in the energy-sensitive slave layer. In the true acting photoresist, the exposed region becomes soluble, but in the self-resistance, the exposed region becomes insoluble. In any case: the pattern is created in a photoresist or energy-sensitive layer, and this pattern can then be transferred down to its underlying layer by various etching mechanisms. In the case where the energy pattern causes or generates an electric charge, the electric charge may thus be accumulated at or under the energy sensitive layer, which may cause the deformation of the pattern in the energy sensitive layer. These two deformations will cause huge image placement errors and errors. This is a dielectric energy sensitive material (please read the precautions on the back before filling this page) Order J0 4-

565745 五 、發明説明（2) A7 B7 料，譬如光阻，被曝露於荷電射束時，譬如電子束或離子 =、此介％敏感性層會蓄積來自該射束之電荷。經蓄 何會引進電場’其在達到足夠量時會使射束扭曲並 =成射束在能量敏感性材料上之誤置。這會在該層中所形 成之圖樣上造成誤差。 .逼可藉由在能量敏感性層上方、下方或内部配置一層導 二性材料而避免，後者可用以排出所蓄積之電荷及移除或 減少不想要之電場。 導電性有機聚合物爲一種電子材料，其係結合金屬之電 奋質，與金屬之加工性能及機械性質特徵。此種聚合物之 二例’包括製自可溶性先質之聚對苯乙晞、聚對苯、聚苯 二聚t ☆、聚畊、聚呋喃、聚吡咯、聚硒苯、聚對苯硫 4^ $乙块’其組合及其與其他單體聚合物及共 水物之摻合物。 此等聚合物爲共軛系、统，其係藉由摻雜而成爲導電性。 物之未經摻雜或非導電性形式，於本文中係稱爲導 ^、來合物&先質。此聚合物之經摻雜或導電性形式，於 文中係稱爲導電性聚合物。 、、導電性聚合物可作爲電荷散逸薄塗層使用”乂防止在上 ::用中帶電。此外具有供很大數目之其他應用領域 m ’譬如靜電性荷電/放電（ESC/ESD)保護、電磁 =陶)防護、光阻、電鍍，金屬與最後金屬替代物之防 :w，思即佈、線’塑膠微型電路，供各種互連技術用之導 氧性糊劑（焊料替代物）等。 本縣尺㈣ (諳先閲讀背面之注意事項再填寫本頁)565745 V. Description of the invention (2) When A7 B7 materials, such as photoresist, are exposed to a charged beam, such as an electron beam or ions, the% sensitive layer of this medium will accumulate the charge from the beam. The stored electric field is introduced, which will distort the beam when it reaches a sufficient amount and = misplace the beam on the energy sensitive material. This causes errors in the patterns formed in this layer. Force can be avoided by disposing a layer of conductive material above, below or inside the energy sensitive layer, which can be used to discharge the accumulated charge and remove or reduce unwanted electric fields. Conductive organic polymer is an electronic material that combines the electrical properties of metals with the processability and mechanical properties of metals. Two examples of such polymers include polyparaphenylene terephthalate, polyparaphenylene, polyphenylene dimer t ☆, polyphenylene, polyfuran, polypyrrole, polyselenebenzene, polyparaphenylenesulfide made from soluble precursors4 ^ $ 乙 块 'its combination and its blend with other monomer polymers and co-hydrates. These polymers are conjugated systems, which are made conductive by doping. The un-doped or non-conductive form of the substance is referred to herein as the conductive, precursor & precursor. The doped or conductive form of this polymer is referred to herein as the conductive polymer. 、 Conductive polymer can be used as a thin layer for charge dissipation. "Prevention of charge on :: in use. In addition, it has a large number of other applications m 'such as electrostatic charge / discharge (ESC / ESD) protection, (Electromagnetic = ceramic) protection, photoresist, electroplating, metal and final metal substitutes: w, think cloth, wire 'plastic microcircuits, oxygen conducting pastes (solder substitutes) for various interconnection technologies, etc. . The prefecture's ruler (谙 Please read the notes on the back before filling in this page)

、1T I# ^65745 A7 B7 五、發明説明（3)1T I # ^ 65745 A7 B7 V. Description of the invention (3)

聚苯胺類之導電性聚合物，已被証實係 應用使用之最有希望且最適合之導電性聚合物廣㈣两: 合物具有優越環境安定性及提供 此I 造多種可溶性衍生物。例如，吾人：㈣合成。可製 5,3卿中揭示—種新賴水溶聚：在吴國專利 述内容係併於本文供參考。此等水群，其陳 意即具有低_。此等聚合物之酸性，在許多生 顧慮。例如，若使用聚芝 于夕應用上產生 声，則^、匕作U阻頂部上之電荷散逸塗 阻對酸具接端敏感性。=在目前常用之光 於塑膠或Μ卜、，料電性聚合物塗敷 引致二 巾，此酸可能產生重大問題，譬如 引致降解、腐蝕等等。 因此、，—般期望能約控制經摻雜導電性聚合物之pH値， 此進仃而不會衝擊導電性。本文係描述具有經控制碑 ^之導電性聚合組合物，及製造此種聚合物之方法。 目的 經漪部屮夾標準局一3C工消费合作社印公 本發月之項目的係爲提供一種具有經控制ρΗ値之導電 性聚合物。 ，.本發月 < 項目的係爲提》共-種形成具有經控制pH値之 導電性聚合物之方法。 、 i^發明之-項目的係爲提供-種形成具有經控制pH値之 導電性聚合物之方法，其方式是包含酸中和官能基伴隨著 本紙張尺度適則，_家榡伞(7ns ) Λ4^ 6 - (21 Οχ 297公釐） 565745Polyaniline-based conductive polymers have been proven to be the most promising and suitable conductive polymers for use in applications. The compounds have excellent environmental stability and provide a variety of soluble derivatives. For example, I: ㈣ Synthesis. It can be revealed in 5,3 that a kind of Xinlai water-soluble polymer is described in Wu Guo patent and is incorporated herein by reference. These water clusters have a low meaning. The acidity of these polymers is a concern for many people. For example, if polyzide is used to generate sound in the application, the charge dissipation coating on the top of the U-block U-block is sensitive to acid termination. = At present, it is commonly used in plastics or plastics, and the coating of electrical and polymer materials causes two towels. This acid may cause major problems, such as causing degradation and corrosion. Therefore, it is generally expected that the pH of the doped conductive polymer can be controlled approximately, which does not impact the conductivity. This article describes a conductive polymeric composition with a controlled tablet, and a method of making such a polymer. Purpose This issue of the project this month is to provide a conductive polymer with controlled ρΗ 値. This month's project is to provide a total of a method for forming a conductive polymer with a controlled pH. The invention of the project is to provide a method for forming a conductive polymer having a controlled pH, by including an acid-neutralizing functional group with the appropriate size of this paper, _ 家 榡 伞 (7ns ) Λ4 ^ 6-(21 〇χ 297mm) 565745

經濟部屮次ίί^-^u V,消抡合竹杉印y 為導電性聚合物。 本發明I —項目的係爲提供_種形成具有經控制値之 導％性聚口物之方法，其方式是以適當鹼處理該酸性導電 性聚合物’以中和酸官能基度至受控程度。 本發明之一項目的係爲提供一種具有表面之結構，該表 面包含具有經控制pH値之導電性聚合物。 本發明I另一項目的係爲提供一種在表面上且 聚合物圖樣之結構。 〃 &月摘述 本發明之廣義方面爲一種具有經控制pH値之$電性物質 組合物。 、 本發明（另-廣義方面爲—種具有表面之結構，於該表 面上具有一種具有經控制pH値之導電性聚合物。 本發明之更特定方面爲一種具有表面之結構，於該表面 上具有由一種具有經控制pH値之導電性聚合物所形成之圖 樣。 本發明足另一廣義方面爲一種結構，其具有：一個表面 ;多個薄層，在該表面上；該多個薄層中至少一個係製自 能量敏感性材料；至少另一層係製自導電性聚合物；此導 電性聚合物含有酸官能基；且該導電性聚合物具有預定 値。 ’、 本發明足另一廣義方面爲一種在表面上配置具有經控制 pH値之導電性聚合物之方法。 本發明之另一個更特定方面爲一種在表面上配置多個薄 本紙浓尺度適州中K S家標蜱) Λ4規格（210X 297公釐了 (諳先閱讀背面之注意事項再填寫本頁} 一裝-The Ministry of Economic Affairs 屮 次 ί ^-^ u V, the elimination of combined bamboo fir seal y is a conductive polymer. The I-item of the present invention is to provide a method for forming a polymer with controlled conductivity, in a manner of treating the acidic conductive polymer with an appropriate base to neutralize the acid functionality to a controlled level. degree. One aspect of the present invention is to provide a structure having a surface including a conductive polymer having a controlled pH. Another aspect of the present invention is to provide a structure with a polymer pattern on the surface. 〃 & Month Summary A broad aspect of the present invention is a $ electric substance composition having a controlled pH. The present invention (another broad aspect is a structure having a surface on which a conductive polymer having a controlled pH 値 is provided. A more specific aspect of the present invention is a structure having a surface on the surface It has a pattern formed by a conductive polymer having a controlled pH 値. Another broad aspect of the present invention is a structure having: a surface; a plurality of thin layers on the surface; the plurality of thin layers At least one of them is made from an energy-sensitive material; at least another layer is made from a conductive polymer; the conductive polymer contains an acid functional group; and the conductive polymer has a predetermined 値. The present invention is in another broad sense. One aspect is a method for disposing a conductive polymer having a controlled pH on the surface. Another more specific aspect of the present invention is a method for disposing a plurality of thin papers on the surface with a thick scale of KS family mark in Shizhou, KS) Λ4 specification (210X 297mm (谙 Please read the notes on the back before filling out this page)

、1T i# 經渋部中决枕沐而h_T消贽合竹社印製 五、發明説明（e) 於80°C下經塗敷後烘 對於光阻石印沒有影嚮。刀鐘。發現由於聚苯胺洪烤，故 如具有及未具有聚笨胺頂塗層之之存放， 如可見及者，聚苯胺伤# η 心伃裒瑚。 係停止實驗。係延長聚合物之存放期至24天，此時 説明 成之：構係針對具有經控制PH値之導電性聚合物及以龙製 ^結構m施本發明之此 = 自可溶性先質之經取抑命土· 貝灼馬製 、聚苯胺、㈣：心 取代之聚對苯、聚對笨乙缔 聚-苯1乙：，;T、聚對苯硫、聚吱喃m 莓取人从、 及其組合，以及其單體之共聚物。供此 等來a物用之通式可表 飞T參閱頒了 Angelopoulos等人之美國專利 二取J /、陳述内容係併於本文供參考。本發明係參考 取三=口物頜型加以描述，其爲一種經取代或未經取代之 \苯胺 <具有圖1中所示通式之聚苯胺共聚物，其中各 R可Ή或任何有機或無機基團；各&可爲相同或不同·其 :各R可爲Η或任何有機或無機基團，各Rl可爲相同或不 同舍X=\1，罕父佳爲χέ2，及y具有0至1之數値。有機基團 i男例爲烷基或芳基。無機基團之實例爲si與&。此清單 僅爲舉例而已並非限制。 導電性聚合物形式之先質，係示於圖la中。此係爲聚合 物或基料聚合物之未經摻雜形式。圖比顯示以摻雜劑摻雜 之來苯胺。若使聚笨胺鹼曝露至陽離子性物種QA，則此 聚合物亞胺部份之氮原子變成被Q +陽離子取代，而形成、 1T i # It is printed by the pillow of the Ministry of Economic Affairs and printed by h_T. The description of the invention (e) After baking at 80 ° C, it has no effect on the photoresist lithography. Knife clock. It was found that due to the flooding of polyaniline, if it is stored with and without a polybenzyl top coating, if visible, polyaniline hurts the heart. Department stopped the experiment. It is to extend the storage period of the polymer to 24 days. At this time, it is described as follows: the structure is directed to the conductive polymer with controlled pH 値 and the structure of the dragon is used to apply the present invention. This is obtained from the soluble precursor Suppressed soil · Made by bezoar, polyaniline, osmium: heart-substituted poly-p-phenylene, poly-p-phenylene, poly-phenylene: 1 ;, T, poly-p-phenylene sulfide, polystyrene, berries And combinations thereof, and copolymers of their monomers. The general formulae used for these things can be shown in the US patent issued by Angelopoulos et al. The present invention is described with reference to three = mouth-jaw type, which is a substituted or unsubstituted \ aniline < polyaniline copolymer having the general formula shown in FIG. 1, wherein each R may be fluorene or any organic Or an inorganic group; each & may be the same or different · which: each R may be Η or any organic or inorganic group, each Rl may be the same or different X = \ 1, Han Jiajia is χ 2 and y Has a number from 0 to 1. Examples of the organic group i are alkyl or aryl. Examples of inorganic groups are si and &. This list is only an example and not a limitation. The precursors in the form of conductive polymers are shown in Figure la. This is an undoped form of the polymer or base polymer. The figure shows aniline doped with dopants. If the polybenzylamine is exposed to the cationic species QA, the nitrogen atom of the imine part of the polymer will be replaced by Q + cations, and formed

Iyl^ ；丨«私衣---- {M先閱讀背面之注意事項再填寫本頁jIyl ^; 丨 «Private clothes ---- {M Please read the notes on the back before filling in this page j

、1T i* 4、纸依尺度適州中囤囚家標嗥(7^； -9 - '4規格（2丨〇χ 297公釐） 565745 A7 -------B7 五、發明説明（7) 篛翠綠鹽，如圖lb中所示。Q +可選自H +及有機或 離子，！例如烷基或金屬。 QA可爲質子酸’其中q爲氫。當使用質子酸似以接雜聚 苯胺時，聚苯胺亞胺部份之氮原子係被質子化。此翁翠綠 驗形式係極大地被共振作用安定化。此等電荷係經過氮原 子=芳族環分佈，使得亞胺與胺氮不能區別。經摻雜形式 &lt;實際結構ϋ去定域化之聚半酿基陽離子，如 中所示。 聚苯胺可以多種氧化狀態存在。此聚合物之翡翠綠形式 係指由大約相等數目之苯構體單位與醌型單位所組成之材 料（於圖1中y ^ 0.5)。翡翠綠聚合物可被還原成無色翡翠綠 聚合物，其中於圖1中y=1。此聚合物之無色翡翠綠鹼形 式，在環境條件中不安定。翡翠綠聚合物可被氧化成波尼 瓜苯胺（pemigraniline)形式，其中y = 〇 ;但是，此聚合物之完 全氧化形式亦有不安定之傾向。大體上而言，介於y = 〇與 y = i中間之其他氧化狀態是可能的。聚苯胺之翡翠綠鹼形 式係爲最安定形式。由於其環境安定性，故其係爲已被最 廣a研％之聚苯胺形式，且爲適合工業技術應用之形式。 本發明之最佳具體實施例爲聚苯胺之翡翠綠鹼形式，其中 y具有大約〇.5之數値。 正如可自圖lc見及者，經摻雜之聚苯胺爲酸性，因其通 常係被質子酸摻雜。摻雜劑可包括單一分子、寡聚物及聚 合物。例如，吾人在先前曾描述一系列水溶性聚苯胺，其 係於多元酸存在下，經由使苯胺聚合而製成，其係描述於 本紙張尺度適州中國S家標枣((’NS ) Λ4規格（210 X 297公f ) ---；-I^-I—I (諳先閱讀背面之注意事項再填寫本頁) 、11 J· 565745 A 7 __________B7 五、發明説明（8 ) &quot; 一' 美國專利5,370,825中，其陳述内容係併於本文供參考。杏 聚苯胺在聚合反應期間形成時，其係環繞多元酸包覆，而 造成聚苯胺/多元酸之摻合物（圖2)。多元酸之實例爲聚 苯乙烯磺酸、聚丙烯醯胺基丙烷磺酸等，如在（專利中 所述者。在最後導電性聚苯胺/多元酸摻合物中，多元酸 具有官能性磺酸基，其並不被用來摻雜聚苯胺。因此，有 自由態磺酸基使得聚苯胺頗具酸性。自由態磺酸基之數目 係決定聚合物之酸度或pH値。剛製成時，聚合物可極具酸 性，pH = 1 至 1.5。 圖3描繪具有過量酸官能基度之經摻雜聚苯胺之一般視 圖。此酸可在聚苯胺主鏈上及/或在掺雜劑分子之抗衡陰 離子上。在將聚苯胺塗敷於光阻或酸敏感性塑膠或金屬上 時’此過量酸產生重大顧慮。例如，在塗敷聚苯胺於光阻 頂邵上以防止在電子束照射或SEM度量期間帶電時，聚笨 胺之酸官能基度會污染光阻。 於工業上之大邵份光阻，均以化學方式放大（CA),包括 光酸發生劑（pAG)及含有酸敏感性可去阻斷基團之聚合物。 於照射時，PAG係形成酸。此酸開始使聚合物上之酸敏感 性耳能基去阻斷。達成高性能CA光阻之關鍵，係爲僅必須 催化量之酸即可起動極有效之去保護反應。其原因爲在照 射時形成之酸僅爲觸媒而已。當其開始使酸敏感性官能基 去除保護時，其他酸係自去保護機制釋出，於是其係充作 觸媒供隨後去保護作用使用。因此，一質子係開始自動催 化 &lt; 級聯反應。由於此機制，故CA光阻極有效，並具有極 木紙張尺度適規格)-—— (請先閲讀背面之注意事項再填寫本頁} 一裝· 、11 565745 A7 B7 五、發明説明（9 ) 向敏感性。同時，由於此種對酸之敏感性，故其易於被任 何微量酸3染，於是破壞光阻之優越石印性能。因此，其 係爲能夠控制任何被塗敷至〇八光阻上方/其中/或其下^ 〈材料pH値之關鍵。CA光阻亦對溫度具敏感性，因爲酸 擴散會發生而使得未經曝光之區域曝露至酸。伴隨著自由 態酸之溫度，會破壞CA光阻之石印性能。 酸通常可催化金屬腐蝕、塑膠之降解等。因此，一般期 主把夠&amp;制導兒性聚合物之最後pH値，以防止此等問題。 爲控制聚苯胺材料之阳値，故將酸性聚苯胺以中和劑譬 如通當鹼處理’以中和一部份或全部酸基團”匕鹼係以適 合調整其pH値從〇至14，較佳爲1至7，且最佳爲1至5之量 ’加入聚苯胺中。 j當鹼之清單包&amp;··氫氧化四甲基銨、氫氧化四乙銨、 氫氧化四丁基銨、Z乙胺、吡啶、第三-丁氧化物、嗎福 林：四氫吡咯酮、氫氧化鉀、氫氧化鈉、氫氧化鋰、氫氧 ，三苯基锍，一級、二級及三級胺類，質子海綿、氫化鈉 等。此清單僅爲舉例而已並非限制。 實例： 呈篛翠綠形式之未經取代之聚苯胺，係在inhci*，使 用過氧二@酸按作爲氧化劑，#苯胺之化學氧化聚合法合 成而得。聚苯胺亦可以電化學方式經氧化聚合，如由 W_ Huang，b. Humphrey 與 A G MacDia〇nid，在' 】 \__1: 82,2385，1986中所陳述者。在化學合成中，導電性聚 笨胺鹽酸鹽（翡翠綠鹽酸鹽）會從溶液沈澱。使此聚合反應 -12 (諳先閲讀背面之注意事項再填寫本頁)、 1T i * 4. Paper according to the standard in Shizhou. (7 ^; -9-'4 size (2 丨 〇χ 297mm) 565745 A7 ------- B7 V. Description of the invention (7) Emerald green salt, as shown in Figure lb. Q + can be selected from H + and organic or ionic, such as alkyl or metal. QA can be a protonic acid, where q is hydrogen. When using a protonic acid, it seems like When doped with polyaniline, the nitrogen atom of the polyaniline imine part is protonated. This Weng Cui green test system is greatly stabilized by resonance. These charges are distributed through nitrogen atoms = aromatic rings, making the imine Indistinguishable from amine nitrogen. Doped form &lt; actual structure ϋ delocalized polyhemamyl cation as shown in the figure. Polyaniline can exist in various oxidation states. The emerald green form of this polymer refers to A material composed of an equal number of benzene conformation units and quinone units (y ^ 0.5 in Figure 1). Emerald green polymers can be reduced to colorless emerald green polymers, where y = 1 in Figure 1. This polymerization The colorless form of the emerald green base is unstable in environmental conditions. The emerald green polymer can be oxidized to ponigra niline) form, where y = 〇; however, the fully oxidized form of this polymer also tends to be unstable. In general, other oxidation states between y = 〇 and y = i are possible. Polyaniline The emerald green alkali form is the most stable form. Due to its environmental stability, it is a polyaniline form that has been the most widely studied, and is a form suitable for industrial technology applications. The best embodiment of the present invention Is the emerald green base form of polyaniline, where y has a number of approximately 0.5. As can be seen from Figure lc, the doped polyaniline is acidic because it is usually doped with a proton acid. Doping Agents can include single molecules, oligomers, and polymers. For example, we have previously described a series of water-soluble polyanilines, which are made by polymerizing aniline in the presence of a polyacid, which is described on this paper scale Shizhou China S Family Standard Date (('NS) Λ4 Specification (210 X 297 male f) ---; -I ^ -I-I (谙 Please read the precautions on the back before filling this page), 11 J · 565745 A 7 __________B7 V. Description of Invention (8) &quot; I 'US Patent 5,370,8 25, the content of which is incorporated herein by reference. When apricot polyaniline is formed during the polymerization reaction, it is wrapped around a polyacid, resulting in a polyaniline / polyacid blend (Figure 2). Examples are polystyrene sulfonic acid, polypropylene amidopropane sulfonic acid, etc., as described in the (patent. In the final conductive polyaniline / polyacid blend, the polyacid has a functional sulfonic acid group, It is not used to dope polyaniline. Therefore, the presence of free-state sulfonic acid groups makes polyaniline quite acidic. The number of free-state sulfonic acid groups determines the acidity or pH of the polymer. When freshly made, the polymer can be extremely acidic with pH = 1 to 1.5. Figure 3 depicts a general view of a doped polyaniline with excess acid functionality. This acid may be on the polyaniline backbone and / or on the counter anion of the dopant molecule. When polyaniline is applied to a photoresist or acid sensitive plastic or metal &apos; this excess acid creates significant concerns. For example, when polyaniline is applied to the photoresist to prevent it from being charged during electron beam irradiation or SEM measurement, the acid functionality of polybenzylamine can contaminate the photoresist. The major photoresists in the industry are chemically amplified (CA), including photoacid generators (pAG) and polymers containing acid-sensitive deblocking groups. Upon irradiation, PAGs form acids. This acid begins to block acid-sensitive ear energy groups on the polymer. The key to achieving high-performance CA photoresist is to start a highly effective deprotection reaction with only a catalytic amount of acid. The reason is that the acid formed during the irradiation is only the catalyst. When it begins to remove protection from acid-sensitive functional groups, other acids are released from the deprotection mechanism, so it acts as a catalyst for subsequent deprotection. As a result, a proton system began to automatically catalyze the <cascade reaction. Due to this mechanism, the CA photoresist is extremely effective and has the proper specifications of the extremely wood paper.) ----- (Please read the precautions on the back before filling out this page} One pack ·, 11 565745 A7 B7 V. Description of the invention (9 ) To the sensitivity. At the same time, due to this sensitivity to acid, it is easy to be stained with any trace of acid 3, so the superior lithography performance of photoresist is destroyed. Therefore, it is able to control any coating to 08 light The key to resist above / wherein / or below ^ <material pH 値. CA photoresist is also sensitive to temperature, because acid diffusion will occur and expose unexposed areas to acid. Accompanying the temperature of free state acid, Will destroy the lithographic properties of CA photoresist. Acid usually catalyzes metal corrosion, plastic degradation, etc. Therefore, in the general period, the final pH of the &amp; guiding child polymer is sufficient to prevent these problems. In order to control polyaniline Material is impotence, so acidic polyaniline is treated with a neutralizing agent such as Tongdang alkali to 'neutralize some or all of the acid groups.' The alkali is suitable to adjust its pH from 0 to 14, preferably 1 To 7, and optimally in an amount of 1 to 5 In the list of amines, the list of bases includes &amp; · tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, Zethylamine, pyridine, tertiary-butoxide, and morpholin: Tetrahydropyrrolidone, potassium hydroxide, sodium hydroxide, lithium hydroxide, hydroxide, triphenylphosphonium, primary, secondary and tertiary amines, proton sponges, sodium hydride, etc. This list is only an example and not a limitation. Example: Unsubstituted polyaniline in the form of turquoise green, which is synthesized in inhci *, using peroxodi @ acid as the oxidant, and chemical synthesis of #aniline. Polyaniline can also be electrochemically oxidized Polymerization, as stated by W_ Huang, b. Humphrey and AG MacDiaonid, in '] \ __ 1: 82, 2385, 1986. In chemical synthesis, conductive polybenzylamine hydrochloride (emerald green hydrochloric acid) Salt) will precipitate from the solution. Make this polymerization -12 (谙 Read the precautions on the back before filling this page)

565745 A7 —-：______B7 五、發明説明（10) (請先閱讀背面之注意事項再填寫本頁) 進行數小時，然後將粉末過濾，以過量瓜鹽酸洗滌。然後 ，經由與0·1 Μ氫氧化.銨反應，使翡翠綠鹽酸鹽轉化成非導 電性或未經摻雜之翡翠綠鹼。接著將翡翠綠鹼過濾，使用 氯氧化銨洗條，然後使用甲醇洗滌並乾燥。在此階段之聚 合物，係呈未經摻雜之翡翠綠鹼形式，爲粉末。 ΙΦ 呈翡翠綠形式之經取代（無論是在芳族環上或在氮上）之 聚苯胺，係以如上述之相同方式合成，但在聚合反應中使 用經適當取代之苯胺單體。共聚物係經由一或多種單體之 氧化聚合製成。不爲鹽酸之其他酸·，亦可用於聚合反應中 。含水醋酸、硫酸，有機磺酸，譬如含水甲苯磺酸、十二 基苯磺酸、樟腦磺酸等。鄰-乙氧基取代之聚苯胺，係如 上述，在1Ν鹽酸中，藉鄰-乙氧基苯胺之氧化聚合製成。 具有不同量之鄰-乙氧基含量之共聚物，係在爪鹽酸水溶 液中，經由聚合鄰_乙氧基苯胺與苯胺合成而得。鄰-乙氧 基含量在最後聚合物中之量，係經由改變此單體在最初聚 合反應中之進料比加以控制。 經取代與未經取代之篛翠綠鹼粉末，通常係經由使粉末 落解在有機溶劑中以進行之。未經取代之翡翠綠鹼係以5_ 10%濃度溶解在ΝΜΡ或DMPU中。此溶液可用以旋轉塗覆翡 翠綠驗聚合物薄膜於矽晶圓、石英晶圓、鹽板等之上。此 等薄膜係在500 Α至1.0微米之譜。較厚薄膜（在5〇至2〇〇微米 之譜）係藉溶液鑄膜技術製成，其中係將溶液倒入鋁盤或 坡堝皿中，並放置在60。〇眞空烘箱中24小時。此溶液亦可 用以將材料製成結構零件或製成纖維。經取代之翡翠綠鹼 本纸張尺度適川中國S家標苹(TnS ) Λ4規格（ 210X 297公t ) 565745 A7 -______B7 五、發明説明（1彳） ~— ’譬如鄰-乙氧基取代之翡翠綠鹼，係比未經取代之翁翠 綠驗吏可溶。此聚合物可溶解於環己酮、四氫呋喃、乳酸 乙酯等等之中。於環己酮中製成一種溶液（5%固體），並將 此溶液用以製成薄膜（薄的及厚的）。 呈未經摻雜形式之聚苯胺，可以譬如鹽酸、醋酸、甲酸 、聚苯乙烯磺酸、丙烯醯胺基丙烷磺酸、聚丙烯酸等摻雜 劑處理，以使此材料導電。 此水溶性聚苯胺係按美國專利5,37〇,825中所述製成，其陳 述内容係併於本文供參考。剛製成之聚合物具有阳値爲 I·9。藉由添加鹼，譬如氫氧化四曱基銨，使pH値增加至 Z〇，至2.)，至3.0及至5.0。聚苯胺粉末可以固態使用鹼溶 液處理。可使聚苯胺溶解，並以鹼在溶液中進行處理。可 將聚苯胺製成薄膜或結構零件，並以鹼溶液處理。再者， 來苯胺可在合成期間按下述進行處理：當聚苯胺自反應混 合物分離時，可將其以鹼溶液洗滌。 於下文給予之實例中，係使用聚苯胺作爲散逸塗層，位 於介電能量敏感性材料，正色調與負色調光阻兩者之頂部 〇 實例1 ··使用於正色調光阻UV3頂部上之聚苯胺 使用於此實驗中之能量敏感性光阻係爲，其爲一種 由mM/Shipley製造之市售遠uv光阻。此材料具有習知且經 記載之電子束敏感性。將此光阻於485〇rpm下旋轉塗覆，以 獲得大約0.32微米之厚度，並在14〇r下烘烤3分鐘。將水 溶性聚苯胺藉旋轉塗覆，塗敷於經烘烤^3光阻之頂部。 本紙張尺度❹) (請先閲讀背面之注意事項再填寫本頁) 一裝·565745 A7 —-: ______B7 V. Description of the invention (10) (Please read the precautions on the back before filling this page) After several hours, filter the powder and wash with excess citric acid. Emerald green hydrochloride is then converted to non-conductive or un-doped emerald green base by reaction with 0.1 M ammonium hydroxide. The emerald green alkali was then filtered, the bars were washed with ammonium oxychloride, then washed with methanol and dried. The polymer at this stage is in the form of an un-doped emerald green base and is a powder. IΦ Polyaniline substituted in the emerald green form (either on the aromatic ring or on the nitrogen) was synthesized in the same manner as described above, but an appropriately substituted aniline monomer was used in the polymerization reaction. Copolymers are made by the oxidative polymerization of one or more monomers. Other acids that are not hydrochloric acid can also be used in the polymerization reaction. Aqueous acetic acid, sulfuric acid, and organic sulfonic acids, such as aqueous toluenesulfonic acid, dodecylbenzenesulfonic acid, and camphorsulfonic acid. The ortho-ethoxy substituted polyaniline is prepared as described above by the oxidative polymerization of ortho-ethoxyaniline in 1N hydrochloric acid. Copolymers with different amounts of ortho-ethoxy groups are obtained by synthesizing ortho-ethoxyaniline and aniline in claw hydrochloric acid aqueous solution. The amount of o-ethoxy group content in the final polymer is controlled by changing the feed ratio of this monomer in the initial polymerization reaction. Substituted and unsubstituted scopolamine powders are usually carried out by dissolving the powder in an organic solvent. Unsubstituted emerald green base is dissolved in NMP or DMPU at a concentration of 5-10%. This solution can be used to spin-coat the emerald green polymer film on silicon wafers, quartz wafers, salt plates, etc. These films are in the 500 A to 1.0 micron spectrum. Thicker films (in the range of 50 to 200 microns) are made by solution casting technology, where the solution is poured into an aluminum pan or pitcher and placed at 60 ° C. 〇 Empty the oven for 24 hours. This solution can also be used to make materials into structural parts or into fibers. Substituted emerald green alkali The paper size is suitable for Sichuan China S standard Ping (TnS) Λ4 specification (210X 297g t) 565745 A7 -______ B7 V. Description of the invention (1 彳) ~ — 'such as o-ethoxy substitution The emerald green base is more soluble than the unsubstituted Weng Cui green inspector. This polymer is soluble in cyclohexanone, tetrahydrofuran, ethyl lactate, and the like. Make a solution (5% solids) in cyclohexanone and use this solution to make a film (thin and thick). Polyaniline in an undoped form can be treated with dopants such as hydrochloric acid, acetic acid, formic acid, polystyrenesulfonic acid, acrylaminopropanesulfonic acid, polyacrylic acid, etc. to make the material conductive. This water-soluble polyaniline is made as described in U.S. Patent 5,37,825, the contents of which are incorporated herein by reference. The freshly made polymer has impotence of I · 9. By adding a base such as tetramethylammonium hydroxide, the pH is increased to Z0, to 2.), to 3.0 and to 5.0. The polyaniline powder can be solid-state treated with an alkali solution. Polyaniline can be dissolved and treated with a base in solution. Polyaniline can be made into films or structural parts and treated with an alkaline solution. Furthermore, leniidine can be treated during synthesis as follows: When polyaniline is separated from the reaction mixture, it can be washed with an alkaline solution. In the examples given below, polyaniline is used as a dissipative coating, which is located on top of a dielectric energy-sensitive material, both positive-tone and negative-tone photoresists. The energy-sensitive photoresist used in this experiment was polyaniline, which is a commercially available far UV photoresist manufactured by mM / Shipley. This material has a known and documented electron beam sensitivity. This photoresist was spin-coated at 4850 rpm to obtain a thickness of about 0.32 micrometers, and baked at 14 r for 3 minutes. The water-soluble polyaniline was spin-coated on top of the baked photoresist. Dimensions of this paper 请) (Please read the precautions on the back before filling this page)

、1T .II I- 1 · 565745 A7 ----------B7 五、發明説明（12) (請先閱讀背面之注意事項再填寫本頁) 由於UV3爲以化學方式放大之光阻，故來自空氣鹼 性化合物或被塗覆於光阻頂部上之物質之污染，具有阻礙 光阻成像性質之可能性。爲#求解決此項問，將具有不 同pH値之導電性塗層塗敷於之頂部。進行其他實驗， 以測定導電性層之處理條件係如何影嚮光阻之成像性質。 在此等實驗中，係檢驗在旋轉塗覆後烘烤（pAB)導電性層， 及在曝光後烘烤步驟（PEB)期間導電性頂塗層之不存在;存 在。曝光係於25 KeV電子束工具上進行。 曰聚苯胺之pH値對於UV3石印性質之作用，係經由使υπ 晶圓構圖進行檢驗，該晶圓已塗覆ρΗι·9與阳5之聚苯胺。 在此等貝知中，並未對聚苯胺施予塗敷後烘烤。由於此烘 烤爲額外處理步驟，故在製造環境中，這會轉化成較昂貴 之程序。在一組實驗中，係將聚苯胺於曝光之後但在曝光 後烘烤之則，在水中沖洗。在第二組實驗中，係在曝光後 烘烤期間，將聚苯胺留在適當位置上，並於顯像前立即沖 洗。孩實驗之結果可在表1中明瞭。 經湞部屮^s^-^u工消费合竹y印Ϊ 、自此等結果，可獲得之結論是聚苯胺之處理與阳値對於 光阻I石印具有顯著影嚮。若聚苯胺於ΡΕΒ期間留在適當 位置上，則依材料之ρΗ値而定，光阻回應係爲不同。對於 低pH値變型ρΗ = 19而言，光阻變薄且圖樣不見。這表示聚 苯胺中之故官能基在烘烤步驟期間擴散至光阻中，造成聚 合物去阻斷及光阻變薄（參閲圖4)。對於高pH値材料pH = 5 而&amp; ’右聚笨胺在PEB期間留在適當位置上，則光阻不會 像°义表示被添加以調整pH値之鹼，係污染UV3光阻。 本祕尺度適 565745 A7 B7 五、發明説明（13) 匕驗係Μ除酸，而造成供化學作用在光阻中發生。若聚苯 ： ^--·衣一丨 (請先閲讀背面之注意事項再填寫本頁) ，在ΡέΒ之前被移除，則其顯示對光阻之石印無影嚮Γ獲 知優越解析與敏感性（參閱圖5)。 曰進行其他實驗，以測定在塗敷後烘烤聚苯胺對於石印術 是否有任何影嚮。使用1.9ρΗ材料與25pH材料，在8(rc下 以5分鐘烘烤進行試驗。於PEB之前，將聚苯胺沖洗。與未 經烘烤試樣比較，石印結果未改變（圖6 &amp; 7)。 、 使用低pH値材料及於PEB前沖洗，於上進行存放期 拭驗。對X.射線與光罩應用而言，典型上係預先塗覆基材 ’並儲存直到準備使用爲止。使用以化學方式放大之光阻 ，由於環境污染，故此光阻不能夠儲存太久。頂塗層有時 係：以延長光阻之存放期，從其被塗覆時至曝光，及從曝 光土 PEB。進仃實驗以測足聚苯胺是否有效作爲旧3之頂 塗層。在此等實驗中，UV3係以聚苯胺塗覆並在室溫下儲 存不同時期。光阻之存放期爲5·8天，然而使用聚苯胺時， =係延伸到至少22天（圖8)。此時係停止實驗。 經淖部中次标準局h-τ消贽合作社印製 實例2 :在負色調光阻CGR頂部上之聚苯胺 ，亦發現聚苯胺係有效地塗覆於負型光阻&lt;：(^上。已發現 增加CGR之存放職4小時至24小時。cg㈣常比+色調 UV3光阻較不安定。 貧例3 :在pmma與SNR頂部上之聚苯胺 亦在電子束聚甲基丙晞酸甲酿光阻之頂部上及在 -色調SNR光阻上測試聚苯胺。在兩種情況中，已發現若在 PEB程序之前將其移除，則聚苯胺不會污染光阻。 娜尺度樹_家料規格（210X29'U) 565745 五、發明説明（14)、 1T .II I- 1 · 565745 A7 ---------- B7 V. Description of the invention (12) (Please read the notes on the back before filling this page) Because UV3 is a chemically amplified light Contamination, so the pollution from air basic compounds or materials coated on top of the photoresist has the possibility of hindering the photoresist imaging properties. In order to solve this problem, a conductive coating with different pH is applied on top. Other experiments were performed to determine how the processing conditions of the conductive layer affect the imaging properties of the photoresist. In these experiments, the presence of the conductive top coat during spin-baking (pAB) and the conductive top coat during the post-exposure baking step (PEB) was examined. Exposure was performed on a 25 KeV electron beam tool. The effect of pH 値 of polyaniline on the properties of UV3 lithography is examined by patterning a wafer of υπ, which has been coated with polyaniline of ρΗι · 9 and yang5. Among these know-how, polyaniline is not subjected to post-coating baking. Since this baking is an additional processing step, in a manufacturing environment, this translates into a more expensive procedure. In one set of experiments, polyaniline was rinsed in water after exposure but baked after exposure. In the second set of experiments, the polyaniline was left in place during post-exposure baking and rinsed immediately before development. The results of the child experiment can be seen in Table 1. According to the results of the Ministry of Industry and Technology, the results obtained from these results indicate that the treatment of polyaniline and impotence have a significant influence on the photoresist I lithography. If the polyaniline stays in place during the PEB, the photoresist response is different depending on the ρΗ 値 of the material. For the low pH 値 variant ρΗ = 19, the photoresist becomes thinner and the pattern is missing. This means that the functional groups in the polyaniline diffuse into the photoresist during the baking step, causing the polymer to deblock and thin the photoresist (see Figure 4). For high pH materials with pH = 5 and &amp; ′ dextran is left in place during PEB, the photoresist will not be added as a base to adjust the pH of the alkali, which will contaminate the UV3 photoresist. The standard of this secret is 565745 A7 B7. V. Description of the invention (13) The test is to remove the acid, which causes the chemical reaction to occur in the photoresist. If polyphenylene: ^-· yiyi 丨 (please read the precautions on the back and then fill out this page), it will be removed before ΡέΒ, then it will show the shadowless direction of the photoresist lithography to learn the superior resolution and sensitivity (See Figure 5). Other experiments were performed to determine if baking polyaniline after coating had any effect on lithography. Using 1.9ρΗ material and 25pH material, bake at 8 (rc for 5 minutes to test. Rinse the polyaniline before PEB. Compared with the unbaked sample, the lithography results are unchanged (Figure 6 &amp; 7) 、 Use low pH materials and rinse before PEB, and perform the storage period swabbing. For X-ray and photomask applications, the substrate is typically pre-coated and stored until ready for use. Use to Chemically amplified photoresist, due to environmental pollution, the photoresist cannot be stored for too long. The top coating is sometimes: to extend the storage period of the photoresist, from when it is applied to exposure, and from exposed soil PEB. Experiments were performed to determine whether polyaniline was effective as a top coating for the old 3. In these experiments, UV3 was coated with polyaniline and stored at room temperature for different periods of time. The storage period of the photoresist was 5 · 8 days However, when using polyaniline, = is extended to at least 22 days (Figure 8). At this time, the experiment is stopped. Printed by the Ministry of Standards and Technology Bureau h-τ Consumer Cooperative Cooperative Society Example 2: On top of the negative-tone photoresist CGR Polyaniline on the above, also found that polyaniline is effectively coated on negative photoresist &lt;: (^ Top. It has been found that the storage time of CGR is increased from 4 hours to 24 hours. The cg ratio is often less stable than the + UV UV3 photoresist. Poor example 3: Polyaniline on top of pmma and SNR is also in electron beam polymethyl propylene. Polyaniline was tested on top of the galvanic acid photoresist and on the -tone SNR photoresist. In both cases, it has been found that polyaniline does not contaminate the photoresist if it is removed before the PEB procedure. Nanoscale Tree_Family Specification (210X29'U) 565745 V. Description of Invention (14)

已發現聚苯胺爲一種有斂了百、、各紅1 P ’攻頂塗層放電層。若處理條件與 pH値鳇良好地控制，則可將並 (請先閱讀背面之注意事項再填寫本頁) 4 j和其塗敷於光阻上，而不會使光 阻石印結果降質。最良好結果係當聚苯胺在光阻PEB之前 移除時獲得。若在PEB之前將其移除，則其pH値對於光阻 似乎沒有顯著影嚮。若聚苯胺於pEB期間留在其上，則在 聚苯胺中之酸會冷染光阻，且若添加太多鹼以中和聚苯胺 酸度，則此鹼亦可能冷染光阻。因此，控制聚苯胺之阳値 是重要的。爲獲得最良好結果，PH値應在1與5之間，更 佳係在1.5與5之間，且最佳係在u與3之間。 光阻之清單包括：uvx系列（IBM/Shipley產品），包括羥基 苯乙締/甲基丙烯酸第三-丁酯共聚物，及其與其他可聚 合單位譬如苯乙烯、甲基丙烯酸甲酯等之三聚物，甲基丙 烯酸酯/丙烯酸酯聚合物，譬如聚甲基丙烯酸甲酯及其衍 生物，SNR、CGR、KRS、Zep，含矽光阻，PBS (聚丁烷砜） ’有機金屬光阻，含酚醛清漆光阻，酚醛清漆/重氨基醌 光阻等。此光阻可爲+色調或_色調；其可爲單層光阻或多 層光阻；以化學方式放大及非化學方式放大。下列美國專 利係描述可用以實施本發明之光阻，其係併於本文供參考 經？^部中次if^-^n-T消抡合社印製 5,580,694, 5,554,485, 5,545,509, 5,492,793, 5,401，614, 5,296,332, 5,240,812， 5,071，730, 4,491，628, 5,585,220, 5,561，194, 5,547,812, 5,498,765, 5,486,267， \ 5,482,817, 5,464,726, 5,380,621，5,374,500, 5,372,912, 5,342,727, 5,304,457， 5,300,402, 5,278,010, 5,272,042, 5,266,444, 5，198，153, 5，164,278, 5，102,772， 5,098,816, 5,059,512, 5,055,439, 5,047,568, 5,045,431，5,026,624, 5,019,481， -17 表纸張尺度適川中國囤家標净.（n\s ) Λ4規格（210X 297公釐） 565745 A7 B7 五、發明説明（15) (請先閲讀背面之注意事項再填寫本頁) 4,940,651，4,939,070, 4,931，379, 4,822,245, 4,800，152, 4,760,013, 4,551，418, 5,338,8ί8, 5,322,765, 5,250,395, 4,613,398, 4,552,833, 5,457,005, 5,422,223, 5,338,818, 5,322,765, 5,312,717, 5,229,256, 5,286,599, 5,270，151，5,250,395, 5,238,773, 5,229,256, 5,229,251，5,215,861，5,204,226, 5，115,095, 5，110,711， 5,059,512, 5,041，358, 5,023，164, 4,999,280, 4,981，909, 4,908,298, 4,867,838, 4,816，112, 4,810,601，4,808,511，4,782,008, 4,770,974, 4,693,960, 4,692,205, 4,665,006, 4,657,845, 4,613,398, 4,603，195, 4,601，913, 4,599,243, 4,552,833, 4,507,331，4,493,855, 4,464,460, 4,430，153, 4,307，179, 4,307，178, 5,362,599, 4,397,937, 5,567,569, 5,342,727, 5,294,680, 5,273,856, 4,980,264, 4,942，108, 4,880,722, 4,853,315, 4,601，969, 4,568,631，4,564,575, 4,552,831，4,522,911， 4,464,458, 4,409,319, 4,377,633, 4,339,522, 4,259,430, 5,209,815, 4,211，834, 5,260，172, 5,258,264, 5,227,280, 5,024,896, 4,904,564, 4,828,964, 4,745,045, 4,692,205, 4,606,998, 4,600,683, 4,499,243, 4，S67，132, 4,564,584, 4,562,091， 4,539,222, 4,493,855, 4,456,675, 4,359,522, 4,289,573, 4,284,706, 4,238,559, 4,224,361, 4,212,935, 4,204,009, 5,091,103, 5,124,927, 5,378,511, 5,366,757, 4,590,094, 4,886,727, 5,268,260, 5,391,464, 5,115,090, 5,114,826, 4,886,734, 4,568,601, 4,678,850, 4,543,319, 4,524,126, 4,497,891, 4,414,314, 4,414,059, 4,398,001，4,389,482, 4,379,826, 4,379,833, 4，187,331。 亦發現聚苯胺係爲加強光阻存放期之保護性導電塗層。 其基本功能爲清除通常會擴散至光阻中之周圍污染物。 CGR係代表負型DUV以化學方式放大之光阻。其化學成 ' 份爲聚羥基苯乙烯，MDT作爲光酸發生劑（PAG)，及粉末連 結劑作爲交聯劑。SNR爲Shipley負型DUV以化學方式放大之 光阻。SNR代表Shipley負型光阻。其爲一種聚羥基苯乙烯。 —-~~—____ — __-18-_ 本纸張尺度適州家標苹（fNS ) Λ4規格（210X 297公釐) &quot; 565745 A7 -______ Β7___ 五、發明説明（16) 其含有三聚氰胺交聯劑與PAG。KRS爲一種正正型遠取以 化學方式放大之光阻。KRS代表縮酮光阻系統。其化學成 份爲聚羥基苯乙烯，及縮醛保護之聚羥基苯乙烯作爲共聚 物。PAG爲三氟曱烷磺酸三苯基銃。UV3爲IBM/Shipley正型 DUV以化學方式放大之光阻。其含有聚輕基苯乙晞，與甲 基丙烯酸第三-丁酯共聚物。PAG爲第三-丁基苯基鋏樟腦 磺酸鹽。ZEP爲電子束光阻。其並非以化學方式放大。其 含有α氯基甲基丙烯酸酯與α甲基苯乙烯共聚物。 表1 : (請先閲讀背面之注意事項再填It?本頁} 聚苯胺之pH値 無聚苯胺/只 有光阻（對照物 ) 1.9 5 於PEB (曝光後 烘烤）之前沖洗 (劑量/石印術） 未沖洗 6 uC /平方公分 :解析0.25微米 影像 6 uC /平方公分 ;解析0.25微米 影像 於PEB之後沖洗 (劑量/石印術） 5.5 uC /平方公分 ;解析0.25微米影 像 6 uC /平方公分； 光阻變薄；圖樣 消失（酸） •，過光作 分像自學 t 顯.f, 方會除&quot;t 平不清酸 1C樣驗之} 61圖量阻用 訂 d 广/十、反口乃 正、改變及改 之精神與範圍下將可發生 己針對較佳具體實施例加以描述，但許 良，對於熟諳此藝者而言，在未偏離本 IT -ΓΓ- ^ .1 本纸张尺度適州中國四家標冷(7^ -19- Μ規格（210X 297公漦）It has been found that polyaniline is a discharge layer with a top coat of 1 P ', each having a concentration of 100%. If the processing conditions and pH are well controlled, you can apply (Please read the precautions on the back before filling this page) 4 j and apply it on the photoresist, without degrading the photoresist lithography results. The best results were obtained when the polyaniline was removed before the photoresist PEB. If it is removed before PEB, its pH 値 does not seem to have a significant effect on photoresist. If polyaniline remains on it during pEB, the acid in the polyaniline will cold-stain the photoresist, and if too much base is added to neutralize the polyaniline acidity, the base may also cold-stain the photoresist. Therefore, it is important to control impotence of polyaniline. For best results, PH 値 should be between 1 and 5, more preferably between 1.5 and 5, and most preferably between u and 3. The photoresist list includes: UVX series (IBM / Shipley products), including hydroxystyrene / three-butyl methacrylate copolymers, and other polymerizable units such as styrene, methyl methacrylate, etc. Terpolymer, methacrylate / acrylate polymer, such as polymethyl methacrylate and its derivatives, SNR, CGR, KRS, Zep, silicon-containing photoresist, PBS (polybutane sulfone) Resistance, novolac-containing photoresist, novolac / heavy aminoquinone photoresist, etc. This photoresist can be a + tone or a _ tone; it can be a single-layer photoresist or a multi-layer photoresist; chemically amplified and non-chemically amplified. The following U.S. patents describe photoresists that can be used to implement the present invention, which are incorporated herein by reference? Printed by the Ministry of Foreign Affairs if ^-^ nT Consumers' Association 5,580,694, 5,554,485, 5,545,509, 5,492,793, 5,401,614, 5,296,332, 5,240,812, 5,071,730, 4,491,628, 5,585,220, 5,561,194, 5,547,812, 5,498,765, 5,486,267 , \ 5,482,817, 5,464,726, 5,380,621, 5,374,500, 5,372,912, 5,342,727, 5,304,457, 5,300,402, 5,278,010, 5,272,042, 5,266,444, 5,198,153, 5,164,278, 5,102,772, 5,098,816, 5,059,512, 5,055,439,045,626,461,568 5,019,481, -17 The paper size is suitable for Sichuan China's domestic standard. (N \ s) Λ4 size (210X 297 mm) 565745 A7 B7 V. Description of the invention (15) (Please read the precautions on the back before filling in this (Pages) 4,940,651, 4,939,070, 4,931,379, 4,822,245, 4,800,152, 4,760,013, 4,551,418, 5,338,8ί8, 5,322,765, 5,250,395, 4,613,398, 4,552,833, 5,457,005, 5,422,223, 5,338,818, 5,322,765, 5,312,717, 5,229,256, 5,286,270 151,5,250,395, 5,238,773, 5,229,256, 5,229,251, 5,215,861, 5,204,226, 5,115,095, 5, 110,711, 5,059,512, 5,041,358, 5,023,164, 4,999,280, 4 , 981,909, 4,908,298, 4,867,838, 4,816,112, 4,810,601, 4,808,511, 4,782,008, 4,770,974, 4,693,960, 4,692,205, 4,665,006, 4,657,845, 4,613,398, 4,603,195, 4,601,913, 4,599,243, 4,552,833, 4,507,331, 4,464,493,4,493,855 , 153, 4,307,179, 4,307,178, 5,362,599, 4,397,937, 5,567,569, 5,342,727, 5,294,680, 5,273,856, 4,980,264, 4,942,108, 4,880,722, 4,853,315, 4,601,969, 4,568,631, 4,564,458, 4,552,831, 4,522,911, 4,464,458,377,409 , 4,339,522, 4,259,430, 5,209,815, 4,211,834, 5,260,172, 5,258,264, 5,227,280, 5,024,896, 4,904,564, 4,828,964, 4,745,045, 4,692,205, 4,606,998, 4,600,683, 4,499,243, 4, S67, 132, 4,564,584, 4,562,091, 4,539,222, 4,539,222 , 4,359,522, 4,289,573, 4,284,706, 4,238,559, 4,224,361, 4,212,935, 4,204,009, 5,091,103, 5,124,927, 5,378,511, 5,366,757, 4,590,094, 4,886,727, 5,268,260, 5,391,464, 5,115,414, 413, 419, 413, 419, 413, 419, 413, 419, 413, 419, 413, 413, 419, 413, 419, 413, 418, 413, 419, 413, 419, 413, 419, 413, 419, 413, 459, 413, 413, 385, 601, 413, 459, 413, 459, 413, 385, 601, 413, 385, 601, 413, 497, 413, 497, 413, 497, 413, 459, 413, 4, 589, 413, 4, 5, 6, 4, 4, 6, 5, 4, 6, 6, 4, 5, 6, 5, 4, 5, 621, 4, 289, 573, 4, 289, 573, 4, 284, 706, 4, 238, 559, 4 , 4,398,001 , 4,389,482, 4,379,826, 4,379,833, 4,187,331. Polyaniline is also found to be a protective conductive coating that enhances the shelf life of photoresists. Its basic function is to remove surrounding contaminants that would normally diffuse into the photoresist. CGR stands for chemically amplified photoresist for negative DUV. Its chemical composition is polyhydroxystyrene, MDT is used as a photoacid generator (PAG), and powder binder is used as a crosslinking agent. SNR is the photoresist chemically amplified by Shipley negative DUV. SNR stands for Shipley Negative Photoresistor. It is a polyhydroxystyrene. —- ~~ —____ — __- 18-_ The paper size is Shizhou Family Standard Ping (fNS) Λ4 size (210X 297 mm) &quot; 565745 A7 -______ Β7 ___ 5. Description of the invention (16) It contains melamine Combination agent with PAG. KRS is a positive positive photoresist that is chemically amplified. KRS stands for ketal photoresist system. Its chemical composition is polyhydroxystyrene, and acetal-protected polyhydroxystyrene is used as a copolymer. PAG is triphenylphosphonium trifluoromethanesulfonate. UV3 is a chemically amplified photoresist for IBM / Shipley positive DUV. It contains poly (phenylene acetofluorene) and a tertiary-butyl methacrylate copolymer. PAG is tertiary-butyl phenyl camphor sulfonate. ZEP is an electron beam photoresist. It is not chemically amplified. It contains an alpha chloromethacrylate and an alpha methylstyrene copolymer. Table 1: (Please read the precautions on the back before filling it? This page} pH of polyaniline 値 no polyaniline / photoresist only (control) 1.9 5 Rinse before PEB (bake after exposure) (dose / lithography) Technique: Unprocessed 6 uC / cm2: Analyze 0.25 micron image 6 uC / cm2; Analyze 0.25 micron image after PEB and rinse (dose / lithography) 5.5 uC / cm2; Analyze 0.25 micron image 6 uC / cm2; The photoresist becomes thinner; the pattern disappears (acid) •, self-taught after the light is taken as a sub-image. F, will be removed &quot; t plain acid 1C sample test} 61 dimensional resistance order d wide / ten, negative Mouth is right, change and the spirit and scope of change will be described with reference to the preferred embodiment, but Xu Liang, for those skilled in this art, has not deviated from this IT -ΓΓ- ^ .1 paper Standard Shizhou China four standard cold (7 ^ -19- Μ specifications (210X 297 cm)

Claims (1)

565745 第087112832號專利申請案 中文申請專利範圍修正本（91年11月） A8 B8 C8 D8 六、申請專利範園565745 Patent Application No. 087112832 Amendment of Chinese Patent Application Scope (November 91) A8 B8 C8 D8 6. Application for Patent Park 一個表面； 多個薄層，在該表面上； 該多個薄層中至少一個包含一種能量敏感性材料； 至少另一個該薄層包含一種導電性聚合物； 該導電性聚合物含有酸官能基度； 該導電性聚合物具有由酸中和用之官能基度所提供之 預定pH值； 該pH值係經預定在1至7之範圍内； 該能量敏感性材料係選自包括羥基苯乙烯/甲基丙婦 酸第三-丁酯共聚物，及羥基苯乙烯/甲基丙烯酸第 三-丁醋共聚物與苯乙烯及甲基丙烯酸甲酯之三聚物， 甲基丙烯酸酯/丙烯酸酯聚合物，及甲基丙烯酸酯/ 丙烯酸酿聚合物之衍生物，含矽光阻，聚丁烷砜，有 機金屬光阻，含酚醛清漆之光阻，及酚醛清漆/重氮 基醌光阻； 該酸中和用之官能基度係選自包括氫氧化四甲基銨、 氫氧化四乙銨、氫氧化四丁基銨、三乙胺、吡啶、第 三-丁氧化物、嗎福啉、四氫吡咯酮、氫氧化鉀、氫氧 化飾、氫氧化嫂、氫氧化三苯基锍，一級、二級及三 級胺類，質子海綿，氫化鈉； 遠導電性聚合物係選自包括製自可溶性先質之經取代 與未經取代之聚對苯、聚對苯乙婦、聚苯胺、聚啡、 聚嘧吩、聚對苯硫、聚呋喃、聚吡咯、聚硒苯、聚乙 本紙張尺度咖十國國家樣準(CNS)織格(21GX297公釐y 565745 A8 B8 C8A surface; a plurality of thin layers on the surface; at least one of the plurality of thin layers includes an energy sensitive material; at least another one of the thin layers includes a conductive polymer; the conductive polymer contains an acid functional group The conductive polymer has a predetermined pH value provided by a functional group for acid neutralization; the pH value is predetermined to be in a range of 1 to 7; the energy-sensitive material is selected from the group consisting of hydroxystyrene / Methacrylic acid third-butyl ester copolymer, and terpolymer of hydroxystyrene / methacrylic acid third-butyl vinegar copolymer with styrene and methyl methacrylate, methacrylate / acrylate Polymers, and derivatives of methacrylate / acrylic polymers, containing silicon photoresist, polybutane sulfone, organometallic photoresist, novolac-containing photoresist, and novolac / diazoquinone photoresist; The degree of functionality of the acid neutralization is selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, pyridine, tertiary-butoxide, morpholine, Tetrahydropyrrolidone, potassium hydroxide, hydroxide , Europium hydroxide, triphenylphosphonium hydroxide, primary, secondary and tertiary amines, proton sponges, sodium hydride; The teleconductive polymer is selected from the group consisting of substituted and unsubstituted precursors made from soluble precursors. Polyparaphenylene, polyphenylene oxide, polyaniline, polymorphine, polypyrimidine, polyparaphenylene sulfide, polyfuran, polypyrrole, polyselenebenzene, and polyethylene paper Grid (21GX297 mm y 565745 A8 B8 C8 玦，及其組合，以及其與其 單體之共聚物，其中該能量 4合物與該表面之間，該導 感性材料提供保護性頂塗層 材料之存放期。 他聚合物之摻合物，及其 敏感性材料介於該導電性 電性聚合物係對該能量敏 ’於是增加該能量敏感性 2· -種包含導電性聚合物之光阻結構的製造方法，其包 含· k 於一表面上配置多個薄層； 4多個薄層中至少_個包含_種能量敏感性材料； 至另一個该薄層包含一種導電性聚合物； 該導電性聚合物含有酸官能基度； 違導電性聚合物具有由酸中和用之官能基度所提供之 預定pH值； 訂 該pH值係經預定在1至7之範圍内；Rhenium, and combinations thereof, and copolymers thereof with their monomers, wherein the conductive material provides a shelf life of the protective topcoat material between the energy compound and the surface. Blends of other polymers and their sensitive materials are interposed between the conductive electric polymer system and the energy sensibility, so the energy sensitivity is increased. A method for manufacturing a photoresist structure including a conductive polymer , Which includes: · a plurality of thin layers are disposed on a surface; at least one of the four thin layers includes energy-sensitive materials; to another the thin layer includes a conductive polymer; the conductive polymer Contains acid functionality; The non-conductive polymer has a predetermined pH value provided by the functionality of the acid neutralization; the pH value is predetermined to be in the range of 1 to 7; 該能量敏感性材料係選自包括羥基苯乙烯/甲基丙烯 酸第二-丁酷共聚物，及羥基苯乙烯/甲基丙烯酸第 二-丁醋共聚物與苯乙烯及甲基丙烯酸甲酯之三聚物， 甲基丙烯酸酯/丙烯酸酯聚合物，及甲基丙烯酸酯/ 丙烯酸酯聚合物之衍生物，含矽光阻，聚丁烷颯，有 機金屬光阻，含酚醛清漆之光阻，及酚醛清漆//重氮 基酿光阻； 該酸中和用之官能基度係選自包括氫氧化四甲基銨、 氫氧化四乙銨、氫氧化四丁基銨、三乙胺、吡啶、第 三-丁氧化物、嗎福琳、四氫晚洛酮、氫氧化钟、氫氧 -2- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐） 565745 A8 B8 C8 ______D8 _ 六、申請專利範園 化鈉、氫氧化鋰、氫氧化三苯基锍，一級、二級及三 級胺類，質子海綿，氫化鈉； 該導電性聚合物係選自包括製自可溶性先質之經取代 與未經取代之聚對苯、聚對苯乙烯、聚苯胺、聚畊、 聚嘧吩、聚對苯硫、聚呋喃、聚吡咯、聚；66苯、聚乙 块，及其組合，以及其與其他聚合物之掺合物，及其 單體之共聚物；以及 加熱該能量敏感性材料，及在該加熱之前，移除該導 電性聚合物。 3.根據申請專利範圍第2項之方法，其中該導電性聚合物 係在該能量敏感性材料顯像期間移除。 4·根據申請專利範圍第2項之方法，其中該導電性聚合物 係在該能量敏感性材料顯像之前移除。 5·根據申請專利範圍第1項之結構，其中該導電性聚合物 為水溶性。 -3- ^紙張尺度適财® ®家料(⑶S) A视格_X297公釐）The energy sensitive material is selected from the group consisting of a hydroxystyrene / second methacrylic acid copolymer and a hydroxystyrene / second methacrylic acid copolymer and styrene and methyl methacrylate. Polymers, methacrylate / acrylate polymers, and methacrylate / acrylate polymer derivatives, containing silicon photoresist, polybutane fluorene, organometallic photoresist, novolac containing photoresist, and Novolac // diazo-based photoresist; the functional group used for acid neutralization is selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, pyridine, Third-Butoxide, Morpholine, Tetrahydroproxone, Bell Hydroxide, Hydroxyl-2- This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 565745 A8 B8 C8 ______D8 _ 6. Apply for a patent Fanyuan sodium, lithium hydroxide, triphenylphosphonium hydroxide, primary, secondary and tertiary amines, proton sponge, sodium hydride; The conductive polymer is selected from the group consisting of soluble precursors Substituted and unsubstituted polyparaphenylene, polyparaphenylene , Polyaniline, polyculture, polypyrimidine, polyparaphenylene sulfide, polyfuran, polypyrrole, poly; 66 benzene, polyethylene blocks, and combinations thereof, and blends with other polymers, and monomers thereof Copolymer; and heating the energy-sensitive material, and removing the conductive polymer before the heating. 3. The method according to item 2 of the patent application scope, wherein the conductive polymer is removed during the development of the energy sensitive material. 4. The method according to item 2 of the scope of patent application, wherein the conductive polymer is removed before the energy sensitive material is developed. 5. The structure according to item 1 of the scope of patent application, wherein the conductive polymer is water-soluble. -3- ^ Paper Standards Seco ® ® Home Supplies (⑶S) A View Grid_X297mm)