TWI243409B

TWI243409B - Immersion fluid for immersion lithography, and method of performing immersion lithography

Info

Publication number: TWI243409B
Application number: TW93124633A
Authority: TW
Inventors: Yee-Chia Yeo; Burn-Jeng Lin; Chenming Hu
Original assignee: Taiwan Semiconductor Mfg
Priority date: 2003-08-25
Filing date: 2004-08-17
Publication date: 2005-11-11
Also published as: SG109582A1; TW200509214A; CN100535753C; CN1655061A

Abstract

An immersion lithographic system comprises an optical surface, an immersion fluid with a pH less than 7 contacting at least a portion of the optical surface, and a semiconductor structure having a topmost photoresist layer wherein a portion of the photoresist is in contact with the immersion fluid. Further, a method for illuminating a semiconductor structure having a topmost photoresist layer comprising the steps of: introducing an immersion fluid into a space between an optical surface and the photoresist layer wherein the immersion fluid has a pH of less than 7, and directing light preferably with a wavelength of less than 450 nm through the immersion fluid and onto the photoresist.

Description

1243409 九、發明說明：【發明所屬之技術領域】 /本發明係關於-種半導體元件的製程，特別是關於浸潤式微影技術之系統、方法及其所使用之浸潤流體。【先前技術】在典型的微影系統中，為了分辨如影像、線條或是鱗高解析的圖形時1微影系統必須達到高解析的程度。找產業的微影系統裡，一般係直接將光投影至-絲層上，明形化—電極元件。微料統已經在1C產業上被使用了幾十年了’並且未來期望用來解決5G奈錄寬及其以下的製成。所以改善微影系統的解析度已經變成半導體IC晶片製造廠商製作高密度和高速度半導體1C晶片最重要的課題之一。山旦〜對於微影系統，其解析度R係由R=kl眶公式所決定，其中kl是微 ❹數’ λ是影像光源的操作波長，而數值孔徑NA是由勝弧㈣公式來 =出’其切肢緖中角辭開雜，而η係為在微影減和欲圖形化基材之間充填空隙之材料的折射率。 ,般來彳彳―種方法可用來調整微影似彳的解析度，以改善微影技術。百先’係'縮減影像光源的操作波長λ，例如：以&1243409 IX. Description of the invention: [Technical field to which the invention belongs] / The present invention relates to the manufacturing process of a semiconductor device, in particular, a system and method for immersion lithography technology, and an infiltration fluid used by the same. [Prior art] In a typical lithography system, in order to distinguish graphics such as images, lines, or scales, a lithography system must reach a high resolution level. In the industry's lithography system, generally, the light is directly projected onto the silk layer, and the electrode component is sharpened. Micro-material systems have been used in the 1C industry for decades' and are expected to be used in the future to solve 5G nano-record width and below. Therefore, improving the resolution of the lithography system has become one of the most important topics for semiconductor IC chip manufacturers to produce high-density and high-speed semiconductor 1C chips. Shandan ~ For the lithography system, the resolution R is determined by the R = kl orbital formula, where kl is the micro chirp number 'λ is the operating wavelength of the image light source, and the numerical aperture NA is calculated by the winning arc formula. The angle of its incision is intricate, and η is the refractive index of the material that fills the gap between the lithography and the substrate to be patterned. As usual, a method can be used to adjust the lithography-like resolution to improve the lithography technology. Baixian ’is used to reduce the operating wavelength λ of the image light source, for example: &

奈_替G射、_賴波長；近來，長已丁喊到157奈米，甚至減小到極短紫外光(EUV)的波長。第二種方法係使用提升解析度的技術，例如使_位移光罩及偏細射以減少微影常數h 2，該微影常數kl值可㈣.6減小賴。第三種方法則是透過光學設計、 :造技術及計量控制的改善，來提昇數值孔徑财值，目前數值孔徑NA 已可由0.35增加至約〇·8。然而’上述改善解析度所慣用的方法已經接近 ^和技術的極限了，例如，祖值(也就是^)係由η值所限制，假如使用-具有自由空間(free space)的光學系統，此時η值係為i，因此ΝΑ的 0503-A30493TWF 5 1243409 值的上限也就是1。一相對衣般之微影技術，近年來，浸潤式微影技術已經發展到可以允找步i曰加NA值(數值孔控）。在浸潤式微影技術中，一欲被圖形化之基材係被⑴帛在#具有㊄折射率的液體或是—種浸潤流體下進形微影製程以圖木化’如此-來，具有該高折射率(n>1)的流體會填滿於該微影系統最外側之光學單兀(例如：透鏡)及基質之間的空隙(原本係由空氣填滿），請參妝如第1圖所不之浸潤式微影技術系統，因此利用此種方法，透鏡可以被，汁以具有大於1之να值。過氟聚醚(PFPE)、環辛烷及去離子水(DL_water) 等具有焉折射率的流體，都可使用於浸潤式微影技術中。由於na值不會被侷限於1 ’朗制式微影技術可較_般郷猶提供較更為精密的微影製程解析度。運用於浸潤式微影技術的高折射率流體應該滿足下列幾項要求：該流體對於所使用具有特定波長的光線必财低的吸㈣數；此外，該流體必須修具有適度高的折鱗以修正整個系統的折射率；再者，該流體必須與基板上的光阻及光學裝置(鏡頭)具有化學上的相容性及良好的接觸性。以下是一些具體實例的相關參考資料的總整理： ⑴ M· Switkes 專人所發表之美國專利“Meth〇ds and apparatus employing an index matching medium”，該申請案之公開號係 us 2〇〇2/〇163629。 (2) J· S. Batchelder 專人所發表之美國專利“Method for optical inspection and lithography，，，該發明之專利號係 US59〇〇354。 (3) Κ· Takahashi 專人所發表之美國專利projecti〇n exposure apparatus，’，該發明之專利號係 US561〇683。 (4) T. R. Corle專人所發表之美國專利“[池观叩办system employing a soMimmersicm lens”，美國專利序號 US5121256。 (5) J· A· Hoffiiagle 等人，於期刊 “j. Vacuum 义化腦 and Techn〇1〇gy B，，Nai is the wavelength of G, and Lai; recently, Chang Ding has shouted to 157 nanometers, and even reduced to the extremely short ultraviolet (EUV) wavelength. The second method is to use a technique for improving the resolution, for example, using a shift mask and a thin shot to reduce the lithography constant h 2. The value of the lithography constant kl can be reduced by ㈣.6. The third method is to improve the numerical aperture financial value through the improvement of optical design, manufacturing technology and measurement control. At present, the numerical aperture NA has been increased from 0.35 to about 0.8. However, the above-mentioned conventional methods for improving resolution are close to the limits of ^ and technology. For example, the ancestral value (that is, ^) is limited by the value of η. If an optical system with free space is used, this The time η value is i, so the upper limit of the NA 0503-A30493TWF 5 1243409 value is 1. In contrast to clothing-like lithography technology, in recent years, immersion lithography technology has been developed to allow the step i to add NA value (numerical hole control). In the immersion lithography technology, a substrate to be patterned is immersed in a liquid with a refractive index or-a type of immersion fluid into the lithography process to map wood. The fluid with high refractive index (n > 1) will fill the gap between the optical unit (such as a lens) on the outermost side of the lithography system and the substrate (originally filled by air). The immersion lithography technology system is not shown in the figure, so with this method, the lens can be made to have a να value greater than 1. Perfluorinated polyether (PFPE), cyclooctane, and deionized water (DL_water) can be used in immersion lithography technology. Since the value of na will not be limited to 1 ′ long-format lithography technology, it can provide a more precise lithography process resolution than _ general. The high refractive index fluid used in immersion lithography technology should meet the following requirements: the fluid must have a low absorption number for the light with a specific wavelength used; in addition, the fluid must be modified with a moderately high scale to correct The refractive index of the entire system; furthermore, the fluid must have chemical compatibility and good contact with the photoresist and optical device (lens) on the substrate. The following is a summary of relevant references for some specific examples: 美国 US patent "Meth〇ds and apparatus employing an index matching medium" published by M. Switkes, the publication number of this application is US 2000 / 〇 163629. (2) US patent "Method for optical inspection and lithography" issued by J. Batchelder, and the patent number of this invention is US5900354. (3) US patent issued by "K. Takahashi" exposure apparatus, ', the patent number of this invention is US561〇683. (4) US patent "[池观叩办 system employing a soMimmersicm lens" issued by TR Corle, US patent No. US5121256. (5) J · A · Hoffiiagle et al., In the journal "j. Vacuum 义化脑 and Techn〇1〇gy B,

vol. 17，no. 6，pp. 3306-3309，1999 所揭露之文章 Liquid immersion 0503-A30493TWF 6 1243409 deep-ultraviolet interferometric lithography ⑹ M· Switkes 等人於期刊 J· Vacuum Science and Techn〇]〇gy B，v〇1 19, no. 6, pp. 2353-2356, 2000 所揭露之文章“Immersi〇n lith〇graphy 泣 157 nm”。在傳統之浸〉?械微影技射，係财作為浸麟體，然而該作為浸潤流體的水之pH健沒有被進-步控齡的。如此—來，微影技術所使用之光阻（特別疋化學放大光阻）會被浸潤流體或是水的氫氧離子(〇兄)污染。此外’某些光料鏡所使狀材料，例如氟簡，亦會在水中有—定的溶解度。因此，傳統之浸潤式微影技魅法提供_具有較低氫氧離子濃度的浸潤流體以防止光學透鏡所使狀難在浸麟射溶解。因此’研發出更佳之浸满式微影技術及方法，以改善習知技術所產生之問題，係半導體技術中一項急待研究之目標。【發明内容】本發明係揭露-種浸潤式微影_，包括—浸猶體填人由一最外声的辟讀=表面及—與其相隔的光阻層之間的空間。另一方面，本發明更進乂揭4種適用於浸潤式微影技術系統中之浸濁流體。用以較佳實施例，一具有小於7之pH值的浸潤流體係被使用以舁一先學π件之部分表面接觸。 ⑼較佳實關，—賴式微料、齡使用—波長小於如；:一=象浸潤式微影系統包括-光學_ 層形成於其上表面’収，一光阻光阻層之部分表面接觸。d，、謂顺體之pH鶴小於7且與該矣此外，本發明之又—較佳實施例係揭露-對具有-光阻μ 表面之半導體結構 ^光阻糾成於其上在—光學元件之η 去係包括以下步驟：首先， "Λ，、相隔的光阻層之間的空間注入pH值小於7的vol. 17, no. 6, pp. 3306-3309, 1999 Liquid immersion 0503-A30493TWF 6 1243409 deep-ultraviolet interferometric lithography ⑹ M. Switkes et al. in the journal J. Vacuum Science and Techn. , V〇1 19, no. 6, pp. 2353-2356, 2000 The article "ImmersiON Lithography 157 nm" was disclosed. In traditional immersion, mechanical lithography, the system is used as a immersion body, but the pH of water, which is used as a immersion fluid, has not been advanced. In this way, the photoresist (especially chemically amplified photoresist) used by lithography technology will be contaminated by hydroxide ions (〇 brother) infiltrating the fluid or water. In addition, some materials made of optical lenses, such as fluorine, also have a certain solubility in water. Therefore, the traditional immersion lithography technique provides an immersion fluid with a lower concentration of hydroxide ions to prevent the shape caused by the optical lens from being difficult to dissolve in the immersion beam. Therefore, the development of better immersion lithography technology and methods to improve the problems caused by the conventional technology is an urgent research target in semiconductor technology. [Summary of the Invention] The present invention discloses a type of immersion lithography, including-immersion and filling of the human body by an external sound reading = surface and-the space between the photoresist layer separated from it. On the other hand, the present invention further discloses four types of immersion fluid suitable for use in the immersion lithography system. In a preferred embodiment, an infiltration flow system having a pH value of less than 7 is used to contact a part of the surface of the first-learned pi member. ⑼Better practice,-Lai-type micro-materials, age-use-the wavelength is less than, such as: a = elephant immersion lithography system includes-an optical layer is formed on its upper surface ', a part of the surface of a photoresist photoresist layer contacts. d, the pH of the cis-body is less than 7 and in addition to this, in addition, another-preferred embodiment of the present invention is disclosed-for a semiconductor structure with-photoresistance μ surface ^ photoresistance is corrected on-optics The η removal of the element includes the following steps: First, " Λ, the space between the separated photoresist layers is injected with a pH value less than 7

0503-A30493TWF 1243409 /文潤流體，接著提供一光能量直接穿過該浸潤流體至該光卩且居上再者，本發明之再一較佳實施例係揭露一對具有一光阻^形成於其上表面之半導體結構照光(illuminating)的方法，該法係包括町步驟·首’先上在一光學元件之表面及一與其相隔的光阻層之間的空間注入pH 、浸潤流體，接著照射一光線直接穿過該浸濶流體至該光阻層上，的線之波長較佳係小於450奈米。 /、〆光為使本發明之結構、操作方法及特徵能更_賴，下施例，並配合所附圖式，作詳細說明如下：、牛乂土貫【實施方式】統及^本^具_錄實糊，魏明符合本發—式微影系 _式微心仏九源20,而邊光源2〇發射一光能量過-透鏡22，織這麵量束2_—鮮3Q和—絲元雜㈣，= 的—最外她5G °娜外峨5G和感光材料空間有-浸潤流體60填充，而感光材料7〇係形成於—半導體元 =較佳實施例中’該半導體元件基板8〇可以是其上以形成有積體電路的半導體基板。舉例來說，該丰暮辦- 、砂曰从⑽.〜α 件基板⑽可以是—具有電晶體之石夕曰曰基姉物.-早晶雜板或是―錢絕緣板）。而該感光㈣7〇可以是_轨層或是其罩維中，感光材料70可以被圖形化成 + &季乂仏貝關形化感光材料層可用來作為，例如， ^寸之® 刻罩幕，亦可絲製作長度5G奈米^^树(或是其他傳導材料)之餘外，該圖形化感光材料層亦可用來白、金屬乳化丰導體(M〇S)閘道。此 t作为200奈米或其以下尺寸的金屬導0503-A30493TWF 1243409 / Wen Run fluid, and then provide a light energy directly through the infiltration fluid to the light beam and above it, another preferred embodiment of the present invention is to expose a pair of photoresist ^ formed on A method for illuminating a semiconductor structure on an upper surface of the semiconductor structure. The method includes the steps of: firstly, injecting a pH, a wetting fluid, and then irradiating a space between the surface of an optical element and a photoresist layer spaced therefrom A light beam passes directly through the immersion fluid to the photoresist layer, and the wavelength of the line is preferably less than 450 nm. In order to make the structure, operation method and features of the present invention more detailed, the following examples and the accompanying drawings will be described in detail as follows: With _recording true, Wei Ming conforms to the present-style lithography system_style micro-heart 仏 Jiuyuan 20, while the side light source 20 emits a light energy over-lens 22, weaving this surface beam 2_— 鲜 3Q 和 — 丝元Miscellaneous, =-the outermost 5G ° Na 5e and the photosensitive material space is filled with-infiltration fluid 60, and the photosensitive material 70 is formed in-semiconductor element = in the preferred embodiment 'the semiconductor element substrate 8o. It may be a semiconductor substrate on which an integrated circuit is formed. For example, the Feng Mu Office, Sand said from ⑽. ~ Α pieces of substrate ⑽ can be-Shi Xi Yue said with a transistor.-Early-crystal hybrid board or "money insulation board". The photosensitive material 70 can be a _ track layer or its cover dimension, and the photosensitive material 70 can be patterned into a + & quarter-shaped shaped photosensitive material layer can be used as, for example, ^ inch of ® engraved mask In addition to making 5G nanometer trees (or other conductive materials), the patterned photosensitive material layer can also be used for white and metal emulsion conductors (MOS) gateways. This t acts as a metal guide for sizes of 200 nm and below

0503-A30493TWF 1243409 線(例如：銅金屬鑲嵌線）。該半導體元件基板80係被一晶圓支撐台座85所支樓。請泉照第1圖，該浸潤流體60係配置在該最外層透鏡50及該感光材料7〇之間。在此為了要簡化並強調本發明，因此只繪出該最外層透鏡50及該感光材料7〇之間的^:潤流體60。然而，在該感光材料70之圖形化的過程十，該基板⑽及/ 或該台座85可以被浸潤在該浸潤流體6〇中。第2a圖係為該微影系統1〇之該最外層透鏡5〇、該感光材料與其之間的該浸潤流體60的放大示意圖。該最外層透鏡5〇係與該浸潤流體6〇相接觸。在一傳統微影系統中，該浸潤流體60係為水。然而，其他例如環辛烷和過氟聚醚(PFPE)亦可作為浸潤流體60。該浸潤流體6〇包含有氫氧離子 (OH) ’斋忒次潤流體60係水，氫氧離子會因水的解離而存在，如以下之平衡式所示： Η20(1Γ>Η+㈣+ΟΙΓ㈣（公式 I) 其中Η+是氫軒，〇Η·是餘軒。丨及aq符號分別代表液體與水溶液狀態。浸潤流體60係與該感光材料7〇之上表面9〇相接觸，如第％圖所示，在介面90和一部分的感光材料或是光阻7〇接觸。其中，該感光材料70可例如為-以193奈米、157.奈米或是更小的波長做為影像光源的光阻層。當預定區域的感光材料70在—㈣量的光能量束21下曝光時，則被曝光部份的感光材料70會產生—光催化劑。該感光材料％可例如為一化學增幅型(CA)光阻，其可廣泛的顧於具有193奈米或157奈米波長的微影技術中。該藉由曝光所產生的催化劑通常係一可釋放出酸的催化劑，通常用HA表示。舉例來說，催化劑似會質子化一光阻高分子材料賴類官能基，形成較易溶解的酸並且同時再產生質子或是氣離子(h+)，這個質子或是氳離子會再去質子化其他醋類官能基，然後再形成其他會溶解的酸並又再生成H+。這個質子化、形成可溶解的酸類、再生質子等連續的反應叫做0503-A30493TWF 1243409 wire (for example: copper metal inlaid wire). The semiconductor element substrate 80 is supported by a wafer support base 85. As shown in FIG. 1, the infiltration fluid 60 is disposed between the outermost lens 50 and the photosensitive material 70. In order to simplify and emphasize the present invention, only the fluid 60 between the outermost lens 50 and the photosensitive material 70 is drawn. However, during the patterning process of the photosensitive material 70, the substrate and / or the pedestal 85 may be wetted in the wetted fluid 60. Figure 2a is an enlarged schematic view of the outermost lens 50 of the lithography system 10, the photosensitive material and the wetting fluid 60 therebetween. The outermost lens 50 is in contact with the infiltration fluid 60. In a conventional lithography system, the infiltration fluid 60 is water. However, other materials such as cyclooctane and perfluoropolyether (PFPE) may be used as the wetting fluid 60. The infiltrating fluid 60 contains hydroxide ions (OH) 'Zaiyu Jirun fluid 60 series water, hydroxide ions will exist due to the dissociation of water, as shown in the following equilibrium formula: Η20 (1Γ > Η + ㈣ + ΟΙΓ㈣ (Formula I) where Η + is hydrogen, 〇Η · is Yuxuan. The symbols 丨 and aq represent the state of liquid and aqueous solution, respectively. The infiltration fluid 60 is in contact with the surface 90 of the photosensitive material 70, as As shown in the figure, the interface 90 is in contact with a portion of a photosensitive material or a photoresist 70. Among them, the photosensitive material 70 may be, for example, 193 nm, 157. nm, or a smaller wavelength as the image light source. When the photosensitive material 70 in a predetermined area is exposed under a large amount of light energy beam 21, the exposed portion of the photosensitive material 70 will generate a photocatalyst. The percentage of the photosensitive material may be, for example, a chemical increase. Type (CA) photoresist, which can be widely used in lithography technology with a wavelength of 193 nm or 157 nm. The catalyst produced by exposure is usually a catalyst that can release acid, which is usually represented by HA For example, the catalyst seems to protonate a photoresistive polymer material Lai-type functional groups form a more soluble acid and generate protons or gas ions (h +) at the same time. This proton or europium ion will deprotonate other vinegar functional groups, and then form other soluble acids and H + is formed again. This continuous reaction such as protonation, formation of soluble acids, regeneration of protons is called

0503-A30493TWF 9 1243409 化學增幅型反應。區域100 第2b圖係顯示浸潤流體60(水)與已曝光的感光材料7〇之間界面如的 -個放大透視圖100。值得注意的是，該可釋放出酸的催化劑可能以似的形式存在或是解離成H+和A.之形式。如同本發明所教示的，該浸潤流體6〇 t如有大量的氫氧離子存在是十分不適#的，_該賴流體⑹的氯氧離子110會擴散到該感光材料7〇與浸潤流體6〇接觸的表面，並且中和該酸催化劑。因此，在該感光材料70與浸潤流體6〇接觸的區域，該感光材料 70照光所產生的酸催化劑會進一步被消耗，導致在鄰近該界面卯的該感光材料70其所進行的化學增幅型反應速率下降。請參照第3a圖，在例如以氫氧化四甲銨(TMAH)溶液作為顯影液顯影該曝光後之感光材料70(光阻)之後，該光阻曝光的部分2〇〇會被溶解。然而，由於被曝光的感光材料70在其鄰近界面9〇的區域之化學增幅型反應速率較低，使得其在顯影步驟的溶解範圍變小。這樣的結果導致如第如圖所不具有T形剖面的光阻線21〇的形成。因此，若是該感光材料表面不斷有酸催化劑被中和的情況產生的話，該圖形化後的感光材料70會具有較寬之線寬Li。 ’ 根據本發明之一較佳實施例，該浸潤流體6〇的〇ff離子濃度係被控制以低於10 We/l(或是m〇1/dm3，其中m〇1.、L和dm符號分別代表莫耳、公升和公寸）。本發明藉由減少〇H_離子的濃度使其小於1(r7m〇ie/L，如此來，在已曝光的光阻表面區域的酸催化劑被消耗的量會受到壓制。因此，藉由減少OH_離子的濃度及擴散到光關〇H•離子的量，該圖形化後的感光材料220會有如第3b圖所示的較佳線寬L2的光阻圖案。在浸潤流體60中加入過量的質子或是氳離子係為一種減少水中〇h離子的/辰度的方去。在水中加入額外的氫離子會使公式1的平衡式向左移動，如此一來可使OH-離子的濃度小於10_7m〇le/L。於浸潤流體6〇中加入酸可改變該浸潤流體6〇的氫離子濃度會，而酸的種類可例如為乙基氧酸或是甲0503-A30493TWF 9 1243409 Chemically amplified reaction. Area 100. Figure 2b shows an enlarged perspective view 100 of the interface between the infiltrating fluid 60 (water) and the exposed photosensitive material 70. It is worth noting that the acid-releasing catalyst may exist in a similar form or dissociate into the form of H + and A. As taught by the present invention, the infiltration fluid 60t is very uncomfortable if a large number of hydroxide ions are present. The chloride ion 110 of the lysing fluid will diffuse to the photosensitive material 70 and the infiltration fluid 60. The contacted surface and neutralizes the acid catalyst. Therefore, in the area where the photosensitive material 70 is in contact with the infiltrating fluid 60, the acid catalyst generated by the photosensitive material 70 light is further consumed, resulting in a chemically amplified reaction performed by the photosensitive material 70 adjacent to the interface. The rate drops. Referring to FIG. 3a, after the exposed photosensitive material 70 (photoresist) is developed using, for example, a tetramethylammonium hydroxide (TMAH) solution as a developing solution, the exposed portion 200 of the photoresist will be dissolved. However, the chemically amplified reaction rate of the exposed photosensitive material 70 in the region adjacent to the interface 90 is low, so that its dissolution range in the developing step becomes smaller. Such a result leads to the formation of a photoresist line 21o which does not have a T-shaped cross section as shown in FIG. Therefore, if an acid catalyst is continuously neutralized on the surface of the photosensitive material, the patterned photosensitive material 70 will have a wide line width Li. '' According to a preferred embodiment of the present invention, the 0ff ion concentration of the infiltration fluid 60 is controlled to be lower than 10 We / l (or m〇1 / dm3, where m01, L, and dm symbols (Representing Mor, liter, and liter). In the present invention, the amount of acid catalyst consumed in the exposed photoresist surface area is suppressed by reducing the concentration of OH ion to less than 1.0 (r7mioie / L). Therefore, by reducing the OH _ The concentration of ions and the amount of ions diffused to the light source, the patterned photosensitive material 220 will have a photoresist pattern with a better line width L2 as shown in FIG. 3b. An excessive amount of immersion fluid 60 is added. The proton or erbium ion system is a way to reduce the 0h ion in the water. Adding extra hydrogen ions to the water will move the equilibrium formula of formula 1 to the left, so that the concentration of OH- ions is less than 10_7mole / L. Adding an acid to the infiltrating fluid 60 can change the hydrogen ion concentration of the infiltrating fluid 60, and the type of acid can be, for example, ethyloxy acid or formic acid.

0503-A30493TWF 10 1243409 基氧酸等有機酸’亦可柄鹽酸或是稀硫酸等無機酸，亦可城合用之。、、曲因此’根據本發明之—難實關，驗潤趙具有—較過量的氯離 ^辰度以減低伟式+氫氧離子的濃度，減本發明，紐職體中的氨料的濃度較佳應大於⑽敵，也就是說該浸潤流體6〇的pH值應該取好1、於7 ’風軒的濃度結溫(㈣度)下比較好在約爪7缝化至約讥減/L的範圍内，或者在約‘ο·至約i〇-4m〇ie/L的範圍内，或者在、’=() mole/L至約Kr5m()le/L的翻内’甚至最佳係在㈣々mow 至約1〇咖1e/ L的範圍内。符合以上氫離子濃度的條件下，浸潤流體的 PH值係小於7，較佳係在約2至7之間，更佳係在約4至7之間或約$至 :之間’甚至最佳在係在約6至7之間。pH值定義為切幻，其中[幻是虱離子的料濃度’在制流體6G巾加人酸可進—錢善光_化學放大效應。 *第^圖係顯示該浸潤流體6〇(即水)與最外層透鏡50接觸的截面圖，而弟^圖雜秘雕體6G(水)與最外層透鏡％之暇學表面Μ的放大透視圖’該最外層透鏡5G之表面有可能會有極小部份溶於浸潤流體卜魏鏡嚇_二氧切、树、氣化__是氣蝴卿。以本㈣之1佳實施例所使用的吨化触鏡材料⑽ 鈣離子(Ca2+)和就離子(κ)，如下所示： ·Μ办成0503-A30493TWF 10 1243409 Organic acids such as oxyacid 'can also be treated with inorganic acids such as hydrochloric acid or dilute sulfuric acid, and can also be used in combination. According to the present invention—difficult to practice, Zhaorun Zhao has—a relatively large amount of chlorine ionization to reduce the concentration of Wei + hydroxide ion, and reduce the ammonia content in the New Zealand body according to the present invention. The concentration should preferably be greater than the enemy, that is to say, the pH value of the infiltrating fluid 60 should be good. 1. It should be better at a junction temperature (㈣) of 7 'Fengxuan. / L, or in the range of about 'ο · to about 〇-4m〇ie / L, or in the range of' = () mole / L to about Kr5m () le / L 'or even the most The best range is from ㈣々mow to about 10 coffee 1e / L. Under the conditions of the above hydrogen ion concentration, the pH value of the infiltrating fluid is less than 7, preferably between about 2 to 7, more preferably between about 4 to 7 or about $ to: 'or even the best. The tie is between about 6 and 7. The pH value is defined as cut magic, where [magic is the material concentration of lice ions' and the acid can be added to the fluid 6G towel—Qian Shanguang_Chemical amplification effect. * Figure ^ shows a cross-sectional view of the infiltrating fluid 60 (that is, water) in contact with the outermost lens 50, and Figure ^ is a magnified perspective of the miscellaneous sculpture 6G (water) and the outermost lens% Figure 'The surface of the outermost lens 5G may have a very small part dissolved in the infiltrating fluid. Wei Wei Jing _ dioxin, tree, gasification _ is Qi butterfly. Taking the tonified contact lens material used in the first preferred embodiment of the present invention, the calcium ion (Ca2 +) and the ion (κ) are as follows:

CaF2(s)->Ca2+(aq)+2F(aq) 公式(II) 在室溫下’約猶4莫耳的固體氟化妈可溶於PH值為⑷公升水中。該浸潤流體雜持-定的，如此—來，化猶鏡養才會以—固定濃 ί 水較。轉的量會目社翻_日_增加(如 t，'m__溶解度不相同，以致於造成透鏡表面的又'嚴、。甚至會造成影像扭曲及儀器故障等情形發生。将。f水:在不同pH值(或是酸度)的水中，其莫耳溶解度的關 '、。虽7 ’ P從7降低時，也就是酸性增加，邮的溶解度也會因而增CaF2 (s)-> Ca2 + (aq) + 2F (aq) Formula (II) At room temperature, about 4 moles of solid fluorinated molybdenum is soluble in water with a pH of ⑷ liters. The infiltration fluid is heterogeneous-fixed, so that—in the future, the chemical culture will be fixed—thick water. The amount of rotation will be increased by the number of days (such as t, 'm__, solubilities are not the same, which will cause the lens surface to be' rigorous'. It may even cause image distortion and instrument failure. Will be .f water: In water with different pH value (or acidity), its Moore's solubility is important. Although 7 'P decreases from 7, it means that the acidity increases, so the solubility of the post will also increase.

0503-A30493TWF 1243409 ΐ 4 θ' ^CaF2 ° 離子奶县二曰=、原因主要係因為氣離子的濃度。若氫離子過量，則氫溶液的產生·、11與鼠離子(F)結合而使平衡式向右獅，導致氫氟酸(HF)水 H(aq)+F(aq) ->HF(aq)公式(ΙΠ) 因為氟離子在產生氫氟酸時被消耗了，所以公式(II)的平衡式便合向右移動，造成更多的邮固體溶解，如此一來便會加速透鏡caF2材㈣^ 因此’當pH值維持於7以下時，雖可減少對酸催化劑消耗的影響，但阳不可太低判右太低則會導致Cab透鏡材料嚴重的溶解。因此本發明所述之浸潤流體其PH值大體係在小於7的範圍，較佳係在2至7，更㈣在4至7，最佳則是在5到7，甚至在6到7之間。、，根據本^明之另—I父佳貫施例可知，利賴離子效應可以減少透鏡材例如’若外層透鏡SG之材㈣c迅，舰浸淑體⑽(水）含有4濃度的氟離子，即可壓抑邮的溶解。根據_子效應，額外添加的氟離子會使公式⑼向左邊移動，可有效的壓抑邮的溶解。一請參照第6圖，隨著浸潤流體内之氟離子濃度的增加，則CaF2的莫耳 /合解度會減少。具體的作法可為在水中加人高溶解性的含氟的化合物，例城化納、氟化卸、氫氣酸或是以上之混合，以本發明之另—較佳實施例來况’齡氟之化合物氫鏡較佳麵氫氟酸，而讀氟_氣化納的混合尤佳。本發明所述之制流體其氟離子濃度係大於疆·趾，較佳係大於0.05mole/L，最佳係大於01 m〇le/L。此外，值得注意的是，本發明所述之浸潤式微影系統更可包含其它已知適用於浸献微影技術的作法，舉例來說，紐潤式微影祕可以在最外層透鏡和被曝光部分的晶圓之間用浸潤流體來浸潤；另一作法則是將整片晶圓浸潤在該浸·體巾;再者，亦可將整條台都浸潤在紐潤流體中。0503-A30493TWF 1243409 ΐ 4 θ '^ CaF2 ° Ionic milk county II =, the reason is mainly due to the concentration of gas ions. If the hydrogen ion is excessive, the generation of hydrogen solution, 11 and the rat ion (F) combine to make the equilibrium to the right, resulting in hydrofluoric acid (HF) water H (aq) + F (aq)-> HF ( aq) Formula (II) Because the fluoride ion is consumed when generating hydrofluoric acid, the balance of formula (II) moves to the right, causing more postal solids to dissolve, which will accelerate the lens caF2 material. ㈣ ^ Therefore, when the pH value is maintained below 7, although the effect on the consumption of the acid catalyst can be reduced, the positive and negative values cannot be too low, which will cause serious dissolution of the Cab lens material. Therefore, the infiltration fluid of the present invention has a large pH value in the range of less than 7, preferably 2 to 7, more preferably 4 to 7, and most preferably 5 to 7, or even 6 to 7. . According to another example of this and the first example by the father and the father, the favorable ion effect can reduce the lens material such as' if the material of the outer lens SG is fast, the ship immersion body (water) contains 4 concentrations of fluoride ions, Can suppress the dissolution of the post. According to the sub-effect, the additional fluoride ion will move the formula ⑼ to the left, which can effectively suppress the dissolution of the post. Please refer to Fig. 6. As the fluoride ion concentration in the infiltrating fluid increases, the molar / combination degree of CaF2 decreases. The specific method may be adding a highly soluble fluorine-containing compound to the water, such as sodium sulfide, fluorinated hydrogen, hydrogen acid, or a mixture of the above. According to another-preferred embodiment of the present invention, the "fluorine" The compound hydrogen mirror is preferably facing hydrofluoric acid, and the reading of fluorine-gasification soda is particularly preferred. The fluoride ion concentration of the production fluid of the present invention is greater than that of Xinjiang · Toe, preferably greater than 0.05 mole / L, and most preferably greater than 01 mole / L. In addition, it is worth noting that the immersion lithography system described in the present invention may further include other methods known to be suitable for immersion lithography. For example, the new-type lithography can be applied to the outermost lens and the exposed part. Infiltration fluid is used to infiltrate between the wafers; another method is to infiltrate the entire wafer into the immersion body towel; furthermore, the entire table can be infiltrated into the fluid.

0503-A30493TWF 12 1243409 雖然本發明已以-較佳實施姻露如±，料並翻錄定本發明，任何熟習此技藝者’在不脫縣發明之精神和範_，#可作些許之更動與潤飾，a此本發明之職範目當視後附之巾鱗婦_界定者為準。 0503-A30493TWF 13 1243409 【圖式簡單說明】第1圖係顯示一浸潤式微影技術系統的示意圖。第2a圖及第％圖係說明浸潤流體(例如：水)之氫氧基(〇tr)與欲曝光的光阻層(感光材料)之間所產生之作用的示意圖。第3a圖係顯示受浸潤流體中之驗(氳氧基、〇H-)污染的光阻層其戶斤|有之T型剖面的示意圖。第3b圖係顯示末受浸潤流體中之鹼(氫氧基、0Η·)污染的光阻層其所具有之較佳光阻剖面的示意圖。第4a圖和第牝圖係說明浸潤流體(例如··水)之氫基(矿)與光學元件隨鏡材料)之間所產生之作用的示意圖。第5圖係說明不同pH值的浸潤流體下與氣化妈透鏡之溶解度的關係。第6圖係顯示不同浸潤流體的F濃度與氟化鈣透鏡溶解度的關係。【主要元件符號說明】影像光源〜20 ; 透鏡〜22 ; 光學元件模組〜40 ; 最外層透鏡〜50 ; 感光材料〜70 ; 晶圓支撐台座〜85 ; 放大透視圖〜1〇〇、3〇〇 ; 光阻曝光的部分〜200 ; 光阻線〜220 ; 水〜H2〇 ; 催化劑〜HA ; 線寬〜L、L2 ; 浸潤式微影技術系統〜1(); 光能量束〜21 ; 遮罩〜30 ; 光學表面〜51 ; 浸潤流體〜60 ; 半導體元件基板〜8〇 ; 感光材料之上表面〜9〇 ; 擴政至感光材料之氫氧離子〜11〇 ; 具有T形剖面的光阻線〜21〇 ; 氫氧離子〜ΟΙΓ ; 氫離子〜H+ ; 催化劑之酸根〜A-;0503-A30493TWF 12 1243409 Although the present invention has been implemented in a preferred manner, such as ±, the present invention is expected to be transcribed and transcribed. Anyone skilled in this art 'is in the spirit and model of the invention in Buxian County. aThis job description of the present invention shall be subject to the attached scale_wife. 0503-A30493TWF 13 1243409 [Brief description of the drawings] Figure 1 shows a schematic diagram of an immersion lithography system. Figures 2a and% are schematic diagrams illustrating the effect between the hydroxyl group (0tr) of the infiltration fluid (e.g., water) and the photoresist layer (photosensitive material) to be exposed. Fig. 3a is a schematic diagram showing a T-shaped cross section of a photoresist layer contaminated with osmium (OH, OH-) in an infiltrating fluid. Figure 3b is a schematic diagram showing a preferred photoresistive section of a photoresist layer that is not contaminated with alkali (hydroxyl, 0Η ·) in the infiltration fluid. Figures 4a and 牝 are schematic diagrams illustrating the effect between the hydrogen-based (mine) of an infiltration fluid (e.g., water) and the optical element with the lens material). Figure 5 illustrates the relationship between the solubility of the gasification lens and the infiltration fluid at different pH values. Figure 6 shows the relationship between the F concentration of different infiltration fluids and the solubility of calcium fluoride lenses. [Description of main component symbols] Image light source ~ 20; lens ~ 22; optical element module ~ 40; outermost lens ~ 50; photosensitive material ~ 70; wafer support base ~ 85; enlarged perspective view ~ 100, 3〇〇; Photoresist exposed part ~ 200; Photoresist line ~ 220; Water ~ H2〇; Catalyst ~ HA; Line width ~ L, L2; Immersion lithography system ~ 1 (); Light energy beam ~ 21; Mask ~ 30; Optical surface ~ 51; Wetting fluid ~ 60; Semiconductor element substrate ~ 80; Upper surface of photosensitive material ~ 90; Expanded to hydroxyl ion of photosensitive material ~ 11; Photoresistance line with T-shaped cross section ~ 21〇; hydroxide ion ~ 〇ΙΓ; hydrogen ion ~ H +; acid radical of the catalyst ~ A-;

0503-A30493TWF 14 1243409 氟化鈣〜CaF2 ; 鈣離子〜Ca2+ ; 氟離子〜Γ ; 氫氟酸〜HF。 0503-A30493TWF 150503-A30493TWF 14 1243409 Calcium fluoride ~ CaF2; Calcium ion ~ Ca2 +; Fluoride ion ~ Γ; Hydrofluoric acid ~ HF. 0503-A30493TWF 15

Claims

124340S124633號申請專利範圍4严於·-—— _正日期：94.7.27 ^日條(灸)正替換贾十、申請專利範圍·· 一— 一一 1·一種浸潤式微影系統，包含：一光學表面；以及一 pH值小於7的浸潤流體，其中該浸潤流體至少與一部份之該光學表面接觸。 2.如申請專利範圍第1項所述之浸潤式微影系統，其中該浸潤流體包含水。 3·如申請專利範圍第2項所述之浸潤式微影系統，其中該浸潤流體之 pH值係介於2至7之間。 4.如申請專利範圍第3項所述之浸潤式微影系統，其中該浸潤流體之 pH值係介於4至7之間。 5·如申請專利範圍第4項所述之浸潤式微影系統，其中該浸潤流體之 pH值係介於5至7之間。 6.如申請專利範圍第5項所述之浸潤式微影系統，其中該浸潤流體之 pH值係介於6至7之間。 7·如申請專利範圍第1項所述之浸潤式微影系統，其中該浸潤流體之氫離子濃度係介於KT7mole/L至l(T2mole/L的範圍内 8·如申請專利範圍第1項所述之浸潤式微影系統，其中該浸潤流體之氫離子濃度係介於l(T7mole/L至10_4mole/L的範圍内 9.如申請專利範圍第1項所述之浸潤式微影系統，其中該浸潤流體之氫離子濃度係介於l(T7mole/L至l(T5mole/L的範圍内 10·如申請專利範圍第1項所述之浸潤式微影系統，其中該浸潤流體之氫離子濃度係介於l(T7mole/L至10_6mole/L的範圍内。 11·如申請專利範圍第1項所述之浸潤式微影系統，其中該光學表面包含二氧化石夕。 12.如申請專利範圍第1項所述之浸潤式微影系統，其中該光學表面包 0503-A30493TWF1 16 543409 ~ 月修(戈)正替換頁含熔矽(fused silica)。 13. 如申請專利範圍第丨項所述之浸潤式微影系統，其中該光學表面包含氟化約。 14. 如申請專利範圍第13項所述之浸潤式微影系統，更包含一含氟之化合物溶於該浸潤流體中。 I5·如申請專利範圍第14項所述之浸潤式微影系統，其中該含氟之化合物係擇自由氟化鈉、氟化卸、氫氟酸及其所組合之族群中。 16·如申請專利範圍第13項所述之浸潤式微影系統，其中該浸潤流體之氣離子》辰度係大於0.01mole/L。 17. 如申睛專利範圍第ι6項所述之浸潤式微影系統，其中該浸潤流體之氟離子》農度係大於0.05mole/L。 18. 如申凊專利範圍第I?項所述之浸潤式微影系統，其中該浸潤流體之氣離子濃度係大於0.1mole/L。 19·如申請專利範圍第i項所述之浸潤式微影系統，更包括一半導體元件基板位於該光學表面下方，其中該半導體元件基板之最上層具有一光阻層。 2〇·如申請專利範圍帛19項所述之浸潤式微影系統，其中該細層包含化學增幅型光阻。 21. 如申請專難目第19項所述之制式微影祕，其巾紐潤流體係與該光阻層之一部分接觸。 22. 如申請專利範圍第19項所述之浸潤式微影系統，其中該半導體元件基板係浸潤在該浸潤流體中。 23·如申請專利範圍第19項所述之浸潤式微影系統，更包括一支撐台座配置於該半導體元件基板之下。 24·如申請專讎圍第23顧述之湖式微影祕，其中該支撐台座係浸潤在該浸潤流體中。 0503-A30493TWF1 17 正替換頁 95 ’種β潤式微影系統，其具有一波長小於197nm的影像光源，包含: 一光學表面； PH值小於7的水溶液，該水溶液至少與一部份之該光學表面接觸；以及 ^半導體元件基板，其中該半導體元件基板之最上層具有一光阻層，光a層之—部分係與該水溶液接觸。 26·如申請專利範圍第25項所述之浸潤式微影系統，其中該水溶液之 pH值係介於2至7之間。 27·如申請專利範圍帛％項所述之浸潤式微影系統，其中該水溶液之 pH值係介於5至7之間。 28·如申請專利範圍第27項所述之浸潤式微影系統，其中該水溶液之 pH值係介於6至7之間。含二=11請專纖圍第25項所述之制式微影魏，射該光學表面包含氟m㈣專娜圍第25顿述之浸㈣微料統，財該光學表面包合物25細㈣嶋㈣含-含氣之化 32·如申請專利範圍第31項所述之浸潤一物係擇自由氣化納、氟化卸、氫氟酸及其所組合之族群中、。該3氣之化合 33.如申請專利範圍第25項述之 ^ 。離子濃度係大於_mGle/L。心“錢，其中該水溶液之亂 34·如申請專利範圍第25項所述之浸潤式微化學增幅型光阻。凡"甲涊九阻層包含 35.如t請細讓25項舰之勤試微料基板係浸潤在該水溶液中。 /、中導體70件 0503-A30493TWF1 18 1243^ 4Θ9—-_ — 月Θ日修(致)正替換頁 36·如申請專利範i第25項所述之浸配置於該半導體元件基板之下。 ^统，更包括—切台座 37·如申請專利範圍第36項所述之浸潤式浸潤在該水驗巾。錢’財該切台座係 =·-種對具有—光阻層形成於其上之铸體結構導入-PH值小於7的浸潤流體於—光學、去’包含：表面及—光阻層間的空間柁以及提供一光能量直接穿過該浸潤流體至該光阻層上。 39·如申請專利範圍第％項所述之對具有—光體結_光的方法，其中該浸潤越包含水。 '於其上之半導 4〇.如申請專利範圍第38項所述之對具有一體結構照光的方法，財該浸潤越之pH值係介於2^^上之半導 41·如申請專利細第4G項所述之對具體結構照光的方法，其中該浸潤流體之pH值係介於4至7之;之半導 42. 如申請專利範圍第41項所述之對具有一光阻層形^間體結構照光的方法，其中該浸潤流體之pH值齡於///於其上之半導，士，/ fm 〇 43. 如申請專利範圍第42項所述之對具有—光阻層形成於其體結構照光的方法，其中該浸潤流體之pH值係介於6 牛钕、王 / 間〇 44. 如申請專鄕圍第38柄述之對具有—光阻層形纽其體結構照光的方法，其中該浸潤流體之氫離子濃度係介於…·7 、 l(T2mole/L 的範圍内。 mole/L 至 45·如申請專利範圍第44項所述之對具有—光阻層形成於盆上體結構照光的方法，其中該浸潤流體之氫離子濃度係介於仞二' 10_4mole/L的範圍内、 mo e 至 46·如申請專利範圍帛μ項所述之對具有一光阻層形成於其上之半導體結構知、光的方法，其中該浸潤流體之氫離子濃度係介於1〇_7迅〇1^乙至 0503-A30493TWF1 19124340S124633 No. 4 patent application scope is stricter than --- _ Positive date: 94.7.27 ^ Japanese article (moxibustion) is replacing Jia X. Patent application scope ... One — one one 1 — An immersion lithography system, including: An optical surface; and an infiltration fluid having a pH value less than 7, wherein the infiltration fluid is in contact with at least a portion of the optical surface. 2. The immersion lithography system according to item 1 of the patent application scope, wherein the immersion fluid comprises water. 3. The immersion lithography system according to item 2 of the scope of patent application, wherein the pH value of the immersion fluid is between 2 and 7. 4. The immersion lithography system according to item 3 of the scope of patent application, wherein the pH value of the immersion fluid is between 4 and 7. 5. The immersion lithography system according to item 4 of the scope of the patent application, wherein the pH value of the immersion fluid is between 5 and 7. 6. The immersion lithography system according to item 5 of the scope of patent application, wherein the pH value of the immersion fluid is between 6 and 7. 7. The immersion lithography system described in item 1 of the scope of patent application, wherein the hydrogen ion concentration of the infiltration fluid is in the range of KT7mole / L to 1 (T2mole / L) 8. The immersion lithography system described above, wherein the hydrogen ion concentration of the immersion fluid is in the range of 1 (T7mole / L to 10_4mole / L. 9. The immersion lithography system according to item 1 of the patent application range, wherein the immersion The hydrogen ion concentration of the fluid is between l (T7mole / L to l (T5mole / L) 10. The immersion lithography system described in item 1 of the patent application range, wherein the hydrogen ion concentration of the infiltrating fluid is between l (T7mole / L to 10_6mole / L. 11. The immersion lithography system as described in item 1 of the patent application scope, wherein the optical surface contains dioxide. 12. As described in the first patent application scope The immersion lithography system described above, wherein the optical surface package 0503-A30493TWF1 16 543409 ~ Yue Xiu (Ge) is replacing the page containing fused silica. 13. The immersion lithography system described in item 丨 of the scope of patent application Where the optical surface contains a fluorinated approx. 14. The immersion lithography system according to item 13 of the patent application scope, further comprising a fluorine-containing compound dissolved in the immersion fluid. I5. The immersion lithography system according to item 14 of the patent application scope, wherein the fluorine-containing lithography system The compound is selected from the group consisting of free sodium fluoride, fluorinated unloading, hydrofluoric acid and combinations thereof. 16. The immersion lithography system as described in item 13 of the patent application scope, wherein the gas ions of the immersion fluid The degree is greater than 0.01 mole / L. 17. The immersion lithography system as described in item 6 of the Shen Jing patent scope, wherein the fluoride ion of the infiltrating fluid is greater than 0.05 mole / L. The immersion lithography system according to item I, wherein the gas ion concentration of the immersion fluid is greater than 0.1 mole / L. 19. The immersion lithography system according to item i of the patent application scope, further comprising a semiconductor element substrate It is located below the optical surface, wherein the uppermost layer of the semiconductor element substrate has a photoresist layer. 20. The immersion lithography system according to the scope of application patent No. 19, wherein the fine layer includes a chemically amplified photoresist. 21. According to the application of the lithography system described in item 19 of the Special Difficulty Project, the towel flow system is in contact with a part of the photoresist layer. 22. The immersion lithography system described in item 19 of the scope of patent application, The semiconductor element substrate is immersed in the immersion fluid. 23. The immersion lithography system described in item 19 of the scope of application for a patent, further comprising a support base disposed under the semiconductor element substrate. 24. If an application is required The 23rd Gushu's lake-type lithography secret, wherein the support platform is immersed in the immersion fluid. 0503-A30493TWF1 17 Positive Replacement Page 95 'Beta lithography system, which has an image light source with a wavelength less than 197 nm, including: an optical surface; an aqueous solution with a pH value less than 7, which is at least part of the optical surface Contact; and a semiconductor element substrate, wherein the uppermost layer of the semiconductor element substrate has a photoresist layer, and a portion of the light a layer is in contact with the aqueous solution. 26. The immersion lithography system according to item 25 of the scope of patent application, wherein the pH of the aqueous solution is between 2 and 7. 27. The immersion lithography system according to item 帛% of the scope of the patent application, wherein the pH of the aqueous solution is between 5 and 7. 28. The immersion lithography system according to item 27 of the scope of patent application, wherein the pH of the aqueous solution is between 6 and 7. Contains 2 = 11, the lithography system described in item 25 of the optical fiber, and the optical surface contains fluorine immersion micro-materials described in the 25th example of the optical fiber, and the optical surface inclusion compound 25 fine嶋㈣Containing-containing gas 32. As described in item 31 of the scope of the patent application, the infiltration of a substance is selected from the group consisting of free gasification, fluorination, hydrofluoric acid, and combinations thereof. The combination of the three gases 33. As described in item 25 of the scope of patent application. The ion concentration is greater than _mGle / L. "The money, in which the chaos of the aqueous solution is 34. As described in the scope of the application for patent scope of 25 types of immersion microchemical amplification type photoresistor. Where " Medium Nine barrier layer contains 35. If t, please make 25 items The sample substrate is immersed in the aqueous solution. / 70 middle conductors 0503-A30493TWF1 18 1243 ^ 4Θ9 — — — — Month Θ Day repair (to) Replacement page 36 · As described in the 25th item of the patent application The immersion is arranged under the semiconductor element substrate. The system also includes a cutting base 37. The immersion type infiltration in the water test towel as described in item 36 of the scope of patent application. A kind of infusion fluid having a photoresist layer formed thereon is introduced with an infiltrating fluid having a pH value of less than 7 to the optics, including the surface and the space between the photoresist layers, and providing a light energy to pass directly through the Wetting fluid onto the photoresist layer. 39. The method of having -photon junction_light as described in item% of the scope of the patent application, wherein the wetting more contains water. The method for illuminating light with an integrated structure as described in the 38th scope of the patent application The pH value of Run Yue is a semiconductor between 2 ^^. 41. The method of illuminating a specific structure as described in item 4G of the patent application, wherein the pH of the wetting fluid is between 4 and 7; Semiconductor 42. The method for illuminating an interstitial structure with a photoresist layer as described in item 41 of the scope of the patent application, wherein the pH value of the infiltration fluid is at the level of the semiconductor on the //, / fm 〇43. The method for irradiating light with a photoresist layer formed on the body structure as described in item 42 of the scope of application for patent, wherein the pH of the infiltration fluid is between 6 Nd, Wang / room 〇44. For example, the method for illuminating a structure having a photoresist layer-shaped button body structure described in Application No. 38, wherein the hydrogen ion concentration of the infiltrating fluid is in the range of ... 7, l (T2mole / L. Mole) / L to 45 · The method for irradiating a photoresist layer with a photoresist layer formed on the upper body structure as described in item 44 of the scope of the patent application, wherein the hydrogen ion concentration of the infiltration fluid is in the range of 仞 2 '10_4mole / L Mo, from 46 to 46. The half of the pair with a photoresist layer formed thereon as described in the scope of the patent application Known structure, light method, wherein the hydrogen ion concentration of the fluid wetting line between 1〇_7 fast 〇1 ^ B to 0503-A30493TWF1 19

HT mole/L的範圍内於其上之半導 l〇-7mole/L 至 47.如申請專利範圍第46項所述之對具有一光阻層形成體結構照光的方法，其中該浸潤流體之氫離子濃度係介於 U) mole/L的範圍内。 48·如申請專利範圍第38項所述之對具有一光阻層形成於其上之體結構照光的方法，其中該光學表面包含二氧化矽。 /、一 v 奶·如申請專利範圍第38項所述之對具有-光阻層形成於其上體結構照光的方法，其中該光學表面包含氟化鈣。 /、 5〇·如申請專利範圍第38項所述之對具有一光阻層體結構照辆方法，其中驗麻體包含水。成u之半導雕51.如申請專利範圍第5〇項所述之對具有一光阻層形成於其上之半曾體結構照光的方法，更包含-含II之化合物溶於該浸顺體巾。’、干¥ 氟化鉀、氫氟酸及其所組合之族群中 52.如申請專利制第51項所述之對具有—光阻層形成於其上體結構照光的方法，其中該含氟之化合物係擇自由敗化納、、 53.如申請專利範圍第49項所述之對具有一光阻声體結構照光的方法，其中該浸濁流體之氣離子濃度係大;;〇ϋ之半導 %如申請專利細第49項所述之對具有—触層形成糾上體結構照光的綠’其巾驗·撤㈣子濃度敍於⑽加。随。、 55·如中請專利綱第49項所述之對具有—光阻層形成於其上 -結構照光龄法’其巾該顏越之_子濃度敍純1咖随。 56.如申請補細第38項所述之對具有—光阻層形成於其上^ 體結構照光的方法，其中該光阻層包含化學增幅型光阻。、 57·如申請專利細第38猶述之對具有—光阻層形成於其上之體結構照光的方法’其中該浸濁流體係與該光阻層之—部八接觸、、 %如申請專利範圍第38項所述之對具有一光阻層形刀成於其^之半導 0503-A30493TWF1 20 ㈣ ——.__^ ~*----—— J '構'、、'光的方法，其中該半導體元件基板係浸潤在該浸潤流體中。 59·如巾請專利細第38項所述之對具有—光阻層形成於其上之半導 —、’、°構照光的方法，其中該半導體元件基板係配置於一支撐台库上。机如申請專利範圍第59項所述之對具有一光阻層形成^其上之半導構照光的方法，其中該支撐台座係浸潤在該浸潤流體中。、體請專利顧第38項所述之對具有—光阻層形雜其上之半導 m構知、光的方法，包含對該光阻層進行顯影。 =·如申請專利細第61項所述之對具有—紘飾絲其上之 ―:構照光的方法，其帽該光阻層進行顯影之步驟包括浸顺光阻層於氫氣化四甲銨溶液。曰及種對具有-光阻層形成於其上之半導體結構照光的方法，包么. 導入- PH值小於7的水溶液於-光學表面及—光阻層間的空間匕中3;以提供一光能量直接穿過該水溶液至該光阻層上，复佳係小於·奈米。 -中該錢之波長較 64·如申請專利範圍第63項所述之對具有一光阻層形體結構照光的方法，其中該水溶液之pH值係介於2至7之間之卞導 65. 如申請專利範圍第64項所述之對具有一光阻層形雜其上體結構照光的方法，其中該水溶液之pH值係介於5至7之間。〃 V 66. 如申請專利範圍第65項所述之對具有一光阻層形成曰於其體結構照光的方法，其中該水溶液之pH值係介於6至7之間。 ^ 67. 如申請專利範圍第63項所述之對具有—光阻層形成於其體結構照光的方法，其中該光學表面包含二氧化矽。、 V 68. 如申請專利範圍第63項所述之對具有一光阻層形成於其體結構照光的方法，其中該光學表面包含氟化鈣。、 ^ 69. 如申請專利範圍第63項所述之對具有-光阻層形成於其上之半導 0503-A30493TWF1 21 體、〜構Η?、光的方法，更包含一含氟之化合物溶於該水溶液中。 7〇·如申請專利範圍第69項所述之對具有一光阻層形成於其上之半導體結構照光的方法，其中該含1之化合物係擇自由氣化鈉、氟、Ρ 酸及其所組合之族群中。、風氣几如申請專利範圍第63項所述之對具有一光阻層形成於其上之體結構照光的方法，其巾該水溶液之氟離子濃賴大於a〇lm〇ie/L。丁、 •如申請專利範圍帛63項所述之對具有一雜層形成於其上之半首體結構照光的方法，其中該光阻層包含化學增幅型光阻。 V 73·如申請專利範圍第63項所述之對具有一光阻層形成於直體結構照光的方法，其巾該半導體元件基㈣制在該水_巾。V 74.如申請專利範圍第63項所述之對具有一光阻層形成於其上眷體結構照光的方法，其中該半導體元件基板係配置於一支撑么座上辱乃·如申請專纖圍第74項職之對具[紘層形^ ^ ° 體結構照光的方法，其中該支樓台座係浸潤在該水溶液中。；’、、 0503-A30493TWF1 22The HT mole / L ranges from 10-7mole / L to 47. The method of illuminating a structure having a photoresist layer-forming structure as described in item 46 of the patent application range, wherein The hydrogen ion concentration is in the range of mol / L. 48. The method of illuminating a body structure having a photoresist layer formed thereon as described in item 38 of the scope of the patent application, wherein the optical surface comprises silicon dioxide. A method of illuminating a photoresist layer with a photoresist layer formed on the body structure as described in item 38 of the patent application, wherein the optical surface includes calcium fluoride. / 、 50. The method of applying a photoresist structure to a vehicle as described in item 38 of the scope of the patent application, wherein the anaesthetic body contains water. The semi-conducting engraving 51. The method of illuminating a semi-tendron structure having a photoresist layer formed thereon as described in item 50 of the scope of the patent application, further comprising-dissolving a compound containing II in the dipping Body towel. 'Dry ¥ Potassium fluoride, hydrofluoric acid and their combined group 52. The method for irradiating light with a photoresist layer formed on the upper body structure as described in item 51 of the patent application system, wherein the fluorine The compound is selected to be freely destroyed. 53. The method for illuminating a photoresist with a photoresistive sound structure as described in item 49 of the patent application scope, wherein the gas ion concentration of the immersed fluid is large; 〇ϋ 之The semiconducting% is as described in item 49 of the patent application, and the concentration of the “green” which has a contact layer to form the corrective body structure and its light absorption and removal is described in detail. Follow. 55. As described in Item 49 of the Chinese Patent Application, the pair has-a photoresist layer is formed thereon-a structured photo-light age method ", and the towel of this yue-yin concentration of the sub-concentration is pure. 56. The method for illuminating a photoresist layer with a photoresist layer formed thereon as described in item 38 of the application, wherein the photoresist layer includes a chemically amplified photoresist. 57. As described in Patent Application No. 38, the method for illuminating a body structure having a photoresist layer formed thereon, wherein the immersion turbulence flow system is in contact with the photoresist layer— The pair described in item 38 of the range has a photoresist layer-shaped knife formed from its semiconductor 0503-A30493TWF1 20 ㈣ ——.__ ^ ~ * ----—— J 'struct' ,, 'light method Wherein the semiconductor element substrate is immersed in the immersion fluid. 59. The method for arranging light having a semiconductor having a photoresist layer formed thereon as described in item 38 of the patent application, wherein the semiconductor element substrate is arranged on a support library. The method for illuminating a semiconductor having a photoresist layer on the photoresist layer as described in item 59 of the scope of the patent application, wherein the support base is immersed in the immersion fluid. Please refer to the method described in Item 38 of the patent for the structure and light method of a semiconductor having a photoresist layer mixed thereon, including developing the photoresist layer. = · As described in item 61 of the patent application, the method of arranging light on the silk-covered light: the step of capping the photoresist layer for development includes dipping the photoresist layer in tetramethylammonium hydrogenate Solution. It refers to a method for illuminating a semiconductor structure having a -photoresist layer formed thereon, including a package. An aqueous solution having a pH value of less than 7 is introduced into the optical surface and the space between the photoresist layer 3 to provide a light. The energy passes directly through the aqueous solution onto the photoresist layer, and the compound is less than nanometer. -The wavelength of the money is more than 64. The method of illuminating a photoresist structure with a photoresist layer as described in item 63 of the patent application range, wherein the pH of the aqueous solution is between 2 and 7 and 65. The method for irradiating an upper body structure having a photoresist layer as described in item 64 of the scope of the patent application, wherein the pH of the aqueous solution is between 5 and 7. 〃 V 66. The method of illuminating a body structure having a photoresist layer as described in item 65 of the scope of patent application, wherein the pH of the aqueous solution is between 6 and 7. ^ 67. The method for irradiating light with a photoresist layer formed on a bulk structure as described in item 63 of the scope of the patent application, wherein the optical surface comprises silicon dioxide. V 68. The method for illuminating a body having a photoresist layer formed on a bulk structure as described in item 63 of the scope of the patent application, wherein the optical surface comprises calcium fluoride. ^ 69. As described in item 63 of the scope of patent application, the method for forming a semiconductor having a photoresist layer on which 0503-A30493TWF1 21 body, ~ ?,?, Light, and further comprising a fluorine-containing compound solution In this aqueous solution. 70. The method of illuminating a semiconductor structure having a photoresist layer formed thereon as described in item 69 of the scope of the patent application, wherein the compound containing 1 is selected from the group consisting of free gaseous sodium, fluorine, p-acid, and others. In the group of groups. 2. Atmosphere The method of illuminating a body structure having a photoresist layer formed thereon as described in item 63 of the scope of the patent application, the concentration of fluoride ions in the aqueous solution is greater than almolie / L. D. The method of illuminating a half-body structure having a heterolayer formed thereon as described in item 63 of the scope of patent application, wherein the photoresist layer comprises a chemically amplified photoresist. V 73. The method for illuminating a straight structure having a photoresist layer as described in item 63 of the scope of the patent application, wherein the semiconductor element is based on the water-towel. V 74. The method for illuminating a body structure having a photoresist layer formed thereon as described in item 63 of the scope of patent application, wherein the semiconductor element substrate is disposed on a supporting base. The method of illuminating the structure with the structure of [74layer shape ^ ^ °] around the 74th position, wherein the platform of the branch is soaked in the aqueous solution. ; ’, 0503-A30493TWF1 22