201009929 六、發明說明： 【發明所屬之技術領域】 液晶面板的基板、電子 形成之基板中’從基极 置。 本發明係關於於半導體晶圓、 電路基板等之使用阻劑來進行圖案 去除圖案形成後的阻劑之方法及裝 【先前技術】 於半導體、硬碟、液晶顯示器、 雷 顯示器等之製造製程中，於蝕列二 土板或平面 係於基板上形雜議㈣為保朗。在此，於 = 中被覆於對象物表面之聚合物殘渣等之無用物，必須= 步驟後予以祕而去除。在此，_膜的去除可使用^ 電漿灰化，⑵藉由化學藥品予以去除之技術。例如，對於 在各步驟變得無用之阻劑，1係採用藉由依據等向性電 衆之灰化而去除大部分’然後例如以硫酸與過氧化氣的混 合液，將殘餘的殘邊物予以溶解/分解而去除之去除方法^ 當植入能量較小時，由於變質層的厚度並非較厚，所 以可藉由等向性電漿處理及濕式處理，不會殘留殘渣而全 部去除。然而，於蝕刻後所生成之殘渣聚合物，或是高劑 量植入後之阻劑表面的變質層，則難以完全去除。尤其是 對於離子植入後的變質阻劑，隨著植入量的增加，亦增加 該去除的困難性。目刖一般為1 El 6ion/cm2的植入量，而 於此植入量之情形令，若進行一次的灰化，則於濕式洗淨 中可能有難以完全去除有機物之情況，而不得不進行複數 次相同步驟，且因情況不同有可能無法去除。此時會導致 320559 3 201009929 -成本提高且良率降低之問題。作為此離子植入後的阻劑剝 .離方法，例如揭示有-種於藉纟_Reactive⑹ .Etching :反應性離子蝕刻）進行處理後，進行下流式灰化 (down How ashing)來去除阻劑之技街（非專利文獻u。 [非專利文獻 ^Semiconductor World 1993. 3 P118 至 125 【發明内容】 (發明所欲解決之課題） • 近年來，隨著半導體裝置的高積體化 '高性能化，使 元件的精細化亦跟著進行《因此，即使有少許的殘渣殘留 於半導體基板上，亦成為產生缺失之原因，導致製品良率 的降低等問題。於前述非專利文獻.1中，雖然於論文中未 記載殘渣的產生，但藉由目前的分析技術對處理後的基板 進行解析’可確認到殘渣的產生。此可視為，若僅欲以電 漿處理來完全去除阻劑，變質層或未變質層中所包含之植 • 入的離子或雜質，與電漿及氣體之間會形成化合物=作為 殘渣殘留之故。再者，去除該殘渣乃極為困難。亦即，根 據#專利文獻1所記載的方法，會產生難以去除之殘涪， 結果成為製品缺失的產生之原因。 此外，對於離子植入後之變質層的去除，由於在離子 植入少驟中所植入之離子於阻劑上面較多，所以上面的變 質層軾厚而難以去除，使處理時間增長。若處 則因，，的熱容易產生凸爆(popping)。在此，時上的長凸 爆曰阻劑内部所殘留之水分或殘留的有機溶劑，因灰 320559 4 201009929 化時的加熱產生急速膨服而破裂之現象。再者’為人所知 . 者，因該凸爆而飛散於表面氧化膜之變質層，係難以去除。 因此，本發明為了解決上述課題，係以提供一種即使 是離子植入後的阻劑，亦不會殘留殘渣而可全部去除之方 法為目的。 (用以解決課題之手段） 本發明（1)為一種阻劑去除方法，是從具有表面為變質 層之阻劑的基板中去除阻劑之阻劑去除方法，其特徵為包 • 含：非等向性電漿處理步驟，係對前述基板進行非等向性 電漿處理來去除前述變質層的至少一部分；以及濕式洗淨 步驟，係於前述非等向性電漿處理步驟後，以處理媒體來 去除前述基板上的阻劑。 本發明（2)為前述發明（1)之阻劑去除方法，其中，在 前述非等向性電漿處理步驟後且為前述濕式洗淨步驟前， 更包含等向性電漿處理步驟，係對前述基板進行等向性電 0 漿處理來去除前述變質層。 本發明（3)為前述發明（1)或（2)之阻劑去除方法，其 中，於前述濕式洗淨步驟中，係使用臭氧水。 本發明（4)為前述發明（3)之阻劑去除方法，其中，係 對前述臭氧水進行加溫而予以使用。 本發明（5)為前述發明（1)至（4)中任一項之阻劑去除 方法，其中，於前述非等向性電漿處理步驟中，係施加偏 壓電力。 本發明C6)為前述發明（5)之阻劑去除方法，其中，係 5 320559 201009929 一邊調節前述偏壓電力的施加電力來進行。 本發明（7)為前述發明（1)至（6)中任一項之阻劑去除 . 方法，其中，於前述非等向性電漿處理步驟及/或前述等 向性電漿處理步驟中，係因應阻劑表面之變質層的形成條 件來控制電漿氣體的接觸時間，使未變質層的大部分殘留。 本發明（8)為前述發明（1)至（7)中任一項之阻劑去除 方法，其中，於前述非等向性電漿處理步驟及/或前述等 向性電漿處理步驟中，係因應於阻劑去除中所排出之反應 • 氣體的分析結果來進行步驟控制，使未變質層的大部分殘 留。 本發明（9)為前述發明（1)至（8)中任一項之阻劑去除 方法，其中，於前述非等向性電漿處理步驟及/或前述等 向性電漿處理步驟中，係將前述基板的溫度，維持在可提 供能夠以電漿來去除前述.變質層之熱能之溫度以上、且未 滿凸爆產生溫度之溫度。 ❹ 本發明（1 〇 )為一種阻劑去除系統（例如阻劑去除系統 SI、S2)，是從基板中去除表面為變質層之阻劑之阻劑去除 系統，其特徵為具備用以去除阻劑表面的變質層之非等向 性電漿處理裝置（例如非等向性電漿處理裝置100、非等向 性/等向性電漿處理裝置500)，此非尊向性電漿處理裝置 係具有：氣體供應部（例如氣體供應部111、511);電漿生 成部（例如電漿生成部130、530)，係對從前述氣體供應部 所供應之氣體進行電漿處理而生成電漿氣體；偏壓電力施 加部（例如偏壓電力施加部140、540)，係對前述電漿氣體 6 320559 201009929 • 賦予非等向性；以及機台部（例如機台150、550)，係使從 前述電漿生成部所供應之電漿氣體接觸於基板。 本發明（11)為前述發明（10)之阻劑去除系統（例如阻 劑去除系統SI、S2)，其係具有等向性電漿處理裝置（例如 等向性電漿處理裝置200、非等向性/等向性電漿處理裝 置 500) 〇 本發明（12)為前述發明（11)之阻劑去除系統（例如阻 劑去除系統S2)，其中，前述非等向性電漿處理裝置亦可 • 產生等向性電漿（例如非等向性/等向性電漿處理裝置 500) 〇 本發明（13)為前述發明（12)之阻劑去除系統（例如阻 劑去除系統S2)，其中，可進行前述偏壓電力施加部的導 通（ON)/切斷（OFF)控制（例如具有開關543之非等向性/ 等向性電漿處理裝置·500)。 · 本發明（14)為前述發明（13)之阻劑去除系統（例如阻 φ 劑去除系統S2 )，其中，前述偏壓電力施加部可進行施加 電力的調節（例如具有電力調整手段544之非等向性/等 向性電漿處理裝置500)。 本發明（15)為前述發明（11)之阻劑去除系統（例如阻 劑去除系統S1)，其中，前述等向性電漿處理裝置（例如等 向性電漿處理裝置200)係與前述非等向性電漿處理裝置獨 立地另外具有：氣體供應部（例如氣體供應部211);等向 性電漿產生部（例如電漿生成部220)，係對從前述氣體供 應部所供應之氣體進行電漿處理；以及機台部（例如機台 320559 201009929 * 230)，係使從前述等向性電漿產生部所供應之電漿氣體接 觸於基板。 . 本發明（16)為前述發明（10)至（15)中任一項之阻劑去 除系統（例如阻劑去除系統SI、S2)，其係具有濕式洗淨裝 * 置（例如濕式洗淨裝置300)。 本發明（17)為前述發明（16)之阻劑去除系統（例如阻 劑去除系統SI、S2)，其中，前述濕式洗淨裝置係具有： 處理媒體供應部（例如處理媒體供應部310);以及機台部 • (例如機台320)，係使從前述處理媒體供應部所供應之處 理媒體接觸於前述基板。 本發明（18)為前述發明（17)之阻劑去除系統（例如阻 劑去除系統SI、S2)，其更具有臭氧水生成部（例如臭氧水 生成部314) 〇 本發明（19)為前述發明（17)或（18)之阻劑去除系統 (例如阻劑去除系統SI、S2)，其係具有加熱前述處理媒體 φ 之加熱部（例如加熱部312)。 在此說明於本說明書中所使用之各種用詞的意義。所 謂的「變質層」，是指離子植入阻劑或側壁保護膜。所謂的 「系統」，不僅是指將各構成要件一體地收容之「裝置」， 即使各構成要件配置於物理上所區隔之位置（例如工廠）， 或是各構成要件彼此未連接為可進行資訊傳達，只要具備 申請專利範圍中所規定之功能之構成要件來構成全體，則 相當於該系統。所謂的「未變質層的大部分殘留」，是指不 去除未變質層，並且以不會產生因電漿處理所造成之殘渣 8 320559 201009929 之程度’使未變質層殘留。 (發明之效果） • 根據本發明（1)之方法，即使為離子植入後，亦不會殘 ‘ 留殘渣而可去除阻劑。此外，於非等向性電漿製程中，由 於去除速度較快，所以可進行低溫處理，而在不會 爆下進行處理。 凸 根據本發明（2)之方法，可達到即使當僅以非等向性電 ❼漿處理無法完全去除側面的變質層等時，亦可藉由接著該 非等向性電漿處理後連續進行之等向性電漿處理製程，而" 去除所殘餘之側面的變質層之效果。 根據本發明（3)之方法及本發明（18)之系統，藉由在濕 式洗淨步驟中使用臭氧水，可達到下列效果，例如，不需 使用如加熱硫酸般之使用上及保存上均較危險且對環户 ==樂劑’此外，不需使用如含有氟之對環境負擔較 乱體，而能夠在短時間内有效率地從基板去除 ❿ 生變質之p且劑。 矛' 面產 =本發明⑷之方法及本判⑽之系統，可 门、7的活性，而有效地去除阻劑之效果。 根據本發％⑸之方法，藉㈣ & 易使電激具有非等向性之效果。了達到】 電力树明⑻之方法，藉由-邊調節偏壓電力的施; 行水平方^，可制調節電㈣非等向性程度，而同^ 订尺千方向的電漿處理之效果。 夺2 根據本發明⑺之方法，不需無意義的延長電裝氣心 320559 9 201009929 接觸時間，可達到提高步锦 7根據本發明（8)之方法， 襞處理步驟及/或等向性電 的時間效率之效果。 根據本發明（9)之方法， 劑的去除之效果。 的時間效率之效果。 可於最佳時機停止非等向性電 後處理步驟，而達到提高步驟 可達到不會產生凸爆而促進阻 根據本發明（10)之系 到提高步驟的時間效率之 根據本發明（11)之系 裝置，可達到於進行非等 等向性電漿處理之效果。 統，可有效率地去除變質層，達 效果。 统，藉由更具有等向性電漿處理 向性電漿處理後，有效率地進行 ^據本㈣⑽，非等向性f漿處理裝置亦可 產生等向性電漿，藉此， 1·生電装處㈣達到更有效率地進行從非等向 性電装處理移至4向性電聚處理之步驟之效果。 根據本發明（13)之系 ^ ^ ^ 糸統，可進行偏壓電力施加部的導 通/切斷控制，藉此，可 了達到更有效率地進行非等向性/ 等向性的切換之效果。 ，據本發明（⑷之系統，藉由設定為可進行偏壓電力 的調_可達到調節電漿的非等向性程度，而同時進行水 平方向的電漿處理之效果。 根據本發明（15)之系統，當為非等向性電聚的處理時 間較長之試料¥ ’於非等向性處理結束後’再於其他反應 室進行等向性處理，藉此，可達到提升包含至濕式處理為 止之全體的處理量之效果。 10 320559 201009929 根據本發明⑽之系統，可達到可 - 洗淨步驟之效果。 双+地移在濕式 根據本發明⑽之系統，藉由所謂的 具有於電漿處理後可有效率地搬運至濕式反應^處理，乃 =處=發明為藉由葉片式處理來進行。洗= :=的再次附著)的問題之效果。:(=: 為^葉片式處理來進行滿式洗淨，當使=發明 具有適合於維持高溫高濃度的臭氧水之效果欠時，係 【實施方式】 <阻劑去除裝置> 第_一形熊_ 第1圖係顯示第-形態之阻劑 阻劑去除系⑽係由非等向性錄處理裝統^概略圖。 各裝置之間’配置有椒=裝40置0=構成。此外，於 續地進行全㈣者。在此較理想為可自動且連 可由對象物保持部4G卜用錢前述保動H疋， 402、以及可將該保持部4〇1及動段4 作部 度之支撐體403所構成。 調即於適當高 性電漿虛理-^ 非等向性電漿處理裝置1〇〇 a 非等向性電漿產生部120，係#^、有·耽體供應部ill; ^ '、隹'從前述氣體供應部所供庫 之_電聚狀態而產生非等向性電浆;以及機台： 320559 11 201009929 * 係設置基板並使前述電漿氣體接觸於該基板的表面。此^ 外，亦可因應必要而具有··將藉由前述電漿生成部所生成 . 之電漿氣體導引至處理對象物表面之導引手段16〇、處理 反應室170、或對前述處理反應室進行減壓之減屢手段 * 180。 非等向性電漿產生部120係具有：電漿生成部13〇， 係使從氣體供應部所供應之氣體成為電漿狀態；以及 電力施加部140，係用以對前述電漿賦予非等向性。電衆 籲 生成部130只要可使藉由氣體供應手段所供應之氣體形成 為電漿者，則無任何限定，例如，可具有高頻線圈132圍 • 繞該電漿生成部本體131之構成，再將高頻電源133連接 ' 於該高頻線圈，並以可供應預定頻率的電流之方式所連 接。此外，亦可採用該高頻以外之電漿生成機構。例如有 ECR(Electron Cyclotron Resonance:電子迴旋加速器共 振）電漿、ICP(Inductively Coupled Plasma :電感耦合電 ❿ 漿）電漿、螺旋波電漿等。 偏壓電力施加部140係具有偏壓電極141、以及對前 述偏壓電極施加電力之偏壓電源142。 由於因本裝置所進行之電漿處理而在基板上產生熱， 或是因溫度過低而無法進行依據電漿之變質層的去除”，'因 j機台15G較佳為設置可冷卻/加熱該基板之機台溫度調 節M90在此，機台溫度調節部⑽並無特別限定，例 如可由^度控制用的溫水/冷水生成部191及圖中未顯示 的水循壤抓路所構成。藉此，可藉由從該溫水/冷水生成 12 320559 201009929 - 部所供應之溫水或冷水對該基板進行加熱或冷卻，而將基 板上的溫度設定為預定溫度。 此外，減壓手段180只要可降低處理反應室内的壓 力，則無特別限定，可由可吸引處理反應室内的空氣之真 • 空泵181、配置於前述真空泵與處理反應室之間之氣體分 析器182、以及配置於前述氣體分析器與處理反應室之間 之閥183所構成。 等向性雷漿處理桊詈 等向性電漿處理裝置200係具有：氣體供應部211 ; 電漿生成部220,係使從前述氣體供應部所供應之氣體成 為電漿狀態；以及機台230，係設置基板並使前述電漿氣 體接觸於該基板的表面。此外，亦可因應必要而具有：將 藉由前述電漿生成部所生成之電漿氣體導引至處理對象物 表面之導引手段240、處理反應室250、或對前述處理反應 室進行減壓之減壓手段260。 φ 電聚生成部220只要可使藉由氣體供應手段所供應之 氣體形成為電聚者’則無任何限定’例如，可且有高.頻線 圈222圍繞該電漿生成部本體221之構成，再將高頻電源 223連接於該高頻線圈，並以可供應預定頻率的電流之方 式所連接。此外，亦可採用該高頻以外之電聚生成機構。 例如有ECR電漿、ICP電漿、螺旋波電漿等。 導引手段240並無任何限定，例如，較佳為經由以 英等絕緣體所形成之離子阻隔板241，將電聚氣^供 對象物而構成。 ' ~ 320559 13 201009929 =於：本裝置所進行之電漿處理而在基板上 無法進行依細之變質層的去除：、因 節^70在置可冷卻/加熱該基板之機台溫度調 如;機台溫度調㈣27G並無特別限定，例 =由溫度控制㈣溫水/冷水生成部271及圖中未顯干 的水循環流路所構成。藉此，可#由從該溫水二、201009929 VI. Description of the Invention: [Technical Field of the Invention] The substrate of the liquid crystal panel and the substrate formed of electrons are disposed from the base. The present invention relates to a method for performing a pattern removal pattern after forming a resist on a semiconductor wafer, a circuit substrate, or the like, and a method of manufacturing a semiconductor, a hard disk, a liquid crystal display, a thunder display, or the like in a manufacturing process. In the eclipse of the two soil plates or planes on the substrate, the shape of the (4) is Bao Lang. Here, the use of the polymer residue or the like which is covered on the surface of the object in = must be removed after the step = step. Here, the removal of the film can be performed by using plasma ashing, and (2) by chemical removal. For example, for a resist that becomes useless at each step, 1 is used to remove most of the 'by the ashing of the isotropic electricity, and then, for example, a mixture of sulfuric acid and peroxygen gas, the residual residue Removal method for dissolving/decomposing and removing ^ When the implantation energy is small, since the thickness of the altered layer is not thick, it can be completely removed by the isotropic plasma treatment and the wet treatment without leaving residue. However, the residue polymer formed after etching, or the altered layer on the surface of the resist after the high dose implantation, is difficult to completely remove. Especially for the metamorphic resist after ion implantation, as the amount of implantation increases, the difficulty of the removal is also increased. The target is generally 1 El 6 ion / cm 2 implant volume, and the situation of this implant amount, if one ashing, it may be difficult to completely remove the organic matter in the wet cleaning, but have to The same steps are performed multiple times and may not be removed depending on the situation. This will result in 320559 3 201009929 - the problem of increased cost and lower yield. As a method of resist stripping after ion implantation, for example, it is disclosed that it is treated by deuterium _Reactive (6). Etching: reactive ion etching, and then subjected to down ashing to remove the resist. [Technical Document] [Non-Patent Document [Semiconductor World 1993. 3 P118 to 125] [Explanation] The problem to be solved by the invention In recent years, with the high integration of semiconductor devices, high performance Therefore, the refinement of the device is carried out. Therefore, even if a small amount of residue remains on the semiconductor substrate, the defect is caused, and the yield of the product is lowered. In the above Non-Patent Document 1, Although the generation of the residue is not described in the paper, the analysis of the substrate after the analysis by the current analysis technique can confirm the generation of the residue. This can be regarded as if the resist is completely removed by the plasma treatment, and the metamorphic layer is removed. Or the ions or impurities contained in the unaltered layer form a compound with the plasma and the gas = as a residue residue. Moreover, it is extremely necessary to remove the residue. In other words, according to the method described in #Patent Document 1, a residue which is difficult to remove is generated, and as a result, a defect of the product is caused. Further, the removal of the deteriorated layer after ion implantation is due to ion implantation. The ions implanted in the few steps are more on the resist, so the upper metamorphic layer is thick and difficult to remove, so that the processing time is increased. If it is, the heat is likely to cause popping. The water remaining in the long convex blasting agent or the residual organic solvent is ruptured by the rapid expansion of the ash 320559 4 201009929. It is known as the other. Therefore, in order to solve the above problems, the present invention provides a method of removing all the residue without leaving a residue even after the ion implantation, in order to solve the above problems. The object of the present invention is to provide a method for removing a resist, which is a method for removing a resist from a substrate having a resist having a surface of a metamorphic layer, and is characterized by the same. a package comprising: an anisotropic plasma treatment step of performing an anisotropic plasma treatment on the substrate to remove at least a portion of the altered layer; and a wet cleaning step in the aforesaid anisotropic electricity After the slurry treatment step, the resist on the substrate is removed by the treatment medium. The invention (2) is the method for removing a resist according to the invention (1), wherein after the anisotropic plasma treatment step and Before the wet cleaning step, the method further comprises an isotropic plasma treatment step of performing an isotropic plasma treatment on the substrate to remove the altered layer. The invention (3) is the aforementioned invention (1) or (2) The method for removing a resist, wherein ozone water is used in the wet cleaning step. The invention of claim 4, wherein the ozone water is heated and used. The method of removing a resist according to any one of the above aspects (1) to (4), wherein the bias power is applied in the step of treating the anisotropic plasma. The invention C6) is the method for removing a resist according to the invention (5), wherein the method of adjusting the applied electric power of the bias electric power is performed in a state of 5 320559 201009929. The present invention (7) is the method for removing a resist according to any one of the above aspects (1) to (6), wherein the method is in the aforesaid anisotropic plasma treatment step and/or the aforementioned isotropic plasma treatment step The contact time of the plasma gas is controlled according to the formation conditions of the altered layer on the surface of the resist, so that most of the unaltered layer remains. The method of removing a resist according to any one of the above aspects (1) to (7), wherein, in the aforesaid anisotropic plasma treatment step and/or the aforementioned isotropic plasma treatment step, The step control is performed in accordance with the analysis result of the reaction and gas discharged from the resist removal, so that most of the unaltered layer remains. The present invention (9) is the method for removing a resist according to any one of the above aspects (1) to (8), wherein in the aforesaid anisotropic plasma treatment step and/or the aforementioned isotropic plasma treatment step, The temperature of the substrate is maintained at a temperature sufficient to provide a temperature at which the thermal energy of the altered layer can be removed by plasma, and is less than the temperature at which the blast occurs. The present invention (1 〇) is a resist removal system (for example, a resist removal system SI, S2), which is a resist removal system that removes a resisting agent whose surface is a metamorphic layer from a substrate, and is characterized in that it is provided for removing a resist. An anisotropic plasma processing apparatus for a metamorphic layer on the surface of the agent (for example, an anisotropic plasma processing apparatus 100, an anisotropic/isotropic plasma processing apparatus 500), the non-advanced plasma processing apparatus The gas supply unit (for example, the gas supply units 111 and 511) and the plasma generation unit (for example, the plasma generation unit 130 and 530) perform plasma treatment on the gas supplied from the gas supply unit to generate a plasma. a gas; a bias power applying unit (for example, a bias power applying unit 140, 540) for imparting anisotropy to the plasma gas 6 320559 201009929; and a machine unit (for example, a machine 150, 550) The plasma gas supplied from the plasma generating portion is in contact with the substrate. The invention (11) is the resist removal system (for example, the resist removal system SI, S2) of the above invention (10), which has an isotropic plasma processing apparatus (for example, an isotropic plasma processing apparatus 200, a non-etc. The directional/isotropic plasma processing apparatus 500) The invention (12) is the resist removal system (for example, the resist removal system S2) of the above invention (11), wherein the anisotropic plasma processing apparatus is also An isotropic plasma can be generated (for example, an anisotropic/isotropic plasma processing apparatus 500). The invention (13) is a resist removal system (for example, a resist removal system S2) of the aforementioned invention (12), Among them, the ON/OFF control of the bias power application unit (for example, the anisotropy/isotropic plasma processing apparatus 500 having the switch 543) can be performed. The invention (14) is the resist removal system (for example, the φ-removing agent removal system S2) of the invention (13), wherein the bias power application unit can perform adjustment of applied power (for example, having the power adjustment means 544) Isotropic/isotropic plasma processing apparatus 500). The invention (15) is the resist removal system (for example, the resist removal system S1) of the above invention (11), wherein the isotropic plasma processing apparatus (for example, the isotropic plasma processing apparatus 200) is the same as the aforementioned non- The isotropic plasma processing apparatus independently has a gas supply unit (for example, a gas supply unit 211) and an isotropic plasma generating unit (for example, a plasma generating unit 220) for supplying the gas supplied from the gas supply unit. The plasma treatment is performed; and the machine unit (for example, the machine 320559 201009929 * 230) contacts the plasma gas supplied from the isotropic plasma generating portion to the substrate. The invention (16) is the resist removal system (for example, the resist removal system SI, S2) according to any one of the aforementioned inventions (10) to (15), which has a wet cleaning device (for example, wet type) Washing device 300). The invention (17) is the resist removal system (for example, the resist removal systems SI, S2) of the above invention (16), wherein the wet cleaning apparatus has: a processing medium supply unit (for example, the processing medium supply unit 310) And a machine unit (for example, the machine 320) that contacts the processing medium supplied from the processing medium supply unit to the substrate. The invention (18) is the resist removal system (for example, the resist removal system SI, S2) of the invention (17), which further has an ozone water generating unit (for example, the ozone water generating unit 314). The present invention (19) is the aforementioned The resist removal system (for example, the resist removal systems SI, S2) of the invention (17) or (18), which has a heating portion (for example, the heating portion 312) for heating the processing medium φ. The meaning of the various terms used in this specification is described herein. The so-called "metamorphic layer" refers to an ion implantation resist or a sidewall protective film. The term "system" refers not only to "devices" in which the respective components are integrally housed, but even if the constituent elements are physically spaced apart (for example, a factory), or the constituent elements are not connected to each other. The information transmission is equivalent to the system as long as it has the constituent elements of the functions specified in the scope of application for patents. The so-called "most of the residue of the unaltered layer" means that the unaltered layer is not removed, and the unaltered layer remains in such a degree that the residue due to the plasma treatment does not occur 8 320559 201009929. (Effects of the Invention) According to the method of the invention (1), even after ion implantation, the residue is not left to be removed and the resist can be removed. In addition, in the non-isotropic plasma process, since the removal speed is fast, it is possible to perform low-temperature treatment without treatment. According to the method of the invention (2), even when the metamorphic layer or the like on the side cannot be completely removed by the treatment of the anisotropic electric pulverization, it can be continuously performed by the subsequent treatment with the anisotropic plasma. An isotropic plasma treatment process, and " removes the effect of the metamorphic layer on the remaining side. According to the method of the invention (3) and the system of the invention (18), by using ozone water in the wet cleaning step, the following effects can be attained, for example, without using, for example, heating sulfuric acid and storing It is more dangerous and it is not suitable for the ring household == agent. In addition, it is not necessary to use a fluorine-containing environmentally burdensome body, and it is possible to efficiently remove the metamorphism from the substrate in a short time. Spear's surface production = the method of the invention (4) and the system of the present invention (10), which can effectively remove the effect of the resist. According to the method of %(5) of the present invention, it is easy to make the electric shock have an anisotropic effect by (4) & To reach the method of Power Tree Ming (8), by adjusting the bias voltage power to the horizontal level, the degree of non-isotropicity can be adjusted, and the effect of the plasma processing in the same direction . According to the method of the invention (7), the contact time can be increased without the meaningless extension of the capacitor center 320559 9 201009929, and the method according to the invention (8), the treatment step and/or the isotropic electricity can be achieved. The effect of time efficiency. The effect of the removal of the agent according to the method of the invention (9). The effect of time efficiency. The non-isotropic electrical post-processing step can be stopped at an optimal timing, and the step of improving can be achieved without causing a blast to promote the time efficiency of the step (10) according to the invention (10) to the step of improving (11) The device can achieve the effect of non-isotropic plasma treatment. The system can effectively remove the metamorphic layer and achieve the effect. According to the above (4) (10), the non-isotropic f-treatment device can also produce isotropic plasma by treating the directional plasma with more isotropic plasma treatment. The power generation device (4) achieves the effect of more efficiently performing the step of moving from the non-isotropic electrical assembly process to the 4-directional electrical polymerization process. According to the system of the invention (13), the on/off control of the bias power applying unit can be performed, whereby the anisotropy/isotropic switching can be performed more efficiently. effect. According to the system of the invention (4), it is possible to adjust the degree of anisotropy of the plasma by setting the bias voltage of the bias voltage, and simultaneously perform the plasma processing in the horizontal direction. According to the present invention (15) In the system, when the processing time for the non-isotropic electropolymerization is long, 'after the non-isotropic treatment is finished', the isotropic treatment is performed in the other reaction chambers, thereby improving the inclusion to the wetness. The effect of the total amount of treatment until the treatment is processed. 10 320559 201009929 According to the system of the invention (10), the effect of the washable step can be achieved. Double + ground shifting in the wet system according to the invention (10), by means of so-called After the plasma treatment, it can be efficiently transported to the wet reaction treatment, which is the effect of the problem that the invention is carried out by the blade treatment. The washing = := reattachment). : (=: Full-washing is performed for the blade type treatment, and when the invention has an effect of maintaining ozone water having a high temperature and a high concentration, the embodiment is <Resistant removal device> One-shaped bear _ Figure 1 shows the first-form resisting agent removal system (10) is a schematic diagram of the non-isotropic recording processing system. [Between the devices, there is a set of peppers = 40 sets of 0 = composition. In addition, it is preferable to carry out all of the fourth (fourth). It is preferable that the object holding unit 4G can automatically use the aforementioned holding H疋, 402, and the holding unit 4〇1 and the moving section 4 can be used. A part of the support body 403. The adjustment is a suitable high-plasma dynamism-^ an anisotropic plasma processing apparatus 1〇〇a an isotropic plasma generating unit 120, which is #^,有·耽The body supply portion ill; ^ ', 隹' generates an anisotropic plasma from the state of the electricity supplied from the gas supply portion; and the machine table: 320559 11 201009929 * sets the substrate and contacts the plasma gas On the surface of the substrate, if necessary, the plasma gas generated by the plasma generating portion may be guided to The guiding means 16 for processing the surface of the object, the processing chamber 170, or the means for reducing the pressure of the processing chamber * 180. The non-isotropic plasma generating unit 120 has a plasma generating unit 13 The gas supplied from the gas supply unit is in a plasma state, and the power application unit 140 is configured to impart anisotropy to the plasma. The electric power generation unit 130 can be provided by a gas supply means. The supplied gas is formed into a plasma, and is not limited. For example, the high frequency coil 132 may be surrounded by the plasma generating unit body 131, and the high frequency power source 133 may be connected to the high frequency coil. It is connected in such a manner that a current of a predetermined frequency can be supplied. In addition, a plasma generating mechanism other than the high frequency can be used, for example, ECR (Electron Cyclotron Resonance) plasma, ICP (Inductively Coupled Plasma) The electric current is applied to the plasma, the spiral wave plasma, etc. The bias power application unit 140 includes a bias electrode 141 and a bias power source 142 that applies electric power to the bias electrode. The plasma treatment by the device generates heat on the substrate, or the removal of the deteriorated layer according to the plasma cannot be performed because the temperature is too low," because the j machine 15G is preferably provided to cool/heat the substrate. The machine temperature adjustment unit (10) is not particularly limited, and may be composed of, for example, a warm water/cold water generation unit 191 for controlling the degree and a water-sucking road that is not shown in the figure. The temperature on the substrate can be set to a predetermined temperature by heating or cooling the substrate from the warm/cold water generated 12 320559 201009929 - supplied warm or cold water. Further, the pressure reducing means 180 is not particularly limited as long as the pressure in the processing reaction chamber can be lowered, and may be a gas pump 181 that can suck the air in the processing chamber, and a gas analyzer 182 disposed between the vacuum pump and the processing chamber. And a valve 183 disposed between the gas analyzer and the processing chamber. The isotropic slurry treatment apparatus 2000 includes: a gas supply unit 211; a plasma generation unit 220 that causes a gas supplied from the gas supply unit to be in a plasma state; and a machine 230 The substrate is disposed and the plasma gas is brought into contact with the surface of the substrate. Further, if necessary, the guide means 240 for guiding the plasma gas generated by the plasma generating unit to the surface of the object to be processed, the processing chamber 250, or decompressing the processing chamber may be provided. Decompression means 260. The φ electropolymer generation unit 220 is not limited as long as the gas supplied by the gas supply means can be formed as a polymerizer. For example, the high frequency coil 222 can be formed around the plasma generation unit body 221. The high frequency power source 223 is connected to the high frequency coil and connected in such a manner as to supply a current of a predetermined frequency. In addition, an electropolymerization mechanism other than the high frequency may be employed. For example, there are ECR plasma, ICP plasma, spiral wave plasma, and the like. The guiding means 240 is not limited in any way. For example, it is preferable that the ion-blocking member 241 formed of an insulator such as a ferrous alloy is provided with an electric gas. ' ~ 320559 13 201009929 =:: The plasma treatment carried out by the device can not remove the fine metamorphic layer on the substrate: the temperature of the machine can be cooled/heated by the node 70; The temperature adjustment of the machine (4) 27G is not particularly limited. For example, the temperature control (4) warm water/cold water generation unit 271 and the water circulation flow path which is not dried in the drawing are used. By this, can be # from the warm water II
:所供!、之或冷水對該基板進行加熱或冷卻:7而將ί 板上的溫度設定為預定溫度。 、土 此外’減壓手段26ϋ只要可降低處理 力’則無特別μ ’可由可吸引處理反應室内的 於前述真空泵與處理反應室之間之氣趙分 置於料氣齡娜祕理反應室之間 濕式洗洚奘罟·' 濕式洗淨裝置300係具有：處理媒體供應部3丨〇、以 及使從前述處理制供應频供狀處轉體_於基板 之機台320。在此，處理媒體供應部31〇係由處理媒體供 應槽31卜用以加熱處理媒體之加熱部312、以及將處理媒 體供應至基板之供應噴嘴313所構成。圖中，加熱部幻2 係配置於處理媒體供應槽311與供應喷嘴313之間，作並 不限定於此，亦可設置於供應槽内。此外，較佳為於;、、 處理媒體供應槽311内設置臭氧水生成部314(^^未蔡’ 第二形熊 32〇559 14 201009929 • 第2圖係顯示第二形態之阻劑去除系統S2的概略圖。 阻劑去除系統S2係由：可進行非等向性電漿處理與等向性 - 電漿處理的切換之非等向性/等向性電漿處理裝置500、 以及濕式洗淨裝置300所構成。由於濕式洗淨裝置3〇〇係 與前述第-形態之阻劑去除系統S1的濕式洗淨裝置為相 同構成，所以在此係附加同一符號並省略該詳細說明。此 外，於本形悲中，較佳為亦於非等向性/等向性電漿處理 裝置500與濕式洗淨裝置300之間，配置有搬運裝置。 由於此搬運裝置400亦與前述第一形態之阻劑去除系統以 的搬運裝置400為相同構成，所以在此係附加同一符號並 省略該詳細說明。 電漿虛理-署 非等向性/等向性電聚處理裝置500係具有：氣體供 511 ’非等向性/等向性電聚產生部52〇，係使從前述 氣體供應部所供應之氣體成為電聚狀態而產生非等向性電 _等向性電聚’以及機台55〇 ,係設置基板並使前述電 裝氣體接觸於該基板的表面。此外，亦可因應必要而具有： 將藉由前述電漿生成部所生成之電漿氣體導引至處理對象 物表面之導引手段560、處理反應室570、或對前述處理反 應室進行減壓之減壓手段58〇。 非等向性/等向性電漿產生部520係具有：電漿生成 部530 ’係使從氣體供應部所供應之氣體成為電漿狀態； 以及偏壓電力施加部540，係用以對前述電漿賦予非等向 性。電聚生成部530只要可使藉由氣體供應手段所供應之 15 320559 201009929 氣體形成為電漿者，則無任何限定， 圈532圍繞該電衆生成部本體531 高頻線 533連接於該高頻線圈，並以可供應 將同頻電源 式所連接。此外，亦可採用該高㈣外之電漿生成機構方 例如有ECR電漿、ICP電漿、螺旋波電漿等。 偏壓電力施加部540係具有㈣電極⑷ 壓電極施加電壓之偏壓電源542、可對偏壓電極進^電^ 施加的導通/切_制之開_ 543、以及可調 之電力調整手1 544。藉由該偏壓電歷施加的 控制，可進行非等向性電轉理與等向性《處理的切換 、β由於因本裝置所進行之電漿處理而在基板上產生熱， 或是因溫度過低^無法進行依據電衆之變質層的去心 此機台550較佳為設置可冷卻/加熱該基板:機台：产調 節部59G。，在此’機台溫度調節部咖並|特別限定^ 如可由溫度控制用的溫水/冷水 = :::成。藉此，可藉_溫=1 板上的溫度設定為::::基板進行加熱或冷卻’而將基 此外，減壓手於 力，則無特別限定H要可降低處理反應室内的壓 空栗58卜配置於^由可吸引處理反應室内的空氣之真 析考582、以爲；則述真空泵與處理反應室之間之氣體分 之閥583所構成配置於前述氣體分析器與處理反應室之間 <阻劑去除方法> 320559 16 201009929 ' 本發明之阻劑去除方法係包含非等向性電漿處理步驟 . 及濕式洗淨步驟。此外，亦可因應必要而包含等向性電漿 . 處理步驟。以下係依據圖式來說明本發明之實施形態。第 3圖（a)係顯示在表面形成有Si〇2層之石夕晶圓基板1的表面 ‘ 形成有阻劑2之狀況。阻劑2的表面形成有變質層2a，於 阻劑2的内侧具有未變質層2b。該變質層2a並無特別限 定，例如可藉由離子植入等非等向性處理來形成，由於該 離子從第3圖的上方朝向下方植入，所以上方係形成較厚 • 的厚度。對該基板1進行非等向性電漿處理，而如第3圖 (b)所示般，僅去除變質層2a上部的一部分（非等向性電漿 處理步驟）。接著進行等向性電漿處理，而如第3圖（c)所 示般，去除變質層2a(等向性電漿處理步驟）。然後如第3 圖（d)所示，使成為未變質層2b之阻劑接觸於處理媒體而 予以去除（濕式洗淨步驟）。以下係詳細敘述非等向性電漿 處理步驟、等向性電漿處理步驟、以及濕式洗淨步驟的各 φ 項步驟。 非等向性電漿處理步驟 非等向性電漿處理步驟係對具有表面由變質層所構成 之阻劑之基板，進行非等向性電漿處理。在此，所謂的非 等向性電漿處理，是指深度方向的處理速度較水平方向的 處理速度還大之灰化。於非等向性電漿處理步驟中，首先 產生電漿氣體，然後藉由偏壓電力的施加，對該電漿氣體 賦予非等向性，並使電漿氣體接觸於基板表面。 在此詳細說明偏壓電力的施加。本最佳形態之非等向 17 320559 201009929 ' 性電漿處理步驟之電漿的非等向性調節，主要可藉由偏壓 電力的施加來進行。亦即，以偏壓電力的施加來調整處理 • 條件，亦可藉此進行等向性處理，而將形成於基板上的阻 . 劑表面之變質層2a予以去除。例如當變質層2&為粒子植 入後的硬化層時，由於該離子往阻劑的深度方向植入，所 以阻劑上部的變質層變得較厚，且阻劑側面的變質層變得 相對較薄。因此，可配合該變質層的形狀，設定適當的條 件並進行非等向性電漿處理，而藉此迅速地去除變質層 2a。若可迅速的去除，則可抑制阻劑之表面溫度的上升， 並避免凸爆的問題。在此，施加於偏壓電極之電力，係因 變質層的性質而有所不同，但較佳為例如5〇w至1〇〇〇w， 更佳為500W至1000W。若電力愈強.，則可提升變質層的去 除速度。另一方面，若電力太強，則因濺鍍效果使變質層 表I離，該碎片會飛散至晶圓表面而可能難以去除。此外， 當欲降低因偏壓電力對晶圓表面所造成之損害時’電力較 低者較佳。 所使用之氣體的種類並無特別限定，例如有氫氣、氧 氣、氮氣、水蒸氣、CF4或這些氣體的組合。這些氣體當中， 若使用氫氣，由於氳原子能夠僅生成作為一個原子的共有 鍵、所以變質層的成分容易低分子量化，而達到不易殘 留阻劑殘渣之效果。此外，若使用02氣體，可達到快速處 理之效果。尤其當進行等向性電漿處理時，於非等向性電 漿處理中，可使用〇2氣體迅速地去除，然後於等向性電衆 處理中，使用H2氣體，在不會殘留殘渣下完美地去除變質 320559 201009929 層。 在此說明於各種形成條件下控制接觸時間之方法。因 . 形成條件而產生變化者，為變質層的厚度及緊緻度（硬度、 離子濃度）。 . 若變質層的厚度較厚，則須增加接觸時間。決定厚度 之條件，為植入離子種類、植入能量。離子種類係以B、P 及As為中心，離子的大小較小者，可植入至阻劑深處，使 變質層變厚。因此，若植入能量相同，則B的變質層厚度 _ 最厚。關於植入能量，由於為控制離子植入深度之參數， 所以植入能量愈大，變質層愈厚。 再者，若變質層的厚度相同且使植入量增多，則須增 加接觸時間。此外，因離子種類的不同，若為原子量較大 的離子，則凝聚力較高，所以接觸時間變長。亦即，因離 • 子種類的不同，尤其因原子量的不同，可觀察出對變質層 的厚度及緊緻度之影響。因此，一般而言，係具有：雖然 φ 較小的B較As更容易去除，但由於變質層的厚度較厚，而 導致接觸時間增長之取捨關係。除此之外，雖然As不易去 除，但從實驗結果來看，變質層的厚度乃最為有效。因此， 變質層較薄的As相對容易處理。 關於因應反應氣體分析結果之步驟控制，並無特別限 定，例如可使用下列自動控制，亦即，採用反應室内的電 漿發光光譜，檢測出製程氣體與變質層中所含有之離子之 間的反應物之光譜，於光譜消失之時點，可判斷為變質層 完全去除並結束步驟。 19 320559 201009929 ’纟此’機台溫度較佳為維持在可提供_依據電聚來 去除變.質層之熱能之溫度以上，且未滿凸爆產生温度之溫 .度，雖無特別限定，但較佳為例如為i〇(rc以下的溫度， 更佳為挑至80°c。藉由設定在該溫度範圍，乃不易產生 凸爆’且具有充分的表面溫度，所以可使電聚氣體與變質 阻劑產生反應而予以去除。當於離子植入前施以uv硬化處 理時，由於凸爆溫度上升，所以可於更高的溫度中進行處 理。該溫度調整可藉由第-形態、第二形態的機台溫度調 即部來進打調签。機台溫度可藉由設置在電漿機台表面附 ，之1度感；i!iH來測量。溫度感測器的種類並無特別限 定，例如可藉由熱電偶來測量。 .I向性電漿處理舟 丄向性電漿處理步驟係對具有經非等向性電漿處理後 進/-算2生灰化之表面由變f層所構成之阻劑之基板， 理。在此，所謂的等向性電漿處理，是 之電漿處理。理速度與水平方㈣處理速度為同等程度 氣、之氣體的種類並無特別限定，例如有氫氣、氧 若使用1了 Λ氣、這些氣體的組合。這些氣體當中， 姓，所以力風氣能夠僅生成作為一個原子的共有鍵 ;阻=:的成分容易低分子量化 ’ ^達到不易殘 形成tt說明於各種形成條件下控制接觸時間之方法。因 形成條件而產生變化者，為變質層的厚度及緊敏度（硬度 320559 20 201009929 . 離子濃度）。 . 若變質層的厚度較厚，則須增加接觸時間。決定厚度 . 之條件，為植入離子種類、植入能量。離子種類係以B、P 及As為中心，離子的大小較小者，可植入至阻劑深處，使 * 變質層變厚。因此，若植入能量相同，則B的變質層厚度 最厚。關於植入能量，由於為控制離子植入深度之參數， 所以植入能量愈大，變質層愈厚。 再者，若變質層的厚度相同且使植入量增多，則須增 ❿ 加接觸時間。此外，因離子種類的不同，若為原子量較大 的離子，則凝聚力較高，所以接觸時間變長。亦即，因離 子種類的不同，尤其因原子量的不同，可觀察出對變質層 的厚度及緊緻度之影響。因此，一般而言，係具有雖然較 小的B較As更容易去除，但由於變質層的厚度較厚，而導 致接觸時間增長之取捨關係。除此之外，雖然As不易去 除，但從實驗結果來看，變質層的厚度乃最為有效。因此， _ 變質層較薄的As相對容易處理。 關於因應反應氣體分析結果之步驟控制，並無特別限 定，例如可使用下列自動控制，亦即，採用反應室内的電 漿發光光譜，檢測出製程氣體與變質層中所含有之離子之 間的反應物之光譜，於光譜消失之時點，可判斷為變質層 完全去除並結束步驟。 在此，機台溫度較佳為維持在可提供能夠依據電漿來 去除變質層之熱能之溫度以上，且未滿凸爆產生溫度之溫 度，雖無特別限定，但較佳為例如l〇〇°C以下的溫度，更 21 320559 201009929 佳為40C至80C。藉由設定在該溫度範圍，乃不易產生凸 - 爆，且具有充分的表面溫度，所以可使電漿氣體與變質阻 - 劑產生反應而予以去除。當於離子植入前施以UV硬化處理 時’由於凸爆溫度上升，所以可於更高的溫度中進行處理。 該溫度調整可藉由第一形態、第二形態的機台溫度調節部 來進行調整。機台溫度可藉由設置在電漿機台表面附近之 溫度感測器來測量。溫度感測器的種類並無特別限定，例 如可藉由熱電偶來測量。 • 濕式洗淨·步驟 於濕式洗淨步鄉中，係藉由處理媒體來去除藉由前述 非等向性電漿處理步驟及/或等向性電漿處理步驟使變質 層去除後之阻劑。在此，濕式洗淨可使用一般所知的技術， 例如有藥劑去除、水蒸氣照射、混相流體照射等。此外， .處理媒體並無特別限定，例如有機能水、藥劑、水、水蒸 氣等◊在此，作為機能水，可使用臭氧水或氫水，亦可於 • 這些機能水中添加鹽酸等藥劑來使用。在此，藥劑可使用 硫酸一過氧化氫、鹽酸—過氧化氫、氫氟酸、緩衝氫氟酸 水溶液等之無機酸系藥劑；氨一過氧化氫等之無機鹼系藥 劑’烧基本續酸（alkylbenzene sulfonates)等之有機酸系 藥劑’或是乙醇胺（ethanolamine)等之有機鹼系藥劑。當 中，較佳為使用臭氧水。當使用臭氧水時，為了提高臭氧 水的活性而在短時間内去除未變質層2b，可對臭氧水進行 加溫’雖無特別限定，但最適範圍為70°C至80¾。 [實施例] 320559 22 201009929 * 以llOkeV的植入能量、植入角度7°，將P離子植入 . 至阻劑圖案至lE16ion/cm2的植入量為止，以調整出試 , 料。第4圖係顯示離子植入後的阻劑圖案之剖面SEM(掃描 式電子顯微鏡）影像。第4圖中的2a為變質層，2b為未變 * 質層。使用具有可施加偏壓電壓之ICP電漿處理裝置及臭 氧水洗淨裝置之Aurora(Aqua Science社製）對該試料進行 處理。處理内容為，係於機台溫度為601：、〇2氣體流量 400cc、反應室内壓力400mTorr、偏壓電壓500W的非等向 ❹ 性電漿條件下，進行150秒的處理，之後於溫度60°C、H2 氣體流量lOOOcc、反應室内壓力500mTorr、電漿電壓2000W 的等向性電漿條件下’進行200秒的處理。第5圖係顯示 該電漿處理後之剖面SEM影像。第5圖中的2b，為處理後 的未變質層。之後以80°C、9〇ppm的條件，對此進行電漿 處理後的試料施以90秒的臭氧水處理。第6圖係顯示處理 後的晶圓表面之剖面SEM影像。圖中的3為晶圓表面，離 ⑩ 子植入後的阻劑可不留殘渣而完全去除。 (產業利用可能性） 本發明可廣泛利用於從基板去除阻劑之步驟。 【圖式簡單說明】 帛1 ®係顯示第i態之阻縣除系統的概念圖。 第2圖係顯示第二形態之阻劑去除系統的概念圖。 第3圖（a)至⑷係顯示本最佳形態之阻劑去除步驟的 概念圖。 第4圖係顯示於實施例中所使用之離子植入後的阻劑 320559 23 201009929 圖案之剖面SEM影像。 第5圖係顯示實施例之電漿處理後的剖面SEM影像。 第6圖係顯示實施例之臭氧水處理後的晶圓表面之剖 面SEM影像。 【主要元件符號說明】: The supplied substrate, or cold water, is heated or cooled: 7 and the temperature on the plate is set to a predetermined temperature. In addition, the soil decompression means 26, as long as the treatment capacity can be reduced, there is no special μ', which can be placed in the reaction chamber of the reaction chamber between the vacuum pump and the treatment reaction chamber. The wet cleaning apparatus 300 includes a processing medium supply unit 3 and a machine 320 that rotates the substrate from the processing unit to the substrate. Here, the processing medium supply unit 31 is constituted by the processing medium supply tank 31, the heating unit 312 for heating the processing medium, and the supply nozzle 313 for supplying the processing medium to the substrate. In the figure, the heating unit is disposed between the processing medium supply tank 311 and the supply nozzle 313, and is not limited thereto, and may be provided in the supply tank. Further, it is preferable that the ozone water generating unit 314 is disposed in the processing medium supply tank 311 (^^未蔡' second type bear 32〇559 14 201009929 • Fig. 2 shows the second form resist removal system Schematic diagram of S2. The resist removal system S2 is an anisotropic/isotropic plasma processing apparatus 500 capable of performing an anisotropic plasma treatment and an isotropic-plasma treatment, and a wet type The wet cleaning device 3 has the same configuration as the wet cleaning device of the resist removal system S1 of the above-described first embodiment, and therefore the same reference numerals will be given thereto, and the detailed description will be omitted. Further, in this case, it is preferable that a transfer device is disposed between the anisotropic/isotropic plasma processing apparatus 500 and the wet cleaning apparatus 300. Since the conveying apparatus 400 is also as described above Since the conveying device 400 of the resist removal system of the first embodiment has the same configuration, the same reference numerals will be given thereto, and the detailed description will be omitted. The plasma-virtual-isometric/isotropic electropolymerization processing apparatus 500 Has: gas for 511 'non-isotropic/isotropic electropolymerization The raw portion 52 is configured such that the gas supplied from the gas supply unit is in an electropolymerized state to generate an anisotropic electro-isotropic electropolymerization and a machine 55, and a substrate is provided and the electric gas is contacted. Further, the surface of the substrate may be provided with: a guiding means 560 for guiding the plasma gas generated by the plasma generating portion to the surface of the object to be processed, a processing chamber 570, or the foregoing The pressure reducing means 58 for treating the reaction chamber is decompressed. The non-isotropic/isotropic plasma generating unit 520 has a plasma generating unit 530' that causes the gas supplied from the gas supply unit to be in a plasma state; And the bias power applying unit 540 is configured to impart anisotropy to the plasma. The electropolymer generating unit 530 does not have any gas as long as the 15 320559 201009929 gas supplied by the gas supply means can be formed. The ring 532 is connected to the high frequency line 533 around the high frequency line 533 of the electricity generating unit body 531, and is connected to the same frequency power supply type. Further, the high (four) external plasma generating mechanism can also be used. For example, there is ECR Pulp, ICP plasma, spiral plasma, etc. The bias power application unit 540 is a bias power supply 542 having a voltage applied to the (4) electrode (4), and a conduction/cutting method capable of applying a bias voltage to the bias electrode. _ 543, and adjustable power adjustment hand 1 544. By the control applied by the bias voltage, the anisotropic electrical and anisotropic switching can be performed, and β is performed by the device. The plasma is processed to generate heat on the substrate, or the temperature is too low. ^The centering of the deterioration layer according to the electricity cannot be performed. The machine 550 is preferably arranged to cool/heat the substrate: the machine: the production adjustment unit 59G In this case, the temperature adjustment unit of the machine is specially limited. For example, warm water/cold water can be used for temperature control =::. Therefore, the temperature on the plate can be set to :::: the substrate is heated or cooled. In addition, if the pressure is reduced, the pressure is not particularly limited, and the pressure in the reaction chamber can be reduced. The pump 58 is disposed in the air chamber 582 which can be attracted to the processing chamber, and the gas valve 583 between the vacuum pump and the processing chamber is disposed in the gas analyzer and the processing chamber. <Resistant Removal Method> 320559 16 201009929 The resist removal method of the present invention comprises an anisotropic plasma treatment step and a wet cleaning step. In addition, it is also possible to include isotropic plasma as needed. Hereinafter, embodiments of the present invention will be described based on the drawings. Fig. 3(a) shows a state in which the resist 2 is formed on the surface of the wafer substrate 1 on which the Si〇2 layer is formed. The surface of the resist 2 is formed with an altered layer 2a, and the inside of the resist 2 has an unaltered layer 2b. The altered layer 2a is not particularly limited. For example, it can be formed by an isotropic treatment such as ion implantation. Since the ions are implanted from the upper side toward the lower side of Fig. 3, the upper portion is formed to have a thicker thickness. The substrate 1 is subjected to an anisotropic plasma treatment, and as shown in Fig. 3(b), only a part of the upper portion of the altered layer 2a is removed (a non-isotropic plasma treatment step). Next, an isotropic plasma treatment is performed, and as shown in Fig. 3(c), the altered layer 2a is removed (isotropic plasma treatment step). Then, as shown in Fig. 3(d), the resist which becomes the unaltered layer 2b is removed by contact with the treatment medium (wet washing step). Hereinafter, each of the φ steps of the anisotropic plasma treatment step, the isotropic plasma treatment step, and the wet cleaning step will be described in detail. An anisotropic plasma treatment step The anisotropic plasma treatment step performs an anisotropic plasma treatment on a substrate having a resist having a surface composed of a deteriorated layer. Here, the term "non-isotropic plasma processing" means that the processing speed in the depth direction is larger than the processing speed in the horizontal direction. In the non-isotropic plasma processing step, a plasma gas is first generated, and then the plasma gas is imparted with anisotropy by application of bias power, and the plasma gas is brought into contact with the surface of the substrate. The application of the bias power is explained in detail herein. The non-isotropy of the best form 17 320559 201009929 'The anisotropic adjustment of the plasma of the plasma processing step can be mainly performed by the application of bias power. That is, the treatment condition can be adjusted by the application of the bias power, and the isotropic treatment can be performed to remove the altered layer 2a on the surface of the resist formed on the substrate. For example, when the metamorphic layer 2& is a hardened layer after particle implantation, since the ions are implanted in the depth direction of the resist, the altered layer on the upper portion of the resist becomes thicker, and the altered layer on the side of the resist becomes opposite Thinner. Therefore, an appropriate condition can be set in accordance with the shape of the altered layer and an anisotropic plasma treatment can be performed, whereby the altered layer 2a can be quickly removed. If it can be removed quickly, it can suppress the rise of the surface temperature of the resist and avoid the problem of convex explosion. Here, the electric power applied to the bias electrode differs depending on the nature of the altered layer, but is preferably, for example, 5 〇w to 1 〇〇〇w, more preferably 500 W to 1000 W. If the power is stronger, the removal speed of the metamorphic layer can be improved. On the other hand, if the power is too strong, the spoiled layer will be separated by the sputtering effect, and the debris will fly to the surface of the wafer and may be difficult to remove. In addition, when it is desired to reduce the damage caused to the wafer surface by the bias power, the lower power is preferred. The type of the gas to be used is not particularly limited, and examples thereof include hydrogen gas, oxygen gas, nitrogen gas, water vapor, CF4 or a combination of these gases. Among these gases, when hydrogen gas is used, since the ruthenium atom can form only a common bond as one atom, the component of the altered layer is likely to have a low molecular weight, and the effect of not easily remaining the residue of the resist is obtained. In addition, if 02 gas is used, the effect of rapid processing can be achieved. Especially when performing isotropic plasma treatment, in the anisotropic plasma treatment, 〇2 gas can be quickly removed, and then in the isotropic electricity treatment, H2 gas is used, and no residue remains. Perfectly removes the metamorphic 320559 201009929 layer. A method of controlling the contact time under various formation conditions is described herein. The change in the formation conditions is the thickness and compactness (hardness, ion concentration) of the metamorphic layer. If the thickness of the metamorphic layer is thick, the contact time must be increased. The conditions for determining the thickness are implanted ion species and implanted energy. The ion species are centered on B, P, and As, and the smaller the ion size, can be implanted deep into the resist to thicken the metamorphic layer. Therefore, if the implant energy is the same, the thickness of the metamorphic layer of B is _ thickest. Regarding the implantation energy, since the parameter for controlling the depth of ion implantation is made, the larger the implantation energy, the thicker the metamorphic layer. Furthermore, if the thickness of the altered layer is the same and the amount of implantation is increased, the contact time must be increased. Further, depending on the type of ions, if the ions are large in atomic weight, the cohesive force is high, so the contact time becomes long. That is, the influence on the thickness and the compactness of the metamorphic layer can be observed depending on the type of the ion, especially the atomic weight. Therefore, in general, it is preferable that although B having a smaller φ is easier to remove than As, the thickness of the metamorphic layer is thicker, resulting in a trade-off relationship of contact time growth. In addition, although As is not easy to remove, the thickness of the metamorphic layer is most effective from the experimental results. Therefore, the As, which is a thinner metamorphic layer, is relatively easy to handle. The step control in response to the analysis result of the reaction gas is not particularly limited. For example, the following automatic control can be used, that is, the reaction between the process gas and the ion contained in the altered layer can be detected by using the plasma luminescence spectrum in the reaction chamber. The spectrum of the object can be judged as the metamorphic layer is completely removed and the step is terminated when the spectrum disappears. 19 320559 201009929 The temperature of the machine is preferably maintained at a temperature above the temperature at which the thermal energy of the variable layer is removed, and the temperature is not full, and although not particularly limited, However, it is preferably, for example, i 〇 (temperature below rc, more preferably picks up to 80 ° C. By setting it in this temperature range, it is difficult to generate a convex explosion and has a sufficient surface temperature, so that an electropolymerized gas can be obtained It is removed by reaction with the metamorphic resist. When uv hardening is applied before ion implantation, the temperature of the blasting can be increased at a higher temperature. The temperature can be adjusted by the first form, In the second form, the temperature of the machine is adjusted, and the temperature of the machine can be measured by setting a degree of sensitivity on the surface of the plasma machine; i!iH. The type of temperature sensor is not Particularly limited, for example, can be measured by a thermocouple. The I directional plasma treatment of the slanting plasma processing step is performed on the surface having an anaerobic plasma treatment and then undergoing ashing. The substrate of the resist formed by the f layer, here, the so-called isotropic The slurry treatment is a plasma treatment, and the treatment speed is not particularly limited as long as the treatment speed is the same as that of the horizontal (four) treatment, for example, hydrogen gas and oxygen are used, and a combination of these gases is used. Among them, the surname, so the force can only generate a common bond as an atom; the composition of resistance =: is easy to low molecular weight ' ^ to achieve non-residual formation tt illustrates the method of controlling contact time under various formation conditions. The change is the thickness and tightness of the metamorphic layer (hardness 320559 20 201009929 . Ion concentration). If the thickness of the metamorphic layer is thicker, the contact time must be increased. The thickness is determined. Into the energy. The ion species is centered on B, P and As. The smaller the size of the ion, can be implanted deep into the resist, making the metamorphic layer thicker. Therefore, if the implantation energy is the same, the deterioration of B The thickness of the layer is the thickest. Regarding the implantation energy, the larger the implantation energy, the thicker the metamorphic layer, because the thickness of the metamorphic layer is the same. When the amount of implantation is increased, it is necessary to increase the contact time. In addition, depending on the type of ion, if the ion is larger in atomic weight, the cohesive force is higher, so the contact time becomes longer, that is, depending on the type of ion, especially Depending on the atomic weight, the effect on the thickness and compactness of the metamorphic layer can be observed. Therefore, in general, although the smaller B is easier to remove than As, the thickness of the metamorphic layer is thicker. In addition, although As is not easy to remove, the thickness of the metamorphic layer is most effective from the experimental results. Therefore, the thiner As of the metamorphic layer is relatively easy to handle. The step control of the result is not particularly limited. For example, the following automatic control can be used, that is, the spectrum of the reactant between the process gas and the ion contained in the altered layer is detected by using the plasma luminescence spectrum in the reaction chamber. When the spectrum disappears, it can be judged that the metamorphic layer is completely removed and the step is ended. Here, the temperature of the stage is preferably maintained at a temperature higher than the temperature at which the thermal energy of the altered layer can be removed depending on the plasma, and is not full of the temperature at which the blast occurs, and is not particularly limited, but is preferably, for example, l〇〇. Temperature below °C, more 21 320559 201009929 Good for 40C to 80C. By setting it within this temperature range, it is less likely to cause a bump and a full surface temperature, so that the plasma gas can be removed by reacting with the metamorphic resistor. When UV hardening is applied before ion implantation, the treatment can be carried out at a higher temperature due to the rise in the temperature of the blast. This temperature adjustment can be adjusted by the machine temperature adjustment unit of the first aspect and the second aspect. The table temperature can be measured by a temperature sensor placed near the surface of the plasma machine. The type of the temperature sensor is not particularly limited, and can be measured, for example, by a thermocouple. • Wet cleaning step in the wet cleaning step by removing the metamorphic layer by the processing medium to remove the metamorphic layer by the a non-isotropic plasma processing step and/or the isotropic plasma processing step Resistor. Here, the wet cleaning can be carried out by a generally known technique such as drug removal, water vapor irradiation, mixed-phase fluid irradiation, or the like. Further, the processing medium is not particularly limited. For example, organic water, chemicals, water, water vapor, etc. may be used here. As functional water, ozone water or hydrogen water may be used, and hydrochloric acid or the like may be added to these functional waters. use. Here, as the agent, an inorganic acid-based agent such as sulfuric acid-hydrogen peroxide, hydrochloric acid-hydrogen peroxide, hydrofluoric acid or a buffered hydrofluoric acid aqueous solution; an inorganic-base agent such as ammonia-hydrogen peroxide; An organic acid-based agent such as "alkylbenzene sulfonates" or an organic base-based agent such as ethanolamine. Among them, ozone water is preferably used. When ozone water is used, the ozone water can be heated while removing the unaltered layer 2b in a short time in order to increase the activity of the ozone water. The temperature range is not particularly limited, but the optimum range is 70 ° C to 803⁄4. [Examples] 320559 22 201009929 * P ions were implanted at an implantation energy of llOkeV at an implantation angle of 7°. The amount of implantation of the resist pattern to lE16ion/cm2 was adjusted to adjust the test material. Fig. 4 is a cross-sectional SEM (scanning electron microscope) image showing a resist pattern after ion implantation. In Fig. 4, 2a is an altered layer, and 2b is an unaltered layer. The sample was treated with Aurora (Aqua Science Co., Ltd.) having an ICP plasma processing apparatus capable of applying a bias voltage and an ozone water washing apparatus. The treatment content is performed under the condition of non-isotropic plasma of the machine table temperature of 601:, 〇2 gas flow rate 400 cc, reaction chamber pressure 400 mTorr, and bias voltage 500 W, for 150 seconds, and then at a temperature of 60°. C, H2 gas flow rate 1000 cc, reaction chamber pressure 500 mTorr, plasma voltage 2000 W under isotropic plasma conditions '200 seconds of treatment. Figure 5 shows a cross-sectional SEM image of the plasma treated. 2b in Fig. 5 is the unmodified layer after the treatment. Thereafter, the sample subjected to the plasma treatment was subjected to ozone water treatment for 90 seconds under the conditions of 80 ° C and 9 〇 ppm. Figure 6 shows a cross-sectional SEM image of the surface of the wafer after processing. 3 in the figure is the surface of the wafer, and the resist after 10 implants can be completely removed without leaving residue. (Industrial Utilization Possibilities) The present invention can be widely utilized in the step of removing a resist from a substrate. [Simple description of the diagram] 帛1® shows the conceptual diagram of the system of the yin-counter in addition to the system. Figure 2 is a conceptual diagram showing the resist removal system of the second form. Fig. 3 (a) to (4) are conceptual views showing the resist removal step of the present preferred embodiment. Figure 4 is a graph showing the cross-sectional SEM image of the pattern after the ion implantation of the resist used in the examples 320559 23 201009929. Fig. 5 is a cross-sectional SEM image showing the plasma treatment of the examples. Fig. 6 is a cross-sectional SEM image showing the surface of the wafer after the ozone water treatment of the example. [Main component symbol description]
1 基板· 2 阻劑 2a 變質層 2b 未變質層 100 非等向性電漿處理裝置 111 ' 211 ' 511 氣體供應部 120 非等向性電漿產生部 130 、 220 、 530 電漿生成部 131 ' 221 ' 531 電漿生成部本體 132 、 222 、 532 南頻線圈 133 、 223 、 533 南頻電源 140、540 偏壓電力施加部 141、541 偏壓電極 142、542 偏壓電源 150、230、320、550 機台 160 、 240 、 560 導引手段 170 ' 250 、 570 處理反應室 180 、 260 、 580 減壓手段 181 ' 261 ' 581 真空泵182、262、582 氣體分析器 183 、 263 、 583 閥 190、270、590 機台溫度調節部 191、271、591 溫水/冷水生成部 200 等向性電漿處理裝置 24 320559 201009929 241 離子阻隔板 300 洗淨裝置 310 處理媒體供應部 311 處理媒體供應槽 312 加熱部 313 供應喷嘴 314 臭氧水生成部 400 搬運裝置 401 對象物保持部 402 動作部（動作手段） 403 支撐體 500 非等向性/等向性電漿處理裝置 520 非等向性/等向性電漿產生部 543 開關 544 電力調整手段 SI ' S2 阻劑去除系統1 substrate·2 resist 2a modified layer 2b unaltered layer 100 anisotropic plasma processing apparatus 111 '211 ' 511 gas supply unit 120 anisotropic plasma generating unit 130, 220, 530 plasma generating unit 131 ' 221 ' 531 plasma generating unit body 132, 222, 532 south frequency coil 133, 223, 533 south frequency power supply 140, 540 bias power applying unit 141, 541 bias electrode 142, 542 bias power source 150, 230, 320, 550 machine 160, 240, 560 guiding means 170 '250, 570 processing reaction chamber 180, 260, 580 decompression means 181 '261 ' 581 vacuum pump 182, 262, 582 gas analyzer 183, 263, 583 valve 190, 270 590 machine temperature adjustment unit 191, 271, 591 warm water/cold water generation unit 200 isotropic plasma processing device 24 320559 201009929 241 ion blocking plate 300 cleaning device 310 processing medium supply unit 311 processing medium supply tank 312 heating unit 313 Supply nozzle 314 Ozone water generating unit 400 Transport device 401 Object holding unit 402 Operating unit (operation means) 403 Support 500 Non-isotropic/isotropic plasma processing equipment 520 anisotropic / isotropic plasma generating portion 543 switches the power adjusting means 544 SI 'S2 resist removal system
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