、發明説明（ 1 _ _ 發明之背景 1. 登明之領域 -- 本發明係關於一種清除殘餘物之方法，更具體而言，係 ，於一種於積體電路製造過程中，於介層洞蝕刻後^除殘 留在介層洞四周的殘餘物之方法。 ^ 2. 立前技藝之說明 於製造積體電路中介層洞的過程，必須以蝕刻方式形成 A層洞。孩介層洞於蝕刻後會有殘餘物，特別是高分子殘 餘物，殘留在積體電路，特別是該介層洞的侧壁上。因此 ，於餘刻介層、;同以及去除光阻後，必帛進行殘餘物的 清除。 以下針對餘刻形成介層洞與去除光阻後形成殘餘物、以 及習知清除殘餘物的方法做一說明。當進行蝕刻製程以形 成介層洞時，蝕刻過程所產生的高分子物會殘留在介層洞 侧土。忒同分子物的產生，一般係由於姓刻物質與光阻等 於姓刻過程中反應後所產生。蚀刻形成介層洞後進行去除 光阻步驟’一般去除光阻步騾的光阻灰化（ashing)流程 係使用電漿，將光阻灰化後加以清除。此時殘餘物依然會， 殘留在介層洞侧壁上。 由於介層洞的殘餘物會造成介層洞的尺寸控制不易，並 且影響積體電路的電性效能，因此接著進行介層洞蝕刻後 的清除殘餘物製程。習知方法係使用由漢誠公司所代理 ASHLAND之ACT93 5溶液清洗，然後進行水洗，其清洗 私序一般係依序進行5至3 0分鐘的ACT 93 5溶液清洗、1至 ^紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背*之注t:事項再填寫本頁) -訂 經濟部智慧財產局員工消費合作社印製 5099732. Description of the invention (1 _ _ Background of the invention 1. The field of the invention-The present invention relates to a method for removing residues, more specifically, to a process for etching a via in a integrated circuit during the manufacturing process of integrated circuits ^ Method for removing the residues left around the vias. ^ 2. The description of the previous technique in the process of manufacturing the interposer holes in the integrated circuit must form the A-layer holes by etching. After the vias are etched There will be residues, especially polymer residues, remaining on the integrated circuit, especially on the sidewall of the interlayer hole. Therefore, after the interlayer is etched and the photoresist is removed, the residue must be carried out. The following is a description of the formation of interlayer holes and the formation of residues after removal of photoresist, and the conventional method of removing the residues. When the etching process is performed to form the interlayer holes, the polymer produced by the etching process Residues will remain in the soil on the side of the interstitial cavity. The production of different molecules is generally caused by the reaction between the engraved material and the photoresist equal to the last engraved process. The photoresist removal step is performed after the formation of the interlayer cavity. Photoresist The step of the photoresist ashing process uses a plasma to ash the photoresist and remove it. At this time, the residue will still remain on the sidewall of the via. Because the residue of the via will cause The size of the via is difficult to control, and it affects the electrical performance of the integrated circuit. Therefore, the process of removing the residue after the via is etched. The conventional method is to use the ACT93 5 solution of ASHLAND, which is represented by Hancheng. It is then washed with water. The cleaning sequence is generally 5 to 30 minutes of ACT 93 5 solution cleaning, 1 to ^ paper size applicable to China National Standard (CNS) A4 specifications (210X297 mm) (please read the back first) Note t: Please fill in this page again for matters)-Ordered by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economy 509973
ίο分鐘的異丙醇清洗、1至10分鐘去離子水的快速傾倒洗濯 (QDR ’ qUick_dump rinse) 、1至10分鐘的最終清洗以 及約1 0分鐘的乾燥等程序。 習知清除殘餘物方法的缺點在於，所使用的A c τ 9 3 5溶液 係 種包含喪胺（hydroxyl amine )、鄰苯二紛（ catechol )水以及乙醇胺（monoethanolamine)之驗 性’谷液’其會產生幾基負離子（Ο H -)並與介層洞以下的金 屬層反應產生沉澱物。舉鋁金屬為例，其產生的反應式如 下：οο minutes of isopropyl alcohol cleaning, 1 to 10 minutes of deionized water rapid pour (QDR ′ qUick_dump rinse), 1 to 10 minutes of final cleaning, and about 10 minutes of drying and other procedures. The disadvantage of the conventional method of removing residues is that the A c τ 9 3 5 solution used is an experimental 'cereal' containing hydroxyl amine, catechol water, and monoethanolamine. It will generate a few base ions (0 H-) and react with the metal layer below the via to produce a precipitate. Taking aluminum as an example, the reaction formula is as follows:
Al-+ 30H^ Al(〇H)3(s, gel) 雖然部分沉澱物接著會再與羥基負離子（〇Η·)產生如下 的反應並溶於水中而被帶走： Α1(0Η)3 + 〇Η_ — Α1(0Η)4· 合Υ疋如果程序控制不當，清洗效果不夠，該沉澱物就 會形成問《。再纟，金屬層被侵姓會變成一個嚴重的問題 ，特別是如果異丙醇清洗以及快速傾倒洗濯無法帶走由 A C Τ所快速產生的幾基負離子。 經濟部智慧財產局員工消費合作社印製 再者，光阻灰化步驟與清除殘餘物製程的ACT以及異丙 醇清洗係分㈣不同機台處理，製造程序比較複雜，程序 控制比較不容易。再者’其中所使用的有機物質如異丙醇 、羥胺、鄰苯二酚以及乙醇胺等，不僅需要二次處理 且會影響環境。 本發明針對上述習知技術使㈣性溶液所產生金屬層户 兹以及程序控制等缺點，提出-使用氧氣以及含氟氣體:Al- + 30H ^ Al (〇H) 3 (s, gel) Although some of the precipitate will then react with the hydroxyl anion (〇Η ·) and dissolve in water to be taken away: Α1 (0Η) 3 + 〇Η_ — Α1 (0Η) 4 · If the program is not properly controlled and the cleaning effect is insufficient, the precipitate will form. Furthermore, the invasion of the metal layer will become a serious problem, especially if the isopropyl alcohol cleaning and the rapid dumping washing cannot take away the several negative ions quickly generated by ACT. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Furthermore, the photoresist ashing step and the ACT for removing residues and isopropyl alcohol cleaning are separated into different machines. The manufacturing process is more complicated and the process control is not easy. Moreover, the organic substances used therein, such as isopropyl alcohol, hydroxylamine, catechol, and ethanolamine, require not only secondary treatment but also affect the environment. The present invention addresses the shortcomings of the metal layer produced by the alkaline solution and the program control by the conventional technology mentioned above, and proposes-using oxygen and fluorine-containing gas:
本紙張尺度適用 5^)9973 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（3 ) 乾式清除殘餘物方法。 發明之概述 本發明之一目的在提供一種於介層洞触刻後清除殘餘物 的方法。其使用乾式的氧氣以及含氟氣體電漿，可以避免 習知技術造成金屬層侵蝕的缺點。並且，由於本發明的乾 式清除方法可以於與光阻灰化相同的機台中進行，進一步 更能夠簡化流程，增進生產效率，並且兼顧環境保護的要 求。 為了達成上述目的並避免上述習知技術的缺點，本發明 揭示一種於介層洞蚀刻後清除殘餘物的方法，包含下列步 騾：提供一侧壁具有殘餘物之積體電路的介層洞，將該介 層洞暴露於一包含氧氣以及含氟氣體之電漿中，以及以水 洗濯並移除該殘餘物。於一具體較佳實施例中，本發明另 揭示一種於介層洞姓刻後清除殘餘物的方法，該介層洞係 位於一基材上之金屬層上，且四周係由一介電層所包圍， 而該殘餘物係位於該介層洞的周圍與該介電層之間，包含 下列步騾：將該具有介層洞之基材置於一反應室内，通入 一包含氧氣以及含氣氣體之氣體於該反應室内，形成一氧 氣以及含氟氣體之電漿於該反應室内，該氧氣以及含氟氣 體之電漿作用於該殘餘物，終止該氧氣以及含氟氣體之電 漿的形成，以及使用純水洗濯該具有介層洞之基材以移除 該殘餘物。其中，該含氟氣體係選自三氟化氮，六氟化硫 及四氟化碳。 藉由本發明所揭示之方法，介層洞於I虫刻形成後殘餘物 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注惫事項再填寫本頁)This paper is applicable to the standard 5 ^) 9973 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (3) Dry residue removal method. SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for removing residues after a via hole is etched. The use of dry oxygen and fluorine-containing gas plasma can avoid the disadvantages of metal layer erosion caused by conventional techniques. In addition, since the dry cleaning method of the present invention can be performed in the same machine as photoresist ashing, the process can be further simplified, production efficiency can be improved, and environmental protection requirements can be taken into consideration. In order to achieve the above-mentioned objective and avoid the disadvantages of the conventional techniques, the present invention discloses a method for removing residues after etching of a via hole, which includes the following steps: providing a via hole having an integrated circuit with a residue on a sidewall, The via is exposed to a plasma containing oxygen and a fluorine-containing gas, and the residue is washed with water and removed. In a specific preferred embodiment, the present invention further discloses a method for removing residues after the engraving of a via hole, which is located on a metal layer on a substrate and surrounded by a dielectric layer. It is surrounded, and the residue is located between the periphery of the interlayer hole and the dielectric layer, and includes the following steps: placing the substrate with the interlayer hole in a reaction chamber, and passing in a gas containing oxygen and containing The gas in the gas forms a plasma of oxygen and fluorine-containing gas in the reaction chamber. The plasma of oxygen and fluorine-containing gas acts on the residue, and the plasma of the oxygen and fluorine-containing gas is terminated. Forming, and washing the substrate with interlayer holes using pure water to remove the residue. The fluorine-containing gas system is selected from nitrogen trifluoride, sulfur hexafluoride, and carbon tetrafluoride. By the method disclosed in the present invention, the residue after the formation of the interstitial hole in the worm is formed. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm). (Please read the note on the back before filling out this page. )
5^)9973 A7 B7 五、發明説明（4 ) 的清除將更有效率，可以避免金屬層侵蝕的問題，並且具 較佳具體實例之說明 經濟部智慧財產局員工消費合作社印製 有兼顧環境保護的優點。 圖式簡單說明 1 圖la顯示於蝕刻形成介層洞後殘餘物殘留在介層洞侧壁； ； 圖lb顯示光阻灰化後殘餘物依然殘留在介層洞侧壁； ； 圖1 c顯示清除殘餘物後之介層洞。 丨 圖式元件符號說明 , ； 1 基材 2金屬層 ： 3 介電層 4 光阻 5 殘餘物 6 介層洞 f清毛閱漬背S-之生春事頃再嗔寫本頁) 訂 以下請參考圖la至圖lc說明介層洞於蝕刻後進行灰化以 及α除S餘物時之結構變化。圖1 a顯示位於基材1上的金屬 層2，其上具有介電層3以及光阻4。如同習於技藝人士所了 解者，該基材丨一般可以是矽晶圓，而該金屬層2與該基Mi <間可能介有其它介電層或導線等各種層次。於蝕刻形成 介層洞6後，殘餘物5殘留在介層洞6的侧壁。殘餘物產生的 原因 #又疋因為電漿ί虫刻物質，例如八說化四碳，與光阻 產生反應後形成高分子殘餘物，於钱刻完畢後依然留在介 層洞6的側壁。 圖lb顯示進一步光阻灰化（ashing)後的介層洞結構。 該介層洞6係由一介電層3所包圍，且位於一基材1上之金屬 層2上。殘餘物5係位於該介層洞6的周圍與該介電層3之間 ’也就是在介層洞6的侧壁。一般光阻灰化流程係以氧氣、 本紙張尺度適用中國國家榡準（CNS ) A4規格（210X297公釐） 509973 A7 B7 五 、發明説明（ 經濟部智慧財產局員工消費合作社印製 氧氣/氮氣、或者氧氣/氮氣/氫氣等氣體形成電漿，以將光 阻灰化並清除之，但疋，殘餘物5依然會留在介層洞6的侧 壁0 圖lc顯示清除殘餘物後之介層洞，也是本發明清除殘餘 物之方法實施後之結果。以下，以一具體實施例詳細說明 本發明之方法。 首先，係將該介層洞暴露於一包含氧氣以及三氟化氮之 電漿中，最後以水洗濯並移除該殘餘物。清除殘餘物的方 法包含下列步騾：將該具有介層洞6之基材丨置於一反應室 内，通入一包含氧氣以及三氟化氮之氣體於該反應室内， 形成一氧氣以及二氟化氮之電漿於該反應室内，該氧氣以 及三氟化氮之電漿作用於該殘餘物5，其中電衆處理的條件 如下： 反應室壓力··介於1 000毫托耳（mT〇rr)至2〇〇〇毫托耳 之間，較佳者為1 5 0 0毫托耳； 功率：介於800瓦特至1 500瓦特之間，較佳者為ιι〇〇 特； 氧氣與含說乳體之氣體體積流量比：介於1〇1至4〇 1 間；比例越小者’例如10: i，則損失的氧化物 1 〇 s s )會比較多。 於本發明之一實施例中，係通入2 〇 〇 〇 b · c . C .m之氧氣， 以及100 s.c.c.m之三氟化氮氣體，於溫 又下進行雷 處理約60秒。於本發明之另一具體實施 十 、 电聚係以 源開關反覆開與關的脈衝動作操作之， η 杈外凊除效率 本紙張尺度適用中國國家( CNS ) M規格^γ1〇χ^公董） 瓦 之 漿 電 (請先閲讀背赴之注务事項再填寫本頁)5 ^) 9973 A7 B7 V. The description of the invention (4) will be more efficient, which can avoid the problem of metal layer erosion, and there are better specific examples to explain that the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has printed environmental protection The advantages. Brief description of the drawing 1 FIG. 1a shows that the residue remains on the side wall of the via after the via hole is formed by etching; FIG. 1b shows that the residue still remains on the side wall of the via after the photoresist ashing; FIG. 1c shows Interstitial holes after removal of residue.丨 Illustration of Symbols of Schematic Elements; 1 Substrate 2 Metal Layer: 3 Dielectric Layer 4 Photoresistor 5 Residue 6 Interlayer Holes f Cleansing and Reading Back S-Life's Spring Events are reproduced on this page) Order the following Please refer to FIG. 1 to FIG. 1C to describe the structural changes of the via hole after ashing and α removal of S residues after etching. Figure 1a shows a metal layer 2 on a substrate 1 with a dielectric layer 3 and a photoresist 4 thereon. As understood by those skilled in the art, the substrate can generally be a silicon wafer, and the metal layer 2 and the base Mi < may have other layers such as other dielectric layers or wires. After the via hole 6 is formed by etching, the residue 5 remains on the sidewall of the via hole 6. Reasons for the residue #Also, because the plasma engraved material, such as eight carbons, reacts with the photoresist to form a polymer residue, which remains on the sidewall of the interlayer hole 6 after the money is engraved. Figure lb shows the via structure after further photoresist ashing. The interlayer hole 6 is surrounded by a dielectric layer 3 and is located on the metal layer 2 on a substrate 1. The residue 5 is located between the periphery of the via hole 6 and the dielectric layer 3 ′, that is, on the sidewall of the via hole 6. The general photoresist ashing process is based on oxygen. This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 509973 A7 B7. 5. Description of the invention (Printed oxygen / nitrogen, Or oxygen / nitrogen / hydrogen gas forms a plasma to ash and remove the photoresist, but alas, the residue 5 will still remain on the sidewall of the interlayer hole 6. Figure lc shows the interlayer after the residue is removed The hole is also the result of the method for removing residues of the present invention. Hereinafter, the method of the present invention will be described in detail with a specific embodiment. First, the interlayer hole is exposed to a plasma containing oxygen and nitrogen trifluoride. Finally, the residue is washed with water and removed. The method of removing the residue includes the following steps: placing the substrate with the interstitial hole 6 in a reaction chamber, and passing in a gas containing oxygen and nitrogen trifluoride The gas in the reaction chamber forms a plasma of oxygen and nitrogen difluoride in the reaction chamber, and the plasma of oxygen and nitrogen trifluoride acts on the residue 5. The conditions for the treatment of the electric mass are as follows: Chamber pressure · Between 1 000 millitorr (mT0rr) and 2000 millitorr, preferably 1 500 millitorr; Power: between 800 watts and 1,500 watts The preferred ratio is ιι〇〇; the volumetric flow rate of oxygen to the gas containing milk: between 101 and 401; the smaller the ratio, such as 10: i, the lost oxide 1 〇ss) will be more. In one embodiment of the present invention, 2000 b.c.c.m of oxygen gas and 100 s.c.c.m. of nitrogen trifluoride gas are applied, and the lightning treatment is performed at a temperature of about 60 seconds. In another specific implementation of the present invention, ten, the electropolymerization is performed by the pulse action of the source switch repeatedly turning on and off, η outside the removal efficiency This paper standard applies to China National (CNS) M specifications ^ γ1〇χ ^ ) Watamura Electric (please read the note on the back and fill in this page)
五 其開與關的時間比例約為5 : i。 使用含氟氣體配合稀釋氣 效地將殘餘物分解。含氟：氧斤形成的電漿，可以有 明藉由運用, 矾肢—般係用於蝕刻製程，本發 乃猎由運用含藏氣體的特性，配人 、主 不愈 刻後的殘餘物，可以達到者 口 ^ w目除介層洞蝕 體的選擇係依製程要有效^除殘餘物的目的。含氟氣 ― 要求的不同而有所不同，H士、 二氟化氮、六氟化硫以及氟 、又口，以 及等向神r. 四鼠化碳乳體而T，化學活性以 氟化硫以及四氟化鲈·炊“ 依-為二貺化氮、六 人w 然而對於半導體製程所經常使用的 介電物質氧化層（_)，例如二氧切而言，：： 以及四氟化碳的㈣率比三氟化氮大，因此如果待 餘物的表面物質是氧化層，且使用的氣體是六氟化碳或者 四氟化碳’則必須調整㈣條件，例如降低 降低電漿清洗的時間。 戈者 經濟部智慧財產局員工消費合作社印製 f漿反應完成後終止該氧氣以及三氟化氮之電漿的形成 ，最後，使用純水洗濯該具有介層洞6之基材i以移除該殘 餘物5，其中該純水係指一般熟習於此行業之技藝人士:能 充分了解之用於積體電路清洗晶圓片之純水，其至少是2. 離子水等級以上之純水。該以純水洗濯之處理時間及步騾 如下： 一 λ 快速傾倒洗濯：較佳者5.0分鐘，一般為3 〇分鐘至7 〇分 鐘之間； 最終洗濯：較佳者6 · 0分鐘，一般為2 · 〇分鐘至丨〇 . 〇分鐘 之間；以及 本紙張尺度適用中國國家標準（CNS ) A4規格(210X-2W公釐) A7 B7 五 、發明説明（ 乾燥：較佳者10.0分鐘，一般為6.0分鐘至14 〇分鐘之間 〇 經由本發明所揭示之於介層洞蝕刻後清除殘餘物的方法 蜮餘物能夠以乾式清洗的方法去除，避免使用有機溶劑 而且避免介電層以下的金屬層受到侵蝕，可以有效且方便 地清除殘餘物。 以上所述之詳細說明’僅為本發明之較佳樣態而已，並 非據以限足本發明之保護範圍；凡其它未發 示猜神下之衍生或改變，均應該由下】 範圍所界定。 、力心甲叫專利 (請先閎讀背之注秦事項再填寫本頁)Five The ratio of its opening and closing time is about 5: i. The residue is effectively decomposed by using a fluorine-containing gas in combination with a dilution gas. Containing fluorine: the plasma formed by oxygen can be used by the alum limbs—usually used in the etching process. It can achieve the purpose of removing the cavities of the interstitial cavity according to the process to effectively remove the residue. Fluorine-containing gas-different requirements, H Shi, nitrogen difluoride, sulfur hexafluoride and fluorine, and mouth, and isotropic God r. Tetra-ratified carbon emulsion and T, chemical activity to fluorinated Sulfur and perfluorinated perch.--Is nitrogen dioxide, six people w However, for dielectric oxide layers (_) often used in semiconductor manufacturing processes, such as dioxin: :: and tetrafluoride The rate of carbon is greater than that of nitrogen trifluoride, so if the surface material of the residue is an oxide layer, and the gas used is carbon hexafluoride or carbon tetrafluoride, you must adjust the radon conditions, such as reducing the plasma cleaning. After the completion of the plasma printing reaction of the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the formation of the plasma of oxygen and nitrogen trifluoride was terminated. Finally, the substrate with the interstitial hole 6 was washed with pure water In order to remove the residue 5, the pure water refers to those skilled in the industry: can fully understand the pure water used in integrated circuit cleaning wafers, which is at least 2. ion water level above the Pure water. The processing time and steps for washing with pure water are as follows : One lambda rapid pouring washing: preferably 5.0 minutes, generally between 30 minutes and 70 minutes; final washing: better 60 minutes, generally between 2.0 minutes to 丨 0.0 minutes ; And this paper size applies the Chinese National Standard (CNS) A4 specification (210X-2W mm) A7 B7 V. Description of the invention (Drying: preferably 10.0 minutes, generally between 6.0 minutes and 140 minutes. Through the present invention The disclosed method for removing residues after the etching of the interlayer holes can be removed by dry cleaning, avoiding the use of organic solvents and preventing the metal layers below the dielectric layer from being eroded, and the residues can be effectively and conveniently removed. The detailed descriptions above are only the preferred aspects of the present invention, and are not intended to limit the scope of protection of the present invention; all other derivatives or changes under the condition of no guessing should be defined by the scope below] . Lixin Jia is called a patent (please read the Qin notes in the back first and then fill out this page)
經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm)