12733¾ itwfdoc/ooe 九、發明說明： 【發明所屬之技術領域】127333⁄4 itwfdoc/ooe IX. Description of the invention: [Technical field to which the invention belongs]
關於本ίΓ是有關於—種半導體清洗製程，^特別是有 關於-種光_離組合物及方法。 W 【先前技術】 之—㈣餘要的步驟 5 ’先罩面的元件圖案，是先藉著微影製 ί=ΓΛ然後再利用_製程，來完成整= 膜，將成丰㈣的Γ終目的。這層經過微影與㈣的薄 式全體:'的-部分。以金氧半導體元件或互補 (Si〇2、+i牛的製程為例’這層薄膜可缺二氧化石夕 allow 4iiit 1 匕石夕（Sl3N4)、複晶石夕(P〇ly-Si)、1呂合金(A1 耸。:5 、銅合金或是磷石夕玻壤(Phos—ate ，PSG) 經過構成半導體元件的主要材料’都必須 層地二=的;::以侧 务於I^來兒在般形成導體圖案的製程中，通常會 或it,序形成一層氧化矽層與-層導體層(複Μ 圖Ϊ化光料如紹、銅等)後，再於此導體層上形成一 雜靖曝;二=層作為_罩幕’利用乾 再去除触層層如㈣，似彡解翻案。之後 (〇二，的方法是以臭氧灰化 層後，再次入熱硫酸溶液中或以有機 ltwf.doc/006 驗，配極性溶液清洗。然而，以臭氧灰化及熱硫酸法並無 法，全去除光阻殘留物。因此，經臭氧灰化與熱硫酸處理 之曰曰片仍系要浸入稀釋的氫氟酸液體中，而且浸入氫氟酸 溶液之時間不能太長，以避免晶片上之氧化物層或金屬導 線受到腐蝕。 至於使用有機鹼清洗能有效去除光阻殘留物，卻會 對金屬導線元件及金屬阻障層造成腐蝕。所以加上一使用 有機/谷劑清洗的步驟，以去除光阻剝離組合物中的驗性成 份，降低後續以去離子水水洗製程中其鹼性成分對金屬導 線元件造成腐蝕，但是對金屬導線元件的仍造成一定程度 的腐姓。因此，光阻剝離組合物仍是未來發展的重點。 【發明内容】 有鑑於此，本發明之一目的為提供一種光阻剝離組 合物，可以有效的移除乾蝕刻後殘留於導體圖案上之光阻 殘留物’並避免導體圖案受到清洗液腐姓。 本發明之另一目的為提供一種光阻剝離方法，可以 簡化光阻剝離製程。 本發明提出一種光阻剝離組合物，至少是由醇胺化 合物、二醇類化合物(carbitol)及N，N-二曱基乙醢胺(凡义 dimethyl acetamine，DMAC)所組成。其中，醇胺化合物 之比例範圍例如是20wt%至80wt%。二醇類化合物(carbitol) 之比例範圍例如是20wt%至80wt%。N，N-二曱基乙醯胺 (N，N-dimethyl acetamine，DMAC)之比例範圍例如是 O.lwt%至 15wt% 〇 12733¾ ltwf.doc/006 依照本發明一較佳實施例所述之光阻剝離組合物， 八中胺醇化合物係選自乙醇胺（咖n〇ethan〇iamine， MEA)、N_甲基乙醇胺、N，N•二甲基乙醇胺、义乙基乙醇 胺、N-甲基其乙基乙醇胺、耶-二乙基乙醇胺所組之族 群。 、 依照本發明一較佳實施例所述之光阻剝離組合物， 其中一醇類化合物(carbitol)係選自單丁 _ 一縮貳[乙二 醇Kdiethylene glyC〇i mon〇butyi ether，BDG)、單乙醚一 縮底[乙二醇]、二甲喊一縮武[乙二醇]、二乙醚一縮貳[乙 二醇]、二丁醚一縮貳[乙二醇]、醋酸單丁醚一縮貳[乙二 醇]所組之族群。 本發明提出一種光阻剝離方法。首先，提供一晶圓， 此晶圓上具有經乾蝕刻後之一圖案，該圖案表面上具有一 光阻殘留物。然後以包括醇胺化合物、二醇類化合物 (carbitol)及 N，N-二甲基乙醯胺(N，N_dimethyl acetamine， DMAC)的光阻剝離組合物移除該光阻殘留物，其中醇胺 化合物之比例範圍為2〇wt%至80wt°/。、二醇類化合物 (carbltol)之比例範圍為20wt%至80wt%以及N，N-二曱基 乙醯 &c (N，N-dimethyl acetamine，DMAC)之比例範圍為 O.lwt%至 15wt%。 依照本發明一較佳實施例所述之光阻剝離方法，更 包括在以光阻剝離組合物清洗後，再以一去離水進行 洗。 依照本發明一較佳實施例所述之光阻剝離方法，其 12733^ ltwf.doc/006 12733^ ltwf.doc/006 的、特徵和優點能更明 ’並配合所附圖式，作詳 為讓本發明之上述和其他目 顯易懂，下文特舉一較佳實施例 細說明如下。 【實施方式】 首先，說明本發明之光阻剝離組合物。 本發明之光阻剝離組合物，包括醇胺化合物、二醇 類化合物（carbitol)及N，N_二曱基乙醯胺(N，N dimethyl acetamine，DMAC)所組成。 醇胺化s物例如是乙醇胺（m〇n〇ethan〇iamine, MEA)、N_曱基乙醇胺、__二甲基乙醇胺、N-乙基乙醇 胺、N_甲基，N-乙基乙醇胺、n，N-二乙基乙醇胺等。醇胺 化合物之比例範圍例如是2〇wt%至80wt%。在本發明之 光阻剝離組合物中，可以單獨使用一種醇胺化合物，或者 也可以合併兩種以上之醇胺化合物而使用之。 二醇類化合物例如是單丁醚一縮家[乙二 醇](diethylene glycol monobutyl ether，BDG)、單乙醚— 縮貳[乙二醇]、二甲醚一縮貳[乙二醇]、二乙醚一縮武[乙 二醇]、二丁醚一縮貳[乙二醇]、醋酸單丁醚一縮武[乙二 ]專。一知類化合物(caxbitol)之比例範圍例如是2〇wt% 至80wt%。在本發明之光阻剝離組合物中，可以單獨使 用一種二醇類化合物，或者也可以合併兩種以上之二醇類 化合物而使用之。 ltwf.doc/006 N，N 一 曱基乙醯胺(N，N-dimethyl acetamine，DMAC) 之比例紅圍例如是O.lwt%至15wt%。 /使用本發明之光阻剝離組合物可以有效的去除乾蝕 Μ後光《胃物。而且’在本發明之光阻祕組合物可以 在有效地移除光組殘留物之同時，防止金屬表面受到腐 餘0 以下i特舉出實驗例1、實驗例2、實驗例3、實驗 例4、比較例以詳細的說明本發明。其中，實驗例1、實 驗例2 :實驗Μ 3、實驗爿4、tb較例之成分及組成如下 ~~離組合物所包含之成分及纟表Regarding this, there is a semiconductor cleaning process, and in particular, there is a light-off composition and method. W [Prior Art] - (4) The remaining steps 5 'The first component of the mask pattern is to use the lithography system ί = ΓΛ and then use the _ process to complete the whole film, the end of Cheng Feng (four) purpose. This layer is lithographically and (4) thin all: '--part. Take the MOS device or the complementary (Si〇2, +i cattle process as an example). This film can be deficient in the dioxide. allowallow 4iiit 1 匕石夕(Sl3N4), 晶晶石(P〇ly-Si) , 1 Lu alloy (A1 tower.: 5, copper alloy or Phosphorus (PS)) The main material that constitutes the semiconductor component must be layered ==; ^In the process of forming a conductor pattern, a layer of yttrium oxide layer and a layer of conductor layer (such as ruthenium, copper, etc.) are usually formed or sequentially, and then on the conductor layer. Forming a miscellaneous exposure; the second layer acts as a _mask to dry and then remove the contact layer such as (4), which seems to solve the problem. After that, the method is to ash the layer and then enter the hot sulfuric acid solution again. Or use the organic ltwf.doc/006 test, with a polar solution to clean. However, the ozone ashing and hot sulfuric acid method can not completely remove the photoresist residue. Therefore, the ointment treated by ozone ashing and hot sulfuric acid still Is to be immersed in a dilute hydrofluoric acid liquid, and the time of immersion in the hydrofluoric acid solution should not be too long to avoid oxide layer or metal on the wafer. The wire is corroded. As for the use of organic alkali cleaning, the photoresist residue can be effectively removed, but the metal wire component and the metal barrier layer are corroded. Therefore, an organic/grain cleaning step is added to remove the photoresist stripping combination. The test composition in the material reduces the subsequent corrosion of the metal wire component by the alkaline component in the deionized water water washing process, but still causes a certain degree of corrosion to the metal wire component. Therefore, the photoresist stripping composition is still SUMMARY OF THE INVENTION In view of the above, it is an object of the present invention to provide a photoresist stripping composition which can effectively remove photoresist residues remaining on a conductor pattern after dry etching and avoid conductor patterns. It is another object of the present invention to provide a photoresist stripping method which can simplify the photoresist stripping process. The present invention provides a photoresist stripping composition, which is at least composed of an alcohol amine compound and a glycol compound (carbitol). And N,N-dimercaptoacetamide (DMA), wherein the ratio of the proportion of the alcohol amine compound For example, it is 20% by weight to 80% by weight. The ratio of the carbitol ranges, for example, from 20% by weight to 80% by weight. The ratio of N, N-dimethyl acetamine (DMAC) ranges, for example. O.lwt% to 15wt% 〇127333⁄4 ltwf.doc/006 A photoresist stripping composition according to a preferred embodiment of the present invention, the octaaminol compound is selected from the group consisting of ethanolamine (ca n〇ethan〇iamine, MEA) ), N-methylethanolamine, N,N-dimethylethanolamine, ethylethanolamine, N-methylethylethanolamine, yt-diethylethanolamine group. The photoresist stripping composition according to the preferred embodiment of the present invention, wherein the carbitol is selected from the group consisting of dimethyl ketone (ethylene glycol Kdiethylene glyC〇i mon〇butyi ether, BDG). , monoethyl ether-shrinking bottom [ethylene glycol], dimethyl shark-shrinking [ethylene glycol], diethyl ether-hydrazine [ethylene glycol], dibutyl ether-condensed hydrazine [ethylene glycol], acetic acid monobutyl The group of ether-condensed oxime [ethylene glycol]. The present invention provides a photoresist stripping method. First, a wafer is provided having a pattern after dry etching having a photoresist residue on the surface. The photoresist residue is then removed with a photoresist stripping composition comprising an alcohol amine compound, a carbitol, and N,N-dimethylacetamine (DMAC), wherein the alcoholamine The ratio of the compound ranges from 2% by weight to 80% by weight. The ratio of the carbol is in the range of 20% by weight to 80% by weight and the ratio of N,N-dimethylacetate (DMAC) is in the range of 0.1% by weight to 15% by weight. %. The photoresist stripping method according to a preferred embodiment of the present invention further comprises washing with a stripping composition after washing with the photoresist stripping composition. According to a photoresist stripping method according to a preferred embodiment of the present invention, the features and advantages of 12733^ltwf.doc/006 12733^ltwf.doc/006 can be more clearly defined and matched with the drawings. The above and other objects of the present invention will become apparent from the following detailed description. [Embodiment] First, the photoresist release composition of the present invention will be described. The photoresist stripping composition of the present invention comprises an alcohol amine compound, a carbitol and N, N dimethyl acetamine (DMAC). The alcohol aminated substance is, for example, ethanolamine (m〇n〇ethan〇iamine, MEA), N_mercaptoethanolamine, __dimethylethanolamine, N-ethylethanolamine, N-methyl, N-ethylethanolamine, n, N-diethylethanolamine and the like. The proportion of the alcoholamine compound ranges, for example, from 2% by weight to 80% by weight. In the photoresist release composition of the present invention, an alcohol amine compound may be used alone or two or more alcohol amine compounds may be used in combination. The diol compound is, for example, diethylene glycol monobutyl ether (BDG), monoethyl ether - condensed oxime [ethylene glycol], dimethyl ether condensed oxime [ethylene glycol], Ether-shrinking [ethylene glycol], dibutyl ether-hydrazine [ethylene glycol], acetic acid monobutyl ether-shrinking [Ethylene] special. The ratio of a compound (caxbitol) is, for example, 2% by weight to 80% by weight. In the photoresist release composition of the present invention, a diol compound may be used singly or two or more diol compounds may be used in combination. Lww.doc/006 N, N-N-dimethyl acetamine (DMAC) The ratio red square is, for example, 0.1% by weight to 15% by weight. / Using the photoresist stripping composition of the present invention, it is possible to effectively remove dry etching and "light." Moreover, in the photo-blocking composition of the present invention, the metal surface can be prevented from being subjected to corrosion by 0 while effectively removing the residue of the light group. Experimental Example 1, Experimental Example 2, Experimental Example 3, and Experimental Example 4. Comparative Example The present invention will be described in detail. Among them, the experimental example 1, the experimental example 2: the experimental Μ 3, the experimental 爿 4, the composition and composition of the tb comparative example are as follows ~ ~ from the composition of the components and 纟 table
<測試片之製備> i m序於基底上形錢切氮切堆疊岸 後基底上形成—層圖案化光阻層，並以圖案^ /铭/氮化破堆案化光阻層所暴露之氮化石夕 隹$層，而形成導體圖案。以上述方式製作出 12733¾ ltwf.doc/006 多個測試片，並分別以實驗例1、實驗例2、實驗例3、 實驗例4、比較例之光阻剝離組合物處理測試片，然後利 用掃瞄式電子顯微鏡(scanning electron microsocope，SEM) 觀察以實驗例1、實驗例2、實驗例3、實驗例4、比較例 之光阻剝離組合物處理後各個測試片上之導體圖案，並比 車父實驗例1、實驗例2、實驗例3、實驗例4、比較例之差 異0 然後，以實驗例1、實驗例2、實驗例3、實驗例4、 比較例之光阻剝離組合物處理測試片例如是以浸泡，噴灑 (spray)或旋轉喷灑(spin etch)之方式剝離清洗經乾刻後 附著於導體圖案表面之絲殘留物。接著，在對光阻= 光阻剝離組合物 ?進!離清洗後’再使用子水進行清洗，以除去 下表2係以實驗例丨、實驗例2、 给 4、比較例之光阻剝離組合物處理測試片'驗二5义:例 阻剝離時間與光阻剝離厚度的關係表。 刀内光 ltwf.doc/006 ltwf.doc/006 查一2光阻剝除時間产厚度關^^ 組另1?\ 0 1 2 3 5 0〜1分 0〜5分 光阻^ 〖虫刻厚度(埃） 名虫刻率< :埃/分） 比較例 5666 5622.5 5590.5 5517 5327.5 43.5 67.7 實驗例1 6281.5 6281 6206.5 6114 5900 0.5 76.3 實驗例2 5595.5 5592.5 5514 5430.5 5254.5 3 68.2 實驗例3 6325 6315.5 6270.5 6197 6004 9.5 64.2 實驗例1 6074 6061.5 6041.5 5977.5 5804 12.5 54 以下’說明比較例與實驗例1之差異。 明參照表2，在比較例中並未添加二曱基乙翻 胺(N，N_dimethyl acetamine，DMAC)，而其他各實驗例 ^ 句有添加 N，N-二曱基乙醯胺(N，N-dimethyl acetamine， mac)。在〇〜5分内的總蝕刻速率並無太大差異，而y 二例在〇〜1分的起始蝕刻率(43·59埃/分)遠大於實驗例 二起始蝕刻率(〇·5埃/分）。其中，因光阻剝離組合物中ν，ν<Preparation of test piece> The im sequence is formed on the substrate, and a layered patterned photoresist layer is formed on the substrate after the deposition of the substrate, and is exposed by the patterned photoresist layer. The nitride nitride layer is formed into a conductor pattern. A plurality of test pieces of 127333⁄4 ltwf.doc/006 were prepared in the above manner, and the test pieces were treated with the photoresist stripping compositions of Experimental Example 1, Experimental Example 2, Experimental Example 3, Experimental Example 4, and Comparative Examples, respectively, and then scanned. Scanning electron microsocope (SEM) was used to observe the conductor patterns on each test piece after the photoresist stripping compositions of Experimental Example 1, Experimental Example 2, Experimental Example 3, Experimental Example 4, and Comparative Example, and compared with the car master. Experimental Example 1, Experimental Example 2, Experimental Example 3, Experimental Example 4, and Comparative Example Differences 0 Then, the photoresist samples of Experimental Example 1, Experimental Example 2, Experimental Example 3, Experimental Example 4, and Comparative Example were treated. The sheet is, for example, immersed, sprayed or spin etched to remove the silk residue adhering to the surface of the conductor pattern after dry etching. Next, after the photoresist = photoresist stripping composition was washed in and removed from the cleaning, the water was again washed to remove the photoresist from the following Table 2, Experimental Example, Experimental Example 2, and 4. Comparative Example The composition treatment test piece's test 2: 5: the relationship between the peeling time and the peeling thickness of the resist. Knife internal light ltwf.doc/006 ltwf.doc/006 Check 1 2 photoresist stripping time production thickness ^^ Group 1?\ 0 1 2 3 5 0 0~1 min 0~5 min photoresist ^ 〖Insect thickness (A) Nominal rate < : angstrom / minute) Comparative Example 5666 5622.5 5590.5 5517 5327.5 43.5 67.7 Experimental Example 1 6281.5 6281 6206.5 6114 5900 0.5 76.3 Experimental Example 2 5595.5 5592.5 5514 5430.5 5254.5 3 68.2 Experimental Example 3 6325 6315.5 6270.5 6197 6004 9.5 64.2 Experimental Example 1 6074 6061.5 6041.5 5977.5 5804 12.5 54 The following 'describes the difference between the comparative example and Experimental Example 1. Referring to Table 2, in the comparative example, N, N-dimethyl acetamine (DMAC) was not added, and other experimental examples were added with N,N-dimercaptoacetamide (N, N). -dimethyl acetamine, mac). The total etch rate in 〇~5 minutes is not much different, and the initial etch rate (43·59 Å/min) in y~1 is much larger than the initial etch rate in experimental example (〇· 5 angstroms / min). Where ν, ν is due to the photoresist stripping composition
甲基乙 δ&胺(N，N-dimethyl acetamine，DMAC)的有益， =起始轉的不同，對導趙圖案之氣：二t 隹宜層產生的結果如圖1及圖2所示。 之、、主π參照圖1及圖2所繪示之分別以比較例及實驗例丄 圖。^先溶液處理後之導體圖案的掃描式電子顯微鏡照相 i铁^圖1所示，以比較例之清洗溶液處理後之導體圖案， =導體圖案上之光阻殘留物已被清除乾淨，但是導體 ^ 之鋁層與氮化石夕層卻受到侵姓。而如圖2，以實驗例 10 ltwf.doc/006 1之清洗溶液處理後之導體圖案，其上之光阻殘留物 全被清除乾淨，且導體圖案之氮化_g/氮 = 未受到雜。 u均 由上述實驗例之結果可知，本發明之清洗液除了可 以有效的移除附著在圖案之光阻殘留物之外，還不合 底或金屬導體造成腐餘現象，而可以保持圖案之二, 々因此可以提高製程裕度(prGeess windGW)、提高清洗ς率、 即啗溶劑耗損，而且能夠降低成本並增加產能。 、此外在本發明光阻剝離方法，在剝離製程後 必如習知紋t財機溶财洗时除総 的驗性成分，可簡化光阻剝離製程。 歇口物中 雖然本發明已以較佳實施例揭露如上，然盆並 ;=:明二任:熟習此技藝者，在不脫離本發明之精 2辄_ ’當可作些許之更動與卿，因此本發 護範圍當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 # 之二 【主要元件符號說明】The benefit of N, N-dimethyl acetamine (DMAC) is different from that of the initial rotation. The gas produced by the two-dimensional layer is shown in Fig. 1 and Fig. 2. Referring to Fig. 1 and Fig. 2, the main π is shown by a comparative example and an experimental example. ^ Scanning electron microscopy of the conductor pattern after solution treatment, as shown in Fig. 1, the conductor pattern after the cleaning solution of the comparative example, = the photoresist residue on the conductor pattern has been cleaned, but the conductor ^ The aluminum layer and the nitride layer are invaded. 2, in the conductor pattern treated with the cleaning solution of the experimental example 10 ltwf.doc/006 1, the photoresist residue on the photoresist pattern is completely removed, and the nitride pattern of the conductor pattern _g/nitrogen = not contaminated . u can be seen from the results of the above experimental examples, in addition to the effective removal of the photoresist residue attached to the pattern, the cleaning liquid of the present invention does not contain the bottom or the metal conductor causes the residual phenomenon, and can maintain the pattern 2, Therefore, the process margin (prGeess wind GW) can be increased, the cleaning rate can be improved, that is, the solvent consumption can be reduced, and the cost can be reduced and the productivity can be increased. In addition, in the photoresist stripping method of the present invention, after the stripping process, it is necessary to simplify the photoresist stripping process by knowing the intrinsic component of the pattern. Although the present invention has been disclosed above in the preferred embodiment, the same is true; =: Ming Er Ren: Those skilled in the art, without departing from the essence of the present invention, can be made a little more Therefore, the scope of this protection is subject to the definition of the patent application scope attached. [Simple description of the diagram] #二 [Main component symbol description]