TW200927997A

TW200927997A - Composition for post-grinding cleaning

Info

Publication number: TW200927997A
Application number: TW96149139A
Authority: TW
Inventors: Song-Yuan Chang; Wen-Tsai Tsai; Min-Ghui Lu; Po-Yuan Shen
Original assignee: Uwiz Technology Co Ltd
Priority date: 2007-12-21
Filing date: 2007-12-21
Publication date: 2009-07-01
Also published as: TWI371504B

Abstract

A composition for post-grinding cleaning of this invention at least comprises at least one acidic material and a corrosion inhibitor, in which the corrosion inhibitor is at least selected from a group consisting of sarcosine, the salt thereof or the composition thereof, and the pH value of the composition is about 0.5-5. The micro particle, metallic ion, organic material and remaining benzotriazole ( BTA, abbreviation of benzotriazole) on the surface of the wafer processed by CMP are not only removed but also the surface of the processed object is protected against corrosion through performing multiple surface cleaning process by using the composition for post-grinding cleaning.

Description

200927997 九、發明說明：【發明所屬之技術領域】本發明係有關一種後研磨清潔組成物，主要提供兮曰圓在CMP製程後，可利用該後研磨清潔組成物進行表洗，以去除晶圓表面之微粒、金屬離子、有機物以及殘留之BTA ’並可保護加工物件表面，避免被腐姓。 ❹ 【先前技術】化學機械拋光或平坦化（CMP)係一項用於平坦化半導體組件或基板頂端表面之半導體製造程序的技術。該半導體組件-般係由石夕基晶圓，其具有形成於晶圓中或晶圓上之主動區及由金屬（一般為鋼或鎢）所形成沿著晶圓沉積在蝕刻線中以便連接該等主動區之内連接線。利用 CMP程序移除已沉積在半導體組件上之過量銅以便平坦化該表面。CMP程序一般包括在受控條件下靠著濕拋光表 Ο面旋轉該半導體基板。該化學拋光劑包括研磨材料（如氧化鋁或二氧化矽），而化學助劑則可為pH值緩衝劑、氧化劑或界面活性劑等。當然，CMp研磨對象不同時，其所需使用的研磨材料亦有所差異。如在銅CMP製程中使用之銅研磨材料係加入氫氧化銨及氫氟酸（HF)。另外，由於銅極易氧化及腐蝕，因此在銅CMP製程中，經常加入含有三氮唑（triazole)的溶液以保護被研磨晶圓的鋼圖案，並避免在研磨後等待下—製程時發生銅腐蚀 ’例如於研磨液中加入苯并***（benzotriazole，以下簡稱為βΤΑ)作 200927997 為銅腐钱抑制劑以保護銅膜表面。而晶圓經過研磨之後’表面勢必殘留大量研磨粉體與金屬離子。因此，在CMP製程後，緊接著必須進行多次表面清洗製程，以去除這些微粒、金屬離子、有機物等二目前業界清除晶圓表面微粒、金屬離子、有機物仍以濕式化學清洗法（wet chemical cleaning)為大宗，其以 Ο 〇液狀酸鹼溶劑與去離子水之混合物作為化學清洗劑清洗晶圓表面’隨後潤濕再乾燥之程序。 ' /月' 然而，由於銅CMP製程中作為銅腐蝕抑制劑之bta 係具有黏著性且不易去除，因此習知清洗步驟分別加入酸性與鹼性之化學藥劑以降低ΒΤΑ黏性，並配合擦洗方法以期於清洗其他微粒、金屬離子與有機物的同時去除ΒΤΑ，但是利用習知技術清洗過之晶圓表面仍具有殘留之 ΒΤΑ。且由於習知銅CMP後清洗製程僅藉由加入之化學藥劑降低BTA黏性，無法將bta完全清除，導致BTA殘留於晶圓表面，甚至在晶圓表面黏結成塊，造成污染。此殘留於晶圓表面之BTA會造成電阻值升高、熱效應以及後續形成之薄膜與銅之介面不佳的問題，使得晶圓可靠度下降’故BTA已被確認為是化學機械研磨後晶圓清洗時常見的有機污染源。【發明内容】本發明之主要目的即在提供一種後研磨清潔組成物於該晶圓在CMP製程後，可利用該後研磨清潔組成物進行 200927997 表面清洗，以去除晶圓表面之微粒、金屬離子、有機物以及殘留之βΤΑ，並可保護加工物件表面免於例如為清潔溶液的侵蝕性質、氧化作用、後清潔腐蝕、化學所生電流侵姓、或光感應侵钱。為達上揭目的，本發明之後研磨清潔組成物至少包含有：至少一種酸性物質以及腐蝕抑制劑，其中，該腐蝕抑制劑係為一選自至少包含肌胺酸及其鹽類化合物或其組合物，且該組合物之PH值約為〇. 5〜5。【實施方式】本發明之特點，可參閱本案圖式及實施例之詳細說明而獲得清楚地暸解。本發明「後研磨清潔組成物」，該後研磨清潔組成物包含有：至少/種酸性物質、腐蝕抑制劑以及溶劑，該至 C種酸性物質的實例包括’但非限於樺檬酸、草酸、Γ 酸、氨基三甲基填酸、卜經基亞乙基工磷二氣曼膦酸丁烧义2,4-三叛酸、氨基三亞甲基鱗酸二丄：甲六甲基—(四甲基)“雜、⑽酸n二甲基、1，5磷酸-六甲基乙烯二胺五甲基、丙7 一酸、蘋果醋酸、丙酸、丁酸、戊酸、己酸、破拍酸审;二酸、馬來酸，紗酸、曱磺酸、苯績酸、f本雜一 ^ 产其芏錯妒、已二胺四乙酸、二乙烯三胺五乙酸、二 :基二)⑽三乙酸或其組合二於中，該酸性物質係佔組成物總重G. 重 200927997 其中，本發明之腐蝕抑制劑可以為肌胺酸及其鹽類化合物等肌胺酸化合物，該肌胺酸及其鹽類之實例包括，但非限於肌胺酸（sarcosine)、200927997 IX. INSTRUCTIONS: [Technical Field] The present invention relates to a post-grinding cleaning composition, which mainly provides a round-back after the CMP process, and can be used for surface cleaning by using the post-grinding cleaning composition to remove the wafer. Surface particles, metal ions, organic matter and residual BTA 'can protect the surface of the processed object to avoid being rotted. ❹ [Prior Art] Chemical mechanical polishing or planarization (CMP) is a technique used to planarize semiconductor fabrication processes for semiconductor components or substrate top surfaces. The semiconductor component is generally formed by a Shih-Ji wafer having an active region formed in or on the wafer and formed by a metal (generally steel or tungsten) deposited along the wafer in an etch line for connection The connecting lines within the active areas. Excess copper that has been deposited on the semiconductor component is removed using a CMP process to planarize the surface. The CMP process generally involves rotating the semiconductor substrate against the wet polishing surface under controlled conditions. The chemical polishing agent includes an abrasive material (e.g., aluminum oxide or cerium oxide), and the chemical auxiliary agent may be a pH buffering agent, an oxidizing agent, or a surfactant. Of course, when the CMp is rubbed differently, the abrasive materials used will vary. Copper abrasive materials used in copper CMP processes are added with ammonium hydroxide and hydrofluoric acid (HF). In addition, since copper is easily oxidized and corroded, in a copper CMP process, a solution containing triazole is often added to protect the steel pattern of the wafer to be polished, and to avoid copper waiting for the next process after grinding. Corrosion 'For example, benzotriazole (hereinafter referred to as βΤΑ) is added to the polishing liquid as 200927997 as a copper rot money inhibitor to protect the surface of the copper film. After the wafer is ground, the surface is bound to leave a large amount of abrasive powder and metal ions. Therefore, after the CMP process, multiple surface cleaning processes must be performed to remove these particles, metal ions, organic matter, etc. The current industry removes wafer surface particles, metal ions, and organic materials by wet chemical cleaning (wet chemical). Cleaning) is a process in which a mixture of a liquid acid-base solvent and deionized water is used as a chemical cleaning agent to clean the surface of the wafer, followed by wetting and drying. '/月' However, since the bta system as a copper corrosion inhibitor in the copper CMP process is adhesive and difficult to remove, the conventional cleaning step adds an acidic and alkaline chemical to reduce the viscous viscosity, and is combined with the scrubbing method. It is expected to remove ruthenium while cleaning other particles, metal ions and organic matter, but the surface of the wafer cleaned by conventional techniques still has residual defects. Moreover, since the conventional copper post-CMP cleaning process only reduces the BTA viscosity by adding a chemical agent, the bta cannot be completely removed, and the BTA remains on the surface of the wafer, and even the surface of the wafer is stuck into a block, causing contamination. This BTA remaining on the surface of the wafer causes an increase in resistance, thermal effects, and subsequent poor film-to-copper interface, resulting in reduced wafer reliability. Therefore, BTA has been identified as a chemical mechanically polished wafer. A common source of organic contamination when cleaning. SUMMARY OF THE INVENTION The main object of the present invention is to provide a post-grinding cleaning composition after the CMP process, the post-grinding cleaning composition can be used for surface cleaning of 200927997 to remove particles and metal ions on the surface of the wafer. , organic matter and residual βΤΑ, and can protect the surface of the processed object from, for example, the aggressive nature of the cleaning solution, oxidation, post-cleaning corrosion, chemical current intrusion, or light-induced intrusion. In order to achieve the above object, the abrasive cleaning composition of the present invention comprises at least: at least one acidic substance and a corrosion inhibitor, wherein the corrosion inhibitor is one selected from the group consisting of at least sarcosine and a salt thereof or a combination thereof 5〜5。 The pH of the composition is about 5. 5~5. [Embodiment] The features of the present invention can be clearly understood by referring to the detailed description of the drawings and the embodiments. The "post-grinding cleaning composition" of the present invention, the post-grinding cleaning composition comprises: at least / an acidic substance, a corrosion inhibitor, and a solvent, and examples of the C-type acidic substance include 'but not limited to succinic acid, oxalic acid, Γ acid, aminotrimethyl acid, pyridyl ethylene, phosphorus, gas, phosphinic acid, butyl, 2,4-tritoponic acid, aminotrimethylene phthalate, dimethyl sulfonate ) "hetero, (10) acid n dimethyl, 1,5 phosphate - hexamethylethylene diamine pentamethyl, propan 7 acid, apple acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, broken acid test Diacid, maleic acid, yoghurt, sulfonium sulfonic acid, benzoic acid, f, heterogeneous, 产, 芏, 二, 二, diethylenetetraacetic acid, diethylene triamine pentaacetic acid, di: yl 2) (10) Acetic acid or a combination thereof, wherein the acidic substance accounts for the total weight of the composition G. Weight 200927997 wherein the corrosion inhibitor of the present invention may be a sarcosine compound such as sarcosine and a salt thereof, the sarcosine and Examples of salts thereof include, but are not limited to, sarcosine,

式一 (CH3NHCH2COOH，CAS= 107-97-1) 月桂酿肌胺酸（lauroyl sarcosine)、Formula 1 (CH3NHCH2COOH, CAS = 107-97-1) Laurel sarcosine,

式二 (C15H29NO3 > CAS 97-78-9) N-趨基肌胺酸（N-acyl sarcosine)、椰油醯基肌胺 ❹酸（cocoyl sarcosine)、油醯肌胺酸（oleoyl sarcosine)、硬脂醯肌胺酸（stearoyl sarcosine)、及肉苴謹酿肌胺酸（myristoyl sarcosine)或其鐘鹽、納鹽、鉀鹽、或胺鹽等或其混合物；例如月桂醯肌胺酸鈉鹽 (Sodium n-Lauroyl Sarcosinate)、Formula 2 (C15H29NO3 > CAS 97-78-9) N-acyl sarcosine, cocoyl sarcosine, oleoyl sarcosine, Stearoyl sarcosine, and myristoyl sarcosine or its clock salt, sodium salt, potassium salt, or amine salt, or the like; or a mixture thereof; (Sodium n-Lauroyl Sarcosinate),

8 200927997 式三【CH3(CH2)10CON(CH3)CH2COONa，CAS 137-16-6】椰油醯基肌胺酸鈉8 200927997 Formula 3 [CH3(CH2)10CON(CH3)CH2COONa,CAS 137-16-6] Sodium citrate

(RC〇N(CH3)CH2COONa, CAS 61791-59-1) 且該腐钱抑制劑係佔組成物總重之〇· 0001至1重量 % 0 以下係藉由特定之具體實施例進一步說明本發明之特點與功效’但非用於限制本發明之範疇。實施例一根據表一所列，利用對照例1至4成份所組成之後研磨清潔組成物，進行後CMP清潔試驗，並比較各對照例中晶圓表面銅的損耗率，其中，該對照例4係為ESC 784，其製造廠商為 ATMI (Advanced Technology Materials, Inc) ’成份％j\mine(胺）類之鹼性成分。_ 檸檬酸，％草酸，％月桂醯肌胺酸鹽，ppm 椰油醯基肌胺酸鹽，ppm pH 對照例1 0.2 0.2 0 0 3 對照例2 0.2 0.2 0 20 3 對照例3 0.2 0.2 20 0 3 對照例4 1-------- ------ ------ 13.5 表一 9 200927997 晶圓表面清洗試驗係根據下列條件進行：晶圓類型：8吋之覆銅薄膜晶圓，厚度為2000A 清洗設備：0ntrak post CMP brush box (Lam Research, CA USA)。清洗測試係將2片覆銅薄膜晶圓置放於Ontrak post CMP brush box中，並利用不同清潔組成物進行清洗，而該清洗之流速為300 ml/min，且各晶圓係於2個brush box(分別為boxl以及box2)中進行清洗，而清洗時間總〇共為50秒後，再利用TXRF (全反射X-射線螢光光譜於各晶圓上5個位置點進行針測，以測量清洗前、後銅的平均厚度以及銅的損耗率（copper loss)結果紀錄於表 TXRF 5point AVG 清洗前清洗前清洗前後之差值操作時間Box 1/ B Box 2 銅的平均厚度（A) 銅的平均厚度（A) 銅的損耗率 (A/min) 對照例1 30/20 sec 2191.76 2168.98 22.78 30/20 sec 2195.38 2174.84 20.54 對吗例2 30/20 sec 2208.62 2191.46 17.16 30/20 sec 2102.28 2176.5 15.78 對照例3 30/20 sec 2189.18 2176.22 12.96 30/20 sec 2201.4 2187.7 13.72 對照例4 30/20 sec 2203. 08 2165. 64 37.44 30/20 sec 2203.3 2146.12 57.18 表二根據表二結果可知，該對照例1與對照例4中，對照例1之銅的損耗率係小於對照例4,故使用具有酸性成分 * 之後研磨清潔組成物較鹼性成分之後研磨清潔組成物，更 200927997 可降低銅的損耗率，而對照例2、3之鋼的損耗率又小於對照例1 ’而大幅度的小於對照例4之鋼的損耗率，故添加有月桂醯肌胺酸鹽或椰油醯基肌胺酸鹽等肌胺酸及其鹽類化合物等肌胺酸化合物’作為腐蝕抑制劑之後研磨清潔劑’會大幅降低銅的扣耗率’故該本發明腐钱抑制劑可提供較佳之抑制腐蝕能力’可有效地保護該加工物件表面，避免被腐敍。實施例二〇同樣根據表一所列’利用對照例1至4成份所組成之後研磨清潔組成物，進行後CMP清潔試驗，並比較各對照例中氟矽玻璃（FSG)表面銅的殘留率。晶圓表面清洗試驗係根據下列條件進行：晶圓類型：8吋之覆銅及氟矽玻璃薄膜晶圓设備· Ontrak post CMP brush box (Lam Research, CA USA)以及 Mirra Polisher (Applied Materials, USA)。 ❹ 清洗測試係先將2片銅晶圓樣品置放於Mirra(RC〇N(CH3)CH2COONa, CAS 61791-59-1) and the decoction inhibitor is 〇·0001 to 1% by weight of the total weight of the composition. The following is further illustrated by the specific examples. The features and functions are not intended to limit the scope of the invention. Example 1 According to Table 1, according to the composition of Comparative Examples 1 to 4, the cleaning composition was ground, the post-CMP cleaning test was performed, and the loss rate of the copper on the wafer surface in each of the comparative examples was compared, wherein the comparative example 4 It is ESC 784, and its manufacturer is an alkaline component of ATMI (Advanced Technology Materials, Inc) 'component %j\mine (amine). _ Citric acid, % oxalic acid, % lauric acid creatine, ppm cocoyl sarcosine, ppm pH Comparative Example 1 0.2 0.2 0 0 3 Comparative Example 2 0.2 0.2 0 20 3 Comparative Example 3 0.2 0.2 20 0 3 Comparative Example 4 1-------- ------ ------ 13.5 Table 1 9 200927997 Wafer surface cleaning test is carried out according to the following conditions: Wafer type: 8 覆 copper Film wafer, thickness 2000A Cleaning equipment: 0ntrak post CMP brush box (Lam Research, CA USA). The cleaning test placed two copper-clad film wafers in an Ontrak post CMP brush box and cleaned them with different cleaning compositions at a flow rate of 300 ml/min and each wafer tied to 2 brushes. The boxes (boxl and box2, respectively) are cleaned, and the cleaning time is totaled for 50 seconds. Then, using TXRF (total reflection X-ray fluorescence spectrum, the needle is measured at 5 positions on each wafer to measure The average thickness of copper before and after cleaning and the copper loss are recorded in the table TXRF 5point AVG Before and after cleaning Before cleaning, the difference between operation time Box 1/ B Box 2 Average thickness of copper (A) Copper Average thickness (A) Loss rate of copper (A/min) Comparative Example 1 30/20 sec 2191.76 2168.98 22.78 30/20 sec 2195.38 2174.84 20.54 Exact example 2 30/20 sec 2208.62 2191.46 17.16 30/20 sec 2102.28 2176.5 15.78 Example 3 30/20 sec 2189.18 2176.22 12.96 30/20 sec 2201.4 2187.7 13.72 Comparative Example 4 30/20 sec 2203. 08 2165. 64 37.44 30/20 sec 2203.3 2146.12 57.18 Table 2 According to the results of Table 2, the Comparative Example 1 and In Comparative Example 4, The loss rate of the copper of the first example is smaller than that of the comparative example 4, so that after cleaning the composition with the acidic component* and grinding the cleaning composition, the cleaning composition is ground, and the 200927997 can reduce the loss rate of copper, and the control examples 2 and 3 The loss rate of steel is smaller than that of Comparative Example 1 and is much smaller than the loss rate of steel of Comparative Example 4, so creatinine such as lauric acid creatine or cocoyl sarcosinate and its salts are added. The creatinine compound as a corrosion inhibitor after grinding as a corrosion inhibitor can greatly reduce the deduction rate of copper. Therefore, the corrosive inhibitor of the present invention can provide a better corrosion inhibiting ability to effectively protect the surface of the processed article. Avoid rot. Example 2 〇 Also according to Table 1 'Use of the components of Comparative Examples 1 to 4 to grind the cleansing composition, perform post-CMP cleaning test, and compare the surface of fluorocarbon glass (FSG) in each control. Residual ratio of copper The wafer surface cleaning test was performed according to the following conditions: Wafer type: 8 覆 copper and fluorocarbon glass film wafer equipment · Ontrak post CMP brush box (Lam Research, CA USA) and Mirra Polisher (Applied Materials, USA).清洗 Cleaning test first placed 2 copper wafer samples in Mirra

Polisher中進行拋光製程約60秒後，其表面會產生一些廢棄物，然後再進行一次拋光製程約10秒後，會產生更多的廢棄物例如微粒或金屬離子。再將晶圓置放於Ontrak post CMP brush box，並利用不同清潔組成物進行清洗，而該清洗之流速為300 ml/min ’且各晶圓係於2個brush box(分別為boxl以及 box2)中進行清洗，而清洗時間總共為50秒後，再利用 200927997 TXRF (全反射X-射線螢光光譜）並於各晶圓上3個位置點【其座標位置分別為（-87, 0)、（0, 0)、（87, 0)】進行針測，以測量銅原子的輻射強度，以得知該晶圓表面銅原子的含量*並將該結果紀錄於表三。After about 60 seconds of polishing in the Polisher, some waste will be generated on the surface, and then a polishing process will take about 10 seconds to produce more waste such as particles or metal ions. The wafer is placed in the Ontrak post CMP brush box and cleaned with different cleaning compositions at a flow rate of 300 ml/min ' and each wafer is tied to 2 brush boxes (boxl and box2, respectively) Cleaning is performed, and after a total of 50 seconds of cleaning time, 200927997 TXRF (Total Reflection X-Ray Fluorescence Spectroscopy) is used and 3 points on each wafer [the coordinates are respectively (-87, 0), (0, 0), (87, 0)] A needle test was performed to measure the radiation intensity of copper atoms to know the content of copper atoms on the surface of the wafer* and the results are reported in Table 3.

CuK intensity, * El0 atoms/cm2 座標 (-87,0) (〇,〇) (87,0) 對照例1 0 0 0 對照例2 0 0 0.01 對照例3 0 0 0 對照例4 對照例4 0.08 0 0 6.4 3.48 0 表三根據表三結果可知，該對照例1及3中各位置點之表面銅原子含量係為0,而對照例2中僅於其中一位置點 (87, 0)有微量銅原子殘留，而對照例4其中一組數值中該位置點（-87,0)有較多的銅原子殘留，而另一組數值中該位置點（-87, 0)以及（0, 0)具有更多的銅原子殘留，故對照例1、2及3中添加有月桂醯肌胺酸鹽或椰油醯基肌胺酸 0 鹽等肌胺酸及其鹽類化合物等肌胺酸化合物，作為腐蝕抑制劑之後研磨清潔劑，可使得清洗後晶圓表面銅的殘留率較低。實施例三同樣根據表一所列，利用對照例1至4成份所組成之後研磨清潔組成物，進行後CMP清潔試驗，並比較各對照例中表面BTA以及銅氧化物（Copper Oxides)的殘留率。晶圓表面清洗試驗係根據下列條件進行：晶圓類型：8吋之覆銅薄膜晶圓 12 200927997 設備：Ontrak post CMP brush box (Lam Research, CA USA)以及 Mirra Polisher。該晶圓利用銅的研磨組成物於該Mirra Polisher進行約60秒的研磨拋光製程，而該銅的研磨組成物中含有 lOOppm的BAT，再將晶圓浸泡於〇. 3重量百分比的BAT 溶液中進行預清洗約30秒後，將該晶圓置於Ontrak post CMP brush box進行後清洗，該清洗時間總共為50秒（分別於boxl中30秒以及box2中20秒），並配合清潔組合〇物之流速為300 ml/min，再進行沖洗及乾燥，最後再利用 TIME-OF-FLIGHT SECONDARY ION MASS SPECTROMETRY(飛行型2次離子質量分析裝置；TOF SIMS) 分別偵測分析，於預清洗及後清洗後晶圓表面之殘渣，並將該結果紀錄於表四。CuK intensity, * El0 atoms/cm2 coordinates (-87, 0) (〇, 〇) (87, 0) Comparative Example 1 0 0 0 Comparative Example 2 0 0 0.01 Comparative Example 3 0 0 0 Comparative Example 4 Comparative Example 4 0.08 0 0 6.4 3.48 0 Table 3 According to the results of Table 3, the surface copper atom content of each of the control points 1 and 3 is 0, while in Comparative Example 2, only one of the positions (87, 0) has a trace amount. The copper atom remains, and in the case of the control group 4, the position point (-87, 0) has more copper atoms remaining, and the other set of values is the position point (-87, 0) and (0, 0). ) There are more copper atom residues, so creatinine compounds such as lauric acid such as lauric acid creatine or cocoyl sarcosine 0 salt and their salt compounds are added to Comparative Examples 1, 2 and 3. After grinding the cleaning agent as a corrosion inhibitor, the residual rate of copper on the surface of the wafer after cleaning is low. Example 3 was also prepared according to Table 1, using the components of Comparative Examples 1 to 4, followed by grinding the cleaning composition, performing a post-CMP cleaning test, and comparing the residual ratio of surface BTA and copper oxide (Copper Oxides) in each of the comparative examples. . The wafer surface cleaning test was performed according to the following conditions: Wafer type: 8 覆 copper-clad film wafer 12 200927997 Equipment: Ontrak post CMP brush box (Lam Research, CA USA) and Mirra Polisher. The wafer was subjected to a grinding and polishing process of about 60 seconds on the Mirra Polisher using a polishing composition of copper, and the copper polishing composition contained 100 ppm of BAT, and the wafer was immersed in a 3 wt% BAT solution. After pre-cleaning for about 30 seconds, the wafer was placed in an Ontrak post CMP brush box for post-cleaning for a total of 50 seconds (30 seconds in boxl and 20 seconds in box2, respectively), combined with cleaning combination The flow rate is 300 ml/min, and then rinsed and dried. Finally, the TIME-OF-FLIGHT SECONDARY ION MASS SPECTROMETRY (flying type 2 ion mass spectrometer; TOF SIMS) is used for detection and analysis, pre-cleaning and post-cleaning. The residue on the surface of the wafer was recorded and the results are reported in Table 4.

Species 種類 Mass Peak, m/z 預清洗後清洗/ 對照例2 後清洗/ 對照例3 後清洗/ 對照例4 I. Element 0 16 4355 644 9707 12059 OH 17 2766 317 11264 10582 Cl 35 580 3 251 959 II. Carbon-Nitrogen CN 26 7034 66 2587 1823 III. Copper Oxides Cu 63 78 143 289 456 CuO 79 18 4 119 321 CuOHx 80 21 2 283 512 Cu〇2Hx 96 13 3 157 276 IV. Oxygen-Oi^anics CH〇2 45 159 1 1696 5183 c2h3o2 59 29 1 337 1771 13 200927997 c3h5〇2 73 23 1 42 185 C3H503 89 233 7 79 966 V.BTA C6H4N3 118 4474 215 615 300 CuC6H5N3 182 98 6 43 20 CuC,2H8N6 299 3623 28 19 3 VI· Nitrate N〇3 62 37 2 38 112 I VII. Sulfate, Sulfite S03 80 46 1 88 140 S04H 97 14 3 92 326 表四Species Type Mass Peak, m/z Pre-cleansing wash / Control Example 2 Post-cleaning / Comparative Example 3 Post-cleaning / Comparative Example 4 I. Element 0 16 4355 644 9707 12059 OH 17 2766 317 11264 10582 Cl 35 580 3 251 959 II Carbon-Nitrogen CN 26 7034 66 2587 1823 III. Copper Oxides Cu 63 78 143 289 456 CuO 79 18 4 119 321 CuOHx 80 21 2 283 512 Cu〇2Hx 96 13 3 157 276 IV. Oxygen-Oi^anics CH〇2 45 159 1 1696 5183 c2h3o2 59 29 1 337 1771 13 200927997 c3h5〇2 73 23 1 42 185 C3H503 89 233 7 79 966 V.BTA C6H4N3 118 4474 215 615 300 CuC6H5N3 182 98 6 43 20 CuC, 2H8N6 299 3623 28 19 3 VI· Nitrate N〇3 62 37 2 38 112 I VII. Sulfate, Sulfite S03 80 46 1 88 140 S04H 97 14 3 92 326 Table IV

根據表四結果可知，其中針對BTA以及銅的氧化物 (Copper Oxides)而言，該對照例2及3中ΒΤΑ的殘留率小於對照例4的殘留率，而對照例2及3中銅氧化物的殘留率同樣小於對照例4的殘留率，故添加有月桂醯肌胺酸或椰油醯基肌胺酸之後研磨清潔組成物，可使得清洗後晶圓表面具有較低之BTA以及銅氧化物的殘留。由上述各實施例可知本發明相較於習有係具有下列優點： 1、本發明之後研磨清潔組成物具有較佳之腐蝕抑制劑’提供較佳之抑制腐蝕能力，可有效地保護該加工物件 (晶圓）表面，以降低加工物件（晶圓）表面銅的損耗率。 2、利用本發明之後研磨清潔組成物清洗後，該加工物件（晶圓）表面具有較低銅的殘留率。 3、利用本發明之後研磨清潔組成物清洗後’該加工物件（晶圓）表面具有較低BTA以及銅氧化物的殘留率。 4、利用本發明之後研磨清潔組成物清洗後’該加工 200927997 物件（晶圓）表面之BTA大幅減少，避免因殘留之BTA造成之電阻值升高、熱效應以及後續形成之薄膜與銅之介面不佳的問題，以確保該加工物件（晶圓）之可靠度。本發明之技術内容及技術特點巳揭示如上，然而熟悉本項技術之人士仍可能基於本發明之揭示而作各種不背離本案發明精神之替換及修飾。因此，本發明之保護範圍應不限於實施例所揭示者，而應包括各種不背離本發明之替換及修飾，並為以下之申請專利範圍所涵蓋。〇【圖式簡單說明】無【主要元件代表符號說明】無 ❹ 15According to the results of Table 4, in the case of BTA and copper oxide (Copper Oxides), the residual ratio of ruthenium in Comparative Examples 2 and 3 was smaller than that of Comparative Example 4, and the copper oxides in Comparative Examples 2 and 3 The residual rate is also lower than that of the comparative example 4, so the addition of the lauric creatinine or cocoyl creatinine after grinding the cleaning composition can make the surface of the wafer have a lower BTA and copper oxide after cleaning. Residue. It can be seen from the above embodiments that the present invention has the following advantages over the conventional ones: 1. The abrasive cleaning composition of the present invention has a better corrosion inhibitor to provide better corrosion inhibition capability, and can effectively protect the processed article (crystal Round) surface to reduce the loss rate of copper on the surface of the workpiece (wafer). 2. After the abrasive cleaning composition is cleaned by the present invention, the surface of the workpiece (wafer) has a lower residual ratio of copper. 3. After the abrasive cleaning composition is cleaned by the present invention, the surface of the processed article (wafer) has a lower residual ratio of BTA and copper oxide. 4. After the cleaning composition is cleaned by the present invention, the BTA of the surface of the workpiece 200927997 is greatly reduced, and the resistance value caused by the residual BTA is increased, the thermal effect and the subsequent film-to-copper interface are not formed. Good question to ensure the reliability of the processed object (wafer). The technical content and technical features of the present invention are disclosed above, but those skilled in the art can still make various substitutions and modifications without departing from the spirit and scope of the invention. Therefore, the scope of the present invention should be construed as being limited by the scope of the appended claims. 〇 [Simple diagram description] None [Main component representative symbol description] None ❹ 15

Claims

200927997 十、申請專利範圍： 1、一種後研磨清潔組成物，至少包含有：至少一種酸性物質；以及腐餘抑制劑；其中’該腐餘抑制劑係為一選自至少包含肌胺酸及其鹽類化合物或其組合物’且該組合物之pH值約為〇. 5〜5。 2、如請求項1所述後研磨清潔組成物，其中該肌胺酸及其鹽類化合物包括’但非限於肌胺酸（sarc〇sine)、 ❹酿基肌胺酸（N-acyl sarcosine)、月桂醯肌胺酸（lauroyl sarcosine)、椰油酿基肌胺酸（c〇c〇yi sarc〇sine)、油醯肌胺酸（〇le〇yl sarcosine)、硬脂醯肌胺酸（stearoyl sarcosine)、及肉菫蔻酿肌胺酸（myrist〇yi sarcosine) 或其鐘鹽、納鹽、卸鹽、或胺鹽或其組合物。 3、如請求項1所述後研磨清潔組成物，其中該肌胺酸及其鹽類化合物可以為肌胺酸（sarcosine)，該肌胺酸之化學式如式一：200927997 X. Patent application scope: 1. A post-grinding cleaning composition comprising at least: at least one acidic substance; and a residual inhibitor; wherein 'the residual inhibitor is one selected from the group consisting of at least sarcosine and 5〜5。 The salt compound or a combination thereof, and the pH of the composition is about 〇. 5~5. 2. Grinding the cleansing composition as described in claim 1, wherein the sarcosine and its salt compounds include, but are not limited to, sarcium sine, N-acyl sarcosine. , lauroyl sarcosine, coconut oil creatinine (c〇c〇yi sarc〇sine), oil creatinine (〇le〇yl sarcosine), stearin sarcosine (stearoyl) Sarcosine), and myristium sarcosine or its clock salt, sodium salt, salt, or amine salt or a combination thereof. 3. Grinding the cleansing composition as described in claim 1, wherein the creatinine and its salt compound may be sarcosine, and the chemical formula of the sarcosine is as shown in formula 1:

式一 (CH3NHCH2COOH，CAS= 107-97-1)。 4、如請求項1所述後研磨清潔組成物，其中該肌胺酸及其鹽類化合物可以為月桂醯肌胺酸，該月桂醯肌胺酸之化學式如式二： 200927997Formula one (CH3NHCH2COOH, CAS = 107-97-1). 4. Grinding the cleansing composition as described in claim 1, wherein the creatinine and its salt compound may be lauric acid, and the chemical formula of the lauric acid is as follows: 200927997

式二 (C15H29N03，CAS 97-78-9)。 5、如請求項1所述後研磨清潔組成物，其中該肌胺酸及其鹽類化合物可以為月桂醯肌胺酸鈉鹽，該月桂醯肌胺 ❹ 酸鈉鹽之化學式如式三：Equation 2 (C15H29N03, CAS 97-78-9). 5. The cleansing composition is ground as described in claim 1, wherein the creatinine and its salt compound may be sodium lauric acid, and the chemical formula of the sodium lauric acid sodium citrate is as shown in formula 3:

式三【CH3(CH2>C0N(CH3)CH2C00Na，CAS 137-16-6】。 6、如請求項1所述後研磨清潔組成物，其中該肌胺酸〇及其鹽類化合物可以為椰油醯基肌胺酸鈉，該椰油醯基肌胺酸鈉之化學式如式四：Formula 3 [CH3(CH2>C0N(CH3)CH2C00Na, CAS 137-16-6] 6. Grinding the cleansing composition as described in claim 1, wherein the sarcosinate and its salt compound may be coconut oil Sodium thioglycolate, the chemical formula of sodium cocoyl sarcosinate is as shown in formula 4:

式四。 7、如請求項1所述後研磨清潔組成物，其中該酸性物質可以為檸檬酸、草酸、磷酸、氨基三曱基磷酸、1-羥基 17 200927997 磉亞乙基1，1-二磷酸、2-膦酸丁烷-1，2, 4-三羧酸、氨基三亞曱基膦酸、1，4氨酸六曱基-(四曱基）1，4磷酸、1，5磷酸-二乙烯三胺五甲基、1，5磷酸-六曱基乙烯三胺五曱基、丙二酸、乳酸、醋酸、丙酸、丁酸、戊酸、己酸、玻ίά酸、己二酸、蘋果酸、馬來酸，酒石酸、曱磺酸、苯磺酸、曱苯磺酸、十二烷基苯磺酸、乙二胺四乙酸、二乙烯三胺五乙酸、三甘胺酸、Ν-(羥乙基）乙二胺三乙酸或其組合物。 8、如請求項1所述後研磨清潔組成物，其中該酸性物〇質佔組成物總重之0. 01至10%。 9、如請求項1所述後研磨清潔組成物，其中該蝕刻抑制劑佔組成物總重之0. 0001至1%。 200927997 七、指定代表圖： (一）本案指定代表圖為：第（無）圖。 (二) 本代表圖之元件符號簡單說明：無八、本案若有化學式時，請揭示最能顯示發明特徵的化學式:Equation four. 7. Grinding the cleaning composition as described in claim 1, wherein the acidic substance may be citric acid, oxalic acid, phosphoric acid, aminotrimercaptophosphoric acid, 1-hydroxy 17 200927997 磉ethylene 1,1-diphosphate, 2 - phosphonic acid butane-1,2,4-tricarboxylic acid, aminotrimethylenephosphonic acid, 1,4-hexacycline-(tetradecyl) 1,4 phosphate, 1,5 phosphate-diethylene three Amine pentamethyl, 1,5-phosphate-hexamethylethylene triamine pentadecyl, malonic acid, lactic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, boric acid, adipic acid, malic acid , maleic acid, tartaric acid, sulfonic acid, benzenesulfonic acid, terephthalic acid, dodecylbenzenesulfonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triglycine, hydrazine-(hydroxyl Ethyl) ethylenediaminetriacetic acid or a combination thereof. 01至10百分比。 The amount of the total weight of the composition of the composition of the total weight of the composition of the composition of the composition of the composition of the first embodiment. 0001至1%。 The etch inhibitor of the composition of the total weight of the composition of the total weight of the composition of 0. 0001 to 1%. 200927997 VII. Designation of the representative representative: (1) The representative representative of the case is: (No). (2) A brief description of the symbol of the representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:

❹ 式一❹ style one

式二Formula 2

式四 4 200927997 月h修(吏)止腎換頁Type 4 4 200927997 month h repair (吏) stop kidney page

【CH3(CH2)10CON(CH3)CH2COONa，CAS 137-16-6】椰油醯基肌胺酸鈉[CH3(CH2)10CON(CH3)CH2COONa,CAS 137-16-6] Sodium citrate

式四Four

(RCON(CH3)CH2COONa, CAS 61791-59-1) 且該腐蝕抑制劑係佔組成物總重之〇. 0001至1重量 % ° 以下係藉由特定之具體實施例進一步說明本發明之特點與功效，但非用於限制本發明之範疇。實施例~ 〇根據表一所列’利用對照例1至4成份所組成之後研磨清潔組成物，進行後CMP清潔試驗，並比較各對照例中晶圓表面銅的損耗率’其中，該對照例4係為ESC 784，其製is·薇商為 ATMI (Advanced Technology Materials, 對照例1 對照例3 檸樣酸，％草酸,％月桂醯肌胺酸鹽，ppm 椰油醯基肌胺酸鹽，ppm pH 0.2 0.2 0 0 3 0.2 0.2 0 20 3 0.2 0.2 20 0 3 —~~~~~-- 13.5 9 200927997(RCON(CH3)CH2COONa, CAS 61791-59-1) and the corrosion inhibitor is based on the total weight of the composition. 0001 to 1% by weight or less. The characteristics of the present invention are further illustrated by specific embodiments. Efficacy, but not intended to limit the scope of the invention. EXAMPLES 〇 According to Table 1, after the composition of Comparative Examples 1 to 4 was used, the cleaning composition was ground, and a post-CMP cleaning test was performed, and the loss rate of copper on the wafer surface in each of the comparative examples was compared, wherein the comparative example 4 is ESC 784, and its is Weiwei is ATMI (Advanced Technology Materials, Comparative Example 1 Comparative Example 3, Lime-like acid, % oxalic acid, % lauric acid creatinine, ppm cocoyl sarcosine, Ppm pH 0.2 0.2 0 0 3 0.2 0.2 0 20 3 0.2 0.2 20 0 3 —~~~~~-- 13.5 9 200927997

ο 1 式二 (C15H29N03，CAS 97-78-9)。 Ο 5、如請求項1所述後研磨清潔組成物，其中該肌胺酸及其鹽類化合物可以為月桂醯肌胺酸鈉鹽，該月桂醯肌胺酸鈉鹽之化學式如式三：ο 1 Equation 2 (C15H29N03, CAS 97-78-9). Ο 5. Grinding the cleaning composition as described in claim 1, wherein the creatinine and its salt compound may be sodium lauric acid, and the chemical formula of the sodium lauric acid sodium salt is as shown in formula 3:

式三【CH3(CH2)1()C(M(CH3)CH2C00Na，CAS 137-16-6】。 ❹ 6、如請求項1所述後研磨清潔組成物，其中該肌胺酸及其鹽類化合物可以為椰油醯基肌胺酸鈉，該椰油醯基肌胺酸鈉之化學式如式四： Ο Να+ 式四。 7、如請求項1所述後研磨清潔組成物，其中該酸性物質可以為檸檬酸、草酸、磷酸、氨基三曱基磷酸、1-羥基 17Formula 3 [CH3(CH2)1()C(M(CH3)CH2C00Na, CAS 137-16-6]. ❹ 6. Grinding the cleansing composition as described in claim 1, wherein the sarcosine and its salts The compound may be sodium cocoyl-sodium sarcosinate, and the chemical formula of the sodium cocoyl-sodium sarcosinate is as shown in the following formula: Ο Να+ is four. 7. After grinding the cleaning composition as described in claim 1, wherein the acidity is The substance may be citric acid, oxalic acid, phosphoric acid, aminotrimercaptophosphoric acid, 1-hydroxyl 17

200927997 °[(〇\^\[^\ ' 七、指定代表圖： (一）本案指定代表圖為：第（無）圖。 (二）本代表圖之元件符號簡單說明：無八、本案若有化學式時，請揭示最能顯示發明特徵的化學式:200927997 °[(〇\^\[^\ ' VII. Designated representative map: (1) The representative representative figure of this case is: (None) figure. (2) The symbol of the symbol of this representative figure is simple: No. When there is a chemical formula, please reveal the chemical formula that best shows the characteristics of the invention:

式一Formula one

式四 4Equation 4 4