TW201224090A - Chemical-mechanical polishing slurry - Google Patents

Chemical-mechanical polishing slurry Download PDF

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TW201224090A
TW201224090A TW100134049A TW100134049A TW201224090A TW 201224090 A TW201224090 A TW 201224090A TW 100134049 A TW100134049 A TW 100134049A TW 100134049 A TW100134049 A TW 100134049A TW 201224090 A TW201224090 A TW 201224090A
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Taiwan
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polishing liquid
acid
liquid according
organic
polishing
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TW100134049A
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Chinese (zh)
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TWI573847B (en
Inventor
wei-hong Song
Ying Yao
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Anji Microelectronics Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/32115—Planarisation
    • H01L21/3212—Planarisation by chemical mechanical polishing [CMP]

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

Disclosed is a chemical-mechanical polishing slurry for planarizing a barrier layer, at least comprising abrasive particles, a metal chelating agent, combined metal corrosion inhibitors, an organic solvent, and an oxidant. The polishing slurry has a high removal rate for a medium material and a low dielectric material, a good surface defect correction capability, and good stability, and can effectively alleviate the remaining of a metal compound on a polishing pad.

Description

201224090 六、發明說明： 【發明所屬之技術領域】 本發明涉及一種化學機械拋光液。 【先前技術】 銅互連的平坦化通常採用三步法，即銅的粗拋，軟著陸和阻擋 層的拋光。而阻擋層的拋光是非常關鍵的步驟，因為它的目的是去 除组阻擋層，清理表面所有金屬殘留和有機物殘留等，並停止在工 藝要求的厚度，形成銅互聯線，這一步決定著最終的表面形貌、可 罪性和電學特性。隨著45nm技術的發展以及新材料尤其是低介電 材料的應用，對包括表面污染物顆粒，蝶形凹陷，厚度分佈，拋光 均一'丨生、表面潔淨度以及低介電材料的去除速率等等關鍵參數都有 了更咼的要求。特別是表面污染物控制、電性能和可靠性方面，其 精度和範圍越來小，越來越苛刻，電阻值在不同線寬的分佈，電遷 移特性’擊穿電壓（VBD)分佈以及時間相關介質擊穿（TDDB) 等等都更加_於輯層的拋光。再者’低介電材料的機械強度也 要求CMP工藝更加溫和雜護介質層峨械完整性，拋光耗材的 成本控制也要求拋光液的低成本和拋光塾的長壽命，這些都對阻擂 層的拋光提iH 了更大的賊，可贱沒有縣和高品f的阻擋層拋 光，技術節點的進—步推進將*可能實現。在阻騎的拋光過程甲 會出現金屬雜和介質材料赖，金屬物賊留，有機物質殘留， 201224090 拋光均一性等問題，因為各個晶片廠的製造工藝有不同的側重點， 所以對阻擋層的平坦化也有不同的要求，現今的拋光液市場，還沒 有一支拋光液能夠解決所有的問題，尤其是對4511111及以下製(制） 程中’阻騎的厚度更薄’封裝(封蓋)_以及齡紐料的物性 特點，都使得拋光㈣配謂拋光性能的變化更加敏感，尤其是對 表面缺陷的修正能力，拋光均—性和穩定性等方面都有近乎苛刻的 要求。本專利提供一種阻擋層拋光液，具有較高的二氧化石夕去除 速率和可_低介電材料去除速率，表面污雜較低，拋光塾無金 屬物質殘留拋綠，並具有較強的表面缺陷修概力。且成本低廉 使用方便。 【發明内容】 本發明要解決的技術問題是：解決銅的去除隨雙氧水變化敏 感、拋光過程中抛光塾上金屬物質殘留、提高低介電材料 的問題。解決_晶圓上表面缺陷的校正能力的問題。〃 本發明提供了—種化學賊拋綠，包含町組分： 一種磨料、—種金屬顧抑制劑組合、-種螯合劑、-種氧化 劑、一種有機溶劑。 最優料是二氧化石夕溶膠，氣相法二氧化石夕。粒徑為20_200nm， 2Gnm。磨料含量為丨—逐，較好的為纖 ，腐财卩糊組合包括—種蝴化合物， 物，一種场侧膦蝴她。其巾，规合物^三201224090 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a chemical mechanical polishing liquid. [Prior Art] The planarization of copper interconnects is usually carried out in a three-step process, namely, copper throwing, soft landing, and polishing of the barrier layer. The polishing of the barrier layer is a very critical step because its purpose is to remove the group barrier layer, clean all metal residues and organic residues on the surface, and stop at the thickness required by the process to form a copper interconnect. This step determines the final Surface topography, sinfulness and electrical properties. With the development of 45nm technology and the application of new materials, especially low dielectric materials, including surface contaminant particles, butterfly depression, thickness distribution, polishing uniformity, surface cleanliness and removal rate of low dielectric materials, etc. Other key parameters have more stringent requirements. Especially in terms of surface contaminant control, electrical properties and reliability, its accuracy and range are getting smaller and more demanding, the resistance value is distributed in different line widths, electromigration characteristics 'breakdown voltage (VBD) distribution and time correlation Dielectric breakdown (TDDB) and so on are all more polished. Furthermore, the mechanical strength of the low dielectric material also requires the CMP process to be more gentle and to maintain the mechanical integrity of the dielectric layer. The cost control of the polishing consumable also requires the low cost of the polishing solution and the long life of the polishing crucible. The polishing of the iH has a larger thief, but there is no barrier polishing of the county and high-quality f, and the advancement of the technology node will be possible. In the polishing process of the riding resistance, there will be metal impurities and dielectric materials, metal thieves, organic matter residues, 201224090 polishing uniformity, etc., because the manufacturing process of each wafer factory has different emphasis, so the barrier layer There are also different requirements for flattening. In today's polishing liquid market, there is not a single polishing solution that can solve all the problems, especially for the thinner thickness of the 'resistance ride' package (cover) for the 4511111 and below. _ and the physical properties of the ageing materials make the polishing (four) with a more sensitive change in polishing performance, especially the ability to correct surface defects, polishing uniformity and stability have almost strict requirements. The patent provides a barrier layer polishing liquid, which has a high removal rate of the dioxide and a low dielectric material removal rate, a low surface contamination, a polished metal, no metal residue, and a strong surface. Defect repair. And the cost is low and easy to use. SUMMARY OF THE INVENTION The technical problem to be solved by the present invention is to solve the problem that copper removal is sensitive to changes in hydrogen peroxide, polishing of metal residues on the crucible during polishing, and improvement of low dielectric materials. Solve the problem of the ability to correct surface defects on the wafer. 〃 The present invention provides a chemical thief throwing green, comprising a component: an abrasive, a metal-inhibitor combination, a chelating agent, an oxidizing agent, and an organic solvent. The optimum material is a dioxide dioxide sol, a gas phase method of sulphur dioxide. The particle size is 20-200 nm, 2 Gnm. The abrasive content is 丨-, preferably, the fiber, and the rot-mix combination includes a butterfly compound, a field-side phosphine butterfly. Its towel, the rule ^ three

S 201224090 氮嗤（BTA)及其仿生物，水溶性聚合物為聚丙烯酸及其鹽或聚丙 烯酸共聚物，所述的大分子有機膦為多氨基多趟基亞曱基膦酸 (ΡΑΡΕΜΡ )或有機鱗酸脂例如多元醇填酸醋（pApE )。βτα的濃 度範圍為0.01-0.5% ’最好的是(u_〇.2%，水溶性聚合物的濃度為 0.01-1% ’最好的是在0.05-0.2% ’大分子有機膦或有機磷酸脂的含 量在 0.01%_1%，最好的為 0.05-0.5%。 螯合劑為一元羧酸或多元羧酸，或者有機膦^例如醋酸，草酸， 丙二酸，檸檬酸，酒石酸，丁二酸，己二酸等，有機鱗為，2_鱗酸 基丁烧-1，2，4-三羧酸（PBTCA)，2_羥基膦醯基乙酸（HPAA)， 羥基亞乙基二膦酸（hedp)’乙二胺四曱叉膦酸五鈉（EDTMp)， 氨基三曱叉繼（ATMP)，等，螯合_添加量為__1%，最佳 的為 0.1-0.5%。 其中’有機溶劑為醇類或峨有機溶劑，較好的為乙醇、丙醇、 乙二醇、丙二醇、丙三醇、二乙二醇；乙二醇曱醚、乙二醇乙醚、 乙二醇丁趟、丙二醇曱醚，丙二醇⑽、丙二醇_、丙二醇丁醚、 乙一醇單甲喊、_乙二醇單乙趟、二乙二醇丁喊、二丙二醇甲峻、 二丙二醇⑽、二丙二醇丙醚等。有機溶劑的添加量為叫〇%， 最好的是1-5%。 上述含量均為質量百分比含量。 其中，氧化料過氧化物或過硫化物，過氧化氫，過氧化納， 過氧化鉀’過氧化笨甲醯’過硫酸納，過硫酸鉀，過硫酸銨等 、本發明的化學機械拋絲進—步包括：殺菌峨變劑，如聚季 錄鹽等。 201224090 本發明的化學機械拋光液pH值為2-5，較佳的為3_4。 本發明中：磨料的作用是去除反應掉的表面金屬材料和非金屬 材料。螯合劑的作用是徹底清楚拋光後表面的金屬物質殘留。複合 防腐劑的作収賴金屬不被雜，另外對氧化綱合翻敏感程 度’保護凹陷處的金屬不被快速絲’飾對前㈣表面缺陷進行 修補。有機溶劑的作用是改變拋光液在晶片和拋光塾上的吸附性 能，溶解去除有機物_和金屬㈣殘留，延長拋光墊壽命，提高 拋光穩定性。並能-定程度的提高二氧切和lGw_k材料的去除^ 率，並抑制銅的絲’改善拋綠在晶片她光墊上面的擴散行 為，改善管晶(芯)内不同線寬結構的拋光均一性。 本發明的有益效果是：採用金屬顧抑制敝合，有效保護金 屬在拋光雜中免受雜，魏校轉簡，翻平坦化 的效果，期有機溶劑來改魏料與拋缝和晶片之 為，來降低拋光墊上金屬殘留物的水準’進—步提高拋光塾壽命， 提高產能’此外械溶劑也能—定程度的雕對不嶋層的抛光選 擇比’更餅制玉藝要求的厚度分佈和表面性貌。 【實施方式】 步闡述本發明的優勢 下面通過具體實施方式來進_ 拋光條件： 抛光塾：Fujibopad 抛光條件：70/90rpm 201224090 拋光液流量：1 〇〇ml/min 靜態腐触速率：將新鮮拋光的銅片放入聚液中浸潰15min，測 量前後的膜層厚度。 蝶形凹陷：採用TEOS封蓋的BD854圖形晶圓，測量80um 金屬塊的蝶形凹陷。 切片内的拋光均一性：為一個管晶(芯)内不同線寬的蝶形凹陷。 表1、實施例1〜11 實施例 金屬腐蝕抑制劑組合 蝥合劑 有機 溶劑 氧化 劑 其它添 加劑 pH值 參比拋光 液 Anji阻棺層抛 光液（商業化） 0.3% 殺菌劑 3.00 實施例1 10% 二氧化矽 lOOnm 0.2% BTA 0.2% 丙 二酸 0.3% 殺菌劑 3.00 實施例2 10% 二氧化矽 lOOnm 0.2% BTA 0.0 (5% PAA 0.2% 丙 二酸 0.3% 殺菌劑 3.00 實施例3 10% 二氧化矽 lOOnm 0.2% BTA 0.05% PAA 0.1% PAPEMP 0.2% 丙 二酸 0.3% 殺菌劑 3.00 實施例4 10% 二氧化矽 lOOnm 0.2% BTA 0.05% PAA 0.1% PAPEMP 0.2% 丙 二酸 2%二乙二 醇單乙醚 0.3% 殺菌劑 3.00 實施例5 10% 二氧化矽 lOOnm 0.2% BTA 0.05% PAA 0.1% PAPEMP 0.2% 丙 二酸 5%乙二醇 丁醚 0.3% 殺菌劑 3.00 實施例6 10% 二氧化矽 lOOnm 0.2% BTA 0.1% PAA 共聚物 0.1% PAPE 0.2%丁 二酸 2%乙二醇 甲醚 0.3% 殺菌劑 3.00 實施例7 10% 二氧化矽 lOOnm 0-2% BTA 0.1% PAA 共聚物 0-1% PAPE 0.2%檸 檬酸 2%丙二醇 甲醚 0.3% 殺菌劑 3.00 實施例8 10% 二氧化矽 lOOnm 0.2% BTA 0.1% PAA 共聚物 0.1% PAPEMP 0.2% PBTCA 2% 二乙二 醇甲醚 0.3% 殺菌劑 3.00 201224090 實施例9 5% 二氧化矽 lOOnm 0.2% BTA 0.1% PAA 共聚物 0.1% PAPEMP 0.2% PBTCA 5%乙二醇 0.3% 殺菌劑 3.00 實施例10 30% 二氧化矽 20nm 0.5% BTA 0.01% PAA 0.01% PAPEMP 0.1%酒 石酸 1%丙二醇 乙醚 0.3% 殺菌劑 5.00 實施例11 1% 二氧化矽 200nm 0.01% BTA 0.1% PAA m PAPEMP 0.5% 酒 石酸 10%乙二醇 丁醚 0.3% 殺菌劑 2.00 註：參比拋光液為市售的阻擋層拋光液 表2、實施例1〜11的實施效果資料 TEOS BD1 Cu Ta Corrosion SER pre pos WIDNU 拋光墊 金屬殘留物 對比拋光液 655 343 490 419 No 1.5 455 462 500A 深綠色 殘留物 實施例1 723 352 202 406 No 1 320 -260 淺綠色 殘留物 實例2 715 328 495 415 No 1.2 752 748 淺綠色 殘留物 實例3 732 364 272 426 No 2 462 210 淺綠色 殘留物 實例4 971 620 235 495 No 1 366 60 180A 無金屬 殘留物 實例5 895 608 246 502 No 1.2 478 135 200A 無金屬 殘留物 實例6 867 635 276 496 no 1.1 520 212 無明顯-金屬殘留物 實例7 906 598 236 486 No 1.5 440 i35 無明顯金屬 殘留物 實例8 882 584 247 468 No 1.2 653 327 無明顯金屬 殘留物 實例9 635 423 326 386 No 1 320 50 無明顯金屬 殘留物 實例10 1658 1024 284 825 No 1.2 695 •240 無明顯金屬 殘留物 實例11 362 255 223 375 No 1.1 425 286 無明顯金屬 殘留物 SER :靜態腐蝕速率；Corrosion :金屬腐蝕；TEOS :二氧化矽；BD1 :低介電材料（黑 鑽1) ; Ta:阻擋層金屬钽；Pre.阻擋層拋光前的蝶形凹陷；pos。：阻擋層拋光後的蝶形 凹陷；WIDNU : —個管晶(芯)内的拋光均一性。 201224090 從上述實施例中我們可以看出，與對比抛光液，本專利特有的 拋光液具有更多的優點。 從圖1可赠出’細金制麟糊組合錢將金屬鋼的 去除速率隨雙氧水變化的敏感程度調整到卫藝要求的範圍，即不能 太敏感以至於讀難喻制，又錢過於雜，造成厚度分佈不可 調0 從圖2-4可以看出’有機溶劑的加人，改變了拋光液在晶片和 拋光墊上的吸_散性能。從岐變了各種膜層材料縣除逮率。 進而改變官晶⑻内的拋光均—性。加人有機麵，能夠一定程度 上提高介質材料包括二氧姆（PETE〇s)和低介電材料⑽^ 的，除速率’降低金屬銅的去除，這樣可以更好的改善表面缺陷， 使得表面形貌能夠滿足工藝要求。 採用本專利特有的金屬雜抑制敝合，可以得 金屬對氧化綱敏感度，使得金屬的厚度控做容易通過二$ 和乳化劑濃度線上縱。也可以更好的修正軟著陸階段金屬表 蝶形凹陷。有齡_加人配合該金屬賴抑軸組合大大改 切片級的均-性’使制—管晶⑻内不同線寬的表面凹陷的· 幅度降低到200埃以下，性能得到了很大的改善。 【圖式簡單說明】 圖1為不同金屬腐钱抑制劑組合下銅去除速率隨雙氧水、 變化情況； 7 /辰又的 201224090 圖2為二氧化矽的去除速率隨有機溶劑濃度的變化情況。 圖3為低介電材料的抛光速率隨有機溶劑添加量的變化情況。 圖4為金屬去除速率隨有機溶劑添加量的變化。 【主要元件符號說明】 (無）S 201224090 Nitrogen tellurium (BTA) and its imitation organism, the water-soluble polymer is polyacrylic acid and its salt or polyacrylic acid copolymer, and the macromolecular organophosphine is polyaminopolydecylphosphinic acid (ΡΑΡΕΜΡ) or Organic lactic acid esters such as polyols filled with vinegar (pApE). The concentration of βτα ranges from 0.01 to 0.5%. The best is (u_〇.2%, the concentration of water-soluble polymer is 0.01-1% 'best is 0.05-0.2% 'macromolecule organic phosphine or organic The content of the phosphate ester is 0.01%_1%, preferably 0.05-0.5%. The chelating agent is a monocarboxylic acid or a polycarboxylic acid, or an organic phosphine such as acetic acid, oxalic acid, malonic acid, citric acid, tartaric acid, dibutyl Acid, adipic acid, etc., organic scales, 2_ squarytin butyrate-1,2,4-tricarboxylic acid (PBTCA), 2-hydroxyphosphonium thioglycolic acid (HPAA), hydroxyethylidene diphosphonic acid (hedp) 'Ethylenediamine tetraindole phosphopentapentate (EDTMp), aminotriterpene (ATMP), etc., chelation_addition amount is __1%, optimally 0.1-0.5%. The organic solvent is an alcohol or hydrazine organic solvent, preferably ethanol, propanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol; ethylene glycol oxime ether, ethylene glycol ether, ethylene glycol butyl hydrazine , propylene glycol oxime ether, propylene glycol (10), propylene glycol _, propylene glycol butyl ether, ethyl ketone monomethyl sulfonate, _ ethylene glycol monoethyl hydrazine, diethylene glycol butyl sulfonate, dipropylene glycol methyl thiophene, dipropylene glycol (10), dipropylene glycol Ether, etc. The amount of the organic solvent added is 〇%, preferably 1-5%. The above contents are all percentage by mass. Among them, oxidized peroxide or persulfide, hydrogen peroxide, sodium peroxide, The potassium oxyhydroxide 'peroxidized benzoic acid sulfonate 'sodium persulfate, potassium persulfate, ammonium persulfate, etc., the chemical mechanical ripper of the present invention includes: a bactericidal mutator, such as a polyquarium salt, etc. 201224090 The chemical mechanical polishing liquid has a pH of 2-5, preferably 3_4. In the present invention, the role of the abrasive is to remove the surface metal material and the non-metal material which are reacted. The function of the chelating agent is to thoroughly understand the metal of the polished surface. Residues of substances. The composite preservatives do not interfere with the metal, and the degree of sensitivity to oxidation is 'protected the metal in the depression is not repaired by the fast wire' to the front (four) surface defects. The role of the organic solvent is to change the polishing. The adsorption performance of the liquid on the wafer and the polishing crucible dissolves and removes organic matter and metal (4) residues, prolongs the life of the polishing pad, improves polishing stability, and can improve the degree of dioxo and lGw_k materials to a certain extent. In addition to the ^ rate, and suppressing the copper wire 'improves the diffusion behavior of the greening on the wafer above her optical pad, improving the polishing uniformity of different line width structures in the tube crystal (core). The beneficial effect of the invention is: using metal to suppress Cohesion, effectively protect the metal from polishing in the polishing, the effect of turning the flat and flattening, and the organic solvent to change the level of the metal residue on the polishing pad. Step-by-step to improve the life of the polishing crucible and increase the productivity. In addition, the mechanical solvent can also be used to determine the thickness distribution and surface appearance of the non-defective layer of the engraving layer. [Embodiment] Steps Advantages of the Invention The following is by way of specific embodiments. Polishing conditions: Polishing Fu: Fujibopad Polishing conditions: 70/90 rpm 201224090 Polishing fluid flow rate: 1 〇〇ml/min Static rotting rate: placing freshly polished copper sheets into a poly The film thickness was measured before and after the liquid was immersed for 15 min. Butterfly-shaped depression: The butterfly-shaped depression of the 80um metal block was measured using a TEOS-capped BD854 graphic wafer. Polishing uniformity within the slice: a butterfly-shaped depression of different line widths within a tube (core). Table 1, Examples 1 to 11 Examples Metal corrosion inhibitor combination chelating agent Organic solvent oxidizing agent Other additives pH reference polishing solution Anji barrier layer polishing solution (commercialized) 0.3% bactericide 3.00 Example 1 10% dioxide矽lOOnm 0.2% BTA 0.2% malonic acid 0.3% bactericide 3.00 Example 2 10% cerium oxide lOOnm 0.2% BTA 0.0 (5% PAA 0.2% malonic acid 0.3% bactericide 3.00 Example 3 10% cerium oxide LOOnm 0.2% BTA 0.05% PAA 0.1% PAPEMP 0.2% malonic acid 0.3% fungicide 3.00 Example 4 10% cerium oxide lOOnm 0.2% BTA 0.05% PAA 0.1% PAPEMP 0.2% malonic acid 2% diethylene glycol single Ether 0.3% bactericide 3.00 Example 5 10% cerium oxide lOOnm 0.2% BTA 0.05% PAA 0.1% PAPEMP 0.2% malonic acid 5% ethylene glycol butyl ether 0.3% bactericide 3.00 Example 6 10% cerium oxide lOOnm 0.2% BTA 0.1% PAA copolymer 0.1% PAPE 0.2% succinic acid 2% ethylene glycol methyl ether 0.3% bactericide 3.00 Example 7 10% cerium oxide lOOnm 0-2% BTA 0.1% PAA copolymer 0-1 % PAPE 0.2% citric acid 2% propylene glycol methyl ether 0.3% bactericide 3.00 Example 8 10% Ceria 100 nm 0.2% BTA 0.1% PAA Copolymer 0.1% PAPEMP 0.2% PBTCA 2% Diethylene glycol methyl ether 0.3% Fungicide 3.00 201224090 Example 9 5% Ceria 100 nm 0.2% BTA 0.1% PAA Copolymer 0.1 % PAPEMP 0.2% PBTCA 5% ethylene glycol 0.3% bactericide 3.00 Example 10 30% cerium oxide 20 nm 0.5% BTA 0.01% PAA 0.01% PAPEMP 0.1% tartaric acid 1% propylene glycol ether 0.3% bactericide 5.00 Example 11 1% Ceria 200 nm 0.01% BTA 0.1% PAA m PAPEMP 0.5% tartaric acid 10% ethylene glycol butyl ether 0.3% bactericide 2.00 Note: The reference polishing liquid is a commercially available barrier polishing liquid. Table 2, Examples 1 to 11 Effect data TEOS BD1 Cu Ta Corrosion SER pre pos WIDNU Polishing pad metal residue contrast polishing liquid 655 343 490 419 No 1.5 455 462 500A Dark green residue Example 1 723 352 202 406 No 1 320 -260 Light green residue example 2 715 328 495 415 No 1.2 752 748 Light green residue example 3 732 364 272 426 No 2 462 210 Light green residue example 4 971 620 235 495 No 1 366 60 180A Example of metal free residue 5 895 608 246 502 No 1.2 478 13 5 200A Metal-free residue example 6 867 635 276 496 no 1.1 520 212 No obvious - metal residue example 7 906 598 236 486 No 1.5 440 i35 No obvious metal residue Example 8 882 584 247 468 No 1.2 653 327 No visible metal Residue example 9 635 423 326 386 No 1 320 50 No significant metal residue Example 10 1658 1024 284 825 No 1.2 695 •240 No obvious metal residue Example 11 362 255 223 375 No 1.1 425 286 No significant metal residue SER: Static corrosion rate; Corrosion: metal corrosion; TEOS: cerium oxide; BD1: low dielectric material (black diamond 1); Ta: barrier metal ruthenium; Pre. : Butterfly-shaped depression after polishing of the barrier layer; WIDNU: - Polishing uniformity in a tube crystal (core). 201224090 From the above examples, we can see that the polishing liquid unique to this patent has more advantages than the comparative polishing liquid. From Figure 1, you can give the 'fine gold-based paste combination money to adjust the metal steel removal rate with the sensitivity of the hydrogen peroxide change to the range of the requirements of the art, that is, not too sensitive to read difficult, and too much money, resulting in thickness The distribution is not adjustable. From Figure 2-4, it can be seen that the addition of organic solvents changes the absorption and dispersion properties of the polishing solution on the wafer and the polishing pad. From the change of the various film materials, the county arrest rate. Further, the polishing uniformity in the official crystal (8) is changed. Adding organic surface can improve the dielectric materials to a certain extent, including dioxin (PETE〇s) and low dielectric materials (10)^, in addition to the rate of 'reduced metal copper removal, which can better improve surface defects, making the surface The shape can meet the process requirements. By using the unique metal hetero-inhibition coupling of this patent, the sensitivity of the metal to the oxidation group can be obtained, so that the thickness of the metal can be easily controlled by the two-dimensional and the concentration of the emulsifier on the line. It is also possible to better correct the metal-shaped butterfly depression in the soft landing stage. The age-plus plus the metal-reducing axis combination greatly changed the homogeneity of the slice level, so that the surface depression of different line widths in the system-tube crystal (8) was reduced to less than 200 angstroms, and the performance was greatly improved. . [Simple description of the diagram] Figure 1 shows the removal rate of copper with hydrogen peroxide in different combinations of metal decay inhibitors. 7 / Chen 201224900 Figure 2 shows the removal rate of cerium oxide with the concentration of organic solvent. Figure 3 shows the polishing rate of a low dielectric material as a function of the amount of organic solvent added. Figure 4 shows the change in metal removal rate with the amount of organic solvent added. [Main component symbol description] (none)

Claims (1)

201224090 七、申請專利範圍·· 、一種用於阻擔層平坦化的化學機械拋光液，包含： a) —種磨料； b) —種金屬腐钱抑制劑組合； c) 一種螯合劑； d) —種有機溶劑； e) —種氧化劑。 2、如睛求項1所述拋光液，其特徵在於，所述磨料是 矽溶膠。 九匕 3、 如凊求項1所舰紐，其特徵在於，所述磨料粒 20-200nm ° 4、 如凊求項3所述拋絲，其·在於，所述磨料粒徑 30-120nm 〇 5如明求項1所述拋光液，其特徵在於，所述磨料含量 l-30wt%。 月求項5所述抛光液，其特徵在於，所述磨料含量 5_20wt%。 月求員1所述拋光液，其特徵在於，所述金屬腐餘抑制 it 麵化合物，—種切㈣合齡—歓分子有機 膦或有機磷酸酯。 8如：求項7所述誠液，其特徵在於，所述销化合物為 及其何生物，所述水溶性聚合物為聚丙烯酸及其鹽或丙稀酸的 201224090 共聚物’所述的大分子有機膦或有機鱗酸酯為多狄基多喊基四亞甲 基膦酸或多元醇填酸酉旨。 9、 如請求項8所述拋光液，其特徵在於，所述坐類化合物的 濃度為0.01-0.5wt%，所述水溶性聚合物的濃度為0.01-1 wt%，所述 大分子有機膦或有機碟酸酯的含量為〇.〇l%_lwt〇/0。 10、 如請求項9所述拋光液，其特徵在於，所述唑類化合物的 濃度為0.1-0.2wt°/〇，所述水溶性聚合物的濃度為〇.〇5-〇.2wt%，所 述大分子有機膦或有機磷酸酯的含量為〇 〇5_〇 5wt%。 11、 如請求項1所述拋光液，其特徵在於，所述螯合劑為有機 酸。 12、 如請求項η所述拋光液，其特徵在於，所述有機酸為一 元或多元竣酸或有機膦。 13、 如請求項11所述拋光液，其特徵在於，所述一元或多元 羧酸選自草酸、丙二酸、檸檬酸、酒石酸、丁二酸中的一種或多種， 所述有機膦選自PBTCA、HPAA、HEDP、EDTMP和ATMP中的 一種或多種。 14、 如请求項η所述抛光液’其特徵在於，所述螯合劑的添 加量為 0.01-lwt%。 15如δ青求項14所述抛光液，其特徵在於，所述聲合劑的添 加量為 0.1-0.5wt0/。。 16、 如請求項1所述拋光液，其特徵在於，所述有機溶劑為醇 類或醚類有機溶劑。 17、 如請求項16所述拋光液，其特徵在於，所述有機溶劑為 201224090 選自乙醇、丙酿 醚、乙二醇乙喊醇、丙二醇、丙三醇、二乙二醇;乙二醇甲 丙醚、丙二醇丁醚、二乙一醢輩甲齡 内-_、内二醇 丁瞇、二丙二醇_ 料㈣、二乙二醇單⑽、二乙二醇 種。 甲醚、二丙二醇⑽和二丙二醇_中的1或多 量為輸綠，恤祕，所糊溶劑的含 二:項18嶋液，編在於，所述有機_ 2〇、如請求項丨所述抛光液，其特徵在於，所述氧化劑為 化物和/或過硫化物。 乳 2卜如請求項20所述拋光液，其特徵在於，所述氧化劑選自 過氧化氫、過氧化鈉、過氧讀、職化笨甲醯、過碰鈉、過硫 酸和過硫酸按中的·-種或多種。 22、 如請求項1所述滅液，其特徵在於，所述拋光液進一步 包含聚季銨鹽。 23、 如請求項1所述拋光液，其特徵在於，所述拋光液pH值 為2-5 24、如請求項23所述拋光液，其特徵在於，所述抛光液pH值 為3-4 13201224090 VII. Patent application scope · · A chemical mechanical polishing solution for flattening the resistive layer, comprising: a) an abrasive; b) a metal decay inhibitor combination; c) a chelating agent; d) An organic solvent; e) an oxidizing agent. 2. The polishing liquid according to item 1, wherein the abrasive is a cerium sol. 9. The article of claim 1, wherein the abrasive grain is 20-200 nm ° 4, as described in claim 3, wherein the abrasive has a particle size of 30-120 nm. 5. The polishing liquid according to claim 1, wherein the abrasive content is from 1 to 30% by weight. The polishing liquid according to Item 5, characterized in that the abrasive content is 5-20% by weight. The polishing liquid according to claim 1, wherein the metal corrosion inhibits the it surface compound, and the seed is cut into four (4) age-inorganic phosphine or organic phosphate. 8: The liquid of claim 7, wherein the pin compound is a large amount of the same, and the water-soluble polymer is a polyacrylic acid and a salt thereof or a copolymer of acrylic acid 201224090 The molecular organophosphine or organic sulphate is a polydido-based tetramethylene phosphonic acid or a polyhydric acid. 9. The polishing liquid according to claim 8, wherein the concentration of the compound is 0.01-0.5 wt%, the concentration of the water-soluble polymer is 0.01-1 wt%, and the macromolecular organophosphine. Or the content of the organic dish ester is 〇.〇l%_lwt〇/0. 10. The polishing liquid according to claim 9, wherein the concentration of the azole compound is 0.1-0.2 wt./〇, and the concentration of the water-soluble polymer is 〇.〇5-〇.2 wt%. The content of the macromolecular organophosphine or organophosphate is 〇〇5_〇5 wt%. The polishing liquid according to claim 1, wherein the chelating agent is an organic acid. 12. The polishing liquid according to claim η, wherein the organic acid is mono- or poly-decanoic acid or an organic phosphine. The polishing liquid according to claim 11, wherein the mono or polycarboxylic acid is one or more selected from the group consisting of oxalic acid, malonic acid, citric acid, tartaric acid, and succinic acid, and the organic phosphine is selected from the group consisting of One or more of PBTCA, HPAA, HEDP, EDTMP, and ATMP. 14. The polishing liquid as claimed in claim η, characterized in that the chelating agent is added in an amount of from 0.01 to 1% by weight. The polishing liquid according to the item 14, wherein the sonicating agent is added in an amount of 0.1 to 0.5 wt%. . The polishing liquid according to claim 1, wherein the organic solvent is an alcohol or an ether organic solvent. The polishing liquid according to claim 16, wherein the organic solvent is 201224090, which is selected from the group consisting of ethanol, glyceryl ether, ethylene glycol, propylene glycol, glycerin, diethylene glycol, and ethylene glycol; Methyl ether, propylene glycol butyl ether, diethyl phthalate, glycerol, dipropylene glycol, tetraethylene glycol mono(10), diethylene glycol. One or more of methyl ether, dipropylene glycol (10) and dipropylene glycol _ are green, and the solvent of the paste contains two: Item 18 sputum, according to the organic _ 2 〇, as described in the claim A polishing liquid characterized in that the oxidizing agent is a compound and/or a persulfide. The polishing liquid according to claim 20, wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, sodium peroxide, peroxyl read, occupational amazon, sodium, persulfate and persulfate. - kind or multiple. 22. The liquid phase removal according to claim 1, wherein the polishing liquid further comprises a polyquaternium. The polishing liquid according to claim 1, wherein the polishing liquid has a pH of 2 to 24, and the polishing liquid according to claim 23, wherein the polishing liquid has a pH of 3-4. 13
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