TW201249976A - Chemical-mechanical polishing liquid - Google Patents

Chemical-mechanical polishing liquid Download PDF

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TW201249976A
TW201249976A TW101120379A TW101120379A TW201249976A TW 201249976 A TW201249976 A TW 201249976A TW 101120379 A TW101120379 A TW 101120379A TW 101120379 A TW101120379 A TW 101120379A TW 201249976 A TW201249976 A TW 201249976A
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Taiwan
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polishing liquid
polishing
liquid according
triazole
amino
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TW101120379A
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Chinese (zh)
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TWI510605B (en
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Chen Wang
hua-feng He
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Anji Microelectronics Shanghai
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Publication of TWI510605B publication Critical patent/TWI510605B/en

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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
    • C09G1/04—Aqueous dispersions
    • 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
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions
    • 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
    • H01L21/02002—Preparing wafers
    • H01L21/02005—Preparing bulk and homogeneous wafers
    • H01L21/02008—Multistep processes
    • H01L21/0201—Specific process step
    • H01L21/02024—Mirror polishing
    • 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)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

A chemical-mechanical polishing liquid comprising: polishing particles, water, an azole compound, and piperazine. The polishing liquid enables high-speed polishing of silicon, and the system has high stability and low comprehensive cost for semi-conductor processing.

Description

201249976 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】 隨著半導體技術的不斷發展，以及大型積體電路互連層的不斷增加， 導電層和絕緣介質層的平坦化技術變得尤為關鍵。由IBM公司二十世紀80 · 年代首創的化學機械研磨（CMP)技術被認為是目前全域平坦化的最有效 的方法。 化學機械研磨（CMP)由化學作用和機械作用和兩種作用結合而成。 它的設備通常個帶雜紐（pad)的研磨纟（pG脇ngtable) ，及一個 用於承載晶片（wafer)的研磨頭(carrier)組成。其中研磨頭固定住晶片，然 後將晶片的正面壓在研磨墊上。當進行化學機械研磨時，研磨頭在拋光墊 (pad)上線性移動或是沿著與研磨台一樣的運動方向旋轉。與此同時，含 .有研磨劑的漿液(slurry)被滴到拋光塾（pad)上，並因離心作用平輔在拋 光墊（pad)上。晶片（wafer)表面在機械和化學的雙重作用下實現全域平 坦化。 在新興的TSV (ThroughSilieonVia)技财，尤其是在晶背減薄 (backside thinning)日寺’對石夕要求具有非常高的拋光速度。提高石夕拋光速 度的方法有很多種，通常以加強化學作用為主。 US2002032987公開了 -種用醇胺作為添加劑的抛光液，以提高多晶矽 (Poly siUcon)的去除速率（rem〇valrate)，其中添加麵選2_ (二甲氨基） 3 201249976 -2-甲基-1-丙醇。 US2002151252公開了一種含具有多個羧酸結構的絡合劑的拋光液，用 於提高多晶石夕去除速率’其中優選的絡合劑是EDTA (乙二胺四乙酸）和 DTPA (二乙基三胺五乙酸）。 EP1072662公開了一種含孤對電子和雙鍵產生離域結構的有機物的拋 光液’以提向多晶矽（Poly silicon)的去除速率（rem〇valrate)，優選化合 物是胍類的化合物及其鹽。 US2006014390公開了 一種用於提高多晶矽的去除速率的拋光液，其包 含重量百分比為4.25〜18.5%研磨劑和重量百分比為仏仍〜丨5。/。的添加 劑。其中添加劑主要選自季銨鹽、季胺域和乙醇胺等有機域(鹼）。此外，該 拋光液還包含非離子型表面活性劑，例如乙二醇或丙二醇的均聚或共聚產 物。 US7452481B2公開了用氧化鍅、四元以上的羧酸、季銨域(鹼)的組合物 提高石夕的拋光速度的方法。 CN101492592A公開了用唑提高矽的拋光速度的方法。由於該方法中唑 的鹽類為賴和艘’使得拋光液齡存在歡性差關題。因為為了使 酸性的唾（例如TAZ) pH值調到鹼性，實施例中用氫氧化卸或氫氧化納調 知pH值，引入的鈉離子和鉀離子會造成膠體穩定性下降。同時這些金屬離 子會造成半導體的金屬離子污染。降低元器件的可靠性。 以上方法提高矽的拋光速度有限，尤其在新興的TSV (Thr〇ughsmc()n Via)技術中，難以滿足對矽要有非常高的拋光速度的要求。 201249976 【發明内容】 本發明解決的技術問題是提供一種化學機械拋光液，實現了你t的石夕 拋光速度。 本發明的化學機械拋光液，其包含研磨顆粒、水、唑類化合物和呱嗪。 本發明發現唑類化合物和呱嗪的組合對矽（無論是單晶矽，還是多晶矽） 都具有非常高的拋光速度。不僅如此，該拋光液系統還具有非常高的膠體 . 穩定性。本發明的組合還可以繼續包含四曱基氫氧化銨（TMAH)，用於進 : 一步提高拋光速度。 在本發明中，唾類化合物選自三氮0坐和四氮唾及其衍生物中的一種或 多種。 在本發明中，唑類化合物為1，2,4-三氮唑，3-氨基-1，2,4-三氮唑，5-氨 基-1，2,4-三氮唑，5-羧基·3-氨基-1，2,4-三氮唑和苯並三氮唑、i-H四氮唑、 5-氨基四氮唑中的一種或多種。 在本發明中，唑類化合物的質量百分比濃度為1〜8〇/〇。 - 在本發明中，研磨顆粒選自Si02、Al2〇3、Ce02、SiC和Si3N4中的一 . 種或多種。 在本發明中，研磨顆粒的質量百分比濃度為1〜2〇〇/0。 在本發明中，呱嗪的質量百分比濃度為丨〜川％。 在本發明中，四甲基氫氧化銨的質量百分比濃度為丨〜⑺％。 在本發明中，拋光液的pH值為9〜12。 本發明所用試劑及原料均市售可得。 本發明的積極進步效果在於： 201249976 1) 解決了矽的拋光速度低’並且膠體不穩定的問題； 2) 實現了很高的矽拋光速度。大幅提高了 TSV (Throughsmc〇nVia) 技術中，矽的拋光能力，提高了產能； 3) 降低了半導體加工的綜合成本。 【實施方式】 下面通過具體實施例進一步闡述本發明的優點，但本發明的保護範圍 不僅僅局限於下述實施例。 製備實施例 表1給出了本發明的化學賊拋光液實施例1〜13的配方， 絲1中所列組分及其含量，在去離子水中混合均勻，帛調節綱 到所需pH值’即可製得化學機械抛光液。 序號 研磨劑濃 度（％) 〇坐 唑的濃度 (%) 呱嗪濃度 (%) TMAH 濃201249976 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a chemical mechanical polishing liquid. [Prior Art] With the continuous development of semiconductor technology and the increasing number of interconnect layers of large integrated circuits, the planarization technology of conductive layers and insulating dielectric layers has become particularly critical. The chemical mechanical polishing (CMP) technology pioneered by IBM in the 1980s is considered to be the most effective method for global planarization. Chemical mechanical polishing (CMP) is a combination of chemical and mechanical action and two functions. Its equipment usually consists of a padded grinding ram (pG ngtable) and a carrier for carrying wafers. The polishing head holds the wafer and then presses the front side of the wafer against the polishing pad. When chemical mechanical polishing is performed, the polishing head moves linearly on the polishing pad or in the same direction of motion as the polishing table. At the same time, the slurry containing the abrasive is dropped onto the polishing pad and is applied to the polishing pad by centrifugation. The wafer surface achieves global flatness under both mechanical and chemical effects. In the emerging TSV (ThroughSilieonVia) technology, especially in the backside thinning day temple, it is required to have a very high polishing speed. There are many ways to increase the speed of Shi Xi's polishing, usually by strengthening the chemical action. US2002032987 discloses a polishing solution using an alcoholamine as an additive to increase the removal rate of polysia (Poly siUcon), wherein the addition of 2_(dimethylamino) 3 201249976 -2-methyl-1- Propanol. US2002151252 discloses a polishing fluid comprising a complexing agent having a plurality of carboxylic acid structures for increasing the rate of polycrystalline stone removal. The preferred complexing agent is EDTA (ethylenediaminetetraacetic acid) and DTPA (diethyltriamine). Pentaacetic acid). EP 1072662 discloses a polishing liquid containing a lone pair of electrons and a double bond to produce an organic structure of a delocalized structure to promote the removal rate of polysilicon, preferably a compound of a terpenoid and a salt thereof. US2006014390 discloses a polishing liquid for increasing the removal rate of polycrystalline silicon, which comprises a weight percentage of 4.25 to 18.5% of abrasive and a weight percentage of 仏 still 丨5. /. Additive. The additive is mainly selected from an organic domain (base) such as a quaternary ammonium salt, a quaternary ammonium domain and an ethanolamine. Further, the polishing liquid further contains a nonionic surfactant such as a homopolymer or copolymerized product of ethylene glycol or propylene glycol. U.S. Patent No. 7,452,481 B2 discloses the use of a composition of cerium oxide, a quaternary carboxylic acid or a quaternary ammonium (base) to increase the polishing rate of the stone. CN101492592A discloses a method of increasing the polishing rate of tantalum with azole. Because the salt of the azole in this method is the reliance on the vessel, the polishing liquid age is inferior. Since the pH of the acidic saliva (e.g., TAZ) is adjusted to be alkaline, the pH is adjusted by dehydration or sodium hydroxide in the examples, and the introduced sodium ions and potassium ions cause a decrease in colloidal stability. At the same time, these metal ions can cause metal ion contamination of the semiconductor. Reduce the reliability of components. The above method improves the polishing speed of the crucible, and especially in the emerging TSV (Thr〇ughsmc() n Via) technology, it is difficult to meet the requirement for a very high polishing speed. 201249976 SUMMARY OF THE INVENTION The technical problem to be solved by the present invention is to provide a chemical mechanical polishing liquid, which realizes the polishing speed of your stone. The chemical mechanical polishing liquid of the present invention comprises abrasive particles, water, an azole compound, and a pyridazine. The present inventors have found that the combination of an azole compound and a oxazine has a very high polishing rate for ruthenium (whether single crystal ruthenium or polycrystalline ruthenium). Not only that, the polishing fluid system also has a very high colloid. Stability. The combination of the present invention may further comprise tetrakisperyl ammonium hydroxide (TMAH) for further polishing in one step. In the present invention, the salivary compound is selected from one or more of triazide and tetrazole and its derivatives. In the present invention, the azole compound is 1,2,4-triazole, 3-amino-1,2,4-triazole, 5-amino-1,2,4-triazole, 5-carboxyl group One or more of 3-amino-1,2,4-triazole and benzotriazole, iH tetrazolium, 5-aminotetrazole. In the present invention, the mass percentage concentration of the azole compound is 1 to 8 Å/〇. - In the present invention, the abrasive particles are selected from one or more of SiO 2 , Al 2 〇 3 , Ce 02 , SiC and Si 3 N 4 . In the present invention, the mass percentage of the abrasive particles is 1 to 2 Torr/0. In the present invention, the mass percentage concentration of azine is 丨~川%. In the present invention, the mass percentage concentration of tetramethylammonium hydroxide is 丨~(7)%. In the present invention, the polishing liquid has a pH of 9 to 12. The reagents and starting materials used in the present invention are commercially available. The positive progress of the present invention is: 201249976 1) Solving the problem that the polishing speed of the crucible is low and the colloid is unstable; 2) A high crucible polishing speed is achieved. Significantly improved the polishing ability of the TSV (Throughsmc〇nVia) technology, increased productivity; 3) Reduced the overall cost of semiconductor processing. [Embodiment] Advantages of the present invention will be further clarified by specific embodiments, but the scope of protection of the present invention is not limited only to the following embodiments. PREPARATION EXAMPLES Table 1 shows the formulations of Examples 1 to 13 of the chemical thief polishing liquid of the present invention, the components listed in the wire 1 and their contents, uniformly mixed in deionized water, and adjusted to the desired pH value. A chemical mechanical polishing liquid can be obtained. No. Abrasive concentration (%) 〇 azole concentration (%) azine concentration (%) TMAH thick

1 1本發明的化學機械拋光液實施例丨〜丨3的配方 研磨 劑 201249976 例4 實施 例5 Si02 10 3·氣基-1，2,4-三氮唑 8 6 0 9 實施 例6 Si02 10 3-氨基-1，2,4-三氮唑 6 10 0 10 實施 例7 Si02 20 4-氨基-1，2,4-三氤唑 1 5 10 12 實施 例8 Ce〇2 I 5-氨基-1，2,4-三氮唑 4 6 2 11 實施 例9 Al2〇3 1 5-後基-3-氨基 -1，2,4-三氮唑 4 1 5 11 實施 例10 Si3N4 1 笨並三氮唑 4 6 0 11 實施 例11 SiC 1 苯並三氮唑 4 6 1 11 實施 例12 Si02 5 1-H四氮吐 2 4 6 11 實施 例13 Si02 5 5-氨基四氮唑 2 4 6 11 效果實施例 拋光條件：拋光機台為Logitech (英國）1PM52型，polytex拋光塾， 4cmx4cm正方形晶圓（Wafer)，研磨壓力3psi，研磨台轉速70轉/分鐘，研 磨頭自轉轉速150轉/分鐘，拋光液滴加速度100 ml/分鐘。 表2對比例1〜2及實施例1~丨3拋光效果對比 序號 研磨 劑 研磨劑 濃度 (%) 0坐 唑的濃 度（％) 0瓜唤i農 度（％) TMAH 濃度 (%) pH 矽拋光 速度 (A/min) 30天内 研磨劑 顆粒平 均粒徑 增加值 (A) 11 (用 對比 Si〇2 5 無 無 無 無 氫氧化 2100 20 例1 鉀調 pH) 對比 1，2,4-三 11 (用 15分鐘 例2 Si〇2 5 氮唑 4 無 無 氫氧化 4200 後分 鉀調 層，沉澱 201249976 pH) 實施 例1 Si02 5 1，2,4·三 氮唑 4 8 0 11 9000 0 實施 例2 Si02 5 1，2,4-三 氮峻 4 10 0 11 9500 0 實施 例3 Si02 5 1，2,4-三 氮唑 4 10 4 11 9700 0 實施 例4 Si02 5 1，2,4-三 氮嗤 4 10 8 11 11000 0 實施 例5 Si02 10 3-氨基 -1，2,4-三 氮坐 8 6 0 9 7730 0 實施 例6 Si02 10 3-氧基 -1，2,4-三 氮唑 6 10 0 10 7000 0 實施 例7 Si〇2 20 4-氨基 -1,2,4-=. 氮唑 1 5 10 12 9100 0 實施 例8 Ce〇2 1 5-氨基 -1，2,4-三 氮唑 4 6 2 11 8400 0 實施 例9 Al2〇3 1 5-叛基 •3-氨基 -1，2,4-三 氮唑 4 1 5 11 7200 0 實施 例10 Si3N4 1 笨並三 氮唑 4 6 0 11 8800 0 實施 例11 SiC l 笨並三 氣0坐 4 6 1 11 9600 0 實施 例12 Si〇2 5 1-H四氮 ojj» 2 4 6 11 7010 0 實施 例13 Si02 5 5-氨基 四氮唑 2 4 6 11 7350 0 對比例1表明：單一的二氧化；g夕拋矽的速度不高，只有21〇〇A/min。對 比例2表明：在同樣條件下，拋光液中加入ΤΑζ〇,2,4_三氮唑)，可以將矽 的抛光速度提高2倍。但是，該體系.认a 由於含有金屬離子（鉀離子），體系很 不穩定’ 15分鐘後就會出現拋光顆粒 I成凝膠、沉澱。伴隨著沉澱現象的 201249976 發生，拋光液也逐漸失效。 對比例2和實施例2比較後表明，加入呱嗪可使拋光速度提高2倍。 實施例3、4表明，進一步含有四甲基氫氧化銨，拋光速度會進—步提 高。 實施例1〜7表明，在用二氧化矽做研磨劑時，不同的唑類和呱嗪的組 合都可以顯著提高矽的拋光速度。 . 實施例8〜13表明，選用A1A、Ce〇2、Sic和Si3N4作為研磨劑時，不 . 同的唑類和呱嗪的組合也可以顯著提高矽的拋光速度。 實施例1〜13同時還表明’嗤類和呱嗪的組合使得拋光液體系由原先的 不穩定（5分鐘後分層’沉殿）變得十分穩定（3〇天内研磨綱粒平均粒 徑沒有變化）。穩定效果十分顯著。 由以上資料表明，本發明的化學機械拋光液具有以下優點： 1) 解決了矽的拋光速度低，並且膠體不穩定的問題； 2) 實現了很高的石夕拋光速度。大幅提高了 Tsv (Thr〇ughsiiic⑽匈 . 技術辛，矽的拋光能力，提高了產能； '： 3)降低了半導體加工的综合成本。 以上對本發明的具體實施例進行了詳細描述，但其只是作為範例，本 發明並不限制於以上描述的具體實施例。對於本領域技術人員而言，任何 對本發明進行的等同修改和替代也都在本發明的範嘴之中。因此，在不脫 離本發明的精神和範圍下所作的均等變換和修改，都應涵蓋在本發明的範 圍内。 9 201249976 【圖式簡單說明】 (無） 【主要元件符號說明】 (無）1 1 Chemical mechanical polishing liquid of the present invention Example 研磨~丨3 formulation abrasive 201249976 Example 4 Example 5 Si02 10 3· gas-based-1,2,4-triazole 8 6 0 9 Example 6 Si02 10 3-amino-1,2,4-triazole 6 10 0 10 Example 7 Si02 20 4-Amino-1,2,4-triazole 1 5 10 12 Example 8 Ce〇2 I 5-Amino- 1,2,4-triazole 4 6 2 11 Example 9 Al2〇3 1 5-postyl-3-amino-1,2,4-triazole 4 1 5 11 Example 10 Si3N4 1 Stupid Azole 4 6 0 11 Example 11 SiC 1 benzotriazole 4 6 1 11 Example 12 Si02 5 1-H tetrazine spit 2 4 6 11 Example 13 Si02 5 5-aminotetrazolium 2 4 6 11 Effect Examples Polishing conditions: Polishing machine is Logitech (UK) 1PM52 type, polytex polishing crucible, 4cmx4cm square wafer (Wafer), grinding pressure 3psi, grinding table rotation speed 70rev/min, grinding head rotation speed 150rev/min, Polishing droplet acceleration is 100 ml/min. Table 2 Comparative Example 1 to 2 and Example 1 to 丨3 Polishing Effect Comparison No. Abrasive Abrasive Concentration (%) 0 Separation Concentration (%) 0 唤 i i agronomy (%) TMAH concentration (%) pH 矽Polishing speed (A/min) Average particle size increase of abrasive particles within 30 days (A) 11 (Compared with Si〇2 5 No or no hydroxide 2100 20 Case 1 Potassium pH adjustment) Comparison 1,2,4-3 11 (using 15 minutes for example 2 Si〇2 5 azole 4 without hydroxide 4200 after potassium partitioning, precipitation 201249976 pH) Example 1 Si02 5 1,2,4·triazole 4 8 0 11 9000 0 Implementation Example 2 Si02 5 1,2,4-trinitrogen 4 10 0 11 9500 0 Example 3 Si02 5 1,2,4-triazole 4 10 4 11 9700 0 Example 4 Si02 5 1,2,4- Triazepine 4 10 8 11 11000 0 Example 5 Si02 10 3-Amino-1,2,4-triazo sit 8 6 0 9 7730 0 Example 6 Si02 10 3-oxy-1,2,4-tri Azole 6 10 0 10 7000 0 Example 7 Si〇2 20 4-amino-1,2,4-=. Azol 1 5 10 12 9100 0 Example 8 Ce〇2 1 5-Amino-1,2, 4-triazole 4 6 2 11 8400 0 Example 9 Al2〇3 1 5 - Rebel 3-amino-1,2,4-triazole 4 1 5 11 7200 0 Example 10 Si3N4 1 benzotriazole 4 6 0 11 8800 0 Example 11 SiC l Stupid and three gas 0 sitting 4 6 1 11 9600 0 Example 12 Si〇2 5 1-H tetranitrogen ojj» 2 4 6 11 7010 0 Example 13 Si02 5 5-aminotetrazolium 2 4 6 11 7350 0 Comparative Example 1 indicates: single Dioxide; g 矽 throwing speed is not high, only 21 〇〇 A / min. Proportion 2 shows that under the same conditions, bismuth, 2,4-triazole can be added to the polishing solution to increase the polishing rate of ruthenium by a factor of two. However, the system recognizes that due to the presence of metal ions (potassium ions), the system is very unstable. After 15 minutes, the polishing particles I become gelled and precipitated. With the occurrence of precipitation in 201249976, the polishing fluid gradually failed. Comparison of Comparative Example 2 with Example 2 shows that the addition of pyridazine can increase the polishing speed by a factor of two. Examples 3 and 4 show that, further containing tetramethylammonium hydroxide, the polishing rate is further increased. Examples 1 to 7 show that when cerium oxide is used as the abrasive, the combination of different azoles and azines can significantly increase the polishing rate of ruthenium. Examples 8 to 13 show that when A1A, Ce〇2, Sic and Si3N4 are selected as the abrasives, the combination of the same azoles and azines can also significantly increase the polishing speed of the ruthenium. Examples 1 to 13 also show that the combination of hydrazine and pyridazine makes the polishing liquid system very stable from the original instability (layering after 5 minutes) (the average particle size of the abrasive particles within 3 days is not Variety). The stability effect is very significant. It is indicated by the above information that the chemical mechanical polishing liquid of the present invention has the following advantages: 1) The problem of low polishing speed of the crucible and instability of the colloid is solved; 2) A high polishing speed of the stone is achieved. Significantly improved Tsv (Thr〇ughsiiic (10) Hungary. Technically, the polishing ability of enamel, increased productivity; ': 3) Reduced the overall cost of semiconductor processing. The specific embodiments of the present invention have been described in detail above, but by way of example only, the invention is not limited to the specific embodiments described above. Any equivalent modifications and substitutions made to the invention are also within the scope of the invention. Accordingly, equivalent changes and modifications may be made without departing from the spirit and scope of the invention. 9 201249976 [Simple description of the diagram] (none) [Explanation of main component symbols] (none)

Claims (1)

201249976 七、申請專利範圍： 卜一種化學機械拋光液’其包含：研磨顆粒、水、唑類化合物和°瓜嗪。 2、 如請求項1所述的拋光液’其特徵在於：所述的研磨顆粒選自Si02、 Al2〇3、Ce02、SiC和Si3N4中的一種或多種。 3、 如請求項1或2所述的拋光液’其特徵在於：所述的研磨顆粒的質 量百分比濃度為1~20%。 4、 如請求項1所述的拋光液’其特徵在於：所述的唑類化合物選自三 氮唑和四氮唑及其衍生物中的一種或多種。 ·. 5、 如請求項4所述的拋光液’其特徵在於：所述的唑類化合物為1,2,4-三氮唑，3-氨基_i，2,4-三氮唑’ 5-氧基-1，2,4-三氮唑，5-叛基-3-氨基-i，2,4-三氮°坐、苯並三氮〇坐、1-H四氮。坐、5-氨基四氮〇坐中的一種或多種。 6、 如請求項1所述的拋光液，其特徵在於：所述的唑類化合物的質量 百分比濃度為1〜8〇/。。 7、 如請求項1所述的拋光液’其特徵在於：所述的狐嗓的質量百分比 . 濃度為1〜10%。 8、 如請求項1所述的拋光液’其特徵在於：所述拋光液還含有四曱基 氫氧化敍。 9、 如請求項8所述的拋光液’其特徵在於：所述的四曱基氫氧化銨的 質量百分比濃度為1〜10%。 10、 如請求項1所述的拋光液，其特徵在於：所述拋光液的pH值為 9 〜12。 11、 如請求項1-10任一項所述的拋光液，其特徵在於：所述拋光液用 201249976 於拋光單晶矽或多晶矽。 八、圖式· (無）201249976 VII. Patent application scope: A chemical mechanical polishing liquid containing: abrasive particles, water, azole compounds and guarazine. 2. The polishing liquid according to claim 1, wherein the abrasive particles are one or more selected from the group consisting of SiO 2 , Al 2 〇 3, Ce 02, SiC, and Si 3 N 4 . 3. The polishing liquid according to claim 1 or 2, wherein the abrasive particles have a mass concentration of 1 to 20%. 4. The polishing liquid according to claim 1, wherein the azole compound is one or more selected from the group consisting of triazole and tetrazole and derivatives thereof. 5. The polishing liquid according to claim 4, characterized in that the azole compound is 1,2,4-triazole, 3-amino-i, 2,4-triazole '5 -oxy-1,2,4-triazole, 5-tresyl-3-amino-i, 2,4-triazole, sitting, benzotriazinium, 1-H tetranitrogen. One or more of sitting, 5-aminotetrazolium. 6. The polishing liquid according to claim 1, wherein the azole compound has a mass percentage concentration of 1 to 8 Å. . 7. The polishing liquid according to claim 1 which is characterized in that the mass percentage of the fox is . 1 to 10%. 8. The polishing liquid according to claim 1, wherein the polishing liquid further contains tetradecyl hydroxide. 9. The polishing liquid according to claim 8, wherein the tetrakis ammonium hydroxide has a mass percentage concentration of from 1 to 10%. 10. The polishing liquid according to claim 1, wherein the polishing liquid has a pH of 9 to 12. The polishing liquid according to any one of claims 1 to 10, wherein the polishing liquid is used for polishing single crystal germanium or polycrystalline germanium with 201249976. Eight, schema · (none)
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