WO2011006348A1 - Chemical mechanical polishing liquid - Google Patents

Chemical mechanical polishing liquid Download PDF

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Publication number
WO2011006348A1
WO2011006348A1 PCT/CN2010/001036 CN2010001036W WO2011006348A1 WO 2011006348 A1 WO2011006348 A1 WO 2011006348A1 CN 2010001036 W CN2010001036 W CN 2010001036W WO 2011006348 A1 WO2011006348 A1 WO 2011006348A1
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WO
WIPO (PCT)
Prior art keywords
polishing liquid
polishing
chemical mechanical
crown
mechanical polishing
Prior art date
Application number
PCT/CN2010/001036
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French (fr)
Chinese (zh)
Inventor
王晨
宋伟红
姚颖
Original Assignee
安集微电子(上海)有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to CN2009100547120A priority Critical patent/CN101955731A/en
Priority to CN200910054712.0 priority
Application filed by 安集微电子(上海)有限公司 filed Critical 安集微电子(上海)有限公司
Publication of WO2011006348A1 publication Critical patent/WO2011006348A1/en

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Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment 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
    • H01L21/3105After-treatment
    • H01L21/31051Planarisation of the insulating layers
    • H01L21/31053Planarisation of the insulating layers involving a dielectric removal step
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09GPOLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00Polishing compositions
    • C09G1/02Polishing compositions containing abrasives or grinding agents
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/14Anti-slip materials; Abrasives
    • C09K3/1454Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463Aqueous liquid suspensions

Abstract

A chemical mechanical polishing liquid comprises silicon dioxide abrasive particles and crown ethers, and the pH of the polishing liquid is not greater than 7. The chemical mechanical polishing liquid can significantly improve the polishing rate of silicon nitride, while relatively reduce the dosages of chemical substances in the polishing liquid, so as to further reduce environmental pollution.

Description

一种化学机械抛光液 技术领域  Chemical mechanical polishing liquid
本发明涉及一种化学机械抛光液。  The present invention relates to a chemical mechanical polishing liquid.
技术背景 technical background
随着半导体技术的不断发展, 以及大规模集成电路互连层的不断增加, 导电层和绝缘介质层的平坦化技术变得尤为关键。二十世纪 80年代,由 IBM 公司首创的化学机械研磨(CMP)技术被认为是目前全局平坦化的最有效的 方法。  With the continuous development of semiconductor technology and the increasing number of interconnect layers of large-scale integrated circuits, the planarization technology of conductive layers and dielectric layers has become particularly critical. In the 1980s, the chemical mechanical polishing (CMP) technology pioneered by IBM was considered the most effective method for global planarization.
化学机械研磨(CMP)由化学作用、机械作用以及这两种作用结合而成。 它通常由一个带有抛光垫的研磨台, 及一个用于承载芯片的研磨头组成。其 中研磨头固定住芯片, 然后将芯片的正面压在抛光垫上。 当进行化学机械研 磨时, 研磨头在抛光垫上线性移动或是沿着与研磨台一样的运动方向旋转。 与此同时, 含有研磨剂的浆液被滴到抛光垫上, 并因离心作用平铺在抛光垫 上。 芯片表面在机械和化学的双重作用下实现全局平坦化。  Chemical mechanical polishing (CMP) is a combination of chemical action, mechanical action, and both. It usually consists of a polishing table with a polishing pad and a polishing head for carrying the chip. The polishing head holds the chip and then presses the front side of the chip 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 laid flat on the polishing pad by centrifugation. The surface of the chip achieves global planarization under both mechanical and chemical effects.
Si3N4 CMP的目的是通过抛光, 去除过量的氮化硅, 形成所需的平坦的 表面。所用的抛光液多以机械作用为主。研磨颗粒通常是高浓度的二氧化硅。 The purpose of Si 3 N 4 CMP is to remove excess silicon nitride by polishing to form the desired flat surface. The polishing liquid used is mostly mechanical. The abrasive particles are typically high concentrations of silica.
US6239032公开了一种向二氧化硅研磨液中加入磷酸及其衍生物提高 Si3N4抛光速度的方法,该体系中,二氧化硅研磨颗粒的直径优选低于 10nm; US20060084270A1 公开了一种向二氧化硅研磨液中加入特定的酸性添加剂 提高 Si3N4抛光速度的方法, 这类以醋酸为代表的添加剂在 85%的水相中对 Si3N4的侵蚀速度(etching rate)小于 0.1nm/hr, 该体系中, 二氧化硅研磨粒 的直径优选低于 50nm。 US 6,239,032 discloses a process for adding phosphoric acid and its derivatives to a silica slurry to increase the polishing rate of Si 3 N 4 , wherein the diameter of the silica abrasive particles is preferably less than 10 nm; US 20060084270 A1 discloses a A method for increasing the polishing rate of Si 3 N 4 by adding a specific acidic additive to the silica slurry. Such an additive represented by acetic acid has an etching rate of less than 0.1 for Si 3 N 4 in 85% of the aqueous phase. Nm / hr, in this system, the diameter of the silica abrasive particles is preferably less than 50 nm.
上述专利中引入磷酸、 醋酸等酸性物质, 会降低研磨液的 pH值, 为了 调节 pH值, 会进一步引入硝酸、 氢氧化钾、 氨水等酸碱 pH调节剂, 导致 电解质浓度的增加, 继而会导致研磨液稳定性的下降。 另外, 磷酸类物质会 影响其他抛光对象的抛光速度, (例如通常会提高 TEOS 、 Cu的抛光速度)。 因此在某些应用中, 磷酸、 醋酸等酸性物质会变得不适合作为添加剂使用。 The introduction of an acidic substance such as phosphoric acid or acetic acid in the above patent will lower the pH of the polishing liquid, and in order to adjust the pH value, an acid-base pH adjuster such as nitric acid, potassium hydroxide or ammonia water may be further introduced, resulting in An increase in the concentration of the electrolyte, in turn, leads to a decrease in the stability of the slurry. In addition, phosphoric acid substances affect the polishing rate of other polished objects (for example, the polishing rate of TEOS and Cu is usually increased). Therefore, in some applications, acidic substances such as phosphoric acid and acetic acid may become unsuitable for use as an additive.
发明内容 Summary of the invention
本发明的目的是解决现有技术中研磨液稳定性低,抛光速度较低,对 pH 值影响较大, 且会造成对半导体器件的离子污染的缺陷。提供一种能显著提 高 Si3N4抛光速度化学机械抛光液。 The object of the present invention is to solve the defects in the prior art that the polishing liquid has low stability, low polishing speed, large influence on pH value, and ion pollution to a semiconductor device. A chemical mechanical polishing liquid capable of significantly improving the polishing rate of Si 3 N 4 is provided.
本发明的技术方案如下: 一种化学机械抛光液,包含:二氧化硅研磨颗粒、冠醚, 该抛光液的 pH 值不大于 7。  The technical scheme of the present invention is as follows: A chemical mechanical polishing liquid comprising: silica abrasive particles, crown ether, and the pH of the polishing liquid is not more than 7.
本发明中,所述的二氧化硅研磨颗粒为 Fumed Si02 (气相二氧化硅)和 /或 colloidal Si02 (胶体二氧化硅)。 In the present invention, the silica abrasive particles are Fumed SiO 2 (fumed silica) and/or colloidal SiO 2 (colloidal silica).
本发明中, 所述的二氧化硅研磨颗粒的含量为质量百分比 0. 1〜50%。 本发明中, 所述冠醚, 包括 12县 4、 15县 5、 18-冠 -6、 二苯 -18-冠 -6 和二氮 -18-冠 -6, 优选 18-冠 -6。  〜50%。 The content of the content of the mass fraction of 0. 1~50%. In the present invention, the crown ether includes 12 counties 4, 15 counties 5, 18-crown-6, diphenyl-18-crown-6 and dinitro-18-crown-6, preferably 18-crown-6.
本发明中, 所述的冠醚含量为质量百分比 0. 1〜10 %。  1〜10以上。 The content of the crown ether is 0. 1~10%.
本发明中, pH值优选 1-4.  In the present invention, the pH is preferably 1-4.
本发明还可以进一步包含其他常规添加剂,如加入络合剂进一步提高其 他非金属的抛光速度; 加入表面活性剂用于改善 wafer表面的清洗, 等等。  The present invention may further comprise other conventional additives such as the addition of a complexing agent to further increase the polishing rate of other non-metals; the addition of a surfactant for improving the cleaning of the wafer surface, and the like.
本发明的积极效果是: 显著提升氮化硅的抛光速度。 由于冠醚本身不是 电解质, 不含金属离子, 因此不会造成对半导体器件的离子污染。 此外, 由 于对氮化硅抛光速率的提高, 减少了抛光时间, 提高了生产效率, 降低了制 造成本。 由于抛光速率的提高, 还可以相对降低拋光液中化学品的用量, 从 而进一步减少环境污染 The positive effects of the present invention are: Significantly increase the polishing rate of silicon nitride. Since the crown ether itself is not an electrolyte and does not contain metal ions, it does not cause ionic contamination of the semiconductor device. In addition, since the polishing rate of silicon nitride is increased, the polishing time is reduced, the production efficiency is improved, and the manufacturing cost is lowered. Due to the increased polishing rate, the amount of chemicals in the polishing solution can be relatively reduced, And further reduce environmental pollution
具体实施方式 detailed description
下面通过具体实施例来进一步阐述本发明。  The invention is further illustrated by the following examples.
按照表 1中的配方, 将各组分简单混合到去离子水中, 用酸性 pH调节 剂 (例如 HN03)调节到所需要的 pH值, 即可得到本发明的化学机械抛光 表 1、 实施例 1-10 According to the formulation in Table 1, the components are simply mixed into deionized water and adjusted to the desired pH with an acidic pH adjuster (for example, HNO 3 ) to obtain the chemical mechanical polishing table of the present invention. 1-10
效果实施例: Effect example:
下面将本发明的优选实施例与现有技术中的化学机械抛光液进行抛光 对比, 进一步阐述本发明的优点。  The advantages of the present invention are further illustrated by polishing a preferred embodiment of the present invention in comparison with prior art chemical mechanical polishing solutions.
抛光条件:抛光机台为 Logitech (英国) 1PM52型, 12英寸 politex抛 光垫(pad), 4cm*4cm正方形 Wafer,研磨压力 4 psi,研磨台(polishing table) 转速 70转 /分钟,研磨头 (carrier)自转转速 150转 /分钟,抛光液滴加速度 100 ml I min0 Polishing conditions: Polishing machine is Logitech (UK) 1PM52 type, 12 inch politex toss Pad, 4cm*4cm square Wafer, grinding pressure 4 psi, polishing table rotation speed 70 rpm, rotation speed of the rotation of the carrier 150 rpm, polishing droplet acceleration 100 ml I min 0
表 2本发明实施例 6~10与对比例 1配方及效果对比  Table 2 Inventive Example 6~10 and Comparative Example 1 Formulation and Effect Comparison
从以上效果实施例可以看出, 和不加冠醚的对比例 1相比, 在抛光液中 加入冠醚,可以显著提升氮化硅的抛光速度。其中 18-冠 -6的作用最为明显。. As can be seen from the above effect examples, the addition of the crown ether to the polishing liquid can significantly increase the polishing speed of the silicon nitride as compared with the comparative example 1 without the crown ether. Among them, 18-crown-6 has the most obvious effect. .

Claims

权利要求 Rights request
1.一种化学机械抛光液, 包含: 二氧化硅研磨颗粒、冠醚, 所述抛光液 的 pH值不大于 7。 A chemical mechanical polishing liquid comprising: silica abrasive particles, crown ether, and a pH of the polishing liquid of not more than 7.
2.如权利要求 1所述的抛光液, 其特征在于: 所述的二氧化硅研磨颗粒 为气相二氧化硅和 /或胶体二氧化硅。  The polishing liquid according to claim 1, wherein the silica abrasive particles are fumed silica and/or colloidal silica.
3.如权利要求 1所述的抛光液, 其特征在于: 所述的二氧化硅研磨颗粒 的含量为质量百分比 0. 1〜50%。  1〜50%。 The content of the content of the mass percentage of 0. 1~50%.
4.如权利要求 1所述的抛光液, 其特征在于: 所述冠醚选自 12-冠 -4、 15-冠 -5、 18-冠 -6、 二苯 -18-冠 -6和二氮 -18-冠 -6中的一种或多种。  The polishing liquid according to claim 1, wherein: the crown ether is selected from the group consisting of 12-crown-4, 15-crown-5, 18-crown-6, diphenyl-18-crown-6, and One or more of nitrogen-18-crown-6.
5.如权利要求 1所述的抛光液, 其特征在于: 所述的冠醚含量为质量百 分比 0. 1~10 %。  The content of the crown ether is a mass percentage of 0.1 to 10%.
6.如权利要求 1所述的抛光液,其特征在于:所述抛光液的 pH值为.1-4。  The polishing liquid according to claim 1, wherein the polishing liquid has a pH of from 1 to 4.
PCT/CN2010/001036 2009-07-13 2010-07-12 Chemical mechanical polishing liquid WO2011006348A1 (en)

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CN200910054712.0 2009-07-13

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CN104263247B (en) * 2014-09-16 2016-11-30 青岛玉兰祥商务服务有限公司 A kind of method of silicon nitride ceramics chemically mechanical polishing

Citations (3)

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US6458290B1 (en) * 1998-09-03 2002-10-01 Micron Technology, Inc. Isolation and/or removal of ionic contaminants from planarization fluid compositions using macrocyclic polyethers
CN1676563A (en) * 2004-03-29 2005-10-05 Cmp罗姆和哈斯电子材料控股公司 Compositions and methods for chemical mechanical planarization of tungsten and titanium
CN101040021A (en) * 2004-10-12 2007-09-19 卡伯特微电子公司 Cmp composition with a polymer additive for polishing noble metals

Family Cites Families (3)

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Publication number Priority date Publication date Assignee Title
US6099604A (en) * 1997-08-21 2000-08-08 Micron Technology, Inc. Slurry with chelating agent for chemical-mechanical polishing of a semiconductor wafer and methods related thereto
JPH11176773A (en) * 1997-12-12 1999-07-02 Toshiba Corp Polishing method
JP4954462B2 (en) * 2004-10-19 2012-06-13 株式会社フジミインコーポレーテッド Composition for selective polishing of silicon nitride film and polishing method using the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6458290B1 (en) * 1998-09-03 2002-10-01 Micron Technology, Inc. Isolation and/or removal of ionic contaminants from planarization fluid compositions using macrocyclic polyethers
CN1676563A (en) * 2004-03-29 2005-10-05 Cmp罗姆和哈斯电子材料控股公司 Compositions and methods for chemical mechanical planarization of tungsten and titanium
CN101040021A (en) * 2004-10-12 2007-09-19 卡伯特微电子公司 Cmp composition with a polymer additive for polishing noble metals

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