WO2014059744A1 - Alkaline chemical-mechanical polishing solution - Google Patents

Alkaline chemical-mechanical polishing solution Download PDF

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Publication number
WO2014059744A1
WO2014059744A1 PCT/CN2013/000980 CN2013000980W WO2014059744A1 WO 2014059744 A1 WO2014059744 A1 WO 2014059744A1 CN 2013000980 W CN2013000980 W CN 2013000980W WO 2014059744 A1 WO2014059744 A1 WO 2014059744A1
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Prior art keywords
polishing fluid
fluid according
polishing
acid
quaternary ammonium
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PCT/CN2013/000980
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French (fr)
Chinese (zh)
Inventor
王晨
何华锋
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安集微电子（上海）有限公司
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Publication of WO2014059744A1 publication Critical patent/WO2014059744A1/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
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • 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

Definitions

  • This invention relates to an alkaline chemical mechanical polishing liquid, and more particularly to an alkaline chemical mechanical polishing liquid for a barrier layer.
  • CMP Chemical mechanical polishing
  • the barrier layer is typically interposed between silicon dioxide and copper lines to block the diffusion of copper ions into the dielectric layer.
  • the copper above the barrier layer is first removed. Since the polishing speed of copper is very fast at this time, various defects (for example, butterfly defecting, and erosion erosion) are formed.
  • copper CMP is usually required to stop on the barrier layer, and then another special barrier polishing solution is removed to remove the barrier layer (such as germanium), and the butterfly defect polishing and erosion erosion are corrected to achieve a global flattened.
  • the polishing rate of copper by an acid barrier polishing liquid is easily adjusted by hydrogen peroxide, and the hydrogen peroxide is stable, but the polishing speed for silicon dioxide and germanium is slow;
  • the polishing rate of the alkaline barrier polishing liquid to copper is not easily adjusted by hydrogen peroxide, and the hydrogen peroxide is unstable, but the polishing speed of silica and TiN is faster.
  • US7241725 and US7300480 use imine, ruthenium, and iridium to increase the polishing rate of the barrier layer.
  • US7491252B2 uses cesium hydrochloride to increase the polishing rate of the barrier layer.
  • US7790618B2 uses an imine derivative and a polyethylene glycol sulfate surfactant for polishing the barrier layer.
  • the above patents increase the polishing speed of the barrier layer, but do not well protect the erosion of the thin line region.
  • CN101665664A The use of a quaternary ammonium salt cationic surfactant inhibits low dielectric materials (eg BD) polishing speed.
  • the cationic quaternary ammonium salt contains a long chain of C8 or higher, but most of the quaternary ammonium salt type cationic surfactant having a long chain of C8 or higher significantly inhibits the polishing rate of silica (OXIDE) and prevents polishing.
  • EP 2119353 A1 uses poly(methyl vinyl ether) for the polishing of barrier layers containing Low-K materials.
  • US 2008/0276543 A1 uses a mixture of formamidine, guanidine and polyvinylpyrrolidone (PVP) for the polishing of the barrier layer.
  • PVP polyvinylpyrrolidone
  • EP0373501 B1 discloses a fine polishing liquid which uses an organic polymer such as polyvinylpyrrolidone (PVP) to adjust the hydrodynamic properties of the polishing liquid, improve the flatness of the surface of the silicon wafer, and reduce defects.
  • PVP polyvinylpyrrolidone
  • this fine polishing liquid cannot be used for polishing containing metallic materials (copper, bismuth).
  • the technical problem to be solved by the present invention is to provide an alkaline chemical mechanical polishing liquid. While adjusting the polishing speed of various materials such as barrier layer, dielectric layer and copper, it can well protect the erosion of the thin line region, and the silicon wafer has a high global flatness.
  • an alkaline chemical mechanical polishing liquid comprising abrasive particles, an azole compound, a complexing agent, one or more selected from the group consisting of C1 to C4 quaternary ammonium bases, An oxidizing agent, a surfactant and water that regulate the flatness of the surface of the wafer.
  • the abrasive particles are gas phase SiO 2 and/or sol SiO 2 , preferably sol SiO 2 .
  • the abrasive particles have a concentration of 5 to 25 wt%.
  • the azole compound is selected from the group consisting of triazole and its derivatives, preferably BTA and/or TTA and derivatives thereof, of which TTA and its derivatives are preferred.
  • the azole compound has a mass percentage of 0.02 to 0.2% by weight.
  • the complexing agent is an amino acid, citric acid and/or an organic phosphonic acid.
  • the organic phosphonic acid is preferably hydroxyethylidene diphosphonic acid (HEDP) and/or 2-butylbutane-1, 2,
  • the organic acid has a mass percentage of 0.05 to 0.4% by weight. .
  • the C1 to C4 quaternary ammonium base is selected from one or more of TMAH, TBAH, butyltrimethylammonium hydroxide and tributylmethylammonium hydroxide, preferably TBAH.
  • the C1 to C4 quaternary ammonium base has a mass percentage of 0.05 to 1 wt%.
  • the oxidizing agent is hydrogen peroxide and a derivative thereof, preferably hydrogen peroxide.
  • the oxidizing agent has a mass percentage of 0.1 to 1% by weight.
  • the surfactant which adjusts the surface flatness of the silicon wafer is polyvinylpyrrolidone (PVP).
  • the polyvinylpyrrolidone (PVP) has a mass percentage of 0.01 to 1% by weight.
  • the polishing liquid has a pH of 9 to 12.
  • the polishing liquid further comprises a pH adjusting agent, wherein the pH adjusting agent is a base or an acid, wherein the base is KOH, and the acid is HNO 3 .
  • the polishing liquid as described above can be applied to the polishing barrier layer.
  • Polyvinylpyrrolidone can be used to adjust the flatness of the surface of the wafer.
  • the C1-C4 quaternary ammonium base can be used to effectively control the erosion of the thin line region of the copper wire.
  • the reagents, materials and products used in the present invention are commercially available.
  • the positive progress of the present invention is that -
  • the formula contains C1 ⁇ C4 quaternary ammonium base. Different from the quaternary ammonium salt surfactant containing C8 or above, it does not form bubbles and can also be used as an organic base. , adjust the pH value, better than KOH, and do not introduce metal ions. Summary of the invention
  • the polishing liquid was prepared in accordance with the ingredients of the respective examples in Table 1 and their ratios, and mixed uniformly.
  • TTA is methyl benzotriazole, commercially available
  • polishing liquid formulations in Table 1 were tested in accordance with the following experimental conditions.
  • Polishing conditions Mirra machine, fujibo pad, speed 93/87, polishing pressure: 1.5psL Slurry flow 200mL/min. Enter the above parameters in the Mirra machine, for 8 inch silicon dioxide wafer, BD wafer, copper silicon The wafer and the silicon wafer containing the thin line of copper wire were polished for 1 min, washed, dried, and tested to obtain the polishing results of Table 2.
  • Comparative Example 1, 2 It can be seen from Comparative Example 1, 2 that in the absence of quaternary ammonium base and PVP, the erosion of the thin wire region of the copper wire is severe, and the flatness of the surface of the silicon wafer is not good.
  • C1 ⁇ C4 quaternary ammonium base and PVP were added, and the erosion of the thin wire region of the copper wire was remarkably improved, and the effect of the global flattening of the silicon wafer was better.
  • the polishing liquid of the present invention can protect the erosion of the thin line region and improve the surface smoothness of the silicon wafer while adjusting the polishing speed of various materials such as silicon dioxide, barrier layer and copper. degree.
  • wt% of the present invention refers to the mass percentage.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

The present invention provides an alkaline polishing solution for polishing a barrier layer, comprising grinding particles, an azole compound, C1-C4 quaternary ammonium alkali, an oxidant, water, and a surface active agent for adjusting surface flatness of a silicon slice. The polishing solution can effectively control erosion of a fine copper wire area, and realize overall planarization rapidly.

Description

一种碱性化学机械抛光液 本发明涉及一种碱性化学机械抛光液， 更具体地说， 涉及一种用于阻挡 层的碱性化学机械抛光液。 技术背景  BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to an alkaline chemical mechanical polishing liquid, and more particularly to an alkaline chemical mechanical polishing liquid for a barrier layer. technical background
化学机械抛光 （CMP) ， 是实现芯片表面平坦化的最有效方法。  Chemical mechanical polishing (CMP) is the most effective way to achieve surface flattening of the chip.
阻挡层通常介于二氧化硅和铜线之间，起到阻挡铜离子向介电层扩散的 作用。 抛光时， 首先阻挡层之上的铜被去除。 由于此时铜的抛光速度很快， 会形成各种缺陷（例如： 蝶形缺陷 dishing, 和侵蚀 erosion) 。 在抛光铜时， 通常要求铜 CMP先停止在阻挡层上，然后换另外一种专用的阻挡层抛光液， 去除阻挡层 （例如钽） ， 同时对蝶形缺陷 dishing和侵蚀 erosion进行修正， 实现全局平坦化。  The barrier layer is typically interposed between silicon dioxide and copper lines to block the diffusion of copper ions into the dielectric layer. When polishing, the copper above the barrier layer is first removed. Since the polishing speed of copper is very fast at this time, various defects (for example, butterfly defecting, and erosion erosion) are formed. When polishing copper, copper CMP is usually required to stop on the barrier layer, and then another special barrier polishing solution is removed to remove the barrier layer (such as germanium), and the butterfly defect polishing and erosion erosion are corrected to achieve a global flattened.
商业化的阻挡层抛光液有酸性和碱性两种， 各有优缺点。 例如酸性阻挡 层抛光液对铜的抛光速度容易通过双氧水调节， 且双氧水稳定， 但是对二氧 化硅和 ΉΝ的抛光速度较慢；  Commercial barrier coatings are available in both acidic and alkaline forms, each with advantages and disadvantages. For example, the polishing rate of copper by an acid barrier polishing liquid is easily adjusted by hydrogen peroxide, and the hydrogen peroxide is stable, but the polishing speed for silicon dioxide and germanium is slow;
碱性阻挡层抛光液对铜的抛光速度不容易通过双氧水调节，且双氧水不 稳定， 但是对二氧化硅和 TiN的抛光速度较快。  The polishing rate of the alkaline barrier polishing liquid to copper is not easily adjusted by hydrogen peroxide, and the hydrogen peroxide is unstable, but the polishing speed of silica and TiN is faster.
随着技术的不断发展， Low-K材料被引入半导体制程， 这样， 阻挡层的 抛光液、 在继铜、 钽、 二氧化硅之后， 对 Low-K材料的抛光速度也提出了 更高的要求。  With the continuous development of technology, Low-K materials have been introduced into the semiconductor process, so that the polishing liquid of the barrier layer, after copper, tantalum and silicon dioxide, also puts higher requirements on the polishing speed of the Low-K material. .
在现有的阻挡层抛光技术中， US7241725、 US7300480用亚胺、 肼、 胍提升阻挡层的抛光速度。 US7491252B2用盐酸胍提升阻挡层的抛光速度。  In the existing barrier polishing technique, US7241725 and US7300480 use imine, ruthenium, and iridium to increase the polishing rate of the barrier layer. US7491252B2 uses cesium hydrochloride to increase the polishing rate of the barrier layer.
US7790618B2用到亚胺衍生物和聚乙二醇硫酸盐表面活性剂，用于阻挡层 的抛光。 以上专利提高了阻挡层的抛光速度， 但是不能很好地保护细线区的 侵烛 (erosion) 。 US7790618B2 uses an imine derivative and a polyethylene glycol sulfate surfactant for polishing the barrier layer. The above patents increase the polishing speed of the barrier layer, but do not well protect the erosion of the thin line region.
CN101665664A用季铵盐阳离子表面活性剂可抑制低介电材料 （例如 BD) 的抛光速度。 所述的阳离子季铵盐含有 C8以上的长链， 但是 C8以上 长链的大多数季铵盐型阳离子表面活性剂会显著抑制二氧化硅（OXIDE)的 抛光速度， 会阻止抛光。 CN101665664A The use of a quaternary ammonium salt cationic surfactant inhibits low dielectric materials (eg BD) polishing speed. The cationic quaternary ammonium salt contains a long chain of C8 or higher, but most of the quaternary ammonium salt type cationic surfactant having a long chain of C8 or higher significantly inhibits the polishing rate of silica (OXIDE) and prevents polishing.
EP2119353A1 使用 poly(methyl vinyl ether)用于含 Low-K材料的阻 挡层的抛光。 US2008/0276543A1 用甲脒、胍类以及聚乙烯吡咯垸酮（PVP) 的混合物用于阻挡层的抛光。这些配方在铜线细线区， 尤其是在碱性抛光条 件下， 容易形成很深的侵蚀 （Erosion) ， 硅片 （wafer) 表面平坦度的问题 需要通过其他方法解决。  EP 2119353 A1 uses poly(methyl vinyl ether) for the polishing of barrier layers containing Low-K materials. US 2008/0276543 A1 uses a mixture of formamidine, guanidine and polyvinylpyrrolidone (PVP) for the polishing of the barrier layer. These formulations are prone to deep erosion in the thin copper wire area, especially under alkaline polishing conditions. The problem of wafer surface flatness needs to be solved by other methods.
EP0373501 B1 公开了一种精抛液， 用有机聚合物， 例如聚乙烯吡咯烷 酮（PVP)调节抛光液的流体力学特性， 改善硅片表面的平坦度，减少缺陷。 但是这种精抛液， 不能用于含有金属材料 （铜、 钽） 的抛光。  EP0373501 B1 discloses a fine polishing liquid which uses an organic polymer such as polyvinylpyrrolidone (PVP) to adjust the hydrodynamic properties of the polishing liquid, improve the flatness of the surface of the silicon wafer, and reduce defects. However, this fine polishing liquid cannot be used for polishing containing metallic materials (copper, bismuth).
在以上现有技术中， 并没有一种抛光液可以在调节二氧化硅、 low-K 材料、 阻挡层、 铜等多种材料抛光速度的同时， 做到很好地保护、 调节细线 区的侵蚀 （erosion), 同时硅片具有较高的全局平整度。 发明概要  In the above prior art, there is no polishing liquid which can adjust and adjust the fine line area while adjusting the polishing speed of various materials such as silica, low-K material, barrier layer and copper. Erosion, while the silicon wafer has a high global flatness. Summary of invention
本发明所要解决的技术问题是提供一种碱性化学机械抛光液。 在调节 阻挡层、 介电层、 铜等多种材料抛光速度的同时， 做到很好地保护细线区的 侵蚀 （erosion), 同时硅片具有较高的全局平整度。  The technical problem to be solved by the present invention is to provide an alkaline chemical mechanical polishing liquid. While adjusting the polishing speed of various materials such as barrier layer, dielectric layer and copper, it can well protect the erosion of the thin line region, and the silicon wafer has a high global flatness.
本发解决上述技术问题所采用的技术方案是： 一种碱性化学机械抛光 液， 包含研磨颗粒， 唑类化合物， 络合剂， 选自 C1~C4季铵碱中的一种或 者多种， 氧化剂， 调节硅片表面平整度的表面活性剂和水。  The technical solution adopted by the present invention to solve the above technical problems is: an alkaline chemical mechanical polishing liquid comprising abrasive particles, an azole compound, a complexing agent, one or more selected from the group consisting of C1 to C4 quaternary ammonium bases, An oxidizing agent, a surfactant and water that regulate the flatness of the surface of the wafer.
在本发明中， 所述的研磨颗粒为气相 Si02和 /或溶胶 Si02， 优选溶胶 Si02。 In the present invention, the abrasive particles are gas phase SiO 2 and/or sol SiO 2 , preferably sol SiO 2 .
在本发明中， 所述的研磨颗粒浓度为质量百分比含量为 5〜25wt%。  In the present invention, the abrasive particles have a concentration of 5 to 25 wt%.
在本发明中， 所述的唑类化合物选自三氮唑及其衍生物， 优选 BTA和 / 或 TTA及其衍生物， 其中， 优选 TTA及其衍生物。 在本发明中， 所述的唑类化合物的质量百分比含量为 0.02~0.2wt%。 在本发明中， 所述的络合剂为氨基酸、柠檬酸和 /或有机膦酸。其中， 所 述的有机膦酸优选为羟基亚乙基二膦酸 （HEDP) 和 /或 2-磷酸丁烷 -1， 2，In the present invention, the azole compound is selected from the group consisting of triazole and its derivatives, preferably BTA and/or TTA and derivatives thereof, of which TTA and its derivatives are preferred. In the present invention, the azole compound has a mass percentage of 0.02 to 0.2% by weight. In the present invention, the complexing agent is an amino acid, citric acid and/or an organic phosphonic acid. Wherein, the organic phosphonic acid is preferably hydroxyethylidene diphosphonic acid (HEDP) and/or 2-butylbutane-1, 2,
4-三羟酸（JH-906), 更优选为为羟基亚乙基二膦酸 （HEDP)。 4-trihydroxy acid (JH-906), more preferably hydroxyethylidene diphosphonic acid (HEDP).
在本发明中， 所述的有机酸质量百分比含量为 0.05~0.4wt%。 .  In the present invention, the organic acid has a mass percentage of 0.05 to 0.4% by weight. .
在本发明中， 所述的 C1~C4季铵碱选自 TMAH、 TBAH、丁基三甲基氢 氧化铵和三丁基甲基氢氧化铵中的一种或多种， 优选 TBAH。  In the present invention, the C1 to C4 quaternary ammonium base is selected from one or more of TMAH, TBAH, butyltrimethylammonium hydroxide and tributylmethylammonium hydroxide, preferably TBAH.
在本发明中， 所述的 C1~C4季铵碱的质量百分比含量为 0.05~lwt%。 在本发明中， 所述的氧化剂为过氧化氢及其衍生物， 优选过氧化氢。 在本发明中， 所述的氧化剂的质量百分比含量为 0.1~lwt%。  In the present invention, the C1 to C4 quaternary ammonium base has a mass percentage of 0.05 to 1 wt%. In the present invention, the oxidizing agent is hydrogen peroxide and a derivative thereof, preferably hydrogen peroxide. In the present invention, the oxidizing agent has a mass percentage of 0.1 to 1% by weight.
在本发明中，所述的调节硅片表面平整度的表面活性剂为聚乙烯吡咯垸 酮 （PVP)。  In the present invention, the surfactant which adjusts the surface flatness of the silicon wafer is polyvinylpyrrolidone (PVP).
在本发明中， 所述的聚乙烯吡咯垸酮 （PVP ) 的质量百分比含量为 0.01〜lwt%。  In the present invention, the polyvinylpyrrolidone (PVP) has a mass percentage of 0.01 to 1% by weight.
在本发明中， 所述的抛光液 pH值为 9~12。  In the present invention, the polishing liquid has a pH of 9 to 12.
在本发明中， 所述抛光液还包含 pH值调节剂， 其中， pH值调节剂为碱 或酸， 其中， 所述的碱为 KOH， 所述的酸为 HN03。 In the present invention, the polishing liquid further comprises a pH adjusting agent, wherein the pH adjusting agent is a base or an acid, wherein the base is KOH, and the acid is HNO 3 .
如上所述的抛光液可应用在抛光阻挡层。  The polishing liquid as described above can be applied to the polishing barrier layer.
聚乙烯吡咯垸酮可应用在调节硅片表面的平整度。  Polyvinylpyrrolidone can be used to adjust the flatness of the surface of the wafer.
C1-C4季铵碱可应用在有效控制铜线细线区的侵蚀。  The C1-C4 quaternary ammonium base can be used to effectively control the erosion of the thin line region of the copper wire.
本发明所用试剂、 原料以及产品均市售可得。  The reagents, materials and products used in the present invention are commercially available.
本发明的积极进步效果在于- The positive progress of the present invention is that -
1 ) 通过调节多种材料的抛光速度， 显著提高硅片表面的平整度。 1) Significantly improve the flatness of the silicon wafer surface by adjusting the polishing speed of various materials.
2) 有效控制铜线细线区的侵蚀 （erosion), 同时配方中含有 C1~C4季 铵碱， 不同于含 C8以上的季铵盐表面活性剂， 不会形成泡沬， 还可以作为 有机碱， 调节 PH值， 优于 KOH， 不引入金属离子。 发明内容 2) Effectively control the erosion of the thin wire area of the copper wire. At the same time, the formula contains C1~C4 quaternary ammonium base. Different from the quaternary ammonium salt surfactant containing C8 or above, it does not form bubbles and can also be used as an organic base. , adjust the pH value, better than KOH, and do not introduce metal ions. Summary of the invention
下面通过具体实施例进一步阐述本发明的优点，但本发明的保护范围不 仅仅局限于下述实施例。  The advantages of the present invention are further illustrated by the following specific examples, but the scope of the present invention is not limited to the following embodiments.
按照表 1中各实施例的成分及其比例配制抛光液， 混合均匀。  The polishing liquid was prepared in accordance with the ingredients of the respective examples in Table 1 and their ratios, and mixed uniformly.
表 1本发明实施例 1-9以及对比例 1-2的配方  Table 1 Formulations of Inventive Examples 1-9 and Comparative Examples 1-2
过  Over
C1 C4季铵 氧 表面活性 研磨颗粒 唑类化合物 络合剂 H 碱 化 剂 序  C1 C4 quaternary ammonium oxygen surface active abrasive particles azole compound complexing agent H alkalizing agent
氢  Hydrogen
号  number
浓 浓  Thick
浓度 浓度 浓度 种 浓度 种类 度 种类 种类 种类 度  Concentration concentration concentration species concentration degree species type species degree
wt% wt% wt% 类 wt% t% wt% 对  Wt% wt% wt% class wt% t% wt% pair
溶胶  Sol
比 15 BTA 0.1 甘讀 0.1 0.2 10 Si02  Than 15 BTA 0.1 Gan reading 0.1 0.2 10 Si02
例 1  example 1
对  Correct
溶胶  Sol
比 15 BTA 0.1 柠檬酸 0.1 0.2 10 Si02  Than 15 BTA 0.1 citric acid 0.1 0.2 10 Si02
例 2  Example 2
实  Real
溶胶  Sol
施 15 BTA 0.02 JH-906 0.05 TMAH 0.05 0.1 PVP 0.5 10 Si02  15 BTA 0.02 JH-906 0.05 TMAH 0.05 0.1 PVP 0.5 10 Si02
例 1  example 1
实  Real
溶胶  Sol
施 15 TTA 0.1 HEDP 0.1 TBAH 0.2 0.2 PVP 0.2 10 Si02  15 TTA 0.1 HEDP 0.1 TBAH 0.2 0.2 PVP 0.2 10 Si02
例 2  Example 2
实  Real
溶胶  Sol
施 10 TTA 0.1 HEDP 0.1 TBAH 0.1 0.4 PVP 0.3 10 Si02  10 TTA 0.1 HEDP 0.1 TBAH 0.1 0.4 PVP 0.3 10 Si02
例 3  Example 3
实  Real
溶胶  Sol
施 10 TTA 0.1 HEDP 0.1 TBAH 0.1 0.2 PVP 0.5 10 Si02  10 TTA 0.1 HEDP 0.1 TBAH 0.1 0.2 PVP 0.5 10 Si02
例 4  Example 4
实  Real
溶胶  Sol
施 5 BTA 0.02 JH-906 0.05 TMAH 0, 05 0.5 PVP 0.01 9 Si02  5 BTA 0.02 JH-906 0.05 TMAH 0, 05 0.5 PVP 0.01 9 Si02
例 5  Example 5
实  Real
溶胶 IRGAMET  Sol IRGAMET
施 15 0.1 HEDP 0.3 ' TBAH 0.2 0.4 PVP 0.5 10 Si02 42*  15 15 HEDP 0.3 ' TBAH 0.2 0.4 PVP 0.5 10 Si02 42*
例 6 实 甲  Example 6 Real A
溶胶  Sol
施 15 TTA 0.1 HEDP 0.1 1 1 PVP 1 11 Si02  15 TTA 0.1 HEDP 0.1 1 1 PVP 1 11 Si02
例 7  Example 7
铵 三丁 Ammonium Sanding
实 基甲  Real base
溶胶  Sol
施 25 TTA 0. 1 HEDP 0. 2 基氢 0. 5 0. 4 PVP 0. 4 12 Si02  25 TTA 0. 1 HEDP 0. 2 base hydrogen 0. 5 0. 4 PVP 0. 4 12 Si02
例 8 氧化  Example 8 oxidation
铵  Ammonium
实  Real
气相  Gas phase
施 15 TTA 0. 2 HEDP 0. 4 TBAH 0. 5 0. 4 PVP 0. 5 10 Si02  15 TTA 0. 2 HEDP 0. 4 TBAH 0. 5 0. 4 PVP 0. 5 10 Si02
例 9  Example 9
(其中， IRGAMET 42* 为 TTA衍生物） （TTA为甲基苯骈三氮唑， 市售可得)  (Where IRGAMET 42* is a TTA derivative) (TTA is methyl benzotriazole, commercially available)
进一步将表 1中的抛光液配方根据下述实验条件进行试验。 Further, the polishing liquid formulations in Table 1 were tested in accordance with the following experimental conditions.
抛光条件： Mirra机台， fujibo pad, 转速 93/87， 抛光压力： 1.5psL Slurry流量 200mL/min. 在 Mirra机台中输入上述参数， 对 8寸的二氧化 硅硅片， BD硅片， 铜硅片和含有铜线细线区的硅片进行 1 min地抛光， 清 洗、 干燥、 检测并得到表 2 的抛光结果。 表 2本发明实施例 1-9以及对比例 1-2的抛光结果  Polishing conditions: Mirra machine, fujibo pad, speed 93/87, polishing pressure: 1.5psL Slurry flow 200mL/min. Enter the above parameters in the Mirra machine, for 8 inch silicon dioxide wafer, BD wafer, copper silicon The wafer and the silicon wafer containing the thin line of copper wire were polished for 1 min, washed, dried, and tested to obtain the polishing results of Table 2. Table 2 Polishing results of Examples 1-9 and Comparative Examples 1-2 of the present invention
钽抛光速 二氧化硅 细线区 铜抛光速度 硅片表面平整度  钽 polishing speed, silica, fine line area, copper polishing speed, wafer surface flatness
序号 度 抛光速度 (0. 18*0. 18um)  No. Degree Polishing speed (0. 18*0. 18um)
(A/min) (NU%)  (A/min) (NU%)
(A/min) (A/min) erosion (nm) 对比例  (A/min) (A/min) erosion (nm)
500 1010 400 6 50  500 1010 400 6 50
1  1
对比例  Comparative example
510 1012 360 7 60  510 1012 360 7 60
2  2
实施例  Example
530 1013 300 2 4  530 1013 300 2 4
1  1
实施例  Example
590 1100 310 3 5  590 1100 310 3 5
2  2
实施例  Example
510 801 320 3 5  510 801 320 3 5
3  3
实施例  Example
510 820 300 3 2  510 820 300 3 2
4  4
实施例  Example
400 604 404 2 10  400 604 404 2 10
5  5
实施例  Example
530 1100 350 4 6 实施例 530 1100 350 4 6 Example
540 1200 300 3 10 540 1200 300 3 10
7 7
实施例  Example
700 1500 600 3 5  700 1500 600 3 5
8  8
实施例  Example
570 900 650 3 5  570 900 650 3 5
9  9
从对比例 1， 2 可以看出， 没有季铵碱和 PVP存在下， 铜线的细线区 侵蚀 （erosion ) 严重， 硅片表面平整度不好。 实施例 1 至 9中， 加入了 C1~C4季铵碱和 PVP， 铜线的细线区侵蚀（erosion) 显著改善， 硅片全局 平坦化的效果更好。 It can be seen from Comparative Example 1, 2 that in the absence of quaternary ammonium base and PVP, the erosion of the thin wire region of the copper wire is severe, and the flatness of the surface of the silicon wafer is not good. In Examples 1 to 9, C1~C4 quaternary ammonium base and PVP were added, and the erosion of the thin wire region of the copper wire was remarkably improved, and the effect of the global flattening of the silicon wafer was better.
综合而言， 采用本发明的抛光液在调节二氧化硅、 阻挡层、 铜等多种 材料抛光速度的同时， 做到很好地保护细线区的侵蚀 （erosion ) , 提高了硅 片表面平整度。  In general, the polishing liquid of the present invention can protect the erosion of the thin line region and improve the surface smoothness of the silicon wafer while adjusting the polishing speed of various materials such as silicon dioxide, barrier layer and copper. degree.
应当理解的是， 本发明所述 wt%均指的是质量百分含量。  It should be understood that the wt% of the present invention refers to the mass percentage.
以上对本发明的具体实施例进行了详细描述， 但其只是作为范例， 本发 明并不限制于以上描述的具体实施例。对于本领域技术人员而言， 任何对本 发明进行的等同修改和替代也都在本发明的范畴之中。 因此， 在不脱离本发 明的精神和范围下所作的均等变换和修改， 都应涵盖在本发明的范围内。  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 of the present 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.

Claims

权利要求 Rights request
1、 一种碱性化学机械抛光液， 含有： 研磨颗粒， 唑类化合物， 络合 剂， 选自 C1〜C4季铵碱中的一种或者多种， 氧化剂， 调节硅片表面平整度 的表面活性剂和水。 1. An alkaline chemical mechanical polishing liquid, containing: abrasive particles, azole compounds, complexing agents, one or more selected from C1 to C4 quaternary ammonium bases, oxidants, and a surface for adjusting the flatness of the silicon wafer surface active agent and water.
2、 根据权利要求 1所述的抛光液， 其特征在于， 所述的研磨颗粒为气 相 Si02和 /或溶胶 Si02。 2. The polishing fluid according to claim 1, characterized in that the abrasive particles are gas phase SiO 2 and/or sol SiO 2 .
3、 根据权利要求 2所述的抛光液， 其特征在于， 所述的研磨颗粒为溶 胶 Si02。 3. The polishing fluid according to claim 2, characterized in that the abrasive particles are sol Si0 2 .
4、 根据权利要求 1所述的抛光液， 其特征在于， 所述的研磨颗粒浓度 为质量百分比含量为 5~25wt%。 4. The polishing fluid according to claim 1, characterized in that the concentration of the abrasive particles is 5 to 25 wt% by mass.
5、 根据权利要求 1所述的抛光液， 其特征在于， 所述的唑类化合物选 自三氮唑及其衍生物。 5. The polishing fluid according to claim 1, characterized in that the azole compound is selected from triazole and its derivatives.
6、 根据权利要求 5所述的抛光液， 其特征在于， 所述的三氮唑及其衍 生物为 BTA和 /或 TTA及其衍生物。 6. The polishing fluid according to claim 5, characterized in that the triazole and its derivatives are BTA and/or TTA and its derivatives.
7、 根据权利要求 6所述的抛光液， 其特征在于， 所述的三氮唑为 TTA 及其衍生物。 7. The polishing fluid according to claim 6, wherein the triazole is TTA and its derivatives.
8、 根据权利要求 1所述的抛光液， 其特征在于， 所述的唑类化合物的 质量百分比含量为 0.02〜0.2wt%。 8. The polishing fluid according to claim 1, characterized in that the mass percentage content of the azole compound is 0.02~0.2wt%.
9、 根据权利要求 1所述的抛光液， 其特征在于， 所述的络合剂为氨基 酸、 柠檬酸和 /或有机膦酸。 9. The polishing fluid according to claim 1, wherein the complexing agent is amino acid, citric acid and/or organic phosphonic acid.
10、 根据权利要求 9所述的抛光液， 其特征在于， 所述的有机膦酸为羟 基亚乙基二膦酸 （HEDP) 和 /或 2-磷酸丁垸 -1， 2， 4-三羟酸（JH-906)。 10. The polishing fluid according to claim 9, characterized in that the organic phosphonic acid is hydroxyethylene diphosphonic acid (HEDP) and/or 2-butyl phosphate-1,2,4-trihydroxy Acid (JH-906).
11、 根据权利要求 10所述的抛光液， 其特征在于， 所述的有机膦酸为 羟基亚乙基二膦酸 （HEDP) . 11. The polishing fluid according to claim 10, wherein the organic phosphonic acid is hydroxyethylene diphosphonic acid (HEDP).
12、 根据权利要求 9所述的有机酸质量百分比含量为 0.05~0.4wt%。 - 12. The organic acid mass percentage content according to claim 9 is 0.05~0.4wt%. -
13、 根据权利要求 1所述的抛光液， 其特征在于， 所述的 C1~C4季铵 碱选自 TMAH、 TBAH、 丁基三甲基氢氧化铵和三丁基甲基氢氧化铵中的一 种或多种。 13. The polishing fluid according to claim 1, characterized in that, the C1~C4 quaternary ammonium The base is selected from one or more of TMAH, TBAH, butyltrimethylammonium hydroxide and tributylmethylammonium hydroxide.
14、 根据权利要求 13所述的抛光液， 其特征在于， 所述的 C1〜C4季铵 碱为 TBAH。 14. The polishing fluid according to claim 13, characterized in that the C1~C4 quaternary ammonium base is TBAH.
15、 根据权利要求 1所述的抛光液， 其特征在于， 所述的 C1〜C4季铵 碱的质量百分比含量为 0.05~lwt%。 15. The polishing fluid according to claim 1, characterized in that the mass percentage content of the C1~C4 quaternary ammonium base is 0.05~1wt%.
16、 根据权利要求 1所述的抛光液， 其特征在于， 所述的氧化剂为过氧 化氢及其衍生物。 16. The polishing fluid according to claim 1, wherein the oxidizing agent is hydrogen peroxide and its derivatives.
17、 根据权利要求 16所述的抛光液， 其特征在于， 所述的氧化剂为过 氧化氢。 . 17. The polishing fluid according to claim 16, wherein the oxidizing agent is hydrogen peroxide. .
18、 根据权利要求 1所述的抛光液， 其特征在于， 所述的氧化剂的质量 百分比含量为 0.1~lwt%。 18. The polishing fluid according to claim 1, characterized in that the mass percentage content of the oxidant is 0.1~1wt%.
19、 根据权利要求 1所述的抛光液， 其特征在于， 所述的调节硅片表面 平整度的表面活性剂为聚乙烯吡咯垸酮 （PVP)。 19. The polishing fluid according to claim 1, characterized in that the surfactant for adjusting the flatness of the silicon wafer surface is polyvinylpyrrolidone (PVP).
20、 根据权利要求 1所述的抛光液， 所述的聚乙烯吡咯垸酮 （PVP) 的 质量百分比含量为 0.01〜lwt%。 20. The polishing fluid according to claim 1, the mass percentage content of the polyvinylpyrrolidone (PVP) is 0.01~1wt%.
21、 根据权利要求 1所述的抛光液， 其特征在于， 所述的抛光液 pH值 为 9~12。 21. The polishing fluid according to claim 1, characterized in that the pH value of the polishing fluid is 9~12.
22、 根据权利要求 21所述的抛光液， 其特征在于， 所述抛光液还包含 pH值调节剂， 其中， pH值调节剂为碱或酸。 22. The polishing liquid according to claim 21, wherein the polishing liquid further contains a pH adjuster, wherein the pH adjuster is an alkali or an acid.
23、 根据权利要求 22所述的抛光液， 其特征在于， 所述的碱为 KOH。 23. The polishing fluid according to claim 22, wherein the alkali is KOH.
24、 根据权利要求 22所述的抛光液， 其特征在于， 所述的酸为 HN03。24. The polishing fluid according to claim 22, characterized in that the acid is HNO 3 .
25、 如权利要求 .1-24任一项所述的抛光液在抛光阻挡层中的应用。25. Application of the polishing liquid according to any one of claims 1 to 24 in the polishing barrier layer.
26、 聚乙烯吡咯垸酮在调节硅片表面平整度中的应用。 26. Application of polyvinylpyrrolidone in adjusting the surface flatness of silicon wafers.
27、 C1-C4季铵碱在有效控制铜线细线区的侵蚀中的应用。 27. The application of C1-C4 quaternary ammonium bases in effectively controlling corrosion in the fine line areas of copper wires.
PCT/CN2013/000980 2012-10-17 2013-08-22 Alkaline chemical-mechanical polishing solution WO2014059744A1 (en)

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