WO2022143718A1 - 一种化学机械抛光液及其使用方法 - Google Patents

一种化学机械抛光液及其使用方法 Download PDF

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WO2022143718A1
WO2022143718A1 PCT/CN2021/142292 CN2021142292W WO2022143718A1 WO 2022143718 A1 WO2022143718 A1 WO 2022143718A1 CN 2021142292 W CN2021142292 W CN 2021142292W WO 2022143718 A1 WO2022143718 A1 WO 2022143718A1
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acid
mechanical polishing
chemical mechanical
polishing liquid
polishing
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PCT/CN2021/142292
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English (en)
French (fr)
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周靖宇
马健
荆建芬
倪宇飞
宋凯
汪国豪
周文婷
杨征
王拓
许芃亮
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安集微电子科技（上海）股份有限公司
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Publication of WO2022143718A1 publication Critical patent/WO2022143718A1/zh

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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
    • H01L21/302—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
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • 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
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing

Definitions

  • the invention relates to the field of chemical mechanical polishing, in particular to a chemical mechanical polishing liquid and a method for using the same.
  • CMP chemical mechanical polishing
  • abrasive head moves linearly on the polishing pad or rotates in the same direction of motion as the polishing table.
  • the slurry containing the abrasive is dripped onto the polishing pad and spreads on the polishing pad due to centrifugal action.
  • the chip surface is globally planarized under the dual action of mechanics and chemistry.
  • carbon-containing materials such as silicon carbide and amorphous carbon have the characteristics of wide band gap, high thermal conductivity, high critical breakdown electric field, high electron saturation migration rate, and high chemical stability.
  • high-power, high-density integrated electronic devices have huge application potential.
  • carbon-containing materials are very stable at room temperature, are not prone to chemical reactions, and have good resistance to mechanical grinding. Therefore, it is difficult for commonly used chemical-mechanical polishing liquids to achieve high polishing speeds when polishing carbon-containing materials.
  • CN102464944A adds strong oxidizing agents such as permanganic acid, manganic acid and their salts to the polishing liquid to improve the chemical mechanical polishing rate of carbonaceous materials.
  • the present invention provides a polishing liquid and a method for using the same.
  • the by-products of the polishing process can directly interact with the inorganic acid without affecting the removal rate. and its salts react to form soluble manganese complexes, thereby avoiding the deposition of by-products of the polishing process on the polishing pad, prolonging the service life of the polishing pad, and reducing defects on the wafer surface after polishing.
  • the chemical mechanical polishing liquid in the present invention includes a chemical mechanical polishing liquid, including abrasives, oxidizing agents, inorganic acids and salts thereof, and water.
  • the inorganic acid is selected from hydrobromic acid, hydroiodic acid, hydrotelluric acid, boric acid, perboric acid, metaboric acid, bromic acid, iodic acid, chromic acid, manganese acid, arsenic acid, tungstic acid, molybdic acid, selenic acid, One or more of telluric acid, lead acid, meta-aluminate, meta-arsenous acid, phosphoric acid, hypophosphorous acid and pyrophosphoric acid; the salts are selected from one or more of potassium salt, sodium salt or ammonium salt kind.
  • the oxidant is potassium permanganate.
  • the abrasive is selected from one or more of manganese dioxide, aluminum oxide, ceria, titanium dioxide single-component abrasives and composite abrasives coated with silicon dioxide, aluminum oxide, ceria, and titanium dioxide on the surface .
  • the mass percentage content of the abrasive is 0.1-10%.
  • the particle size of the abrasive is in the range of 50-500 nm.
  • the mass percentage content of the oxidant is 0.01-1%.
  • the mass percentage content of the inorganic acid and its salts is 0.01-2%.
  • the mass percentage content of the inorganic acid and its salts is 0.1-0.5%.
  • the pH value of the chemical mechanical polishing solution is 2-6.
  • the polishing liquid of the present invention can be prepared by concentrating the components other than the oxidizing agent, diluted with deionized water before use, and adding the oxidizing agent to the concentration range of the present invention.
  • the present invention provides a method for using the chemical mechanical polishing liquid of the present invention, comprising: using the chemical mechanical polishing liquid of the present invention for chemical mechanical polishing of carbonaceous materials.
  • the present invention has the advantages that inorganic acids and their salts are added to the chemical mechanical polishing solution, which reduces the residue of polishing by-products on the surface of the polishing pad, and reduces the surface damage of the wafer after polishing. defect.
  • the polishing liquids of Comparative Examples 1-4 and Example 1-50 of the present application were prepared, and then a certain concentration of oxidant solution, inorganic acid and its salts and abrasives were mixed evenly, and the mass percentage of water was added to 100%, use KOH or HNO 3 to adjust the polishing liquid to the desired pH value.
  • the blank amorphous carbon was polished according to the following conditions. Specific polishing conditions: polishing machine is Reflexion LK, polishing pad IC1010 polishing pad, 300mm wafer, grinding pressure 2.5psi, grinding disc speed 93 rpm, grinding head speed 87 rpm, polishing fluid flow rate 300ml/min, The polishing time was 1 min.
  • the measured polishing effect data of Comparative Examples 1-4 and Examples 42-50 are recorded in Table 2.
  • the degree of cleanliness of the polishing pad surface is described as follows:
  • the polishing liquid of the embodiment of the present invention has a higher amorphous carbon removal rate.
  • the polishing liquids of Comparative Examples 1-3 contain single-component abrasives, and the polishing liquids of Comparative Example 4 use composite abrasives and potassium permanganate as oxidants, which have a certain removal rate of amorphous carbon, but the surface cleanliness of the polishing pad after polishing poor.
  • the polishing liquids of Comparative Examples 42, 44 and 45 added inorganic acids and their salts, and the removal rate of amorphous carbon was slightly reduced, but the polishing pads could be effectively reduced. Surface polishing by-products remain, significantly improving pad surface cleanliness.
  • polishing solutions of Examples 42-50 of the present invention can ensure a higher amorphous carbon removal rate by selecting abrasives, oxidants, inorganic acids and their salts with appropriate particle sizes, and adjusting the appropriate pH value. At the same time, the residue of polishing by-products on the surface of the polishing pad is reduced, and the surface cleanliness of the polishing pad is significantly improved.
  • the blank amorphous carbon was polished according to the following conditions and the number of surface defects was detected. Specific polishing conditions:
  • Polishing conditions polishing machine is Reflexion LK, polishing pad IC1010 polishing pad, 300mm wafer, grinding pressure 2.5psi, grinding disc speed 93 rpm, grinding head speed 87 rpm, polishing fluid flow rate 300ml/min, polishing The time is 1min.
  • the surface defect counts of the blank wafers after polishing were detected with a surface defect scanner SP2, and the results of the obtained surface defect counts are listed in Table 3.
  • Example 48 46
  • Example 49 37
  • Example 50 59
  • the comparative examples 1-4 did not use inorganic acids and their salts, and the number of defects on the surface of the amorphous carbon wafer after polishing was in the range of 350 to 450, while the inorganic acids and their salts were used in the present invention.
  • the polishing solutions of Examples 47-50 significantly improved the surface defects of amorphous carbon after polishing, the number of surface defects was reduced to within the range of 30-70, and the number of surface defects of amorphous carbon was greatly reduced.
  • polishing liquids of Comparative Examples 1-4 and Examples 47-50 the blank silicon carbide was polished according to the following conditions. Specific polishing conditions: polishing machine is Reflexion LK, polishing pad IC1010 polishing pad, 300mm wafer, grinding pressure 2.5psi, grinding disc speed 93 rpm, grinding head speed 87 rpm, polishing fluid flow rate 300ml/min, The polishing time was 1 min.
  • the measured polishing effect data of Comparative Examples 1-4 and Examples 47-50 are recorded in Table 4.
  • the present invention uses the polishing liquids of Examples 47-50 of inorganic acid and salts thereof, and still has a relatively high amount of silicon carbide. Removal rate, while reducing the polishing pad by-product residue on the polishing pad surface, and improving the cleaning degree of the polishing pad surface.
  • the present invention ensures that the polishing liquid has a high removal rate for carbonaceous materials under acidic conditions, reduces the residual polishing by-products on the surface of the polishing pad after polishing, and reduces the Defects on the wafer surface.

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

Abstract

本发明旨在提供一种用于含碳材料的抛光液及其使用方法。所述化学机械抛光液，包含磨料、氧化剂和无机酸及其盐类，该抛光液在维持较高的含碳材料去除速率的同时，有效减少了抛光垫表面的抛光副产物残留，显著提升了抛光垫表面清洁程度，延长了抛光垫的使用寿命，降低了抛光后晶圆表面的缺陷。

Description

一种化学机械抛光液及其使用方法 技术领域
本发明涉及化学机械抛光领域，尤其涉及一种化学机械抛光液及其使用方法。
背景技术
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抛光(CMP)技术被认为是目前全局平坦化的最有效的方法。化学机械抛光(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。当进行化学机械抛光时，研磨头在抛光垫上线性移动或是沿着与研磨台相同的运动方向旋转。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。
碳化硅、无定形碳等含碳材料作为新一代宽带隙半导体材料，具有宽带隙、高热导率、高临界击穿电场、高电子饱和迁移速率、高化学稳定性等特点，在高温、高频、大功率、高密度集成电子器件等方面具有巨大的应用潜力。然而含碳材料在常温下非常稳定，不易发生化学反应，对机械力研磨的耐受性很好，因此常用的化学机械抛光液在抛光含碳材料时，难以获得较高的抛光速度。
通常需要用氧化剂将含碳材料氧化后去除。常用的氧化剂为双氧水，但双氧水的氧化能力较弱，无法获得理想的去除速率。CN102464944A在抛光液中添加高锰酸、锰酸及其盐类等强氧化剂来提高含碳材料的化学机械抛光速率。在使用高锰酸、锰酸及其盐类作为氧化剂对含碳材料抛光过程中，由于高锰酸、锰酸等氧化剂被还原后会不可避免地生成颜色较深的副产物，而且容易沉积在抛光垫的表面和孔洞中，从而造成抛光副产物在抛光垫上的聚集，影响抛光垫寿命，而且导致抛光后的表面缺陷增加。
发明内容
为了解决上述问题，本发明提供一种抛光液及其使用方法，通过在抛光液中加入无机酸及其盐类，在较少影响去除速率的情况下，使得抛光过程副产物可以直接和无机酸及其盐类发生反应，形成可溶性的锰络合物，从而避免抛光过程的副产物在抛光垫上沉积，延长了抛光垫的使用寿命，同时降低了抛光后晶圆表面的缺陷。
具体的，本发明中的化学机械抛光液包含一种化学机械抛光液，包含磨料、氧化剂、无机酸及其盐类和水。
所述无机酸选自氢溴酸、氢碘酸、氢碲酸、硼酸、过硼酸、偏硼酸、溴酸、碘酸、铬酸、锰酸、砷酸、钨酸、钼酸、硒酸、碲酸、铅酸、偏铝酸、偏亚砷酸、磷酸、次磷酸、焦磷酸中的一种或多种；所述盐类选自钾盐、钠盐或铵盐中的一种或多种。
所述氧化剂为高锰酸钾。
所述磨料选自二氧化锰、三氧化二铝、二氧化铈、二氧化钛单组分磨料以及表面包覆二氧化硅、三氧化二铝、二氧化铈、二氧化钛的复合磨料中一种或多种。
本发明中，所述磨料的质量百分比含量为0.1-10％。
本发明中，所述磨料的粒径范围为50-500nm。
本发明中，所述氧化剂的质量百分比含量为0.01-1％。
本发明中，所述无机酸及其盐类的质量百分比含量为0.01-2％。
本发明中，所述无机酸及其盐类的质量百分比含量为0.1-0.5％。
本发明中，所述化学机械抛光液的pH值为2-6。
本发明的抛光液可以将除氧化剂以外的组分浓缩配置，使用前用去离子水稀释并加入氧化剂至本发明的浓度范围。
另一方面，本发明提供了一种本发明中化学机械抛光液的使用方法，包括：将本发明的化学机械抛光液用于含碳材料的化学机械抛光。
与现有技术相比较，本发明的优势在于：在所述化学机械抛光液中加入无机酸及其盐类，减少了抛光副产物在抛光垫表面的残留，同时降低了抛光后晶圆表面的缺陷。
具体实施方式
下面结合具体实施例，详细阐述本发明的优势。
根据表1中所给配方，配置本申请对比例1-4与实施例1-50的抛光液，随后将一定浓度的氧化剂溶液、无机酸及其盐类与磨料混合均匀，用水补足质量百分比至100％，使用KOH或HNO 3将抛光液调节至所需pH值即可。
表1对比例1-4和实施例1-50的抛光液成分、含量及其pH
Figure PCTCN2021142292-appb-000001
Figure PCTCN2021142292-appb-000002
Figure PCTCN2021142292-appb-000003
效果实施例1
采用对比例1-4和实施例42-50的抛光液，按照下述条件对空片无定形碳进行抛光。具体抛光条件：抛光机台为Reflexion LK，抛光垫IC1010抛光垫，300mm晶圆，研磨压力2.5psi，研磨盘转速93转/分钟，研磨头转速87转/分钟，抛光液流速为300ml/min，抛光时间为1min。测得对比例1-4和实施例42-50的抛光效果数据记于表2。
表2对比例1-4和实施例42-50的抛光效果数据
抛光液 无定形碳去除速率(A/min) 抛光垫表面清洁程度
对比例1 30 +++
对比例2 180 ++++
对比例3 55 +++
对比例4 175 ++++
实施例42 178 ++
实施例43 58 +
实施例44 172 +
实施例45 179 +
实施例46 180 +
实施例47 241 +
实施例48 229 ++
实施例49 185 ++
实施例50 203 +
其中抛光垫表面清洁程度按以下方式进行描述：
++++抛光垫表面有严重污染；+++抛光垫表面有明显污染；++抛光垫表面有少量污染；+抛光垫表面无明显污染。
由表2可见，与对比例相比，本发明实施例的抛光液具有较高的无定形碳去除速率。对比例1-3的抛光液含有单组分的磨料，对比例4抛光液选用了复合磨料和高锰酸钾作为氧化剂，具有一定的无定形碳的去除速率，但抛光后抛光垫表面清洁程度较差。与对比例2、3和4的抛光液相比，实施例42、44和45的抛光液添加了无机酸及其盐类，其无定形碳的去除速率略有降低，但能够有效减少抛光垫表面的抛光副产物残留，显著改善了抛光垫表面清洁程度。
由此可见，本发明的实施例42-50抛光液通过选择合适的粒径的磨料、氧化剂及无机酸及其盐类，并调节合适的pH值，在保证较高的无定形碳去除速率的同时，减少抛光副产物在抛光垫表面的残留，显著改善了抛光垫的表面清洁程度。
效果实施例2
采用对比例1-4和本发明实施例47-50的抛光液，按照下述条件对空片无定形碳进行抛光并检测表面缺陷数量。具体抛光条件：
抛光条件：抛光机台为Reflexion LK，抛光垫IC1010抛光垫，300mm晶圆，研磨压力2.5psi，研磨盘转速93转/分钟，研磨头转速87转/分钟，抛光液流速为300ml/min，抛光时间为1min。用表面缺陷扫描仪SP2检测抛光后空白晶圆的表面缺陷数，所得的表面缺陷数的结果列于表3。
表3对比例1-4和实施例47-50的抛光后无定形碳表面缺陷数
抛光液 无定形碳表面缺陷数(>80nm)(颗)
对比例1 396
对比例2 419
对比例3 387
对比例4 425
实施例47 63
实施例48 46
实施例49 37
实施例50 59
由表3可见，对比例1-4未使用无机酸及其盐类，抛光后无定形碳晶圆表面的缺陷数量350～450颗的范围内，而在本发明中使用无机酸及其盐类的实施例47～50的抛光液对抛光后无定形碳表面缺陷有显著改善，表面缺陷数量减少至30～70颗的范围内，无定形碳表面缺陷数量大幅度降低。
效果实施例3
采用对比例1-4和实施例47-50的抛光液，按照下述条件对空片碳化硅进行抛光。具体抛光条件：抛光机台为Reflexion LK，抛光垫IC1010抛光垫，300mm晶圆，研磨压力2.5psi，研磨盘转速93转/分钟，研磨头转速87转/分钟，抛光液流速为300ml/min，抛光时间为1min。测得对比例1-4和实施例47-50的抛光效果数据记于表4。
表4对比例1-4和实施例47-50的碳化硅抛光效果数据
抛光液 碳化硅去除速率(A/min) 抛光垫表面清洁程度
对比例1 220 +++
对比例2 674 +++
对比例3 281 ++++
对比例4 659 +++
实施例47 802 ++
实施例48 748 +
实施例49 683 +
实施例50 705 +
由表4可见，与未添加无机酸及其盐类的对比例1-4相比，本发明使用无机酸及其盐类的实施例47-50的抛光液，仍有较高的碳化硅的去除速率，同时减少抛光垫表面的抛光垫副产物残留，提高抛光垫表面清洁程度。
综上所述，本发明通过添加无机酸及其盐类，在酸性条件下保证抛光液对含碳材料具有较高的去除速率，减少抛光后抛光垫表面的抛光副产物残留，同时降低抛光后晶圆表面的缺陷。
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。

Claims (11)

  1. 一种化学机械抛光液，其特征在于，
    包含磨料、氧化剂、无机酸及其盐类和水。
  2. 如权利要求1所述的化学机械抛光液，其特征在于，
    所述无机酸选自氢溴酸、氢碘酸、氢碲酸、硼酸、过硼酸、偏硼酸、溴酸、碘酸、铬酸、锰酸、砷酸、钨酸、钼酸、硒酸、碲酸、铅酸、偏铝酸、偏亚砷酸、磷酸、次磷酸、焦磷酸中的一种或多种；
    所述盐类选自钾盐、钠盐或铵盐中的一种或多种。
  3. 如权利要求1所述的化学机械抛光液，其特征在于，
    所述氧化剂为高锰酸钾。
  4. 如权利要求1所述的化学机械抛光液，其特征在于，
    所述磨料选自二氧化锰、三氧化二铝、二氧化铈、二氧化钛单组分磨料以及表面包覆二氧化硅、三氧化二铝、二氧化铈、二氧化钛的复合磨料中一种或多种。
  5. 如权利要求1所述的化学机械抛光液，其特征在于，
    所述磨料的质量百分比含量为0.1-10％。
  6. 如权利要求1所述的化学机械抛光液，其特征在于，
    所述磨料的粒径范围为50-500nm。
  7. 如权利要求1所述的化学机械抛光液，其特征在于，
    所述氧化剂的质量百分比含量为0.01-1％。
  8. 如权利要求1所述的化学机械抛光液，其特征在于，
    所述无机酸及其盐类的质量百分比含量为0.01-2％。
  9. 如权利要求8所述的化学机械抛光液，其特征在于，
    所述无机酸及其盐类的质量百分比含量为0.1-0.5％。
  10. 如权利要求1所述的化学机械抛光液，其特征在于，
    所述化学机械抛光液的pH值为2-6。
  11. 一种化学机械抛光液的使用方法，其特征在于，
    将如权利要求1-10中任一项所述的化学机械抛光液用于含碳材料的化学机械抛光。
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