WO2021135807A1 - 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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WO2021135807A1
WO2021135807A1 PCT/CN2020/133616 CN2020133616W WO2021135807A1 WO 2021135807 A1 WO2021135807 A1 WO 2021135807A1 CN 2020133616 W CN2020133616 W CN 2020133616W WO 2021135807 A1 WO2021135807 A1 WO 2021135807A1
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Prior art keywords
chemical mechanical
mechanical polishing
polishing liquid
titanium dioxide
polishing
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PCT/CN2020/133616
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English (en)
French (fr)
Inventor
马健
荆建芬
姚颖
周靖宇
杨俊雅
黄悦锐
蔡鑫元
陆弘毅
王雨春
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安集微电子（上海）有限公司
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Priority to KR1020227021943A priority Critical patent/KR20220119628A/ko
Publication of WO2021135807A1 publication Critical patent/WO2021135807A1/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
    • 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
    • C09K3/1436—Composite particles, e.g. coated particles
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
    • H01L21/76819—Smoothing of the dielectric
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/7684—Smoothing; Planarisation

Definitions

  • the invention relates to the field of chemical mechanical polishing, in particular to a chemical mechanical polishing liquid and a method of use thereof.
  • CMP chemical mechanical polishing
  • the operating instrument of chemical mechanical polishing usually consists of a polishing table with a polishing pad and a polishing head for carrying chips.
  • the grinding head fixes the chip, and then presses the front side of the chip on the polishing pad.
  • the polishing head moves linearly on the polishing pad or rotates in the same direction as the polishing table.
  • the slurry containing the abrasive is dropped onto the polishing pad, and the slurry is spread on the polishing pad due to centrifugal action.
  • the chip surface achieves global planarization under the dual action of mechanical and chemical.
  • carbon-containing materials such as silicon carbide and amorphous carbon are used as a new generation of wide band gap semiconductor materials.
  • High frequency, high power, high-density integrated electronic devices and other aspects 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, it is difficult to obtain high polishing speeds in common chemical mechanical polishing liquids when polishing carbon-containing materials.
  • CN102464944A Adding strong oxidizing agents such as permanganic acid, manganic acid and their salts to the polishing liquid, and using silicon dioxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), cerium oxide (CeO 2 ) and titanium dioxide (TiO 2 ) and other abrasives are used as abrasive particles to increase the chemical mechanical removal rate of carbon-containing materials, but the polishing rate of carbon-containing materials is still low, which cannot meet the requirements of semiconductor processes.
  • silicon dioxide SiO 2
  • Al 2 O 3 aluminum oxide
  • CeO 2 cerium oxide
  • TiO 2 titanium dioxide
  • the present invention aims to provide a chemical mechanical polishing liquid and a method of use thereof, by adding two or more metals of ceria, titanium dioxide, manganese dioxide and aluminum oxide to the polishing liquid.
  • the composite oxide particles in which the oxides coat each other can increase the polishing rate of carbon-containing materials.
  • the present invention provides a chemical mechanical polishing liquid, which includes composite abrasive particles, an oxidizer, and water.
  • the composite abrasive particles are composite oxide particles in which two or more metal oxides selected from the group consisting of ceria, titanium dioxide, manganese dioxide and aluminum oxide are coated with each other.
  • the composite abrasive particles are selected from the group consisting of titanium dioxide particles coated with aluminum oxide, titanium dioxide particles coated with manganese dioxide, ceria particles coated with titanium dioxide, and two aluminum oxide particles coated on the surface.
  • the mass percentage concentration of the composite abrasive particles is 0.1-10%.
  • the mass percentage concentration of the composite abrasive particles is 0.5-5.0%
  • the particle size of the composite abrasive particles is 50-500 nm.
  • the particle size of the composite abrasive particles is 50-350 nm.
  • the oxidant is selected from one or more of chlorate, perchlorate, iodate, periodate, permanganate, hydrogen peroxide, monopersulfate, and persulfate;
  • the oxidant is potassium permanganate.
  • the mass percentage concentration of the oxidant is 0.01-1%.
  • the mass percentage concentration of the oxidant is 0.05 to 0.5%
  • the pH value of the chemical mechanical polishing liquid is 2-6.
  • the pH value of the chemical mechanical polishing liquid is 2 ⁇ 4
  • the chemical mechanical polishing liquid in the present invention may also contain other additives in the art such as pH adjusters and bactericides.
  • the present invention provides a method for using the chemical mechanical polishing liquid of the present invention, including: using the chemical mechanical polishing liquid of the present invention for chemical mechanical polishing of carbon-containing materials.
  • the chemical mechanical polishing liquid of the present invention can be configured by condensing components other than the oxidizing agent. Before use, dilute with deionized water and add an oxidizing agent to the concentration range of the present invention for use.
  • the chemical mechanical polishing liquid provided by the present invention and the method of use thereof include a composite oxide in which two or more metal oxides of ceria, titanium dioxide, manganese dioxide and aluminum oxide are mutually coated into the polishing liquid Particles can effectively increase the grinding rate of carbon-containing materials.
  • Table 1 shows the components and contents of Examples 1-15 of the chemical mechanical polishing liquid of the present invention. According to the formula given in the table, a certain concentration of oxidant solution and composite abrasive particles are mixed uniformly, and water is used to make up the mass percentage to 100%. Use KOH or HNO 3 to adjust the pH of the polishing liquid to the desired pH.
  • Table 2 shows examples 16-24 and comparative examples 1-4 of the chemical mechanical polishing liquid of the present invention. According to the formula given in the table, a certain concentration of oxidant solution and composite abrasive particles are mixed uniformly, and the mass percentage is made up with water To 100%. Use KOH or HNO 3 to adjust the pH of the polishing liquid to the desired pH.
  • polishing machine is Reflexion LK, polishing pad IC1010 polishing pad, 300mm wafer, grinding pressure 2.5psi, grinding disc rotation speed 93 rpm, grinding head rotation speed 87 rpm, polishing fluid flow rate 300ml/min, polishing The time is 1 min.
  • the removal rate of amorphous carbon by each polishing liquid was measured and recorded in Table 3.
  • comparative examples 1 to 3 use single-component abrasive particles
  • comparative example 4 uses composite abrasives, but does not add a suitable oxidizer, and the removal rate of amorphous carbon is relatively low.
  • the polishing liquids of Examples 16-24 of the present invention can significantly increase the removal rate of amorphous carbon by selecting appropriate components, composite abrasive particles of appropriate particle size, and oxidizing agent, and adjusting the appropriate pH value.
  • polishing machine is Reflexion LK
  • polishing pad IC1010 polishing pad 300mm wafer
  • grinding pressure 2.5psi grinding disc rotation speed 93 rpm
  • grinding head rotation speed 87 rpm polishing fluid flow rate 300ml/min
  • polishing fluid flow rate 300ml/min polishing The time is 1 min.
  • the measurement of the removal rate of silicon carbide by each polishing solution is recorded in Table 4.
  • the single-component abrasive particles are used in Comparative Examples 1 to 3, and the composite abrasive is used in Comparative Example 4, but no suitable oxidant is added, so the removal rate of silicon carbide is relatively low.
  • the polishing liquid of Examples 21-24 of the present invention can significantly increase the removal rate of silicon carbide by selecting appropriate components, composite abrasive particles of appropriate particle size, and oxidizing agent, and adjusting a proper pH value.
  • the present invention increases the removal rate of amorphous carbon, silicon carbide and other carbonaceous materials by the polishing solution by adding composite abrasive particles to the polishing solution.

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

Abstract

一种化学机械抛光液，包括：复合研磨颗粒、氧化剂和水，其中，所述复合研磨颗粒为选自二氧化铈、二氧化钛、二氧化锰和三氧化二铝中的两种或多种金属氧化物相互包覆的复合氧化物颗粒。该化学机械抛光液可用于含碳材料的化学机械抛光。

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，具体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，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。化学机械抛光的操作仪器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一样的运动方向旋转。与此同时，将含有研磨剂的浆液滴到抛光垫上，浆液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。
因具有宽带隙、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，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，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。但是由于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。
CN102464944A在抛光液中添加高锰酸、锰酸及其盐类等强氧化剂，并使用二氧化硅(SiO 2)、三氧化二铝(Al 2O 3)、二氧化铈(CeO 2)和二氧化钛(TiO 2)等磨料作为研磨颗粒，来提高含碳材料的化学机械去除速率，然而含碳材料的研磨速率仍然偏低，不能满足半导体工艺要求。
发明内容
为了解决上述技术问题，本发明旨在提供一种化学机械抛光液及其使用方法，通过在抛光液中加入二氧化铈、二氧化钛、二氧化锰和三氧化二铝中的两种或多种金属氧化物相互包覆的复合氧化物颗粒，提高含碳材料的研磨速率。
具体地，本发明提供了一种化学机械抛光液，包括复合研磨颗粒、氧化剂和水。
其中，所述复合研磨颗粒为选自二氧化铈、二氧化钛、二氧化锰和三氧化二铝中的两种或多种金属氧化物相互包覆的复合氧化物颗粒。优选地，所述复合研磨颗粒选自表 面包覆三氧化二铝的二氧化钛颗粒，表面包覆二氧化锰的二氧化钛颗粒，表面包覆二氧化钛的二氧化铈颗粒，表面包覆三氧化二铝的二氧化铈颗粒，表面包覆二氧化锰和三氧化二铝的二氧化钛颗粒，表面包覆二氧化钛的二氧化锰颗粒，表面包覆二氧化钛的三氧化二铝颗粒中的一种或多种。
本发明中，所述复合研磨颗粒的质量百分比浓度为0.1～10％。优选地，所述复合研磨颗粒的质量百分比浓度为0.5～5.0％
本发明中，所述复合研磨颗粒的粒径为50～500nm。优选地，所述复合研磨颗粒的粒径为50～350nm。
本发明中，所述氧化剂选自氯酸盐，高氯酸盐，碘酸盐，高碘酸盐，高锰酸盐，双氧水，单过硫酸盐，过硫酸盐中的一种或多种；优选地，所述氧化剂为高锰酸钾。
本发明中，所述氧化剂的质量百分比浓度为0.01～1％。优选地，所述氧化剂的质量百分比浓度为0.05～0.5％
本发明中，所述化学机械抛光液的pH值为2～6。优选地，所述化学机械抛光液的pH值为2～4
本发明中的化学机械抛光液中，还可以包含pH调节剂和杀菌剂等其他本领域的添加剂。
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。
本发明的化学机械抛光液可以将除氧化剂以外的组分浓缩配置。在使用前，用去离子水进行稀释并添加氧化剂至本发明的浓度范围使用。
本发明提供的化学机械抛光液及其使用方法，通过在抛光液中加入二氧化铈、二氧化钛、二氧化锰和三氧化二铝中的两种或多种金属氧化物相互包覆的复合氧化物颗粒，可以有效提高含碳材料的研磨速率。
具体实施方式
下面通过具体实施例进一步阐述本发明的优势，但本发明的保护范围不仅仅局限于下述实施例。
实施例一
表1给出了本发明的化学机械抛光液的实施例1～15的组分及其含量，按表中所给配方，将一定浓度的氧化剂溶液与复合研磨颗粒混合均匀，用水补足质量百分比至100％。用KOH或HNO 3调节抛光液的pH值至所需pH值即可。
表1 本发明实施例1～15的抛光液组分及其含量
Figure PCTCN2020133616-appb-000001
实施例二
表2给出了本发明的化学机械抛光液的实施例16～24和对比实施例1～4，按表中所给配方，将一定浓度的氧化剂溶液与复合研磨颗粒混合均匀，用水补足质量百分比至100％。用KOH或HNO 3调节抛光液的pH值至所需pH值即可。
表2 本发明实施例16～24和对比例1～4的抛光液组分及其含量
Figure PCTCN2020133616-appb-000002
效果实施例一
使用对比例1～4和本发明实施例16～24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300ml/min，抛光时间为1min。测量各抛光液对无定形碳的去除速率记于表3。
表3 对比例1～4与实施例16～24抛光液对无定形碳的去除速率
Figure PCTCN2020133616-appb-000003
由表3可见，对比例1～3分别选用单组分研磨颗粒，对比例4虽然采用复合磨料，但没有添加合适的氧化剂，其无定形碳的去除速率较低。本发明实施例16～24的抛光液，通过选择合适组分、合适粒径的复合研磨颗粒以及氧化剂，通过调节合适的pH值，能够显著提高无定形碳的去除速率。
效果实施例二
使用对比例1～3和本发明实施例21～24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300ml/min，抛光时间为1min。测量各抛光液对碳化硅的去除速率记于表4。
表4 对比例1～3与实施例21～24抛光液对碳化硅的去除速率
Figure PCTCN2020133616-appb-000004
Figure PCTCN2020133616-appb-000005
由表4可见，对比例1～3分别选用单组分研磨颗粒，对比例4虽然采用复合磨料，但没有添加合适的氧化剂，其碳化硅的去除速率较低。本发明实施例21～24的抛光液，通过选择合适组分、合适粒径的复合研磨颗粒以及氧化剂，通过调节合适的pH值，能够显著提高碳化硅去除速率。
综上所述，本发明通过在抛光液中添加复合研磨颗粒，提高了抛光液对无定形碳、碳化硅等含碳材料的去除速率。
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 (10)

  1. 一种化学机械抛光液，包括：复合研磨颗粒、氧化剂和水
  2. 根据权利要求1所述的化学机械抛光液，其特征在于，
    所述复合研磨颗粒为选自二氧化铈、二氧化钛、二氧化锰和三氧化二铝中的两种或多种金属氧化物相互包覆的复合氧化物颗粒。
  3. 根据权利要求2所述的化学机械抛光液，其特征在于，
    所述复合研磨颗粒选自表面包覆三氧化二铝的二氧化钛颗粒，表面包覆二氧化锰的二氧化钛颗粒，表面包覆二氧化钛的二氧化铈颗粒，表面包覆三氧化二铝的二氧化铈颗粒，表面包覆二氧化锰和三氧化二铝的二氧化钛颗粒，表面包覆二氧化钛的二氧化锰颗粒，表面包覆二氧化钛的三氧化二铝颗粒中的一种或多种。
  4. 根据权利要求1所述的化学机械抛光液，其特征在于，
    所述复合研磨颗粒的质量百分比浓度为0.1～10％。
  5. 根据权利要求1所述的化学机械抛光液，其特征在于，
    所述复合研磨颗粒的粒径为50～500nm。
  6. 根据权利要求1所述的化学机械抛光液，其特征在于，
    所述氧化剂选自氯酸盐、高氯酸盐、碘酸盐、高碘酸盐、高锰酸盐、双氧水、单过硫酸盐、过硫酸盐中的一种或多种。
  7. 根据权利要求6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。
  8. 根据权利要求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浓度为0.01～1％。
  9. 根据权利要求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。
  10. 一种化学机械抛光液的使用方法，其特征在于，
    权利要求1～9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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