WO2018099109A1 - 具有高氮化硅选择性的化学机械抛光液 - Google Patents

具有高氮化硅选择性的化学机械抛光液 Download PDF

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WO2018099109A1
WO2018099109A1 PCT/CN2017/094349 CN2017094349W WO2018099109A1 WO 2018099109 A1 WO2018099109 A1 WO 2018099109A1 CN 2017094349 W CN2017094349 W CN 2017094349W WO 2018099109 A1 WO2018099109 A1 WO 2018099109A1
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mechanical polishing
chemical mechanical
polishing liquid
liquid according
compound
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PCT/CN2017/094349
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周文婷
荆建芬
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安集微电子科技（上海）股份有限公司
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Priority to US16/464,856 priority Critical patent/US11111413B2/en
Publication of WO2018099109A1 publication Critical patent/WO2018099109A1/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
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • 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
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/02—Etching, surface-brightening or pickling compositions containing an alkali metal hydroxide
    • 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
    • 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
    • H01L21/3105—After-treatment
    • H01L21/31051—Planarisation of the insulating layers
    • H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step

Definitions

  • the present invention relates to the field of chemical mechanical polishing liquids, and more particularly to a chemical mechanical polishing liquid having high silicon nitride selectivity.
  • the steps of removing the silicon nitride layer are performed at various stages, for example, in the step of forming the element isolation structure, it is necessary to remove the silicon nitride layer as a barrier.
  • a silicon nitride removal step is usually performed at a high temperature of about 150 ° C by a wet etching treatment using, for example, a phosphoric acid/nitric acid mixed solution, and a polishing step containing abrasive grains is rarely used;
  • STI shallow trench isolation
  • CN102604541 proposes to use silica particles, aryl dicarboxylic acid and phenylacetic acid compounds to improve the selectivity ratio of SiN to oxide, but the Oxide polishing rate is higher.
  • the SiN/Teos selection ratio is relatively low; as in CN 1796482, it is proposed to increase the polishing rate of SiN by adding 85% aqueous solution of at least one of formic acid, acetic acid, oxalic acid, adipic acid and lactic acid, and the choice of SiN and Oxide.
  • CN101906270 provides a polishing solution in which a nitrogen-containing compound containing a ring mechanism is used to improve the stability, storage time and use of the polishing solution. Life, but does not involve the polishing effect of the material;
  • the polishing principle of oxide polishing prior to silicon nitride polishing has been emphasized, and therefore, the silicon nitride layer is generally used as a termination layer during the chemical mechanical planarization process. This is because the polishing rate of the entire substrate is lowered after the silicon nitride layer is exposed.
  • the oxide line width becomes smaller, and it is desirable that the polishing system utilized has a selectivity for polishing silicon nitride in preference to polishing of an oxide, which is formed on the surface of the substrate. Defects in the oxide circuit are minimized. Therefore, the search for a polishing liquid having a selectivity for polishing silicon nitride in preference to polishing of an oxide is a problem to be solved in the art.
  • the present invention proposes a chemical mechanical polishing liquid having high silicon nitride selectivity, which can provide a higher SiN polishing speed and a lower Teos polishing speed, and has a higher SiN/Teos Polishing rate selection ratio.
  • the present invention provides a chemical mechanical polishing liquid having high silicon nitride selectivity, comprising abrasive particles and a compound containing one or more carboxyl groups.
  • the abrasive particles are silica particles.
  • the mass percentage concentration of the abrasive particles is preferably from 0.5 to 8 wt%, preferably from 1 to 5 wt%.
  • the compound containing one or more carboxyl groups includes one or more of a pyridine compound, a piperidine compound, a pyrrolidine compound or a pyrrole compound and a derivative thereof.
  • the compound containing one or more carboxyl groups includes 2-carboxypyridine, 3-carboxypyridine, 4-carboxypyridine, 2,3-dicarboxypyridine, 2,4-dicarboxypyridine, 2,6 - Carboxypyridine, 3,5-dicarboxypyridine, 2-carboxypiperidine, 3-carboxypiperidine, 4-carboxypiperidine, 2,3-dicarboxypiperidine, 2,4-dicarboxypiperidine, 2 ,6-dicarboxypiperidine, 3,5-dicarboxypiperidine, 2-carboxypyrrolidine, 3-carboxypyrrolidine, 2,4-dicarboxypyrrolidine, 2,5-dicarboxypyrrolidine, 2-carboxyl One or more of pyrrole, 3-carboxypyrrole, 2,5-dicarboxypyrrole, 3,4-dicarboxypyridine, and the like.
  • the mass percentage of the compound having one or more carboxyl groups is preferably from 0.01 to 0.5% by weight, preferably from 0.01 to 0.3% by weight.
  • the chemical mechanical polishing liquid has a pH greater than 1.5 units of pKa1 of the compound containing one or more carboxyl groups, and is less than 6.5.
  • the chemical mechanical polishing liquid further contains a pH adjuster and a bactericide.
  • the pH adjusting agent comprises one or more of HNO 3 , KOH, K 2 HPO 4 and KH 2 PO 4 .
  • the bactericide comprises 5-chloro-2-methyl-4-isothiazolin-3-one (CIT), 2-methyl-4-isothiazolinone (MIT), 1,2-phenylene One or more of isothiazolinone (BIT), iodopropynyl carbamate (IPBC), 1,3-dimethylol-5,5-methylhydantoin (DMDMH), and the like.
  • CIT 5-chloro-2-methyl-4-isothiazolin-3-one
  • MIT 2-methyl-4-isothiazolinone
  • BIT isothiazolinone
  • IPBC iodopropynyl carbamate
  • DDMH 1,3-dimethylol-5,5-methylhydantoin
  • the sterilant has a mass percentage concentration of 0.02-0.2 wt%.
  • the present invention has a higher SiN polishing speed and a lower Teos polishing speed, and has a higher SiN/Teos polishing rate selection ratio;
  • the present invention can greatly reduce defects in the oxide wiring on the surface of the substrate.
  • polishing conditions Mirra machine, IC1010pad, speed 93/87, polishing pressure: 1.5 psi.
  • the polishing flow rate was 150 ml/min.
  • the above parameters were entered in the Mirra machine, and 8 inch silicon nitride and silicon dioxide were polished for 1 min, washed, dried, tested and polished.
  • the pH of the silicon nitride was higher than that of the Pka1 (1.0) 1.5 unit of 2-carboxypyridine, and the silicon dioxide was lower in speed, silicon nitride and The polishing rate of silicon oxide is selected to be high.
  • the carboxyl compound has both a carboxyl group and a nitrogen-containing structure in the molecular structure. When the pH is greater than 1.5 units of Pka1, the nitrogen-containing structure is attracted to the silica abrasive particles, so that the carboxyl structure is exposed and the silicon nitride surface is encountered.
  • the polishing rate of silica can reduce the defects of silicon nitride as a termination layer in STI polishing.
  • the use of a high silicon nitride/silicon dioxide selective ratio polishing liquid can utilize the high silicon nitride removal efficiency and greatly improve the overall polishing efficiency.

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

Abstract

一种具有高氮化硅选择性的化学机械抛光液，其含有研磨颗粒及含一个或多个羧基基团的化合物。该抛光液具有较高的SiN抛光速度和较低的Teos抛光速度，具有较高的SiN/Teos的抛光速率选择比；使用该抛光液可大大减少基板表面上的氧化物线路中的缺陷，具有优异的市场应用前景。

Description

[根据细则37.2由ISA制定的发明名称]　具有高氮化硅选择性的化学机械抛光液 技术领域
本发明涉及化学机械抛光液领域，尤其涉及一种具有高氮化硅选择性的化学机械抛光液。
背景技术
在半导体装置的生产过程中，其各个阶段都要进行去除氮化硅层的步骤，例如在形成元素分离结构的步骤中，需要除去作为阻挡出的氮化硅层。但是迄今为止，这种氮化硅的去除步骤通常需要在约150℃的高温下，通过使用例如磷酸/硝酸混合溶液的湿法刻蚀处理进行，很少采用含有磨粒的抛光步骤；又，在隔离半导体器件各元件的浅沟槽隔离(STI)工艺中，其中，需要在硅基板上形成氮化硅层，经由蚀刻或光刻法形成浅沟槽，并沉积介电层以填充这些沟槽，由于以此方式形成的沟槽或线路深度的变化，通常需要将过量的介电材料沉积在基板顶部上以确保所有沟槽完全填满，然后通过化学机械平坦化工艺来移除过量的介电材料(例如氧化物)以暴露出氮化硅层，当氮化硅层暴露出来时，化学机械抛光系统的基板的最大面积覆盖氮化硅，氮化硅必须随后进行抛光以获得高度平坦且均匀的表面。
目前，对氮化硅层抛光的研究众多，例如CN102604541，提出利用二氧化硅颗粒，芳基二羧酸、苯乙酸类化合物，来提高SiN与oxide的选择比，但其Oxide抛光速度较高，而SiN/Teos选择比相对较低；又如CN 1796482提出通过添加甲酸、乙酸、草酸、己二酸和乳酸中至少一种形成85％水溶液，来提高SiN的抛光速度，及SiN与Oxide的选择比，但是单纯地提高SiN的速度，并未涉及同时改变Oxide抛光速率；CN101906270提供了一种抛光液，其中用含有环状机构的含氮化合物来提高抛光液的稳定性、存储时间和使用 寿命，但不涉及材料的抛光效果；
可以看出，在以往的实践中，一直强调氧化物抛光优先于氮化硅抛光的抛光原则，因此，氮化硅层通常在化学机械平坦化工艺期间用作终止层。这是因为在氮化硅层暴露后，基材整体的抛光速率会降低。但是，随着蚀刻技术的进步，氧化物线宽变得更小，进而期望所利用的抛光系统具有对氮化硅的抛光优先于对氧化物的抛光的选择性，这使得形成于基板表面上的氧化物线路中的缺陷减至最少。因此，寻求一种具有对氮化硅的抛光优先于对氧化物的抛光的选择性的抛光液是本领域亟待解决的问题。
发明内容
为解决上述问题，本发明提出一种具有高氮化硅选择性的化学机械抛光液，该抛光液可以提供较高的SiN抛光速度和较低的Teos抛光速度，具有较高的SiN/Teos的抛光速率选择比。
具体地，本发明提供一种具有高氮化硅选择性的化学机械抛光液，其中，含有研磨颗粒及含一个或多个羧基基团的化合物。
其中，所述研磨颗粒为二氧化硅颗粒。
其中，所述研磨颗粒的质量百分比浓度较佳为0.5～8wt％，优选为1％～5wt％。
其中，所述含一个或多个羧基基团的化合物包括吡啶化合物、哌啶化合物、吡咯烷化合物或吡咯化合物及其衍生物中的一种或多种。
优选地，所述含一个或多个羧基基团的化合物包括2-羧基吡啶、3-羧基吡啶、4-羧基吡啶、2，3-二羧基吡啶、2，4-二羧基吡啶、2，6-而羧基吡啶，3，5-二羧基吡啶、2-羧基哌啶，3-羧基哌啶，4-羧基哌啶，2，3-二羧基哌啶，2，4-二羧基哌啶，2，6-二羧基哌啶，3，5-二羧基哌啶，2-羧基吡咯烷，3-羧基吡咯烷，2，4-二羧基吡咯烷，2，5-二羧基吡咯烷，2-羧基吡咯，3-羧基吡咯，2，5-二羧基吡咯，3，4-二羧基吡啶等中的一种或多种。
其中，所述含一个或多个羧基基团的化合物的质量百分比浓度较佳为0.01～0.5wt％，优选为0.01～0.3wt％。
其中，所述化学机械抛光液的pH值大于所述含一个或多个羧基基团的化合物的pKa1的1.5个单位，并且小于6.5。
其中，所述化学机械抛光液中还含有pH调节剂及杀菌剂。
其中，所述pH调节剂包括HNO3、KOH、K2HPO4和KH2PO4中的一种或多种。
其中，所述杀菌剂包括5-氯-2-甲基-4-异噻唑啉-3-酮(CIT)，2-甲基-4-异噻唑啉酮(MIT)，1，2-苯丙异噻唑啉酮(BIT)，碘代丙炔基氨基甲酸酯(IPBC)，1，3-二羟甲基-5，5-甲基海因(DMDMH)等中的一种或多种。
其中，所述杀菌剂的质量百分比浓度为0.02-0.2wt％。
与现有技术相比较，本发明的积极进步效果在于：
1)本发明具有较高的SiN抛光速度和较低的Teos抛光速度，具有较高的SiN/Teos的抛光速率选择比；
2)本发明可大大减少基板表面上的氧化物线路中的缺陷。
具体实施方式
具体实施例以及对比按表1中所给配方，将所有组分溶解混合均匀，用水补足质量百分比至100％。用pH调节剂调节pH至期望值。
表1对比例及实施例的具体组分及其含量
Figure PCTCN2017094349-appb-000001
Figure PCTCN2017094349-appb-000002
按表1配方的抛光液根据下述实验条件进行实验。
具体抛光条件：Mirra机台，IC1010pad，转速93/87，抛光压力：1.5psi。抛光流量150ml/min。在Mirra机台中输入上述参数，对8寸氮化硅、二氧化硅进行1min抛光，清洗、干燥、检测并得到抛光结果。
从对比例1的结果可以看出，用单纯的SiO2进行抛光，氮化硅的抛光速 度很低，二氧化硅的抛光速度却比较高，氮化硅与二氧化硅的选择性是反向的。从实施例与对比例2和对比例3的结果看到，相较于含有其他羧酸以及其他杂环酸的抛光浆料，本发明的氮化硅速度地提升幅度大，并且降低了二氧化硅的抛光速度，具有很高的氮化硅与二氧化硅的抛光速率选择比。从实施例与对比例4的结果，pH在大于2-羧基吡啶的Pka1(1.0)1.5单位的情况下，氮化硅的抛光速度较高，二氧化硅的速度较低，氮化硅与二氧化硅的抛光速率选择比高。本专利中羧基化合物在分子结构中同时带有羧基以及含氮结构，在pH大于1.5单位Pka1时，含氮结构与二氧化硅研磨颗粒相吸引，使得羧基结构暴露在外，遇到氮化硅表面后，由于异性电荷相吸，这样大大增加了研磨颗粒和氮化硅表面的相互作用，降低了研磨颗粒与二氧化硅晶片表面的相互作用，增加了氮化硅晶片的抛光速度，同时降低了二氧化硅的抛光速度。利用高的氮化硅/二氧化硅选择比的抛光液，可以降低STI抛光中氮化硅作为终止层带来的缺陷。另外在用二氧化硅作为终止层的结构中，使用高的氮化硅/二氧化硅选择比的抛光液，可利用高的氮化硅的去除效率，大大提高了整体的抛光效率。
应当注意的是，本发明的实施例有较佳的实施性，且并非对本发明作任何形式的限制，任何熟悉该领域的技术人员可能利用上述揭示的技术内容变更或修饰为等同的有效实施例，但凡未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何修改或等同变化及修饰，均仍属于本发明技术方案的范围内。

Claims (13)

  1. 一种具有高氮化硅选择性的化学机械抛光液，其特征在于，含有研磨颗粒及含一个或多个羧基基团的化合物。
  2. 如权利要求1所述的化学机械抛光液，其特征在于，所述研磨颗粒为二氧化硅颗粒。
  3. 如权利要求1所述的化学机械抛光液，其特征在于，所述研磨颗粒的质量百分比浓度为0.5～8wt％。
  4. 如权利要求3所述的化学机械抛光液，其特征在于，所述研磨颗粒的质量百分比浓度为1％～5wt％。
  5. 如权利要求1所述的化学机械抛光液，其特征在于，所述含一个或多个羧基基团的化合物为吡啶化合物、哌啶化合物、吡咯烷化合物或吡咯化合物及其衍生物中的一种或多种。
  6. 如权利要求5所述的化学机械抛光液，其特征在于，所述含一个或多个羧基基团的化合物为2-羧基吡啶、3-羧基吡啶、4-羧基吡啶、2，3-二羧基吡啶、2，4-二羧基吡啶、2，6-而羧基吡啶，3，5-二羧基吡啶、2-羧基哌啶，3-羧基哌啶，4-羧基哌啶，2，3-二羧基哌啶，2，4-二羧基哌啶，2，6-二羧基哌啶，3，5-二羧基哌啶，2-羧基吡咯烷，3-羧基吡咯烷，2，4-二羧基吡咯烷，2，5-二羧基吡咯烷，2-羧基吡咯，3-羧基吡咯，2，5-二羧基吡咯，3，4-二羧基吡啶中的一种或多种。
  7. 如权利要求1所述的化学机械抛光液，其特征在于，所述含一个或多个羧基基团的化合物的质量百分比浓度为0.01～0.5wt％。
  8. 如权利要求7所述的化学机械抛光液，其特征在于，所述含一个或多个羧基基团的化合物的质量百分比浓度为0.01～0.3wt％。
  9. 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值大于所述含一个或多个羧基基团的化合物的pKa1的1.5个单位，并且小于6.5。
  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中还含有pH调节剂及杀菌剂。
  11. 如权利要求10所述的化学机械抛光液，其特征在于，所述pH调节剂包括HNO3、KOH、K2HPO4和KH2PO4中的一种或多种。
  12. 如权利要求10所述的化学机械抛光液，其特征在于，所述杀菌剂包括5-氯-2-甲基-4-异噻唑啉-3-酮(CIT)，2-甲基-4-异噻唑啉酮(MIT)，1，2-苯丙异噻唑啉酮(BIT)，碘代丙炔基氨基甲酸酯(IPBC)，1，3-二羟甲基-5，5-甲基海因(DMDMH)中的一种或多种。
  13. 如权利要求10所述的化学机械抛光液，其特征在于，所述杀菌剂的质量百分比浓度为0.02-0.2wt％。
PCT/CN2017/094349 2016-11-29 2017-07-25 具有高氮化硅选择性的化学机械抛光液 WO2018099109A1 (zh)

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