WO2018099111A1 - 一种氮化硅化学机械抛光液 - Google Patents

一种氮化硅化学机械抛光液 Download PDF

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WO2018099111A1
WO2018099111A1 PCT/CN2017/094363 CN2017094363W WO2018099111A1 WO 2018099111 A1 WO2018099111 A1 WO 2018099111A1 CN 2017094363 W CN2017094363 W CN 2017094363W WO 2018099111 A1 WO2018099111 A1 WO 2018099111A1
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silicon nitride
mechanical polishing
chemical mechanical
polishing liquid
liquid according
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PCT/CN2017/094363
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French (fr)
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周文婷
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安集微电子科技（上海）股份有限公司
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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

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  • the present invention relates to a chemical mechanical polishing liquid in a semiconductor manufacturing process.
  • it relates to a silicon nitride chemical mechanical polishing liquid having high selectivity.
  • a step of removing a silicon nitride layer is performed at each stage, for example, in the step of forming an elemental separation structure, a silicon nitride layer as a barrier layer is removed.
  • STI shallow trench isolation
  • the silicon nitride layer When the silicon nitride layer is exposed, as the largest area of the chemical mechanical polishing system substrate, the silicon nitride must be subsequently polished to obtain a highly flat and uniform surface. Since the overall polishing rate is lowered after the silicon nitride layer is exposed, it has been emphasized in the past practice that oxide polishing needs to take precedence over silicon nitride polishing. Also, during the chemical mechanical planarization process, a silicon nitride layer is typically used as the termination layer. As the etching technique advances, the oxide line width decreases, and it is generally desired that the polishing system employed can preferentially polish silicon nitride in preference to polishing of the oxide such that it is formed in the oxide line on the surface of the substrate. The defects are minimized.
  • Past device designs have focused on the chemical mechanical planarization selectivity of silicon dioxide and silicon nitride, ie, the removal rate of silicon dioxide is higher relative to the removal rate of silicon nitride.
  • the silicon nitride layer acts as a stop layer for chemical mechanical planarization.
  • the removal rate of silicon nitride is higher relative to the removal rate of polysilicon.
  • the polysilicon layer acts as a stop layer for chemical mechanical planarization.
  • the technical problem to be solved by the present invention is to provide a polishing ratio selection ratio of silicon nitride and silicon dioxide, and a polishing ratio of silicon nitride to polysilicon polishing speed, and at the same time, can have a significantly improved silicon nitride polishing speed and low A chemical mechanical polishing solution for the polishing rate of silicon dioxide and polysilicon.
  • the present invention provides a silicon nitride chemical mechanical polishing liquid comprising water and abrasive particles, which simultaneously contain a heterocyclic compound containing one or more carboxyl groups, a polyamine acid and an alkanolamine compound, a pH adjuster and Fungicide.
  • the abrasive particles are silica particles, and the concentration thereof is preferably from 0.5% to 8% by mass, preferably from 1% to 5% by mass.
  • the heterocyclic 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, and non-limiting examples include 2 -Carboxypyridine, 3-carboxypyridine, 4-carboxypyridine, 2,3-dicarboxypyridine, 2,4-dicarboxypyridine, 2,6-dicarboxypyridine, 3,5-dicarboxypyridine, 2-carboxypiperidin Pyridine, 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-carboxypyrrole, 3-carboxypyrrole, 2,5-dicarboxypyr
  • the polyamine acid and the alkanolamine compound are hydroxyalkyl ammonium salts of polycarboxylic acid polymers, such as BYK company products ANTI-TERRA-250, DISPERBYK, DISPERBYK-180, DISPERBYK-181, DISPERBYK-187, etc. .
  • the concentration thereof is preferably from 0.001% to 0.5% by mass, preferably from 0.01% to 0.1%.
  • the bactericide may be selected from the group consisting of 5-chloro-2-methyl-4-isothiazolin-3-one (CIT), 2-methyl-4-isothiazolinone (MIT), 1,2- Phenylisothiazolinone (BIT), iodopropynyl carbamate (IPBC), 1,3-dimethylol-5,5-methylhydantoin (DMDMH), etc., preferably in a concentration by mass 0.02% - 0.2%.
  • CIT 5-chloro-2-methyl-4-isothiazolin-3-one
  • MIT 2-methyl-4-isothiazolinone
  • BIT 1,2- Phenylisothiazolinone
  • IPBC iodopropynyl carbamate
  • DDMH 1,3-dimethylol-5,5-methylhydantoin
  • the pH adjusting agent comprises one or more of HNO 3 , KOH, K 2 HPO 4 or KH 2 PO 4 .
  • the pH of the polishing liquid is greater than 1.5 units of pKa1 of the heterocyclic compound containing one or more carboxyl groups and less than 6.5.
  • the present invention adds a heterocyclic compound containing one or more carboxyl groups, and has a pH greater than 1.5 units of pKa1 of the above component and less than 6.5.
  • Such compounds have both a carboxyl group and a nitrogen-containing structure in the molecular structure, and the nitrogen-containing structure is attracted to the silica abrasive particles, so that the carboxyl structure is exposed, and after encountering the silicon nitride surface, the heterogeneous charge is greatly increased due to attraction.
  • the interaction between the abrasive particles and the surface of the silicon nitride significantly increases the polishing speed of the silicon nitride wafer; at the same time, since the charges are mutually exclusive, the interaction between the abrasive particles and the silicon dioxide wafer is reduced, and the polishing speed of the silicon dioxide is suppressed, further Significantly increase the polishing rate selection ratio of silicon nitride and silicon dioxide.
  • the addition of polyamine and an alkanolamine compound covers the surface of the polysilicon, reduces the interaction between the abrasive particles and the surface of the polysilicon, inhibits the polishing speed of the polysilicon, and significantly increases the selection ratio of silicon nitride to polysilicon, thereby significantly increasing the nitridation.
  • the polishing speed of silicon and has a low polishing speed of silicon dioxide and polysilicon.
  • Table 1 shows the components of the polishing solution of Comparative 1-3 and Examples 1-10 of the present invention and their contents. According to the formula in the table, all the components are dissolved and uniformly mixed, and the mass percentage is made up to 100% with water. The pH adjuster is adjusted to a suitable pH value and allowed to stand to prepare each polishing liquid.
  • the specific polishing conditions are: Mirra machine, IC1010pad, speed 93/87, polishing pressure 1.5 psi, polishing flow 150 ml/min. Enter the above parameters in the Mirra machine, polish, clean, dry, and test the 8-inch silicon nitride and silicon dioxide for 1 min, and obtain the polishing results.
  • the addition of polyamine and alkanolamine compounds reduced the polishing rate of polysilicon and significantly increased the selectivity of silicon nitride to polysilicon.
  • the present invention also provides a high selectivity ratio of silicon nitride to silicon dioxide and silicon nitride to polysilicon.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

本发明涉及一种高选择性氮化硅的化学机械抛光液，包括水和研磨颗粒，同时还包括含一个或多个羧基基团的杂环类化合物、聚胺酸与烷醇胺化合物、pH调节剂和杀菌剂。本发明的抛光液可以提高氮化硅与二氧化硅抛光速度选择比，以及氮化硅与多晶硅抛光速度选择比，同时能够具有显著提高的氮化硅抛光速度以及减小的二氧化硅和多晶硅抛光速度，就有良好的市场应用前景。

Description

一种氮化硅化学机械抛光液 技术领域
本发明涉及半导体制造工艺中的一种化学机械抛光液。尤其涉及一种具有高选择性的氮化硅化学机械抛光液。
背景技术
在半导体装置的生产中，在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，要除去作为阻挡层的氮化硅层。
其中，对于用于隔离半导体器件的方法，大量注意力放在浅沟槽隔离(STI)工艺上。在硅基板上形成的氮化硅层，经由蚀刻或光刻法形成浅沟槽，且使用沉积介电层来填充这些沟槽。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。然后通常需要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，作为化学机械抛光系统基板的最大面积，氮化硅必须随后进行抛光以获得高度平坦且均匀的表面。由于氮化硅层暴露后整体抛光速率会降低，因此，在以往的实践中，一直强调氧化物抛光需优先于氮化硅抛光。并且，在化学机械平坦化工艺期间，氮化硅层通常被用作终止层。随着蚀刻技术的进步，氧化物线宽减小，通常期望所采用的抛光系统对氮化硅的抛光能够优先于对氧化物的抛光的选择性，使得形成于基板表面上的氧化物线路中的缺陷减至最少。
过去的器件设计侧重于二氧化硅与氮化硅的化学机械平面化选择性，即相对于氮化硅的去除速率，二氧化硅的去除速率更高。在这些器件设计中，氮化硅层作为化学机械平面化的终止层。
近来，一些器件设计需要化学机械抛光组合具有氮化硅与多晶硅的选择性，即相对于多晶硅的去除速率，氮化硅的去除速率更高。在这些器件设计中，多晶硅层作为化学机械平面化的终止层。
发明内容
本发明所要解决的技术问题是提供一种可以提高氮化硅与二氧化硅抛光速度选择比，以及氮化硅与多晶硅抛光速度选择比，同时能够具有显著提高的氮化硅抛光速度以及低的二氧化硅和多晶硅抛光速度的化学机械抛光液。
本发明提供一种氮化硅化学机械抛光液，其中含有水和研磨颗粒，其同时含有含一个或多个羧基基团的杂环类化合物、聚胺酸与烷醇胺化合物，pH调节剂和杀菌剂。
其中，所述的研磨颗粒为二氧化硅颗粒，其浓度较佳为质量百分比0.5％-8％，优选为1％-5％。
其中，所述的含一个或多个羧基基团的杂环类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，非限制性实例包括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、2，6-二羧基吡啶，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，其浓度较佳为质量百分比0.01％-0.5％，优选为0.01％-0.3％。
其中，所述的聚胺酸与烷醇胺化合物为多元羧酸聚合物的羟烷基铵盐，例如BYK公司产品ANTI-TERRA-250，DISPERBYK，DISPERBYK-180，DISPERBYK-181，DISPERBYK-187等。其浓度较佳为质量百分比0.001％-0.5％，优选为0.01％-0.1％。
其中，所述杀菌剂可选自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，优选浓度为质量百分比0.02％-0.2％。
其中，所述的pH调节剂包含HNO3、KOH、K2HPO4或KH2PO4的一种或多种。
其中，所述抛光液的pH值大于所述含一个或多个羧基基团的杂环类化合物的pKa1的1.5个单元且小于6.5。
与现有技术相比较，本发明的技术优势在于：
本发明添加了含一个或多个羧基基团的杂环类化合物，且pH值大于上述组分pKa1的1.5个单位且小于6.5。此类化合物在分子结构中同时带有羧基以及含氮结构，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，大大增加了研磨颗粒和氮化硅表面的相互作用，显著提高氮化硅晶片的抛光速度；同时由于电荷相互排斥，降低了研磨颗粒和二氧化硅晶片的相互作用，抑制二氧化硅的抛光速度，进一步显著提高氮化硅与二氧化硅的抛光速度选择比。加入聚胺酸与烷醇胺化合物，覆盖在多晶硅表面，降低了研磨颗粒与多晶硅表面的相互作用，抑制了多晶硅的抛光速度，显著提高氮化硅与多晶硅的选择比，从而能够显著提高氮化硅的抛光速度并且具有低的二氧化硅和多晶硅的抛光速度。
具体实施方式
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实例范围之中。
对比例1-3和实施例1-10
表1给出了本发明的抛光液对比例1-3和实施例1-10的组分及其含量，按表中配方，将所有组分溶解混合均匀，用水补足质量百分比至100％，用pH调节剂调节至合适的pH值，静置，可制得各抛光液。
表1本发明的抛光液对比例1-3及实施例1-10配方
Figure PCTCN2017094363-appb-000001
Figure PCTCN2017094363-appb-000002
按表1配方的抛光液根据下述实验条件进行实验。
具体抛光条件为：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，用单纯的二氧化硅进行抛光，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。从对比例2与对比例3的结果，pH在大于2-羧基吡啶的Pka1(0.99)1.5个单位的情况下，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选择比高。从实施例与对比例2，3聚胺酸与烷醇胺化合物的加入，降低了多晶硅的抛光速度，显著提高了氮化硅与多晶硅的选择比。本发明同时提供了高的氮化硅与二氧化硅和氮化硅与多晶硅的选择比。
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 (15)

  1. 一种氮化硅化学机械抛光液，包括水和研磨颗粒，其特征在于，同时还包括含一个或多个羧基基团的杂环类化合物，聚胺酸与烷醇胺化合物，pH调节剂和杀菌剂。
  2. 如权利要求1所述的氮化硅化学机械抛光液，其特征在于，所述的研磨颗粒为二氧化硅颗粒。
  3. 如权利要求1所述的氮化硅化学机械抛光液，其特征在于，所述的研磨颗粒的浓度为质量百分比0.5％-8％。
  4. 如权利要求3所述的氮化硅化学机械抛光液，其特征在于，所述的二氧化硅颗粒的浓度为质量百分比1％-5％。
  5. 如权利要求1所述的氮化硅化学机械抛光液，其特征在于，所述的含一个或多个羧基基团的杂环类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所述的氮化硅化学机械抛光液，其特征在于，所述的含一个或多个羧基基团的杂环类化合物包括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、2，6-二羧基吡啶，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所述的氮化硅化学机械抛光液，其特征在于，所述的含一个或多个羧基基团的杂环类化合物的浓度为质量百分比0.01～0.5％。
  8. 如权利要求7所述的氮化硅化学机械抛光液，其特征在于，所述的含一个或多个羧基基团的杂环类化合物的优选浓度为质量百分比0.01～0.3％。
  9. 如权利要求1所述的氮化硅化学机械抛光液，其特征在于，所述的聚胺酸与烷醇胺化合物为多元羧酸聚合物的羟烷基铵盐。
  10. 如权利要求1所述的氮化硅化学机械抛光液，其特征在于，所述的聚胺酸与烷醇胺化合物浓度为质量百分比0.001％-0.5％。
  11. 如权利要求9所述的氮化硅化学机械抛光液，其特征在于，所述的聚胺酸与烷醇胺化合物的浓度为质量百分比为0.01％-0.1％。
  12. 如权利要求1所述的氮化硅化学机械抛光液，其特征在于，所述的杀菌剂包括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)的一种或多种。
  13. 如权利要求1所述的氮化硅化学机械抛光液，其特征在于，所述的杀菌剂浓度为质量百分比0.02％-0.2％。
  14. 如权利要求1所述的氮化硅化学机械抛光液，其特征在于，所述的pH调节剂包含HNO3、KOH、K2HPO4或KH2PO4的一种或多种。
  15. 如权利要求1所述的氮化硅化学机械抛光液，其特征在于，所述抛光液pH值大于所述含一个或多个羧基基团的杂环类化合物pKa1的1.5个单元且小于6.5。
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