WO2014089907A1 - 一种化学机械抛光液的应用 - Google Patents
一种化学机械抛光液的应用 Download PDFInfo
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- WO2014089907A1 WO2014089907A1 PCT/CN2013/001499 CN2013001499W WO2014089907A1 WO 2014089907 A1 WO2014089907 A1 WO 2014089907A1 CN 2013001499 W CN2013001499 W CN 2013001499W WO 2014089907 A1 WO2014089907 A1 WO 2014089907A1
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- Prior art keywords
- acid
- use according
- polishing
- silicon
- abrasive particles
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- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 239000001230 potassium iodate Substances 0.000 description 1
- 229940093930 potassium iodate Drugs 0.000 description 1
- 235000006666 potassium iodate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- 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
-
- 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
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
- H01L21/0201—Specific process step
- H01L21/02024—Mirror 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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
Definitions
- Silicon (monocrystalline/polycrystalline silicon) materials are widely used in integrated circuits. Fabrication of silicon wafers requires many manufacturing processes, including crystal growth, slicing, grinding, etching, polishing, and cleaning. Among them, chemical mechanical polishing is used to remove excess material and surface defects such as scratches, surface topography defects, etc. formed in other processes, making it useful for manufacturing integrated circuits.
- the silicon chemical mechanical polishing liquid which is usually sold has a higher polishing rate. After polishing, the surface roughness of the wafer is high, the surface is hydrophobic, and it is difficult to clean after polishing, which is prone to defects such as water stains, residual particles, and high haze. These defects have an impact on the yield of the semiconductor device.
- some special cleaning liquids are usually used to clean the polished silicon wafers. Although the abrasive particles can be reduced after cleaning, the haze defects can be reduced, but the surface roughness of the wafer cannot be reduced. Therefore, a new polishing method and polishing solution are needed to solve this problem at the same time.
- metal impurities such as metal itself, metal hydroxide, metal oxide may adhere to and remain on the surface of the silicon wafer, and the reliability of these metal impurities may be semiconductor devices. Etc.
- the present invention captures and removes these metal impurities that may be present by the addition of some complexing agents.
- a Japanese patent JP2011082372(A) discloses a cleaning liquid for a silicon wafer containing an inorganic ammonium salt (ammonium chloride, ammonium carbonate, etc.), hydrogen peroxide and water, and the cleaning liquid further contains ammonium hydroxide for adjustment. pH and increase cleaning ability.
- the use of the cleaning liquid can suppress the decrease in the haze level. It is possible to suppress the drop in the haze level, but it does not improve the surface roughness after polishing.
- a polishing fluid comprising abrasive particles, a pH adjusting agent, a water soluble thickener and a chelating agent, wherein the chelating agent comprises at least one acetic acid chelating agent and a chelating agent is disclosed in US Pat. a phosphate chelating agent.
- the polishing solution can reduce the number of defects of the product, and reduce the roughness and haze of the product.
- the effect of the water-soluble thickener is sufficient to reduce the coalescence of the silicon monoxide particles and to reduce the spot defects on the round surface.
- the action of the acetic acid chelating agent and/or the phosphoric acid chelating agent is to reduce or prevent the residual of metal ions on the surface of the round and further improve the dispersion stability of the silica.
- the composition is complicated, and the stability of the polishing liquid is not good enough when the acetic acid chelating agent or the phosphoric acid chelating agent is used alone (large particles increase with the daytime).
- the use of a chelating agent containing sodium ions increases the amount of sodium ions in the polishing solution, which may affect the reliability of the wafer due to residual sodium ions. Summary of the invention
- the invention provides an application of a chemical mechanical polishing liquid capable of precipitating a low contact angle on a surface of a silicon wafer during polishing of a silicon substrate, the polishing liquid containing abrasive particles and an oxidizing agent, and may further contain at least one complexing agent .
- the polishing liquid can be used for the second step polishing of the silicon wafer, that is, the first step uses a silicon chemical mechanical polishing liquid having a high silicon removal rate to remove a large amount of silicon, and the second step uses the polishing liquid of the present invention to remove a small amount of silicon.
- the abrasive particles are one or more of silica, alumina, doped aluminum or aluminum-coated silica, ceria, titania, and polymer abrasive particles, preferably two. Silicon oxide.
- the content is 0.5 to 20% by weight, preferably 1 to 5% by weight; and the particle diameter is 20 to 200 nm, preferably 20 to 120 nm.
- the oxidizing agent is hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, persulfate, percarbonate, periodic acid, perchloric acid, perboric acid, potassium permanganate And one or more of ferric nitrate. Hydrogen peroxide is preferred.
- the content is 0.01 to 5 wt%, preferably 0.05 to 1 wt%.
- the pH of the polishing liquid is more than 7, preferably 9 to 12.
- the polishing liquid of the present invention may further contain at least one complexing agent, and the complexing agent is any suitable additive capable of forming a soluble compound with a metal ion, and the complexing agent may
- the gold ions that may be present on the polished material are dissolved and removed to avoid residual residues in the substrate and affect the reliability of the road.
- Suitable complexing agents include aminocarboxylates, rhodium carboxylic acids, organic phosphonic acids and organic amines. The aminocarboxylates are selected from the group consisting of glycine, alanine, valine, leucine, valine, and styrene.
- the organic carboxylic acid is acetic acid, oxalic acid And one or more of citric acid, tartaric acid, malonic acid, succinic acid, malic acid, lactic acid, gallic acid and sulfosalicylic acid; said organic phosphonic acid is 2-phosphonic acid butyl hydrazine-1 , 2, 4-tricarboxylic acid, aminotrimethylene phosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediaminete
- the above chemical mechanical polishing liquid further includes a conventional modifier in the art such as a pH adjuster, a viscosity modifier, an antifoaming agent, and a bactericide.
- a conventional modifier in the art such as a pH adjuster, a viscosity modifier, an antifoaming agent, and a bactericide.
- the above chemical mechanical polishing liquid can prepare a component other than the oxidizing agent into a concentrated sample, which is diluted with deionized water to the concentration range of the present invention and added with an oxidizing agent before use.
- the polishing substrate is a silicon substrate including single crystal silicon and polycrystalline silicon.
- the polishing liquid of the present invention can be used for the second step polishing of a silicon wafer, that is, a silicon chemical mechanical polishing liquid having a high silicon removal rate is used to remove a large amount of silicon in the first step, and the second step uses the polishing liquid of the present invention to remove a small amount of silicon.
- Silicon improving the surface roughness after polishing, improving the hydrophilicity of the surface of the silicon wafer, is beneficial to reduce the adsorption of abrasive particles, reduce the haze, reduce surface defects, and facilitate the removal of metal ion impurities that may exist in the process.
- the slurry of the present invention can reduce the roughness of the surface of the silicon-based wafer after polishing
- the paddle of the present invention can improve the hydrophilicity of the surface of the silicon-based wafer after polishing, thereby facilitating 3)
- the slurry of the present invention is advantageous for removing metal ion impurities that may be present in the process.
- Figure 1 Optical microscopy of the surface of a silicon wafer after polishing and cleaning in the first step
- Figure 2 Optical microscopy of the surface of the silicon wafer after the second step of polishing and cleaning with Comparative 2;
- Figure 3 Optical microscopy of the surface of the silicon wafer after the second step of polishing and cleaning with Example 1;
- Figure 4 Implementation Example 10 An optical micrograph of the surface of a silicon wafer after the second step of polishing and cleaning.
- the reagents and starting materials used in the present invention are commercially available.
- the polishing liquid of the present invention can be obtained by simply and uniformly mixing the above components.
- Table 1 shows the chemical mechanical polishing liquid formulations of the present invention. The percentages described below are all percentage by mass.
- Polishing solution AnjiDPP1550 chemical mechanical polishing solution.
- Polishing machine 8" Mirra, polishing pad Dow IC1010, polishing disk and polishing head rotation speed of 93/87 rpm, lower pressure 3 psi o
- Polishing wafer silicon wafer, after polishing, clean the silicon wafer with deionized water in the cleaning machine.
- Second step polishing conditions The silicon wafer after the first polishing is polished with the polishing liquid of the present invention, and after polishing, the silicon wafer is cleaned with deionized water in a cleaning machine.
- Polishing machine 8" Mirra, polishing pad Fujibo H7000, polishing disc and polishing head rotation speed of 93/87rpm, lower pressure 3psi.
- the polishing liquid used for the second step polishing and polishing results are shown in Table 1 and Figures 1 ⁇ 4. Silicon wafers and roughness Sichuan XE-300P sub-force! uU mirror measurement, the contact angle of water on the surface of the silicon after polishing is measured by DSA 100 contact angle measuring instrument, the polished silicon wafer sheet and the grinding particles The residual condition was observed by an optical microscope. Table 1 Results of the polishing liquid of the present invention and the polishing of the first: 3 ⁇ 4 piece after polishing
- the surface roughness of the silicon wafer after the second polishing step is performed by using the polishing liquids 1 to 22 of the present invention.
- the surface contact angles are reduced to different extents, which is beneficial to reduce the surface defects after polishing.
- Figures 3 and 4 are optical microscope images of the surface of the polished silicon wafers of Examples 1 and 10, respectively. It is beneficial to the cleaning after polishing. After cleaning, no abrasive particles remain on the surface of the silicon wafer.
- the addition of complexing agent has no significant effect on the silicon removal rate, surface roughness after polishing and surface hydrophilicity. However, the complexing agent is added. After that, it will help remove metal ion impurities that may be carried in the semiconductor process.
- wt% of the present invention refers to the mass percentage.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
本发明揭示了一种化学机械抛光液在硅基材料抛光中的应用,该抛光液至少含有研磨颗粒和氧化剂。该抛光液可用于抛光硅基材料如多晶硅和单晶硅,抛光后的硅基晶片表面粗糙度低,亲水性好,有利于降低表面缺陷。
Description
一种化学机械抛光液的应用
技术领域
背景技术
硅(单晶硅 /多晶硅)材料在集成电路中被广泛应用, 硅片的制造需要很 多生产工艺步骤, 包括晶体生长, 切片, 研磨, 刻蚀, 抛光和清洗。 其中, 化学机械抛光被用来去除多余的材料和在其他制程中形成的表面缺陷如划 伤、 表面形貌缺陷等, 使之可用于制造集成电路。
为了保证产能, 通常巿售的硅化学机械抛光液的抛光速率较高, 抛光后 晶片后表面粗糙度高, 表面疏水, 抛光后清洗困难, 容易出现水渍、 研磨颗 粒残留、 雾度高等缺陷。 这些缺陷会对半导体器件的良率产生影响。 在工业 生产中, 通常会使用一些特殊的清洗液来清洗抛光后的硅晶片, 清洗后虽然 能减少磨料颗粒残留、 雾度缺陷等, 但却无法降低晶片表面粗糙度。 因此需 要使用一种新的抛光方法和抛光液来同时解决这个问题。
另一方面, 在实施了研磨、 蚀刻、 抛光等处理后, 可能有金属杂质如金 属本身、 金属氢氧化物、 金属氧化物附着、 残存于硅晶片表面, 这些金属杂 质会对半导体器件的可靠性等产生影响。本发明通过添加一些络合剂来捕获 和除去这些可能存在的金属杂质。
一日本专利 JP2011082372(A) 揭示了一种用于硅晶片的清洗液,其含有 无机铵盐 (氯化铵、 碳酸铵等), 过氧化氢和水, 该清洗液还包含氢氧化铵 来调节 pH并增加清洗能力。 使用该清洗液可抑制雾度水平的下降。 可以抑 制雾度水平的下降, 但不能改善抛光后的表面粗糙度。
一美国专利 US200619685A1揭示了一种抛光液, 其含有研磨颗粒, pH 调节剂, 水溶性增稠剂和螯合剂, 其中螯合剂包含至少一种醋酸螯合剂和一
种磷酸螯合剂。 该抛光液可减少品 而的缺陷数量, 降低品 而粗糙度 和雾度。 水溶性增稠剂的作用足减少一氧化硅颗粒的聚结, 减少品圆表面的 光点缺陷。醋酸螯合剂和 /或磷酸螯合剂的作用是减少或防止金属离子在品圆 表面的残留并且进一步提高二氧化硅的分散稳定性。 成分复杂, 单独使用醋 酸螯合剂或磷酸螯合剂时抛光液稳定性不够好 (大颗粒随吋间增加)。 使用 含有钠离子的螯合剂, 使得抛光液里的钠离子含量增加, 可能因钠离子残留 对晶圆的可靠性产生影响。 发明内容
本发明提供了一种化学机械抛光液的应用, 该抛光液在硅基材抛光中能 降水在硅晶片表面低接触角, 该抛光液含有研磨颗粒和氧化剂, 还可以含有 至少一种络合剂。 该抛光液可用于硅晶片的第二步抛光, 即在第一步使用具 有很高硅去除速率的硅化学机械抛光液去除大量的硅,第二步使用本发明的 抛光液去除少量的硅,改善抛光后的表面粗糙度,提高硅晶片表面的亲水性, 有利于减少研磨颗粒的吸附, 降低雾度, 降低表面缺陷, 并有利于去除制程 中可能存在的金属离子杂质。
在本发明中, 所述的研磨颗粒为二氧化硅、 氧化铝、 掺杂铝或覆盖铝的 二氧化硅、 二氧化铈、 二氧化钛、 高分子研磨颗粒中的一种或多种, 优选为 二氧化硅。含量为 0.5〜20wt%, 优选为 1〜5wt%;粒径为 20〜200nm, 优选 为 20〜120nm。
在本发明中, 所述的氧化剂为过氧化氢、 过氧化脲、 过氧甲酸、 过氧乙 酸、 过硫酸盐、 过碳酸盐、 高碘酸、 高氯酸、 高硼酸、 高锰酸钾和硝酸铁中 的一种或多种。 优选为过氧化氢。 含量为 0.01 ~5wt%,优选为 0.05〜1wt%。
在本发明中, 所述的抛光液的 pH大于 7, 优选为 9~12。
在本发明中, 本发明的抛光液还可以含有至少一种络合剂, 所述的络合 剂为任何合适的可与金属离子形成可溶性化合物的添加剂, 该络合剂可以将
抛光甚材上可能存在的金 离子溶解去除, 避免残留在基材中而影响 路的 可靠性。 合适的络合剂包括氨羧化合物, 冇机羧酸, 有机膦酸和有机胺等所 述的氨羧化合物选自甘氨酸、 丙氨酸、缬氨酸、亮氨酸、 脯氨酸、 苯丙氨酸、 酪氨酸、 色氨酸、 赖氨酸、 精氨酸、 组氨酸、 丝氨酸、 天冬氨酸、 苏氨酸、 谷氨酸、 天冬酰胺、 谷氨酰胺、 氨三乙酸、 乙二胺四乙酸、 环己垸四乙酸、 乙二胺二琥珀酸、 二乙烯三胺五乙酸和三乙烯四胺六乙酸中的一种或多种; 所述的有机羧酸为醋酸、 草酸、 柠檬酸、 酒石酸、 丙二酸、 丁二酸、 苹果酸、 乳酸、没食子酸和磺基水杨酸中的一种或多种; 所述的有机膦酸为 2-膦酸丁 垸 -1, 2, 4-三羧酸、 氨基三甲叉膦酸、 羟基乙叉二膦酸、 乙二胺四甲叉膦 酸、 二乙烯三胺五甲叉膦酸、 2-羟基膦酸基乙酸、 乙二胺四甲叉膦酸和多氨 基多醚基甲叉膦酸中的一种或多种; 所述的有机胺为乙二胺、 二乙烯三胺、 五甲基二乙烯三胺、 多乙烯多胺、 三乙烯四胺、 四乙烯五胺; 所述的盐为钾 盐和 /或铵盐。 络合剂的含量为 0.01〜5wt%, 优选为 0.01〜1wt%。
上述的化学机械抛光液, 其中, 还包括 pH调节剂, 粘度调节剂, 消泡 剂, 杀菌剂等本领域常规的添加剂。
上述的化学机械抛光液可将除氧化剂以外的组分制备成浓缩样品, 使用 前用去离子水稀释到本发明的浓度范围并添加氧化剂即可。
在本发明中, 所述的抛光基材为硅基材, 包括单晶硅和多晶硅。
本发明的抛光液可用于硅晶片的第二步抛光, 即在第一步使用具有很高 硅去除速率的硅化学机械抛光液去除大量的硅, 第二步使用本发明的抛光液 去除少量的硅, 改善抛光后的表面粗糙度, 提高硅晶片表面的亲水性, 有利 于减少研磨颗粒的吸附, 降低雾度, 降低表面缺陷, 并有利于去除制程中可 能存在的金属离子杂质。
本发明的技术效果在于:
1 ) 本发明的浆料可以降低抛光后硅基晶片表面的粗糙度;
2 ) 本发明的桨料可以提高硅基晶片抛光后表面的亲水性, 从而有利于
3 ) 本发明的浆料有利于去除制程屮可能存在的金属离子杂质。 附图说明
图 1 : 第一步抛光并清洗后的硅晶片表面光学显微镜图;
图 2: 用对比 2进行第二步抛光并清洗后的硅晶片表面光学显微镜图; 图 3 :用实施例 1进行第二步抛光并清洗后的硅晶片表面光学显微镜图; 图 4: 用实施例 10进行第二步抛光并清洗后的硅晶片表面光学显微镜 图。 具体实施方式
本发明所用试剂及原料均巿售可得。本发明的抛光液由上述成分简单均 匀混合即可制得。
下面通过具体实施方式来进一步阐述本发明的优势。但本发明包括但不 限于实施例的具体配方和组成。 制备实施例
表 1给出了本发明的化学机械抛光液配方。以下所述百分含量均为质量 百分比含量。
第一步抛光条件: 抛光液: AnjiDPP1550化学机械抛光液。 抛光机台: 8" Mirra, 抛光垫 Dow IC1010, 抛光盘和抛光头转速为 93/87rpm,下压力 3psi o 抛光晶片: 硅晶片, 抛光后在清洗机台内用去离子水清洗硅晶片。
第二步抛光条件: 将第一步抛光后的硅晶片用本发明的抛光液进行抛 光, 抛光后在清洗机台内用去离子水清洗硅晶片。抛光机台: 8" Mirra, 抛光 垫 Fujibo H7000, 抛光盘和抛光头转速为 93/87rpm, 下压力 3psi。 第二步抛 光所用抛光液及抛光结果见表 1和图 1〜4。
硅品片 而粗糙度川 XE-300P 子力 !uU 镜测量所得,水在抛光后硅品 表面的接触角用 DSA 100接触角测量仪所测得, 抛光后的硅品片表而的研 颗粒残留状况通过光学显微镜观察。 表 1 本发明的抛光液及第—:歩抛光后的 ¾品片抛光的结果
石 ΐ粗 水在石 t 糙度 品片表
Si ±·
o 面的接 实施 研磨颗粒 氧化剂 络合剂 pH 除速率
(A/min) 触角 例 (nm)
(度) 对比
1 / 1 1 1 0.396 58
1
对比
3%SiO2(70nm) 1 1 10 3970 0.169 55.3
2
对比 0.1%甘氨
3% Si02 (70nm) 1 10 3729 0.135 60 3 酸
0.1%过氧化
1 3% Si02 (70nm) 1 10 3145 0.136 4.1
氢
0.1% 过氧
2 3% Si02 (70nm) 1 8 2680 0.130 31.1
化氢
0.1% 过氧
3 3% Si02 (70nm) 1 9 3000 0.216 7.1
化氢
0.1% 过氧
4 3% Si02 (70nm) 1 1 1 3420 0.172 9
化氢
0.1% 过氧
5 3% Si02 (70nm) 1 12 3500 0.171 9.2
化氢
0.1% 过氧
6 2.5% Si02 (70nm) 1 10 1986 0.156 2.3
化氢
0.1% 过氧
7 1.5%SiO2(70nm) 1 10 1037 0.149 2.4
化氢
0.1% 过氧
8 1% SiO, (70nm) 1 10 202 0.214 2.4
化氢
0.15%过氧
9 3% SiO, (70nm) 1 10 2591 0.19 2.9
化氢
0.1%甘氨
10 3% Si02 (70nm) 10 3345 0.131 4.8
酸
0.3% 过氧 0.1%甘氨
1 1 3% SiO, (70nm) 10 2607 0.182 2.1
化氢 酸
0.5% 过氧 0.1%甘氨
12 3% Si02 (70nm) 10 2145 0.171 2.1
化氢 酸
1% 过氧化 0.1%甘氨
13 3% Si02 (70nm) 10 1097 0.151 2.1
氢 酸
0.1% 过氧
14 3% Si02 (70nm) 1%甘氨酸 10 3421 0.152 6.6
化氢
0.1 " ', 过¾ 0.5%乙 :
1 3% Si02 (80 10 3356 0.225 4.4
化_ 胺
0.01 %
】 0.1 % 过¾
6 3% SiO: (80nm) 亚乙基 : 10 3360 0.293 3.1
化 M
膦酸
0.1 %卄氨
17 3% SiO: (80nm) 1 %过硫酸饺 10 2600 0.308 46.3
酸
0.1%甘氨
18 5% Si02 (80nm) 0.1%碘酸钾 10 4050 0.129 31.1
酸
0.05%过氧
19 10% Si02 (40nm) 1 9 5200 0.1 17 17.5
化氢
5% 过氧化
20 20% Si02 (20nm) 5%脯氨酸 9 1800 0.109 2.6
氢
0.1 % 过氧 0.1 %甘氨
21 3% Si02 ( 120nm) 10 4650 0.137 8.0
化氢 酸
0.5% Si02 0.01%过氧
22 1 1 1 2710 0.167 38.0
(200nm) 化氢 由表 1结果可见, 第一步抛光后硅晶片表面粗糙度和水在硅晶片表面的 接触角都较高 (见对比 1 )。 抛光后晶片表面研磨颗粒残留较多 (见图 1 用不添加氧化剂的对比实施例 2和 3抛光后, 硅晶片表面粗糙度降低, 但水 在硅晶片表面的接触角与第一步抛光后一样, 表面疏水, 不利于抛光后的清 洗,清洗后表面仍有较多研磨颗粒残留(见图 2)。而采用本发明的抛光液 1〜 22进行第二步抛光后,硅晶片表面的粗糙度和表面接触角均有不同程度的降 低, 有利于降低抛光后表面缺陷。 图 3和 4分别为实施例 1和 10抛光后的 硅晶片表面光学显微镜图。 从图中可见, 添加了氧化剂后, 有利于抛光后的 清洗,清洗后硅晶片表面无研磨颗粒残留,而且,添加络合剂对硅去除速率, 抛光后的表面粗糙度和表面亲水性均无明显影响。 但是添加了络合剂后, 将 有助于去除在半导体制程中可能带入的金属离子杂质。
应当理解的是, 本发明所述 wt%均指的是质量百分含量。
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
权利要求
1、 一种抛光液在硅基材抛光中降低水在硅晶片表而接触角中的应用, 其 特征在于: 所述抛光液包含研磨颗粒以及氧化剂。
2、 如权利要求 1所述的应用, 其特征在于: 所述的研磨颗粒选自二氧化 硅、 氧化铝、 掺杂铝或覆盖铝的二氧化硅、 二氧化铈、 二氧化钛和高分子研 磨颗粒中的一种或多种。
3、 如权利要求 2所述的应用,其特征在于:所述的研磨颗粒为二氧化硅。
4、 如权利要求 1 所述的应用, 其特征在于: 所述的研磨颗粒的含量为 0.5〜20wt%。
5、 如权利要求 4所述的应用,其特征在于:所述的研磨颗粒的含量为 1〜 5wt% c
6、 如权利要求 1 所述的应用, 其特征在于: 所述的研磨颗粒的粒径为 20〜200nm。
7、 如权利要求 6 所述的应用, 其特征在于: 所述的研磨颗粒的粒径为 20〜120nm。
8、 如权利要求 1所述的应用,其特征在于:所述的氧化剂选自过氧化氢、 过氧化脲、 过氧甲酸、 过氧乙酸、 过硫酸盐、 过碳酸盐、 高碘酸、 高氯酸、 高硼酸、 高锰酸钾和硝酸铁中的一种或多种。
9、 如权利要求 8所述的应用, 其特征在于: 所述的氧化剂为过氧化氢。
10、 如权利要求 1 所述的应用, 其特征在于: 所述的氧化剂的含量为 0.0卜 5wt%。
1 1、 如权利要求 1 所述的应用, 其特征在于: 所述的氧化剂的含量为 0.05〜1wt%。
12、 如权利要求 1所述的应用, 其特征在于: 所述的抛光液的 pH大于 7。
13、 如权利要求 12所述的应用,其特征在于:所述的抛光液的 pH为 9~12。
15、 如权利要求 14所述的 用, 其特征在于: 所述的络合剂为能与金属 离子形成可溶性化合物的添加剂。
16、 如权利要求 15所述的应用, 其特征在于: 所述的络合剂为氨羧化合 物, 有机羧酸, 有机膦酸和 /或有机胺。
17、 如权利要求 16所述的应用, 其特征在于: 所述的氨羧化合物选自甘 氨酸、 丙氨酸、 缬氨酸、 亮氨酸、 脯氨酸、 苯丙氨酸、 酪氨酸、 色氨酸、 赖 氨酸、 精氨酸、 组氨酸、 丝氨酸、 天冬氨酸、 苏氨酸、 谷氨酸、 天冬酰胺、 谷氨酰胺、 氨三乙酸、 乙二胺四乙酸、 环己烷四乙酸、 乙二胺二琥珀酸、 二 乙烯三胺五乙酸和三乙烯四胺六乙酸中的一种或多种; 所述的有机羧酸为醋 酸、 草酸、 柠檬酸、 酒石酸、 丙二酸、 丁二酸、 苹果酸、 乳酸、 没食子酸和 磺基水杨酸中的一种或多种; 所述的有机膦酸为 2-膦酸丁烷 -1, 2, 4-三羧 酸、 氨基三甲叉膦酸、 羟基乙叉二膦酸、 乙二胺四甲叉膦酸、 二乙烯三胺五 甲叉膦酸、 2-羟基膦酸基乙酸、 乙二胺四甲叉膦酸和多氨基多醚基甲叉膦酸 中的一种或多种;所述的有机胺为乙二胺、二乙烯三胺、五甲基二乙烯三胺、 多乙烯多胺、 三乙烯四胺、 四乙烯五胺; 所述的盐为钾盐和 /或铵盐。
18、 如权利要求 14所述的应用,其特征在于:所述络合剂的含量为 0.01〜 5wt% o
19、 如权利要求 18所述的应用,其特征在于:所述络合剂的含量为 0.01〜 1wt%。
20、 如权利要求 1所述的应用, 其特征在于: 所述的硅基材包括单晶硅和 多晶 。
21、 如权利要求 1所述的应用, 其特征在于, 所述抛光液还具备改善抛光 后硅的表面粗糙度, 提高硅晶片表面的亲水性的作用。
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CN110205034A (zh) * | 2019-06-24 | 2019-09-06 | 苏州大学 | 氮化镓化学机械抛光液及其制备方法 |
CN110423999A (zh) * | 2019-08-30 | 2019-11-08 | 深圳市天得一环境科技有限公司 | 一种不锈钢表面亲水处理方法 |
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CN113528028A (zh) * | 2021-08-23 | 2021-10-22 | 长鑫存储技术有限公司 | 化学机械抛光液、半导体结构及其制备方法 |
CN115895451A (zh) * | 2021-09-30 | 2023-04-04 | 昆山欣谷微电子材料有限公司 | 一种用于制备亲水性表面硅片的碱性抛光液组合物 |
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