WO2013082863A1 - Polishing liquid for tsv blocking layer - Google Patents

Polishing liquid for tsv blocking layer Download PDF

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Publication number
WO2013082863A1
WO2013082863A1 PCT/CN2012/001016 CN2012001016W WO2013082863A1 WO 2013082863 A1 WO2013082863 A1 WO 2013082863A1 CN 2012001016 W CN2012001016 W CN 2012001016W WO 2013082863 A1 WO2013082863 A1 WO 2013082863A1
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Prior art keywords
polishing liquid
liquid according
acid
concentration
silicon nitride
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PCT/CN2012/001016
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French (fr)
Chinese (zh)
Inventor
宋伟红
姚颖
孙展龙
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安集微电子（上海）有限公司
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Priority to SG11201402831SA priority Critical patent/SG11201402831SA/en
Priority to KR1020147015534A priority patent/KR20140100953A/en
Publication of WO2013082863A1 publication Critical patent/WO2013082863A1/en

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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
    • C09K3/1454—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
    • H01L21/04—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]
    • 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
    • H01L21/76898—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics formed through a semiconductor substrate

Definitions

  • the present invention relates to a polishing liquid, and more particularly to a chemical mechanical polishing liquid for polishing a TSV barrier layer.
  • TSV Through-Silicon-Via via
  • 3D TSV is the latest technology for interconnecting chips by making vertical conduction between the chip and the chip, between the wafer and the wafer. Unlike previous IC package bonding and bump overlay technology, TSV enables the chip to be stacked in the three-dimensional direction with the highest density and smallest form factor, greatly improving chip speed and low power consumption. Its main advantages are: Minimal size and weight, integrating different kinds of technologies into a single package, replacing long 2D interconnects with short vertical interconnects, reducing parasitic effects and power consumption.
  • TSV production needs to open different layers of materials, including silicon materials, various insulating or conductive thin film layers in ICs.
  • materials including silicon materials, various insulating or conductive thin film layers in ICs.
  • the thickness of various film layers is also relatively high, which requires a high removal rate and a suitable polishing option in the CMP process.
  • the maximum correction of the prode to defects can be achieved, and the silicon nitride layer can be stopped, and the corrosion and defects of the metal can not be generated, and the surface particles are controlled within the scope of the process. This puts higher demands on the CMP of the through-silicon via barrier layer.
  • TSV barrier polishing fluids There are currently no reports of commercial TSV barrier polishing fluids. Summary of invention
  • the object of the present invention is to solve the above problems in the prior art, and to provide a high silica dielectric material removal rate and a high polishing selectivity ratio for silicon nitride, which has high defects for the prode. Correction ability, chemical mechanical polishing fluid with good corrosion and defects, and good stability.
  • a TSV barrier layer polishing liquid characterized by comprising the following components: an abrasive, a group of alloys, a protective agent, a complexing agent, an oxidizing agent, a silicon nitride inhibitor, and a pH adjusting agent.
  • the abrasive is silica sol or fumed silica.
  • the abrasive has a particle size of from 20 to 200 nm, preferably from 40 to 120 nm.
  • the abrasive content is from 10 to 50%, preferably from 20 to 30%.
  • the combined metal protecting agent comprises an azole compound and a water soluble polymer.
  • the azole compound is benzotriazole and a derivative thereof; and the water-soluble polymer is polyacrylic acid and a copolymer thereof.
  • the concentration of the azole compound is 0.01-0.5%; and the concentration of the water-soluble polymer is 0.005-0.1%.
  • the concentration of the azole compound is 0.05-0.2%; and the concentration of the water-soluble polymer is 0.01-0.05%.
  • the complexing agent is selected from one or more of the group consisting of organic phosphoric acid, PBTCA, HPAA, HEDP, EDTMP and ATMP.
  • concentration of the complexing agent is from 0.05% to 1%, preferably from 0.1% to 0.5%.
  • the silicon nitride inhibitor is a formaldehyde polycondensate of a naphthalene sulfonate having the following formula: among them:
  • the concentration of the silicon nitride inhibitor ranges from 50 ppm to 0.1%.
  • the silicon nitride inhibitor is methylene bis naphthalenesulfonic acid disodium salt, methyl naphthalenesulfonic acid formaldehyde polycondensate and/or benzyl naphthalenesulfonic acid formaldehyde polycondensate.
  • the pH adjusting agent is an organic carboxylic acid.
  • organic carboxylic acid is selected from one or more of oxalic acid, malonic acid, succinic acid, citric acid and tartaric acid.
  • the oxidizing agent is a peroxide or a persulfide.
  • the oxidizing agent is selected from one or more of hydrogen peroxide, sodium peroxide, potassium peroxide, benzoyl peroxide, sodium persulfate, potassium persulfate and ammonium persulfate.
  • the polishing liquid also includes: a bactericidal anti-fungal agent.
  • the bactericidal mold inhibitor is a quaternary ammonium salt active agent.
  • the polishing liquid has a pH of 2-5, preferably 3 ⁇ 4.
  • the removal rate of silicon nitride is less than 100 A/min, and the selection ratio is 15-20. It can better stop the silicon nitride layer, the complexing agent and the combined metal protective agent, and protect the metal copper well. No metal corrosion is found, and the metal removal rate of the hydrogen peroxide is mild and linear.
  • the fine line area of the polished surface is clear and sharp, free of particulate matter and organic matter residues.
  • the front-end and the polished defects have a large correction, and have better planarization efficiency. After soaking, it has good corrosion resistance.
  • Figures 1 and 2 show the surface topography of the polished pattern
  • Figures 3 and 4 are pictures of the surface soaked in the polishing solution
  • Figure 5-7 is a schematic view of the polished surface of the TSV through-silicon via barrier layer before and after polishing, wherein: Figure 5 is a schematic diagram of the through-wafer before through-silicon via (TSV) polishing.
  • TSV through-silicon via
  • FIG. 6 is a schematic diagram of a silicon through hole (TSV) copper polished after polishing
  • FIG. 7 is a schematic diagram of a polished through-silicon via (TSV) barrier layer after polishing
  • Polishing pad IC pad
  • Polishing fluid flow 100ml/min
  • Static Corrosion Rate Freshly polished copper sheets were immersed in a slurry for 15 min to measure the thickness of the film before and after.
  • Butterfly depression The depression of the 80um metal block was measured using a Semitech 854 graphic wafer.
  • Polishing uniformity within the slice a butterfly-shaped depression of different line widths within a die.
  • Blank wafer PETEOS, Ta, Cu, Si3N4 Table 1, Formulations of Examples 1-7 and Comparative Polishing Solutions
  • BTA benzotriazole
  • PAA polyacrylic acid
  • PBTCA 2-phosphonic acid - 1,2,4-tricarboxylic acid butane
  • DISN1 methylene bisnaphthalenesulfonic acid disodium salt
  • DISN2 methylnaphthalenesulfonate formaldehyde condensate
  • DISN3 benzylnaphthalenesulfonate methyl drunk condensate.
  • HPAA 2-m zm HEDP: Hydroxyethylidene diphosphonic acid.
  • the reference polishing liquid is a commercially available barrier polishing liquid. Table 2, effect data
  • the polishing liquid has a higher removal rate of Ta and SiO2 than the comparative polishing liquid, and the removal rate of silicon nitride is less than 100 A/min after the addition of the silicon nitride inhibitor.
  • the ratio is 15-20. It can better stop the silicon nitride layer, the complexing agent and the combined metal protective agent, and protect the metal copper well. No metal corrosion is found, and the metal removal rate of the hydrogen peroxide is mild and linear.
  • the fine line area of the polished surface is clear and sharp, free of particulate matter and organic matter residues.
  • the front-end and the polished defects have a large correction, and have better planarization efficiency. After soaking, there is no significant change in the surface of the graphic sheet, indicating good corrosion resistance.

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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 Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

A chemical-mechanical polishing liquid, applicable to a through-silicon-via (TSV) blocking layer, at least comprises an abrasive, a composite copper corrosion inhibitor, a complexing agent, and a silicon nitride modifier. The polishing liquid has a high silicon dioxide removal speed and a low silicon nitride removal speed, so as to implement effective planarization on the blocking layer and stop the silicon nitride layer, so as to form a through-silicon hole, and at the same time not to cause metal corrosion, thereby achieving the high defect correction capability and the low surface pollutant index.

Description

一种 TSV阻挡层抛光液 技术领域  TSV barrier layer polishing liquid
本发明涉及一种抛光液， 尤其涉及一种用于抛光 TSV阻挡层的化学机 械抛光液。 技术背景  The present invention relates to a polishing liquid, and more particularly to a chemical mechanical polishing liquid for polishing a TSV barrier layer. technical background
参见图 5-7， 为了提高 IC的性能、进一步缩小尺寸、 降低功耗和成本， 小尺 寸 3D TSV (TSV, Through -Silicon-Via硅通孔）封装技术也由此应运而生。 See Figure 5-7. In order to improve IC performance, further downsizing, and reduce power consumption and cost, small-size 3D TSV (TSV, Through-Silicon-Via via) packaging technology has emerged.
3D TSV是通过在芯片和芯片之间、 晶圆和晶圆之间制作垂直导通， 实现芯 片之间互连的最新技术。 与以往 IC封装键合和使用凸点的叠加技术不同， TSV能够使芯片在三维方向堆叠的密度最大，外形尺寸最小，大大改善芯片 速度和低功耗的性能。其主要优势表现为： 具有最小的尺寸和重量， 将不同 种类的技术集成到单个封装中， 用短的垂直互连代替长的 2D互连， 降低寄 生效应和功耗等。  3D TSV is the latest technology for interconnecting chips by making vertical conduction between the chip and the chip, between the wafer and the wafer. Unlike previous IC package bonding and bump overlay technology, TSV enables the chip to be stacked in the three-dimensional direction with the highest density and smallest form factor, greatly improving chip speed and low power consumption. Its main advantages are: Minimal size and weight, integrating different kinds of technologies into a single package, replacing long 2D interconnects with short vertical interconnects, reducing parasitic effects and power consumption.
TSV制程的集成方式非常多， 但都面临一个共同的难题， 即 TSV制作都 需要打通不同材料层，包括硅材料、 IC中各种绝缘或导电的薄膜层。例如金 属铜， 阻挡层金属钽， 二氧化硅绝缘层以及氮化硅停止层等， 各种膜层的厚 度也比较高， 这就需要在 CMP过程中具有较高的去除速率和合适的抛光选 择比， 才能实现对前程缺陷的最大矫正， 并停止在氮化硅层， 同时不能产生 金属的腐蚀和缺陷， 表面颗粒物控制在工艺要求的范围。这对硅通孔阻挡层 的 CMP提出了更高的要求。目前还没有商业化的 TSV阻挡层抛光液的报道。 发明概要 There are many integration methods for TSV processes, but they all face a common problem. TSV production needs to open different layers of materials, including silicon materials, various insulating or conductive thin film layers in ICs. For example, metallic copper, barrier metal ruthenium, silicon dioxide insulating layer, and silicon nitride stop layer, etc., the thickness of various film layers is also relatively high, which requires a high removal rate and a suitable polishing option in the CMP process. In comparison, the maximum correction of the prode to defects can be achieved, and the silicon nitride layer can be stopped, and the corrosion and defects of the metal can not be generated, and the surface particles are controlled within the scope of the process. This puts higher demands on the CMP of the through-silicon via barrier layer. There are currently no reports of commercial TSV barrier polishing fluids. Summary of invention
本发明的目的是解决上述现有技术中存在的问题，提供一种具有较高的 二氧化硅介质材料去除速率和较高的对氮化硅的抛光选择比，对前程的缺陷 具有较高的校正能力， 不产生金属腐蚀和缺陷， 稳定性较好的化学机械抛光 液。  The object of the present invention is to solve the above problems in the prior art, and to provide a high silica dielectric material removal rate and a high polishing selectivity ratio for silicon nitride, which has high defects for the prode. Correction ability, chemical mechanical polishing fluid with good corrosion and defects, and good stability.
本发明的技术方案如下：  The technical solution of the present invention is as follows:
一种 TSV阻挡层抛光液， 其特征在于， 包含以下组分： 磨料、 组合金 属保护剂、 络合剂、 氧化剂、 氮化硅抑制剂和 pH调节剂。  A TSV barrier layer polishing liquid characterized by comprising the following components: an abrasive, a group of alloys, a protective agent, a complexing agent, an oxidizing agent, a silicon nitride inhibitor, and a pH adjusting agent.
其中， 所述磨料是二氧化硅溶胶或气相法二氧化硅。所述磨料的粒径为 20-200nm， 较佳的为 40-120nm。 所述磨料含量为 10-50%， 较佳的为 20-30%。  Wherein the abrasive is silica sol or fumed silica. The abrasive has a particle size of from 20 to 200 nm, preferably from 40 to 120 nm. The abrasive content is from 10 to 50%, preferably from 20 to 30%.
其中， 组合金属保护剂包括一种唑类化合物和一种水溶性聚合物。  Wherein, the combined metal protecting agent comprises an azole compound and a water soluble polymer.
其中， 所述的唑类化合物为苯并三氮唑及其衍生物； 所述水溶性聚合物 为聚丙烯酸及其共聚物。  Wherein the azole compound is benzotriazole and a derivative thereof; and the water-soluble polymer is polyacrylic acid and a copolymer thereof.
其中， 所述唑类化合物的浓度为 0.01-0.5%; 所述水溶性聚合物的浓度 为 0.005-0.1%。优选的， 所述唑类化合物的浓度为 0.05-0.2%; 所述水溶性 聚合物的浓度为 0.01-0.05%。  Wherein the concentration of the azole compound is 0.01-0.5%; and the concentration of the water-soluble polymer is 0.005-0.1%. Preferably, the concentration of the azole compound is 0.05-0.2%; and the concentration of the water-soluble polymer is 0.01-0.05%.
其中， 所述的络合剂选自有机磷酸， PBTCA, HPAA, HEDP, EDTMP 和 ATMP中的一种或多种。所述络合剂的浓度为 0.05% -1%,优选 0.1-0.5%。  Wherein the complexing agent is selected from one or more of the group consisting of organic phosphoric acid, PBTCA, HPAA, HEDP, EDTMP and ATMP. The concentration of the complexing agent is from 0.05% to 1%, preferably from 0.1% to 0.5%.
其中，所述氮化硅抑制剂为一种萘磺酸盐的甲醛缩聚物，具有以下通式:
Figure imgf000003_0001
其中：
Figure imgf000004_0001
， 所述氮化硅抑制 剂的浓度从 50ppm到 0.1%。 Wherein, the silicon nitride inhibitor is a formaldehyde polycondensate of a naphthalene sulfonate having the following formula:
Figure imgf000003_0001
among them:
Figure imgf000004_0001
The concentration of the silicon nitride inhibitor ranges from 50 ppm to 0.1%.
其中， 所述氮化硅抑制剂为亚甲基双萘磺酸二钠盐， 甲基萘磺酸甲醛缩 聚物和 /或苄基萘磺酸甲醛缩聚物。  Wherein, the silicon nitride inhibitor is methylene bis naphthalenesulfonic acid disodium salt, methyl naphthalenesulfonic acid formaldehyde polycondensate and/or benzyl naphthalenesulfonic acid formaldehyde polycondensate.
其中， 所述 pH调节剂为一种有机羧酸。  Wherein the pH adjusting agent is an organic carboxylic acid.
其中， 所述有机羧酸选自草酸， 丙二酸， 丁二酸， 柠檬酸和酒石酸中的 一种或多种。  Wherein the organic carboxylic acid is selected from one or more of oxalic acid, malonic acid, succinic acid, citric acid and tartaric acid.
其中， 所述氧化剂为过氧化物或过硫化物。 所述氧化剂选自过氧化氢， 过氧化钠， 过氧化钾， 过氧化苯甲酰， 过硫酸钠， 过硫酸钾和过硫酸铵中的 一种或多种。  Wherein the oxidizing agent is a peroxide or a persulfide. The oxidizing agent is selected from one or more of hydrogen peroxide, sodium peroxide, potassium peroxide, benzoyl peroxide, sodium persulfate, potassium persulfate and ammonium persulfate.
其中， 抛光液还包括： 杀菌防霉变剂。所述杀菌防霉变剂为季铵盐活性 剂。  Among them, the polishing liquid also includes: a bactericidal anti-fungal agent. The bactericidal mold inhibitor is a quaternary ammonium salt active agent.
其中， 所述抛光液的 pH值为 2-5， 优选 3~4。  Wherein, the polishing liquid has a pH of 2-5, preferably 3~4.
本发明具备的有益效果是：  The beneficial effects of the invention are:
具有更高的 Ta和 Si02的去除速率，氮化硅的去除速率小于 100A/min， 选择比达到 15-20。 能够较好地停止在氮化硅层， 络合剂以及组合金属保护 剂的共同作用下， 很好的保护金属铜， 未发现金属腐蚀， 且金属的去除速率 碎双氧水呈温和的线性变化。抛光后表面的细线区域清晰锐利， 无颗粒物和 有机物质残留等污染物。此外，对前程同抛光后的缺陷具有较大幅度的校正, 具有较好的平坦化效率。 浸泡后， 具有较好的抗腐蚀性能。 附图说明 With a higher removal rate of Ta and SiO 2 , the removal rate of silicon nitride is less than 100 A/min, and the selection ratio is 15-20. It can better stop the silicon nitride layer, the complexing agent and the combined metal protective agent, and protect the metal copper well. No metal corrosion is found, and the metal removal rate of the hydrogen peroxide is mild and linear. The fine line area of the polished surface is clear and sharp, free of particulate matter and organic matter residues. In addition, the front-end and the polished defects have a large correction, and have better planarization efficiency. After soaking, it has good corrosion resistance. DRAWINGS
图 1、 2为抛光后图形片的表面形貌；  Figures 1 and 2 show the surface topography of the polished pattern;
图 3、 4为在抛光液中浸泡过的表面图片；  Figures 3 and 4 are pictures of the surface soaked in the polishing solution;
图 5-7为 TSV硅通孔阻挡层抛光前后的抛面示意图， 其中： 图 5为硅通孔（TSV)抛光前抛面示意图  Figure 5-7 is a schematic view of the polished surface of the TSV through-silicon via barrier layer before and after polishing, wherein: Figure 5 is a schematic diagram of the through-wafer before through-silicon via (TSV) polishing.
图 6为硅通孔（TSV)铜抛光后抛面示意图  Figure 6 is a schematic diagram of a silicon through hole (TSV) copper polished after polishing
图 7为硅通孔（TSV) 阻挡层抛光后抛面示意图  Figure 7 is a schematic diagram of a polished through-silicon via (TSV) barrier layer after polishing
发明内容 Summary of the invention
下面通过具体实施方式来进一步阐述本发明的优势。  Advantages of the present invention are further illustrated by the following detailed description.
抛光条件：  Polishing conditions:
抛光垫： IC pad  Polishing pad: IC pad
抛光条件： 70/90rpm  Polishing conditions: 70/90 rpm
抛光液流量： 100ml/min  Polishing fluid flow: 100ml/min
静态腐蚀速率： 将新鲜抛光的铜片放入浆液中浸渍 15min， 测 前后的膜层厚度。  Static Corrosion Rate: Freshly polished copper sheets were immersed in a slurry for 15 min to measure the thickness of the film before and after.
蝶形凹陷： 采用 Semitech 854图形晶圆测量 80um金属块的 形凹陷。  Butterfly depression: The depression of the 80um metal block was measured using a Semitech 854 graphic wafer.
切片内的抛光均一性： 为一个管芯内不同线宽的蝶形凹陷。 空白晶片： PETEOS, Ta， Cu， Si3N4 表 1、 实施例 1-7与对比抛光液的配方 Polishing uniformity within the slice: a butterfly-shaped depression of different line widths within a die. Blank wafer: PETEOS, Ta, Cu, Si3N4 Table 1, Formulations of Examples 1-7 and Comparative Polishing Solutions
Figure imgf000006_0001
Figure imgf000006_0001
BTA: 苯并三氮唑， PAA: 聚丙烯酸， PBTCA: 2-膦酸 -1,2,4-三羧酸丁烷。 DISN1, 亚甲 基双萘磺酸二钠盐， DISN2: 甲基萘磺酸盐甲醛縮合物， DISN3: 苄基萘磺酸盐甲醉缩合物。 BTA: benzotriazole, PAA: polyacrylic acid, PBTCA: 2-phosphonic acid - 1,2,4-tricarboxylic acid butane. DISN1, methylene bisnaphthalenesulfonic acid disodium salt, DISN2: methylnaphthalenesulfonate formaldehyde condensate, DISN3: benzylnaphthalenesulfonate methyl drunk condensate.
HPAA: 2-m zm HEDP: 羟基乙叉二膦酸。 参比抛光液为市售的阻挡层抛光液。 表 2、 效果数据 HPAA: 2-m zm HEDP: Hydroxyethylidene diphosphonic acid. The reference polishing liquid is a commercially available barrier polishing liquid. Table 2, effect data
Figure imgf000007_0001
从图 14中可以看出， 本抛光液和对比抛光液相比， 具有更高的 Ta和 Si02 的去除速率， 添加氮化硅抑制剂后， 使得氮化硅的去除速率小于 100A/min, 选择比达到 15-20。 能够较好地停止在氮化硅层， 络合剂以及组 合金属保护剂的共同作用下， 很好的保护金属铜， 未发现金属腐蚀， 且金属 的去除速率碎双氧水呈温和的线性变化。 抛光后表面的细线区域清晰锐利， 无颗粒物和有机物质残留等污染物。此外，对前程同抛光后的缺陷具有较大 幅度的校正， 具有较好的平坦化效率。 浸泡后， 图形片表面无明显变化， 显 示了较好的抗腐蚀性能。
Figure imgf000007_0001
As can be seen from Fig. 14, the polishing liquid has a higher removal rate of Ta and SiO2 than the comparative polishing liquid, and the removal rate of silicon nitride is less than 100 A/min after the addition of the silicon nitride inhibitor. The ratio is 15-20. It can better stop the silicon nitride layer, the complexing agent and the combined metal protective agent, and protect the metal copper well. No metal corrosion is found, and the metal removal rate of the hydrogen peroxide is mild and linear. The fine line area of the polished surface is clear and sharp, free of particulate matter and organic matter residues. In addition, the front-end and the polished defects have a large correction, and have better planarization efficiency. After soaking, there is no significant change in the surface of the graphic sheet, indicating good corrosion resistance.

Claims

权利要求 Rights request
I、 一种 TSV阻挡层抛光液， 其特征在于， 包含以下组分： 磨料、 组合 金属保护剂、 络合剂、 氧化剂、 氮化硅抑制剂和 pH调节剂。 I. A TSV barrier polishing fluid comprising the following components: an abrasive, a combination metal protectant, a complexing agent, an oxidizing agent, a silicon nitride inhibitor, and a pH adjusting agent.
2： 如权利要求 1所述的抛光液， 其特征在于， 所述磨料是二氧化硅溶 胶或气相法二氧化硅。  The polishing liquid according to claim 1, wherein the abrasive is silica sol or fumed silica.
3、 如权利要求 1或 2所述的抛光液， 其特征在于， 所述磨料的粒径为 20-200nm。  The polishing liquid according to claim 1 or 2, wherein the abrasive has a particle diameter of 20 to 200 nm.
4、 如权利要求 3所述的抛光液， 其特征在于， 所述磨料的粒径为 4C 20nm。  The polishing liquid according to claim 3, wherein the abrasive has a particle diameter of 4C 20 nm.
5、 如权利要求 1 或 2所述的抛光液， 其特征在于， 所述磨料含量为 10-50%。  The polishing liquid according to claim 1 or 2, wherein the abrasive content is 10-50%.
6、如权利要求 5所述的抛光液，其特征在于，所述磨料含量为 20-30%。  The polishing liquid according to claim 5, wherein the abrasive content is 20 to 30%.
7、 如权利要求 1所述的抛光液， 其特征在于， 所述组合金属保护剂包 括一种唑类化合物和一种水溶性聚合物。  The polishing liquid according to claim 1, wherein the combined metal protecting agent comprises an azole compound and a water-soluble polymer.
8、 如权利要求 7所述的抛光液， 其特征在于， 所述的唑类化合物为苯 并三氮唑及其衍生物； 所述水溶性聚合物为聚丙烯酸及其共聚物。  The polishing liquid according to claim 7, wherein the azole compound is benzotriazole and a derivative thereof; and the water-soluble polymer is polyacrylic acid and a copolymer thereof.
9、 如权利要求 1所述的抛光液， 其特征在于， 所述唑类化合物的浓度 为 0.01-0.5%; 所述水溶性聚合物的浓度为 0.005-0.1%。  The polishing liquid according to claim 1, wherein the concentration of the azole compound is 0.01 to 0.5%; and the concentration of the water-soluble polymer is 0.005 to 0.1%.
10、如权利要求 9所述的抛光液，其特征在于， 所述唑类化合物的浓度 为 0.05-0.2%; 所述水溶性聚合物的浓度为 0.01-0.05%。  The polishing liquid according to claim 9, wherein the concentration of the azole compound is 0.05 to 0.2%; and the concentration of the water-soluble polymer is 0.01 to 0.05%.
II、如权利要求 1所述的抛光液， 其特征在于， 所述的络合剂选自有机 磷酸， PBTCA, HPAA, HEDP, EDTMP和 ATMP中的一种或多种。 The polishing liquid according to claim 1, wherein the complexing agent is selected from the group consisting of organic One or more of phosphoric acid, PBTCA, HPAA, HEDP, EDTMP and ATMP.
12、 如权利要求 1 所述的抛光液， 其特征在于， 所述络合剂的浓度为 0.05% -1%。  The polishing liquid according to claim 1, wherein the concentration of the complexing agent is 0.05% to 1%.
13、 如权利要求 12所述的抛光液， 其特征在于， 所述络合剂的浓度为 0.1-0.5%。  The polishing liquid according to claim 12, wherein the complexing agent has a concentration of 0.1 to 0.5%.
14、如权利要求 1所述的抛光液， 其特征在于， 所述氮化硅抑制剂为一 种萘磺酸盐的甲醛缩聚物， 具有以下通式：
Figure imgf000009_0001
The polishing liquid according to claim 1, wherein the silicon nitride inhibitor is a formaldehyde polycondensate of a naphthalenesulfonate having the following formula:
Figure imgf000009_0001
15、 如权利要求 14所述的抛光液， 其特征在于， 所述氮化硅抑制剂为 亚甲基双萘磺酸二钠盐， 甲基萘磺酸甲醛缩聚物和 /或苄基萘磺酸甲醛缩聚 物。 The polishing liquid according to claim 14, wherein the silicon nitride inhibitor is methylene bis naphthalenesulfonic acid disodium salt, methyl naphthalenesulfonic acid formaldehyde polycondensate and/or benzyl naphthalenesulfonate. Acid formaldehyde polycondensate.
16、 如权利要求 1所述的抛光液， 其特征在于， 所述 pH调节剂为一种 有机羧酸。  The polishing liquid according to claim 1, wherein the pH adjuster is an organic carboxylic acid.
17、 如权利要求 16所述的抛光液， 其特征在于， 所述有机羧酸选自草 酸， 丙二酸， 丁二酸， 柠檬酸和酒石酸中的一种或多种。  The polishing liquid according to claim 16, wherein the organic carboxylic acid is one or more selected from the group consisting of oxalic acid, malonic acid, succinic acid, citric acid and tartaric acid.
18、如权利要求 1所述的抛光液， 其特征在于， 所述氧化剂为过氧化物 或过硫化物。  The polishing liquid according to claim 1, wherein the oxidizing agent is a peroxide or a persulfide.
19、 如权利要求 18所述的抛光液， 其特征在于， 所述氧化剂选自过氧 化氢， 过氧化钠， 过氧化钾， 过氧化苯甲酰， 过硫酸钠， 过硫酸钾和过硫酸 铵中的一种或多种。 （此处氧化剂需要每一种都出现在实施例中至少一次）The polishing liquid according to claim 18, wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, sodium peroxide, potassium peroxide, benzoyl peroxide, sodium persulfate, potassium persulfate and persulfuric acid. One or more of ammonium. (here oxidants need to be present at least once in the examples)
20、如权利要求 1所述的抛光液， 其特征在于， 所述抛光液还包括： 杀 菌防霉变剂。 The polishing liquid according to claim 1, wherein the polishing liquid further comprises: a bactericidal mold inhibitor.
21、 如权利要求 20所述的抛光液， 其特征在于， 所述杀菌防霉变剂为 季铵盐活性剂。  The polishing liquid according to claim 20, wherein the bactericidal mold inhibitor is a quaternary ammonium salt active agent.
22、 如权利要求 1所述的抛光液， 其特征在于， 所述抛光液的 pH值为 The polishing liquid according to claim 1, wherein a pH of the polishing liquid is
2-5。 2-5.
23、 如权利要求 22所述的抛光液， 其特征在于， 所述抛光液的 pH值 为 3~4。  The polishing liquid according to claim 22, wherein the polishing liquid has a pH of 3 to 4.
24、如权利要求 1所述的抛光液， 其特征在于，所述氮化硅抑制剂的浓 度从 50ppm到 0.1%。  The polishing liquid according to claim 1, wherein the silicon nitride inhibitor has a concentration of from 50 ppm to 0.1%.
PCT/CN2012/001016 2011-12-07 2012-07-30 Polishing liquid for tsv blocking layer WO2013082863A1 (en)

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CN103173127B (en) * 2011-12-23 2016-11-23 安集微电子（上海）有限公司 A kind of chemical mechanical polishing liquid for the planarization of silicon through-hole blocking layer
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101130665A (en) * 2006-08-25 2008-02-27 安集微电子（上海）有限公司 Polishing solution used for polishing low-dielectric materials
CN101168847A (en) * 2006-09-04 2008-04-30 株式会社荏原制作所 Electrolytic liquid for electrolytic polishing and electrolytic polishing method
WO2008157293A1 (en) * 2007-06-15 2008-12-24 Basf Se Controlling passivating film properties using colloidal particles polyelectrolytes, and ionic additives for copper chemical mechanical planarization

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6083840A (en) * 1998-11-25 2000-07-04 Arch Specialty Chemicals, Inc. Slurry compositions and method for the chemical-mechanical polishing of copper and copper alloys
US6964600B2 (en) * 2003-11-21 2005-11-15 Praxair Technology, Inc. High selectivity colloidal silica slurry
DE602006002900D1 (en) * 2005-03-09 2008-11-13 Jsr Corp Aqueous dispersion for chemical mechanical polishing, kit for their preparation and chemical-mechanical polishing process
WO2006112519A1 (en) * 2005-04-14 2006-10-26 Showa Denko K.K. Polishing composition
KR20080042043A (en) * 2005-09-09 2008-05-14 아사히 가라스 가부시키가이샤 Polishing agent, method for polishing surface to be polished, and method for manufacturing semiconductor integrated circuit device
WO2008013226A1 (en) * 2006-07-28 2008-01-31 Showa Denko K.K. Polishing composition
US20080149884A1 (en) * 2006-12-21 2008-06-26 Junaid Ahmed Siddiqui Method and slurry for tuning low-k versus copper removal rates during chemical mechanical polishing
JP5317436B2 (en) * 2007-06-26 2013-10-16 富士フイルム株式会社 Polishing liquid for metal and polishing method using the same
TW200923055A (en) * 2007-11-20 2009-06-01 Anji Microelectronics Co Ltd Chemical mechanical polishing slurry for low-k material
CN101463227B (en) * 2007-12-21 2013-06-12 安集微电子（上海）有限公司 Chemico-mechanical polishing solution for barrier layer
CN101463225A (en) * 2007-12-21 2009-06-24 安集微电子（上海）有限公司 Chemico-mechanical polishing solution for barrier layer
JP5441345B2 (en) * 2008-03-27 2014-03-12 富士フイルム株式会社 Polishing liquid and polishing method
JP5314329B2 (en) * 2008-06-12 2013-10-16 富士フイルム株式会社 Polishing liquid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101130665A (en) * 2006-08-25 2008-02-27 安集微电子（上海）有限公司 Polishing solution used for polishing low-dielectric materials
CN101168847A (en) * 2006-09-04 2008-04-30 株式会社荏原制作所 Electrolytic liquid for electrolytic polishing and electrolytic polishing method
WO2008157293A1 (en) * 2007-06-15 2008-12-24 Basf Se Controlling passivating film properties using colloidal particles polyelectrolytes, and ionic additives for copper chemical mechanical planarization

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