WO2019129103A1 - 一种化学机械抛光液 - Google Patents

一种化学机械抛光液 Download PDF

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WO2019129103A1
WO2019129103A1 PCT/CN2018/124049 CN2018124049W WO2019129103A1 WO 2019129103 A1 WO2019129103 A1 WO 2019129103A1 CN 2018124049 W CN2018124049 W CN 2018124049W WO 2019129103 A1 WO2019129103 A1 WO 2019129103A1
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chemical mechanical
mechanical polishing
polishing liquid
liquid according
acid
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PCT/CN2018/124049
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English (en)
French (fr)
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马健
荆建芬
杨俊雅
宋凯
蔡鑫元
汪国豪
姚颖
卞鹏程
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安集微电子（上海）有限公司
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Priority to US16/958,391 priority Critical patent/US11746257B2/en
Publication of WO2019129103A1 publication Critical patent/WO2019129103A1/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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F3/00—Brightening metals by chemical means
    • C23F3/04—Heavy metals
    • 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
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • 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
    • H01L21/3205—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

  • the invention relates to the field of chemical mechanical polishing liquids, in particular to a metal chemical mechanical polishing liquid.
  • an integrated circuit contains millions of transistors. Based on traditional aluminum or aluminum alloy interconnects, a large number of transistors that can be quickly switched are integrated, which reduces the signal transmission speed and consumes a large amount of energy during the current transfer process, thus hindering the development of semiconductor technology to some extent.
  • the copper interconnect can only be fabricated by a damascene process. That is, a trench is formed in the first layer, and a copper barrier layer and copper are filled in the trench to form a metal wire and overlying the dielectric layer. Thereafter, the excess copper/copper barrier layer on the dielectric layer is removed by chemical mechanical polishing, leaving a single interconnect line in the trench.
  • the chemical mechanical polishing process of copper is generally divided into three steps.
  • the first step uses a higher downforce to remove a large amount of copper on the surface of the substrate and leave a certain thickness of copper at a fast and efficient removal rate.
  • the lower removal rate removes the remaining metallic copper and stops at the barrier layer.
  • step 3 the barrier layer and a portion of the dielectric layer and metallic copper are removed by a barrier polishing solution to achieve planarization.
  • the metal layer is partially recessed above the copper wire.
  • the copper on the dielectric material is easily removed (higher) at the bulk pressure, while the copper at the depression is subjected to a lower polishing pressure than the bulk pressure, and the copper removal rate is small.
  • the height difference of the copper is gradually reduced to achieve planarization.
  • the chemical action of the copper polishing solution is too strong and the static etching rate is too high, the passivation film of copper is easily removed even at a lower pressure (such as a copper line depression), resulting in planarization efficiency. Reduced, the dished dish after polishing increases. Therefore, for the chemical mechanical polishing of copper, on the one hand, it is necessary to remove excess copper on the barrier layer as soon as possible, and on the other hand, it is necessary to minimize the dishing of the polished copper wire.
  • the line width is narrower and narrower, and the dielectric layer uses a low dielectric with low mechanical strength ( Low-k) materials
  • the number of layers of wiring is also more and more
  • the requirements for copper chemical mechanical polishing are also higher and higher. It is required to reduce the polishing pressure while ensuring the removal rate of copper, improve the flattening of the surface of the copper wire, and control surface defects.
  • the linewidth cannot be reduced indefinitely, and the semiconductor industry no longer relies on integrating more devices on a single chip to improve performance, but instead shifts to multi-chip packages.
  • the rear copper wire has a dish shape and has no defects such as copper residue and corrosion after polishing.
  • the present invention provides a metal chemical mechanical polishing liquid by adding a broad distribution of silica abrasive particles, a benzene ring-free azole-based corrosion inhibitor, and a polyacrylic anionic surfactant to a polishing liquid.
  • the combination improves the polishing selectivity ratio of the copper to tantalum barrier layer, improves the dishing of the copper wire after polishing and the erosion of the dielectric layer, and has no defects such as copper residue and corrosion after polishing.
  • the present invention provides a chemical mechanical polishing liquid comprising silica abrasive particles, a corrosion inhibitor, a complexing agent, an oxidizing agent, and at least one polyacrylic anionic surfactant.
  • the abrasive particles have an average particle diameter of from 60 to 140 nm, more preferably from 80 to 120 nm.
  • the abrasive particles have a particle size distribution index (PdI) of from 0.1 to 0.6.
  • PdI particle size distribution index
  • the abrasive particles have a concentration of from 0.05 to 2% by weight, more preferably from 0.1 to 1% by weight.
  • the polyacrylic anionic surfactant is a polyacrylic acid homopolymer and/or copolymer and a salt of a polyacrylic acid homopolymer and/or copolymer.
  • the polyacrylic acid homopolymer is polyacrylic acid and/or polymaleic acid;
  • the polyacrylic acid copolymer is a polyacrylic acid-polyacrylate copolymer and/or a polyacrylic acid-polymaleic acid copolymer
  • the salt of the polyacrylic acid homopolymer and/or copolymer is a potassium salt, an ammonium salt and/or a sodium salt.
  • the polyacrylic anionic surfactant has a molecular weight of from 1,000 to 10,000, more preferably from 2,000 to 5,000.
  • the polyacrylic anionic surfactant has a concentration of 0.0005 to 0.5% by weight, more preferably 0.001 to 0.1% by weight.
  • the complexing agent is an aminocarboxylate compound and a salt thereof.
  • the complexing agent is selected from the group consisting of glycine, alanine, valine, leucine, valine, phenylalanine, tyrosine, tryptophan, lysine, arginine, group Amino acid, serine, aspartic acid, glutamic acid, asparagine, glutamine, ammonia triacetic acid, ethylenediaminetetraacetic acid, cyclohexanediaminetetraacetic acid, ethylenediamine disuccinic acid, diethylenetriamine One or more of pentaacetic acid and triethylenetetramine hexaacetic acid.
  • the complexing agent is present in an amount of from 0.1 to 5% by weight, more preferably from 0.5 to 3% by weight.
  • the corrosion inhibitor is one or more of a benzene ring-free azole compound.
  • the corrosion inhibitor is selected from the group consisting of 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 3, 5-diamino-1,2,4-triazole, 5-carboxy-3-amino-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole
  • 1,2,4-triazole 3-amino-1,2,4-triazole
  • 4-amino-1,2,4-triazole 3, 5-diamino-1,2,4-triazole, 5-carboxy-3-amino-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole
  • 5-acetic acid-1H-tetrazole 5-methyltetrazolium and 5-amino-1H-tetrazole.
  • the corrosion inhibitor is contained in an amount of 0.001 to 2% by weight, more preferably 0.005 to 1% by weight.
  • the oxidizing agent is hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, persulfate, percarbonate, periodic acid, perchloric acid, perboric acid, potassium permanganate and ferric nitrate One or more of them.
  • the oxidizing agent is hydrogen peroxide.
  • the concentration of the oxidizing agent is from 0.05 to 5% by weight, more preferably from 0.1 to 3% by weight.
  • the chemical mechanical polishing liquid has a pH of 6 to 9.
  • the polishing liquid of the present invention may further include other usual additives such as a pH adjuster, a viscosity modifier, an antifoaming agent, etc. to achieve a polishing effect.
  • the polishing liquid of the present invention can be used in a concentrated configuration, diluted with deionized water at the time of use, and added with an oxidizing agent to the concentration range of the present invention.
  • Example 2 is a topographical view of a dense line array region in a copper pattern chip polished in Example 25.
  • Table 1 shows Examples 1 to 4 of the chemical mechanical polishing liquid of the present invention. According to the formulation given in the table, the components other than the oxidizing agent were uniformly mixed, and the mass percentage was made up to 100% with water. Adjust to the desired pH with KOH or HNO 3 . Add oxidizing agent before use and mix well.
  • Table 2 shows Examples 25 to 35 and Comparative Examples 1 to 6 of the chemical mechanical polishing liquid of the present invention, according to the formulation given in the table, the components other than the oxidizing agent were uniformly mixed, and the mass percentage was made up to 100 with water. %. Adjust to the desired pH with KOH or HNO 3 . Add oxidizing agent before use and mix well.
  • the empty copper (Cu) and tantalum (Ta) were polished using the comparative polishing liquid 1-6 and the polishing liquid 5 of the present invention under the following conditions.
  • polishing conditions lower pressure 1.5 psi, 2.0 psi; polishing disc and polishing head speed 73/67 rpm, polishing pad IC1010, polishing liquid flow rate 350 ml/min, polishing machine table 12" Reflexion LK, polishing time 1 min.
  • the patterned copper wafer was polished using the comparative polishing liquid and the polishing liquid of the present invention under the following conditions.
  • Polishing conditions polishing disc and polishing head rotation speed 73/67 rpm, polishing pad IC1010, polishing liquid flow rate 350 ml/min, polishing machine table 12" Reflexion LK. Polished patterned copper wafer was polished on the polishing disc 1 with a pressure of 2 psi to Residual copper was about 4000 A, and then residual copper was removed on a polishing disc 2 with a pressure of 1.5 psi. A 5/1 um (copper wire/silica) array on a patterned copper wafer was measured using an XE-300P atomic force microscope. The dishing value (Dishing) and the dielectric layer erosion value (Erosion) are shown in Table 3.
  • Table 3 compares the polishing effects of the polishing liquids 1 to 6 and the polishing liquids 25 to 35 of the present invention.
  • Comparative Polishing Liquid 1, 2 and Examples 25 and 26 it can be seen from Comparative Polishing Liquid 1, 2 and Examples 25 and 26 that when the abrasive particles have a large particle size but a narrow particle size distribution (less PdI) or a small particle size but a large particle size distribution (PdI) When it is large, the polishing speed of Cu is relatively low. Only the particle size and distribution of the abrasive particles are within a certain range, and the polishing speed of Cu is increased. The addition of a polyacrylic anionic surfactant controls the removal rate of Ta to a lower state, thereby achieving a high Cu/Ta polishing selectivity ratio of up to 2,200. Further, in comparison with Comparative Examples 1-6, the polishing liquid example 25 was able to further control the dishing value and the dielectric layer erosion value of the wafer while having an ultra-high Cu/Ta polishing selection ratio.
  • the surface topography of the dense line array region in which the copper wire width of the copper pattern chip polished in Comparative Example 5 and Example 25 is 5 micrometers and the dielectric material width is 1 micrometer is used.
  • Comparative Example 5 as a polishing liquid
  • the polished copper wire has 89.1 nm nano dish dishing and 59.2 nm dielectric layer etching; and using Example 25 as a polishing liquid, polished copper
  • the wire dish type depression is reduced to 43 nm, and the dielectric layer erosion is reduced to 0.2 nm.
  • the polishing liquid of the present invention has a remarkable effect on the surface morphology of the polished surface, particularly the erosion of the dielectric layer.
  • Example 25 in combination with the components of Example 25 and Comparative Example 6, it was found that the combination of the azole ring corrosion inhibitor benzotriazole and the polyacrylic anionic surfactant having a benzene ring was selected, although the removal of hydrazine was reduced. The rate, but greatly reduced the copper removal rate, could not effectively remove copper.
  • Comparative Examples 3 and 4 were added using a combination of an azole corrosion inhibitor without a benzene ring and a polyacrylic anionic surfactant, but the pH of Comparative Example 3 was too low, copper and The removal rate of ruthenium is also high, resulting in large dishing and dielectric layer erosion. The pH of Comparative Example 4 was too high, resulting in a greatly reduced copper removal rate and inability to effectively remove copper.
  • the present invention not only ensures high copper removal rate but also reduces surface defects by using abrasive particles of PdI within a certain range. And by adding a combination of a benzene ring-free azole-free corrosion inhibitor and a polyacrylic anionic surfactant to the polishing liquid, the high removal rate of copper is maintained, the removal rate of the ruthenium barrier layer is lowered, and polishing is improved.
  • the effect of the liquid on the polishing selectivity ratio of the copper to the ruthenium barrier layer; the polishing of the wafer of the present invention can improve the dishing and dielectric corrosion of the polished copper wire, and has no copper residue after polishing and No defects such as corrosion.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

本发明公开了一种化学机械抛光液，所述化学机械抛光液包含二氧化硅研磨颗粒，腐蚀抑制剂，络合剂，氧化剂，和至少一种聚丙烯酸类阴离子表面活性剂。本发明的化学机械抛光液能够提高铜去除速率的同时降低钽的去除速率，改善抛光后铜线的碟形凹陷、介质层侵蚀。

Description

一种化学机械抛光液 技术领域
本发明涉及化学机械抛光液领域，尤其涉及一种金属化学机械抛光液。
背景技术
随着半导体技术的发展，电子部件的微小化，一个集成电路中包含了数以百万计的晶体管。基于传统的铝或是铝合金互连线整合了大量能迅速开关的晶体管，降低了信号传递速度，并且在电流传递过程中消耗了大量能源，因此，在一定程度上阻碍了半导体技术的发展。
为此，人们开始寻找具有更高电学性质的材料来取代铝。众所周知，铜的电阻小，拥有良好的导电性，能够加快电路中晶体管间信号的传递速度，还可提供更小的寄生电容能力，从而减小电路对于电迁移的敏感性。因此，上述电学优点使得铜在半导体技术发展中具有良好的发展前景。
但，在铜的集成电路制造过程中，人们发现铜会迁移或扩散进入到集成电路的晶体管区域，从而对于半导体中的晶体管性能产生不利影响，因而铜的互连线只能通过镶嵌工艺制造，即：在第一层里形成沟槽，在沟槽内填充铜阻挡层和铜，以形成金属导线并覆盖在介电层上。其后，通过化学机械抛光将介电层上多余的铜/铜阻挡层除去，最终在沟槽里留下单个互连线。
铜的化学机械抛光过程一般分为3个步骤，第1步采用较高的下压力，以快且高效的去除速率去除衬底表面上大量的铜并留下一定厚度的铜，第2步用较低去除速率去除剩余的金属铜并停在阻挡层，第3步再用阻挡层抛光液去除阻挡层及部分介电层和金属铜，从而实现平坦化。
然而，在铜抛光前，金属层在铜线上方有部分凹陷。抛光时，介质材料 上的铜在主体压力下(较高)易于被去除，而凹陷处的铜所受的抛光压力比主体压力低，铜去除速率小。随着抛光的进行，铜的高度差会逐渐减小，从而达到平坦化。但是在抛光过程中，如果铜抛光液的化学作用太强，静态腐蚀速率太高，则铜的钝化膜即使在较低压力下(如铜线凹陷处)也易于被去除，导致平坦化效率降低，抛光后的碟形凹陷增大。因此，对于铜的化学机械抛光而言，一方面需要尽快去除阻挡层上多余的铜，另一方面需要尽量减小抛光后铜线的碟形凹陷。
随着集成电路的发展，一方面，在传统的IC行业中，为了提高集成度，降低能耗，缩短延迟时间，线宽越来越窄，介电层使用机械强度较低的低介电(low-k)材料，布线的层数也越来越多，为了保证集成电路的性能和稳定性，对铜化学机械抛光的要求也越来越高。要求在保证铜的去除速率的情况下降低抛光压力，提高铜线表面的平坦化，控制表面缺陷。另一方面，由于物理局限性，线宽不能无限缩小，半导体行业不再单纯地依赖在单一芯片上集成更多的器件来提高性能，而转向于多芯片封装。
随着半导体制造工艺的发展，为了使铜在半导体技术中更好的应用，亟需一种金属化学机械抛光液，能够提供铜的去除速率，以及铜与钽阻挡层的抛光选择比，改善抛光后铜线的碟形，且抛光后无铜残留和腐蚀等缺陷。
发明内容
为了解决上述问题，本发明提供了一种金属化学机械抛光液，通过在抛光液中添加宽分布二氧化硅研磨颗粒、不含苯环的氮唑类腐蚀抑制剂和聚丙烯酸类阴离子表面活性剂的组合，提高了铜与钽阻挡层的抛光选择比，改善抛光后铜线的碟形凹陷和介质层侵蚀，且抛光后无铜残留和腐蚀等缺陷
本发明提供了一种化学机械抛光液，所述化学机械抛光液包含二氧化硅研磨颗粒，腐蚀抑制剂，络合剂，氧化剂，和至少一种聚丙烯酸类阴离子表面活性剂。
优选地，所述研磨颗粒的平均粒径为60～140nm，更优选地为80～120nm。
优选地，所述研磨颗粒的粒径分布指数(PdI)为0.1～0.6。
优选地，所述研磨颗粒的浓度为0.05～2wt％，更优选地为0.1～1wt％。
优选地，所述聚丙烯酸类阴离子表面活性剂为聚丙烯酸均聚物和/或共聚物及聚丙烯酸均聚物和/或共聚物的盐。
优选地，所述聚丙烯酸类均聚物为聚丙烯酸和/或聚马来酸；所述聚丙烯酸类共聚物为聚丙烯酸-聚丙烯酸酯共聚物和/或聚丙烯酸-聚马来酸共聚物；所述聚丙烯酸均聚物和/或共聚物的盐为钾盐、铵盐和/或钠盐。
优选地，所述聚丙烯酸类阴离子表面活性剂的分子量为1,000～10,000，更优选地为2,000～5,000。
优选地，所述聚丙烯酸类阴离子表面活性剂浓度为0.0005～0.5wt％，更优选地为0.001～0.1wt％
优选地，所述络合剂为氨羧化合物及其盐。
优选地，所述络合剂选自甘氨酸、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、谷氨酸、天冬酰胺、谷氨酰胺、氨三乙酸、乙二胺四乙酸、环己二胺四乙酸、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。
优选地，所述络合剂含量为0.1～5wt％，更优选地为0.5～3wt％。
优选地，所述腐蚀抑制剂为不含苯环的氮唑类化合物中的一种或多种。
优选地，所述腐蚀抑制剂选自1，2，4-三氮唑、3-氨基-1，2，4-三氮唑、4-氨基-1，2，4-三氮唑、3，5-二氨基-1，2，4-三氮唑、5-羧基-3-氨基-1，2，4-三氮唑、3-氨基-5-巯基-1，2，4-三氮唑、5-乙酸-1H-四氮唑、5-甲基四氮唑和5-氨基-1H-四氮唑中的一种或多种。
优选地，所述腐蚀抑制剂的含量为0.001～2wt％，更优选地为0.005～1wt％。
优选地，所述氧化剂为过氧化氢、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。
优选地，所述氧化剂为过氧化氢。
优选地，所述氧化剂的浓度为0.05～5wt％，更优选地为0.1～3wt％。
优选地，所述化学机械抛光液的pH为6～9。
本发明的抛光液中还可以包括其他常用添加剂如pH调节剂，粘度调节剂，消泡剂等来达到抛光效果。
本发明的抛光液可以浓缩配置，在使用时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。
与现有技术相比较，本发明的技术优势在于：
1.提高铜去除速率的同时降低钽的去除速率；
2.可以改善抛光后铜线的碟形凹陷和介质层侵蚀；
附图说明
图1为使用对比例5抛光后的铜图形芯片中的密线阵列区表面形貌图；
图2为使用实施例25抛光后的铜图形芯片中的密线阵列区表面形貌图。
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点，但本发明的保护范围不仅仅局限于下述实施例。
表1给出了本发明的化学机械抛光液的实施例1～4，按表中所给配方，将除氧化剂以外的其他组分混合均匀，用水补足质量百分比至100％。用KOH或HNO 3调节到所需要的pH值。使用前加氧化剂，混合均匀即可。
表1本发明的抛光液1～24
Figure PCTCN2018124049-appb-000001
Figure PCTCN2018124049-appb-000002
Figure PCTCN2018124049-appb-000003
Figure PCTCN2018124049-appb-000004
Figure PCTCN2018124049-appb-000005
效果实施例
表2给出了本发明的化学机械抛光液的实施例25～35及对比实施例1～6，按表中所给配方，将除氧化剂以外的其他组分混合均匀，用水补足质量百分比至100％。用KOH或HNO 3调节到所需要的pH值。使用前加氧化剂，混合均匀即可。
表2对比实施例1～6和实施例25～35
Figure PCTCN2018124049-appb-000006
Figure PCTCN2018124049-appb-000007
采用对比抛光液1-6和本发明的抛光液5按照下述条件对空片铜(Cu) 和钽(Ta)进行抛光。
具体抛光条件：下压力1.5psi，2.0psi；抛光盘及抛光头转速73/67rpm，抛光垫IC1010，抛光液流速350ml/min，抛光机台为12”Reflexion LK，抛光时间为1min。
采用对比抛光液和本发明的抛光液按照下述条件对含图形的铜晶圆进行抛光。
抛光条件：抛光盘及抛光头转速73/67rpm，抛光垫IC1010，抛光液流速350ml/min，抛光机台为12”Reflexion LK。在抛光盘1上用2psi的下压力抛光有图案的铜晶片至残留铜约4000A，然后再在抛光盘2上用1.5psi的下压力将残留的铜去除。用XE-300P原子力显微镜测量有图案的铜晶片上5/1um(铜线/二氧化硅)的阵列处的蝶型凹陷值(Dishing)和介质层侵蚀值(Erosion)，结果如表3。
表3对比抛光液1～6和本发明抛光液25～35的抛光效果
Figure PCTCN2018124049-appb-000008
Figure PCTCN2018124049-appb-000009
参阅表2和表3可知，由对比抛光液1，2与实施例25，26可知，当研磨颗粒的粒径大但粒径分布窄(PdI小)或粒径小但粒径分布宽(PdI大)时，Cu的抛光速度都比较低。只有研磨颗粒的粒径和分布在一定范围内，Cu的抛光速度提高。聚丙烯酸类阴离子表面活性剂的加入可控制Ta的去除速率呈较低状态，从而实现高的Cu/Ta抛光选择比，可达2200。此外，与对比例1-6相比，抛光液实施例25在具有超高Cu/Ta抛光选择比的基础上，同时能进一步控制晶圆的碟形凹陷值和介质层侵蚀值。
进一步参阅图1及图2，其分别为使用对比例5及实施例25抛光后的铜图形芯片中铜线宽为5微米，介电材料宽为1微米的密线阵列区表面形貌图。从图中可以看出，使用对比例5作为抛光液，抛光后的铜线存在89.1纳米纳米的碟型凹陷和59.2纳米的介质层侵蚀；而使用本实施例25作为抛光液，抛光后的铜线碟型凹陷减低至43纳米，介质层侵蚀降至0.2纳米，本发明的抛光液对抛光后的表面形貌特别是介质层的侵蚀的减低效果非常显著。同时，结合实施例25与对比例6的组分比较可发现，选择带有苯环的唑类腐蚀抑制剂苯并三氮唑和聚丙烯酸类阴离子表面活性剂的组合，虽然能降低钽的去除速率，但大大抑制了铜的去除速率，无法有效地去除铜。与本发明实施例25相比，对比例3和4加入采用了不带苯环的唑类腐蚀抑制剂和聚丙烯酸类阴离子表面活性剂的组合，但对比例3的pH值过低，铜和钽的去除速率也较高，导致碟型凹陷和介质层侵蚀均较大。而对比例4的pH值过高，导致铜的去除速率大大降低，无法有效去除铜。
综上所述，本发明通过使用PdI在一定范围内的研磨颗粒，既保证了高的铜去除速率，又降低了表面缺陷。和通过在抛光液中添加不含苯环的氮唑类腐蚀抑制剂和聚丙烯酸类阴离子表面活性剂的组合，维持了铜的高去除速率，降低了钽阻挡层的去除速率，实现了提高抛光液对铜与钽阻挡层的抛光选择比的功效；本发明用于晶片的抛光可改善抛光后铜线的碟型凹陷(Dishing)和介质层侵蚀(Erosion)，且抛光后无铜残留物以及无腐蚀等缺陷。
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 (25)

  1. 一种化学机械抛光液，其特征在于，所述化学机械抛光液包含二氧化硅研磨颗粒，腐蚀抑制剂，络合剂，氧化剂，和至少一种聚丙烯酸类阴离子表面活性剂。
  2. 如权利要求1所述的化学机械抛光液，其特征在于，所述研磨颗粒的平均粒径为60～140nm。
  3. 如权利要求2所述的化学机械抛光液，其特征在于，所述研磨颗粒的平均粒径为80～120nm。
  4. 如权利要求1所述的化学机械抛光液，其特征在于，所述研磨颗粒的粒径分布指数(PdI)为0.1～0.6。
  5. 如权利要求1所述的化学机械抛光液，其特征在于，所述研磨颗粒的浓度为0.05～2wt％。
  6. 如权利要求5所述的化学机械抛光液，其特征在于，所述研磨颗粒的浓度为0.1～1wt％。
  7. 如权利要求1所述的化学机械抛光液，其特征在于，所述聚丙烯酸类阴离子表面活性剂为聚丙烯酸均聚物和/或共聚物及聚丙烯酸均聚物和/或共聚物的盐。
  8. 如权利要求7所述的化学机械抛光液，其特征在于，所述聚丙烯酸类均聚物为聚丙烯酸和/或聚马来酸；所述聚丙烯酸类共聚物为聚丙烯酸-聚丙烯酸酯共聚物和/或聚丙烯酸-聚马来酸共聚物；所述聚丙烯酸均聚物和/或共聚物的盐为钾盐、铵盐和/或钠盐。
  9. 如权利要求1所述的化学机械抛光液，其特征在于，所述聚丙烯酸类阴离子表面活性剂的分子量为1,000～10,000。
  10. 如权利要求9所述的化学机械抛光液，其特征在于，所述聚丙烯酸类阴离子表面活性剂的分子量为2,000～5,000。
  11. 如权利要求1所述的化学机械抛光液，其特征在于，所述聚丙烯酸类阴离子表面活性剂浓度为0.0005～0.5wt％。
  12. 如权利要求11所述的化学机械抛光液，其特征在于，所述聚丙烯酸类阴离子表面活性剂浓度为0.001～0.1wt％。
  13. 如权利要求1所述的化学机械抛光液，其特征在于，所述络合剂为氨羧化合物及其盐。
  14. 如权利要求13所述的化学机械抛光液，其特征在于，所述络合剂选自甘氨酸、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、谷氨酸、天冬酰胺、谷氨酰胺、氨三乙酸、乙二胺四乙酸、环己二胺四乙酸、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。
  15. 如权利要求1所述的化学机械抛光液，其特征在于，所述络合剂含量为0.1～5wt％。
  16. 如权利要求15所述的化学机械抛光液，其特征在于，所述络合剂含量为0.5～3wt％。
  17. 如权利要求1所述的化学机械抛光液，其特征在于，所述腐蚀抑制剂为不含苯环的氮唑类化合物中的一种或多种。
  18. 如权利要求17所述的化学机械抛光液，其特征在于，所述腐蚀抑制剂选自1，2，4-三氮唑、3-氨基-1，2，4-三氮唑、4-氨基-1，2，4-三氮唑、3，5-二氨基-1，2，4-三氮唑、5-羧基-3-氨基-1，2，4-三氮唑、3-氨基-5-巯基-1，2，4-三氮唑、5-乙酸-1H-四氮唑、5-甲基四氮唑和5-氨基-1H-四氮唑中的一种或多种。
  19. 如权利要求1所述的化学机械抛光液，其特征在于，所述腐蚀抑制剂的含量为0.001～2wt％。
  20. 如权利要求19所述的化学机械抛光液，其特征在于，所述腐蚀抑制剂的含量为0.005～1wt％。
  21. 如权利要求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。
  22. 如权利要求21所述的化学机械抛光液，其特征在于，所述氧化剂为过氧化氢。
  23. 如权利要求1所述的化学机械抛光液，其特征在于，所述氧化剂的浓度为0.05～5wt％。
  24. 如权利要求23所述的化学机械抛光液，其特征在于，所述氧化剂的浓度为0.1～3wt％。
  25. 如权利要求1～24任一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为6～9。
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