CN111004579B - Alkaline polishing solution for reducing CMP defects of multilayer copper interconnection barrier layer and preparation method thereof - Google Patents
Alkaline polishing solution for reducing CMP defects of multilayer copper interconnection barrier layer and preparation method thereof Download PDFInfo
- Publication number
- CN111004579B CN111004579B CN201911184055.1A CN201911184055A CN111004579B CN 111004579 B CN111004579 B CN 111004579B CN 201911184055 A CN201911184055 A CN 201911184055A CN 111004579 B CN111004579 B CN 111004579B
- Authority
- CN
- China
- Prior art keywords
- polishing solution
- chelating agent
- surfactant
- defects
- deionized water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 66
- 230000007547 defect Effects 0.000 title claims abstract description 53
- 230000004888 barrier function Effects 0.000 title claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 11
- 239000010949 copper Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000002738 chelating agent Substances 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims description 36
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 30
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 19
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 19
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- 239000006172 buffering agent Substances 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 229940063953 ammonium lauryl sulfate Drugs 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims 1
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- 239000013543 active substance Substances 0.000 abstract description 32
- 239000004094 surface-active agent Substances 0.000 abstract description 26
- 125000000129 anionic group Chemical group 0.000 abstract description 12
- 239000006185 dispersion Substances 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 238000013329 compounding Methods 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 abstract description 4
- 239000006184 cosolvent Substances 0.000 abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 47
- 238000012360 testing method Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 238000012544 monitoring process Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 230000001502 supplementing effect Effects 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- GTGUCSIFKYFMNY-UHFFFAOYSA-N dodecylazanium;hydrogen sulfate Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCN GTGUCSIFKYFMNY-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 description 1
- BYACHAOCSIPLCM-UHFFFAOYSA-N 2-[2-[bis(2-hydroxyethyl)amino]ethyl-(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)CCN(CCO)CCO BYACHAOCSIPLCM-UHFFFAOYSA-N 0.000 description 1
- 230000005653 Brownian motion process Effects 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 229940093928 potassium nitrate Drugs 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000001472 potassium tartrate Substances 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- 235000011005 potassium tartrates Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
本发明属于抛光液领域，具体涉及一种用于降低多层铜互连阻挡层CMP缺陷的碱性抛光液及其制备方法。抛光液由下述组分组成，按质量份百分比计：硅溶胶5‑20％，螯合剂0.1‑5％，表面活性剂0.001‑5％，氧化剂0.001‑10％，去离子水余量；其中，所述的表面活性剂为非离子活性剂和阴离子活性剂进行复配获得。本发明抛光液呈碱性，pH为7.5‑11，不腐蚀设备，不污染环境。本发明使用纳米SiO2溶胶作为抛光液磨料，其浓度高，分散度好、硬度小。本发明由硅溶胶、螯合剂、表面活性剂、助溶剂、氧化剂和去离子水组成，成分简单，稳定性好，价格便宜。
The invention belongs to the field of polishing liquids, and in particular relates to an alkaline polishing liquid for reducing CMP defects of multilayer copper interconnection barrier layers and a preparation method thereof. The polishing liquid is composed of the following components, calculated by mass percentage: 5-20% of silica sol, 0.1-5% of chelating agent, 0.001-5% of surfactant, 0.001-10% of oxidant, and the balance of deionized water; wherein , and the surfactant is obtained by compounding a nonionic active agent and an anionic active agent. The polishing liquid of the invention is alkaline and has a pH of 7.5-11, which does not corrode equipment and does not pollute the environment. The invention uses nano-SiO2 sol as polishing liquid abrasive, which has high concentration, good dispersion and low hardness. The invention is composed of silica sol, chelating agent, surfactant, cosolvent, oxidant and deionized water, and has simple components, good stability and low price.
Description
Technical Field
The invention belongs to the field of polishing solution, and particularly relates to alkaline polishing solution for reducing the CMP defects of a multilayer copper interconnection barrier layer and a preparation method thereof.
Background
At present, the development trend of integrated circuit technology is as follows: increased wafer size, increased number of active devices, and reduced feature size. Planarization becomes more challenging and also places more stringent requirements on planarization, a flat surface, as little surface damage as possible, and a sufficiently small surface roughness. The role of Chemical Mechanical Planarization (CMP) is becoming more important as a key technology for global Planarization of large-size wafer chips.
CMP is used as a main planarization technology, which achieves planarization of a material surface through chemical reaction and mechanical friction, is applied to very large scale integrated circuits, and has local and global planarization effects. However, various defects may be formed on the surface of the workpiece during the CMP process. Including residues (organic residues and copper residues), particle adsorption, corrosion, scratch and the like, which all affect the reliability, electrical performance and other properties of the device, and more seriously may cause the functional failure of the device.
Scratch defects, which are the most common defects in the CMP process, are mainly generated in the mechanical rubbing process, which may reduce the thickness of the wiring metal, increase the resistance, and deteriorate the electromigration resistance. The micro-scratches are mainly caused by large particles (particle size >0.5 μm) in the polishing slurry. And the generation of the scratch defects is not irreversible, the generated scratch defects cannot be removed or reduced, and the scratch defects can be further reduced only by researching the generation reasons of the scratch defects. The formation of scratches is critical because they affect the yield and reliability of the device. It has been found that CMP scratches not only cause initial failure, but also long term reliability failure, and can lead to device failure, yield loss, and potential reliability problems. Previous researchers have mentioned reducing the amount of large particles and thus scratching by adding a slurry filtration system, but the abrasive particles in the slurry tend to stick to each other to form agglomerates when they come into contact due to brownian motion. Therefore, it is necessary to invent a polishing solution capable of effectively reducing scratch defects.
Disclosure of Invention
The invention aims to provide an alkaline polishing solution for reducing the CMP defects of a multi-layer copper interconnection barrier layer and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
an alkaline polishing solution for reducing the CMP defects of a multi-layer copper interconnection barrier layer comprises the following components in percentage by mass:
wherein, the surfactant is obtained by compounding a nonionic active agent and an anionic active agent.
The surfactant is one or a mixture of any nonionic surfactant and anionic surfactant selected from dodecyl dimethyl amine oxide OA, fatty alcohol-polyoxyethylene ether JFC, FA/O surfactant, fatty alcohol-polyoxyethylene ether AEO-7, polyvinylpyrrolidone PVP, fatty alcohol-polyoxyethylene ether ammonium sulfate AESA, sodium dodecyl sulfate SDS, sodium dodecyl benzene sulfonate SDBS, ammonium dodecyl sulfate ADS and dodecyl benzene sulfonate LABSA.
The pH value of the alkaline polishing solution is 7.5-11.
The mass percent of the surfactant is 0.26-0.75%, and the non-surfactant in the surfactant contains fatty alcohol polyoxyethylene ether.
The surfactant is a compound of fatty alcohol-polyoxyethylene ether, ammonium lauryl sulfate and dodecyl dimethyl amine oxide, and the mass ratio of the surfactant is 4 parts of fatty alcohol-polyoxyethylene ether; 2 parts of ammonium dodecyl sulfate; 1.5 parts of dodecyl dimethyl amine oxide.
Preferably, the alkaline polishing solution for reducing the CMP defects of the multilayer copper interconnection barrier layer comprises the following components in parts by mass:
more preferably, the alkaline polishing solution for reducing the CMP defects of the multilayer copper interconnection barrier layer comprises the following components in parts by mass:
the particle size of the silica sol is 50nm-90nm, and the dispersion degree is +/-3%; the chelating agent is one or any mixture of FA/O chelating agent, tetrahydroxyethyl ethylenediamine, ethylenediamine and triethanolamine;
the cosolvent is one or any mixture of potassium nitrate, potassium citrate, potassium tartrate, ammonium citrate and ammonium sulfate; the oxidant is one or any mixture of hydrogen peroxide, peroxyacetic acid, ammonium persulfate, potassium persulfate and potassium periodate.
The invention also comprises a preparation method of the alkaline polishing solution for reducing the CMP defects of the multilayer copper interconnection barrier layer, which comprises the following specific steps:
solution A: adding a chelating agent, a surfactant, a cosolvent and an oxidant into a proper amount of deionized water in sequence according to the component amounts, and uniformly stirring in a step-by-step mixing manner;
and B, liquid B: weighing silica sol according to the components, and adding the silica sol into a proper amount of deionized water;
and adding the solution A into the solution B in a mode of stirring while pouring, and finally complementing the solution A with deionized water.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts the compounding of the nonionic active agent and the anionic active agent, and can reduce the number of large particles in the polishing solution through the steric hindrance effect. The addition of the composite active agent in the polishing solution obviously reduces the number of large particles in the polishing solution. Due to the surface effect of the nano material, the surface of the SiO2 particle has a plurality of charges or functional groups and high surface energy, and the characteristics determine that the surface energy of the SiO2 particle tends to be small and agglomeration phenomenon occurs. After the composite active agent is added into the polishing solution, the hydrophilic group of the anionic active agent is fully extended in the aqueous solution, and the lipophilic group is adsorbed on the surface of the particles to form a layer of film. When the particles are close to each other, the repulsion energy exists in the boundary area, so that the particles can keep enough safe distance to generate steric hindrance effect, further the molecular reaction activity is reduced, and the collision focus and gravity sedimentation of the particles are hindered. The active agent adsorbed on the surface of the particle not only repels surrounding particles by its own charge, but also prevents particles moving brownian from approaching by hydrophobic groups and steric resistance effect, thereby generating a composite stabilization effect. The nonionic surfactant has the functions of penetration, infiltration and dispersion, is introduced into the polishing solution to reduce the contact angle and the surface tension, greatly enhances the infiltration and the permeability, and is better spread on the polished surface. The synergistic effect of the surfactants reduces the agglomeration capacity of the particles, so that the abrasive particles keep a stable state with the lowest energy, and finally the stability of the whole system is achieved, so that the number of large particles in the polishing solution is reduced, and the number of surface defects in the barrier layer CMP is reduced.
The polishing solution of the invention is alkaline, has pH of 7.5-11, does not corrode equipment, and does not pollute the environment.
The invention uses the nano SiO2 sol as the polishing liquid abrasive, and has high concentration, good dispersion degree and small hardness.
The invention is composed of silica sol, chelating agent, surfactant, cosolvent, oxidant and deionized water, and has simple components, good stability and low price.
The preparation method is simple, the raw materials are all made in China, and the method is suitable for the requirement of large-scale industrial production.
Drawings
FIG. 1 is a schematic illustration of the effect of different composite active agent concentrations of the present invention on the number of surface defects during barrier CMP.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the accompanying drawings and preferred embodiments.
Example one (Sample 1, S1) contains no surfactant:
taking 250g of silica sol with the abrasive mass fraction of 40%, wherein the grain diameter is 50nm-90nm, and the dispersion degree is +/-3%; 10g of FA/O II chelating agent which is used as a pH value regulator, a buffering agent and a chelating agent and does not contain metal ions; 0.05g of hydrogen peroxide. The preparation method comprises the following steps: sequentially adding the FA/O II chelating agent, hydrogen peroxide and silica sol into a proper amount of deionized water according to the component weight, uniformly stirring in a step-by-step mixing mode, finally supplementing the deionized water to 1000g, and continuously uniformly stirring.
And (3) test monitoring: the pH value of the polishing solution is 9.5, and the particle size is 80-120 nm.
Defect testing experiment: using the prepared polishing solution to an AMAT-LK CMP type polishing machine produced by Applied Materials; working pressure Z1：1psi、Z2：1.7psi、Z3：1.5psi、Z4：1.5psi、Z51.5 psi; the rotational speed of the throwing disc is 80 r/min; the head throwing speed is 78 r/min; polishing ofThe liquid flow rate was 300 ml/min. Polishing a 300mm pattern sheet, cleaning, detecting defects by using a Scanning Electron Microscope (SEM), and obtaining 30000+ particles of total defects. Defect map (as shown in S1 in fig. 1).
Example two (Sample 2, S2) surfactant contains only nonionic surfactant:
taking 250g of silica sol with the abrasive mass fraction of 40%, wherein the grain diameter is 50nm-90nm, and the dispersion degree is +/-3%; 10g of FA/O II chelating agent which is used as a pH value regulator, a buffering agent and a chelating agent and does not contain metal ions; 0.1g,0.5g,1g,1.5g and 3g of dodecyl dimethyl amine oxide and 0.05g of hydrogen peroxide are respectively taken. The preparation method comprises the following steps: sequentially adding an FA/O II chelating agent, dodecyl dimethyl amine Oxide (OA), hydrogen peroxide and silica sol into a proper amount of deionized water according to the component amount, uniformly stirring in a step-by-step mixing mode, finally supplementing the deionized water to 1000g, and continuously uniformly stirring. And (3) test monitoring: the pH value of the polishing solution is 9.5, and the particle size is 80-110 nm.
Defect testing experiment: using the prepared polishing solution to an AMAT-LK CMP type polishing machine produced by Applied Materials; working pressure Z1：1psi、Z2：1.7psi、Z3：1.5psi、Z4：1.5psi、Z51.5 psi; the rotational speed of the throwing disc is 80 r/min; the head throwing speed is 78 r/min; the flow rate of the polishing solution was 300 ml/min. Polishing a 300mm pattern sheet, cleaning, detecting defects by using a Scanning Electron Microscope (SEM), and obtaining 12000, 10000, 7863, 7900 and 7932 total defects respectively. Defect map (as shown in S2 in fig. 1).
In example three (Sample 3, S3), the surfactant is a combination of an anionic active agent and a nonionic active agent, the mass ratio of the anionic active agent to the nonionic active agent is 0.1-3:1, and the mass percentage of the surfactant in the polishing solution is 0.11-0.4%.
Taking 250g of silica sol with the abrasive mass fraction of 40%, wherein the grain diameter is 50nm-90nm, and the dispersion degree is +/-3%; 10g of FA/O II chelating agent which is used as a pH value regulator, a buffering agent and a chelating agent and does not contain metal ions; taking 0.1g,0.5g,1g,1.5g and 3g of ammonium dodecyl sulfate respectively; 1g of dodecyl dimethyl amine oxide and 0.05g of hydrogen peroxide. The preparation method comprises the following steps: adding the FA/O II chelating agent, ammonium dodecyl sulfate, dodecyl dimethyl amine oxide, hydrogen peroxide and silica sol into a proper amount of deionized water in turn according to the component amount, uniformly stirring in a step-by-step mixing mode, finally supplementing the deionized water to 1000g, and continuously uniformly stirring. And (3) test monitoring: the pH value of the polishing solution is 9.5, and the particle size is 80-105 nm.
Defect testing experiment: using the prepared polishing solution to an AMAT-LK CMP type polishing machine produced by Applied Materials; working pressure Z1：1psi、Z2：1.7psi、Z3：1.5psi、Z4：1.5psi、Z51.5 psi; the rotational speed of the throwing disc is 80 r/min; the head throwing speed is 78 r/min; the flow rate of the polishing solution was 300 ml/min. Polishing a 300mm pattern sheet, cleaning, and detecting defects by using a Scanning Electron Microscope (SEM), wherein 3500, 3210, 2500, 1899 and 1923 defects are obtained. Defect map (as shown in S3 in fig. 1).
Example four (Sample 4, S4), the surfactant is a combination of an anionic active agent and a nonionic active agent, and the mass ratio of the anionic active agent to the nonionic active agent is 1.5: 1.1-4, and the mass percentage in the polishing solution is 0.26-0.55%, and the surface active agent contains fatty alcohol polyoxyethylene ether.
Taking 250g of silica sol with the abrasive mass fraction of 40%, wherein the grain diameter is 50nm-90nm, and the dispersion degree is +/-3%; 10g of FA/O II chelating agent which is used as a pH value regulator, a buffering agent and a chelating agent and does not contain metal ions; respectively taking 0.1g,0.5g,1g,1.5g and 3g of fatty alcohol-polyoxyethylene ether; 1.5g of ammonium dodecyl sulfate, 1g of dodecyl dimethyl amine oxide and 0.05g of hydrogen peroxide. The preparation method comprises the following steps: sequentially adding an FA/O II chelating agent, fatty alcohol-polyoxyethylene ether, ammonium dodecyl sulfate, dodecyl dimethyl amine oxide, hydrogen peroxide and silica sol into a proper amount of deionized water according to the component amount, uniformly stirring in a step-by-step mixing manner, finally supplementing to 1000g with deionized water, and continuously uniformly stirring. And (3) test monitoring: the pH value of the polishing solution is 9.5, and the particle size is 80-105 nm. And (3) test monitoring: the pH value of the polishing solution is 9.5, and the particle size is 85-105 nm.
Defect testing experiment: by means of prepared throwersPolishing the optical liquid on an AMAT-LK CMP type polishing machine produced by Applied Materials; working pressure Z1：1psi、Z2：1.7psi、Z3：1.5psi、Z4：1.5psi、Z51.5 psi; the rotational speed of the throwing disc is 80 r/min; the head throwing speed is 78 r/min; the flow rate of the polishing solution was 300 ml/min. The 300mm pattern piece was polished, cleaned, and then examined for defects by Scanning Electron Microscopy (SEM), and a defect map (shown as S4 in fig. 1) was obtained, in which the total number of defects was 1003, 700, 600, 450, and 312, respectively. Defect map (as shown in S4 in fig. 1).
Example five (Sample 5, S5): the surfactant is a compound of an anionic active agent and a nonionic active agent, and the mass ratio of the anionic active agent to the nonionic active agent is 2: 5.5, the mass percent of the polishing solution is 0.75%, and the surfactant contains fatty alcohol-polyoxyethylene ether.
Taking 250g of silica sol with the abrasive mass fraction of 40%, wherein the grain diameter is 50nm-90nm, and the dispersion degree is +/-3%; 10g of FA/O II chelating agent which is used as a pH value regulator, a buffering agent and a chelating agent and does not contain metal ions; taking 4g of fatty alcohol-polyoxyethylene ether; 2g of ammonium dodecyl sulfate; dodecyl dimethyl amine oxide 1.5 g; 0.05g of hydrogen peroxide. The preparation method comprises the following steps: sequentially adding an FA/O II chelating agent, dodecyl ammonium sulfate, dodecyl dimethyl amine oxide, fatty alcohol-polyoxyethylene ether, hydrogen peroxide and silica sol into a proper amount of deionized water according to the component weight, uniformly stirring in a step-by-step mixing manner, finally supplementing the deionized water to 1000g, and continuously uniformly stirring.
And (3) test monitoring: the pH value of the polishing solution is 9.5, and the particle size is 85-100 nm.
Defect testing experiment: using the prepared polishing solution to an AMAT-LK CMP type polishing machine produced by Applied Materials; working pressure Z1：1psi、Z2：1.7psi、Z3：1.5psi、Z4：1.5psi、Z51.5 psi; the rotational speed of the throwing disc is 80 r/min; the head throwing speed is 78 r/min; the flow rate of the polishing solution was 300 ml/min. The 300mm pattern piece was polished, then cleaned, and then examined for defects by Scanning Electron Microscopy (SEM), and a total number of defects of 29 were obtained. Defect map (as shown in S5 in fig. 1).
Example six (Sample 6, S6): the surfactant is a compound of an anionic active agent and a nonionic active agent, and the mass ratio of the anionic active agent to the nonionic active agent is 6: 15, and the mass percent of the polishing solution is 2.1%, and the surfactant contains fatty alcohol-polyoxyethylene ether.
Taking 250g of silica sol with the abrasive mass fraction of 40%, wherein the grain diameter is 50nm-90nm, and the dispersion degree is +/-3%; 10g of FA/O II chelating agent which is used as a pH value regulator, a buffering agent and a chelating agent and does not contain metal ions; 5g of dodecyl dimethyl amine oxide; 6g of dodecylamine sulfate (anion); 10g of fatty alcohol-polyoxyethylene ether; 0.05g of hydrogen peroxide. The preparation method comprises the following steps: sequentially adding an FA/O II chelating agent, dodecyl ammonium sulfate, dodecyl dimethyl amine oxide, fatty alcohol-polyoxyethylene ether, hydrogen peroxide and silica sol into a proper amount of deionized water according to the component weight, uniformly stirring in a step-by-step mixing manner, finally supplementing the deionized water to 1000g, and continuously uniformly stirring.
And (3) test monitoring: the pH value of the polishing solution is 9.5, and the particle size is 80-110 nm.
Defect testing experiment: using the prepared polishing solution to an AMAT-LK CMP type polishing machine produced by Applied Materials; working pressure Z1：1psi、Z2：1.7psi、Z3：1.5psi、Z4：1.5psi、Z51.5 psi; the rotational speed of the throwing disc is 80 r/min; the head throwing speed is 78 r/min; the flow rate of the polishing solution was 300 ml/min. Polishing a 300mm pattern piece, cleaning, detecting defects by using a Scanning Electron Microscope (SEM), and obtaining 1236 defects. Defect map (as shown in S6 in fig. 1).
As can be seen from the defect diagram in FIG. 1, the surface defects can be effectively reduced by compounding different active agents. Comparing S2 and S3 in fig. 1, it can be seen that the compounding of ammonium dodecyl sulfate and dodecyl dimethyl amine oxide can significantly reduce the number of defects, because ammonium dodecyl sulfate has good dispersing and wetting effects, and dodecyl dimethyl amine oxide improves the stability and dispersibility of silica nanoparticles, reduces particle aggregation, and further reduces defects, but the defect number is not as expected. Comparing S3, S4 and S5 in FIG. 1, it can be seen that fatty alcohol-polyoxyethylene ether is more effective in reducing surface defects, and fatty alcohol-polyoxyethylene ether has strong osmotic effect and can significantly reduce contact angles. The three active agents are compounded to obviously reduce the surface tension of the polishing solution, so that the wetting surface is improved and the uniformity is improved. The contact angle is small enough, improves the spreading behavior of polishing solution, reduces polishing friction, avoids the particle aggregation in the polishing process simultaneously, reduces the adsorption capacity of wafer surface, and then reduces the defect. Comparing S5 and S6 in fig. 1, it can be seen that as the mass fraction of the composite active agent continues to increase, the number of defects also increases, and the number of large particles in the polishing slurry also increases. This is because when the surfactant is excessive, free surfactant molecules bridge between particles to cause aggregation of particles, so that the number of large particles in the polishing slurry increases (more significantly, the particle diameter is greater than 5 μm); secondly, because the active agent has a foaming function, the foam in the polishing solution is increased along with the increase of the mass fraction of the active agent, and the foam floating on the surface of the polishing solution is easy to form crystals and scratch; the results of fig. 1 thus appear. The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911184055.1A CN111004579B (en) | 2019-11-27 | 2019-11-27 | Alkaline polishing solution for reducing CMP defects of multilayer copper interconnection barrier layer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911184055.1A CN111004579B (en) | 2019-11-27 | 2019-11-27 | Alkaline polishing solution for reducing CMP defects of multilayer copper interconnection barrier layer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111004579A CN111004579A (en) | 2020-04-14 |
| CN111004579B true CN111004579B (en) | 2021-08-06 |
Family
ID=70112247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911184055.1A Active CN111004579B (en) | 2019-11-27 | 2019-11-27 | Alkaline polishing solution for reducing CMP defects of multilayer copper interconnection barrier layer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111004579B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112355884B (en) * | 2020-11-05 | 2022-04-08 | 河北工业大学 | Control method for CMP rate selectivity of multi-layer copper interconnection barrier layer |
| CN112322190A (en) * | 2020-11-05 | 2021-02-05 | 河北工业大学 | Multilayer copper interconnect barrier layer polishing solution and preparation method thereof |
| CN114591684B (en) * | 2022-02-18 | 2024-01-30 | 浙江开化元通硅业有限公司 | Environment-friendly chemical mechanical polishing solution based on high-purity spherical silica sol, and preparation method and polishing method thereof |
| CN115058198A (en) * | 2022-03-21 | 2022-09-16 | 康劲 | Novel polishing solution and preparation method and application thereof |
| CN115056117A (en) * | 2022-03-21 | 2022-09-16 | 康劲 | Polishing process for preventing scratches in CMP (chemical mechanical polishing) |
| CN116814166A (en) * | 2023-06-05 | 2023-09-29 | 深圳市众望丽华微电子材料有限公司 | Low-residue coarse polishing solution suitable for large-size silicon wafer and preparation method thereof |
| CN119639353B (en) * | 2024-12-25 | 2025-09-19 | 河北工业大学创新研究院(石家庄) | Alkaline polishing liquid for TSV titanium barrier layer and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101358108A (en) * | 2007-08-03 | 2009-02-04 | 罗门哈斯电子材料Cmp控股股份有限公司 | Selective barrier polishing slurry |
| CN101358109A (en) * | 2007-08-03 | 2009-02-04 | 罗门哈斯电子材料Cmp控股股份有限公司 | Polishing Slurries for Polymer Barrier Removal |
| CN101372089A (en) * | 2006-12-21 | 2009-02-25 | 杜邦纳米材料气体产品有限公司 | Method and slurry for tuning low-k versus copper removal rate during chemical mechanical polishing |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100491072C (en) * | 2006-06-09 | 2009-05-27 | 河北工业大学 | Method for controlling disc-like pit during chemically mechanical polishing for ULSI multiple-layered copper wiring |
-
2019
- 2019-11-27 CN CN201911184055.1A patent/CN111004579B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372089A (en) * | 2006-12-21 | 2009-02-25 | 杜邦纳米材料气体产品有限公司 | Method and slurry for tuning low-k versus copper removal rate during chemical mechanical polishing |
| CN101358108A (en) * | 2007-08-03 | 2009-02-04 | 罗门哈斯电子材料Cmp控股股份有限公司 | Selective barrier polishing slurry |
| CN101358109A (en) * | 2007-08-03 | 2009-02-04 | 罗门哈斯电子材料Cmp控股股份有限公司 | Polishing Slurries for Polymer Barrier Removal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111004579A (en) | 2020-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111004579B (en) | Alkaline polishing solution for reducing CMP defects of multilayer copper interconnection barrier layer and preparation method thereof | |
| JP5474400B2 (en) | Semiconductor wetting agent, polishing composition and polishing method using the same | |
| CN113881349B (en) | Polishing liquid and polishing method for chemical mechanical polishing of silicon carbide wafer silicon surface | |
| US9458415B2 (en) | Post chemical-mechanical-polishing (post-CMP) cleaning composition comprising a specific sulfur-containing compound and a sugar alcohol or a polycarboxylic acid | |
| CN101050348B (en) | Etchant composition, composition for polishing, method for producing polishing composition and polishing method | |
| CN115160934B (en) | Super-hydrophilic large-size silicon fine polishing liquid and preparation and use methods thereof | |
| CN110951400A (en) | Polishing liquid for reducing surface defects in multi-layer cobalt interconnect barrier layer CMP and preparation method thereof | |
| CN102112566A (en) | A chemical mechanical polishing fluid | |
| Yang et al. | Composite surfactant based on AEO and ADS for colloidal silica particles removal in post CMP cleaning of copper interconnection | |
| CN104530987A (en) | Composition for finishing polish of silicon wafer and preparation method of composition | |
| Zhao et al. | The effect of non-ionic surfactants on the removal of cerium oxide particles in STI CMP post cleaning | |
| CN113667546A (en) | Cleaning agent composition used after silicon wafer processing | |
| JP5575735B2 (en) | Polishing composition concentrate | |
| CN116144270A (en) | Polishing solution and preparation method thereof | |
| CN113881510B (en) | Chemical mechanical polishing cleaning liquid and using method thereof | |
| CN113122143B (en) | A kind of chemical mechanical polishing liquid and its application in copper polishing | |
| CN114686106A (en) | A chemical mechanical polishing liquid for tungsten polishing | |
| CN106118491B (en) | It is a kind of for alkalescence polishing liquid of thin copper film barrier layer cobalt and preparation method thereof | |
| JP2020053677A (en) | Intermediate raw material, and polishing composition and surface treatment composition using the same | |
| Zhang et al. | Effect of FA/O II surfactant as a complex non-ionic surfactant on copper CMP | |
| CN100462203C (en) | Roughness Control Method in ULSI Multilayer Copper Wiring Chemical Mechanical Polishing | |
| CN111378366B (en) | Chemical mechanical polishing solution and application thereof | |
| CN1861726A (en) | Aluminium wiring polishing fluid for super large scale integrated circuit | |
| TWI830295B (en) | Nanocolloidal particles, preparation methods, cleaning agents and cleaning methods containing the same | |
| TW202033692A (en) | Chemical-mechanical polishing slurry and its use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |