CN113004801B - Chemical mechanical polishing solution - Google Patents
Chemical mechanical polishing solution Download PDFInfo
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- CN113004801B CN113004801B CN201911327408.9A CN201911327408A CN113004801B CN 113004801 B CN113004801 B CN 113004801B CN 201911327408 A CN201911327408 A CN 201911327408A CN 113004801 B CN113004801 B CN 113004801B
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- 238000005498 polishing Methods 0.000 title claims abstract description 69
- 239000000126 substance Substances 0.000 title claims abstract description 27
- 230000007797 corrosion Effects 0.000 claims abstract description 50
- 238000005260 corrosion Methods 0.000 claims abstract description 50
- 239000003112 inhibitor Substances 0.000 claims abstract description 21
- 229960000643 adenine Drugs 0.000 claims abstract description 17
- 229930024421 Adenine Natural products 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 15
- 229960004556 tenofovir Drugs 0.000 claims description 8
- VCMJCVGFSROFHV-WZGZYPNHSA-N tenofovir disoproxil fumarate Chemical group OC(=O)\C=C\C(O)=O.N1=CN=C2N(C[C@@H](C)OCP(=O)(OCOC(=O)OC(C)C)OCOC(=O)OC(C)C)C=NC2=C1N VCMJCVGFSROFHV-WZGZYPNHSA-N 0.000 claims description 8
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229960001997 adefovir Drugs 0.000 claims description 5
- WOZSCQDILHKSGG-UHFFFAOYSA-N adefovir depivoxil Chemical compound N1=CN=C2N(CCOCP(=O)(OCOC(=O)C(C)(C)C)OCOC(=O)C(C)(C)C)C=NC2=C1N WOZSCQDILHKSGG-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 51
- 239000010937 tungsten Substances 0.000 abstract description 51
- 229910052721 tungsten Inorganic materials 0.000 abstract description 49
- 229910052751 metal Inorganic materials 0.000 abstract description 21
- 239000002184 metal Substances 0.000 abstract description 21
- 230000003068 static effect Effects 0.000 abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 9
- 239000003381 stabilizer Substances 0.000 abstract description 6
- 229910001930 tungsten oxide Inorganic materials 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 11
- 235000012431 wafers Nutrition 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- QRBPRPXDUFXPGR-UHFFFAOYSA-N 2-methoxypropyl dihydrogen phosphate Chemical compound COC(C)COP(O)(O)=O QRBPRPXDUFXPGR-UHFFFAOYSA-N 0.000 description 1
- PJAXDEAQLSDROT-UHFFFAOYSA-N NC1(C(O)=O)N=CN=C2N=CN=C12 Chemical compound NC1(C(O)=O)N=CN=C2N=CN=C12 PJAXDEAQLSDROT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- SUPKOOSCJHTBAH-UHFFFAOYSA-N adefovir Chemical compound NC1=NC=NC2=C1N=CN2CCOCP(O)(O)=O SUPKOOSCJHTBAH-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- 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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
-
- 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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
The invention provides a chemical mechanical polishing solution, comprising: abrasive particles, catalyst, stabilizer, corrosion inhibitor containing adenine organic acid structure, oxidant, water and pH regulator. The polishing device can polish tungsten and silicon oxide simultaneously, maintain a high polishing rate on tungsten metal, a medium polishing rate on silicon oxide, inhibit static corrosion of tungsten metal efficiently, and improve the surface condition of polished metal.
Description
Technical Field
The invention relates to a chemical mechanical polishing solution.
Background
Modern semiconductor integrated circuits are a collection of millions of tiny components on a substrate that function in concert by forming an interconnect structure through multiple layers of interconnects. For example, a typical multi-layer interconnect structure includes a first metal layer, a dielectric layer, and a second or more metal layers. Each layer structure is prepared by Physical Vapor Deposition (PVD), chemical Vapor Deposition (CVD), plasma Enhanced Chemical Vapor Deposition (PECVD), etc., and then a new layer is formed thereon. As layers of material are deposited and removed, the uppermost surface of the wafer becomes uneven. These non-uniformities may lead to various defects in the product, and therefore the planarization techniques of the conductive layer and the insulating dielectric layer become critical. In the twentieth century, the chemical mechanical polishing technology initiated by IBM corporation was considered the most effective method of global planarization at present.
In recent years, tungsten has been increasingly used in semiconductor circuit fabrication. Tungsten, which has strong electromigration resistance at high current densities, forms good ohmic contact with silicon and is therefore often used to make metal vias and contacts, while using bonding layers such as TiN and Ti to bond it to SiO 2 And (5) connection. Chemical mechanical polishing may be used to polish tungsten to reduce the tungsten layer and corresponding bond line thickness to obtain exposed SiO 2 Flat surface of the surface. In this process, the oxide film is first removed by an etchant that reacts with tungsten and converts it into a soft oxide film, and then by mechanical grinding. The concrete mode is as follows: the wafer is held on the polishing head and its front surface is brought into contact with the polishing pad. The polishing head moves over the polishing pad relative to the wafer. At the same time, polishing is performed by injecting a polishing composition ("slurry") between the wafer and the polishing pad, the slurry lying on the polishing pad by centrifugation. However, in practical applications, tungsten or its oxides may be converted to soluble salts by inclusion of reactive oxidizing agents, corrosive compounds, etc. in the polishing slurry, causing unexpected corrosion of tungsten, leading to dishing or erosion of the surface. For example, severe corrosion may form deep tungsten vias, resulting in uneven tungsten surfaces further present on the next layer of metal/non-metal elements, complicating the deposition of metal layers on subsequent layers of the device, and thus resulting in poor electrical contact problems. Corrosion can also lead to "keyhole" phenomena, which can also cause serious contact problems, resulting in reduced yields.
To address this problem, it is desirable to incorporate a corrosion inhibitor into the polishing composition. For example, U.S. patent No. 6136711 discloses methods of using amino acids as corrosion inhibitors for tungsten polishing that can inhibit tungsten corrosion to some extent. U.S. patent No. 6083419 discloses a polishing composition comprising an oxazolidine, sulfide, and an azimuthally tungsten corrosion inhibitor that best results in a reduction of about 97% corrosion, but no data is given for polishing rate, etc. U.S. Pat. No. 3,182,62 disclosesA polishing composition using polyethylenimine as a tungsten corrosion inhibitor can significantly reduce static corrosion of tungsten at room temperature. However, at temperatures greater than 40 degrees, the effect is generally, and even if only 3ppm of tungsten is added, the polishing rate of tungsten is greatly reduced (by about 30%). U.S. patent No. 8865013 discloses a tungsten polishing composition comprising a bis-quaternary corrosion inhibitor. The composition can well inhibit static corrosion of tungsten metal, but the oxidant is KIO 3 Instead of hydrogen peroxide, results in a very low tungsten polishing rate for the composition. U.S. Pat. No. 3,182 discloses a tungsten polishing composition in which a modified permanent positive charge is used>15 mV) of abrasive particles and quaternary ammonium salt corrosion inhibitors having long alkyl chains. Although the system can well inhibit the corrosion of tungsten, the preparation of the grinding particles is complicated, the cost is high, and the tungsten polishing rate is not high.
Disclosure of Invention
In order to solve the technical defects that the chemical mechanical polishing solution in the prior art cannot simultaneously realize high polishing rate on tungsten metal, medium polishing rate on silicon oxide and high-efficiency inhibition on static corrosion of tungsten metal, the invention provides the chemical mechanical polishing solution, which comprises the following components: abrasive particles, catalyst, stabilizer, corrosion inhibitor containing adenine organic acid structure, oxidant, water and pH regulator.
Further, the adenine organic acid structure-containing corrosion inhibitor has an adenine and simultaneously has a bridging group (R) and an organic acid substituent on adenine, and the adenine organic acid structure-containing corrosion inhibitor has the following structure:
wherein the bridging group R is selected from alkylene groups (e.g. (CH 2 ) n N=1 to 6), or alkyl bridges containing heteroatoms (e.g. O, N, S) (e.g. (CH) 2 ) n O(CH 2 ) m N=1-3, m=1-3; and/or (CH) 2 ) n NH(CH 2 ) m N=1-3, m=1-3; and/or (CH) 2 ) n S(CH 2 ) m N=1-3, m=1-3), wherein the heteroatom is not limited to O, N, S already listed in the application, but may be other atoms;
x is selected from the group consisting of C, P, S,
when x=c, n=1, m=1;
when x=p, n=2, m=1;
when x=s, n=1, m=2.
Further, the corrosion inhibitor containing adenine organic acid structure is tenofovir ((R) -9- (2-methoxypropyl phosphate) -adenine, and the chemical formula is C 9 H 14 N 5 O 4 P), or adefovir (9- (2-phosphonomethoxyethyl) adenine, formula: c (C) 8 H 12 N 5 O 4 P)。
Further, the concentration of the corrosion inhibitor containing the adenine organic acid structure is in the range of 0.005% to 0.1%.
Further, the concentration of the corrosion inhibitor containing the adenine organic acid structure ranges from 0.005% to 0.05%.
Further, the abrasive particles are SiO 2 。
Further, the concentration of the abrasive particles ranges from 0.5% to 3%.
Further, the concentration of the abrasive particles ranges from 1% to 3%.
Further, the catalyst is a metal cation catalyst.
Further, the metal cation catalyst is ferric nitrate nonahydrate.
Further, the concentration range of the ferric nitrate nonahydrate is 0.01% -0.1%.
Further, the concentration range of the ferric nitrate nonahydrate is 0.01% -0.07%.
Further, the stabilizer is an organic stabilizer.
Further, the organic stabilizer is a carboxylic acid that can complex with iron.
Further, the carboxylic acid which can be complexed with the iron is one or more of phthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, citric acid and maleic acid.
Further, the carboxylic acid that can be complexed with iron is malonic acid.
Further, the concentration of the malonic acid ranges from 0.08% to 0.27%.
Further, the concentration of the malonic acid ranges from 0.1% to 0.27%.
Further, the oxidant is H 2 O 2 。
Further, the concentration of the oxidizing agent is 1 to 2%.
Further, the pH adjuster is HNO3.
Further, the pH value is 2-4. When the pH is less than 2, the chemical mechanical polishing solution is a dangerous article, and the pH is more than 4, so that the defects of unstable grinding particles, precipitation of Fe and the like can be caused.
It should be understood that the percentages in the concentrations described in the present invention refer to mass percent.
All reagents of the invention are commercially available.
Compared with the prior art, the invention has the advantages that:
the invention provides a chemical mechanical polishing solution, which can polish tungsten and silicon oxide simultaneously, can maintain a higher polishing rate on tungsten metal, can maintain a medium polishing rate on silicon oxide, can efficiently inhibit static corrosion of tungsten metal, and can improve the surface condition of polished metal.
Detailed Description
Advantages of the invention will be described in detail below with reference to the drawings and the detailed description.
The following is a detailed description of the chemical mechanical polishing composition of the invention for polishing tungsten by way of specific examples to provide a better understanding of the invention, but the following examples are not intended to limit the scope of the invention.
Examples
The specific examples and comparative examples were prepared according to the formulations given in table 1, all components were dissolved and mixed uniformly, and water was used to make up the mass percent to 100%. The pH is adjusted to the desired value with a pH adjustor.
TABLE 1 species of each component and corresponding concentrations in each example and comparative example
Effect example
Polishing and static etch tests were performed on tungsten wafers, silicon oxide wafers according to the following experimental conditions according to the formulations of table 1, resulting in the results of table 2.
Specific polishing conditions: the polishing machine table was a 12 inch machine table, reflexion LK, pressure 3.0psi, polishing disk and polishing head rotation speed 93/87rpm, polishing pad IC1010, polishing fluid flow rate 150ml/min, polishing time 1 minute.
Static corrosion test of tungsten: about 5cm by 5cm tungsten wafers were immersed in the polishing slurry at room temperature or preheated at 45 c for 2 minutes and rinsed. Before the wafer was put in and after the wafer was taken out for cleaning, the thickness of the wafer metal layer was measured using a four-point probe tester (model RT 70/RG 7B) from Napson corporation, respectively, to obtain a corrosion value.
TABLE 2 polishing rates of tungsten wafers and tungsten metal Corrosion rates at different temperatures for the respective examples and comparative examples
Examples 1-5 and 10-14 show that the chemical mechanical polishing solution can polish tungsten at a high speed, can inhibit static corrosion of tungsten at 25 ℃ and 40 ℃ effectively (corrosion rate is less than 35A/min), and has more obvious corrosion inhibition effect at room temperature than other temperatures. It is seen from examples 1-3, 10-14 that for the preferred corrosion inhibitors tenofovir, adefovir, it was found that the corrosion inhibition effect was correspondingly better with increasing amounts of corrosion inhibitor, wherein when the tenofovir concentration reached 0.1%, even the static corrosion of tungsten could be completely inhibited (corrosion rate 0). Specifically, as the concentration of the adenine organic acid structure-containing corrosion inhibitor increases from 0.005% of example 11 to 0.03% of example 10, to 0.05% of example 12, to 0.07% of example 13, to 0.1% of example 14, the corresponding tungsten corrosion rates are 18, 11, 2, 1, 0, respectively, at 25 ℃; at 40 ℃, the corresponding tungsten corrosion rates were 33, 29, 16, 5, 0, respectively. Furthermore, it is seen from examples 10-14 that the chemical mechanical polishing liquid containing tenofovir had no significant effect on the tungsten polishing rate, while having no effect on the silicon oxide polishing rate.
It is apparent from examples 3 and 5 that the chemical mechanical polishing solutions containing tenofovir and the chemical mechanical polishing solution containing adefovir have similar magnitudes of tungsten polishing rate, silicon oxide polishing rate, and effect of inhibiting static corrosion of tungsten.
Comparison of comparative example 1 and examples 4 and 10 shows that the chemical mechanical polishing liquid without adding the corrosion inhibitor containing adenine organic acid structure has no technical effect of inhibiting static corrosion of tungsten on the basis of the same abrasive particles, catalyst, stabilizer, oxidant and pH, and there is obvious corrosion of tungsten.
Comparison of comparative example 2 and example 10 shows that the chemical mechanical polishing liquid containing adenine itself cannot inhibit static corrosion of tungsten, whereas the chemical mechanical polishing liquid containing tenofovir has a technical effect of inhibiting static corrosion of tungsten metal.
Comparison of comparative example 3 and examples 4 and 10 shows that although the chemical mechanical polishing liquid containing 6-carboxyadenine can also suppress corrosion of tungsten to some extent, it is not as effective as tenofovir and adefovir.
In summary, the chemical mechanical polishing solution overcomes the technical defect that the prior art cannot simultaneously realize high polishing rate on tungsten metal, medium polishing rate on silicon oxide and high-efficiency inhibition on static corrosion of tungsten metal.
The above description of the specific embodiments of the present invention has been given by way of example only, and the present invention is not limited to the above described specific embodiments. Any equivalent modifications and substitutions for the present invention will occur to those skilled in the art, and are also within the scope of the present invention. Accordingly, equivalent changes and modifications are intended to be included within the scope of the present invention without departing from the spirit and scope thereof.
Claims (6)
1. A chemical mechanical polishing solution comprising: abrasive particles, a catalyst, malonic acid, a corrosion inhibitor comprising an adenine organic acid structure, an oxidizing agent, water, and a pH adjustor,
the grinding particles are SiO 2 The concentration range of the grinding particles is 0.5% -3%;
the catalyst is ferric nitrate nonahydrate, and the concentration range of the ferric nitrate nonahydrate is 0.0-0.1 percent;
the concentration range of the malonic acid is 0.08-0.27%;
the corrosion inhibitor containing the adenine organic acid structure is tenofovir or adefovir, and the concentration range of the corrosion inhibitor containing the adenine organic acid structure is 0.005-0.1%;
the oxidant is H 2 O 2 The concentration of the oxidant is 1-2%;
the pH value is 2-4; the% refers to mass percent content.
2. The chemical mechanical polishing solution according to claim l, wherein the concentration of the corrosion inhibitor containing an adenine organic acid structure is in the range of 0.005% to 0.05%.
3. The chemical mechanical polishing solution according to claim l, wherein the concentration of the abrasive particles is in the range of l% to 3%.
4. The chemical mechanical polishing solution according to claim l, wherein the concentration of the ferric nitrate nonahydrate is in the range of 0.01% -0.07%.
5. The chemical mechanical polishing solution according to claim l, wherein the concentration of malonic acid is in the range of 0.1% to 0.27%.
6. The chemical mechanical polishing liquid according to claim l, wherein the pH adjustor is HNO 3 。
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911327408.9A CN113004801B (en) | 2019-12-20 | 2019-12-20 | Chemical mechanical polishing solution |
| PCT/CN2020/133606 WO2021121047A1 (en) | 2019-12-20 | 2020-12-03 | Chemical-mechanical polishing liquid |
| KR1020227020762A KR20220120569A (en) | 2019-12-20 | 2020-12-03 | chemical mechanical polishing liquid |
| TW109143716A TW202132492A (en) | 2019-12-20 | 2020-12-10 | Chemical mechanical polishing slurry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911327408.9A CN113004801B (en) | 2019-12-20 | 2019-12-20 | Chemical mechanical polishing solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113004801A CN113004801A (en) | 2021-06-22 |
| CN113004801B true CN113004801B (en) | 2024-03-12 |
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| CN201911327408.9A Active CN113004801B (en) | 2019-12-20 | 2019-12-20 | Chemical mechanical polishing solution |
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| KR (1) | KR20220120569A (en) |
| CN (1) | CN113004801B (en) |
| TW (1) | TW202132492A (en) |
| WO (1) | WO2021121047A1 (en) |
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| CN109545736A (en) * | 2017-09-21 | 2019-03-29 | 罗门哈斯电子材料Cmp控股股份有限公司 | Cmp method for cobalt |
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| EP2234145B1 (en) * | 2007-12-21 | 2013-02-20 | Wako Pure Chemical Industries, Ltd. | Etching agent, etching method and liquid for preparing etching agent |
| JP6631520B2 (en) * | 2014-07-09 | 2020-01-15 | 日立化成株式会社 | Polishing liquid for CMP and polishing method |
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2019
- 2019-12-20 CN CN201911327408.9A patent/CN113004801B/en active Active
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2020
- 2020-12-03 KR KR1020227020762A patent/KR20220120569A/en unknown
- 2020-12-03 WO PCT/CN2020/133606 patent/WO2021121047A1/en active Application Filing
- 2020-12-10 TW TW109143716A patent/TW202132492A/en unknown
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| IN184462B (en) * | 1994-03-22 | 2000-08-26 | Norton Co | |
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| CN101496143A (en) * | 2006-07-28 | 2009-07-29 | 昭和电工株式会社 | Polishing composition |
| CN101720352A (en) * | 2007-05-17 | 2010-06-02 | 高级技术材料公司 | Be used for removing the new antioxidant of filling a prescription behind the CPM |
| CN102197124A (en) * | 2008-10-21 | 2011-09-21 | 高级技术材料公司 | Copper cleaning and protection formulations |
| CN101775256A (en) * | 2009-01-14 | 2010-07-14 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
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| TW201226489A (en) * | 2010-12-23 | 2012-07-01 | Anji Microelectronics Co Ltd | Chemical mechanical polishing fluid |
| CN104334706A (en) * | 2012-03-18 | 2015-02-04 | 安格斯公司 | Post-CMP formulation having improved barrier layer compatibility and cleaning performance |
| CN109545736A (en) * | 2017-09-21 | 2019-03-29 | 罗门哈斯电子材料Cmp控股股份有限公司 | Cmp method for cobalt |
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Also Published As
| Publication number | Publication date |
|---|---|
| TW202132492A (en) | 2021-09-01 |
| WO2021121047A1 (en) | 2021-06-24 |
| CN113004801A (en) | 2021-06-22 |
| KR20220120569A (en) | 2022-08-30 |
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