CN113004801A - Chemical mechanical polishing solution - Google Patents
Chemical mechanical polishing solution Download PDFInfo
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- CN113004801A CN113004801A CN201911327408.9A CN201911327408A CN113004801A CN 113004801 A CN113004801 A CN 113004801A CN 201911327408 A CN201911327408 A CN 201911327408A CN 113004801 A CN113004801 A CN 113004801A
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- chemical mechanical
- mechanical polishing
- polishing solution
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- adenine
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- 238000005498 polishing Methods 0.000 title claims abstract description 88
- 239000000126 substance Substances 0.000 title claims abstract description 45
- 230000007797 corrosion Effects 0.000 claims abstract description 51
- 238000005260 corrosion Methods 0.000 claims abstract description 51
- 239000003112 inhibitor Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 229960000643 adenine Drugs 0.000 claims abstract description 21
- 229930024421 Adenine Natural products 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 6
- 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 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 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
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 claims description 5
- 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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 150000007524 organic acids Chemical group 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 49
- 239000010937 tungsten Substances 0.000 abstract description 49
- 229910052721 tungsten Inorganic materials 0.000 abstract description 47
- 230000003068 static effect Effects 0.000 abstract description 14
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 9
- 229910001930 tungsten oxide Inorganic materials 0.000 abstract description 2
- 235000012431 wafers Nutrition 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000000463 material Substances 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
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 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
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 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
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 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
- 238000009472 formulation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052755 nonmetal 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
- 230000002829 reductive effect Effects 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
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, which comprises: abrasive particles, a catalyst, a stabilizer, a corrosion inhibitor containing an adenine organic acid structure, an oxidant, water, and a pH adjuster. The polishing solution can polish tungsten and silicon oxide simultaneously, realize high polishing rate on tungsten metal and moderate polishing rate on silicon oxide, efficiently inhibit static corrosion of tungsten metal 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 formed by assembling millions of tiny components on a substrate, which are interconnected by multi-level interconnects to function accordingly. For example, a typical multilayer interconnect structure includes a first metal layer, a dielectric layer, and a second or more metal layers. Each layer structure is prepared by techniques such as Physical Vapor Deposition (PVD), Chemical Vapor Deposition (CVD), and Plasma Enhanced Chemical Vapor Deposition (PECVD), 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 unevenness may cause various defects of products, and thus planarization techniques of the conductive layer and the insulating dielectric layer become critical. In the 80's of the twentieth century, chemical mechanical polishing technology pioneered by IBM corporation was considered to be the most effective method of global planarization at present.
In recent years, tungsten has been increasingly used in semiconductor circuit fabrication. Tungsten, because of its high electromigration resistance at high current densities, forms good ohmic contacts with silicon and is therefore often used to make metal vias and contacts, while using adhesion layers, such as TiN and Ti, to bond with SiO2And (4) connecting. Chemical mechanical polishing can be used to perform polishing of tungsten to reduce the thickness of the tungsten layer and corresponding bond line to obtain exposed SiO2A planar surface of the surface. In this process, an etchant that reacts with tungsten is first converted into a soft oxide film, and then the oxide film is removed 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 relative to the wafer over the polishing pad. At the same time, polishing is performed by injecting a polishing composition ("slurry") between the wafer and the polishing pad, and the slurry is spread on the polishing pad by centrifugation. However, in practical applications, because the polishing slurry contains active oxidizing agent, corrosive compound, etc., tungsten or its oxide can be converted into soluble salt, which causes unexpected corrosion of tungsten, resulting in dishing or erosion of the surface. For example, severe erosion may form deep tungsten vias, resulting in an uneven tungsten surface further presented on the next layer of metal/non-metal elements, complicating the deposition of a metal layer on subsequent layers of the device, resulting in poor electrical contactAnd (5) problems are solved. Corrosion can also lead to "keyhole" phenomena, which can also cause serious contact problems, resulting in reduced yield.
To address this problem, it is desirable to add a corrosion inhibitor to the polishing composition. For example, US patent No. 6136711 discloses a method of using an amino acid as a tungsten polishing corrosion inhibitor, which can inhibit corrosion of tungsten to some extent. U.S. Pat. No. 6,983,419 discloses polishing compositions containing oxazolidine, sulfide, and azacyclotungsten corrosion inhibitors which provide an optimum effect of corrosion reduction of about 97%, but no data are given on polishing rates and the like. US patent 8858819 discloses a polishing combination with polyethyleneimine as a tungsten corrosion inhibitor that significantly reduces static corrosion of tungsten at room temperature. However, at temperatures greater than 40 degrees, the effect is general, and the polishing rate of tungsten decreases significantly (by about 30%) even if only 3ppm is added. U.S. patent No. 8865013 discloses a tungsten polishing composition containing a bis-quaternary corrosion inhibitor. The composition can inhibit static corrosion of metal tungsten, but the oxidant is KIO3Rather than hydrogen peroxide, results in very low tungsten polishing rates for the composition. U.S. patent No. 9566686 discloses a tungsten polishing composition using a modified permanent positive charge>15mV) and a quaternary ammonium salt corrosion inhibitor having a long alkyl chain. Although the system can better 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 can not simultaneously realize high polishing rate on tungsten metal, can keep medium polishing rate on silicon oxide and can efficiently inhibit the static corrosion of the tungsten metal, the invention provides the chemical mechanical polishing solution, which comprises the following components in percentage by weight: abrasive particles, a catalyst, a stabilizer, a corrosion inhibitor containing an adenine organic acid structure, an oxidant, water, and a pH adjuster.
Further, the corrosion inhibitor containing an adenine organic acid structure has an adenine, and has a bridging group (R) and an organic acid substituent on the adenine, and the structure of the corrosion inhibitor containing an adenine organic acid structure is as follows:
wherein the bridging group R is selected from alkylene (e.g., (CH)2)nN-1-6), or an alkyl bridge containing a heteroatom (e.g. O, N, S) (e.g. (CH)2)nO(CH2)mN is 1-3, m is 1-3; and/or (CH)2)nNH(CH2)mN is 1-3, m is 1-3; and/or (CH)2)nS(CH2)mN-1-3, m-1-3), wherein the heteroatom is not limited to O, N, S already listed in the application, but can be other atoms;
x is selected from the group consisting of C, P, S,
when X is C, n is 1, m is 1;
when X is P, n is 2, m is 1;
when X is S, n is 1 and m is 2.
Further, the corrosion inhibitor containing adenine organic acid structure is tenofovir ((R) -9- (2-methoxypropyl phosphate) -adenine with chemical formula C9H14N5O4P), or adefovir (9- (2-phosphonomethoxyethyl) adenine, formula: c8H12N5O4P)。
Furthermore, the concentration range of the corrosion inhibitor containing the adenine organic acid structure is 0.005-0.1%.
Furthermore, the concentration range of the corrosion inhibitor containing the adenine organic acid structure is 0.005-0.05%.
Further, the abrasive particles are SiO2。
Further, the concentration range of the grinding particles is 0.5% -3%.
Further, the concentration range of the grinding particles is 1-3%.
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 capable of being complexed with 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 range of the malonic acid is 0.08% -0.27%.
Further, the concentration range of the malonic acid is 0.1% -0.27%.
Further, the oxidant is H2O2。
Further, the concentration of the oxidant is 1-2%.
Further, the pH adjusting agent is HNO 3.
Further, the pH value is 2-4. When the pH is less than 2, the chemical mechanical polishing solution is dangerous, and the pH is more than 4, which can cause the defects of unstable grinding particles, Fe precipitation and the like.
It should be understood that% in the concentrations described herein all refer to mass percent.
All of the 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 simultaneously polish tungsten and silicon oxide, realize the maintenance of higher polishing rate on tungsten metal and medium polishing rate on silicon oxide, efficiently inhibit the static corrosion of tungsten metal and improve the surface condition of polished metal.
Detailed Description
The advantages of the invention are explained in detail below with reference to specific embodiments.
The chemical mechanical polishing composition for polishing tungsten of the present invention is described in detail below by way of specific examples to provide a better understanding of the invention, but the following examples do not limit the scope of the invention.
Examples
According to specific examples and the formula given in the table 1, all the components are dissolved and mixed uniformly, and water is used for complementing the mass percent to 100 percent. The pH is adjusted to the desired value with a pH adjusting agent.
TABLE 1 component types and their corresponding concentrations in the examples and comparative examples
Examples of effects
Tungsten wafers and silicon oxide wafers were polished and subjected to static corrosion testing according to the formulations of table 1 and the experimental conditions described below, resulting in the results of table 2.
The specific polishing conditions are as follows: the polishing machine is a 12-inch machine Reflexion LK of applied materials company, the pressure is 3.0psi, the rotating speed of the polishing disk and the polishing head is 93/87rpm, the polishing pad IC1010, the flow rate of the polishing solution is 150ml/min, and the polishing time is 1 minute.
Static corrosion testing of tungsten: a tungsten wafer of about 5cm x 5cm was immersed in either room temperature or preheated 45 c polishing slurry for 2 minutes, and then rinsed out. Before the wafer was put in and after the wafer was taken out and cleaned, the thickness of the metal layer of the wafer was measured using a four-point probe tester (model RT 70/RG 7B) of Napson corporation, respectively, to obtain a corrosion value.
TABLE 2 polishing rates for various examples and comparative examples polished tungsten wafers and corrosion rates for tungsten metal at different temperatures
Examples 1-5 and 10-14 show that the chemical mechanical polishing solution of the invention can perform high-speed polishing of tungsten, and can effectively inhibit static corrosion of tungsten (the corrosion rate is less than 35A/min) at both 25 ℃ and 40 ℃, and the corrosion inhibition effect of the chemical mechanical polishing solution of the invention at room temperature is more obvious than that at other temperatures. From examples 1-3, 10-14, it can be seen that for the preferred corrosion inhibitors tenofovir and adefovir, the corrosion inhibition effect becomes better with increasing amount of corrosion inhibitor, wherein when the concentration of tenofovir reaches 0.1%, the static corrosion of tungsten can be completely inhibited (corrosion rate is 0). Specifically, as the concentration of the corrosion inhibitor containing an adenine organic acid structure was increased from 0.005% in example 11 to 0.03% in example 10, to 0.05% in example 12, to 0.07% in example 13, to 0.1% in example 14, the corresponding tungsten corrosion rates were 18, 11, 2, 1, 0, respectively, at 25 ℃; at 40 ℃, the corresponding tungsten etch rates were 33, 29, 16, 5, 0, respectively. In addition, it can be seen from examples 10 to 14 that the chemical mechanical polishing solution containing tenofovir had no significant effect on the tungsten polishing rate and had no effect on the polishing rate of silicon oxide.
It can be seen from examples 3 and 5 that the tungsten polishing rate, the silicon oxide polishing rate, and the effect of inhibiting tungsten static corrosion are similar in the chemical mechanical polishing solution containing tenofovir and the chemical mechanical polishing solution containing adefovir.
By comparing comparative example 1 with examples 4 and 10, it is found that the chemical mechanical polishing solution without the corrosion inhibitor containing adenine organic acid structure has no technical effect of inhibiting static corrosion of tungsten and has obvious corrosion of tungsten on the basis that the abrasive particles, the catalyst, the stabilizer, the oxidant and the pH are the same.
By comparing comparative example 2 and example 10, it was found that the chemical mechanical polishing solution containing adenine itself could not inhibit static corrosion of tungsten, while the chemical mechanical polishing solution containing tenofovir had the technical effect of inhibiting static corrosion of tungsten metal.
By comparing comparative example 3 with examples 4 and 10, it was found that although the chemical mechanical polishing liquid containing 6-carboxyadenine can inhibit the corrosion of tungsten to some extent, it is not as effective as tenofovir and adefovir.
In summary, the chemical mechanical polishing solution provided by the invention overcomes the technical defects that the prior art can not simultaneously realize high polishing rate on tungsten metal, moderate polishing rate on silicon oxide and high-efficiency static corrosion inhibition on tungsten metal.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (23)
1. A chemical mechanical polishing solution comprising: abrasive particles, a catalyst, a stabilizer, a corrosion inhibitor containing an adenine organic acid structure, an oxidant, water, and a pH adjuster.
2. The chemical mechanical polishing solution according to claim 1, wherein the corrosion inhibitor containing an adenine organic acid structure has an adenine, and has a bridging group (R) and an organic acid substituent on the adenine, and the corrosion inhibitor containing an adenine organic acid structure has the following structure:
wherein the bridging group R is selected from an alkylene group or a heteroatom-containing alkyl bridge,
x is selected from one or more of C, P, S,
when X is C, n is 1, m is 1;
when X is P, n is 2, m is 1;
when X is S, n is 1 and m is 2.
3. The chemical mechanical polishing solution according to claim 2, wherein the corrosion inhibitor containing an adenine organic acid structure is tenofovir or adefovir.
4. The chemical mechanical polishing solution according to claim 3, wherein the concentration of the corrosion inhibitor containing an adenine organic acid structure is in the range of 0.005% to 0.1%.
5. The chemical mechanical polishing solution according to claim 4, wherein the concentration of the corrosion inhibitor containing an adenine organic acid structure is in the range of 0.005% to 0.05%.
6. The chemical mechanical polishing solution according to claim 1, wherein the abrasive particles are SiO2。
7. The chemical mechanical polishing solution according to claim 6, wherein the concentration of the abrasive particles is in the range of 0.5% to 3%.
8. The chemical mechanical polishing solution according to claim 7, wherein the concentration of the abrasive particles is in the range of 1% to 3%.
9. The chemical mechanical polishing solution of claim 1 wherein the catalyst is a metal cation catalyst.
10. The chemical mechanical polishing solution of claim 9, wherein the metal cation catalyst is ferric nitrate nonahydrate.
11. The chemical mechanical polishing solution of claim 10, wherein the concentration of the ferric nitrate nonahydrate ranges from 0.01% to 0.1%.
12. The chemical mechanical polishing solution of claim 11, wherein the concentration of the ferric nitrate nonahydrate ranges from 0.01% to 0.07%.
13. The chemical mechanical polishing solution according to claim 1, wherein the stabilizer is an organic stabilizer.
14. The chemical mechanical polishing solution according to claim 13, wherein the organic stabilizer is a carboxylic acid capable of complexing with iron.
15. The chemical mechanical polishing solution according to claim 14, wherein the carboxylic acid capable of complexing with iron is one or more of phthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, citric acid, and maleic acid.
16. The chemical mechanical polishing solution according to claim 15, wherein the carboxylic acid capable of complexing with iron is malonic acid.
17. The chemical mechanical polishing solution of claim 16 wherein the concentration of malonic acid ranges from 0.08% to 0.27%.
18. The chemical mechanical polishing solution of claim 17, wherein the concentration of the malonic acid ranges from 0.1% to 0.27%.
19. Chemical mechanical polishing as recited in claim 1A light liquid, the oxidant is H2O2。
20. The chemical mechanical polishing solution according to claim 1, wherein the concentration of the oxidizing agent is 1 to 2%.
21. The chemical mechanical polishing solution according to claim 1, wherein the pH adjusting agent is HNO3。
22. The chemical mechanical polishing solution according to claim 1, having a pH of 2 to 4.
23. The chemical mechanical polishing solution according to claim 2, wherein the alkylene group is (CH)2) n, n is 1-6; the heteroatom-containing alkyl bridge is (CH)2)nO(CH2) m, n is 1-3, m is 1-3; and/or (CH)2)nNH(CH2) m n ═ 1-3, m ═ 1-3; and/or (CH)2)nS(CH2)m，n＝1-3，m＝1-3。
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
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| 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 TWI860432B (en) | 2019-12-20 | 2020-12-10 | Chemical mechanical polishing slurry |
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| CN201911327408.9A CN113004801B (en) | 2019-12-20 | 2019-12-20 | Chemical mechanical polishing solution |
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| KR (1) | KR20220120569A (en) |
| CN (1) | CN113004801B (en) |
| WO (1) | WO2021121047A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| TW202132492A (en) | 2021-09-01 |
| KR20220120569A (en) | 2022-08-30 |
| CN113004801B (en) | 2024-03-12 |
| WO2021121047A1 (en) | 2021-06-24 |
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