CN111378373A - Chemical mechanical polishing solution for polishing tungsten - Google Patents
Chemical mechanical polishing solution for polishing tungsten Download PDFInfo
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- 238000005498 polishing Methods 0.000 title claims abstract description 139
- 239000000126 substance Substances 0.000 title claims abstract description 35
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 29
- 239000010937 tungsten Substances 0.000 title claims abstract description 29
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 9
- 150000007524 organic acids Chemical class 0.000 claims abstract description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 239000003381 stabilizer Substances 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 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
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 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
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 65
- 239000000377 silicon dioxide Substances 0.000 abstract description 33
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 7
- 238000003475 lamination Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- -1 potassium ferricyanide Chemical compound 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- KTYVHLCLTPLSGC-UHFFFAOYSA-N amino propanoate Chemical compound CCC(=O)ON KTYVHLCLTPLSGC-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000006061 abrasive grain Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920000289 Polyquaternium Polymers 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229960005191 ferric oxide Drugs 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (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 for polishing tungsten, which comprises silica sol, ferric nitrate and an organic acid complexing agent, wherein the surface of abrasive particles of the silica sol is treated by a silane coupling agent, and the pH value of the polishing solution is 4.0-5.5. According to the chemical mechanical polishing solution for polishing tungsten, the polishing solution has a higher silicon dioxide polishing speed under the condition of low solid content of an abrasive by adjusting the pH value, can remove tungsten residues at a depression formed in a lamination effect, improves the polishing quality and improves the yield; reduces the manufacturing cost of the product and is beneficial to high-power concentration.
Description
Technical Field
The invention relates to the technical field of semiconductor polishing, in particular to a chemical mechanical polishing solution for polishing tungsten.
Background
With the continuous development of semiconductor technology and the increasing of interconnect layers of large scale integrated circuits, the planarization technology of conductive layers and insulating dielectric layers becomes especially critical, wherein the Chemical Mechanical Polishing (CMP) technology initiated by IBM corporation in the 80's of the twentieth century is considered to be the most effective method for global planarization at present. Chemical Mechanical Polishing (CMP) is a technique for achieving planarization by chemical action, mechanical action, and a combination of these two actions; it generally consists of a polishing table with a polishing pad and a polishing head for carrying the chip. The grinding head fixes the chip, then presses the front surface of the chip on the polishing pad, and when the chemical mechanical polishing is carried out, the grinding head moves linearly on the polishing pad or rotates along the same movement direction as the grinding table; at the same time, the slurry containing the abrasive is dropped onto the polishing pad and is spread on the polishing pad by centrifugation. The chip surface is globally planarized under the dual actions of mechanical and chemical.
The main mechanisms of Chemical Mechanical Polishing (CMP) of metal layers are believed to be: oxidizing the metal surface to form a film by using an oxidizing agent, and mechanically removing the film by using a grinding agent represented by silicon dioxide and aluminum oxide to generate a new metal surface; the new metal surface produced continues to be oxidized, and these two actions work synergistically.
Tungsten, one of the targets of Chemical Mechanical Polishing (CMP), has high electromigration resistance at high current densities and forms good ohmic contact with silicon, and thus can be used as a metal filling and diffusion barrier layer for contact windows and via holes.
Chemical Mechanical Polishing (CMP) of tungsten currently has several methods, such as: kaufman et al reported a method for tungsten Chemical Mechanical Polishing using potassium ferricyanide ("Chemical Mechanical Polishing for Chemical patterning patterns W Metal Features chips", Journal of the Electrochemical Polishing, Vol.138, No.11, 1991, 11 months), a slurry formulation for tungsten Chemical Mechanical Polishing (CMP) disclosed in U.S. Pat. No. 5,310, which contains potassium ferricyanide and silica abrasives, along with acetate as a pH buffer. Potassium ferricyanide has limited its widespread use because it decomposes to highly toxic hydrocyanic acid under ultraviolet or solar irradiation, as well as in acidic media.
US patent US5527423The chemical mechanical polishing liquid for metal layer, the polishing method for semiconductor wafer disclosed in U.S. Pat. No. 006008119A, and the chemical mechanical polishing slurry for tungsten disclosed in U.S. Pat. No. 6284151, etc. all use Fe (NO)3)3The/alumina system is used for tungsten mechanical polishing (CMP). The polishing system has advantages in static etch rate (static etch), but has significant disadvantages in product defects (defects) due to the use of alumina as an abrasive. Meanwhile, the high-concentration ferric nitrate enables the pH value of the polishing solution to be strong acid, so that equipment is seriously corroded, rust is generated, and the polishing pad is polluted. In addition, high concentration of iron ions as mobile metal ions severely reduces the reliability of semiconductor devices.
While the metal CMP polishing composition disclosed in U.S. Pat. No. 5,58288 uses ferric nitrate as a catalyst and hydrogen peroxide as an oxidizer to perform tungsten CMP, it is noted that in this patent, various transition metal elements are mentioned, and only the iron element, which has been experimentally confirmed to be significantly effective, is used, so that the practical effect and scope of the invention are very limited. Although the method greatly reduces the dosage of ferric nitrate, the ferric ions still exist, and the Fenton reaction is generated between the ferric ions and hydrogen peroxide, so that the hydrogen peroxide can be rapidly and violently decomposed and failed, and the polishing solution has the problem of poor stability.
The polishing slurry disclosed in the US patent 5980775 and the polishing slurry disclosed in the US patent 6068787 are based on the US patent 5958288, and an organic acid is added as a stabilizer, so that the decomposition rate of hydrogen peroxide is improved, but the decomposition rate of hydrogen peroxide is still high, and generally the hydrogen peroxide concentration is reduced by more than 10% within two weeks, so that the polishing speed is reduced, and the polishing solution is gradually decomposed and loses efficacy.
Because the static corrosion speed of tungsten in the system of iron and hydrogen peroxide is fast, the production yield is directly influenced, and a static corrosion inhibitor of tungsten needs to be further added for the purpose. Both the polishing composition comprising an inhibitor of tungsten etching, as disclosed in chinese patent CN1326199C, and the polishing composition comprising an inhibitor of tungsten etching, as disclosed in CN1966594A, have an inhibitor of tungsten etching added to a system of hydrogen peroxide and an iron catalyst to inhibit corrosion of tungsten.
In the polishing process of tungsten, there are high requirements for dishing (dishing) and surface flatness (uniformity). US patent US5980775 discloses a method of improving the flatness of silicon wafers using positively charged abrasive particles, while using polyquaterniums. Polyquaternary ammonium salts generally reduce the oxide rate and increase the W/oxide selectivity. Theoretically, the polishing solution is easy to stop on the oxide surface, so that the flatness of the silicon wafer is easy to control. However, in the actual silicon wafer production process, each layer is not completely flat due to the lamination effect, and tungsten remains in the field oxide pits. For the polishing solution with high W/oxide selectivity ratio, when the polishing solution is polished to the silicon dioxide layer, the removal amount of the silicon dioxide is close to 0, and then tungsten residues at the silicon wafer recess can not be removed by polishing. Therefore, the proper polishing solution with a certain silicon dioxide removing amount can remove the tungsten residues in the laminated effect and the concave part by continuously thinning the silicon wafer.
The usual method of increasing the polishing rate of silica is to increase the solids content of the abrasive particles, but this method is very uneconomical. In addition, the polishing liquid is difficult to be concentrated at a high concentration due to the high solid content. The invention provides another technical scheme, and the polishing solution realizes a method for still having higher silicon dioxide polishing speed under the condition of low solid content by adjusting the pH value.
Therefore, it is highly desirable to develop a chemical mechanical polishing solution for polishing tungsten, which can solve the problem of how to achieve a higher polishing rate of silicon dioxide with a low solid content of the abrasive in the polishing solution for tungsten.
Disclosure of Invention
In order to solve the problems, the invention provides a chemical mechanical polishing solution for polishing tungsten, which has a higher polishing speed of silicon dioxide under the condition of low solid content of an abrasive by adjusting the pH value.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a chemical mechanical polishing solution for polishing tungsten comprises silica sol, ferric nitrate and an organic acid complexing agent, wherein the surface of abrasive particles of the silica sol is treated by a silane coupling agent, and the pH value of the polishing solution is 4.0-5.5.
Preferably, the silica sol has a solid content of 0.5% to 5%.
Preferably, the mass percentage content of the ferric nitrate is 0.02% -0.2%.
Preferably, the organic acid complexing agent is selected from one or more of malonic acid, succinic acid, tartaric acid, oxalic acid and citric acid.
Preferably, the content of the organic acid complexing agent is 0.04-4% by mass.
Preferably, the pH stabilizer also comprises a pH stabilizer, wherein the pKa value of the pH stabilizer is 4.0-5.0.
Preferably, the pH stabilizer is selected from one or more of propionic acid, acetic acid, n-butyric acid, isobutyric acid, n-valeric acid, n-hexanoic acid, adipic acid, benzoic acid.
Preferably, the content of the pH stabilizer is 0.05-2% by mass.
Preferably, the chemical mechanical polishing solution further contains hydrogen peroxide.
Compared with the prior art, the chemical mechanical polishing solution for polishing tungsten has the following beneficial effects:
according to the chemical mechanical polishing solution for polishing tungsten, the polishing solution has a higher silicon dioxide polishing speed under the condition of low solid content of an abrasive by adjusting the pH value, can remove tungsten residues at a depression formed in a lamination effect, improves the polishing quality and improves the yield; reduces the manufacturing cost of the product and is beneficial to high-power concentration.
Drawings
FIG. 1 is a summary graph of pH versus polishing rate obtained from the polishing data for each of the examples of the present invention and comparative examples.
Detailed Description
The present invention will be further described with reference to the following specific examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.
The reagents and starting materials used in the present invention are commercially available.
The wt% of the invention refers to mass percentage content.
The polishing conditions in the following examples and comparative examples of the present invention were: diluting the polishing solution with 9 times of water by weight, adding 2.5% hydrogen peroxide, and polishing with a Mirra machine with a polishing pad IC1010 and a polishing pressure of 3 psi.
Examples 1-8 and comparative examples:
the polishing solution is prepared according to the components and the proportion of the components in each example and each comparative example in the table 1, the components are uniformly mixed, the mass percent is complemented to 100 percent by water, and the pH value is adjusted to the required pH value by nitric acid or KOH.
TABLE 1 formulation of specific examples of the invention and comparative examples
In Table 1, A is a conventional silica and B is synthesized from a conventional silica and triethoxysiloxane aminopropionate.
As can be seen from Table 1, the polishing liquids of comparative examples 1 to 13, which used conventional silica as abrasive grains and had a pH in the range of 2 to 8, had only the highest polishing rates for silica
The polishing rate of the polishing solution to the silicon dioxide tends to decrease with the increase of the pH. On the other hand, the polishing solutions of examples 1 to 3 of the present invention, which used the abrasive grains obtained by synthesizing conventional silica and triethoxysiloxane aminopropionate, exhibited excellent polishing rates for silica in the pH range of 4 to 5.5, all in the range of
The above.
The number of polishing in Table 1The pH value-polishing rate are summarized in FIG. 1. As can be seen from fig. 1, the pH value has a significant effect on the polishing rate of silicon dioxide by the polishing liquid. Wherein, the polishing liquid using the conventional silicon dioxide as the abrasive particles has the highest polishing rate to the silicon dioxide when the pH value of the polishing liquid is 2-3, which is about
Left and right; when the pH of the polishing solution is increased, the polishing rate of the polishing solution to silicon dioxide begins to decrease, and when the pH of the polishing solution is about 5, the polishing rate of the polishing solution to silicon dioxide reaches a minimum value about
Left and right; when the pH of the polishing solution continues to increase, the polishing rate of the polishing solution to silicon dioxide hardly changes. In the polishing solution of the abrasive particles synthesized by the conventional silicon dioxide and the triethoxysiloxane aminopropionate, when the pH of the polishing solution is within the range of 2-5, the polishing rate of the polishing solution to the silicon dioxide is increased continuously along with the increase of the pH of the polishing solution, and the highest polishing rate can be reached
Left and right; when the pH value of the polishing solution continues to increase, the polishing rate of the polishing solution to the silicon dioxide gradually decreases, and the polishing solution tends to be stable when the pH value of the polishing solution reaches 7, and the minimum value is about
Left and right. Therefore, when the polishing solution using the abrasive particles B of the present invention has a polishing rate for silicon dioxide within a range of pH 4 to 5.5, the polishing rate that cannot be achieved by ordinary silicon dioxide abrasive particles can be achieved. The polishing solution of the embodiment of the invention can realize higher silicon dioxide polishing speed under the condition of low solid content of the grinding agent by adjusting the pH value, can remove tungsten residues at the depression formed in the lamination effect, improves the polishing quality and improves the yield.
Examples 9 to 17:
due to the nature of silica sols, the pH changes with the time of standing. In order to stabilize the pH value, a pH stabilizer may be further added to the formulation system for stabilizing the pH value. Useful pH stabilizers are selected from weak acids with pKa values between 4.0 and 5.0, such as propionic acid (pKa: 4.87), acetic acid (pKa: 4.76), n-butyric acid (pKa: 4.82), isobutyric acid (pKa: 4.85), n-valeric acid (pKa: 4.86), n-hexanoic acid (pKa: 4.86), adipic acid (pKa: 4.42), benzoic acid (pKa: 4.2).
The polishing solution is prepared according to the components and the proportion thereof in each example in the table 2, mixed evenly, water is used for complementing the mass percent to 100 percent, and nitric acid or KOH is used for adjusting the pH value to the required value.
TABLE 2 formulation of specific examples of the invention
As can be seen from Table 2, the chemical mechanical polishing solution of the present invention has not only an excellent polishing rate of tungsten, but also a high polishing rate of silicon dioxide, and after being left for a period of time, the polishing solution can still achieve a high polishing rate of silicon dioxide, thereby greatly increasing the service life of the tungsten polishing solution.
It should be noted that the embodiments of the present invention have been described in terms of preferred embodiments, and not by way of limitation, and that those skilled in the art can make modifications and variations of the embodiments described above without departing from the spirit of the invention.
Claims (9)
1. The chemical mechanical polishing solution for polishing tungsten is characterized by comprising silica sol, ferric nitrate and an organic acid complexing agent, wherein the surface of abrasive particles of the silica sol is treated by a silane coupling agent, and the pH value of the polishing solution is 4.0-5.5.
2. The chemical mechanical polishing solution of claim 1, wherein the silica sol has a solid content of 0.5% to 5%.
3. The chemical mechanical polishing solution according to claim 1, wherein the content of the ferric nitrate is 0.02 to 0.2 percent by mass.
4. The chemical mechanical polishing solution of claim 1, wherein the organic acid complexing agent is selected from one or more of malonic acid, succinic acid, tartaric acid, oxalic acid, and citric acid.
5. The chemical mechanical polishing solution according to claim 1 or 4, wherein the organic acid complexing agent is contained in an amount of 0.04% to 4% by mass.
6. The chemical mechanical polishing solution of claim 1, further comprising a pH stabilizer, wherein the pKa of the pH stabilizer is from 4.0 to 5.0.
7. The chemical mechanical polishing solution of claim 6, wherein the pH stabilizer is selected from one or more of propionic acid, acetic acid, n-butyric acid, isobutyric acid, n-valeric acid, n-caproic acid, adipic acid, and benzoic acid.
8. The chemical mechanical polishing solution according to claim 6, wherein the pH stabilizer is contained in an amount of 0.05 to 2% by mass.
9. The chemical mechanical polishing solution according to claim 1, further comprising hydrogen peroxide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811627123.2A CN111378373A (en) | 2018-12-28 | 2018-12-28 | Chemical mechanical polishing solution for polishing tungsten |
| TW108148033A TWI838447B (en) | 2018-12-28 | 2019-12-27 | Chemical-mechanical polishing slurry for polishing tungsten |
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| CN201811627123.2A CN111378373A (en) | 2018-12-28 | 2018-12-28 | Chemical mechanical polishing solution for polishing tungsten |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113583572A (en) * | 2021-07-09 | 2021-11-02 | 万华化学集团电子材料有限公司 | Tungsten chemical mechanical polishing solution and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051126A (en) * | 2009-11-06 | 2011-05-11 | 安集微电子（上海）有限公司 | Polishing solution for tungsten chemical mechanical polishing |
| CN102533121A (en) * | 2010-12-27 | 2012-07-04 | 安集微电子（上海）有限公司 | Chemically mechanical polishing solution for polishing tungsten |
| CN102816528A (en) * | 2011-06-08 | 2012-12-12 | 安集微电子（上海）有限公司 | Chemical-mechanical polishing solution for polishing tungsten |
| CN102816529A (en) * | 2011-06-08 | 2012-12-12 | 安集微电子（上海）有限公司 | Tungsten chemical-mechanical polishing solution being beneficial for cleaning after polishing |
| CN102850937A (en) * | 2011-06-29 | 2013-01-02 | 安集微电子科技(上海)有限公司 | Chemical mechanical polishing (CMP) liquid |
| CN106661430A (en) * | 2014-06-25 | 2017-05-10 | 嘉柏微电子材料股份公司 | Tungsten chemical-mechanical polishing composition |
-
2018
- 2018-12-28 CN CN201811627123.2A patent/CN111378373A/en active Pending
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2019
- 2019-12-27 TW TW108148033A patent/TWI838447B/en active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051126A (en) * | 2009-11-06 | 2011-05-11 | 安集微电子（上海）有限公司 | Polishing solution for tungsten chemical mechanical polishing |
| CN102533121A (en) * | 2010-12-27 | 2012-07-04 | 安集微电子（上海）有限公司 | Chemically mechanical polishing solution for polishing tungsten |
| CN102816528A (en) * | 2011-06-08 | 2012-12-12 | 安集微电子（上海）有限公司 | Chemical-mechanical polishing solution for polishing tungsten |
| CN102816529A (en) * | 2011-06-08 | 2012-12-12 | 安集微电子（上海）有限公司 | Tungsten chemical-mechanical polishing solution being beneficial for cleaning after polishing |
| CN102850937A (en) * | 2011-06-29 | 2013-01-02 | 安集微电子科技(上海)有限公司 | Chemical mechanical polishing (CMP) liquid |
| CN106661430A (en) * | 2014-06-25 | 2017-05-10 | 嘉柏微电子材料股份公司 | Tungsten chemical-mechanical polishing composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113583572A (en) * | 2021-07-09 | 2021-11-02 | 万华化学集团电子材料有限公司 | Tungsten chemical mechanical polishing solution and application thereof |
| CN113583572B (en) * | 2021-07-09 | 2022-08-05 | 万华化学集团电子材料有限公司 | Tungsten chemical mechanical polishing solution and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202027175A (en) | 2020-07-16 |
| TWI838447B (en) | 2024-04-11 |
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