KR101741989B1 - Slurry composition for poly silicon film polishing - Google Patents
Slurry composition for poly silicon film polishing Download PDFInfo
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- KR101741989B1 KR101741989B1 KR1020150180038A KR20150180038A KR101741989B1 KR 101741989 B1 KR101741989 B1 KR 101741989B1 KR 1020150180038 A KR1020150180038 A KR 1020150180038A KR 20150180038 A KR20150180038 A KR 20150180038A KR 101741989 B1 KR101741989 B1 KR 101741989B1
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- KR
- South Korea
- Prior art keywords
- acid
- choline
- polishing
- hydroxide
- polysilicon film
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1436—Composite particles, e.g. coated particles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
Abstract
Description
The present invention relates to a slurry composition for polishing a polysilicon film.
As the semiconductor devices are diversified and highly integrated, a finer pattern forming technique is used, thereby complicating the surface structure of the semiconductor device and increasing the step difference of the surface films. A chemical mechanical polishing (CMP) process is used as a planarization technique for removing a step in a specific film formed on a substrate in manufacturing a semiconductor device. For example, an interlayer dielectric (ILD) and a shallow trench isolation (STI) insulating film for insulation between chips are formed in a process for removing an insulating film formed in an excessive amount for interlayer insulation. And a process for forming a metal conductive film such as wiring, contact plugs, via contacts, and the like.
In general, there are various kinds of slurry compositions depending on the kind and characteristics of the object to be removed. There is a need for a chemical mechanical polishing slurry composition capable of controlling the removal rate of the silicon oxide film exposed in the polishing of the polysilicon film. Thus, a slurry composition capable of uniformly polishing a semiconductor substrate is required because the removal rate of the silicon oxide film is small while the removal rate of the polysilicon film is high, and the polishing selectivity of the polysilicon film to the oxide film is high.
It is an object of the present invention to provide a slurry composition for polishing a polysilicon film capable of realizing a high polishing rate of a polysilicon film and an excellent polishing selectivity of a polysilicon film to an oxide film .
However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.
According to one embodiment of the present invention, a first selection ratio improver; A second selective ratio improver; Organic acids; And abrasive grains. The present invention also provides a slurry composition for polishing a polysilicon film.
The first selection ratio improver may be one comprising a quaternary amine, choline, a salt thereof, or a derivative thereof.
The quaternary amine, a salt thereof or a derivative thereof may be at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetracyclopropylammonium hydroxide, tetra Tetrabutylammonium hydroxide, butylammonium hydroxide, tetraisobutylammonium hydroxide, tetrapentylammonium hydroxide, tetracyclopentylammonium hydroxide, tetrahexylammonium hydroxide, tetracyclohexylammonium hydroxide, tetramethylammonium chloride, tetra Butyl ammonium chloride, trimethyl benzyl ammonium chloride, triethyl benzyl ammonium chloride, tributyl benzyl ammonium chloride, trioctyl methyl ammonium chloride, trimethyldodecyl ammonium chloride, N-lauryl pyridinium chloride, dimethyl pyrrolidinium At least one selected from the group consisting of boron trichloride, tridecyl ammonium bromide, tetraethyl ammonium bromide, tetra-n-butyl ammonium bromide, and dimethylpyrrolidinium bromide .
The choline, its salt or a derivative thereof may be selected from the group consisting of choline hydroxide, choline fluoride, choline chloride, choline base, choline bromide, Choline iodide, choline dihydrogen citrate, choline bitartrate, choline bicarbonate, choline citrate, choline ascorbate, Choline borate, choline theophyllinate, choline gluconate, acetylcholine chloride, acetylcholine bromide, and methacholine chloride. And at least one selected from the group consisting of
The second selection ratio improver may be at least one selected from the group consisting of propylamine, dibutylamine, tributylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, ethanolamine, isopropylamine, diethanolamine, Amino-2-methyl-1-propanol (AMP), 2,2-dimethyl-1,3-diaminopropane, hexamethylenediamine, 3-methylaminopropyl Amino-2-methyl-1-propanol, 1-amino-2-propanol, 3- Dimethylamino-2-propanol, 1-dimethylamino-2-propanol, 3-dimethylamino-1-propanol, 2- Ethanolamine, N-propyldiethanolamine, N-isopropyldiethanolamine, N- (2-methylpropyl) diethanolamine, Nn-butyldi 2-t-butylaminoethanol, N-cyclohexyldiethanolamine, 2- (dimethylamino) ethanol, 2-diethylaminoethanol, Amino-2-pentanol, 2- [bis (2-hydroxyethyl) amino] -2-methyl-1-propanol, 2- [bis Amino-2-methyl-1-propanol, tris (hydroxymethyl) aminomethane, triisopropanolamine, and 5 -Dimethylaminopentylamine, or a salt thereof.
The first selection ratio improver and the second selection ratio improver may be 0.01 wt% to 5 wt%, respectively, of the slurry composition for polishing a polysilicon film.
The organic acid is at least one selected from the group consisting of citric acid, acetic acid, adipic acid, lactic acid, phthalic acid, gluconic acid, glycolic acid, propionic acid, oxalic acid, succinic acid, malonic acid, malic acid, tartaric acid, maleic acid, picolinic acid, nicotinic acid, isonicotinic acid, But are not limited to, adipic acid, adipic acid, adipic acid, adipic acid, fumaric acid, isophthalic acid, terephthalic acid, itaconic acid, mandelic acid, phenylacetic acid, 1-naphthoic acid At least one selected from the group consisting of citric acid, citric acid, citric acid, citric acid, citric acid, citric acid, citric acid, citric acid, citric acid,
The organic acid may be 0.01 wt% to 5 wt% of the slurry composition for polishing the polysilicon film.
Wherein the abrasive particles comprise at least one selected from the group consisting of a metal oxide coated with a metal oxide, an organic substance or an inorganic substance, and the metal oxide in a colloidal state, and the metal oxide is at least one selected from the group consisting of silica, ceria, zirconia, alumina, At least one selected from the group consisting of titania, barium titania, germania, manganese, and magnesia.
And the average particle size of the abrasive grains is 10 nm to 300 nm.
The abrasive grains may be 0.1 wt% to 10 wt% of the slurry composition for polishing the polysilicon film.
The pH of the slurry composition for polishing the polysilicon film may be 9 to 12.
The slurry composition for polishing a polysilicon film may have a polishing selectivity of 10 to 500 for a polysilicon film to an oxide film.
The slurry composition for polishing a polysilicon film according to an embodiment of the present invention includes both the first selective ratio improver and the second selection ratio improver so that the high polishing rate of the polysilicon film in the alkali region and the excellent polishing rate of the polysilicon film Can be implemented.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. In addition, terms used in this specification are terms used to appropriately express the preferred embodiments of the present invention, which may vary depending on the user, the intention of the operator, or the practice of the field to which the present invention belongs. Therefore, the definitions of these terms should be based on the contents throughout this specification. Like reference symbols in the drawings denote like elements.
Throughout the specification, when an element is referred to as "comprising ", it means that it can include other elements as well, without excluding other elements unless specifically stated otherwise.
Hereinafter, the slurry composition for polishing a polysilicon film of the present invention will be described in detail with reference to examples and drawings. However, the present invention is not limited to these embodiments and drawings.
According to one embodiment of the present invention, a first selection ratio improver; A second selective ratio improver; Organic acids; And abrasive grains. The present invention also provides a slurry composition for polishing a polysilicon film.
The slurry composition for polishing a polysilicon film according to an embodiment of the present invention includes the first selection ratio improver and the second selection ratio improver so that the high polishing rate of the polysilicon film in the alkali region and the excellent polishing selectivity of the polysilicon film Can be implemented.
In the present invention, the first selective non-enhancing agent and the second selective non-enhancing agent can serve as a pH adjusting agent and can realize a high polishing rate of the polysilicon film when the first selective non-enhancing agent and the second selective non- .
The first selection ratio improver may be a quaternary ammonium base compound, for example, a quaternary amine, choline, a salt thereof, or a derivative thereof.
The quaternary amine, a salt thereof or a derivative thereof may be at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetracyclopropylammonium hydroxide, tetra Tetrabutylammonium hydroxide, butylammonium hydroxide, tetraisobutylammonium hydroxide, tetrapentylammonium hydroxide, tetracyclopentylammonium hydroxide, tetrahexylammonium hydroxide, tetracyclohexylammonium hydroxide, tetramethylammonium chloride, tetra Butyl ammonium chloride, trimethyl benzyl ammonium chloride, triethyl benzyl ammonium chloride, tributyl benzyl ammonium chloride, trioctyl methyl ammonium chloride, trimethyldodecyl ammonium chloride, N-lauryl pyridinium chloride, dimethyl pyrrolidinium And at least one selected from the group consisting of chloride, trimethylphenyl ammonium bromide, triethylbenzyl ammonium bromide, tetramethyl ammonium bromide, tetraethyl ammonium bromide, tetra-n-butyl ammonium bromide and dimethylpyrrolidinium bromide have.
The choline, its salt or a derivative thereof may be selected from the group consisting of choline hydroxide, choline fluoride, choline chloride, choline base, choline bromide, Choline iodide, choline dihydrogen citrate, choline bitartrate, choline bicarbonate, choline citrate, choline ascorbate, Choline borate, choline theophyllinate, choline gluconate, acetylcholine chloride, acetylcholine bromide, and methacholine chloride. And at least one selected from the group consisting of
The second selection ratio improver may be an amine compound such as propylamine, dibutylamine, tributylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, Amino-2-methyl-1-propanol (AMP), 2,2-dimethyl-1,3-diaminopropane, hexa Propylamine, 3- (dimethylamino) propylamine, 4-dimethylaminobutylamine, 2-diethylamino-2-methyl-1-propanol, Dimethylamino-1-propanol, 2-ethylamino-1-ethanol, 1- (dimethylamino) 2-propanol, N-methyldiethanolamine, N-propyldiethanolamine, N-isopropyldiethanolamine, N- (2- N-cyclohexyldiethanolamine, 2- (dimethylamino) ethanol, 2-diethylaminoethanol, 2-dipropylaminoethanol, 2-diethylaminoethanol, 2-amino-2-pentanol, 2- [bis (2-hydroxyethyl) amino] -2-methyl-1-propanol (2-hydroxyethyl) amino] -2-propanol, N, N-bis (2-hydroxypropyl) ethanolamine, 2- Methyl) aminomethane, tri-isopropanolamine, and 5-dimethylaminopentylamine.
The first selective non-enhancing agent and the second selective non-enhancing agent may be added in an amount to adjust the pH of the slurry composition for polishing a polysilicon film of the present invention, and the pH of the slurry composition for polishing the polysilicon film is preferably 9 to 12 It may be an alkaline region. Preferably, the first selection ratio improver and the second selection ratio improver may be added in an amount of 0.01 wt% to 5 wt%, respectively, in the slurry composition for polishing a polysilicon film. When the first selective ratio improver and the second selective ratio improver are less than 0.01% by weight in the slurry composition for polishing the polysilicon film, it is difficult to realize a desired selectivity ratio, and in the case of more than 5% by weight, surface defects may be increased.
The organic acid is at least one selected from the group consisting of citric acid, acetic acid, adipic acid, lactic acid, phthalic acid, gluconic acid, glycolic acid, propionic acid, oxalic acid, succinic acid, malonic acid, malic acid, tartaric acid, maleic acid, picolinic acid, nicotinic acid, isonicotinic acid, But are not limited to, adipic acid, adipic acid, adipic acid, adipic acid, fumaric acid, isophthalic acid, terephthalic acid, itaconic acid, mandelic acid, phenylacetic acid, 1-naphthoic acid At least one selected from the group consisting of citric acid, citric acid, citric acid, citric acid, citric acid, citric acid, citric acid, citric acid, citric acid,
The organic acid may be 0.01 wt% to 5 wt% of the slurry composition for polishing the polysilicon film. If the organic acid is less than 0.01% by weight in the slurry composition for polishing the polysilicon film, it may exhibit low polishing characteristics for the polysilicon film, and if it exceeds 5% by weight, surface defects may be increased.
Wherein the abrasive particles comprise at least one selected from the group consisting of a metal oxide coated with a metal oxide, an organic substance or an inorganic substance, and the metal oxide in a colloidal state, and the metal oxide is at least one selected from the group consisting of silica, ceria, zirconia, alumina, At least one selected from the group consisting of titania, barium titania, germania, manganese, and magnesia. Preferably, a metal oxide in a colloidal state can be used.
The abrasive grains may be 0.1 wt% to 10 wt% of the slurry composition for polishing the polysilicon film. When the abrasive grains are less than 0.1 wt% in the slurry composition for polishing the polysilicon film, the polishing rate of the polysilicon film is decreased. When the abrasive grains are more than 10 wt%, scratches are likely to occur in the polysilicon film due to abrasive grains.
And the average particle size of the abrasive grains is 10 nm to 300 nm. If the abrasive grains are less than 10 nm, there is a problem that the polishing rate is lowered and there is a problem that the selection ratio is difficult to implement. When the abrasive grains are more than 300 nm, it is difficult to control the surface defects, the polishing rate and the selection ratio.
The abrasive grains may include those prepared by the liquid phase method. The liquid phase method includes a sol-gel method in which an abrasive particle precursor is caused to undergo a chemical reaction in an aqueous solution and crystals are grown to obtain fine particles, a coprecipitation method in which abrasive particle ions are precipitated in an aqueous solution, A hydrothermal synthesis method such as a hydrothermal synthesis method.
The slurry composition for polishing a polysilicon film may have a polishing selectivity of 10 to 500 for a polysilicon film to an oxide film. The polishing rate of the polysilicon film to the oxide film is high and the semiconductor substrate can be uniformly polished.
The polysilicon film polishing slurry composition may have a polysilicon film polishing rate of 1,000 A / min to 5,000 A / min, and an oxide film polishing rate of 10 A / min to 100 A / min.
In addition, the slurry composition may contain water or a water solvent containing the same as a medium for dissolving or dispersing the respective components described above.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
[Example 1]
0.3% by weight of citric acid was added to ultrapure water and mixed at a high speed. 0.1% by weight of tetramethylammonium hydroxide (TMAH) was added as a quaternary ammonium base compound, and 2-amino- 0.6% by weight of propanol (AMP-95) was added thereto to adjust the pH to 10, and 0.5% by weight of colloidal silica was added thereto at a high speed to prepare a slurry composition having a particle size of 60 nm.
[Example 2]
Except that 0.1 wt% of choline hydroxide was added instead of tetramethylammonium hydroxide (TMAH) as a quaternary ammonium base compound and 0.6 wt% of AMP-95 was added so that the pH was 10, a slurry A composition was prepared.
[Comparative Example]
A slurry composition was prepared in the same manner as in Example 1 except that 0.15% by weight of potassium hydroxide (KOH) was added as a primary amine so as to have a pH of 11 instead of 2-amino-2-methylpropanol (AMP- Respectively.
[Polishing condition]
The slurry compositions of Examples 1 and 2 and Comparative Examples of the present invention were used to polish wafers under the following polishing conditions, and the results were compared.
1. Grinding machine: ST # 01 (KCStech)
2. Polishing pad: K7
3. Polishing target film: Polysilicon film (Poly-Si), polytetraethylorthosilicate (PETEOS)
4. Platen RPM (Platen RPM): 100 rpm
5. Carrier RPM (carrier RPM): 103 rpm
6. Wafer pressure: 7.5 psi
7. Polishing time: Polysilicon film 30 seconds, oxide film 60 seconds
8. Flow rate: 250 ml / min
Table 1 shows results of polishing rate of poly-Si and PETEOS films and polymorph / oxide film selection ratio after polishing using the slurry compositions of Examples 1 and 2 and Comparative Examples of the present invention.
Silica
(weight%)
(weight%)
(weight%)
(weight%)
Hydlock
side
(weight%)
(weight%)
It can be seen that the polishing slurry compositions of Examples 1 and 2 of the present invention can realize a high polishing rate of the polysilicon film and realize a high selectivity ratio of the polysilicon film to the oxide film in comparison with the comparative example.
While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. This is possible. Therefore, the scope of the present invention should not be limited by the described embodiments, but should be determined by the equivalents of the appended claims, as well as the appended claims.
Claims (13)
A second selective ratio improver;
Organic acids; And
Abrasive particles;
Lt; / RTI >
The first selection ratio improver includes a quaternary amine, choline, a salt thereof, or a derivative thereof,
The quaternary amine, a salt thereof or a derivative thereof may be at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetracyclopropylammonium hydroxide, tetra At least one selected from the group consisting of butylammonium hydroxide, tetraisobutylammonium hydroxide, tetrapentylammonium hydroxide, tetracyclopentylammonium hydroxide, tetrahexylammonium hydroxide, and tetracyclohexylammonium hydroxide. And includes any one of them,
The choline, its salt or a derivative thereof may be selected from the group consisting of choline hydroxide, choline fluoride, choline chloride, choline base, choline bromide, Choline iodide, choline dihydrogen citrate, choline bitartrate, choline bicarbonate, choline citrate, choline ascorbate Choline borate, choline theophyllinate, choline gluconate, acetylcholine chloride, acetylcholine bromide, and methacholine chloride. And at least one selected from the group consisting of
The second selection ratio enhancer may be selected from the group consisting of 2-amino-2-methyl-1-propanol (AMP), 2-diethylamino- Dimethylamino-2-propanol, N-methyldiethanolamine, N-methyldiethanolamine, N-methyldiethanolamine, N- Butyldiethanolamine, N-cyclohexyldiethanolamine, N-cyclohexyldiethanolamine, 2- (dimethyl (2-methylpropyl) diethanolamine, N- 2-amino-2-pentanol, 2-amino-2-butanol, 2- (2-hydroxyethyl) amino] -2-propanol, N, N-bis (2-hydroxyethyl) Ethanolamine, 2-amino-2- Butyl-1-propanol, tris (hydroxymethyl) it will include at least one selected from the group consisting of amino methane and isopropanol amine triazole,
The organic acid may be at least one selected from the group consisting of citric acid, adipic acid, lactic acid, phthalic acid, gluconic acid, glycolic acid, oxalic acid, succinic acid, malonic acid, malic acid, tartaric acid, maleic acid, dinicotinic acid, dipiconic acid, lutidonic acid, At least one selected from the group consisting of valeric acid, aspartic acid, suberic acid, fumaric acid, isophthalic acid, terephthalic acid, itaconic acid, mandelic acid, 1,2,3,4-butanetetracarboxylic acid and glutamic acid However,
Wherein the abrasive particles comprise at least one selected from the group consisting of silica coated with an organic material or an inorganic material, and colloidal silica.
A slurry composition for polishing a polysilicon film.
Wherein each of the first selective ratio improver and the second selective ratio improver is 0.01 wt% to 5 wt% of the slurry composition for polishing a polysilicon film.
Wherein the organic acid is 0.01 wt% to 5 wt% of the slurry composition for polishing the polysilicon film.
Wherein the average particle size of the abrasive grains is 10 nm to 300 nm.
Wherein the abrasive grains are 0.1 wt% to 10 wt% of the slurry composition for polishing the polysilicon film.
Wherein the pH of the slurry composition for polishing a polysilicon film is in the range of 9 to 12.
Wherein the polishing slurry composition for polishing a polysilicon film has a polishing selectivity of a polysilicon film to an oxide film of 10 to 500.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20190072981A (en) * | 2017-12-18 | 2019-06-26 | 주식회사 케이씨텍 | Chemical mechanical polishing slurry composition of wafer contaning poly-silicon |
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| KR20190072981A (en) * | 2017-12-18 | 2019-06-26 | 주식회사 케이씨텍 | Chemical mechanical polishing slurry composition of wafer contaning poly-silicon |
| KR102533088B1 (en) * | 2017-12-18 | 2023-05-17 | 주식회사 케이씨텍 | Chemical mechanical polishing slurry composition of wafer contaning poly-silicon |
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