KR20140146881A - Composition for forming neutral layer and method for forming directed self assembly resist pattern using the same - Google Patents
Composition for forming neutral layer and method for forming directed self assembly resist pattern using the same Download PDFInfo
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Abstract
Description
The present invention relates to a composition for forming a neutral layer and a method for forming a self-assembled resist pattern using the same, and more particularly, to a method for forming a self-assembled resist pattern by selectively exposing a neutral layer without forming a guide pattern And a method for forming self-assembled resist patterns using the same.
In order to miniaturize and integrate a semiconductor device, it is necessary to form a finer circuit pattern. For this purpose, improvement of an exposure apparatus or improvement of a pattern forming method has been researched. Improving the exposure equipment has the disadvantage that the initial investment costs are incurred and the utilization of the existing equipment is lowered, so it is preferable to improve the pattern formation method.
As one of the improved pattern formation processes, a directed self-assembly (DSA) pattern formation process using a self-alignment of a block copolymer (BCP) is considered to be a limitation of an optical pattern formation process. It is expected that a resist pattern having a pattern line width size of 20 nm or less can be realized. The DSA process is a method of forming a fine resist pattern by grafting the orientation characteristics of a block copolymer to an existing photoresist pattern forming process and orienting the block copolymer in a certain direction. Specifically, in the DSA process, a predetermined photoresist pattern (guide pattern) is formed by using a conventional ArF, KrF, or I-line photoresist composition on a substrate such as a wafer or an ITO glass Then, BCP is coated on the space between the photoresist patterns and heated to form a BCP coating film. Next, the coated thin film is heated to a temperature not lower than the glass transition temperature (Tg) of the BCP to rearrange the BCP (self-aligning or self-aligning) and remove a part of the rearranged BCP, An alignment resist pattern can be obtained (see Patent Document 10-2010-0126190, Patent Application No. 10-2011-0098838 (filed on September 29, 2011)).
In order to form a fine pattern by self-alignment, a neutral layer should generally be formed as a lower film of BCP. In the case of silicon wafers or ITO glasses used in semiconductors or LCD processes, they have different polarities depending on the material, which interferes with the self-alignment of the BCPs arranged in accordance with the polarity, thereby making it difficult to form a pattern. For example, when the non-polar portion of the BCP is located adjacent to the lower film and the lower film is made of a polar material, when the lower film is made of a nonpolar material, the polar portion of the BCP is positioned adjacent to the lower film, The lamellar structure pattern of the horizontal alignment can not be formed and a horizontal alignment lamellar structure is formed. Therefore, in order to vertically align the BCP and form a lamellar structural pattern, it is necessary to form a neutral layer under the BCP.
In order to form such a neutral layer, a compound having an intermediate polarity value between a polar portion and a non-polar portion of BCP has been conventionally used, and a PS-r-PMMA (polystyrene-r-poly (methylmethacylate) A polymer compound in which a polar portion and a non-polar portion are mixed, such as a styrene homopolymer, a styrene homopolymer, and a random copolymer of styrene and epoxy (polystyrene-r-epoxy) are used. However, in the case of forming a neutral layer by only the above-mentioned compound having an intermediate polarity value, the formed neutral layer functions only as a neutral layer regardless of exposure or non-exposure. In addition, in order to form the self-aligned resist pattern by the induced self-assembly process using the conventional neutral layer, there is a disadvantage that the guide pattern must be formed as described above.
It is an object of the present invention to provide a composition for forming a neutral layer capable of forming a self-aligned resist pattern by an induced self-assembly process without forming a guide pattern, and a self-assembled resist pattern forming method using the self-assembled resist pattern.
Another object of the present invention is to provide a composition for forming a neutral layer capable of selectively forming a neutral layer and controlling the formation region of the induced self-assembled pattern, and a method of forming a self-assembled pattern resist using the composition.
It is still another object of the present invention to provide a composition for forming a neutral layer which can simplify the whole process since it is unnecessary to form a guide pattern, and a self-assembled resist pattern forming method using the same.
In order to accomplish the above object, the present invention provides a polymer comprising a repeating unit represented by the following formula (1); Acid generators; A crosslinking agent; And a solvent for forming a neutral layer.
[Chemical Formula 1]
In the above formula (1), R 1 is a hydrogen atom or a methyl group, and x and y are 40 to 90 mol% and 10 to 60 mol%, respectively, in mole% of each repeating unit constituting the polymer.
The present invention also provides a method for manufacturing a semiconductor device, comprising the steps of: applying the composition for forming a neutral layer on a substrate; forming a lower film by removing the solvent from the applied composition for forming a neutral layer; Partially exposing the lower film so that the portion where the resist pattern is to be formed is not exposed and the portion where the resist pattern is not formed is exposed; Coating a block copolymer solution obtained by dissolving a block copolymer in an organic solvent on the partially exposed lower film and then heating to form a block copolymer coating film; And heating the substrate on which the block copolymer coating film is formed to a temperature not lower than a glass transition temperature (Tg) of the block copolymer to obtain a self alignment pattern and etching the self alignment pattern. to provide.
According to the composition for forming a neutral layer and the method for forming a self-assembled pattern derived therefrom according to the present invention, it is possible to form a self-aligned resist pattern without forming a guide pattern, It is possible to simplify the resist pattern forming process by induced self-assembly.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing a change in the nanostructure of a block copolymer according to a copolymer component ratio of a block copolymer. FIG.
Figure 2 shows that when a resist pattern is formed by forming a conventional bottom film (neutral layer) and annealing the block copolymer on top of the bottom film, a pattern is formed not only in the central region of the cell but also in the bulk region of the cell Scanning electron microscope picture.
FIG. 3 is a cross-sectional view illustrating a method of forming a resist pattern by forming a lower film using the composition for forming a neutral layer according to the present invention, partially exposing the lower film, and then annealing the block copolymer at an upper portion of the lower film, A scanning electron microscope photograph showing the difference in the resist pattern formed in the unexposed area.
Hereinafter, the present invention will be described in detail.
The composition for forming a neutral layer according to the present invention comprises at least one polymer selected from the group consisting of (i) a polymer comprising a repeating unit represented by the following formula (1), (ii) an acid generator, (iii) a crosslinker, and . The polymer comprising a repeating unit represented by the following formula (1) is a polymer having a repeating unit represented by the following general formula (1) That is, a neutral layer. Hereinafter, if necessary, a polymer containing a repeating unit represented by the following formula (1) is referred to as a polymer for forming a neutral layer, a polymer for forming a lower film, or simply a polymer.
[Chemical Formula 1]
In Formula 1, R 1 is a hydrogen atom or a methyl group, and x and y are 40 to 90 mol% and 10 to 60 mol%, preferably 60 to 90 mol%, respectively, as molar percentages of the respective repeating units constituting the polymer Mol% and 10 to 40 mol%, more preferably 65 to 80 mol% and 20 to 35 mol%, respectively. For example, the x: y may have a molar ratio of 5: 5, 6: 4, 7: 3, 8: 2, The polymer for forming a neutral layer has a weight average molecular weight (Mw) of 3,000 to 100,000, preferably 5,000 to 30,000, more preferably 5,000 to 15,000, and a polydispersity (PD) 3.0, and more preferably 1.2 to 2.0. If the weight average molecular weight (Mw) of the polymer is too small or too large, there is a fear that a neutral film of a uniform film quality may not be formed. When the content of each repeating unit in the polymer is out of the above range, the change in physical properties due to heating or exposure is too small or too large to achieve the object of the present invention.
The polymer for forming a neutral layer may be prepared by polymerizing styrene vinyl and (meth) acrylic acid by a conventional polymeric polymerization method, wherein azobis ((meth) acrylic acid) Isobutyronitrile) (AIBN) may be used. In the polymer for forming a neutral layer, the content of each repeating unit is proportional to the content of the monomer used, and the polymer for forming the neutral layer may be a block or a random copolymer.
The acid generator (ii) used in the composition for forming a neutral layer according to the present invention generates an acid component by light or heat, and thereby the (i) neutral layer forming polymer and (iii) the crosslinking agent To promote cross-linking. Examples of the acid generator include a photo acid generator (PAG) that generates an acid component by exposure or a thermal acid generator (TAG) that generates an acid component by heating. Can be used. In some cases, one compound acts as the photoacid generator and the thermal acid generator. In the present invention, the acid generator may be used singly or in a mixture of one or more. As the photoacid generator, a sulfonium salt compound, an iodonium salt compound or a mixture thereof may be used. Specific examples thereof include triphenylsulfonium triflate, phthalimidotrifluoromethanesulfonate, trifluoromethanesulfonate, dinitrobenzyl tosylate, n-decyl disulfone, naphthylimidotrifluoro methanesulfonate, diphenyl iodide salt triflate, diphenyl iodide salt nona Plate, diphenyl iodide salt hexafluorophosphate, diphenyl iodide salt hexafluoroarsenate, diphenyl iodide salt hexafluoroantimonate, diphenyl para methoxy phenylsulfonium triflate, diphenyl para toluenesulfonium triflate , Diphenyl para tertiary butylphenylsulfonium triflate, diphenyl paraisobutylphenylsulfonium Triflate, tetrabutylphenylsulfonium triflate, diphenyl para-methoxyphenylsulfonium nonaplate, diphenyl para-toluenesulfonium nonaplate, diphenyl parathetic butylphenylsulfonium nonaplate, diphenyl para Hexafluoroarsenate, triphenylsulfonium hexafluoroantimonate, dibutylnaphthylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate Plates, mixtures thereof and the like can be used. A representative example of the photoacid generator is triphenylsulfonium triflate represented by the following formula (2).
(2)
As the thermal acid generator, compounds such as carbonate ester, sulfonate ester and phosphate ester can be used. Specific examples thereof include cyclohexyl nonafluorobutanesulfonate, But are not limited to, norbornyl nonafluorobutane sulfonate, tricyclodecanyl nonafluorobutane sulfonate, adamantyl nonafluorobutane sulfonate, cyclohexyl nonafluorobutanecarbonate, Tricyclodecanyl nonafluorobutanecarbonate, adamantyl nonafluorobutane carbonate, nonafluorobutane phosphonate, norbornyl nonafluorobutane phosphate, tri (norbornyl) nonafluorobutane, bis Cyclodecanyl nonafluorobutane phosphine Ah it may be just a nonafluoro butyl use butane phosphate, and mixtures thereof. A representative example of the thermal acid generator is a compound represented by the following general formula (3).
(3)
The crosslinker (iii) used in the composition for forming a neutral layer according to the present invention is for crosslinking the polymer for forming a neutral layer to change physical properties (polarity, nonpolarity, hydrophilicity, hydrophobicity, etc.) of the neutral layer . As the crosslinking agent, a usual crosslinking agent capable of crosslinking with the polymer for forming a neutral layer may be used without limitation. Examples of the crosslinking agent include a compound having a carbon-carbon double bond capable of binding with the hydroxyl group (-OH) of the polymer for forming a neutral layer, and a hydroxyl-based crosslinking agent. Typically, Or 5 can be exemplified.
[Chemical Formula 4]
[Chemical Formula 5]
As the solvent (iv) used in the composition for forming a neutral layer according to the present invention, the neutral layer forming polymer, the acid generator and the crosslinking agent are dissolved and easily removed in the spin coating process, A conventional organic solvent capable of forming a layer (lower layer film) can be used. Examples of the solvent include cyclohexanone, cyclopentanone, gamma-butyrolactone, N, N-dimethylacetamide, N, N-dimethylformamide, Dimethyl sulfoxide, N-methyl pyrrolidone (NMP), tetrahydrofurfural alcohol, propylene glycol monomethyl ether (PGME), propylene glycol mono Organic solvents such as propylene glycol monomethyl ether acetate (PGMEA) and ethyl lactate may be used alone or in combination.
In the composition for forming a neutral layer according to the present invention, the content of (i) the polymer for forming a neutral layer is 6 to 15% by weight, preferably 7 to 12% by weight. If the content of the polymer is less than 6% by weight, the lower film may not be formed. If the content of the polymer is higher than 15% by weight, properties such as uniformity of the formed lower film may deteriorate and a lower film (coating film) There is a concern. The content of the acid generator is 1 to 10% by weight, preferably 3 to 6% by weight, based on the whole composition. If the content of the acid generator is less than 1% by weight, the amount of the acid required for the crosslinking reaction may be insufficient and the physical properties of the lower film may be insufficiently changed. If the content is more than 10% by weight, There is a risk of contamination of the equipment and there is no particular benefit. The content of the crosslinking agent is 1 to 10% by weight, preferably 4 to 8% by weight, based on the whole composition. If the content of the crosslinking agent is less than 1% by weight, the physical properties of the lower film may be insufficiently changed. If the content of the crosslinking agent exceeds 10% by weight, the crosslinking reaction occurs excessively to hinder the annealing process, The remaining cross-linking agent has a problem of causing fumes in the process and contaminating the equipment. The content of the solvent is, for example, 75 to 90% by weight, excluding the neutral layer forming polymer, the crosslinking agent and the acid generator.
Next, a method of forming an induced self-assembly pattern according to the present invention will be described.
In order to form the self-assembled resist pattern induced in accordance with the present invention, first, the above-mentioned composition for forming a neutral layer is applied on a substrate (etching layer) such as a silicon wafer, aluminum or glass, To remove the solvent to form a lower film. The step of applying the composition for forming a neutral layer may be performed by a conventional method such as spin coating or roller coating, and the step of removing the solvent from the applied composition for forming a neutral layer may be carried out by using a device such as a high temperature plate, ≪ / RTI > by heating the applied composition. The heating temperature is usually 90 to 240 占 폚, preferably 150 to 220 占 폚, and more preferably 180 to 210 占 폚. If the heating temperature is less than 90 占 폚, the solvent of the composition for forming a neutral layer may not be sufficiently removed or a lower film may not be formed. On the other hand, if the heating temperature exceeds 240 ° C, the composition of the lower film may be chemically unstable. After the lower film is formed, the lower film is partially exposed (for example, using a mask) so that the portion where the resist pattern is formed is not exposed and the portion where the resist pattern is not formed is exposed. A block copolymer solution prepared by dissolving a block copolymer (BCP) such as polystyrene-block-polymethylmethacrylate in an organic solvent is applied to the upper part of the partially exposed lower film and then heated to form a block To form a copolymer coating film. FIG. 1 is a graph showing the change in the nanostructure of a block copolymer according to the ratio of the copolymer component of the block copolymer. As shown in FIG. 1, the block copolymer has various nanostructures Lt; / RTI > Next, the substrate on which the block copolymer coating film is formed is annealed at a temperature higher than the glass transition temperature (Tg) of the block copolymer, for example, for 1 to 600 minutes to obtain a self- A fine resist pattern is formed by etching the self-alignment pattern (for example, dry etching, O 2 RIE (reactive ion etching)). In the etching step, the polar portion (methyl methacrylate portion) of BCP is removed, and a fine resist pattern is formed.
In the case where the composition for forming a neutral layer according to the present invention forms a resist pattern lower film (neutral layer), the neutral layer forming polymer, the acid generator and the crosslinking agent react with each other to form the neutral layer forming polymer and the crosslinking agent The process in which the properties of the neutral layer are changed by cross-linking can be represented, for example, by the following reaction formula (1). As shown in the following Reaction Scheme 1, the hydroxyl group (-OH) of the polymer for forming a neutral layer may react with the carbon-carbon double bond of the crosslinking agent to form an acetal moiety.
[Reaction Scheme 1]
In the above Reaction Scheme 1, x and y are as defined in Formula 1, and R is each independently a hydrogen atom or another crosslinking group (for example, a hydrocarbon group containing a carbon-carbon double bond) of a linker , R 'is a brief representation of the remainder of the linker except for the CH 2 = CHOCH 2 - moiety.
When the resist lower film (neutral layer) is formed using the composition for forming a neutral layer according to the present invention and the formed lower film is partially exposed, the neutral layer forming polymer and the crosslinking agent are crosslinked in the exposed region, The physical properties are changed and the function of the neutral layer is lost, so that the vertical self-alignment pattern of the block copolymer (BCP) is not formed. On the other hand, in the non-exposed region, the lower film serves as the original neutral layer that self-orientes the block copolymer in the vertical direction. That is, in the neutral layer formed in accordance with the present invention, in the non-exposure region, the self-alignment pattern of the block copolymer can be formed since it has the characteristic (polarity) of the neutral layer similar to the conventional neutral layer. On the other hand, in the exposure area, the neutral layer-forming polymer, which is a random copolymer of styrene and (meth) acrylic acid (PS-r-PAA), reacts with a crosslinking agent to cause, for example, an acetal protection reaction, The physical properties of the polymer change from hydrophilic to hydrophobic. If the polymer forming the lower film is changed to a hydrophobic polymer, the characteristics of the neutral layer are lost. Therefore, even when the block copolymer is coated on the upper part and annealed, the vertical direction self orientation of the block copolymer is not achieved. As such, the properties of the neutral layer formed in accordance with the present invention change by heating and / or exposure. Therefore, according to the present invention, since a vertical pattern of a block copolymer (BCP) is selectively formed in the exposed region and the non-exposed region, a directed self-assembly (DSA) Only an optional self-aligned resist pattern can be formed. Further, according to the present invention, it is possible to suppress the formation of unwanted patterns in the bulk region of the semiconductor pattern, which is currently a problem. Figure 2 shows that when a resist pattern is formed by forming a conventional bottom film (neutral layer) and annealing the block copolymer on top of the bottom film, a pattern is formed not only in the central region of the cell but also in the bulk region of the cell It is a scanning electron microscope photograph. Further, when the composition for forming a neutral layer according to the present invention is used, there is no need to form a conventional photoresist pattern (guide pattern), and therefore, it is not necessary to form an organic antireflection film in the DSA step. Therefore, according to the present invention, by forming the resist lower film into a single layer (mono-layer), the process can be simplified and the process time can be shortened.
Hereinafter, the present invention will be described in more detail by way of specific examples and comparative examples. The following examples illustrate the present invention and are not intended to limit the scope of the present invention.
[Examples 1 to 4, Comparative Examples 1 to 8] Formation and evaluation of resist pattern by induced self-assembly
A composition for forming a neutral layer containing a polymer, an acid generator and a crosslinking agent in the contents shown in the following Table 1 and the remaining solvent (propylene glycol monomethyl ether acetate: PGMEA) was applied to a cleaned silicon (Si) substrate by spin coating ), And then heat-treated at 205 DEG C for 60 seconds to form a 400 nm thick lower film (organic single layer). The substrate on which the lower film was formed was partially exposed using a ASP-2000 apparatus under nitrogen-free conditions of a hot plate. Next, PS-b-PMMA (polystyrene-b-poly methylmethacrylate, PS: PMMA = 24,000: 24,000, molecular weight of each block, PMMA fraction was about 0.5) as a block copolymer on the partially exposed lower film, Solution was spin-coated to form a block copolymer thin film, annealed at 250 ° C for 120 seconds, and then etched to form a resist pattern. The surface of the block copolymer thin film having the resist pattern formed thereon was observed with a scanning electron microscope (SEM), and a vertically aligned resist pattern self-assembled (aligned) on the thin film of the block copolymer formed on the exposed portion and the non- Were formed. The results are shown in Table 1. In the following Table 1, "O" indicates that a pattern is formed, and "X" A scanning electron microscope (SEM) photograph of the top surface of the nanostructured block copolymer film formed in Example 1 is shown in FIG. As shown in FIG. 3, when a lower film is formed using the composition for forming a neutral layer according to the present invention, and the exposed film is partially exposed and then subjected to an induced self-assembly (DSA) And the vertical alignment pattern is formed in the unexposed portion. In the self-assembled (aligned) vertical alignment pattern of the nanostructures thus formed, PS is the substrate and PMMA exhibits the plate-like structure.
Exposure
In Table 1, when no crosslinking agent or acid generator is present, no pattern is formed in the unexposed portion, and when the crosslinking agent or acid generator is in a trace amount such as 0.001% by weight in Table 1 A pattern is not formed in the non-exposed portion even when it is added. Wherein x and y are respectively 70 mol% and 30 mol%, R 1 is a methyl group, and the weight average molecular weight (Mw) is 5,000 to 30,000 mol%, and the polymer is a polymer for forming a neutral layer, 6,000. Crosslinking agents 1 and 2 are compounds represented by formulas (4) and (5), respectively, and acid generating elements (1) and (2) are compounds represented by formulas (2) and (3), respectively.
Claims (10)
An acid generator which promotes crosslinking between the polymer for forming a neutral layer and the crosslinking agent by generating an acid component by light or heat;
A crosslinking agent for crosslinking the polymer for forming a neutral layer to change physical properties of the neutral layer; And
And a solvent capable of forming the neutral layer by dissolving the neutral layer-forming polymer, the acid generator, and the crosslinking agent.
[Chemical Formula 1]
In the above formula (1), R 1 is a hydrogen atom or a methyl group, and x and y are 40 to 90 mol% and 10 to 60 mol%, respectively, in mole% of each repeating unit constituting the polymer.
(2)
(3)
[Chemical Formula 4]
[Chemical Formula 5]
[Chemical Formula 1]
In Formula 1, R 1 is a hydrogen atom or a methyl group, and x and y are 40 to 90 mol% and 10 to 60 mol%, respectively, in mol% of the respective repeating units constituting the polymer;
Partially exposing the lower film so that the portion where the resist pattern is to be formed is not exposed and the portion where the resist pattern is not formed is exposed;
Coating a block copolymer solution obtained by dissolving a block copolymer in an organic solvent on the partially exposed lower film and then heating to form a block copolymer coating film; And
Heating the substrate on which the block copolymer coating film is formed to a temperature higher than the glass transition temperature (Tg) of the block copolymer to obtain a self-aligned pattern, and etching the self-aligned pattern.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016195449A1 (en) * | 2015-06-04 | 2016-12-08 | 주식회사 엘지화학 | Neutral layer composition |
| WO2018101741A1 (en) * | 2016-11-30 | 2018-06-07 | 주식회사 엘지화학 | Laminate |
| WO2019013602A1 (en) * | 2017-07-14 | 2019-01-17 | 주식회사 엘지화학 | Neutral layer composition |
| KR20190020984A (en) * | 2017-08-22 | 2019-03-05 | 에스케이이노베이션 주식회사 | Random copolymer for forming neutral layer and laminate for forming pattern comprising the same, method for patterning using the same |
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2013
- 2013-06-18 KR KR1020130069760A patent/KR20140146881A/en not_active Application Discontinuation
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| JP2018519379A (en) * | 2013-12-06 | 2018-07-19 | エルジー・ケム・リミテッド | Neutral layer composition |
| WO2016195449A1 (en) * | 2015-06-04 | 2016-12-08 | 주식회사 엘지화학 | Neutral layer composition |
| US10532546B2 (en) | 2015-06-04 | 2020-01-14 | Lg Chem, Ltd. | Composite for neutral layer |
| WO2018101741A1 (en) * | 2016-11-30 | 2018-06-07 | 주식회사 엘지화학 | Laminate |
| US11174360B2 (en) | 2016-11-30 | 2021-11-16 | Lg Chem, Ltd. | Laminate for patterned substrates |
| US11732098B2 (en) | 2016-11-30 | 2023-08-22 | Lg Chem, Ltd. | Laminate for patterned substrates |
| WO2019013602A1 (en) * | 2017-07-14 | 2019-01-17 | 주식회사 엘지화학 | Neutral layer composition |
| CN110869442A (en) * | 2017-07-14 | 2020-03-06 | 株式会社Lg化学 | Neutral layer composition |
| US11732072B2 (en) | 2017-07-14 | 2023-08-22 | Lg Chem, Ltd. | Neutral layer composition |
| KR20190020984A (en) * | 2017-08-22 | 2019-03-05 | 에스케이이노베이션 주식회사 | Random copolymer for forming neutral layer and laminate for forming pattern comprising the same, method for patterning using the same |
| US11643488B2 (en) | 2017-08-22 | 2023-05-09 | Sk Innovation Co., Ltd. | Random copolymer, laminate, and method for forming pattern |
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