Patent Application
20220137511
This U.S. non-provisional patent application claims priority under 35 U.S.C. § 119 to Korean Patent Application No. 10-2020-0144301, filed on Nov. 2, 2020, the entire contents of which are hereby incorporated by reference.
The present disclosure herein relates to a resist composition, and more particularly, to a resist composition used for forming a resist pattern.
Photolithography may include an exposure process and a development process. The performance of the exposure process may include exposing a resist film to light with a specific wavelength to induce the change of the chemical structure of the resist film. The performance of the development process may include selectively removing an exposed part or an unexposed part by using a solubility difference between the exposed part and the unexposed part of the resist film.
Recently, according to the increase of integration and miniaturization of semiconductor devices, the constituent elements of the semiconductor device are required to have minute pitches and widths. There is an increasing importance issue on a resist compound for forming minute patterns.
The task for solving of the present disclosure is to provide a resist composition having high sensitivity to light and improved patterning properties.
The task for solving of the present disclosure is not limited to the aforementioned tasks, and unreferred other tasks may be clearly understood by a person skilled in the art from the description below.
The inventive concept relates to a resist composition and a method of forming a pattern using the same. According to the inventive concept, the composition may include a copolymer represented by Formula 1.
In Formula 1, R1, R2, R3, R4, R5 and R6 are each independently any one selected among hydrogen, deuterium and alkyl of 1 to 3 carbon atoms, A is a single bond, an alkyl group of 1 to 5 carbon atoms, an alkyl ether group of 1 to 8 carbon atoms, an ether alkyl group of 1 to 8 carbon atoms, an alkyl ester group of 1 to 8 carbon atoms, carbonate, or an acetal group of 1 to 8 carbon atoms, R10 is an alkyl group of 1 to 16 carbon atoms, R20 is perhalogenated alkyl of 2 to 16 carbon atoms, perhalogenated alkyl ether perhalogenated alkyl of 2 to 16 carbon atoms, or halogenated-arene of 2 to 16 carbon atoms, “a” is any one integer selected from 1 to 11, and “n” is any one integer selected from 10 to 150.
In an embodiment, the composition may further include a photo acid generator.
In an embodiment, in Formula 1, R20 may be perfluoroalkyl of 2 to 11 carbon atoms or perfluoroalkyl ether perfluoroalkyl of 2 to 11 carbon atoms.
In an embodiment, a material represented by Formula 1 may include a material represented by Formula 2.
In Formula 2, R1, R2, R3, R4, R5 and R6 are each independently any one selected among hydrogen, deuterium and alkyl of 1 to 3 carbon atoms, A is a single bond, an alkyl group of 1 to 5 carbon atoms, an alkyl ether group of 1 to 8 carbon atoms, an ether alkyl group of 1 to 8 carbon atoms, an alkyl ester group of 1 to 8 carbon atoms, carbonate, or an acetal group of 1 to 8 carbon atoms, each X is independently any one selected among F, Cl, Br and I, “a” is any one integer selected from 1 to 11, “b” is any one integer selected from 1 to 15, R11, R12 and R13 are each independently an alkyl group of 1 to 5 carbon atoms, and “n” is any one integer selected from 10 to 150.
In an embodiment, in Formula 2, X and Y may be F.
In an embodiment, A in Formula 1 may be represented by Formula A.
In Formula A, R31 and R32 are each independently any one selected from a single bond or a divalent alkyl group of 1 to 3 carbon atoms, and * is a part bonded to a benzene ring.
In an embodiment, the copolymer may have a glass transition temperature of about 110° C. to about 150° C., and the copolymer may have a polydispersity index of about 1 to about 1.5.
In an embodiment, a material represented by Formula 1 may include a material represented by Formula 3A.
In Formula 3A, “n” is an integer between 10 and 150.
In an embodiment, a material represented by Formula 1 may include a material represented by Formula 3B.
In Formula 3B, “n” is any one integer selected from 10 to 150.
In an embodiment, a material represented by Formula 1 may include a material represented by Formula 3C.
In Formula 3C, “n” may be any one integer selected from 10 to 150.
According to the inventive concept, the method of forming a pattern may include applying a compound represented by Formula 1 below on a substrate to form a resist film; and patterning the resist film.
In Formula 1, R1, R2, R3, R4, R5 and R6 are each independently any one selected among hydrogen, deuterium and alkyl of 1 to 3 carbon atoms, A is a single bond, an alkyl group of 1 to 5 carbon atoms, an alkyl ether group of 1 to 8 carbon atoms, an ether alkyl group of 1 to 8 carbon atoms, an alkyl ester group of 1 to 8 carbon atoms, carbonate, or an acetal group of 1 to 8 carbon atoms, R10 is an alkyl group of 1 to 16 carbon atoms, R20 is perhalogenated alkyl of 2 to 16 carbon atoms, perhalogenated alkyl ether perhalogenated alkyl of 2 to 16 carbon atoms, or halogenated-arene of 2 to 16 carbon atoms, “a” is any one integer selected from 1 to 11, and “n” is any one integer selected from 10 to 150.
In an embodiment, the patterning of the resist film may include exposing the resist film to light to form an exposed part and an unexposed part; and performing a development process using a developing solution on the resist film.
In an embodiment, the developing solution may include a polar developing solution, and the performing of the development process may include removing the exposed part of the resist film.
In an embodiment, the developing solution may include a nonpolar developing solution, and the performing of the development process may include removing the unexposed part of the resist film.
The accompanying drawings are included to provide a further understanding of the inventive concept, and are incorporated in and constitute a part of this specification. The drawings illustrate exemplary embodiments of the inventive concept and, together with the description, serve to explain principles of the inventive concept. In the drawings:
Preferred embodiments of the inventive concept will be explained with reference to the accompany drawings for sufficient understanding of the configurations and effects of the inventive concept. The inventive concept may, however, be embodied in various forms, have various modifications and should not be construed as limited to the embodiments set forth herein. The embodiments are provided to complete the disclosure of the inventive concept through the explanation of the embodiments and to completely inform a person having ordinary knowledge in this technical field to which the inventive concept belongs of the scope of the inventive concept. A person having ordinary knowledge in this technical field might understand suitable environments in which the inventive concept may be performed.
The terms used herein are to explain the embodiments but are not to limit the inventive concept. In the disclosure, the singular forms are intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms “comprises” and/or “comprising,” used in the disclosure, specify the presence of stated materials, elements, steps and/or devices, but do not preclude the presence or addition of one or more other materials, elements, steps and/or devices.
In the disclosure, an alkyl group may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. The carbon number of the alkyl group is not specifically limited, but the alkyl group may be an alkyl group of 1 to 3 carbon atoms. Examples of the alkyl group may include a methyl group, an ethyl group and a propyl group, without limitation.
In the disclosure, examples of halogen may include fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), without limitation.
In the disclosure, the term “substituted or unsubstituted” corresponds to substituted or unsubstituted with one or more substituents selected from the group consisting of a hydrogen atom, a deuterium, a halogen atom, an ether group, a halogenated alkyl group, a halogenated alkoxy group, a halogenated ether group, an alkyl group and a hydrocarbon ring group. In addition, each of the example substituents may be substituted or unsubstituted. For example, an alkyl ether group may be interpreted as an ether group.
In the disclosure, a perhalogenated alkyl group may include perhalogenated alkyl ether perhalogenated alkyl group, and a perfluoroalkyl group may include perfluoroalkyl ether perfluoroalkyl group.
In the disclosure, an alkyl group may include a monovalent alkyl group, a divalent alkyl group, a trivalent alkyl group and a tetravalent alkyl group.
In the chemical formulae in the disclosure, in the case where a chemical bond is not drawn where a chemical bond is required, it may mean that a hydrogen atom is bonded at that position, unless otherwise defined.
In the disclosure, same reference symbol may refer to the same constituent element throughout the text.
Hereinafter, a composition according to the inventive concept will be explained.
According to the inventive concept, the composition may be a resist composition. The resist composition may be used for forming a pattern or for manufacturing a semiconductor device. For example, the resist composition may be used in a patterning process for manufacturing a semiconductor device. The resist composition may be an extreme ultraviolet (EUV) resist composition, a long wavelength ultraviolet resist composition, or an electron beam resist composition. The extreme ultraviolet may mean ultraviolet having a wavelength of about 10 nm to about 124 nm, particularly, about 13.0 nm to about 13.9 nm, more particularly, about 13.4 nm to about 13.6 nm. The long wavelength ultraviolet may mean ultraviolet having a wavelength of about 360 nm to about 370 nm. According to embodiments, the composition may include a copolymer. Particularly, the copolymer may be an alternating copolymer. The copolymer may show excellent mechanical strength. The copolymer may be represented by Formula 1 below.
In Formula 1, R1, R2, R3, R4, R5 and R6 may be each independently any one selected among hydrogen, deuterium and alkyl of 1 to 3 carbon atoms, A may be a single bond, an alkyl group of 1 to 5 carbon atoms, an alkyl ether group of 1 to 8 carbon atoms, an ether alkyl group of 1 to 8 carbon atoms, an alkyl ester group of 1 to 8 carbon atoms, carbonate, or an acetal group of 1 to 8 carbon atoms, R10 may be an alkyl group of 1 to 16 carbon atoms, R20 may be perhalogenated alkyl of 2 to 16 carbon atoms, perhalogenated alkyl ether perhalogenated alkyl of 2 to 16 carbon atoms, or halogenated-arene of 2 to 16 carbon atoms, “a” may be any one integer selected from 1 to 11, and “n” may be any one integer selected from 10 to 150.
According to an embodiment, in Formula 1, R10 may be tertiary alkyl of 1 to 15 carbon atoms.
R20 of Formula 1 may be a fluoroalkyl group of 2 to 11 carbon atoms. For example, R20 may be perfluoroalkyl of 2 to 11 carbon atoms or perfluoroalkyl ether perfluoroalkyl of 2 to 11 carbon atoms.
According to an embodiment, in Formula 1, R20 may be —(CbY2b)—CX3, X and Y may be each independently any one selected from H, F, Cl, Br, or I, and “b” may be an integer between 1 and 15.
In another embodiment, in Formula 1, R20 may be fluorine-substituted fluoroarene.
According to embodiments, a material represented by Formula 1 may include a material represented by Formula 2.
In Formula 2, each X is independently any one selected from F, Cl, Br or I, “b” is any one integer selected from 1 to 15, R11, R12 and R13 are each independently an alkyl group of 1 to 5 carbon atoms, and “a”, A, Ru, R2, R3, R4, R5, R6 and “n” are the same as defined in Formula 1.
According to an embodiment, X and Y in Formula 2 may be each independently F or I. For example, X and Y may be F.
In an embodiment, in Formula 1 and Formula 2, A may be a divalent alkyl group of 1 to 5.
According to another embodiment, in Formula 1 and Formula 2, A may be a group represented by Formula A.
In Formula A, R31 and R32 may be each independently any one selected from a single bond or a divalent alkyl group of 1 to 3 carbon atoms, and * may be a part bonded to a benzene ring.
The group represented by Formula A may include the groups represented by Formula A1 and Formula A2 below.
In Formula A1 and Formula A2, * may be a part bonded to a benzene ring.
According to embodiments, a material represented by Formula 2 may include at least one selected from materials represented by Formula 3A, Formula 3B and Formula 3C below.
In Formula 3A, “n” may be an integer selected from 10 and 150.
In Formula 3B, “n” may be any one integer selected from 10 to 150.
In Formula 3C, “n” may be any one integer selected from 10 to 150.
According to another embodiment, R20 in Formula 1 may be any one selected from the groups represented by Formula 4-1 to Formula 4-3 below.
—CF2CHFO(CF2)3OCF3 [Formula 4-2]
—CF2CHFO(CF2)2CF3 [Formula 4-3]
In the explanation below, a perhalogenated alkyl group may be defined to include a perhalogenated alkyl ether perhalogenated alkyl group, and the perhalogenated alkyl group may be defined to include a perfluoroalkyl ether perfluoroalkyl group.
The resist composition according to embodiments may further include a photo acid generator (PAG). The photo acid generator may include, for example, the materials represented by Formula 5 and Formula 6 below. The material represented by Formula 5 may be a nonionic photo acid generator. The material represented by Formula 6 may be an ionic photo acid generator.
According to embodiments, the composition may include a copolymer, and the copolymer may include a first polymerization unit and a second polymerization unit. The first polymerization unit may be induced from a maleimide monomer which is substituted with a halogenated alkyl group. The halogenated alkyl group may be represented by R20 in Formula 1. A resist film includes a compound represented by Formula 1 and may show improved sensitivity and light absorbance during an exposure process. Accordingly, the efficiency of the manufacturing process of a semiconductor device may be improved. In this case, the sensitivity means sensitivity to ultraviolet or electron beam, and the light absorbance may be absorbance of ultraviolet or electron beam. The ultraviolet may include extreme ultraviolet or long wavelength ultraviolet. By the irradiation of the light, intermolecular bonding reaction between halogenated alkyl groups may be generated. The intermolecular bonding reaction may be crosslinking reaction. As a result of the intermolecular bonding reaction, an exposed part of a resist film may have a chemical structure different from an unexposed part.
In an embodiment, in a development process of a resist film, a developing solution may include a high fluorine-based solution. In Formula 1, R20 may include a halogenated alkyl group (for example, perhalogenated alkyl group). The resist film may include a plurality of the same elements (halogen elements) as the developing solution, and may be easily dissolved in the developing solution. The halogen may be fluorine.
The second polymerization unit may be different from the first polymerization unit. The second polymerization unit may be induced from a styrene monomer in which an acid-cleavable protective group is substituted. The acid-cleavable protective group may include an alkyl group bonded to an oxygen atom. For example, the acid-cleavable protective group may be represented by —OR10 in Formula 1.
In a post-exposure bake (PEB) process, the decomposition reaction of the acid-cleavable protective group of a copolymer may be generated. For example, the bond between oxygen (O) and R10 of —OR10 may be cleaved. If R10 includes a tertiary alkyl group, a product may be stabilized even further, and the decomposition reaction may be accelerated. The photo acid generator may produce an acid by light. The acid may mean hydrogen cations. The acid may act as a catalyst, and by the acid catalyst, the decomposition reaction of the acid-cleavable protective group may be accelerated. Accordingly, the resist film may show improved sensitivity. The decomposition reaction of the acid-cleavable protective group in an exposure process may be performed by, for example, Reaction 1A, Reaction 1B, or Reaction 1C.
According to embodiments, after the decomposition reaction, the second polymerization unit of the copolymer (for example, a polymerization unit including styrene) may have a —OH group. Accordingly, the second polymerization unit of the copolymer may show polarity. The exposed part of the resist film may have high solubility in a polar developing solution. The exposed part of the resist film may have reduced solubility in a nonpolar developing solution. Accordingly, the precision of patterning in a development process may be improved.
If the chemical composition or chemical structure of a resist material is nonuniform, the resolution properties of a resist pattern and the line-edge roughness (LER) properties may be deteriorated. According to the inventive concept, the copolymer is an alternating copolymer and may have uniform chemical composition and uniform chemical structure. Particularly, since the first polymerization unit and the second polymerization unit are alternately arranged, halogenation functional groups and acid-cleavable protective groups may be distributed uniformly in a compound. If multiple copolymers represented by Formula 1 are provided, the total number ratio of the halogenation functional groups and the total number ratio of the acid-cleavable protective groups of the multiple copolymers may be substantially the same. A resist film including the copolymer may show high resolution during an exposure process. In a development process, any one among the exposed part and the unexposed part of the resist film may be dissolved uniformly with respect to a developing solution. Accordingly, a resist pattern may be formed with minute widths and pitches.
Since the copolymer is an alternating copolymer, the copolymer may have narrow molecular weight distribution according to polymerization conditions. The molecular weight distribution may be evaluated by a polydispersity index. The polydispersity index (hereinafter, PDI) of the copolymer may commonly have a value of about 2. According to the inventive concept, a polymer having a polydispersity index of “about 1.5 or less” may be prepared through controlling the conditions of polymerization reaction. For example, the polydispersity index of the copolymer may be about 1 to about 1.5. For example, if the copolymer satisfies the reduced polydispersity index conditions, the copolymer may show improved uniformity of a chemical composition and improved uniformity of a chemical structure. Accordingly, if a resist pattern is formed using the copolymer, the resolution of the resist pattern may be improved even further. The resist pattern may have improved line-edge roughness (LER) properties and/or improved line width roughness (LWR) properties.
The composition includes a copolymer and a halogenated alkyl group (for example, a perhalogenated alkyl group), and may have a relatively high glass transition temperature. For example, the compound may have a glass transition temperature of about 110° C. to about 150° C. Accordingly, a pattern formed using the composition may have high durability and stability.
According to embodiments, a resist composition may not include a metal element. Accordingly, contamination problems due to a metal element may not be generated. The contamination may include contamination of equipments or contamination of the constituent elements of a semiconductor device.
The resist composition according to embodiments may have the merits of a non-chemically amplified photoresist (nCAR). For example, the resist composition may show excellent resolution. The resist composition may show the merits of a chemically amplified photoresist (CAR). For example, the resist composition may show excellent sensitivity.
Hereinafter, a method of preparing a compound according to embodiments will be explained.
The preparation of a compound according to embodiments may include synthesizing a first monomer, synthesizing a second monomer, and performing polymerization reaction of the first monomer and the second monomer.
The first monomer may include maleimide to which a halogenated alkyl group is bonded. The synthesis of the first monomer may include substituting hydrogen bonded to the nitrogen of the maleimide with a high fluoroalkyl chain by applying Mitsunobu reaction conditions. For example, the synthesis of the first monomer may be performed by Reaction 2 below.
(In Reaction 2, DIAD is diisopropyl azocarboxylate, and PPh3 is triphenylphosphine.)
The second monomer may include styrene to which an acid-cleavable protective group is bonded or styrene derivatives to which an acid-cleavable protective group is bonded. For example, 4-tert-butoxystyrene (hereinafter, tBOS) may be used as the second monomer. The synthesis of the second monomer may be performed by Reaction 3. For example, hydroxybenzaldehyde is used as a starting material, and Wittig reaction may be performed with respect to the starting material. The carbonyl group of hydroxybenzaldehyde is transformed into alkene, and tert-butyl acetate and tert-butoxycarbonyl are introduced to a hydroxyl functional group to prepare 4-(tert-butyl acetate)styrene (hereinafter, tBAST) and 4-[(tert-butoxycarbonyl)oxy]styrene (hereinafter, tBOCST), respectively.
(In Reaction 3, THF is tetrahydrofuran, and DMAP is dimethylaminopyridine.)
The polymerization reaction of the first monomer and the second monomer may be performed by reversible addition fragmentation chain transfer (RAFT) polymerization reaction. The styrene and/or styrene derivatives of the second monomer may have double bonds with high electron density, and the first monomer may have double bonds with deficient electrons. Accordingly, through the RAFT polymerization reaction of the first monomer and the second monomer, an alternating copolymer may be synthesized. In the polymerization reaction, 4-cyano-4-dodecyl sulfanylthiocarbonyl)sulfanyl pentanoi c acid (hereinafter, CDSTSP) may be used as a RAFT agent, and 2,2′-azobis(2-methylpropionitrile) (hereinafter, AIBN) may be used as a polymerization initiator.
For example, the polymerization reaction of the first monomer and the second monomer may be performed according to Reaction 4A, Reaction 4B, or Reaction 4C below. The product of Reaction 4A may be a material represented by Formula 3A. The product of Reaction 4B may be a material represented by Formula 3B. The product of Reaction 4C may be a material represented by Formula 3C.
Hereinafter, a method of forming a pattern using the composition according to embodiments and a method of manufacturing a semiconductor device will be explained.
Referring to
A resist composition may be prepared. The resist composition may include the above-explained copolymer and a photo acid generator. The resist composition may be applied on the lower film 200 to form the resist film 300. The application of the resist composition may be performed by spin coating. On the applied resist composition, a heat treatment process may be additionally performed. The heat treatment process may be performed at about 80° C. to about 200° C. The heat treatment process may correspond to a bake process of the resist film 300.
Referring to
The second part 320 of the resist film 300 may not be exposed to the light 500. The second part 320 of the resist film 300 may be an unexposed part. The chemical structure of the copolymer in the second part 320 of the resist film 300 may not be changed. Accordingly, after completing the irradiation of the light 500, the first part 310 and the second part 320 of the resist film 300 may have different chemical structures.
According to embodiments, a post-exposure bake (PEB) process may be further performed on the resist film 300. In the post-exposure bake process, the decomposition reaction of an acid-cleavable protective group may arise. For example, a bond between oxygen (O) and R10 of —OR10 may be cleaved, and a —OH group may be formed. The decomposition reaction of the acid-cleavable protective group may be performed according to the above-explained Reaction 1A, Reaction 1B, or Reaction 1C. In the post-exposure bake process, a photo acid generator may produce an acid, and the acid may act as a catalyst. By the acid, the decomposition reaction of the acid-cleavable protective group may be promoted. After an exposure process, the second polymerization unit of the copolymer in the first part 310 of the resist film 300 (for example, a polymerization unit including styrene) may have an OH group. Due to the OH group, the polarity of the first part 310 of the resist film 300 may increase.
The crosslinked network structure of the copolymer may prevent the diffusion of an acid from the first part 310 to the second part 320 of the resist film 300. Accordingly, an OH group may not be formed in the second part 320 of the resist film 300. The first part 310 of the resist film 300 may have different properties from the second part 320. For example, the first part of the resist film 300 may be polar, and the second part 320 may be nonpolar.
After the exposure process, the photo mask 400 may be removed.
Referring to
If the chemical composition or chemical structure of a resist material is nonuniform, the resist material may be dissolved in the developing solution relatively nonuniformly. According to embodiments, the copolymer is an alternating copolymer, and multiple copolymers may have substantially the same composition ratio. Accordingly, in a development process, the selectivity of the second part 320 against the first part 310 of the resist film 300 may increase. The second part 320 of the resist film 300 may be uniformly dissolved in the developing solution. Accordingly, the resist pattern 300P formed from the resist composition may have a narrow width W. For example, the width W of the resist pattern 300P may be about 20 nm to about 300 nm. The resist pattern 300P formed from the composition may include multiple pattern parts, and a distance D between the pattern parts may be relatively narrow. For example, the distance D between the pattern parts of the resist pattern 300P may be about 20 nm to about 300 nm.
According to embodiments, the high fluorine-based solution is used as the developing solution, and the developing solution may have low surface tension. Accordingly, the pattern collapse of the resist pattern 300P during the development process may be prevented. The pattern collapse may mean the collapse of a part of the resist film 300 developed (for example, the second part 320) during drying due to the surface tension of a solvent. The development process of the resist pattern 300P may be performed chemically stably. Accordingly, the resist pattern 300P may be formed with a minute width W and distance D.
As in
Referring to
According to embodiments, the lower pattern 200P may be the constituent element of a semiconductor device. For example, the lower pattern 200P may be a semiconductor patter, conductive pattern, or insulating pattern in the semiconductor device.
Referring to
After that, a development process may be performed on the resist film 300 to form a resist pattern 300P. The development process may be performed by the method explained referring to
By the polar developing solution, the first part 310 of the resist film 300 may be removed to form a resist pattern 300P′. However, since the second part 320 of the resist film 300 is nonpolar, the second part 320 may not be removed by the developing solution. The resist pattern 300P′ may correspond to the second part 320 of the resist film 300. The resist pattern 300P′ may be a positive tone pattern. The ranges of the width W′ and distance D′ of the resist pattern 300P′ may be substantially the same as the width W and distance D of the resist pattern 300P in
Referring to
As referred to in embodiments, after exposing to ultraviolet light about 360 nm to about 370 nm, the formation of a positive pattern or a negative pattern may be determined according to the polar or nonpolar characteristics of a developing solution. However, if short wavelength light, including extreme ultraviolet (UV) or electron beam is irradiated, crosslinking by a fluorinated chain may act as a main mechanism, and solubility change may not arise in a polar developing solution, and a negative pattern may be formed by a nonpolar developing solution.
Hereinafter, referring to the experimental examples of the inventive concept, the preparation of a resist composition and the formation of a resist pattern will be explained. In the explanation of the experimental examples, room temperature may mean about 25° C.
1. Preparation of Compounds
(1) Synthesis of First Monomer (RFMI6 Introducing a Perfluoroalkylated Chain)
To a round-bottom flask (100 cm3), triphenylphosphine (2.70 g, 10.3 mmol) and tetrahydrofuran (hereinafter, THF) (25 cm3) were added to prepare a solution. After stirring, the solution was cooled to about 0° C. To the solution cooled, diisopropyl azodicarboxylate (2.10 g, 10.3 mmol) was added dropwisely to prepare a reaction mixture. The reaction mixture was stirred for about 10 minutes. A solution of 5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluorodecan-1-ol (4.80 g, 12.4 mmol) dissolved in THF (10 cm3) was added to the reaction mixture. The reaction mixture was kept at about 0° C. for about 5 minutes using an ice bath, and maleimide (1.00 g, 10.3 mmol) was added to the reaction mixture. The ice bath was removed, and the reaction mixture was stirred at room temperature (about 25° C.) for about 12 hours to perform the reaction. The reaction may be performed by Reaction 2. After finishing the reaction, ethyl acetate was added to the reaction mixture, and extraction was performed. An extract including a product in ethyl acetate was washed with water and a saturated sodium chloride aqueous solution. Then, an organic solution in which the product was dissolved was separated. To the organic solution thus separated, anhydrous MgSO4 was injected and stirred to remove moisture in the product. The product was filtered and concentrated. The product was purified through column chromatography (stationary phase: silica gel, mobile phase: ethyl acetate:hexane=1:4) to obtain a final product (RFMI6) of a white solid.
[Yield Analysis]
The mass of the final product (RFMI6) was 3.50 g. The yield was analyzed as 72%.
[Nuclear Magnetic Resonance (NMR) Analysis]
The chemical shift values (δ) of the material thus synthesized, measured by 1H NMR (400 MHz, CDCl3) were 6.71 (s, 2H), 3.56 (t, J=7 Hz, 2H), 2.19-2.00 (m, 2H), 1.75-1.58 (m, 4H).
Accordingly, the final product thus synthesized (RFMI6) was confirmed as 1-(5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluorodecyl)-1H-pyrrole-2,5-dione.
(2) Synthesis and Preparation of Second Monomer
To a one-neck, round-bottom flask (250 cm3), methyltriphenylphosphonium bromide (13.2 g, 36.8 mmol) and tetrahydrofuran (48 cm3) were injected, and potassium tert-butoxide (6.9 g, 61.5 mmol) was added to prepare a mixture. The mixture was stirred at room temperature for about 10 minutes. After that, a solution of 4-hydroxybenzaldehyde (3 g, 24.6 mmol) dissolved in THF (24 cm3) was added to the mixture. The mixture was stirred at room temperature for about 1 hour. A saturated ammonium chloride aqueous solution was added to the mixture to finish the reaction. The reaction was finished, and a product was formed. Under vacuum distillation conditions, THE in the product was removed. The product was added to dichloromethane (DMC) and extracted. The extracted product was washed with water and a saturated sodium chloride aqueous solution. Accordingly, an organic solution in which the product was dissolved was separated. To the organic solution thus separated, anhydrous MgSO4 was injected and stirred to remove moisture in the product. The product was filtered and concentrated. The product was purified through column chromatography (stationary phase: silica gel, mobile phase: ethyl acetate:hexane=1:9) to obtain a final product of a bright yellow solid.
[Yield Analysis]
The mass of the final product was 3.62 g. The yield was analyzed as 92%.
[Nuclear Magnetic Resonance (NMR) Analysis]
The chemical shift values (6) of the material thus synthesized, measured by 1H NMR (400 MHz, CDCl3) were 7.3 (d, J=8.5 Hz, 2H), 6.79 (d, J=8.6 Hz, 2H), 6.65 (d, J=17.6 Hz 2H), 5.60 (d, J=17.6 Hz, 1H), 5.12 (d, J=17.6 Hz, 1H), 4.94 (s, 1H).
Accordingly, the final product thus synthesized was confirmed as 4-hydroxystyrene.
To a one-neck, round-bottom flask (100 cm3), 4-hydroxystryene (1.53 g, 12.7 mmol), potassium carbonate (3.52 g, 25.50 mmol), sodium iodide (3.81 g, 25.47 mmol), 18-crown-6 (0.34 g, 1.27 mmol), and acetone (30 cm3) were added to prepare a mixture. The mixture was stirred at room temperature for about 5 minutes. To the mixture, tert-butyl bromoacetate (4.97 g, 25.47 mmol) was added dropwisely, and by using a refluxing cooler, the mixture was stirred at a temperature of about 80° C. for about 20 hours to perform the reaction. After finishing the reaction, a product was extracted using ethyl acetate. The product thus extracted was washed with water and a saturated sodium chloride aqueous solution. To the product thus obtained, anhydrous MgSO4 was injected and stirred to remove moisture in the product. The product was filtered and concentrated. The product was purified through column chromatography (stationary phase: silica gel, mobile phase: ethyl acetate:hexane=1:9). A final product (tBAST) of a colorless liquid was obtained.
[Yield Analysis]
The mass of the final product was 2.05 g. The yield was analyzed as 90%.
[Nuclear Magnetic Resonance (NMR) Analysis]
The chemical shift values (6) of the material thus synthesized, measured by 1H NMR (400 MHz, CDCl3) were 7.34 (d, J=8 Hz, 2H), 6.85 (d, J=8.4 Hz, 2H), 6.64 (m, 1H), 5.61 (d, J=17.2 Hz, 2H), 5.14 (d, J=10.4 Hz, 2H), 4.51 (s, 2H), 1.49 (s, 9H).
Accordingly, the final product thus synthesized was confirmed as tert-butyl 2-(4-vinylphenoxy)acetate.
To a one-neck, round-bottom flask (50 cm3), 4-hydroxystyrene (1.24 g, 10.3 mmol) and 4-dimethylaminopyridine (0.63 g, 5.16 mmol) were added to prepare a mixture. To the mixture, anhydrous THE (12 cm3) was injected for dissolution. A solution of di-tert-butyl dicarbonate (9.01 g, 41.28 mmol) dissolved in anhydrous THE (6 cm3) was added to the mixture and reacted at room temperature for about 1 hour. After finishing the reaction, the product thus obtained was added to ethyl acetate for extraction. The product thus extracted was washed with water and a saturated sodium chloride aqueous solution. Then, an organic solution in which the product was dissolved was separated. To the organic solution thus separated, anhydrous MgSO4 was injected and stirred to remove moisture in the product. The product was filtered and concentrated, and then, purified through column chromatography (stationary phase: silica gel, mobile phase: ethyl acetate:hexane=1:9). A final product (tBOCST) of a colorless liquid was obtained.
[Yield Analysis]
The mass of the final product was 2.05 g. The yield was analyzed as 90%.
[Nuclear Magnetic Resonance (NMR) Analysis]
The chemical shift values (6) of the material thus synthesized, measured by 1H NMR (400 MHz, CDCl3) were 7.4 (d, J=8.4 Hz, 2H), 7.12 (d, J=8.4 Hz, 2H), 6.69 (m, 1H), 5.69 (d, J=18.4 Hz, 2H), 5.25 (d, J=11.2 Hz, 2H), 1.56 (s, 9H).
Accordingly, the final product thus synthesized was confirmed as 4-[(tert-butoxycarbonyl)oxy]styrene.
To a Schlenk tube (25 cm3), 1-(5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluorodecyl)-1H-pyrrole-2,5-dione (RFMI6) (0.5 g, 1.06 mmol) synthesized above, 4-tert-butoxystyrene (purchased from SigmaAldrich) (0.187 g, 1.06 mmol), 4-cyano-4(dodecylsulfanylthiocarbonyl)sulfanyl pentanoic acid (CDSTSP) (0.01 g, 0.027 mmol) and 2,2′-azobis(2-methylpropionitrile) (AIBN) (0.002 g, 0.013 mmol) were added under a nitrogen atmosphere to prepare a solution. Benzotrifluoride (3 cm3) bubbled with a nitrogen gas was injected into the solution under nitrogen conditions. A series of freeze-pump-thaw processes was repeated three times to remove oxygen in the solution. The solution was stirred at a temperature of about 90° C. for about 12 hours. Then, the solution in the tube was added to hexane (50 cm3) dropwisely to form a precipitate. The precipitate was filtered and dried. 0.5 g of a final product of P(RFMI6-tBOS) was obtained.
[Nuclear Magnetic Resonance (NMR) Analysis]
Referring to
To a Schlenk tube (25 cm3), 1-(5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluorodecyl)-1H-pyrrole-2,5-dione (RFMI6) (0.5 g, 1.06 mmol), tert-butyl 2-(4-vinylphenoxy)acetate (0.25 g, 1.06 mmol), 4-cyano-4(dodecylsulfanylthiocarbonyl)sulfanyl pentanoic acid (CDSTSP) (0.01 g, 0.027 mmol) and 2,2′-azobis(2-methylpropionitrile) (AIBN) (0.002 g, 0.013 mmol) were added under a nitrogen atmosphere to prepare a solution. Benzotrifluoride (3 cm3) bubbled with a nitrogen gas was injected into the solution under nitrogen conditions. A series of a freeze process, a pump process, and a thaw process was repeated three times to remove oxygen in the solution. The solution was stirred at a temperature of about 90° C. for about 12 hours. Then, the solution in the tube was added to hexane (50 cm3) dropwisely to form a precipitate. The precipitate was filtered and dried. 0.65 g of a final product of P(RFMI6-tBAST) was obtained.
[Nuclear Magnetic Resonance (NMR) Analysis]
Referring to
To a Schlenk tube (25 cm3), 1-(5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluorodecyl)-1H-pyrrole-2,5-dione (RFMI6) (0.5 g, 1.06 mmol) synthesized above, 4-(tert-butoxycarbonyloxy)styrene (tBOCST) (0.23 g, 1.06 mmol), 4-cyano-4(dodecylsulfanylthiocarbonyl)sulfanyl pentanoic acid (CDSTSP) (0.01 g, 0.027 mmol), and 2,2′-azobis(2-methylpropionitrile) (AIBN) (0.002 g, 0.013 mmol) were added under a nitrogen atmosphere to prepare a solution. Benzotrifluoride (3 cm3) bubbled with a nitrogen gas was injected into the solution under nitrogen conditions. A series of a freeze process, a pump process, and a thaw process was repeated three times to remove oxygen in the solution. The solution was stirred at a temperature of about 90° C. for about 12 hours. Then, the solution in the tube was added to hexane (50 cm3) dropwisely to form a precipitate. The precipitate was filtered and dried. 0.59 g of a final product of P(RFMI6-tBOCST) was obtained.
[Nuclear Magnetic Resonance (NMR) Analysis]
Referring to
To a Schlenk tube (25 cm3), RFMI6 (0.40 g, 0.85 mmol) synthesized above, styrene (0.09 g, 0.85 mmol), and 2,2′-azobis(2-methylpropionitrile) (AIBN) (0.01 g, 0.06 mmol) were added under a nitrogen atmosphere. Benzotrifluoride (6 cm3) bubbled with a nitrogen gas was injected into the mixture under nitrogen conditions. Then, the mixture was stirred at a temperature of about 80° C. for about 12 hours to perform the reaction shown in Reaction 5 below. Then, to the solution in the tube, hexane (50 cm3) was added dropwisely to form a precipitate. The precipitate was filtered and dried. A final product of P(RFMI6-St) was obtained.
(In Reaction 5, “n” may be an integer between 10 and 150.)
In PF-7600 (purchased from 3M Co.), P(RFMI6-tBOS) (10 wt/vol %) and a photo acid generator of nonafluorobutanesulfonyloxy-1,8-naphthalimide were dissolved to prepare a resist solution. In this case, the nonafluorobutanesulfonyloxy-1,8-naphthalimide was about 5 wt % of the P(RFMI6-tBOS).
The resist solution of Experimental Example 2A was applied on a silicon substrate at about 1000 rpm for about 60 seconds by spin coating. The coated solution was heated at about 110° C. for about 1 minute to form a resist thin film.
By the same method as Experimental Example 2A, a resist solution was prepared. However, the resist solution was prepared using P(RFMI6-tBAST) instead of P(RFMI6-tBOS).
By the same method as Experimental Example 2A, a resist solution was prepared. However, the resist solution was prepared using P(RFMI6-tBOCST) instead of P(RFMI6-tBOS).
On the resist thin film of Experimental Example 2B, ultraviolet of about 365 nm (i-line) was irradiated under conditions of 120 mJ/cm2, followed by heating at about 80° C. for about 1 minute. The resist thin film was developed using PF-7600 for about 60 seconds. As a result of the development process, the formation of a negative tone pattern was observed.
By the same method as Experimental Example 2A, a resist solution was prepared. However, the resist solution was prepared using P(RFMI6-tBAST) instead of P(RFMI6-tBOS). By using the resist solution, a resist thin film and a resist pattern were formed by the same method as Experimental Example 2B. After that, the evaluation of ultraviolet lithography was performed by the same method as in Experimental Example 3A, and the formation of a negative tone pattern was observed.
By the same method as Experimental Example 2A, a resist solution was prepared. However, the resist solution was prepared using P(RFMI6-tBOCST) instead of P(RFMI6-tBOS). By using the resist solution, a resist thin film and a resist pattern were formed by the same method as Experimental Example 2B. After that, the evaluation of ultraviolet lithography was performed by the same method as in Experimental Example 3A, and the formation of a negative tone pattern was observed.
A resist thin film was formed by the same method as in Experimental Example 2B. However, the resist solution was applied after treating a silicon substrate with hexamethyldisilazane (HMDS).
On the resist thin film, ultraviolet of about 365 nm (i-line) was irradiated under conditions of 80 mJ/cm2, followed by heating at about 90° C. for about 1 minute to perform a post-exposure bake (PEB) process. A developing solution was prepared by mixing a 0.26 M TMAH aqueous solution and isopropyl alcohol (IPA) in a volume ratio of 70%:30%. By using the developing solution, a development process was performed with respect to the exposed resist thin film for about 30 seconds. After the development process, a washing process was performed using DI water. As a result of the development process and washing process, the formation of a positive tone pattern was observed.
By the same method as Experimental Example 2A, a resist solution was prepared. However, the resist solution was prepared using P(RFMI6-tBAST) instead of P(RFMI6-tBOS). By using the resist solution, a resist thin film and a resist pattern were formed by the same method as Experimental Example 2B. After that, the evaluation of ultraviolet lithography was performed by the same method as in Experimental Example 4A, and the formation of a positive tone pattern was observed.
By the same method as Experimental Example 2A, a resist solution was prepared. However, the resist solution was prepared using P(RFMI6-tBOCST) instead of P(RFMI6-tBOS). By using the resist solution, a resist thin film and a resist pattern were formed by the same method as Experimental Example 2B. After that, the evaluation of ultraviolet lithography was performed by the same method as in Experimental Example 4A, and the formation of a positive tone pattern was observed.
In PF-7600 (purchased from 3M Co.), a material represented by Formula 6A below was dissolved to prepare a resist solution. A resist thin film was formed by the same method as in Experimental Example 3.
(In Formula 6A, “n” may be an integer between 10 and 150.)
In PF-7600 (purchased from 3M Co.), a material represented by Formula 6B below was dissolved to prepare a resist solution. A resist thin film was formed by the same method as in Experimental Example 3.
(In Formula 6B, “n” may be an integer between 10 and 150.)
In PF-7600, P(RFMI6-tBOS) (3 wt/vol %) was dissolved to prepare a resist solution. The resist solution was applied on a silicon substrate at about 2000 rpm for about 60 seconds by spin coating. The coated resist solution was heated at about 110° C. for about 1 minute to form a resist thin film with a thickness of about 100 nm.
Under an acceleration voltage of about 80 keV, an electron beam of about 50 to about 1,500 μC/cm2 was irradiated onto the resist thin film. On the exposed resist thin film, a development process was performed using PF-7600 for about 30 seconds. A thickness was measured through Alpha-step® D-300 stylus profiler manufactured by Kla-Tencor Co. to evaluate solubility properties.
In PF-7600, P(RFMI6-tBOS) (3 wt/vol %) and a photo acid generator of nonafluorobutanesulfonyloxy-1,8-naphthalimide were dissolved to prepare a resist solution. In this case, the nonafluorobutanesulfonyloxy-1,8-naphthalimide was about 10 wt % of the P(RFMI6-tBOS).
The resist solution thus prepared was applied on a silicon substrate at about 2000 rpm for about 60 seconds by spin coating. The coated resist solution was heated at about 110° C. for about 1 minute to form a resist thin film with a thickness of about 100 nm.
Under an acceleration voltage of about 80 keV, an electron beam of about 50 to about 1,500 μC/cm2 was irradiated onto the resist thin film. The exposed resist thin film was heated at about 100° C. for about 1 minute to perform a post-exposure bake (PEB) process. Then, on the resist thin film, a development process was performed using PF-7600 for about 30 seconds. A thickness was measured through Alpha-step® D-300 stylus profiler manufactured by Kla-Tencor Co. to evaluate solubility properties.
In PF-7600, P(RFMI6-tBOS) (3 wt/vol %) was dissolved to prepare a resist solution. The resist solution was applied on a silicon substrate at about 2000 rpm for about 60 seconds by spin coating. The coated resist solution was heated at about 110° C. for about 1 minute to form a resist thin film with a thickness of about 100 nm.
Under an acceleration voltage of about 80 keV, an electron beam of about 50 to about 1,500 μC/cm2 was irradiated onto the resist thin film. On the resist thin film, a development process was performed using PF-7600 for about 30 seconds. A thickness was measured through Alpha-step® D-300 stylus profiler manufactured by Kla-Tencor Co. to evaluate solubility properties.
In PF-7600, P(RFMI6-tBOS) (3 wt/vol %) and a photo acid generator of triphenylsulfonium nonaflate (TPS-Nf) were dissolved to prepare a resist solution. In this case, the triphenylsulfonium nonaflate (TPS-Nf) was about 10 wt % of the P(RFMI6-tBOS).
The resist solution thus prepared was applied on a silicon substrate at about 2000 rpm for about 60 seconds by spin coating. The coated resist solution was heated at about 110° C. for about 1 minute to form a resist thin film with a thickness of about 100 nm.
Under an acceleration voltage of about 80 keV, an electron beam of about 50 to about 1,500 μC/cm2 was irradiated onto the resist thin film. The exposed resist thin film was heated at about 100° C. for about 1 minute to perform a post-exposure bake (PEB) process. Then, on the resist thin film, a development process was performed using PF-7600 for about 30 seconds. A thickness was measured through Alpha-step® D-300 stylus profiler manufactured by Kla-Tencor Co. to evaluate solubility properties.
In PF-7600, P(RFMI6-tBOS) (3 wt/vol %) was dissolved to prepare a resist solution. The resist solution was applied on a silicon substrate at about 2000 rpm for about 60 seconds by spin coating. The coated resist solution was heated at about 110° C. for about 1 minute to form a resist thin film with a thickness of about 100 nm.
Under an acceleration voltage of about 80 keV, an electron beam of about 20 to about 600 μC/cm2 was irradiated onto the resist thin film. On the resist thin film, a development process was performed using PF-7600 or n-butyl acetate (nBA) for about 30 seconds. A thickness was measured through Alpha-step® D-300 stylus profiler manufactured by Kla-Tencor Co. to evaluate solubility properties.
A resist solution was prepared, a thin film was formed, and an exposure process was performed by the same method as in Experimental Example 7A. However, the development process after the exposure process was performed using n-butyl acetate (nBA). The solubility properties of the resist thin film were evaluated.
In PF-7600, P(RFMI6-tBOS) (3 wt/vol %) and a photo acid generator of triphenylsulfonium nonaflate (TPS-Nf) were dissolved to prepare a resist solution. In this case, the triphenylsulfonium nonaflate (TPS-Nf) was about 10 wt % of the P(RFMI6-tBOS).
The resist solution thus prepared was applied on a silicon substrate at about 2250 rpm for about 60 seconds by spin coating. The coated resist solution was heated at about 110° C. for about 1 minute to form a resist thin film with a thickness of about 100 nm.
Under an acceleration voltage of about 80 keV, an electron beam of about 20 to about 600 μC/cm2 was irradiated onto the resist thin film. Then, on the resist thin film, a development process was performed using PF-7600 for about 30 seconds. A thickness was measured through Alpha-step® D-300 stylus profiler manufactured by Kla-Tencor Co. to evaluate solubility properties.
A resist solution was prepared, a thin film was formed, and an exposure process was performed by the same method as in Experimental Example 7C. However, the development process after the exposure process was performed using n-butyl acetate (nBA). The solubility properties of the resist thin film were evaluated.
In PF-7600, P(RFMI6-tBOS) (3 wt/vol %) and a photo acid generator of triphenylsulfonium nonaflate (TPS-Nf) were dissolved to prepare a resist solution. In this case, the triphenylsulfonium nonaflate (TPS-Nf) was about 10 wt % of the P(RFMI6-tBOS).
The resist solution thus prepared was applied on a silicon substrate at about 2250 rpm for about 60 seconds by spin coating. The coated resist solution was heated at about 110° C. for about 1 minute to form a resist thin film with a thickness of about 100 nm.
Under an acceleration voltage of about 80 keV, an electron beam of about 20 to about 600 μC/cm2 was irradiated onto the resist thin film. The exposed resist thin film was heated at about 110° C. for about 1 minute to perform a post-exposure bake (PEB) process. Then, on the resist thin film, a development process was performed using PF-7600 for about 30 seconds. A thickness was measured through Alpha-step® D-300 stylus profiler manufactured by Kla-Tencor Co. to evaluate solubility properties.
A resist solution was prepared, a thin film was formed, and an exposure process and a post-exposure bake process were performed by the same method as in Experimental Example 7E. However, the development process after the exposure process was performed using n-butyl acetate (nBA). The solubility properties of the resist thin film were evaluated.
In PF-7600, P(RFMI6-tBOS) (3 wt/vol %) and a photo acid generator of nonafluorobutanesulfonyloxy-1,8-naphthalimide were dissolved to prepare a resist solution. In this case, the nonafluorobutanesulfonyloxy-1,8-naphthalimide was about 5 wt % of the P(RFMI6-tBOS).
A resist thin film was formed using the resist solution by the same method as in Experimental Example 2B. However, the resist thin film was formed into a thickness of about 100 nm.
Under an acceleration voltage of about 80 keV, an electron beam of about 50 to about 1,500 μC/cm2 was irradiated onto the resist thin film. The exposed resist thin film was heated at about 80° C. for about 1 minute to perform a post-exposure bake (PEB) process. Then, on the resist thin film, a development process was performed using PF-7600 for about 30 seconds. A thickness was measured through Alpha-step® D-300 stylus profiler manufactured by Kla-Tencor Co. to evaluate solubility properties.
A resist solution was prepared by the same method as in Experimental Example 8A. However, the resist solution was prepared by using P(RFMI6-tBAST) instead of P(RFMI6-tBOS). By using the resist solution, a resist thin film was formed by the same method as in Experimental Example 6A, and the solubility properties of the resist thin film were evaluated.
A resist solution was prepared by the same method as in Experimental Example 8A. However, the resist solution was prepared by using P(RFMI6-tBOCST) instead of P(RFMI6-tBOS). By using the resist solution, a resist thin film was formed by the same method as in Experimental Example 6A, and the solubility properties of the resist thin film were evaluated.
In PF-7600, P(RFMI6-tBOS) (3 wt/vol %) and a photo acid generator of triphenylsulfonium nonaflate (TPS-Nf) were dissolved to prepare a resist solution. In this case, the triphenylsulfonium nonaflate (TPS-Nf) was about 5 wt % of the P(RFMI6-tBOS).
A resist thin film was formed using the resist solution by the same method as in Experimental Example 2B. However, the resist thin film was formed into a thickness of about 100 nm.
Under an acceleration voltage of about 80 keV, an electron beam of about 50 to about 1,500 μC/cm2 was irradiated onto the resist thin film. The exposed resist thin film was heated at about 80° C. for about 1 minute to perform a post-exposure bake (PEB) process. Then, on the resist thin film, a development process was performed using PF-7600 for about 30 seconds. A thickness was measured through Alpha-step® D-300 stylus profiler manufactured by Kla-Tencor Co. to evaluate solubility properties.
A resist solution was prepared by the same method as in Experimental Example 9A. However, the resist solution was prepared by using P(RFMI6-tBAST) instead of P(RFMI6-tBOS). By using the resist solution, a resist thin film was formed by the same method as in Experimental Example 6A, and the solubility properties of the resist thin film were evaluated.
A resist solution was prepared by the same method as in Experimental Example 9A. However, the resist solution was prepared by using P(RFMI6-tBOCST) instead of P(RFMI6-tBOS). By using the resist solution, a resist thin film was formed by the same method as in Experimental Example 6A, and the solubility properties of the resist thin film were evaluated.
In PF-7600, P(RFMI6-tBOS) (3 wt/vol %) and a photo acid generator of nonafluorobutanesulfonyloxy-1,8-naphthalimide were dissolved to prepare a resist solution. In this case, the nonafluorobutanesulfonyloxy-1,8-naphthalimide was about 5 wt % of the P(RFMI6-tBOS).
The resist solution was applied on a silicon substrate at about 1250 rpm for about 60 seconds by spin coating. The coated solution was heated at about 110° C. for about 1 minute to form a resist thin film.
Under an acceleration voltage of about 80 keV, an electron beam of about 50 to about 1,500 μC/cm2 was irradiated onto the resist thin film. The exposed resist thin film was heated at about 80° C. for about 1 minute to perform a post-exposure bake (PEB) process. Then, on the resist thin film, a development process was performed using PF-7600 for about 30 seconds to form a resist pattern. As a result of the development process, a negative tone resist pattern with a size of about tens of nanometers was formed.
A resist solution was prepared by the same method as in Experimental Example 2A. However, the resist solution was prepared by using P(RFMI6-tBAST) instead of P(RFMI6-tBOS). By using the resist solution, a resist thin film and a resist pattern were formed by the same method as in Experimental Example 7A. The resist pattern was a negative tone pattern with a size of tens of nanometers.
A resist solution was prepared by the same method as in Experimental Example 2A. However, the resist solution was prepared by using P(RFMI6-tBOCST) instead of P(RFMI6-tBOS). By using the resist solution, a resist thin film was formed by the same method as in Experimental Example 7A. As a result of a development process, a negative tone pattern with a size of tens of nanometers was formed.
In PF-7600, P(RFMI6-tBOS) (1.3 wt/vol %) was dissolved to prepare a resist solution. The resist solution was applied on a silicon substrate at about 1250 rpm for about 60 seconds by spin coating. The coated solution was heated at about 110° C. for about 1 minute to form a resist thin film with a thickness of about 50 nm.
Under an acceleration voltage of about 80 keV, an electron beam of about 50 to about 1,500 μC/cm2 was irradiated onto the resist thin film. On the resist thin film, a development process was performed using PF-7600 for about 30 seconds. As a result of the development process, a negative tone resist pattern with a size of about tens of nanometers was formed.
In PF-7600, P(RFMI6-tBOS) (1.3 wt/vol %) and a photo acid generator of nonafluorobutanesulfonyloxy-1,8-naphthalimide were dissolved to prepare a resist solution. In this case, the nonafluorobutanesulfonyloxy-1,8-naphthalimide was about 10 wt % of the P(RFMI6-tBOS).
The resist solution was applied on a silicon substrate at about 1250 rpm for about 60 seconds by spin coating. The coated solution was heated at about 110° C. for about 1 minute to form a resist thin film with a thickness of about 50 nm.
Under an acceleration voltage of about 80 keV, an electron beam of about 50 to about 1,500 μC/cm2 was irradiated onto the resist thin film. The exposed resist thin film was heated at about 100° C. for about 1 minute to perform a post-exposure bake (PEB) process. Then, on the resist thin film, a development process was performed using PF-7600 for about 30 seconds. As a result of the development process, a negative tone resist pattern with a size of about tens of nanometers was formed.
In PF-7600, P(RFMI6-tBOS) (3 wt/vol %) was dissolved to prepare a resist solution.
The resist solution was applied on a silicon substrate at about 2000 rpm for about 60 seconds by spin coating. The coated solution was heated at about 110° C. for about 1 minute to form a thin film with a thickness of about 100 nm.
Under an acceleration voltage of about 80 keV, extreme ultraviolet was irradiated onto the resist thin film under conditions of about 5 to about 30 mJ/cm2. Then, on the resist thin film, a development process was performed using PF-7600 for about 30 seconds to form a resist pattern. By measuring the thickness of the resist pattern according to the exposure dose, the change of solubility properties were observed.
In PF-7600, P(RFMI6-tBOS) (3 wt/vol %) and a photo acid generator of nonafluorobutanesulfonyloxy-1,8-naphthalimide were dissolved to prepare a resist solution. In this case, the nonafluorobutanesulfonyloxy-1,8-naphthalimide was about 10 wt % of the P(RFMI6-tBOS).
The resist solution was applied on a silicon substrate at about 2000 rpm for about 60 seconds by spin coating. The coated solution was heated at about 110° C. for about 1 minute to form a thin film with a thickness of about 100 nm.
Under an acceleration voltage of about 80 keV, extreme ultraviolet was irradiated onto the resist thin film under conditions of about 5 to about 30 mJ/cm2. Then, on the resist thin film, a development process was performed using PF-7600 for about 30 seconds. By measuring the thickness of a resist pattern according to the exposure dose, the change of solubility properties were observed.
In PF-7600, P(RFMI6-tBOS) (3 wt/vol %) was dissolved to prepare a resist solution.
The resist solution was applied on a silicon substrate at about 2000 rpm for about 60 seconds by spin coating. The coated solution was heated at about 110° C. for about 1 minute to form a thin film with a thickness of about 100 nm.
Under an acceleration voltage of about 80 keV, extreme ultraviolet was irradiated onto the resist thin film under conditions of about 5 to about 30 mJ/cm2. Then, on the resist thin film, a development process was performed using PF-7600 for about 30 seconds to form a resist pattern. By measuring the thickness of the resist pattern according to the exposure dose, the change of solubility properties were observed.
In PF-7600, P(RFMI6-tBOS) (3 wt/vol %) and a photo acid generator of triphenylsulfonium nonaflate were dissolved to prepare a resist solution. In this case, the triphenylsulfonium nonaflate was about 5 wt % of the P(RFMI6-tBOS).
The resist solution was applied on a silicon substrate at about 200 rpm for about 60 seconds by spin coating. The coated solution was heated at about 110° C. for about 1 minute to form a thin film with a thickness of about 100 nm.
Under an acceleration voltage of about 80 keV, extreme ultraviolet was irradiated onto the resist thin film under conditions of about 5 to about 30 mJ/cm2. Then, on the resist thin film, a development process was performed using PF-7600 for about 30 seconds. By measuring the thickness of a resist pattern according to the exposure dose, the change of solubility properties were observed.
Table 1 shows measured results of the number average molecular weight (Mn), polydispersity index (PDI), and glass transition temperature of Experimental Example 1A, Experimental Example 1B, Experimental Example 1C, and Comparative Example 1. The number average molecular weight and the polydispersity index were analyzed by gel permeation chromatography (hereinafter, GPC) and nuclear magnetic resonance spectrum (1H NMR). The glass transition temperature was measured through difference scanning calorimetry (hereinafter, DSC) analysis.
Referring to Table 1, Experimental Example 1A, Experimental Example 1B, and Experimental Example 1C showed higher glass transition temperatures than that of Comparative Example 1.
It could be confirmed that Experimental Example 1A, Experimental Example 1B, and Experimental Example 1C showed relatively low polydispersity indexes. Particularly, the polydispersity indexes of Experimental Example 1A, Experimental Example 1B, and Experimental Example 1C were analyzed as about 1.0 to about 1.5.
Table 2 shows evaluation results of solubility properties of Experimental Example 1A, Experimental Example 1B, and Experimental Example 1C. The solubility properties were evaluated for coating solvents. In Table 2, O means soluble, and X means insoluble.
Referring to Table 2, the compounds formed in Experimental Example 1A, Experimental Example 1B, and Experimental Example 1C showed solubility with respect to cyclohexanone and PF-7600 before exposure. However, through Experimental Examples 2A, 2C and 2D, it could be confirmed that PF-7600 showed capacity of forming a uniform thin film for three compounds.
Table 3A shows evaluation results of solubility properties for the developing solutions of the resist patterns of Experimental Example 3A, Experimental Example 3B, Experimental Example 3C under the I-line exposure. Table 3B shows evaluation results of solubility properties for the developing solutions of the resist patterns of Experimental Example 4A, Experimental Example 4B, and Experimental Example 4C under the I-line exposure. In Table 3A and Table 3B, O means that solubility change was shown before and after the exposure, X means that solubility change was not shown before and after the exposure, and A means that solubility change was shown before and after the exposure, but a residual film was partially present. In Table 3A and Table 3B3, a mixture solution of TMAH and IPA was prepared by mixing 0.26 M tetramethyl ammonium hydroxide (TMAH) and isopropanol (IPA) in a volume ratio of 7:3.
Referring to Table 3A, the resist patterns of Experimental Example 3A, Experimental Example 3B, and Experimental Example 3C showed excellent solubility with respect to PF-7600. If the resist films of Experimental Example 3A, Experimental Example 3B, and Experimental Example 3C are developed using PF-7600, negative resist patterns with a uniform line width may be formed.
Referring to Table 3B, the resist patterns of Experimental Example 4A, Experimental Example 4B, and Experimental Example 4C showed excellent solubility with respect to the mixture solution of TMAH and IPA. If the resist films of Experimental Example 4A, Experimental Example 4B, and Experimental Example 4C are developed using the mixture solution of TMAH and IPA, positive resist patterns with a uniform line width may be formed.
Table 4 showed evaluation results of solubility properties with respect to the developing solutions of the resist patterns of Experimental Example 3A, and Experimental Example 4A. The resist pattern of Experimental Example 4A was formed using a mixture solution of TMAH and IPA in a volume ratio of 5:2 as a developing solution.
Referring to Table 4, the resist pattern of Experimental Example 3A was prepared using a nonpolar developing solution of PF-7600. As a result of a development process, the resist pattern was formed as a negative tone pattern.
The resist pattern of Experimental Example 4A was prepared using a mixture solution of TMAH and IPA, which is a polar developing solution. As a result of a development process, the resist pattern was formed as a positive tone pattern.
Table 5 shows evaluation results of solubility properties on the developing solutions of resist patterns of Experimental Example 8A, Experimental Example 8, and Experimental Example 8C under the exposure of extreme ultraviolet and electron beam. In Table 5, O means that solubility change was shown before and after the exposure, X means that solubility change was not shown before and after the exposure, and A means that solubility change was shown before and after the exposure, but a residual film was partially present. In Table 5, a mixture solution of TMAH and TPA was prepared by mixing 0.26 M tetramethyl ammonium hydroxide (TMAH) and isopropanol (IPA) in a volume ratio of 7:3.
Referring to Table 5, the resist patterns of Experimental Example 8A, Experimental Example 8B, and Experimental Example 8C showed definite solubility change with respect to PF-7600 and n-butyl acetate (nBA) before and after the exposure. If the resist films of Experimental Example 7A, Experimental Example 7B, Experimental Example 7C, Experimental Example 7D, Experimental Example 7E, and Experimental Example 7F are developed using PF-7600 and n-butyl acetate, negative resist patterns may be formed.
Referring to
Referring to
Referring to
Referring to
Referring to
Referring to
Table 6 shows evaluated results on patterning properties of Experimental Example 10A, Experimental Example 10B, and Experimental Example 10C. A critical dimension (CD) may correspond to the width W of a resist pattern 300P of
Referring to
According to embodiments, the resist compositions include the copolymer represented by Formula 3A, and the resist films may have high sensitivity in a lithography process using electron beam.
Table 7 shows evaluated results of patterning properties of Experimental Example 11A and Experimental Example 11B. A critical dimension (CD) may correspond to the width W of a resist pattern 300P of
Referring to Table 7, in the case where the electron beam dose was about 1300 μC/cm2, the resist pattern of Experimental Example 11A showed a critical dimension of about 50 nm. In the case where the electron beam dose was about 850 μC/cm2, the resist pattern of Experimental Example 11B showed a critical dimension of about 50 nm. The resist pattern of Experimental Example 11A and the resist pattern of Experimental Example 11B showed excellent line-edge roughness properties and line width roughness properties.
According to embodiments, the resist compositions further included a photo acid generator, and the resist films showed high sensitivity in a lithography process using electron beam. Though the resist pattern further includes a photo acid generator, the resist pattern may show excellent resolution. The resolution of the resist pattern may be evaluated by the line-edge roughness properties and the line width roughness properties.
Referring to
Referring to
According to embodiments, the resist compositions further included a photo acid generator, and the resist films showed improved sensitivity in a lithography process using extreme ultraviolet.
According to the inventive concept, the composition includes an alternating copolymer and may show a uniform composition and narrow molecular weight distribution. The alternating copolymer may be prepared using a maleimide monomer having a highly halogenated alkyl group. By using the composition, a resist film may be formed. The resist film may have high sensitivity to light. The alternating copolymer may be prepared using a styrene monomer having an acid-cleavable protective group. Accordingly, the solubility of the resist film in a developing solution may be improved. The resolution of the resist pattern may be improved.
Although the embodiments of the present invention have been described, it is understood that the present invention should not be limited to the embodiments, but various changes and modifications can be made by one ordinary skilled in the art within the spirit and scope of the present invention as hereinafter claimed.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2020-0144301 | Nov 2020 | KR | national |
