WO2012133050A1 - Dérivé de thiacalix[4]arène - Google Patents

Dérivé de thiacalix[4]arène Download PDF

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WO2012133050A1
WO2012133050A1 PCT/JP2012/057196 JP2012057196W WO2012133050A1 WO 2012133050 A1 WO2012133050 A1 WO 2012133050A1 JP 2012057196 W JP2012057196 W JP 2012057196W WO 2012133050 A1 WO2012133050 A1 WO 2012133050A1
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arene
thiacalix
group
synthesis
derivative
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PCT/JP2012/057196
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English (en)
Japanese (ja)
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佐藤　誠
真由美 岸
誠司 東野
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株式会社トクヤマ
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D341/00—Heterocyclic compounds containing rings having three or more sulfur atoms as the only ring hetero atoms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the present invention relates to a thiacalix [4] arene derivative suitably used for a semiconductor device, a semiconductor integrated circuit, and a pattern for forming a fine structure represented by an imprint mold, a photomask, or the like.
  • the present invention also relates to a resist material containing the thiacalix [4] arene derivative, and a method of forming a pattern using the resist.
  • a lithography method using a photoresist in a manufacturing process such as a semiconductor element such as a semiconductor integrated circuit (LSI) or the like, a photomask in which a pattern of an electronic circuit is formed of a light shielding material on a transparent substrate, and an imprint mold Micro processing is done.
  • a thin film of photoresist is formed on a silicon substrate or a quartz substrate on which a light shielding thin film is laminated, and high energy radiation such as excimer laser, X-ray, electron beam or the like is selectively added to this. Only a portion is irradiated to form a latent image of a pattern, and thereafter, a resist pattern obtained by developing is used as a mask for etching.
  • a photosensitive material called a resist material dissolved in an organic solvent is coated on a substrate having a layer to be processed on the surface, and the organic solvent is evaporated by prebaking to form a resist. Form a film.
  • the resist film is partially irradiated with light, and an unnecessary portion of the resist film is dissolved and removed using a developing solution to form a resist pattern on the substrate.
  • the layer to be processed on the substrate having this resist pattern as a mask is dry etched or wet etched.
  • micropatterning is completed by removing the resist pattern.
  • a wide variety of organic resists sensitive to electron beams are known, and resist patterns are formed by various methods.
  • a polymer thin film of an ethylenically unsaturated monomer such as polymethyl methacrylate is provided on a substrate as a resist film, and then a predetermined image is formed by irradiating an electron beam, and a low molecular weight ketone such as acetone
  • Patent Document 1 A method of forming a fine pattern by developing using a kind is proposed (see Patent Document 1).
  • a thin film of a resist material containing a chloromethylated calix [4] arene derivative is provided as a resist film, and then electron beam irradiation is performed to form a predetermined image, and ethyl lactate, propylene glycol monomethyl ether, or A method of forming a fine pattern by developing using 2-heptanone or the like has been proposed (see Patent Document 2).
  • an object of the present invention is to provide a resist material capable of preventing (reducing) adhesion between line patterns in a wider range of exposure dose than conventional calix [4] arene derivatives even when forming a plurality of line patterns, and
  • An object of the present invention is to provide a compound (calix [4] arene derivative) used for the material. (Hereinafter, the effect of preventing (reducing) adhesion between line patterns with a wide exposure amount may be described as "good resolution”.)
  • Another object of the present invention is to provide a method of forming a resist pattern using the resist material.
  • the present inventors diligently studied to achieve the above object. And it examined whether the above-mentioned subject could be solved by improving ring structure. As a result, the resolution of the thiacalix [4] arene derivative is improved by introducing a —S— group (sulfur atom) instead of a methylene group as a group connecting the benzene ring and the benzene ring in the molecule.
  • the present invention has been completed.
  • R 1 is an alkyl group, an acetyl group or an allyl group, and four R 1 s may be the same as or different from one another.
  • R 2 is a hydrogen atom or a halogenated methyl group, and four R 2 may be the same as or different from each other.
  • thiacalix [4] arene derivative shown by
  • a resist material comprising the thiacalix [4] arene derivative.
  • a resist pattern forming method comprises the steps of forming a latent image and developing the latent image.
  • the thiacalix [4] arene derivative of the present invention is a compound in which a sulfur atom is introduced instead of the cross-linking methylene group of the conventional calix [4] arene derivative, and even when a plurality of line patterns are formed, It is possible to form a good pattern of resolution with a wide exposure amount.
  • a compound into which an allyl group is introduced that is, a compound in which R 1 is an allyl group in the formula (1)
  • a resist material having high sensitivity is useful as a resist material having high sensitivity.
  • FIG. 7 shows sensitivity curvature of Example 1.
  • FIG. It is the electron microscope photograph which observed the pattern formed by exposure amount 10nC / cm of Example 1, and full pitch (fp) 35 nm by 100,000 times the magnification of this. It is the electron microscope photograph which observed the pattern formed by exposure amount 10nC / cm of 35 comparative examples, and full pitch (fp) of the comparative example 1 by 100,000 times the magnification of this.
  • the thiacalix [4] arene derivative of the present invention is a compound represented by the following formula (1).
  • R 1 is an alkyl group, an acetyl group or an allyl group.
  • the four R 1 s may be the same as or different from each other. That is, although R 1 is present four in the molecule, all four may be the same or different. In addition, three R 1 s may be the same group and one may be a different group.
  • R 1 is a group in which two are the same group, and the other two groups are different groups from the previous two, and even if these other two groups are the same as each other, they are different groups. It may be
  • the alkyl group includes an alkyl group having 1 to 10 carbon atoms, and may be linear or branched. Specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, isobutyl group, t-butyl group and hexyl group.
  • R 1 is an alkyl group having 1 to 5 carbon atoms in order to enhance the solubility of the compound of the above formula (1) in various solvents to facilitate the formation of a resist film. Is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable.
  • R 1 is preferably an alkyl group having 1 to 3 carbon atoms, an acetyl group, or an allyl group in order to obtain a resist material with high sensitivity, and to obtain a resist material with higher sensitivity
  • two or more of R 1 are allyl groups.
  • R 2 is a hydrogen atom or a halogenated methyl group.
  • the four R 2 s may be the same as or different from each other. That is, although R 2 is present four in the molecule, all four R 2 s may be the same or different. In addition, three R 2 s may be the same group and one may be a different group. Furthermore, R 2 is a group in which two are the same group, and the other two groups are different from the above two groups, and even if these other two groups are the same as each other, they are different groups. It may be
  • halogenated methyl group what is a group which has one halogen atom is preferable.
  • the halogen atom include chlorine atom, bromine atom and iodine atom, among which chlorine atom is preferable. That is, the most preferred group is chloromethyl group.
  • the halogenated methyl group serves as a crosslinking point when exposed to high energy rays, which contributes to high sensitivity. Therefore, it is preferable that at least one group of four R 2 be a halogenated methyl group. More preferable is a case where a group of 2 or more and 4 or less of four R 2 is a halogenated methyl group. More preferable is the case where 3 or more and 4 or less of the four R 2 groups are halogenated methyl groups, and particularly preferable is the case where all the R 2 groups are halogenated methyl groups.
  • the greatest feature of the present invention is that a sulfur atom (—S— group) is introduced instead of the bridging methylene group of the conventional calix [4] arene derivative.
  • the thiacalix [4] arene derivative represented by the above formula (1) into which this sulfur atom is introduced exhibits an improved resolution.
  • the optimal exposure amount of each thiacalix [4] arene derivative differs depending on the type of substituent, a good pattern can be formed with a wide range of exposure amounts.
  • the thiacalix [4] arene derivative of the present invention incorporating a sulfur atom has the same substituent and has a cross-linking methylene group It is understood that the range of the exposure amount which can prevent (reduce) adhesion (adhesion) between the line patterns is wider than that of the calix [4] arene derivative, and hence the range of the line pattern production conditions is wide.
  • n is preferably 0 to 2, more preferably 0 to 1, and 0 Is most preferred.
  • a compound in which two or more of R 1 are allyl groups is particularly preferable because it exhibits higher sensitivity.
  • those showing a high sensitivity preferably are compounds in which n is 0 to 2 and two or more of R 1 are allyl groups.
  • Compounds that exhibit high sensitivity more preferably are compounds in which n is 0 to 1 and two or more of R 1 are allyl groups, and those that exhibit the highest sensitivity are n is 0 and R is All 1 is a compound which is an allyl group.
  • Non-Patent Document “Honbashi et al .: “Journal of Organic Chemistry", Vol. 68) Methods described in Non-Patent Document (LHOTAK et al., "Tetrahedron Letters", vol. 41, pp. 9339 to 9344 (2000)) can be employed. At this time, the number of n can be prepared by adjusting the reaction conditions.
  • a halogenated methyl group is introduced into the compound into which an alkyl group, an acetyl group or an allyl group has been introduced, if necessary, by the above method. That is, hydrogen of the benzene ring is converted to a halogenated methyl group.
  • a method for introducing a halogenated methyl group it is described, for example, in JP-A-11-255766 and non-patent literature (KASYAN et al .: “Tetrahedron Letters", vol. 44, pp. 7167-7170, 2003). Method can be adopted.
  • the reaction conditions can be prepared the introduction percentage of methyl halide group to R 2.
  • the thiacalix [4] arene derivative of the present invention can be produced.
  • the structure of the obtained thiacalix [4] arene derivative can be determined by IR, NMR, LC-MS and the like.
  • LC-MS gives characteristic signals derived from sulfur compounds.
  • the sulfur atom has three isotopes of mass numbers 32, 33 and 34, and the abundance ratios thereof are 95.06%, 0.74% and 4.2%, respectively. Therefore, in addition to the molecular ion peak M, a relatively strong M + 2 peak can be detected. Further, the number of sulfur atoms contained in one molecule can also be estimated from the peak intensity of M + 2.
  • the present invention also provides a resist material comprising the thiacalix [4] arene derivative. Next, this resist material will be described.
  • the resist material of the present invention contains the thiacalix [4] arene derivative represented by the above formula (1).
  • the thiacalix [4] arene derivative represented by the above formula (1) may be used alone or in combination of two or more. That is, the four R 1 s and the four R 2 s may be a mixture of different groups.
  • the resist material of the present invention includes ethyl lactate (EL), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl propionate, n-butyl acetate, in addition to the thiacalix [4] arene derivative.
  • EL ethyl lactate
  • PGME propylene glycol monomethyl ether
  • PMEA propylene glycol monomethyl ether acetate
  • ethyl propionate ethyl propionate
  • n-butyl acetate ethyl propionate
  • n-butyl acetate ethyl propionate
  • n-butyl acetate ethyl propionate
  • n-butyl acetate ethyl propionate
  • n-butyl acetate ethyl propionate
  • n-butyl acetate eth
  • the resist material of the present invention can also contain known additives such as surfactants, if necessary.
  • the resist material of the present invention after dissolving all the components such as the thiacalix [4] arene derivative and the additive which is optionally blended, in the above organic solvent, filtration is performed using a membrane filter or the like as necessary.
  • a membrane filter or the like as necessary.
  • the content of the thiacalix [4] arene derivative contained in the prepared resist material may be appropriately determined according to the desired thickness of the resist film, the type of the thiacalix [4] arene derivative, and the like. Although it is good, it is usually 0.1 to 10% by mass.
  • Such resist materials can be used to form a pattern. Next, a method of forming this resist pattern will be described.
  • ⁇ Method of forming resist pattern> In order to form a resist pattern using the resist material, the following method may be employed. Specifically, after applying the resist material onto a substrate to be treated, a step of prebaking to form a resist film, and selectively exposing the resist film with high energy rays to form a latent image of a desired pattern. A resist pattern can be formed by performing the forming step and the developing step. Each step will be described in detail below.
  • the substrate on which the resist film is laminated is not particularly limited, and an oxide film, a nitride film, a metal thin film or the like is formed on a known substrate such as a silicon substrate, a photomask and the above substrate. A substrate is used.
  • the resist material is coated on these substrates by a known method such as spin coating, and baked to form a resist film containing the thiacalix [4] arene derivative.
  • a known method such as spin coating
  • baked it is preferable to carry out heat treatment at a temperature of 80 to 130 ° C. for about 10 seconds to 5 minutes using a hot plate or the like.
  • the film thickness of the formed resist film may be suitably determined in accordance with the application etc. to be used, but it is usually 5 to 300 nm.
  • a resist film containing the thiacalix [4] arene derivative can be formed on a substrate.
  • the step of selectively exposing the resist film to high energy rays to form a latent image of a pattern will be described.
  • ⁇ Step of forming a latent image of a pattern> high energy rays are selectively exposed on the resist film on the substrate obtained in the resist film forming step to form a latent image of a pattern.
  • the high energy beam is not particularly limited as long as it is a radiation source capable of forming a latent image on the resist film by energy irradiation, and examples thereof include an electron beam, an X-ray, and an ion beam.
  • the portion to which the high energy ray is exposed may be appropriately determined according to the pattern to be formed. Therefore, a known method can be adopted as a method of selectively exposing high energy rays, and for example, direct exposure or irradiation through a mask may be performed.
  • a latent image of a pattern can be formed on the resist film.
  • a substrate obtained by the above method that is, a resist film containing the above-mentioned thiacalix [4] arene derivative is laminated, and the resist film is selectively exposed to high energy rays to form a pattern.
  • the substrate on which the latent image is formed (hereinafter, also simply referred to as a substrate obtained in the latent image forming step) may be developed with a developer containing an organic solvent.
  • the latent image is developed by removing a portion of the resist film which is not exposed to the high energy beam with a developer containing an organic solvent.
  • the developing solution used in this development uses a solvent having different dissolution rates in the exposed area and the unexposed area.
  • the developer used in the present invention includes ethyl lactate (EL), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl propionate, n-butyl acetate, 2-butyl acetate used as a solvent for resist materials.
  • PGME propylene glycol monomethyl ether
  • PMEA propylene glycol monomethyl ether acetate
  • ethyl propionate ethyl propionate
  • n-butyl acetate ethyl propionate
  • 2-butyl acetate 2-butyl acetate
  • xylene xylene
  • alcohols ethanol, isopropyl alcohol and the like
  • glycol ethers hydrofluoroalkyl ether and the like
  • the method for developing the substrate obtained in the latent image forming step using the developer is not particularly limited, and a known method can be adopted. Specifically, a method of dipping the substrate in a bath filled with the developer (dip method), a method of placing the developer on the substrate surface (paddle method), a method of spraying the developer onto the substrate The spray method is generally used. Among these methods, the paddle method or the spray method is preferred in order to reduce particles.
  • the substrate obtained in the latent image forming step or the heat treatment step is usually the above developer at a temperature of 10 ° C. to 35 ° C., preferably 15 ° C. to 30 ° C. Apply and leave still or continue spraying the developer on the substrate for a predetermined time.
  • the settling time or spraying time is not particularly limited, but is preferably 30 seconds or more and 5 minutes or less in consideration of throughput.
  • the substrate on which the resist pattern has been formed by development according to the above method is, if necessary, removed of the remaining developer and the like by a rinse liquid.
  • the organic solvent used as the rinse solution may be the same as or different from the developer described above, but preferably has a boiling point of 150 ° C. or less at atmospheric pressure, and 120 ° C. or less in consideration of easiness of drying. Is more preferable.
  • the above-mentioned development step and this rinse step can be alternately repeated about 2 to 10 times.
  • a fine resist pattern is formed by combining the thiacalixarene derivative and the developer.
  • the resist material was spin-coated on a 4-inch silicon wafer and baked on a hot plate at 110 ° C. for 60 seconds to form a resist film having a thickness of about 35 nm (as a solid) (resist film forming step).
  • an electron beam lithography system CABL-9210TF manufactured by Crestec is used to adjust the electron beam irradiation dose at an acceleration voltage of 50 kV and a beam current of 100 pA on the resist film formed on the silicon wafer (adjusting the exposure dose) And 200 ⁇ m wide line & space pattern for sensitivity evaluation and full pitch (fp) 50, 40 and 35 nm wide line & space pattern for resolution evaluation (latent image forming step).
  • IPA isopropyl alcohol
  • the sensitivity and resolution of the resist pattern thus obtained were evaluated by the following method.
  • the sensitivity curve for Example 1 is shown in FIG.
  • the sensitivity curve is obtained by measuring the film thickness of the exposed portion using a film thickness measuring instrument, the exposure amount on the horizontal axis, and the film thickness on the vertical axis. In the same manner as in each of the examples and the comparative examples, such a sensitivity curve was created, and the exposure amount (D) was determined. Specifically, as shown in FIG. 1, the approximate straight line at the rising portion of the sensitivity curve (a straight line rising to the right shown by the dotted line in the figure) and the approximate straight line at the flat portion (the horizontal straight line shown by the dotted line in the figure). And the exposure amount at the intersection (about 1.4 mC / cm 2 in FIG. 1) was determined as the exposure amount (D).
  • FIG. 2 shows an electron micrograph (magnification of 100,000 times) of the pattern produced at a full pitch of 35 nm and an exposure dose of 10 nC / cm in Example 1
  • FIG. 3 shows a full pitch of 35 nm and an exposure dose of 10 nC / cm in Comparative Example 1.
  • the electron micrograph (magnification of 100,000 times) of the produced pattern was shown.
  • Synthesis Example 1 Synthesis of Thiacalix [4] arene Derivative of Example 1>
  • the reaction is carried out in the order of first t-butylation reaction, secondly introduction reaction of methyl group, and lastly chloromethylation reaction, Thiacalix [4] arene was synthesized.
  • thiacalix [4] arene was synthesized by the following t-butylation reaction according to the following method.
  • the reaction mixture was transferred to a separatory funnel, and 600 ml of chloroform was added to separate the organic phase.
  • the aqueous phase is then extracted 10 times with 300 ml of chloroform and combined with the organic phase.
  • the organic phase was predried over anhydrous magnesium sulfate and filtered.
  • the solvent was distilled off with an evaporator to obtain a mixture of white crystals and a brown liquid.
  • the mixture was added with 500 ml of methanol, refluxed for 30 minutes, and allowed to cool.
  • the white crystals were filtered through a Kiriyama funnel and washed with 150 ml of methanol.
  • the reaction mixture was poured into 800 ml of 0.1 N hydrochloric acid to quench the reaction.
  • the reaction mixture was transferred to a separatory funnel, and 200 ml of chloroform was added to separate the organic phase.
  • the aqueous phase is then extracted five times with 200 ml of chloroform and combined with the organic phase.
  • the organic phase was then washed with 20% aqueous sodium chloride solution, predried over anhydrous magnesium sulfate and filtered.
  • the solvent was distilled off with an evaporator to obtain a brown liquid. While stirring, 80 ml of chloroform and 200 ml of methanol were slowly added to the brown liquid to reprecipitate.
  • the reaction mixture was transferred to a separatory funnel, and 300 ml of chloroform was added to separate the organic phase.
  • the aqueous phase is extracted twice with 300 ml of chloroform and combined with the organic phase.
  • the organic phase was washed twice with 500 ml of water and it was confirmed that the pH of the aqueous phase had become neutral.
  • the organic phase was predried over anhydrous magnesium sulfate and filtered.
  • the solvent was distilled off with an evaporator to obtain a brown liquid.
  • Synthesis Example 2 Synthesis of Thiacalix [4] arene Derivative of Example 2>
  • the chloromethylation reaction was carried out using methoxythiacalix [4] arene synthesized in Synthesis Example 1 as a raw material.
  • the chloromethylation reaction was carried out in the same manner as in Synthesis Example 1 except that the preparation amount was changed.
  • the charge amount is 8.0 g (0.014 mol) of methoxythiacalix [4] arene, 3.4 g (0.042 mol) of chloromethyl methyl ether, 0.5 g (0.004 mol) of zinc chloride and 100 ml of dehydrated chloroform.
  • the yield was 42.2%, and the HPLC purity was 98.7%.
  • Synthesis Example 3 Synthesis of Thiacalix [4] arene Derivative of Example 3 Using thiacalix [4] arene synthesized in Synthesis Example 1 as a raw material, first, acetoxythiacalix [4] arene is synthesized, and then chloromethyl is introduced by introducing a halogenated methyl group (chloromethylation). Acetoxythiacalix [4] arene was synthesized. First, acetoxythiacalix [4] arene was synthesized by the following method.
  • the reaction mixture was slowly poured into 600 ml of 0.2 N sulfuric acid to quench the reaction. Thereafter, the mixture was well stirred for 1 hour or more, transferred to a separatory funnel, and 500 ml of chloroform was added to separate an organic phase.
  • the aqueous phase is extracted three times with 200 ml of chloroform and combined with the organic phase.
  • the organic phase was washed three times with 300 ml of water, and it was confirmed that the pH of the aqueous phase became neutral.
  • the organic phase was predried over anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator to obtain a white solid.
  • the white solid was dissolved in 600 ml chloroform and then 1200 ml methanol was slowly added with stirring to reprecipitate. The solid was filtered through a Kiriyama funnel and washed with 200 ml of methanol. The obtained white solid was dried under vacuum (50 ° C., 12 hours or more) to obtain 17.6 g of the target product, acetoxythiacalix [4] arene. The yield was 58.7%, and the HPLC purity was 99.1%. Subsequently, introduction of a halogenated methyl group (chloromethyl group) was performed by the following method.
  • Synthesis Example 4 Synthesis of Thiacalix [4] arene Derivative of Example 4 First, an allyloxythiacalix [4] arene is synthesized using the thiacalix [4] arene synthesized in Synthesis Example 1 as a raw material, and then chloromethylation to give a chloromethylallyloxythiacalix [4]. An arene was synthesized. First, the synthesis of aryloxythiacalix [4] arene was performed by the following method.
  • Synthesis Example 6 Synthesis of Thiacalix [4] arene Derivative of Example 6> Using thiacalix [4] arene synthesized in Synthesis Example 1 as a raw material, first, dimethoxythiacalix [4] arene is synthesized, then, an acetyl group is introduced, and finally, a chloromethylated (halogenated methyl group Introduction: Chloromethyldimethoxydiacetoxythiacalix [4] arene was synthesized by carrying out the reaction in the order of reaction. First, dimethoxythiacalix [4] arene was synthesized by the following method.
  • the reaction mixture was poured into 800 ml of 0.1 N hydrochloric acid to quench the reaction.
  • the reaction mixture was transferred to a separatory funnel, and 200 ml of chloroform was added to separate the organic phase.
  • the aqueous phase is then extracted five times with 200 ml of chloroform and combined with the organic phase.
  • the organic phase was then washed with 20% aqueous sodium chloride solution, predried over anhydrous magnesium sulfate and filtered.
  • the solvent was distilled off with an evaporator to obtain a brown liquid. With stirring, 80 ml of chloroform and 200 ml of methanol were slowly added to the brown liquid to reprecipitate.
  • the solid was filtered through a Kiriyama funnel and washed with 100 ml of methanol.
  • the obtained beige solid was dried under vacuum (for 12 hours or more at 50 ° C.) to obtain 8.3 g of the target product dimethoxythiacalix [4] arene.
  • the yield was 65.5%, and the HPLC purity was 98.7%.
  • the synthesis of dimethoxydiacetoxythiacalix [4] arene was carried out by introducing an acetyl group.
  • Synthesis Example 7 Synthesis of Thiacalix [4] arene Derivative of Example 7 Using dimethoxythiacalix [4] arene synthesized in Synthesis Example 5 as a raw material, first, dimethoxydiaryloxythiacalix [4] arene is synthesized and then chloromethylated to obtain chloromethyldimethoxydiaryloxyl. Thiacalix [4] arene was synthesized. First, the synthesis of dimethoxydiaryroxycalix [4] arene was carried out by the following method.
  • Synthesis Example 8 Synthesis of Thiacalix [4] arene Derivative of Example 8 Using dimethoxydiallyloxythiacalix [4] arene synthesized in Synthesis Example 6 as a raw material, trichloromethyldimethoxydiaryloxythiacalix [4] arene was synthesized by chloromethylation according to the following method.
  • dimethoxydiallyloxythiacalix [4] arene 8.5 g (0.014 mol), chloromethyl methyl ether 3.4 g (0.042 mol), zinc chloride 0.5 g (0.004 mol) and dehydrated chloroform 100 ml It is. The yield was 6.3%, and the HPLC purity was 98.1%. The structure was identified by 1 H-NMR and LC-MS.
  • Example 1 and Comparative Example 1 and Comparative Example 2 Example 4 and Comparative Example 3, Example 5 and Comparative Example 4, Example 6 and Comparative Example 5, and Example 7 and Comparative Example
  • the thiacalix [4] arene derivative of the example and the calixarene derivative of the comparative example have the same structure except that the former contains an S atom and the latter contains a methylene group. It is understood that the former can form a good pattern over a wider range of exposure dose than the latter, though it is possessed.

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Abstract

L'invention concerne un dérivé de thiacalix[4]arène décrit par la formule (1). (Dans la formule, R1 représente un groupe alkyle, un groupe acétyle ou un groupe allyle, et les quatre incidences de R1 peuvent être le même groupe ou un groupe différent. R2 représente un atome d'hydrogène ou un groupe méthyle halogéné, et les quatre incidences de R2 peuvent être le même groupe ou un groupe différent.) Le dérivé de thiacalix[4]arène est caractérisé en ce qu'il présente une résolution supérieure à celle des dérivés de calixarène classiques au niveau des motifs pour le façonnage d'un corps à structure fine, représenté par des dispositifs de semi-conducteurs, des circuits intégrés de semi-conducteurs et des moules destinés à l'impression, ou dans des résines photosensibles à un faisceau électronique utilisées dans la fabrication de photomasques.
PCT/JP2012/057196 2011-03-31 2012-03-21 Dérivé de thiacalix[4]arène WO2012133050A1 (fr)

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KR20200037146A (ko) * 2017-07-27 2020-04-08 디아이씨 가부시끼가이샤 레지스트 재료

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010001825A1 (fr) * 2008-07-03 2010-01-07 コニカミノルタビジネステクノロジーズ株式会社 Toner et procédé de fabrication de toner
WO2010134639A1 (fr) * 2009-05-21 2010-11-25 株式会社トクヤマ Procédé pour la formation d'un motif de réserve, et solution de révélation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010001825A1 (fr) * 2008-07-03 2010-01-07 コニカミノルタビジネステクノロジーズ株式会社 Toner et procédé de fabrication de toner
WO2010134639A1 (fr) * 2009-05-21 2010-11-25 株式会社トクヤマ Procédé pour la formation d'un motif de réserve, et solution de révélation

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
0. KASYAN ET AL.: "Tetraallyl Ethers of Thiacalix [4]arenes in the 1,3-Alternate Conformation", JOURNAL OF CHEMICAL CRYSTALLOGRAPHY, vol. 41, no. 3, 7 September 2010 (2010-09-07), pages 332 - 337, XP019882310, DOI: doi:10.1007/s10870-010-9883-7 *
J. LANG ET AL.: "Conformational Flexibility of a Novel Tetraethylether of Thiacalix[4]arene. A Comparison with the ''Classical'' Methylene- Bridged Compounds", TETRAHEDRON LETTERS, vol. 40, no. 2, 1999, pages 373 - 376, XP004152556, DOI: doi:10.1016/S0040-4039(98)02315-6 *
M.SIMANOVA ET AL.: "Synthesis and conformational behaviour of lower-rim tetraacetylated thiacalix[4]arenes", TETRAHEDRON LETTERS, vol. 49, no. 6, 2008, pages 1026 - 1029, XP022417909, DOI: doi:10.1016/j.tetlet.2007.12.004 *
P.LHOTAK ET AL.: "Tetraalkylated 2,8,14,20- Tetrathiacalix[4]arenes: Novel Infinite Channels in the Solid State", TETRAHEDRON LETTERS, vol. 39, no. 48, 1998, pages 8915 - 8918, XP004140964, DOI: doi:10.1016/S0040-4039(98)01950-9 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200037146A (ko) * 2017-07-27 2020-04-08 디아이씨 가부시끼가이샤 레지스트 재료
KR102490291B1 (ko) 2017-07-27 2023-01-20 디아이씨 가부시끼가이샤 레지스트 재료

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