WO2015174072A1

WO2015174072A1 - Compounders for enhancing generation of chemical species

Info

Publication number: WO2015174072A1
Application number: PCT/JP2015/002388
Authority: WO
Inventors: Satoshi Enomoto; Yusuke Suga
Original assignee: Toyo Gosei Co Ltd
Current assignee: Toyo Gosei Co Ltd
Priority date: 2014-05-13
Filing date: 2015-05-11
Publication date: 2015-11-19
Anticipated expiration: 2016-11-13
Also published as: JP2017516144A

Abstract

A reagent that enhances acid generation of a photoacid generator and composition containing such reagent is disclosed.

Description

Compounders for Enhancing Generation of Chemical Species

　This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application Serial No.61/992.722 filed on May 13, 2014, the disclosure of which is hereby incorporated herein in its entirety by the reference.

　Several aspects of the present invention relates to the fields of material enhancing a generation of a chemical species such as acid and base. Typical examples of materials relating to an aspect of the present invention can be used as constituent of photoresist compositions which can be applied to fabrication of interlayer insulating films of devices such as liquid crystal display (LCD), organic electroluminescent display (OLED) and semiconductor device.

　Current high-resolution lithographic processes are based on chemically amplified resists (CARs) and are used to pattern features with fine dimensions.

　Method for forming pattern features with fine dimensions is disclosed in US 7851252 (filed on February 17, 2009).

BRIEF SUMMARY

　A substance relating to an aspect of the present invention is characterized by that: such substance absorbs a light of which wavelength is equal to or longer than 220 nm; and such substance is capable of sensitizing a compounder to enhance a formation of a chemical species from at least one of the substance and the compounder.

　A substance relating to an aspect of the present invention is characterized by that: the substance is capable of donating an energy or an electron to a compounder or accepting an energy or an electron from a compounder by an exposure of the substance to a first electromagnetic ray and a first particle ray to enhance a formation of a chemical species from at least one of the substance and the compounder.

　With regard to such substance, it is preferred that the chemical species is at least one of acid and base.

　With regard to such substance, it is preferred that the chemical species is at least one of Broensted acid and Broensted base.

　With regard to such substance, it is preferred that the substance has a following characteristic: a molar absorption coefficient of the substance at 400 nm when measured in a solution is equal to or lower than 200. Since such substance has high optical transmittance in the visible light range, such substance may be suitable for material used for fabrication of electro-optical device such as display device or patterning thick films. Even though such substance remains in such electro-optical device after fabrication of such device, such may not impair functions of such device.

　With regard to such substance, it is preferred that the substance has a following characteristic: a molar absorption coefficient of the substance at 400 nm when measured in a solution is equal to or lower than 100.

　With regard to such substance, it is preferred that the substance has a following characteristic: a ratio of an absorbance at 365 nm (“Ab365”) to an absorbance at 400 nm (“Ab400”) when measured in a solution is equal to or greater than 2.0. Since such substance has a large difference of absorbance at 365 nm and 400 nm, such substance may show high photoreactivity with irradiation with an ultraviolet light while high optical transmittance in the visible light range. Therefore, even though such substance remains in such electro-optical device after fabrication of such device, such may not impair functions of such device.

　With regard to such substance, it is preferred that the substance has a following characteristic: a ratio of an absorbance at 365 nm (“Ab365”) to an absorbance at 400 nm (“Ab400”) when measured in a solution is equal to or greater than 50.

　With regard to such substance, it is preferred that the substance has a following characteristic: a ratio of an absorbance at 365 nm (“Ab365”) to an absorbance at 400 nm (“Ab400”) when measured in a film is equal to or greater than 100.

　With regard to such substance, it is preferred that the substance is capable of accepting the energy or the electron from the compounder to enhance the chemical species from the substance.

　With regard to such substance, it is preferred that the substance is capable of being converted into a reactive intermediate by accepting the electron from the compounder.

　With regard to such substance, it is preferred that the reactive intermediate is capable of generating the chemical species.

　With regard to such substance, it is preferred that the reactive intermediate is an anion radical.

　A reagent relating to an aspect of the present invention is characterized by that: the reagent is capable of generating a compounder in at least one of a composition including the reagent, a liquid containing the composition and a film of the composition; and the compounder is capable of enhancing formation of a first chemical species from at least one of the compounder and a substance by an interaction of the compounder with the substance.

　With regard to such reagent, it is preferred that such interaction is promoted by an exposure of the composition, the liquid and the film to at least one of a first electromagnetic ray and a first particle ray.

　With regard to such reagent, it is preferred that the compounder is formed through a reaction of the reagent with a second chemical species generated from the compounder.

　With regard to such reagent, it is preferred that: the first chemical species is also generated from the reagent without any interaction with the compounder; and the compounder is formed by a reaction of the reagent with the first chemical species.

　With regard to such reagent, it is preferred that the compounder is capable of donating an electron to the reagent.

　With regard to such reagent, it is preferred that the reagent is capable of generating the compounder through processes triggered by supplying energy to the film.

　With regard to such reagent, it is preferred that a conjugation length of the compounder is longer than a conjugation length of the reagent.

　With regard to such reagent, it is preferred that: the reagent has at least two pi-electron systems; the compounder has at least two pi-electron systems; and an electronic interaction between the at least two pi-electron systems in the compounder is stronger than an electronic interaction between the at least two pi-electron systems in the reagent.

　A composition relating to an aspect of the present invention includes any one of the aforementioned substances and any one of the compounders.

　A composition relating to an aspect of the present invention includes any one of the aforementioned substances and a reagent capable of generating any one of the compounders.

　With regard to such composition, it is preferred that the substance is a photoacid generator (PAG).

　With regard to the composition, it is preferred that the composition further includes a compound. Such compound may react with the chemical species.

　A polymer relating to an aspect of the present invention includes a first moiety capable of interacting with a substance; and a second moiety which is to react with a chemical species.

　With regard to such polymer, it is preferred that the first moiety donates energy or an electron to the substance or accepts energy or an electron from the substance.

　With regard to such polymer, it is preferred that the polymer further includes a third moiety from which the chemical species is to be generated.

　With regard to such composition, it is preferred that the composition is characterized by that the composition is used for formation of an interlayer insulating film of a device.

　With regard to such composition, it is preferred that the interlayer insulating film is formed of at least one portion of the composition.

　A polymer relating to an aspect of the present invention includes: a third moiety capable of being converted into a fourth moiety capable of interacting with a substance; and a fifth moiety which is to react with a chemical species.

　With regard to such polymer, it is preferred that the third moiety is converted into the fourth moiety by reacting with the chemical species.

　A composition relating to an aspect of the present invention includes any one of the aforementioned reagents; and any one of the aforementioned substances.

　A method for manufacturing a device relating to an aspect of the present invention is characterized by that the method being carried out by using the aforementioned composition.

　A method for manufacturing a device relating to an aspect of the present invention includes: applying a liquid containing any one of the aforementioned compositions to a member such that a coating film including the composition is formed on the member; and exposing the coating film to at least one of a first electromagnetic ray and a first particle ray such that a first portion of the coating film is exposed to the at least one of the first electromagnetic ray and the first particle ray while a second portion of the coating film is not exposed to the at least one of the first electromagnetic ray and the first particle ray.

　With regard to such method, it is preferred that the method further includes: removing the fist portion.

　With regard to such method, it is preferred that the method further includes: etching the member such that a third portion of the member on which the first portion has been present is etched.

　With regard to such method, it is preferred that the electromagnetic ray is a light of a wavelength ranges from 300 nm to 400 nm.

　With regard to such method, it is preferred that a contact hole is formed by the removing of the first portion.

　With regard to such method, it is preferred that the method further includes: forming an active layer before the applying of the liquid containing the composition is carried out; and connecting the active layer to an electrode by disposing a conductive material in the contact hole.

　A method for manufacturing a device relating to an aspect of the present invention is characterized by that the method being carried out by using any one of the aforementioned compositions.

　A method for manufacturing a device relating to an aspect of the present invention includes: applying a liquid containing any one of the aforementioned compositions to a member such that a coating film including such composition is formed on the member; and exposing the coating film to at least one of the first electromagnetic ray and the first particle ray such that a first portion of the coating film is exposed to the at least one of the first electromagnetic ray and the first particle ray while a second portion of the coating film is not exposed to the at least one of the first electromagnetic ray and the first particle ray.

　With regard to such method, it is preferred that such method further includes: removing the first portion.

　With regard to such method, it is preferred that such method further includes: etching the member such that a third portion of the member on which the first portion has been present is etched.

　With regard to such method, it is preferred that the first electromagnetic ray is a light of a wavelength ranges from 300 nm to 400 nm.

　With regard to such method, it is preferred that the method further includes: forming an active layer before the applying of the liquid containing the composition is carried out; and connecting the active layer to an electrode by disposing a conductive material at least in the contact hole.

　With regard to such method, it is preferred that the compounder is not excited by the exposing of the coating film.

　With regard to such method, it is preferred that the compounder does not absorb the first electromagnetic ray.

　With regard to such composition, it is preferred that the compounder does not absorb the first electromagnetic ray.

　With regard to such composition, it is preferred that the compounder is not excited by the first electromagnetic ray.

　A compounder that assists generation of a chemical species such as acid and a composition are disclosed in the present invention. Typically, such compounder assists the generation of Broensted acid or Broensted base from a precursor. Furthermore, such compounder can　be applied to enhancement of the generation of Lewis acid or Lewis base.

　Typically, such compounder in its ground state or excited state donates energy or an electron to a precursor or accepts energy or an electron from a precursor to form a reactive intermediate or an excited state of the precursor which can easily generate a chemical species. Such compounder can have existed in unchanged form until such compounder interacts or reacts with the precursor. Alternatively, such compounder can be generated from a reagent in situ before such compounder interacts or reacts with the precursor. In that case, such compounder can be generated in situ by a reaction of such reagent or an intermediate generated from such reagent with a chemical species. Alternatively, such compounder can be generated by a unimolecular reaction of such reagent. It is preferred that such compounder exhibits longer cutoff wavelength in its absorption spectrum than such reagent.

　A compounder relating to an aspect of the present invention has following characteristics: the compounder absorbs a light of which wavelength is equal to or longer than 220 nm; and the compounder is capable of sensitizing a precursor to generate a chemical species from the precursor.

　A reagent relating to an aspect of the present invention is capable of generating the compounder mentioned above. Typically, supply of energy to a film containing such reagent generates the compounder from the reagent. The compounder has a longer conjugation length than the reagent.

　A reagent relating to an aspect of the present invention has at least two pi-electron systems of the reagent. A compounder having at least two pi-electron systems is generated from such reagent. An electronic interaction between the at least two pi-electron systems in such compounder is stronger than an electronic interaction between the at least two pi-electron systems in the reagent. Such reagent generates the compounder through processes triggered by supplying energy to the film.

　Typical examples for such compounder are diaryl ketones such as alkoxy (or aryloxy) benzophenone, arylalkyl ketones and carbazoles. For example, a composition relating to an aspect of the present invention contains at least one of such compounder and reagent which is to form such compounder, a precursor which is to form a chemical species, and a compound that is to react with the chemical species. Such composition can be applied as a photoresist to fabrication of a device such as semiconductor device and electro-optical device. A typical example of such precursor is PAG while a typical example of such compound is a polymer containing a substituent which is acid-dissociable. Typically, a set of processes for fabricating devices includes a step in which the composition is applied to a member to form a coating film and a step in which the coating film is exposed to a light of which wavelength is longer than 200 nm.

　In case that such compounder is used as a constituent of a photoresist composition which can be applied to interlayer insulating films of display device such as LCD and OLED, it is preferred that such compounder has very low absorption coefficient at wavelengths equal to or longer than 400 nm since the interlayer insulating films of such display device transmits visible lights or lights having wavelengths longer than 400 nm. It is more preferred that such compounder exhibits little absorption at wavelengths equal to or longer than 400 nm.

　A composition relating to an aspect of the present invention contains a precursor which is to generate a chemical species and at least one of such compounder and such reagent mentioned above. Typical examples of such reagent have a shorter cutoff wavelength than such compounder formed from such reagent. Even if a coating film formed by such composition is thick, a light penetrates deeply into the coating film and such compounder can be generated even in the depths of the coating film.

　Typically, such precursor is a PAG. The composition can further contain a compound capable of reacting with the chemical species. Such composition can be used as a photoresist for formation of an interlayer insulating film of a device or constituent material for at least one portion of an interlayer insulating film of a device.

　A polymer relating to an aspect of the present invention includes a first moiety capable of acting as a photosensitizing moiety　and　a second moiety which is to react with a chemical species.　Such polymer may further include a third moiety which is to generate the chemical species.

　A method for manufacturing a device relating to an aspect of the present invention is carried out by using such composition or such polymer mentioned above. The composition may contain at least one of such compounders mentioned above and such reagents.

　A method for manufacturing a device relating an aspect of the present invention includes the following steps: a first of application of a liquid containing the composition mentioned above to a member such that a coating film including the composition is formed on the member; a second step of an irradiation of the coating film with at least one of a electromagnetic ray and a particle ray such that a first portion of the coating film is irradiated with the at least one of the electromagnetic ray and the particle ray while a second portion of the coating film is not irradiated with the at least one of the electromagnetic ray and the particle ray; and a third step of removal of the fist portion.

　Such method can further include a step of etching of the member such that a third portion of the member on which the first portion has been present is etched.

　In such method, a contact hole can be formed by the removal of the first portion. Such method can further include a step of formation of an active layer. The active layer can be connected to an electrode such as a pixel electrode by disposing a conductive material at least in the contact hole.

　 In such method, a light of a wavelength ranges from 350 nm to 400 nm can be used as the electromagnetic ray used for such method.

　An agent relating to an aspect of the present invention is characterized by that the agent suppresses growth of an absorption band during an exposure of at least one of a composition including the agent, a solution of the composition and a film formed of the composition to at least one of a light and a particle ray.

　With regard to the agent, it is preferred that the absorption band is at a wavelength equal to or longer than 400 nm.

　An agent relating to an aspect of the present invention is characterized by that the agent is capable of quenching a reactive intermediate generated during an exposure of at least one of a composition including the agent, a solution of the composition and a film formed of the composition to at least one of a light and a particle ray.

　With regard to the agent, it is preferred that the reactive intermediate is a radical.

　With regard to the agent, it is preferred that the agent does not quench acid.

　With regard to the agent, it is preferred that the agent does not absorb a light equal to or longer than 400 nm.

　A composition relating to an aspect of the present invention includes any one of the above agent; and a substance which is capable of generating a chemical species.

　With regard to such composition, it is preferred that the chemical species is generated from the substance by the exposure of the at least one of the composition including the agent, the solution and the film to the at least one of the light and the particle ray.

　With regard to such composition, it is preferred that the substance is a photoacid generator.

　With regard to such composition, it is preferred that the composition further includes a compounder which is capable of enhancing a generation of the chemical species from the substance.

　With regard to such composition, it is preferred that the composition further includes a regent which is capable of generating a compounder which is capable of enhancing a generation of the chemical species from the substance.

　With regard to such composition, it is preferred that the compounder is excited by the at least one of the light and the particle ray.

　With regard to such composition, it is preferred that the compounder in its excited state donates an electron or energy to the substance.

　With regard to such composition, it is preferred that the compounder in its excited state accepts an electron or energy from the substance.

　With regard to such composition, it is preferred that the compounder does not absorb a light of which wavelength is longer than 400 nm.

　A composition relating to an aspect of the present invention includes: a substance; and a reagent.

　Such reagent may be converted into a compounder. Typically, such compounder is formed by deprotection reaction of such reagent.

　With regard to such composition, it is preferred that the molar ratio of such reagent to such substance is in a range from 0.3 to 5.0. It is more preferred that the molar ratio of such reagent to such substance is in range from 0.5 to 2.0.

　Typical examples of such substance are photoacid generator, photobase generator and radical initiator.

　With regard to such composition, such composition may contain such compounder instead of such reagent.

　With regard to such composition, it is preferred that the substance is capable of donating an energy or an electron to a compounder converted from the reagent or accepting an energy or an electron from the compounder by an exposure of the composition to a first electromagnetic ray and a first particle ray to enhance a formation of a chemical species from at least one of the substance and the compounder; and a ratio of an absorbance of the substance at 365 nm (“Ab365”) to an absorbance of the substance at 400 nm (“Ab400”) when measured in a solution is equal to or greater than 20.

　With regard to such composition, it is preferred that the ratio of the absorbance of the substance at 365 nm (“Ab365”) to the absorbance of the substance at 400 nm (“Ab400”) when measured in a solution is equal to or greater than 50.

　With regard to such composition it is preferred that the ratio of the absorbance of the substance at 365 nm (“Ab365”) to the absorbance at 400 nm (“Ab400”) when measured in a film is equal to or greater than 100.

　With regard to such composition it is preferred that the chemical species is at least one of acid and base.

　With regard to such composition, it is preferred that: the substance has a following characteristic: and a molar absorption coefficient of the substance at 400 nm when measured in a solution is equal to or lower than 200.

　With regard to such composition, it is preferred that the substance is capable of accepting the energy or the electron from the compounder to enhance the chemical species from the substance.

　With regard to such composition, it is preferred that a conjugation length of the compounder is longer than a conjugation length of the reagent.

　With regard to such composition it is preferred that: the reagent has at least two pi-electron systems; the compounder has at least two pi-electron systems; and an electronic interaction between the at least two pi-electron systems in the compounder is stronger than an electronic interaction between the at least two pi-electron systems in the reagent.

　With regard to such composition it is preferred that the substance is a photoacid generator (PAG).

　With regard to such composition it is preferred that the composition further includes a compound.

　With regard to such composition it is preferred that the compound reacts with the chemical species.

　With regard to such composition it is preferred that the composition being characterized by that the composition is used for formation of an interlayer insulating film of a device.

　With regard to such composition, it is preferred that the composition further includes an inhibitor which suppresses degradation of an optical transmittance.

　Such inhibitor may suppress coloring of a film formed of such composition.

　Such inhibitor may quench a reactive intermediate such as radical formed by photoirradiation.

　With regard to such composition, it is preferred that the molar ratio of such inhibitor to such compounder or such reagent is in a range from 1.0 to 20.0. It is more preferred that the molar ratio of such inhibitor to such compounder or such reagent is in a range from 5.0 to 10.0.

　With regard to such composition it is preferred that the inhibitor suppresses the transmittance at a wavelength equal to or longer than 400 nm.

　A method relating to an aspect of the present invention includes: applying a liquid containing any one of the compositions to a member such that a coating film including the composition is formed on the member; and exposing the coating film to at least one of a first electromagnetic ray and a first particle ray such that a first portion of the coating film is exposed to the at least one of the first electromagnetic ray and the first particle ray while a second portion of the coating film is not exposed to the at least one of the first electromagnetic ray and the first particle ray.

　With regard to such method, it is preferred that the method further includes: removing the first portion.

　With regard to such method, it is preferred that the exposing of the coating film is carried out such that compounder does not absorb a light of which wavelength is longer than 400 nm.

　In the drawings, which illustrate what is currently considered to be the best mode for carrying out several aspects of the present invention:

[Fig.1]　FIG. 1 shows temporal changes of absorption spectra of films formed compositions relating to an aspect of the present invention.

[Fig.2]　FIG. 2 shows fabrication processes of a device such as integrated circuit (IC) using a photoresist relating to an aspect of the present invention.

[Figs.3A-3D]　FIGs. 3A to 3D show fabrication processes of a display device such as organic electroluminescent device (OLED) using a photoresist relating to an aspect of the present invention.

DETAILED DESCRIPTION

Experimental Procedures:
　Synthesis of 2,2’,4,4’-tetramethoxybenzophenone (Compounder A)

　2.00 g of 2, 2’, 4, 4’-tetrahydroxybenzophenone 3.68g of dimethyl sulfate and 4.03 g of potassium carbonate are dissolved in 12.0 g of acetone. The mixture is stirred at reflux temperature for 8 hours. Since then, the mixture is cooled to 25 degrees Celsius and it is further stirred 10minutes after addition of 60.0g of water and a deposit is filtrated. Then the deposit is dissolved in 20.0g ethyl acetate and the organic phase is washed with water. Thereafter, ethyl acetate is distilled away, and the resultant is purified by recrystallization using 15.0 g of ethanol. Thereby 1.40 g of 2, 2’, 4, 4’-tetramethoxybenzophenone is obtained.

　Synthesis of bis-(2,4-dimethoxyphenyl)-dimethoxymethane

　7.0 g of 2,2’,4,4’-tetramethoxybenzophenone, is dissolved in 27.8 g of thionyl chloride. The mixture is stirred at reflux temperature for 5 hours. Since then, thionyl chloride is distilled away and the resultant is dissolved in 15 g of toluene. Then the prepared solution is added dropwise over 1h to 30.1 g of methanol solution containing 5.0 g of sodium methoxide at 5 degrees Celsius. After the addition is completed, the mixture is warmed up to 25 degrees Celsius with stirring for 2 hours. Then, the mixture is further stirred after an addition of 50 g of pure water. Then methanol is distilled away, and the resultant is extracted by 35 g of toluene and the organic phase is washed with water. Thereafter, toluene is distilled away. Thereby　3.87 g of crude bis-(2,4-dimethoxyphenyl)-dimethoxymethane is obtained as an oil.

　Synthesis of 2,2-bis-(2,4-dimethoxyphenyl)-1,3-dioxolane (Reagent A)

　3.8 g of crude bis-(2,4-dimethoxyphenyl)-dimethoxymethane, 0.03 g of compher sulfonic acid and 2.03 g of ethyleneglycol are dissolved in 5.7 g of tetrahydrofran. The mixture is stirred at 25 degrees Celsius for 72 hours. Since then, the organic solvents are distilled away and the resultant is dissolved in 11 g of dichloromethane. Then, the mixture is further stirred after addition of 5 % aqueous solution of sodium carbonate and the organic phase is washed with 5 % aqueous solution of sodium carbonate and water. Thereafter, dichloromethane is distilled away, and the residue is purified by silica gel column chromatography (ethyl acetate: hexane: triethylamine = 10:90:0.01). Thereby 2.5 g of 2,2-bis-(2,4-dimethoxyphenyl)-1,3-dioxolane (Reagent A) is obtained.

　Synthesis of 2,4-dimethoxy-4’-methoxy-benzophenone (Compounder B)
Synthesis of 2,4-dimethoxy-4’-methoxy-benzophenone as a target substance is synthesized and obtained according to the synthesis of Compounder A mentioned above, except for using 2,4-dimethoxy-4’-hydroxybenzophenone instead of 2,2’,4,4’-tetrahydroxybenzophenone for the synthesis of Compounder A.

　Synthesis of 2,4-dimethoxy-4’-(2-vinyloxy-ethoxy)-benzophenone

　2.00 g of 2,4-dimethoxy-4’-hydroxybenzophenone, 2.48g of 2-chloroethyl vinyl ether and 3.21g of potassium carbonate are dissolved in 12.0 g of dimethyl formamide. The mixture is stirred at 110 degrees Celsius for 15 hours. Since then, the mixture is cooled to 25 degrees Celsius and it is further stirred after addition of 60.0 g of water. Then extracted with 24.0 g toluene and the organic phase is washed with water. Thereafter, toluene is distilled away. Thereby 3.59 g of 2,4-dimethoxy-4’-(2-vinyloxy-ethoxy)-benzophenone is obtained.

　Synthesis of 2,4-dimethoxy-4’-(2-hydroxy-ethoxy)-benzophenone

　3.59 g of 2,4-dimethoxy-4’-(2-vinyloxy-ethoxy)-benzophenone, 0.28 g of pyridinium p-toluenesulfonate and 2.1 g of water are dissolved in 18.0 g of acetone. The mixture is stirred at 35 degrees Celsius for 12 hours. Since then, the mixture is further stirred after addition of 3 % aqueous solution of sodium carbonate. Then extracted with 28.0 g ethyl acetate and the organic phase is washed with water. Thereafter, ethyl acetate is distilled away. Thereby 3.04 g of 2,4-dimethoxy-4’-(2-hydroxy-ethoxy)-benzophenone is obtained.

　Synthesis of 2, 4-dimethoxy-4’-(2-methacryloxy-ethyl)-benzophenone (Compounder C).

　3.0 g of 2, 4-dimethoxy-4’-(2-hydroxy-ethoxy)-benzophenone and 1.7 g of methacrylic anhydride are dissolved in 21 g of tetrahydrofuran. 1.2 g of triethylamine dissolved in 3.6g of tetrahydrofuran is added dropwise to the tetrahydrofuran solution containing 2, 4-dimethoxy-4’-(2-hydroxy-ethoxy)-benzophenone over 10 minutes. After that the mixture is stirred at 25 degrees Celsius for 3 hours. Since then, the mixture is further stirred after addition of water. Then extracted with 30g ethyl acetate and the organic phase is washed with water. Thereafter, ethyl acetate is distilled away, and the residue is purified by silica gel column chromatography (ethyl acetate: hexane = 1:9). Thereby 2.72 g of 2, 4-dimethoxy-4’-(2-methacryloxy-ethyl)- benzophenone is obtained.

　Synthesis of 2, 4-dimethoxy-4’-(2-acetoxy-ethoxy)-benzophenone

　Synthesis of 2, 4-dimethoxy-4’-(2-acetoxy-ethoxy)-benzophenone as a target substance is synthesized and obtained according to the synthesis of Compoounder C mentioned above, except for using acetic anhydride instead of methacrylic anhydride for the synthesis of Compounder C.

　Synthesis of (2, 4-dimethoxyphenyl)-[4’-(2-hydroxy-ethoxy)-phenyl]-dimethoxymethane

　Synthesis of (2, 4-dimethoxyphenyl)-[4’-(2-hydroxy-ethoxy)-phenyl]-dimethoxymethane as a target substance is synthesized and obtained according to the synthesis of bis-(2,4-dimethoxyphenyl)-dimethoxymethane mentioned above , except for using 2, 4-dimethoxy-4’-(2-acetoxy-ethyl)-benzophenone instead of 2,2’,4,4’-tetramethoxybenzophenone for the synthesis of bis-(2,4-dimethoxyphenyl)-dimethoxymethane.

　Synthesis of 2-(2, 4-dimethoxyphenyl)-2-[4’-(2-hydroxy-ethoxy)-phenyl]-1,3-dioxolane

　Synthesis of 2-(2, 4-dimethoxyphenyl)-2-[4’-(2-hydroxy-ethoxy)-phenyl]-1,3-dioxolane as a target substance is synthesized and obtained according to the synthesis of the Reagent A mentioned above, except for using (2, 4-dimethoxyphenyl)-[4’-(2-hydroxy-ethoxy)-phenyl]-dimethoxymethane instead of bis-(2,4-dimethoxyphenyl)-dimethoxymethane for the synthesis of Reagent A.

　2-(2, 4-dimethoxyphenyl)-2-[4’-(2-methacyloxy-ethoxy)-phenyl]-1,3-dioxolane (Reagent B).

　Synthesis of 2-(2, 4-dimethoxyphenyl)-2-[4’-(2-methacyloxy-ethoxy)-phenyl]-1,3-dioxolane as a target substance is synthesized and obtained according to the synthesis of the Compounder C mentioned above, except for using (2, 4-dimethoxyphenyl)-[4’-(2-hydroxy-ethoxy)-phenyl]-dimethoxymethane instead of 2, 4-dimethoxy-4’-(2-hydroxy-ethoxy)-benzophenone for the synthesis of Compounder C.

　A solution containing 5.0 g of α-methacryloyloxy-γ-butylolactone, 6.03 g of 2-methyladamantane-2-methacrylate, and 4.34 g of 3-hydroxyadamantane-1-methacrylate, 0.51 g of dimethyl-2,2’-azobis(2-methylpropionate)-3-hydrocyadamantane-1-methacrylate, and 26.1 g of tetrahydrofuran is prepared. The prepared solution is added dropwise over 4 hours to 20.0 g of tetrahydrofuran placed in flask with stirring and boiling. After the addition of the prepared solution, the mixture is heated to reflux for 2 hours and cooled to room temperature. Addition of the mixture by drops to a mixed liquid containing 160 g of hexane and 18 g of tetrahydrofuran with vigorously stirring precipitates the copolymer. The copolymer is isolated by filtration. Purification of the copolymer is carried out by vacuum drying following twice washings by 70 g of hexane, and thereby 8.5 g of white powder of the copolymer is obtained.

　A solution containing 1.2 g of 4-Hydroxyphenylmethacrylate, 9.2 g of α-methacryloyloxy-γ-butylolactone, 8.0 g of 2-methyladamantane-2-methacrylate, 9.5 g of 3-hydroxyadamantane-1-methacrylate, 0.31 g of butyl mercaptane, 0.51 g of dimethyl-2,2’ -azobis(2-methylpropionate) and 32.4 g of tetrahydrofuran is prepared. The prepared solution is added dropwise over 4 hours to 11.0 g of tetrahydrofuran placed in flask with stirring and boiling under nitrogen atmosphere. After the addition of the prepared solution, the mixture is heated to reflux for 2 hours and cooled to room temperature. Addition of the mixture by drops to a mixed liquid containing 286 g of hexane and 32 g of tetrahydrofuran with vigorously stirring precipitates the copolymer. The copolymer is isolated by filtration. Purification of the copolymer is carried out by vacuum drying following twice washings by 100 g of hexane, and thereby 20 g of white powder of the copolymer (Resin B) is obtained.

　A solution containing 0.82 g of (2, 4-dimethoxyphenyl)-[4’-(2-methacryloxy-ethyl)-phenyl]-benzophenone, 3.0 g of α-methacryloyloxy-γ-butylolactone, 2.6 g of 2-methyladamantane-2-methacrylate, 3.1 g of 3-hydroxyadamantane-1-methacrylate, 0.20 g of butyl mercaptane, 0.51 g of dimethyl-2,2’ -azobis(2-methylpropionate) and 11.2 g of tetrahydrofuran is prepared. The prepared solution is added dropwise over 4 hours to 8.0 g of tetrahydrofuran placed in flask with stirring and boiling under nitrogen atmosphere. After the addition of the prepared solution, the mixture is heated to reflux for 2 hours and cooled to room temperature. Addition of the mixture by drops to a mixed liquid containing 110 g of hexane and 11 g of tetrahydrofuran with vigorously stirring precipitates the copolymer. The copolymer is isolated by filtration. Purification of the copolymer is carried out by vacuum drying following twice washings by 40 g of hexane, and thereby 7.1 g of white powder of the copolymer (Resin C) is obtained.

　A solution containing 0.92 g of 2-(2, 4-dimethoxyphenyl)-2-[4’-(2-methacyloxy-ethoxy)-phenyl]-1,3-dioxolane, 3.0 g of α-methacryloyloxy-γ-butylolactone, 2.6 g of 2-methyladamantane-2-methacrylate, 3.1 g of 3-hydroxyadamantane-1-methacrylate, 0.20 g of butyl mercaptane, 0.51 g of dimethyl-2,2’ -azobis(2-methylpropionate) and 11.2 g of tetrahydrofuran is prepared. The prepared solution is added dropwise over 4 hours to 8.0 g of tetrahydrofuran placed in flask with stirring and boiling under nitrogen atmosphere. After the addition of the prepared solution, the mixture is heated to reflux for 2 hours and cooled to room temperature. Addition of the mixture by drops to a mixed liquid containing 110 g of hexane and 11 g of tetrahydrofuran with vigorously stirring precipitates the copolymer. The copolymer is isolated by filtration. Purification of the copolymer is carried out by vacuum drying following twice washings by 40 g of hexane, and thereby 6.8 g of white powder of the copolymer (Resin D) is obtained.

　Preparation of samples for evaluation (the “Evaluation Samples”)

　Evaluation Samples 1-16 are prepared by dissolving 2000mg in cyclohexanone when the samples are used for sensitivity evaluation and 1000mg in cyclohexanone when the samples are used for transmittance degradation evaluation. (i) 0.032 mmol of a PAG selected from a group of consisting of phenyl dibenzothionium nonafuorobutanesulfonate (PBpS-PFBS), 4-thiophenyl-phenyl diphenylsulfonium nonafluorobutanesulfonate (PSDPS-PFBS), N-hydroxynaphtalimide trifluolomethanesulfonate (NHNI-Nf) and N-hydroxyphthalimide triafluolomethanesulfonate (NHPI-Nf), (ii) 450 mg of a resin selected from a group consisting of Resins A, B, C and D, and (iii) at least one additive selected from a group consisting of Compounders and/or Reagent A mentioned above, or (iv) 0 mmol of additive, and (v) 45 mg of a transmittance degradation inhibitor containing phenoxy group such as poly-p-hydroxystyrene (PHS) and 2, 6-di-tert-butyl-p-cresol (BHT) for Evaluation Samples.

　Table1 shows detail of compositions of Evaluation Samples 1-16.

　Evaluation of Sensitivity

　Before applying an Evaluation Sample to a Si wafer, hexamethyldisilazane (HMDS, Tokyo Chemical Industry) is spin-coated at 2000 rpm for 20 seconds on the surface of Si wafer and baked at 110 degrees Celsius for 1 min. Then, an Evaluation Sample is spin-coated on the surface Si wafers which has been treated with HMDS at 2000 rpm for 20 seconds to form a coating film. The prebake of the coating film is performed at 110 degrees Celsius for 60 seconds. Then the coating film of the Evaluation Sample is exposed to an ultraviolet (UV) light of which wavelength is 365 nm (i-line) output from an UV exposure system (HMW-661C-3 ORC manufacturing Co. LTD.). After that the UV light exposure, a post-exposure-bake (PEB) is carried out at 110 degrees Celsius for 60 seconds. The coating film is developed with NMD-3 (tetra-methyl ammonium hydroxide 2.38 %, Tokyo Ohka Kogyo) for 20 seconds at 25 degrees Celsius and rinsed with deionized water for 10 seconds. The thickness of the coating film measured using film thickness measurement tool is approximately 500 nm. Thereafter, a sensitivity (E0 sensitivity) is evaluated by measuring the dose size to form a pattern constituted by 100μm lines where the thickness of the coating film is not zero and 100μm spaces where the thickness of the coating film is zero using UV exposure system, and dose for E0 sensitivity is calculated by means of a measurement of illuminance of UV source by 365nm illuminometer (USHIO UIT-150, UVD-S365).

　Evaluation of visible light transmittance degradation

　Evaluation Sample is spin-coated on the surface quartz wafers at 1500 rpm for 20 seconds to form a coating film. The prebake of the coating film is performed at 110 degrees Celsius for 5 minutes. The thickness of the coating film measured using film thickness measurement tool is approximately 5 μm. Then an Evaluation Sample is measured by ultraviolet-visible spectroscopy to evaluate the transmittance of films at 400 nm before UV light irradiation. Thereafter, the coating film of the Evaluation Sample is exposed to a UV light of which intensity is three times higher than E0 which is estimated by the sensitivity evaluation explained above. The exposure to UV light is carried out by using a light of which wavelength is 365 nm (i-line) output from an UV exposure system (HMW-661C-3 ORC manufacturing Co. LTD.).

　After that the UV light exposure, an Evaluation Sample is measured by ultraviolet-visible spectroscopy to evaluate the transmittance of films at 400 nm.

　Dose for dose size is calculated by means of a measurement of illuminance of UV source by 365nm illuminometer (USHIO UIT-150, UVD-S365) and transmittance of 20μm film thickness is calculated based on the transmittance for the film having thickness of 5μm in this transmittance evaluation.

　Table 2 shows the dose sizes corresponding to E0 sensitivities and transmittances measured for the Evaluation Samples 1 to 16. Formation of acid by an irradiation by the i-line UV exposure is not observed for Evaluation Samples 1.

　The E0 sensitivities of Evaluation Sample 2 containing Compounder A is higher than that of Evaluation Sample 3 of which constituents are identical with those of Evaluation Sample 2 except for Compounder B. Evaluation Sample 5 containing Compounder A is higher than that of Evaluation Sample 7 of which constituents are identical with those of Evaluation Sample 5 except for Compounder B. This indicates that Compounder A is higher electron-donating ability than Compounder B.

　Evaluation Sample 15 contains Resin C, PBpS-PFBS, PHS and cyclohexaonone while Evaluation Sample 7 contains Resin A, PBpS-PFBS, Compounder B, PHS and cyclohexanone. The constituents of Evaluation Sample 15 are identical with those of Evaluation Sample 7 except for Resin C and Compounder B. Resin C has C-1 moieties which can function as photosensitizers instead of Compounder B, which is considered to have electron-donating ability similar to C-1 moieties. However, the sensitivity of Evaluation Sample 15 is higher than that of Evaluation Sample 7. This is considered to be due to homogeneous dispersion of the C-1 moieties acting as photosensitizers.

　Evaluation Sample 4 contains Compounder A which can act as a photosensitizer right from the start and Reagent A, which is protected by a protecting group such as dialkoxy acetal and to form a corresponding photosensitizer through reaction with acid.

　Both Reagent A and photosensitizers to be formed from Reagent A have two pi-electron systems. An electronic interaction between the two pi-electron systems of Reagent A is weaker than that of the corresponding photosensitizer. The two pi-electron systems of such photosensitizer interact mutually through pi electrons or unshared electron pair of carbonyl group of the photosensitizer. Due to such electronic interaction in the photosensitizer, such photosensitizer can absorb a longer-wavelength light.

　The same holds true for Evaluation Sample 16 because Evaluation Sample 16 contains Compounder A and Resin D having D-1 moieties which are protected by a protecting group such as dialkoxy acetal and to form corresponding photosensitizing moieties through a reaction with acid.

　The conjugation lengths of such reagent and moieties protected by protecting group are shorter than that of the corresponding photosensitizer and the photosensitizing moieties, respectively. In the photosensitizer and the photosensitizing moieties, the pi electrons are delocalized through electronic interactions of the two pi-electron systems through pi electrons or unshared electron pair of carbonyl group.

　Addition of such reagent or incorporation of such protected moieties provides a composition containing such reagent and PAG and with preservation stability and a film formed from such composition with the long-term reliability because such reagent or moieties is hard to absorb a longer-wavelength UV light due to a weaker electronic interaction between the two pi-electron systems. Such composition is especially useful for constituent material for film such as insulating film or planarizing film of a display device because suppression of formation of acid can be attained during normal operation of the display device.

　Each of Compounders D, E, F and derivatives thereof are also preferably used as a photosensitizer. Each of the Compounders have electron donating character which can function as a photosensitizer by an UV light exposure.

　FIG. 1 shows temporal changes of absorption spectra of films which are formed from Evaluation Samples 2 (a) and 6 (b) and each of which has film-thickness of 5μm. Evaluation Sample 2 contains no transmittance degradation inhibitor while Evaluation Sample 6 contains BHT as transmittance degradation inhibitor.

　The films formed both of the samples show little absorption bands at wavelengths longer than 400 nm. In contrast, a difference between the samples is observed after irradiations of the films. The remarkable growth of absorption band at wavelengths longer than 400 nm is observed for Evaluation Sample 2 while no remarkable growth of absorption band at wavelengths longer than 400 nm is observed for Evaluation Sample 6.

　A transmittance degradation inhibitor like BHT is considered to suppress remarkable growth of absorption band or maintain high transmittance by quenching a reactive intermediate such as radical generated during an exposure of a film to a light or a particle ray

　Therefore, addition of such transmittance degradation inhibitor to composition is especially effective for a constituent of a photoresist used for fabrication of an interlayer insulating film of display device such as liquid crystal device and organic electroluminescent device because such interlayer is required to pass visible lights generated during normal operation of such devices.

　Such transmittance degradation inhibitor is also useful for a constituent of an interlayer insulating film of such display device.

　Compounders A and B hardly absorb a light of which wavelength is longer than 400 nm. Each of them is useful as a constituent of an interlay insulating film as well as a constituent of photoresist used for fabrication of an interlayer insulating film of display device, since, if a substance which can acts as a photosensitizer or PAG by absorbing a visible light remains in an interlayer insulating film, acid is generated even during normal operations and deteriorates display device.

　FIG. 2 shows fabrication processes of a device such as integrated circuit (IC) using a photoresist including Reagent A and a small amount of Compounder A obtained by the processes by the above procedures.

　A silicon wafer is provided. The surface of silicon wafer is oxidized by heating the silicon wafer in the presence of oxygen gas.

　A solution of a chemically-amplified resist (CAR) composition including an Reagent A, resin, and PAG is applied to the surface of an Si wafer by spin coating to form a coating film. The coating film is prebaked.

　An irradiation of the coating film with a light of which wavelength is equal to or longer 220 nm through a mask is carried out after prebake of the Si wafer. A typical light source for the irradiation of the coating film is i-line or g-line. Initially, the PAG generates a small quantity of acid by absorbing the light directly. An encounter of reagent A with the small quantity of acid yields a deprotection reaction of Reagent A to form a photosensitizer in situ. The deprotection reaction of resin A is induced by acid generated by photoreaction of the photoacid generator and assistance by the photosensitizer formed in situ.

　The conjugation length of the photosensitizer is longer than the conjugation length of the reagent. The reagent has at least two pi-electron systems. By formation of multiple bond through the deprotection reaction of the reagent, the electronic interaction between the at least two pi-electron systems in the photosensitizer is stronger than the electronic interaction between the at least two pi-electron systems in the reagent.

　The coating film and the silicon wafer are exposed to the light. After that, the remaining film is removed.

　An electronic device such as integrated circuit is fabricated utilizing the processes shown in FIG. 2. The deterioration of the device due to the irradiation with a light is suppressed compared to existing photoresists since times for irradiation of the coating film can be shortened.

　FIGs. 3A to 3D show fabrication processes for active matrix-type organic electroluminescent device.

　(a) Underlayer 2 is formed on a Substrate 1 such as glass substrate, quartz substrate and plastic substrate. Semiconductor film 4 which is formed by patterning is formed on Underlayer 2. Typically, Semiconductor film 4 is made of low-temperature polysilicon. Amorphous silicon or metal oxide can also be used as material for Semiconductor film 4. Gate insulating film 3 is formed such that Gate insulating film 3 covers Semiconductor film 4. Gate electrode 5 is formed over Gate insulating film 3 such that Gate electrode 5 and Semiconductor film 4 face each other across Gate insulating film 3.

　(b) Coating film 6 is disposed by spin-coating of a composition containing Resin E such that Coating film 6 covers Gate electrode 5 and Gate insulating film 3. E-1 moiety of Resin E is to react with a chemical species such as acid generated from photoacid generating moiety E-5 to form a corresponding deprotected moiety which can act as a photosensitizing moiety. In other words, such photosensitizing moiety formed in situ can interact with a moiety through electron exchange. According to circumstances, compounder which can act as photosensitizer in its own such as Compounder A and Compounder B can be contained in the composition. Resin E may further include a moiety acting as a photosensitizer in its own like C-1 in addition to E-1, E-2, E-3, E-4, E-5 and E-6.

　(c) Coating film 6 is irradiated with a light of which wavelength 365 nm through Photomask 8 after Coating film 6 is subjected to prebake treatment. Only a portion of Coating film 6 is exposed to a light passing through Opening 7.

　(d) The exposed portion of Coating film 6 by the light is removed by development to form Contact hole 10. Coating film 6 is converted into First interlayer insulating film 9 by a heat treatment carried out at a temperature higher than 150 degrees centigrade following formation of Contact hole 6.

　(e) Pixel electrode 11 which is electrically connected to Semiconductor film 4 is formed. Typically, Pixel electrode 11 is made of Indium Tin Oxide (ITO) or magnesium-silver alloy.

　(f) Coating film 12 is disposed by spin-coating process such that Coating film 12 covers Pixel electrode 11 and First interlayer insulating film 9.

　(g) Coating film 12 is irradiated with a light of which wavelength 365 nm through Photomask 14 after Coating film 12 is subjected to prebake treatment. Only a portion of Coating film 12 is exposed to a light passing through Opening 13.

　(h) The exposed portion of Coating film 12 by the light is removed by development. Coating film 12 is converted into Second interlayer insulating film 14 by a heat treatment carried out at a temperature higher than 150 degrees centigrade following removal of the exposed portion of Coating film 12.

　(i) Hole transport layer 15, Light emitting layer 16 and Electron transporting layer 17 are formed by vacuum vapor deposition via mask in this order. Common electrode 18 is formed over Electron transporting layer 17 and Second interlayer insulating film 14. Protection film 19 is formed over Common electrode 18.

Claims

A composition, comprising:
a substance; and
a reagent,
wherein:
the substance is capable of donating an energy or an electron to a compounder converted from the reagent or accepting an energy or an electron from the compounder by an exposure of the composition to a first electromagnetic ray and a first particle ray to enhance a formation of a chemical species from at least one of the substance and the compounder; and
a ratio of an absorbance of the substance at 365 nm (“Ab365”) to an absorbance of the substance at 400 nm (“Ab400”) when measured in a solution is equal to or greater than 20.
The composition of claim 1,
wherein the ratio of the absorbance of the substance at 365 nm (“Ab365”) to the absorbance of the substance at 400 nm (“Ab400”) when measured in a solution is equal to or greater than 50.
The composition of claim 1 or 2,
wherein the ratio of the absorbance of the substance at 365 nm (“Ab365”) to the absorbance at 400 nm (“Ab400”) when measured in a film is equal to or greater than 100.
The composition of any one of claims 1-3,
wherein the chemical species is at least one of acid and base.
The composition of any one claims 1-4,
wherein the substance has a following characteristic:
a molar absorption coefficient of the substance at 400 nm when measured in a solution is equal to or lower than 200.
The composition of any one of claims 1-5,
wherein the substance is capable of accepting the energy or the electron from the compounder to enhance the chemical species from the substance.
The composition of any one of claims 1-6,
wherein a conjugation length of the compounder is longer than a conjugation length of the reagent.
The composition of any one of claims 1-7,
wherein:
the reagent has at least two pi-electron systems;
the compounder has at least two pi-electron systems; and
an electronic interaction between the at least two pi-electron systems in the compounder is stronger than an electronic interaction between the at least two pi-electron systems in the reagent.
[Claim 9] The composition of any one of claims 1-8,
wherein the substance is a photoacid generator (PAG).
The composition of any one of claims 1-9, further comprising:
a compound.
The composition of claim 10,
wherein the compound reacts with the chemical species.
The composition of any one of claims 1-11,
wherein the composition is characterized by that the composition is used for formation of an interlayer insulating film of a device.
The composition of any one of claims 1-12, further comprising:
an inhibitor which suppresses degradation of an optical transmittance.
The composition of claim 13,
wherein the inhibitor suppresses the transmittance at a wavelength equal to or longer than 400 nm.
A method for manufacturing a device, the method comprising:
applying a liquid containing the composition of any one of claims 1-14 to a member such that a coating film including the composition is formed on the member; and
exposing the coating film to at least one of a first electromagnetic ray and a first particle ray such that a first portion of the coating film is exposed to the at least one of the first electromagnetic ray and the first particle ray while a second portion of the coating film is not exposed to the at least one of the first electromagnetic ray and the first particle ray.
The method of claim 15, further comprising:
removing the first portion.
The method of claim 15 or 16, further comprising:
etching the member such that a third portion of the member on which the first portion has been present is etched.
The method of any one of claims 15-17,
wherein the first electromagnetic ray is a light of a wavelength ranges from 300 nm to 400 nm.
The method of any one of claims 15-18, further comprising:
forming an active layer before the applying of the liquid containing the composition is carried out; and
connecting the active layer to an electrode by disposing a conductive material at least in the contact hole.
The method of any one of claims 15-19,
wherein the exposing of the coating film is carried out such that compounder does not absorb a light of which wavelength is longer than 400 nm.