CN113200858A - Synthesis based on triptycene derivative monomolecular resin, positive photoresist and application of positive photoresist in photoetching - Google Patents

Synthesis based on triptycene derivative monomolecular resin, positive photoresist and application of positive photoresist in photoetching Download PDF

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CN113200858A
CN113200858A CN202010049066.5A CN202010049066A CN113200858A CN 113200858 A CN113200858 A CN 113200858A CN 202010049066 A CN202010049066 A CN 202010049066A CN 113200858 A CN113200858 A CN 113200858A
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李嫕
胡盛文
陈金平
于天君
曾毅
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Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention provides a novel monomolecular resin based on triptycene derivatives, and a preparation method and application thereof. The resin has the characteristics of high glass transition temperature, good stability, small and single molecular size and the like, and can be widely applied to the field of photoetching, in particular to application in positive photoresist. The positive photoetching film or the positive photoresist composition prepared by the invention has better advantages in electron beam lithography and extreme ultraviolet lithography. The triptycene derivative disclosed by the invention is simple in synthetic process, convenient in separation and purification of a reaction intermediate and a final product, suitable for industrial production and wide in application prospect.

Description

Synthesis based on triptycene derivative monomolecular resin, positive photoresist and application of positive photoresist in photoetching
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a triptycene derivative monomolecular resin-based synthesis and positive photoresist and application thereof in photoetching.
Background
Photoresists, also known as photoresists, are etch-resistant thin film materials whose solubility changes upon irradiation or radiation by light sources such as ultraviolet light, excimer laser, electron beam, ion beam, or x-ray, and are widely used in microfabrication of integrated circuits and semiconductor discrete devices. The photoresist is used as an etching barrier layer, and a required fine pattern can be transferred to a substrate to be processed from the mask plate, so that the pattern transfer is realized. To achieve higher precision pattern transfer, the exposure wavelength of the photoresist is shifted from the broad spectrum ultraviolet in the direction of g-line (436nm) → i-line (365 nm) → KrF (248nm) → ArF (193nm) → EUV (13.5 nm). The current research focus is the extreme ultraviolet lithography technology, the exposure wavelength used by the technology is 13.5nm, the high-resolution lithography below 10nm can be achieved, and the corresponding photoresist has more rigorous requirements. The traditional photoresist main body material usually adopts polymer resin with the molecular weight of 5000-15000 daltons, and the polymer material has great influence on the edge roughness or line width roughness of an exposure pattern due to large molecular size, wide molecular weight distribution, molecular chain winding and the like, and cannot meet the requirement of more fine lithography.
The monomolecular resin is a small molecular compound with relatively low molecular mass, presents a stable amorphous state and has a glass transition temperature. Compared with the traditional polymer photoresist, the molecule has monodispersity and small gyration radius, simultaneously has the thermal stability and film forming property of the polymer, and is a novel photoresist main body material. The monomolecular resin designed by taking triptycene as the core can fully utilize the advantages of the structure, such as high glass transition temperature, good thermal stability and the like. Meanwhile, the spatial solid geometrical skeleton of the rigid structure can effectively inhibit the crystallinity of compound molecules and better form a film. The monomolecular resin is used as a main material of a positive photoresist, can be applied to photoetching, and is particularly suitable for high-resolution extreme ultraviolet and electron beam photoetching.
Disclosure of Invention
In order to improve the problems, the invention provides a triptycene derivative shown as a formula (A):
Figure BDA0002370472000000021
wherein R is1、R2、R3、R4、R5、R6Identical or different, independently of one another, from hydrogen or from 1 to 5RaSubstituted aryl, heteroaryl; r1And R2Group R3And R4Group R5And R6In three groups of substituents, each group has at least one substituent of 1-5RaSubstituted aryl, heteroaryl; each RaIdentical OR different, independently of one another, from hydrogen, OR-ORbSaid R isbIs an acid-sensitive group, R in the molecule of the formula (A)aAt least one is-ORb。
The acid-sensitive group refers to a group which can react under acidic conditions, thereby being removed from the main body.
In one embodiment of the invention, the acid-sensitive group Rbis-CR1-O-R1、-CO-O-R1、 -CH2-CO-O-R1、
Figure BDA0002370472000000022
Wherein R is1Identical or different, independently of one another, from the group unsubstituted or optionally substituted by one, two or more Rs2Substituted with the following groups: c1-15Alkyl radical, C3-20A cycloalkyl group;
Figure BDA0002370472000000023
optionally by one, two or more Rs on the ring2Substitution;
m is any integer of 1 to 4,
Figure BDA0002370472000000024
represents a bond of the group to the host structure;
Rs2identical or different, independently of one another, from the following groups: NO2Halogen, C1-15Alkyl radical, C1-15Alkoxy radical, C3-20A cycloalkyl group.
In one embodiment, said R is1Is a quilt C1-6Alkyl substituted or unsubstituted the following groups: c1-6Alkyl radical, C3-8Monocyclic cycloalkyl, C7-12Bridged cycloalkyl.
According to an embodiment of the invention, R1、R2、R3、R4、R5、R6The same or different, independently from each other, are selected from hydrogen or substituted by 1,2 or 3RaSubstituted C6-10Aryl, heteroaryl; r1And R2Group R3And R4Group R5And R6In three groups of substituents, each group has at least one substituent substituted by 1,2, or 3RaSubstituted C6-10Aryl, heteroaryl; each RaIdentical OR different, independently of one another, from hydrogen, OR-ORbR in each molecule of formula (A)aAt least one is-ORb；
According to an embodiment of the invention, R1、R2、R3、R4、R5、R6Identical or different, independently of one another, from hydrogen or substituted by 1,2 or 3RaSubstituted phenyl; r1And R2Group R3And R4Group R5And R6In three groups of substituents, each group has at least one substituent being substituted by 1,2 or 3RaSubstituted phenyl; each RaIdentical OR different, independently of one another, from hydrogen OR-ORbR in each molecule of formula (A)aAt least one is-ORb；
According to an embodiment of the invention, R1、R2、R3、R4、R5、R6Identical or different, independently of one another, from hydrogen or
Figure BDA0002370472000000031
And R is1And R2Group R3And R4Group R5And R6In three groups of substituents, each group has at least one substituent of
Figure BDA0002370472000000032
Each RaIdentical OR different, independently of one another, from hydrogen OR-ORbR in each molecule of formula (A)aAt least one is-ORb；
Preferably, the group RbSelected from the group consisting of:
Figure BDA0002370472000000033
wherein the content of the first and second substances,
Figure BDA0002370472000000034
represents a connecting bond;
preferably, the present invention also provides compounds represented by formula (I), formula (II) and formula (III):
Figure BDA0002370472000000041
wherein: ra1、Ra2、Ra3And the above-mentioned RaThe definitions are the same;
according to an embodiment of the invention, the triptycene derivative is selected from the following structures:
Figure BDA0002370472000000042
wherein Boc represents
Figure BDA0002370472000000043
Substituent, AD represents
Figure BDA0002370472000000044
BH represents
Figure BDA0002370472000000045
And (4) a substituent.
The invention also provides a preparation method of the triptycene derivative shown in the formula (A), which comprises the following steps:
1) carrying out Suzuki coupling reaction on the compound a and a compound b to obtain a compound c, wherein the compound b is selected from 1-5Ra' substituted arylboronic acids, arylboronic acid esters, heteroarylboronic acids or heteroarylboronic acid esters, such as: 3, 4-dimethoxyphenylboronic acid, 4-methoxyphenylboronic acid, 3, 5-dimethoxyphenylboronic acid; ra' selected from C1-12Alkoxy or aryl radicals C1-6Alkoxy, such as methoxy, ethoxy, benzyloxy;
Figure BDA0002370472000000046
wherein R is1'、R2'、R3'、R4'、R5'、R6' same or different, independently from each other, are selected from hydrogen, fluorine, chlorine, bromine or iodine and are not simultaneously hydrogen;
R1”、R2”、R3”、R4”、R5”、R6"identical or different, independently of one another, from hydrogen or substituted by 1 to 5Ra' substituted aryl or heteroaryl, and not both hydrogen; ra' selected from C1-12Alkoxy or aryl radicals C1-6Alkoxy, such as methoxy, ethoxy, benzyloxy;
2) reacting the compound c with a reducing agent to obtain a compound d;
Figure BDA0002370472000000051
wherein R is1”'、R2”'、R3”'、R4”'、R5”'、R6"' are the same or different and are independently selected from hydrogen or aryl or heteroaryl substituted with 1,2 or 3 OH, and are not simultaneously hydrogen;
3) reacting compound d with compound RbReacting L to obtain the triptycene derivative shown as the formula (A), wherein L is a leaving group or L and RbForm a group containing RbAcid anhydride of RbAs has been described above, in the above-mentioned,
Figure BDA0002370472000000052
wherein R is1、R2、R3、R4、R5、R6As defined above.
According to the invention, the compound RbL is, for example, di-tert-butyl dicarbonate, adamantane- α -chloroacetate, norbornyl chloroacetate.
The reducing agent is selected, for example, from boron tribromide or boron trichloride.
The invention also provides the use of the compound (A) for a host material of a photoresist.
The invention also provides a positive photoresist composition, which comprises the triptycene derivative shown as the formula (A), a photoacid generator and a photoresist solvent;
in the invention, the weight of the triptycene derivative shown in the formula (A) is 1-10 wt% of the total weight of the positive photoresist composition, the weight of the photoacid generator is 0.01-1 wt%, and the balance is a photoresist solvent.
In the invention, the photoacid generator is selected from ionic or non-ionic photoacid generators, and comprises one or more of triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorobutylsulfonate, bis (4-tert-butylphenyl) iodonium p-toluenesulfonate and N-hydroxynaphthalimide trifluoromethanesulfonate.
In the invention, the photoresist solvent is selected from one or more of propylene glycol monomethyl ether acetate, ethyl lactate, ethylene glycol monomethyl ether or cyclohexanone.
The invention also provides a positive photoresist film comprising the compound represented by the formula (A).
The invention also provides a preparation method of the positive photoresist film, which comprises the step of applying the positive photoresist composition on a substrate to form a film. The application method is a spin coating method.
In one embodiment, the substrate may be a silicon wafer.
The invention also provides the positive photoresist composition and the application of the positive photoresist film in photoetching.
According to the present invention, the lithography is 248nm lithography, 193nm lithography, extreme ultraviolet lithography (EUV), nanoimprint lithography, or electron beam lithography, and particularly, the positive photoresist composition, the positive photoresist coating, is used for electron beam lithography and extreme ultraviolet lithography.
Advantageous effects
The invention provides a series of novel monomolecular resins based on triptycene derivatives represented by formula (A). It has the characteristics of high glass transition temperature (more than 100 ℃) and good thermal stability. The monomolecular resin has a determined molecular structure, is small and single in molecular size, and well meets the requirement of photoetching.
The invention fully utilizes the characteristic that the triptycene has a spatial solid geometric framework, and can effectively inhibit the crystallization of molecules, so that the photoresist taking the monomolecular resin as a main material is easy to form a film.
The synthesis process of the monomolecular resin is simple, the reaction intermediate and the final product can be separated from the system through recrystallization or precipitation, and the method is suitable for industrial production.
Definition and description of terms
Unless defined otherwise, all technical and scientific terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the claimed subject matter belongs.
The term "alkyl" is understood to mean having from 1 to 12A straight or branched chain saturated monovalent hydrocarbon group of carbon atoms. For example, "C1-6Alkyl "denotes straight and branched chain alkyl groups having 1,2, 3,4, 5, or 6 carbon atoms. The alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a 2-methylbutyl group, a 1-ethylpropyl group, a 1, 2-dimethylpropyl group, a neopentyl group, a 1, 1-dimethylpropyl group, a 4-methylpentyl group, a 3-methylpentyl group, a 2-ethylbutyl group, a 1-ethylbutyl group, a 3, 3-dimethylbutyl group, a 2, 2-dimethylbutyl group, a 1, 1-dimethylbutyl group, a 2, 3-dimethylbutyl group, a 1, 3-dimethylbutyl group or a 1, 2-dimethylbutyl group, or the like, or isomers thereof.
The term "alkoxy" is to be understood as meaning-O-C1-12Alkyl radical, wherein C1-12Alkyl groups have the above definitions.
The term "cycloalkyl" is understood to mean a saturated monovalent monocyclic, bicyclic or polycyclic hydrocarbon ring (also referred to as fused ring hydrocarbon ring) having 3 to 20, preferably 3 to 10, carbon atoms. Bicyclic or polycyclic cycloalkyl groups include fused cycloalkyl, bridged cycloalkyl, spirocycloalkyl; the fused ring refers to a fused ring structure formed by two or more ring structures sharing two adjacent ring atoms with each other (i.e., sharing one bond). The bridged ring refers to a condensed ring structure formed by two or more than two ring structures sharing two non-adjacent ring atoms. The spiro ring refers to a fused ring structure formed by two or more cyclic structures sharing one ring atom with each other. For example, the cycloalkyl group may be C3-8Monocyclic cycloalkyl, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or is C7-12And cyclic cycloalkyl groups such as decalin ring; or may be C7-12Bridged cycloalkyl radicals, e.g. norbornane, adamantane, bicyclo [2,2 ]]Octane.
The term "aryl" is to be understood as meaning a mono-, bi-or tricyclic hydrocarbon ring of monovalent or partial aromaticity having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, preferably "C6-8Aryl ". The term "C6-8Aryl "is understood to mean preferably having 6,7 or 8Monocyclic, bicyclic or tricyclic hydrocarbon rings of monovalent or partially aromatic character by carbon atoms ('C')6-14Aryl group "), in particular a ring having 6 carbon atoms (" C6Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C9Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C10Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C13Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C)14Aryl), such as anthracenyl. When said C is6-10When the aryl group is substituted, it may be mono-or polysubstituted. And, the substitution site thereof is not limited, and may be, for example, ortho-, para-or meta-substitution.
The term "heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: having 5 to 20 ring atoms and comprising 1 to 5 heteroatoms independently selected from N, O and S, such as "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: which has 5, 6,7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and which contains 1 to 5, preferably 1 to 3 heteroatoms independently selected from N, O and S and, in addition, can be benzo-fused in each case. In particular, heteroaryl is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl and the like and their benzo derivatives, such as benzofuranyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like, and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl, and the like; or azocinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like.
Drawings
FIG. 1 is a differential scanning calorimetry trace and a thermogram of example 3(2,7, 14-tris- (3, 4-di-tert-butylcarbonatylphenyl) triptycene) according to the present invention.
FIG. 2 is a differential scanning calorimetry graph and a thermogravimetry graph of example 4(2,3,6,7,14, 15-hexa- (4-adamantylphenyl acetate) triptycene) of the present invention.
FIG. 3 is a Scanning Electron Microscope (SEM) image of EUV lithography fringes of positive photoresist film formation of the bulk material of example 3(2,7, 14-tris- (3, 4-di-tert-butylcarbonate phenyl) triptycene) of the present invention.
FIG. 4 is a Scanning Electron Microscope (SEM) image of electron beam lithography stripes of positive photoresist film formation of example 4(2,3,6,7,14, 15-hexa- (4-adamantylphenyl acetate) triptycene) host material of the present invention.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The 2,3,6,7,14, 15-hexabromotriptycene, 2,7, 14-tribromotriptycene and 2,6, 14-tribromotriptycene of the present invention can be prepared by referring to the prior documents of Nature chemistry, 2014,6, 774-. (such bromo compounds are commercially available, some methods for their preparation are also provided below)
Example 1
Preparation of 2,3,6,7,14, 15-hexabromotriptycene
Figure BDA0002370472000000091
The method comprises the following specific steps: at 500Into a mL reaction flask were added triptycene (3.0g, 11.80mmol), iron powder (0.085g, 1.52mmol) and 200mL chloroform, and the reaction was stirred at room temperature. Bromine (3.8mL, 11.80g, 73.84mmol) was added to the reaction, stirred vigorously and refluxed. After 4h of reaction, the reaction was completed, the reaction solution was cooled to room temperature, and then washed with saturated sodium sulfite solution and water, and the organic layer was spin-dried to obtain a yellow solid. Recrystallization of the yellow solid from acetone gave 5g of pure colorless crystals in 60% yield.1H NMR(400MHz,CDCl3):δ(ppm)7.62(s,6H),5.23(s,2H)。
Example 2
Preparation of 2,6, 14-tribromotriptycene and 2,7, 14-tribromotriptycene (involving nitration, reduction and bromination of triptycene)
1) Nitration of triptycenes
Figure BDA0002370472000000101
The method comprises the following specific steps: triptycene (2.5g, 10mmol) and 100mL concentrated nitric acid were added to a 250mL reaction flask, and the reaction was warmed to 75 ℃ and stirred for 24 h. When the reaction is finished, the reaction solution is cooled to room temperature, the reaction solution is dripped into 1000mL of water, and the precipitate is collected. The precipitate was separated by column chromatography to give 2,6, 14-trinitrotriptycene (2.5g, 65%) and 2,7, 14-trinitrotriptycene (0.82g, 21%) as white solids.
2,6, 14-trinitrotriptycene1H NMR(300MHz,CDCl3):δ5.82(s,1H),5.84(s,1H), 7.62-7.67(m,3H),8.03-8.07(m,3H),8.32-8.34(m,3H)；
2,7, 14-trinitrotriptycene1H NMR(300MHz,CDCl3):δ5.80(s,1H),5.84(s,1H), 7.62(d,J＝8.2Hz,3H),8.05(dd,J＝8.2,2.2Hz,3H),8.34(d,J＝2.2Hz,3H)。
2) Reduction of 2,6, 14-trinitrotriptycene
Figure BDA0002370472000000102
The method comprises the following specific steps: in a 100mL reaction flask2,6, 14-trinitrotriptycene (1.0g, 2.6mmol), 1.5mL hydrazine hydrate, Raney Ni (1.0g) and 20mL tetrahydrofuran were added and the reaction was warmed to 60 ℃ and stirred for 3 h. At the end of the reaction, the reaction mixture was cooled to room temperature, filtered, and the solvent was distilled off under reduced pressure to obtain a white solid (760mg, 99%).1H NMR(300MHz,CDCl3):δ3.47(s,6H),5.01(s,1H), 5.04(s,1H),6.21-6.26(m,3H),6.69-6.73(m,3H),7.04-7.07(m,3H)。
The reduction of the 2,7, 14-trinitrotriptycene is the same as the above, the yield is 99 percent,1H NMR(300MHz,CDCl3):δ 3.40(s,6H),4.97(s,1H),5.05(s,1H),6.23(dd,J＝7.7,2.1Hz,3H),6.70(d,J＝7.7 Hz,3H),7.03(d,J＝2.1Hz,3H)。
3) bromination of 2,6, 14-triaminotriptycene
Figure BDA0002370472000000111
The method comprises the following specific steps: 2,6, 14-triaminotriptycene (1.0g, 3.6mmol), 3mL of concentrated bromic acid and 10mL of water were added to a 100mL reaction flask, the reaction was placed in an ice-water bath, and an aqueous solution of sodium nitrite (0.8g, 12.6 mmol) was added dropwise. After the reaction was stirred for 20min, the reaction mixture was slowly added to a refluxing solution of cuprous bromide (2.2g, 15.0mmol) and hydrobromic acid (5 mL). The reaction system is stirred and refluxed for 2 hours, and is extracted by dichloromethane after being cooled, washed by water and dried by anhydrous sodium sulfate. The solvent was removed by distillation under reduced pressure, and the crude product was recrystallized from ethanol to give 1.1g of a white solid in 67% yield.1H NMR(300MHz,CDCl3):δ5.26(s, 1H),5.29(s,1H),7.12(dd,J＝7.8,1.8Hz,3H),7.20(d,J＝7.8Hz,3H),7.49(d,J＝1.8 Hz,3H)。
The bromination of 2,7, 14-triaminotriptycene is as above, the yield is 63 percent,1H NMR(300MHz,CDCl3):δ 5.25(s,1H),5.31(s,1H),7.13(dd,J)7.8,1.8Hz,3H),7.21(d,J＝7.8Hz,3H),7.49 (d,J＝1.8Hz,3H)。
example 3
A process for the preparation of 2,7, 14-tris- (3, 4-di-tert-butylcarbonate ylphenyl) triptycene, the process comprising the steps of:
1) the preparation of 2,7, 14-tri- (3, 4-dimethoxyphenyl) triptycene has the following synthetic route:
Figure BDA0002370472000000112
the method comprises the following specific steps: under the protection of high-purity nitrogen, 2,7, 14-tribromotriptycene (975.6mg,2mmol,1.0eq), tetratriphenylphosphine palladium (230mg,0.2mmol,0.1eq), 3, 4-dimethoxyphenylboronic acid (1.64g,9mmol,4.5eq) and 30mL of redistilled toluene are added into a 100mL Schlenk reaction bottle, and after stirring and dissolving, 6mL of ethanol solution and 2M Na are added into the reaction bottle2CO33mL of aqueous solution, heating the reaction solution to 60-100 ℃, refluxing for 12h, cooling to room temperature, extracting with dichloromethane/water, combining organic layers, washing the organic layers once with saturated saline solution, and drying with anhydrous sodium sulfate. And (4) carrying out suction filtration, and distilling the filtrate under reduced pressure to obtain a gray solid. The solid was dissolved with 5mL of dichloromethane, precipitated into 100mL of ethanol, filtered, and oven dried in vacuo to give 1.2g of a white solid in 91% yield.1H NMR(400MHz,CDCl3):δ(ppm)6.97-6.99(d,3H， benzene),6.80-6.82(d,3H，benzene),7.08(s,3H，benzene),7.32-7.36(d,3H， benzene),7.41-7.45(d,3H，benzene),7.50(s,3H，benzene),5.82(s,2H，-CH), 3.93-3.94(d,18H,-OCH3). MS (MALDI-TOF) m/z 662.3, calculated value (C)44H38O6) m/z＝662.4(M+)。
2) The preparation of 2,7, 14-tri- (3, 4-dihydroxyphenyl) triptycene has the following synthetic route:
Figure BDA0002370472000000121
the method comprises the following specific steps: adding 2,7, 14-tris- (3, 4-dimethoxyphenyl) triptycene (662mg, 1mmol,1.0eq) and 30mL of dichloromethane into a 100mL reaction bottle, dissolving in nitrogen atmosphere, dropwise adding a boron tribromide dichloromethane solution (1.0mL, 10.0mmol, 10.0eq) into the reaction solution at a low temperature of-78 ℃ by using a syringe, reacting the reaction system at-78 ℃ for 1h, gradually raising the temperature to room temperature, and continuing to reactThe reaction was continued for 12h, and 10mL of ice water was slowly added to the reaction system to quench the reaction. The reaction solution was washed with water to neutrality, washed with saturated brine once and dried over anhydrous sodium sulfate. Suction filtration and reduced pressure distillation of the filtrate gave 540mg of a white solid in 93% yield.1H NMR(400MHz,CDCl3) δ (ppm)6.95 to 6.99(d,3H, benzene),6.83 to 6.87 (d,3H, benzene),7.21(s,3H, benzene),7.32 to 7.36(d,3H, benzene),7.41 to 7.45(d,3H, benzene),7.50(s,3H, benzene),5.86(s,2H, -CH),5.42(s,6H, -OH). MS (MALDI-TOF) m/z 578.1, calculated value (C)38H26O6)m/z＝578.0(M+)。
3) The preparation of 2,7, 14-tri- (3, 4-di-tert-butylcarbonate phenyl) triptycene (compound (1)) has the following synthetic route:
Figure BDA0002370472000000131
in the reaction scheme, Boc represents
Figure BDA0002370472000000132
The substituent, DMAP, is known under the Chinese name 4-dimethylaminopyridine.
The method comprises the following specific steps: 2,7, 14-tris- (3, 4-dihydroxyphenyl) triptycene (578.1mg, 1mmol,1.0eq), Boc anhydride (di-tert-butyl dicarbonate) (2.0g, 9mmol,9.0eq) and 20mL of dry tetrahydrofuran were charged in a 100mL reaction flask, stirred to dissolve completely under nitrogen, a catalytic amount of DMAP (12.2mg, 0.1mmol,0.1eq) was added to the solution to initiate the reaction, and stirred at room temperature for 24 h. The reaction solution was extracted with dichloromethane/water, and the organic phase was washed twice with water and once with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain a semisolid substance. The semi-solid was dissolved in 4mL of tetrahydrofuran and precipitated dropwise into 100mL of ethanol to give 0.95g of a white solid in 80% yield.1H NMR(400MHz, CDCl3):δ(ppm)6.97-6.99(d,3H，benzene),6.80-6.82(d,3H，benzene),7.08(s,3H， benzene),7.32-7.36(d,3H，benzene),7.41-7.45(d,3H，benzene),7.50(s,3H， benzene),5.82(s,2H，-CH),1.55(d,54H,-O(CH3)3). MS (MALDI-TOF) m/z 1179.3, calculated value (C)68H74O18)m/z＝1179.2(M+)。
Example 4
Preparation of Compound (2)
Figure BDA0002370472000000133
AD represents
Figure BDA0002370472000000134
The preparation method comprises the following steps:
1) the preparation of 2,3,6,7,14, 15-hexa- (4-methoxyphenyl) triptycene has the following synthetic route:
Figure BDA0002370472000000141
the method comprises the following specific steps: under the protection of high-purity nitrogen, 2,3,6,7,14, 15-hexabromotriptycene (728mg,1mmol,1.0eq), palladium tetratriphenylphosphine (115mg,0.1mmol,0.1eq), 4-methoxyphenylboronic acid (1.4g,9mmol,9.0eq) and 20mL of redistilled toluene are added into a 100mL Schlenk reaction flask, 5mL of ethanol solution and 2M Na are added into the reaction flask after stirring and dissolving2CO32mL of aqueous solution, heating the reaction solution to 60-100 ℃, refluxing for 12h, cooling to room temperature, extracting with dichloromethane/water, combining organic layers, washing the organic layers once with saturated saline solution, and drying with anhydrous sodium sulfate. And (4) carrying out suction filtration, and distilling the filtrate under reduced pressure to obtain a gray solid. The solid was dissolved with 4mL dichloromethane, precipitated in 100mL ethanol, filtered and oven dried in vacuo to afford 803mg of a white solid in 90% yield.1H NMR(400MHz，CDCl3):δ(ppm)7.48(s,6H， benzene),7.01-7.03(d,12H，benzene),6.74-6.76(d,12H，benzene),5.59(s,2H， -CH),3.77(s,18H,-OCH3). MS (MALDI-TOF) m/z 891.1, calculated value (C)62H50O6) m/z＝891.2(M+)。
2) The preparation of 2,3,6,7,14, 15-hexa- (4-hydroxyphenyl) triptycene has the following synthetic route:
Figure BDA0002370472000000142
the method comprises the following specific steps: adding 2,3,6,7,14, 15-hexa- (4-methoxyphenyl) triptycene (890mg, 1mmol,1.0eq) and 40mL of dichloromethane into a 100mL reaction bottle, dissolving under nitrogen atmosphere, dropwise adding a dichloromethane solution (2.0mL, 10.0mmol, 10.0eq) of boron tribromide into the reaction liquid at low temperature of-78 ℃ by using an injector, placing the reaction system at-78 ℃ for reaction for 1h, gradually raising the temperature to room temperature, continuing the reaction for 12h, slowly adding 15mL of ice water into the reaction system, and quenching the reaction, wherein white solids are separated out. Filtering to obtain white solid, dissolving in ethyl acetate, washing with water to neutrality, washing with saturated saline solution once, and drying with anhydrous sodium sulfate. Suction filtration and reduced pressure distillation of the filtrate gave 750mg of a white solid in 93% yield.1H NMR(400MHz，CDCl3) Delta (. delta.,. sup.49 (s,6H, benzene),7.05-7.08(d,12H, benzene),6.79-6.78(d,12H, benzene),5.61(s,2H, -CH),5.46(s,6H, -OH). MS (MALDI-TOF) m/z 806.3, calculated value (C)56H38O6)m/z＝806.5(M+)。
3) The preparation of 2,3,6,7,14, 15-hexa- (4-adamantylphenyl acetate) triptycene has the following synthetic route:
Figure BDA0002370472000000151
in the reaction formula, AD represents
Figure BDA0002370472000000152
The method comprises the following specific steps: a100 mL reaction flask was charged with 2,3,6,7,14, 15-hexa- (4-hydroxyphenyl) triptycene (806mg, 1mmol,1.0eq), tetrabutylammonium bromide (800mg, 2.4mmol, 2.4eq), potassium carbonate (5.6g, 40mmol) and N-methylpyrrolidone (NMP, 50mL), stirred at room temperature for 2h, and the reaction mixture was slowly dropped with adamantane α -chloroacetate (2.9g, 12mmol, 12eq) in NMP(20mL) the solution was heated to 60 ℃ and reacted for 48 h. After the reaction was completed, the reaction solution was cooled to room temperature, the reaction solution was extracted with ethyl acetate/water, the organic phase was washed once with 3 wt% oxalic acid solution and water, respectively, the organic layers were combined, dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and recrystallization was performed with ethyl acetate/n-hexane mixed solvent to obtain 1.6g of a white solid with a yield of 78%.1H NMR(400MHz，CDCl3) Delta (. delta.) (ppm)7.48(s,6H, benzene), 7.01-7.03(d,12H, benzene),6.74-6.76(d,12H, benzene),5.59(s,2H, -CH), 1.67-1.70(m, 114H). MS (MALDI-TOF) m/z 2044.1, calculated value (C)134H146O18) m/z＝2044.3(M+)。
Example 5
Preparation of Compound (3)
Figure BDA0002370472000000161
AD represents
Figure BDA0002370472000000163
The preparation method comprises the following steps:
1) the preparation of 2,6, 14-tri- (3, 5-dimethoxyphenyl) triptycene has the following synthetic route:
Figure BDA0002370472000000162
the method comprises the following specific steps: under the protection of high-purity nitrogen, 2,6, 14-tribromotriptycene (975.6mg,2mmol,1.0eq), palladium tetratriphenylphosphine (230mg,0.2mmol,0.1eq), 3, 5-dimethoxyphenylboronic acid (1.64g,9mmol,4.5eq) and 30mL of redistilled toluene are added into a 100mL Schlenk reaction bottle, and after stirring and dissolving, 6mL of ethanol solution and 2MNa are added into the reaction bottle2CO33mL of aqueous solution, heating the reaction solution to 60-100 ℃, refluxing for 12h, cooling to room temperature, extracting with dichloromethane/water, combining organic layers, washing the organic layers once with saturated saline solution, and drying with anhydrous sodium sulfate. And (4) carrying out suction filtration, and distilling the filtrate under reduced pressure to obtain a gray solid. Dissolve the solid with 4mL of dichloromethaneAfter decomposition, precipitation in 100mL of ethanol, filtration and drying in a vacuum oven gave 1.3g of a white solid with a yield of 98%.1H NMR(400MHz,CDCl3):δ(ppm)6.96(s,3H， benzene),7.14(s,6H，benzene),7.20(s,3H，benzene),7.32-7.36(d,3H，benzene), 7.45(d,3H，benzene),5.82(s,2H，-CH),3.93-3.94(s,18H,-OCH3). MS (MALDI-TOF) m/z 662.3, calculated value (C)44H38O6)m/z＝662.4(M+)。
2) The preparation of 2,6, 14-tri- (3, 5-dihydroxyphenyl) triptycene has the following synthetic route:
Figure BDA0002370472000000171
the method comprises the following specific steps: adding 2,6, 14-tris- (3, 5-dimethoxyphenyl) triptycene (662mg, 1mmol,1.0eq) and 30mL of dichloromethane into a 100mL reaction bottle, dissolving in nitrogen atmosphere, dropwise adding a boron tribromide dichloromethane solution (1.0mL, 10.0mmol, 10.0eq) into the reaction solution at a low temperature of-78 ℃ by using a syringe, reacting the reaction system at-78 ℃ for 1h, gradually raising the temperature to room temperature, continuing to react for 12h, and slowly adding 10mL of ice water into the reaction system to quench the reaction. The reaction solution was washed with water to neutrality, washed with saturated brine once and dried over anhydrous sodium sulfate. Suction filtration and reduced pressure distillation of the filtrate gave 540mg of a white solid in 93% yield.1H NMR(400MHz,CDCl3) δ (ppm)6.97(s,3H, benzene),7.16(s,6H, benzene),7.22(s,3H, benzene),7.34-7.35(d,3H, benzene),7.45(d,3H, benzene), 5.85(s,2H, -CH),3.93-3.94(s,6H, -OH). MS (MALDI-TOF) m/z 578.1, calculated value (C)38H26O6)m/z＝578.0(M+)。
3) The preparation of 2,6, 14-tri- (3, 5-norbornanyl phenyl diacetate) triptycene has the following synthetic route formula:
Figure BDA0002370472000000172
in the reaction formula, BH represents
Figure BDA0002370472000000173
And (4) a substituent.
The method comprises the following specific steps: 2,6, 14-tris- (3, 5-dihydroxyphenyl) triptycene (578.1mg, 1mmol,1.0eq), tetrabutylammonium bromide (800mg, 2.4mmol, 2.4eq), potassium carbonate (5.6g, 40mmol) and N-methylpyrrolidone (NMP, 50mL) were added to a 100mL reaction flask, stirred at room temperature for 2h, a solution of norbornyl chloroacetate (2.9g, 12mmol, 12eq) in NMP (20mL) was slowly dropped into the reaction solution, and the temperature was raised to 60 ℃ for reaction for 48 h. After the reaction was completed, the reaction solution was cooled to room temperature, the reaction solution was extracted with ethyl acetate/water, the organic phase was washed once with 3 wt% oxalic acid solution and water, respectively, the organic layers were combined, dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and recrystallization was carried out with ethyl acetate/n-hexane mixed solvent to obtain 1.1g of a white solid with a yield of 70%.1H NMR(400MHz，CDCl3):δ(ppm)6.95(s,3H，benzene),7.12(s,6H， benzene),7.21(s,3H，benzene),7.32-7.36(d,3H，benzene),7.45(d,3H，benzene), 5.83(s,2H，-CH),1.63-1.70(m,90H,-OCH3). MS (MALDI-TOF) m/z 1576.2, calculated value (C)98H110O18)m/z＝1576.4(M+)。
Example 6
The thermal properties of 2,7, 14-tris- (3, 4-di-tert-butylcarbonate-ylphenyl) triptycene (compound (1)) prepared in example 3 are shown in FIG. 1 by differential scanning calorimetry and thermogravimetric analysis, and the glass transition temperature reaches 150 ℃ or higher, which shows good thermal stability.
Example 7
A positive photoresist composition comprising 2,7, 14-tris- (3, 4-di-tert-butylcarbonatophenyl) triptycene prepared in example 3, Propylene Glycol Monomethyl Ether Acetate (PGMEA), and triphenylsulfonium triflate. The specific method comprises the following steps: the 2,7, 14-tris- (3, 4-di-tert-butylcarbonate phenyl) triptycene prepared in example 3 was dissolved in Propylene Glycol Monomethyl Ether Acetate (PGMEA) to prepare a solution with a mass concentration of 5%, 0.1 wt% of triphenylsulfonium trifluoromethanesulfonate was added as a photoacid generator, the solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-on solution, a spin-on film was formed on an acid-base treated silicon substrate, the film was baked at 100 ℃ for 3 minutes, and the prepared film was subjected to an extreme ultraviolet exposure experiment at an upper sea light source interference light reticle station (BL08U1B) with an exposure period of 140nm to obtain very uniform photo-etched stripes, which had a resolution of 44.1nm as shown in fig. 2.
Example 8
A positive photoresist composition comprising the compound (2) prepared in example 4, cyclohexanone and triphenylsulfonium perfluorobutylsulfonate. The specific method comprises the following steps: the compound (2) prepared in example 4 was dissolved in cyclohexanone to prepare a solution with a mass concentration of 10%, 0.1 wt% of triphenylsulfonium perfluorobutylsulfonate as a photoacid generator was added, and the solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-on solution, and a film was formed on an acid-base treated silicon substrate by spin coating, and was baked at 100 ℃ for 3 minutes, and the film obtained was subjected to an electron beam exposure experiment with an exposure period of 150nm to obtain a very uniform photo-etching fringe, the resolution of which was 59.5nm as shown in fig. 4.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A triptycene derivative represented by the formula (A):
Figure FDA0002370471990000011
wherein R is1、R2、R3、R4、R5、R6Identical or different, independently of one another, from hydrogen or from 1 to 5RaSubstituted aryl, heteroaryl; r1And R2Group R3And R4Group R5And R6In three groups of substituents, each group has at least one substituent of 1-5RaSubstituted aryl, heteroaryl; each RaIdentical OR different, independently of one another, from hydrogen, OR-ORbSaid R isbIs an acid-sensitive group, R in the molecule of the formula (A)aAt least one is-ORb；
The acid-sensitive group refers to a group which can react under an acidic condition so as to be removed from the main body;
preferably, the acid-sensitive group Rbis-CR1-O-R1、-CO-O-R1、-CH2-CO-O-R1、
Figure FDA0002370471990000012
Wherein R is1Identical or different, independently from each other, from the following groups unsubstituted or optionally substituted by one, two or more Rs 2: c1-15Alkyl radical, C3-20A cycloalkyl group;
Figure FDA0002370471990000013
optionally substituted on the ring with one, two or more Rs 2;
m is any integer of 1 to 4,
Figure FDA0002370471990000014
represents a bond of the group to the host structure;
rs2, which are identical or different, are independently selected from the following groups: NO2Halogen, C1-15Alkyl radical, C1-15Alkoxy radical, C3-20A cycloalkyl group;
preferably, said R is1Is a quilt C1-6Alkyl substituted or unsubstituted the following groups: c1-6Alkyl radical, C3-8Monocyclic cycloalkyl, C7-12Bridged cycloalkyl.
2. The triptycene derivative of claim 1, wherein R is1、R2、R3、R4、R5、R6The same or different, independently from each other, are selected from hydrogen or substituted by 1,2 or 3RaSubstituted C6-10Aryl, heteroaryl; r1And R2Group R3And R4Group R5And R6In three groups of substituents, each group has at least one substituent substituted by 1,2, or 3RaSubstituted C6-10Aryl, heteroaryl; each RaIdentical OR different, independently of one another, from hydrogen, OR-ORbR in each molecule of formula (A)aAt least one is-ORb(ii) a The R isbHaving the definition set forth in claim 1.
3. The triptycene derivative of claim 1, wherein R is1、R2、R3、R4、R5、R6Identical or different, independently of one another, from hydrogen or substituted by 1,2 or 3RaSubstituted phenyl; r1And R2Group R3And R4Group R5And R6In three groups of substituents, each group has at least one substituent being substituted by 1,2 or 3RaSubstituted phenyl; each RaIdentical OR different, independently of one another, from hydrogen OR-ORbR in each molecule of formula (A)aAt least one is-ORb(ii) a The R isbHaving the definition set forth in claim 1.
4. The triptycene derivative of claim 1, wherein R is1、R2、R3、R4、R5、R6Identical or different, independently of one another, from hydrogen or
Figure FDA0002370471990000021
And R is1And R2Group R3And R4Group R5And R6In three groups of substituents, each group has at least one substituent of
Figure FDA0002370471990000022
Each RaIdentical OR different, independently of one another, from hydrogen OR-ORbR in each molecule of formula (A)aAt least one is-ORb；
The group RbSelected from the group consisting of:
Figure FDA0002370471990000023
wherein the content of the first and second substances,
Figure FDA0002370471990000024
represents a connecting bond;
preferably, the present invention also provides compounds represented by formula (I), formula (II) and formula (III):
Figure FDA0002370471990000031
wherein: ra1、Ra2、Ra3And RaThe definitions are the same;
preferably, the triptycene derivative is selected from the following structures:
Figure FDA0002370471990000032
wherein Boc represents
Figure FDA0002370471990000034
Substituent, AD represents
Figure FDA0002370471990000035
BH represents
Figure FDA0002370471990000036
And (4) a substituent.
5. A process for the preparation of a triptycene derivative according to any one of claims 1 to 4, comprising the steps of:
1) carrying out Suzuki coupling reaction on the compound a and a compound b to obtain a compound c, wherein the compound b is selected from 1-5Ra' substituted arylboronic acids, arylboronic acid esters, heteroarylboronic acids or heteroarylboronic acid esters, such as: 3, 4-dimethoxyphenylboronic acid, 4-methoxyphenylboronic acid, 3, 5-dimethoxyphenylboronic acid; ra' selected from C1-12Alkoxy or aryl radicals C1-6Alkoxy, such as methoxy, ethoxy, benzyloxy;
Figure FDA0002370471990000033
wherein R is1'、R2'、R3'、R4'、R5'、R6' same or different, independently from each other, are selected from hydrogen, fluorine, chlorine, bromine or iodine and are not simultaneously hydrogen;
R1”、R2”、R3”、R4”、R5”、R6"identical or different, independently of one another, from hydrogen or substituted by 1 to 5Ra' substituted aryl or heteroaryl, and not both hydrogen; ra' selected from C1-12Alkoxy or aryl radicals C1-6Alkoxy, such as methoxy, ethoxy, benzyloxy;
2) reacting the compound c with a reducing agent to obtain a compound d;
Figure FDA0002370471990000041
wherein R is1”'、R2”'、R3”'、R4”'、R5”'、R6"' are the same or different and are independently selected from hydrogen or aryl or heteroaryl substituted with 1,2 or 3 OH, and are not simultaneously hydrogen;
3) reacting compound d with compound Rb-L-reaction of the compound (I),obtaining the triptycene derivative shown as the formula (A), wherein L is a leaving group or L and RbForm a group containing RbAcid anhydride of RbHaving the definition as claimed in claim 1 or 4,
Figure FDA0002370471990000042
wherein R is1、R2、R3、R4、R5、R6Having the definition of any one of claims 1 to 4;
preferably, said compound RbL is, for example, di-tert-butyl dicarbonate, adamantane- α -chloroacetate, norbornyl chloroacetate;
preferably, the reducing agent is selected, for example, from boron tribromide or boron trichloride.
6. Use of a triptycene derivative of any one of claims 1-4 as a host material for a photoresist.
7. A positive-working photoresist composition comprising the triptycene derivative of any one of claims 1-4, a photoacid generator, and a photoresist solvent;
preferably, the mass of the triptycene derivative shown in the formula (A) is 1-10 wt% of the total mass of the positive photoresist composition, the mass of the photoacid generator is 0.01-1 wt%, and the balance is a photoresist solvent;
preferably, the photoacid generator is selected from ionic or non-ionic photoacid generators, including one or more of triphenylsulfonium triflate, triphenylsulfonium perfluorobutyrate, bis (4-tert-butylphenyl) iodonium p-toluenesulfonate, or N-hydroxynaphthalimide trifluoromethanesulfonate;
preferably, the photoresist solvent is selected from one or more of propylene glycol monomethyl ether acetate, ethyl lactate, ethylene glycol monomethyl ether, or cyclohexanone.
8. A positive-working photoresist film comprising the triptycene derivative of any of claims 1-4.
9. The method of producing a positive-working photoresist film according to claim 8, which comprises applying the positive-working photoresist composition according to claim 7 on a substrate to form a film;
preferably, the application mode is a spin coating method;
preferably, the substrate may be a silicon wafer.
10. Use of a positive-working photoresist composition according to claim 7 and/or a positive-working photoresist film according to claim 8 in photolithography;
the photoetching is 248nm photoetching, 193nm photoetching, extreme ultraviolet photoetching (EUV), nano-imprint photoetching or electron beam photoetching;
preferably, the positive photoresist composition, positive photoresist coating are used for electron beam lithography and extreme ultraviolet lithography.
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