CN104557552B - Star-shaped tetraphenylethylene derivative molecular glass, positive photoresist coating and application thereof - Google Patents

Abstract

The invention discloses a star-shaped tetraphenylethylene derivative molecular glass, a positive photoresist, a positive photoresist coating and an application thereof. The star-shaped tetraphenylethylene derivative molecular glass has the following molecular structure: The molecular glass has a simple synthesis process and is suitable for industrial production. Tetraphenylethylene has a rigid three-dimensional geometric framework, which can effectively inhibit molecular crystallization and is easy to form a film. The molecular glass has good properties in various polar solvents. It has high solubility, high glass transition temperature and good thermal stability, which can better meet the requirements of photolithography process. Spin Coating can be used to produce a good film, which can be used as a photoresist and other additives to make a positive photoresist for photolithography.

Description

A star-shaped tetraphenylethylene derivative molecular glass, positive photoresist, positive photolithography Adhesive coating and its application

technical field

The invention belongs to the field of material technology, and in particular relates to a star-shaped tetraphenylethylene derivative molecular glass, a positive photoresist, a positive photoresist coating and an application thereof.

Background technique

Photoresist (also known as photoresist) is a kind of etching-resistant thin film material whose solubility changes after energy radiation such as beam, electron beam, ion beam or x-ray. It is used in the microfabrication of integrated circuits and semiconductor discrete devices. also has wide applications. By coating photoresist on semiconductors, conductors and insulators, the part left after exposure and development can protect the bottom layer, and then use etchant to etch to transfer the required fine patterns from the mask to the substrate. Therefore, photoresist is a key material in microfabrication technology. The rapid development of the semiconductor industry has put forward higher and higher requirements for lithography technology, from the earliest g-line (436nm) lithography, i-line (365nm) lithography, deep ultraviolet 248nm lithography, to the current 193nm lithography, As well as the most promising next-generation extreme ultraviolet (EUV, 13.5nm) lithography, the resolution of lithography technology has developed from micron to nanoscale, and correspondingly higher requirements have been put forward for photoresists. Photoresist with high resolution, high sensitivity and low edge roughness, so that its comprehensive performance can meet the requirements of lithography process has become an important task in the development of lithography technology.

At present, commercial photoresist host materials usually use low-molecular-weight polymers with a molecular weight of 5,000 to 15,000 Daltons, but polymer materials usually affect photolithographic patterns due to reasons such as large molecular volume, polydisperse molecular weight, and molecular chain entanglement. resolution. Molecuar Glasses are a class of small molecular compounds with special structures and functions. These small molecular compounds have exact molecular structure, monodispersity and small radius of gyration, as well as thermal stability and thermal stability of polymers. Film-forming properties are expected to become a new class of photoresist host materials (Adv. Mater. 2008, 20, 3355). Common molecular glasses are mainly branched or ring-shaped compounds with topology, such as rigid structures connected by polyphenyl rings (J.Mater.Chem.2008, 18, 1903; Chem.Mater.2008, 20, 1606) , calixarene structure (J.Mater.Chem.2008,18,3588; J.Mater.Chem.2010,20,4445), etc. Molecular glasses with these structures usually exhibit higher glass transition temperature (Tg) and Very good film-forming properties, which can meet the requirements of photolithography processing technology.

Tetraphenylethylene compounds are a class of luminescent compounds that have been studied more at present (Chem. The coplanar benzene ring structure can effectively inhibit intermolecular crystallization and contribute to film formation. At the same time, tetraphenylethylene has a certain rigidity, high glass transition temperature, and good thermal stability. The design and synthesis is based on the tetraphenylethylene structure. The molecular glass will help to improve the glass transition temperature and film-forming properties of the molecular glass.

Contents of the invention

The first technical problem to be solved by the present invention is to provide a star-shaped tetraphenylethylene derivative molecular glass, which has good solubility in various polar solvents, and adopts the spin coating method (Spin Coating) It can make a good film; it can be used as a photoresist and other additives to make a positive photoresist for photolithography.

In order to solve the first technical problem, the present invention adopts the following technical solutions:

A star-shaped tetraphenylethylene derivative molecular glass has the following molecular structure:

Wherein, the substituent R is an acid-sensitive substituent group.

Preferably, the acid-sensitive substituent is an alkane carbonate substituent or an alkane α-acetate substituent with less than 12 carbon atoms;

More preferably, the acid-sensitive substituent group is a group with the following structure:

In the formula, Indicates the bond to the benzene ring.

The second technical problem to be solved by the present invention is to provide a method for preparing the star-shaped tetraphenylethylene derivative molecular glass, comprising the following preparation steps:

1) Under the protection of high-purity nitrogen or argon, mix tetrakis(4-bromophenyl)ethylene and phenylboride containing methoxy substituents in a molar ratio of 1:4~8, and add 4-8 equivalents, 2M sodium carbonate solution and catalytic amount of tetrakis(triphenylphosphine)palladium, react in toluene at 50-70°C for 6-24 hours to obtain methoxy-substituted tetraphenylethylene derivative;

2) Mix the methoxy-substituted tetraphenylethylene derivative obtained in step 1) with BBr3 at a molar ratio of 1:6~18, react in dry dichloromethane at -50~-80°C, and then gradually Warming up to room temperature, and continuing to react at room temperature, generating tetraphenylethylene derivatives with phenolic hydroxyl groups on the periphery;

3) Under the protection of high-purity nitrogen or argon, mix the adamantane derivatives with phenolic hydroxyl groups on the periphery obtained in step 2) and compounds containing acid-sensitive substituents at a molar ratio of 1:4 to 18, and add catalyst A certain amount of weak base is used as a catalyst, and reacted in a polar solvent under the condition of 25-60°C for 10-48 hours to obtain star-shaped tetraphenylethylene derivative molecular glass.

Preferably, the phenyl boride containing a methoxy substituent is one or a mixture of two of the following substances: p-methoxyphenyl pinacol borane, m-methoxyphenyl pinacol boron alkane, 3,4-dimethoxyphenylpinacol borane, 3,5-dimethoxyphenylpinacol borane, 3,4,5-trimethoxyphenylpinacol borane , p-methoxyphenylboronic acid, m-methoxyphenylboronic acid, 3,4-dimethoxyphenylboronic acid, 3,5-dimethoxyphenylboronic acid, 3,4,5-trimethoxy Phenylboronic acid.

The compound containing the acid-sensitive substituent has the following structure:

In the formula, R is an alkyl chain with less than 12 carbon atoms; X=Cl, Br or I.

Compounds with the following structures are preferred:

In the formula, X=Cl, Br or I.

The third technical problem to be solved by the present invention is to provide a positive photoresist. The main material of the positive photoresist is star-shaped tetraphenylethylene derivative molecular glass surrounded by acid-sensitive substituent groups.

In order to solve the third technical problem, the present invention adopts the following technical solutions:

A kind of positive photoresist, said positive photoresist comprises star-shaped tetraphenylethylene derivative molecular glass surrounded by acid-sensitive substituent groups,

Preferably, the positive photoresist also includes a photoacid generator and a photoresist solvent.

Preferably, the star-shaped tetraphenylethylene derivative molecular glass accounts for 1%-10% by weight of the entire positive photoresist.

Preferably, the photoacid generator is selected from ionic or non-ionic photoacid generators, preferably, the photoacid generator is selected from triphenylsulfonium trifluoromethanesulfonate, perfluorobutylsulfonium One or more of acid triphenylsulfonium salt, p-toluenesulfonic acid bis(4-tert-butylphenyl)iodonium salt or N-hydroxynaphthalimide trifluoromethanesulfonate; the light Resist solvent is selected from one or more in propylene glycol monomethyl ether acetate, ethyl lactate, ethylene glycol monomethyl ether or cyclohexanone; Described photoacid generator consumption accounts for whole positive photoresist weight 0.01%-1%.

The fourth technical problem to be solved by the present invention is to provide a positive photoresist coating.

In order to solve the fourth technical problem, the present invention adopts the following technical solutions:

A positive photoresist coating, the positive photoresist coating is formed by spinning the above positive photoresist on a silicon wafer to obtain a positive photoresist coating.

Preferably, the positive photoresist coating is used in modern lithography technologies such as 248nm lithography, 193nm lithography, extreme ultraviolet lithography, nanoimprint lithography or electron beam lithography, and is especially suitable for extreme ultraviolet lithography. (EUV) lithography process.

Beneficial effects of the present invention:

The star-shaped molecular glass with tetraphenylethylene structure as the core has a simple synthesis process and is suitable for industrial production; tetraphenylethylene has a three-dimensional geometric skeleton, which can effectively inhibit the crystallization of molecules and is easy to form a film; tetraphenylethylene has good Rigid structure, and has the characteristics of high glass transition temperature and good thermal stability, which can better meet the requirements of photolithography process.

Description of drawings

Below in conjunction with accompanying drawing, specific embodiment of the present invention is described in further detail

Fig. 1 is a differential scanning calorimetry curve and a thermogravimetric curve of tetrakis-(7,8-di-tert-butylcarbonate-biphenyl)ethylene of the present invention.

Fig. 2 is a scanning electron microscope (SEM) image of tetrakis-(7,8-di-tert-butylcarbonate-biphenyl)ethylene film of the present invention.

Fig. 3 is an atomic force microscope (AFM) image of tetrakis-(7,8-di-tert-butylcarbonate-biphenyl)ethylene film of the present invention.

Fig. 4 is a scanning electron microscope (SEM) image of tetrakis-(7,8-di-tert-butylcarbonate-biphenyl)ethylene film-forming photolithographic stripes of the present invention.

detailed description

In order to better understand the present invention, the solution of the present invention will be further described through specific examples below, but the protection scope of the present invention should include the entire content of the claims, but is not limited thereto.

The present invention lists two preparation methods of phenylborides containing methoxy substituents for reference.

The synthetic route of 3,5-dimethoxyphenylboride is as follows:

The specific steps are as follows: add 3,5-dimethoxybromobenzene (1.74g, 8.0mmol, 1.0eq) and catalyst PdCl ₂ (PPh ₃ ) ₂ (281mg, 0.4mmol, 0.05eq) in a 100mL Schlenk reaction flask, repeat Vacuum-flush nitrogen three times, add dry redistilled 1,2-dichloroethane (20ml), triethylamine (7ml, 40mmol, 5.0eq) and pinacol borane (HBpin) into the reaction flask with a syringe (3.5ml, 24.0mmol, 3.0eq), the reaction system was warmed up to 90°C, and refluxed for 4h. The reaction system was cooled to room temperature, the reaction solution was poured into 20ml of water to terminate the reaction, the aqueous phase was extracted several times with ethyl acetate, the organic phase was combined, washed once with saturated saline and water respectively, dried over anhydrous magnesium sulfate, and spin-dried to dry the solvent , the obtained product was recrystallized in n-hexane/ethyl acetate to obtain 1.8 g of a white solid with a yield of 85%. ¹ HNMR (400MHz, CDCl ₃ ) δ (ppm) 7.03 (s, 2H, benzene), 6.90 (s, 1H, benzene), 3.84 (s, 6H, -OCH3), 1.33 (s, 12H, -CH3).

The synthetic route of 3,4-dimethoxyphenylboride is similar to that of 3,5-dimethoxyphenylboride, except that the raw material 3,5-dimethoxybromobenzene is changed to 3, 4-Dimethoxybromobenzene.

The synthetic route of 3,4,5-trimethoxyphenylboride is as follows:

The specific steps are as follows: add 3,4,5-trimethoxybromobenzene (1.24g, 5.0mmol, 1.0eq) and catalyst PdCl ₂ (PPh ₃ ) ₂ (176mg, 0.25mmol, 0.05eq) into a 100mL Schlenk reaction flask, Repeat vacuuming-nitrogen three times, add dry redistilled 1,2-dichloroethane (15ml), triethylamine (4.5ml, 25mmol, 5.0eq) and HBpin (2.2ml, 15.0 mmol, 3.0eq), the temperature of the reaction system was raised to 90°C, and the reaction was refluxed for 4h. The reaction system was cooled to room temperature, the reaction solution was poured into 20ml of water, the aqueous phase was extracted several times with ethyl acetate, the organic phases were combined, washed once with saturated saline and water respectively, dried over anhydrous magnesium sulfate, and the solvent was spin-dried. The obtained product was recrystallized in n-hexane/ethyl acetate to obtain 1.2 g of a white solid with a yield of 80%. ¹ HNMR (400MHz, CDCl ₃ ) δ (ppm) 7.03 (s, 2H, benzene), 3.90 (s, 6H, -OCH3), 3.87 (s, 3H, -OCH3), 1.34 (s, 12H, -CH3) .

The present invention lists a preparation method of tetrakis (4-bromophenyl) ethylene for reference.

The synthetic route is as follows:

Add 4,4'-dibromobenzophenone (3.4g, 10mmol, 1.0eq), zinc powder (1.6g, 24mmol, 2.4eq) and 60mL dry tetrahydrofuran into a 250mL three-necked flask. After deoxygenation with nitrogen, place in acetone/liquid nitrogen bath at -78°C to cool. Then TiCl ₄ (2.3g, 12mmol, 1.2eq) was slowly injected into the reaction system through a syringe. After completion, the system was stirred at room temperature for half an hour, and then refluxed overnight. The reaction was stopped, and the reaction solution was filtered through a decompressed silica gel column to remove inorganic salts such as zinc and titanium. The filtrate was collected and spin-dried to obtain a crude product, which was recrystallized in methanol to obtain 2.5 g of white crystals with a yield of 76%. ¹ H NMR (400MHz, CDCl3), δ (ppm) 7.24 (d, 8H, J=8.4Hz), 6.84 (d, 8H, J=8.4Hz).

Example 1

The preparation method of tetrakis-(7,8-di-tert-butylcarbonate base biphenyl) ethylene molecular glass, the method comprises the following steps:

1) Tetra-(7,8-dimethoxybiphenyl)ethylene, the synthetic route is as follows:

Under the protection of high-purity nitrogen, tetrakis(4-bromophenyl)ethylene (648mg, 1.0mmol, 1.0eq), Pd(PPh ₃ ) ₄ (116mg, 0.1mmol, 0.1eq) and Redistilled toluene 15ml, after stirring and dissolving, add 3ml of ethanol solution and 2M Na ₂ CO dissolved in 3,4-dimethoxyphenyl pinacol borane (1320mg, 5.00mmol, 5.0eq) into the reaction flask with a syringe ₃ Aqueous solution 1ml, the reaction solution was heated at 50-70°C and refluxed for 12 hours, cooled to room temperature, extracted with dichloromethane/water, the organic layers were combined, dried over anhydrous sodium sulfate, concentrated under reduced pressure to remove the solvent, and recrystallized in ethanol to obtain a white solid 658 mg, yield 75%. ¹ HNMR (400MHz, CDCl ₃ ) δ (ppm) 7.57 (d, J=8.2Hz, 16H), 7.20-7.08 (m, 8H), 6.95 (d, J=8.4Hz, 4H), 3.84 (d, J =10.9Hz, 24H); MS (MALDI-TOF): m/z=876.0, calcdfor (C ₅₈ H ₅₂ O ₈ ) m/z=876.4 ([M] ⁺ ).

2) Tetra-(7,8-dihydroxybiphenyl)ethylene, the synthetic route is as follows:

Add tetrakis-(7,8-dimethoxybiphenyl)tetraphenylethylene (877mg, 1.0mmol, 1.0eq) and 50ml of dichloromethane into a 250mL three-necked flask, dissolve under nitrogen atmosphere, and store at low temperature -78 At ℃, a solution of boron tribromide in dichloromethane (1.0ml, 10.0mmol, 10.0eq) was added dropwise to the reaction solution with a syringe, and the reaction solution was reacted at -78℃ for 1 hour and then gradually warmed to room temperature, and the reaction was continued for 12 hour, slowly add 10ml of water to the reaction system to quench the reaction, remove the dichloromethane solvent under reduced pressure, and filter the residue to obtain a white solid, which is washed with water and dichloromethane respectively to obtain a solid and then precipitated with methanol/water three times to obtain a light yellow solid 735 mg, yield 96%. ¹ HNMR(400MHz,DMSO-d ₆ )δ(ppm)8.98(s,8H),7.61(d,J=8.4Hz,8H),7.50(d,J=8.4Hz,8H),7.03(s,4H ),6.92(d,J=8.2Hz,4H),6.80(d,J=8.2Hz,4H); MS(MALDI-TOF):m/z=764.5,calcdfor(C ₅₀ H ₃₆ O ₈ )m/ z=764.2([M] ⁺ ).

3) Tetra-(7,8-di-tert-butylcarbonate-based biphenyl)ethylene, the synthetic route is as follows:

In the reaction formula, Boc represents Substituents.

Add tetrakis-(7,8-dihydroxybiphenyl)tetraphenylethylene (765mg, 1.0mmol, 1.0eq), Boc anhydride (di-tert-butyl dicarbonate) (2620mg, 12.0mmol, 12.0 eq) and 20ml of dry tetrahydrofuran were stirred and dissolved under a nitrogen atmosphere, and 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 24h. The reaction solution was extracted with ethyl acetate/water, the organic phase was washed three times with saturated aqueous sodium bisulfate solution and water respectively, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure to obtain a semi-solid mixture in ethyl acetate/n-hexane Recrystallized in medium to obtain 1.28 g of white solid with a yield of 82%. ¹ HNMR (400MHz, CDCl ₃ ) δ (ppm) 7.92–6.80 (m, 28H), 2.19 (s, 12H), 1.51 (d, J=31.7Hz, 72H); MS (MALDI-TOF): m/z =1564.4, calcd for C ₉₀ H ₁₀₀ O ₂₄ m/z=1564.6([M] ⁺ ).

Other similar alkane-containing carbonate substituents Molecular glasses of the structure (C _n =C _1-12 alkyl) are all prepared by similar methods.

Example 2

Four-(8-acetate adamantyl biphenyl) preparation method of ethylene molecular glass, the method may further comprise the steps:

1) Tetra-(8-methoxybiphenyl)ethylene, the synthetic route is as follows:

Under the protection of high-purity nitrogen, tetrakis(4-bromophenyl)ethylene (648mg, 1.0mmol, 1.0eq), Pd(PPh ₃ ) ₄ (116mg, 0.1mmol, 0.1eq) and 15ml of redistilled toluene, after stirring and dissolving, add 3ml of ethanol solution and 2M Na ₂ CO ₃ aqueous solution 1ml of 4-methoxyphenyl pinacol borane (1170mg, 5.00mmol, 5.0eq) into the reaction flask with a syringe , the reaction solution was heated to reflux at 50-70°C for 12h, cooled to room temperature, extracted with dichloromethane/water, the organic layers were combined, dried over anhydrous sodium sulfate, concentrated under reduced pressure to remove the solvent, and recrystallized in ethanol to obtain 545 mg of a white solid. The rate is 72%. ¹ HNMR (400MHz, CDCl ₃ ) δ (ppm) 7.57 (d, J=8.2Hz, 8H), 7.20-7.08 (m, 16H), 6.95 (d, J=8.4Hz, 8H), 3.84 (s, 12H ); MS (MALDI-TOF): m/z=756.3, calcdfor (C ₅₄ H ₄₄ O ₄ ) m/z=756.8 ([M] ⁺ ).

2) Tetra-(8-hydroxybiphenyl)ethylene, the synthetic route is as follows:

Add tetrakis-(8-methoxybiphenyl)tetraphenylethylene (757mg, 1.0mmol, 1.0eq) and 50ml of dichloromethane into a 250mL three-necked flask, dissolve under a nitrogen atmosphere, and at a low temperature of -78°C, A dichloromethane solution of boron tribromide (1.0ml, 10.0mmol, 10.0eq) was added dropwise to the reaction solution with a syringe, and the reaction solution was reacted at -78°C for 1 hour, then gradually warmed to room temperature, and continued to react for 12 hours. Slowly add 10ml of water to the reaction system to quench the reaction, remove the dichloromethane solvent under reduced pressure, and filter the residue to obtain a white solid, which is washed with water and dichloromethane respectively to obtain a solid that is then precipitated three times with methanol/water to obtain 670 mg of a light yellow solid. The rate is 96%. ¹ HNMR(400MHz,CDCl ₃ )δ(ppm)7.58(d,J=8.2Hz,8H), 7.22-7.06(m,16H),7.01(d,J=8.4Hz,8H); MS(MALDI-TOF ): m/z=700.4, calcdfor(C ₅₀ H ₃₆ O ₈ ) m/z=700.2([M] ⁺ ).

3) Synthesis of tetra-(8-adamantyl biphenyl)ethylene molecular glass.

AD in the reaction formula represents Substituents.

Add tetra-(8-hydroxybiphenyl)ethylene (700mg, 1.0mmol, 1.0eq), tetrabutylammonium bromide (400mg, 1.2mmol, 1.2eq), K ₂ CO ₃ (2.8g , 20mmol) and N-methylpyrrolidone (NMP, 50ml), stirred at room temperature for 2 hours, slowly added α-chloroadamantyl acetate (1456.2mg, 6mmol, 6.0eq) in NMP (10ml ) solution, heated to 60°C for 48h. After the reaction was complete, cool to room temperature, extract the reaction solution with ethyl acetate/water, wash the organic phase once with 3 wt% oxalic acid solution and water, combine the organic layers, dry over anhydrous magnesium sulfate, and remove the solvent under reduced pressure. Recrystallized with ethyl acetate/n-hexane mixed solvent to obtain 1275 mg of white solid with a yield of 78%. ¹ HNMR(400MHz,DMSO-d6):δ(ppm)7.59(d,J=8.0Hz,8H),7.22-7.06(m,16H),6.88(d,J=8.4Hz,8H),4.45(s ,8H), 1.67(m,68H). MS (MALDI-TOF): m/z=1524.5, calcdfor C ₁₀₂ H ₁₀₈ O ₁₂ m/z=1524.8 ([M] ⁺ ).

Example 3

The synthetic method of tetrakis-(8-norbornyl acetate-based biphenyl)ethylene molecular glass is the same as in Example 2, except that the raw material α-adamantyl chloroacetate is α-norbornyl chloroacetate.

Example 4

The synthetic method of tetrakis-(7,9-diacetate bridged cyclooctyl biphenyl) ethylene molecular glass is the same as in Example 2, except that the raw material α-chloroacetate adamantyl ester is α-chloroacetate bridged ring octane esters.

Example 5

The thermal properties of tetrakis-(7,8-di-tert-butylcarbonate biphenyl)ethylene prepared in Example 1 are shown in Figure 1 through differential scanning calorimetry and thermogravimetric analysis, and the results show that its glass transition temperature Reached above 150 ℃, with good thermal stability.

Dissolve the compound tetrakis-(7,8-di-tert-butylcarbonate-biphenyl)ethylene in propylene glycol monomethyl ether acetate (PGMEA) to obtain a solution with a mass content of 4%, and add 1% trifluoro Triphenylsulfonium methanesulfonate is a photoacid generator. It is filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution, which is spin-coated on an acid-base treated silicon substrate to form a film. Electron microscope SEM and atomic force microscope AFM were used to analyze the uniformity of the film, as shown in Figures 2 and 3, it can be seen from the figure that the obtained film is very uniform. The prepared film was exposed on the soft X-ray interference lithography line station (BL08U1B) of Shanghai Synchrotron Radiation Light Source, and very uniform lithography stripes were obtained, as shown in Figure 4.

Example 6

Repeat Example 5, the only difference being that the main body material is tetrakis-(8-adamantyl acetate-based biphenyl)ethylene molecular glass (3% by mass) prepared in Example 2, and the solvent is ethylene glycol mono Methyl ether, the acid generator is bis(4-tert-butylphenyl)iodonium p-toluenesulfonate (mass content 0.05%).

Example 7

Repeat Example 5, the only difference is that the main material is tetrakis-(7,8-diacetate norbornyl biphenyl)ethylene (mass content 1%), the solvent is ethyl lactate, and the acid generator is Triphenylsulfonium perfluorobutyl methanesulfonate (mass content 0.01%).

Example 8

Repeat Example 5, the only difference is that the main material is tetrakis-(7,9-diacetate bridged cyclooctyl ester base biphenyl)ethylene (mass content 3%), and the solvent is cyclohexanone, which produces acid The agent is N-hydroxynaphthoimide trifluoromethanesulfonate (mass content 0.5%).

Examples 9-17

Repeat Example 1, the only difference is that in step (1), 3,4-dimethoxyphenyl pinacol borane is used respectively with p-methoxyphenyl pinacol borane, m-methoxy Phenylpinacol borane, 3,5-dimethoxyphenylpinacol borane, 3,4,5-trimethoxyphenylpinacol borane, p-methoxyphenylboronic acid, m- Methoxyphenylboronic acid, 3,4-dimethoxyphenylboronic acid, 3,5-dimethoxyphenylboronic acid, 3,4,5-trimethoxyphenylboronic acid instead.

Example 18

Repeat Example 1, the only difference is that the reaction temperature in step (1) is 50°C, and the reaction time is 24 hours.

Example 19

Example 1 was repeated, the only difference being that the reaction temperature in step (1) was 70° C., and the reaction time was 6 hours.

Example 20-21

Repeat Example 1 except that the reaction temperature in step (2) is -50°C or -80°C.

Example 22

Repeat Example 1, the only difference is that the reaction temperature in step (3) is 25°C, and the reaction time is 48 hours.

Example 23

Example 1 was repeated, the only difference being that the reaction temperature in step (3) was 60° C., and the reaction time was 10 hours.

Apparently, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those of ordinary skill in the art can also make It is impossible to exhaustively list all the implementation modes here, and any obvious changes or changes derived from the technical solutions of the present invention are still within the scope of protection of the present invention.

Claims (14)

1. a star tetraphenylethylene derivative molecular glass, it is characterised in that there is following molecular structure:

Wherein, substituent R is alkanes carbonate substituents or the alkanes α-acetate substituent that carbon number is less than 12.

2. a star tetraphenylethylene derivative molecular glass, it is characterised in that there is following molecular structure:

Wherein, substituent R is to have the group of following structure:

In formula,Represent the connecting key with oxygen atom.

3. the preparation method of the star tetraphenylethylene derivative molecular glass as described in claim 1-2 is arbitrary, its feature exists In, including following preparation process:

1) under high pure nitrogen or argon shield, by four (4-bromophenyl) ethene and containing methoxy substitution base phenyl boride with Mol ratio is the ratio mixing of 1:4～8, is added thereto to 4～8 molar equivalents, and concentration is sodium carbonate liquor and the catalysis of 2M The tetrakis triphenylphosphine palladium of amount, reacts 6～24 hours under the conditions of 50～70 DEG C in toluene, obtains methoxy substitution tetraphenyl Ethene derivatives；

2) by step 1) the methoxy substitution tetraphenylethylene derivative that obtains and BBr₃With mol ratio 1:6～18 mixing, it is being dried Dichloromethane under the conditions of-50～-80 DEG C react, be the most gradually warmed up to room temperature, and continue outside room temperature reaction, generation Shroud has the tetraphenylethylene derivative of phenolic hydroxyl group；

3) under high pure nitrogen or argon shield, by step 2) periphery that obtains with phenolic hydroxyl group tetraphenylethylene derivative with Compound containing R substituent with mol ratio as 1:4～18 mixing, add catalytic amount weak base be catalyst, in polar solvent, React 10～48 hours under the conditions of 25～60 DEG C, obtain star tetraphenylethylene derivative molecular glass；Wherein, when preparation power When profit requires the molecular glass of 1, the compound containing R substituent is:

In formula, R is the alkyl chain that carbon number is less than 12；X=Cl, Br or I；

When preparing the molecular glass of claim 2, the compound containing R substituent is the compound with following structure:

In formula, X=Cl, Br or I.

The preparation method of star tetraphenylethylene derivative molecular glass the most according to claim 3, it is characterised in that step Rapid 1) described in, the phenyl boride containing methoxy substitution base is the one in following material: p-methoxyphenyl gneissic suite boron Alkane, m-methoxyphenyl gneissic suite borine, 3,4-Dimethoxyphenyl gneissic suite borine, 3,5-Dimethoxyphenyl gneissic suite boron Alkane, 3,4,5-trimethoxyphenyl gneissic suite borine, p-methoxyphenyl boric acid, m-methoxyphenyl boric acid, 3,4-dimethoxy Base phenylboric acid, 3,5-dimethoxyphenyl boronic acid, 3,4,5-trimethoxyphenylboronic acid.

5. a positive photoresist, it is characterised in that described positive photoresist includes that the periphery as described in claim 1-2 is R The star tetraphenylethylene derivative molecular glass of substituted radical.

A kind of positive photoresist the most according to claim 5, it is characterised in that described positive photoresist also includes that light acid is produced Raw agent, photoresist solvent.

7. according to the arbitrary described a kind of positive photoresist of claim 5-6, it is characterised in that described star tetraphenylethylene spreads out Biomolecule glass consumption accounts for the 1%～10% of whole positive photoresist weight.

A kind of positive photoresist the most according to claim 6, it is characterised in that described smooth acid producing agent selected from ionic or Nonionic photoacid generators.

9. according to a kind of positive photoresist described in claim 6 or 8, it is characterised in that described smooth acid producing agent is selected from trifluoro Methanesulfonic acid triphenyl sulfosalt, perfluoro butyl sulfonic acid triphenyl sulfosalt, p-methyl benzenesulfonic acid two (4-tert-butyl-phenyl) salt compounded of iodine Or one or more in N-hydroxynaphthylimide fluoroform sulphonate.

A kind of positive photoresist the most according to claim 6, it is characterised in that described photoresist solvent is selected from propane diols One or more in monomethyl ether acetate, ethyl lactate, glycol monoethyl ether or cyclohexanone.

11. a kind of positive photoresists according to claim 8, it is characterised in that described smooth acid producing agent consumption accounts for whole The 0.01%～1% of positive photoresist weight.

12. 1 kinds of positive-tone photo gel coatings, it is characterised in that described positive-tone photo gel coating is that claim 5-11 is any one Described positive photoresist carries out film forming obtain positive-tone photo gel coating by being spin-coated on silicon chip.

The application of 13. 1 kinds of positive-tone photo gel coatings as claimed in claim 12, it is characterised in that described positive photoresist is coated with Layer is in 248nm photoetching, 193nm photoetching, extreme ultraviolet photolithographic, nano-imprint lithography or beamwriter lithography.

The application of 14. positive-tone photo gel coatings as claimed in claim 13, it is characterised in that described positive-tone photo gel coating is used In extreme ultraviolet carving technology.