A class of coumarin-based non-chemically amplified photoresists applicable to lithography of multiple wavelengths, and a preparation method and application thereof

Abstract

The present invention provides a series of main materials of photoresist that are sensitive to multiple wavelengths, namely polymers represented by formula (I). It can be directly spin-coated into a film and applied in I-line, 193 nm lithography, electron beam lithography or extreme ultraviolet lithography. The polymer of the present invention is a non-chemically amplified photoresist, and the absorption wavelength of the polymer can be changed by functionalizing the polymerization monomers, so as to obtain a photoresist material that responds to multiple wavelengths.

Description

Technical Field

[0001] The present invention belongs to the technical field of materials, and particularly relates to a non-chemically amplified photoresist that meets multiple wavelength lithographies, a preparation method thereof, and an application thereof. Background Art

[0002] Photoresist materials are a type of thin film materials whose solubility changes after exposure to visible light, ultraviolet light, extreme ultraviolet light, electron beam or ion beam. After processes such as post-baking, developing, and etching, pattern transfer can be achieved. Among the photoresist materials used for semiconductor device processing, the resolution that can be achieved by G-line (436 nm) photoresist is above 0.5 μm, while the resolution that can be achieved by I-line (365 nm) photoresist is 0.3 - 0.5 μm. Both can be used for the production of larger area electronic products such as liquid crystal flat panel displays. As the exposure wavelength becomes shorter, KrF (248 nm) and ArF (193 nm) photoresists can respectively achieve resolutions of 110 nm and 65 nm. 193 nm immersion lithography can improve the resolution to 32 nm and can be used for the production of image sensors, power ICs, logic ICs, etc. Extreme ultraviolet (13.5 nm) photoresist can achieve a resolution of 32 nm and below, and is mainly used for the production of chips with 7 nm, 5 nm and below. Electron beam photoresist is mainly applied to the production of mask plates. There are dozens of lithography processes in the manufacturing process of large-scale integrated circuits. Different types of photoresists are required, different lithography wavelengths and lithography processes are needed, and the processes are relatively complex and the cost is high.

[0003] According to the reaction mechanism of photoresist after being exposed, photoresists can be divided into chemically amplified and non-chemically amplified photoresists. Chemically amplified photoresists usually consist of a solvent, a main material, a photoacid generator, and other additives. Because the photoacid generator generates acid after being exposed to catalyze the decomposition or cross-linking of the main material to produce solubility differences. This type of photoresist has high sensitivity, contrast, and resolution. However, due to the uneven mixing of the photoacid generator and other additives in the main material, the uneven diffusion of acid, etc., it will affect the line edge roughness of the lithography pattern, especially the high-resolution lithography stripes.

[0004] Non-chemically amplified photoresists include phenolic resin photoresists, polymethyl methacrylate and its derivative photoresists, sulfonium salt-based high-molecular or low-molecular photoresists, and metal organic compound photoresists, etc. They all have good thermal properties and lithography properties. The high-resolution lithography stripes obtained by this type of photoresist through electron beam or extreme ultraviolet lithography usually have very small line edge roughness.

[0005] Although non-chemically amplified photoresists have some performance advantages, however, how to prepare a non-chemically amplified photoresist that can achieve lithography at multiple wavelengths is a major research difficulty in the current lithography field. Summary of the Invention

[0006] To solve the above technical problems, the present invention provides a polymer represented by the following formula (I):

[0007]

[0008] Wherein:

[0009] x and y represent the molar fractions of two monomers in the polymer, 0.2 ≤ x ≤ 1, 0 ≤ y ≤ 0.8, and x + y = 1;

[0010] R is selected from

[0011] R 1 is selected from hydrogen, hydroxyl, CN, halogen, sodium sulfonate, C 1-12 alkyl, C 1-12 alkoxy, halo C 1-12 alkyl or -COC 1-12 alkyl;

[0012] R 2 , R 3 , R 4 , R 5 are the same or different and are independently selected from hydroxyl, CN, halogen, sodium sulfonate, C 1-12 alkyl, C 1-12 alkoxy, C 1-12 alkylthio, halo C 1-12 alkyl, 5-20 membered heteroaryl, -O-C 6-20 aryl, -O-5-20 membered heteroaryl, -O-C 1-12 alkyl-C 6-20 aryl, -O-5-20 membered heteroaryl, -O-C 1-12 alkyl-5-20 membered heteroaryl, -N(C 1-12 alkyl) 2 , -NHC 1-12 alkyl, -N(C 6-20 aryl) 2 , -NHC 6-20 aryl, -S-C 6-20 aryl or -COC 1-12 alkyl;

[0013] R 6 is selected from CN, C 1-12 alkyl, halo C 1-12 alkyl, C 6-20 aryl or 5-20 membered heteroaryl.

[0014] In some embodiments, R is selected from

[0015] R 1Selected from hydrogen, hydroxyl, sodium sulfonate, halogen, C 1-6 alkyl, C 1-6 alkoxy, halo C 1-6 alkyl or -COC 1-6 alkyl;

[0016] R 2 、R 3 、R 4 、R 5 are the same or different and are independently selected from hydrogen, hydroxyl, CN, halogen, C 1-6 alkyl, C 1-6 alkoxy, halo C 1-6 alkyl, C 1-6 alkylthio, 5- to 12-membered heteroaryl, -N(5- to 12-membered heteroaryl) 2 、-N(C 1-6 alkyl) 2 、-NHC 1-6 alkyl, -N(C 6-12 aryl) 2 、-NHC 6-12 aryl, -O-C 1-6 alkyl-C 6-12 aryl, -O-C 6-12 aryl, -S-C 6-12 aryl, -O-C 1-6 alkyl-5- to 12-membered heteroaryl or -COC 1-6 alkyl;

[0017] R 6 is selected from C 1-6 alkyl or halo C 1-6 alkyl.

[0018] In some embodiments, R 1 is selected from hydrogen, hydroxyl, halogen, sodium sulfonate, chloromethyl, bromomethyl, methyl, acetyl, trifluoromethyl or tert-butyl.

[0019] R 2 、R 3 、R 4 、R 5 are the same or different and are independently selected from hydrogen, halogen, methyl, methoxy, ethoxy, propoxy, butoxy, tert-butoxy, phenoxy, benzyloxy, dimethylamino, diethylamino, diphenylamino, carbazolyl, methylthio or phenylthio.

[0020] R 6 is selected from methyl or trifluoromethyl.

[0021] In some embodiments of the present invention, in the polymer, the molar ratio (x:y) of the two monomers is, for example, 1:0, 1:1, 2:1 or 1:4.

[0022] As an example, the polymer of the present invention has the structure shown below:

[0023]

[0024] Wherein, x and y are defined as above.

[0025] According to an embodiment of the present invention, the polymer shown in formula (I) is a copolymer, and the weight-average molecular weight of the copolymer is 5,000 - 100,000 Daltons, for example, 7,000 - 50,000 Daltons, such as 9,000, 14,000, 32,000 or 7,800 Daltons.

[0026] The present invention also provides a method for preparing the polymer shown in formula (I), comprising the following steps:

[0027] When y is 0 in the polymer shown in formula (I), the photosensitive monomer is directly polymerized to obtain the polymer shown in formula (I);

[0028] Or, when y is not 0 in the polymer shown in formula (I), the photosensitive monomer is copolymerized with the styrene monomer to obtain the polymer shown in formula (I);

[0029] Wherein the structure of the photosensitive monomer is shown in formula (III), and the structure of the styrene monomer is shown in formula (IV):

[0030]

[0031] Wherein, R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , x and y are defined as above.

[0032] According to an embodiment of the present invention, the preparation method of the compound of formula (III) is as follows:

[0033] The compound of formula (IV’) reacts with the compound of formula (V’) in dichloromethane, and the base is used as an acid-binding agent to prepare the compound of formula (III):

[0034]

[0035] Wherein, R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are defined as above.

[0036] According to an embodiment of the present invention, the method for preparing the compound of formula (IV') is as follows:

[0037] The compound of formula (V) and hydroxylamine hydrochloride are refluxed in ethanol to prepare the compound of formula (IV'):

[0038]

[0039] wherein, R 2 、R 3 、R 4 、R 5 、R 6 are as defined above.

[0040] According to an embodiment of the present invention, the compound of formula (V) can be directly purchased or prepared by the following method:

[0041] The compound of formula (VI) and p-toluenesulfonic acid or its hydrate are refluxed in chlorobenzene:

[0042]

[0043] wherein, R 2 、R 3 、R 4 、R 5 、R 6 are as defined above.

[0044] According to an embodiment of the present invention, the method for preparing the compound of formula (VI) is as follows:

[0045] The compound of formula (VII), the compound of formula (VII') and piperidine are refluxed in ethanol to prepare the compound of formula (VI):

[0046]

[0047] wherein, R 2 、R 3 、R 4 、R 5 、R 6 are as defined above.

[0048] The compound of formula (VII) can be directly purchased.

[0049] The present invention also provides the use of the polymer shown in the above formula (I) for preparing a photoresist.

[0050] In one embodiment, the photoresist is a single-component photoresist, which contains only the polymer shown in (I) except for the solvent.

[0051] The present invention also provides a photoresist composition, which includes the polymer shown in formula (I).

[0052] According to an embodiment of the present invention, the photoresist composition further includes a photoresist solvent.

[0053] In one embodiment, the photoresist solvent is selected from one, two or more of the following substances: ethyl lactate, butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol dimethyl ether, ethylene glycol monomethyl ether, cyclohexanone, methyl n-amyl ketone, methyl isopentyl ketone.

[0054] The present invention provides a photoresist film prepared by spin-coating the polymer represented by formula (I) in the present invention.

[0055] In one embodiment, the substrate can be a silicon wafer or the like.

[0056] The present invention provides the application of the photoresist film as described above in lithography.

[0057] In one embodiment, the lithography is I-line lithography, 193 nm lithography, electron beam lithography, extreme ultraviolet lithography, 248 nm lithography or 436 nm lithography.

[0058] The beneficial effects of the present invention are as follows:

[0059] The present invention provides a series of photoresist matrix materials that are sensitive to multiple wavelengths, namely the polymer represented by formula (I). It can be directly spin-coated into a film and applied in I-line, 193 nm lithography, electron beam or extreme ultraviolet lithography. The polymer of the present invention is a non-chemically amplified photoresist, and the absorption wavelength of the polymer can be changed by functionalizing the polymerization monomer, so as to obtain a photoresist material that responds to multiple wavelengths.

[0060] The polymer of the present invention has good solubility in various polar solvents, and a film can be prepared by a spin coating process. The polymer has good film-forming properties and meets the requirements of the lithography processing technology.

[0061] The polymer of the present invention can be applied to lithography of multiple wavelengths. It can not only achieve low-resolution I-line lithography, but also achieve high-resolution 193 nm, EUV and electron beam lithography. Using one photoresist to solve multiple process steps simplifies the process flow of electronic devices and can effectively reduce the device processing cost.

[0062] Term Definitions and Explanations

[0063] Unless otherwise defined, all scientific and technical terms herein have the same meaning as commonly understood by those skilled in the art to which the claimed subject matter belongs.

[0064] In this application, the at the partial substituents indicates the connection site.

[0065] "More than" means three or more.

[0066] The term "halogen" means F, Cl, Br or I.

[0067] The term "C 1-12 alkyl" should be understood to mean a straight-chain or branched-chain saturated monovalent hydrocarbon group having 1 to 12 carbon atoms. For example, "C 1-6 alkyl" means straight-chain and branched-chain alkyl groups having 1, 2, 3, 4, 5, or 6 carbon atoms. The alkyl groups are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl, etc. or their isomers.

[0068] The term "C 1-12 alkoxy" should be understood as -O-C 1-12 alkyl, where C 1-12 alkyl has the above definition.

[0069] The term "C 1-12 alkylthio" should be understood as -S-C 1-12 alkyl, where C 1-12 alkyl has the above definition.

[0070] The term "C 6-20 aryl" should be understood to mean a monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 20 carbon atoms and being monovalent aromatic or partially aromatic, preferably "C 6-14 aryl". The term "C 6-14 aryl" should be understood to preferably mean a monocyclic, bicyclic or tricyclic hydrocarbon ring having 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms and being monovalent aromatic or partially aromatic ("C 6-14 aryl"), especially a ring having 6 carbon atoms ("C 6 aryl"), such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C 9 aryl"), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 aryl"), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 aryl"), such as fluorenyl, or a ring having 14 carbon atoms ("C 14 aryl"), such as anthryl. When the C6-20 When the aryl is substituted, it can be mono-substituted or multi-substituted. Moreover, there is no restriction on the substitution site, for example, it can be ortho-substituted, para-substituted or meta-substituted.

[0071] The term "5- to 20-membered heteroaryl" should be understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O and S, such as "5- to 14-membered heteroaryl". The term "5- to 14-membered heteroaryl" should be understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: having 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, especially 5 or 6 or 9 or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3 heteroatoms independently selected from N, O and S and, additionally, 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, thia-4H-pyrazolyl, etc. and their benzo derivatives, such as benzofuryl, benzothienyl, benzoxazolyl, benzoisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl, etc.; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, etc., and their benzo derivatives, such as quinolinyl, quinazolinyl, isoquinolinyl, etc.; or azocinyl, indolizinyl, purinyl, etc. and their benzo derivatives; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, etc.

[0072] The above definition of the term "C 1-12 alkyl" also applies to other groups containing C 1-12 alkyl, such as halo C 1-12 alkyl, -COC 1-12 alkyl, -O-C 1-12 alkyl-C 6-20 aryl, -O-C 1-12 alkyl-5- to 20-membered heteroaryl, -N(C 1-12 alkyl) 2 、-NHC 1-12 alkyl or -COC 1-12 alkyl, etc.

[0073] Similarly, C 6-20 aryl, 5- to 20-membered heteroaryl, etc. have the same definition throughout the text. BRIEF DESCRIPTION OF THE DRAWINGS

[0074] Figure 1 It is the absorption spectrum of Polymer No.1 in acetonitrile solution.

[0075] Figure 2Planar view of the film prepared from Polymer No. 1 by atomic force scanning probe microscopy (AFM).

[0076] Figure 3 SEM image of I-line lithography stripes of Polymer No. 1

[0077] Figure 4 SEM image of electron beam lithography stripes of Polymer No. 1

[0078] Figure 5 SEM image of extreme ultraviolet lithography stripes of Polymer No. 1

[0079] Figure 6 SEM image of I-line lithography stripes of Polymer No. 3

[0080] Figure 7 SEM image of electron beam lithography stripes of Polymer No. 4 Detailed implementation mode

[0081] The technical solution of the present invention will be further described in detail below in combination with specific embodiments. It should be understood that the following embodiments are only used to illustrate and explain the present invention exemplarily, and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0082] Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products, or can be prepared by known methods.

[0083] Example 1

[0084] Prepare Polymer No. 1, and the specific synthesis route is as follows:

[0085]

[0086] Among them, x and y represent the molar fractions of two monomers in the polymer, x is 0.67, and y is 0.33; 1. Compound a 1 Synthesis

[0087] Dissolve 4-methoxy-2-hydroxybenzaldehyde (21.00 g) and ethyl trifluoroacetoacetate (28.00 g) in 200 mL of ethanol, add 1.37 mL of piperidine, react at 80 °C for 12 h, spin dry the solvent, extract with ethyl acetate / water, and dry with anhydrous magnesium sulfate. The obtained product is directly used in the next step.

[0088] 2. Compound b 1 Synthesis

[0089] Take Compound a1 (43.92 g) and p-toluenesulfonic acid monohydrate (2.63 g) were dissolved in 300 mL of chlorobenzene, and the temperature was raised to 130 °C for reaction for 6 h. After the chlorobenzene was evaporated to dryness, it was extracted with toluene and water, and then the water was separated with a water separator for 5 h. The solid precipitated by cooling was compound b. 1 。

[0090] The total yield of the first and second steps was 47%.

[0091] A small amount of the reaction solution of the first step was evaporated to a viscous state and then precipitated in petroleum ether to obtain a yellow solid, and its NMR was as follows

[0092] Compound a 1 : 1 H NMR (400 MHz, CDCl 3 ) δ 7.74 (s, 1H), 7.61 (s, 1H), 7.16 (d, 1H), 6.57 (s, 2H), 4.35 (q, 2H), 3.83 (s, 3H), 1.39 (t, 3H).

[0093] Compound b 1 : 1 H NMR (400 MHz, CDCl 3 ) δ 8.50 (s, 1H), 7.59 (d, 1H), 6.96 (d, 1H), 6.85 (s, 1H), 3.95 (s, 3H).

[0094] 3. Synthesis of compound c 1

[0095] Compound b 1 (15.00 g) was dispersed in 110 mL of ethanol, hydroxylamine hydrochloride (4.95 g) was added, and the mixture was refluxed for 6 hours. After partial ethanol was evaporated, water was added for precipitation, and the mixture was filtered by suction to obtain a yellow solid, which was dried by suction to obtain compound c 1 A total of 14.40 g was obtained, and the yield was 91%.

[0096] 1 H NMR (400 MHz, CDCl 3 ) δ 8.22 (s, 1H), 7.75 (s, 1H), 7.45 (d, 1H), 6.91 (d, 1H), 6.86 (s, 1H), 3.91 (s, 3H).

[0097] 4. Synthesis of 4-styrenesulfonyl chloride

[0098] Sodium 4-styrenesulfonate (10.00 g, 1 eq) and thionyl chloride (24.8 mL, 7 eq) were added to a 250 mL three-necked flask. 15 mL of DMF was slowly added, and then the reaction was carried out overnight at room temperature. The reaction was quenched with cold water, and the reaction solution was extracted with DCM, dried over anhydrous magnesium sulfate, and the solvent was evaporated to obtain a yellow liquid.

[0099] 1 H NMR (400 MHz, CDCl 3 ) δ 7.70 (d, 2H), 7.61 (d, 2H), 6.83–6.75 (m, 1H), 5.96 (d, 1H), 5.52 (d, 1H).

[0100] 5. Synthesis of Compound d 1

[0101] Compound c 1 (9.37 g, 1 eq) and 4-styrenesulfonyl chloride (>8.38 g, 1.44 eq) were dispersed in 100 mL of DCM, and then 7.4 mL, 1.94 eq of triethylamine was added dropwise. The reaction was carried out at room temperature. After 3 h, the reaction solution was extracted with DCM, and column chromatography was carried out with V EA:PE = 1:20, and then column chromatography was carried out with V EA:PE = 1:10 and V DCM:PE = 1:1 to obtain a white solid. The impurities were recrystallized from DCM, and a total of 9.73 g was obtained with a yield of 69%.

[0102] 1 H NMR (400 MHz, CDCl 3 ) δ 7.96 (d, 2H), 7.75 (s, 1H), 7.59 (d, 2H), 7.47 (d, 1H), 6.93 (dd, 1H), 6.85 (d, 1H), 6.78 (dd, 1H), 5.95 (d, 1H), 5.51 (d, 1H), 3.92 (s, 3H).

[0103] 6. Synthesis of Polymer No.1

[0104] Compound d 1 (2.00 g), styrene (0.20 g) and AIBN (22 mg, 1 wt%) were dispersed in 7 mL of tetrahydrofuran. After freeze-pumping three times, the reaction was carried out at 70 °C for 24 h, and the product was precipitated with petroleum ether. The monomers were removed by silica gel column chromatography, and the column was washed with tetrahydrofuran. The product was precipitated in petroleum ether to obtain 1.73 g with a yield of 78%, x:y = d 1 :styrene = 2:1, Mw = 8.6 w.

[0105] 1 H NMR (400 MHz, DMSO-d 6 ​)δ 8.15–6.09 (m, 21H), 3.70 (s, 6H).

[0106] Example 2

[0107] Prepare Polymer No. 2, and the specific synthesis route is as follows:

[0108]

[0109] Among them, x and y represent the molar fractions of two monomers in the polymer, x is 0.5, and y is 0.5;

[0110] 1. Compound a 2 Synthesis

[0111] Dissolve 4-(diethylamino)-2-hydroxybenzaldehyde (10.00 g) and ethyl trifluoroacetoacetate (10.49 g) in 100 mL of ethanol, add 0.52 mL of piperidine, react at 80 °C for 24 h. After rotary evaporation of the solvent, it is a gel-like liquid, dissolve it with a small amount of DCM, precipitate it in 200 mL of petroleum ether, and filter to obtain 14.88 g of yellow powder, with a yield of 80%.

[0112] 1 H NMR (400 MHz, CDCl 3 ) 7.75 (s, 1H), 7.52 (d, 1H), 6.89 (d, 1H), 6.62 (s, 2H), 4.28 (q, 2H), 3.45 (q, 4H), 1.36 (t, 3H), 1.12 (t, 6H).

[0113] 2. Compound b 2 Synthesis

[0114] Dissolve Compound a 2 (14.00 g) and p-toluenesulfonic acid monohydrate (0.74 g) in 140 mL of chlorobenzene, heat up to 130 °C and react for 12 h. After rotary evaporation of chlorobenzene, extract with toluene and water, and then use a water separator to separate water for 5 h. Cool the precipitated solid, and 7.90 g is Compound b 2 , with a yield of 65%.

[0115] 1 H NMR (400 MHz, CDCl 3 ) 7.71 (s, 1H), 7.46 (d, 1H), 6.87 (d, 1H), 6.83 (s, 1H), 3.43 (q, 4H), 1.10 (t, 6H).

[0116] 3. Compound c 2 Synthesis

[0117] Dissolve Compound b 2(7.90 g) was dispersed in 80 mL of ethanol. Hydroxylamine hydrochloride (2.26 g) was added, and the mixture was refluxed for 10 hours. After partially spinning off the ethanol, water was added for precipitation. The mixture was filtered by suction to obtain a yellow solid, which was then dried by suction to obtain Compound c. 2 The total amount was 7.62 g, and the yield was 92%.

[0118] 1 H NMR (400 MHz, CDCl 3 ) δ 8.40 (s, 1H), 7.72 (s, 1H), 7.44 (d, 1H), 6.89 (d, 1H), 6.85 (s, 1H), 3.42 (q, 4H), 1.13 (t, 6H).

[0119] 4. Synthesis of 4 - styrenesulfonyl chloride

[0120] It was consistent with the synthesis method in Step 3 of Example 1.

[0121] 5. Synthesis of Compound d 2

[0122] Compound c 2 (7.62 g, 1 eq) and 4 - styrenesulfonyl chloride (6.79 g) were dispersed in 80 mL of DCM, and then 6.24 mL of triethylamine was added dropwise. The reaction was carried out at room temperature. After 4 h, it was extracted with DCM, dried over anhydrous magnesium sulfate, and purified by column chromatography to obtain a white solid. Then it was recrystallized with DCM to obtain a total of 6.31 g of the product, and the yield was 55%.

[0123] 1 H NMR (400 MHz, CDCl 3 ) δ 7.76 (d, 2H), 7.71 (s, 1H), 7.62 (d, 2H), 7.45 (d, 1H), 6.90 (dd, 1H), 6.83 (d, 1H), 6.72 (dd, 1H), 5.84 (d, 1H), 5.32 (d, 1H), 3.42 (q, 4H), 1.13 (t, 6H).

[0124] 6. Synthesis of Polymer No. 2

[0125] Compound d 2 (5.00 g), 4 - chloromethylstyrene (0.78 g) and AIBN (0.58 g, 10 wt%) were dispersed in 18 mL of tetrahydrofuran. The mixture was frozen and evacuated three times, and then reacted at 70 °C for 24 h. After cooling, it was precipitated in petroleum ether. The monomer was removed by silica gel column, the column was rinsed with tetrahydrofuran, and the product was precipitated in petroleum ether to obtain 5.09 g of the product, and the yield was 80%, x:y = d 2 : 4 - chloromethylstyrene = 1:1, Mw = 32,000.

[0126] 11H NMR (400 MHz, DMSO-d 6 ) δ 8.20–6.13 (m, 12H), 4.66 (s, 2H), 3.39 (s, 4H). Example 3

[0127] Prepare Polymer No. 3, and the specific synthesis route is as follows:

[0128]

[0129] Among them, x and y represent the molar fractions of two monomers in the polymer, x is 0.2, and y is 0.8;

[0130] 1. Synthesis of Compound a 3 Synthesis

[0131] Disperse 3-acetyl-2H-chromen-2-one (9.00 g) in 90 mL of ethanol, add hydroxylamine hydrochloride (4.28 g), reflux for 10 hours, spin out part of the ethanol, add water to precipitate, filter by suction to obtain a yellow solid, and dry by suction to obtain Compound a 3 A total of 9.03 g, with a yield of 93%.

[0132] 1 1H NMR (400 MHz, CDCl 3 ) δ 8.45 (s, 1H), 7.70 (s, 1H), 7.54 (d, 1H), 7.43 (d, 1H), 6.86 (d, 1H), 6.79 (s, 1H), 2.46 (s, 3H).

[0133] 2. Synthesis of Compound b 3 Synthesis

[0134] Disperse Compound a 3 (5.00 g) and 4-vinylbenzoyl chloride (5.91 g) in 50 mL of DCM, then dropwise add 6.82 mL of triethylamine, react at room temperature, extract with DCM after 3 h, dry with anhydrous magnesium sulfate, and column chromatograph to obtain a white solid, and then recrystallize with DCM to obtain a total of 4.92 g of the product, with a yield of 60%.

[0135] 1 1H NMR (400 MHz, CDCl 3 ) δ 7.74 (d, 2H), 7.70 (s, 1H), 7.61 (d, 2H), 7.56 (d, 1H), 7.42 (d, 1H), 6.87 (d, 1H), 6.84 (d, 1H), 6.70 (dd, 1H), 5.82 (d, 1H), 5.29 (d, 1H), 2.48 (s, 3H).

[0136] 3. Synthesis of Polymer No. 3

[0137] Compound b 3 (3.00 g), 4-tert-butylstyrene (3.37 g) and AIBN (1.27 g, 20 wt%) were dispersed in 23 mL of tetrahydrofuran, freeze-pumped three times, and then reacted at 70 °C for 24 h. After cooling, it was precipitated in petroleum ether. The monomer was removed by silica gel column chromatography, the column was flushed with tetrahydrofuran, and the product was precipitated in petroleum ether to obtain 6.78 g of the product, with a yield of 85%, x:y = b 3 :4-tert-butylstyrene = 2:8, Mw = 1.4 w.

[0138] 1 H NMR (400 MHz, DMSO-d 6 ) δ8.24–6.10 (m, 50H), 2.48 (s, 6H).

[0139] Example 4

[0140] Prepare Polymer No. 4, and the specific synthesis route is as follows:

[0141]

[0142] Among them, x is 1, indicating that the molar fraction of monomer d 1 in Polymer No. 4 is 100%;

[0143] 1. Synthesis of Compound a 1 -d 1 The synthesis of

[0144] Compound a 1 -d 1 is the same as the synthesis route in Example 1.

[0145] 2. Synthesis of Polymer No. 4

[0146] Compound d 1 (2.00 g) and AIBN (400 mg, 20 wt%) were dispersed in 7 mL of tetrahydrofuran, freeze-pumped three times, and then reacted at 70 °C for 24 h, and precipitated with petroleum ether. The monomer was removed by silica gel column chromatography, the column was flushed with tetrahydrofuran, and the product was precipitated in petroleum ether to obtain 1.15 g of the product, with a yield of 48%, Mw = 7.8 k.

[0147] 1 H NMR (400 MHz, DMSO-d 6 ) δ8.12–6.07 (m, 8H), 3.72 (s, 3H).

[0148] Example 5

[0149] Measure the ultraviolet absorption of the polymer resin (Polymer No. 1) prepared in Example 1, see attached Figure 1, The result shows that it has strong absorption at 250 - 400 nm and can be applied to I-line lithography and deep ultraviolet lithography.

[0150] Example 6

[0151] Dissolve Polymer No.1 in Example 1 in propylene glycol monomethyl ether acetate (PGMEA) to prepare a 40 mg / mL solution. Filter it through a 0.22 μm pore size filter membrane, spin-coat it on a silicon wafer to form a film, scan the film surface with an atomic force microscope, and analyze the film uniformity. Rq = 0.29, proving that the film has good uniformity. The plan view is shown in the appendix Figure 2 .

[0152] Example 7

[0153] I-line lithography: Dissolve Polymer No.1 in Example 1 in propylene glycol monomethyl ether acetate (PGMEA) with a solid content of 30 mg / mL. Filter it through a 0.22 μm pore size filter membrane, spin-coat it on a silicon wafer, and pre-bake it at 100 °C for 180 seconds. Perform I-line lithography on the prepared film to obtain a lithography stripe with a stripe width of nearly 1 μm and an exposure period of 2 μm. See the appendix Figure 3 .

[0154] Example 8

[0155] Electron beam lithography: Dissolve Polymer No.1 in Example 1 in propylene glycol monomethyl ether acetate (PGMEA) with a solid content of 25 mg / mL. Filter the photoresist solution through a 0.22 μm pore size filter membrane, spin-coat it on a silicon wafer, and pre-bake it at 100 °C for 180 seconds. Use the prepared film for electron beam lithography to obtain a lithography stripe with a period of 50 nm. See the appendix Figure 4 .

[0156] Example 9

[0157] Extreme ultraviolet lithography: Dissolve Polymer No.1 in Example 1 in propylene glycol monomethyl ether acetate (PGMEA) with a solid content of 22 mg / mL. Filter the photoresist solution through a 0.22 μm pore size filter membrane, spin-coat it on a silicon wafer, and pre-bake it at 100 °C for 180 seconds. Use the prepared film for extreme ultraviolet lithography to obtain a lithography stripe with a period of 50 nm. See the appendix Figure 5 .

[0158] Example 10

[0159] I-line lithography: Dissolve Polymer No.3 in Example 3 in propylene glycol monomethyl ether acetate (PGMEA) with a solid content of 35 mg / mL. Filter it through a 0.22 μm pore size filter membrane, spin-coat it on a silicon wafer, and pre-bake it at 100 °C for 180 seconds. Perform I-line lithography on the prepared film to obtain a lithography stripe with a stripe width of nearly 1 μm and an exposure period of 2 μm. See the appendix Figure 6。

[0160] Example 11

[0161] Electron beam lithography: Dissolve Polymer No. 4 in Example 4 in propylene glycol monomethyl ether acetate (PGMEA) with a solid content of 25 mg / mL, filter it with a 0.22-μm pore size filter membrane, spin-coat it on a silicon wafer, and pre-bake it at 100 °C for 180 seconds. The prepared thin film is subjected to electron beam lithography, and lithography stripes with a period of 44 nm can be obtained. See the appendix Figure 7 。

[0162] In summary, the polymers of the present invention can be applied to lithography of multiple wavelengths, and can not only achieve low-resolution I-line lithography, but also achieve high-resolution 193 nm, EUV, and electron beam lithography, etc.

[0163] The above describes the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. The polymer shown in formula (I): （I）； Wherein: x and y represent the molar fractions of two monomers in the polymer, 0.2 ≤ x ≤ 1, 0 ≤ y ≤ 0.8, and x + y = 1; R is selected from or ; R 1 selected from hydrogen, hydroxyl, CN, halogen, sodium sulfonate, C 1-12 alkyl, C 1-12 alkoxy, halo-C 1-12 alkyl or -COC 1-12 alkyl; R 2 、R 3 、R 4 、R 5 are the same or different and are each independently selected from hydrogen, hydroxyl, CN, halogen, sodium sulfonate, C 1-12 alkyl, C 1-12 alkoxy, C 1-12 alkylthio, halo-C 1-12 alkyl, 5-20-membered heteroaryl, -O-C 6 - 20 aryl, -O-5-20-membered heteroaryl, -O-C 1-12 alkyl-C 6 - 20 aryl, -O-C 1-12 alkyl-5-20-membered heteroaryl, -N(C 1-12 alkyl) 2 、-NHC 1-12 alkyl, -N(C 6 - 20 aryl) 2 、-NHC 6 - 20 aryl, -S-C 6 - 20 aryl or -COC 1-12 alkyl; R 6 Selected from CN, C 1-12 alkyl, halo C 1-12 alkyl, C 6 - 20 aryl or 5-20 membered heteroaryl.

2. The polymer according to claim 1, wherein, R is selected from or ; R 1 selected from hydrogen, hydroxyl, sodium sulfonate, halogen, C 1-6 alkyl, C 1-6 alkoxy, halo-C 1-6 alkyl or -COC 1-6 alkyl; R 2 、R 3 、R 4 、R 5 are the same or different and are each independently selected from hydrogen, hydroxyl, CN, halogen, C 1-6 alkyl, C 1-6 alkoxy, halo-C 1-6 alkyl, C 1-6 alkylthio, 5- to 12-membered heteroaryl, -N(C 1-6 alkyl) 2 , -NHC 1-6 alkyl, -N(C 6 - 12 aryl) 2 , -NHC 6 - 12 aryl, -O-C 1-6 alkyl-C 6 - 12 aryl, -O-C 6 - 12 aryl, -S-C 6 - 12 aryl, -O-C 1-6 alkyl-5- to 12-membered heteroaryl or -COC 1-6 alkyl; R 6 selected from C 1-6 alkyl or halo C 1-6 alkyl.

3. The polymer according to claim 2, wherein, R 1 selected from hydrogen, hydroxy, halogen, sodium sulfonate, chloromethyl, bromomethyl, methyl, acetyl, trifluoromethyl or tert-butyl; R 2 、R 3 、R 4 、R 5 are the same or different and are each independently selected from hydrogen, halogen, methyl, methoxy, ethoxy, propoxy, butoxy, tert-butoxy, phenoxy, benzyloxy, dimethylamino, diethylamino, diphenylamino, carbazolyl, methylthio or phenylthio; R 6 Selected from methyl or trifluoromethyl.

4. The polymer according to any one of claims 1 - 3, wherein, The polymer has the structure shown below: ； Wherein, x and y represent the molar fractions of two monomers in the polymer, 0.2 ≤ x ≤ 1, 0 ≤ y ≤ 0.8, and x + y = 1.

5. The polymer according to claim 1, wherein, The weight - average molecular weight of the polymer shown in formula (I) is 5000 - 100000 Daltons.

6. The polymer according to any one of claims 1 - 3, wherein, The molar ratio of x to y is (0.1 - 6):(0 - 1).

7. The preparation method of the polymer according to any one of claims 1 - 6, wherein, Comprises the following steps: When y in the polymer shown in formula (I) is 0, the photosensitive monomer is directly polymerized to obtain the polymer shown in formula (I); Or, when y in the polymer shown in formula (I) is not 0, the photosensitive monomer and the styrene - type monomer are copolymerized to obtain the polymer shown in formula (I); wherein the structure of the photosensitive monomer is shown in formula (III), and the structure of the styrene - type monomer is shown in formula (IV): ； Among them, R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , x, and y have the definitions described in any one of claims 1-5.

8. A photoresist composition, which comprises the polymer shown in formula (I) according to any one of claims 1 - 6.

9. A photoresist film, which is prepared by spin - coating the polymer shown in formula (I) according to any one of claims 1 - 6.

10. The application of the polymer according to any one of claims 1 - 6 in lithography, and the lithography is I - line lithography, 193nm lithography, 248nm lithography, 436nm lithography, electron beam lithography or extreme ultraviolet lithography.

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