A self-degrading polymer based on polybenzyl ether, its preparation method, and a non-chemically amplified photoresist containing the same.

Abstract

This invention discloses a self-decomposing polymer based on polybenzyl ether, its preparation method, and a non-chemical amplification photoresist containing the polymer. The polymer has a general structure as shown in one of the following structures, which can be used as a host material for a single-component non-chemical amplification photoresist. When the prepared polymer film is exposed, cascade self-decomposition occurs through the departure of end groups and the electronic resonance rearrangement of the polybenzyl ether backbone along the main chain, generating low-molecular-weight monomers. This creates a solubility difference between the exposed and unexposed areas, avoiding the low sensitivity problem of traditional non-chemical amplification photoresists. While achieving high sensitivity, the decomposition reaction is confined to a single polymer molecule, resulting in a pattern with low line edge roughness and high resolution. (I, II, III, IV)

Description

Technical Field

[0001] This invention relates to the field of photolithography materials technology. More specifically, it relates to a self-decomposing polymer based on polybenzyl ether, its preparation method, and a non-chemically amplifying photoresist containing the same. Background Technology

[0002] Photoresist, also known as photoresist, is a type of thin-film material whose solubility changes after being irradiated by energy such as light beams, electron beams, or ion beams. It is an indispensable core material in the microelectronics industry for manufacturing large-scale and very large-scale integrated circuits. The photolithography process involves coating photoresist onto the surface of a substrate such as a semiconductor, conductor, or insulator. After exposure and development, the remaining portion protects the underlying layer. Etching then transfers the desired micro-pattern from the photomask to the substrate. Therefore, photoresist is a key material in device microfabrication technology. The rapid development of the semiconductor industry has placed increasingly higher demands on photolithography technology. From the earliest phenolic resin-diazonaphthoquinone photoresists (436nm g-line and 365nm i-line), to deep ultraviolet (248nm and 193nm) photoresists, and then to extreme ultraviolet (13.5nm) and electron beam photoresists, various photolithography materials with different structures and reaction mechanisms have been continuously developed to meet the requirements of different exposure wavelengths and increasingly higher resolution.

[0003] Currently, conventional photoresists are mainly divided into two types: chemical amplification and non-chemical amplification. Conventional high-resolution photoresists still use chemical amplification photoresists, which are generally mixtures. The main components are a resin host material containing acid-sensitive groups, a photoacid generator (PAG), and corresponding additives. "Chemical amplification" refers to the generation of acid by the photoacid generator after light exposure, which triggers a series of chemical reactions, allowing a small number of photons to produce significant changes in solubility. This results in high sensitivity, but also problems such as acid diffusion and uneven component distribution, leading to higher roughness at the edges of the lithographic pattern.

[0004] In contrast, non-chemical amplification photoresists contain photosensitive groups that directly undergo photochemical reactions during exposure, creating a difference in solubility between exposed and unexposed areas. These non-chemical amplification photoresists do not require the addition of acid-generating agents, eliminating problems related to acid diffusion and uneven component distribution. They can produce lithographic patterns with low edge roughness and high resolution, but correspondingly, their sensitivity is lower. Therefore, maximizing sensitivity while maintaining the low edge roughness and high resolution characteristics of non-chemical amplification photoresists is key to expanding their applications. Summary of the Invention

[0005] To address the problems existing in the prior art, the first objective of this invention is to provide a self-immolative polymer based on polybenzyl ether. This polymer can be used as a host material for non-chemically amplified photoresists, enabling the prepared polymer films to simultaneously possess high sensitivity, low line edge roughness, and high resolution.

[0006] A second objective of this invention is to provide a method for preparing the self-decomposing polymer as described above.

[0007] The third objective of this invention is to provide a non-chemical amplification photoresist.

[0008] The fourth objective of this invention is to provide a photoresist coating.

[0009] A fifth object of the present invention is to provide the application of a polymer, a non-chemically amplified photoresist, or a photoresist coating in the preparation of photolithographic patterns.

[0010] To achieve the first objective mentioned above, the present invention adopts the following technical solution:

[0011] This invention discloses a self-degrading polymer based on polybenzyl ether, wherein the polymer has a general formula structure as shown in one of the following structures:

[0012] I, II. III. IV;

[0013] In this context, R1 and R2 each independently represent H or C. 1-10 Alkoxy groups, R1 and R2, can connect to each other to form a five-membered or six-membered ring structure containing 1-2 O atoms;

[0014] R3 represents C 1-10 alkyl;

[0015] R4 and R5 are substituents on the benzene ring, with R4 representing H or C. 1-10 Alkyl group, R5 represents H, -OC (=O)-C 3-10 cycloalkyl, -OC 1-10 Alkyl-C 2-10 alkenyl, -OC 1-10 Alkyl-C 6-10 Any of the aryl groups;

[0016] The value of n is a positive integer ranging from 5 to 2000.

[0017] The end-group structure of the polymer described in this invention is as follows:

[0018] IR, II-R,

[0019] III-R, IV-R

[0020] These end-group structures, acting as leaving groups (LGs), undergo photochemical reactions upon irradiation with ultraviolet (365 nm), deep ultraviolet (248 nm and 193 nm), extreme ultraviolet (13.5 nm), and electron beams. The bonds between these LGs and the polymer backbone break, and the remaining polymer segments undergo electronic resonance rearrangement along the backbone, cascading and self-decomposing into smaller molecular weight monomers V.

[0021] ;

[0022] In this context, R1 and R2 each independently represent H or C. 1-10 Alkyl groups, R1 and R2, can connect to each other to form a five- or six-membered ring structure containing 1-2 oxygen atoms; R3 represents C. 1-10 Alkyl group; R4 and R5 are substituents on the benzene ring, where R4 represents H or C. 1-10 Alkyl group, R5 represents H, -OC (=O)-C 3-10 cycloalkyl, -OC 1-10 Alkyl-C 2-10 alkenyl, -OC 1-10 Alkyl-C 6-10 Any of the aryl groups.

[0023] The polymer described in this invention exhibits high photolithography sensitivity due to the leaving characteristics of its end groups under irradiation by ultraviolet (365nm), deep ultraviolet (248nm and 193nm), extreme ultraviolet (13.5nm) and electron beams, as well as the cascade self-decomposition characteristics resulting from electron resonance rearrangement along the main chain. It also possesses excellent film-forming properties due to its polymer characteristics. Furthermore, the variability of the side chain groups R4 and R5 in the polymer repeating unit allows for flexible control of its glass transition temperature, adhesion to the substrate, mechanical strength, thermal stability, solubility, film-forming properties, and etching resistance, making it suitable for photolithography processing.

[0024] Term "C" 1-10 "Alkyl" should be understood as referring to a straight-chain or branched saturated monovalent hydrocarbon group having 1-10 carbon atoms. For example, "C 1-6"Alkyl" means a straight-chain or branched alkyl group having 1, 2, 3, 4, 5 or 6 carbon atoms, such as 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.

[0025] Term "C" 1-10 "Alkoxy" should be understood as -OC 1-10 Alkyl, wherein C 1-10 Alkyl groups have the above definition.

[0026] Term "C" 3-10 "Cycloalkyl" should be understood as referring to a saturated monovalent monocyclic, bicyclic, or polycyclic hydrocarbon ring (also called a fused ring hydrocarbon ring) with 3-10 carbon atoms. Bicyclic or polycyclic cycloalkyl includes fused cycloalkyl, bridged cycloalkyl, and spirocyclic cycloalkyl; fused ring refers to a fused ring structure formed by two or more cyclic structures sharing two adjacent ring atoms (i.e., sharing a bond). Bridged ring refers to a fused ring structure formed by two or more cyclic structures sharing two non-adjacent ring atoms. Spirocyclic refers to a fused ring structure formed by two or more cyclic structures sharing a single ring atom.

[0027] Term "C" 2-10 "Alkenyl" should be understood as referring to a straight-chain or branched unsaturated hydrocarbon group having 2-10 carbon atoms and containing at least one carbon-carbon double bond (C=C). For example, "C 2-5"Alkenyl" refers to a straight-chain or branched alkenyl group having 2, 3, 4, or 5 carbon atoms and containing at least one carbon-carbon double bond (C=C), such as vinyl, propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, etc. 3-Butenyl, 1-methyl-1-propenyl, 1-ethyl vinyl, 1-methyl-2-propenyl, 2,2-dimethyl-vinyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-3-butenyl, 1-ethyl-2-propenyl, 1-n-propyl vinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-ethyl-1-propenyl, 2-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropyl vinyl, 2-isopropyl vinyl, 2-methyl-2-butenyl, 1,2-dimethyl-1-propenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,2-dimethyl-2-propenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, etc., or their isomers.

[0028] Term "C" 6-10 "Aryl" should be understood to refer to a monocyclic, bicyclic, or tricyclic hydrocarbon ring having 6-10 carbon atoms, exhibiting monovalent aromatic or partially aromatic properties, particularly a ring with 6 carbon atoms ("C6 aryl"), such as phenyl; or a ring with 9 carbon atoms ("C9 aryl"), such as indenyl or indenyl; or a ring with 10 carbon atoms ("C9 aryl"). 10 Aryl groups, such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl.

[0029] The term "C" above 1-10 The definition of "alkyl" also applies to other C-containing compounds. 1-10 Alkyl groups, such as -OC(=O)-C 1-10 Alkyl groups, etc.

[0030] Similarly, C 6-10 Aryl, C 2-10 alkenyl, C 3-10 The cycloalkyl group has the same definition throughout the text.

[0031] Furthermore, the polydispersity index (PDI) of the polymer is ≤2.00, for example, the polydispersity index (PDI) of the polymer is between 1.00 and 1.50, or between 1.00 and 1.30, etc.

[0032] Furthermore, the M of the polymer n For 1000-800000 Daltons, such as 1000-400000 Daltons, such as 1000-80000 Daltons, such as 1000-40000 Daltons; M wThe range is 1,000-1,000,000 Daltons, such as 1,000-500,000 Daltons, such as 1,000-100,000 Daltons, such as 1,000-50,000 Daltons.

[0033] Furthermore, the value of n can be a positive integer from 5 to 1000, a positive integer from 10 to 900, a positive integer from 10 to 800, a positive integer from 100 to 600, etc.

[0034] Furthermore, the polymer described in Formula I is selected from one of the following structures:

[0035]

[0036] .

[0037] Furthermore, the polymer described in Formula II is selected from one of the following structures:

[0038]

[0039] .

[0040] Furthermore, the polymer described in Formula III is selected from one of the following structures:

[0041]

[0042] .

[0043] Furthermore, the polymer described in Formula IV is selected from one of the following structures:

[0044] .

[0045] To achieve the second objective mentioned above, the present invention adopts the following technical solution:

[0046] This invention discloses a method for preparing the polymer as described above, using monomer V for homopolymerization; when the polymer is selected from the structure of formula I, the method includes the following steps:

[0047] Add monomer V to reaction flask A, dissolve it in ultra-dry tetrahydrofuran, and cool it to -40 to -20°C.

[0048] Compound P2-t-Bu and methanol were added to reaction flask B, diluted with ultra-dry tetrahydrofuran, and reacted for 0.5-1 h. The solution was then transferred to reaction flask A and reacted at -40 to -20 °C for 1-3 h.

[0049] After the reaction was completed, the reaction solution was transferred to another reaction flask containing compounds IR-Br and DMAP and filled with N2. The reaction was carried out at -40 to -20°C for 0.5-1 h, then slowly raised to room temperature and continued to react for 9-20 h.

[0050] The reaction solution was precipitated three times in methanol at -30 to -20°C to obtain the polymer shown in Formula I.

[0051] The structures of monomer V and compound IR-Br are shown below:

[0052] ;

[0053] The molar ratio of compound P2-t-Bu, methanol, and monomer V is 1:1-10:10-100;

[0054] The molar ratio of compound IR-Br, DMAP and monomer V is 1:1:2-50.

[0055] Furthermore, when the polymer is selected from the structure of formula II, the following steps are included:

[0056] Add monomer V to reaction flask A, dissolve it in ultra-dry tetrahydrofuran, and cool it to -40 to -20°C.

[0057] Compound P2-t-Bu and methanol were added to reaction flask B, diluted with ultra-dry tetrahydrofuran, and reacted for 0.5-1 h. The solution was then transferred to reaction flask A and reacted at -40 to -20 °C for 1-3 h.

[0058] After the reaction was completed, the reaction solution was transferred to another reaction flask containing compound II-R-Cl and DMAP and filled with N2. The reaction was carried out at -40 to -20°C for 0.5-1 h, then slowly raised to room temperature and continued to react for 9-20 h.

[0059] The reaction solution was precipitated three times in methanol at -30 to -20°C to obtain the polymer shown in Formula II.

[0060] The structures of monomer V and compound II-R-Cl are shown below:

[0061] ;

[0062] The molar ratio of compound P2-t-Bu, methanol, and monomer V is 1:1-10:10-100;

[0063] The molar ratio of compound II-R-Cl, DMAP, and monomer V is 1:1:2-50.

[0064] Furthermore, when the polymer is selected from the structure of formula III, the following steps are included:

[0065] Add monomer V to reaction flask A, dissolve it in ultra-dry tetrahydrofuran, and cool it to -40 to -20°C.

[0066] Compound P2-t-Bu and methanol were added to reaction flask B, diluted with ultra-dry tetrahydrofuran, and reacted for 0.5-1 h. The solution was then transferred to reaction flask A and reacted at -40 to -20 °C for 1-3 h.

[0067] After the reaction was completed, the reaction solution was transferred to another reaction flask containing compound III-R-Br and DMAP and filled with N2. The reaction was carried out at -40 to -20°C for 0.5-1 h, then slowly raised to room temperature and continued to react for 9-20 h.

[0068] The reaction solution was precipitated three times in methanol at -30 to -20°C to obtain the polymer shown in Formula III.

[0069] The structures of monomer V and compound III-R-Br are shown below:

[0070] ;

[0071] The molar ratio of compound P2-t-Bu, methanol, and monomer V is 1:1-10:10-100;

[0072] The molar ratio of compound III-R-Br, DMAP, and monomer V is 1:1:2-50.

[0073] Furthermore, when the polymer is selected from the IV structure, the following steps are included:

[0074] Add monomer V to reaction flask A, dissolve it in ultra-dry tetrahydrofuran, and cool it to -40 to -20°C.

[0075] Compound P2-t-Bu and methanol were added to reaction flask B, diluted with ultra-dry tetrahydrofuran, and reacted for 0.5-1 h. The solution was then transferred to reaction flask A and reacted at -40 to -20 °C for 1-3 h.

[0076] After the reaction was completed, the reaction solution was transferred to another reaction flask containing compound IV-R-Br and DMAP and filled with N2. The reaction was carried out at -40 to -20°C for 0.5-1 h, then slowly raised to room temperature and continued to react for 9-20 h.

[0077] The reaction solution was precipitated three times in methanol at -30 to -20°C to obtain the polymer shown in Formula IV.

[0078] The structures of monomer V and compound IV-R-Br are shown below:

[0079] ;

[0080] The molar ratio of compound P2-t-Bu, methanol, and monomer V is 1:1-10:10-100;

[0081] The molar ratio of compound IV-R-Br, DMAP, and monomer V is 1:1:2-50.

[0082] To achieve the third objective mentioned above, the present invention adopts the following technical solution:

[0083] This invention discloses a non-chemical amplification photoresist, which is a positive photoresist composition. By weight percentage, the non-chemical amplification photoresist comprises 0.1-10 wt% of the polymer described above, which is used as the host material of the non-chemical amplification photoresist.

[0084] Furthermore, by weight percentage, the non-chemical amplification photoresist also includes a solvent;

[0085] The solvent is selected from one or more of propylene glycol methyl ether acetate, propylene glycol methyl ether, N,N-dimethylformamide, cyclohexanone, cyclopentanone, ethyl n-pentanone, ethyl isopentanone, ethanol, acetonitrile, isopropanol, acetone, methyl n-pentanone, methyl isopentanone, anisole, and 1,2-dichloroethane.

[0086] In one embodiment of the present invention, the non-chemical amplification photoresist is a single-component photoresist composed of the polymer and solvent as described above. That is, the non-chemical amplification photoresist contains only one photoresist component other than the solvent, and does not contain an acid-generating agent other than the polymer as described above.

[0087] To achieve the fourth objective mentioned above, the present invention adopts the following technical solution:

[0088] This invention discloses a photoresist coating comprising the non-chemical amplification photoresist as described above.

[0089] Furthermore, the non-chemical amplification photoresist is applied to the substrate surface using a spin coating method to obtain a photoresist coating.

[0090] Furthermore, the substrate is made of silicon wafer or ITO glass.

[0091] Furthermore, the photoresist coating is a thin film of 20-150 nm, for example, the photoresist coating is a 30 nm thin film.

[0092] To achieve the fifth objective mentioned above, the present invention adopts the following technical solution:

[0093] This invention discloses the application of the polymer, non-chemical amplification photoresist, or photoresist coating as described above in the preparation of photolithographic patterns.

[0094] According to the present invention, the polymer, non-chemical amplification photoresist or photoresist coating can be used in modern photolithography technologies such as 365nm photolithography, 248nm photolithography, 193nm photolithography, extreme ultraviolet (EUV) photolithography, nanoimprint lithography or electron beam lithography; it is especially suitable for high-resolution photolithography technologies such as 193nm, electron beam lithography and extreme ultraviolet (EUV) lithography.

[0095] The polymer of this invention has a large molecular weight. When the polymer film is exposed, the end groups of the polymer undergo photochemical reactions and leave. The remaining chain segments undergo cascade self-decomposition through electronic resonance rearrangement along the main chain, generating monomers with small molecular weights. By selecting a solvent that can dissolve the small molecule monomers but not the polymer (e.g., methanol, ethanol, n-propanol) for development, the polymer can be used as the host material for positive photoresist.

[0096] The beneficial effects of this invention are as follows:

[0097] (1) The present invention provides a series of self-decomposing polymers based on polybenzyl ether, which can be used as host materials for non-chemically amplified photoresists, and the raw materials required for their preparation are cheap and readily available, and the synthesis process is simple.

[0098] (2) The polymer provided by this invention has good solubility in various commonly used solvents and can be used to prepare good thin films by spin-coating, which is suitable for the requirements of photolithography. This polymer can be used as the main material of single-component non-chemical amplification photoresist, avoiding the problems of uneven distribution of acid-generating agents and anti-acid diffusion agents in chemical amplification photoresists, uneven acid diffusion, and low sensitivity in traditional non-chemical amplification photoresists. The resulting pattern has high resolution and low line edge roughness.

[0099] (3) The polymer provided by the present invention uses polybenzyl ether as the basic skeleton. It has the cascade self-decomposition characteristics brought about by the electronic resonance rearrangement along the main chain. After the end group is exposed and leaves, it can be completely decomposed into small molecular weight monomers, which greatly improves the sensitivity of the photolithography material. At the same time, the decomposition reaction is confined to a single polymer molecule, reducing the roughness of the line edge.

[0100] (4) The polymer provided by the present invention uses radiation-sensitive groups as end groups. When exposed to ultraviolet light (365nm), deep ultraviolet light (248nm and 193nm), extreme ultraviolet light (13.5nm) and electron beam, the end groups undergo photochemical reactions and leave, so that the polymer can undergo self-decomposition under different irradiation conditions. Therefore, it is suitable for modern photolithography technologies such as 365nm photolithography, 248nm photolithography, 193nm photolithography, extreme ultraviolet (EUV) photolithography, nanoimprint lithography or electron beam lithography.

[0101] (5) The polymer provided by the present invention can be modified by different side chain groups R4 and R5 in the polymer repeating unit to control its glass transition temperature, adhesion between photoresist and substrate, mechanical strength, thermal stability, solubility, film formation and etching resistance, etc., and flexibly control its comprehensive performance, expand the application range of the material and meet the requirements of photolithography process.

[0102] (6) The polymer provided by the present invention can adjust its PDI by adjusting the temperature, time and other conditions of the polymerization process, so that the PDI is as low as 1.1, avoiding the large line edge roughness caused by the wide distribution of polymer molecular weight in conventional polymer photoresists.

[0103] (7) The polymer, non-chemical amplification photoresist or photoresist coating described in this invention are applicable to modern photolithography technologies such as 365nm photolithography, 248nm photolithography, 193nm photolithography, extreme ultraviolet (EUV) photolithography, nanoimprint lithography or electron beam lithography; especially applicable to high-resolution photolithography technologies such as 193nm, electron beam lithography and extreme ultraviolet (EUV) lithography. Attached Figure Description

[0104] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.

[0105] Figure 1 The differential scanning calorimetry curve and thermogravimetric curve are shown for polymer I-1 in Example 1 of the present invention.

[0106] Figure 2 The differential scanning calorimetry (DSC) curve and thermogravimetric analysis (TGA) curve of polymer I-5 in Example 2 of this invention are shown.

[0107] Figure 3 The differential scanning calorimetry (DSC) curve and thermogravimetric analysis (TGA) curve of polymer II-8 in Example 5 of this invention are shown.

[0108] Figure 4 The differential scanning calorimetry (DSC) curve and thermogravimetric analysis (TGA) curve of polymer II-12 in Example 6 of this invention are shown.

[0109] Figure 5 The differential scanning calorimetry (DSC) curve and thermogravimetric analysis (TGA) curve of polymer III-6 in Example 9 of this invention are shown.

[0110] Figure 6 The differential scanning calorimetry (DSC) curve and thermogravimetric curve of polymer IV-1 in Example 10 of this invention are shown.

[0111] Figure 7 This is an atomic force microscope (AFM) scan of the surface morphology of the thin film prepared by spin coating of polymer I-1 in Example 1 of the present invention.

[0112] Figure 8 This is an AFM scan of the surface morphology of the thin film prepared by spin coating of polymer I-5 in Example 2 of the present invention.

[0113] Figure 9 This is an AFM scan of the surface morphology of the thin film prepared by spin coating of polymer II-8 in Example 5 of the present invention.

[0114] Figure 10 This is an AFM scan of the surface morphology of the thin film prepared by spin coating of polymer II-12 in Example 6 of the present invention.

[0115] Figure 11 This is an AFM scan of the surface morphology of the thin film prepared by spin coating of polymer III-6 in Example 9 of the present invention.

[0116] Figure 12 This is an AFM scan of the surface morphology of the thin film prepared by spin coating of polymer IV-1 in Example 10 of the present invention.

[0117] Figure 13 This is a scanning electron microscope (SEM) image of the photolithographic stripes (exposure period of 50 nm) of polymer I-1 used as a positive photoresist in Example 1 of the present invention.

[0118] Figure 14 This is an SEM image of the photolithographic stripes (exposure period of 50nm) of polymer I-5 used as positive photoresist in Example 2 of the present invention.

[0119] Figure 15 This is a SEM image of the photolithographic stripes (exposure period of 60nm) of polymer II-8 used as a positive photoresist in Example 5 of the present invention.

[0120] Figure 16 This is a SEM image of the photolithographic stripes (exposure period of 60nm) of polymer II-12 used as a positive photoresist in Example 6 of the present invention.

[0121] Figure 17 This is a SEM image of the photolithographic stripes (exposure period of 60nm) of polymer III-6 used as a positive photoresist in Example 9 of the present invention.

[0122] Figure 18 This is a SEM image of the photolithographic stripes (exposure period of 60nm) of polymer IV-1 used as a positive photoresist in Example 10 of the present invention. Detailed Implementation

[0123] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments and accompanying drawings, further explains the invention. Similar components in the drawings are indicated by the same reference numerals. Those skilled in the art should understand that the specific description below is illustrative rather than restrictive and should not be construed as limiting the scope of protection of the present invention.

[0124] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0125] Example 1

[0126] The synthetic route for preparing compound VII-1 is as follows:

[0127]

[0128] 2,6-Dimethylphenol (12.2 g, 100 mmol, 1.0 eq) was added to a single-necked flask and dissolved with 20 mL of pyridine by stirring. Benzoyl chloride (15.5 g, 110 mmol, 1.1 eq) was added dropwise under ice bath conditions. After the mixture was brought back to room temperature and stirred for 2 h, it was diluted with ethyl acetate, washed five times with H2O, dried over anhydrous Na2SO4, filtered, and the solvent was removed by vacuum distillation of the filtrate. The mixture was then transferred to a double-necked flask, and 25 mL of trifluoromethanesulfonic acid was added under ice bath and N2 protection. The temperature was raised to 60 °C and the reaction was carried out for 12 h. After cooling to room temperature, the reaction mixture was poured into H2O at 0 °C and extracted once with ethyl acetate. The aqueous phase was adjusted to weakly acidic with NaHCO3 solution and then extracted with ethyl acetate until no absorption was observed in the organic phase under TLC monitoring. The combined organic phases were dried over anhydrous Na2SO4, filtered, and the filtrate was evaporated to dryness to obtain the crude product. The product was precipitated in petroleum ether and filtered to obtain 20.2 g of pink powder, with a yield of 89%.

[0129] 1 H NMR (CDCl3, 400 MHz) δ 7.76-7.74 (m, 2H), 7.59-7.55 (m, 1H), 7.52(s, 2H), 7.52-7.45 (m, 2H), 5.95 (s, 1H), 2.29 (s, 6H); 13 C NMR (CDCl3, 400MHz) δ 196.6, 157.0, 138.4, 132.0, 131.8, 129.9, 129.4, 128.3, 123.2, 16.1.

[0130] The synthetic route for preparing compound VI-1 is as follows:

[0131]

[0132] Compound VII-1 (15 g, 66 mmol, 1.0 eq) was added to a Schlenk flask and dissolved with 120 mL of ethanol by stirring. The process of vacuuming and purging with nitrogen was repeated three times. Under N2 protection, a Pd / C catalyst (5% of the mass of compound VII-1) was added. The process of vacuuming and purging with hydrogen was repeated three times. The reaction solution was bubbled with H2 and stirred vigorously. After the reaction was completed, Pd / C was removed by diatomaceous earth filtration. The filtrate was concentrated by rotary evaporation and column chromatography to give 13 g of a white solid, with a yield of 92%.

[0133] 1 H NMR (CDCl3, 400 MHz) δ 7.99-7.88 (m, 5H), 7.51 (s, 2H), 4.52 (s,2H), 2.88 (s, 6H); 13 C NMR (CDCl3, 400 MHz) δ 151.0, 142.6, 133.3, 129.3,129.1, 128.8, 126.2, 123.5, 41.5, 16.1.

[0134] The synthetic route for preparing compound V-1 is as follows:

[0135]

[0136] Compound III-1 (7 g, 33 mmol, 1.0 eq) was added to a Schlenk flask and dissolved with 250 mL of diethyl ether. Potassium hydroxide (7.77 g, 138 mmol, 4.2 eq) and potassium ferricyanide (43.43 g, 132 mmol, 4.0 eq) were dissolved in 175 mL of H₂O and poured into a constant-pressure dropping funnel. After three cycles of vacuuming and nitrogen purging, the funnel was opened, and the aqueous phase was added all at once. The reaction was vigorously stirred for 1 hour under N₂ protection. The mixture was extracted with Et₂O and H₂O, and the aqueous phase was extracted three times with Et₂O. The combined organic phases were washed once with saturated brine, dried over anhydrous Na₂SO₄, filtered, and the filtrate was distilled under reduced pressure to remove the solvent. The filtrate was then subjected to column chromatography (petroleum ether:dichloromethane = 1:1, v / v) to give 6.24 g of a yellow needle-like solid, in 90% yield.

[0137] 1 H NMR (CDCl3, 400 MHz) δ 7.51 (s, 1H), 7.45-7.38 (m, 5H), 7.15 (s, 1H), 7.04 (s, 1H), 2.05 (s, 6H); 13C NMR (CDCl3, 400 MHz) δ 187.75, 143.1,139.3, 138.0, 136.2, 136.0, 132.2, 131.8, 130.9, 129.7, 129.2, 17.3, 16.7.

[0138] The synthetic route for preparing polymer I-1 is as follows:

[0139]

[0140] Place Schlenk flasks A and B in a forced-air drying oven to dry, then place them in a glove box to cool. Inside the glove box, add compound V-1 (1.4 g, 6.7 mmol, 1.0 eq) to flask A and dissolve it with 2.5 mL of ultra-dry THF. Using two microsyringes, add P2-t-Bu (35 μL, 0.07 mmol, 0.01 eq) and freshly distilled methanol (5.2 μL, 0.13 mmol, 0.02 eq) to flask B and dilute with 1 mL of ultra-dry THF. Bottles A and B were sealed with rubber stoppers and transferred to a fume hood. Bottle A was cooled to -20°C. The solution in bottle B was slowly added dropwise to bottle A using a syringe. After stirring for 70 min, the reaction mixture was transferred to a Schlenk flask containing compound Ia-Br (145 mg, 0.67 mmol, 0.1 eq) and DMAP (82 mg, 0.67 mmol, 0.1 eq) and purged with N2. The mixture was stirred for 1 h, then cooled to room temperature and reacted for another 14 h. The reaction mixture was diluted with 8 mL of THF and added dropwise to 125 mL of methanol frozen at -20°C to precipitate the solid. After settling at -20°C for 20 min, the solid was centrifuged, the supernatant was discarded, and the solid was dissolved in THF. This "dissolution-precipitation-centrifugation" process was repeated three times to obtain 0.95 g of a white solid, with a yield of 68%. n =3.9×10 3 M w =4.9×10 3 PDI=1.25.

[0141] Example 2

[0142] The synthetic route for preparing compound VII-2 is as follows:

[0143]

[0144] 2,6-Dimethylphenol (36.66 g, 300 mmol, 1.0 eq) was added to a round-bottom flask and dissolved in 250 mL of petroleum ether. Then, 51 mL of 37% formaldehyde aqueous solution (678 mmol, 2.26 eq) was added. Next, 55 mL of concentrated hydrochloric acid was slowly added using a constant-pressure dropping funnel, and the reaction was stirred vigorously at room temperature. After 5 hours, stirring was stopped, and the reaction solution was poured into 400 mL of water. The mixture was stirred for 20 minutes, filtered, and the filtered solid was washed three times with H₂O. The solid was then placed in a vacuum drying oven and dried overnight at 70 °C to obtain 38.24 g of a white solid, with a yield of 99%.

[0145] 1 H NMR (CDCl3, 400 MHz): δ 6.79 (s, 4H), 4.46 (s, 2H), 3.70 (s, 2H), 2.20 (s, 12H); 13 C NMR (CDCl3, 101 MHz): δ 150.3, 133.4, 128.9, 122.9, 40.3,15.9; EI-MS: Calculated ([M]): 256.35, found: 256.20.

[0146] The synthetic route for preparing compound VI-2 is as follows:

[0147]

[0148] Compound VII-2 (5.13 g, 20 mmol, 1.0 eq) and 1-adamantaneformyl chloride (4.37 g, 22 mmol, 1.1 eq) were added to a single-necked flask and dissolved with 80 mL of dichloromethane by stirring. Triethylamine (3.67 g, 36 mmol, 1.8 eq) was slowly added dropwise to the flask at room temperature, and the reaction was allowed to proceed for 13 h at room temperature. The reaction was quenched with 1 M hydrochloric acid, extracted three times with dichloromethane, and the combined organic phases were washed with saturated brine, dried over Na₂SO₄ or MgSO₄, filtered, and the filtrate was distilled under reduced pressure to remove the solvent. Column chromatography (petroleum ether:ethyl acetate = 30:1) gave 4 g of a white solid, in 48% yield.

[0149] 1 H NMR (DMSO-d6, 400 MHz): δ 6.89 (s, 2H), 6.74 (s, 2H), 3.65 (s, 2H), 2.11 (s, 6H), 2.04-2.00 (m, 9H), 1.98 (s, 6H), 1.73 (s, 6H); 13C NMR (DMSO-d6,400 MHz): δ 174.4, 151.5, 150.5, 135.0, 133.3, 130.0, 128.8, 127.9, 125.1,42.9, 41.5, 38.9, 37.4, 29.3, 16.0, 15.4.

[0150] The synthetic route for preparing compound V-2 is as follows:

[0151]

[0152] Compound VI-2 (3.3 g, 7.9 mmol, 1.0 eq) was added to a Schlenk flask and dissolved with 120 mL of diethyl ether. Potassium hydroxide (1.86 g, 33.2 mmol, 4.2 eq) and potassium ferricyanide (10.38 g, 31.5 mmol, 4.0 eq) were dissolved in 45 mL of H₂O and poured into a constant-pressure dropping funnel. After three cycles of vacuum evacuation and nitrogen purging, the funnel was opened, and the aqueous phase was added all at once. The mixture was stirred vigorously under N₂ protection and reacted at room temperature for 1 hour. The mixture was extracted with Et₂O and H₂O, and the aqueous phase was extracted three times with Et₂O. The combined organic phases were washed with saturated brine, dried over anhydrous Na₂SO₄, filtered, and the filtrate was distilled under reduced pressure to remove the solvent, yielding 2.83 g of a yellow solid (86% yield).

[0153] 1 H NMR (DMSO-d6, 400 MHz): δ 7.65 (s, 1H), 7.36 (d, 2H, J=4Hz), 7.31(s, 2H), 2.12 (s, 6H), 2.06 (s, 9H), 1.98 (s, 3H), 1.95 (s, 3H), 1.75 (s,6H); 13 C NMR (DMSO-d6, 400 MHz): δ 186.7, 174.4, 152.3, 143.1, 138.6, 132.2,130.5, 129.0, 127.1, 125.9, 42.9, 38.9, 37.4, 29.3, 16.0, 15.8.

[0154] The synthetic route for preparing polymer I-5 is as follows:

[0155]

[0156] Place Schlenk flasks A and B in a forced-air drying oven to dry, then place them in a glove box to cool. Inside the glove box, add compound V-2 (1.67 g, 4.0 mmol, 1.0 eq) to flask A and dissolve it with 20 mL of ultra-dry THF. Using two microsyringes, add P2-t-Bu (40 μL, 0.08 mmol, 0.02 eq) and freshly distilled methanol (16 μL, 0.40 mmol, 0.1 eq) to flask B and dilute with 1 mL of ultra-dry THF. Bottles A and B were sealed with rubber stoppers and transferred to a fume hood. Bottle A was cooled to -20°C. The solution in bottle B was transferred to bottle A using a double-ended needle. After stirring for 2 hours, the reaction solution was transferred using a double-ended needle to another Schlenk flask containing compound Ib-Br (110 mg, 0.4 mmol, 0.1 eq) and DMAP (49 mg, 0.4 mmol, 0.1 eq) and purged with N2. The mixture was stirred for 0.5 hours, then cooled to room temperature and reacted for another 20 hours. The reaction solution turned into a light green turbid liquid. The reaction solution in the flask was diluted with 8 mL of THF and then added dropwise to 100 mL of methanol frozen at -20°C to precipitate the solid. After settling at -20°C for 20 minutes, the solid was centrifuged, the supernatant was discarded, and the solid was dissolved in THF. This "dissolution-precipitation-centrifugation" operation was repeated three times to obtain 1.01 g of white solid, with a yield of 60%. n =7.8×10 3 M w =1.1×10 4 PDI=1.41.

[0157] Example 3

[0158] The synthetic route for preparing compound VI-3 is as follows:

[0159]

[0160] Compound VII-2 (3.0 g, 11.7 mmol, 1.0 eq) was added to a two-necked flask and dissolved in 10 mL of dry DMF to form a colorless, slightly yellow solution. Under nitrogen protection, K₂CO₃ (1.78 g, 12.9 mmol, 1.1 eq) was added, and the mixture was stirred for 60 min. Allyl bromopropene (1.42 g, 11.7 mmol, 1.0 eq) was diluted in 5 mL of dry DMF and slowly added dropwise to the two-necked flask using a constant-pressure dropping funnel under nitrogen protection. After purging with nitrogen for 10 min, the mixture was heated to 60 °C and stirred overnight. The reaction mixture was diluted with an appropriate amount of ethyl acetate and washed twice successively with saturated NH₄Cl solution, H₂O, and saturated brine. The organic phase was dried over anhydrous Na₂SO₄, filtered, and the filtrate was distilled under reduced pressure to remove the solvent, yielding the crude product. Column chromatography (petroleum ether:ethyl acetate = 10:1, v / v) yielded 1.65 g of a green oil, with a yield of 48%.

[0161] 1 H NMR (CDCl3, 400 MHz): δ 6.83 (d, 2H), 6.81 (d, 2H), 6.12 (m, 2H), 5.43 (d, 1H, J=16Hz), 5.26 (d, 1H, J=8Hz), 4.29 (d, 2H, J=4Hz), 3.73 (s, 2H),2.25 (s, 6H), 2.22 (s, 6H); 13 C NMR (CDCl3, 400 MHz): δ 153.6, 150.3,, 135.1, 133.7, 133.6, 129.0, 128.8, 128.2, 125.1, 117.9, 72.2, 41.3, 16.1, 16.0.

[0162] The synthetic route for preparing compound V-3 is as follows:

[0163]

[0164] Compound VI-3 (2.0 g, 6.7 mmol, 1.0 eq) was added to a Schlenk flask and dissolved with 25 mL of diethyl ether. Potassium hydroxide (1.59 g, 28.3 mmol, 4.2 eq) and potassium ferricyanide (8.89 g, 27 mmol, 4.0 eq) were dissolved in 30 mL of H₂O and poured into a constant pressure dropping funnel. After five cycles of vacuum evacuation and nitrogen purging, the aqueous phase was added all at once, and the reaction was stirred for 3 h under N₂ atmosphere. The aqueous phase was separated, extracted three times with Et₂O, and the organic phases were combined, dried over anhydrous MgSO₄, filtered, and the solvent was removed by vacuum distillation of the filtrate to give a yellow solid. Column chromatography (petroleum ether:dichloromethane = 1:1, v / v) gave 1.0 g of yellow solid, with a yield of 50%.

[0165] 1 H NMR (DMSO-d6, 400 MHz): δ 7.66 (s, 1H), 7.32 (d, 2H, J=12Hz), 7.27(d, 2H, J=15Hz), 6.11 (m, 1H), 5.45 (d, 1H, J=16Hz), 5.26 (d, 1H, J=12Hz),4.37 (d, 2H, J=8Hz), 2.28 (s, 6H), 1.98 (s, 3H), 1.94(s, 3H); 13C NMR (DMSO-d6, 400 MHz): δ 186.4, 154.7, 143.6, 138.3, 133.6, 132.5, 131.9, 129.2, 128.9, 127.0, 125.7, 117.9, 72.2, 16.4, 15.8.

[0166] The synthetic route for preparing polymer I-9 is as follows:

[0167]

[0168] Place Schlenk flasks A and B in a forced-air drying oven to dry, then place them in a glove box to cool. Inside the glove box, add compound V-3 (0.44 g, 1.5 mmol, 1.0 eq) to flask A and dissolve it with 8 mL of ultra-dry THF. Using two microsyringes, add P2-t-Bu (15 μL, 0.03 mmol, 0.02 eq) and freshly distilled methanol (6 μL, 0.15 mmol, 0.1 eq) to flask B and dilute with 1 mL of ultra-dry THF. Bottles A and B were sealed with rubber stoppers and transferred to a fume hood. Bottle A was cooled to -18°C. The solution in bottle B was transferred to bottle A using a double-ended needle. After stirring at -18°C for 1.5 h, the reaction solution was transferred using a double-ended needle to another Schlenk flask containing compound Ic-Br (39 mg, 0.15 mmol, 0.1 eq) and DMAP (18 mg, 0.15 mmol, 0.1 eq) and purged with N2. The mixture was stirred for 0.5 h, then cooled to room temperature and reacted for another 20 h. The reaction solution turned into a green turbid liquid. The reaction solution in the flask was added dropwise to 100 mL of methanol frozen at -20°C to precipitate the solid. After settling at -20°C for 20 min, the solid was centrifuged, the supernatant was discarded, and the solid was dissolved in THF. This "dissolution-precipitation-centrifugation" operation was repeated three times to obtain 0.064 g of green solid, with a yield of 15%. n =4.2×10 3 M w =6.2×10 3 PDI=1.48.

[0169] Example 4

[0170] The synthetic route for preparing polymer II-4 is as follows:

[0171]

[0172] Place Schlenk flasks A and B in a forced-air drying oven to dry, then place them in a glove box to cool. Inside the glove box, add compound V-2 (0.62 g, 1.5 mmol, 1.0 eq) to flask A and dissolve it with 8 mL of ultra-dry THF. Using two microsyringes, add P2-t-Bu (15 μL, 0.03 mmol, 0.02 eq) and freshly distilled methanol (1.2 μL, 0.03 mmol, 0.02 eq) to flask B and dilute with 1 mL of ultra-dry THF. Seal bottles A and B with rubber stoppers and transfer them to a fume hood. Cool bottle A to -18°C. Use a double-ended needle to transfer the solution from bottle B to bottle A. Stir the reaction for 1.5 h. Then, use a double-ended needle to transfer the reaction solution to another Schlenk flask containing compound II-a-Cl (32 mg, 0.15 mmol, 0.1 eq) and DMAP (18 mg, 0.15 mmol, 0.1 eq) and purged with N2. Stir for 0.5 h, then return to room temperature and continue the reaction for 20 h. The reaction solution turns into a yellow turbid liquid. Add the reaction solution dropwise to 100 mL of methanol frozen at -20°C to precipitate the solid. After settling at -20°C for 20 min, centrifuge and discard the supernatant. Dissolve the solid in THF. Repeat this "dissolve-precipitate-centrifuge" operation three times to obtain 0.4 g of white solid, with a yield of 65%. n =9.6×10 3 M w =1.1×10 4 PDI=1.15.

[0173] Example 5

[0174] The synthetic route for preparing polymer II-8 is as follows:

[0175]

[0176] Place Schlenk flasks A and B in a forced-air drying oven to dry, then place them in a glove box to cool. Inside the glove box, add compound V-3 (1.18 g, 4 mmol, 1.0 eq) to flask A and dissolve it with 5 mL of ultra-dry THF. Using two microsyringes, add P2-t-Bu (40 μL, 0.08 mmol, 0.02 eq) and freshly distilled methanol (3.2 μL, 0.08 mmol, 0.02 eq) to flask B and dilute with 1 mL of ultra-dry THF. Bottles A and B were sealed with rubber stoppers and transferred to a fume hood. Bottle A was cooled to -30°C. The solution in bottle B was transferred to bottle A using a double-ended needle. After stirring for 2 hours, the reaction solution was transferred using a double-ended needle to another Schlenk flask containing compound II-b-Cl (110 mg, 0.4 mmol, 0.1 eq) and DMAP (49 mg, 0.4 mmol, 0.1 eq) and purged with N2. The mixture was stirred for 0.5 hours, then cooled to room temperature and reacted for another 20 hours, resulting in a yellow turbid liquid. The reaction solution was added dropwise to 100 mL of methanol frozen at -20°C to precipitate the solid. After settling at -20°C for 20 minutes, the solid was centrifuged, the supernatant was discarded, and the solid was dissolved in THF. This "dissolution-precipitation-centrifugation" process was repeated three times to obtain 0.34 g of a green solid, with a yield of 29%. n =5.3×10 3 M w =7.6×10 3 PDI=1.43.

[0177] Example 6

[0178] The synthetic route for preparing compound VI-4 is as follows:

[0179]

[0180] Compound VII-2 (2.05 g, 8 mmol, 1.0 eq) and K₂CO₃ (1.22 g, 8.8 mmol, 1.1 eq) were added to a two-necked flask and dissolved in 8 mL of dry acetone to form a colorless, slightly yellow solution. The mixture was stirred for 30 min. Benzyl bromide (1.23 g, 7.2 mmol, 0.9 eq) was diluted in 4 mL of dry acetone and slowly added dropwise using a constant-pressure dropping funnel. After the addition was complete, the mixture was stirred at 55 °C for 24 h. The solution was diluted with ethyl acetate and washed twice successively with saturated NH₄Cl solution, H₂O, and saturated brine. The organic phase was dried over anhydrous Mg₂SO₄, filtered, and the filtrate was concentrated by rotary evaporation to obtain the crude product. Column chromatography (petroleum ether:ethyl acetate = 50:1, v / v) yielded 1.14 g of a yellow-green solid, with a yield of 41%.

[0181] 1H NMR (CDCl3, 400 MHz): δ 7.49 (d, 2H, J=4Hz), 7.41 (t, 2H, J=6Hz), 7.35 (t, 1H, J=4Hz), 6.85 (s, 1H), 6.82 (s, 1H), 4.79 (s, 2H), 3.75 (s, 2H),2.28 (s, 6H), 2.23 (s, 6H); 13 C NMR (CDCl3, 400 MHz): δ 153.5, 150.7, 136.7,135.0, 133.5, 129.2, 128.8, 128.5, 128.0, 127.8, 124.8, 80.0, 41.5, 16.0.

[0182] The synthetic route for preparing compound V-4 is as follows:

[0183]

[0184] Compound VI-4 (2.14 g, 6.18 mmol, 1.0 eq) was dissolved in 60 mL of diethyl ether with stirring in a Schlenk flask. Potassium hydroxide (1.38 g, 24.6 mmol, 4.0 eq) and potassium ferricyanide (7.73 g, 24 mmol, 4.0 eq) were dissolved in 50 mL of H2O and poured into a constant pressure dropping funnel. After repeating the vacuum-nitrogen purging process five times, the aqueous phase was added, and the reaction was stirred for 0.5 h under a N2 atmosphere. The mixture was extracted with dichloromethane and H2O, and the aqueous phase was extracted three times with dichloromethane. The combined organic phases were dried over anhydrous MgSO4, filtered, and the filtrate was concentrated by rotary evaporation to give 2.14 g of a yellow solid, with a yield of 99%.

[0185] 1 H NMR (DMSO-d6, 400 MHz): δ 7.68 (s, 1H), 7.51 (d, 2H, J=4Hz), 7.43(t, 2H, J=4Hz), 7.38 (t, 1H, J=6Hz), 7.34 (d, 2H, J=8Hz), 7.30 (d, 2H, J=28Hz), 4.87 (s, 2H), 2.31 (s, 6H), 1.99 (s, 3H), 1.95(s, 3H); 13C NMR (DMSO-d6,400 MHz): δ185.7, 154.7, 144.7, 137.8, 136.7, 132.2, 130.8, 129.5, 128.6,128.5, 128.0, 127.8, 126.6, 125.9, 80.0, 16.3, 15.8.

[0186] The synthetic route for preparing polymer II-12 is as follows:

[0187]

[0188] Place Schlenk bottles A and B in a forced-air drying oven to dry. In a glove box, add compound V-4 (1.72 g, 5 mmol, 1.0 eq) to bottle A and dissolve it with 7 mL of ultra-dry THF. Use two microsyringes to add P2-t-Bu (50 μL, 0.1 mmol, 0.02 eq) and freshly distilled methanol (4 μL, 0.1 mmol, 0.02 eq) to bottle B and dilute with 1.5 mL of ultra-dry THF. Seal bottles A and B with rubber stoppers and transfer them to a fume hood. Cool bottle A to -30°C. Use a double-ended needle to transfer the solution from bottle B to bottle A. Stir the reaction for 2 hours. Then, use a double-ended needle to transfer the reaction solution to another Schlenk flask containing compound II-c-Cl (130 mg, 0.5 mmol, 0.1 eq) and DMAP (61 mg, 0.5 mmol, 0.1 eq) and purged with N2. Stir for 1 hour, then return to room temperature and continue the reaction for 15 hours. The reaction solution turns into a yellow turbid liquid. Add the reaction solution dropwise to 100 mL of methanol frozen at -20°C to precipitate the solid. Centrifuge and dissolve the solid in THF. Repeat this "dissolve-precipitate-centrifuge" operation three times to obtain 1.7 g of white solid, with a yield of 99%. n =1.3×10 4 M w =1.4×10 4 PDI=1.07.

[0189] Example 7

[0190] The synthetic route for preparing polymer III-10 is as follows:

[0191]

[0192] Place Schlenk bottles A and B in a forced-air drying oven to dry. In a glove box, add compound V-4 (1.38 g, 4 mmol, 1.0 eq) to bottle A and dissolve it with 7 mL of ultra-dry THF. Use two microsyringes to add P2-t-Bu (40 μL, 0.08 mmol, 0.02 eq) and freshly distilled methanol (3.2 μL, 0.08 mmol, 0.02 eq) to bottle B and dilute with 1 mL of ultra-dry THF. Bottles A and B were sealed with rubber stoppers and transferred to a fume hood. Bottle A was cooled to -20°C. The solution in bottle B was transferred to bottle A using a double-ended needle. After stirring for 2.5 h, the reaction solution was transferred using a double-ended needle to another Schlenk flask containing compound III-c-Br (122 mg, 0.4 mmol, 0.1 eq) and DMAP (49 mg, 0.4 mmol, 0.1 eq) and purged with N2. The mixture was stirred for 0.5 h, then cooled to room temperature and reacted for another 19 h. The reaction solution turned into a pale yellow turbid liquid. The reaction solution in the flask was added dropwise to 100 mL of methanol frozen at -20°C to precipitate the solid. After centrifugation, the solid was dissolved in THF. This "dissolve-precipitate-centrifuge" operation was repeated three times to obtain 1.13 g of white solid, with a yield of 82%. n =6.7×10 3 M w =9.0×10 3 PDI=1.33.

[0193] Example 8

[0194] The synthetic route for preparing polymer III-2 is as follows:

[0195]

[0196] Place Schlenk flasks A and B in a forced-air drying oven to dry, then place them in a glove box to cool. Inside the glove box, add compound V-1 (2.1 g, 10 mmol, 1.0 eq) to flask A and dissolve it with 2 mL of ultra-dry THF. Using two microsyringes, add P2-t-Bu (100 μL, 0.2 mmol, 0.02 eq) and freshly distilled methanol (14 μL, 0.35 mmol, 0.035 eq) to flask B and dilute with 2 mL of ultra-dry THF. Bottles A and B were sealed with rubber stoppers and transferred to a fume hood. Bottle A was cooled to -20°C. The solution in bottle B was slowly added dropwise to bottle A using a syringe. After stirring for 70 min, the reaction mixture was transferred to a Schlenk flask containing compound III-b-Cl (320 mg, 1 mmol, 0.1 eq) and DMAP (122 mg, 1 mmol, 0.1 eq) and purged with N2. The mixture was stirred for 0.5 h, then cooled to room temperature and reacted for another 9 h. The reaction mixture was diluted with 10 mL of THF and added dropwise to 125 mL of methanol frozen at -20°C to precipitate the solid. After settling at -20°C for 20 min, the solid was centrifuged, the supernatant was discarded, and the solid was dissolved in THF. This "dissolution-precipitation-centrifugation" process was repeated three times to obtain 1.2 g of white solid, with a yield of 57%. n =4.9×10 3 M w =6.6×10 3 PDI=1.35.

[0197] Example 9

[0198] The synthetic route for preparing polymer III-6 is as follows:

[0199]

[0200] Place Schlenk flasks A and B in a forced-air drying oven to dry, then place them in a glove box to cool. Inside the glove box, add compound V-2 (2.08 g, 5.0 mmol, 1.0 eq) to flask A and dissolve it with 4 mL of ultra-dry THF. Using two microsyringes, add P2-t-Bu (50 μL, 0.1 mmol, 0.02 eq) and freshly distilled methanol (4 μL, 0.1 mmol, 0.02 eq) to flask B and dilute with 2 mL of ultra-dry THF. Bottles A and B were sealed with rubber stoppers and transferred to a fume hood. Bottle A was cooled to -30°C. The solution in bottle B was slowly added dropwise to bottle A using a syringe. After stirring for 2 hours, the reaction mixture was transferred to a Schlenk flask containing compound III-c-Br (175 mg, 0.5 mmol, 0.1 eq) and DMAP (61 mg, 0.5 mmol, 0.1 eq) and purged with N2. The mixture was stirred for 1 hour, then cooled to room temperature and reacted for another 20 hours. The reaction mixture was then added dropwise to 125 mL of methanol frozen at -20°C to precipitate the solid. After centrifugation, the supernatant was discarded, and the solid was dissolved in THF. This "dissolution-precipitation-centrifugation" process was repeated three times to obtain 1.78 g of a white solid, with a yield of 86%. n =3.8×10 3 M w =4.9×10 3 PDI=1.29.

[0201] Example 10

[0202] The synthetic route for preparing polymer IV-1 is as follows:

[0203]

[0204] Place Schlenk flasks A and B in a forced-air drying oven to dry, then place them in a glove box to cool. Inside the glove box, add compound V-1 (1.05 g, 5.0 mmol, 1.0 eq) to flask A and dissolve it with 2.5 mL of ultra-dry THF. Using two microsyringes, add P2-t-Bu (50 μL, 0.1 mmol, 0.02 eq) and freshly distilled methanol (5 μL, 0.13 mmol, 0.02 eq) to flask B and dilute with 1 mL of ultra-dry THF. Bottles A and B were sealed with rubber stoppers and transferred to a fume hood. Bottle A was cooled to -30°C. The solution in bottle B was slowly added dropwise to bottle A using a syringe. After stirring for 2 hours, the reaction mixture was transferred to a Schlenk flask containing compound IV-R-Br (136 mg, 0.5 mmol, 0.1 eq) and DMAP (61 mg, 0.5 mmol, 0.1 eq) and purged with N2. The mixture was stirred for 1 hour, then cooled to room temperature and reacted for another 18 hours. The reaction mixture was then added dropwise to 125 mL of methanol frozen at -20°C to precipitate the solid. After centrifugation, the supernatant was discarded, and the solid was dissolved in THF. This "dissolution-precipitation-centrifugation" process was repeated three times to obtain 0.83 g of a white solid, with a yield of 79%. n =3.8×10 3 M w =5.2×10 3 PDI=1.36.

[0205] Example 11

[0206] The synthetic route for preparing polymer IV-4 is as follows:

[0207]

[0208] Place Schlenk flasks A and B in a forced-air drying oven to dry. In a glove box, add compound V-4 (1.2 g, 3.5 mmol, 1.0 eq) to flask A and dissolve it with 6 mL of ultra-dry THF. Use two microsyringes to add P2-t-Bu (35 μL, 0.07 mmol, 0.02 eq) and freshly distilled methanol (2.8 μL, 0.07 mmol, 0.02 eq) to flask B and dilute with 1 mL of ultra-dry THF. Seal bottles A and B with rubber stoppers and transfer them to a fume hood. Cool bottle A to -30°C. Use a double-ended needle to transfer the solution from bottle B to bottle A. Stir the reaction for 2 hours. Then, use a double-ended needle to transfer the reaction solution to another Schlenk flask containing compound IV-R-Br (95 mg, 0.35 mmol, 0.1 eq) and DMAP (43 mg, 0.35 mmol, 0.1 eq) and purged with N2. Stir for 0.5 hours, then return to room temperature and continue the reaction for 20 hours. The reaction solution turns into a yellow turbid liquid. Add the reaction solution dropwise to 100 mL of methanol frozen at -20°C to precipitate the solid. Centrifuge and dissolve the solid in THF. Repeat this "dissolve-precipitate-centrifuge" operation three times to obtain 1.0 g of a light green solid, with a yield of 84%. n =4.6×10 3 M w =6.5×10 3 PDI=1.44.

[0209] Example 12

[0210] The thermal stability and glass transition temperature of polymers I-1, I-5, II-8, II-12, III-6, and IV-1 prepared in Examples 1, 2, 5, 6, 9, and 10 were determined. Differential scanning calorimetry (DSC) and thermogravimetric analysis of the polymer in Example 1 are shown below. Figure 1 The differential scanning calorimetry (DSC) curves and thermogravimetric analysis of the polymer in Example 2 are shown below. Figure 2 The differential scanning calorimetry (DSC) curves and thermogravimetric analysis of the polymer in Example 5 are shown in [reference needed]. Figure 3 The differential scanning calorimetry (DSC) and thermogravimetric analysis of the polymer in Example 6 are shown in [reference needed]. Figure 4 The differential scanning calorimetry (DSC) curves and thermogravimetric analysis of the polymer in Example 9 are shown in [reference needed]. Figure 5 The differential scanning calorimetry (DSC) curves and thermogravimetric analysis of the polymer in Example 10 are shown below. Figure 6 The results showed that the thermal decomposition temperature of the polymers was above 200℃, indicating good thermal stability.

[0211] Example 13

[0212] Polymer I-1 from Example 1 was dissolved in propylene glycol methyl ether acetate to prepare a 50 mg / mL solution. This solution was filtered through a 0.22 μm microporous filter to obtain a spin-coating solution. This solution was then spin-coated onto a silicon substrate treated with HMDS. The uniformity of the film was analyzed using atomic force microscopy (AFM). See [link to AFM analysis]. Figure 7 As can be seen from the figure, the resulting film is very uniform.

[0213] Example 14

[0214] Polymer I-5 from Example 2 was dissolved in 1,2-dichloroethane to prepare a 10 mg / mL solution. This solution was filtered through a 0.22 μm microporous filter to obtain a spin-coating solution. A spin-coating was then performed on an HMDS-treated silicon substrate. The film uniformity was analyzed using AFM. (See attached image.) Figure 8 As can be seen from the figure, the resulting film is very uniform.

[0215] Example 15

[0216] Polymer II-8 from Example 5 was dissolved in cyclohexanone to prepare a 25 mg / mL solution. This solution was filtered through a 0.22 μm microporous filter to obtain a spin-coating solution. Spin-coating was then performed on a silicon substrate that had not undergone HMDS treatment. AFM was used to analyze the film uniformity. (See attached image.) Figure 9 As can be seen from the figure, the resulting film is very uniform.

[0217] Example 16

[0218] Polymer II-12 from Example 6 was dissolved in anisole to prepare a 40 mg / mL solution. This solution was filtered through a 0.22 μm microporous filter to obtain a spin-coating solution. A spin-coating was then performed on an HMDS-treated silicon substrate. The film uniformity was analyzed using AFM. (See attached image.) Figure 10 As can be seen from the figure, the resulting film is very uniform.

[0219] Example 17

[0220] Polymer III-6 from Example 9 was dissolved in anisole to prepare a 35 mg / mL solution. This solution was filtered through a 0.22 μm microporous filter to obtain a spin-coating solution. This solution was then spin-coated onto an HMDS-treated silicon substrate. AFM was used to analyze the film uniformity. (See attached image.) Figure 11 As can be seen from the figure, the resulting film is very uniform.

[0221] Example 18

[0222] Polymer IV-1 from Example 10 was dissolved in cyclopentanone to prepare a 30 mg / mL solution. This solution was filtered through a 0.22 μm microporous filter to obtain a spin-coating solution. This solution was then spin-coated onto an HMDS-treated silicon substrate. AFM was used to analyze the film uniformity. (See attached image.) Figure 12 As can be seen from the figure, the resulting film is very uniform.

[0223] Example 19

[0224] A positive photoresist formulation and its electron beam lithography: Polymer I-1 from Example 1 was dissolved in propylene glycol methyl ether acetate to prepare a solution with a mass concentration of 25 mg / ml. The solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution. This solution was then spin-coated onto a silicon substrate treated with HMDS. The substrate was pre-baked at 100°C for 1 minute, and the film thickness was measured using an ellipsometer. The prepared thin film was exposed using an electron beam light source at the National Center for Nanoscience and Technology, with exposure periods of 80 nm, 60 nm, and 50 nm, and exposure doses of 200 μC / cm. 2 250 μC / cm 2 and 300 μC / cm 2 Uniform lithographic stripes can be obtained. The lithographic results for a pattern with an exposure period of 50 nm are shown in [reference needed]. Figure 13 The width of the lithographic stripes is approximately 25 nm, and the LER (Line Edge Ratio) is 3.9 nm. The results show that the obtained pattern simultaneously possesses excellent resolution, sensitivity, and low line edge roughness.

[0225] Example 20

[0226] A positive photoresist formulation and its electron beam lithography: Polymer I-5 from Example 2 was dissolved in 1,2-dichloroethane to prepare a solution with a mass concentration of 7.5 mg / ml. The solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution. This solution was then spin-coated onto a silicon substrate treated with HMDS. The substrate was pre-baked at 75°C for 2 minutes, and the film thickness was measured using an ellipsometer. The prepared film was exposed using an electron beam light source at the National Center for Nanoscience and Technology with exposure periods of 80 nm, 60 nm, and 50 nm, and exposure doses of 125 μC / cm. 2 150 μC / cm 2 and 175 μC / cm 2 Uniform lithographic stripes can be obtained. The lithographic results for a pattern with an exposure period of 50 nm are shown in [reference needed]. Figure 14 The width of the lithographic stripes is approximately 25 nm, and the LER (Line Edge Ratio) is 3.9 nm. The results show that the obtained pattern simultaneously possesses excellent resolution, contrast, and low line edge roughness.

[0227] Example 21

[0228] A positive photoresist formulation and its electron beam lithography: Polymer II-8 from Example 5 was dissolved in cyclohexanone to prepare a solution with a mass concentration of 25 mg / ml. The solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution. Spin-coating was performed on a silicon substrate that had not been treated with HMDS. The substrate was pre-baked at 70°C for 3 minutes, and the film thickness was measured using an ellipsometry. The prepared film was exposed using an electron beam light source at the National Center for Nanoscience and Technology, with exposure periods of 80 nm and 60 nm, and exposure doses of 250 μC / cm. 2 and 275 μC / cm 2 Uniform lithographic stripes can be obtained. The lithographic results for a pattern with an exposure period of 60 nm are shown in [reference needed]. Figure 15 The width of the lithographic stripes is approximately 30 nm, and the LER (Line Edge Ratio) is 4.0 nm. The results show that the obtained pattern simultaneously possesses excellent resolution, contrast, and low line edge roughness.

[0229] Example 22

[0230] A positive photoresist formulation and its electron beam lithography: Polymer II-12 from Example 6 was dissolved in anisole to prepare a solution with a mass concentration of 25 mg / ml. The solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution. This solution was then spin-coated onto a silicon substrate treated with HMDS. The substrate was pre-baked at 110°C for 3 minutes, and the film thickness was measured using an ellipsometer. The prepared film was exposed using an electron beam light source at the National Center for Nanoscience and Technology, with exposure periods of 80 nm and 60 nm, and exposure doses of 300 μC / cm. 2 and 375 μC / cm 2 Uniform lithographic stripes can be obtained. The lithographic results for a pattern with an exposure period of 60 nm are shown in [reference needed]. Figure 16 The width of the lithographic stripes is approximately 30 nm, and the LER (Line Edge Ratio) is 3.8 nm. The results show that the obtained pattern simultaneously possesses excellent resolution, contrast, and low line edge roughness.

[0231] Example 23

[0232] A positive photoresist formulation and its electron beam lithography: Polymer III-6 from Example 9 was dissolved in anisole to prepare a solution with a mass concentration of 25 mg / ml. The solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution. This solution was then spin-coated onto a silicon substrate treated with HMDS. The substrate was pre-baked at 110°C for 3 minutes, and the film thickness was measured using an ellipsometry. The prepared film was exposed using an electron beam light source at the National Center for Nanoscience and Technology, with exposure periods of 80 nm and 60 nm, and exposure doses of 100 μC / cm. 2 and 150 μC / cm 2 Uniform lithographic stripes can be obtained. The lithographic results for a pattern with an exposure period of 60 nm are shown in [reference needed]. Figure 17 The width of the lithographic stripes was 30 nm, and the LER was 3.5 nm. The results show that the obtained pattern has both good resolution and contrast, as well as low line edge roughness.

[0233] Example 24

[0234] A positive photoresist formulation and its electron beam lithography: Polymer IV-1 from Example 10 was dissolved in cyclopentanone to prepare a solution with a mass concentration of 25 mg / ml. The solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution. This solution was then spin-coated onto a silicon substrate treated with HMDS. The substrate was pre-baked at 100°C for 2 minutes, and the film thickness was measured using an ellipsometry. The prepared film was exposed using an electron beam light source at the National Center for Nanoscience and Technology, with exposure periods of 80 nm and 60 nm, and exposure doses of 200 μC / cm. 2 and 225 μC / cm 2 Uniform lithographic stripes can be obtained. The lithographic results for a pattern with an exposure period of 60 nm are shown in [reference needed]. Figure 18 The width of the lithographic stripes was 30 nm, and the LER was 3.9 nm. The results show that the obtained pattern has both good resolution and contrast, as well as low line edge roughness.

[0235] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all the implementation methods here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A non-chemical amplification photoresist, characterized in that, The product comprises, by weight percentage, 0.1-10 wt% of a self-degrading polymer based on polybenzyl ether, which is used as a non-chemically amplified photoresist host material. The polymer has a general formula structure as shown in one of the following structures: I、 II、 III、 IV: In this context, R1 and R2 each independently represent H or C. 1-10 Alkoxy groups, R1 and R2, can connect to each other to form a five-membered or six-membered ring structure containing 1-2 O atoms; R3 represents H or C. 1-10 alkyl; R4 and R5 are substituents on the benzene ring, with R4 representing H or C. 1-10 Alkyl group, R5 represents H, -OC (=O)-C 3-10 cycloalkyl, -OC 1-10 Alkyl-C 2-10 alkenyl, -OC 1-10 Alkyl-C 6-10 Any of the aryl groups; The value of n is a positive integer ranging from 5 to 2000.

2. The non-chemical amplification photoresist according to claim 1, characterized in that, The polydispersity index (PDI) of the polymer is ≤2.

00.

3. The non-chemical amplification photoresist according to claim 1, characterized in that, The polymer's M n For 1000-800000 Daltons, M w It ranges from 1,000 to 1,000,000 Daltons.

4. The non-chemical amplification photoresist according to claim 1, characterized in that, The polymer described in Formula I is selected from one of the following structures: 。 5. The non-chemical amplification photoresist according to claim 1, characterized in that, The polymer described in Formula II is selected from one of the following structures: 。 6. The non-chemical amplification photoresist according to claim 1, characterized in that, The polymer described in Formula III is selected from one of the following structures: 。 7. The non-chemical amplification photoresist according to claim 1, characterized in that, The polymer described in Formula IV is selected from one of the following structures: 。 8. The non-chemical amplification photoresist according to claim 1, characterized in that, When the polymer is selected from the structure of formula I, its preparation method includes the following steps: Add monomer V to reaction flask A, dissolve it in ultra-dry tetrahydrofuran, and cool it to -40 to -20°C. Compound P2-t-Bu and methanol were added to reaction flask B, diluted with ultra-dry tetrahydrofuran, and reacted for 0.5-1 h. The solution was then transferred to reaction flask A and reacted at -40 to -20 °C for 1-3 h. After the reaction was completed, the reaction solution was transferred to another reaction flask containing compounds IR-Br and DMAP and filled with N2. The reaction was carried out at -40 to -20°C for 0.5 to 1 h, then slowly raised to room temperature and continued to react for 9 to 20 h. The reaction solution was precipitated three times in methanol at -30 to -20°C to obtain the polymer shown in Formula I. The structures of monomer V and compound IR-Br are shown below: ； The molar ratio of compound P2-t-Bu, methanol, and monomer V is 1:1-10:10-100; The molar ratio of compound IR-Br, DMAP and monomer V is 1:1:2-50; When the polymer is selected from the structure of formula II, its preparation method includes the following steps: Add monomer V to reaction flask A, dissolve it in ultra-dry tetrahydrofuran, and cool it to -40 to -20°C. Compound P2-t-Bu and methanol were added to reaction flask B, diluted with ultra-dry tetrahydrofuran, and reacted for 0.5-1 h. The solution was then transferred to reaction flask A and reacted at -40 to -20 °C for 1-3 h. After the reaction was completed, the reaction solution was transferred to another reaction flask containing compound II-R-Cl and DMAP and filled with N2. The reaction was carried out at -40 to -20°C for 0.5-1 h, then slowly raised to room temperature and continued to react for 9-20 h. The reaction solution was precipitated three times in methanol at -30 to -20°C to obtain the polymer shown in Formula II. The structures of monomer V and compound II-R-Cl are shown below: ； The molar ratio of compound P2-t-Bu, methanol, and monomer V is 1:1-10:10-100; The molar ratio of compound II-R-Cl, DMAP, and monomer V is 1:1:2-50; When the polymer is selected from the structure of formula III, its preparation method includes the following steps: Add monomer V to reaction flask A, dissolve it in ultra-dry tetrahydrofuran, and cool it to -40 to -20°C. Compound P2-t-Bu and methanol were added to reaction flask B, diluted with ultra-dry tetrahydrofuran, and reacted for 0.5-1 h. The solution was then transferred to reaction flask A and reacted at -40 to -20 °C for 1-3 h. After the reaction was completed, the reaction solution was transferred to another reaction flask containing compound III-R-Br and DMAP and filled with N2. The reaction was carried out at -40 to -20°C for 0.5-1 h, then slowly raised to room temperature and continued to react for 9-20 h. The reaction solution was precipitated three times in methanol at -30 to -20°C to obtain the polymer shown in Formula III. The structures of monomer V and compound III-R-Br are shown below: ； The molar ratio of compound P2-t-Bu, methanol, and monomer V is 1:1-10:10-100; The molar ratio of compound III-R-Br, DMAP, and monomer V is 1:1:2-50; When the polymer is selected from the IV structure, its preparation method includes the following steps: Add monomer V to reaction flask A, dissolve it in ultra-dry tetrahydrofuran, and cool it to -40 to -20°C. Compound P2-t-Bu and methanol were added to reaction flask B, diluted with ultra-dry tetrahydrofuran, and reacted for 0.5-1 h. The solution was then transferred to reaction flask A and reacted at -40 to -20 °C for 1-3 h. After the reaction was completed, the reaction solution was transferred to another reaction flask containing compound IV-R-Br and DMAP and filled with N2. The reaction was carried out at -40 to -20°C for 0.5-1 h, then slowly raised to room temperature and continued to react for 9-20 h. The reaction solution was precipitated three times in methanol at -30 to -20°C to obtain the polymer shown in Formula IV. The structures of monomer V and compound IV-R-Br are shown below: ； The molar ratio of compound P2-t-Bu, methanol, and monomer V is 1:1-10:10-100; The molar ratio of compound IV-R-Br, DMAP, and monomer V is 1:1:2-50.

9. The non-chemical amplification photoresist according to claim 1, characterized in that, The non-chemical amplification photoresist also includes solvents by weight percentage; The solvent is selected from one or more of propylene glycol methyl ether acetate, propylene glycol methyl ether, N,N-dimethylformamide, cyclohexanone, cyclopentanone, ethyl n-pentanone, ethyl isopentanone, ethanol, acetonitrile, isopropanol, acetone, methyl n-pentanone, methyl isopentanone, anisole, and 1,2-dichloroethane.

10. A photoresist coating, characterized in that, Including the non-chemical amplification photoresist as described in any one of claims 1-9.

11. The use of the non-chemical amplification photoresist as described in any one of claims 1-9 or the photoresist coating as described in claim 10 in the preparation of photolithographic patterns.

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