Photoresists based on alkynyl bridging and biphenyl structures, methods of making and use

Abstract

The present application relates to the technical field of carbon ring compounds, and particularly relates to a photoresist based on alkynyl bridging and biphenyl structure, a preparation method and application. The photoresist provided by the present application is based on a biphenyl structure and is constructed by introducing alkynyl as a bridging body, and has a triphenyl skeleton and a conjugated alkynyl group for regulating the glass transition temperature of the molecule, thereby being beneficial to improving the thermal stability and film characteristics of the photoresist based on alkynyl bridging and biphenyl structure; a typical hydrophobic group is introduced on the basis of a polyphenol structure unit, which can not only provide an acid-labile protecting group, but also can reduce the crystallization ability of the photoresist, thereby meeting the performance requirements of a positive molecular glass for a photoetching process. The photoresist is used as a main component to prepare a photoresist layer material, and the obtained etching pattern has a good overall effect. The molecular structure provided by the present application is simple, the synthesis route is simple, the reaction conditions are mild and controllable, and the scale production can be realized.

Description

Technical Field

[0001] This invention relates to the field of carbocyclic compound technology, and in particular to photoetchants based on alkynyl bridging and biphenyl structures, their preparation methods, and applications. Background Technology

[0002] As the wavelength of light sources used in photolithography continues to shrink, the spatial scale of photolithography also decreases. In this context, reducing the molecular size of photoresist film-forming agents to replace traditional polymers is of significant research value. Compared to polymer photoresists, molecular glasses have smaller dimensions and higher dispersion, which is more conducive to obtaining low edge roughness and achieving high resolution. Currently, molecular glasses, represented by polyphenols, cyclic molecules, step-type compounds, and fullerenes, have become important candidate materials for advanced photolithography technologies. Among them, polyphenol molecular glasses have strong modifiability of phenolic hydroxyl groups and can provide protons to promote electron transfer between the exposure area and the photoacid generator, which can significantly improve the resolution of photoresists, showing a clear advantage in the field of photolithography. However, the reported polyphenolic photoetchants have complex structures and relatively cumbersome preparation processes, which increases manufacturing costs and is obviously not conducive to industrial applications.

[0003] Therefore, designing novel and easily prepared molecular glass photoresists is of great significance. Summary of the Invention

[0004] The present invention aims to at least solve one of the technical problems existing in the related art. To this end, the first objective of the present invention is to provide a photoetchant based on an alkynyl-bridged and biphenyl structure; the second objective of the present invention is to provide a method for preparing a photoetchant based on an alkynyl-bridged and biphenyl structure; and the third objective of the present invention is to provide applications of a photoetchant based on an alkynyl-bridged and biphenyl structure.

[0005] To achieve the first objective, the technical solution adopted by this invention is as follows:

[0006] Photoetchants based on alkynyl bridging and biphenyl structures have the following structural formula:

[0007] R1, R2, R3, R4, R5, and R6 are each independently selected from any of the following structural formulas:

[0008] , and .

[0009] This invention is based on the biphenyl structure and constructs a non-planar polyphenyl structure by introducing an alkyne group as a bridging agent. Using the triphenyl (TP) polyphenyl system as the backbone, the conjugated alkyne group regulates the glass transition temperature, thereby improving the thermal stability and thin film properties of photoetchants based on alkyne-bridged and biphenyl structures. Secondly, based on the structural characteristics of molecular glasses and design requirements, a typical hydrophobic group -BOC is introduced into the TP polyphenol structural unit. -BU and -AD It can reduce the crystallization ability of photoetchants and provide acid-instable protective groups, thereby meeting the performance requirements of photolithography for positive molecular glasses.

[0010] Preferably, R1, R2, R3, R4, R5, and R6 are all selected from... The structural formula of the photoetchant based on alkynyl bridging and biphenyl structure is shown below:

[0011]

[0012] Alternatively, R1, R2, R3, R4, R5, and R6 can all be selected from... The structural formula of the photoetchant based on alkynyl bridging and biphenyl structure is shown below:

[0013]

[0014] Alternatively, R1, R2, R3, R4, R5, and R6 can all be selected from... The structural formula of the photoetchant based on alkynyl bridging and biphenyl structure is shown below:

[0015] .

[0016] To achieve the second objective, the technical solution adopted by this invention is as follows:

[0017] A method for preparing the above-mentioned photoetchant based on alkynyl-bridged and biphenyl structures includes the following steps:

[0018] S100. In reaction solvent I, compound I is synthesized by reacting 1,2,4,5-tetrabromobenzene with an acetylene derivative bearing a protecting group.

[0019] S200. In reaction solvent II, compound I undergoes a self-coupling reaction under the action of metal catalyst I to synthesize compound II.

[0020] S300. In reaction solvent III, compound II undergoes a coupling reaction with p-hydroxyphenylboronic acid under the action of metal catalyst II to synthesize compound III.

[0021] S400. In reaction solvent IV, compound III reacts with any of the following substances to synthesize a photoetchant based on an alkynyl-bridged and biphenyl structure:

[0022] Di-tert-butyl dicarbonate, tert-butyl bromoacetate, and 2-chloroacetoxy-2-methyladamantane.

[0023] Preferably, in step S100, the protecting group is selected from silane groups.

[0024] Preferably, in step S200, the metal catalyst I is selected from cuprous iodide.

[0025] Preferably, in step S300, the metal catalyst II is selected from tetra(triphenylphosphine)palladium.

[0026] Preferably, both reaction solvent I and reaction solvent II are selected from a mixed solvent composed of tetrahydrofuran and triethylamine, with a volume ratio of tetrahydrofuran to triethylamine of 3:1 to 4:1.

[0027] Preferably, the reaction solvent III is selected from N,N-dimethylformamide, and the reaction solvent IV is selected from tetrahydrofuran.

[0028] To achieve the third objective, the technical solution adopted by this invention is as follows:

[0029] Based on the application of photoetchants with alkynyl bridging and biphenyl structures, photoresist coating materials are prepared using the above-mentioned photoetchants with alkynyl bridging and biphenyl structures.

[0030] The photoresist coating material comprises the following components by weight percentage:

[0031] The photoetchant based on alkynyl bridging and biphenyl structure is 8%–10%, the photoacid generator is 0.35%–0.45%, the quencher is 0.10%–0.15%, and the balance is solvent.

[0032] The above-described one or more technical solutions in the embodiments of the present invention have at least one of the following technical effects:

[0033] This invention provides a photoetchant based on an alkyne-bridged and biphenyl structure. Based on the biphenyl structure, a non-planar polyphenylene structure is constructed by introducing alkyne groups as bridges. Using the triphenyl (TP) polyphenylene system as the backbone, the conjugated alkyne groups regulate the glass transition temperature, thereby improving the thermal stability and thin film properties of the photoetchant based on the alkyne-bridged and biphenyl structure. Secondly, based on the structural characteristics of molecular glasses and design requirements, typical hydrophobic groups -BOC, -BU, and -AD are introduced into the TP polyphenol structural unit. This reduces the crystallization ability of the photoetchant and provides acid-instable protective groups, thus meeting the performance requirements of photolithography for positive molecular glasses. Therefore, this photoetchant can be used to prepare photoresist coating materials.

[0034] The preparation method provided by this invention has a simple synthetic route and mild and controllable reaction conditions, which is conducive to large-scale production.

[0035] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Attached Figure Description

[0036] Figure 1 This is a photolithographic pattern diagram obtained by using sample 1 as a photoresist coating, provided in the test example of the present invention.

[0037] Figure 2 This is a photolithographic pattern diagram obtained by using sample 2 as a photoresist coating, provided in the test example of the present invention.

[0038] Figure 3 This is a photolithographic pattern diagram obtained by using sample 3 as a photoresist coating, provided in the test example of the present invention. Detailed Implementation

[0039] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention. The following embodiments are used to illustrate this invention, but cannot be used to limit the scope of this invention.

[0040] In the following embodiments, unless otherwise specified, the experimental methods used are conventional methods, and the materials and reagents used are commercially available, unless otherwise specified, and are carried out in accordance with the techniques or conditions described in the literature in this field or in accordance with the product instructions.

[0041] Example 1

[0042] Preparation of TP-BOC The process is as follows:

[0043] I. Preparation of Compound I, the synthetic route is shown below:

[0044] ;

[0045] The preparation process is as follows:

[0046] Under a nitrogen atmosphere, CuI (0.38 g, 2 mmol) was added to a reaction system containing 1,2,4,5-tetrabromobenzene (8.0 g, 0.02 mol), trimethylsilylacetylene (1.96 g, 0.02 mol), tetrahydrofuran (150 mL), and triethylamine (50 mL). The reaction was vigorously stirred at 80°C for 24 h, then allowed to cool naturally to room temperature. The mixture was then filtered and the solvent was removed under reduced pressure. The crude product was subjected to column chromatography (using a mixture of petroleum ether and dichloromethane as the mobile phase). The mixture was separated (volume ratio of the two components was 1:1) to obtain an intermediate. Subsequently, the obtained intermediate was dissolved in a mixed solvent of tetrahydrofuran (80 mL) and methanol (80 mL), and K2CO3 (3.08 g, 0.022 mol) was added. After stirring at room temperature for 2 h, the solvent was removed, and the crude product was separated by column chromatography (mobile phase was a mixed solvent of petroleum ether and dichloromethane in a 1:2 ratio) to obtain compound I (11.79 g), with a yield of 75%. Its characterization data are shown below:

[0047] 1 H NMR (CDCl3): δ 7.84 (s, 1H), 7.45 (d, J =7.8Hz, 1H), 4.01 (s, 1H);

[0048] 13 C NMR (CDCl3): δ 137.80, 136.5, 127.8, 127.40, 126.8, 124.53, 82.3, 81.4.

[0049] II. Preparation of Compound II, the synthetic route is shown below:

[0050] ;

[0051] The preparation process is as follows:

[0052] Compound I (10.14 g, 3 mmol) was dissolved in tetrahydrofuran (200 mL) and triethylamine (50 mL) under a nitrogen atmosphere. CuI (86 mg, 0.45 mmol) and K₂CO₃ (0.62 mg, 4.5 mmol) were then added. The reaction mixture was heated to 160°C and maintained at this temperature with stirring for 24 h. After hot filtration and extraction with dichloromethane, the organic layers were combined, dried over Na₂SO₄, and the solvent was removed under reduced pressure. The crude product was separated by column chromatography (mobile phase: a mixture of petroleum ether and dichloromethane, volume ratio 3:1) to give compound II (4.18 g) in 55% yield. The characterization results are shown below.

[0053] 1 H NMR (CDCl3): δ 7.56 (s, 6H);

[0054] 13 C NMR (CDCl3): δ 135.20, 127.1, 125.2, 91.0.

[0055] III. Preparation of compound III, the synthetic route of which is shown below:

[0056] ;

[0057] The preparation process is as follows:

[0058] Under a nitrogen atmosphere, Pd(PPh3)4 (2.4 g, 2 mmol) was added to a mixture of N,N-dimethylformamide (100 mL) containing compound II (4.0 g, 5.17 mmol), p-hydroxyphenylboronic acid (5.74 g, 41.36 mmol), and K2CO3 (14 g). The reaction mixture was heated to 150°C and stirred for 24 h. The reaction mixture was then poured into ice water, resulting in precipitation. The precipitate was filtered to obtain a filter cake, which was dried and then separated by column chromatography (mobile phase was a mixture of petroleum ether and dichloromethane, volume ratio 1:2) to obtain compound III (2.64 g) in 61% yield. The characterization data are shown below.

[0059] 1 H NMR (CDCl3): δ 7.82 (s, 6H), 7.49 (d, J =8.75 Hz, 12H), 7.03(s, 6H), 6.89(d, J= 8.75 Hz, 12H);

[0060] 13C NMR (CDCl3): δ 158.89, 139.54, 133.38, 132.23, 130.25, 121.75, 116.64, 90.82.

[0061] IV. Preparation of the target compound TP-BOC using compound III, as follows:

[0062] Under a nitrogen atmosphere, compound III (0.85 g, 0.5 mmol), di-tert-butyl dicarbonate (2.49 g, 12.0 mmol), and tetrahydrofuran (20 mL) were added to 100 mL of triceramide. Then, 4-dimethylaminopyridine (6.12 mg, 0.05 mmol) was added. The resulting solution was stirred and reacted overnight. After the reaction was complete, the mixture was quenched with water and extracted with dichloromethane. The organic layer was collected and dried over Na₂SO₄. The crude product was purified by silica gel column chromatography (the mobile phase was a mixture of dichloromethane and ethyl acetate, with a volume ratio of 20:1) to obtain the white solid target product TP-BOC (0.75 g), with a yield of 65%. The characterization data are shown below:

[0063] 1 H NMR (CDCl3): δ 8.05(s, 1H), 8.02-7.98(m, 11H), 7.97(s, 4H), 7.88(s, 1H), 7.71(t, J =7.8 Hz, 1H), 7.66-7.60 (m, 11H), 1.56 (s, 54H);

[0064] 13 C NMR (CDCl3): δ 165.71, 143.90, 139.79, 133.46, 131.41, 130.90, 128.61, 121.76, 90.82, 80.58, 28.37.

[0065] TP-BOC was dissolved in propylene glycol monomethyl ether acetate (solvent), followed by the addition of triphenylsulfonium perfluorobutyl sulfonate (photoacid generator) and triethylamine (quencher) to obtain a mixture. The proportions of each component by mass are as follows: TP-BOC 10%, photoacid generator 0.40%, quencher 0.10%, and solvent 89.5%.

[0066] After stirring the mixture at room temperature in the dark for 4 hours, the mixture was filtered through a 0.2 μM polytetrafluoroethylene (PTFE) membrane filter. The resulting filtrate was the photoetchant composition (referred to as Sample 1), which used TP-BOC as the main etching component.

[0067] Example 2

[0068] Preparation of TP-BU The process is as follows:

[0069] I. Preparation of compounds I to III.

[0070] Prepared according to the synthetic route and preparation process of compounds I to III in Example 1.

[0071] II. Preparation of TP-BU using compound III, the process is as follows:

[0072] Compound III (0.85 g, 0.5 mmol), tert-butyl bromoacetate (1.05 g, 5.0 mmol), tetrabutylammonium bromide (0.18 g, 6.0 mmol), K₂CO₃ (8.1 g, 6 mmol), and 1-methyl-2-pyrrolidone (20 mL) were added to a 250 mL three-necked flask. The mixture was stirred at 80°C for 5 h under a nitrogen atmosphere. The reaction solution was then cooled to room temperature and extracted three times with ethyl acetate. The organic layers were combined, washed with an aqueous solution containing sodium chloride, and dried over anhydrous Na₂SO₄ to obtain the crude product. The crude product was purified by silica gel column chromatography (mobile phase was a mixture of petroleum ether and ethyl acetate, volume ratio 2:1), followed by precipitation with n-hexane to obtain the white solid target product TP-BU (0.51 g), with a yield of 70%. The characterization data are shown below.

[0073] 1 H NMR (CDCl3): δ 7.80 (s, 6H), 7.57 (d, J =8.4 Hz, 12H), 7.09 (d, J= 8.3 Hz, 8H), 7.04 (d, J =8.4 Hz, 2H), 6.96 (d, J =8.4 Hz, 2H), 4.69 (s, 8H), 2.74 (t, J=6.1 Hz, 2H), 2.14 (s, 3H);

[0074] 13C NMR (CDCl3): δ 171.26, 171.22, 168.05, 161.53, 159.37, 158.66, 139.73, 133.54, 133.47, 133.45, 133. 38, 129.53, 121.75, 118.63, 117.43, 117.31, 90.82, 80.74, 80.21, 80.10, 78.29, 73.64, 6 6.46, 63.14, 40.55, 40.26, 38.77, 37.29, 37.17, 36.72, 36.62, 36.44, 36.38, 36.23, 35.12, 35.02, 35.01, 33.62, 31.96, 30.15, 29.81, 29.36, 29.20, 28.96, 21.82, 20.95, 20.92.

[0075] TP-BU was dissolved in propylene glycol monomethyl ether acetate (solvent), followed by the addition of triphenylsulfonium perfluorobutyl sulfonate (photoacid generator) and triethylamine (quencher) to obtain a mixture. The proportions of each component by mass are as follows: TP-BU 9%, photoacid generator 0.35%, quencher 0.15%, and solvent 90.5%.

[0076] After stirring the mixture at room temperature in the dark for 4 hours, the mixture was filtered through a 0.2 μM PTFE membrane filter. The resulting filtrate was the photoetchant composition (referred to as sample 2), which used TP-BU as the main etching component.

[0077] Example 3

[0078] Preparation of TP-AD The process is as follows:

[0079] I. Preparation of compounds I to III.

[0080] Prepared according to the synthetic route and preparation process of compounds I to III in Example 1.

[0081] II. Preparation of TP-AD using compound III, the process is as follows:

[0082] Compound III (0.85 g, 0.5 mmol), 2-chloroacetoxy-2-methyladamantane (1.25 g, 6.0 mmol), tetrabutylammonium bromide (0.19 g, 6.0 mmol), K₂CO₃ (1.4 g, 10 mmol), and 1-methyl-2-pyrrolidone (20 mL) were added to a 250 mL three-necked flask. The mixture was then stirred at 80 °C for 5 h under a nitrogen atmosphere. The reaction solution was cooled to room temperature and extracted three times with ethyl acetate. The organic layers were combined and dried over anhydrous Na₂SO₄ to obtain the crude product. This crude product was purified by silica gel column chromatography (mobile phase: a mixture of petroleum ether and ethyl acetate, volume ratio 3:1) to obtain the white solid target product TP-AD (0.43 g), with a yield of 86%. The characterization data are shown below.

[0083] 1 H NMR (CDCl3): δ 7.80 (s, 1H), 7.57 (d, J =8.4Hz, 2H), 7.09 (d, J =8.4Hz, 2H), 4.63(s, 2H), 1.41(s, 9H);

[0084] 13 C NMR (CDCl3): δ 167.34, 158.66, 139.73, 133.54, 133.38, 129.53, 121.75, 116.79, 90.82, 82.16, 65.31, 27.79.

[0085] TP-AD was dissolved in propylene glycol monomethyl ether acetate (solvent), followed by the addition of triphenylsulfonate perfluorobutyl sulfonate (photoacid generator) and triethylamine (quencher) to obtain a mixture. The proportions of each component by mass are as follows: TP-AD 8%, photoacid generator 0.40%, quencher 0.10%, and solvent 91.5%.

[0086] After stirring the mixture at room temperature in the dark for 4 hours, the mixture was filtered through a 0.2 μM PTFE membrane filter. The resulting filtrate was the photoetchant composition (referred to as sample 3), which used TP-AD as the main etching component.

[0087] Test Example

[0088] Photolithographic patterns were prepared using Sample 1, Sample 2, and Sample 3, prepared in Examples 1, 2, and 3, respectively, as photoresists. The process is as follows:

[0089] Before spin coating, the glass substrate was vacuum-treated for 15 minutes to remove adsorbed gases and moisture from the surface and eliminate static electricity. Then, samples 1, 2, and 3 were coated onto the substrate surface to form photoresist coatings with a thickness of 50–70 nm. Following pre-baking, exposure, post-baking, and development processes, the resulting photolithographic patterns are shown below. Figure 1 , Figure 2 and Figure 3 As shown;

[0090] Among them, the pre-baking temperature of sample 1, sample 2 and sample 3 was 60℃, and the post-baking temperature of sample 1 was 60℃, while that of sample 2 and sample 3 was 130℃.

[0091] The light used for exposure is extreme ultraviolet light;

[0092] The developer was a 2.38 wt% aqueous solution of tetramethylammonium hydroxide;

[0093] from Figure 1 As can be seen, the stripe edges exhibit a sharp edge effect, without any blurring, burrs, or diffusion bands; whether locally or globally, the line width and spacing between stripes maintain near-consistent precision, with no fluctuations in width / density, no breaks, stains, bubbles, or local damage; the stripes remain parallel, without any distortion, shift, or local misalignment; the above results indicate that Sample 1, with TP-BOC as the main etching component, has high photosensitivity and good resolution as a photoresist coating, and still exhibits excellent photolithography performance after 60 days of storage;

[0094] from Figure 2 As can be seen, although a small number of broken lines appear in the pattern, the overall arrangement is neat, the line spacing is relatively uniform, and there are no serious burrs or excessively diffused blurry bands at the edge of the stripes. The coverage and uniformity of the coating on the substrate do not show any overall failure. This result indicates that sample 2, which uses TP-BU as the main etching component, can be used as a photoresist coating and still has good photolithography effect after 60 days of storage.

[0095] from Figure 3 As can be seen, although the edges are slightly blurred, the stripes are arranged in a regular and continuous manner, and the line width and line spacing remain stable without any obvious changes in width or density. This result indicates that sample 3, which uses TP-AD as the main etching component, can be used as a photoresist layer and still has good photolithography effect after 60 days of storage.

[0096] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A photoetchant based on an alkyne-bridged and biphenyl structure, characterized in that, The structural formula is as follows: R1, R2, R3, R4, R5, and R6 are each independently selected from any of the following structural formulas: , and .

2. The photoetchant based on alkynyl bridging and biphenyl structure as described in claim 1, characterized in that, R1, R2, R3, R4, R5, and R6 are all selected from... ; Alternatively, R1, R2, R3, R4, R5, and R6 can all be selected from... ; Alternatively, R1, R2, R3, R4, R5, and R6 can all be selected from... .

3. A method for preparing a photoetchant based on an alkyne-bridged and biphenyl structure, characterized in that, The method for preparing the photoetchant based on alkynyl bridging and biphenyl structure as described in claim 1 or 2 comprises the following steps: S100. In reaction solvent I, compound I is synthesized by reacting 1,2,4,5-tetrabromobenzene with an acetylene derivative bearing a protecting group. ; S200. In reaction solvent II, compound I undergoes a self-coupling reaction under the action of metal catalyst I to synthesize compound II. ; Wherein, the metal catalyst I is selected from cuprous iodide; S300. In reaction solvent III, compound II undergoes a coupling reaction with p-hydroxyphenylboronic acid under the action of metal catalyst II to synthesize compound III. ; The metal catalyst II is selected from tetra(triphenylphosphine)palladium; S400. In reaction solvent IV, compound III reacts with di-tert-butyl dicarbonate to synthesize a photoetchant based on an alkynyl bridge and biphenyl structure, as shown below: ； Alternatively, in reaction solvent IV, compound III reacts with tert-butyl bromoacetate to synthesize a photoetchant based on an alkynyl bridge and a biphenyl structure, as shown below: ； Alternatively, in reaction solvent IV, compound III reacts with 2-chloroacetoxy-2-methyladamantane to synthesize a photoetchant based on an alkynyl bridge and a biphenyl structure, as shown below: 。 4. The method for preparing the photoetchant based on alkynyl bridging and biphenyl structure as described in claim 3, characterized in that, In step S100, the protecting group is selected from silane groups.

5. The method for preparing the photoetchant based on alkynyl bridging and biphenyl structure as described in claim 3, characterized in that, Both reaction solvent I and reaction solvent II are selected from a mixed solvent composed of tetrahydrofuran and triethylamine, with a volume ratio of tetrahydrofuran to triethylamine of 3:1 to 4:

1.

6. The method for preparing the photoetchant based on alkyne bridging and biphenyl structure as described in claim 3, characterized in that, The reaction solvent III is selected from N,N-dimethylformamide, and the reaction solvent IV is selected from tetrahydrofuran.

7. The application of photoetchants based on alkynyl bridging and biphenyl structures, characterized in that, Photoresist coating materials are prepared using the photoetchant based on alkyne bridging and biphenyl structure as described in claim 1 or 2. The photoresist coating material comprises the following components by weight percentage: The photoetchant based on alkynyl bridging and biphenyl structure is 8%–10%, the photoacid generator is 0.35%–0.45%, the quencher is 0.10%–0.15%, and the balance is solvent.

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