Photoinduced etching agent based on alkynyl bridging and biphenyl structure, preparation method and application

Abstract

The invention relates to the technical field of carbocyclic compounds, in particular to a photoinduced etching agent based on alkynyl bridging and biphenyl structures, a preparation method and application. The photoinduced etching agent provided by the invention is based on a biphenyl structure and is constructed by introducing alkynyl as a bridging body, triphenyl is used as a framework, and conjugated alkynyl regulates and controls the molecular glass transition temperature, so that the thermal stability and film characteristics of the photoinduced etching agent based on alkynyl bridging and the biphenyl structure are favorably improved; a typical hydrophobic group is introduced on the basis of a polyphenol structural unit, so that an acid-unstable protecting group can be provided, the crystallization capacity of a photoinduced etching agent can be reduced, and the performance requirement of a photoetching process on positive molecular glass is met. When the photo-induced etching agent is used as a main component to prepare a photo-induced gluing layer material, an obtained etching pattern is good in overall effect. The molecular structure provided by the invention is simple, the synthetic route is concise, the reaction conditions are mild and controllable, and large-scale production is facilitated.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of carbon ring compounds, in particular to a photoresist based on alkynyl bridging and biphenyl structure, a preparation method and application. BACKGROUND

[0002] With the continuous reduction of the wavelength of the light source used in photolithography technology, the spatial scale of photolithography is also reduced. In this case, it is of great research value to reduce the molecular size of the photoresist film former to replace the traditional polymer. Compared with the polymer photoresist, the molecular glass has smaller size and higher dispersity, which is more conducive to obtaining low line edge roughness and realizing high resolution. At present, the molecular glass represented by polyphenolic compounds, cyclic molecules, ladder compounds, fullerenes, etc. has become an important candidate material for advanced photolithography technology. Among them, the phenolic hydroxyl group of the polyphenolic molecular glass has strong modification property, and can provide proton to promote the electron transfer between the exposed area and the photoacid generator, which can significantly improve the resolution of the photoresist, and has obvious advantages in the field of photolithography. However, the reported polyphenolic photoresists have complex structures and cumbersome preparation processes, which increases the manufacturing cost, which is obviously not conducive to industrial application.

[0003] Therefore, it is of great significance to design a new type of molecular glass photoresist which is easy to prepare. SUMMARY

[0004] The present application aims to at least solve one of the problems in the related art. To this end, the first object of the present application is to provide a photoresist based on alkynyl bridging and biphenyl structure; the second object of the present application is to provide a preparation method of the photoresist based on alkynyl bridging and biphenyl structure; and the third object of the present application is to provide an application of the photoresist based on alkynyl bridging and biphenyl structure.

[0005] In order to achieve the first object, the technical solution adopted by the present application is: The photoresist based on alkynyl bridging and biphenyl structure has the following structural formula: R1, R2, R3, R4, R5 and R6 are each independently selected from any one of the following structural formulae: , and .

[0006] The present application is based on a non-planar polyphenyl structure constructed by introducing an alkyne group as a bridging body based on a biphenyl structure, taking a triphenyl (TP) system as a skeleton, and using a conjugated alkyne group to control the glass transition temperature of the molecule, so as to improve the thermal stability and film properties of the photoresist based on the alkyne bridging and biphenyl structure. Secondly, based on the structural characteristics of the molecular glass and the design requirements, the typical hydrophobic group-BOC , -BU and -AD is introduced into the TP polyphenol structure unit, which can not only reduce the crystallization ability of the photoresist, but also provide an acid-labile protecting group, so as to meet the performance requirements of the positive molecular glass for the photoetching process.

[0007] Preferably, R1, R2, R3, R4, R5 and R6 are selected from , and the photoresist based on the alkyne bridging and biphenyl structure has the following structure: or R1, R2, R3, R4, R5 and R6 are selected from , and the photoresist based on the alkyne bridging and biphenyl structure has the following structure: or R1, R2, R3, R4, R5 and R6 are selected from , and the photoresist based on the alkyne bridging and biphenyl structure has the following structure: .

[0008] In order to achieve the second object, the technical scheme adopted by the present application is: The preparation method of the photoresist based on the alkyne bridging and biphenyl structure is used for preparing the photoresist based on the alkyne bridging and biphenyl structure, and comprises the following steps: S100, in a reaction solvent I, 1,2,4,5-tetrabromobenzene is reacted with an acetylene derivative with a protecting group to synthesize compound I; S200, in a reaction solvent II, compound I is subjected to a self-coupling reaction under the action of a metal catalyst I to synthesize compound II; S300, in a reaction solvent III, compound II is subjected to a coupling reaction with p-hydroxyphenylboronic acid under the action of a metal catalyst II to synthesize compound III; S400, in a reaction solvent IV, compound III is reacted with any of the following substances to synthesize the photoresist based on the alkyne bridging and biphenyl structure: di-tert-butyl dicarbonate, tert-butyl bromoacetate and 2-chloroacetoxy-2-methyl adamantane.

[0009] Preferably, in step S100, the protecting group is selected from a silane group.

[0010] Preferably, in step S200, the metal catalyst I is selected from cuprous iodide.

[0011] Preferably, in step S300, the metal catalyst II is selected from tetrakis(triphenylphosphine)palladium.

[0012] Preferably, the reaction solvent I and the reaction solvent II are both selected from a mixed solvent consisting of tetrahydrofuran and triethylamine, and the volume ratio of tetrahydrofuran to triethylamine is 3:1 to 4:1.

[0013] Preferably, the reaction solvent III is selected from N,N-dimethylformamide, and the reaction solvent IV is selected from tetrahydrofuran.

[0014] To achieve the third object, the technical scheme adopted by the present application is: The application of the photoresist based on the alkyne bridging and biphenyl structure is used to prepare a photoresist coating material by using the photoresist based on the alkyne bridging and biphenyl structure. The photoresist coating material comprises the following components in terms of mass ratio: The photoresist based on the alkyne bridging and biphenyl structure is 8% to 10%, the photoacid generator is 0.35% to 0.45%, the quenching agent is 0.10% to 0.15%, and the rest is solvent.

[0015] The above one or more technical solutions in the embodiments of the present application have at least one of the following technical effects: The present application provides a photoresist based on the alkyne bridging and biphenyl structure. Based on the biphenyl structure, a non-planar polyphenyl structure is constructed by introducing an alkyne group as a bridging body, a triphenyl (TP) is used as a skeleton of a polyphenyl system, and a conjugated alkyne group is used to control the glass transition temperature of the molecule, so as to improve the thermal stability and film properties of the photoresist based on the alkyne bridging and biphenyl structure. Secondly, based on the structural characteristics of the molecular glass and the design requirements, a typical hydrophobic group-BOC, -BU and -AD is introduced on the basis of the TP polyphenol structure unit, which can not only reduce the crystallization ability of the photoresist, but also provide an acid-labile protecting group, so as to meet the performance requirements of the positive molecular glass for the photoetching process. Therefore, the photoresist can be used to prepare a photoresist coating material.

[0016] The preparation method provided by the present application has a simple synthesis route, mild and controllable reaction conditions, and is conducive to realizing large-scale production.

[0017] Additional aspects and advantages of the application will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following and / or can be learned by practice of the application. Attached Figure Description

[0018] 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.

[0019] 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.

[0020] 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

[0021] 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.

[0022] 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.

[0023] Example 1 Preparation of TP-BOC The process is as follows: I. Preparation of Compound I, the synthetic route is shown below: ; The preparation process is as follows: To a reaction system containing 1,2,4,5-tetrabromobenzene (8.0 g, 0.02 mol), trimethylsilyacetylene (1.96 g, 0.02 mol), tetrahydrofuran (150 mL) and triethylamine (50 mL) was added CuI (0.38 g, 2 mmol) under nitrogen atmosphere, and the reaction was stirred vigorously at 80 °C for 24 h, and then naturally cooled to room temperature. After filtration and removal of the solvent under reduced pressure, the crude product was separated by column chromatography (petroleum ether and dichloromethane mixed solution, volume ratio 1:1) to obtain the intermediate. Then, 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 (petroleum ether and dichloromethane mixed solution, volume ratio 1:2) to obtain compound I (11.79 g) with a yield of 75%, and the characterization data thereof are as follows: 1 H NMR (CDCI3): δ 7.84 (s, 1H), 7.45 (d, J =7.8 Hz, 1H), 4.01 (s, 1H); 13 C NMR (CDCI3): δ 137.80, 136.5, 127.8, 127.40, 126.8, 124.53, 82.3, 81.4.

[0024] II. Preparation of compound II, the synthetic route is as follows: ; The preparation process is as follows: Under nitrogen atmosphere, compound I (10.14 g, 3 mmol) was dissolved in tetrahydrofuran (200 mL) and triethylamine (50 mL), and then CuI (86 mg, 0.45 mmol) and K2CO3 (0.62 mg, 4.5 mmol) were added. Then, the reaction system was heated to 160 °C, and after stirring and heating at this temperature for 24 h, the reaction system was filtered while hot, and extracted with dichloromethane. After the organic layers were combined and dried with Na2SO4, the solvent was removed under reduced pressure, and the crude product was separated by column chromatography (petroleum ether and dichloromethane mixed solution, volume ratio 3:1) to obtain compound II (4.18 g) with a yield of 55%, and the characterization data thereof are as follows: 1 H NMR (CDCI3): δ 7.56 (s, 6H); 13 C NMR (CDCI3): δ135.20, 127.1, 125.2, 91.0.

[0025] III, the synthetic route of which is shown as follows: ; The preparation process is described as follows: Under a nitrogen atmosphere, a catalyst Pd(PPh3)4(2.4 g, 2 mmol) was added to a mixed system containing compound II (4.0 g, 5.17 mmol), p-hydroxybenzoic acid (5.74 g, 41.36 mmol) and K2CO3(14 g) in N,N-dimethylformamide (100 mL), and the reaction system was heated to 150°C, and then stirred at this temperature for 24 h. The reaction mixture was then poured into ice water, and a precipitate was separated out. The precipitate was filtered, and the filter cake was dried and then separated by column chromatography (the mobile phase was a mixture of petroleum ether and dichloromethane in a volume ratio of 1:2) to obtain compound III (2.64 g) with a yield of 61%, and the characterization data thereof are shown as follows: 1 H NMR (CDCI3): 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); 13 C NMR (CDCI3): δ 158.89, 139.54, 133.38, 132.23, 130.25, 121.75, 116.64, 90.82.

[0026] IV, the target compound TP-BOC is prepared using compound III, and the process is as follows: 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 a 100 mL three-necked flask, and then 4-dimethylaminopyridine (6.12 mg, 0.05 mmol) was added. The resulting solution was stirred overnight, and then quenched with water and extracted with dichloromethane. The organic layer was collected and dried with Na2SO4. The crude product was purified and separated by silica gel column chromatography (the mobile phase was a mixture of dichloromethane and ethyl acetate in a volume ratio of 20:1) to obtain the white solid target product TP-BOC (0.75 g) with a yield of 65%, and the characterization data thereof are shown as follows: 1 H NMR (CDCI3): δ8.05 (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); 13 C NMR (CDCI3): δ 165.71, 143.90, 139.79, 133.46, 131.41, 130.90, 128.61, 121.76, 90.82, 80.58, 28.37.

[0027] TP-BOC was dissolved in propylene glycol monomethyl ether acetate (solvent), followed by the addition of triphenylsulfonium perfluorobutylsulfonate (photoacid generator), triethylamine (quencher), to obtain a mixture; the proportion of each component was as follows: TP-BOC was 10%, photoacid generator was 0.40%, quencher was 0.10%, and solvent was 89.5% by mass fraction. After stirring the mixture at room temperature in the dark for 4h, the filtrate obtained after filtration using a 0.2μM Polytetrafluoroethylene (PTFE) membrane filter was the photoetching agent composition (denoted as sample 1), which used TP-BOC as the main etching component.

[0028] Example 2 Preparation of TP-BU The process was as follows: I. Preparation of compound I- compound III.

[0029] Prepared according to the synthesis route and preparation process of compound I- compound III in example 1.

[0030] II. Preparation of TP-BU using compound III, the process was as follows: To a 250 mL three-necked flask was added 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-pyrrolidinone (20 mL); after stirring the reaction at 80 °C for 5 h under nitrogen atmosphere, the reaction solution was cooled to room temperature, extracted with ethyl acetate three times, combined the organic layers, and dried the combined organic layer with anhydrous Na2SO4, to obtain the crude product, which was purified by silica gel column chromatography (mobile phase was a mixture of petroleum ether and ethyl acetate, the volume ratio of the two was 2:1), followed by precipitation with n-hexane, to obtain the white solid target product TP-BU (0.51 g), the yield was 70%, and its characterization data were as follows; 1 H NMR (CDCI3): 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); 13 C NMR (CDCI3): d 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, 66.46, 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.

[0031] TP-BU was dissolved in propylene glycol monomethyl ether acetate (solvent), then triphenylsulfonium perfluorobutylsulfonate (photoacid generator), triethylamine (quencher) were added to obtain a mixture; the proportions of each component were as follows: TP-BU was 9%, photoacid generator was 0.35%, quencher was 0.15%, and solvent was 90.5% by mass ratio. After the mixture was stirred at room temperature and away from light for 4 h, the filtrate obtained after filtration using a PTFE membrane filter with a specification of 0.2 μM was the photoetching agent composition (denoted as sample 2), which used TP-BU as the main etching component.

[0032] Example 3 Preparation of TP-AD The process was as follows: I. Preparation of compound I-III.

[0033] Prepared according to the synthesis route and preparation process of compound I-III in Example 1.

[0034] II. Preparation of TP-AD using compound III, the process was as follows: Into a 250 mL three-necked flask was added 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-pyrrolidinone (20 mL); then, after stirring at 80 °C for 5 h under a nitrogen atmosphere, the reaction solution was cooled to room temperature, extracted with ethyl acetate three times, the combined organic layers were dried over anhydrous Na2SO4 to obtain a crude product, which was purified by silica gel column chromatography (the mobile phase was a mixture of petroleum ether and ethyl acetate in a volume ratio of 3:1) to obtain the target product TP-AD (0.43 g) as a white solid, with a yield of 86%, and the characterization data thereof were as follows: 1 H NMR (CDCI3): δ 7.80 (s, 1H), 7.57 (d, J = 8.4 Hz, 2H), 7.09 (d, J = 8.4 Hz, 2H), 4.63 (s, 2H), 1.41 (s, 9H); 13 C NMR (CDCI3): 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.

[0035] TP-AD was dissolved in propylene glycol monomethyl ether acetate (solvent), followed by the addition of triphenylsulfonium perfluorobutylsulfonate (photoacid generator), triethylamine (quencher) to obtain a mixture; the proportions of each component were as follows: TP-AD 8%, photoacid generator 0.40%, quencher 0.10%, solvent 91.5% by mass; After stirring the mixture at room temperature for 4 h in the dark, the filtrate obtained after filtration using a PTFE membrane filter with a specification of 0.2 μM was the photoetching agent composition (denoted as sample 3), which used TP-AD as the main etching component.

[0036] Test Example Samples 1, 2 and 3 prepared using Example 1, Example 2 and Example 3, respectively, were used as photoresists to prepare lithographic patterns, as follows: The glass substrate was vacuum treated for 15 min before spin coating to remove adsorbed gases and moisture on the surface of the glass substrate and to eliminate static electricity, and then samples 1, 2 and 3 were coated on the surface layer of the substrate to form a photoresist coating layer with a thickness of 50-70 nm. Subsequently, pre-baking, exposure, post-baking and development were performed in sequence to obtain the lithographic patterns shown in Figure 1 , Figure 2 and Figure 3 , respectively. The pre-baking temperature for samples 1, 2 and 3 was 60°C, and the post-baking temperature for samples 1, 2 and 3 was 60°C, 130°C and 130°C, respectively. The light used for exposure was extreme ultraviolet light. The developer was a 2.38 wt% aqueous solution of tetramethylammonium hydroxide. As can be seen from Figure 1 , the edges of the stripes exhibited sharp edges without any blur, ragged edges or diffusion bands; the line width of the stripes and the spacing between the stripes were maintained with almost uniform precision, without any fluctuations in width / density, broken stripes, spots, bubbles or local damage; the stripes were parallel without any twisting, shifting or local misalignment; the above results show that sample 1, which used TP-BOC as the main etching component, had high photosensitivity and good resolution as a photoresist coating layer, and still had excellent lithographic etching effects after 60 days of storage; As can be seen from Figure 2 , although a small amount of broken stripes appeared in the pattern, the overall arrangement was regular, the line spacing was uniform, the edges of the stripes did not exhibit severe ragged edges or excessive diffusion blur, and the coating layer did not exhibit overall failure on the substrate; this result shows that sample 2, which used TP-BU as the main etching component, could be used as a photoresist coating layer, and still had good lithographic etching effects after 60 days of storage; As can be seen fromFigure 3 It can be seen that although the edge is slightly blurred, the overall arrangement of the stripes is regular, keeps continuous state, the line width and line spacing remain stable, and there is no obvious wide / narrow / dense variation phenomenon. The results show that sample 3 using TP-AD as the main component of etching can be used as a photoresist layer, and still has good photoetching effect after being stored for 60 days.

[0037] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application, but not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that the technical solutions recorded in the foregoing examples can still be modified, or some technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A photoetchant based on an alkynyl-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. 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. 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: Di-tert-butyl dicarbonate, tert-butyl bromoacetate, and 2-chloroacetoxy-2-methyladamantane.

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 alkyne bridging and biphenyl structure as described in claim 3, characterized in that, In step S200, the metal catalyst I is selected from cuprous iodide.

6. The method for preparing the photoetchant based on alkyne bridging and biphenyl structure as described in claim 3, characterized in that, In step S300, the metal catalyst II is selected from tetra(triphenylphosphine)palladium.

7. 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.

8. The method for preparing the photoetchant based on alkynyl 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.

9. 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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