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CN114114840B - Positive photoetching material based on tannic acid, preparation method thereof, photoresist system and application thereof in preparation of micro-nano circuit - Google Patents

Positive photoetching material based on tannic acid, preparation method thereof, photoresist system and application thereof in preparation of micro-nano circuit Download PDF

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CN114114840B
CN114114840B CN202111418612.9A CN202111418612A CN114114840B CN 114114840 B CN114114840 B CN 114114840B CN 202111418612 A CN202111418612 A CN 202111418612A CN 114114840 B CN114114840 B CN 114114840B
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tannic acid
photoresist
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mass
reaction
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CN114114840A (en
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汤紫成
康文兵
陈欢
赵莉苹
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Shandong University
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
    • C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
    • C07H13/08—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals directly attached to carbocyclic rings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

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  • Materials For Photolithography (AREA)

Abstract

The invention provides a positive photoetching material based on tannic acid, a preparation method thereof, a photoresist system and application thereof in preparing a micro-nano circuit.

Description

Positive photoetching material based on tannic acid, preparation method thereof, photoresist system and application thereof in preparation of micro-nano circuit
Technical Field
The invention relates to a positive photoetching material based on tannic acid, a preparation method thereof, a photoresist system and application thereof in preparing a micro-nano circuit, and belongs to the technical field of high polymer photosensitive imaging.
Background
Micro-nano circuits refer to conductive lines used in microelectronic processes to connect microelectronic elements, and are commonly used in the fields of lithography, wearable electronics, and the like. At present, a common deposition method of a micro-nano circuit uses metal ink, a cosurfactant and a stabilizer as raw materials, and uses an inkjet printing mode to deposit on a substrate (such as PDMS, PET, PI). The method has the following two main disadvantages: 1. the method is an ex-situ deposition method, and a stabilizer is needed to avoid the agglomeration of metal particles and the oxidization of the metal particles; 2. to achieve good conductivity, repeated ink ejection is required a plurality of times, and the resolution of the drawn line is not high enough due to the surface tension of the droplet.
The photolithography is a commonly used method for preparing a high-resolution micro-nano circuit, and in the process of constructing the circuit by the photolithography, a commonly used photoresist component is a phenolic resin and epoxy resin system, the resolution of the circuit is lower due to the molecular chain entanglement effect between polymers, and the synthesis process of the phenolic resin pollutes the environment and can release harmful gas to human bodies. The current photoetching method for preparing the micro-nano circuit comprises the following steps: firstly, preparing metal powder, uniformly mixing the metal powder with photoresist, drawing a circuit through photoetching, and annealing and sintering to obtain a conductive circuit, wherein the circuit obtained by the method has poor conductive performance because of a physical mixed ex-situ system; direct photoreduction, i.e., the irradiation of metal salt precursors in a photoresist, has also been used to construct circuits, but the local overheating effect of the laser can lead to uncontrollable growth and particle aggregation effects, leading to irreversible loss of electrical properties. If the particle growth is controlled by chemical reduction after photoetching and chemical plating, the problems of circuit resolution and functions can be well solved, and the photoresist at the moment not only bears the patterning function, but also can provide a carrier for conductive functionalization. Therefore, the construction of micro-nano circuits using a photolithography-electroless plating method has attracted considerable attention.
The photoetching-chemical plating method has the advantages that the photoetching system is selected to achieve high resolution of the micro-nano circuit, and simultaneously realize excellent mechanical property and electric conductivity, and the photoetching system is essentially an in-situ system of compounding nano metal and polymer. In a composite in-situ system of metal and polymer, the electrical performance depends on the density of nano metal particles in the polymer and the bonding capability between the nano metal particles and the polymer, obviously, the higher the density is, the better the electrical performance is, and the good bonding capability between the polymer/substrate and the metal can avoid an island growth mode at the initial stage of the metal particles, reduce unnecessary scattering of electrons, thereby reducing the conductive percolation threshold of the material, and realizing the good conductive capability in a shorter time; the mechanical properties depend on the structure of the composite system, and require good uniformity, ductility, and strong binding energy of the metal and polymer.
Tannic acid is a biological macromolecular material, has wide biological sources, is environment-friendly and low in price, can be used for preparing photoresist, and has rich phenolic hydroxyl groups, excellent adhesion and metal reducing capability, and benzene rings in the tannic acid provide sufficient rigidity and mechanical strength. However, tannic acid is used as a photoresist material, and has problems that: the toughness is insufficient, and the self-agglomeration phenomenon is easy to occur in an organic solvent due to the abundant phenolic hydroxyl groups, so that the application of the modified phenolic resin is limited; and the tannic acid coating has poor continuity and is rough, so that the good conductivity is required to be realized for a long time in the post-treatment electroless plating process.
Therefore, in order to avoid the resolution problem caused by chain entanglement of the traditional polymer resin and the pollution problem caused in the process of producing the resin, and simultaneously consider the performance requirement of a metal polymer in-situ system on the polymer, tannic acid is modified, the toughness and film forming property of tannic acid are improved, a positive photoetching material integrating photoetching property and conductive functionalization is obtained, and the preparation of a circuit with excellent conductive property and high resolution by utilizing the material has important significance. For this purpose, the present invention is proposed.
Disclosure of Invention
Aiming at the defects of the prior art, particularly the defects of lower resolution and poorer conductivity of the traditional method for drawing the micro-nano circuit based on the ink jet printing technology of metal ink, the invention provides a tannic acid-based positive photoetching material, a preparation method thereof, a photoresist system and application thereof in preparing the micro-nano circuit. The positive photoetching material is obtained by grafting tannic acid with di-tert-butyl dicarbonate and methacryloyl chloride in turn, and a photoresist system with tert-butoxycarbonyl and 2-methyl-1-propenyl grafted tannic acid as main components is used for photoetching to obtain a coating with good film forming property, and then a micro-nano circuit with high resolution and excellent conductivity is obtained through chemical plating.
The technical scheme of the invention is as follows:
a positive photoetching material based on tannic acid has a structural formula shown in a general formula I:
Wherein the substituents R are each independently selected from tert-butoxycarbonyl, 2-methyl-1-propenyl or H, and the molar ratio of tert-butoxycarbonyl, 2-methyl-1-propenyl and H in the substituents R is 0.1-0.7:0.1-0.4:0.1-0.3.
According to the preferred embodiment of the present invention, the molar ratio of t-butoxycarbonyl, 2-methyl-1-propenyl and H in the substituent R is 0.5-0.7:0.2-0.3:0.1-0.2.
According to the present invention, the above-mentioned positive photoresist material based on tannic acid is prepared by one of the following methods:
Method i: under the protection of nitrogen, tannic acid and di-tert-butyl dicarbonate are added into a solvent A, and then a catalyst is added for reaction, so that a reaction liquid is obtained; then adding triethylamine into the obtained reaction liquid under the protection of nitrogen at the temperature of 0-8 ℃, then dropwise adding methacryloyl chloride, then heating to room temperature for reaction, and after the reaction is completed, obtaining the positive photoetching material based on tannic acid through post-treatment; or alternatively, the first and second heat exchangers may be,
Method ii: under the protection of nitrogen, tannic acid is added into a solvent A at the temperature of 0-8 ℃, triethylamine is added, methacryloyl chloride is added dropwise, and then the reaction solution is obtained after the reaction is carried out at room temperature; and under the protection of nitrogen, adding di-tert-butyl dicarbonate into the obtained reaction solution, adding a catalyst for reaction, and after the reaction is finished, performing post-treatment to obtain the tannic acid-based positive photoetching material.
According to the invention, the molar ratio of di-tert-butyl dicarbonate to tannic acid in process i or process ii is preferably 3-21:1, more preferably 15-21:1.
According to the preferred embodiment of the present invention, in the method i or the method ii, the solvent a is a mixed solvent of acetone and the solvent B, wherein the volume ratio of the acetone to the solvent B in the mixed solvent is 1:4-6; the solvent B is N, N-dimethylformamide or N-methylpyrrolidone; the ratio of the volume of the solvent A to the mass of the tannic acid is 5-20 mL/1 g.
Preferably according to the invention, the catalyst in process i or process ii is 4-dimethylaminopyridine or triethylamine; the mass of the catalyst is 0.3-1% of the total mass of tannic acid and di-tert-butyl dicarbonate; the catalyst is dropwise added into the system in the form of catalyst acetone solution, the concentration of the catalyst acetone solution is 0.01-0.02g/mL, and the dropwise adding time is 10-15min.
According to a preferred embodiment of the invention, in process i or process ii, the tannic acid and di-tert-butyl dicarbonate are reacted for a period of time of from 10 to 16 hours.
According to a preferred embodiment of the invention, the molar ratio of triethylamine to methacryloyl chloride in process i or process ii is 1:1.
Preferably according to the invention, the molar ratio of methacryloyl chloride to tannic acid in process i or process ii is 2.5 to 10:1, more preferably 5 to 7.5:1; the dripping time of the methacryloyl chloride is 10-15min.
According to a preferred embodiment of the invention, in process i or process ii, the reaction time with methacryloyl chloride after the temperature has been raised to room temperature is from 8 to 12 hours.
According to a preferred embodiment of the invention, the post-treatment step in method i or method ii is: pouring the obtained reaction solution into water with the volume of 6-10 times, separating out a solid product, washing the solid product with water for 3-5 times, dissolving the solid product in ethyl acetate, drying the solid product with anhydrous magnesium sulfate, removing the solvent, and drying the obtained solid in vacuum to obtain the tannic acid-based positive photoetching material. The specific grafting ratio of the tert-butoxycarbonyl group and the 2-methyl-1-propylene group in the R substituent of the obtained product is calculated by nuclear magnetism hydrogen spectrum.
The ratio of hydroxyl groups substituted by tert-butoxycarbonyl groups and 2-methyl-1-propenyl groups in tannic acid has an important influence on the alkali resistance of the photoetching material, and the alkali resistance of a sample with the ratio of hydroxyl groups substituted (namely the molar ratio of tert-butoxycarbonyl groups to 2-methyl-1-propenyl groups in all substituents R, also called a grafting ratio) below 0.4 is poor; and the ratio of t-butoxycarbonyl protection (i.e., the molar ratio of t-butoxycarbonyl in all substituents R) is too high, the 2-methyl-1-propenyl grafting ratio is low (i.e., the molar ratio of 2-methyl-1-propenyl in all substituents R), and the resulting material has poor film forming properties, so that it is necessary to ensure that the molar ratio of t-butoxycarbonyl, 2-methyl-1-propenyl to H is within the scope of the present invention, and the molar ratio of t-butoxycarbonyl, 2-methyl-1-propenyl to H is preferably 0.5 to 0.7:0.2 to 0.3:0.1 to 0.2.
The invention also provides a photoresist system containing the positive photoresist material based on tannic acid, wherein the photoresist system comprises the positive photoresist material based on tannic acid, a solvent C, a photoacid generator and a cross-linking agent, and the solid content of the photoresist system is 15-25%, and the solid content is calculated according to the mass of the positive photoresist material based on tannic acid; the mass of the photoacid generator is 4-6% of that of the positive photoetching material based on tannic acid, and the mass of the cross-linking agent is 5-10% of that of the positive photoetching material based on tannic acid.
Preferably, the solvent C is propylene glycol methyl ether acetate or propylene glycol methyl ether.
Preferably, the photoacid generator is a combination of photoacid 3D (i.e., (E) -2- (4-methoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine) and photoacid PAG103 (i.e., (Z) -2- ((E) -2- ((propylsulfonyl) oxyimino) thiophene-3 (2H) -ethylene) -2- (o-tolyl) acetonitrile), wherein the photoacid 3D and photoacid PAG103 mass ratio is 1:1; the molecular formulas of photoacid 3D and photoacid PAG103 are shown in formulas II and III, respectively:
Preferably, the cross-linking agent is pentaerythritol triacrylate or pentaerythritol tetraacrylate.
According to the present invention, the above-mentioned method for preparing a photoresist system containing a tannic acid-based positive photoresist material is not particularly limited, and for example, the following method can be employed: and (3) dissolving the positive photoetching material based on tannic acid, the photoacid generator and the cross-linking agent in the solvent C, uniformly mixing, and filtering by using a polytetrafluoroethylene filter with the diameter of 0.22 microns to obtain the photoresist system containing the positive photoetching material based on tannic acid.
According to the invention, the use of the above-described photoresist system containing tannic acid-based positive photoresist materials for the preparation of micro-nano circuits by a photo-lithography-electroless process.
Preferably, according to the application of the present invention, the lithography process is: spin-coating a photoresist system on a substrate, and performing pre-baking, 365nm exposure, post-baking, development, 405nm exposure and baking to obtain a substrate coated with a photoetching coating; the thickness of the photoetching coating is 500nm-900nm; the substrate is not particularly limited, and may be a silicon wafer, a glass substrate, or the like; the developing solution in the developing process is a tetramethyl ammonium hydroxide solution with the mass concentration of 2.38 wt%; the pre-baking, exposure, post-baking, developing and baking are all common processes in the field.
Preferably, according to the application of the present invention, the electroless plating process is: soaking the substrate coated with the photoetching coating in a plating solution for 30-50min at 50-60 ℃, taking out, flushing with ultrapure water, and purging with nitrogen to obtain a micro-nano circuit; the plating solution is prepared by the following steps: dissolving metal salt in water, fully stirring, and adding ammonia water until the solution is clear; adding formaldehyde solution, sodium citrate and polyvinylpyrrolidone, stirring thoroughly, adding acetic acid, and adjusting pH to 8-9.
Further preferably, the metal salt is silver nitrate, copper nitrate or zinc nitrate; the ratio of the mass of the metal salt to the volume of water is 5-30 mg/1 mL;
Further preferably, the mass concentration of the ammonia water is 25wt%; the addition amount of the ammonia water is not particularly limited, and the formed precipitation vanishing solution is clarified, preferably a metal ammonia salt complex is formed, and may be slightly excessive;
further preferably, the formaldehyde solution has a mass concentration of 20-25wt%; the volume ratio of the formaldehyde solution to the water is 0.4-1:100;
Further preferably, the mass ratio of polyvinylpyrrolidone to metal salt in the plating solution is 1-2:1; the mass ratio of the sodium citrate to the metal salt is 1-2:1.
The present invention is not described in detail in the prior art.
The invention has the technical characteristics and beneficial effects that:
1. The positive photoetching material of the invention takes tannic acid as a main body, and adopts a one-pot method to react with di-tert-butyl dicarbonate and methacryloyl chloride in sequence to synthesize tannic acid resin with phenolic hydroxyl protected by tert-butyl carbonate and replaced by 2-methyl-1-propenyl carbonyl, wherein the tert-butoxy carbonyl is an acid sensitive group, and only certain acidity and temperature are needed for dissociation; the grafted 2-methyl-1-propenyl carbonyl can be polymerized by a photoacid generator under ultraviolet irradiation, the film forming continuity and alkali resistance of tannic acid are improved, a dense continuous film can reduce the percolation threshold of a material in the chemical plating process, and excellent conductivity is realized in a short time with the help of recovered phenolic hydroxyl groups, so that a micro-nano circuit obtained by chemical plating of the photoresist has high resolution and excellent conductivity.
2. The polymerization of the positive photoetching material is initiated only by illumination at room temperature, the photoetching coating containing the circuit is prepared by ultraviolet exposure, development and baking at 365nm, then the positive photoetching material in the photoresist in the unexposed area is subjected to ultraviolet exposure for the second time, the crosslinking is realized by baking, the recovery of phenolic hydroxyl is realized, the subsequent electroless metal plating reduction site is provided, the reducibility of the phenolic hydroxyl and the good film forming property of a crosslinked network are provided, the in-situ growth of metal nano particles can be realized by the coating within a shorter electroless plating time, the electric conduction of the coating is realized, and the micro-nano circuit with excellent electric conductivity and appearance is prepared in a short time. The tannic acid resin can be applied to a photoetching method for preparing a micro-nano level circuit.
3. In the preparation process of the micro-nano circuit, a double exposure process is adopted, the first exposure is carried out by 365nm ultraviolet to obtain a conductive pattern, and then the second exposure is carried out by 405nm ultraviolet to expose a first unexposed area (namely a mask area), so that the photo-induced crosslinking of a positive photoetching material and the recovery of phenolic hydroxyl groups of tannic acid are realized, the crosslinking of the positive photoetching material improves the film forming property and alkali resistance of tannic acid, so that excellent conductivity is realized rapidly in the electroless plating process, and the recovered hydroxyl groups can provide metal reduction sites, thereby obtaining the micro-nano circuit; and the pattern exposed at 365nm only once has poor alkali resistance and poor conductivity after the subsequent electroless plating.
Drawings
FIG. 1 is a schematic flow chart of the photolithography-electroless plating process of the present invention.
FIG. 2 is a nuclear magnetic resonance spectrum of a positive tannic acid-based photolithography material prepared in example 1, wherein A is a characteristic peak of hydrogen on a benzene ring, B is a characteristic peak of hydrogen on tert-butyl, D is a characteristic peak of hydrogen on methylene in a carbon-carbon double bond, and the corresponding integration area is in parentheses.
FIG. 3 is an infrared spectrum showing the change of the functional groups of the entire photoresist composition during the photolithography process in example 3.
Fig. 4 is an optical microscope photograph of the photoresist line obtained in example 3.
Fig. 5 is an optical microscope photograph of the circuit obtained in example 3.
FIG. 6 is a cross-sectional scanning electron microscope image of the circuit obtained in example 3.
Detailed Description
The invention will be further illustrated with reference to specific examples, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
Example 1
A preparation method of a positive photoetching material based on tannic acid comprises the following steps:
(1) 4.25g of tannic acid is dried in a vacuum drying oven in advance, then is dissolved in a mixed solvent of 10mL of acetone and 40mL of N-methylpyrrolidone, after the complete dissolution, 10.00g of di-tert-butyl dicarbonate is added under the condition of nitrogen protection and stirring, 10mL of 4-dimethylaminopyridine acetone solution with the concentration of 0.01g/mL is dropwise added after stirring for 10min, and the dropwise adding time is 15min; then, the reaction was carried out at room temperature for 12 hours to obtain a reaction solution.
(2) Under the protection of nitrogen, under the ice bath condition of 0-5 ℃, 1.31g of triethylamine is added into the reaction liquid obtained in the step (1), then 1.36g of methacryloyl chloride is slowly added dropwise, the dropwise adding time is 15min, then the reaction liquid is heated to room temperature, and the reaction is carried out for 9h at the room temperature. After the reaction was stopped, the reaction solution was poured into 500mL of ultrapure water, the precipitated product was washed with ultrapure water for 4 times, the washed product was dissolved in 100mL of ethyl acetate, dried over anhydrous magnesium sulfate, and the solvent was removed by spin evaporation, and the obtained product was dried under vacuum at 40℃for 8 hours to obtain a tannic acid-based positive-working photolithographic material as white yellowish powder.
The nuclear magnetic hydrogen spectrum of the tannic acid-based positive lithography material prepared in this example is shown in fig. 2, the grafting ratio is calculated by nuclear magnetism, the grafting ratio of tert-butoxycarbonyl group is 0.6,2-methyl-1-propenyl group is 0.2, i.e. the molar ratio of tert-butoxycarbonyl group, 2-methyl-1-propenyl group and H is 0.6:0.2:0.2.
Example 2
A method for preparing a photoresist system of a positive photoresist material based on tannic acid, comprising the steps of:
1g of the tannic acid-based positive photoetching material prepared in example 1 is added into 5g of propylene glycol methyl ether, 30mg of photoacid 3D and 30mg of photoacid PAG103 are added, 50mg of pentaerythritol triacrylate is added, and after ultrasonic mixing is carried out at room temperature, a polytetrafluoroethylene filter with the thickness of 0.22 microns is used for filtering, thus obtaining the tannic acid-based positive photoetching material.
Example 3
Using the photoresist system obtained in example 2, a micro-nano circuit was prepared using a photolithography-electroless plating process, as follows:
(1) The photoresist system obtained in the example 2 is spin-coated on the surface of a two-inch silicon wafer, the specific process flows comprise spin coating, pre-baking, 365nm ultraviolet exposure, post-baking, developing, 405nm ultraviolet exposure and baking, the silicon wafer coated with the photoetching coating is obtained, the silicon wafer coated with the photoresist line is obtained, the developing is carried out by using tetramethyl ammonium hydroxide developing solution with the mass concentration of 2.38wt%, and the specific process parameters are shown in the following table 1.
TABLE 1
The infrared spectrogram of the functional group change of the whole component of the photoresist system in the photoetching process is shown in figure 3, and the main observation position is CH 3(2875cm-1),C＝C(813cm-1,1629cm-1),OH(3400cm-1). The grafted tannic acid product showed a disappearance of the OH peak, a presence of CH 3(2875cm-1) and a presence of the double bond c=c (813 cm -1,1629cm-1) peak in the infrared spectrum, due to the substantial reduction of the boc protection OH relative to tannic acid; chemical change of photoresist film: after the 365nm ultraviolet irradiation exposure and post-baking, the OH (3400 cm -1) peak reappears, the C=C (813 cm -1,1629cm-1) peak is slightly reduced, and the C=C (813 cm -1,1629cm-1) peak disappears after the 405nm ultraviolet irradiation, so that the 405nm irradiation induced crosslinking effect is better than 365nm photoinitiated crosslinking.
The optical microscope image of the photoresist line obtained in this example is shown in fig. 4, the photoresist surface is smoother, the line width is 80 μm, and the pattern is clear.
(2) 1G of silver nitrate is dissolved in 100mL of water, ammonia water with the mass concentration of 25wt% is gradually added dropwise until the solution with the precipitation disappeared is clear, and 0.5mL of ammonia water is added dropwise altogether; adding 0.5mL of formaldehyde solution with the mass concentration of 25wt%, 1g of sodium citrate and 1g of polyvinylpyrrolidone into the solution, stirring for 15min, and dropwise adding acetic acid to adjust the pH of the system to 9 after the solution is completely dissolved to obtain a plating solution; heating the plating solution to 60 ℃, and adding the silicon wafer coated with the photoetching coating into the plating solution to soak for 40min; and after 40min, taking out the silicon wafer, flushing with ultrapure water, and purging with nitrogen to obtain the micro-nano circuit.
The optical microscope image and the cross-section scanning electron microscope image of the micro-nano circuit obtained by the embodiment are respectively shown in fig. 5 and 6, and as can be seen from fig. 5, after chemical plating, silver nano particles grow on the surface of tannin photoresist in situ, and the surface of the photoresist is obviously covered by the silver nano particles; as can be seen from fig. 6, the photoresist cross section is uniformly distributed by silver nanoparticles, and exhibits a layered structure.
The micro-nano circuit obtained by the embodiment has the advantages of 0.03 ohm resistance and excellent conductivity by using a four-probe resistance meter.
Comparative example 1
A method for preparing a tannic acid-based positive photoresist material is as described in example 1, except that: the amount of the di-tert-butyl dicarbonate added in the step (1) is 1.1g, and 1.1mL of 4-dimethylaminopyridine acetone solution with the concentration of 0.01g/mL is dropwise added; the amount of methacryloyl chloride added in step (2) was 0.45g and 0.44g of triethylamine was added.
The positive photoetching material obtained in the comparative example is used for preparing a photoetching coating layer because the ratio of hydroxyl groups to be replaced is low, and the obtained photoetching coating layer is dissolved in a developing solution for 30 seconds and has poor alkali resistance.
Comparative example 2
A method for preparing a tannic acid-based positive photoresist material is as described in example 1, except that: the amount of the di-tert-butyl dicarbonate added in the step (1) is 12.5g, and 11.8mL of 4-dimethylaminopyridine acetone solution with the concentration of 0.01g/mL is added dropwise; the amount of methacryloyl chloride added in step (2) was 0.45g and 0.44g of triethylamine was added.
The positive photoetching materials prepared in the comparative example are used for preparing conductive circuits by referring to the methods of the examples 2 and 3, and the obtained material has low crosslinking degree under 405nm light because the grafting ratio of 2-methyl-1-propenyl is less than 0.1, so that the circuit patterns are easy to separate in the electroless plating process, and the film forming property is poor.
Comparative example 3
A method of preparing a photoresist system for tannic acid based positive working lithography is described in example 2, except that: the amount of the crosslinking agent added was 15% of the tannic acid-based positive-working lithography material.
The circuit was fabricated using the photoresist system described above using the method of example 3, and the resolution of the resulting circuit was low, and the resistance of the micro-nano circuit obtained in this comparative example was measured to be 200 ohms using a four-probe resistance meter, with reduced conductivity.

Claims (9)

1. A photoresist system comprising a tannic acid-based positive photoresist material, wherein the tannic acid-based positive photoresist material has a structural formula as shown in formula I:
wherein the substituents R are each independently selected from tert-butoxycarbonyl, 2-methyl-1-propenyl carbonyl or H, and the molar ratio of tert-butoxycarbonyl, 2-methyl-1-propenyl and H in the substituents R is 0.1-0.7:0.1-0.4:0.1-0.3;
the preparation method of the tannic acid-based positive photoetching material adopts one of the following methods:
Method i: under the protection of nitrogen, tannic acid and di-tert-butyl dicarbonate are added into a solvent A, and then a catalyst is added for reaction, so that a reaction liquid is obtained; then adding triethylamine into the obtained reaction liquid under the protection of nitrogen at the temperature of 0-8 ℃, then dropwise adding methacryloyl chloride, then heating to room temperature for reaction, and after the reaction is completed, obtaining the positive photoetching material based on tannic acid through post-treatment; or alternatively, the first and second heat exchangers may be,
Method ii: under the protection of nitrogen, tannic acid is added into a solvent A at the temperature of 0-8 ℃, triethylamine is added, methacryloyl chloride is added dropwise, and then the reaction solution is obtained after the reaction is carried out at room temperature; under the protection of nitrogen, di-tert-butyl dicarbonate is added into the obtained reaction liquid, then a catalyst is added for reaction, and after the reaction is completed, the positive photoetching material based on tannic acid is obtained through post-treatment;
in the method i or the method ii, the solvent A is a mixed solvent of acetone and the solvent B, and the solvent B is N, N-dimethylformamide or N-methylpyrrolidone; the catalyst in the method i or the method ii is 4-dimethylaminopyridine or triethylamine;
The photoresist system comprises a positive photoresist material based on tannic acid, a solvent C, a photoacid generator and a cross-linking agent, wherein the solid content of the photoresist system is 15-25%, and the solid content is calculated according to the mass of the positive photoresist material based on tannic acid; the mass of the photoacid generator is 4-6% of that of the positive photoetching material based on tannic acid, and the mass of the cross-linking agent is 5-10% of that of the positive photoetching material based on tannic acid; the solvent C is propylene glycol methyl ether acetate or propylene glycol methyl ether; the photoacid generator is a combination of photoacid 3D and photoacid PAG103, wherein the mass ratio of the photoacid 3D to the photoacid PAG103 is 1:1; the cross-linking agent is pentaerythritol triacrylate or pentaerythritol tetraacrylate.
2. The photoresist system comprising a tannic acid based positive working photoresist material according to claim 1, wherein the molar ratio of t-butoxycarbonyl, 2-methyl-1-propenyl and H in the substituent R is 0.5-0.7:0.2-0.3:0.1-0.2.
3. The photoresist system comprising a tannic acid based positive working photoresist material according to claim 1, characterized in that the molar ratio of di-tert-butyl dicarbonate to tannic acid in process i or process ii is 3-21:1;
In the method i or the method ii, the volume ratio of the acetone to the solvent B in the mixed solvent is 1:4-6; the ratio of the volume of the solvent A to the mass of the tannic acid is 5-20 mL/1 g.
4. The photoresist system comprising a tannic acid based positive working photoresist material according to claim 1, characterized in that the molar ratio of di-tert-butyl dicarbonate to tannic acid in process i or process ii is 15-21:1.
5. The photoresist system comprising a tannic acid based positive working photoresist material according to claim 1, characterized in that the mass of the catalyst in method i or method ii is 0.3-1% of the total mass of tannic acid and di-tert-butyl dicarbonate; the catalyst is dropwise added into the system in the form of catalyst acetone solution, wherein the concentration of the catalyst acetone solution is 0.01-0.02g/mL, and the dropwise adding time is 10-15min; the reaction time of tannic acid and di-tert-butyl dicarbonate is 10-16h.
6. The photoresist system comprising a tannic acid based positive working photoresist material according to claim 1, characterized in that the molar ratio of triethylamine to methacryloyl chloride in method i or method ii is 1:1; the mol ratio of the methacryloyl chloride to the tannic acid is 2.5-10:1; the dripping time of the methacryloyl chloride is 10-15min; the reaction time with the methacryloyl chloride is 8 to 12 hours after the temperature is raised to the room temperature;
The post-treatment steps are as follows: pouring the obtained reaction solution into water with the volume of 6-10 times, separating out a solid product, washing the solid product with water for 3-5 times, dissolving the solid product in ethyl acetate, drying the solid product with anhydrous magnesium sulfate, removing the solvent, and drying the obtained solid in vacuum to obtain the tannic acid-based positive photoetching material.
7. Use of a photoresist system containing a tannic acid based positive photoresist material according to claim 1 for the preparation of micro-nano circuits by a photo-chemical plating process.
8. The use of a photoresist system according to claim 7, wherein the lithography process is: spin-coating a photoresist system on a substrate, and performing pre-baking, 365nm exposure, post-baking, development, 405nm exposure and baking to obtain a substrate coated with a photoetching coating;
The electroless plating process comprises the following steps: soaking the substrate coated with the photoetching coating in a plating solution for 30-50min at 50-60 ℃, taking out, flushing with ultrapure water, and purging with nitrogen to obtain a micro-nano circuit; the plating solution is prepared by the following steps: dissolving metal salt in water, fully stirring, and adding ammonia water until the solution is clear; adding formaldehyde solution, sodium citrate and polyvinylpyrrolidone, stirring thoroughly, adding acetic acid, and adjusting pH to 8-9.
9. Use of a photoresist system according to claim 8, wherein the thickness of the photolithographic coating is 500nm-900nm; the developing solution in the developing process is a tetramethyl ammonium hydroxide solution with the mass concentration of 2.38 wt%;
The metal salt is silver nitrate, copper nitrate or zinc nitrate; the ratio of the mass of the metal salt to the volume of water is 5-30 mg/1 mL; the mass concentration of the ammonia water is 25wt%; the mass concentration of the formaldehyde solution is 20-25wt%; the volume ratio of the formaldehyde solution to the water is 0.4-1:100; the mass ratio of polyvinylpyrrolidone to metal salt in the plating solution is 1-2:1; the mass ratio of the sodium citrate to the metal salt is 1-2:1.
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