A gold nanocluster photoresist with co-initiator and method

Abstract

The application discloses a kind of gold nanocluster photoresist and method of adding co-initiator, belong to micro-nano processing manufacturing and photosensitive material technical field.The photoresist includes gold nanocluster 0.01wt%-30wt%, co-initiator 1wt%-10wt%, polymerization active monomer 95wt%-70wt% and organic solvent 0.1wt%-5wt% by mass percentage content calculation, wherein, co-initiator is thiol or amine.The application can significantly improve solubility and light transmittance by adding thiol or amine in gold nanocluster photoresist, and special interaction is generated with gold nanocluster, the photoresist has ultra-high sensitivity, ultra-low threshold, excellent printing effect;It can realize the ultra-low power processing of metal-polymer 3D structure, and also can realize ultraviolet light curing.

Description

Technical Field

[0001] The present invention belongs to the technical field of micro-nano processing and photosensitive materials, and specifically relates to a gold nanocluster two-photon photoresist with added co-initiator and a micro-nano 3D printing and photopatterning method thereof. Background Art

[0002] Two-photon 3D printing, also known as micro-nano 3D printing, is the most representative micro-nano 3D printing technology of the 21st century. It boasts unique advantages, including ultra-high three-dimensional precision and powerful stereolithography capabilities. Two-photon printing is essentially a 3D writing technology; it eliminates the need to create complex objects layer by layer and can create microstructures with submicron features in a relatively simple manner. These properties stem from the nonlinear optical properties of light absorption and the subsequent polymerization chemistry in two-photon 3D printing. Unlike traditional single-photon polymerization, in the two-photon printing process, two photons are simultaneously absorbed by the photosensitive material. The total energy from the two photons resonates with the energy difference between the ground and excited states. Due to the nonlinear absorption properties that occur during this process, two-photon printing achieves higher resolution than single-photon polymerization.

[0003] However, most current two-photon 3D printing methods use two-photon photoresists composed of organic resin monomers and organic small molecule initiators. These materials have low initiator content, resulting in low processing sensitivity and poor mechanical properties of the processed structures. The use of metal-polymer composites can significantly improve the mechanical properties of 3D structures. Currently, organic-inorganic composite 3D structures can be created by adding metal ions or inorganic nanoparticles to the photoresist and then performing two-photon 3D printing. Alternatively, a metal layer can be deposited onto an organic 3D structure. However, these methods suffer from low processing precision, complex steps, or a single, uniform structure.

[0004] Under laser, due to the presence of inorganic nanoparticles, the strong light scattering effect will reduce the 3D printing resolution. It is difficult to effectively control the processing accuracy of the structure through two-photon 3D printing by two-photon reduction of metal ions. The technical literature (QiLi, et al. Mechanical nanolattices printed using nanocluster-based photoresists, Science. 2022) developed gold / silver metal nanocluster-based two-photon photoresist for the first time. This ultra-small metal nanocluster does not cause light scattering and lead to a decrease in the resolution of the 3D structure. Metal nanoclusters have good solubility in polymerization-active monomers, which can realize the "one-step" 3D printing of organic-inorganic composite materials without the need for complex post-processing. The technical literature (Jin Tang, et al. Two-Orders-of-Magnitude Enhancement of Photoinitiation Activity via a Simple Surface Engineering of Metal Nanoclusters, Angew. Chem. Int. Ed. 2024) obtained a cluster two-photon photoresist with higher sensitivity, but due to its high concentration and low transmittance, it cannot meet the needs of high-throughput two-photon 3D printing of complex three-dimensional structures at low power.

[0005] Photoinitiators are divided into Type I and Type II. Type I initiators generate free radicals by breaking chemical bonds inside the molecule under light conditions, thereby initiating subsequent chemical reactions. Type II initiators generate free radicals by absorbing hydrogen and are usually used together with hydrogen proton donors (coinitiators). Type II initiators usually have a significant improvement in initiation performance after the addition of a co-initiator. Traditional small molecule Type II co-initiators have a significant improvement in two-photon initiation performance after the addition of amines, but no significant improvement in initiation performance has been found after the addition of thiols. The gold nanoclusters invented this time are the first discovered Type II cluster initiators. Unlike traditional organic small molecule photoinitiators, not only will there be a significant improvement after the addition of amines, but the improvement in initiation performance will be even greater after the addition of thiols. The printing sensitivity has reached an extremely high level, and it has excellent processability. Summary of the Invention

[0006] The present invention aims to overcome the shortcomings of the prior art and provide a gold nanocluster photoresist and method for adding a coinitiator (thiol or amine). The present invention is based on the micro-nano 3D printing of gold nanocluster photoresists with added coinitiators. This method enables the printing of 3D structures in a single step, exhibiting extremely high sensitivity, a very low processing threshold, and excellent solubility and processing properties. Furthermore, based on the photocuring properties of the gold nanocluster photoresist with added coinitiators under ultraviolet light, the present method achieves the first photopatterning under ultraviolet light conditions using gold nanoclusters as photoinitiators.

[0007] The specific technical solutions adopted in the present invention are as follows:

[0008] In a first aspect, the present invention provides a gold nanocluster photoresist with added co-initiator, comprising 0.01wt%-30wt% of gold nanoclusters, 1wt%-10wt% of co-initiator, 95wt%-70wt% of polymerization active monomers and 0.1wt%-5wt% of organic solvent, calculated by mass percentage.

[0009] Preferably, the gold nanoclusters are Au 25 (SC8H 17 ) 18 ,Au 25 (SC 10 H 21 ) 18 ,[Au 25 (PPh3) 10 (SC8H 17 )5] 2+ ,Au 25 (SC6H 12 OH) 18 ,Au 25 (SC3H6) 18 ,[Au 25 (PPh3) 10 (SC3H6)5] 2+ ,[Au 25 (PPh3) 10 (SC6H 12 OH)5] 2+ ,Au 25 (SC2H4Ph) 18 ,Au 25 (SCH2Ph) 18 ,Au 25 (SC6H 13 ) 18 Any one or a combination of two or more.

[0010] Preferably, the co-initiator is a thiol or an amine; the thiol is benzyl mercaptan, benzyl mercaptan, phenylethyl mercaptan, phenylpropyl mercaptan, butyl mercaptan, pentyl mercaptan, hexyl mercaptan, octyl mercaptan, nonyl mercaptan, decanethiol, cyclohexyl mercaptan, adamantane mercaptan, pentaerythritol tetrakis (3-mercaptopropionic acid) ester, p-phenylenedithiol, m-phenylenedithiol, o-phenylenedithiol, p-phenylmethyl mercaptan, m-phenylmethyl mercaptan, o-phenylmethyl mercaptan, p-phenylenedithiol, m-phenylenedithiol, any one or a combination of two or more of thiol, o-phenylenedithiol and hexanedithiol; and any one or a combination of two or more of amine, including aniline, benzylamine, phenylethylamine, amphetamine, triethylamine, butylamine, pentylamine, hexylamine, octylamine, nonylthiolamine, decylamine, cyclohexylamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, p-benzylamine, m-benzylamine, o-benzylamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine and hexylenediamine.

[0011] Preferably, the polymerization active monomer is any one of polyethylene glycol diacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, polydipentaerythritol pentaacrylate, acrylic-cage polysilsesquioxane, neopentyl glycol diacrylate, dipentaerythritol hexaacrylate and diurethane dimethacrylate, or a combination of two or more thereof.

[0012] Preferably, the organic solvent is any one or a combination of two or more of methanol, ethanol, isopropanol, ethyl ether, diethanol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, γ-butyrolactone, di(ethylene glycol) diethyl ether, methyl isobutyl ketone diethanol monoethyl ether, acetone, dichloromethane, chloroform, n-hexane, toluene, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide.

[0013] In a second aspect, the present invention provides a method for preparing a gold nanocluster photoresist with the addition of a coinitiator, as follows:

[0014] 0.01wt%-30wt% of gold nanoclusters calculated by mass percentage and 1wt%-5wt% of organic solvent are uniformly mixed, and then 95wt%-70wt% of polymerization active monomers calculated by mass percentage are added, and finally 1wt%-10wt% of coinitiator calculated by mass percentage is added, and the mixed solution is stirred and dispersed for 5-30 minutes to obtain a gold nanocluster photoresist with added coinitiator.

[0015] In a third aspect, the present invention provides a micro-nano 3D printing method based on a gold nanocluster photoresist with the addition of a co-initiator, as follows:

[0016] The gold nanocluster photoresist with added coinitiator as described in any one of the first aspects or the gold nanocluster photoresist with added coinitiator obtained by the preparation method described in the second aspect is 3D printed using a two-photon 3D printing system; the obtained 3D structure is then developed in a developer and blown dry with nitrogen to obtain the 3D structure of the gold nanocluster photoresist with added coinitiator.

[0017] Preferably, in the two-photon 3D printing system, the laser wavelength is 780 nm, the laser power is 0.25-50 mW, the laser pulse is 120 fs, the laser frequency is 80 MHz, and the printing speed is 0.1-100 mm / s.

[0018] Preferably, the developer is any one of propylene glycol methyl ether acetate, isopropyl alcohol, and dichloromethane, or a combination of two or more thereof, and the developing time is 2-40 minutes.

[0019] In a fourth aspect, the present invention provides a 3D structure of a gold nanocluster photoresist with a co-initiator added, prepared by the micro-nano 3D printing method as described in the third aspect.

[0020] In the fifth aspect, the present invention provides an application of a gold nanocluster photoresist with an added co-initiator in photopatterning. Specifically, the gold nanocluster photoresist with an added co-initiator as described in any one of the first aspects or the gold nanocluster photoresist with an added co-initiator obtained by the preparation method described in the second aspect is placed in a mold and cured under an ultraviolet light source with a wavelength of 365nm.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The gold nanocluster photoresist with added co-initiator prepared by the present invention uses gold nanoclusters as initiators and thiols or amines as co-initiators. It has excellent processing performance (extremely high processing sensitivity and extremely low processing threshold), can process a variety of complex 3D structures, and can achieve photopatterning under ultraviolet light conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is an electron microscope image of the three-dimensional structure of the photoresist obtained in Example 1 after micro-nano 3D printing.

[0024] Figure 2 This is a light microscope image of the block structure of the photoresist obtained in Example 1 after micro-nano 3D printing.

[0025] Figure 3 This is a light microscope image of the three-dimensional structure of the photoresist obtained in Example 2 after micro-nano 3D printing.

[0026] Figure 4This is a light microscope image of the block structure of the photoresist obtained in Example 3 after micro-nano 3D printing.

[0027] Figure 5 This is a light microscope image of the frame structure of the photoresist obtained in Example 4 after micro-nano 3D printing.

[0028] Figure 6 This is a light microscope image of the frame structure of the photoresist obtained in Example 5 after micro-nano 3D printing.

[0029] Figure 7 This is a light microscope image of the frame structure of the photoresist obtained in Example 6 after micro-nano 3D printing.

[0030] Figure 8 This is a photo of the photoresist obtained in Example 1 after being cured by ultraviolet light. DETAILED DESCRIPTION

[0031] In order to illustrate the present invention more clearly, the present invention will be further described below in conjunction with preferred embodiments and accompanying drawings. However, it should be understood by those skilled in the art that these embodiments are only examples. The numerous variations, changes and substitutions that can be thought of by those skilled in the art do not exceed the present invention. It should be understood that in the practice of the present invention, various replacements of the embodiments of the present invention described in this application document can be adopted. The attached claims are intended to limit the scope of the present invention, and the methods and structures within the scope of these claims and their equivalents should be covered thereby. For those examples where specific conditions are not specified, the conditions are carried out according to conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments involved without indicating the manufacturer are all conventional products available commercially.

[0032] First, the present invention provides a gold nanocluster photoresist with added co-initiator, the composition of the material mainly includes (calculated by mass percentage): 0.01wt%-30wt% of gold nanoclusters, 1wt%-10wt% of co-initiator, 95wt%-70wt% of polymerization active monomers and 0.1wt%-5wt% of organic solvent.

[0033] As a preferred embodiment of the present invention, the gold nanoclusters can be made of Au 25 (SC8H 17 ) 18 ,Au 25 (SC 10 H 21 ) 18 ,[Au 25 (PPh3) 10 (SC8H 17 )5] 2+ ,Au 25 (SC6H 12OH) 18 ,Au 25 (SC3H6) 18 ,[Au 25 (PPh3) 10 (SC3H6)5] 2+ ,[Au 25 (PPh3) 10 (SC6H 12 OH)5] 2 ,Au 25 (SC2H4Ph) 18 ,Au 25 (SCH2Ph) 18 and Au 25 (SC6H 13 ) 18 The co-initiator can be a thiol or an amine. Wherein, the thiol is any one of benzyl mercaptan, benzyl mercaptan, phenylethyl mercaptan, phenylpropyl mercaptan, butyl mercaptan, pentyl mercaptan, hexyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan, cyclohexyl mercaptan, adamantane mercaptan, pentaerythritol tetrakis(3-mercaptopropionate), p-phenylenedithiol, m-phenylenedithiol, o-phenylenedithiol, p-phenylmethyl mercaptan, m-phenylmethyl mercaptan, o-phenylmethyl mercaptan, p-phenylenedithiol, m-phenylenedithiol, o-phenylenedithiol and hexyl mercaptan, or a combination of two or more thereof; the amine is any one of aniline, benzylamine, phenylethylamine, amphetamine, triethylamine, butylamine, pentylamine, hexylamine, octylamine, nonyl mercaptanamine, decylamine, cyclohexylamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, p-benzylamine, m-benzylamine, o-benzylamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine and hexylenediamine, or a combination of two or more thereof. The polymerization active monomer can be any one of polyethylene glycol diacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, polydipentaerythritol pentaacrylate, acrylic-cage polysilsesquioxane, neopentyl glycol diacrylate, dipentaerythritol hexaacrylate, and diurethane dimethacrylate, or a combination of two or more thereof. The organic solvent can be any one of ether, diethanol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, γ-butyrolactone, diethylene glycol diethyl ether, methyl isobutyl ketone diethanol monoethyl ether, acetone, dichloromethane, chloroform, n-hexane, toluene, tetrahydrofuran, N,N-dimethylformamide methanol, ethanol, and isopropyl alcohol, or a mixture of two or more thereof.

[0034] Secondly, for the gold nano cluster photoresist of above-mentioned interpolation mercaptan, can make by uniformly mixing each component. Specifically, in the preparation process, can first evenly mix the gold nano cluster 0.01wt%-30wt% and organic solvent 0.1wt%-5wt% calculated with mass percentage content, then add polymerization activity monomer 95wt%-70wt% calculated with mass percentage content, disperse with stirring (preferably ultrasonic dispersion time is 5-30min), finally splash into 1wt%-10wt% mercaptan calculated with mass percentage content, obtain the gold nano cluster photoresist of interpolation mercaptan. For the gold nano cluster photoresist of above-mentioned interpolation amine, can make by uniformly mixing each component. Specifically, during the preparation process, 0.01wt%-30wt% of gold nanoclusters calculated by mass percentage and 0.1wt%-5wt% of organic solvent can be uniformly mixed first, and then 95wt%-70wt% of polymerization active monomer calculated by mass percentage is added, stirred and dispersed (preferably the ultrasonic dispersion time is 5-30min), and finally 1wt%-10wt% of amine calculated by mass percentage is dropped to obtain a gold nanocluster photoresist with added amine.

[0035] Based on the gold nanocluster photoresist with the addition of a co-initiator, the present invention also prepared a 3D structure, and the two-photon 3D printing method (i.e., micro-nano 3D printing method) used is as follows:

[0036] The gold nanocluster photoresist with the co-initiator added is 3D printed using a two-photon 3D printing system. The resulting 3D structure is then developed in a developer and dried with nitrogen to obtain a 3D structure of the gold nanocluster photoresist with the co-initiator added.

[0037] As a preferred embodiment of the present invention, during the operation of the two-photon 3D printing system, the laser wavelength is set to 780 nm, the laser power is set to 0.25-50 mW, the laser pulse is set to 120 fs, the laser frequency is set to 80 MHz, and the printing speed is set to 0.1-100 mm / s.

[0038] As a preferred embodiment of the present invention, the developer is preferably any one of propylene glycol methyl ether acetate, isopropyl alcohol, and dichloromethane, or a mixture of two or more thereof, and the developing time is 2-40 minutes.

[0039] Finally, based on the gold nanocluster photoresist with added coinitiator, the present invention also achieves photopatterning by ultraviolet light irradiation. The specific implementation method is as follows:

[0040] The gold nanocluster photoresist with the co-initiator added was dripped into the mold and the photoresist was tested at a wavelength of 365 nm and a power of 1 W / cm 2 The photocured polymer pattern can be obtained by irradiating the surface with ultraviolet light for 3 to 5 minutes.

[0041] In the present invention, the gold nanoclusters with added co-initiators have high initiation performance, and the photoresist has excellent processing performance (extremely high processing sensitivity and extremely low processing threshold), realizing the "one-step" processing of metal-polymer 3D structures, and realizing the metal-polymer photopatterning for the first time.

[0042] The method and effects of the present invention will be specifically described below through examples.

[0043] Example 1

[0044] Take 1 mg Au 25 (SC2H4Ph) 18 The mixture was ultrasonically dispersed in 20 μL of dichloromethane for 2 minutes, and then 99 mg of pentaerythritol triacrylate was added, followed by 5 μL of phenylethyl mercaptan. The mixture was stirred and dispersed at room temperature for 5 minutes to obtain a gold nanocluster photoresist with phenylethyl mercaptan added.

[0045] Example 2

[0046] Take 1 mg Au 25 (SC2H4Ph) 18 The mixture was ultrasonically dispersed in 20 μL of dichloromethane for 2 minutes, and then 99 mg of pentaerythritol triacrylate was added, followed by 5 μL of benzyl mercaptan. The mixture was stirred and dispersed at room temperature for 5 minutes to obtain a gold nanocluster photoresist with benzyl mercaptan added.

[0047] Example 3

[0048] Take 1 mg Au 25 (SC2H4Ph) 18 The mixture was ultrasonically dispersed in 20 μL of dichloromethane for 2 minutes, and then 99 mg of pentaerythritol triacrylate was added, followed by 5 μL of phenylethylamine. The mixture was stirred and dispersed at room temperature for 5 minutes to obtain a gold nanocluster photoresist with phenylethylamine added.

[0049] Example 4

[0050] Take 1 mg Au 25 (SC2H4Ph) 18 The mixture was ultrasonically dispersed in 20 μL of dichloromethane for 2 minutes, and then 99 mg of pentaerythritol triacrylate was added, followed by 5 μL of benzylamine. The mixture was stirred and dispersed at room temperature for 5 minutes to obtain a gold nanocluster photoresist with benzylamine added.

[0051] Example 5

[0052] Take 1 mg Au 25 (SCH2Ph) 18The mixture was ultrasonically dispersed in 20 μL of dichloromethane for 2 minutes, and then 99 mg of pentaerythritol triacrylate was added, followed by 5 μL of phenylethyl mercaptan. The mixture was stirred and dispersed at room temperature for 5 minutes to obtain a gold nanocluster photoresist with phenylethyl mercaptan added.

[0053] Example 6

[0054] Take 1 mg Au 25 (SCH2Ph) 18 The mixture was ultrasonically dispersed in 20 μL of dichloromethane for 2 minutes, and then 99 mg of pentaerythritol triacrylate was added, followed by 5 μL of benzyl mercaptan. The mixture was stirred and dispersed at room temperature for 5 minutes to obtain a gold nanocluster photoresist with benzyl mercaptan added.

[0055] Example 7

[0056] In a light-proof environment, an appropriate amount of the gold nanocluster photoresist with added thiol (phenylethyl mercaptan) obtained in Example 1 was smeared on a glass slide and 3D printed under a 780nm titanium sapphire femtosecond laser with a femtosecond laser pulse of 120fs, a laser frequency of 80MHz, a laser power of 1mW, and a printing speed of 5mm / s to obtain the following: Figure 1 As can be seen from the figure, the structure processed using the material obtained in Example 1 has a stable three-dimensional morphology.

[0057] Example 8

[0058] In a light-proof environment, an appropriate amount of the gold nanocluster photoresist with added thiol (phenylethyl mercaptan) obtained in Example 1 was smeared on a glass slide and 3D printed under a 780nm titanium sapphire femtosecond laser. The femtosecond laser pulse was 120fs, the laser frequency was 80MHz, the scanning rates were 5, 10, 30, 50, 70, 90, and 110mm / s, and the laser powers were 0.25, 0.5, 0.75, and 1.0mW, respectively. Figure 2 The three-dimensional block structure shown in the figure. As can be seen from the figure, the block structure collapses, which is due to the low printing laser power, resulting in insufficient structure polymerization. This ultra-low laser power indicates that the thiol-added gold nanocluster photoresist has an ultra-low polymerization threshold and ultra-high sensitivity.

[0059] Example 9

[0060] In a light-proof environment, an appropriate amount of the gold nanocluster photoresist with added thiol (benzyl mercaptan) obtained in Example 2 was smeared on a glass slide and 3D printed under a 780nm titanium sapphire femtosecond laser. The femtosecond laser pulse was 120fs, the laser frequency was 80MHz, the scanning rates were 5, 10, 30, 50, 70, 90, and 110mm / s, and the laser powers were 0.3, 0.4, 0.5, and 0.6mW, respectively. Figure 3The three-dimensional structure shown in the figure. As can be seen from the figure, the square structure collapses, which is due to the low printing laser power, resulting in insufficient structure polymerization. This ultra-low laser power indicates that the thiol-added gold nanocluster photoresist has an ultra-low polymerization threshold and ultra-high sensitivity.

[0061] Example 10

[0062] In a light-proof environment, an appropriate amount of the gold nanocluster photoresist with added amine (phenylethylamine) obtained in Example 3 was smeared on a glass slide, and 3D printing was performed under a 780nm titanium sapphire femtosecond laser. The femtosecond laser pulse was 120fs, the laser frequency was 80MHz, the scanning rates were 5, 10, 30, 50, 70, 90, and 110mm / s, and the laser power was 0.2, 0.4, and 0.6mW, respectively. Figure 4 The three-dimensional structure shown in the figure. As can be seen from the figure, the square structure collapses, which is due to the low printing laser power, resulting in insufficient structure polymerization. This ultra-low laser power indicates that the amine-added gold nanocluster photoresist has an ultra-low polymerization threshold and ultra-high sensitivity.

[0063] Example 11

[0064] In a light-proof environment, an appropriate amount of the gold nanocluster photoresist with added amine (benzylamine) obtained in Example 4 was smeared on a glass slide and 3D printed under a 780nm titanium sapphire femtosecond laser. The femtosecond laser pulse was 120fs, the laser frequency was 80MHz, the scanning rates were 5, 10, 30, 50, 70, 90, and 110mm / s, and the laser power was 0.5, 1.0, and 1.5mW, respectively. Figure 5 The three-dimensional structure shown in the figure. As can be seen from the figure, the square structure collapses, which is due to the low printing laser power, resulting in insufficient structure polymerization. This ultra-low laser power indicates that the amine-added gold nanocluster photoresist has an ultra-low polymerization threshold and ultra-high sensitivity.

[0065] Example 12

[0066] In a light-proof environment, an appropriate amount of the gold nanocluster photoresist with added thiol (phenylethyl mercaptan) obtained in Example 5 was smeared on a glass slide and 3D printed under a 780nm titanium sapphire femtosecond laser. The femtosecond laser pulse was 120fs, the laser frequency was 80MHz, the scanning rates were 5, 10, 30, 50, 70, 90, and 110mm / s, and the laser power was 1, 2, 3, 4, and 5mW, respectively. Figure 6 The three-dimensional structure shown in the figure. As can be seen from the figure, the square structure collapses, which is due to the low printing laser power, resulting in insufficient structure polymerization. This ultra-low laser power indicates that the thiol-added gold nanocluster photoresist has an ultra-low polymerization threshold and ultra-high sensitivity.

[0067] Example 13

[0068] In a light-proof environment, an appropriate amount of the gold nanocluster photoresist with added thiol (benzyl mercaptan) obtained in Example 6 was smeared on a glass slide and 3D printed under a 780nm titanium sapphire femtosecond laser. The femtosecond laser pulse was 120fs, the laser frequency was 80MHz, the scanning rates were 5, 10, 30, 50, 70, 90, and 110mm / s, and the laser power was 0.5, 1, 1.5, and 2.0mW, respectively. Figure 7 The three-dimensional structure shown in the figure. As can be seen from the figure, the square structure collapses, which is due to the low printing laser power, resulting in insufficient structure polymerization. This ultra-low laser power indicates that the thiol-added gold nanocluster photoresist has an ultra-low polymerization threshold and ultra-high sensitivity.

[0069] Example 14

[0070] In a light-proof environment, take an appropriate amount of the gold nanocluster photoresist with added thiol (phenylethyl mercaptan) obtained in Example 1 and drop it into the mold, and use a wavelength of 365nm and a power of 0.03-1W / cm 2 The photoresist is cured by irradiating with ultraviolet light for 1-5 minutes. Figure 8 The solid shown in FIG1 emits red fluorescence, which indicates that the photoresist can be polymerized under UV light, achieving photopatterning.

[0071] Thus, the gold nanocluster photoresist with the addition of a coinitiator of the present invention exhibits excellent processing properties (extremely high processing sensitivity and extremely low processing threshold), capable of processing various complex 3D structures and achieving photopatterning under ultraviolet light conditions. The addition of thiols or amines to the gold nanocluster photoresist significantly improves solubility and transmittance, and produces a special interaction with the gold nanoclusters, resulting in the photoresist having ultrahigh sensitivity, an ultralow threshold, and excellent printing effects. It also enables ultralow-power processing of metal-polymer 3D structures while also enabling UV curing.

[0072] The embodiment described above is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Persons skilled in the art may make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, any technical solution obtained by equivalent substitution or equivalent transformation falls within the scope of protection of the present invention.

Claims

1. A gold nanocluster photoresist with a co-initiator, characterized in that: The invention comprises 0.01 wt%-0.76 wt% of gold nanoclusters, 1 wt%-10 wt% of a co-initiator, 95 wt%-70 wt% of a polymerization active monomer, and 0.1 wt%-5 wt% of an organic solvent, calculated by weight percentage; The gold nanoclusters are Au 25 (SC8H 17 ) 18 , Au 25 (SC 10 H 21 ) 18 , [Au 25 (PPh3) 10 (SC8H 17 )5] 2+ , Au 25 (SC6H 12 OH) 18 , Au 25 (SC3H6) 18 , [Au 25 (PPh3) 10 (SC3H6)5] 2+ , [Au 25 (PPh3) 10 (SC6H 12 OH)5] 2+ ,Au 25 (SC2H4Ph) 18 , Au 25 (SCH2Ph) 18 , Au 25 (SC6H 13 ) 18 Any one or a combination of two or more.

2. The gold nanocluster photoresist with added coinitiator according to claim 1, characterized in that: The co-initiator is a thiol or an amine; the thiol is benzyl mercaptan, benzyl mercaptan, phenylethyl mercaptan, phenylpropyl mercaptan, butyl mercaptan, pentyl mercaptan, hexyl mercaptan, octyl mercaptan, nonyl mercaptan, decanethiol, cyclohexyl mercaptan, adamantane mercaptan, pentaerythritol tetrakis (3-mercaptopropionic acid) ester, p-phenylenedithiol, m-phenylenedithiol, o-phenylenedithiol, p-phenylmethyl mercaptan, m-phenylmethyl mercaptan, o-phenylmethyl mercaptan, p-phenylenedithiol, m-phenylenedithiol, Any one or a combination of two or more of o-phenylenedithiol and hexanedithiol; the amine is any one or a combination of two or more of aniline, benzylamine, phenylethylamine, amphetamine, triethylamine, butylamine, pentylamine, hexylamine, octylamine, nonylthiolamine, decylamine, cyclohexylamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, p-benzylamine, m-benzylamine, o-benzylamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine and hexylenediamine.

3. The gold nanocluster photoresist with added coinitiator according to claim 1, characterized in that: The polymerization active monomer is any one of polyethylene glycol diacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, polydipentaerythritol pentaacrylate, acrylic-cage polysilsesquioxane, neopentyl glycol diacrylate, dipentaerythritol hexaacrylate and diurethane dimethacrylate, or a combination of two or more thereof.

4. The gold nanocluster photoresist with added coinitiator according to claim 1, characterized in that: The organic solvent is any one of methanol, ethanol, isopropanol, ethyl ether, diethanol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, γ-butyrolactone, di(ethylene glycol) diethyl ether, methyl isobutyl ketone diethanol monoethyl ether, acetone, dichloromethane, chloroform, n-hexane, toluene, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide, or a combination of two or more thereof.

5. A method for preparing a gold nanocluster photoresist with a co-initiator added as claimed in any one of claims 1 to 4, characterized in that: The details are as follows: 0.01 wt%-0.76 wt% of gold nanoclusters and 1 wt%-5 wt% of an organic solvent, calculated by mass percentage, are uniformly mixed, and then 95 wt%-70 wt% of a polymerization active monomer, calculated by mass percentage, is added. Finally, 1 wt%-10 wt% of a co-initiator, calculated by mass percentage, is added. The mixture is stirred and dispersed for 5-30 minutes to obtain a gold nanocluster photoresist with the co-initiator added.

6. A micro-nano 3D printing method based on gold nanocluster photoresist with the addition of a co-initiator, characterized in that: The details are as follows: The gold nanocluster photoresist with added coinitiator as described in any one of claims 1 to 4 or the gold nanocluster photoresist with added coinitiator obtained by the preparation method according to claim 5 is 3D printed using a two-photon 3D printing system; the obtained 3D structure is then developed in a developer and blown dry with nitrogen to obtain a 3D structure of the gold nanocluster photoresist with added coinitiator.

7. The micro-nano 3D printing method according to claim 6, characterized in that: In the 3D printing system, the laser wavelength is 780 nm, the laser power is 0.25-50 mW, the laser pulse is 120 fs, the laser frequency is 80 MHz, and the printing speed is 0.1-100 mm / s; the developer is any one or a combination of two or more of propylene glycol methyl ether acetate, isopropyl alcohol, and dichloromethane, and the development time is 2-40 min.

8. A 3D structure of a gold nanocluster photoresist with a co-initiator prepared by the micro-nano 3D printing method according to claim 6.

9. Application of a gold nanocluster photoresist containing a co-initiator in photopatterning, characterized in that: The gold nanocluster photoresist with added coinitiator according to any one of claims 1 to 4 or the gold nanocluster photoresist with added coinitiator obtained by the preparation method according to claim 5 is placed in a mold and cured under an ultraviolet light source with a wavelength of 365 nm.

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