Organic-inorganic complex nanoparticle as well as preparation method and application thereof

Abstract

The invention discloses an organic-inorganic complex nanoparticle as well as a preparation method and application thereof.The nanoparticle is obtained by performing rapid reaction and assembly on metal alcoholate, an organic ligand and water in a mixing cavity through an instantaneous nano-precipitation technology, and the organic-inorganic complex nanoparticle with zirconium oxide as a core and zirconium oxide as a core is obtained. Organic-inorganic complex nanoparticles of organic ligands with specific structures are wrapped on the peripheries of the organic-inorganic complex nanoparticles through chemical bonding. The invention also discloses a composition formula containing the organic-inorganic complex nanoparticles and a patterning method. The nano particles are good in dispersity, uniform in size and high in batch stability, solubility change can be generated in the ultraviolet band to the extreme ultraviolet band and under electron beam irradiation, and patterning processing can be achieved without an additional photosensitizer.

Description

Technical Field

[0001] This invention relates to the field of new materials technology, specifically to an organic-inorganic complex nanoparticle, its preparation method, and its application. Background Technology

[0002] Organic-inorganic complex nanoparticles, due to their unique core-shell structure and tunable physicochemical properties, show broad application prospects in catalysis, energy storage, biomedicine, and electronic devices. These materials typically consist of a metal oxide core and an organic ligand shell, combining the high stability of inorganic materials with the modifiability of organic materials. However, traditional preparation methods (such as hydrothermal methods, sol-gel methods, and coprecipitation methods) often suffer from harsh reaction conditions, non-uniform product size, and poor dispersibility, limiting their further application. In recent years, transient nanoprecipitation technology has emerged as a new method for preparing nanomaterials due to its advantages of simple operation, mild reaction conditions, and controllable product size. This technology achieves homogeneous nucleation and growth of nanoparticles by rapidly mixing precursor solutions and utilizing microfluidic or eddy current mixing, effectively avoiding the aggregation phenomenon caused by uneven reaction rates in traditional methods. However, existing research on the preparation of organic-inorganic complex nanoparticles using transient nanoprecipitation is limited, especially regarding the precise assembly of metal oxide cores with specific organic ligands (such as acrylic acid derivatives and benzoic acid derivatives), which remains a challenge.

[0003] In addition, common metal oxide-organic hybrid materials mainly face the following technical bottlenecks: First, the products obtained by traditional preparation methods often have uneven organic ligand coating, which makes the materials prone to aggregation or performance degradation during application; Second, the organic ligands in existing materials have single functions, mostly playing only a stabilizing and dispersing role, and lacking active sites that can be further chemically modified; Third, conventional synthesis processes have insufficient precision in controlling the size of nanoparticles, making it difficult to achieve monodisperse preparation in the range of 1~5nm.

[0004] Therefore, to address the aforementioned problems, this invention provides an organic-inorganic complex nanoparticle, its preparation method, and its application. A novel organic-inorganic complex nanoparticle is developed, with zirconium oxide as the core and an organic ligand of a specific structure encapsulated by chemical bonding. This unique structural design offers the following advantages: the metal oxide core provides excellent thermal stability and mechanical strength; the organic ligand not only ensures good dispersibility of the material in solvents, but also introduces various active functional groups that provide abundant reaction sites for subsequent functionalization modifications; and the precise size control of 1–4 nm enables the material to exhibit unique quantum confinement and surface effects. Summary of the Invention

[0005] The purpose of this invention is to provide an organic-inorganic complex nanoparticle, its preparation method and application, so as to obtain complex nanoparticles with uniform size and good dispersibility.

[0006] The objective of this invention is achieved through the following technical solution: An organic-inorganic complex nanoparticle, prepared by transient nanoprecipitation technology, has a metal-oxygen bridging core composed of zirconium oxide and an organic ligand encapsulated by chemical bonding; wherein the organic ligand is selected from one or more of acrylic acid and its derivatives, benzoic acid and its derivatives. Preferably, the organic-inorganic complex nanoparticles have photoreactive groups; the photoreactive groups are selected from one or more of carbon-carbon double bonds, ester groups, carboxyl groups, acyl groups, acyl groups, and aldehyde groups.

[0007] Preferably, the size of the organic-inorganic complex nanoparticles is 1 nm to 4 nm.

[0008] Preferably, the structural formula of the acrylic acid and its derivatives is as follows: ; R1, R2, and R3 are independently selected from one or more of H, halogens, R, and OR, where R is a C1-C4 alkyl chain.

[0009] Preferably, the acrylic acid and its derivatives are selected from one or more of the following structures: ; ; ; ; ; ; ; ; ; ; ; .

[0010] Preferably, the structural formula of the benzoic acid and its derivatives is as follows: ;

[0011] R4 is independently selected from one or more of H, halogen, carbonyl, hydroxyl, amino, R, OR, CN, NO2, SO3R, where R is a C1~C4 chain alkyl group and its substituted derivatives.

[0012] Preferably, the benzoic acid and its derivatives are selected from one or more of the following structures: ; ; ; ; ; ; ; ; ; ; ; .

[0013] This application also claims a method for preparing the above-mentioned organic-inorganic complex nanoparticles, comprising the following steps: S1. Mixing a metal alkoxide, an organic ligand, and an organic solvent yields stream 1; S2, Use deionized water as stream 2; S3. Simultaneously inject streams 1 and 2 at a flow rate of 1~70 mL / min into the counter-current vortex mixer and collect the resulting nano suspension. S4. Stir the obtained nano suspension at 20~80℃ for 12~48h. S5. After the reaction is complete, add an antisolvent to the product to precipitate the nanoparticles. After centrifugation, remove excess solvent and dry the remaining solid in a vacuum oven to obtain the final product.

[0014] Preferably, the metal alkoxide is zirconium isopropoxide or zirconium n-propoxide.

[0015] Preferably, the molar ratio of the metal alkoxide to the organic ligand is 1:(0.5~10).

[0016] Preferably, the molar ratio of the metal alkoxide to deionized water in stream 2 is 1:(55~100).

[0017] Preferably, the organic solvent in step S1 is selected from one or more of tetrahydrofuran, ethyl acetate, n-butyl acetate, acetone, ethanol, methanol, and dichloromethane.

[0018] This application also provides an organic-inorganic complex nanoparticle composition, which is obtained by dispersing the inorganic-organic complex nanoparticles in an organic dispersant.

[0019] Due to the application of the above technical solution, the present invention has the following beneficial effects compared with the prior art: 1. This invention employs instantaneous nanoprecipitation technology to achieve efficient and controllable synthesis of organic-inorganic complex nanoparticles. The preparation process is simple and easy to implement, the reaction conditions are mild, no complex equipment is required, and the obtained nanoparticles have good dispersibility, uniform size, and high batch stability. 2. The organic-inorganic complex nanoparticles proposed in this invention differ from existing quantum dots in that they are directly connected by chemical bonds between a metal-oxygen bridge core and an organic ligand. The metal oxide core provides good stability, while the organic ligand imparts tunable surface properties and exhibits photoreactive characteristics. They can react under various irradiation conditions such as ultraviolet, deep ultraviolet, electron beam, and extreme ultraviolet, without the need for additional photoacid generators, photocatalysts, or free radical initiators, thus simplifying the application system. The abundant functional groups on the surface (such as carboxyl groups and ester groups) provide convenience for subsequent functionalization modification. 3. The present invention can achieve controllable changes in solubility under irradiation conditions, making it suitable for precision patterning. It has excellent dispersibility and stability, making it easy to apply in different solvent systems. The metal-ligand combination is flexible and variable, and can be designed to meet different application requirements. 4. The preparation process of this invention is simple, easy to scale up for production, has good industrialization prospects, the raw materials are readily available, the cost is controllable, it is conducive to practical application and promotion, the product has high purity, the post-processing is simple, and it meets environmental protection requirements. Attached Figure Description

[0020] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, some of the drawings in the following description are some embodiments of the present invention. For those skilled in the art, other drawings can be made based on these drawings without creative effort.

[0021] Figure 1 This is a schematic diagram of the apparatus for preparing nanoparticles using transient nanoprecipitation technology in Embodiment 1 of the present invention; Figure 2 The infrared spectra of zirconium ethyl acrylate nanoparticles and ethyl acrylic acid in Example 1 of this invention are shown. Figure 3 This is a comparison diagram of the particle size of zirconium methacrylate from Example 2 of the present invention and zirconium methacrylate synthesized by the conventional sol-gel method in Comparative Example 3; Figure 4 This is Example 2 of the present invention at 120 mJ / cm 2 Light micrograph of a micron-sized pattern obtained after deep ultraviolet exposure and development at a certain dose; Figure 5 This is Example 2 of the present invention at 120 mJ / cm 2 Light micrograph of 1μm lines obtained after deep ultraviolet exposure and development at a certain dose; Figure 6 This is Example 2 of the present invention at 1~20 μC / cm 2 Light micrograph obtained after electron beam exposure and development at a certain dose; Figure 7 This is Example 2 of the present invention at 20 μC / cm 2 Scanning electron microscope image of 500nm lines obtained after electron beam exposure and development at a certain dose; Figure 8 This is Example 2 of the present invention at 20 μC / cm 2 Scanning electron microscope image of 250nm lines obtained after electron beam exposure and development at a certain dose;

[0022] Figure 9 This is Example 2 of the present invention at 20 μC / cm 2 Scanning electron microscope (SEM) image of 50 nm lines obtained after electron beam exposure and development at a specific dose. Detailed Implementation

[0023] To provide a clearer understanding of the technical features, objectives, and effects of this invention, specific implementation schemes are now described in detail.

[0024] The present invention will be further described below with reference to embodiments, but the present invention is not limited to the following embodiments. The implementation conditions used in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not specified are conventional conditions in the industry. The technical features involved in the various embodiments of the present invention can be combined with each other as long as they do not conflict with each other.

[0025] Example 1 See appendix Figure 1 -Appendix Figure 2 This embodiment provides a method for preparing organic-inorganic complex nanoparticles, including the following steps: S1. Mix 1.845g of isopropoxide-zirconium isopropanol complex with 5mL of ethyl acrylic acid and 10mL of tetrahydrofuran to obtain stream 1. S2 and stream 2 each contain 7.5 mL of deionized water; S3. Two CNC injection pumps are used to control the flow rate of the streams. The flow rate of stream 1 is controlled at 50 mL / min and the flow rate of stream 2 is controlled at 25 mL / min. The two streams of material collide and mix rapidly in the counter-current vortex mixer to obtain a nano suspension. The formed nano suspension is collected. S4. The obtained nano suspension was stirred at 65°C for 16 hours. S5. After the reaction was complete, 50 mL of deionized water was slowly added to the product, resulting in a precipitate. After centrifugation, the upper solvent layer was removed, and the obtained solid was dried in a vacuum oven at 40 °C for 8 hours to obtain zirconium ethyl acrylate nanoparticles. The obtained zirconium ethyl acrylate was characterized using Fourier transform infrared spectroscopy, and the results are as follows: Figure 2 As shown, the infrared spectrum of zirconium ethyl acrylate nanoparticles is located at 1690 cm⁻¹. -1The characteristic peak of carboxylic acid at 1550 cm⁻¹ disappeared, and was replaced by a peak at 1550 cm⁻¹. -1 The characteristic peaks at the location belong to metal carboxylates, proving that ethyl acrylic acid is linked to the metal oxide through coordinate bonds.

[0026] Example 2 See appendix Figure 3 -Appendix Figure 9 This embodiment provides a method for preparing organic-inorganic complex nanoparticles, including the following steps: S1. Mix 1.845g of isopropoxide-zirconium isopropanol complex with 5mL of methacrylic acid and 10mL of tetrahydrofuran to obtain stream 1. S2 and stream 2 each contain 7.5 mL of deionized water; S3. Two CNC injection pumps are used to control the flow rate of the streams. The flow rate of stream 1 is controlled at 50 mL / min and the flow rate of stream 2 is controlled at 25 mL / min. The two streams of material collide and mix rapidly in the counter-current vortex mixer to obtain a nano suspension. The formed nano suspension is collected. S4. The obtained nano suspension was stirred at 65°C for 16 hours. S5. After the reaction is complete, 50 mL of deionized water is slowly added to the product. A precipitate forms. After centrifugation, the upper solvent layer is removed, and the obtained solid is dried in a vacuum oven at 40°C for 8 hours to obtain zirconium methacrylate nanoparticles. Dynamic light scattering particle size analysis shows that the average diameter of the prepared nanoparticles is approximately 1.25 nm, while the diameter of zirconium methacrylate particles prepared by the traditional sol-gel method is approximately 2.46 nm. Figure 3 As shown.

[0027] Example 3 This embodiment provides a method for preparing organic-inorganic complex nanoparticles, including the following steps: S1. Mix 1.845g of isopropoxide-zirconium isopropanol complex with 5mL of methacrylic acid and 10mL of tetrahydrofuran to obtain stream 1. S2 and stream 2 each contain 7.5 mL of deionized water; S3. Two CNC injection pumps are used to control the flow rate of the streams. The flow rate of stream 1 is controlled at 50 mL / min and the flow rate of stream 2 is controlled at 25 mL / min. The two streams of material collide and mix rapidly in the counter-current vortex mixer to obtain a nano suspension. The formed nano suspension is collected. S4. The obtained nano suspension was stirred at 25°C for 28 hours. S5. After the reaction is complete, slowly add 50 mL of deionized water to the product. A precipitate will form. After centrifugation, remove the upper solvent layer and place the obtained solid in a vacuum oven at 40 °C for 8 hours to obtain zirconium methacrylate nanoparticles.

[0028] Example 4 This embodiment provides a method for preparing organic-inorganic complex nanoparticles, including the following steps: S1. 1.845g of isopropoxide-zirconium isopropanol complex was mixed with 2.38g of benzoic acid and 15mL of tetrahydrofuran to obtain stream 1. S2 and stream 2 each contain 7.5 mL of deionized water; S3. Two CNC injection pumps are used to control the flow rate of the streams. The flow rate of stream 1 is controlled at 50 mL / min and the flow rate of stream 2 is controlled at 25 mL / min. The two streams of material collide and mix rapidly in the counter-current vortex mixer to obtain a nano suspension. The formed nano suspension is collected. S4. The obtained nano suspension was stirred at 65°C for 16 hours. S5. After the reaction is complete, slowly add 50 mL of deionized water to the product. A precipitate will form. After centrifugation, remove the upper solvent and place the obtained solid in a vacuum oven at 40 °C for 8 hours to obtain zirconium benzoate nanoparticles.

[0029] Comparative Example 1 This comparative example includes the following steps: S1. 1.845 g of isopropoxide-zirconium isopropanol complex was mixed with 0.1 mL of methacrylic acid and 14.9 mL of tetrahydrofuran to obtain stream 1; S2 and stream 2 each contain 7.5 mL of deionized water; S3. Two CNC injection pumps are used to control the flow rate of the streams. The flow rate of stream 1 is controlled at 50 mL / min and the flow rate of stream 2 is controlled at 25 mL / min. The two streams of material collide and mix rapidly in the counter-current vortex mixer to obtain a nano suspension. The formed nano suspension is collected. S4. The obtained nano suspension was stirred at 65°C for 16 hours.

[0030] Because the molar ratio of methacrylic acid to zirconium isopropoxide in this comparative example is only 0.2:1, which is less than 0.5:1, the content of methacrylic acid is too low, and insoluble zirconium oxide precipitate is produced after the reaction, so the organic-inorganic complex nanoparticles cannot be obtained.

[0031] Comparative Example 2 This comparative example includes the following steps: S1. Mix 1.845g of isopropoxide-zirconium isopropanol complex with 5mL of methacrylic acid and 3mL of tetrahydrofuran to obtain stream 1. S2 and stream 2 are 4 mL of deionized water; S3. Two CNC injection pumps are used to control the flow rate of the streams. The flow rate of stream 1 is controlled at 50 mL / min and the flow rate of stream 2 is controlled at 25 mL / min. The two streams of material collide and mix rapidly in the counter-current vortex mixer to obtain a nano suspension. The formed nano suspension is collected. S4. The obtained nano suspension was stirred at 65°C for 16 hours. Since the molar ratio of water to zirconium isopropoxide in this comparative example is only 46:1, which is less than 55:1, the water content is too low, resulting in the formation of insoluble zirconium oxide precipitate after the reaction, and thus the organic-inorganic complex nanoparticles cannot be obtained.

[0032] Comparative Example 3 See appendix Figure 3 This comparative example provides a method for preparing zirconium methacrylate using the sol-gel method, comprising the following steps: S1. Take 387 mg of zirconium isopropoxide complex and 3.5 mL of methacrylic acid in a 15 mL flask and stir at room temperature for 15 minutes under nitrogen protection. S2. Stir at 65℃ for 10 minutes to obtain a clear precursor solution. Prepare a mixed solution with 0.1 mL of water and 0.9 mL of methacrylic acid, and slowly add it dropwise to the precursor solution. The addition is completed in about 45 minutes. S3. The mixture was stirred at 65°C for 20 hours to obtain a white precipitate. The reaction was carried out under nitrogen protection. S4. Take the solution and precipitate into a centrifuge tube, centrifuge at 8000 rpm for 10 minutes, and separate the precipitate; S5. After dissolving the precipitate with acetone, excess water was added to remove excess methacrylic acid. This process was repeated twice. The product was then obtained after drying in a vacuum oven at 60°C for 12 hours. In this comparative example, zirconium methacrylate was synthesized using the sol-gel method. This method is complex and suitable for small-scale synthesis in the laboratory, but it is difficult to scale up.

[0033] The organic-inorganic complex nanoparticles prepared in Example 2 were dispersed in an organic dispersant to obtain an organic-inorganic complex nanoparticle composition. The organic-inorganic complex nanoparticle composition and the patterning method are as follows:

[0034] Take 50 mg of zirconium methacrylate nanoparticles from Example 2, dissolve them in propylene glycol methyl ether acetate to prepare a 1 g solution; spin-coat the solution on a two-inch silicon wafer at 2000 rpm for 1 min, and then bake it at 110°C for 1 min to form a thin film on the silicon wafer surface. The film thickness was measured using an ellipsometry and found to be 56 nm. A silicon wafer coated with a thin film is exposed through a photomask to a 248nm deep ultraviolet light source at a dose of 120mJ / cm². 2Then, it was developed with a developer, resulting in different patterns, such as Figures 4-5 As shown; The silicon wafer coated with a thin film was exposed using an electron beam source, and sensitivity tests were conducted using different exposure doses, with an initial dose of 1 μC / cm. 2 1μC / cm interval 2 Tested at 1~20μC / cm 2 The dosage and results are as follows Figure 6 As shown, this demonstrates that the composition exhibits high sensitivity under electron beam exposure; Use 20μC / cm 2 Electron beam exposure of the thin film with specific dosages yielded line patterns at 500nm, 250nm, and 50nm, such as... Figures 7-9 As shown, the linewidth to blank ratio (L / S) of 50nm is 1:3, while the linewidth to blank ratio of the other patterns is 1:1.

[0035] In summary, this invention utilizes transient nanoprecipitation technology to achieve efficient and controllable synthesis of organic-inorganic complex nanoparticles. The preparation process is simple and easy to implement, with mild reaction conditions, requiring no complex equipment, and exhibiting wide applicability to materials. The resulting nanoparticles demonstrate good dispersibility, uniform size, and high batch stability. The organic-inorganic complex nanoparticles proposed in this invention possess photoreactive properties, with the metal oxide core providing excellent stability and the organic ligands imparting tunable surface properties. They can react under various irradiation conditions, including ultraviolet, deep ultraviolet, electron beam, and extreme ultraviolet, without the need for additional photoacid generators or photocatalysts. The invention uses oxidizing agents or free radical initiators, simplifying the application system. The abundant functional groups on the surface (such as carboxyl groups, ester groups, etc.) facilitate subsequent functionalization modification. The invention can achieve controllable changes in solubility under irradiation conditions, making it suitable for precision patterning. It has excellent dispersibility and stability, making it easy to apply in different solvent systems. The metal-ligand combination is flexible and variable, and can be designed to meet different application requirements. The preparation process of this invention is simple, easy to scale up for production, and has good industrialization prospects. The raw materials are readily available, the cost is controllable, which is conducive to practical application and promotion. The product has high purity, simple post-processing, and meets environmental protection requirements.

[0036] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. An organic-inorganic complex nanoparticle, characterized in that, The organic-inorganic complex nanoparticles are prepared by transient nanoprecipitation technology and are metal-oxygen cluster structures obtained by direct chemical bonding between a metal-oxygen bridge composed of zirconium oxide and an external organic ligand; wherein the organic ligand is selected from one or more of acrylic acid and its derivatives, benzoic acid and its derivatives.

2. The organic-inorganic complex nanoparticles as described in claim 1, characterized in that, The organic-inorganic complex nanoparticles have photoreactive groups; the photoreactive groups are selected from one or more of carbon-carbon double bonds, ester groups, carboxyl groups, acyl groups, acyl groups, and aldehyde groups.

3. The organic-inorganic complex nanoparticles as described in claim 1, characterized in that, The size of the organic-inorganic complex nanoparticles is 1 nm to 4 nm.

4. The organic-inorganic complex nanoparticles as described in claim 1, characterized in that, The structural formulas of acrylic acid and its derivatives are shown below: ； R1, R2, and R3 are independently selected from one or more of H, halogens, R, and OR, where R is a C1-C4 alkyl chain.

5. The organic-inorganic complex nanoparticles as described in claim 4, characterized in that, The acrylic acid and its derivatives are selected from one or more of the following structures: ； ； ； ； ； ； ； ； ； ； ； 。 6. The organic-inorganic complex nanoparticles as described in claim 1, characterized in that, The structural formulas of the benzoic acid and its derivatives are shown below: ； R4 is independently selected from one or more of H, halogen, carbonyl, hydroxyl, amino, R, OR, CN, NO2, SO3R, where R is a C1~C4 chain alkyl group and its substituted derivatives.

7. The organic-inorganic complex nanoparticles as described in claim 6, characterized in that, The benzoic acid and its derivatives are selected from one or more of the following structures: ； ； ； ； ； ； ； ； ； ； ； 。 8. A method for preparing organic-inorganic complex nanoparticles as described in any one of claims 1 to 7, characterized in that, Includes the following steps: S1. Mixing a metal alkoxide, an organic ligand, and an organic solvent yields stream 1; S2, Use deionized water as stream 2; S3. Simultaneously inject streams 1 and 2 at a flow rate of 1~70 mL / min into the counter-current vortex mixer and collect the resulting nano suspension. S4. Stir the obtained nano suspension at 20~80℃ for 12~48h. S5. After the reaction is complete, add an antisolvent to the product to precipitate the nanoparticles. After centrifugation, remove excess solvent and dry the remaining solid in a vacuum oven to obtain the final product.

9. The method for preparing organic-inorganic complex nanoparticles as described in claim 8, characterized in that, The metal alkoxide is zirconium isopropoxide or zirconium n-propoxide.

10. The method for preparing organic-inorganic complex nanoparticles as described in claim 8, characterized in that, The molar ratio of the metal alkoxide to the organic ligand is 1:(0.5~10); the molar ratio of the metal alkoxide to deionized water in stream 2 is 1:(55~100).

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