An organic-inorganic complex nanoparticle, a preparation method and application thereof

Abstract

The application discloses an organic-inorganic complex nanoparticle and a preparation method and application thereof, the nanoparticle is prepared from metal alcoholate, organic ligand and water through instant nano precipitation technology in a mixing cavity to rapidly react and assemble, and the organic-inorganic complex nanoparticle with a zirconium oxide core and an organic ligand with a specific structure wrapped outside through chemical bonding is obtained. The application further discloses a composition formula containing the organic-inorganic complex nanoparticle and a patterning method. The nanoparticle disclosed by the application has good dispersibility, uniform size and high batch stability, can change solubility under ultraviolet to extreme ultraviolet wave bands and electron beam irradiation, and can realize patterning processing without additional photosensitizers.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of new materials, in particular to an organic-inorganic complex nanoparticle and a preparation method and application thereof. BACKGROUND

[0002] The organic-inorganic complex nanoparticle has a unique core-shell structure and controllable physical and chemical properties, and has broad application prospects in the fields of catalysis, energy storage, biomedicine, electronic devices, etc. This kind of material is usually composed of a metal oxide inner core and an organic ligand shell, and has high stability of inorganic materials and modifiability of organic materials. However, the traditional preparation methods (such as hydrothermal method, sol-gel method, coprecipitation method, etc.) often have problems such as harsh reaction conditions, non-uniform product size, poor dispersion, etc., which limit its further application. In recent years, the transient nanometer precipitation technology has become a new method for preparing nanometer materials due to its simple operation, mild reaction conditions, controllable product size, etc. This technology realizes the homogeneous nucleation and growth of nanoparticles by rapidly mixing precursor solutions and using microfluidic or vortex mixing to effectively avoid the agglomeration phenomenon caused by uneven reaction rate in traditional methods. However, there are few studies on the preparation of organic-inorganic complex nanoparticles by using the transient nanometer precipitation method in the existing technology, especially in the precise assembly of metal oxide inner core and specific organic ligand (such as acrylic acid derivative, benzoic acid derivative).

[0003] In addition, the common metal oxide-organic hybrid material mainly faces the following technical bottlenecks: first, the product obtained by the traditional preparation method often has the problem of uneven coating of organic ligand, which leads to easy agglomeration or performance degradation of the material in the application process; second, the organic ligand of the existing material is single in function, and most of them only play a stabilizing and dispersing role, lacking active sites for further chemical modification; third, the conventional synthesis process has insufficient size control precision of nanoparticles, making it difficult to realize monodisperse preparation in the range of 1-5 nm.

[0004] Therefore, in view of the above problems, the present application provides an organic-inorganic complex nanoparticle and a preparation method and application thereof, and a new type of organic-inorganic complex nanoparticle is developed. The material takes zirconium oxide as the core, and the specific structure of the organic ligand is wrapped around the periphery by chemical bonding; this unique structural design has the following advantages: the metal oxide core provides excellent thermal stability and mechanical strength; the organic ligand not only ensures the good dispersibility of the material in the solvent, but also provides rich reaction sites for subsequent functionalization modification by introducing multiple active functional groups; the precise size control of 1-4 nm makes the material exhibit unique quantum confinement effect and surface effect. SUMMARY

[0005] The present application aims to provide an organic-inorganic complex nanoparticle, a preparation method and application thereof, so as to obtain a complex nanoparticle with uniform size and good dispersity.

[0006] The present application achieves the above-mentioned purpose by the following technical solutions.

[0007] An organic-inorganic complex nanoparticle is prepared by a transient nanometer precipitation technology, has a metal oxygen bridge core composed of zirconium oxide, and is wrapped with an organic ligand on the periphery through chemical bonding; wherein the organic ligand is selected from one or more of acrylic acid and its derivatives, benzoic acid and its derivatives.

[0008] Preferably, the organic-inorganic complex nanoparticle has a photo-induced reactive group; the photo-induced reactive group is selected from one or more of a carbon-carbon double bond, an ester group, a carboxyl group, an acyloxy group, an acyl group, and an aldehyde group.

[0009] Preferably, the size of the organic-inorganic complex nanoparticle is 1 nm to 4 nm.

[0010] Preferably, the structure of the acrylic acid and its derivatives is as follows:

[0011] ;

[0012] wherein R1, R2, R3 are independently selected from one or more of H, halogen, R, OR, wherein R is C1-C4 alkyl.

[0013] Preferably, the acrylic acid and its derivatives are selected from one or more of the following structures:

[0014] ; ; ; ; ; ; ; ; ; ; ; .

[0015] Preferably, the structure of the benzoic acid and its derivatives is as follows:

[0016] ;

[0017] wherein R4 is independently selected from one or more of H, halogen, carbonyl, hydroxyl, amino, R, OR, CN, NO2, SO3R, wherein R is C1-C4 alkyl and its substitutes.

[0018] Preferably, the benzoic acid and its derivatives are selected from one or more of the following structures:

[0019] ; ; ; ; ; ; ; ; ; ; ; .

[0020] The present application also claims a method for preparing the above organic-inorganic complex nanoparticles, comprising the following steps:

[0021] S1, mixing a metal alcoholate, an organic ligand and an organic solvent to obtain stream 1;

[0022] S2, deionized water as stream 2;

[0023] S3, injecting stream 1 and stream 2 into a head-on vortex mixer at a flow rate of 1-70 mL / min, and collecting the formed nanosuspension;

[0024] S4, stirring the obtained nanosuspension at 20-80℃ for 12-48h;

[0025] S5, after the reaction is completed, adding an anti-solvent to the product to precipitate the nanoparticles, removing the excess solvent after centrifugation, and drying the remaining solid in a vacuum oven to obtain the final product.

[0026] Preferably, the metal alcoholate is zirconium isopropoxide or zirconium n-propyl alcoholate.

[0027] Preferably, the molar ratio of the metal alcoholate to the organic ligand is 1:(0.5-10).

[0028] Preferably, the molar ratio of the metal alcoholate to the deionized water in stream 2 is 1:(55-100).

[0029] Preferably, the organic solvent in step S1 is selected from one or more of tetrahydrofuran, ethyl acetate, n-butyl acetate, acetone, ethanol, methanol, dichloromethane.

[0030] The present application also provides an organic-inorganic complex nanoparticle composition, which is obtained by dispersing the inorganic-organic complex nanoparticles in an organic dispersant.

[0031] Due to the use of the above technical solution, the present application has the following beneficial effects compared with the prior art:

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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

[0036] 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.

[0037] Figure 1 This is a schematic diagram of the apparatus for preparing nanoparticles using transient nanoprecipitation technology in Embodiment 1 of the present invention;

[0038] Figure 2 The infrared spectra of zirconium ethyl acrylate nanoparticles and ethyl acrylic acid in Example 1 of this invention are shown.

[0039] 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;

[0040] Figure 4 This is Example 2 of the present invention at 120 mJ / cm 2Optical microscope image of the micron-scale pattern obtained after developing the deep ultraviolet exposure at a dose of 120 mJ / cm

[0041] Figure 5 is the optical microscope image of the 1 μm line obtained after developing the deep ultraviolet exposure at a dose of 120 mJ / cm 2

[0042] Figure 6 is the optical microscope image obtained after developing the electron beam exposure at a dose of 1~20 μC / cm 2

[0043] Figure 7 is the optical microscope image obtained after developing the electron beam exposure at a dose of 20 μC / cm 2

[0044] Figure 8 is the scanning electron microscope image of the 500 nm line obtained after developing the electron beam exposure at a dose of 20 μC / cm 2

[0045] Figure 9 is the scanning electron microscope image of the 250 nm line obtained after developing the electron beam exposure at a dose of 20 μC / cm 2 DETAILED DESCRIPTION

[0046] In order to have a clearer understanding of the technical features, objectives and effects of the present application, the specific embodiments will be described in detail.

[0047] The present application will be further described below in conjunction with the embodiments, but the present application 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 noted are the conventional conditions in the industry. The technical features involved in each embodiment of the present application can be combined with each other as long as there is no conflict.

[0048] Embodiment 1

[0049] Referring to the accompanying drawings, the present application provides a preparation method of organic-inorganic complex nanoparticles, comprising the following steps: Figure 1 - the accompanying drawings, the present application provides a preparation method of organic-inorganic complex nanoparticles, comprising the following steps: Figure 2 The present embodiment provides a preparation method of organic-inorganic complex nanoparticles, comprising the following steps:

[0050] S1, 1.845 g of zirconium isopropoxide isopropoxide complex is uniformly mixed with 5 mL of ethyl acrylic acid and 10 mL of tetrahydrofuran to obtain stream 1;

[0051] S2, stream 2 is 7.5 mL of deionized water;

[0052] ​​​​​S3, two digital controlled syringe pumps were used to control the flow rate of the streams, the flow rate of stream 1 was controlled at 50 mL / min, and the flow rate of stream 2 was controlled at 25 mL / min, the two streams were mixed rapidly in a opposed vortex mixer to obtain a nano-suspension, and the nano-suspension was collected;

[0053] S4, the obtained nano-suspension was stirred at 65°C for 16 hours to react;

[0054] S5, after the reaction was completed, 50 mL of deionized water was slowly added to the product, and a precipitate was generated, the upper solvent was removed after centrifugation, and the obtained solid was placed in a vacuum oven at 40°C for 8 hours to obtain zirconium ethyl acrylic acid nanoparticles; the obtained zirconium ethyl acrylic acid was characterized by a Fourier transform infrared spectrometer, and the results are shown in Figure 2 It can be seen from the infrared spectrum of the zirconium ethyl acrylic acid nanoparticles that the carboxylic acid characteristic peak at 1690 cm -1 was disappeared, and a characteristic peak at 1550 cm -1 belonging to a metal carboxylate was generated instead, which proved that the ethyl acrylic acid was connected to the metal oxide through a coordination bond.

[0055] Example 2

[0056] Referring to the accompanying Figure 3 - the accompanying Figure 9 , the embodiment provides a preparation method of an organic-inorganic complex nano-particle, which comprises the following steps:

[0057] S1, 1.845 g of zirconium isopropyl alcohol isopropyl alcohol complex was uniformly mixed with 5 mL of methyl acrylic acid and 10 mL of tetrahydrofuran to obtain stream 1;

[0058] S2, stream 2 was 7.5 mL of deionized water;

[0059] S3, two digital controlled syringe pumps were used to control the flow rate of the streams, the flow rate of stream 1 was controlled at 50 mL / min, and the flow rate of stream 2 was controlled at 25 mL / min, the two streams were mixed rapidly in a opposed vortex mixer to obtain a nano-suspension, and the nano-suspension was collected;

[0060] S4, the obtained nano-suspension was stirred at 65°C for 16 hours to react;

[0061] S5, after the reaction was completed, 50 mL of deionized water was slowly added to the product, and a precipitate was generated, the upper solvent was removed after centrifugation, and the obtained solid was placed in a vacuum oven at 40°C for 8 hours to obtain zirconium ethyl acrylic acid nanoparticles; the obtained zirconium ethyl acrylic acid was characterized by a Fourier transform infrared spectrometer, and the results are shown in Figure 3as shown.

[0062] Example 3

[0063] The present example provides a preparation method of organic-inorganic complex nanoparticles, comprising the following steps:

[0064] S1, 1.845 g of zirconium isopropoxide isopropoxide complex is uniformly mixed with 5 mL of methacrylic acid and 10 mL of tetrahydrofuran to obtain stream 1;

[0065] S2, stream 2 is 7.5 mL of deionized water;

[0066] S3, two numerical control 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 are quickly collided and mixed in a counter-rotating vortex mixer to obtain a nano-suspension, and the formed nano-suspension is collected;

[0067] S4, the obtained nano-suspension is stirred at 25°C for 28h;

[0068] S5, after the reaction is completed, 50 mL of deionized water is slowly added to the product, a precipitate is generated, the upper solvent is removed after centrifugation, and the obtained solid is placed in a vacuum oven at 40°C for drying for 8 hours to obtain zirconium methacrylate nanoparticles.

[0069] Example 4

[0070] The present example provides a preparation method of organic-inorganic complex nanoparticles, comprising the following steps:

[0071] S1, 1.845 g of zirconium isopropoxide isopropoxide complex is uniformly mixed with 5 mL of methacrylic acid and 10 mL of tetrahydrofuran to obtain stream 1;

[0072] S2, stream 2 is 7.5 mL of deionized water;

[0073] S3, two numerical control 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 are quickly collided and mixed in a counter-rotating vortex mixer to obtain a nano-suspension, and the formed nano-suspension is collected;

[0074] S4, the obtained nano-suspension is stirred at 65°C for 16h;

[0075] S5, after the reaction is completed, 50 mL of deionized water is slowly added to the product, a precipitate is generated, the upper solvent is removed after centrifugation, and the obtained solid is placed in a vacuum oven at 40°C for drying for 8 hours to obtain zirconium methacrylate nanoparticles.

[0076] Comparative Example 1

[0077] This comparative example includes the following steps:

[0078] S1, 1.845 g of zirconium isopropoxide isopropoxide complex is mixed with 0.1 mL of methacrylic acid and 14.9 mL of tetrahydrofuran to obtain stream 1;

[0079] S2, stream 2 is 7.5 mL of deionized water;

[0080] S3, two numerical control 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 are quickly collided and mixed in a counter-rotating vortex mixer to obtain a nano-suspension, and the formed nano-suspension is collected;

[0081] S4, the obtained nano-suspension is stirred at 65°C for 16h;

[0082] Since 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 zirconia precipitate is produced after reaction, and the organic-inorganic complex nanoparticles cannot be obtained.

[0083] Comparative Example 2

[0084] This comparative example includes the following steps:

[0085] S1, 1.845 g of zirconium isopropoxide isopropoxide complex is mixed with 5 mL of methacrylic acid and 3 mL of tetrahydrofuran to obtain stream 1;

[0086] S2, stream 2 is 4 mL of deionized water;

[0087] S3, two numerical control 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 are quickly collided and mixed in a counter-rotating vortex mixer to obtain a nano-suspension, and the formed nano-suspension is collected;

[0088] S4, the obtained nano-suspension is stirred at 65°C for 16h;

[0089] Since the molar ratio of water to zirconium isopropoxide in this comparative example is only 46:1, which is less than 55:1, the content of water is too low, and insoluble zirconia precipitate is produced after reaction, and the organic-inorganic complex nanoparticles cannot be obtained.

[0090] Comparative Example 3

[0091] Referring to the accompanying Figure 3 , this comparative example provides a method for preparing zirconium methacrylate using a sol-gel method, which includes the following steps:

[0092] S1, take 387 mg of zirconium isopropyl alcohol isopropyl alcohol complex with 3.5 mL of methacrylic acid in a 15 mL flask, stirring at room temperature for 15 minutes under nitrogen protection;

[0093] S2, stirring at 65°C for 10 minutes to obtain a clear precursor solution, 0.1 mL of water and 0.9 mL of methacrylic acid are configured into a mixed solution, which is slowly added dropwise to the precursor solution, and the dropwise addition is completed in about 45 minutes;

[0094] S3, the mixture is stirred at 65°C for 20 hours to obtain a white precipitate, and the reaction process is carried out under nitrogen protection;

[0095] S4, take out the solution and the precipitate to a centrifugal tube, centrifuge at 8000 rpm for 10 minutes, and separate the precipitate;

[0096] S5, use acetone to dissolve the precipitate, add excess water to obtain a precipitate to remove excess methacrylic acid, repeat the washing twice, and then put it into a 60°C vacuum oven for 12 hours to obtain the product; the zirconium methacrylate prepared by the sol-gel method in this comparative example has complex steps and is suitable for small-scale synthesis in the laboratory, and it is difficult to scale up.

[0097] The organic-inorganic complex nanoparticles prepared in Example 2 are dispersed in an organic dispersant to obtain an organic-inorganic complex nanoparticle composition, and the patterning method is as follows:

[0098] Take 50 mg of zirconium methacrylate nanoparticles in Example 2, dissolve in propylene glycol methyl ether acetate to configure 1 g of solution; spin coating on a two-inch silicon wafer at a speed of 2000 rpm for 1 min, and then baking at 110°C for 1 min, so as to form a thin film on the surface of the silicon wafer, and use an ellipsometer to measure the film thickness, the thickness is 56 nm;

[0099] The silicon wafer coated with the thin film is exposed to a 248 nm deep ultraviolet light source through a mask, and the exposure dose is 120 mJ / cm 2 , and then developed with a developer to obtain different patterns, as shown in Figures 4-5 ;

[0100] The silicon wafer coated with the thin film is exposed to an electron beam source, and different exposure doses are used for sensitivity test, the initial dose is 1 μC / cm 2 , the interval is 1 μC / cm 2 , and the dose of 1~20 μC / cm 2 is tested, and the results are shown in Figure 6 , which proves that the composition has high sensitivity under electron beam exposure;

[0101] The thin film was electron beam exposed with a dose of 20 μC / cm 2 Line patterns of 500 nm, 250 nm and 50 nm were obtained, as shown in Fig. Figures 7-9 The line width to space (L / S) ratio of the 50 nm line pattern was 1:3, and the L / S ratio of the other line patterns was 1:1.

[0102] In summary, the present application realizes efficient and controllable synthesis of organic-inorganic complex nanoparticles by using the instant nanometer precipitation technology, and has the advantages of simple and easy preparation process, mild reaction condition, no need of complex equipment, wide material applicability, good dispersion, uniform size, high batch stability, etc. The organic-inorganic complex nanoparticles provided by the present application have the advantages of good stability provided by the metal oxide core, adjustable surface properties provided by the organic ligand, photo-induced reaction characteristics, reaction under various irradiation conditions such as ultraviolet, deep ultraviolet, electron beam and extreme ultraviolet, no need of additional photoacid generator, photocatalyst or free radical initiator, simplified application system, convenience for subsequent functional modification provided by the rich functional groups (such as carboxyl and ester groups) on the surface, controllable solubility under irradiation conditions, application in precise patterning, excellent dispersion and stability, application in different solvent systems, flexible and variable metal-ligand combination, targeted design according to different application requirements, simple preparation process, easy scale-up production, good industrialization prospect, easy availability of raw materials, controllable cost, high product purity, simple post-treatment, environmental protection, etc.

[0103] The above-described embodiments only express several embodiments of the present application, and the description is relatively specific and detailed, but it should not be understood as a limitation on the scope of the patent. It should be noted that for ordinary skilled persons in the art, several modifications and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the appended claims.

Claims

1. A method for preparing an organic-inorganic complex nanoparticle, characterized by, The method comprises the following steps: S1, mixing a metal alcoholate, an organic ligand and an organic solvent to obtain a stream 1; S2, deionized water as stream 2; S3, controlling the stream 1 and the stream 2 at a flow rate of 1-70 mL / min and injecting them into a vortex mixer at the same time, and collecting the formed nanosuspension; S4, stirring the obtained nanosuspension at 20-80℃ for 12-48h; S5, after the reaction, adding an anti-solvent to the product to precipitate the nanoparticles, removing the excess solvent after centrifugation, and drying the remaining solid in a vacuum oven to obtain the final product; The organic-inorganic complex nanoparticles are prepared by a transient nanometer precipitation technology, and are metal oxygen cluster structures obtained by directly bonding a metal oxygen bridge composed of zirconium oxide and a peripheral organic ligand; wherein the organic ligand is selected from one or more of acrylic acid and its derivatives, benzoic acid and its derivatives; The size of the organic-inorganic complex nanoparticles is 1-4nm; The structure of the acrylic acid and its derivatives is as follows: ； R1, R2, R3 are independently selected from one or more of H, halogen, R, OR, wherein R is C1-C4 alkyl; The structure of the benzoic acid and its derivatives is as follows: ； R4 is independently selected from one or more of H, halogen, carbonyl, hydroxyl, amino, R, OR, CN, NO2, SO3R, wherein R is C1-C4 alkyl; The metal alcoholate is zirconium isopropoxide or zirconium n-propyl alcoholate.

2. The method for preparing organic-inorganic complex nanoparticles as described in claim 1, characterized in that, The acrylic acid and its derivatives are selected from one or more of the following structures: ； ； ； ； ； ； ； ； ； ； ； 。 3. The method for preparing organic-inorganic complex nanoparticles as described in claim 1, characterized in that, The benzoic acid and its derivatives are selected from one or more of the following structures: ； ； ； ； ； ； ； ； ； ； ； 。 4. The method for preparing organic-inorganic complex nanoparticles as described in claim 1, characterized in that, The organic-inorganic complex nanoparticles have a photo-reactive group; the photo-reactive group is selected from one or more of a carbon-carbon double bond, an ester group, a carboxyl group, an acyloxy group, an acyl group, and an aldehyde group.

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

Images