CN113651357A - Zirconium oxide nano particle, preparation method thereof, photoresist composition and application thereof - Google Patents
Zirconium oxide nano particle, preparation method thereof, photoresist composition and application thereof Download PDFInfo
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- CN113651357A CN113651357A CN202110862938.4A CN202110862938A CN113651357A CN 113651357 A CN113651357 A CN 113651357A CN 202110862938 A CN202110862938 A CN 202110862938A CN 113651357 A CN113651357 A CN 113651357A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
- G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses zirconium oxide nanoparticles, a preparation method thereof, a photoresist composition and application thereof. The preparation method of the zirconium oxide nano particles comprises the following steps: providing or preparing a zirconium salt solution comprising a first solvent and a zirconium salt dispersed in the first solvent; adding a ligand into the zirconium salt solution, and uniformly mixing to prepare a zirconium-containing reaction system; heating the zirconium-containing reaction system, and controlling the heating temperature to be 40-100 ℃ to generate zirconium oxide in the zirconium-containing reaction system; the heating was stopped and left to stand until a solid component precipitated. The preparation method of the zirconium oxide nano particles can obviously reduce the particle size of the zirconium oxide nano particles and improve the uniformity of particle size distribution, and further can effectively improve the resolution of developed patterns when the zirconium oxide nano particles are used as photoresist.
Description
Technical Field
The invention relates to the technical field of photoetching, in particular to zirconium oxide nanoparticles, a preparation method thereof, a photoresist composition and application thereof.
Background
Photolithography (lithography) is the heart of the semiconductor industry and is a prerequisite for the fabrication of large scale integrated circuits. The most advanced lithography technology in the semiconductor industry, 193nm liquid immersion deep ultraviolet lithography, is approaching its physical limit, and extreme-ultraviolet lithography (extreme-ultraviolet lithography) with a wavelength of 13.5nm (or shorter) is considered as the next generation lithography with great potential for development.
At present, the photoetching materials mainly comprise three main types, namely polymer type, molecular glass type and metal oxide nano particles. A polymer type photoresist is a commonly used deep ultraviolet photoresist. The size of the polymer chain segment in the polymer type photoresist is generally between 6nm and 10nm, which inevitably causes the photoetching pattern to have the roughness of 3nm to 5nm or even more than 5nm, and seriously influences the photoetching process node of 30nm or less. This factor makes it difficult for polymeric lithographic materials to meet the practical requirements of euv lithography. The metal oxide nanoparticle-type photoresist has a size of several nanometers, which is advantageous for reducing the roughness of the photolithographic pattern. Compared with the traditional polymer type photoetching material, the transition metal element can show stronger absorption characteristics under the extreme ultraviolet band.
For metal oxide nanoparticle photoresists, the size of the particle size and the uniformity of the particle size distribution significantly affect the solubility change during the development process, and thus the resolution of the developed pattern. It is difficult to obtain nanoparticles having a small particle diameter and a uniform particle diameter distribution in the conventional art, which limits further improvement of the resolution of the pattern after development.
Disclosure of Invention
In view of the above, it is necessary to provide a method for producing zirconium oxide nanoparticles having a small particle diameter and a uniform particle diameter distribution. Correspondingly, the zirconium oxide nano particles, the photoresist composition and the specific application of the photoresist composition are also provided.
According to one embodiment of the present invention, a method for preparing zirconium oxide nanoparticles includes the steps of:
providing or preparing a zirconium salt solution comprising a first solvent and a zirconium salt dispersed in the first solvent;
adding a ligand into the zirconium salt solution, and uniformly mixing to prepare a zirconium-containing reaction system;
heating the zirconium-containing reaction system, and controlling the heating temperature to be 40-100 ℃ to generate zirconium oxide in the zirconium-containing reaction system;
the heating was stopped and left to stand until a solid component precipitated.
In one embodiment, the zirconium salt is selected from one or more of zirconium carboxylate, zirconium sulfonate, zirconium alkoxide, zirconium halide, zirconium nitrate, and zirconium sulfate.
In one embodiment, the first solvent is selected from one or more of alcohols, esters, and hydrocarbons.
In one embodiment, the ligand is selected from carboxylic acid ligands.
In one embodiment, in the zirconium-containing reaction system, the ratio of the amount of zirconium ions in the zirconium salt to the amount of the ligand substance is 1 (0.1-10).
In one embodiment, in the process of heating the zirconium-containing reaction system, the zirconium-containing reaction system is reacted for 6 to 24 hours at a temperature of 70 to 100 ℃, for 3 to 12 hours at a temperature of 50 to 70 ℃ and for 3 to 12 hours at a temperature of 40 to 50 ℃ in sequence.
In one embodiment, after standing to precipitate a solid component, the method further comprises the steps of obtaining the solid component by filtration and drying the solid component.
In one embodiment, the zirconium salt solution contains 40 to 80% by mass of the zirconium salt.
Correspondingly, the zirconium oxide nano-particles are prepared by the preparation method of the zirconium oxide nano-particles according to any one of the embodiments.
In one embodiment, the zirconium oxide particles are crystals having a particle size between 1nm and 3 nm.
In another aspect, another embodiment of the present invention further provides a use of the zirconium oxide nanoparticles prepared by the method for preparing zirconium oxide nanoparticles according to any one of the above embodiments in a photoresist.
Specifically, a photoresist composition comprising: a second solvent, and a photosensitizer and a photolithographic material dispersed in the second solvent, wherein the photolithographic material comprises the zirconium oxide nanoparticles prepared by the preparation method of the zirconium oxide nanoparticles according to any one of the embodiments.
In one embodiment, the photoresist composition comprises 1-15 wt% of the photoresist material and 0.005-1.5 wt% of the photosensitizer.
In yet another aspect, another embodiment of the present invention also provides a use of the photoresist composition according to any one of the above embodiments for preparing a lithographic pattern.
Specifically, in the preparation of the lithographic pattern, exposure is performed using an extreme ultraviolet lithography system or an electron beam lithography system.
In some conventional methods for preparing zirconium oxide nanoparticles, a zirconium salt and a ligand are generally added into a solution at the same time and uniformly mixed, and then the zirconium oxide nanoparticles are prepared by adding water for hydrolysis, but the zirconium oxide prepared by such a mixing method is generally complex in crystal form, does not have a fixed crystal structure, and the finally obtained powder is generally white in color.
In the method for preparing zirconium oxide nanoparticles provided in the above embodiment, a zirconium salt solution is prepared in advance, a ligand is added to the zirconium salt solution, and the zirconium salt solution is mixed uniformly, and the temperature is controlled to control the thermodynamic process of the reaction of the zirconium salt solution, so that zirconium oxide nanoparticles with uniform size and the same molecular structure are formed and can be precipitated in the form of crystals.
Drawings
FIG. 1 is an X-ray single crystal diffraction structural pattern of zirconium oxide nanoparticles obtained in example 1;
FIG. 2 is a dynamic light scattering spectrum of zirconium oxide nanoparticles obtained in example 1;
FIG. 3 is a schematic diagram of the surface topography of the photoresist obtained in Experimental example 3 after etching and developing.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. Preferred embodiments of the present invention are presented herein. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. As used herein, "plurality" includes two and more than two items. As used herein, "above a certain number" should be understood to mean a certain number and a range greater than a certain number.
Other than as shown in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
According to one embodiment of the present invention, a method for preparing zirconium oxide nanoparticles is characterized by comprising the steps of:
providing or preparing a zirconium salt solution comprising a first solvent and a zirconium salt dispersed in the first solvent;
adding a ligand into the zirconium salt solution, and uniformly mixing to prepare a zirconium-containing reaction system;
heating the zirconium-containing reaction system, and controlling the heating temperature to be 40-100 ℃ to generate zirconium oxide in the zirconium-containing reaction system;
the heating was stopped and left to stand until a solid component precipitated.
Wherein the zirconium salt solution may be prepared by itself or may be commercially available.
In some conventional methods for preparing zirconium oxide nanoparticles, a zirconium salt and a ligand are added into a solution together and mixed uniformly, and then the zirconium oxide nanoparticles are prepared by adding water for hydrolysis, but the zirconium oxide nanoparticles prepared by such a mixing method have large and non-uniform sizes, and finally only white powder in a non-crystalline state can be obtained.
In the method for preparing zirconium oxide nanoparticles provided in the above embodiment, a zirconium salt solution is prepared in advance, a ligand is added to the zirconium salt solution, the zirconium salt solution is mixed uniformly, the thermodynamic process of the reaction of the zirconium salt solution is controlled by controlling the temperature, zirconium oxide nanoparticles with uniform size and the same molecular structure are formed, and the zirconium oxide nanoparticles are precipitated in the form of crystals. The molecular structure of the zirconium oxide nanoparticles can be obtained through X-ray single crystal diffraction.
In one specific example, before the ligand is added to the zirconium salt solution, a step of dispersing a zirconium salt in a first solvent to prepare a zirconium salt solution is further included. After the zirconium salt is uniformly dispersed in the first solvent, the ligand is further added to the zirconium salt solution to prepare a zirconium-containing reaction system.
In one specific example, the zirconium salt is selected from salts having zirconium ions, such as one or more of zirconium carboxylate, zirconium sulfonate, zirconium alkoxide, zirconium halide, zirconium nitrate, and zirconium sulfate. In particular, the zirconium salt may be a zirconium alkoxide.
In one specific example, the first solvent is selected from the group consisting of first solvents capable of dissolving the zirconium salt used. Alternatively, the first solvent may be one or more of alcohols, esters, and hydrocarbons.
In one specific example, the ligand is selected from carboxylic acid ligands. Optionally, the ligand is selected from one or more of methacrylic acid, acrylic acid and 3, 3-dimethylacrylic acid.
The ligand will coat around the zirconium oxide particles after the reaction. Meanwhile, the ligand has a certain stabilizing effect on the formation of zirconium oxide crystal grains. In one specific example, in the zirconium-containing reaction system, the ratio of the amount of zirconium ions in the zirconium salt to the amount of the ligand substance is 1 (0.1-10).
In one specific example, after the ligand is added to the zirconium salt solution, stirring is further adopted to uniformly mix the ligand and the zirconium salt solution. The stirring mode can be stirring rod stirring, mechanical stirring or magnetic stirring. Alternatively, the means of stirring is magnetic stirring. The stirring time is based on uniformly mixing the zirconium salt solution and the ligand, and the stirring time is not suitable to be too long. In one specific example, the stirring time is 1min to 10min, and optionally, the stirring time is 5 min.
Further, by controlling the specific temperature conditions in the reaction process, the thermodynamic process of the reaction can be further optimized, and the zirconium oxide with more uniform nano-particle size and single crystal shape can be obtained. In one specific example, in the process of heating the zirconium-containing reaction system, the zirconium-containing reaction system is reacted for 6 to 24 hours at a temperature of 70 to 100 ℃, for 3 to 12 hours at a temperature of 50 to 70 ℃ and for 3 to 12 hours at a temperature of 40 to 50 ℃ in sequence. The temperature of the reaction system is lowered stepwise, and the particle diameter of the zirconium oxide particles obtained by the production can be made more uniform.
In one specific example, after the heating of the zirconium-containing reaction system is stopped, the reaction system is required to be kept still for 24 to 72 hours, so that the reaction system gradually reaches a state with the lowest energy, and the zirconium element is precipitated in the form of zirconium oxide crystals, wherein the precipitated zirconium oxide crystals have the advantages of uniform particle size distribution and small particle size. Optionally, in the process of standing, the temperature of the zirconium-containing reaction system is controlled to be 15-35 ℃. Further, the zirconium-containing reaction system may be controlled to stand at room temperature.
In one specific example, after standing to precipitate a solid component, the method further comprises the steps of obtaining the solid component by filtration and drying the solid component. Alternatively, the manner of drying the solid component is vacuum drying. The temperature for vacuum drying may be normal temperature, for example, 15 ℃ to 35 ℃.
In one specific example, the content of the zirconium salt in the zirconium salt solution is 40 to 80% by mass.
The inventors found that by reasonably controlling the addition sequence of each raw material and the temperature condition of the reaction process, the reaction system containing zirconium salt can spontaneously form crystalline zirconium oxide nanoparticles during standing, which may benefit from the fact that under the conditions optimized by the method, the formed zirconium oxide nanoparticles have uniform size and the same molecular structure, and can obtain the zirconium oxide nanoparticle material in the form of crystals.
Furthermore, the invention also provides zirconium oxide nanoparticles, which are prepared by the preparation method of the zirconium oxide nanoparticles.
Specifically, the zirconium oxide nanoparticles comprise zirconium oxide particles and ligands coating the zirconium oxide nanoparticles, wherein the zirconium oxide is in a crystal shape, and the particle size of the zirconium oxide nanoparticles is between 1nm and 3 nm.
Further, the zirconium oxide nanoparticles can be applied to photoresist.
According to another embodiment of the present invention, a photoresist composition comprises: a second solvent, and a photosensitizer and a photolithographic material dispersed in the second solvent. The photolithographic material comprises zirconium oxide nanoparticles prepared according to the preparation method of zirconium oxide nanoparticles in at least one embodiment.
In one specific example, the weight percentage of the photoresist material in the photoresist composition is 1% to 15%. Optionally, the weight percentage of the lithography material is 5% to 15%. Further optionally, the weight percentage of the lithography material is 8% to 12%.
In one specific example, the weight percentage of the photosensitizer in the photoresist composition is 0.005% to 1.5%. Optionally, the photosensitizer is present in an amount of 0.1% to 1.5% by weight. Further optionally, the photosensitizer is 0.5 to 1.5 weight percent. For example, when the amount of the sensitizer is less than 0.5%, the sensitivity is too low; when the amount of the photosensitizer is more than 1.5%, the photosensitivity is high, which is not favorable for obtaining a high-resolution pattern.
Further, in one specific example, the sensitizer may be selected from photoacid generators. The photoacid generator can include one or more of onium salts, nitrobenzyl compounds, diazo compounds, N-hydroxyimide sulfonates, and halotriazines. Specifically, the triphenylsulfonium triflate, triphenylsulfonium perfluorobutylsulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, p-nitrobenzyl alcohol, diazomethine compounds, diazonaphthoquinone sulfonate, N-hydroxynaphthoylimide triflate, 2- (4-methoxyvinyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine are included, but not limited thereto. N-hydroxynaphthalimide triflate is preferred.
In one specific example, the second solvent in the photoresist composition is one or more of ethyl lactate, butyl acetate, propylene glycol methyl ether acetate, methanol, ethanol, and propanol. Alternatively, the solvent in the photoresist composition is Propylene Glycol Methyl Ether Acetate (PGMEA).
In some other specific examples, the photoresist composition further includes a stabilizer, a leveling agent, a dispersant, or a thickener.
The stabilizer may include, but is not limited to, isoamyl alcohol, n-hexyl alcohol, glycerol, n-hexane, and the like. The stabilizer can ensure the stable chemical performance of the photoresist composition, keep chemical balance, reduce the surface tension of the photoresist composition, and prevent the effects of light, thermal decomposition or oxidative decomposition and the like.
The leveling agent may include, but is not limited to, acrylic compounds, silicone-based compounds, fluorocarbon-based compounds, and the like. The leveling agent has the functions of adjusting the viscosity and the fluidity of a photoresist system and increasing the film forming uniformity.
The dispersant may be a lignosulfonate, such as sodium, calcium, ammonium lignosulfonate, and the like.
The thickener may include, but is not limited to, hydroxymethylcellulose, sodium alginate, hydroxymethyl, hydroxyethylcellulose ether, chitosan, polyacrylamide, and the like.
The photoresist composition can be applied to various lithography technologies, such as 254nm ultraviolet lithography, 365nm ultraviolet lithography, deep ultraviolet lithography, extreme ultraviolet lithography or electron beam lithography, and the like. Preferably, the metal oxide nanoparticles in the photoresist composition have a uniform crystal configuration and an extremely narrow grain size distribution, so that the photoresist composition can show extremely high resolution, and is particularly suitable for extreme ultraviolet lithography or electron beam lithography.
Further, the present invention also provides a method for forming a lithographic pattern, referring to fig. 1, which includes the following steps S100 to S400.
Step S100, applying a photoresist composition according to the above embodiments on a substrate.
Wherein the photoresist composition can be applied to the substrate using conventional equipment such as a spin coater. Prior to application, the photoresist composition is preferably filtered through a filter having a pore size of 0.22 μm. The substrate may be a silicon wafer or a quartz wafer, and may include a silicon wafer or a quartz wafer on which sensors, circuits, transistors, and the like are formed.
Step S200, removing the solvent in the photoresist composition to form a photoresist film.
Specifically, the solvent in the photoresist composition may be removed by drying at a temperature of 50 ℃ to 130 ℃, and the drying time may be 10s to 300 s.
Step S300, exposing the photoresist film under radiation.
Specifically, the obtained photoresist film is exposed to radiation using an exposure system. The exposure system can be a 254nm ultraviolet low-pressure mercury lamp exposure system, a 365nm ultraviolet high-pressure mercury lamp exposure system, a deep ultraviolet lithography system, an extreme ultraviolet lithography system or an electron beam lithography system. Specifically, the photoresist film may be exposed to radiation of an electron beam.
And step S400, developing the exposed photoresist film by using a developer to form a photoetching pattern.
In particular, when forming a photoresist pattern, a mask plate is required to shield light to form a photoresist pattern of a desired shape. Wherein the developer may be one or more of isopropanol, toluene, o-xylene, m-xylene, p-xylene, cyclohexane, n-heptane, n-pentane, 4-methyl-2-pentanol, propylene glycol methyl ether acetate, ethyl acetate, 1, 4-dioxane, and butyl acetate.
In order that the invention may be more readily understood and put into practical effect, reference is also made to the following more specific and detailed examples and comparative examples. The embodiments of the present invention and their advantages will also be apparent from the description of specific examples and comparative examples below, and the performance results.
The raw materials used in the following examples are all commercially available without specific reference.
Example 1
20g of the prepared zirconium salt solution with the mass concentration of 70% and 20g of methacrylic acid are taken, and the methacrylic acid and the zirconium salt solution are mixed and then are stirred for 5min by magnetic force at room temperature so as to be mixed uniformly. In the zirconium salt solution, the zirconium salt is zirconium isopropoxide and the solvent is n-propanol.
After stirring is stopped, heating the reaction system to 80 ℃, and keeping the reaction system to react for 18 hours at the temperature of 80 ℃; cooling the reaction system to 60 ℃, and keeping the reaction system to react for 6 hours at 80 ℃; then the reaction system is cooled to 40 ℃, the reaction system is kept under the condition of 40 ℃ for continuous reaction for 6 hours, and finally the reaction system is cooled to room temperature (about 25 ℃).
And standing the reaction system at room temperature for 2 days to precipitate a solid component in the reaction system, wherein the precipitated solid component is colorless and transparent. And separating the solid component by filtering, and placing the solid component in a vacuum oven to be dried for 6 hours at room temperature so as to completely dry the solid component and obtain the zirconium oxide nano particles.
Example 2
20g of the prepared zirconium salt solution with the mass concentration of 70% and 20g of methacrylic acid are taken, and the methacrylic acid and the zirconium salt solution are mixed and then are stirred for 5min by magnetic force at room temperature so as to be mixed uniformly. In the zirconium salt solution, the zirconium salt is zirconium isopropoxide and the solvent is n-propanol.
After stirring is stopped, heating the reaction system to 65 ℃, and keeping the reaction system to react for 24 hours under the condition of 65 ℃; finally, the reaction was cooled to room temperature (about 25 ℃ C.).
And standing the reaction system at room temperature for 2 days to precipitate a solid component in the reaction system, wherein the precipitated solid component is colorless and transparent. And separating the solid component by filtering, and placing the solid component in a vacuum oven to be dried for 6 hours at room temperature so as to completely dry the solid component and obtain the zirconium oxide nano particles.
Comparative example 1
14g of zirconium isopropoxide and 20g of methacrylic acid were taken and simultaneously added to 6g of n-propanol, followed by magnetic stirring at room temperature for 5min to allow uniform mixing.
After stirring is stopped, heating the reaction system to 65 ℃, and keeping the reaction system to react for 24 hours under the condition of 65 ℃; finally, the reaction was cooled to room temperature (about 25 ℃ C.).
And standing the reaction system at room temperature for 2 days to precipitate a solid component in the reaction system, wherein the precipitated solid component is white powder. And separating the solid component by filtering, and placing the solid component in a vacuum oven to be dried for 6 hours at room temperature so as to completely dry the solid component and obtain the zirconium oxide nano particles.
Comparative example 2
And (3) taking 20g of 70% zirconium salt solution and 20g of methacrylic acid, mixing the methacrylic acid and the zirconium salt solution, and then magnetically stirring for 5min at room temperature to uniformly mix the two. In the zirconium salt solution, the zirconium salt is zirconium isopropoxide and the solvent is n-propanol.
After stirring is stopped, heating the reaction system to 65 ℃, adding a mixture of 1.8g of methacrylic acid and 0.2g of water, and keeping the reaction system at 65 ℃ for continuous reaction for 18 hours; a mixture of 1.8g of methacrylic acid and 0.2g of water was added thereto, and the reaction was continued at 65 ℃ for 6 hours.
Pouring the reaction system into 60g of water, centrifuging and washing with clear water to separate out solid components in the reaction system, wherein the separated solid components are white powder. Vacuum drying at 65 deg.c for 4 hr to obtain nanometer zirconium oxide particle.
The following experimental examples were tested for each of the above examples and comparative examples.
Experimental example 1: the obtained zirconium oxide nanoparticle samples were tested by an X-ray single crystal diffractometer, and the results can be seen in table 1, and the X-ray single crystal diffractometer test pattern of example 1 can be seen in fig. 1.
Experimental example 2: the size distribution of the resulting zirconium oxide nanoparticle samples was measured by a dynamic light scattering instrument, and the results are shown in table 1, and the dynamic light scattering spectra of example 1 and comparative example 2 are shown in table 1.
Experimental example 3: the zirconium oxide nanoparticles obtained in example 1 were used to prepare a photoresist composition, which was further exposed and developed, specifically including the following steps:
dispersing the zirconium oxide nanoparticles obtained in the embodiment 1 in propylene glycol monomethyl ether acetate, and adding N-hydroxynaphthalimide trifluoromethanesulfonate as a photoacid generator to prepare a photoresist composition, wherein the mass content of the zirconium oxide nanoparticles is 10%, the mass content of the photoacid generator is 1%, and the balance is propylene glycol monomethyl ether acetate;
spin-coating the prepared photoresist composition on the surface of a silicon wafer, and pre-baking at 100 ℃ to remove the solvent;
exposing under an extreme ultraviolet (wavelength of 13.5nm) exposure system to form a stripe pattern;
the silicon wafer was immersed in isopropanol and developed, and the patterns on the silicon substrate were observed with a scanning electron microscope, and the test results are shown in fig. 3.
TABLE 1
| Crystal form | Particle size distribution | |
| Example 1 | Crystal | 1nm～3nm |
| Example 2 | Crystal | 1nm～3nm |
| Comparative example 1 | Amorphous substance | 3nm～12nm |
| Comparative example 2 | Amorphous substance | 3nm～12nm |
FIG. 1 is the result of X-ray single crystal diffractometer testing of example 1, which shows that the zirconium oxide nanoparticles obtained in example 1 have a regular crystal structure.
FIG. 2 is a graph showing the particle size distribution of zirconium oxide nanoparticles obtained in example 1, which was measured by a dynamic light scattering instrument, and it was found that the particle size distribution of the zirconium oxide nanoparticles was between 1nm and 3nm, and the number of particles was concentrated around 2 nm.
FIG. 3 shows the fringe pattern after exposure and development, with the scale bar at the bottom left labeled 100nm and the 21nm at the top right indicating the line width of a single fringe. From fig. 3, it can be seen that, by using the crystalline zirconium oxide nanoparticles prepared in example 1 as a lithography material, a lithography pattern with a line width of 21nm with sharp edges can be obtained under the etching of an electron beam exposure system. The photoresist can obtain 21nm photoetching characteristic dimension, and can obtain the requirement of 7nm process node in the CPU process.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (13)
1. A preparation method of zirconium oxide nano particles is characterized by comprising the following steps:
providing or preparing a zirconium salt solution comprising a first solvent and a zirconium salt dispersed in the first solvent;
adding a ligand into the zirconium salt solution, and uniformly mixing to prepare a zirconium-containing reaction system;
heating the zirconium-containing reaction system, and controlling the heating temperature to be 40-100 ℃ to generate zirconium oxide in the zirconium-containing reaction system;
the heating was stopped and left to stand until a solid component precipitated.
2. The method of claim 1, wherein the zirconium salt is selected from one or more of zirconium carboxylate, zirconium sulfonate, zirconium alkoxide, zirconium halide, zirconium nitrate, and zirconium sulfate.
3. The method according to claim 1, wherein the first solvent is one or more selected from the group consisting of an alcohol solvent, an ester solvent, and a hydrocarbon solvent.
4. The method of claim 1, wherein the ligand is selected from carboxylic acid ligands.
5. The method for producing zirconium oxide nanoparticles according to any one of claims 1 to 4, wherein the ratio of the amount of zirconium ions in the zirconium salt to the amount of the ligand substance in the zirconium-containing reaction system is 1 (0.1 to 10).
6. The method for preparing zirconium oxide nanoparticles according to any one of claims 1 to 4, wherein the zirconium-containing reaction system is reacted at a temperature of 70 ℃ to 100 ℃ for 6 to 24 hours, at a temperature of 50 ℃ to 70 ℃ for 3 to 12 hours, and at a temperature of 40 ℃ to 50 ℃ for 3 to 12 hours, in this order, while the zirconium-containing reaction system is heated.
7. The method for producing zirconium oxide nanoparticles according to any one of claims 1 to 4, further comprising a step of obtaining the solid component by filtration and drying the solid component after the step of standing until the solid component is precipitated.
8. The method according to any one of claims 1 to 4, wherein the zirconium salt is contained in the zirconium salt solution in an amount of 40 to 80% by mass.
9. Zirconium oxide nanoparticles, characterized by being produced by the method for producing zirconium oxide nanoparticles according to any one of claims 1 to 8.
10. A photoresist composition, comprising: a second solvent, and a sensitizer and a photolithographical material dispersed in the second solvent, the photolithographical material comprising zirconium oxide nanoparticles according to claim 9.
11. The photoresist composition of claim 10, wherein the photoresist material is present in an amount of 1 to 15% by weight and the sensitizer is present in an amount of 0.005 to 1.5% by weight.
12. Use of a photoresist composition according to claim 10 or 11 in the preparation of a lithographic pattern.
13. Use of the photoresist composition according to claim 12 for preparing a lithographic pattern, wherein the exposure is carried out using an extreme ultraviolet lithography system or an electron beam lithography system in preparing the lithographic pattern.
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| CN114527630A (en) * | 2022-04-21 | 2022-05-24 | 之江实验室 | Femtosecond laser direct writing method for zirconium dioxide micro-nano pattern |
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| CN103588247A (en) * | 2013-11-05 | 2014-02-19 | 北京理工大学 | Novel method for carrying out solvothermal synthesis to obtain monodisperse high-crystallinity zirconia quantum dots |
| CN111948904A (en) * | 2020-08-13 | 2020-11-17 | 清华大学 | Photoresist composition, method for forming photolithographic pattern using the same, and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103588247A (en) * | 2013-11-05 | 2014-02-19 | 北京理工大学 | Novel method for carrying out solvothermal synthesis to obtain monodisperse high-crystallinity zirconia quantum dots |
| CN111948904A (en) * | 2020-08-13 | 2020-11-17 | 清华大学 | Photoresist composition, method for forming photolithographic pattern using the same, and use thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114527630A (en) * | 2022-04-21 | 2022-05-24 | 之江实验室 | Femtosecond laser direct writing method for zirconium dioxide micro-nano pattern |
| CN114527630B (en) * | 2022-04-21 | 2022-08-05 | 之江实验室 | Femtosecond laser direct writing method for zirconium dioxide micro-nano pattern |
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