A three-dimensional IGZO nanoparticle and its preparation method and application
By controlling the size and morphology of IGZO particles, three-dimensional IGZO nanoparticles were prepared, which solved the problem of poor dispersion of nano-scale IGZO particles, and achieved efficient and low-cost preparation of high-quality semiconductor films.
Patent Information
- Application Number
- CN202411669829.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-21
- Publication Date
- 2025-04-04
AI Technical Summary
Prior Art When preparing IGZO films, the agglomeration and uneven size of nanoscale IGZO particles lead to poor dispersion, and a dispersant is required to add a dispersant to affect the performance of the final film.
Three-dimensional IGZO nanoparticles were prepared by controlling the D90 size of IGZO particles at 150-300 nm and adopting a cube form, combining high-pressure heat treatment and precise control of the sintering temperature, which significantly improved their dispersion in solution.
The uniform dispersion of IGZO nanoparticles in various solvents is achieved, the ink preparation process is simplified, the density and electrical properties of the film are improved, and the production cost is reduced.
Smart Images
Figure CN119750636A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of semiconductor thin films and relates to three-dimensional IGZO nanoparticles and a preparation method and application thereof. Background Art
[0002] With the development of emerging electronic technologies, especially the rise of wearable electronic devices and flexible displays, the importance of thin film integrated circuits has become increasingly prominent, and the demand for thin film materials has gradually shifted towards low cost, flexibility and high stability. In this context, metal oxides such as ZnO (zinc oxide), In2O3 (indium oxide) and IGZO (indium gallium zinc oxide) have attracted widespread attention due to their excellent physical and chemical properties. These materials not only have high carrier mobility and low film preparation temperature (room temperature to 350°C), but also show good light transmittance, making them ideal for flexible electronic devices.
[0003] In particular, IGZO, as an advanced n-type semiconductor metal oxide, stands out for its unique properties: high mobility, low off-state current, excellent optical transmittance and wide bandgap (about 3.5eV). These properties make IGZO very suitable for making high-performance flexible thin-film transistors (TFTs), and can be widely used in flexible liquid crystal displays, sensors, detectors and even biomedical devices. In order to meet the preparation needs of flexible electronic devices, successfully attaching a layer of IGZO film on a flexible substrate has become one of the key technologies.
[0004] There are various technical means for preparing IGZO thin films, including but not limited to magnetron sputtering, pulsed laser deposition, sol-gel method, chemical vapor deposition, atomic layer deposition, and pulsed DC magnetron sputtering. Although deposition and sputtering techniques are limited in industrial applications due to their high cost, they are still indispensable methods for preparing display devices. In contrast, the sol-gel method is particularly suitable for temperature-sensitive organic film substrates because it can react at lower temperatures, although this method is still mainly limited to the laboratory research stage. It is worth noting that printable or printable inks prepared using nano-sized IGZO particles are gradually becoming a research hotspot due to their efficient production and economical characteristics. For example, Huaxing Optoelectronics has developed a method for manufacturing OLED-TFTs through inkjet printing technology, which not only reduces production costs but also simplifies certain steps in the manufacturing process, such as reducing one photolithography process. However, even so, due to the complex structure of the display panel and involving multiple layers, it is still necessary to combine a variety of different technical means throughout the manufacturing process. In addition, even in the application of inkjet printing technology, the preparation of IGZO semiconductor layers usually relies on the relatively inefficient chemical vapor deposition method.
[0005] The key to further preparing IGZO ink is to prepare small-sized (<2μm) IGZO with uniform morphology, suitable microscopic size, and good semiconductor performance. Nobuko Fukuda et al. prepared IGZO nanoparticles by sol-gel method and then prepared them into ink (J. Mater. Chem. C, 2014, 2, 2448–2454). Gyoujin Cho et al. obtained nano-IGZO particles by sol-gel method, ball milling after sintering, and centrifugation (Adv. Electron. Mater. 2018, 1800078). The above work shows the possibility of preparing ink by nano-IGZO and further processing IGZO film. However, due to problems such as particle agglomeration and uneven particle size, it is necessary to introduce ultrasound, ball milling, centrifugation and other processes in the early stage of preparing ink, and the yield is not high; and due to problems such as agglomeration and uneven size, dispersants need to be added during the preparation of ink, resulting in the problem of decreased performance of the final IGZO film. Summary of the invention
[0006] The purpose of the present invention is to address the above-mentioned problems existing in the prior art and to propose a three-dimensional IGZO nanoparticle that can be better dispersed in various solvents to prepare n-type semiconductor ink for printing / inkjet printing.
[0007] The purpose of the present invention can be achieved by the following technical solutions:
[0008] A three-dimensional IGZO nanoparticle, wherein the three-dimensional IGZO nanoparticle is in a cubic form and has a particle size D90 of 150-300 nm.
[0009] The present invention can significantly improve the dispersibility of IGZO particles in the solution by strictly controlling the D90 size of IGZO particles to 150-300nm, forming a stable and uniform dispersion. This dispersion can further be used to prepare a slurry suitable for printing technology, thereby realizing efficient and low-cost preparation of semiconductor films. In addition, since these cubic particles of the present invention can be closely packed together, this not only helps to improve the density of the film, but also effectively reduces the contact resistance between particles, thereby improving the overall electrical properties of the semiconductor film. This method not only simplifies the preparation process of semiconductor films, but also provides new possibilities for the large-scale production and application of flexible electronic devices.
[0010] The present invention also provides a method for preparing the above three-dimensional IGZO nanoparticles, the method comprising the following steps:
[0011] S1, sequentially adding In salt, Ga salt and Zn salt into water and stirring to obtain a mixed solution;
[0012] S2, then adding an alkaline additive, stirring and adjusting the pH, and then performing a high pressure heat treatment;
[0013] S3, after the heat treatment, washing and drying are performed in sequence, and finally a high-temperature sintering treatment is performed to obtain three-dimensional IGZO nanoparticles.
[0014] In the above-mentioned method for preparing three-dimensional IGZO nanoparticles, the molar ratio of In salt, Ga salt and Zn salt in step S1 is 1:(1-2):(1-3).
[0015] In the above-mentioned method for preparing three-dimensional IGZO nanoparticles, the salt in step S1 includes at least one of nitrate, chloride, sulfate, and acetate.
[0016] In the above-mentioned method for preparing three-dimensional IGZO nanoparticles, the alkaline additive in step S2 is ammonia water or ethanolamine in a mass ratio of 1: (0.5-1.5).
[0017] In the above method for preparing three-dimensional IGZO nanoparticles, the pH in step S2 is adjusted to 6-12.
[0018] In the above-mentioned method for preparing three-dimensional IGZO nanoparticles, the temperature in step S2 high-pressure heat treatment is 150-240°C and the air pressure is 5-10MPa. In the process of preparing three-dimensional IGZO nanoparticles of the present invention, high-pressure heat treatment is a key link. The temperature needs to be controlled at 150 to 240°C, and a pressure of 5 to 10MPa is applied at the same time. Under this condition, the IGZO nanoparticles gradually grow into a cubic form through the Oswald ripening mechanism. Oswald ripening is a process in which small particles are dissolved and redeposited on the surface of large particles, thereby promoting particle growth and maintaining consistency of shape. However, the control of pressure in the present invention is crucial: if the pressure is too high, it will cause excessive growth of particles, resulting in excessive particles, which will in turn cause agglomeration, affecting the dispersibility of the particles and the performance of the final product; on the contrary, if the pressure is too low, it will not provide sufficient driving force to make the particles grow in the required cubic form, resulting in irregular particle shape or failure to generate. Therefore, the precise control of the temperature and pressure conditions during the heat treatment process of the present invention is crucial to obtaining ideal three-dimensional cubic IGZO nanoparticles. This method not only ensures the quality of the nanoparticles, but also provides a reliable basis for the subsequent dispersion preparation and printing preparation of semiconductor films.
[0019] In the above-mentioned method for preparing three-dimensional IGZO nanoparticles, the drying treatment in step S3 includes at least one of freeze drying and spray drying.
[0020] In the above-mentioned method for preparing three-dimensional IGZO nanoparticles, the high-temperature sintering temperature is 700-1200°C. The present invention strictly controls the sintering temperature between 700 and 1200°C. This temperature range is selected to ensure that the IGZO nanoparticles can form a good crystalline structure while maintaining a cubic form. If the sintering temperature is too low, below 700°C, it may cause insufficient crystallinity of IGZO, affecting its electrical properties and stability. On the contrary, if the temperature is too high, exceeding 1200°C, it may destroy the already formed cubic structure, causing deformation or agglomeration of the particles, which will also affect the performance of the final product.
[0021] The present invention also provides a printing paste for a flexible thin film transistor, wherein the printing paste is prepared from the three-dimensional IGZO nanoparticles.
[0022] Compared with the prior art, the present invention has the following beneficial effects:
[0023] The present invention successfully prepared IGZO nanoparticles in the shape of three-dimensional cubes with a particle size D90 between 150 and 300 nanometers. Nanoparticles of this specific morphology and size exhibit excellent dispersibility and can be evenly distributed in a variety of solvents, thus making it possible to prepare high-quality n-type semiconductor inks. These inks are particularly suitable for printing and inkjet printing technologies, which can not only improve production efficiency but also ensure the consistency and reliability of the produced thin-film semiconductor functional modules. Using this technology, large-scale and low-cost manufacturing of flexible electronic devices, such as flexible displays, sensors and other key components of smart devices, can be achieved, greatly promoting the development and commercialization of flexible electronic technology. In addition, by precisely controlling the size and morphology of the nanoparticles, the performance of the ink can be further optimized to meet the special needs of different application scenarios. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] Figure 1 This is a scanning electron microscope morphology image of cubic IGZO nanoparticles in Example 1;
[0025] Figure 2 This is a scanning electron microscope morphology image of cubic IGZO nanoparticles in Example 2;
[0026] Figure 3 This is the EDS spectrum element distribution diagram of the cubic IGZO nanoparticles in Example 2;
[0027] Figure 4 This is a scanning electron microscope morphology image of cubic IGZO nanoparticles of Comparative Example 1;
[0028] Figure 5 This is a scanning electron microscope morphology image of cubic IGZO nanoparticles of comparative example 2. DETAILED DESCRIPTION
[0029] The following are specific embodiments of the present invention, which further describe the technical solutions of the present invention, but the present invention is not limited to these embodiments.
[0030] Embodiment 1:
[0031] S1, sequentially adding 0.05M indium nitrate, 0.05M gallium nitrate, and 0.1M zinc acetate into water and stirring to dissolve to obtain a mixed solution;
[0032] S2. Slowly drop ammonia water and ethanolamine in a mass ratio of 1:1 to completely precipitate the mixture, and then adjust the pH to 11 after stirring;
[0033] S3, then subjecting the reaction solution to high pressure heat treatment at a temperature of 210° C. and a gas pressure of 8 MPa for 10 h to obtain an IGZO precursor;
[0034] S4. The IGZO precursor is washed and freeze-dried, and the dried powder is sintered at 900° C. for 3 hours in a tube furnace to obtain cubic IGZO nanoparticles.
[0035] Embodiment 2:
[0036] S1, sequentially add 0.1M indium nitrate, 0.1M gallium nitrate, and 0.15M zinc acetate into water and stir to dissolve to obtain a mixed solution;
[0037] S2. Slowly drop ammonia water and ethanolamine in a mass ratio of 1:1 to completely precipitate the mixture, and then adjust the pH to 11 after stirring;
[0038] S3, then subjecting the reaction solution to high pressure heat treatment at a temperature of 150° C. and an air pressure of 5 MPa for 10 h to obtain an IGZO precursor;
[0039] S4. The IGZO precursor was washed and freeze-dried, and the dried powder was sintered at 950° C. for 3 hours in a tube furnace to obtain cubic IGZO nanoparticles.
[0040] Embodiment 3:
[0041] S1, sequentially adding 0.2M indium nitrate, 0.2M gallium nitrate and 0.2M zinc acetate into water and stirring to dissolve to obtain a mixed solution;
[0042] S2. Slowly drop ammonia water and ethanolamine in a mass ratio of 1:1 to completely precipitate the mixture, and then adjust the pH to 11 after stirring;
[0043] S3, then the reaction solution is subjected to high pressure heat treatment at a temperature of 240°C and an air pressure of 10 MPa for 10 h to obtain an IGZO precursor
[0044] S4. The IGZO precursor is washed and freeze-dried, and the dried powder is sintered in a tube furnace at 1200° C. for 3 hours to obtain cubic IGZO nanoparticles.
[0045] Comparative Example 1:
[0046] S1, sequentially adding 0.05M indium nitrate, 0.05M gallium nitrate, and 0.1M zinc acetate into water and stirring to dissolve to obtain a mixed solution;
[0047] S2. Slowly drop ammonia water and ethanolamine in a mass ratio of 1:1 to completely precipitate the mixture, and then adjust the pH to 11 after stirring;
[0048] S3, then subjecting the reaction solution to high pressure heat treatment at a temperature of 210° C. and an air pressure of 15 MPa for 10 h to obtain an IGZO precursor;
[0049] S4. The IGZO precursor is washed and freeze-dried, and the dried powder is sintered at 900° C. for 3 hours in a tube furnace to obtain cubic IGZO nanoparticles.
[0050] Comparative Example 2:
[0051] S1, sequentially adding 0.05M indium nitrate, 0.05M gallium nitrate, and 0.1M zinc acetate into water and stirring to dissolve to obtain a mixed solution;
[0052] S2. Slowly drop ammonia water and ethanolamine in a mass ratio of 1:1 to completely precipitate the mixture, and then adjust the pH to 11 after stirring;
[0053] S3, then subjecting the reaction solution to high pressure heat treatment at a temperature of 210° C. and an air pressure of 1 MPa for 10 h to obtain an IGZO precursor;
[0054] S4. The IGZO precursor is washed and freeze-dried, and the dried powder is sintered at 900° C. for 3 hours in a tube furnace to obtain cubic IGZO nanoparticles.
[0055] from Figure 1-3 It can be seen that under the conditions of specified pH, metal salt concentration, proportional temperature, etc., a cubic IGZO precursor with relatively uniform size can be obtained, and the precursor can be further subjected to heat treatment to obtain IGZO nanocubes.
[0056] Figure 4 This is a scanning electron microscope morphology of cubic IGZO nanoparticles in comparative example 1; it can be seen from the figure that when the reaction pressure is too high, the IGZO precursor particles grow to a larger size, about 1 μm, and are prone to agglomeration, which affects the subsequent dispersion of IGZO.
[0057] Figure 5This is a scanning electron microscope morphology of cubic IGZO nanoparticles of comparative example 2. It can be seen from the figure that when the gas pressure is too low, only a small part of the cubic particle precursor is generated, and most of them are irregular particles.
[0058] In summary, the present invention successfully prepared IGZO nanoparticles in the shape of three-dimensional cubes with a particle size D90 between 150 and 300 nanometers. Nanoparticles of this specific morphology and size exhibit excellent dispersion properties and can be evenly distributed in a variety of solvents, thus providing the possibility of preparing high-quality n-type semiconductor inks. These inks are particularly suitable for printing and inkjet printing technology, which can not only improve production efficiency, but also ensure the consistency and reliability of the produced thin-film semiconductor functional modules. Using this technology, large-scale and low-cost manufacturing of flexible electronic devices, such as flexible displays, sensors and other key components of smart devices, can be achieved, greatly promoting the development and commercialization of flexible electronic technology.
[0059] The parts of the embodiments herein that are not exhaustive of the midpoint values of the technical scope claimed for protection by the present invention and the new technical solutions formed by equivalent replacement of single or multiple technical features in the technical solutions of the embodiments are also within the scope claimed for protection by the present invention; at the same time, in all the listed or unlisted embodiments of the scheme of the present invention, each parameter in the same embodiment merely represents an example of its technical solution (i.e., a feasible solution), and there is no strict coordination and limitation relationship between the parameters, wherein the parameters can be replaced with each other without violating the axioms and the claims of the present invention, unless otherwise stated.
[0060] The technical means disclosed in the scheme of the present invention are not limited to the technical means disclosed in the above technical means, but also include technical schemes composed of any combination of the above technical features. The above is a specific implementation of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications are also regarded as the protection scope of the present invention.
[0061] The specific embodiments described herein are merely examples of the spirit of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in similar ways, but they will not deviate from the spirit of the present invention or exceed the scope defined by the appended claims.
Claims
1. A three-dimensional IGZO nanoparticle, characterized in that: The three-dimensional IGZO nanoparticles are in a cubic shape, and the particle size D90 is 150-300 nm.
2. A method for preparing three-dimensional IGZO nanoparticles as claimed in claim 1, characterized in that: The method comprises the following steps: S1, sequentially adding In salt, Ga salt and Zn salt into water and stirring to obtain a mixed solution; S2, then adding an alkaline additive, stirring and adjusting the pH, and then performing a high pressure heat treatment; S3, after the heat treatment, washing and drying are performed in sequence, and finally a high-temperature sintering treatment is performed to obtain three-dimensional IGZO nanoparticles.
3. The method for preparing three-dimensional IGZO nanoparticles according to claim 2, characterized in that: The molar ratio of In salt, Ga salt and Zn salt in step S1 is 1:(1-2):(1-3).
4. The method for preparing three-dimensional IGZO nanoparticles according to claim 2, characterized in that: The salt in step S1 includes at least one of nitrate, chloride, sulfate and acetate.
5. The method for preparing three-dimensional IGZO nanoparticles according to claim 2, characterized in that: The alkaline additive in step S2 is ammonia water and ethanolamine in a mass ratio of 1: (0.5-1.5).
6. The method for preparing three-dimensional IGZO nanoparticles according to claim 2, characterized in that: In step S2, the pH is adjusted to 6-12.
7. The method for preparing three-dimensional IGZO nanoparticles according to claim 2, characterized in that: In step S2, the temperature of the high pressure heat treatment is 150-240°C and the gas pressure is 5-10MPa.
8. The method for preparing three-dimensional IGZO nanoparticles according to claim 2, characterized in that: The drying process in step S3 includes at least one of freeze drying and spray drying.
9. The method for preparing three-dimensional IGZO nanoparticles according to claim 2, characterized in that: The high temperature sintering temperature is 700-1200℃.
10. A printing paste for a flexible thin film transistor, characterized in that: The printing paste is prepared from the three-dimensional IGZO nanoparticles according to claim 1.