CN117747435A

CN117747435A - Precursor solution for surface energy directional assembly processing technology and preparation method thereof

Info

Publication number: CN117747435A
Application number: CN202211123645.5A
Authority: CN
Inventors: 柴智敏; 路新春; 张经纬
Original assignee: Tsinghua University
Current assignee: Tsinghua University
Priority date: 2022-09-15
Filing date: 2022-09-15
Publication date: 2024-03-22

Abstract

Precursor solution for surface energy directional assembly processing technology, preparation method of the precursor solution, pattern preparation method adopting surface energy directional assembly processing technology, and method for preparing electronic device by adopting surface energy directional assembly processing technology. The precursor solution comprises: alcohols or alcohol ethers organic solvents, precursor salts of metal oxides, and stabilizers.

Description

Precursor solution for surface energy directional assembly processing technology and preparation method thereof

Technical Field

The present disclosure relates to the field of surface energy directional assembly processing technology, and in particular, to a precursor solution for a surface energy directional assembly processing technology, a preparation method of the precursor solution, a pattern preparation method adopting the surface energy directional assembly processing technology, and a method for preparing an electronic device adopting the surface energy directional assembly processing technology.

Background

The thin film transistor (Thin Film Transistors, TFT) is a core element of the display screen for controlling the lighting and turning off of the pixel. For example, an 8K high definition display screen has 7680x4320 pixels, and 1-7 thin film transistors are required to control each pixel to perform monochrome display, and 1-7 hundred million thin film transistors are required for the whole display screen. The thin film transistor comprises a semiconductor active layer, a source electrode, a drain electrode, a gate insulating layer and a gate electrode four-layer structure. Currently, commercial thin film transistors are manufactured mainly through traditional integrated circuit processes, and involve processes such as vacuum thin film deposition, photolithography, dry etching, wet etching and the like, wherein the cost of the vacuum thin film deposition process accounts for very high proportion of the total processing cost, and approximately accounts for 42% of the total processing cost. If the vacuum thin film deposition process is replaced, the processing cost of the thin film transistor is greatly reduced. In addition, the vacuum film deposition process is not compatible with the flexible substrate, and development of flexible display technology is restricted.

In contrast, the surface energy directional assembly processing technology has the inherent advantages of no need of expensive equipment and process, simple equipment, realization of flexible large-area production and the like, and becomes an ideal technology for processing semiconductor components, in particular to an ideal technology for processing a new generation of flexible display screen.

Disclosure of Invention

According to an embodiment of the present disclosure, there is provided a precursor solution for a surface energy directional assembly processing technique, comprising: alcohols or alcohol ethers organic solvents, precursor salts of metal oxides, and stabilizers.

For example, the organic solvent is a high boiling point solvent having a boiling point in the range: t is more than or equal to 230 ℃ and less than or equal to 300 ℃.

For example, the high boiling point solvent is selected from one or more of diethylene glycol, ethylene glycol phenyl ether, propylene glycol phenyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, dipropylene glycol butyl ether, triethylene glycol methyl ether, triethylene glycol diethyl ether, triethylene glycol butyl ether, tripropylene glycol methyl ether, and tripropylene glycol butyl ether.

For example, the organic solvent is a low boiling point solvent having a boiling point in the range of: t is less than or equal to 50 ℃ and less than 230 ℃.

For example, the low boiling point solvent is selected from one or more of ethanol, ethylene glycol, isopropanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol isopropyl ether, ethylene glycol butyl ether, ethylene glycol t-butyl ether, ethylene glycol hexyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-propyl ether, propylene glycol isopropyl ether, propylene glycol n-butyl ether, propylene glycol t-butyl ether, diethylene glycol methyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol dibutyl ether, diethylene glycol hexyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether.

For example, the precursor salt is selected from one or more of an acetate salt of a metal, a nitrate salt of a metal, and a chloride salt of a metal, and the metal is selected from one or more of zinc, gallium, indium, tin, hafnium, and aluminum.

For example, the stabilizer includes carboxylic acids and/or organic amines.

For example, the stabilizer is selected from one or more of acetic acid, citric acid, ethanolamine, diethanolamine, triethanolamine, and acetylacetone.

For example, the precursor solution further includes a surfactant that adjusts the surface tension of the precursor solution.

For example, the precursor solution has a surface tension ranging from 15mN/m to 72mN/m and a viscosity ranging from 0.8cp to 49cp.

For example, the solvent is a high boiling point solvent having a boiling point in the range: t is more than or equal to 230 ℃ and less than or equal to 300 ℃, the surface tension of the precursor solution ranges from 29mN/m to 50mN/m, and the viscosity ranges from 4cp to 49cp; the solvent is a low boiling point solvent, and the boiling point range is as follows: the temperature T is more than or equal to 50 ℃ and less than 230 ℃, the surface tension of the precursor solution ranges from 15mN/m to 72mN/m, and the viscosity ranges from 0.8cp to 20cp.

For example, the surfactant is selected from one or more of triton X-100, alkylphenol ethoxylates and fatty alcohol ethoxylates.

For example, the precursor solution also includes a fuel.

For example, the fuel is selected from one or more of ethylene glycol, urea, acetylacetone, and tetramethyltriazine.

For example, the organic solvent may be present in an amount of 60% to 99.5% by weight, the precursor salt of the metal oxide may be present in an amount of 0.3% to 20% by weight, the stabilizer may be present in an amount of 0.1% to 10% by weight, the surfactant may be present in an amount of 0.1% to 15% by weight, and the fuel may be present in an amount of 0 to 20% by weight, based on the total weight of the precursor solution.

For example, the precursor solution is composed of the organic solvent, the precursor salt of the metal oxide, the stabilizer, the surfactant, and the fuel.

For example, the ratio of the precursor salt of the metal oxide to the mass concentration of the stabilizer is: 1:1-1:3, wherein the weight ratio of the precursor salt of the metal oxide to the stabilizer is as follows: 1:1 to 5:1.

According to an embodiment of the present disclosure, there is provided a method for preparing a precursor solution as described above, including: step S1: adding the precursor salt of the metal oxide into the organic solvent and stirring to obtain a mixed solution; step S2: adding the stabilizer into the mixed solution and stirring; if the mixed solution is not clear, repeating the adding of the stabilizer and stirring until the mixed solution is clear.

For example, the method further comprises: adding a surfactant and/or a fuel to the clarified mixed solution.

For example, the precursor solution includes precursor salts of the first to n-th metal oxides, n being 2 or more; and the method comprises: sequentially performing step S1 and step S2 to obtain a clarified first mixed solution comprising a precursor salt of the first metal oxide; adding a precursor salt of a second metal oxide to the clarified first mixed solution and stirring to obtain a second mixed solution comprising the precursor salt of the first metal oxide and the precursor salt of the second metal oxide; adding a stabilizer and stirring if the second mixed solution is not clear, and repeatedly executing the addition of the stabilizer and stirring if the second mixed solution is still not clear until the second mixed solution is clear; and so on until the precursor salt of the nth metal oxide is added to the clarified nth-1 mixed solution and stirred to obtain an nth mixed solution including the precursor salts of the first to nth metal oxides; and adding the stabilizing agent and stirring if the nth mixed solution is not clear, and repeatedly executing the adding of the stabilizing agent and stirring if the nth mixed solution is still not clear until the nth mixed solution is clear.

For example, the precursor salts of the first through n-th metal oxides are salts of n different metals, respectively, the n different metals including indium; and the precursor salt of the first metal oxide is a salt of indium.

For example, the method further comprises: adding a surfactant and/or a fuel to the clarified nth mixed solution.

According to an embodiment of the present disclosure, there is provided a pattern preparation method, which adopts a surface energy directional assembly processing technique, including: providing a substrate; treating the substrate such that the substrate has hydrophilic regions; applying a precursor solution as described above to the substrate, the precursor solution selectively adsorbing to the hydrophilic region; drying the precursor solution to obtain a dried product; annealing the dried product in an oxygen-containing environment to obtain a pattern of metal oxides.

For example, processing the substrate includes: subjecting the entire substrate to hydrophilic treatment to obtain the hydrophilic region; or carrying out hydrophobic treatment on the whole substrate, and carrying out hydrophilic treatment on a local area of the substrate by matching with a mask plate so as to obtain the hydrophilic area; or carrying out hydrophilic treatment on the whole substrate, and carrying out hydrophobic treatment on a local area of the substrate by matching with a mask plate so as to obtain the hydrophilic area.

For example, the hydrophilic treatment includes: one or more of oxygen plasma treatment, piranha solution soaking, laser irradiation, and treatment with UV-O3; and the hydrophobic treatment comprises: the SAM layer is formed and the organic solution used to form the SAM layer includes one or more of trimethoxysilanes, triethoxysilanes, trichlorosilane, and phosphonic acids.

The precursor solution is applied to the substrate, for example, by a pulling method, a slot coating method, a blade coating method, or a spin coating method.

For example, the organic solvent is a high boiling point solvent having a boiling point in the range: t is more than or equal to 230 ℃ and less than or equal to 300 ℃; the precursor solution includes a surfactant; the method comprises the following steps: the precursor solution is applied to the substrate in an environment of arbitrary relative humidity and dried.

For example, the organic solvent is a high boiling point solvent having a boiling point in the range: t is more than or equal to 230 ℃ and less than or equal to 300 ℃; the method comprises the following steps: the precursor solution is applied to the substrate in an environment having a relative humidity above 40% rh and/or the precursor solution is dried in an environment having a relative humidity above 40% rh.

For example, the organic solvent is a low boiling point solvent, and the boiling point T ranges from: t is more than or equal to 50 ℃ and less than 230 ℃; the method comprises the following steps: the precursor solution is applied to the substrate in an environment having a relative humidity of 30% rh or less and/or the precursor solution is dried in an environment having a relative humidity of 30% rh or less.

For example, annealing the dried product, including: a first annealing process and a second annealing process are sequentially performed, wherein the temperature of the first annealing process is lower than the temperature of the second annealing process, and the duration of the first annealing process is shorter than the duration of the second annealing process.

For example, the temperature of the first annealing process is 25 ℃ to 200 ℃, and the duration of the first annealing process is less than or equal to 30 minutes; and the temperature of the second annealing process is 50-1000 ℃, and the duration of the second annealing process is less than or equal to 2 hours.

For example, the pattern of the metal oxide is a semiconductor pattern, and the precursor salt of the metal oxide is selected from one or more of zinc acetate, zinc nitrate, zinc chloride, indium acetate, indium nitrate, indium chloride, gallium acetate, gallium nitrate, gallium chloride, tin acetate, tin nitrate, tin tetrachloride, and stannous chloride.

For example, the pattern of the metal oxide is a conductive pattern, and the precursor salt of the metal oxide is one or more selected from the group consisting of indium acetate, indium nitrate, indium chloride, tin acetate, tin nitrate, tin tetrachloride, and stannous chloride.

For example, the pattern of the metal oxide is an insulating pattern, and the precursor salt of the metal oxide is selected from one or more of hafnium tetrachloride, hafnium oxychloride, hafnium ethoxide, hafnium isopropoxide, hafnium n-butoxide, aluminum acetate and aluminum nitrate.

For example, the pattern of the metal oxide has a size of 500nm or more.

According to an embodiment of the present disclosure, there is provided a method of manufacturing an electronic device comprising a semiconductor layer, a conductor layer and an insulating layer using a surface energy directed assembly process technique, wherein the method comprises manufacturing at least one of the semiconductor layer, the conductor layer and the insulating layer of the electronic device using the method as described above.

For example, a method of making an electronic device using surface energy directed assembly processing techniques, comprising: and preparing a preceding layer of the semiconductor layer, the conductor layer and the insulating layer of the electronic device, and then preparing a following layer of the semiconductor layer, the conductor layer and the insulating layer of the electronic device, wherein during the preparation of the following layer of the semiconductor layer, the conductor layer and the insulating layer of the electronic device, a local region of the substrate is subjected to a hydrophobic treatment to obtain a hydrophilic region for adsorbing the following layer, the hydrophobic treatment comprises forming a SAM layer, and an organic solution for forming the SAM layer comprises one or more of trimethoxysilanes and triethoxysilanes.

For example, the number of the cells to be processed, trimethoxysilanes include trimethoxy (1H, 2H-nonafluorohexyl) silane trimethoxy (1H, 2H-tridecafluoron-octyl) silane, trimethoxy (1H, 2H-heptadecafluorodecyl) silane one or more of octadecyltrimethoxysilane, hexadecyltrimethoxysilane, dodecyltrimethoxysilane and octyltrimethoxysilane; and triethoxysilanes include triethoxy (1H, 2H-nonafluorohexyl) silane triethoxy-1H, 2H-tridecyl fluoro-n-octyl silane, 1H, 2H-perfluoro decyl triethoxy silane one or more of octadecyltriethoxysilane, hexadecyltriethoxysilane, dodecyl triethoxysilane, hexyl triethoxysilane, and butyl triethoxysilane.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings of the embodiments will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present disclosure, not to limit the present disclosure.

FIG. 1 is a schematic diagram of the relationship between relative humidity and pattern fill rate in the preparation of a pattern using a high boiling point organic solvent for a precursor solution according to an embodiment of the present disclosure;

FIG. 2 is a schematic diagram of the relationship between relative humidity and pattern fill rate when preparing a pattern using a low boiling point organic solvent for a precursor solution according to an embodiment of the present disclosure;

FIG. 3 is a schematic diagram of the relationship between relative humidity and pattern fill rate when preparing a pattern using a high boiling point organic solvent and including a surfactant for a precursor solution according to an embodiment of the present disclosure;

FIG. 4 is a flow diagram of a method of preparing a precursor solution according to an embodiment of the present disclosure;

FIG. 5 is a schematic diagram of a metal oxide thin film transistor;

FIG. 6 is a graph of Id-Vg for the metal oxide thin film transistor shown in FIG. 5;

FIG. 7 is a schematic diagram of a capacitor structure;

FIG. 8 is a C-V plot of the capacitance shown in FIG. 7;

FIG. 9 is a schematic diagram of a four probe method for testing the performance of a metal oxide electrode;

FIG. 10 is an I-V graph of a metal oxide electrode;

FIG. 11 is a schematic diagram of a metal oxide thin film transistor;

fig. 12 is an Id-Vg plot of the metal oxide thin film transistor shown in fig. 11.

Detailed Description

For the purpose of making the objects, technical solutions and advantages of the embodiments of the present disclosure more apparent, the technical solutions of the embodiments of the present disclosure will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present disclosure. It will be apparent that the described embodiments are some, but not all, of the embodiments of the present disclosure. All other embodiments, which can be made by one of ordinary skill in the art without the need for inventive faculty, are within the scope of the present disclosure, based on the described embodiments of the present disclosure.

Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this disclosure belongs. The terms "first," "second," and the like in the description and in the claims, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The word "comprising" or "comprises", and the like, means that elements or items preceding the word are included in the element or item listed after the word and equivalents thereof, but does not exclude other elements or items. "inner", "outer", "upper", "lower", etc. are used merely to denote relative positional relationships, which may also change accordingly when the absolute position of the object to be described changes.

The drawings in this disclosure are not necessarily to scale, and the specific dimensions and numbers of individual structures may be determined according to actual needs. The drawings described in the present disclosure are only schematic in structure.

The surface energy directional assembly processing technology utilizes the selective adsorption of a solution on a substrate with surface energy difference to realize the processing and manufacturing of a micro-nano structure, and the technology mainly comprises the following steps: (1) Processing hydrophilic patterns on the surface of a hydrophobic substrate or processing hydrophobic patterns on the surface of the hydrophilic substrate to form a hydrophobic region and a hydrophilic region, wherein the surfaces of the hydrophilic patterns and the hydrophilic substrate are mainly provided with polar functional groups, the surface energy is high and used as the hydrophilic region, the surfaces of the hydrophobic substrate and the hydrophobic patterns are mainly provided with nonpolar groups, and the surface energy is low and used as the hydrophobic region; (2) Applying a solution to the substrate, the solution being selectively adsorbed to effect directional assembly, in particular, the solution being adsorbed to the hydrophilic region and not to the hydrophobic region; (3) Drying the solution adsorbed to the hydrophilic area to form a micro-nano pattern structure on the surface of the substrate.

At present, the following technical problems to be solved are mainly existed in the manufacture of semiconductor components such as thin film transistors by using surface energy directional assembly processing technology:

(1) How does the process resolution increase? The resolution of the current surface energy directional assembly processing technique is on the order of hundred microns and is not matched with the current thin film transistors used for flat panel display. The low processing resolution not only reduces the screen resolution, but also causes a reduction in the screen aperture ratio and deterioration in brightness. As the hydrophilic region decreases in size below hundred microns, its adhesion to the nanoparticle solution may change significantly, making directional assembly more difficult to achieve.

(2) How to achieve high shape accuracy? Hundreds of millions of thin film transistors are needed for driving an 8K high-definition display screen to work, and high graphic shape precision is the basis for guaranteeing the uniformity of screen display.

(3) How does high thickness uniformity be achieved? The thin film transistor comprises a semiconductor active layer, a source electrode, a drain electrode, a gate insulating layer and a gate electrode four-layer structure, and the high thickness uniformity can obviously reduce the interlayer leakage probability and prolong the service life of a screen.

Furthermore, there is currently no systematic study of precursor solutions for surface energy directed assembly processing techniques. In order to solve the problems of resolution, processing precision and thickness uniformity described above, it is necessary to develop and study a specific and systematic precursor solution for surface energy directional assembly processing technology. In addition, a semiconductor device such as a thin film transistor includes a four-layer structure of a semiconductor layer, a source and drain electrode, a gate insulating layer, and a gate electrode, and it is necessary to provide a general precursor solution and a general and simple method for preparing the precursor solution, which are suitable for preparing the semiconductor layer, the conductor layer, and the insulating layer.

According to an embodiment of the present disclosure, there is provided a precursor solution for a surface energy directional assembly processing technique, comprising: alcohols or alcohol ethers organic solvents, precursor salts of metal oxides, and stabilizers. The precursor solution and the surface energy directional assembly processing technology are matched to prepare patterns with micro-nano magnitude (for example, 500 nm), precise shape and uniform thickness; the precursor solution according to the embodiment of the disclosure can form conductive patterns, semiconductor patterns and insulating patterns by selecting and matching different precursor salts, and has wide applicability; and see the description below regarding the formulation of the precursor solution, the formulation method of the precursor solution according to the embodiments of the present disclosure is simple and quick. In addition, compared with the existing vacuum film deposition technology, the embodiment of the disclosure has the advantages that no vacuum environment is needed for solution preparation or pattern preparation, and the cost is low; compared with the existing ink-jet printing technology, the embodiment of the disclosure is beneficial to realizing high-resolution and high-precision graphics; compared with the existing sol-gel method, the embodiment of the disclosure can rapidly prepare the patterned micro-nano electronic component on a large scale.

For example, according to embodiments of the present disclosure, the organic solvent is a high boiling point solvent having a boiling point in the range of: t is more than or equal to 230 ℃ and less than or equal to 300 ℃. In the case where the organic solvent is a high boiling point solvent, the precursor solution according to the embodiments of the present disclosure is used to prepare a pattern with little environmental requirements, and a pattern with high resolution and shape accuracy can be obtained in an environment of any relative humidity. In addition, in the case where the organic solvent is a high boiling point solvent, the pattern is prepared in an environment where the relative humidity is high (i.e., the relative humidity is 40% rh or more), the resolution and shape accuracy of the pattern can be further improved, and the coffee ring effect of the pattern can be greatly reduced or even eliminated, effectively improving the thickness uniformity of the pattern. For example, using the filling rate as a measure of shape accuracy, the ideal filling rate for producing a pattern is 100%. Fig. 1 is a schematic diagram of the relationship between relative humidity and pattern filling rate when preparing a pattern in the case where a precursor solution according to an embodiment of the present disclosure employs a high boiling point organic solvent. Referring to fig. 1, in the case of using a high boiling point solvent and not adding a surfactant as described below to a precursor solution, the filling rate of the pattern prepared in an environment of any relative humidity can reach 60% or more, indicating that the pattern accuracy is high; the filling rate of the pattern prepared under the environment with high relative humidity (namely, the relative humidity is 40% RH or more) can reach 80% or more, which indicates that the pattern precision is further improved. In addition, in the case where the organic solvent is a high boiling point solvent, the pattern is prepared in an environment with high relative humidity (i.e., a relative humidity of 40% rh or more), the coffee ring effect of the pattern can be greatly reduced or even eliminated, and the thickness uniformity of the pattern is good. For example, preparing a pattern in an environment with a high relative humidity (i.e., a relative humidity above 40% RH) includes: the precursor solution is applied to the substrate in an environment of high relative humidity (i.e., a relative humidity of 40% rh or more) and/or the precursor solution that has been applied to the substrate is dried in an environment of high relative humidity (i.e., a relative humidity of 40% rh or more).

For example, according to embodiments of the present disclosure, the high boiling point solvent is selected from one or more of diethylene glycol, ethylene glycol phenyl ether, propylene glycol phenyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, dipropylene glycol butyl ether, triethylene glycol methyl ether, triethylene glycol diethyl ether, triethylene glycol butyl ether, tripropylene glycol methyl ether, and tripropylene glycol butyl ether. For example, according to embodiments of the present disclosure, the high boiling point solvent is selected from one or more of diethylene glycol, ethylene glycol phenyl ether, propylene glycol phenyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol butyl ether.

For example, according to embodiments of the present disclosure, the organic solvent is a low boiling point solvent having a boiling point in the range of: t is less than or equal to 50 ℃ and less than 230 ℃. Fig. 2 is a schematic diagram of the relationship between relative humidity and pattern filling rate when preparing a pattern in the case where a precursor solution according to an embodiment of the present disclosure employs a low boiling point organic solvent. Referring to fig. 2, in the case where the organic solvent is a low boiling point solvent, a pattern with high resolution and shape accuracy can be obtained by preparing a pattern in an environment with low relative humidity (i.e., a relative humidity of 30% rh or less) using the precursor solution according to the embodiment of the present disclosure. For example, preparing a pattern in an environment with low relative humidity (i.e., a relative humidity of 30% rh or less) includes: the precursor solution is applied to the substrate in an environment of low relative humidity (i.e., a relative humidity of 30% rh or less) and/or the precursor solution that has been applied to the substrate is dried in an environment of low relative humidity (i.e., a relative humidity of 30% rh or less).

For example, according to embodiments of the present disclosure, the low boiling point solvent is selected from one or more of ethanol, ethylene glycol, isopropanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol isopropyl ether, ethylene glycol butyl ether, ethylene glycol tertiary butyl ether, ethylene glycol hexyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-propyl ether, propylene glycol isopropyl ether, propylene glycol n-butyl ether, propylene glycol tertiary butyl ether, diethylene glycol methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol dibutyl ether, diethylene glycol hexyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether. For example, the low boiling point solvent is selected from one or more of ethanol, ethylene glycol, isopropanol.

For example, according to embodiments of the present disclosure, the precursor salt is selected from one or more of an acetate salt of a metal, a nitrate salt of a metal, and a chloride salt of a metal, and the metal is selected from one or more of zinc, gallium, indium, tin, hafnium, and aluminum. According to embodiments of the present disclosure, patterns of different conductivities may be prepared by selecting different precursor salts or by selecting different combinations of precursor salts. For example, the precursor salt is selected from one or more of zinc acetate, zinc nitrate, zinc chloride, indium acetate, indium nitrate, indium chloride, gallium acetate, gallium nitrate, gallium chloride, tin acetate, tin nitrate, tin tetrachloride, and stannous chloride, in which case zinc oxide, indium oxide, gallium oxide, tin oxide, indium zinc oxide, zinc tin oxide, indium gallium oxide, zinc tin oxide, indium zinc tin oxide, indium gallium zinc oxide, and indium gallium zinc oxide may be formed using the precursor solution according to embodiments of the present disclosure for forming a semiconductor layer, for example, the semiconductor layer may be used as an active layer of a thin film transistor. For example, the precursor salt is selected from one or more of indium acetate, indium nitrate, indium chloride, tin acetate, tin nitrate, tin tetrachloride, and stannous chloride, in which case indium tin oxide may be formed using the precursor solution according to embodiments of the present disclosure for forming a conductive layer, for example, the conductive layer is used as a source-drain electrode or a gate electrode of a thin film transistor. For example, the precursor salt is selected from one or more of hafnium tetrachloride, hafnium oxychloride, hafnium ethoxide, hafnium isopropoxide, hafnium n-butoxide, aluminum acetate, aluminum nitrate, in which case aluminum oxide, hafnium oxide may be formed using the precursor solution according to embodiments of the present disclosure for forming an insulating layer, for example, the insulating layer is used as a gate insulating layer of a thin film transistor.

For example, in accordance with embodiments of the present disclosure, the function of the stabilizer is to help better dissolve the precursor salt in the organic solvent to obtain a clear precursor solution. The clarification of the precursor solution indicates that the precursor salt is well dissolved in the organic solvent, thereby providing guarantee for preparing the patterns with high resolution, precise shape and uniform thickness. According to the embodiment of the disclosure, other chemical reagents are not needed to be added to assist the dissolution of the precursor salt besides the stabilizer, so that the preparation of the precursor solution is simple and easy to realize. For example, stabilizers include carboxylic acids and/or organic amines. Still further, for example, the stabilizer is selected from one or more of acetic acid, citric acid, ethanolamine, diethanolamine, triethanolamine, and acetylacetone. For example, a precursor solution having a transmittance of 80% or greater and no tyndall effect is present indicates that the precursor solution is a clear solution.

For example, according to embodiments of the present disclosure, the mass concentration ratio of the precursor salt of the metal oxide to the substance of the stabilizer is: 1:1-1:3. If the ratio is greater than 3, the precursor solution may instead not be clarified. Referring to the description below regarding the formulation of precursor solutions according to embodiments of the present disclosure, precursor salts of metal oxides are first added to an organic solvent and stirred to obtain a mixed solution; adding a stabilizer into the mixed solution and stirring to help the precursor salt to be better dissolved; the addition of the stabilizer and stirring may be repeated a number of times until the mixed solution is clear. It should be noted that, although the stabilizer may be added repeatedly, the total amount of the added stabilizer needs to be ensured: the mass concentration ratio of the precursor salt of the metal oxide to the substance of the stabilizer is as follows: 1:1-1:3. For example, the ratio of the mass concentration of the precursor salt of the metal oxide to the mass concentration of the stabilizer is: in the case of 1:1-1:3, the weight ratio of the precursor salt of the metal oxide to the stabilizer is: 1:1 to 5:1.

For example, according to embodiments of the present disclosure, the precursor solution further includes a surfactant that adjusts the surface tension of the precursor solution. The surfactant may reduce interfacial tension between two liquids, between a gas and a liquid, or between a solid and a liquid; the addition of the surfactant, whether the organic solvent is a high boiling point solvent or a low boiling point solvent, is advantageous in improving the shape accuracy of the pattern and the resolution of the pattern, and can reduce the environmental requirements when preparing the pattern. Fig. 3 is a schematic diagram of the relationship between relative humidity and pattern filling rate when preparing a pattern in the case where a precursor solution according to an embodiment of the present disclosure employs a high boiling point organic solvent and includes a surfactant. Referring to fig. 3, the addition of the surfactant to the precursor solution using the high boiling point solvent can achieve 80% or more of the filling rate of the pattern prepared in an environment of any relative humidity, which means that the pattern has very high accuracy, and that the addition of the surfactant reduces the environmental requirements in preparing the pattern. For example, by adding a surfactant to a precursor solution using a high boiling point solvent and preparing a pattern in an environment having a high relative humidity (i.e., a relative humidity of 40% rh or more), the resolution and shape accuracy of the pattern can be further improved, and the coffee ring effect of the pattern can be greatly reduced or even eliminated, effectively improving the thickness uniformity of the pattern.

For example, according to the embodiment of the disclosure, after the surfactant is added, the surface tension of the precursor solution ranges from 15mN/m to 72mN/m, and the viscosity ranges from 0.8cp to 49cp, so that further assurance is provided for preparing patterns with high resolution, precise shape and uniform thickness. For example, the solvent is a high boiling point solvent, in which case the precursor solution has a surface tension ranging from 29mN/m to 50mN/m and a viscosity ranging from 4cp to 49cp, which is advantageous for preparing a pattern having high resolution, precise shape, and uniform thickness. For example, the solvent is a low boiling point solvent, in which case the precursor solution has a surface tension ranging from 15mN/m to 72mN/m and a viscosity ranging from 0.8cp to 20cp, which is advantageous for preparing a pattern having high resolution, precise shape, and uniform thickness.

For example, according to embodiments of the present disclosure, the surfactant is selected from one or more of triton X-100, alkylphenol ethoxylates, fatty alcohol ethoxylates.

For example, according to embodiments of the present disclosure, the precursor solution further includes a fuel. As described below, the precursor solution according to embodiments of the present disclosure is used to prepare a pattern including an annealing step, the fuel may undergo a partial oxidation-reduction exothermic reaction during the annealing process, the generated energy may be effective to promote impurity decomposition and metal oxide lattice formation, and the combustion reaction, once initiated, may reduce the requirement for external heat energy supply, even without external heat supply. In addition, the fuel may undergo a partial oxidation-reduction exothermic reaction during the annealing process, which is advantageous for reducing the annealing temperature and realizing low-temperature annealing, so that patterns may be prepared on more types of substrates using the precursor solution according to the embodiments of the present disclosure.

For example, according to embodiments of the present disclosure, the fuel is selected from one or more of ethylene glycol, urea, acetylacetone, and tetramethyltriazine.

For example, according to embodiments of the present disclosure, the organic solvent is 60% to 99.5% by weight, the precursor salt of the metal oxide is 0.3% to 20% by weight, the stabilizer is 0.1% to 10% by weight, the surfactant is 0.1% to 15% by weight, and the fuel is 0 to 20% by weight, based on the total weight of the precursor solution. Further, for example, the weight ratio of precursor salt of metal oxide to stabilizer is: 1:1 to 5:1; by adding the stabilizer and controlling the amount of the stabilizer in a suitable range, a clear precursor solution is advantageously obtained.

For example, according to embodiments of the present disclosure, the precursor solution is composed of an organic solvent, a precursor salt of a metal oxide, a stabilizer, a surfactant, and a fuel. That is, the precursor solution according to the embodiment of the present disclosure includes only the above 5 components, except that the above 5 components do not include other components, so the precursor solution according to the embodiment of the present disclosure has a simple component, which is advantageous in simplifying the preparation process of the precursor solution.

For example, according to embodiments of the present disclosure, the precursor solution does not include a viscosity modifier. That is, according to the embodiments of the present disclosure, the viscosity of the precursor solution is not adjusted by specifically adding the viscosity modifier, so that the precursor solution according to the embodiments of the present disclosure has simple components, which is advantageous in simplifying the preparation process of the precursor solution.

According to an embodiment of the present disclosure, there is also provided a method of preparing the precursor solution as described above. Fig. 4 is a flow diagram of a method of preparing a precursor solution according to an embodiment of the present disclosure. Referring to fig. 4, the method includes: step S1: adding a precursor salt of the metal oxide into an organic solvent and stirring to obtain a mixed solution; step S2: adding a stabilizer into the mixed solution and stirring; if the mixed solution is not clear, repeating the adding of the stabilizer and stirring until the mixed solution is clear. It can be seen that the precursor solution according to the embodiments of the present disclosure is simple to prepare, does not require a vacuum environment, and can obtain a clear solution without the addition of other chemical agents other than stabilizers to aid dissolution. In the preparation method of the precursor solution according to the embodiment of the disclosure, the precursor salt of the metal oxide and the stabilizer are separately added into the organic solvent, that is, the precursor salt of the metal oxide is added into the organic solvent first, then the stabilizer is added, and the amount of the stabilizer is adjusted according to the actual condition of whether the solution is clear or not, so that the flexibility of solution preparation is improved. It should be noted that, as described above, although the addition of the stabilizer may be repeated plural times, the total amount of the stabilizer to be added needs to be ensured: the mass concentration ratio of the precursor salt of the metal oxide to the substance of the stabilizer is as follows: 1:1-1:3. For example, according to an embodiment of the present disclosure, the method of preparing a precursor solution further includes: adding a surfactant and/or fuel to the clarified mixed solution. For example, in the case of adding both the surfactant and the fuel to the clarified mixed solution, the surfactant may be added first and then the fuel may be added, or both the surfactant and the fuel may be added simultaneously. For example, in performing step S1 and step S2, heating may also be performed simultaneously to promote dissolution of the precursor salt of the metal oxide.

For example, the precursor solution according to an embodiment of the present disclosure includes precursor salts of first to n-th metal oxides, n being 2 or more in total. In this case, the method of preparing a precursor solution according to an embodiment of the present disclosure includes:

sequentially performing step S1 and step S2 to obtain a clarified first mixed solution comprising a precursor salt of the first metal oxide;

adding a precursor salt of the second metal oxide to the clarified first mixed solution and stirring to obtain a second mixed solution comprising the precursor salt of the first metal oxide and the precursor salt of the second metal oxide; adding the stabilizer and stirring if the second mixed solution is not clear, and repeatedly executing the addition of the stabilizer and stirring if the second mixed solution is still not clear until the second mixed solution is clear;

and so on until the precursor salt of the nth metal oxide is added to the clarified nth-1 mixed solution and stirred to obtain an nth mixed solution including the precursor salts of the first to nth metal oxides; adding the stabilizer and stirring if the nth mixed solution is not clear, and repeatedly executing the adding of the stabilizer and stirring if the nth mixed solution is still not clear until the nth mixed solution is clear. It can be seen that the precursor solution according to the embodiments of the present disclosure is simple to prepare, does not require a vacuum environment, and can obtain a clear solution without the addition of other chemical agents other than stabilizers to aid dissolution. It should be noted that, as described above, although the addition of the stabilizer may be repeated plural times, the total amount of the stabilizer to be added needs to be ensured: the mass concentration ratio of the precursor salt of the n metal oxides to the substances of the stabilizing agent is as follows: 1:1-1:3. For example, according to an embodiment of the present disclosure, the method of preparing a precursor solution further includes: adding a surfactant and/or a fuel to the clarified nth mixed solution. For example, in the case of adding both the surfactant and the fuel to the clarified nth mixed solution, the surfactant may be added first and then the fuel may be added, or the surfactant and the fuel may be added simultaneously. For example, heating may also be performed simultaneously during the above preparation to promote dissolution of the precursor salt of the metal oxide.

For example, according to an embodiment of the present disclosure, the precursor salts of the above-described first to n-th metal oxides are salts of n different metals, respectively; in the process of preparing the precursor salt, the precursor salt of the first metal oxide is dissolved first, then the precursor salt of the second metal oxide is dissolved, and the like, and finally the precursor salt of the n-th metal oxide is dissolved, so that clear precursor solution is obtained, and the preparation of patterns with high resolution, precise shape and uniform thickness is facilitated. If the precursor salts of the first to n-th metal oxides are added together to the solvent, the resulting solution is difficult to clarify, which is disadvantageous for preparing patterns with high resolution, precise shape, and uniform thickness. For example, according to an embodiment of the present disclosure, the n different metals described above include indium; and the precursor salt of the first metal oxide is a salt of indium. Indium salts are relatively insoluble; according to the embodiment of the disclosure, the precursor salt of the first metal oxide is indium salt, that is, in the process of preparing the precursor solution, the indium salt is dissolved first, and then the salts of other metals are dissolved, so that the dissolution sequence is favorable for fully dissolving the indium salt, thereby being favorable for preparing a clear precursor solution, and providing guarantee for preparing patterns with high resolution, precise shape and uniform thickness.

According to an embodiment of the present disclosure, there is also provided a pattern preparation method using a surface energy directional assembly processing technique. The pattern preparation method comprises the following steps: providing a substrate; treating the substrate such that the substrate has hydrophilic regions; applying a precursor solution according to embodiments of the present disclosure as described above to a substrate, the precursor solution selectively adsorbing to a hydrophilic region; drying the precursor solution to obtain a dried product; the dried product is annealed in an oxygen-containing environment to obtain a pattern of metal oxides. It can be seen that the graphics preparation method according to the embodiments of the present disclosure is simple, fast, and does not require a vacuum environment.

For example, according to embodiments of the present disclosure, the substrate is a rigid substrate, such as a silicon substrate, a silicon oxide substrate, a sapphire substrate, a glass substrate, a quartz substrate, and the like. For example, the substrate is a flexible substrate, such as, for example, a polyimide substrate, a PET substrate, and the like.

For example, according to an embodiment of the present disclosure, processing a substrate includes: performing hydrophilic treatment on the whole substrate to obtain a hydrophilic region; or the whole substrate is subjected to hydrophobic treatment, and the mask plate is matched to carry out hydrophilic treatment on the local area of the substrate so as to obtain a hydrophilic area; or carrying out hydrophilic treatment on the whole substrate, and carrying out hydrophobic treatment on a local area of the substrate by matching with a mask plate so as to obtain a hydrophilic area. In the first case described above, where the entire substrate is hydrophilic, the pattern of metal oxide will cover the entire substrate. In the second and third cases described above, the substrate includes both hydrophilic and hydrophobic regions, and the precursor solution is selectively adsorbed to the hydrophilic regions, so that the pattern of the metal oxide is formed in the hydrophilic regions and substantially conforms to the shape of the hydrophilic regions, and the closer the pattern of the metal oxide is to the shape of the hydrophilic regions, the higher the filling ratio of the pattern and the better the shape accuracy. For example, in the second case described above, the mask plate includes openings, the regions of the substrate exposed by the openings form hydrophilic regions, and the regions of the substrate not leaked out of the openings form hydrophobic regions. For example, in the third case, the mask plate includes an opening, the region of the substrate exposed by the opening forms a hydrophobic region, and the region of the substrate not leaked by the opening forms a hydrophilic region. In the second and third cases, the photoresist may be further used, the photoresist is patterned by using a mask plate, the patterned photoresist is used as a mask to perform a local process on the substrate, and then the photoresist is removed.

For example, according to an embodiment of the present disclosure, the above-described hydrophilic treatment includes: one or more of oxygen plasma treatment, piranha solution soaking, laser irradiation, and UV-O3 treatment. For example, the laser irradiation is excimer laser irradiation, and the wavelength of the laser may be 172nm or 222nm or 254nm. For example, piranha solution is prepared by using concentrated sulfuric acid with the concentration of 98% and hydrogen peroxide with the concentration of 30%, and the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide is 2:1.

For example, according to an embodiment of the present disclosure, the above-described hydrophobic treatment includes: a SAM layer (Self Assembled Monolayer, self-assembled monolayer) is formed, and the organic solution used to form the SAM layer comprises one or more of trimethoxysilanes, triethoxysilanes, trichlorosilane, and phosphonic acids. For example, the number of the cells to be processed, trimethoxysilanes include trimethoxy (1H, 2H-nonafluorohexyl) silane trimethoxy (1H, 2H-tridecafluoron-octyl) silane, trimethoxy (1H, 2H-heptadecafluorodecyl) silane one or more of octadecyltrimethoxysilane, hexadecyltrimethoxysilane, dodecyltrimethoxysilane and octyltrimethoxysilane. For example, the number of the cells to be processed, triethoxysilanes include triethoxy (1H, 2H-nonafluorohexyl) silane triethoxy-1H, 2H-tridecyl fluoro-n-octyl silane, 1H, 2H-perfluoro decyl triethoxy silane one or more of octadecyltriethoxysilane, hexadecyltriethoxysilane, dodecyl triethoxysilane, hexyl triethoxysilane, and butyl triethoxysilane. For example, the trichlorosilane includes one or more of trichloro (1 h,2 h-tridecyl-fluoro-n-octyl) silane, trichloro-octadecyl silane, trichloro (hexadecyl) silane, tetradecyl-trichloro-silane, dodecyl-trichloro-silane, and decyl-trichloro-silane. For example, the phosphonic acids include one or more of (1 h,2 h-heptadecafluorodecyl) phosphonic acid and n-hexadecylphosphoric acid. By the above solution, a SAM layer excellent in performance can be obtained to be used as a hydrophobic region.

For example, according to embodiments of the present disclosure, the precursor solution is applied to the substrate by a pulling method, a slot coating method, a knife coating method, or a spin coating method.

For example, according to embodiments of the present disclosure, the organic solvent is a high boiling point solvent, the boiling point ranges from: t is more than or equal to 230 ℃ and less than or equal to 300 ℃; the precursor solution includes a surfactant; the pattern preparation method comprises the following steps: the precursor solution is applied to the substrate and dried in an environment of arbitrary relative humidity. Referring to fig. 3, in the case where the precursor solution includes a surfactant, the requirement for the environmental conditions is small when the precursor solution including a high boiling point solvent is used to prepare the pattern, and the filling rate of the prepared pattern can reach 80% or more in an environment of any relative humidity, indicating that the pattern accuracy is very high.

For example, according to embodiments of the present disclosure, the organic solvent is a high boiling point solvent, the boiling point range being: t is more than or equal to 230 ℃ and less than or equal to 300 ℃; the pattern preparation method comprises the following steps: the precursor solution is applied to the substrate in an environment having a relative humidity above 40% rh and/or the precursor solution is dried in an environment having a relative humidity above 40% rh. In this case, the shape accuracy of the prepared pattern is high (as shown in fig. 1), and the coffee ring effect of the pattern is greatly reduced or even eliminated, and the thickness uniformity of the pattern is good. In the above case, the precursor solution may or may not include a surfactant; the precursor solution includes a surfactant, and thus the shape accuracy and resolution of the pattern may be further improved. For example, it is preferable to apply the precursor solution to the substrate in an environment having a relative humidity of 40% RH or more and dry the precursor solution in an environment having a relative humidity of 40% RH or more. For example, the step of applying the precursor solution and the step of drying the precursor solution may be performed in a humidity-adjustable chamber in order to obtain a relative humidity above 40% RH. For example, the humidity of the chamber may be increased by blowing a moisture-bearing gas into the chamber, and the humidity of the chamber may be decreased by blowing a drying gas into the chamber.

For example, according to embodiments of the present disclosure, the organic solvent is a low boiling point solvent, the boiling point range being: t is more than or equal to 50 ℃ and less than 230 ℃; the pattern preparation method comprises the following steps: the precursor solution is applied to the substrate in an environment having a relative humidity of 30% rh or less and/or the precursor solution is dried in an environment having a relative humidity of 30% rh or less. In this case, as shown in fig. 2, the shape accuracy of the prepared pattern is high. In the above case, the precursor solution may or may not include a surfactant; the precursor solution includes a surfactant, and thus the shape accuracy and resolution of the pattern may be further improved. For example, it is preferable to apply the precursor solution to the substrate in an environment having a relative humidity of 30% RH or less and dry the precursor solution in an environment having a relative humidity of 30% RH or less. For example, the step of applying the precursor solution and the step of drying the precursor solution may be performed in a humidity-adjustable chamber in order to obtain a relative humidity below 30% rh. For example, the humidity of the chamber may be increased by blowing a moisture-bearing gas into the chamber, and the humidity of the chamber may be decreased by blowing a drying gas into the chamber.

For example, drying the precursor solution may remove at least a portion of the organic solvent and the stabilizer, according to embodiments of the present disclosure.

For example, according to an embodiment of the present disclosure, annealing the dried product includes: the first annealing process and the second annealing process are sequentially performed, wherein the temperature of the first annealing process is lower than the temperature of the second annealing process, and the duration of the first annealing process is shorter than the duration of the second annealing process. By the above two-stage annealing, the precursor salt of the metal oxide can be sufficiently converted into the metal oxide. Further, for example, the temperature of the first annealing process is 25 ℃ to 200 ℃, and the duration of the first annealing process is 30 minutes or less; and the temperature of the second annealing process is 50-1000 ℃, and the duration of the second annealing process is less than or equal to 2 hours. It can be seen that by the addition of fuel, low temperature annealing is achieved.

For example, in accordance with embodiments of the present disclosure, the organic solvent and stabilizer are substantially removed during the drying and annealing process.

For example, according to embodiments of the present disclosure, the pattern of the metal oxide prepared is a semiconductor pattern, in which case the precursor salt of the metal oxide is selected from one or more of zinc acetate, zinc nitrate, zinc chloride, indium acetate, indium nitrate, indium chloride, gallium acetate, gallium nitrate, gallium chloride, tin acetate, tin nitrate, tin tetrachloride, and stannous chloride.

For example, according to embodiments of the present disclosure, the pattern of the metal oxide is a conductive pattern, in which case the precursor salt of the metal oxide is selected from one or more of indium acetate, indium nitrate, indium chloride, tin acetate, tin nitrate, tin tetrachloride, and stannous chloride.

For example, according to an embodiment of the present disclosure, the pattern of the metal oxide is prepared as an insulating pattern, in which case the precursor salt of the metal oxide is selected from one or more of hafnium tetrachloride, hafnium oxychloride, hafnium ethoxide, hafnium isopropoxide, hafnium n-butoxide, aluminum acetate and aluminum nitrate.

For example, according to embodiments of the present disclosure, the size of the pattern of the metal oxide prepared is 500nm or more. The patterns of the metal oxide prepared according to the embodiment of the disclosure can be as small as 500nm, which indicates that the resolution of the prepared patterns is high.

For example, according to an embodiment of the present disclosure, there is also provided a method of manufacturing an electronic device including a semiconductor layer, a conductor layer, and an insulating layer using a surface energy directional assembly process technique, wherein the method of manufacturing an electronic device includes manufacturing at least one of the semiconductor layer, the conductor layer, and the insulating layer of the electronic device using the pattern manufacturing method described above. For example, the electronic device is a thin film transistor, the semiconductor layer is an active layer of the thin film transistor, the conductor layer is a gate electrode and a source-drain electrode of the thin film transistor, and the insulating layer is a gate insulating layer of the thin film transistor. For example, the semiconductor layer, the conductor layer and the insulating layer of the electronic device are respectively prepared by the pattern preparation method. According to the embodiment of the disclosure, the electronic component with large area, high precision and high resolution can be quickly prepared, and the electronic component can be prepared by a full solution method.

For example, in accordance with an embodiment of the present disclosure, a method of fabricating an electronic device using a surface energy directed assembly processing technique, comprising: preparing a preceding layer of the semiconductor, conductor and insulator layers of the electronic device, followed by preparing a following layer of the semiconductor, conductor and insulator layers of the electronic device; in the process of preparing a later layer in the semiconductor layer, the conductor layer and the insulating layer of the electronic device, carrying out hydrophobic treatment on a local area of the substrate by matching with a mask plate so as to obtain a hydrophilic area for adsorbing the later layer, wherein the hydrophobic treatment comprises forming a SAM layer, and an organic solution for forming the SAM layer comprises one or more of trimethoxy silane and triethoxy silane. In the process of preparing the semiconductor layer, the conductor layer and the insulating layer of the electronic device, the SAM layer is formed by adopting trimethoxy silane and/or triethoxy silane to obtain a hydrophobic region, so that the influence on the previous layer of the electronic device, which is formed in the preparation process, is minimal, and the shape change and even falling of the previous layer, which is formed, can be avoided.

For example, the number of the cells to be processed, trimethoxysilanes include trimethoxy (1H, 2H-nonafluorohexyl) silane trimethoxy (1H, 2H-tridecafluoron-octyl) silane, trimethoxy (1H, 2H-heptadecafluorodecyl) silane one or more of octadecyltrimethoxysilane, hexadecyltrimethoxysilane, dodecyltrimethoxysilane and octyltrimethoxysilane. For example, the number of the cells to be processed, triethoxysilanes include triethoxy (1H, 2H-nonafluorohexyl) silane triethoxy-1H, 2H-tridecyl fluoro-n-octyl silane, 1H, 2H-perfluoro decyl triethoxy silane one or more of octadecyltriethoxysilane, hexadecyltriethoxysilane, dodecyl triethoxysilane, hexyl triethoxysilane, and butyl triethoxysilane.

Example 1: preparation of metal oxide thin film transistor

In example 1, a precursor solution according to an embodiment of the present disclosure was used to prepare a semiconductor active layer of a metal oxide thin film transistor. Fig. 5 is a schematic diagram of a structure of a metal oxide thin film transistor.

(1) Preparing a precursor solution:

sequentially dissolving 1.752g of indium acetate hydrate and 0.61g of ethanolamine in 19.24g of propylene glycol methyl ether, and fully stirring for several hours under the heating condition of 40 ℃ to obtain a clear and transparent solution; then 0.256g of gallium nitrate hydrate and 0.61g of ethanolamine are dissolved in the solution in turn, and the mixture is fully stirred for a plurality of hours under the heating condition of 40 ℃ to obtain clear and transparent solution; finally, 0.659g of zinc acetate dihydrate and 0.61g of ethanolamine are sequentially dissolved in the solution, and the solution is fully stirred for a plurality of hours under the condition of heating at 40 ℃ until the solution is clear and transparent, so that a precursor solution for use is obtained. The precursor salt of the metal oxide in the precursor solution accounts for 11.23 percent of the total weight, the organic solvent accounts for 81.05 percent of the total weight, and the stabilizer accounts for 7.72 percent of the total weight.

(2) Preparation of a metal oxide thin film transistor:

1) Referring to fig. 5, a silicon oxide layer is formed as a gate insulating layer 02 on a silicon substrate 01, the silicon substrate 01 is used as a gate electrode, and the gate insulating layer 02 is treated so as to have a hydrophilic region;

2) Referring to fig. 5, using the pulling method, a precursor solution is applied to the gate insulating layer 02 at 25 ℃ under an ambient condition of a relative humidity of 10% rh, dried for 30min, subjected to a first annealing process at 150 ℃ for 5min, and subjected to a second annealing process at 400 ℃ for 1h, to obtain a pattern 04 of a metal oxide. The pattern 04 of metal oxide serves as a semiconductor active layer of the thin film transistor. During the drying and annealing process, the organic solvent and the stabilizer are sufficiently removed.

3) Referring to fig. 5, an Al layer of 50nm is evaporated on the active layer 04 as the source and drain electrodes 03.

Fig. 6 is an Id-Vg plot of the metal oxide thin film transistor shown in fig. 5. The graph illustrates that the performance of the thin film transistor meets the standard, and the semiconductor characteristics of the semiconductor active layer 04 prepared using the precursor solution according to the embodiment of the present disclosure meet the standard.

Example 2: preparation of capacitor

In example 2, a precursor solution according to an embodiment of the present disclosure was used to prepare an insulating dielectric layer of a capacitor. Fig. 7 is a schematic structural diagram of a capacitor.

(1) Preparing a precursor solution:

hafnium oxide octahydrate 0.41g and ethanolamine 0.061g are dissolved in 19.32g of ethylene glycol methyl ether in turn and fully stirred for a plurality of hours under the heating condition of 40 ℃ until the mixture is clear, so that a precursor solution for use is obtained. The precursor salt of the metal oxide in the precursor solution accounts for 2.07 percent of the total weight, the organic solvent accounts for 97.62 percent of the total weight, and the stabilizer accounts for 0.31 percent of the total weight.

(2) Preparation of a capacitor:

1) Referring to fig. 7, the silicon layer 11 is treated to make the whole hydrophilic area, and the silicon layer is used as a first polar plate of the capacitor;

2) Referring to fig. 7, a precursor solution is spin-coated on a silicon layer 11, dried at 25 ℃ under an environmental condition of relative humidity 10% rh for 30min, subjected to a first annealing process at 150 ℃ for 5min, and subjected to a second annealing process at 400 ℃ for 1h, to obtain a metal oxide film 12. The metal oxide film 12 serves as an insulating dielectric layer of the capacitor. During the drying and annealing process, the organic solvent and the stabilizer are sufficiently removed.

3) Referring to fig. 7, an Al layer of 50nm is evaporated on the metal oxide film 12 as the second plate 13 of the capacitor.

FIG. 8 is a C-V plot of the capacitance shown in FIG. 7. The graph illustrates that the performance of the capacitor meets the insulation characteristics of the insulating dielectric layer 12 prepared using the precursor solution according to an embodiment of the present disclosure.

Example 3: preparation of metal oxide electrodes

In example 3, a metal oxide electrode was prepared using a precursor solution according to an embodiment of the present disclosure.

(1) Preparing a precursor solution:

sequentially dissolving 0.762g of indium acetate hydrate and 0.183g of ethanolamine in 19.32g of ethylene glycol methyl ether, and fully stirring for several hours under the heating condition of 40 ℃ to obtain a clear and transparent solution; then 0.137g of stannic chloride pentahydrate and 0.183g of ethanolamine are dissolved in the solution in turn, and the mixture is fully stirred for a plurality of hours under the condition of heating at 40 ℃ until the mixture is clear, thus obtaining a precursor solution for use. The precursor salt of the metal oxide in the precursor solution accounts for 4.37 percent of the total weight, the organic solvent accounts for 93.85 percent of the total weight, and the stabilizer accounts for 1.78 percent of the total weight.

(2) Preparation of a metal oxide electrode:

1) Treating the silicon oxide substrate to provide a hydrophilic region;

2) The precursor solution was applied to a silicon oxide substrate using a pulling method, dried at 25 ℃ under an environmental condition of relative humidity 10% rh for 30min, subjected to a first annealing process at 150 ℃ for 5min, and subjected to a second annealing process at 400 ℃ for 1h, to obtain a patterned metal oxide film. The patterned metal oxide film is used as a metal oxide electrode. During the drying and annealing process, the organic solvent and the stabilizer are sufficiently removed.

In the performance test of the metal oxide electrode prepared by the example, a four-probe method is adopted. For example, a photoresist layer is first spin-coated on a metal oxide electrode, the photoresist is patterned by a photolithography process, aluminum is evaporated, the portion uncovered by the photoresist leaves aluminum after stripping the photoresist, the aluminum evaporated by the photoresist covered portion is stripped along with the photoresist, thereby preparing four aluminum electrodes, and the resistivity of the metal oxide electrode can be measured by a four-probe method. Fig. 9 is a schematic diagram of a four-probe method for testing performance of a metal oxide electrode, wherein reference numeral 21 indicates a probe for applying a current signal in the four-probe method test, reference numeral 22 indicates a metal oxide electrode to be tested, reference numeral 23 indicates a probe for measuring a voltage signal in the four-probe method test, and reference numeral 24 indicates a substrate (e.g., a silicon oxide substrate).

Fig. 10 is an I-V plot of a metal oxide electrode. The graph illustrates that the conductivity of a metal oxide electrode prepared using a precursor solution according to an embodiment of the present disclosure meets the criteria.

Example 4: preparation of metal oxide thin film transistor

In example 4, an active layer, a gate electrode, a gate insulating layer, and a source and drain electrode of a metal oxide thin film transistor were respectively prepared using a precursor solution according to an embodiment of the present disclosure. Fig. 11 is a schematic diagram of a structure of a metal oxide thin film transistor.

(1) Preparing a precursor solution:

sequentially dissolving 1.752g of indium acetate hydrate and 0.61g of ethanolamine in 19.24g of propylene glycol methyl ether, and fully stirring for several hours under the heating condition of 40 ℃ to obtain a clear and transparent solution; then 0.256g of gallium nitrate hydrate and 0.61g of ethanolamine are dissolved in the solution in turn, and the mixture is fully stirred for a plurality of hours under the heating condition of 40 ℃ to obtain clear and transparent solution; finally, 0.659g of zinc acetate dihydrate and 0.61g of ethanolamine are sequentially dissolved in the solution, and the solution is fully stirred for a plurality of hours under the condition of heating at 40 ℃ until the solution is clear and transparent, so that a precursor solution A which can be used is obtained. The precursor salt of the metal oxide in the precursor solution A accounts for 11.23 percent of the total weight, the organic solvent accounts for 81.05 percent of the total weight, and the stabilizer accounts for 7.72 percent of the total weight.

Hafnium oxide octahydrate 0.41g and ethanolamine 0.061g are dissolved in 19.24g propylene glycol methyl ether in turn and fully stirred for a plurality of hours under the heating condition of 40 ℃ until the mixture is clear, so as to obtain a precursor solution B which can be used. The precursor salt of the metal oxide in the precursor solution B accounts for 2.08 percent of the total weight, the organic solvent accounts for 97.61 percent of the total weight, and the stabilizer accounts for 0.31 percent of the total weight.

Sequentially dissolving 0.762g of indium acetate hydrate and 0.183g of ethanolamine in 19.24g of propylene glycol methyl ether, and fully stirring for several hours under the heating condition of 40 ℃ to obtain a clear and transparent solution; then 0.137g of stannic chloride pentahydrate and 0.183g of ethanolamine are dissolved in the solution in turn, and the mixture is fully stirred for a plurality of hours under the condition of heating at 40 ℃ until the mixture is clarified, thus obtaining a precursor solution C which can be used. The precursor salt of the metal oxide in the precursor solution C accounts for 4.35 percent of the total weight, the organic solvent accounts for 93.88 percent of the total weight, and the stabilizer accounts for 1.77 percent of the total weight.

(2) Preparation of a metal oxide thin film transistor:

referring to fig. 11, the glass substrate 35 is treated so as to have a hydrophilic region;

referring to fig. 11, a precursor solution a is applied to a substrate using a pulling method, dried for 30min at an ambient condition of 25 ℃ and a relative humidity of 10% rh, subjected to a first annealing process for 5min at 150 ℃ and subjected to a second annealing process for 1h at 400 ℃ to obtain a patterned metal oxide thin film. The patterned metal oxide film serves as the active layer 34 of the metal oxide thin film transistor. In the drying and annealing processes, the organic solvent and the stabilizer in the precursor solution A are sufficiently removed;

Referring to fig. 11, a substrate 35 having an active layer 34 is treated to have a hydrophilic region;

referring to fig. 11, a precursor solution C is applied to a substrate 35 having an active layer 34, using a pulling method, dried for 30min at 25 ℃ under an ambient condition of a relative humidity of 10% rh, subjected to a first annealing process for 5min at 150 ℃, and subjected to a second annealing process for 1h at 400 ℃ to obtain a patterned metal oxide thin film. The patterned metal oxide film serves as the source and drain electrodes 33 of the metal oxide thin film transistor. During the drying and annealing processes, the organic solvent and the stabilizer in the precursor solution C are sufficiently removed;

referring to fig. 11, a substrate 35 having a source-drain electrode 33 and an active layer 34 is processed to have a hydrophilic region;

referring to fig. 11, a precursor solution B is applied to a substrate 35 having a source and drain electrode 33 and an active layer 34 using a pulling method, dried for 30min at 25 ℃ under an environmental condition of a relative humidity of 10% rh, subjected to a first annealing process for 5min at 150 ℃, and subjected to a second annealing process for 1h at 400 ℃ to obtain a patterned metal oxide thin film. The patterned metal oxide film serves as the gate insulating layer 32 of the metal oxide thin film transistor. In the drying and annealing processes, the organic solvent and the stabilizer in the precursor solution B are sufficiently removed;

Referring to fig. 11, a substrate 35 having a gate insulating layer 32, a source-drain electrode 33, and an active layer 34 is treated so as to have a hydrophilic region;

referring to fig. 11, a precursor solution C is applied to a substrate 35 having a gate insulating layer 32, a source drain electrode 33, and an active layer 34 using a pulling method, dried at 25 ℃ under an environmental condition of a relative humidity of 10% rh for 30min, subjected to a first annealing process at 150 ℃ for 5min, and subjected to a second annealing process at 400 ℃ for 1h, to obtain a patterned metal oxide thin film. The patterned metal oxide film serves as the gate electrode 31 of the metal oxide thin film transistor. During the drying and annealing process, the organic solvent and stabilizer in the precursor solution C are sufficiently removed.

Fig. 12 is an Id-Vg plot of the metal oxide thin film transistor shown in fig. 11. The graph illustrates that the performance of the thin film transistor meets the performance standard of the gate electrode 31, the gate insulating layer 32, the source drain electrode 33, and the active layer 34 of the metal oxide thin film transistor prepared using the precursor solution according to the embodiment of the present disclosure.

The foregoing is merely exemplary embodiments of the present disclosure and is not intended to limit the scope of the disclosure, which is defined by the appended claims.

Claims

1. A precursor solution for use in a surface energy directed assembly processing technique, comprising: alcohols or alcohol ethers organic solvents, precursor salts of metal oxides, and stabilizers.

2. The precursor solution of claim 1 wherein,

the organic solvent is a high boiling point solvent, and the boiling point range is as follows: t is more than or equal to 230 ℃ and less than or equal to 300 ℃.

3. The precursor solution of claim 2 wherein,

the high boiling point solvent is selected from one or more of diethylene glycol, ethylene glycol phenyl ether, propylene glycol phenyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, dipropylene glycol butyl ether, triethylene glycol methyl ether, triethylene glycol diethyl ether, triethylene glycol butyl ether, tripropylene glycol methyl ether and tripropylene glycol butyl ether.

4. The precursor solution of claim 1 wherein,

the organic solvent is a low boiling point solvent, and the boiling point range is as follows: t is less than or equal to 50 ℃ and less than 230 ℃.

5. The precursor solution of claim 4 wherein,

the low boiling point solvent is selected from one or more of ethanol, ethylene glycol, isopropanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol isopropyl ether, ethylene glycol butyl ether, ethylene glycol tertiary butyl ether, ethylene glycol hexyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-propyl ether, propylene glycol isopropyl ether, propylene glycol n-butyl ether, propylene glycol tertiary butyl ether, diethylene glycol methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol dibutyl ether, diethylene glycol hexyl ether, dipropylene glycol methyl ether and dipropylene glycol dimethyl ether.

6. The precursor solution of claim 1, wherein the precursor salt is selected from one or more of an acetate salt of a metal, a nitrate salt of a metal, and a chloride salt of a metal, and the metal is selected from one or more of zinc, gallium, indium, tin, hafnium, and aluminum.

7. The precursor solution of claim 1, wherein the stabilizer comprises carboxylic acids and/or organic amines.

8. The precursor solution of claim 7, wherein the stabilizer is selected from one or more of acetic acid, citric acid, ethanolamine, diethanolamine, triethanolamine, and acetylacetone.

9. The precursor solution of any one of claims 1-8, further comprising a surfactant that adjusts the surface tension of the precursor solution.

10. The precursor solution according to claim 9, wherein the precursor solution has a surface tension ranging from 15mN/m to 72mN/m and a viscosity ranging from 0.8cp to 49cp.

11. The precursor solution of claim 10 wherein,

the solvent is a high boiling point solvent, and the boiling point range is as follows: t is more than or equal to 230 ℃ and less than or equal to 300 ℃, the surface tension of the precursor solution ranges from 29mN/m to 50mN/m, and the viscosity ranges from 4cp to 49cp;

The solvent is a low boiling point solvent, and the boiling point range is as follows: the temperature T is more than or equal to 50 ℃ and less than 230 ℃, the surface tension of the precursor solution ranges from 15mN/m to 72mN/m, and the viscosity ranges from 0.8cp to 20cp.

12. The precursor solution of claim 9, wherein the surfactant is selected from one or more of triton X-100, alkylphenol ethoxylates, fatty alcohol ethoxylates.

13. The precursor solution of any one of claims 1-8, further comprising a fuel.

14. The precursor solution of claim 13, wherein the fuel is selected from one or more of ethylene glycol, urea, acetylacetone, and tetramethyltriazine.

15. The precursor solution of claim 13 wherein,

based on the total weight of the precursor solution, the weight percentage of the organic solvent is 60-99.5%, the weight percentage of the precursor salt of the metal oxide is 0.3-20%, the weight percentage of the stabilizer is 0.1-10%, the weight percentage of the surfactant is 0.1-15%, and the weight percentage of the fuel is 0-20%.

16. The precursor solution of claim 13, wherein the precursor solution consists of the organic solvent, a precursor salt of the metal oxide, the stabilizer, the surfactant, and the fuel.

17. The precursor solution according to any one of claims 1-8, wherein the mass concentration ratio of the precursor salt of the metal oxide to the substance of the stabilizer is: 1:1-1:3, wherein the weight ratio of the precursor salt of the metal oxide to the stabilizer is as follows: 1:1 to 5:1.

18. A method of preparing the precursor solution of any one of claims 1-17, comprising:

step S1: adding the precursor salt of the metal oxide into the organic solvent and stirring to obtain a mixed solution;

step S2: adding the stabilizer into the mixed solution and stirring; if the mixed solution is not clear, repeating the adding of the stabilizer and stirring until the mixed solution is clear.

19. The method of claim 18, further comprising:

adding a surfactant and/or a fuel to the clarified mixed solution.

20. The method of claim 18, wherein,

the precursor solution comprises precursor salts of first to n-th metal oxides, wherein n is more than or equal to 2; and is also provided with

The method comprises the following steps:

Adding a precursor salt of a second metal oxide to the clarified first mixed solution and stirring to obtain a second mixed solution comprising the precursor salt of the first metal oxide and the precursor salt of the second metal oxide; adding a stabilizer and stirring if the second mixed solution is not clear, and repeatedly executing the addition of the stabilizer and stirring if the second mixed solution is still not clear until the second mixed solution is clear;

and so on until the precursor salt of the nth metal oxide is added to the clarified nth-1 mixed solution and stirred to obtain an nth mixed solution including the precursor salts of the first to nth metal oxides; and adding the stabilizing agent and stirring if the nth mixed solution is not clear, and repeatedly executing the adding of the stabilizing agent and stirring if the nth mixed solution is still not clear until the nth mixed solution is clear.

21. The method of claim 20, wherein,

the precursor salts of the first to n-th metal oxides are salts of n different metals, respectively, the n different metals including indium; and is also provided with

The precursor salt of the first metal oxide is a salt of indium.

22. The method of claim 20, further comprising:

Adding a surfactant and/or a fuel to the clarified nth mixed solution.

23. A pattern preparation method adopts a surface energy directional assembly processing technology, which comprises the following steps:

providing a substrate;

treating the substrate such that the substrate has hydrophilic regions;

applying the precursor solution of any one of claims 1-17 to the substrate, the precursor solution selectively adsorbing to the hydrophilic region;

drying the precursor solution to obtain a dried product;

annealing the dried product in an oxygen-containing environment to obtain a pattern of metal oxides.

24. The method of claim 23, wherein treating the substrate comprises:

subjecting the entire substrate to hydrophilic treatment to obtain the hydrophilic region; or alternatively

Performing hydrophobic treatment on the whole substrate, and performing hydrophilic treatment on a local area of the substrate by matching with a mask plate to obtain the hydrophilic area; or alternatively

And carrying out hydrophilic treatment on the whole substrate, and carrying out hydrophobic treatment on a local area of the substrate by matching with a mask plate so as to obtain the hydrophilic area.

25. The method of claim 24, wherein,

the hydrophilic treatment comprises: one or more of oxygen plasma treatment, piranha solution soaking, laser irradiation, and treatment with UV-O3; and is also provided with

The hydrophobic treatment comprises: the SAM layer is formed and the organic solution used to form the SAM layer includes one or more of trimethoxysilanes, triethoxysilanes, trichlorosilane, and phosphonic acids.

26. The method of claim 23, wherein the precursor solution is applied to the substrate by a draw down method, a slot coating method, a knife coating method, or a spin coating method.

27. The method of claim 23, wherein,

the organic solvent is a high boiling point solvent, and the boiling point range is as follows: t is more than or equal to 230 ℃ and less than or equal to 300 ℃;

the precursor solution includes a surfactant;

the method comprises the following steps: the precursor solution is applied to the substrate in an environment of arbitrary relative humidity and dried.

28. The method of claim 23, wherein,

the method comprises the following steps: the precursor solution is applied to the substrate in an environment having a relative humidity above 40% rh and/or the precursor solution is dried in an environment having a relative humidity above 40% rh.

29. The method of claim 23, wherein,

The organic solvent is a low-boiling point solvent, and the range of the boiling point T is as follows: t is more than or equal to 50 ℃ and less than 230 ℃;

the method comprises the following steps: the precursor solution is applied to the substrate in an environment having a relative humidity of 30% rh or less and/or the precursor solution is dried in an environment having a relative humidity of 30% rh or less.

30. The method of claim 23, wherein annealing the dried product comprises: a first annealing process and a second annealing process are sequentially performed, wherein the temperature of the first annealing process is lower than the temperature of the second annealing process, and the duration of the first annealing process is shorter than the duration of the second annealing process.

31. The method of claim 30, wherein,

the temperature of the first annealing process is 25-200 ℃, and the duration of the first annealing process is less than or equal to 30 minutes; and is also provided with

The temperature of the second annealing process is 50-1000 ℃, and the duration of the second annealing process is less than or equal to 2 hours.

32. The method of any one of claims 23-31, wherein the pattern of metal oxide is a semiconductor pattern and the precursor salt of metal oxide is selected from one or more of zinc acetate, zinc nitrate, zinc chloride, indium acetate, indium nitrate, indium chloride, gallium acetate, gallium nitrate, gallium chloride, tin acetate, tin nitrate, tin tetrachloride, and stannous chloride.

33. The method of any of claims 23-31, wherein the pattern of the metal oxide is a conductive pattern and the precursor salt of the metal oxide is selected from one or more of indium acetate, indium nitrate, indium chloride, tin acetate, tin nitrate, tin tetrachloride, and stannous chloride.

34. The method of any of claims 23-31, wherein the pattern of the metal oxide is an insulating pattern and the precursor salt of the metal oxide is selected from one or more of hafnium tetrachloride, hafnium oxychloride, hafnium ethoxide, hafnium isopropoxide, hafnium n-butoxide, aluminum acetate, and aluminum nitrate.

35. The method of any of claims 23-31, wherein the pattern of metal oxide has a size of 500nm or greater.

36. A method of making an electronic device comprising a semiconductor layer, a conductor layer, and an insulating layer using a surface energy directed assembly processing technique, wherein the method comprises making at least one of the semiconductor layer, the conductor layer, and the insulating layer of the electronic device using the method of any one of claims 23-35.

37. The method of fabricating an electronic device using surface energy directed assembly processing techniques according to claim 36, comprising:

Preparing a preceding layer of the semiconductor layer, the conductor layer and the insulating layer of the electronic device, and thereafter preparing a following layer of the semiconductor layer, the conductor layer and the insulating layer of the electronic device, wherein,

in the process of preparing a subsequent layer of the semiconductor layer, the conductor layer and the insulating layer of the electronic device, a partial region of the substrate is subjected to a hydrophobic treatment to obtain a hydrophilic region for adsorbing the subsequent layer, the hydrophobic treatment including formation of a SAM layer, and an organic solution for forming the SAM layer including one or more of trimethoxysilanes and triethoxysilanes.

38. The method of fabricating an electronic device using surface energy directed assembly processing techniques as recited in claim 37, wherein,

trimethoxysilanes include trimethoxy (1H, 2H-nonafluorohexyl) silane trimethoxy (1H, 2H-tridecafluoron-octyl) silane, trimethoxy (1H, 2H-heptadecafluorodecyl) silane one or more of octadecyltrimethoxysilane, hexadecyltrimethoxysilane, dodecyltrimethoxysilane and octyltrimethoxysilane; and is also provided with

Triethoxysilanes include triethoxy (1H, 2H-nonafluorohexyl) silane triethoxy-1H, 2H-tridecyl fluoro-n-octyl silane, 1H, 2H-perfluoro decyl triethoxy silane one or more of octadecyltriethoxysilane, hexadecyltriethoxysilane, dodecyl triethoxysilane, hexyl triethoxysilane, and butyl triethoxysilane.