CN107644806A - The graphical preparation method of the orderly self assembly of metal oxide and metal-oxide film - Google Patents

Abstract

An embodiment of the present invention provides a method for preparing metal oxide ordered self-assembly patterning and a metal oxide thin film. The method includes: performing hydrophobic treatment on the surface of a hydrophilic substrate, or performing hydrophilic treatment on the surface of a hydrophobic substrate. treatment to form two hydrophilic and hydrophobic interfaces with different surface energies, and a micro-nano pattern arrangement structure of a specific shape is formed between the two interfaces; the metal oxide precursor is coated on the formed substrate with the micro-nano pattern arrangement structure On the surface, the self-assembly behavior of wetting and dewetting occurs spontaneously, and a patterned ordered metal oxide film is obtained. On the other hand, an embodiment of the present invention provides a metal oxide thin film prepared by the above-mentioned metal oxide ordered self-assembly patterning preparation method. The above technical solution has the following beneficial effects: the method has the advantages of no damage, low consumption materials, and one-time patterning, and is applicable to both hard substrates (glass, silicon dioxide, silicon, etc.) and flexible substrates (PET, PDMS, PI, etc.).

Description

Patterned preparation method of metal oxide ordered self-assembly and metal oxide thin film

technical field

The invention relates to the technical field of metal oxide semiconductors, in particular to a method for preparing a metal oxide ordered self-assembly pattern and a metal oxide thin film.

Background technique

Compared with silicon and organic semiconductor materials, metal oxide semiconductors have the advantages of high electron mobility (over 10 cm ² /volt·s), high transparency, and good uniformity over a large area. Due to the considerable potential of metal oxide thin films, there are a wide range of applications in sensors, solar cells, non-volatile memory devices, and ultra-high-resolution flat panel displays.

Traditional metal oxide semiconductors usually use vacuum-assisted technology, such as sputtering (PVD\PECVD) or pulsed laser ablation (PLA). However, since different metal materials in the target have different evaporation rates, the stoichiometric ratio of metal elements will change after the target is used many times, which will affect the performance of metal oxide semiconductors. The solution method to prepare metal oxide semiconductor technology can strictly control the stoichiometric ratio of metal elements. Moreover, the solution method has the advantages of low-temperature preparation, is compatible with flexible substrates, and has the potential to prepare flexible electronic circuits.

In order to achieve high integration, low leakage current, and low parasitic resistance and capacitance, high-performance integrated electronic circuits require precise patterning processes. In order to realize the application of metal oxide semiconductors in integrated electronic circuits, it is very important to realize high-precision patterning of metal oxide semiconductors. At present, the patterning process of metal oxide semiconductors is mainly a subtractive process, such as photolithography and etching, but photolithography and etching patterning will damage metal oxide semiconductors and waste raw materials. The etchant also pollutes the environment. A one-time patterning process with no damage and low consumables is particularly important.

Contents of the invention

The embodiment of the present invention provides a metal oxide ordered self-assembly patterning preparation method and a metal oxide thin film. The metal oxide thin film is prepared with no damage, low material consumption, and one-time patterning, and is also suitable for rigid substrates (glass , silicon dioxide, silicon, etc.) and flexible substrates (PET, PDMS, PI, etc.).

On the one hand, an embodiment of the present invention provides a method for preparing metal oxide ordered self-assembly patterning, the method comprising:

Hydrophobic treatment is performed on the surface of the hydrophilic substrate, or hydrophilic treatment is performed on the surface of the hydrophobic substrate to form two hydrophilic and hydrophobic interfaces with different surface energies, and a micro-nano pattern arrangement structure of a specific shape is formed between the two interfaces ;

The metal oxide precursor is coated on the formed substrate with the micro-nano pattern arrangement structure, the self-assembly behavior of wetting and dewetting occurs spontaneously, and a patterned ordered metal oxide film is obtained.

On the other hand, an embodiment of the present invention provides a metal oxide thin film prepared by the above-mentioned metal oxide ordered self-assembly patterning preparation method.

The above technical solution has the following beneficial effects: the method has the advantages of no damage, low consumption materials, one-time specific position patterning, and is applicable to both hard substrates (glass, silicon dioxide, silicon, etc.) and flexible substrates (PET, PDMS, PI, etc.). The patterning method described in the embodiment of the present invention utilizes the surface energy difference between the hydrophilic and hydrophobic interfaces to realize the precipitation of the metal oxide semiconductor precursor in the hydrophilic pattern area, and the patterned metal oxide thin film obtained in the embodiment of the present invention can be applied For high efficiency, large-scale preparation of field effect transistor devices, sensor devices and solar cell devices.

Description of drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments of the present invention. Those skilled in the art can also obtain other drawings based on these drawings without creative work.

Fig. 1 is a flowchart of a patterned preparation method of ordered self-assembly of metal oxides according to an embodiment of the present invention.

Fig. 2 is the contact angle on a clean silica surface (without hydrophilic/hydrophobic treatment) described in the embodiment of the present invention.

Fig. 3 is the contact angle of the silicon dioxide surface treated with the hydrophobic material HMDS according to the embodiment of the present invention.

Fig. 4 is the contact angle of the HMDS-coated silicon dioxide surface after UV ozone is used for hydrophilic treatment according to the embodiment of the present invention.

Fig. 5 is a schematic diagram of the preparation of a metal oxide thin film matrix by using the hydrophobic material HMDS and UV ozone for hydrophilic treatment to obtain a hydrophilic and hydrophobic graphic matrix according to an embodiment of the present invention.

Fig. 6 is a metal oxide thin film matrix prepared from a patterned matrix obtained by hydrophilic treatment of the hydrophobic material HMDS and UV ozone in an embodiment of the present invention.

Fig. 7 is the contact angle of the silicon dioxide surface treated with the hydrophobic material CYTOP according to the embodiment of the present invention.

Fig. 8 is the contact angle of the silicon dioxide surface after hydrophilic treatment by hydrophobic material CYTOP and plasma etching according to the embodiment of the present invention.

9 is a schematic diagram of a metal oxide thin film matrix prepared by using hydrophobic material CYTOP and plasma etching to perform hydrophilic treatment to obtain a hydrophilic and hydrophobic pattern matrix according to an embodiment of the present invention.

FIG. 10 is a metal oxide thin film matrix prepared from a patterned matrix obtained by using hydrophobic material CYTOP and plasma etching for hydrophilic treatment according to an embodiment of the present invention.

Fig. 11 is a schematic diagram of a metal oxide thin film matrix prepared by using hydrophobic material CYTOP and a photolithographic lift-off process to obtain a matrix of hydrophilic and hydrophobic patterns according to an embodiment of the present invention.

Fig. 12 is a metal oxide film matrix prepared by using the hydrophobic material CYTOP and the hydrophilic-hydrophobic pattern matrix obtained by the photolithography lift-off process according to the embodiment of the present invention.

Fig. 13 is a metal oxide film matrix prepared by using the hydrophilic-hydrophobic patterned matrix obtained on the flexible substrate-PI according to the embodiment of the present invention.

FIG. 14 is a device structure of an oxide transistor according to an embodiment of the present invention.

FIG. 15 is an embodiment of the present invention using an InGaZnO thin film matrix to prepare a metal oxide transistor matrix.

detailed description

The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some, not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

As shown in Figure 1, it is a flow chart of a method for preparing a metal oxide ordered self-assembly pattern according to an embodiment of the present invention, and the method includes:

101. Perform hydrophobic treatment on the surface of the hydrophilic substrate, or perform hydrophilic treatment on the surface of the hydrophobic substrate to form two hydrophilic and hydrophobic interfaces with different surface energies, and form micro-nano patterns of specific shapes between the two interfaces arrangement structure;

102. Coating the metal oxide precursor on the formed substrate having the micro-nano pattern arrangement structure, spontaneously occur the self-assembly behavior of wetting and dewetting, and obtain a patterned ordered metal oxide film.

Preferably, the hydrophilic substrate comprises: glass, quartz, silicon dioxide, silicon or other hard or flexible substrates through hydrophilic treatment; the hydrophilic treatment method comprises: ultraviolet ozone irradiation or plasma body bombardment; the hydrophilic treatment material includes: aminopropyltriethoxysilane APTES, piranha solution;

The hydrophobic substrate includes: untreated or all hard or flexible substrates through hydrophobic treatment; the hydrophobic treatment material includes: octadecyltrichlorosilane, hexamethyldisilamine, polydimethylsilane base silicone, polytetrafluoroethylene or perfluororesin CYTOP.

Preferably, the thickness of the micro-nano pattern is in the range of 0.01 μm to 100 μm, and the characteristic size of the micro-nano pattern structure is in the range of 1 μm to 5000 μm.

Preferably, the micro-nano-pattern arrangement structure of a specific shape includes: regular micro-nano-patterns and irregular micro-nano-patterns; the regular micro-nano-patterns include: circles, squares, and triangles.

Preferably, the withstand temperature range of the micro-nano pattern structure is -10°C to 600°C.

Preferably, the metal oxide precursor is coated on the formed substrate with the micro-nano pattern arrangement structure, the self-assembly behavior of wetting and dewetting occurs spontaneously, and a patterned ordered metal is obtained. Oxide thin film process, including spin coating, scraping coating, drop coating, pulling, spray coating.

Preferably, the method also includes:

Dissolving one or more metal salts as the solute of the metal oxide precursor in a solvent to configure the metal oxide precursor, the concentration of the metal oxide precursor is less than 1mol/L; wherein:

The solute of the metal oxide precursor contains one or more of the following metal elements: indium In, gallium Ga, zinc Zn, tin Sn, aluminum Al, zirconium Zr, iridium Ir;

The solvent of the metal oxide precursor includes: an organic solvent or an inorganic solvent; the organic solvent includes: dimethoxyethanol, DMF, acetylacetone, ethylene glycol, ethanol; the inorganic solvent includes: deionized water , ammonia, hydrogen peroxide.

Preferably, the metal oxide precursor is coated on the formed substrate with the micro-nano pattern arrangement structure, and after the self-assembly behavior of wetting and dewetting occurs spontaneously, it is obtained by annealing one or more times. In the patterned ordered metal oxide thin film, the annealing temperature range is 80°C to 500°C.

Preferably, hydrophilicity and hydrophobicity are relative concepts. When forming two hydrophilic-hydrophobic interfaces with different surface energies, the static pure water contact angle of the metal oxide in the hydrophobic region of the substrate is different from the static pure water contact angle in the hydrophilic region. The difference is greater than 30°.

The embodiment of the present invention also provides a metal oxide thin film prepared by the above-mentioned metal oxide ordered self-assembly patterning preparation method.

The above technical solution has the following beneficial effects: the method has the advantages of no damage, low consumption materials, one-time specific position patterning, and is applicable to both hard substrates (glass, silicon dioxide, silicon, etc.) and flexible substrates (PET, PDMS, PI, etc.). The patterning method described in the embodiment of the present invention utilizes the surface energy difference between the hydrophilic and hydrophobic interfaces to realize the precipitation of the metal oxide semiconductor precursor in the hydrophilic pattern area, and the patterned metal oxide thin film obtained in the embodiment of the present invention can be applied For high efficiency, large-scale preparation of field effect transistor devices, sensor devices and solar cell devices.

The patterned ordered metal oxide thin film obtained in the embodiment of the present invention can be applied in the preparation of field effect transistor devices, sensor devices or solar cell devices. The patterned and ordered metal oxide thin film obtained in the embodiment of the present invention can be applied in the preparation of rigid electronic devices. The patterned ordered metal oxide thin film obtained in the embodiment of the present invention can be applied in the preparation of flexible electronic devices.

As shown in FIG. 2 , it is the contact angle on a clean silica surface (without hydrophilic/hydrophobic treatment) described in the embodiment of the present invention. The above-mentioned technical solutions of the embodiments of the present invention are described in detail below through application examples:

Application example 1:

As shown in FIG. 3 , the contact angle of the silicon dioxide surface treated with the hydrophobic material HMDS according to the present invention is 81.2°. As shown in FIG. 4 , the contact angle of the HMDS-coated silica surface after UV ozone treatment according to the present invention is 4.8°. However, according to the process flow shown in Figure 5, two regions with different surface free energies can be produced simultaneously on the same substrate, and the difference in contact angle is 76.4°. Utilizing this difference, the metal oxide thin film matrix can be prepared by self-assembly on the substrate. The specific implementation is as follows.

The first is to formulate the metal oxide precursor. Indium(III) nitrate hydrate (Grade 99.9%) purchased from Sigma-Aldrich was dissolved in organic solvent 2-methoxyethanol (anhydrous, 99.8%) at a concentration of 0.1 mol/L. Finally, it was placed on a magnetic vibration stirrer and stirred at 800 rpm for 3 hours to obtain the precursor of indium oxide.

Next, according to the process flow shown in FIG. 5 , the substrate 41 is subjected to hydrophilic and hydrophobic treatment. The substrate 41 we choose in this embodiment is a silicon wafer with 100nm silicon dioxide. First, cut and clean the silicon wafer, cut a 4-inch silicon wafer into a size of 1.5cm×1.5cm, and then cut the silicon wafer 41 Submerged in acetone with a purity of 99.99%, ethanol with a purity of 99.99%, and deionized water for 30 minutes, and then ultrasonically cleaned the silicon wafer 41 for 30 minutes. Bake for 10 minutes to remove residual water vapor on the silicon wafer 41 . The dried silicon wafer 41 was placed on a desktop coating machine, and the HMDS film 42 was spin-coated (the rotation speed was 2000 rpm, and the time was 60 s). Next, a patterned metal mask 43 is placed on the silicon wafer coated with the HMDS film 42 . It was then placed in a UV ozone machine and treated with UV light (hυ) 44 for 3 minutes. Two regions with different surface free energies can be obtained.

Finally, an indium oxide thin film matrix is prepared on a patterned hydrophilic and hydrophobic substrate. The coating method selected in this embodiment is spin coating. The rotating speed of spin coating is 3000rpm, and the time is 30s. The precursor matrix 45 of indium oxide can be obtained. Finally, anneal at 350 degrees Celsius for one hour on a hot plate to obtain a thin film matrix 45 of indium oxide, as shown in FIG. 6 .

Application example 2:

As shown in FIG. 7 , the contact angle of the silicon dioxide surface treated with the hydrophobic material CYTOP according to the present invention is 116.4°. As shown in FIG. 8 , the contact angle of the CYTOP coated silicon dioxide surface after the plasma etching treatment according to the present invention is 18.6. However, according to the process flow shown in FIG. 9 , two regions with different surface free energies can be simultaneously produced on the same substrate, and the difference in contact angle is 97.8°. Utilizing this difference, the metal oxide thin film matrix can be prepared by self-assembly on the substrate. The specific implementation is as follows.

The first is to formulate the metal oxide precursor. The hydrate (Grade99.9%) of tin dichloride purchased from Sigma Aldrich is dissolved in organic solvent 2-methoxyethanol (anhydrous, 99.8%) according to the concentration of 0.15mol/L, and then The upper equimolar concentration of acetylacetone. Finally, it was placed on a magnetic vibration stirrer and stirred at a speed of 800 rpm for 3 hours to obtain the precursor of tin oxide.

Next, according to the process flow shown in FIG. 9 , the substrate is subjected to hydrophilic and hydrophobic treatment. The substrate we choose in this embodiment is a silicon wafer 81 with 100nm silicon dioxide. The first is to cut and clean the silicon wafer. A 4-inch silicon wafer is cut into a size of 1.5cm×1.5cm, and then the silicon wafer 81 is sequentially immersed in acetone with a purity of 99.99%, ethanol with a purity of 99.99%, and ultrasonically cleaned in deionized water for 30 minutes each. Minutes, and then use nitrogen to blow away the residual moisture, place the silicon wafer 81 on a hot plate at 110° C., and bake for 10 minutes to remove the residual moisture. The dried silicon wafer 81 is placed on a desktop coater, and the CYTOP film 82 is spin-coated, first at a speed of 500r/m for 10s, and then at a speed of 5000r/m for 40s. CYTOP solution is obtained by preparing CYTOP and CYTOP solvent at a mass ratio of 1:6. Next, place the silicon wafer spin-coated with CYTOP film 82 on a hot plate at 120° C. and bake for 30 minutes. After baking, remove the sample. After the sample is cooled to room temperature, the metal mask plate 83 is placed on the sample, and then put into the plasma machine, and treated with O2plasma 84 for 90s. It can be patterned, and two regions with different surface free energies can be obtained.

Finally, a tin oxide film matrix is prepared on a patterned hydrophilic and hydrophobic substrate. The coating method selected in this embodiment is oblique drop coating, and the precursor pattern 85 of tin oxide can be obtained. Finally, after annealing at 400 degrees Celsius, a thin film pattern 85 of tin oxide can be obtained, as shown in FIG. 10 .

Application example 3:

As shown in FIG. 7 , the contact angle of the silicon dioxide surface treated with the hydrophobic material CYTOP according to the present invention is 116.4°. As shown in FIG. 8 , the contact angle of the CYTOP coated silicon dioxide surface after the plasma etching treatment according to the present invention is 18.6. However, according to the process flow shown in FIG. 9 , two regions with different surface free energies can be simultaneously produced on the same substrate, and the difference in contact angle is 97.8°. Utilizing this difference, the metal oxide thin film matrix can be prepared by self-assembly on the substrate. The specific implementation is as follows.

The first is to formulate the metal oxide precursor. Indium (III) nitrate hydrate (Grade 99.9%) and zinc salt hydrate (Grade 99.999%) purchased from Sigma Aldrich, according to the concentration of 0.15mol/L, respectively Dissolve in the organic solvent 2-methoxyethanol (anhydrous, 99.8%), and then put the respective metal nitrate solutions on a magnetic stirrer and stir at 800 rpm for 2 hours. Then mix according to the volume ratio of indium:zinc=1:1 to obtain an indium-zinc mixed solution. Next, the indium-zinc mixed solution was placed on a magnetic vibration stirrer and stirred at a speed of 800 rpm for 2 hours to obtain the precursor of InZnO.

Next, according to the process flow shown in FIG. 9 , the substrate is subjected to hydrophilic and hydrophobic treatment. The substrate we choose in this embodiment is a PI substrate 81 with a thickness of 5 μm. First, cut and clean the PI substrate, cut the PI substrate 4A into 4cm×4cm, then immerse the PI substrate 81 in acetone with a purity of 99.99%, ethanol with a purity of 99.99%, and deionized water for ultrasonic cleaning. After 30 minutes, nitrogen gas is used to retain moisture, and the PI substrate 81 is placed on a hot plate at 110° C., and baked for 10 minutes to remove residual moisture. The dried PI substrate 81 was placed on a desktop coater, and the CYTOP film 82 was spin-coated, first at a speed of 500r/m for 10s, and then at a speed of 5000r/m for 40s. CYTOP solution is obtained by preparing CYTOP and CYTOP solvent at a mass ratio of 1:6. Next, put the PI substrate 81 spin-coated with the CYTOP thin film 82 on a hot plate at 120° C. and bake for 30 minutes. After baking, remove the sample. After the sample is cooled to room temperature, the metal mask plate 83 is placed on the sample, and then put into the plasma machine, and treated with O2plasma 84 for 90s. A graphical matrix can be formed, and two regions with different surface free energies can be obtained.

Finally, an InZnO thin film matrix is prepared on a patterned hydrophilic and hydrophobic substrate. The coating method selected in this embodiment is scrape coating. Drop the InZnO precursor on the edge of the patterned PI substrate 81, then place the glass rod above the solution, use capillary action to form a capillary bridge, and finally drag the glass rod (capillary bridge) in a fixed direction to form InZnO Precursor Matrix 85 . Finally, after annealing at 300 degrees Celsius, the InZnO film matrix 85 can be obtained, as shown in FIG. 13 .

Application example 4:

As shown in Figure 2, the contact angle on a clean glass surface (without hydrophilic/hydrophobic treatment) is 48.7°. As shown in FIG. 7 , the contact angle of the glass surface treated with the hydrophobic material CYTOP according to the present invention is 116.4°. However, according to the process flow shown in FIG. 11 , two regions with different surface free energies can be simultaneously produced on the same substrate, and the difference in contact angle is 67.7°. Utilizing this difference, the metal oxide thin film matrix can be prepared by self-assembly on the substrate. And the metal oxide transistor matrix is prepared by using the metal oxide thin film matrix. The specific implementation is as follows.

The first is to formulate the metal oxide precursor. Indium (III) nitrate hydrate (Grade 99.9%), zinc salt hydrate (Grade 99.999%) and gallium (III) nitrate hydrate (crystalline, Grade 99.9%) purchased from Sigma-Aldrich, According to the concentration of 0.05mol/L, dissolve in the organic solvent 2-methoxyethanol (anhydrous, 99.8%). Then the respective metal nitrate solutions were placed on a magnetic stirrer and stirred at a speed of 800 rpm for 2 hours. Then mix according to the volume ratio of indium:zinc:gallium=6:3:1 to obtain an indium-zinc-gallium mixed solution. Next, the indium-zinc-gallium mixed solution was placed on a magnetic vibration stirrer and stirred at a speed of 800 rpm for 2 hours to obtain the precursor of InGaZnO.

Next, according to the process flow shown in FIG. 11 , the substrate is subjected to hydrophilic and hydrophobic treatment. The substrate we choose in this embodiment is a silicon wafer 101 with 100nm silicon dioxide. Firstly, the silicon wafer 101 is cleaned, and the silicon wafer 101 is sequentially soaked in acetone with a purity of 99.99%, ethanol with a purity of 99.99%, and deionized water for 30 minutes, and then the residual moisture is blown away with nitrogen gas, and the silicon wafer 101 is placed on the Bake on a hot plate at 110°C for 10 minutes to remove residual water vapor.

The dried silicon wafer 101 is placed on a table-top coating machine (KW-4A type, Institute of Microelectronics, Chinese Academy of Sciences), and the photoresist 102 (viscosity is 30MPa) is spin-coated, and first rotated at a speed of 500r/m for 9s, Then rotate at a speed of 2000r/m for 40s. Next, place the silicon wafer spin-coated with the photoresist 102 on a hot plate at 120° C. and bake for 2 minutes. After the baking is completed, take out the sample, wait for the sample to cool to room temperature, put the sample in the exposure machine, and UV exposure treatment for 21s. Then immerse the sample in the developer solution paired with the photoresist for 1 min, and finally rinse with deionized water and blow dry.

Then, the CYTOP film 103 was spin-coated on the photoresist-patterned substrate using a desktop coater at a spin-coating speed of 5000 rpm for 60 s. Next, put the sample on a hot plate at 100° C. and bake it for 6 minutes to cure the CYTOP film 103 . Finally, soak the sample in acetone with a purity of 99.99% for 10 minutes, and remove the photoresist 102 . Finally, the substrate on which the CYTOP thin film 103 is imaged remains.

Finally, the InGaZnO thin film matrix 104 is prepared on the patterned hydrophilic and hydrophobic substrate. The coating method selected in this embodiment is scrape coating. Drop the precursor of InGaZnO on the edge of the patterned substrate, then place the glass rod above the solution, use capillary action to form a capillary bridge, and finally drag the glass rod (capillary bridge) in a fixed direction to form InGaZnO Precursor Matrix 104 . Finally, after annealing at 350 degrees Celsius, the InGaZnO film matrix 104 can be obtained, as shown in FIG. 12 .

Next, the matrix of metal oxide transistors is prepared by using the matrix of InGaZnO films 104 . The device structure of the oxide transistor is shown in Figure 14. The oxide transistor includes a gate electrode 131, an insulating layer 132, an active channel layer 133, source and drain electrodes 134, 135, and a CYTOP thin film 136. The structure of the oxide transistor is a bottom Gate top contact, the gate electrode is N-type heavily doped silicon 131, the insulating layer is 100nm silicon dioxide 132, the active channel layer is the thin film matrix 133 of InGaZnO prepared in this embodiment, and the source and drain electrodes are made of metal The aluminum electrodes 134 and 135 are prepared by thermal evaporation on the mask plate. The matrix of metal oxide transistors prepared by using the thin film matrix of InGaZnO is shown in FIG. 15 .

Application examples of the present invention The above-mentioned technical scheme has the following beneficial effects: the method has the advantages of no damage, low consumables, and one-time specific position patterning, and is applicable to both hard substrates (glass, silicon dioxide, silicon, etc.) and flexible substrates. Substrate (PET, PDMS, PI, etc.). The patterning method described in the embodiment of the present invention utilizes the surface energy difference between the hydrophilic and hydrophobic interfaces to realize the precipitation of the metal oxide semiconductor precursor in the hydrophilic pattern area, and the patterned metal oxide thin film obtained in the embodiment of the present invention can be applied For high efficiency, large-scale preparation of field effect transistor devices, sensor devices and solar cell devices.

The patterned ordered metal oxide thin film obtained in the application examples of the present invention can be applied in the preparation of field effect transistor devices, sensor devices or solar cell devices. The patterned and ordered metal oxide thin film obtained in the application example of the present invention can be applied in the preparation of rigid electronic devices. The patterned and ordered metal oxide thin film obtained in the application example of the present invention can be applied in the preparation of flexible electronic devices.

It is understood that the specific order or hierarchy of steps in the processes disclosed is an example of exemplary approaches. Based upon design preferences, it is understood that the specific order or hierarchy of steps in the processes may be rearranged without departing from the scope of the present disclosure. The accompanying method claims present elements of the various steps in a sample order, and are not meant to be limited to the specific order or hierarchy described.

In the foregoing Detailed Description, various features are grouped together in a single embodiment to simplify the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claimed embodiments of the subject matter require more features than are expressly recited in each claim. Rather, as the following claims reflect, the invention lies in less than all features of a single disclosed embodiment. Thus the following claims are hereby expressly incorporated into the Detailed Description, with each claim standing on its own as a separate preferred embodiment of this invention.

The foregoing description of the disclosed embodiments was provided to enable any person skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may also be applied to other embodiments without departing from the spirit and scope of the disclosure. Thus, the present disclosure is not intended to be limited to the embodiments presented herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

The foregoing description includes illustrations of one or more embodiments. Of course, it is impossible to describe all possible combinations of components or methods to describe the above-mentioned embodiments, but those skilled in the art should recognize that various embodiments can be further combined and permuted. Accordingly, the embodiments described herein are intended to embrace all such alterations, modifications and variations that fall within the scope of the appended claims. Furthermore, to the extent that the term "comprises" is used in the specification or claims, the word is encompassed in a manner similar to the term "comprises" as interpreted when "comprises" is used as a link in the claims. Furthermore, any use of the term "or" in the specification of the claims is intended to mean a "non-exclusive or".

The specific embodiments described above have further described the purpose, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above descriptions are only specific embodiments of the present invention and are not intended to limit the scope of the present invention. Protection scope, within the spirit and principles of the present invention, any modification, equivalent replacement, improvement, etc., shall be included in the protection scope of the present invention.

Claims (10)

1. the graphical preparation method of a kind of orderly self assembly of metal oxide, it is characterised in that methods described includes：

In hydrophilic substrate surface, hydrophobic treatment is carried out, or in hydrophobic substrate surfaces, carries out hydrophilic treated, forms surface energy Different two kinds of interfaces of hydrophobe, and the micro-nano graph arrangement architecture of given shape is formed between two kinds of interfaces；

Metal oxide precursor is coated on the substrate with the micro-nano graph arrangement architecture formed, it is spontaneous to moisten The wet and self assembly behavior of wetting removal, obtain patterned orderly metal-oxide film.

2. the graphical preparation method of the orderly self assembly of metal oxide as claimed in claim 1, it is characterised in that the hydrophilic lining Bottom includes：Glass, quartz, silica, silicon or the other hard or flexible substrate by hydrophily processing；At the hydrophily Reason method includes：UV ozone irradiates or plasma bombardment；The hydrophily processing material includes：Aminopropyl-triethoxy silicon Alkane APTES, piranha solution；

The hydrophobic substrate includes：All hard or flexible substrate undressed or Jing Guo hydrophobic treatment；The hydrophobicity Processing material includes：Octadecyl trichlorosilane alkane, hmds, dimethyl silicone polymer, polytetrafluoroethylene (PTFE) or perfluor tree Fat CYTOP.

3. the graphical preparation method of the orderly self assembly of metal oxide as claimed in claim 1, it is characterised in that the micro-nano figure The thickness range of shape is 0.01 μm~100 μm, and the feature size range of micro-nano graphic structure is 1 μm~5000 μm.

4. the graphical preparation method of the orderly self assembly of metal oxide as claimed in claim 1, it is characterised in that the specific shape The micro-nano graph arrangement architecture of shape includes：Regular micro-nano graph and irregular micro-nano graph；The regular micro-nano graph includes： Circular, square, triangle.

5. the graphical preparation method of the orderly self assembly of metal oxide as claimed in claim 1, it is characterised in that the micro-nano figure The tolerable temperature scope of shape structure is -10 DEG C~600 DEG C.

6. the graphical preparation method of the orderly self assembly of metal oxide as claimed in claim 1, it is characterised in that realize described incite somebody to action Metal oxide precursor is coated on the substrate with the micro-nano graph arrangement architecture formed, and spontaneous generation is soaked and gone The self assembly behavior of wetting, the technique for obtaining patterned metal-oxide film in order, including spin coating, blade coating, drop coating, carry Draw, spraying.

7. the graphical preparation method of the orderly self assembly of metal oxide as claimed in claim 6, it is characterised in that methods described is also Including：

Solute using the metal salt of one or more as the metal oxide precursor, dissolves in a solvent, to configure gold Belong to oxide precursor, the concentration of the metal oxide precursor is less than 1mol/L；Wherein：

The solute of the metal oxide precursor, include the one or more in following metallic element：Indium In, gallium Ga, zinc Zn, Tin Sn, aluminium Al, zirconium Zr, iridium Ir；

The solvent of the metal oxide precursor, comprising：Organic solvent or inorganic solvent；The organic solvent includes：Diformazan Ethoxy-ethanol, DMF, acetylacetone,2,4-pentanedione, ethylene glycol, ethanol；The inorganic solvent includes：Deionized water, ammoniacal liquor, hydrogen peroxide.

8. the graphical preparation method of the orderly self assembly of metal oxide as claimed in claim 6, it is characterised in that described by metal Oxide precursor is coated on the substrate with the micro-nano graph arrangement architecture formed, spontaneous generation wetting and wetting removal Self assembly behavior after, obtain patterned orderly metal-oxide films, the temperature of the annealing by one or many annealing It is 80 DEG C~500 DEG C to spend scope.

9. such as the orderly graphical preparation method of self assembly of metal oxide any one of claim 1-8, it is characterised in that When the different two kinds of interfaces of hydrophobe of formation surface energy, static pure water of the metal oxide in underlay substrate hydrophobic region Contact angle is more than 30 ° with the static pure water contact angle difference in hydrophilic region.

A kind of 10. graphical preparation method system of the orderly self assembly of metal oxide described in any claim in claim 1 to 9 Standby obtained metal-oxide film.