CN107644806A - The graphical preparation method of the orderly self assembly of metal oxide and metal-oxide film - Google Patents
The graphical preparation method of the orderly self assembly of metal oxide and metal-oxide film Download PDFInfo
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- CN107644806A CN107644806A CN201710763547.0A CN201710763547A CN107644806A CN 107644806 A CN107644806 A CN 107644806A CN 201710763547 A CN201710763547 A CN 201710763547A CN 107644806 A CN107644806 A CN 107644806A
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Abstract
The embodiment of the present invention, which provides the graphical preparation method of the orderly self assembly of metal oxide and metal-oxide film, methods described, to be included：In hydrophilic substrate surface, hydrophobic treatment is carried out, or in hydrophobic substrate surfaces, carries out hydrophilic treated, forms the different two kinds of interfaces of hydrophobe of surface energy, 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, spontaneous generation wetting and the self assembly behavior of wetting removal, obtains patterned orderly metal-oxide film.On the other hand, the embodiments of the invention provide the metal-oxide film that a kind of graphical preparation method of above-mentioned orderly self assembly of metal oxide is prepared.Above-mentioned technical proposal has the advantages that：This method possesses not damaged, low-material-consumption, disposable patterned advantage, and is applied to rigid substrate (glass, silica, silicon etc.) and flexible substrate (PET, PDMS, PI etc.) simultaneously.
Description
Technical field
The present invention relates to metal oxide semiconductor techniques field, more particularly to the orderly self assembly of metal oxide are graphical
Preparation method and metal-oxide film.
Background technology
Compared with silicon and organic semiconducting materials, metal-oxide semiconductor (MOS) has high electron mobility (more than 10cm2/
Weber), the good advantage of the high grade of transparency, large-area uniformity.Because metal-oxide film has sizable potentiality, passing
Sensor, solar cell, non-volatile memory devices and ultrahigh resolution flat-panel monitor on be widely used.
Traditional metal-oxide semiconductor (MOS), such as generally use vacuum aided technology, sputtering (PVD PECVD) or pulse swash
Light ablation (PLA).But because metal material different in target possesses different evaporation rates, target is after a number of uses, golden
The stoichiometric proportion of category element can change, and then influence the performance of metal-oxide semiconductor (MOS).And solwution method prepares metal
Oxide semiconductor technology, it can strictly control the stoichiometric proportion of metallic element.And solwution method technique possesses low temperature preparation
Advantage, it is compatible with flexible substrate, possess the potentiality for preparing flexible electronic circuit.
In order to realize high integrated level, low leakage current and low dead resistance and parasitic capacitance etc., high performance collection
Accurate patterning process is needed into electronic circuit.And in order to realize metal-oxide semiconductor (MOS) answering in integrated electronic circuit
With realizing that the high accuracy of metal-oxide semiconductor (MOS) is graphical extremely important.At present, the figure chemical industry of metal-oxide semiconductor (MOS)
Skill is mainly that subtraction formula technique, such as chemical wet etching, but chemical wet etching can graphically damage metal-oxide semiconductor (MOS), and is wasted
Raw material.Etching liquid also pollutes the environment.The disposable patterning process of not damaged low-material-consumption is particularly important.
The content of the invention
The embodiment of the present invention provides a kind of graphical preparation method of orderly self assembly of metal oxide and metal oxide is thin
Film, with not damaged, low-material-consumption, metal-oxide film is graphically disposably prepared, and be applied to rigid substrate (glass simultaneously
Glass, silica, silicon etc.) and flexible substrate (PET, PDMS, PI etc.).
On the one hand, it is described the embodiments of the invention provide a kind of graphical preparation method of the orderly self assembly of metal oxide
Method includes：
In hydrophilic substrate surface, hydrophobic treatment is carried out, or in hydrophobic substrate surfaces, carries out hydrophilic treated, forms table
The different two kinds of interfaces of hydrophobe of face energy, 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, spontaneous hair
Raw wetting and the self assembly behavior of wetting removal, obtain patterned orderly metal-oxide film.
On the other hand, the embodiments of the invention provide a kind of graphical preparation method of above-mentioned orderly self assembly of metal oxide
The metal-oxide film being prepared.
Above-mentioned technical proposal has the advantages that：This method possesses not damaged, low-material-consumption, disposable ad-hoc location figure
The advantages of shape, and it is applied to rigid substrate (glass, silica, silicon etc.) and flexible substrate (PET, PDMS, PI simultaneously
Deng).Graphic method described in the embodiment of the present invention utilizes the surface energy difference at two kinds of interfaces of hydrophobe, realizes metal oxide half
Conductor precursor body hydrophilic pattern region sedimentation, and the embodiment of the present invention obtain patterned metal sull can apply
In high benefit, FET device is prepared on a large scale, senser element prepares and solar cell device.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is a kind of graphical preparation method flow chart of the orderly self assembly of metal oxide of the embodiment of the present invention.
Fig. 2 is in the contact angle of clean silica surface (not doing parent/hydrophobic treatment) described in the embodiment of the present invention.
Fig. 3 is the contact angle of the silica surface after hydrophobic material HMDS processing described in the embodiment of the present invention.
Fig. 4 is connecing for the HMDS coating silicon dioxides surface after UV ozone does hydrophilic treated described in the embodiment of the present invention
Feeler.
Fig. 5 is that the embodiment of the present invention does hydrophily processing gained hydrophobe figure using hydrophobic material HMDS and UV ozone
Matrix prepares the schematic diagram of metal-oxide film matrix.
Fig. 6 is the graphical square that the embodiment of the present invention does hydrophily processing gained using hydrophobic material HMDS and UV ozone
Metal-oxide film matrix prepared by battle array.
Fig. 7 is the contact angle of the silica surface after hydrophobic material CYTOP processing described in the embodiment of the present invention.
Fig. 8 is dioxy of the embodiment of the present invention after hydrophobic material CYTOP and plasma etching do hydrophily processing
The contact angle on SiClx surface.
Fig. 9 is the embodiment of the present invention using hydrophobic material CYTOP and plasma etching, and to do hydrophily processing gained close and distant
The schematic diagram of metal-oxide film matrix prepared by water pattern matrix.
Figure 10 is the figure that the embodiment of the present invention does hydrophily processing gained using hydrophobic material CYTOP and plasma etching
Metal-oxide film matrix prepared by shape matrix.
Figure 11 is that the embodiment of the present invention is close and distant using gained after hydrophobic material CYTOP and photoetching lift-off PROCESS FOR TREATMENTs
The schematic diagram of metal-oxide film matrix prepared by water pattern matrix.
Figure 12 is hydrophobe figure of the embodiment of the present invention obtained by using hydrophobic material CYTOP and photoetching lift-off techniques
Metal-oxide film matrix prepared by shape matrix.
Figure 13 is in flexible substrate using the embodiment of the present invention --- it is prepared by the graphical matrix of hydrophobe of the upper gained of PI
Metal-oxide film matrix.
Figure 14 is the device architecture of oxide transistor of the embodiment of the present invention.
Figure 15 is that the embodiment of the present invention prepares MOS transistor matrix using InGaZnO film matrix.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made
Embodiment, belong to the scope of protection of the invention.
As shown in figure 1, be a kind of graphical preparation method flow chart of the orderly self assembly of metal oxide of the embodiment of the present invention,
Methods described includes：
101st, in hydrophilic substrate surface, hydrophobic treatment is carried out, or in hydrophobic substrate surfaces, carries out hydrophilic treated, shape
Hydrophobe two kind interfaces different into surface energy, and the micro-nano graph arrangement architecture of given shape is formed between two kinds of interfaces；
102nd, metal oxide precursor is coated on the substrate with the micro-nano graph arrangement architecture formed, from
Wetting and the self assembly behavior of wetting removal occur for hair, obtain patterned orderly metal-oxide film.
Preferably, the hydrophilic substrate includes：Glass, quartz, silica, silicon are handled other hard by hydrophily
Matter or flexible substrate；The hydrophily processing method includes：UV ozone irradiates or plasma bombardment；The hydrophily processing
Material includes：Aminopropyl triethoxysilane APTES, piranha solution；
The hydrophobic substrate includes：All hard or flexible substrate undressed or Jing Guo hydrophobic treatment；It is described to dredge
Aqueous treatment material includes：Octadecyl trichlorosilane alkane, hmds, dimethyl silicone polymer, polytetrafluoroethylene (PTFE) or complete
Fluororesin CYTOP.
Preferably, the thickness range of the micro-nano graph is 0.01 μm~100 μm, the characteristic size model of micro-nano graphic structure
Enclose for 1 μm~5000 μm.
Preferably, the micro-nano graph arrangement architecture of the given shape includes：Regular micro-nano graph and irregular micro-nano
Figure；The regular micro-nano graph includes：Circular, square, triangle.
Preferably, the tolerable temperature scope of the micro-nano graphic structure is -10 DEG C~600 DEG C.
Preferably, realize it is described by metal oxide precursor be coated in formed there is the micro-nano graph arrangement architecture
Substrate on, spontaneous generation wetting and the self assembly behavior of wetting removal, obtain it is patterned in order metal-oxide film work
Skill, including spin coating, blade coating, drop coating, lifting, spraying.
Preferably, methods described also includes：
Using one or more metal salt as the metal oxide precursor solute, dissolving in a solvent, with
Metal oxide precursor is put, 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：
Dimethoxy-ethanol, DMF, acetylacetone,2,4-pentanedione, ethylene glycol, ethanol；The inorganic solvent includes：Deionized water, ammoniacal liquor, hydrogen peroxide.
Preferably, it is described that metal oxide precursor is coated in the lining with the micro-nano graph arrangement architecture formed
On bottom, after spontaneous generation wetting and the self assembly behavior of wetting removal, patterned gold in order is obtained by one or many annealing
Belong to sull, the temperature range of the annealing is 80 DEG C~500 DEG C.
Preferably, hydrophobe is a relative concept, when the different two kinds of interfaces of hydrophobe of formation surface energy, the metal
Static pure water contact angle of the oxide in underlay substrate hydrophobic region is more than with the static pure water contact angle difference in hydrophilic region
30°。
The embodiment of the present invention additionally provides a kind of graphical preparation method of orderly self assembly of above-mentioned metal oxide and is prepared into
The metal-oxide film arrived.
Above-mentioned technical proposal has the advantages that：This method possesses not damaged, low-material-consumption, disposable ad-hoc location figure
The advantages of shape, and it is applied to rigid substrate (glass, silica, silicon etc.) and flexible substrate (PET, PDMS, PI simultaneously
Deng).Graphic method described in the embodiment of the present invention utilizes the surface energy difference at two kinds of interfaces of hydrophobe, realizes metal oxide half
Conductor precursor body hydrophilic pattern region sedimentation, and the embodiment of the present invention obtain patterned metal sull can apply
In high benefit, FET device is prepared on a large scale, senser element prepares and solar cell device.
Graphical metal-oxide film in order obtained by the embodiment of the present invention can be applied to preparing field effect transistor
Application in tube device, senser element or solar cell device.Graphical orderly metal oxygen obtained by the embodiment of the present invention
Compound film can be applied to preparing the preparation of rigid electronic device.Graphical metal oxidation in order obtained by the embodiment of the present invention
Thing film can be applied to preparing flexible electronic device preparation.
As shown in Fig. 2 it is in the contact of clean silica surface (not doing parent/hydrophobic treatment) described in the embodiment of the present invention
Angle.Above-mentioned technical proposal of the embodiment of the present invention is described in detail below by way of application example：
Application example 1：
As shown in figure 3, the contact angle of the silica surface of the present invention after hydrophobic material HMDS processing is
81.2°.As shown in figure 4, the contact angle for being the HMDS coating silicon dioxides surface of the present invention after the processing of UV ozone is
4.8°.And the technological process according to Fig. 5, on the same substrate, two kinds of different regions of surface free energy can be produced simultaneously, its
The difference of contact angle is 76.4 °.Using the difference, it may be implemented in self assembly on substrate and prepare metal-oxide film matrix.Tool
Body is implemented as follows.
It is preparing metal oxide precursor first.By the water of indium (III) nitrate bought from Sigma-Aldrich
Compound (Grade 99.9%), according to 0.1mol/L concentration, it is dissolved in organic solvent 2-methyl cellosolve (anhydrous, 99.8%).
Finally place it in magnetic to shake on agitator, stirred 3 hours with 800rpm rotating speeds, you can obtain the presoma of indium oxide.
Then according to technological process shown in Fig. 5, close and distant water process is carried out to substrate 41.We select in this embodiment
Substrate 41 be to have the silicon chip of 100nm silica, be cutting, cleaning silicon chip first, 4 inches of silicon chip cut into 1.5cm
× 1.5cm sizes, then by silicon chip 41 be immersed in successively purity be 99.99% acetone, purity be 99.99% ethanol and deionization
It is cleaned by ultrasonic in water each 30 minutes, then the residual moisture of silicon chip 41 is blown away with nitrogen, and silicon chip 41 is placed on to 110 DEG C of hot plate
On, heat is dried 10 minutes, removes the steam remained on silicon chip 41.The silicon chip 41 of drying is placed on desk-top sol evenning machine, spin coating
HMDS films 42 (rotating speed 2000rpm, time 60s).Then it is placed with figure on the silicon chip coated with HMDS films 42
Metal mask version 43.Then put it into UV ozone machines, handled 3 minutes with UV light (h υ) 44.It can obtain two kinds of surfaces
The different region of free energy.
It is finally to prepare indium oxide film matrix in patterned hydrophobe substrate.The film side selected in this embodiment
Method is spin coating.The rotating speed of spin coating is 3000rpm, time 30s.It can obtain forerunner's volume matrix 45 of indium oxide.Finally in heat
On plate, 350 degrees Celsius of one hours of annealing, you can obtain the film matrix 45 of indium oxide, see Fig. 6.
Application example 2：
As shown in fig. 7, the contact angle of the silica surface of the present invention after hydrophobic material CYTOP processing is
116.4°.As shown in figure 8, it is connecing for the CYTOP coating silicon dioxides surface of the present invention after plasma etch processes
Feeler is 18.6.And the technological process according to Fig. 9, on the same substrate, it is different that two kinds of surface free energies can be produced simultaneously
Region, the difference of its contact angle is 97.8 °.Using the difference, it may be implemented in self assembly on substrate and prepare metal-oxide film
Matrix.Specific implementation is as follows.
It is preparing metal oxide precursor first.By the hydrate for the stannous chloride bought from Sigma-Aldrich
(Grade99.9%), according to 0.15mol/L concentration, organic solvent 2-methyl cellosolve (anhydrous, 99.8%) is dissolved in, then add
The acetylacetone,2,4-pentanedione of upper equimolar concentration.Finally place it in magnetic to shake on agitator, stirred 3 hours with 800rpm rotating speed, you can
Obtain the presoma of tin oxide.
Followed by the technological process according to Fig. 9, close and distant water process is carried out to substrate.We select in this embodiment
Substrate be the silicon chip 81 for having 100nm silica.It is cutting, cleaning silicon chip first, 4 inches of silicon chip is cut into 1.5cm
× 1.5cm sizes, then by silicon chip 81 be immersed in successively purity be 99.99% acetone, purity be 99.99% ethanol and deionization
It is cleaned by ultrasonic in water each 30 minutes, then residual moisture is blown away with nitrogen, and silicon chip 81 is placed on 110 DEG C of hot plate, heat is dried
10 minutes, remove residual steam.The silicon chip 81 of drying is placed on desk-top sol evenning machine, spin coating CYTOP films 82, first with
500r/m speed rotation 10s, then 40s is rotated with 5000r/m speed.CYTOP solution be by CYTOP and CYTOP solvents by
It is 1 according to mass ratio:6 concentration prepares gained.Then the silicon chip that spin coating there are CYTOP films 82 is placed on 120 DEG C of hot plate and dried
Roasting 30min.After baking, sample is taken out.Treat that sample is cooled to room temperature, after metal mask version 83 is placed on sample, then
Put into plasma machines, O2plasma 84 handles 90s.It can be formed graphically, obtain two kinds of different areas of surface free energy
Domain.
It is finally to prepare SnO 2 thin film matrix in patterned hydrophobe substrate.The film selected in this embodiment
Method is inclination drop coating, you can obtains forerunner's volume graphic 85 of tin oxide.Finally oxygen is can obtain by 400 degrees Celsius of annealing
Change the film pattern 85 of tin, see Figure 10.
Application example 3：
As shown in fig. 7, the contact angle of the silica surface of the present invention after hydrophobic material CYTOP processing is
116.4°.As shown in figure 8, it is connecing for the CYTOP coating silicon dioxides surface of the present invention after plasma etch processes
Feeler is 18.6.And the technological process according to Fig. 9, on the same substrate, it is different that two kinds of surface free energies can be produced simultaneously
Region, the difference of its contact angle is 97.8 °.Using the difference, it may be implemented in self assembly on substrate and prepare metal-oxide film
Matrix.Specific implementation is as follows.
It is preparing metal oxide precursor first.By from Sigma-Aldrich buy will be from Sigma-Aldrich
The hydrate (Grade 99.9%) and zinc salt hydrate (Grade 99.999%) of indium (III) nitrate of purchase, according to
0.15mol/L concentration, organic solvent 2-methyl cellosolve (anhydrous, 99.8%) is dissolved in respectively, then by respective metal nitre
Acid salt solution, it is placed on magnetic and shakes on agitator, is stirred 2 hours with 800rpm rotating speed.According still further to indium：Zinc=1:1 volume ratio, mix
Close, obtain indium-zinc mixed solution.Then by indium-zinc mixed solution, it is placed on magnetic and shakes on agitator, 2 is stirred with 800rpm rotating speed
Hour, you can obtain InZnO presoma.
Followed by the technological process according to Fig. 9, close and distant water process is carried out to substrate.We select in this embodiment
Substrate be 5 μ m-thicks PI substrates 81.It is cutting, cleaning PI substrates first, the PI substrates of 4A sizes is cut into 4cm × 4cm
Size, then by PI substrates 81 be immersed in successively purity be 99.99% acetone, purity be in 99.99% ethanol and deionized water
It is cleaned by ultrasonic each 30 minutes, then with nitrogen residual moisture, and PI substrates 81 are placed on 110 DEG C of hot plate, heat is dried 10 minutes,
Remove the steam of residual.The PI substrates 81 of drying are placed on desk-top sol evenning machine, spin coating CYTOP films 82, first with 500r/m
Speed rotation 10s, then 40s is rotated with 5000r/m speed.CYTOP solution is according to quality by CYTOP and CYTOP solvents
Than for 1:6 concentration prepares gained.Then the PI substrates 81 that spin coating there are CYTOP films 82 are placed on 120 DEG C of hot plate and toasted
30min.After baking, sample is taken out.Treat that sample is cooled to room temperature, after metal mask version 83 is placed on sample, then put
Enter in plasma machines, O2plasma 84 handles 90s.Graphical matrix can be formed, it is different to obtain two kinds of surface free energies
Region.
It is finally to prepare InZnO film matrix in patterned hydrophobe substrate.The film side selected in this embodiment
Method is blade coating.InZnO presomas are dropped in into the patterned edge of PI substrates 81, glass bar is then placed on superjacent, profit
With capillarity, capillary bridge is formed, it is last toward fixed-direction dragging glass bar (capillary bridge), you can before forming InZnO
Drive volume matrix 85.InZnO film matrix 85 is finally can obtain by 300 degrees Celsius of annealing, sees Figure 13.
Application example 4：
As shown in Fig. 2 the contact angle in clean glass surface (not doing parent/hydrophobic treatment) is 48.7 °.As shown in fig. 7, it is
The contact angle of glass surface of the present invention after hydrophobic material CYTOP processing is 116.4 °.And according to Figure 11
Technological process, on the same substrate, two kinds of different regions of surface free energy can be produced simultaneously, the difference of its contact angle is
67.7°.Using the difference, it may be implemented in self assembly on substrate and prepare metal-oxide film matrix.And aoxidized using the metal
Thing film matrix prepares MOS transistor matrix.Specific implementation is as follows.
It is preparing metal oxide precursor first.By the water of indium (III) nitrate bought from Sigma-Aldrich
Compound (Grade 99.9%), zinc salt hydrate (Grade 99.999%) and gallium (III) nitrate hydrate (crystallization,
Grade 99.9%), respectively according to 0.05mol/L concentration, it is dissolved in organic solvent 2-methyl cellosolve (anhydrous, 99.8%).
Then by respective metal-nitrate solutions, it is placed on magnetic and shakes on agitator, is stirred 2 hours with 800rpm rotating speed.According still further to indium：
Zinc：Gallium=6:3:1 volume ratio, mixing, obtains indium-zinc-gallium mixed solution.Then by indium-zinc-gallium mixed solution, it is placed on magnetic
Shake on agitator, stirred 2 hours with 800rpm rotating speed, you can obtain InGaZnO presoma.
Followed by the technological process according to Figure 11, close and distant water process is carried out to substrate.We select in this embodiment
Substrate is the silicon chip 101 for having 100nm silica.It is cleaning silicon chip 101 first, silicon chip 101 is immersed in purity successively
It is to be cleaned by ultrasonic in 99.99% ethanol and deionized water each 30 minutes for 99.99% acetone, purity, then residual is blown away with nitrogen
Moisture, and silicon chip 101 is placed on 110 DEG C of hot plate, heat is dried 10 minutes, removes the steam of residual.
The silicon chip 101 of drying is placed on desk-top sol evenning machine (KW-4A types, Chinese Academy of Sciences Microelectronics Institute), revolved
Resist coating 102 (viscosity 30MPa), 9s is first rotated with 500r/m speed, then 40s is rotated with 2000r/m speed.Then
The silicon chip that spin coating has photoresist 102 is placed on 120 DEG C of hot plate and toasts 2min.After baking, sample is taken out, treats that sample is cold
But to room temperature, sample is placed in exposure machine, UV exposure-processeds 21s.Sample is immersed again in the developer solution matched with photoresist
Interior development 1min, finally with deionized water rinsing and dry up.
Then on the substrate of photoetching offset plate figure, desk-top sol evenning machine, spin coating CYTOP films 103, spin coating rotating speed are used
5000rpm, time 60s.Then sample is placed on 100 DEG C of hot plate, heat dries 6min, solidification CYTOP films 103.Finally
Sample is immersed in purity as 10min in 99.99% acetone, removes photoresist 102.Finally leave the image conversion of CYTOP films 103
Substrate.
It is finally to prepare InGaZnO film matrix 104 in patterned hydrophobe substrate.The painting selected in this embodiment
Film method is blade coating.InGaZnO presoma is dropped in into patterned substrate edge edge, then glass bar is placed on solution
Side, using capillarity, capillary bridge is formed, it is last toward fixed-direction dragging glass bar (capillary bridge), you can be formed
InGaZnO forerunner's volume matrix 104.InGaZnO film matrix 104 is finally can obtain by 350 degrees Celsius of annealing, is seen
Figure 12.
MOS transistor matrix is prepared followed by using InGaZnO 104 gusts of film square.Oxide transistor
Device architecture is shown in that Figure 14 oxide transistors include gate electrode 131, insulating barrier 132, active channel layer 133, source-drain electrode
134th, 135, the structure of the oxide transistor of CYTOP films 136. is bottom gate top contact, and gate electrode is N-type heavily doped silicon
131, insulating barrier is 100nm silica 1 32, and active channel layer is the film square of the InGaZnO prepared by the implementation case
Battle array 133, source-drain electrode are the aluminium electrodes 134,135 prepared with metal mask version by hot evaporation.Utilize InGaZnO film square
Battle array prepares MOS transistor matrix and sees Figure 15.
Application example above-mentioned technical proposal of the present invention has the advantages that：This method possesses not damaged, low-material-consumption, one
The advantages of secondary property specific location graphical, and it is applied to rigid substrate (glass, silica, silicon etc.) and flexible substrate simultaneously
(PET, PDMS, PI etc.).Graphic method described in the embodiment of the present invention utilizes the surface energy difference at two kinds of interfaces of hydrophobe, realizes
Metal-oxide semiconductor (MOS) presoma hydrophilic pattern region sedimentation, and the embodiment of the present invention obtain patterned metal oxidation
Thing film can be applied to high benefit, prepare FET device on a large scale, senser element prepares and solar cell device.
Graphical metal-oxide film in order obtained by application example of the present invention can be applied to preparing field-effect crystalline substance
Application in body tube device, senser element or solar cell device.Graphical gold in order obtained by application example of the present invention
Category sull can be applied to preparing the preparation of rigid electronic device.Graphical gold in order obtained by application example of the present invention
Category sull can be applied to preparing flexible electronic device preparation.
It should be understood that the particular order or level of the step of during disclosed are the examples of illustrative methods.Based on setting
Count preference, it should be appreciated that during the step of particular order or level can be in the feelings for the protection domain for not departing from the disclosure
Rearranged under condition.Appended claim to a method gives the key element of various steps with exemplary order, and not
It is to be limited to described particular order or level.
In above-mentioned detailed description, various features combine in single embodiment together, to simplify the disclosure.No
This open method should be construed to reflect such intention, i.e. the embodiment of theme claimed needs to compare
The more features of feature clearly stated in each claim.On the contrary, as appended claims is reflected
Like that, the present invention is in the state fewer than whole features of disclosed single embodiment.Therefore, appended claims
It is hereby expressly incorporated into detailed description, wherein each claim is alone as the single preferred embodiment of the present invention.
To enable any technical staff in the art to realize or using the present invention, disclosed embodiment being entered above
Description is gone.To those skilled in the art；The various modification modes of these embodiments will be apparent from, and this
The General Principle of text definition can also be applied to other embodiments on the basis of the spirit and scope of the disclosure is not departed from.
Therefore, the disclosure is not limited to embodiments set forth herein, but most wide with principle disclosed in the present application and novel features
Scope is consistent.
Described above includes the citing of one or more embodiments.Certainly, in order to above-described embodiment is described and description portion
The all possible combination of part or method is impossible, but it will be appreciated by one of ordinary skill in the art that each implementation
Example can do further combinations and permutations.Therefore, embodiment described herein is intended to fall into appended claims
Protection domain in all such changes, modifications and variations.In addition, with regard to the term used in specification or claims
"comprising", the mode that covers of the word are similar to term " comprising ", just as " including " solved in the claims as link word
As releasing.In addition, the use of any one term "or" in the specification of claims is to represent " non-exclusionism
Or ".
Above-described embodiment, the purpose of the present invention, technical scheme and beneficial effect are carried out further
Describe in detail, should be understood that the embodiment that the foregoing is only the present invention, be not intended to limit the present invention
Protection domain, within the spirit and principles of the invention, any modification, equivalent substitution and improvements done etc., all should include
Within 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.
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