CN109735816A - Vanadium dioxide fexible film and preparation method thereof - Google Patents
Vanadium dioxide fexible film and preparation method thereof Download PDFInfo
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- CN109735816A CN109735816A CN201910145023.4A CN201910145023A CN109735816A CN 109735816 A CN109735816 A CN 109735816A CN 201910145023 A CN201910145023 A CN 201910145023A CN 109735816 A CN109735816 A CN 109735816A
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Abstract
A kind of vanadium dioxide fexible film and its method comprising following steps: step 1, the epitaxial growth oxide buffer layer in rigid substrate, the epitaxial growth vanadium dioxide film again on oxide buffer layer；Step 2, in one layer of the spin coating of vanadium dioxide film surface organic support protective film, and it is dry；Step 3 removes oxide buffer layer by wet etching, and the vanadium dioxide film that obtained organic support protective film is protected is transferred in flexible substrate and is stood and makes it dry；Step 4, organic support protective film that bonding is washed using organic solvent, and it is dried to obtain vanadium dioxide fexible film.Preparation process of the present invention is simple, at low cost, controllability is strong, realizes the flexibility of the vanadium dioxide film of preferred orientation, is of great significance to the flexible device based on vanadium dioxide film is expanded.
Description
Technical field
The present invention relates to thin film epitaxy preparation technical fields, more particularly to a kind of vanadium dioxide fexible film and its preparation
Method.
Background technique
With the rise of artificial intelligence, have developed all kinds of portable devices, this to the volume of functional material in equipment, again
Whether amount, integrated level can be bent etc. and to propose challenge.For traditional body material, thin-film material has body
Product is small, light-weight, the features such as being easily integrated, is widely used in each field, thus the thin-film material with specific function by
Extensive concern, it is however generally that they may have electricity, optical, magnetics and acoustics etc. particularity
Matter can be used for developing sensor, memory, solar battery, energy converter etc. based on these properties.Flexible thin-film material then has
The features such as standby flexible, foldable, compared with traditional stiffness films material, flexible thin-film material's scope of application is wider, more
There is application prospect.
Vanadium dioxide is a kind of typical metal-insulator transition material, metal-insulator transition temperature near 68 DEG C,
The variation of the optical transmittance occurred in phase transition process, the mutation of resistance value are the interested focuses of researcher, so that dioxy
Change vanadium photoswitch, intelligent glass coating, Mott transistor, memristor, strain gauge, gas sensor, temperature sensor,
Thermal actuator etc. has great potentiality.Well-crystallized, the vanadium dioxide film haveing excellent performance generally require at high temperature
Growth, this requires flexible substrates to be able to bear higher temperature, and has suitable lattice parameter, limits to a certain extent
Application of the vanadium dioxide in flexible electronic device is made.
To sum up, it currently needs to find the good vanadium dioxide fexible film of one kind applied widely, simple process, controllability
Preparation method.
Summary of the invention
In view of this, the main purpose of the present invention is to provide a kind of vanadium dioxide fexible film and preparation method thereof, with
Phase at least is partially solved at least one of above-mentioned the technical issues of referring to.
To achieve the above object, technical scheme is as follows:
As one aspect of the present invention, a kind of preparation method of vanadium dioxide fexible film, including following step are provided
It is rapid:
Step 1, the epitaxial growth oxide buffer layer in rigid substrate, the epitaxial growth again on the oxide buffer layer
Vanadium dioxide film；
Step 2, in one layer of vanadium dioxide film surface spin coating organic support protective film, and it is dry；
Step 3 removes the oxide buffer layer by wet etching, by the two of the protection of obtained organic support protective film
Vanadium oxide film is transferred in flexible substrate and stands and makes it dry；
Step 4, organic support protective film that bonding is washed using organic solvent, and it is dried to obtain vanadium dioxide flexible thin
Film.
As another aspect of the present invention, vanadium dioxide made from a kind of utilization preparation method as described above is provided
Fexible film, comprising:
Flexible substrate is polyethylene terephthalate, polyimides, polyphenylene sulfide or polyether-ether-ketone flexible thin
Film；And
Vanadium dioxide film has preferred orientation, is formed in the flexible substrate.
As another aspect of the invention, a kind of flexible contact sensor is provided, comprising:
Vanadium dioxide fexible film made from preparation method as described above comprising flexible substrate and be formed in described
Vanadium dioxide film in flexible substrate；And flexible electrode, it is formed on vanadium dioxide film；
Wherein, the vanadium dioxide film has preferred orientation.
It can be seen from the above technical proposal that a kind of vanadium dioxide fexible film and preparation method thereof of the invention at least has
There is one of following beneficial effect:
(1) present invention is using oxide buffer layer as sacrificial layer, and epitaxial growth preferentially takes on oxide buffer layer first
To vanadium dioxide film, the flexibility of vanadium dioxide film is then realized by etching transfer, preparation process has stringent meaning
Controllability in justice；
(2) present invention selects zinc oxide as oxide buffer layer, using hydrochloric acid solution as corrosive liquid, can guarantee right
It keeps vanadium dioxide object mutually good while oxide buffer layer is corroded, there is outstanding selectivity；
(3) preparation process of the present invention is simple, at low cost, controllability is strong, applied widely, and substrate and organic solvent etc. can weigh
It is multiple to utilize, there is important impetus to realization vanadium dioxide flexible electronic device development.
Detailed description of the invention
Fig. 1 is the process that the embodiment of the present invention prepares vanadium dioxide fexible film based on oxide buffer layer wet etching
Figure；
Fig. 2 is the XRD spectra of vanadium dioxide fexible film after transfer of the embodiment of the present invention；
Fig. 3 is that electric current changes over time curve graph when the contact sensor of preparation of the embodiment of the present invention tests human pulse.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in further detail.
The invention discloses a kind of vanadium dioxide fexible films and preparation method thereof, suitable by growing in rigid substrate
Sacrificial layer material and preferred orientation vanadium dioxide film, by wet etching transfer can then obtain vanadium dioxide flexible
Film helps to realize application of the vanadium dioxide film material in terms of wearable device, oxide flexible electronic device.
In an exemplary embodiment of the present invention, a kind of preparation method of vanadium dioxide fexible film is provided, such as Fig. 1 institute
Show comprising following steps:
Step 1, the epitaxial growth oxide buffer layer in rigid substrate, the epitaxial growth dioxy again on oxide buffer layer
Change vanadium film；
In this step, rigid substrate is, for example, sapphire, mica, titanium dioxide or magnesium lead niobate-lead titanates (PMN-PT)
Substrate etc..
Oxide buffer layer is preferably zinc oxide, is grown by magnetron sputtering, and the temperature of growth is room temperature to 800
DEG C, preferably 400~800 DEG C, atmosphere is the mixed gas atmosphere of argon gas and oxygen, and oxygen concentration can be according to the target used
Material and process condition are adjusted, and the target used is zinc oxide target or zinc target etc..It is worth noting that, need to select has properly
The material of lattice parameter can make vanadium dioxide film epitaxial growth on it as oxide buffer layer.Preferably, oxidation
Object buffer layer with a thickness of 10nm~2 μm；It wherein needs to select suitable buffer layer thickness, thickness is excessively thin may to be caused to corrode
Solution is not easily accessible, and extends etching time, and thickness may cause the decline of epitaxial film quality later, influence subsequent fexible film
Quality and corresponding device performance.
Vanadium dioxide film is grown by magnetron sputtering, and the temperature of growth is 100~900 DEG C, preferably 350~
750 DEG C, atmosphere be argon gas and oxygen mixed gas atmosphere or pure argon atmosphere, the selection of atmosphere type and
Oxygen concentration therein can be adjusted according to specifically used target and process condition, and the target used is vanadic anhydride
Target, vanadium trioxide target or vanadium metal target etc..As preferred vanadium dioxide film with a thickness of 20nm~1.5 μm.
In the present embodiment, using c-plane sapphire substrate, Sapphire Substrate successively uses acetone before growing, and dehydrated alcohol and goes
Ionized water is cleaned by ultrasonic 15 minutes respectively；Respectively using Zinc oxide powder compacting target and vanadic anhydride business target, oxidation
The growth temperature of zinc is 600 DEG C, and with a thickness of 200nm, growth gasses atmosphere is the mixed gas atmosphere of argon gas and oxygen；Titanium dioxide
The growth temperature of vanadium is 550 DEG C, and with a thickness of 200nm, the atmosphere of growth is in argon gas and oxygen mixed gas atmosphere.
Step 2, one layer of the spin coating of vanadium dioxide film surface organic support protective film in above-mentioned growth, and it is dry；
Organic support protective film is by the way that rosin, polymethyl methacrylate (PMMA), paraffin or black wax etc. is organic
Progress spin coating obtains after object is dissolved in organic solvent, and organic solvent is ethyl alcohol, acetone or toluene etc..Organic support protective film is to dioxy
Change vanadium film to play a protective role, can prevent vanadium dioxide film in subsequent operation from rupturing.
In the present embodiment, business black wax is dissolved in toluene solution, then in one layer of black wax support of vanadium dioxide surface spin coating
Protective layer, the revolving speed of spin coating is between 1500~2500 revs/min, and in drying at room temperature.
Step 3 removes oxide buffer layer by wet etching, by the titanium dioxide of the obtained organic support protective film of bonding
Vanadium film is transferred in flexible substrate and stands and makes it dry；
This step can carry out wet etching in acid solution or aqueous slkali to remove oxide buffer layer, preferably 5%~
30% hydrochloric acid solution has good etch selectivities to zinc oxide while accelerating corrosion rate.It is noticeable
It is, if selecting conventional phosphoric acid corrosion liquid etc., it is very slow to will lead to corrosion rate, and etch selectivities are bad.
Flexible substrate be, for example, polyethylene terephthalate (PET), polyimides (PI), polyphenylene sulfide (PPS) or
The conventional flexibles films such as polyether-ether-ketone (PEEK), preparation method of the invention have universality, no longer need to the resistance to of flexible substrate
The performances such as high temperatures and lattice parameter are particularly limited.
In the present embodiment, there is the vanadium dioxide film of black wax support protective layer to be placed in above-mentioned hydrochloric acid solution surface spin coating
In, wherein spin coating has facing upward for black wax.Oxide buffer layer corrosion over time finishes, and black wax supports protective layer viscous
The vanadium dioxide film of conjunction is separated with substrate, wherein black wax upwardly, the vanadium dioxide for being bonded black wax using flexible substrate
Film takes out from hydrochloric acid solution, cleans in deionized water twice, so that vanadium dioxide film is transferred in flexible substrate,
It is placed in dry environment, is completely dried to film.
Step 4, organic support protective film that bonding is washed using organic solvent, and it is dried to obtain vanadium dioxide flexible thin
Film.
The organic solvent that this step uses is ethyl alcohol, acetone or toluene etc..
In the present embodiment, the black wax support protective layer of bonding is cleaned up using toluene solution, specific operating method
It is to tilt fexible film, using dropper in one section of high toluene solution that drips, receives toluene solution in other end reagent bottle
Then in drying at room temperature, vanadium dioxide fexible film can be obtained until black wax is completely dissolved completely with the black wax of dissolution.
Fig. 2 is the XRD spectra of vanadium dioxide fexible film after transfer of the embodiment of the present invention, from XRD spectra it can be seen that turning
In addition to the peak XRD of substrate PET, only (020) face peak of vanadium dioxide after shifting.XRD spectra after transfer shows vanadium dioxide
Object is mutually good.
Further, plating gold electrode using some conventional methods on obtained vanadium dioxide fexible film surface can make
At contact sensor, concrete operations are as follows: vanadium dioxide fexible film is fixed on to the stainless steel mask plate of customization with high temperature gummed tape
On, gold electrode is deposited using vapor deposition instrument, for gold electrode having a size of 5mm*5mm, gold electrode spacing is 0.1mm, gold electrode with a thickness of
500nm.Fig. 3 is that the contact sensor of preparation of the embodiment of the present invention tests human pulse electric current and changes over time curve graph, can be with
It was found that the flexible device design based on the preparation of vanadium dioxide fexible film is simple, practicability is good.
In conclusion the present invention grows the vanadium dioxide film of oxide buffer layer and preferred orientation first, it is then spin coated onto
Protective layer is supported, wet etching oxide sacrificial layer is recycled, is separated to substrate and vanadium dioxide, takes out two using fexible film
Vanadium oxide film finally cleans the flexible vanadium dioxide film that support protective layer can be obtained well-crystallized, have excellent performance.This hair
Bright preparation process is simple, at low cost, strong, the most of material of controllability can be recycled, solve outside the flexible vanadium dioxide of preparation
Prolong the problem of film, effectively expands the application range of vanadium dioxide film.
So far, attached drawing is had been combined the present embodiment is described in detail.According to above description, those skilled in the art
It should be to the present invention is based on a kind of vanadium dioxide fexible films and preparation method thereof clear understanding.Preparation process of the present invention
Simply, at low cost, it solves the problems, such as to prepare vanadium dioxide fexible film, for expanding vanadium dioxide device in flexible electronic
Application in field and wearable device is of great importance.
It should be noted that in attached drawing or specification text, the implementation for not being painted or describing is affiliated technology
Form known to a person of ordinary skill in the art, is not described in detail in field.In addition, the above-mentioned definition to each element and method is simultaneously
It is not limited only to various specific structures, shape or the mode mentioned in embodiment, those of ordinary skill in the art can carry out letter to it
It singly changes or replaces, such as: oxide buffer layer or vanadium dioxide growth also can be used pulse laser deposition or atomic beam heavy
The methods of product.
It should also be noted that, can provide the demonstration of the parameter comprising particular value herein, but these parameters are without definite etc.
In corresponding value, but analog value can be similar in acceptable error margin or design constraint.In addition, unless specifically described
Or the step of must sequentially occurring, there is no restriction for the sequences of above-mentioned steps in listed above, and can be changed according to required design
Or it rearranges.And above-described embodiment can be mixed with each other and be arranged in pairs or groups using or with other realities based on the considerations of design and reliability
It applies a mix and match to use, i.e., the technical characteristic in different embodiments can freely form more embodiments.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in protection of the invention
Within the scope of.
Claims (10)
1. a kind of preparation method of vanadium dioxide fexible film, which is characterized in that the preparation method comprises the following steps:
Step 1, the epitaxial growth oxide buffer layer in rigid substrate, the epitaxial growth dioxy again on the oxide buffer layer
Change vanadium film；
Step 2, in one layer of vanadium dioxide film surface spin coating organic support protective film, and it is dry；
Step 3 removes the oxide buffer layer by wet etching, the titanium dioxide that obtained organic support protective film is protected
Vanadium film is transferred in flexible substrate and stands and makes it dry；
Step 4, organic support protective film that bonding is washed using organic solvent, and it is dried to obtain vanadium dioxide fexible film.
2. preparation method according to claim 1, which is characterized in that in step 1, the rigid substrate is sapphire, cloud
Female, titanium dioxide or magnesium lead niobate-lead titanates (PMN-PT) substrate.
3. preparation method according to claim 1, which is characterized in that in step 1, the oxide buffer layer is oxidation
Zinc, the temperature of growth are room temperature to 800 DEG C, and preferably 400~800 DEG C, atmosphere is the mixed gas atmosphere of argon gas and oxygen
It encloses, the target used is zinc oxide target or zinc target.
4. preparation method according to claim 1, which is characterized in that in step 1, the vanadium dioxide film growth
Temperature is 100~900 DEG C, and preferably 350~750 DEG C, atmosphere is the mixed gas atmosphere or straight argon of argon gas and oxygen
Atmosphere is enclosed, and the target used is vanadic anhydride target, vanadium trioxide target or vanadium metal target.
5. preparation method according to claim 1, which is characterized in that in step 1, the thickness of the oxide buffer layer
For 10nm~2 μm；The vanadium dioxide film with a thickness of 20nm~1.5 μm.
6. preparation method according to claim 1, which is characterized in that in step 2, organic support protective film is logical
Progress spin coating after rosin, polymethyl methacrylate (PMMA), paraffin or black wax are dissolved in organic solvent is crossed to obtain, it is described organic
Solvent is ethyl alcohol, acetone or toluene.
7. preparation method according to claim 1, which is characterized in that in step 3, by setting step 2 obtained device
Wet etching is carried out in corrosive liquid, the corrosive liquid is acid solution or alkali, preferably, the corrosive liquid is 5%~30%
Hydrochloric acid solution.
8. preparation method according to claim 1, it is characterised in that:
In step 3, the flexible substrate is polyethylene terephthalate (PET) or polyimides (PI), polyphenylene sulfide
(PPS) or polyether-ether-ketone (PEEK) fexible film；And/or
In step 4, the organic solvent used is ethyl alcohol, acetone or toluene.
9. vanadium dioxide fexible film made from a kind of preparation method using as described in claim 1 to 8 any one, packet
It includes:
Flexible substrate is polyethylene terephthalate, polyimides, polyphenylene sulfide or polyether-ether-ketone fexible film；With
And
Vanadium dioxide film has preferred orientation, is formed in the flexible substrate.
10. a kind of flexible contact sensor, comprising:
Vanadium dioxide fexible film made from preparation method as described in claim 1 to 8 any one comprising flexible substrate
And it is formed in the vanadium dioxide film in the flexible substrate；And
Flexible electrode is formed on the vanadium dioxide film；
Wherein, the vanadium dioxide film has preferred orientation.
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| CN201910145023.4A CN109735816A (en) | 2019-02-26 | 2019-02-26 | Vanadium dioxide fexible film and preparation method thereof |
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| CN201910145023.4A CN109735816A (en) | 2019-02-26 | 2019-02-26 | Vanadium dioxide fexible film and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075698A (en) * | 2020-08-18 | 2022-02-22 | 中国科学院半导体研究所 | Preparation method of cobalt ferrite flexible single crystal film |
| RU2793624C1 (en) * | 2022-12-01 | 2023-04-04 | федеральное государственное автономное образовательное учреждение высшего образования "Южный федеральный университет" | Switchable two-band filter on surface acoustic waves |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105845771A (en) * | 2016-05-01 | 2016-08-10 | 上海大学 | High-performance VO2 thermal-sensitive film employing buffer layer for inducing growth and preparation method of high-performance VO2 thermal-sensitive film |
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2019
- 2019-02-26 CN CN201910145023.4A patent/CN109735816A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105845771A (en) * | 2016-05-01 | 2016-08-10 | 上海大学 | High-performance VO2 thermal-sensitive film employing buffer layer for inducing growth and preparation method of high-performance VO2 thermal-sensitive film |
Non-Patent Citations (1)
| Title |
|---|
| 廖非易: "《电子科技大学博士毕业论文》", 30 June 2018 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075698A (en) * | 2020-08-18 | 2022-02-22 | 中国科学院半导体研究所 | Preparation method of cobalt ferrite flexible single crystal film |
| RU2793624C1 (en) * | 2022-12-01 | 2023-04-04 | федеральное государственное автономное образовательное учреждение высшего образования "Южный федеральный университет" | Switchable two-band filter on surface acoustic waves |
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Application publication date: 20190510 |