CN206921493U - Graphene-based laminated film with cavity - Google Patents
Graphene-based laminated film with cavity Download PDFInfo
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- CN206921493U CN206921493U CN201720798830.2U CN201720798830U CN206921493U CN 206921493 U CN206921493 U CN 206921493U CN 201720798830 U CN201720798830 U CN 201720798830U CN 206921493 U CN206921493 U CN 206921493U
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
- H01P11/00—Apparatus or processes specially adapted for manufacturing waveguides or resonators, lines, or other devices of the waveguide type
- H01P11/008—Manufacturing resonators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
- H01P7/00—Resonators of the waveguide type
- H01P7/06—Cavity resonators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
- H01Q1/364—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith using a particular conducting material, e.g. superconductor
- H01Q1/368—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith using a particular conducting material, e.g. superconductor using carbon or carbon composite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
- H01Q1/38—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith formed by a conductive layer on an insulating support
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/52—Means for reducing coupling between antennas; Means for reducing coupling between an antenna and another structure
- H01Q1/521—Means for reducing coupling between antennas; Means for reducing coupling between an antenna and another structure reducing the coupling between adjacent antennas
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Abstract
The utility model provides a kind of graphene-based laminated film with cavity, including：Bottom graphene film；The nanocrystalline pattern unit for the multiple repeated arrangements being formed on bottom graphene film；Each nanocrystalline pattern unit has the first nano crystal array and the second nanocrystalline support column around the first nano crystal array；The top of second nanocrystalline support column is higher than the top of the first nano crystal array；Top layer graphene film is covered at the top of nanocrystalline pattern unit, and with the top contact of the second nanocrystalline support column and do not contacted with the top of the first nano crystal array, form multiple closed cavities between multiple nanocrystalline pattern units and top layer graphene；Wherein, each closed cavity between top layer graphene film, the second nanocrystalline support column, the first nano crystal array by surrounding.Graphene-based laminated film of the present utility model can apply to antenna and obtain different frequency responses, and different sensitivity is obtained for sensor.
Description
Technical field
It the utility model is related to technical field of semiconductors, and in particular to a kind of graphene-based laminated film of cavity.
Background technology
Graphene is the best a kind of novel nano-material of most thin, maximum intensity, the electrical and thermal conductivity having now been found that, it is anti-
Tensile strength is about 100 times of ordinary steel, can bear about 2 tons of weight, and have good pliability.The electricity of graphene
Transport factor is 140 times of electron mobility in silicon, and temperature stability is high, and surface resistance is lower than copper, silver, be at room temperature it is conductive most
Good material.The specific surface area of graphene is big, and thermal conductivity is 36 times of silicon so that graphene has in terms of flexible conductive film
Important application.In optical means, the single-layer graphene absorptivity vertical to visible ray and near infrared band light is only 2.3%, right
The light non-selectivities of all wave bands absorbs, to from visible ray to Terahertz broadband light have absorption etc..
Due to the above-mentioned characteristic of graphene, graphene has in numerous areas such as mobile device, Aero-Space, new energy batteries
There is application potential.Particularly flexible and transparent device turns into one of trend of modern device development, therefore, how by graphene application
In various flexible and transparent devices be significant.
Utility model content
In order to overcome problem above, the utility model aim to provide a kind of graphene-based laminated film with cavity and its
Preparation method, more it is widely applied so that graphene has in flexible and transparent devices field.
In order to achieve the above object, the utility model provides a kind of graphene-based laminated film with cavity, and it is wrapped
Include：
Bottom graphene film；
The nanocrystalline pattern unit for the multiple repeated arrangements being formed on bottom graphene film；Each nanocrystalline pattern list
Member has the first nano crystal array and the second nanocrystalline support column around the first nano crystal array；Second nanocrystalline branch
The top of dagger is higher than the top of the first nano crystal array；
Top layer graphene film, be covered at the top of the nanocrystalline pattern unit, and with the second nanocrystalline support column
Top contact and do not contacted with the top of the first nano crystal array, formed between multiple nanocrystalline pattern units and top layer graphene
Multiple closed cavities；Wherein, each closed cavity is by top layer graphene film, the second nanocrystalline support column, the first nanocrystalline battle array
Surrounded between row.
Preferably, the single nanocrystalline pattern unit is rounded, rectangle or bow tie.
Preferably, the first nano crystal array is in Archimedes's array arrangement, or equidistantly matrix arrangement, or butterfly knot shape row
Cloth.
Preferably, adjacent nanocrystalline pattern unit shares one or more second nanocrystalline support columns, or adjacent receives
Second nanocrystalline support column of the brilliant pattern unit of rice is in contact connection.
Preferably, organic nano-EMI material is set between adjacent nanocrystalline pattern unit.
Preferably, the material of first nano crystal array is metal nano material；The second nanocrystalline support column
Material is insulating materials.
Preferably, the material of the described second nanocrystalline support column is metal oxide materials.
Preferably, the material of the described second nanocrystalline support column is identical with the material of first nano crystal array.
Preferably, first nano crystal array use for nano-wire array, the second nanocrystalline support column uses
For nano-pillar.
The utility model utilizes bottom graphene film, nano crystal array, nanocrystalline support column and top layer graphene film
Multiple closed cavities are built between graphene film jointly, due to bottom graphene film, top layer graphene film and nanocrystalline
Pattern unit is nanoscale, is had preferably flexible so that closed cavity can be with bottom graphene film, top layer graphene
The deformation of film and nanocrystalline pattern unit and change, also, due to the first nano crystal array, top layer graphene film and
Bottom graphene film is respectively provided with higher specific surface area, so that change of the graphene-based laminated film for the external world is visited
Survey is more sensitive, and sensitivity is higher.
When bottom graphene film, top layer graphene film and nanocrystalline pattern unit are by environmental stimuli, closing is empty
The volume and shape of chamber can change therewith, so that caused light, electric signal or resonant frequency produce difference, so as to improve
Detectivity, or different resonant frequencies is obtained, realize the tunability of resonant frequency.
Firstly, since bottom graphene film surface is connected with the first nano crystal array, top layer graphene film and second
Nanocrystalline support column is connected, and when the first nano crystal array is semi-conducting material, the first nano crystal array is in closed cavity
Temperature, the change such as pressure can produce perceptual signal, the external world is sent to by bottom graphene film, and utilize closed cavity
To cause incident wavelength to produce resonance, increase signal intensity so that top layer graphene film and bottom graphene film are sent out
The electric signal generation difference sent is more obvious, so as to realize the purpose of high sensitivity detection.
Secondly, when the first nano crystal array is metal, and the second nanocrystalline support column is insulating materials, the second nanocrystalline branch
Dagger realizes the isolation of abutting closure cavity, and has different height in different nanocrystalline pattern units by setting
First nano crystal array of the first nano crystal array, the first nano crystal array of different pattern or different materials, so as to obtain not
Same resonant frequency, and cause incident wavelength to produce resonance using closed cavity, increase signal intensity, realize effectively more
Frequency is received and dispatched or detection, improves the application flexibility of device.
Therefore, the graphene-based laminated film of the present utility model with cavity, can apply to photoelectric field as day
Line, sensor etc., so as to widen the application of graphene film；, can be by adjusting nanocrystalline pattern list when for antenna
The pattern of member and the pattern of closed cavity obtain the photoresponse to different frequency, when for sensor, can pass through tune
The pattern of whole nanocrystalline pattern unit and the pattern of closed cavity obtain higher sensitivity.By adjusting graphene film
The number of plies, can obtain it is transparent and with good flexibility laminated film so that of the present utility model graphene-based compound
Film can bend to different shapes, further widen the application field of graphene film.
Brief description of the drawings
Fig. 1 is the nanocrystalline pattern list in the graphene-based laminated film with cavity of embodiment one of the present utility model
The cross section structure schematic diagram of member
Fig. 2 is a kind of nanocrystalline figure in the graphene-based laminated film with cavity of embodiment one of the present utility model
The cross section structure schematic diagram of case unit
Fig. 3 is a kind of nanocrystalline figure in the graphene-based laminated film with cavity of embodiment one of the present utility model
The overlooking the structure diagram of case unit
Fig. 4 is a kind of nanocrystalline figure in the graphene-based laminated film with cavity of embodiment one of the present utility model
The overlooking the structure diagram of case unit
Fig. 5 is a kind of schematic flow sheet of preparation method of the graphene-based laminated film of embodiment one of the present utility model
Fig. 6 is the flow signal of another preparation method of the graphene-based laminated film of embodiment one of the present utility model
Figure
Fig. 7 is the nanocrystalline pattern list in the graphene-based laminated film with cavity of embodiment two of the present utility model
The cross section structure schematic diagram of member
Fig. 8 is a kind of nanocrystalline figure in the graphene-based laminated film with cavity of embodiment two of the present utility model
The cross section structure schematic diagram of case unit
Fig. 9 is a kind of nanocrystalline figure in the graphene-based laminated film with cavity of embodiment two of the present utility model
The overlooking the structure diagram of case unit
Figure 10 is a kind of nanocrystalline in the graphene-based laminated film with cavity of embodiment two of the present utility model
The overlooking the structure diagram of pattern unit
Figure 11 is a kind of flow signal of preparation method of the graphene-based laminated film of embodiment two of the present utility model
Figure
Figure 12 is that the flow of another preparation method of the graphene-based laminated film of embodiment one of the present utility model is shown
It is intended to
Embodiment
To make content of the present utility model more clear understandable, below in conjunction with Figure of description, to of the present utility model interior
Appearance is described further.Certain the utility model is not limited to the specific embodiment, known to those skilled in the art
General replacement be also covered by the scope of protection of the utility model.
Embodiment one
The utility model is described in further detail below in conjunction with accompanying drawing 1~6 and specific embodiment.It should be noted that
Accompanying drawing using very simplified form, using non-accurately ratio, and only to it is convenient, clearly reach and aid in illustrating this reality
Apply the purpose of example.
Referring to Fig. 1, a kind of graphene-based laminated film with cavity of the present embodiment, including：Bottom graphene is thin
Film 101, the nanocrystalline pattern unit 103 for the multiple repeated arrangements being formed on bottom graphene film 101, and top layer graphite
Alkene film 102.
Each nanocrystalline pattern unit 103 has the first nano crystal array 1032 and positioned at the first nano crystal array 1032
Second nanocrystalline support column 1031 of surrounding；The top of second nanocrystalline support column 1031 is higher than the first nano crystal array 1032
Top；As shown in figure 1, the first nano crystal array 1032 has the nano-wire array that can be, but not limited to equidistantly arrange to form, the
Two nanocrystalline support columns 1031 are nano-pillar.Here the second nanocrystalline support column 1031 is used to support top layer graphene film
102, it is therefore advantageous to, the diameter of the second nanocrystalline support column 1031 is more than the straight of the nano wire of the first nano crystal array 3032
Footpath, so as to effectively be supported to top layer graphene film 102, then, in the present embodiment, in order to keep higher light to pass through
Rate, top layer graphene film 102 is using monoatomic layer or the thickness of multiple atomic layers, and quality is very light, and multiple single second receive
The brilliant support column 1031 of rice completely can support top layer graphene film 102.
Referring to Fig. 1, top layer graphene film 102 is covered in the top of nanocrystalline pattern unit 103, and with second
The top contact of nanocrystalline support column 1031 and do not contacted with the top of the first nano crystal array 1032, multiple nanocrystalline pattern lists
Multiple closed cavities are formed between member 103 and top layer graphene film 102；Wherein, each closed cavity is thin by top layer graphene
Surrounded between film 102, the second nanocrystalline support column 1031, the first nano crystal array 1032.So, due to the second nanocrystalline support
Post 1031 determines the height of closed cavity, and the area of the first nano crystal array 1032 determines the bottom area of closed cavity, then,
First nano crystal array 1032 and the second nanocrystalline support column 1031 have together decided on the volume of closed cavity, can be according to difference
Application field adjust the first nano crystal array 1032 and the difference in height of the second nanocrystalline support column 1031 and first nanometer
The area of brilliant array 1032.When the graphene-based laminated film of the present embodiment is used for antenna, the first nano crystal array 1032
Highly it is the 20~50% of the height of the second nanocrystalline support column 1031, regulates and controls bottom graphene film 101 using voltage
Reception or tranmitting frequency, and regulate and control reception or the tranmitting frequency of the first nano crystal array 1032, so as to significantly more efficient
Frequency needed for reception or transmitting.When the graphene-based laminated film of the present embodiment is used for pressure sensor, the first nanocrystalline battle array
The ratio of the height of row 1032 and the height of the second nanocrystalline support column 1031 can be up to the 90%, or even first nano crystal array
1032 are in contact with top layer graphene film 102, to realize effective detection.When the graphene-based laminated film of the present embodiment is used
, it is necessary to which higher light transmission rate, now, the height of the first nano crystal array 1032 are received with second when on transparent material or device
The height of the brilliant support column 1031 of rice is not more than 10%, preferably, the height of the first nano crystal array 1032 is 2~10nm, so as to
Ensure good light transmission rate and transparency.
Here, Fig. 2~4 are referred to, it is necessary to illustrate, in Fig. 2~4, black represents bottom graphene film 101, in vain
Color circle represents the nano wire in the first nano crystal array, here in order to express clearly briefly, illustrate only in Fig. 2~4 positioned at the
The bottom graphene film 101 of one nano crystal array bottom.In the present embodiment, the pattern of nanocrystalline pattern unit 103 can have
Many kinds, for example, as shown in Fig. 2 the pattern of single nanocrystalline pattern unit 103 can be with rounded, now, the first nanocrystalline battle array
Row 1032 can be in that Archimedian screw shape is arranged, so as to strengthen the response to different frequency, the second nanocrystalline support column 1031
It is in annular around the first nano crystal array 1032；For another example as shown in figure 3, the pattern of single nanocrystalline pattern unit 103 can
With rectangular, now, equally matrix is arranged in the first nano crystal array 1032, so as to strengthen the response to different frequency,
Second nanocrystalline support column 1031 surrounds 1032 rectangular ring of the first nano crystal array；For another example as shown in figure 4, single nanometer
The pattern of brilliant pattern unit 103 can be in monosymmetric bow tie, now, in the first nano crystal array 1032 equally
Triangular array is arranged, and so as to strengthen the response to different frequency, the second nanocrystalline support column 1031 surrounds the first nanocrystalline battle array
Row 1032 are also in symmetrical bow tie；These patterns cause the graphene-based laminated film of the present embodiment advantageously in for
Antenna, because circular, rectangle and butterfly structure are able to when graphene-based laminated film is powered to different frequency generations
Different response so that the application of graphene-based laminated film is more flexible.It is as shown in figs. 2 to 4, adjacent in the present embodiment
Nanocrystalline pattern unit 103 shares one or more second nanocrystalline support columns 1031, or adjacent nano crystalline substance pattern unit 103
The second nanocrystalline support column 1031 be in contact connection so that adjacent annular is intersecting, (as shown in Figure 2 second is nanocrystalline
Support column 1031) or tangent, adjacent rectangle have common edge (as shown in Figure 3 the second nanocrystalline support column 1031) or
Adjacent bow tie has common edge (the second nanocrystalline support column 1031 as shown in Figure 4).In the present embodiment, receive when first
The material of the brilliant array 1032 of rice is metal nano material, for example, titanium, copper metal etc.；Second nanocrystalline support column 1031
Material is insulating materials, can be metal oxide materials, such as zinc oxide etc..When the graphene-based laminated film of the present embodiment
During for antenna, it can be played using the second nanocrystalline support column 1031 of insulating materials and isolate adjacent nanocrystalline pattern unit
103 effect, avoid the crosstalk between adjacent nano crystalline substance pattern unit 103 so that each nanocrystalline pattern unit 103 can answer
For different frequencies and mutual crosstalk is avoided, or, the first nano crystal array of different nanocrystalline pattern units 103
1032 material differs, so as to obtain the collection or transmitting to different frequency.When the graphene-based laminated film of the present embodiment
During for sensor, the material of the second nanocrystalline support column 1031 can be identical with the material of the first nano crystal array 1032, makes
Nanocrystalline pattern unit 103 that must be all is detected jointly, and bottom graphene film 101 and top layer graphene film 102 are made
For bottom electrode and Top electrode；Certainly, the material of the second nanocrystalline support column 1031 can also be with the first nano crystal array 1032
Material differs, as long as can be used for making the first nano crystal array 1032 and the second nanocrystalline support column 1031 to carry out
Electrical conduction.
Referring to Fig. 5, in the present embodiment, for the preparation method of the above-mentioned graphene-based laminated film with cavity,
Following process can be taken：
Step A01：One bottom graphene film is provided；
Specifically, bottom graphene film here can be monoatomic-layer graphene film, or 2~3 layers of original
Sublayer graphene film；In the present embodiment, bottom graphene film can be, but not limited to use chemical vapor deposition on copper-based bottom
Prepared by area method, thermal decomposition method, the bottom graphene film prepared adsorbs and peeled away with copper-based bottom using PMMA,
Then, bottom graphene film is transferred in another substrate in clamping PMMA, for example, silicon substrate, quartz substrate etc., subsequently
The substrate is carried in step A02~A07 preparation process, after step A07, the substrate is removed, due to base
Bottom, which is simply played, eats support effect, therefore, substrate is no longer described in subsequent step A02~A07 description.
Step A02：A mask is formed on bottom graphene film；And it is nanocrystalline that initial second is defined on mask
Support column area of the pattern and the first nano crystal array region；
Specifically, it can be, but not limited to form mask, the material of mask on bottom graphene film using techniques such as spin coatings
Expect it can is etch layer, such as photoresist or inorganic mask.Here, etch layer is preferably used, because organic
The etching selection ratio of mask differs greatly with the second nanocrystalline support column, the first nanocrystalline support column, grapheme material, can be compared with
Easily remove.
Step A03：The second nanocrystalline support column pattern in nanocrystalline pattern unit is etched in the mask, to expose
Bottom graphene film；
Specifically, the second nanocrystalline support column pattern can be etched in photoresist mask using photoetching process.
Step A04：The two nanocrystalline support column of growth regulation on exposed bottom graphene film；
Specifically, here, the nano-pillar of the pattern of the second nanocrystalline support column, the material of the second nanocrystalline support column can be with
For insulated by oxide medium, can be, but not limited to using aqua-solution method, chemical vapour deposition technique, electrochemical plating etc. come growth regulation
Two nanocrystalline support columns, preferably, aqua-solution method is used, will not be to bottom graphene because the growth temperature of aqua-solution method is low
Film and photoresist mask damage or destructiveness is slighter.
Step A05：One layer of new mask is covered in the structure for completing step A04, and removes the first nano crystal array area
The mask in domain and new mask；New mask shelters the bottom graphene film outside the first nano crystal array region；
Specifically, can be, but not limited to cover new mask again using spin coating method, the material of new mask can be with step A02
Mask material it is identical, be photoresist, then, using photoetching process remove the first nano crystal array region all photoetching
Glue exposes the bottom graphene film below the first nano crystal array region；New photoresist is by the first nano crystal array region
The bottom graphene film of ambition shelters from.
Step A06：In the first nanocrystalline battle array of bottom graphene film superficial growth of the first nano crystal array region exposure
Row；
Specifically, the first nanocrystalline pattern of the first nano crystal array here is nano wire, can be, but not limited to adopt
The first nano crystal array is grown with aqua-solution method, chemical vapour deposition technique, electrochemical plating etc., preferably, using the aqueous solution
Method, because the growth temperature of aqua-solution method is low, bottom graphene film and photoresist mask will not be damaged or destroyed
Lesser extent is micro-.
Step A07：All masks are removed, and above the first nano crystal array, at the top of the second nanocrystalline support column
Top layer graphene film is covered, so as to by being enclosed between top layer graphene film, the second nanocrystalline support column, the first nano crystal array
Into closed cavity.
Specifically, it can be, but not limited to remove all photoresists using the method for wet etching, it is then possible to using conventional
Graphene shifting process, top layer graphene film is covered in above the first nano crystal array, the second nanocrystalline support capital
Portion, the second nanocrystalline support column top braces top layer graphene film, so as in top layer graphene film and the first nanocrystalline battle array
Closed cavity is formed between row.Top layer graphene film can be monoatomic layer thickness, 2~3 atomic layer level thickness, so that it is guaranteed that top
The light transmission rate of layer graphene film.
Referring to Fig. 6, in the present embodiment, in the above-mentioned graphene-based laminated film with cavity, receive when first
The material of the brilliant array of rice and the material of the second nanocrystalline support column are mutually at the same time it can also taking following preparation method：
Step B01：One bottom graphene film is provided；
Specifically, bottom graphene film here can be monoatomic-layer graphene film, or 2~3 layers of original
Sublayer graphene film；In the present embodiment, bottom graphene film can be, but not limited to use chemical vapor deposition on copper-based bottom
Prepared by area method, thermal decomposition method, the bottom graphene film prepared adsorbs and peeled away with copper-based bottom using PMMA,
Then, bottom graphene film is transferred in another substrate in clamping PMMA, for example, silicon substrate, quartz substrate etc., subsequently
The substrate is carried in step B02~B07 preparation process, after step B07, the substrate is removed, due to base
Bottom, which is simply played, eats support effect, therefore, substrate is no longer described in subsequent step B02~B07 description.
Step B02：A mask is formed on bottom graphene film；And it is nanocrystalline that initial second is defined on mask
Support column area of the pattern and the first nano crystal array region；
Specifically, it can be, but not limited to form mask, the material of mask on bottom graphene film using techniques such as spin coatings
Expect it can is etch layer, such as photoresist or inorganic mask.Here, etch layer is preferably used, because organic
The etching selection ratio of mask differs greatly with the second nanocrystalline support column, the first nanocrystalline support column, grapheme material, can be compared with
Easily remove.
Step B03：The initial second nanocrystalline support column pattern in nanocrystalline pattern unit is etched in the mask, with sudden and violent
Expose bottom graphene film；
Specifically, the initial second nanocrystalline support column pattern can be etched in photoresist mask using photoetching process.
Explanation is needed exist for, during due to the first nano crystal array of subsequent growth, initial second nanocrystalline support column continued growth, because
This, the diameter of initial second nanocrystalline support column pattern is smaller than the diameter of the second required nanocrystalline support column.
Step B04：The initial second nanocrystalline support column is grown on exposed bottom graphene film；
Specifically, here, the nano-pillar of the pattern of the second nanocrystalline support column, the material of the second nanocrystalline support column can be with
For insulated by oxide medium, can be, but not limited to using aqua-solution method, chemical vapour deposition technique, electrochemical plating etc. come growth regulation
Two nanocrystalline support columns, preferably, aqua-solution method is used, will not be to bottom graphene because the growth temperature of aqua-solution method is low
Film and photoresist mask damage or destructiveness is slighter.
Step B05：Remove the mask in the first nano crystal array region；
Specifically, it can be, but not limited to get rid of the photoresist in the first nano crystal array region using photoetching process.
Step B06：On the bottom graphene film surface and initial second nanometer of the first nano crystal array region exposure
Continued growth is nanocrystalline at the top of brilliant support column, so that initial second nanocrystalline support column is grown to serve as final second nanometer
Brilliant support column, and go out the first nano crystal array in exposed bottom graphene film superficial growth；
Specifically, the first nanocrystalline pattern of the first nano crystal array here is nano wire, can be, but not limited to adopt
The first nano crystal array is grown with aqua-solution method, chemical vapour deposition technique, electrochemical plating etc., preferably, using the aqueous solution
Method, because the growth temperature of aqua-solution method is low, bottom graphene film and photoresist mask will not be damaged or destroyed
Lesser extent is micro-.
It should be noted that during being grown due to the first nano crystal array, initial second nanocrystalline support column is also sudden and violent
It is exposed in growing environment, also continued growth while the first nano crystal array grows of initial second nanocrystalline support column so that
Initial second nanocrystalline support column grows tall, and diameter also becomes big, so as to ultimately form the second of required size the nanocrystalline support column
And first nano crystal array, the monitoring on the growth of the first nano crystal array and initial second nanocrystalline support column can lead to
The process conditions such as adjustment reaction time, reaction pressure, reaction temperature are crossed to control.
Step B07：Remaining mask is removed, and above the first nano crystal array, at the top of the second nanocrystalline support column
Top layer graphene film is covered, so as to by being enclosed between top layer graphene film, the second nanocrystalline support column, the first nano crystal array
Into closed cavity.
Specifically, it can be, but not limited to remove all photoresists using the method for wet etching, it is then possible to using conventional
Graphene shifting process, top layer graphene film is covered in above the first nano crystal array, the second nanocrystalline support capital
Portion, the second nanocrystalline support column top braces top layer graphene film, so as in top layer graphene film and the first nanocrystalline battle array
Closed cavity is formed between row.Top layer graphene film can be monoatomic layer thickness or two to three layers of atomic layer level thickness, so as to
Ensure the light transmission rate of top layer graphene film.
The setting of the closed cavity of the present embodiment, it can apply in more photoelectric devices, for example, resonance can be used as
Chamber, can as pressure detection chamber, can be as antenna response cavity etc., those skilled in the art are by the stone of the present embodiment
The arrangement of closed cavity in mertenyl laminated film makes rationally deformation and can be applied to different occasions.
In addition, the graphene-based laminated film of the present embodiment also has good pliability, flexible device can apply to
In.
Embodiment two
The utility model is described in further detail below in conjunction with accompanying drawing 7~12 and specific embodiment.It should be noted that
Accompanying drawing using very simplified form, using non-accurately ratio, and only to it is convenient, clearly reach and aid in illustrating this reality
Apply the purpose of example.
Referring to Fig. 7, the graphene-based laminated film with cavity of the present embodiment two includes：Bottom graphene film
201, the nanocrystalline pattern unit 203 for the multiple repeated arrangements being formed on bottom graphene film 201, and top layer graphene
Film 202.Each nanocrystalline pattern unit 203 has the first nano crystal array 2032 and positioned at the first nano crystal array 2032
Second nanocrystalline support column 2031 of surrounding.The graphene-based laminated film of the present embodiment two and embodiment one have cavity
The difference of graphene-based laminated film is：In the present embodiment two, organic nano screen is provided between nanocrystalline pattern unit 203
Cover material 204.Specifically, second the receiving of being arranged on adjacent different nanocrystalline pattern units 203 of organic nano shielding material 204
Between the brilliant support column 2031 of rice.
Fig. 8~10 are referred to, it is necessary to which explanation, black represent bottom graphene film 101, white circular represents that first receives
Nano wire in the brilliant array of rice, in order to express clearly briefly, illustrate only positioned at the first nano crystal array bottom in Fig. 8~10
Bottom graphene film 201.Here, the pattern of nanocrystalline pattern unit 203 can have many kinds, such as single nanocrystalline pattern
The pattern of unit 203 can be with rounded, as shown in figure 8, corresponding first nano crystal array 2032 can be in Archimedian screw shape
Arrangement, the second nanocrystalline support column 2031 is in annular around the first nano crystal array 2032；Single nanocrystalline pattern unit 203
Pattern can with rectangular, as shown in figure 9, in corresponding first nano crystal array 2032 equally matrix arrange, second receives
The brilliant support column 2031 of rice surrounds 2032 rectangular ring of the first nano crystal array；The pattern of single nanocrystalline pattern unit 203 may be used also
With in monosymmetric bow tie, as shown in Figure 10, equally triangle battle array in corresponding first nano crystal array 2032
Row arrangement, the second nanocrystalline rectangle of support column 2031 is also in symmetrical bow tie around the first nano crystal array 2032.This reality
The surrounding of nanocrystalline pattern unit 203 applied in example is surrounded by organic nano shielding material 204, prevents nanocrystalline pattern unit
Signal cross-talk between 203.
It should be noted that multiple nanocrystalline pattern units 203 in the present embodiment two can also be arranged in different shapes
Shape or matrix respond different frequencies, according to detection environment obtain different sensitivity.
Figure 11 is referred to, in the present embodiment, for the system of the graphene-based laminated film with cavity of the present embodiment two
Preparation Method, following process can be taken：
Step C01：One bottom graphene film is provided；
Specifically, bottom graphene film here can be monoatomic-layer graphene film, or 2~3 layers of original
Sublayer graphene film.In the present embodiment, bottom graphene film can be, but not limited to use chemical vapor deposition on copper-based bottom
Prepared by area method, thermal decomposition method, the bottom graphene film prepared adsorbs and peeled away with copper-based bottom using PMMA,
Then, bottom graphene film is transferred in another substrate in clamping PMMA, for example, silicon substrate, quartz substrate etc., subsequently
The substrate is carried in step C02~C07 preparation process, after step C07, the substrate is removed, due to base
Bottom, which is simply played, eats support effect, therefore, substrate is no longer described in subsequent step C02~C07 description.
Step C02：One layer of organic nano shielding material is formed on bottom graphene film as mask；And in mask
On define the second nanocrystalline support column area of the pattern and the first nano crystal array region；
Specifically, it can be, but not limited to form organic nano shielding material on bottom graphene film using techniques such as spin coatings
Material is used as mask.In addition, the etching selection ratio of organic nano shielding material and the second nanocrystalline support column, the first nanocrystalline support
Post, grapheme material differ greatly, and can be easier to remove.Here organic nano shielding material can be used for adjacent nano crystalline substance
The crosstalks such as electromagnetic wave, frequency between pattern unit.
Step C03：The second nanocrystalline support column pattern in nanocrystalline pattern unit is etched in the mask, to expose
Bottom graphene film；
Specifically, for the etching of organic shielding material, photoetching and etching technics can be used, on organic shielding material
Photoresist is coated, through photoetching process, etches the pattern of nanocrystalline pattern unit, then using plasma dry method in the photoresist
Etching, the pattern of nanocrystalline pattern unit is etched in organic shielding material.Then, photoresist is removed.
Step C04：The two nanocrystalline support column of growth regulation on exposed bottom graphene film；
Specifically, here, the nano-pillar of the pattern of the second nanocrystalline support column, the material of the second nanocrystalline support column can be with
For insulated by oxide medium, can be, but not limited to using aqua-solution method, chemical vapour deposition technique, electrochemical plating etc. come growth regulation
Two nanocrystalline support columns, preferably, aqua-solution method is used, will not be to bottom graphene because the growth temperature of aqua-solution method is low
Film and photoresist mask damage or destructiveness is slighter.
Step C05：One layer of organic nano shielding material is covered again as new mask in the structure for completing step C04, and
And remove the mask in the first nano crystal array region and new mask；New mask is by the bottom stone outside the first nano crystal array region
Black alkene film masking；
Specifically, can be, but not limited to cover new organic nano shielding material again as new mask using spin coating method,
Then, all organic nano shielding materials in the first nano crystal array region are removed using photoetching and etching technics to be included newly
Organic nano shielding material is so as to exposing the bottom graphene film below the first nano crystal array region；Finally remove photoetching
Glue；New organic nano shielding material shelters from the bottom graphene film of the first nano crystal array region ambition.
Step C06：In the first nanocrystalline battle array of bottom graphene film superficial growth of the first nano crystal array region exposure
Row；
Specifically, the first nanocrystalline pattern of the first nano crystal array here is nano wire, can be, but not limited to adopt
The first nano crystal array is grown with aqua-solution method, chemical vapour deposition technique, electrochemical plating etc., preferably, using the aqueous solution
Method, because the growth temperature of aqua-solution method is low, bottom graphene film and photoresist mask will not be damaged or destroyed
Lesser extent is micro-.
Step C07：The new mask above the second nanocrystalline support column is removed, is retained between adjacent nanocrystalline pattern unit
Remaining organic nano shielding material, and above the first nano crystal array, at the top of the second nanocrystalline support column cover top
Layer graphene film, so as to by surrounding closing between top layer graphene film, the second nanocrystalline support column, the first nano crystal array
Cavity, and between adjacent nanocrystalline pattern unit there is machine nano-EMI material to be isolated.
Specifically, the locality protection between adjacent nanocrystalline pattern unit can be got up using photoresist mask, light
Photoresist mask leaves opening above the second nanocrystalline support column, then removes the second nanocrystalline support column using wet corrosion technique
The new organic nano shielding material of top, so as to remain with remaining organic nano screen between adjacent nanocrystalline pattern unit
Cover and just carry out material；It is then possible to using conventional graphene shifting process, it is nanocrystalline that top layer graphene film is covered in first
Above array, at the top of the second nanocrystalline support column, the second nanocrystalline support column top braces top layer graphene film, so as to push up
Closed cavity is formed between layer graphene film and the first nano crystal array.Top layer graphene film can be monoatomic layer thickness
Or two to three layers of atomic layer level thickness, so that it is guaranteed that the light transmission rate of top layer graphene film.
Refer to Figure 12, in the present embodiment two, in the graphene-based laminated film with cavity of the present embodiment two,
When the material of the material of the first nano crystal array and the second nanocrystalline support column is mutually at the same time it can also taking following preparation method：
Step D01：One bottom graphene film is provided；
Specifically, bottom graphene film here can be monoatomic-layer graphene film, or 2~3 layers of original
Sublayer graphene film.In the present embodiment, bottom graphene film can be, but not limited to use chemical vapor deposition on copper-based bottom
Prepared by area method, thermal decomposition method, the bottom graphene film prepared adsorbs and peeled away with copper-based bottom using PMMA,
Then, bottom graphene film is transferred in another substrate in clamping PMMA, for example, silicon substrate, quartz substrate etc., subsequently
The substrate is carried in step D02~D07 preparation process, after step D07, the substrate is removed, due to base
Bottom, which is simply played, eats support effect, therefore, substrate is no longer described in subsequent step D02~D07 description.
Step D02：One layer of organic nano shielding material is formed on bottom graphene film as mask；And in mask
On define the initial second nanocrystalline support column area of the pattern and the first nano crystal array region；
Specifically, it can be, but not limited to form organic nano shielding material on bottom graphene film using techniques such as spin coatings
Material is used as mask.In addition, the etching selection ratio of organic nano shielding material and the second nanocrystalline support column, the first nanocrystalline support
Post, grapheme material differ greatly, and can be easier to remove.Here organic nano shielding material can be used for adjacent nano crystalline substance
The crosstalks such as electromagnetic wave, frequency between pattern unit.
Step D03：The initial second nanocrystalline support column pattern in nanocrystalline pattern unit is etched in the mask, with sudden and violent
Expose bottom graphene film；
Specifically, for the etching of organic nano shielding material, photoetching and etching technics can be used, in organic screen material
Photoresist is coated on material, through photoetching process, etches the pattern of nanocrystalline pattern unit, then using plasma in the photoresist
Dry etching, the pattern of nanocrystalline pattern unit is etched in organic shielding material.Then, photoresist is removed.
Step D04：The initial second nanocrystalline support column is grown on exposed bottom graphene film；
Specifically, here, the nano-pillar of the pattern of the second nanocrystalline support column, the material of the second nanocrystalline support column can be with
For insulated by oxide medium, can be, but not limited to using aqua-solution method, chemical vapour deposition technique, electrochemical plating etc. come growth regulation
Two nanocrystalline support columns, preferably, aqua-solution method is used, will not be to bottom graphene because the growth temperature of aqua-solution method is low
Film and photoresist mask damage or destructiveness is slighter.
Step D05：The mask in the first nano crystal array region is removed, is retained between adjacent nanocrystalline pattern unit region
Mask；
Specifically, can be, but not limited between being covered in adjacent nano crystalline substance pattern unit region using photoresist mask,
There is opening to expose the first nano crystal array region in photoresist mask, so as to by the organic of the first nano crystal array region
Nano-EMI material is got rid of, and is retained the organic nano shielding material between adjacent nanocrystalline pattern unit region, is finally gone
Except residual photoresist.
Step D06：The bottom graphene film surface of exposure and the second nanocrystalline branch in the first nano crystal array region
Continued growth is nanocrystalline at the top of dagger, so that initial second nanocrystalline support column is grown to serve as the nanocrystalline branch of final second
Dagger, and go out the first nano crystal array in exposed bottom graphene film superficial growth；
Specifically, the first nanocrystalline pattern of the first nano crystal array here is nano wire, can be, but not limited to adopt
The first nano crystal array is grown with aqua-solution method, chemical vapour deposition technique, electrochemical plating etc., preferably, using the aqueous solution
Method, because the growth temperature of aqua-solution method is low, bottom graphene film and photoresist mask will not be damaged or destroyed
Lesser extent is micro-.
It should be noted that during being grown due to the first nano crystal array, initial second nanocrystalline support column is also sudden and violent
It is exposed in growing environment, also continued growth while the first nano crystal array grows of initial second nanocrystalline support column so that
Initial second nanocrystalline support column grows tall, and diameter also becomes big, so as to ultimately form the second of required size the nanocrystalline support column
And first nano crystal array, the monitoring on the growth of the first nano crystal array and initial second nanocrystalline support column can lead to
The process conditions such as adjustment reaction time, reaction pressure, reaction temperature are crossed to control.
Step D07：Above the first nano crystal array, top layer graphene film is covered at the top of the second nanocrystalline support column,
So that by surrounding closed cavity between top layer graphene film, the second nanocrystalline support column, the first nano crystal array, and in phase
Between adjacent nanocrystalline pattern unit there is machine nano-EMI material to be isolated.
Specifically, conventional graphene shifting process can be used, it is nanocrystalline that top layer graphene film is covered in first
Above array, at the top of the second nanocrystalline support column, the second nanocrystalline support column top braces top layer graphene film, so as to push up
Closed cavity is formed between layer graphene film and the first nano crystal array.Due to adjacent more nanocrystalline than being remained in the D05 of state
Organic nano shielding material between pattern unit region, the organic nano shielding material of the reservation are used to isolate adjacent nanometer
Brilliant pattern unit.Here top layer graphene film can be monoatomic layer thickness or two to three layers of atomic layer level thickness, so as to really
Protect the light transmission rate of top layer graphene film.
Although the utility model is disclosed as above with preferred embodiment, the right embodiment is illustrated only for the purposes of explanation
, the utility model is not limited to, those skilled in the art is not before the spirit and scope of the utility model is departed from
Some change and retouching can be made by putting, and the protection domain that the utility model is advocated should be to be defined described in claims.
Claims (9)
- A kind of 1. graphene-based laminated film with cavity, it is characterised in that including：Bottom graphene film；The nanocrystalline pattern unit for the multiple repeated arrangements being formed on bottom graphene film；Each nanocrystalline pattern unit tool There are the first nano crystal array and the second nanocrystalline support column around the first nano crystal array；Second nanocrystalline support column Top be higher than the first nano crystal array top；Top layer graphene film, be covered at the top of the nanocrystalline pattern unit, and with the top of the second nanocrystalline support column Contact and do not contacted with the top of the first nano crystal array, formed between multiple nanocrystalline pattern units and top layer graphene multiple Closed cavity；Wherein, each closed cavity by top layer graphene film, the second nanocrystalline support column, the first nano crystal array it Between surround.
- 2. the graphene-based laminated film according to claim 1 with cavity, it is characterised in that single described nanocrystalline Pattern unit is rounded, rectangle or bow tie.
- 3. the graphene-based laminated film according to claim 2 with cavity, it is characterised in that the first nano crystal array In Archimedes's array arrangement, or equidistantly matrix arrangement, or the arrangement of butterfly knot shape.
- 4. the graphene-based laminated film according to claim 1 with cavity, it is characterised in that adjacent nanocrystalline figure Case units shared the second nanocrystalline support column of one or more, or the second nanocrystalline support column of adjacent nano crystalline substance pattern unit Be in contact connection.
- 5. the graphene-based laminated film according to claim 1 with cavity, it is characterised in that adjacent nanocrystalline figure Organic nano-EMI material is set between case unit.
- 6. the graphene-based laminated film according to claim 1 with cavity, it is characterised in that described first is nanocrystalline The material of array is metal nano material；The material of the second nanocrystalline support column is insulating materials.
- 7. the graphene-based laminated film according to claim 6 with cavity, it is characterised in that described second is nanocrystalline The material of support column is metal oxide materials.
- 8. the graphene-based laminated film according to claim 1 with cavity, it is characterised in that described second is nanocrystalline The material of support column is identical with the material of first nano crystal array.
- 9. the graphene-based laminated film with cavity according to claim 1~8 any one, it is characterised in that institute State that the first nano crystal array uses for nano-wire array, the second nanocrystalline support column use for nano-pillar.
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| CN108534921A (en) * | 2018-03-26 | 2018-09-14 | 京东方科技集团股份有限公司 | Pressure sensor, display device |
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| CN111024281B (en) * | 2018-10-09 | 2021-12-07 | 中国移动通信集团设计院有限公司 | Pressure sensing device, preparation method and pressure sensing system |
| CN109581059A (en) * | 2018-12-13 | 2019-04-05 | 南京邮电大学 | A kind of preparation method based on graphene/up-conversion luminescence nanometer crystal composite material variable-resistance transducer |
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| US9166271B2 (en) * | 2012-06-01 | 2015-10-20 | Purdue Research Foundation | Tunable cavity resonator including a plurality of MEMS beams |
| CN102856139B (en) * | 2012-09-07 | 2015-04-15 | 福州大学 | Surface-conduction electron emission source based on graphene |
| KR101603207B1 (en) * | 2013-01-29 | 2016-03-14 | 삼성전자주식회사 | Manufacturing methdo of nano sturucture semiconductor light emitting device |
| CN105340369A (en) * | 2013-02-06 | 2016-02-17 | 伊利诺伊大学评议会 | Stretchable electronic systems with containment chambers |
| CN106155416B (en) * | 2016-07-07 | 2019-05-07 | 无锡第六元素电子薄膜科技有限公司 | A kind of composite membrane touch sensing and preparation method thereof |
| CN106409518A (en) * | 2016-10-09 | 2017-02-15 | 全普光电科技(上海)有限公司 | Graphene-based composite thin film, self-cleaning solar thin film cell and preparation method |
| CN106348244B (en) * | 2016-10-09 | 2019-03-05 | 全普光电科技(上海)有限公司 | A kind of graphene-based nanowire composite structures and preparation method thereof |
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| CN108534921A (en) * | 2018-03-26 | 2018-09-14 | 京东方科技集团股份有限公司 | Pressure sensor, display device |
| CN108534921B (en) * | 2018-03-26 | 2021-01-26 | 京东方科技集团股份有限公司 | Pressure sensor and display device |
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