CN106409518A - Graphene-based composite thin film, self-cleaning solar thin film cell and preparation method - Google Patents

Graphene-based composite thin film, self-cleaning solar thin film cell and preparation method Download PDF

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Publication number
CN106409518A
CN106409518A CN201610880943.7A CN201610880943A CN106409518A CN 106409518 A CN106409518 A CN 106409518A CN 201610880943 A CN201610880943 A CN 201610880943A CN 106409518 A CN106409518 A CN 106409518A
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China
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layer
film
graphene
transparent
nano
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Chinese (zh)
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汪际军
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Quanpu Semiconductor Technology (Shenzhen) Co., Ltd.
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Qualper Optoelectronics Technology (shanghai) Co Ltd
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Priority to CN201610880943.7A priority Critical patent/CN106409518A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
    • H01G9/2077—Sealing arrangements, e.g. to prevent the leakage of the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Abstract

The invention provides a graphene-based composite thin film, a self-cleaning solar thin film cell and a preparation method. A continuous photo catalytic nanometer thin film is perpendicularly grown on the graphene thin film, the composite thin film is used as a light transmitting layer, relatively high light transmittance of the composite thin film used as the light transmitting layer is ensured due to high transmittance of the graphene thin film, and a self-cleaning function is achieved by the photo catalytic nanometer thin film; and furthermore, the graphene-based composite thin film is used as an electrode layer, the conductive rate is improved by means of rapid carrier mobility of the graphene thin film, the loss of a battery during photoelectric conversion is reduced, the nanometer thin film perpendicular to the graphene thin film is used as a dye migration passage, the dye migration rate is improved, and the power generation efficiency is further improved.

Description

Graphene-based laminated film, automatically cleaning solar film battery and preparation method
Technical field
The present invention relates to technical field of semiconductors and in particular to a kind of graphene-based laminated film and preparation method thereof, from Cleaning solar film battery and preparation method thereof.
Background technology
Development with semiconductor technology and the continuous reduction of technology node, traditional silicon materials have shown many limits System and defect, due to a kind of novel nano material that Graphene is the thinnest in the world at present, intensity highest, electrical and thermal conductivity performance are the strongest Material, so Graphene becomes the succedaneum of preferable silicon.Graphene film preparation and performance have received global concern With widely studied, graphene film is expected to be applied to because having quick carrier mobility, high rigidity and flexibility In semiconductor device.
However, the energy gap of Graphene is zero, and semi-conducting material is requirement has certain energy gap, therefore grinds Study carefully and how to be applied in semiconductor applications be significant by the above-mentioned advantage of graphene film.Generally quasiconductor is received Rice material is combined to prepare with Graphene and has the composite construction that the above-mentioned advantage of Graphene also has semiconducting behavior concurrently concurrently, however, Growth on Graphene for the semiconductor nano material is more difficult, and this is also a difficult problem for industry；Although someone is in Graphene Continuous nano material film is prepared on thin film, but these nano material films are easy to come off, limit this composite junction The application of structure；In order to improve the conjugation of nano material film and graphene film, can attempt thin using reducing nano material The method of the thickness of film, and to play nanometer in order to continuous nano material film is grown further on graphene film The performance of material film and the flexibility etc. improving graphene-based composite construction, are more desirable to receiving of on graphene film growth The thickness of rice material film is reduced to ultra-thin or even several nanometer of thickness, however so cannot continuous nano material thin Film.
Additionally, there is following defect in existing solaode：Solaode is exposed in the air for a long time and causes itself Cleaning problems, and light utilization efficiency is relatively low, and generating efficiency is low, volume is larger, and solaode can not become according to external environment Change and accomplish self-protection effectively.For example, when running into the rainy day, solaode is exposed among rainwater, when being in night, Solaode now can not absorb sunlight and has been operated and be also exposed in the air, thus causing the dirt of solaode Dye and service life reduction.Therefore, on the premise of the transmitance not affecting solaode, improve generating efficiency can also make for research Solaode has self-cleaning function concurrently, is significant.
Content of the invention
In order to overcome problem above, the present invention is intended to provide a kind of graphene-based laminated film and graphene-based multiple with this Close the solar film battery based on thin film, to make very thin continuous nano material is grown on this graphene film thin Film, and so that solar film battery is had while self-cleaning function can also improve generating efficiency.
In order to achieve the above object, a kind of graphene-based laminated film of the present invention is it is characterised in that include：One Graphene The thin film and vertical-growth nano thin-film on described graphene film；The plane of described nano thin-film is thin with described Graphene Film is vertical；The bottom of described nano thin-film is bonded by chemical bond phase with described graphene film；The material of described nano thin-film For conductor photocatalysis material.
Preferably, described graphene film is the graphene film of two-layer atomic layer or the Graphene of three layers of atomic layer is thin Film.
Preferably, described nano thin-film has multiple micro- engraved structures, thus constituting nano net.
Preferably, the spacing between adjacent described micro- engraved structure is not more than 10nm.
Preferably, described nano net is grown perpendicular to transparent substrates by nano wire and the side of adjacent nanowires contacts shape Become nano thin-film, then etch the micro- void region of formation through nano thin-film.
Preferably, it is bonded by chemical bond phase between the described nano wire contacting.
Preferably, the diameter of nano wire is the thickness of described nano thin-film.
Preferably, the thickness of described nano thin-film is not more than 10nm.
Preferably, described conductor photocatalysis material is wide band gap semiconducter catalysis material.
Preferably, described wide band gap semiconducter catalysis material is titanium alloy nano line and/or zinc alloy nano-wire.
Preferably, described graphene film has multiple described nano thin-films being arranged in array.
In order to achieve the above object, present invention also offers a kind of preparation method of above-mentioned graphene-based laminated film, It includes：
Step 01：One graphene film is provided；
Step 02：Nano thin-film is grown on described graphene film；The nano thin-film place plane being grown perpendicular to Described graphene film, the bottom of described nano thin-film is bonded by chemical bond phase with graphene film.
Preferably, also include after described step 02：Step 03, etches multiple described micro- engrave on described nano thin-film Hollow structure, thus form nano net.
Preferably, in described step 03, using plasma lithographic technique or laser-induced thermal etching are etching described micro- hollow out Structure.
Preferably, in described step 02, the growth course of nano thin-film includes：
Step 021, prepares 1-dimention nano sub-array on the transparent substrate；
Step 022, with nanometer sub-array as base, every nanometer seed bent to growth nanowire, thus forming nanometer Linear array；
Step 023, the side of adjacent nanowires contacts with each other, thus forming the nano thin-film perpendicular to transparent substrates.
Preferably, in described step 021, the preparation that wherein at least has row of one dimensional nanometer sub-array includes：First, Form nanometer seed precursor solution on the transparent substrate, after being dried, form nanometer seed thin film；Secondly, lured using laser Waveguide technology marks nanoscale vestige in described nanometer seed thin film, and nanoscale mark region induces a nanometer sub-array.
Preferably, the live width of described nanoscale vestige is equal to or more than the diameter of nanometer seed, described nanometer sub-array The width of region is equal to the live width of described nanoscale vestige.
Preferably, in described step 021, the preparation that wherein at least has row of one dimensional nanometer sub-array includes：
First, form one layer of mask on a transparent substrate；
Then, mask is carried out with photoetching and/or etching forms one nanoscale opening；
Finally, nanometer sub-array is formed on the transparent substrates that nanoscale opening is exposed.
Preferably, when the material of mask is photosensitivity material, etched on mask using photoetching process and receive together Meter level opening；When the material of mask is inorganic material, using photoetching and etching technics or only with anisotropic etching work Skill to etch one nanoscale opening on mask.
Preferably, in described step 022, to be grown using chemical vapour deposition technique, aqua-solution method or electrochemical plating and to receive Rice noodle.
In order to achieve the above object, present invention also offers a kind of graphene-based automatically cleaning solar film battery, its from Top to bottm it is disposed with light transmission layer, transparent electrode layer and light conversion layer, incident illumination is successively through light transmission layer and transparent electrical Pole layer, enters back into light conversion layer, and light conversion layer carries out opto-electronic conversion after absorbing incident illumination and produces electricity；Light-transmitting layer has Above-mentioned graphene-based laminated film, wherein, the bottom of described graphene film is located at transparent electrode layer upper surface.
Preferably, described transparent electrode layer adopts the graphene-based laminated film described in claim 1, in light-transmitting layer The contact of graphene film lower surface is provided with transparent substrate, the graphene film close-fitting transparent substrate layer following table of transparent electrode layer Face, the nano thin-film in the graphene-based laminated film of transparent electrode layer is located at the lower surface of its graphene film.
Preferably, it is provided with scalable flexible and transparent protective layer above described light transmission layer, described scalable flexible saturating Between bright protective layer and described light transmission layer, there is space, to avoid described scalable flexible and transparent protective layer and described light transmission Layer contacts；The edge of described scalable flexible and transparent protective layer is connected with insulating supporting structure, the bottom of insulating supporting structure Around the edge being arranged at described light transmission layer accordingly, thus supporting scalable flexible and transparent protective layer；Described scalable soft Property protective clear layer by stretching or curling is realizing the masking to described light transmission layer or exposure.
Preferably, the state of curling include from inside to outside a-circle-by-a-circle rolling and form a volume.
Preferably, described scalable flexible and transparent protective layer has two-layer, and ground floor is hydrophilic clear layer, in light It is less than during set intensity of illumination threshold value according to intensity and protects light transmission layer, thus reducing scalable flexible and transparent protective layer and light Organic pollution in transmission layer；The second layer is hydrophobic transparent layer, for exceeding set humidity threshold in ambient humidity When protect light transmission layer, thus suppress moisture enter described light transmission layer and enter solar film battery in；Hydrophilic is transparent It is connected with another insulating supporting structure, for isolating and supporting two-layer clear layer between layer and the edge of hydrophobic transparent layer.
Preferably, described insulating supporting structure includes insulating supporting structure and lower insulating supporting structure；Described exhausted Edge supporting construction is located at the top of described lower insulating supporting structure, and the width of described upper insulating supporting structure is lower exhausted less than described The width of edge supporting construction is so that the part that lower insulating supporting structure is located inside upper insulating supporting structure comes out and is used for Support one layer of scalable flexible and transparent protective layer being located on lower insulating supporting structure；The top of upper insulating supporting structure is used for propping up One layer of scalable flexible and transparent protective layer that support is located on upper insulating supporting structure.
Preferably, also there are controller, the first transducer, the second transducer and diagnosis apparatuss, controller is mutually electric with diagnosis apparatuss Even, diagnosis apparatuss are electrically connected with transducer phase；The graphene-based laminated film of light transmission layer includes：Optical detection region, shines for detecting It is mapped to intensity of illumination on solaode；And humidity search coverage, for detecting the humidity around solaode；
Optical detection region is electrically connected with the first transducer phase, for detecting the intensity of illumination of surrounding and producing the signal of telecommunication and send out Give the first transducer, this signal of telecommunication is converted to intensity of illumination data is activation to diagnosis apparatuss by the first transducer, and diagnosis apparatuss judge Whether this intensity of illumination data is higher than set intensity of illumination threshold value；If it has, then diagnosis apparatuss send contraction signal to control Device, controller controls described scalable flexible and transparent protective layer to execute crimping action；If it has not, then diagnosis apparatuss send stretch signal To controller, controller controls described scalable flexible and transparent protective layer to execute stretching；
Humidity search coverage is electrically connected with the second transducer phase, for detecting the humidity of surrounding and producing signal of telecommunication transmission To the second transducer, this signal of telecommunication is converted to humidity data and is sent to diagnosis apparatuss by the second transducer, and diagnosis apparatuss judge this humidity Whether data is higher than set humidity threshold；If it has not, then diagnosis apparatuss send contraction signal to controller, controller controls institute State scalable flexible and transparent protective layer execution crimping action；If it has, then diagnosis apparatuss send stretch signal to controller, controller Described scalable flexible and transparent protective layer is controlled to execute stretching.
Preferably, in the range of set intensity of illumination, described humidity threshold is set for described intensity of illumination threshold value Humidity range in.
Preferably, described hydrophilic clear layer and described hydrophobic transparent layer default conditions are rolled state.
Preferably, described hydrophilic clear layer is the graphene film of monolayer atomic layer.
Preferably, described hydrophobic transparent layer is the graphene film of two-layer or three layers of atomic layer.
Preferably, described light conversion layer is dye-sensitized layer, also has bottom electrode layer in light conversion layer bottom.
In order to achieve the above object, present invention also offers a kind of above-mentioned graphene-based automatically cleaning solar film battery Preparation method, it includes：
Step 0001：Prepare a light conversion layer；
Step 0002：Transparent electrode layer is formed on light conversion layer；
Step 0003：Light transmission layer is formed on transparent electrode layer.
Preferably, after described step 0003, also include：Form insulating supporting structure in the marginal area of light transmission layer； Then, the edge bottom of scalable flexible and transparent protective layer is accordingly bonded in described insulating supporting structure surface, thus The edge of scalable flexible and transparent protective layer is made to be connected on insulating supporting structure.
The graphene-based laminated film of the present invention and solar film battery, on graphene film, vertical-growth goes out continuously Nanometer Thin Films by Sol-Gel Method, during using this laminated film as light transmission layer, the high permeability of graphene film ensure that this THIN COMPOSITE Film, as the higher light transmission rate of light transmission layer, realizes self-cleaning function using Nanometer Thin Films by Sol-Gel Method；Further, adopt With this graphene-based laminated film as electrode layer, improve conductive speed using the quick carrier mobility of graphene film Rate, reduces the loss in opto-electronic conversion for the battery, by the use of the nano thin-film perpendicular to graphene film as dye migration passage, Improve dye migration speed, and then improve generating efficiency.
Brief description
Fig. 1 a is the cross section structure schematic diagram of the solar film battery of embodiments of the invention one
Fig. 1 b is the overlooking the structure diagram of the rounded solar film battery of embodiments of the invention one
Fig. 1 c is the overlooking the structure diagram of the solar film battery being rectangle of embodiments of the invention one
Fig. 2 is the scalable flexible and transparent protective layer of embodiments of the invention one in schematic diagram when crimping
Fig. 3 is each structural relation schematic diagram of the solaode of embodiments of the invention one
Fig. 4 is the hydrophilic transparent layer of embodiments of the invention one and hydrophobic clear layer on daytime and state during fine day is illustrated Figure
Fig. 5 is the hydrophilic transparent layer of embodiments of the invention one and hydrophobic clear layer on daytime and the state during rainy day is illustrated Figure
Fig. 6 is the hydrophilic transparent layer of embodiments of the invention one and hydrophobic clear layer at night and state during fine day is illustrated Figure
Fig. 7 is the hydrophilic transparent layer of embodiments of the invention one and hydrophobic clear layer at night and the state during rainy day is illustrated Figure
Fig. 8 is the overlooking the structure diagram of the graphene-based laminated film of embodiments of the invention one
Fig. 9 is the cross section structure schematic diagram of the graphene-based laminated film of embodiments of the invention one
Figure 10 is the flow process of the preparation method of graphene-based automatically cleaning solar film battery of embodiments of the invention two Schematic diagram
Figure 11-15 is each of the preparation method of graphene-based automatically cleaning solar film battery of embodiments of the invention two Preparation process schematic diagram
Figure 16-19 is the upper insulating supporting structure of embodiments of the invention two and prepared by the preparation of lower insulating supporting structure Each step schematic diagram of journey
Figure 20 is the schematic flow sheet of the preparation method of graphene-based laminated film of embodiments of the invention two
Figure 21-23 is each step schematic diagram of the preparation method of graphene-based laminated film of embodiments of the invention two
Figure 24-26 is each step schematic diagram of the nano thin-film growth course of embodiments of the invention two
Figure 27-28 is each step schematic diagram of the preparation process of one-dimensional nano line array of embodiments of the invention two
Figure 29-31 is each step schematic diagram of the preparation process of one-dimensional nano line array of embodiments of the invention two
Specific embodiment
For making present disclosure more clear understandable, below in conjunction with Figure of description, present disclosure is made into one Step explanation.Certainly the invention is not limited in this specific embodiment, the general replacement known to those skilled in the art Cover within the scope of the present invention.
Embodiment one
Below in conjunction with accompanying drawing 1-9 and specific embodiment, the present invention is described in further detail.It should be noted that, accompanying drawing is equal In the form of very simplification, use non-accurately ratio, and only in order to conveniently, clearly to reach aid illustration the present embodiment Purpose.
Refer to Fig. 1 a, the graphene-based automatically cleaning solar film battery of the present embodiment, is that dye sensitization of solar is thin Film battery, it includes：It is disposed with light transmission layer G03, transparent electrode layer G02 and light conversion layer G01 from top to bottom, this In, in light conversion layer G01 bottom, also there is bottom electrode layer G04；Incident illumination is successively through light transmission layer G03 and transparent electrode layer G02, enters back into light conversion layer G01, and light conversion layer G01 carries out opto-electronic conversion after absorbing incident illumination and produces electricity；Light transmission Layer G03 is graphene-based laminated film, as shown in Figure 1a, the graphene-based laminated film bag of the light transmission layer G03 of the present embodiment Include：Graphene film D031；Nano thin-film D032 (shown in dotted line inframe) on graphene film D031 for the vertical-growth；This reality Apply and multiple row nano thin-film D032 is had on graphene film D031 in example.The plane of nano thin-film D032 and graphene film D031 Vertically.Please continue to refer to Fig. 1 a, the bottom of graphene film D031 is located at transparent electrode layer G02 upper surface.Light conversion layer G01 can Think dye-sensitized layer, automatically cleaning solar film battery also has another electrode layer, come for dyestuff two electrode layers it Between conversion and migration passage is provided, in such as Fig. 1 a, arrow show dye migration direction, thus improving photoelectric transformation efficiency.This In adopt graphene-based laminated film, make use of its high light transmission rate and the photocatalytic semiconductor material can be with catalyzing organic To realize the self-cleaning function of solaode.And, in light transmission layer G03, nano thin-film D032 is perpendicular to graphene film D031 grows, and there is also certain spacing between multiple nano thin-film D032, can also be by arranging multiple nano thin-films Spacing between D032 to reach photocatalysis efficiency and the light transmission rate of optimum, for example, light transmission layer G03 in an OK range In graphene film D031 on there are multiple nano thin-film D032 being arranged in array, and the nanometer in light transmission layer G03 Spacing between thin film D032 be more than 10nm, thus not as traditional nano thin-film be covered in (mutually flat on graphene film The light transmission rate OK) leading to graphene film substantially reduces problem appearance, thus, do not interfere with the entirety of solaode Light transmission rate and light conversion efficiency.Preferably, nano thin-film D032 has multiple micro- engraved structures, thus constituting nano net, come Effectively improve photocatalysis efficiency and automatical cleaning ability.
In the present embodiment, transparent electrode layer G02 is also adopted by graphene-based laminated film；Specifically, light-transmitting layer G03's The contact of graphene film D031 lower surface is provided with transparent substrate D023, and the graphene film D021 of transparent electrode layer G02 is tight Patch transparent substrate D023 lower surface, the nano thin-film D022 in the graphene-based laminated film of transparent electrode layer G02 is located at it The lower surface of graphene film D021.Here, transparent electrode layer G02 adopts graphene-based laminated film, using graphene film Outstanding electric conductivity improving conductivity reduce loss, and the nano thin-film D022 insertion perpendicular to graphene film D021 Passage can be provided for the migration of dyestuff in light conversion layer G01, improve mobility and conversion efficiency, further, nano thin-film D022 has multiple micro- engraved structures, thus constituting nano net, to improve the capture ability to dyestuff, improves the effect that generates electricity further Rate.Here, in transparent electrode layer G02, the density of nano thin-film D022 should also be as the problem in view of light transmission rate, nano thin-film It is slightly larger that spacing between D022 can be arranged, preferably, between the nano thin-film D022 in transparent electrode layer G02 Spacing is more than 10nm.
In the present embodiment, please continue to refer to Fig. 1 a, it is additionally provided with scalable flexible and transparent protection above light transmission layer G03 Layer C1, C2, have space between scalable flexible and transparent protective layer C1, C2 and light transmission layer G03, to avoid scalable flexible saturating Bright protective layer C1, C2 are contacted with light transmission layer G03；The edge of scalable flexible and transparent protective layer C1 is connected with lower insulating supporting Structure Z1, the material of lower insulating supporting structure Z1 here is insulant, and the bottom part ring of lower insulating supporting structure Z1 is around setting In the edge of corresponding light transmission layer G03, thus supporting scalable flexible and transparent protective layer C1；Scalable flexible and transparent protective layer C1, C2 to realize the masking to light transmission layer G03 or exposure by stretching or crimping.Here curling can include from inside to outside one That encloses rolls and forms a volume, as shown in Figure 2.When extended, the state from volume flexes outward in plane.With regard to volume The active force that bent or stretching execution need to be used includes electric field force or the electrostatic force that the external world gives, and for example, default conditions are in Curling, makes scalable flexible and transparent protective layer C1, C2 have the normality of curling using memory technique such as stress memory, works as needs When scalable flexible and transparent protective layer C1, C2 stretch, electric field can be applied to scalable flexible and transparent protective layer C1, C2, making can Telescopic flexible protective clear layer C1, C2 surface produce identical charges, due to curling so that scalable flexible and transparent protective layer C1, C2 has the adjacently situated surfaces of curling, according to principle of same-sex repulsion, between the adjacently situated surfaces of curling mutually exclusive so that scalable soft Property protective clear layer C1, C2 gradually extend.
Specifically, please continue to refer to Fig. 1 a, scalable flexible and transparent protective layer C1, C2 have two-layer, and ground floor is hydrophilic Property clear layer C1, for protecting light transmission layer when intensity of illumination is less than set intensity of illumination threshold value, thus reducing itself Organic pollution and light transmission layer G03 organic pollution；The second layer is hydrophobic transparent layer C2, in ambient humidity Exceed and protect light transmission layer G03 during set humidity threshold, thus suppressing moisture to enter light transmission layer G03 and enter solar energy In hull cell.It should be noted that the present invention is suitable to the in the vertical direction of hydrophilic transparent layer C1 and hydrophobic clear layer C2 Sequence is not restricted, for example, hydrophilic transparent layer C1 may be located on hydrophobic clear layer C2 it is also possible to be located at hydrophobic clear layer C2 it Under.Here, intensity of illumination threshold value can be in the range of set intensity of illumination, and humidity threshold can be in set humidity model In enclosing.
In the present embodiment, lower insulating supporting structure Z1 is additionally provided with insulating supporting structure Z2, upper insulating supporting structure Z2 and lower insulating supporting structure Z1 can be integrally formed or molding twice, and the width of upper insulating supporting structure Z2 is little In lower insulating supporting structure Z1 width so that lower insulating supporting structure Z1 be located at upper insulating supporting structure Z2 inside partly sudden and violent Expose and be used for supporting the hydrophilic transparent layer C1 being located on lower insulating supporting structure Z1；The top of upper insulating supporting structure Z2 is used In supporting the hydrophobic clear layer C2 being located on upper insulating supporting structure Z2, so that two-layer clear layer C1, C2 are located at down respectively On insulating supporting structure Z1 and upper insulating supporting structure Z2, the top of upper insulating supporting structure Z2 and lower insulating supporting structure Z1's Top has certain spacing, for isolating two-layer protective clear layer C1, C2, and leaves the transparent of enough space empty lower floors Protective layer C1 is crimped or stretches；Upper insulating supporting structure Z2 and lower insulating supporting structure Z1 is around the side of light transmission layer G03 Edge is arranged.In the present embodiment, hydrophilic transparent layer C1 can be the graphene film of monolayer atomic layer, and hydrophobic clear layer C2 can be Two-layer or the graphene film of three layers of atomic layer.In the present embodiment, the width of lower insulating supporting structure Z1 is more than upper insulating supporting The width of structure Z2 is so that the hydrophilic transparent of hydrophobic clear layer C2 on upper insulating supporting structure Z2 and lower insulating supporting structure Z1 Layer C1 does not interfere with each other when executing curling or stretching respectively.
In the present embodiment, when solar film battery is circular, incorporated by reference to Fig. 1 a and Fig. 1 b, upper insulating supporting structure Z2 Become narrow gradually to B side from A side, but highly constant；Lower insulating supporting structure Z1 is constant or gradually broaden to B side width from A side, But it is highly constant；Certainly, the height of upper insulating supporting structure Z2 can also be gradually to uprise or become short, lower insulating supporting structure Z1 Height can also be gradually to uprise or become short, upper insulating supporting structure Z2 and lower insulating supporting structure Z1 gradually uprises or gradually The trend becoming short can be consistent or contrary；So, protective clear layer C1, C2, in curling or stretching, extension, can obtain To powerful support, also can save shared because of this gradual change width of upper insulating supporting structure Z2 and lower insulating supporting structure Z1 Light transmission layer G03 superjacent air space, and upper insulating supporting structure Z2 and lower insulating supporting structure Z1 gradual change width cooperate, So that the hydrophilic transparent layer C1 of hydrophobic clear layer C2 on upper insulating supporting structure Z2 and lower insulating supporting structure Z1 is respectively Do not interfere with each other when execution curling or stretching.Meanwhile, one end of the hydrophobic clear layer C2 on upper insulating supporting structure Z2 is solid Surely it is bonded to insulating supporting structure Z1 region the widest (A side dotted line frame), the hydrophilic transparent layer on lower insulating supporting structure Z1 One end retainingf key of C1 is together in lower insulating supporting structure Z1 region the widest (B side dotted line frame).Preferably, the solar energy of circle is thin Film battery is in the fixing one end A side dotted line frame being bonded hydrophobic clear layer C2 of upper insulating supporting structure Z2 and lower insulating supporting structure Z1 One end of fixing bonding hydrophilic transparent layer C1 (B side dotted line frame) is set to straight line plane rather than arc surface, dotted line frame in such as Fig. 1 b Shown, dotted line frame also may indicate that the position of fixing bonding arranges the plane that is in line.
In the present embodiment, when solar film battery is for rectangle, go up insulating supporting structure Z2 and lower insulation accordingly It is rectangle that supporting construction Z1 overlooks figure, and incorporated by reference to Fig. 1 a and Fig. 1 c, upper insulating supporting structure Z2 gradually becomes to D side from C side Narrow, but highly constant；Lower insulating supporting structure Z1 is constant or gradually broaden to D side width from C side, but highly constant；Certainly, on The height of insulating supporting structure Z2 can also be gradually to uprise or become short, and the height of lower insulating supporting structure Z1 can also be gradually Uprise or become short, upper insulating supporting structure Z2 and lower insulating supporting structure Z1 gradually uprises or gradually becomes short trend can phase one Cause or contrary；Meanwhile, one end retainingf key of the hydrophobic clear layer C2 on upper insulating supporting structure Z2 is together in upper insulating supporting structure Z2 side the widest (shown in the dotted line frame of C side), one end retainingf key of the hydrophilic transparent layer C1 on lower insulating supporting structure Z1 together in Lower insulating supporting structure Z1 side the widest (shown in the dotted line frame of D side).
Also, it should be noted the overall structure of the solar film battery of the present invention can also be square, oval Etc. other structures.
Refer to Fig. 3, the graphene-based automatically cleaning solar film battery of the present embodiment also has controller, the first conversion Device, the second transducer and diagnosis apparatuss, controller is electrically connected with diagnosis apparatuss phase, and diagnosis apparatuss are electrically connected with transducer phase；The stone of light transmission layer Mertenyl laminated film includes：Optical detection region, is irradiated to intensity of illumination on solaode for detecting；And humidity detects Region, for detecting the humidity around solaode；
Optical detection region is electrically connected with the first transducer phase, for detecting the intensity of illumination of surrounding and producing the signal of telecommunication and send out Give the first transducer, this signal of telecommunication is converted to intensity of illumination data is activation to diagnosis apparatuss by the first transducer, and diagnosis apparatuss judge Whether this intensity of illumination data is higher than set intensity of illumination threshold value；If it has, then diagnosis apparatuss send contraction signal to control Device, controller controls the hydrophilic transparent layer execution crimping action of scalable flexible and transparent protective layer；If it has not, then diagnosis apparatuss send To controller, controller controls the hydrophilic transparent layer execution stretching of described scalable flexible and transparent protective layer to stretch signal；
Humidity search coverage is electrically connected with the second transducer phase, for detecting the humidity of surrounding and producing signal of telecommunication transmission To the second transducer, this signal of telecommunication is converted to humidity data and is sent to diagnosis apparatuss by the second transducer, and diagnosis apparatuss judge this humidity Whether data is higher than set humidity threshold；If it has not, then diagnosis apparatuss send contraction signal to controller, controller controls institute State the hydrophobic clear layer execution crimping action of scalable flexible and transparent protective layer；If it has, then diagnosis apparatuss send stretch signal to Controller, controller controls the hydrophobic clear layer execution stretching of described scalable flexible and transparent protective layer.
Additionally, entirely in graphene-based automatically cleaning solar film battery, light transmission layer G03, transparent electrode layer G02 all adopt With another clear superiority of graphene film it is exactly：Due to the good heat conductivity of graphene film, can radiate in time, it is to avoid Because heat effect produces the problem that expansion or shrinkage causes deformation between the structure at all levels of automatically cleaning solar film battery, Thus improve the service life of solaode and the performance that permanent holding is good.Meanwhile, graphene-based when the present embodiment Automatically cleaning solar film battery can be applied to the occasion of printing opacity, for example, be applied on window, be applied to computer or handss Machine screen first-class naturally it is also possible to be applied to not need the occasion of printing opacity.When light conversion layer is also adopted by flexible material, this enforcement The graphene-based automatically cleaning solar film battery of example be possible to realize bending come the occasion to adapt to there is given shape so that this The solar film battery application of embodiment is more flexible.
In the present embodiment, hydrophilic clear layer C2 and hydrophobic transparent layer C1 default conditions are rolled state；Intensity of illumination The setting of threshold value can count a suitable model according to the illumination on daytime that one day is experienced for 24 hours and the illumination at night Enclose, here, when daytime is to have solar irradiation, solaode can collect sunlight, now, do not block light transmission Layer；When night is not have sunlight, solaode can not mobile phone sunlight, now, if for a long time expose light Transmission layer can pollute, and can be extended using hydrophilic transparent layer, shelter from light transmission layer, thus reducing light transmission layer Pollution, and because using hydrophilic transparent layer, organic pollution is not easy to be attached to hydrophilic transparent layer surface, drops further The low pollution of hydrophilic transparent layer；The setting of humidity threshold should be solaode receptible humidity maximum limit, But for safer consideration, humidity threshold can be arranged extremely low, when rainy, the humidity now being detected is much Beyond humidity threshold, therefore, when rainy, need to cover up light transmission layer using hydrophobic clear layer；When fine day, will dredge Water clear layer is accepted, and does not block light transmission layer, it is to avoid excessively to affect the transmission of sunlight at many levels.It should be noted that this In intensity of illumination in addition to using sunlight, light can also be utilized, such as daylight lamp etc. is realizing opto-electronic conversion.
Hereinafter refer to Fig. 4～7 to describe the change with environment of the stretching, extension of hydrophilic transparent layer and hydrophobic clear layer or rolled state Change, and so that hydrophilic transparent layer is located at below hydrophobic clear layer be as a example described below.
Refer to Fig. 4, Fig. 4 is the hydrophilic transparent layer of embodiments of the invention one and hydrophobic clear layer on daytime and during fine day View, now, hydrophilic transparent layer C1 all becomes rolled state with hydrophobic clear layer C2, so that sunlight can be straight Access is mapped to light transmission layer G03, it is to avoid the consumption of sunlight；
Refer to Fig. 5, Fig. 5 is the hydrophilic transparent layer of embodiments of the invention one and hydrophobic clear layer on daytime and during the rainy day View, now, hydrophilic transparent layer C1 be in rolled state, hydrophobic clear layer C2 be in extended configuration so that moisture Light transmission layer G03 can not be entered, realize the protection to light transmission layer G03, and, only blocked with layer of transparent layer C2, relatively The consumption to sunlight can be reduced although rainy day sunlight is weaker in two-layer clear layer C1, C2, but still can utilize.
Refer to Fig. 6, Fig. 6 is the hydrophilic transparent layer of embodiments of the invention one and hydrophobic clear layer at night and during fine day View, now, hydrophilic transparent layer C1 be in extended configuration, hydrophobic clear layer C2 be in rolled state, hydrophilic transparent layer C1 Block light transmission layer so that solaode carries out automatically cleaning protection when not working to light transmission layer G03.
Refer to Fig. 7, Fig. 7 is the hydrophilic transparent layer of embodiments of the invention one and hydrophobic clear layer at night and during the rainy day View, now, hydrophilic transparent layer C1 be in extended configuration, hydrophobic clear layer C2 be in extended configuration, hydrophobic clear layer C2 Rainwater can be excluded and enter light transmission layer G03, hydrophilic transparent layer C1 can also carry out automatically cleaning protection further.
It should be noted that hydrophilic transparent layer C1 in the present embodiment, hydrophobic clear layer C2 with daytime, night, fine day Various states with the rainy day are example, and other rational states are arranged still within protection scope of the present invention；Meanwhile, this Bright solaode can also utilize the luminous energy of other forms to light using being not limited to sunlight, certainly, coordinates various fields Close and environment, hydrophilic transparent layer, hydrophobic clear layer can show different mated condition, and various conversion are all in the think of of the present invention Within thinking.
Next, in light transmission layer G03 in the graphene-based automatically cleaning solar film battery of specific descriptions the present embodiment And transparent electrode layer G02 graphene-based laminated film structure, in the present embodiment, in light transmission layer G03 and thoroughly The structure of the graphene-based laminated film of prescribed electrode layer G02 is identical.Refer to Fig. 8 and Fig. 9, the graphene-based of the present embodiment is combined Thin film includes：One graphene film 101；Nano thin-film (shown in dotted line inframe) on graphene film 101 for the vertical-growth；This Illustrate only two row nano-wire arrays on graphene film 101 in the accompanying drawing 8 and 9 of embodiment, then the graphite of the present embodiment Multiple row nano-wire array is had on alkene thin film 101, accompanying drawing 8 and 9 is only intended to illustrate, but this is not used in the protection limiting the present invention Scope.The plane of nano thin-film (shown in dotted line inframe) is vertical with transparent substrates 101；Nano thin-film has multiple micro- engraved structures 103, thus forming nano net, and the bottom of nano thin-film is bonded by chemical bond phase with graphene film 101；Nano thin-film Material is conductor photocatalysis material.In the present embodiment, micro- engraved structure 103 is in the array arrangement being alternately staggered, micro- hollow out knot Structure 103 may be located at the side wall touching position of the nano wire 102 constituting nano thin-film it is also possible to be located on nano wire 102.Here Nano thin-film be to be grown perpendicular to graphene film 101 by nano wire 102 and the side of adjacent nanowires 102 contacts and formed Nano thin-film, further can etch through nano thin-film and form micro- void region 103.Meanwhile, the nano wire 102 contacting it Between be bonded by chemical bond phase, can lead in adjacent nano due to contacting during the lateral growth of adjacent nanowires 102 The a certain degree of continued growth in line 102 interface, thus due to there being these chemical bonds between these nano wires 102 of contacting In conjunction with and more firm, thus constituting a nano thin-film.Here, the diameter of nano wire 102 is the thickness of nano thin-film, can With diameter when controlling adjacent nanowires 102 to contact by controlling growth technique such as time, temperature etc., thus forming institute Need the nano thin-film of thickness；The height of nano thin-film can also be controlled by controlling growth technique, thus obtaining relatively thin simultaneously And shorter nano thin-film, to improve specific surface area and the photocatalytic activity of nano thin-film, nano thin-film can also be avoided simultaneously The blocked up or too high transparency reducing entirely graphene-based laminated film.Preferably, the thickness of nano thin-film is not more than 10nm, For example, 5-7nm.Preferably, the graphene film 101 of the present embodiment is single-layer graphene film.
In the present embodiment, because nano thin-film needs to realize photo-catalysis capability with photocatalysis performance, therefore, receive The material of rice thin film is conductor photocatalysis material.Preferably, catalysis material is broad-band gap catalysis material.Accordingly, receive Rice noodle 102 can also be wide band gap semiconducter nano wire, for example, titanium alloy nano line or zinc alloy nano-wire, and, both The cost of alloy material is relatively low, advantageously in large-scale production.Wherein, titanium alloy nano line can be chosen as titanium dioxide Nano wire, zinc alloy nano-wire can be chosen as zinc oxide nanowire；The crystal formation of titanium dioxide nano thread can be Ca-Ti ore type Or rutile-type, the crystal formation of zinc oxide nanowire is hexahedron structure.
It should be noted that when nanowire sidewalls contact, merging between nanowire sidewalls, for example, if nano wire For titanic oxide material, then merge between adjacent nano line side wall.
In the present embodiment, micro- engraved structure 103 can be nanometer level microporous, preferably, nanometer level microporous can be not more than 10nm is it is preferable that no more than 5nm；Preferably, the spacing between adjacent micro- engraved structure 103 is not more than 10nm.Micro- hollow out knot The setting of structure 103, not only increases the specific surface area of nano net, also improves the adsorption efficiency of nano net, meanwhile, micro- hollow out knot For another kind of angle, be equivalent in nano net is that multiple less nanostructureds are constituted to the nano net that structure 103 is formed, Thus further increasing the photocatalysis effect of nano net.It should be noted that micro- engraved structure of the present invention is not limited to this reality Apply the nanometer level microporous of example, shape is not limited to circle, can also be other shapes, such as：Regular polygon, irregular figure etc. are all Can, the invention is not limited in this regard.
Further, in order to not affect the light transmission rate of entirely graphene-based laminated film, multiple nano thin-films are in array Arrangement, and the spacing between adjacent nano thin film should be slightly larger, preferably, the spacing between adjacent nano thin film is more than 10nm.
Additionally, nano net can be also used for filtration, detection of gas.When micro- engraved structure 103 is nanometer level microporous, particularly When spacing between adjacent micro- engraved structure 103 is not more than 10nm, can be also used for the filtration of bigger molecule.
Embodiment two
Below in conjunction with accompanying drawing 10-27 and specific embodiment, the present invention is described in further detail.It should be noted that, accompanying drawing All in the form of very simplification, use non-accurately ratio, and only in order to conveniently, clearly to reach aid illustration the present embodiment Purpose.
Refer to Figure 10, the graphene-based automatically cleaning solar film battery in the present embodiment two, to above-described embodiment one Preparation method, including：
Step 0001：Refer to Figure 11, prepare a light conversion layer G01；
Specifically, step 0001 specifically includes：One substrate SUB is provided；In substrate SUB preparation bottom electrode layer G04 and Light conversion layer G01；Light conversion layer G01 can change organic layer for dye sensitization light.
Step 0002：Refer to Figure 12, transparent electrode layer G02 is formed on light conversion layer G01；
Step 0003：Refer to Figure 13, light transmission layer G03 is formed on transparent electrode layer G02.
In the present embodiment, also include step 0004 after step 0003：Refer to Figure 14, on the side of light transmission layer G03 Edge region forms insulating supporting structure Z1, Z2；Then, will be corresponding for the edge bottom of scalable flexible and transparent protective layer C1, C2 Be bonded in insulating supporting structure Z1, Z2 surface, so that the edge of scalable flexible and transparent protective layer C1, C2 is connected to On insulating supporting structure Z1, Z2.Here insulating supporting structure Z1, Z2 can be insulating barrier, scalable flexible and transparent protective layer C1, C2 can be graphene film.
It should be noted that here, the upper insulating supporting structure Z2 with regard to above-described embodiment one and lower insulating supporting structure The preparation of Z1 can include：First, depositing insulating layer, then using but be not limited to photoetching and etching technics to etch upper insulation Support structure Z2 and the pattern of lower insulating supporting structure Z1, for example, it is possible to first etch the upper insulating supporting structure Z2 of certain depth Pattern, then the pattern etching lower insulating supporting structure Z1；Or：First deposit the first layer insulating, then using but do not limit The pattern of lower insulating supporting structure Z1 is etched in photoetching and etching technics in the first layer insulating；It is coated with photoresist, and Form the area of the pattern of upper insulating supporting structure Z2 through photoetching in the photoresist, then deposit the second layer insulating in photoresist In the area of the pattern of upper insulating supporting structure Z2, then remove remaining photoresist, thus obtaining insulating supporting structure Z2.This Outward it is contemplated that deposition and the damage to light transmission layer G03 for the etching technics, can adopt and insulating supporting structure Z1, Z2 are bonded in The technique of light transmission layer G03 marginal area, it specifically includes：First, refer to Figure 16, depositing insulating layer on a substrate J01 J02, then, refer to Figure 17, through photoetching and etching thus preparing insulating supporting structure Z2 on inverted in insulating barrier J02 With lower insulating supporting structure Z1；Refer to Figure 18 again, this substrate J01 be inverted, thus by upper insulating supporting structure Z2 and Lower insulating supporting structure Z1 is inverted；And adopt bonding technology, make bottom and the light transmission layer of lower insulating supporting structure Z1 The marginal area phase bonding of G03；Finally, refer to Figure 19, substrate J01 is peeled off, for example, substrate J01 is had using readily soluble Substrate J01 can be eroded by machine material using corresponding medicinal liquid；Or, substrate SUB and upper insulation are made using chemical liquid The interface peel that support structure Z2 contacts.If the substrate SUB material employed in substrate J01 adopted here and step 0001 Material is identical, can erode using identical medicinal liquid or using being bonded of identical medicinal liquid destruction substrate SUB and bottom electrode layer G04, And destroy being bonded of substrate J01 and upper insulating supporting structure Z2, thus the two is peeled off together.
Also include step 0005 afterwards：Refer to Figure 15, the structure completing step 0004 is separated with substrate SUB. Detailed description with regard to the graphene-based automatically cleaning solaode of the present embodiment two may refer to embodiment one, no longer superfluous here State.
Next, being described in further details to the method for the graphene-based laminated film of preparation embodiment one.
Refer to Figure 20, to illustrate as a example two row nano-wire arrays on graphene film in the present embodiment two, but this It is not used in and limit the scope of the invention.In the present embodiment, the preparation side of the graphene-based laminated film of above-described embodiment one Method includes：
Step 01：Refer to Figure 21, a graphene film 101 is provided；Here, preferably, this graphene film is monolayer Graphene film, the preparation with regard to single-layer graphene film can be prepared using chemical meteorology deposition method, high-temperature decomposition etc., This is that those skilled in the art could be aware that, repeats no more here.
Step 02：Refer to Figure 22, growth nano thin-film (shown in dotted line inframe) on graphene film 101；Grown Nano thin-film place plane perpendicular to graphene film 101, chemical bond is passed through with graphene film 101 in the bottom of nano thin-film Mutually it is bonded；Chemical bond is between atom and the atom of material composition of graphene film 101 in nano film material composition Bonding, for example, the material of nano thin-film is titanium dioxide, then the titanium atom of titanium dioxide and/or or oxygen atom thin with Graphene The carbon atom phase bonding of film 101 obtains Ti-C key and/or C-O key.
In the present embodiment, after step 02, can also include：
Step 03：Refer to Figure 23, nano thin-film (shown in dotted line inframe) etches multiple micro- engraved structures 103. Here it is possible to using plasma lithographic technique or laser-induced thermal etching are etching micro- engraved structure 103.
Specifically, in the present embodiment, nano thin-film in step 02 taking the growth of one layer of nano thin-film to be as a example described below Growth course, it includes：
Step 021, refers to Figure 24, prepares 1-dimention nano sub-array 201 on graphene film 101；For example, metatitanic acid Seed solution or zinc acetate seed solution, this is that those skilled in the art could be aware that, repeats no more here.
Step 022, refers to Figure 25, and with nanometer sub-array 201 as base, every nanometer seed song is to growth nanowire 202, thus forming nano-wire array；Here it is possible to using chemical vapour deposition technique, aqua-solution method or electrochemical plating next life Long nano wire 202.For example, titanium dioxide nano thread is prepared using hydro-thermal method, solution concentration is placed in for 0.04M precursor solution In reactor, at a temperature of 100～150 DEG C, constant temperature grows 01～0.5 hour, finally can get diameter less than the two of 10nm Titanium oxide nano wire.Again for example, zinc oxide nanowire is prepared using hydro-thermal method, solution concentration is put for 0.05M precursor solution In reactor, at a temperature of 90～140 DEG C, constant temperature grows 01～0.5 hour, finally can get the oxygen that diameter is less than 10nm Change zinc nano wire.Preparation with regard to nano wire is also the ordinary skill in the art, is that those skilled in the art could be aware that, this In repeat no more.
Step 023, refers to Figure 26, and the side of adjacent nanowires contacts with each other, thus being formed perpendicular to graphene film Nano thin-film.The diameter of the nano wire 203 in step 023 is all higher than the diameter of the nano wire 202 in step 022, step 023 In the length of nano wire 203 be all higher than the length of the nano wire 202 in step 022, for example, be further continued for above-mentioned growth conditionss not Become, extend growth time 0.1～0.5 hour so that nano wire cross growth contacts, thus forming required nano titania Thin film or zinc oxide nano film.The growth technique of nano wire can adopt conventional method, for example, it is possible to by other conditions not Become, extend growth time, or the longitudinal growth realizing nano wire by the different growth temperature of two steps or precursor concentration And cross growth.
Here, realize the controlled of nanowire diameter when nanowire sidewalls contact with each other and can take following manner：
It is possible, firstly, to by substantial amounts of experiment obtain other conditions constant when, under precursor solution concentration permanence condition Nano wire longitudinal direction average growth rate and horizontal average growth rate；And when other conditions are constant, dense in precursor solution Nano wire longitudinal direction average growth rate and horizontal average growth rate under conditions of different such as concentration M1 of degree or M2；In the same manner, also may be used To obtain nano wire longitudinal direction average growth rate and the horizontal average growth rate under the conditions of different temperatures P1 or P2.
Then, according to the average growth rate tried to achieve, under the conditions of corresponding growing environment, set the target of nano wire Diameter D and target length L；
Then, the position of nano wire, according to aimed dia D, is set on a transparent substrate, and the position of nano wire that is to say kind The position of son；The theoretical pitch of seed is also D, it may appear that multiple seed assembles situation, as long as the model in D in actual process There is at least one seed, so, if form one-dimensional continuous nanometer seed membrane can achieve in enclosing；Furthermore, it is also possible to Combined using template and etching technics, the preparation of specific 1-dimention nano sub-array will be in subsequent detailed description.
Then, the calculating of the growth time with regard to step 22 and step 23 and diameter can adopt following process：
A kind of method is：Set and average for D/ longitudinal growth speed is obtained required time t1, L/ average transverse is grown speed Rate obtains required time t2 it is contemplated that required nanowire diameter is the principal element determining nanometer thickness of net, no matter t1 and t2 Size how, and selected actual growth time t should be greater than or is equal to time t1；In the premise that nanowire growth environment is constant Under, substantially step 022 and step 023 are continuous processes, and the total growth time that only need to arrange nano wire is t.
Another kind of method is：Can receive according under conditions of precursor solution concentration difference when other conditions are constant Rice noodle longitudinal direction average growth rate and horizontal average growth rate, using the aimed dia D setting nano wire and target length L, Select the precursor concentration for step 022 and step 023 respectively, and calculate corresponding growth time, now, step 022 The concentration of precursor solution is set to M1, and growth time is set to T1；The concentration of the precursor solution of step 023 is set to M2, then basis Nano wire longitudinal direction average growth rate V1 (being obtained by many experiments before) under concentration M1, obtains step 022 complete The diameter D1=V1*T1 of nano wire after one-tenth；Again by aimed dia D-D1, obtain difference in diameter D2, then, according under concentration M2 Nano wire longitudinal direction average growth rate V2 (being obtained by many experiments before), when obtaining the growth needed for step 023 Between T2=D2/V2.Should in the case of, preferably, selected precursor solution concentration M1 ＜ M2 is so that the horizontal life of step 023 Long-time shortening.
Yet another method is：Can be indulged according to nano wire under conditions of growth temperature difference when other conditions are constant To average growth rate and horizontal average growth rate, using the aimed dia D setting nano wire and target length L, select respectively Select the precursor concentration for step 022 and step 023, and calculate corresponding growth time, now, the growth temperature of step 022 Degree is set to P1, and growth time is set to T1；The growth temperature of step 023 is set to P2, then according to the nano wire under growth temperature P1 Longitudinal average growth rate V1 (being obtained by many experiments before), obtains the diameter D1 of nano wire after the completion of step 022 =V1*T1；Again by aimed dia D-D1, obtain difference in diameter D2, then, longitudinally flat according to the nano wire under growth temperature P2 All growth rates V2 (being obtained by many experiments before), obtain the growth time T2=D2/V2 needed for step 023.Should In the case of, preferably, selected growth temperature P1 ＜ P2 so that step 023 the cross growth time shorten.
It should be noted that the concrete technology with regard to the preparation of Seed Layer, the longitudinal growth of nano wire and cross growth is equal It is that those skilled in the art could be aware that.
The preparation process of wherein row of one dimensional nanometer sub-array is described below in detail.
In the present embodiment, the preparation that wherein at least has row of one dimensional nanometer sub-array can include：
First, refer to Figure 27, graphene film forms nanometer seed precursor solution, after being dried, form nanometer kind Sub- thin film 301；Here, various nanometer seed presomas are different because of the difference of nano material, for example, zinc-oxide nano seed Precursor solution can be zinc acetate solution, and the precursor solution of nano titania seed can be titanium chloride solution etc., This is that those skilled in the art could be aware that, repeats no more here.
Secondly, refer to Figure 28, nanoscale vestige is marked in nanometer seed thin film 301 using induced with laser technology, receives (in Figure 28 shown in dotted line frame) induces nanometer sub-array 302 for meter level mark region.Here, the live width of nanoscale vestige is permissible Equal to or more than the diameter of nanometer seed, the width of nanometer sub-array 302 region is equal to the live width of nanoscale vestige.Relatively Good, the live width of nanoscale vestige is less than 5nm, and further, the live width of nanoscale vestige can less for example be less than 1nm, so that the diameter of the nanometer seed growing is less than 5nm or even 1nm, and the nano wire that goes out of subsequent growth is straight Footpath is unlikely to excessive, or even in below 5nm.It should be noted that because the nanoscale vestige of induced with laser is continuous and line Wide ultra-fine so that seed spacing in nanometer sub-array and seed diameter are respectively less than the live width of nanoscale vestige.
Additionally, in the present embodiment, the preparation that wherein at least has row of one dimensional nanometer sub-array can also adopt following step Suddenly：
First, refer to Figure 29, one layer of mask 401 is formed on graphene film；
Then, refer to Figure 30, mask 401 is carried out with photoetching and/or etching forms one nanoscale opening 402；Here, When the material of mask 401 is photosensitivity material, one nanoscale can be etched on mask 401 using photoetching process and open Mouth 402；When the material of mask 401 is inorganic material, can carve using photoetching and etching technics or only with anisotropy Etching technique to etch one nanoscale opening 402 on mask 401.With regard to the formation of this nanoscale opening 402, using existing Photoetching process can accomplish 10nm, 7nm 7nm, 5nm, 3nm included below technology using be repeated several times exposure and extreme ultraviolet Photoetching (EUV) technology can be achieved on.Therefore, the nanoscale opening 402 of the present embodiment can accomplish the live width of below 10nm, Nanometer the diameter of seed and the diameter of spacing and the nano wire being formed be also atomic little, the nano thin-film of the present embodiment and Nano net is expected to produce on a large scale and apply.
Finally, refer to Figure 31, and combine Figure 30, the graphene film that nanoscale opening 402 is exposed is formed and receives Rice sub-array 403.Here it is possible to adopt physical vaporous deposition, sol-gal process, spraying process, galvanoplastic, magnetron sputtering method Nanometer sub-array 403 is formed on the graphene film that nanoscale opening is exposed；Or by seed solution spin coating or drop in It is dried after on the graphene film that nanoscale opening 402 is exposed and form nanometer sub-array 403.With regard to nanometer sub-array 403 formation can adopt common process, adopted the precursor solution of different nano materials for different nano materials To prepare, usually spin-coating method, instillation nanometer seed precursor solution are formed in nanoscale opening, through indifferent gas style As nitrogen dries up, form nanometer seed precursor film, nanometer kind can be made through such as not higher than 100 DEG C of temperature of low-temperature heat A nanometer sub-array is crystallized out, this is also that those skilled in the art could be aware that, repeats no more here in sub- precursor film.By Live width in nanoscale opening 402 is superfine so that the diameter of nanometer seed and spacing are all less, so that the nano wire being formed Diameter, the thickness of nano thin-film and nano net thickness all in nanoscale for example in below 10nm, thus having obtained size Minimum nano net, has higher specific surface area, further suppress existing superfine nanoparticle agglomerates and wave particle dualism Problem, therefore, the graphene-based laminated film of the present embodiment has higher photocatalysis efficiency and good transparency, Ke Yiying For transparent material in need field, for example window, screen, on clear glass, these transparent materials can be made certainly For the transparent substrates of graphene-based laminated film, not only can transmission applications in photovoltaic art, be also used as molecular sieve and carry out The filtration of molecular level, sterilization, elimination harmful gass, can also carry out detection of gas and be applied in gas sensor, and application In medical treatment, biological field etc..
Although the present invention with preferred embodiment disclose as above, so described embodiment illustrate only for the purposes of explanation and , it is not limited to the present invention, if those skilled in the art can make without departing from the spirit and scope of the present invention Dry change and retouching, the protection domain that the present invention is advocated should be to be defined described in claims.

Claims (34)

1. a kind of graphene-based laminated film is it is characterised in that include：One graphene film and vertical-growth are in described graphite Nano thin-film on alkene thin film；The plane of described nano thin-film is vertical with described graphene film；The bottom of described nano thin-film It is bonded by chemical bond phase with described graphene film；The material of described nano thin-film is conductor photocatalysis material.
2. graphene-based laminated film according to claim 1 is it is characterised in that described graphene film is two-layer atom The graphene film of layer or the graphene film of three layers of atomic layer.
3. graphene-based laminated film according to claim 1 is it is characterised in that described nano thin-film has multiple micro- engrave Hollow structure, thus constitute nano net.
4. graphene-based laminated film according to claim 3 is it is characterised in that between adjacent described micro- engraved structure Spacing be not more than 10nm.
5. graphene-based laminated film according to claim 1 it is characterised in that described nano net by nano wire perpendicular to The side of transparent substrates growth and adjacent nanowires contacts formation nano thin-film, then etches through nano thin-film and form micro- vacancy section Domain.
6. graphene-based laminated film according to claim 5 is it is characterised in that logical between the described nano wire that contacts Cross chemical bond phase bonding.
7. graphene-based laminated film according to claim 5 is it is characterised in that the diameter of nano wire is described nanometer The thickness of thin film.
8. graphene-based laminated film according to claim 7 is it is characterised in that the thickness of described nano thin-film is not more than 10nm.
9. graphene-based laminated film according to claim 1 is it is characterised in that described conductor photocatalysis material is width Gap semiconductor catalysis material.
10. graphene-based laminated film according to claim 9 is it is characterised in that described wide band gap semiconducter photocatalysis Material is titanium alloy nano line and/or zinc alloy nano-wire.
11. graphene-based laminated films according to claim 1 are it is characterised in that have many on described graphene film The individual described nano thin-film being arranged in array.
The preparation method of the graphene-based laminated film described in a kind of 12. claim 1 is it is characterised in that include：
Step 01：One graphene film is provided；
Step 02：Nano thin-film is grown on described graphene film；The nano thin-film place plane being grown is perpendicular to described Graphene film, the bottom of described nano thin-film is bonded by chemical bond phase with graphene film.
The preparation method of 13. transparent photocatalyzing thin film according to claim 12 is it is characterised in that after described step 02 Also include：Step 03, etches multiple described micro- engraved structures, thus forming nano net on described nano thin-film.
The preparation method of 14. transparent photocatalyzing thin film according to claim 13 it is characterised in that in described step 03, Using plasma lithographic technique or laser-induced thermal etching are etching described micro- engraved structure.
The preparation method of the 15. transparent photocatalyzing thin film according to claim 12 or 13 is it is characterised in that described step 02 In, the growth course of nano thin-film includes：
Step 021, prepares 1-dimention nano sub-array on the transparent substrate；
Step 022, with nanometer sub-array as base, every nanometer seed bent to growth nanowire, thus forming a nanometer linear array Row；
Step 023, the side of adjacent nanowires contacts with each other, thus forming the nano thin-film perpendicular to transparent substrates.
The preparation method of 16. transparent photocatalyzing thin film according to claim 15 is it is characterised in that in described step 021 In, the preparation that wherein at least has row of one dimensional nanometer sub-array includes：First, form nanometer seed on the transparent substrate Precursor solution, forms nanometer seed thin film after being dried；Secondly, drawn in described nanometer seed thin film using induced with laser technology Go out nanoscale vestige, nanoscale mark region induces a nanometer sub-array.
The preparation method of 17. transparent photocatalyzing thin film according to claim 16 is it is characterised in that described nanoscale vestige Live width be equal to or more than the diameter of nanometer seed, the width of described nanometer sub-array region is equal to described nanoscale trace The live width of mark.
The preparation method of 18. transparent photocatalyzing thin film according to claim 15 it is characterised in that in described step 021, The preparation that wherein at least has row of one dimensional nanometer sub-array includes：
First, form one layer of mask on a transparent substrate；
Then, mask is carried out with photoetching and/or etching forms one nanoscale opening；
Finally, nanometer sub-array is formed on the transparent substrates that nanoscale opening is exposed.
The preparation method of 19. transparent photocatalyzing thin film according to claim 18 is it is characterised in that the material working as mask is During photosensitivity material, one nanoscale opening is etched on mask using photoetching process；When the material of mask is inorganic material During material, using photoetching and etching technics or only with anisotropic etch process to etch on mask together with nanoscale open Mouthful.
The preparation method of 20. transparent photocatalyzing thin film according to claim 15 it is characterised in that in described step 022, Nano wire is grown using chemical vapour deposition technique, aqua-solution method or electrochemical plating.
A kind of 21. graphene-based automatically cleaning solar film batteries, it is disposed with light transmission layer, transparency electrode from top to bottom Layer and light conversion layer, incident illumination, successively through light transmission layer and transparent electrode layer, enters back into light conversion layer, and light conversion layer absorbs Carry out opto-electronic conversion after incident illumination and produce electricity；It is characterized in that, described light-transmitting layer has the graphite described in claim 1 Thiazolinyl laminated film, wherein, the bottom of described graphene film is located at transparent electrode layer upper surface.
22. graphene-based automatically cleaning solar film batteries according to claim 21 are it is characterised in that described transparent electrical Pole layer adopts the graphene-based laminated film described in claim 1, in the graphene film lower surface contact setting of light-transmitting layer Have a transparent substrate, the graphene film close-fitting transparent substrate layer lower surface of transparent electrode layer, transparent electrode layer graphene-based Nano thin-film in laminated film is located at the lower surface of its graphene film.
23. graphene-based automatically cleaning solar film batteries according to claim 21 are it is characterised in that saturating in described light Cross and above layer, be provided with scalable flexible and transparent protective layer, between described scalable flexible and transparent protective layer and described light transmission layer There is space, to avoid described scalable flexible and transparent protective layer to contact with described light transmission layer；Described scalable flexible saturating The edge of bright protective layer is connected with insulating supporting structure, and the bottom part ring of insulating supporting structure is around being arranged at described light transmission accordingly The edge of layer, thus support scalable flexible and transparent protective layer；Described scalable flexible and transparent protective layer passes through to stretch or crimps To realize the masking to described light transmission layer or exposure.
24. graphene-based automatically cleaning solar film batteries according to claim 23 it is characterised in that curling state Form a volume including a-circle-by-a-circle rolling from inside to outside.
25. graphene-based automatically cleaning solar film batteries according to claim 23 are it is characterised in that described scalable Flexible and transparent protective layer has two-layer, and ground floor is hydrophilic clear layer, strong for being less than set illumination in intensity of illumination Light transmission layer is protected, thus reducing the organic pollution on scalable flexible and transparent protective layer and light transmission layer during degree threshold value；The Two layers is hydrophobic transparent layer, for protecting light transmission layer when ambient humidity exceedes set humidity threshold, thus suppressing Moisture enters described light transmission layer and enters in solar film battery；The edge of hydrophilic clear layer and hydrophobic transparent layer it Between be connected with another insulating supporting structure, for isolating and supporting two-layer clear layer.
26. graphene-based automatically cleaning solar film batteries according to claim 25 are it is characterised in that described insulation Supporting construction includes insulating supporting structure and lower insulating supporting structure；Described upper insulating supporting structure is located at described lower insulation The top of support structure, and the width of described upper insulating supporting structure be less than described lower insulating supporting structure width so that lower absolutely The part that edge supporting construction is located inside upper insulating supporting structure comes out and is used for supporting positioned at lower insulating supporting structure One layer of scalable flexible and transparent protective layer；The top of upper insulating supporting structure is used for supporting on upper insulating supporting structure One layer of scalable flexible and transparent protective layer.
27. graphene-based automatically cleaning solar film batteries according to claim 25 are it is characterised in that also have control Device, the first transducer, the second transducer and diagnosis apparatuss, controller is electrically connected with diagnosis apparatuss phase, and diagnosis apparatuss are electrically connected with transducer phase；Light The graphene-based laminated film of transmission layer includes：Optical detection region, is irradiated to intensity of illumination on solaode for detecting；With And humidity search coverage, for detecting the humidity around solaode；
Optical detection region is electrically connected with the first transducer phase, for detecting the intensity of illumination of surrounding and producing the signal of telecommunication and be sent to First transducer, this signal of telecommunication is converted to intensity of illumination data is activation to diagnosis apparatuss by the first transducer, and diagnosis apparatuss judge this light According to intensity data whether higher than set intensity of illumination threshold value；If it has, then diagnosis apparatuss send contraction signal to controller, control Device processed controls described scalable flexible and transparent protective layer to execute crimping action；If it has not, then diagnosis apparatuss send stretch signal to control Device processed, controller controls described scalable flexible and transparent protective layer to execute stretching；
Humidity search coverage is electrically connected with the second transducer phase, for detecting the humidity of surrounding and producing the signal of telecommunication and be sent to Two transducers, this signal of telecommunication is converted to humidity data and is sent to diagnosis apparatuss by the second transducer, and diagnosis apparatuss judge this humidity data Whether higher than set humidity threshold；If it has not, then diagnosis apparatuss send contraction signal to controller, controller control is described can Telescopic flexible protective clear layer executes crimping action；If it has, then diagnosis apparatuss send stretch signal to controller, controller controls Described scalable flexible and transparent protective layer executes stretching.
28. graphene-based automatically cleaning solar film batteries according to claim 25 are it is characterised in that described illumination is strong , in the range of set intensity of illumination, described humidity threshold is in set humidity range for degree threshold value.
29. graphene-based automatically cleaning solar film batteries according to claim 25 are it is characterised in that described hydrophilic Clear layer and described hydrophobic transparent layer default conditions are rolled state.
30. graphene-based automatically cleaning solar film batteries according to claim 25 are it is characterised in that described hydrophilic Clear layer is the graphene film of monolayer atomic layer.
31. graphene-based automatically cleaning solar film batteries according to claim 25 are it is characterised in that described hydrophobicity Clear layer is the graphene film of two-layer or three layers of atomic layer.
32. graphene-based automatically cleaning solar film batteries according to claim 21 are it is characterised in that described light is changed Layer is dye-sensitized layer, also has bottom electrode layer in light conversion layer bottom.
The preparation method of the graphene-based automatically cleaning solar film battery described in a kind of 33. claim 21 it is characterised in that Including：
Step 0001：Prepare a light conversion layer；
Step 0002：Transparent electrode layer is formed on light conversion layer；
Step 0003：Light transmission layer is formed on transparent electrode layer.
34. preparation methoies according to claim 33 are it is characterised in that after described step 0003, also include：Saturating in light The marginal area crossing layer forms insulating supporting structure；Then, by the edge bottom of scalable flexible and transparent protective layer accordingly It is bonded in described insulating supporting structure surface, so that the edge of scalable flexible and transparent protective layer is connected to insulating supporting structure On.
CN201610880943.7A 2016-10-09 2016-10-09 Graphene-based composite thin film, self-cleaning solar thin film cell and preparation method Pending CN106409518A (en)

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