CN105826471B - A kind of double bionical sunken light have polymer solar battery of Plasmon Surface Resonance effect and preparation method thereof concurrently - Google Patents

A kind of double bionical sunken light have polymer solar battery of Plasmon Surface Resonance effect and preparation method thereof concurrently Download PDF

Info

Publication number
CN105826471B
CN105826471B CN201610171636.1A CN201610171636A CN105826471B CN 105826471 B CN105826471 B CN 105826471B CN 201610171636 A CN201610171636 A CN 201610171636A CN 105826471 B CN105826471 B CN 105826471B
Authority
CN
China
Prior art keywords
light
tio
preparation
layer
butterfly
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201610171636.1A
Other languages
Chinese (zh)
Other versions
CN105826471A (en
Inventor
郭文滨
李质奇
沈亮
温善鹏
周敬然
董玮
张歆东
阮圣平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin University
Original Assignee
Jilin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin University filed Critical Jilin University
Priority to CN201610171636.1A priority Critical patent/CN105826471B/en
Publication of CN105826471A publication Critical patent/CN105826471A/en
Application granted granted Critical
Publication of CN105826471B publication Critical patent/CN105826471B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/87—Light-trapping means
    • 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
    • Y02E10/549—Organic PV cells

Abstract

A kind of double bionical sunken light based on the antireflective of moth eye and the sunken light of butterfly's wing scale have polymer solar battery of Plasmon Surface Resonance effect and preparation method thereof concurrently, belong to organic polymer solar cell technical field.The solar cell is successively by TiO2Moth eye antireflection layer, ITO Conducting Glass, imitative butterfly's wing scale fall into light TiO2The PCDTBT of electron transfer layer, doping gold or Nano silver grain:PCBM active layers, MoO3Hole transmission layer and Ag anodes composition.The present invention falls into the light convergence of optical interface using moth eye and butterfly's wing structure and light field redistribution effect improves solar cell properties, in combination with active layer nanoparticle doped, device light is improved using its surface plasmon resonance effect to utilize, carrier transport is improved simultaneously, and then increases substantially organic solar batteries efficiency.

Description

A kind of double bionical sunken light have the polymer solar of Plasmon Surface Resonance effect concurrently Battery and preparation method thereof
Technical field
The invention belongs to organic polymer solar cell technical field, and in particular to one kind is based on the antireflective of moth eye and butterfly Double bionical sunken light of the sunken light of butterfly wing scale have polymer solar battery and its preparation of Plasmon Surface Resonance effect concurrently Method.
Background technology
Polymer solar battery because its is flexible, flexible, inexpensive, be easy to large area to produce the advantages that for new energy send out Exhibition provides a new road, and document report has higher effect based on co-mixing system transoid polymer solar battery Rate, but due to the low influence of organic matter carrier mobility itself, to reduce Carrier recombination, general active layer thickness is kept In 100nm or so, however, relatively thin active layer is unfavorable for the absorption of light, therefore, solves polymer solar battery active layer and inhale The shortcomings that yield is low, it is the problem of researcher must face further to improve battery efficiency.Researcher all over the world tastes Pinging various methods improves device property, improves device performance, for example, the polymer of the wider ABSORPTION EDGE of development, improves device The methods of structure, and made in the present invention by bionic method and the double imitative of light is fallen into based on the antireflective of moth eye and butterfly's wing scale Raw sunken photopolymer solar cell, improves effective utilization to sunshine, and be total to using nanoparticle surface plasma Effect of shaking improves light and utilized, and strengthens carrier transport, further improves the performance of polymer solar battery,
The content of the invention
The double of light are fallen into based on the antireflective of moth eye and butterfly's wing scale bionical had concurrently it is an object of the invention to provide a kind of Organic polymer solar cell of gas ions surface resonance effect and preparation method thereof.
This method falls into the light convergence of optical interface using moth eye and butterfly's wing structure and light field redistribution effect improves the sun Energy battery performance, in combination with active layer nanoparticle doped, its surface plasmon resonance effect is utilized to improve device light profit With, while carrier transport is improved, and then increase substantially polymer solar battery efficiency.
Double bionical sunken light of the present invention that light is fallen into based on the antireflective of moth eye and butterfly's wing scale have plasma concurrently Prepared by the polymer solar battery of surface resonance effect mainly include three parts：1st, the preparation of anti-moth eye antireflection layer；2、 Imitative butterfly's wing scale falls into the preparation of photosphere；3rd, nanoparticle doped.
Double bionical sunken light of the present invention that light is fallen into based on the antireflective of moth eye and butterfly's wing scale have plasma concurrently The preparation of the polymer solar battery biomimetic features of surface resonance effect uses a variety of methods, simplifies preparation technology, saves Cost.
Polymer solar battery of the present invention, it is characterised in that：From bottom to up, successively by TiO2Moth eye antireflective Layer, ITO Conducting Glass, fall into light TiO2The PCDTBT of electron transfer layer, doping gold or Nano silver grain:PCBM active layers, MoO3Hole transmission layer and Ag anodes composition.
Moth eye anti-reflection structure is prepared at the ITO back sides using two sol-gal process, template, anode oxidizing process, is used Sol-gal process, template are in TiO2Electron transfer layer prepares the bionical light trapping structure of butterfly's wing.Meanwhile adulterated in active layer Gold or Nano silver grain, increase the utilization of light using nanoparticle surface plasma resonance effect, so as to improve the property of device Can, wherein the thickness of moth eye antireflection layer is 40~60nm, PCDTBT：The thickness of PCBM active layers is 100~200nm, MoO3 The thickness of hole transmission layer is 3~5nm, the thickness of Ag anodes is 80~120nm.
Double bionical sunken light of the present invention that light is fallen into based on the antireflective of moth eye and butterfly's wing scale have plasma body surface concurrently The polymer solar battery preparation method of face resonance effects.Its step is as follows：
1、TiO2The preparation of moth eye antireflection layer
1)TiO2The preparation of colloidal sol
At 20~30 DEG C, 10~30mL butyl titanate (Beijing Yi Li chemical plant) is added drop-wise to equipped with 60~100mL In the reaction vessel of absolute ethyl alcohol (Beijing Chemical Plant), magnetic agitation 60~90 minutes (time constant-temperature magnetic stirring apparatus), then drip Add 5~20mL glacial acetic acid (Beijing Chemical Plant), stir 30~90min, obtain the yellow solution of homogeneous transparent；Then add 5~20mL acetylacetone,2,4-pentanediones (Tianjin chemical reagent factory), 30~90min is stirred, adds 20~40mL absolute ethyl alcohols, by 5~ 20mL deionized waters are slowly dropped in above-mentioned solution with 2~6mL/min speed, continue stirring 2~3 days, are obtained uniformly thoroughly Bright faint yellow colloidal sol, ageing 3~5 days is placed, obtains TiO2Colloidal sol.
2) substrate cleans
ITO Conducting Glass is cleaned by ultrasonic 10~20 minutes using acetone, ethanol and deionized water successively, Ran Houyong Nitrogen dries up；
3)TiO2The preparation of moth eye antireflection layer
Using two step anodizings, by the use of high-purity aluminum foil as antireflective impression formboard, experiment use profile for 20mm × The high-purity aluminum foil that 15mm × 0.5mm purity is 99.9% is raw material, is used after machinery flattening.
The first step, using high-purity aluminum foil as anode, copper sheet is negative electrode, and 0.3~0.6M oxalic acid gives as solvent and corrosive agent 2~6h of corrosive aluminum foil under the conditions of 30~50V of voltage, 2~5 DEG C of solvent temperature；
Second step, the aluminium foil that previous step obtains are anode, and copper sheet is negative electrode, and 4~7Wt% phosphoric acid is as solvent and corrosion Agent；Under the conditions of 30~50V of given voltage, 30~90 DEG C of solvent temperature continue 2~6h of corrosive aluminum foil, by control corrosion rate temperature, Anode voltage, etchant concentration, aluminium foil surface corrosion depth and width can be effectively controlled, surface, which can be prepared, to be had The aluminium foil of cone-shaped groove array, turbination groove array 40~60nm of the length of side, 40~60nm of cycle, 40~60nm of height.
Moth eye antireflection layer is prepared in the glass surface of Conducting Glass using alignment formula nano hot stamping technology, Its process includes：
First by obtained TiO2Colloidal sol is spin-coated on the glass surface of the ITO Conducting Glass after cleaning, and spin coating turns Speed is 1000~4000rpm, and spin-coating time is 10~30s, obtained TiO2The thickness range of sol layer is 40~60nm；
The glass surface of ITO Conducting Glass is put into marking press upwards, using aluminium foil prepared above as antireflective pressure Stamp version, pressed temperature is set as 70~130 DEG C, pressurize temperature is 130~150 DEG C, and the dwell time is 10~20min, pressure release Temperature is 30~60 DEG C, so as in TiO2Impressing obtains conical array on sol layer, array simulation moth ocular structure, Neng Gouyou Effect reduces the reflex for incident light；Conical array base diameter 40~60nm, 40~60nm of cycle, height 40~ 60nm；1~3h is finally calcined under the conditions of 300~500 DEG C, is naturally cooling to room temperature, so as in the glass of ITO Conducting Glass Glass surface obtains TiO2Moth eye antireflection layer, 40~60nm of its thickness range；Two, bionical light trapping structure polymer solar battery Preparation
1) substrate cleans
The back side is carried into TiO2The ITO electro-conductive glass of moth eye antireflection layer is entered using acetone, ethanol and deionized water successively Row cleaning, is then dried up with nitrogen；
2) light TiO is fallen into2The preparation of electron transfer layer
The monodisperse layer of a diameter of 300~500nm polystyrene PS beads is by being done in the self assembly of water/Air Interface What method was formed.First, prepare mass fraction 5wt%~10wt% PS beads water and ethanol (volume ratio of water and ethanol is 1：1) single dispersing liquid；Secondly, add deionized water in culture dish, and to deionized water surface be slowly added to PS beads water and Ethanol single dispersing liquid, the small clubs of PS scatter in the water surface, continuously add dispersion liquid until PS beads are paved with the whole water surface；Then, to The water surface instills 2wt%~5wt% C12H25NaO4The S aqueous solution adjusts the surface tension of the water surface, makes the arrangement of PS beads close, and then Control to adjust the PS bead sizes of space；Subsequently, ITO Conducting Glass is inserted in water at a slant and slowly lifted, make row Close PS beads monodisperse layer is arranged to be transferred in ITO Conducting Glass；Finally, the ITO of PS bead monodisperse layers will be loaded with Conducting Glass is dried 15~30 minutes under the conditions of 90 DEG C~150 DEG C in Muffle furnace and removes solvent, so as in ITO conduction glass Glass surface obtains close-packed arrays, the orderly small ball arrays of two-dimentional PS；The ITO electro-conductive glass covered with the small ball arrays of PS that will be obtained Substrate transverse is slowly immersed in TiO23~5 minutes (TiO in sol solution2Colloidal sol collocation method is same as above), make TiO2Colloidal sol fills up The gap of PS bead templates；Then, will be from TiO2The ITO Conducting Glass taken out in sol solution 350 in Muffle furnace~ Annealed 1.5~2.5 hours under the conditions of 500 DEG C, naturally cool to room temperature；PS beads are carbonized under the high temperature conditions, leave two-dimentional bowl Shape hollow out array structure, so as to obtain the sunken light TiO of two-dimensional structure on ITO surfaces2Electron transfer layer array, the array configuration mould Intend hollow type butterfly's wing, can effectively change the issue of inside battery light field, increase the absorption of sunshine, the diameter of the array 350~450nm, height about 170~230nm, 350~450nm of cycle.
3) preparation of active layer
Using 1-2- dichloro-benzenes as solvent, using PCDTBT as donor material, PCBM is acceptor material, according to giving acceptor material matter Measure ratio 1：4 ratio is configured to the active layer solution of 5mg/mL~20mg/mL concentration, while adulterates 0.1 in active layer solution The nanometer particle materials such as~5wt% Ag or Au, then, in TiO2Spin coating active layer solution on electron transfer layer, spin coating turn Speed is 1000~3000rpm, and spin-coating time is 10~30s, and the thickness of obtained active layer is 50~150nm；
4) preparation of hole transmission layer and the preparation of electrode
In pressure 2 × 10-4~5 × 10-4Under the conditions of Pa, MoO is deposited in active layer surface3(Chinese medicines group chemical reagent has Limit company) hole transmission layer, thickness is 3~5nm, and the speed of growth is
Finally in MoO3On hole transmission layer, 3 × 10-4~5 × 10-4Ag is deposited under Pa, and (Chinese medicines group chemical reagent has Limit company) electrode, thickness is 80~150nm, and the speed of growth isSo as to obtain of the present invention being based on nanometer hot pressing The transoid light trapping structure cascade connection type polymer solar battery of print technology.
Brief description of the drawings
Fig. 1：The bionical position schematic diagram of double Biomimetic Polymers solar cells of the present invention；
Fig. 2：The structural representation of polymer solar battery of the present invention；
Fig. 3：The photoelectricity of transoid polymer solar battery prepared by the present invention and traditional transoid polymer solar battery Flow curve；
Fig. 4：The light of transoid polymer solar battery prepared by the present invention and traditional transoid polymer solar battery is inhaled Receive curve；
Fig. 5：Imitative moth eye antireflective stamp fabrication schematic flow sheet；
Fig. 6：The preparation flow schematic diagram of bionical light trapping structure polymer solar battery.
As shown in figure 1, the bionical position schematic diagram of double Biomimetic Polymers solar cells of the present invention, left side is the present invention Moth eye is simulated in simulated butterfly's wing, right side by the present invention.
As shown in Fig. 2 the structural representation of polymer solar battery of the present invention, 1 is TiO2Anti- moth eye antireflective Layer, 2 be ITO Conducting Glass, and 3 be TiO2Electron transfer layer, 4 be the PCDTBT of doping Au nanometer particle materials:PCBM lives Property layer, 5 be MoO3Hole transmission layer, 6 be Ag electrodes.
As shown in figure 3, in 100mw/cm2Xenon light shining under measured V-I characteristic curves, A is to use structure of the present invention Solar cell, B is traditional ITO/TiO2/PCDTBT:PCBM/MoO3The solar cell of/Ag structures.Fig. 3 results explanation is originally The transoid polymer solar battery A prepared is invented compared with traditional transoid polymer solar battery B photocurrent curves, its Battery short circuit electric current, fill factor, curve factor, energy conversion efficiency significantly improve.
As shown in figure 4, transoid polymer solar cell device A and traditional transoid polymer solar prepared by the present invention The contrast of battery device B absorption curves.Fig. 4 results illustrate the transoid polymer solar battery A of the invention prepared and tradition Transoid polymer solar battery B light is compared, and its light absorbs significantly improves.
As shown in figure 5, anode two-step penetration method corrosive aluminum foil, for step a to prepare high-purity aluminum foil, step b is that the first step is rotten Obtained preliminary masterplate is lost, step c is the moth eye antireflective masterplate that second step corrodes to obtain.
As shown in fig. 6, the preparation flow schematic diagram of bionical light trapping structure polymer solar battery, step a is that substrate is pre- Processing, step b are growth PS beads, and step c is growth TiO2, step d is that high annealing obtains the bowl-shape hollow out array junctions of two dimension Structure, step e are growth activity layer, and step f is growth MoO3With Ag electrodes.
Embodiment
One, TiO2The preparation of moth eye antireflection layer
(1) one layer of TiO is prepared on ITO surfaces using sol-gel method2Film, its detailed process include：25 DEG C of room temperature Under, 10mL butyl titanate (Beijing Yi Li chemical plant) is added drop-wise to the cone of the absolute ethyl alcohol (Beijing Chemical Plant) equipped with 60mL In shape bottle, stir 60 minutes (time constant-temperature magnetic stirring apparatus), then 10mL glacial acetic acid (Beijing Chemical Plant), magnetic agitation is added dropwise 30min, obtain the yellow solution of homogeneous transparent；Then 10mL acetylacetone,2,4-pentanedione (Tianjin chemical reagent factory), stirring are added 30min, 30mL absolute ethyl alcohols are added, then 10mL deionized waters are slowly dropped in above-mentioned solution with 2mL/min speed, Continue stirring one day or for more time, obtain the faint yellow colloidal sol of homogeneous transparent, place ageing three days, obtained TiO2Colloidal sol.
(2) substrate cleans
ITO electro-conductive glass is cleaned by ultrasonic 20 minutes using acetone, ethanol and deionized water successively, then blown with nitrogen Dry
(3)TiO2The preparation of moth eye antireflection layer
Using two step anodizings, by the use of high-purity aluminum foil as antireflective impression formboard, experiment use profile for 20mm × The aluminium flake that 15mm × 0.5mm purity is 99.9% is raw material, and two step anodizings are tested after machinery flattens.
The first step, using high-purity aluminum foil as anode, copper sheet is negative electrode, and the change of ammeter record current is accessed in circuit.It is given Voltage 40V, 0.5M oxalic acid corrodes as solvent and corrosive agent to aluminium foil, controls 4 DEG C, etching time 4h of solvent temperature, Using drawing water, the circulatory system is stirred to solution, solvent strength is kept uniform, is advantageous to the uniform progress of corrosion；
Second step, using the aluminium foil that previous step obtains as anode, copper sheet is negative electrode, use instead 6Wt% phosphoric acid to aluminium foil after It is continuous to be corroded, given voltage 50V, 60 DEG C, etching time 4h of solvent temperature is controlled, surface, which is prepared, has back taper recessed The aluminium foil of groove array, back taper groove array length of side 45nm, cycle 45nm, height 45nm.
Imitative moth eye anti-reflection is prepared in the glass surface of ITO Conducting Glass using alignment formula nano hot stamping technology Layer is penetrated, its process includes：
First by obtained TiO2Colloidal sol is spin-coated on the glass surface of the ITO Conducting Glass after cleaning, and spin coating turns Speed is 3000rpm, spin-coating time 20s；Obtained TiO2The thickness range of sol layer is 50nm.
The glass surface of ITO Conducting Glass is put into marking press upwards, using aluminium foil prepared above as antireflective pressure Stamp version, pressed temperature is set as 70 DEG C, pressurize temperature is 100 DEG C, dwell time 15min, and pressure release temperature is 50 DEG C, so as to In TiO2Sol layer imprints to obtain conical array, array simulation moth ocular structure, can effectively reduce for the anti-of incident light The effect of penetrating；Conical array diameter 45nm, cycle 45m, height 50nm；2h finally is calcined under the conditions of 450 DEG C, is naturally cooling to Room temperature, so as to which the glass surface in ITO Conducting Glass obtains TiO2Moth eye antireflection layer, its thickness range 50nm.
Two, the preparation of bionical light trapping structure polymer solar battery
1) substrate cleans
ITO electro-conductive glass of the back side with anti-reflection structure is clear to front using acetone, ethanol and deionized water successively Wash, then dried up with nitrogen；
2) light TiO is fallen into2The preparation of electron transfer layer
The monodisperse layer of a diameter of 420nm polystyrene PS beads is by the self assembly method shape in water/Air Interface Into.First, preparing the monodispersed water/ethanol of PS beads that mass fraction is 5w%, (volume ratio of water and ethanol is 1:1) mix Close solution；Secondly, deionized water is loaded in culture dish, and PS beads are slowly injected to deionized water surface with microsyringe Monodisperse liquor, the small clubs of PS scatter in the water surface, continue injection until bead be paved with the whole water surface；Then, instilled to the water surface 2wt% C12H25NaO4The S aqueous solution adjusts the surface tension of the water surface, control PS bead arrangements；Subsequently, glass substrate is tilted In insertion water and slowly lift, PS beads is transferred in glass substrate；Finally, the glass of PS bead monodisperse layers will be loaded with Substrate is dried 25 minutes under the conditions of 100 DEG C in Muffle furnace and removes solvent, so as to obtain close-packed arrays in glass substrate surface, have The small ball arrays of two-dimentional PS of sequence；The glass substrate film normal that will be covered with the small ball arrays of PS is slowly immersed in TiO2Sol solution The middle 5 minutes time, after substrate is totally immersed into, it is slowly lifted, makes TiO2Colloidal sol fills up the gap of PS bead templates；So Afterwards, will be from TiO2The glass substrate film taken out in sol solution is annealed 2 hours in Muffle furnace under the conditions of 450 DEG C, naturally cold But to room temperature；PS beads are carbonized under the high temperature conditions, leave the bowl-shape hollow out array structure of two dimension, so as to obtain two on ITO surfaces Tie up the sunken light TiO of structure2Electron transfer layer array, array configuration simulation hollow type butterfly's wing, can effectively change battery Internal light field issue, increase the absorption of sunshine, the diameter 420nm of the array, height about 210nm.
3) preparation of active layer
Using 1-2- dichloro-benzenes as solvent, using PCDTBT as donor material, PCBM is acceptor material in mass ratio 1：4 are configured to The active layer solution of 7mg/mL concentration, at the same in active layer solution adulterate 1wt% Au nanometer particle materials, then, TiO2Spin coating active layer solution on electron transfer layer, spin coating rotating speed are 2000rpm, spin-coating time 20s；Obtained active layer Thickness is 100nm；
4) sample is taken out, is put into SD400B type multi-source temperature control organic vapors molecule deposition systems, pressure be 5 × 10-4Under Pa, MoO is deposited on active layer3(Chemical Reagent Co., Ltd., Sinopharm Group) hole transmission layer, thickness 4nm, growth Speed is
5) sample is taken out, is put into SD400B type multi-source temperature control organic vapors molecule deposition systems, pressure be 5 × 10-4Under Pa, Ag electrodes, thickness 100nm are deposited on vanadium pentoxide films, the speed of growth is

Claims (5)

1. a kind of double bionical sunken light that light is fallen into based on the antireflective of moth eye and butterfly's wing scale have Plasmon Surface Resonance effect concurrently The preparation method for the polymer solar battery answered, its step are as follows：
(1)TiO2The preparation of moth eye antireflection layer
1. using high-purity aluminum foil as anode, copper sheet is negative electrode, 0.3~0.6M oxalic acid as solvent and corrosive agent, given voltage 30~ 2~6h of corrosive aluminum foil under the conditions of 50V, 2~5 DEG C of solvent temperature；
2. using 1. aluminium foil that step obtains as anode, copper sheet is negative electrode, and 4~7wt% phosphoric acid gives electricity as solvent and corrosive agent Continue 2~6h of corrosive aluminum foil under the conditions of 30~50V of pressure, 30~90 DEG C of solvent temperature, so as to obtain turbination in aluminium foil surface Groove array, back taper groove array 40~60nm of diameter, 40~60nm of cycle, 40~60nm of height；
3. by TiO2The glass surface of the ITO Conducting Glass of colloidal sol spin coating after cleaning, spin coating rotating speed be 1000~ 4000rpm, spin-coating time are 10~30s, obtained TiO2The thickness range of sol layer is 40~60nm；
4. the glass surface of 3. ITO Conducting Glass that step obtains is put into marking press upwards, the aluminium 2. prepared with step Paper tinsel is antireflective impression formboard, sets pressed temperature as 70~130 DEG C, and pressurize temperature is 130~150 DEG C, the dwell time 10 ~20min, pressure release temperature is 30~60 DEG C, so as in TiO2Impressing obtains conical array, conical array bottom on sol layer A diameter of 40~the 60nm in portion, cycle are 40~60nm, are highly 40~60nm, array simulation moth ocular structure, can effectively be subtracted The small reflex for incident light；
5. 4. ITO Conducting Glass that step is obtained is calcined 1~3h under the conditions of 300~500 DEG C, room is naturally cooling to Temperature, so as to which TiO is prepared in the glass surface in ITO Conducting Glass2Moth eye antireflection layer, its thickness range 40~ 60nm；
(2) preparation of bionical light trapping structure polymer solar battery
1. fall into light TiO2The preparation of electron transfer layer
A：Deionized water is added in culture dish, and the water and ethanol single dispersing of PS beads are slowly added to deionized water surface Liquid, PS beads scatter in the water surface, continuously add dispersion liquid until PS beads are paved with the whole water surface；Then 2wt% is instilled to the water surface ~5wt% C12H25NaO4The S aqueous solution adjusts the surface tension of the water surface, makes the arrangement of PS beads close, and then it is small to control to adjust PS The ball size of space；Subsequently, the ITO Conducting Glass that step (1) obtains is inserted in water at a slant and slowly lifted, make row Close PS beads monodisperse layer is arranged to be transferred on the ITO surfaces of ITO Conducting Glass；Finally, single point of PS beads will be loaded with The ITO Conducting Glass for dissipating layer dries 15~30 minutes removal solvents under the conditions of 90 DEG C~150 DEG C, so as to conductive in ITO The ITO surfaces of glass substrate obtain close-packed arrays, the orderly small ball arrays of two-dimentional PS；
B：The obtained ITO Conducting Glass covered with the small ball arrays of PS is vertically slowly immersed in TiO23 in sol solution~ 5 minutes, make TiO2Colloidal sol fills up the gap of PS bead templates；Then, will be from TiO2The ITO electro-conductive glass taken out in sol solution Substrate is annealed 1.5~2.5 hours under the conditions of 350~500 DEG C, naturally cools to room temperature；PS beads are carbonized under the high temperature conditions, The bowl-shape hollow out array structure of two dimension is left, so as to obtain the sunken light TiO of two-dimensional structure on the ITO surfaces of ITO Conducting Glass2 Electron transfer layer, array configuration simulation hollow type butterfly's wing, can effectively change the issue of inside battery light field, increase the sun The absorption of light, 350~450nm of diameter of the array, height 170~230nm, 350~450nm of cycle；
2. the preparation of active layer
First, using 1-2- dichloro-benzenes as solvent, using PCDTBT as donor material, PCBM is acceptor material in mass ratio 1：4 prepare Into the active layer solution of 5mg/mL~20mg/mL concentration, while 0.1~5wt% of doping Ag or Au receive in active layer solution Nanoparticle material；
Then, the sunken light TiO 1. prepared in step2Spin coating active layer solution on electron transfer layer, spin coating rotating speed be 1000~ 3000rpm, spin-coating time are 10~30s, and the thickness of obtained active layer is 50~150nm；
3. the preparation of hole transmission layer and the preparation of electrode
In pressure 2 × 10-4~5 × 10-4Under the conditions of Pa, MoO is deposited in active layer surface3Hole transmission layer, thickness are 3~5nm, The speed of growth is
Finally in MoO3On hole transmission layer, 3 × 10-4~5 × 10-4Under the conditions of Pa be deposited Ag electrodes, thickness be 80~ 150nm, the speed of growth areThe double bionical sunken of light is fallen into based on the antireflective of moth eye and butterfly's wing scale so as to be prepared Light has the polymer solar battery of Plasmon Surface Resonance effect concurrently.
2. a kind of double bionical sunken light that light is fallen into based on the antireflective of moth eye and butterfly's wing scale as claimed in claim 1 are had concurrently The preparation method of the polymer solar battery of gas ions surface resonance effect, it is characterised in that：TiO2The preparation of colloidal sol be At 20~30 DEG C, 10~30mL butyl titanate is added drop-wise in the reaction vessel equipped with 60~100mL absolute ethyl alcohols, magnetic force Stirring 60~90 minutes, then 5~20mL glacial acetic acid is added dropwise, 30~90min is stirred, obtains the yellow solution of homogeneous transparent； Then 5~20mL acetylacetone,2,4-pentanediones are added, 30~90min is stirred, adds 20~40mL absolute ethyl alcohols；Finally 5~20mL is gone Ionized water is slowly dropped in above-mentioned solution with 2~6mL/min speed, continues stirring 2~3 days, obtains the light of homogeneous transparent Yellow sol, ageing 3~5 days is placed, obtains TiO2Colloidal sol.
3. a kind of double bionical sunken light that light is fallen into based on the antireflective of moth eye and butterfly's wing scale as claimed in claim 1 are had concurrently The preparation method of the polymer solar battery of gas ions surface resonance effect, it is characterised in that：ITO Conducting Glass it is clear It is to be cleaned by ultrasonic ITO Conducting Glass 10~20 minutes using acetone, ethanol and deionized water successively to wash, and then uses nitrogen Drying.
4. a kind of double bionical sunken light that light is fallen into based on the antireflective of moth eye and butterfly's wing scale as claimed in claim 1 are had concurrently The preparation method of the polymer solar battery of gas ions surface resonance effect, it is characterised in that：The water and ethanol list of PS beads Dispersion liquid is that a diameter of 300~500nm polystyrene PS beads are scattered in water and ethanol to be configured to mass fraction 5wt% The volume ratio of~10wt% single dispersing liquid, water and ethanol is 1：1.
5. a kind of double bionical sunken light that light is fallen into based on the antireflective of moth eye and butterfly's wing scale have Plasmon Surface Resonance effect concurrently The polymer solar battery answered, it is characterised in that：It is to be prepared as the method described in Claims 1 to 4 any one.
CN201610171636.1A 2016-03-24 2016-03-24 A kind of double bionical sunken light have polymer solar battery of Plasmon Surface Resonance effect and preparation method thereof concurrently Expired - Fee Related CN105826471B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610171636.1A CN105826471B (en) 2016-03-24 2016-03-24 A kind of double bionical sunken light have polymer solar battery of Plasmon Surface Resonance effect and preparation method thereof concurrently

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610171636.1A CN105826471B (en) 2016-03-24 2016-03-24 A kind of double bionical sunken light have polymer solar battery of Plasmon Surface Resonance effect and preparation method thereof concurrently

Publications (2)

Publication Number Publication Date
CN105826471A CN105826471A (en) 2016-08-03
CN105826471B true CN105826471B (en) 2018-02-27

Family

ID=56524477

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610171636.1A Expired - Fee Related CN105826471B (en) 2016-03-24 2016-03-24 A kind of double bionical sunken light have polymer solar battery of Plasmon Surface Resonance effect and preparation method thereof concurrently

Country Status (1)

Country Link
CN (1) CN105826471B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109461819A (en) * 2018-10-30 2019-03-12 浙江海洋大学 A kind of the flexible solar battery material and preparation method of high optoelectronic transformation efficiency
CN109972168A (en) * 2019-04-16 2019-07-05 厦门大学 Multiple sunken light nanometer titanium dioxide Ti electrode and its preparation method and application
CN111785836B (en) * 2020-06-27 2022-12-16 上海师范大学 Solar cell with hole transport layer with moth eye structure and preparation method thereof
CN112563428A (en) * 2020-12-04 2021-03-26 南开大学 Electronic transmission layer decorated by nano structure
CN112909178B (en) * 2021-01-18 2022-07-08 香港科技大学深圳研究院 Light trap substrate, preparation method and application thereof, and semitransparent solar cell

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008034687A (en) * 2006-07-31 2008-02-14 Toppan Printing Co Ltd Photoelectric conversion element
CN101866958A (en) * 2010-05-14 2010-10-20 河海大学常州校区 Biomimetic antireflection film of solar cell and preparation method thereof
CN101866959A (en) * 2010-05-14 2010-10-20 中国科学院上海微***与信息技术研究所 Broad-spectrum wide angle absorption solar cell moth-eye antireflection structure and preparation method thereof
JP2013179217A (en) * 2012-02-29 2013-09-09 Sharp Corp Solar cell and manufacturing method for the same
CN104395784A (en) * 2012-06-22 2015-03-04 夏普株式会社 Antireflection structure, transfer mold, production methods therefor, and display device
CN104487179A (en) * 2012-07-19 2015-04-01 日产化学工业株式会社 Structure having stainproof microrelief surface and process for producing same
CN105229790A (en) * 2013-07-03 2016-01-06 索尼公司 The manufacture method of solid imaging element, solid imaging element and electronic installation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008034687A (en) * 2006-07-31 2008-02-14 Toppan Printing Co Ltd Photoelectric conversion element
CN101866958A (en) * 2010-05-14 2010-10-20 河海大学常州校区 Biomimetic antireflection film of solar cell and preparation method thereof
CN101866959A (en) * 2010-05-14 2010-10-20 中国科学院上海微***与信息技术研究所 Broad-spectrum wide angle absorption solar cell moth-eye antireflection structure and preparation method thereof
JP2013179217A (en) * 2012-02-29 2013-09-09 Sharp Corp Solar cell and manufacturing method for the same
CN104395784A (en) * 2012-06-22 2015-03-04 夏普株式会社 Antireflection structure, transfer mold, production methods therefor, and display device
CN104487179A (en) * 2012-07-19 2015-04-01 日产化学工业株式会社 Structure having stainproof microrelief surface and process for producing same
CN105229790A (en) * 2013-07-03 2016-01-06 索尼公司 The manufacture method of solid imaging element, solid imaging element and electronic installation

Also Published As

Publication number Publication date
CN105826471A (en) 2016-08-03

Similar Documents

Publication Publication Date Title
CN105826471B (en) A kind of double bionical sunken light have polymer solar battery of Plasmon Surface Resonance effect and preparation method thereof concurrently
CN105529404B (en) A kind of organic solar batteries with two-dimensional nano bowl array light trapping structure and preparation method thereof
CN103219467B (en) Flexible polymer solar battery of corrugated structures and preparation method thereof
CN107195789B (en) A kind of preparation method of inorganic mixed halogen perovskite thin film and its application in terms of preparing solar battery
CN104701023B (en) A kind of carbon electrode material of perovskite thin film solar cell and preparation method thereof
CN105047821B (en) The transoid polymer solar battery and preparation method modified based on active layer and transport layer
CN107033892B (en) A kind of polythiophene/tungsten trioxide nano-rod electrochromic material and preparation method thereof
CN101752094B (en) Electrode in a photonic crystal structure mixed with nano metal and making method thereof
CN104916784A (en) Inversion light trapping structure cascade organic solar cell and preparation method thereof
CN103022267A (en) Production method of ZnO spherical-empty-shell nanoparticle array
CN105489769A (en) Preparation method of cathode and anode-modified perovskite solar cell
CN108767113B (en) TiO22Nano column-Au nano particle composite array, preparation method and application thereof
CN109888108A (en) A kind of perovskite solar battery and preparation method thereof of large biological molecule modification
CN105762286B (en) The preparation method of counter opal structure perovskite thin film and corresponding solar battery
CN107946467A (en) A kind of polymer solar battery based on multiple light trapping structure and preparation method thereof
CN101419867B (en) Nano composite electrode preparation for dye sensitization solar cell
CN106058059B (en) A kind of complementary type plasma resonance organic solar batteries and preparation method thereof based on active layer doping and transport layer modification
CN110098337A (en) A kind of stannic oxide/zinc oxide compound nano wire material and preparation method thereof
CN103839689B (en) Electrode of used by dye sensitization solar battery dopen Nano gold and preparation method thereof
CN102983275A (en) Polymer solar cell with water-soluble vanadium pentoxide hole-transport layer and fabrication method of polymer solar cell
CN108878660A (en) A kind of Ag/ZnO nuclear shell structure nano rod array electrode material preparation method
CN103280528B (en) A kind of polymer solar battery
CN106449996B (en) One kind being based on onion carbon nano-particles/Ag combination electrode organic solar batteries and preparation method thereof
CN113644202B (en) Organic solar cell prepared by spontaneous orientation film forming method and preparation method thereof
CN110212096A (en) Organic solar batteries and preparation method thereof based on the molybdenum trioxide hole transmission layer with light trapping structure

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180227

Termination date: 20210324

CF01 Termination of patent right due to non-payment of annual fee