CN107602823B - A kind of bionical honeycomb macropore ordered structure is to receptor semiconducting polymer film, preparation method and applications - Google Patents
A kind of bionical honeycomb macropore ordered structure is to receptor semiconducting polymer film, preparation method and applications Download PDFInfo
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Abstract
A kind of bionical honeycomb macropore ordered structure belongs to high molecular nanometer structure and energy stores and switch technology field to receptor semiconducting polymer film, preparation method and its application in terms of photoelectric conversion.Semi-conducting polymer of the present invention has to receptor structure, its absorption spectrum is made to cover most of visible light region.The present invention uses water surface development method, in the bionical honeycomb macroporous membrane that the water surface is self-assembly of.Film of the invention has on a large scale orderly bionical honeycomb macroporous structure, can effectively increase diffusing reflection of the incident light in film, enhances light-use；The contact area of film and electrolyte is increased simultaneously；Be conducive to charge in film to acceptor molecule structure to transmit, to improve the transfer efficiency that luminous energy is converted to electric energy.Compared with it does not have structured smooth film, the photoelectric current of bionical honeycomb macroporous membrane promises to be the material of practical application in polymer solar battery than high ten times of photoelectric current of the smooth film under zero-bias.
Description
Technical field
The invention belongs to high molecular nanometer structure and energy stores and switch technology fields, and in particular to a kind of bionical honeycomb
Shape macropore ordered structure is to receptor semiconducting polymer film, preparation method and its application in terms of photoelectric conversion.
Background technique
Expanding economy leads to energy consumption sustainable growth, and energy shortage and environmental problem are with rapid economic development
The problem of must facing.Countries in the world all suffer from the dual-pressure that energy ongoing shortage and environment constantly deteriorate at present.
For economic sustainable development, realize that the sustainable utilization of renewable resource is an effective way.Photoelectric conversion material is in base
Plinth research and industrial circle all receive more and more attention, and in materials science field, polymer material is since being born it, just
The material always generally favored.The class of polymer material is very rich, and application field is also very extensive, wherein organic partly lead
Body polymer material has the application of multiplicity, such as organic light emission due to its particular semiconductor characteristic in various photoelectric devices
Diode (OLED), organic field effect tube (OFET) and organic solar batteries (OSC) etc..Under normal conditions, You Jiban
The performance of conductor device has very big association with the molecular structure of used material.In the marked improvement of modern synthesis chemistry
Background under, scientist, which has been developed, a variety of has the-polymer molecule of conjugated structure.There are also very for this kind of polymer molecule
Good extinction coefficient, delocalized electron and photoelectric properties.With going deep into for research, scientist wishes to absorb by width and narrow band gap half
The design of Conductive polymers improves the efficiency of photoelectric conversion with synthesis.Jong-Cheol Lee(ACS
) et al. Appl.Mater.Inter.2017,9,12617-12628. devising a kind of has donor-receptor (D-A) structure alternating
Conjugated polymer, by giving the tunability of receptor group, the adjustable absorption band including polymer, molecular entergy level and current-carrying
Transport factor etc..It can be seen that Development of Novel gives acceptor molecule, it is an effective way for improving photoelectric conversion efficiency.
It is generally believed that the principal element for influencing photoelectric conversion efficiency includes light capture rate, bandwidth, electron-hole
Separative efficiency and electronics transporting rate etc..For these influence factors, scientific research personnel proposes a variety of solutions, wherein
It is reduced and is reflected by nanostructure, improving optical energy utilization efficiency is one of research hotspot.In recent years, it has been reported and utilizes structure
Orderly nanostructure is made to reduce the method for reflection and increase the utilization of luminous energy, such as: nano-imprint lithography and electron beam erosion
It carves (Nano Letters 2013,13,5329-5335), colloidal deposition/photoetching (Langmuir 2014,30,10481-
10486.), block copolymer auxiliary colloid assembling (Nanoscale 2014,6,7576-7584.) and LBL self-assembly method
(Energy&Environmental Science 2011,4,3930-3941) etc..By being analyzed above as it can be seen that scientist passes through
Different nanostructures is constructed, the luminous energy capture rate for improving electrode is to improve a kind of effective way of photoelectric conversion efficiency.But
It is that these researchs are also far from satisfying industrial demand.
In conclusion constructing nano junction using this new polymers developing novel polymer molecular structure simultaneously
Structure both can make polymer keep its primitive character in nano structured unit in this way, and the nanostructure itself formed also can
It plays a role, and this design is conducive to the volume and interface performance of the optimised devices in device fabrication process, to actually answering
With being of great significance.In inorganic material research field, there is the adjusting by nanostructure, improved photoelectric conversion efficiency
Report.For example, the multi-level nano-structure with bigger serface and light scattering can be improved to the photoelectric conversion efficiency of device
(Journal of Alloys and Compounds 2017,703,251-257.).At present by surface texture optimization thus
The report for improving the photoelectric conversion efficiency of Polymer Optoelectronic response device is few.Hae Jung Son et al. utilizes donor group
Orientations obtained superperformance all-polymer solar battery (Advance Energy Mater.2017,7,
1601365.).In our pervious work, graphene is assembled by the bee with antireflective property by the method for self assembly
Nest shape nanostructure, the nano structure membrane electrode clearly enhance photoelectric current generation (J.Mater.Chem.A, 2015,3,
12016-12022.).There is presently no the honeycomb macropore ordered structures for being applied to photoelectric conversion to give receptor semi-conducting polymer
The relevant report of film.Because of the invention low cost and easy-operating magnanimity preparation honeycomb macropore ordered structure gives receptor semiconductor
The method of thin polymer film is of great significance.
Summary of the invention
The object of the present invention is to provide a kind of bionical honeycomb macropore ordered structures to receptor semiconducting polymer film, system
Preparation Method and the application in terms of photoelectric conversion should can be used for the photoelectricity of photoelectric conversion device to receptor semiconducting polymer film
Pole, to improve the photoelectric conversion efficiency of polymer light electrode.
The bionical honeycomb macropore ordered structure that the present invention uses to receptor semiconducting polymer film is expanded using the water surface
Zhan Fa is self-assembly of in the water surface, so that its absorption spectrum is covered most of visible light region, the film to acceptor molecule structure
With large-scale bionical honeycomb macropore ordered structure.The film, can be effective in the anode as photoelectric conversion device
Diffusing reflection of the increase incident light in film, improve the capture rate of luminous energy, enhance light-use；Bionical honeycomb macropore simultaneously
Ordered structure increases the contact area of film and electrolyte；And light is improved to the good carrier mobility rate of receptor structure
The separation and transmission efficiency of raw electron-hole, obtain with the polymer based photovoltaic switching device for improving photoelectric respone efficiency.
Compared with flat membrane, the photoelectric response performance of bionical honeycomb macroporous membrane improves 10 times.Other than with wide in range absorption region,
It is practical in polymer solar battery that enhancing photoelectric conversion performance can be such that bionical honeycomb-patterned ordered macroporous structure film promises to be
The material of application.
Photoelectric device of the invention have that preparation method is simple, photoelectric conversion efficiency is obviously improved and with novel high score
The advantages that sub- material is mutually compatible with.It can be seen that structure by analyzing the above relevant report for improving inorganic material optoelectronic pole transfer efficiency
It builds and gives receptor semi-conducting polymer bionical honeycomb macroporous membrane optoelectronic pole, while improving luminous energy capture rate and photoproduction electricity
The separation of son-hole and transmission efficiency are to improve the effective way of photoelectric conversion efficiency.But related construct semi-conducting polymer
The method of bionical honeycomb macropore ordered structure is also very limited, this to construct bionical honeycomb macropore by functional molecular itself and have
The report that sequence structure assembles preparation is also fewer, and especially bionical honeycomb macropore ordered structure gives acceptor polymer
It is not yet reported that in the application of photovoltaic research field.The present invention gives receptor semi-conducting polymer, further self assembly by synthesis
It prepares and gives receptor semi-conducting polymer bionical honeycomb macropore ordered structure, to be prepared imitative to receptor semi-conducting polymer
Raw honeycomb macropore ordered structure film.
The present invention designs the bionical honeycomb macropore ordered structure semiconducting polymer film of preparation, and there is macropore orderly to tie
Structure can improve photoelectric conversion efficiency by following several respects simultaneously: (1) orderly macropore ordered structure can reduce the anti-of light
Increase scattering is penetrated, luminous energy capture rate is improved；(2) be conducive to the separation and transmitting of photo-generate electron-hole to acceptor molecule structure；
(3) functional molecular is conducive to the volume and interface performance of optimised devices in device fabrication process as structure construction unit；(4)
Macropore ordered structure assembly has big surface area, facilitates the diffusion of electrolyte.Therefore the bionical honeycomb that we design
Macropore ordered structure assembly not only has advantage on light-use, while also having tribute to the electrochemical reaction of device inside
It offers, photoelectric conversion efficiency can be improved from many aspects.
A kind of bionical honeycomb macropore ordered structure of the present invention to receptor semiconducting polymer film preparation method,
Its step are as follows:
1) synthesis of receptor structure semi-conducting polymer PID-TBT is given:
A) bis- (4,4,5,5- tetramethyl -1,3,2- dioxole -2- of bis- (2- the ethylhexyl) -6,6'- of 1,1'-
Base)-[bis- indanylidene of 3,3N'-] -2,2'- diketone (ID-B) synthesis: by bis- (the 2- ethyls of the bromo- 1,1'- of 1~2g 6,6'- bis-
Hexyl)-[3,3'- bis- indanylidene] -2,2'- diketone, bis- (pinacol combined) two boron of 1.5~3g, [1,1'- is bis- by 0.07~0.1g
(diphenylphosphine) ferrocene] palladium chloride, 0.9~2g potassium acetate is dissolved in the anhydrous Isosorbide-5-Nitrae-dioxane of 20~30mL；Mixing
Solution heats 36~72 hours at nitrogen protection, 60~80 DEG C, then cools to room temperature；Pass through silica dehydrator column chromatography (two
Chloromethanes: volume ratio=1:1 of n-hexane is as eluant, eluent) after purification, final product ID-B is obtained, is dark brown solid；
B) synthesis of receptor structure semi-conducting polymer PID-TBT is given: by 0.7~1.2g ID-B, 0.6~1.2g4,7-
Two (the bromo- 4- hexyl of 5--thiophene -2- base)-diazosulfides (TBT), 0.02~0.04g tetrabutylammonium bromide, 12~18mL are dense
Degree is 2M aqueous sodium carbonate, is added in 20~40mL toluene under nitrogen protection, stirring 30~0.02 is added after sixty minutes
~0.04g tetra- (triphenyl phosphorus) palladium, heating stirring 48~72 hours at 70~95 DEG C；
The polymer of more preferable extinction property in order to obtain needs to carry out end capping reaction, and the present invention uses two kinds of end blocking methods:
Method 1), it is added dissolved with 0.04~0.08g (4,4,5,5- tetramethyls -1,3,2- dioxaborolan alkane-in Xiang Shangshu system
2- yl) benzene 1~5mL toluene solution；After continuing stirring 3~5 hours, 0.4~0.6mL bromobenzene is injected, and futher stir 3~
Stop heating after 5 hours；Method 2), 0.07~0.1g phenyl boric acid is added in Xiang Shangshu system, after continuing reflux 20~40 hours
Stop heating；After method 1) or method 2) mixture be cooled to room temperature after, mixture is slowly poured into methanol, after filtering
Obtain crude product；After crude product is purified 50~70 hours with Soxhlet extractor, after being dissolved and filtered with tetrahydrofuran, methanol is heavy
Shallow lake product obtains semi-conducting polymer PID-TBT, and molecular formula is as follows:
Corresponding polymer English name are as follows:
PID-TBT:
poly[{1,1’-bis(2-ethylhexyl)-[3,3’-biindolinylidene]-2,2’-dione-6,6’-
diyl}-co-{4,7-di-2-hexylthiophenthienyl-2,1,3-benzothiadiazole}]
2) preparation of the bionical honeycomb macropore ordered structure to receptor semiconducting polymer film:
We construct bionical honeycomb macropore ordered structure film using water surface development method, the specific steps are as follows: by 10
~100mg PID-TBT is added in 1~10mL organic solvent or carbon disulfide, and 10~80 μ L solution is taken to pour after completely dissolution
Onto water surface, after organic solvent or carbon disulfide evaporating completely, thus left on water surface diameter be 0.5~1.5cm,
With a thickness of the PID-TBT film of 1~5 μm of blue brown；Then the PID-TBT film is transferred to using the method vertically lifted
In substrate (substrates such as ito glass, FTO glass, quartz glass, silicon wafer), after moisture evaporating completely, this is obtained in substrate surface
The invention bionical honeycomb macropore ordered structure film of PID-TBT.
Organic solvent described in step 2) is the mixture of one or more of chloroform, methylene chloride, benzene or toluene.
It is of the present invention to prepare bionical honeycomb macropore ordered structure to the method use of receptor semiconducting polymer film
Equipment is simple, mild condition, chemical reagent used are cheap and easy to get.In macropore ordered structure film, the average-size of hole is
0.5~3 μm, the average distance between hole is 0.2~1.0 μm.
Macropore ordered structure film prepared by the present invention has orderly bionical honeycomb structure, and being used as optoelectronic pole can
Dramatically increase the capture rate of luminous energy, and its big surface area effectively promoted in photochemical reaction the diffusion of electrolyte and
The separation and transmitting of photo-generate electron-hole.The experimental results showed that the photoelectric respone of the macropore ordered structure film as optoelectronic pole
Performance increases significantly than the flat membrane without macropore ordered structure of same material, quick in electrooptical device especially dyestuff
It is with important application prospects to change area of solar cell.
Detailed description of the invention
Fig. 1: absorption spectrum of the polymer P ID-TBT in chloroform solvent in the embodiment of the present invention.
The scanning electricity of Fig. 2: the PID-TBT being prepared in the embodiment of the present invention bionical honeycomb macropore ordered structure film
The electron scanning micrograph (b) of mirror photo (a) and partial enlargement, wherein the illustration in b is obtained in embodiment 1
The optical photograph of the bionical honeycomb macropore ordered structure film of PID-TBT.
Fig. 3: the PID-TBT in the PID-TBT flat membrane (curve 1) and quartz substrate in quartz substrate prepared by embodiment 1
The reflectance spectrum of bionical honeycomb macropore ordered structure film (curve 2)；
Fig. 4: the PID-TBT that (a) embodiment 1 is prepared bionical honeycomb macropore ordered structure film is (bent in illumination
Line 1) and dark condition under (curve 2) current density with scanning voltage change curve, and (b) the bionical honeycomb of PID-TBT
The photoelectric respone curve of macropore ordered structure film (curve 1) and PID-TBT flat membrane (curve 2).
Specific embodiment
More detailed description is done to technical solution of the present invention with specific embodiment below, but the example is not constituted to this
The limitation of invention.
Embodiment 1
1) synthesis of receptor structure semi-conducting polymer PID-TBT is given:
A) bis- (4,4,5,5- tetramethyl -1,3,2- dioxole -2- of bis- (2- the ethylhexyl) -6,6'- of 1,1'-
Base)-[bis- indanylidene of 3,3N'-] -2,2'- diketone (ID-B) synthesis: by bis- (the 2- ethyl hexyls of the bromo- 1,1'- of 1g 6,6'- bis-
Base)-[3,3'- bis- indanylidene] -2,2'- diketone, bis- (pinacol combined) two boron of 1.5g, 0.07g [1,1'- bis- (diphenylphosphines)
Ferrocene] palladium chloride, 0.9g potassium acetate is dissolved in the anhydrous Isosorbide-5-Nitrae-dioxane of 20mL.Mixed solution under nitrogen protection,
It heats 48 hours, then cools to room temperature at 80 DEG C.Pass through silica dehydrator column chromatography (methylene chloride: n-hexane volume ratio=1:1
As eluant, eluent) after purification, final product is obtained, is dark brown solid, product quality 0.86g.
1H-NMR(CDCl3) δ (ppm): 9.13 (d, J=7.9Hz, 2H), 7.48 (d, J=7.9Hz, 2H), 7.16 (s,
2H),3.68(m,4H),1.90(bs,2H),1.48–1.19(m,40H),0.92(m,12H)；13C-NMR(125MHz,CDCl3)δ
(ppm):168.1,144.4,134.3,128.8,128.6,124.2,113.5,84.0,83.43,44.1,37.4,30.6,
29.6,28.6,25.0,24.8,24.1,23.0,14.1,10.7.
B) synthesis of PID-TBT: by 0.7g ID-B, 0.6g 4,7- bis- (the bromo- 4- hexyl of 5--thiophene -2- base)-benzo thiophene
Diazole (TBT), 0.02g tetrabutylammonium bromide, 12mL concentration are 2M aqueous sodium carbonate, are added to 20mL first under nitrogen protection
In benzene, after stirring half an hour, 0.02g tetra- (triphenyl phosphorus) palladium is added, heating stirring at 95 DEG C, after 48 hours, addition contains
The toluene solution of 0.04g (4,4,5,5- tetramethyl -1,3,2- dioxaborolan alkane -2- base) benzene.Continue stirring 3 hours
Afterwards, 0.4mL bromobenzene is injected, and stops heating after futher stirring 3 hours.After object to be mixed is cooled to room temperature, mixture is delayed
Slow pours into methanol, and crude product is obtained after filtering.In order to further obtain the product of high-purity, by crude product Soxhlet extraction
After device purifies 50 hours, after being dissolved and filtered with tetrahydrofuran, methanol extraction product obtains semi-conducting polymer PID-TBT, produces
The quality of object is 0.7g.
1H-NMR(CDCl3)δ(ppm):9.30–9.11(m,2H),8.16–6.92(m,8H),3.82–3.62(m,4H),
2.91–2.60(m,4H),2.01–1.14(m,34H),1.04–0.64(m,62H).GPC:Mn=5,278, Mw=9,518, PDI
=1.80.
2) preparation of the bionical honeycomb macropore ordered structure film of PID-TBT:
We construct the bionical honeycomb macropore ordered structure film of PID-TBT using water surface development method.Specific steps are such as
Under: 10mg PID-TBT is added in 1mL chloroform, 10 μ L solution is taken to be poured on water surface after completely dissolution, it is complete to chloroform
After pervaporation, the film for the blue brown that diameter is 0.5cm is left on water surface.Then by the PID-TBT film on water surface
It is transferred on ito glass using the method vertically lifted, after moisture evaporating completely is complete, so that it may obtain the bionical bee of PID-TBT
Nest shape macropore ordered structure film, the average-size of hole are 0.5 μm, and the average distance between hole is 0.2 μm, with a thickness of 2 μ
m。
1 comparative experiments of embodiment: the preparation of PID-TBT flat membrane.
The preparation of PID-TBT flat membrane is operated such as each step of embodiment 1, the difference is that the step 2) of embodiment 1, is by 10
μ L, the chloroformic solution that concentration is 10mg/mL PID-TBT molecule are poured on ito glass, then in the item of relative humidity < 30%
Make chloroform solvent volatilization preparation flat membrane, diameter 0.5cm, with a thickness of 1 μm under part.
1 performance test of embodiment
The bionical honeycomb macropore ordered structure film of PID-TBT produced by the present invention is used as optoelectronic pole, using CHI660E
Electrochemical workstation (Shanghai Chen Hua company) (platinum filament is to electrode, and Ag/AgCl is reference electrode) under three-electrode system, with
The aqueous sodium persulfate solution of 0.5M is electrolyte, and 300W xenon lamp is light source, carries out photoelectric respone test to optoelectronic pole.PID-TBT is imitative
Raw honeycomb macropore ordered structure film and the photocurrent values of PIID-DTB flat membrane are respectively 0.0088mA/cm2And 0.0008mA/
cm2, illustrate that the bionical honeycomb macropore ordered structure film of PID-TBT of preparation has superior photoelectric response performance.
Absorption spectrum of the polymer P ID-TBT in chloroform solvent in 1 embodiment of the present invention of attached drawing.PID-TBT molecule exists
Visible region (section 400nm-800nm) has wide in range and strong absorption.
Fig. 2: the scanning electron microscope of the bionical honeycomb macropore ordered structure film of PID-TBT of 1 preparation in the embodiment of the present invention
The electron scanning micrograph (b) of photo (a) and partial enlargement, wherein the illustration in b is PID- obtained in embodiment 1
The optical photograph of the bionical honeycomb macropore ordered structure film of TBT；The shown bionical honeycomb macropore ordered structure film of PID-TBT
Orderly bionical cellular structures are all presented in very big range, the average-size of hole is 0.5 μm, between hole
Average distance is 0.2 μm.
Fig. 3: the PID-TBT in the PID-TBT flat membrane (curve 1) and quartz substrate in quartz substrate prepared by embodiment 1
The reflectance spectrum of bionical honeycomb macropore ordered structure film (curve 2)；The bionical honeycomb macropore of PID-TBT as shown in the figure is orderly
Structural membrane ratio PID-TBT flat membrane can reduce by 7% light reflection.
Fig. 4: the PID-TBT that (a) embodiment 1 is prepared bionical honeycomb macropore ordered structure film is (bent in illumination
Line 1) and dark condition under (curve 2) current density with scanning voltage change curve, and (b) the bionical honeycomb of PID-TBT
The photoelectric respone curve of macroporous membrane (curve 1) and PID-TBT flat membrane (curve 2)；As shown in Fig. 4 (a), relative in dark,
Under light illumination, the photoelectric current of the bionical honeycomb macropore ordered structure film of PID-TBT is sharply increased with scanning voltage.Such as Fig. 4
(b) shown in, the photoelectric current of the bionical honeycomb macroporous membrane of PID-TBT and PID-TBT flat membrane distinguishes 0.0088mA/cm2With
0.0008mA/cm2。
Embodiment 2
Such as each step operation of embodiment 1, the difference is that embodiment 2 synthesizes the step of semi-conducting polymer is use not
Together.Specific step is as follows: a) synthesis of ID-B: by bis- (2- ethylhexyl)-[bis- indanes of 3,3'- of the bromo- 1,1'- of 2g 6,6'- bis-
Subunit] -2,2'- diketone, bis- (pinacol combined) two boron of 3g, 0.1g [1,1'- bis- (diphenylphosphine) ferrocene] palladium chloride, 2g second
Sour potassium is dissolved in the anhydrous 1,4- dioxane of 30mL.Mixed solution under nitrogen protection, heats 72 hours at 60 DEG C, then cold
But to room temperature.After purification by silica dehydrator column chromatography (methylene chloride: n-hexane volume ratio=1:1 is as eluant, eluent), it obtains
Final product is dark brown solid.
B) synthesis of PID-TBT: by 1.2g ID-B, 1.2g 4,7- bis- (the bromo- 4- hexyl of 5--thiophene -2- base)-benzo thiophene
Diazole (TBT), 0.04g tetrabutylammonium bromide, 18mL concentration are 2M aqueous sodium carbonate, are added to 40mL first under nitrogen protection
In benzene, after stirring half an hour, 0.04g tetra- (triphenyl phosphorus) palladium is added, at 95 DEG C after heating stirring 72 hours, be added dissolved with
The 5mL toluene solution of 0.08g (4,4,5,5- tetramethyl -1,3,2- dioxaborolan alkane -2- base) benzene continues stirring 5 hours
Afterwards, 0.6mL bromobenzene is injected.Stop heating after continuing stirring 5 hours.It is after object to be mixed is cooled to room temperature, mixture is slow
It pours into methanol, crude product is obtained after filtering.In order to further obtain the product of high-purity, crude product is mentioned with Soxhlet extractor
After pure 70 hours, after being dissolved and filtered with tetrahydrofuran, methanol extraction product obtains semi-conducting polymer PID-TBT.1H-NMR
(CDCl3) consistent with the shift value of embodiment 1.GPC:Mn=10275, Mw=15367, PDI=1.69.
The step of bionical honeycomb macroporous membrane prepared by embodiment 2, is consistent with embodiment 1, flat between obtained hole
Distance is 0.3 μm, and hole size is 0.5 μm.
Embodiment 3
Such as each step operation of embodiment 1, the difference is that embodiment 2 synthesizes the step of semi-conducting polymer is use not
Together.Specific step is as follows: a) synthesis of ID-B: by bis- (2- ethylhexyl)-[bis- indanes of 3,3'- of the bromo- 1,1'- of 2g 6,6'- bis-
Subunit] -2,2'- diketone, bis- (pinacol combined) two boron of 2g, 0.09g [1,1'- bis- (diphenylphosphine) ferrocene] palladium chloride,
1.5g potassium acetate is dissolved in the anhydrous 1,4- dioxane of 30mL.Mixed solution under nitrogen protection, heats 72 hours at 80 DEG C,
It then cools to room temperature.It is purified by silica dehydrator column chromatography (methylene chloride: n-hexane volume ratio=1:1 is as eluant, eluent)
Afterwards, final product is obtained, is dark brown solid.
B) synthesis of PID-TBT: by 1.2g ID-B, 1.2g 4,7- bis- (the bromo- 4- hexyl of 5--thiophene -2- base)-benzo thiophene
Diazole (TBT), 0.04g tetrabutylammonium bromide, 18mL concentration are 2M aqueous sodium carbonate, are added to 40mL first under nitrogen protection
In benzene, after stirring half an hour, 0.04g tetra- (triphenyl phosphorus) palladium is added, at 85 DEG C after heating stirring 72 hours, 0.1g benzene is added
Boric acid stops heating after continuing reflux 40 hours.After object to be mixed is cooled to room temperature, mixture is slowly poured into methanol,
Crude product is obtained after filtering.In order to further obtain the product of high-purity, after crude product is purified 70 hours with Soxhlet extractor,
After being dissolved and filtered with tetrahydrofuran, methanol extraction product obtains semi-conducting polymer PID-TBT.
The step of bionical honeycomb macroporous membrane prepared by embodiment 3, is consistent with embodiment 1, flat between obtained hole
Distance is 0.3 μm, and hole size is 0.5 μm.
Embodiment 4
Such as each step operation of embodiment 1, the difference is that bionical honeycomb macropore is orderly tied in the step 2) of embodiment 4
The preparation method of structure is different, specific as follows: 100mg PID-TBT being added in 10mL carbon disulfide, takes 80 μ after completely dissolution
L solution is poured on the water surface, and in about 2 minutes after carbon disulfide evaporating completely, the indigo plant palm fibre that diameter is 1.5cm can be left on the water surface
The film of color.Then by the PID-TBT film transfer to FTO glass on water surface, after moisture evaporating completely is complete, so that it may
To the bionical honeycomb macropore ordered structure film of PID-TBT.
The average-size of the laminated film Hole of preparation is 1 μm, and the average distance between hole is 0.8 μm.
Embodiment 5
As each step of embodiment 1 operates, unlike embodiment 5 step 2) bionical honeycomb macropore ordered structure
Preparation method is different, specific as follows: 60mg PID-TBT being added in 10mL methylene chloride, takes 50 μ L solution after completely dissolution
It is poured on the water surface, in about 2 minutes after methylene chloride evaporating completely, the thin of the blue brown that diameter is 1cm can be left on the water surface
Film.Then by the PID-TBT film transfer to quartz glass on water surface, after moisture evaporating completely is complete, so that it may obtain
The bionical honeycomb macropore ordered structure film of PID-TBT.
The average-size of the laminated film Hole of preparation is 3 μm, and the average distance between hole is 1 μm.
Embodiment 6
As each step of embodiment 1 operates, unlike embodiment 6 step 2) bionical honeycomb macropore ordered structure
Preparation method is different, specific as follows: 50mg PID-TBT being added in 10mL benzene, 40 μ L solution is taken to be poured into after completely dissolution
On the water surface, in about 2 minutes after benzene evaporating completely, the film for the blue brown that diameter is 0.8cm can be left on the water surface.Then by water
In PID-TBT film transfer to silicon wafer on surface, after moisture evaporating completely is complete, so that it may obtain the bionical honeycomb of PID-TBT
Macropore ordered structure film.
The average-size of the laminated film Hole of preparation is 2.5 μm, and the average distance between hole is 1 μm.
Claims (5)
1. a kind of bionical honeycomb macropore ordered structure is to the preparation method of receptor semiconducting polymer film, its step are as follows:
1) synthesis of receptor structure semi-conducting polymer PID-TBT is given:
A) bis- (2- the ethylhexyl) -6,6'- of 1,1'- bis- (4,4,5,5- tetramethyl -1,3,2- dioxole -2- bases)-[3,
Bis- indanylidene of 3N'-] -2,2'- diketone (ID-B) synthesis: by the bromo- 1,1'- of 1~2g 6,6'- bis- bis- (2- ethylhexyls) -
[3,3'- bis- indanylidene] -2,2'- diketone, bis- (pinacol combined) two boron of 1.5~3g, 0.07~0.1g [1,1'- bis- (diphenyl
Phosphine) ferrocene] palladium chloride, 0.9~2g potassium acetate is dissolved in the anhydrous Isosorbide-5-Nitrae-dioxane of 20~30mL；Mixed solution is in nitrogen
Gas shielded heats 36~72 hours at 60~80 DEG C, then cools to room temperature；After purification by silica dehydrator column chromatography, it obtains
Final product ID-B is dark brown solid, wherein methylene chloride: volume ratio=1:1 of n-hexane is as eluant, eluent；
B) synthesis of receptor structure semi-conducting polymer PID-TBT is given: by 0.7~1.2g ID-B, 0.6~1.2g 4,7- bis-
(the bromo- 4- hexyl of 5--thiophene -2- base)-diazosulfide, 0.02~0.04g tetrabutylammonium bromide, 12~18mL concentration are 2M carbon
Acid sodium aqueous solution is added under nitrogen protection in 20~40mL toluene, stirring 30~0.02~0.04g tetra- is added after sixty minutes
(triphenyl phosphorus) palladium, heating stirring 48~72 hours at 70~95 DEG C；
End capping reaction, method 1), it is added dissolved with 0.04~0.08g (4,4,5,5- tetramethyls -1,3,2- dioxy in Xiang Shangshu system
Miscellaneous boron heterocycle pentane -2- base) benzene 1~5mL toluene solution；After continuing stirring 3~5 hours, 0.4~0.6mL bromobenzene is injected, and
Stop heating after futher stirring 3~5 hours；Method 2), 0.07~0.1g phenyl boric acid is added in Xiang Shangshu system, continues to flow back
Stop heating after 20~40 hours；
After method 1) or method 2) mixture be cooled to room temperature after, mixture is slowly poured into methanol, is obtained after filtering
Crude product；After crude product is purified 50~70 hours with Soxhlet extractor, after being dissolved and filtered with tetrahydrofuran, methanol extraction is produced
Object obtains molecular formula semi-conducting polymer PID-TBT as follows,
2) preparation of the bionical honeycomb macropore ordered structure to receptor semiconducting polymer film:
10~100mg PID-TBT is added in 1~10mL organic solvent or carbon disulfide, takes 10~80 μ L after completely dissolution
Solution is poured on water surface, after organic solvent or carbon disulfide evaporating completely, so that leaving diameter on water surface is 0.5
~1.5cm, with a thickness of the PID-TBT film of 1~5 μm of blue brown；Then the PID-TBT film is utilized into the side vertically lifted
Method is transferred in substrate, and after moisture evaporating completely, it is thin to obtain the bionical honeycomb macropore ordered structure of PID-TBT in substrate surface
Film.
2. a kind of bionical honeycomb macropore ordered structure as described in claim 1 is to the preparation of receptor semiconducting polymer film
Method, it is characterised in that: organic solvent is the mixture of one or more of chloroform, methylene chloride, benzene or toluene.
3. a kind of bionical honeycomb macropore ordered structure as described in claim 1 is to the preparation of receptor semiconducting polymer film
Method, it is characterised in that: substrate is ito glass, FTO glass, quartz glass or silicon wafer.
4. a kind of bionical honeycomb macropore ordered structure gives receptor semiconducting polymer film, it is characterised in that: wanted by right
1~3 any one method is asked to be prepared.
5. a kind of bionical honeycomb macropore ordered structure as claimed in claim 4 turns to receptor semiconducting polymer film in photoelectricity
Change the application of aspect.
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| CN104211981A (en) * | 2014-09-11 | 2014-12-17 | 北京航空航天大学 | Self-assembled forming method of multilevel honeycomb micropore polymer film |
| CN104245670A (en) * | 2012-04-06 | 2014-12-24 | 捷恩智株式会社 | Benzofluorene compound, material for light-emitting layer which is produced using said compound, and organic electroluminescent element |
| CN104465118A (en) * | 2014-12-14 | 2015-03-25 | 吉林大学 | Honeycomb structure graphene/ZnO nanorod composite film, manufacturing method and application |
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| CN104245670A (en) * | 2012-04-06 | 2014-12-24 | 捷恩智株式会社 | Benzofluorene compound, material for light-emitting layer which is produced using said compound, and organic electroluminescent element |
| CN104211981A (en) * | 2014-09-11 | 2014-12-17 | 北京航空航天大学 | Self-assembled forming method of multilevel honeycomb micropore polymer film |
| CN104465118A (en) * | 2014-12-14 | 2015-03-25 | 吉林大学 | Honeycomb structure graphene/ZnO nanorod composite film, manufacturing method and application |
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