CN108281553A - A kind of poly- 3,4- ethene dioxythiophenes cladding tungsten oxide nanometer stick, preparation method and applications - Google Patents
A kind of poly- 3,4- ethene dioxythiophenes cladding tungsten oxide nanometer stick, preparation method and applications Download PDFInfo
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Abstract
The present invention relates to one kind poly- 3,4 ethene dioxythiophenes coat tungsten oxide nanometer stick, preparation method and applications, in a solvent by tungsten oxide nano dispersion made from hydro-thermal reaction, EDOT is added and reacts to obtain blue solution, then the drying after sedimentation removal PEDOT and tungsten oxide nano.Processing step is simple and mild condition, can obtain poly- 3 uniformly and be in neutrality, the tungsten oxide nanometer stick of 4 ethene dioxythiophenes cladding；The tungsten oxide nanometer stick has higher fermi level or work content, corrosion of the PSS to anode substrate can be effectively reduced, to improve efficiency and the service life of perovskite solar cell；And it energy level and perovskite material energy level it is closer, can be used as the hole transmission layer of perovskite solar cell, efficiently extract, transmit photohole, and then improve the energy conversion efficiency of perovskite solar cell.
Description
Technical field
The invention belongs to photovoltaic material fields, are related to a kind of hole transport layer material of perovskite solar cell, specifically
It is related to a kind of poly- 3,4- ethene dioxythiophenes cladding tungsten oxide nanometer stick, preparation method and poly- 3,4- ethene dioxythiophenes cladding
The application of tungsten oxide nanometer stick.
Background technology
Perovskite solar cell has the characteristics such as light weight, flexibility be good, at low cost, environmentally friendly, is current novel energy
The hot spot of area research.Hole transmission layer is a kind of functional material between anode and photoactive layer, can effectively be collected
And transporting holes, inhibit hole and electronics compound.Therefore, select suitable hole mobile material for optimizing perovskite solar energy
The photoelectric conversion efficiency and device performance of battery play the role of vital.
Currently, for the perovskite solar cell with p-i-n structure, most common hole transport layer material is
PEDOT：PSS；But its cost is higher, thermal stability is poor, and polystyrolsulfon acid (PSS) acidity can corrode more by force anode, to
Reduce the stability of perovskite solar cell.Therefore, a series of transition metal oxides are (such as：NiOX、MoOX、VOX、CuOXWith
WOXDeng) it is used as hole transport layer material, to improve the stability of perovskite solar cell, while reducing the perovskite sun
The cost of energy battery.Compared to other different materials, tungsten oxide (WOX) with chemical stability is good, W/O stoichiometries are adjustable
Control, the advantages that level structure is controllable, carrier mobility is high, cheap.But WOXWork content about 4.6~4.8eV, with
The valence-band level (5.3~5.4eV) of perovskite mismatches, and is unfavorable for the collection and transmission of photohole, therefore be not a kind of reason
The hole mobile material thought.Therefore, to WOXNano material is modified or is modified, and is prepared and is suitable for perovskite solar cell
Hole transport layer material will be with important scientific meaning and economic value.
Invention content
A kind of poly- 3,4- ethene dioxythiophenes cladding oxygen is provided the invention aims to overcome the deficiencies in the prior art
Change the preparation method of tungsten nanometer rods.
In order to achieve the above objectives, the technical solution adopted by the present invention is：A kind of poly- 3,4- ethene dioxythiophenes cladding oxidation
The preparation method of tungsten nanometer rods in a solvent by tungsten oxide nano dispersion made from hydro-thermal reaction is added EDOT and reacts blue
Color solution, then the drying after sedimentation removal PEDOT and tungsten oxide nano.
Optimally, the tungsten oxide nano is that tungsten salt presoma is dissolved in progress hydro-thermal reaction in the first solvent to be made；
The tungsten salt presoma is tungsten hexachloride；First solvent is one or more in ethyl alcohol, methanol, ethylene glycol and isopropanol
The temperature of the mixture of composition, the hydro-thermal reaction is 150~200 DEG C.
Optimally, the solvent is water, and the dispersion concentration of the tungsten oxide nano is≤50mg/mL.
Optimally, the length of the tungsten oxide nano is 100~500nm, and width is 5~50nm.
Further, the ratio of the tungsten oxide nano and the EDOT are 10~50mg：5~25 μ L.
Optimally, be added after the EDOT room temperature, be stirred continuously under conditions of reaction react blue molten within 20~50 days
Liquid, the mixing speed are 500~700 revs/min.
Another object of the present invention is to provide a kind of poly- 3,4-rthylene dioxythiophene cladding tungsten oxide nanometer stick, it is by upper
The method stated is made.
It is still another object of the present invention to provide a kind of above-mentioned poly- 3,4- ethene dioxythiophenes to coat tungsten oxide nanometer stick
Using the poly- 3,4-rthylene dioxythiophene cladding tungsten oxide nanometer stick is scattered in solvent and forms dispersion liquid, then will be described
Dispersion liquid spin coating is on substrate and heating anneal forms hole transmission layer；Or by itself and PEDOT:PSS is mixed to form hole biography
Defeated layer.
Optimally, the substrate is tin indium oxide or the tin oxide glass substrate of fluorine doped.
Optimally, the poly- 3,4-rthylene dioxythiophene coats tungsten oxide nanometer stick in PEDOT:Doping concentration in PSS
For 0.5~5mg/mL
Since above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：The poly- 3,4- second of the present invention
Alkene dioxy thiophene coats the preparation method of tungsten oxide nanometer stick, and processing step is simple and mild condition, can obtain uniformly and be in
The tungsten oxide nanometer stick of neutral poly- 3,4- ethene dioxythiophenes cladding；The tungsten oxide nanometer stick have higher fermi level or
Work content can effectively reduce corrosion of the PSS to anode substrate, to improve efficiency and the service life of perovskite solar cell；And
Its energy level and the energy level of perovskite material are closer, can be used as the hole transmission layer of perovskite solar cell, effectively
Extraction, transmission photohole, and then improve the energy conversion efficiency of perovskite solar cell.
Description of the drawings
Fig. 1 coats the picture of tungsten oxide nanometer stick for poly- 3,4- ethene dioxythiophenes obtained in embodiment 2：(a)WOXIt receives
Rice noodles, (b) WOXThe scanning electron microscope (SEM) photograph (SEM) of@PEDOT nanometer rods；
Fig. 2 coats the picture of tungsten oxide nanometer stick for poly- 3,4- ethene dioxythiophenes obtained in embodiment 2：(a)WOX@
The transmission electron microscope picture (SEM) of PEDOT nanometer rods, (b) elemental scan distribution map；
Fig. 3 is PEDOT:PSS and WOXNano wire, WOXThe ultraviolet photoelectron spectroscopy of@PEDOT nanometer rods (embodiment 2)
(UPS) figure；
Fig. 4 is the present invention with WOX@PEDOT nanometer rods are shown as the structure of the perovskite solar cell of hole transmission layer
It is intended to；Wherein 1 is cathode (Ag), and 2 be cathode buffer layer (BCP), and 3 be electron transfer layer (PC61BM), 4 be calcium titanium ore bed
(CH3NH3IxPbCl3-X), 5 be hole transmission layer (WOX、WOX@PEDOT、PEDOT:PSS or PEDOT:PSS-WOX@PEDOT), 6
For anode (ITO electro-conductive glass)；
Fig. 5 is perovskite solar cell Current density-voltage (J-V) curve obtained in different embodiments of the invention
Figure；
Fig. 6 is that the present invention is based on the photoelectric conversion efficiency decay patterns of the perovskite solar cell of different hole transmission layers.
Specific implementation mode
The preparation method of the poly- 3,4-rthylene dioxythiophene cladding tungsten oxide nanometer stick of the present invention, by oxygen made from hydro-thermal reaction
Change tungsten nanowires dispersion in a solvent, EDOT (i.e. 3,4-rthylene dioxythiophene) is added and reacts to obtain blue solution, then is gone through sedimentation
Except dry after PEDOT (i.e. poly- 3,4- ethene dioxythiophenes) and tungsten oxide nano.This method processing step is simple and item
Part is mild, can obtain the tungsten oxide nanometer stick for the poly- 3,4-rthylene dioxythiophene cladding uniformly and being in neutrality.
The tungsten oxide nano is that tungsten salt presoma is dissolved in progress hydro-thermal reaction in the first solvent to be made；The tungsten salt
Presoma is tungsten hexachloride；First solvent is the Conventional solvents that can dissolve tungsten salt presoma, such as selected from ethyl alcohol, methanol,
Ethylene glycol and isopropanol) in one or more compositions mixture, the temperature of the hydro-thermal reaction is preferably 150~200 DEG C.
The solvent is the Conventional solvents that can be dissolved EDOT and have good dispersion to tungsten oxide nano, such as water；The tungsten oxide
The dispersion concentration of nano wire be usually≤50mg/mL, and preferably >=10mg/m because when tungsten oxide nano dispersion concentration mistake
Gao Shihui influences its dispersibility.The length of the tungsten oxide nano obtained is preferably 100~500nm, and width is preferably 5~
50nm.The ratio of the tungsten oxide nano and the EDOT need to control in suitable range, usually 10~50mg：5
~25 μ L, preferably 35mg：8~24 μ L.Be added after the EDOT room temperature, be stirred continuously under conditions of reaction react within 20~50 days
Blue solution (being typically navy blue) is obtained, mixing speed is 500~700 revs/min.
Poly- 3,4-rthylene dioxythiophene obtained above coats tungsten oxide nanometer stick, has higher fermi level or work(
Letter can effectively reduce corrosion of the PSS to anode substrate, to improve efficiency and the service life of perovskite solar cell；And it
Energy level and perovskite material energy level it is closer, can be used as the hole transmission layer of perovskite solar cell.Concrete application
It is as follows：The poly- 3,4- ethene dioxythiophenes cladding tungsten oxide nanometer stick is scattered in be formed in solvent (with solvent above-mentioned) and is divided
Dispersion liquid, then simultaneously heating anneal forms hole transmission layer on substrate by the dispersion liquid spin coating；Or by itself and PEDOT:PSS is mixed
Conjunction forms hole transmission layer.Substrate is tin indium oxide or the tin oxide glass substrate of fluorine doped.The poly- 3,4- ethene dioxythiophenes
Tungsten oxide nanometer stick is coated in PEDOT:Doping concentration in PSS is 0.5~5mg/mL.
Below in conjunction with embodiment, invention is further explained.
Embodiment 1
The present embodiment provides a kind of poly- 3,4- ethene dioxythiophenes cladding tungsten oxide nanometer stick (referred to as WOX@PEDOT receive
Rice stick) and preparation method thereof, specially：
(a) WO is preparedXNano wire (can refer to document：Journal of Materials Chemistry A,2013,1,
6125-6129)：By WCl6It is dissolved in the solution (stirring 15 minutes to be completely dissolved) that a concentration of 12.5mg/mL is configured in ethyl alcohol；
Solution is transferred in hydrothermal reaction kettle, is reacted at 180 DEG C 24 hours and generates WOXNano wire after being cooled to room temperature, uses deionization
Each eccentric cleaning of water, ethyl alcohol 3 times, after be put into it is dried overnight in 45 DEG C of vacuum drying ovens, it is for use (shown in such as Fig. 1 (a))；
(b) WO is preparedX@PEDOT nanometer rods：Take the WO of 35mgXNano wire is dispersed in 1mL deionized waters, and 8 μ L are added dropwise
EDOT, 30 days (500~800rpm of rotating speed) is sufficiently stirred under room temperature to solution becomes navy blue；3~7 days are then allowed to stand with removal
The PEDOT and WO of sedimentationXNano wire, obtains uniform navy blue aqueous solution, and freeze-drying obtains WOX@PEDOT nanometer rods are about
28mg。
Embodiment 2
The present embodiment provides a kind of poly- 3,4- ethene dioxythiophenes cladding tungsten oxide nanometer stick (referred to as WOX@PEDOT receive
Rice stick) and preparation method thereof, and it is almost the same in embodiment 1, unlike：In step (b), the EDOT of dropwise addition is 16 μ
L。
Embodiment 3
The present embodiment provides a kind of poly- 3,4- ethene dioxythiophenes cladding tungsten oxide nanometer stick (referred to as WOX@PEDOT receive
Rice stick) and preparation method thereof, and it is almost the same in embodiment 1, unlike：In step (b), the EDOT of dropwise addition is 24 μ
L。
Embodiment 4
The present embodiment provides a kind of poly- 3,4- ethene dioxythiophenes cladding tungsten oxide nanometer stick (referred to as WOX@PEDOT receive
Rice stick) and preparation method thereof, and it is almost the same in embodiment 1, unlike：In step (a), the WO of 10mg is takenXNanometer
Line is dispersed in 1mL deionized waters.
Embodiment 5
The present embodiment provides a kind of poly- 3,4- ethene dioxythiophenes cladding tungsten oxide nanometer stick (referred to as WOX@PEDOT receive
Rice stick) and preparation method thereof, and it is almost the same in embodiment 1, unlike：In step (a), the WO of 50mg is takenXNanometer
Line is dispersed in 1mL deionized waters.
Comparing embodiment 1-3 is it can be found that WO relative to 35mg/1mLXNano wire aqueous solution, preferably EDOT are added
Amount is 16 μ L, the very few WO of EDOT amounts of additionXThe yield of@PEDOT nanometer rods is slightly lower, and the EDOT amounts being added are more than 16 μ L yields
Do not significantly improve.In addition, comparing embodiment 1, embodiment 4 and embodiment 5 are it can be found that WOXThe concentration of nano wire is relatively low then
WOXThe yield of@PEDOT nanometer rods is relatively low, WOXThe higher then WO of concentration of nano wireXThe yield of@PEDOT nanometer rods is higher.Therefore,
Under conditions of EDOT additions are certain, WOXThe yield and WO of@PEDOT nanometer rodsXThe concentration of nano wire is related.Implemented by five
Similar WO can be obtained in exampleX@PEDOT nanometer rods, pattern are characterized by SEM (shown in such as Fig. 1 (b)), WOXThe length of nano wire is about
200-300nm, wide about 5-20nm；The product obtained after reaction obviously shortens, the clearly visible clad in surface；TEM characterizes (Fig. 2
(a)) it shows, WOX@PEDOT nanometer rods have apparent nucleocapsid, the WO of size about 5 × 20nmXIt is enclosed with outside nanometer rods poly-
Close nitride layer, WOXThe spacing of lattice of nanometer rods is aboutCorresponding to WO2.72[010] face, long axis direction perpendicular to
[010] face.Characterization result shows the polymerization of EDOT not only in WOXNanostructured surface occurs, and can occur along its [010] face,
To block WOx nano wires to form WOX@PEDOT nanometer rods.TEM Elemental redistributions sweep test (Fig. 2 (b)) display not only has
W, O element exist, also C, and S elements exist, and further prove PEDOT in WOXNanorod surfaces exist.XPS analysis result is aobvious
Show WOXThe W elements of@PEDOT nanorod surfaces are with W5+Oxidation state exists, therefore there are a large amount of oxygen vacancies.And in WOXNano wire
Surface W6+/W5+Than about 4.2, W5+Content it is relatively low.These results show that EDOT polymerize in WOx nanostructured surfaces and generate
By W while PEDOT6+It is reduced to W5+, to generate a large amount of oxygen vacancies.Due to a large amount of oxygen vacancies of metal oxide surface
In the presence of may change its electrical properties, therefore we further characterize its valence electron structure with ultraviolet photoelectron spectroscopy (UPS), obtain
To secondary electron end side as shown in figure 3, WO can be calculatedXWork content about-the 5.2eV of@PEDOT nanometer rods is higher than WOX's
Work content (- 4.8eV) and slightly above PEDOT:The work content (- 5.1eV) of PSS, lowest unoccupied molecular orbital (LUMO) energy with perovskite material
Grade (- 5.3~-5.4eV) more matches, and being conducive to the collection and transmission of photohole in calcium titanium ore bed, (above-mentioned test uses
It is the WO in embodiment 2XNano wire and WOX@PEDOT nanometer rods).
Embodiment 6
The present embodiment provides a kind of applications that poly- 3,4- ethene dioxythiophenes coat tungsten oxide nanometer stick (to prepare and be based on
WOXThe hole transmission layer and perovskite solar cell of@PEDOT nanometer rods), specially：
Configuration concentration is the WO of 10mg/mLXThe@PEDOT nanometer rods aqueous solution (WO prepared using embodiment 2X@
PEDOT nanometer rods), ultrasound makes it be uniformly dispersed in 20 minutes and filters for use；In the ITO Conducting Glass cleaned up,
Spin coating WOX@PEDOT nanometer rods solution applies condition：2000 revs/min of spin coating rotating speed, rotational time 40 seconds, and in air 150
DEG C annealing 5 minutes；Repeat spin coating it is primary and in air 150 DEG C anneal 10 minutes, obtain the sky of thickness moderate (being about 20nm)
Cave transport layer.
Then in WOXThe perovskite that spin coating a layer thickness is about 300nm on the ITO substrates of@PEDOT hole transmission layers modification
(CH3NH3PbI3-xClx) photosensitive layer (and use CH3NH2I (100mg), PbCl2(50mg), PbI2DMF solution (500 μ of (50mg)
L spin coating) is carried out), spin coating rotating speed is 4000rpm, spin-coating time 40s；It under a nitrogen atmosphere, will be at calcium titanium ore bed heating anneal
Reason, annealing temperature are 80 DEG C, and annealing time is 2 hours；The spin coating electron transfer layer on calcium titanium ore bed, use are a concentration of again
The PC of 20mg/mL61BM chlorobenzene solutions, 2000 revs/min of spin coating rotating speed, rotational time 40 seconds；Electron transfer layer is put under vacuum
After setting 30 minutes, in surface spin coating cathode buffer layer, using the aqueous isopropanol of a concentration of 0.5mg/mL BCP, spin coating rotating speed
4000 revs/min, rotational time 30 seconds；Finally in vacuum cavity, (concrete structure is such as the Ag electrodes that evaporation thickness is about 100nm
Shown in Fig. 4).
Under the light intensity irradiation of AM1.5, the open-circuit voltage of the perovskite solar cell is 1.00V, and short circuit current is
17.25mA·cm-2, fill factor 76.78%, photoelectric conversion efficiency is 13.24% (referring to table 1), and J-V characteristic curves are as schemed
Shown in 5.
Embodiment 7
The present embodiment provides the application that a kind of poly- 3,4-rthylene dioxythiophene coats tungsten oxide nanometer stick, it and embodiment 4
In it is almost the same, unlike：Obtained thickness of hole transport layer is about 10nm, than thin in embodiment 4.
Under the light intensity irradiation of AM1.5, the open-circuit voltage of the perovskite solar cell is 0.939V, and short circuit current is
17.876mA·cm-2, fill factor 56.01%, photoelectric conversion efficiency is 9.4% (referring to table 1), J-V characteristic curves such as Fig. 5
It is shown.
Embodiment 8
The present embodiment provides the application that a kind of poly- 3,4-rthylene dioxythiophene coats tungsten oxide nanometer stick, it and embodiment 4
In it is almost the same, unlike：Obtained thickness of hole transport layer is about 40nm, than thick in embodiment 4.
Under the light intensity irradiation of AM1.5, the open-circuit voltage of the perovskite solar cell is 0.891V, and short circuit current is
18.08mA·cm-2, fill factor 56.13%, photoelectric conversion efficiency is 9.04% (referring to table 1), J-V characteristic curves such as Fig. 5
It is shown.
Comparing embodiment 4, embodiment 5 and embodiment 6 are as can be seen that (i.e. spin coating is a concentration of with the condition of embodiment 4
The WO of 10mg/mLX@PEDOT nanometer rods solution is twice) prepare thickness of hole transport layer it is moderate, the calcium prepared on this basis
The photoelectric conversion efficiency highest of titanium ore solar cell.
Embodiment 9
The present embodiment provides the applications that a kind of poly- 3,4-rthylene dioxythiophene coats tungsten oxide nanometer stick, specially：
Configuration concentration is the WO of 1mg/mLX@PEDOT nanometer rods aqueous solutions, with PEDOT:PSS solution by volume 1:1 is mixed
It closes, ultrasound makes it be uniformly dispersed in 20 minutes, and filtering is for use；In the ITO Conducting Glass cleaned up, spin coating WOX@
PEDOT:PEDOT:PSS solution applies condition：2000 revs/min of spin coating rotating speed, rotational time 40 seconds, and in air 150 DEG C move back
Fire 5 minutes, repeat the above process, corotation apply twice, finally in air 150 DEG C anneal 10 minutes.
Then in WOXThe perovskite that spin coating a layer thickness is about 300nm on the ITO substrates of@PEDOT hole transmission layers modification
(CH3NH3PbI3-xClx) photosensitive layer (and use CH3NH2I (100mg), PbCl2(50mg), PbI2DMF solution (500 μ of (50mg)
L spin coating) is carried out), spin coating rotating speed is 4000rpm, spin-coating time 40s；It under a nitrogen atmosphere, will be at calcium titanium ore bed heating anneal
Reason, annealing temperature are 80 DEG C, and annealing time is 2 hours.The spin coating electron transfer layer on calcium titanium ore bed, use are a concentration of again
The PC of 20mg/mL61BM chlorobenzene solutions, 2000 revs/min of spin coating rotating speed, rotational time 40 seconds.Electron transfer layer is put under vacuum
After setting 30 minutes, in surface spin coating cathode buffer layer, using the aqueous isopropanol of a concentration of 0.5mg/mL BCP, spin coating rotating speed
4000 revs/min, rotational time 30 seconds.Finally in vacuum cavity, Ag electrodes that evaporation thickness is about 100nm.
Under the light intensity irradiation of AM1.5, the open-circuit voltage of the perovskite solar cell is 0.987V, and short circuit current is
20.93mA·cm-2, fill factor 71.31%, photoelectric conversion efficiency is 14.73% (referring to table 1), and J-V characteristic curves are as schemed
Shown in 5.
Embodiment 10
The present embodiment provides the application that a kind of poly- 3,4-rthylene dioxythiophene coats tungsten oxide nanometer stick, it and embodiment 7
In it is almost the same, unlike：Configuration concentration is the WO of 5mg/mLX@PEDOT nanometer rods aqueous solutions, with PEDOT:PSS solution
By volume 1:1 mixing.
Under the light intensity irradiation of AM1.5, the open-circuit voltage of the perovskite solar cell is 0.927V, and short circuit current is
18.04mA·cm-2, fill factor 76.13%, photoelectric conversion efficiency is 12.74% (referring to table 1), and J-V characteristic curves are as schemed
Shown in 5.
Comparative example 1
This comparative example provides a kind of application of tungsten oxide nanometer stick, it with it is almost the same in embodiment 6, unlike：
Using only WOXNano wire makes hole transmission layer.
Under the light intensity irradiation of AM1.5, the open-circuit voltage of the perovskite solar cell is 0.508V, and short circuit current is
8.56mA·cm-2, fill factor 33.61%, photoelectric conversion efficiency is 1.46% (referring to table 1), J-V characteristic curves such as Fig. 5
It is shown.
Comparative example 2
This comparative example provides a kind of PEDOT:PSS makees the application of hole transmission layer, it with it is almost the same in embodiment 9,
Unlike：PEDOT is only applied in the ITO Conducting Glass cleaned up:PSS films are to obtain hole transmission layer.
Under the light intensity irradiation of AM1.5, the open-circuit voltage of the perovskite solar cell is 0.949V, and short circuit current is
19.88mA·cm-2, fill factor 70.27%, photoelectric conversion efficiency is 13.26% (referring to table 1), and J-V characteristic curves are as schemed
Shown in 5.
Embodiment 6, embodiment 9 and comparative example 1, comparative example 22 are compared, it can be seen that WOX@PEDOT nanometer rods are as empty
Its hole transporting property of hole transport materials is much better than WOXNano wire, the PEDOT with commercialization:PSS hole mobile materials are suitable.
Using WOX@PEDOT nanometer rods adulterate PEDOT:PSS hole transmission layers can further improve its hole transport efficiency, to improve
The photoelectric conversion efficiency of perovskite solar cell.The performance parameter such as table of the perovskite solar cell prepared in above-mentioned each example
Shown in 1.
The performance parameter table of the perovskite solar cell prepared in 1 embodiment 6-10 of table, comparative example 1-2
Experimental example 1
This example provides the stability test of the perovskite device of above-mentioned different hole transmission layers, specifically：Implementation will be passed through
Perovskite solar cell prepared by example 6, embodiment 9 and comparative example 2 is stored in glove box (N2Atmosphere, room temperature), respectively
Test its stability.The i.e. PCE of three kinds of perovskite solar cells shown in Fig. 6 with storage time variation (decaying) curve, from
As can be seen that perovskite solar cell prepared by embodiment 6 has highest stability in Fig. 6, PCE is still kept just after 35 days
The 95% of initial value.Perovskite solar cell prepared by embodiment 7 and comparative example 1 PCE after 35 days has decayed 15% He respectively
23%, only the 85% of initial value and 77%.This is because PEDOT:PSS has stronger acidity, can cause one to ITO electrode
Determine the corrosion of degree, therefore is based on PEDOT:The stability of the perovskite solar cell of PSS is worst.Prepared by embodiment 6
WOX@PEDOT hole transmission layers are neutrality, avoid the corrosion of ITO electrode, therefore be based on WOXThe perovskite battery of@PEDOT exists
Do not decay substantially under storage condition.In embodiment 9, PEDOT:The hole transmission layer of PSS is due to WOX@PEDOT nanometer rods
Doping, acidity slightly reduce, and slow down the corrosion to ITO electrode, therefore stablize relative to the perovskite solar cell of comparative example 2
Property slightly promoted.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of poly- 3,4-rthylene dioxythiophene cladding tungsten oxide nanometer stick, it is characterised in that：By hydro-thermal reaction
Tungsten oxide nano dispersion obtained in a solvent, is added EDOT and reacts to obtain blue solution, then through sedimentation removal PEDOT and oxidation
It is dry after tungsten nanowires.
2. the preparation method of poly- 3,4-rthylene dioxythiophene cladding tungsten oxide nanometer stick, feature exist according to claim 1
In：The tungsten oxide nano is that tungsten salt presoma is dissolved in progress hydro-thermal reaction in the first solvent to be made；The tungsten salt forerunner
Body is tungsten hexachloride；First solvent is the mixing of one or more compositions in ethyl alcohol, methanol, ethylene glycol and isopropanol
The temperature of object, the hydro-thermal reaction is 150~200 DEG C.
3. the preparation method of poly- 3,4-rthylene dioxythiophene cladding tungsten oxide nanometer stick, feature exist according to claim 1
In：The solvent is water, and the dispersion concentration of the tungsten oxide nano is≤50mg/mL.
4. the preparation method of poly- 3,4-rthylene dioxythiophene cladding tungsten oxide nanometer stick, feature exist according to claim 1
In：The length of the tungsten oxide nano is 100~500nm, and width is 5~50nm.
5. the preparation method of poly- 3,4-rthylene dioxythiophene cladding tungsten oxide nanometer stick, feature exist according to claim 4
In：The ratio of the tungsten oxide nano and the EDOT are 10~50mg：5~25 μ L.
6. the preparation method of poly- 3,4-rthylene dioxythiophene cladding tungsten oxide nanometer stick, feature exist according to claim 1
In：Be added after the EDOT room temperature, be stirred continuously under conditions of reaction react to obtain within 20~50 days blue solution, the stirring is fast
Degree is 500~700 revs/min.
7. a kind of poly- 3,4-rthylene dioxythiophene coats tungsten oxide nanometer stick, it is characterised in that：It in claim 1 to 6 by appointing
The preparation method of the one poly- 3,4- ethene dioxythiophenes cladding tungsten oxide nanometer stick is made.
8. the application of poly- 3,4-rthylene dioxythiophene cladding tungsten oxide nanometer stick described in claim 7, it is characterised in that：It will be described
Poly- 3,4-rthylene dioxythiophene cladding tungsten oxide nanometer stick, which is scattered in solvent, forms dispersion liquid, then the dispersion liquid is spin-coated on
On substrate and heating anneal forms hole transmission layer；Or by itself and PEDOT:PSS is mixed to form hole transmission layer.
9. the application of poly- 3,4-rthylene dioxythiophene cladding tungsten oxide nanometer stick according to claim 8, it is characterised in that：Institute
It is tin indium oxide or the tin oxide glass substrate of fluorine doped to state substrate.
10. the application of poly- 3,4-rthylene dioxythiophene cladding tungsten oxide nanometer stick according to claim 8, it is characterised in that：
The poly- 3,4- ethene dioxythiophenes coat tungsten oxide nanometer stick in PEDOT:Doping concentration in PSS is 0.5~5mg/mL.
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