CN109860396A - A kind of perovskite solar battery and preparation method and its polymer/fullerene derivate charge transport layer - Google Patents
A kind of perovskite solar battery and preparation method and its polymer/fullerene derivate charge transport layer Download PDFInfo
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Abstract
The invention discloses a kind of perovskite solar battery and preparation method and its polymer/fullerene derivate charge transport layer, which is followed successively by glass substrate, charge transport layer, perovskite absorbed layer, polymer/fullerene derivate charge transport layer, buffer layer and metal electrode from top to bottom；Wherein polymer/fullerene derivate charge transport layer is the heterojunction structure that polymer and fullerene derivate are formed；It can make to be formed between donor and receptor mutually to separate by doping, and when concentration ratio is suitable for, it will form good electron propagation ducts, coverage effect is good, reduces charge transport layer defect, reduces Carrier recombination, to reduce leakage current, promotes electron-transport.By comparison, it was found that, the dielectric constant of the perovskite battery charge transport layer of the structure significantly improves about 24% relative to pure fullerene derivate, and other performances do not reduce, and the highest photoelectric conversion efficiency for the perovskite solar cell prepared can reach 20.60%.
Description
[technical field]
The invention belongs to solar-photovoltaic technology fields, and in particular to a kind of perovskite solar battery and preparation method with
Its polymer/fullerene derivate charge transport layer.
[background technique]
Since two thousand nine, the novel perovskite solar battery of organic inorganic hybridization for its excellent properties to cause greatly
Concern.The perovskite solar battery structure of mainstream at present, is divided into formal structure and transconfiguration.Transconfiguration is compared to formal knot
The characteristics of structure has hysteresis effect small, does not need high temperature, is more nearly commercialized requirement.However, pure fullerene derivate
There are various defects for charge transport layer, cause battery efficiency low.
[summary of the invention]
It is an object of the invention to overcome the above-mentioned prior art, a kind of perovskite solar battery and preparation are provided
Method and its polymer/fullerene derivate charge transport layer.This method by by it is polymer-doped enter fullerene derivate electricity
In lotus transport layer, so that charge transport layer is the bulk heterojunction structure that polymer and fullerene derivate are formed, formed preferable
Electron propagation ducts improve electron-transport efficiency.
In order to achieve the above objectives, the present invention is achieved by the following scheme:
A kind of polymer of perovskite solar battery/fullerene derivate charge transport layer, the polymer/fullerene
Derivative charge transport layer is the bulk heterojunction structure of polymer and fullerene derivate.
A further improvement of the present invention is that:
Preferably, in polymer/fullerene derivate charge transport layer, the molar ratio of polymer and fullerene derivate is
(0-500): (1-200).
Preferably, in polymer/fullerene derivate charge transport layer, the molar ratio of polymer and fullerene derivate is
(0-100): (1-200).
Preferably, in polymer/fullerene derivate charge transport layer, the molar ratio of polymer and fullerene derivate is
(0-50): (1-100).
Preferably, polymer PCDTBT, F8TBT, P3HT or PFDTBT, fullerene derivate C60, ICBA, PCBM
Or Bis-C60.
A kind of perovskite solar battery, including be sequentially overlapped glass substrate, charge transport layer, perovskite absorbed layer,
Polymer/fullerene derivate charge transport layer, buffer layer and metal electrode；The polymer/fullerene derivate charge passes
Defeated layer is any of the above-described kind of polymer/fullerene derivate charge transport layer.
Preferably, perovskite absorbed layer is ABX3Structure, wherein A is organic or inorganic cation；B is metal cation；
X is nonmetallic ion.
Preferably, A CH3NH3 +、NH2CH=NH2 +、Cs+Or Ca2+；B is Pb2+、Sn2+、Bi3+Or Ti4+；X is F-、Cl-、
Br-、I-Or O2-。
Preferably, buffer layer is the macromolecular carbonaceous material that a layer thickness is 1-100nm, and molecular weight is greater than 500.
Preferably, macromolecular carbonaceous material is BCP, PEI, Bis-C60Or C60。
Preferably, macromolecular carbonaceous material is the carbon containing semiconductor material of macromolecular, conductivity 10-10~10-1。
A kind of preparation method of the perovskite solar battery of any one of the above, comprising the following steps:
Step 1, glass substrate is prepared；
Step 2, charge transport layer is prepared on a glass substrate；
Step 3, perovskite absorbed layer is prepared on charge transport layer；
Step 4, polymer/fullerene derivate charge transport layer is prepared on perovskite absorbed layer；
Step 5, buffer layer is prepared in polymer/fullerene derivate charge of the electron transport layer；
Step 6, metal electrode is prepared on the buffer layer.
Preferably, in step 4, polymer/fullerene derivate charge transport layer precursor solution is passed through into spin-coating method
It is spin-coated on perovskite absorbed layer, prepares polymer/fullerene derivate charge transport layer.
Preferably, it is (0~500) that the polymer/fullerene derivate charge transport layer precursor liquid, which is molar ratio: (1
~200) mixed solution of polymer and fullerene derivate.
Preferably, in step 4, polymer/fullerene derivate charge transport layer is with a thickness of 10~100nm.
Preferably, after charge transport layer preparation, after the preparation of perovskite absorbed layer and polymer/fullerene derivate is electric
It is post-processed after the preparation of lotus transport layer.
Preferably, it post-processes to be heat-treated, heat treatment temperature is 40-500 DEG C, time 1-100min.
Compared with prior art, the invention has the following advantages:
The invention discloses a kind of polymer of perovskite solar battery/fullerene derivate charge transport layer, the electricity
Lotus transport layer is the bulk heterojunction structure of polymer and fullerene derivate；The present invention in fullerene derivate charge by transmitting
Doped polymer in layer forms body heterojunction；When the bulk heterojunction structure is applied to perovskite battery, it is capable of forming good
Electron propagation ducts, coverage effect is good, can reduce the defect state density of perovskite light absorbing layer, reduces Carrier recombination, from
And leakage current is reduced, promote electron-transport.
The invention also discloses a kind of perovskite solar battery, which is followed successively by glass from top to bottom
Glass substrate, charge transport layer, perovskite absorbed layer, polymer/fullerene derivate charge transport layer, buffer layer and metal electricity
Pole；Wherein polymer/fullerene derivate charge transport layer is the bulk heterojunction structure that polymer and fullerene derivate are formed；
The present invention forms body heterojunction by introducing polymer into fullerene derivate.It can make donor (polymer) by doping
It is formed between receptor (fullerene derivate) and is mutually separated, and when concentration ratio is suitable for, it is logical to will form good electron-transport
Road, coverage effect is good, can reduce the defect state density of perovskite light absorbing layer, Carrier recombination is reduced, to reduce electric leakage
Stream promotes electron-transport.By comparison, it was found that the dielectric constant of the perovskite battery charge transport layer of the structure is relative to pure
Fullerene derivate significantly improves about 24%, and other performances do not reduce, and the perovskite solar cell prepared is most
High-photoelectric transformation efficiency can reach 20.60%, this expands business for the electron-transport efficiency of promotion perovskite solar cell
Using playing the role of enlightenment.
The invention also discloses a kind of preparation method of perovskite solar battery, pass through limitation polymer in preparation process
With the ratio of fullerene derivate, so that the polymer prepared and fullerene derivate charge transport layer surfacing, covering
Property it is good, and then improve electron-transport rate；.
[Detailed description of the invention]
Fig. 1 is the molecular structure of polymer (PCDTBT) and fullerene derivate (PCBM)；
Fig. 2 is the perovskite solar battery structure figure for making charge transport layer based on bulk heterojunction that the present invention prepares；
Fig. 3 is the AFM figure of charge transport layer film prepared by embodiment 1 and comparative example；
Wherein, the surface topography map that (a) figure is PCBM；(b) surface topography map that figure is BHJ；
(c) the mutually separation figure that figure is PCBM；(d) the mutually separation figure that figure is BHJ.
Fig. 4 is the SEM cross-sectional view of the completed device of charge transport layer prepared by embodiment 1 and comparative example；
Wherein, the SEM cross-sectional view that (a) figure is PCBM；(b) cross-sectional view that figure is BHJ.
Fig. 5 is the absorption spectrum comparison diagram of charge transport layer prepared by embodiment 1 and comparative example 1.
Fig. 6 is the electrochemical impedance comparison diagram of charge transport layer prepared by embodiment 1 and comparative example 1.
[specific embodiment]
Below with reference to specific embodiment and attached drawing, the present invention is described in further detail.The invention discloses one kind
The polymer of perovskite solar battery/fullerene derivate charge transport layer.The efficient perovskite battery from top to bottom according to
It is secondary for glass substrate, charge transport layer, perovskite absorbed layer, polymer and fullerene derivate charge transport layer, buffer layer and
Metal electrode；The polymer and fullerene derivate charge transport layer are that the body that polymer and fullerene derivate are formed is heterogeneous
Junction structure.The preparation method of the efficient perovskite battery specifically includes the following steps:
Step 1, ITO/FTO glass substrate is prepared
First dust-free paper is soaked with ethyl alcohol, clean ITO/FTO glass, and successively use using acetone, isopropanol, ethyl alcohol as
Cleaning solution ultrasonic cleaning, every based cleaning liquid scavenging period are 30min；After cleaning terminates, uses and be dried with nitrogen as ITO/FTO glass
Glass substrate is spare.In preparation process, substrate of glass is wiped clean by using the dust-free paper soaked, and clear using multiple kinds of cleaning agent
It washes, the spot of glass surface can be cleaned up；ITO/FTO glass is handled by the UV ozone of certain time, to ITO/FTO
Glass carries out surface modification and improves substrate surface compatibility, guarantees that precursor solution can good drawout.
Step 2, charge transport layer is prepared in FTO glass substrate
Glass substrate is put into UV ozone processor and handles 10~15min to increase compatibility, then, uses high-temp glue
Band reserves electrode evaporation position, guarantees adhesive tape compacting while marking；By spin-coating method by charge transport layer precursor solution
Spin coating prepares charge transport layer on a glass substrate, and the dosage of charge transport layer precursor solution is 50~200uL, spin coating revolving speed
For 2000~5000rpm, the time is 30~60s, and the sample for then obtaining spin coating is placed in 40-500 DEG C of thermal station the 1- that anneals
100min, guarantee obtain required phase.It is cooled to room temperature after annealing, prevents temperature from impacting to next step spin-coating step；
All operations in the step are operated in air.The material of charge transport layer can be graphene oxide, PEDOT:
PSS, PolyTPD or NiOx.Corresponding charge transport layer precursor solution can be PEDOT:PSS dispersion liquid, graphene oxide
Precursor liquid, PolyTPD precursor liquid or NiOx precursor liquid.
Step 3, perovskite absorbed layer is prepared on charge transport layer
Step 3.1 prepares perovskite precursor solution
Perovskite precursor solution can be MAPbI3Precursor solution, FAPbI3Precursor solution, FA0.95Cs0.05PbI3
Precursor solution, (FAPbI3)0.85(MAPbBr3)0.15Precursor solution, CsPbI3Precursor solution, CsPbIBr2Presoma is molten
Liquid, CsPbBr3Precursor solution, CsPbF3Precursor solution, CaTiO3(barium titanate), MASnI3Precursor solution, MA3Bi2I9
Precursor solution, MAPbCl3Precursor solution or MAPbCl3Precursor solution；The concentration of perovskite precursor solution be 0.8~
1.2mol/L；FA in above-mentioned chemical formula is the abbreviation that first is narrowed, and MA is the abbreviation of methylamine, when perovskite precursor solution is
MAPbI3When precursor solution, preparation process is as follows.
(1) synthesis of methylamines base iodine
The hydriodic acid aqueous solution of 10~50mL 33wt% methylethylolamine solution and 5~20mL 57wt% is added sequentially to
In round-bottomed flask, and stirred 6 hours at -5~20 DEG C.The solution being stirred is steamed at 30~80 DEG C using revolving instrument
It evaporates, remove solvent, obtain impure yellow-white methylamino iodine sediment.Impure methylamino iodine is re-dissolved using dehydrated alcohol
Anhydrous ether recrystallization is added later, purifies 1~5 time repeatedly, the product after being purified for sediment；Finally, being dried using vacuum
Case is 24 hours dry at 25~80 DEG C by purified product, and pure methylamino iodine (MA) is made.Master in perovskite absorbed layer
It wants raw material methylamino iodine for laboratory preparation, can be improved the degree of purity of methylamino iodine, improve the quality of perovskite absorbed layer.
(2) perovskite precursor solution is prepared
According to molar ratio 1:(0.6~1.5) mixing lead iodide (PbI2) and methylamino iodine, form solute, by solute according to
The concentration of 0.8~1.2mol/L is dissolved in DMF and DMSO in the mixed solvent and is prepared into Process liquor, DMF and DMSO in solvent
Mixed proportion is 4:1；Configured Process liquor is heated 6 hours at 25~70 DEG C, perovskite precursor solution is made.
(3) perovskite absorbed layer is prepared
Glass substrate/the charge transport layer that will be cooled to room temperature is quickly transferred to spin coating perovskite light absorbing layer in glove box
Film prepares perovskite absorbed layer by spin-coating method on charge transport layer, before spin coating, has to the nitrogen of latex examination gloves case
Atmosphere avoids extraneous factor from impacting the preparation of film.Spin coating proceeding is divided into two parts: first segment is 500~1500rpm,
Duration 20s~30s；Second segment is 2000~4000rpm, 10~60s of duration；When second segment rotation Tu technique is surplus last
When 10~30s, 100~150 μ L chlorobenzenes are rapidly added drop-wise to the sample of rotation, and (chlorobenzene is anti-solvent here, it can be induced
Perovskite rapid crystallization), the chlorobenzene that the range is measured is added drop-wise on perovskite absorbed layer in the period, can spin coating come out
Film it is flat and smooth, covering is complete.After spin coating, sample is annealed 1-100min at 40-500 DEG C.It is then cooling, it is made
Perovskite absorbed layer, the ingredient of entire perovskite battery is glass substrate/charge transport layer/perovskite absorbed layer at this time.Calcium titanium
Mine absorbed layer is ABX3Structure, different according to the type of precursor liquid, perovskite absorbed layer type is different；Wherein, A be it is organic or
Inorganic cation；B is metal cation；X is nonmetallic ion.Corresponding A is CH3NH3 +、NH2CH=NH2 +、Cs+Or Ca2+；B
For Pb2+、Sn2+、Bi3+Or Ti4+；X is F-、Cl-、Br-、I-Or O2-。
Step 4, polymer/fullerene derivate charge transport layer is prepared
The mixing molar ratio of mixed polymer and fullerene derivate, polymer and fullerene derivate is (0~500):
(1~200), it is preferred that the ratio is (0~100): (1~200)；It is furthermore preferred that the ratio is (0~50): (1~100)；
Prepare polymer/fullerene derivate charge transport layer precursor solution；30~100uL polymer/fullerene is derivative
The precursor solution of object charge transport layer is spin-coated on perovskite absorbed layer by spin-coating method.By polymer and fullerene before spin coating
The precursor solution of derivative charge transport layer is with the Teflon filtration film filtering in 0.45 μm of aperture, by filtered forerunner
Liquid solution drops evenly and carries out spin coating on above-mentioned perovskite thin film, and spin coating revolving speed is 3000~7000rpm, and spin-coating time is
20~60s, entire spin coating process anneal sample 1- after spin coating in glove box in 40-500 DEG C of thermal station
100min, the purpose of annealing are that charge transport layer is made to have good configuration of surface.It is polymer and richness that ingredient is made after annealing
The charge transport layer of ene derivative is strangled, the group of sample becomes glass substrate/charge transport layer/perovskite absorbed layer/polymerization at this time
Object and fullerene derivate charge transport layer.Specifically, polymer can for PCDTBT, F8TBT, P3HT and PFDTBT etc.,
Fullerene derivate can be C60, ICBA, PCBM and Bis-C60 etc., PCBM PC60BM, PC70BM etc..
Step 5, buffer layer is prepared
150uL macromolecular carbonaceous material solution is added dropwise on above-mentioned sample after cooling, with 3000~6000rpm, 30
The rotation Tu technique rotation Tu of~60s obtains macromolecular carbonaceous material buffer layer, and the group of sample becomes glass substrate/charge transmission at this time
Layer/perovskite absorbed layer/polymer and fullerene derivate charge transport layer/macromolecular carbonaceous material；Macromolecular carbonaceous material
For 1-100 nanometers of a layer thickness of macromolecular carbonaceous material, molecular weight is greater than 500；Preferably, macromolecular carbonaceous material is big point
The carbon containing semiconductor material of son, conductivity are (10-10~10-1)；Such as BCP, PEI, Bis-C60Or C60Deng.
Step 6, evaporation metal electrode
Sample made from step 5 is placed into mask plate, is transferred in evaporating compartment room, evaporation thickness is 100 in evaporating compartment room
The metal electrode of~200nm, the effective area of mask plate are 0.09cm2；The metal electrode can be Al electrode or Ag electrode.
Final perovskite solar battery is prepared through the above steps, and the ingredient of perovskite solar cell is from top to bottom
It is followed successively by glass substrate/charge transport layer/perovskite absorbed layer/polymer and fullerene derivate charge transport layer/macromolecular
Carbonaceous material/metal electrode.The polymer and fullerene derivate charge transport layer of the perovskite solar cell are by polymer
The heterojunction structure formed is combined with fullerene derivate.
The battery device prepared is subjected to incident photon-to-electron conversion efficiency test, test process are as follows: at room temperature, use
The solar simulator of 2400 model of Keithley company is 100mW/cm in light intensity2Battery effect is carried out under the conditions of (AM 1.5G)
Rate test, sweep speed are 0.3~0.4V/s, and delay time 10-50ms, the step width of scanning is 0.01~0.02V.
Fig. 1 is PCBM the and PCDTBT molecular structure used when the present invention prepares charge transport layer；Fig. 2 is present invention system
Standby hetero-junctions out makees the perovskite solar battery structure figure of charge transport layer.
Fig. 3 is the AFM surface topography for the charge transport layer that the embodiment of the present invention 1 and comparative example 1 are prepared and mutually separates figure
As comparison diagram, the bulk heterojunction that the surface topography map of comparison diagram (a) and figure (c) can see embodiment 1 can be formed continuously
Film, it is sufficient to perovskite surface is completely covered, and then there is very big hole in the PCBM film that comparative example 1 is prepared, and
The test result of SEM is consistent below.It is single-phase for can see PCBM film from the phase separate picture of (b) and (d), and passes through implementation
There is uniform mutually separation in bulk heterojunction (BHJ) film that example 1 is prepared, mutually separates scale about 15nm, this suitable phase
It is highly beneficial to the transmission of carrier to separate scale, because the transmission range of carrier is generally less than 10nm in organic material.
Fig. 4 is the SEM cross-sectional view for the perovskite solar cell completed device that comparative example 1 and embodiment 1 are prepared；Comparison
(a) figure and (b) figure of Fig. 4 can be seen that since PCBM film forming is poor, and perovskite light-absorption layer cannot be covered by PCBM completely, and
Perovskite can be then completely covered in the bulk heterojunction that embodiment 1 is prepared.
Fig. 5 be comparative example 1 prepare based on PCBM prepared as charge transport layer and embodiment 1 and bulk heterojunction
(BHJ) make the absorption spectrum comparison diagram of charge transport layer.As can be seen from the figure bulk heterojunction (BHJ) film is in 500-630nm
There is absorption at place, is conducive to the short-circuit current density for improving battery.
Fig. 6 is the electrochemical impedance comparison for making charge transport layer based on PCBM and bulk heterojunction of comparative example 1 and embodiment 1
Figure.Electrochemical impedance (EIS) is the effective means for studying carrier transport at perovskite solar battery median surface, we test
Using PCBM and bulk heterojunction as the EIS of the perovskite solar battery of charge transport layer, pass through the equivalent circuit in illustration
It is fitted.We can significantly see from figure, and when making charge transport layer using bulk heterojunction, device resistance figure has smaller
Circular arc, illustrate that the carrier transport resistance under the conditions of this is smaller, that is to say, that bulk heterojunction have better electron-transport
Ability can be good at inhibiting carrier in the compound of charge transport layer and calcium titanium ore bed interface.
All of above test shows that the bulk heterojunction of polymer polymerizing object and fullerene derivate composition is to prepare high property
The effective charge transport layer of perovskite solar battery can be inverted.
Embodiment 1
Step 1, FTO glass substrate is prepared
First dust-free paper is soaked with ethyl alcohol, clean FTO glass, and successively use using acetone, isopropanol, ethyl alcohol as clean
Liquid ultrasonic cleaning, every based cleaning liquid scavenging period are 30min；Cleaning terminate after, use be dried with nitrogen it is standby as FTO glass substrate
With.
Step 2, PEDOT:PSS charge transport layer is prepared in FTO glass substrate
After FTO substrate of glass is blown clean, it is put into UV ozone processor and handles 15min to increase compatibility, so
Electrode evaporation position is reserved with high temperature gummed tape afterwards, guarantee adhesive tape compacting while being marked；By spin-coating method by PEDOT:PSS points
Dispersion liquid, which is spin-coated in FTO glass substrate, prepares hollow transport layer, and the dosage of PEDOT:PSS dispersion liquid is 100uL, and spin coating revolving speed is
4000rpm, time 45s, the FTO/PEDOT:PSS that spin coating is obtained are placed in 150 DEG C of thermal station the 10min that anneals, and electricity is made
Lotus transport layer.
Step 3, perovskite absorbed layer is prepared on PEDOT:PSS charge transport layer
Step 3.1 prepares perovskite precursor solution
(1) synthesis of methylamines base iodine
The hydriodic acid aqueous solution of the 33wt% methylethylolamine solution of 24mL and the 57wt% of 10mL is added sequentially to round bottom
In flask, and stirred 4 hours at 0 DEG C.The solution being stirred is distilled at 60 DEG C using revolving instrument, removes solvent, is obtained
To the methylamino iodine sediment of impure yellow-white.Impure methylamino iodine sediment is re-dissolved using dehydrated alcohol, later
Anhydrous ether recrystallization is added, purifies 3 times repeatedly, the product after being purified；Finally, using vacuum drying oven by product at 60 DEG C
Pure methylamino iodine is made in lower drying 24 hours.
(2) perovskite precursor solution is prepared
According to molar ratio 1:1 mixing lead iodide and methylamino iodine, solute is formed, solute is dissolved according to the concentration of 1mol/L
It is prepared into Process liquor in a solvent；By configured Process liquor in 60 DEG C of heating 6h, perovskite precursor solution is made；
(3) perovskite absorbed layer is prepared
Perovskite absorbed layer is prepared by spin-coating method on charge transport layer, will be cooled to the FTO/PEDOT:PSS of room temperature
Substrate is quickly transferred to spin coating perovskite light absorbing layer film in glove box.Before spin coating, the atmosphere of latex examination gloves case；Spin coating work
Skill is divided into two parts: first segment is 1000rpm, duration 20s；Second segment is 3000rpm, duration 40s；Work as second segment
When rotation Tu technique remains last 15s, rapidly 100 μ L chlorobenzenes are added drop-wise on the sample of rotation；After spin coating, sample is existed
Anneal 10min at 100 DEG C.It is then cooling, perovskite absorbed layer is made.
Step 4, PCTDBT and PCBM charge transport layer is prepared
According to molar ratio 1:4.5 mixing PCTDBT and PCBM, the precursor solution of charge transport layer is prepared, after annealing
FTO/PEDOT:PSS/MAPbI3Sample is cooled to room temperature, with the Teflon filtration film filtering 80uL's in 0.45 μm of aperture
The precursor solution of PCTDBT and PCBM charge transport layer, by filtered PCTDBT and PCBM charge transport layer precursor solution
It drops evenly and is carried out on above-mentioned perovskite thin film, carry out spin coating in glove box, spin coating revolving speed is 5000rpm, when spin coating
Between be 40s, revolve Tu after sample is placed on in 70 DEG C of thermal station the 10min that anneals.
Step 5,150uL BCP solution is added dropwise on above-mentioned sample after cooling, with 5000rpm, the rotation Tu technique of 45s
Rotation Tu obtains BCP buffer layer.
Step 6, above-mentioned sample is placed into mask plate, be transferred in evaporating compartment room, evaporation thickness is 150nm in evaporating compartment room
Ag electrode, the effective area of mask plate is 0.09cm2；It is FTO/PEDOT:PSS/MAPbI that structure, which is made,3/PCDTBT-doped
The perovskite solar cell of PCBM/PCB/Ag, wherein charge transport layer is to combine the heterogeneous junction formed by PCTDBT and PCBM
Structure.
The battery device prepared is subjected to incident photon-to-electron conversion efficiency test, the photoelectricity which prepares battery device turns
Change efficiency is 20.6% after tested.
See Table 1 for details for the detailed process parameter of embodiment 2- embodiment 31-table 6, the parameter being not directed in table with embodiment 1
It is identical.
The preparation process parameter of 1 embodiment 2- embodiment 6 of table
The preparation process parameter of 2 embodiment 7- embodiment 11 of table
The preparation process parameter of 3 embodiment 12- embodiment 16 of table
The preparation process parameter of 4 embodiment 17- embodiment 21 of table
The preparation process parameter of 5 embodiment 22- embodiment 26 of table
The preparation process parameter of 6 embodiment 27- embodiment 31 of table
Comparative example 1
Form bulk heterojunction charge transport layer using PCDTBT doping PC60BM: PC60BM and PCTDBT is matched；PC60BM:
PCTDBT=1:0；
Other steps are same as Example 1.
Form bulk heterojunction charge transport layer using PCDTBT doping PC60BM: PC60BM and PCTDBT is matched；PC60BM:
PCTDBT=0:1；
Other steps are same as Example 1.
It is 100mW/ in light intensity using the solar simulator of 2400 models of Keithley company under room temperature environment
cm2Device is carried out to the perovskite solar cell of embodiment 1-3, comparative example 1 and comparative example 2 preparation respectively under the conditions of (AM 1.5G)
The test of part incident photon-to-electron conversion efficiency, test result is as follows table 6.
Table 6 compares highest photoelectric conversion efficiency
It can be obtained by upper table analysis, form bulk heterojunction using PCDTBT doping PCBM and prepare efficient perovskite solar-electricity
The highest photoelectric conversion efficiency of the battery of pond method preparation is integrally higher than the highest photoelectricity of the solar battery of original material preparation
Transfer efficiency.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (17)
1. a kind of polymer of perovskite solar battery/fullerene derivate charge transport layer, which is characterized in that the polymerization
Object/fullerene derivate charge transport layer is the bulk heterojunction structure of polymer and fullerene derivate.
2. a kind of polymer/fullerene derivate charge transport layer of perovskite solar battery according to claim 1,
It is characterized in that, the molar ratio of polymer and fullerene derivate is (0- in polymer/fullerene derivate charge transport layer
500): (1-200).
3. a kind of polymer/fullerene derivate charge transport layer of perovskite solar battery according to claim 1,
It is characterized in that, the molar ratio of polymer and fullerene derivate is (0- in polymer/fullerene derivate charge transport layer
100): (1-200).
4. a kind of polymer/fullerene derivate charge transport layer of perovskite solar battery according to claim 1,
It is characterized in that, the molar ratio of polymer and fullerene derivate is (0- in polymer/fullerene derivate charge transport layer
50): (1-100).
5. a kind of polymer/fullerene derivate charge transport layer of perovskite solar battery according to claim 1,
It is characterized in that, polymer be PCDTBT, F8TBT, P3HT or PFDTBT, fullerene derivate C60, ICBA, PCBM or
Bis-C60。
6. a kind of perovskite solar battery, which is characterized in that including be sequentially overlapped glass substrate, charge transport layer, calcium titanium
Mine absorbed layer, polymer/fullerene derivate charge transport layer, buffer layer and metal electrode；The polymer/fullerene is derivative
Object charge transport layer is any polymer/fullerene derivate charge transport layer described in claim 1-5.
7. a kind of perovskite solar battery according to claim 6, which is characterized in that perovskite absorbed layer is ABX3Knot
Structure, wherein A is organic or inorganic cation；B is metal cation；X is nonmetallic ion.
8. a kind of perovskite solar battery according to claim 7, which is characterized in that A CH3NH3 +、NH2CH=NH2 +、Cs+Or Ca2+；B is Pb2+、Sn2+、Bi3+Or Ti4+；X is F-、Cl-、Br-、I-Or O2-。
9. a kind of perovskite solar battery according to claim 6, which is characterized in that buffer layer is that a layer thickness is 1-
The macromolecular carbonaceous material of 100nm, molecular weight are greater than 500.
10. a kind of perovskite solar battery according to claim 9, which is characterized in that macromolecular carbonaceous material is
BCP、PEI、Bis-C60Or C60。
11. a kind of perovskite solar battery according to claim 9, which is characterized in that macromolecular carbonaceous material is big
The carbon containing semiconductor material of molecule, conductivity 10-10~10-1。
12. a kind of preparation method of perovskite solar battery described in claim 6-11 any one, which is characterized in that packet
Include following steps:
Step 1, glass substrate is prepared；
Step 2, charge transport layer is prepared on a glass substrate；
Step 3, perovskite absorbed layer is prepared on charge transport layer；
Step 4, polymer/fullerene derivate charge transport layer is prepared on perovskite absorbed layer；
Step 5, buffer layer is prepared in polymer/fullerene derivate charge of the electron transport layer；
Step 6, metal electrode is prepared on the buffer layer.
13. a kind of preparation method of perovskite solar battery according to claim 12, which is characterized in that in step 4,
Polymer/fullerene derivate charge transport layer precursor solution is spin-coated on perovskite absorbed layer by spin-coating method, is made
Standby polymer/fullerene derivate charge transport layer.
14. a kind of preparation method of perovskite solar battery according to claim 13, which is characterized in that the polymerization
Object/fullerene derivate charge transport layer precursor liquid is that molar ratio is (0~500):
The polymer of (1~200) and the mixed solution of fullerene derivate.
15. a kind of preparation method of perovskite solar battery according to claim 12, which is characterized in that in step 4,
Polymer/fullerene derivate charge transport layer is with a thickness of 10~100nm.
16. a kind of preparation method of perovskite solar battery according to claim 12, which is characterized in that charge transmission
After layer preparation, after being carried out after the preparation of perovskite absorbed layer and after polymer/fullerene derivate charge transport layer preparation
Reason.
17. a kind of preparation method of perovskite solar battery according to claim 16, which is characterized in that post-process and be
Heat treatment, heat treatment temperature are 40-500 DEG C, time 1-100min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110416412A (en) * | 2019-07-16 | 2019-11-05 | 常州大学 | It is a kind of for improving the electron transfer layer and preparation method of reversed perovskite solar cell stability |
| CN110444672A (en) * | 2019-07-25 | 2019-11-12 | 武汉理工大学 | A kind of fullerene derivate, preparation method and application |
| CN110581221A (en) * | 2019-08-08 | 2019-12-17 | 上海黎元新能源科技有限公司 | Ion additive doped electron transport layer of perovskite solar cell, preparation method and application |
| CN111081882A (en) * | 2019-11-28 | 2020-04-28 | 暨南大学 | D-A system electron transport layer and preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105470403A (en) * | 2015-12-29 | 2016-04-06 | 苏州大学 | Preparation method of cross-linked fullerene bulk heterojunction perovskite solar cell |
| CN106654020A (en) * | 2017-01-24 | 2017-05-10 | 中国科学院上海硅酸盐研究所 | Bulk-heterojunction perovskite thin film, production method thereof and solar cell |
| CN107994121A (en) * | 2017-11-15 | 2018-05-04 | 南京邮电大学 | A kind of electron transfer layer of modifying improves the method for perovskite solar cell properties |
-
2019
- 2019-03-20 CN CN201910214690.3A patent/CN109860396B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105470403A (en) * | 2015-12-29 | 2016-04-06 | 苏州大学 | Preparation method of cross-linked fullerene bulk heterojunction perovskite solar cell |
| CN106654020A (en) * | 2017-01-24 | 2017-05-10 | 中国科学院上海硅酸盐研究所 | Bulk-heterojunction perovskite thin film, production method thereof and solar cell |
| CN107994121A (en) * | 2017-11-15 | 2018-05-04 | 南京邮电大学 | A kind of electron transfer layer of modifying improves the method for perovskite solar cell properties |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110416412A (en) * | 2019-07-16 | 2019-11-05 | 常州大学 | It is a kind of for improving the electron transfer layer and preparation method of reversed perovskite solar cell stability |
| CN110416412B (en) * | 2019-07-16 | 2022-12-16 | 常州大学 | Electron transport layer for improving stability of reverse perovskite solar cell and preparation method |
| CN110444672A (en) * | 2019-07-25 | 2019-11-12 | 武汉理工大学 | A kind of fullerene derivate, preparation method and application |
| CN110444672B (en) * | 2019-07-25 | 2021-07-02 | 武汉理工大学 | Fullerene derivative, preparation method and application thereof |
| CN110581221A (en) * | 2019-08-08 | 2019-12-17 | 上海黎元新能源科技有限公司 | Ion additive doped electron transport layer of perovskite solar cell, preparation method and application |
| CN111081882A (en) * | 2019-11-28 | 2020-04-28 | 暨南大学 | D-A system electron transport layer and preparation method and application thereof |
| CN111162174A (en) * | 2019-12-30 | 2020-05-15 | 电子科技大学 | Perovskite solar cell based on organic bulk heterojunction and preparation method thereof |
| CN112071985A (en) * | 2020-08-04 | 2020-12-11 | 浙江大学 | Interface engineering method for improving full-spectrum stability of perovskite solar cell |
| CN112071985B (en) * | 2020-08-04 | 2022-07-22 | 浙江大学 | Interface engineering method for improving full spectrum stability of perovskite solar cell |
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