CN107591482A - A kind of perovskite solar cell with phase separation structure and preparation method thereof - Google Patents
A kind of perovskite solar cell with phase separation structure and preparation method thereof Download PDFInfo
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Abstract
A kind of perovskite solar cell with phase separation structure and preparation method thereof, belongs to solar cell preparing technical field.The perovskite solar cell with phase separation structure includes phase separation structure, the metal electrode of electrically conducting transparent substrate, the electron transfer layer being sequentially formed on electrically conducting transparent substrate, perovskite light-absorption layer and hole transmission layer.The mixed solution of perovskite light absorbent and hole mobile material is added dropwise in the region to be deposited of the present invention on the electron transport layer, separating for light-absorption layer and cavitation layer is realized by the difference of the hydrophilic-hydrophobic degree of two kinds of materials under the collective effect of fexible film and film layer, and then obtain the phase separation structure of perovskite light-absorption layer and hole transmission layer, it is easy to operate, cost is low, it effectively prevent the generation of impurity between adjacent layer, the complex centre of perovskite light absorbent is reduced, is advantageous to the preparation of large area perovskite solar cell.
Description
Technical field
The invention belongs to solar cell preparing technical field, and in particular to a kind of perovskite with phase separation structure is too
Positive energy battery and preparation method thereof.
Background technology
Perovskite solar cell is a kind of solar cell using hybrid inorganic-organic perovskite material as light-absorption layer,
Perovskite light absorbent has suitable extinction band gap, bipolarity carrier transport characteristic, longer carrier diffusion length etc.
Feature, excellent opto-electronic conversion performance is made it have, be expected to turn into the sun of a new generation efficiently, inexpensive, large area is all solid state
Can battery.
Perovskite solar cell generally use spin-coating method is successively prepared, and electricity is prepared by the method for spin coating and annealing
Sub- transport layer, perovskite light-absorption layer, hole transmission layer etc., layer of metal electrode is finally deposited and is used as to electrode.This method operates
Complexity, cost is high, and easily produces impurity in adjacent interlayer in preparation process, is unfavorable for next layer of attachment, while can draw
Enter complex centre, have a negative impact to the performance of battery.
The content of the invention
A kind of the defects of present invention exists for background technology, it is proposed that new perovskite sun with phase separation structure
Energy battery and preparation method thereof, handle to obtain the phase point of the light-absorption layer of perovskite solar cell and hole transmission layer by a step
Easy to operate from structure, cost is low, effectively prevent the generation of impurity between adjacent layer, reduces perovskite light absorbent
Complex centre, be advantageous to the preparation of large area perovskite solar cell.
Technical scheme is as follows：
A kind of perovskite solar cell with phase separation structure, including electrically conducting transparent substrate, be sequentially formed in it is transparent
Phase separation structure, the metal electrode of electron transfer layer, perovskite light-absorption layer and hole transmission layer on conductive substrates.
Further, the phase separation structure of the perovskite light-absorption layer and hole transmission layer is obtained using following steps：a.
The edge adhesive thickness of electron transfer layer on electrically conducting transparent substrate is formed at is 0.005~0.05 mm flexible thin
Film, to form region to be deposited；B. 10~50 μ L/cm are added dropwise on the region to be deposited that step a is obtained2Perovskite light-absorption layer
The mixed solution of material and hole mobile material；In the mixed solution concentration of perovskite extinction layer material be 0.2~
0.9mmol/mL, the concentration of hole mobile material is 10~55mg/mL；C. the electrically conducting transparent for having mixed solution is added dropwise in step b
Cover layer in substrate, makes film layer be brought into close contact with mixed solution, after standing 1~5min, be positioned over 90 on warm table~
15~60s is heated at a temperature of 240 DEG C, takes the film layer of covering off, then 10~30min is heated at 80~100 DEG C, obtains calcium titanium
The phase separation structure of ore deposit light-absorption layer and hole transmission layer.
A kind of preparation method of the perovskite solar cell with phase separation structure, comprises the following steps：
Step 1, electron transfer layer is prepared on substrate；
The flexibility that step 2, the edge adhesive thickness of the electron transfer layer obtained in step 1 are 0.005~0.05mm
Film, to form region to be deposited；
Step 3,10~50 μ L/cm are added dropwise on the region to be deposited that step 2 obtains2Perovskite extinction layer material and hole
The mixed solution of transmission material；The concentration of perovskite extinction layer material is 0.2~0.9mmol/mL in the mixed solution, empty
The concentration of hole transport materials is 10~55mg/mL；
Step 4, step 3 be added dropwise have cover layer on the substrate of mixed solution, make film layer close with mixed solution
Fitting, after standing 1~5min, 15~60s of heating at a temperature of 90~240 DEG C is positioned on warm table, takes the film of covering off
Layer, then 10~30min is heated at 80~100 DEG C, obtain the phase separation structure of perovskite light-absorption layer and hole transmission layer；
Metal electrode is prepared on the phase separation structure of step 5, the perovskite light-absorption layer obtained in step 4 and hole transmission layer
As to electrode, you can obtain the perovskite solar cell with phase separation structure.
Further, it can also be added before step 3 processing and the surface of the electron transfer layer after step 2 processing is changed
Property processing the step of；The method of the modification is UV-ozone, plasma, the thing of surface deposition change hydrophilic and hydrophobic
Matter or be soaked in change surface hydrophilic and hydrophobic solution in the methods of, it is described change surface hydrophilic and hydrophobic material be PEI (poly- second
Alkene imines), glycine, alanine, serine etc..
Further, substrate described in step 1 is FTO glass, ito glass, AZO (the ZnO transparent conductive glass of aluminium doping
Glass), the electrically conducting transparent substrate such as flexible ITO, PET (polyethylene terephthalate) or PEN (PEN).
Further, electron transport layer materials described in step 1 are TiO2、ZnO、SnO2Or Zn2SnO4Deng (former using ALD
Sublayer deposits), spin coating or be prepared the methods of Best-Effort request.
Further, mesoporous supporting layer, the mesoporous material of mesoporous supporting layer can be also prepared on electron transfer layer described in step 1
For TiO2、ZnO、SiO2、Al2O3、SiTiO3、ZrO2Or Zn2SnO4Deng.
Further, fexible film described in step 2 be polyimides (PI), polytetrafluoroethylene (PTFE) (PTFE), polyethylene (PE),
Polyvinyl chloride (PVC), polyethylene terephthalate (PET), polypropylene (PP) or polystyrene (PS) etc..
Further, the mixed solution described in step 3 is molten for the mixing of perovskite extinction layer material and hole mobile material
Liquid；Wherein, perovskite light-absorption layer materials chemistry formula is ABmX3-m, A=CH3NH3、C4H9NH3、 NH2=CHNH2Or Cs etc., B are
Pb, Sn etc., X Cl, Br, I etc.；Hole mobile material is Spiro-OMeTAD, PTAA (poly- [double (4- phenyl) (2,4,6- tri-
Aminomethyl phenyl) amine]), P3HT (poly- 3- hexyl thiophenes), PEDOT:PSS (poly- 3,4-rthylene dioxythiophene/poly styrene sulfonate)
Or NPB (N, N '-diphenyl-N, N '-two (1- naphthyls) -1,1 '-biphenyl -4,4 '-diamines) etc..
Further, the solvent of mixed solution described in step 3 be DMF (DMF), N, N- dimethyl second
In one kind in acid amides (DMA), dimethyl sulfoxide (DMSO) (DMSO), γ-fourth lactones (GBL), or chlorobenzene (CB) and above-mentioned solvent
A kind of mixed solvent, or toluene (TL) and a kind of mixed solvent in above-mentioned solvent.
Further, film layer described in step 4 is fexible film or ganoine thin film, and its thickness is 0.005~0.05 mm,
Material is polyimides (PI), polytetrafluoroethylene (PTFE) (PTFE), polyethylene (PE), polyvinyl chloride (PVC), poly terephthalic acid second two
Alcohol ester (PET), polypropylene (PP) or polystyrene (PS) etc..
Further, metal electrode described in step 5 is gold, silver, carbon or aluminium etc..
Beneficial effects of the present invention are：
Region to be deposited dropwise addition perovskite light absorbent and hole mobile material on the electron transport layer of the invention mixes
Solution is closed, extinction is realized by the difference of the hydrophilic-hydrophobic degree of two kinds of materials under the collective effect of fexible film and film layer
Layer and the separation of cavitation layer, and then the phase separation structure of perovskite light-absorption layer and hole transmission layer is obtained, easy to operate, cost
It is low, the generation of impurity between adjacent layer is effectively prevent, the complex centre of perovskite light absorbent is reduced, is advantageous to large area
The preparation of perovskite solar cell.
Brief description of the drawings
Fig. 1 is the structural representation of the perovskite solar cell provided by the invention with phase separation structure；From lower and
On be followed successively by phase separation structure 3, the metal of electrically conducting transparent substrate 1, electron transfer layer 2, perovskite light-absorption layer and hole transmission layer
Electrode 4, wherein, ● hole mobile material is represented,Represent perovskite light absorbent；
Fig. 2 is the preparation process of the phase separation structure of perovskite light-absorption layer of the present invention and hole transmission layer；Wherein, a is band
The electrically conducting transparent substrate of electron transfer layer, b is to adhere to fexible film in the edge of electron transfer layer, to form area to be deposited
Domain, c is the mixed solution that perovskite extinction layer material and hole mobile material are added dropwise in the region to be deposited of formation, and is covered
Film layer, d heat for the obtained device architectures of step c are positioned on warm table, and e is to be heated after the film layer of covering is taken off
The perovskite light-absorption layer and hole transmission layer phase separation structure of formation；
Fig. 3 is the enlarged drawing of step c in Fig. 2；
Fig. 4 is the I-V curve with phase separation structure perovskite solar cell that the embodiment of the present invention obtains；
Fig. 5 is FTO/TiO in the embodiment of the present invention2The section SEM shape appearance figures of/phase separation structure.
Embodiment
With reference to the accompanying drawings and examples, technical scheme is described in detail.
As shown in figure 1, the structural representation for the perovskite solar cell provided by the invention with phase separation structure；
The phase separation structure of electrically conducting transparent substrate 1, electron transfer layer 2, perovskite light-absorption layer and hole transmission layer is followed successively by from bottom to top
3rd, metal electrode 4.
Embodiment
A kind of preparation method of the perovskite solar cell with phase separation structure, specifically includes following steps：
Step 1, choose 1.95cm*1.95cm sizes FTO glass be used as substrate, successively using cleaning agent, KOH satisfy
With ethanol solution, deionized water, acetone, deionized water, ethanol, deionized water cleaning, dried up with nitrogen, then ultraviolet-smelly
It is stand-by that 30min is handled under oxygen；
Step 2,35uL 2M HCl added in 2.53mL ethanol, be well mixed, obtain solution A；By 369uL isopropyl oxygen
Base titanium is added in 2.53mL ethanol, is well mixed, is obtained solution B；During solution B stirs, solution A is slowly added dropwise
Into solution B, continue stirring 2 hours, the TiO clarified2Precursor liquid C；
The TiO that drop step 2 obtains in step 3, the FTO glass after step 1 processing2Precursor liquid C, then with 2000r's
After rotating speed rotation 50s, 15min is heated with 150 DEG C of temperature on warm table, finally anneal 30min at 500 DEG C, obtains
TiO2Electron transfer layer；
Step 4, by 276.6mg PbI2, 95.4mg CH3NH3I and 25mg spiro-OMeTAD adds 1mL N, N- bis-
In NMF (DMF), 12h is stirred, obtains solution D；
Step 5, the TiO obtained in step 32The edge of electron transfer layer stick wide 0.5cm, 0.05 mm of thickness it is poly-
Imide membrane, 15min is then handled under the conditions of UV-ozone, form region to be deposited；
Step 6, the region to be deposited dropwise addition 20uL solution Ds in step 5 formation, then thickness is 0.01mm in surface cover
Polyethylene film (PE), polyethylene film is brought into close contact with solution, stand 3min after, be positioned on warm table at 100 DEG C
At a temperature of heat 35s, take the polyethylene film of covering off by certain angle, then 20min is heated at 100 DEG C, obtain perovskite
The phase separation structure of light-absorption layer and hole transmission layer；
Step 7, the gold of the film surface evaporation 80nm thickness obtained in step 6 are as to electrode, you can have described in obtaining
The perovskite solar cell of phase separation structure.
Fig. 4 is the I-V curve for the perovskite solar cell that the embodiment of the present invention obtains；It is the calcium titanium for obtaining embodiment
Ore deposit solar cell is in AM1.5,100mW/cm2Xenon lamp under using three-electrode method test what is obtained, wherein, scanning voltage 0-
1.2V, sweep speed 100mV/s.As shown in Figure 4, the perovskite solar cell that the embodiment of the present invention obtains is in hole transport
Layer Spiro-OMeTAD obtains 3.12% efficiency in the case of undoping；Wherein, short circuit current 5.88mA/cm2, open
Road voltage is 0.79V, fill factor, curve factor 0.67.
Fig. 5 is FTO/TiO in the embodiment of the present invention2The section SEM shape appearance figures of/phase separation structure；From Fig. 5, implement
Perovskite light-absorption layer and the thickness of the phase separation structure of hole transmission layer prepared by example is for 290nm or so, and wherein the superiors are about
80nm continuous unsetting layer is rich in spiro-OMeTAD material areas, with sizing grains for rich in perovskite under it
Material area, it is only 1/3rd of calcium titanium ore bed thickness prepared by common successively method rich in perovskite material area thickness.
Claims (10)
1. a kind of perovskite solar cell with phase separation structure, including electrically conducting transparent substrate, it is sequentially formed in transparent lead
Phase separation structure, the metal electrode of electron transfer layer, perovskite light-absorption layer and hole transmission layer on electric substrate.
2. the perovskite solar cell according to claim 1 with phase separation structure, it is characterised in that the calcium titanium
The phase separation structure of ore deposit light-absorption layer and hole transmission layer is obtained using following steps：A. the electricity on electrically conducting transparent substrate is formed at
The edge adhesive thickness of sub- transport layer is 0.005~0.05mm fexible film, to form region to be deposited；B. in step
10~50 μ L/cm are added dropwise on the region to be deposited that a is obtained2The mixed solution of perovskite extinction layer material and hole mobile material；
The concentration of perovskite extinction layer material is 0.2~0.9mmol/mL in the mixed solution, and the concentration of hole mobile material is 10
~55mg/mL；C. being added dropwise in step b has cover layer in the electrically conducting transparent substrate of mixed solution, after standing 1~5min, puts
15~60s of heating at a temperature of 90~240 DEG C is placed on warm table, takes the film layer of covering off, then 10 are heated at 80~100 DEG C
~30min, obtain the phase separation structure of perovskite light-absorption layer and hole transmission layer.
3. a kind of preparation method of the perovskite solar cell with phase separation structure, comprises the following steps：
Step 1, electron transfer layer is prepared on substrate；
The fexible film that step 2, the edge adhesive thickness of the electron transfer layer obtained in step 1 are 0.005~0.05mm,
To form region to be deposited；
Step 3,10~50 μ L/cm are added dropwise on the region to be deposited that step 2 obtains2Perovskite extinction layer material and hole transport
The mixed solution of material；The concentration of perovskite extinction layer material is 0.2~0.9mmol/mL in the mixed solution, hole transport
The concentration of material is 10~55mg/mL；
Step 4, it is added dropwise in step 3 and has a cover layer on the substrate of mixed solution, after standing 1~5min, is positioned over warm table
On 15~60s is heated at a temperature of 90~240 DEG C, take the film layer of covering off, then 10~30min is heated at 80~100 DEG C,
Obtain the phase separation structure of perovskite light-absorption layer and hole transmission layer；
Metal electrode conduct is prepared on the phase separation structure of step 5, the perovskite light-absorption layer obtained in step 4 and hole transmission layer
To electrode, you can obtain the perovskite solar cell with phase separation structure.
4. the preparation method of the perovskite solar cell according to claim 3 with phase separation structure, its feature exist
In the step of being modified processing to the surface of the electron transfer layer after step 2 processing is added in step 3 processing before.
5. the preparation method of the perovskite solar cell according to claim 3 with phase separation structure, its feature exist
In substrate described in step 1 is FTO glass, ito glass, AZO, flexible ITO, PET or PEN.
6. the preparation method of the perovskite solar cell according to claim 3 with phase separation structure, its feature exist
In electron transport layer materials described in step 1 are TiO2、ZnO、SnO2Or Zn2SnO4, carried using ald, spin coating or dipping
Pulling method is prepared；It is TiO that material can be also prepared on the electron transfer layer2、ZnO、SiO2、Al2O3、SiTiO3、ZrO2Or
Zn2SnO4Mesoporous supporting layer.
7. the preparation method of the perovskite solar cell according to claim 3 with phase separation structure, its feature exist
In fexible film described in step 2 is polyimides, polytetrafluoroethylene (PTFE), polyethylene, polyvinyl chloride, polyethylene terephthalate
Ester, polypropylene or polystyrene.
8. the preparation method of the perovskite solar cell according to claim 3 with phase separation structure, its feature exist
In the mixed solution described in step 3 is perovskite extinction layer material and the mixed solution of hole mobile material；Wherein, perovskite
Light-absorption layer materials chemistry formula is ABmX3-m, A=CH3NH3、C4H9NH3、NH2=CHNH2Or Cs, B are Pb or Sn, X Cl, Br, I；
Hole mobile material is Spiro-OMeTAD, PTAA, P3HT, PEDOT:PSS or NPB.
9. the preparation method of the perovskite solar cell according to claim 3 with phase separation structure, its feature exist
In the solvent of, mixed solution described in step 3 be DMF, DMA, dimethyl sulfoxide (DMSO), γ-
One kind in fourth lactones, either a kind of mixed solvent in chlorobenzene and above-mentioned solvent or toluene and one in above-mentioned solvent
The mixed solvent of kind.
10. the preparation method of the perovskite solar cell according to claim 3 with phase separation structure, its feature exist
Be fexible film or ganoine thin film in, film layer described in step 4, its thickness is 0.005~0.05mm, material be polyimides,
Polytetrafluoroethylene (PTFE), polyethylene, polyvinyl chloride, polyethylene terephthalate, polypropylene or polystyrene.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108321298A (en) * | 2018-02-12 | 2018-07-24 | 西北工业大学 | A kind of high efficiency planar heterojunction perovskite thin film solar cell and preparation method |
| CN110395859A (en) * | 2019-07-24 | 2019-11-01 | 西安理工大学 | A kind of anode material and preparation method suitable for electrochemistry Treatment of Sludge |
| CN113517405A (en) * | 2021-07-09 | 2021-10-19 | 广西大学 | High-performance self-powered perovskite type photoelectric detector based on CsI ion doped hole transport layer and preparation method thereof |
| CN116728387A (en) * | 2023-08-14 | 2023-09-12 | 之江实验室 | Self-powered miniature soft robot based on photovoltaic and piezoelectric materials |
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| CN104124295A (en) * | 2014-08-12 | 2014-10-29 | 中国乐凯集团有限公司 | Planar heterogeneous perovskite solar cell and preparation method thereof |
| CN105967172A (en) * | 2016-05-06 | 2016-09-28 | 电子科技大学 | Preparation method of foldable graphene thin film of large area |
| US20170194103A1 (en) * | 2015-11-16 | 2017-07-06 | Pusan National University Industry-University Cooperation Foundation | Novel triphenylamine derivatives and photovoltaic device including the same |
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| CN104124295A (en) * | 2014-08-12 | 2014-10-29 | 中国乐凯集团有限公司 | Planar heterogeneous perovskite solar cell and preparation method thereof |
| US20170194103A1 (en) * | 2015-11-16 | 2017-07-06 | Pusan National University Industry-University Cooperation Foundation | Novel triphenylamine derivatives and photovoltaic device including the same |
| CN105967172A (en) * | 2016-05-06 | 2016-09-28 | 电子科技大学 | Preparation method of foldable graphene thin film of large area |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108321298A (en) * | 2018-02-12 | 2018-07-24 | 西北工业大学 | A kind of high efficiency planar heterojunction perovskite thin film solar cell and preparation method |
| CN110395859A (en) * | 2019-07-24 | 2019-11-01 | 西安理工大学 | A kind of anode material and preparation method suitable for electrochemistry Treatment of Sludge |
| CN110395859B (en) * | 2019-07-24 | 2022-01-07 | 西安理工大学 | Anode material suitable for electrochemical sludge treatment and preparation method thereof |
| CN113517405A (en) * | 2021-07-09 | 2021-10-19 | 广西大学 | High-performance self-powered perovskite type photoelectric detector based on CsI ion doped hole transport layer and preparation method thereof |
| CN113517405B (en) * | 2021-07-09 | 2023-04-18 | 广西大学 | High-performance self-powered perovskite type photoelectric detector based on CsI ion doped hole transport layer and preparation method thereof |
| CN116728387A (en) * | 2023-08-14 | 2023-09-12 | 之江实验室 | Self-powered miniature soft robot based on photovoltaic and piezoelectric materials |
| CN116728387B (en) * | 2023-08-14 | 2023-12-19 | 之江实验室 | Self-powered miniature soft robot based on photovoltaic and piezoelectric materials |
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