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CN108400249A - A kind of perovskite solar cell and preparation method thereof based on high transparency conductive nickel acid lanthanum hole transmission layer - Google Patents

A kind of perovskite solar cell and preparation method thereof based on high transparency conductive nickel acid lanthanum hole transmission layer Download PDF

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Publication number
CN108400249A
CN108400249A CN201810187406.3A CN201810187406A CN108400249A CN 108400249 A CN108400249 A CN 108400249A CN 201810187406 A CN201810187406 A CN 201810187406A CN 108400249 A CN108400249 A CN 108400249A
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layer
lanio
hole transmission
solar cell
transmission layer
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CN108400249B (en
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陈炜
张艳君
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Huazhong University of Science and Technology
Ezhou Institute of Industrial Technology Huazhong University of Science and Technology
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Huazhong University of Science and Technology
Ezhou Institute of Industrial Technology Huazhong University of Science and Technology
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14Carrier transporting layers
    • H10K50/15Hole transporting layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00Constructional details relating to the organic devices covered by this subclass
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
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  • Manufacturing & Machinery (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The invention discloses one kind being based on high transparency conduction LaNiO3Trans- planar structure perovskite solar cell of hole transmission layer and preparation method thereof.Trans- planar structure perovskite solar cell of the present invention includes transparent conductive substrate, hole transmission layer, perovskite light-absorption layer, electron transfer layer, interface-modifying layer, metal electrode.The trans- planar structure perovskite solar cell has good conductivity, high optical transmittance and higher work function, and by LaNiO3Conductive film can be to avoid perovskite light-absorption layer with transparent electrode as hole transmission layer contact, prevent the compound of interface carrier.

Description

A kind of perovskite solar cell based on high transparency conductive nickel acid lanthanum hole transmission layer And preparation method thereof
Technical field
The invention discloses one kind being based on high transparency conduction LaNiO3The perovskite solar cell of hole transmission layer and its Preparation method belongs to new material area of solar cell.
Background technology
With the development of the social economy, the mankind are continuously increased the use demand of the energy, but the fossil energies such as oil, coal Because exhaustive exploitation and energy pollution have been used limitation, the exploitation of new energy to become very urgent.Solar energy is as one The reproducible clean energy resource of kind, inexhaustible, solar cell is a kind of device for converting light energy into electric energy, Therefore, development solar cell is the important trend of new energy.
Perovskite material is because it is with narrow band gap, strong light absorption, high carrier mobility, small exciton bind energy, system The features such as standby simple for process and of low cost, attract the very big concern of researcher, develops rapidly perovskite solar energy in recent years Battery, photoelectric conversion efficiency have reached authentication efficiency 22.7%, become the research hotspot of solar cell of new generation.
Typical perovskite solar cell includes meso-hole structure and planar structure, calcium titanium ore bed be both light absorbing layer and It is electron hole transport layer, the electron hole of generation is transmitted separately to transparent conductive electrode and metal electrode.In trans- planar junction In structure perovskite solar cell, when not adding hole transmission layer, transparent conductive electrode and perovskite light-absorption layer energy level are not Match, interface carrier is compound serious.Currently, common hole transport layer material can be divided into three classes:Inorganic, polymerization species and Small molecule class.Polymerizeing species hole mobile material has the dissolubility of difference and uncertain molecular weight, small molecule class hole transport Material has synthesis step long, to ultraviolet unstability, limits its development.Inorganic hole transporter has higher sky Cave mobility, good stability become good hole mobile material.
Invention content
In state natural sciences fund (51672094,51661135023), state key development project Under the support energetically of (2016YFC0205002) and Central China University of Science and Technology's autonomous innovation research foundation (2016JCTD111), this hair The bright one kind that provides is based on high transparency conductive nickel acid lanthanum (LaNiO3) hole transmission layer perovskite solar cell and its preparation Method, it is intended to not solve trans- planar structure perovskite solar cell transparent conductive electrode and perovskite light-absorption layer energy level not Match, the problem of interface carrier is compound serious and device inside ohmic loss.
An aspect of of the present present invention is related to a kind of based on high transparency conduction LaNiO3The perovskite solar-electricity of hole transmission layer Pond, it is characterised in that:The perovskite solar cell includes successively:Transparent conductive substrate, hole transmission layer, perovskite extinction Layer, electron transfer layer, interface-modifying layer, metal electrode, wherein the hole transmission layer is LaNiO3Conductive film.
Another aspect of the present invention relates to one kind being based on high transparency conduction LaNiO3The perovskite solar energy of hole transmission layer The preparation method of battery, it is characterised in that:This approach includes the following steps:
(1) hole transmission layer is prepared in transparent conductive substrate;
(2) perovskite light-absorption layer is prepared on the hole transport layer;
(3) electron transfer layer is prepared on the perovskite light-absorption layer;
(4) interface-modifying layer is prepared on the electron transport layer;
(5) metal electrode is prepared on the interface-modifying layer;
Wherein, the hole transmission layer described in step (1) is LaNiO3Conductive film.
The detailed description of the invention
Term " transparent conductive substrate " used in the present invention is the transparent electrode using transparent material as substrate.The substrate Select the transparent materials such as glass, flexiplast;Transparent electrode is located on the inner surface of the substrate, common transparent electrode material Can be fluorine tin-oxide (FTO), indium tin oxide (ITO) or new oxide of aluminium (AZO) etc..
Term " hole transmission layer " used in the present invention is collected comes from perovskite absorbed layer injected holes with transmission, and Play the role of stopping electronics.
Term " perovskite light-absorption layer " used in the present invention can generate electricity by the energy of photon in absorption sunlight Son-hole pair, and respectively by electronics, hole transport to corresponding electronics or hole transmission layer.
Term " electron transfer layer " used in the present invention is for collecting and transmitting the electricity injected from perovskite absorbed layer Son, and play the role of stopping hole.
Term " interface-modifying layer " used in the present invention can transmit electronics, stop hole.By increasing modifying interface Layer can form Ohmic contact in interface between electrode, improve the efficiency of the transmission and metal electrode collection electronics of electronics.
In certain specific embodiments of the present invention, transparent conductive substrate used in the present invention is selected from FTO conduction glass Glass, ITO electro-conductive glass or AZO electro-conductive glass.
In certain specific embodiments of the present invention, perovskite light-absorption layer used in the present invention is ABX3, A= CH3NH3 +、CH(NH2)2 +、Cs+Or mixtures thereof;B=Pb2+、Sn2+Or mixtures thereof;X=Cl-、Br-、I-Or mixtures thereof.
In certain specific embodiments of the present invention, electron transfer layer used in the present invention is C60、C70Or fullerene Derivative PC61CM、PC71BM。
In certain specific embodiments of the present invention, interface-modifying layer used in the present invention is LiF, 2,9- diformazans Base -4,7- diphenyl -1,10- ferrosins (hereinafter referred to as " BCP "), TiOx
In certain specific embodiments of the present invention, metal electrode used in the present invention is Ag, Al.
It is of the present invention to be based on high transparency conduction LaNiO3The preparation method of the perovskite solar cell of hole transmission layer, It includes:
(1) hole transmission layer is prepared in transparent conductive substrate;
(2) perovskite light-absorption layer is prepared on the hole transport layer;
(3) electron transfer layer is prepared on the perovskite light-absorption layer;
(4) interface-modifying layer is prepared on the electron transport layer;
(5) metal electrode is prepared on the interface-modifying layer.
Wherein, the hole transmission layer described in step (1) is LaNiO3Conductive film.
It is prepared in the present invention described based on high transparency conduction LaNiO3Certain of the perovskite solar cell of hole transmission layer In a little specific embodiments, in step (1) using glass cleaner, deionized water, industrial alcohol, absolute ethyl alcohol, acetone according to Secondary cleaning transparent conductive substrate, is respectively ultrasonically treated 20min, and nitrogen drying uses;La (the NO3)3·6H2O and NiN2O6· 6H2The molar ratio of O is 1:1;Prepare the LaNiO that molar concentration is 0.01-0.1mol/L3Precursor solution is spin-coated to transparent Above conductive substrates, rotating speed is 3000-5000 revolutions per seconds, about 30 seconds time;400-900 DEG C of heating plate is annealed 0.5-6 hours, cold But to room temperature.
It is prepared in the present invention described based on high transparency conduction LaNiO3Certain of the perovskite solar cell of hole transmission layer In a little specific embodiments, the perovskite precursor A PbX that molar concentration is 1-2mol/L is prepared in step (2)3Solution, will It is spin-coated on LaNiO3On hole transmission layer, rotating speed is 4000-6000 revolutions per seconds, 30 seconds time;70-300 DEG C of heating plate annealing 5- 120min is cooled to room temperature.
It is prepared in the present invention described based on high transparency conduction LaNiO3Certain of the perovskite solar cell of hole transmission layer In a little specific embodiments, the PCBM solution of 5-30mg/ml is prepared in step (3), is spin-coated on perovskite light-absorption layer, Rotating speed is 1000-3000 revolutions per seconds, 30 seconds time;70 DEG C of heating plates annealing 5-60min, are cooled to room temperature.
It is prepared in the present invention described based on high transparency conduction LaNiO3Certain of the perovskite solar cell of hole transmission layer In a little specific embodiments, BCP saturated solutions are prepared in step (4), on the electron transport layer by its spin coating, rotating speed is 4000-6000 revolutions per seconds, 30 seconds time;70 DEG C of heating plates annealing 5-60min, are cooled to room temperature.
It is prepared in the present invention described based on high transparency conduction LaNiO3Certain of the perovskite solar cell of hole transmission layer In a little specific embodiments, in step (5), by Ag or Al thermal evaporation depositions to BCP interface-modifying layers, deposition rate is 0.05-1 angstroms per seconds, deposition thickness 60-300nm, area 0.09-10cm2
Description of the drawings
Fig. 1 is trans- planar structure perovskite solar battery structure schematic diagram of the present invention;Wherein, it 1 is led to be transparent Electric substrate, 2 be hole transmission layer, 3 be perovskite light-absorption layer, 4 be electron transfer layer, 5 be interface-modifying layer, 6 be metal electrode.
Fig. 2 is the LaNiO of the embodiment of the present invention3The X-ray diffractogram of film.
Fig. 3 is the LaNiO of the embodiment of the present invention3The ultraviolet photoelectron spectroscopy figure of film.
Fig. 4 is the scanning electron microscope (SEM) photograph of FTO electro-conductive glass of the present invention.
Fig. 5 is the LaNiO on FTO electro-conductive glass of the present invention3The scanning electron microscope (SEM) photograph of film.
Fig. 6 is that whether there is or not LaNiO on FTO electro-conductive glass of the present invention3The UV-Visible absorption curve comparison of film Figure.
Fig. 7 is that whether there is or not LaNiO on the FTO electro-conductive glass of the present invention3The photoelectric current of film-voltage tester curve comparison figure.
Embodiment
In order to better understand the above technical scheme, in conjunction with appended figures and specific embodiments to upper Technical solution is stated to be described in detail.
Shown in reagent and raw material following article table 1 used in the present invention:
1 reagent used in the present invention of table and raw material
Instrument
Magnetic stirring apparatus (MR Hei-standard, German Heidolph companies)
Titanium-base warm table (PZ28-3TD, German Harry gestigkeit company)
Spin coating instrument (KW-4A, Chinese Academy of Sciences Microelectronics Institute)
Vacuum thermal evaporation equipment (RV 10, German IKA companies)
A kind of preparation method of perovskite solar cell of the present invention includes:
S1:FTO electro-conductive glass is cleaned successively using glass cleaner, deionized water, industrial alcohol, absolute ethyl alcohol, acetone, Each to be ultrasonically treated 20min, nitrogen drying uses.
S2:LaNiO is prepared on FTO electro-conductive glass3Layer
La(NO3)3·6H2O and NiN2O6·6H2O is as solute, according to 1:1 molar ratio, with the molar concentration of La 0.05mol/L, which is dissolved in ethylene glycol monomethyl ether solution, is used as precursor solution.By LaNiO3Precursor solution is spin-coated to transparent lead Above electric substrate, rotating speed is 2000 revolutions per seconds, 30 seconds time;600 DEG C of heating plates are annealed 0.5 hour, cooled to room temperature.
S3:Perovskite light-absorption layer is prepared on LaNiO3 layers
It is 1 by molar ratio:1 PbI2Powder and CH3NH3I powder mixed dissolution is in volume ratio DMF:DMSO=4:1 it is mixed It closes in solution, and stirring obtains the CH that Pb molar concentrations are 1.5mol/L to dissolving at 30 DEG C3NH3PbI3Solution.It will be above-mentioned Perovskite precursor solution is spin-coated on LaNiO3On hole transmission layer, rotating speed is 6000 revolutions per seconds, 30 seconds time;100 DEG C of heating plates Anneal 10min, cooled to room temperature.
S4:Electron transfer layer is prepared on perovskite light-absorption layer
It weighs a certain amount of PCBM to incorporate in chlorobenzene, is configured to the solution of 20mg/ml, 45 liquid are stirred to dissolving, will be prepared PCBM solution be spin-coated on perovskite light-absorption layer, rotating speed be 1500 revolutions per seconds, 30 seconds time;Heating plate annealing 10min when 70, Cooled to room temperature.
S5:Interface-modifying layer is prepared on the electron transport layer
BCP is incorporated in methanol, saturated solution is configured to, the BCP saturated solutions of preparation is spin-coated on PCBM electron-transports On layer, rotating speed is 6000 revolutions per seconds, 30 seconds time;Heating plate annealing 10min, cooled to room temperature when 70.
S6:Metal electrode is prepared on interface-modifying layer
Thermal evaporation apparatus pressure is evacuated to 5*10-4After Pa, evaporation power supply is opened, Ag thermal evaporation depositions to the interfaces BCP are repaiied It adorns on layer, deposition rate is 0.1 angstroms per second, deposition thickness 80nm, area 0.09cm2
LaNiO3The characterization of film
The present invention is using PANalytical B.V.X- diffractometers to LaNiO of the present invention3Film carries out X-ray and spreads out Analysis test is penetrated, XRD diffraction patterns are obtained, as shown in Fig. 2, 32.1 °, 47.1 ° and 58.5 °, corresponding is LaNiO respectively3Crystal (110), the characteristic peak position of (200) and (211) crystal face illustrates that the film prepared is LaNiO3Crystal.
Using Ecopia HMS-3000 Hall effect testers to LaNiO of the present invention3Film is tested, and is surveyed The results are shown in Table 2 for amount, illustrates LaNiO3Film has good conductivity, is 3.827 × 102S/cm can be effectively reduced The internal resistance of cell loses.
2. LaNiO of the present invention of table3The Hall effect test result of film
Using KratosAXIS-ULTRA DLD-600W photoelectron spectrographs to LaNiO of the present invention3Film carries out purple Outer photoelectron spectroscopy test, for measurement result as shown in figure 3, the combination of relatively low cut-off can be 0.41eV, corresponding is top of valence band Combination to the distance of fermi level, higher cut-off can be 16.48eV, and the combination of higher position cut-off is subtracted with 21.21eV to be obtained To be LaNiO3Work function WF be 4.73eV.Illustrate LaNiO3Hole transmission layer has higher work function, prepares transparent Electro-conductive glass can improve the work function of electrode, promote the collection in hole, to improve the energy conversion efficiency of device;Simultaneously LaNiO3Hole transmission layer can be to avoid perovskite light-absorption layer with transparent electrode contact, prevent the compound of interface carrier.
LaNiO is prepared on FTO electro-conductive glass using 200 scanning electron microscope observables of FEI Sirion3Comparison before and after layer Figure, as shown in Figure 4 and Figure 5, illustrates LaNiO3Film uniform fold is on FTO electro-conductive glass.
Using PerkinElmerlambda 950UV/Vis/NIR on FTO electro-conductive glass with/without LaNiO3Film carries out Uv-visible absorption spectrum is tested, and UV-Visible absorption curve comparison figure is obtained, as shown in fig. 6, the comparison diagram explanation LaNiO3Film has high optical transmittance, and film absorptivity is only 2%, reduces optical absorption loss.
The efficiency test system formed using solar simulator and 2400 digital sourcemeters of Keithley is right at room temperature With/without LaNiO on FTO electro-conductive glass3Film measures.Measurement result is as shown in fig. 7, obtain with LaNiO3It is passed as hole The photovoltaic parameter of the perovskite solar cell of defeated layer is short circuit current 20.7mA/cm2, open-circuit voltage 1.06V, fill factor 79.3, energy conversion efficiency 17.4, performance is apparently higher than no LaNiO3Perovskite solar cell as hole transmission layer.
Although preferred embodiments of the present invention have been described, it is created once a person skilled in the art knows basic Property concept, then additional changes and modifications may be made to these embodiments.So it includes excellent that the following claims are intended to be interpreted as It selects embodiment and falls into all change and modification of the scope of the invention.Obviously, those skilled in the art can be to the present invention Carry out various modification and variations without departing from the spirit and scope of the present invention.If in this way, these modifications and changes of the present invention Within the scope of the claims of the present invention and its equivalent technology, then the present invention is also intended to exist comprising these modification and variations It is interior.

Claims (10)

1. one kind being based on high transparency conduction LaNiO3The perovskite solar cell of hole transmission layer, it is characterised in that:The calcium titanium Mine solar cell includes successively:Transparent conductive substrate, hole transmission layer, perovskite light-absorption layer, electron transfer layer, modifying interface Layer, metal electrode, wherein the hole transmission layer is LaNiO3Conductive film.
2. being based on high transparency conduction LaNiO as described in claim 13The perovskite solar cell of hole transmission layer, feature exist In:The transparent conductive substrate is selected from FTO electro-conductive glass, ITO electro-conductive glass or AZO electro-conductive glass.
3. being based on high transparency conduction LaNiO as described in claim 13The perovskite solar cell of hole transmission layer, feature exist In:The perovskite light-absorption layer is ABX3, A=CH3NH3 +、CH(NH2)2 +、Cs+Or mixtures thereof;B=Pb2+、Sn2+Or its mixing Object;X=Cl-、Br-、I-Or mixtures thereof.
4. being based on high transparency conduction LaNiO as described in claim 13The perovskite solar cell of hole transmission layer, feature exist In:The electron transfer layer is C60、C70Or fullerene derivate PC61CM、PC71BM。
5. being based on high transparency conduction LaNiO as described in claim 13The perovskite solar cell of hole transmission layer, feature exist In:The interface-modifying layer is LiF, 2,9- dimethyl -4,7- diphenyl -1,10- ferrosins, TiOx
6. being based on high transparency conduction LaNiO as described in claim 13The perovskite solar cell of hole transmission layer, feature exist In:The metal electrode is Ag, Al.
7. claim 1-6 is any described based on high transparency conduction LaNiO3The system of the perovskite solar cell of hole transmission layer Preparation Method includes the following steps:
(1) hole transmission layer is prepared in transparent conductive substrate;
(2) perovskite light-absorption layer is prepared on the hole transport layer;
(3) electron transfer layer is prepared on the perovskite light-absorption layer;
(4) interface-modifying layer is prepared on the electron transport layer;
(5) metal electrode is prepared on the interface-modifying layer.
Wherein, the hole transmission layer described in step (1) is LaNiO3Conductive film.
8. preparation method as claimed in claim 7, which is characterized in that in step (1), preparation molar concentration is 0.01- The LaNiO of 0.1mol/L3Precursor solution is spin-coated to above transparent conductive substrate, and rotating speed is 3000-5000 revolutions per seconds, 400-900 DEG C of heating plate is annealed 0.5-6 hours.
9. preparation method as claimed in claim 7, which is characterized in that it is 1-2mol/L to prepare molar concentration in step (2) Perovskite precursor A PbX3Solution is spin-coated on LaNiO3On hole transmission layer, rotating speed is 4000-6000 revolutions per seconds, time 30 seconds;70-300 DEG C of heating plate annealing 5-120min, is cooled to room temperature.
10. preparation method as claimed in claim 7, which is characterized in that the PCBM for preparing 5-30mg/ml in step (3) is molten Liquid is spin-coated on perovskite light-absorption layer, and rotating speed is 1000-3000 revolutions per seconds, 30 seconds time;70 DEG C of heating plates annealing 5- 60min is cooled to room temperature.
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CN113206198A (en) * 2021-04-19 2021-08-03 武汉大学 Preparation method of lanthanum nickelate nanoparticle hole transport layer, trans-perovskite solar cell and preparation method of trans-perovskite solar cell
CN116284783A (en) * 2023-04-06 2023-06-23 华中科技大学 Perovskite solar cell based on multifunctional copolymer/metal composite electrode and preparation method thereof
CN116284783B (en) * 2023-04-06 2024-05-03 华中科技大学 Perovskite solar cell based on multifunctional copolymer/metal composite electrode and preparation method thereof

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