CN114447228A - Perovskite solar cell with microcavity structure and preparation method thereof - Google Patents

Perovskite solar cell with microcavity structure and preparation method thereof Download PDF

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CN114447228A
CN114447228A CN202210106786.XA CN202210106786A CN114447228A CN 114447228 A CN114447228 A CN 114447228A CN 202210106786 A CN202210106786 A CN 202210106786A CN 114447228 A CN114447228 A CN 114447228A
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layer
perovskite
solar cell
metal layer
microcavity
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邵宇川
丁国育
郑毅帆
郭鑫
史亦沣
李清源
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Shanghai Institute of Optics and Fine Mechanics of CAS
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/87—Light-trapping means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
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Abstract

The invention discloses a preparation method of a perovskite solar cell microcavity, which comprises the following steps of forming a microcavity by a first metal layer, a middle perovskite medium, a first charge transmission layer, a second charge transmission layer and a second metal layer which are arranged above an ITO glass substrate; the method for preparing the perovskite solar cell microcavity has wide universality, and can grow a high-quality perovskite dielectric film above the metal layer to obtain a resonant cavity working aiming at the absorption edge. The perovskite solar cell with the microcavity prepared by the method is enhanced by modulating the optical field of long wave, the current is obviously improved, and the toxicity of the perovskite solar cell can be greatly reduced.

Description

Perovskite solar cell with microcavity structure and preparation method thereof
Technical Field
The invention relates to the technical field of perovskite solar cells, in particular to a perovskite solar cell with a microcavity structure and a preparation method thereof.
Background
Perovskite Solar Cells (PSC) are a new solar cell technology developed in recent years, and lead-halogen perovskite materials mixed with organic and inorganic materials are adopted as light absorption layers, and lead-halogen perovskite materials have the characteristics of flexible components, adjustable band gap, high light absorption, long carrier diffusion distance, high carrier transmission rate and the like, so that the PSC attracts extensive attention of researchers in the field of photoelectrons. The band gap of the solar cell can be continuously adjusted from 1.2-2.9 eV according to different components, and the solar cell has great potential in the field of solar cells.
However, it is currently difficult for high efficiency perovskite solar cells to avoid the use of lead-containing raw materials, and one of the main rational ways of attenuation is physical lead reduction, i.e. reduction of the thickness of the lead-containing perovskite light absorbing layer. The thickness of a traditional perovskite light absorption layer is 700-1000 nm, and theoretical calculation proves that the thickness of the perovskite light absorption layer can reach more than 80% of efficiency of a standard device only by 200nm at least, and toxicity is reduced by 50% at least. However, since the absorption coefficient of perovskite is very high at short wavelength and low at long wavelength, the energy of long-wave part (>700nm) is not utilized by directly reducing the thickness of perovskite light absorption layer through concentration regulation and anti-solvent time regulation, so that the efficiency of the device is difficult to further improve. In the mature thin-film solar cells (gallium arsenide cells, copper indium gallium selenide cells and the like), an effective method for solving the problems is to make micro-cavities in the solar cells and improve the absorption of long waves by regulating and controlling the light field. However, for perovskite solar cells, due to the characteristics of solution-based fabrication, the quality of coating the perovskite light absorption layer on the metal layer is limited by the interfacial properties, and it is also a minor challenge to fabricate dielectric layers of a certain thickness.
Disclosure of Invention
The invention aims to solve the problems that: how to stably obtain the perovskite solar cell with the microcavity structure, how to improve the growth quality of the medium in the microcavity, so as to realize the light field regulation and control and further realize the enhancement of light absorption.
In order to solve the problems, the technical scheme of the invention is as follows:
in one aspect, the invention provides a perovskite solar cell with a microcavity structure, which comprises a substrate, a transparent conducting layer, a first charge transport layer, a perovskite light absorption layer, a second charge transport layer and a second metal layer which are sequentially stacked; the light-emitting diode is characterized in that a first metal layer is arranged between the transparent conducting layer and the first charge transmission layer, the first metal layer is used as a microcavity light-in end, and the second metal layer is used as a microcavity light-out end.
Preferably, the transparent conducting layer is made of one of Indium Tin Oxide (ITO) or fluorine-doped tin oxide (FTO), and the thickness of the transparent conducting layer is 100-600 nm.
Preferably, the first metal layer is a metal material with high reflectivity and conductivity, and is one of gold Au, silver Ag and copper Cu, and the thickness of the first metal layer is 5-15 nm.
Preferably, the heat treatment temperature in the step (1) is 80-120 ℃, and the time is 1-5 min; and (3) performing heat treatment on the precursor of the first charge transport layer in the step (2) at the temperature of 30-50 ℃.
Preferably, the time interval between the completion of the heat treatment in the step (2) and the preparation of the first charge transport layer is 0 to 3 seconds.
Preferably, the first charge transport layer and the second charge transport layer should have transport characteristics of different charges, wherein the electron transport material includes: using titanium dioxide TiO2SnO, tin dioxide2Zinc oxide ZnO, C60Solution, [6,6 ]]-phenyl radical C61Any one of methyl butyrate solutions with the thickness of 20-120 nm; the hole transport material adopts triphenylamine derivative and 2,2,7, 7-tetra [ N, N-di (4-methoxyphenyl) amino]9, 9-spirobifluorene Spiro-OMeTAD, poly-3, 4-ethylenedioxythiophene, polystyrene sulfonate PEDOT PSS, poly (3-hexylthiophene) P3HT, 2,3,5, 6-tetrafluoro-7, 7,8, 8-tetracyanodimethane-doped polytriazoloylamines PTAA: F4-TCNQ, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine]PTAA, cuprous thiocyanate CuSCN, nickel oxide NiOxAny one of them, the thickness is 10 to 200 nm.
Preferably, ABX is used as the perovskite light absorption layer3Type three-dimensional perovskite of formula ABX3The different ions in (1) are selected as follows: positive monovalent cationA, methylamine MA is selected+Formamidine FA+Potassium, K+Rb, Rb+Cesium Cs+Any one kind of ion and any combination of several kinds of ions; a positive divalent metal cation B selected from lead Pb2+Germanium Ge2+Sn, Sn2+Any one kind of ion and any combination of several kinds of ions; a monovalent anion X selected from chlorine Cl-Bromine Br-Iodine I-Any one kind of ion and any combination of several kinds of ions.
Preferably, the perovskite light absorption layer adopts two-dimensional perovskite in the material, and the molecular formula of the two-dimensional perovskite is L2An-1BnX3n+1Or L2An-1BnX3n+1The different ions in (1) are selected as follows: the three ions of positive univalent cation A, positive divalent metal cation B and negative univalent anion X are selected as the three-dimensional perovskite; monovalent organic cation A1Selecting phenylethylamine PEA+Butylamine BA+Ethylamine EA+Dimethylamine DMA+Methyltriethylammonium MTEA+Guanidine GA+2-Thienylmethylammonium ThMA+Any one kind of ion and any combination of several kinds of ions; a divalent organic cation A23-aminomethyl piperidine 3AMP is selected2+4-Aminomethylpiperidine 4AMP2+3-aminomethylpyridine 3AMPY2+4-aminomethylpyridine 4AMPY2+EDA, ethylenediamine2+DPA of N, N-dimethylaniline2+Propane 1, 3-diammonium PDA 2+1, 4-butanediamine BDA 2+2, 5-diaminomethylthiophene ThDMA2+P-xylylenediamine PDMA2+N, N-dimethylethylenediamine DMDEA2+Any one kind of ion and any combination of several kinds of ions.
Preferably, the second metal layer is one of gold Au, silver Ag and copper Cu, and has a thickness of 90-300 nm.
On the other hand, the invention also provides a preparation method of the perovskite solar cell with the microcavity structure, which comprises the following steps:
(1) preparing a first metal layer on the transparent conducting layer to be used as a light-entering end of the microcavity, and carrying out heat treatment to enable the first metal layer and the transparent conducting layer to be in a micro-heating state;
(2) carrying out heat treatment on the precursor of the first charge transport layer, preparing the slightly heated first charge transport layer on the first metal layer, and then carrying out annealing treatment;
(3) preparing a perovskite light absorption layer on the first charge transport layer, and carrying out annealing treatment;
(4) after a second charge transport layer is prepared on the perovskite light absorption layer, annealing treatment is carried out;
(5) and preparing a second metal layer on the second charge transport layer to serve as a microcavity light-emitting end and an electrode.
Compared with the prior art, the invention has the advantages that:
first, because the first metal layer is used as the light incidence end and the light reflection end, and the second metal layer is used as the light reflection end, the light resonates in the cavity, the field enhancement effect is generated, and the loss of the light energy is reduced.
And secondly, as the first metal layer and the first charge transmission layer are subjected to heat treatment, the stress between the films is reduced, and the grown perovskite light absorption layer has the characteristics of high film forming quality, small film defect density and low surface roughness, so that the efficiency of the perovskite solar cell with the microcavity structure is greatly improved.
The process for preparing the thin film resonant cavity has wide universality, is suitable for preparation processes of various types of solar cells, can be well adapted to an industrial wet film preparation process, and has great commercial value;
and fourthly, the PSC prepared by the invention has extremely high light absorption rate and efficiency at the whole wavelength, and simultaneously, the toxicity is lower than that of the conventional PSC by more than 40%. The invention can greatly promote the application of the PSC in commercialization, so that the toxicity reaches various environmental protection standards.
Drawings
FIG. 1 is a schematic flow diagram of a perovskite solar cell microcavity fabrication process in accordance with the present invention.
Fig. 2 is a schematic view of the structure of a device prepared by the present invention.
In the figure: the thin film transistor comprises a substrate (1), a transparent conductive layer (2), a first metal layer (3), a first charge transport layer (4), a perovskite light absorption layer (5), a second charge transport layer (6) and a second metal layer (7).
The specific implementation mode is as follows:
the invention is further explained below with reference to the drawings and examples.
Example 1: cleaning a substrate consisting of a substrate and a transparent conducting layer by using a conventional solvent, then carrying out ultraviolet ozone treatment for 15min, preparing a Cu first metal layer (evaporation, 10nm) on the substrate, slightly heating a PTAA hole transport layer solution (the temperature of the heating table is 40 ℃, heating for 5min) on the heating table, heating a substrate containing a metal layer on the heating table (the temperature of the heating table is 40 ℃, heating for 3min), preparing a PTAA hole transport layer (spin coating 2000rpm, 30s) on the substrate, and annealing for 10min to obtain PTAA with the thickness of 10 nm. The perovskite precursor solution was deposited on top of the PTAA layer (chlorobenzene was added dropwise at 4000rpm,60s, 45s spin). And transferring the film to a hot bench (the temperature of the hot bench is 100 ℃) to carry out thermal annealing on the perovskite film for 20min, and finally obtaining the perovskite film with the thickness of 400 nm. Cooling the film to normal temperature and evaporating C60The electron transmission layer is 40nm, and the Cu second metal layer is evaporated by 90 nm. V of the prepared PSCOC＝1.03V,JSC＝22.13mA/cm2And FF is 0.75, PCE is 17.2%, the light amplitude of 750nm is enhanced by 3.3 times, the light absorptivity of more than 650nm reaches more than 85%, and the same power toxicity is reduced by 33%.
Example 2: cleaning a substrate consisting of a substrate and a transparent conducting layer by using a conventional solvent, then carrying out ultraviolet ozone treatment for 15min, preparing an Au first metal layer (evaporation, 10nm) on the substrate, slightly heating a PTAA hole transport layer solution (the temperature of the heating table is 40 ℃, heating for 5min) on the heating table, heating a substrate containing the metal layer on the heating table (the temperature of the heating table is 40 ℃, heating for 3min), preparing a PTAA hole transport layer (spin coating 2000rpm, 30s) on the substrate, and annealing for 10min to obtain PTAA with the thickness of 10 nm. The perovskite precursor solution was deposited on top of the PTAA layer (chlorobenzene was added dropwise at 4000rpm,60s, 45s spin). And transferring the film to a hot bench (the temperature of the hot bench is 100 ℃) to carry out thermal annealing on the perovskite film for 20min, and finally obtaining the perovskite film with the thickness of 410 nm. Cooling the film to normal temperature and evaporating C60The electron transmission layer is 40nm, and the Cu second metal layer is evaporated by 90 nm. V of the prepared PSCOC＝1.01V,JSC21.53mA/cm2, 0.76 FF, 16.67% PCE, 3.1 times increased 750nm light amplitude, 84% or more light absorption rate at 650nm, and 31% lower toxicity.
Example 3: cleaning a substrate consisting of a substrate and a transparent conducting layer by using a conventional solvent, then carrying out ultraviolet ozone treatment for 15min, preparing a Cu first metal layer (evaporation, 10nm) on the substrate, slightly heating a PTAA hole transport layer solution (the temperature of the heating table is 40 ℃, heating for 5min) on the heating table, heating a substrate containing a metal layer on the heating table (the temperature of the heating table is 40 ℃, heating for 3min), preparing a PTAA hole transport layer (spin coating 2000rpm, 30s) on the substrate, and annealing for 10min to obtain PTAA with the thickness of 10 nm. The perovskite precursor solution was deposited on top of the PTAA layer (chlorobenzene was added dropwise at 4000rpm,60s, 45s spin). And transferring the film to a hot bench (the temperature of the hot bench is 100 ℃) to carry out thermal annealing on the perovskite film for 20min, and finally obtaining the perovskite film with the thickness of 410 nm. Cooling the film to normal temperature and evaporating C60The electron transmission layer is 40nm, and the Cu second metal layer is evaporated by 90 nm. V of the prepared PSCOC＝1.04V,JSC22.03mA/cm2, 0.74 FF, 17.09% PCE, 3.2 times increased 750nm light amplitude, 84% or more light absorption rate over 650nm, and 33% reduced toxicity.
Example 4: cleaning a substrate consisting of a substrate and a transparent conducting layer by using a conventional solvent, then carrying out ultraviolet ozone treatment for 15min, preparing a Cu first metal layer (evaporation, 10nm) on the substrate, slightly heating a PTAA hole transport layer solution (the temperature of the heating table is 40 ℃, heating for 5min) on the heating table, heating a substrate containing a metal layer on the heating table (the temperature of the heating table is 40 ℃, heating for 3min), preparing a PTAA hole transport layer (spin coating 2000rpm, 30s) on the substrate, and annealing for 10min to obtain PTAA with the thickness of 10 nm. The perovskite precursor solution was deposited on top of the PTAA layer (chlorobenzene was added dropwise at 4000rpm,60s, 45s spin). And transferring the film to a hot bench (the temperature of the hot bench is 100 ℃) to carry out thermal annealing on the perovskite film for 20min, and finally obtaining the perovskite film with the thickness of 410 nm. Cooling the film to normal temperature and evaporating C60The electron transmission layer is 40nm, and the Cu second metal layer is evaporated by 90 nm. V of the prepared PSCOC＝1.03V,JSC22.03mA/cm2, 0.76 FF, 17.57% PCE, 3.3 times increased 750nm light amplitude, 85% over 650nm light absorption rate and 34% lower toxicity.
Example 5: cleaning a substrate consisting of a substrate and a transparent conducting layer by using a conventional solvent, then carrying out ultraviolet ozone treatment for 15min, preparing a Cu first metal layer (evaporation, 10nm) on the substrate, slightly heating a PTAA hole transport layer solution (the temperature of the heating table is 40 ℃, heating for 5min) on the heating table, heating a substrate containing a metal layer on the heating table (the temperature of the heating table is 40 ℃, heating for 3min), preparing a PTAA hole transport layer (spin coating 2000rpm, 30s) on the substrate, and annealing for 10min to obtain PTAA with the thickness of 10 nm. The perovskite precursor solution was deposited on top of the PTAA layer (chlorobenzene was added dropwise at 4000rpm,60s, 45s spin). And transferring the film to a hot bench (the temperature of the hot bench is 100 ℃) to carry out thermal annealing on the perovskite film for 20min, and finally obtaining the perovskite film with the thickness of 410 nm. Cooling the film to normal temperature and evaporating C60The electron transmission layer is 40nm, and the Cu second metal layer is evaporated by 90 nm. V of the prepared PSCOC＝1.02V,JSC21.73mA/cm2, FF 0.76, PCE 16.94%, 750nm light amplitude increased by 3.2 times, 650nm light absorption rate over 84%, same power toxicity reduced by 32%.
The present invention has been illustrated by the above embodiments, but it should be understood that the above embodiments are for illustrative and descriptive purposes only and are not intended to limit the invention to the scope of the described embodiments. Furthermore, it will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that many variations and modifications may be made in accordance with the teachings of the present invention, which variations and modifications are within the scope of the present invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (9)

1. A perovskite solar cell with a microcavity structure comprises a substrate (1), a transparent conducting layer (2), a first charge transmission layer (4), a perovskite light absorption layer (5), a second charge transmission layer (6) and a second metal layer (7) which are sequentially stacked; the light-emitting diode is characterized in that a first metal layer (3) is arranged between the transparent conducting layer (2) and the first charge transmission layer (4), the first metal layer (3) is used as a microcavity light-in end, and the second metal layer (7) is used as a microcavity light-out end.
2. The perovskite solar cell with the microcavity structure as claimed in claim 1, wherein the thickness of the perovskite light absorption layer is 100-500 nm, and the lead content is less than 50% of that of a conventional perovskite solar cell.
3. The perovskite solar cell with the microcavity structure according to claim 1, wherein the first metal layer (3) is a metal material having strong reflectivity and electrical conductivity, and the second metal layer (7) is a metal material having a high work function.
4. The perovskite solar cell having a microcavity structure according to claim 3, wherein: the first metal layer (3) is made of one of gold Au, silver Ag and copper Cu, and the thickness of the first metal layer is 5-15 nm.
5. The perovskite solar cell with microcavity structure according to claim 1, characterized in that the perovskite light absorption layer (5) for absorbing incident light is ABX3A photovoltaic material of a three-dimensional perovskite structure; or is L2An-1BnX3n+1Or L2An-1BnX3n+1A photovoltaic material of a two-dimensional perovskite structure.
6. The perovskite solar cell with the microcavity structure according to claim 1, wherein the first charge transport layer (4) and the second charge transport layer (5) are an electron transport layer and a hole transport layer, respectively, or a transport layer and an electron transport layer, respectively.
7. A preparation method of a perovskite solar cell with a microcavity structure is characterized by comprising the following steps:
(1) preparing a first metal layer on the transparent conducting layer to be used as a light-entering end of the microcavity, and carrying out heat treatment to enable the first metal layer and the transparent conducting layer to be in a micro-heating state;
(2) carrying out heat treatment on the precursor of the first charge transport layer, preparing the slightly heated first charge transport layer on the first metal layer, and then carrying out annealing treatment;
(3) preparing a perovskite light absorption layer on the first charge transport layer, and carrying out annealing treatment;
(4) after a second charge transport layer is prepared on the perovskite light absorption layer, annealing treatment is carried out;
(5) and preparing a second metal layer on the second charge transport layer to serve as a microcavity light-emitting end and an electrode.
8. The method for preparing a microcavity in a perovskite solar cell according to claim 7, wherein the method comprises the following steps: the heat treatment temperature in the step (1) is 80-120 ℃, and the time is 1-5 min; and (3) performing heat treatment on the precursor of the first charge transport layer in the step (2) at the temperature of 30-50 ℃.
9. The method of claim 7, wherein the method comprises: and (3) the time interval between the completion of the heat treatment in the step (2) and the preparation of the first charge transport layer is 0-3 s.
CN202210106786.XA 2022-01-28 2022-01-28 Perovskite solar cell with microcavity structure and preparation method thereof Pending CN114447228A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115498110A (en) * 2022-11-17 2022-12-20 无锡众能光储科技有限公司 Perovskite solar cell with composite structure and preparation method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115498110A (en) * 2022-11-17 2022-12-20 无锡众能光储科技有限公司 Perovskite solar cell with composite structure and preparation method

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