CN117156886A - Perovskite/silicon heterojunction stacked solar cell with improved carrier transport properties - Google Patents

Perovskite/silicon heterojunction stacked solar cell with improved carrier transport properties Download PDF

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CN117156886A
CN117156886A CN202311075783.5A CN202311075783A CN117156886A CN 117156886 A CN117156886 A CN 117156886A CN 202311075783 A CN202311075783 A CN 202311075783A CN 117156886 A CN117156886 A CN 117156886A
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layer
dielectric layer
solar cell
perovskite
silicon
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张华�
何博
何永才
董鑫
丁蕾
赵双双
张富
高亚军
刘江
徐希翔
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Longi Green Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/10—Organic photovoltaic [PV] modules; Arrays of single organic PV cells
    • H10K39/15—Organic photovoltaic [PV] modules; Arrays of single organic PV cells comprising both organic PV cells and inorganic PV cells
    • 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
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
    • 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
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/86—Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers
    • 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
    • H10K30/88—Passivation; Containers; Encapsulations
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The application provides a perovskite/silicon heterojunction laminated solar cell which comprises a silicon substrate cell, a composite layer, a hole transmission layer, a first dielectric layer, a perovskite absorption layer, a second dielectric layer and an electron transmission layer which are sequentially laminated, wherein the first dielectric layer and the second dielectric layer promote cross-interface transmission of carriers. According to the perovskite/silicon heterojunction laminated solar cell, the dielectric layer is introduced between the perovskite absorption layer and the electron transmission layer as well as between the perovskite absorption layer and the hole transmission layer, so that non-radiative recombination of an interface is passivated, and meanwhile, separation and transmission of carriers are enhanced, so that V of the perovskite/silicon heterojunction laminated solar cell is improved OC And FF.

Description

Perovskite/silicon heterojunction stacked solar cell with improved carrier transport properties
Technical Field
The application belongs to the technical field of solar cells, and particularly relates to a perovskite/silicon heterojunction laminated solar cell with improved carrier transmission performance.
Background
Recently, the world record efficiency of perovskite/crystalline silicon laminated solar cells breaks through 33.7%, and the theoretical limit efficiency of each perovskite or crystalline silicon single cell is exceeded. The perovskite of the ternary mixed cation (CsFAMA) of organic-inorganic metal halogen is mostly adopted as a perovskite sub-cell of the high-efficiency perovskite/crystalline silicon laminated solar cell device, and an inverted (p-i-n) device structure is usually preferred in consideration of lower parasitic absorption and a preparation process capable of being processed at a low temperature; meanwhile, a self-assembled monolayer (SAM) material and a fullerene derivative material are selected as a classical hole selective transport layer (HTL) and electron selective transport layer (ETL). However, many researches show that the perovskite light absorption layer and the fullerene derivative ETL interface have obvious non-radiative recombination, and the recombination mechanism behind the perovskite light absorption layer has not been clearly explained at present; in addition, there is also a greater recombination when the perovskite is in direct contact with the underlying metal oxide conductive/composite layer, thereby limiting the device from achieving a higher open circuit voltage (V OC )。
Whether the lower interface of the HTL/perovskite light absorption layer or the upper interface of the perovskite light absorption layer/ETL, the whole device can obtain V closest to the limit only when the carriers in the perovskite are output as much as possible OC The two most significant factors affecting this process are energy level matching and the defect state of the table interface. If the energy levels are not matched, energy level bending is generated at the interface, so that perovskite light is absorbedThe fermi level of the collector is less than its internal quasi-fermi level, and the device can output V OC Often determined by the fermi level, thus yielding V OC Is a loss of (2); likewise, if there are defect states at the upper and lower surface interfaces of the perovskite, carriers generated inside the perovskite light absorbing layer are highly likely to be recombined by these defects. In contrast, for the HTL/perovskite light absorbing layer lower interface, in addition to energy level matching and interface defects, there may be situations where the perovskite light absorbing layer is in direct contact with the composite layer metal oxide, which may result in carriers separated from the perovskite being directly recombined.
Disclosure of Invention
The present application is directed to a perovskite/silicon heterojunction stacked solar cell having improved carrier transport properties.
In particular, the application relates to the following aspects:
1. a perovskite/silicon heterojunction laminated solar cell comprises a silicon substrate cell, a composite layer, a hole transmission layer, a first dielectric layer, a perovskite absorption layer, a second dielectric layer and an electron transmission layer which are laminated in sequence,
wherein the first dielectric layer and the second dielectric layer promote cross-interface transport of carriers.
2. The solar cell of item 1, wherein the dipole moment of the first dielectric layer and the second dielectric layer material is 2D or greater.
3. The perovskite/silicon heterojunction laminated solar cell comprises a silicon substrate cell, a composite layer, a hole transmission layer, a first dielectric layer, a perovskite absorption layer, a second dielectric layer and an electron transmission layer which are laminated in sequence, wherein dipole moments of materials of the first dielectric layer and the second dielectric layer are more than or equal to 2D.
4. The solar cell according to item 1 or 3, wherein a material of the first dielectric layer is selected from one or more of 4-methoxyphenethyl amine bromide (OMe-pei), 4-fluorophenethyl amine iodide (F-pei), 4-chlorophenylethyl amine iodide (Cl-pei), potassium iodide, and potassium chloride.
5. The solar cell according to item 1 or 3Wherein the material of the second dielectric layer is selected from 1, 3-diaminopropane dihydroiodate (PDADI) 2 ) Ethylenediamine dihydroiodide (EDADI) 2 ) 1, 4-butanediamine hydroiodidate (BDADI) 2 ) 1, 6-hexamethylenediamine Hydroiodidate (HDADI) 2 ) One or more of imidazole hydroiodides (IMI).
6. The solar cell of item 1 or 3, wherein the material of the first dielectric layer is OMe-pei and the material of the second dielectric layer is PDADI 2 。
7. The solar cell of item 1 or 3, wherein the first dielectric layer has a thickness of 1-5nm.
8. The solar cell of item 1 or 3, wherein the second dielectric layer has a thickness of 0.5-1nm.
9. The solar cell of item 1 or 3, wherein the first dielectric layer and the second dielectric layer are prepared by solution spin coating.
10. The solar cell according to item 9, wherein when the first dielectric layer is prepared by a solution spin coating method, a concentration of the material of the first dielectric layer in the solution used is 1 to 5mg/mL.
11. The solar cell according to item 9, wherein when the second dielectric layer is prepared by a solution spin coating method, a concentration of the material of the second dielectric layer in the solution used is 0.5 to 1mg/mL.
12. The solar cell according to item 1 or 3, wherein the solar cell further comprises a buffer layer and a transparent conductive oxide layer, which are sequentially stacked, on a side of the electron transport layer remote from the silicon substrate cell.
According to the perovskite/silicon heterojunction laminated solar cell, the dielectric layer is introduced between the perovskite absorption layer and the electron transmission layer as well as between the perovskite absorption layer and the hole transmission layer, so that non-radiative recombination of an interface is passivated, and meanwhile, separation and transmission of carriers are enhanced, so that V of the perovskite/silicon heterojunction laminated solar cell is improved OC And FF.
Drawings
FIG. 1 is a schematic diagram of a stacked solar cell of the present application;
figure 2 shows the effect of a material with a relatively large dipole moment on carrier extraction and transport.
Reference numerals:
1 silicon substrate cell, 2 composite layer, 3 hole transport layer, 4 first dielectric layer, 5 perovskite absorption layer, 6 second dielectric layer, 7 electron transport layer, 8 buffer layer, 9 transparent conductive oxide layer, 10 antireflection layer
Detailed Description
The application will be further illustrated with reference to the following examples, which are to be understood as merely further illustrating and explaining the application and are not to be construed as limiting the application.
Unless defined otherwise, technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application, the materials and methods are described herein below. In case of conflict, the present specification, including definitions therein, will control and materials, methods, and examples, will control and be in no way limiting. The application is further illustrated below in connection with specific examples, which are not intended to limit the scope of the application.
In order to solve the problems of the prior art, the application provides a perovskite/silicon heterojunction laminated solar cell, which comprises a silicon substrate cell 1, a composite layer 2, a hole transport layer 3, a first dielectric layer 4, a perovskite absorption layer 5, a second dielectric layer 6 and an electron transport layer 7 which are sequentially laminated, as shown in fig. 1. Conventional perovskite/silicon heterojunction stacked solar cells do not comprise the first dielectric layer 4 and the second dielectric layer 6 of the present application. The first dielectric layer 4 and the second dielectric layer 6 of the application can promote the cross-interface transmission of carriers, namely promote the transmission of holes and electrons at the two interfaces of the perovskite absorption layer 5 and the hole transmission layer 3 and the perovskite absorption layer 5 and the electron transmission layer 7.
The materials of the first dielectric layer 4 and the second dielectric layer 6 are materials with relatively large dipole moments, for example, dipole moments greater than or equal to 2D, for example, 2D, 3D, 4D, 5D, 6D, 7D, 8D, 9D, 10D, 12D, 15D, 20D, 25D, 30D, 35D, and 40D, and any range between these values. The dipole moment of each material can be interrogated by means of a tool book.
In a specific embodiment, the dipole moment of the first dielectric layer 4 is 10D or more, and the dipole moment of the second dielectric layer 6 is 10D or more.
The material with larger dipole moment can promote the redistribution of charges at the interface between the light absorption layer (namely the perovskite absorption layer) and the transmission layer by introducing an additional electric field, thereby causing the change of work function of the light absorption active layer/the transmission layer, leading the interface energy level to be more matched, and finally leading the carriers to be extracted and transmitted more effectively. The effect of introducing a material with a relatively large dipole moment as a dielectric layer is shown in fig. 2, where fig. 2a is the transport of carriers in the case where no dielectric layer is present between the electron transporting layer and the light absorbing layer, and in the case where no dielectric layer is present between the hole transporting layer and the light absorbing layer, and fig. 2b is the transport of carriers in the case where a dielectric layer is introduced between the electron transporting layer and the light absorbing layer, and in the case where a dielectric layer is present between the hole transporting layer and the light absorbing layer. The additional electric field introduced by the dielectric layer is directional and has a magnitude, so that different materials are needed for the two interfaces, and the effect of 'charge extraction' can be enhanced more effectively when the additional electric field is consistent with the electric field of the previous interface of the light absorption layer/charge transmission layer. For example, on the electron transport side, electron acceptor materials such as lewis acids, ammonium salts, etc. should be selected; on the hole transport side, electron donor materials such as lewis bases, ionic salts, etc. should be selected. Meanwhile, in any device structure, carrier extraction on the electron transport side is generally weaker than hole transport measurement, so that when a dielectric layer with a large dipole moment is selected, the dipole moment of the dielectric layer on the electron transport side should be equal to or greater than that on the hole transport side, for example, in an inverted device structure (anode/hole transport layer/light absorption layer/electron transport layer/cathode), that is, the dipole moment of the first dielectric layer (hole transport layer/first dielectric layer/light absorption layer) should be equal to that of the second dielectric layer (light absorption layer/second dielectric layer/electron transport layer); for the formal device structure (anode/electron transport layer/light absorption layer/hole transport layer/cathode), the dipole moment of the first dielectric layer (electron transport layer/first dielectric layer/light absorption layer) should be equal to or larger than that of the second dielectric layer (light absorption layer/second dielectric layer/hole transport layer).
In a specific embodiment, the first dielectric layer 4 is one or more of 4-methoxyphenethyl amine bromide (OMe-pei), 4-fluorophenethyl amine iodide (F-pei), 4-chlorophenylethyl amine iodide (Cl-pei), potassium iodide, and potassium chloride.
In a specific embodiment, the second dielectric layer 6 is 1, 3-diaminopropane dihydroiodate (PDADI) 2 ) Ethylenediamine dihydroiodide (EDADI) 2 ) 1, 4-butanediamine hydroiodidate (BDADI) 2 ) 1, 6-hexamethylenediamine Hydroiodidate (HDADI) 2 ) One or more of imidazole hydroiodides (IMI).
In a specific embodiment, the material of the first dielectric layer 4 is OMe-pei and the material of the second dielectric layer 6 is PDADI 2 。
In a specific embodiment, the thickness of the first dielectric layer 4 is 1-5nm, which may be, for example, 1nm, 1.5nm, 2nm, 2.5nm, 3nm, 3.5nm, 4nm, 4.5nm, 5nm, and any range between these values.
In a specific embodiment, the thickness of the second dielectric layer 6 is 0.5-1nm, which may be, for example, 0.5nm, 0.6nm, 0.7nm, 0.8nm, 0.9nm, 1nm, and any range between these values.
Both the first dielectric layer 4 and the second dielectric layer 6 may be prepared using methods known in the art, such as solution spin coating. When the first dielectric layer is prepared by using a solution spin coating method, the concentration of the material of the first dielectric layer in the solution used is 1 to 5mg/mL, and for example, may be 1mg/mL, 1.5mg/mL, 2mg/mL, 2.5mg/mL, 3mg/mL, 3.5mg/mL, 4mg/mL, 4.5mg/mL, 5mg/mL, and any range between these values. As the solvent for the solution, ethanol, dimethoxyethanol, N-dimethylformamide, dimethyl sulfoxide and the like can be used.
When the second dielectric layer is prepared using a solution spin coating method, the concentration of the material of the second dielectric layer in the solution used is 0.5 to 1mg/mL, and may be, for example, 0.5mg/mL, 0.6mg/mL, 0.7mg/mL, 0.8mg/mL, 0.9mg/mL, 1mg/mL, and any range between these values. The solvent of the solution may be isopropyl alcohol, methanol or the like, and isopropyl alcohol is preferable.
The silicon substrate cell 1 may be any of various substrate cells known in the art as suitable for perovskite/silicon heterojunction stacked cells. The silicon-based battery 1 can be in a planar structure or a suede structure, and each layer prepared on the silicon-based battery 1 is conformal with the silicon-based battery 1.
The material of the composite layer 2 can be Indium Tin Oxide (ITO), zinc-doped indium oxide (IZO), aluminum-doped zinc oxide (AZO), etc., and the thickness is 1-20nm. The composite layer 2 can be prepared by Physical Vapor Deposition (PVD), radio frequency magnetron sputtering, atomic layer vacuum deposition, plasma enhanced chemical vapor deposition, chemical vapor deposition and the like.
The material of the hole transport layer 3 may be an organic transport layer material such as [2- (3, 6-dimethoxy-9H-carbazol-9-yl) ethyl ]]Phosphonic acid (OMe-2 PACz), poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine](PTAA) or the like, also can be an inorganic transport layer material, such as NiMgOx, V 2 O 5 MoOx, niOx, etc. The thickness of the hole transport layer is 1-5nm. The hole transport layer can be prepared by spin coating, atomic layer deposition, evaporation and the like.
The perovskite absorption layer 5 material has a chemical formula of AB (X n Y 1-n ) 3 Wherein A is typically CH 3 NH 3 (MA)、NH 2 ＝CHNH 2 Monovalent cations such as (FA) or Cs; b is usually a divalent metal ion such as Pb, sn, etc.; x, Y is typically a halogen anion such as Cl, br or I, and X is not equal to Y; n=1, 2, 3; according to different preparation processes, the thickness range of the perovskite light absorption layer can reach 500-1000nm.
The electron transport layer 7 may be an organic transport layer material, such as PC 61 BM, BCP, etc., also inorganic transport layer materials, such as C 60 、ZnO、TiO 2 、SnO 2 Etc. The thickness of the electron transport layer is 8-20nm. The electron transport layer can be prepared by sol-gel, atomic layer deposition, thermal evaporation and the like.
Further, as shown in fig. 1, the solar cell further includes a buffer layer 8 and a transparent conductive oxide layer 9, which are sequentially stacked, on a side of the electron transport layer 7 away from the silicon substrate cell 1.
Wherein the material of the buffer layer 8 can be TiO 2 、SnO 2 、SiO 2 、Al 2 O 3 、Fe 2 O 3 、Cu 2 O, alZnO, etc., with a thickness of 10-15nm. The buffer layer 8 may be prepared by atomic layer deposition, thermal evaporation, spin coating, and the like.
The material of the transparent conductive oxide layer 9 may be ITO, IZO, ITiO, IWO or the like with a thickness of 30-70nm. The transparent conductive oxide layer 9 can be prepared by adopting a radio frequency magnetron sputtering method, a vacuum evaporation deposition method, a chemical vapor deposition method and the like.
It will be appreciated by those skilled in the art that the preparation method of the present application further includes a step of preparing an electrode, and further may include a step of preparing an antireflection layer according to actual needs. The electrode is made of Au, ag, cu or C, preferably Ag, and has a thickness of 300-1000nm. The material of the antireflection layer can be MgF 2 、LiF、PDMS、SiO 2 Etc., preferably MgF 2 The thickness is 100-130nm.
In a specific embodiment, the perovskite/silicon heterojunction laminated solar cell comprises a silicon substrate cell 1, a composite layer 2, a hole transmission layer 3, a first dielectric layer 4, a perovskite absorption layer 5, a second dielectric layer 6, an electron transmission layer 7, a buffer layer and a transparent conductive oxide layer 8 which are laminated in sequence, wherein the first dielectric layer 4 is one or more than two of 4-methoxyphenethyl amine bromide (OMe-PEAI), 4-fluorophenethyl amine iodide (F-PEAI), 4-chlorophenethyl amine iodide (Cl-PEAI), potassium iodide and potassium chloride; the second dielectric layer 6 is 1, 3-diaminopropane dihydroiodate (PDADI) 2 ) Ethylenediamine dihydroiodide (EDADI) 2 ) 1, 4-butanediamine hydroiodidate (BDADI) 2 ) 1, 6-hexamethylenediamine Hydroiodidate (HDADI) 2 ) One or more than two of imidazole hydroiodides (IMI), wherein the thickness of the first dielectric layer is 1-5nm, and the thickness of the second dielectric layer is 0.5-1nm.
The perovskite/silicon heterojunction laminated solar cell is formed by forming a perovskite absorption layer 5 and an electron transport layer7, a dielectric layer is introduced between the perovskite absorption layer 5 and the hole transmission layer 3, so that non-radiative recombination of an interface is passivated, and meanwhile, separation and transmission of carriers are enhanced, thereby improving V of the perovskite/silicon heterojunction laminated solar cell OC And FF.
Examples
Example 1
As shown in fig. 1, the titanium ore/silicon heterojunction laminated solar cell comprises a silicon substrate cell 1, a composite layer 2, a hole transport layer 3, a first dielectric layer 4, a perovskite absorption layer 5, a second dielectric layer 6, an electron transport layer 7, a buffer layer 8, a transparent conductive oxide layer 9 and an antireflection layer 10 which are laminated in sequence.
The preparation method of the laminated battery comprises the following steps:
(1) Providing a silicon-based cell
The silicon-based battery 1 is a SHJ structure silicon-based battery substrate and comprises a C-Si layer, a double-sided intrinsic amorphous silicon a-Si H (i) layer, a front n-type doped passivation layer, a back p-type doped passivation layer, a back metal oxide conductive layer and a back Ag electrode layer; cutting with laser to obtain 2×2cm 2 Is provided.
(2) Preparation of composite layers
ITO was prepared as a composite layer 2 on a silicon substrate cell 1 using a Physical Vapor Deposition (PVD) method, with a thickness ranging from 1 to 20nm.
(3) Preparation of hole transport layer
And spin-coating OMe-2PACz dimethoxy ethanol solution with the concentration of 1mg/mL on the crystalline silicon cell substrate on which the ITO is deposited to serve as a hole transport layer 3. Specifically, 100 mu L of OMe-2PACz dimethoxy ethanol solution is sucked by a liquid-transferring gun, spin-coated for 30s at a rotating speed of 3000rpm, and immediately placed on a hot table for heating at 100 ℃ for 10min after spin-coating is finished; the thickness of the hole transport layer 3 is 1-5nm.
(4) Preparing a first dielectric layer
A first dielectric layer 4 of OMe-PEAI material was prepared on the hole transport layer 3 using a solution spin coating method. Wherein the concentration of OMe-PEAI in the solution used by the solution spin-coating method is 2mg/mL, the solvent is ethanol, specifically, 100 mu L of OMe-PEAI ethanol solution is taken by a liquid-transferring gun, and is spin-coated for 30s at a rotating speed of 3000rpm on a hole-transporting layer substrate with OMe-2PACz, and the thickness is 1-2nm without treatment after spin-coating.
(5) Preparation of perovskite absorber layer
A perovskite light absorbing layer 5 is prepared in a one-step process on the first dielectric layer 4. Specifically, spin-coating perovskite precursor solution, taking 100 mu L of perovskite precursor solution to drop on a substrate on which a high work function dielectric passivation layer is deposited by a liquid-transferring gun, spin-coating for 50s by using a rotating speed of 3000rpm, and immediately placing on a heat table for heating and annealing at 110 ℃ for 30min after spin-coating, wherein the perovskite comprises Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 ) 3 The precursor solution is PbI 2 /PbBr 2 The mixed solution of/FAI/MABr/CsI (solvent is DMF: DMSO=4:1 mixed solvent, total mass is 1.5 mM/mL). The perovskite absorber layer thickness was about 800nm.
(6) Preparing a second dielectric layer
Preparation of a material PDADI on the perovskite light absorbing layer 5 using solution spin coating 2 Is provided, the second dielectric layer 6 of (a). In which PDADI in solution used in solution spin coating 2 The concentration of (2) was 0.5mg/mL, and the solvent was isopropanol. Specifically, 100. Mu.L of PDADI was taken with a pipette 2 The isopropanol solution is dripped on the substrate for preparing the perovskite light absorption layer, and is spin-coated for 30 seconds at a rotation speed of 5000rpm, and the thickness is 0.5-1nm without treatment after spin-coating is finished.
(7) Preparation of an electron transport layer
Vapor deposition of C60 as electron transport layer 7 on second dielectric layer 7 using a thermal vapor deposition apparatus at a vapor deposition rate ofThe thickness is 8-20nm.
(8) Preparation of buffer layer
Preparation of SnO on electron transport layer 7 Using an atomic layer vacuum deposition System 2 The buffer layer 8 is deposited at 80 ℃ and has a thickness of 10-15nm.
(9) Preparation of transparent conductive oxide layer
An ITO transparent conductive oxide layer 9 was prepared on the buffer layer 8 using a Physical Vapor Deposition (PVD) system, with a thickness ranging from 30 to 70nm.
(10) Preparation of the back electrode
The back electrode is prepared from Ag with a film thickness of 300-1000nm.
(11) Preparation of an antireflection layer
Preparation of MgF using electron beam thermal evaporation deposition system 2 The thickness of the antireflection layer is 100-130nm.
Example 2
The titanium ore/silicon heterojunction laminated solar cell comprises a silicon substrate cell 1, a composite layer 2, a hole transmission layer 3, a first dielectric layer OMe-PEAI, a perovskite absorption layer 5 and a second dielectric layer BDADI which are laminated in sequence 2 An electron transport layer 7, a buffer layer 8, a transparent conductive oxide layer 9, an antireflection layer 10.
The preparation method of the laminated battery comprises the following steps:
(1) Providing a silicon-based cell
The silicon-based battery 1 is a SHJ structure silicon-based battery substrate and comprises a C-Si layer, a double-sided intrinsic amorphous silicon a-Si H (i) layer, a front n-type doped passivation layer, a back p-type doped passivation layer, a back metal oxide conductive layer and a back Ag electrode layer; cutting with laser to obtain 2×2cm 2 Is provided.
(2) Preparation of composite layers
ITO was prepared as a composite layer 2 on a silicon substrate cell 1 using a Physical Vapor Deposition (PVD) method, with a thickness ranging from 1 to 20nm.
(3) Preparation of hole transport layer
And spin-coating OMe-2PACz dimethoxy ethanol solution with the concentration of 1mg/mL on the crystalline silicon cell substrate on which the ITO is deposited to serve as a hole transport layer 3. Specifically, 100 mu L of OMe-2PACz dimethoxy ethanol solution is sucked by a liquid-transferring gun, spin-coated for 30s at a rotating speed of 3000rpm, and immediately placed on a hot table for heating at 100 ℃ for 10min after spin-coating is finished; the thickness of the hole transport layer 3 is 1-5nm.
(4) Preparing a first dielectric layer
A first dielectric layer 4 of OMe-PEAI material was prepared on the hole transport layer 3 using a solution spin coating method. Wherein the concentration of OMe-PEAI in the solution used by the solution spin-coating method is 2mg/mL, the solvent is ethanol, specifically, 100 mu L of OMe-PEAI ethanol solution is taken by a liquid-transferring gun, and is spin-coated for 30s at a rotating speed of 3000rpm on a hole-transporting layer substrate with OMe-2PACz, and the thickness is 1-2nm without treatment after spin-coating.
(5) Preparation of perovskite absorber layer
A perovskite light absorbing layer 5 is prepared in a one-step process on the first dielectric layer 4. Specifically, spin-coating perovskite precursor solution, taking 100 mu L of perovskite precursor solution to drop on a substrate on which a high work function dielectric passivation layer is deposited by a liquid-transferring gun, spin-coating for 50s by using a rotating speed of 3000rpm, and immediately placing on a heat table for heating and annealing at 110 ℃ for 30min after spin-coating, wherein the perovskite comprises Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 ) 3 The precursor solution is PbI 2 /PbBr 2 The mixed solution of/FAI/MABr/CsI (solvent is DMF: DMSO=4:1 mixed solvent, total mass is 1.5 mM/mL). The perovskite absorber layer thickness was about 800nm.
(6) Preparing a second dielectric layer
Preparation of a Material BDADI on the perovskite light absorbing layer 5 Using solution spin coating 2 Is provided, the second dielectric layer 6 of (a). BDADI in solution for use in solution spin coating 2 The concentration of (2) was 0.3mg/mL, and the solvent was isopropanol. Specifically, 100. Mu.L of BDADI was taken with a pipette 2 The isopropanol solution is dripped on the substrate for preparing the perovskite light absorption layer, and is spin-coated for 30 seconds at a rotation speed of 5000rpm, and the thickness is 0.5-1nm without treatment after spin-coating is finished.
(7) Preparation of an electron transport layer
Vapor deposition of C60 as electron transport layer 7 on second dielectric layer 7 using a thermal vapor deposition apparatus at a vapor deposition rate ofThe thickness is 8-20nm.
(8) Preparation of buffer layer
Using atomic layer vacuum depositionPreparation of SnO on the electron transport layer 7 by the deposition system 2 The buffer layer 8 is deposited at 80 ℃ and has a thickness of 10-15nm.
(9) Preparation of transparent conductive oxide layer
An ITO transparent conductive oxide layer 9 was prepared on the buffer layer 8 using a Physical Vapor Deposition (PVD) system, with a thickness ranging from 30 to 70nm.
(10) Preparation of the back electrode
The back electrode is prepared from Ag with a film thickness of 300-1000nm.
(11) Preparation of an antireflection layer
Preparation of MgF using electron beam thermal evaporation deposition system 2 The thickness of the antireflection layer is 100-130nm.
Comparative example 1
The titanium ore/silicon heterojunction stacked solar cell of this comparative example is different from example 1 only in that it does not include the first dielectric layer 4 and the second dielectric layer 6, i.e., includes the silicon substrate cell 1, the composite layer 2, the hole transport layer 3, the perovskite absorption layer 5, the electron transport layer 7, the buffer layer 8, the transparent conductive oxide layer 9, and the antireflection layer 10, which are stacked in this order.
The manufacturing method of the laminate battery is different from example 1 in that it does not include step (4) and step (6), and specifically includes the steps of:
(1) Providing a silicon-based cell
The silicon-based battery 1 is a SHJ structure silicon-based battery substrate and comprises a C-Si layer, a double-sided intrinsic amorphous silicon a-Si H (i) layer, a front n-type doped passivation layer, a back p-type doped passivation layer, a back metal oxide conductive layer and a back Ag electrode layer; cutting with laser to obtain 2×2cm 2 Is provided.
(2) Preparation of composite layers
ITO was prepared as a composite layer 2 on a silicon substrate cell 1 using a Physical Vapor Deposition (PVD) method, with a thickness ranging from 1 to 20nm.
(3) Preparation of hole transport layer
And spin-coating OMe-2PACz dimethoxy ethanol solution with the concentration of 1mg/mL on the crystalline silicon cell substrate on which the ITO is deposited to serve as a hole transport layer 3. Specifically, 100 mu L of OMe-2PACz dimethoxy ethanol solution is sucked by a liquid-transferring gun, spin-coated for 30s at a rotating speed of 3000rpm, and immediately placed on a hot table for heating at 100 ℃ for 10min after spin-coating is finished; the thickness of the hole transport layer 3 is 1-5nm.
(4) Preparation of perovskite absorber layer
A perovskite light absorbing layer 5 is prepared in a one-step process on the hole transporting layer 3. Specifically, spin-coating perovskite precursor solution, taking 100 mu L of perovskite precursor solution to drop on a substrate on which a high work function dielectric passivation layer is deposited by a liquid-transferring gun, spin-coating for 50s by using a rotating speed of 3000rpm, and immediately placing on a heat table for heating and annealing at 110 ℃ for 30min after spin-coating, wherein the perovskite comprises Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 ) 3 The precursor solution is PbI 2 /PbBr 2 The mixed solution of/FAI/MABr/CsI (solvent is DMF: DMSO=4:1 mixed solvent, total mass is 1.5 mM/mL). The perovskite absorber layer thickness was about 800nm.
(5) Preparation of an electron transport layer
C60 is evaporated as an electron transport layer 7 on the perovskite absorption layer 5 using a thermal evaporation apparatus at an evaporation rate ofThe thickness is 8-20nm.
(6) Preparation of buffer layer
Preparation of SnO on electron transport layer 7 Using an atomic layer vacuum deposition System 2 The buffer layer 8 is deposited at 80 ℃ and has a thickness of 10-15nm.
(7) Preparation of transparent conductive oxide layer
An ITO transparent conductive oxide layer 9 was prepared on the buffer layer 8 using a Physical Vapor Deposition (PVD) system, with a thickness ranging from 30 to 70nm.
(8) Preparation of the back electrode
The back electrode is prepared from Ag with a film thickness of 300-1000nm.
(9) Preparation of an antireflection layer
Preparation of MgF using electron beam thermal evaporation deposition system 2 The thickness of the antireflection layer is 100-130nm.
Comparative example 2
The titanium ore/silicon heterojunction stacked solar cell of this comparative example is different from example 1 only in that it does not include the second dielectric layer 6, that is, includes the silicon substrate cell 1, the composite layer 2, the hole transport layer 3, the first dielectric layer 4, the perovskite absorption layer 5, the electron transport layer 7, the buffer layer 8, the transparent conductive oxide layer 9, and the antireflection layer, which are stacked in this order.
The manufacturing method of the laminate battery is different from example 1 in that step (6) is not included, and specifically includes the steps of:
(1) Providing a silicon-based cell
The silicon-based battery 1 is a SHJ structure silicon-based battery substrate and comprises a C-Si layer, a double-sided intrinsic amorphous silicon a-Si H (i) layer, a front n-type doped passivation layer, a back p-type doped passivation layer, a back metal oxide conductive layer and a back Ag electrode layer; cutting with laser to obtain 2×2cm 2 Is provided.
(2) Preparation of composite layers
ITO was prepared as a composite layer 2 on a silicon substrate cell 1 using a Physical Vapor Deposition (PVD) method, with a thickness ranging from 1 to 20nm.
(3) Preparation of hole transport layer
And spin-coating OMe-2PACz dimethoxy ethanol solution with the concentration of 1mg/mL on the crystalline silicon cell substrate on which the ITO is deposited to serve as a hole transport layer 3. Specifically, 100 mu L of OMe-2PACz dimethoxy ethanol solution is sucked by a liquid-transferring gun, spin-coated for 30s at a rotating speed of 3000rpm, and immediately placed on a hot table for heating at 100 ℃ for 10min after spin-coating is finished; the thickness of the hole transport layer 3 is 1-5nm.
(4) Preparing a first dielectric layer
A first dielectric layer 4 of OMe-PEAI material was prepared on the hole transport layer 3 using a solution spin coating method. Wherein the concentration of OMe-PEAI in the solution used by the solution spin-coating method is 2mg/mL, the solvent is ethanol, specifically, 100 mu L of OMe-PEAI ethanol solution is taken by a liquid-transferring gun, and is spin-coated for 30s at a rotating speed of 3000rpm on a hole-transporting layer substrate with OMe-2PACz, and the thickness is 1-2nm without treatment after spin-coating.
(5) Preparation of perovskite absorber layer
A perovskite light absorbing layer 5 is prepared in a one-step process on the hole transporting layer 3. Specifically, spin-coating perovskite precursor solution, taking 100 mu L of perovskite precursor solution to drop on a substrate on which a high work function dielectric passivation layer is deposited by a liquid-transferring gun, spin-coating for 50s by using a rotating speed of 3000rpm, and immediately placing on a heat table for heating and annealing at 110 ℃ for 30min after spin-coating, wherein the perovskite comprises Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 ) 3 The precursor solution is PbI 2 /PbBr 2 The mixed solution of/FAI/MABr/CsI (solvent is DMF: DMSO=4:1 mixed solvent, total mass is 1.5 mM/mL). The perovskite absorber layer thickness was about 800nm.
(6) Preparation of an electron transport layer
Vapor deposition of C60 as electron transport layer 7 on LiF dielectric layer using thermal vapor deposition apparatus at a rate ofThe thickness is 8-20nm.
(7) Preparation of buffer layer
Preparation of SnO on electron transport layer 7 Using an atomic layer vacuum deposition System 2 The buffer layer 8 is deposited at 80 ℃ and has a thickness of 10-15nm.
(8) Preparation of transparent conductive oxide layer
An ITO transparent conductive oxide layer 9 was prepared on the buffer layer 8 using a Physical Vapor Deposition (PVD) system, with a thickness ranging from 30 to 70nm.
(9) Preparation of the back electrode
The back electrode is prepared from Ag with a film thickness of 300-1000nm.
(10) Preparation of an antireflection layer
Preparation of MgF using electron beam thermal evaporation deposition system 2 The thickness of the antireflection layer is 100-130nm.
Comparative example 3
The titanium ore/silicon heterojunction stacked solar cell of this comparative example is different from example 1 only in that it does not include the first dielectric layer 4, that is, includes the silicon substrate cell 1, the composite layer 2, the hole transport layer 3, the perovskite absorption layer 5, the second dielectric layer 6, the electron transport layer 7, the buffer layer 8, the transparent conductive oxide layer 9, and the antireflection layer, which are stacked in this order.
The manufacturing method of the laminate battery is different from example 1 in that step (4) is not included, and specifically includes the steps of:
(1) Providing a silicon-based cell
The silicon-based battery 1 is a SHJ structure silicon-based battery substrate and comprises a C-Si layer, a double-sided intrinsic amorphous silicon a-Si H (i) layer, a front n-type doped passivation layer, a back p-type doped passivation layer, a back metal oxide conductive layer and a back Ag electrode layer; cutting with laser to obtain 2×2cm 2 Is provided.
(2) Preparation of composite layers
ITO was prepared as a composite layer 2 on a silicon substrate cell 1 using a Physical Vapor Deposition (PVD) method, with a thickness ranging from 1 to 20nm.
(3) Preparation of hole transport layer
And spin-coating OMe-2PACz dimethoxy ethanol solution with the concentration of 1mg/mL on the crystalline silicon cell substrate on which the ITO is deposited to serve as a hole transport layer 3. Specifically, 100 mu L of OMe-2PACz dimethoxy ethanol solution is sucked by a liquid-transferring gun, spin-coated for 30s at a rotating speed of 3000rpm, and immediately placed on a hot table for heating at 100 ℃ for 10min after spin-coating is finished; the thickness of the hole transport layer 3 is 1-5nm.
(4) Preparation of perovskite absorber layer
A perovskite light absorbing layer 5 is prepared in a one-step process on the hole transporting layer 3. Specifically, spin-coating perovskite precursor solution, taking 100 mu L of perovskite precursor solution to drop on a substrate on which a high work function dielectric passivation layer is deposited by a liquid-transferring gun, spin-coating for 50s by using a rotating speed of 3000rpm, and immediately placing on a heat table for heating and annealing at 110 ℃ for 30min after spin-coating, wherein the perovskite comprises Cs 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 ) 3 The precursor solution is PbI 2 /PbBr 2 The mixed solution of/FAI/MABr/CsI (solvent is DMF: DMSO=4:1 mixed solvent, total mass is 1.5 mM/mL). The perovskite absorber layer thickness was about 800nm.
(5) Preparing a second dielectric layer
Preparation of a material PDADI on the perovskite light absorbing layer 5 using solution spin coating 2 Is provided, the second dielectric layer 6 of (a). In which PDADI in solution used in solution spin coating 2 The concentration of (2) was 0.5mg/mL, and the solvent was isopropanol. Specifically, 100. Mu.L of PDADI was taken with a pipette 2 The isopropanol solution is dripped on the substrate for preparing the perovskite light absorption layer, and is spin-coated for 30 seconds at a rotation speed of 5000rpm, and the thickness is 0.5-1nm without treatment after spin-coating is finished.
(6) Preparation of an electron transport layer
Vapor deposition of C60 as electron transport layer 7 on LiF dielectric layer using thermal vapor deposition apparatus at a rate ofThe thickness is 8-20nm.
(7) Preparation of buffer layer
Preparation of SnO on electron transport layer 7 Using an atomic layer vacuum deposition System 2 The buffer layer 8 is deposited at 80 ℃ and has a thickness of 10-15nm.
(8) Preparation of transparent conductive oxide layer
An ITO transparent conductive oxide layer 9 was prepared on the buffer layer 8 using a Physical Vapor Deposition (PVD) system, with a thickness ranging from 30 to 70nm.
(9) Preparation of the back electrode
The back electrode is prepared from Ag with a film thickness of 300-1000nm.
(10) Preparation of an antireflection layer
Preparation of MgF using electron beam thermal evaporation deposition system 2 The thickness of the antireflection layer is 100-130nm.
The relevant parameters of the main dielectric layer materials of the above examples and comparative examples are shown in table 1.
TABLE 1
The laminated solar cells prepared in the above examples and comparative examples were subjected to performance test. The results are shown in Table 2.
TABLE 2
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Claims (12)

1. A perovskite/silicon heterojunction laminated solar cell comprises a silicon substrate cell, a composite layer, a hole transmission layer, a first dielectric layer, a perovskite absorption layer, a second dielectric layer and an electron transmission layer which are laminated in sequence,
wherein the first dielectric layer and the second dielectric layer promote cross-interface transport of carriers.
2. The solar cell of claim 1, wherein dipole moments of the first and second dielectric layer materials are 2D or greater.
3. The perovskite/silicon heterojunction laminated solar cell comprises a silicon substrate cell, a composite layer, a hole transmission layer, a first dielectric layer, a perovskite absorption layer, a second dielectric layer and an electron transmission layer which are laminated in sequence, wherein dipole moments of materials of the first dielectric layer and the second dielectric layer are more than or equal to 2D.
4. A solar cell according to claim 1 or 3, wherein the material of the first dielectric layer is selected from one or more of 4-methoxyphenethyl amine bromide (OMe-PEAI), 4-fluorophenethyl amine iodide (F-PEAI), 4-chlorophenylethyl amine iodide (Cl-PEAI), potassium iodide, potassium chloride.
5. A solar cell according to claim 1 or 3, wherein the material of the second dielectric layer is selected from 1, 3-diaminopropane dihydroiodate (PDADI) 2 ) Ethylenediamine dihydroiodide (EDADI) 2 ) 1, 4-butanediamine hydroiodidate (BDADI) 2 ) 1, 6-hexamethylenediamine Hydroiodidate (HDADI) 2 ) One or two of imidazole hydroiodides (IMI)More than one.
6. A solar cell according to claim 1 or 3, wherein the material of the first dielectric layer is OMe-pei and the material of the second dielectric layer is PDADI 2 。
7. A solar cell according to claim 1 or 3, wherein the thickness of the first dielectric layer is 1-5nm.
8. A solar cell according to claim 1 or 3, wherein the thickness of the second dielectric layer is 0.5-1nm.
9. The solar cell of claim 1 or 3, wherein the first dielectric layer and the second dielectric layer are prepared by solution spin coating.
10. The solar cell of claim 9, wherein when the first dielectric layer is prepared by solution spin coating, a concentration of the material of the first dielectric layer in the solution used is 1-5mg/mL.
11. The solar cell of claim 9, wherein when the second dielectric layer is prepared by solution spin coating, a concentration of the material of the second dielectric layer in the solution used is 0.5-1mg/mL.
12. The solar cell according to claim 1 or 3, wherein the solar cell further comprises a buffer layer and a transparent conductive oxide layer, which are sequentially stacked, on a side of the electron transport layer remote from the silicon substrate cell.
CN202311075783.5A 2023-08-24 2023-08-24 Perovskite/silicon heterojunction stacked solar cell with improved carrier transport properties Pending CN117156886A (en)

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