Preparation method of mixed self-assembly monomolecular layer and perovskite battery

Abstract

The invention discloses a preparation method of a mixed self-assembled monomolecular layer and a perovskite battery. The preparation method comprises the following steps: providing a carrier; a mixed self-assembled monomolecular layer and a perovskite layer are prepared on a carrier, the mixed self-assembled monomolecular layer is located on the surface of the perovskite layer, and the mixed self-assembled monomolecular layer comprises a first self-assembled monomolecular layer and a second self-assembled monomolecular layer, the material of the first self-assembled monomolecular layer and the material of the second self-assembled monomolecular layer have at least one same group. The invention provides a novel method for preparing a mixed self-assembly monomolecular layer, which is beneficial to extraction of charges and inhibition of non-radiative recombination.

Description

Technical Field

[0001] The invention belongs to the technical field of solar energy, and in particular relates to a preparation method of a hybrid self-assembled monolayer and a perovskite battery. Background Art

[0002] Perovskite solar cells (PSCs) have developed rapidly due to their high power conversion efficiency (PCE), simple manufacturing process and high cost-effectiveness. Trans-PSCs currently have a certified PCE of 26.7%, showing great application potential in the global energy system. Despite significant progress in PSCs, the PCE of PSCs has not yet reached the maximum theoretical efficiency defined by the Shockley-Queisser (SQ) limit, which is mainly attributed to defects in perovskite films and corresponding interface defects.

[0003] Currently, most high-performance inverse PSCs are based on self-assembled monolayers (SAMs) as hole-selective layers (HSLs), such as Me-2PACz, Me-4PACz, and MeO-2PACz. Although the dipole moment of the widely used SAMs plays a crucial role in the charge transfer process, it is challenging to achieve defect passivation at the perovskite bottom interface. SAM molecules tend to aggregate due to their amphiphilic nature, which hinders the formation of a high-density monolayer on a fully covered substrate. This phenomenon is not conducive to achieving optimal interfacial contact and crystallization of perovskite films.

[0004] In the prior art, the SAM coverage is improved by using a mixed SAM strategy of MeO-2PACz and perfluorotripropylamine (FC-3283) to accelerate carrier transport, promote perovskite growth, adjust surface energy levels and inhibit non-radiative recombination; or 6dPA is added to the Me-4PACz solution to improve the wettability of the Me-4PACz hole-selective monolayer, thereby significantly improving the device performance; or 2PACz is used as the initial HSL, and then a layer of Me-4PACz is spin-coated for modification. This interface engineering changes the surface potential distribution of 2PACz on the ITO surface, improves the quality of the perovskite film, and effectively inhibits non-radiative recombination. By preparing a mixed SAM, the coverage of the SAM on the conductive substrate can be greatly improved, hole extraction can be enhanced, and non-radiative recombination at the interface can be inhibited. At the same time, the growth of the perovskite film can be promoted, the internal stress of the perovskite can be released, and the crystallization quality of the perovskite can be improved.

[0005] However, in the prior art, mixed SAM is prepared by a traditional one-step method, that is, one or more SAM molecules are mixed and prepared by spin coating, which cannot achieve the passivation effect inside the perovskite and will cause random arrangement of one or more SAMs, which is not conducive to charge extraction and suppression of non-radiative recombination.

[0006] Therefore, in view of the above technical problems, it is necessary to provide a method for preparing a hybrid self-assembled monolayer and a perovskite battery. Summary of the invention

[0007] The object of the present invention is to provide a method for preparing a hybrid self-assembled monolayer and a perovskite battery, which can promote charge extraction and inhibit non-radiative recombination.

[0008] In order to achieve the above purpose, the technical solution provided by an embodiment of the present invention is as follows:

[0009] A method for preparing a hybrid self-assembled monolayer, the method comprising the following steps:

[0010] Provide a carrier;

[0011] A hybrid self-assembled monolayer and a perovskite layer are prepared on a carrier, wherein the hybrid self-assembled monolayer is located on the surface of the perovskite layer, and the hybrid self-assembled monolayer includes a first self-assembled monolayer and a second self-assembled monolayer, wherein the material of the first self-assembled monolayer and the material of the second self-assembled monolayer have at least one identical group.

[0012] In one embodiment, preparing a hybrid self-assembled monolayer and a perovskite layer on a carrier comprises the following steps:

[0013] preparing a first self-assembled monolayer on a support;

[0014] A second self-assembled monolayer and a perovskite layer are prepared on the first self-assembled monolayer, wherein the second self-assembled monolayer is formed on the lower surface of the perovskite layer, and the second self-assembled monolayer is mixed with the first self-assembled monolayer to form a mixed self-assembled monolayer.

[0015] In one embodiment, the carrier is a conductive substrate.

[0016] In one embodiment, preparing a hybrid self-assembled monolayer and a perovskite layer on a carrier comprises the following steps:

[0017] Preparing a perovskite layer and a second self-assembled monolayer on a carrier, wherein the second self-assembled monolayer is formed on an upper surface of the perovskite layer;

[0018] A first self-assembled monolayer is prepared on the perovskite layer, and the first self-assembled monolayer is mixed with the second self-assembled monolayer to form a mixed self-assembled monolayer.

[0019] In one embodiment, the carrier is a conductive substrate and an electron transport layer located on the conductive substrate.

[0020] In one embodiment, the second self-assembled monolayer is partially located in the perovskite layer.

[0021] In one embodiment, the material of the second self-assembled monolayer is a combination of one or more dimethylacridine-based self-assembled monolayer materials; and / or,

[0022] The general structural formula of the material of the perovskite layer is ABX 3 structure.

[0023] In one embodiment, the material of the second self-assembled monolayer is DMAcPA, and the material of the first self-assembled monolayer is MeO-2PACz; and / or,

[0024] The material of the perovskite layer is Cs x FA y MA 1-x-y Pb(I z Br 3-z ).

[0025] In one embodiment, preparing the second self-assembled monolayer and the perovskite layer comprises the following steps:

[0026] Providing a perovskite precursor solution, and adding a second self-assembled monolayer material to the perovskite precursor solution;

[0027] The perovskite layer is prepared by an anti-solvent extraction method, and the material of the second self-assembled monolayer in the perovskite precursor solution is squeezed onto the surface of the perovskite layer to form a second self-assembled monolayer.

[0028] Another embodiment of the present invention provides a technical solution as follows:

[0029] A perovskite battery, comprising a hybrid self-assembled monolayer prepared according to the above preparation method.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] The present invention proposes a novel method for preparing a hybrid self-assembled monolayer, in which a second self-assembled monolayer is formed on the surface of a perovskite layer by an anti-solvent extraction method, and is blended with the original first self-assembled monolayer to form a hybrid self-assembled monolayer, which is beneficial to charge extraction and suppression of non-radiative recombination, and can also passivate defects inside the perovskite, thereby improving the performance of the perovskite battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments recorded in the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0033] Figure 1 It is a schematic structural diagram of a self-assembled monolayer and a perovskite layer stacked on a conductive substrate in Comparative Example 1 of the present invention;

[0034] Figure 2 It is a schematic flow chart of the preparation method of the hybrid self-assembled monolayer in Embodiment 1 of the present invention;

[0035] Figure 3 It is a schematic structural diagram of a hybrid self-assembled monolayer and a perovskite layer stacked on a conductive substrate in Embodiment 1 of the present invention;

[0036] Figure 4 It is a schematic structural diagram of the perovskite solar cell in Embodiment 1 of the present invention;

[0037] Figure 5 It is a schematic structural diagram of the perovskite solar cell in Embodiment 2 of the present invention.

[0038] Main reference numeral description:

[0039] 1 - Conductive substrate, 11 - Glass substrate, 12 - Indium tin oxide transparent conductive thin film, 2 - Hole transport layer, 3 - Perovskite layer, 4 - Electron transport layer, 5 - Electrode layer, 6 - Hole blocking layer. Detailed implementation manners

[0040] In order to enable those skilled in the art to better understand the technical solutions in the present invention, the following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0041] The present invention discloses a preparation method of a hybrid self-assembled monolayer, including the following steps:

[0042] Provide a carrier;

[0043] A mixed self-assembled monolayer and a perovskite layer are prepared on a carrier. The mixed self-assembled monolayer is located on the surface of the perovskite layer. The mixed self-assembled monolayer includes a first self-assembled monolayer and a second self-assembled monolayer. The material of the first self-assembled monolayer and the material of the second self-assembled monolayer have at least one identical group.

[0044] The present invention is further described below with reference to specific examples.

[0045] Comparative Example 1:

[0046] Ginseng Figure 1 As shown, the self-assembled monolayer in this comparative example is a single-layer self-assembled monolayer, the self-assembled monolayer is prepared on a conductive substrate, and the perovskite layer is located on the single-layer self-assembled monolayer.

[0047] Since the SAM molecules are amphiphilic and tend to aggregate, it is difficult for the single-layer self-assembled monolayer in this embodiment to form a high-density monolayer that completely covers the conductive substrate, thereby generating vacancy defects, affecting the crystal growth and interface contact of the perovskite layer, and non-radiative recombination losses at the interface.

[0048] Embodiment 1:

[0049] Ginseng Figure 2 As shown, the method for preparing the hybrid self-assembled monolayer in this embodiment includes the following steps:

[0050] Provide a carrier;

[0051] A mixed self-assembled monolayer and a perovskite layer are prepared on a carrier. The mixed self-assembled monolayer is located on the surface of the perovskite layer. The mixed self-assembled monolayer includes a first self-assembled monolayer and a second self-assembled monolayer. The material of the first self-assembled monolayer and the material of the second self-assembled monolayer have at least one identical group.

[0052] Specifically, preparing the second self-assembled monolayer and the perovskite layer comprises the following steps:

[0053] Providing a perovskite precursor solution, and adding a second self-assembled monolayer material to the perovskite precursor solution;

[0054] The perovskite layer is prepared by an anti-solvent extraction method, and the material of the second self-assembled monolayer in the perovskite precursor solution is squeezed to the surface of the perovskite layer to form a second self-assembled monolayer.

[0055] The material of the second self-assembled monolayer is a combination of one or more dimethylacridine-based self-assembled monolayer materials, or organic molecules that can be squeezed out to the perovskite interface during the anti-solvent extraction process.

[0056] Specifically, the material of the first self-assembled monolayer in this embodiment includes but is not limited to MeO-2PACz, the chemical formula of which is The material of the second self-assembled monolayer includes but is not limited to DMAcPA, the chemical formula of which is

[0057] It should be understood that the material of the first self-assembled monolayer and the material of the second self-assembled monolayer should have at least one common group in order to achieve blending of the first self-assembled monolayer and the second self-assembled monolayer.

[0058] The general structural formula of the material of the perovskite layer in this embodiment is ABX 3 structure.

[0059] Specifically, the material of the perovskite layer in this embodiment is Cs x FA y MA 1-x-y Pb(I z Br 3-z ).

[0060] More specifically, the solutes of the perovskite precursor solution in this embodiment include cesium iodide (CsI), methylammonium bromide (MABr), methylammonium chloride (MACl), lead bromide (PbBr 2 ), lead iodide (PbI 2 ), formamidine iodide (FAI), the material of the perovskite layer is (FA 0.95 MA 0.05 ) 0.95 Cs 0.05 Pb(I 0.95 Br 0.05 ) 3 .

[0061] In this embodiment, by adding the material of the second self-assembled monolayer to the perovskite precursor solution, during the anti-solvent extraction crystallization process, this SAM molecule can be squeezed to the bottom of the perovskite layer, thereby blending with the first self-assembled monolayer to form a mixed self-assembled monolayer.

[0062] Combination Figure 3 As shown, compared with Comparative Example 1, the hybrid self-assembled monolayer in this embodiment can fill the vacancies. At the same time, the second self-assembled monolayer is partially located in the perovskite layer, which has a passivation effect on the grain boundary defects inside the perovskite.

[0063] Ginseng Figure 4 As shown, the perovskite cell in this embodiment is a trans-structured perovskite solar cell, which includes a conductive substrate 1, a hole transport layer 2, a perovskite layer 3, an electron transport layer 4 and an electrode layer 5 from bottom to top.

[0064] Among them, the conductive substrate 1 is a glass substrate 11 and an indium tin oxide (ITO) transparent conductive film 12 stacked on the glass substrate, the hole transport layer 2 is a mixed self-assembled monolayer, the material of the electron transport layer 4 includes but is not limited to fullerene derivative (PCBM) material, and the electrode layer is a silver electrode.

[0065] In this embodiment, the carrier is a conductive substrate 1, and the preparation of a hybrid self-assembled monolayer and a perovskite layer 3 on the carrier includes the following steps:

[0066] preparing a first self-assembled monolayer on a support;

[0067] A perovskite layer 3 and a second self-assembled monolayer are prepared on the first self-assembled monolayer. The second self-assembled monolayer is formed on the lower surface of the perovskite layer. The second self-assembled monolayer is mixed with the first self-assembled monolayer to form a mixed self-assembled monolayer as a hole transport layer 2 of the perovskite battery.

[0068] Exemplarily, the perovskite cell in this embodiment further includes a hole blocking layer 6 located between the electron transport layer 4 and the electrode layer 5 , and the material of the hole blocking layer 6 is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) material.

[0069] It is worth noting that in this embodiment, the hybrid self-assembled monolayer is directly used as the hole transport layer in the perovskite cell. In many other embodiments, it can also be used only as an interface modification layer. The perovskite cell includes but is not limited to the structure in this embodiment. The perovskite cell can be a single-junction or multi-junction perovskite cell with a variety of band gaps.

[0070] Embodiment 2:

[0071] The preparation method of the hybrid self-assembled monolayer in this embodiment is substantially the same as that in Embodiment 1, except that the perovskite cell in this embodiment is a perovskite cell with a formal structure.

[0072] Ginseng Figure 5 As shown, the perovskite cell in this embodiment includes a conductive substrate 1, an electron transport layer 4, a perovskite layer 3, a hole transport layer 2 and an electrode layer 5 from bottom to top, and the hybrid self-assembled monolayer directly serves as the hole transport layer 2 of the perovskite cell.

[0073] In this embodiment, the carrier is a conductive substrate 1 and an electron transport layer 4 located on the conductive substrate 1, and the preparation of a hybrid self-assembled monolayer and a perovskite layer on the carrier includes the following steps:

[0074] A perovskite layer and a second self-assembled monolayer are prepared on a carrier, wherein the second self-assembled monolayer is formed on an upper surface of the perovskite layer;

[0075] A first self-assembled monolayer is prepared on the perovskite layer, and the first self-assembled monolayer is mixed with the second self-assembled monolayer to form a mixed self-assembled monolayer as the hole transport layer 2 of the perovskite battery.

[0076] Exemplarily, a hole blocking layer 6 is provided between the conductive substrate 1 and the electron transport layer 4 in this embodiment.

[0077] It can be seen from the above technical solution that the present invention has the following beneficial effects:

[0078] The present invention proposes a novel method for preparing a hybrid self-assembled monolayer, in which a second self-assembled monolayer is formed on the surface of a perovskite layer by an anti-solvent extraction method, and is blended with the original first self-assembled monolayer to form a hybrid self-assembled monolayer, which is beneficial to charge extraction and suppression of non-radiative recombination, and can also passivate defects inside the perovskite, thereby improving the performance of the perovskite battery.

[0079] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations falling within the meaning and scope of the equivalent elements of the claims be included in the invention. Any reference numeral in a claim should not be considered as limiting the claim to which it relates.

[0080] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A method for preparing a hybrid self-assembled monolayer, characterized in that: The preparation method comprises the following steps: Provide a carrier; A hybrid self-assembled monolayer and a perovskite layer are prepared on a carrier, wherein the hybrid self-assembled monolayer is located on the surface of the perovskite layer, and the hybrid self-assembled monolayer includes a first self-assembled monolayer and a second self-assembled monolayer, wherein the material of the first self-assembled monolayer and the material of the second self-assembled monolayer have at least one identical group.

2. The method for preparing a hybrid self-assembled monolayer according to claim 1, characterized in that: The preparation of a hybrid self-assembled monolayer and a perovskite layer on a support comprises the following steps: preparing a first self-assembled monolayer on a support; A second self-assembled monolayer and a perovskite layer are prepared on the first self-assembled monolayer, wherein the second self-assembled monolayer is formed on the lower surface of the perovskite layer, and the second self-assembled monolayer is mixed with the first self-assembled monolayer to form a mixed self-assembled monolayer.

3. The method for preparing a hybrid self-assembled monolayer according to claim 2, characterized in that: The carrier is a conductive substrate.

4. The method for preparing a hybrid self-assembled monolayer according to claim 1, characterized in that: The preparation of a hybrid self-assembled monolayer and a perovskite layer on a support comprises the following steps: Preparing a perovskite layer and a second self-assembled monolayer on a carrier, wherein the second self-assembled monolayer is formed on an upper surface of the perovskite layer; A first self-assembled monolayer is prepared on the perovskite layer, and the first self-assembled monolayer is mixed with the second self-assembled monolayer to form a mixed self-assembled monolayer.

5. The method for preparing a hybrid self-assembled monolayer according to claim 4, characterized in that: The carrier is a conductive substrate and an electron transport layer located on the conductive substrate.

6. The method for preparing a hybrid self-assembled monolayer according to claim 1, characterized in that: The second self-assembled monolayer is partially located in the perovskite layer.

7. The method for preparing a hybrid self-assembled monolayer according to claim 1, characterized in that: The material of the second self-assembled monolayer is a combination of one or more dimethylacridine-based self-assembled monolayer materials; and / or, The general structural formula of the material of the perovskite layer is ABX3 structure.

8. The method for preparing a hybrid self-assembled monolayer according to claim 1, characterized in that: The material of the second self-assembled monolayer is DMAcPA, and the material of the first self-assembled monolayer is MeO-2PACz; and / or, The material of the perovskite layer is Cs x FA y MA 1-x-y Pb(I z Br 3-z ).

9. The method for preparing a hybrid self-assembled monolayer according to claim 2 or 4, characterized in that: The preparation of the second self-assembled monolayer and the perovskite layer comprises the following steps: Providing a perovskite precursor solution, and adding a second self-assembled monolayer material to the perovskite precursor solution; The perovskite layer is prepared by an anti-solvent extraction method, and the material of the second self-assembled monolayer in the perovskite precursor solution is squeezed onto the surface of the perovskite layer to form a second self-assembled monolayer.

10. A perovskite battery, characterized in that: The perovskite cell comprises a hybrid self-assembled monolayer prepared by the preparation method according to any one of claims 1 to 9.

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