Composite self-assembly monomolecular layer and application thereof, solar cell module and preparation method thereof

Abstract

The invention relates to the technical field of perovskite solar cells, and provides a composite self-assembled monomolecular layer, application of the composite self-assembled monomolecular layer, a solar cell module and a preparation method of the solar cell module. The first composite self-assembly monomolecular layer and the second composite self-assembly monomolecular layer are combined and designed into a double-layer structure; the first composite self-assembly monomolecular layer is prepared from a first composite self-assembly monomolecular layer material, and the second composite self-assembly monomolecular layer is prepared from a second composite self-assembly monomolecular layer material; or, a composite self-assembled monomolecular mixed layer, the composite self-assembled monomolecular mixed layer being prepared by mixing a first composite self-assembled monomolecular layer material and a second composite self-assembled monomolecular layer material. A composite SAMs functional structure formed by multiple layers / multiple materials is adopted, the SAMs are effectively induced to form specific orientation arrangement in the anchoring process through the pi-pi stacking effect, and the passivation effect is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of perovskite solar cells, and in particular to a composite self-assembled monolayer and its application, a solar cell component and its preparation method. Background Art

[0002] In the research of perovskite solar cells (PSCs), interface engineering is one of the important strategies to improve device efficiency and stability. Self-assembled monolayers (SAMs) have been widely used in recent years to modify the perovskite / charge transport layer interface.

[0003] Although SAMs have shown great potential in improving the performance of PSCs, their practical application still faces many key issues, mainly reflected in the following aspects:

[0004] 1. SAMs molecular design issues: The molecular structure of SAMs directly affects its adsorption capacity and energy level arrangement on the perovskite surface. Although the currently commonly used SAMs molecules (such as carboxylic acids, phosphoric acids, silanes, etc.) can effectively passivate perovskite surface defects, there is still uncertainty about the matching of their energy levels with the perovskite or charge transport layer. For example: 1) Insufficient energy level offset: Although some SAMs (such as 4-fluorobenzoic acid) can improve hole transport, the HOMO energy level does not match the perovskite valence band (VB) sufficiently, resulting in reduced interfacial charge extraction efficiency. 2) Limitations in molecular dipole regulation: The dipole moment of SAMs is crucial to the bending of the perovskite surface energy band, but the dipole direction and strength of the existing molecular library are difficult to precisely control, affecting the improvement of the open circuit voltage (Voc). In addition, the chemical bonding mechanism between the functional groups at the end of the SAMs molecules (such as -COOH, -PO3H2) and the perovskite surface is still unclear, which may lead to unstable passivation effect or intensified interfacial recombination.

[0005] 2. SAMs film uniformity and coverage issues: The film quality of SAMs directly affects the interface passivation effect and charge transfer performance. However, due to the heterogeneity of the chemical properties of the substrate and the perovskite surface (such as the type and density of dangling bonds, uneven ion distribution, etc.), SAMs are prone to the following problems during solution processing: 1) Non-uniform adsorption: Insufficient adsorption sites of SAMs molecules on transparent metal oxide conductive substrates (TCO), nickel oxide (NiOx) or perovskite grain boundaries / defect sites may lead to low local coverage, forming unpassivated areas and becoming non-radiative recombination centers. 2) Multi-molecular layer aggregation: SAMs in some polar solvents (such as ethanol and isopropanol) may form multi-layer stacking structures in the film due to molecular agglomeration, increasing the interface resistance. 3) Substrate dependence: The crystal orientation of different perovskite components (such as FAPbI3 and MAPbI3) has significant differences in the adsorption energy of SAMs, resulting in poor universality of the same SAMs material for different perovskite films.

[0006] 3. Challenges in the long-term stability of SAMs: The stability of perovskite devices under humidity, heat, light or electric fields is closely related to the durability of the SAMs layer. Current research has found that: 1) Thermodynamic instability: Some SAMs (such as thiols) break the chemical bonds formed with TCO or perovskite at high temperatures (≥85°C), and are easily chemically desorbed from the surface, resulting in regeneration of interface defects and device failure. 2) Photochemical degradation: Ultraviolet light may trigger photooxidation of SAMs molecules (such as those containing benzene ring structures), destroying their passivation function. 3) Ion migration-induced failure: The migration of I- or MA+ in the perovskite under the action of an electric field may penetrate the SAMs layer, react with the charge transport layer or electrode material, and accelerate the degradation of device performance.

[0007] 4. Process compatibility issues in large-scale preparation: The industrial application of SAMs needs to solve the following process bottlenecks: 1) Narrow solution processing window: The adsorption time, concentration and solvent selection of SAMs are extremely sensitive to the film quality, and are difficult to be compatible with large-area coating (such as slit coating and roll-to-roll process). 2) Poor batch repeatability: SAMs generally require low-concentration solutions to ensure the effect of interface treatment, but in large-area coating or scraping processes, it is difficult to ensure the uniformity of the SAMs layer on a large-area substrate, affecting the device yield. 3) Cost and environmental protection: The synthesis steps of some high-performance SAMs (such as fluorine-containing compounds) are complex and may involve toxic solvents, which do not meet the requirements of green manufacturing.

[0008] The above problems seriously restrict the further promotion of SAMs in efficient and stable perovskite photovoltaic devices. It is urgent for technicians in this field to design a composite self-assembled monolayer to solve the above problems. Summary of the Invention

[0009] In order to solve the above technical problems, the present invention provides a composite self-assembled monolayer, comprising:

[0010] a first composite self-assembled monolayer and a second composite self-assembled monolayer, wherein the first composite self-assembled monolayer and the second composite self-assembled monolayer are combined to form a double-layer structure; the first composite self-assembled monolayer is prepared from the first composite self-assembled monolayer material, and the second composite self-assembled monolayer is prepared from the second composite self-assembled monolayer material;

[0011] Or, a composite self-assembled monomolecular mixed layer, wherein the composite self-assembled monomolecular mixed layer is prepared by mixing a first composite self-assembled monomolecular layer material and a second composite self-assembled monomolecular layer material.

[0012] Furthermore, the double-layer structure includes a first composite self-assembled monolayer stacked on an upper layer of a second composite self-assembled monolayer, or a first composite self-assembled monolayer stacked on a lower layer of the second composite self-assembled monolayer.

[0013] Furthermore, the first composite self-assembled monolayer material includes one or more combinations of 4PACz, Me-4PACz, MeO-4PACz, 2PACz, Me-2PACz, and MeO-2PACz.

[0014] Furthermore, the second composite self-assembled monolayer material includes one or more phosphate polyesters and / or sulfonic acid polyesters including triphenyl sulfonate (TSP) and triphenyl phosphate (THP).

[0015] The second aspect of the present invention provides an application of a composite self-assembled monolayer in perovskite photovoltaic technology.

[0016] The third aspect of the present invention provides a solar cell assembly, comprising a transparent conductive metal oxide layer, a hole transport layer, a composite self-assembled monolayer, a perovskite active layer, an electron transport layer and an electrode layer sequentially arranged on a substrate.

[0017] Furthermore, it includes a transparent conductive metal oxide layer, a hole transport layer, a first composite self-assembled monolayer, a second composite self-assembled monolayer, a perovskite active layer, an electron transport layer and an electrode layer which are sequentially arranged on a substrate.

[0018] Furthermore, it includes a transparent conductive metal oxide layer, a hole transport layer, a second composite self-assembled monolayer, a first composite self-assembled monolayer, a perovskite active layer, an electron transport layer and an electrode layer which are sequentially arranged on a substrate.

[0019] Furthermore, it includes a transparent conductive metal oxide layer, a hole transport layer, a composite self-assembled monomolecular mixed layer, a perovskite active layer, an electron transport layer and an electrode layer which are sequentially arranged on a substrate.

[0020] A fourth aspect of the present invention provides a method for preparing a solar cell module, the method comprising:

[0021] (1.1) Preparation of a transparent conductive metal oxide layer: A layer of transparent conductive metal oxide approximately 100 nanometers thick is deposited on the substrate surface by a combination of one or more coating processes selected from magnetron sputtering, reactive plasma sputtering, electron beam coating, atomic layer deposition, and chemical vapor deposition. After coating, the sample is annealed at 200°C for 5 minutes on a heating table or in a vacuum drying oven and then cooled to room temperature to obtain a transparent metal oxide layer. The transparent conductive metal oxide layer includes one or more combinations of tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), indium phosphate (IWO), and indium zonate (IZO).

[0022] (1.2) Preparation of hole transport layer: Deposit a layer of hole transport material with a thickness of approximately 10 nm on the surface of the transparent conductive metal oxide layer by one or more combinations of spin coating, doctor blade coating, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition methods; wherein the hole transport material is one or more combinations of nickel oxide (NiOx), polytriarylamine (PTAA), cuprous thiocyanate (CuSCN) (poly(3,4-ethylenedioxythiophene):polystyrene sulfonate) (PEDOT:PSS), poly(3-hexylthiophene) (P3HT), and molybdenum disulfide (MoS2);

[0023] (1.3) Preparation of a first composite self-assembled monolayer: depositing a first self-assembled monolayer material layer having a thickness of about 1-3 nm on the surface of the hole transport layer by one or more of spin coating, doctor blade coating, slit coating, and screen printing; wherein the first self-assembled monolayer material layer comprises one or more of 4PACz, Me-4PACz, MeO-4PACz, 2PACz, Me-2PACz, and MeO-2PACz;

[0024] (1.4) Preparation of a second composite self-assembled monolayer: Depositing a layer of a second self-assembled monolayer material having a thickness of approximately 1-3 nm on the surface of the first composite self-assembled monolayer by one or more of spin coating, doctor blade coating, slit coating, and screen printing; wherein the second composite self-assembled monolayer comprises one or more phosphate polyesters and / or sulfonic acid polyesters including TSP and THP;

[0025] (1.5) Preparation of perovskite active layer: Depositing a perovskite precursor film on the surface of the second composite self-assembled monolayer by one or more of spin coating, doctor blading, slit coating, screen printing, and thermal evaporation coating methods. The film is then subjected to solvent extraction, wherein the extraction treatment is one or more of vacuum chamber drying (VCD), air knife blowing, or anti-solvent method. Finally, the film is annealed on a heating table or in an oven at 100-200°C for 10-30 minutes to obtain a perovskite film having a thickness of approximately 1 μm. The perovskite film comprises one or more of formamidine-based perovskite, methylamine-based perovskite, and cesium-based perovskite.

[0026] (1.6) Electron transport layer preparation: A layer of electron transport material is formed on the surface of the perovskite active layer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition. The electron transport material includes one or more of tin oxide (SnOx), fullerene (C60), titanium oxide (TiO2), zinc oxide (ZnO), and fullerene derivatives (PCBM).

[0027] (1.7) Electrode layer preparation: A layer of electrode material approximately 100 nanometers thick is prepared on the surface of the electron transport layer by one or more of the following methods: thermal evaporation, magnetron sputtering, and plasma deposition. The electrode material comprises one or more of gold, silver, copper, and transparent electrodes such as indium tin oxide (ITO), fluorine-doped tin oxide (FTO), indium tungsten oxide (IWO), and indium zinc oxide (IZO).

[0028] A fifth aspect of the present invention provides a method for preparing a solar cell module, the method comprising:

[0029] (2.1) Preparation of a transparent conductive metal oxide layer: A layer of transparent conductive metal oxide approximately 100 nanometers thick is deposited on the substrate surface by a combination of one or more coating processes selected from magnetron sputtering, reactive plasma sputtering, electron beam coating, atomic layer deposition, and chemical vapor deposition. After coating, the sample is annealed at 200°C for 5 minutes on a heating table or in a vacuum drying oven and then cooled to room temperature to obtain a transparent metal oxide layer. The transparent conductive metal oxide layer includes one or more combinations of tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), indium phosphate (IWO), and indium zonate (IZO).

[0030] (2.2) Preparation of hole transport layer: Deposit a layer of hole transport material with a thickness of approximately 10 nm on the surface of the transparent conductive metal oxide layer by one or more combinations of spin coating, doctor blading, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition methods; wherein the hole transport material is one or more combinations of nickel oxide (NiOx), polytriarylamine (PTAA), cuprous thiocyanate (CuSCN) (poly(3,4-ethylenedioxythiophene):polystyrene sulfonate) (PEDOT:PSS), poly(3-hexylthiophene) (P3HT), and molybdenum disulfide (MoS2);

[0031] (2.3) Preparation of a second composite self-assembled monolayer: Depositing a second self-assembled monolayer material layer having a thickness of approximately 1-3 nm on the surface of the hole transport layer by one or more of spin coating, doctor blade coating, slit coating, and screen printing; wherein the second self-assembled monolayer material layer comprises one or more phosphate polyesters and / or sulfonic acid polyesters including TSP and THP;

[0032] (2.4) Preparation of a first composite self-assembled monolayer: depositing a first self-assembled monolayer material layer having a thickness of about 1-3 nm on the surface of the second composite self-assembled monolayer by one or more of spin coating, doctor blade coating, slit coating, and screen printing; wherein the first self-assembled monolayer material layer comprises one or more of 4PACz, Me-4PACz, MeO-4PACz, 2PACz, Me-2PACz, and MeO-2PACz;

[0033] (2.5) Preparation of the perovskite active layer: Depositing a perovskite precursor film on the surface of the first composite self-assembled monolayer by one or more of spin coating, doctor blading, slit coating, screen printing, and thermal evaporation coating methods. The film is then subjected to solvent extraction, wherein the extraction treatment is one or more of vacuum chamber drying (VCD), air knife blowing, or anti-solvent method. Finally, the film is annealed on a heating plate or in an oven at 100-200°C for 10-30 minutes to obtain a perovskite film having a thickness of approximately 1 μm. The perovskite film comprises one or more of formamidinium-based perovskite, methylamine-based perovskite, and cesium-based perovskite.

[0034] (2.6) Electron transport layer preparation: A layer of electron transport material is formed on the surface of the perovskite active layer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition. The electron transport material includes one or more of tin oxide (SnOx), fullerene (C60), titanium oxide (TiO2), zinc oxide (ZnO), and fullerene derivatives (PCBM).

[0035] (2.7) Electrode layer preparation: A layer of electrode material approximately 100 nanometers thick is prepared on the surface of the electron transport layer by one or more of thermal evaporation, magnetron sputtering, and plasma deposition methods; wherein the electrode material comprises one or more of gold, silver, copper, and transparent electrodes such as indium tin oxide (ITO), fluorine-doped tin oxide (FTO), indium tungsten oxide (IWO), and indium zinc oxide (IZO).

[0036] A sixth aspect of the present invention provides a method for preparing a solar cell module, the method comprising:

[0037] (3.1) Preparation of a transparent conductive metal oxide layer: A layer of transparent conductive metal oxide approximately 100 nanometers thick is deposited on the substrate surface by a combination of one or more coating processes selected from magnetron sputtering, reactive plasma sputtering, electron beam coating, atomic layer deposition, and chemical vapor deposition. After coating, the sample is annealed at 200°C for 5 minutes in a heating table or vacuum drying oven and then cooled to room temperature to obtain a transparent metal oxide layer. The transparent conductive metal oxide layer includes one or more combinations of tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), indium phosphate (IWO), and indium zonate (IZO).

[0038] (3.2) Preparation of hole transport layer: Deposit a layer of hole transport material with a thickness of approximately 10 nm on the surface of the transparent conductive metal oxide layer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition. The hole transport material is one or more of nickel oxide (NiOx), polytriarylamine (PTAA), cuprous thiocyanate (CuSCN) (poly(3,4-ethylenedioxythiophene):polystyrene sulfonate) (PEDOT:PSS), poly(3-hexylthiophene) (P3HT), and molybdenum disulfide (MoS2).

[0039] (3.3) Preparation of a composite self-assembled monomolecular mixed layer: a first self-assembled monomolecular material and a second self-assembled monomolecular material are mixed and dissolved in water or an alcohol solvent by blending and blending to form a mixed solution; a layer of self-assembled monomolecular composite material with a thickness of about 1-3 nm is deposited on the surface of the hole transport layer by one or more combinations of spin coating, blade coating, slit coating, and screen printing; wherein the first self-assembled monomolecular material comprises one or more of 4PACz, Me-4PACz, MeO-4PACz, 2PACz, Me-2PACz, and MeO-2PACz; and the second self-assembled monomolecular material comprises one or more of phosphate polyesters and / or sulfonic acid polyesters including TSP and THP;

[0040] (3.4) Preparation of perovskite active layer: Depositing a perovskite precursor film on the surface of the composite self-assembled monolayer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, or thermal evaporation. The film is then subjected to solvent extraction, wherein the extraction is one or more of vacuum chamber drying (VCD), air knife blowing, or anti-solvent method. Finally, the film is annealed on a heating plate or in an oven at 100-200°C for 10-30 minutes to obtain a perovskite film having a thickness of approximately 1 μm. The perovskite film comprises one or more of formamidinium-based perovskite, methylamine-based perovskite, and cesium-based perovskite.

[0041] (3.5) Electron transport layer preparation: Forming a layer of electron transport material on the surface of the perovskite active layer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition; wherein the electron transport material includes one or more of tin oxide (SnOx), fullerene (C60), titanium oxide (TiO2), zinc oxide (ZnO), and fullerene derivatives (PCBM);

[0042] (3.6) Electrode layer preparation: A layer of electrode material approximately 100 nanometers thick is prepared on the surface of the electron transport layer by one or more of thermal evaporation, magnetron sputtering, and plasma deposition methods; wherein the electrode material comprises one or more of gold, silver, copper, and transparent electrodes such as indium tin oxide (ITO), fluorine-doped tin oxide (FTO), indium tungsten oxide (IWO), and indium zinc oxide (IZO).

[0043] The present invention has the following beneficial effects:

[0044] (1) The present invention designs a new self-assembled monolayer, which is designed by combining a first composite self-assembled monolayer and a second composite self-assembled monolayer, wherein the first composite self-assembled monolayer and the second composite self-assembled monolayer are designed to form a double-layer structure; or a composite self-assembled monolayer material and a second composite self-assembled monolayer material are mixed to prepare a composite self-assembled monolayer, and a composite SAMs functional structure formed by multiple layers / multiple materials is adopted, and a π-π stacking effect is used to effectively induce SAMs to form a specific orientation arrangement during the anchoring process, thereby improving the passivation effect; the SAMs in the composite self-assembled monolayer contain carbazole groups and phosphate groups, wherein the phosphate groups are anchored to Ni vacancies in NiOx, and the carbazole groups form hydrogen bonds or van der Waals forces with perovskite, thereby effectively enhancing the stable chemical bonding between SAMs and the hole transport layer and perovskite, reducing physical adsorption with smaller forces, and enhancing the thermal stability of SAMs;

[0045] (2) The molecular end groups of the composite self-assembled monolayer of the present invention can selectively passivate vacancy defects on the surface of NiOx and perovskite, thereby increasing the open circuit voltage (Voc) and fill factor (FF) and effectively reducing the non-radiative recombination of carriers in the component;

[0046] (3) The dipole moments of the bottom SAMs and the upper SAMs in the double-layer structure of the present invention are independently controllable in size and direction, and can be vertically superimposed. By changing the combination and thickness of different layers of SAMs, the gradient regulation of energy levels can be achieved. The dipole moments of different terminal groups (-CH3, -NH2, -COOH) of different SAMs in the composite self-assembled monomolecular mixed layer can be mixed and superimposed to form an energy level slope. By changing the ratio of different types of SAMs, the energy level structure can be continuously and controllably adjusted. Therefore, the energy band arrangement at the perovskite / charge transport layer interface can be precisely controlled to reduce the charge extraction barrier.

[0047] (4) The composite self-assembled monolayer of the present invention has a large steric hindrance, which ensures that the SAMs are evenly dispersed on the surface of the hole transport layer and reduces the problem of uneven perovskite film formation caused by the agglomeration of the SAMs themselves, providing a good growth template for perovskite; it can meet the process requirements of film uniformity of <5% for large-area components such as slit coating and blade coating;

[0048] (5) In the present invention, when preparing the composite self-assembled monolayer, the first composite self-assembled monolayer material and the second composite self-assembled monolayer material are mixed and dissolved in water or an alcohol solvent. No toxic or harmful solvents are involved in the production process, which meets the requirements of green manufacturing. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 It is a schematic structural diagram of the solar cell assembly in the present invention.

[0050] Figure 2 Schematic diagram of the structure of the solar cell assembly in Example 1.

[0051] Figure 3 Schematic diagram of the structure of the solar cell assembly in Example 2.

[0052] Figure 4 Schematic diagram of the structure of the solar cell assembly in Example 3.

[0053] Figure 5 This is a schematic structural diagram of the solar cell assembly in Comparative Example 1.

[0054] Figure 6 This is a comparison chart of the normalized photoelectric conversion efficiency of the solar cells prepared in Example 1 and Comparative Example 1 subjected to a thermal stability test.

[0055] Figure 7This is a comparison chart of the normalized photoelectric conversion efficiency of the solar cell modules prepared in Examples 1 to 3 after encapsulation and subjected to 85° C. / 85% humidity pressure testing. DETAILED DESCRIPTION

[0056] The technical solution of the present invention is further described in detail below in conjunction with specific embodiments, but this embodiment is not intended to limit the present invention. All similar structures and similar variations of the present invention should be included in the scope of protection of the present invention. The semicolons in the present invention represent the relationship of and, and the English letters in the present invention are case-sensitive.

[0057] like Figure 1 As shown, the present invention provides a composite self-assembled monolayer 1, comprising:

[0058] A first composite self-assembled monolayer 11 and a second composite self-assembled monolayer 12 are combined to form a bilayer structure; the bilayer structure includes the first composite self-assembled monolayer 11 stacked on the upper layer of the second composite self-assembled monolayer 12, or the first composite self-assembled monolayer 11 stacked on the lower layer of the second composite self-assembled monolayer 12. The first composite self-assembled monolayer 11 is prepared from a first composite self-assembled monolayer material, and the second composite self-assembled monolayer 12 is prepared from a second composite self-assembled monolayer material; the second composite self-assembled monolayer 12 uses a π-π stacking effect to effectively induce SAMs to form a specific orientation arrangement during the anchoring process, thereby improving the passivation effect;

[0059] Alternatively, the composite self-assembled monomolecular mixed layer 13 is prepared by mixing a first composite self-assembled monomolecular layer material and a second composite self-assembled monomolecular layer material.

[0060] The first composite self-assembled monolayer 11 , the second composite self-assembled monolayer 12 and the composite self-assembled monolayer mixed layer 13 in the present invention are all novel SAMs, and possess the basic characteristics of SAMs.

[0061] The double-layer structure designed by combining the first composite self-assembled monolayer 11 and the second composite self-assembled monolayer 12 constructs an interface structure with vertical functional partitioning by sequentially depositing two self-assembled molecular layers with different functions on the substrate surface. Its core principle is to achieve precise control of interface characteristics through layered functionalization. Specifically, the dipole moment size and direction of the bottom SAMs and the upper SAMs are independently controllable and can be vertically superimposed. By changing the combination and thickness of different layers of SAMs, energy level gradient control can be achieved. The SAMs in the bottom layer establish chemical contact with the substrate to form a bonding framework, which plays a role in surface energy regulation and defect passivation; the SAMs in the upper layer form a regular and specific oriented molecular arrangement on the substrate surface framework, which is responsible for charge transfer. The interface dipole moment of the double-layer structure designed by combining the first composite self-assembled monolayer 11 and the second composite self-assembled monolayer 12 is increased, accelerating the directional extraction of carriers; the dipole moment size and direction of the bottom SAMs and the upper SAMs are independently controllable and can be vertically superimposed. By changing the combination and thickness of different layers of SAMs, the gradient control of the energy level can be achieved. The dipole moments of different terminal groups (-CH3, -NH2, -COOH) of different SAMs in the composite self-assembled monolayer can be mixed and superimposed to form an energy level slope. By changing the ratio of different types of SAMs, continuous and controllable adjustment of the energy level structure can be achieved. Therefore, the energy band arrangement of the perovskite / charge transfer layer interface can be precisely controlled to reduce the charge extraction barrier; the dipole moments of different terminal groups (-CH3, -NH2, -COOH) of different SAMs in the composite self-assembled monolayer 13 can be mixed and superimposed to form an energy level slope. By changing the ratio of different types of SAMs, continuous and controllable adjustment of the energy level structure can be achieved. Therefore, the composite self-assembled monolayer in the present invention can finely adjust the interface energy level, reduce voltage loss, and can passivate multi-mode defects.

[0062] Since different SAMs have different steric hindrances and reaction activities, the mixed SAMs process takes advantage of this feature. By co-adsorbing two or more self-assembled molecules with different functions on the substrate surface, an ordered interface structure with a synergistic effect is formed. Therefore, the composite self-assembled monomolecular mixed layer has stronger interfacial chemical stability; uniform material distribution is achieved on a large area scale; mixed SAMs meet the process compatibility requirements of large-scale preparation, and compared with independent two-layer SAMs, the preparation process steps and production equipment are reduced.

[0063] The molecular end groups of the composite self-assembled monolayer of the present invention can selectively passivate vacancy defects on the surfaces of NiOx and perovskite, thereby increasing the open circuit voltage (Voc) and fill factor (FF) and effectively reducing non-radiative recombination of carriers in the component.

[0064] The first composite self-assembled monolayer material includes one or more combinations of [4-(9H-carbazol-9-yl)butyl]phosphonic acid (4PACz), [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (Me-4PACz), [4-(3,6-dimethoxy-9H-carbazol-9-yl)butyl]phosphonic acid (MeO-4PACz), [4-(9H-carbazol-9-yl)ethyl]phosphonic acid (2PACz), [4-(3,6-dimethyl-9H-carbazol-9-yl)ethyl]phosphonic acid (Me-2PACz), and [4-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid (MeO-2PACz). The second composite self-assembled monolayer material includes one or more phosphate polyesters and / or sulfonic acid polyesters including triphenyl sulfonate (TSP) and triphenyl phosphate (THP).

[0065] like Figure 1 As shown, the application of the composite self-assembled monolayer of the present invention in perovskite photovoltaic technology. The solar cell module prepared therefrom includes a transparent conductive metal oxide layer 3, a hole transport layer 4, a composite self-assembled monolayer 1, a perovskite active layer 5, an electron transport layer 6, and an electrode layer 7, which are sequentially arranged on a substrate 2.

[0066] Example 1

[0067] like Figure 2 As shown, this embodiment provides a solar cell assembly, including a transparent conductive metal oxide layer 3, a hole transport layer 4, a second composite self-assembled monolayer 12, a first composite self-assembled monolayer 11, a perovskite active layer 5, an electron transport layer 6 and an electrode layer 7, which are sequentially arranged on a substrate 2. The specific preparation method includes:

[0068] (2.1) Preparation of a transparent conductive metal oxide layer: A layer of transparent conductive metal oxide approximately 100 nanometers thick is deposited on the substrate surface by a combination of one or more coating processes selected from magnetron sputtering, reactive plasma sputtering, electron beam coating, atomic layer deposition, and chemical vapor deposition. After coating, the sample is annealed at 200°C for 5 minutes on a heating table or in a vacuum drying oven and then cooled to room temperature to obtain a transparent metal oxide layer. The transparent conductive metal oxide layer includes one or more combinations of tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), indium phosphate (IWO), and indium zonate (IZO).

[0069] (2.2) Preparation of hole transport layer: Deposit a layer of hole transport material with a thickness of approximately 10 nm on the surface of the transparent conductive metal oxide layer by one or more combinations of spin coating, doctor blading, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition methods; wherein the hole transport material is one or more combinations of nickel oxide (NiOx), polytriarylamine (PTAA), cuprous thiocyanate (CuSCN) (poly(3,4-ethylenedioxythiophene):polystyrene sulfonate) (PEDOT:PSS), poly(3-hexylthiophene) (P3HT), and molybdenum disulfide (MoS2);

[0070] (2.3) Preparation of a second composite self-assembled monolayer: Depositing a second self-assembled monolayer material layer having a thickness of approximately 1-3 nm on the surface of the hole transport layer by one or more of spin coating, doctor blade coating, slit coating, and screen printing; wherein the second self-assembled monolayer material layer comprises one or more phosphate polyesters and / or sulfonic acid polyesters including TSP and THP;

[0071] (2.4) Preparation of a first composite self-assembled monolayer: depositing a first self-assembled monolayer material layer having a thickness of about 1-3 nm on the surface of the second composite self-assembled monolayer by one or more of spin coating, doctor blade coating, slit coating, and screen printing; wherein the first self-assembled monolayer material layer comprises one or more of 4PACz, Me-4PACz, MeO-4PACz, 2PACz, Me-2PACz, and MeO-2PACz;

[0072] (2.5) Preparation of the perovskite active layer: Depositing a perovskite precursor film on the surface of the first composite self-assembled monolayer by one or more of spin coating, doctor blading, slit coating, screen printing, and thermal evaporation coating methods. The film is then subjected to solvent extraction, wherein the extraction treatment is one or more of vacuum chamber drying (VCD), air knife blowing, or anti-solvent method. Finally, the film is annealed on a heating plate or in an oven at 100-200°C for 10-30 minutes to obtain a perovskite film having a thickness of approximately 1 μm. The perovskite film comprises one or more of formamidinium-based perovskite, methylamine-based perovskite, and cesium-based perovskite.

[0073] (2.6) Electron transport layer preparation: A layer of electron transport material is formed on the surface of the perovskite active layer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition. The electron transport material includes one or more of tin oxide (SnOx), fullerene (C60), titanium oxide (TiO2), zinc oxide (ZnO), and fullerene derivatives (PCBM).

[0074] (2.7) Electrode layer preparation: A layer of electrode material approximately 100 nanometers thick is prepared on the surface of the electron transport layer by one or more of thermal evaporation, magnetron sputtering, and plasma deposition methods; wherein the electrode material comprises one or more of gold, silver, copper, and transparent electrodes such as indium tin oxide (ITO), fluorine-doped tin oxide (FTO), indium tungsten oxide (IWO), and indium zinc oxide (IZO).

[0075] Example 2

[0076] like Figure 3 As shown, this embodiment provides a solar cell assembly, including a transparent conductive metal oxide layer 3, a hole transport layer 4, a composite self-assembled monomolecular mixed layer 13, a perovskite active layer 5, an electron transport layer 6 and an electrode layer 7 sequentially arranged on a substrate 2. The specific preparation method thereof includes:

[0077] (3.1) Preparation of a transparent conductive metal oxide layer: A layer of transparent conductive metal oxide approximately 100 nanometers thick is deposited on the substrate surface by a combination of one or more coating processes selected from magnetron sputtering, reactive plasma sputtering, electron beam coating, atomic layer deposition, and chemical vapor deposition. After coating, the sample is annealed at 200°C for 5 minutes in a heating table or vacuum drying oven and then cooled to room temperature to obtain a transparent metal oxide layer. The transparent conductive metal oxide layer includes one or more combinations of tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), indium phosphate (IWO), and indium zonate (IZO).

[0078] (3.2) Preparation of hole transport layer: Deposit a layer of hole transport material with a thickness of approximately 10 nm on the surface of the transparent conductive metal oxide layer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition. The hole transport material is one or more of nickel oxide (NiOx), polytriarylamine (PTAA), cuprous thiocyanate (CuSCN) (poly(3,4-ethylenedioxythiophene):polystyrene sulfonate) (PEDOT:PSS), poly(3-hexylthiophene) (P3HT), and molybdenum disulfide (MoS2).

[0079] (3.3) Preparation of a composite self-assembled monomolecular mixed layer: a first self-assembled monomolecular material and a second self-assembled monomolecular material are mixed, and the first self-assembled monomolecular material and the second self-assembled monomolecular material are blended and dissolved in water or an alcohol solvent in a ratio of 9:1 to 9:10 to form a mixed solution; a layer of self-assembled monomolecular composite material layer with a thickness of about 1-3 nm is deposited on the surface of the hole transport layer by one or more combinations of spin coating, blade coating, slit coating, and screen printing; wherein the first self-assembled monomolecular material comprises one or more of 4PACz, Me-4PACz, MeO-4PACz, 2PACz, Me-2PACz, and MeO-2PACz; and the second self-assembled monomolecular material comprises one or more of phosphate polyesters and / or sulfonic acid polyesters including TSP and THP;

[0080] (3.4) Preparation of perovskite active layer: Depositing a perovskite precursor film on the surface of the composite self-assembled monolayer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, or thermal evaporation. The film is then subjected to solvent extraction, wherein the extraction is one or more of vacuum chamber drying (VCD), air knife blowing, or anti-solvent method. Finally, the film is annealed on a heating plate or in an oven at 100-200°C for 10-30 minutes to obtain a perovskite film having a thickness of approximately 1 μm. The perovskite film comprises one or more of formamidinium-based perovskite, methylamine-based perovskite, and cesium-based perovskite.

[0081] (3.5) Electron transport layer preparation: Forming a layer of electron transport material on the surface of the perovskite active layer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition; wherein the electron transport material includes one or more of tin oxide (SnOx), fullerene (C60), titanium oxide (TiO2), zinc oxide (ZnO), and fullerene derivatives (PCBM);

[0082] (3.6) Electrode layer preparation: A layer of electrode material approximately 100 nanometers thick is prepared on the surface of the electron transport layer by one or more of thermal evaporation, magnetron sputtering, and plasma deposition methods; wherein the electrode material comprises one or more of gold, silver, copper, and transparent electrodes such as indium tin oxide (ITO), fluorine-doped tin oxide (FTO), indium tungsten oxide (IWO), and indium zinc oxide (IZO).

[0083] Example 3

[0084] like Figure 4As shown, this embodiment provides a solar cell assembly, including a transparent conductive metal oxide layer 3, a hole transport layer 4, a first composite self-assembled monolayer 11, a second composite self-assembled monolayer 12, a perovskite active layer 5, an electron transport layer 6 and an electrode layer 7, which are sequentially arranged on a substrate 2. The specific preparation method is as follows:

[0085] (1.1) Preparation of a transparent conductive metal oxide layer: A layer of transparent conductive metal oxide approximately 100 nanometers thick is deposited on the substrate surface by a combination of one or more coating processes selected from magnetron sputtering, reactive plasma sputtering, electron beam coating, atomic layer deposition, and chemical vapor deposition. After coating, the sample is annealed at 200°C for 5 minutes on a heating table or in a vacuum drying oven and then cooled to room temperature to obtain a transparent metal oxide layer. The transparent conductive metal oxide layer includes one or more combinations of tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), indium phosphate (IWO), and indium zonate (IZO).

[0086] (1.2) Preparation of hole transport layer: Deposit a layer of hole transport material with a thickness of approximately 10 nm on the surface of the transparent conductive metal oxide layer by one or more combinations of spin coating, doctor blade coating, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition methods; wherein the hole transport material is one or more combinations of nickel oxide (NiOx), polytriarylamine (PTAA), cuprous thiocyanate (CuSCN) (poly(3,4-ethylenedioxythiophene):polystyrene sulfonate) (PEDOT:PSS), poly(3-hexylthiophene) (P3HT), and molybdenum disulfide (MoS2);

[0087] (1.3) Preparation of a first composite self-assembled monolayer: depositing a first self-assembled monolayer material layer having a thickness of about 1-3 nm on the surface of the hole transport layer by one or more of spin coating, doctor blade coating, slit coating, and screen printing; wherein the first self-assembled monolayer material layer comprises one or more of 4PACz, Me-4PACz, MeO-4PACz, 2PACz, Me-2PACz, and MeO-2PACz;

[0088] (1.4) Preparation of a second composite self-assembled monolayer: Depositing a layer of a second self-assembled monolayer material having a thickness of approximately 1-3 nm on the surface of the first composite self-assembled monolayer by one or more of spin coating, doctor blade coating, slit coating, and screen printing; wherein the second composite self-assembled monolayer comprises one or more phosphate polyesters and / or sulfonic acid polyesters including TSP and THP;

[0089] (1.5) Preparation of perovskite active layer: Depositing a perovskite precursor film on the surface of the second composite self-assembled monolayer by one or more of spin coating, doctor blading, slit coating, screen printing, and thermal evaporation coating methods. The film is then subjected to solvent extraction, wherein the extraction treatment is one or more of vacuum chamber drying (VCD), air knife blowing, or anti-solvent method. Finally, the film is annealed on a heating table or in an oven at 100-200°C for 10-30 minutes to obtain a perovskite film having a thickness of approximately 1 μm. The perovskite film comprises one or more of formamidine-based perovskite, methylamine-based perovskite, and cesium-based perovskite.

[0090] (1.6) Electron transport layer preparation: A layer of electron transport material is formed on the surface of the perovskite active layer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition. The electron transport material includes one or more of tin oxide (SnOx), fullerene (C60), titanium oxide (TiO2), zinc oxide (ZnO), and fullerene derivatives (PCBM).

[0091] (1.7) Electrode layer preparation: A layer of electrode material approximately 100 nanometers thick is prepared on the surface of the electron transport layer by one or more of the following methods: thermal evaporation, magnetron sputtering, and plasma deposition. The electrode material comprises one or more of gold, silver, copper, and transparent electrodes such as indium tin oxide (ITO), fluorine-doped tin oxide (FTO), indium tungsten oxide (IWO), and indium zinc oxide (IZO).

[0092] Comparative Example 1

[0093] like Figure 5 As shown, the comparative example provides a common solar cell, whose structure includes a substrate 2, a transparent metal oxide 3, a hole transport layer 4, a SAMs layer (self-assembled monolayer) 10, a perovskite active layer 5, an electron transport layer 6 and a counter electrode 7. The above layers are connected by vertical stacking. The specific preparation method includes:

[0094] (4.1) Preparation of a transparent conductive metal oxide layer: A layer of transparent conductive metal oxide approximately 100 nanometers thick is deposited on the substrate surface by a combination of one or more coating processes selected from magnetron sputtering, reactive plasma sputtering, electron beam coating, atomic layer deposition, and chemical vapor deposition. After coating, the sample is annealed at 200°C for 5 minutes on a heating table or in a vacuum drying oven and then cooled to room temperature to obtain a transparent metal oxide layer. The transparent conductive metal oxide layer includes one or more combinations of tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), indium phosphate diphosphate (IWO), and indium zonate (IZO).

[0095] (4.2) Preparation of hole transport layer: Deposit a layer of hole transport material with a thickness of approximately 10 nm on the surface of the transparent conductive metal oxide layer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition. The hole transport material is one or more of nickel oxide (NiOx), polytriarylamine (PTAA), cuprous thiocyanate (CuSCN) (poly(3,4-ethylenedioxythiophene):polystyrene sulfonate) (PEDOT:PSS), poly(3-hexylthiophene) (P3HT), and molybdenum disulfide (MoS2).

[0096] (4.3) Preparation of SAMs (self-assembled monolayers): Deposit a monolayer of approximately 1-3 nm thick on the surface of the hole transport layer by one or more combinations of spin coating, doctor blade coating, slit coating, and screen printing. The monolayer comprises one or more combinations of carbazole derivatives, including 4PACz.

[0097] (4.4) Preparation of the perovskite active layer: A perovskite precursor film is deposited on the surface of the SAMs layer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, or thermal evaporation. The film is then subjected to solvent extraction, wherein the extraction is one or more of vacuum chamber drying (VCD), air knife blowing, or anti-solvent method. Finally, the film is annealed on a heating plate or in an oven at 100-200°C for 10-30 minutes to obtain a perovskite film with a thickness of approximately 1 μm. The perovskite film comprises one or more of formamidine-based perovskite, methylamine-based perovskite, and cesium-based perovskite.

[0098] (4.5) Preparation of electron transport layer: Forming a layer of electron transport material on the surface of the perovskite active layer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition. The electron transport material includes one or more of tin oxide (SnOx), fullerene (C60), titanium oxide (TiO2), zinc oxide (ZnO), and fullerene derivatives (PCBM).

[0099] (4.6) Electrode layer preparation: A layer of electrode material approximately 100 nanometers thick is prepared on the surface of the electron transport layer by one or more of thermal evaporation, magnetron sputtering, and plasma deposition methods; wherein the electrode material comprises one or more of gold, silver, copper, and transparent electrodes such as indium tin oxide (ITO), fluorine-doped tin oxide (FTO), indium tungsten oxide (IWO), and indium zinc oxide (IZO).

[0100] The solar cell modules prepared in Example 1, Example 2, Example 3 and Comparative Example 1 were subjected to the following treatments under standard AM1.5G illumination conditions:

[0101] Each prepared solar cell module was placed in an open circuit state, that is, without connecting an external load, and the voltage across the battery was measured using a high-impedance voltmeter to obtain the open circuit voltage (Voc);

[0102] The positive and negative electrodes of each prepared solar cell module were short-circuited, and the current during the short circuit was measured with an ammeter. The current was then divided by the effective area of ​​the battery to obtain the short-circuit current density Jsc;

[0103] The current-voltage (IV) characteristic curves of each prepared solar cell module under different loads were measured. The maximum power point (Pmax), open circuit voltage (Voc), and short circuit current (Isc) of the solar cell were obtained from the IV curves. The fill factor (FF) was calculated using the formula: FF = Pmax / (Voc × Isc).

[0104] The output power of each prepared solar cell module is measured and then divided by the power of the incident light to obtain the photoelectric conversion efficiency (PCE). The calculation formula is: PCE = Pmax / Pin, where Pin is the power of the incident light, which can be calculated based on the light intensity and the cell area.

[0105] The data obtained from the above calculations for the solar cell modules prepared in Example 1, Example 2, Example 3 and Comparative Example 1 are shown in Table 1.

[0106] Table 1

[0107] serial number <![CDATA[V oc (V)]]> <![CDATA[J sc (mAcm -1 )]]> FF(%) PCE (%) Example 1 8.09 3.29 82.87 22.04 Example 2 7.96 3.21 82.36 21.01 Example 3 7.95 3.24 80.33 20.69 Comparative Example 1 7.87 3.24 76.05 19.41

[0108] As can be seen from Table 1, the performance of the solar cell modules prepared by Examples 1 to 3 is significantly higher than that of the solar cell module prepared by Comparative Example 1 under standard AM1.5G lighting conditions. Among them, the open circuit voltages of the solar cell modules prepared by Examples 1, 2 and 3 are 8.09 V, 7.96 V and 7.95 V, respectively, which are about 2.7% higher than the open circuit voltage of the traditional solar cell module prepared in Comparative Example 1. In particular, the open circuit voltage of the solar cell module prepared by Example 1 is significantly higher than that of the traditional solar cell module prepared in Comparative Example 1, indicating that the solar cell module prepared by this scheme can establish a higher potential difference when converting light energy into electrical energy, which is beneficial to improving the overall performance of the battery. The short circuit current density of the solar cell modules prepared by Examples 1, 2, 3 and Comparative Example 1 is 3.29 mA / cm 2 , 3.21mA / cm 2 , 3.24mA / cm 2and 3.24 mA / cm 2 , indicating that the solar modules prepared by this scheme are not significantly different from traditional solar cell modules in terms of light absorption and carrier collection; the fill factors of the solar modules prepared by Example 1, Example 2 and Example 3 are 82.87%, 82.36% and 80.33% respectively, which are about 9.0% higher than the fill factor of the traditional solar cell module prepared in Comparative Example 1, indicating that the solar group prepared by this scheme can more effectively convert photogenerated current and voltage into actually usable electrical energy, and its performance is better than that of traditional solar cell modules; the photoelectric conversion efficiency of the solar modules prepared by Example 1, Example 2 and Example 3 are 22.04%, 21.01% and 20.69% respectively, which is about 13.5% higher than the photoelectric conversion efficiency of the traditional solar cell module prepared in Comparative Example 1.

[0109] In order to compare the thermal stability of the solar cell modules prepared in this solution with that of the traditional solar cell modules, the solar cell modules prepared in Example 1 and Comparative Example 1 were placed in an environmental chamber with precisely controlled temperature, and cyclically treated from room temperature to a high temperature (e.g., 85°C) and then back to room temperature. The open circuit voltage, short circuit current, and fill factor of the solar cell modules at different time points (e.g., 0h, 20h, 70h, and 480h) were calculated to obtain the calculated normalized photoelectric conversion efficiency at the corresponding time. The curve fitted by the calculated results is shown as follows: Figure 6 As shown in the figure, it can be seen that the normalized photoelectric conversion efficiency of the solar cell module prepared by Example 1 decays slowly and with a small amplitude over time, and is still close to 0.9 au after 480 hours, indicating that it can effectively maintain its photoelectric conversion ability in a thermal environment and has excellent thermal stability; the normalized photoelectric conversion efficiency of the solar cell module prepared by Comparative Example 1 decays significantly faster, and drops to about 0.6 au after 480 hours, reflecting that the thermal environment damages its performance more significantly and its thermal stability is poor, indicating that the solar cell module prepared by the present invention has strong "thermal drop resistance" ability, good thermal stability, and its performance in a thermal environment is better than that of traditional solar cell modules.

[0110] In addition, in order to conduct accelerated aging tests to simulate the long-term effects of extreme hot and humid environments on devices and quickly expose potential failure risks through accelerated aging mechanisms, the solar cell modules prepared in Examples 1 to 3 were packaged and subjected to a stress test at 85°C / 85% humidity. The open circuit voltage, short circuit current, and fill factor of the solar cell modules at different time points (e.g., 0h, 20h, 70h, and 480h) were calculated to obtain the calculated normalized photoelectric conversion efficiency at the corresponding time. The curve fitted by the calculated results is shown in FIG. Figure 7As shown in the figure, it can be seen that the normalized photoelectric conversion efficiency of the solar cell modules prepared by Examples 1 to 3 decays slowly and slightly over time, and is still close to 0.9 au after 480 hours, indicating that it has excellent thermal stability in the harsh damp heat aging test at 85°C / 85% humidity; it indicates that the solar cell modules prepared by the present invention have strong resistance to moisture and heat and good thermal stability.

[0111] Therefore, the solar cell module prepared by this solution is superior to the traditional solar cell module in all aspects of performance. This approach utilizes a novel self-assembled monolayer (SAM) structure with a multilayer / multi-material composite SAMs functional structure. This structure utilizes a π-π stacking effect to effectively induce a specific orientation of the SAMs during the anchoring process, thereby enhancing the passivation effect. This specific orientation is due to the fact that the two opposite end groups of the SAMs contain carbazole and phosphate groups, respectively, which can only chemically react with specific functional groups. The phosphate group forms a strong chemical contact with the metal oxide (such as NiOx) and is anchored to the metal oxide surface. The carbazole group, on the other hand, has a specific van der Waals force or weak hydrogen bond interaction with the perovskite, thus forming a vertically oriented molecular arrangement between the perovskite and metal oxide layers on a macroscopic scale. The SAMs in the composite SAM contain carbazole and phosphate groups, of which the phosphate groups anchor to the Ni vacancies in NiOx, while the carbazole and phosphate groups form hydrogen bonds or van der Waals forces with the perovskite, effectively strengthening the stable chemical bonding between the SAMs and the hole transport layer and perovskite, reducing the physical adsorption with weaker forces, and enhancing the thermal stability of the SAMs.

[0112] The molecular end groups of the composite self-assembled monolayer can selectively passivate the vacancy defects on the surfaces of NiOx and perovskite, thereby increasing the open circuit voltage (Voc) and fill factor (FF) and effectively reducing the non-radiative recombination of carriers in the components.

[0113] The composite self-assembled monolayer can precisely regulate the energy band arrangement at the perovskite / charge transfer layer interface and reduce the charge extraction barrier.

[0114] The composite self-assembled monolayer itself has a large steric hindrance, which ensures that SAMs are evenly dispersed on the surface of the hole transport layer and reduces the problem of uneven perovskite film formation caused by the agglomeration of SAMs themselves, providing a good growth template for perovskite; it can meet the process requirements of film uniformity of <5% for large-area components such as slit coating and blade coating.

[0115] When preparing the composite self-assembled monomolecular mixed layer, the first composite self-assembled monomolecular layer material and the second composite self-assembled monomolecular layer material are mixed and dissolved in water or alcohol solvent. No toxic or harmful solvents are involved in the production process, which meets the requirements of green manufacturing.

[0116] Although the preferred embodiments of the present application have been described, those skilled in the art may make additional changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present application.

Claims

1. A composite self-assembled monolayer, characterized in that include: A first composite self-assembled monolayer and a second composite self-assembled monolayer, wherein the first composite self-assembled monolayer and the second composite self-assembled monolayer are combined to form a double-layer structure; The first composite self-assembled monolayer is prepared from a first composite self-assembled monolayer material, and the second composite self-assembled monolayer is prepared from a second composite self-assembled monolayer material; Or, a composite self-assembled monomolecular mixed layer, wherein the composite self-assembled monomolecular mixed layer is prepared by mixing a first composite self-assembled monomolecular layer material and a second composite self-assembled monomolecular layer material.

2. A composite self-assembled monolayer according to claim 1, characterized in that: The double-layer structure includes a first composite self-assembled monolayer stacked on an upper layer of a second composite self-assembled monolayer, or a first composite self-assembled monolayer stacked on a lower layer of the second composite self-assembled monolayer.

3. A composite self-assembled monolayer according to claim 1, characterized in that: The first composite self-assembled monolayer material includes one or more combinations of 4PACz, Me-4PACz, MeO-4PACz, 2PACz, Me-2PACz, and MeO-2PACz.

4. A composite self-assembled monolayer according to claim 1, characterized in that: The second composite self-assembled monolayer material includes one or more phosphate polyesters and / or sulfonic acid polyesters including TSP and THP.

5. Use of the composite self-assembled monolayer according to any one of claims 1 to 4 in perovskite photovoltaic technology.

6. A solar cell module, characterized in that: The invention comprises a transparent conductive metal oxide layer, a hole transport layer, a composite self-assembled monolayer according to any one of claims 1 to 4, a perovskite active layer, an electron transport layer and an electrode layer which are sequentially arranged on a substrate.

7. A solar cell assembly according to claim 6, characterized in that: The invention comprises a transparent conductive metal oxide layer, a hole transport layer, a first composite self-assembled monolayer, a second composite self-assembled monolayer, a perovskite active layer, an electron transport layer and an electrode layer which are sequentially arranged on a substrate.

8. A solar cell assembly according to claim 6, characterized in that: The invention comprises a transparent conductive metal oxide layer, a hole transport layer, a second composite self-assembled monolayer, a first composite self-assembled monolayer, a perovskite active layer, an electron transport layer and an electrode layer which are sequentially arranged on a substrate.

9. A solar cell assembly according to claim 6, characterized in that: The invention comprises a transparent conductive metal oxide layer, a hole transport layer, a composite self-assembled monomolecular mixed layer, a perovskite active layer, an electron transport layer and an electrode layer which are sequentially arranged on a substrate.

10. A method for preparing a solar cell module, characterized in that: The method is applicable to the solar cell assembly according to claim 7, and the preparation method comprises: (1.1) Preparation of a transparent conductive metal oxide layer: A layer of transparent conductive metal oxide approximately 100 nanometers thick is deposited on the substrate surface by a combination of one or more coating processes selected from magnetron sputtering, reactive plasma sputtering, electron beam coating, atomic layer deposition, and chemical vapor deposition. After coating, the sample is annealed at 200°C for 5 minutes on a heating table or in a vacuum drying oven and then cooled to room temperature to obtain a transparent metal oxide layer. The transparent conductive metal oxide layer includes one or more combinations of ITO, FTO, IWO, and IZO. (1.2) Preparation of hole transport layer: A hole transport material layer with a thickness of about 10 nm is deposited on the surface of the transparent conductive metal oxide layer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition; wherein the hole transport material is NiO x , one or more combinations of PTAA, CuSCN, PEDOT:PSS, P3HT and MoS2; (1.3) Preparation of a first composite self-assembled monolayer: depositing a first self-assembled monolayer material layer having a thickness of about 1-3 nm on the surface of the hole transport layer by one or more of spin coating, doctor blade coating, slit coating, and screen printing; wherein the first self-assembled monolayer material layer comprises one or more of 4PACz, Me-4PACz, MeO-4PACz, 2PACz, Me-2PACz, and MeO-2PACz; (1.4) Preparation of a second composite self-assembled monolayer: Depositing a layer of a second self-assembled monolayer material having a thickness of approximately 1-3 nm on the surface of the first composite self-assembled monolayer by one or more of spin coating, doctor blade coating, slit coating, and screen printing; wherein the second composite self-assembled monolayer comprises one or more phosphate polyesters and / or sulfonic acid polyesters including TSP and THP; (1.5) Preparation of the perovskite active layer: Deposit a perovskite precursor film on the surface of the second composite self-assembled monolayer by one or more of spin coating, doctor blading, slit coating, screen printing, and thermal evaporation. The film is then subjected to solvent extraction and annealed on a heating plate or in an oven at 100-200°C for 10-30 minutes to obtain a perovskite film having a thickness of approximately 1 μm. The perovskite film comprises one or more of formamidine-based perovskite, methylamine-based perovskite, and cesium-based perovskite. (1.6) Preparation of electron transport layer: A layer of electron transport material is formed on the surface of the perovskite active layer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition; wherein the electron transport material includes SnO x , one or more of C60, TiO2, ZnO and PCBM; (1.7) Electrode layer preparation: A layer of electrode material approximately 100 nanometers thick is prepared on the surface of the electron transport layer by one or more of thermal evaporation, magnetron sputtering, and plasma deposition methods; wherein the electrode material comprises one or more of gold, silver, copper and ITO, FTO, IWO, and IZO.

11. A method for preparing a solar cell module, characterized in that: The method is applicable to the solar cell assembly according to claim 8, and the preparation method comprises: (2.1) Preparation of a transparent conductive metal oxide layer: A layer of transparent conductive metal oxide approximately 100 nanometers thick is deposited on the substrate surface by a combination of one or more coating processes selected from magnetron sputtering, reactive plasma sputtering, electron beam coating, atomic layer deposition, and chemical vapor deposition. After coating, the sample is annealed at 200°C for 5 minutes on a heating table or in a vacuum drying oven and then cooled to room temperature to obtain a transparent metal oxide layer. The transparent conductive metal oxide layer includes one or more combinations of ITO, FTO, IWO, and IZO. (2.2) Preparation of hole transport layer: A hole transport material layer with a thickness of about 10 nm is deposited on the surface of the transparent conductive metal oxide layer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition; wherein the hole transport material is NiO x , one or more combinations of PTAA, CuSCN, PEDOT:PSS, P3HT and MoS2; (2.3) Preparation of a second composite self-assembled monolayer: Depositing a second self-assembled monolayer material layer having a thickness of approximately 1-3 nm on the surface of the hole transport layer by one or more of spin coating, doctor blade coating, slit coating, and screen printing; wherein the second self-assembled monolayer material layer comprises one or more phosphate polyesters and / or sulfonic acid polyesters including TSP and THP; (2.4) Preparation of a first composite self-assembled monolayer: depositing a first self-assembled monolayer material layer having a thickness of about 1-3 nm on the surface of the second composite self-assembled monolayer by one or more of spin coating, doctor blade coating, slit coating, and screen printing; wherein the first self-assembled monolayer material layer comprises one or more of 4PACz, Me-4PACz, MeO-4PACz, 2PACz, Me-2PACz, and MeO-2PACz; (2.5) Preparation of the perovskite active layer: Deposit a perovskite precursor film on the surface of the first composite self-assembled monolayer by one or more of spin coating, doctor blading, slit coating, screen printing, and thermal evaporation. The film is then subjected to solvent extraction and annealed on a heating plate or in an oven at 100-200°C for 10-30 minutes to obtain a perovskite film having a thickness of approximately 1 μm. The perovskite film comprises one or more of formamidine-based perovskite, methylamine-based perovskite, and cesium-based perovskite. (2.6) Preparation of electron transport layer: A layer of electron transport material is formed on the surface of the perovskite active layer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition; wherein the electron transport material includes SnO x , one or more of C60, TiO2, ZnO and PCBM; (2.7) Electrode layer preparation: A layer of electrode material approximately 100 nanometers thick is prepared on the surface of the electron transport layer by one or more of thermal evaporation, magnetron sputtering, and plasma deposition methods; wherein the electrode material comprises one or more of gold, silver, copper and ITO, FTO, IWO, and IZO.

12. A method for preparing a solar cell module, characterized in that: The method is applicable to the solar cell assembly according to claim 9, and the preparation method comprises: (3.1) Preparation of a transparent conductive metal oxide layer: A layer of transparent conductive metal oxide approximately 100 nanometers thick is deposited on the substrate surface by a combination of one or more coating processes selected from magnetron sputtering, reactive plasma sputtering, electron beam coating, atomic layer deposition, and chemical vapor deposition. After coating, the sample is annealed at 200°C for 5 minutes on a heating table or in a vacuum drying oven and then cooled to room temperature to obtain a transparent metal oxide layer. Transparent conductive metal oxides include one or more combinations of ITO, FTO, IWO, and IZO. (3.2) Preparation of hole transport layer: A hole transport material layer with a thickness of about 10 nm is deposited on the surface of the transparent conductive metal oxide layer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition; wherein the hole transport material is NiO x , one or more combinations of PTAA, CuSCN, PEDOT:PSS, P3HT and MoS2; (3.3) Preparation of a composite self-assembled monomolecular mixed layer: a first self-assembled monomolecular material and a second self-assembled monomolecular material are mixed and dissolved in water or an alcohol solvent by blending and blending to form a mixed solution; a layer of self-assembled monomolecular composite material with a thickness of about 1-3 nm is deposited on the surface of the hole transport layer by one or more combinations of spin coating, blade coating, slit coating, and screen printing; wherein the first self-assembled monomolecular material comprises one or more of 4PACz, Me-4PACz, MeO-4PACz, 2PACz, Me-2PACz, and MeO-2PACz; and the second self-assembled monomolecular material comprises one or more of phosphate polyesters and / or sulfonic acid polyesters including TSP and THP; (3.4) Preparation of the perovskite active layer: Deposit a thin film of perovskite precursor on the surface of the composite self-assembled monolayer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, or thermal evaporation. The film is then subjected to solvent extraction and annealed on a heating plate or in an oven at 100-200°C for 10-30 minutes to obtain a perovskite film having a thickness of approximately 1 μm. The perovskite film comprises one or more of formamidinium-based perovskite, methylamine-based perovskite, and cesium-based perovskite. (3.5) Preparation of electron transport layer: A layer of electron transport material is formed on the surface of the perovskite active layer by one or more of the following methods: spin coating, doctor blade coating, slit coating, screen printing, magnetron sputtering, reactive plasma deposition, atomic layer deposition, and chemical vapor deposition; wherein the electron transport material includes SnO x , one or more of C60, TiO2, ZnO and PCBM; (3.6) Electrode layer preparation: A layer of electrode material approximately 100 nanometers thick is prepared on the surface of the electron transport layer by one or more of thermal evaporation, magnetron sputtering, and plasma deposition methods; wherein the electrode material comprises gold, silver, copper and one or more of ITO, FTO, IWO, and IZO.

Images