Structural integrated energy skin with hierarchical pore confined hybrid superstructure

Abstract

The application belongs to the technical field of structural energy, and particularly relates to a structural integrated energy skin with hierarchical pore limited hybrid superstructure. The energy skin comprises: a two-dimensional covalent organic framework film as a continuous phase host framework, a photoelectric active guest component located in the pore structure of the host framework and penetrating through the thickness direction of the film, a molecular level interface passivation layer introduced by a gate vapor pulse and discontinuously distributed on the host-guest heterojunction interface, and a charge selective contact structure. The host framework has a first pore structure for interface limitation and a second pore structure for guest transmission. During preparation, the guest is generated in situ in a limited space by gas phase permeation, and its grain boundary fusion is induced by passivation and flash solidification in cooperation with the gate vapor pulse. The application constructs a trinity physical constraint architecture of host-guest-interface, effectively inhibits ion migration and non-radiative recombination, realizes high stability output in a complex environment, and is suitable for mobile carrier load bearing skin.

Description

Technical Field

[0001] This invention belongs to the field of structural energy technology, specifically relating to a structurally integrated energy skin with a hierarchical pore-confined hybrid superstructure. Background Technology

[0002] Existing high-efficiency photoelectric active materials (such as halide perovskites and metal chalcogenides) typically face inherent defects such as low ion migration barriers and sensitivity to interface defects. Under the coupled effects of water and oxygen, thermal stress, and mechanical loads, they are prone to phase degradation and performance decline. In mobile applications such as drones, spacecraft, and intelligent vehicles, materials need to withstand high-frequency vibration, bending deformation, and severe hygrothermal cycling stress for extended periods. Localized stress concentrations often lead to microcrack initiation and a sharp increase in deep-level nonradiative recombination.

[0003] Traditional solutions often rely on multilayered device structures combined with thick external physical encapsulation barriers. However, this "extended protection" not only greatly increases the system's dead weight, making it difficult to achieve lightweight integration with load-bearing structures, but also means that once the encapsulation layer suffers microscopic mechanical damage, the active medium will be rapidly exposed and fail.

[0004] Therefore, the industry urgently needs an endogenous superstructure solution that breaks through the reliance on traditional packaging and achieves the synergy of "physical confinement, chemical stability and continuous charge transport" at the microscopic scale of materials. Summary of the Invention

[0005] To address the problems existing in the prior art, this invention provides a structurally integrated energy skin with a hierarchical pore-confined hybrid superstructure. This invention uses a two-dimensional covalent organic framework (COF) as the continuous phase host skeleton, forms photoelectric active guests in situ within its hierarchical pore-confined environment, and prepares a stable-output structurally integrated energy skin through gas-phase interface passivation and flash curing. By constructing a three-in-one microphysical constraint architecture of "host-guest-interface," this invention achieves stable service in extreme environments and quasi-ballistic charge collection of high-energy photoelectric active materials without heavy encapsulation.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: The first aspect of this invention provides a structurally integrated energy skin with a hierarchical pore-confined hybrid superstructure, comprising: The host framework is a two-dimensional covalent organic framework film of continuous phase, wherein the host framework has at least two pore structures with different feature sizes, including a first pore structure and a second pore structure, wherein the feature size of the first pore structure is smaller than that of the second pore structure; The photoelectroactive guest component is located within at least the second pore structure of the host framework. The photoelectroactive guest component is a photoelectroactive semiconductor phase that exhibits structural instability or chemical instability in a free state, and forms a continuous photoelectroactive guest phase that extends through the film thickness direction for charge transport within the confined environment of the host framework. A molecular-level interface passivation layer is formed by passivation molecules introduced by a gated vapor pulse. The passivation molecules are selectively anchored at the heterogeneous interface between the host backbone and the photoelectroactive guest component in a discontinuous distribution manner, which is used to suppress the ion migration or nonradiative recombination of the photoelectroactive guest component. The charge-selective contact structure includes a hole-selective contact layer and an electron-selective contact layer that match the energy levels of the host framework.

[0007] Furthermore, the first pore structure is a micropore with a characteristic pore size of 0.5-5 nm, used to provide interface confinement effect, chemical potential regulation or ion migration inhibition; the second pore structure is a mesopore or macropore with a characteristic pore size of 5-200 nm, formed by surfactant micellization physical template, used to accommodate the photoelectric active guest components and form charge transport pathways.

[0008] Furthermore, the photoelectric active guest component has a grain boundary fusion structure induced by a short-duration high-energy light pulse, and the effective carrier collection length Lc of the continuous phase of the photoelectric active guest satisfies: Lc ≥ 0.8d, where d is the physical thickness of the organic framework film.

[0009] Furthermore, the photoelectric active guest component is selected from inorganic perovskite, quasi-two-dimensional perovskite, metal chalcogenide nanocrystals, organic-inorganic hybrid perovskite, or a combination thereof.

[0010] Furthermore, the molecular-level interface passivation layer is distributed discontinuously on the surface of the host framework in an atomic or island-like manner, and does not form a continuous covering film; the passivation molecules are selectively anchored to unsaturated metal sites on the surface of the photoactive guest component through their end groups.

[0011] Furthermore, the metal chalcogenide nanocrystals are AgBiS2, the organic-inorganic hybrid semiconductor is MAPbI3, and when the photoactive guest component is AgBiS2, the passivating molecule is 1-dodecyl mercaptan (DDT); when the photoactive guest component is perovskite, the passivating molecule is octylamine iodine (OAI).

[0012] A second aspect of the present invention provides a method for preparing the above-mentioned integrated energy skin with hierarchical pore-confined hybrid superstructure, comprising the following steps: Step S1: On a substrate with a first charge-selective contact layer, a continuous two-dimensional covalent organic framework film with a first pore structure and a second pore structure is prepared as a host skeleton by solution phase self-assembly and dynamic covalent crystallization reaction. Step S2: The guest precursor is introduced into the pores of the host skeleton by vapor phase infiltration, and in-situ crystallization or solid-phase transformation is carried out in a confined space to generate a continuous photoelectric active guest phase that runs through the thickness direction of the thin film. Step S3: Passivating small molecules are introduced through gated vapor pulses to anchor them discontinuously at the host-guest heterogeneous interface; then, the hybrid film is subjected to flash curing to induce grain boundary fusion of the photoelectric active guest components; Step S4: Deposit a second charge-selective contact layer on top of the hybrid film to complete the fabrication of the energy skin.

[0013] Further, in step S1, after the sol containing amine monomers and aldehyde monomers is mixed with a surfactant and coated, a physical template for the second pore structure is formed by evaporation-induced self-assembly (EISA), and then imine condensation and dynamic self-correction (DCC) occur under heating conditions to form the host skeleton.

[0014] Furthermore, in step S2, a spatial atomic layer deposition method is used to induce the guest precursor to self-limitedly adsorb on the pore wall by a combination of low-dose precursor vapor pulses and long-term immersion. Subsequently, a reaction gas is introduced to perform in-situ confined crystallization to generate the photoelectric active guest continuous phase.

[0015] Furthermore, in step S3, the flash curing is performed using a xenon lamp array light pulse to achieve solid-phase welding of the photoelectric active guest components while ensuring that the host skeleton does not undergo thermal degradation.

[0016] This invention employs an innovative process chain of "self-assembly to construct the host skeleton, spatial atomic layer deposition for restricted in-situ crystallization, gated vapor pulse passivation, and flash light pulse curing" to ensure the completion of hybrid thin film construction and grain boundary welding at low temperatures (≤120℃).

[0017] Compared with the prior art, the beneficial effects of the present invention are: (1) Extreme microscopic solidification (intrinsic stress resistance): This invention breaks through the traditional external encapsulation, and uses the physical spatial confinement of micropores and the chemical anchoring of passivated small molecules to lock the ion migration path from the atomic / molecular scale, fundamentally eliminating phase separation and degradation caused by damp heat and mechanical stress.

[0018] (2) Topological continuous transport (high-efficiency collection): This invention cleverly utilizes a mesoporous physical template network to make the originally fragile guest material grow into a "through steel bar" with grain boundary fusion characteristics in the thickness direction, realizing quasi-ballistic charge transport across physical thickness (Lc ≥ 0.8d), which greatly reduces leakage loss.

[0019] (3) Extremely lightweight and integrated: The continuous phase COF skeleton in this invention has both flexibility and structural rigidity. It can be directly co-cured or bonded with composite material substrates such as carbon fiber, completely eliminating the glass cover plate and heavy back plate, and achieving the ultimate goal of "both bearing load and generating electricity".

[0020] (4) Platform-based expansion: The photoelectric active guest components described in this invention can be various unstable high-energy materials, which can be stabilized through the same host-guest-interface constraint logic, and have good material replaceability and engineering adaptability. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the host-guest-interface triadic superstructure of the present invention, wherein 10 is the host framework, 11 is the first pore structure, 12 is the second pore structure, 20 is the photoelectric active guest component, and 30 is the molecular-level interface passivation layer. Detailed Implementation

[0022] The specific embodiments of the present invention will be further described below. It should be noted that these descriptions are for the purpose of aiding understanding the present invention, but do not constitute a limitation thereof. Furthermore, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0023] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the experimental materials used in the following embodiments are all available through conventional commercial channels.

[0024] Terminology Explanation: "First hole structure" and "second hole structure" are used to express the relative characteristic size relationship of hole structures and their functional division, wherein the characteristic size of the first hole structure is smaller than that of the second hole structure.

[0025] "Discontinuous distribution" refers to the fact that passivated molecules do not form a continuous covering film, but selectively exist at the heterogeneous interface in an atomic or island-like form.

[0026] Formation of the host framework: The host framework can be prepared into a two-dimensional COF film through solution interface reaction, surface-induced polymerization, or other methods that can form a continuous film. The host framework preferably has a smaller pore structure that can achieve interface confinement and a larger pore structure that can accommodate and facilitate transport. The larger pore structure can be introduced by monomer geometry, interlayer stacking defects, or mismatches.

[0027] In-situ formation of the guest: After the guest precursor is introduced into the host skeleton pores through gas phase infiltration, it undergoes confined crystallization or solid-phase transformation in a confined environment, so that the guest forms a continuous phase that runs through the thickness direction of the film in the second pore structure.

[0028] Interface passivation: Passivating small molecules are introduced in the gas phase, selectively anchoring them at the host-guest heterogeneous interface. These passivating small molecules interact with the interface through covalent bonds, coordination bonds, hydrogen bonds, or strong dipole interactions, thereby reducing interface defect states and inhibiting ion migration. The passivation layer is maintained in a discontinuous distribution to avoid overall blockage of charge transport channels.

[0029] Selective contact: Hole-selective contact layer and electron-selective contact layer are respectively set on the upper and lower surfaces of the energy skin to match the energy levels of the host framework in order to achieve selective charge collection and reduce interfacial recombination.

[0030] The effective carrier collection length (Lc) described in this invention can be obtained by combining bias-dependent external quantum efficiency (EQE) testing with transmission model fitting, which is a conventional method in the art.

[0031] Example 1: Preparation of a structurally integrated energy skin (AgBiS2 as the guest material) This embodiment provides an integrated energy skin based on a two-dimensional covalent organic framework (COF) and an in-situ chalcogenide (AgBiS2) hybrid structure. The overall device configuration adopts a stack of "hole transport layer / hybrid active layer / electron transport layer", and the total film thickness (compliance active skin thickness) is controlled at approximately 200 nm. The specific fabrication steps are as follows: Step S1: Formation of the continuous phase two-dimensional hierarchical porous COF host framework (1) Material ratio: The trifunctional amine monomer TAPB (1,3,5-tris(4-aminophenyl)benzene, concentration 10 mg / mL) and the difunctional aldehyde monomer TPA (terephthalaldehyde, concentration 5.7 mg / mL, molar ratio approximately 2:3) were dissolved in a mixed solvent of 1,4-dioxane and mesitylene (volume ratio 1:1), and 0.2 mL of 3M acetic acid was added as a catalyst. Subsequently, 5 wt% of Pluronic F127 as a surfactant was added, and the mixture was stirred to form a homogeneous sol.

[0032] (2) EISA and self-assembly: The sol was sprayed at 3000 rpm onto a substrate coated with a 40 nm hole-selective contact layer (NiO). x Spin-coat the substrate for 30 s. Place it in a controlled evaporation chamber at 60°C for 30 minutes, during which solvent evaporation induces micellization (EISA) of Pluronic F127, forming a physical template for the second pore structure (mesopore).

[0033] (3) Dynamic covalent crystallization: The film was transferred to a sealed reactor and reacted at 120°C for 24 hours. The amine and aldehyde underwent imine condensation and dynamic self-correction (DCC) in the micelle gaps. After the surfactant was finally eluted, a two-dimensional COF host framework with a thickness of about 120 nm and vertical orientation was obtained. It contains micropores (first pore structure, ~1.5 nm) and mesopores (second pore structure, pore depth-to-diameter ratio of about 1:1, characteristic size of about 12-15 nm).

[0034] Step S2: Spatial ALD Infiltration and Confined In-situ Formation of Photoactive Guests Using Space Atomic Layer Deposition (ALD) technology: (1) Pretreatment: Vacuum pretreatment at 100 Pa and 70℃ for 30 min to remove adsorbed water in the pores.

[0035] (2) Precursor co-permeation: The cavity temperature is set to 110 ℃, Ag (pivalate) vapor is pulsed and soaked for 60s to allow it to self-adsorb on the pore wall; the temperature is raised to 140℃, Bi (thd)3 vapor is pulsed and soaked for 60s to form Ag / Bi precursor co-distribution.

[0036] (3) In-situ sulfidation: H2S vapor was introduced at a pressure of 300 Pa for 20 minutes for in-situ sulfidation reaction. The reactants diffused in the solid phase in the confined space and finally formed a continuous AgBiS2 crystal liner in situ with a thickness of 120 nm.

[0037] Step S3: Gated vapor pulse atomic-level interface passivation and flash curing (1) Steric hindrance targeted passivation: 1-dodecathiol (DDT) gated vapor pulses (1 s) are introduced into the reaction chamber. Thanks to the steric hindrance effect, its -SH end group is precisely and discontinuously anchored to the unsaturated metal sites on the AgBiS2 surface, avoiding the formation of the insulating dead layer.

[0038] (2) Transient grain boundary fusion (Flash Curing): using a total energy density of 25 J / cm² 2The xenon lamp array uses light pulses to perform flash curing. This short-duration, high-energy thermal shock wave can precisely penetrate and induce interfacial fusion (solid-state welding) between guest nanocrystals, while the extremely short thermal relaxation time perfectly ensures that the organic COF framework is protected from thermal degradation.

[0039] Step S4: Construction of the top electrode A 40 nm thick electron-selective contact layer (SnO2 and an extremely thin silver electrode grid) is thermally evaporated or atomically deposited on top of the hybrid layer, bringing the total thickness of the energy skin to ~200 nm.

[0040] After testing, the final technical specifications of the materials and devices are as follows: (1) Effective carrier collection length (Lc): After bias-dependent EQE fitting, Lc=185 nm, which is much larger than the physical thickness d of the active layer (120 nm), satisfying Lc≧0.8d, which confirms quasi-ballistic charge transport.

[0041] (2) Electrical terminal parameters: Open circuit voltage Voc = 0.58V (extremely high for AgBiS2 material), dark-state reverse saturation current density J0 as low as 1.5×10 -7 mA / cm 2 .

[0042] (3) Environmental stability: After 1000 hours of extreme aging test with continuous UV irradiation and 5Grms mechanical vibration, the device power retention rate is as high as 95%, demonstrating the excellent reliability of the architecture as an aerospace load-bearing skin.

[0043] Comparative Example 1: Performance degradation due to lack of interface passivation and flash curing After completing "Step S2 (in-situ sulfidation)" in Example 1, this comparative example skips "Step S3" directly, that is, it does not perform DDT-gated passivation and step-by-step flash curing, and directly deposits the top electrode.

[0044] Technical indicator comparison: Due to the presence of incompletely reacted ligands in the pores and the lack of fusion at the grain boundaries, severe leakage current and non-radiative recombination occur.

[0045] (1) When Lc drops sharply to 75 nm (<0.8d), vertical charge collection is hindered.

[0046] (2) Voc drops to 0.35V, J0 rises to 8.2×10 -4 mA / cm 2 .

[0047] (3) After the same 1000-hour UV+vibration test, the power retention rate was only 55%, proving that without this core process, the structural energy use requirements cannot be met.

[0048] Comparative Example 2: Using conventional MAPbI3 perovskite as the guest material This comparative example aims to verify the performance when the in-situ generated guest is replaced with a conventional organic-inorganic hybrid perovskite (MAPbI3).

[0049] Differences in process parameters: Compared with Example 1, the host framework preparation was the same as in step S1 (thickness 120 nm). In step S2, a vapor deposition method was used instead: PbI2 was first evaporated and infiltrated at 100 °C (equivalent thickness 100 nm), followed by the introduction of methylamine iodine (MAI) vapor at 120 °C for 2 hours to generate MAPbI3 within the pores. In step S3, the passivation molecules were replaced with octylamine iodine (OAI) vapor specific to perovskites, and the flash curing energy was reduced to 15 J / cm. 2 (To avoid thermal decomposition of organic components). The total film thickness is also controlled at 200 nm.

[0050] Technical Indicators Comparison: (1) Initial electrical properties: Due to the excellent light absorption properties of perovskite, the initial performance is excellent (Lc=190nm, Voc=1.05V, J0=3.1×10). -8 mA / cm 2 ).

[0051] (2) Shortcomings in extreme environment stability: In the same 1000-hour UV + vibration test (with an operating temperature of 85℃), due to the inherent soft lattice and high ion mobility of MAPbI3, it is very easy to undergo phase transition and degradation under stress coupling. After the test, the power retention rate dropped sharply to 78%.

[0052] In summary, although the COF confinement framework can significantly improve the stability of traditional perovskites (typically, pure perovskite films retain less than 30% of their capacity under this test), to create a "structurally integrated energy skin" for harsh service environments, it is necessary to use the preferred all-inorganic / strongly covalent guest (such as AgBiS2) of this invention in conjunction with a passivation and curing process to achieve more than 95% mission-grade environmental stability.

[0053] The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and these variations still fall within the protection scope of the present invention.

Claims

1. A structurally integrated energy skin with a hierarchical pore-confined hybrid superstructure, characterized in that, include: The host framework is a two-dimensional covalent organic framework film of continuous phase, wherein the host framework has at least two pore structures with different feature sizes, including a first pore structure and a second pore structure, wherein the feature size of the first pore structure is smaller than that of the second pore structure; A photoelectric active guest component is located within at least the second pore structure of the host framework. The photoelectric active guest component is a photoelectric active semiconductor phase and forms a continuous photoelectric active guest phase that extends through the thickness direction of the thin film for charge transport within the confined environment of the host framework. A molecular-level interface passivation layer comprising passivation molecules, wherein the passivation molecules are selectively anchored at the heterogeneous interface between the host backbone and the photoelectroactive guest component in a discontinuous distribution manner, for suppressing ion migration or interfacial nonradiative recombination of the photoelectroactive guest component. The charge-selective contact structure includes a hole-selective contact layer and an electron-selective contact layer that match the energy levels of the host framework.

2. The integrated energy skin with a hierarchical pore-confined hybrid superstructure according to claim 1, characterized in that, The first pore structure is a micropore with a characteristic pore size of 0.5-5 nm, used to provide interface confinement effect, chemical potential regulation or ion migration inhibition; the second pore structure is a mesopore or macropore with a characteristic pore size of 5-200 nm, formed by surfactant micellization physical template, used to accommodate the photoelectric active guest components and form charge transport pathways.

3. The integrated energy skin with a hierarchical pore-confined hybrid superstructure according to claim 1, characterized in that, The photoelectric active guest component has a grain boundary fusion structure induced by light pulse, and the effective carrier collection length Lc of the continuous phase of the photoelectric active guest satisfies: Lc ≥ 0.8d, where d is the physical thickness of the organic framework film.

4. The integrated energy skin with a hierarchical pore-confined hybrid superstructure according to claim 1, characterized in that, The photoelectric active guest component is selected from inorganic perovskite, quasi-two-dimensional perovskite, metal chalcogenide nanocrystals, organic-inorganic hybrid perovskite, or combinations thereof.

5. The integrated energy skin with a hierarchical pore-confined hybrid superstructure according to claim 1, characterized in that, The molecular-level interface passivation layer is distributed discontinuously on the surface of the host skeleton at the atomic level or in an island-like manner, and does not form a continuous covering film; the passivation small molecules are selectively anchored to unsaturated metal sites on the surface of the photoactive guest component through their end groups.

6. A structurally integrated energy skin with a hierarchical pore-confined hybrid superstructure according to claim 4 or 5, characterized in that, The metal chalcogenide nanocrystals are AgBiS2, the organic-inorganic hybrid semiconductor is MAPbI3, and when the photoactive guest component is AgBiS2, the passivating molecule is 1-dodecyl mercaptan; when the photoactive guest component is perovskite, the passivating molecule is octylamine iodine.

7. A method for preparing a structurally integrated energy skin with a hierarchical pore-confined hybrid superstructure as described in any one of claims 1-5, characterized in that, Includes the following steps: Step S1: On a substrate with a first charge-selective contact layer, a continuous two-dimensional covalent organic framework film with a first pore structure and a second pore structure is prepared as a host skeleton by solution phase self-assembly and dynamic covalent crystallization reaction. Step S2: The guest precursor is introduced into the pores of the host skeleton by vapor phase infiltration, and in-situ crystallization or solid-phase transformation is carried out in a confined space to generate a continuous photoelectric active guest phase that runs through the thickness direction of the thin film. Step S3: Passivating small molecules are introduced through gated vapor pulses to anchor them discontinuously at the host-guest heterogeneous interface; then, the hybrid film is subjected to flash curing to induce grain boundary fusion of the photoelectric active guest components; Step S4: Deposit a second charge-selective contact layer on top of the hybrid film to complete the fabrication of the energy skin.

8. The method for preparing a structurally integrated energy skin with a hierarchical pore-confined hybrid superstructure according to claim 7, characterized in that, In step S1, after the sol containing amine monomers and aldehyde monomers is mixed with a surfactant and coated, a physical template for the second pore structure is formed by evaporation-induced self-assembly. Subsequently, imine condensation and dynamic self-correction occur under heating conditions to form the host skeleton.

9. The method for preparing a structurally integrated energy skin with a hierarchical pore-confined hybrid superstructure according to claim 7, characterized in that, In step S2, a spatial atomic layer deposition method is used to induce the self-limiting adsorption of the guest precursor on the pore wall by a combination of precursor vapor pulse and immersion. Subsequently, a reaction gas is introduced to perform in-situ confined crystallization to generate the photoelectric active guest continuous phase.

10. The method for preparing a structurally integrated energy skin with a hierarchical pore-confined hybrid superstructure according to claim 7, characterized in that, In step S3, a xenon lamp array light pulse is used to perform flash curing, thereby achieving solid-phase welding of photoelectric active guest components while ensuring that the host skeleton does not undergo thermal degradation.

Images