Gas phase infiltration - in situ formation assembly method of hierarchical porous host frameworks and on-line acceptance method

Abstract

The application belongs to the technical field of photoelectric functional film manufacturing, and particularly relates to a hierarchical pore host framework gas phase permeation-in-situ formation assembly method and an online acceptance method. The assembly method takes a two-dimensional covalent organic framework film with a first pore structure and a second pore structure as a host framework; a guest precursor is introduced by pulse gas phase permeation for in-situ crystallization in a low-temperature confined space; then, an interface passivation molecule is introduced by gas phase permeation to form a discontinuous passivation layer, and flash solidification is used to induce grain boundary fusion and form a continuous guest phase; subsequently, an upper contact structure for electrical measurement is formed, a bias-dependent external quantum efficiency and a dark state current-voltage curve are obtained, an effective carrier collection characteristic length and a reverse saturation current density are fitted, and process acceptance and correction instructions are generated accordingly. The application is suitable for closed-loop intelligent manufacturing of complex and hybrid films, and greatly improves the yield of mass production.

Description

Technical Field

[0001] This invention belongs to the field of optoelectronic functional thin films and intelligent manufacturing technology, specifically relating to a vapor phase infiltration-in-situ formation assembly method and an online acceptance method for a hierarchical pore host framework. Background Technology

[0002] High-energy conversion thin films (such as perovskites and metal chalcogenides) are highly susceptible to ion migration, interfacial debonding, and deep-level recombination under complex service environments such as damp heat, vibration, and stress alternation, leading to a rapid decline in photoelectric conversion efficiency. Traditional multilayer heterojunction thin film manufacturing typically relies on solution coating processes, which not only suffer from process bottlenecks such as solvent erosion of the underlying layer, stress concentration within the film, and poor uniformity of large-area film formation, but also make it extremely difficult to achieve high-quality bonding on load-bearing structural surfaces with complex curvatures.

[0003] Two-dimensional covalent organic frameworks (COFs) with hierarchical porosity exhibit great potential as host framework materials in energy conversion (such as structurally integrated energy skins) due to their highly ordered pore arrays. They are typically filled with optoelectronically active materials such as perovskites or quantum dots as guest materials. However, traditional liquid-phase processes are prone to micro / mesopore blockage and cannot accurately repair defect states and grain boundaries at the host-guest interface.

[0004] To address this issue, vapor-phase infiltration combined with gated pulse passivation and flash curing has become the preferred solution for constructing high-quality hybrid superstructures. However, in industrial mass production, due to the complexity of the confined space at the nanoscale, there is a lack of effective online detection methods in traditional processes to determine whether microscopic channels are completely filled and connected by the substrate, and whether grain boundaries have achieved physical fusion. Once the film is formed, the internal state is like a "black box," resulting in extremely low yields in large-scale manufacturing. There is an urgent need for an intelligent manufacturing system that can accurately visualize the internal assembly quality and has the capability for online closed-loop process control. Summary of the Invention

[0005] The core objective of this invention is to solve the aforementioned industrialization challenges by providing a vapor-phase in-situ assembly method and an online acceptance method for a hierarchical pore host framework. The core advantage of this invention lies in the deep closed-loop synergy between the advanced "vapor-phase assembly-pulse passivation-flash curing" process and the "dual-parameter online acceptance" method.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A method for vapor-phase permeation-in-situ assembly and online acceptance of a hierarchical pore host framework 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 photoelectroactive 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 the confined space to generate a continuous photoelectroactive guest phase that runs through the thickness direction of the film. Step S3: Introduce interface passivation molecules through gated vapor pulses to anchor them discontinuously at the host-guest heterogeneous interface; then perform flash curing on the hybrid film to induce grain boundary fusion of photoelectric active guest components; Step S4: Deposit a second charge-selective contact layer and a top electrode on top of the hybrid thin film to complete the fabrication of the test device; Step S5: Perform online acceptance testing on the process line to obtain the bias-dependent external quantum efficiency (EQE) curve and dark-state current-voltage (JV) curve; Step S6: Extract the effective carrier collection characteristic length L from the bias-dependent EQE curve fitting. c,eff The reverse saturation current density J0 is extracted from the dark-state JV curve fitting. Step S7: Extract L c,eff The J0 value is compared with a preset threshold. If the Go criterion is met, the acceptance is passed. If it falls into the No-Go interval, a feedback instruction is generated to automatically correct the infiltration time of the guest precursor in step S2 or the number of gated vapor pulses and flash curing energy parameters in step S3.

[0007] Furthermore, the two-dimensional covalent organic framework film in step S1 is an imine-type COF film, and the characteristic size of the first pore structure is smaller than that of the second pore structure.

[0008] Furthermore, in step S2, the photoelectric active guest precursor is one or more combinations of an organic-inorganic hybrid perovskite precursor, an all-inorganic perovskite precursor, or a chalcogenide quantum dot precursor.

[0009] Furthermore, the gated vapor pulse process in step S3 includes: introducing passivating molecules containing organohalide vapor, organosulfide vapor, or organophosphine vapor for a single pulse exposure. exp Seconds, then vacuum pumping t vac A second constitutes a complete pulse cycle.

[0010] Furthermore, the flash curing process in step S3 employs short-duration high-energy xenon lamp array light pulses to provide thermal shock waves that penetrate the thin film and induce solid-phase welding between guest nanocrystals, while avoiding thermal degradation of the organic host framework.

[0011] Further, in step S6, the responsivity of the external quantum efficiency spectrum near the long-wavelength absorption limit under different bias voltages V is fitted using the Hecht equation: EQE(V) ∝ (L c,eff / d) [1 - exp(-d / L c,eff Extract the effective carrier collection characteristic length L. c,eff , where d is the physical thickness of the film.

[0012] Furthermore, the criterion logic in step S7 is as follows: Acceptance thresholds are defined as follows: the lower limit of the critical collection length is set to 0.6d; the upper limit of the critical reverse saturation current density is set to the baseline value J. 0_ref ×10; If L c,eff ≥0.6d and J0≤J 0_ref If the value is ×10, it is determined to be a qualified GO and is released to proceed to the next process. If L c,eff If the time is less than 0.6d, it is determined that the connectivity of the object is limited, and the feedback control system increases the infiltration time of the object precursor in step S2. If J0 > J 0_ref If the value is ×10, it is determined that the grain boundary is not fused or the interface defect dominates the composite. The feedback control system increases the number of gated vapor pulses in step S3 or adjusts the flash curing energy.

[0013] Furthermore, in step S4, both the second charge-selective contact layer and the top electrode are prepared using a solvent-free vacuum dry deposition process to avoid damaging the solidified micro-interfaces inside the hybrid film.

[0014] A second aspect of the present invention provides a production control system for performing the above-described online acceptance method, comprising: Photoelectric measurement equipment is configured to acquire bias-dependent EQE curves and dark-state JV curves of the test device on the process line; The data processing terminal, communicatively connected to the photoelectric measurement device, includes a processor and a memory. The processor executes stored instructions to: extract the effective carrier collection feature length L from the bias-dependent EQE curve fitting. c,eff The reverse saturation current density J0 is extracted from the dark-state JV curve fitting. The online control equipment for process parameters is controlled by the data processing terminal, which extracts L... c,eff The process parameter is compared with a preset threshold, and when it is determined to be No-Go, a correction command is output to the online control device for the process parameters to automatically adjust the vapor phase permeation time, the number of gated vapor pulses, or the flash curing energy.

[0015] Compared with the prior art, the beneficial effects of the present invention are: When the online acceptance system extracts L c,eff When J0 accurately identifies abnormalities in the internal physical state of the thin film, in-situ compensation integrating diagnosis and treatment can be implemented. Specifically: Extensive physical model derivations and experiments show that when the extracted effective carrier collection characteristic length L... c,eff When the thickness is less than 60% of the physical thickness (i.e., 0.6d), it means that the vertical connectivity of the object in the channel in step S2 is severely limited (the channel is not filled or is open). At this time, the system automatically feeds back to increase the gas phase permeation time. When the reverse saturation current density J0 exceeds 10 times the ideal reference value, it means that the non-radiative recombination of the interface in step S3 is too high or the grain boundary is not fused. The system will automatically increase the number of gated passivation pulses or increase the thermal shock wave energy of flash curing.

[0016] The dual-parameter threshold selected in this invention has both strong physical guidance significance and engineering application value, fundamentally opening up the "last mile" for complex hybrid energy skins to move from the laboratory to large-scale yield control. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the hierarchical pore structure and the photoelectric active guest component structure formed by gas phase infiltration-in situ in this 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

[0018] 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.

[0019] 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.

[0020] Terminology Explanation: 1. Effective carrier collection characteristic length (L) c,eff , Effective Carrier Collection Length) Physical definition: refers to the average spatial distance that photogenerated carriers can effectively transport under the drive of a built-in electric field or an external bias voltage before nonradiative recombination occurs and are eventually collected by the contact electrode.

[0021] Characterization significance in this invention (connectivity probe): In hierarchical pore-confined hybrid superstructures, L c,eff This directly reflects the physical filling saturation and three-dimensional connectivity of photoelectroactive guest components within the pores of the two-dimensional COF host framework. Because this invention employs a vapor-phase infiltration process, if L... c,eff Much smaller than the physical thickness d of the film (e.g., L) c,eff If the time is less than 0.6d, it means that the guest material has not completely penetrated the channel, and there is a macroscopic open circuit, void, or severe "dead hole" effect (i.e., "restricted guest connectivity"). Therefore, this parameter is used in this invention as a direct closed-loop criterion for automatically extending the gas phase permeation time.

[0022] 2. Reverse Saturation Current Density (J0) Physical definition: According to the ideal diode model (Shockley Diode Equation), it refers to the background leakage current density of a semiconductor heterojunction device in a dark environment, caused by thermally excited minority carrier diffusion and defect recombination in the depletion region.

[0023] Characterization significance in this invention (defect state probe): Within the highly confined host-guest nanospace, the large specific surface area readily breeds defects. In this invention, J0 serves as a probe for evaluating the defect state density and grain boundary passivation quality at heterogeneous interfaces. If J0 is abnormally high (e.g., exceeding the baseline reference value J...), it indicates a defect. 0_ref If the energy density is 10 times higher than the host-guest energy density, it indicates that effective fusion has not been achieved between the guest crystals, or that there are a large number of unpassivated dangling bonds at the host-guest interface, leading to severe nonradiative recombination losses. Therefore, this parameter is used in this invention as a direct closed-loop criterion for automatically increasing the number of passivation vapor pulses and improving the flash curing energy.

[0024] Example 1: Preparation and acceptance of organic-inorganic hybrid perovskite (MAPbI3) as the host. Step S1: Host skeleton preparation FTO conductive glass with a surface resistivity of 15 Ω / □ was selected as the substrate. The substrate was sequentially ultrasonically cleaned with deionized water, acetone, and isopropanol for 15 min each, dried with nitrogen, and then treated under UV-ozone for 15 min. A commercial SnO2 colloidal dispersion, diluted with deionized water to a mass fraction of 2.5 wt%, was spin-coated at 4000 rpm for 30 s and annealed at 150 °C for 30 min to obtain a first charge-selective contact layer with a thickness of approximately 30 nm. Subsequently, the COF precursor sol was prepared: 1,3,5-tris(4-aminophenyl)benzene (TAPB, 10 mg / mL) and terephthalaldehyde (TPA, 5.7 mg / mL, TAPB:TPA molar ratio of 2:3) were dissolved in a mixed solvent of 1,4-dioxane / trimethylbenzene (volume ratio 1:1), 0.2 mL of 3 mol / L acetic acid was added as a catalyst, and 5 wt% of Pluronic F127 as a surfactant was added. The mixture was then magnetically stirred at room temperature for 30 min to form a homogeneous sol. The sol was spin-coated onto the SnO2 / FTO substrate at 3000 rpm for 30 s, and then placed in a controlled evaporation environment at 60 °C for 30 min to induce evaporation-induced self-assembly (EISA) to form a physical template for the second pore structure. Subsequently, it was transferred to a sealed reactor and reacted at 120 °C for 24 h, resulting in imine condensation and dynamic covalent self-correction. After the reaction, the surfactant was eluted sequentially with anhydrous ethanol and tetrahydrofuran, and the film was vacuum-dried at 80 °C for 1 h to obtain an imine-type two-dimensional COF host framework film with a thickness d of 120 nm. Ellipsometry and cross-sectional SEM characterization showed that the characteristic pore size of the first pore structure was approximately 1.5 nm, and the characteristic pore size of the second pore structure was 12-15 nm.

[0025] Step S2: In-situ transformation of the gas-phase infiltration guest The substrate carrying the host framework was placed in a dual-source vacuum permeation chamber and pre-vacuumed at 70°C and 100 Pa for 30 min to remove adsorbed water in the pores. The substrate temperature was then maintained at 100°C. First, the PbI2 evaporation source (evaporation boat temperature 340°C) was turned on to introduce PbI2 vapor for 10 min and allowed to stand for 10 min to wet the substrate, so that the lead precursor was preferentially adsorbed on the inner wall of the second pore structure. Then, the MAI evaporation source (evaporation boat temperature 145°C) was turned on to allow MAI vapor and residual PbI2 vapor to permeate together at 300 Pa for 30 min. After that, the temperature was raised to 120°C under nitrogen protection and held for 10 min to complete the in-situ transformation in the confined space, resulting in a continuous MAPbI3 guest phase that runs through the thickness direction of the film.

[0026] Step S3: Gated vapor pulse passivation and flash curing The reaction chamber was cooled to 90°C, and octylamine iodine (OAI) vapor was introduced for gated pulse passivation. Each cycle had an exposure time (texp) of 60 s, followed by a vacuum (tvac) of 300 s, repeated for three cycles. This allowed OAI to anchor in a discontinuous island-like manner at uncoordinated Pb sites on the host-guest heterojunction interface and MAPbI3 grain boundaries. After passivation, a xenon lamp array was used for flash curing with a pulse width of 1.8 ms, three pulses, and a total energy density of 15 J / cm³. 2 This is to induce the fusion of guest grain boundaries and prevent the thermal decomposition of organic guests.

[0027] Step S4: Dry device fabrication ≤5×10 -4 Under a vacuum of Pa, 30 nm of carbon 60 (C60) was first thermally evaporated as a second charge-selective contact layer, followed by the deposition of 80 nm of silver (Ag) as the top electrode at a rate of 0.1–0.2 nm / s. The effective test area was 0.09 cm². 2 This yields test devices for online acceptance testing.

[0028] Steps S5-S7: Online Acceptance and Feedback Closed Loop Under nitrogen protection at 25℃, bias-dependent EQE curves and dark-state JV curves were acquired using an inline photoelectric measurement system on the production line. EQE curves were acquired in 0.1 V steps within a bias range of 0 to -1.0 V near the long-wavelength absorption limit (730-800 nm), while dark-state JV curves were acquired within a range of -0.2 to 1.0 V. L was obtained by fitting the curve to the Hecht equation. c,eff =110 nm, corresponding to 110 / 120=0.91d; J0=1.2×10⁻⁶ after fitting the dark-state JV. -7 mA / cm 2 Below the preset upper limit J 0_ref ×10. The system determines that this batch of devices is Go (good) and releases them to the next process.

[0029] Example 2: Preparation and acceptance of chalcogenide quantum dots (AgBiS2) as the host Step S1: The host framework was prepared in the same way as in Example 1, using the same SnO2 / FTO substrate pretreatment, TAPB / TPA / F127 sol formulation and EISA-DCC film preparation conditions to obtain an imine-type two-dimensional COF host framework film with a thickness d of 120 nm, a first pore structure of about 1.5 nm and a second pore structure of 12-15 nm.

[0030] Step S2: Vapor-phase confined infiltration and in-situ sulfidation The substrate carrying the host framework was placed in a space atomic layer permeation chamber and pretreated under vacuum at 70°C and 100 Pa for 30 min. The chamber temperature was then set to 110°C, Ag (pivalate) vapor was pulsed for 1 s and soaked for 60 s, followed by purging with nitrogen for 90 s. The chamber temperature was then raised to 140°C, Bi (thd)3 vapor was pulsed for 1 s and soaked for 60 s, followed by purging with nitrogen for 90 s. This Ag / Bi dual precursor sequence was repeated for three supercycles, allowing the Ag and Bi precursors to form a co-distributed adsorption layer within the second pore structure. The chamber temperature was then adjusted to 120°C, and H2S vapor was introduced at 300 Pa for 20 min, allowing the Ag and Bi precursors adsorbed on the pore walls to undergo in-situ sulfidation within the confined space, generating a continuous AgBiS2 guest phase spanning the film thickness.

[0031] Step S3: Gated vapor pulse passivation and flash curing The reaction chamber was cooled to 80°C, and 1-dodecathiol (DDT) vapor was introduced for gated pulse passivation. Each vapor exposure lasted 1 s, followed by 300 s of vacuuming, repeated for three cycles to anchor 1-DDT molecules to unsaturated metal sites on the AgBiS2 surface in a discontinuous distribution. After passivation, a xenon lamp array was used for flash curing with a pulse width of 2.0 ms, three pulses, and a total energy density of 25 J / cm³. 2 To induce grain boundary fusion between AgBiS2 nanocrystals.

[0032] Step S4: Dry device fabrication ≤5×10 -4 Under a vacuum of Pa, 30 nm of carbon 60 (C60) was first thermally evaporated as a second charge-selective contact layer, followed by the deposition of 80 nm of silver (Ag) as the top electrode at a rate of 0.1–0.2 nm / s. The effective test area was 0.09 cm². 2 This yields test devices for online acceptance testing.

[0033] Steps S5-S7: Online Acceptance and Feedback Closed Loop Under nitrogen protection at 25℃, bias-dependent EQE curves and dark-state JV curves were acquired using an inline photoelectric measurement device on the process line. EQE curves were acquired in 0.1 V steps within a bias range of 0 to -1.0 V near the long-wavelength absorption limit (850-950 nm), while dark-state JV curves were acquired within a range of -0.2 to 1.0 V. L was obtained by fitting the curve to the Hecht equation. c,eff =105 nm, corresponding to 105 / 120 = 0.875 d; J0 = 2.1 × 10⁻⁶ after fitting with JV in the dark state. -7 mA / cm 2 Below the preset upper limit J 0_ref×10. The system determines that this batch of devices is Go (good) and releases them to the next process.

[0034] Comparative Example 1: Traditional liquid phase spin coating method for filling (simulating step S2 abnormality) Preparation process: Skip step S2 (vapor permeation) and directly spin-coat the MAI and PbI2 solutions onto the COF surface. The remaining steps are the same.

[0035] Acceptance results: Due to extremely rapid solvent evaporation causing mesopore blockage, L was measured during online extraction. c,eff The wavelength is only 35 nm (0.29d < 0.6d). The system determines this as a No-Go process and triggers an alarm: the liquid phase method cannot form a confined penetrating phase, and it is necessary to switch to the gas phase permeation process.

[0036] Comparative Example 2: Missing Pulse Passivation and Flash Curing (Simulation Step S3 Abnormality) Preparation process: After completing step S2, step S3 is skipped directly. OAI vapor passivation and xenon lamp flash curing are not performed. The top electrode is deposited directly.

[0037] Acceptance result: L was measured c,eff = 90 nm (0.75d) satisfies the connectivity requirement, but the dark state J0 surges to 8.5 × 10 -5 mA / cm 2 (Exceeding the limit by a thousand times). The system determined it to be a No-Go error. The terminal determined that the grain boundary was not fused / interface leakage, and immediately output a closed-loop command to the process parameter control equipment: requiring the gated vapor pulse to be reactivated in the next batch, and verifying the trigger energy of the xenon lamp curing equipment.

[0038] The core data of Examples 1-2 and Comparative Examples 1-2 are compared in Table 1 below.

[0039] Table 1. Comparison of Core Data Example 1 In-situ crystallization through vapor phase penetration <![CDATA[Execute (OAI pulse +25 J / cm 2 Flash fixation)]]> 110 nm 0.91d <![CDATA[1.2 ×10 -7 ]]> Go (Release to the next process) Example 2 Spatial ALD confined sulfurization <![CDATA[Execute (DDT pulse + 25 J / cm 2 Flash fixation)]]> 105 nm 0.87d <![CDATA[2.1 ×10 -7 ]]> Go (Release to the next process) Comparative Example 1 Liquid phase spin coating implement 35 nm 0.29d <![CDATA[6.5 ×10 -6 ]]> No-Go (Instruction: Extend infiltration time) Comparative Example 2 In-situ crystallization through vapor phase penetration Not executed (grain boundary defect exists) 90 nm 0.75d <![CDATA[8.5 ×10 -5 ]]> No-Go (Command: Increase passivation pulse / curing energy) 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 method for vapor-phase permeation-in-situ formation assembly and online acceptance of a hierarchical pore host skeleton, 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 photoelectroactive 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 the confined space to generate a continuous photoelectroactive guest phase that runs through the thickness direction of the film. Step S3: Introduce interface passivation molecules through gated vapor pulses to anchor them discontinuously at the host-guest heterogeneous interface; then perform flash curing on the hybrid film to induce grain boundary fusion of photoelectric active guest components; Step S4: Deposit a second charge-selective contact layer and a top electrode on top of the hybrid thin film to complete the fabrication of the test device; Step S5: Perform online acceptance testing on the process line to obtain the bias-dependent external quantum efficiency curve and dark-state current-voltage curve; Step S6: Extract the effective carrier collection characteristic length L from the bias-dependent external quantum efficiency curve fitting. c,eff The reverse saturation current density J0 is extracted from the dark-state current-voltage curve fitting. Step S7: Extract L c,eff The J0 value is compared with a preset threshold. If the Go criterion is met, the acceptance is passed. If it falls into the No-Go interval, a feedback instruction is generated to automatically correct the infiltration time of the guest precursor in step S2 or the number of gated vapor pulses and flash curing energy parameters in step S3.

2. The method for vapor-phase permeation-in-situ formation assembly and online acceptance of a hierarchical pore host skeleton according to claim 1, characterized in that, The two-dimensional covalent organic framework film in step S1 is an imine-type COF film, and the characteristic size of the first pore structure is smaller than that of the second pore structure.

3. The method for vapor-phase permeation-in-situ formation assembly and online acceptance of a hierarchical pore host skeleton according to claim 1, characterized in that, In step S2, the photoelectroactive guest precursor is one or more combinations of organic-inorganic hybrid perovskite precursor, all-inorganic perovskite precursor, or chalcogenide quantum dot precursor.

4. The method for vapor-phase permeation-in-situ formation assembly and online acceptance of a hierarchical pore host skeleton according to claim 1, characterized in that, The gated vapor pulse process in step S3 includes: introducing passivating molecules containing organohalide vapor, organosulfide vapor, or organophosphorus vapor for a single pulse exposure. exp Seconds, then vacuum pumping t vac A second constitutes a complete pulse cycle.

5. The method for vapor-phase permeation-in-situ formation assembly and online acceptance of a hierarchical pore host skeleton according to claim 1, characterized in that, The flash curing process in step S3 uses xenon lamp array light pulses to provide thermal shock waves that penetrate the thin film and induce solid-phase welding between guest nanocrystals, while avoiding thermal degradation of the organic host skeleton.

6. The method for vapor-phase permeation-in-situ formation assembly and online acceptance of a hierarchical pore host skeleton according to claim 1, characterized in that, In step S6, the response of the external quantum efficiency spectrum at the long-wavelength absorption limit under different bias voltages V is fitted using the Hecht equation: EQE(V) ∝ (L c,eff / d) [1 - exp(-d / L c,eff Extract the effective carrier collection characteristic length L. c,eff , where d is the physical thickness of the film.

7. A method for vapor-phase permeation-in-situ formation assembly and online acceptance of a hierarchical pore host skeleton according to claim 1 or 6, characterized in that, The criterion logic in step S7 is as follows: Acceptance thresholds are defined as follows: the lower limit of the critical collection length is set to 0.6d; the upper limit of the critical reverse saturation current density is set to the baseline value J. 0_ref ×10; If L c,eff ≥0.6d and J0≤J 0_ref If the value is ×10, it is determined to be a qualified GO and is released to proceed to the next process. If L c,eff If the time is less than 0.6d, it is determined that the connectivity of the object is limited, and the feedback control system increases the infiltration time of the object precursor in step S2. If J0 > J 0_ref If the value is ×10, it is determined that the grain boundary is not fused or the interface defect dominates the composite. The feedback control system increases the number of gated vapor pulses in step S3 or adjusts the flash curing energy.

8. The method for vapor-phase permeation-in-situ formation assembly and online acceptance of a hierarchical pore host skeleton according to claim 1, characterized in that, In step S4, both the second charge-selective contact layer and the top electrode are prepared using a solvent-free vacuum dry deposition process to avoid damaging the solidified micro-interfaces inside the hybrid film.

9. A production control system for executing the online acceptance method according to any one of claims 1-8, characterized in that, include: The photoelectric measurement equipment is configured to acquire the bias-dependent external quantum efficiency curve and dark-state current-voltage curve of the test device on the process line; The data processing terminal, communicatively connected to the photoelectric measurement device, includes a processor and a memory. The processor executes stored instructions to: extract the effective carrier collection feature length L from the bias-dependent external quantum efficiency curve fitting. c,eff The reverse saturation current density J0 is extracted from the dark-state current-voltage curve fitting. The online control equipment for process parameters is controlled by the data processing terminal, which extracts L... c,eff The process parameter is compared with a preset threshold, and when it is determined to be No-Go, a correction command is output to the online control device for the process parameters to automatically adjust the vapor phase permeation time, the number of gated vapor pulses, or the flash curing energy.

Images