Online integrated photoluminescence test device and test method

Abstract

The application discloses an online integrated photoluminescence testing device and a testing method. The online integrated photoluminescence testing device adopts an in-situ integrated architecture of a deposition unit, a photoluminescence testing unit and an atmosphere control unit. An optical module of the photoluminescence testing unit is communicated with a deposition chamber through a light transmission window equipped with an opening and closing shutter assembly. A time sequence coordination module realizes precise linkage of a deposition process, a testing process and the shutter opening and closing assembly. The atmosphere control unit continuously maintains a low-oxygen and low-water environment of a testing area. The testing method realizes a closed loop process of system initialization, parameter presetting, film deposition, in-situ PL testing, data determination and shutdown maintenance, and completes in-situ sealed testing after film deposition. The application can completely avoid atmospheric exposure pollution in the sample transfer process, realize real-time linkage of the testing and deposition processes, and the total time consumption of single sample testing is less than or equal to 30 seconds, which significantly improves the testing efficiency and the accuracy of quality evaluation, and can be directly adapted to the online quality control requirements of industrial production.

Description

Technical Field

[0001] This invention relates to the field of perovskite thin film preparation technology, and in particular to an online integrated photoluminescence testing device and testing method. Background Technology

[0002] Perovskite solar cells have become a hot research topic in the photovoltaic field due to their significant advantages such as high photoelectric conversion efficiency and low-cost fabrication. The quality parameters of the perovskite precursor inorganic salt thin film (such as PbI2 / PbBr2 mixed film) directly determine the crystallinity, defect state density, and final photoelectric conversion efficiency of the subsequent perovskite thin film. Therefore, accurate detection and control of the quality of this type of precursor film is crucial.

[0003] Photoluminescence (PL) testing is an effective technique for evaluating thin film quality. By detecting key characteristic parameters such as emission peak position, emission intensity, and full width at half maximum (FWHM), the compositional uniformity, lattice integrity, and defect state of the thin film can be quickly determined. In existing technologies, PL testing for perovskite precursor inorganic salt thin films mostly employs an offline testing mode. This means that after film deposition, the sample must be removed from the deposition equipment and transferred to a dedicated PL testing device for analysis. However, this offline testing mode has the following technical drawbacks: 1. Samples are inevitably exposed to the atmospheric environment during transfer, which can easily lead to moisture absorption, oxidation, and secondary contamination, severely affecting the authenticity and accuracy of the test results; 2. Real-time linkage between test data and the deposition process cannot be achieved, making it difficult to dynamically optimize and adjust deposition process parameters based on test results, which is detrimental to closed-loop quality control in industrial mass production; 3. The testing process is cumbersome, with additional steps such as sample transfer and environmental pretreatment taking a long time, resulting in low testing efficiency and failing to meet the pace requirements of industrial mass production. Summary of the Invention

[0004] The purpose of this invention is to provide an online integrated photoluminescence testing device and method, which can realize in-situ, closed PL testing after thin film deposition, effectively avoid secondary pollution, establish a real-time correlation between test parameters and deposition process, thereby improving the accuracy of quality control and testing efficiency, and meeting the needs of industrial mass production.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is: an online integrated photoluminescence testing device for in-situ quality detection of perovskite precursor inorganic salt thin films, comprising:

[0006] The deposition unit includes a vapor deposition apparatus body for depositing perovskite precursor inorganic salt thin films. The vapor deposition apparatus body has a sealed light-transmitting window, and an opening / closing baffle assembly is provided at the light-transmitting window.

[0007] The photoluminescence testing unit includes an optical module, a timing coordination module, and a data processing module. The optical module is located at the light-transmitting window and, after being opened by the opening and closing baffle assembly, connects to the optical path of the vapor deposition equipment body for directional introduction of excitation light and export of fluorescence signals to the vapor deposition equipment body. The timing coordination module is connected to both the deposition unit and the optical module for timing matching of the deposition and testing processes. The data processing module is used to acquire deposition parameters and test data in real time.

[0008] An atmosphere control unit, which is connected to the deposition unit and the photoluminescence testing unit, is used to maintain a low-oxygen, low-water testing atmosphere inside each unit.

[0009] As a further optimization, the perovskite precursor inorganic salt film includes a PbI2 film, a PbBr2 film, or a mixed film of PbI2 and PbBr2.

[0010] As a further optimization, the main body of the vapor deposition equipment has a deposition chamber, which is equipped with a temperature control unit, a vacuum control unit, a sample stage, and a quartz evaporation source. The quartz evaporation source is located below the bearing surface of the sample stage. The light-transmitting window includes a flange hole disposed on the main body of the vapor deposition equipment and communicating with the deposition chamber. High-transmittance quartz glass is sealed inside the flange hole. The opening and closing baffle assembly includes a drive component and a light-shielding plate disposed at the output end of the drive component. The light-shielding plate is driven to open or cover the light-transmitting window.

[0011] As a further optimization, the optical module includes an excitation source, a beam control component, an optical filter component, a beam splitter component, and a detection component; the excitation source is a 405nm or 450nm visible light semiconductor laser; the beam control component includes a collimating-focusing lens group and a fluorescence collecting lens; the collimating-focusing lens group is connected to the excitation source via an optical fiber coupler for focusing and introducing the excitation light; the fluorescence collecting lens is used to converge and export the fluorescence signal to the optical filter component and then to the beam splitter component; the detection component includes a photomultiplier tube or a CCD detector for detecting the fluorescence signal exported by the beam splitter component.

[0012] As a further optimization, the timing coordination module includes a digital delay pulse generator and a timing controller; the timing control accuracy of the digital delay pulse generator is ≤1ns, and it can be set to start the test with a delay of 0.1-1s after deposition is completed. The timing controller is electrically connected to the opening and closing baffle assembly, controlling the baffle to open 0.05-0.2s before the test and close 0.05-0.2s after the test is completed.

[0013] As a further optimization, the atmosphere control unit includes an inert gas supply component, a flow control component, and an impurity detection component; the inert gas supply component is a high-purity Ar gas supply system with a purity ≥99.999%; the flow control component is a flow controller that can adjust the inert gas flow rate to 5-100 sccm; and the impurity detection component is an online oxygen / moisture sensor with a detection accuracy ≤0.1ppm.

[0014] This invention also provides an online integrated photoluminescence testing method, which uses the above-mentioned online integrated photoluminescence testing device for in-situ quality detection of perovskite precursor inorganic salt thin films, and includes the following steps:

[0015] S1) Start-up and calibration: Turn on the deposition unit, photoluminescence test unit and atmosphere control unit, and preheat; perform wavelength calibration and intensity calibration on the photoluminescence test unit; execute the vacuum-inert gas replacement procedure through the atmosphere control unit to establish a low-oxygen and low-water atmosphere;

[0016] S2) Parameter preset: Set deposition parameters, photoluminescence test parameters, and timing coordination parameters through the data processing module;

[0017] S3) Thin film deposition: The target perovskite precursor inorganic salt thin film is deposited through the deposition unit. After the deposition is completed, a deposition completion signal is sent to the timing coordination module.

[0018] S4) In-situ photoluminescence test: The timing coordination module responds to the deposition completion signal and controls the opening and closing baffle assembly to open according to the preset timing sequence. The optical module collects multi-point photoluminescence signals of the thin film on the deposition station.

[0019] S5) Data processing and judgment: The data processing module performs background subtraction and feature parameter extraction on the acquired signal to complete the thin film quality judgment;

[0020] S6) Reset after test: The timing coordination module controls the opening and closing of the baffle assembly to close, maintain the inert gas purging for a preset time, and then shut down each unit.

[0021] As a further optimization, the vacuum-inert gas replacement procedure is repeated 2-4 times.

[0022] As a further optimization, the multi-point acquisition mode acquires photoluminescence signals from the center of the thin film and at least two edge points, with each point acquisition lasting 2-5 seconds; the data processing module automatically subtracts background signals using a Gaussian fitting algorithm, and the total test time for a single sample is ≤30 seconds.

[0023] As a further optimization, the characteristic parameters include emission peak position, emission intensity, and half-width at half-maximum (WHM). When the emission peak position deviation is less than a set value, the emission intensity fluctuation is less than a set value, and the WHM is less than a set value, the film quality is determined to be qualified.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] 1. Through the in-situ integrated design of the "deposition-test" module, the shared chamber space and atmosphere maintenance system completely eliminate the sample transfer process, avoid moisture absorption and oxidation contamination caused by atmospheric exposure, and ensure that the test data truly reflects the intrinsic quality of the film;

[0026] 2. It is equipped with an opening and closing baffle assembly, which can realize the time linkage of "closing during the deposition stage and opening during the testing stage", which can effectively block the optical contamination caused by the raw material vapor adhering to the window surface during the deposition process and ensure the accuracy of the test;

[0027] 3. The timing coordination module enables the timing coordination of deposition and testing. Test data is fed back to the host computer in real time, and the deposition process parameters can be dynamically optimized based on this data to form a closed-loop quality control and accurately adapt to the needs of industrial mass production.

[0028] 4. The total testing time for a single sample is ≤30 seconds, with no need for offline transfer and preprocessing steps, which greatly improves testing efficiency and can accurately match the cycle time requirements of industrial mass production;

[0029] 5. Through the collaborative design of precise optical path calibration, automatic background subtraction, and multi-point acquisition, the accuracy and stability of PL feature parameter extraction are ensured, providing reliable data support for thin film quality assessment. Attached Figure Description

[0030] Figure 1 This is a schematic diagram of the online integrated photoluminescence testing device of the present invention.

[0031] Figure 2 This is a schematic diagram of the optical module of the present invention. Detailed Implementation

[0032] The following are specific embodiments of the present invention, which further describe the technical solution of the present invention, but the present invention is not limited to these embodiments.

[0033] like Figures 1 to 2As shown, an online integrated photoluminescence testing device is used for in-situ quality testing of perovskite precursor inorganic salt films. It includes a deposition unit 10, a photoluminescence testing unit 20, and an atmosphere control unit 30. The deposition unit 10 includes a vapor deposition equipment body 101 with a deposition chamber 100 for depositing the perovskite precursor inorganic salt film 10A. The vapor deposition equipment body 101 has a sealed light-transmitting window 102, and an opening / closing baffle assembly 103 is provided at the light-transmitting window 102. The photoluminescence testing unit 20 includes an optical module 21, a timing coordination module, and a data processing module. The timing coordination module and the data processing module are integrated... Inside the chassis module 22, which is connected to the host computer 23, the optical module 21 is located at the light-transmitting window 102. After being opened by the opening and closing baffle assembly 103, it is connected to the optical path of the vapor deposition equipment body 101 and used for the directional introduction of excitation light and the export of fluorescence signal to the vapor deposition equipment body 101. The timing coordination module is connected to the deposition unit 10 and the optical module 21 respectively for the timing matching of the actions of the deposition process and the testing process. The data processing module is used to collect deposition parameters and test data in real time. The atmosphere control unit 30 is connected to the deposition unit 10 and the photoluminescence test unit 20 to maintain the low oxygen and low water test atmosphere inside each unit.

[0034] In this invention, the perovskite precursor inorganic salt film may include a PbI2 film, a PbBr2 film, or a mixed film of PbI2 and PbBr2. The perovskite precursor inorganic salt film 10A is deposited in the deposition chamber 100 of the vapor deposition apparatus body 101. During this process, the opening and closing baffle assembly 103 closes the light-transmitting window 102 to ensure the smooth progress of the deposition process. After the deposition process is completed, the opening and closing baffle assembly 103 opens the light-transmitting window 102, and the first optical module 21 activates, directing its excitation light into the deposition chamber 100 of the vapor deposition apparatus body 101, acting on the perovskite precursor inorganic salt film 10A. The generated fluorescence signal is exported through the light-transmitting window 102 from the deposition chamber 100 of the vapor deposition apparatus body 101 to the second optical module 21'. After the second optical module 21' processes the fluorescence signal, the data is fed back to the data processing module for data processing and judgment. During the deposition process and photoluminescence process, the timing coordination module matches the various action processes. In this invention, the opening and closing baffle assembly 103 is fixedly installed inside the deposition chamber 100 adjacent to the light-transmitting window 102 and electrically connected to the timing coordination module to realize the timing linkage of "closing during the deposition stage and opening during the testing stage". This can effectively block the optical pollution caused by the raw material vapor adhering to the window surface during the deposition process, thereby achieving in-situ sealed integration. Moreover, the deposition and photoluminescence share the chamber space and atmosphere maintenance system, completely eliminating the sample transfer process and avoiding moisture absorption and oxidation pollution caused by atmospheric exposure, ensuring that the test data truly reflects the intrinsic quality of the film.

[0035] Preferably, the deposition chamber 100 of the vapor deposition apparatus body 101 is equipped with a sample stage 11, a temperature control unit 12, a quartz evaporation source 13, and a vacuum control unit 14. The quartz evaporation source 13 is located below the bearing surface of the sample stage 11. The perovskite precursor inorganic salt film 10A is deposited on the sample stage 11 through a substrate, forming an upward deposition structure with the evaporation source below and the sample above. After the deposition process, in one embodiment, the excitation light path adopts a "bottom-up" introduction method, and the fluorescence signal adopts a "lateral" method. The "downward export" method can avoid mutual interference between excitation light and fluorescence signal, and improve the signal-to-noise ratio of signal detection; the light transmission window 102 includes a flange hole set on the main body 101 of the vapor deposition equipment and connected to the deposition chamber 100. The flange hole is sealed with high-transmittance quartz glass with a transmittance of ≥95% and is suitable for the 400-700nm test band; the opening and closing baffle assembly 103 includes a driving component and a light shield set at the output end of the driving component. The light shield can be opened or covered by the driving component.

[0036] The optical module (including the first optical module 21 and the second optical module 21') includes an excitation source 211, a beam control component, an optical filter component 212, a beam splitter component 213, and a detection component 214. The excitation source 211 is a 405nm or 450nm visible light semiconductor laser. The beam control component includes a collimating-focusing lens group and a fluorescence collecting lens. For the first optical module 21, it is used to emit excitation light. It has a collimating-focusing lens group, which is used to connect to the excitation source 211 through an optical fiber coupler for focusing and introducing the excitation light. For the second optical module 21', it is used to collect fluorescence signals. It has a fluorescence collecting lens, which is used to converge and export the fluorescence signal to the optical filter component 212 and then to the beam splitter component 213. The detection component 214 includes a photomultiplier tube or a CCD detector for detecting the fluorescence signal exported by the beam splitter component 213. This application utilizes excitation light emitted from excitation source 211 to excite electronic transitions in the perovskite precursor inorganic salt film 10A, and then evaluates the film quality by detecting the characteristic parameters of the fluorescence signal released during the transition process. The specific testing principle is as follows: 1. Excitation stage: Excitation source 211 outputs excitation light with a wavelength of 405 nm or 450 nm according to the composition characteristics of the film sample. After the excitation light accurately irradiates the surface of the film sample, the electrons in the sample absorb photon energy and transition from the ground state to the excited state; 2. Fluorescence emission stage: Electrons in the excited state are unstable and rapidly transition back to the ground state, releasing a fluorescence signal of a specific wavelength; 3. Signal screening stage: The fluorescence signal passes through optical filter component 212 to filter out residual stray light from the excitation light, retaining only the target fluorescence signal of 450-720 nm; 4. Spectroscopic detection stage: The screened fluorescence signal enters spectroscopic component 213 (monochromatic instrument) for wavelength dispersion, and the fluorescence signal is then analyzed. After the fluorescence signals of different wavelengths are separated, they are transmitted to the detection component 214 (such as a high-sensitivity photodetector). The detector converts the optical signal into an electrical signal. 5. Data processing stage: After the electrical signal is amplified and filtered by the signal conditioning module 215, it is transmitted to the host computer 22 (equipped with a LabVIEW control platform). The host computer 22 performs background subtraction through Gaussian fitting algorithm and extracts characteristic parameters such as emission peak position, emission intensity, and full width at half maximum. These parameters directly reflect the compositional uniformity, lattice integrity and defect state of the thin film, and finally complete the accurate determination of the thin film quality.

[0037] By setting and arranging the first optical module 21 and the second optical module 21', the phenomenon of mutual interference between excitation light and fluorescence signal can be effectively avoided, as mentioned above, combined with Figure 1As shown, the first optical module 21 is located at the bottom, and its excitation light path adopts a "bottom-up" input method. The fluorescence signal is "side-down" exported and received by the second optical module 21' located on the side. In another embodiment, the excitation light can be emitted from one side and the fluorescence signal can be collected from the other side. Alternatively, the excitation light can be emitted from one side and the fluorescence signal can be collected from the bottom. In the above different methods, only the relative positions of the first optical module 21 and the second optical module 21' need to be adjusted.

[0038] The core function of the timing coordination module is to achieve timing coordination control of the deposition end signal, the test start signal and the opening and closing action of the baffle. The timing coordination module includes a digital delay pulse generator and a timing controller. The timing control accuracy of the digital delay pulse generator is ≤1ns. It can be set to start the test with a delay of 0.1-1s after the deposition is completed. The timing controller is electrically connected to the opening and closing baffle assembly, controlling the baffle to open 0.05-0.2s before the test and close 0.05-0.2s after the test is completed.

[0039] The atmosphere control unit 30 shares a high-purity Ar gas supply system with the deposition unit 10. The atmosphere control unit 30 includes an inert gas supply component, a flow control component, and an impurity detection component. The inert gas supply component is a high-purity Ar gas supply system with a purity ≥99.999%. The flow control component is a flow controller that can adjust the inert gas flow rate to 5-100 sccm. A miniature Ar purging channel (flow rate 10-20 sccm) is added in the area of ​​the light-transmitting window 102. The impurity detection component is an online oxygen / moisture sensor with a detection accuracy ≤0.1ppm, ensuring that the O2 / H2O content in both the deposition and testing areas is <1 ppm.

[0040] This invention also provides an online integrated photoluminescence testing method, which uses the above-mentioned online integrated photoluminescence testing device for in-situ quality detection of perovskite precursor inorganic salt thin films, and includes the following steps:

[0041] S1) Start-up and calibration: Turn on the deposition unit, photoluminescence test unit and atmosphere control unit, and preheat for 30 minutes; use standard fluorescent samples (such as Rhodamine B, quinine sulfate) to perform wavelength and intensity calibration on the photoluminescence test unit; execute the vacuum-inert gas replacement procedure through the atmosphere control unit, that is, start the vacuum-Ar replacement procedure, repeat 3 times, and ensure that the O2 / H2O content in the chamber and test area is <1ppm to establish a low oxygen and low water atmosphere;

[0042] S2) Parameter preset: Deposition parameters, photoluminescence test parameters, and timing parameters are set through the data processing module. Deposition parameters (temperature, vacuum, deposition rate, film thickness), test parameters (excitation wavelength 405nm / 450nm, excitation power 5-10mW, scanning range 450-700nm, scanning speed 200nm / min), and timing parameters (the opening and closing baffle assembly 103 closes during the deposition stage, the test starts 0.5s after the deposition is completed, the opening and closing baffle assembly 103 automatically opens 0.1s before the test, and the opening and closing baffle assembly 103 automatically closes 0.1s after the test is completed) are set through the host computer 23.

[0043] S3) Thin film deposition: The target perovskite precursor inorganic salt thin film is deposited through the deposition unit. After the deposition is completed, a deposition completion signal is sent to the timing coordination module.

[0044] S4) In-situ photoluminescence test: The timing coordination module responds to the deposition completion signal and controls the opening and closing baffle assembly to open according to the preset timing sequence. The optical module collects photoluminescence signals from multiple points on the film at the deposition station. That is, in response to the "deposition completion" signal, the automatic opening and closing baffle assembly is first controlled to open automatically according to the preset timing sequence. Then, the laser and PMT are started. Excitation light is introduced to the sample surface at the deposition station through the first optical module 21. The fluorescence signal is collected at 3 points (center + 2 edges) through the second optical module 21'. The collected data is transmitted to the host computer 23 in real time.

[0045] S5) Data Processing and Judgment: The host computer 23 performs background subtraction using a Gaussian fitting algorithm and extracts key feature parameters such as peak position (λ_max), luminescence intensity (I), and full width at half maximum (FWHM). The data processing time is ≤10s / sample. If the extracted parameters meet the qualified conditions of "single luminescence peak, peak position deviation ≤5nm, intensity fluctuation ≤10%, and FWHM ≤30nm", it is judged as qualified and a "pass" signal is generated. If the qualified conditions are not met, an alarm mechanism is triggered, and the cause of the abnormality and the corresponding process adjustment suggestions (such as deposition temperature adjustment, deposition rate adjustment, or atmosphere parameter adjustment) are displayed. After the test is completed, the timing coordination module controls the opening and closing baffle assembly 103 to close automatically.

[0046] S6) Reset after testing: After the batch test is completed, first turn off the excitation source and detector, maintain Ar purging for 10 minutes to clean the quartz window, and then turn off the power of each module in sequence. After every 50 batches of tests, calibrate and maintain the optical components and sensors to ensure the stability of the equipment.

[0047] The following are examples of testing different perovskite precursor inorganic salt thin films using the above-described online integrated photoluminescence device and testing method:

[0048] Example 1: In-line integrated PL testing of perovskite precursor inorganic salt thin films

[0049] The deposition unit includes a vapor deposition system equipped with a quartz evaporation source, a temperature control unit (control accuracy ±1℃), and a vacuum control unit (ultimate vacuum ≤5 Pa); the photoluminescence testing unit includes a 405nm semiconductor laser as the excitation source (power adjustment range 0-50mW), a high-transmittance quartz window with 96% transmittance, and an electromagnetically driven automatic opening and closing baffle (response time ≤50 ms, closure seal ≤10⁻³ Pa·L / s), a monochromator with a resolution of 0.5nm, a PMT response time of 0.5ms, a digital delay pulse generator with timing accuracy of 0.1ns, and a LabVIEW control platform on the host computer; the atmosphere control unit uses high-purity Ar gas with a purity of 99.999%, a micro Ar purge channel flow rate of 15sccm, and an oxygen / moisture sensor with a detection accuracy of 0.05ppm.

[0050] The specific testing steps are as follows:

[0051] S1) System initialization: Turn on each module and preheat for 30 minutes; use Rhodamine B standard sample to complete wavelength calibration (calibration error 0.3 nm) and intensity calibration; start the vacuum-Ar replacement program 3 times and check to confirm that the O2 / H2O content in the chamber is 0.08 ppm;

[0052] S2) Parameter presets: Deposition parameters are set as follows: evaporation source temperature 190℃, deposition vacuum 12Pa, deposition rate 0.4nm / s, film thickness 200nm; test parameters are set as follows: excitation wavelength 405nm, excitation power 8mW, scan range 450-700nm, scan speed 200nm / min; timing coordination parameters are set as follows: the baffle assembly is closed during the deposition stage, the test is started 0.5s after the deposition is completed, the baffle assembly is opened 0.1s before the test, and the baffle assembly is closed 0.1s after the test is completed.

[0053] S3) Thin film deposition: Control the evaporation rate of CsBr source + PbBr2 source to be close to 1:1, start the deposition program, and after completing the deposition of 200nm thin film, the deposition unit sends a "deposition completion signal" to the timing coordination module.

[0054] S4) In-situ PL test: The host computer calls the background signal of the blank ITO / SnO2 substrate, starts the laser and PMT, and completes the signal acquisition of the sample at the center, left edge and right edge of the deposition station. The acquisition time of each point is 3s.

[0055] S5) Data processing and judgment: After the host computer completes the background subtraction, it extracts parameters through Gaussian fitting algorithm: peak position 521nm, luminescence intensity 8500 a.u., FWHM 25nm. All parameters meet the qualification standard and generate a "pass" signal; after the test is completed, the timing coordination module immediately controls the automatic opening and closing of the baffle to avoid contaminants adhering to the window during subsequent chamber operations.

[0056] S6) System shutdown and maintenance: After the test is completed, turn off the laser and PMT, start Ar purging for 10 minutes, and then turn off the power of each module in sequence.

[0057] The test data in this embodiment exhibits excellent stability, with peak deviation of 2 nm and intensity fluctuation of 6% at the three test points, both meeting the qualification standards. No moisture absorption or oxidation was observed in the samples, and the test data accurately reflects the intrinsic quality of the film. The total testing time for a single sample was 28 seconds, significantly better than offline testing (single sample testing time ≥ 10 minutes). To quantify the performance difference between the online testing of this invention and traditional offline testing, Table 1 lists the key parameter comparison data for the online and offline testing of Example 1:

[0058] Table 1 Comparison of online and offline test results for Example 1

[0059] Test type Peak position (nm) Luminous intensity (au) Full width at half maximum (nm) Peak position deviation (nm) Intensity fluctuation (%) Single sample testing time Sample status Online testing 522 8500 25 2 6 28 s Non-hygroscopic and non-oxidizing Offline testing 528 6200 38 6 27 12 min Slightly absorbs moisture

[0060] Table 1 shows that the offline test results were: peak position 528nm (shifted by 6nm), luminescence intensity 6200 a.u. (decreased by 27%), FWHM 38nm (exceeding the acceptable standard), slight moisture absorption marks on the sample surface, and the test data could not truly reflect the intrinsic quality of the film. The total test time for a single sample was 12 minutes. In this embodiment, the peak position deviation and intensity fluctuation of the online test were significantly smaller than those of the offline test, the half-width at half-maximum (WHM) was narrower, and the test time was only about 1 / 25 of that of the offline test. At the same time, the online test can avoid sample moisture absorption and oxidation, ensuring that the test data truly reflects the intrinsic quality of the film, fully demonstrating the technical advantages of the present invention. By comparison, it can be seen that the device and method of the present invention can effectively avoid atmospheric exposure pollution during sample transfer, significantly improve test efficiency and test accuracy, and have outstanding technical advantages.

[0061] Example 2: In-line integrated PL testing of pure PbI2 perovskite precursor thin films

[0062] The photoluminescence testing unit includes a 405nm semiconductor laser as the excitation source (power adjustment range 0-50mW), a high-transmittance quartz window with 96% transmittance, and an electromagnetically driven automatic opening and closing baffle (response time ≤50ms, closure tightness ≤10). -3The instrument features a monochromator with a resolution of 0.5 nm, a high-sensitivity PMT (response time 0.5 ms), a digital delay pulse generator with a timing accuracy of 0.1 ns, and a LabVIEW control platform on the host computer. The atmosphere control unit provides high-purity Ar gas with a purity of 99.999%, a micro Ar purge channel with a flow rate of 18 sccm, and an oxygen / moisture sensor with a detection accuracy of 0.05 ppm.

[0063] The specific testing steps are as follows:

[0064] S1) System initialization: Turn on each module and preheat for 30 minutes; use Rhodamine B standard sample to complete wavelength calibration (calibration error 0.2nm) and intensity calibration; start the vacuum-Ar replacement program 3 times and check to confirm that the O2 / H2O content in the chamber is 0.07ppm;

[0065] S2) Parameter presets: Deposition parameters are set as follows: evaporation source temperature 200℃, deposition vacuum degree 10Pa, deposition rate 0.3nm / s, film thickness 220nm; test parameters are set as follows: excitation wavelength 405nm, excitation power 7mW, scan range 450-700nm, scan speed 200nm / min; timing coordination parameters are set as follows: the baffle assembly is closed during the deposition stage, the test is started 0.5s after the deposition is completed, the baffle assembly is opened 0.1s before the test, and the baffle assembly is closed 0.1s after the test is completed.

[0066] S3) Thin film deposition: Add 99.95% pure PbI2 powder to the evaporation source, start the deposition program, and after completing the deposition of a 220nm pure PbI2 thin film, the deposition unit sends a "deposition complete signal" to the timing coordination module.

[0067] S4) In-situ PL test: The host computer calls the background signal of the blank ITO substrate, starts the laser and PMT, and completes the signal acquisition of three points on the sample at the deposition station: center, left edge and right edge. Each point is acquired for 3 seconds.

[0068] S5) Data processing and judgment: After the host computer completes the background subtraction, it extracts the parameters through the Gaussian fitting algorithm: peak position 512nm, luminous intensity 8800a.u., FWHM 26nm. If the parameters meet the qualification standard, a "pass" signal is generated; after the test is completed, the opening and closing baffle assembly closes synchronously.

[0069] S6) System shutdown maintenance: Turn off the laser and PMT, start Ar purging for 10 minutes, and then turn off the power to each module in sequence.

[0070] This embodiment achieves accurate testing of pure PbI2 precursor films. The peak position deviation at the three test points is 1.8 nm, and the intensity fluctuation is 5.5%, demonstrating excellent data stability. No moisture absorption or oxidation was observed in the sample, and the test data accurately reflects the intrinsic quality of the film. The total testing time for a single sample is 27 seconds, which is suitable for the mass production testing requirements of pure perovskite precursor films. To accurately quantify the test data details of Example 2, Table 2 lists the specific PL characteristic parameters of the three test points in Example 2.

[0071] Table 2. Values ​​of three points tested online in Example 2

[0072] Test points Peak position (nm) Luminous intensity (au) Full width at half maximum (nm) Data collection duration (s) Center point 512 8820 26 3 Left edge point 513 8750 26 3 Right edge point 511 8880 26 3

[0073] As shown in Table 2, the peak positions at the three test points are concentrated between 511-513 nm, with a peak position deviation of only 1 nm; the luminescence intensity is within the range of 8750-8880 a.u., with small intensity fluctuations; and the full width at half maximum (FWHM) is consistently 26 nm. All parameters meet the qualification standards of "peak position deviation ≤ 5 nm, intensity fluctuation ≤ 10%, and FWHM ≤ 30 nm," further confirming the excellent quality of the pure PbI2 film and the accuracy of the test method of this invention. To verify the testing advantages of this invention for pure component films, Table 3 lists the key parameter comparison data of the online test and the corresponding offline test in Example 2:

[0074] Table 3 Comparison of online and offline tests in Example 2

[0075] Test type Peak position (nm) Luminous intensity (au) Full width at half maximum (nm) Peak position deviation (nm) Intensity fluctuation (%) Single sample testing time Sample status Online testing 512 8800 26 1.8 5.5 27 s Non-hygroscopic and non-oxidizing Offline testing 515 6500 39 8 30 13 min Slightly absorbs moisture

[0076] As shown in Table 3, for pure PbI2 films, the peak position deviation and intensity fluctuation of the online test are much smaller than those of the offline test, and the full width at half maximum (FWHM) is narrower; the test time is only 27s, which is only 1 / 28 of that of the offline test (13min); at the same time, the online test can avoid the sample absorbing moisture and oxidation, ensuring that the test data truly reflects the intrinsic quality of the film, which fully demonstrates the adaptability and testing advantages of this invention for pure component perovskite precursor films.

[0077] The specific embodiments described herein are merely illustrative of the spirit of the invention. Those skilled in the art to which this invention pertains may make various modifications or additions to the described specific embodiments or use similar methods to substitute them, without departing from the spirit of the invention or exceeding the scope defined by the appended claims.

Claims

1. An online integrated photoluminescence testing device, characterized in that, In-situ quality control of perovskite precursor inorganic salt films, including: The deposition unit includes a vapor deposition apparatus body for depositing perovskite precursor inorganic salt thin films. The vapor deposition apparatus body has a sealed light-transmitting window, and an opening / closing baffle assembly is provided at the light-transmitting window. The photoluminescence testing unit includes an optical module, a timing coordination module, and a data processing module. The optical module is located at the light-transmitting window and, after being opened by the opening and closing baffle assembly, connects to the optical path of the vapor deposition equipment body for directional introduction of excitation light and export of fluorescence signals to the vapor deposition equipment body. The timing coordination module is connected to both the deposition unit and the optical module for timing matching of the deposition and testing processes. The data processing module is used to acquire deposition parameters and test data in real time. An atmosphere control unit, which is connected to the deposition unit and the photoluminescence testing unit, is used to maintain a low-oxygen, low-water testing atmosphere inside each unit.

2. The online integrated photoluminescence testing device according to claim 1, characterized in that, The perovskite precursor inorganic salt film includes a PbI2 film, a PbBr2 film, or a mixed film of PbI2 and PbBr2.

3. The online integrated photoluminescence testing device according to claim 1, characterized in that, The vapor deposition apparatus has a deposition chamber, which contains a temperature control unit, a vacuum control unit, a sample stage, and a quartz evaporation source. The quartz evaporation source is located below the sample stage's bearing surface. The light-transmitting window includes a flange hole disposed on the vapor deposition apparatus and communicating with the deposition chamber. High-transmittance quartz glass is sealed inside the flange hole. The opening and closing baffle assembly includes a drive component and a light-shielding plate disposed at the output end of the drive component. The light-shielding plate is driven to open or cover the light-transmitting window.

4. The online integrated photoluminescence testing device according to claim 1, characterized in that, The optical module includes an excitation source, a beam control component, an optical filter component, a beam splitter component, and a detection component. The excitation source is a 405nm or 450nm visible light semiconductor laser. The beam control component includes a collimating-focusing lens group and a fluorescence collecting lens. The collimating-focusing lens group is connected to the excitation source via an optical fiber coupler for focusing and introducing the excitation light. The fluorescence collecting lens is used to converge and export the fluorescence signal to the optical filter component and then to the beam splitter component. The detection component includes a photomultiplier tube or a CCD detector for detecting the fluorescence signal exported by the beam splitter component.

5. The online integrated photoluminescence testing device according to claim 1, characterized in that, The timing coordination module includes a digital delay pulse generator and a timing controller; the timing control accuracy of the digital delay pulse generator is ≤1ns, and it can be set to start the test with a delay of 0.1-1s after deposition is completed. The timing controller is electrically connected to the opening and closing baffle assembly, and controls the baffle to open 0.05-0.2s before the test and close 0.05-0.2s after the test is completed.

6. The online integrated photoluminescence testing device according to claim 1, characterized in that, The atmosphere control unit includes an inert gas supply component, a flow control component, and an impurity detection component; the inert gas supply component is a high-purity Ar gas supply system with a purity ≥99.999%; the flow control component is a flow controller that can adjust the inert gas flow rate to 5-100 sccm; and the impurity detection component is an online oxygen / moisture sensor with a detection accuracy ≤0.1ppm.

7. An online integrated photoluminescence testing method, characterized in that, The online integrated photoluminescence testing device described in any one of claims 1 to 6 is used for in-situ quality testing of perovskite precursor inorganic salt films, and includes the following steps: S1) Start-up and calibration: Turn on the deposition unit, photoluminescence test unit and atmosphere control unit, and preheat; perform wavelength calibration and intensity calibration on the photoluminescence test unit; execute the vacuum-inert gas replacement procedure through the atmosphere control unit to establish a low-oxygen and low-water atmosphere; S2) Parameter preset: Set deposition parameters, photoluminescence test parameters, and timing coordination parameters through the data processing module; S3) Thin film deposition: The target perovskite precursor inorganic salt thin film is deposited through the deposition unit. After the deposition is completed, a deposition completion signal is sent to the timing coordination module. S4) In-situ photoluminescence test: The timing coordination module responds to the deposition completion signal and controls the opening and closing baffle assembly to open according to the preset timing sequence. The optical module collects multi-point photoluminescence signals of the thin film on the deposition station. S5) Data processing and judgment: The data processing module performs background subtraction and feature parameter extraction on the acquired signal to complete the thin film quality judgment; S6) Reset after test: The timing coordination module controls the opening and closing of the baffle assembly to close, maintain the inert gas purging for a preset time, and then shut down each unit.

8. The online integrated photoluminescence testing method according to claim 7, characterized in that, The vacuum-inert gas replacement procedure is repeated 2-4 times.

9. The online integrated photoluminescence testing method according to claim 7, characterized in that, The multi-point acquisition mode acquires photoluminescence signals from the center of the thin film and at least two edge points, with each point acquisition lasting 2-5 seconds. The data processing module automatically subtracts background signals using a Gaussian fitting algorithm, and the total test time for a single sample is ≤30 seconds.

10. The online integrated photoluminescence testing method according to claim 7, characterized in that, The characteristic parameters include emission peak position, emission intensity, and half-width at half-maximum (WHM). When the emission peak position deviation is less than a set value, the emission intensity fluctuation is less than a set value, and the WHM is less than a set value, the film quality is deemed to be qualified.

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