WO2022161117A1 - Germanium-based perovskite photoelectric material, application thereof and preparation method therefore, and device and manufacturing method therefor - Google Patents

Germanium-based perovskite photoelectric material, application thereof and preparation method therefore, and device and manufacturing method therefor Download PDF

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WO2022161117A1
WO2022161117A1 PCT/CN2022/070070 CN2022070070W WO2022161117A1 WO 2022161117 A1 WO2022161117 A1 WO 2022161117A1 CN 2022070070 W CN2022070070 W CN 2022070070W WO 2022161117 A1 WO2022161117 A1 WO 2022161117A1
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perovskite
solution
germanium
light
ito glass
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杨得鑫
狄大卫
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浙江大学
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the invention belongs to the fields of optoelectronic devices and material science, and specifically relates to germanium-based perovskite optoelectronic materials, applications, preparation methods, devices and device preparation methods, and can be applied to high-end display devices, flexible display devices, lighting and the like.
  • germanium-based halide perovskite materials can also be used as common light-emitting films and phosphors; they can also be used as core materials to prepare scintillators, lasers, light-emitting transistors, and solar cells.
  • Metal halide perovskite materials are core semiconductor materials for next-generation display, lighting, solar energy, lasers, scintillators, and light-emitting transistors. They have the advantages of tunable emission wavelength, high spectral purity, high luminous efficiency, and can be prepared by solution methods .
  • LEDs perovskite light-emitting diodes
  • EQE device efficiency of perovskite LEDs
  • perovskite LEDs Compared with commercialized organic light-emitting diodes (OLEDs), perovskite LEDs have the advantages of low cost, pure color, wide color gamut, narrow emission spectrum, and high mobility, and are expected to replace OLEDs as the mainstream product of next-generation high-end display devices. .
  • this patent will partially replace the Pb element with germanium (Ge), an environmentally friendly element. And the use of reasonable long-chain molecules and additives to further enhance the luminescence properties of such Ge-Pb blended perovskite systems. Finally, through a reasonable preparation process, we not only reduced the toxicity of halide perovskite, but also improved the optoelectronic properties and luminous efficiency of halide perovskite thin films and perovskite LED devices.
  • germanium germanium
  • the preparation process of such low-toxicity perovskite materials can not only be used as light-emitting films and phosphors, but also as core semiconductor materials in scintillators, lasers, light-emitting transistors and solar cells.
  • the present invention proposes germanium-based perovskite photoelectric materials, applications, preparation methods, devices and device preparation methods.
  • a germanium-based perovskite photoelectric material is a light-emitting layer material, and its structure is A' 2 (AMX 3 ) n-1 MX 4 ; wherein n ⁇ [1, ⁇ ), wherein A' is PEA, PBA, OAm, TEA or PMA; A is Cs, EA, FA or MA, M is B 1-y Ge y , wherein B is Pb, Sn, Mn, Zn, Cd, Co, Cu, Ni, X is Cl, Br, or I.
  • the light-emitting layer material is: PEA 2 (CsPb 0.9 Ge 0.1 Br 3 ) 2 Pb 0.9 Ge 0.1 Br 4 .
  • the material of the light-emitting layer is: AB 1-y Ge y X 3 ; wherein n is infinite.
  • a germanium-based perovskite optoelectronic material is used in a variety of optoelectronic devices, including solar cells, light-emitting diodes, detectors, fluorescent films, phosphors, semiconductor transistors, lasers, etc. Optoelectronic devices and materials.
  • a method for preparing a germanium-based perovskite photoelectric material comprises the following steps: thermal evaporation, magnetron sputtering, MOCVD, ALD, spraying, printing, solution spin coating, and vacuum calcination.
  • a germanium-based perovskite optoelectronic device comprising an electrode, a hole transport layer, an electron transport layer and a light-emitting layer; its structure is as follows from top to bottom: a first electrode, a light-emitting layer, a hole transport layer and a second electrode ; wherein the light-emitting layer is A' 2 (AMX 3 ) n-1 MX 4 ; wherein n ⁇ [1, ⁇ ), wherein A' is PEA, PBA, OAm, TEA or PMA; A is Cs, EA, FA or MA, M is B 1-y Ge y , wherein B is Pb, Sn, Mn, Zn, Cd, Co, Cu, Ni, and X is Cl, Br, or I.
  • a method for preparing a germanium-based perovskite optoelectronic device characterized in that the method specifically comprises the following steps:
  • Step (2) adding DMSO solvent to the weighed powder to make its concentration 0.2mmol/ml;
  • Step (3) adding a stirring bar to the A' 2 (AMX 3 ) n-1 MX 4 precursor solution, and placing it in a magnetic stirrer and stirring for 24 hours;
  • Step (4) until the solution is completely dissolved, add the additive 18-crown-6 solution and continue to stir for one hour;
  • Step (5) using a disposable needle and filter head to filter the solution to obtain a clear perovskite precursor solution
  • Step (6) use high-purity nitrogen to dry the ITO glass cleaned in acetone and isopropanol;
  • Step (7) put ITO glass into high-power ozone generator, and process 30 minutes in high-concentration ozone environment;
  • Step (8) set the acceleration of the glue dispenser to 5000 rpm/s 2 , the rotational speed to 5000 rpm/s, and the time to be 90 s, and place the clean ITO glass that has been ozonated on the glue dispenser tray;
  • Step (9) take 30 ⁇ l of PVK solution with a concentration of 6 mg/ml, spread the solution on the surface of the ITO glass, and then start spin coating for about 60s;
  • Step (10) placing the suspension-coated ITO/PVK film on a baking glue hot stage at 100-150° C. and annealing for 10 minutes to obtain a dense PVK film;
  • Step (11) after it is completely cooled, place the ITO glass on the suspension coater that has been set in step (8), take 30 ⁇ l of the perovskite precursor solution in step (5), click to start rotating, and wait until its speed reaches At 5000 rpm, drop a drop of A' 2 (AMX 3 ) n-1 MX 4 perovskite precursor solution, and after the solution is fully spread out for 15-25 seconds, drop 200 ⁇ l of ultra-dry ethyl acetate ( C 4 H 8 O 2 ) solution;
  • Step (12) placing the ITO glass on which the perovskite film has been suspended and coated on a baking glue hot table at 50-100° C. for annealing for 10 minutes;
  • Step (13) after the perovskite film is completely cooled, put it into the vapor deposition apparatus; take the electron transport layer material TPBi powder, the intermediate transition layer LiF powder and the electrode Al particles and put them on the corresponding evaporation boat of the vapor deposition apparatus, First, 40-70nm TPBi was evaporated, then 0.5-3nm LiF was evaporated, and 50-100nm Al was evaporated. Finally, the devices that had been evaporated were packaged to test their electroluminescence efficiency, electroluminescence spectrum, current Density-voltage-brightness and other optoelectronic properties.
  • the suspension coater stops rotating 65-75 seconds after dropping 200 ⁇ l of the ultra-dry ethyl acetate C 4 H 8 O 2 solution.
  • the heating temperature of the ITO glass after spin-coating the PVK solution is 120° C.
  • the perovskite film on the PVK is annealed on a 70° C. glue hot stage for 10 minutes.
  • the thickness of the TPBi vapor deposition is 50 nm
  • the thickness of the LiF vapor deposition is 1 nm
  • the thickness of the Al vapor deposition is 80 nm.
  • the hole transport layer PVK and the perovskite film are suspended on the ITO glass by the suspension coating method, and then the electron transport layer TPBi and the electrode LiF/Al are evaporated by thermal evaporation. While ensuring the electroluminescence efficiency, the difficulty of experimentally preparing perovskite light-emitting devices is reduced, and the content of heavy metal lead in the entire device is also reduced.
  • Figure 1 Structural characterization of germanium-lead perovskite samples.
  • a XRD results of perovskite films deposited on silicon substrates with different germanium mole fractions.
  • b The XRD patterns and the corresponding refinement results of the Rietveld structure refinement of the perovskite samples containing 10% Ge using the TOPAS-V6 software.
  • c The perovskite crystal structure obtained after structure refinement by Rietveld method.
  • Fig. 2.a UV-Vis absorption spectrum and PL spectrum of 10%Ge perovskite film.
  • d Transient PL decay curves of germanium-lead perovskite films.
  • e Effective PL lifetime and PL tail decay lifetime of perovskite films with 10%-50% Ge content.
  • Figure 3.a Schematic diagram of the structure of the perovskite LED device.
  • b Energy band diagram of each transport layer, light-emitting layer and electrode of the device.
  • c STEM-HAADF image of the cross-section sample.
  • d EDS elemental maps of Cs, Pb and Ge.
  • e EL spectra of the device under different bias voltages.
  • f The functional relationship between the device luminous efficiency (EQE) and the current density of the perovskite thin films with different Ge (0mol%, 10mol% and 20mol%) contents.
  • g Current density-voltage-luminance (J-V-L) characteristic maps of perovskite LED devices with 10% Ge substitution.
  • XRD X-ray diffraction
  • the surface morphologies of the halide perovskite thin films were obtained using atomic force microscopy (AFM) and scanning electron microscopy (SEM).
  • the grain distribution of the film and the lattice fringes of the perovskite crystal were studied by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). distribution in the film. Fluorescence photon lifetimes were measured using an Edinburgh Instruments FLS900 spectrometer.
  • the photoluminescence quantum efficiency (PLQY) and photoexcitation spectrum (PL) were obtained using the integrating sphere spectroscopic test system built in the laboratory. ).)).
  • the tested laser wavelength is 405nm
  • the fluorescence spectrum is mainly measured by Ocean Optics' spectrometer (USB4000).
  • Electroluminescence efficiency (EQE) was measured using a Keithley 2400 source meter and an Everfine OLED-200 commercial OLED performance analysis system.
  • Step (1) weigh CsBr, PbBr 2 and PEABr according to the molar ratio of 1:1:0.4, and put them into the sample bottle;
  • Step (2) adding the weighed powder in 1ml DMSO solvent, and its concentration is 0.2mmol/ml;
  • Step (3) adding a stirring bar to the CsPb 1-x Ge x Br 3 precursor solution, and putting it into a magnetic stirrer to stir;
  • Step (4) until the solution is completely dissolved, add the additive 18-crown-6 solution and continue to stir for one hour;
  • Step (5) using a disposable needle and filter head to filter the solution to obtain a clear perovskite precursor solution
  • Step (6) use high-purity nitrogen to dry the ITO glass cleaned in acetone and isopropanol;
  • Step (7) put ITO glass into high-power ozone generator, and process 30 minutes in high-concentration ozone environment;
  • Step (8) set the acceleration of the glue dispenser to 5000 rpm/s 2 , the rotational speed to 5000 rpm/s, and the time to be 90 s, and place the clean ITO glass that has been ozonated on the glue dispenser tray;
  • Step (9) take 30 ⁇ l of PVK solution with a concentration of 6 mg/ml, spread the solution on the surface of the ITO glass, and then start spin coating for about 60s;
  • Step (10) placing the ITO/PVK film after suspension coating on a 120° C. glue hot stage for annealing for 10 minutes to obtain a dense PVK film;
  • Step (11) after it is completely cooled, place the ITO glass on the suspension coater that has been set in step (8), take 30 ⁇ l of the perovskite precursor solution in step (5), click to start rotating, and wait until its speed reaches At 5000 rpm, drop a drop of CsPb 1-x Ge x Br 3 perovskite precursor solution, and after the solution is fully spread out for 21 seconds, drop 200 ⁇ l of ultra-dry ethyl acetate (C 4 H 8 O 2 ) within one second. ) solution;
  • Step (12) placing the ITO glass on which the perovskite film has been suspended and coated on a 70° C. glue hot table for annealing for 10 minutes;
  • Step (13) After the perovskite film is completely cooled, put it into the vapor deposition apparatus. Take the electron transport layer material TPBi powder, the intermediate transition layer LiF powder and the electrode Al particles and put them on the corresponding evaporation boat of the evaporation apparatus, first evaporate 50nm TPBi, then evaporate 1nm LiF, and finally evaporate 80nm Al. Finally, the vapor-deposited device was packaged, and its electroluminescence efficiency (EQE), electroluminescence spectrum (EL), current density-voltage-brightness (J-V-L) and other optoelectronic properties were tested.
  • EQE electroluminescence efficiency
  • EL electroluminescence spectrum
  • J-V-L current density-voltage-brightness
  • the result of XRD structure refinement can be obtained as shown in Fig. 1c: the crystal structure of perovskite CsPb 1-x Ge x Br 3 is an orthorhombic structure.
  • the incorporation of Ge element makes the octahedral structure of perovskite more distorted (Fig. 1d).
  • Figure 5 shows the change of the unit cell volume of the perovskite after the substitution of different Ge elements.
  • STEM scanning transmission electron microscopy
  • Figure 2 shows the optical properties of the perovskite CsPb 1-x Ge x Br 3 and the surface morphology of the film
  • the positions of absorption peaks and PL peaks are around 520 nm and 515 nm, respectively.
  • Figure 2d is a graph of the fluorescence lifetime (PL decay) of the perovskite, and the laser wavelength of the solid-state laser used is 450 nm.
  • Figure 2e shows the trend of effective PL lifetime and PL tail decay lifetime. With the increase of Ge element substitution, both the fluorescence decay lifetime and the effective lifetime showed an increasing trend.
  • Figure 3 mainly shows the device structure and optoelectronic properties of perovskite LED devices.
  • Figure 3 a is a schematic structural diagram of the device, the device structure is ITO/PVK/Perovskite/TPBi/LiF/Al, where PVK is the hole transport layer, TPBi is the electron transport layer, LiF/Al and ITO are the electrode layers, calcium Titanite is the light-emitting layer.
  • Figure 3b is a diagram of the energy level structure between the layers of the perovskite LED device.
  • Figure 3c is the cross-sectional view of the device prepared by the experiment obtained by STEM-HAADF, and the specific thickness of each layer can be seen through the STEM-HAADF spectrum; and
  • Figure 3d is the element distribution of EDS taken from the position shown in the box of Figure 3c.
  • Figure 3e shows the EL spectra of the device at different voltages. It is found that the EL peaks do not have obvious red shifts at different voltages, indicating the stability of the electro-spectroscopy.
  • the inset is a physical image of the perovskite LED device in operation.
  • Figure 3f shows the functional relationship between the device luminous efficiency (EQE) and the current density of the perovskite films with different Ge (0mol%, 10mol% and 20mol%) content, where when the replacement amount of Ge is 10%, the device The efficiency value EQE reached the highest (8.9%), indicating that the partial replacement of Ge not only reduced the amount of Pb, but also improved the optoelectronic properties of the device.
  • Figure 3g is the current density-voltage-luminance (JVL) characteristic map of the perovskite LED device with 10% Ge substitution, and it is found that its maximum luminance is about 10000 cd/m 2 .
  • JVL current density-voltage-luminance
  • Step (1) weigh CsI, PbI 2 , GeI 2 and PEAI according to a molar ratio of 1:0.9:0.1:0.4, and put them into a sample bottle;
  • Step (2) adding DMSO solvent to the weighed powder to make its concentration 0.2mmol/ml;
  • Step (3) adding a stirring bar into the CsPb 1-x Ge x I 3 precursor solution, and putting it into a magnetic stirrer to stir;
  • Step (4) until the solution is completely dissolved, add the additive 18-crown-6 solution and continue to stir for one hour;
  • Step (5) filter the solution using a disposable syringe and filter head
  • Step (6) use high-purity nitrogen to dry the ITO glass cleaned in acetone and isopropanol;
  • Step (7) put ITO glass into high-power ozone generator, and process 30 minutes in high-concentration ozone environment;
  • Step (8) set the acceleration of the glue dispenser to 5000 rpm/s 2 , the rotational speed to 5000 rpm/s, and the time to be 90 s, and place the clean ITO glass that has been ozonated on the glue dispenser tray;
  • Step (9) take 30 ⁇ l of PVK solution with a concentration of 6 mg/ml, spread the solution on the surface of the ITO glass, and then start spin coating for about 60s;
  • Step (10) placing the ITO/PVK film after suspension coating on a 120° C. glue hot stage for annealing for 10 minutes to obtain a dense PVK film;
  • Step (11) after it is completely cooled, place the ITO glass on the suspension coater that has been set in step (8), take 30 ⁇ l of the perovskite precursor solution in step (5), click to start rotating, and wait until its speed reaches At 5000 rpm, drop a drop of CsPb 1-x Ge x I 3 perovskite precursor solution, and after the solution is fully spread out for 21 seconds, drop 200 ⁇ l of ultra-dry ethyl acetate (C 4 H 8 O 2 ) within one second. ) solution;
  • Step (12) placing the ITO glass on which the perovskite film has been suspended and coated on a 70° C. glue hot table for annealing for 10 minutes;
  • Step (13) After the perovskite film is completely cooled, put it into the vapor deposition apparatus. Take the electron transport layer material TPBi powder, the intermediate transition layer LiF powder and the electrode Al particles and put them on the corresponding evaporation boat of the evaporation apparatus, first evaporate 50nm TPBi, then evaporate 1nm LiF, and finally evaporate 80nm Al. Finally, the vapor-deposited device was packaged, and its electroluminescence efficiency (EQE), electroluminescence spectrum (EL), current density-voltage-brightness (J-V-L) and other optoelectronic properties were tested.
  • EQE electroluminescence efficiency
  • EL electroluminescence spectrum
  • J-V-L current density-voltage-brightness
  • Step (1) weigh FABr, PbBr 2 , GeBr 2 and PEABr according to a molar ratio of 1:0.7:0.3:0.4, and put them into a glass bottle;
  • Step (2) adding DMSO solvent to the weighed powder to make its concentration 0.2mmol/ml;
  • Step (3) adding a stirring bar to the FAPb 1-x Ge x Br 3 precursor solution, and putting it into a magnetic stirrer to stir;
  • Step (4) until the solution is completely dissolved, add the additive 18-crown-6 solution and continue to stir for one hour;
  • Step (5) filter the solution using a disposable syringe and filter head
  • Step (6) use high-purity nitrogen to dry the ITO glass cleaned in acetone and isopropanol;
  • Step (7) put ITO glass into high-power ozone generator, and process 30 minutes in high-concentration ozone environment;
  • Step (8) set the acceleration of the glue dispenser to 5000 rpm/s 2 , the rotational speed to 5000 rpm/s, and the time to be 90 s, and place the clean ITO glass that has been ozonated on the glue dispenser tray;
  • Step (9) take 30 ⁇ l of PVK solution with a concentration of 6 mg/ml, spread the solution on the surface of the ITO glass, and then start spin coating for about 60s;
  • Step (10) placing the ITO/PVK film after suspension coating on a 120° C. glue hot stage for annealing for 10 minutes to obtain a dense PVK film;
  • Step (11) after it is completely cooled, place the ITO glass on the suspension coater that has been set in step (8), take 30 ⁇ l of the perovskite precursor solution in step (5), click to start rotating, and wait until its speed reaches At 5000 rpm, drop a drop of FAPb 1-x Ge x Br 3 perovskite precursor solution, and after the solution is fully spread out for 21 seconds, drop 200 ⁇ l of ultra-dry ethyl acetate (C 4 H 8 O 2 ) within one second. ) solution;
  • Step (12) placing the ITO glass on which the perovskite film has been suspended and coated on a 70° C. glue hot table for annealing for 10 minutes;
  • Step (13) After the perovskite film is completely cooled, put it into the vapor deposition apparatus. Take the electron transport layer material TPBi powder, the intermediate transition layer LiF powder and the electrode Al particles and put them on the corresponding evaporation boat of the evaporation apparatus, first evaporate 50nm TPBi, then evaporate 1nm LiF, and finally evaporate 80nm Al. Finally, the devices that have been evaporated were packaged and tested for their electroluminescence efficiency (EQE), electroluminescence spectrum (EL), current density-voltage-brightness (J-V-L) and other optoelectronic properties.
  • EQE electroluminescence efficiency
  • EL electroluminescence spectrum
  • J-V-L current density-voltage-brightness
  • Step (1) weigh EABr, PbBr 2 , GeBr 2 and PEABr according to a molar ratio of 1:0.6:0.4:0.4, and put them into a glass bottle;
  • Step (2) adding DMSO solvent to the weighed powder to make its concentration 0.2mmol/ml;
  • Step (3) adding a stirring bar to the EAPb 1-x Ge x Br 3 precursor solution, and putting it into a magnetic stirrer to stir;
  • Step (4) until the solution is completely dissolved, add the additive 18-crown-6 solution and continue to stir for one hour;
  • Step (5) filter the solution using a disposable syringe and filter head
  • Step (6) use high-purity nitrogen to dry the ITO glass cleaned in acetone and isopropanol;
  • Step (7) put ITO glass into high-power ozone generator, and process 30 minutes in high-concentration ozone environment;
  • Step (8) set the acceleration of the glue dispenser to 5000 rpm/s 2 , the rotational speed to 5000 rpm/s, and the time to be 90 s, and place the clean ITO glass that has been ozonated on the glue dispenser tray;
  • Step (9) take 30 ⁇ l of PVK solution with a concentration of 6 mg/ml, spread the solution on the surface of the ITO glass, and then start spin coating for about 60s;
  • Step (10) placing the ITO/PVK film after suspension coating on a 120° C. glue hot stage for annealing for 10 minutes to obtain a dense PVK film;
  • Step (11) after it is completely cooled, place the ITO glass on the suspension coater that has been set in step (8), take 30 ⁇ l of the perovskite precursor solution in step (5), click to start rotating, and wait until its speed reaches At 5000 rpm, drop a drop of EAPb 1-x Ge x Br 3 perovskite precursor solution, and after the solution is fully spread out for 21 seconds, drop 200 ⁇ l of ultra-dry ethyl acetate (C 4 H 8 O 2 ) within one second. ) solution;
  • Step (12) placing the ITO glass on which the perovskite film has been suspended and coated on a 70° C. glue hot table for annealing for 10 minutes;
  • Step (13) After the perovskite film is completely cooled, put it into the vapor deposition apparatus. Take the electron transport layer material TPBi powder, the intermediate transition layer LiF powder and the electrode Al particles and put them on the corresponding evaporation boat of the evaporation apparatus, first evaporate 50nm TPBi, then evaporate 1nm LiF, and finally evaporate 80nm Al. Finally, the devices that have been evaporated were packaged and tested for their electroluminescence efficiency (EQE), electroluminescence spectrum (EL), current density-voltage-brightness (J-V-L) and other optoelectronic properties.
  • EQE electroluminescence efficiency
  • EL electroluminescence spectrum
  • J-V-L current density-voltage-brightness
  • Step (1) weigh CsBr, PbBr 2 , GeBr and PEABr according to a molar ratio of 1:0.8:0.2:0.4, and put them into a glass bottle;
  • Step (2) adding DMSO solvent to the weighed powder to make its concentration 0.2mmol/ml;
  • Step (3) adding a stirring bar to the CsPb 1-x Ge x Br 3 precursor solution, and putting it into a magnetic stirrer to stir;
  • Step (4) until the solution is completely dissolved, add the additive 18-crown-6 solution and continue to stir for one hour;
  • Step (5) filter the solution using a disposable syringe and filter head
  • Step (6) use high-purity nitrogen to dry the ITO glass cleaned in acetone and isopropanol;
  • Step (7) put ITO glass into high-power ozone generator, and process 30 minutes in high-concentration ozone environment;
  • Step (8) set the acceleration of the glue dispenser to 5000 rpm/s 2 , the rotational speed to 5000 rpm/s, and the time to be 90 s, and place the clean ITO glass that has been ozonated on the glue dispenser tray;
  • Step (9) take 30 ⁇ l of PVK solution with a concentration of 6 mg/ml, spread the solution on the surface of the ITO glass, and then start spin coating for about 60s;
  • Step (10) placing the ITO/PVK film after suspension coating on a 120° C. glue hot stage for annealing for 10 minutes to obtain a dense PVK film;
  • Step (11) after it is completely cooled, place the ITO glass on the suspension coater that has been set in step (8), take 30 ⁇ l of the perovskite precursor solution in step (5), click to start rotating, and wait until its speed reaches At 5000 rpm, drop a drop of CsPb 1-x Ge x Br 3 perovskite precursor solution, and after the solution is fully spread out for 21 seconds, drop 200 ⁇ l of ultra-dry ethyl acetate (C 4 H 8 O 2 ) within one second. ) solution;
  • Step (12) placing the ITO glass on which the perovskite film has been suspended and coated on a 70° C. glue hot table for annealing for 10 minutes;
  • Step (13) After the perovskite film is completely cooled, put it into the vapor deposition apparatus. Take the electron transport layer material TPBi powder, the intermediate transition layer LiF powder and the electrode Al particles and put them on the corresponding evaporation boat of the evaporation apparatus, first evaporate 50nm TPBi, then evaporate 1nm LiF, and finally evaporate 80nm Al. Finally, the devices that have been evaporated were packaged and tested for their electroluminescence efficiency (EQE), electroluminescence spectrum (EL), current density-voltage-brightness (J-V-L) and other optoelectronic properties.
  • EQE electroluminescence efficiency
  • EL electroluminescence spectrum
  • J-V-L current density-voltage-brightness
  • Step (1) weigh CsBr, PbBr 2 , GeBr and PEABr according to a molar ratio of 1:0.7:0.3:0.4, and put them into a glass bottle;
  • Step (2) adding DMSO solvent to the weighed powder to make its concentration 0.2 ⁇ mol/ml;
  • Step (3) adding a stirring bar to the CsPb 1-x Ge x Br 3 precursor solution, and putting it into a magnetic stirrer to stir;
  • Step (4) until the solution is completely dissolved, add the additive 18-crown-6 solution and continue to stir for one hour;
  • Step (5) filter the solution using a disposable syringe and filter head
  • Step (6) use high-purity nitrogen to dry the ITO glass cleaned in acetone and isopropanol;
  • Step (7) put ITO glass into high-power ozone generator, and process 30 minutes in high-concentration ozone environment;
  • Step (8) set the acceleration of the glue dispenser to 5000 rpm/s 2 , the rotational speed to 5000 rpm/s, and the time to be 90 s, and place the clean ITO glass that has been ozonated on the glue dispenser tray;
  • Step (9) take 30 ⁇ l of PVK solution with a concentration of 6 mg/ml, spread the solution on the surface of the ITO glass, and then start spin coating for about 60s;
  • Step (10) placing the ITO/PVK film after suspension coating on a 120° C. glue hot stage for annealing for 10 minutes to obtain a dense PVK film;
  • Step (11) after it is completely cooled, place the ITO glass on the suspension coater that has been set in step (8), take 30 ⁇ l of the perovskite precursor solution in step (5), click to start rotating, and wait until its speed reaches At 5000 rpm, drop a drop of CsPb 1-x Ge x Br 3 perovskite precursor solution, and after the solution is fully spread out for 21 seconds, drop 200 ⁇ l of ultra-dry ethyl acetate (C 4 H 8 O 2 ) within one second. ) solution;
  • Step (12) placing the ITO glass on which the perovskite film has been suspended and coated on a 70° C. glue hot table for annealing for 10 minutes;
  • Step (13) After the perovskite film is completely cooled, put it into the vapor deposition apparatus. Take the electron transport layer material TPBi powder, the intermediate transition layer LiF powder and the electrode Al particles and put them on the corresponding evaporation boat of the evaporation apparatus, first evaporate 50nm TPBi, then evaporate 1nm LiF, and finally evaporate 80nm Al. Finally, the devices that have been evaporated were packaged and tested for their electroluminescence efficiency (EQE), electroluminescence spectrum (EL), current density-voltage-brightness (J-V-L) and other optoelectronic properties.
  • EQE electroluminescence efficiency
  • EL electroluminescence spectrum
  • J-V-L current density-voltage-brightness

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Abstract

Disclosed are a germanium-based perovskite photoelectric material, an application thereof and a preparation method therefore, and a device and a manufacturing method therefor. A germanium-based halogen perovskite material can also be applied as a common light-emitting film and fluorescent powder, and can also be used as a core material to prepare scintillators, lasers, light-emitting transistors, and solar cells, etc. The manufacturing process of the device reduces the difficulty of experimentally manufacturing a perovskite light-emitting device while ensuring the electroluminescent efficiency, and also reduces the content of heavy metal lead in the entire device.

Description

一种锗基钙钛矿光电材料、应用、制备方法及器件和器件制备方法A germanium-based perovskite photoelectric material, application, preparation method, device and device preparation method 技术领域technical field
本发明属于光电子器件和材料科学领域，具体涉及锗基钙钛矿光电材料、应用、制备方法及器件和器件制备方法，可应用于高端显示设备、柔性显示设备和照明等。另外，此类锗基卤族钙钛矿材料还可应用为普通的发光薄膜、荧光粉；也可作为核心材料制备闪烁体、激光器、发光晶体管和太阳能电池等。The invention belongs to the fields of optoelectronic devices and material science, and specifically relates to germanium-based perovskite optoelectronic materials, applications, preparation methods, devices and device preparation methods, and can be applied to high-end display devices, flexible display devices, lighting and the like. In addition, such germanium-based halide perovskite materials can also be used as common light-emitting films and phosphors; they can also be used as core materials to prepare scintillators, lasers, light-emitting transistors, and solar cells.
背景技术Background technique
金属卤族钙钛矿材料是下一代显示、照明、太阳能、激光器、闪烁体和发光晶体管等设备的核心半导体材料，具有发射波长可调、光谱纯度高、发光效率高、可用溶液法制备等优点。再光电领域，从2014年在剑桥大学卡文迪许实验室首次发现室温下发光的钙钛矿发光二极管(LED)后，仅经历了四年，到2018年，钙钛矿LED的器件效率(EQE)就多次突破20％，接近商用型OLED的效率值。而相比已商业化的有机发光二极管(OLEDs)，钙钛矿LED具有成本低、颜色纯、色域宽、发射光谱窄、迁移率高等优势，有望取代OLEDs成为下一代高端显示设备的主流产品。Metal halide perovskite materials are core semiconductor materials for next-generation display, lighting, solar energy, lasers, scintillators, and light-emitting transistors. They have the advantages of tunable emission wavelength, high spectral purity, high luminous efficiency, and can be prepared by solution methods . In the field of optoelectronics, it has only been four years since the first discovery of perovskite light-emitting diodes (LEDs) that emit light at room temperature in the Cavendish Laboratory of Cambridge University in 2014. By 2018, the device efficiency of perovskite LEDs ( EQE) has exceeded 20% many times, which is close to the efficiency value of commercial OLEDs. Compared with commercialized organic light-emitting diodes (OLEDs), perovskite LEDs have the advantages of low cost, pure color, wide color gamut, narrow emission spectrum, and high mobility, and are expected to replace OLEDs as the mainstream product of next-generation high-end display devices. .
但是，到目前为止，普遍使用的APbX 3(A＝MA,FA,Cs,EA和Rb；X＝Br,Cl和I)卤族钙钛矿光电材料，因其B位元素含重金属铅(Pb)而严重的限制其商业化应用。因此，降低铅的使用量成为了钙钛矿LED研究的热点。基于低铅钙钛矿太阳能电池的成功经验，大量研究工作主要关注于使用低毒性的锡离子(Sn 2+)部分或者全部替代铅元素，从而达到降低体系毒性的目的。但是，在钙钛矿LED领域，发现Sn元素的引入，极大的降低了钙钛矿薄膜和器件的发光性能和EQE值。其中部分原因是因为Sn 2+非常容易氧化成Sn 4+，从而容易在卤族钙钛矿的晶体结构中诱导大量的空位，进而极大的降低了卤族钙钛矿材料的稳定性和发光性能。因此，急需寻找一种环境友好型元素，在降低卤族钙钛矿体系毒性的同时，也不会显著降低钙钛矿LED器件的光电性能。 However, so far, the commonly used APbX 3 (A=MA, FA, Cs, EA and Rb; X=Br, Cl and I) halide perovskite optoelectronic materials, because the B-site element contains heavy metal lead (Pb ) and severely limit its commercial application. Therefore, reducing the amount of lead used has become a hot topic in perovskite LED research. Based on the successful experience of low-lead perovskite solar cells, a lot of research work mainly focuses on the use of low-toxic tin ions (Sn 2+ ) to partially or completely replace lead elements, so as to reduce the toxicity of the system. However, in the field of perovskite LEDs, it was found that the introduction of Sn element greatly reduced the luminescence performance and EQE value of perovskite films and devices. Part of the reason is that Sn 2+ is very easily oxidized to Sn 4+ , which easily induces a large number of vacancies in the crystal structure of the halide perovskite, which greatly reduces the stability and luminescence of the halide perovskite material. performance. Therefore, there is an urgent need to find an environmentally friendly element that can reduce the toxicity of halide perovskite systems without significantly reducing the optoelectronic properties of perovskite LED devices.
为了降低卤族钙钛矿光电材料中铅的含量同时还能维持甚至提升其光电性能，本专利将使用环境友好型元素锗(Ge)部分替代Pb元素。并且使用合理的长链分子和添加剂进一步提升此类Ge-Pb共混钙钛矿体系的发光性能。最终，我们通过合理的制备工艺，不仅降低了卤族钙钛矿的毒性，还提升了卤族钙钛矿薄膜和钙钛矿LED器件的光电性 能和发光效率。基于钙钛矿材料优异的光电性能和半导体特性，此类低毒性钙钛矿材料的制备工艺，不仅可以应用为发光薄膜和荧光粉，还可作为核心的半导体材料应用在闪烁体、激光器、发光晶体管和太阳能电池等领域。In order to reduce the lead content in the halogen perovskite optoelectronic material while maintaining or even improving its optoelectronic properties, this patent will partially replace the Pb element with germanium (Ge), an environmentally friendly element. And the use of reasonable long-chain molecules and additives to further enhance the luminescence properties of such Ge-Pb blended perovskite systems. Finally, through a reasonable preparation process, we not only reduced the toxicity of halide perovskite, but also improved the optoelectronic properties and luminous efficiency of halide perovskite thin films and perovskite LED devices. Based on the excellent optoelectronic properties and semiconductor properties of perovskite materials, the preparation process of such low-toxicity perovskite materials can not only be used as light-emitting films and phosphors, but also as core semiconductor materials in scintillators, lasers, light-emitting transistors and solar cells.
发明内容SUMMARY OF THE INVENTION
本发明针对现有技术不足，提出了锗基钙钛矿光电材料、应用、制备方法及器件和器件制备方法。Aiming at the deficiencies of the prior art, the present invention proposes germanium-based perovskite photoelectric materials, applications, preparation methods, devices and device preparation methods.
一种锗基钙钛矿光电材料，为一种发光层材料，其结构为A’ 2(AMX 3) n-1MX 4；其中n∈[1,∞)，其中A’为PEA、PBA、OAm、TEA或PMA；A为Cs、EA、FA或MA，M为B 1-yGe y，其中B为Pb、Sn、Mn、Zn、Cd、Co、Cu、Ni，X为Cl、Br、或I。 A germanium-based perovskite photoelectric material is a light-emitting layer material, and its structure is A' 2 (AMX 3 ) n-1 MX 4 ; wherein n∈[1,∞), wherein A' is PEA, PBA, OAm, TEA or PMA; A is Cs, EA, FA or MA, M is B 1-y Ge y , wherein B is Pb, Sn, Mn, Zn, Cd, Co, Cu, Ni, X is Cl, Br, or I.
作为优选，所述的发光层材料为：PEA 2(CsPb 0.9Ge 0.1Br 3) 2Pb 0.9Ge 0.1Br 4。 Preferably, the light-emitting layer material is: PEA 2 (CsPb 0.9 Ge 0.1 Br 3 ) 2 Pb 0.9 Ge 0.1 Br 4 .
作为优选，所述的发光层材料为：AB 1-yGe yX 3；其中n为无穷大。 Preferably, the material of the light-emitting layer is: AB 1-y Ge y X 3 ; wherein n is infinite.
一种锗基钙钛矿光电材料的应用，一种锗基钙钛矿光电材料应用于多种光电器件方面，包括太阳能电池、发光二极管、探测器、荧光薄膜、荧光粉、半导体晶体管、激光等光电子器件和材料方面。Application of a germanium-based perovskite optoelectronic material, a germanium-based perovskite optoelectronic material is used in a variety of optoelectronic devices, including solar cells, light-emitting diodes, detectors, fluorescent films, phosphors, semiconductor transistors, lasers, etc. Optoelectronic devices and materials.
一种锗基钙钛矿光电材料的制备方法，方法为：采用热蒸镀、磁控溅射、MOCVD、ALD、喷涂、印刷、溶液旋涂法、真空煅烧法制备。A method for preparing a germanium-based perovskite photoelectric material. The method comprises the following steps: thermal evaporation, magnetron sputtering, MOCVD, ALD, spraying, printing, solution spin coating, and vacuum calcination.
一种锗基钙钛矿光电器件，包括电极、空穴传输层、电子传输层和发光层；其结构为从上到下依次为：第一电极、发光层、空穴传输层和第二电极；其中所述的发光层为A’ 2(AMX 3) n-1MX 4；其中n∈[1,∞)，其中A’为PEA、PBA、OAm、TEA或PMA；A为Cs、EA、FA或MA，M为B 1-yGe y，其中B为Pb、Sn、Mn、Zn、Cd、Co、Cu、Ni，X为Cl、Br、或I。 A germanium-based perovskite optoelectronic device, comprising an electrode, a hole transport layer, an electron transport layer and a light-emitting layer; its structure is as follows from top to bottom: a first electrode, a light-emitting layer, a hole transport layer and a second electrode ; wherein the light-emitting layer is A' 2 (AMX 3 ) n-1 MX 4 ; wherein n∈[1,∞), wherein A' is PEA, PBA, OAm, TEA or PMA; A is Cs, EA, FA or MA, M is B 1-y Ge y , wherein B is Pb, Sn, Mn, Zn, Cd, Co, Cu, Ni, and X is Cl, Br, or I.
一种锗基钙钛矿光电器件的制备方法，其特征在于，该方法具体包括以下步骤：A method for preparing a germanium-based perovskite optoelectronic device, characterized in that the method specifically comprises the following steps:
步骤(1)、将四种材料依次按照1:1-y:y:0.4，摩尔比称量，并放入样品瓶中，其中y＝0,0.1,0.2,0.3,0.4和0.5，其中材料一为：CsX、EAX、FAX或MAX，材料二为PbX 2、Sn X 2、Mn X 2、Zn X 2、Cd X 2、Co X 2、Cu X 2、Ni X 2，材料三为GeZ，材料四为PEAX、PBAX、OAmX、TEAX或PMAX，X＝Cl、Br或I；Z＝Br、I； Step (1), weigh the four materials in sequence according to the molar ratio of 1:1-y:y:0.4, and put them into a sample bottle, where y=0, 0.1, 0.2, 0.3, 0.4 and 0.5, where the material One is: CsX, EAX, FAX or MAX, the second material is PbX 2 , Sn X 2 , Mn X 2 , Zn X 2 , Cd X 2 , Co X 2 , Cu X 2 , Ni X 2 , the third material is GeZ, Material four is PEAX, PBAX, OAmX, TEAX or PMAX, X=Cl, Br or I; Z=Br, I;
步骤(2)、将称量完的粉体加入DMSO溶剂使其浓度为0.2mmol/ml；Step (2), adding DMSO solvent to the weighed powder to make its concentration 0.2mmol/ml;
步骤(3)、将搅拌子加入A’ 2(AMX 3) n-1MX 4前驱体溶液中，并将其放入磁力搅拌机中搅拌24小时； Step (3), adding a stirring bar to the A' 2 (AMX 3 ) n-1 MX 4 precursor solution, and placing it in a magnetic stirrer and stirring for 24 hours;
步骤(4)、待溶液完全溶解，加入添加剂18-冠醚-6溶液并继续搅拌一个小时；Step (4), until the solution is completely dissolved, add the additive 18-crown-6 solution and continue to stir for one hour;
步骤(5)、使用一次性针管和过滤头将溶液过滤，获得澄清的钙钛矿前驱体溶液；Step (5), using a disposable needle and filter head to filter the solution to obtain a clear perovskite precursor solution;
步骤(6)、将在丙酮和异丙醇清洗完成的ITO玻璃使用高纯氮气吹干；Step (6), use high-purity nitrogen to dry the ITO glass cleaned in acetone and isopropanol;
步骤(7)、将ITO玻璃放入高功率臭氧发生器中，在高浓度臭氧环境中处理30分钟；Step (7), put ITO glass into high-power ozone generator, and process 30 minutes in high-concentration ozone environment;
步骤(8)、设置匀胶机加速度为5000转/s 2，转速为5000转/s，时间为90s，将已经打完臭氧的清洁ITO玻璃放在匀胶机托盘上； Step (8), set the acceleration of the glue dispenser to 5000 rpm/s 2 , the rotational speed to 5000 rpm/s, and the time to be 90 s, and place the clean ITO glass that has been ozonated on the glue dispenser tray;
步骤(9)、取30μl浓度为6mg/ml的PVK溶液，将溶液铺满ITO玻璃表面，然后开始旋涂大约60s；Step (9), take 30 μl of PVK solution with a concentration of 6 mg/ml, spread the solution on the surface of the ITO glass, and then start spin coating for about 60s;
步骤(10)、将悬涂完成的ITO/PVK薄膜放置在100-150℃的烤胶热台上退火10分钟，获得致密的PVK薄膜；Step (10), placing the suspension-coated ITO/PVK film on a baking glue hot stage at 100-150° C. and annealing for 10 minutes to obtain a dense PVK film;
步骤(11)、待其完全冷却后将ITO玻璃放置在步骤(8)已经设置好的悬涂机上，取30μl步骤(5)中钙钛矿前驱体溶液，先点击开始旋转，待其速度达到5000转/s时，滴下一滴A’ 2(AMX 3) n-1MX 4钙钛矿前驱体溶液，待溶液全部铺展开15-25秒之后，在一秒内滴下200μl超干乙酸乙酯(C 4H 8O 2)溶液； Step (11), after it is completely cooled, place the ITO glass on the suspension coater that has been set in step (8), take 30 μl of the perovskite precursor solution in step (5), click to start rotating, and wait until its speed reaches At 5000 rpm, drop a drop of A' 2 (AMX 3 ) n-1 MX 4 perovskite precursor solution, and after the solution is fully spread out for 15-25 seconds, drop 200 μl of ultra-dry ethyl acetate ( C 4 H 8 O 2 ) solution;
步骤(12)、将已经悬涂完钙钛矿薄膜的ITO玻璃放置在50-100℃的烤胶热台上退火10min；Step (12), placing the ITO glass on which the perovskite film has been suspended and coated on a baking glue hot table at 50-100° C. for annealing for 10 minutes;
步骤(13)、待钙钛矿薄膜完全冷却后放入蒸镀仪中；取电子传输层物质TPBi粉体，中间过渡层LiF粉体和电极Al颗粒放入蒸镀仪的对应蒸发舟上，先蒸镀40-70nm TPBi，而后蒸镀0.5-3nm的LiF，最后蒸镀50-100nm的Al；最后对已经蒸镀完成的器件进行封装，测试其电致发光效率、电致发光谱、电流密度-电压-亮度等光电性能。Step (13), after the perovskite film is completely cooled, put it into the vapor deposition apparatus; take the electron transport layer material TPBi powder, the intermediate transition layer LiF powder and the electrode Al particles and put them on the corresponding evaporation boat of the vapor deposition apparatus, First, 40-70nm TPBi was evaporated, then 0.5-3nm LiF was evaporated, and 50-100nm Al was evaporated. Finally, the devices that had been evaporated were packaged to test their electroluminescence efficiency, electroluminescence spectrum, current Density-voltage-brightness and other optoelectronic properties.
作为优选，滴下200μl超干乙酸乙酯C 4H 8O 2溶液后65-75秒后，悬涂机停止旋转。 Preferably, the suspension coater stops rotating 65-75 seconds after dropping 200 μl of the ultra-dry ethyl acetate C 4 H 8 O 2 solution.
作为优选，旋涂PVK溶液后的ITO玻璃加热温度为120℃，所述的在PVK上的钙钛矿薄膜放在70℃的烤胶热台上退火10min。Preferably, the heating temperature of the ITO glass after spin-coating the PVK solution is 120° C., and the perovskite film on the PVK is annealed on a 70° C. glue hot stage for 10 minutes.
作为优选，所述的TPBi蒸镀的厚度是50nm，LiF蒸镀的厚度是1nm，Al蒸镀的厚度是80nm。Preferably, the thickness of the TPBi vapor deposition is 50 nm, the thickness of the LiF vapor deposition is 1 nm, and the thickness of the Al vapor deposition is 80 nm.
本发明的有益效果：本发明的通过悬涂方法在ITO玻璃上悬涂了空穴传输层PVK以及钙钛矿薄膜，而后使用热蒸镀的方法蒸镀电子传输层TPBi和电极LiF/Al。在保证电致发光效率的同时，降低了实验制备钙钛矿发光器件的难度，也降低了整个器件重金属铅的含量。Beneficial effects of the present invention: In the present invention, the hole transport layer PVK and the perovskite film are suspended on the ITO glass by the suspension coating method, and then the electron transport layer TPBi and the electrode LiF/Al are evaporated by thermal evaporation. While ensuring the electroluminescence efficiency, the difficulty of experimentally preparing perovskite light-emitting devices is reduced, and the content of heavy metal lead in the entire device is also reduced.
附图说明Description of drawings
图1.锗-铅钙钛矿样品的结构表征。a，在不同锗摩尔分数的硅衬底上沉积钙钛矿薄膜的XRD结果。b、使用TOPAS-V6软件对含10％Ge的钙钛矿样品进行Rietveld法结构精修的XRD图谱及相应的精修结果。c、通过Rietveld法结构精修后获得的钙钛矿晶体结构图。d、三维钙钛矿CsPb 1-xGe xBr 3晶胞参数的变化(x＝0,0.1,0.2,0.3,0.4和0.5)。e、高角环形暗场像-扫描透射电子像(STEM-HAADF)展示了CsPb 1-xGe xBr 3(x＝0.1)钙钛矿截面在不同区域的晶粒尺寸和晶格条纹。 Figure 1. Structural characterization of germanium-lead perovskite samples. a, XRD results of perovskite films deposited on silicon substrates with different germanium mole fractions. b. The XRD patterns and the corresponding refinement results of the Rietveld structure refinement of the perovskite samples containing 10% Ge using the TOPAS-V6 software. c, The perovskite crystal structure obtained after structure refinement by Rietveld method. d, Variation of the unit cell parameters of the three-dimensional perovskite CsPb 1-x Ge x Br 3 (x=0, 0.1, 0.2, 0.3, 0.4 and 0.5). e, High-angle annular dark-field image-scanning transmission electron image (STEM-HAADF) shows the grain size and lattice fringes of the CsPb 1-x Ge x Br 3 (x=0.1) perovskite cross-section in different regions.
图2.a、10％Ge钙钛矿膜的UV-Vis吸收谱图和PL谱图。b、Ge含量分别为10％-50％的UV-Vis吸收谱图(从上到下依次为x＝0,0.1,0.2,0.3,0.4和0.5)。c、CsPb 1-xGe xBr 3钙钛矿薄膜随着Ge含量的变化(x＝0,0.1,0.2,0.3,0.4和0.5)与光致发光量子效率(PLQE)之间的函数关系式。d、锗-铅钙钛矿薄膜的瞬态PL衰减曲线。e、钙钛矿薄膜Ge含量10％-50％的有效PL寿命和PL尾部衰减寿命。 Fig. 2.a, UV-Vis absorption spectrum and PL spectrum of 10%Ge perovskite film. b. UV-Vis absorption spectra with Ge content ranging from 10% to 50% respectively (from top to bottom, x=0, 0.1, 0.2, 0.3, 0.4 and 0.5). c. The functional relationship between the photoluminescence quantum efficiency (PLQE) of CsPb 1-x Ge x Br 3 perovskite films with the change of Ge content (x = 0, 0.1, 0.2, 0.3, 0.4 and 0.5) . d, Transient PL decay curves of germanium-lead perovskite films. e, Effective PL lifetime and PL tail decay lifetime of perovskite films with 10%-50% Ge content.
图3.a、钙钛矿LED器件结构示意图。b、器件各传输层、发光层和电极的能带图。c、截面样本的STEM-HAADF图像。d、Cs,Pb和Ge的EDS元素图。e、不同偏压下的器件EL谱图。插图:LED工作的照片。f、不同Ge(0mol％、10mol％和20mol％)含量钙钛矿薄膜的器件发光效率(EQE)与电流密度之间的函数关系式。g，Ge替代量为10％的钙钛矿LED器件的电流密度-电压-亮度(J-V-L)特征图谱。Figure 3.a. Schematic diagram of the structure of the perovskite LED device. b, Energy band diagram of each transport layer, light-emitting layer and electrode of the device. c, STEM-HAADF image of the cross-section sample. d, EDS elemental maps of Cs, Pb and Ge. e, EL spectra of the device under different bias voltages. Inset: Photo of the LED at work. f, The functional relationship between the device luminous efficiency (EQE) and the current density of the perovskite thin films with different Ge (0mol%, 10mol% and 20mol%) contents. g, Current density-voltage-luminance (J-V-L) characteristic maps of perovskite LED devices with 10% Ge substitution.
图4.低铅卤族钙钛矿薄膜CsPb 1-xGe xBr 3(x＝0,0.1,0.2,0.3,0.4和0.5)的X射线衍射(XRD)以及全谱拟合图。 Figure 4. X-ray diffraction (XRD) and full spectrum fitting of low lead halide perovskite films CsPb 1-x Ge x Br 3 (x=0, 0.1, 0.2, 0.3, 0.4 and 0.5).
图5.使用XRD结构精修后得到的Ge含量从0％-50％的钙钛矿晶胞体积。Figure 5. Perovskite unit cell volume with Ge content from 0%-50% obtained after structure refinement using XRD.
具体实施方式Detailed ways
本专利采用简单、低成本的溶液旋涂法制备CsPb 1-xGe xBr 3(x＝0,0.1,0.2,0.3,0.4和0.5)钙钛矿发光薄膜，通过添加一定量的长链分子苯乙基溴化胺(PEABr)和添加剂18-冠醚-6(C 12H 24O 6)进一步提升卤族钙钛矿薄膜的发光性能。而后设计了一个简单的器件模型，使用旋涂和蒸镀相结合的方式做成了少铅钙钛矿光电器件。使用X射线衍射(XRD)获得材料的晶体结构信息。使用原子力显微镜(AFM)和扫描电子显微镜(SEM)获得卤族钙钛矿薄膜的表面形貌。用大角度环形暗场扫描透射电子显微镜(HAADF-STEM)研究了薄膜的晶粒分布和钙钛矿晶体的晶格条纹，其配套的X射线能量色散谱(EDS)的Mapping模式探究了各个元素在薄膜中的分布情况。测量荧光光子寿命使用的是爱丁堡仪器FLS900光谱仪。光致发光量子效率(PLQY)和光致激发光谱(PL)使用了实验室搭建的积分球光谱测试系统获得，具体的测试方法主要参考剑桥 大学Richard Friend教授发表的论文(Advanced Materials 9,230-232(1997).)。其中，测试的激光波长为405nm，荧光光谱主要通过海洋光学的光谱仪(USB4000)测得。测量电致发光效率(EQE)使用的是Keithley 2400源表和Everfine OLED-200商用OLED性能分析系统。 This patent adopts a simple and low-cost solution spin coating method to prepare CsPb 1-x Ge x Br 3 (x=0, 0.1, 0.2, 0.3, 0.4 and 0.5) perovskite luminescent thin films, by adding a certain amount of long-chain molecules Phenethylamine bromide (PEABr) and additive 18-crown-6 (C 12 H 24 O 6 ) further enhance the luminescence properties of halogen perovskite thin films. Then a simple device model was designed, and a lead-less perovskite optoelectronic device was fabricated by a combination of spin coating and evaporation. The crystal structure information of the material was obtained using X-ray diffraction (XRD). The surface morphologies of the halide perovskite thin films were obtained using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The grain distribution of the film and the lattice fringes of the perovskite crystal were studied by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). distribution in the film. Fluorescence photon lifetimes were measured using an Edinburgh Instruments FLS900 spectrometer. The photoluminescence quantum efficiency (PLQY) and photoexcitation spectrum (PL) were obtained using the integrating sphere spectroscopic test system built in the laboratory. ).)). Among them, the tested laser wavelength is 405nm, and the fluorescence spectrum is mainly measured by Ocean Optics' spectrometer (USB4000). Electroluminescence efficiency (EQE) was measured using a Keithley 2400 source meter and an Everfine OLED-200 commercial OLED performance analysis system.
实施例1：Example 1:
步骤(1)、将CsBr、PbBr 2和PEABr按照1：1：0.4的摩尔比称量，并放入样品瓶中； Step (1), weigh CsBr, PbBr 2 and PEABr according to the molar ratio of 1:1:0.4, and put them into the sample bottle;
步骤(2)、将称量完的粉体加入1ml DMSO溶剂中，其浓度为0.2mmol/ml；Step (2), adding the weighed powder in 1ml DMSO solvent, and its concentration is 0.2mmol/ml;
步骤(3)、将搅拌子加入CsPb 1-xGe xBr 3前驱体溶液中，并将其放入磁性搅拌机中搅拌； Step (3), adding a stirring bar to the CsPb 1-x Ge x Br 3 precursor solution, and putting it into a magnetic stirrer to stir;
步骤(4)、待溶液完全溶解，加入添加剂18-冠醚-6溶液并继续搅拌一个小时；Step (4), until the solution is completely dissolved, add the additive 18-crown-6 solution and continue to stir for one hour;
步骤(5)、使用一次性针管和过滤头将溶液过滤，获得澄清的钙钛矿前驱体溶液；Step (5), using a disposable needle and filter head to filter the solution to obtain a clear perovskite precursor solution;
步骤(6)、将在丙酮和异丙醇清洗完成的ITO玻璃使用高纯氮气吹干；Step (6), use high-purity nitrogen to dry the ITO glass cleaned in acetone and isopropanol;
步骤(7)、将ITO玻璃放入高功率臭氧发生器中，在高浓度臭氧环境中处理30分钟；Step (7), put ITO glass into high-power ozone generator, and process 30 minutes in high-concentration ozone environment;
步骤(8)、设置匀胶机加速度为5000转/s 2，转速为5000转/s，时间为90s，将已经打完臭氧的清洁ITO玻璃放在匀胶机托盘上； Step (8), set the acceleration of the glue dispenser to 5000 rpm/s 2 , the rotational speed to 5000 rpm/s, and the time to be 90 s, and place the clean ITO glass that has been ozonated on the glue dispenser tray;
步骤(9)、取30μl浓度为6mg/ml的PVK溶液，将溶液铺满ITO玻璃表面，然后开始旋涂大约60s；Step (9), take 30 μl of PVK solution with a concentration of 6 mg/ml, spread the solution on the surface of the ITO glass, and then start spin coating for about 60s;
步骤(10)、将悬涂完成的ITO/PVK薄膜放置在120℃的烤胶热台上退火10分钟，获得致密的PVK薄膜；Step (10), placing the ITO/PVK film after suspension coating on a 120° C. glue hot stage for annealing for 10 minutes to obtain a dense PVK film;
步骤(11)、待其完全冷却后将ITO玻璃放置在步骤(8)已经设置好的悬涂机上，取30μl步骤(5)中钙钛矿前驱体溶液，先点击开始旋转，待其速度达到5000转/s时，滴下一滴CsPb 1-xGe xBr 3钙钛矿前驱体溶液，待溶液全部铺展开21秒之后，在一秒内滴下200μl超干乙酸乙酯(C 4H 8O 2)溶液； Step (11), after it is completely cooled, place the ITO glass on the suspension coater that has been set in step (8), take 30 μl of the perovskite precursor solution in step (5), click to start rotating, and wait until its speed reaches At 5000 rpm, drop a drop of CsPb 1-x Ge x Br 3 perovskite precursor solution, and after the solution is fully spread out for 21 seconds, drop 200 μl of ultra-dry ethyl acetate (C 4 H 8 O 2 ) within one second. ) solution;
步骤(12)、将已经悬涂完钙钛矿薄膜的ITO玻璃放置在70℃的烤胶热台上退火10min；Step (12), placing the ITO glass on which the perovskite film has been suspended and coated on a 70° C. glue hot table for annealing for 10 minutes;
步骤(13)、待钙钛矿薄膜完全冷却后放入蒸镀仪中。取电子传输层物质TPBi粉体，中间过渡层LiF粉体和电极Al颗粒放入蒸镀仪的对应蒸发舟上，先蒸镀50nm TPBi，而后蒸镀1nm的LiF，最后蒸镀80nm的Al。最后对已经蒸镀完成的器件进行封装， 测试其电致发光效率(EQE)、电致发光谱(EL)、电流密度-电压-亮度(J-V-L)等光电性能。Step (13): After the perovskite film is completely cooled, put it into the vapor deposition apparatus. Take the electron transport layer material TPBi powder, the intermediate transition layer LiF powder and the electrode Al particles and put them on the corresponding evaporation boat of the evaporation apparatus, first evaporate 50nm TPBi, then evaporate 1nm LiF, and finally evaporate 80nm Al. Finally, the vapor-deposited device was packaged, and its electroluminescence efficiency (EQE), electroluminescence spectrum (EL), current density-voltage-brightness (J-V-L) and other optoelectronic properties were tested.
如图1a所示为CsPb 1-xGe xBr 3(x＝0,0.1,0.2,0.3,0.4和0.5)薄膜的XRD图谱。图1b是x＝0.1时XRD的结构精修图，通过XRD结构精修结果可以得到如图1c所示：钙钛矿CsPb 1-xGe xBr 3的晶体结构为正交结构。图4展示了钙钛矿40％PEABr：CsPb 1-xGe xBr 3(x＝0,0.1,0.2,0.3,0.4和0.5)的结构精修结果，发现随着Ge元素的变化，可以调控2维(2D)结构钙钛矿和3维(3D)结构钙钛矿的比例。另外，Ge元素的掺入，使得钙钛矿的八面体结构变得更为的扭曲(图1d)。图5为不同Ge元素替代之后，钙钛矿的晶胞体积的变化情况，通过图5可以发现，当x＝0.2时钙钛矿CsPb 1-xGe xBr 3的晶胞体积最小，其晶胞体积的变化趋势为先下降后上升。图1e为使用像差校扫描透射电子显微镜(STEM)观测到的x＝0.1时钙钛矿CsPb 1-xGe xBr 3在不同区域的晶粒分布情况，并且纳米晶的尺寸大约为8±1nm。图2为钙钛矿CsPb 1-xGe xBr 3的光学性能和薄膜的表面形貌，图2a为钙钛矿CsPb 1-xGe xBr 3(x＝0.1)的PL和UV-Vis吸收图谱，吸收峰和PL峰的位置分别在520nm和515nm附近。图2b为CsPb 1-xGe xBr 3(x＝0,0.1,0.2,0.3,0.4和0.5)UV-Vis吸收谱图，可以发现当x＝0.4时在430nm附近出现了二维相的吸收峰，而x＝0,0.1,0.2,0.3,0.4和0.5钙钛矿的三维峰的位置基本处于515nm附近。图2c为使用光谱仪-积分球系统测得的钙钛矿CsPb 1-xGe xBr 3(x＝0,0.1,0.2,0.3,0.4和0.5)的光致发光量子效率(PLQE)，PLQE的值随着Ge替代量的增加呈现出先上升后下降的趋势。图2d为钙钛矿的荧光寿命(PL decay)图，所使用固态激光器的激光波长为450nm。图2e为有效PL寿命和PL尾部衰减寿命趋势图，随着Ge元素替代量的增加，荧光衰减寿命和有效寿命都呈现增加的趋势，直到Ge替换量达到40％时，荧光寿命和有效寿命都达到了顶点。图2f为钙钛矿CsPb 1-xGe xBr 3(x＝0和0.1)的扫描电子显微镜(SEM)和原子力显微镜(AFM)的图谱，通过对比发现：Ge元素的替换可以在一定程度上提升薄膜质量。图3主要为钙钛矿LED器件的器件结构和光电性能。图3的a图是器件的结构示意图，器件结构为ITO/PVK/Perovskite/TPBi/LiF/Al，其中PVK为空穴传输层，TPBi为电子传输层，LiF/Al和ITO为电极层，钙钛矿为发光层。图3b为钙钛矿LED器件各层之间的能级结构图。图3c为通过STEM-HAADF获得的实验所制备器件截面图，通过STEM-HAADF图谱可以看到各层的具体厚度；而图3d为取自图3c方框所示位置的EDS元素分布情况，发现Cs，Pb和Ge三个元素较为均匀的分布在钙钛矿薄膜中。图3e为不同电压下的器件EL谱图，发现在不同电压下，EL峰没有发生明显的红 移现象，说明了电致光谱的稳定性。插图为钙钛矿LED器件工作时的实物图。图3f为不同Ge(0mol％、10mol％和20mol％)含量钙钛矿薄膜的器件发光效率(EQE)与电流密度之间的函数关系式，其中当Ge的替换量为10％时，器件的效率值EQE达到了最高(8.9％)，说明Ge的部分替换不仅降低了Pb的用量，还同时提升了器件的光电性能。图3g为Ge替代量为10％的钙钛矿LED器件的电流密度-电压-亮度(J-V-L)特征图谱，发现其最大的亮度大约为10000cd/m 2。 Figure 1a shows the XRD patterns of the CsPb 1-x Ge x Br 3 (x=0, 0.1, 0.2, 0.3, 0.4 and 0.5) thin films. Fig. 1b is the structure refinement diagram of XRD when x=0.1. The result of XRD structure refinement can be obtained as shown in Fig. 1c: the crystal structure of perovskite CsPb 1-x Ge x Br 3 is an orthorhombic structure. Figure 4 shows the structural refinement results of perovskite 40% PEABr:CsPb 1-x Ge x Br 3 (x=0, 0.1, 0.2, 0.3, 0.4 and 0.5), and it is found that with the change of Ge element, it can be tuned The ratio of 2-dimensional (2D) structured perovskites to 3-dimensional (3D) structured perovskites. In addition, the incorporation of Ge element makes the octahedral structure of perovskite more distorted (Fig. 1d). Figure 5 shows the change of the unit cell volume of the perovskite after the substitution of different Ge elements. It can be found from Figure 5 that when x=0.2, the unit cell volume of the perovskite CsPb 1-x Ge x Br 3 is the smallest, and its crystal The change trend of cell volume was first decreased and then increased. Figure 1e shows the grain distribution of perovskite CsPb 1-x Ge x Br 3 in different regions observed by aberration-corrected scanning transmission electron microscopy (STEM) at x=0.1, and the size of the nanocrystals is about 8± 1nm. Figure 2 shows the optical properties of the perovskite CsPb 1-x Ge x Br 3 and the surface morphology of the film, and Figure 2a shows the PL and UV-Vis absorption of the perovskite CsPb 1-x Ge x Br 3 (x=0.1) In the spectrum, the positions of absorption peaks and PL peaks are around 520 nm and 515 nm, respectively. Figure 2b is the UV-Vis absorption spectrum of CsPb 1-x Ge x Br 3 (x = 0, 0.1, 0.2, 0.3, 0.4 and 0.5), it can be found that when x = 0.4, the absorption of the two-dimensional phase appears near 430 nm peaks, while the positions of the three-dimensional peaks of x=0, 0.1, 0.2, 0.3, 0.4 and 0.5 perovskite are substantially around 515 nm. Figure 2c is the photoluminescence quantum efficiency (PLQE) of the perovskite CsPb 1-x Ge x Br 3 (x=0, 0.1, 0.2, 0.3, 0.4 and 0.5) measured using a spectrometer-integrating sphere system, the PLQE The value first increased and then decreased with the increase of Ge substitution. Figure 2d is a graph of the fluorescence lifetime (PL decay) of the perovskite, and the laser wavelength of the solid-state laser used is 450 nm. Figure 2e shows the trend of effective PL lifetime and PL tail decay lifetime. With the increase of Ge element substitution, both the fluorescence decay lifetime and the effective lifetime showed an increasing trend. When the Ge replacement amount reached 40%, both the fluorescence lifetime and the effective lifetime both increased. reached the apex. Figure 2f shows the scanning electron microscope (SEM) and atomic force microscope (AFM) patterns of the perovskite CsPb 1-x Ge x Br 3 (x=0 and 0.1). By comparison, it is found that the replacement of Ge element can to a certain extent Improve film quality. Figure 3 mainly shows the device structure and optoelectronic properties of perovskite LED devices. Figure 3 a is a schematic structural diagram of the device, the device structure is ITO/PVK/Perovskite/TPBi/LiF/Al, where PVK is the hole transport layer, TPBi is the electron transport layer, LiF/Al and ITO are the electrode layers, calcium Titanite is the light-emitting layer. Figure 3b is a diagram of the energy level structure between the layers of the perovskite LED device. Figure 3c is the cross-sectional view of the device prepared by the experiment obtained by STEM-HAADF, and the specific thickness of each layer can be seen through the STEM-HAADF spectrum; and Figure 3d is the element distribution of EDS taken from the position shown in the box of Figure 3c. It is found that The three elements Cs, Pb and Ge are relatively uniformly distributed in the perovskite film. Figure 3e shows the EL spectra of the device at different voltages. It is found that the EL peaks do not have obvious red shifts at different voltages, indicating the stability of the electro-spectroscopy. The inset is a physical image of the perovskite LED device in operation. Figure 3f shows the functional relationship between the device luminous efficiency (EQE) and the current density of the perovskite films with different Ge (0mol%, 10mol% and 20mol%) content, where when the replacement amount of Ge is 10%, the device The efficiency value EQE reached the highest (8.9%), indicating that the partial replacement of Ge not only reduced the amount of Pb, but also improved the optoelectronic properties of the device. Figure 3g is the current density-voltage-luminance (JVL) characteristic map of the perovskite LED device with 10% Ge substitution, and it is found that its maximum luminance is about 10000 cd/m 2 .
实施例2：Example 2:
步骤(1)、将CsI、PbI 2、GeI 2和PEAI按照1:0.9:0.1:0.4，摩尔比称量，并放入样品瓶中； Step (1), weigh CsI, PbI 2 , GeI 2 and PEAI according to a molar ratio of 1:0.9:0.1:0.4, and put them into a sample bottle;
步骤(2)、将称量完的粉体加入DMSO溶剂使其浓度为0.2mmol/ml；Step (2), adding DMSO solvent to the weighed powder to make its concentration 0.2mmol/ml;
步骤(3)、将搅拌子加入CsPb 1-xGe xI 3前驱体溶液中，并将其放入磁力搅拌机中搅拌； Step (3), adding a stirring bar into the CsPb 1-x Ge x I 3 precursor solution, and putting it into a magnetic stirrer to stir;
步骤(4)、待溶液完全溶解，加入添加剂18-冠醚-6溶液并继续搅拌一个小时；Step (4), until the solution is completely dissolved, add the additive 18-crown-6 solution and continue to stir for one hour;
步骤(5)、使用一次性针管和过滤头将溶液过滤；Step (5), filter the solution using a disposable syringe and filter head;
步骤(6)、将在丙酮和异丙醇清洗完成的ITO玻璃使用高纯氮气吹干；Step (6), use high-purity nitrogen to dry the ITO glass cleaned in acetone and isopropanol;
步骤(7)、将ITO玻璃放入高功率臭氧发生器中，在高浓度臭氧环境中处理30分钟；Step (7), put ITO glass into high-power ozone generator, and process 30 minutes in high-concentration ozone environment;
步骤(8)、设置匀胶机加速度为5000转/s 2，转速为5000转/s，时间为90s，将已经打完臭氧的清洁ITO玻璃放在匀胶机托盘上； Step (8), set the acceleration of the glue dispenser to 5000 rpm/s 2 , the rotational speed to 5000 rpm/s, and the time to be 90 s, and place the clean ITO glass that has been ozonated on the glue dispenser tray;
步骤(9)、取30μl浓度为6mg/ml的PVK溶液，将溶液铺满ITO玻璃表面，然后开始旋涂大约60s；Step (9), take 30 μl of PVK solution with a concentration of 6 mg/ml, spread the solution on the surface of the ITO glass, and then start spin coating for about 60s;
步骤(10)、将悬涂完成的ITO/PVK薄膜放置在120℃的烤胶热台上退火10分钟，获得致密的PVK薄膜；Step (10), placing the ITO/PVK film after suspension coating on a 120° C. glue hot stage for annealing for 10 minutes to obtain a dense PVK film;
步骤(11)、待其完全冷却后将ITO玻璃放置在步骤(8)已经设置好的悬涂机上，取30μl步骤(5)中钙钛矿前驱体溶液，先点击开始旋转，待其速度达到5000转/s时，滴下一滴CsPb 1-xGe xI 3钙钛矿前驱体溶液，待溶液全部铺展开21秒之后，在一秒内滴下200μl超干乙酸乙酯(C 4H 8O 2)溶液； Step (11), after it is completely cooled, place the ITO glass on the suspension coater that has been set in step (8), take 30 μl of the perovskite precursor solution in step (5), click to start rotating, and wait until its speed reaches At 5000 rpm, drop a drop of CsPb 1-x Ge x I 3 perovskite precursor solution, and after the solution is fully spread out for 21 seconds, drop 200 μl of ultra-dry ethyl acetate (C 4 H 8 O 2 ) within one second. ) solution;
步骤(12)、将已经悬涂完钙钛矿薄膜的ITO玻璃放置在70℃的烤胶热台上退火10min；Step (12), placing the ITO glass on which the perovskite film has been suspended and coated on a 70° C. glue hot table for annealing for 10 minutes;
步骤(13)、待钙钛矿薄膜完全冷却后放入蒸镀仪中。取电子传输层物质TPBi粉体，中间过渡层LiF粉体和电极Al颗粒放入蒸镀仪的对应蒸发舟上，先蒸镀50nm TPBi，而后蒸镀1nm的LiF，最后蒸镀80nm的Al。最后对已经蒸镀完成的器件进行封装， 测试其电致发光效率(EQE)、电致发光谱(EL)、电流密度-电压-亮度(J-V-L)等光电性能。Step (13): After the perovskite film is completely cooled, put it into the vapor deposition apparatus. Take the electron transport layer material TPBi powder, the intermediate transition layer LiF powder and the electrode Al particles and put them on the corresponding evaporation boat of the evaporation apparatus, first evaporate 50nm TPBi, then evaporate 1nm LiF, and finally evaporate 80nm Al. Finally, the vapor-deposited device was packaged, and its electroluminescence efficiency (EQE), electroluminescence spectrum (EL), current density-voltage-brightness (J-V-L) and other optoelectronic properties were tested.
实施例3：Example 3:
步骤(1)、将FABr、PbBr 2、GeBr 2和PEABr按照1:0.7:0.3:0.4，摩尔比称量，并放入玻璃瓶中； Step (1), weigh FABr, PbBr 2 , GeBr 2 and PEABr according to a molar ratio of 1:0.7:0.3:0.4, and put them into a glass bottle;
步骤(2)、将称量完的粉体加入DMSO溶剂使其浓度为0.2mmol/ml；Step (2), adding DMSO solvent to the weighed powder to make its concentration 0.2mmol/ml;
步骤(3)、将搅拌子加入FAPb 1-xGe xBr 3前驱体溶液中，并将其放入磁力搅拌机中搅拌； Step (3), adding a stirring bar to the FAPb 1-x Ge x Br 3 precursor solution, and putting it into a magnetic stirrer to stir;
步骤(4)、待溶液完全溶解，加入添加剂18-冠醚-6溶液并继续搅拌一个小时；Step (4), until the solution is completely dissolved, add the additive 18-crown-6 solution and continue to stir for one hour;
步骤(5)、使用一次性针管和过滤头将溶液过滤；Step (5), filter the solution using a disposable syringe and filter head;
步骤(6)、将在丙酮和异丙醇清洗完成的ITO玻璃使用高纯氮气吹干；Step (6), use high-purity nitrogen to dry the ITO glass cleaned in acetone and isopropanol;
步骤(7)、将ITO玻璃放入高功率臭氧发生器中，在高浓度臭氧环境中处理30分钟；Step (7), put ITO glass into high-power ozone generator, and process 30 minutes in high-concentration ozone environment;
步骤(8)、设置匀胶机加速度为5000转/s 2，转速为5000转/s，时间为90s，将已经打完臭氧的清洁ITO玻璃放在匀胶机托盘上； Step (8), set the acceleration of the glue dispenser to 5000 rpm/s 2 , the rotational speed to 5000 rpm/s, and the time to be 90 s, and place the clean ITO glass that has been ozonated on the glue dispenser tray;
步骤(9)、取30μl浓度为6mg/ml的PVK溶液，将溶液铺满ITO玻璃表面，然后开始旋涂大约60s；Step (9), take 30 μl of PVK solution with a concentration of 6 mg/ml, spread the solution on the surface of the ITO glass, and then start spin coating for about 60s;
步骤(10)、将悬涂完成的ITO/PVK薄膜放置在120℃的烤胶热台上退火10分钟，获得致密的PVK薄膜；Step (10), placing the ITO/PVK film after suspension coating on a 120° C. glue hot stage for annealing for 10 minutes to obtain a dense PVK film;
步骤(11)、待其完全冷却后将ITO玻璃放置在步骤(8)已经设置好的悬涂机上，取30μl步骤(5)中钙钛矿前驱体溶液，先点击开始旋转，待其速度达到5000转/s时，滴下一滴FAPb 1-xGe xBr 3钙钛矿前驱体溶液，待溶液全部铺展开21秒之后，在一秒内滴下200μl超干乙酸乙酯(C 4H 8O 2)溶液； Step (11), after it is completely cooled, place the ITO glass on the suspension coater that has been set in step (8), take 30 μl of the perovskite precursor solution in step (5), click to start rotating, and wait until its speed reaches At 5000 rpm, drop a drop of FAPb 1-x Ge x Br 3 perovskite precursor solution, and after the solution is fully spread out for 21 seconds, drop 200 μl of ultra-dry ethyl acetate (C 4 H 8 O 2 ) within one second. ) solution;
步骤(12)、将已经悬涂完钙钛矿薄膜的ITO玻璃放置在70℃的烤胶热台上退火10min；Step (12), placing the ITO glass on which the perovskite film has been suspended and coated on a 70° C. glue hot table for annealing for 10 minutes;
步骤(13)、待钙钛矿薄膜完全冷却后放入蒸镀仪中。取电子传输层物质TPBi粉体，中间过渡层LiF粉体和电极Al颗粒放入蒸镀仪的对应蒸发舟上，先蒸镀50nm TPBi，而后蒸镀1nm的LiF，最后蒸镀80nm的Al。最后对已经蒸镀完成的器件进行封装，测试其电致发光效率(EQE)、电致发光谱(EL)、电流密度-电压-亮度(J-V-L)等光电性能。Step (13): After the perovskite film is completely cooled, put it into the vapor deposition apparatus. Take the electron transport layer material TPBi powder, the intermediate transition layer LiF powder and the electrode Al particles and put them on the corresponding evaporation boat of the evaporation apparatus, first evaporate 50nm TPBi, then evaporate 1nm LiF, and finally evaporate 80nm Al. Finally, the devices that have been evaporated were packaged and tested for their electroluminescence efficiency (EQE), electroluminescence spectrum (EL), current density-voltage-brightness (J-V-L) and other optoelectronic properties.
实施例4：Example 4:
步骤(1)、将EABr、PbBr 2、GeBr 2和PEABr按照1:0.6:0.4:0.4，摩尔比称量，并放入玻璃瓶中； Step (1), weigh EABr, PbBr 2 , GeBr 2 and PEABr according to a molar ratio of 1:0.6:0.4:0.4, and put them into a glass bottle;
步骤(2)、将称量完的粉体加入DMSO溶剂使其浓度为0.2mmol/ml；Step (2), adding DMSO solvent to the weighed powder to make its concentration 0.2mmol/ml;
步骤(3)、将搅拌子加入EAPb 1-xGe xBr 3前驱体溶液中，并将其放入磁性搅拌机中搅拌； Step (3), adding a stirring bar to the EAPb 1-x Ge x Br 3 precursor solution, and putting it into a magnetic stirrer to stir;
步骤(4)、待溶液完全溶解，加入添加剂18-冠醚-6溶液并继续搅拌一个小时；Step (4), until the solution is completely dissolved, add the additive 18-crown-6 solution and continue to stir for one hour;
步骤(5)、使用一次性针管和过滤头将溶液过滤；Step (5), filter the solution using a disposable syringe and filter head;
步骤(6)、将在丙酮和异丙醇清洗完成的ITO玻璃使用高纯氮气吹干；Step (6), use high-purity nitrogen to dry the ITO glass cleaned in acetone and isopropanol;
步骤(7)、将ITO玻璃放入高功率臭氧发生器中，在高浓度臭氧环境中处理30分钟；Step (7), put ITO glass into high-power ozone generator, and process 30 minutes in high-concentration ozone environment;
步骤(8)、设置匀胶机加速度为5000转/s 2，转速为5000转/s，时间为90s，将已经打完臭氧的清洁ITO玻璃放在匀胶机托盘上； Step (8), set the acceleration of the glue dispenser to 5000 rpm/s 2 , the rotational speed to 5000 rpm/s, and the time to be 90 s, and place the clean ITO glass that has been ozonated on the glue dispenser tray;
步骤(9)、取30μl浓度为6mg/ml的PVK溶液，将溶液铺满ITO玻璃表面，然后开始旋涂大约60s；Step (9), take 30 μl of PVK solution with a concentration of 6 mg/ml, spread the solution on the surface of the ITO glass, and then start spin coating for about 60s;
步骤(10)、将悬涂完成的ITO/PVK薄膜放置在120℃的烤胶热台上退火10分钟，获得致密的PVK薄膜；Step (10), placing the ITO/PVK film after suspension coating on a 120° C. glue hot stage for annealing for 10 minutes to obtain a dense PVK film;
步骤(11)、待其完全冷却后将ITO玻璃放置在步骤(8)已经设置好的悬涂机上，取30μl步骤(5)中钙钛矿前驱体溶液，先点击开始旋转，待其速度达到5000转/s时，滴下一滴EAPb 1-xGe xBr 3钙钛矿前驱体溶液，待溶液全部铺展开21秒之后，在一秒内滴下200μl超干乙酸乙酯(C 4H 8O 2)溶液； Step (11), after it is completely cooled, place the ITO glass on the suspension coater that has been set in step (8), take 30 μl of the perovskite precursor solution in step (5), click to start rotating, and wait until its speed reaches At 5000 rpm, drop a drop of EAPb 1-x Ge x Br 3 perovskite precursor solution, and after the solution is fully spread out for 21 seconds, drop 200 μl of ultra-dry ethyl acetate (C 4 H 8 O 2 ) within one second. ) solution;
步骤(12)、将已经悬涂完钙钛矿薄膜的ITO玻璃放置在70℃的烤胶热台上退火10min；Step (12), placing the ITO glass on which the perovskite film has been suspended and coated on a 70° C. glue hot table for annealing for 10 minutes;
步骤(13)、待钙钛矿薄膜完全冷却后放入蒸镀仪中。取电子传输层物质TPBi粉体，中间过渡层LiF粉体和电极Al颗粒放入蒸镀仪的对应蒸发舟上，先蒸镀50nm TPBi，而后蒸镀1nm的LiF，最后蒸镀80nm的Al。最后对已经蒸镀完成的器件进行封装，测试其电致发光效率(EQE)、电致发光谱(EL)、电流密度-电压-亮度(J-V-L)等光电性能。Step (13): After the perovskite film is completely cooled, put it into the vapor deposition apparatus. Take the electron transport layer material TPBi powder, the intermediate transition layer LiF powder and the electrode Al particles and put them on the corresponding evaporation boat of the evaporation apparatus, first evaporate 50nm TPBi, then evaporate 1nm LiF, and finally evaporate 80nm Al. Finally, the devices that have been evaporated were packaged and tested for their electroluminescence efficiency (EQE), electroluminescence spectrum (EL), current density-voltage-brightness (J-V-L) and other optoelectronic properties.
实施例5：Example 5:
步骤(1)、将CsBr、PbBr 2、GeBr和PEABr按照1:0.8:0.2:0.4，摩尔比称量，并放入玻璃瓶中； Step (1), weigh CsBr, PbBr 2 , GeBr and PEABr according to a molar ratio of 1:0.8:0.2:0.4, and put them into a glass bottle;
步骤(2)、将称量完的粉体加入DMSO溶剂使其浓度为0.2mmol/ml；Step (2), adding DMSO solvent to the weighed powder to make its concentration 0.2mmol/ml;
步骤(3)、将搅拌子加入CsPb 1-xGe xBr 3前驱体溶液中，并将其放入磁性搅拌机中搅拌； Step (3), adding a stirring bar to the CsPb 1-x Ge x Br 3 precursor solution, and putting it into a magnetic stirrer to stir;
步骤(4)、待溶液完全溶解，加入添加剂18-冠醚-6溶液并继续搅拌一个小时；Step (4), until the solution is completely dissolved, add the additive 18-crown-6 solution and continue to stir for one hour;
步骤(5)、使用一次性针管和过滤头将溶液过滤；Step (5), filter the solution using a disposable syringe and filter head;
步骤(6)、将在丙酮和异丙醇清洗完成的ITO玻璃使用高纯氮气吹干；Step (6), use high-purity nitrogen to dry the ITO glass cleaned in acetone and isopropanol;
步骤(7)、将ITO玻璃放入高功率臭氧发生器中，在高浓度臭氧环境中处理30分钟；Step (7), put ITO glass into high-power ozone generator, and process 30 minutes in high-concentration ozone environment;
步骤(8)、设置匀胶机加速度为5000转/s 2，转速为5000转/s，时间为90s，将已经打完臭氧的清洁ITO玻璃放在匀胶机托盘上； Step (8), set the acceleration of the glue dispenser to 5000 rpm/s 2 , the rotational speed to 5000 rpm/s, and the time to be 90 s, and place the clean ITO glass that has been ozonated on the glue dispenser tray;
步骤(9)、取30μl浓度为6mg/ml的PVK溶液，将溶液铺满ITO玻璃表面，然后开始旋涂大约60s；Step (9), take 30 μl of PVK solution with a concentration of 6 mg/ml, spread the solution on the surface of the ITO glass, and then start spin coating for about 60s;
步骤(10)、将悬涂完成的ITO/PVK薄膜放置在120℃的烤胶热台上退火10分钟，获得致密的PVK薄膜；Step (10), placing the ITO/PVK film after suspension coating on a 120° C. glue hot stage for annealing for 10 minutes to obtain a dense PVK film;
步骤(11)、待其完全冷却后将ITO玻璃放置在步骤(8)已经设置好的悬涂机上，取30μl步骤(5)中钙钛矿前驱体溶液，先点击开始旋转，待其速度达到5000转/s时，滴下一滴CsPb 1-xGe xBr 3钙钛矿前驱体溶液，待溶液全部铺展开21秒之后，在一秒内滴下200μl超干乙酸乙酯(C 4H 8O 2)溶液； Step (11), after it is completely cooled, place the ITO glass on the suspension coater that has been set in step (8), take 30 μl of the perovskite precursor solution in step (5), click to start rotating, and wait until its speed reaches At 5000 rpm, drop a drop of CsPb 1-x Ge x Br 3 perovskite precursor solution, and after the solution is fully spread out for 21 seconds, drop 200 μl of ultra-dry ethyl acetate (C 4 H 8 O 2 ) within one second. ) solution;
步骤(12)、将已经悬涂完钙钛矿薄膜的ITO玻璃放置在70℃的烤胶热台上退火10min；Step (12), placing the ITO glass on which the perovskite film has been suspended and coated on a 70° C. glue hot table for annealing for 10 minutes;
步骤(13)、待钙钛矿薄膜完全冷却后放入蒸镀仪中。取电子传输层物质TPBi粉体，中间过渡层LiF粉体和电极Al颗粒放入蒸镀仪的对应蒸发舟上，先蒸镀50nm TPBi，而后蒸镀1nm的LiF，最后蒸镀80nm的Al。最后对已经蒸镀完成的器件进行封装，测试其电致发光效率(EQE)、电致发光谱(EL)、电流密度-电压-亮度(J-V-L)等光电性能。Step (13): After the perovskite film is completely cooled, put it into the vapor deposition apparatus. Take the electron transport layer material TPBi powder, the intermediate transition layer LiF powder and the electrode Al particles and put them on the corresponding evaporation boat of the evaporation apparatus, first evaporate 50nm TPBi, then evaporate 1nm LiF, and finally evaporate 80nm Al. Finally, the devices that have been evaporated were packaged and tested for their electroluminescence efficiency (EQE), electroluminescence spectrum (EL), current density-voltage-brightness (J-V-L) and other optoelectronic properties.
实施例6：Example 6:
步骤(1)、将CsBr、PbBr 2、GeBr和PEABr按照1:0.7:0.3:0.4，摩尔比称量，并放入玻璃瓶中； Step (1), weigh CsBr, PbBr 2 , GeBr and PEABr according to a molar ratio of 1:0.7:0.3:0.4, and put them into a glass bottle;
步骤(2)、将称量完的粉体加入DMSO溶剂使其浓度为0.2μmol/ml；Step (2), adding DMSO solvent to the weighed powder to make its concentration 0.2 μmol/ml;
步骤(3)、将搅拌子加入CsPb 1-xGe xBr 3前驱体溶液中，并将其放入磁性搅拌机中搅拌； Step (3), adding a stirring bar to the CsPb 1-x Ge x Br 3 precursor solution, and putting it into a magnetic stirrer to stir;
步骤(4)、待溶液完全溶解，加入添加剂18-冠醚-6溶液并继续搅拌一个小时；Step (4), until the solution is completely dissolved, add the additive 18-crown-6 solution and continue to stir for one hour;
步骤(5)、使用一次性针管和过滤头将溶液过滤；Step (5), filter the solution using a disposable syringe and filter head;
步骤(6)、将在丙酮和异丙醇清洗完成的ITO玻璃使用高纯氮气吹干；Step (6), use high-purity nitrogen to dry the ITO glass cleaned in acetone and isopropanol;
步骤(7)、将ITO玻璃放入高功率臭氧发生器中，在高浓度臭氧环境中处理30分钟；Step (7), put ITO glass into high-power ozone generator, and process 30 minutes in high-concentration ozone environment;
步骤(8)、设置匀胶机加速度为5000转/s 2，转速为5000转/s，时间为90s，将已经打完臭氧的清洁ITO玻璃放在匀胶机托盘上； Step (8), set the acceleration of the glue dispenser to 5000 rpm/s 2 , the rotational speed to 5000 rpm/s, and the time to be 90 s, and place the clean ITO glass that has been ozonated on the glue dispenser tray;
步骤(9)、取30μl浓度为6mg/ml的PVK溶液，将溶液铺满ITO玻璃表面，然后开始旋涂大约60s；Step (9), take 30 μl of PVK solution with a concentration of 6 mg/ml, spread the solution on the surface of the ITO glass, and then start spin coating for about 60s;
步骤(10)、将悬涂完成的ITO/PVK薄膜放置在120℃的烤胶热台上退火10分钟，获得致密的PVK薄膜；Step (10), placing the ITO/PVK film after suspension coating on a 120° C. glue hot stage for annealing for 10 minutes to obtain a dense PVK film;
步骤(11)、待其完全冷却后将ITO玻璃放置在步骤(8)已经设置好的悬涂机上，取30μl步骤(5)中钙钛矿前驱体溶液，先点击开始旋转，待其速度达到5000转/s时，滴下一滴CsPb 1-xGe xBr 3钙钛矿前驱体溶液，待溶液全部铺展开21秒之后，在一秒内滴下200μl超干乙酸乙酯(C 4H 8O 2)溶液； Step (11), after it is completely cooled, place the ITO glass on the suspension coater that has been set in step (8), take 30 μl of the perovskite precursor solution in step (5), click to start rotating, and wait until its speed reaches At 5000 rpm, drop a drop of CsPb 1-x Ge x Br 3 perovskite precursor solution, and after the solution is fully spread out for 21 seconds, drop 200 μl of ultra-dry ethyl acetate (C 4 H 8 O 2 ) within one second. ) solution;
步骤(12)、将已经悬涂完钙钛矿薄膜的ITO玻璃放置在70℃的烤胶热台上退火10min；Step (12), placing the ITO glass on which the perovskite film has been suspended and coated on a 70° C. glue hot table for annealing for 10 minutes;
步骤(13)、待钙钛矿薄膜完全冷却后放入蒸镀仪中。取电子传输层物质TPBi粉体，中间过渡层LiF粉体和电极Al颗粒放入蒸镀仪的对应蒸发舟上，先蒸镀50nm TPBi，而后蒸镀1nm的LiF，最后蒸镀80nm的Al。最后对已经蒸镀完成的器件进行封装，测试其电致发光效率(EQE)、电致发光谱(EL)、电流密度-电压-亮度(J-V-L)等光电性能。Step (13): After the perovskite film is completely cooled, put it into the vapor deposition apparatus. Take the electron transport layer material TPBi powder, the intermediate transition layer LiF powder and the electrode Al particles and put them on the corresponding evaporation boat of the evaporation apparatus, first evaporate 50nm TPBi, then evaporate 1nm LiF, and finally evaporate 80nm Al. Finally, the devices that have been evaporated were packaged and tested for their electroluminescence efficiency (EQE), electroluminescence spectrum (EL), current density-voltage-brightness (J-V-L) and other optoelectronic properties.

Claims (10)

  1. 一种锗基钙钛矿光电材料，其特征在于：为一种发光层材料，其结构为A’ 2(AMX 3) n-1MX 4；其中n∈[1,∞)，其中A’为PEA、PBA、OAm、TEA或PMA；A为Cs、EA、FA或MA，M为B 1-yGe y，其中B为Pb、Sn、Mn、Zn、Cd、Co、Cu、Ni，X为Cl、Br、或I。 A germanium-based perovskite photoelectric material is characterized in that: it is a light-emitting layer material, and its structure is A' 2 (AMX 3 ) n-1 MX 4 ; wherein n∈[1,∞), wherein A' is PEA, PBA, OAm, TEA or PMA; A is Cs, EA, FA or MA, M is B 1-y Ge y , wherein B is Pb, Sn, Mn, Zn, Cd, Co, Cu, Ni, X is Cl, Br, or I.
  2. 根据权力要求1所述的一种锗基钙钛矿光电材料，其特征在于：所述的发光层材料为：PEA 2(CsPb 0.9Ge 0.1Br 3) 2Pb 0.9Ge 0.1Br 4。 The germanium-based perovskite optoelectronic material according to claim 1, wherein the material of the light-emitting layer is: PEA 2 (CsPb 0.9 Ge 0.1 Br 3 ) 2 Pb 0.9 Ge 0.1 Br 4 .
  3. 根据权力要求1所述的一种锗基钙钛矿光电材料，其特征在于：所述的发光层材料为：AB 1-yGe yX 3；其中n为无穷大。 The germanium-based perovskite optoelectronic material according to claim 1, wherein the light-emitting layer material is: AB 1-y Ge y X 3 , wherein n is infinite.
  4. 根据权力要求1所述的一种锗基钙钛矿光电材料，其特征在于：所述的发光层材料的结构为：2维，3维，量子点，准二维结构。A germanium-based perovskite optoelectronic material according to claim 1, characterized in that: the structure of the light-emitting layer material is: 2-dimensional, 3-dimensional, quantum dot, and quasi-two-dimensional structure.
  5. 根据权力要求1所述的一种锗基钙钛矿光电材料的应用，其特征在于：一种锗基钙钛矿光电材料应用于多种光电器件方面，包括太阳能电池、发光二极管、探测器、荧光薄膜、荧光粉、半导体晶体管、激光等光电子器件和材料方面。The application of a germanium-based perovskite optoelectronic material according to claim 1, characterized in that: a germanium-based perovskite optoelectronic material is applied to a variety of optoelectronic devices, including solar cells, light-emitting diodes, detectors, Fluorescent films, phosphors, semiconductor transistors, lasers and other optoelectronic devices and materials.
  6. 根据权力要求1所述的一种锗基钙钛矿光电材料的制备方法，其特征在于：采用热蒸镀、磁控溅射、MOCVD、ALD、喷涂、印刷、溶液旋涂法、真空煅烧法制备。The method for preparing a germanium-based perovskite photoelectric material according to claim 1, characterized in that: using thermal evaporation, magnetron sputtering, MOCVD, ALD, spraying, printing, solution spin coating, vacuum calcination preparation.
  7. 一种锗基钙钛矿光电器件，其特征在于：包括电极、空穴传输层/注入层、电子传输层/注入层和发光层；其结构为从一端到另一端依次为：阴极、电子传输/注入层、发光层/光吸收层、空穴传输/注入层、阳极；其中所述的发光层为A’ 2(AMX 3) n-1MX 4；其中n∈[1,∞)，其中A’为PEA、PBA、OAm、TEA或PMA；A为Cs、EA、FA或MA，M为B 1-yGe y，其中B为Pb、Sn、Mn、Zn、Cd、Co、Cu、Ni，X为Cl、Br、或I。 A germanium-based perovskite photoelectric device is characterized in that: comprising an electrode, a hole transport layer/injection layer, an electron transport layer/injection layer and a light-emitting layer; its structure is as follows from one end to the other end: a cathode, an electron transport layer /injection layer, light-emitting layer/light absorption layer, hole transport/injection layer, anode; wherein the light-emitting layer is A' 2 (AMX 3 ) n-1 MX 4 ; wherein n∈[1,∞), wherein A' is PEA, PBA, OAm, TEA or PMA; A is Cs, EA, FA or MA, M is B 1-y Ge y , wherein B is Pb, Sn, Mn, Zn, Cd, Co, Cu, Ni , X is Cl, Br, or I.
  8. 根据权力要求7所述的一种锗基钙钛矿光电器件的制备方法，其特征在于，该方法具体包括以下步骤：The method for preparing a germanium-based perovskite optoelectronic device according to claim 7, wherein the method specifically comprises the following steps:
    步骤(1)、将四种材料依次按照1:1-y:y:0.4，摩尔比称量，并放入样品瓶中，其中y＝0-1，其中材料一为：CsX、EAX、FAX或MAX，材料二为PbX 2、Sn X 2、Mn X 2、Zn X 2、Cd X 2、Co X 2、Cu X 2、Ni X 2，材料三为GeZ，材料四为PEAX、PBAX、OAmX、TEAX或PMAX，X＝Cl、Br或I；Z＝Br、I； Step (1), weigh the four materials in sequence according to the molar ratio of 1:1-y:y:0.4, and put them into the sample bottle, where y=0-1, and the first material is: CsX, EAX, FAX Or MAX, material 2 is PbX 2 , Sn X 2 , Mn X 2 , Zn X 2 , Cd X 2 , Co X 2 , Cu X 2 , Ni X 2 , material 3 is GeZ, material 4 is PEAX, PBAX, OAmX , TEAX or PMAX, X=Cl, Br or I; Z=Br, I;
    步骤(2)、将称量完的粉体加入DMSO溶剂；Step (2), adding the DMSO solvent to the weighed powder;
    步骤(3)、将搅拌子加入A’ 2(AMX 3) n-1MX 4前驱体溶液中，并将其放入磁力搅拌机中搅拌24小时； Step (3), adding a stirring bar to the A' 2 (AMX 3 ) n-1 MX 4 precursor solution, and placing it in a magnetic stirrer and stirring for 24 hours;
    步骤(4)、待溶液完全溶解，加入添加剂18-冠醚-6溶液并继续搅拌一个小时；Step (4), until the solution is completely dissolved, add the additive 18-crown-6 solution and continue to stir for one hour;
    步骤(5)、使用一次性针管和过滤头将溶液过滤，获得澄清的钙钛矿前驱体溶液；Step (5), using a disposable needle and filter head to filter the solution to obtain a clear perovskite precursor solution;
    步骤(6)、将在丙酮和异丙醇清洗完成的ITO玻璃使用高纯氮气吹干；Step (6), use high-purity nitrogen to dry the ITO glass cleaned in acetone and isopropanol;
    步骤(7)、将ITO玻璃放入高功率臭氧发生器中，在高浓度臭氧环境中处理30分钟；Step (7), put ITO glass into high-power ozone generator, and process 30 minutes in high-concentration ozone environment;
    步骤(8)、设置匀胶机加速度为5000转/s 2，转速为5000转/s，时间为90s，将已经打完臭氧的清洁ITO玻璃放在匀胶机托盘上； Step (8), set the acceleration of the glue dispenser to 5000 rpm/s 2 , the rotational speed to 5000 rpm/s, and the time to be 90 s, and place the clean ITO glass that has been ozonated on the glue dispenser tray;
    步骤(9)、取30μl浓度为6mg/ml的PVK溶液，将溶液铺满ITO玻璃表面，然后开始旋涂大约60s；Step (9), take 30 μl of PVK solution with a concentration of 6 mg/ml, spread the solution on the surface of the ITO glass, and then start spin coating for about 60s;
    步骤(10)、将悬涂完成的ITO/PVK薄膜放置在100-150℃的烤胶热台上退火10分钟，获得致密的PVK薄膜；Step (10), placing the suspension-coated ITO/PVK film on a baking glue hot stage at 100-150° C. and annealing for 10 minutes to obtain a dense PVK film;
    步骤(11)、待其完全冷却后将ITO玻璃放置在步骤(8)已经设置好的悬涂机上，取30μl步骤(5)中钙钛矿前驱体溶液，先点击开始旋转，待其速度达到5000转/s时，滴下一滴A’ 2(AMX 3) n-1MX 4钙钛矿前驱体溶液，待溶液全部铺展开15-25秒之后，在一秒内滴下200μl超干乙酸乙酯溶液； Step (11), after it is completely cooled, place the ITO glass on the suspension coater that has been set in step (8), take 30 μl of the perovskite precursor solution in step (5), click to start rotating, and wait until its speed reaches At 5000 rpm, drop a drop of A' 2 (AMX 3 ) n-1 MX 4 perovskite precursor solution, and after the solution is fully spread out for 15-25 seconds, drop 200 μl of ultra-dry ethyl acetate solution within one second ;
    步骤(12)、将已经悬涂完钙钛矿薄膜的ITO玻璃放置在50-100℃的烤胶热台上退火10min；Step (12), placing the ITO glass on which the perovskite film has been suspended and coated on a baking glue hot table at 50-100° C. for annealing for 10 minutes;
    步骤(13)、待钙钛矿薄膜完全冷却后放入蒸镀仪中；取电子传输层物质TPBi粉体，中间过渡层LiF粉体和电极Al颗粒放入蒸镀仪的对应蒸发舟上，先蒸镀40-70nm TPBi，而后蒸镀0.5-3nm的LiF，最后蒸镀50-100nm的Al；最后对已经蒸镀完成的器件进行封装，测试其电致发光效率、电致发光谱、电流密度-电压-亮度。Step (13), after the perovskite film is completely cooled, put it into the vapor deposition apparatus; take the electron transport layer material TPBi powder, the intermediate transition layer LiF powder and the electrode Al particles and put them on the corresponding evaporation boat of the vapor deposition apparatus, First, 40-70nm TPBi was evaporated, then 0.5-3nm LiF was evaporated, and 50-100nm Al was evaporated. Finally, the devices that had been evaporated were packaged to test their electroluminescence efficiency, electroluminescence spectrum, current Density-Voltage-Brightness.
  9. 根据权力要求8所述的一种锗基钙钛矿光电器件的制备方法，其特征在于：滴下200μl超干乙酸乙酯C 4H 8O 2溶液后65-75秒后，悬涂机停止旋转；所述的DMSO溶剂的浓度为0.2mmol/ml。 The method for preparing a germanium-based perovskite photoelectric device according to claim 8, wherein the suspension coater stops rotating 65-75 seconds after dripping 200 μl of the ultra-dry ethyl acetate C 4 H 8 O 2 solution ; The concentration of the DMSO solvent is 0.2 mmol/ml.
  10. 根据权力要求8所述的一种锗基钙钛矿光电器件的制备方法，其特征在于：所述的TPBi蒸镀的厚度是50nm，LiF蒸镀的厚度是1nm，Al蒸镀的厚度是80nm。The method for preparing a germanium-based perovskite optoelectronic device according to claim 8, wherein the thickness of the TPBi evaporation is 50 nm, the thickness of the LiF evaporation is 1 nm, and the thickness of the Al evaporation is 80 nm .
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