A CsPbI3 perovskite battery containing heterogeneous mixed fluorescent labeling material and its preparation method

Abstract

The present invention discloses a CsPbI3 perovskite cell containing a heterogeneous mixed fluorescent marker material and a preparation method thereof. The method comprises adding an RBITC material to a perovskite precursor solution, spin-coating the solution, and then annealing the solution. The RBITC contains groups such as -SCN, -COOH, and -N-R. During the annealing process of the perovskite film, the -SCN is converted into HSCN and volatilized in the form of gas. The volatilization process regulates the perovskite crystallization process, delays crystallization, and reduces film defects. The -COOH in the RBITC also interacts with related defects such as lead and iodine in the perovskite film in the form of Lewis acid-base or hydrogen bonds, thereby reducing the film defect state density, reducing non-radiative recombination losses, and improving the cell efficiency.

Description

Technical Field

[0001] The present invention belongs to the technical field of perovskite solar cell preparation, and specifically relates to a CsPbI3 perovskite cell containing a heterogeneous mixed fluorescent marker material and a preparation method thereof. Background Art

[0002] Traditional fossil energy reserves are limited, and their use can lead to significant problems such as environmental pollution and excessive carbon emissions. Solar energy, due to its renewability and cleanliness, has become an ideal green energy source, and the efficient development and utilization of solar energy has become a focus of current attention. Solar cells are devices that directly convert solar energy into electrical energy, providing an important avenue for the development and utilization of solar energy. Perovskite solar cells are a new type of thin-film battery that uses perovskite materials as a light-absorbing layer. Their photoelectric conversion efficiency has increased from 3.8% in 2009 to 26.1% today. The commercialization of perovskite cells is being actively promoted, making them a new type of thin-film battery with great industrial application prospects.

[0003] Currently, high-efficiency perovskite cells primarily utilize organic-inorganic hybrid perovskites as their light-absorbing layer. However, the organic components are susceptible to escaping under the influence of heat and humidity, resulting in poor cell stability. Replacing the organic components with inorganic components to construct an all-inorganic CsPbI3 perovskite cell can significantly improve device stability. However, the photoelectric conversion efficiency of all-inorganic perovskite cells is relatively low, primarily due to the multiple phase transitions that occur during film formation, leading to a high number of internal defects. Summary of the Invention

[0004] The purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art and provide a CsPbI3 perovskite cell containing a heterogeneous mixed fluorescent labeling material and a preparation method thereof, so as to solve the problems of many defects and poor performance of the all-inorganic CsPbI3 perovskite solar cells prepared by the prior art.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] A method for preparing a perovskite cell containing a heterogeneous mixed fluorescent marker material, wherein a perovskite precursor solution is coated on the surface of an electron transport layer and then annealed to obtain a perovskite absorption layer;

[0007] The solutes of the perovskite precursor solution are HPbI3, CsI and RBITC, and the solvent is a mixed solvent of DMF and DMSO.

[0008] A further improvement of the present invention is:

[0009] Preferably, the concentration of RBITC in the perovskite precursor solution is 0.25 mg / mL to 2 mg / mL.

[0010] Preferably, the volume ratio of DMF to DMSO in the solvent is 8.5:1.5.

[0011] Preferably, the molar ratio of HPbI3 to CsI is 0.745:0.825.

[0012] Preferably, the perovskite precursor solution is coated on the electron transport layer by a spin coating process.

[0013] Preferably, the spin coating process includes two stages, the first stage has a rotation speed of 500-1000 rpm and a spin coating time of 5-20 s; the second stage has a rotation speed of 2000-3000 rpm and a spin coating time of 30-50 s.

[0014] Preferably, the annealing temperature is 150~190 o C, annealing time is 40~60 min.

[0015] A perovskite cell containing a heterogeneous mixed fluorescent marker material, the perovskite cell comprising a conductive glass, an electron transport layer, a perovskite absorption layer, a hole transport layer and a gold film arranged in sequence from bottom to top;

[0016] The perovskite absorption layer is CsPbI3, and RBITC chemicals are added to the perovskite absorption layer.

[0017] Preferably, the electron transport layer is TiO2, and the hole transport layer is Spiro-OMeTAD.

[0018] Preferably, the thickness of the electron transport layer is 40-50 nm.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] The present invention discloses a preparation method of a CsPbI3 perovskite battery comprising a heterogeneous mixed fluorescent marker material. The method comprises adding RBITC material to a perovskite precursor solution, annealing after spin coating, and containing groups such as -SCN, -COOH, and -NR in RBITC. During the annealing process of the perovskite film, -SCN is converted to HSCN and volatilized in the form of a gas. The volatilization process regulates the perovskite crystallization process, which can delay the crystallization process. The prepared film has few defects. The -COOH in RBITC can also interact with related defects such as lead and iodine in the perovskite film in the form of Lewis acid-base or hydrogen bonds, thereby reducing the film defect state density, reducing non-radiative recombination losses, and improving battery efficiency. However, the carboxyl group is hydrophilic, which makes the prepared perovskite absorption layer hydrophobic. In the present invention, the -NR of RBITC contains a strongly hydrophobic group, which can hinder the influence of water molecules on the perovskite, further improving the environmental stability of the battery. Therefore, the photoelectric conversion efficiency of the all-inorganic CsPbI3 perovskite cell constructed based on RBITC increased from 18.41% to 20.41%. The unencapsulated cell can still maintain 89.14% of the initial efficiency after being placed in air for 980 hours.

[0021] The present invention also discloses a perovskite cell containing a heterogeneous mixed fluorescent marker material. The perovskite absorption layer crystals in the perovskite cell have a passivation effect, which makes the perovskite film of better quality, with fewer pores in the film, more dense, and larger grain size. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 Schematic diagram of the structure of the all-inorganic perovskite solar cell prepared by the present invention;

[0023] In the figure: 1 is conductive glass, 2 is electron transport layer, 3 is perovskite absorption layer, 4 is hole transport layer, and 5 is metal electrode;

[0024] Figure 2 3 is a performance comparison chart of the inorganic perovskite solar cell with and without RBITC added as described in Example 1 of the present invention;

[0025] Figure 3 1 are planar SEM scans of the inorganic perovskite solar cell with and without RBITC added as described in Example 1 of the present invention; wherein (a) is a planar SEM scan of the perovskite film without RBITC added; (b) is a planar SEM scan of the perovskite film with RBITC added (0.5 mg / mL);

[0026] Figure 4 3 is a comparative XRD graph of the inorganic perovskite solar cell with and without RBITC added as described in Example 1 of the present invention;

[0027] Figure 5 is Pb in Example 1 of the present invention 2+ , I - 、Cs + XPS mechanism diagram of the interaction between Pb and RBITC; (a) shows the Pb in the perovskite film without and with RBITC 2+ XPS graph of I in pure CsI and CsI with RBITC added - XPS graph of CsI in pure CsI and CsI with RBITC added. + XPS graph;

[0028] Figure 6 UPS diagrams of the inorganic perovskite solar cell with and without RBITC added as described in Example 1 of the present invention;

[0029] Figure 7 3 is a comparison chart of the efficiency stability of the inorganic perovskite solar cell with and without RBITC added as described in Example 1 of the present invention;

[0030] Figure 8 3 is a comparative XRD graph of the air stability of the inorganic perovskite film with and without RBITC added as described in Example 1 of the present invention;

[0031] Figure 9 3 is a comparison diagram of the contact angles of the perovskite film as the concentration of the RBITC drug increases as described in Example 5 of the present invention;

[0032] Figure 10 PL comparison diagram of the perovskite film as the concentration of RBITC chemical increases as described in Example 5 of the present invention;

[0033] Figure 11 This is a comparison chart of the carrier lifetime (TRPL) in the perovskite film as the concentration of the RBITC drug increases as described in Example 5 of the present invention. DETAILED DESCRIPTION

[0034] The present invention is further described in detail below with reference to the accompanying drawings and specific embodiments:

[0035] One embodiment of the present invention discloses a method for optimizing CsPbI3 perovskite cells using heterogeneous mixed fluorescent marker materials, comprising the following steps:

[0036] Step 1, cleaning the conductive glass substrate;

[0037] The conductive glass substrate 1 is a fluorine-doped tin oxide (FTO) conductive glass, which is ultrasonically cleaned in ultrapure water with glass cleaning agent for 10 to 30 minutes. The ultrapure water is replaced every 30 minutes to clean the residual cleaning agent on the glass. The conductive glass is then blown dry with a nitrogen gun.

[0038] Step 2, preparing an electron transport layer;

[0039] The electron transport layer was prepared on the conductive glass substrate by water bath deposition. The material of the electron transport layer was TiO2. The deposition time was 40 min to 1 h. The FTO glass was treated with ultraviolet ozone for 15 min. 4.5 mL of TiCl4 was dropped on 200 mL of ice. After the ice melted to the size of a thumb, it was placed in 70 o The thickness of the prepared TiO2 electron transport layer is 40-50 nm.

[0040] Step 3, preparing an all-inorganic perovskite light absorption layer;

[0041] (1) Prepare an all-inorganic perovskite precursor solution; dissolve HPbI3, CsI, and rhodamine isothiocyanate B (RBITC) in a mixed solvent of DMF and DMSO (8.5 / 1.5, V / V) to prepare a perovskite precursor solution; the RBITC concentration is 0.25 mg / mL~2 mg / mL.

[0042] (2) The all-inorganic perovskite precursor solution was spin-coated on the surface of the electron transport layer. The spin coating was divided into two stages: the first stage had a rotation speed of 500-1000 rpm and a spin coating time of 5-20 s; the second stage had a rotation speed of 2000-3000 rpm and a spin coating time of 30-50 s; the spin coating was followed by annealing treatment; the annealing temperature was 150 o C~190 o C, the annealing time is 40~60 min to obtain the perovskite absorption layer.

[0043] Step 4, preparing a hole transport layer;

[0044] A hole transport layer was prepared on the thin film prepared in step 3 by spin coating, wherein the spin coating speed was 3000-5000 rpm and the spin coating time was 20-40 s; the material of the hole transport layer was Spiro-OMeTAD solution.

[0045] Step 5, evaporating electrodes;

[0046] A gold electrode with a thickness of 80-100 nm was evaporated on the hole transport layer prepared in step 4. The cell area was 0.09 cm 2 , and obtain perovskite solar cells.

[0047] The battery structure prepared by the above method includes (1), conductive glass (2), electron transport layer (3), perovskite absorption layer (4), hole transport layer and (5), metal electrode stacked in sequence from bottom to top.

[0048] Comparative Example

[0049] Step 1: Ultrasonic clean the conductive glass in ultrapure water with glass detergent for 10 to 30 minutes, replace the ultrapure water every 30 minutes to clean the residual detergent on the glass, and then blow dry the conductive glass with a nitrogen gun.

[0050] Step 2: hydrothermal deposition method, 70 o C oven for 55 min, and deposit a layer of TiO2 on the cleaned FTO surface as an electron transport layer. The FTO glass was treated with ultraviolet ozone for 15 min, 4.5 mL of TiCl4 was dropped on 200 mL of ice, and after the ice melted to the size of a thumb, it was placed in a 70 o The thickness of the prepared TiO2 electron transport layer is 40-50nm.

[0051] Step 3: Dissolve hydrogen lead iodide (HPbI3) and cesium iodide (CsI) (n:n = 0.745:0.825) in a mixed solvent of DMF and DMSO (V / V = 8.5 / 1.5) to prepare a CsPbI3 perovskite precursor solution with a concentration of 0.745 M. Stir the perovskite precursor solution for 24 h.

[0052] Step 4: Spin-coat the prepared inorganic CsPbI3 perovskite precursor solution on the electron transport layer to prepare the perovskite absorption layer; the spin-coating process is divided into two stages: the first stage has a rotation speed of 1000 rpm and a spin-coating time of 10 s; the second stage has a rotation speed of 3000 rpm and a spin-coating time of 40 s; the annealing process is carried out at 170 o Annealing on hot plate C for 50 min.

[0053] Step 5: Spin-coat the hole transport layer Spiro-OMeTAD on the perovskite layer using a spin coating method. Dissolve Spiro-OMeTAD powder (90 mg), lithium salt (22 μL), and t-BP (36 μL) in 1 mL of chlorobenzene to obtain a Spiro-OMeTAD solution with a concentration of 90 mg / mL. Spin-coating at a speed of 5000 rpm for 40 s to obtain a hole transport layer.

[0054] Step 6: Evaporate an 80 nm thick gold film on the hole transport layer Spiro-OMeTAD. The cell area is 0.09 cm 2, and obtain perovskite solar cells.

[0055] Example 1

[0056] Step 1: Ultrasonic clean the conductive glass in ultrapure water with glass detergent for 10 to 30 minutes, replace the ultrapure water every 30 minutes to clean the residual detergent on the glass, and then blow dry the conductive glass with a nitrogen gun.

[0057] Step 2: using hydrothermal deposition method, 70 o C oven for 55 min, and deposit a layer of TiO2 on the cleaned FTO surface as an electron transport layer. The FTO glass was treated with ultraviolet ozone for 15 min, 4.5 mL of TiCl4 was dropped on 200 mL of ice, and after the ice melted to the size of a thumb, it was placed in a 70 o The thickness of the prepared TiO2 electron transport layer is 40-50nm.

[0058] Step 3: Prepare a CsPbI3 perovskite precursor solution with a concentration of 0.745 M by dissolving hydrogen lead iodide (HPbI3) and cesium iodide (CsI) (n:n = 0.745:0.825) and 0.5 mg of RBITC in a mixed solvent of DMF and DMSO (MA molecules will be formed during heating, which will form HSCN gas with RBITC drugs) (V / V = 8.5 / 1.5). Stir the perovskite precursor solution for 24 h.

[0059] Step 4: Spin-coat the prepared inorganic CsPbI3 perovskite precursor solution on the electron transport layer to prepare the perovskite absorption layer; the spin-coating process is divided into two stages: the first stage has a rotation speed of 1000 rpm and a spin-coating time of 10 s; the second stage has a rotation speed of 3000 rpm and a spin-coating time of 40 s; the annealing process is carried out at 170 o Annealing on hot plate C for 50 min.

[0060] Step 5: Spin-coat the hole transport layer Spiro-OMeTAD on the perovskite layer using a spin coating method. Dissolve Spiro-OMeTAD powder (90 mg), lithium salt (22 μL), and t-BP (36 μL) in 1 mL of chlorobenzene to obtain a Spiro-OMeTAD solution with a concentration of 90 mg / mL. Spin-coating at a speed of 5000 rpm for 40 s to obtain a hole transport layer.

[0061] Step 6: Evaporate an 80 nm thick gold film on the hole transport layer Spiro-OMeTAD. The cell area is 0.09 cm 2 , and obtain perovskite solar cells.

[0062] Compared with the inorganic perovskite solar cell without RBITC in the comparative example, the inorganic perovskite solar cell with RBITC added in this embodiment has a greatly improved open circuit voltage, and the final cell efficiency is 20.41%.

[0063] In this example, an inorganic perovskite cell structure based on heterogeneous mixed labeled fluorescent materials is obtained. Figure 1 As shown, it includes 1 for conductive glass, 2 for electron transport layer, 3 for perovskite absorption layer, 4 for hole transport layer, and 5 for metal electrode.

[0064] like Figure 2 As shown, the inorganic perovskite solar cell with RBITC added in this embodiment is compared with the inorganic perovskite solar cell without RBITC added in the comparative example. The open circuit voltage and fill factor are improved, and the cell efficiency is also greatly improved, increasing from 18.41% to 20.41%.

[0065] like Figure 3 As shown in the SEM scanning comparison diagram of the inorganic perovskite solar cell with RBITC added and the inorganic perovskite solar cell without RBITC added in the comparative example, it can be seen that the perovskite film with the addition of RBITC material has better quality, fewer film pores, is denser, and has larger grain size.

[0066] like Figure 4 The figure shows an XRD comparison of an inorganic perovskite solar cell with RBITC added and an inorganic perovskite solar cell without RBITC added in the comparative example. It can be seen from the figure that the crystallinity of the perovskite film is enhanced and the lead iodide residue is reduced after the addition of RBITC.

[0067] like Figure 5 As shown in the figure, compared with the inorganic perovskite film without RBITC in the comparative example, the 4f of Pb moves toward the low binding energy direction. At the same time, from the XPS of pure CsI and CsI with RBITC, it can be seen that the 3d of I and the 3d of Cs both have obvious displacements toward the low binding energy direction, indicating that the chemical environment of the 4f of Pb, the 3d of I and the 3d of Cs have changed, resulting in a passivation effect.

[0068] like Figure 6 The figure shows a comparison of the UPS performance of an inorganic perovskite film with RBITC added and a comparative inorganic perovskite film without RBITC. The figure shows that the conduction and valence bands of the film with RBITC added are both improved, and the energy levels of the film are more closely aligned with those of the Spiro-OMeTAD hole transport layer.

[0069] like Figure 7Figure 2 shows a stability comparison of an inorganic perovskite solar cell with RBITC added and a control cell without RBITC. The figure shows that the cell with RBITC added maintains an efficiency of 89.14% after nearly 1000 hours of storage. Compared to the control, the optimized device exhibits significantly enhanced stability.

[0070] like Figure 8 Figure 2 shows an XRD comparison of the air stability of a perovskite film with RBITC added and a control film without RBITC. The figure shows that the film with RBITC added did not undergo a phase transition after 120 hours of storage at 0-25% humidity; instead, its crystallinity weakened, and no other perovskite phases formed. The XRD pattern of the control film, however, shows a phase transition after 120 hours of storage. This indicates that the optimized film exhibits superior stability.

[0071] Example 2

[0072] In this example, the concentration of RBITC added was 0.25 mg / mL, and the other steps were the same as in Example 1. In this example, the efficiency of the inorganic perovskite solar cell was 20.02%.

[0073] Example 3

[0074] In this example, the concentration of RBITC added was 1 mg / mL, and the other steps were the same as in Examples 1 and 2. In this example, the efficiency of the inorganic perovskite solar cell was 19.22%.

[0075] Example 4

[0076] In this example, the concentration of RBITC added was 2 mg / mL, and the other steps were the same as in Examples 1, 2, and 3. In this example, the efficiency of the inorganic perovskite solar cell was 17.12%.

[0077] Example 5

[0078] Step 1: Ultrasonic clean the conductive glass in ultrapure water with glass detergent for 20 minutes, replace the ultrapure water every 30 minutes to clean the residual detergent on the glass, and then blow dry the conductive glass with a nitrogen gun.

[0079] Step 2: hydrothermal deposition method, 70 o C oven for 50 min, and deposit a layer of TiO2 on the cleaned FTO surface as an electron transport layer. The FTO glass was treated with ultraviolet ozone for 15 min, 4.5 mL of TiCl4 was dropped on 200 mL of ice, and after the ice melted to the size of a thumb, it was placed in a 70 oThe thickness of the prepared TiO2 electron transport layer is 40-50 nm.

[0080] Step 3: Hydrogen lead iodide (HPbI3) and cesium iodide (CsI) (n:n = 0.745:0.825) and 0.25 mg, 0.5 mg, and 1 mg of RBITC were dissolved in a mixed solvent of DMF and DMSO (V / V = 8.5 / 1.5) to prepare a CsPbI3 perovskite precursor solution with a concentration of 0.745 M. The perovskite precursor solution was stirred for 10 h for standby use.

[0081] Step 4: Spin-coat the prepared inorganic CsPbI3 perovskite precursor solution on the electron transport layer to prepare the perovskite absorption layer; the spin-coating process is divided into two stages: the first stage has a rotation speed of 1000 rpm and a spin-coating time of 10 s; the second stage has a rotation speed of 3000 rpm and a spin-coating time of 40 s; the annealing process is carried out at 170 o Annealing was performed on a hot plate at C for 45 min.

[0082] Step 5: Spin-coat the hole transport layer Spiro-OMeTAD on the perovskite layer using a spin coating method. Dissolve Spiro-OMeTAD powder (90 mg), lithium salt (22 μL), and t-BP (36 μL) in 1 mL of chlorobenzene to obtain a Spiro-OMeTAD solution with a concentration of 90 mg / mL. Spin-coating at a speed of 5000 rpm for 40 s to obtain a hole transport layer.

[0083] Step 6: Evaporate an 80 nm thick gold film on the hole transport layer Spiro-OMeTAD. The cell area is 0.09 cm 2 , and obtain perovskite solar cells.

[0084] In this embodiment, inorganic perovskite films with different concentrations of RBITC are added, such as Figure 9 As shown in the figure, as the concentration of RBITC increases, the contact angle of the perovskite film increases, indicating that the hydrophobicity of the film is enhanced, which verifies that the optimized film is more stable in the air.

[0085] like Figure 10 、 11 As shown in the figure, the PL peak of the perovskite film at a concentration of 0.5 mg / mL RBITC is the strongest and the carrier lifetime is the longest, indicating that the carrier concentration in the perovskite film under this condition is high. It also verifies that the defects of the perovskite film are reduced and non-radiative recombination is reduced under this condition.

[0086] Example 6

[0087] Step 1: Ultrasonic clean the conductive glass in ultrapure water with glass detergent for 10 to 30 minutes, replace the ultrapure water every 30 minutes to clean the residual detergent on the glass, and then blow dry the conductive glass with a nitrogen gun.

[0088] Step 2: hydrothermal deposition method, 70 o C oven for 1 h, and deposit a layer of TiO2 on the cleaned FTO surface as an electron transport layer. The FTO glass was treated with ultraviolet ozone for 15 min, 4.5 mL of TiCl4 was dropped on 200 mL of ice, and after the ice melted to the size of a thumb, it was placed in a 70 o The thickness of the prepared TiO2 electron transport layer is 40-50 nm.

[0089] Step 3: Hydrogen lead iodide (HPbI3) and cesium iodide (CsI) (n:n = 0.745:0.825) and 0.5 mg of RBITC were dissolved in a mixed solvent of DMF and DMSO (V / V = 8.5 / 1.5) to prepare a CsPbI3 perovskite precursor solution with a concentration of 0.745 M. The perovskite precursor solution was stirred for 20 h.

[0090] Step 4: Spin-coat the prepared inorganic CsPbI3 perovskite precursor solution on the electron transport layer to prepare the perovskite absorption layer; the spin-coating process is divided into two stages: the first stage has a rotation speed of 1000 rpm and a spin-coating time of 10 s; the second stage has a rotation speed of 3000 rpm and a spin-coating time of 40 s; the annealing process is carried out at 190 o Anneal on hot plate C for 15 min.

[0091] Step 5: Spin-coat the hole transport layer Spiro-OMeTAD on the perovskite layer using a spin coating method. Dissolve Spiro-OMeTAD powder (90 mg), lithium salt (22 μL), and t-BP (36 μL) in 1 mL of chlorobenzene to obtain a Spiro-OMeTAD solution with a concentration of 90 mg / mL. Spin-coating at a speed of 4500 rpm for 40 s to obtain a hole transport layer.

[0092] Step 6: Evaporate an 80 nm thick gold film on the hole transport layer Spiro-OMeTAD. The cell area is 0.09 cm 2 , and obtain perovskite solar cells.

[0093] Example 7

[0094] Step 1: ultrasonically clean the conductive glass in ultrapure water with glass cleaning agent for 10 to 30 minutes, replace the ultrapure water every 30 minutes to clean the residual cleaning agent on the glass, and then blow dry the conductive glass with a nitrogen gun.

[0095] Step 2: hydrothermal deposition method, 70 o C oven for 1 h, and deposit a layer of TiO2 on the cleaned FTO surface as an electron transport layer. The FTO glass was treated with ultraviolet ozone for 15 min, 4.5 mL of TiCl4 was dropped on 200 mL of ice, and after the ice melted to the size of a thumb, it was placed in a 70 o The thickness of the prepared TiO2 electron transport layer is 40-50 nm.

[0096] Step 3: Hydrogen lead iodide (HPbI3) and cesium iodide (CsI) (n:n = 0.745:0.825) and 0.5 mg of RBITC were dissolved in a mixed solvent of DMF and DMSO (V / V = 8.5 / 1.5) to prepare a CsPbI3 perovskite precursor solution with a concentration of 0.745 M. The perovskite precursor solution was stirred for 10 h.

[0097] Step 4: Spin-coat the prepared inorganic CsPbI3 perovskite precursor solution on the electron transport layer to prepare the perovskite absorption layer; the spin-coating process is divided into two stages: the first stage has a rotation speed of 1000 rpm and a spin-coating time of 10 s; the second stage has a rotation speed of 2000 rpm and a spin-coating time of 40 s; the annealing process is carried out at 160 o Annealing was performed on a hot plate at C for 60 min.

[0098] In step 5, a hole transport layer (Spiro-OMeTAD) was spin-coated on the perovskite layer. Spiro-OMeTAD powder (90 mg), lithium salt (22 μL), and t-BP (36 μL) were dissolved in 1 mL of chlorobenzene to obtain a Spiro-OMeTAD solution with a concentration of 90 mg / mL. The hole transport layer was prepared by spin coating at a speed of 5000 rpm for 40 s.

[0099] Step 6: Evaporate an 80 nm thick gold film on the hole transport layer Spiro-OMeTAD. The cell area is 0.09 cm 2 , and obtain perovskite solar cells.

[0100] Example 8

[0101] Step 1: ultrasonically clean the conductive glass in ultrapure water with glass cleaning agent for 10 to 30 minutes, replace the ultrapure water every 30 minutes to clean the residual cleaning agent on the glass, and then blow dry the conductive glass with a nitrogen gun.

[0102] Step 2: hydrothermal deposition method, 70 o C oven for 1 h, and deposit a layer of TiO2 on the cleaned FTO surface as an electron transport layer. The FTO glass was treated with ultraviolet ozone for 15 min, 4.5 mL of TiCl4 was dropped on 200 mL of ice, and after the ice melted to the size of a thumb, it was placed in a 70 o The thickness of the prepared TiO2 electron transport layer is 40-50 nm.

[0103] Step 3: Hydrogen lead iodide (HPbI3) and cesium iodide (CsI) (n:n = 0.745:0.825) and 0.5 mg of RBITC were dissolved in a mixed solvent of DMF and DMSO (V / V = 8.5 / 1.5) to prepare a CsPbI3 perovskite precursor solution with a concentration of 0.745 M. The perovskite precursor solution was stirred for 10 h.

[0104] Step 4: Spin-coat the prepared inorganic CsPbI3 perovskite precursor solution on the electron transport layer to prepare the perovskite absorption layer; the spin-coating process is divided into two stages: the first stage is at a speed of 500 rpm and a spin-coating time of 20 s; the second stage is at a speed of 2500 rpm and a spin-coating time of 35 s; the annealing process is at 150 o Annealing was performed on a hot plate at C for 60 min.

[0105] In step 5, a hole transport layer (Spiro-OMeTAD) was spin-coated on the perovskite layer. Spiro-OMeTAD powder (90 mg), lithium salt (22 μL), and t-BP (36 μL) were dissolved in 1 mL of chlorobenzene to obtain a Spiro-OMeTAD solution with a concentration of 90 mg / mL. The hole transport layer was prepared by spin coating at a speed of 5000 rpm for 40 s.

[0106] Step 6: Evaporate an 80 nm thick gold film on the hole transport layer Spiro-OMeTAD. The cell area is 0.09 cm 2 , and obtain perovskite solar cells.

[0107] Example 9

[0108] Step 1: ultrasonically clean the conductive glass in ultrapure water with glass cleaning agent for 10 to 30 minutes, replace the ultrapure water every 30 minutes to clean the residual cleaning agent on the glass, and then blow dry the conductive glass with a nitrogen gun.

[0109] Step 2: hydrothermal deposition method, 70 o C oven for 1 h, and deposit a layer of TiO2 on the cleaned FTO surface as an electron transport layer. The FTO glass was treated with ultraviolet ozone for 15 min, 4.5 mL of TiCl4 was dropped on 200 mL of ice, and after the ice melted to the size of a thumb, it was placed in a 70 o The thickness of the prepared TiO2 electron transport layer is 40-50 nm.

[0110] Step 3: Hydrogen lead iodide (HPbI3) and cesium iodide (CsI) (n:n = 0.745:0.825) and 0.5 mg of RBITC were dissolved in a mixed solvent of DMF and DMSO (V / V = 8.5 / 1.5) to prepare a CsPbI3 perovskite precursor solution with a concentration of 0.745 M. The perovskite precursor solution was stirred for 10 h.

[0111] Step 4: Spin-coat the prepared inorganic CsPbI3 perovskite precursor solution on the electron transport layer to prepare the perovskite absorption layer; the spin-coating process is divided into two stages: the first stage is at a speed of 800 rpm and a spin-coating time of 5 s; the second stage is at a speed of 2200 rpm and a spin-coating time of 50 s; the annealing process is carried out at 170 o Annealing on hot plate C for 50 min.

[0112] In step 5, a hole transport layer (Spiro-OMeTAD) was spin-coated on the perovskite layer. Spiro-OMeTAD powder (90 mg), lithium salt (22 μL), and t-BP (36 μL) were dissolved in 1 mL of chlorobenzene to obtain a Spiro-OMeTAD solution with a concentration of 90 mg / mL. The hole transport layer was prepared by spin coating at a speed of 5000 rpm for 40 s.

[0113] Step 6: Evaporate an 80 nm thick gold film on the hole transport layer Spiro-OMeTAD. The cell area is 0.09 cm 2 , and obtain perovskite solar cells.

[0114] Example 10

[0115] Step 1: ultrasonically clean the conductive glass in ultrapure water with glass cleaning agent for 10 to 30 minutes, replace the ultrapure water every 30 minutes to clean the residual cleaning agent on the glass, and then blow dry the conductive glass with a nitrogen gun.

[0116] Step 2: hydrothermal deposition method, 70 o C oven for 1 h, and deposit a layer of TiO2 on the cleaned FTO surface as an electron transport layer. The FTO glass was treated with ultraviolet ozone for 15 min, 4.5 mL of TiCl4 was dropped on 200 mL of ice, and after the ice melted to the size of a thumb, it was placed in a 70 o The thickness of the prepared TiO2 electron transport layer is 40-50 nm.

[0117] Step 3: Hydrogen lead iodide (HPbI3) and cesium iodide (CsI) (n:n = 0.745:0.825) and 0.5 mg of RBITC were dissolved in a mixed solvent of DMF and DMSO (V / V = 8.5 / 1.5) to prepare a CsPbI3 perovskite precursor solution with a concentration of 0.745 M. The perovskite precursor solution was stirred for 10 h.

[0118] Step 4: Spin-coat the prepared inorganic CsPbI3 perovskite precursor solution on the electron transport layer to prepare the perovskite absorption layer; the spin-coating process is divided into two stages: the first stage has a rotation speed of 600 rpm and a spin-coating time of 10 s; the second stage has a rotation speed of 2800 rpm and a spin-coating time of 30 s; the annealing process is carried out at 180 o Annealing on hot plate C for 40 min.

[0119] In step 5, a hole transport layer (Spiro-OMeTAD) was spin-coated on the perovskite layer. Spiro-OMeTAD powder (90 mg), lithium salt (22 μL), and t-BP (36 μL) were dissolved in 1 mL of chlorobenzene to obtain a Spiro-OMeTAD solution with a concentration of 90 mg / mL. The hole transport layer was prepared by spin coating at a speed of 5000 rpm for 40 s.

[0120] Step 6: Evaporate an 80 nm thick gold film on the hole transport layer Spiro-OMeTAD. The cell area is 0.09 cm 2 , and obtain perovskite solar cells.

[0121] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a perovskite cell containing heterogeneous mixed fluorescent labeling materials, characterized in that: The perovskite precursor solution is coated on the surface of the electron transport layer and then annealed to obtain the perovskite absorption layer; The solutes of the perovskite precursor solution are HPbI3, CsI and RBITC, and the solvent is a mixed solvent of DMF and DMSO.

2. The method for preparing a perovskite cell comprising a heterogeneous mixed fluorescent marker material according to claim 1, characterized in that: The concentration of RBITC in the perovskite precursor solution is 0.25 mg / mL to 2 mg / mL.

3. The method for preparing a perovskite cell comprising a heterogeneous mixed fluorescent marker material according to claim 1, characterized in that: The volume ratio of DMF and DMSO in the solvent was 8.5:1.

5.

4. The method for preparing a perovskite cell comprising a heterogeneous mixed fluorescent marker material according to claim 1, characterized in that: The molar ratio of HPbI3 to CsI is 0.745:0.

825.

5. The method for preparing a perovskite cell comprising a heterogeneous mixed fluorescent marker material according to claim 1, characterized in that: The perovskite precursor solution is coated on the electron transport layer through a spin coating process.

6. The method for preparing a perovskite cell comprising a heterogeneous mixed fluorescent marker material according to claim 5, characterized in that: The spin coating process includes two stages. In the first stage, the rotation speed is 500-1000 rpm and the spin coating time is 5-20 s; in the second stage, the rotation speed is 2000-3000 rpm and the spin coating time is 30-50 s.

7. The method for preparing a perovskite cell comprising a heterogeneous mixed fluorescent marker material according to claim 1, characterized in that: The annealing temperature is 150~190 o C, annealing time is 40~60 min.

8. A perovskite cell comprising a heterogeneous mixed fluorescent marker material, characterized in that: The perovskite cell comprises a conductive glass, an electron transport layer, a perovskite absorption layer, a hole transport layer and a gold film arranged in sequence from bottom to top; The perovskite absorption layer is CsPbI3, and RBITC chemicals are added to the perovskite absorption layer.

9. The perovskite cell comprising heterogeneous mixed fluorescent marker materials according to claim 8, characterized in that: The electron transport layer is TiO2, and the hole transport layer is Spiro-OMeTAD.

10. The perovskite cell comprising heterogeneous mixed fluorescent marker materials according to claim 8, characterized in that: The thickness of the electron transport layer is 40-50 nm.

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