CN115784629B - Tin-containing double perovskite material film and in-situ solution preparation method and application thereof - Google Patents
Tin-containing double perovskite material film and in-situ solution preparation method and application thereof Download PDFInfo
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- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
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Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E10/542—Dye sensitized solar cells
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Abstract
The invention belongs to the field of photoelectric functional film materials, and discloses a tin-containing double perovskite material film, an in-situ solution preparation method and application thereof. The in-situ solution preparation method provided by the invention avoids the steps of adding raw materials at high temperature or preparing precursor solution at first when preparing the Cs 2SnI6 film by a solution method in the prior art; meanwhile, high vacuum, inert atmosphere or expensive equipment involved in the solid-phase method preparation process is avoided; experiments prove that the prepared Cs 2SnI6 film has good characteristics of high purity, high oriented growth and air stability, and the absorption coefficient in the visible light range reaches 10 4cm‑1 orders of magnitude.
Description
Technical Field
The invention belongs to the field of photoelectric functional film materials, and particularly relates to a tin-containing double perovskite material film, and a preparation method and application thereof.
Background
Perovskite material ABX 3, a is a monovalent cation of Cs, rb, CH 3NH3, or CH 2 nh=ch, etc.; b is Pb or Sn; and X is Cl, br, I or a mixture thereof, and perovskite materials have been successfully used in perovskite solar cells, dye sensitized solar cells, light emitting diodes, photodetectors and the like due to the advantages of high absorption coefficient, high carrier mobility, narrow band gap and the like. However, these materials suffer from long-term instability problems associated with phase changes or environmental hydrolysis. In addition, perovskite containing soluble Pb 2+ is toxic and therefore not environmentally friendly. Therefore, the development of lead-free and stable perovskite materials with similar optoelectronic properties is an internationally hot topic.
In recent years, double perovskite material A 2SnI6 (wherein A is a positive monovalent cation, such as inorganic ions like Li +,Na+,K+,Rb+,Cs+ and organic ions like [ (CH 3)4N]+,[CH3NH3]+,[CH2NH＝CH]+) has attracted increasing research interest and has a wide prospect in various applications.
Taking Cs 2SnI6 as an example, common methods for preparing Cs 2SnI6 are solid phase methods and solution methods. The solid phase process generally involves a vacuum or inert atmosphere, requires expensive equipment, is inconvenient to operate, and is not easy to prepare on a large scale, see publication No. doi.org/10.1080/21663831.2017.1346525, subject name Atwo-stepdryprocessforCs2SnI6 perovskitethinfilm. The reported solution processes, although not complex, usually result in Cs 2SnI6 containing CsI impurities or generally require the addition of starting materials at high temperatures or the prior preparation of precursor solutions, see publication doi.org/10.1016/j.solen.2020.06.101, subject name Solar cell using spray casted Cs2SnI6 perovskite thin films on chemical bath deposited CdS yielding high open circuit voltage.
Disclosure of Invention
Aiming at the problems existing in the prior art, the main purpose of the invention is to provide an in-situ solution preparation method of a tin-containing double perovskite material film, which has simple preparation process and easy operation, wherein the main component or the only component of the tin-containing double perovskite material film is A 2SnI6, wherein A is positive monovalent cations.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The invention provides a method for preparing an in-situ solution of a tin-containing double perovskite material A 2SnI6 film, which comprises the following steps:
Step one: reactant raw materials including AI, namely iodide of positive monovalent cations, snI 2 and I 2 are mixed according to the molar mass ratio of (1.5-2.5): 1:1, mixing and dissolving the raw materials in an organic solvent, wherein the organic solvent is Ethylene Glycol Methyl Ether (EGME) or an ethylene glycol methyl ether derivative, and the total mass of the raw materials AI, snI 2 and I 2 accounts for 150-300 mg/ml of the volume of the organic solvent to obtain primary pulp;
Step two: coating the primary pulp obtained in the step one on a substrate, and performing heat treatment to obtain the tin-containing double perovskite material film;
it should be noted that the whole preparation process may be performed under any atmosphere, including air and inert gas;
wherein the chemical structural formula of the organic solvent is as follows:
Wherein R 1、R2 and R 3 can be the same or different and are independently selected from any one of hydrogen atom, halogen atom, nitro, cyano, acyl, sulfonyl, alkyl, alkoxy, alkylthio, trifluoromethyl, benzene ring, naphthalene, anthracene, pyrene, perylene and fluorene; when R 1＝R2＝R3, the structural formula I is EGME; .
Further, the foregoing method for preparing an in-situ solution of a tin-containing double perovskite material a 2SnI6 film, wherein: in step two, coating methods include, but are not limited to, spin coating, drop coating, knife coating, and spray coating.
Further, the foregoing method for preparing an in-situ solution of a tin-containing double perovskite material a 2SnI6 film, wherein: in step two, the substrate may be any supporting carrier including, but not limited to, FTO and ITO.
Further, the foregoing method for preparing an in-situ solution of a tin-containing double perovskite material a 2SnI6 film, wherein: in the second step, the heat treatment temperature is 50-240 ℃.
In the double perovskite material a 2SnI6, a is positive monovalent cation, including but not limited to Li +,Na+,K+,Rb+,Cs+ inorganic ion and [ (CH 3)4N]+,[CH3NH3]+,[CH2 nh=ch ] organic ion, it should be noted that, when the prepared tin-containing double perovskite material a 2SnI6 film is a Cs 2SnI6 film, in the preparation method, raw materials CsI, snI 2 and I 2 are mixed and dissolved in the organic solvent according to a molar ratio of 2±50%:1, and preferably, the total mass of the raw materials CsI, snI 2 and I 2 accounts for 300mg/ml of the volume of the organic solvent, so as to obtain a primary slurry, and further preferably, the primary slurry is coated on a substrate by spin coating and then drop coating.
The invention provides application of the tin-containing double perovskite material film as a solid electrolyte of a solid dye sensitized solar cell.
The principle of the application: according to the in-situ solution preparation method of the tin-containing double perovskite material A 2SnI6 film, provided by the application, the organic solvents of ethylene glycol methyl ether EGME and derivatives thereof which have similar solubility to reactants AI, snI 2 and I 2 and are easy to volatilize are selected, and moreover, the organic solvents have high solubility to a product A 2SnI6, so that the high-purity A 2SnI6 film can be obtained under the condition of in-situ solution preparation under the condition of proper concentration based on the raw materials and solvents.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
Compared with the solid state method for preparing the A 2SnI6 film in the prior art, see published literature Atwo-step dry process for Cs, snI6 perovskite thin film, DOI number doi.org/10.1080/21663831.2017.1346525, the method prepares the A 2SnI6 film by an in-situ solution method, the preparation can be carried out under the condition of a conventional air environment, high vacuum and inert atmosphere are unnecessary preparation conditions, expensive equipment is not needed, the preparation cost and the operation difficulty are greatly reduced, and the in-situ solution method proves that the A 2SnI6 phase film with high purity can be obtained;
Compared with the solution method in the prior art, see publication Solar cell using spray casted Cs2SnI6perovskite thin films on chemical bath deposited CdS yielding high open circuit voltage,DOI No. doi.org/10.1016/j.solener.2020.06.101, even if the strategy of excessive SnI 2 is adopted, the phase purity of the film is improved to a certain extent, but the operation is still complicated, and precursor solution needs to be prepared firstly; then spraying a precursor solution by using a spraying method, depositing a film under a high-temperature hot plate, directly mixing and dissolving the raw materials in the in-situ solution method in the selected organic solvent, and obtaining the high-purity A 2SnI6 film by adopting a spin coating or drip coating film making mode, so that the operation is simpler and more convenient, the starting material is not required to be added at high temperature or the precursor solution is not required to be prepared firstly, the preparation period is greatly shortened, and the preparation cost is also reduced;
The Cs 2SnI6 film prepared by the in-situ solution preparation method of the tin-containing double perovskite material film is proved to be high-purity and oriented and grown, in addition, the film is uniform and has a flat surface, the absorption coefficient of the film in a visible light range reaches 10 4cm-1 orders, the band gap is about 1.50eV, the proper material performances are favorable for the film to be used as solid electrolyte of a solid dye sensitized solar cell, and the performances are favorable for the short circuit current density J SC, the open circuit voltage V OC and the filling factor FF of the device, so that the conversion efficiency PCE of the device is improved finally, and the film has wide application prospect;
The Cs 2SnI6 film prepared by the in-situ solution preparation method of the tin-containing double perovskite material film has proved to have excellent air stability.
Drawings
FIG. 1 is an XRD pattern of a Cs 2SnI6 film prepared according to example 1 of the present invention based on spin coating followed by drop coating of 50mg/ml of raw slurry;
FIG. 2 is an XRD pattern of a Cs 2SnI6 film prepared according to example 2 of the present invention based on spin coating followed by drop coating of 100mg/ml of raw slurry;
FIG. 3 is an XRD pattern for a Cs 2SnI6 film prepared in accordance with example 3 of the present invention based on 200mg/ml of a magma spin-on followed by drop-on;
FIG. 4a is an XRD pattern of a Cs 2SnI6 film prepared according to example 4 of the present invention based on spin coating followed by drop coating of 300mg/ml of raw stock;
FIG. 4b is an SEM image of a Cs 2SnI6 film of example 4 based on spin-coating followed by drop-coating of 300mg/ml of a precursor according to the present invention;
FIG. 4c is a Raman spectrum of a Cs 2SnI6 film of example 4 of the present invention based on spin coating followed by drop coating of 300mg/ml of a raw stock;
FIG. 4d is a UV-vis spectrum of a Cs 2SnI6 film of example 4 of the present invention based on spin coating followed by drop coating of 300mg/ml of a magma;
FIG. 5a is an XRD pattern of a film of Cs 2SnI6 prepared in example 1 of the present invention after long-term exposure to air;
FIG. 5b is an XRD pattern of a film of Cs 2SnI6 prepared in example 2 of the present invention after long-term exposure to air;
FIG. 5c is an XRD pattern of a film of Cs 2SnI6 prepared in example 3 of the present invention after long-term exposure to air;
FIG. 5d is an XRD pattern of a film of Cs 2SnI6 prepared in example 4 of the present invention after long-term exposure to air;
FIG. 6 is an XRD pattern of a Cs 2SnI6 film prepared according to example 5 of the present invention based on spin-on 300mg/ml magma;
FIG. 7 is an XRD pattern of a film of Cs 2SnI6 prepared according to example 6 of the present invention based on drop-on 300mg/ml of raw stock;
FIG. 8 is an XRD pattern of a Cs 2SnI6 film prepared in accordance with example 7 of the present invention based on drop-on 300mg/ml of virgin pulp and a FTO/N719-dyedTiO 2 substrate;
FIG. 9 is an XRD pattern of a Cs 2SnI6 film prepared in accordance with example 8 of the present invention based on drop-on 300mg/ml of virgin stock and FTO/Pt substrate;
FIG. 10 is an XRD pattern of Rb 2SnI6 film prepared according to example 9 of the present invention based on drop-on 300mg/ml stock;
FIG. 11 is an XRD pattern of [ (CH 3)4N]2SnI6) film according to the present invention prepared by dropping 300mg/ml of raw slurry in example 10;
FIG. 12 is an XRD pattern of a Cs 2SnI6 film prepared according to example 11 of the present invention based on 150mg/ml of a drop-on-board syrup;
FIG. 13 is an XRD pattern of Cs 2SnI6 film prepared in comparative example 1 of the present invention;
FIG. 14 is an XRD pattern of Cs 2SnI6 film prepared in comparative example 2 of the present invention;
Fig. 15 is a device structure diagram of a solid dye-sensitized solar cell according to an embodiment of the device according to the present invention based on the Cs 2SnI6 thin film in example 4.
FIG. 16 is a J-V plot of an embodiment of the device of the present invention.
Detailed Description
The invention is further described in detail below with reference to the drawings and the specific embodiments, so that the technical scheme of the invention is easier to understand and master; however, these examples are not intended to limit the present invention, and other applications, variations and modifications are also included in the present invention, which are within the essential scope of the present invention.
The in-situ solution preparation method of the tin-containing perovskite material A 2SnI6 (A is positive monovalent cation) film comprises the following steps:
example 1
Cs 2SnI6 film prepared by spin coating followed by drop coating of 50mg/ml of the stock.
The preparation process comprises the following steps: according to 2:1: 1a raw material CsI (22.67 mg), snI 2 (16.26 mg) and I 2 (11.07 mg) were mixed in 1ml of an organic solvent EGME to obtain a raw slurry having a concentration of 50 mg/ml; taking a certain amount of obtained raw slurry, spin-coating and then dripping the raw slurry onto an FTO glass substrate, wherein the spin-coating comprises the following steps: sucking the primary pulp by a pipetting gun and injecting the primary pulp on a substrate, wherein the rotating speed of a spin coater is 2000 rpm, and the spin coater works for 20 seconds; the dripping operation is as follows: the original slurry is sucked by a liquid-transferring gun and cast on the substrate after spin coating, then the substrate is transferred to a hot plate, and then the heat treatment is carried out for 10 minutes at 85 ℃ and then for 3 minutes at 110 ℃ to obtain the Cs 2SnI6 film.
FIG. 1 is an XRD pattern of the Cs 2SnI6 film prepared in this example, and it can be seen that the 2-theta diffraction peaks are 13.18 °, 26.53 °, 30.73 °, 37.88 °, 44.01 ° and 54.63 ° respectively attributed to the (111), (222), (400), (422), (440) and (444) planes in the cubic double perovskite Cs 2SnI6 (JCPDSNo.73-0330), and in addition, diffraction peaks attributed to CsI (JCPDSNo.06-0311), i.e., at 27.59 °, 39.42 °, 48.79 ° and 56.97 °, can be observed.
Example 2
Cs 2SnI6 film prepared by spin coating followed by drop coating of 100mg/ml of the stock.
The preparation process differs from example 1 only in that: this embodiment is according to 2:1:1, mixing raw materials CsI (45.34 mg), snI 2 (32.53 mg) and I 2 (22.15 mg) into 1ml of an organic solvent EGME to obtain a raw slurry with the concentration of 100 mg/ml; the subsequent operation was the same as in example 1.
FIG. 2 is an XRD pattern of the Cs 2SnI6 film prepared in this example, and it can be seen that the 2-theta diffraction peaks are 13.18 °, 26.53 °, 30.73 °, 37.88 °, 44.01 ° and 54.63 ° respectively assigned to the (111), (222), (400), (422), (440) and (444) planes in the cubic double perovskite Cs 2SnI6 (JCCPDSNo. 73-0330), and in addition, diffraction peaks assigned to CsI (JCCPDSNo. 06-0311), i.e., located at 27.59 °, 39.42 °, 48.79 ° and 56.97 °, are observed, but the intensities of these diffraction peaks are reduced as compared with those in example 1.
Example 3
A film of Cs 2SnI6 prepared by spin coating followed by drop coating of 200mg/ml of the stock.
The preparation process differs from example 1 only in that: this embodiment is according to 2:1: 1a raw material CsI (90.69 mg), snI 2 (65.05 mg) and I 2 (44.30 mg) were mixed in 1ml of an organic solvent EGME to obtain a raw slurry having a concentration of 200 mg/ml; the subsequent operation was the same as in example 1.
FIG. 3 is an XRD pattern of the Cs 2SnI6 film prepared in this example, and it can be seen that the 2-theta diffraction peaks are 13.18 °, 26.53 °, 30.73 °, 37.88 °, 44.01 ° and 54.63 ° respectively attributed to (111), (222), (400), (422), (440) and (444) in the cubic double perovskite Cs 2SnI6 (JCCPDSNo. 73-0330), and furthermore, one diffraction peak attributed to CsI (JCCPDSNo. 06-0311), i.e., at 27.59 °, was significantly reduced as compared with those in examples 1 and 2.
Example 4
Cs 2SnI6 film prepared by spin coating followed by drop coating of 300mg/ml of the stock.
The preparation process differs from example 1 only in that: this embodiment is according to 2:1: 1a raw material CsI (135.20 mg), snI 2 (96.98 mg) and I 2 (66.04 mg) were mixed in 1ml of an organic solvent EGME to obtain a raw slurry having a concentration of 300 mg/ml; the subsequent operation was the same as in example 1.
The characterization of the structure and optical properties of the Cs 2SnI6 film prepared in this example is as follows; of these, fig. 4a is an XRD pattern of the prepared Cs 2SnI6 film, and it can be seen that the 2-theta diffraction peaks are 13.18 °, 26.53 ° and 54.63 ° respectively attributed to (111), (222) and (444) planes in cubic double perovskite Cs 2SnI6 (jcpdsno. 73-0330), indicating that Cs 2SnI6 in this case is grown along the <111> crystal plane orientation, and furthermore, no diffraction peak attributed to impurity is observed, indicating that Cs 2SnI6 in this case is of high purity; FIG. 4b is a surface SEM image of a Cs 2SnI6 film, which shows that there is a distinct regular octahedral structure throughout the image and coverage/uniformity is good; FIG. 4c is a Raman diagram of a Cs 2SnI6 film, it can be seen that the highest Raman peak at 125.2cm -1 is attributed to Sn-I symmetric stretching of the SnI 6]2- octahedron in Cs 2SnI6, another Raman peak at 245.2cm -1 is a higher order mode of Sn-I asymmetric stretching, and furthermore, no obvious impurity Raman peak is observed, which indicates that the Cs 2SnI6 film at this time has good crystallinity and purity, consistent with XRD results; FIG. 4d is a UV-vis diagram of a Cs 2SnI6 film, which shows two distinct peaks around 294 and 370nm, and further, absorption coefficients in the visible range of about 2.7-4.2X10 4cm-1. The band gap of the film was calculated to be about 1.50eV in combination with the Tauc formula. Overall, this example yields a high purity and oriented grown Cs 2SnI6 film with an absorption coefficient on the order of 10 4cm-1 and a band gap of about 1.50eV.
The air stability of the Cs 2SnI6 films prepared in examples 1 to 4 was examined as follows:
When the Cs 2SnI6 films prepared in examples 1 to 4 were left to stand under ambient conditions (without any sealing means, at a temperature of about 25 ℃ and a relative humidity of about 60%) for 85 days, fig. 5a, 5b, 5c and 5d show XRD patterns after the Cs 2SnI6 films prepared in examples 1 to 4, respectively, it can be seen that the impurity diffraction peaks ascribed to CsI were gradually reduced in the Cs 2SnI6 films prepared in examples 1 to 3; in addition, the diffraction peak attributed to Cs 2SnI6 in the <111> direction was enhanced, indicating that Cs 2SnI6 was gradually aligned in one direction. For the Cs 2SnI6 film prepared in example 4, no remaining XRD diffraction peaks were observed except for the <111> direction of Cs 2SnI6 during this period, indicating good environmental stability.
Example 5
A Cs 2SnI6 film prepared by spin coating 300mg/ml of the stock.
The preparation process comprises the following steps: according to 2:1: 1a raw material CsI (135.20 mg), snI 2 (96.98 mg) and I 2 (66.04 mg) were mixed in 1ml of an organic solvent EGME to obtain a raw slurry having a concentration of 300 mg/ml; spin-coating a certain amount of the obtained raw slurry on an FTO glass substrate, wherein the spin-coating operation is as follows: the stock was sucked by a pipette and injected onto a substrate, the spin rate of a spin coater was 2000 rpm, the spin coater was operated for 20 seconds, and then the substrate was transferred to a hot plate, and then heat-treated at 85℃for 10 minutes and then at 110℃for 3 minutes, to thereby obtain a Cs 2SnI6 film of the present invention.
The XRD patterns of the Cs 2SnI6 films produced in this example are shown in FIG. 6. The 2 theta diffraction peaks of 13.18 °, 26.53 ° and 54.63 ° are assigned to (111), (222) and (444) planes in the cubic double perovskite Cs 2SnI6 (jcpdsno. 73-0330), respectively. Furthermore, only one diffraction peak attributed to CsI (jcpdsno. 06-0311), i.e. at 27.59 °, was observed, but the intensity was very low. That is, this example gives a relatively high purity and oriented-grown Cs 2SnI6 film.
Example 6
A film of Cs 2SnI6 was prepared by drop coating 300mg/ml of the stock.
The preparation process comprises the following steps: according to 2:1: 1a raw material CsI (135.20 mg), snI 2 (96.98 mg) and I 2 (66.04 mg) were mixed in 1ml of an organic solvent EGME to obtain a raw slurry having a concentration of 300 mg/ml; and (3) dripping a certain amount of obtained raw slurry onto the FTO glass substrate, wherein the dripping operation is as follows: the original slurry is sucked by a liquid-transferring gun to be cast on a substrate, the substrate is transferred to a hot plate, and then the substrate is firstly heat-treated for 10 minutes at 85 ℃ and then heat-treated for 3 minutes at 110 ℃ to obtain the Cs 2SnI6 film.
The XRD patterns of the Cs 2SnI6 films produced in this example are shown in FIG. 7. The 2 theta diffraction peaks of 13.18 °, 26.53 ° and 54.63 ° are assigned to (111), (222) and (444) planes in the cubic double perovskite Cs 2SnI6 (jcpdsno. 73-0330), respectively. In addition, the diffraction peak of CsI was observed to be negligible. That is, this example also gives a high purity and oriented-grown Cs 2SnI6 film.
Example 7
A film of Cs 2SnI6 was prepared by drop coating 300mg/ml of the stock onto the FTO/N719-dyedTiO 2.
The preparation process comprises the following steps: according to 2:1:1 a raw material CsI (135.20 mg), snI 2 (96.98 mg) and I 2 (66.04 mg) were mixed in 1ml of an organic solvent EGME to obtain a raw slurry having a concentration of 300 mg/ml; a certain amount of the obtained raw pulp is dripped on the FTO/N719-dyedTiO 2, wherein the dripping operation is as follows: the raw slurry is sucked by a liquid-transferring gun and cast on the FTO/N719-dyedTiO 2 substrate, the substrate is transferred to a hot plate, and then the heat treatment is carried out for 10 minutes at 85 ℃ and then for 3 minutes at 110 ℃ to obtain the FTO/N719-dyedTiO 2/Cs2SnI6 film.
The XRD patterns of the FTO/N719-dyedTiO 2/Cs2SnI6 films produced by this example are shown in FIG. 8. The 2 theta diffraction peaks of 13.18 °, 26.53 ° and 54.63 ° are assigned to (111), (222) and (444) planes in the cubic double perovskite Cs 2SnI6 (jcpdsno. 73-0330), respectively. Furthermore, no impurity diffraction peak was observed. That is, this example also resulted in a high purity and oriented grown film of Cs 2SnI6 on FTO/N719-dyedTiO 2. Preliminary demonstration shows that the high-purity and oriented-growth Cs 2SnI6 film can be coated on the photo-anode of the dye-sensitized solar cell.
Example 8
A film of Cs 2SnI6 was prepared by drop coating 300mg/ml of the stock onto FTO/Pt.
The preparation process comprises the following steps: according to 2:1:1 a raw material CsI (135.20 mg), snI 2 (96.98 mg) and I 2 (66.04 mg) were mixed in 1ml of an organic solvent EGME to obtain a raw slurry having a concentration of 300 mg/ml; a certain amount of obtained raw slurry is dripped on FTO/Pt, wherein the dripping operation is as follows: the raw slurry is sucked by a liquid-transferring gun and is dripped on an FTO/Pt substrate, the substrate is transferred to a hot plate, and then the heat treatment is carried out for 10 minutes at 85 ℃ and then for 3 minutes at 110 ℃ to obtain the FTO/Pt/Cs 2SnI6 film.
The XRD patterns of the FTO/Pt/Cs 2SnI6 films produced in this example are shown in FIG. 9. The 2 theta diffraction peaks of 13.18 °, 26.53 ° and 54.63 ° are assigned to (111), (222) and (444) planes in the cubic double perovskite Cs 2SnI6 (jcpdsno. 73-0330), respectively. Furthermore, no impurity diffraction peak was observed. That is, this example also resulted in a high purity and oriented grown Cs 2SnI6 film on FTO/Pt. Preliminary demonstration shows that the high-purity and oriented-growth Cs 2SnI6 film can be coated on the counter electrode of the dye-sensitized solar cell.
Example 9
Rb 2SnI6 film prepared by drop coating 300mg/ml of raw stock.
The preparation process comprises the following steps: according to 2:1:1, raw materials RbI (110.50 mg), snI 2 (96.98 mg) and I 2 (66.04 mg) are mixed into 1ml of an organic solvent EGME to obtain a raw slurry with a concentration of 300 mg/ml; and (3) dripping a certain amount of obtained raw slurry onto the FTO glass substrate, wherein the dripping operation is as follows: the raw slurry is sucked by a liquid-transferring gun to be cast on a substrate, the substrate is transferred to a hot plate, and then the substrate is firstly subjected to heat treatment for 10 minutes at 85 ℃ and then is subjected to heat treatment for 3 minutes at 110 ℃ to obtain the Rb 2SnI6 film.
The XRD patterns of Rb 2SnI6 films prepared in this example are shown in FIG. 10. The 2 theta diffraction peaks of 13.21 °, 26.60 ° and 54.78 ° are assigned to (111), (222) and (444) planes in cubic double perovskite Rb 2SnI6 (jcpdsno. 73-0330), respectively. In addition, few diffraction peaks ascribed to RbI were observed. Namely, this example gives a high purity and oriented grown Rb 2SnI6 film.
Example 10
A [ (CH 3)4N]2SnI6 film) was prepared by dropping 300mg/ml of the stock.
The preparation process comprises the following steps: according to 2:1:1 (CH 3)4NI(104.52mg)、SnI2 (96.98 mg) and I 2 (66.04 mg) are mixed in 1ml of organic solvent EGME to obtain raw slurry with the concentration of 300mg/ml, a certain amount of the raw slurry is dripped on an FTO glass substrate, wherein the dripping operation is that the raw slurry is sucked by a pipetting gun and dripped on the substrate, the substrate is transferred to a hot plate, and then the substrate is firstly heat-treated for 10 minutes at 85 ℃ and then heat-treated for 3 minutes at 110 ℃ to obtain the [ (CH 3)4N]2SnI6) film.
As shown in FIG. 11, three distinct diffraction peaks corresponding to the (111), (222) and (511) planes in the cubic double perovskite Cs 2SnI6 (JCPSS No. 73-0330) were observed at 13.35 DEG, 26.41 DEG and 40.06 DEG in XRD patterns of [ (CH 3)4N]2SnI6) films obtained in this example, and it was considered that the high purity [ (CH 3)4N]2SnI6) film was obtained in this example because of the difference in radii of Cs + and [ (CH 3)4N]+ ].
Example 11
A film of Cs 2SnI6 prepared by drop coating 150mg/ml of the stock.
The preparation process comprises the following steps: according to 2:1: 1a raw material CsI (67.60 mg), snI 2 (48.49 mg) and I 2 (33.02 mg) were mixed in 1ml of an organic solvent EGME to obtain a raw slurry having a concentration of 150 mg/ml; and (3) dripping a certain amount of obtained raw slurry onto the FTO glass substrate, wherein the dripping operation is as follows: the original slurry is sucked by a liquid-transferring gun to be cast on a substrate, the substrate is transferred to a hot plate, and then the substrate is firstly heat-treated for 10 minutes at 85 ℃ and then heat-treated for 3 minutes at 110 ℃ to obtain the Cs 2SnI6 film.
The XRD patterns of the Cs 2SnI6 films produced in this example are shown in FIG. 12. The 2 theta diffraction peaks of 13.18 °, 26.53 °, 30.70 °, 44.01 °, and 54.63 ° are assigned to (111), (222), (400), (440), and (444) planes in the cubic double perovskite Cs 2SnI6 (jcpdsno. 73-0330), respectively. In addition, only diffraction peaks of CsI of relatively low intensity were observed, and it is considered that this example gave a relatively high purity Cs 2SnI6 film.
Example 12
A Cs 2SnI6 film prepared by drop coating 350mg/ml of the stock.
The preparation process comprises the following steps: according to 2:1: 1a raw material CsI (158.60 mg), snI 2 (113.77 mg) and I 2 (77.47 mg) were mixed in 1ml of an organic solvent EGME to obtain a raw slurry having a concentration of 350 mg/ml; however, at this time, a small amount of black precipitate was observed at the bottom of the magma, and it was preliminarily judged that at this time, the magma concentration was too high and a part of Cs 2SnI6 was not dissolved but precipitated.
Comparative example 1
According to 2:1:1 feed ratio raw materials CsI (67.60 mg), snI 2 (48.49 mg) and I 2 (33.02 mg) were mixed in 1ml of a common organic solvent DMF to obtain a raw slurry with a concentration of 150 mg/ml; the Cs 2SnI6 film of the present invention was obtained by dropping the raw slurry, and the specific experimental procedure was the same as in example 6.
As shown in fig. 13, which shows the XRD pattern of the Cs 2SnI6 film obtained in this comparative example, it can be seen that a large number of 2θ diffraction peaks ascribed to CsI impurity are generated at this time, compared with that of Cs 2SnI6, which has few diffraction peaks and low intensity.
Comparative example 2
According to 2:1, mixing the raw materials CsI (135.20 mg) and SnI 4 (163.02 mg) into 1ml of an organic solvent EGME to obtain a raw slurry with the concentration of 300 mg/ml; the Cs 2SnI6 film of the present invention was obtained by dropping the raw slurry, and the specific experimental procedure was the same as in example 6.
As shown in fig. 14, which shows the XRD patterns of the Cs 2SnI6 thin films obtained in the comparative example, it can be seen that the 2-theta diffraction peaks are 13.18 °, 26.53 °, 30.70 °, 44.01 ° and 54.63 ° respectively, which are assigned to the (111), (222), (400), (440) and (444) planes in the cubic double perovskite Cs 2SnI6 (jcpdsno. 73-0330), and it is noted that the intensities of the diffraction peaks of (400) and (440) are very low and almost negligible. It can be said that Cs 2SnI6 in this case is grown along the <111> crystal plane orientation. Furthermore, no diffraction peaks ascribed to impurities were observed, indicating that Cs 2SnI6 in this case was of high purity and grown in an oriented manner.
Device embodiments and testing
The specific device structure shown in fig. 15 is specifically prepared by using the Cs 2SnI6 film in example 4 to prepare a solid dye-sensitized solar cell, and the specific preparation process is as follows:
firstly, soaking plasma-treated FTO glass in a deionized water solution of 0.05M titanium tetrachloride at 70 ℃ for 50 minutes, and then rinsing with deionized water and ethanol in sequence; heating the soaked substrate at 180 ℃ for 20 minutes to form a compact TiO 2 barrier layer; after cooling, an ethanol solution of TiO 2 nanoparticles (p 25) was electrosprayed (E-spray) onto the substrate to deposit a mesoporous TiO 2 film, about 7-8 microns thick; sintering the mesoporous TiO 2 film in the atmosphere at 480 ℃ for 30 minutes; the photoanode was then prepared by immersing the substrate with sintered TiO 2 in an N719 dye solution (3 x 10 4 M) at room temperature for 12 hours. A film of Cs 2SnI6 was then deposited on the TiO 2 photo-anode using the procedure described above. Counter electrodes were obtained by spin-coating chloroplatinic acid (99.9%, heptaChroma) onto FTO substrates and sintering at 420 ℃ for 20 minutes, followed by fabrication of Cs 2SnI6 films thereon. Finally, during the annealing process: for photoanode, at 85 ℃ for 10 minutes, then at 110 ℃ for 3 minutes; the counter electrode was held at 95 ℃ for 10 minutes, then at 110 ℃ for 3 minutes, the two electrodes were bonded together, and then additional Cs 2SnI6 solution was injected into the gap between the two electrodes by vacuum backfilling of pre-drilled holes in the counter electrode.
Placing the manufactured device on a hot plate with the temperature of 120 ℃ for 3-5 minutes to remove EGME solvent; after the device is cooled to room temperature, sealing the preformed hole by epoxy resin; the effective area of the device was 0.25cm 2.
As shown in the J-V graph of fig. 16, the prepared solid-state dye-sensitized solar cell was tested for photovoltaic performance, i.e., am1.5g, with an intensity of 100mWcm under a solar simulator XD-300. Photocurrent-voltage J-V curves were measured using Keithley 2400. The test results show that the short-circuit current density J SC of the device is 13.21mA/cm 2, the open-circuit voltage V OC is 0.70V, and the photoelectric conversion efficiency PCE is 7.05%, which almost represents the highest performance in the same type of solid dye-sensitized solar cell.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof; the present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (9)
1. A preparation method of an in-situ solution of a tin-containing double perovskite material film is characterized by comprising the following steps of: the method comprises the following steps:
Step one: the reactants are prepared into iodide AI, snI 2 and I 2 of positive monovalent cations according to the molar mass ratio of (1.5-2.5): 1:1, mixing and dissolving the raw materials in an organic solvent, wherein the organic solvent is ethylene glycol methyl ether EGME or an ethylene glycol methyl ether derivative, and the total mass of the raw materials AI, snI 2 and I 2 accounts for 150-300 mg/ml of the volume of the organic solvent to obtain primary pulp;
Step two: coating the primary pulp obtained in the step one on a substrate, and performing heat treatment to obtain the tin-containing double perovskite material film;
The organic solvent is Ethylene Glycol Methyl Ether (EGME) or an ethylene glycol methyl ether derivative, namely the organic solvent is shown in the following structural formula:
Wherein R 1、R2 and R 3 can be the same or different and are independently selected from any one of hydrogen atom, halogen atom, nitro, cyano, acyl, sulfonyl, alkyl, alkoxy, alkylthio, trifluoromethyl, benzene ring, naphthalene, anthracene, pyrene, perylene and fluorene;
The positive monovalent cation A is selected from any one of Li+,Na+,K+,Rb+,Cs+、[(CH3)4N]+,[CH3NH3]+,[CH2NH=CH]+.
2. The method for preparing the in-situ solution of the tin-containing double perovskite material film according to claim 1, wherein the method comprises the following steps of: the coating mode is any one of spin coating, drop coating, knife coating or spray coating.
3. The method for preparing an in-situ solution of a tin-containing double perovskite material film according to claim 1, wherein iodide AI of positive monovalent cations is CsI, namely CsI, snI 2 and I 2 are used as raw materials.
4. A method for preparing an in situ solution of a tin-containing double perovskite material film according to claim 3, wherein the ratio of the total mass of the raw materials CsI, snI 2 and I 2 to the volume of the organic solvent is 300mg/ml.
5. A method for preparing an in situ solution of a tin-containing double perovskite material film according to claim 3, wherein the primary slurry is coated on a substrate by spin coating followed by drip coating.
6. The method for preparing the in-situ solution of the tin-containing double perovskite material film according to claim 1, wherein the method comprises the following steps of: the substrate is FTO or ITO.
7. The method for preparing the in-situ solution of the tin-containing double perovskite material film according to claim 1, wherein the method comprises the following steps of: the temperature of the heat treatment is 50-240 ℃.
8. A thin film of a double perovskite material prepared by the in situ solution preparation method of a thin film of a double perovskite material containing tin as claimed in any one of claims 1 to 7.
9. The use of the thin film of double perovskite material according to claim 8 as a solid electrolyte for a solid dye sensitized solar cell.
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