CN108091766B - N-type doped electron transport layer and TiO2Method for producing layered perovskite cells - Google Patents
N-type doped electron transport layer and TiO2Method for producing layered perovskite cells Download PDFInfo
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Abstract
The invention provides an n-type doped electron transport layer and TiO2A method of making a layered perovskite battery, comprising the steps of: (1) FTO transparent conductive glass substrate cleaning and TiO2Preparation of thin film, deposition of TiO2Putting the mixture into a drying oven for later use; (2) preparing a Bis-PCBM and DMC composite membrane; (3) spin-on coating with deposited TiO2On the FTO; (4) preparing a perovskite thin film; (5) preparing a Spiro-OMeTAD film, and spin-coating on the FTO in the step (4); (6) evaporating MoO on a Spiro-OMeTAD film by adopting an evaporation method3And an Ag electrode. The method can improve the electron mobility and the electric conductivity of the thin film, promote the improvement of the photoelectric conversion efficiency of the device, make the surface of the thin film smoother, can be used as a good substrate for the deposition and growth of a subsequent perovskite layer, can slow down the degradation process of the perovskite layer, and improves the stability of the device.
Description
Technical Field
The invention belongs to the field of photovoltaic devices, and particularly relates to an n-type doped electron transport layer and TiO2A method of making a layered perovskite battery.
Background
Organic-inorganic hybrid perovskite solar cells are considered to be an energy form comparable to inorganic silicon solar cells due to their unique optical characteristics and simple fabrication process. Through the development of several years, although the photoelectric conversion efficiency thereof has exceeded 22%, it is a necessary condition to manufacture a perovskite solar cell having high efficiency and long-term stability to realize commercialization thereof. The perovskite solar cell has two device structures of a planar type and a porous type, and the planar type perovskite cell is widely concerned by a simple preparation process and a low-temperature thin film processing technology. In planar structures, the structure of adjacent interface layers, in addition to the perovskite layer itself, strongly influences the stability of the device. Ideal world ofThe face material should have desirable physical, chemical and electronic properties, including appropriate energy levels, high conductivity, high solvent resistance, and low light absorption. In addition, the interfacial film needs to have good wettability as a primer layer for perovskite thin film deposition and growth. Recently, various interface materials have been used in the planar structure PSC to prevent moisture, oxygen, and ultraviolet light from entering the perovskite layer, with the aim of improving the stability of the battery. The most advanced perovskite solar cells reported at present use titanium dioxide (TiO)2) As a structure of an Electron Transport Layer (ETL). Although titanium dioxide has good electron selectivity, surface adsorption of oxygen and ultraviolet light may limit further improvements in the efficiency and stability of perovskite solar cells. A series of intensive studies have been conducted on materials, thin film fabrication techniques, device structures, and physical mechanisms. Wherein by adjusting TiO2And perovskite layers are effective strategies to further improve the efficiency and stability of perovskites. Fullerene materials can effectively slow down decomposition of perovskite as a modification layer, but the potential application of fullerene materials in batteries can still be limited due to the inherent problem of low electron mobility and conductivity of fullerene materials.
One strategy to improve electron mobility and conductivity of fullerenes is to increase the free electron concentration by efficient electron transfer from n-type dopants to the host material using n-type doping techniques. But few studies have been reported on n-doped electron selective materials due to the lack of efficient and stable n-type dopants. Furthermore, chemical doping of solution processed films is more challenging than vacuum evaporation, as the problem of solvent attack needs to be considered in the multilayer film deposition process. Organic based n-type dopants are considered as an alternative to solution processed film doping compared to inorganic n-type dopants based on alkali or alkali metal salts, since they have good solubility in common organic solvents and do not undergo atomic diffusion. (pentamethylcyclopentadienyl) cobalt (DMC) has an ionization energy of 3.3eV or less, which makes it a powerful reducing agent and a more n-doped host material. The invention utilizes the strong reducing power of DMC and is based on solution treatment dopingThe process successfully realizes the high-efficiency n-type doping of a Bis adduct (Bis-PCBM) of phenyl-C70-methyl butyrate. And provides an n-type doped electron transport layer TiO2In the preparation method of the perovskite battery with the double-layer structure electron transmission layer formed by the layers, DMC doping provides a series of functions of adjusting energy levels, the electron mobility of the Bis-PCBM film is improved, the conductivity of the film is improved, and therefore effective electron extraction is provided on the cathode side. Bis-PCBM: the DMC composite membrane also presents a stable three-dimensional framework, has good solvent resistance, and can delay the degradation process of a perovskite layer. In addition, DMC doped Bis-PCBM films exhibit a smooth morphology, which facilitates subsequent deposition and growth of perovskite films. The new ETL that has been developed demonstrates potential commercial applications for fabricating highly efficient and stable planar perovskite solar cells. Furthermore, this discovery also provides a new approach to n-type doping of fullerenes using DMC-like metallocenes.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the defect of poor stability of the existing perovskite, an n-type doped electron transport layer and TiO2The preparation method of the perovskite solar cell of the layer utilizes the strong reducing capability of DMC, and is based on the solution treatment doping process, so that the high-efficiency n-type doping of Bis-PCBM is successfully realized, the electron mobility of the Bis-PCBM film is improved, the conductivity of the film is improved, effective electron extraction is provided at the cathode side, the internal defects of the device are reduced, the decomposition of perovskite is inhibited, and the high-efficiency and stable perovskite solar cell is prepared.
The technical scheme is as follows: n-type doped electron transport layer and TiO2A method of making a layered perovskite battery, comprising the steps of:
(1) FTO transparent conductive glass substrate cleaning and TiO2Preparing a film: repeatedly ultrasonically cleaning the FTO transparent conductive glass substrate with deionized water, acetone and ethanol for 3 times, drying at 100 ℃ until the solvent and water are completely removed, treating the treated FTO transparent conductive glass substrate with an ultraviolet lamp and ozone for 25 min, and depositing an electron transport layer TiO on the treated FTO transparent conductive glass substrate2Putting the mixture into a 100 ℃ oven for standby;
(2) preparing a Bis-PCBM and DMC composite membrane: dissolving 5mg of Bis-PCBM in 2-8mL of chlorobenzene, stirring for 4h to obtain a Bis-PCBM solution, dissolving a doping agent DMC in ethanol to prepare a precursor solution with the concentration of 0.2-0.8mg/mL, and doping the precursor solution in the Bis-PCBM solution;
(3) spin-coating on the deposited electron transport layer TiO2The spin coating speed of the FTO transparent conductive glass substrate is 4000r/min, the spin coating time is 40s, annealing treatment is carried out after the spin coating, the annealing temperature is 100 ℃, and the annealing time is 10 min;
(4) preparing a perovskite thin film: dissolving 180mg of methylammonium iodide and 553mg of lead iodide in 1mL of mixed solution of dimethyl sulfoxide and gamma-butyrolactone, wherein the volume ratio of the dimethyl sulfoxide to the gamma-butyrolactone is 3:7, stirring for 5h to obtain a perovskite solution, spin-coating the perovskite solution on the FTO transparent conductive glass substrate in the step (3), wherein the spin-coating speed is 2000r/min at a low speed, 20s at a high speed, 4000r/min at a high speed and 40s at a high speed, dripping chlorobenzene as an anti-solvent at the 20 th s at the high speed stage, and annealing after spin-coating, wherein the annealing temperature is 100 ℃ and the annealing time is 10 min;
(5) 2,2',7' -tetrakis- (N, N-di-p-methoxyphenylamine) -9,9' -spirobifluorene (Spiro-OMeTAD) thin film preparation: dissolving 90mg of Spiro-OMeTAD in 1mL of chlorobenzene, stirring for 3h to obtain a Spiro-OMeTAD solution, and spin-coating on the FTO transparent conductive glass substrate in the step (4) at the spin-coating speed of 4000r/min for 40s to obtain a uniform hole transport layer;
（6） MoO3and Ag electrode preparation: evaporating MoO on a Spiro-OMeTAD film by adopting an evaporation method3And an Ag electrode.
Further preferably, TiO in the step (1)2The deposition method of (1) was to add 4.5mL of titanium tetrachloride solution to 200mL of ultrapure water and perform a deposition reaction at 70 ℃ for 1 hour.
Further preferably, the volume ratio of the precursor solution to the Bis-PCBM solution in the step (2) is 0.05-1.0%.
Further preferably, MoO in step (6)3The thickness is 10 nm, and the thickness of the Ag electrode is 100 nm.
The perovskite battery prepared by the method is provided by the invention.
The perovskite battery has the following device structure: FTO/TiO2(Bis-PCBM) DMC/perovskite thin film/Spiro-OMeTAD/MoO3/Ag。
Has the advantages that: the invention relates to an n-type doped electron transport layer and TiO2The preparation method of the perovskite battery with the layers has the following advantages: (1) n-type doping of fullerene is realized by a novel solution treatment method; (2) the DMC doping can adjust the energy level of the Bis-PCBM film, improve the electron mobility and the conductivity of the film, further improve the short-circuit current of the device and promote the photoelectric conversion efficiency of the device; (3) after the DMC is used for doping Bis-PCBM, the surface of the film is smoother and can be used as a good substrate for the deposition and growth of a subsequent perovskite layer, so that the perovskite film is more uniform and compact in crystallization; (4) the Bis-PCBM/DMC composite membrane also presents a stable three-dimensional framework, has good solvent resistance, can slow down the degradation process of a perovskite layer, and improves the stability of a device; (5) mixing Bis-PCBM: processing of DMC composite membranes on TiO2After coating, the TiO can be passivated2On the surface, the internal defects of the perovskite solar cell are reduced, and the hysteresis phenomenon of the device is effectively improved; (6) the method is novel, the manufacturing process is simple and convenient, the manufacturing difficulty is low, and the device performance is stable.
Drawings
Fig. 1 is a schematic structural view of a perovskite cell of the present invention.
In FIG. 2, (a) is TiO2Atomic force microscope images of the film; (b) for spin coating on TiO2Atomic force microscope images of Bis-PCBM films on the film; (c) for spin coating on TiO2Atomic force microscope image of Bis-PCBM on film DMC (degree of doping 0.1 wt%); (d) is TiO2Scanning electron microscope images of the perovskite of the film; (e) for spin coating on TiO2Scanning electron microscope images of the perovskite of Bis-PCBM films on the film; (f) for spin coating on TiO2Scanning electron microscopy images of perovskite on Bis-PCBM DMC (degree of doping 0.1 wt%) composite membranes on membranes.
FIG. 3 is TiO2Perovskite film on film, spinCoated on TiO2Perovskite film on Bis-PCBM film on film and spin coating on TiO2X-ray diffraction pattern of perovskite film on Bis-PCBM DMC (degree of doping 0.1 wt%) composite film on the film.
Fig. 4 is a graph of normalized power conversion efficiency as a function of time in the perovskite solar cells of comparative example 2 and example 2 without encapsulation under the same storage conditions.
FIG. 5 shows conductivity values of Bis-PCBM films at different DMC doping concentrations.
Fig. 6 is a J-V positive and negative direction voltage scan of the perovskite cell devices of comparative example 2 and example 2.
Fig. 7 is a graph of the photoelectric characteristics of the perovskite cell devices of comparative example 2 and example 2.
FIG. 8 is an absorption spectrum of Bis-PCBM and Bis-PCBM to DMC (degree of doping of 0.1 wt%) membranes before and after rinsing with a mixed solvent of γ -butyrolactone and dimethyl sulfoxide.
Detailed Description
Example 1
N-type doped electron transport layer and TiO2A method of making a layered perovskite battery, comprising the steps of:
(1) FTO transparent conductive glass substrate cleaning and TiO2Preparing a film: repeatedly ultrasonically cleaning the FTO transparent conductive glass substrate with deionized water, acetone and ethanol for 3 times, drying at 100 ℃ until the solvent and water are completely removed, treating the treated FTO transparent conductive glass substrate with an ultraviolet lamp and ozone for 25 min, and depositing an electron transport layer TiO on the treated FTO transparent conductive glass substrate2Putting the mixture into a 100 ℃ oven for standby;
(2) preparing a Bis-PCBM and DMC composite membrane: dissolving 5mg of Bis-PCBM in 2mL of chlorobenzene, stirring for 4h to obtain a Bis-PCBM solution, dissolving a doping agent DMC in ethanol to prepare a precursor solution with the concentration of 0.2mg/mL, and doping the precursor solution in the Bis-PCBM solution, wherein the volume ratio of the two is 0.05%;
(3) spin-coating on the deposited electron transport layer TiO2The spin coating speed and the spin coating time of the FTO transparent conductive glass substrate are 4000r/minThe time is 40s, annealing treatment is carried out after spin coating, the annealing temperature is 100 ℃, and the time is 10 min;
(4) preparing a perovskite thin film: dissolving 180mg of methylammonium iodide and 553mg of lead iodide in 1mL of mixed solution of dimethyl sulfoxide and gamma-butyrolactone, wherein the volume ratio of the dimethyl sulfoxide to the gamma-butyrolactone is 3:7, stirring for 5h to obtain a perovskite solution, spin-coating the perovskite solution on the FTO transparent conductive glass substrate in the step (3), wherein the spin-coating speed is 2000r/min at a low speed, 20s at a high speed, 4000r/min at a high speed and 40s at a high speed, dripping chlorobenzene as an anti-solvent at the 20 th s at the high speed stage, and annealing after spin-coating, wherein the annealing temperature is 100 ℃ and the annealing time is 10 min;
(5) preparation of a Spiro-OMeTAD film: dissolving 90mg of Spiro-OMeTAD in 1mL of chlorobenzene, stirring for 3h to obtain a Spiro-OMeTAD solution, and spin-coating on the FTO transparent conductive glass substrate in the step (4) at the spin-coating speed of 4000r/min for 40s to obtain a uniform hole transport layer;
（6） MoO3and Ag electrode preparation: evaporating MoO on a Spiro-OMeTAD film by adopting an evaporation method3And Ag electrodes, in which MoO3The thickness is 10 nm, and the thickness of the Ag electrode is 100 nm.
The perovskite cell has the following device structure: FTO/TiO2Bis-PCBM: DMC/perovskite thin film/Spiro-OMeTAD/MoO3/Ag。
Example 2
N-type doped electron transport layer and TiO2A method of making a layered perovskite battery, comprising the steps of:
(1) FTO transparent conductive glass substrate cleaning and TiO2Preparing a film: repeatedly ultrasonically cleaning the FTO transparent conductive glass substrate with deionized water, acetone and ethanol for 3 times, drying at 100 ℃ until the solvent and water are completely removed, treating the treated FTO transparent conductive glass substrate with an ultraviolet lamp and ozone for 25 min, and depositing an electron transport layer TiO on the treated FTO transparent conductive glass substrate2Putting the mixture into a 100 ℃ oven for standby;
(2) preparing a Bis-PCBM and DMC composite membrane: dissolving 5mg of Bis-PCBM in 2mL of chlorobenzene, stirring for 4h to obtain a Bis-PCBM solution, dissolving a doping agent DMC in ethanol to prepare a precursor solution with the concentration of 0.2mg/mL, and doping the precursor solution in the Bis-PCBM solution, wherein the volume ratio of the two is 0.1%;
(3) spin-coating on the deposited electron transport layer TiO2The spin coating speed of the FTO transparent conductive glass substrate is 4000r/min, the spin coating time is 40s, annealing treatment is carried out after the spin coating, the annealing temperature is 100 ℃, and the annealing time is 10 min;
(4) preparing a perovskite thin film: dissolving 180mg of methylammonium iodide and 553mg of lead iodide in 1mL of mixed solution of dimethyl sulfoxide and gamma-butyrolactone, wherein the volume ratio of the dimethyl sulfoxide to the gamma-butyrolactone is 3:7, stirring for 5h to obtain a perovskite solution, spin-coating the perovskite solution on the FTO transparent conductive glass substrate in the step (3), wherein the spin-coating speed is 2000r/min at a low speed, 20s at a high speed, 4000r/min at a high speed and 40s at a high speed, dripping chlorobenzene as an anti-solvent at the 20 th s at the high speed stage, and annealing after spin-coating, wherein the annealing temperature is 100 ℃ and the annealing time is 10 min;
(5) preparation of a Spiro-OMeTAD film: dissolving 90mg of Spiro-OMeTAD in 1mL of chlorobenzene, stirring for 3h to obtain a Spiro-OMeTAD solution, and spin-coating on the FTO transparent conductive glass substrate in the step (4) at the spin-coating speed of 4000r/min for 40s to obtain a uniform hole transport layer;
（6） MoO3and Ag electrode preparation: evaporating MoO on a Spiro-OMeTAD film by adopting an evaporation method3And Ag electrodes, in which MoO3The thickness is 10 nm, and the thickness of the Ag electrode is 100 nm.
The perovskite cell has the following device structure: FTO/TiO2Bis-PCBM: DMC/perovskite thin film/Spiro-OMeTAD/MoO3/Ag。
Example 3
N-type doped electron transport layer and TiO2A method of making a layered perovskite battery, comprising the steps of:
(1) FTO transparent conductive glass substrate cleaning and TiO2Preparing a film: repeatedly ultrasonically cleaning an FTO transparent conductive glass substrate for 3 times by using deionized water, acetone and ethanol, then drying at 100 ℃ until the solvent and the moisture are completely removed, and carrying out transparent treatment on the treated FTOTreating the conductive glass substrate with ultraviolet lamp and ozone for 25 min, and depositing electron transport layer TiO on the treated FTO transparent conductive glass substrate2Putting the mixture into a 100 ℃ oven for standby;
(2) preparing a Bis-PCBM and DMC composite membrane: dissolving 5mg of Bis-PCBM in 2mL of chlorobenzene, stirring for 4h to obtain a Bis-PCBM solution, dissolving a doping agent DMC in ethanol to prepare a precursor solution with the concentration of 0.2mg/mL, and doping the precursor solution in the Bis-PCBM solution, wherein the volume ratio of the two is 0.3%;
(3) spin-coating on the deposited electron transport layer TiO2The spin coating speed of the FTO transparent conductive glass substrate is 4000r/min, the spin coating time is 40s, annealing treatment is carried out after the spin coating, the annealing temperature is 100 ℃, and the annealing time is 10 min;
(4) preparing a perovskite thin film: dissolving 180mg of methylammonium iodide and 553mg of lead iodide in 1mL of mixed solution of dimethyl sulfoxide and gamma-butyrolactone, wherein the volume ratio of the dimethyl sulfoxide to the gamma-butyrolactone is 3:7, stirring for 5h to obtain a perovskite solution, spin-coating the perovskite solution on the FTO transparent conductive glass substrate in the step (3), wherein the spin-coating speed is 2000r/min at a low speed, 20s at a high speed, 4000r/min at a high speed and 40s at a high speed, dripping chlorobenzene as an anti-solvent at the 20 th s at the high speed stage, and annealing after spin-coating, wherein the annealing temperature is 100 ℃ and the annealing time is 10 min;
(5) preparation of a Spiro-OMeTAD film: dissolving 90mg of Spiro-OMeTAD in 1mL of chlorobenzene, stirring for 3h to obtain a Spiro-OMeTAD solution, and spin-coating on the FTO transparent conductive glass substrate in the step (4) at the spin-coating speed of 4000r/min for 40s to obtain a uniform hole transport layer;
（6） MoO3and Ag electrode preparation: evaporating MoO on a Spiro-OMeTAD film by adopting an evaporation method3And Ag electrodes, in which MoO3The thickness is 10 nm, and the thickness of the Ag electrode is 100 nm.
The perovskite cell has the following device structure: FTO/TiO2Bis-PCBM: DMC/perovskite thin film/Spiro-OMeTAD/MoO3and/Ag. Example 4
N-type doped electron transport layer and TiO2Method for producing a layered perovskite cell, comprising the following stepsThe method comprises the following steps:
(1) FTO transparent conductive glass substrate cleaning and TiO2Preparing a film: repeatedly ultrasonically cleaning the FTO transparent conductive glass substrate with deionized water, acetone and ethanol for 3 times, drying at 100 ℃ until the solvent and water are completely removed, treating the treated FTO transparent conductive glass substrate with an ultraviolet lamp and ozone for 25 min, and depositing an electron transport layer TiO on the treated FTO transparent conductive glass substrate2Putting the mixture into a 100 ℃ oven for standby;
(2) preparing a Bis-PCBM and DMC composite membrane: dissolving 5mg of Bis-PCBM in 2mL of chlorobenzene, stirring for 4h to obtain a Bis-PCBM solution, dissolving a doping agent DMC in ethanol to prepare a precursor solution with the concentration of 0.2mg/mL, and doping the precursor solution in the Bis-PCBM solution, wherein the volume ratio of the two is 0.5%;
(3) spin-coating on the deposited electron transport layer TiO2The spin coating speed of the FTO transparent conductive glass substrate is 4000r/min, the spin coating time is 40s, annealing treatment is carried out after the spin coating, the annealing temperature is 100 ℃, and the annealing time is 10 min;
(4) preparing a perovskite thin film: dissolving 180mg of methylammonium iodide and 553mg of lead iodide in 1mL of mixed solution of dimethyl sulfoxide and gamma-butyrolactone, wherein the volume ratio of the dimethyl sulfoxide to the gamma-butyrolactone is 3:7, stirring for 5h to obtain a perovskite solution, spin-coating the perovskite solution on the FTO transparent conductive glass substrate in the step (3), wherein the spin-coating speed is 2000r/min at a low speed, 20s at a high speed, 4000r/min at a high speed and 40s at a high speed, dripping chlorobenzene as an anti-solvent at the 20 th s at the high speed stage, and annealing after spin-coating, wherein the annealing temperature is 100 ℃ and the annealing time is 10 min;
(5) preparation of a Spiro-OMeTAD film: dissolving 90mg of Spiro-OMeTAD in 1mL of chlorobenzene, stirring for 3h to obtain a Spiro-OMeTAD solution, and spin-coating on the FTO transparent conductive glass substrate in the step (4) at the spin-coating speed of 4000r/min for 40s to obtain a uniform hole transport layer;
（6） MoO3and Ag electrode preparation: evaporating MoO on a Spiro-OMeTAD film by adopting an evaporation method3And Ag electrodes, in which MoO3The thickness is 10 nm, and the thickness of the Ag electrode is 100 nm.
The perovskite cell has the following device structure: FTO/TiO2Bis-PCBM: DMC/perovskite thin film/Spiro-OMeTAD/MoO3and/Ag. Example 5
N-type doped electron transport layer and TiO2A method of making a layered perovskite battery, comprising the steps of:
(1) FTO transparent conductive glass substrate cleaning and TiO2Preparing a film: repeatedly ultrasonically cleaning the FTO transparent conductive glass substrate with deionized water, acetone and ethanol for 3 times, drying at 100 ℃ until the solvent and water are completely removed, treating the treated FTO transparent conductive glass substrate with an ultraviolet lamp and ozone for 25 min, and depositing an electron transport layer TiO on the treated FTO transparent conductive glass substrate2Putting the mixture into a 100 ℃ oven for standby;
(2) preparing a Bis-PCBM and DMC composite membrane: dissolving 5mg of Bis-PCBM in 8mL of chlorobenzene, stirring for 4h to obtain a Bis-PCBM solution, dissolving a doping agent DMC in ethanol to prepare a precursor solution with the concentration of 0.8mg/mL, and doping the precursor solution in the Bis-PCBM solution, wherein the volume ratio of the two is 1.0%;
(3) spin-coating on the deposited electron transport layer TiO2The spin coating speed of the FTO transparent conductive glass substrate is 4000r/min, the spin coating time is 40s, annealing treatment is carried out after the spin coating, the annealing temperature is 100 ℃, and the annealing time is 10 min;
(4) preparing a perovskite thin film: dissolving 180mg of methylammonium iodide and 553mg of lead iodide in 1mL of mixed solution of dimethyl sulfoxide and gamma-butyrolactone, wherein the volume ratio of the dimethyl sulfoxide to the gamma-butyrolactone is 3:7, stirring for 5h to obtain a perovskite solution, spin-coating the perovskite solution on the FTO transparent conductive glass substrate in the step (3), wherein the spin-coating speed is 2000r/min at a low speed, 20s at a high speed, 4000r/min at a high speed and 40s at a high speed, dripping chlorobenzene as an anti-solvent at the 20 th s at the high speed stage, and annealing after spin-coating, wherein the annealing temperature is 100 ℃ and the annealing time is 10 min;
(5) preparation of a Spiro-OMeTAD film: dissolving 90mg of Spiro-OMeTAD in 1mL of chlorobenzene, stirring for 3h to obtain a Spiro-OMeTAD solution, and spin-coating on the FTO transparent conductive glass substrate in the step (4) at the spin-coating speed of 4000r/min for 40s to obtain a uniform hole transport layer;
（6） MoO3and Ag electrode preparation: evaporating MoO on a Spiro-OMeTAD film by adopting an evaporation method3And Ag electrodes, in which MoO3The thickness is 10 nm, and the thickness of the Ag electrode is 100 nm.
The perovskite cell has the following device structure: FTO/TiO2Bis-PCBM: DMC/perovskite thin film/Spiro-OMeTAD/MoO3/Ag。
Comparative example 1
A preparation method of a perovskite solar cell comprises the following steps:
(1) FTO transparent conductive glass substrate cleaning and TiO2Preparing a film: repeatedly ultrasonically cleaning the FTO transparent conductive glass substrate with deionized water, acetone and ethanol for 3 times, drying at 100 ℃ until the solvent and water are completely removed, treating the treated FTO transparent conductive glass substrate with an ultraviolet lamp and ozone for 25 min, and depositing an electron transport layer TiO on the treated FTO transparent conductive glass substrate2Putting the mixture into a 100 ℃ oven for standby;
(2) preparing a perovskite thin film: dissolving 180mg of methylammonium iodide and 553mg of lead iodide in 1mL of mixed solution of dimethyl sulfoxide and gamma-butyrolactone, wherein the volume ratio of the dimethyl sulfoxide to the gamma-butyrolactone is 3:7, stirring for 5h to obtain a perovskite solution, and spin-coating the perovskite solution on the TiO deposited on the electron transport layer2On the FTO transparent conductive glass substrate, the spin coating speed is 2000r/min at a low speed, 20s at a high speed, 4000r/min at a high speed and 40s at a high speed, chlorobenzene is dripped as an anti-solvent at the 20 th s of the high-speed stage, and annealing treatment is carried out after spin coating, wherein the annealing temperature is 100 ℃ and the annealing time is 10 min;
(3) preparation of a Spiro-OMeTAD film: dissolving 90mg of Spiro-OMeTAD in 1mL of chlorobenzene, stirring for 3h to obtain a Spiro-OMeTAD solution, and spin-coating on the FTO transparent conductive glass substrate in the step (2) at the spin-coating speed of 4000r/min for 40s to obtain a uniform hole transport layer;
（4） MoO3and Ag electrode preparation: evaporating MoO on a Spiro-OMeTAD film by adopting an evaporation method3And Ag electrodes, in which MoO3The thickness of the film is 10 nm,the thickness of the Ag electrode is 100 nm.
The perovskite cell has the following device structure: FTO/TiO2Perovskite thin film/cyclone-OMeTAD/MoO3/Ag。
Comparative example 2
A preparation method of a perovskite solar cell comprises the following steps:
(1) FTO transparent conductive glass substrate cleaning and TiO2Preparing a film: repeatedly ultrasonically cleaning the FTO transparent conductive glass substrate with deionized water, acetone and ethanol for 3 times, drying at 100 ℃ until the solvent and water are completely removed, treating the treated FTO transparent conductive glass substrate with an ultraviolet lamp and ozone for 25 min, and depositing an electron transport layer TiO on the treated FTO transparent conductive glass substrate2Putting the mixture into a 100 ℃ oven for standby;
(2) preparing a Bis-PCBM membrane: dissolving 5mg of Bis-PCBM in 8mL of chlorobenzene, stirring for 4 hours to obtain a Bis-PCBM solution,
spin-coating on the deposited electron transport layer TiO2The spin coating speed of the FTO transparent conductive glass substrate is 4000r/min, the spin coating time is 40s, annealing treatment is carried out after the spin coating, the annealing temperature is 100 ℃, and the annealing time is 10 min;
(3) preparing a perovskite thin film: dissolving 180mg of methylammonium iodide and 553mg of lead iodide in 1mL of mixed solution of dimethyl sulfoxide and gamma-butyrolactone, wherein the volume ratio of the dimethyl sulfoxide to the gamma-butyrolactone is 3:7, stirring for 5h to obtain a perovskite solution, spin-coating the perovskite solution on the FTO transparent conductive glass substrate in the step (3), wherein the spin-coating speed is 2000r/min at a low speed, 20s at a high speed, 4000r/min at a high speed and 40s at a high speed, dripping chlorobenzene as an anti-solvent at the 20 th s at the high speed stage, and annealing after spin-coating, wherein the annealing temperature is 100 ℃ and the annealing time is 10 min;
(4) preparation of a Spiro-OMeTAD film: dissolving 90mg of Spiro-OMeTAD in 1mL of chlorobenzene, stirring for 3h to obtain a Spiro-OMeTAD solution, and spin-coating on the FTO transparent conductive glass substrate in the step (4) at the spin-coating speed of 4000r/min for 40s to obtain a uniform hole transport layer;
（5） MoO3and Ag electrode preparation: by evaporation method in Spiro-OMoO vapor deposition on MeTAD film3And Ag electrodes, in which MoO3The thickness is 10 nm, and the thickness of the Ag electrode is 100 nm.
The perovskite cell has the following device structure: FTO/TiO2[ two ] -PCBM/perovskite thin film/Spiro-OMeTAD/MoO3/Ag。
As can be seen from fig. 2, when a layer of Bis-PCBM was spin coated onto the membrane, the roughness and titania phase of the perovskite, Bis-PCBM was reduced, and when trace amounts of DMC were incorporated into the Bis-PCBM, the roughness was significantly reduced, facilitating the subsequent deposition of a perovskite layer.
As can be seen in fig. 3, the deposition was on Bis-PCBM: the crystallinity of perovskite on the DMC composite membrane is obviously improved.
Claims (6)
1. N-type doped electron transport layer and TiO2A method of making a layered perovskite battery, characterized by: the method comprises the following steps:
(1) FTO transparent conductive glass substrate cleaning and TiO2Preparing a film: repeatedly ultrasonically cleaning the FTO transparent conductive glass substrate with deionized water, acetone and ethanol for 3 times, drying at 100 ℃ until the solvent and water are completely removed, treating the treated FTO transparent conductive glass substrate with an ultraviolet lamp and ozone for 25 min, and depositing an electron transport layer TiO on the treated FTO transparent conductive glass substrate2Putting the mixture into a 100 ℃ oven for standby;
(2) preparing a Bis-PCBM and (pentamethylcyclopentadiene) cobalt composite membrane: dissolving 5mg of Bis-PCBM in 2-8mL of chlorobenzene, stirring for 4h to obtain a Bis-PCBM solution, dissolving a dopant (pentamethylcyclopentadiene) cobalt in ethanol to prepare a precursor solution with the concentration of 0.2-0.8mg/mL, and doping the precursor solution in the Bis-PCBM solution;
(3) spin-coating on the deposited electron transport layer TiO2The spin coating speed of the FTO transparent conductive glass substrate is 4000r/min, the spin coating time is 40s, annealing treatment is carried out after the spin coating, the annealing temperature is 100 ℃, and the annealing time is 10 min;
(4) preparing a perovskite thin film: dissolving 180mg of methylammonium iodide and 553mg of lead iodide in 1mL of mixed solution of dimethyl sulfoxide and gamma-butyrolactone, wherein the volume ratio of the dimethyl sulfoxide to the gamma-butyrolactone is 3:7, stirring for 5h to obtain a perovskite solution, spin-coating the perovskite solution on the FTO transparent conductive glass substrate in the step (3), wherein the spin-coating speed is 2000r/min at a low speed, 20s at a high speed, 4000r/min at a high speed and 40s at a high speed, dripping chlorobenzene as an anti-solvent at the 20 th s at the high speed stage, and annealing after spin-coating, wherein the annealing temperature is 100 ℃ and the annealing time is 10 min;
(5) preparation of a Spiro-OMeTAD film: dissolving 90mg of Spiro-OMeTAD in 1mL of chlorobenzene, stirring for 3h to obtain a Spiro-OMeTAD solution, and spin-coating on the FTO transparent conductive glass substrate in the step (4) at the spin-coating speed of 4000r/min for 40s to obtain a uniform hole transport layer;
（6） MoO3and Ag electrode preparation: evaporating MoO on a Spiro-OMeTAD film by adopting an evaporation method3And an Ag electrode.
2. An n-type doped electron transport layer and TiO according to claim 12A method of making a layered perovskite battery, characterized by: TiO in the step (1)2The deposition method of (1) was to add 4.5mL of titanium tetrachloride solution to 200mL of ultrapure water and perform a deposition reaction at 70 ℃ for 1 hour.
3. An n-type doped electron transport layer and TiO according to claim 12A method of making a layered perovskite battery, characterized by: the volume ratio of the precursor solution to the Bis-PCBM solution in the step (2) is 0.05-1.0%.
4. An n-type doped electron transport layer and TiO according to claim 12A method of making a layered perovskite battery, characterized by: MoO in the step (6)3The thickness is 10 nm, and the thickness of the Ag electrode is 100 nm.
5. A perovskite battery produced by the method as claimed in any one of claims 1 to 4.
6. The perovskite battery of claim 5The structure is as follows: FTO/TiO2[ Bis ] -PCBM (pentamethylcyclopentadiene) cobalt/perovskite thin film/Spiro-OMeTAD/MoO3/Ag。
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