CN109065720B - Perovskite solar cell with accurately doped crystal boundary and preparation method thereof - Google Patents

Perovskite solar cell with accurately doped crystal boundary and preparation method thereof Download PDF

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CN109065720B
CN109065720B CN201810243472.8A CN201810243472A CN109065720B CN 109065720 B CN109065720 B CN 109065720B CN 201810243472 A CN201810243472 A CN 201810243472A CN 109065720 B CN109065720 B CN 109065720B
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田辉
张京
熊启
陆超杰
侯大刚
诸跃进
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Ningbo University
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Abstract

The invention relates to a perovskite solar cell with accurately doped crystal boundaries and a preparation method thereof, which are characterized in that: conductive glass layer, compact titanium dioxide film, titanium-doped CH3NH3PbI3Polycrystalline film, hole transport material layer, evaporated silver electrode layer, and Ti-doped CH3NH3PbI3The polycrystalline film is formed by doping titanium ions at grain boundaries, annealing and in-situ forming grain boundary defect passivated CH3NH3PbI3The molar number of the titanium ions of the polycrystalline film is 0.01-5% of that of the lead ions. By doping the titanium element, the invention effectively inhibits the combination of current carriers of a p-n junction in the battery at a crystal boundary, so that the parallel parasitic resistance is increased, and the filling factor, the photocurrent density and the photoelectric conversion efficiency of the battery are improved. Meanwhile, the doping proportion of the titanium element is optimized, and the photoelectric conversion efficiency is further improved.

Description

Perovskite solar cell with accurately doped crystal boundary and preparation method thereof
Technical Field
The invention relates to a perovskite solar cell with accurately doped crystal boundaries and a preparation method thereof.
Background
The perovskite solar cell has low cost and good performance, and the preparation is simple and is highly valued by scientific research and the industry. Since the perovskite material is used for the solar cell in 2009, the efficiency is over 22 percent at present and is 5 times of the initial cell efficiency, and after novel thin film solar cells such as dye-sensitized solar cells and organic solar cells are thrown away, the perovskite solar cells are low-cost thin film solar cells which are developed rapidly in three years.
The structural core of the perovskite solar cell is a perovskite crystal form (ABX)3) The organometallic halide light absorbing material of (a). In this perovskite ABX3In the structure, A is methylamino (CH)3NH3) B is metallic lead atom, and X is halogen atom such as chlorine, bromine, iodine, etc. Currently, in high efficiency perovskite type solar cells, the most common perovskite material is lead iodide methylamine (CH)3NH3PbI3) Its band gap is about 1.6 eV, extinction coefficient is high, and several hundreds of nano-thick films can fully absorb sunlight below 800 nm. Moreover, the material is simple to prepare and contains PbI2And CH3NH3And (3) spin-coating the solution I at normal temperature and dropwise adding chlorobenzene for extraction to obtain a uniform film. The above characteristics make the perovskite structure CH3NH3PbI3The absorption of visible light and partial near infrared light can be realized, and the generated photogenerated carriers are not easy to recombine, so that the energy loss is small, which is the root cause for the high efficiency of the perovskite type solar cell.
Perovskite solar cells currently have a variety of structures: mesoscopic cells containing porous titanium dioxide, planar cells without porous titanium dioxide, superstructure mesoscopic cells containing porous insulating oxides (alumina, zirconia), etc.
Currently, research focuses on adjusting the performance of organic-inorganic hybrid perovskites by adjusting the a site, the B site and the X site, so as to further optimize the photoelectric conversion performance of the perovskites. At present, by spin coating from solution and annealing, it is difficult to obtain a single-crystal planar thin film. The polycrystalline film has large specific surface area and more surface defects, so that charge recombination inside the device is serious. Lead iodide doping of perovskite films to suppress grain boundary defects has been reported. However, there are few reports of doping with other elements of the perovskite grain boundaries thereof and suppressing defects and recombination thereof. And because the doped element has very small ionic radius, the defect position at the crystal boundary can not be doped accurately, and the repeatability of a battery device can not be ensured, other elements need to be explored for doping to improve the performance of the battery.
In summary, the problems of the prior art are as follows:
1) organic-inorganic hybrid perovskite material CH3NH3PbI3Needs to be further optimized to improve the photoelectric conversion performance;
2) at present, elements doping the crystal boundary affect the open-circuit voltage and the repeatability of the battery, and the problem of carrier recombination caused by the crystal boundary defect is not solved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a crystal boundary-accurately-doped perovskite solar cell for improving defects in a polycrystalline forming process by perovskite doping and a preparation method thereof.
The technical scheme adopted by the invention for solving the problems is as follows: a perovskite solar cell with accurately doped crystal boundaries, characterized in that: conductive glass layer, compact titanium dioxide film, titanium-doped CH3NH3PbI3Polycrystalline film, hole transport material layer and evaporated silver electrode layer, titanium doped CH3NH3PbI3The polycrystalline film is formed by doping titanium ions at grain boundaries, annealing and in-situ forming grain boundary defect passivated CH3NH3PbI3The molar number of the titanium ions of the polycrystalline film is 0.01-5% of that of the lead ions.
The particle radius of the titanium ions is less than CH3NH3PbI3Grain radius of polycrystalline film.
The thickness of the compact titanium dioxide film is 20-200 nanometers, and the titanium is doped with CH3NH3PbI3The thickness of the polycrystalline film is 200 nm-1.5 microns, the thickness of the hole transmission material layer is 50-500 nm, and the thickness of the evaporated silver electrode layer is 50-200 nm.
The hole transport material layer is spiro-MeOTAD or 3-hexyl substituted polythiophene.
A preparation method of a perovskite solar cell with accurately doped crystal boundaries is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: dissolving iodomethylamine and lead iodide in N, N-dimethylformamide according to the molar ratio of 1:1, adding titanium tetrachloride, and uniformly stirring to form a perovskite solution;
step two: depositing a compact titanium dioxide film on the conductive glass by using a sol-gel method; treating the compact titanium dioxide film at 300-500 ℃, then carrying out titanium tetrachloride treatment, and sintering for later use;
step three: depositing the perovskite solution on a compact titanium dioxide film by a chlorobenzene extraction process by using a spin coater, and baking for 30 minutes at the temperature of 40-100 ℃ to crystallize the perovskite solution on the compact titanium dioxide film into titanium-doped CH3NH3PbI3A polycrystalline film;
step IV: uniformly spin-coating organic solution of hole transport material on titanium-doped CH3NH3PbI3Forming a hole transport material layer on the polycrystalline film;
step five: and (3) evaporating the silver-evaporated electrode layer on the hole transport material layer by using an evaporation method.
The material of the hole transport material layer is spiro-MeOTAD, and the preparation steps of the organic solution of the hole transport material are as follows: dissolving spirol-MeOTAD in chlorobenzene, adding tetrabutyl pyridine with the molar number of 80% of spirol-MeOTAD and lithium bistrifluoromethanesulfonylimide with the molar number of 30% of spirol-MeOTAD, and uniformly stirring, wherein the molar concentration of spirol-MeOTAD is 0.5-1.5M.
In the perovskite solution, the molar concentrations of iodomethylamine and lead iodide are both controlled to be 0.8-1.2M.
Compared with the prior art, the invention has the advantages that: uses titanium with relatively small ionic radius to dope CH3NH3PbI3. Since titanium ions are much smaller than perovskite grains, they can dope grain boundary defects during the formation of perovskite polycrystals. The doping of the titanium element effectively inhibits the combination of current carriers of a p-n junction in the battery at a crystal boundary, so that the parallel connection is realizedThe generated resistance is increased, thereby improving the cell filling factor, the photocurrent density and the photoelectric conversion efficiency. Meanwhile, the doping proportion of the titanium element is optimized, and the photoelectric conversion efficiency is further improved.
Drawings
FIG. 1 shows CH in example 2 of the present invention3NH3PbI3EDS plot of lattice, Ti, Pb.
FIG. 2 is an SEM photograph of comparative example and example 2 of the present invention.
FIG. 3 is a plot of the current-voltage characteristics of comparative example and examples 1-4 of the present invention.
FIG. 4 is CH for comparative example and examples 1 to 4 of the present invention3NH3PbI3Steady state PL photoluminescence spectra of polycrystalline films/glasses.
FIG. 5 is CH for comparative example and examples 1 to 4 of the present invention3NH3PbI3Steady state PL photoluminescence spectra of polycrystalline films/conducting glasses.
Detailed Description
The present invention will be described in further detail below by way of examples with reference to the accompanying drawings, which are illustrative of the present invention and are not to be construed as limiting the present invention.
Preparation of TiCl4N, N-dimethylformamide solution of (1): taking pure TiCl41 ml of the liquid was added to 10 ml of pure alcohol (stored in a refrigerator) to obtain 1M TiCl4The alcohol solution of (1). 50 microlitres of TiCl are taken4The alcohol solution was added to 950. mu.l of N, N-Dimethylformamide (DMF), and the solution was diluted to obtain 0.05M TiCl4A solution; take 100. mu.l of TiCl4Was added to 900. mu.l of N, N-Dimethylformamide (DMF) and diluted to give 0.1M TiCl4A solution; taking 200 microliter of TiCl4Is added to 800. mu.l of N, N-Dimethylformamide (DMF) and diluted to give 0.2M TiCl4A solution; 500 microliter of TiCl are taken4Was added to 500. mu.l of N, N-Dimethylformamide (DMF), and diluted to give 0.5M TiCl4And (3) solution.
Comparative example.
This example prepared pure CH3NH3PbI3Perovskite solar cell.
First, 0.461 g of PbI was weighed2And 0.159 g of CH3NH3And (3) dissolving the I into 1 ml of N, N-Dimethylformamide (DMF), and uniformly stirring and mixing to form a perovskite solution.
Depositing a layer of dense titanium dioxide film (100 nanometers) on the conductive glass layer by using a sol-gel method; the compact titanium dioxide film is treated at 450 ℃ and then treated with titanium tetrachloride, and is sintered for later use.
The perovskite solution is deposited on the compact titanium dioxide film by a chlorobenzene extraction process by using a spin coater. The perovskite solution is crystallized into CH by accurately controlling the temperature to be baked for 30 minutes at 40-100 DEG C3NH3PbI3A polycrystalline film.
A chlorobenzene solution of a hole transport material spiro-MeOTAD (with a concentration of 0.6M, added with tetrabutyl pyridine (tBP) with a molar number of 80% of the spiro-MeOTAD and lithium bistrifluoromethanesulfonylimide (Li-TFSI) with a molar number of 30% of the spiro-MeOTAD) was uniformly spin-coated on CH3NH3PbI3Polycrystalline film, forming a hole transport material layer.
And (3) evaporating the silver-evaporated electrode layer on the hole transport material layer by using an evaporation method.
CH in this embodiment3NH3PbI3The thickness of the polycrystalline film is 600 nanometers, the thickness of the hole transmission material layer is 300 nanometers, and the thickness of the evaporated silver electrode layer is 90 nanometers.
In a room temperature environment, a xenon lamp is used for simulating sunlight, and the light intensity is 95.6mW/cm2(model number of solar simulator: Newport 91192A) under the condition, the perovskite solar cell (the effective illumination area is 0.07 cm)2) The photoelectric conversion efficiency of (1) was 14.0% (short-circuit current density 22.2 mAcm)-2Open circuit voltage 1.09V, fill factor 0.61).
Example 1.
Preparation of titanium-doped CH3NH3PbI3Of a solution of N, N-dimethylformamide having a molar concentration of Ti of 0.05% of that of lead iodide, for use in the preparation of a pharmaceutical compositionAnd preparing the perovskite solar cell.
First, 0.461 g of PbI was weighed2With 0.159 g CH3NH3I are dissolved in 1 ml of N, N-Dimethylformamide (DMF) together, stirred and mixed evenly, and then 0.05M TiCl is dripped410 microliter of the solution is stirred evenly to become perovskite solution for standby.
Depositing a layer of dense titanium dioxide film (100 nanometers) on the conductive glass layer by using a sol-gel method; the compact titanium dioxide film is treated at 450 ℃ and then treated with titanium tetrachloride, and is sintered for later use.
The perovskite solution is deposited on the compact titanium dioxide film by a chlorobenzene extraction process by using a spin coater. The perovskite solution is crystallized into titanium-doped CH by accurately controlling the temperature to be baked for 30 minutes at 40-100 DEG C3NH3PbI3A polycrystalline film.
A chlorobenzene solution of a hole transport material spiro-MeOTAD (with a concentration of 0.6M, added with tetrabutyl pyridine (tBP) with a molar number of 80% of the spiro-MeOTAD and lithium bistrifluoromethanesulfonylimide (Li-TFSI) with a molar number of 30% of the spiro-MeOTAD) was uniformly spin-coated on CH3NH3PbI3Polycrystalline film, forming a hole transport material layer.
And (3) evaporating the silver-evaporated electrode layer on the hole transport material layer by using an evaporation method.
CH in this embodiment3NH3PbI3The thickness of the polycrystalline film is 600 nanometers, the thickness of the hole transmission material layer is 300 nanometers, and the thickness of the evaporated silver electrode layer is 90 nanometers.
Titanium doped CH in this example3NH3PbI3The thickness of the polycrystalline film is 600 nanometers, the thickness of the hole transmission material layer is 300 nanometers, and the thickness of the evaporated silver electrode layer is 90 nanometers.
In a room temperature environment, a xenon lamp is used for simulating sunlight, and the light intensity is 95.6mW/cm2(model number of solar simulator: Newport 91192A) under the condition, the modified perovskite solar cell (the effective illumination area is 0.07 cm)2) The photoelectric conversion efficiency of (1) was 14.8% (short-circuit current density: 19.0 mAcm)-2Open circuit voltage 1.10V, fill factor0.70) which is about 6.0% higher than the unmodified solar cell efficiency. It can be seen that trace Ti doping reduces the short circuit current, but the fill factor is greatly improved. Referring to fig. 4, doping 0.05% of titanium element effectively increases CH, compared to the undoped sample3NH3PbI3Photoluminescence intensity of the polycrystalline film indicates that the doped sample inhibits charge recombination in the crystal. Referring to fig. 5, the luminous intensity of the perovskite layer doped with 0.05% of titanium on the conductive glass is reduced, which indicates that the carrier transport capability of the perovskite layer is enhanced by doping 0.05% of titanium element. This is due to the introduction of Ti doping to CH3NH3PbI3The formation of polycrystals has an effect, resulting in a reduction in current. But a trace amount of Ti is doped in CH3NH3PbI3And the crystal boundary defect effectively inhibits the recombination of carriers, and simultaneously increases the transmission capability of the carriers, thereby greatly improving the filling factor of the battery.
Example 2.
Preparation of titanium-doped CH3NH3PbI3The molar concentration of Ti is 0.1 percent of that of lead iodide, and the N, N-dimethylformamide solution is used for preparing the perovskite solar cell.
First, 0.461 g of PbI was weighed2With 0.159 g CH3NH3I are dissolved in 1 ml of N, N-Dimethylformamide (DMF) together, stirred and mixed evenly, and then 0.1M TiCl is dripped410 microliter of the solution is stirred evenly to become perovskite solution for standby.
Depositing a layer of dense titanium dioxide film (100 nanometers) on the conductive glass layer by using a sol-gel method; the compact titanium dioxide film is treated at 450 ℃ and then treated with titanium tetrachloride, and is sintered for later use.
The perovskite solution is deposited on the compact titanium dioxide film by a chlorobenzene extraction process by using a spin coater. The perovskite solution is crystallized into titanium-doped CH by accurately controlling the temperature to be baked for 30 minutes at 40-100 DEG C3NH3PbI3A polycrystalline film.
Adding chlorobenzene solution (with concentration of 0.6M and mole number of 80% of spirol-MeOTAD) of hole transport material spirol-MeOTADUniformly spin-coating pyridine (tBP) and 30 mol% of spiro-MeOTAD lithium bistrifluoromethanesulfonylimide (Li-TFSI)) on CH3NH3PbI3Polycrystalline film, forming a hole transport material layer.
And (3) evaporating the silver-evaporated electrode layer on the hole transport material layer by using an evaporation method.
CH in this embodiment3NH3PbI3The thickness of the polycrystalline film is 600 nanometers, the thickness of the hole transmission material layer is 300 nanometers, and the thickness of the evaporated silver electrode layer is 90 nanometers.
Titanium doped CH in this example3NH3PbI3The thickness of the polycrystalline film is 600 nanometers, the thickness of the hole transmission material layer is 300 nanometers, and the thickness of the evaporated silver electrode layer is 90 nanometers.
In a room temperature environment, a xenon lamp is used for simulating sunlight, and the light intensity is 95.6mW/cm2(model number of solar simulator: Newport 91192A) under the condition, the modified perovskite solar cell (the effective illumination area is 0.07 cm)2) The photoelectric conversion efficiency of (1) was 17.4% (short-circuit current density 22.3 mAcm)-2Open circuit voltage 1.09V, fill factor 0.72), efficiency over unmodified solar cell (14.0%, short circuit current density 22.2 mAcm)-2Open circuit voltage 1.09V, fill factor 0.61) improved by 24.3%. It can be seen that the fill factor is greatly improved by doping the cell. Doping with 0.1% titanium element increases CH compared to the undoped sample, see fig. 43NH3PbI3The luminescence intensity of the polycrystalline film indicates that the doped sample inhibits charge recombination in the crystal. Referring to fig. 5, the luminous intensity of the perovskite layer doped with 0.1% titanium on the conductive glass layer is greatly reduced, which indicates that the carrier transport capability of the perovskite layer is effectively enhanced by doping 0.1% titanium element. The reason for improving the performance of the perovskite doped with 0.1 percent of Ti is that a proper amount of Ti is doped at the defect position of the perovskite crystal boundary, so that the compounding of current carriers is effectively inhibited, the transmission capability of the current carriers is greatly increased, and the filling factor of the battery is greatly improved. This example is the best example.
See fig. 1. CH (CH)3NH3PbI3EDS diagram of crystal lattice is part a of FIG. 1, TiThe EDS diagram of (1) is a portion b, and the EDS diagram of Pb is a portion c of FIG. 1. Comparing the part b with the part a, the Ti element is intensively distributed in CH3NH3PbI3Grain boundaries of the crystal lattice; comparison of part c with part a revealed that the Pb element was uniformly distributed in CH3NH3PbI3Within the crystal lattice. The element Ti is illustrated in CH3NH3PbI3The crystal lattice plays a role of passivating defects, so that the compounding of carriers in the perovskite polycrystal is inhibited, and the transmission of the carriers of the device is facilitated.
See fig. 2. Part a in FIG. 2 is CH of a comparative example3NH3PbI3SEM photograph of polycrystalline film, part b is CH of this example3NH3PbI3SEM image of polycrystalline film. The coordinate scale in fig. 2 is 1 μm. FIG. 2 illustrates that with Ti element doping, the perovskite grains are slightly smaller than the undoped perovskite grains, thereby reducing the formation of large defects at the perovskite polycrystalline grain boundaries.
Example 3.
Preparation of titanium-doped CH3NH3PbI3The molar concentration of Ti in the N, N-dimethylformamide solution is 0.2 percent of that of lead iodide, and the N, N-dimethylformamide solution is used for preparing the perovskite solar cell.
First, 0.461 g of PbI was weighed2With 0.159 g CH3NH3I are dissolved in 1 ml of N, N-Dimethylformamide (DMF) together, stirred and mixed evenly, and then 0.2M TiCl is dripped410 microliter of the solution is stirred evenly to become perovskite solution for standby.
Depositing a layer of dense titanium dioxide film (100 nanometers) on the conductive glass layer by using a sol-gel method; the compact titanium dioxide film is treated at 450 ℃ and then treated with titanium tetrachloride, and is sintered for later use.
The perovskite solution is deposited on the compact titanium dioxide film by a chlorobenzene extraction process by using a spin coater. The perovskite solution is crystallized into titanium-doped CH by accurately controlling the temperature to be baked for 30 minutes at 40-100 DEG C3NH3PbI3A polycrystalline film.
A solution of the hole transport material spiro-MeOTAD in chlorobenzene (0.6M in concentration) was addedTetrabutylpyridine (tBP) with 80 mol% of spiro-MeOTAD and lithium bistrifluoromethanesulfonylimide (Li-TFSI)) with 30 mol% of spiro-MeOTAD were uniformly spin-coated on CH3NH3PbI3Polycrystalline film, forming a hole transport material layer.
And (3) evaporating the silver-evaporated electrode layer on the hole transport material layer by using an evaporation method.
CH in this embodiment3NH3PbI3The thickness of the polycrystalline film is 600 nanometers, the thickness of the hole transmission material layer is 300 nanometers, and the thickness of the evaporated silver electrode layer is 90 nanometers.
Titanium doped CH in this example3NH3PbI3The thickness of the polycrystalline film is 600 nanometers, the thickness of the hole transmission material layer is 300 nanometers, and the thickness of the evaporated silver electrode layer is 90 nanometers.
In a room temperature environment, a xenon lamp is used for simulating sunlight, and the light intensity is 95.6mW/cm2(model number of solar simulator: Newport 91192A) under the condition, the modified perovskite solar cell (the effective illumination area is 0.07 cm)2) The photoelectric conversion efficiency of (1) (short-circuit current density: 20.1 mAcm)-2Open circuit voltage 1.10V, fill factor 0.637), and unmodified solar cell efficiency (14.0%, short circuit current density 22.2mAcm @)-2Open circuit voltage 1.09V, fill factor 0.61) are not widely separated. It can be seen, however, that the fill factor is increased by doping, while the short circuit current density is reduced. In comparison to the undoped sample, see fig. 4, titanium was doped with 0.2% CH3NH3PbI3The polycrystalline film has a reduced luminous intensity. Referring to FIG. 5, the conductive glass layer is titanium doped with 0.2% CH3NH3PbI3The polycrystalline film had a reduced luminescence intensity but an increased luminescence intensity compared to the sample doped with 0.1%. This is due to the fact that 0.2% Ti still acts at the perovskite grain boundaries, however, as the doping level of Ti increases the CH is affected3NH3PbI3The formation of polycrystalline film causes impurity defects, which affect the increase of the battery current.
Example 4.
Preparation of titanium-doped CH3NH3PbI3N, N-dimethylAnd (3) a basic formamide solution with the molar concentration of Ti being 0.5% of that of lead iodide is used for preparing the perovskite solar cell.
First, 0.461 g of PbI was weighed2With 0.159 g CH3NH3I are dissolved in 1 ml of N, N-Dimethylformamide (DMF) together, stirred and mixed evenly, and then 0.5M TiCl is dripped410 microliter of the solution is stirred evenly to become perovskite solution for standby.
Depositing a layer of dense titanium dioxide film (100 nanometers) on the conductive glass layer by using a sol-gel method; the compact titanium dioxide film is treated at 450 ℃ and then treated with titanium tetrachloride, and is sintered for later use.
The perovskite solution is deposited on the compact titanium dioxide film by a chlorobenzene extraction process by using a spin coater. The perovskite solution is crystallized into titanium-doped CH by accurately controlling the temperature to be baked for 30 minutes at 40-100 DEG C3NH3PbI3A polycrystalline film.
A chlorobenzene solution of a hole transport material spiro-MeOTAD (with a concentration of 0.6M, added with tetrabutyl pyridine (tBP) with a molar number of 80% of the spiro-MeOTAD and lithium bistrifluoromethanesulfonylimide (Li-TFSI) with a molar number of 30% of the spiro-MeOTAD) was uniformly spin-coated on CH3NH3PbI3Polycrystalline film, forming a hole transport material layer.
And (3) evaporating the silver-evaporated electrode layer on the hole transport material layer by using an evaporation method.
CH in this embodiment3NH3PbI3The thickness of the polycrystalline film is 600 nanometers, the thickness of the hole transmission material layer is 300 nanometers, and the thickness of the evaporated silver electrode layer is 90 nanometers.
Titanium doped CH in this example3NH3PbI3The thickness of the polycrystalline film is 600 nanometers, the thickness of the hole transmission material layer is 300 nanometers, and the thickness of the evaporated silver electrode layer is 90 nanometers.
In a room temperature environment, a xenon lamp is used for simulating sunlight, and the light intensity is 95.6mW/cm2(model number of solar simulator: Newport 91192A) and the doped perovskite solar cell (the effective illumination area is 0.07 cm)2) The photoelectric conversion efficiency of the photoelectric conversion element is 11.7 percent(short-circuit current density 20.0mAcm-2Open circuit voltage 1.08V, fill factor 0.540), specific solar cell efficiency (14.0%, short circuit current density 22.2 mAcm) over unmodified solar cell-2Open circuit voltage 1.09V, fill factor 0.61) is greatly reduced. It can be seen that the short circuit current density and fill factor are greatly reduced by doping. In comparison to the undoped sample, see fig. 4, titanium was doped with 0.5% CH3NH3PbI3The polycrystalline film has a greatly reduced luminous intensity. Referring to FIG. 5, the conductive glass layer is titanium doped with 0.5% CH3NH3PbI3The polycrystalline film has reduced luminous intensity, but is greatly improved compared with perovskite with 0.1 percent of doped titanium. The excessive Ti doping seriously influences the formation of ore titanium ore polycrystal, causes more impurity defects, increases the recombination probability of current carriers, and greatly reduces the short-circuit current and the filling factor.
In addition, it should be noted that the specific embodiments described in the present specification may be different in the components, the shapes of the components, the names of the components, and the like, and the above description is only an illustration of the structure of the present invention. Equivalent or simple changes in the structure, characteristics and principles of the invention are included in the protection scope of the patent. Various modifications, additions and substitutions for the specific embodiments described may occur to those skilled in the art without departing from the scope of the invention as defined in the accompanying claims.

Claims (7)

1. A perovskite solar cell with accurately doped crystal boundaries, characterized in that: conductive glass layer, compact titanium dioxide film and titanium tetrachloride-doped CH3NH3PbI3Polycrystalline film, hole transport material layer and evaporated silver electrode layer, titanium tetrachloride doped CH3NH3PbI3The polycrystalline film is formed by doping titanium ions at grain boundaries, annealing and in-situ forming grain boundary defect passivated CH3NH3PbI3Polycrystalline film, the mole number of titanium ion is lead0.01-5% of the mole number of the ions.
2. The grain boundary precisely doped perovskite solar cell of claim 1, wherein: the particle radius of the titanium ion is less than CH3NH3PbI3Grain radius of polycrystalline film.
3. The grain boundary precisely doped perovskite solar cell according to claim 1 or 2, characterized in that: the thickness of the compact titanium dioxide film is 20-200 nanometers, and the titanium tetrachloride is doped with CH3NH3PbI3The thickness of the polycrystalline film is 200 nm-1.5 microns, the thickness of the hole transmission material layer is 50-500 nm, and the thickness of the evaporated silver electrode layer is 50-200 nm.
4. The grain boundary precisely doped perovskite solar cell of claim 3, wherein: the hole transport material layer is spiro-MeOTAD or 3-hexyl substituted polythiophene.
5. A method for preparing a grain boundary precisely doped perovskite solar cell as claimed in any one of claims 1 to 4, characterized in that: the method comprises the following steps:
the method comprises the following steps: dissolving iodomethylamine and lead iodide in N, N-dimethylformamide according to the molar ratio of 1:1, adding titanium tetrachloride, and uniformly stirring to form a perovskite solution;
step two: depositing a compact titanium dioxide film on the conductive glass by using a sol-gel method; treating the compact titanium dioxide film at 300-500 ℃, then carrying out titanium tetrachloride treatment, and sintering for later use;
step three: depositing the perovskite solution on a compact titanium dioxide film by a chlorobenzene extraction process by using a spin coater, and baking for 30 minutes at the temperature of 40-100 ℃ to crystallize the perovskite solution on the compact titanium dioxide film into titanium tetrachloride-doped CH3NH3PbI3A polycrystalline film;
step IV: uniformly spin-coating organic solution of hole transport material on titanium tetrachlorideHetero CH3NH3PbI3Forming a hole transport material layer on the polycrystalline film;
step five: and evaporating the silver electrode layer on the hole transport material layer by using an evaporation method.
6. The method for preparing the perovskite solar cell with the precisely doped grain boundary according to claim 5, wherein the method comprises the following steps: the hole transport material layer is made of spiro-MeOTAD, and the preparation steps of the organic solution of the hole transport material are as follows: dissolving spiromesiad in chlorobenzene, wherein the molar concentration of spiromesiad is 0.5-1.5M, adding tetrabutyl pyridine accounting for 80% of the molar number of spiromesiad and lithium bistrifluoromethanesulfonylimide accounting for 30% of the molar number of spiromesiad, and uniformly stirring.
7. The method for preparing the perovskite solar cell with the precisely doped grain boundary according to claim 6, wherein the method comprises the following steps: in the perovskite solution, the molar concentrations of iodomethylamine and lead iodide are controlled to be 0.8-1.2M.
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Publication number Priority date Publication date Assignee Title
CN110854276B (en) * 2019-12-04 2021-10-12 华东理工大学 Preparation method and application of titanium tetrafluoride passivated perovskite battery interface
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CN112133836B (en) * 2020-09-08 2022-09-06 宁波大学 Perovskite solar cell prepared by in-situ growth

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105642131A (en) * 2014-11-13 2016-06-08 中国科学院大连化学物理研究所 Method for stabilizing perovskite structure oxygen permeation membrane through nanoparticles
CN105702865A (en) * 2016-04-05 2016-06-22 河北大学 Metal-ion-doped perovskite thin film, preparation method and application therefor
KR20160085720A (en) * 2015-01-08 2016-07-18 한국화학연구원 Fabrication Method of Device Having Inorganic-Orgaic Hybrid Perovskites Compound Film and the Device thereof
CN106170877A (en) * 2014-02-26 2016-11-30 联邦科学和工业研究组织 The method forming the photosensitive layer of perovskite light-sensitive unit
CN106299139A (en) * 2016-09-14 2017-01-04 宁波大学 The perovskite solaode of a kind of ion doping and manufacture method thereof
WO2017108710A1 (en) * 2015-12-21 2017-06-29 Imec Vzw Doped titanate
CN107210367A (en) * 2014-12-19 2017-09-26 联邦科学和工业研究组织 The method for forming the photoactive layer of photoelectric device
CN107275487A (en) * 2017-06-08 2017-10-20 华东师范大学 A kind of perovskite solar cell of efficient stable and preparation method thereof
CN107369764A (en) * 2017-06-29 2017-11-21 北京科技大学 A kind of perovskite solar cell and preparation method for adulterating lead acetate trihydrate

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170330693A1 (en) * 2016-05-11 2017-11-16 Board Of Trustees Of Michigan State University Interlayer Additives For Highly Efficient And Hysteresis-Free Perovskite-Based Photovoltaic Devices

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106170877A (en) * 2014-02-26 2016-11-30 联邦科学和工业研究组织 The method forming the photosensitive layer of perovskite light-sensitive unit
CN105642131A (en) * 2014-11-13 2016-06-08 中国科学院大连化学物理研究所 Method for stabilizing perovskite structure oxygen permeation membrane through nanoparticles
CN107210367A (en) * 2014-12-19 2017-09-26 联邦科学和工业研究组织 The method for forming the photoactive layer of photoelectric device
KR20160085720A (en) * 2015-01-08 2016-07-18 한국화학연구원 Fabrication Method of Device Having Inorganic-Orgaic Hybrid Perovskites Compound Film and the Device thereof
WO2017108710A1 (en) * 2015-12-21 2017-06-29 Imec Vzw Doped titanate
CN105702865A (en) * 2016-04-05 2016-06-22 河北大学 Metal-ion-doped perovskite thin film, preparation method and application therefor
CN106299139A (en) * 2016-09-14 2017-01-04 宁波大学 The perovskite solaode of a kind of ion doping and manufacture method thereof
CN107275487A (en) * 2017-06-08 2017-10-20 华东师范大学 A kind of perovskite solar cell of efficient stable and preparation method thereof
CN107369764A (en) * 2017-06-29 2017-11-21 北京科技大学 A kind of perovskite solar cell and preparation method for adulterating lead acetate trihydrate

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Efficient perovskite solar cells by metal ion doping;Wang, JTW et al.;《ENERGY & ENVIRONMENTAL SCIENCE》;20161231;第2900页 *
Enhanced optical absorption via cation doping hybrid lead iodine perovskites;Tang, ZK et al.;《SCIENTIFIC REPORTS》;20170810;第2页 *
钛掺杂钙钛矿制备高效率钙钛矿太阳能电池;田辉 et al.;《Researchgate》;20180131;abstract *

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