CN104795499B - Perovskite-based solar cell of organic inorganic hybridization and preparation method thereof - Google Patents

Abstract

The invention relates to an organic-inorganic hybrid perovskite-based solar cell and a preparation method thereof. The cell of the invention includes a substrate and a transparent electrode stacked on the substrate in sequence, an electron transport layer, an ultra-thin alignment layer, a perovskite Ore absorbing layer, hole transport layer and counter electrode. Before the perovskite light-absorbing layer is prepared by the liquid phase method, the ultra-thin alignment layer is formed by modifying the surface of the electron transport layer or the hole transport layer with a micro-nano structure. Through the macrocyclic structure effect of molecules in the ultra-thin oriented layer, the directional growth of perovskite crystals is controlled, crystal regularity is improved, and internal defects are reduced. Effectively increase the carrier diffusion length inside the perovskite layer and prevent the recombination of electron-hole pairs inside and at the interface of the perovskite layer, thereby significantly improving the photoelectric conversion efficiency and stability of the battery. At the same time, the directional template effect of the ultra-thin oriented layer makes the crystal quality of the perovskite light-absorbing layer not easily affected by the film-forming conditions, improves the repeatability of device preparation, and makes the low-temperature solution method more suitable for the industrial production of large-area perovskite solar cells .

Description

Organic-inorganic hybrid perovskite-based solar cell and preparation method thereof

technical field

The invention relates to the technical field of perovskite-based thin-film solar cells, in particular to an organic-inorganic hybrid perovskite-based solar cell and a preparation method thereof.

Background technique

Organic-inorganic hybrid perovskite-based solar cells have shown excellent optoelectronic performance and great potential in recent years. With the development of perovskite solar cell technology, the photoelectric conversion efficiency of cell devices based on this light-absorbing material is as high as 19.3%.

The crystallization quality of the perovskite light-absorbing layer and its interface control with the electrode modification layer are crucial to the photoelectric performance of the battery, directly affecting the conversion efficiency and stability of the battery. The preparation methods of perovskite light-absorbing layer mainly include liquid phase method, gas phase assisted liquid phase method, gas phase co-evaporation deposition method, etc. The liquid-phase method does not require high-temperature and high-vacuum processes, has a simple process, and is suitable for large-scale industrial production. It is currently the main method for preparing perovskite light-absorbing layers.

In the existing perovskite-based solar cell structure, the _perovskite light-absorbing layer is generally deposited directly on the surface of the electrode modification layer (such as the surface _{of TiO 2} , ZnO, PEDOT:PSS, etc.) by a liquid phase method. I rapidly self-assemble into nano-scale perovskite tiny grains during the coating process. It is difficult to control the nucleation of perovskite grains and the growth direction of the film layer. The dense perovskite film reduces the diffusion length of carriers, and the recombination of electron-hole pairs is serious. The liquid phase method is affected by various factors such as the composition ratio, concentration, solvent, and spin coating speed of the precursor solution. It is difficult to control the crystallization quality, and the morphology of the film after crystallization is different. It greatly limits the industrialization process of perovskite-based solar cells.

Contents of the invention

The technical problem to be solved by the present invention is to provide an organic-inorganic hybrid perovskite-based solar cell with an ultra-thin alignment layer for the above-mentioned existing problems and deficiencies.

Another technical problem solved by the present invention is to provide a preparation method for this organic-inorganic hybrid perovskite-based solar cell.

In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:

An organic-inorganic hybrid perovskite-based solar cell, including a substrate, a transparent electrode, an electron transport layer, an ultrathin alignment layer, a perovskite light-absorbing layer, a hole transport layer and a counter electrode sequentially stacked on the substrate .

An organic-inorganic hybrid perovskite-based solar cell, including a substrate, a transparent electrode, a hole transport layer, an ultra-thin alignment layer, a perovskite light-absorbing layer, an electron transport layer and a counter electrode sequentially stacked on the substrate .

In the above-mentioned organic-inorganic hybrid perovskite-based solar cell, the ultra-thin alignment layer is composed of ring-shaped molecules whose cavity inner diameter can complex with lead ions, and the ring-shaped molecules are selected from monobenzo 15-crown-5, Styryl 15-crown-5, dibenzo-15-crown-5, dibenzo-18-crown-6, N,N-dimethylnitrile ethyldiaza-18-crown-6, tetraphenyl Porphyrin, tetrakis(2-hydroxy-1-naphthyl)porphyrin, tetrakis(2-methoxy-1-naphthyl)porphyrin, tetra-p-tert-butylcalix[4]arene, tetra-p-tert-butyl Calix[6]arene, tetraazobenzoic acid calix[4]arene, tetraamido-substituted calix[4]arene, dibromodipropoxycalix[4]arene, β-cyclodextrin and its derivatives One of.

In the above-mentioned organic-inorganic hybrid perovskite-based solar cell, the thickness of the ultra-thin alignment layer is 0.5-15 nm, preferably 0.6-10 nm.

In the above-mentioned organic-inorganic hybrid perovskite-based solar cell, the perovskite light-absorbing layer is formed of one or more materials with a general chemical formula of ABX _m Y _3-m crystal structure, wherein A is CH ₃ NH ₃ , C ₄ H ₉ NH ₃ or NH ₂ =CHNH ₂ ; B is Pb, Sn; X, Y are Cl, Br, I; m is 1, 2 or 3, and the thickness of the perovskite light-absorbing layer is 100- 1000nm, preferably 150-550nm.

In the above-mentioned organic-inorganic hybrid perovskite-based solar cell, the electron transport layer is formed of any semiconductor material among TiO ₂ , SnO ₂ , ZnO, PC ₆₁ BM, PC ₇₁ BM, TIPD, ICBA or C60-bis; The thickness of the electron transport layer is 5-150nm, preferably 10-50nm.

In the above-mentioned organic-inorganic hybrid perovskite-based solar cell, the hole transport layer can be formed by using an organic material or an inorganic material, and the organic material is selected from Spiro-OMeTAD, P3HT, PCPDTBT, PEDOT:PSS, NPB and TPD Any one; the inorganic material is selected from any one of CuI, CuSCN, NiO, V ₂ O ₅ and MoO ₃ ; the thickness of the hole transport layer is 5-500nm, preferably 10-150nm.

For the above-mentioned organic-inorganic hybrid perovskite-based solar cell, the composition and mass parts of the coating solution of the ultra-thin alignment layer are:

Cyclic molecules 0.05-5%;

Strong polar organic solvents 95-99.95%.

The cyclic molecules are monobenzo 15-crown-5, styryl 15-crown-5, dibenzo 15-crown-5, dibenzo 18-crown-6, N,N-dimethylnitrile Ethyldiaza-18-crown-6, tetraphenylporphyrin, tetrakis(2-hydroxy-1-naphthyl)porphyrin, tetrakis(2-methoxy-1-naphthyl)porphyrin, tetra- p-tert-butylcalix[4]arene, tetra-p-tert-butyl[6]calix[4]arene, tetraazobenzoylcalix[4]arene, tetraamido-substituted calix[4]arene, dibromodipropoxy One of calix[4]arene, β-cyclodextrin and its derivatives;

Strong polar organic solvent is one or more in dimethylformamide (DMF), dimethyl sulfoxide (DMSO), chloroform, dichloromethane, acetonitrile, pyridine, tetrahydrofuran, ethylene glycol, preferably di Methylformamide (DMF), Dimethylsulfoxide (DMSO).

A method for preparing an organic-inorganic hybrid perovskite-based solar cell, comprising:

Uniformly dispersing the cyclic molecular material in an organic solvent to prepare a transparent and uniform ultra-thin alignment layer solution;

Depositing the solution on the surface of the electron transport layer or the hole transport layer to form a thin film layer by scrape coating, spin coating, spray coating, inkjet printing or pulling method;

The thin film layer is dried in the air at 30-150° C. for 10-120 minutes to form an ultra-thin alignment layer.

A method for preparing an organic-inorganic hybrid perovskite-based solar cell, comprising: uniformly dispersing the ring-shaped molecular material in an organic solvent, and preparing a transparent and uniform ultra-thin alignment layer solution;

Depositing the solution on the surface of the electron transport layer or the hole transport layer by scrape coating, spin coating or spray coating to form a thin film layer;

The thin film layer is dried in the air at 45-120° C. for 20-90 minutes to form an ultra-thin alignment layer.

Compared with the existing direct solution method for preparing perovskite technology, the beneficial effects of the present invention are as follows:

(1) In the present invention, by adding an ultra-thin orientation layer, the cavity of the ring molecule in the ultra-thin orientation layer and the complexation of lead ions can make the perovskite crystal grow directionally during self-assembly, improve crystal regularity, and reduce calcium Defects inside the titanium crystal form a highly crystalline and uniform perovskite layer; effectively increase the carrier diffusion length inside the perovskite layer, prevent electron-hole pairs from recombining inside and at the interface of the perovskite layer, and significantly improve the photoelectric conversion of the battery efficiency and stability.

(2) The cyclic molecules in the ultra-thin alignment layer of the present invention can act as an alignment template, so that the crystal quality of the perovskite light-absorbing layer is not easily affected by the film-forming conditions, and the repeatability of device preparation is improved.

(3) The present invention is applicable to the preparation of perovskite-based solar cells with various structures, making the low-temperature solution method more suitable for the industrial production of large-area perovskite solar cells.

Description of drawings

FIG. 1 is a schematic structural view of an organic-inorganic hybrid perovskite-based solar cell according to the present invention.

Fig. 2 is a schematic structural diagram of another solar cell of the present invention.

The symbols in the figure are represented as: 1-substrate, 2-transparent electrode, 3-electron transport layer, 4-ultra-thin alignment layer, 5-perovskite light-absorbing layer; 6-hole transport layer; 7-counter electrode.

detailed description

In order to make the technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings. The description here is only limited to explaining the present invention, and is not intended to limit the protection scope of the present invention.

The schematic diagram of the structure of Fig. 1 includes a substrate 1, a transparent electrode 2 arranged on the substrate 1, an electron transport layer 3 of semiconductor material is formed on the transparent electrode 2, an ultra-thin alignment layer 4 is formed on the electron transport layer 3, and A perovskite light-absorbing layer 5 formed on the ultra-thin alignment layer 4 , a hole transport layer 6 formed on the perovskite light-absorber layer 5 , and a counter electrode 7 formed on the hole transport layer 6 .

Another structural schematic diagram of Fig. 2, which includes a substrate 1, a transparent electrode 2 arranged on the substrate 1, a hole transport layer 6 is formed on the transparent electrode 2, and an ultra-thin alignment layer is formed on the hole transport layer 6 4. A perovskite light-absorbing layer 5 formed on the ultra-thin alignment layer 4 , an electron transport layer 3 formed on the perovskite light-absorbing layer 5 , and a counter electrode 7 formed on the electron transport layer 3 .

In the organic-inorganic hybrid perovskite-based solar cell shown in Figure 1, before the perovskite light-absorbing layer is prepared by the liquid phase method, the surface of the electron transport layer is modified with a micro-nano structure to form an ultra-thin alignment layer. The preparation method includes The following steps:

1) Clean the transparent electrode, etch the electrode pattern and then clean, dry, and UV/ozone treatment;

2) preparing an electron transport layer on the transparent electrode;

3) Perform interface modification on the surface of the electron transport layer to form an ultra-thin alignment layer;

4) On the surface of the ultra-thin alignment layer, grow a perovskite light-absorbing layer;

5) Depositing a hole transport layer on the surface of the perovskite light-absorbing layer;

6) Prepare a counter electrode on the hole transport layer.

In the organic-inorganic hybrid perovskite-based solar cell shown in Figure 2, before using the liquid phase method to prepare the perovskite light-absorbing layer, the surface of the hole transport layer is modified with a micro-nano structure to form an ultra-thin alignment layer. The preparation method Include the following steps:

1) Clean the transparent electrode, etch the electrode pattern and then clean, dry, and UV/ozone treatment;

2) preparing a hole transport layer on the transparent electrode;

3) Carry out interface modification on the surface of the hole transport layer to form an ultra-thin alignment layer;

4) On the surface of the ultra-thin alignment layer, grow a perovskite light-absorbing layer;

5) Depositing an electron transport layer on the surface of the perovskite light-absorbing layer;

6) Prepare a counter electrode on the electron transport layer.

Take the structure of organic-inorganic hybrid perovskite-based solar cells shown in Figure 1 as an example.

Before preparing the perovskite light-absorbing layer 5 by using the liquid phase method, the electron transport layer 3 is interface-modified to form an ultra-thin alignment layer 4 . The ultra-thin alignment layer 4 is composed of ring-shaped molecules whose cavity inner diameter can complex with lead ions. Through the macrocyclic structure effect of the ring-shaped molecules, the cavity is complexed with the lead ions in _PbI2 molecules, and a layer of uniform arrangement is rapidly formed. The PbI ₂ crystal nucleus clothed controls the growth direction of the PbI ₂ crystal, so that the perovskite crystal grows directional during self-assembly, improves the crystal regularity, and reduces the internal defects of the perovskite crystal. The composition and mass fraction of the ultra-thin alignment layer solution are: 0.05-5% of cyclic molecules; 95-99.95% of strong polar organic solvents.

Cyclic molecules selected from the group consisting of: monobenzo 15-crown-5, styryl 15-crown-5, dibenzo 15-crown-5, dibenzo 18-crown-6, N,N-dimethylnitrile Ethyldiaza-18-crown-6, tetraphenylporphyrin, tetrakis(2-hydroxy-1-naphthyl)porphyrin, tetrakis(2-methoxy-1-naphthyl)porphyrin, tetra- p-tert-butylcalix[4]arene, tetra-p-tert-butyl[6]calix[4]arene, tetraazobenzoylcalix[4]arene, tetraamido-substituted calix[4]arene, dibromodipropoxy Any material such as calix[4]arene, β-cyclodextrin and its derivatives.

The thickness of the ultra-thin alignment layer is 0.5-15nm, preferably 0.6-10nm; the thickness>15nm hinders the transmission of holes from the perovskite light-absorbing layer 5 to the hole-transporting layer 6; the thickness<0.5nm, the film cannot be complete and uniform Covering the surface of the electron transport layer 3, it cannot fully play the role of crystal orientation.

The preparation method of the ultra-thin alignment layer 4 is: uniformly dispersing the ring-shaped molecular material in an organic solvent to prepare a transparent and uniform ultra-thin alignment layer solution; Deposit on the surface of the electron transport layer to form a thin film layer by using method, inkjet printing method or pulling method; dry the thin film layer in air at 30-150°C for 10-120min to form an ultra-thin alignment layer.

Use strong polar organic solvents, including one or more of dimethylformamide (DMF), dimethyl sulfoxide (DMSO), chloroform, dichloromethane, acetonitrile, pyridine, tetrahydrofuran, and ethylene glycol , preferably DMF, DMSO.

The perovskite light-absorbing layer 5 is deposited on the surface of the ultra-thin alignment layer 4 for absorbing sunlight. The perovskite light-absorbing layer 5 is formed from one or more materials whose general chemical formula is ABX _m Y _3-m crystal structure, where A=CH ₃ NH ₃ , C ₄ H ₉ NH ₃ , NH ₂ =CHNH ₂ ; B=Pb, Sn; X, Y=Cl, Br, I; m=1,2,3. The thickness of the perovskite light-absorbing layer film can be 100-1000nm, preferably 150-550nm; if the thickness is greater than 1000nm, electrons and holes cannot be transported to the external circuit in time and recombine inside; if the thickness is less than 100nm, sunlight cannot be fully absorbed.

The perovskite light-absorbing layer 5 can be realized by any one of liquid-phase one-step method, liquid-phase two-step method and gas-assisted liquid-phase method. Liquid-phase one-step method: Dissolve equimolar amounts of PbX ₂ (X=Cl, Br, I) and organic ammonium iodide (CH ₃ NH ₃ I) in γ-butyrolactone or DMF to make a precursor solution, Spin coating on the surface of the ultra-thin alignment layer to form a perovskite light-absorbing layer. The liquid-phase two-step method can be spin-coating and then dipping: dissolve PbI ₂ in DMF solvent, spin-coat on the surface of the ultra-thin alignment layer, and then soak the dried PbI ₂ -layer film in a certain concentration of CH ₃ NH ₃ X(X =Cl, Br, I) solution, after annealing at a certain temperature, a perovskite light-absorbing layer is formed. The liquid-phase two-step method can also be two-step spin coating. First, _PbI2 is dissolved in DMF or DMSO solvent, and then spin-coated on the surface of the ultra-thin alignment layer, and then _CH3NH3X (X= _Cl , Br, I) The perovskite light-absorbing layer is formed by spin-coating on the surface of _PbI2 layer in isopropanol solution and annealed at a certain temperature. The gas-assisted liquid-phase method is to spin-coat the PbI ₂ film first, and then place it in CH ₃ NH ₃ I vapor to slowly form a perovskite light-absorbing layer.

The electron transport layer 3 can be formed by any semiconductor material in TiO ₂ , SnO ₂ , ZnO, PC ₆₁ BM, PC ₇₁ BM, TIPD, ICBA or C ₆₀ -bis; the thickness of the electron transport layer is 5- 150nm, preferably 10-50nm.

Hole transport layer 6 can adopt organic material or inorganic material to form, described organic material is selected from any one in Spiro-OMeTAD, P3HT, PCPDTBT, PEDOT:PSS, NPB and TPD; Described inorganic material is selected from CuI, CuSCN Any one of , NiO, V ₂ O ₅ and MoO ₃ ; the thickness of the hole transport layer is 5-500nm, preferably 10-150nm.

The counter electrode is generally made of materials with higher work function, such as gold, silver, copper, aluminum and other metals, which can be produced by vacuum evaporation and other manufacturing methods.

Another structure of organic-inorganic hybrid perovskite-based solar cells is to form an ultra-thin alignment layer 4 on the hole transport layer 6, and a perovskite light-absorbing layer 5 is formed on the ultra-thin alignment layer 4, and the perovskite An electron transport layer 3 is formed on the light absorbing layer; the rest are the same.

The present invention will be further described in detail below in conjunction with specific examples.

Example 1

The first step is to prepare a transparent electrode:

The ITO conductive glass was etched with concentrated hydrochloric acid to form an electrode pattern, and then ultrasonically cleaned with detergent, deionized water, absolute ethanol, acetone, and isopropanol for 10 minutes, then dried with nitrogen, and treated with UV/ozone for 20 minutes.

The second step is to prepare the electron transport layer:

The precursor solution of nano-TiO ₂ particle colloid was coated on the surface of the transparent electrode by screen printing method, and then placed in a muffle furnace for high temperature sintering at 450 °C for 30 min to form an electron transport layer with a thickness of 45 nm.

The third step is to prepare an ultra-thin alignment layer:

Uniformly dispersing the monobenzo-15-crown-5 cyclic molecular material with a mass fraction of 1% in a chloroform solvent with a mass fraction of 99% to prepare a transparent and uniform ultra-thin alignment layer solution;

The above prepared solution was scraped to form a film with a thickness of 6 nm on the surface of the electron transport layer;

The film prepared above was dried in air at 30° C. for 120 min to form an ultra-thin alignment layer.

The fourth step is to prepare the perovskite light-absorbing layer:

Under the protection of nitrogen, the perovskite light-absorbing layer was prepared on the surface of the interface modification layer by a liquid-phase one-step method, and equal amounts of PbI ₂ and CH ₃ NH ₃ I were dissolved in DMF solution to make a precursor solution with a concentration of 40wt%. Take a certain solution and spin-coat it on the surface of the interface modification layer at a speed of 3000rpm for 30s, then heat and anneal at 100°C for 45min to form a 210nm thick CH ₃ NH ₃ PbI ₃ perovskite light-absorbing layer.

The fifth step is to prepare the hole transport layer:

Under the protection of nitrogen, the hole transport layer was prepared on the perovskite light-absorbing layer by spin coating method, 80mg spiro-OMeTAD, 28.5ml t-BP, 17.5ml Li-TFSI were added to 1ml chlorobenzene, and dissolved to prepare The solution was spin-coated on the surface of the perovskite light-absorbing layer at a rotational speed of 4000 rpm for 30 s to obtain a hole transport layer with a thickness of 100 nm.

The sixth step is to prepare the counter electrode:

A gold electrode was prepared by thermal evaporation on the surface of the hole transport layer, and a gold film with a thickness of 100 nm was vacuum evaporated to form a counter electrode under a vacuum degree of 5×10 ^-4 Pa.

The device structure of organic-inorganic hybrid perovskite-based solar cells prepared by the above method is shown in Figure 1: G/ITO/TiO ₂ /monobenzo15-crown-5/CH ₃ NH ₃ PbI ₃ /spiro-OMeTAD/ Au, the effective area is 0.09cm ² , the photoelectric conversion efficiency data is shown in Table 1, the test conditions: spectral distribution AM1.5G, light intensity 1000W/m ² , AAA solar simulator (Japan SAN-EI company XES-502S+ELS155 type ), the IV curve was measured with a Keithly2400 digital source meter, and all tests were carried out in an atmospheric environment (25°C, 45RH%).

Example 2

Except for the third step, the preparation method of other steps is the same as that of Example 1.

The third step is to prepare an ultra-thin alignment layer:

Uniformly dispersing the tetraphenylporphyrin ring molecular material with a mass fraction of 0.5% in a dichloromethane solvent with a mass fraction of 99.5% to prepare a transparent and uniform ultra-thin alignment layer solution;

Form the above prepared solution on the surface of the electron transport layer by spin-coating to form a film with a thickness of 2nm;

The film prepared above was dried in air at 60° C. for 90 minutes to form an ultra-thin alignment layer.

The device structure of organic-inorganic hybrid perovskite-based solar cells prepared by the above method is shown in Figure 1: G/ITO/TiO ₂ /tetraphenylporphyrin/CH ₃ NH ₃ PbI ₃ /spiro-OMeTAD/Au, The effective area is 0.09cm ² , the photoelectric conversion efficiency data are shown in Table 1, and the test conditions are the same as in Example 1.

Example 3

Except for the third step, the preparation method of other steps is the same as that of Example 1.

The third step is to prepare an ultra-thin alignment layer:

Uniformly dispersing 0.05% by mass of dibenzo-18-crown-6 cyclic molecular material in 99.95% by mass of dimethylformamide solvent to prepare a transparent and uniform ultra-thin alignment layer solution;

The above prepared solution is sprayed to form a film with a thickness of 0.6 nm on the surface of the electron transport layer;

The film prepared above was dried in air at 120° C. for 30 minutes to form an ultra-thin alignment layer.

The device structure of organic-inorganic hybrid perovskite-based solar cells prepared by the above method is shown in Figure 1: G/ITO/TiO ₂ /dibenzo18-crown-6/CH ₃ NH ₃ PbI ₃ /spiro-OMeTAD /Au, the effective area is 0.09 cm ² , the photoelectric conversion efficiency data are shown in Table 1, and the test conditions are the same as in Example 1.

Example 4

Except for the third step, the preparation method of other steps is the same as that of Example 1.

The third step is to prepare an ultra-thin alignment layer:

Uniformly dispersing the β-cyclodextrin cyclic molecular material with a mass fraction of 2.5% in an ethylene glycol solvent with a mass fraction of 97.5% to prepare a transparent and uniform ultra-thin alignment layer solution;

Form the above prepared solution on the surface of the electron transport layer by inkjet printing to form a thin film with a thickness of 9 nm;

The film prepared above was dried in air at 90° C. for 60 minutes to form an ultra-thin alignment layer.

The device structure of organic-inorganic hybrid perovskite-based solar cells prepared by the above method is shown in Figure 1: G/ITO/TiO ₂ /β-cyclodextrin/CH ₃ NH ₃ PbI ₃ /spiro-OMeTAD/Au, The effective area is 0.09cm ² , the photoelectric conversion efficiency data are shown in Table 1, and the test conditions are the same as in Example 1.

Example 5

Except for the third step, the preparation method of other steps is the same as that of Example 1.

The third step is to prepare an ultra-thin alignment layer:

The four-p-tert-butyl[4]calixarene cyclic molecular material with a mass fraction of 5% is uniformly dispersed in a dimethyl sulfoxide solvent with a mass fraction of 95%, and a transparent and uniform ultra-thin oriented layer solution;

The above-mentioned prepared solution is passed through the surface of the electron transport layer by the pulling method to form a film with a thickness of 15nm;

The film prepared above was dried in air at 150° C. for 10 minutes to form an ultra-thin alignment layer.

The device structure of the organic-inorganic hybrid perovskite-based solar cell prepared by the above method is shown in Figure 1: G/ITO/TiO ₂ /Tetrakis-p-tert-butyl[4]calixarene/CH ₃ NH ₃ PbI ₃ /spiro-OMeTAD/Au, the effective area is 0.09cm ² , the photoelectric conversion efficiency data are shown in Table 1, and the test conditions are the same as in Example 1.

Example 6

The first step is to prepare a transparent electrode:

The ITO conductive glass was etched with concentrated hydrochloric acid to form an electrode pattern, and then ultrasonically cleaned with detergent, deionized water, absolute ethanol, acetone, and isopropanol for 10 minutes, then dried with nitrogen, and treated with UV/ozone for 20 minutes.

The second step is to prepare the hole transport layer:

The PEDOT:PSS coating solution was coated by spin coating, the speed of the homogenizer was 5000rpm, spin coating was performed for 30s, and then dried at 150°C for 10min to form a film to form a hole transport layer with a thickness of 40nm.

The third step is to prepare an ultra-thin alignment layer:

Uniformly dispersing the monobenzo-15-crown-5 cyclic molecular material with a mass fraction of 1% in a chloroform solvent with a mass fraction of 99% to prepare a transparent and uniform ultra-thin alignment layer solution;

The above prepared solution was scraped to form a film with a thickness of 6 nm on the surface of the hole transport layer;

The film prepared above was dried in air at 30° C. for 120 min to form an ultra-thin alignment layer.

The fourth step is to prepare the perovskite light-absorbing layer:

Under the protection of nitrogen, the perovskite light-absorbing layer was prepared on the surface of the ultra-thin alignment layer by a liquid-phase two-step method. An appropriate amount of PbI ₂ powder was dissolved in DMF solvent at a concentration of 1mol/L, and the PbI ₂ solution was spin-coated on the ultra-thin alignment layer. The surface of the layer was spin-coated at 6000rpm for 30s and dried in the air to obtain a PbI ₂ layer. Spin-coat the CH ₃ NH ₃ I isopropanol solution with a concentration of 40mg/ml on the surface of the PbI ₂ layer at a speed of 6000rpm for 30s, then heat and anneal at 100°C for 30min to form a 300nm-thick CH ₃ NH ₃ PbI ₃ perovskite absorbing light Floor.

The fifth step is to prepare the electron transport layer:

An electron transport layer was prepared on the surface of the perovskite light-absorbing layer. The PCBM chlorobenzene solution with a concentration of 20 mg/ml was spin-coated on the surface of the perovskite layer at a speed of 1000 rpm for 40 s. After spin coating, it was dried in the air to form an electron transport layer with a thickness of 45 nm.

The sixth step is to prepare the counter electrode:

A gold electrode was prepared by thermal evaporation on the surface of the electron transport layer, and an aluminum film with a thickness of 100 nm was vacuum evaporated to form a counter electrode under a vacuum degree of 5×10 ^-4 Pa.

The device structure of organic-inorganic hybrid perovskite-based solar cells prepared by the above method is shown in Figure 2: G/ITO/PEDOT:PSS/monobenzo15-crown-5/CH ₃ NH ₃ PbI ₃ /PCBM /Al, the effective area is 0.09cm ² , the photoelectric conversion efficiency data are shown in Table 2, the test conditions: spectral distribution AM1.5G, light intensity 1000W/m ² , AAA solar simulator (Japan SAN-EI company XES-502S+ELS155 type), the IV curve was measured with a Keithly2400 digital source meter, and all tests were carried out in an atmospheric environment (25°C, 45RH%).

Example 7

Except for the third step, the preparation method of other steps is the same as in Example 6.

The third step is to prepare an ultra-thin alignment layer:

Uniformly dispersing the tetraphenylporphyrin ring molecular material with a mass fraction of 0.5% in a dichloromethane solvent with a mass fraction of 99.5% to prepare a transparent and uniform ultra-thin alignment layer solution;

The above prepared solution was spin-coated to form a film with a thickness of 2 nm on the surface of the hole transport layer;

The film prepared above was dried in air at 60° C. for 90 minutes to form an ultra-thin alignment layer.

The device structure of organic-inorganic hybrid perovskite-based solar cells prepared by the above method is shown in Figure 2: G/ITO/PEDOT:PSS/tetraphenylporphyrin/CH ₃ NH ₃ PbI ₃ /PCBM/Al, effective The area is 0.09cm ² , the photoelectric conversion efficiency data are shown in Table 2, and the test conditions are the same as in Example 6.

Example 8

Except for the third step, the preparation method of other steps is the same as in Example 6.

The third step is to prepare an ultra-thin alignment layer:

Uniformly dispersing 0.05% by mass of dibenzo-18-crown-6 cyclic molecular material in 99.95% by mass of dimethylformamide solvent to prepare a transparent and uniform ultra-thin alignment layer solution;

The solution prepared above is sprayed to form a film with a thickness of 0.6 nm on the surface of the hole transport layer;

The film prepared above was dried in air at 120° C. for 30 minutes to form an ultra-thin alignment layer.

The device structure of organic-inorganic hybrid perovskite-based solar cells prepared by the above method is shown in Figure 2: G/ITO/PEDOT:PSS/Dibenzo-18-crown-6/CH ₃ NH ₃ PbI ₃ /PCBM/ Al, the effective area is 0.09cm ² , the photoelectric conversion efficiency data are shown in Table 2, and the test conditions are the same as in Example 6.

Example 9

Except for the third step, the preparation method of other steps is the same as in Example 6.

The third step is to prepare an ultra-thin alignment layer:

Uniformly dispersing the β-cyclodextrin cyclic molecular material with a mass fraction of 2.5% in an ethylene glycol solvent with a mass fraction of 97.5% to prepare a transparent and uniform ultra-thin alignment layer solution;

Form the above prepared solution on the surface of the hole transport layer by inkjet printing to form a thin film with a thickness of 9nm;

The film prepared above was dried in air at 90° C. for 60 minutes to form an ultra-thin alignment layer.

The device structure of organic-inorganic hybrid perovskite-based solar cells prepared by the above method is shown in Figure 2: G/ITO/PEDOT:PSS/β-cyclodextrin/CH ₃ NH ₃ PbI ₃ /PCBM/Al, effective The area is 0.09cm ² , the photoelectric conversion efficiency data are shown in Table 2, and the test conditions are the same as in Example 6.

Example 10

Except for the third step, the preparation method of other steps is the same as in Example 6.

The third step is to prepare an ultra-thin alignment layer:

The four-p-tert-butyl[4]calixarene cyclic molecular material with a mass fraction of 5% is uniformly dispersed in a dimethyl sulfoxide solvent with a mass fraction of 95%, and a transparent and uniform ultra-thin oriented layer solution;

Form the above prepared solution on the surface of the hole transport layer by a pulling method to form a thin film with a thickness of 15nm;

The film prepared above was dried in air at 150° C. for 10 minutes to form an ultra-thin alignment layer.

The device structure of organic-inorganic hybrid perovskite-based solar cells prepared by the above method is shown in Figure 2: G/ITO/PEDOT:PSS/tetra-p-tert-butylcalix[4]arene/CH ₃ NH ₃ PbI ₃ /PCBM/Al, the effective area is 0.09cm ² , the photoelectric conversion efficiency data are shown in Table 2, and the test conditions are the same as in Example 6.

Comparative example 1

No ultra-thin alignment layer:

The preparation method of other steps is the same as that of Example 1.

The device structure of organic-inorganic hybrid perovskite-based solar cells prepared by the above method is shown in Figure 1: G/ITO/TiO ₂ /CH ₃ NH ₃ PbI ₃ /spiro-OMeTAD/Au, with an effective area of 0.09 cm ² , the photoelectric conversion efficiency data are shown in Table 1, and the test conditions are the same as in Example 1.

Comparative example 2

No ultra-thin alignment layer.

The preparation method of other steps is the same as that of Example 6.

The device structure of the organic-inorganic hybrid perovskite-based solar cell prepared by the above method is shown in Figure 2: G/ITO/PEDOT:PSS/CH ₃ NH ₃ PbI ₃ /PCBM/Al, the effective area is 0.09cm ² , The photoelectric conversion efficiency data are shown in Table 2, and the test conditions are the same as in Example 6.

Table 1: Data of battery structure examples and comparative examples shown in Figure 1

Table 2: Data of battery structure examples and comparative examples shown in Figure 2

The descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications should also belong to the protection scope of the claims of the present invention.

Claims (10)

1. An organic-inorganic hybrid perovskite-based solar cell is characterized in that the cell structure is a substrate and a transparent electrode, an electron transport layer, an ultra-thin alignment layer, and a perovskite stacked on the substrate in sequence The light absorbing layer, the hole transport layer and the counter electrode, or the battery structure is a substrate and a transparent electrode, a hole transport layer, an ultrathin alignment layer, a perovskite light absorbing layer, an electron transport layer and a counter electrode stacked on the substrate in sequence. electrode; The ultra-thin alignment layer is composed of cyclic molecules whose cavity inner diameter can be complexed with lead ions, and the cyclic molecules are selected from monobenzo 15-crown-5, styryl 15-crown-5, diphenyl And 15-crown-5, dibenzo-18-crown-6, N,N-dimethylnitrile ethyl diaza-18-crown-6, tetraphenylporphyrin, tetrakis (2-hydroxy-1- Naphthyl)porphyrin, tetrakis(2-methoxy-1-naphthyl)porphyrin, tetra-p-tert-butylcalix[4]arene, tetra-p-tert-butyl[6]calixarene, tetraazobenzene One of formate calix[4]arene, tetraamido-substituted calix[4]arene, dibromodipropoxycalix[4]arene, β-cyclodextrin and its derivatives; The thickness of the ultra-thin alignment layer is 0.5-15nm. 2 . The organic-inorganic hybrid perovskite-based solar cell according to claim 1 , wherein the thickness of the ultra-thin alignment layer is 0.6-10 nm. 3. The organic-inorganic hybrid perovskite-based solar cell according to claim 2, characterized in that, the perovskite light-absorbing layer is composed of a kind of crystal structure of ABX _m Y _3-m type or A variety of materials are formed, where A is CH ₃ NH ₃ , C ₄ H ₉ NH ₃ or NH ₂ =CHNH ₂ ; B is Pb, Sn; X, Y are Cl, Br, I; m is 1, 2 or 3, The thickness of the perovskite light-absorbing layer is 100-1000nm. 4 . The organic-inorganic hybrid perovskite-based solar cell according to claim 3 , wherein the thickness of the perovskite light-absorbing layer is 150-550 nm. 5. The organic-inorganic hybrid perovskite-based solar cell according to claim 4, wherein the electron transport layer is made of TiO ₂ , SnO ₂ , ZnO, PC ₆₁ BM, PC ₇₁ BM, TIPD, ICBA or any semiconductor material in C60-bis; the thickness of the electron transport layer is 5-150nm. 6 . The organic-inorganic hybrid perovskite-based solar cell according to claim 5 , wherein the electron transport layer has a thickness of 10-50 nm. 7. The organic-inorganic hybrid perovskite-based solar cell according to claim 6, wherein the hole transport layer is formed of an organic material or an inorganic material, and the organic material is selected from Spiro-OMeTAD, P3HT , PCPDTBT, PEDOT:PSS, NPB and any one in TPD; Described inorganic material is selected from any one in CuI, CuSCN, NiO, V ₂ O ₅ and MoO ₃ ; The thickness of described hole transport layer 10-150nm. 8. The organic-inorganic hybrid perovskite-based solar cell according to claim 7, wherein the composition and parts by mass of the coating solution of the ultra-thin alignment layer are: Cyclic molecules 0.05-5%; Strong polar organic solvent 95-99.95%; The strong polar organic solvent is one or more of dimethylformamide (DMF), dimethylsulfoxide (DMSO), chloroform, dichloromethane, acetonitrile, pyridine, tetrahydrofuran and ethylene glycol. 9. The method for preparing an organic-inorganic hybrid perovskite-based solar cell according to any one of claims 1-8, characterized in that, comprising: Uniformly dispersing the cyclic molecular material in an organic solvent to prepare a transparent and uniform ultra-thin alignment layer solution; Depositing the solution on the surface of the electron transport layer or the hole transport layer to form a thin film layer by scrape coating, spin coating, spray coating, inkjet printing or pulling method; The thin film layer is dried in the air at 30-150° C. for 10-120 minutes to form an ultra-thin alignment layer. 10. The preparation method of the organic-inorganic hybrid perovskite-based solar cell according to claim 9, characterized in that, comprising: Uniformly dispersing the cyclic molecular material in an organic solvent to prepare a transparent and uniform ultra-thin alignment layer solution; Depositing the solution on the surface of the electron transport layer or the hole transport layer by scrape coating, spin coating or spray coating to form a thin film layer; The thin film layer is dried in the air at 45-120° C. for 20-90 minutes to form an ultra-thin alignment layer.