A method for preparing a perovskite layer and a solar cell

Abstract

The present invention provides a method for preparing a perovskite layer and a solar cell. The perovskite solar cell includes a multi-layer structure, and the multi-layer structure includes a substrate, a tin dioxide transport layer, a binding and modification layer, a lead-based perovskite layer, a hole transport layer, and a back electrode layer arranged in sequence; wherein, the binding and modification layer is formed by nano-microspheres, the nano-microspheres are tin dioxide nano-microspheres, and lead iodide is encapsulated in the tin dioxide nano-microspheres. By introducing the binding and modification layer, it has a good effect of compensating for the gap between the tin dioxide transport layer and the lead-based perovskite layer, and because it is a nano-microsphere material, its dispersibility and lubricity are very excellent, and it will not affect the electron transport efficiency. Moreover, the tin dioxide nano-microspheres have good binding with the tin dioxide transport layer, and the encapsulated lead iodide has good binding with the perovskite layer.

Description

Technical Field

[0001] The present invention relates to a method for preparing a perovskite layer and a solar cell. Background Art

[0002] With the continuous development of economy and technology, the application and popularization of clean energy have been relatively extensive. Obtaining and using more efficient and less polluting energy is the basic direction for future social development and scientific progress.

[0003] Clean energy includes various types, and their generation principles are also different. For example, wind energy, nuclear energy, and solar energy are all typical clean energies.

[0004] Among them, solar energy is a very important representative of clean energy. Solar cells have been adopted in many daily appliances such as water heaters, lighting lamps, watches, etc. In the development of solar cells, one of the current research hotspots is perovskite-type solar cells. It utilizes the semiconductor structure of perovskite-type organic-inorganic metal halides, which can be used as a light-absorbing material and is also called the third-generation solar cell. After data testing, its photoelectric conversion efficiency value has exceeded 20%.

[0005] In the multi-layer structure of a solar cell, generally including a perovskite layer and an electron transport layer, these two layers are directly adjacent. However, in the prior art, it has been found that the gap between these two layers results in poor contact effect, so that its photoelectric conversion efficiency cannot reach a better level. Moreover, the existence of this gap also makes the perovskite light-absorbing layer more vulnerable to the erosion of external oxygen substances, thus reducing its service life. Summary of the Invention

[0006] To solve the problems existing in the above technology, the present invention provides a method capable of filling and modifying the gap between the electron transport layer and the perovskite layer.

[0007] A perovskite solar cell provided by the present invention, the perovskite solar cell includes a multi-layer structure, and the multi-layer structure includes a substrate, a tin dioxide transport layer, a binding and modifying layer, a lead-based perovskite layer, a hole transport layer, and a back electrode layer arranged in sequence; wherein, the binding and modifying layer is formed by nano-microspheres, the nano-microspheres are tin dioxide nano-microspheres, and lead iodide is encapsulated in the tin dioxide nano-microspheres.

[0008] The beneficial effects of the above solution are as follows: By introducing the combined modification layer, it has a good effect of filling and supplementing the gap between the tin dioxide transport layer and the lead-based perovskite layer. Moreover, since it is a material of nanospheres, its dispersibility and lubricity are very excellent, which will not affect the electron transport efficiency. And the tin dioxide nanospheres have good binding properties with the tin dioxide transport layer, while the encapsulated lead iodide has good binding properties with the perovskite layer. That is, through the setting of this material that adsorbs by affinity contact at both ends, the filling of the intermediate layer is realized. And, the introduction of iodide ions will also correspondingly enhance the efficiency performance of the perovskite layer.

[0009] A preferred solution is that the nanospheres are composite nanospheres formed by tin dioxide nanospheres and graphene nanospheres.

[0010] The beneficial effects of the above solution are as follows: By introducing graphene, it can significantly increase the electrical conductivity, that is, improve the efficiency of electron transfer and photoelectric conversion between the two layers, and with the good dispersibility of the combined modification layer, graphene forms a uniformly dispersed effect between the layers.

[0011] A preferred solution is that the substrate is fluorine-doped tin oxide or aluminum-doped zinc oxide, and the thickness of the substrate is 100 nanometers to 500 nanometers; the tin dioxide transport layer forms an electron transport layer, and the thickness of the tin dioxide transport layer is 100 nanometers to 300 nanometers; the combined modification layer is 20 nanometers to 100 nanometers; the lead-based perovskite layer is a light-absorbing material of the ABX3 type, where A is cesium ion, formamidinium ion or methylammonium ion, B is lead element, and X is halogen, and the thickness of the lead-based perovskite layer is 200 nanometers to 500 nanometers; the hole transport layer is NiO, V2O5, CuO or CuSCN, and the thickness of the hole transport layer is 100 nanometers to 200 nanometers; the thickness of the back electrode layer is 100 nanometers to 200 nanometers.

[0012] A preparation method of a perovskite layer provided by the present invention includes the following steps:

[0013] S1: Prepare a substrate.

[0014] S2: Prepare a tin dioxide transport layer as an electron transport layer on the substrate.

[0015] S3: Prepare a combined modification layer on the tin dioxide transport layer, wherein the combined modification layer is formed by nanospheres, the nanospheres are tin dioxide nanospheres, and lead iodide is encapsulated in the tin dioxide nanospheres.

[0016] S4: Prepare a lead-based perovskite layer on the combined modification layer.

[0017] S5: A hole transport layer is formed on the lead-based perovskite layer.

[0018] S6: A back electrode layer is formed on the hole transport layer.

[0019] A preferred solution includes the following steps. After the substrate is cleaned, it is dried with nitrogen.

[0020] The tin dioxide transport layer forms a thin film on the substrate by magnetron sputtering.

[0021] The binding modification layer is loaded on the tin dioxide transport layer by spin coating, and then the lead-based perovskite layer is loaded on the binding modification layer by spin coating again.

[0022] The hole transport layer is deposited on the lead-based perovskite layer by spin coating.

[0023] The back electrode layer forms a thin film on the hole transport layer by evaporation coating.

[0024] A preferred solution includes the following steps. The preparation process of the nano-microspheres of the binding modification layer is as follows: Triphenyltin chloride Ph3SnCl is added to absolute ethanol to obtain a basic solution; at the same time, an NaOH solution is prepared; a uniformly dispersed anhydrous ethanol solution of PbI2 is prepared; the basic solution is slowly dropped into the NaOH solution, and then the anhydrous ethanol solution of PbI2 is slowly dropped; then it is stirred and heated for a certain time; the prepared product is washed and centrifuged to obtain a tin dioxide solid product, which is then dispersed in a solvent for spin coating to form the binding modification layer.

[0025] A preferred solution includes the following steps. The tin dioxide solid product is mixed with graphene nano-microspheres to obtain a composite nano-microsphere product, and the composite nano-microsphere product is uniformly dispersed in a solvent for spin coating to form the binding modification layer.

[0026] A preferred solution includes the following steps. The dosage of triphenyltin chloride is 1 mmol, the absolute ethanol is 100 ml, the concentration of NaOH is 0.01 mmol / ml, the temperature is 150 to 160 °C, and the reaction time is 5 to 10 hours; the molar ratio of PbI2 added to triphenyltin chloride Ph3SnCl is 1:5 to 1:20; in addition, the weight ratio of graphene nano-microspheres in the composite nano-microsphere product is 1% to 10%. Description of the Drawings

[0027] Figure 1It is a schematic cross-sectional view of the perovskite solar cell provided by the present invention. Detailed implementation manners

[0028] First embodiment:

[0029] A perovskite solar cell provided by the present invention, the perovskite solar cell includes a multi-layer structure, and the multi-layer structure includes a substrate, a tin dioxide transport layer, a binding modification layer, a lead-based perovskite layer, a hole transport layer, and a back electrode layer which are sequentially arranged; wherein, the binding modification layer is formed by nano-microspheres, the nano-microspheres are tin dioxide nano-microspheres, and lead iodide is encapsulated in the tin dioxide nano-microspheres.

[0030] A preparation method of a perovskite layer provided by the present invention includes the following steps

[0031] S1: Prepare a substrate.

[0032] S2: Prepare a tin dioxide transport layer as an electron transport layer on the substrate.

[0033] S3: Prepare a binding modification layer on the tin dioxide transport layer, wherein the binding modification layer is formed by nano-microspheres, the nano-microspheres are tin dioxide nano-microspheres, and lead iodide is encapsulated in the tin dioxide nano-microspheres;

[0034] S4: Prepare a lead-based perovskite layer on the binding modification layer;

[0035] S5: Prepare a hole transport layer on the lead-based perovskite layer;

[0036] S6: Prepare a back electrode layer on the hole transport layer.

[0037] In a further preferred step, after the substrate is cleaned, it is dried by nitrogen;

[0038] The tin dioxide transport layer forms a thin film on the substrate by magnetron sputtering;

[0039] The binding modification layer is loaded on the tin dioxide transport layer by spin coating, and the lead-based perovskite layer is loaded on the binding modification layer again by spin coating;

[0040] The hole transport layer is deposited on the lead-based perovskite layer by spin coating;

[0041] The back electrode layer forms a thin film on the hole transport layer by evaporating electrodes.

[0042] Through the introduction of the combined modification layer, it has a good effect of compensating for the gap between the tin dioxide transport layer and the lead-based perovskite layer. And since it is a material of nano microspheres, its dispersibility and lubricity are very excellent and will not affect the electron transport efficiency. Moreover, the tin dioxide nano microspheres have good bonding with the tin dioxide transport layer, and the encapsulated lead iodide has good bonding with the perovskite layer. That is, through the setting of this material with affinity contact adsorption at both ends, the filling of the intermediate layer is realized. And, the introduction of iodide ions will correspondingly enhance the efficiency performance of the perovskite layer.

[0043] Second Embodiment:

[0044] The nano microspheres are composite nano microspheres formed by tin dioxide nano microspheres and graphene nano microspheres. Through the introduction of graphene, it can significantly increase the electrical conductivity, that is, improve the efficiency of electron transfer and photoelectric conversion between the two layers. And due to the good dispersibility of the combined modification layer, graphene forms a uniformly dispersed effect between the layers. In a better composite method, these two kinds of nano microspheres are respectively added into a solvent, then stirred and mixed, and then dried after being uniform to obtain a solid composite nano material, or the solution after stirring and mixing can be directly used for spin coating to form a combined nano layer.

[0045] The substrate is fluorine-doped tin oxide or aluminum-doped zinc oxide, and the thickness of the substrate is 100 nanometers to 500 nanometers; the tin dioxide transport layer forms an electron transport layer, and the thickness of the tin dioxide transport layer is 100 nanometers to 300 nanometers; the combined modification layer is 20 nanometers to 100 nanometers; the lead-based perovskite layer is a light-absorbing material of the ABX3 type, where A is cesium ion, formamidinium ion or methylamine ion, B is lead element, and X is halogen, and the thickness of the lead-based perovskite layer is 200 nanometers to 500 nanometers; the hole transport layer is NiO, V2O5, CuO or CuSCN, and the thickness of the hole transport layer is 100 nanometers to 200 nanometers; the thickness of the back electrode layer is 100 nanometers to 200 nanometers.

[0046] Including the following steps, the preparation process of the nano microspheres of the combined modification layer is: adding triphenyltin chloride Ph3SnCl into absolute ethanol to obtain a basic solution; additionally, preparing a NaOH solution at the same time; additionally preparing a solution of PbI2 in absolute ethanol; slowly dropping the basic solution into the NaOH solution, and then slowly dropping the PbI2 absolute ethanol solution; then stirring and heating for a certain time; washing and centrifuging and drying the prepared product to obtain a tin dioxide solid product, and then dispersing it in a solvent for the spin coating step to form the combined modification layer.

[0047] The tin dioxide solid product is mixed with graphene nanospheres to obtain a composite nanosphere product, and the composite nanosphere product is uniformly dispersed in a solvent for a spin coating step to form the bonding modification layer.

[0048] The dosage of triphenyltin chloride is 1 mmol, absolute ethanol is 100 ml, the concentration of NaOH is 0.01 mmol / ml, the temperature is 150 °C to 160 °C, and the reaction time is 5 hours to 10 hours; the molar ratio of PbI2 added to triphenyltin chloride Ph3SnCl is 1:5 to 1:20; in addition, the weight ratio of graphene nanospheres in the composite nanosphere product is 1% to 10%.

[0049] To further illustrate that the solar cell provided by the present invention has obvious beneficial effects, specific experimental examples and their corresponding efficiency values are given below for comparison and illustration.

[0050] Experimental Example 1: The solar cell obtained by the method of the first embodiment of the present invention, that is, including a substrate substrate, a tin dioxide transport layer, a bonding modification layer, a lead-based perovskite layer, a hole transport layer, and a back electrode layer arranged in sequence; wherein, the bonding modification layer is formed by nanospheres, the nanospheres are tin dioxide nanospheres, and lead iodide is encapsulated in the tin dioxide nanospheres. The molar ratio of PbI2 added to triphenyltin chloride Ph3SnCl is 1:20.

[0051] Experimental Example 2: On the basis of Experimental Example 1, in the bonding nanolayer of Experimental Example 2, the nanospheres are composite nanospheres formed by tin dioxide nanospheres and graphene nanospheres. And, for the proportion of the amount of graphene, which are 1%, 3%, 5%, and 10% respectively, Experimental Example 21, Experimental Example 22, Experimental Example 23, and Experimental Example 24 are obtained respectively.

[0052] Control Example: By using the method of the prior art, the obtained solar cell includes a substrate substrate, a tin dioxide transport layer, a lead-based perovskite layer, a hole transport layer, and a back electrode layer arranged in sequence, that is, it does not include a bonding modification layer.

[0053] In the above examples, the substrate substrate uses an FTO plate, the lead-based perovskite layer uses CH3NH3PbCl3, and the hole transport layer is V2O5.

[0054] Group Efficiency value Experimental Example 1 11.5% Experimental Example 21 13.2% Experimental Example 22 13.9% Experimental Example 23 13.7% Experimental Example 24 13.0% Control Example 7.7%

[0055] Table 1 is the data of the photoelectric efficiency values obtained by the perovskite solar cell provided by the present invention under different experimental examples.

Claims

1. A perovskite solar cell, characterized in that, The perovskite solar cell includes a multi-layer structure, which includes a substrate, a tin dioxide transport layer, a binding modification layer, a lead-based perovskite layer, a hole transport layer, and a back electrode layer arranged in sequence; wherein, the binding modification layer is formed by nano-microspheres, the nano-microspheres are tin dioxide nano-microspheres, and lead iodide is encapsulated in the tin dioxide nano-microspheres; The preparation process of the nano-microspheres of the binding modification layer is as follows: adding triphenyltin chloride Ph3SnCl to absolute ethanol to obtain a basic solution; additionally, preparing a NaOH solution simultaneously; additionally preparing a solution of PbI2 in absolute ethanol; slowly dropping the basic solution into the NaOH solution, and then slowly dropping the PbI2 absolute ethanol solution; then stirring and heating for a certain period of time; the prepared product is washed and centrifugally dried to obtain a tin dioxide solid product, and then dispersed in a solvent for spin coating to form the binding modification layer; Among them, the dosage of triphenyltin chloride is 1 mmol, the absolute ethanol is 100 ml, the concentration of NaOH is 0.01 mmol / ml, the temperature is 150 to 160 °C, and the reaction time is 5 to 10 hours; the molar ratio of added PbI2 to triphenyltin chloride Ph3SnCl is 1:5 to 1:

20.

2. The perovskite solar cell according to claim 1, characterized in that, The nano-microspheres are composite nano-microspheres formed by tin dioxide nano-microspheres and graphene nano-microspheres.

3. The perovskite solar cell according to claim 1, characterized in that The substrate is fluorine-doped tin oxide or aluminum-doped zinc oxide, and the thickness of the substrate is 100 nm to 500 nm; The tin dioxide transport layer forms an electron transport layer, and the thickness of the tin dioxide transport layer is 100 nm to 300 nm; The binding modification layer is 20 nm to 100 nm; The lead-based perovskite layer is a light-absorbing material of the ABX3 type, where A is cesium ion, formamidinium ion or methylammonium ion, B is lead element, and X is halogen, and the thickness of the lead-based perovskite layer is 200 nm to 500 nm; The hole transport layer is NiO, V2O5, CuO or CuSCN, and the thickness of the hole transport layer is 100 nm to 200 nm; The thickness of the back electrode layer is 100 nm to 200 nm.

4. A method for preparing a perovskite layer, characterized in that, Including the following steps, S1: Prepare a substrate; S2: Prepare a tin dioxide transport layer as an electron transport layer on the substrate; S3: Prepare a binding modification layer on the tin dioxide transport layer, wherein the binding modification layer is formed by nano-microspheres, the nano-microspheres are tin dioxide nano-microspheres, and lead iodide is encapsulated in the tin dioxide nano-microspheres; S4: Prepare a lead-based perovskite layer on the binding modification layer; S5: Prepare a hole transport layer on the lead-based perovskite layer; S6: Prepare a back electrode layer on the hole transport layer.

5. The method for preparing a perovskite layer according to claim 4, wherein Including the following steps, after the substrate is cleaned and dried by nitrogen; The tin dioxide transport layer forms a thin film on the substrate by magnetron sputtering; The binding modification layer is loaded on the tin dioxide transport layer by spin coating, and the lead-based perovskite layer is loaded on the binding modification layer again by spin coating; The hole transport layer is deposited on the lead-based perovskite layer by spin coating; The back electrode layer forms a thin film on the hole transport layer by vapor deposition of electrodes.

6. The method for preparing the perovskite layer according to claim 5, characterized in that, It includes the following steps. The tin dioxide solid product is mixed with graphene nanospheres to obtain a composite nanosphere product, and the composite nanosphere product is uniformly dispersed in a solvent for the spin coating step to form the binding modification layer.

7. The method for preparing the perovskite layer according to claim 6, wherein The weight ratio of graphene nanospheres in the composite nanosphere product is 1% to 10%.

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