CN104409642B - Preparation method of perovskite/P-type quantum dot composite solar cell - Google Patents

Abstract

The invention discloses a preparation method of a perovskite/P-type quantum dot composite solar cell, belonging to the field of solar cells and nanotechnologies. The perovskite/P-type quantum dot composite solar cell disclosed by the invention is composed of a transparent conducting electrode (1), a compact layer (2), an n-type semiconductor mesoporous layer (3), a perovskite-phase light absorbing layer (4), a p-type semiconductor quantum dot layer (5) and a counter electrode (6). A p-type semiconductor quantum dot is Cu2O, CuI, CuInS2, PbS, PbSe or Sb2S3; expensive organic hole-transport material is replaced; therefore, a photon-generated carrier in the solar cell can be effectively separated; composite of electron and holes is reduced; and the filling factor and the photoelectric conversion efficiency are obviously increased. The perovskite/P-type quantum dot composite solar cell disclosed by the invention is high in photoelectric conversion efficiency, simple in preparation process, low in raw material cost and easy to carry out industrialization implementation.

Description

A kind of preparation method of perovskite/P-type quantum dot composite structure solar cell

technical field

The invention belongs to the technical field of solar cells, and relates to a design scheme of a perovskite/P-type quantum dot composite structure solar cell and a preparation method thereof.

Background technique

Solar energy is an inexhaustible renewable clean energy for human beings. Among the effective utilization of solar energy, the photovoltaic utilization of solar energy is the fastest growing and most dynamic research field in recent years. Perovskite solar cells increase the photoelectric conversion efficiency by an average of 3% per year, which has attracted great attention from the academic community, and was selected as one of the top ten scientific and technological advances in 2013 by Science magazine.

Perovskite solar cells inherit and develop the structure of sensitized solar cells. In 2009, Tsutomu Miyasaka and others assembled a perovskite solar cell with a liquid electrolyte structure and achieved a photoelectric conversion efficiency of 3.81% (Akihiro Kojima and Tsutomu Miyasaka, et al. JACS, 2009, 131:6050-6051); in 2012 Michael et al. replaced the liquid electrolyte to prepare an all-solid-state perovskite solar cell with a photoelectric conversion performance of more than 9% (Hui-Seon Kim and Michael et al.Sci Rep,2012,2:1-7); With the further development of perovskite solar cell research work, planar heterojunction perovskite solar cells, as a new breakthrough, have achieved high In 2014, Yang Yang et al. optimized the perovskite solar cell with a planar junction structure, and the performance broke through 19% (Huanping and Yang Yang, et al. Science, 2014, 345:542-546). However, these high-efficiency perovskite solar cells usually use expensive organic substances (such as spiro-OMeTAD, P3HT, etc.) It has caused problems such as complex preparation, poor stability and strong toxicity, which is not conducive to research work.

Hole transport materials used in perovskite solar cells need to have the characteristics of high hole transport rate, energy level structure matching, good stability and low cost. At present, the reported hole transport materials in perovskite solar cells mainly include organic spiro-OMeTAD, P3HT, PTAA, etc. and inorganic substances CuI and CuSCN. Huazhong University of Science and Technology disclosed a semiconductor perovskite solar cell and its preparation method (application number: 201410357461.4), which involves a preparation method of a mesoporous hole collection layer composed of nano-oxide particles. The Shanghai Institute of Technical Physics, Chinese Academy of Sciences discloses a perovskite solar cell with an inorganic compound as a hole transport layer (application number: 201410121154.6) and a perovskite solar cell with zinc telluride as a hole transport layer (application number : 201410120455.7). Organic hole transport materials are helpful to obtain high-efficiency perovskite solar cell devices, but they need to be improved by adding a variety of additives and are expensive, which is not conducive to research work, while the photoelectric conversion efficiency of inorganic hole transport materials still needs to be improved. The development and preparation of a hole transport material with stable chemical properties, matching energy level structure and low preparation cost is of great significance to the research of perovskite solar cells.

Contents of the invention

The object of the present invention is to provide a perovskite/P-type quantum dot composite structure solar cell design and its preparation method, which can effectively separate solar cells by replacing expensive organic hole transport materials with p-type semiconductor quantum dot materials. The photogenerated carriers in the photoresist reduce the recombination of electrons and holes, and significantly improve the fill factor and photoelectric conversion efficiency.

A method for preparing a perovskite/P-type quantum dot composite structure solar cell, the perovskite/P-type quantum dot composite structure solar cell is composed of a transparent conductive electrode (1), a dense layer (2), an n-type semiconductor mesopore Layer (3), perovskite phase light-absorbing layer (4), p-type semiconductor quantum dot layer (5) and counter electrode (6), the specific preparation steps are as follows:

(a) Prepare a dense layer (2) on the transparent conductive electrode (1): use a spin coating process to coat the oxide precursor solution with a molar concentration of 0.05 to 0.3 on the transparent conductive electrode (1) at 2000 to 5000 rpm ), after sintering at 300-500 degrees Celsius, an oxide dense layer (2) with a thickness of 10-80 nanometers is obtained;

(b) Preparation of n-type semiconductor mesoporous layer (3): Disperse nanometer n-type semiconductor oxides with a particle size of 20 to 50 in absolute ethanol at a mass ratio of 1:2 to 1:5, and use 2000 to 6000 revolutions per minute spin-coating on the dense layer (2), and sintering at 300-500 degrees Celsius to obtain an n-type semiconductor mesoporous layer (3) with a thickness of 150-800 nanometers;

(c) Preparation of perovskite phase light-absorbing layer (4): lead chloride (PbCl ₂ ) or lead iodide (PbI ₂ ) and methylamino iodide (CH ₃ NH ₃ I) in a molar ratio of 1:1～1 : 4 is dissolved in NN dimethylformamide (DMF) solvent to form a precursor solution with a concentration of 0.5 to 1.5 moles, which is coated on the semiconductor mesoporous layer (3) by spin coating at 1000 to 5000 rpm, and heated at 70 to 100 degrees Celsius After heating for 10-60 minutes, an organic-inorganic hybrid CH ₃ NH ₃ PbI _(3-x) Cl _x or CH ₃ NH ₃ PbI ₃ perovskite phase light-absorbing layer (4) with a covering layer thickness of 50-500 nanometers is obtained;

(d) Preparation of the p-type semiconductor quantum dot layer (5): Spin-coat the p-type quantum dot colloidal solution with a molar concentration of 0.05 to 1.0 on the perovskite layer (4) at 1000 to 5000 rpm. heating at 50-100° C. for 5-40 minutes to obtain a p-type semiconductor quantum dot layer (5) with a thickness of 5-500 nanometers;

(e) The counter electrode is to vapor-deposit a layer of gold or silver counter electrode (6) with a thickness of 50-100 nanometers on the surface of the quantum dot layer (5) by vacuum thermal evaporation or electron beam evaporation.

The transparent conductive electrode is fluorine-doped tin oxide (FTO) or indium-doped tin oxide (ITO) transparent conductive glass.

The oxide precursor solution for preparing the dense layer is diisopropyl dititanate n-butanol solution or zinc acetate ethylene glycol methyl ether solution.

The material of the n-type semiconductor mesoporous layer is titanium dioxide (TiO ₂ ) or zinc oxide (ZnO) semiconductor oxide.

The p-type semiconductor quantum dot material is Cu ₂ O, CuI, CuInS ₂ , PbS, PbSe or Sb ₂ S ₃ .

Advantages of the inventive method

The invention uses the p-type semiconductor quantum dot material with simple preparation process and low cost to replace the expensive organic hole transport material, and is an ideal hole transport material. The main advantages are as follows:

1) Adjust the bandgap of quantum dots by controlling the size of p-type quantum dots, and match the energy level of perovskite light-absorbing materials to form a sandwich-like p-i-n junction solar cell;

2) The p-type semiconductor quantum dot material fully penetrates into the pores of the perovskite material and forms a close contact at the interface, which is conducive to the separation of carriers, reduces the recombination of electrons and holes, and significantly improves the filling factor;

3) The p-type quantum dot material has the advantages of controllable band gap, easy modification, simple preparation process and good stability, which simplifies the preparation method while reducing the research cost.

Description of drawings

Figure 1 is a schematic diagram of the structure of a perovskite/P-type quantum dot composite structure solar cell: 1 is a transparent conductive electrode, 2 is a dense layer, 3 is an n-type semiconductor mesoporous layer, 4 is a perovskite phase light-absorbing layer, 5 is P-type semiconductor quantum dot layer, 6 is a counter electrode;

Fig. 2 is the SEM photograph of the perovskite/P-type quantum dot composite structure solar cell prepared by the present invention.

Fig. 3 is the current-voltage (I-V) curve of the perovskite/P-type quantum dot composite structure solar cell prepared in the present invention.

detailed description

Example 1

a) Ultrasonic cleaning of FTO or ITO conductive glass with deionized water, acetone and ethanol in sequence for 15 minutes each, followed by plasma cleaning for 15 minutes after drying. Prepare the n-butanol precursor solution of diisopropyl dititanate or the ethylene glycol methyl ether precursor solution of zinc acetate with a concentration of 0.05-0.3M, mix it evenly, and drop it on the FTO or ITO conductive glass, with 2000 Spin coating at ~5000 rpm for 20-50 seconds, dry at 70 degrees Celsius and sinter at 500 degrees Celsius for 10-50 minutes; b) choose ZnO or TiO ₂ with a particle size of 20 nanometers and absolute ethanol according to 1: 3.5 Mass ratio dilution, using spin coating process, spin coating at 5000 rpm for ₃₀ seconds, drying at 70 degrees Celsius and then sintering at 500 degrees Celsius for ₃₀ minutes _; Dissolve in DMF solution at 1: ₃ to form a precursor solution with a PbCl concentration of 0.8M. Using a spin coating process, spin coating at 2000 rpm for 30 seconds and heat at 100 degrees Celsius for 30 minutes; d) add a concentration of 0.5 M's Cu ₂ O quantum dot colloid is spin-coated at 2000 rpm for 30 seconds, and dried at 50 degrees Celsius; e) select a specific mask to cover the surface of the above sample, and use a vacuum thermal evaporation machine to evaporate A gold counter electrode was plated with a thickness of 60 nm.

Table 1 Effect of different dense layers on solar cell performance

Example 2

a) Ultrasonic cleaning of FTO or ITO conductive glass with deionized water, acetone and ethanol in sequence for 15 minutes each, followed by plasma cleaning for 15 minutes after drying. Prepare the n-butanol precursor solution of diisopropyl dititanate with a concentration of 0.15M, mix it evenly and drop it on the FTO conductive glass, spin-coat it at 2000 rpm for 30 seconds, dry it at 70 degrees Celsius and place it Sinter at 500 degrees Celsius for 10 to 50 minutes; b) Dilute TiO ₂ or ZnO with a particle size of 20 nanometers and absolute ethanol at a mass ratio of 1:2 to 1:5, and use a spin coating process at 2000 to 6000 rpm Min spin coating for 30 seconds, dried at 70 degrees Celsius and then placed at 500 degrees Celsius for 30 minutes to sinter; c) PbCl ₂ and CH ₃ NH ₃ I were dissolved in DMF solution at a molar ratio of 1:3 to form PbCl ₂ with a concentration of 0.8M precursor solution, using a spin coating process, spin coating at 2000 rpm for 30 seconds, and heating at 100 degrees Celsius for 30 minutes; d) Cu ₂ O quantum dot colloid with a concentration of 0.5M using a spin coating process Spin coating at 2000 rpm for 30 seconds, and dry at 50 degrees Celsius; e) select a specific mask to cover the surface of the above sample, and use a vacuum thermal evaporation machine to evaporate a layer of gold counter electrode with a thickness of 60 nanometers.

Table 2 Effect of different n-type semiconductor materials on solar cell performance

Example 3

a) Ultrasonic cleaning of the FTO conductive glass with deionized water, acetone and ethanol in sequence for 15 minutes each, followed by plasma cleaning for 15 minutes after drying. Prepare the n-butanol precursor solution of diisopropyl dititanate with a concentration of 0.15M, mix it evenly and drop it on the FTO conductive glass, spin-coat it at 2000 rpm for 30 seconds, dry it at 70 degrees Celsius and place it Sintering at 500 degrees Celsius for 10 to 50 minutes; b) Dilute TiO ₂ with a particle size of 20 nanometers and absolute ethanol at a mass ratio of 1:3.5, using a spin-coating process, spin-coating at 5000 rpm for 30 seconds, at 70 After drying at 500°C, sintering for 30 minutes; c) (1) spin coating method: prepare a DMF solution of PbCl ₂ and 2.4M CH ₃ NH ₃ I with a concentration of 0.8M, and use a spin coating process to Spin coating at 2000 rpm for 30 seconds, evenly coat the mixed solution on the mesoporous layer, and heat at 100 degrees Celsius for 10 to 60 minutes; (2) Solution method: spin coat a layer on the mesoporous layer by spin coating PbI ₂ with a thickness of 10-500 nanometers, after heating at 70 degrees Celsius for 30 minutes, pre-soaked in isopropanol solution for 1-2 seconds, and quickly transferred to CH ₃ NH ₃ I isopropanol solution with a concentration of 0.06 molar concentration , after 25 seconds of reaction, take it out, wash it, dry it, and heat it at 70 degrees Celsius for 30 minutes; d) Spin-coat the Cu ₂ O quantum dot colloid with a concentration of 0.5M at 2000 rpm for 30 seconds on the Drying at 50 degrees Celsius; e) Select a specific mask to cover the surface of the above sample, and use a vacuum thermal evaporation machine to evaporate a layer of gold counter electrode with a thickness of 60 nanometers.

Table 3 The influence of different preparation processes of perovskite phase light-absorbing layer on the performance of solar cells

Example 4

a) Ultrasonic cleaning of the FTO conductive glass with deionized water, acetone and ethanol in sequence for 15 minutes each, followed by plasma cleaning for 15 minutes after drying. Prepare the n-butanol precursor solution of diisopropyl dititanate with a concentration of 0.15M, mix it evenly and drop it on the FTO conductive glass, spin-coat it at 2000 rpm for 30 seconds, dry it at 70 degrees Celsius and place it Sintering at 500 degrees Celsius for 10 to 50 minutes; b) Dilute TiO ₂ with a particle size of 20 nanometers and absolute ethanol at a mass ratio of 1:3.5, using a spin-coating process, spin-coating at 5000 rpm for 30 seconds, at 70 After drying at 500°C for 30 minutes, sintering at 500°C; c) dissolving PbCl ₂ and CH ₃ NH ₃ I in a DMF solution with a molar ratio of 1:3 to form a precursor solution with a PbCl ₂ concentration of 0.8M, using Spin coating process, spin coating at 2000 rpm for 30 seconds, and heat at 100 degrees Celsius for 30 minutes; d) Cu ₂ O, CuI, CuInS, PbS, PbSe and Sb ₂ S ₃ quantum dots with a molar concentration of 0.05 to 1.0 The colloid is spin-coated at a speed of 1000-5000 revolutions per minute for 10-60 seconds, and dried at 50 degrees Celsius; e) select a specific mask to cover the surface of the above sample, and use a vacuum thermal evaporation machine to evaporate A gold counter electrode was plated with a thickness of 60 nm.

Table 4 Effect of different p-type semiconductor quantum dot materials on solar cell performance

Claims (3)

1. the preparation method of a kind of perovskite/p-type quantum dot composite construction solaode, it is characterised in that be by electrically conducting transparent Electrode (1), compacted zone (2), the mesoporous layer of n-type semiconductor (3), Perovskite Phase light-absorption layer (4), p-type semiconductor quantum dot layer (5) and Electrode (6) is constituted, concrete preparation process is as follows：

A () prepares compacted zone (2) in transparency conductive electrode (1)：Using spin coating proceeding, will with 2000～5000 revs/min The oxide precursor liquid solution of 0.05～0.3 molar concentration is coated in transparency conductive electrode (1), 300～500 degrees Celsius of burnings of Jing After knot, the oxide compacting layer (2) that thickness is 10～80 nanometers is obtained；

The preparation of the mesoporous layer of (b) n-type semiconductor (3)：By the n-type semiconductor oxide in mass ratio 1 that particle diameter is 20～50 nanometers: 2～1:5 are scattered in dehydrated alcohol, are covered on compacted zone (2) with 2000～6000 revs/min of spin coatings, and Jing 300～500 takes the photograph After family name's degree sintering, the mesoporous layer of the n-type semiconductor (3) that thickness is 150～800 nanometers is obtained；

The preparation of (c) Perovskite Phase light-absorption layer (4)：By lead chloride (PbCl₂) or lead iodide (PbI₂) and methylamino iodine (CH₃NH₃I) In molar ratio 1:1～1:4 are dissolved in N-N dimethylformamides (DMF) solvent, form 0.5～1.5 molar concentration precursor aqueous solution, It is covered on the mesoporous layer of quasiconductor (3) with 1000～5000 revs/min of spin coatings, 70～100 degrees Centigrades of Jing 10～60 minutes Afterwards, the organic inorganic hybridization thing CH that overburden cover is 50～500 nanometers is obtained₃NH₃PbI_(3-x)Cl_xOr CH₃NH₃PbI₃Perovskite Phase light-absorption layer (4)；

The preparation of (d) p-type semiconductor quantum dot layer (5)：By the p-type quantum dot colloid solution of 0.05～1.0 molar concentration, with 1000～5000 revs/min of kind spin coatings are covered on calcium titanium ore bed (4), and 50～100 DEG C of Jing is heated 5～40 minutes, and it is 5 to obtain thickness ～500 nanometers of p-type semiconductor quantum dot layer (5)；

(e) be to electrode using vacuum thermal evaporation or electron beam evaporation plating quantum dot layer surface (5) evaporation a layer thickness be 50～ 100 nanometers of golden or silver is to electrode (6)；

Wherein transparency conductive electrode is fluorine doped tin oxide (FTO) or indium doped tin oxide (ITO) transparent conducting glass；

The oxide precursor solution for preparing compacted zone is that two metatitanic acid diisopropyl ester butanol solutions or zinc acetate ethylene glycol monomethyl ether are molten Liquid.

2. the preparation method of a kind of perovskite according to claim 1/p-type quantum dot composite construction solaode, its It is characterised by, the mesoporous layer material of n-type semiconductor is titanium dioxide (TiO₂) or Zinc Oxide (ZnO) conductor oxidate.

3. the preparation method of a kind of perovskite according to claim 1/p-type quantum dot composite construction solaode, its It is characterised by, p-type semiconductor quanta point material is Cu₂O、CuI、CuInS₂, PbS, PbSe or Sb₂S₃。