CN212991123U

CN212991123U - Perovskite solar cell based on composite hole transport layer

Info

Publication number: CN212991123U
Application number: CN202021037541.9U
Authority: CN
Inventors: 章文峰; 林埔安; 黄跃龙
Original assignee: Southwest Petroleum University
Current assignee: Southwest Petroleum University
Priority date: 2020-06-09
Filing date: 2020-06-09
Publication date: 2021-04-16
Anticipated expiration: 2030-06-09

Abstract

The utility model provides a perovskite solar cell based on compound hole transport layer belongs to perovskite solar cell technical field. The composite hole transport layer comprises a PEDOT PSS layer, a hole modification layer is arranged on the PEDOT PSS layer, the hole modification layer is a film of amphiphilic molecules, two ends of the amphiphilic molecules are respectively a polar group and a non-polar group, and the amphiphilic molecules further comprise ester groups. The perovskite solar cell prepared based on the composite hole transport layer improves the yield of PEDOT: the conductivity of the PSS layer improves PEDOT: the PSS is matched with the interface energy level of the perovskite active layer, and meanwhile, the ester group in the amphiphilic molecule inhibits the defects generated on the interface, reduces carrier capture sites, and greatly improves the energy conversion efficiency of the titanium ore solar cell.

Description

Perovskite solar cell based on composite hole transport layer

Technical Field

The utility model relates to a perovskite solar cell technical field, especially a perovskite solar cell based on compound hole transport layer and preparation method thereof.

Background

The generalized perovskite has an ABX3 structure, generally a cubic or octahedral structure, and the A ion is usuallyRefers to organic cations, most commonly

Others such as

(formamidine) and

(ethylamino) also has application where the B ion refers to a metal cation, primarily Pb²⁺And Sn²⁺The X ion being a halide anion, i.e. I^-、Br^-、Cl^-And the like. Perovskite Solar Cells (PSCs) have the advantages of being adaptable to flexible substrates due to excellent photoelectric properties, so that flexible devices can be manufactured, efficiency and cost can be considered, the Perovskite solar cells are judged to be one of ten years of technological progress by scientific magazines in 2013, and the Perovskite solar cells are one of the most potential materials in third-generation solar cells. The high-performance perovskite solar cell is mainly determined by the material properties of all components, mainly determined by the material properties of three main functional layers of a core part hole transmission layer/a perovskite light absorption layer/an electron transmission layer and the matching degree among the three main functional layers, wherein the matching degree can influence the transmission process of current carriers on an interface, a plurality of deep level defects exist at the interface and are sites for recombination reaction of electrons and holes, and therefore interface modification becomes one of main directions for improving the photoelectric conversion efficiency of the perovskite solar cell.

Wherein the weight ratio is based on PEDOT: the trans structure of the PSS hole transport layer is suitable for the preparation of flexible batteries, but PEDOT: the perovskite solar cell with the PSS as the hole transport layer has some disadvantages, namely PEDOT: PSS also has a low mobility, which slows the extraction of holes from the perovskite active layer, while PEDOT: the PSS and the perovskite active layer are not well matched in energy level, and the photoelectric conversion efficiency of the titanium ore solar cell is further reduced.

In view of this, a simpler and more convenient way of increasing PEDOT: the mobility of PSS also reduces or improves PEDOT: the PSS is matched with the energy level of the perovskite active layer, so that the energy conversion efficiency of the perovskite solar cell is improved, and the perovskite solar cell has important economic value and scientific research value.

SUMMERY OF THE UTILITY MODEL

The utility model discloses a solve above technical problem, the utility model provides a perovskite solar cell based on compound hole transport layer and preparation method thereof.

The technical scheme of the utility model as follows:

a perovskite solar cell based on a composite hole transport layer sequentially comprises a transparent substrate, a transparent electrode, a composite hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer and a counter electrode from bottom to top;

the composite hole transport layer comprises a poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonate layer, a hole modification layer is arranged on the poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonate layer, the poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonate layer is connected with the transparent electrode, and the hole modification layer is connected with the perovskite active layer;

the thickness of the poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate layer is 20-100 nm; the thickness of the hole modification layer is 2-15 nm.

Further, the thickness of the poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate layer is 20-60 nm.

Further, the thickness of the hole modification layer is 5-10 nm.

To sum up, owing to adopted above-mentioned technical scheme, the beneficial effects of the utility model are that:

the utility model discloses at PEDOT: the PSS layer is coated with a layer of amphiphilic molecules to form a composite hole transport layer, so that the yield of PEDOT is improved: electrical conductivity of the PSS layer, perovskite solar cell prepared using the prepared composite hole transport layer, PEDOT: the PSS is matched with the interface energy level of the perovskite active layer, and meanwhile, the ester group in the amphiphilic molecule inhibits the defects generated on the interface, reduces carrier capture sites, and greatly improves the energy conversion efficiency of the titanium ore solar cell.

Drawings

FIG. 1 is a schematic diagram of a perovskite solar cell structure;

FIG. 2 is a molecular schematic of glyceryl monostearate;

fig. 3 is a voltage-current characteristic curve of a perovskite solar cell prepared according to an embodiment of the present invention and a comparative example;

fig. 4 is an energy level diagram prepared according to an embodiment of the present invention and a comparative example;

description of the drawings: 1-transparent substrate, 2-transparent electrode, 31-PEDOT, PSS layer, 32-hole modification layer, 4-perovskite active layer, 5-electron transmission layer, 6-hole barrier layer and 7-counter electrode.

Detailed Description

All features disclosed in this specification may be combined in any combination, except features and/or steps that are mutually exclusive.

The present invention will be described in detail with reference to the accompanying drawings.

The utility model provides a compound hole transport layer can improve PEDOT: conductivity of the PSS layer, wherein PEDOT: the PSS layer represents poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate. The composite hole transport layer includes PEDOT, a PSS layer 31; PSS layer 31 is provided with a hole modification layer 32, and the hole modification layer 32 is a film prepared from amphiphilic molecules; the amphiphilic molecule comprises a polar group and a non-polar group, and also comprises an ester group. The amphiphilic molecule comprises one or more of 1-octanoyl-rac-glycerol (C11H22O4), glyceryl monocaprate (C13H26O4), glyceryl laurate (C15H30O4), glyceryl monomyristate (C17H34O4), glyceryl 1-palmitate (C19H38O4), glyceryl linoleate (C21H38O4), glyceryl monooleate (C21H40O4), glyceryl monostearate (C21H42O4), vitamin C stearate, (C24H42O7) glyceryl erucate (C25H48O4) and glyceryl linoleate (C25H50O 4).

The PEDOT PSS layer 31 has a thickness of 20-100nm, preferably 20-60 nm.

The thickness of the hole modification layer 32 is 2-15nm, and the preferable thickness is 5-10 nm.

The weight ratio of PEDOT to PSS in the PEDOT to PSS layer 31 is 1: 2-1: 8, and the preferable weight ratio is 1: 6

Fig. 1 provides a perovskite solar cell based on a composite hole transport layer, which sequentially comprises a transparent substrate 1, a transparent electrode 2, a composite hole transport layer, a perovskite active layer 4, an electron transport layer 5, a hole blocking layer 6 and a counter electrode 7 from bottom to top. The upper surface of the transparent substrate 1 is provided with a transparent electrode 2, the transparent electrode 2 is preferably FTO or ITO, the upper surface of the transparent electrode 2 is provided with a PEDOT/PSS layer 31, the upper surface of the PEDOT/PSS layer 31 is provided with a hole modification layer 32, the upper surface of the perovskite active layer 4 is provided with a titanium ore active layer, the upper surface of the perovskite active layer 4 is provided with an electron transport layer 5, the electron transport layer 5 is preferably [6,6] -phenyl-C61-isopropyl butyrate (PCBM), the upper surface of the electron transport layer 5 is provided with a hole blocking layer 6 Bathocuproine (BCP), the upper surface of the bathocuproine layer is provided with a counter electrode 7, and the counter electrode 7 is preferably silver, so that the perovskite solar cell is.

Example 1

To further illustrate the effect of amphiphilic molecules as the hole modification layer 32 to prepare the composite hole transport layer, glycerol monostearate (C21H42O4) is selected for illustration in this example, and the molecular diagram is shown in fig. 2, wherein one end of the molecule contains a polar group (hydrophilic end) and the other end contains a non-polar group (hydrophobic end), and the amphiphilic molecules further include an ester group.

The present embodiment provides a specific composite hole transport layer and a method for preparing the same.

The composite hole transport layer comprises a PEDOT PSS layer 31 and Glyceryl Monostearate (GMS), wherein the thickness of the PEDOT PSS layer 31 is 40 nm; the thickness of the GMS layer was 8 nm.

The preparation method comprises the following steps: preparing a substrate with a hole transport layer, namely a transparent electrode 2 (ITO) deposited on the upper surface of a transparent substrate 1 (transparent glass in the position) and used as a substrate of the hole transport layer, respectively cleaning the substrate with deionized water, ethanol, acetone, isopropanol and ethanol, blow-drying the substrate with nitrogen after cleaning is finished, and then treating the substrate with ultraviolet ozone for 15 min;

placing the substrate on a spin coater, filtering an aqueous solution of PEDOT: PSS from Heraeus, model number CLEVIOS _ P _ VP _ AI _4083, with a 0.45 μm filter membrane, the weight ratio of PEDOT to PSS in the aqueous solution of PEDOT: PSS being 1: 6, then uniformly coating the entire substrate at a spin speed of 4000rpm for a spin time of 40s, placing the substrate on a hot table after the spin coating is finished and annealing at 150 ℃ for 10min to obtain PEDOT with a thickness of about 40 nm: PSS layer, then coating GMS methanol solution on PEDOT PSS layer 31, wherein the concentration of the GMS methanol solution is 0.5mg/ml, the rotating speed is 5000rpm, the rotating time is 40s, and after the spin coating is finished, the composite hole transport layer formed by the PEDOT PSS/GMS is placed on a hot bench and annealed at 110 ℃ for 10 min.

Example 2

The embodiment provides a preparation method of a perovskite solar cell based on a composite hole transport layer based on embodiment 1, and the preparation method comprises the following steps:

the preparation method comprises the following steps:

(1) preparation work: preparing a substrate with a hole transport layer, namely a transparent electrode 2 (ITO) deposited on the upper surface of a transparent substrate 1 (transparent glass in the position), respectively cleaning the substrate with deionized water, ethanol, acetone, isopropanol and ethanol, blow-drying the substrate with nitrogen after cleaning is finished, and then treating the substrate with ultraviolet ozone for 15 min.

(2) Preparation of PEDOT PSS/GMS composite hole transport layer: placing the substrate on a spin coater, filtering an aqueous solution of PEDOT: PSS with a model of CLEVOS _ P _ VP _ AI _4083 from Heraeus company by using a 0.45 μm filter membrane, wherein the weight ratio of PEDOT to PSS in the aqueous solution of PEDOT: PSS is 1: 6, then uniformly coating the whole substrate, wherein the rotating speed is 4000rpm, the rotating time is 40s, and after the spin coating is finished, placing on a hot bench, annealing at 150 ℃ for 10min to obtain PEDOT with the thickness of about 40 nm: and (3) coating a PSS layer, then coating a GMS methanol solution on the PEDOT PSS layer 31, wherein the GMS methanol solution concentration is 0.5mg/ml, the rotation speed is 5000rpm, the rotation time is 40s, and after the spin coating is finished, the GMS layer is placed on a hot table and annealed at 110 ℃ for 10min to obtain a GMS layer with the thickness of about 8nm, so that the composite hole transport layer consisting of the PEDOT PSS/GMS is obtained.

(3) Preparation of perovskite light absorption layer: the titanium ore active layer is prepared by mixing titanium ore active layer with a molar ratio of 1: 1, dissolving PbI2 and MAI in a mixed solvent of DMSO and DMF, wherein the volume ratio of the DMF to the DMSO is 7: 3, stirring for 12 hours at 60 ℃ under the protection of inert gas (such as N2) to obtain a perovskite precursor MAPbI3 solution, spin-coating the obtained perovskite precursor solution on the composite hole transport layer at normal temperature by a one-step solution spin coating method, wherein the spin coating parameter is 4000rpm, the spin coating time is 40s, dropwise adding an anti-solvent (such as a chlorobenzene solution) in the spin coating process, and then annealing for 5 minutes on a 100 ℃ hot bench to obtain the perovskite light absorption layer with the thickness of about 350 nm;

(4) preparation of the electron transport layer 5: dissolving PCBM in chlorobenzene solvent to obtain PCBM solution with a dissolution concentration of 20mg/ml, and spin-coating the PCBM solution on the perovskite light absorption layer with spin-coating parameters of 2000rpm, spin-coating time of 40s and thickness of about 40nm to obtain the electronic transmission layer 5;

(5) preparation of the hole blocking layer 6: dissolving BCP in isopropanol solvent to obtain BCP solution with the dissolving concentration of 0.5mg/ml, spin-coating the BCP solution on the electron transport layer 5 with the spin-coating parameter of 5000rpm and the spin-coating time of 40s to obtain a hole blocking layer 6BCP layer with the thickness of about 8 nm;

(6) preparation of counter electrode 7: silver with the thickness of 80nm is evaporated on the hole blocking layer 6 as a counter electrode 7 under the vacuum condition, and the perovskite solar cell based on the composite hole transport layer is obtained.

The voltammogram (J-V curve) of the perovskite solar cell prepared in this example under xenon lamp irradiation of 100mW/cm2 is shown in fig. 3, and the energy level diagram of the surface of each layer material of the perovskite solar cell prepared according to this example is shown in fig. 4.

This example provides comparative examples:

preparation of perovskite solar cell based on PEDOT PSS hole transport layer:

(1) preparation work: a substrate with a transparent electrode 2ITO deposited on the upper surface of transparent glass as a hole transport layer is purchased from the market, the substrate is respectively cleaned by deionized water, ethanol, acetone, isopropanol and ethanol, the substrate is blow-dried by nitrogen after cleaning is finished, and then the substrate is treated by ultraviolet ozone for 15 min.

(2) Preparation of PEDOT PSS hole transport layer: placing the substrate on a spin coater, filtering an aqueous solution of PEDOT: PSS with a 0.45 μm filter membrane of the Heraeus company model number CLEVIS _ P _ VP _ AI _4083, wherein the weight ratio of PEDOT to PSS in the aqueous solution of PEDOT: PSS is 1: 6, then uniformly coating the whole substrate, the rotating speed is 4000rpm, the rotating time is 40s, placing the substrate on a hot bench after the spin coating is finished, and annealing at 150 ℃ for 10min to obtain PEDOT with the thickness of about 40 nm: and (3) placing the PSS layer on a hot bench, and annealing at 110 ℃ for 10min to obtain a PEDOT (polymer doped sapphire substrate) and a hole transport layer of the PSS layer 31.

The voltammograms (J-V curves) of the perovskite solar cells prepared in examples and comparative examples under 100mW/cm2 xenon lamp irradiation are shown in fig. 3, and the energy level profiles of the layer materials of the perovskite solar cells are shown in fig. 4.

According to the above examples and comparative examples, in combination with fig. 3, the photoelectric conversion efficiency of the perovskite solar cell based on the PEDOT: PSS/GMS composite hole transport layer is 16.18%, the photoelectric conversion efficiency of the perovskite solar cell based on the PEDOT: PSS hole transport layer is 12.23%, the efficiency is improved by about 32%, and it can be seen from fig. 3 that the open-circuit voltage Voc, the short-circuit current Jsc and the fill factor FF are improved in the performance parameters, and the improvement of the photoelectric conversion efficiency is derived from three aspects. First, according to the schematic diagram of the molecular structure of GMS in fig. 1, GMS has a hydrophilic end at one end and a hydrophobic end at the other end, and a methanol solution of GMS is spin-coated on a PEDOT: PSS film, so that the surface PEDOT: conformation changes of PEDOT chain and PSS chain in PSS, the content ratio of PEDOT to PSS is increased, and the change causes the ratio of PEDOT: the PSS film has high conductivity and high carrier transport speed. And secondly, the GMS contains ester groups, the MAPbI3 active layer is spin-coated on the PEDOT PSS/GMS composite hole transport layer, and the ester groups in the GMS can inhibit the generation of Pb vacancies at the interface of the PEDOT PSS/MAPbI3 active layer, reduce active sites for capturing carriers to generate recombination reaction, and improve the interface of the hole transport layer and the active layer. Finally, as shown in fig. 4, the energy loss of holes in perovskite transported to the PEDOT: PSS/GMS composite hole transport layer was smaller than the energy loss transported to the PEDOT: PSS hole transport layer based on the fact that the work function of the PEDOT: PSS/GMS composite hole transport layer was 5.31eV, the work function of the PEDOT: PSS hole transport layer based on the fact that the work function of the perovskite active layer 4 was 4.98eV, and the valence band of the perovskite active layer 4 was 5.40 eV. Therefore, the photoelectric conversion efficiency of the perovskite solar cell with the PEDOT-PSS/GMS composite hole transport layer is greatly improved.

The above is the embodiment of the present invention. The utility model discloses not limited to above-mentioned embodiment, anybody should learn the structural change who makes under the enlightenment of the utility model, all with the utility model discloses have the same or close technical scheme, all fall into the utility model discloses an within the protection scope.

Claims

1. The perovskite solar cell based on the composite hole transport layer is characterized by comprising a transparent substrate (1), a transparent electrode (2), the composite hole transport layer, a perovskite active layer (4), an electron transport layer (5), a hole blocking layer (6) and a counter electrode (7) from bottom to top in sequence;

the composite hole transport layer comprises a poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonate layer (31), a hole modification layer (32) is arranged on the poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonate layer (31), the poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonate layer (31) is connected with the transparent electrode (2), and the hole modification layer (32) is connected with the perovskite active layer (4);

the thickness of the poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate layer (31) is 20-100 nm; the thickness of the hole modification layer 32 is 2-15 nm.

2. A composite hole transport layer based perovskite solar cell as claimed in claim 1, characterized in that the thickness of the poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate layer (31) is 20-60 nm.

3. A composite hole transport layer based perovskite solar cell according to claim 1 or 2, characterized in that the thickness of the hole modification layer (32) is 5-10 nm.