CN214672679U

CN214672679U - Perovskite solar cell structure

Info

Publication number: CN214672679U
Application number: CN202121080088.4U
Authority: CN
Inventors: 黄斌; 张赟; 赵志国; 秦校军; 肖平; 赵东明; 邬俊波; 李新连; 李梦洁; 夏渊; 熊继光; 董超; 刘家梁; 王百月; 梁思超
Original assignee: Huaneng Clean Energy Research Institute; Huaneng Renewables Corp Ltd
Current assignee: Huaneng Clean Energy Research Institute; Huaneng Renewables Corp Ltd
Priority date: 2021-05-19
Filing date: 2021-05-19
Publication date: 2021-11-09
Anticipated expiration: 2031-05-19

Abstract

The utility model discloses a perovskite solar cell structure belongs to perovskite solar cell preparation technical field. The PEDOT, PSS film and the polyacid film deposited on the PEDOT, PSS film are used as a transparent electrode layer and/or a hole transport layer, the transparent electrode can replace a novel transparent electrode of a traditional ITO transparent electrode, and meanwhile, the novel transparent electrode has high conductivity and high light transmittance in a visible light area, and the novel ITO transparent electrode has the advantages that a functional layer has high conductivity and is beneficial to charge collection and hole transport; the performance of the functional layer film can be regulated and controlled by adjusting the component proportion of the film, and the preparation process is simple and easy to implement, environment-friendly and low in cost. The foundation the utility model discloses a perovskite solar cell of transparent electrode preparation possesses higher charge collection efficiency and the lower charge loss of electrode interface department, and then possesses higher photoelectric conversion efficiency.

Description

Perovskite solar cell structure

Technical Field

The utility model belongs to the technical field of the perovskite solar cell preparation, a perovskite solar cell structure is related to.

Background

The perovskite solar cell is a novel organic/inorganic grocery cell, and the basic structure of the perovskite solar cell comprises a transparent electrode, a hole transport layer, a perovskite active layer, an electron transport layer and a metal electrode layer. Transparent electrodes in perovskite cells generally refer to functional layers with a substrate material and can be generally classified into the following categories: the doped metal Oxide transparent electrode comprises ITO (Indium Tin Oxide), FTO (fluorine doped Tin Oxide), ATO (aluminum doped Tin Oxide), AZO (aluminum doped zinc Oxide) and the like, and the processing technology is generally sputtering film formation; secondly, carbon material transparent electrodes, such as Carbon Nanotubes (CNTs) and Graphene (Graphene), are processed into films by dispersing the electrodes into a solvent through high-power ultrasound or chemical modification and the like and processing the solution; thirdly, the metal nanowires, the metal nano grids and the ultrathin metal film transparent electrodes, the metal species comprise silver, copper, gold and the like, and the processing technology comprises solution processing, thermal evaporation, sputtering and the like; and fourthly, the doped conducting polymer is processed into a film by a solution process.

The ITO transparent electrode is limited in large-scale application for a long time to a certain extent due to a plurality of factors such as complex processing technology, high cost of required equipment, cost disadvantage caused by limited reserves of indium materials, fragility of the materials and the like. The doped conductive polymer has higher conductivity (10 to 10)⁵S/m), the band gap is easy to adjust by means of chemical synthesis, doping and the like, and the characteristics of solution-soluble processing and the like are realized, so that the transparent electrode has unique advantages in the aspect of application. PEDOT is a conductive polymer material developed by Bayer company in Germany in 1988 and having the characteristics of simple molecular structure, small band gap, high conductivity and the like, and then the conductive polymer material is used for realizing high conductivity (>1000S/cm), good thermal stability in an oxidized state, high light transmittance (transmittance in a visible light region-95%, film thickness)<30nm) and the like are widely applied to the fields of organic thin film solar cells, organic light emitting diodes, organic field effect transistors, electrochromic devices and the like. On the other hand, in order to solve the problem that the insolubility of PEDOT per se limits the application,water-soluble sodium polystyrene sulfonate (PSSA) was introduced. The introduction of PSSA realizes the soluble solution processing of PEDOT, and widens the application field thereof. However, the presence of PSS in the film also reduces the conductive properties of PEDOT.

In order to solve the problem of relatively weak conductivity of the PEDOT/PSS film, it has been reported that the conductivity of the film is improved by adding a surfactant and an amphoteric compound to a PEDOT/PSS aqueous solution, or by adding a strong acid, a strong base or a salt compound to the surface of the PEDOT/PSS film. The reported methods for improving the conductivity, such as the method of adding an additive into a solution, have little influence on the improvement of the conductivity, and the methods of surface treatment, such as strong acid treatment and strong alkali treatment, have dangerous reaction conditions and low environmental friendliness.

SUMMERY OF THE UTILITY MODEL

In order to overcome the defects of low conductivity improvement effect and dangerous reaction conditions in the technology for improving the conductivity of the PEDOT/PSS film in the prior art, the utility model aims to provide a perovskite solar cell structure.

In order to achieve the above purpose, the utility model adopts the following technical scheme to realize:

a perovskite solar cell structure comprises a transparent electrode layer, a perovskite active layer, an electron transport layer and a metal electrode layer from bottom to top in sequence,

the transparent electrode layer comprises a transparent substrate and a substrate material laid on the upper surface of the transparent substrate;

the substrate material comprises a PEDOT PSS film and a polyacid film deposited on the PEDOT PSS film.

Preferably, the polyacid film is a molybdate film, phosphomolybdate film, tungstate film, or phosphotungstate film.

Preferably, a hole transport layer is further arranged between the transparent electrode layer and the perovskite active layer.

Further preferably, the hole transport layer is a PTAA semiconductor material or a PEDOT: PSS film.

Preferably, the thickness of the substrate material is 30-150 nm.

Preferably, the transparent substrate is glass, a PET material, a PI material, or a PC material.

Preferably, the thickness of the perovskite active layer is 200-800 nm.

Preferably, the thickness of the metal electrode layer is 50-500 nm.

Preferably, the thickness of the electron transport layer is 10 to 100 nm.

Preferably, the metal electrode layer is made of Cu, Ag, Au, Al, Ni, Fe, or a metal alloy.

Compared with the prior art, the utility model discloses following beneficial effect has:

the utility model provides a perovskite solar cell structure, a transparent electrode can replace a novel transparent electrode of a traditional ITO transparent electrode, and has high conductivity and high light transmittance in a visible light area, and a PEDOT film and a polyacid film deposited on the PEDOT film are used as a transparent electrode layer and a hole transmission layer, so that the perovskite solar cell structure has the advantages that the functional layer has high conductivity, and is beneficial to charge collection and hole transmission; the performance of the functional layer film can be regulated and controlled by adjusting the component proportion of the film, and the preparation process is simple and easy to implement, environment-friendly and low in cost. The foundation the utility model discloses a perovskite solar cell of transparent electrode preparation possesses higher charge collection efficiency and the lower charge loss of electrode interface department, and then possesses higher photoelectric conversion efficiency.

Drawings

FIG. 1 is a basic structural diagram of a perovskite solar cell;

FIG. 2 is a schematic structural diagram of a perovskite solar cell without a hole transport layer;

FIG. 3 is a schematic diagram of the molecular structure of a compound; wherein (a) is PEDOT, PSS molecular structural formula; (b) is a molecular structural formula of PTAA;

FIG. 4 is a graph of the transmittance spectra of different types of transparent electrodes at the wavelength band of 350-900 nm;

fig. 5 is a graph of current density versus voltage for the perovskite solar cell prepared in the example.

Wherein: 1-a transparent electrode layer; 2-a hole transport layer; a 3-perovskite active layer; 4-an electron transport layer; 5-metal electrode layer.

Detailed Description

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

example 1

A perovskite solar cell structure is shown in figure 2 and is characterized by sequentially comprising a transparent electrode layer 1, a perovskite active layer 3, an electron transport layer 4 and a metal electrode layer 5 from bottom to top,

the transparent electrode layer 1 comprises a transparent substrate and a substrate material laid on the upper surface of the transparent substrate;

the substrate material comprises a PEDOT PSS film and a polyacid film deposited on the PEDOT PSS film. The thickness of the substrate material was 150 nm. The thickness of the perovskite active layer 3 was 800nm, the thickness of the metal electrode layer 5 was 500nm, and the thickness of the electron transport layer 4 was 100 nm.

Example 2

As shown in fig. 1, a hole transport layer 2 is further disposed between the transparent electrode layer 1 and the perovskite active layer 3, and the hole transport layer 2 is a PTAA semiconductor material. The thickness of the substrate material was 30 nm. The thickness of the perovskite active layer 3 was 200nm, the thickness of the metal electrode layer 5 was 50nm, and the thickness of the electron transport layer 4 was 10 nm. The remaining features are the same as in example 1.

Example 3

As shown in FIG. 1, a hole transport layer 2 is further arranged between the transparent electrode layer 1 and the perovskite active layer 3, and the thickness of the hole transport layer 2 is 50nm, wherein the hole transport layer is made of a PTAA semiconductor material substrate material. The thickness of the perovskite active layer 3 was 300nm, the thickness of the metal electrode layer 5 was 100nm, and the thickness of the electron transport layer 4 was 30 nm. The remaining features are the same as in example 1.

Example 4

As shown in fig. 1, the substrate material has a thickness of 100 nm. The thickness of the perovskite active layer 3 was 500nm, the thickness of the metal electrode layer 5 was 70nm, and the thickness of the electron transport layer 4 was 50 nm. The remaining features are the same as in example 1.

The transparent substrate is made of glass, a PET material, a PI material, or a PC material.

The perovskite solar cell structure described in the above examples was prepared by the following examples.

Example 5 (reference):

the preparation method of the perovskite solar cell based on the ITO transparent electrode comprises the following steps:

step 1) dissolving 2mg of PTAA (molecular structural formula is shown in figure 3) in 1ml of toluene solvent under nitrogen atmosphere, stirring overnight at room temperature until the PTAA is completely dissolved to prepare a hole transport layer precursor solution;

step 2) the method for cleaning the patterned ITO glass comprises the following steps: the method comprises the following steps: a) immersing the glass in water added with surfactant such as detergent, and performing ultrasonic treatment (power 70W) for 10 min twice; b) after the glass is washed by water until no foam exists, soaking the glass in deionized water for 10 minutes by ultrasonic waves (with the power of 70W) twice; c) immersing the glass in acetone for 10 minutes by ultrasonic waves (power of 70W) twice; d) the glass was immersed in absolute ethanol or isopropanol for 10 minutes twice with ultrasound (power 70W). After 15 minutes of UVO treatment, moving the film into a glove box protected by nitrogen for later use;

and 3) spin-coating the precursor solution of the PTAA hole transport layer obtained in the step (1) on the ITO glass obtained in the step (2), wherein the spin-coating speed is 6000rpm/min, the spin-coating time is 30 seconds, then annealing is carried out for 30 minutes at 100 ℃, and the thickness of the film is about 30nm, so that the hole transport layer 2 is obtained.

Step 4) taking 1290.8mg of PbI₂And 445.2mg of MAI in a mixed solvent of DMF and DMSO (the volume ratio of DMF to DMSO is 4:1), stirring at normal temperature overnight to obtain a perovskite precursor solution, wherein the total concentration of solute in the solution is 1.4 mol/ml.

Step 5) taking 12.5mg of PC₆₁BM is dissolved in 1ml of toluene solvent, and stirred overnight at normal temperature to obtain the precursor solution of the electron transport layer, wherein the concentration of the solution is 12.5 mg/ml.

Step 6) spin-coating the perovskite precursor solution obtained in the step (3) on the hole transport layer 2 obtained in the step (3): the whole spin coating process is divided into three steps, firstly spin coating for 3 seconds at 4000 rpm/min; then spin-coating at 5000rpm/min for 30 seconds; finally, 200 mul of chlorobenzene (anti-solvent) is dripped when the high-speed spin coating is carried out for 11 seconds at 5000rpm/min, all the anti-solvent is dripped within 2 seconds, and the thickness of the perovskite active layer 3 is controlled to be about 500 nm.

And 7) annealing the wafer obtained in the step (6) at 75 ℃ for 2 minutes under the nitrogen protection environment, and then heating to 90 ℃ for annealing for 4 minutes.

Step 8) spin coating the PC obtained in the step (4) on the chip obtained in the step (7)₆₁And (3) spin coating the BM solution at 4000rpm/min for 3 seconds and 5000rpm/min for 30 seconds, wherein the film thickness is about 20 nm.

Step 9) moving the sheet prepared in the step (8) into a vacuum evaporation chamber, and vacuumizing until the vacuum degree is lower than 4 x 10^-4After Pa, preparing the electron transmission layer 4 by a thermal evaporation deposition method; c₆₀The evaporation rate is less than 0.05 angstrom/second, and the film thickness is 20 nm; the evaporation rate of BCP is less than 0.1 angstrom/second, and the film thickness is 9 nm.

Step 10) preparing silver electrode as metal electrode layer 5 from the sheet prepared in step (9) by thermal evaporation deposition method, and controlling vacuum degree to be lower than 4 x 10^-4Pa, the evaporation rate is 1-2 angstroms/second, and the thickness of the silver electrode is 100nm, so that the perovskite battery device is prepared.

Example 6

PSS film is perovskite solar cell of transparent electrode based on PEDOT of molybdic acid primary processing, and the preparation method is as follows: the structure is shown in figure 1.

And step 1), selecting PH1000 as a precursor solution of a PEDOT (Poly ethylene terephthalate) PSS (Poly ethylene sulfide) transparent electrode.

And 2) dropwise adding the solution obtained in the step 1 onto the cleaned and UVO-treated glass substrate, preparing the transparent electrode layer 1 by adopting a spin-coating method, wherein the spin-coating speed is 2000rpm/min, the film thickness is about 50nm, and then annealing for 30 minutes at 120 ℃ in air for later use.

Step 3)25mg of molybdic acid was dissolved in 50ml of methanol solvent, and stirred at room temperature until completely dissolved (clear and transparent solution), to prepare a molybdic acid solution for the first surface treatment, the solution concentration being 0.5 mg/ml.

And 4), soaking the transparent electrode layer 1 obtained in the step (2) into the molybdic acid solution obtained in the step (3) for 30 minutes.

And step 5), rinsing the transparent electrode layer 1 soaked in the step (4) for 2-3 times by using an anhydrous methanol solvent, then annealing at 120 ℃ for 30 minutes, transferring into a nitrogen-protected glove box for later use, and using the once-treated PEDOT (PSS) film as the transparent electrode layer 1 of the perovskite solar cell.

The other functional layers, hole transport layer 2, perovskite active layer 3, electron transport layer 4 and metal electrode layer 5, were prepared as in example 5.

Example 7

Perovskite solar cell preparation based on one-time treatment (treatment of molybdic acid solution with different concentrations) of PEDOT (Poly ethylene terephthalate): PSS (Poly ethylene sulfide) thin film as transparent electrode layer

The procedure of example 6 was repeated except that the concentration of the molybdic acid solution was changed to 1 mg/ml.

Example 8

The procedure of example 6 was repeated except that the concentration of the molybdic acid solution was changed to 2 mg/ml.

Example 9

The procedure of example 6 was repeated except that the concentration of the molybdic acid solution was changed to 5 mg/ml.

Example 10

Perovskite solar cell preparation based on transparent electrode made of PEDOT (Polytetrafluoroethylene) PSS (Polytetrafluoroethylene) thin film subjected to primary treatment (treatment by molybdic acid solution with different concentrations)

The procedure of example 6 was repeated except that the concentration of the molybdic acid solution was changed to 10 mg/ml.

Example 11

Preparation of perovskite solar cell based on PEDOT (polymer stabilized ethylene terephthalate) PSS (patterned sapphire substrate) film subjected to two-time treatment as transparent electrode layer

(1) Preparation of secondary treatment precursor solution of molybdic acid solution: in a nitrogen-blanketed glove box, 0.5mg of molybdic acid was dissolved in 1ml of methanol solvent, and stirred at room temperature until completely dissolved (clear transparent solution), to obtain a molybdic acid solution for the second surface treatment, the concentration of the solution being 0.5 mg/ml.

(2) And (3) dropwise adding the molybdic acid solution with lower concentration prepared in the step (6) to the surface of the transparent electrode subjected to primary treatment prepared in the third embodiment, and spin-coating the molybdic acid solution with low concentration by a glue-spreading method at a spin-coating speed of 3000rpm/min for 30 seconds, wherein the treated transparent electrode is not required to be treated and directly enters the next step.

The preparation of the other functional layers such as the perovskite active layer 3, the electron transport layer 4 and the metal electrode layer 5 is as described in example 5.

Example 12

Preparation of perovskite battery with PEDOT (polymer stabilized organic light emitting diode) PSS (polymer stabilized zirconia) film treated on basis of phosphomolybdic acid as transparent electrode layer

The procedure of example 7 was repeated except for replacing the molybdic acid solution with a phosphomolybdic acid solution having the same concentration (1 mg/ml).

Example 13

Preparation of perovskite battery with PEDOT (polymer stabilized ethylene terephthalate) PSS (polymer stabilized zirconia) film subjected to secondary treatment based on phosphomolybdic acid as transparent electrode layer

The procedure of example 11 was repeated except that the molybdic acid solution was replaced with a phosphomolybdic acid solution having the same concentration (the concentration of the phosphomolybdic acid solution for the first surface treatment was 1mg/ml, and the concentration of the phosphomolybdic acid solution for the second surface treatment was 0.5 ml/ml).

Example 14

PSS film as transparent electrode layer 1 and hole transport layer 2, the structure is shown in FIG 2.

The procedure of example 11 was repeated except that the molybdic acid solution was replaced with a tungstic acid solution of the same concentration (the concentration of the first surface-treated phosphomolybdic acid solution was 1mg/ml, and the concentration of the second surface-treated phosphomolybdic acid solution was 0.5 ml/ml).

Example 15

Preparation of perovskite battery with PEDOT (Poly ethylene terephthalate) (PSS) film as transparent electrode layer 1 and hole transport layer 2 based on phosphotungstic acid secondary treatment

The procedure of example 11 was repeated except that the molybdic acid solution was replaced with a phosphotungstic acid solution of the same concentration (the concentration of the first surface-treated phosphomolybdic acid solution was 1mg/ml, and the concentration of the second surface-treated phosphomolybdic acid solution was 0.5 ml/ml).

It should be noted that the molecular structural formulas of PEDOT, PSS and PTAA used in the examples are shown in FIG. 3.

The ITO glass cleaning method comprises the following steps: a) immersing the glass into water added with a surfactant such as detergent for 10-15 minutes by ultrasonic treatment (power is 20-70W), and carrying out ultrasonic treatment twice; b) after the glass is washed by water until no foam exists, soaking the glass into deionized water for 10-15 minutes by ultrasonic waves (with the power of 20-70W) twice; c) immersing the glass into acetone for 10-15 minutes by ultrasonic waves (with the power of 20-70W) twice; d) immersing the glass into absolute ethyl alcohol or isopropanol, and carrying out ultrasonic treatment (power is 20-70W) for 10-15 minutes twice. After 15 minutes of UVO treatment, the sample was transferred into a nitrogen-protected glove box for further use. The transparent substrate can be made of glass, PET, PI or PC material; the solution film-forming method includes spin coating, wire bar coating, slit extrusion coating, printing and the like.

The ITO transparent electrode and the transparent electrodes prepared in examples 6 to 15 were subjected to a transmittance test in the visible ray region, and the results are shown in fig. 4.

The test results show that the light transmittance of the simple PH1000 film in the long-wave band region above 550nm is obviously lower than that of the ITO film, and the light transmittance of the transparent electrode (example 6, example 7, example 8, example 9, example 10 and example 12) treated by molybdic acid or phosphomolybdic acid for one time in the region (550-900nm) is obviously improved. Wherein a preferred concentration range exists for the treatment of the transparent electrode. When the transparent electrode is treated twice, the test result proves that the light transmittance of molybdic acid, tungstic acid, phosphomolybdic acid and phosphotungstic acid in the whole test area (350-900nm) is obviously superior to that of the ITO transparent electrode, and the average light transmittance is more than 85%. Wherein, the light transmittance of the phosphomolybdic acid and the phosphotungstic acid is more than 90 percent. To sum up the result shows the utility model provides a novel transparent electrode is superior to wide application's ITO transparent electrode in the aspect of visible light zone luminousness.

The cells prepared in the above examples were subjected to a photoelectric property test:

the cell was illuminated with a solar simulator (xenon lamp as light source) at a standard solar light intensity (AM1.5G, 100 mW/cm)²) Tests were performed using silicon diodes (with KG9 visible filter) calibrated in the national renewable energy laboratory. The performance parameters of the batteries were measured and are shown in table 1, and the current density-voltage curve is shown in fig. 5.

Table 1 perovskite solar cell performance parameter table prepared according to different embodiments

Performance test data for perovskite solar cells prepared according to different examples show that: when polyacid primary treatment is adopted, the difference between the surface work function of the transparent electrode and the HOMO energy level between the perovskite active layers is considered, so that compared with a reference battery, the open-circuit voltage and the short-circuit current are both reduced to a certain extent; the surface work function of the transparent electrode after secondary treatment is optimized to a certain degree, so that the open-circuit voltage and the filling factor are superior to those of a reference cell, and the photoelectric conversion efficiency is equivalent to or higher than that of the reference cell.

The above results demonstrate that the PEDOT film of the present invention can be used as both the transparent electrode layer and the hole transport layer of a perovskite cell; in summary, the perovskite solar cell structure has the advantages of simple processing technology, easy realization of large-scale preparation, environmental friendliness, low cost and the like.

The above contents are only for explaining the technical idea of the present invention, and the protection scope of the present invention cannot be limited thereby, and any modification made on the basis of the technical solution according to the technical idea of the present invention all fall within the protection scope of the claims of the present invention.

Claims

1. A perovskite solar cell structure is characterized by sequentially comprising a transparent electrode layer (1), a perovskite active layer (3), an electron transport layer (4) and a metal electrode layer (5) from bottom to top,

the transparent electrode layer (1) comprises a transparent substrate and a substrate material laid on the upper surface of the transparent substrate;

2. The perovskite solar cell structure according to claim 1, wherein a hole transport layer (2) is further provided between the transparent electrode layer (1) and the perovskite active layer (3).

3. The perovskite solar cell structure according to claim 2, wherein the hole transport layer (2) is a PTAA semiconductor material.

4. The perovskite solar cell structure of claim 1, wherein the substrate material has a thickness of 30 to 150 nm.

5. The perovskite solar cell structure of claim 1, wherein the polyacid film is a molybdate film, a phosphomolybdate film, a tungstate film, or a phosphotungstate film.

6. The perovskite solar cell structure of claim 1, wherein the transparent substrate is a glass, a PET material, a PI material, or a PC material.

7. The perovskite solar cell structure according to claim 1, wherein the thickness of the perovskite active layer (3) is 200 to 800 nm.

8. The perovskite solar cell structure according to claim 1, wherein the thickness of the metal electrode layer (5) is 50 to 500 nm.

9. The perovskite solar cell structure according to claim 1, wherein the thickness of the electron transport layer (4) is 10 to 100 nm.

10. The perovskite solar cell structure according to claim 1, wherein the metal electrode layer (5) is made of Cu, Ag, Au, Al, Ni, Fe or a metal alloy.