CN107464882A - A kind of organic inorganic hybridization perovskite solar cell and preparation method thereof - Google Patents

Abstract

The invention discloses an organic-inorganic hybrid perovskite solar cell and a preparation method thereof. The preparation method of the present invention is to deposit a layer of semiconductor dense layer by spray pyrolysis on the transparent conductive electrode; then spray the mixed cation organic-inorganic hybrid perovskite solution on the semiconductor dense layer by thermal substrate spraying method to form a layer Mixed cation organic-inorganic hybrid perovskite film light-absorbing layer; then prepare a hole transport layer on the surface of the light-absorbing layer; finally use thermal evaporation to evaporate gold electrodes to obtain organic-inorganic hybrid perovskite solar cells. The invention adopts thermal substrate spraying method to prepare organic-inorganic hybrid perovskite solar cells, simplifies the preparation process, can quickly prepare large-area perovskite thin films, and is conducive to large-scale application; and the invention optimizes mixed cation organic-inorganic The ratio between the components of the hybrid perovskite solution allows the crystal grain size of the obtained solar cell to exceed 500nm, and the stability is good.

Description

A kind of organic-inorganic hybrid perovskite solar cell and preparation method thereof

technical field

The invention belongs to the technical field of solar energy utilization. More specifically, the invention relates to a novel organic-inorganic hybrid perovskite solar cell and a preparation method thereof.

Background technique

Organic-inorganic hybrid perovskite solar cells (hereinafter referred to as perovskite solar cells) stand out among many new solar cells, attracting the attention of many scientific researchers, and were selected as one of the top ten scientific breakthroughs in 2013 by "Science" one. The light-absorbing material used in this battery is an organic-inorganic hybrid ABX ₃ , where A is a +1-valent organic cation selected from methylamine ions (CH ₃ NH ₃ ⁺ ), ethylamine ions (C ₂ H ₅ NH ₃ ⁺ ) or methyl ether ion (NH ₂ CH=NH ₂ ⁺ ), B is a +2-valent metal ion selected from Sn ²⁺ or Pb ²⁺ , X is a halogen ion selected from Cl ^- , Br ^- or I ^- , is a typical perovskite crystal structure, so the cell is called a perovskite solar cell. Due to its all-solid-state form, it can avoid the problems caused by liquid electrolytes and obtain high conversion efficiency. In just a few years, its photoelectric conversion efficiency has increased from 3.8% in 2009 to 22.1% in 2016. This development speed It is unprecedented, and perovskite solar cells have great potential and application prospects.

Single-cation perovskite materials, such as MAPbI ₃ , have relatively poor stability due to poor crystallinity, while mixed-cation perovskite material systems, such as FAMAPbI ₃ , have larger ionic radius of FA ⁺ compared with MA ⁺ Showing superiority in crystallization kinetics, the incorporation of MA ⁺ can reduce crystal defects and improve crystallinity. Br-doped mixed cation perovskite systems, such as (FAPbI ₃ ) _x (MAPbBr ₃ ) _(1-x) , can adjust the energy gap of perovskite by adjusting the content of Br, and further improve the light conversion efficiency of perovskite materials. and its stability.

At present, the preparation methods of mixed cation perovskite absorbing layer mainly include spin coating method and flash evaporation method, which are not conducive to large-scale application, and the prepared perovskite crystal grain size does not exceed 300nm, and the stability is also poor.

Contents of the invention

The object of the present invention is to: overcome the defects of existing perovskite solar cells with poor stability and grains not exceeding 300nm, and provide an organic solar cell with high stability, suitable for large-scale production, and grains exceeding 500nm. -Inorganic hybrid perovskite solar cell and its preparation method.

In order to achieve the above object of the invention, the present invention provides a method for preparing an organic-inorganic hybrid perovskite solar cell, which comprises the following steps:

(1) Depositing a semiconductor dense layer on the transparent conductive electrode by spray pyrolysis;

(2) Spraying the mixed cation organic-inorganic hybrid perovskite solution on the semiconductor dense layer described in step (1) by thermal substrate spraying method to form a layer of mixed cation organic-inorganic hybrid perovskite film light-absorbing layer;

(3) preparing a hole transport layer on the surface of the mixed cation organic-inorganic hybrid perovskite film light-absorbing layer described in step (2);

(4) Using thermal evaporation to evaporate gold electrodes to obtain organic-inorganic hybrid perovskite solar cells;

Wherein, the general structural formula of the organic-inorganic hybrid perovskite is (FAPbI ₃ ) _x (MAPbBr ₃ ) _(1-x) , and x is 0.7-0.9.

As a preferred technical solution of the method for preparing the organic-inorganic hybrid perovskite solar cell of the present invention, in step (1), the transparent conductive electrode is fluorine-doped tin oxide or aluminum-doped zinc oxide.

As a preferred technical solution of the method for preparing the organic-inorganic hybrid perovskite solar cell of the present invention, the substrate is a glass substrate or a plastic substrate.

As a preferred technical scheme of the preparation method of the organic-inorganic hybrid perovskite solar cell of the present invention, in step (1), the semiconductor dense layer is made of TiO ₂ , ZnO or SnO ₂ as raw materials, and is sprayed by pyrolysis obtained by deposition.

As a preferred technical solution of the preparation method of the organic-inorganic hybrid perovskite solar cell of the present invention, in step (1), the thickness of the semiconductor dense layer is 30-200 nm.

As a preferred technical scheme of the preparation method of the organic-inorganic hybrid perovskite solar cell of the present invention, the preparation method of the mixed cation organic-inorganic hybrid perovskite solution is to mix FAI:PbI ₂ :MABr:PbBr ₂ According to the molar ratio of 0.7～0.9:0.7～0.9:0.1～0.3:0.1～0.3 mixed into the mixed solution of N,N-dimethylformamide and dimethyl sulfoxide, and N,N-dimethylformamide The mass ratio of amide and dimethyl sulfoxide is 7-9.5:1.

As a preferred technical scheme of the preparation method of the organic-inorganic hybrid perovskite solar cell of the present invention, in step (2), the concentration of the mixed cation organic-inorganic hybrid perovskite solution is 0.1 to 0.5 mol/ L.

As a preferred technical scheme of the preparation method of the organic-inorganic hybrid perovskite solar cell of the present invention, in step (2), in the hot substrate spraying method, the carrier gas is nitrogen, and the carrier gas pressure is 2 to 4 Atmospheric pressure, hot substrate temperature is 110-150°C, spray rate is 1-2g/min, spraying time is 10-15s, annealing temperature is 100-150°C, annealing time is 8-20min.

In order to achieve the purpose of the above invention, the present invention also provides an organic-inorganic hybrid perovskite solar cell, which is prepared by the above preparation method.

Compared with the prior art, the present invention has the following beneficial effects:

In the prior art, organic-inorganic hybrid perovskite films are mostly formed by spin-coating in an inert atmosphere, which makes it difficult to prepare large-area films, and the grain size is mostly around 300nm, resulting in poor stability. The invention prepares the organic-inorganic hybrid perovskite thin film by thermal substrate spraying method, which can be realized in the atmospheric environment, does not require a harsh gas environment, and reduces the preparation conditions; the prepared organic-inorganic hybrid perovskite The film is dense, and the grain size can exceed 500nm. The photoelectric conversion efficiency of the prepared organic-inorganic hybrid perovskite solar cell exceeds 12%. After 80 days of storage, the photoelectric conversion efficiency decreases by no more than 5%, and the stability is excellent.

Description of drawings

The organic-inorganic hybrid perovskite solar cell and its preparation method and beneficial effects of the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

Fig. 1 is the organic-inorganic hybrid perovskite solar cell structure of the present invention, wherein, 1 is a transparent conductive electrode (FTO), 2 is a semiconductor dense layer, 3 is a perovskite light-absorbing layer, and 4 is a hole transport layer, 5 is a metal electrode.

Fig. 2 is an SEM image of the (FAPbI ₃ ) _0.85 (MAPbBr ₃ ) _0.15 organic-inorganic hybrid perovskite film of Example 2 of the present invention.

Fig. 3 is the JV curves of (FAPbI ₃ ) _0.85 (MAPbBr ₃ ) _0.15 organic-inorganic hybrid perovskite solar cells stored for 0 days and 80 days in Example 2 of the present invention.

detailed description

In order to make the object, technical solution and beneficial technical effect of the present invention clearer, the present invention will be further described in detail below in conjunction with the examples. It should be understood that the embodiments described in this specification are only for explaining the present invention, not for limiting the present invention, and the parameters and proportions of the embodiments can be selected according to local conditions and have no substantial influence on the results.

Example 1

(1) Deposit a dense layer of _TiO2 on the transparent conductive electrode: add 1g of tetraisopropyl titanate to 1g of acetylacetone and 3g of ethanol to prepare a _TiO2 precursor, and deposit it by spray pyrolysis at 450 °C 50 nm thick _TiO2 dense layer.

(2) Preparation of mixed cation organic-inorganic hybrid perovskite solution: the molar ratio FAI:PbI ₂ :MABr:PbBr ₂ =0.70:070:0.30:0.30 mixture is added to the mixed solution of DMSO and DMF, the mixture of DMF and DMSO The mass ratio is 9:1, and the concentration of the obtained mixed cation organic-inorganic hybrid perovskite solution is 0.3mol/L.

(3) Deposition of perovskite film on TiO ₂ dense layer: In atmospheric environment, the perovskite film was prepared by hot substrate spraying method, in which the carrier gas was N ₂ , the spray gun pressure was 3 atmospheres, and the temperature of the hot substrate was 130 ℃, control the spraying time, the film thickness is 200nm, and then anneal at 100℃ for 15min.

(4) The hole transport layer material (Spiro-OMeTAD) was spin-coated at 4000rpm to form a film. The preparation method of the hole transport layer was: 72.3mg Spiro-OMeTAD was added to 1ml chlorobenzene, stirred until clear, and then added 28.8ul of TBP and 17.5ul of Li-TFSI solution were stirred for 1min.

(5) Finally, a 50nm gold electrode is deposited by thermal evaporation.

The grain size of the prepared perovskite film is 400nm, and the light conversion efficiency of the organic-inorganic hybrid perovskite solar cell is 10.60%. After 80 days, the tested photoelectric conversion efficiency is 9.57%.

Example 2

(1) Deposit a dense layer of _TiO2 on the transparent conductive electrode: add 1g of tetraisopropyl titanate to 1g of acetylacetone and 3g of ethanol to prepare a _TiO2 precursor, and deposit it by spray pyrolysis at 450 °C 50 nm thick _TiO2 dense layer.

(2) Preparation of mixed cation organic-inorganic hybrid perovskite solution: the molar ratio FAI:PbI ₂ :MABr:PbBr ₂ =0.85:0.85:0.15:0.15 mixture is added to the mixed solution of DMSO and DMF, the mixture of DMF and DMSO The mass ratio is 9:1, and the concentration of the obtained mixed cation organic-inorganic hybrid perovskite solution is 0.3 mol/L.

(3) Deposition of perovskite film on TiO ₂ dense layer: In atmospheric environment, the perovskite film was prepared by hot substrate spraying method, in which the carrier gas was N ₂ , the spray gun pressure was 3 atmospheres, and the temperature of the hot substrate was 130 ℃, control the spraying time, the film thickness is 200nm, and then anneal at 100℃ for 15min.

(4) The hole transport layer material (Spiro-OMeTAD) was spin-coated at 4000rpm to form a film. The preparation method of the hole transport layer was: 72.3mg Spiro-OMeTAD was added to 1ml chlorobenzene, stirred until clear, and then added 28.8ul of TBP and 17.5ul of Li-TFSI solution were stirred for 1min.

(5) Finally, a 50nm gold electrode is deposited by thermal evaporation.

The grain size of the prepared perovskite film is 500nm, and the light conversion efficiency of the organic-inorganic hybrid perovskite solar cell is 12.08%. After 80 days, the tested photoelectric conversion efficiency is 12.36%.

Example 3

(1) Deposit a dense layer of _TiO2 on the transparent conductive electrode: add 1g of tetraisopropyl titanate to 1g of acetylacetone and 3g of ethanol to prepare a _TiO2 precursor, and deposit it by spray pyrolysis at 450 °C 50 nm thick _TiO2 dense layer.

(2) Preparation of mixed cation organic-inorganic hybrid perovskite solution: the molar ratio FAI:PbI ₂ :MABr:PbBr ₂ =0.90:0.90:0.10:0.10 mixture is added to the mixed solution of DMSO and DMF, the mixture of DMF and DMSO The mass ratio is 9:1, and the concentration of the obtained mixed cation organic-inorganic hybrid perovskite solution is 0.3 mol/L.

(3) Deposition of perovskite film on TiO ₂ dense layer: In atmospheric environment, the perovskite film was prepared by hot substrate spraying method, in which the carrier gas was N ₂ , the spray gun pressure was 3 atmospheres, and the temperature of the hot substrate was 130 ℃, control the spraying time, the film thickness is 200nm, and then anneal at 100℃ for 15min.

(4) The hole transport layer material (Spiro-OMeTAD) was spin-coated at 4000rpm to form a film. The preparation method of the hole transport layer was: 72.3mg Spiro-OMeTAD was added to 1ml chlorobenzene, stirred until clear, and then added 28.8ul of TBP and 17.5ul of Li-TFSI solution were stirred for 1min.

(5) Finally, a 50nm gold electrode is deposited by thermal evaporation.

The grain size of the prepared perovskite thin film is 450nm, and the light conversion efficiency of the organic-inorganic hybrid perovskite solar cell is 11.24%. After 80 days, the tested photoelectric conversion efficiency is 10.75%.

Example 4

The difference from Example 2 is that the temperature of the hot substrate is 110°C, the grain size of the prepared perovskite film is 300nm, and the light conversion efficiency of the organic-inorganic hybrid perovskite solar cell is 10.20%. After 80 days, the tested The photoelectric conversion efficiency was 9.32%.

Example 5

The difference from Example 2 is that the temperature of the hot substrate is 120°C, the grain size of the prepared perovskite film is 350nm, and the light conversion efficiency of the organic-inorganic hybrid perovskite solar cell is 11.00%. After 80 days, the tested The photoelectric conversion efficiency was 10.37%.

Example 6

The difference from Example 2 is that the temperature of the hot substrate is 140°C, the grain size of the prepared perovskite film is 500nm, and the light conversion efficiency of the organic-inorganic hybrid perovskite solar cell is 11.70%. After 80 days, the tested The photoelectric conversion efficiency was 11.22%.

Example 7

The difference from Example 2 is that the temperature of the hot substrate is 150°C, the grain size of the prepared perovskite film is 450nm, and the light conversion efficiency of the organic-inorganic hybrid perovskite solar cell is 11.55%. After 80 days, the tested The photoelectric conversion efficiency was 10.48%.

Example 8

The difference from Example 2 is that the annealing time is 8min, the grain size of the prepared perovskite film is 300nm, and the light conversion efficiency of the organic-inorganic hybrid perovskite solar cell is 9.25%. After 80 days, the photoelectric conversion of the test The efficiency is 8.18%.

Example 9

The difference from Example 2 is that the annealing time is 10min, the grain size of the prepared perovskite film is 350nm, and the light conversion efficiency of the organic-inorganic hybrid perovskite solar cell is 10.45%. After 80 days, the photoelectric conversion of the test The efficiency is 9.37%.

Example 10

The difference from Example 2 is that the annealing time is 12min, the grain size of the prepared perovskite film is 400nm, and the light conversion efficiency of the organic-inorganic hybrid perovskite solar cell is 11.20%. After 80 days, the photoelectric conversion of the test The efficiency is 10.91%.

Example 11

The difference from Example 2 is that the annealing time is 18min, the grain size of the prepared perovskite film is 450nm, and the light conversion efficiency of the organic-inorganic hybrid perovskite solar cell is 11.82%. After 80 days, the photoelectric conversion of the test The efficiency is 11.21%.

Example 12

The difference from Example 2 is that the annealing time is 20min, the grain size of the prepared perovskite film is 450nm, and the light conversion efficiency of the organic-inorganic hybrid perovskite solar cell is 11.49%. After 80 days, the photoelectric conversion of the test The efficiency is 10.85%.

Example 13

The difference from Example 2 is DMF:DMSO=7:1, the prepared perovskite film grain size is 300nm, and the light conversion efficiency of the organic-inorganic hybrid perovskite solar cell is 10.47%. After 80 days, the test The photoelectric conversion efficiency is 9.75%.

Example 14

The difference from Example 2 is that DMF:DMSO=8:1, the prepared perovskite film grain size is 400nm, and the light conversion efficiency of organic-inorganic hybrid perovskite solar cell is 10.83%. After 80 days, the test The photoelectric conversion efficiency is 10.25%.

Example 15

The difference from Example 2 is that DMF:DMSO=9.5:1, the prepared perovskite film grain size is 500nm, and the light conversion efficiency of organic-inorganic hybrid perovskite solar cell is 11.53%. After 80 days, the test The photoelectric conversion efficiency is 11.05%.

Comparative example 1

(1) Deposit a dense layer of _TiO2 on the transparent conductive electrode: add 1g of tetraisopropyl titanate to 1g of acetylacetone and 3g of ethanol to prepare a _TiO2 precursor, and deposit it by spray pyrolysis at 450 °C 50 nm thick _TiO2 dense layer.

(2) Prepare mixed cation organic-inorganic hybrid perovskite solution: add the molar ratio FAI:PbI ₂ :MAI=0.85:1:0.15 mixture to the mixed solution of DMSO and DMF, the mass ratio of DMF and DMSO is 9: 1. The concentration of the obtained mixed cation organic-inorganic hybrid perovskite solution is 0.3mol/L.

(3) Deposition of perovskite film on TiO ₂ dense layer: In atmospheric environment, the perovskite film was prepared by hot substrate spraying method, in which the carrier gas was N ₂ , the spray gun pressure was 3 atmospheres, and the temperature of the hot substrate was 130 ℃, control the spraying time, the film thickness is 200nm, and then anneal at 100℃ for 15min.

(4) The hole transport layer material (Spiro-OMeTAD) was spin-coated at 4000rpm to form a film. The preparation method of the hole transport layer was: 72.3mg Spiro-OMeTAD was added to 1ml chlorobenzene, stirred until clear, and then added 28.8ul of TBP and 17.5ul of Li-TFSI solution were stirred for 1min.

(5) Finally, a 50nm gold electrode is deposited by thermal evaporation.

The grain size of the prepared perovskite film is 400nm, and the light conversion efficiency of the organic-inorganic hybrid perovskite solar cell is 11.28%. After 80 days, the tested photoelectric conversion efficiency is 7.36%.

Comparative example 2

(1) Deposit a dense layer of _TiO2 on the transparent conductive electrode: add 1g of tetraisopropyl titanate to 1g of acetylacetone and 3g of ethanol to prepare a _TiO2 precursor, and deposit it by spray pyrolysis at 450 °C 50 nm thick _TiO2 dense layer.

(2) Preparation of mixed cation organic-inorganic hybrid perovskite solution: the molar ratio FAI:PbI ₂ :MABr:PbBr ₂ =0.85:0.85:0.15:0.15 mixture is added to the mixed solution of DMSO and DMF, the mixture of DMF and DMSO The mass ratio is 9:1, and the concentration of the obtained mixed cation organic-inorganic hybrid perovskite solution is 0.3 mol/L.

(3) Deposit perovskite film on TiO ₂ dense layer: in glove box, prepare perovskite film by spin coating method, spin coating speed is 4000r/min, spin coating perovskite solution volume is 40ul, spin coating The time is 30s, diethyl ether is added dropwise to remove the solvent during spin coating, and then annealed at 100°C for 15min.

(4) The hole transport layer material (Spiro-OMeTAD) was spin-coated at 4000rpm to form a film. The preparation method of the hole transport layer was: 72.3mg Spiro-OMeTAD was added to 1ml chlorobenzene, stirred until clear, and then added 28.8ul of TBP and 17.5ul of Li-TFSI solution were stirred for 1min.

(5) Finally, a 50nm gold electrode is deposited by thermal evaporation.

The grain size of the prepared perovskite film is 300nm, and the light conversion efficiency of the organic-inorganic hybrid perovskite solar cell is 10.42%. After 80 days, the tested photoelectric conversion efficiency is 6.26%.

Table 1 Example 2 solar cell performance parameters

V _oc (V) J _sc (mA/cm ² ) FF PCE 0day 1.08 17.83 62.7% 12.08% 80 days 1.08 17.63 64.9% 12.36%

Note: V _oc is the open circuit voltage, J _sc is the short circuit current, FF is the fill factor, and PCE is the photoelectric conversion efficiency of the battery.

Table 2 Statistics of perovskite solar cell efficiency in each embodiment

Table 3 comparative example 1 perovskite solar cell efficiency

Table 4 comparative example 2 perovskite solar cell efficiency

According to the disclosure and teaching of the above specification, those skilled in the art to which the present invention pertains can also make appropriate changes and modifications to the above embodiment. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and changes to the present invention should also fall within the protection scope of the claims of the present invention. In addition, although some specific terms are used in this specification, these terms are only for convenience of description and do not constitute any limitation to the present invention.

Claims (9)

1. a kind of preparation method of hybrid inorganic-organic perovskite solar cell, it is characterised in that comprise the following steps：

(1) layer of semiconductor compacted zone is deposited by spray pyrolysis in transparent conductive electrode；

(2) mixed-cation hybrid inorganic-organic perovskite solution is sprayed at step (1) described half by hot substrate spraying process On conductor compacted zone, one layer of mixed-cation hybrid inorganic-organic perovskite thin film light-absorption layer is formed；

(3) hole transport is prepared in step (2) the mixed-cation hybrid inorganic-organic perovskite thin film extinction layer surface Layer；

(4) using thermal evaporation evaporation gold electrode, hybrid inorganic-organic perovskite solar cell is obtained；

Wherein, the general structure of the hybrid inorganic-organic perovskite is (FAPbI₃)_x(MAPbBr₃)_(1-x), x is 0.7~0.9.

2. the preparation method of hybrid inorganic-organic perovskite solar cell according to claim 1, it is characterised in that In step (1), the transparent conductive electrode is fluorine doped tin oxide or Al-Doped ZnO.

3. the preparation method of hybrid inorganic-organic perovskite solar cell according to claim 1, it is characterised in that The substrate is substrate of glass or plastic-substrates.

4. the preparation method of hybrid inorganic-organic perovskite solar cell according to claim 1, it is characterised in that In step (1), the semiconductor compacted zone is with TiO₂, ZnO or SnO₂For raw material, deposit to obtain by spray pyrolysis.

5. the preparation method of hybrid inorganic-organic perovskite solar cell according to claim 4, it is characterised in that In step (1), the thickness of the semiconductor compacted zone is 30~200nm.

6. the preparation method of hybrid inorganic-organic perovskite solar cell according to claim 1, it is characterised in that The preparation method of the mixed-cation hybrid inorganic-organic perovskite solution is by FAI:PbI₂:MABr:PbBr₂According to mole Than 0.7~0.9:0.7~0.9:0.1~0.3:0.1~0.3 is mixed to join DMF and dimethyl sulfoxide (DMSO) In mixed solution, and the mass ratio of DMF and dimethyl sulfoxide (DMSO) is 7~9.5:1.

7. the preparation method of hybrid inorganic-organic perovskite solar cell according to claim 6, it is characterised in that In step (2), the concentration of the mixed-cation hybrid inorganic-organic perovskite solution is 0.1~0.5mol/L.

8. the preparation method of hybrid inorganic-organic perovskite solar cell according to claim 1, it is characterised in that In step (2), in the hot substrate spraying process, carrier gas is nitrogen, and nebulizer gas pressure is 2~4 atmospheric pressure, and hot substrate temperature is 110~150 DEG C, spray speed is 1~2g/min, and spray time is 10~15s, and annealing temperature is 100~150 DEG C, annealing time 8 ~20min.

9. the preparation side of hybrid inorganic-organic perovskite solar cell described in any one claim in claim 1~8 The hybrid inorganic-organic perovskite solar cell that method is prepared.