CN113394343A - Back-incident p-i-n structure perovskite solar cell and preparation method thereof - Google Patents
Back-incident p-i-n structure perovskite solar cell and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 27
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000005751 Copper oxide Substances 0.000 claims abstract description 59
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 58
- 230000005525 hole transport Effects 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 239000002073 nanorod Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims description 33
- 238000000137 annealing Methods 0.000 claims description 24
- 239000011521 glass Substances 0.000 claims description 21
- 230000031700 light absorption Effects 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 13
- 238000004528 spin coating Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical group C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 230000005540 biological transmission Effects 0.000 claims description 5
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 claims description 2
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 9
- 238000005286 illumination Methods 0.000 description 9
- 239000002120 nanofilm Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- 238000000861 blow drying Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000012459 cleaning agent Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 238000002207 thermal evaporation Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
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- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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Abstract
本发明公开了一种背入射p‑i‑n钙钛矿太阳电池及其制备方法，利用垂直生长于FTO衬基上的氧化铜纳米棒阵列作为钙钛矿太阳电池的空穴传输层，并制成以FTO为阴极和透明复合电极（V2O5/Ag/V2O5）为阳极的背入射钙钛矿太阳电池。发现氧化铜纳米棒阵列构筑的背入射p‑i‑n钙钛矿太阳电池的短路电流密度为23.98 mA/cm2，效率为17.46%；与氧化铜纳米薄膜空穴传输层制备的钙钛矿电池相比，氧化铜纳米阵列空穴传输层制备的钙钛矿电池的短路电流密度和效率大幅度提升，短路电流密度提高了约1.4倍，效率增加了约1.7倍。
The invention discloses a back-incidence p-i-n perovskite solar cell and a preparation method thereof. A copper oxide nanorod array vertically grown on a FTO substrate is used as a hole transport layer of the perovskite solar cell, and the A back-incidence perovskite solar cell with FTO as cathode and transparent composite electrode (V 2 O 5 /Ag/V 2 O 5 ) as anode was fabricated. It is found that the short-circuit current density of the back-incident p‑i‑n perovskite solar cell constructed by the copper oxide nanorod array is 23.98 mA/cm 2 and the efficiency is 17.46%; Compared with the battery, the short-circuit current density and efficiency of the perovskite battery prepared by the copper oxide nanoarray hole transport layer are greatly improved, the short-circuit current density is increased by about 1.4 times, and the efficiency is increased by about 1.7 times.
Description
Technical Field
The invention relates to the field of nano semiconductor materials and new energy, in particular to a perovskite solar cell structure and a preparation method thereof.
Background
Hybrid perovskite structure material (CH) synthesized based on organic methylamine and inorganic lead iodide3NH3PbI3) The solar cell prepared has attracted much attention because of its advantages such as high photoelectric conversion efficiency (the highest efficiency is over 22% at present), low cost, and easy preparation [ Nature,2019,567,511 ]. At present, most of high-performance perovskite solar cells are adoptedBy TiO2An n-i-p type device structure constructed by a mesoporous layer/perovskite layer/hole transport layer. TiO 22Require high temperature preparation
While dopants in the Spiro-OMeTAD decrease cell stability [ Science,2017,358,739; advanced Energy Materials,2018,8,1701883 ]. Later, one adopted PEDOT: PSS/perovskite layer/PC61The p-i-n type battery device constructed by BM has relatively simple process, low annealing temperature of the film and small J-V hysteresis effect, and gradually arouses wide interest. The photoelectric conversion efficiency of the device structure is slightly lower than that of an n-i-p structure device, namely, the current PEDOT, PSS, perovskite layer and PC61BM-structured devices have efficiencies in excess of 18% [ Energy ]&Environmental Science,2015,8,1602 ]. The main role of the hole transport layer is to collect and transport photogenerated holes injected from the perovskite thin film layer, thereby realizing effective electron-hole separation, and is an important component of the perovskite solar cell, however, the PEDOT organic hole transport layer commonly used in the structure of the p-i-n device is not ideal because of the imperfect electron blocking performance and the relatively low work function (-5.0eV), thereby causing the open circuit voltage to be generally between 0.95 and 1.0V; on the other hand, the PEDOT, i.e. PSS, has acidity, is very easy to corrode a conductive glass electrode, is not beneficial to the collection of holes, and also reduces the stability of the device [ Nanoscale,2016,8, 11403; [ MEANS FOR solving PROBLEMS ] is provided. PSS material is one of the important research directions of perovskite solar cells.
Compared with the traditional organic hole transport layer, the p-type semiconductor copper oxide material has the characteristics of rich source, low cost, stable air, simple preparation process and the like; more importantly, the valence band energy level and CH of copper oxide3NH3PbI3Are well matched to achieve efficient injection and transport of holes, and thus are successfully used in hole transport layers of perovskite solar cells [ Journal of Materials Chemistry a,2017,5,20381 ]. However, it is not difficult to find that copper oxide as a hole transport layer is all the copper oxide in the study of perovskite solar cells at presentIs a planar thin film structure which greatly limits the active contact area of the perovskite and the copper oxide.
For example, patent CN111463349A discloses a method for improving the stability of perovskite solar cells, but the patent uses a thin film of copper oxide (the contact area of copper oxide with perovskite is small) and it is a bottom incidence structure. When the light enters from the bottom, the copper oxide absorbs visible light, so that the acquisition of photons by the perovskite thin film is influenced, and the problem is avoided by the top incident structure.
Disclosure of Invention
The invention aims to provide a perovskite solar cell and a preparation method thereof, which are used for solving the problem that the contact area between a hole transport layer of the existing p-i-n perovskite solar cell and perovskite is limited, so that the collection loss of photoproduction holes in the perovskite solar cell is caused.
The technical scheme for solving the technical problems comprises the following steps:
a back incidence p-i-n structure perovskite solar cell sequentially comprises a cathode, a copper oxide array, a perovskite light absorption layer, an electron transmission layer and an anode.
The cathode is transparent conductive glass.
The transparent conductive glass is one of fluorine tin oxide, indium tin oxide and aluminum zinc oxide.
The perovskite light absorption layer is selected from CH3NH3PbI3、CH3NH3PbBr3Or CH3NH3PbIxBr1-xOne type of film.
The electronic transmission layer is PC61BM。
The anode is a transparent composite electrode (V)2O5/Ag/V2O5)。
The preparation method of the perovskite solar cell with the back incidence p-i-n structure comprises the following steps:
(1) processing an FTO conductive film;
(2) preparing a copper oxide nano array hole transport layer;
(3) preparing a perovskite light absorption layer;
(4) preparing an electron transport layer;
(5) and (4) preparing a transparent composite electrode.
The preparation steps of the copper oxide nano array hole transport layer are as follows:
(1) dissolving copper acetate in ethanol, and stirring at room temperature to obtain a blue clear transparent solution;
(2) spin-coating the solution on clean FTO conductive glass through a spin coater to obtain a uniform copper acetate film;
(3) annealing in a muffle furnace to obtain a compact copper oxide film;
(4) placing the copper oxide nano-rod array in an aqueous solution consisting of copper nitrate trihydrate and hexamethylenetetramine, sealing, and reacting in an oven at 90 ℃ for 1-2 hours to obtain the copper oxide nano-rod array.
The perovskite light absorption layer is CH3NH3PbI3The perovskite light absorption layer is prepared by the following specific steps: (1) will CH3NH2And PbI2Adding the mixture into an organic mixed solvent, wherein the organic mixed solvent is prepared from gamma-butyrolactone and dimethyl sulfoxide according to a volume ratio of 7: 3, preparing; then stirring to obtain yellow clear perovskite precursor liquid;
(2) spin-coating the perovskite precursor solution on the copper oxide nanorod array obtained in the step by using a spin coater in a nitrogen glove box, and annealing the substrate by using a heating plate in the nitrogen glove box to obtain CH3NH3PbI3A perovskite light absorbing layer.
The preparation method of the electron transport layer comprises the following steps:
(1) will PC61BM powder is dissolved in chlorobenzene;
(2) spin-coating the above solution on CH in a nitrogen glove box by a spin coater3NH3PbI3A perovskite light-absorbing layer;
(3) the substrate was annealed using a hot plate in a nitrogen glove box.
In the present invention, we utilize copper oxide nanoparticlesThe array replaces a copper oxide thin film, which greatly increases the contact area of copper oxide and perovskite, thereby better separating and transferring photogenerated holes in the perovskite; meanwhile, the nanorod array provides a direct hole transmission channel, and the interface charge recombination degree can be reduced, so that the photoelectric performance of the perovskite solar cell can be further improved. In addition, the geometric dimension and the spatial distribution of the array are not easy to change in the using process, the change of the morphological structure of the optical active layer under the illumination temperature is avoided, and the stability of the structure and the performance of the battery is improved. We use a transparent electrode (V)2O5/Ag/V2O5) The conventional top metal electrode is replaced, and the back incidence p-i-n structural perovskite solar cell with the copper oxide nano array as the hole transport layer is obtained.
The invention has the beneficial effects that:
(1) according to the invention, the copper oxide array is adopted to replace the conventional planar thin film as a hole transport layer to prepare the back-incidence p-i-n perovskite solar cell, so that the photocurrent of the cell can be obviously improved. In the invention, the planar copper oxide film is used as a hole transport layer, and the short-circuit current density and the efficiency of the battery are respectively 16.71mA/cm2And 10.21%; PSS film as hole transport layer, and short-circuit current density and efficiency of the cell are 16.35mA/cm2And 10.56%; after the copper oxide array is used as a hole transport layer, the short-circuit current density and efficiency of the cell can obtain 23.98mA/cm2And 17.46%, the cell performance is significantly enhanced.
(2) According to the invention, the copper oxide array is used as a hole transport layer, so that the contact area between the copper oxide and the perovskite can be greatly increased, the photoproduction holes in the perovskite can be better separated and transferred, the collection performance of the holes is improved, and the photocurrent of the battery is improved.
(3) The back-incident p-i-n perovskite solar cell is simple and convenient in preparation method, low in equipment requirement, suitable for large-scale application and high in application value in the fields of photovoltaic materials, low-price solar cell devices and the like.
Drawings
FIG. 1 is a schematic structural diagram of a back-incident p-i-n perovskite solar cell of the present invention; the numerical designations in the drawings illustrate the following: 1. a cathode; 2. a copper oxide nanoarray hole transport layer; 3. CH (CH)3NH3PbI3A perovskite light-absorbing layer; 4. an electron transport layer; 5. and an anode.
Fig. 2 shows the current-voltage performance of a back-incident p-i-n perovskite solar cell under illumination (AM1.5) according to the embodiment of the present invention. Wherein, (a) is the current-voltage performance of the cell under illumination (AM1.5) using 1h copper oxide nanoarrays as hole transport layer, i.e. example 1; (b) in order to use 1.5h copper oxide nanoarrays as the current-voltage performance of the hole transport layer cell under illumination (AM1.5), i.e. example 2; (c) current-voltage performance for cells using 2h copper oxide nanoarrays as hole transport layer under illumination (AM1.5), i.e. example 3.
Fig. 3 shows the current-voltage performance of a back-incident p-i-n perovskite solar cell provided by the comparative example of the invention under illumination (AM 1.5). Wherein (a) is the current-voltage performance of the cell under illumination (AM1.5) using a copper oxide nano-film as a hole transport layer, i.e. comparative example 1; (b) PSS film as hole transport layer cell Current-Voltage performance under illumination (AM1.5), comparative example 2.
Detailed Description
Example 1
Processing the FTO conductive film: and ultrasonically cleaning the FTO conductive glass by using a glass cleaning agent, acetone and isopropanol, blow-drying by using nitrogen, and carrying out ultraviolet-ozone treatment for 30 minutes.
The preparation method of the copper oxide nano array hole transport layer comprises the following steps:
(1) 0.02 g of copper acetate was dissolved in 10ml of ethanol and stirred at room temperature for 12 hours to give a blue, clear and transparent solution.
(2) And (3) rotationally coating the solution on clean FTO conductive glass at the rotating speed of 2000 revolutions per minute by a spin coater to obtain a uniform copper acetate film.
(3) Annealing in a muffle furnace at 350 deg.C for 30 minutes to obtain a compact copper oxide film.
(4) Placing the mixture into an aqueous solution consisting of 0.25mol/L copper nitrate trihydrate and 0.25mol/L hexamethylenetetramine, sealing, and reacting in an oven at 90 ℃ for 1 hour to obtain the copper oxide nanorod array.
CH3NH3PbI3The preparation steps of the perovskite light absorption layer are as follows:
(1) adding 209mg of CH3NH2And 581mg of PbI2Added to 1ml of an organic mixed solvent composed of γ -butyrolactone and dimethyl sulfoxide in a volume ratio of 7: 3, and preparing the product. Then stirring for 2h at 80 ℃ to obtain a yellow clear perovskite precursor solution.
(2) Spin-coating the perovskite precursor solution on the copper oxide nanorod array obtained in the step by using a spin coater in a nitrogen glove box, and annealing the substrate by using a heating plate in the nitrogen glove box to obtain CH3NH3PbI3The annealing temperature of the perovskite light absorption layer is 80 ℃, and the annealing time is 10 minutes.
The preparation steps of the electron transport layer are as follows:
(1) mixing 15mg of PC61BM powder was dissolved in 1ml of chlorobenzene.
(2) The solution was spin coated on CH in a nitrogen glove box by a spin coater at 2000 rpm3NH3PbI3On the perovskite light absorbing layer.
(3) The substrate was annealed in a nitrogen glove box using a hot plate at 80 ℃ for 5 minutes.
Preparing a transparent composite electrode: v with the thickness of 10nm is firstly deposited on the electron transport layer in a vacuum plating cavity by means of thermal evaporation2O5Then silver was deposited to a thickness of 9nm and finally V to a thickness of 40nm2O5。
Example 2
Processing the FTO conductive film: and ultrasonically cleaning the FTO conductive glass by using a glass cleaning agent, acetone and isopropanol, blow-drying by using nitrogen, and carrying out ultraviolet-ozone treatment for 30 minutes.
The preparation method of the copper oxide nano array hole transport layer comprises the following steps:
(1) 0.02 g of copper acetate was dissolved in 10ml of ethanol and stirred at room temperature for 12 hours to give a blue, clear and transparent solution.
(2) And (3) rotationally coating the solution on clean FTO conductive glass at the rotating speed of 2000 revolutions per minute by a spin coater to obtain a uniform copper acetate film.
(3) Annealing in a muffle furnace at 350 deg.C for 30 minutes to obtain a compact copper oxide film.
(4) Placing the mixture into an aqueous solution consisting of 0.25mol/L copper nitrate trihydrate and 0.25mol/L hexamethylenetetramine, sealing, and reacting in an oven at 90 ℃ for 1.5 hours to obtain the copper oxide nanorod array.
CH3NH3PbI3The preparation steps of the perovskite light absorption layer are as follows:
(1) adding 209mg of CH3NH2And 581mg of PbI2Added to 1ml of an organic mixed solvent composed of γ -butyrolactone and dimethyl sulfoxide in a volume ratio of 7: 3, and preparing the product. Then stirring for 2h at 80 ℃ to obtain a yellow clear perovskite precursor solution.
(2) Spin-coating the perovskite precursor solution on the copper oxide nanorod array obtained in the step by using a spin coater in a nitrogen glove box, and annealing the substrate by using a heating plate in the nitrogen glove box to obtain CH3NH3PbI3The annealing temperature of the perovskite light absorption layer is 80 ℃, and the annealing time is 10 minutes.
The preparation steps of the electron transport layer are as follows:
(1) mixing 15mg of PC61BM powder was dissolved in 1ml of chlorobenzene.
(2) The solution was spin coated on CH in a nitrogen glove box by a spin coater at 2000 rpm3NH3PbI3On the perovskite light absorbing layer.
(3) The substrate was annealed in a nitrogen glove box using a hot plate at 80 ℃ for 5 minutes.
Preparing a transparent composite electrode: the electron transport layer is firstly deposited with the thickness of 10nm on the electron transport layer by means of thermal evaporation in a vacuum plating chamberV of2O5Then silver was deposited to a thickness of 9nm and finally V to a thickness of 40nm2O5。
Example 3
Processing the FTO conductive film: and ultrasonically cleaning the FTO conductive glass by using a glass cleaning agent, acetone and isopropanol, blow-drying by using nitrogen, and carrying out ultraviolet-ozone treatment for 30 minutes.
The preparation method of the copper oxide nano array hole transport layer comprises the following steps:
(1) 0.02 g of copper acetate was dissolved in 10ml of ethanol and stirred at room temperature for 12 hours to give a blue, clear and transparent solution.
(2) And (3) rotationally coating the solution on clean FTO conductive glass at the rotating speed of 2000 revolutions per minute by a spin coater to obtain a uniform copper acetate film.
(3) Annealing in a muffle furnace at 350 deg.C for 30 minutes to obtain a compact copper oxide film.
(4) Placing the mixture into an aqueous solution consisting of 0.25mol/L copper nitrate trihydrate and 0.25mol/L hexamethylenetetramine, sealing, and reacting in an oven at 90 ℃ for 2 hours to obtain the copper oxide nanorod array.
CH3NH3PbI3The preparation steps of the perovskite light absorption layer are as follows:
(1) adding 209mg of CH3NH2And 581mg of PbI2Added to 1ml of an organic mixed solvent composed of γ -butyrolactone and dimethyl sulfoxide in a volume ratio of 7: 3, and preparing the product. Then stirring for 2h at 80 ℃ to obtain a yellow clear perovskite precursor solution.
(2) Spin-coating the perovskite precursor solution on the copper oxide nanorod array obtained in the step by using a spin coater in a nitrogen glove box, and annealing the substrate by using a heating plate in the nitrogen glove box to obtain CH3NH3PbI3The annealing temperature of the perovskite light absorption layer is 80 ℃, and the annealing time is 10 minutes.
The preparation steps of the electron transport layer are as follows:
(1) mixing 15mg of PC61BM powder was dissolved in 1ml of chlorobenzene.
(2) Nitrogen glove boxThe solution was spin coated on CH by spin coater at 2000 rpm3NH3PbI3On the perovskite light absorbing layer.
(3) The substrate was annealed in a nitrogen glove box using a hot plate at 80 ℃ for 5 minutes.
Preparing a transparent composite electrode: v with the thickness of 10nm is firstly deposited on the electron transport layer in a vacuum plating cavity by means of thermal evaporation2O5Then silver was deposited to a thickness of 9nm and finally V to a thickness of 40nm2O5。
Comparative example 1
Comparative example 1 is a back-incident p-i-n perovskite solar cell prepared with a copper oxide nano-film hole transport layer.
Processing the FTO conductive film: and ultrasonically cleaning the FTO conductive glass by using a glass cleaning agent, acetone and isopropanol, blow-drying by using nitrogen, and carrying out ultraviolet-ozone treatment for 30 minutes.
The preparation method of the copper oxide nano film hole transport layer comprises the following steps:
(1) 0.02 g of copper acetate was dissolved in 10ml of ethanol and stirred at room temperature for 12 hours to give a blue, clear and transparent solution.
(2) And (3) rotationally coating the solution on clean FTO conductive glass at the rotating speed of 2000 revolutions per minute by a spin coater to obtain a uniform copper acetate film.
(3) Annealing in a muffle furnace at 350 deg.C for 30 minutes to obtain a compact copper oxide film.
CH3NH3PbI3The preparation steps of the perovskite light absorption layer are as follows:
(1) adding 209mg of CH3NH2And 581mg of PbI2Added to 1ml of an organic mixed solvent composed of γ -butyrolactone and dimethyl sulfoxide in a volume ratio of 7: 3, and preparing the product. Then stirring for 2h at 80 ℃ to obtain a yellow clear perovskite precursor solution.
(2) Spin-coating the perovskite precursor solution on the copper oxide nano-film obtained in the step by using a spin coater in a nitrogen glove box, and annealing the substrate by using a heating plate in the nitrogen glove boxTo obtain CH3NH3PbI3The annealing temperature of the perovskite light absorption layer is 80 ℃, and the annealing time is 10 minutes.
The preparation steps of the electron transport layer are as follows:
(1) mixing 15mg of PC61BM powder was dissolved in 1ml of chlorobenzene.
(2) The solution was spin coated on CH in a nitrogen glove box by a spin coater at 2000 rpm3NH3PbI3On the perovskite light absorbing layer.
(3) The substrate was annealed in a nitrogen glove box using a hot plate at 80 ℃ for 5 minutes.
Preparing a transparent composite electrode: v with the thickness of 10nm is firstly deposited on the electron transport layer in a vacuum plating cavity by means of thermal evaporation2O5Then silver was deposited to a thickness of 9nm and finally V to a thickness of 40nm2O5。
Comparative example 2
Comparative example 2 is a back-incident p-i-n perovskite solar cell prepared from a PEDOT PSS organic thin film hole transport layer.
Processing the FTO conductive film: and ultrasonically cleaning the FTO conductive glass by using a glass cleaning agent, acetone and isopropanol, blow-drying by using nitrogen, and carrying out ultraviolet-ozone treatment for 30 minutes.
Preparation of PEDOT PSS organic hole transport layer: firstly, filtering a PEDOT/PSS solution by using a 0.45-micrometer filter head, and then spin-coating the PEDOT/PSS solution on a clean FTO conductive substrate by using a spin coater under the air, wherein the spin-coating speed is 4500 rpm for 60 s. And then heat-treated at 145 ℃ for 10 minutes in air to obtain a PEDOT PSS film layer as a hole transport layer.
CH3NH3PbI3The preparation steps of the perovskite light absorption layer are as follows:
(1) adding 209mg of CH3NH2And 581mg of PbI2Added to 1ml of an organic mixed solvent composed of γ -butyrolactone and dimethyl sulfoxide in a volume ratio of 7: 3, and preparing the product. Then stirring for 2h at 80 ℃ to obtain a yellow clear perovskite precursor solution.
(2) Spin-coating the perovskite precursor solution on the copper oxide nano-film obtained in the step by using a spin coater in a nitrogen glove box, and annealing the substrate by using a heating plate in the nitrogen glove box to obtain CH3NH3PbI3The annealing temperature of the perovskite light absorption layer is 80 ℃, and the annealing time is 10 minutes.
The preparation steps of the electron transport layer are as follows:
(1) mixing 15mg of PC61BM powder was dissolved in 1ml of chlorobenzene.
(2) The solution was spin coated on CH in a nitrogen glove box by a spin coater at 2000 rpm3NH3PbI3On the perovskite light absorbing layer.
(3) The substrate was annealed in a nitrogen glove box using a hot plate at 80 ℃ for 5 minutes.
Preparing a transparent composite electrode: v with the thickness of 10nm is firstly deposited on the electron transport layer in a vacuum plating cavity by means of thermal evaporation2O5Then silver was deposited to a thickness of 9nm and finally V to a thickness of 40nm2O5。
The current-voltage (J-V) performance characterization results of the perovskite solar cells prepared in the embodiments 1, 2, 3, 1 and 2 under illumination (AM1.5) are shown in the attached figure 2. The J-V test is completed in an air room temperature environment; the short-circuit current density and the efficiency of the perovskite battery prepared by the copper oxide nano film hole transport layer are respectively 16.71mA/cm2And 10.21%. The short-circuit current density and the efficiency of the perovskite battery prepared by the PEDOT-PSS nano film hole transport layer are respectively 16.35mA/cm2And 10.56%. Compared with the perovskite battery prepared by the copper oxide nano film and the PEDOT/PSS organic film hole transport layer, the perovskite battery prepared by the copper oxide nano array hole transport layer has greatly improved short-circuit current density and efficiency, and the detailed comparison is shown in Table 1.
Table 1.
Note: the J-V performance test is completed in a laboratory environment, and the effective area of the battery is 16mm2；Voc、JscFF and η are the open circuit voltage, short circuit current, fill factor and conversion efficiency of the cell, respectively.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and those skilled in the art can make various corresponding changes and modifications according to the present invention without departing from the spirit and the essence of the present invention, but these corresponding changes and modifications should fall within the protection scope of the appended claims.
Claims (10)
1. A back incidence p-i-n structure perovskite solar cell is characterized in that: the cathode, the copper oxide array, the perovskite light absorption layer, the electron transmission layer and the anode are sequentially included.
2. A back-incident p-i-n structural perovskite solar cell as claimed in claim 1, wherein: the cathode is transparent conductive glass.
3. A back-incident p-i-n structural perovskite solar cell as claimed in claim 1, wherein: the transparent conductive glass is one of fluorine tin oxide, indium tin oxide and aluminum zinc oxide.
4. A back-incident p-i-n structural perovskite solar cell as claimed in claim 1, wherein: the perovskite light absorption layer is selected from CH3NH3PbI3、CH3NH3PbBr3Or CH3NH3PbIxBr1-xOne type of film.
5. A back-incident p-i-n structural perovskite solar cell as claimed in claim 1, wherein: the electronic transmission layer is PC61BM。
6. A back-incident p-i-n structural perovskite solar cell as claimed in claim 1, wherein: the anode is a transparent composite electrode (V)2O5/Ag/V2O5）。
7. A method of manufacturing a back-incident p-i-n structural perovskite solar cell according to claim 1, comprising the steps of:
processing an FTO conductive film;
preparing a copper oxide nano array hole transport layer;
preparing a perovskite light absorption layer;
preparing an electron transport layer;
and (4) preparing a transparent composite electrode.
8. The method for preparing a back-incident p-i-n structural perovskite solar cell as claimed in claim 7, wherein the step of preparing the copper oxide nanoarray hole transport layer is as follows:
(1) dissolving copper acetate in ethanol, and stirring at room temperature to obtain a blue clear transparent solution;
(2) spin-coating the solution on clean FTO conductive glass through a spin coater to obtain a uniform copper acetate film;
(3) annealing in a muffle furnace to obtain a compact copper oxide film;
(4) placing the copper oxide nano-rod array in an aqueous solution consisting of copper nitrate trihydrate and hexamethylenetetramine, sealing, and reacting in an oven at 90 ℃ for 1-2 hours to obtain the copper oxide nano-rod array.
9. The method for preparing a back-incident p-i-n perovskite solar cell as claimed in claim 7, wherein the perovskite light absorption layer is CH3NH3PbI3The perovskite light absorption layer is prepared by the following specific steps:
(1) will CH3NH2And PbI2Adding into an organic mixed solventThe organic mixed solvent consists of
Butyrolactone and dimethyl sulfoxide in a volume ratio of 7: 3, preparing; then stirring to obtain yellow clear perovskite precursor liquid;
(2) spin-coating the perovskite precursor solution on the copper oxide nanorod array obtained in the step by using a spin coater in a nitrogen glove box, and annealing the substrate by using a heating plate in the nitrogen glove box to obtain CH3NH3PbI3A perovskite light absorbing layer.
10. The method for preparing a back-incident p-i-n structural perovskite solar cell as claimed in claim 7, wherein the electron transport layer is prepared by the following specific method:
(1) will PC61BM powder is dissolved in chlorobenzene;
(2) spin-coating the above solution on CH in a nitrogen glove box by a spin coater3NH3PbI3A perovskite light-absorbing layer;
(3) the substrate was annealed using a hot plate in a nitrogen glove box.
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