LARGE-AREA PEROVSKITE FILM AND PEROVSKITE SOLAR CELL OR MODULE AND FABRICATION METHOD THEREOF
20170287648 · 2017-10-05
Inventors
Cpc classification
H10K71/441
ELECTRICITY
Y02E10/542
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H10K30/20
ELECTRICITY
H10K85/1135
ELECTRICITY
H10K85/111
ELECTRICITY
H10K30/10
ELECTRICITY
H10K39/10
ELECTRICITY
H10K71/13
ELECTRICITY
International classification
Abstract
A method of fabricating a large-area perovskite film includes steps of: providing a precursor solution on a conductive substrate to form a film, wherein the perovskite is represented by a formula of ABX.sub.3, and the solutes of the precursor solution at least comprises A, B and X; and applying an anti-solvent or Infrared light on the film. The fabrication methods of a large-area perovskite film and a perovskite solar cell or module are also disclosed.
Claims
1. A method of fabricating a perovskite film, comprising steps of: providing a precursor solution on a conductive substrate by slot die coating to form a film, wherein a perovskite is represented by a formula of ABX.sub.3, and solutes of the precursor solution at least comprises A, B and X; and immersing the film in an anti-solvent so as to form the perovskite film; wherein perovskite crystals of the perovskite film are continuously and evenly distributed on the conductive substrate, and areas of the perovskite film and the conductive substrate are 5˜10000 cm.sup.2.
2. The method of claim 1, wherein the anti-solvent induces the film to generate perovskite crystals; and wherein, A is at least one of alkali metal ions, CH.sub.3NH.sub.3.sup.+, and NH.sub.2CH═NH.sub.2.sup.+, B is at least one of Pb, Sn, and Ge, and X is at least one of halogen (F, Cl, Br or I), PF.sub.6, and SCN.
3. The method of claim 1, wherein a solvent of the precursor solution is DMF, DMSO, GBL, or a mixture thereof.
4. The method of claim 1, wherein the anti-solvent is thiophene and its derivative, iodobenzene, ether, chlorobenzene, dichlorobenzene, toluene, benzene, or a mixture thereof.
5. The method of claim 1, further comprising a step of: annealing the film so as to grow bigger perovskite grains.
6. The method of claim 1, wherein the film is immersed in the anti-solvent so as to apply the anti-solvent on the film, and an amount of perovskite crystals generated in the film depends on an immersion time of the film in the anti-solvent.
7. A method of fabricating a perovskite film, comprising steps of: providing a precursor solution on a conductive substrate by slot die coating to form a film, wherein a perovskite is represented by a formula of ABX.sub.3, and solutes of the precursor solution at least comprises A, B and X; and irradiating an Infrared light on the film so as to form the perovskite film; wherein perovskite crystals of the perovskite film are continuously and evenly distributed on the conductive substrate, and areas of the perovskite film and the conductive substrate are 5˜10000 cm.sup.2.
8. The method of claim 7, wherein, A is at least one of alkali metal ions, CH.sub.3NH.sub.3.sup.+, and NH.sub.2CH═NH.sub.2.sup.+, B is at least one of Pb, Sn, and Ge, and X is at least one of halogen (F, Cl, Br or I), PF.sub.6, and SCN.
9. The method of claim 7, wherein a solvent of the precursor solution is DMF, DMSO, GBL, or a mixture thereof.
10. The method of claim 7, wherein the Infrared light used to induce the film to generate the perovskite crystals has a wavelength between 750˜2000 nm.
11. The method of claim 7, further comprising a step of: annealing the film so as to grow the perovskite crystals.
12. A method of fabricating a perovskite solar cell or module, comprising steps of: providing a conductive substrate; forming a first carrier transporting layer on the conductive substrate; providing a precursor solution on the first carrier transporting layer by slot die coating to form a film, wherein a perovskite is represented by a formula of ABX.sub.3, and solutes of the precursor solution at least comprises A, B and X; immersing the film in an anti-solvent or irradiated with Infrared light; transforming the film into a perovskite film; annealing the film to grow bigger perovskite grains; forming a second carrier transporting layer on the perovskite film; and forming an electrode layer on the second carrier transporting layer; wherein perovskite crystals of the perovskite film are continuously and evenly distributed on the conductive substrate, and areas of the perovskite film and the conductive substrate are 5˜10000 cm.sup.2.
13. The method of claim 12, wherein the conductive substrate is a transparent conductive glass or a flexible transparent conductive substrate; wherein the first carrier transporting layer is a hole transporting layer or an electron transporting layer, while the second carrier transporting layer is an electron transporting layer or a hole transporting layer, and the electrode layer is a cathode layer or an anode layer; wherein the hole transporting layer comprises one or any combinations of PEDOT:PSS, V.sub.2O.sub.5, NiO, In.sub.2O.sub.3, graphene, MoS, MoSe, Spiro-OMeTAD, polyalkyl-thiophene, and MoO.sub.3; wherein the electron transporting layer comprises one or any combinations of 6,6-phenyl-C61-butyric acid methyl ester (PC.sub.61 BM), 6,6-phenyl-C71-butyric acid methyl ester, (PC.sub.71BM), Indene-C60 bisadduct (ICBA), C.sub.60, C.sub.70, LiF, Ca, TiO.sub.2, Bathocuproine (BCP), ZrO, ZnO, polyethylenimine (PEI), and poly[(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctyl-fluorene) (PFN); and wherein the electrode layer comprises one or any combinations of Ca, Al, Ag, Pd, and Au.
14. A perovskite solar cell or module, comprising: a conductive substrate having an area ranged from 5 cm.sup.2 to 10000 cm.sup.2; a first carrier transporting layer deposited on the conductive substrate; a perovskite film having a continuous and homogeneous morphology, wherein an area of the film is greater than 5 cm.sup.2; a second carrier transporting layer deposited on the perovskite film; and an electrode layer deposited on the second carrier transporting layer.
15. The perovskite solar cell or module of claim 12, wherein the perovskite film in the cell or module is polycrystalline.
16. The perovskite solar cell or module of claim 12, which is applied to an environment with an illumination of 0.1˜100 mW/cm.sup.2.
17. The perovskite solar cell or module of claim 12, wherein the electrode layer is made of silver.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] The invention will become more fully understood from the detailed description and accompanying drawings, which are given for illustration only, and thus are not limitative of the present invention, and wherein:
[0032]
[0033]
[0034]
[0035]
[0036]
[0037]
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[0040]
DETAILED DESCRIPTION OF THE INVENTION
[0041] The present invention will be apparent from the following detailed description, which proceeds with the reference to the accompanying drawings, wherein the same references relate to the same elements.
[0042] Perovskite is a group of ceramic material having a general chemical formula of ABX.sub.3. Herein, A is at least one of alkali metal ions, CH.sub.3NH.sub.3.sup.+, and NH.sub.2CH═NH.sub.2.sup.+, B is at least one of Pb, Sn, and Ge, and X is at least one of halogen (F, Cl, Br or I), PF.sub.6, and SCN.
[0043]
[0044] The step S101 is to provide a precursor solution on a conductive substrate to form a film, wherein a perovskite is represented by a formula of ABX.sub.3, and solutes of the precursor solution at least comprises A, B and X.
[0045] The step S102 is to apply an anti-solvent on the film or irradiate with the Infrared light.
[0046] In the steps S101 and S102, the precursor solution and anti-solution can be provided by a proper method other than the evaporation process. For example, the precursor solution can be provided on the conductive substrate by spin coating, slot die coating, ink-jet printing, screen printing, immersing or daubing, and the anti-solution can be applied to the film by spin coating, slot die coating, ink-jet printing, printing, immersing or daubing or the film was treated with the irradiation of Infrared light. Accordingly, the present invention can fabricate the large-area perovskite film without using the evaporation process, so that the expensive evaporation equipment is not needed. Besides, the time for vacuuming the chamber can be saved.
[0047] In this embodiment, the solvent of the precursor solution is DMF, DMSO, GBL, or a mixture thereof. The anti-solvent is thiophene and its derivative, iodobenzene, ether, CB, DCB, toluene, benzene, or a mixture thereof. The anti-solvent is just a solvent. The wavelength of the Infrared light is 750 nm-2000 nm.
[0048] For example, in order to fabricate a CH.sub.3NH.sub.3PbI.sub.3 perovskite film, the solvent for the precursor solution thereof is DMF, and the solutes are PbI.sub.2 and CH.sub.3NH.sub.3I (preferably 40 wt %). In addition, the anti-solvent is thiophene. In more detailed, the solute A of the precursor solution includes at least one of alkali metal ions, CH.sub.3NH.sub.3.sup.+, and NH.sub.2CH═NH.sub.2.sup.+, the solute B includes at least one of Pb, Sn, and Ge, and the solute X includes at least one of halogen (F, Cl, Br or I), PF.sub.6, and SCN.
[0049] To be noted, the applying speed of the anti-solution or Infrared light can affect the quality of the resulting perovskite film. In some cases, if the anti-solution is applied too slowly, the fabricated perovskite film will have bad quality. In other cases, the Infrared illuminating intensity is too low, the fabricated perovskite film will have bad quality. Besides, the manufacturing parameters, such as the composition and concentration of the precursor solution, the spin coating program, the type of the anti-solution, the film immersion time, and the intensity of Infrared light can also affect the quality of the perovskite film. For example, the crystallization speed, crystallization level, or grain size of the perovskite film is affected by these processing parameters. Accordingly, the quality of the perovskite film can be precisely controlled by adjusting the above-mentioned processing parameters.
[0050] In the step S101, the precursor solution can be applied on the conductive substrate by spin coating, slot die coating, ink-jet printing, screen printing, immersing or daubing. In practice, a spin coater is utilized to apply the precursor solution on the conductive substrate (spin coating). In one aspect, the precursor solution can also be applied on the conductive substrate through a slot die for performing the slot die coating. In one aspect, a nozzle is utilized to eject the precursor solution on the conductive substrate (ink-jet printing). In one aspect, a screen printer is utilized to print the precursor solution on the conductive substrate. In one aspect, the conductive substrate is immersed in the precursor solution (immersing). In one aspect, a brush or tool is utilized to scribble the precursor solution on the conductive substrate (daubing). In addition, the conductive substrate can be a transparent or an opaque substrate, and it can be a flexible or inflexible substrate. For example, the conductive substrate can be a transparent conductive glass or a flexible transparent conductive substrate.
[0051] In the step S102, the anti-solvent can be applied on the film by spin coating, slot die coating, ink-jet printing, printing, immersing or daubing. The generation speed of the perovskite crystals in the film depends on the type of anti-solvent and the applying speed of the anti-solvent. For example, when the anti-solvent is applied on the film by spin coating, the generation speed of the perovskite crystals in the film depends on the speed of the anti-solvent dropped on the film. When the film is immersed in the anti-solvent, the amount of the perovskite crystals grown in the film depends on the time for immersing the film in the anti-solvent.
[0052] In the step S102, an Infrared light can be applied on the film.
[0053] The perovskite crystals grown in the film are continuously and evenly distributed on the conductive substrate, and the area of the film may be greater than 5 cm.sup.2. For example, the distribution area of the perovskite crystals is between 5 cm.sup.2 and 10000 cm.sup.2. In this case, the area of the conductive substrate is also greater than 5 cm.sup.2 (e.g. between 5 cm.sup.2 and 10000 cm.sup.2).
[0054] In this embodiment, the large-area and uniform perovskite (ABX.sub.3) film is rapidly fabricated by solution process and anti-solution or Infrared light induced crystallization. The applied anti-solvent or Infrared light can induce the film, which is made by the precursor solution, to generate perovskite crystals. In more detailed, the film made from the precursor solution contains the perovskite components. The solvent of the film can be replaced, after contacting with the anti-solvent, by the anti-solvent to generate the perovskite crystals. The solvent of the film will evaporate after irradiating with the Infrared light. If the anti-solvent (or Infrared light) is continuously applied to all over the film, the perovskite crystals can be continuously generated at the whole film. Accordingly, the film can be transformed into a continuous and homogeneous perovskite film. In this embodiment, the perovskite crystals of the film are polycrystalline.
[0055] In addition, the method of fabricating a large-area perovskite film may further include an annealing step, which is to anneal the film at 100° C. for 20 minutes or heating with Infrared irradiation. This annealing step can further help the growth of the perovskite crystals. In practice, the generated perovskite film, after applying the anti-solvent or Infrared light, can be recrystallized in the annealing step, so that the grain size of the perovskite film increased.
[0056]
[0057] Referring to
[0058] With reference to
[0059] Next, a first carrier transporting layer 12 is formed on the conductive substrate 11 by spin coating or other methods (step S202). Since the solar module 1 of this embodiment has an inverted structure, the first carrier transporting layer 12 is a hole transporting layer, which can be PEDOT:PSS or any suitable material that can transport holes.
[0060] Afterwards, the step S203 is to provide a precursor solution on the first carrier transporting layer 12 to form a film. The solutes of the precursor solution includes PbI.sub.2 and CH.sub.3NH.sub.3I (40 wt %), and the solvent thereof is DMF. For example, the precursor solution can be provided on the first carrier transporting layer 12 by spin coating (3000 RPM for 50 seconds) so as to form the film. Then, the step S204 is to immerse the film in the anti-solvent or irradiate the film with Infrared light at the last second of the spin. In the step S204, the anti-solvent can replace the solvent containing in the film. In this embodiment, the anti-solvent is thiophene. In the step S205, after anti-solvent dropping and/or thermal annealing, the film transformed into a high quality CH.sub.3NH.sub.3PbI.sub.3 film. The obtained perovskite film can be used as the active layer 13 of the solar module 1.
[0061] In this embodiment, the perovskite film is a continuous and homogeneous film, and the area of the film is greater than 5 cm.sup.2 (e.g. between 5 cm.sup.2 and 10000 cm.sup.2). In addition, the steps S203 to S205 are similar to the steps S101 to S102, so the manufacturing processes for the steps S203 to S205 can be referred to the above-mentioned processes of the steps S101 to S102.
[0062] Next, a second carrier transporting layer 14 is formed on the perovskite film (the active layer 13) by spin coating, thermal evaporation or other methods (step S206). Since the solar module 1 of this embodiment has an inverted structure, the second carrier transporting layer 14 is an electron transporting layer, which can be made of 6,6-phenyl-C61-butyric acid methyl ester (PC.sub.61BM), 6,6-phenyl-C71-butyric acid methyl ester (PC.sub.71 BM0, indene-C60 bisadduct (ICBA), C.sub.60, C.sub.70, fullerene derivatives, LiF, Ca, TiO.sub.2, bathocuproine (BCP), ZrO, ZnO, Polyethylenimine (PEI), poly[(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctyl-fluorene) (PFN), or any suitable material that can transport electrons.
[0063] Finally, an electrode layer 15 is formed on the second carrier transporting layer 14 by evaporation or other methods (step S207). Since the solar module 1 of this embodiment has an inverted structure, the electrode layer 15 is a cathode, which can be made of Ca, Al, Ag, Pd, Au or their combinations.
[0064] In another aspect, the solar module 1 has a regular structure. In this aspect, the first carrier transporting layer 12 is an electron transporting layer, which can be made of TiO.sub.2, ZnO, poly[(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctyl-fluorene) (PFN), polyethylenimine (PEI), ZrO, or any suitable material that can transport electrons. The second carrier transporting layer 14 is a hole transporting layer, which can be made of V.sub.2O.sub.5, 2,2′,7,7′-Tetrakis[N,N-di(4-methoxy-phenyl)amino]-9,9′-spiro-bifluorene (Spiro-OMeTAD), NiO.sub.x, In.sub.2O.sub.3, WO.sub.3, MoO.sub.3, or any suitable material that can transport holes. The electrode layer 15 is an anode, which can be made of Ag or Au.
[0065]
[0066]
[0067] As shown in the following table, compared with the conventional perovskite solar cell or module, the perovskite solar cell or module of the present invention configured with an active layer of the above-mentioned large-area perovskite film has better PCE and higher FF. Besides, compared with the conventional perovskite solar cell or module, the perovskite solar cell or module of the present invention does not have the current hysteresis as the curves shown in
TABLE-US-00001 perovskite Area of active solar cell layer module (cm.sup.2) PCE (%) FF Conventional 4 12.6 0.69 Present 11 15.4 0.77 invention Conventional: W. Qiu, T. Merckx,.sup.a M. Jaysankar, C. Masse de la Huerta, L. Rakocevic, W. Zhang, U. W. Paetzold, R. Gehlhaar,.sup.a L. Froyen,.sup.b J. Poortmans, D. Cheyns, H. J. Snaith and P. Heremans. Pinhole-free perovskite films for efficient solar modules._Energy Environ. Sci., 2016, 9, 484-489.
[0068]
[0069]
[0070] The perovskite solar module made of the above-mentioned fabricating method contains a high quality, large-area perovskite film functioned as the active layer. Accordingly, even in an environment with weak light source (0.1˜100 mW/cm.sup.2), it can still generate sufficient current and voltage to charge the battery of a cell phone, electrolyze water to produce hydrogen, or as a power source for a magnetic motor. As shown in
[0071] In summary, the invention utilizes the solution process and anti-solution crystallization to rapidly fabricate the large-area perovskite film instead of using the expensive evaporation equipment, so that the manufacturing time and cost can be reduced. In addition, the method of the present invention can control the crystallization rate, crystallization level and grain size of the perovskite film based on the type of the anti-solvent, the applied speed of the anti-solvent, the film immersion time or the Infrared light illumination intensity and time, thereby a high-quality large-area perovskite film can be made. Besides, the invention can further precisely control the crystallization rate, crystallization level and grain size of the perovskite film by adjusting the composition and concentration of the precursor solution and the parameters of the spin coating or immersion processes as well as the light illumination intensity and time, thereby the uniform and high-quality large-area perovskite film was fabricated. The large-area perovskite film fabricated by the invention can be used as the active layer of the solar cell or module. The large-area perovskite solar cell or module has an excellent power conversion efficiency and without current hysteresis.
[0072] Furthermore, the large-area perovskite solar cell or module has an excellent power conversion efficiency, and the perovskite has a strong absorption in the visible light. Accordingly, even in an environment with weak lighting (0.1˜100 mW/cm.sup.2), it can still be applied to charge the battery of a cell phone, electrolyze water to produce hydrogen, or be a power source for a magnetic motor.
[0073] Although the invention has been described with reference to specific embodiments, this description is not meant to be construed in a limiting sense. Various modifications of the disclosed embodiments, as well as the alternative embodiments, will be apparent to persons skilled in the art. It is, therefore, contemplated that the appended claims will cover all modifications that fall within the true scope of the invention.