Disclosure of Invention
The invention provides a perovskite solar cell, and aims to solve the problem that the photoelectric conversion efficiency of the perovskite solar cell in the prior art is influenced due to low charge transmission and collection efficiency of a hole transmission layer.
The present invention is thus achieved, providing a perovskite solar cell comprising:
a transparent conductive substrate;
the hole transport layer comprises a compact layer arranged on the transparent conductive substrate and a nano array layer which is arranged on the compact layer and is made of inorganic hole transport materials;
a perovskite light absorption layer disposed over the nanoarray layer;
an electron transport layer disposed over the perovskite light absorption layer; and
and the metal electrode is arranged on the electron transmission layer.
Preferably, the inorganic hole transport material is NiOX、CuSCN、CuI、V2O5、Cu2Any one of O.
Preferably, the inorganic hole transport material is NiOX。
Preferably, the transparent conductive substrate comprises a transparent glass substrate and a transparent conductive film which are sequentially arranged from bottom to top, and the compact layer is arranged on the transparent conductive film.
Preferably, the transparent conductive film is any one of an ITO film, an FTO film, an IWO film, and an ICO film.
Preferably, the thickness of the compact layer is 20-30 nm; and/or the thickness of the nano array layer is 10-20nm, and the total thickness of the hole transport layer is 30-50 nm.
The invention also provides a solar cell module which comprises the perovskite solar cell.
The invention also provides a photovoltaic system which comprises the solar cell module.
The invention also provides a preparation method of the perovskite solar cell, which comprises the following steps:
cleaning the transparent conductive substrate;
preparing a dense layer on the transparent conductive substrate;
preparing a nano array layer composed of an inorganic hole transport material on the compact layer, wherein the nano array layer and the compact layer form a hole transport layer;
preparing a perovskite light absorption layer on the nano-array layer;
preparing an electron transport layer over the perovskite light absorption layer;
and preparing a metal electrode on the electron transport layer.
Preferably, the step of cleaning the transparent conductive substrate comprises:
wiping the surface of the transparent conductive substrate, sequentially ultrasonically cleaning the transparent conductive substrate for 15-20 minutes by using a cleaning agent, deionized water, acetone and ethanol, drying the transparent conductive substrate in an oven, and introducing O3UV treatment for 10-20 minutes.
Preferably, the inorganic hole transport material is NiOX。
Preferably, the step of preparing a dense layer on the transparent conductive substrate comprises:
and depositing the compact layer on the transparent conductive substrate by adopting a magnetron sputtering method.
Preferably, the step of preparing a nanoarray layer of inorganic hole transport material over the dense layer comprises:
and placing an AAO template on the compact layer, depositing an inorganic hole transport material into the AAO template by adopting a magnetron sputtering method, taking out the AAO template after deposition is finished, and forming a nano array layer consisting of the inorganic hole transport material on the compact layer.
Preferably, the perovskite light absorption layer is an organic-inorganic hybrid perovskite material; the step of preparing a perovskite light absorption layer over the hole transport layer includes:
preparing a precursor solution for preparing the perovskite light absorption layer;
and coating the precursor solution on the hole transport layer, and annealing for 10-15 minutes after coating to finish the preparation of the perovskite light absorption layer.
Preferably, the material of the electron transport layer is SnO2A nanoparticle; the step of preparing an electron transport layer over the perovskite light absorption layer comprises:
SnO2And dissolving the nano particles and deionized water in a volume ratio of 1:5, coating the dissolved nano particles on the perovskite light absorption layer, and annealing to obtain the electron transmission layer.
Preferably, the metal electrode is a silver electrode; the step of preparing a metal electrode over the electron transport layer includes: depositing a silver electrode on the electron transport layer by thermal evaporation
According to the perovskite solar cell, the hole transmission layer formed by the compact layer and the nano array layer is arranged, and the nano array layer has the ordered array structure vertical to the compact layer, so that a direct transmission channel can be provided for holes; meanwhile, the nano array layers have ordered intervals, so that the perovskite crystals of the perovskite light absorption layer can be uniformly and effectively permeated, the effective contact area between the perovskite light absorption layer and the hole transmission layer is increased, the rapid separation and conduction of photon-generated carriers are promoted, the crystallization quality of the perovskite light absorption layer is also improved, and the photoelectric conversion efficiency of the perovskite battery is improved; in addition, due to the efficient transmission characteristic of the nano array, the thickness of the prepared hole transmission layer is far lower than that of the traditional perovskite battery, so that the efficiency of the battery is ensured, and the material cost is saved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
According to the perovskite solar cell, the hole transmission layer formed by the compact layer and the nano array layer is arranged, and the nano array layer has the ordered array structure vertical to the compact layer, so that a direct transmission channel can be provided for holes; meanwhile, the nano array layers have ordered intervals, so that the perovskite crystals of the perovskite light absorption layer can be uniformly and effectively permeated, the effective contact area between the perovskite light absorption layer and the hole transmission layer is increased, the rapid separation and conduction of photon-generated carriers are promoted, the crystallization quality of the perovskite light absorption layer is also improved, and the photoelectric conversion efficiency of the perovskite battery is improved; in addition, due to the efficient transmission characteristic of the nano array, the thickness of the prepared hole transmission layer is far lower than that of the hole transmission layer of the traditional perovskite battery, so that the efficiency of the battery is guaranteed, and the material cost is saved.
Example one
Referring to fig. 1, an embodiment of the invention provides a perovskite solar cell, including:
a transparent conductive substrate 1;
the hole transport layer 2 comprises a compact layer 21 arranged on the transparent conductive substrate 1 and a nano array layer 22 which is arranged on the compact layer 21 and is made of inorganic hole transport materials;
a perovskite light absorption layer 3 provided on the nanoarray layer 22;
an electron transport layer 4 provided on the perovskite light absorption layer 3; and
and a metal electrode 5 disposed on the electron transport layer 4.
As an embodiment of the present invention, the transparent conductive substrate 1 includes a transparent glass substrate 11 and a transparent conductive film 12, which are sequentially disposed from bottom to top, and the dense layer 21 is disposed on the transparent conductive film 12. The transparent glass substrate 11 is used for transmitting sunlight, and the transparent conductive film 12 is used for transmitting light and conducting electricity.
As an embodiment of the present invention, the transparent conductive film 12 is any one of an ITO film, an FTO film, an IWO film, and an ICO film. In practical application, any one of an ITO film, an FTO film, an IWO film, and an ICO film may be selected. Preferably, the transparent conductive film 12 is an ITO film, and since the ITO film has a suitable work function, holes can be effectively extracted from the hole transport layer 2, which is beneficial to improving the efficiency of the battery.
As one embodiment of the present invention, the inorganic hole transport material is NiOX、CuSCN、CuI、V2O5、Cu2Any one of O.
In the embodiment of the present invention, the hole transport layer 2 is composed of the dense layer 21 and the nano array layer 22. The nano-array layer 22 is formed by nano-arrays of inorganic hole transport materials, so that the nano-array layer 22 is formed by nano-array structures of inorganic hole transport materials. The inorganic hole transport material nano array structure is formed by a plurality of inorganic hole transport material nano wires which are vertical to the compact layer 21 in an ordered array, so that the nano array layer 22 has an ordered nano array structure which is vertical to the compact layer 21, a direct transport channel can be provided for a hole, and compared with the method of adopting compact NiOXNiO with thin film or compact and mesoporous structureXThin film as hole transport layerThe perovskite solar cell can improve the charge transmission and collection efficiency; meanwhile, the nano array layer 22 formed by the inorganic hole transmission material nano array structure has ordered spacing, so that the perovskite crystals of the perovskite light absorption layer 3 can be uniformly and effectively permeated, the effective contact area between the perovskite light absorption layer 3 and the hole transmission layer 2 is increased, the rapid separation and conduction of photon-generated carriers are promoted, the crystallization quality of the perovskite light absorption layer 3 is also improved, and the photoelectric conversion efficiency of the perovskite battery is improved. In addition, due to the efficient transmission characteristic of the nano array layer 22, the thickness of the prepared hole transmission layer 2 is far lower than that of the hole transmission layer 2 of the traditional perovskite battery, so that the efficiency of the battery is guaranteed, and the material cost is saved.
As a preferred embodiment of the present invention, the dense layer 21 and the nanoarray layer 22 are both made of an inorganic hole transport material. Preferably, the inorganic hole transport material is NiOXThe compact layer 21 and the nano-array layer 22 are both NiOXThe material is used for the transmission of holes. Using NiOXThe material is used for preparing a compact layer 21 and a nano array layer 22, compared with an organic conducting polymer material, NiOXThe preparation method has the advantages of low preparation cost and high interface stability, and can ensure that the manufacturing cost of the battery is low and the efficiency of the battery is higher.
As an embodiment of the present invention, the thickness of the dense layer 21 is 20 to 30nm, so that electrons can be better collected and conducted. The thickness of the dense layer 21 can be set according to actual needs.
As an embodiment of the present invention, the thickness of the nanoarray layer 22 is 10-20nm, and the total thickness of the hole transport layer is 30-50 nm. Compared with the dense NiOXNiO with thin film or compact and mesoporous structureXThe film is used as a hole transport layer, and due to the efficient transport characteristic of the nano array layer 22, the thickness of the prepared hole transport layer is far lower than that of the traditional perovskite battery, so that the efficiency of the battery is ensured, and the material cost is saved.
As an embodiment of the present invention, the thickness of the electron transport layer 4 is 98-100nm, which ensures that the electron transport layer 4 has a good electron transport effect.
As an embodiment of the invention, the material of the electron transport layer 4 is PCBM, TiO2、ZnO、SnO2At least one of (1). Preferably, the material of the electron transport layer 4 is SnO2The nano-particles enable the electron transport layer 4 to have good electron transport effect.
According to the perovskite solar cell, the hole transmission layer formed by the compact layer and the nano array layer is arranged, and the nano array layer has the ordered array structure vertical to the compact layer, so that a direct transmission channel can be provided for holes; meanwhile, the nano array layers have ordered intervals, so that the perovskite crystals in the perovskite light absorption layer can be uniformly and effectively permeated, the effective contact area between the perovskite layer and the hole transmission layer is increased, the rapid separation and conduction of photon-generated carriers are promoted, the crystallization quality of the perovskite thin film is also improved, and the photoelectric conversion efficiency of the perovskite battery is improved; in addition, due to the efficient transmission characteristic of the nano array, the thickness of the prepared hole transmission layer is far lower than that of the hole transmission layer of the traditional perovskite battery, so that the efficiency of the battery is guaranteed, and the material cost is saved.
Example two
Referring to fig. 2, the present invention further provides a method for manufacturing a perovskite solar cell, which is used to manufacture the perovskite solar cell of the first embodiment, and the method includes the following steps:
step S1, cleaning the transparent conductive substrate 1;
as one embodiment of the present invention, the transparent conductive substrate 1 is ITO conductive glass. The ITO conductive glass is manufactured by plating a layer of transparent conductive film 12 on a transparent glass substrate 11 by a magnetron sputtering method.
In this step, the step of cleaning the transparent conductive substrate 1 includes: wiping the surface of the transparent conductive substrate 1, then ultrasonically cleaning the transparent conductive substrate 1 for 15-20 minutes by using a cleaning agent, deionized water, acetone and ethanol in sequence, and finally cleaningThe transparent conductive substrate 1 enters an oven for drying and is introduced with O3UV treatment for 10-20 minutes.
Specifically, ITO conductive glass with the transmissivity of more than 80% is used as a transparent conductive substrate 1, the surface of the ITO conductive glass is wiped by dipping ethanol in dust-free paper, then the ITO conductive glass is sequentially ultrasonically cleaned for 15-20 minutes by detergent, deionized water, acetone and ethanol, the ITO conductive glass is dried in a ventilation oven, and O is introduced into the ventilation oven3After UV treatment for 20 minutes, the transparent conductive substrate 1 is cleaned.
Step S2, preparing a dense layer 21 on the transparent conductive substrate 1;
as an embodiment of the present invention, the material of the dense layer 21 is an inorganic hole transport material. It is preferred. The material of the compact layer 21 is NiOX(ii) a The step of preparing the dense layer 21 on the transparent conductive substrate 1 includes: NiO is formed by adopting a magnetron sputtering methodXDepositing on the transparent conductive substrate 1 to form the dense layer 21.
Step S3, preparing a nano array layer 22 made of inorganic hole transport material on a compact layer 21, wherein the nano array layer 22 and the compact layer 21 form a hole transport layer 2;
as an embodiment of the present invention, step S3 includes:
and placing the AAO template 10 on the compact layer 21, depositing an inorganic hole transport material into the AAO template 10 by adopting a magnetron sputtering method, taking out the AAO template after the deposition is finished, and forming a nano array layer 3 consisting of the inorganic hole transport material on the compact layer 21. Preferably, the inorganic hole transport material is NiOX。
Specifically, NiO is formed by magnetron sputtering as shown in FIG. 3XDeposited into the mesh openings 100 in the AAO form 10 to form NiO perpendicular to the dense layer 21 within the mesh openings 100 in the AAO form 10XThe nano wire is taken out after the deposition is finished, and a plurality of NiO can be formed on the compact layer 21XA nano-array layer 22 of nano-wire arrays.
The AAO template 10 may be prepared in advance before step S1, and the specific preparation process of the AAO template is as follows:
annealing an aluminum foil with the purity of 99.999% at 150 ℃ for 2h, cooling, placing the aluminum foil in an acetone solution, and ultrasonically cleaning to remove surface stains;
placing the aluminum foil in ethanol (CH)3CH2OH), perchloric acid (HClO)4) Performing electrochemical polishing in the mixed solution to obtain a super-pure aluminum foil with a smooth and clean surface;
aluminum foil is placed in oxalic acid electrolyte with aluminum as anode and platinum as cathode, and is anodized at 100V at 5 deg.C, and saturated copper chloride (CuCl)2)、HClO4Dissolving the mixed solution to remove the residual aluminum material;
finally, a 5 wt% phosphoric acid solution (H) is used3PO4) The barrier layer on the aluminum sheet was removed, and after washing with water and air-drying, an AAO template 10 having a pore diameter of 100nm was obtained, and the obtained AAO template (anodized aluminum) was as shown in fig. 3.
Step S4, preparing a perovskite light absorption layer 3 on the nanoarray layer 22;
in this step, the perovskite light absorption layer 3 is an organic-inorganic hybrid perovskite material with a general formula ABX3. Wherein A is CH3NH3 +(MA+)、CH(CH2)2+(FA+)、Cs+B is Pb2+、Sn2+、Ge2+Wherein X is Cl-、Br-、I-At least one of (1).
As a preferred embodiment of the present invention, the material of the perovskite light absorption layer 3 is an MA + -free organic-inorganic hybrid perovskite material FA0.91Cs0.09PbI3。
As an embodiment of the present invention, the step of preparing the perovskite light absorption layer 3 over the nanoarray layer 22 includes:
preparing a precursor solution for preparing the perovskite light absorption layer 3;
the precursor solution is coated on the nano-array layer 22, and annealing is performed for 10-15 minutes after coating, so that the preparation of the perovskite light absorption layer 3 is completed.
Specifically, first, FA is performed0.91Cs0.09PbI3Preparing precursor solution of PbI2(ii) a FAI; CsI is added into DMF/DMSO mixed solution with the volume ratio of 4.75:1 according to the chemical ratio of 1:0.91:0.09 until the solution concentration is 1.25mol/L, and then MaCl is added into the solution until the concentration is 23 mol% so as to stabilize perovskite phase formation, and FA is obtained0.91Cs0.09PbI3Precursor solution and slot-die slit coating method for coating FA0.91Cs0.09PbI3The precursor solution is coated on the nano-array layer 22, and the perovskite light absorption layer 3 is prepared by annealing at 160 ℃ for 10-15 minutes after coating.
Step S5, preparing an electron transport layer 4 on the perovskite light absorption layer 3;
as an embodiment of the invention, the material of the electron transport layer 4 is PCBM, TiO2、ZnO、SnO2At least one of (1). Preferably, the material of the electron transport layer 4 is SnO2And (3) nanoparticles.
In the present embodiment, the step of preparing the electron transport layer 4 over the perovskite light absorption layer 3 includes:
SnO2The nano particles and deionized water are dissolved in a volume ratio of 1:5, and the dissolved nano particles are coated on the perovskite light absorption layer 3 and annealed to obtain the electron transport layer 4. Wherein the thickness of the electron transport layer 4 is 98-100nm, and the annealing temperature is 150 ℃.
In step S6, a metal electrode 5 is prepared on the electron transport layer 4.
As a preferred embodiment of the present invention, the metal electrode 5 is a silver electrode. Besides this embodiment, the material of the metal electrode 5 may be one of Au, Cu, and C.
As an embodiment of the present invention, the step of preparing the metal electrode 5 on the electron transport layer 4 includes: and depositing a silver electrode on the electron transport layer 4 by adopting a thermal evaporation method.
According to the perovskite solar cell preparation method provided by the embodiment of the invention, the hole transport layer formed by the compact layer and the nano array layer is prepared, and compared with the traditional perovskite solar cell, the perovskite solar cell prepared by the method can improve the charge transmission and collection efficiency; meanwhile, the hole transmission layers of the nano array structure have ordered intervals, so that perovskite crystals of the perovskite light absorption layer can be uniformly and effectively permeated, the effective contact area between the perovskite light absorption layer and the hole transmission layers is increased, the rapid separation and conduction of photon-generated carriers are promoted, the crystallization quality of the perovskite light absorption layer is also improved, and the photoelectric conversion efficiency of the perovskite battery is improved; in addition, due to the efficient transmission characteristic of the nano array, the thickness of the prepared hole transmission layer is far lower than that of the traditional perovskite battery, so that the efficiency of the battery is ensured, and the material cost is saved.
EXAMPLE III
The invention also provides a solar cell module comprising the perovskite solar cell of the first embodiment. According to the solar cell module, the perovskite solar cell is arranged, and compared with the conventional perovskite solar cell, the perovskite solar cell of the first embodiment can improve the charge transmission and collection efficiency and the photoelectric conversion efficiency of the perovskite solar cell, so that the power generation efficiency of the solar cell module can be improved.
Example four
The invention further provides a photovoltaic system comprising the solar cell module of the third embodiment. According to the photovoltaic system, by applying the solar cell module, the power generation efficiency of the photovoltaic system can be improved.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.