Mesoscopic framework for organic-inorganic perovskite based photoelectric conversion device and method for manufacturing the same

Abstract

The invention discloses a perovskite solar cell and a method of fabrication thereof. The perovskite solar cell sequentially comprises a transparent electrode, a mesoporous P-I-N framework and a counter electrode from the bottom to top; the mesoporous P-I-N framework is composed of an n-type semiconductor layer, an insulating layer, and a p-type semiconductor layer in a sequentially stacked mode, and the n-type semiconductor layer, the insulating layer and the p-type semiconductor layer all comprise mesopores filled with a perovskite material. The preparation method sequentially includes preparing the mesoporous P-I-N framework on a transparent conductive substrate through a spin-coating method or a screen printing method, filling with the perovskite material and preparing the counter electrode layer.

Claims

1. An organic-inorganic perovskite based solar cell comprising a conductive substrate, an ETL/active layer/HTL component, and a negative electrode, wherein the ETL/active layer/HTL component is disposed between the conductive substrate and the negative electrode, and the ETL/active layer/HTL component comprises: a mesoporous P-I-N framework containing a mesoporous n-type semiconductor layer, a mesoporous insulating layer, and a mesoporous p-type semiconductor layer; and an organic-inorganic perovskite light absorbing material; wherein: the mesoporous n-type semiconductor layer is disposed on the conductive substrate; the mesoporous insulating layer is disposed between the mesoporous n-type semiconductor layer and the mesoporous p-type semiconductor layer; the mesoporous p-type semiconductor layer is in contact with the negative electrode; the organic-inorganic perovskite light absorbing material is present in mesopores of the mesoporous n-type semiconductor layer; the organic-inorganic perovskite light absorbing material is present in mesopores of the mesoporous insulating layer; and the organic-inorganic perovskite light absorbing material is present in mesopores of the mesoporous p-type semiconductor layer.

2. The organic-inorganic perovskite based solar cell of claim 1, wherein the mesoporous n-type semiconductor being the electron transport layer is made of semiconductor particles selected from the group consisting of Si, TiO.sub.2, SnO.sub.2, ZnO, Zn.sub.2SnO.sub.4, Nb.sub.2O.sub.5, WO.sub.3, BaTiO.sub.3, SrTiO.sub.3, and a mixture thereof.

3. The organic-inorganic perovskite based solar cell of claim 1, wherein the mesoporous p-type semiconductor as hole transport layer is made of semiconductor particles selected from the group consisting of NiO, CuO, CuSCN, CuI, CuGaO.sub.2, CuCrO.sub.2, CuAlO.sub.2, and a mixture thereof.

4. The organic-inorganic perovskite based solar cell of claim 1, wherein the mesoporous insulating layer is made of semiconductor particles selected from the group consisting of ZrO.sub.2, Al.sub.2O.sub.3, SiO.sub.2, SiC, Si.sub.3N.sub.4, Ca.sub.3(PO.sub.4).sub.2, and a mixture thereof.

5. The organic-inorganic perovskite based solar cell of claim 1, wherein the conductive substrate is indium tin oxide (ITO) film substrate, fluorine-doped tin oxide (FTO), film substrate, ZnOGa.sub.2O.sub.3 film substrate, ZnO-Al.sub.2O.sub.3 film substrate, or tin-based oxides film substrate.

6. The organic-inorganic perovskite based solar cell of claim 1, wherein one additional blocking layer is deposited onto the conductive substrate to form an intervening layer between the conductive substrate and the mesoporous P-I-N framework.

7. The organic-inorganic perovskite based solar cell of claim 1, wherein the negative electrode is gold (Au), silver (Ag), aluminum (Al), copper (Cu), platinum (Pt), nickel (Ni), or carbon (C).

8. The organic-inorganic perovskite based solar cell of claim 1, wherein the organic-inorganic perovskite material has a formula of CH.sub.3NH.sub.3PbX.sub.mY.sub.3-m, wherein m is an integer from 1 to 3; and X and Y are independently selected from the group consisting of iodine (I), bromine (Br), and chlorine (CI).

9. An organic-inorganic perovskite based solar cell comprising a conductive substrate, a mesoporous P-I-N framework, and a negative electrode, wherein the mesoporous P-I-N framework is disposed between the conductive substrate and the negative electrode, and the mesoporous P-I-N framework comprises a mesoporous n-type semiconductor layer, a mesoporous insulating layer, and a mesoporous p-type semiconductor layer and further comprises an organic-inorganic perovskite light absorbing material; wherein: the organic-inorganic perovskite light absorbing material is present in mesopores of the mesoporous n-type semiconductor layer; the organic-inorganic perovskite light absorbing material is present in mesopores of the mesoporous insulating layer; the organic-inorganic perovskite light absorbing material is present in mesopores of the mesoporous p-type semiconductor layer; the mesoporous n-type semiconductor layer is disposed on the conductive substrate; the mesoporous insulating layer is disposed between the mesoporous n-type semiconductor layer and the mesoporous p-type semiconductor layer; the mesoporous p-type semiconductor layer is in contact with the negative electrode; the mesoporous n-type semiconductor is made of semiconductor particles selected from the group consisting of Si, TiO.sub.2, SnO.sub.2, ZnO, Zn.sub.2SnO.sub.4, Nb.sub.2O.sub.5, WO.sub.3, BaTiO.sub.3, SrTiO.sub.3, and a mixture thereof; the mesoporous insulating layer is made of semiconductor particles selected from the group consisting of ZrO.sub.2, Al.sub.2O.sub.3, SiO.sub.2, SiC, Si.sub.3N.sub.4, Ca.sub.3(PO.sub.4).sub.2, and a mixture thereof; and the mesoporous p-type semiconductor is made of semiconductor particles selected from the group consisting of NiO, CuO, CuSCN, Cut CuGaO.sub.2, CuCrO.sub.2, CuAlO.sub.2, and a mixture thereof.

10. The solar cell of claim 9, wherein the conductive substrate is indium tin oxide (ITO) film substrate, fluorine-doped tin oxide (FTO) film substrate, ZnOGa.sub.2O.sub.3 film substrate, ZnO-Al.sub.2O.sub.3 film substrate, or tin-based oxides film substrate.

11. The solar cell of claim 9, wherein one additional blocking layer is deposited onto the conductive substrate to form an intervening layer between the conductive substrate and the mesoporous P-I-N framework.

12. The solar cell of claim 9, wherein the negative electrode is gold (Au), silver (Ag), aluminum (Al), copper (Cu), platinum (Pt), nickel (Ni), or carbon (C).

13. The solar cell of claim 9, wherein the organic-inorganic perovskite material has a formula of CH.sub.3NH.sub.3PbX.sub.mY.sub.3-m, wherein: m is an integer from 1 to 3; and X and Y are independently selected from the group consisting of iodine (I), bromine (Br), and chlorine (CI).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic view of a mesoporous inorganic P-I-N scaffold or mesoporous inorganic P-I-N metal oxides framework comprising mesoporous inorganic n-type semiconductor layer (N), mesoporous insulating layer (I) and mesoporous inorganic p-type semiconductor layer (P).

(2) FIG. 2 is a schematic view of a perovskite solar cell with mesoporous inorganic P-I-N scaffold or mesoporous inorganic P-I-N metal oxides framework comprising a transparent conductive substrate (1), an additional blocking layer being dense layer (2), a mesoporous inorganic n-type semiconductor layer (3), a mesoporous insulating layer (4), an inorganic mesoporous p-type semiconductor layer (5), a negative electrode (6) being used as counter electrode.

(3) FIG. 3 is a current density-voltage (J-V) curve of the perovskite solar cell with mesoporous inorganic P-I-N scaffold filled with organic-inorganic perovskite (TiO.sub.2/Al.sub.2O.sub.3/NiO/(CH.sub.3NH.sub.3PbI.sub.3)).

(4) FIG. 4 is energy band diagrams of each layer of a photoelectric conversion device having mesoporous inorganic TiO.sub.2/Al.sub.2O.sub.3/NiO scaffold filled with organic-inorganic perovskite (CH.sub.3NH.sub.3PbI.sub.3).

(5) FIG. 5 shows scanning electron microscopy (SEM) pictures (A) of a surface morphology of organic-inorganic perovskite material, (B) of the cross-section of the mesoporous inorganic P-I-N scaffold filled with organic-inorganic perovskite.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(6) The present invention relates to an efficient perovskite solar cell being fabricated from ETL/active layer/HTL component comprising a mesoporous inorganic P-I-N metal oxides framework or scaffold filled with an organic-inorganic perovskite light absorption material. Thus, the present invention provides a novel ETL/active layer/HTL component, which may be used in photoelectric conversion devices, preferably wherein the devices are free of other organic hole transport material.

(7) The present invention also relates to a solar cell perovskite, which sequentially comprises a bottom-transparent electrode, a P-I-N mesoporous framework and a P-I-N electrode, and wherein said mesoporous framework comprises the n-type semiconductor layer, an insulating layer, p-type semiconductor layer under a sequentially stacked configuration, the n-type semiconductor layer, the insulating layer and the p-type semiconductor layer containing mesopores, the n-type semiconductor layer, the insulating layer and the p-type mesoporous semiconductor layer being filled with a perovskite material. A dense layer for electron or hole barrier is provided between the transparent electrode and the P-I-N mesoporous framework.

(8) In addition, the inorganic charge transport layers including ETL and HTL are prefabricated before the preparation of active layer, which makes the processing of charge transport layer more easily. Especially, the hole transport layer is a mesoporous inorganic p-type semiconductor material, which reduces the costs and simplify the preparation.

(9) Thus the present invention provides an organic-inorganic perovskite based solar cell, which comprises a conductive substrate, an ETL/active layer/HTL component, and a negative electrode.

(10) The ETL/active layer/HTL component comprises a mesoporous n-type semiconductor layer, a mesoporous insulating layer, a mesoporous p-type semiconductor layer, and an organic-inorganic perovskite absorbing material. Said mesoporous layers are filled with organic-inorganic perovskite absorbing material.

(11) The mesoporous n-type semiconductor as electron transport layer is an inorganic material. Said mesoporous n-type semiconductor can be made of semiconductor particles. Suitable semiconductor particles comprise material selected from Si, TiO.sub.2, SnO.sub.2, ZnO, Zn.sub.2SnO.sub.4, Nb.sub.2O.sub.5, WO.sub.3, BaTiO.sub.3 or SrTiO.sub.3 or any combination thereof. They may comprise material selected from TiO.sub.2, SnO.sub.2, ZnO, Zn.sub.2SnO.sub.4, Nb.sub.2O.sub.5, WO.sub.3, BaTiO.sub.3, SrTiO.sub.3, Preferably, the semiconductor particles are selected from TiO.sub.2 and ZnO most preferably TiO.sub.2. The average diameter of the semiconductor particles may be from 10 to 200 nm. Preferably, the average diameter of the semiconductor particles is from 10 to 100 nm, 10 to 50 nm. Furthermore, the thickness of the mesoporous semiconductor layer is in the range from 50 nm to 1000 nm, preferably from 50 to 600 nm.

(12) The mesoporous p-type semiconductor as hole transport layer can be made of semiconductor particles. Suitable semiconductor particles comprise material selected from NiO, CuO, CuSCN, CuI, CuGaO.sub.2, CuCrO.sub.2 or CuAlO.sub.2 or any combination thereof. Preferably, the semiconductor particles are selected from NiO. The average diameter of the semiconductor particles may from 10 to 500 nm, from 10 to 400 nm. Preferably, the average diameter of the semiconductor particles is from 10 to 100 nm. Furthermore, the thickness of the mesoporous semiconductor layer is in the range from 50 nm to 1000 nm, preferably from 100 to 800 nm.

(13) The mesoporous insulating layer can be made of semiconductor particles. Suitable semiconductor particles comprise a material selected from ZrO.sub.2, Al.sub.2O.sub.3, SiO.sub.2, SiC, Si.sub.3N.sub.4, Ca.sub.3(PO.sub.4).sub.2 or any combination thereof. Preferably the semiconductor particles are selected from ZrO.sub.2, and Al.sub.2O.sub.3. The average diameter of the semiconductor particles may be from 10 to 500 nm, from 10 to 400 nm. Preferably, the average diameter of the semiconductor particles is from 10 to 100 nm. Furthermore, the thickness of the mesoporous semiconductor layer is in the range from 50 nm and 1000 nm, preferably from 100 to 800 nm.

(14) The conductive substrate is selected from indium tin oxide (ITO) film substrate, fluorine-doped tin oxide (FTO) film substrate, ZnOGa.sub.2O.sub.3 film substrate, ZnOAl.sub.2O.sub.3 film substrate, or tin-based oxides film substrate. Preferably the transparent conductive substrate is a glass substrate covered by a fluorine-doped tin oxide (FTO). The specific examples of the transparent substrate include, but are not limited to, transparent inorganic substrates, such as quartz and glass; transparent plastic substrates, such as poly(ethylene terephthalate) (PET), poly(ethylene 2,6-naphthalate) (PEN), polycarbonate (PC), polyethylene (PE), polypropylene (PP), and polyimide (PI). Preferably, the material of the transparent substrate is glass.

(15) One additional blocking layer or dense layer is optional and is deposited onto the conductive substrate to be an intervening layer between the conductive substrate and the mesoporous inorganic P-I-N scaffold or metal oxides framework composing the ETL/active layer/HTL component to separate the substrate and the perovskite material. The dense layer or additional blocking layer comprises metal oxide selected from TiO.sub.2, ZnO and NiO

(16) The negative electrode is selected from gold (Au), silver (Ag), aluminum (Al), copper (Cu), platinum (Pt), nickel (Ni), carbon (C), or the like. Furthermore, the metal negative electrode is gold (Au) with a thickness of range between 50 nm and 200 nm. Additionally, the negative electrode is porous Carbon (C) with a thickness of range between 5 um and 15 um.

(17) The organic-inorganic perovskite material is of the formula CH.sub.3NH.sub.3PbX.sub.mY.sub.3-m, wherein m represents an integer of 1 to 3; X and Y represent at least one of iodine (I), bromine (Br), and chlorine (Cl). Preferably the organic-inorganic perovskite material is CH.sub.3NH.sub.3PbI.sub.3.

(18) The present invention also relates a method for manufacturing a perovskite solar cell, and the method is presented as follows.

(19) First, a conductive substrate is coated by deposition of a mesoporous inorganic N-type semiconductor layer, and said deposition being followed by successive depositions of a mesoporous inorganic insulating layer and of a mesoporous inorganic P-type semiconductor layer. Thus a mesoporous inorganic P-I-N metal oxides framework of scaffold is obtained. In a further step, an organic-inorganic perovskite solution is deposited into the mesoporous inorganic P-I-N metal oxides framework and this step is followed by the formation of a negative electrode onto the mesoporous inorganic framework filled with the perovskite material, so as to form an organic-inorganic perovskite solar cell. Or a porous negative electrode is formed onto the mesoporous inorganic P-I-N metal oxides framework without perovskite material and this step is followed by the filling of said framework with the perovskite material, so as to form an organic-inorganic perovskite solar cell.

(20) The semiconductor particles are prepared in a form of a paste or slurry, and then the transparent conductive substrate is coated with the paste. Additionally, the coating can be held for one time or many times, in order to obtain a mesoporous semiconduct layer with a suitable thickness. The mesoporous inorganic P-I-N metal oxides framework consists of multiple layers scaffold, wherein each layer of the multiple layers scaffold is formed by semiconductor particles with the same or different diameters. For example, the N-type TiO.sub.2 semiconductor particles with a diameter from 10 to 50 nm are coated in a thickness from 50 to 600 nm onto the conductive substrate or the additional blocking layer. Then the Al.sub.2O.sub.3 semiconductor particles with a diameter from 10 to 100 nm are coated in a thickness from 100 to 800 nm thereon. Further then, a P-type NiO semiconductor particles with a diameter from 10 to 100 nm are coated in a thickness of 100 to 800 nm.

(21) One additional blocking layer is deposited on the conductive substrate before the coating of the mesoporous inorganic metal oxides scaffold layer to separate the substrate and the organic-inorganic perovskite material.

(22) The deposition of mesoporous inorganic semiconductor layers involves a method selected from spin coating, roll coating, printing, ink-jet printing, lithography, stamping and any combination thereof.

(23) After depositing the mesoporous inorganic P-I-N metal oxides framework, said mesoporous inorganic P-I-N metal oxides framework is annealed for 30-40 minutes at 400-500 C.

(24) The step of filling perovskite solution into mesoporous inorganic layers may be performed by deposition with a method selected from dipping, spin coating, or drop casting.

(25) After the filling of the mesoporous inorganic layers with the organic-inorganic perovskite solution, the light absorption material is annealed for 10-30 minutes at 60-80 C.

(26) The invention also relates to a method of producing a perovskite solar cell, comprising the steps of:

(27) 1) preparing a P-I-N mesoporous framework on a transparent conductive substrate, comprising: uniformly coating of the slurry of particles of n-type semiconductor material of size from 10-100 nm after the formation of a transparent conductive substrate (1) coated by a spin coating method or a screen printing method onto the transparent conductive substrate and drying the slurry to remove the solvent to form n-type semiconductor layer having a thickness from 50-600 nm; uniformly coating the slurry of particles of the insulating material having a size from 10-400 nm by a spin coating method or a screen printing onto the n-type semiconductor layer, and drying the slurry to remove the solvent to form an insulating layer having a thickness from 100-800 nm; uniformly coating the slurry of particles of by p-type semiconductor material having a size from 10-400 nm by spin coating method or a screen printing method, and drying the slurry to remove the solvent to form a p-type semiconductor layer having a thickness from 100-800 nm; sintering the slurries forming the P-I-N structure/framework to remove the original organic linking agent at 400 to 500 C. to form mesopores in the n-type semiconductor layer, the insulating layer and the p-type semiconductor layer, whereby mesoporous P-I-N structure is formed onto the transparent conductive substrate;

(28) Or, uniformly coating of the slurry of particles of p-type semiconductor material of size from 10-400 nm after the formation of a transparent conductive substrate (1) coated by a spin coating method or a screen printing method onto the transparent conductive substrate and drying the slurry to remove the solvent to form p-type semiconductor layer having a thickness from 100-800 nm; uniformly coating the slurry of particles of the insulating material having a size from 10-400 nm by a spin coating method or a screen printing onto the n-type semiconductor layer, and drying the slurry to remove the solvent to form an insulating layer having a thickness from 100-800 nm; uniformly coating the slurry of particles of by n-type semiconductor material having a size from 10-100 nm by spin coating method or a screen printing method, and drying the slurry to remove the solvent to form a n-type semiconductor layer having a thickness from 50-600 nm; sintering the slurries forming the P-I-N structure/framework to remove the original organic linking agent at 400 to 500 C. to form mesopores in the n-type semiconductor layer, the insulating layer and the p-type semiconductor layer, whereby mesoporous P-I-N structure is formed onto the transparent conductive substrate;

(29) 2) filling with perovskite materials, and preparing the electrode layer, comprising: filling by spin coating or drop coating perovskite material into the n-type semiconductor layer, insulating layer and p-type semiconductor layers mesoporous framework (P-I-N framework) and preparing an electrode layer onto the P-I-N mesoporous framework;

(30) or preparing the porous electrode layer onto the P-I-N mesoporous framework, and filling by spin coating or drop coating perovskite materials into the mesoporous P-I-N framework.

(31) The solid content of the inorganic nanoparticles represent 18 wt %, the appropriate inorganic nanoparticles in an organic linking agent being constituted by the slurry of the p-type semiconductor material, the slurry of n-type semiconductor material and the insulating material in solvent, wherein the solvent is terpineol and the organic linking agent being ethyl cellulose. The mass ratio of the inorganic nanoparticles and the organic linking agent is 1:0.6.

(32) The method of the invention further comprises, before step 1), a step of depositing a dense layer of electrons or holes blocking layer by spray pyrolysis method onto the transparent conductive substrate.

(33) In the step 2) of the method of the invention, the porous electrode layer is selected from a porous carbon electrode or a metal electrode.

(34) In one embodiment of the present invention, the negative electrode gold (Au) is deposited by thermal evaporation of metal on the mesoporous inorganic P-I-N metal oxides framework filled with perovskite material.

(35) The negative electrode Carbon (C) is deposited by printing onto the mesoporous inorganic P-I-N metal oxides framework, which can be already filled with the organic-inorganic perovskite material. Or the negative electrode is porous Carbon (C) is deposited by printing onto the mesoporous inorganic P-I-N metal oxides framework before being filled with the organic-inorganic perovskite material; the filling process with the organic-inorganic perovskite solution can be carried through the porous Carbon (C) negative electrode.

(36) More and more solar panel structures use perovskite materials, which involves the need to strictly control the film quality and film thickness as well as the process maturity of the hole transport layer being organic materials. All these organic materials are expensive and increase the costs of solar devices. Further the long-term stability of these organic materials as well as solar devices based on these materials represent challenges for the preparation of said device. The use of inorganic materials in the preparation hole transport layer is difficult and requires specific equipment and conditions to obtain high quality, appropriate film thickness, which increases the production cost of solar cells. The invention solves the perovskite solar cell preparation process complexity, high cost of production of technical problems. Using the mesoporous P-I-N framework and, in particular, a hole transport layer using a mesoporous inorganic material for the p-type semiconductor reduces the cost of raw materials, and also lowers the requirements for film quality and thickness usually needed for the hole transport layer. It only requires the use of simple inexpensive method such as spin-coating method or a screen printing method to obtain the mesoporous structures, simplifying the production process and improve the yield by reducing production costs. Using mesoporous structure for the hole transport layer suppresses carrier recombination effects inside the solar cell, effectively improving the energy conversion efficiency of solar cells up to 14% and simplifying the perovskite solar cell preparation process, reducing the costs while ensuring the perovskite high energy conversion efficiency of solar cells and creating good prospects for industrial application.

(37) The mesoporous inorganic P-I-N scaffold filled with organic-inorganic perovskite includes a mesoporous inorganic n-type semiconductor layer (3), a mesoporous inorganic p-type semiconductor (5), and a mesoporous inorganic insulating layer (4) inserts between layer (3) and layer (5). The organic-inorganic perovskite is infiltrated into the mesoporous scaffold as a light absorption material. The key element of the present invention is that the mesoporous inorganic charge transport layers are prepared before being filled by the light absorption material (organic-inorganic perovskite).

(38) The mesoporous inorganic n-type semiconductor layer (3) comprises a material which can be selected from TiO.sub.2, SnO.sub.2, ZnO, Zn.sub.2SnO.sub.4, Nb.sub.2O.sub.5, WO.sub.3, BaTiO.sub.3 or SrTiO.sub.3 or any combination thereof.

(39) The mesoporous inorganic p-type semiconductor layer (5) comprises a material which can be selected from NiO, CuO, CuSCN, CuI, CuGaO.sub.2, CuCrO.sub.2 or CuAlO.sub.2 or any combination thereof. The mesoporous inorganic insulating layer 4 can be selected from ZrO.sub.2, AlO.sub.2O.sub.3, SiO.sub.2, SiC, Si.sub.3N.sub.4, Ca.sub.3(PO.sub.4).sub.2 or any combination thereof.

(40) For example, TiO.sub.2, Al.sub.2O.sub.3, NiO nanocrystalline slurry with a particle size range between 10 nm and 100 nm can be used in the present invention. Furthermore, the mesoporous semiconductor layers can be formed by using a spin coating process or a printing process with a film thickness range between 50 nm and 1000 nm.

(41) The light absorption material filled in mesoporous semiconductor layers is made of organic-inorganic perovskite represented by the formula CH.sub.3NH.sub.3PbX.sub.mY.sub.3-m, wherein m represents an integer of 1 to 3; X and Y represent at least one of iodine (I), bromine (Br), and chlorine (Cl).

(42) The conductive substrate (1) can be independently selected from FTO glass substrate, ITO glass substrate, AZO glass substrate or IZO glass substrate. For example, FTO glass substrate can be used in the present invention.

(43) One additional blocking layer (2) may be deposited as an intervening layer between the conductive substrate, which may be any one of the aforementioned transparent substrate, e.g. FTO glass substrate, and the mesoporous inorganic P-I-N metal oxides framework, said framework being filled or not with organic-inorganic perovskite material. Said additional blocking layer is to separate the conductive substrate, e.g. FTO glass substrate, and the perovskite material.

(44) In one embodiment, the additional blocking layer (2) as being a hole blocking layer is formed onto the FTO conductive substrate by spray pyrolysis or spin coating. The thickness of the additional blocking layer (2) is from 30-100 nm. For example, a 60 nm thick TiO.sub.2 may be used.

(45) In one embodiment, the negative electrode (6) is formed onto the hole transport layer (5) by vapor deposition. The negative electrode (6) can be selected from metals selected from gold (Au), silver (Ag), aluminum (Al), copper (Cu), platinum (Pt), nickel (Ni), carbon (C) or the like. The thickness of the negative electrode (6) is from 50 to 150 nm. For example, a 100 nm thick gold (Au) metal coating may be used.

(46) The negative electrode (6) is formed onto the hole transport layer (5) by screen printing. In a specific embodiment, the negative electrode (6) is porous carbon electrode. The thickness of the negative electrode (6) is from 5 to 15 m. A carbon electrode with a thickness of 10 m may be used in the present invention.

(47) The present invention further provides a method for manufacturing a perovskite solar cell, comprising

(48) a first step, wherein a conductive substrate is coated with a mesoporous inorganic N-type semiconductor layer by deposition, followed by the deposition of a mesoporous inorganic insulating layer onto the N-type semiconductor and a mesoporous inorganic P-type semiconductor layer onto said inorganic insulating layer to obtain the mesoporous inorganic P-I-N metal oxides framework. Subsequently, the organic-inorganic perovskite solution is deposited or filled into the mesoporous inorganic P-I-N metal oxides framework, followed by a step wherein a negative electrode is formed onto the mesoporous inorganic P-I-N metal oxides framework filled with the organic-inorganic perovskite material; Or subsequently to the step of the deposition of the mesoporous inorganic P-I-N metal oxides framework, a porous negative electrode is formed onto the mesoporous inorganic P-I-N metal oxides framework free of the organic-inorganic perovskite material, followed by a step wherein said framework is filled by the organic-inorganic perovskite material is.

(49) Further, the mesoporous inorganic P-I-N metal oxides framework is annealed for 30-40 minutes at 400-500 C. before the filling process with the organic-inorganic perovskite material.

(50) Furthermore, the perovskite solution used as light absorption material is filled into the mesoporous inorganic layers of the mesoporous inorganic P-I-N metal oxides framework, light absorption material is annealed for 10-30 minutes at 60-80 C.

(51) Finally, in a particular embodiment, a negative electrode being in gold (Au) is deposited by thermal evaporation onto the mesoporous inorganic P-I-N metal oxides framework filled with perovskite material.

(52) In another particular embodiment, a negative electrode being in Carbon (C) is deposited by printing on the mesoporous inorganic P-I-N metal oxides framework being filled with organic-inorganic perovskite material and annealed for 10-30 minutes at 80-100 C.

(53) In a further particular embodiment, the negative electrode is porous Carbon (C) is deposited by printing onto the mesoporous inorganic P-I-N metal oxides framework free of organic-inorganic perovskite material, and before the filling process of perovskite, the multiple-layers of said framework is annealed for 30-40 minutes at 400-500 C.

(54) The organic-inorganic perovskite based solar cell may comprise a dense layer of metal oxide selected from TiO.sub.2, ZnO, NiO; a mesoporous inorganic n-type semiconductor layer comprising at least one of a mesoporous material selected from TiO.sub.2, SnO.sub.2, ZnO, Zn.sub.2SnO.sub.4, Nb.sub.2O.sub.5, WO.sub.3, BaTiO.sub.3, SrTiO.sub.3; a mesoporous insulating barrier layer comprising at least one of a mesoporous material selected from ZrO.sub.2, Al.sub.2O.sub.3, SiO.sub.2, SiC, Si.sub.3N.sub.4, Ca.sub.3(PO.sub.4).sub.2; a p-type semiconductor mesoporous layer comprising at least one of a mesoporous material selected from NiO, CuO, CuSCN, CuI, CuGaO.sub.2, CuCrO.sub.2 or CuAlO.sub.2; a metal electrode layer comprising a metal selected from Au, Ag and Al or an electrode being a conductive carbon mesoporous or a pair thereof; and the multilayers of mesoporous material may be filled with one or more perovskites of formula (CH.sub.3NH.sub.3)PbX.sub.mY.sub.3-m, wherein X, YCl, Br, I; m=0 to 3, preferably perovskite is iodine lead methylamine (CH.sub.3NH.sub.3PbI.sub.3).

(55) The organic-inorganic perovskite based solar cell may be obtained after the preparation by overlaying the mesoporous inorganic n-type semiconductor layer, the mesoporous insulating barrier layer and the mesoporous inorganic p-type semiconductor layer by spin coating method or screen printing method or the like and sintering said mesoporous multilayers, sintering at temperatures from 400-500 C. for 30 min.

(56) Porous carbon conductive electrode is prepared by screen printing on the multi-layer film and dried by sintering at temperature from 400-500 C. for 30 min. The thickness of said electrode is from 2-10 m.

(57) The metal electrode is prepared by vapor deposition method at a high vacuum (10-5 Pa) condition. The thickness of said metal electrode is from 50-200 nm.

(58) The present invention is described more concretely with reference to the following examples, which, however, are not intended to restrict the scope of the invention.

EXAMPLES

Example 1

(59) Preparation of a Mesoporous Inorganic P-I-N Metal Oxides Framework

(60) The substrate of the device was a glass substrate covered with fluorine-doped tin oxide (FTO), wherein the thickness of the glass substrate was 4 mm and the electric resistance of the glass substrate is 10. A blocking layer of TiO.sub.2 was deposited on the FTO glass by spray pyrolysis deposition with di-isopropoxytitanium bis(acetyl acetonate) (TiDIP, 75% in isopropanol, Aldrich) solution at 450 C. A mesoporous inorganic N-type semiconductor layer was coated by screen printing method using a paste containing TiO.sub.2 particles with diameter of 20 nm (DSL. 18NR-T, 20 nm, Dyesol, Austrilia) for one time or several times. The thickness of the TiO.sub.2 layer was 400 nm, and then dried in 125 C. for 10 min. Then, a mesoporous inorganic insulating layer was coated by the same screen printing method using a paste containing Al.sub.2O.sub.3 particles with diameter of 20 nm (Aladdin, 20 nm, China). The thickness of the TiO.sub.2 layer was 400 nm, and then dried in 125 C. for 10 min. Additionally, a mesoporous inorganic P-type layer was coated by the same screen printing method using a paste containing NiO particles with diameter of 20 nm (Inframat, 20 nm, USA), wherein the thickness of the NiO layer was 600 nm. Finally, the coated glass substrate was sintered at 400-500 C. for 30 min, and the thickness of the mesoporous inorganic P-I-N metal oxides framework was 1.4 m.

Example 2

(61) Preparation of a Mesoporous Inorganic P-I-N Metal Oxides Framework

(62) The process for preparing the mesoporous inorganic P-I-N metal oxides framework of the present embodiment was the same as that described in Example 1, except that the TiO.sub.2 particles was substituted with the ZnO particles with diameter of 10 nm and the thickness of ZnO layer was 200 nm. Then, the coated glass substrate was sintered at 500 C. for 30 min, and the thickness of the mesoporous inorganic P-I-N metal oxides framework was 1.2 m.

Example 3

(63) Preparation of a Mesoporous Inorganic P-I-N Metal Oxides Framework

(64) The process for preparing the mesoporous inorganic P-I-N metal oxides framework of the present embodiment was the same as that described in Example 1, except that the Al.sub.2O.sub.3 particles was substituted with the ZrO.sub.2 particles with diameter of 50 nm and the thickness of ZrO.sub.2 layer was 600 nm. Then, the coated glass substrate was sintered at 500 C. for 30 min, and the thickness of the mesoporous inorganic P-I-N metal oxides framework was 1.6 m.

Example 4

(65) Preparation of a Mesoporous Inorganic P-I-N Metal Oxides Framework

(66) The process for preparing the mesoporous inorganic P-I-N metal oxides framework of the present embodiment was the same as that described in Example 1, except that the size of NiO particles was change to 50 nm and the thickness of NiO layer was 1000 nm. Then, the coated glass substrate was sintered at 500 C. for 30 min, and the thickness of the mesoporous inorganic P-I-N metal oxides framework was 1.8 m.

Example 5

(67) Preparation of a Perovskite Solar Cell

(68) The filling of CH.sub.3NH.sub.3PbI.sub.3 into the mesoporous framework prepared by Example 1 was carried out by a two-step deposition technique. At the beginning, PbI.sub.2 solution (32 wt % in DMF) was dropped into the mesoporous framework followed by annealing at 70 C. for 30 min. In the second step, the cell was dipped into CH.sub.3NH.sub.3I solution (10 mg/ml in isopropanol) for 20-30 sec, and then annealed at 70 C. for another 30 min. During the dip and the annealing, the CH.sub.3NH.sub.3PbI.sub.3 was formed, indicated by the dark brown color of the electrode. After the negative electrode was deposited by evaporating 100 nm of gold (Au) under pressure of 10.sup.5 Torr, a perovskite solar cell of the present embodiment was obtained.

Example 6

(69) Preparation of a Perovskite Solar Cell

(70) The filling of CH.sub.3NH.sub.3PbI.sub.3 into the mesoporous framework prepared by Example 1 was carried out by a two-step deposition technique. At the beginning, PbI.sub.2 solution (32 wt % in DMF) was dropped into the mesoporous framework followed by annealing at 70 C. for 30 min. In the second step, the cell was dipped into CH.sub.3NH.sub.3I solution (10 mg/ml in isopropanol) for 20-30 sec, and then annealed at 70 C. for another 30 min. During the dip and the annealing, the CH.sub.3NH.sub.3PbI.sub.3 was formed, indicated by the dark brown color of the electrode. Finally, devices were completed by depositing commercial carbon paste on top of the perovskite film by doctor-blading technique. After drying at 100 C. for 30 min, a perovskite solar cell of the present embodiment was obtained.

Example 7

(71) Preparation of a Perovskite Solar Cell

(72) Porous carbon negative electrode (carbon black/graphite: 4/1) was subsequently prepared by screen printing on the mesoporous framework prepared by Example 1 before the filling of perovskite. The coated glass substrate was sintered at 400-500 C. for 30 min, and the thickness of the porous carbon negative electrode was 10 m. Then the filling of CH.sub.3NH.sub.3PbI.sub.3 into the mesoporous framework prepared by Embodiment 1 was carried out by a two-step deposition technique. At the beginning, PbI.sub.2 solution (32 wt % in DMF) was dropped into the mesoporous framework through the upper porous carbon electrode and then followed by annealing at 70 C. for 30 min. In the second step, the cell was dipped into CH.sub.3NH.sub.3I solution (10 mg/ml in isopropanol) for 10-20 min. During the dip, the CH.sub.3NH.sub.3PbI.sub.3 was formed, indicated by the dark brown color of the electrode. After drying at 60 C. for 20-30 min, a perovskite solar cell was obtained.

Example 8

(73) Preparation of a Perovskite Solar Cell

(74) The process for preparing the perovskite solar cell of the present embodiment was the same as that described in Example 7, except that the mesoporous framework prepared by Example 1 was substituted with the mesoporous framework prepared by Example 2.

Example 9

(75) Preparation of a Perovskite Solar Cell

(76) The process for preparing the perovskite solar cell of the present embodiment was the same as that described in Example 7, except that the mesoporous framework prepared by Example 1 was substituted with the mesoporous framework prepared by Example 3.

Example 10

(77) Preparation of a Perovskite Solar Cell

(78) The process for preparing the perovskite solar cell of the present embodiment was the same as that described in Example 7, except that the mesoporous framework prepared by Example 1 was substituted with the mesoporous framework prepared by Example 4.

(79) The short circuit current (J.sub.SC), open circuit voltage (V.sub.OC), filling factor (FF), photoelectric conversion efficiency (PCE), and incident photon-to-current conversion efficiency (IPCE) of the perovskite solar cells prepared by Embodiments 5-10 were measured under the illumination of AM 1.5 stimulated light. The testing results are shown in the following Table 1.

(80) TABLE-US-00001 TABLE 1 Perovskite solar cell J.sub.SC (mA cm.sup.2) V.sub.OC (mV) FF PCE (%) Example 5 16.51 904 0.70 10.90 Example 6 16.50 902 0.71 10.57 Example 7 19.62 915 0.76 13.65 Example 8 18.28 923 0.72 12.14 Example 9 17.56 916 0.71 11.41 Example 10 17.22 908 0.70 10.95

(81) Referring to Table 1, testing results of the Examples 5-7 discloses comparison of photoelectronic performance parameters of the perovskite solar cell with different negative electrode 6. It can be seen that the embodiment 5 and 6, wherein gold (Au) or carbon (C) electrode is deposited by evaporating or doctor-blading technique after the perovskite has been filled the mesoporous inorganic P-I-N metal oxides framework, both have lower photoelectric performance characteristics compared with the Example 7. In Example 7, the porous carbon electrode is directly deposited on the mesoporous framework before the perovskite filling. The reason of the performance difference of the above-mentioned embodiments is that the postprocessing of negative electrode on the active component (ETL/active layer/HTL) has negative effects on the organic-inorganic perovskite, which cause a relatively lower photoelectronic performance of the devices.

(82) It can be seen from the results given in Table 1 that photoelectric performance characteristics of devices of embodiment 7-10 have relatively good performance, especially TiO.sub.2/Al.sub.2O.sub.3/NiO/C(CH.sub.3NH.sub.3PbI.sub.3) of embodiment 7 has preferable values of V.sub.OC=915 mV, J.sub.SC=19.62 mA cm.sup.2, FF=0.76 and PCE=13.65%. FIG. 3 shows the current density-voltage (J-V) curve of the perovskite solar cell with TiO.sub.2/Al.sub.2O.sub.3/NiO as mesoporous inorganic P-I-N metal oxides framework with a thickness of 1.4 m. The reason of the performance difference of the above-mentioned embodiments is that the intrinsic characteristics of semiconductor such as energy level, electricity, and optical property as well as the particle size and film thickness will influence the photoelectric performance of the devices.

(83) FIG. 4 shows energy band diagrams of each layer of a device having FTO/TiO.sub.2/Al.sub.2O.sub.3/NiO/C(CH.sub.3NH.sub.3PbI.sub.3) component the light is absorbed by the organic-inorganic perovskite, the conduction and valence permitting electron injection and hole transportation to the TiO.sub.2 and to the NiO layer, respectively. Following light excitation, carriers are created in the perovskite light absorption material (CH.sub.3NH.sub.3PbI.sub.3) and injects negative and positive charge carrier in the respective electron transport layer (TiO.sub.2) and hole transport layer (NiO), which subsequently are collected as photocurrent at the front (FTO) and back (C) contacts of the cell. For the insulating layer Al.sub.2O.sub.3, charge injection cannot be happened because the mismatch of energy band, which is serve as insulating layer to avoid the direct contact between electron transport layer TiO.sub.2 (ETL) and electron transport layer NiO (HTL).

(84) Furthermore, FIG. 5A is a cross-sectional scanning electron microscopy (SEM) photography of the FTO/TiO.sub.2/Al.sub.2O.sub.3/NiO/C architecture which the FTO glass substrate is coated with a mesoporous inorganic TiO.sub.2/Al.sub.2O.sub.3/NiO metal oxides framework combined with a porous carbon electrode, which is prepared by screen printing. The film thickness of the mesoporous inorganic P-I-N metal oxides framework is 1.2-1.6 m, and the thickness of the porous carbon electrode is 10-12 m. FIG. 5B is a cross-sectional scanning electron microscopy (SEM) photograph of the mesoporous TiO.sub.2/Al.sub.2O.sub.3/NiO framework filled with perovskite. The filling of CH.sub.3NH.sub.3PbI.sub.3 into the mesoporous framework is carried out by the two-step deposition technique, it can be seen that continuous organic-inorganic perovskite absorption layer is formed in mesoporous of inorganic framework.

(85) Although the present invention has been explained in relation to its preferred embodiment, it is to be understood that many other possible modifications and variations can be made without departing from the scope of the invention as hereinafter claimed.