Passivating barrier layers in contact with perovskites for solar cells

Abstract

Provided is a hybrid organic-inorganic solar cell comprising a substrate, a transparent conductive oxide (TCO) layer deposited on the substrate, an n-type electron transport material (ETM) layer, a p-type hole transport material (HTM) layer, an i-type perovskite layer, and an electrode layer, wherein the substrate layer is arranged in a nip stack or a p-i stack, and a passivation barrier layer is disposed between (i) the perovskite and the HTM, (ii) the perovskite and the ETM, (iii) the perovskite and the HTM, and the perovskite and the ETM, or (iv) the TCO and the ETM, and the ETM and the perovskite, and the perovskite and the HTM, or (v) the substrate and the TCO, and the TCO and the ETM, and the ETM and the perovskite, and the perovskite layer and the HTM, or (vi) a pair of ETM layers, or (vii) a pair of HTM layers. [Selection diagram] Figure 3N

Description

Detailed Description of the Invention

[0001] [Field of the Invention] The present invention relates to solar cells, and more particularly to passivation barrier layers disposed between layers of a solar cell stack.

[0002] [Background of the invention] Perovskite materials are of interest for photovoltaic solar cell applications, but suffer from material stability issues. Such issues can arise from exposure to other materials used in the fabrication of the solar cell as well as environmental exposure (water, oxygen, etc.) over the cell's lifetime. Attempts have been made to create passivating barrier layers on the perovskite layer of solar cells, but to date have met with limited success.

[0003] There is a need for a passivation barrier layer disposed on perovskite solar cells to enhance performance.

[0004] [Summary of the Invention] To address the needs in the art, a hybrid organic-inorganic solar cell is provided, which includes a substrate, a transparent conductive oxide (TCO) layer deposited on the substrate, an electron transport material (ETM) layer that is an n-type layer, a hole transport material (HTM) layer that is a p-type layer, at least one passivation barrier layer, a perovskite layer that is an i-type layer, and an electrode layer, wherein the substrate, the TCO layer, the ETM layer, the perovskite layer, the HTM layer, and the electrode layer are arranged in a nip stack, or the substrate, the TCO layer, the HTM layer, the perovskite layer, the ETM layer, and the electrode layer are arranged in a pin stack, and the at least one passivation barrier layer (i) between a perovskite layer and an HTM layer, or (ii) between a perovskite and an ETM layer, or (iii) between a perovskite and an HTM layer, and between a perovskite layer and an ETM, or (iv) between a TCO layer and an ETM layer, and between an ETM layer and a perovskite layer, and between a perovskite layer and an HTM layer, or (v) between a substrate and a TCO layer, and between a TCO layer and an ETM layer, and between an ETM layer and a perovskite layer, and between a perovskite layer and an HTM layer, or (vi) between a pair of ETM layers, or (vii) between a pair of HTM layers.

[0005] According to one aspect of the present invention, the material of the ETM layer comprises fullerene, ZnOS, TiO, SnO, ZnO, CdS, SbS, BiS, or any combination thereof, where the fullerene comprises PCBM or C, and the fullerene is doped or undoped.

[0006] In another embodiment of the present invention, the material of the HTM layer is P3HT, spiro-OMeTAD, PEDOT:PSS, NiO x , MoO x , WO x , CuO x , CuSCN, V2O5, MoS2, CuGaO2, PTAA, poly-TPD, PbS, or any combination thereof, wherein P3HT, spiro-OMeTAD, PTAA, and poly-TPD are doped or undoped.

[0007] In a further aspect of the invention, the material of the TCO layer comprises In2O3:SnO2 (ITO), In2O3:H, SnO2:F (FTO), SnO2, ZnO:Al, ZnO:B or any combination thereof.

[0008] In yet another aspect of the invention, the material of the electrode layer comprises In2O3:SnO2 (ITO), In2O3:H, ZnO:Al, ZnO:B, SnO2, C, Au, Ag, Cu, Ni or Al.

[0009] According to one aspect of the present invention, the material of the passivation barrier layer is Al2O3, SnO2, TiO2, ZnO, NiO, MoO x , CuO x ,CuGaO x , Y2O3, SiN x , SiO2, Ta2O5, Triflurorobutylamine hydroiodide (TFBA), AlF x , LiF or PbI2.

[0010] In yet another aspect of the invention, the electrode adjacent to the substrate may be semi-transparent over a non-transparent electrode.

[0011] In a further aspect of the invention, the material of the perovskite layer is CH3NH3PbI3, CH3NH3PbCl3, CH3NH3PbBr3, CH3NH3PbI 3-x Cl x , CH3NH3PbI 3-x Br x , HC(NH2)2PbI3, HC(NH2)2PbCl3, HC(NH2)2PbBr3, HC(NH2)2PbI 3-x Cl x , HC(NH2)2PbI 3-x Br x , [HC(NH2)2] 1-x Cs x PbI3, [HC(NH2)2] 1-x Cs x PbI 3-y Br y , CsPbI 3-x Br x, CH3NH3Pb 1-x Sn x I 3-y Br y , (CH3NH3) 1-x-y [HC(NH2)2] y Cs x PbI 3-z Br z , (CH3NH3) 1-x-y [HC(NH2)2] y Cs x Pb 1-z Sn z I 3-δ Br δ , and (CH3NH3) 1-x-y-z [HC(NH2)2] z Cs y Rb x PbI 3-δ Br δ In one embodiment, the Pb in the perovskite is partially or completely replaced by other Group IV elements. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 shows an exemplary ALD schematic for fabricating a passivation barrier layer in a hybrid organic-inorganic solar cell, according to one embodiment of the present invention. [Figure 2A] 2A-2C show X-ray diffraction (XRD) spectra of perovskite films (2A) immediately after fabrication (day 0) with and without AlO in contact with a passivating barrier layer, (2B) without a passivating barrier layer, and (2C) in contact with a passivating barrier layer, according to one embodiment of the present invention. [Figure 2B] 2A-2C show X-ray diffraction (XRD) spectra of perovskite films (2A) immediately after fabrication (day 0) with and without AlO in contact with a passivating barrier layer, (2B) without a passivating barrier layer, and (2C) in contact with a passivating barrier layer, according to one embodiment of the present invention. [Figure 2C]2A-2C show X-ray diffraction (XRD) spectra of perovskite films (2A) immediately after fabrication (day 0) with and without AlO in contact with a passivating barrier layer, (2B) without a passivating barrier layer, and (2C) in contact with a passivating barrier layer, according to one embodiment of the present invention. [Figure 3A] 3A-3O show schematic diagrams of passivation barrier layers being deposited on hybrid organic-inorganic pin and nip solar cells according to one embodiment of the present invention. [Figure 3B] 3A-3O show schematic diagrams of passivation barrier layers being deposited on hybrid organic-inorganic pin and nip solar cells according to one embodiment of the present invention. [Figure 3C] 3A-3O show schematic diagrams of passivation barrier layers being deposited on hybrid organic-inorganic pin and nip solar cells according to one embodiment of the present invention. [Figure 3D] 3A-3O show schematic diagrams of passivation barrier layers being deposited on hybrid organic-inorganic pin and nip solar cells according to one embodiment of the present invention. [Figure 3E] 3A-3O show schematic diagrams of passivation barrier layers being deposited on hybrid organic-inorganic pin and nip solar cells according to one embodiment of the present invention. [Figure 3F] 3A-3O show schematic diagrams of passivation barrier layers being deposited on hybrid organic-inorganic pin and nip solar cells according to one embodiment of the present invention. [Figure 3G] 3A-3O show schematic diagrams of passivation barrier layers being deposited on hybrid organic-inorganic pin and nip solar cells according to one embodiment of the present invention. [Figure 3H] 3A-3O show schematic diagrams of passivation barrier layers being deposited on hybrid organic-inorganic pin and nip solar cells according to one embodiment of the present invention. [Figure 3I]3A-3O show schematic diagrams of passivation barrier layers being deposited on hybrid organic-inorganic pin and nip solar cells according to one embodiment of the present invention. [Figure 3J] 3A-3O show schematic diagrams of passivation barrier layers being deposited on hybrid organic-inorganic pin and nip solar cells according to one embodiment of the present invention. [Figure 3K] 3A-3O show schematic diagrams of passivation barrier layers being deposited on hybrid organic-inorganic pin and nip solar cells according to one embodiment of the present invention. [Figure 3L] 3A-3O show schematic diagrams of passivation barrier layers being deposited on hybrid organic-inorganic pin and nip solar cells according to one embodiment of the present invention. [Figure 3M] 3A-3O show schematic diagrams of passivation barrier layers being deposited on hybrid organic-inorganic pin and nip solar cells according to one embodiment of the present invention. [Figure 3N] 3A-3O show schematic diagrams of passivation barrier layers being deposited on hybrid organic-inorganic pin and nip solar cells according to one embodiment of the present invention. [Figure 3O] 3A-3O show schematic diagrams of passivation barrier layers being deposited on hybrid organic-inorganic pin and nip solar cells according to one embodiment of the present invention. [Figure 4A] FIG. 4A is a graph showing experimental data of degradation without Al 2 O 3 in contact with the passivation barrier layer. [Figure 4B] FIG. 4B is a graph showing experimental data of reduced degradation using Al 2 O 3 in contact with a passivation barrier layer, according to one embodiment of the present invention. [Figure 5A] FIG. 5A is a graph showing experimental data of degradation without Al 2 O 3 in contact with the passivation barrier layer. [Figure 5B] FIG. 5B is a graph showing experimental data of reduced degradation using Al 2 O 3 in contact with a passivation barrier layer, according to one embodiment of the present invention. [Figure 6A] FIG. 6A is a graph comparing cell performance immediately after fabrication (day 0) with and without Al 2 O 3 in contact with a passivating barrier layer, according to one embodiment of the present invention. [Figure 6B] FIG. 6B is a graph of substantially no degradation with Al 2 O 3 in contact with a passivating barrier layer, according to one embodiment of the present invention.

[0013] [Detailed explanation] The present invention provides improved devices and processes for fabricating at least one passivation barrier layer in perovskite solar cells, which exhibit superior performance. Thus, the problem of high instability of hybrid organic-inorganic IV-halide perovskite solar cells is successfully addressed.

[0014] According to one example of the present invention, a thin (e.g., between 0.2 nm and a few nanometers thick) Al2O3 passivation barrier layer is used to seal the sensitive perovskite layer. The Al2O3 passivation barrier layer protects the perovskite layer during further deposition of an electron-selective or hole-sensitive contact layer and over the lifetime of the usable solar cell device against water, water vapor, and oxygen, but it does not prevent the formation of low-resistance contacts to the perovskite layer. Here, the Al2O3 passivation barrier layer is thin enough to provide a tunnel contact for the solar cell. The Al2O3 passivation barrier layer is preferably deposited using atomic layer deposition (ALD) from trimethylaluminum (TMA) and HO at 100°C. An exemplary ALD process for this is represented diagrammatically in Figure 1. In this example, the inventors used four ALD deposition cycles. The number of ALD cycles is preferably between 1 and 10, and more preferably between 5 and 10.

[0015] X-ray diffraction (XRD) spectra of perovskite films with and without ALD Al2O3 on top are shown in Figure 2A. There is no obvious change in the crystalline structure of the perovskite film before and after the deposition of ALD Al2O3 on top, as confirmed by the characteristic peaks (14.1°, 28.4°, and 43.2°) present in both individual spectra, which can be assigned to the (110), (220), and (330) peaks of CH3NH3PbI3. After exposure to moisture, degradation of the perovskite without the ALD Al2O3 passivation barrier layer on top is evident from the appearance of a new peak at 12.6° in the XRD spectrum of Figure 2B. This peak is assigned to the (001) diffraction peak of PbI2 and is formed as a result of the transformation of the perovskite upon exposure to oxygen and moisture. In contrast, when exposed to the same humidity conditions, the XRD spectrum of perovskite with ALD Al2O3 on top (Figure 2C) does not show this 12.6° characteristic peak of PbI2, confirming that the ALD Al2O3 in contact with the perovskite acts as a passivating barrier layer, enhancing its stability.

[0016] 3A-3O show hybrid organic-inorganic solar cells including a substrate, a transparent conductive oxide (TCO) layer deposited on the substrate, an electron transport material (ETM) layer which is an n-type layer, a hole transport material (HTM) layer which is a p-type layer, at least one passivation barrier layer, a perovskite layer which is an i-type layer, and an electrode layer, where the substrate, TCO layer, ETM layer, perovskite layer, HTM layer, and electrode layer are arranged in a nip stack, or the substrate, TCO layer, HTM layer, perovskite layer, ETM layer, and electrode layer are arranged in a pin stack, and the at least one passivation barrier layer is (i) a perovskite layer and an HTM layer, or (ii) between a perovskite and an ETM layer, or (iii) between a perovskite and an HTM layer, and between a perovskite layer and an ETM, or (iv) between a TCO layer and an ETM layer, and between an ETM layer and a perovskite layer, and between a perovskite layer and an HTM layer, or (v) between a substrate and a TCO layer, and between a TCO layer and an ETM layer, and between an ETM layer and a perovskite layer, and between a perovskite layer and an HTM layer, or (vi) between a pair of ETM layers, or (vii) between a pair of HTM layers.

[0017] While the configurations shown in Figures 3C-3D (passivating barrier layer between perovskite and electron transport material (ETM) shown in both pin and nip configurations) and Figures 3E-3F (barrier layers between perovskite and HTM, and between perovskite and ETM shown in both pin and nip configurations) are also possible, the experimental data relate to the configuration shown in Figures 3A-3B (passivating barrier layer between perovskite and hole transport material (HTM) shown in both pin and nip configurations). Here, a key feature of all examples is that the passivating barrier layer is directly on top of the photoactive perovskite layer. Figures 3G-3N show passivating barrier layers between multiple layers in hybrid organic-inorganic pin and nip solar cells according to embodiments of the present invention. Perovskite solar cells include two electrodes, at least one of which should be transparent. Therefore, one of the electrodes may be non-transparent. FIG. 3O shows a solar cell stack having a transparent conductive oxide layer distal to the substrate layer and a non-transparent or semi-transparent electrode proximate to the substrate layer.

[0018] Therefore, in a further embodiment of the present invention, the electrode closest to the substrate may be semi-transparent over a non-transparent one. In Figures 3A-3L, the TCO is always closest to the substrate. However, if the top electrode is transparent, the electrode closest to the substrate may be non-transparent.

[0019] According to one aspect of the present invention, the material of the ETM layer comprises fullerene, ZnOS, TiO, SnO, ZnO, CdS, SbS, BiS, or any combination thereof, where the fullerene comprises PCBM or C, where the fullerene is doped or undoped.

[0020] In another embodiment of the present invention, the material of the HTM layer is P3HT, spiro-OMeTAD, PEDOT:PSS, NiO x , MoO x , WO x , CuO x, CuSCN, V2O5, MoS2, CuGaO2, PTAA, poly-TPD, PbS, or any combination thereof, wherein P3HT, spiro-OMeTAD, PTAA, and poly-TPD are doped or undoped.

[0021] In a further aspect of the invention, the material of the TCO layer comprises In2O3:SnO2 (ITO), In2O3:H, SnO2:F (FTO), SnO2, ZnO:Al or ZnO:B or any combination thereof.

[0022] In yet another aspect of the invention, the material of the electrode layer comprises In2O3:SnO2 (ITO), In2O3:H, ZnO:Al, ZnO:B, SnO2, C, Au, Ag, Cu, Ni or Al.

[0023] According to one aspect of the present invention, the material of the passivation barrier layer is Al2O3, SnO2, TiO2, ZnO, NiO, MoO3, CuO, CuGaO2, Y2O3, SiN x , SiO2, Ta2O5, trifluorobutylamine hydroiodide (TFBA), AlF x , LiF or PbI2.

[0024] In a further aspect of the invention, the material of the perovskite layer is CH3NH3PbI3, CH3NH3PbCl3, CH3NH3PbBr3, CH3NH3PbI 3-x Cl x , CH3NH3PbI 3-x Br x , HC(NH2)2PbI3, HC(NH2)2PbCl3, HC(NH2)2PbBr3, HC(NH2)2PbI 3-x Cl x , HC(NH2)2PbI 3-x Br x , [HC(NH2)2] 1-x Cs x PbI3, [HC(NH2)2] 1-x Cs x PbI 3-y Br y , CsPbI 3-x Br x, CH3NH3Pb 1-x Sn x I 3-y Br y , (CH3NH3) 1-x-y [HC(NH2)2] y Cs x PbI 3-z Br z , (CH3NH3) 1-x-y [HC(NH2)2] y Cs x Pb 1-z Sn z I 3-δ Br δ , and (CH3NH3) 1-x-y-z [HC(NH2)2] z Cs y Rb x PbI 3-δ Br δ In one embodiment, the Pb in the perovskite is partially or completely replaced by other Group IV elements.

[0025] In the first example, poly(3-hexylthiophene) (P3HT) is used as the hole transport material. Figure 4A shows the degradation without Al2O3 in contact with a passivating barrier layer. Figure 4B shows the reduced degradation with Al2O3 in contact with a passivating barrier layer.

[0026] In the second example, 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9'-spirobifluorene (spiro-OMeTAD) is used as the hole transport material. Figure 5A shows the degradation without Al2O3 in contact with the passivation barrier layer. Figure 5B shows the reduced degradation with Al2O3 in contact with the passivation barrier layer.

[0027] In a third example, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is used as the hole transport material. Figure 6A compares the cell performance immediately after fabrication (day 0) with and without an Al2O3 passivation barrier layer. It can be seen that without the use of an Al2O3 passivation barrier layer, the cell does not fabricate properly. With the use of an Al2O3 passivation barrier layer, the cell has excellent initial IV performance. Furthermore, Figure 6B shows that there is virtually no degradation with the Al2O3 passivation barrier layer. In the case of PEDOT:PSS as the HTM, the Al2O3 layer is important not only to protect the device from moisture but also to enable the fabrication of perovskite cells using PEDOT:PSS as the HTM.

[0028] In all cases, there was no initial degradation in cell efficiency when an Al2O3 passivation barrier layer was used compared to cells without the passivation barrier layer. The cells were exposed to 40% humidity ambient conditions for 15 days, then 60% humidity for another 10 days, and then ambient laboratory atmosphere (60-75% humidity) for another 30 days. The passivation barrier layer provided greatly improved device stability under humid conditions. While IV performance was maintained for structures with the passivation barrier layer, the performance of cells without the passivation barrier layer significantly decreased over time.

[0029] The present invention is described herein with reference to several exemplary embodiments, which are intended to be illustrative in all respects rather than restrictive. Thus, the present invention is susceptible to many variations in the implementation detailed, which may be derived by those skilled in the art from the description contained herein. For example, an ETM (or HTM) has three main functions: 1.Excellent electron transport (excellent hole transport); 2. Excellent hole-blocking properties (excellent electron-blocking properties); and 3. Barrier properties, including passivation functionality and chemical diffusion barrier functionality where passivation functionality (i.e. chemical reaction or physical absorption with reactive species with adjacent layer(s)) can have two effects: (i) reduction of bulk and / or interface recombination (this applies to the perovskite layer and to the interface of the perovskite with adjacent layers), and (ii) prevention of degradation reactions involving the above-mentioned reactive species (this applies to any of the layers in the stack).

[0030] Additionally, the compound diffusion barrier functionality includes protection against H2O, CO2, O2, solvents, and decomposition materials of other layers (e.g., MAI, etc.).

[0031] Furthermore, the above-mentioned properties can be realized in several layers. For example, an ETM can consist of one electron transport layer, one hole blocking layer, and one passivation barrier layer. However, it is also possible to combine two or three properties in a single layer. Of course, additional passivation barrier layers can be introduced to protect the layers that make up the ETM, HTM, TCO, and electrodes. Therefore, the barriers can be arranged in different ways, as depicted in many device stacks.

[0032] All such variations are considered to be within the scope and concept of the present invention as defined by the following claims and their legal equivalents.

Claims

1. a) a substrate; b) a transparent conductive oxide (TCO) layer deposited on said substrate; c) an electron transport material (ETM) layer, including an n-type layer; d) a hole transport material (HTM) layer, including a p-type layer; e) at least one passivation barrier layer; f) a perovskite layer including an i-type layer, and g) Electrode layer wherein the substrate, the TCO layer, the ETM layer, the perovskite layer, the HTM layer and the electrode layer are arranged in an nip stack, or the substrate, the TCO layer, the HTM layer, the perovskite layer, the ETM layer and the electrode layer are arranged in a pin stack, the at least one passivation barrier layer comprising: disposed between the TCO layer and the ETM layer, between the ETM layer and the perovskite layer, and between the perovskite layer and the HTM layer; The passivation barrier layer is made of SnO ２ , ZnO, NiO ｘ , MoO ｘ , CuO ｘ ,CuGaO ｘ , Y ２ O ３ , Ta ２ O ５ , and PbI ２ 1. A hybrid organic-inorganic solar cell comprising a material selected from the group consisting of:

2. 10. The hybrid organic-inorganic solar cell of claim 1, wherein the at least one passivation barrier layer is further disposed between the substrate and the TCO layer.

3. The ETM layer is made of fullerene, ZnOS, TiO ｘ , SnO ｘ , ZnO ｘ , CdS, Sb ２ S ３ and Bi ２ S ３ 10. The hybrid organic-inorganic solar cell of claim 1, comprising a material selected from the group consisting of:

4. 4. The hybrid organic-inorganic solar cell of claim 3, wherein the material selected is a fullerene, and the fullerene comprises PCBM or C60.

5. The HTM layer is composed of P3HT, spiro-OMeTAD, PEDOT:PSS, NiO ｘ , MoO ｘ , W.O. ｘ , CuO ｘ , Cu[SCN] ｘ , V ２ O ５ , MoS ２ ,CuGaO ２ 10. The hybrid organic-inorganic solar cell of claim 1, comprising a material selected from the group consisting of PTAA, poly-TPD, and PbS.

6. P3HT, spiro-OMeTAD, PEDOT:PSS, NiO ｘ , MoO ｘ , W.O. ｘ , CuO ｘ , Cu[SCN] ｘ , V ２ O ５ , MoS ２ ,CuGaO ２ 6. The hybrid organic-inorganic solar cell of claim 5, wherein in the group consisting of P3HT, spiro-OMeTAD, PTAA, poly-TPD and PbS, the P3HT, spiro-OMeTAD, PTAA and poly-TPD are doped or undoped.

7. The material of the TCO layer is In ２ O ３ : SnO ２ (ITO), In ２ O ３ : H, SnO ２ :F(FTO), SnO ２ ZnO:Al and ZnO:B.

8. The material of the electrode layer is In ２ O ３ : SnO ２ (ITO), In ２ O ３ :H, ZnO:Al, ZnO:B, SnO ２ , C, Au, Ag, Cu, Ni and Al.

9. 10. The hybrid organic-inorganic solar cell of claim 1, wherein the electrode layer adjacent the substrate comprises a non-transparent electrode layer.

10. The perovskite layer is CH ３ NH ３ PbI ３ 、CH ３ NH ３ PbCl ３ 、CH ３ NH ３ PbBr ３ 、CH ３ NH ３ PbI ３－ｘ Cl ｘ 、CH ３ NH ３ PbI ３－ｘ Br ｘ 、HC(NH ２ ) ２ PbI ３ 、HC(NH ２ ) ２ PbCl ３ 、HC(NH ２ ) ２ PbBr ３ 、HC(NH ２ ) ２ PbI ３－ｘ Cl ｘ 、HC(NH ２ ) ２ PbI ３－ｘ Br ｘ 、[HC(NH ２ ) ２ １－ｘ Cs ｘ PbI ３ 、CsPbI ３－ｘ [[ID=8​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ ３ NH ３ ) １－ｘ－ｙ [HC(NH ２ ) ２ ] ｙ Cs ｘ Pb １－ｚ Sn ｚ I ３－δ Br δ , and (CH ３ NH ３ ) １－ｘ－ｙ－ｚ [HC(NH ２ ) ２ ] ｚ Cs ｙ Rb ｘ PbI ３－δ Br δ 10. The hybrid organic-inorganic solar cell of claim 1, comprising a material selected from the group consisting of:

11. CH ３ NH ３ PbI ３ 、CH ３ NH ３ PbCl ３ 、CH ３ NH ３ PbBr ３ 、CH ３ NH ３ PbI ３－ｘ Cl ｘ 、CH ３ NH ３ PbI ３－ｘ Br ｘ 、HC(NH ２ ) ２ PbI ３ 、HC(NH ２ ) ２ PbCl ３ 、HC(NH ２ ) ２ PbBr ３ 、HC(NH ２ ) ２ PbI ３－ｘ Cl ｘ 、HC(NH ２ ) ２ PbI ３－ｘ Br ｘ 、[HC(NH ２ ) ２ ] １－ｘ Cs ｘ PbI ３ 、CsPbI ３－ｘ Br ｘ 、[HC(NH ２ ) ２ ] １－ｘ Cs ｘ PbI ３－ｙ Br ｙ 、CH ３ NH ３ Pb １－ｘ Sn ｘ I ３－ｙ Br ｙ 、(CH ３ NH ３ ) １－ｘ－ｙ [HC(NH ２ ) ２ ] ｙ Cs ｘ PbI ３－ｚ Br ｚ 、(CH ３ NH ３ ) １－ｘ－ｙ [HC(NH ２ ) ２ ] ｙ Cs ｘ Pb １－ｚ Sn ｚ I ３－δ Br δ , and (CH ３ NH ３ ) １－ｘ－ｙ－ｚ [HC(NH ２ ) ２ ] ｚ Cs ｙ Rb ｘ PbI ３－δ Br δ 11. The hybrid organic-inorganic solar cell of claim 10, wherein in the group of perovskite layers consisting of:

Images