Architecture for Efficient Monolithic Bifacial Perovskite-CdSeTe Tandem Thin Film Solar Cells and Modules

Abstract

An optoelectronic device comprising two photovoltaic absorber materials of CdSeTe and perovskite and their functional component layers that are monolithically integrated into a bifacial tandem solar cell structure.

Claims

1. A bifacial tandem solar cell comprising: at least one subcell of perovskite; at least one subcell of CdSeTe; two transparent and conductive electrodes, position at opposite ends of the bifacial tandem solar cell, an interconnecting layer between the at least one perovskite subcell and the at least one CdSeTe subcell to monolithically integrate the two subcells; and wherein the maximum solar-to-electricity power conversion efficiency for the bifacial tandem solar cell is greater than 40%.

2. The bifacial tandem solar cell according to claim 1 wherein the primary illumination direction is from the perovskite subcell, and the secondary illumination direction is the CdSeTe subcell.

3. The bifacial tandem solar cell according to claim 1 wherein the perovskite subcell comprises metal halide perovskites with a general formula of ABX.sub.3, wherein A is methylamine (MA), formamidine (FA), or cesium (Cs), or a combination thereof, and B is lead (Pb), tin (Sn), X is iodine (I), bromine (Br), chlorine (Cl), or a combination thereof; and wherein the bandgap of the perovskite layer can vary from 1.1 to 3.0 eV by tuning the ABX.sub.3 composition.

4. The bifacial tandem solar cell according to claim 1 wherein the CdSeTe subcell comprises cadmium chalcogenide compounds CdSe.sub.xTe.sub.1-x, wherein x value varies from 0 to 1; and wherein the bandgap of the CdSeTe layer can vary from 1.35 to 1.5 eV.

5. The bifacial tandem solar cell according to claim 1 wherein a kind of glass-to-glass encapsulation is carried out in a nitrogen atmosphere to protect the perovskite subcell from degradation.

6. An optoelectronic device comprising: two photovoltaic absorber materials of CdSeTe and perovskite; at least one functional component layer; and wherein the photovoltaic absorber materials are monolithically integrated into a bifacial tandem solar cell structure.

7. The optoelectronic device according to claim 6 wherein the photocurrent-voltage characteristics in the tandem device can be modulated by the rear-side illumination conditions, wherein the open-circuit voltage (V.sub.OC), short-circuit current density (J.sub.SC), fill factor (FF), and equivalent power conversion efficiency (PCE) all increase with increasing rear-side illumination intensity.

8. A method of preparing a bifacial Perovskite-CdSeTe tandem solar cell comprising; preparing a transparent conducting oxide (TCO) electrode coated glass substrate; depositing an n-type window layer for CdSeTe solar cells; forming a back buffer surface layer for CdSeTe devices; depositing an interconnecting layer; depositing an electron transport layer (ETL) for the perovskite subcell; depositing a hole transport layer (HTL) for the perovskite subcell; depositing a front TCO layer; and depositing a front metal grid.

9. The method of claim 6, wherein the interconnecting layer is omitted, and the electrical connection of perovskite and CdSeTe subcells are formed by the back buffer surface layer for CdSeTe subcell and the ETL for the perovskite subcell.

Description

IN THE DRAWINGS

[0008] FIG. 1 is an illustration of a cross-sectional view of a bifacial Perovskite-CdSeTe tandem solar cell structure 100. A tandem device comprises a CdSeTe subcell and a perovskite subcell monolithically integrated by an interconnecting layer. Light can enter a bifacial Perovskite-CdSeTe tandem solar cell from both sides of the device.

[0009] FIG. 2 is a top view of a substrate comprising six bifacial Perovskite-CdSeTe tandem solar cells.

[0010] FIG. 3 is an illustration of a cross-sectional view of a bifacial FA.sub.0.8CS.sub.0.2Pb(I.sub.0.7Br.sub.0.3).sub.3—CdTe tandem solar cell.

[0011] FIG. 4 is a SEM cross-sectional image of a bifacial FA.sub.0.8CS.sub.0.2Pb(I.sub.0.7Br.sub.0.3).sub.3—CdTe tandem solar cell.

[0012] FIG. 5 is a graph displaying current density-voltage curves of a bifacial FA.sub.0.8CS.sub.0.2Pb(I.sub.0.7Br.sub.0.3).sub.3—CdTe tandem solar cell illuminated concurrently with 1 sun equivalent intensity from the perovskite side and 0.25 sun equivalent intensity from the CdTe side and illuminated from single-side with 1 sun intensity.

[0013] FIG. 6 is a graph displaying current density-voltage curves of single-junction semitransparent perovskite and CdTe solar cells.

[0014] FIG. 7 is an illustration of a cross-sectional view of a bifacial MAPbI.sub.3—CdSeTe tandem solar cell.

[0015] FIG. 8 is a graph displaying current density-voltage curves of a bifacial MAPbI.sub.3—CdSeTe tandem solar cell illuminated concurrently with 1 sun equivalent intensity from the perovskite side and 0.35 sun equivalent intensity from the CdSeTe side and illuminated from single-side with 1 sun intensity.

[0016] FIG. 9 is a graph displaying the detailed balance efficiency limit of bifacial tandem solar cells under different back illumination conditions.

[0017] FIG. 10 is a schematic of photocurrent modulation in a bifacial tandem device by rear-side illumination (albedo light).

[0018] FIG. 11 is a graph displaying current density-voltage curves of a bifacial MAPbI.sub.3—CdSeTe tandem solar cell illuminated concurrently with 1 sun equivalent intensity from the perovskite side and various light intensities from the CdSeTe side. External quantum efficiency curves of MAPbI.sub.3 and CdSeTe subcells measured under different back-side light biasing conditions.

[0019] FIG. 12 is a top and bottom view of a bifacial perovskite-CdSeTe tandem device encapsulated in a glass-to-glass encapsulation.

DETAILED DESCRIPTION OF THE INVENTION

[0020] The optoelectronic tandem device 100 fabrication comprises the following steps:

[0021] S101: preparing a transparent conducting oxide (TCO) electrode 102 coated glass substrate 101. TCO layer includes materials such as fluorine-doped tin oxide (FTO) 115, indium tin oxide (ITO) 116, aluminum-doped zinc oxide (AZO) 117, indium doped zinc oxide (IZO), hydrogen doped indium oxide (IO:H) and others. This layer can be prepared by sputtering, chemical bath deposition, and other methods. The TCO layer has a thickness of 100 to 300 nm.

[0022] S102: depositing an n-type window layer 103 for CdSeTe solar cells. Window layer materials are metal compounds comprising of elements of cadmium, oxygen, sulfide, selenide, zinc, magnesium, tin, indium. This layer can be prepared by sputtering, chemical bath deposition, physical vapor deposition, atomic layer deposition, electrochemical deposition, and other methods. The window layer has a thickness of 5 to 100 nm. The window layer is optional and can be omitted in some cases.

[0023] S103: depositing CdSeTe absorber layer 104. The molecular ratio of Cd to Se in the chemical composition of Cd.sub.xSe.sub.1-xTe determines the absorption bandgap of the CdSeTe absorber layer. The CdSeTe absorber layer is treated with CdCl.sub.2 heat treatment and is doped with Cu or a group-V dopant, including phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi). This layer can be prepared by sputtering, sublimation, physical vapor deposition, and other methods. The CdSeTe layer has a thickness of 500 to 5000 nm.

[0024] S104: forming a back buffer surface layer 105 for CdSeTe devices. The back buffer layer typically has p-type conductivity and provides an Ohmic contact to the rear electrode of CdSeTe solar cells. This layer is optional and sometimes refers to as a back surface treatment in CdTe-based photovoltaic technology. The back surface layer can be a pure substance or metal compounds. The elements used in this layer include zinc, magnesium, copper, aluminum, gallium, chromium, iron, oxygen, sulfur, selenium, tellurium, iodine, bromine, chlorine, carbon, and others. This layer can also be organic or small molecule materials such as 2,2′,7,7′-Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′-spirobifluorene (Spiro-OMeTAD) 118, 2,2′,7,7′-Tetra(N,N-di-p-tolyl)amino-9,9-spirobifluorene (Spiro-TTB), Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), Poly(3-hexylthiophene-2,5-diyl) (P3HT), Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS), Poly(4-butyltriphenylamine) (Poly-TPD), copper(II) phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), copper(II) thiocyanate (CuSCN), etc. This layer can be prepared by sputtering, evaporation, sublimation, physical vapor deposition, chemical solution, and other methods. This layer has a thickness of 5 to 100 nm.

[0025] S105: depositing an interconnecting layer 106. This layer provides electrical connections of perovskite and CdSeTe subcells. This layer can be metal compounds or organic materials. The elements used in this layer include zinc, indium, tin, magnesium, aluminum, oxygen, sulfur, selenium, tellurium, carbon, and others. This layer can be prepared by sputtering, evaporation, atomic layer deposition, spin-coating, blade coating, spraying, slot-die coating, and other methods. The interconnecting layer has a thickness of 10 to 120 nm. The interconnecting layer is also called the recombination layer. The interconnecting layer is optional and can be omitted in some cases.

[0026] S106: depositing electron transport layer (ETL) 107 for the perovskite subcell. ETL materials are typically metal compounds comprising of elements of tin, titanium, zinc, indium, gallium, aluminum, niobium, oxygen. This layer can also be organic or small molecule materials such as fullerene (C.sub.60) and its derivatives, phenyl-C61-butyric acid methyl ester (PCBM). This layer can be prepared by sputtering, evaporation, atomic layer deposition, spin-coating, blade coating, spraying, slot-die coating, and other methods. The ETL has a thickness of 10 to 50 nm.

[0027] S107: depositing perovskite absorber layer 108. Perovskite materials comprise of elements of carbon, nitrogen, hydrogen, cesium, rubidium, potassium, lead, tin, germanium, chlorine, bromine, iodine, fluorine, sulfur. The metal halide perovskites have a general chemical formula of ABX.sub.3, where A is an organic or inorganic monovalent cation, B is a divalent metal cation, and X is halide ion. Typical A cations include methylammonium (MA), formamidinium (FA), cesium (Cs), rubidium (Rb), and other alkylammonium and arylammonium. Typical B cations include lead (Pb), tin (Sn), germanium (Ge), and other Group IVA metals. Typical X cations include chlorine (Cl), bromine (Br), iodine (I). The chemical composition includes alloys of various perovskites. The bandgap of the perovskite layer can be varied from 1.1 to 3.0 eV by tailoring the perovskite composition. This layer can be prepared by evaporation, chemical vapor deposition, spin-coating, blade coating, spraying, slot-die coating, printing, and other methods. The perovskite absorber layer has a thickness of 200 to 1000 nm.

[0028] S108: depositing a hole transport layer (HTL) 109 for the perovskite subcell. HTL materials include p-type organic polymers and molecules and inorganic compounds comprising of elements of carbon, nitrogen, hydrogen, oxygen, sulfur, phosphorus, nickel, copper, zinc, lithium, cobalt, iron, lead, zirconium, hafnium. Typical examples of organic HTLs include 2,2′,7,7′-Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′-spirobifluorene (Spiro-OMeTAD), 2,2′,7,7′-Tetra(N,N-di-p-tolyl)amino-9,9-spirobifluorene (Spiro-TTB), Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), Poly(3-hexylthiophene-2,5-diyl) (P3HT), Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS), Poly(4-butyltriphenylamine) (Poly-TPD), copper(II) phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), copper(II) thiocyanate (CuSCN), etc. This layer can be prepared by evaporation, chemical vapor deposition, spin-coating, blade coating, spraying, slot-die coating, printing, and other methods. The HTL has a thickness of 10 to 200 nm.

[0029] S109: depositing front TCO layer 110. This layer includes materials such as indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), indium doped zinc oxide (IZO), hydrogen doped indium oxide (IO:H) and others. This layer can be prepared by sputtering, evaporation, and other methods. The front TCO layer has a thickness of 100 to 300 nm.

[0030] S110: depositing front metal grid 111. The grid materials include silver, gold, aluminum, copper, nickel, indium, chromium, molybdenum, and others. This layer can be prepared by sputtering, evaporation, and other methods. The metal grid has a thickness of 100 to 5000 nm.

[0031] It is understood that the photovoltaic devices of the present invention may further include various additional components known in the art, such as additional buffer layers, anti-reflective coatings, encapsulant, front cover glass sheet, and additional wiring or electrical connections.

Examples

[0032] This Example describes the application of bifacial FA.sub.0.8Cs.sub.0.2Pb(I.sub.0.7Br.sub.0.3).sub.3—CdTe tandem solar cells.

[0033] FIG. 2 shows the top view picture of six bifacial tandem solar cells fabricated on a glass substrate following the fabrication process. As an example, the substrate has a size of 1 inch by 1 inch contains six bifacial tandem cells with an active area of 0.25 cm.sup.2 for each cell. These devices have been used to demonstrate the device structure design and fundamental photovoltaic performance. The substrate and cell size can be arbitrary and expand to large sizes for minimodule and solar panel applications.

[0034] FIG. 3 shows the detailed device structure used in this example, comprising of a film stack of glass/FTO/CdS/CdTe/CuAlO.sub.2/ITO/SnO.sub.2/FA.sub.0.8CS.sub.0.2Pb(I.sub.0.7Br.sub.0.3).sub.3/spiro-OMeTAD/ITO/Ag (grid). The CdTe absorber layer has a thickness of 1 to 3 μm and a bandgap of 1.45 eV. The FA.sub.0.8CS.sub.0.2Pb(I.sub.0.7Br.sub.0.3).sub.3 absorber layer has a thickness of 200 to 350 nm and a bandgap of 1.75 eV. The cross-sectional scanning electron microscopic (SEM) image of a bifacial FA.sub.0.8CS.sub.0.2Pb(I.sub.0.7Br.sub.0.3).sub.3—CdTe tandem solar cell is shown in FIG. 4.

[0035] An example of current density-voltage characteristics of the bifacial tandem device is shown in FIG. 5. The illumination condition is selected to be a concurrent bifacial light source with the primary light with one Sun intensity, equivalent to 100 mW/cm.sup.2, incidents on the top side (perovskite subcell), and the secondary light with approximately 0.25 sun intensity, equivalent to 25 mW/cm.sup.2, incidents on the bottom side (CdTe subcell) to mimic the scattered and reflected light from the ground in a practical application. The device delivers a power conversion efficiency of 15.4% with respect to the AM1.5G standard condition and an open-circuit voltage of 1.638 V, a short circuit current density of 14.9 mA/cm.sup.2, and a fill factor of 63.1%. FIG. 5 also shows the current density-voltage characteristics of the device under different light illumination conditions, including (1) front-only illumination and (2) back-only illumination, both at 1 Sun intensity. Compared with one-side illumination, bifacial illumination shows a substantial improvement in power conversion. The bifacial perovskite-CdTe tandem cell exhibits a higher power output than corresponding semitransparent single-junction wide-bandgap perovskite cell and CdTe cell with power conversion efficiencies of 13.8% and 13.5%, respectively, as shown in the J-V curves in FIG. 6.

[0036] Another example is given for a bifacial perovskite-CdSeTe tandem cell based on the combination of a MAPbI.sub.3 perovskite top subcell and a CdSeTe bottom subcell.

[0037] FIG. 7 shows the detailed device structure used in this example, comprising of a film stack of glass/FTO/CdSeTe/CuSCN/SnO.sub.2/MAPbI.sub.3/spiro-OMeTAD/ITO/Ag (grid). The CdSeTe absorber layer has a thickness of 2 to 4 μm and a bandgap of 1.35 eV. The MAPbI.sub.3 absorber layer has a thickness of 300 to 700 nm and a bandgap of 1.60 eV. This kind of bifacial tandem device does not require an interconnecting layer. The perovskite and CdSeTe subcells are electrically connected by the back buffer layer for CdSeTe subcell and the ETL of perovskite subcell.

[0038] An example of current density-voltage characteristics of the bifacial tandem device is shown in FIG. 8. For the bifacial illumination, one Sun intensity, equivalent to 100 mW/cm.sup.2, incidents on the top side (perovskite subcell), and the secondary light with approximately 0.35 sun intensity, equivalent to 35 mW/cm.sup.2, incidents on the bottom side (CdSeTe subcell). The device delivers a power conversion efficiency of 19.0% with respect to the AM1.5G standard condition and an open-circuit voltage of 1.722 V, a short circuit current density of 14.9 mA/cm.sup.2, and a fill factor of 74.1%. FIG. 8 also shows the current density-voltage characteristics of the device under different light illumination conditions, including (1) front-only illumination and (2) back-only illumination, both at 1 Sun intensity. Compared with one-side illumination, bifacial illumination shows a substantial improvement in power conversion.

[0039] The bifacial design is a key to enable high-efficiency perovskite-CdSeTe tandem solar cells and modules. The tandem cells perform poorly with single-side illuminations. This is mainly because the dominant junction (p-n junction) of CdSeTe subcell is located near the glass substrate, and thus not close to the interconnecting layer. If the tandem cell is only illuminated from the perovskite side, photons passing the perovskite top cell will be absorbed in the CdSeTe region near the interconnecting layer, in which there is no effective field to separate photo-generated electron-hole pairs, resulting in a low short-circuit current density (J.sub.SC) and open-circuit voltage (V.sub.OC). On the other hand, if the tandem cell is only illuminated from the CdSeTe (glass) side, photons are only absorbed by the CdSeTe layer and the perovskite subcell operates in the “dark”, and therefore, showing an extremely low current density. The bifacial illumination overcomes these shortfalls, leading to both high V.sub.OC and J.sub.SC, and, therefore, high powder conversion efficiency.

[0040] Detailed balance efficiency analysis shown in FIG. 9 compares the maximum solar-to-electricity power conversion efficiency of the photovoltaic devices of present invention under different back illumination conditions. For various bandgap combinations of perovskite and CdSeTe, maximum efficiencies are higher than 40%, significantly higher than the efficiency limits of single-junction solar cells.

[0041] The photovoltaic devices of present invention allow photocurrent modulation by the rear-side illumination or albedo light. Because the two subcells in a tandem device are electrically connected in series, the current flow through the whole tandem device is constant. Therefore, the photocurrent in a tandem device is determined by the albedo light from the rear-side illumination, as shown in FIG. 10.

[0042] FIG. 11 shows an example of the photocurrent modulation of a bifacial perovskite-CdTeSe tandem device by rear-side illumination conditions. The photocurrent of the tandem cells increases with increasing the rear-side illumination intensity and saturate at above 0.4 sun intensity. The tandem devices show higher V.sub.OC, J.sub.SC, and fill factor with increasing rear-side illumination intensity. FIG. 9 also shows the external quantum efficiency (EQE) curves of the perovskite subcell measured under different rear-side illumination intensities, which demonstrates the photocurrent modulation effect by the rear-side illumination intensity.

[0043] An example of glass-to-glass encapsulation of the photovoltaic devices of the present invention using sealant, front cover glass sheet, and additional wiring or electrical connections is shown in FIG. 12. The encapsulation process is carried out in a nitrogen atmosphere to protect the perovskite subcell from degradation. A metal busbar is connected to the metal grid of the photovoltaic device and extended out of the encapsulation package as the external contact. A piece of front cover glass sheet is attached to the FTO coated glass substrate and sealed by using ultraviolet light cured epoxy. This kind of glass-to-glass encapsulation help protect perovskite subcells from degradation and make the tandem devices more durable. We observed almost no degradation of device performance after 6 months of storage of the encapsulated tandem devices in ambient air.