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KR-20260065899-A - Optoelectronic components comprising inorganic perovskite subcells and a process for manufacturing such inorganic perovskite subcells of the optoelectronic components

KR20260065899AKR 20260065899 AKR20260065899 AKR 20260065899AKR-20260065899-A

Abstract

The present invention relates to an optoelectronic component (100) comprising a transparent front electrode (2), a rear electrode (8), and a stack (20) disposed between the front electrode (2) and the rear electrode (8) - the stack (20) comprises an inorganic perovskite subcell (12), wherein the inorganic perovskite subcell (12) has an n-i-p cell architecture - and a process for manufacturing the inorganic perovskite subcell (12) of the optoelectronic component (100) by vacuum deposition on a substrate (1) - wherein the inorganic perovskite subcell (12) has an n-i-p cell architecture -.

Inventors

  • 바이스, 안드레
  • 레, 푸옹
  • 우리히, 크리스티안

Assignees

  • 헬리아텍 게엠베하

Dates

Publication Date
20260511
Application Date
20240910
Priority Date
20230911

Claims (17)

  1. A photoelectric component (100), preferably a photoelectric element, comprises a transparent front electrode (2), a rear electrode (8), and a stack (20) arranged between the front electrode (2) and the rear electrode (8), wherein the stack (20) comprises an inorganic perovskite subcell (12). The inorganic perovskite subcell (12) is characterized by having a nip cell architecture comprising the following layers in order, the optoelectronic component (100): b) an n-type layer (4) comprising a fullerene or a fullerene derivative as an electron transport material (ETM); c) an intrinsic perovskite layer (5) comprising at least one inorganic perovskite as an absorbent material; and d) a doped p-type layer (7) comprising a hole transport material (HTM) and at least one p-dopant; Here, the n-type layer b) (4) of the inorganic perovskite subcell (12) faces the front electrode (2).
  2. In claim 1, at least one inorganic perovskite is a fully inorganic perovskite, preferably a three-dimensional halide perovskite, a diovskite, or a combination thereof, and preferably the three-dimensional halide perovskite has the formula ABX3 , where A is selected from Cs, Na, K, Rb, or a combination thereof; B is selected from Pb, Sn, Ge, Cu, Fe, Ga, Eu, Sr, Ti, Mn, Bi, Zn, Mg, Ca, Ba, Y, Yb, Co, In, Sb, Bi, Ag, Ni, Ho, Er, Tb, Sm, La, or a combination thereof; X is selected from F, Cl, Br, I , or a combination thereof; preferably the diovskite has the formula A2BCX6 , where A is selected from Cs, Rb, or a combination thereof; B is selected from Cu, Ag, Hg, Au, or a combination thereof; C is selected from Sb, Bi, In, or a combination thereof; and X is selected from F, Cl, Br, I, or a combination thereof, photoelectronic component (100).
  3. In claim 1 or 2, the inorganic perovskite a of the intrinsic perovskite layer c)(5) is a photoelectronic component (100) selected from the group consisting of CsPbI₃ , CsPbBrI₂ , CsPbBr₂I , CsPbBr₃ , CsPbCl₂I , CsPbClI₂ , CsPbCl₃ , CsPbBr₂Cl , CsPbBrCl₂ , and CsPbBrClI, or a mixture thereof.
  4. In any one of claims 1 to 3, the intrinsic perovskite layer c)(5) is directly arranged in the n-type layer b)(4), the photoelectronic component (100).
  5. A photoelectronic component (100), wherein in any one of claims 1 to 4, the n-type layer b)(4) is an intrinsic n-type layer b)(4), and preferably the layer thickness of the intrinsic n-type layer b)(4) is 10 nm to 50 nm, preferably 10 nm to 30 nm.
  6. In any one of claims 1 to 5, the fullerene or fullerene derivative of the n-type layer b)(4) is selected from the group consisting of C60, C70, C76, C80, C82, C84, C86, C90 and C94, or derivatives thereof, and the derivative is preferably a halogenated fullerene, a hydroxylated fullerene, a carboxylated fullerene, or an aminated fullerene, and preferably the fullerene is C60, C70 and/or a derivative thereof, more preferably fullerene C60, a photoelectronic component (100).
  7. In any one of claims 1 to 6, the inorganic perovskite subcell (12) further comprises an n-type layer b) (4) in the order of layers, preferably an n-doped n-type layer b1) (3) before the intrinsic n-type layer b) (4), and preferably the n-type layer b) (4) is directly arranged on the n-doped n-type layer b1) (3), the optoelectronic component (100).
  8. An optoelectronic component (100), wherein, in any one of claims 1 to 7, the ratio of the p-dopant of the doped p-type layer (7) is at most 30 weight%, preferably at most 20 weight%, or preferably at most 10 weight%.
  9. In any one of claims 1 to 8, an intrinsic p-type layer d1)(6) comprising at least one hole transport material (HTM) is arranged between an intrinsic perovskite layer c)(5) and a doped p-type layer d)(7), and preferably, the hole transport material (HTM) of the intrinsic p-type layer d1)(6) is an organic material, a photoelectronic component (100).
  10. In any one of claims 1 to 9, the hole transport material (HTM) of the doped p-type layer c)(7) and/or the intrinsic p-type layer c1)(6) is an organic material and/or the p-dopant of the doped p-type layer c)(7) is an organic p-dopant, preferably the p-dopant has a LUMO that is more negative than -4.0 eV, preferably more negative than -4.5 eV, or preferably more negative than -5.0 eV, a photoelectronic component (100).
  11. In any one of claims 1 to 10, the intrinsic perovskite layer c)(5) has a layer thickness of 50 nm to 500 nm, preferably 50 nm to 400 nm, preferably 50 nm to 300 nm, preferably 100 nm to 500 nm, preferably 100 nm to 400 nm, preferably 100 nm to 300 nm, preferably 100 nm to 200 nm, preferably 150 nm to 300 nm, or preferably 200 nm to 500 nm, a photoelectronic component (100).
  12. In any one of claims 1 to 11, the optoelectronic component (100) is a single-junction, tandem-junction, or multi-junction device, preferably in a tandem-junction or multi-junction device, at least one additional subcell (13) comprises an organic photoactive layer (10) having a narrow bandgap, and at least one donor and at least one acceptor absorber material forms a donor/acceptor heterojunction.
  13. A process for manufacturing an inorganic perovskite subcell (12) of a photoelectronic component (100), preferably according to any one of claims 1 to 12, by vacuum deposition on a substrate (1), wherein the inorganic perovskite subcell (12) has a nip cell architecture, and the process, ii) a step of applying n-type layer b)(4) by evaporating a fullerene or fullerene derivative as an electron transport material (ETM); iii) a step of applying an intrinsic perovskite layer c)(5) comprising at least one inorganic perovskite as an absorbent material by co-evaporating at least the first precursor and the second precursor - each of the first precursor and the second precursor is independently selected from the group consisting of CsCl, CsBr, CsI, PbCl2 , PbBr2 , and PbI2 -; iv) a step of applying a doped p-type layer d)(7) by co-evaporating a hole transport material (HTM) and at least one p-dopant; and v) A process comprising the step of obtaining an inorganic perovskite subcell (12) of a photoelectronic component (100).
  14. In claim 13, the process is such that the temperature of the substrate (1) is 20°C to 120°C, preferably 20°C to 80°C, preferably 20°C to 60°C, or preferably 20°C to 40°C.
  15. A process according to claim 13 or 14, wherein the thermal annealing of the intrinsic perovskite layer c)(5) is performed during or after step iii) at a temperature of 20°C to 120°C, preferably 20°C to 80°C, preferably 20°C to 60°C, preferably 20°C to 50°C, preferably 20°C to 40°C, or preferably 20°C to 30°C, or the thermal annealing of the intrinsic perovskite layer c)(5) is not performed during or after the application of the intrinsic perovskite layer c)(5) in step iii).
  16. A process according to any one of claims 13 to 15, wherein an intrinsic p-type layer (6) is applied by vacuum deposition of a hole transport material (HTM) in an additional step iv1) after step iii) and before step iv).
  17. A process according to any one of claims 13 to 16, wherein the substrate (1) comprises a film, preferably the film is formed by a polymer layer, and preferably the substrate (1) is flexible.

Description

Optoelectronic components comprising inorganic perovskite subcells and a process for manufacturing such inorganic perovskite subcells of the optoelectronic components The present invention relates to an optoelectronic component comprising a transparent front electrode, a rear electrode, and a stack disposed between the front electrode and the rear electrode—the stack comprises an inorganic perovskite subcell, wherein the inorganic perovskite subcell has an n-i-p cell architecture—and a process for manufacturing the inorganic perovskite subcell of the optoelectronic component by vacuum deposition on a substrate—wherein the inorganic perovskite subcell has an n-i-p cell architecture. The power conversion efficiency (PCE) of perovskite solar cells (PSCs) has increased significantly over the past few years. Perovskite solar cells are receiving increasing attention due to their photophysical properties as well as their commercial applications. Perovskite solar cells can be manufactured by solution-processing technology or by vacuum deposition. Manufacturing perovskite solar cells by vacuum deposition, a technology widely adopted in the coating and semiconductor industries, is advantageous for large-scale production. Vacuum deposition allows for strict control over the composition and thickness of the layers in perovskite solar cells. Vacuum deposition of perovskite solar cells generally involves co-sublimating at least two types of precursors in a vacuum chamber to form a perovskite structure together. Avila et al. ('Vapor-Deposited Perovskites: The Route to High-Performance Solar Cell Production?', Joule 1, 2017, November 15, 431-442) disclose the basic principles of perovskite deposition technology. The most widely employed vacuum-based technology is dual-source co-deposition of perovskite precursors, which allows for control of the composition of the final film. Fully inorganic perovskites require high-temperature treatment or post-annealing to modify the morphology of the deposited perovskite structure. Organic-inorganic ("hybrid") perovskites typically exhibit low thermal stability due to the volatile organic cations used. Furthermore, vacuum deposition of hybrid perovskites is very difficult due to the differing vapor pressures of their respective precursors. Fully inorganic perovskites possess higher intrinsic thermal stability compared to hybrid perovskites because they lack volatile cations. This higher toughness makes them more suitable for industrial applications, and fully inorganic perovskites are known to be processable by deposition. Chiang et al. (ACS, Energy Lett., 2020, 5, 2498-2504) disclose multi-source vacuum deposition of methylammonium-free perovskite solar cells having high-quality morphological, structural, and optoelectronic properties. The production of fin solar cells by vacuum deposition is sensitive to various parameters including substrate, annealing temperature, and evaporation rate. Qiu et al. (Aggregate., 2021, 2, 66-83) disclose the deposition of inorganic lead halide perovskites in solar cells by controlling the precursor crystallization kinetics to perform a post-deposition treatment. However, in the case of vacuum-deposited inorganic perovskites, high substrate temperatures are required during processing, or a post-annealing step, particularly a thermal annealing step, is required after the deposition of the layer. This is typically performed at high temperatures exceeding 150°C, and in most cases even exceeding 250°C, to form a stable perovskite structure with high power conversion efficiency (PCE). Such annealing steps represent additional processing steps requiring time and energy. Furthermore, these annealing steps require that all components of the stack and the substrate beneath the fully inorganic perovskite layer be able to withstand the conditions of the annealing step, which clearly limits the choice of materials. In particular, annealing at such high temperatures is not applicable to temperature-sensitive substrates, such as PET polymer films, that enable the production of flexible solar cells. In particular, the substrate used for stack deposition must be able to withstand the conditions of elevated substrate temperatures during deposition and/or temperatures during the annealing step. However, many different types of substrates, particularly films, such as many PET films, begin to change their mechanical properties starting at approximately 100°C to 120°C. Belt tension typically applied in roll-to-roll processes can cause serious problems for PET-based films if the processing temperature exceeds 100°C or even higher. Vacuum under acceptable conditions for the substrate. Even the best heat-stabilized PET films, such as the biaxially oriented PET product ST504 from DuPont, still exhibit shrinkage of 0.05% to 0.1% at temperatures starting from 150°C. Shrinkage exceeding 0.1% leads to positional shifting of already applied structures (e.g., laser structuring), resul