Search

KR-102964334-B1 - PHOTOVOLTAIC DEVICE BASED ON SELF-ASSEMBLED TWO-DIMENSIONAL PEROVSKITE

KR102964334B1KR 102964334 B1KR102964334 B1KR 102964334B1KR-102964334-B1

Abstract

The present invention relates to a photovoltaic device comprising a two-dimensional perovskite formed by self-assembly between a perovskite and an electron transport layer, and a method for manufacturing the same.

Inventors

  • 조윌렴
  • 김지현

Assignees

  • 이화여자대학교 산학협력단

Dates

Publication Date
20260513
Application Date
20250121
Priority Date
20240502

Claims (18)

  1. A first passivation layer containing an ammonium salt; An electron transport layer formed on the first passivation layer and comprising a metal oxide; A perovskite layer formed on the electron transport layer above; and A second passivation layer formed on the above perovskite layer and comprising a compound represented by the following chemical formula 1 As a perovskite photovoltaic device comprising, It includes a two-dimensional perovskite formed by self-assembly at the interface between the electron transport layer and the perovskite layer, The above two-dimensional perovskite comprises a compound represented by the following chemical formula 3, Perovskite photovoltaic device: [Chemical Formula 1] R 1 NH 3 X 1 , In the above chemical formula 1, R1 is a C5-20 alkyl group, X1 is F, Cl, Br, or I, and [Chemical Formula 3] (R 1 NH 3 ) 2 MX 1 4 , In the above chemical formula 3, R1 is a C5-20 alkyl group, M is Pb, Sn, Cu, Ni, Co, Fe, Mn, Pd, Cd, Ge, Cs, Eu, or a combination thereof, and X1 is F, Cl, Br, or I.
  2. In Article 1, The above ammonium salts are NH₄Cl (ammonium chloride), NH₄Br (ammonium bromide) , NH₄I (ammonium iodide), NH₄F (ammonium fluoride), NH₄NO₃ (ammonium nitrate), ( NH₄ ) ₂CO₃ (ammonium carbonate), NH₄HCO₃ (ammonium bicarbonate ) , ( NH₄ ) ₂SO₄ (ammonium sulfate), ( NH₄ ) ₂S₂O₅ (ammonium persulfate ), NH₄HSO₃ (ammonium hydrogen sulfate), NH₄HSO₄ (ammonium hydrogen sulfate ) , NH₄ClO₄ (ammonium perchlorate ) , CH₃COONH₄ ( ammonium acetate ) , C₆H₅COONH₄ (ammonium benzoate ) , and NH₄H₂PO₄ A perovskite photovoltaic device comprising one or more selected from (ammonium dihydrogen phosphate), (NH₄)₂HPO₄ ( ammonium hydrogen phosphate), NH₄SCN (ammonium thiocyanate), NH₄BF₄ (ammonium tetrafluoroborate), and NH₄PF₆ (ammonium hexafluorophosphate).
  3. delete
  4. delete
  5. In Article 1, A perovskite photovoltaic device in which the above two-dimensional perovskite comprises OA2PbI4 .
  6. In Article 1, A perovskite photovoltaic device comprising one or more selected from SnO2 , TiO2 , ZnO, WO3 , RuO2 , La x Sr 1-x CoO3 , La x Sr 1-x MnO3 , BaSnO3 , and LaNiO3 , wherein 0 < x ≤ 0.5.
  7. In Article 5, A perovskite photovoltaic device in which the C 1s X-ray photoelectron spectroscopy (XPS) spectrum of the interface between the electron transport layer and the perovskite layer exhibits a peak detected at 291 eV to 294 eV by the OA2PbI4 .
  8. In Article 1, A perovskite photovoltaic device further comprising a substrate, a first electrode, a hole transport layer, and/or a second electrode.
  9. Forming a first passivation layer containing an ammonium salt on a first electrode; Forming an electron transport layer comprising a metal oxide on the first passivation layer; Forming a perovskite layer on the electron transport layer; and Forming a second passivation layer comprising a compound represented by the following chemical formula 1 on the perovskite layer. A method for manufacturing a perovskite photovoltaic device comprising, A two-dimensional perovskite is formed by self-assembly at the interface between the electron transport layer and the perovskite layer, and The above two-dimensional perovskite comprises a compound represented by the following chemical formula 3, Method for manufacturing a perovskite photovoltaic device: [Chemical Formula 1] R 1 NH 3 X 1 , In the above chemical formula 1, R1 is a C5-20 alkyl group, X1 is F, Cl, Br, or I, and [Chemical Formula 3] (R 1 NH 3 ) 2 MX 1 4 , In the above chemical formula 3, R1 is a C5-20 alkyl group, M is Pb, Sn, Cu, Ni, Co, Fe, Mn, Pd, Cd, Ge, Cs, Eu, or a combination thereof, and X1 is F, Cl, Br, or I.
  10. In Article 9, The above ammonium salts are NH₄Cl (ammonium chloride), NH₄Br (ammonium bromide) , NH₄I (ammonium iodide), NH₄F (ammonium fluoride), NH₄NO₃ (ammonium nitrate), ( NH₄ ) ₂CO₃ (ammonium carbonate), NH₄HCO₃ (ammonium bicarbonate ) , ( NH₄ ) ₂SO₄ (ammonium sulfate), ( NH₄ ) ₂S₂O₅ (ammonium persulfate ), NH₄HSO₃ (ammonium hydrogen sulfate), NH₄HSO₄ (ammonium hydrogen sulfate ) , NH₄ClO₄ (ammonium perchlorate ) , CH₃COONH₄ ( ammonium acetate ) , C₆H₅COONH₄ (ammonium benzoate ) , and NH₄H₂PO₄ A method for manufacturing a perovskite photovoltaic device comprising one or more selected from (ammonium dihydrogen phosphate), (NH₄)₂HPO₄ ( ammonium hydrogen phosphate), NH₄SCN (ammonium thiocyanate), NH₄BF₄ (ammonium tetrafluoroborate), and NH₄PF₆ (ammonium hexafluorophosphate).
  11. delete
  12. In Article 9, A method for manufacturing a perovskite photovoltaic device, wherein the metal oxide comprises one or more selected from SnO2 , TiO2 , ZnO, WO3 , RuO2 , La x Sr 1-x CoO3 , La x Sr 1-x MnO3 , BaSnO3 , and LaNiO3 , and 0 < x ≤ 0.5.
  13. In Article 9, A method for manufacturing a perovskite photovoltaic device, wherein forming the first passivation layer comprises applying a first passivation solution containing the ammonium salt.
  14. In Article 13, A method for manufacturing a perovskite photovoltaic device, wherein the ammonium salt concentration of the first passivation solution is 1 mM to 1000 mM.
  15. In Article 9, A method for manufacturing a perovskite photovoltaic device, wherein forming the second passivation layer comprises applying a second passivation solution containing a compound represented by Chemical Formula 1.
  16. In Article 15, A method for manufacturing a perovskite photovoltaic device, wherein the concentration of the compound represented by Chemical Formula 1 in the second passivation solution is 1 mM to 1000 mM.
  17. In Article 9, A method for manufacturing a perovskite photovoltaic device, comprising forming the first passivation layer, the electron transport layer, and the second passivation layer, and then further performing UV ozone treatment on each of them.
  18. In Article 17, A method for manufacturing a perovskite photovoltaic device, wherein the above UV ozone treatment is performed for 1 minute to 100 minutes.

Description

Photovoltaic device based on self-assembled two-dimensional perovskite The present invention relates to a photovoltaic device comprising a two-dimensional perovskite formed by self-assembly between a perovskite and an electron transport layer, and a method for manufacturing the same. Metal halide perovskite solar cells have garnered attention due to continuous improvements in power conversion efficiency (PCE), the use of cost-effective materials, and simple solution-based fabrication processes. However, halide-based perovskites present a problem in that electronic and ionic conduction occurs primarily through iodine vacancies that cause unbalanced local stoichiometric changes, leading to material degradation in narrow-bandgap perovskites and phase separation in wide-bandgap perovskites. Furthermore, charge accumulation at the interface, which contributes to early degradation, is influenced by the electron transport layer (ETL) composed of oxide materials. To address these issues and improve the performance of solar cell devices, various passivation strategies for perovskites have been studied, ranging from the introduction of additives during precursor synthesis to interfacial passivation applied above or below the perovskite layer. However, certain passivation materials in solar cells present a problem in that they act as major factors degrading device performance by causing not only electron charges but also ionic defects at the interface and the accumulation of bulk non-uniformity. FIG. 1 is a schematic diagram showing the structure of perovskite photovoltaic devices (M1, M2, and M3) in one embodiment of the present invention. FIG. 2 schematically illustrates ions formed according to the passivation of the SnO2 electron transport layers of M1, M2, and M3 in one embodiment of the present invention. FIG. 3 shows, in one embodiment of the present invention, (a) a schematic diagram of the process of forming OA2PbI4 , a two-dimensional perovskite, through the diffusion of OA + and NH4 + , and (b) a transport barrier value of NH4 + obtained through computing simulation. FIG. 4 shows the C 1s X-ray photoelectron spectroscopy measurement results at the SnO2 electron transport layer and perovskite interface of M1, M2, and M3 in one embodiment of the present invention. FIG. 5a, b, and c show the cross-sectional transmission electron microscope (TEM) measurement results of M3, M2, and M1, respectively, in one embodiment of the present invention. FIG. 6 shows the photoluminescence measurement results at the SnO2 electron transport layer and perovskite interface of M1, M2, and M3 in one embodiment of the present invention. FIG. 7 shows the scanning electron microscope measurement results of the perovskite surfaces of M1, M2, and M3 in one embodiment of the present invention. FIG. 8 shows the X-ray diffraction measurement results of the perovskite surfaces of M1, M2, and M3 in one embodiment of the present invention. FIG. 9 shows the results of the time-of-flight secondary ion mass spectrometry measurements of M1 and M2 in one embodiment of the present invention. FIG. 10 shows the results of evaluating the photoelectric device characteristics of M1, M2, and M3 in one embodiment of the present invention. FIG. 11 shows the results of evaluating the long-term stability of photovoltaic devices M1, M2, and M3 in one embodiment of the present invention. Hereinafter, embodiments and examples of the present invention are described in detail with reference to the attached drawings so that those skilled in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments and examples described herein. Furthermore, in order to clearly explain the present invention in the drawings, parts unrelated to the explanation have been omitted, and similar parts throughout the specification have been given similar reference numerals. Throughout this specification, when a part is described as being "connected" to another part, this includes not only cases where they are "directly connected," but also cases where they are "electrically connected" with other elements interposed between them. Throughout this specification, when a component is described as being located "on" another component, this includes not only cases where a component is in contact with another component, but also cases where another component exists between the two components. Throughout this specification, when a part is described as "comprising" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components. Terms of degree used in this specification, such as “about,” “substantially,” etc., are used to mean at or near the stated value when inherent manufacturing and material tolerances are presented in the stated meaning, and are used to prevent unscrupulous infringers from unfairly e