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US-20260130043-A1 - PASSIVATING PEROVSKITE OPTOELECTRONIC DEVICES

US20260130043A1US 20260130043 A1US20260130043 A1US 20260130043A1US-20260130043-A1

Abstract

Perovskite optoelectronic devices, e.g., solar cells, are provided, which comprise a perovskite layer comprising a perovskite; and chemical passivating ligands bound to the perovskite of the perovskite layer, wherein the chemical passivating ligands comprise a thioether group, —SR′, wherein R′ is an alkyl group.

Inventors

  • Mercouri G. Kanatzidis
  • Edward Hartley Sargent
  • Bin Chen
  • Cheng Liu
  • Yi Yang

Assignees

  • NORTHWESTERN UNIVERSITY

Dates

Publication Date
20260507
Application Date
20251031

Claims (20)

  1. 1 . A perovskite optoelectronic device comprising a perovskite layer comprising a perovskite; and chemical passivating ligands bound to the perovskite of the perovskite layer, wherein the chemical passivating ligands comprise a thioether group, —SR′, wherein R′ is an alkyl group.
  2. 2 . The perovskite optoelectronic device of claim 1 , wherein the alkyl group is unsubstituted.
  3. 3 . The perovskite optoelectronic device of claim 1 , wherein the alkyl group has from 1 to 8 carbon atoms.
  4. 4 . The perovskite optoelectronic device of claim 1 , wherein the alkyl group is a linear alkyl.
  5. 5 . The perovskite optoelectronic device of claim 1 , wherein R′ is methyl.
  6. 6 . The perovskite optoelectronic device of claim 1 , wherein the chemical passivating ligands further comprise a linking group covalently bound to the thioether group and an additional perovskite binding group covalently bound to the linking group.
  7. 7 . The perovskite optoelectronic device of claim 6 , wherein the additional perovskite binding group is an ammonium group, —NH 3 + .
  8. 8 . The perovskite optoelectronic device of claim 6 , wherein the linking group is an alkyl group.
  9. 9 . The perovskite optoelectronic device of claim 1 , wherein the chemical passivating ligands are selected from those having formula + H 3 N—R—SR′, wherein R and R′ are independently selected alkyl groups.
  10. 10 . The perovskite optoelectronic device of claim 9 , wherein R and R′ are independently selected unsubstituted, linear alkyl groups having from 1 to 8 carbon atoms.
  11. 11 . The perovskite optoelectronic device of claim 1 , wherein the chemical passivating ligands are selected from 3-(methylthio)propylammonium, 2-(methylthio)ethylammonium, and combinations thereof.
  12. 12 . The perovskite optoelectronic device of claim 1 , further comprising field-effect passivating ligands bound to the perovskite of the perovskite layer.
  13. 13 . The perovskite optoelectronic device of claim 12 , wherein the field-effect passivating ligands each comprise two ammonium groups.
  14. 14 . The perovskite optoelectronic device of claim 12 , wherein the field-effect passivating ligands are selected from alkyldiammonium compounds.
  15. 15 . The perovskite optoelectronic device of claim 12 , wherein the field-effect passivating ligands are selected from ethane-1,2-diammonium, propane-1,3-diammonium, and combinations thereof.
  16. 16 . The perovskite optoelectronic device of claim 1 configured as a perovskite solar cell comprising a hole transport layer, an electron transport layer, the perovskite layer between the hole transport layer and the electron transport layer, and the chemical passivating ligands bound to the perovskite of the perovskite layer.
  17. 17 . The perovskite optoelectronic device of claim 16 , further comprising field-effect passivating ligands bound to the perovskite of the perovskite layer.
  18. 18 . The perovskite optoelectronic device of claim 17 , wherein the chemical passivating ligands and the field-effect passivating ligands are located at an interface formed between the electron transport layer and the perovskite layer.
  19. 19 . The perovskite optoelectronic device of claim 18 , wherein the chemical passivating ligands are selected from those having formula + H 3 N—R—SR′, wherein R and R′ are independently selected alkyl groups; the field-effect passivating ligands are selected from alkyldiammonium compounds; and the perovskite has formula ABX 3 , wherein A is a protonated amine; B is a divalent metal ion; and X is an anion bound to B.
  20. 20 . The perovskite optoelectronic device of claim 19 , wherein the chemical passivating ligands are selected from 3-(methylthio)propylammonium, 2-(methylthio)ethylammonium, and combinations thereof and the field-effect ligands are selected from ethane-1,2-diammonium, propane-1,3-diammonium, and combinations thereof.

Description

CROSS-REFERENCE TO RELATED APPLICATION The present application claims priority to U.S. Provisional Patent Application No. 63/715,373, filed on Nov. 1, 2024, the entire contents of which are incorporated herein by reference. REFERENCE TO GOVERNMENT RIGHTS This invention was made with government support under 70NANB1911005 awarded by the National Institute of Standards and Technology. The government has certain rights in the invention. BACKGROUND Certified power conversion efficiencies (PCEs)>25% have been widely reported for perovskite solar cells (PSCs) in the regular (n-i-p) structure. Although inverted (p-i-n) PSCs have potential advantages because of their stability, low-temperature processing, and compatibility with integration into tandem solar cells, their reported PCEs rarely surpass 24% under the stringent quasi-steady-state (QSS) protocol. SUMMARY Perovskite optoelectronic devices, e.g., solar cells, are provided, which comprise a perovskite layer and passivating ligands bound thereto. The passivating ligands comprise chemical passivating ligands and, in embodiments according to a dual passivation scheme, may further comprise field-effect passivating ligands. The Example below describes an illustrative dual passivation scheme in which methylthio molecules were used to passivate surface defects and suppress recombination through strong coordination and hydrogen bonding, along with diammonium molecules to repel minority carriers and reduce contact-induced interface recombination achieved through field-effect passivation. The approach led to a fivefold increase in carrier lifetime and a threefold reduction in photoluminescence quantum yield loss. This approach enabled a certified quasi-steady-state PCE of 25.1% for inverted PSCs with stable operation at 65° C. for >2,000 hours in ambient air. Monolithic all-perovskite tandem solar cells were also fabricated with 28.1% PCE. Embodiments of a perovskite optoelectronic device are provided that comprise a perovskite layer comprising a perovskite; and chemical passivating ligands bound to the perovskite of the perovskite layer, wherein the chemical passivating ligands comprise a thioether group, —SR′, wherein R′ is an alkyl group. Other principal features and advantages of the disclosure will become apparent to those skilled in the art upon review of the following drawings, the detailed description, and the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Illustrative embodiments of the disclosure will hereafter be described with reference to the accompanying drawings, wherein like numerals denote like elements. FIGS. 1A-1D. Passivation at the perovskite/ETL interface. FIGS. 1A, 1B show a schematic of the perovskite surface without passivation (FIG. 1A) and with both chemical and field-effect passivation (FIG. 1i). FIG. 1C shows chemical structures of the diammonium and ammonium ligands investigated in the Example, below. FIG. 1D shows PCEs of control vs. passivated PSCs using different passivation ligands and combinations thereof. FIGS. 2A-2H. The process of passivation through the methylthio group on perovskite surfaces. FIG. 2A shows binding energies of ammonium ligands with clean and defective perovskite surfaces with the typical iodide vacancy. FIG. 2B shows electrostatic potential (p) of 3MTPA and AA ligands. FIG. 2C shows calculated charge density difference of anchoring ammonium ligands onto the perovskite surface with I vacancies. The open circles indicate the positions of I vacancies. The atoms in the structures are differentiated by different shading. FIG. 2D shows calculated charge density difference showing the hydrogen bond formation between 3MTPA and FA. FIG. 2E shows the proton NMR spectra of FAI, FAI with AAI, and FAI with 3MTPAI. FIG. 2F shows high-resolution Pb 4f XPS peaks of the perovskite films. FIG. 2G shows SIMS mapping of signal ratios of 3MTPA:PDA and AA:PDA for perovskite samples with PDAI2/3MTPAI (1:2 molar ratio) and PDAI2/AAI (1:2 molar ratio) bimolecular passivation. FIG. 2H shows PL intensity distribution of the 1 cm by 1 cm perovskite film post-synthetic treated by spray coating with ink 1 of PDAI2/3MTPAI and ink 2 of PDAI2/AAI solution centered around the diagonal corners. FIGS. 3A-3E. Diammonium-methylthio dual passivation DMDP strategy working principle. FIG. 3A shows GIWAXS patterns of the control and DMDP-based perovskite films. FIG. 3B shows TRPL of the perovskite films treated with different ligands. FIG. 3C shows the energy level difference between the conduction band maximum and Fermi level for the perovskite films treated with different ligands. FIG. 3D shows ligand-concentration-dependent PLQY of the perovskite films, PLQY loss of the perovskite films after C60 deposition, and PCEs of devices. For DMDP, the concentration of 3MTPAI was varied, while the PDAI2 concentration was optimized and maintained at 6 mM. FIG. 3E is a schematic diagram showing the inhibition of interface recombination by PDAI2 and the suppre