IP Library › Granted Patent US 12,334,279
Granted Patent B2
US 12,334,279 · App. 18/558,473 · Granted Jun 17, 2025

Compositions and methods for modifying perovskite surfaces

Inventors: Kai Zhu (Littleton, CO); Fei Zhang (Tianjin, CN)
Assignee: Alliance for Sustainable Energy, LLC
H01G9/2009C07F19/005H10K30/10H10K30/151H10K30/40H10K85/50H10K30/50
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,334,279
App. No.
18/558,473
Granted
Jun 17, 2025
Kind
B2
Abstract

The present disclosure relates to a composition that includes a first layer that includes a perovskite and a second layer that includes a perovskitoid, where the perovskite has a first crystalline structure defined by ABX 3 , the perovskitoid has a second crystalline structure defined by A′B 2 X 6 , where A is a first cation, B is a second cation, X is an anion, and A′ is a third cation having either a 1+ charge or a 2+ charge.

Claims (43)

1. A composition comprising:

a first layer comprising a perovskite; and

a second layer comprising a perovskitoid, wherein:

the perovskite has a first crystalline structure comprising ABX 3 ,

the perovskitoid has a second crystalline structure comprising A′B 2 X 6 ,

A comprises a first cation, B comprises a second cation, X comprises an anion, and A′ comprises a third cation having either a 1+ charge or a 2+ charge.

2. The composition of claim 1 , wherein A′ has a characteristic length between 2.53 Å and 7.62 Å.

3. The composition of claim 2 , wherein the characteristic length is between 2.72 Å and 7.06 Å.

4. The composition of claim 1 , wherein the second crystalline structure comprises a 3D crystal structure.

5. The composition of claim 4 , wherein the 3D structure has a centrosymmetric orthorhombic space group Pbam.

6. The composition of claim 1 , wherein the second crystalline structure is characterized by having at least one octahedra dimer having a composition consisting of Pb 2 I 6 2− .

7. The composition of claim 1 , wherein A′ comprises at least one of N-methyl-1,3-propane diammonium (Me-PDA) or 1,4-bis(aminomethyl)benzene (p-PBA).

8. The composition of claim 7 , wherein the second crystalline structure comprises at least one of (Me-PDA)Pb 2 I 6 or (p-PBA)Pb 2 I 6 .

9. The composition of claim 1 , wherein:

the perovskite comprises FA 1−x−y MA x C Sy Pb(I 1−z Br z ) 3 ,

0≤x≤1, 0≤y≤1, and 0≤z≤1.

10. The composition of claim 1 , wherein the second layer has a surface roughness less than or equal to about 16 nm.

11. The composition of claim 1 , wherein the composition has a yield mobility product (φΣμ) of at least about 50.0 cm 2 /Vs.

12. The composition of claim 1 , wherein the composition has a charge-carrier lifetime of at least about 1.5 microseconds.

13. The composition of claim 1 , wherein the composition has an out-of-plane charge transport between (1-3)×10 −3 cm 2 V −1 s −1 and 1×10 −1 cm 2 V −1 s −1 .

14. The composition of claim 1 , wherein the second layer uniformly covers the first layer.

15. The composition of claim 1 , wherein the first layer has a thickness between about 100 nm and about 2000 nm.

16. The composition of claim 1 , wherein the second layer has a thickness between about 1 nm and about 100 nm.

17. The composition of claim 1 , wherein the composition has a charge-carrier lifetime between 1.5 microseconds and 5.0 microseconds.

18. The composition of claim 1 , wherein the composition is characterized by a peak at less than 10°, as measured by XRD.

19. A device comprising:

a first layer comprising a perovskite; and

a second layer comprising a perovskitoid, wherein:

the perovskite has a first crystalline structure comprising ABX 3 ,

the perovskitoid has a second crystalline structure comprising A′B 2 X 6 ,

A comprises a first cation, B comprises a second cation, X comprises an anion, and A′ comprises a third cation having either a 1+ charge or a 2+ charge.

20. A device comprising, in order:

a glass substrate;

a layer comprising fluorine-doped tin oxide;

a layer comprising compact TiO 2 ;

a layer comprising mesoporous TiO 2 ;

a layer comprising a perovskite;

a layer comprising a perovskitoid;

a layer comprising a hole-transport material (HTL); and

a metal layer, wherein:

the perovskite has a first crystalline structure comprising ABX 3 ,

the perovskitoid has a second crystalline structure comprising A′B 2 X 6 ,

A comprises a first cation, B comprises a second cation, X comprises an anion, and A′ comprises a third cation having either a 1+ charge or a 2+ charge.

Assignments (3)
CHANGE OF NAME Recorded Dec 16, 2025
From: ALLIANCE FOR SUSTAINABLE ENERGY, LLC
To: ALLIANCE FOR ENERGY INNOVATION, LLC
Reel/Frame 073993/0276 →
CONFIRMATORY LICENSE Recorded Mar 4, 2024
From: ALLIANCE FOR SUSTAINABLE ENERGY, LLC
To: U.S. DEPARTMENT OF ENERGY
Reel/Frame 066633/0464 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 1, 2023
From: ZHU, KAI; ZHANG, FEI
To: ALLIANCE FOR SUSTAINABLE ENERGY, LLC
Reel/Frame 065423/0208 →
Continuity (2)
Provisional Application 63192918 · May 25, 2021
Related Publication 20240224549A1 · Jul 4, 2024
References Cited (37)
US 20220059780A1 · Zhu et al. · 2022 [cited by applicant]
Zhang et al., “Surface lattice engineering through three-dimensional lead iodide perovskitoid for high-performance perovskite solar cells”, Chem 7, 774-785, Mar. 11, 2021. (Year: 2021). [cited by examiner]
Pham et al., “1D Pyrrolidinium Lead Iodide for Efficient and Stable Perovskite Solar Cells”, Energy Technol. 2020, 8, 1900918. (Year: 2020). [cited by examiner]
Chen, P. et al., “In Situ Growth of 2D Perovskite Capping Layer for Stable and Efficient Perovskite Solar Cells,” Advanced Functional Materials, vol. 28, 2018, 10 pages. [cited by applicant]
Chen, X. et al., “Impact of Layer Thickness on the Charge Carrier and Spin Coherence Lifetime in Two-Dimensional Layered Perovskite Single Crystals,” ACS Energy Letters, vol. 3, 2018, 7 pages. [cited by applicant]
Gangadharan, D.T. et al., “Search for stability at lower dimensions: current trends and future prospects of layered perovskite solar cells,” RSC Energy & Environmental Science, vol. 12, 2019, 30 pages. [cited by applicant]
Gao, L. et al., “Enhanced Charge Transport by Incorporating Formamidinium and Cesium Cations into Two-Dimensional Perovskite Solar Cells,” Angewandte Chemie, vol. 131, 2019, 5 pages. [cited by applicant]
Jiang, Q. et al., “Surface passivation of perovskite film for efficient solar cells,” Nature Photonics, vol. 13, Jul. 2019, 10 pages. [cited by applicant]
Kim, D.H. et al., “300% Enhancement of Carrier Mobility in Uniaxial-Oriented Perovskite Films Formed by Topotactic-Oriented Attachment,” Advanced Materials, vol. 29, 2017, 8 pages. [cited by applicant]
Khenkin, M.V. et al., “Consensus statement for stability assessment and reporting for perovskite photovoltaics based on ISOS procedures,” Nature Energy, vol. 5, Jan. 2020, 15 pages. [cited by applicant]
Koh, T.M. et al., “Enhancing moisture tolerance in efficient hybrid 3D/2D perovskite photovoltaics,” RSC Journal of Materials Chemistry A, vol. 6, 2018, 7 pages. [cited by applicant]
Li, G. et al.., “Polysulfide Regulation by the Zwitterionic Barrier toward Durable Lithium-Sulfur Batteries,” Journal of the American Chemical Society, vol. 142, 2020, 10 pages. [cited by applicant]
Li, X. et al., “Three-Dimensional Lead Iodide Perovskitoid Hybrids with High X-ray Photoresponse,” Journal of the American Chemical Society, vol. 142, 2020, 13 pages. [cited by applicant]
Liang, L. et al., “Efficient Perovskite Solar Cells by Reducing Interface-Mediated Recominationa: a Bulky Amine Approach,” Advanced Energy Materials, vol. 10, 2020, 12 pages. [cited by applicant]
Liu, B. et al., “Interfacial charge behaior modulation in 2D/3D perovskite heterostructure for potential high-performance solar cells,” Nano Energy, vol. 59, 2019, 6 pages. [cited by applicant]
Liu, X. et al., “Dopant-free and low-cost molecular “bee” hole-transporting materials for efficient and stable perovskite solar cells,” RSC Journal of Materials Chemistry C, vol. 5, 2017, 7 pages. [cited by applicant]
Liu, Y. et al., “Ultrahydrophobic 3D/2D fluoroarene bilayer-based water-resistant perovskite solar cells with efficiencies exceeding 22%,” Science Advances, vol. 5, 2019, 9 pages. [cited by applicant]
Liu, Y. et al., “Stabilization of Highly Efficient and Stable Phase-Pure FAPbI3 Perovskite Solar Cells by Molecularly Tailored 2D-Overlayers,” Angew. Chem. Int. Ed., vol. 59, 2020, 7 pages. [cited by applicant]
Lu, H. et al., “Spin-dependent charge transport through 2D chiral hybrid lead-iodide perovskites,” Science Advances, vol. 5, 2019, 8 pages. [cited by applicant]
Luo, D. et al., “Enhanced photovoltage for inverted planar heterojunction perovskite solar cells,” Science, vol. 360, 2018, 6 pages. [cited by applicant]
Mao, L. et al., “Hybrid Dion-Jacobson 2D Lead Iodide Perovskites,” Journal of the American Chemical Society, vol. 140, 2018, 9 pages. [cited by applicant]
Min, H. et al., “Efficient, stable solar cells by using inherent bandgap of α-phase formamidinium lead iodide,” Science, vol. 366, 2019, 6 pages. [cited by applicant]
Niu, T. et al., “Interfacial Engineering at the 2D/3D Heterojunction for High-Performance Perovskite Solar Cells,” Nano Letters, vol. 19, 2019, 10 pages. [cited by applicant]
Perkins, C. et al., “Surfactant-assisted growth of CdS thin films for photovoltaic applications,” Journal of Vac. Sci. Technol. A 24(3), May/Jun. 2006, 8 pages. [cited by applicant]
Stoumpos, C. S. et al., “Structure-Band Gap Relationships in Hexagonal Polytypes and Low-Dimensional Structures of Hybrid Tin Iodide Perovskites,” ACS Inorganic Chemistry, vol. 56, 2017, 18 pages. [cited by applicant]
Wang, Y. et al., “Efficient α-CsPbI3 Photovoltaics with Surface Terminated Organic Cations,” Joule, vol. 2, 2018, 12 pages. [cited by applicant]
Xiao, C. et al., Junction Quality of SnO2-Based Perovskite Solar Cells Investigated by Nanometer-Scale Electrical Potential Profiling, Applied Materials & Interfaces, vol. 9, 2017, 8 pages. [cited by applicant]
Ye, J. Y. et al., “Enhancing Charge Transport of 2D Perovskite Passivation Agent for Wide-Bandgap Perovskite Solar Cells Beyond 21%,” Solar RRL, vol. 4, 2020, 8 pages. [cited by applicant]
Zhang, F. et al., “Additive Engineering for Efficient and Stable Perovskite Solar Cells,” Advanced Energy Materials, vol. 10, 2020, 26 pages. [cited by applicant]
Zhang, F. et al., “Enhanced Charge Transport in 2D Perovskites via Fluorination of Organic Cation,” Journal of the American Chemical Society, vol. 141, 2019, 8 pages. [cited by applicant]
Zhang, F. et al., “Advances in two-dimensional organic-inorganic hybrid perovskites,” RSC Energy & Environmental Science, vol. 13, 2020, 33 pages. [cited by applicant]
Zhang, F. et al., “Surface lattice engineering through three-dimensional lead iodide perovskitoid for high-performance perovskite solar cells,” Chem, vol. 7, 2021, 13 pages. [cited by applicant]
Zhao, H. et al., “Enhanced stability and optoelectronic properties of MAPbI3 films by a cationic surface-active agent for perovskite solar cells,” RSC Journal of Materials Chemistry A, vol. 6, 2018, 10 pages. [cited by applicant]
Zhou, Q. et al., “High-Performance Perovskite Solar Cells with Enhanced Environmental Stability Based on a (p-FC6H4C2H4NH3)2[PbI4] Capping Layer,” Advanced Energy Materials, vol. 9, 2019, 11 pages. [cited by applicant]
Zhu, H. et al., “Tailored Amphiphilic Molecular Mitigators for Stable Perovskite Solar Cells with 23.5% Efficiency,” Advanced Materials, vol. 32, 2020, 8 pages. [cited by applicant]
Zhu, K. et al., “3D/2D multidimensional perovskites: Balance of high performance and stability for perovskite solar cells,” Elsevier Science, vol. 11, 2018, 9 pages. [cited by applicant]
PCT/US22/30709 Search Report and Written Opinion, issued Sep. 29, 2022; 7 pages total. [cited by applicant]