Phonon Properties and Lattice Dynamics of Two- and Tri-Layered Lead Iodide Perovskites Comprising Butylammonium and Methylammonium Cations—Temperature-Dependent Raman Studies DOI Open Access
Mirosław Mączka, Szymon Smółka, Maciej Ptak

et al.

Materials, Journal Year: 2024, Volume and Issue: 17(11), P. 2503 - 2503

Published: May 22, 2024

Hybrid lead iodide perovskites are promising photovoltaic and light-emitting materials. Extant literature data on the key optoelectronic luminescent properties of hybrid indicate that these affected by electron–phonon coupling, dynamics organic cations, degree lattice distortion. We report temperature-dependent Raman studies BA2MAPb2I7 BA2MA2Pb3I10 (BA = butylammonium; MA methylammonium), which undergo two structural phase transitions. obtained in broad temperature (360–80 K) wavenumber (1800–10 cm−1) ranges show ordering BA+ cations triggers higher transition, whereas freezing MA+ occurs below 200 K, leading to onset low-temperature transition. This is associated with significant deformation inorganic sublattice, as evidenced changes observed mode region. Our results show, therefore, spectroscopy a very valuable tool for monitoring separate different perovskites, comprising “perovskitizer” interlayer cations.

Language: Английский

Effect of Halide Tuning on the Structural, Dielectric, and Optical Properties of Two-Dimensional 2-Chloroethylammonium Lead Halides DOI Creative Commons
Mirosław Mączka,

Jan Kudrawiec,

Katarzyna Fedoruk

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 26, 2025

Layered hybrid organic–inorganic lead halides have gained a lot of attention for optoelectronic applications. A notable subset within this category is perovskites comprising halogenated amines since they may exhibit reduced band gap or polar order. We synthesized three compounds 2-chloroethylammonium (CEA+) cations, with the chemical formula CEA2PbX4 (X = Cl, Br, I). X-ray diffraction studies show that at room temperature (RT), CEA2PbBr4 and CEA2PbI4 crystallize in Pbnm symmetry, ordered CEA+ cations. undergo one structural phase transition (PT) into disordered Pmnm near 315 360 K, respectively. CEA2PbCl4 shows different packing organic chains oriented perpendicularly to perovskite layers. It undergoes two PTs 332 203 K from high-temperature (HT) I4/mmm partially intermediate completely low-temperature (LT) unknown space group. All emit photoluminescence (PL): orange, yellow-green, yellow CEA2PbI4, CEA2PbCl4, CEA2PbBr4, respectively, bromide exhibits very high quantum efficiency 48%. Overall, our findings halide engineering strongly modulates hydrogen halogen bonding strength, affecting arrangement building units, molecular dynamics, thus properties.

Language: Английский

Citations

0
Unprecedented Richness of Temperature‐ and Pressure‐Induced Polymorphism in 1D Lead Iodide Perovskite DOI
Marcin Saski, Szymon Sobczak, Paulina Ratajczyk

et al.

Small, Journal Year: 2024, Volume and Issue: unknown

Published: May 30, 2024

Abstract Inherent features of metal halide perovskites are their softness, complex lattice dynamics, and phase transitions spectacularly tuning structures properties. While the structural transformations well described classified in 3D perovskites, 1D analogs much less understood. Herein, both temperature‐ pressure‐dependent evolutions a AcaPbI 3 perovskitoid incorporating acetamidinium (Aca) cation examined. The study reveals existence nine phases δ‐AcaPbI , which present most diverse polymorphic collection among known perovskite materials. Interestingly, pressure‐triggered perovskotoid exhibit fundamentally different natures: thermal mainly associated with collective translations rigid polyanionic units ordering/disordering dynamics Aca cations, while compression primarily affects inorganic polymer chains. Moreover, 1‐D chains featuring face‐sharing connection mode PbI 6 octahedra Pb···Pb distances significantly shortened compared to corner‐sharing frameworks, hence operating van der Waals territory. Strikingly, good correlation is found between pressure evolution bandgap values indicating that structures, contacts Pb 2+ ions one critical parameters determining

Language: Английский

Citations

3
Low-Temperature Persistent Disorder and Lattice Dynamics in a Luminescent 1D Hybrid Lead Halide: Implications and Insights DOI Creative Commons

Andrzej Nowok,

Mirosław Mączka, Anna Gągor

et al.

Chemistry of Materials, Journal Year: 2024, Volume and Issue: 36(13), P. 6588 - 6597

Published: June 24, 2024

Hybrid organic–inorganic halides have traditionally been viewed as materials that adopt well-ordered structural phases at low temperatures. In this article, we report a one-dimensional perovskitoid aminoguanidinium lead iodide (AGAPbI3) with first-order phase transition 400/369 K (during heating/cooling) breaks away from rule. Specifically, demonstrate the transformation to low-temperature monoclinic C2/c does not entirely suppress motions associated organic AGA+ cation, leading phenomenon which call now persistent disorder. Indeed, it is still possible observe pronounced dynamics of its terminal NH2 group least, gradually slows down upon cooling and impacts PbI64– octahedra. As result, an unusually high activation energy 0.6 eV related relaxation dynamics, approximately 1 order magnitude higher than those observed in conventional hybrid halides. We illustrate ongoing dynamic processes profoundly influence temperature-dependent third-harmonic generation response photoluminescence, latter characterized by two broad emission peaks large Stokes shifts. Lastly, emphasize cations can symmetry-equivalent positions within AGAPbI3, revealing between static high-temperature disorder types compound.

Language: Английский

Citations

3
Multi-Noncentrosymmetric Polar Order in 2D Hybrid Lead Chloride with Broadband Emission and High-Temperature Second-Harmonic Generation Switching DOI Creative Commons
Mirosław Mączka, Jan K. Zaręba, Anna Gągor

et al.

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: 16(44), P. 60564 - 60575

Published: Oct. 24, 2024

Two-dimensional lead halide perovskites represent a fascinating class of hybrid semiconductors for solar cell, light-emitting, nonlinear optical (NLO), and ferroelectric applications. A notable subset within this category is luminescent ferroelectrics, which have garnered considerable attention their potential in integrated photoelectronic devices. In study, we employed an organic amine halogenation strategy (also referred to as halogen engineering), renowned its efficacy inducing polar order through crystal engineering. Consequently, synthesized layered Ruddlesden-Popper (RP) chloride comprising 3-chloropropylammonium cations (CPA

Language: Английский

Citations

3
B-Site Mixing Effects in Hybrid Perovskites: Phase Transitions and Dielectric Response of MAPb1–xSnxBr3 DOI Creative Commons

Gabrielius Rimkus,

Sergejus Balčiūnas, Hanna R. Petrosova

et al.

Chemistry of Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 29, 2025

Ion-mixing is a highly effective strategy for tuning the performance and stability of photovoltaic devices based on hybrid perovskites. Despite many works concentrating A- X-site mixing effects, comprehensive study effects B-site structural dynamic properties MA-based perovskites still absent. In this work, we investigate mixed lead–tin halide MAPb1–xSnxBr3 using multitechnique experimental approach including differential scanning calorimetry, dielectric spectroscopy, nuclear quadrupole resonance experiments. We map phase diagram system, which reveals that slightly stabilizes cubic affects MA cation dynamics ordering, although observed are less prominent compared with mixing. Our results provide insights into complex interplay in mixed-metal contributing to their potential optimization applications.

Language: Английский

Citations

0
Pyro-phototronic effect enhanced self-powered photodetectors: A review on perovskite materials DOI

Xiaodi Jia,

Shujie Jiao, Song Yang

et al.

Next Materials, Journal Year: 2025, Volume and Issue: 8, P. 100563 - 100563

Published: March 4, 2025

Language: Английский

Citations

0
New hybrid thiocyanates: Crystal structures, optical properties and unusual dielectric switching properties DOI

Soulayma Mtar,

Mirosław Mączka, Szymon Smółka

et al.

Inorganic Chemistry Communications, Journal Year: 2025, Volume and Issue: unknown, P. 114358 - 114358

Published: March 1, 2025

Language: Английский

Citations

0
Temperature- and Pressure-Dependent Raman and Photoluminescence Studies of Corrugated Imidazolium-Methylhydrazinium Lead Bromide DOI Creative Commons
Mirosław Mączka, José Avelar S. da Silva, W.P. Gomes

et al.

The Journal of Physical Chemistry C, Journal Year: 2024, Volume and Issue: 128(21), P. 8698 - 8707

Published: May 20, 2024

Alternating cations in interlayer space (ACI) perovskites are attractive optoelectronic materials. In this work, temperature- and pressure-dependent Raman photoluminescence studies of (110)-derived ACI perovskite comprising imidazolium (IM+) methylhydrazinium (MHy+) reported. Temperature-dependent spectra show a gradual increase the lattice dynamics weak changes at structural phase transition near 350 K. Photoluminescence reveal that IMMHyPbBr4 exhibits strong broadband emission related to self-trapped excitons narrow attributed free localized excitons. Small value activation energy (107 ± 10 meV) large Stokes shift proves on deep defects. Pressure-dependent low pressure, compression is accommodated mainly by squeezing organic layers, which leads tilts IM+ hydrogen-bond strength. The presence strongly first-order pressure-induced observed between 1.25 1.53 GPa analysis indicates associated with sudden freezing molecular accompanied tilting distortion PbBr6 octahedra. This decrease layer thickness should affect dielectric constant layers thus modify confinement exciton binding energy. spectroscopy provides, therefore, evidence pressure-enhanced hydrogen bonding plays major role tuning properties perovskites. confirms assumption, showing bandgap narrowing due combined effect Pb–Br bond shortening confinement. also remarkable stability compression, making material for light-emitting applications broad temperature pressure ranges.

Language: Английский

Citations

2
Phase Diagram and Dielectric Response of Hybrid Lead Halide Hollow Perovskites: A Universal Behavior of Molecular Cation Mixing DOI Creative Commons

Gabrielius Rimkus,

Sergejus Balčiūnas, Maciej Ptak

et al.

Chemistry of Materials, Journal Year: 2024, Volume and Issue: 36(15), P. 7397 - 7405

Published: July 23, 2024

Mixing of molecular cations in hybrid lead halide perovskites is used to effectively tune the stability and performance photovoltaic devices based on these compounds. Upon introduction bulky such as ethylenediammonium (EN), perovskite framework becomes locally broken resulting so-called hollow perovskites. Here, we use a set different experimental techniques probe structural phase transitions, cation dynamics, dielectric response methylammonium-based MA1–xENxPb1–0.7xI3–0.4x containing amounts EN (x ≤ 0.26). We determine temperature–composition diagram this system show that results stabilization desirable high-symmetry cubic phase, transitions become partially suppressed. Broadband spectroscopy experiments are study dynamics for fractions EN. For high levels EN, observe signatures dipolar glass formation. Our findings indicate universal trend upon mixing independent size charge incorporated guest MAPbI3.

Language: Английский

Citations

2
Organic cations in halide perovskite solid solutions: exploring beyond size effects DOI
F. B. Minussi, Rogério Marcos Silva, J.C.S. Moraes

et al.

Physical Chemistry Chemical Physics, Journal Year: 2024, Volume and Issue: 26(31), P. 20770 - 20784

Published: Jan. 1, 2024

Organic A-site substituting cations with same sizes have remarkably different effects on the structure, phase transitions, electrical behavior, and stability of halide perovskite solid solutions.

Language: Английский

Citations

2