The layer edge states or low energy state (LES) in 2D hybrid organic–inorganic perovskites demonstrate a prolonged carrier lifetime for better performance of optoelectronic devices. However, the fundamental understanding of LES in 2D perovskites is still inconclusive. Herein, a photoluminescence (PL) study of LES in 2D Ruddlesden–Popper perovskites is presented withn = 2 andn = 3 from their cleaved cross sections that are more stable than the natural edge. The PL measurements clearly observe reversible, and irreversible surface relaxations (case I and case II) in three laser intensity ranges, further supported by a PL excitation cycle from low to high laser intensity, and vice versa. The PL wavelength of LES is tunable with laser intensity and blueshifts with increasing laser intensity during irreversible surface relaxation process (case I). Fluorescence lifetime imaging (FLIM) shows that the LES has a longer lifetime than the band‐edge emission in the sample without a photodegradation, while the BE lifetime becomes relatively longer in the area with a photodegradation. The presented laser tunable LES and the related irreversible relaxation process provide a new insight that can help improve the photostability in 2D perovskites and understand roles of LESs in optoelectronic device performance.
more »
« less
Enhanced Photoluminescence and Prolonged Carrier Lifetime through Laser Radiation Hardening and Self-Healing in Aged MAPbBr3 Perovskites Encapsulated in NiO Nanotubes
Organic-inorganic perovskites hold great promise as optoelectronic semiconductors for pure color light emitting and photovoltaic devices. However, challenges persist regarding their photostability and chemical stability, which limit their extensive applications. This paper investigates the laser radiation hardening and self-healing-induced properties of aged MAPbBr3 perovskites encapsulated in NiO nanotubes (MAPbBr3@NiO) using photoluminescence (PL) and fluorescence lifetime imaging (FLIM). After deliberately subjecting the MAPbBr3@ NiO to atmospheric conditions for two years, the sample remains remarkably stable. It exhibits no changes in PL wavelength during UV laser irradiation and self-healing. Furthermore, exposure to UV light at 375 nm enhances the PL of the self-healed MAPbBr3@NiO. FLIM analysis sheds light on the mechanism behind photodegradation, self-healing, and PL enhancement. The results indicate the involvement of many carrier-trapping states with low lifetime events and an increase in peak lifetime after self-healing. The formation of trapping states at the perovskite/nanotube interface is discussed and tested. This study provides new insights into the dynamics of photo-carriers during photodegradation and self-healing in organic-inorganic perovskites.
more »
« less
- Award ID(s):
- 2128367
- PAR ID:
- 10529774
- Publisher / Repository:
- MDPI
- Date Published:
- Journal Name:
- Micromachines
- Volume:
- 14
- Issue:
- 9
- ISSN:
- 2072-666X
- Page Range / eLocation ID:
- 1706
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
All-inorganic lead halide perovskites have been extensively studied in the past several years due to their superior stability against moisture, oxygen, light, and heat compared with their organic–inorganic counterparts. CsPbBr3 with suitable band gap and ultrahigh photoluminescence quantum yield is a promising candidate for pure green emitter in the backlighting display to fill the so-called “green gap.” Here, vapor-phase growth of CsPbBr3 microspheres is reported for highly efficient pure green light emission. The as-synthesized microspheres exhibit a stronger photoluminescence (PL) intensity with a photoluminescence quantum yield of 75% resulting from the lower energy of longitudinal optical phonons revealed by temperature dependent PL studies. Importantly, with the diameter increasing from 2 to 50 μm the PL peak positions of the microspheres can be readily tuned from 527 to 539 nm, well filling the so-called “green gap.” The red-shift with increasing diameter can be ascribed to the reabsorption process during the photon propagation inside the microspheres. The studies provide a route to improve the photoluminescence quantum yield in all-inorganic lead halide perovskites, but also suggest an alternative approach to achieve the pure green emission for the backlighting display.more » « less
-
Abstract Achieving efficient and stable blue light‐emitting perovskite nanocrystals is a significant challenge for next‐generation optoelectronic devices. Here, a dual‐ligand surface engineering strategy is reported for quasi‐2D CsPbBr3nanoplatelets (NPLs) synthesized via ligand‐assisted reprecipitation. By synergistically co‐introducing didodecyldimethylammonium bromide to passivate bromine vacancies and hexylphosphonic acid to bind undercoordinated lead ions, the NPLs achieved a remarkable photoluminescence quantum yield of 93.7% and a narrow full‐width at half‐maximum of 19.27 nm. The enhanced photoluminescence (PL) lifetime (6.35 ns), reduced crystal disorder, slower bleach recovery kinetics, and improved thermal stability suggest that the suppressed non‐radiative pathways and strong exciton confinement (Eb = 141.76 meV) result from effective surface defect passivation and enhanced radiative recombination. Additionally, surface and structural characterizations confirmed the successful dual‐ligand integration and improved crystal integrity. The treated NPLs retained ∼57% PL under 450 min of ultraviolet (UV) light and ∼55% PL under 70% relative humidity, demonstrating strong UV and moisture stability. A prototype white light‐emitting device fabricated by integrating dual‐ligand‐treated NPLs achieves a wide color gamut (121% National Television System Committee, 90.4% ITU‐R Recommendation BT.2020), demonstrating their potential for high‐performance optoelectronics. This approach promotes defect suppression in low‐dimensional perovskites, paving the way for stable and efficient blue emitters.more » « less
-
Abstract A new approach to generate a two‐photon up‐conversion photoluminescence (PL) by directly exciting the gap states with continuous‐wave (CW) infrared photoexcitation in solution‐processing quasi‐2D perovskite films [(PEA)2(MA)4Pb5Br16withn= 5] is reported. Specifically, a visible PL peaked at 520 nm is observed with the quadratic power dependence by exciting the gap states with CW 980 nm laser excitation, indicating a two‐photon up‐conversion PL occurring in quasi‐2D perovskite films. Decreasing the gap states by reducing thenvalue leads to a dramatic decrease in the two‐photon up‐conversion PL signal. This confirms that the gap states are indeed responsible for generating the two‐photon up‐conversion PL in quasi‐2D perovskites. Furthermore, mechanical scratching indicates that the different‐n‐value nanoplates are essentially uniformly formed in the quasi‐2D perovskite films toward generating multi‐photon up‐conversion light emission. More importantly, the two‐photon up‐conversion PL is found to be sensitive to an external magnetic field, indicating that the gap states are essentially formed as spatially extended states ready for multi‐photon excitation. Polarization‐dependent up‐conversion PL studies reveal that the gap states experience the orbit–orbit interaction through Coulomb polarization to form spatially extended states toward developing multi‐photon up‐conversion light emission in quasi‐2D perovskites.more » « less
-
null (Ed.)The past decade has witnessed tremendous advances in synthesis of metal halide perovskites and their use for a rich variety of optoelectronics applications. Metal halide perovskite has the general formula ABX 3 , where A is a monovalent cation (which can be either organic ( e.g. , CH 3 NH 3 + (MA), CH(NH 2 ) 2 + (FA)) or inorganic ( e.g. , Cs + )), B is a divalent metal cation (usually Pb 2+ ), and X is a halogen anion (Cl − , Br − , I − ). Particularly, the photoluminescence (PL) properties of metal halide perovskites have garnered much attention due to the recent rapid development of perovskite nanocrystals. The introduction of capping ligands enables the synthesis of colloidal perovskite nanocrystals which offer new insight into dimension-dependent physical properties compared to their bulk counterparts. It is notable that doping and ion substitution represent effective strategies for tailoring the optoelectronic properties ( e.g. , absorption band gap, PL emission, and quantum yield (QY)) and stabilities of perovskite nanocrystals. The doping and ion substitution processes can be performed during or after the synthesis of colloidal nanocrystals by incorporating new A′, B′, or X′ site ions into the A, B, or X sites of ABX 3 perovskites. Interestingly, both isovalent and heterovalent doping and ion substitution can be conducted on colloidal perovskite nanocrystals. In this review, the general background of perovskite nanocrystals synthesis is first introduced. The effects of A-site, B-site, and X-site ionic doping and substitution on the optoelectronic properties and stabilities of colloidal metal halide perovskite nanocrystals are then detailed. Finally, possible applications and future research directions of doped and ion-substituted colloidal perovskite nanocrystals are also discussed.more » « less
An official website of the United States government
