Induced Chirality in Halide Perovskite Clusters through Surface Chemistry

Forde, Aaron; Ghosh, Dibyajyoti; Kilin, Dmitri S.; Evans, Amanda C.; Tretiak, Sergei; Neukirch, Amanda

doi:10.1021/acs.jpclett.1c04060

Cited by 15 publications

(16 citation statements)

References 35 publications

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“…For a low (S)-3-ABA-concentration (1:9 (S)-3-ABA/DMAPbI 3 :DMAPbI 3 precursor solution mixing ratio), no CD signal is observed, and only weak signals can be detected for the 3:7 and 1:1 ratios. In agreement with theoretical models on perovskite clusters, [40] the signal intensity grows significantly, if the amino acid content is increased further. A maximum is reached between a 7:3 and a 9:1 ratio.…”

Section: Resultssupporting

confidence: 88%

“…DFT calculations have shown that for multidentate ligands the CD effect is governed by the exact binding configuration of the organic. [ 40 ] This suggests that under excess of 3‐ABA a higher surface coverage can be achieved, which hence decreases the CD intensity through partial differences in the binding geometry of the chiral component. Overall, this concentration dependence represents a facile and straightforward approach to adjust the CD intensity by controlling the amount of amino acid available for surface functionalization.…”

Section: Resultsmentioning

confidence: 99%

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Strong Induced Circular Dichroism in a Hybrid Lead‐Halide Semiconductor Using Chiral Amino Acids for Crystallite Surface Functionalization

Heindl

Kodalle

Fehn

et al. 2022

Advanced Optical Materials

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Chirality is a desired property in functional semiconductors for optoelectronic, catalytic, and spintronic applications. Here, introducing enantiomerically‐pure 3‐aminobutyric acid (3‐ABA) into thin films of the 1D semiconductor dimethylammonium lead iodide (DMAPbI3) is found to result in strong circular dichroism (CD) in the optical absorption. X‐ray diffraction and grazing incidence small angle X‐ray scattering (GISAXS) are applied to gain molecular‐scale insights into the chirality transfer mechanism, which is attributed to a chiral surface modification of DMAPbI3 crystallites. This study demonstrates that the CD signal strength can be controlled by the amino‐acid content relative to the crystallite surface area. The CD intensity is tuned by the composition of the precursor solution and the spin‐coating time, thereby achieving anisotropy factors (gabs) as high as 1.75 × 10–2. Grazing incidence wide angle scattering reveals strong preferential ordering that can be suppressed via tailored synthesis conditions. Different contributions to the chiroptical properties are resolved by a detailed analysis of the CD signal utilizing an approach based on the Mueller matrix model. This report of a novel class of chiral hybrid semiconductors with precise control over their optical activity presents a promising approach for the design of circularly polarized light detectors and emitters.

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Section: Resultssupporting

confidence: 88%

Section: Resultsmentioning

confidence: 99%

Strong Induced Circular Dichroism in a Hybrid Lead‐Halide Semiconductor Using Chiral Amino Acids for Crystallite Surface Functionalization

Heindl

Kodalle

Fehn

et al. 2022

Advanced Optical Materials

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“…For example, chiral lanthanide complexes have the highest g lum value reported but a poor PLQY (3% for powder) . In Figure a,b, there exists the mirror-like CPL signal attributed to the different chirality, which is well consistent with previous reports. − The CPL spectra of (R/S-MBA) 4 Cu 4 I 8 ·2H 2 O are mirror-like in the region of 350–700 nm with a peak at around 519 nm. In Figure c, Δ I represents the gap value between I L (LCP) and I R (RCP).…”

supporting

confidence: 88%

Chiral Hybrid Copper(I) Iodide Single Crystals Enable Highly Selective Ultraviolet-Pumped Circularly Polarized Luminescence Applications

Song

Liu

et al. 2022

J. Phys. Chem. Lett.

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Light-emitting diodes (LEDs) with the circularly polarized luminescence features have attracted attention to the promising applications ranging from solid-state lighting and displays to bioencoding and anticounterfeiting. The prerequisite of circularly polarized luminescence is highly emissive chiral materials. Here, we demonstrated that (R/S-MBA) 4 Cu 4 I 8 •2H 2 O (MBA = α-methylbenzylaminium) and acentric Gua 6 Cu 4 I 10 (Gua = guanidinium) single crystals were grown on the basis of Gua 3 Cu 2 I 5 by the slow evaporation method. (R/S-MBA) 4 Cu 4 I 8 •2H 2 O single crystals exhibited excellent circularly polarized luminescence (CPL) characteristics. More importantly, ultraviolet-pumped LEDs (UV-LEDs) based on (R/S-MBA) 4 Cu 4 I 8 •2H 2 O and Gua 6 Cu 4 I 10 single crystals exhibit a higher optical selectivity when exposed to right-handed and left-handed circular polarization (RCP and LCP) conditions. (S-MBA) 4 Cu 4 I 8 •2H 2 O single crystals and Gua 6 Cu 4 I 10 single crystals induced by the (R)-MBA cation exhibit the different polarized light intensities at PL peak positions in different λ/4 waveplate polarizer angle directions, which provides new possibilities for the further applications from 3D displays to spintronics, as well as anticounterfeiting.

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“…The extent to which subtle differences in ligand structure and orientation result in significant changes in CD shape and magnitude indicates that the mechanism of the optical activity observed is likely a result of chiral molecular dipole and transition dipole coupling. [ 46 ] Such chirality transfer originates from coupling of the static dipole of the chiral surface ligand to the transition dipole moment of the perovskite nanocrystal, and the resulting CD spectrum is dependent on the specific binding configuration of the ligand. [ 46 ] Changes to the electronic structure of the NPLs by altering either the A‐site cation or halide composition resulted in a decreased CD signal intensity, supporting this theory (Figures and , Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

“…[ 46 ] Such chirality transfer originates from coupling of the static dipole of the chiral surface ligand to the transition dipole moment of the perovskite nanocrystal, and the resulting CD spectrum is dependent on the specific binding configuration of the ligand. [ 46 ] Changes to the electronic structure of the NPLs by altering either the A‐site cation or halide composition resulted in a decreased CD signal intensity, supporting this theory (Figures and , Supporting Information). The drastic difference in the magnitude of g abs between DMBA and other chiral ligands suggests that long‐range ordering may be present for this ligand, resulting in a chiral amplification which is not observed for MBA, EBA, or CHEA.…”

Section: Resultsmentioning

confidence: 99%

Chiral Perovskite Nanoplatelets Exhibiting Circularly Polarized Luminescence through Ligand Optimization

Hubley

Bensalah‐Ledoux

Baguenard

et al. 2022

Advanced Optical Materials

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absorption or emission of circularly polarized light is referred to as circular dichroism (CD) or circularly polarized luminescence (CPL), and leads to many practical technologies such as 3D displays, spintronics, quantum computing, drug screening, anti-counterfeiting, and photoelectric devices. [1][2][3][4][5][6] However, realizing such technologies requires the development of sources of circularly polarized light. Conventionally this involves filtering unpolarized light using an optical polarizer, the drawbacks of which include both decrease in intensity and need for additional optical elements. Current methods seek to circumvent these issues by producing direct sources of CPL, leading to device miniaturization, lower production costs, lower energy consumption, and faster data processing rates. [7] Small organic chiral fluorophores can be used for this purpose, but typically suffer from weak CPL with luminescence dissymmetry values on the order of g lum = 10 −4 to g lum = 10 −2 . [8,9] Additionally, many of these organic molecules show optical activity in the UV-range, whereas applications often require emission in the visible spectrum. One of the solutions is to couple chiral organic molecules with semiconductor nanocrystals (NCs), consequently achieving direct CPL in the visible spectrum. [10] Doing so, it is possible to achieve much stronger chiroptical signals. [11,12] Ligand-induced chirality has been shown to induce optical activity in semiconductor nanocrystals. [13] This involves the incorporation of chiral ligands either directly in the synthesis of colloidal nanocrystals, or through post-synthetic surface treatment. [14] This can result in new optical activity at the characteristic wavelengths corresponding to excitonic transitions of the NC, and both circular dichroism and circularly polarized luminescence can be observed. [15] However, materials showing CPL are less common than those exhibiting CD. [16] Furthermore, to produce high-performance CPL emitters through ligandinduced chirality requires both a chiral molecule compatible with the NC surface, and a NC with superior optoelectronic properties including narrow emission line width, high photoluminescence quantum yield, and a wide range of color tunability.Hybrid organic-inorganic perovskite nanocrystals meet these optoelectronic prerequisites, making them ideal candidates for Chiral halide perovskite nanocrystals have many applications in nextgeneration optoelectronic devices due to their interaction with polarized light. Through careful selection of chiral organic surface ligands, control over the circular dichroism (CD) and circularly polarized luminescence (CPL) of these materials can be achieved. However, while recent developments of CD-active perovskites have seen significant advances, effective CPL remains a challenge. Here, colloidal perovskite nanoplatelets are synthesized exhibiting room temperature CPL with dissymmetry factors up to g lum = 4.3 × 10 −3 and g abs = 8.4 × 10 −3 . Methylammonium lead bromide nanoplatelets are synthesized ...

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Induced Chirality in Halide Perovskite Clusters through Surface Chemistry

Cited by 15 publications

References 35 publications

Strong Induced Circular Dichroism in a Hybrid Lead‐Halide Semiconductor Using Chiral Amino Acids for Crystallite Surface Functionalization

Strong Induced Circular Dichroism in a Hybrid Lead‐Halide Semiconductor Using Chiral Amino Acids for Crystallite Surface Functionalization

Chiral Hybrid Copper(I) Iodide Single Crystals Enable Highly Selective Ultraviolet-Pumped Circularly Polarized Luminescence Applications

Chiral Perovskite Nanoplatelets Exhibiting Circularly Polarized Luminescence through Ligand Optimization

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