Orientation Control of Two-Dimensional Perovskites by Incorporating Carboxylic Acid Moieties

Arai, Ryosuke; Yoshizawa‐Fujita, Masahiro; Takeoka, Yuko; Rikukawa, Masahiro

doi:10.1021/acsomega.7b00421

Cited by 13 publications

(17 citation statements)

References 27 publications

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“…The peaks were also blue-shifted as the Br − content was increased. This was reported to be a result of exciton absorption attributed to the 2D quantum confinement [13]. Similar results were also observed for PbI 2 crystal intercalated with organic molecules [14].…”

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confidence: 83%

“…An additional diffraction peak at approximately 9.01°(marked with a black arrow), corresponding to the interlayer d-spacing of 9 7 Å, was also observed. This peak provided an evidence of the formation of a 2D perovskite layered structure [13]. This could be due to the relatively small ionic radius of Br − and the intercalation of the organic moiety from 5-AVAI, which allowed the formation of layered structure [5,13].…”

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confidence: 94%

“…This peak provided an evidence of the formation of a 2D perovskite layered structure [13]. This could be due to the relatively small ionic radius of Br − and the intercalation of the organic moiety from 5-AVAI, which allowed the formation of layered structure [5,13]. In general, the perovskites made from mixed organic cations, especially with large 5-AVA cations, could produce a 2D layered structure [5].…”

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confidence: 97%

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The Synthesis of 2D CH₃NH₃PbI₃ Perovskite Films with Tunable Bandgaps by Solution Deposition Route

Loryuenyong

Thongpon

Saudmalai

et al. 2019

International Journal of Photoenergy

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Nowadays, organo-lead halide is one of the most interesting materials for perovskite solar cells. This is because of its ease of fabrication, long absorption wavelength region, and long diffusion length. In this study, we investigated the bandgap tuning of hybrid mixed-halide perovskite films. The films were prepared by sequential two-step deposition technique, using 5-ammonium valeric acid iodide (5-AVAI), PbI2, and a mixture of CH3NH3I and CH3NH3Br as precursor solutions. The results confirmed the formation of 2D perovskites in the presence of 5-AVAI. The obtained films had higher moisture resistance, better surface coverage, and smaller grain size, compared to the films without 5-AVAI. With the introduction of Br− ions, the change in the lattice parameter was observed. The bandgap was also found to increase with increasing Br− content.

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confidence: 83%

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confidence: 94%

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confidence: 97%

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The Synthesis of 2D CH₃NH₃PbI₃ Perovskite Films with Tunable Bandgaps by Solution Deposition Route

Loryuenyong

Thongpon

Saudmalai

et al. 2019

International Journal of Photoenergy

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“…Due to the presence of defects from both cations and anions on the PQD surface, complete passivation requires ligands that can provide both positive and negative charges. Thus, the combination of amines and acids to generate ammonium and carboxyl groups is essential for effective passivation …”

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confidence: 99%

Synergistic Surface Passivation of CH₃NH₃PbBr₃ Perovskite Quantum Dots with Phosphonic Acid and (3‐Aminopropyl)triethoxysilane

Vickers

Rao

et al. 2019

Chemistry A European J

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CH 3 NH 3 PbBr 3 perovskite quantum dots (PQDs) are synthesized by using four different linear alkyl phosphonic acids (PAs) in conjunction with (3-aminopropyl)triethoxysilane (APTES) as capping ligands. The resultant PQDs are characterizedb ym eanso fX RD, TEM, Ramans pectroscopy, FTIR spectroscopy,U V/Vis, photoluminescence( PL), time-resolved PL, and X-ray photoelectrons pectroscopy (XPS). PA chain length is shownt oc ontrol the PQD size (ca. 2.9-4.2 nm) and excitonic absorption band positions (l = 488-525 nm), with shorter chain lengths corresponding to smaller sizes and bluer absorptions. All samples show ah igh PL quantumy ield (ca. 46-83 %) and high PL stability;t his is in-dicative of al ow density of band gap trap states and effective surface passivation.S tabilityi sh igher for smaller PQDs; this is attributed to better passivation due to better solubility and less steric hindrance of the shorter PA ligands. Based on the FTIR, Raman, and XPS results, it is proposed that Pb 2 + and CH 3 NH 3 + surface defectsa re passivated by RÀPO 3 2À or RÀPO 2 (OH) À ,w hereasB r À surface defects are passivated by RÀNH 3 + moieties. This study establishes the combination of PA and APTESl igandsa sah ighly effective dual passivation systemf or the synergistic passivation of multiple surface defects of PQDst hrough primarily ionic bonding.

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“… 20 , 30 For example, the [PbX 6 ] 4– layers behave as semiconductors, while the organic spacer is insulating. 31 Such structural anisotropy also has mechanical advantages: the photoluminescence of macroscopic stacks of 2D layered perovskites can be tuned by moderate external pressures due to the related anisotropy of the transition dipole moments, 32 and the layered structure allows for mechanical exfoliation of single flakes with a defined number of octahedral layers and their transfer on suitable substrates. 14 The organic/inorganic bilayer structure behaves mechanically as an organic composite material reinforced by the octahedral layers, with out-of-plane weak bonds (van der Waals) and in-plane strong bonds (covalent or ionic), generating rigid cages when increasing the number of inorganic layers.…”

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Directional Anisotropy of the Vibrational Modes in 2D-Layered Perovskites

et al. 2020

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The vibrational modes in organic/inorganic layered perovskites are of fundamental importance for their optoelectronic properties. The hierarchical architecture of the Ruddlesden–Popper phase of these materials allows for distinct directionality of the vibrational modes with respect to the main axes of the pseudocubic lattice in the octahedral plane. Here, we study the directionality of the fundamental phonon modes in single exfoliated Ruddlesden–Popper perovskite flakes with polarized Raman spectroscopy at ultralow frequencies. A wealth of Raman bands is distinguished in the range from 15 to 150 cm –1 (2–15 meV), whose features depend on the organic cation species, on temperature, and on the direction of the linear polarization of the incident light. By controlling the angle of the linear polarization of the excitation laser with respect to the in-plane axes of the octahedral layer, we gain detailed information on the symmetry of the vibrational modes. The choice of two different organic moieties, phenethylammonium (PEA) and butylammonium (BA), allows us to discern the influence of the linker molecules, evidencing strong anisotropy of the vibrations for the (PEA) 2 PbBr 4 samples. Temperature-dependent Raman measurements reveal that the broad phonon bands observed at room temperature consist of a series of sharp modes and that such mode splitting strongly differs for the different organic moieties and vibrational bands. Softer molecules such as BA result in lower vibrational frequencies and splitting into fewer modes, while more rigid molecules such as PEA lead to higher frequency oscillations and larger number of Raman peaks at low temperature. Interestingly, in distinct bands the number of peaks in the Raman bands is doubled for the rigid PEA compared to the soft BA linkers. Our work shows that the coupling to specific vibrational modes can be controlled by the incident light polarization and choice of the organic moiety, which could be exploited for tailoring exciton–phonon interaction, and for optical switching of the optoelectronic properties of such 2D layered materials.

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Orientation Control of Two-Dimensional Perovskites by Incorporating Carboxylic Acid Moieties

Cited by 13 publications

References 27 publications

The Synthesis of 2D CH₃NH₃PbI₃ Perovskite Films with Tunable Bandgaps by Solution Deposition Route

The Synthesis of 2D CH₃NH₃PbI₃ Perovskite Films with Tunable Bandgaps by Solution Deposition Route

Synergistic Surface Passivation of CH₃NH₃PbBr₃ Perovskite Quantum Dots with Phosphonic Acid and (3‐Aminopropyl)triethoxysilane

Directional Anisotropy of the Vibrational Modes in 2D-Layered Perovskites

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Orientation Control of Two-Dimensional Perovskites by Incorporating Carboxylic Acid Moieties

Cited by 13 publications

References 27 publications

The Synthesis of 2D CH3NH3PbI3 Perovskite Films with Tunable Bandgaps by Solution Deposition Route

The Synthesis of 2D CH3NH3PbI3 Perovskite Films with Tunable Bandgaps by Solution Deposition Route

Synergistic Surface Passivation of CH3NH3PbBr3 Perovskite Quantum Dots with Phosphonic Acid and (3‐Aminopropyl)triethoxysilane

Directional Anisotropy of the Vibrational Modes in 2D-Layered Perovskites

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The Synthesis of 2D CH₃NH₃PbI₃ Perovskite Films with Tunable Bandgaps by Solution Deposition Route

The Synthesis of 2D CH₃NH₃PbI₃ Perovskite Films with Tunable Bandgaps by Solution Deposition Route

Synergistic Surface Passivation of CH₃NH₃PbBr₃ Perovskite Quantum Dots with Phosphonic Acid and (3‐Aminopropyl)triethoxysilane