Electronic Structure and Optical Properties of α-CH3NH3PbBr3 Perovskite Single Crystal

Park, Ji-Sang; Choi, Sukgeun; Yan, Yong; Yang, Ye; Luther, Joseph M.; Wei, Su‐Huai; Parilla, Philip A.; Zhu, Kai

doi:10.1021/acs.jpclett.5b01699

Cited by 141 publications

(130 citation statements)

References 34 publications

Supporting

Mentioning

116

Contrasting

Unclassified

Order By: Relevance

“…The bandgap, which is the difference between the energy levels of the valence band maximum and conduction band minimum, is calculated to be 2.16 eV, in reasonable agreement with the experimental bandgap of 2.33 eV [80,81]. showing some tentative intermolecular bond-distances and bond-angles of approach for the formation of intermolecular contacts (in Å and deg, respectively).…”

Section: Resultssupporting

confidence: 81%

Halogen in materials design: Revealing the nature of hydrogen bonding and other non-covalent interactions in the polymorphic transformations of methylammonium lead tribromide perovskite

Varadwaj

Marques

Yamashita

2018

Materials Today Chemistry

View full text Add to dashboard Cite

Methylammonium lead tribromide (CH 3 NH 3 PbBr 3 ) perovskite as a photovoltaic material has attracted a great deal of recent interest. Factors that are important in their application in optoelectronic devices include their fractional contribution of the composition of the materials as well as their microscopic arrangement that is responsible for the formation of well-defined macroscopic structures. CH 3 NH 3 PbBr 3 assumes different polymorphs (orthorhombic, tetragonal and cubic) depending on the evolution temperature of the bulk material. An understanding of the structure of these compounds will assist in rationalizing how halogen-centered non-covalent interactions play an important role in the rational design of these materials. Density functional theory (DFT) calculations have been performed on polymorphs of CH 3 NH 3 PbBr 3 to demonstrate that the H atoms on C of the methyl group in CH 3 NH 3 + entrapped within a PbBr 6 4-perovskite cage are not electronically innocent, as is often contended. We show here that these H atoms are involved in attractive interactions with the surrounding bromides of corner-sharing PbBr 6 4-octahedra of the CH 3 NH 3 PbBr 3 cage to form Br•••H(-C) hydrogen bonding interactions. This is analogous to the way the H atoms on N of the -NH 3 + group in CH 3 NH 3 + form Br•••H(-N) hydrogen bonding interactions to stabilize the structure of CH 3 NH 3 PbBr 3 . Both these hydrogen bonding interactions are shown to persist regardless of the nature of the three polymorphic forms of CH 3 NH 3 PbBr 3 . These, together with the Br•••C(-N) carbon bonding, the Br•••N(-C) pnictogen bonding, and the Br•••Br lump-hole type intermolecular non-covalent interactions identified for the first time in this study, are shown to be collectively responsible for the eventual emergence of the orthorhombic geometry of the CH 3 NH 3 PbBr 3 system. These conclusions are arrived at from a systematic analysis of the results obtained from combined DFT, Quantum Theory of  Corresponding Supporting Information and the ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/xxxxxxx Atoms in Molecules (QTAIM), and Reduced Density Gradient Non-Covalent Interaction (RDG-NCI) calculations carried out on the three temperature-dependent polymorphic geometries of CH 3 NH 3 PbBr 3 .

show abstract

Section: Resultssupporting

confidence: 81%

Halogen in materials design: Revealing the nature of hydrogen bonding and other non-covalent interactions in the polymorphic transformations of methylammonium lead tribromide perovskite

Varadwaj

Marques

Yamashita

2018

Materials Today Chemistry

View full text Add to dashboard Cite

show abstract

“…According to previous publication, the lasing in microplates possesses whispering gallery modes with spacing

Δ λ = \frac{λ^{2}}{n_{ref} d}

where λ is the central wavelength of the narrowed emission peak, d is the effective cavity length, n ref is the refraction index of MAPbBr 3 . According to previous report, the n ref is ≈2.378 at photon energy of 2.34 eV . Then the cavity length d can be found to be around

4 \times \sqrt{2} \times l

, which indicates a twice round trip of light transport inside the microcavity.…”

Section: Size‐dependence and Whispering Gallery Mode (Wgm) Lasingmentioning

confidence: 63%

Two‐Photon Optical Properties in Individual Organic–Inorganic Perovskite Microplates

Wei

et al. 2017

Advanced Optical Materials

View full text Add to dashboard Cite

yield [15][16][17] make these metal-halide perovskites also promising for applications in light emitting diodes (LEDs) and lasers. [18][19][20][21][22][23] Specifically speaking, amplified spontaneous emission (ASE) has been demonstrated in metal-halide perovskite thin films. Multiphoton pumped upconverted photoluminescence (PL) and coherent light emission have been achieved with perovskite single crystals and nanocrystals (NCs). [24][25][26][27][28][29][30][31][32][33][34] Metal-halide perovskite lasing has been demonstrated with various microcavity structures. [35][36][37][38] For use as coherent light source, the lasing threshold obtained is also highly dependent on the optical cavity, which is formed by the close loop light reflection from the nanostructure surfaces that becomes a standing wave cavity resonator. The regular shape of the perovskite microstructures with various sizes differs in various optical confinement abilities, which suggests that lasing in perovskite microstructures possesses size-dependent behavior. [39][40][41][42] Hence, a clearer understanding of the size-dependent coherent light emission behavior is crucial for developing metal-halide perovskite on chip nanolasers. Furthermore, the photogenerated species (especially in CH 3 NH 3 PbBr 3 (MAPbBr 3 )) and their contribution to the lasing performance in these perovskites have not been fully revealed. [43] The exciton binding energy in 3D MAPbBr 3 has been estimated with various techniques. However, the reported values are highly controversial and covered a wide range from 25 to 150 meV. [44][45][46][47][48] Unlike the confirmed excitonic emission in MAPbBr 3 NCs, due to the extremely large exciton binding energy (≈375 meV), [49] it Metal-halide perovskites are recently extensively investigated as light absorbing material in solar cells. The outstanding optoelectronic properties and tunable light emission of the perovskites also make them promising candidates for light emitting diodes and lasers. However, understanding the relevant mechanisms and processes of the dependence of perovskite light emission on temperature and crystal size is still challenging. Herein, the CH 3 NH 3 PbBr 3 monocrystals of different sizes are uniformly excited by two-photon absorption at 800 nm (100 fs, 1 KHz). In contrast to the reported relative large exciton binding energy (≈76 meV) and spectrum clearly resolved excitonic absorption, the light emission origin in CH 3 NH 3 PbBr 3 microcrystals at room temperature is unambiguously determined to be dominated by free electron-hole bimolecular recombination. The coherent light emission threshold of CH 3 NH 3 PbBr 3 microcrystal increases with temperature, which is closely related to the temperature induced transition from exciton gas to free charge carriers. In addition, the coherent light emission threshold is found to decrease with the microcrystal size, which could be well interpreted by the interaction between the optical confinement, defect density, and cavity quantum electrodynamics effect. These results pre...

show abstract

“…Over the last 2 years, an increasing number of researchers have begun studying single‐crystalline perovskites, including crystal preparations,21, 27, 28, 43, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65 property studies,21, 27, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80 and applications 56, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91. For example, an extremely long carrier lifetime (up to 20 µs) and carrier diffusion length (175 µm) have been found,21 which has received a great deal of attention.…”

Section: Perovskite Materialsmentioning

confidence: 99%

Recent Progress in Single‐Crystalline Perovskite Research Including Crystal Preparation, Property Evaluation, and Applications

2017

View full text Add to dashboard Cite

Organic–inorganic lead halide perovskites are promising optoelectronic materials resulting from their significant light absorption properties and unique long carrier dynamics, such as a long carrier lifetime, carrier diffusion length, and high carrier mobility. These advantageous properties have allowed for the utilization of lead halide perovskite materials in solar cells, LEDs, photodetectors, lasers, etc. To further explore their potential, intrinsic properties should be thoroughly investigated. Single crystals with few defects are the best candidates to disclose a variety of interesting and important properties of these materials, ultimately, showing the increased importance of single‐crystalline perovskite research. In this review, recent progress on the crystallization, investigation, and primary device applications of single‐crystalline perovskites are summarized and analyzed. Further improvements in device design and preparation are also discussed.

show abstract

Electronic Structure and Optical Properties of α-CH₃NH₃PbBr₃ Perovskite Single Crystal

Cited by 141 publications

References 34 publications

Halogen in materials design: Revealing the nature of hydrogen bonding and other non-covalent interactions in the polymorphic transformations of methylammonium lead tribromide perovskite

Halogen in materials design: Revealing the nature of hydrogen bonding and other non-covalent interactions in the polymorphic transformations of methylammonium lead tribromide perovskite

Two‐Photon Optical Properties in Individual Organic–Inorganic Perovskite Microplates

Recent Progress in Single‐Crystalline Perovskite Research Including Crystal Preparation, Property Evaluation, and Applications

Contact Info

Product

Resources

About