Tunable photoluminescence from sheet-like black phosphorus crystal by electrochemical oxidation

Gan, Zhixing; Sun, Li; Wu, Xuepeng; Meng, Ming; Jin, Shangtai; Chu, Paul K.

doi:10.1063/1.4926727

Cited by 35 publications

(32 citation statements)

References 28 publications

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“…As we reported previously, the structural characterization including XRD and Raman confirm the transition from red phosphorus to BP . BP bulks fabricated by the same conditions were used as precursors in this work.…”

Section: Resultssupporting

confidence: 58%

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Hierarchical self‐assembly of black phosphorus quantum dots with quantum confinement effects to a centimeter‐scale membrane

Meng

Gan

Zhang

et al. 2017

Physica Status Solidi (b)

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The self‐assembly of simple building blocks to complex superstructures is significant for engineering materials with enhanced and synergistic properties. In this work, black phosphorus quantum dots (BPQDs) showing quantum confinement effects were prepared. The BPQDs are hierarchically self‐assembled to paper‐like membranes as large as in the centimeter range in two main stages: aggregation driven by Brownian motions due to minimization of the surface free energy and an interfacial self‐concentrating process by capillary interactions. Moreover, from the absorption band edges, the band gap of BPQDs is estimated to be about 1.3 eV, which is evidently larger than the 0.8 eV of bulk black phosphorus. The remarkable extension of the band gap indicates the quantum confinement effects of the electrons. The Raman spectrum of BPQDs shows that all the phonon modes shift to lower frequencies and broaden dramatically compared with that of the bulk BP, which suggests phonon confinement effects.

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Section: Resultssupporting

confidence: 58%

“…Then, the BPQDs were prepared by the combination of bath and probe sonication, which has been widely used for the fabrication of MoS 2 QDs . The small BP crystals were dispersed in the DMF and treated by bath sonication for at least 20 h intermittently.…”

Section: Resultsmentioning

confidence: 99%

Hierarchical self‐assembly of black phosphorus quantum dots with quantum confinement effects to a centimeter‐scale membrane

Meng

Gan

Zhang

et al. 2017

Physica Status Solidi (b)

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“…The main difficulty arises from the sensitivity of black phosphorus to its environment, notably its high reactivity when exposed to air and laser light. 10,21,22 25 . The latter value was related to the simultaneous observation of charged exciton emission at around 1.62 eV.…”

Section: 1819mentioning

confidence: 99%

Excitons in atomically thin black phosphorus

et al. 2016

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Raman scattering and photoluminescence spectroscopy are used to investigate the optical properties of single layer black phosphorus obtained by mechanical exfoliation of bulk crystals under an argon atmosphere. The Raman spectroscopy, performed in situ on the same flake as the photoluminescence measurements, demonstrates the single layer character of the investigated samples. The emission spectra, dominated by excitonic effects, display the expected in plane anisotropy. The emission energy depends on the type of substrate on which the flake is placed due to the different dielectric screening. Finally, the blue shift of the emission with increasing temperature is well described using a two oscillator model for the temperature dependence of the band gap.Black phosphorus, the most stable of all the allotropes of phosphorus, has been intensively studied by different experimental methods from the early fifties of the last century.1-7 Bulk black phosphorus is a semiconductor, with a band gap of about 0.335 eV.1,4 The orthorombic bulk crystal has a layered structure, with atomic layers bound by weak van der Waals interactions. A single atomic layer is puckered, with the phosphorus atoms being parallel in the (010) plane. 3,8,9 Atomically thin monolayers have been recently isolated using mechanical exfoliation, 10 adding black phosphorus to the rapidly growing family of emerging two dimensional materials. The band gap of black phosphorus is always direct and can be tuned from 0.3 eV to the nearly visible part of the spectrum 11,12 . In contrast, graphene is gapless, 13 and the transition metals dichalcogenides (TMDs) have an indirect gap in bulk phase and only monolayer TMDs have a direct gap.14 Moreover, black phosphorus exhibits a strong in-plane anisotropy 11,12,[15][16][17] , absent in graphene and TMDs. Additionally, the relatively high mobilities measured at room temperature combined with the direct band gap result in an on/off ratio for FET transistors of the order of 10 5 . 26 The exciton binding energy and consequently the emission energy strongly depend on the dielectric environment (substrate) 10,27 . This could partially explain the wide range of values for the black phosphorus emission energy found in the literature, possibly related also to a slightly different composition of the SiO 2 substrates employed. Moreover, owing to the limited life time of the samples, the various characterization techniques used to identify monolayer black phosphorus (e.g. atomic force microscopy, Raman spectroscopy) could not always be performed on the same flake where the optical response was investigated.In this paper we present a systematic investigation of the optical properties of monolayers of black phosphorus. We analyze the properties of the emission as a function of the dielectric constant of the substrate, excitation power, polarization and temperature. The single layer character of the investigated flakes is demonstrated using in situ Raman measurements on the same flake used for the PL. We show that the PL emission ...

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“…Compared with the planar structure of graphene45 the characteristic puckered layered structure of phosphorene provides a larger space for lithium storage, which leads to a higher energy density in the charged state and allows phosphorene to be a promising anode material for lithium ion batteries678. Furthermore, black phosphorus is a semiconductor material, but the small band gap (0.3 eV) limits its applications as a photoluminescence (PL) emitter910. Phosphorene exhibits a PL emission at 855 nm because its band gap is expanded to approximately 1.45 eV due to the confinement effect11.…”

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confidence: 99%

Intense, stable and excitation wavelength-independent photoluminescence emission in the blue-violet region from phosphorene quantum dots

Zhang

Wang

et al. 2016

Sci Rep

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Nanoscale phosphorene quantum dots (PQDs) with few-layer structures were fabricated by pulsed laser ablation of a bulk black phosphorus target in diethyl ether. An intense and stable photoluminescence (PL) emission of the PQDs in the blue-violet wavelength region is clearly observed for the first time, which is attributed to electronic transitions from the lowest unoccupied molecular orbital (LUMO) to the highest occupied molecular orbital (HOMO) and occupied molecular orbitals below the HOMO (H-1, H-2), respectively. Surprisingly, the PL emission peak positions of the PQDs are not red-shifted with progressively longer excitation wavelengths, which is in contrast to the cases of graphene and molybdenum disulphide quantum dots. This excitation wavelength-independence is derived from the saturated passivation on the periphery and surfaces of the PQDs by large numbers of electron-donating functional groups which cause the electron density on the PQDs to be dramatically increased and the band gap to be insensitive to the quantum size effect in the PQDs. This work suggests that PQDs with intense, stable and excitation wavelength-independent PL emission in the blue-violet region have a potential application as semiconductor-based blue-violet light irradiation sources.

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Tunable photoluminescence from sheet-like black phosphorus crystal by electrochemical oxidation

Cited by 35 publications

References 28 publications

Hierarchical self‐assembly of black phosphorus quantum dots with quantum confinement effects to a centimeter‐scale membrane

Hierarchical self‐assembly of black phosphorus quantum dots with quantum confinement effects to a centimeter‐scale membrane

Excitons in atomically thin black phosphorus

Intense, stable and excitation wavelength-independent photoluminescence emission in the blue-violet region from phosphorene quantum dots

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