Large-Area Oxidized Phosphorene Nanoflakes Obtained by Electrospray for Energy-Harvesting Applications (original) (raw)
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Small Methods, 2019
Interest in 2D layered materials is growing exponentially across various scientific and industrial fields due to their attractive properties. [1] In 2014, phosphorene, the monolayer 2D analogue of semiconducting black phosphorus (BP), was introduced to the A simple and fast "top-down" protocol is introduced herein to prepare solution processable few-layer phosphorene nanosheets using vortex fluidic mediated exfoliation under near-infrared (NIR) pulsed laser irradiation. This novel shear-exfoliation method requires short processing times and produces highly crystalline, atomically thin phosphorene nanosheets (4.3 ± 0.4 nm). The asprepared phosphorene nanosheets are used as an effective electron transporting material (ETM) for low-temperature processed, planar n-i-p perovskite solar cells (PSCs). With the addition of phosphorene, the average power conversion efficiency (PCE) increases from 14.32% to 16.53% with a maximum PCE of 17.85% observed for the phosphorene incorporated PSCs which is comparable to the devices made using the traditional high-temperature protocol. Experimental and theoretical (density-functional theory) investigations reveal the PCE improvements are due to the high carrier mobility and suitable band energy alignment of the phosphorene. The work not only paves the way for novel synthesis of 2D materials, but also opens a new avenue in using phosphorene as an efficient ETM in photovoltaic devices.
The Role of Water in the Preparation and Stabilization of High-Quality Phosphorene Flakes
Advanced Materials Interfaces, 2015
Since the first reports by P.D. Ye [1] and Y. Zhang [2] on the micromechanical exfoliation of bulk layered black phosphorus (BP) were published in January 2014, [3] more than two hundred papers have been published up to today, dealing with experimental and mostly theoretical studies on phosphorene, the two-dimensional BP monolayer. [4] The so called "renaissance" of black phosphorus arises from the unique properties of this material, endowed with a direct band gap of 0.3 eV in the bulk which increases to 2.0 eV going down to the monolayer. In addition to its intrinsic semiconducting properties, its puckered structure [5] gives anisotropic in-plane properties that make BP and its 2D derivative, phosphorene, very promising candidates for nanoelectronics and nanophotonics applications. [6] Therefore, the preparation of high quality single and fewlayer nanosheets of BP has attracted enormous interest in the scientific community. First the micromechanical cleavage (Scotch tape method) was applied successfully as mentioned above, then the liquid exfoliation [7] and the electrochemical exfoliation [8] of black phosphorus (BP) were explored as well. Several groups were working simultaneously and independently on the liquid exfoliation of BP under sonication. Therefore, distinct contributions came out in a relatively short time. [7] In particular, Hersam [7c] and Salehi-Khojin [7d] performed successfully the liquid exfoliation of BP in dimethylsulfoxide (DMSO) and dimethylformamide, both having a high dielectric
A Perspective on Recent Advances in Phosphorene Functionalization and its Application in Devices
European Journal of Inorganic Chemistry
Phosphorene, the 2D material derived from black phosphorus, has recently attracted a lot of interest for its properties, suitable for applications in material science. In particular, the physical features and the prominent chemical reactivity on its surface render this nanolayered substrate particularly promising for electrical and optoelectronic applications. In addition, being a new potential ligand for metals, it opens the way for a new role of the inorganic chemistry in the 2D world, with special reference to the field of catalysis. The aim of this review is to summarize the state of the art in this subject and to present our most recent results in preparation, functionalization and use of phosphorene and its decorated derivatives. In particular, we discuss several key points, which are currently under investigation: the synthesis, the characterization by theoretical calculations, the high pressure behaviour of black phosphorus, as well as decoration with nanoparticles and encapsulation in polymers. Finally, device fabrication and electrical transport measurements are overviewed on the basis of recent literature and new results collected in our laboratories.
A Perspective on Recent Advances in Phosphorene Functionalization and Its Applications in Devices
European Journal of Inorganic Chemistry, 2018
Phosphorene, the 2D material derived from black phosphorus, has recently attracted a lot of interest for its properties, suitable for applications in material science. In particular, the physical features and the prominent chemical reactivity on its surface render this nanolayered substrate particularly promising for electrical and optoelectronic applications. In addition, being a new potential ligand for metals, it opens the way for a new role of the inorganic chemistry in the 2D world, with special reference to the field of catalysis. The aim of this review is to summarize the state of the art in this subject and to present our most recent results in preparation, functionalization and use of phosphorene and its decorated derivatives. In particular, we discuss several key points, which are currently under investigation: the synthesis, the characterization by theoretical calculations, the high pressure behaviour of black phosphorus, as well as decoration with nanoparticles and encapsulation in polymers. Finally, device fabrication and electrical transport measurements are overviewed on the basis of recent literature and new results collected in our laboratories.
Control of Surface and Edge Oxidation on Phosphorene
ACS applied materials & interfaces, 2017
Phosphorene is emerging as an important two-dimensional semiconductor, but controlling the surface chemistry of phosphorene remains a significant challenge. Here, we show that controlled oxidation of phosphorene determines the composition and spatial distribution of the resulting oxide. We used X-ray photoemission spectroscopy to measure the binding energy shifts that accompany oxidation. We interpreted these spectra by calculating the binding energy shift for 24 likely bonding configurations, including phosphorus oxides and hydroxides located on the basal surface or edges of flakes. After brief exposure to high-purity oxygen or high-purity water vapor at room temperature, we observed phosphorus in the +1 and +2 oxidation states; longer exposures led to a large population of phosphorus in the +3 oxidation state. To provide insight into the spatial distribution of the oxide, transmission electron microscopy was performed at several stages during the oxidation. We found crucial differ...
Phosphorene oxides: bandgap engineering of phosphorene by oxidation
Physical Review B
We show that oxidation of phosphorene can lead to the formation of a new family of planar (2D) and tubular (1D) oxides and sub-oxides, most of them insulating. This confers to black phosphorus a native oxide that can be used as barrier material and protective layer. Further, the bandgap of phosphorene oxides depends on the oxygen concentration, suggesting that controlled oxidation can be used as a means to engineer the bandgap. For the oxygen saturated composition, P$_2$O$_5$, both the planar and tubular phases have a large bandgap energy of about 8.5eV, and are transparent in the near UV. These two forms of phosphorene oxides are predicted to have the same formation enthalpy as o$^\prime$-P$_2$O$_5$, the most stable of the previously known forms of phosphorus pentoxide.
A Ray of Hope for Future Technology: Phosphorene
Indian Journal of Science and Technology, 2017
In the recent times, two dimensional layered single crystals attracted huge attention to their tunable mechanical, optical and electronic properties which have potential applications in future nanoelectronics and optoelectronics for large scale integration in low power technology. Phosphorene, the single- or few layer form of black phosphorus, was lately investigated as a two dimension layered material with motivating promising applications in the field of nanoelectronics and optoelectronics. However, there is still a need for developing its fundamental properties, design schemes and growth techniques. In this context, we review about the recent progress in phosphorene studies, primarily on the fabrication process, properties, forthcoming applications and challenges. In this article, the anisotropic properties (electronic, optoelectronic, thermoelectric and mechanical) of phosphorene, due to its puckered structure is also highlighted. The extraordinary properties of phosphorene make it a future material for designing and fabrication of nanodevices, and more fundamental and technological developments can be established in the near future.
The Critical Role of Substrate in Stabilizing Phosphorene Nanoflake: A Theoretical Exploration
Journal of the American Chemical Society, 2016
Phosphorene, a new two-dimensional (2D) semiconductor, has received much interest due to its robust direct band gap and high charge mobility. Currently, however, phosphorene can only be produced by mechanical or liquid exfoliation, and it is still a significant challenge to directly epitaxially grow phosphorene, which greatly hinders its mass production and thus applications. In epitaxial growth, the stability of nanoscale cluster or flake on a substrate is crucial. Here, we perform ab initio energy optimizations and molecular dynamics simulations to explore the critical role of substrate on the stability of a representative phosphorene flake. Our calculations show that the stability of the phosphorene nanoflake is strongly dependent on the interaction strength between the nanoflake and substrate. Specifically, the strong interaction (0.75 eV/P atom) with Cu(111) substrate breaks up the phosphorene nanoflake, while the weak interaction (0.063 eV/P atom) with h-BN substrate fails to ...