Economic Synthesis of High Quality InP Nanocrystals Using Calcium Phosphide as the Phosphorus Precursor

Li, Liansheng; Protière, Myriam; Reiß, Peter

doi:10.1021/cm7035579

Cited by 132 publications

(148 citation statements)

References 18 publications

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“…4 The strategies developed to produce colloidal InP QDs can be roughly divided in two groups. The first group includes high reactivity P(-III) precursors such as tris(trimethylsilyl)phosphine [(TMS)3P] 5-7 or phosphine [PH3], 8 and the second group utilizes lower reactivity P(0) and P(+III) precursors such as trioctylphosphine (TOP), 9 P4, 10 or PCl3. 11 Based on size dispersion -a key parameter to be minimized for most QD-based applications -P(-III) precursors give the best results.…”

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confidence: 99%

Economic and Size-Tunable Synthesis of InP/ZnE (E = S, Se) Colloidal Quantum Dots.

et al. 2015

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ABSTRACT:We present synthesis protocols, based on indium halide and aminophosphine precusors, that allow for the economic, up-scaled production of InP Quantum Dots (QDs). The reactions attain a close to full yield conversion -with respect to the indium precursor -and we demonstrate that size tuning at full chemical yield is possible by straightforward adaptations of the reaction mixture. In addition, we present ZnS and ZnSe shell growth procedures that lead to InP/ZnS and InP/ZnSe core/shell QDs that emit from 510 nm to 630 nm with an emission linewidth between 46 nm and 63 nm. This synthetic method is an important step towards performing Cd-free QDs, and it could help the transfer of colloidal QDs from the academic field to product applications.Colloidal QDs have rapidly evolved from a lab-scale invention of academic interest to new, useful building blocks widely applied in various fields of nanoscience and technology research.1 This is mainly due to high precision, synthetic schemes developed for cadmium chalcogenide QDs, 2 which have made available monodisperse QD ensembles that preserve the unique, size-tunable optoelectronic properties of individual QDs. The restrictions several countries have imposed on the use of cadmium however question the long term feasibility of product applications relying on cadmium-chalcogenide based QDs, hence the quest for Cd-free alternatives.3 This search has mainly focused on CuInS2 and InP where, similar to CdSe, size quantization enables the bandgap transition to be tuned across most of the visible spectrum. Especially InP QDs combine a reduced toxicity with emission characteristics close to those of CdSe-based QDs. 4 The strategies developed to produce colloidal InP QDs can be roughly divided in two groups. The first group includes high reactivity P(-III) precursors such as tris(trimethylsilyl)phosphine [(TMS)3P] 5-7 or phosphine [PH3], 8 and the second group utilizes lower reactivity P(0) and P(+III) precursors such as trioctylphosphine (TOP), 9 P4, 10 or PCl3. 11 Based on size dispersion -a key parameter to be minimized for most QD-based applications -P(-III) precursors give the best results. In particular, (TMS)3P has been the most commonly used phosphorous precursor, where optimized protocols yield emission lines with a full width at half maximum (FWHM) of 40-60 nm.12 Unfortunately, (TMS)3P is a costly and pyrophoric precursor that tends to decompose and forms lethally toxic PH3 in contact with air. This renders upscaled (TMS)3P-based InP production elusive and may explain why InP QDs are far less studied than CdSe QDs. Opposite from the high reactivity P(-III) precursors, protocols to synthesize InP QDs with low reactivity precursors yield QDs with too large a size-dispersion for most of the potential applications.Recently, an innovative and potentially efficient alternative to make InP QDs has been published by Song et al.. 13 These authors use tris(dimethylamino)phosphine [(DMA)3P] as a phosphorous precursor, which can be classified as a low-reactive P(+III) precurso...

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Economic and Size-Tunable Synthesis of InP/ZnE (E = S, Se) Colloidal Quantum Dots.

et al. 2015

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“…This method relies on an expensive TMSP precursor as a phosphorus precursor, which performs a hampering scale-up of the synthesis. In(tBu2P)3, [23] Na3P, [24] Ca3P, [25] PCl3 [26] and as well as white phosphorus(P4) [27] have been studied as alternative phosphorus precursors for phosphorus precursors which are less costly in synthesis and less toxic.…”

Section: History Of Inp Qdsmentioning

confidence: 99%

Large-Scale Synthesis of Highly Luminescent InP@ZnS Quantum Dots Using Elemental Phosphorus Precursor

et al. 2017

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Colloidal quantum dots can control the bandgap by controlling the particle size, and are capable of solution processing, which is cost competitive, and has a narrow half width of the emission wavelength.Using these characteristics, it is possible to utilize various kinds of LED, solar cell, and bio imaging.Among them, indium phosphide (InP) quantum dots have a bandgap capable of emitting light in the near-infrared region from the visible light region, and are less toxic to humans and the environment than cadmium-based quantum dots, and are attracting attention as next generation light emitting materials.However, the limited choice and high cost of P precursors have a negative impact on their practical applicability. In this work, I report the large-scale synthesis of highly luminescent InP@ZnS QDs from an elemental P precursor (P4), which was simply synthesized via the sublimation of red P powder. The size of the InP QDs was controlled by varying the reaction parameters such as the reaction time and temperature, and the type of In precursors. This way, the photoluminescence properties of the synthesized InP@ZnS QDs could be easily tuned across the entire visible range, while their quantum yield could be increased up to 60% via the optimization of reaction conditions. Furthermore, possible reaction pathways for the formation of InP QDs using the P4 precursor have been investigated with nuclear magnetic resonance spectroscopy and it was demonstrated that the direct reaction of P4 precursor with In precursor produces InP structures without the formation of intermediate species. The large-scale production of InP@ZnS QDs was demonstrated by yielding more than 6 g of QDs per onebatch reaction.In the case of InP using different precursor P except the Tris(Trimethylsilyl) phosphine ((TMS)3P) there has been a problem that the size distribution is poor. Two kinds of P precursors with different reactivities were used to separate the nucleation and growth processes and to induce growth along the Lamer mechanism to produce uniform particles. For this, (TMS)3P and DEAP were used as fast reacting P precursors, and P4 was used as a slow reacting P precursor. Through this, the possibility of uniform particle formation was observed. I strongly believe that the newly developed approach bears the potential to be widely used for manufacturing inexpensive high-quality QD emitters. Blank page Contents

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“…When coating, the dangling bonds are passivated with atoms of the shell, resulting in the dramatic enhancement of the PL efficiency. As an example, the QY of naked InP NCs is generally inferior to 0.1 per cent but after being coated with ZnS, the QY of the resulting InP/ZnS C/S QDs increases up to 22 per cent [141]. In the majority of cases, the materials chosen for the shell are semiconductors which have a wider band gap than those of the core (C/S system called type I structure) in order to provide electronic insulation thanks to the confinement of both electrons and holes in the core (figure 9b).…”

Section: Quantum Dotsmentioning

confidence: 99%

New generation of magnetic and luminescent nanoparticles for in vivo real-time imaging

et al. 2013

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One contribution of 10 to a Theme Issue 'Molecular-, nano-and micro-devices for real-time in vivo sensing'. A new generation of optimized contrast agents is emerging, based on metallic nanoparticles (NPs) and semiconductor nanocrystals for, respectively, magnetic resonance imaging (MRI) and near-infrared (NIR) fluorescent imaging techniques. Compared with established contrast agents, such as iron oxide NPs or organic dyes, these NPs benefit from several advantages: their magnetic and optical properties can be tuned through size, shape and composition engineering, their efficiency can exceed by several orders of magnitude that of contrast agents clinically used, their surface can be modified to incorporate specific targeting agents and antifolding polymers to increase blood circulation time and tumour recognition, and they can possibly be integrated in complex architecture to yield multi-modal imaging agents. In this review, we will report the materials of choice based on the understanding of the basic physics of NIR and MRI techniques and their corresponding syntheses as NPs. Surface engineering, water transfer and specific targeting will be highlighted prior to their first use for in vivo realtime imaging. Highly efficient NPs that are safer and target specific are likely to enter clinical application in a near future.

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Economic Synthesis of High Quality InP Nanocrystals Using Calcium Phosphide as the Phosphorus Precursor

Cited by 132 publications

References 18 publications

Economic and Size-Tunable Synthesis of InP/ZnE (E = S, Se) Colloidal Quantum Dots.

Economic and Size-Tunable Synthesis of InP/ZnE (E = S, Se) Colloidal Quantum Dots.

Large-Scale Synthesis of Highly Luminescent InP@ZnS Quantum Dots Using Elemental Phosphorus Precursor

New generation of magnetic and luminescent nanoparticles for in vivo real-time imaging

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