White phosphorus and metal nanoparticles: a versatile route to metal phosphide nanoparticles

Carenco, Sophie; Demange, Michel; Shi, Jing; Boissière, Cédric; Sánchez, Clément; Floch, Pascal Le; Mézailles, Nicolas

doi:10.1039/c0cc00684j

Cited by 57 publications

(64 citation statements)

References 39 publications

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“…Solid Ni 2 P particles have also been made by the reaction of either nickel particles or Ni(C 8 H 12 ) 2 with P 4 . 102,103 In this chapter, we have shown how the chemistry described previously can be applied to the synthesis of more unusual materials. This demonstrates how general the chemistry is and how most materials should be accessible using the synthetic pathways described.…”

Section: Other Pnictide-based Materialsmentioning

confidence: 98%

The Preparation of Other Chalcogenides and Pnictide Nanomaterials

2014

Semiconductor Quantum Dots

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It could be argued that the organometallic route to quantum dots (QDs) has found the most success with chalcogen-containing semiconducting particles, as the II-VI and IV-VI families of materials are easily prepared yielding exceptionally high-quality QDs. Other families of technically important semiconductors incorporating chalcogens have also been prepared, notably I-III-VI materials, which have potential applications in solar energy, especially CuInSe 2 , which has a bandgap between 1.04 eV (ca. 1190 nm) and 1.10 eV (ca. 1125 nm), and an exciton radius of 21.2 nm. 1 The related material CuInS 2 , with a bandgap of ca. 1.53 eV (810 nm) and an excitonic diameter of 8.2 nm, 2,3 has also been prepared. Most of the synthetic pathways described are similar in their approach, apart from the preparation of I-III-VI QDs using single-source precursors, which is covered in Chapter 7.The ternary compound CuInSe 2 has been synthesised in the form of spherical QDs, ca. 4 nm in diameter, by the injection of InCl 3 and CuCl, dissolved in trioctylphosphine (TOP), in trioctylphosphine oxide (TOPO) at 100 C, followed by the injection of trioctylphosphine selenide (TOPSe) an hour later at 250 C and growth for 1 day. 4,5 The particles, isolated by the usual solvent/non-solvent interaction, exhibited a band edge at ca. 420 nm and broad emission with a maximum at 440 nm. This emission prole is in stark contrast to other reports of Cu-In-Se materials, which have optical properties predominantly in the red/infrared region, and may have some

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Section: Other Pnictide-based Materialsmentioning

confidence: 98%

The Preparation of Other Chalcogenides and Pnictide Nanomaterials

2014

Semiconductor Quantum Dots

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“…This coalescence results in an increased saturation magnetization compared to the thin films of MnSb (thickness 5 nm), followed by increased polar magnetic dichroism, which is an indication of the active magneto-optical properties of these MnSb dots. While the synthesis of colloidal transition metal phosphide particles has become quite routine, [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] and precedent exists for colloidal transition metal arsenide nanoparticles; [23][24][25][26][27][28][29] examples of antimonide colloids that exhibit narrow size polydispersity are quite few and typically limited to main group semiconductors. These nanostructures comprise nearly 50% of the MnSb film.…”

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confidence: 99%

Synthesis of colloidal MnSb nanoparticles: consequences of size and surface characteristics on magnetic properties

et al. 2016

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A solution phase methodology was developed for the formation of discrete colloidal MnSb nanoparticles using dimanganesedecacarbonyl and triphenylantimony as the main reaction components. Stoichiometric reactions result in significant Sb impurities, but these can be eliminated by the use of excess Mn reagent, limiting the reaction time, and using a lower temperature (280 °C) relative to that commonly employed for MnP or MnAs synthesis (330-360 °C). The resultant MnSb nanoparticles are, when evidenced by both powder X-ray diffraction and transmission electron microscopy, ca. 14 nm in diameter and exhibit low polydispersity (13±1.7 nm). High Angle Annular Dark Field-Scanning Transmission Electron Microscopy and energy dispersive line scan data revealed that the as-synthesized MnSb nanoparticles are coreshell in nature, having a MnSb core and an amorphous manganese oxide shell. Evidence is presented supporting a pathway for decomposition of MnSb nanoparticles driven by formation of MnO 2 and Sb due to reaction with adventitious O 2 . The MnSb nanoparticles are superparamagnetic at room temperature, and exhibit suppressed moments attributed to surface oxidation arising from the high surface area and intrinsic oxophilicity of Mn. IntroductionBinary and ternary intermetallic compounds formed by combination of 3d transition metals and pnicogens X (X=P, As, Sb or Bi) are of special interest due to their various electronic and magnetic properties. 1 Among transition metal pnictides, manganese arsenide (MnAs), manganese 15 external magnetic field of 100 Oe. The FC plot shows a gradual increase of molar magnetization with decrease of temperature from 320 K which then saturates at temperatures roughly below 50 K. In the ZFC curve, the sample shows a broad maximum in the range of 245-255 K, near the intersection of the FC with the ZFC curve. Collectively, the above behavior suggests superparamagnetic behavior. Under FC conditions, the magnetic moments of the particles are frozen along the direction of applied magnetic field upon cooling, producing saturation at lowtemperature. In contrast, for ZFC samples, the moments are frozen in random orientation at low temperature, and start to align in the field upon heating, reaching a maximum at the blocking temperature,T B , above which superparamagnetic behavior is exhibited, resulting in a drop in magnetization again. The T B depends on the volume of the nanoparticle, the presence of anisotropy (shape or magnetocrystalline), as well as the time-scale of the measurement (~10 -9 s for DC magnetometry). In the present case the peak corresponding to T B is relatively broad suggesting a distribution of values reflecting the polydispersity of the sample. 38 We attribute the irregularity in both FC and ZFC plots around 43 K to a small leak of oxygen into the sample chamber that makes a condensed film of oxygen, resulting a para-antiferromagnetic transition of oxygen around 43 K. 39

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“…[57] However, all these approaches were unable to provide a reliable synthesis route for monodispersed and highly luminescent InP-based QDs. In this work, I developed a synthesis of InP and InP@ZnS QDs using P4 as a P precursor, which had been simply synthesized from red P powder.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, several attempts have been made to use P4 and related compounds as precursors for the synthesis of InP QDs via solvothermal reactions. [56,57] For example, Xie et al reported the solvothermal synthesis of InP nanocrystals using P4 precursor in the presence of the reducing agent KBH4. [56] The size of synthesized nanocrystals was in the range of 11−20 nm, and, further, nanorods with a diameter of 150 nm were produced.…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, it restricts the large-scale production of InP QDs due to its sensitivity to temperature homogeneity of the reaction batch. Thus, there have been significant research efforts to develop alternative P precursors such as Na3P, [24] Ca3P, [25] and PC13, [26] as well as P4 [56,57] . P is one of the relatively abundant elements and typically exists as a phosphate form, which is converted industrially to elemental P, such as white P (P4) and red P allotropes.…”

Section: Introductionmentioning

confidence: 99%

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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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White phosphorus and metal nanoparticles: a versatile route to metal phosphide nanoparticles

Abstract: P(4) reaction with metal NPs (In, Pb, Zn) provides an easy access to the corresponding metal phosphide NPs in a soft and stoichiometric reaction. Size-influence on the reactivity is investigated in the case of indium.

Cited by 57 publications

References 39 publications

The Preparation of Other Chalcogenides and Pnictide Nanomaterials

The Preparation of Other Chalcogenides and Pnictide Nanomaterials

Synthesis of colloidal MnSb nanoparticles: consequences of size and surface characteristics on magnetic properties

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

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