Versatile Tri(pyrazolyl)phosphanes as Phosphorus Precursors for the Synthesis of Highly Emitting InP/ZnS Quantum Dots

Panzer, René; Guhrenz, Chris; Haubold, Danny; Hübner, René; Gaponik, Nikolai; Eychmüller, Alexander; Weigand, Jan J.

doi:10.1002/anie.201705650

Cited by 25 publications

(20 citation statements)

References 43 publications

(49 reference statements)

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“…Due to the high reaction temperatures an alloying process near the interface of the core and shell material shifts the (111) reflexes toward the pure zinc‐containing shell material. This can be explained by a partial migration of zinc ions into the InAs core region, as it is also observed in the synthesis of InP/ZnS QDs . TEM measurements of the resulting spherical InAs/ZnS QDs exhibit an increase in the nanoparticle size compared to the original core particles and confirms additionally the growth of a ZnS protective layer (Figure S4, Supporting Information).…”

Section: Resultssupporting

confidence: 59%

“…All glassware was oven‐dried at 160 °C prior to use. Tris(3,5‐dimethylpyrazolyl)phosphane 2 and the 0.5 m P(OLA) 3 stock‐solution was obtained according to literature procedures …”

Section: Methodsmentioning

confidence: 99%

“…In recent years group III–V semiconductor materials gained tremendous attention as less toxic surrogates for group II–VI nanomaterials in optoelectronic devices . Thereby, InAs QDs are one of the most promising candidates for near infrared (NIR) and short‐wave infrared applications, such as bioimaging, photovoltaics, photodetectors, and lasers .…”

Section: Introductionmentioning

confidence: 99%

“…In previous work we introduced tripyrazolylphosphanes (P(pyr) 3 , e.g., pyr = 3,5‐dimethylpyrazole, 2 ) for the convenient preparation of a long term stable (>6 months) P(OLA) 3 stock solution and its application for the synthesis of highly emitting InP/ZnS QDs . Derivatives of P(pyr) 3 are accessible on a multigram scale and represent a safe to handle, less toxic surrogate for cancerogenic hexaalkylphosphorous triamide derivatives such as tris‐dimethylaminophosphane (P(NMe 2 ) 3 ) and tris‐diethylaminophosphane (P(NEt 2 ) 3 ).…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of NIR‐Emitting InAs‐Based Core/Shell Quantum Dots with the Use of Tripyrazolylarsane as Arsenic Precursor

Tietze

Panzer

Starzynski

et al. 2018

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arsenic precursor [2,16] besides the less reactive tris(trimethylgermyl)arsane (As(GeMe 3 ) 3 ) [17] or highly toxic arsine gas (AsH 3 ). [18] Recently, Srivastava et al. [19] and Grigel et al. [20] highlighted tris(dimethylamino)arsane (As(NMe 2 ) 3 ) as commercially available pre cursor for the facile synthesis of InAs QDs. Mechanistically, As(NMe 2 ) 3 undergoes a transamination reaction with the solvent and reagent oleylamine (OLAH) to give trioleyl arsane (As(OLA) 3 ) under the release of three equivalents of flammable dimethylamine. The reaction of As(OLA) 3 with indium(III) chloride (InCl 3 ) to InAs QDs does not proceed without the subsequent addition of a reducing agent for which typically diisobutylaluminum hydride (DIBALH) [19] and nowadays also trioleylphosphane (P(OLA) 3 ) [20] or a N,Ndimethylethylamine com plex (DMEAAlH 3 ) [21] are used. In the case of DIBALH and DMEA AlH 3 , the As-N bonds are cleaved to give in situ (OLA) x AsH 3x species which react with the indium precursor to InAs QDs. [22,23] With the applied concentration of DIBALH the size of InAs QDs can be tuned according to the method by Srivastava et al. [19] By contrast, the approach by Grigel et al. [20] applies in situ generated P(OLA) 3 as reducing agent for the InAs QD synthesis (Scheme 1). This species is known to act both, as a remarkably efficient phos phorus precursor and reducing agent for the preparation of InP QDs. [24][25][26] Grigel et al. [20] pointed out that phase pure InAs QDs are obtained since P(OLA) 3 only provides the electrons required for the reduction of As(OLA) 3 to InAs (Scheme 1).In previous work we introduced tripyrazolylphosphanes (P(pyr) 3 , e.g., pyr = 3,5dimethylpyrazole, 2) for the convenient preparation of a long term stable (>6 months) P(OLA) 3 stock solution and its application for the synthesis of highly emitting InP/ZnS QDs. [5,6] Derivatives of P(pyr) 3 are accessible on a multigram scale and represent a safe to handle, less toxic sur rogate for cancerogenic hexaalkylphosphorous triamide deriva tives such as trisdimethylaminophosphane (P(NMe 2 ) 3 ) and tris diethylaminophosphane (P(NEt 2 ) 3 ). Moreover, the release of cor rosive, flammable, and gaseous dialkylamines (Me 2 NH, Et 2 NH) during the transamination with OLAH is prevented. The released pyrazoles can easily be recovered in high yields (>94%) and reused for the precursor synthesis. The tripyrazolylarsane (As(pyr) 3 , e.g., pyr = 3,5dimethylpyrazole, 1) analogues are envisioned to react similarly, thus, representing a convenient to handle and stable arsenic precursor for the InAs QD synthesis. Tris(3,5-dimethylpyrazolyl)arsane (1) is introduced as a low-cost and convenient to handle arsenic precursor for the straight forward synthesis of InAs quantum dots (QDs). Transamination of 1 with the solvent oleylamine (OLAH) gives trioleylarsane (As(OLA) 3 ) which in the presence of the reducing agents diisobutylaluminum hydride (DIBAL-H) or trioleylphosphane (P(OLA) 3 ) yields InAsQDs via a typical hot injection approach. The size of the obtain...

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Section: Resultssupporting

confidence: 59%

“…All glassware was oven‐dried at 160 °C prior to use. Tris(3,5‐dimethylpyrazolyl)phosphane 2 and the 0.5 m P(OLA) 3 stock‐solution was obtained according to literature procedures …”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis of NIR‐Emitting InAs‐Based Core/Shell Quantum Dots with the Use of Tripyrazolylarsane as Arsenic Precursor

Tietze

Panzer

Starzynski

et al. 2018

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“…3 This economic perspective has inspired the recent development of protocols that use aminophosphines, a cheap and easyto-use phosphorus precursor, to produce InP QDs with stateof-the-art emission characteristics. [4][5][6][7][8] Even so, differences remain with Cd-based QDs. For example, whereas the photoluminescence quantum yield (PLQY) of Cd-based QDs can reach 90-100 %, 9,10 a PLQY of 70 % at best is more typical of InP-based QDs.…”

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confidence: 99%

Interfacial Oxidation and Photoluminescence of InP-Based Core/Shell Quantum Dots

et al. 2018

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Indium phosphide colloidal quantum dots (QDs) are emerging as an efficient cadmium-free alternative for optoelectronic applications. Recently, syntheses based on easy-to-implement aminophosphine precursors have been developed. We show by solid-state nuclear magnetic resonance spectroscopy that this new approach allows oxide-free indium phosphide core or core/shell quantum dots to be made. Importantly, the oxide-free core/shell interface does not help in achieving higher luminescence efficiencies. We demonstrate that in the case of InP/ZnS and InP/ZnSe QDs, a more pronounced oxidation concurs with a higher photoluminescence efficiency. This study suggests that a II–VI shell on a III–V core generates an interface prone to defects. The most efficient InP/ZnS or InP/ZnSe QDs are therefore made with an oxide buffer layer between the core and the shell: it passivates these interface defects but also results in a somewhat broader emission line width.

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Green InP/ZnSeS/ZnS Core Multi‐Shelled Quantum Dots Synthesized with Aminophosphine for Effective Display Applications

Liu

Lou

Ding

et al. 2021

Adv Funct Materials

102

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InP quantum dots (QDs) are emerging as promising materials for replacing cadmium‐based QDs in view of their heavy metal‐free and tunable luminescence. However, the development of InP QD materials still lags due to the expensive and flammable phosphorus precursors, and also the unsatisfactory repeatability caused by the fast nucleation rate. Adopting lowly reactive P precursor aminophosphine can overcome this issue, but their low photoluminescence quantum yield (PLQY) and widening line widths do not apply to the practical application. Through engineering, the core‐shell structure of QD, significantly promoted green emissions of QDs were obtained with PLQY of 95% and full width and half maximum (FWHM) of 45 nm, which demonstrated the highest PLQY record obtained from the aminophosphine system. Moreover, due to the residue halogen atoms on the QD surface as inorganic ligands to prevent further oxidization, these InP QDs demonstrated the ultra‐long operational lifetime (over 1000 h) for QDs based color enhancement film. By optimizing the device structure, an inverted green InP quantum dot light‐emitting diode (QLED) with external quantum efficiency (EQE) of 7.06% was also demonstrated, which showed a significant promise of these InP QDs in highly effective optoelectronic devices.

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Versatile Tri(pyrazolyl)phosphanes as Phosphorus Precursors for the Synthesis of Highly Emitting InP/ZnS Quantum Dots

Cited by 25 publications

References 43 publications

Synthesis of NIR‐Emitting InAs‐Based Core/Shell Quantum Dots with the Use of Tripyrazolylarsane as Arsenic Precursor

Synthesis of NIR‐Emitting InAs‐Based Core/Shell Quantum Dots with the Use of Tripyrazolylarsane as Arsenic Precursor

Interfacial Oxidation and Photoluminescence of InP-Based Core/Shell Quantum Dots

Green InP/ZnSeS/ZnS Core Multi‐Shelled Quantum Dots Synthesized with Aminophosphine for Effective Display Applications

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