Ion Exchange Synthesis of III–V Nanocrystals

Beberwyck, Brandon J.; Alivisatos, A. Paul

doi:10.1021/ja309416c

Cited by 143 publications

(172 citation statements)

References 48 publications

(77 reference statements)

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“…It has recently been used to produce GaAs, InAs, GaP, and InP with relatively narrow size dispersions, while avoiding the challenges associated with the traditional so-called hot-injection synthesis. [21][22][23] This synthetic route also has the advantage of preserving the original NC conformation, opening up the control of shape in these zinc blende NCs, including 1D rods and 2D sheets. A potential drawback is the incomplete removal of Cu that is used in an intermediate stage, and often quenches the PL.…”

Section: Synthesis Of Non-toxic Alternativesmentioning

confidence: 99%

A sustainable future for photonic colloidal nanocrystals

2015

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Colloidal nanocrystals - produced in a growing variety of shapes, sizes and compositions - are rapidly developing into a new generation of photonic materials, spanning light emitting as well as energy harvesting applications. Precise tailoring of their optoelectronic properties enables them to satisfy disparate application-specific requirements. However, the presence of toxic heavy metals such as cadmium and lead in some of the most mature nanocrystals is a serious drawback which may ultimately preclude their use in consumer applications. Although the pursuit of non-toxic alternatives has occurred in parallel to the well-developed Cd- and Pb-based nanocrystals, synthetic challenges have, until recently, curbed progress. In this review, we highlight recent advances in the development of heavy-metal-free nanocrystals within the context of specific photonic applications. We also describe strategies to transfer some of the advantageous nanocrystal features such as shape control to non-toxic materials. Finally, we present recent developments that have the potential to make substantial impacts on the quest to attain a balance between performance and sustainability in photonics.

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Section: Synthesis Of Non-toxic Alternativesmentioning

confidence: 99%

A sustainable future for photonic colloidal nanocrystals

2015

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“…This study follows an increasing number of contributions in this eld from various research groups, including those from Alivisatos and co-workers. For example, the usefulness of cation exchange reactions in nanomaterials has been demonstrated in the formation of CdS-Ag 2 S nanorods via partial exchange, 5 creation of CdS-Cu 2 S nanorods via a formation process that is different compared to that for CdS-Ag 2 S nanorods, 6 synthesis of CdSe/CdS nanorods to PbSe/PbS nanorods through Cu 2 Se/Cu 2 S assembly, 7 synthesis of group III-V (InP, InAs, GaP, and GaAs) nanocrystals from cadmium pnictide nanocrystals, 8 transformation of CdSe (core)-CdS (pod) to Cu 2Àx Se (core)-Cu 2 S (pod), 9 sequential formation from CdSe to Cu 2 Se to ZnSe, 14 These studies collectively indicate the wide diversity of exchanging the cationic component in semiconductor nanoparticles with another cation that oen differs in size and/or charge. Additionally, the cation exchange reaction in semiconductor nanoparticles is faster compared to the corresponding bulk phase reactions, enabling the easy accessibility of these reactions in routine chemical laboratories.…”

Section: Introductionmentioning

confidence: 99%

Role of reactant concentration and identity of added cation in controlling emission from post-synthetically modified terbium incorporated zinc sulfide nanoparticles: an avenue for the detection of lead(ii) cations

2018

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This work reports the photophysical properties of 1-thioglycerol capped hydrophilic terbium cation incorporated (doped) regime compared to in bulk environments. The results presented provide an avenue for the detection of heavy metal ions in general and Pb 2+ in particular, with a limit of detection that is at least in the range of sub-ppm, using either the broad ZnS or sharp Tb 3+ emission, respectively. This strategy provides an avenue to combine (i) the extremely sensitive and easily accessible analytical technique of photoluminescence spectroscopy, (ii) post-synthetic modification reactions in semiconductor nanoparticles that can be performed with less experimental demand, (iii) time-gated measurement related to the longer luminescence lifetime of terbium cations and (iv) the simultaneous use of broad ZnS nanoparticle and sharp Tb 3+ emission from the same assembly, helping eliminate false positive results.

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“…10,17 Finally, new exciting directions are represented by the possibility to synthesize NCs of III–V semiconductors with this strategy. 29 …”

Section: Introductionmentioning

confidence: 99%

Sn Cation Valency Dependence in Cation Exchange Reactions Involving Cu_2-xSe Nanocrystals

et al. 2014

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We studied cation exchange reactions in colloidal Cu2-xSe nanocrystals (NCs) involving the replacement of Cu+ cations with either Sn2+ or Sn4+ cations. This is a model system in several aspects: first, the +2 and +4 oxidation states for tin are relatively stable; in addition, the phase of the Cu2-xSe NCs remains cubic regardless of the degree of copper deficiency (that is, “x”) in the NC lattice. Also, Sn4+ ions are comparable in size to the Cu+ ions, while Sn2+ ones are much larger. We show here that the valency of the entering Sn ions dictates the structure and composition not only of the final products but also of the intermediate steps of the exchange. When Sn4+ cations are used, alloyed Cu2–4ySnySe NCs (with y ≤ 0.33) are formed as intermediates, with almost no distortion of the anion framework, apart from a small contraction. In this exchange reaction the final stoichiometry of the NCs cannot go beyond Cu0.66Sn0.33Se (that is Cu2SnSe3), as any further replacement of Cu+ cations with Sn4+ cations would require a drastic reorganization of the anion framework, which is not possible at the reaction conditions of the experiments. When instead Sn2+ cations are employed, SnSe NCs are formed, mostly in the orthorhombic phase, with significant, albeit not drastic, distortion of the anion framework. Intermediate steps in this exchange reaction are represented by Janus-type Cu2-xSe/SnSe heterostructures, with no Cu–Sn–Se alloys.

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Ion Exchange Synthesis of III–V Nanocrystals

Cited by 143 publications

References 48 publications

A sustainable future for photonic colloidal nanocrystals

A sustainable future for photonic colloidal nanocrystals

Role of reactant concentration and identity of added cation in controlling emission from post-synthetically modified terbium incorporated zinc sulfide nanoparticles: an avenue for the detection of lead(ii) cations

Sn Cation Valency Dependence in Cation Exchange Reactions Involving Cu_2-xSe Nanocrystals

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Ion Exchange Synthesis of III–V Nanocrystals

Cited by 143 publications

References 48 publications

A sustainable future for photonic colloidal nanocrystals

A sustainable future for photonic colloidal nanocrystals

Role of reactant concentration and identity of added cation in controlling emission from post-synthetically modified terbium incorporated zinc sulfide nanoparticles: an avenue for the detection of lead(ii) cations

Sn Cation Valency Dependence in Cation Exchange Reactions Involving Cu2-xSe Nanocrystals

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Sn Cation Valency Dependence in Cation Exchange Reactions Involving Cu_2-xSe Nanocrystals