Indium arsenide quantum dots: an alternative to lead-based infrared emitting nanomaterials

Jalali, Houman Bahmani; Trizio, Luca De; Manna, Liberato; Stasio, Francesco Di

doi:10.1039/d2cs00490a

Cited by 19 publications

(32 citation statements)

References 213 publications

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“…This is attributed to the highly reactive and strongly coordinated precursors normally used (Section 2.2), in addition to the covalent nature of the resultant III-V QDs. 56,[81][82][83] For instance, when synthesising InP, it is widely accepted the P(SiR 3 ) 3 precursor is all but depleted in the nucleation phase. Consequently, the growth stage is driven by an Ostwald ripening process.…”

Section: Single-source Precursorsmentioning

confidence: 99%

Colloidal III–V quantum dots: a synthetic perspective

Gazis¹,

Cartlidge

Matthews

2023

J. Mater. Chem. C

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Section: Single-source Precursorsmentioning

confidence: 99%

Colloidal III–V quantum dots: a synthetic perspective

Gazis¹,

Cartlidge

Matthews

2023

J. Mater. Chem. C

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“…43 More covalent III−V NCs are an alternate material set, prompting research in developing surface chemical treatments to tailor NC assemblies. 44 For example, Na 2 S treatments exchange surface ligands, reducing d and enriching the NCs in S 2− , n-doping the NC assemblies as sulfur is a low-lying donor in III−V materials. The treatment can be carried out via solution or solid-state exchange or their combination (Figure 6A).…”

Section: Semiconductor Nc Assembliesmentioning

confidence: 99%

“…However, acutely toxic Cd and Pb are on the Restriction of Hazardous Substances (RoHS) Directive, and the ease of bond dissociation for their chalcogenides poses bans on their use in consumer electronics . More covalent III–V NCs are an alternate material set, prompting research in developing surface chemical treatments to tailor NC assemblies …”

Section: Introductionmentioning

confidence: 99%

Surface Engineering of Metal and Semiconductor Nanocrystal Assemblies and Their Optical and Electronic Devices

Choi

Lee

et al. 2023

Acc. Chem. Res.

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Conspectus Colloidal nanocrystals (NCs) are composed of inorganic cores and organic or inorganic ligand shells and serve as building blocks of NC assemblies. Metal and semiconductor NCs are well known for the size-dependent physical properties of their cores. The large NC surface-to-volume ratio and the space between NCs in assemblies places significant importance on the composition of the NC surface and ligand shell. Nonaqueous colloidal NC syntheses use relatively long organic ligands to control NC size and uniformity during growth and to prepare stable NC dispersions. However, these ligands create large interparticle distances that dilute the metal and semiconductor NC properties of their assemblies. In this Account, we describe postsynthesis chemical treatments to engineer the NC surface and design the optical and electronic properties of NC assemblies. In metal NC assemblies, compact ligand exchange reduces the interparticle distance and drives an insulator-to-metal transition tuning the dc resistivity over a 1010 range and the real part of the optical dielectric function from positive to negative across the visible-to-IR region. Juxtaposing NC and bulk metal thin films in bilayers allows the differential chemical and thermal addressability of the NC surface to be exploited in device fabrication. Ligand exchange and thermal annealing densifies the NC layer, creating interfacial misfit strain that triggers folding of the bilayers and is used to fabricate, with only one lithography step, large-area 3D chiral metamaterials. In semiconductor NC assemblies, chemical treatments such as ligand exchange, doping, and cation exchange control the interparticle distance and composition to add impurities, tailor stoichiometry, or make entirely new compounds. These treatments are employed in longer studied II–VI and IV–VI materials and are being developed as interest in III–V and I–III–VI2 NC materials grows. NC surface engineering is used to design NC assemblies with tailored carrier energy, type, concentration, mobility, and lifetime. Compact ligand exchange increases the coupling between NCs but can introduce intragap states that scatter and reduce the lifetime of carriers. Hybrid ligand exchange with two different chemistries can enhance the mobility-lifetime product. Doping increases carrier concentration, shifts the Fermi energy, and increases carrier mobility, creating n- and p-type building blocks for optoelectronic and electronic devices and circuits. Surface engineering of semiconductor NC assemblies is also important to modify device interfaces to allow the stacking and patterning of NC layers and to realize excellent device performance. It is used to construct NC-integrated circuits, exploiting the library of metal, semiconductor, and insulator NCs, to achieve all-NC, solution-fabricated transistors.

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“…Although a wide range of semiconductor NCs have been synthesized successfully, the ones studied most extensively are the II–VI and IV–VI semiconductors, such as CdSe and PbS, which have been exploited for optoelectronic and biomedical applications. , Despite the establishment of well-developed synthetic routes for these NCs and their appealing properties, the toxicity of cadmium and lead imposes problems for using them in some particular applications, especially those involving exposure to biological systems . This calls for exploring alternatives to these materials, which can replicate the optical properties of the II–VI and IV–VI NCs and potentially replace them in the various applications . This has led to a considerable effort to reveal alternative luminescent and photoactive metal chalcogenide compounds consisting of earth-abundant and less toxic elements.…”

Section: Introductionmentioning

confidence: 99%

“…4 This calls for exploring alternatives to these materials, which can replicate the optical properties of the II−VI and IV−VI NCs and potentially replace them in the various applications. 5 This has led to a considerable effort to reveal alternative luminescent and photoactive metal chalcogenide compounds consisting of earth-abundant and less toxic elements. Amongst several options, I−III−VI 2 semiconductor quantum dots (QDs) have proven themselves as outstanding candidates to serve as an alternative for their more toxic counterparts.…”

Section: ■ Introductionmentioning

confidence: 99%

Composition-Dependent Optical Properties of Cu–Zn–In–Se Colloidal Nanocrystals Synthesized via Cation Exchange

et al. 2023

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Copper chalcogenide-based nanocrystals (NCs) are a suitable replacement for toxic Cd/Pb chalcogenide-based NCs in a wide range of applications including photovoltaics, optoelectronics, and biological imaging. However, despite rigorous research, direct synthesis approaches of this class of compounds suffer from inhomogeneous size, shape, and composition of the NC ensembles, which is reflected in their broad photoluminescence (PL) bandwidths. A partial cation exchange (CE) strategy, wherein host cations in the initial binary copper chalcogenide are replaced by incoming cations to form ternary/quaternary multicomponent NCs, has been proven to be instrumental in achieving better size, shape, and composition control to this class of nanomaterials. Additionally, adopting synthetic strategies which help to eliminate inhomogeneities in the NC ensembles can lead to narrower PL bandwidths, as was shown by single-particle studies on I−III−VI 2 -based semiconductor NCs. In this work, we formulate a two-step colloidal synthesis of Cu−Zn−In−Se (CZISe) NCs via a partial CE pathway. The first step is the synthesis of Cu 2−x Se NCs, which serve as a template for the subsequent CE reaction. The second step is the incorporation of the In 3+ and Zn 2+ guest cations into the synthesized Cu 2−x Se NCs via simultaneous injection of both metal precursors, which results in gradient-alloyed CZISe NCs with a Zn-rich surface. The as-synthesized NCs exhibit near-infrared (NIR) PL without an additional shell growth, which is typically required in most of the developed protocols. The photoluminescence quantum yield (PLQY) of these Cu chalcogenide-based NCs reaches 20%. These NCs also exhibit intriguingly narrow PL bands, which challenges the notion of broad PL bands being an inherent property of this class of NCs. Additionally, a variation in the feed ratios of the incoming cations, i.e., In/Zn, results in the variation of the composition of the synthesized NCs. Henceforth, the optical properties of these NCs could be tuned by a simple variation of the composition of the NCs achieved by varying the feed ratios of the incoming cations. Within a narrow size distribution, the PL maxima range from 980 to 1060 nm, depending on the composition of the NCs. Post-synthetic surface modification of the synthesized NCs enabled the replacement of the parent long-chain organic ligands with smaller species, which is essential for their prospective applications requiring efficient charge transport. With PL emission extended into the NIR, the synthesized NCs are suitable for an array of potential applications, most importantly in the area of solar energy harvesting and bioimaging. The large Stokes shift inherent to these materials, their absorption in the solar range, and their NIR PL within the biological window make them suitable candidates.

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Indium arsenide quantum dots: an alternative to lead-based infrared emitting nanomaterials

Abstract: Colloidal indium arsenide quantum dots are promising RoHS-compliant building blocks for near infrared photonic, optoelectronic and biomedical applications.

Cited by 19 publications

References 213 publications

Colloidal III–V quantum dots: a synthetic perspective

Colloidal III–V quantum dots: a synthetic perspective

Surface Engineering of Metal and Semiconductor Nanocrystal Assemblies and Their Optical and Electronic Devices

Composition-Dependent Optical Properties of Cu–Zn–In–Se Colloidal Nanocrystals Synthesized via Cation Exchange

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