Anne C. Berends

Prospects of Colloidal Copper Chalcogenide Nanocrystals

Over the past few years, colloidal copper chalcogenide nanocrystals (NCs) have emerged as promising alternatives to conventional Cd and Pb chalcogenide NCs. Owing to their wide size, shape, and composition tunability, Cu chalcogenide NCs hold great promise for several applications, such as photovoltaics, lighting and displays, and biomedical imaging. They also offer characteristics that are unparalleled by Cd and Pb chalcogenide NCs, such as plasmonic properties. Moreover, colloidal Cu chalcogenide NCs have low toxicity, potentially lower costs, and excellent colloidal stability. This makes them attractive materials for the large-scale deployment of inexpensive, sustainable, and environmentally benign solution-processed devices. Nevertheless, the synthesis of colloidal Cu chalcogenide NCs, especially that of ternary and quaternary compositions, has yet to reach the same level of mastery as that available for the prototypical Cd chalcogenide based NCs. This review provides a concise overview of this rapidly advancing field, sketching the state of the art and highlighting the key challenges. We discuss recent developments in the synthesis of size-, shape-, and composition-controlled NCs of Cu chalcogenides, with emphasis in strategies to circumvent the limitations arising from the need to precisely balance the reactivities of multiple precursors in synthesizing ternary and quaternary compositions. In this respect, we show that topotactic cation-exchange reactions are a promising alternative route to complex multinary Cu chalcogenide NCs and hetero-NCs, which are not attainable by conventional routes. The properties and potential applications of Cu chalcogenide NCs and hetero-NCs are also addressed.

Radiative and Nonradiative Recombination in CuInS2 Nanocrystals and CuInS2-Based Core/Shell Nanocrystals

Luminescent copper indium sulfide (CIS) nanocrystals are a potential solution to the toxicity issues associated with Cd- and Pb-based nanocrystals. However, the development of high-quality CIS nanocrystals has been complicated by insufficient knowledge of the electronic structure and of the factors that lead to luminescence quenching. Here we investigate the exciton decay pathways in CIS nanocrystals using time-resolved photoluminescence and transient absorption spectroscopy. Core-only CIS nanocrystals with low quantum yield are compared to core/shell nanocrystals (CIS/ZnS and CIS/CdS) with higher quantum yield. Our measurements support the model of photoluminescence by radiative recombination of a conduction band electron with a localized hole. Moreover, we find that photoluminescence quenching in low-quantum-yield nanocrystals involves initially uncoupled decay pathways for the electron and hole. The electron decay pathway determines whether the exciton recombines radiatively or nonradiatively. The development of high-quality CIS nanocrystals should therefore focus on the elimination of electron traps.

Non-blinking single-photon emitters in silica

Samples for single-emitter spectroscopy are usually prepared by spin-coating a dilute solution of emitters on a microscope cover slip of silicate based glass (such as quartz). Here, we show that both borosilicate glass and quartz contain intrinsic defect colour centres that fluoresce when excited at 532 nm. In a microscope image the defect emission is indistinguishable from spin-coated emitters. The emission spectrum is characterised by multiple peaks with the main peak between 2.05 and 2.20 eV, most likely due to coupling to a silica vibration with an energy that varies between 160 and 180 meV. The defects are single-photon emitters, do not blink, and have photoluminescence lifetimes of a few nanoseconds. Photoluminescence from such defects may previously have been misinterpreted as originating from single nanocrystal quantum dots.

Ultrathin One- and Two-Dimensional Colloidal Semiconductor Nanocrystals: Pushing Quantum Confinement to the Limit

Research on ultrathin nanomaterials is one of the fastest developing areas in contemporary nanoscience. The field of ultrathin one- (1D) and two-dimensional (2D) colloidal nanocrystals (NCs) is still in its infancy, but offers the prospect of production of ultrathin nanomaterials in liquid-phase at relatively low costs, with versatility in terms of composition, size, shape, and surface control. In this Perspective, the state of the art in the field is concisely outlined and critically discussed to highlight the essential concepts and challenges. We start by presenting a brief overview of the ultrathin colloidal 1D and 2D semiconductor NCs prepared to date, after which the synthesis strategies and formation mechanisms of both 1D and 2D NCs are discussed. The properties of these low-dimensional materials are then reviewed, with emphasis on the optical properties of luminescent NCs. Finally, the future prospects for the field are addressed.

Interplay Between Surface Chemistry, Precursor Reactivity and Temperature Determines Outcome of ZnS Shelling Reactions on CuInS2 Nanocrystals

ZnS shelling of I–III–VI2 nanocrystals (NCs) invariably leads to blue-shifts in both the absorption and photoluminescence spectra. These observations imply that the outcome of ZnS shelling reactions on I–III–VI2 colloidal NCs results from a complex interplay between several processes taking place in solution, at the surface of, and within the seed NC. However, a fundamental understanding of the factors determining the balance between these different processes is still lacking. In this work, we address this need by investigating the impact of precursor reactivity, reaction temperature, and surface chemistry (due to the washing procedure) on the outcome of ZnS shelling reactions on CuInS2 NCs using a seeded growth approach. We demonstrate that low reaction temperatures (150 °C) favor etching, cation exchange, and alloying regardless of the precursors used. Heteroepitaxial shell overgrowth becomes the dominant process only if reactive S- and Zn-precursors (S-ODE/OLAM and ZnI2) and high reaction temperatures (210 °C) are used, although a certain degree of heterointerfacial alloying still occurs. Remarkably, the presence of residual acetate at the surface of CIS seed NCs washed with ethanol is shown to facilitate heteroepitaxial shell overgrowth, yielding for the first time CIS/ZnS core/shell NCs displaying red-shifted absorption spectra, in agreement with the spectral shifts expected for a type-I band alignment. The insights provided by this work pave the way toward the design of improved synthesis strategies to CIS/ZnS core/shell and alloy NCs with tailored elemental distribution profiles, allowing precise tuning of the optoelectronic properties of the resulting materials.

Anisotropic 2D Cu2–xSe Nanocrystals from Dodecaneselenol and Their Conversion to CdSe and CuInSe2 Nanoparticles

We present the synthesis of colloidal anisotropic Cu2–xSe nanocrystals (NCs) with excellent size and shape control, using the unexplored phosphine-free selenium precursor 1-dodecaneselenol (DDSe). This precursor forms lamellar complexes with Cu(I) that enable tailoring the NC morphology from 0D polyhedral to highly anisotropic 2D shapes. The Cu2–xSe NCs are subsequently used as templates in postsynthetic cation exchange reactions, through which they are successfully converted to CdSe and CuInSe2 quantum dots, nanoplatelets, and ultrathin nanosheets. The shape of the template hexagonal nanoplatelets is preserved during the cation exchange reaction, despite a substantial reorganization of the anionic sublattice, which leads to conversion of the tetragonal umangite crystal structure of the parent Cu2–xSe NCs into hexagonal wurtzite CdSe and CuInSe2, accompanied by a change of both the thickness and the lateral dimensions of the nanoplatelets. The crystallographic transformation and reconstruction of the product NCs are attributed to a combination of the unit cell dimensionalities of the parent and product crystal phases and an internal ripening process. This work provides novel tools for the rational design of shape-controlled colloidal anisotropic Cu2–xSe NCs, which, besides their promising optoelectronic properties, also constitute a new family of cation exchange templates for the synthesis of shape-controlled NCs of wurtzite CdSe, CuInSe2, and other metal selenides that cannot be attained through direct synthesis approaches. Moreover, the insights provided here are likely applicable also to the direct synthesis of shape-controlled NCs of other metal selenides, since DDSe may be able to form lamellar complexes with several other metals.

Formation of Colloidal Copper Indium Sulfide Nanosheets by Two-Dimensional Self-Organization

Colloidal 2D semiconductor nanosheets (NSs) are an interesting new class of materials due to their unique properties. However, synthesis of these NSs is challenging, and synthesis procedures for materials other than the well-known Pb- and Cd-chalcogenides are still underdeveloped. In this paper, we present a new approach to make copper indium sulfide (CIS) NSs and study their structural and optical properties. The CIS NSs form via self-organization and oriented attachment of 2.5 nm chalcopyrite CuInS2 nanocrystals (NCs), yielding triangular- and hexagonal-shaped NSs with a thickness of ∼3 nm and lateral dimensions ranging from 20 to 1000 nm. The self-organization is induced by fast cation extraction, leading to attractive dipolar interactions between the NCs. Primary amines play a crucial role in the formation of the CIS NSs, both by forming in situ the cation extracting agent, and by preventing the attachment of NCs to the top and bottom facets of the NSs. Moreover, DFT calculations reveal that the amines are essential to stabilize the covellite crystal structure of the product CIS NSs. The NSs are indium-deficient and the off-stoichiometry gives rise to a plasmon resonance in the NIR spectral window.