Copper-doped semiconductors are classic phosphor materials that have been used in a variety of applications for many decades. Colloidal copper-doped semiconductor nanocrystals have recently attracted a great deal of interest because they combine the solution processability and spectral tunability of colloidal nanocrystals with the unique photoluminescence properties of copper-doped semiconductor phosphors. Although ternary and quaternary semiconductors containing copper, such as CuInS2 and Cu2ZnSnS4, have been studied primarily in the context of their photovoltaic applications, when synthesized as colloidal nanocrystals, these materials have photoluminescence properties that are remarkably similar to those of copper-doped semiconductor nanocrystals. This review focuses on the luminescent properties of colloidal copper-doped, copperbased, and related copper-containing semiconductor nanocrystals. Fundamental investigations into the luminescence of copper-containing colloidal nanocrystals are reviewed in the context of the well-established luminescence mechanisms of bulk copper-doped semiconductors and copper(I) molecular coordination complexes. The use of colloidal copper-containing nanocrystals in applications that take advantage of their luminescent properties, such as bio-imaging, solid-state lighting, and luminescent solar concentrators, is also discussed. a Measured at 20 K b Measured in a PV device 2. Synthesis and Structural Characterization of Colloidal Copper-Containing Nanocrystals Progress in the synthesis of luminescent copper-doped colloidal semiconductor NCs mirrors that in the synthesis of colloidal semiconductor NCs in general. The earliest reports from the mid-1980s through the 1990s describe the synthesis of copper-doped CdS and ZnS colloidal NCs by simply adding small amounts of copper salts to the aqueous-phase arrested precipitation reactions

Understanding the structural and compositional origins of midgap states in semiconductor nanocrystals is a longstanding challenge in nanoscience. Here, we report a broad variety of reagents useful for photochemical reduction of colloidal CdSe quantum dots, and we establish that these reactions proceed via a dark surface prereduction step prior to photoexcitation. Mechanistic studies relying on the specific properties of various reductants lead to the proposal that this surface prereduction occurs at oxidized surface selenium sites. These results demonstrate the use of small-molecule inorganic chemistries to control the physical properties of colloidal QDs and provide microscopic insights into the identities and reactivities of their localized surface species.

Colloidal Cu-doped CdSe/CdS core/shell semiconductor nanocrystals (NCs) are investigated in their as-prepared and degenerately n-doped forms using time-resolved photoluminescence and transient-absorption spectroscopies. Photoluminescence from Cu:CdSe/CdS NCs is dominated by recombination of delocalized conduction-band (CB) electrons with copper-localized holes. In addition to prominent bleaching of the first excitonic absorption feature, transient-absorption measurements show bleaching of the sub-bandgap copper-to-CB charge-transfer (MLCT) absorption band and also reveal a photoinduced midgap valence-band (VB)-to-copper charge-transfer (LMCT) absorption band that extends into the near-infrared, as predicted by recent computations. The photoluminescence of these NCs is substantially diminished upon introduction of excess CB electrons via photodoping. Time-resolved photoluminescence measurements reveal that the MLCT excited state is still formed upon photoexcitation of the n-doped Cu:CdSe/CdS NCs, but its luminescence is quenched by a fast (picosecond) three-carrier trap-assisted Auger recombination process involving two CB electrons and one copper-bound hole.

Colloidal semiconductor nanocrystals offer a unique opportunity to bridge molecular and bulk semiconductor redox phenomena. Here, potentiometric titration is demonstrated as a method for quantifying the Fermi levels and charging potentials of free-standing colloidal n-type ZnO nanocrystals possessing between 0 and 20 conduction-band electrons per nanocrystal, corresponding to carrier densities between 0 and 1.2 × 10(20) cm(-3). Potentiometric titration of colloidal semiconductor nanocrystals has not been described previously, and little precedent exists for analogous potentiometric titration of any soluble reductants involving so many electrons. Linear changes in Fermi level vs charge-carrier density are observed for each ensemble of nanocrystals, with slopes that depend on the nanocrystal size. Analysis indicates that the ensemble nanocrystal capacitance is governed by classical surface electrical double layers, showing no evidence of quantum contributions. Systematic shifts in the Fermi level are also observed with specific changes in the identity of the charge-compensating countercation. As a simple and contactless alternative to more common thin-film-based voltammetric techniques, potentiometric titration offers a powerful new approach for quantifying the redox properties of colloidal semiconductor nanocrystals.

A fundamental understanding of the rich electronic structures of electronically doped semiconductor nanocrystals is vital for assessing the utility of these materials for future applications from solar cells to redox catalysis. Here, we examine the use of magnetic circular dichroism (MCD) spectroscopy to probe the infrared localized surface plasmon resonances of p-CuSe, n-ZnO, and tin-doped InO (n-ITO) nanocrystals. We demonstrate that the MCD spectra of these nanocrystals can be analyzed by invoking classical cyclotron motions of their excess charge carriers, with experimental MCD signs conveying the carrier types (n or p) and experimental MCD intensities conveying the cyclotron splitting magnitudes. The experimental cyclotron splittings can then be used to quantify carrier effective masses (m*), with results that agree with bulk in most cases. MCD spectroscopy thus offers a unique measure of m* in free-standing colloidal semiconductor nanocrystals, raising new opportunities to investigate the influence of various other synthetic or environmental parameters on this fundamentally important electronic property.