Development of light-emitting diodes (LEDs) based on colloidal quantum dots is driven by attractive properties of these fluorophores such as spectrally narrow, tunable emission and facile processibility via solution-based methods. A current obstacle towards improved LED performance is an incomplete understanding of the roles of extrinsic factors, such as non-radiative recombination at surface defects, versus intrinsic processes, such as multicarrier Auger recombination or electron-hole separation due to applied electric field. Here we address this problem with studies that correlate the excited state dynamics of structurally engineered quantum dots with their emissive performance within LEDs. We find that because of significant charging of quantum dots with extra electrons, Auger recombination greatly impacts both LED efficiency and the onset of efficiency roll-off at high currents. Further, we demonstrate two specific approaches for mitigating this problem using heterostructured quantum dots, either by suppressing Auger decay through the introduction of an intermediate alloyed layer, or by using an additional shell that impedes electron transfer into the quantum dot to help balance electron and hole injection.

The influence of a CdSexS1-x interfacial alloyed layer on the photophysical properties of core/shell CdSe/CdS nanocrystal quantum dots (QDs) is investigated by comparing reference QDs with a sharp core/shell interface to alloyed structures with an intermediate CdSexS1-x layer at the core/shell interface. To fully realize the structural contrast, we have developed two novel synthetic approaches: a method for fast CdS-shell growth, which results in an abrupt core/shell boundary (no intentional or unintentional alloying), and a method for depositing a CdSexS1-x alloy layer of controlled composition onto the CdSe core prior to the growth of the CdS shell. Both types of QDs possess similar size-dependent single-exciton properties (photoluminescence energy, quantum yield, and decay lifetime). However the alloyed QDs show a significantly longer biexciton lifetime and up to a 3-fold increase in the biexciton emission efficiency compared to the reference samples. These results provide direct evidence that the structure of the QD interface has a significant effect on the rate of nonradiative Auger recombination, which dominates biexciton decay. We also observe that the energy gradient at the core-shell interface introduced by the alloyed layer accelerates hole trapping from the shell to the core states, which results in suppression of shell emission. This comparative study offers practical guidelines for controlling multicarrier Auger recombination without a significant effect on either spectral or dynamical properties of single excitons. The proposed strategy should be applicable to QDs of a variety of compositions (including, e.g., infrared-emitting QDs) and can benefit numerous applications from light emitting diodes and lasers to photodetectors and photovoltaics.

Luminescent solar concentrators serving as semitransparent photovoltaic windows could become an important element in net zero energy consumption buildings of the future. Colloidal quantum dots are promising materials for luminescent solar concentrators as they can be engineered to provide the large Stokes shift necessary for suppressing reabsorption losses in large-area devices. Existing Stokes-shift-engineered quantum dots allow for only partial coverage of the solar spectrum, which limits their light-harvesting ability and leads to colouring of the luminescent solar concentrators, complicating their use in architecture. Here, we use quantum dots of ternary I-III-VI2 semiconductors to realize the first large-area quantum dot-luminescent solar concentrators free of toxic elements, with reduced reabsorption and extended coverage of the solar spectrum. By incorporating CuInSexS2-x quantum dots into photo-polymerized poly(lauryl methacrylate), we obtain freestanding, colourless slabs that introduce no distortion to perceived colours and are thus well suited for the realization of photovoltaic windows. Thanks to the suppressed reabsorption and high emission efficiencies of the quantum dots, we achieve an optical power efficiency of 3.2%. Ultrafast spectroscopy studies suggest that the Stokes-shifted emission involves a conduction-band electron and a hole residing in an intragap state associated with a native defect.

Solution-processed semiconductor quantum dot solar cells offer a path towards both reduced fabrication cost and higher efficiency enabled by novel processes such as hot-electron extraction and carrier multiplication. Here we use a new class of low-cost, low-toxicity CuInSexS2−x quantum dots to demonstrate sensitized solar cells with certified efficiencies exceeding 5%. Among other material and device design improvements studied, use of a methanol-based polysulfide electrolyte results in a particularly dramatic enhancement in photocurrent and reduced series resistance. Despite the high vapour pressure of methanol, the solar cells are stable for months under ambient conditions, which is much longer than any previously reported quantum dot sensitized solar cell. This study demonstrates the large potential of CuInSexS2−x quantum dots as active materials for the realization of low-cost, robust and efficient photovoltaics as well as a platform for investigating various advanced concepts derived from the unique physics of the nanoscale size regime.

Luminescent CuInS 2 (CIS) quantum dots (QDs) exhibit highly efficient intragap emission and long, hundreds-ofnanoseconds radiative lifetimes. These spectral properties, distinct from structurally similar II−VI QDs, can be explained by the involvement of intragap defect states containing a localized hole capable of coupling with a conduction band electron for a radiative transition. However, the absolute energies of the intragap and band-edge states, the structure of the emissive defect(s), and the role and origin of nonemissive decay channels still remain poorly understood. Here, we address these questions by applying methods of spectral electrochemistry. Cyclic voltammetry measurements reveal a well-defined intragap state whose redox potential is close to that of the Cu x defect state (where x = 1+ or 2+). The energy offset of this state from the valence band accounts well for the apparent photoluminescence Stokes shift observed in optical spectra. These results provide direct evidence that Cu-related defects serve as emission centers responsible for strong intragap emission from CIS QDs. We then use in situ spectroelectrochemistry to reveal two distinct emission pathways based on the differing oxidation states of Cu defects, which can be controlled by altering QD stoichiometry (1+ for stoichiometric QDs and 2+ for Cu-deficient QDs).