Numerical Model to Simulate Electrochemical Charging of Nanocrystal Films.

Electrochemical charging of nanocrystal films opens up new possibilities for designing quantum dot-based device structures, but a solid theoretical framework of this process and its limitations is lacking. In this work, drift-diffusion simulations are employed to model the charging of nanocrystal films and gain insight into the electrochemical doping process. Through steady state simulations it is shown that the Fermi level and doping density in the nanocrystal film depend on the concentration of the electrolyte in addition to the value of the applied potential.

Permanent Electrochemical Doping of Quantum Dot Films through Photopolymerization of Electrolyte Ions.

Quantum dots (QDs) are considered for devices like light-emitting diodes (LEDs) and photodetectors as a result of their tunable optoelectronic properties. To utilize the full potential of QDs for optoelectronic applications, control over the charge carrier density is vital. However, controlled electronic doping of these materials has remained a long-standing challenge, thus slowing their integration into optoelectronic devices.

Quantitative Electrochemical Control over Optical Gain in Quantum-Dot Solids.

Solution-processed quantum dot (QD) lasers are one of the holy grails of nanoscience. They are not yet commercialized because the lasing threshold is too high: one needs >1 exciton per QD, which is difficult to achieve because of fast nonradiative Auger recombination. The threshold can, however, be reduced by electronic doping of the QDs, which decreases the absorption near the band-edge, such that the stimulated emission (SE) can easily outcompete absorption.

Engineering the Band Alignment in QD Heterojunction Films via Ligand Exchange.

Colloidal quantum dots (QDs) allow great flexibility in the design of optoelectronic devices, thanks to their size-dependent optical and electronic properties and the possibility to fabricate thin films with solution-based processing. In particular, in QD-based heterojunctions, the band gap of both components can be controlled by varying the size of the QDs. However, control over the band alignment between the two materials is required to tune the dynamics of carrier transfer across a heterostructure.

Electrochemical Modulation of the Photophysics of Surface-Localized Trap States in Core/Shell/(Shell) Quantum Dot Films.

In this work, we systematically study the spectroelectrochemical response of CdSe quantum dots (QDs), CdSe/CdS core/shell QDs with varying CdS shell thicknesses, and CdSe/CdS/ZnS core/shell/shell QDs in order to elucidate the influence of localized surface trap states on the optoelectronic properties. By correlating the differential absorbance and the photoluminescence upon electrochemically raising the Fermi level, we reveal that trap states near the conduction band (CB) edge give rise to nonradiative recombination pathways regardless of the CdS shell thickness, evidenced by quenching of the photoluminescence before the CB edge is populated with electrons. This points in the direction of shallow trap states localized on the CdS shell surface that give rise to nonradiative recombination pathways.

Enhancing the stability of the electron density in electrochemically doped ZnO quantum dots.

Electronic doping of semiconductor nanomaterials can be efficiently achieved using electrochemistry. However, the injected charge carriers are usually not very stable. After disconnecting the cell that is used for electrochemical doping, the carrier density drops, typically in several minutes.

On the Stability of Permanent Electrochemical Doping of Quantum Dot, Fullerene, and Conductive Polymer Films in Frozen Electrolytes for Use in Semiconductor Devices.

Semiconductor films that allow facile ion transport can be electronically doped via electrochemistry, where the amount of injected charge can be controlled by the potential applied. To apply electrochemical doping to the design of semiconductor devices, the injected charge has to be stabilized to avoid unintentional relaxation back to the intrinsic state. Here, we investigate methods to increase the stability of electrochemically injected charges in thin films of a wide variety of semiconductor materials, namely inorganic semiconductors (ZnO NCs, CdSe NCs, and CdSe/CdS core/shell NCs) and organic semiconductors (P3DT, PCBM, and C).

Tuning and Probing the Distribution of Cu and Cu Trap States Responsible for Broad-Band Photoluminescence in CuInS Nanocrystals.

The processes that govern radiative recombination in ternary CuInS (CIS) nanocrystals (NCs) have been heavily debated, but recently, several research groups have come to the same conclusion that a photoexcited electron recombines with a localized hole on a Cu-related trap state. Furthermore, it has been observed that single CIS NCs display narrower photoluminescence (PL) line widths than the ensemble, which led to the conclusion that within the ensemble there is a distribution of Cu-related trap states responsible for PL. In this work, we probe this trap-state distribution with in situ photoluminescence spectroelectrochemistry.