Engineering topics
Pinchetti, Valerio
Publications and source records attributed to Pinchetti, Valerio.
Colloidal Semiconductor Nanocrystal Lasers and Laser Diodes
Lasers and optical amplifiers based on solution-processable materials have been long-desired devices for their compatibility with virtually any substrate, scalability, and ease of integration with on-chip photonics and electronics. These devices have been pursued across a wide range of materials including polymers, small molecules, perovskites, and chemically prepared colloidal semiconductor nanocrystals, also commonly referred to as colloidal quantum dots. The latter materials are especially attractive for implementing optical-gain media as in addition to being compatible with inexpensive and easily scalable chemical techniques, they offer multiple advantages derived from a zero-dimensional character of their electronic states. These include a size-tunable emission wavelength, low optical gain thresholds, and weak sensitivity of lasing characteristics to variations in temperature. Here we review the status of colloidal nanocrystal lasing devices, most recent advances in this field, outstanding challenges, and the ongoing progress toward technological viable devices including colloidal quantum dot laser diodes.
Electrically driven amplified spontaneous emission from colloidal quantum dots
Colloidal quantum dots (QDs) are attractive materials for realizing solution-processable laser diodes that could benefit from size-controlled emission wavelengths, low optical-gain thresholds and ease of integration with photonic and electronic circuits. However, the implementation of such devices has been hampered by fast Auger recombination of gain-active multicarrier states, poor stability of QD films at high current densities and the difficulty to obtain net optical gain in a complex device stack wherein a thin electroluminescent QD layer is combined with optically lossy charge-conducting layers. Here we resolve these challenges and achieve amplified spontaneous emission (ASE) from electrically pumped colloidal QDs. The developed devices use compact, continuously graded QDs with suppressed Auger recombination incorporated into a pulsed, high-current-density charge-injection structure supplemented by a low-loss photonic waveguide. These colloidal QD ASE diodes exhibit strong, broadband optical gain and demonstrate bright edge emission with instantaneous power of up to 170 μW.
Optical and Magneto-Optical Properties of Donor-Bound Excitons in Vacancy-Engineered Colloidal Nanocrystals
Controlled insertion of electronic states within the band gap of semiconductor nanocrystals (NCs) is a powerful tool for tuning their physical properties. One compelling example is II–VI NCs incorporating heterovalent coinage metals in which hole capture produces acceptor-bound excitons. To date, the opposite donor-bound exciton scheme has not been realized because of the unavailability of suitable donor dopants. Here, we produce a model system for donor-bound excitons in CdSeS NCs engineered with sulfur vacancies (V S ) that introduce a donor state below the conduction band (CB), resulting in long-lived intragap luminescence. V S -localized electrons are almost unaffected by trapping, and suppression of thermal quenching boosts the emission efficiency to 85%. Magneto-optical measurements indicate that the V S are not magnetically coupled to the NC bands and that the polarization properties are determined by the spin of the valence-band photohole, whose spin flip is massively slowed down due to suppressed exchange interaction with the donor-localized electron.
Intrinsic and Extrinsic Exciton Recombination Pathways in AgInS 2 Colloidal Nanocrystals
Ternary I-III-VI 2 nanocrystals (NCs), such as AgInS 2 and CuInS 2 , are garnering interest as heavy-metal-free materials for photovoltaics, luminescent solar concentrators, LEDs, and bioimaging. The origin of the emission and absorption properties in this class of NCs is still a subject of debate. Recent theoretical and experimental studies revealed that the characteristic Stokes-shifted and long-lived luminescence of stoichiometric CuInS 2 NCs arises from the detailed structure of the valence band featuring two sublevels with different parity. The same valence band substructure is predicted to occur in AgInS 2 NCs, yet no experimental confirmation is available to date. Here, we use complementary spectroscopic, spectro-electrochemical, and magneto-optical investigations as a function of temperature to investigate the band structure and the excitonic recombination mechanisms in stoichiometric AgInS 2 NCs. Transient transmission measurements reveal the signatures of two subbands with opposite parity, and photoluminescence studies at cryogenic temperatures evidence a dark state emission due to enhanced exchange interaction, consistent with the behavior of stoichiometric CuInS 2 NCs. Lowering the temperature as well as applying reducing electrochemical potentials further suppress electron trapping, which represents the main nonradiative channel for exciton decay, leading to nearly 100% emission efficiency.
Evidence for the Band-Edge Exciton of CuInS 2 Nanocrystals Enables Record Efficient Large-Area Luminescent Solar Concentrators
Ternary I-III-VI 2 nanocrystals (NCs), such as CuInS 2 , are receiving attention as heavy-metals-free materials for solar cells, luminescent solar concentrators (LSCs), LEDs, and bio-imaging. The origin of the optical properties of CuInS 2 NCs are however not fully understood. A recent theoretical model suggests that their characteristic Stokes-shifted and long-lived luminescence arises from the structure of the valence band (VB) and predicts distinctive optical behaviours in defect-free NCs: the quadratic dependence of the radiative decay rate and the Stokes shift on the NC radius. If confirmed, this would have crucial implications for LSCs as the solar spectral coverage ensured by low-bandgap NCs would be accompanied by increased re-absorption losses. Here, by studying stoichiometric CuInS 2 NCs, it is revealed for the first time the spectroscopic signatures predicted for the free band-edge exciton, thus supporting the VB-structure model. At very low temperatures, the NCs also show dark-state emission likely originating from enhanced electron-hole spin interaction. In this study, the impact of the observed optical behaviours on LSCs is evaluated by Monte Carlo ray-tracing simulations. Based on the emerging device design guidelines, optical-grade large-area (30×30 cm 2 ) LSCs with optical power efficiency (OPE) as high as 6.8% are fabricated, corresponding to the highest value reported to date for large-area devices.
Dual-Emitting Dot-in-Bulk CdSe/CdS Nanocrystals with Highly Emissive Core- and Shell-Based Trions Sharing the Same Resident Electron
Colloidal CdSe nanocrystals (NCs) overcoated with an ultrathick CdS shell, also known as dot-in-bulk (DiB) structures, can support two types of excitons, one of which is core-localized and the other, shell-localized. In the case of weak “sub-single-exciton” pumping, emission alternates between the core- and shell-related channels, which leads to two-color light. This property makes these structures uniquely suited for a variety of photonic applications as well as ideal model systems for realizing complex excitonic quasi-particles that do not occur in conventional core/shell NCs. Furthermore, we show that the DiB design can enable an unusual regime in which the same long-lived resident electron can endow trionlike characteristics to either of the two excitons of the DiB NC (core- or shell-based). These two spectrally distinct trion states are apparent in the measured photoluminescence (PL) and spin dynamics of core and shell excitons conducted over a wide range of temperatures and applied magnetic fields. Low-temperature PL measurements indicate that core- and shell-based trions are characterized by a nearly ideal (~100%) emission quantum yield, suggesting the strong suppression of Auger recombination for both types of excitations. Polarization-resolved PL experiments in magnetic fields of up to 60 T reveal that the core- and the shell-localized trions exhibit remarkably similar spin dynamics, which in both cases are controlled by spin-flip processes involving a heavy hole.
Quantized Electronic Doping towards Atomically Controlled “Charge-Engineered” Semiconductor Nanocrystals
“Charge engineering” of semiconductor nanocrystals (NCs) through so-called electronic impurity doping is a long-standing challenge in colloidal chemistry and holds promise for ground-breaking advancements in many optoelectronic, photonic, and spin-based nanotechnologies. To date, our knowledge is limited to a few paradigmatic studies on a small number of model compounds and doping conditions, with important electronic dopants still unexplored in nanoscale systems. Equally importantly, fine-tuning of charge engineered NCs is hampered by the statistical limitations of traditional approaches. The resulting intrinsic doping inhomogeneity restricts fundamental studies to statistically averaged behaviors and complicates the realization of advanced device concepts based on their advantageous functionalities. We aim to address these issues by realizing the first example of II–VI NCs electronically doped with an exact number of heterovalent gold atoms, a known p-type acceptor impurity in bulk chalcogenides. Single-dopant accuracy across entire NC ensembles is obtained through a novel non-injection synthesis employing ligand-exchanged gold clusters as “quantized” dopant sources to seed the nucleation of CdSe NCs in organic media. Structural, spectroscopic, and magneto-optical investigations trace a comprehensive picture of the physical processes resulting from the exact doping level of the NCs. Gold atoms, doped here for the first time into II–VI NCs, are found to incorporate as nonmagnetic Au + species activating intense size-tunable intragap photoluminescence and artificially offsetting the hole occupancy of valence band states. Fundamentally, the transient conversion of Au + to paramagnetic Au 2+ (5d 9 configuration) under optical excitation results in strong photoinduced magnetism and diluted magnetic semiconductor behavior revealing the contribution of individual paramagnetic impurities to the macroscopic magnetism of the NCs. Altogether, our results demonstrate a new chemical approach toward NCs with physical functionalities tailored to the single impurity level and offer a versatile platform for future investigations and device exploitation of individual and collective impurity processes in quantum confined structures.