Nanostructure Engineering and Doping of Conjugated Carbon Nitride Semiconductors for Hydrogen Photosynthesis

Quantum dots are a unique class of emitters with size-tunable emission wavelengths, saturated emission colors, near-unity luminance efficiency, inherent photo- and thermal- stability and excellent solution processability. Quantum dots have been used as down-converters for back-lighting in liquid-crystal displays to improve color gamut, leading to the booming of quantum-dot televisions in consumer market. In the past few years, efficiency and lifetime of electroluminescence devices based on quantum dots achieved tremendous progress. These encouraging facts foreshadow the commercialization of quantum-dot light-emitting diodes (QLEDs), which promises an unprecedented generation of cost-effective, large-area, energy-saving, wide-color-gamut, ultra-thin and flexible displays. Here we provide a Progress Report, covering interdisciplinary aspects including material chemistry of quantum dots and charge-transporting layers, optimization and mechanism studies of prototype devices and processing techniques to produce large-area and high-resolution red-green-blue pixel arrays. We also identify a few key challenges facing the development of active-matrix QLED displays.

Quantum-Dot Light-Emitting Diodes for Large-Area Displays: Towards the Dawn of Commercialization.

Fluorinated n-type conjugated polymers are used as efficient electron acceptor to demonstrate high-performance all-polymer solar cells. The exciton generation, dissociation, and charge-transporting properties of blend films are improved by using these fluorinated n-type polymers to result in enhanced photocurrent and suppressed charge recombination.

Fluoro‐Substituted n‐Type Conjugated Polymers for Additive‐Free All‐Polymer Bulk Heterojunction Solar Cells with High Power Conversion Efficiency of 6.71%

Recent advances and the current status of challenging light-harvesting nanomaterials, such as semiconducting quantum dots (QDs), metal nanoparticles, semiconductor–metal heterostructures, π-conjugated semiconductor nanoparticles, organic–inorganic heterostructures, and porphyrin-based nanostructures, have been highlighted in this review. The significance of size-, shape-, and composition-dependent exciton decay dynamics and photoinduced energy transfer of QDs is addressed. A fundamental knowledge of these photophysical processes is crucial for the development of efficient light-harvesting systems, like photocatalytic and photovoltaic ones. Again, we have pointed out the impact of the metal-nanoparticle-based surface energy transfer process for developing light-harvesting systems. On the other hand, metal–semiconductor hybrid nanostructures are found to be very promising for photonic applications due to their exciton–plasmon interactions. Potential light-harvesting systems based on dye-doped π-conjugated s...

Nanoscale Strategies for Light Harvesting

Herein, the assembly of CsPbBr3 QD/AlOx inorganic nanocomposite, using atomic layer deposition (ALD) for the growth of the amorphous alumina matrix (AlOx), is proven as a novel protection scheme for this new class of QDs. The nucleation and growth process of AlOx on the QD surface was thoroughly investigated by a miscellanea of techniques which highlighed the importance of the interaction between the ALD precursor and the QD surface to uniformely coat the QDs while preserving the optoelectronic properties. These nanocomposites show an exceptional stability against exposure to air (for at least 45 days), irradiation under simulated solar spectrum (for at least 8h), to thermal treatment (at least up to 200oC in air), and finally against immersion in water. The method was extended to assembly CsPbBrxI3-x QD/AlOx and CsPbI3 QD/AlOx nanocomposites which were more stable compared to the pristine QD films.

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CsPbBr3 QD/AlOx Inorganic Nanocomposites with Exceptional Stability in Water, Light, and Heat

Colloidal quantum dots (QDs) are promising materials for use in solar cells, light-emitting diodes, lasers, and photodetectors, but the mechanism and length of exciton transport in QD materials is not well understood. We use time-resolved optical microscopy to spatially visualize exciton transport in CdSe/ZnCdS core/shell QD assemblies. We find that the exciton diffusion length, which exceeds 30 nm in some cases, can be tuned by adjusting the inorganic shell thickness and organic ligand length, offering a powerful strategy for controlling exciton movement. Moreover, we show experimentally and through kinetic Monte Carlo simulations that exciton diffusion in QD solids does not occur by a random-walk process; instead, energetic disorder within the inhomogeneously broadened ensemble causes the exciton diffusivity to decrease over time. These findings reveal new insights into exciton dynamics in disordered systems and demonstrate the flexibility of QD materials for photonic and optoelectronic applications.

Subdiffusive Exciton Transport in Quantum Dot Solids

A thin-film transistor: An n-type polymer semiconductor, poly(2,3-bis(perfluorohexyl)thieno[3,4-b]pyrazine), was synthesized through a Pd-catalyzed polycondensation employing a perfluorinated multiphase solvent system. This is the first example of an n-type polymer semiconductor with exclusive solubility in fluorinated solvents. The fabrication of organic field effect transistors containing this new n-type polymer semiconductor is shown.

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An Air-Stable Low-Bandgap n-Type Organic Polymer Semiconductor Exhibiting Selective Solubility in Perfluorinated Solvents

Excitonic energy transfer among colloidal nanocrystal quantum dots (QDs) is responsible for exciton transport in many QD optoelectronic devices. While Forster theory has successfully accounted for the distance scaling of energy transfer in many QD systems, the overall magnitude of the Forster radius in close-packed QD solids remains an open question. Here, we use spectrally resolved transient photoluminescence quenching to measure the magnitude of the Forster radius in blended donor–acceptor QD assemblies. For blends of CdSe/CdZnS core/shell QDs consisting of 4.0 nm diameter donors (λmax,em ≈ 550 nm) and 5.5 nm acceptors (λmax,abs ≈ 590 nm), we measure energy transfer rates per donor–acceptor pair that are 10–100 times faster than the predictions of Forster theory. These rates correspond to an effective Forster radius of 8–9 nm, compared to a theoretical Forster radius of 5–6 nm. We discuss possible sources for the discrepancy between theory and experiment—including the magnitude of the absorption cross s...

Magnitude of the Förster Radius in Colloidal Quantum Dot Solids

Recent experimental and theoretical results have highlighted the surprisingly dominant role of acoustic phonons in regulating dynamic processes in nanocrystals. While it has been known for many years that acoustic phonon frequencies in nanocrystals depend on their size, strategies for tuning acoustic phonon energy at a given fixed size were not available. Here, we show that acoustic phonon frequencies in colloidal quantum dots (QDs) can be tuned through the choice of the surface ligand. Using low-frequency Raman spectroscopy, we explore the dependence of the l = 0 acoustic phonon resonance in CdSe QDs on ligand size, molecular weight, and chemical functionality. On the basis of these aggregated observations, we conclude that the primary mechanism for this effect is mass loading of the QD surface and that interactions between ligands and with the surrounding environment play a comparatively minor yet non-negligible role.

Modulation of Low-Frequency Acoustic Vibrations in Semiconductor Nanocrystals through Choice of Surface Ligand

The measured low frequency vibrational energies of some quantum dots (QDs) deviate from the predictions of traditional elastic continuum models. Recent experiments have revealed that these deviations can be tuned by changing the ligands that passivate the QD surface. This observation has led to speculation that these deviations are due to a mass-loading effect of the surface ligands. In this article, we address this speculation by formulating a continuum elastic theory that includes the dynamical loading by elastic surface ligands. We demonstrate that this model is capable of accurately reproducing the l = 0 phonon energy across a variety of different QD samples, including cores with different ligand identities and epitaxially grown CdSe/CdS core/shell heterostructures. We highlight that our model performs well even in the small QD regime, where traditional elastic continuum models are especially prone to failure. Furthermore, we show that our model combined with Raman measurements can be used to infer the elastic properties of surface bound ligands, such as sound velocities and elastic moduli, that are otherwise challenging to measure.

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A. Jolene Mork

Papers

Subdiffusive Exciton Transport in Quantum Dot Solids

An Air-Stable Low-Bandgap n-Type Organic Polymer Semiconductor Exhibiting Selective Solubility in Perfluorinated Solvents

Magnitude of the Förster Radius in Colloidal Quantum Dot Solids

Modulation of Low-Frequency Acoustic Vibrations in Semiconductor Nanocrystals through Choice of Surface Ligand

Including surface ligand effects in continuum elastic models of nanocrystal vibrations