Igor Fedin

Low-Threshold Stimulated Emission Using Colloidal Quantum Wells

The use of colloidal semiconductor nanocrystals for optical amplification and lasing has been limited by the need for high input power densities. Here we show that colloidal nanoplatelets produce amplified spontaneous emission with thresholds as low as 6 μJ/cm(2) and gain as high as 600 cm(-1), both a significant improvement over colloidal nanocrystals; in addition, gain saturation occurs at pump fluences 2 orders of magnitude higher than the threshold. We attribute this exceptional performance to large optical cross-sections, slow Auger recombination rates, and narrow ensemble emission line widths.

Picosecond energy transfer and multiexciton transfer outpaces Auger recombination in binary CdSe nanoplatelet solids

Fluorescence resonance energy transfer (FRET) enables photosynthetic light harvesting, wavelength downconversion in light-emitting diodes (LEDs), and optical biosensing schemes. The rate and efficiency of this donor to acceptor transfer of excitation between chromophores dictates the utility of FRET and can unlock new device operation motifs including quantum-funnel solar cells, non-contact chromophore pumping from a proximal LED, and markedly reduced gain thresholds. However, the fastest reported FRET time constants involving spherical quantum dots (0.12-1 ns; refs 7-9) do not outpace biexciton Auger recombination (0.01-0.1 ns; ref. 10), which impedes multiexciton-driven applications including electrically pumped lasers and carrier-multiplication-enhanced photovoltaics. Few-monolayer-thick semiconductor nanoplatelets (NPLs) with tens-of-nanometre lateral dimensions exhibit intense optical transitions and hundreds-of-picosecond Auger recombination, but heretofore lack FRET characterizations. We examine binary CdSe NPL solids and show that interplate FRET (∼6-23 ps, presumably for co-facial arrangements) can occur 15-50 times faster than Auger recombination and demonstrate multiexcitonic FRET, making such materials ideal candidates for advanced technologies.

Red, Yellow, Green, and Blue Amplified Spontaneous Emission and Lasing Using Colloidal CdSe Nanoplatelets

There have been multiple demonstrations of amplified spontaneous emission (ASE) and lasing using colloidal semiconductor nanocrystals. However, it has been proven difficult to achieve low thresholds suitable for practical use of nanocrystals as gain media. Low-threshold blue ASE and lasing from nanocrystals is an even more challenging task. Here, we show that colloidal nanoplatelets (NPLs) with electronic structure of quantum wells can produce ASE in the red, yellow, green, and blue regions of the visible spectrum with low thresholds and high gains. In particular, for blue-emitting NPLs, the ASE threshold is 50 μJ/cm(2), lower than any reported value for nanocrystals. We then demonstrate red, yellow, green, and blue lasing using NPLs with different thicknesses. We find that the lateral size of NPLs does not show any strong effect on the Auger recombination rates and, correspondingly, on the ASE threshold or gain saturation. This observation highlights the qualitative difference of multiexciton dynamics in CdSe NPLs and other quantum-confined CdSe materials, such as quantum dots and rods. Our measurements of the gain bandwidth and gain lifetime further support the prospects of colloidal NPLs as solution-processed optical gain materials.

Assessment of Anisotropic Semiconductor Nanorod and Nanoplatelet Heterostructures with Polarized Emission for Liquid Crystal Display Technology

Semiconductor nanorods can emit linear-polarized light at efficiencies over 80%. Polarization of light in these systems, confirmed through single-rod spectroscopy, can be explained on the basis of the anisotropy of the transition dipole moment and dielectric confinement effects. Here we report emission polarization in macroscopic semiconductor-polymer composite films containing CdSe/CdS nanorods and colloidal CdSe nanoplatelets. Anisotropic nanocrystals dispersed in polymer films of poly butyl-co-isobutyl methacrylate (PBiBMA) can be stretched mechanically in order to obtain unidirectionally aligned arrays. A high degree of alignment, corresponding to an orientation factor of 0.87, was achieved and large areas demonstrated polarized emission, with the contrast ratio I∥/I⊥ = 5.6, making these films viable candidates for use in liquid crystal display (LCD) devices. To some surprise, we observed significant optical anisotropy and emission polarization for 2D CdSe nanoplatelets with the electronic structure of quantum wells. The aligned nanorod arrays serve as optical funnels, absorbing unpolarized light and re-emitting light from deep-green to red with quantum efficiencies over 90% and high degree of linear polarization. Our results conclusively demonstrate the benefits of anisotropic nanostructures for LCD backlighting. The polymer films with aligned CdSe/CdS dot-in-rod and rod-in-rod nanostructures show more than 2-fold enhancement of brightness compared to the emitter layers with randomly oriented nanostructures. This effect can be explained as the combination of linearly polarized luminescence and directional emission from individual nanostructures.

Direct optical lithography of functional inorganic nanomaterials

Patterning without polymers Nanoscale patterning usually requires multiple steps to mask, pattern, and develop sequential layers. One overriding concern is to obtain compatibility between all the materials, as well as the patterning techniques used, to ensure accurate and clean processing. Wang et al. use light-responsive ligands to change the solubility of nanocrystals in specific solvents, so that development can be done by simple redispersion of nanocrystals in dark regions (see the Perspective by Striccoli). The process can fully utilize the advantages of conventional semiconductor processing, but without the need for photoresists, because the nanocrystals are only deposited where they are exposed to light. Science, this issue p. 385; see also p. 353 Inorganic ligand ion pairs allow for polymer-free optical patterning of inorganic materials. Photolithography is an important manufacturing process that relies on using photoresists, typically polymer formulations, that change solubility when illuminated with ultraviolet light. Here, we introduce a general chemical approach for photoresist-free, direct optical lithography of functional inorganic nanomaterials. The patterned materials can be metals, semiconductors, oxides, magnetic, or rare earth compositions. No organic impurities are present in the patterned layers, which helps achieve good electronic and optical properties. The conductivity, carrier mobility, dielectric, and luminescence properties of optically patterned layers are on par with the properties of state-of-the-art solution-processed materials. The ability to directly pattern all-inorganic layers by using a light exposure dose comparable with that of organic photoresists provides an alternate route for thin-film device manufacturing.

Auger-Limited Carrier Recombination and Relaxation in CdSe Colloidal Quantum Wells.

Using time-resolved photoluminescence spectroscopy, we show that two-exciton Auger recombination dominates carrier recombination and cooling dynamics in CdSe nanoplatelets, or colloidal quantum wells. The electron-hole recombination rate depends only on the number of electron-hole pairs present in each nanoplatelet, and is consistent with a two-exciton recombination process over a wide range of exciton densities. The carrier relaxation rate within the conduction and valence bands also depends only on the number of electron-hole pairs present, apart from an initial rapid decay, and is consistent with the cooling rate being limited by reheating due to Auger recombination processes. These Auger-limited recombination and relaxation dynamics are qualitatively different from the carrier dynamics in either colloidal quantum dots or epitaxial quantum wells.

Colloidal CdSe Quantum Rings

Semiconductor quantum rings are of great fundamental interest because their non-trivial topology creates novel physical properties. At the same time, toroidal topology is difficult to achieve for colloidal nanocrystals and epitaxially grown semiconductor nanostructures. In this work, we introduce the synthesis of luminescent colloidal CdSe nanorings and nanostructures with double and triple toroidal topology. The nanorings form during controlled etching and rearrangement of two-dimensional nanoplatelets. We discuss a possible mechanism of the transformation of nanoplatelets into nanorings and potential utility of colloidal nanorings for magneto-optical (e.g., Aharonov-Bohm effect) and other applications.

Probing the Surface of Colloidal Nanomaterials with Potentiometry in Situ

Colloidal nanomaterials represent an important branch of modern chemistry. However, we have very little understanding of molecular processes that occur at the nanocrystal (NC) surface during synthesis and post-synthetic modifications. Here we show that potentiometry can be used to study the surface of colloidal NCs under realistic reaction conditions. Potentiometric titrations of CdSe and InP nanostructures provide information on the active surface area, the affinity of ligands to the NC surface, and the surface reaction kinetics. These studies can be carried out at different temperatures in polar and nonpolar media for NCs of different sizes and shapes. In situ potentiometry can provide real-time feedback during synthesis of core-shell nanostructures.

A room temperature continuous-wave nanolaser using colloidal quantum wells

Colloidal semiconductor nanocrystals have emerged as promising active materials for solution-processable optoelectronic and light-emitting devices. In particular, the development of nanocrystal lasers is currently experiencing rapid progress. However, these lasers require large pump powers, and realizing an efficient low-power nanocrystal laser has remained a difficult challenge. Here, we demonstrate a nanolaser using colloidal nanocrystals that exhibits a threshold input power of less than 1 μW, a very low threshold for any laser using colloidal emitters. We use CdSe/CdS core-shell nanoplatelets, which are efficient nanocrystal emitters with the electronic structure of quantum wells, coupled to a photonic-crystal nanobeam cavity that attains high coupling efficiencies. The device achieves stable continuous-wave lasing at room temperature, which is essential for many photonic and optoelectronic applications. Our results show that colloidal nanocrystals are suitable for compact and efficient optoelectronic devices based on versatile and inexpensive solution-processable materials.Colloidal nanocrystals are a promising material for easy-to-fabricate nanolasers, but suffer from high threshold powers. Here, the authors combine colloidal quantum wells with a photonic-crystal cavity into a stable, continuous-wave room-temperature nanolaser with a threshold below one microwatt

Size-Dependent Biexciton Quantum Yields and Carrier Dynamics of Quasi-Two-Dimensional Core/Shell Nanoplatelets

Quasi-two-dimensional nanoplatelets (NPLs) possess fundamentally different excitonic properties from zero-dimensional quantum dots. We study lateral size-dependent photon emission statistics and carrier dynamics of individual NPLs using second-order photon correlation (g(2)(τ)) spectroscopy and photoluminescence (PL) intensity-dependent lifetime analysis. Room-temperature radiative lifetimes of NPLs can be derived from maximum PL intensity periods in PL time traces. It first decreases with NPL lateral size and then stays constant, deviating from the electric dipole approximation. Analysis of the PL time traces further reveals that the single exciton quantum yield in NPLs decreases with NPL lateral size and increases with protecting shell thickness, indicating the importance of surface passivation on NPL emission quality. Second-order photon correlation (g(2)(τ)) studies of single NPLs show that the biexciton quantum yield is strongly dependent on the lateral size and single exciton quantum yield of the NPLs. In large NPLs with unity single exciton quantum yield, the corresponding biexciton quantum yield can reach unity. These findings reveal that by careful growth control and core-shell material engineering, NPLs can be of great potential for light amplification and integrated quantum photonic applications.