Emerging Atomic Energy Levels in Zero-Dimensional Silicon Quantum Dots.

Driven by the emergence of colloidal semiconductor quantum dots (QDs) of tunable emission wavelengths, characteristic of exciton absorption peaks, outstanding photostability and solution processability in device fabrication have become a key tool in the development of nanomedicine and optoelectronics. Diamond cubic crystalline silicon (Si) QDs, with a diameter larger than 2 nm, terminated with hydrogen atoms are known to exhibit bulk-inherited spin and valley properties. Herein, we demonstrate a newly discovered size region of Si QDs, in which a fast radiative recombination on the order of hundreds of picoseconds is responsible for photoluminescence (PL). Despite retaining a crystallographic structure like the bulk, controlling their diameters in the 1.1-1.7 nm range realizes the strong PL with continuous spectral tunability in the 530-580 nm window, the narrow spectral line widths without emission tails, and the fast relaxation of photogenerated carriers. In contrast, QDs with diameters greater than 1.8 nm display the decay times on the microsecond order as well as the previous Si QDs. In addition to the five-orders-of-magnitude variation in the PL decay time, a systematic study on the temperature dependence of PL properties suggests that the energy structure of the smaller QDs does not retain an indirect band gap character. It is discussed that a 1.7 nm diameter is critical to undergo changes in energy structure from bulky to molecular configurations.

Reductant-free colloidal synthesis of near-IR emitting germanium nanocrystals: role of primary amine.

High temperature colloidal synthesis without using hazardous reducing agent is demonstrated here to develop a straight forward pathway for synthesizing near-IR (NIR) light emitting germanium nanocrystals (Ge NCs). The NCs were prepared by heating a mixture of germanium (II) iodide and organoamine. This article presents an important role of the primary amine which serves as a reducing agent as well as an inhibitor against oxidation by comparing with the tertiary amine. Interestingly, the difference in chemical reactivity between each amine causes the difference in major structural phase of the products. An efficient route to produce NIR light emitting Ge NCs is demonstrated.

Colloidal silicon quantum dots: synthesis and luminescence tuning from the near-UV to the near-IR range.

This review describes a series of representative synthesis processes, which have been developed in the last two decades to prepare silicon quantum dots (QDs). The methods include both top-down and bottom-up approaches, and their methodological advantages and disadvantages are presented. Considerable efforts in surface functionalization of QDs have categorized it into (i) a two-step process and (ii) in situ surface derivatization. Photophysical properties of QDs are summarized to highlight the continuous tuning of photoluminescence color from the near-UV through visible to the near-IR range. The emission features strongly depend on the silicon nanostructures including QD surface configurations. Possible mechanisms of photoluminescence have been summarized to ascertain the future challenges toward industrial use of silicon-based light emitters.

Controlled electrostatic assembly of quantum dots vis-à-vis their electronic coupling and transport gap.

We correlate the electronic coupling between quantum dots and the transport gap of nanoparticle-passivated Si substrates. We vary the length of the stabilizers of CdS nanoparticles, which in turn alters the particle-to-particle separation and hence the electronic coupling between them. We also control the electronic coupling using time-restricted electrostatic-assembly of quantum dots, using short periods of time so that an incomplete monolayer or a sub-monolayer of CdS forms. In such a sub-monolayer, the nanoparticles remain isolated from each other with a controllable particle-to-particle separation. From electronic absorption spectroscopy of multilayer films and atomic force microscopy of a monolayer, we evidenced sub-monolayer formation in the controlled electrostatic assembly process. We measure the current-voltage characteristics of nanoparticle-passivated substrates with a scanning tunnelling microscope; we show that the transport gap of nanoparticle-passivated substrates depends on the electronic coupling between CdS particles in the monolayer.

High Aspect Ratio and Post-Processing Free Silver Nanowires as Top Electrodes for Inverted-Structured Photodiodes.

Silver nanowires (Ag NWs) as transparent conducting electrodes are widely used in many applications such as organic light-emitting diodes (OLEDs), polymer light-emitting diodes, touch screens, solar cells, and transparent heaters. In this work, using a large-scale synthesis, the synthesized Ag NWs had a high aspect ratio of 2820. The Ag NWs could be applied as a top transparent electrode in a device by simple drop-casting without any post-processing steps. The fabricated device comprised 4,4'-bis(carbazol-9-yl)biphenyl/MoO3 organic/inorganic layers which are parts of the inverted structure OLEDs or solar cells. The photodiode characteristics at the UV range were observed in the device. The ability of Ag NWs to replace opaque metals as top electrodes in a device has been demonstrated.

Inverted Device Architecture for Enhanced Performance of Flexible Silicon Quantum Dot Light-Emitting Diode.

Here we report for the first time highly flexible quantum dot light-emitting diodes (QLEDs), in which a layer of red-emitting colloidal silicon quantum dots (SiQDs) works as the optically active component, by replacing a rigid glass substrate with a thin sheet of polyethylene terephthalate (PET). The enhanced optical performance for electroluminescence (EL) at room temperature in air is achieved by taking advantage of the inverted device structure. Our QLEDs do not exhibit parasitic EL emissions from the neighboring compositional layers or surface states of QDs over a wide range of driving voltages and do not exhibit a shift in the EL peak position as the operational voltage increases. Compared to the previous Si-QLEDs with a conventional device structure, our QLED has a longer device operational lifetime and a long-lived EQE value. The currently obtained brightness (∼5000 cd/m2), the 3.1% external quantum efficiency (EQE), and a turn-on voltage as low as 3.5 V are sufficiently high to encourage further developments of Si-QLEDs.

Origin of the Photoluminescence Quantum Yields Enhanced by Alkane-Termination of Freestanding Silicon Nanocrystals: Temperature-Dependence of Optical Properties.

On the basis of the systematic study on temperature dependence of photoluminescence (PL) properties along with relaxation dynamics we revise a long-accepted mechanism for enhancing absolute PL quantum yields (QYs) of freestanding silicon nanocrystals (ncSi). A hydrogen-terminated ncSi (ncSi:H) of 2.1 nm was prepared by thermal disproportination of (HSiO1.5)n, followed by hydrofluoric etching. Room-temperature PL QY of the ncSi:H increased twentyfold only by hydrosilylation of 1-octadecene (ncSi-OD). A combination of PL spectroscopic measurement from cryogenic to room temperature with structural characterization allows us to link the enhanced PL QYs with the notable difference in surface structure between the ncSi:H and the ncSi-OD. The hydride-terminated surface suffers from the presence of a large amount of nonradiative relaxation channels whereas the passivation with alkyl monolayers suppresses the creation of the nonradiative relaxation channels to yield the high PL QY.

Functional double-shelled silicon nanocrystals for two-photon fluorescence cell imaging: spectral evolution and tuning.

Functional near-IR (NIR) emitting nanoparticles (NPs) adapted for two-photon excitation fluorescence cell imaging were obtained starting from octadecyl-terminated silicon nanocrystals (ncSi-OD) of narrow photoluminescence (PL) spectra having no long emission tails, continuously tunable over the 700-1000 nm window, PL quantum yields exceeding 30%, and PL lifetimes of 300 µs or longer. These NPs, consisting of a Pluronic F127 shell and a core made up of assembled ncSi-OD kept apart by an octadecyl (OD) layer, were readily internalized into the cytosol, but not the nucleus, of NIH3T3 cells and were non-toxic. Asymmetrical field-flow fractionation (AF4) analysis was carried out to determine the size of the NPs in water. HiLyte Fluor 750 amine was linked via an amide link to NPs prepared with Pluronic-F127-COOH, as a first demonstration of functional NIR-emitting water dispersible ncSi-based nanoparticles.

Atomic water channel controlling remarkable properties of a single brain microtubule: correlating single protein to its supramolecular assembly.

Microtubule nanotubes are found in every living eukaryotic cells; these are formed by reversible polymerization of the tubulin protein, and their hollow fibers are filled with uniquely arranged water molecules. Here we measure single tubulin molecule and single brain-neuron extracted microtubule nanowire with and without water channel inside to unravel their unique electronic and optical properties for the first time. We demonstrate that the energy levels of a single tubulin protein and single microtubule made of 40,000 tubulin dimers are identical unlike conventional materials. Moreover, the transmitted ac power and the transient fluorescence decay (single photon count) are independent of the microtubule length. Even more remarkable is the fact that the microtubule nanowire is more conducting than a single protein molecule that constitutes the nanowire. Microtubule's vibrational peaks condense to a single mode that controls the emergence of size independent electronic/optical properties, and automated noise alleviation, which disappear when the atomic water core is released from the inner cylinder. We have carried out several tricky state-of-the-art experiments and identified the electromagnetic resonance peaks of single microtubule reliably. The resonant vibrations established that the condensation of energy levels and periodic oscillation of unique energy fringes on the microtubule surface, emerge as the atomic water core resonantly integrates all proteins around it such that the nanotube irrespective of its size functions like a single protein molecule. Thus, a monomolecular water channel residing inside the protein-cylinder displays an unprecedented control in governing the tantalizing electronic and optical properties of microtubule.

Efficient Dual-Modal NIR-to-NIR Emission of Rare Earth Ions Co-doped Nanocrystals for Biological Fluorescence Imaging.

A novel approach has been developed for the realization of efficient near-infrared to near-infrared (NIR-to-NIR) upconversion and down-shifting emission in nanophosphors. The efficient dual-modal NIR-to-NIR emission is realized in a ß-NaGdF4/Nd(3+)@NaGdF4/Tm(3+)-Yb(3+) core-shell nanocrystal by careful control of the identity and concentration of the doped rare earth (RE) ion species and by manipulation of the spatial distributions of these RE ions. The photoluminescence results reveal that the emission efficiency increases at least 2-fold when comparing the materials synthesized in this study with those synthesized through traditional approaches. Hence, these core-shell structured nanocrystals with novel excitation and emission behaviors enable us to obtain tissue fluorescence imaging by detecting the upconverted and down-shifted photoluminescence from Tm(3+) and Nd(3+) ions, respectively. The reported approach thus provides a new route for the realization of high-yield emission from RE ion doped nanocrystals, which could prove to be useful for the design of optical materials containing other optically active centers.