Sohee Jeong

Steric-Hindrance-Driven Shape Transition in PbS Quantum Dots: Understanding Size-Dependent Stability

Ambient stability of colloidal nanocrystal quantum dots (QDs) is imperative for low-cost, high-efficiency QD photovoltaics. We synthesized air-stable, ultrasmall PbS QDs with diameter (D) down to 1.5 nm, and found an abrupt transition at D ≈ 4 nm in the air stability as the QD size was varied from 1.5 to 7.5 nm. X-ray photoemission spectroscopy measurements and density functional theory calculations reveal that the stability transition is closely associated with the shape transition of oleate-capped QDs from octahedron to cuboctahedron, driven by steric hindrance and thus size-dependent surface energy of oleate-passivated Pb-rich QD facets. This microscopic understanding of the surface chemistry on ultrasmall QDs, up to a few nanometers, should be very useful for precisely and accurately controlling physicochemical properties of colloidal QDs such as doping polarity, carrier mobility, air stability, and hot-carrier dynamics for solar cell applications.

Photoenhancement of a Quantum Dot Nanocomposite via UV Annealing and its Application to White LEDs

IO N Colloidal semiconductor quantum dots (QDs) have attracted a great deal of attention due to their unique physical characteristics such as nanometer scale size, size-tunable optical properties, high photostability, and wide absorption spectrum. Various QD applications such as biological imaging, photovoltaic device, light-emitting diode (LED), and memory have been widely studied in science and engineering. [ 1–8 ]

Ultrastable PbSe Nanocrystal Quantum Dots via in Situ Formation of Atomically Thin Halide Adlayers on PbSe(100)

The fast degradation of lead selenide (PbSe) nanocrystal quantum dots (NQDs) in ambient conditions impedes widespread deployment of the highly excitonic, thus versatile, colloidal NQDs. Here we report a simple in situ post-synthetic halide salt treatment that results in size-independent air stability of PbSe NQDs without significantly altering their optoelectronic characteristics. From TEM, NMR, and XPS results and DFT calculations, we propose that the unprecedented size-independent air stability of the PbSe NQDs can be attributed to the successful passivation of under-coordinated PbSe(100) facets with atomically thin PbX2 (X = Cl, Br, I) adlayers. Conductive films made of halide-treated ultrastable PbSe NQDs exhibit markedly improved air stability and behave as an n-type channel in a field-effect transistor. Our simple in situ wet-chemical passivation scheme will enable broader utilization of PbSe NQDs in ambient conditions in many optoelectronic applications.

Continuous extraction of highly pure metallic single-walled carbon nanotubes in a microfluidic channel

Highly pure metallic single-walled carbon nanotubes were continuously extracted from a mixture of semiconducting and metallic species using a nondestructive, scalable method. Two laminar streams were generated in an H-shaped microfluidic channel with two inlets and two outlets. The flow conditions were carefully controlled to minimize diffusive and convective transport across the boundary between the two flows. Dielectrophoretic force from the embedded electrode at the junction extracted metallic nanotubes from a stream of nanotube suspension toward the other stream of buffer solution without nanotubes. The highly pure metallic and enriched semiconducting nanotubes were obtained simultaneously at each outlet using this novel approach. Excellent selectivity was verified by electrical transport measurement, absorption, and Raman spectroscopic analysis.

Air-Stable and Efficient PbSe Quantum-Dot Solar Cells Based upon ZnSe to PbSe Cation-Exchanged Quantum Dots.

We developed a single step, cation-exchange reaction that produces air-stable PbSe quantum dots (QDs) from ZnSe QDs and PbX2 (X = Cl, Br, or I) precursors. The resulting PbSe QDs are terminated with halide anions and contain residual Zn cations. We characterized the PbSe QDs using UV-vis-NIR absorption, photoluminescence quantum yield spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. Solar cells fabricated from these PbSe QDs obtained an overall best power conversion efficiency of 6.47% at one sun illumination. The solar cell performance without encapsulation remains unchanged for over 50 days in ambient conditions; and after 50 days, the National Renewable Energy Laboratory certification team certified the device at 5.9%.

Efficient electron transfer in functional assemblies of pyridine-modified NQDs on SWNTs

Nanocrystal quantum dot (NQD)/single-walled carbon nanotube (SWNT) hybrid nanomaterials were synthesized, assembled into field effect transistors (FETs) via dielectrophoresis (DEP), and characterized optically and electronically. The pyridine moiety functioned as a short, noncovalent linker between the NQDs and SWNTs and allowed more efficient carrier transfer through the assemblies without deleteriously altering electronic structures. Photoluminescence studies of the resulting assemblies support an efficient carrier transfer process in CdSe-py-SWNTs unlike that of CdSe/ZnS-py-SWNTs. The use of DEP as a means of controlling the assembly process allowed the creation of a SWNT array containing densely packed CdSe NQDs across a 2 mum gap between electrodes. Observations and characterization of the photocurrent, resistivity, gate dependence, and optical properties of these systems suggest efficient electron transfer from photoexcited NQDs to SWNTs.

The Scaling of the Effective Band Gaps in Indium−Arsenide Quantum Dots and Wires

Colloidal InAs quantum wires having diameters in the range of 5-57 nm and narrow diameter distributions are grown from Bi nanoparticles by the solution-liquid-solid (SLS) mechanism. The diameter dependence of the effective band gaps (DeltaE(g)s) in the wires is determined from photoluminescence spectra and compared to the experimental results for InAs quantum dots and rods and to the predictions of various theoretical models. The DeltaE(g) values for InAs quantum dots and wires are found to scale linearly with inverse diameter (d(-1)), whereas the simplest confinement models predict that DeltaE(g) should scale with inverse-square diameter (d(-2)). The difference in the observed and predicted scaling dimension is attributed to conduction-band nonparabolicity induced by strong valence-band-conduction-band coupling in the narrow-gap InAs semiconductor.

Facile synthesis of uniform large-sized InP nanocrystal quantum dots using tris(tert-butyldimethylsilyl)phosphine.

Colloidal III-V semiconductor nanocrystal quantum dots [NQDs] have attracted interest because they have reduced toxicity compared with II-VI compounds. However, the study and application of III-V semiconductor nanocrystals are limited by difficulties in their synthesis. In particular, it is difficult to control nucleation because the molecular bonds in III-V semiconductors are highly covalent. A synthetic approach of InP NQDs was presented using newly synthesized organometallic phosphorus [P] precursors with different functional moieties while preserving the P-Si bond. Introducing bulky side chains in our study improved the stability while facilitating InP formation with strong confinement at a readily low temperature regime (210°C to 300°C). Further shell coating with ZnS resulted in highly luminescent core-shell materials. The design and synthesis of P precursors for high-quality InP NQDs were conducted for the first time, and we were able to control the nucleation by varying the reactivity of P precursors, therefore achieving uniform large-sized InP NQDs. This opens the way for the large-scale production of high-quality Cd-free nanocrystal quantum dots.

Improvement in carrier transport properties by mild thermal annealing of PbS quantum dot solar cells

We studied the effect of post-deposition thermal annealing in the preparation of PbS quantum dot (QD) solar cells. We find an optimal annealing temperature that improves the power conversion efficiency by a factor of 1.5 for different sized QDs with bandgaps of 1.65 and 1.27 eV. We examined the onset of the photocurrent response and correlated that with domain grain growth and find that annealing the PbS QD array at 120 °C causes little change in the PbS QD size, bandgap, and open-circuit voltage and yet leads to an increase in the carrier transport as realized by an improved current response. We also find a decrease in the activation energy of a shallow trap, which also likely contributes to the improvement in the solar cell efficiency.

Thermal behavior of a quantum dot nanocomposite as a color converting material and its application to white LED.

We present a novel nanocomposite, a mixture of a CdSe/CdS/ZnS red quantum dot (QD), an Sr(2)SiO(4):Eu green phosphor and silicone resin for a color converting material. The temperature rise and the optical characteristics of the nanocomposite due to the addition of the QD have been investigated in terms of QD content ratio and the mixing components. The experimental results suggested that a small addition of QDs generated a large amount of heat during light conversion at the wavelength of QD emission. Considering the temperature rise in a nanocomposite, we applied 0.2 wt% QDs on an InGaN blue LED chip. As a result, we could achieve a white LED device with a high color rendering index of 83.2, a high luminance of 65.86 lm W(-1) and a moderate temperature increase of 94 °C. The white LED converted by the newly developed QD-phosphor nanocomposite has great potential in future illumination.