Tailored growth of single-crystalline InP tetrapods.

Despite the technological importance of colloidal covalent III-V nanocrystals with unique optoelectronic properties, their synthetic process still has challenges originating from the complex energy landscape of the reaction. Here, we present InP tetrapod nanocrystals as a crystalline late intermediate in the synthetic pathway that warrants controlled growth. We isolate tetrapod intermediate species with well-defined surfaces of (110) and ([Formula: see text]) via the suppression of further growth. An additional precursor supply at low temperature induces [Formula: see text]-specific growth, whereas the [110]-directional growth occurs over the activation barrier of 65.7 kJ/mol at a higher temperature, thus finalizes into the (111)-faceted tetrahedron nanocrystals. We address the use of late intermediates with well-defined facets at the sub-10 nm scale for the tailored growth of covalent III-V nanocrystals and highlight the potential for the directed approach of nanocrystal synthesis.

III-V colloidal nanocrystals: control of covalent surfaces.

Colloidal quantum dots (QDs) are nanosized semiconductors whose electronic features are dictated by the quantum confinement effect. The optical, electrical, and chemical properties of QDs are influenced by their dimensions and surface landscape. The surface of II-VI and IV-VI QDs has been extensively explored; however, in-depth investigations on the surface of III-V QDs are still lagging behind. This Perspective discusses the current understanding of the surface of III-V QDs, outlines deep trap states presented by surface defects, and suggests strategies to overcome challenges associated with deep traps. Lastly, we discuss a route to create well-defined facets in III-V QDs by providing a platform for surface studies and a recently reported approach in atomistic understanding of covalent III-V QD surfaces using the electron counting model with fractional dangling bonds.

Energy level tuned indium arsenide colloidal quantum dot films for efficient photovoltaics.

We introduce indium arsenide colloidal quantum dot films for photovoltaic devices, fabricated by two-step surface modification. Native ligands and unwanted oxides on the surface are peeled off followed by passivating with incoming atomic or short ligands. The near-infrared-absorbing n-type indium arsenide colloidal quantum dot films can be tuned in energy-level positions up to 0.4 eV depending on the surface chemistry, and consequently, they boost collection efficiency when used in various emerging solar cells. As an example, we demonstrate p-n junction between n-type indium arsenide and p-type lead sulfide colloidal quantum dot layers, which leads to a favorable electronic band alignment and charge extraction from both colloidal quantum dot layers. A certified power conversion efficiency of 7.92% is achieved without additionally supporting carrier transport layers. This study provides richer materials to explore for high-efficiency emerging photovoltaics and will broaden research interest for various optoelectronic applications using the n-type covalent nanocrystal arrays.

Enhancement of Hot Electron Flow in Plasmonic Nanodiodes by Incorporating PbS Quantum Dots.

The enhancement of hot electron generation using plasmonic nanostructures is a promising strategy for developing photovoltaic devices. Here, we show that hot electron flow generated in plasmonic Au/TiO2 nanodiodes by incident light can be amplified when PbS quantum dots are deposited onto the surface of the nanodiodes. The effect is attributed to efficient extraction of hot electrons via a three-dimensional Schottky barrier, thus giving new pathways for hot electron transfer. We also demonstrate a correlation between the photocurrent and Schottky barrier height when using PbS quantum dots with varying size and ligand treatments that allow us to control the electric properties (e.g., band gap and Fermi level, respectively) of the PbS quantum dots. This simple method introduces a new technique for further improving the power conversion efficiency of thin-film photovoltaic devices.

Facet-Specific Ligand Interactions on Ternary AgSbS2 Colloidal Quantum Dots.

Silver dimetal chalcogenide (Ag-V-VI2 ) ternary quantum dots (QDs) are emerging lead-free materials for optoelectronic devices due to their NIR band gaps, large absorption coefficients, and superior electronic properties. However, thin film-based devices of the ternary QDs still lag behind due to the lack of understanding of the surface chemistry, compared to that of lead chalcogenide QDs even with the same crystal structure. Herein the surface ligand interactions of AgSbS2 QDs, synthesized with 1-dodecanethiol used as a stabilizer, are studied. For nonpolar (1 0 0) surfaces, it is suggested that the thiolate ligands are associated with the crystal lattices, thus preventing surface oxidation by protecting sulfur after air-exposure, as confirmed through optical and surface chemical analysis. Otherwise, silver rich (1 1 1) surfaces are passivated by thiolate ligands, allowing ligand exchange processes for the conductive films. This in-depth investigation of the surface chemistry of ternary QDs will prompt the performance enhancement of their optoelectronic devices.

Supersonically Spray-Coated Colloidal Quantum Dot Ink Solar Cells.

Controlling the thickness of quantum dot (QD) films is difficult using existing film formation techniques, which employ pre-ligand-exchanged PbS QD inks, because of several issues: 1) poor colloidal stability, 2) use of high-boiling-point solvents for QD dispersion, and 3) limitations associated with one-step deposition. Herein, we suggest a new protocol for QD film deposition using electrical double-layered PbS QD inks, prepared by solution-phase ligand exchange using methyl ammonium lead iodide (MAPbI3). The films are deposited by the supersonic spraying technique, which facilitates the rapid evaporation of the solvent and the subsequent deposition of the PbS QD ink without requiring a post-deposition annealing treatment for solvent removal. The film thickness could be readily controlled by varying the number of spraying sweeps made across the substrate. This spray deposition process yields high-quality n-type QD films quickly (within 1 min) while minimizing the amount of the PbS QD ink used to less than 5 mg for one device (300-nm-thick absorbing layer, 2.5 × 2.5 cm2). Further, the formation of an additional p-layer by treatment with mercaptopropionic acid allows for facile hole extraction from the QD films, resulting in a power conversion efficiency of 3.7% under 1.5 AM illumination.

Halide-Amine Co-Passivated Indium Phosphide Colloidal Quantum Dots in Tetrahedral Shape.

Wet chemical synthesis of covalent III-V colloidal quantum dots (CQDs) has been challenging because of uncontrolled surfaces and a poor understanding of surface-ligand interactions. We report a simple acid-free approach to synthesize highly crystalline indium phosphide CQDs in the unique tetrahedral shape by using tris(dimethylamino) phosphine and indium trichloride as the phosphorus and indium precursors, dissolved in oleylamine. Our chemical analyses indicate that both the oleylamine and chloride ligands participate in the stabilization of tetrahedral-shaped InP CQDs covered with cation-rich (111) facets. Based on density functional theory calculations, we propose that fractional dangling electrons of the In-rich (111) surface could be completely passivated by three halide and one primary amine ligands per the (2×2) surface unit, satisfying the 8-electron rule. This halide-amine co-passivation strategy will benefit the synthesis of stable III-V CQDs with controlled surfaces.

High performance of PbSe/PbS core/shell quantum dot heterojunction solar cells: short circuit current enhancement without the loss of open circuit voltage by shell thickness control.

We fabricated heterojunction solar cells with PbSe/PbS core shell quantum dots and studied the precisely controlled PbS shell thickness dependency in terms of optical properties, electronic structure, and solar cell performances. When the PbS shell thickness increases, the short circuit current density (JSC) increases from 6.4 to 11.8 mA cm(-2) and the fill factor (FF) enhances from 30 to 49% while the open circuit voltage (VOC) remains unchanged at 0.46 V even with the decreased effective band gap. We found that the Fermi level and the valence band maximum level remain unchanged in both the PbSe core and PbSe/PbS core/shell with a less than 1 nm thick PbS shell as probed via ultraviolet photoelectron spectroscopy (UPS). The PbS shell reduces their surface trap density as confirmed by relative quantum yield measurements. Consequently, PbS shell formation on the PbSe core mitigates the trade-off relationship between the open circuit voltage and the short circuit current density. Finally, under the optimized conditions, the PbSe core with a 0.9 nm thick shell yielded a power conversion efficiency of 6.5% under AM 1.5.

Synthesis of colloidal InSb nanocrystals via in situ activation of InCl3.

Indium antimonide (InSb), a narrow band gap III-V semiconductor is a promising infrared-active material for various optoelectronic applications. Synthetic challenge of colloidal InSb nanocrystals (NCs) lies in the limited choice of precursors. Only a few successful synthetic schemes involving highly toxic stibine (SbH3) or air- and moisture-sensitive metal silylamides (In[N(Si-(Me)3)2]3 or Sb[N(Si-(Me)3)2]3) as the precursor have been reported. We found that commercially available precursors InCl3 and Sb[NMe2]3 directly form highly crystalline colloidal InSb nanocrystals in the presence of a base such as LiN(SiMe3)2 or nBuLi. The mean size of the particles can be controlled by simply changing the activating base. This approach offers a one-pot synthesis of InSb NCs from readily available chemicals without the use of complex organometallic precursors.

Continuous flow purification of nanocrystal quantum dots.

Colloidal quantum dot (QD) purification is typically conducted via repeating precipitation-redispersion involving massive amounts of organic solvents and has been the main obstacle in mass production of QDs with dependable surface properties. Our results show that the electric field apparently affects the streamlining of QDs and that we could continuously collect stably dispersed QDs by the electrophoretic purification process. The purification yield increases as the electric potential difference increases or the flow rate decreases, but reaches an asymptotic value. The yield can be further improved by raising the absolute magnitude of the mobility of QDs with the addition of solvents with high dielectric constants. The continuous purification process sheds light on industrial production of colloidal nanomaterials.

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.

One-Step Deposition of Photovoltaic Layers Using Iodide Terminated PbS Quantum Dots.

We present a one-step layer deposition procedure employing ammonium iodide (NH4I) to achieve photovoltaic quality PbS quantum dot (QD) layers. Ammonium iodide is used to replace the long alkyl organic native ligands binding to the QD surface resulting in iodide terminated QDs that are stabilized in polar solvents such as N,N-dimethylformamide without particle aggregation. We extensively characterized the iodide terminated PbS QD via UV-vis absorption, transmission electron microscopy (TEM), thermogravimetric analysis (TGA), FT-IR transmission spectroscopy, and X-ray photoelectron spectroscopy (XPS). Finally, we fabricated PbS QD photovoltaic cells that employ the iodide terminated PbS QDs. The resulting QD-PV devices achieved a best power conversion efficiency of 2.36% under ambient conditions that is limited by the layer thickness. The PV characteristics compare favorably to similar devices that were prepared using the standard layer-by-layer ethandithiol (EDT) treatment that had a similar layer thickness.

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.

Notochordal cells influence gene expression of inflammatory mediators of annulus fibrosus cells in proinflammatory cytokines stimulation.

OBJECTIVE: Notochordal cells in the intervertebral disc interact with nucleus pulposus (NP) cells and support the maintenance of disc homeostasis by regulation of matrix production. However, the influence of notochordal cells has not been evaluated in the annulus fibrosus (AF), which is the primary pain generator in the disc. We hypothesized that the notochordal cell has the capacity to modulate inflammatory mediators secreted by AF cells secondary to stimulation. METHODS: Notochordal and AF cells were isolated from adult New Zealand white rabbits. AF pellets were cultured with notochordal cell clusters or in notochordal cell-conditioned media (NCCM) for 24 or 48 hours with proinflammatory cytokines at varying concentrations. Gene expression in AF pellets were assayed for nitric oxide synthase (iNOS), cyclo-oxygenase (COX)-2, and interleukin (IL)-6 by real time reverse transcriptase polymerase chain reaction (RT-PCR). RESULTS: AF pellet in NCCM significantly decreased the iNOS and COX-2 messenger ribonucleic acid (mRNA) levels compared to AF pellets alone and AF pellets with notochordal cells (p < 0.05). AF pellet resulted in dose-dependent iNOS and COX-2 expression in response to IL-1beta, stimulation, demonstrating that 1 ng/ml for 24 hours yielded a maximal response. AF pellet in NCCM significantly decreased the expression of iNOS and COX-2 in response to 1ng/ml IL-1beta, stimulation at 24 hours (p < 0.05). There was no difference in IL-6 expression compared to AF pellets alone or AF pellets with notochordal cell clusters. CONCLUSION: We conclude that soluble factors from notochordal cells mitigate the gene expression of inflammatory mediators in stimulated AF, as expected after annular injury, suggesting that notochordal cells could serve as a novel therapeutic approach in symptomatic disc development.