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Quantum-confined states of semiconductor nanocrystals offer unique opportunities for selective light-activated photochemistry and generation of specific reactive oxygen (ROS) and nitrogen (RNS) species. Recently, assessment of different ROS and RNS species identified intracellular light-activated superoxide as the prime candidate for selective nanotherapeutic treatments in countering the threat of multidrug-resistant (MDR) pathogens. Here, we show that by carefully tuning the composition of ternary zinc cadmium telluride (Zn 1- x Cd x Te) quantum dots (QDs), we can engineer the bandgap, electronic states, and the resultant reduction and oxidation potentials, thereby changing the light-activated superoxide generation by these QDs. Using QDs with low cadmium content as alternative candidates for selective light-activated therapy, we show negligible toxicity of these QDs to mammalian cells while maintaining high treatment efficacy against MDR pathogens. These low nanomolar doses of QDs required for therapeutic intervention contain less cadmium than other environmental factors like consuming tubular potatoes, leafy vegetables, animal meat, or even fresh water, further alleviating concerns of elemental toxicity. These results provide design principles for developing different QDs as selective therapeutics to counter the growing threat of antimicrobial-resistant infections.

Several nanoscale electronic methods have been proposed for high-throughput single-molecule nucleic acid sequence identification. While many studies display a large ensemble of measurements as "electronic fingerprints" with some promise for distinguishing the DNA and RNA nucleobases (adenine, guanine, cytosine, thymine, and uracil), important metrics such as accuracy and confidence of base calling fall well below the current genomic methods. Issues such as unreliable metal-molecule junction formation, variation of nucleotide conformations, insufficient differences between the molecular orbitals responsible for single-nucleotide conduction, and lack of rigorous base calling algorithms lead to overlapping nanoelectronic measurements and poor nucleotide discrimination, especially at low coverage on single molecules. Here, we demonstrate a technique for reproducible conductance measurements on conformation-constrained single nucleotides and an advanced algorithmic approach for distinguishing the nucleobases. Our quantum point contact single-nucleotide conductance sequencing (QPICS) method uses combed and electrostatically bound single DNA and RNA nucleotides on a self-assembled monolayer of cysteamine molecules. We demonstrate that by varying the applied bias and pH conditions, molecular conductance can be switched ON and OFF, leading to reversible nucleotide perturbation for electronic recognition (NPER). We utilize NPER as a method to achieve >99.7% accuracy for DNA and RNA base calling at low molecular coverage (∼12×) using unbiased single measurements on DNA/RNA nucleotides, which represents a significant advance compared to existing sequencing methods. These results demonstrate the potential for utilizing simple surface modifications and existing biochemical moieties in individual nucleobases for a reliable, direct, single-molecule, nanoelectronic DNA and RNA nucleotide identification method for sequencing.

We present a novel plasmonic antenna structure, a split-wedge antenna, created by splitting an ultrasharp metallic wedge with a nanogap perpendicular to its apex. The nanogap can tightly confine gap plasmons and boost the local optical field intensity in and around these opposing metallic wedge tips. This three-dimensional split-wedge antenna integrates the key features of nanogaps and sharp tips, i.e., tight field confinement and three-dimensional nanofocusing, respectively, into a single platform. We fabricate split-wedge antennas with gaps that are as small as 1 nm in width at the wafer scale by combining silicon V-grooves with template stripping and atomic layer lithography. Computer simulations show that the field enhancement and confinement are stronger at the tip-gap interface compared to what standalone tips or nanogaps produce, with electric field amplitude enhancement factors exceeding 50 when near-infrared light is focused on the tip-gap geometry. The resulting nanometric hotspot volume is on the order of λ 3 /10 6 . Experimentally, Raman enhancement factors exceeding 10 7 are observed from a 2 nm gap split-wedge antenna, demonstrating its potential for sensing and spectroscopy applications.

Several nanoelectronic techniques have been explored to distinguish the sequence of nucleic acids in DNA macromolecules. Identification of unique electronic signatures using nanopore conductance, tunneling spectroscopy, or other nanoelectronic techniques depends on electronic states of the DNA nucleotides. While several experimental and computational studies have focused on interaction of nucleobases with different substrates, the effect of nucleic acid biochemistry on its electronic properties has been largely unexplored. Here, we present correlated measurements of frontier molecular orbitals and higher-order electronic states for four DNA nucleobases (adenine, cytosine, thymine, and guanine), and first-principle quantum chemical density functional theoretical (DFT) computations. Using different pH conditions in our experiments, we show that small changes in the biochemical state of these nucleic acids strongly affect the intrinsic electronic structure, measured using scanning tunneling spectroscopy (STS). In our experimental measurements and computations, significant differences were observed between the position of frontier orbitals and higher-energy states between protonated and unprotonated nucleic acids, isomers, and different keto-enol tautomer's formed in these nucleotides, leading to their facile identification. Furthermore, we show unique "electronic fingerprints" for all nucleotides (A, G, T, C) using STS, with most distinct states identified at acidic pH. These results can have important implications for identification of nucleic acid sequences in DNA molecules using a high-throughput nanoelectronic identification technique.

Metal-oxide nanotubes provide large surface areas and functionalizable surfaces for a variety of optical and electronic applications. Here we report air-tunable rectifying behavior, depletion width modulation, and two-dimensional (2D) charge conduction in hollow titanium-dioxide nanotubes. The metal contact forms a Schottky-diode in the nanotubes, and the rectification factor (on/off ratio) can be varied by more than 3 orders of magnitude (1-2 × 10(3)) as the air pressure is increased from 2 mTorr to atmospheric pressure. This behavior is explained using a change in depletion width of these thin nanotubes by adsorption of water vapor on both surfaces of a hollow nanotube, and the resulting formation of a metal-insulator-semiconductor (MIS) junction, which controls the 2D charge conduction properties in thin oxide nanotubes.

The development of two-dimensional (2D) nanomaterials has revealed novel physical properties, like high carrier mobilities and the tunable coupling of charge carriers with phonons, which can enable wide-ranging applications in optoelectronic and thermoelectric devices. While mechanical exfoliation of graphene and some transition metal dichalcogenides (e.g., MoS2, WSe2) has enabled their fabrication as 2D semiconductors and integration into devices, lack of similar syntheses for other 2D semiconductor materials has hindered further progress. Here, we report measurements of fundamental charge carrier interactions and optoelectronic properties of 2D nanomaterials made from two-monolayers-thick PbX, CdX, Cu2X, and Ag2X (X = S, Se) using colloidal syntheses. Extremely low coupling of charge carriers with phonons (2-6-fold lower than bulk and other low-dimensional semiconductors), high carrier mobilities (0.2-1.2 cm(2) V(-1) s(-1), without dielectric screening), observation of infrared surface plasmons in ultrathin 2D semiconductor nanostructures, strong quantum-confinement, and other multiexcitonic properties (different phonon coupling and photon-to-charge collection efficiencies for band-edge and higher-energy excitons) can pave the way for efficient solution-processed devices made from these 2D nanostructured semiconductors.

Quantum dots (QDs) are semiconductor nanocrystallites with multiple size-dependent quantum-confined states that are being explored for utilizing broadband radiation. While DNA has been used for the self-assembly of nanocrystals, it has not been investigated for the formation of simultaneous conduction pathways for transporting multiple energy charges or excitons. These exciton shelves can be formed by coupling the conduction band, valence band, and hot-carrier states in QDs with different HOMO-LUMO levels of DNA nucleobases, resulting from varying degrees of conjugation in the nucleobases. Here we present studies on the electronic density of states in four naturally occurring nucleobases (guanine, thymine, cytosine, and adenine), which energetically couple to quantized states in semiconductor QDs. Using scanning tunneling spectroscopy of single nanoparticle-DNA constructs, we demonstrate composite DOS of chemically coupled DNA oligonucleotides and cadmium chalcogenide QDs (CdS, CdSe, CdTe). While perfectly aligned CdTe QD-DNA states lead to exciton shelves for multiple energy charge transport, mismatched energy levels in CdSe QD-DNA introduce intrabandgap states that can lead to charge trapping and recombination. Although further investigations are required to study the rates of charge transfer, recombination, and back-electron transfer, these results can have important implications for the development of a new class of nanobioelectronics and biological transducers.

A rapid increase in anthropogenic emission of greenhouse gases, mainly carbon dioxide, has been a growing cause for concern. While photocatalytic reduction of carbon dioxide (CO2) into solar fuels can provide a solution, lack of insight into energetic pathways governing photocatalysis has impeded study. Here, we utilize measurements of electronic density of states (DOS), using scanning tunneling microscopy/spectroscopy (STM/STS), to identify energy levels responsible for photocatalytic reduction of CO2-water in an artificial photosynthetic process. We introduce desired states in titanium dioxide (TiO2) nanoparticles, using metal dopants or semiconductor nanocrystals, and the designed catalysts were used for selective reduction of CO2 into hydrocarbons, alcohols, and aldehydes. Using a simple model, we provide insights into the photophysics governing this multielectron reduction and design a new composite photocatalyst based on overlapping energy states of TiO2 and copper indium sulfide (CIS) nanocrystals. These nanoparticles demonstrate the highest selectivity for ethane (>70%) and a higher efficiency of converting ultraviolet radiation into fuels (4.3%) using concentrated sunlight (>4 Sun illumination), compared with platinum-doped TiO2 nanoparticles (2.1%), and utilize hot electrons to tune the solar fuel from alkanes to aldehydes. These results can have important implications for the development of new inexpensive photocatalysts with tuned activity and selectivity.

Upconversion of infrared radiation into visible light has been investigated for applications in photovoltaics and biological imaging. However, low conversion efficiency due to small absorption cross-section for infrared light (Yb(3+)), and slow rate of energy transfer (to Er(3+) states) has prevented application of upconversion photoluminescence (UPL) for diffuse sunlight or imaging tissue samples. Here, we utilize resonant surface plasmon polaritons (SPP) waves to enhance UPL in doped-lanthanide nanocrystals. Our analysis indicates that SPP waves not only enhance the electromagnetic field, and hence weak Purcell effect, but also increase the rate of resonant energy transfer from Yb(3+) to Er(3+) ions by 6 fold. While we do observe strong metal mediated quenching (14-fold) of green fluorescence on flat metal surfaces, the nanostructured metal is resonant in the infrared and hence enhances the nanocrystal UPL. This strong Coulombic effect on energy transfer can have important implications for other fluorescent and excitonic systems too.

The template-stripping method can yield smooth patterned films without surface contamination. However, the process is typically limited to coinage metals such as silver and gold because other materials cannot be readily stripped from silicon templates due to strong adhesion. Herein, we report a more general template-stripping method that is applicable to a larger variety of materials, including refractory metals, semiconductors, and oxides. To address the adhesion issue, we introduce a thin gold layer between the template and the deposited materials. After peeling off the combined film from the template, the gold layer can be selectively removed via wet etching to reveal a smooth patterned structure of the desired material. Further, we demonstrate template-stripped multilayer structures that have potential applications for photovoltaics and solar absorbers. An entire patterned device, which can include a transparent conductor, semiconductor absorber, and back contact, can be fabricated. Since our approach can also produce many copies of the patterned structure with high fidelity by reusing the template, a low-cost and high-throughput process in micro- and nanofabrication is provided that is useful for electronics, plasmonics, and nanophotonics.

Inexpensive, reproducible, and high-throughput fabrication of nanometric apertures in metallic films can benefit many applications in plasmonics, sensing, spectroscopy, lithography, and imaging. Here we use template-stripping to pattern periodic nanohole arrays in optically thick, smooth Ag films with a silicon template made via nanoimprint lithography. Ag is a low-cost material with good optical properties, but it suffers from poor chemical stability and biocompatibility. However, a thin silica shell encapsulating our template-stripped Ag nanoholes facilitates biosensing applications by protecting the Ag from oxidation as well as providing a robust surface that can be readily modified with a variety of biomolecules using well-established silane chemistry. The thickness of the conformal silica shell can be precisely tuned by atomic layer deposition, and a 15 nm thick silica shell can effectively prevent fluorophore quenching. The Ag nanohole arrays with silica shells can also be bonded to polydimethylsiloxane (PDMS) microfluidic channels for fluorescence imaging, formation of supported lipid bilayers, and real-time, label-free SPR sensing. Additionally, the smooth surfaces of the template-stripped Ag films enhance refractive index sensitivity compared with as-deposited, rough Ag films. Because nearly centimeter-sized nanohole arrays can be produced inexpensively without using any additional lithography, etching, or lift-off, this method can facilitate widespread applications of metallic nanohole arrays for plasmonics and biosensing., (© 2011 American Chemical Society)

We conduct measurements of photocharging of PbSe and PbS nanocrystal quantum dots (NQDs) as a function of excitation energy (ℏω). We observe a rapid growth of the degree of photocharging with increasing ℏω, which indicates an important role of hot-carrier transfer in the photoionization process. The corresponding spectral dependence exhibits two thresholds that mark the onsets of weak and strong photocharging. Interestingly, both thresholds are linked to the NQD band gap energy (E(g)) and scale as ∼1.5E(g) and ∼3E(g), indicating that the onsets of photoionization are associated with specific nanocrystal states (tentatively, 1P and 2P, respectively) and are not significantly dependent on the energy of external acceptor sites. For all samples, the hot-electron transfer probability increases by nearly 2 orders of magnitude as photon energy increases from 1.5 to 3.5 eV, although at any given wavelength the photoionization probability shows significant sample-to-sample variations (∼10(-6) to 10(-3) for 1.5 eV and ∼10(-4) to 10(-1) for 3.5 eV). In addition to the effect of the NQD size, these variations are likely due to differences in the properties of the NQD surface and/or the number and identity of external acceptor trap sites. The charge-separated states produced by photoionization are characterized by extremely long lifetimes (20 to 85 s) that become longer with increasing NQD size.

We demonstrate three-dimensional plasmonic nanofocusing of light with patterned metallic pyramids obtained via template stripping. Gratings on the faces of these pyramids convert linearly polarized light into plasmons that propagate toward and converge at a approximately 10 nm apex. Experiments and computer simulations confirm that optical energy is focused into a nanoscale volume (5 x 10(-5) wavelength(3)). Because these structures are easily and reproducibly fabricated, our results could benefit many applications, including imaging, sensing, lithography, and nonlinear spectroscopy.