Bandlike transport in strongly coupled and doped quantum dot solids: a route to high-performance thin-film electronics.

We report bandlike transport in solution-deposited, CdSe QD thin-films with room temperature field-effect mobilities for electrons of 27 cm(2)/(V s). A concomitant shift and broadening in the QD solid optical absorption compared to that of dispersed samples is consistent with electron delocalization and measured electron mobilities. Annealing indium contacts allows for thermal diffusion and doping of the QD thin-films, shifting the Fermi energy, filling traps, and providing access to the bands. Temperature-dependent measurements show bandlike transport to 220 K on a SiO(2) gate insulator that is extended to 140 K by reducing the interface trap density using an Al(2)O(3)/SiO(2) gate insulator. The use of compact ligands and doping provides a pathway to high performance, solution-deposited QD electronics and optoelectronics.

Colloidal Ag2Se intraband quantum dots.

With the emergence of the Internet of Things, wearable electronics, and machine vision, the exponentially growing demands for miniaturization, energy efficiency, and cost-effectiveness have imposed critical requirements on the size, weight, power consumption and cost (SWaP-C) of infrared detectors. To meet this demand, new sensor technologies that can reduce the fabrication cost associated with semiconductor epitaxy and remove the stringent requirement for cryogenic cooling are under active investigation. In the technologically important spectral region of mid-wavelength infrared, intraband colloidal quantum dots are currently at the forefront of this endeavor, with wafer-scale monolithic integration and Auger suppression being the key material capabilities to minimize the sensor's SWaP-C. In this Feature Article, we provide a focused review on the development of sensors based on Ag2Se intraband colloidal quantum dots, a heavy metal-free colloidal nanomaterial that has merits for wide-scale adoption in consumer and industrial sectors.

Low-Temperature Centimeter-Scale Growth of Layered 2D SnS for Piezoelectric Kirigami Devices.

Tin monosulfide (SnS) is a promising piezoelectric material with an intrinsically layered structure, making it attractive for self-powered wearable and stretchable devices. However, for practical application purposes, it is essential to improve the output and manufacturing compatibility of SnS-based piezoelectric devices by exploring their large-area synthesis principle. In this study, we report the chemical vapor deposition (CVD) growth of centimeter-scale two-dimensional (2D) SnS layers at temperatures as low as 200 °C, allowing compatibility with processing a range of polymeric substrates. The intrinsic piezoelectricity of 2D SnS layers directly grown on polyamides (PIs) was confirmed by piezoelectric force microscopy (PFM) phase maps and force-current corroborative measurements. Furthermore, the structural robustness of the centimeter-scale 2D SnS layers/PIs allowed for engraving complicated kirigami patterns on them. The kirigami-patterned 2D SnS layer devices exhibited intriguing strain-tolerant piezoelectricity, which was employed in detecting human body motions and generating photocurrents irrespective of strain rate variations. These results establish the great promise of 2D SnS layers for practically relevant large-scale device technologies with coupled electrical and mechanical properties.

Enhanced thermopower via carrier energy filtering in solution-processable Pt-Sb2Te3 nanocomposites.

This work demonstrates the first solution-processable metal-semiconductor nanocomposites with enhanced thermoelectric properties via carrier energy filtering. Platinum nanocrystals are embedded in a p-type antimony(III) telluride (Sb(2)Te(3)) semiconductor matrix, thus introducing band-bending potentials for holes. By scattering low energy holes, an increase in thermopower is observed. Introduction of Pt nanocrystals also increases carrier concentration thereby partially compensating for reduced electrical conductivity due to the decreased mobility. At room temperature, an improvement in thermoelectric power factor was achieved compared to that of the Sb(2)Te(3) films. This work highlights the possibility of combining a diverse set of n- and p-type semiconductor matrices with nanocrystals to engineer and optimize energy-dependent carrier scattering with the ease of materials processing.

Multiscale periodic assembly of striped nanocrystal superlattice films on a liquid surface.

Self-assembly of nanocrystals (NCs) into periodically ordered structures on multiple length scales and over large areas is crucial to the manufacture of NC-based devices. Here, we report an unusual yet universal approach to rapidly assembling hierarchically organized NC films that display highly periodic, tunable microscale stripe patterns over square centimeter areas while preserving the local superlattice structure. Our approach is based on a drying-driven dynamic assembly process occurring on a liquid surface with the stripe pattern formed by a new type of contact-line instability. Periodic ordering of NCs is realized on microscopic and nanoscopic scales simultaneously without the need of any specialized equipment or the application of external fields. The striped NC superlattice films obtained can be readily transferred to arbitrary substrates for device fabrication. The periodic structure imparts interesting modulation and anisotropy to the properties of such striped NC assemblies. This assembly approach is applicable to NCs with a variety of compositions, sizes, and shapes, offering a robust, inexpensive route for large-scale periodic patterning of NCs.

Peel-and-Stick Integration of Atomically Thin Nonlayered PtS Semiconductors for Multidimensionally Stretchable Electronic Devices.

Various near-atom-thickness two-dimensional (2D) van der Waals (vdW) crystals with unparalleled electromechanical properties have been explored for transformative devices. Currently, the availability of 2D vdW crystals is rather limited in nature as they are only obtained from certain mother crystals with intrinsically possessed layered crystallinity and anisotropic molecular bonding. Recent efforts to transform conventionally non-vdW three-dimensional (3D) crystals into ultrathin 2D-like structures have seen rapid developments to explore device building blocks of unique form factors. Herein, we explore a "peel-and-stick" approach, where a nonlayered 3D platinum sulfide (PtS) crystal, traditionally known as a cooperate mineral material, is transformed into a freestanding 2D-like membrane for electromechanical applications. The ultrathin (∼10 nm) 3D PtS films grown on large-area (>cm2) silicon dioxide/silicon (SiO2/Si) wafers are precisely "peeled" inside water retaining desired geometries via a capillary-force-driven surface wettability control. Subsequently, they are "sticked" on strain-engineered patterned substrates presenting prominent semiconducting properties, i.e., p-type transport with an optical band gap of ∼1.24 eV. A variety of mechanically deformable strain-invariant electronic devices have been demonstrated by this peel-and-stick method, including biaxially stretchable photodetectors and respiratory sensing face masks. This study offers new opportunities of 2D-like nonlayered semiconducting crystals for emerging mechanically reconfigurable and stretchable device technologies.

Thiocyanate-capped nanocrystal colloids: vibrational reporter of surface chemistry and solution-based route to enhanced coupling in nanocrystal solids.

Ammonium thiocyanate (NH(4)SCN) is introduced to exchange the long, insulating ligands used in colloidal nanocrystal (NC) synthesis. The short, air-stable, environmentally benign thiocyanate ligand electrostatically stabilizes a variety of semiconductor and metallic NCs in polar solvents, allowing solution-based deposition of NCs into thin-film NC solids. NH(4)SCN is also effective in replacing ligands on NCs after their assembly into the solid state. The spectroscopic properties of this ligand provide unprecedented insight into the chemical and electronic nature of the surface of the NCs. Spectra indicate that the thiocyanate binds to metal sites on the NC surface and is sensitive to atom type and NC surface charge. The short, thiocyanate ligand gives rise to significantly enhanced electronic coupling between NCs as evidenced by large bathochromic shifts in the absorption spectra of CdSe and CdTe NC thin films and by conductivities as high as (2 ± 0.7) × 10(3) Ω(-1) cm(-1) for Au NC thin films deposited from solution. NH(4)SCN treatment of PbTe NC films increases the conductivity by 10(13), allowing the first Hall measurements of nonsintered NC solids, with Hall effect mobilities of 2.8 ± 0.7 cm(2)/(V·s). Thiocyanate-capped CdSe NC thin films form photodetectors exhibiting sensitive photoconductivity of 10(-5) Ω(-1) cm(-1) under 30 mW/cm(2) of 488 nm illumination with I(photo)/I(dark) > 10(3) and form n-channel thin-film transistors with electron mobilities of 1.5 ± 0.7 cm(2)/(V·s), a current modulation of >10(6), and a subthreshold swing of 0.73 V/decade.

Carrier distribution and dynamics of nanocrystal solids doped with artificial atoms.

Single component and multicomponent nanocrystal (NC) solids represent an exciting new form of condensed matter, as they can potentially capture not only the quantum features of the individual building blocks but also novel collective properties through coupling of NC components. Unlike bulk semiconductors, however, there is no current theory for how introduction of dopants will impact the electronic structure and transport properties of NC solids. Empirically, it is known that in semiconductor NC systems, mixing two different materials of NCs electronically dopes the film. However, it has been challenging to connect the macroscopic measurements of doping effects on transport behavior to a microscopic understanding of how the identity, placement, and abundance of dopants impact these measurements. In this Letter, we report the first temperature-dependent thermopower measurements in doped and undoped NC solids. In combination with temperature-dependent electrical conductivity measurements, how the doping affects the carrier concentration as well as mobility is explored exclusively. These complementary measurements serve as a unique electronic spectroscopy tool to quantitatively reveal the energetics of carriers and electronic states in NC solids.

Vertically Stacked Intraband Quantum Dot Devices for Mid-Wavelength Infrared Photodetection.

Intraband quantum dots are degenerately doped semiconductor nanomaterials that exhibit unique optical properties in mid- to long-wavelength infrared. To date, these quantum dots have been only studied as lateral photoconductive devices, while transitioning toward a vertically stacked structure can open diverse opportunities for investigating advanced device designs. Here, we report the first vertical intraband quantum dot heterojunction devices composed of Ag2Se/PbS/Ag2Se quantum dot stacks that bring the advantage of reduced dark conductivity with a simplified device fabrication procedure. We discuss the improvement in the colloidal synthesis of Ag2Se quantum dots that are critical for vertical device fabrication, identify an important process that determines the mid-wavelength infrared responsivity of the quantum dot film, and analyze the basic device characteristics and key detector performance parameters. Compared to the previous generation of Ag2Se quantum dot-based photoconductive devices, approximately 70 times increase in the mid-wavelength responsivity, at room temperature, is observed.

Midwavelength Infrared p-n Heterojunction Diodes Based on Intraband Colloidal Quantum Dots.

As an emerging member of the colloidal semiconductor quantum dot materials family, intraband quantum dots are being extensively studied for thermal infrared sensing applications. High-performance detectors can be realized using a traditional p-n junction device design; however, the heavily doped nature of intraband quantum dots presents a new challenge in realizing diode devices. In this work, we utilize a trait uniquely available in a colloidal quantum dot material system to overcome this challenge: the ability to blend two different types of quantum dots to control the electrical property of the resulting film. We report on the preparation of binary mixture films containing midwavelength infrared Ag2Se intraband quantum dots and the fabrication of p-n heterojunction diodes with strong rectifying characteristics. The peak specific detectivity at 4.5 µm was measured to be 107 Jones at room temperature, which is an orders of magnitude improvement compared to the previous generation of intraband quantum dot detectors.

High-Performance Oxide-Based p-n Heterojunctions Integrating p-SnOx and n-InGaZnO.

The fabrication of oxide-based p-n heterojunctions that exhibit high rectification performance has been difficult to realize using standard manufacturing techniques that feature mild vacuum requirements, low thermal budget processing, and scalability. Critical bottlenecks in the fabrication of these heterojunctions include the narrow processing window of p-type oxides and the charge-blocking performance across the metallurgical junction required for achieving low reverse current and hence high rectification behavior. The overarching goal of the present study is to demonstrate a simple processing route to fabricate oxide-based p-n heterojunctions that demonstrate high on/off rectification behavior, a low saturation current, and a small turn-on voltage. For this study, room-temperature sputter-deposited p-SnOx and n-InGaZnO (IGZO) films were chosen. SnOx is a promising p-type oxide material due to its monocationic system that limits complexities related to processing and properties, compared to other multicationic oxide materials. For the n-type oxide, IGZO is selected due to the knowledge that postprocessing annealing critically reduces the defect and trap densities in IGZO to ensure minimal interfacial recombination and high charge-blocking performance in the heterojunctions. The resulting oxide p-n heterojunction exhibits a high rectification ratio greater than 103 at ±3 V, a low saturation current of ∼2 × 10-10 A, and a small turn-on voltage of ∼0.5 V. In addition, the demonstrated oxide p-n heterojunctions exhibit excellent stability over time in air due to the p-SnOx with completed reaction annealing in air and the reduced trap density in n-IGZO.

Scalable Van der Waals Two-Dimensional PtTe2 Layers Integrated onto Silicon for Efficient Near-to-Mid Infrared Photodetection.

In recent years, there has been increasing interest in leveraging two-dimensional (2D) van der Waals (vdW) crystals for infrared (IR) photodetection, exploiting their unusual optoelectrical properties. Some 2D vdW materials with small band gap energies such as graphene and black phosphorus have been explored as stand-alone IR responsive layers in photodetectors. However, the devices incorporating these IR-sensitive 2D layers often exhibited poor performances owing to their preparation issues such as limited scalability and air instability. Herein, we explored wafer-scale 2D platinum ditelluride (PtTe2) layers for near-to-mid IR photodetection by directly growing them onto silicon (Si) wafers. 2D PtTe2/Si heterojunctions exhibited wavelength- and intensity-dependent high photocurrents in a spectral range of ∼1-7 µm, significantly outperforming stand-alone 2D PtTe2 layers. The observed superiority is attributed to their excellent Schottky junction characteristics accompanying suppressed carrier recombination as well as optical absorbance competition between 2D PtTe2 layers and Si. The direct and scalable growth of 2D PtTe2 layers was further extended to demonstrate mechanically flexible IR photodetectors.

High-performance thermoelectric silver selenide thin films cation exchanged from a copper selenide template.

Over the past decade, Ag2Se has attracted increasing attention due to its potentially excellent thermoelectric (TE) performance as an n-type semiconductor. It has been considered a promising alternative to Bi-Te alloys and other commonly used yet toxic and/or expensive TE materials. To optimize the TE performance of Ag2Se, recent research has focused on fabricating nanosized Ag2Se. However, synthesizing Ag2Se nanoparticles involves energy-intensive and time-consuming techniques with poor yield of final product. In this work, we report a low-cost, solution-processed approach that enables the formation of Ag2Se thin films from Cu2-x Se template films via cation exchange at room temperature. Our simple two-step method involves fabricating Cu2-x Se thin films by the thiol-amine dissolution of bulk Cu2Se, followed by soaking Cu2-x Se films in AgNO3 solution and annealing to form Ag2Se. We report an average power factor (PF) of 617 ± 82 µW m-1 K-2 and a corresponding ZT value of 0.35 at room temperature. We obtained a maximum PF of 825 µW m-1 K-2 and a ZT value of 0.46 at room temperature for our best-performing Ag2Se thin-film after soaking for 5 minutes. These high PFs have been achieved via full solution processing without hot-pressing.

Colloidal quantum dots for thermal infrared sensing and imaging.

Colloidal quantum dots provide a powerful materials platform to engineer optoelectronics devices, opening up new opportunities in the thermal infrared spectral regions where no other solution-processed material options exist. This mini-review collates recent research reports that push the technological envelope of colloidal quantum dot-based photodetectors toward mid- and long-wavelength infrared. We survey the synthesis and characterization of various thermal infrared colloidal quantum dots reported to date, discuss the basic theory of device operation, review the fabrication and measurement of photodetectors, and conclude with the future prospect of this emerging technology.

Colloidal-annealing of ZnO nanoparticles to passivate traps and improve charge extraction in colloidal quantum dot solar cells.

The popularity of colloidal quantum dot (CQD) solar cells has increased owing to their tunable bandgap, multiple exciton generation, and low-cost solution processes. ZnO nanoparticle (NP) layers are generally employed as electron transport layers in CQD solar cells to efficiently extract the electrons. However, trap sites and the unfavorable band structure of the as-synthesized ZnO NPs have hindered their potential performance. Herein, we introduce a facile method of ZnO NP annealing in the colloidal state. Electrical, structural, and optical analyses demonstrated that the colloidal-annealing of ZnO NPs effectively passivated the defects and simultaneously shifted their band diagram; therefore, colloidal-annealing is a more favorable method as compared to conventional film-annealing. These CQD solar cells based on colloidal-annealed ZnO NPs exhibited efficient charge extraction, reduced recombination and achieved an enhanced power conversion efficiency (PCE) of 9.29%, whereas the CQD solar cells based on ZnO NPs without annealing had a PCE of 8.05%. Moreover, the CQD solar cells using colloidal-annealed ZnO NPs exhibited an improved air stability with 98% retention after 120 days, as compared to that of CQD solar cells using non-annealed ZnO NPs with 84% retention.

Paper Thermoelectrics: Merging Nanotechnology with Naturally Abundant Fibrous Material.

The development of paper-based sensors, antennas, and energy-harvesting devices can transform the way electronic devices are manufactured and used. Herein we describe an approach to fabricate paper thermoelectric generators for the first time by directly impregnating naturally abundant cellulose materials with p- or n-type colloidal semiconductor quantum dots. We investigate Seebeck coefficients and electrical conductivities as a function of temperature between 300 and 400 K as well as in-plane thermal conductivities using Angstrom's method. We further demonstrate equipment-free fabrication of flexible thermoelectric modules using p- and n-type paper strips. Leveraged by paper's inherently low thermal conductivity and high flexibility, these paper modules have the potential to efficiently utilize heat available in natural and man-made environments by maximizing the thermal contact to heat sources of arbitrary geometry.

Photovoltaic Performance of PbS Quantum Dots Treated with Metal Salts.

Recent advances in quantum dot surface passivation have led to a rapid development of high-efficiency solar cells. Another critical element for achieving efficient power conversion is the charge neutrality of quantum dots, as charge imbalances induce electronic states inside the energy gap. Here we investigate how the simultaneous introduction of metal cations and halide anions modifies the charge balance and enhances the solar cell efficiency. The addition of metal salts between QD deposition and ligand exchange with 1,3-BDT results in an increase in the short-circuit current and fill factor, accompanied by a distinct reduction in a crossover between light and dark current density-voltage characteristics.

Protein-directed self-assembly of a fullerene crystal.

Learning to engineer self-assembly would enable the precise organization of molecules by design to create matter with tailored properties. Here we demonstrate that proteins can direct the self-assembly of buckminsterfullerene (C60) into ordered superstructures. A previously engineered tetrameric helical bundle binds C60 in solution, rendering it water soluble. Two tetramers associate with one C60, promoting further organization revealed in a 1.67-Å crystal structure. Fullerene groups occupy periodic lattice sites, sandwiched between two Tyr residues from adjacent tetramers. Strikingly, the assembly exhibits high charge conductance, whereas both the protein-alone crystal and amorphous C60 are electrically insulating. The affinity of C60 for its crystal-binding site is estimated to be in the nanomolar range, with lattices of known protein crystals geometrically compatible with incorporating the motif. Taken together, these findings suggest a new means of organizing fullerene molecules into a rich variety of lattices to generate new properties by design.

Alternative Method of Retrocrural Approach during Celiac Plexus Block Using a Bent Tip Needle.

BACKGROUND: This study sought to determine safe ranges of oblique angle, skin entry point and needle length by reviewing computed tomography (CT) scans and to evaluate the usefulness of a bent tip needle during celiac plexus block (CPB). METHODS: CT scans of 60 CPB patients were reviewed. Image of the uppermost margin of L2 vertebral body was used to measure the minimal and maximal oblique angles and the distances from the midline to skin puncture point. The imaginary needle trajectory distance was calculated by three-dimensional measurement. When the procedure was performed by using a 10° bent tip needle under a 20° oblique X-ray fluoroscopic view, the distance (GF/G'F) from the midline to the actual puncture site was measured. RESULTS: The imaginary safe oblique angle range was 26.4-34.2° and 27.7-36.0° on the right and left, respectively. The distance from the midline to skin puncture point was 6.1-7.6 cm on the right and 6.3-7.6 cm on the left. The needle trajectory distance at minimal angle was 9.6-11.6 cm on the right and 9.5-11.5 cm on the left. The distance of GF/G'F was 5.1-6.5 cm and 5.0-6.4 cm on the right and left, respectively. All imaginary parameters were correlated with BMI except for GF/G'F. All complications were mild and transient. CONCLUSIONS: We identified safe values of angles and distances using a straight needle. Furthermore, using a bent tip needle under a 20° oblique fluoroscopic view, we could safely perform CPB with smaller parameter values.