High-stability pH sensing with a few-layer MoS2 field-effect transistor.

Recently, molybdenum disulfide (MoS2), an emerging 2D material, has become an alternative candidate for ultra-sensitive biosensors due to its semiconducting behavior and the unique layer-by-layer atomic structure. Here, we report on highly stable and repeatable real-time pH sensing with few-layer MoS2 field-effect transistor (FET) biosensors, fabricated with both HfO2 and Al2O3/HfO2 gate dielectrics on top of MoS2 flakes exfoliated from natural crystals onto SiO2/Si samples. Both types of sensors demonstrate a highly linear, stable and repeatable response over a wide pH range with near-ideal pH sensitivity close to the theoretical limit of 59.6 mV pH-1. Ascribing from a different device operation regime in the pH sensing test-subthreshold regime for a sensor with an Al2O3/HfO2 dielectric and linear regime for a sensor with HfO2-a sensor with Al2O3/HfO2 shows significantly higher current sensitivity (∼105-fold) and relatively better linearity than a sensor with HfO2, while the latter shows relatively higher stability and higher repeatability. An Al2O3/HfO2-coated MoS2 FET reveals a high sensitivity or low detection limit of 0.01 pH.

Continuous-wave operation in directly patterned perovskite distributed feedback light source at room temperature.

We report a directly patterned perovskite distributed feedback (DFB) resonator and show narrow amplified spontaneous emission (ASE) at pump powers as low as 0.1 W/cm2 under continuous-wave (CW) optical pumping conditions at room temperature. Compared to the pristine thin film photoluminescence spectrum, a 16-fold reduction in emission linewidth in the MAPbI3 DFB cavity was observed. The direct nanostructuring of perovskites was achieved by thermal nanoimprint lithography. Our findings pave the way toward realizing CW pumped perovskite lasers at room temperature and energy-efficient perovskite light sources.

Nanoimprinted perovskite metasurface for enhanced photoluminescence.

Recently, solution-processed hybrid halide perovskite has emerged as promising materials for advanced optoelectronic devices such as photovoltaics, photodetectors, light emitting diodes and lasers. In the mean time, all-dielectric metasurfaces with high-index materials have attracted attention due to their low-loss and high-efficient optical resonances. Because of its tunable by composition band gap in the visible frequencies, organolead halide perovskite could serve as a powerful platform for realizing high-index, low-loss metasurfaces. However, direct patterning of perovskite by lithography-based technique is not feasible due to material instability under moisture. Here we report novel organolead halide perovskite metasurfaces created by the cost-effective thermal nanoimprint technology. The nanoimprinted perovskite metasurface showed improved surface morphology and enhanced optical absorption properties. Significantly enhanced optical emission with an eight-fold enhancement in photoluminescence (PL) intensity was observed under room temperature. Temperature-dependent PL of perovskite nanograting metasurface was also investigated. Based on our results, we believe that thermal nanoimprint is a simple and cost-effective technique to fabricate perovskite-based metasurfaces, which could have broad impact on optoelectronic and photonic applications.

Sensitive Urine Immunoassay for Visualization of Lipoarabinomannan for Noninvasive Tuberculosis Diagnosis.

Lipoarabinomannan (LAM) is a prospective noninvasive biomarker for tuberculosis (TB) diagnosis. Here, we report a visual immunoassay of high sensitivity for detecting LAM in urine samples toward TB diagnosis. This method uses a DNA-linked immunosorbent of LAM, followed by a transduction cascade into amplified visual signals using quantum dots (QDs) and calcein reaction with Cu2+ and copper nanoparticles (Cu NPs). The limit of detection (LOD) for LAM in the urine reaches 2.5 fg/mL and 25 fg/mL using a fluorometer and length readouts on strips, respectively, demonstrating an ultrahigh sensitivity. The clinical validation of the proposed assay was performed with 147 HIV-negative clinical urine specimens. The results show the sensitivity of test is 94.1% (16/17) for confirmed TB (culture-positive) and 85% (51/60) for unconfirmed TB (clinical diagnosis without positive culture results), respectively, when the test cutoff value is 40 fg/mL for TB. Its specificity is 89.2% (25/28) in non-TB and nontuberculous mycobacterial patients. The area under the curve (AUC) was 0.86 when controls were non-TB and LTBI patients, while the AUC was 0.92 when controls were only non-TB patients. This highly sensitive visual immunoassay of LAM has shown potential for noninvasive diagnosis of TB using urine samples.

Substitution of Ethylammonium Halides Enabling Lead-Free Tin-Based Perovskite Solar Cells with Enhanced Efficiency and Stability.

Tin (Sn)-based perovskite solar cells (PSCs) have attracted extensive attention due to the irlow toxicity and excellent optoelectric properties. Nonetheless, the development of Sn-based PSCs is still hampered by poor film quality due to the fast crystallization and the oxidation from Sn2+ to Sn4+. In this work, we compare and employ three ethylammonium halides, EAX (X = Cl, Br, I) to explore their roles in Sn-based perovskites and solar cells. We find that crystallinity and crystallization orientation of perovskites are optimized with the regulation of EAI. EABr leads to reduced defect density and enhanced crystallinity but also the lowest absorption and the widest band gap owing to the substitution of Br-. Notably, perovskites with EACl exhibit the best crystallinity, lowest defect density, and excellent antioxidant capacity benefiting from the partial substitution of Cl-. Consequently, the EACl-modified device achieves a champion PCE of 12.50% with an improved Voc of 0.79 V. Meanwhile, an unencapsulated EACl device shows excellent shelf stability with negligible efficiency degradation after 5400 h of storage in a N2-filled glovebox, and the encapsulated device retains its initial efficiency after continuous light illumination at the maximum power point for 100 h in air.

Quantum confinement induced performance enhancement in sub-5-nm lithographic Si nanowire transistors.

We demonstrate lithographically fabricated Si nanowire field effect transistors (FETs) with long Si nanowires of tiny cross sectional size (∼3-5 nm) exhibiting high performance without employing complementarily doped junctions or high channel doping. These nanowire FETs show high peak hole mobility (as high as over 1200 cm(2)/(V s)), current density, and drive current as well as low drain leakage current and high on/off ratio. Comparison of nanowire FETs with nanobelt FETs shows enhanced performance is a result of significant quantum confinement in these 3-5 nm wires. This study suggests simple (no additional doping) FETs using tiny top-down nanowires can deliver high performance for potential impact on both CMOS scaling and emerging applications such as biosensing.

Room-temperature quantum confinement effects in transport properties of ultrathin Si nanowire field-effect transistors.

Quantum confinement of carriers has a substantial impact on nanoscale device operations. We present electrical transport analysis for lithographically fabricated sub-5 nm thick Si nanowire field-effect transistors and show that confinement-induced quantum oscillations prevail at 300 K. Our results discern the basis of recent observations of performance enhancement in ultrathin Si nanowire field-effect transistors and provide direct experimental evidence for theoretical predictions of enhanced carrier mobility in strongly confined nanowire devices.

Homogeneous two-dimensional visual and fluorescence analysis of circulating tumor cells in clinical samples via steric hindrance regulated enzymes recognition cleavage and elongation.

Oncology detection technology is significant for the early detection of tumors. The current study reports a new method that uses folate receptor (FR) as circulating tumor cells (CTCs) marker and only folate modified T30 as a probe. This method also uses dual-enzyme assisted amplification strategy for homogeneous fluorescence as well as two-dimensional visual (color and distance) detection of SMMC-7721 liver cancer cells from clinical blood samples. This work was based on the steric hindrance caused by binding between FR and folate to regulate cleavage of folate-T30 by exonuclease I (Exo I) and to inhibit subsequent polymerization and extension reaction of the cleavage product by terminal deoxynucleotidyl transferase (TdT). It explores the use of CdTe QDs to selectively identify Cu2+ and polyT-template Cu NPs as a bridge combined with inkjet printing technology to make test strips that can be read through distance changes. Under fluorometer mode, limit of detection as low as 1 cells/mL was achieved. The color and distance reading modes can identify cells with concentrations as low as 5 and 1 cells/mL, respectively. This CTCs detection approach of fluorescence mode was further validated by using 50 clinical samples of liver cancer patients (19 negative and 31 positive). The results were in good agreement with FR-polymerase chain reaction (FR-PCR) kits, radiologic and pathological techniques. In addition, the quantitative results of distance reading test strips of CTCs in 22 clinical samples (8 negative and 14 positive) were also in 100% agreement with the findings of clinical kits, computed tomography (CT) and pathological tests.

Modeling particle shape-dependent dynamics in nanomedicine.

One of the major challenges in nanomedicine is to improve nanoparticle cell selectivity and adhesion efficiency through designing functionalized nanoparticles of controlled sizes, shapes, and material compositions. Recent data on cylindrically shaped filomicelles are beginning to show that non-spherical particles remarkably improved the biological properties over spherical counterpart. Despite these exciting advances, non-spherical particles have not been widely used in nanomedicine applications due to the lack of fundamental understanding of shape effect on targeting efficiency. This paper intends to investigate the shape-dependent adhesion kinetics of non-spherical nanoparticles through computational modeling. The ligand-receptor binding kinetics is coupled with Brownian dynamics to study the dynamic delivery process of nanorods under various vascular flow conditions. The influences of nanoparticle shape, ligand density, and shear rate on adhesion probability are studied. Nanorods are observed to contact and adhere to the wall much easier than their spherical counterparts under the same configuration due to their tumbling motion. The binding probability of a nanorod under a shear rate of 8 s(-1) is found to be three times higher than that of a nanosphere with the same volume. The particle binding probability decreases with increased flow shear rate and channel height. The Brownian motion is found to largely enhance nanoparticle binding. Results from this study contribute to the fundamental understanding and knowledge on how particle shape affects the transport and targeting efficiency of nanocarriers, which will provide mechanistic insights on the design of shape-specific nanomedicine for targeted drug delivery applications.

Biofriendly bonding processes for nanoporous implantable SU-8 microcapsules for encapsulated cell therapy.

Mechanically robust, cell encapsulating microdevices fabricated using photolithographic methods can lead to more efficient immunoisolation in comparison to cell encapsulating hydrogels. There is a need to develop adhesive bonding methods which can seal such microdevices under physiologically friendly conditions. We report the bonding of SU-8 based substrates through (i) magnetic self assembly, (ii) using medical grade photocured adhesive and (iii) moisture and photochemical cured polymerization. Magnetic self-assembly, carried out in biofriendly aqueous buffers, provides weak bonding not suitable for long term applications. Moisture cured bonding of covalently modified SU-8 substrates, based on silanol condensation, resulted in weak and inconsistent bonding. Photocured bonding using a medical grade adhesive and of acrylate modified substrates provided stable bonding. Of the methods evaluated, photocured adhesion provided the strongest and most stable adhesion.

Homogeneous Visual and Fluorescence Detection of Circulating Tumor Cells in Clinical Samples via Selective Recognition Reaction and Enzyme-Free Amplification.

Here we report a simple all-nucleic-acid enzyme-free catalyzed hairpin assembly assisted amplification strategy with quantum dots (QDs) as the nanoscale signal reporter for homogeneous visual and fluorescent detection of A549 lung cancer cells from clinical blood samples. This work was based on the phenomenon that CdTe QDs can selectively recognize Ag+ and C-Ag+-C and by using mucin 1 as the circulating tumor cells (CTCs) marker and aptamer as the recognition probe. Under optimized conditions, the limits of detections as low as 0.15 fg/mL of mucin 1 and 3 cells/mL of A549 cells were achieved with fluorescence signals. A 1 fg/mL concentration of mucin 1 and 100 cells/mL of A549 can be distinguished by the naked eye. This method was used to quantitatively analyze CTCs in 51 clinical whole blood samples of patients with lung cancer. The levels of CTCs detected in clinical samples by this method were consistent with those obtained using the folate receptor-polymerase chain reaction clinical test kit and correlated with radiologic and pathological findings.

Inhibited cell spreading on polystyrene nanopillars fabricated by nanoimprinting and in situ elongation.

Polymer nanopillars (40-80 nm in diameter and 100 nm in pitch) were fabricated at high density over large areas directly on bulk tissue culture polystyrene plates using nanoimprint lithography. Nanoporous Si molds for imprinting were generated by transfer from an anodic alumina membrane. Ultrahigh aspect ratio polymer nanopillars were formed in a novel procedure using controlled elongation of the imprinted pillars during mold release. The resulting nanopillar arrays show significant changes in surface wettability upon brief O(2) plasma treatment. Human dermal fibroblasts were cultured on the nanopillar surfaces in order to study cell-substrate interaction at the nanoscale. The nanopillar topography shows strong effects on the cell morphology, with pillars of widely varying aspect ratios and surface energies resisting cell spreading. This effect on cell behavior can be rationalized in terms of the cells' requirement to form micron-scale focal adhesions. The study indicates that at the nanoscale, physical factors can supersede the effects of chemical factors on the cell-substratum interaction.

SU-8-based immunoisolative microcontainer with nanoslots defined by nanoimprint lithography.

Cells can secrete biotherapeutic molecules that can replace or restore host function. The transplantation of such cells is a promising therapeutic modality for the treatment of several diseases including type 1 diabetes mellitus. These cellular grafts are encapsulated in semipermeable and immunoisolative membranes to protect them from the host immune system, while allowing the transport of nutrients and small molecules that are required for cell survival and function. The authors report on SU-8-based biocompatible immunoisolative cuboid microcontainers for cell transplantation. Each microcontainer comprises a 300×300×250 or a 1100×1100×250 µm(3) SU-8 hollowed cuboid base that houses the cells and an optically transparent SU-8-based nanoporous lid that closes the device. The hollowed cuboid base was formed by conventional optical lithography to have 8 nl (200×200×200 µm(3)) encapsulation volume for cellular payload. The lid comprises a thick SU-8 slab with an array of cylindrical wells, whose bottom surface is sealed with a thin nanoporous SU-8 membrane. The nanoporous membrane was created from a 100 nm grating (width and spacing) initial silicon mold subjected to a repeated cycle of oxidation and wet etching to achieve a 20 nm wide and 200 nm pitch nano silicon grating. Nanoimprinting and oblique-angle metal deposition, followed by inductively coupled plasma etching were utilized to create 15 nm wide and 350-450 nm deep nanoslots in the thin SU-8 membrane. Isolated mouse islets were encapsulated in the hollowed cuboid base and the nanoporous lid was assembled on top. The penetration of large and small molecules into the microcontainer was observed with fluorescence.

Polystyrene-coated Interdigitated Microelectrode Array to Detect Free Chlorine towards IoT Applications.

We apply interdigitated microelectrode array (IDA) sensors for water quality monitoring. IDA sensors with an ion-sensitive coating show higher sensitivity of about 600 mV with the hypochlorite ion concentration increasing from 0 to 10 ppm more than the traditional sensing method. The response mechanism and selectivity have been studied. Several material components that affect the sensing process were explored. Coupling agents and plasticizer were introduced into the coating material to improve the coating material quality and its adhesion to the electrodes. The stability/repeatability and linearity have been significantly improved.

Room-Temperature Continuous-Wave Operation of Organometal Halide Perovskite Lasers.

Solution-processed organic-inorganic lead halide perovskites have recently emerged as promising gain media for tunable semiconductor lasers. However, optically pumped continuous-wave lasing at room temperature, a prerequisite for a laser diode, has not been realized so far. Here, we report lasing action in a surface-emitting distributed feedback methylammonium lead iodide (MAPbI3) perovskite laser on a silicon substrate at room temperature under continuous-wave optical pumping. This outstanding performance is achieved because of the ultralow lasing threshold of 13 W/cm2, which is enabled by thermal nanoimprint lithography that directly patterns perovskite into a high- Q cavity with large mode confinement, while at the same time, it improves perovskite's emission characteristics. Our results represent a major step toward electrically pumped lasing in organic and thin-film materials as well as the insertion of perovskite lasers into photonic integrated circuits for applications in optical computing, sensing, and on-chip quantum information.

Large Molecular Weight Polymer Solar Cells with Strong Chain Alignment Created by Nanoimprint Lithography.

In this work, strong chain alignment in large molecular weight polymer solar cells is for the first time demonstrated by nanoimprint lithography (NIL). The polymer crystallizations in nonimprinted thin films and imprinted nanogratings with different molecular weight poly(3-hexylthiophene-2,5-diyl) (P3HT) are compared. We first observe that the chain alignment is favored by medium molecular weight (Mn = 25 kDa) P3HT for nonimprinted thin films. However, NIL allows large molecular weight P3HT (>40 kDa) to organize more strongly, which has been desired for efficient charge transport but is difficult to achieve through any other technique. Consequently P3HT/[6,6]-penyl-C61-butyric-acid-methyl-ester (PCBM) solar cells with large molecular weight P3HT nanogratings show a high power conversion efficiency of 4.4%, which is among the best reported P3HT/PCBM photovoltaics devices.

Nanoimprinted Perovskite Nanograting Photodetector with Improved Efficiency.

Recently, organolead halide-based perovskites have emerged as promising materials for optoelectronic applications, particularly for photovoltaics, photodetectors, and lasing, with low cost and high performance. Meanwhile, nanoscale photodetectors have attracted tremendous attention toward realizing miniaturized optoelectronic systems, as they offer high sensitivity, ultrafast response, and the capability to detect beyond the diffraction limit. Here we report high-performance nanoscale-patterned perovskite photodetectors implemented by nanoimprint lithography (NIL). The spin-coated lead methylammonium triiodide perovskite shows improved crystallinity and optical properties after NIL. The nanoimprinted metal-semiconductor-metal photodetectors demonstrate significantly improved performance compared to the nonimprinted conventional thin-film devices. The effects of NIL pattern geometries on the optoelectronic characteristics were studied, and the nanograting pattern based photodetectors demonstrated the best performance, showing approximately 35 times improvement on responsivity and 7 times improvement on on/off ratio compared with the nonimprinted devices. The high performance of NIL-nanograting photodetectors likely results from high crystallinity and favored nanostructure morphology, which contribute to higher mobility, longer diffusion length, and better photon absorption. Our results have demonstrated that the NIL is a cost-effective method to fabricate high-performance perovskite nanoscale optoelectronic devices, which may be suitable for manufacturing of high-density perovskite nanophotodetector arrays and to provide integration with state-of-the-art electronic circuits.

Efficient low bandgap polymer solar cell with ordered heterojunction defined by nanoimprint lithography.

In this work, we demonstrate the feasibility of using nanoimprint lithography (NIL) to make efficient low bandgap polymer solar cells with well-ordered heterojunction. High quality low bandgap conjugated polymer poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) nanogratings are fabricated using this technique for the first time. The geometry effect of PCPDTBT nanostructures on the solar cell performance is investigated by making PCPDTBT/C70 solar cells with different feature sizes of PCPDTBT nanogratings. It is found that the power conversion efficiency (PCE) increases with increasing nanograting height, PCPDTBT/C70 junction area, and decreasing nanograting width. We also find that NIL makes PCPDTBT chains interact more strongly and form an improved structural ordering. Solar cells made on the highest aspect ratio PCPDTBT nanostructures are among the best reported devices using the same material with a PCE of 5.5%.

Effects of nanostructure geometry on nanoimprinted polymer photovoltaics.

We demonstrate the effects of nanostructure geometry on the nanoimprint induced poly(3-hexylthiophene-2,5-diyl) (P3HT) chain alignment and the performance of nanoimprinted photovoltaic devices. Out-of-plane and in-plane grazing incident X-ray diffraction techniques are employed to characterize the nanoimprint induced chain alignment in P3HT nanogratings with different widths, spacings and heights. We observe the dependence of the crystallite orientation on nanostructure geometry such that a larger width of P3HT nanogratings leads to more edge-on chain alignment while the increase in height gives more vertical alignment. Consequently, P3HT/[6,6]-phenyl-C61-butyric-acid-methyl-ester (PCBM) solar cells with the highest density and aspect ratio P3HT nanostructures show the highest power conversion efficiency among others, which is attributed to the efficient charge separation, transport and light absorption.

Applications of Semiconductor Fabrication Methods to Nanomedicine: A Review of Recent Inventions and Techniques.

We live in a world of convergence where scientific techniques from a variety of seemingly disparate fields are being applied cohesively to the study and solution of biomedical problems. For instance, the semiconductor processing field has been primarily developed to cater to the needs of the ever decreasing transistor size and cost while increasing functionality of electronic circuits. In recent years, pioneers in this field have equipped themselves with a powerful understanding of how the same techniques can be applied in the biomedical field to develop new and efficient systems for the diagnosis, analysis and treatment of various conditions in the human body. In this paper, we review the major inventions and experimental methods which have been developed for nano/micro fluidic channels, nanoparticles fabricated by top-down methods, and in-vivo nanoporous microcages for effective drug delivery. This paper focuses on the information contained in patents as well as the corresponding technical publications. The goal of the paper is to help emerging scientists understand and improvise over these inventions.