Blue sensitive sub-band gap negative photoconductance in SnO2/TiO2 NP bilayer oxide transistor.

Large negative photoconductance (NPC) of SnO2/TiO2 nanoparticles (NPs) heterostructure has been observed with thin film transistor (TFT) geometry and has been investigated using sub-bandgap light (blue) illumination. This negative photoconduction has been detected both in accumulation and depletion mode operation, which effectively reduces the carrier mobility (µ) of the TFT. Moreover, the threshold voltage (Vth) widely shifted in the positive direction under illumination. The combined effects of the reduction of mobility and Vth shifting led to a faster reduction of On (or Off) state current under illumination. The negative photosensitivity of this system is as high as 3.2 A W-1, which has been rarely reported in the earlier literature. Moreover, the variation of On (or Off) current, µ and Vth shift is linear with low-intensity blue light. This SnO2/TiO2 NP bilayer channel has been deposited on top of an ionic dielectric (Li-Al2O3) that reduces its operating voltage of this TFT within 2 V. Furthermore, the device has achieved a saturation mobility of 0.4 cm2 V-1 s-1 with an on/off ratio of 7.4 × 103 in the dark. An energy band diagram model has been proposed based on the type-II heterostructure formation between SnO2/TiO2 semiconductors to explain this NPC mechanism. According to the energy band diagram model, adsorbed H2O molecules of TiO2 NPs created a depleted layer in the heterostructure that accelerated the recombination process of photo-generated carriers rather than its transport.

Semi-Transparent, Pixel-Free Upconversion Goggles with Dual Audio-Visual Communication.

The intractable brittleness and opacity of the crystalline semiconductor restrict the prospect of developing low-cost imaging systems. Here, infrared visualization technologies are established with large-area, semi-transparent organic upconversion devices that bring high-resolution invisible images into sight without photolithography. To exploit all photoinduced charge carriers, a monolithic device structure is proposed built on the infrared-selective, single-component charge generation layer of chloroaluminum phthalocyanine (ClAlPc) coupled to two visible light-emitting layers manipulated with unipolar charges. Transient pump-probe spectroscopy reveals that the ClAlPc-based device exhibits an efficient charge dissociation process under forward bias. This process is indicated by the prompt and strong features of electroabsorption screening. Furthermore, by imposing the electric field, the ultrafast excited state dynamic suggests a prolonged charge carrier lifetime from the ClAlPc, which facilitates the charge utilization for upconversion luminance. For the first time, >30% of the infrared photons are utilized without photomultiplication strategies owing to the trivial spectrum overlap between ClAlPc and the emitter. In addition, the device can broadcast the acoustic signal by synchronizing the device frequency with the light source, which enables to operate it in dual audio-visual mode. The work demonstrates the potential of upconversion devices for affordable infrared imaging in wearable electronics.

Transparent organic upconversion devices displaying high-resolution, single-pixel, low-power infrared images perceived by human vision.

Crystalline photodiodes remain the most viable infrared sensing technology of choice, yet the opacity and the limitation in pixel size reduction per se restrict their development for supporting high-resolution in situ infrared images. In this work, we propose an all-organic non-fullerene-based upconversion device that brings invisible infrared signal into human vision via exciplex cohost light-emissive system. The device reaches an infrared-to-visible upconversion efficiency of 12.56% by resolving the 940-nm infrared signal (power density of 103.8 µW cm-2). We tailor a semitransparent (AVT, ~60%), large-area (10.35 cm2), lightweight (22.91 g), single-pixel upconversion panel to visualize the infrared power density down to 0.75 µW cm2, inferring a bias-switching linear dynamic range approaching 80 dB. We also demonstrate the possibility of visualizing low-intensity infrared signals from the Face ID and LiDAR, which should fill the gap in the existing technology based on pixelated complementary metal-oxide semiconductors with optical lenses.

Achieving a Highly Stable Perovskite Photodetector with a Long Lifetime Fabricated via an All-Vacuum Deposition Process.

Hybrid organic-inorganic metal halide perovskites (HOIP) have become a promising visible light sensing material due to their excellent optoelectronic characteristics. Despite the superiority, overcoming the stability issue for commercialization remains a challenge. Herein, an extremely stable photodetector was demonstrated and fabricated with Cs0.06FA0.94Pb(I0.68Br0.32)3 perovskite by an all-vacuum process. The photodetector achieves a current density up to 1.793 × 10-2 A cm-2 under standard one sun solar illumination while maintaining a current density as low as 8.627 × 10-10 A cm-2 at zero bias voltage. The linear dynamic range (LDR) and transient voltage response were found to be comparable to the silicon-based photodetector (Newport 818-SL). Most importantly, the device maintains 95% of the initial performance after 960 h of incessant exposure under one sun solar illumination. The achievements of these outstanding results contributed to the all-vacuum deposition process delivering a film with high stability and good uniformity, which in turn delays the degradation process. The degradation mechanism is further investigated by impedance spectroscopy to reveal the charge dynamics in the photodetector under different exposure times.

Strongly Improving the Sensitivity of Phosphorescence-Based Optical Oxygen Sensors by Exploiting Nano-Porous Substrates.

Sensitivity is one of the crucial factors in determining the quality of a fluorescence/phosphorescence-based gas sensor, and is estimated from the measurement of responses (I0/I, where I0 and I refer to the measured optical intensity of a sensor in absence and presence of analyte molecules) at various concentrations of analytes. In this work, we demonstrate phosphorescence-based optical oxygen sensors fabricated on highly porous anodic aluminum oxide (AAO) membranes showing dramatically high response. These sensors exploit the enormous surface area of the AAO to facilitate the effective interaction between the sensing molecules and the analytes. We spin-coat an AAO membrane (200 nm pore diameter) with a platinum-based oxygen sensing porphyrin dye, platinum(II) meso-tetrakis (pentafluorophenyl) porphyrin (PtTFPP), to fabricate a sensor exhibiting I0/I ~400 at 100% oxygen atmosphere. To address the generality of the AAO membrane, we fabricate a separate sensor with another porphyrin dye, platinum octaethylporphyrin (PtOEP), which exhibits an even higher I0/I of ~500. Both of these sensors offer the highest responses as an optical oxygen sensor hitherto reported. SEM and EDS analysis are performed to realize the effect of the increased surface area of the AAO membrane on the enhanced sensitivity.

Ingenious Fabrication of Ag-Filled Porous Anodic Alumina Films as Powerful SERS Substrates for Efficient Detection of Biological and Organic Molecules.

Surface-enhanced Raman scattering (SERS) has been widely used to effectively detect various biological and organic molecules. This detection method needs analytes adsorbed onto a specific metal nanostructure, e.g., Ag-nanoparticles. A substrate containing such a structure (called SERS substrate) is user-friendly for people implementing the adsorption and subsequent SERS detection. Here, we report on powerful SERS substrates based on efficient fabrication of Ag-filled anodic aluminum oxide (AAO) films. The films contain many nanopores with small as-grown inter-pore gap of 15 nm. The substrates are created by electrochemically depositing silver into nanopores without an additional pore widening process, which is usually needed for conventional two-step AAO fabrication. The created substrates contain well-separated Ag-nanoparticles with quite a small inter-particle gap and a high number density (2.5 × 1010 cm-2). We use one-step anodization together with omitting additional pore widening to improve the throughput of substrate fabrication. Such substrates provide a low concentration detection limit of 10-11 M and high SERS enhancement factor of 1 × 106 for rhodamine 6G (R6G). The effective detection of biological and organic molecules by the substrate is demonstrated with analytes of adenine, glucose, R6G, eosin Y, and methylene blue. These results allow us to take one step further toward the successful commercialization of AAO-based SERS substrates.

Resolving Cross-Sensitivity Effect in Fluorescence Quenching for Simultaneously Sensing Oxygen and Ammonia Concentrations by an Optical Dual Gas Sensor.

Simultaneous sensing of multiple gases by a single fluorescent-based gas sensor is of utmost importance for practical applications. Such sensing is strongly hindered by cross-sensitivity effects. In this study, we propose a novel analysis method to ameliorate such hindrance. The trial sensor used here was fabricated by coating platinum(II) meso-tetrakis(pentafluorophenyl)porphyrin (PtTFPP) and eosin-Y dye molecules on both sides of a filter paper for sensing O2 and NH3 gases simultaneously. The fluorescent peak intensities of the dyes can be quenched by the analytes and this phenomenon is used to identify the gas concentrations. Ideally, each dye is only sensitive to one gas species. However, the fluorescent peak related to O2 sensing is also quenched by NH3 and vice versa. Such cross-sensitivity strongly hinders gas concentration detection. Therefore, we have studied this cross-sensitivity effect systematically and thus proposed a new analysis method for accurate estimation of gas concentration. Comparing with a traditional method (neglecting cross-sensitivity), this analysis improves O2-detection error from -11.4% ± 34.3% to 2.0% ± 10.2% in a mixed background of NH3 and N2.

Scalable Synthesis of a Sub-10 nm Chalcopyrite (CuFeS2) Nanocrystal by the Microwave-Assisted Synthesis Technique and Its Application in a Heavy-Metal-Free Broad-Band Photodetector.

A heavy-metal-free chalcopyrite (CuFeS2) nanocrystal has been synthesized via microwave-assisted growth. Large-scale nanocrystals with an average particle size of 5 nm are fabricated by this technique within a very short period of time without any need for organic ligands. Scanning electron microscopy study (SEM) of individual synthesis steps indicates that aggregates of nanocrystals are formed as flakes during microwave-assisted synthesis. The colloidal solution of the CuFeS2 nanocrystal was prepared by sonicating these flakes. Transmission electron microscopy (TEM) study reveals the growth of sub-10 nm CuFeS2 nanocrystals that are further characterized by X-ray diffraction. UV-visible absorption spectroscopic study shows that the band gap of this nanocrystal is ∼1.3 eV. To investigate the photosensitive nature of this nanocrystal, a bilayer p-n heterojunction photodetector has been fabricated using this nontoxic CuFeS2 nanocrystal as a photoactive material and n-type ZnO as a charge-transport layer. The detectivity of this photodetector reaches above 1012 Jones in visible and near-infrared (NIR) regions under 10 V external bias, which is significantly high for a nontoxic nanocrystal-based photodetector.

An Effective Optical Dual Gas Sensor for Simultaneous Detection of Oxygen and Ammonia.

The development of a simple, low-cost sensor for the effective sensing of multiple gases in industrial or residential zones has been in high demand in recent days. In this article, we have proposed an optical sensor for the dual sensing of oxygen (O2) and ammonia (NH3) gases, which consists of oxygen and ammonia-sensitive fluorescent dyes coated individually on both sides of a glass substrate. An ethyl cellulose (EC) matrix doped with platinum (II) meso-tetrakis (pentafluorophenyl) porphyrin (PtTFPP) serves as the oxygen-sensing material, whereas the NH3-sensing material includes an eosin Y fluorescent indicator immobilized within a cellulose acetate (CA) matrix. Both the oxygen and ammonia-sensitive materials were excited by the same LED light source with a 405 nm peak wavelength, while the corresponding emissions were detected separately for the selective sensing of the gases under study. The dual gas sensor exhibits maximum sensitivities of around 60 and 20 for oxygen and ammonia gases, respectively. The high sensitivity and selectivity of the proposed optical dual sensor suggests the feasibility of the simultaneous sensing of oxygen and ammonia for practical applications.

Versatile Exciplex-Forming Co-Host for Improving Efficiency and Lifetime of Fluorescent and Phosphorescent Organic Light-Emitting Diodes.

We report a new efficient exciplex-forming system consisting of a biscarbazole donor and a triazine-based acceptor. The new exciplex was characterized with a high photoluminescence quantum yield up to 68% and effective thermally activated delayed fluorescence behavior. The BCzPh:3P-T2T (2:1, 30 nm) blend was examined not only as an emitting layer (device D1) but also a reliable co-host of fluorescent and phosphorescent emitters for giving highly efficient exciplex-based organic light-emitting diodes (OLEDs) with a high maximum external quantum efficiency of 15.5 and 29.7% for devices doped with 1 wt % C545T (device D2) and 8 wt % Ir(ppy)2(acac) (device D4), respectively. More strikingly, a strongly enhanced lifetime ( T75 = 16 927 min.) of the C545T-doped device was obtained. The transient electroluminescence measurement as well as capacitance-voltage and impedance-voltage correlations were utilized to explore the factors governing the high efficiency and stability. The obtained results clearly show that the energy transfer and charge transport is highly efficient; they also show the photoelectric semiconducting characteristics of exciplex-based OLEDs, which are significantly different from those of unipolar host-based reference devices D3 (Alq3: 1 wt % C545T) and D5 (CBP: 8 wt % Ir(ppy)2(acac)). Our works have established a systematic protocol to shed light on the mechanisms behind exciplex-based devices. The combined results also confirm the bright prospect of the exciplex-forming system as the co-host for highly efficient and stable OLEDs.

A quantitative characterization of interaction between prion protein with nucleic acids.

Binding of recombinant prion protein with small highly structured RNAs, prokaryotic and eukaryotic prion protein mRNA pseudoknots, tRNA and polyA has been studied by the change in fluorescence anisotropy of the intrinsic tryptophan groups of the protein. The affinities of these RNAs to the prion protein and the number of sites where the protein binds to the nucleic acids do not vary appreciably although the RNAs have very different compositions and structures. The binding parameters do not depend upon pH of the solution and show a poor co-operativity. The reactants form larger nucleoprotein complexes at pH 5 compared to that at neutral pH. The electrostatic force between the protein and nucleic acids dominates the binding interaction at neutral pH. In contrast, nucleic acid interaction with the incipient nonpolar groups exposed from the structured region of the prion protein dominates the reaction at pH 5. Prion protein of a particular species forms larger complexes with prion protein mRNA pseudoknots of the same species. The structure of the pseudoknots and not their base sequences probably dominates their interaction with prion protein. Possibilities of the conversion of the prion protein to its infectious form in the cytoplasm by nucleic acids have been discussed.

A Sequence-Dependent DNA Condensation Induced by Prion Protein.

Different studies indicated that the prion protein induces hybridization of complementary DNA strands. Cell culture studies showed that the scrapie isoform of prion protein remained bound with the chromosome. In present work, we used an oxazole dye, YOYO, as a reporter to quantitative characterization of the DNA condensation by prion protein. We observe that the prion protein induces greater fluorescence quenching of YOYO intercalated in DNA containing only GC bases compared to the DNA containing four bases whereas the effect of dye bound to DNA containing only AT bases is marginal. DNA-condensing biological polyamines are less effective than prion protein in quenching of DNA-bound YOYO fluorescence. The prion protein induces marginal quenching of fluorescence of the dye bound to oligonucleotides, which are resistant to condensation. The ultrastructural studies with electron microscope also validate the biophysical data. The GC bases of the target DNA are probably responsible for increased condensation in the presence of prion protein. To our knowledge, this is the first report of a human cellular protein inducing a sequence-dependent DNA condensation. The increased condensation of GC-rich DNA by prion protein may suggest a biological function of the prion protein and a role in its pathogenesis.

Effect of ionic size compensation by Ag+ incorporation in homogeneous Fe-substituted ZnO: studies on structural, mechanical, optical, and magnetic properties.

Substituting an ion of different size from that of the host element introduces lattice strain and defects. However, this mismatch may be significantly reduced by substituting an additional ion with a compensating size relative to the dopant. Such a double substitution might offer better solubility irrespective of the local distortions as well as the formation of defects in the valence states. Fe-substituted ZnO has been widely reported with conflicting results primarily arising from lack of chemical and structural homogeneity originating from preparation techniques, compositional fluctuations, and equivocal comprehension of actual solubility limits of the dopants. In this study, Ag ion has been incorporated in Fe-substituted ZnO to compensate the ionic size of Zn1-x [Fe0.8Ag0.2] x O (0 ≤ x ≤ 0.03125) by determining the solubility limit of the homogeneous material and their corresponding structural, mechanical, optical and magnetic properties have been investigated thoroughly. Co-substitution rearranges the lattice and leads to better crystal structures with tunable properties related to the amount of substitution.

Exciplex-Forming Cohost for High Efficiency and High Stability Phosphorescent Organic Light-Emitting Diodes.

An exciplex forming cohost system is employed to achieve a highly efficient organic light-emitting diode (OLED) with good electroluminescent lifetime. The exciplex is formed at the interfacial contact of a conventional star-shaped carbazole hole-transporting material, 4,4',4″-tris(N-carbazolyl)-triphenylamine (TCTA), and a triazine electron-transporting material, 2,4,6-tris[3-(1H-pyrazol-1-yl)phenyl]-1,3,5-triazine (3P-T2T). The excellent combination of TCTA and 3P-T2T is applied as the cohost of a common green phosphorescent emitter with almost zero energy loss. When Ir(ppy)2(acac) is dispersed in such exciplex cohost system, OLED device with maximum external quantum efficiency of 29.6%, the ultrahigh power efficiency of 147.3 lm/W, and current efficiency of 107 cd/A were successfully achieved. More importantly, the OLED device showed a low-efficiency roll-off and an operational lifetime (τ80) of ∼1020 min with the initial brightness of 2000 cd/m2, which is 56 times longer than the reference device. The significant difference of device stability was attributed to the degradation of exciplex system for energy transfer process, which was investigated by the photoluminescence aging measurement at room temperature and 100 K, respectively.

Correction: Effect of ionic size compensation by Ag+ incorporation in homogeneous Fe-substituted ZnO: studies on structural, mechanical, optical, and magnetic properties.

[This corrects the article DOI: 10.1039/C8RA02393J.].

Cu1-x Fe x O: hopping transport and ferromagnetism.

Single phase, sol-gel prepared Cu1-x Fe x O (0 ≤ x ≤ 0.125) powders are characterized in terms of structural, electronic and magnetic properties. Using dielectric and magnetic studies we investigate the coupling of electron and spin. The electrical conductivities and activation energies are studied with increasing Fe content. Modelling of experimental conductivity data emphasizes a single hopping mechanism for all samples except x = 0.125, which have two activation energies. Hole doping is confirmed by confirming a majority Fe3+ substitution of Cu2+ in CuO from X-ray photoelectron spectroscopy studies (XPS). Such a substitution results in stabilized ferromagnetism. Fe substitution introduces variation in coercivity as an intrinsic magnetic property in Fe-doped CuO, and not as a secondary impurity phase.

Light scattering from 2D arrays of monodispersed Ag-nanoparticles separated by tunable nano-gaps: spectral evolution and analytical analysis of plasmonic coupling.

Two dimensional arrays of monodispersed Ag-nanoparticles separated by different gaps with sub-10 nm precision are fabricated on anodic alumina substrates with self-organized pores. Light scattering spectra from the arrays evolve with the gaps, revealing plasmonic coupling among the nanoparticles, which can be satisfactorily interpreted by analytical formulae derived from generic dipolar approximation. The general formulism lays down a foundation for predicting the Q factor of an array of metallic nano-particles and its geometric characteristics.

Electrochemically replicated smooth aluminum foils for anodic alumina nanochannel arrays.

A fast electrochemical replication technique has been developed to fabricate large-scale ultra-smooth aluminum foils by exploiting readily available large-scale smooth silicon wafers as the masters. Since the adhesion of aluminum on silicon depends on the time of surface pretreatment in water, it is possible to either detach the replicated aluminum from the silicon master without damaging the replicated aluminum and master or integrate the aluminum film to the silicon substrate. Replicated ultra-smooth aluminum foils are used for the growth of both self-organized and lithographically guided long-range ordered arrays of anodic alumina nanochannels without any polishing pretreatment.

High speed fabrication of aluminum nanostructures with 10 nm spatial resolution by electrochemical replication.

A high fidelity electrochemical replication technique for the rapid fabrication of Al nanostructures with 10 nm lateral resolution has been successfully demonstrated. Aluminum is electrodeposited onto a lithographically patterned Si master using a non-aqueous organic hydride bath of aluminum chloride and lithium aluminum hydride at room temperature. Chemical pretreatment of the Si surface allows a clean detachment of the replicated Al foil from the master, permitting its repetitive use for mass replication. This high throughput technique opens up new possibilities in the fabrication of Al-related nanostructures, including the growth of long range ordered anodic alumina nanochannel arrays.