Poly(N-isopropylacrylamide)-b-Poly(L-lysine)-b-Poly(L-histidine) Triblock Amphiphilic Copolymer Nanomicelles for Dual-Responsive Anticancer Drug Delivery.

A series of ABC triblock poly(N-isopropylacrylamide)75-block-poly(L-lysine)35-block-poly(L-histidine)n (p(NIPAM)75-b-p(Lys)35-b-p(His)N) (N = 35,50,75,100) copolymer bio-conjugates were prepared by combining reversible addition-fragmentation chain transfer polymerization and fast ring-opening polymerization of N-carboxyanhydride a-amino acid using 1,3-dicyclohexylimidazolium hydrogen carbonate as a catalyst. All the resulting triblock copolymers self-assembled into spherical micellar aggregates in aqueous solution, irrespective of the chain length of the histidine block. The micellar aggregates encapsulated the anticancer drug doxorubicin (Dox) and exhibited high drug loading efficiency. Temperature and pH stimuli were applied to investigate the controlled release of Dox. The non-cytotoxic nature of the polymers was investigated using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Cellular uptake of the Dox-loaded micelles revealed that the micelles successfully release Dox in cancer cells in response to pH- and temperature-induced morphological change. In-vitro studies further confirmed that the Dox-loaded triblock copolymer micelle is an excellent platform for drug delivery.

Multi-stimuli-responsive nanomicelles fabricated using synthetic polymer polylysine conjugates for tumor microenvironment dependent drug delivery.

A series of multi-stimuli-responsive poly(N-isopropylacrylamide)30-SS-block-poly(L-lysine)30-block-poly(caprolactone)n (p(NIPAM)30-SS-b-p(Lys)30-b-p(CL)n) (n = 50, 75, 100, 125) triblock copolymers have been synthesized by combining reversible addition-fragmentation chain transfer polymerization of NIPAM, organo-catalyzed ring-opening polymerization (ROP) of Z-lysine N-carboxyanhydride and metal-catalyzed ROP of CL with an azide-alkyne click reaction. The pH-responsive p(Lys) and temperature-responsive p(NIPAM) blocks are tethered by a redox-responsive disulfide linker and biodegradable p(CL) blocks with different lengths are also combined to tune the lower critical solution temperature and drug loading capacity of the resulting polymers. Highly uniform micelles with ∼200 nm size were fabricated by the self-assembly of the resultant copolymers in the presence of doxorubicin (Dox) with a high Dox encapsulation efficiency of around 50%. The combination of the enhanced permeability and retention effect with pH-, temperature- and redox-sensitive tumor microenvironment-responsive drug delivery of the nanomicelles endows them with cell internalization capability for the successful antitumor efficiency. Interestingly, this multi-stimuli-responsive platform makes a distinction from the conventional block copolymer systems by demonstrating fascinating tumor targeting without utilizing any targeting moiety. Thus, the easily accessible multi-stimuli-responsive triblock copolymer can be a promising theranostic system for intracellular drug delivery.

Enhanced Photoinduced Carrier Generation Efficiency through Surface Band Bending in Topological Insulator Bi2Se3 Thin Films by the Oxidized Layer.

Topological insulators (TIs) have become popular in the field of optoelectronic devices because of their broadband and high-sensitivity properties, which are attributed to the narrow band gap of the bulk state and high mobility of the Dirac surface state. Although perfectly grown TIs are known to exhibit strong stability against oxidation, in most cases, the existence of vacancy defects in TIs reacts to air and the characteristics of TIs is affected by oxidation. Therefore, changes in the band structure and electrical characteristics by oxidation should be considered. A significant change occurs because of the oxidation; however, the dependence of the photoresponse of TIs on oxidation has not been studied in detail. In this study, the photoresponsivity of oxidized Bi2Se3 films is enhanced, rather than degraded, after oxidation in air for 24 h, resulting in a maximum responsivity of 140 mA W-1. This responsivity is substantially higher than previously reported values for Bi2Se3. Furthermore, a change in the photoresponse time of Bi2Se3 due to air exposure is systematically observed. Based on variations in the Fermi level and work function, using photoelectron spectroscopy, it is confirmed that the responsivity is improved from the junction effect of the Bi-based surface oxidized layer.

Facile and scalable synthesis of topologically nanoengineered polypeptides with excellent antimicrobial activities.

A facile and scalable strategy for the quick library synthesis of linear-, hinged-, star-, and cyclic-polypeptides with broad-spectrum antimicrobial activity has been reported. The topologically nanoengineered polypeptides show superior antimicrobial activity against Gram-positive and Gram-negative bacteria and low toxicity, allowing screening of architectural polypeptides as mimics of host defense peptides for antimicrobials.

High-Performance Transparent Quantum Dot Light-Emitting Diode with Patchable Transparent Electrodes.

Patchable electrodes are attractive for applications in optoelectronic devices because of their easy and reliable processability. However, development of reliable patchable transparent electrodes (TEs) with high optoelectronic performance is challenging; till now, optoelectronic devices fabricated with patchable TEs have been exhibiting limited performance. In this study, Ag nanowire (AgNW)/poly(methyl methacrylate) (PMMA) patchable TEs are developed and the highly efficient transparent quantum dot light-emitting diodes (QLEDs) using the patchable TEs are fabricated. AgNWs with optimized optoelectronic properties (figure of merit ≈ 3.3 × 10-2) are coated by an ultrathin PMMA nanolayer and transferred to thermal release tapes that enable physical attachment of TEs on the QLEDs without a significant damage to the adjacent active layer. The transparent QLEDs using patchable transparent top electrodes display excellent performance, with the maximum total luminance and current efficiency of 27 310 cd·m-2 and 45.99 cd·A-1, respectively. Fabricated by all-solution-based processes, these QLEDs exhibit the best performance to date among devices adopting patchable top electrodes.

P-N Junction Diode Using Plasma Boron-Doped Black Phosphorus for High-Performance Photovoltaic Devices.

This study used a spatially controlled boron-doping technique that enables a p-n junction diode to be realized within a single 2D black phosphorus (BP) nanosheet for high-performance photovoltaic application. The reliability of the BP surface and state-of-the-art 2D p-n heterostructure's gated junctions was obtained using the controllable pulsed-plasma process technique. Chemical and structural analyses of the boron-doped BP were performed using X-ray photoelectron spectroscopy, transmission electron microscopy, and first-principles density functional theory (DFT) calculations, and the electrical characteristics of a field-effect transistor based on the p-n heterostructure were determined. The incorporated boron generated high electron density at the BP surface. The electron mobility of BP was significantly enhanced to ∼265 cm2/V·s for the top gating mode, indicating greatly improved electron transport behavior. Ultraviolet photoelectron spectroscopy and DFT characterizations revealed the occurrence of significant surface charge transfer in the BP. Moreover, the pulsed-plasma boron-doped BP p-n junction devices exhibited high-efficiency photodetection behavior (rise time: 1.2 ms and responsivity: 11.3 mA/W at Vg = 0 V). This study's findings on the tunable nature of the surface-transfer doping scheme reveal that BP is a promising candidate for optoelectronic devices and advanced complementary logic electronics.

Interface engineering for a stable chemical structure of oxidized-black phosphorus via self-reduction in AlOx atomic layer deposition.

We evaluated the change in the chemical structure between dielectrics (AlOx and HfOx) grown by atomic layer deposition (ALD) and oxidized black phosphorus (BP), as a function of air exposure time. Chemical and structural analyses of the oxidized phosphorus species (PxOy) were performed using atomic force microscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, first-principles density functional theory calculations, and the electrical characteristics of field-effect transistors (FETs). Based on the combined experiments and theoretical investigations, we clearly show that oxidized phosphorus species (PxOy, until exposed for 24 h) are significantly decreased (self-reduction) during the ALD of AlOx. In particular, the field effect characteristics of a FET device based on Al2O3/AlOx/oxidized BP improved significantly with enhanced electrical properties, a mobility of ∼253 cm2 V-1 s-1 and an on-off ratio of ∼105, compared to those of HfO2/HfOx/oxidized BP with a mobility of ∼97 cm2 V-1 s-1 and an on-off ratio of ∼103-104. These distinct differences result from a significantly decreased interface trap density (Dit ∼ 1011 cm-2 eV-1) and subthreshold gate swing (SS ∼ 270 mV dec-1) in the BP device caused by the formation of stable energy states at the AlOx/oxidized BP interface, even with BP oxidized by air exposure.

Highly Efficient and Fully Solution-Processed Inverted Light-Emitting Diodes with Charge Control Interlayers.

In this work, we developed a charge control sandwich structure around QD layers for the inverted QLEDs, the performance of which is shown to exceed that of the conventional QLEDs in terms of the external quantum efficiency (EQE) and the current efficiency (CE). The QD light-emitting layer (EML) is sandwiched with two ultrathin interfacial layers: one is a poly(9-vinlycarbazole) (PVK) layer to prevent excess electrons, and the other is a polyethylenimine ethoxylated (PEIE) layer to reduce the hole injection barrier. The sandwich structure resolves the imbalance between injected holes and electrons and brings the level of balanced charge carriers to a maximum. We demonstrated the highly improved performance of 89.8 cd/A of current efficiency, 22.4% of external quantum efficiency, and 72 814 cd m-2 of maximum brightness with the solution-processed inverted QLED. This sandwich structure (PVK/QD/PEIE), as a framework, can be applied to various QLED devices for enhancing performance.

Al2O3 Passivation Effect in HfO2·Al2O3 Laminate Structures Grown on InP Substrates.

The passivation effect of an Al2O3 layer on the electrical properties was investigated in HfO2-Al2O3 laminate structures grown on indium phosphide (InP) substrate by atomic-layer deposition. The chemical state obtained using high-resolution X-ray photoelectron spectroscopy showed that interfacial reactions were dependent on the presence of the Al2O3 passivation layer and its sequence in the HfO2-Al2O3 laminate structures. Because of the interfacial reaction, the Al2O3/HfO2/Al2O3 structure showed the best electrical characteristics. The top Al2O3 layer suppressed the interdiffusion of oxidizing species into the HfO2 films, whereas the bottom Al2O3 layer blocked the outdiffusion of In and P atoms. As a result, the formation of In-O bonds was more effectively suppressed in the Al2O3/HfO2/Al2O3/InP structure than that in the HfO2-on-InP system. Moreover, conductance data revealed that the Al2O3 layer on InP reduces the midgap traps to 2.6 × 1012 eV-1 cm-2 (compared to that of HfO2/InP, that is, 5.4 × 1012 eV-1 cm-2). The suppression of gap states caused by the outdiffusion of In atoms significantly controls the degradation of capacitors caused by leakage current through the stacked oxide layers.

Polyethylenimine Ethoxylated-Mediated All-Solution-Processed High-Performance Flexible Inverted Quantum Dot-Light-Emitting Device.

We report on an all-solution-processed fabrication of highly efficient green quantum dot-light-emitting diodes (QLEDs) with an inverted architecture, where an interfacial polymeric surface modifier of polyethylenimine ethoxylated (PEIE) is inserted between a quantum dot (QD) emitting layer (EML) and a hole transport layer (HTL), and a MoOx hole injection layer is solution deposited on top of the HTL. Among the inverted QLEDs with varied PEIE thicknesses, the device with an optimal PEIE thickness of 15.5 nm shows record maximum efficiency values of 65.3 cd/A in current efficiency and 15.6% in external quantum efficiency (EQE). All-solution-processed fabrication of inverted QLED is further implemented on a flexible platform by developing a high-performing transparent conducting composite film of ZnO nanoparticles-overcoated on Ag nanowires. The resulting flexible inverted device possesses 35.1 cd/A in current efficiency and 8.4% in EQE, which are also the highest efficiency values ever reported in flexible QLEDs.

Controlling the defects and transition layer in SiO2 films grown on 4H-SiC via direct plasma-assisted oxidation.

The structural stability and electrical performance of SiO2 grown on SiC via direct plasma-assisted oxidation were investigated. To investigate the changes in the electronic structure and electrical characteristics caused by the interfacial reaction between the SiO2 film (thickness ~5 nm) and SiC, X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), density functional theory (DFT) calculations, and electrical measurements were performed. The SiO2 films grown via direct plasma-assisted oxidation at room temperature for 300s exhibited significantly decreased concentrations of silicon oxycarbides (SiOxCy) in the transition layer compared to that of conventionally grown (i.e., thermally grown) SiO2 films. Moreover, the plasma-assisted SiO2 films exhibited enhanced electrical characteristics, such as reduced frequency dispersion, hysteresis, and interface trap density (Dit ≈ 1011 cm-2 · eV-1). In particular, stress induced leakage current (SILC) characteristics showed that the generation of defect states can be dramatically suppressed in metal oxide semiconductor (MOS) structures with plasma-assisted oxide layer due to the formation of stable Si-O bonds and the reduced concentrations of SiOxCy species defect states in the transition layer. That is, energetically stable interfacial states of high quality SiO2 on SiC can be obtained by the controlling the formation of SiOxCy through the highly reactive direct plasma-assisted oxidation process.

Improved electroluminescence of quantum dot light-emitting diodes enabled by a partial ligand exchange with benzenethiol.

In this study, benzenethiol ligands were applied to the surface of CdSe@ZnS core@shell quantum dots (QDs) and their effect on the performance of quantum dot light-emitting diodes (QD-LEDs) was investigated. Conventional long-chained oleic acid (OA) and trioctylphosphine (TOP) capping ligands were partially replaced by short-chained benzenethiol ligands in order to increase the stability of QDs during purification and also improve the electroluminescence performance of QD-LEDs. The quantum yield of the QD solution was increased from 41% to 84% by the benzenethiol ligand exchange. The mobility of the QD films with benzenethiol ligands approximately doubled to 2.42 × 10(-5) cm(2) V(-1) s(-1) from 1.19 × 10(-5) cm(2) V(-1) s(-1) compared to the device consisting of OA/TOP-capped QDs, and an approximately 1.8-fold improvement was achieved over QD-LEDs fabricated with bezenethiol ligand-exchanged QDs with respect to the maximum luminance and current efficiency. The turn-on voltage decreased by about -0.6 V through shifting the energy level of the QDs with benzenethiol ligands compared to conventional OA and TOP ligands.

Tunable White Fluorescent Copper Gallium Sulfide Quantum Dots Enabled by Mn Doping.

Fluorescence of semiconductor quantum dots (QDs) can be tuned by engineering the band gap via size and composition control and further doping them with impurity ions. Targeting on highly bright white-emissive I-III-VI -type copper gallium sulfide (Cu-Ga-S, CGS) host QDs with the entire visible spectral coverage of blue to red, herein, Mn(2+) ion doping, through surface adsorption and lattice diffusion is fulfilled. Upon doping a distinct Mn emission from (4)T1-(6)A1 transition successfully appears in white photoluminescence (PL) of undoped CGS/ZnS core/shell QDs and with varying Mn concentration a systematic white spectral evolution of CGS:Mn/ZnS QDs is achievable with high PL quantum yield retained. The origins of white PL of CGS:Mn/ZnS QDs that is well decomposed into three emission bands are appropriately assigned. The resulting single-phased, doped QDs are then employed as near-UV-to-white down converters for the fabrication of white light-emitting diodes (LEDs). Electroluminescent properties of white QD-LEDs depending on Mn concentration of CGS:Mn/ZnS QDs and forward current are also discussed in detail.

Structural and Electrical Properties of EOT HfO2 (<1 nm) Grown on InAs by Atomic Layer Deposition and Its Thermal Stability.

We report on changes in the structural, interfacial, and electrical characteristics of sub-1 nm equivalent oxide thickness (EOT) HfO2 grown on InAs by atomic layer deposition. When the HfO2 film was deposited on an InAs substrate at a temperature of 300 °C, the HfO2 was in an amorphous phase with an sharp interface, an EOT of 0.9 nm, and low preexisting interfacial defect states. During post deposition annealing (PDA) at 600 °C, the HfO2 was transformed from an amorphous to a single crystalline orthorhombic phase, which minimizes the interfacial lattice mismatch below 0.8%. Accordingly, the HfO2 dielectric after the PDA had a dielectric constant of ∼24 because of the permittivity of the well-ordered orthorhombic HfO2 structure. Moreover, border traps were reduced by half than the as-grown sample due to a reduction in bulk defects in HfO2 dielectric during the PDA. However, in terms of other electrical properties, the characteristics of the PDA-treated sample were degraded compared to the as-grown sample, with EOT values of 1.0 nm and larger interfacial defect states (Dit) above 1 × 10(14) cm(-2) eV(-1). X-ray photoelectron spectroscopy data indicated that the diffusion of In atoms from the InAs substrate into the HfO2 dielectric during the PDA at 600 °C resulted in the development of substantial midgap states.

CdSe/ZnS quantum dot thin film formation by an electrospray deposition process for light-emitting devices.

About 30 nm quantum-dot thin films are formed by electrospray deposition (ESD) process and quantum-dot-light-emitting-diodes (QD-LEDs) are demonstrated. Maximum brightness of 23 000 cd m(-2) and current efficiency of 5.9 cd A(-1) are achieved with the ESD process. The ESD process can be a potential solution for large area quantum dot layers with simple and flexible control.

Effects of nitrogen incorporation in HfO(2) grown on InP by atomic layer deposition: an evolution in structural, chemical, and electrical characteristics.

We investigated the effects of postnitridation on the structural characteristics and interfacial reactions of HfO2 thin films grown on InP by atomic layer deposition (ALD) as a function of film thickness. By postdeposition annealing under NH3 vapor (PDN) at 600 °C, an InN layer formed at the HfO2/InP interface, and ionized NHx was incorporated in the HfO2 film. We demonstrate that structural changes resulting from nitridation of HfO2/InP depend on the film thickness (i.e., a single-crystal interfacial layer of h-InN formed at thin (2 nm) HfO2/InP interfaces, whereas an amorphous InN layer formed at thick (>6 nm) HfO2/InP interfaces). Consequently, the tetragonal structure of HfO2 transformed into a mixture structure of tetragonal and monoclinic because the interfacial InN layer relieved interfacial strain between HfO2 and InP. During postdeposition annealing (PDA) in HfO2/InP at 600 °C, large numbers of oxidation states were generated as a result of interfacial reactions between interdiffused oxygen impurities and out-diffused InP substrate elements. However, in the case of the PDN of HfO2/InP structures at 600 °C, nitrogen incorporation in the HfO2 film effectively blocked the out-diffusion of atomic In and P, thus suppressing the formation of oxidation states. Accordingly, the number of interfacial defect states (Dit) within the band gap of InP was significantly reduced, which was also supported by DFT calculations. Interfacial InN in HfO2/InP increased the electron-barrier height to ∼0.6 eV, which led to low-leakage-current density in the gate voltage region over 2 V.

Characterization of low temperature graphene synthesis in inductively coupled plasma chemical vapor deposition process with optical emission spectroscopy.

Low-temperature graphene was synthesized at 400 degrees C with inductively coupled plasma chemical vapor deposition (PECVD) process. The effects of plasma power and flow rate of various carbon containing precursors and hydrogen on graphene properties were investigated with optical emission spectroscopy (OES). Various radicals monitored by OES were correlated with graphene film properties such as sheet resistance, I(D)/I(G) ratio of Raman spectra and transparency. C2H2 was used as a main precursor and the increase of plasma power enhanced intensity of carbon (C2) radical OES intensity in plasma, reduced sheet resistance and increased transparency of graphene films. The reduced flow rate of C2H2 decreased sheet resistance and increased transparency of graphene films in the range of this study. H2 addition was found to increase sheet resistance, transparency and attributed to reduction of graphene grain and etching graphene layers. OES analysis showed that C2 radicals contribute to graphite networking and sheet resistance reduction. TEM and AFM were applied to provide credible information that graphene had been successfully grown at low temperature.

Polymer and small molecule mixture for organic hole transport layers in quantum dot light-emitting diodes.

The performance of quantum dot light-emitting diodes (QD-LEDs) was investigated for different hole transport layers with small molecules and polymers: poly(4-butyl-phenyl-diphenyl-amine), poly-N-vinylcarbazole (PVK), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-diphenyl-4,4'-diamine, 4,4',4″-tris(N-carbazolyl)-triphenyl-amine (TCTA), and 4,4'-bis(carbazole-9-yl)biphenyl (CBP). The electroluminescence performance of QD-LEDs was considerably improved by adding small molecules (TCTA or CBP) having high hole mobilily to the polymer hole transport material (PVK). The maximal current efficiency of QD-LED-based PVK was improved by 27% upon addition of 20 wt % TCTA due to the hole injection improvement. The lower turn-on voltage, the higher current density, and the higher luminance were achieved by addition of TCTA. The maximal luminance of 40900 cd/m(2) and the highest current efficiency of 14.0 cd/A with the narrow full width at half-maximum (<35 nm) were achieved by the best hole transport layer.

Structural evolution and the control of defects in atomic layer deposited HfO2-Al2O3 stacked films on GaAs.

The structural characteristics and interfacial reactions of bilayered dielectric stacks of 3 nm HfO2/2 nm Al2O3 and 3 nm Al2O3/2 nm HfO2 on GaAs, prepared by atomic layer deposition (ALD), were examined during film growth and the postannealing process. During the postdeposition annealing (PDA) of the Al2O3/HfO2/GaAs structures at 700 °C, large amounts of Ga oxides were generated between the Al2O3 and HfO2 films as the result of interfacial reactions between interdiffused oxygen impurities and out-diffused atomic Ga. However, in the case of the HfO2/Al2O3/GaAs structures, the presence of an Al2O3 buffer layer effectively blocked the out-diffusion of atomic Ga, thus suppressing the formation of Ga oxide. Microstructural analyses showed that HfO2 films that were deposited on Al2O3/GaAs had completely crystallized during the PDA process, even at 700 °C, because of the Al2O3 diffusion barrier. Capacitance-voltage measurements showed a relatively large frequency dispersion of the Al2O3/HfO2/GaAs structure in accumulation capacitance compared to the HfO2/Al2O3/GaAs structure due to a higher interface state density. Conductance results revealed that the Al2O3 buffer layer on GaAs resulted in a significant reduction in gap states in GaAs. The induced gap state in the Al2O3/HfO2/GaAs structure originated from the out-diffusion of atomic Ga into the HfO2 film. Density functional theory calculations supported this conclusion.

Characterization of low-k dielectric SiCOH films deposited with decamethylcyclopentasiloxane and cyclohexane.

Ultra low-k dielectric SiCOH films were deposited with decamethylcyclopentasiloxane (DMCPSO, C10H30O5Si5) and cyclohexane (C6H12) precursors by plasma-enhanced chemical vapor deposition at the deposition temperature between 25 and 200 degrees C and their chemical composition and deposition kinetics were investigated in this work. Low dielectric constants of 1.9-2.4 were obtained due to intrinsic nanoscale pores originating from the relatively large ring structure of DMCPSO and to the relatively large fraction of carbon contents in cyclohexane. Three different deposition regions were identified in the temperature range. Deposition rates increased with temperature below 40 degrees C and decreased as temperature increased to 75 degrees C with apparent activation energies of 56 kJ/mol x K at < 40 degrees C, -26 kJ/mol x K at 40-100 degrees C, respectively. In the temperature region of 40-100 degrees C hydrocarbon deposition and decomposition process compete each other and decomposition becomes dominant, which results in apparent negative activation energy. Deposition rates remain relatively unaffected with further increases of temperature above 100 degrees C. FTIR analysis and deposition kinetic analysis showed that hydrocarbon deposition is the major factor determining chemical composition and deposition rate. The hydrocarbon deposition dominates especially at lower temperatures below 40 degrees C and Si-O fraction increases above 40 degrees C. We believe that dielectric constants of low-k films can be controlled by manipulating the fraction of deposited hydrocarbon through temperature control.