Systematic Doping Control of CVD Graphene Transistors with Functionalized Aromatic Self‐Assembled Monolayers

Recent reports have shown that self‐assembled monolayers (SAMs) can induce doping effects in graphene transistors. However, a lack of understanding persists surrounding the quantitative relationship between SAM molecular design and its effects on graphene. In order to facilitate the fabrication of next‐generation graphene‐based devices it is important to reliably and predictably control the properties of graphene without negatively impacting its intrinsic high performance. In this study, SAMs with varying dipole magnitudes/directions are utilized and these values are directly correlated to changes in performance seen in graphene transistors. It is found that, by knowing the z‐component of the SAM dipole, one can reliably predict the shift in graphene charge neutrality point after taking into account the influence of the metal electrodes (which also play a role in doping graphene). This relationship is verified through density functional theory and comprehensive device studies utilizing atomic force microscopy, X‐ray photoelectron spectroscopy, Raman spectroscopy, and electrical characterization of graphene transistors. It is shown that properties of graphene transistors can be predictably controlled with SAMs when considering the total doping environment. Additionally, it is found that methylthio‐terminated SAMs strongly interact with graphene allowing for a cleaner graphene transfer and enhanced charge mobility.     

Hierarchical Graphene–Carbon Fiber Composite Paper as a Flexible Lateral Heat Spreader

As a low dimensional crystal, graphene attracts great attention as heat dissipation material due to its unique thermal transfer property exceeding the limit of bulk graphite. In this contribution, flexible graphene–carbon fiber composite paper is fabricated by depositing graphene oxide into the carbon fiber precursor followed by carbonization. In this full‐carbon architecture, scaffold of one‐dimensional carbon fiber is employed as the structural component to reinforce the mechanical strength, while the hierarchically arranged two‐dimensional graphene in the framework provides a convenient pathway for in‐plane acoustic phonon transmission. The as‐obtained hierarchical carbon/carbon composite paper possesses ultra‐high in‐plane thermal conductivity of 977 W m^?1 K^?1 and favorable tensile strength of 15.3 MPa. The combined mechanical and thermal performances make the material highly desirable as lateral heat spreader for next‐generation commercial portable electronics.     

Synergistic Computational‐Experimental Approach to Improve Ionene Polymer‐Based Functional Hydrogels

The manifold applications of ionene‐based materials such as hydrogels in daily life, biomedical sciences, and industrial processes are a consequence of their unique physical and chemical properties, which are governed by a judicious balance between multiple non‐covalent interactions. However, one of the most critical aspects identified for a broader use of different polyelectrolytes is the need of raising their gelation efficiency. This work focuses on surfactant‐free ionene polymers 1 ? 3 containing DABCO and N,N′‐(x‐phenylene)dibenzamide (x = ortho‐/meta‐/para‐) linkages as model systems to develop a combined computational‐experimental approach to improve the hydrogelation through a better understanding of the gelation mechanism. Molecular dynamics simulations of isomeric ionenes 1–3 with explicit water molecules point out remarkable differences in the assembly of the polymeric chains in each case. Interchain regions with high degree of hydration (i.e., polymer···water interactions) and zones dominated by polymer···polymer interactions are evident in the case of ortho‐ ( 1 ) and meta‐ ( 2 ) isomeric ionenes, whereas domains controlled by polymer···polymer interactions are practically inexistent in 3 . In excellent agreement, ortho‐ionene 1 provides experimentally the best hydrogels with unique features such as thixotropic behavior and dispersion ability for single‐walles carbon nanotubes.     

Photoresponsive Protein–Graphene–Protein Hybrid Capsules with Dual Targeted Heat‐Triggered Drug Delivery Approach for Enhanced Tumor Therapy

A novel photo‐responsive protein–graphene–protein (PGP) capsule that doubles as a photothermal agent with core/shell structure is constructed by anchoring reduced graphene oxide nanosheets on one‐component protein (lactoferrin) shell through a double emulsion method. PGP capsules can transport fully concealed hydrophilic anticancer cargo, doxorubicin (Dox), with a large payload (9.43 μmol g^‐1) to be later unloaded in a burst‐like manner by photo‐actuation triggered by near‐infrared irradiation. Being biocompatible yet with a high cancer cell targeting efficiency, PGP capsules have successfully eradicated subcutaneous tumors in 10 d following a single 5 min NIR irradiation without distal damage. Besides, the photochemothermal therapy of PGP capsules eradicates tumor cells not only in the light‐treating area but also widely light‐omitted tumor cells, overcoming the tumor recurrence due to efficient cell killing efficacy. These results demonstrate that the PGP capsule is a potential new drug delivery platform for local‐targeting, on‐demand, photoresponsive, combined chemotherapy/hyperthermia for tumor treatment and other biomedical applications.     

Bioinspired Fabrication of Superhydrophobic Graphene Films by Two‐Beam Laser Interference

Reported here is a bioinspired fabrication of superhydrophobic graphene surfaces by means of two‐beam laser interference (TBLI) treatment of graphene oxide (GO) films. Microscale grating‐like structures with tunable periods and additional nanoscale roughness are readily created on graphene films due to laser induced ablation effect. Synchronously, abundant hydrophilic oxygen‐containing groups (OCGs) on GO sheets can be drastically removed after TBLI treatment, which lower its surface energy significantly. The synergistic effect of micro‐nanostructuring and the OCGs removal endows the resultant graphene films with unique superhydrophobicity. Additionally, dual TBLI treatment with 90° rotation is implemented to fabricate superhydrophobic graphene films with two‐dimensional grating‐like structures that can effectively avoid the anisotropic hydrophobicity originated from the grooved structures. Moreover, the superhydrophobic graphene films become conductive due to the laser reduction effect. Unique optical characteristics including transmission diffraction and brilliant structural color are also observed due to the presence of periodic microstructures. As a mask‐free, chemical‐free, and cost‐effective method, the TBLI processing of GO may open up a new way to biomimetic graphene surfaces, and thus hold great promise for the development of novel graphene‐based microdevices.     

Solution Processing Route to Multifunctional Titania Thin Films: Highly Conductive and Photcatalytically Active Nb:TiO2

This paper reports the synthesis of highly conductive niobium doped titanium dioxide (Nb:TiO₂) films from the decomposition of Ti(OEt)₄ with dopant quantities of Nb(OEt)₅ by aerosol‐assisted chemical vapor deposition (AACVD). Doping Nb into the Ti sites results in n‐type conductivity, as determined by Hall effect measurements. The doped films display significantly improved electrical properties compared to pristine TiO₂ films. For 5 at.% Nb in the films, the charge carrier concentration was 2 × 10²¹ cm^?3 with a mobility of 2 cm² V^–1 s^–1 . The corresponding sheet resistance is as low as 6.5 Ω sq^–1 making the films suitable candidates for transparent conducting oxide (TCO) materials. This is, to the best of our knowledge, the lowest reported sheet resistance for Nb:TiO₂ films synthesized by vapour deposition. The doped films are also blue in colour, with the intensity dependent on the Nb concentration in the films. A combination of synchrotron, laboratory and theoretical techniques confirmed niobium doping into the anatase TiO₂ lattice. Computational methods also confirmed experimental results of both delocalized (Ti⁴⁺) and localized polaronic states (Ti³⁺) states. Additionally, the doped films also functioned as photocatalysts. Thus, Nb:TiO₂ combines four functional properties (photocatalysis, electrical conductivity, optical transparency and blue colouration) within the same layer, making it a promising alternative to conventional TCO materials.     

Improved CO2 Capture from Flue Gas by Basic Sites,Charge Gradients,and Missing Linker Defects on Nickel Face Cubic Centered MOFs

The adsorptive properties of the isoreticular series [Ni₈(OH)₄(H₂O)₂(BDP_X)₆] (H₂BDP_X = 1,4‐bis(pyrazol‐4‐yl)benzene‐4‐X with X = H (1), OH (2), NH₂ (3)) can be enhanced by postsynthetic treatment with an excess of KOH in ethanol. In the case of X = H, NH₂, this treatment leads to partial removal of the organic linkers, deprotonation of coordinated water molecules and introduction of extraframework cations, giving rise to materials of K[Ni₈(OH)₅(EtO)‐(H₂O)₂(BDP_X)_5.5] (1@KOH, 3@KOH) formulation, in which the original framework topology is maintained. By contrast, the same treatment with KOH in the [Ni₈(OH)₄(H₂O)₂(BDP_OH)₆] (2) system, enclosing the more acidic phenol residues, leads to a new material containing a larger fraction of missing linker defects and extra‐framework cations as well as phenolate residues, giving rise to the material K₃[Ni₈(OH)₃(EtO)(H₂O)₆(BDP_O)₅] (2@KOH), which also conserves the original face cubic centered (fcu) topology. It is noteworthy that the introduction of missing linker defects leads to a higher accessible pore volume with a concomitant increased adsorption capacity. Moreover, the creation of coordinatively unsaturated metal centers, charge gradients, and phenolate nucleophilic sites in 2@KOH gives rise to a boosting of CO₂ capture features with increased adsorption heat and adsorption capacity, as proven by the measurement of pulse gas chromatography and breakthrough curve measurements of simulated flue gas.     

Porous Cu(I) Triazolate Framework and Derived Hybrid Membrane with Exceptionally High Sensing Efficiency for Gaseous Oxygen

Phosphorescent complexes of precious metal ions are widely studied as optical sensing materials for molecular oxygen. Combining the advantages of luminescent complexes and porous matrixes, porous coordination polymers show great potential for oxygen‐sensing, although their sensitivity, requirement of precious metal, and device fabrication remain challenging issues. In this work, the photoluminescence and oxygen‐sensing properties of the porous Cu(I) triazolate framework [Cu(detz)] (MAF‐2, Hdetz = 3,5‐diethyl‐1,2,4‐trizole) is studied in detail, which shows high chemical stability in moisture and water, very long phosphorescent lifetime (116 μs) and large Stokes shift (14 562 cm^?1), as well as considerable oxygen permeability (1.7 × 10^?11 mol cm^?1 s^?1 bar^?1) at ambient conditions, giving rise to exceptionally high luminescence quenching efficiency of 99.7% at 1 bar O₂ (I ₀/I ₁₀₀ = 356) with a perfectly linear Stern‐Volmer plot (K _SV = 356 bar^?1, R ² = 0.9998), fast response and good reversibility. Further, a counter‐diffusion crystal‐growth method was developed to fabricate MAF‐2 thin films protected by silicone rubbers as the first example of soft membrane oxygen sensor based on coordination polymer or metal‐organic framework, which exhibited extraordinary oxygen‐sensing performance (limit of detection = 0.047 mbar) and outstanding mechanical property, as well as outstanding chemical stability even in an acidic atmosphere.     

Atomistic Origin of the Enhanced Crystallization Speed and n‐Type Conductivity in Bi‐doped Ge‐Sb‐Te Phase‐Change Materials

Phase‐change alloys are the functional materials at the heart of an emerging digital‐storage technology. The GeTe‐Sb₂Te₃ pseudo‐binary systems, in particular the composition Ge₂Sb₂Te₅ (GST), are one of a handful of materials which meet the unique requirements of a stable amorphous phase, rapid amorphous‐to‐crystalline phase transition, and significant contrasts in optical and electrical properties between material states. The properties of GST can be optimized by doping with p‐block elements, of which Bi has interesting effects on the crystallization kinetics and electrical properties. A comprehensive simulational study of Bi‐doped GST is carried out, looking at trends in behavior and properties as a function of dopant concentration. The results reveal how Bi integrates into the host matrix, and provide insight into its enhancement of the crystallization speed. A straightforward explanation is proposed for the reversal of the charge‐carrier sign beyond a critical doping threshold. The effect of Bi on the optical properties of GST is also investigated. The microscopic insight from this study may assist in the future selection of dopants to optimize the phase‐change properties of GST, and also of other PCMs, and the general methods employed in this work should be applicable to the study of related materials, for example, doped chalcogenide glasses.     

Nanoshuttered OLEDs: Unveiled Invisible Auxiliary Electrode

In this study, organic light‐emitting diodes (OLEDs) with enhanced optical properties are fabricated by inserting a nanosized stripe auxiliary electrode layer (nSAEL) between the substrate and an indium tin oxide (ITO) layer. This design can avoid the shortcomings of conventional microsized layers while maintaining high optical uniformity due to the improved conductivity of the electrode. The primary advantage is that the nSAEL (submicrometer scale) is no longer visible to the naked eye. Moreover, the reflective shuttered (grating) structure of the nSAEL increases the forward‐directed light by the microcavity (MC) effect and minimizes the loss of light by the extracting the surface plasmon polariton (SPP) mode. In this study, the degree of the MC and SPP can be controlled with the parameters of the nSAEL by simply conjugating the conditions of laser interference lithography (LIL). Therefore, the current and power efficiencies of the device with an nSAEL with optimized parameters are 1.17 and 1.23 times higher than the reference device at 1000 cd/m², respectively, and at these parameters, the overall sheet resistance is reduced to less than half (48%). All of the processes are verified by comparing the computational simulation results and the experimental results obtained with the actual fabricated device.