Amplifying Charge‐Transfer Characteristics of Graphene for Triiodide Reduction in Dye‐Sensitized Solar Cells

The fabrication and functionalization of large‐area graphene and its electrocatalytic properties for iodine reduction in a dye‐sensitized solar cell are reported. The graphene film, grown by thermal chemical vapor deposition, contains three to five layers of monolayer graphene, as confirmed by Raman spectroscopy and high‐resolution transmission electron microscopy. Further, the graphene film is treated with CF₄ reactive‐ion plasma and fluorine ions are successfully doped into graphene as confirmed by X‐ray photoelectron spectroscopy and UV‐photoemission spectroscopy. The fluorinated graphene shows no structural deformations compared to the pristine graphene except an increase in surface roughness. Electrochemical characterization reveals that the catalytic activity of graphene for iodine reduction increases with increasing plasma treatment time, which is attributed to an increase in catalytic sites. Further, the fluorinated graphene is characterized in use as a counter‐electrode in a full dye‐sensitized solar cell and shows ca. 2.56% photon to electron conversion efficiency with ca. 11 mA cm^?2 current density. The shift in work function in F^? doped graphene is attributed to the shift in graphene redox potential which results in graphene's electrocatalytic‐activity enhancement.     

Growth and Isolation of Large Area Boron‐Doped Nanocrystalline Diamond Sheets: A Route toward Diamond‐on‐Graphene Heterojunction

Many material device applications would benefit from thin diamond coatings, but current growth techniques, such as chemical vapor deposition (CVD) or atomic layer deposition require high substrate and gas‐phase temperatures that would destroy the device being coated. The development of freestanding, thin boron‐doped diamond nanosheets grown on tantalum foil substrates via microwave plasma‐assisted CVD is reported. These diamond sheets (measuring up to 4 × 5 mm in planar area, and 300–600 nm in thickness) are removed from the substrate using mechanical exfoliation and then transferred to other substrates, including Si/SiO₂ and graphene. The electronic properties of the resulting diamond nanosheets and their dependence on the free‐standing growth, the mechanical exfoliation and transfer processes, and ultimately on their composition are characterized. To validate this, a prototypical diamond nanosheet–graphene field effect transistor‐like (DNGfet) device is developed and its electronic transport properties are studied as a function of temperature. The resulting DNGfet device exhibits thermally activated transport (thermionic conductance) above 50 K. Below 50 K a transition to variable range hopping is observed. These findings demonstrate the first step towards a low‐temperature diamond‐based transistor.     

Improving Graphene Diffusion Barriers via Stacking Multiple Layers and Grain Size Engineering

It is shown that the performance of graphene diffusion barriers can be enhanced by stacking multiple layers of graphene and increasing grain size. The focus is on large‐area barriers of graphene grown by chemical vapor deposition (CVD) in the context of passivating an underlying Cu substrate from oxidation in air at 200 °C and use imaging Raman spectroscopy as a tool to temporally and spatially map the barrier performance and to guide barrier design. At 200 °C in air, Cu oxidation proceeds in multiple regimes: first slowly via transport through atomic‐scale grain boundary defects inherent to CVD‐graphene and then more rapidly as the graphene itself degrades and new defects are formed. In the initial regime, the graphene passivates better than previously reported. Whereas oxidation through single sheets primarily occurs through grain boundaries, oxidation through multiple sheets is spatially confined to their intersection. Performance further increases with grain‐size. The degradation of the graphene itself at 200 °C ultimately limits high temperature but suggests superior low temperature barrier performance. This study is expected to improve the understanding of mass transport through CVD‐graphene materials and lead to improved large area graphene materials for barrier applications.     

Large‐Scale Synthesis of Bi‐layer Graphene in Strongly Coupled Stacking Order

Large‐scale synthesis of single‐layer graphene (SLG) by chemical vapor deposition (CVD) has received a lot of attention recently. However, CVD synthesis of AB stacked bi‐layer graphene (BLG) is still challenging. Here, we report synthesis of BLG homogeneously at large scale by thermal CVD. The 2D Raman band of CVD BLG splits into four components, suggesting splitting of electronic bands due to strong interlayer coupling. The splitting of electronic bands in CVD BLG is further evidenced by the study of near infrared absorption and carrier dynamics are probed by transient absorption spectroscopy. UV photoelectron spectroscopy invesigation also indiates CVD BLG possesses different electronic structures to those of CVD SLG. The growth mechanism of BLG is found to be related to catalytic activity of the copper (Cu) surface, which is determined by the purity of Cu foils employed in the CVD process. Our work shows that strongly coupled or even AB stacked BLG can be grown on Cu foils at large scale, which is of particular importance for device applications based on their split electronic bands.     

High‐Performance Hybrid Solar Cell Made from CdSe/CdTe Nanocrystals Supported on Reduced Graphene Oxide and PCDTBT

Core/shell tetrapods synthesized from CdSe and CdTe exhibit a type II band offset that induces separation of charge upon photoexcitation and localizes carriers to different regions of the tetrahedral geometry. CdSe/CdTe nanocrystals immobilized on oleylamine‐functionalized reduced graphene oxide (rGO) sheets can be homogeneously mixed with an organic dye (PCDTBT) to form donor–acceptor dispersed heterojunctions and exhibit a high power conversion efficiency of ～3.3% in solar cell devices. The near‐IR light absorbing type II nanocrystals complement the absorption spectrum of the visible light‐absorbing organics. The high efficiency is attributed to the amine‐functionalized rGO sheets, which allow intimate contact with the nanocrystals and efficient dispersal in the organic matrix, contributing to highly efficient charge separation and transfer at the nanocrystal, rGO, and polymer interfaces.     

Metal‐Free Growth of Nanographene on Silicon Oxides for Transparent Conducting Applications

Conventional methods to prepare large‐area graphene for transparent conducting electrodes involve the wet etching of the metal catalyst and the transfer of the graphene film, which can degrade the film through the creation of wrinkles, cracks, or tears. The resulting films may also be obscured by residual metal impurities and polymer contaminants. Here, it is shown that direct growth of large‐area flat nanographene films on silica can be achieved at low temperature (400 °C) by chemical vapor deposition without the use of metal catalysts. Raman spectroscopy and TEM confirm the formation of a hexagonal atomic network of sp²‐bonded carbon with a domain size of about 3–5 nm. Further spectroscopic analysis reveals the formation of SiC between the nanographene and SiO₂, indicating that SiC acts as a catalyst. The optical transmittance of the graphene films is comparable with transferred CVD graphene grown on Cu foils. Despite the fact that the electrical conductivity is an order of magnitude lower than CVD graphene grown on metals, the sheet resistance remains 1–2 orders of magnitude better than well‐reduced graphene oxides.     

A Generic Synthetic Approach to Large‐Scale Pristine‐Graphene/Metal‐Nanoparticles Hybrids

The homogeneous attachment of metal‐nanoparticles (metal‐NPs) on pristine‐graphene surface to construct pristine‐graphene/metal‐NPs hybrids is highly expected for application in many fields such as transparent electrodes and conductive composites. However, it remains a great challenge since the pristine‐graphene is highly hydrophobic. Here, an environmentally friendly generic synthetic approach to large‐scale pristine‐graphene/metal‐NPs hybrids is presented, by a combinatorial process of exfoliating expanded graphite in N‐methyl pyrrolidone via sonication and centrifugation to achieve the pristine‐graphene, and attaching pre‐synthesized metal‐NPs on the pristine‐graphene in ethanol via van der Waals interactions between the metal‐NPs and the pristine‐graphene. Nanoparticles of different metals (such as Ag, Au, and Pd) with various morphologies (such as sphere, cube, plate, multi‐angle, and spherical‐particle assembling) can be homogeneously attached on the defect‐free pristine‐graphene with controlled packing densities. Both the pristine‐graphene and the metal‐NPs preserve their original intrinsic structures. The as‐synthesized pristine‐graphene/Ag‐NPs hybrids show very high surface‐enhanced Raman scattering activity due to the combined effects of large surface area of the pristine‐graphene to adsorb more target molecules and the electromagnetic enhancement of the Ag‐NPs. This large‐scale synthesis of the pristine‐graphene/metal‐NPs hybrids with tunable shape and packing density of metal‐NPs opens up opportunities for fundamental research and potential applications ranging from devices to transparent electrodes and conductive composites.     

One‐Step Ionic‐Liquid‐Assisted Electrochemical Synthesis of Ionic‐Liquid‐Functionalized Graphene Sheets Directly from Graphite

Graphite, inexpensive and available in large quantities, unfortunately does not readily exfoliate to yield individual graphene sheets. Here a mild, one‐step electrochemical approach for the preparation of ionic‐liquid‐functionalized graphite sheets with the assistance of an ionic liquid and water is presented. These ionic‐liquid‐treated graphite sheets can be exfoliated into functionalized graphene nanosheets that can not only be individuated and homogeneously distributed into polar aprotic solvents, but also need not be further deoxidized. Different types of ionic liquids and different ratios of the ionic liquid to water can influence the properties of the graphene nanosheets. Graphene nanosheet/polystyrene composites synthesized by a liquid‐phase blend route exhibit a percolation threshold of 0.1 vol % for room temperature electrical conductivity, and, at only 4.19 vol %, this composite has a conductivity of 13.84 S m⁻¹, which is 3–15 times that of polystyrene composites filled with single‐walled carbon nanotubes.     

Epoxide Speciation and Functional Group Distribution in Graphene Oxide Paper‐Like Materials

The electronic structure and chemical bonding of three differently prepared samples of graphene oxide paper‐like sheets are studied. Two are created by water filtration of fully oxidized graphene sheets, although one is later intercalated with dodecylamine. The third is created by reducing graphene oxide with hydrazine hydrate. The spectroscopic fingerprints of the aligned epoxide functional groups that unzip the carbon basal plane are found. This unzipping appears to be a result of aging, and the extent to which the basal plane is unzipped can be controlled via the preparation method. In particular, reduction with hydrazine enhances line defect formation, whereas intercalation inhibits the process.The hydroxyl functional group also has a tendency to gather in zones of dense oxidation on the carbon basal plane, a predilection that is not shared by the other prominent functional group species. Finally, the non‐functionalized carbon sites exhibit very similar bonding despite the increase in the sp²/sp³ ratio, confirming that reduction alone is insufficient for producing pristine graphene from graphene oxide. These results are obtained by directly probing the electronic structure of the graphene oxide samples via X‐ray absorption near‐edge structure spectroscopy (XANES) and resonant X‐ray emission spectroscopy (RXES). This work has important significance for the development of graphene oxide as a band gap‐engineered electronic material, as preparation methodology strongly affects not only the initial condition of the sample, but how the electronic structure evolves over time.     

Autonomously Controlled Homogenous Growth of Wafer‐Sized High‐Quality Graphene via a Smart Janus Substrate

The work reports a new method for large‐area growth of graphene films, which have been predicted to have novel and broad applications in the future. While chemical vapor deposition (CVD) is currently the preferred method, it suffers from a rather narrow processing window, and there is also much to be desired in the electrical properties of the CVD films. A new method for large‐area growth of graphene films is reported to overcome the narrow processing window of the CVD method. A composite substrate made of a C‐dissolving top (Ni) layer and a C‐rejecting bottom (Cu) layer is designed, which evolves into a C‐rejecting mixture, to autonomously regulate the C content at an elevated yet stable level at and near the surface over an extended duration. This “smart” substrate promotes graphene formation over a wide temperature‐gas composition window, leading to reliable growth of wafer‐sized graphene films of defined layer‐thickness and superior electrical–optical properties. This “smart”‐substrate strategy can also be implemented on Si and SiO₂ supports, paving the way toward the direct fabrication of large area, graphene‐enabled electronic and photonic devices.     

All‐Carbon Nanoarchitectures as High‐Performance Separation Membranes with Superior Stability

The application of graphene‐based membranes is hindered by their poor stability under practical hydrodynamic conditions. Here, nanocarbon architectures are designed by intercalating surface‐functionalized, small‐diameter, multi‐walled carbon nanotubes (MWCNTs) into reduced graphene oxide (rGO) sheets to create highly stable membranes with improved water permeability and enhanced membrane selectivity. With the intercalation of 10 nm diameter MWCNTs, the water permeability reaches 52.7 L m^?2 h^?1 bar^?1, which is 4.8 times that of pristine rGO membrane and five to ten times higher than most commercial nanofiltration membranes. The membrane also attains almost 100% rejection for three organic dyes of different charges. More importantly, the membrane can endure a turbulent hydrodynamic flow with cross‐flow rates up to 2000 mL min^?1 and a Reynolds number of 4667. Physicochemical characterization reveals that the inner graphitic walls of the MWCNTs can serve as spacers, while nanoscale rGO foliates on the outer walls interconnect with the assimilated rGO sheets to instill superior membrane stability. In contrast, intercalating with single‐walled nanotubes fails to reproduce such stability. Overall, this nanoarchitectured design is highly versatile in creating both graphene‐rich and CNT‐rich all‐carbon membranes with engineered nanochannels, and is regarded as a general approach in obtaining stable membranes for realizing practical applications of graphene‐based membranes.     

Interactions between an Aryl Thioacetate‐Functionalized Zn(II) Porphyrin and Graphene Oxide

The surface modification of graphene oxide (GO) is carried out via the supramolecular functionalization route using a Zn(II)‐porphyrin which is soluble in common organic solvents on basis of long alkyl chains present at the exocyclic positions. This acts as a dispersing agent and decorates the surface of the graphene oxide uniformly, giving rise to a new nanohybrid denoted Zn(II)‐porphyrin@GO. The resulting Zn(II)‐porphyrin@GO nanohybrid forms a stable dispersion in ethanol (as characterized by several different spectroscopic techniques such as UV–vis, Fourier transform infrared, Raman). The morphology of Zn(II)‐porphyrin@GO nanohybrid is investigated by atomic force microscopy (AFM) and transmission electron microscope (TEM)/selected area electron diffraction. Both TEM and AFM measurements indicate that the Zn(II)‐porphyrin self‐assemble onto the surface of graphene oxide sheets. Steady‐state and time‐resolved fluorescence emission studies in the dispersed phase, and as a thin film, point toward the strongly quenched fluorescence emission and lifetime decay, suggesting that energy transfer occurs from the singlet excited state of Zn(II)‐porphyrin unit to GO sheets.     

Layer‐Controlled and Wafer‐Scale Synthesis of Uniform and High‐Quality Graphene Films on a Polycrystalline Nickel Catalyst

Chemical vapor deposition (CVD) provides a synthesis route for large‐area and high‐quality graphene films. However, layer‐controlled synthesis remains a great challenge on polycrystalline metallic films. Here, a facile and viable synthesis of layer‐controlled and high‐quality graphene films on wafer‐scale Ni surface by the sequentially separated steps of gas carburization, hydrogen exposure, and segregation is developed. The layer numbers of graphene films with large domain sizes are controlled precisely at ambient pressure by modulating the simplified CVD process conditions and hydrogen exposure. The hydrogen exposure assisted with a Ni catalyst plays a critical role in promoting the preferential segregation through removing the carbon layers on the Ni surface and reducing carbon content in the Ni. Excellent electrical and transparent conductive performance, with a room‐temperature mobility of ≈3000 cm² V^?1 s^?1 and a sheet resistance as low as ≈100 Ω per square at ≈90% transmittance, of the twisted few‐layer grapheme films grown on the Ni catalyst is demonstrated.     

Water‐Soluble Poly(N‐isopropylacrylamide)–Graphene Sheets Synthesized via Click Chemistry for Drug Delivery

Covalently functionalized graphene sheets are prepared by grafting a well‐defined thermo‐responsive poly(N‐isopropylacrylamide) (PNIPAM) via click chemistry. The PNIPAM‐grafted graphene sheets (PNIPAM‐GS) consist of about 50% polymer, which endows the sheets with a good solubility and stability in physiological solutions. The PNIPAM‐GS exhibits a hydrophilic to hydrophobic phase transition at 33 °C, which is relatively lower than that of a PNIPAM homopolymer because of the interaction between graphene sheets and grafted PNIPAM. Moreover, through π–π stacking and hydrophobic interaction between PNIPAM‐GS and an aromatic drug, the PNIPAM‐GS is able to load a water‐insoluble anticancer drug, camptothecin (CPT), with a superior loading capacity of 15.6 wt‐% (0.185 g CPT per g PNIPAM‐GS). The in vitro drug release behavior of the PNIPAM‐GS‐CPT complex is examined both in water and PBS at 37 °C. More importantly, the PNIPAM‐GS does not exhibit a practical toxicity and the PNIPAM‐GS‐CPT complex shows a high potency of killing cancer cells in vitro. The PNIPAM‐GS is demonstrated to be an effective vehicle for anticancer drug delivery.     

Improved Efficiency of Single‐Layer Polymer Light‐Emitting Devices with Poly(vinylcarbazole) Doubly Doped with Phosphorescent and Fluorescent Dyes as the Emitting Layer

We demonstrate novel organic light‐emitting diode (LED) materials that contain a green phosphorescent dye (dmbpy)Re(CO)₃Cl (dmbpy = 4,4′‐dimethyl‐2,2′‐bipyridine), and a red fluorescent dye 4‐dicyanomethylene‐6‐(p‐dimethylaminostyryl)‐2‐methyl‐4H‐pyran (DCM) as dopants and polyvinylcarbazole (PVK) as the host. The photoluminescence (PL) and electroluminescence (EL) properties of these complex materials were studied. The energy transfer efficiency from PVK host to DCM is increased by the (dmbpy)Re(CO)₃Cl co‐dopant, which has an emission energy between that of PVK and DCM. The (dmbpy)Re(CO)₃Cl, which emits a long‐lived phosphorescence, is used as an energy coupler, providing the possibility to harvest both singlet and triplet energy in the devices. The pure red emission from DCM was observed from PL and EL spectra of (dmbpy)Re(CO)₃‐Cl(> 2.0 wt.‐%):DCM(> 0.5 wt. %) doped PVK films, demonstrating an efficient energy transfer from PVK and (dmbpy)Re(CO)₃‐Cl to DCM. By optimizing the concentration of DCM and (dmbpy)Re(CO)₃Cl in PVK, a maximum EL quantum efficiency of 0.42 cd A^–1 at a current density of 9.5 mA cm^–2 was obtained. The EL quantum efficiency of the doubly doped device is significantly enhanced in comparison with both a DCM‐only doped PVK device and a DCM‐doped PVK device with the green fluorescent dye Alq₃ as co‐dopant. The improvement in the operating characteristics of the phosphorescent and fluorescent dye doubly doped device is attributed to efficient energy transfer in the system, in which both triplet and singlet excitons are used for resultant emission in the polymer device.     

Highly Conductive Carbon Nanotube‐Graphene Hybrid Yarn

An efficient procedure for the fabrication of highly conductive carbon nanotube/graphene hybrid yarns has been developed. To start, arrays of vertically aligned multi‐walled carbon nanotubes (MWNT) are converted into indefinitely long MWNT sheets by drawing. Graphene flakes are then deposited onto the MWNT sheets by electrospinning to form a composite structure that is transformed into yarn filaments by twisting. The process is scalable for yarn fabrication on an industrial scale. Prepared materials are characterized by electron microscopy, electrical, mechanical, and electrochemical measurements. It is found that the electrical conductivity of the composite MWNT‐graphene yarns is over 900 S/cm. This value is 400% and 1250% higher than electrical conductivity of pristine MWNT yarns or graphene paper, respectively. The increase in conductivity is asssociated with the increase of the density of states near the Fermi level by a factor of 100 and a decrease in the hopping distance by an order of magnitude induced by grapene flakes. It is found also that the MWNT‐graphene yarn has a strong electrochemical response with specific capacitance in excess of 111 Fg^?1. This value is 425% higher than the capacitance of pristine MWNT yarn. Such substantial improvements of key properties of the hybrid material can be associated with the synergy of MWNT and graphene layers in the yarn structure. Prepared hybrid yarns can benefit such applications as high‐performance supercapacitors, batteries, high current capable cables, and artificial muscles.     

Thermal and Electrical Properties of Nanocomposites Based on Self‐Assembled Pristine Graphene

Thermodynamically‐driven exfoliation and self‐assembly of pristine graphene sheets is shown to provide thermally and electrically functional polymer composites. The spreading of graphene sheets at a high energy liquid/liquid interface is driven by lowering the overall energy of the system, and provides for the formation of water‐in‐oil emulsions stabilized by overlapping graphene sheets. Polymerization of the oil phase, followed by removal of the dispersed water phase, produces inexpensive and porous composite foams. Contact between the graphene‐stabilized water droplets provides a pathway for electrical and thermal transport through the composite. Unlike other graphene foams, the graphite used to synthesize these composites is natural flake material, with no oxidation, reduction, sonication, high temperature thermal treatment, addition of surfactants, or high shear mixing required. The result is an inexpensive, low‐density material that exhibits Joule heating and displays increasing electrical conductivity with decreasing thermal conductivity.     

Flexible and Transparent Graphene Electrode Architecture with Selective Defect Decoration for Organic Light‐Emitting Diodes

Graphene produced by chemical vapor deposition (CVD) has attracted great interest as a transparent conducting material, due to its extraordinary characteristics such as flexibility, optical transparency, and high conductivity, especially in next‐generation displays. Graphene‐based novel electrodes have the potential to satisfy the important factors for high‐performance flexible organic light‐emitting diodes (OLEDs) in terms of sheet resistance, transmittance, work function, and surface roughness. In this study, flexible and transparent graphene electrode architecture is proposed by adopting a selective defect healing technique for CVD‐grown graphene, which results in several benefits that produce high‐performance devices with excellent stabilities. The proposed architecture, which has a multi‐layer graphene structure treated by a layer‐by‐layer healing process, exhibits significant improvement in sheet resistance with high optical transparency. For improving the charge transport property and mechanical robustness, various defect sites of the CVD‐grown graphene are successfully decorated with gold nanoparticles through a simple electroplating (EP) method. Further, a graphene‐based OLED device that integrates the proposed electrode architecture on flexible substrates is demonstrated. Therefore, this architecture provides a new strategy to fabricate graphene electrode in OLEDs, extending graphene's immense potential as an advanced conductor toward high‐performance, flexible, and transparent displays.     

Defect‐Tolerant Nanocomposites through Bio‐Inspired Stiffness Modulation

A biologically inspired, multilayer laminate structural design is deployed into nanocomposite films of graphene oxide‐poly(methyl methacrylate) (GO‐PMMA). The resulting multilayer GO‐PMMA films show greatly enhanced mechanical properties compared to pure‐graphene‐oxide films, with up to 100% increases in stiffness and strength when optimized. Notably, a new morphology is observed at fracture surfaces: whereas pure‐graphene‐oxide films show clean fracture surfaces consistent with crack initiation and propagation perpendicular to the applied tensile load, the GO‐PMMA multilayer laminates show terracing consistent with crack stopping and deflection mechanisms. As a consequence, these macroscopic GO‐PMMA films become defect‐tolerant and can maintain their tensile strengths as their sample volumes increase. Linear elastic fracture analysis supports these observations by showing that the stiffness modulation introduced by including PMMA layers within a graphene oxide film can act to shield or deflect cracks, thereby delaying failure and allowing the material to access more of its inherent strength. Together, these data clearly demonstrate that desirable defect‐tolerant traits of structural biomaterials can indeed be incorporated into graphene‐ oxide‐based nanocomposites.     

All‐in‐One Phototheranostics: Single Laser Triggers NIR‐II Fluorescence/Photoacoustic Imaging Guided Photothermal/Photodynamic/Chemo Combination Therapy

Development of single near‐infrared (NIR) laser triggered phototheranostics for multimodal imaging guided combination therapy is highly desirable but is still a big challenge. Herein, a novel small‐molecule dye DPP‐BT is designed and synthesized, which shows strong absorption in the first NIR window (NIR‐I) and fluorescence emission in the second NIR region (NIR‐II). Such a dye not only acts as a dual‐modal contrast agent for NIR‐II fluorescence and photoacoustic (PA) imaging, but also serves as a combined therapeutic agent for photothermal therapy (PTT) and photodynamic therapy (PDT). The single NIR laser triggered all‐in‐one phototheranostic nanoparticles are constructed by encapsulating the dye DPP‐BT, chemotherapy drug DOX, and natural phase‐change materials with a folic acid functionalized amphiphile. Notably, under NIR laser irradiation, DOX can effectively release from such nanoparticles via NIR‐induced hyperthermia of DPP‐BT. By intravenous injection of such nanoparticles into Hela tumor‐bearing mice, the tumor size and location can be accurately observed via NIR‐II fluorescence/PA dual‐modal imaging. From in vitro and in vivo therapy results, such nanoparticles simultaneously present remarkable antitumor efficacy by PTT/PDT/chemo combination therapy, which is triggered by a single NIR laser. Overall, this work provides an innovative strategy to design and construct all‐in‐one nanoplatforms for clinical phototheranostics.