Cover Picture: A Hierarchically Structured Ni(OH)2 Monolayer Hollow‐Sphere Array and Its Tunable Optical Properties over a Large Region (Adv. Funct. Mater. 4/2007)

The fabrication of hierarchically structured Ni(OH)₂ monolayer hollow‐sphere arrays with the shell composed of building blocks of nanoflakelets is reported on p. 644 by Weiping Cai and co‐workers. The morphology can be easily controlled by the synthesis parameters, and the arrays show a tunable optical transmission stop band. Tuning can be achieved by changing the size or morphology of the hollow spheres. Such arrays may have potential applications in optical devices, photonic crystals, and as sensors for gas detection. The fabrication of a hierarchically structured Ni(OH)₂ monolayer hollow‐sphere array with the shell composed of building blocks of nanoflakelets is demonstrated based on a colloidal monolayer and electrochemical deposition. The morphology can be easily controlled by the colloidal monolayer and deposition parameters. Importantly, such monolayer hollow‐sphere array shows a morphology‐ and size‐dependent tunable optical transmission stop band. This stop band can be easily tuned from 455–1855 nm by changing the size of the hollow spheres between 1000 and 4500 nm, and also fine‐adjusted by changing the deposition time. The array exhibits a nearly incident‐angle‐independent position of the stop band that 3D photonic crystals do not possess. This structure may have potential applications in optical devices, photonic crystals, and sensors for gas detection.     

Synthesis of Nickel Sulfide Submicrometer‐Sized Hollow Spheres Using a γ‐Irradiation Route

Nickel sulfide (NiS) hollow spheres have been successfully synthesized by γ‐irradiation, at room temperature, of an aqueous PMMA–CS₂–ethanol solution that contains NiSO₄·6H₂O. Electron microscopy results show that the diameter of the NiS hollow spheres and the thickness of the sphere shells are about 500 nm and 20 nm, respectively. The room‐temperature UV‐vis absorption spectrum of the NiS hollow spheres gives a peak centered at around 233 nm (5.56 eV) with a remarkable blue‐shift relative to that of bulk NiS (2.1 eV). This remarkable blue‐shift may be attributed to the small dimensions of the materials. A possible growth mechanism of NiS hollow spheres by γ‐irradiation method is also presented. The successful preparation of NiS hollow spheres on a large scale under mild conditions could be of interest for both applications and fundamental studies.     

Nanometer‐Sized Copper Sulfide Hollow Spheres with Strong Optical‐Limiting Properties

CuS semiconductor nanometer‐sized hollow spheres are successfully synthesized by using a soft‐template method. A possible growth mechanism is proposed. The linear optical property of the CuS hollow spheres is examined by means of photoluminescence spectroscopy at room temperature. The optical‐limiting (OL) property of these nanostructures is characterized by using a nanosecond Q‐switched YAG laser and an optical parametric oscillator pumped with Surelite‐III. A strong OL response is detected for the CuS hollow spheres in both visible and near infrared (NIR) spectral ranges, which makes these promising materials for applications such as the protection of human eyes or as optical sensors for high‐power laser irradiation. The OL mechanism of the CuS hollow‐sphere nanostructure may be the combination of free‐carrier absorption (FCA) and nonlinear scattering.     

3D Hierarchical Co3O4 Twin‐Spheres with an Urchin‐Like Structure: Large‐Scale Synthesis,Multistep‐Splitting Growth,and Electrochemical Pseudocapacitors

Novel, 3D hierarchical Co₃O₄ twin‐spheres with an urchin‐like structure are produced successfully on the large scale for the first time by a solvothermal synthesis of cobalt carbonate hydroxide hydrate, Co(CO₃)_0.5(OH)·0.11H₂O, and its subsequent calcination. The morphology of the precursor, which dominates the structure of the final product, evolves from nanorods to sheaf‐like bundles, to flower‐like structures, to dumbbell‐like particles, and eventually to twin‐spheres, accompanying a prolonged reaction time. A multistep‐splitting growth mechanism is proposed to understand the formation of the 3D hierarchical twin‐spheres of the precursor, based on the time effect on the morphologies of the precursor. The 3D hierarchical Co₃O₄ twin‐spheres are further used as electrode materials to fabricate supercapacitors with high specific capacitances of 781, 754, 700, 670, and 611 F g^?1 at current densities of 0.5, 1, 2, 4, and 8 A g^?1, respectively. The devices also show high charge‐discharge reversibility with an efficiency of 97.8% after cycling 1000 times at a current density of 4 A g^?1.     

Some New Developments in the Synthesis,Functionalization, and Utilization of Monodisperse Colloidal Spheres

This article provides an overview of some recent developments related to the synthesis and functionalization of monodisperse colloidal spheres, a class of colloidal materials that has found widespread use in applications such as the fabrication of photonic crystals, optical sensing, and drug delivery. Traditionally, the choice of materials has been limited to polystyrene and silica. We and other groups have recently expanded the scope of materials by developing a number of methods for producing monodisperse colloidal spheres from various semiconductors and metals. This article is confined to our own work; it covers three different synthetic strategies: the bottom–up approach, the top–down approach, and template‐directed synthesis. The colloidal spheres may have a solid, hollow, or core–shell structure, and the chemical compositions can include Se, Bi, Pb, In, Sn, Cd, Pt, Ag₂Se, CdSe, PbS, or TiO₂. As an example to illustrate the attractive features of these colloidal spheres, we demonstrate the fabrication of Ag₂Se‐based photonic crystals whose stop bands can be thermally switched between two spectral positions.     

Machine Learning‐Enabled Correlation and Modeling of Multimodal Response of Thin Film to Environment on Macro and Nanoscale Using “Lab‐on‐a‐Crystal”

To close the feedback loop between artificial intellegence‐controlled materials synthesis and characterization, material functionality must be rapidly tested. A platform for high‐throughput multifunctional materials characterization is developed using a quartz crystal microbalance with auxiliary in‐plane electrodes and a custom gas/vapor flow cell, enabling simultaneous scanning probe microscopy and electrical, optical, gravimetric, and viscoelastic characterization on the same film under controlled environment. The lab‐on‐a‐crystal in situ multifunctional output allows direct correlations between the gravimetric/viscoelastic, electrical, and optical responses of polymer film in response to environment. When multiple film properties are used to augment the training set for machine learning regression, prediction of material response to the environment improves by a factor of 13 when <5% of the total dataset is used for model training.     

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 Degree of Optical Tunability of Self‐Assembled Photonic‐Plasmonic Crystals by Filling Fraction Modification

The optical properties of two‐dimensional hybrid photonic‐plasmonic crystals are fine‐tuned by modifying the dielectric component of the system. The filling fraction of the dielectric component in monolayers of spheres deposited on gold substrates is controlled by means of oxygen‐plasma etching. Doing so enables spectral tuning of the optical modes of the system. Experiments are performed on both optically passive and active samples showing the possibility for strong modification of the emission properties of samples containing emitters distributed within the spheres. The change in sphere diameter needed to substantially modify the sample's optical response points to a potential use of these samples as sensors or tunable emitting devices if appropriate polymeric components are employed.     

Large‐scale Synthesis of Urchin‐like Mesoporous TiO2 Hollow Spheres by Targeted Etching and Their Photoelectrochemical Properties

A versatile targeted etching strategy is developed for the large‐scale synthesis of urchin‐like mesoporous TiO₂ hollow spheres (UMTHS) with tunable particle size. Its key feature is the use of a low‐temperature hydrothermal reaction of surface‐fluorinated, amorphous, hydrous TiO₂ solid spheres (AHTSS) under the protection of a polyvinylpyrrolidone (PVP) coating. With the confinement of PVP and water penetration, the highly porous AHTSS are selectively etched and hollowed by fluoride without destroying their spherical morphology. Meanwhile TiO₂ hydrates are gradually crystallized and their growth is preferentially along anatase (101) planes, reconstructing an urchin‐like shell consisting of numerous radially arranged single‐crystal anatase nanothorns. Complex hollow structures, such as core–shell and yolk–shell structures, can also be easily synthesized via additional protection of the interior by pre‐filling AHTSS with polyethylene glycol (PEG). The hollowing transformation is elucidated by the synergetic effect of etching, PVP coating, low hydrothermal reaction temperature, and the unique microstructure of AHTSS. The synthesized UMTHS with a large surface area of up to 128.6 m² g^‐1 show excellent light‐harvesting properties and present superior performances in photocatalytic removal of gaseous nitric oxide (NO) and photoelectrochemical solar energy conversion as photoanodes for dye‐sensitized mesoscopic solar cells.     

Synthesis of Optical‐Quality Single‐Crystal β‐BaB2O4 Microwires and Nanowires

The synthesis of optical quality β‐barium borate microwires and nanowires (MNWs) is reported using an organic‐free hydrothermal method with BaCl₂·6H₂O, NaOH, and H₃BO₃ as source materials, and assisted with post‐annealing. As‐synthesized MNWs, with diameters ranging from 500 nm to 2 μm and lengths up to several hundred micrometers, show good optical‐waveguiding capabilities. Based on evanescent coupling between a single BBO MNW waveguide and a fiber taper, propagation losses of 0.30 dB μm^?1 (at 532 nm) and 0.21 dB μm^?1 (at 671 nm) are evaluated, respectively. An evident second‐harmonic generation (SHG) signal at 532 nm with a measured conversion efficiency of about 8.4% is observed when excited by waveguided 1064 nm, picosecond laser pulses within a BBO MNW with a length of the order of 100 μm. The dependence of the SHG conversion efficiency on the MNW diameter is also investigated. These results show a much‐higher SHG efficiency for BBO single‐crystal MNWs compared with bulk crystal, which suggests potential applications in future micro‐/nanoscale nonlinear optical applications such as optical modulation and frequency conversion.     

Synthesis and photoluminescence properties of wash-board belt-like ZnSe nanostructures

Washboard belt-like zinc selenide （ZnSe） nanostructures are successfully prepared by a simple chemical vapor deposi- tion （CVD） technology without catalyst. The phase compositions, morphologies and optical properties of the nanos- tructures are investigated by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, high-resolution transmis- sion electron microscopy （HRTEM） and photoluminescence （PL） spectroscop, respectively. A vapor-liquid mecha- nism is proposed for the formation of ZnSe belt-like structures. Strong PL from the ZnSe nanostructure can be tuned from 462 nm to 440 nm with temperature varying from 1000 ℃ to 1200 ℃, and it is demonstrated that the washboard belt-like ZnSe nanostructures have potential applications in optical and sensory nanotechnology. This method is ex- pected to be applied to the synthesis of other II-VI groups or other group＇s semiconducting materials.     

Metastable Copper‐Phthalocyanine Single‐Crystal Nanowires and Their Use in Fabricating High‐Performance Field‐Effect Transistors

This paper describes a simple, vapor‐phase route for the synthesis of metastable α‐phase copper‐phthalocyanine (CuPc) single‐crystal nanowires through control of the growth temperature. The influence of the growth temperature on the crystal structures, morphology, and size of the CuPc nanostructures is explored using X‐ray diffraction (XRD), optical absorption, and transmission electron microscopy (TEM). α‐CuPc nanowires are successfully incorporated as active semiconductors in field‐effect transistors (FETs). Single nanowire devices exhibit carrier mobilities and current on/off ratios as high as 0.4 cm² V^?1 s^?1 and >10⁴, respectively.     

Sub‐kilogram‐Scale One‐Pot Synthesis of Highly Luminescent and Monodisperse Core/Shell Quantum Dots by the Successive Injection of Precursors

The one‐pot synthesis of core/shell quantum dots (QDs) represents an attractive alternative to conventional synthesis techniques, where the core CdSe QDs are first purified and then an epitaxial shell of the desired thickness is obtained by the slow addition of shell precursors to a solution of the purified QDs at high temperature. We have developed a one‐pot synthesis procedure involving the successive injection of deliberately selected core‐ and shell‐forming reagents at appropriate temperatures. Sub‐kilogram quantities of highly luminescent and monodisperse core/shell QDs with desirable optical properties (full width at half maximum of photoluminescence (PL) band is ca. 30 nm) have been produced by the sequential growth of the core and shell in a controlled manner. This one‐pot method has also been extended to form water‐soluble core/double‐shell CdSe/ZnSe/ZnS QDs exhibiting high PL efficiency and stability.     

Double‐Inverse‐Opal Photonic Crystals: The Route to Photonic Bandgap Switching

Photonic crystals with a complete bandgap can stop the propagation of light of a certain frequency in all directions. We introduce double‐inverse‐opal photonic crystals (DIOPCs) as a new kind of optical switch. In the DIOPC, a movable, weakly scattering sphere is embedded within each pore of the inverse‐opal photonic crystal lattice. Switching between a diffusive reflector and a photonic crystal environment is experimentally demonstrated. Theory shows that a complete bandgap can be realized that can be opened or closed by moving the spheres. This functionality opens up new possibilities for the control of light emission and propagation. The close link and interaction between the chemical synthesis and the computational design and analysis underlines the interdisciplinary focus of this report.     

An Efficient Emulsion‐Induced Interface Assembly Approach for Rational Synthesis of Mesoporous Carbon Spheres with Versatile Architectures

Mesoporous carbon matrix with open pore structure, short diffusion length, and large pore size can favor the in‐pore immobilization of active species and facilitate mass diffusion during catalytic reactions. However, a great difficulty still remains on controllable synthesis of uniform mesoporous carbon spheres with these structural characteristics. Herein, using amphiphilic Pluronic F127 as the surfactant, 1,3,5‐trimethyl benzene (TMB) as the pore swelling and interface‐adjusting agent, and dopamine as the carbon source, a robust emulsion‐induced interface assembly approach for rational synthesis of mesoporous carbon spheres is demonstrated. The interface assembly process, including dopamine polymerization and fusion of TMB/F127/dopamine emulsions, can be regulated by tuning the dosage of dopamine and ammonia water, resulting in mesoporous carbon spheres with tunable pore sizes and versatile architectures, such as vesicles, walnut shapes, spheres with dendritic‐like 3D radially aligned mesochannels (RA‐MC), and isolated spherical mesopores. Moreover, the derived RA‐MC is used as a promising matrix to immobilize ultra‐small Au nanoparticles (≈3 nm). The Au/RA‐MC exhibits no mass diffusion limitations in reduction of 4‐nitrophenol, showing high conversion efficiency and good recyclability. This work paves a new avenue for controllable synthesis of mesoporous carbon spheres with well‐developed mesoporosity and architectures and their application as novel heterogeneous catalysts.     

Salt‐Assisted Synthesis of 2D Materials

2D materials have demonstrated good chemical, optical, electrical, and magnetic characteristics, and offer great potential in numerous applications. Corresponding synthesis technologies of 2D materials that are high‐quality, high‐yield, low‐cost, and time‐saving are highly desired. Salt‐assisted methods are emerging technologies that can meet these requirements for the fabrication of 2D materials. Herein, the recent process for the salt‐assisted synthesis of 2D materials and their typical applications are summarized. First, the properties of salt crystals and molten salts are briefly introduced, and then some examples of 2D materials synthesis with the assistance of salt as well as their representative applications are presented. The underlying mechanisms of salts with different states on the formation of 2D morphology are discussed to aid in the rational design of synthetic route of 2D materials. At last, the challenges and future perspectives for salt‐assisted methods are briefly described. This review provides guidance for the controllable synthesis of 2D materials based on the salt‐assisted approaches.     

Direct Synthesis of Large‐Scale WTe2 Thin Films with Low Thermal Conductivity

Large‐scale, polycrystalline WTe₂ thin films are synthesized by atmospheric chemical vapor reaction of W metal films with Te vapor catalyzed by H₂Te intermediates, paving a way to understanding the synthesis mechanism for low bonding energy tellurides and toward synthesis of single‐crystalline telluride nanoflakes. Through‐plane and in‐plane thermal conductivities of single‐crystal WTe₂ flakes and polycrystalline WTe₂ thin films are measured for the first time. Nanoscale grains and disorder in WTe₂ thin films suppress the in‐plane thermal conductivity of WTe₂ greatly, which is at least 7.5 times lower than that of the single‐crystalline flakes.     

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.     

ZnO Nanotetrapods: Controlled Vapor‐Phase Synthesis and Application for Humidity Sensing

A systematic study on controlled synthesis of ZnO nanotetrapods by combining metal‐vapor transport, oxidative nucleation/growth, fast‐flow quenching, and water‐assisted cleaning is reported. The technique developed in this work makes possible the fabrication of ZnO nanotetrapods with different morphologies, with arm diameters down to 17 nm, and with arm lengths ranging from 50 nm up to a few micrometers. The octa‐twin model is verified for the growth of the ZnO nanotetrapods. Photoluminescence (PL) studies indicate a higher level of surface and subsurface oxygen vacancies for smaller ZnO nanotetrapods. The ZnO nanotetrapods are first used for the fabrication of resistor‐type humidity sensors, which show high sensitivity, quick response/recovery, long lifetime, and a wide range of humidity response. These favorite characteristics of the humidity sensors are ascribed to the unique morphology of the nanotetrapods, which can create a film with faceted pores and large internal surfaces.     

Enhanced Optical Properties and Opaline Self‐Assembly of PPV Encapsulated in Mesoporous Silica Spheres

A new poly(p‐phenylenevinylene) (PPV) composite material has been developed by the incorporation of insoluble PPV polymer chains in the pores of monodisperse mesoporous silica spheres through an ion‐exchange and in situ polymerization method. The polymer distribution within the resultant colloidal particles is characterized by electron microscopy, energy dispersive X‐ray microanalysis, powder X‐ray diffraction, and nitrogen adsorption. It was found that the polymer was selectively incorporated into the mesopores of the silica host and was well distributed throughout the body of the particles. This confinement of the polymer influences the optical properties of the composite; these were examined by UV–vis and fluorescence spectroscopy and time‐correlated single‐photon counting. The results show a material that exhibits an extremely high fluorescence quantum yield (approaching 85%), and an improved resistance to oxidative photobleaching compared to PPV. These enhanced optical properties are further complemented by the overall processability of the colloidal material. In marked contrast to the insolubility of PPV, the material can be processed as a stable colloidal dispersion, and the individual composite spheres can be self‐assembled into opaline films using the vertical deposition method. The bandgap of the opal can be engineered to overlap with the emission band of the polymer, which has significant ramifications for lasing.