Huibiao Liu

Aggregate Nanostructures of Organic Molecular Materials

Conjugated organic molecules are interesting materials because of their structures and their electronic, electrical, magnetic, optical, biological, and chemical properties. However, researchers continue to face great challenges in the construction of well-defined organic compounds that aggregate into larger molecular materials such as nanowires, tubes, rods, particles, walls, films, and other structural arrays. Such nanoscale materials could serve as direct device components. In this Account, we describe our recent progress in the construction of nanostructures formed through the aggregation of organic conjugated molecules and in the investigation of the optical, electrical, and electronic properties that depend on the size or morphology of these nanostructures. We have designed and synthesized functional conjugated organic molecules with structural features that favor assembly into aggregate nanostructures via weak intermolecular interactions. These large-area ordered molecular aggregate nanostructures are based on a variety of simpler structures such as fullerenes, perylenes, anthracenes, porphyrins, polydiacetylenes, and their derivatives. We have developed new methods to construct these larger structures including organic vapor-solid phase reaction, natural growth, association via self-polymerization and self-organization, and a combination of self-assembly and electrochemical growth. These methods are both facile and reliable, allowing us to produce ordered and aligned aggregate nanostructures, such as large-area arrays of nanowires, nanorods, and nanotubes. In addition, we can synthesize nanoscale materials with controlled properties. Large-area ordered aggregate nanostructures exhibit interesting electrical, optical, and optoelectronic properties. We also describe the preparation of large-area aggregate nanostructures of charge transfer (CT) complexes using an organic solid-phase reaction technique. By this process, we can finely control the morphologies and sizes of the organic nanostructures on wires, tubes, and rods. Through field emission studies, we demonstrate that the films made from arrays of CT complexes are a new kind of cathode materials, and we systematically investigate the effects of size and morphology on electrical properties. Low-dimension organic/inorganic hybrid nanostructures can be used to produce new classes of organic/inorganic solid materials with properties that are not observed in either the individual nanosize components or the larger bulk materials. We developed the combined self-assembly and templating technique to construct various nanostructured arrays of organic and inorganic semiconductors. The combination of hybrid aggregate nanostructures displays distinct optical and electrical properties compared with their individual components. Such hybrid structures show promise for applications in electronics, optics, photovoltaic cells, and biology. In this Account, we aim to provide an intuition for understanding the structure-function relationships in organic molecular materials. Such principles could lead to new design concepts for the development of new nonhazardous, high-performance molecular materials on aggregate nanostructures.

Graphdiyne and graphyne: from theoretical predictions to practical construction

Flat carbon (sp(2) and sp) networks endow the graphdiyne and graphyne families with high degrees of π-conjunction, uniformly distributed pores, and tunable electronic properties; therefore, these materials are attracting much attention from structural, theoretical, and synthetic scientists wishing to take advantage of their promising electronic, optical, and mechanical properties. In this Review, we summarize a state-of-the-art research into graphdiynes and graphynes, with a focus on the latest theoretical and experimental results. In addition to the many theoretical predictions of the potential properties of graphdiynes and graphynes, we also discuss experimental attempts to synthesize and apply graphdiynes in the areas of electronics, photovoltaics, and catalysis.

A Multianalyte Chemosensor on a Single Molecule: Promising Structure for an Integrated Logic Gate

A novel fluorescent probe that possess both BODIPY and Rhodamine moieties has been designed for the selective detection of Hg(2+) and Ba(2+) ions on the controlling by a logic gate. The characteristic fluorescence of the Ba(2+)-selective OFF-ON and the Hg(2+)-selective fluorescence bathochromic shift can be observed, and the concept has been used to construct a combinational logic circuit at the molecular level. These results will be useful for further molecular design to mimic the function of the complex logic gates on controlling.

Light-Controlled Organic/Inorganic P−N Junction Nanowires

P-N junctions are of great importance both in modern electronic applications and in understanding other semiconductor devices. Organic/inorganic P-N junction nanowires composed of functional organic molecules and inorganic molecules may be able to realize new or improved chemical and physical properties that were not observed in the individual component on nanosize and their bulk materials. We report herein the fabrication of the organic/inorganic semiconductor P-N junction nanowire and the remarkable performance on the light-controlled diode within a single hybrid P-N junction nanowire. Controlling the conductivity of the P-N junction nanowire by the light irradiation simply to achieve diode work indicates a new way to realize the photoelectric integration in a single nanowire device.

Highly Efficient Electron Transport Obtained by Doping PCBM with Graphdiyne in Planar-Heterojunction Perovskite Solar Cells

Organic-inorganic perovskite solar cells have recently emerged at the forefront of photovoltaics research. Here, for the first time, graphdiyne (GD), a novel two dimension carbon material, is doped into PCBM layer of perovskite solar cell with an inverted structure (ITO/PEDOT:PSS/CH3NH3PbI(3-x)Cl(x)/PCBM:GD/C60/Al) to improve the electron transport. The optimized PCE of 14.8% was achieved. Also, an average power conversion efficiency (PCE) of PCBM:GD-based devices was observed with 28.7% enhancement (13.9% vs 10.8%) compared to that of pure PCBM-based ones. According to scanning electron microscopy, conductive atomic force microscopy, space charge limited current, and photoluminescence quenching measurements, the enhanced current density and fill factor of PCBM:GD-based devices were ascribed to the better coverage on the perovskite layer, improved electrical conductivity, strong electron mobility, and efficient charge extraction. Small hysteresis and stable power output under working condition (14.4%) have also been demonstrated for PCBM:GD based devices. The enhanced device performances indicated the improvement of film conductivity and interfacial coverage based on GD doping which brought the high PCE of the devices and the data repeatability. In this work, GD demonstrates its great potential for applications in photovoltaic field owing to its networks with delocalized π-systems and unique conductivity advantage.

Ordered Nanosphere Alignment of Porphyrin for the Improvement of Nonlinear Optical Properties

There is currently an intensive effort to develop methods for producing materials with two-dimensionally (2D) or threedimensionally (3D) structured patterns and arrays, which are of great importance and interest because of their potential applications in the development of optoelectronic and microelectronic devices, [ 1–4 ] and the fabrication of chemical and biological sensors. [ 5 , 6 ] In the most recent developments, the fabrication of 2D or 3D structured patterns and arrays via colloidal self-assembly is particularly attractive. [ 7–15 ] In addition to being inexpensive, this method offers relative ease of processing and requires short processing time, compared to the stepwise manner of microfabrication techniques. [ 16–20 ] Typical building blocks of these self-assembly are polystyrene (PS) or poly(methyl methacrylate) (PMMA) latex spheres, poly(dimethyl siloxane) (PDMS), silica spheres, emulsion droplets with narrow size distribution. [ 9 , 21–23 ]

Design and Assembly of Rotaxane-Based Molecular Switches and Machines

Mechanically interlocked molecules, such as catenanes and rotaxanes, are at the heart of the development of molecular machines chemistry. They are able to self-organize, self-assemble, and self-control themselves into new materials with potential application as molecular devices. In this review, an overview of some recent progress on molecular machines is given, including new methodologies for their synthesis and self-assembly and their recent applications as dual or multilevel fluorescent molecular switches, as potential sensors, and even as a molecular-level transporter. In one development, a molecular machine containing a charge-transfer chromophore was designed to generate controllable aggregate structures through the reversible movement of a macrocycle over a thread; this was done in order to better understand the application of a molecular shuttle in solid state. Light is shed on how the novel properties and functions of molecular machines are extended, and examples of the ways in which molecular machines have been applied to the design and process of intelligentized systems are provided.

Graphdiyne Oxides as Excellent Substrate for Electroless Deposition of Pd Clusters with High Catalytic Activity

Graphdiyne (GDY), a novel kind of two-dimensional carbon allotrope consisting of sp- and sp(2)-hybridized carbon atoms, is found to be able to serve as the reducing agent and stabilizer for electroless deposition of highly dispersed Pd nanoparticles owing to its low reduction potential and highly conjugated electronic structure. Furthermore, we observe that graphdiyne oxide (GDYO), the oxidation form of GDY, can be used as an even excellent substrate for electroless deposition of ultrafine Pd clusters to form Pd/GDYO nanocomposite that exhibits a high catalytic performance toward the reduction of 4-nitrophenol. The high catalytic performance is considered to benefit from the rational design and electroless deposition of active metal catalysts with GDYO as the support.

Graphdiyne:ZnO Nanocomposites for High-Performance UV Photodetectors.

Graphdiyne (GD), a novel carbon allotrope with a 2D structure comprising benzene rings and carbon-carbon triple bonds, is successfully integrated with ZnO nanoparticles by a wet chemistry method. An ultraviolet photodetector based on these graphdiyne:ZnO nanocomposites exhibits significantly enhanced performance in comparison with a conventional ZnO device. GD may have diverse applications in future optoelectronics.

Self‐Assembly of Functional Molecules into 1D Crystalline Nanostructures

Self-assembled functional nanoarchitectures are employed as important nanoscale building blocks for advanced materials and smart miniature devices to fulfill the increasing needs of high materials usage efficiency, low energy consumption, and high-performance devices. One-dimensional (1D) crystalline nanostructures, especially molecule-composed crystalline nanostructures, attract significant attention due to their fascinating infusion structure and functionality which enables the easy tailoring of organic molecules with excellent carrier mobility and crystal stability. In this review, we discuss the recent progress of 1D crystalline self-assembled nanostructures of functional molecules, which include both a small molecule-derived and a polymer-based crystalline nanostructure. The basic principles of the molecular structure design and the process engineering of 1D crystalline nanostructures are also discussed. The molecular building blocks, self-assembly structures, and their applications in optical, electrical, and photoelectrical devices are overviewed and we give a brief outlook on crucial issues that need to be addressed in future research endeavors.