Thermal conductivity of polymer-based composites: Fundamentals and applications

Thermal management is critical to the performance, lifetime, and reliability of electronic devices. With the miniaturization, integration and functionalization of electronics and the emergence of new applications such as light emitting diodes, thermal dissipation becomes a challenging problem. Addressing this challenge requires the development of novel polymer-based composite materials with enhanced thermal conductivity. In this review, the fundamental design principles of highly thermally conductive composites were discussed. The key factors influencing the thermal conductivity of polymers, such as chain structure, crystallinity, crystal form, orientation of polymer chains, and orientation of ordered domains in both thermoplastics and thermosets were addressed. The properties of thermally conductive fillers (carbon nanotubes, metal particles, and ceramic particles such as boron nitride or aluminum oxide) are summarized at length. The dependence of thermal conductivity of composites on the filler loading, filler aggregate morphology and overall composite structure is also discussed. Special attention is paid to recent advances in controlling the microstructure of polymer composites to achieve high thermal conductivity (novel approaches to control filler orientation, special design of filler agglomerates, formation of continuous filler network by self-assembly process, double percolation approach, etc.). The review also summarizes some emerging applications of thermally conductive polymer composites. Finally, we outline the challenges and outlook for thermally conductive polymer composites.     

Photoelektronische eigenschaften von kristallen aus polymeren mit konjugierter hauptkette

Polyconjugated polymers like poly(acetylene) undergo redox reactions resulting in metal-like conductivity. Due to the complex morphology of the polymer the structure, state of order and the mechanism of carrier generation and transport are not well understood. Two different model systems which are available as well defined single crystals are presented. In polydiacetylene crystals the mobility of charge carriers along isolated and over macroscopic distances defect-free polymer chains can be studied. The radical cation salts of simple arenes serve as models for the structure and charge transfer interactions in the metallic conductive phases of polymers.     

Proliferous polymerisation

Proliferous polymerisation makes it possible to produce polymer in the form of particles of an irregular shape. This polymerisation may be carried out in bulk or in aqueous suspension. The mechanism of polymer proliferation is described for various monomers and monomer combinations and examples of proliferous polymerisation are given for a number of cases. Radical formation by chain rupture of polymer molecules is essential for the growth process. Photochemical initiation of proliferous polymerisation demonstrates the high efficiency of the chain rupturing process. Entanglements of macromolecules are shown to contribute to the formation of an insoluble polymer system with a low degree of equilibrium swelling in good solvents.     

Effect of different side chains on alternating copolymers of benzodithiophene and thiophene in organic solar cells

Polymeric semiconductors offer the dual advantages of lightness and flexibility, facilitating the large-scale production of organic electronic devices. In the present research, electron donor polymers were synthesized incorporating high electron density aromatic units, specifically benzodithiophene (BDT) and thiophene (Th), to explore their efficacy in organic electronics. This systematic study focused on evaluating the impact of varying side chains on the material properties of these polymers. It was found that polymers with Th side chains exhibited significantly enhanced thermal stability, approximately 100°C higher than their alkoxide side chain counterparts. For the polymer PEHO-BDT3HT, a bandgap value of around 1.6 eV was obtained. Furthermore, binary devices were developed using these novel copolymers, among which PDT-BDT3HT demonstrated superior photovoltaic performance, achieving a power conversion efficiency of 1.56% without any optimization. This work not only sheds light on the influence of side chain variations in polymer properties but also showcases the potential of BDT and Th-based copolymers in the field of organic electronics.     

A new approach to functionalize multi-walled carbon nanotubes by the use of functional polymers

A new method to graft a large number of long polymer chains or small functional molecules onto multi-walled carbon nanotubes (MWNTs) indirectly is reported. First, MWNTs were slightly functionalized by reversible addition-fragmentation chain transfer (RAFT) copolymerization of styrene and maleic anhydride using the dithioester groups attached to MWNTs as RAFT agents. The highly reactive maleic anhydride groups could further react with a large number of long polymer chains or small functional molecules with hydroxyl or amino group easily. The resulted MWNTs have good solubility in organic solvents and water; the perfect structure of MWNTs is altered very little from the information of Raman spectra.     

Fabrication and characterisation of polymer thin-films derived from cineole using radio frequency plasma polymerisation

The development of organic polymer thin-films is critical for the progress of many fields including organic electronics and biomedical coatings. This paper describes the fabrication of an organic polymer thin film produced from 1,8-cineole via radio frequency plasma polymerisation. A deposition rate of 55 nm/min was obtained under the polymerisation conditions employed. Infrared spectroscopic analysis demonstrated that some functional groups observed in the monomer were retained after the polymerisation process, while new functional groups were introduced. The refractive index and extinction coefficient were estimated to be 1.543 (at 500 nm) and 0.001 (at 500 nm) respectively. The polymers were shown to be optically transparent. AFM images of the polymer established a very smooth and uniform surface with average roughness of 0.39 nm. Water contact angle data demonstrated that the surface was stable while in contact with water.     

Electric Field Induced Fluorescence Modulation of Single Molecules in PMMA Based on Electron Transfer

We present a method to modulate the fluorescence of non-polar single squaraine-derived rotaxanes molecules embedded in a polar poly(methyl methacrylate) (PMMA) matrix under an external electric field. The electron transfer between single molecules and the electron acceptors in a PMMA matrix contributes to the diverse responses of fluorescence intensities to the electric field. The observed instantaneous and non-instantaneous electric field dependence of single-molecule fluorescence reflects the redistribution of electron acceptors in PMMA induced by electronic polarization and orientation polarization of polar polymer chains in an electric field.     

Recent Progress on Fabrication and Performance of Polymer Composites with Highly Thermal Conductivity

The rise of miniaturized, integrated, and functional electronic devices has intensified the need for heat dissipation. To address this challenge, it is necessary to develop novel thermally conductive polymer composites as packaging materials. In this paper, a number of factors for the construction and design of thermally conductive polymers are concluded. Special attention is focused on the analysis and comparison of the thermally conductive composites prepared by various fillers or strategies to provide guidelines and references for future design of composite materials. The current commonly used preparation strategies of thermally conductive polymer are summarized, such as using a variety of fillers, vacuum filtration, template method, and so on. The challenges of thermally conductive polymer composites are finally sketched. This review can inspire the design of polymer composites with brilliant thermal conductivity.     

Nanomorphology control in aqueous coatings

Using catalytic chain transfer polymerisation (CCTP) in emulsion polymerisation results in efficient molecular weight reduction. An additional benefit of polymers prepared with CCTP is that they have a chain terminal unsaturated group that can be used in a subsequent graft copolymerisation to yield comb-shaped polymer chains. By careful optimisation of the polymer parameters, film properties can be optimised to yield coatings with very interesting combinations of properties.     

Topochemical Reactions of Monomers with Conjugated Triple-Bonds VII Mechanism of Transition from Monomer to Polymer Phase During Solid-State Polymerisation

The lattice-controlled solid-state polymerisation of three different modifications of 2,4-hexadiin-1,6-diol-bis(phenylurethane) was investigated by X-ray and optical methods. The polymerisation is a homogeneous reaction. The polymer grows in the form of single chains within the crystal of the monomer. The chains extend along a definite crystallographic direction. Monomer and polymer are isomorphous and monomer-polymer single crystals of various compositions are obtained up to a quantitative conversion in the case of modification I or III. Phase separation into a mesomorphic polymer and oriented monomer phase was observed on annealing partially polymerised single-crystals of modification II below the transition point to modification III.     

From nanofabrication to self-fabrication--tailored chemistry for control of single molecule electronic devices

Single molecule electronics is a field of research focused on the use of single molecules as electronics components. During the past 15 years the field has concentrated on development of test beds for measurements on single molecules. Bottom-up approaches to single molecule devices are emerging as alternatives to the dominant top-down nanofabrication techniques. One example is solution-based self-assembly of a molecule enclosed by two gold nanorod electrodes. This article will discuss recent attempts to control the self-assembly process by the use of supramolecular chemistry and how to tailor the electronic properties of a single molecule by chemical design.     

Recent advances in electrochromic polymers

Electrochromic polymers are attractive materials with enormous potential in the rapidly developing area of plastic electronics due to their flexibility, low-power consumption, ease of processing and low processing cost. Electrochromic devices created with electrochromic polymers are likely to be alternatives or supplements to the conventional inorganic electrochromic devices, which face challenges of durability and electrochromic properties. Several novel electrochromic polyimides, polyamides, and polynorbornenes prepared via polycondensation, ring-opening metathesis polymerisation (ROMP), etc., are introduced in this article. These various polymer species exhibit high thermal stability and mechanical strength.     

Nanographenes as active components of single-molecule electronics and how a scanning tunneling microscope puts them to work

Single-molecule electronics, that is, realizing novel electronic functionalities from single (or very few) molecules, holds promise for application in various technologies, including signal processing and sensing. Nanographenes, which are extended polycyclic aromatic hydrocarbons (PAHs), are highly attractive subjects for studies of single-molecule electronics because the electronic properties of their flat conjugated systems can be varied dramatically through synthetic modification of their sizes and topologies. Single nanographenes provide high tunneling currents when adsorbed flat onto conducting substrates, such as graphite. Because of their chemical inertness, nanographenes interact only weakly with these substrates, thereby preventing the need for special epitaxial structure matching. Instead, self-assembly at the interface between a conducting solid, such as the basal plane of graphite, and a nanographene solution generally leads to highly ordered monolayers. Scanning tunneling spectroscopy (STS) allows the current-voltage characteristics to be measured through a single molecule positioned between two electrodes; the key to the success of STS is the ability to position the scanning tunneling microscopy (STM) tip freely with respect to the molecule in all dimensions, that is, both parallel and perpendicular to the surface. In this Account, we report the properties of nanographenes having sizes ranging from 0.7 to 3.1 nm and exhibiting various symmetry, periphery, and substitution types. The size of the aromatic system and the nature of its perimeter are two essential features affecting its HOMO-LUMO gap and charge carrier mobility in the condensed phase. Moreover, the extended pi area of larger substituted PAHs improves the degree of self-ordering, another key requirement for high-performance electronic devices. Self-assembly at the interface between an organic solution and the basal plane of graphite allows deposition of single molecules within the well-defined environment of a molecular monolayer. We have used STM and STS to investigate both the structures and electronic properties of these single molecules in situ. Indeed, we have observed key electronic functions, rectification and current control through single molecules, within a prototypical chemical field-effect transistor at ambient temperature. The combination of nanographenes and STM/STS, with the PAHs self-assembled in oriented molecular mono- or bilayers at the interface between an organic solution and the basal plane of graphite and contacted by the STM tip, is a simple, reliable, and versatile system for developing the fundamental concepts of molecular electronics. Our future targets include fast reversible molecular switches and complex molecular electronic devices coupled together from several single-molecule systems.     

Molecular electronics. Synthesis and testing of components

Molecular electronics involves the use of single or small packets of molecules as the fundamental units for computing. While initial targets are the substitution of solid-state wires and devices with molecules, long-range goals involve the development of novel addressable electronic properties from molecules. A comparison of traditional solid-state devices to molecular systems is described. Issues of cost and ease of manufacture are outlined, along with the syntheses and testing of molecular wires and devices.     

Transparent,conductive polystyrene in three dimensional configurations

Development of technologies for constructing three-dimensional (i.e. non-planar) transparent conductive electrodes from polymeric materials is a major goal in diverse applications, including optoelectronic devices, flexible electronics, photovoltaics, and others. We present a facile new strategy for creating conductive, transparent gold layering on polystyrene, a widely-used polymer, in different shapes and surface morphologies. The approach is based upon amine functionalization of the polystyrene surface followed by incubation in an aqueous solution of Au(SCN)₄⁻ and brief plasma treatment. We show that this simple deposition process resulted in a homogeneous, transparent, and highly conductive crystalline Au coating. Importantly, electrical conductivity was attained for long distances, even in highly non-planar surfaces containing physical barriers. We further show that the approach can be employed for fabrication of conductive hollow tubes using electrospun polystyrene fibers as templates. The new synthesis scheme might make possible varied applications in polymer-based electronic and photonic devices.     

Structure and dynamics of polyrotaxane and slide-ring materials

Polyrotaxane (PR), in which cyclic molecules are threaded into a linear polymer chain, has generated great interest because the sliding and rotation of the cyclic molecules on the axial polymer chain lead to unique functional nanomaterials with novel dynamical properties. A typical example of the functional materials is a polyrotaxane network, called slide-ring (SR) material, prepared by cross-linking the cyclic molecules on different PRs. The cross-links composed of two cyclic molecules in a shape of figure-of-eight slide along the polymer chains and the sliding motion gives rise to remarkable physical properties of the SR materials. In order to understand the unique features of the functional materials including SR materials and develop novel applications of PR, it is necessary to reveal the physical properties of PR, especially the sliding motion of the cyclic molecules in PR. In this article, we review the static structure and molecular dynamics of PR based primarily on our recent studies. Furthermore, the difference between SR materials and usual chemical gels in deformation behavior is also described. The findings summarized in this review indicate the significance of the sliding motion of cyclic molecules characterizing PR and SR materials.     

Pulling platinum atomic chains by carbon monoxide molecules

The interaction of carbon monoxide molecules with atomic-scale platinum nanojunctions is investigated by low temperature mechanically controllable break junction experiments. Combining plateau length analysis, two-dimensional conductance-displacement histograms and conditional correlation analysis a comprehensive microscopic picture is proposed about the formation and evolution of Pt-CO-Pt single-molecule configurations. Our analysis implies that before pure Pt monoatomic chains are formed a CO molecule infiltrates the junction, first in a configuration that is perpendicular to the contact axis. This molecular junction is strong enough to pull a monoatomic platinum chain with the molecule being incorporated in the chain. Along the chain formation the molecule can either stay in the perpendicular configuration, or rotate to a parallel configuration. The evolution of the single-molecule configurations along the junction displacement shows quantitative agreement with theoretical predictions, justifying the interpretation in terms of perpendicular and parallel molecular alignment. Our analysis demonstrates that the combination of two-dimensional conductance-displacement histograms with conditional correlation analysis is a useful tool to analyze separately fundamentally different types of junction trajectories in single molecule break junction experiments.     

Design and screening of zwitterionic polymer scaffolds for rapid underwater adhesion and long-term antifouling stability

As key components of antifouling material surfaces, the design and screening of polymer molecules grafted on the substrate are critical. However, current experimental and computational models still retain an empirical flavor due to the complex structure of polymers. Here, we report a simple and general strategy that enables multiscale design and screening of easily synthesized functional polymer molecules to address this challenge. Specifically, the required functions of the antifouling material are decomposed and assigned to different modules of the polymer molecules. By designing different modules, a novel bio-inspired polymer with three zwitterionic poly (sulfobetaine methacrylate) (PSBMA) chains, three catechol (DOPA) anchors (tri-DOPA-PSBMA), and a tris(2-aminoethyl) amine (TREN) scaffold were screened out. Moreover, it was successfully synthesized via an atom transfer radical polymerization (ATRP). The excellent performance of tri-DOPA-PSBMA with a versatile and convenient grafting strategy makes it a promising material for marine devices, biomedical devices, and industrial applications.     

Single-molecule imaging of cell surfaces using near-field nanoscopy

Living cells use surface molecules such as receptors and sensors to acquire information about and to respond to their environments. The cell surface machinery regulates many essential cellular processes, including cell adhesion, tissue development, cellular communication, inflammation, tumor metastasis, and microbial infection. These events often involve multimolecular interactions occurring on a nanometer scale and at very high molecular concentrations. Therefore, understanding how single-molecules localize, assemble, and interact on the surface of living cells is an important challenge and a difficult one to address because of the lack of high-resolution single-molecule imaging techniques. In this Account, we show that atomic force microscopy (AFM) and near-field scanning optical microscopy (NSOM) provide unprecedented possibilities for mapping the distribution of single molecules on the surfaces of cells with nanometer spatial resolution, thereby shedding new light on their highly sophisticated functions. For single-molecule recognition imaging by AFM, researchers label the tip with specific antibodies or ligands and detect molecular recognition signals on the cell surface using either adhesion force or dynamic recognition force mapping. In single-molecule NSOM, the tip is replaced by an optical fiber with a nanoscale aperture. As a result, topographic and optical images are simultaneously generated, revealing the spatial distribution of fluorescently labeled molecules. Recently, researchers have made remarkable progress in the application of near-field nanoscopy to image the distribution of cell surface molecules. Those results have led to key breakthroughs: deciphering the nanoscale architecture of bacterial cell walls; understanding how cells assemble surface receptors into nanodomains and modulate their functional state; and understanding how different components of the cell membrane (lipids, proteins) assemble and communicate to confer efficient functional responses upon cell activation. We anticipate that the next steps in the evolution of single-molecule near-field nanoscopy will involve combining single-molecule imaging with single-molecule force spectroscopy to simultaneously measure the localization, elasticity, and interactions of cell surface molecules. In addition, progress in high-speed AFM should allow researchers to image single cell surface molecules at unprecedented temporal resolution. In parallel, exciting advances in the fields of photonic antennas and plasmonics may soon find applications in cell biology, enabling true nanoimaging and nanospectroscopy of individual molecules in living cells.