Anderson Localization of Phonons in Thermally Superinsulating Graphene Aerogels with Metal-Like Electrical Conductivity.

In the quest to improve energy efficiency and design better thermal insulators, various engineering strategies have been extensively investigated to minimize heat transfer through a material. Yet, the suppression of thermal transport in a material remains elusive because heat can be transferred by multiple energy carriers. Here, the realization of Anderson localization of phonons in a random 3D elastic network of graphene is reported. It is shown that thermal conductivity in a cellular graphene aerogel can be drastically reduced to 0.9 mW m-1 K-1 by the application of compressive strain while keeping a high metal-like electrical conductivity of 120 S m-1 and ampacity of 0.9 A. The experiments reveal that the strain can cause phonon localization over a broad compression range. The remaining heat flow in the material is dominated by charge transport. Conversely, electrical conductivity exhibits a gradual increase with increasing compressive strain, opposite to the thermal conductivity. These results imply that strain engineering provides the ability to independently tune charge and heat transport, establishing a new paradigm for controlling phonon and charge conduction in solids. This approach will enable the development of a new type of high-performance insulation solutions and thermally superinsulating materials with metal-like electrical conductivity.

Universal Strategy for Reversing Aging and Defects in Graphene Oxide for Highly Conductive Graphene Aerogels.

The production of highly stable, defect-free, and electrically conducting 3D graphene structures from graphene oxide precursors is challenging. This is because graphene oxide is a metastable material whose structure and chemistry evolve due to aging. Aging changes the relative composition of oxygen functional groups attached to the graphene oxide and negatively impacts the fabrication and properties of reduced graphene oxide. Here, we report a universal strategy to reverse the aging of graphene oxide precursors using oxygen plasma treatment. This treatment decreases the size of graphene oxide flakes and restores negative zeta potential and suspension stability in water, enabling the fabrication of compact and mechanically stable graphene aerogels using hydrothermal synthesis. Moreover, we employ high-temperature annealing to remove oxygen-containing functionalities and repair the lattice defects in reduced graphene oxide. This method allows obtaining highly electrically conducting graphene aerogels with electrical conductivity of 390 S/m and low defect density. The role of carboxyl, hydroxyl, epoxide, and ketonic oxygen species is thoroughly investigated using X-ray photoelectron and Raman spectroscopies. Our study provides unique insight into the chemical transformations occurring during the aging and thermal reduction of graphene oxide from room temperature up to 2700 °C.

Terahertz charge transport dynamics in 3D graphene networks with localization and band regimes.

Terahertz steady-state and time-resolved conductivity and permittivity spectra were measured in 3D graphene networks assembled in free-standing covalently cross-linked graphene aerogels. Investigation of a transition between reduced-graphene oxide and graphene controlled by means of high-temperature annealing allowed us to elucidate the role of defects in the charge carrier transport in the materials. The THz spectra reveal increasing conductivity and decreasing permittivity with frequency. This contrasts with the Drude- or Lorentz-like conductivity typically observed in various 2D graphene samples, suggesting a significant contribution of a relaxational mechanism to the conductivity in 3D graphene percolated networks. The charge transport in the graphene aerogels exhibits an interplay between the carrier hopping among localized states and a Drude contribution of conduction-band carriers. Upon photoexcitation, carriers are injected into the conduction band and their dynamics reveals picosecond lifetime and femtosecond dephasing time. Our findings provide important insight into the charge transport in complex graphene structures.

High-Temperature Fire Resistance and Self-Extinguishing Behavior of Cellular Graphene.

The ability to protect materials from fire is vital to many industrial applications and life safety systems. Although various chemical treatments and protective coatings have proven effective as flame retardants, they provide only temporary prevention, as they do not change the inherent flammability of a given material. In this study, we demonstrate that a simple change of the microstructure can significantly boost the fire resistance of an atomically thin material well above its oxidation stability temperature. We show that free-standing graphene layers arranged in a three-dimensional (3D) cellular network exhibit completely different flammability and combustion rates from a graphene layer placed on a substrate. Covalently cross-linked cellular graphene aerogels can resist flames in air up to 1500 °C for a minute without degrading their structure or properties. In contrast, graphene on a substrate ignites immediately above 550 °C and burns down in a few seconds. Raman spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric studies reveal that the exceptional fire-retardant and self-extinguishing properties of cellular graphene originate from the ability to prevent carbonyl defect formation and capture nonflammable carbon dioxide gas in the pores. Our findings provide important information for understanding graphene's fire-retardant mechanism in 3D structures/assemblies, which can be used to enhance flame resistance of carbon-based materials, prevent fires, and limit fire damage.

Contact resistance based tactile sensor using covalently cross-linked graphene aerogels.

A movable electrical contact between two materials is one of the most fundamental, simple, and common components in electronics that is used for binary control of a conducting path in an electrical circuit. Here, variable contact resistance between a highly elastic graphene aerogel and a rigid metal electrode is used for the analysis of non-binary pushing and pulling mechanical forces acting on the contact, enabling superior strain and pressure measurements. The variable contact resistance based electromechanical sensors demonstrate superfast, ultrasensitive and quantitative measurements of compressive and tensile stress from -1.18 MPa to 0.55 MPa. The sensors can operate over the temperature range of -60 to 100 °C, cover the whole skin and human motion range, and determine the weight of a grasped object. The measurement of such high forces has only been possible due to the high-temperature induced covalent cross-linking of graphene in the aerogel that provides high strength, durability, and fast response (<0.5 ms) to the sensing element. The study demonstrates the great potential of the contact resistance-controlled sensing, which enables high-precision and reliable measurement of strain and pressure over a remarkable large sensing range, providing new opportunities for applications in human-machine interfaces, robotics, flexible electronics, and haptic technology.

Nucleation and growth of metal-catalyzed silicon nanowires under plasma.

We report the results of a microscopic study of the nucleation and early growth stages of metal-catalyzed silicon nanowires in plasma-enhanced chemical vapor deposition. The nucleation of silicon nanowires is investigated as a function of different deposition conditions and metal catalysts (Sn, In and Au) using correlation of atomic force microscopy and scanning electron microscopy. This correlation method enabled us to visualize individual catalytic nanoparticles before and after the nanowire growth and identify the key parameters influencing the nanowire nucleation under plasma. The size and position of catalytic nanoparticles are found to play a significant role in the nucleation. We demonstrate that only small isolated nanoparticles in the range of 10-20 nm contribute to the nanowire growth under plasma, while larger nanoparticles are inactive because they get buried under a layer of a-Si:H before reaching supersaturation. Systematic analysis of different growth parameters reveals that the nanowire growth in plasma contradicts the vapor-liquid-solid mechanism at thermal equilibrium in many ways. The nanowire growth is much faster and proceeds even at negligible silicon solubility and bellow the eutectic temperature of the metal-silicon alloy. Based on the observations, we propose the nanowire growth under plasma to be characterized by the rapid solidification mechanism, where a crystalline silicon phase emerges from a metastable supersaturated liquid metal-silicon phase in local nonequilibrium.