Defects

Researchers from The University of Warwick, the University of Manchester, Brazil's Universidade Federal do Ceara and Turkey's Izmir Institute of Technology have tackled the long-standing conundrum of why graphene is so much more permeable to protons than expected by theory. 

A decade ago, scientists at The University of Manchester demonstrated that graphene is permeable to protons, nuclei of hydrogen atoms. The unexpected result sparked a debate because theory predicted that it would be extremely hard for a proton to permeate through graphene's dense crystalline structure. This had led to suggestions that protons permeate not through the crystal lattice itself, but through the pinholes in its structure.

Researchers from  the Vinča Institute of Nuclear Sciences, University of Belgrade, Serbia, recently examined the rainbow scattering of photons passing through graphene and how it reveals the structure and imperfections of the material.

While other methods to examine the defects of graphene exist, these have drawbacks. For instance, Raman spectroscopy can not distinguish some defect types, while high-resolution transmission electron microscopy can characterize crystal structure defects with outstanding resolution, but the energetic electrons it uses can degrade the crystal lattice.

Researchers from the University of Amsterdam, New York University and Spain's CSIC have developed a way to build micrometer-size models of atomic graphene using 'patchy particles’ - particles which are large enough to be easily visible in a microscope but small enough to reproduce many of the properties of actual atoms, can interact with the same coordination as the atoms in graphene, and form the same structures.

Using these patchy particles, the team built a model system and used it to obtain insight into the defects in 2D materials, including their formation and evolution over time. 

Researchers from the Chinese Academy of Sciences, the University of Science and Technology of China and North China University of Water Resources and Electric Power have studied the effects of irradiation defects on the work function of graphene electrodes in thermionic energy converters (TECs) and found that the generation of defects in graphene through irradiation would increase the work function and reduce the electron emission capacity.

Schematic diagram of a thermionic energy converter. (Image by ZHAO Ming) 

Graphene has great potential as an electrode coating material for TECs of the microreactor, which can significantly improve the electron emission ability of electrode. Electrode materials will be exposed to irradiation by high-energy particles during TECs use. Previous studies have shown that the types of defects induced by irradiation in graphene are mainly Stone-Wales defects, doping defects, and carbon vacancies. The appearance of defects will affect the adsorption properties of alkali and alkaline earth metals on the graphene surface in the electrode gap, and then change the electron emission properties of the graphene coating.

A team of researchers, led by Director Rod Ruoff at the Center for Multidimensional Carbon Materials (CMCM) within the Institute for Basic Science (IBS) and including graduate students at the Ulsan National Institute of Science and Technology (UNIST), has achieved growth and characterization of large area, single-crystal graphene totally free from wrinkles, folds, or adlayers. It was said to be 'the most perfect graphene that has been grown and characterized, to date'.

Director Ruoff notes: This pioneering breakthrough was due to many contributing factors, including human ingenuity and the ability of the CMCM researchers to reproducibly make large-area single-crystal Cu-Ni(111) foils, on which the graphene was grown by chemical vapor deposition (CVD) using a mixture of ethylene with hydrogen in a stream of argon gas. Student Meihui Wang, Dr. Ming Huang, and Dr. Da Luo along with Ruoff undertook a series of experiments of growing single-crystal and single-layer graphene on such ‘home-made’ Cu-Ni(111) foils under different temperatures.

An international team of researchers in Korea, the UK, Japan, the US and France recently shed light on the mysterious ability of graphene (and other carbon materials) to change its structure and even self-heal defects, by showing that fast-moving carbon atoms catalyze many of the restructuring processes.

Until now, researchers typically explained the structural evolution of graphene defects via a mechanism known as a Stone-Thrower-Wales type bond rotation. This mechanism involves a change in the connectivity of atoms within the lattice, but it has a relatively large activation energy, which makes it seem unlikely to succeed without some form of assistance.

Researchers from Nanjing University in China have developed a method to make large graphene films free of any wrinkles. The ultra-smooth films could enable large-scale production of electronic devices that harness the unique physical and chemical properties of graphene and other 2D materials.

Wrinkles in graphene films grown via chemical vapor deposition appear as jagged white lines at the top of this atomic force microscope image (left), but they disappear when the material is treated with a hydrogen plasma (right). Credit: Nature

Chemical vapor deposition (CVD) is the best-known method for making high-quality graphene sheets. It typically involves growing graphene by pumping methane gas onto copper substrates heated to temperatures around 1,000 °C, and then transferring the graphene to another surface such as silicon. But some of the graphene sticks to the copper surface, and as the graphene and copper expand and contract at different rates, wrinkles form in the graphene sheets. Such wrinkles often present hurdles for charge carriers and lower the film’s conductivity. Other researchers have tried to reduce wrinkles using low growth temperatures or special copper substrates, but the wrinkles have proven difficult to eliminate entirely, according to Libo Gao, a physicist at Nanjing University.

In order for CVD graphene to be used in its intended application, it needs to be transferred from the growth substrate to a target substrate a challenging but extremely important process step. Typically the transfer is done by spin-coating a supporting polymer layer and then chemically dissolving away the copper to release the graphene film from the substrate. The transferred graphene produced in this way is prone to contamination from the chemical agents used to remove the growth substrate as well as defective amorphous carbon generated during the high-temperature CVD growth. It also frequently leads to a substantial amount of polymer particle residue on the graphene generated during the transfer process. A third source of contamination could be airborne particles that are adsorbed onto the graphene surface.

Top: Schematic of the activated carbon-coated lint roller for cleaning the graphene surface. Bottom left: AFM image of unclean graphene on Cu foil. Bottom right: AFM image of superclean graphene on Cu foil. Image taken from Nanowerk

Researchers from Peking University and Tsinghua University in China and University of Manchester in the UK have recently demonstrated that the amorphous carbon contaminants on CVD-produced graphene, which could greatly degrade its properties, can be removed by an activated carbon-coated lint roller, relying on the strong interactions between the amorphous carbon and activated carbon.

According to our information, LG Electronics is aiming to start supplying CVD graphene materials worldwide soon, with an aim to accelerate the adoption of CVD graphene in various applications. LG is collaborating with research groups to identify new applications for graphene sheets.

LG Electronics developed its own roll-to-roll production process in addition to a specific quality control system for its graphene. LG says that its inspection system can manage uniformity deviations in crystal size, defects and electrical properties in its graphene to within 10%.

Researchers at the University of Illinois examined how tiny defects in graphene membranes, formed during fabrication, could be used to improve molecule transport. They found that the defects make a big difference in how molecules move along a membrane surface. Instead of trying to fix these flaws, the team set out to use them to help direct molecules into the membrane pores.

Nanopore membranes have generated interest in biomedical research because they help researchers investigate individual molecules - atom by atom - by pulling them through pores for physical and chemical characterization. This technology could ultimately lead to devices that can quickly sequence DNA, RNA or proteins.