Print Page | Contact Us | Report Abuse | Sign In | Register
Graphene Updates
Blog Home All Blogs

Growing carbon nanotubes with the right twist

Posted By Graphene Council, Monday, December 16, 2019
In a recently published paper in Science Advances, Feng Ding of the Center for Multidimensional Carbon Materials, within the Institute of Basic Science (IBS, South Korea) and colleagues, have achieved the creation of a specific type of carbon nanotubes (CNTs) with a selectivity of 90%, and expanded the current theory that explains the synthesis of these promising nano-cylinders.

CNTs are incredibly strong and light nanomaterials made of carbon with superior current carrying capacity and very high thermal conductivity, making them ideal for electronic applications. Although CNTs are considered as some of the most interesting materials for the future, scientists are still struggling for their controllable synthesis.

The CNTs' shape can be compared to paper tubes: in the same way as a cylinder can be created by rolling a sheet of paper, so CNTs can be imagined as a single layer of graphite rolled up on itself. Similarly, as different tubes can be produced by rolling a paper around its long side, its short side, or diagonally at different angles. Depending on the rolling direction, a graphite layer can produce different CNT structures, some are conducting and others are semiconducting, thus selectively creating a specific type of CNT will be key for their future use, such as building energy efficient computer chips. However, CNTs are not produced by rolling, but are grown nanometer after nanometer, adding carbon at the rim of nano-cylinders, one atom at a time. Despite various studies during the last three decades, the understanding on CNT growth remains very limited and rational experimental design for the growth of specific types of CNTs is challenging.

One of the most promising manufacturing methods for CNT is the chemical vapor deposition (CVD). In this process, metal nanoparticles combined with carbon-containing gases form CNTs inside a high-temperature furnace. On the tip of the tubes, the metal nanoparticles play a critical role as catalysts: they dissociate the carbon source from the gases, and assist the attachment of these carbon atoms to the CNT wall, making the tubes longer and longer. The growth of the CNT terminates once the catalyst particle is encapsulated by graphitic or amorphous carbon.

Carbon atoms are inserted onto the interface between a growing CNT and a catalyst nanoparticle, in active sites of the rim, and are available to incorporate new atoms. A previous model of CNT's growth rate showed that the latter is proportional to the density of these active sites at the interface between CNT and the catalyst, or the specific structure of the CNT.

In this study, the researchers monitored the steady growth of CNTs on a magnesium oxide (MgO) support with carbon monoxide (CO) as the carbon feedstock and cobalt nanoparticles as catalysts at 700oC. The direct experimental measurements of 16 CNTs showed how to expand the previous theory. "It was surprising that the growth rate of a carbon nanotubes only depends on the size of the catalyst particle. This implies that our previous understanding on carbon nanotubes growth was not complete," says Maoshuai He, the first author of the paper.

More specifically, carbon atoms that are deposited on the catalyst particle surface can be either incorporated on the active side of the CNT or removed by etching agents, such as H2, H2O, O2, or CO2. To explain the new experimental observations, the team included the effects of carbon insertion and removal during CNT growth and discovered that the growth rate depends on the catalyst's surface area and tube diameter ratio.

"Compared to the previous model, we added three more factors: the rate of precursor deposition, the rate of carbon removal by etching agents, and the rate of carbon insertion into a carbon nanotube wall. When feedstock dissociation cannot be balanced by carbon etching, the rate of carbon nanotube growth will no longer depend on the structure of the carbon nanotube. On the other hand, the previous theory is still valid if the etching is dominating," explains Ding, a group leader of the Center for Multidimensional Carbon Materials.

Interestingly, the new theory of CNT growth leads to a new mechanism to selectively grow a specific type of CNTs, denoted as (2n, n) CNTs, which is characterized by the maximum number of active sites at the interface between the CNT and the catalyst. This CNT structure would correspond to rolling a sheet of graphite diagonally at an angle of around 19 degrees.

"If there is no carbon etching and the carbon nanotubes growth is slow, carbon atoms on the catalyst surface will accumulate," says Jin Zhang, co-author of the study and professor of Peking University, China. "This may lead to the formation of graphitic or amorphous carbon, which are established mechanisms of carbon nanotube growth termination. In this case, only carbon nanotubes which are able to add carbon atoms on their walls, that is with the highest number of active sites, can survive."

Guided by the new theoretical understanding, the researchers were able to design experiments that produced (2n, n) CNTs with a selectivity of up to 90%: the highest selective growth of this type of CNT was achieved in the absence of any etching agent and with a high feedstock concentration.

Tags:  Carbon Nanotubes  Center for Multidimensional Carbon Materials  Feng Ding  Graphene  Institute of Basic Science  Science Advances 

Share |
PermalinkComments (0)
 

How to enlarge 2D materials as single crystals?

Posted By Graphene Council, Friday, May 31, 2019

What makes something a crystal? When all of its atoms are arranged in accordance with specific mathematical rules, we call the material a single crystal. Like the natural world has its unique symmetry just as snowflakes or honeycombs, the atomic world of crystals is designed by its own structure and symmetry. This material structure has a profound effect on its physical properties as well. Specifically, single crystals play an important role in inducing material's intrinsic properties to its full extent. Faced with the coming end of the miniaturization process that the silicon-based integrated circuit has allowed up to this point, huge efforts have been dedicated to find a single crystalline replacement for silicon.


In search for the transistor of the future, two-dimensional (2D) materials, especially graphene have been the subject of intense research around the world. Being thin and flexible as a result of being only a single layer of atoms, this 2D version of carbon even features unprecedented electricity and heat conductivity. However, the last decade's efforts for graphene transistors have been held up by physical restraints graphene allows no control over electricity flow due to the lack of band gap. Then, what about other 2D materials? A number of interesting 2D materials have been reported to have similar or even superior properties. Still, the lack of understanding in creating ideal experimental conditions for large-area 2D materials has limited their maximum size to just a few mm 2.

Scientists at the Center for Multidimensional Carbon Material (CMCM) within the Institute for Basic Science (IBS) (located in the Ulsan National Institute of Science and Technology (UNIST)) have presented a novel approach to synthesize large-scale of silicon wafer size, single crystalline 2D materials. Prof. Feng Ding and Ms. Leining Zhang in collaboration with their colleagues in Peking University, China and other institutes have found a substrate with a lower order of symmetry than that of a 2D material that facilitates the synthesis of single crystalline 2D materials in a large area. "It was critical to find the right balance of rotational symmetries between a substrate and a 2D material," notes Prof. Feng Ding, one of corresponding authors of this study. The researchers successfully synthesized hBN single crystals of 10*10 cm2 by using a new substrate: a surface nearby Cu (110) that has a lower symmetry of (1) than hBN with (3).

Then, why does symmetry matters? Symmetry, in particular rotational symmetry, describes how many times a certain shape fits on to itself during a full rotation of 360 degrees. The most efficient method to synthesize large-area and single crystals of 2D materials is to arrange layers over layers of small single crystals and grow them upon a substrate. In this epitaxial growth, it is quite challenging to ensure all of the single crystals are aligned in a single direction. Orientation of the crystals is often affected by the underlying substrate. By theoretical analysis, the IBS scientists found that an hBN island (or a group of hBN atoms forming a single triangle shape) has two equivalent alignments on the Cu(111) surface that has a very high symmetry of (6). "It was a common view that a substrate with high symmetry may lead to the growth of materials with a high symmetry. It seemed to make sense intuitively, but this study found it is incorrect," says Ms. Leining Zhang, the first author of the study.

Previously, various substrates such as Cu(111) have been used to synthesize single crystalline hBN in a large area, but none of them were successful. Every effort ended with hBN islands aligning along in several different directions on the surfaces. Convinced by the fact that the key to achieve unidirectional alignment is to reduce the symmetry of the substrate, the researchers made tremendous efforts to obtain vicinal surfaces of a Cu(110) orientation; a surface obtained by cutting a Cu(110) with a small tilt angle. It is like forming physical steps on Cu. As a hBN island tends to place in parallel to the edge of each step, it gets only one preferred alignment. The small tilt angle lowers the symmetry of the surface as well.

They eventually found that a class of vicinal surfaces of Cu (110) can be used to support the growth of hBN with perfect alignment. On a carefully selected substrate with the lowest symmetry or the surface will repeat itself only after a 360degree rotation, hBN has only one preferred direction of alignment. The research team of Prof. Kaihui Liu in Peking University, has developed a unique method to anneal a large Cu foil, up to 10*10 cm2, into a single crystal with the vicinal Cu (110) surface and, with it, they have achieved the synthesis of hBN single crystals of same size.

Besides flexibility and ultrathin thickness, emerging 2D materials can present extraordinary properties when they get enlarged as single crystals. "This study provides a general guideline for the experimental synthesis of various 2D materials. Besides the hBN, many other 2D materials could be synthesized with the large area single crystalline substrates with low symmetry," says Prof. Feng Ding. Notably, hBN is the most representative 2D insulator, which is different from the conductive 2D materials, such as graphene, and 2D semiconductors, such as molybdenum disulfide (MoS2). The vertical stacking of various types of 2D materials, such as hBN, graphene and MoS2, would lead to a large number of new materials with exceptional properties and can be used for numerous applications, such as high-performance electronics, sensors, or wearable electronics."

Tags:  2D materials  Center for Multidimensional Carbon Material  Feng Ding  Graphene  Kaihui Liu  Peking University  Semiconductors 

Share |
PermalinkComments (0)