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David Ruth
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david@rice.edu

Mike Williams
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Fluorine flows in, makes material metal

Rice University lab adds metallic ‘islands’ to 2D semiconductor for electronics

HOUSTON – (Oct. 15, 2018) – By getting in the way, fluorine atoms help a two-dimensional material transform from a semiconductor to a metal in a way that could be highly useful for electronics and other applications.

A study led by Rice materials scientist Pulickel Ajayan and lead author Sruthi Radhakrishnan details a new method to transform tungsten disulfide from a semiconductor to a metallic state.

Fluoridating two-dimensional tungsten disulfide adds metallic islands to the synthetic semiconductor, along with unique optical and magnetic properties, according to researchers at Rice University. Courtesy of the Ajayan Research Group

Other labs have achieved the transformation by adding elements to the material – a process known as doping – but the change has never before been stable. Tests and calculations at Rice showed fluorinating tungsten disulfide locks in the new state, which has unique optical and magnetic properties.

The researchers also noted the transformation’s effect on the material’s tribological properties — a measure of friction, lubrication and wear. In short, adding fluorine makes the material more slippery at room temperature.

The lab’s work is detailed in Advanced Materials.

Tungsten disulfide is a transition metal dichalcogenide (TMD), an atom-thick semiconductor. Unlike graphene, which is a flat lattice of carbon atoms, a TMD incorporates two elements, one a transition metal atom (in this case, tungsten) and the other (sulfur) a chalcogen. The material isn’t strictly flat; the transition metal layer is sandwiched between the chalcogen, forming a three-layered lattice.

Fluoridating two-dimensional tungsten disulfide adds metallic islands to the synthetic semiconductor, along with unique optical and magnetic properties, according to researchers at Rice University. Courtesy of the Ajayan Research Group

TMDs are potential building blocks with other 2D materials for energy storage, electrocatalysis and lubrication, all of which are influenced by the now-stable phase transformation.

Because fluorine atoms are much smaller than the 0.6-nanometer space between the layers of tungsten and sulfur, the researchers said the invasive atoms work their way in between, disrupting the material’s orderly lattice. The fluorine allows the sulfur planes to glide this way or that, and the resulting trade of electrons between the fluorine and sulfur also accounts for the unique properties.

“It was certainly a big surprise. When we started this work, a phase transformation was the last thing we expected to see.” said Radhakrishnan, a former graduate student in Ajayan’s lab and now a module engineer at Intel Corp. in Hillsboro, Ore.

“It is really surprising that the frictional characteristics of fluorinated tungsten disulfide are entirely different from the fluorinated graphene that was studied before,” said co-author Tobin Filleter, an associate professor of mechanical engineering at the University of Toronto. “This is a motivation to study similar 2D materials to explore such interesting behavior.”

The researchers said fluorine appears to not only decrease the bandgap and make the material more conductive but also causes defects that create metallic “islands” along the material’s surface that also display paramagnetic and ferromagnetic properties. “These regions of metallic tungsten disulfide are magnetic and they interfere with each other, creating interesting magnetic properties,” Radhakrishnan said.

Further, because fluorine atoms are electrically negative, they’re also suspected of changing the electron density of neighboring atoms. That changes the material’s optical properties, making it a candidate for sensing and catalysis applications. Radhakrishnan suggested the materials may also be useful in their metallic phase as electrodes for supercapacitors and other energy-storage applications.

Radhakrishnan

Radhakrishnan said different concentrations of fluorine alter the proportion of change to the metallic phase, but the change remained stable in all three concentrations the lab studied.

“The phase transformation, change in properties with functionalization by fluorine and its magnetic and tribological changes are very exciting,” Ajayan said. “This can be extended to other 2D layered materials and I am sure it will open up some captivating applications.”

Co-authors of the paper are Deya Das and Abhishek Singh of the Indian Institute of Science; Liangzi Deng and Paul Chu, a professor of physics at the University of Houston; Filleter, Parambath Sudeep and Guillaume Colas of the University of Toronto; Sadegh Yazdi of the University of Colorado, Boulder; Rice alumnus Chandra Sekhar Tiwary of the Indian Institute of Technology Kharagpur; and graduate student Carlos de los Reyes and Angel Martí, an associate professor of chemistry, bioengineering and materials science and nanoengineering, of Rice.

Ajayan is chair of Rice’s Department of Materials Science and NanoEngineering, the Benjamin M. and Mary Greenwood Anderson Professor in Engineering and a professor of chemistry.

The research was supported by the Air Force Office of Scientific Research, the National Science Foundation, the T.L.L. Temple Foundation, the John J. and Rebecca Moores Endowment, the Texas Center for Superconductivity at the University of Houston, the Natural Sciences and Engineering Research Council of Canada, the Canada Foundation for Innovation, the Erwin Edward Hart Professorship, the Department of Science and Technology Nano Mission at the Indian Institute of Science and a Ramanujan Fellowship from the Government of India.

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Read the abstract at https://onlinelibrary.wiley.com/doi/10.1002/adma.201803366.

Follow Rice News and Media Relations via Twitter @RiceUNews.

Related materials:

Fluorine grants white graphene new powers: http://news.rice.edu/2017/07/14/fluorine-grants-white-graphene-new-powers-2/

Ajayan Research Group: http://ajayan.rice.edu

NanoMechanics and Materials Lab (Filleter group): http://www2.mie.utoronto.ca/labs/nmml/

Ching Wu Chu Group: http://tcsuh.com/people/facultypl/chu_paul/

Department of Materials Science and NanoEngineering: https://msne.rice.edu

George R. Brown School of Engineering: https://engineering.rice.edu

Images for download:

http://news.rice.edu/files/2018/10/1008_PHASE-1-web-2ea4xzl.jpg

Fluoridating two-dimensional tungsten disulfide adds metallic islands to the synthetic semiconductor, along with unique optical and magnetic properties, according to researchers at Rice University. (Credit: Ajayan Research Group/Rice University)

http://news.rice.edu/files/2018/10/1008_PHASE-2-web-2gdh2a7.jpg

Fluoridating two-dimensional tungsten disulfide adds metallic islands to the synthetic semiconductor, along with unique optical and magnetic properties, according to researchers at Rice University. (Credit: Ajayan Research Group/Rice University)

http://news.rice.edu/files/2018/10/1008_PHASE-3-web-2lmaaof.jpg

Rice University alumna Sruthi Radhakrishnan led a project that discovered how to turn a two-dimensional semiconductor, tungsten disulfide, into a metal by doping it with fluorine. The resulting material is stable and could be used for electronics or other applications. (Credit: Jeff Fitlow/Rice University)

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