Expanding the degrees of surface freezing

Mar 31, 2011
Schematic representation of the alkanol monolayer when frozen (left) and melted (right).

(PhysOrg.com) -- As part of the quest to form perfectly smooth single-molecule layers of materials for advanced energy, electronic, and medical devices, researchers at the U.S. Department of Energy's Brookhaven National Laboratory have discovered that the molecules in thin films remain frozen at a temperature where the bulk material is molten. Thin molecular films have a range of applications extending from organic solar cells to biosensors, and understanding the fundamental aspects of these films could lead to improved devices.

The study, which appears in the April 1, 2011, edition of , is the first to directly observe "surface freezing" at the buried interface between bulk liquids and solid surfaces.

"In most materials, you expect that the surface will start to disorder and eventually melt at a temperature where the bulk remains solid," said Brookhaven physicist Ben Ocko, who collaborated on the research with scientists from the European Synchrotron Radiation Facility (ESRF), in France, and Bar-Ilan University, in Israel. "This is because the molecules on the outside are less confined than those packed in the deeper layers and much more able to move around. But surface freezing contradicts this basic idea. In surface freezing, the interfacial layers freeze before the bulk."

In the early 1990s, two independent teams (one at Brookhaven) made the first observation of surface freezing at the vapor interface of bulk alkanes, similar to those in candle wax that contain only carbon and . Surface freezing has since been observed in a range of simple chain molecules and at various interfaces between them.

"The mechanics of surface freezing are still a mystery," said Bar Ilan scientist Moshe Deutsch. "It's puzzling why alkanes and their derivatives show this unusual effect, while virtually all other materials exhibit the opposite, surface melting, effect."

In the most recent study, the researchers discovered that surface freezing also occurs at the interface between a liquid and a solid surface. In a temperature-controlled environment at Brookhaven's National Synchrotron Light Source and the ESRF, the group made contact between a piece of highly polished sapphire and a puddle of liquid alkanol — a long-chain alcohol. The researchers shot a beam of high-intensity x-rays through the interface and by measuring how the x-rays reflected off the sample, the group revealed that the alkanol molecules at the sapphire surface behave very differently from those in the bulk liquid.

According to ESRF scientist Diego Pontoni, "Surprisingly, the alkanol molecules form a perfect frozen monolayer at the sapphire interface at temperatures where the bulk is still liquid." At sufficiently high temperatures, about 30 degrees Celsius above the melting temperature of the bulk alkanol, the monolayer also melts.

The temperature range over which this frozen monolayer exists is about 10 times greater than what's observed at the liquid-vapor interfaces of similar materials. According to Alexei Tkachenko, a theoretical physicist who works at Brookhaven's Center for Functional Nanomaterials , "The temperature range of the surface-frozen layer and its temperature-dependent thickness can be described by a very simple model that we developed. What is remarkable is that the surface layer does not freeze abruptly as in the case of ice, or any other crystal. Rather, a smooth transition occurs over a temperature range of several degrees."

Said Ocko, "These films are better ordered and smoother than all other organic monolayer films created to date."

Moshe Deutsch added, "The results of this study and the theoretical framework which it provides may lead to new ideas on how to make defect-free, single molecule-thick films."

Explore further: Information storage for the next generation of plastic computers

Related Stories

Measuring the Speed of Noble 'Bubbles'

Feb 12, 2010

(PhysOrg.com) -- Using a layer of noble gas "bubbles," scientists at Pacific Northwest National Laboratory devised a straightforward way to measure how fast molecules diffuse in supercooled liquids. Working ...

Filling 'Nanocontainers' with Liquid

Jan 06, 2006

In research that may help advance many emerging nanotechnologies, scientists at the U.S. Department of Energy’s Brookhaven National Laboratory, together with research groups from Harvard University and IBM, ...

Pinning Down Superconductivity to a Single Layer

Oct 29, 2009

(PhysOrg.com) -- Using precision techniques for making superconducting thin films layer-by-layer, physicists at the U.S. Department of Energy's Brookhaven National Laboratory have identified a single layer ...

Recommended for you

Better thermal-imaging lens from waste sulfur

12 hours ago

Sulfur left over from refining fossil fuels can be transformed into cheap, lightweight, plastic lenses for infrared devices, including night-vision goggles, a University of Arizona-led international team ...

How to test the twin paradox without using a spaceship

Apr 16, 2014

Forget about anti-ageing creams and hair treatments. If you want to stay young, get a fast spaceship. That is what Einstein's Theory of Relativity predicted a century ago, and it is commonly known as "twin ...

User comments : 0

More news stories

Better thermal-imaging lens from waste sulfur

Sulfur left over from refining fossil fuels can be transformed into cheap, lightweight, plastic lenses for infrared devices, including night-vision goggles, a University of Arizona-led international team ...

Robotics goes micro-scale

(Phys.org) —The development of light-driven 'micro-robots' that can autonomously investigate and manipulate the nano-scale environment in a microscope comes a step closer, thanks to new research from the ...

Scientists tether lionfish to Cayman reefs

Research done by U.S. scientists in the Cayman Islands suggests that native predators can be trained to gobble up invasive lionfish that colonize regional reefs and voraciously prey on juvenile marine creatures.

Leeches help save woman's ear after pit bull mauling

(HealthDay)—A pit bull attack in July 2013 left a 19-year-old woman with her left ear ripped from her head, leaving an open wound. After preserving the ear, the surgical team started with a reconnection ...

Hackathon team's GoogolPlex gives Siri extra powers

(Phys.org) —Four freshmen at the University of Pennsylvania have taken Apple's personal assistant Siri to behave as a graduate-level executive assistant which, when asked, is capable of adjusting the temperature ...