Researchers ink nanostructures with tiny 'soldering iron'

ScienceDaily (Nov. 7, 2011) — Researchers with the U.S. Department of Energy (DOE)'s Lawrence Berkeley National Laboratory (Berkeley Lab) have shed light on the role of temperature in controlling a fabrication technique for drawing chemical patterns as small as 20 nanometers. This technique could provide an inexpensive, fast route to growing and patterning a wide variety of materials on surfaces to build electrical circuits and chemical sensors, or study how pharmaceuticals bind to proteins and viruses.

One way of directly writing nanoscale structures onto a substrate is to use an atomic force microscope (AFM) tip as a pen to deposit ink molecules through molecular diffusion onto the surface. Unlike conventional nanofabrication techniques that are expensive, require specialized environments and usually work with only a few materials, this technique, called dip-pen nanolithography, can be used in almost any environment to write many different chemical compounds. A cousin of this technique -- called thermal dip-pen nanolithography -- extends this technique to solid materials by turning an AFM tip into a tiny soldering iron.

Dip-pen nanolithography can be used to pattern features as small as 20 nanometers, more than forty thousand times smaller than the width of a human hair. What's more, the writing tip also performs as a surface profiler, allowing a freshly-writ surface to be imaged with nanoscale precision immediately after patterning.

"Tip-based manufacturing holds real promise for precise fabrication of nanoscale devices," says Jim DeYoreo, interim director of Berkeley Lab's Molecular Foundry, a DOE nanoscience research center. "However, a robust technology requires a scientific foundation built on an understanding of material transfer during this process. Our study is the first to provide this fundamental understanding of thermal dip-pen nanolithography."

In this study, DeYoreo and coworkers systematically investigated the effect of temperature on feature size. Using their results, the team developed a new model to deconstruct how ink molecules travel from the writing tip to the substrate, assemble into an ordered layer and grow into a nanoscale feature.

"By carefully considering the role of temperature in thermal dip-pen nanolithography, we may be able to design and fabricate nanoscale patterns of materials ranging from small molecules to polymers with better control over feature sizes and shapes on a variety of substrates," says Sungwook Chung, a staff scientist in Berkeley Lab's Physical Biosciences Division, and Foundry user working with DeYoreo. "This technique helps overcome fundamental length scale limitations without the need for complex growth methods."

DeYoreo and Chung collaborated with a research team from the University of Illinois at Urbana-Champaign that specializes in fabricating specialized tips for AFMs. Here, these collaborators developed a silicon-based AFM tip with a gradient of charge-carrying atoms sprinkled into the silicon such that a higher number reside at the base while fewer sit at the tip. This makes the tip heat up when electricity flows through it, much like the burner on an electric stove.

This 'nanoheater' can then be used to heat up inks applied to the tip, causing them to flow to the surface for fabricating microscale and nanoscale features. The group demonstrated this by drawing dots and lines of the organic molecule mercaptohexadecanoic acid on gold surfaces. The hotter the tip, the larger the feature size the team could draw.

"We are excited about this collaboration with Berkeley Lab, which combines their remarkable nanoscience capabilities with our technology to control temperature and heat flow on the nanometer scale," says co-author William P. King, a University of Illinois professor of mechanical sciences and engineering. "Our ability to control the temperature within a nanometer-scale spot enabled this study of molecular-scale transport. By tuning the hotspot temperature, we can probe how molecules flow to a surface."

"This thermal control over tip-to-surface transfer developed by Professor King's group adds versatility by enabling on-the-fly variations in feature size and patterning of both liquid and solid materials," DeYoreo adds.

Chung is the lead author and DeYoreo the corresponding author of a paper reporting this research in the journal Applied Physics Letters. The paper is titled "Temperature-dependence of ink transport during thermal dip-pen nanolithography." Co-authoring the paper with Chung, DeYoreo and King were Jonathan Felts and Debin Wang.

This work at the Molecular Foundry was supported by DOE's Office of Science and the Defense Advanced Research Projects Agency.

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Edible carbon dioxide sponge: All-natural nanostructures could address pressing environmental problem

ScienceDaily (Sep. 25, 2011) — A year ago Northwestern University chemists published their recipe for a new class of nanostructures made of sugar, salt and alcohol. Now, the same team has discovered the edible compounds can efficiently detect, capture and store carbon dioxide. And the compounds themselves are carbon-neutral.

The porous crystals -- known as metal-organic frameworks (MOFs) -- are made from all-natural ingredients and are simple to prepare, giving them a huge advantage over other MOFs. Conventional MOFs, which also are effective at adsorbing carbon dioxide, are usually prepared from materials derived from crude oil and often incorporate toxic heavy metals.

Other features of the Northwestern MOFs are they turn red when completely full of carbon dioxide, and the carbon capture process is reversible.

The findings, made by scientists working in the laboratory of Sir Fraser Stoddart, Board of Trustees Professor of Chemistry in the Weinberg College of Arts and Sciences, are published in the Journal of the American Chemical Society (JACS).

"We are able to take molecules that are themselves sourced from atmospheric carbon, through photosynthesis, and use them to capture even more carbon dioxide," said Ross S. Forgan, a co-author of the study and a postdoctoral fellow in Stoddart's laboratory. "By preparing our MOFs from naturally derived ingredients, we are not only making materials that are entirely nontoxic, but we are also cutting down on the carbon dioxide emissions associated with their manufacture."

The main component, gamma-cyclodextrin, is a naturally occurring biorenewable sugar molecule that is derived from cornstarch.

The sugar molecules are held in place by metals taken from salts such as potassium benzoate or rubidium hydroxide, and it is the precise arrangement of the sugars in the crystals that is vital to their successful capture of carbon dioxide.

"It turns out that a fairly unexpected event occurs when you put that many sugars next to each other in an alkaline environment -- they start reacting with carbon dioxide in a process akin to carbon fixation, which is how sugars are made in the first place," said Jeremiah J. Gassensmith, lead author of the paper and also a postdoctoral fellow in Stoddart's laboratory. "The reaction leads to the carbon dioxide being tightly bound inside the crystals, but we can still recover it at a later date very simply."

The fact that the carbon dioxide reacts with the MOF, an unusual occurrence, led to a simple method of detecting when the crystals have reached full capacity. The researchers place an indicator molecule, which detects changes in pH by changing its color, inside each crystal. When the yellow crystals of the MOFs are full of carbon dioxide they turn red.

The simplicity of the new MOFs, allied with their low cost and green credentials, have marked them as candidates for further commercialization. Ronald A. Smaldone, also a postdoctoral fellow in Stoddart's group and a co-author of the paper, added, "I think this is a remarkable demonstration of how simple chemistry can be successfully applied to relevant problems like carbon capture and sensor technology."

The National Science Foundation, the U.S. Department of Energy, the Engineering and Physical Sciences Research Council in the U.K., the King Abdulaziz City of Science and Technology (KACST) in Saudi Arabia and the Korea Advanced Institute of Science and Technology (KAIST) in Korea supported the research.

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The above story is reprinted (with editorial adaptations by ScienceDaily staff) from materials provided by Northwestern University. The original article was written by Megan Fellman.

Journal Reference:

Jeremiah J. Gassensmith, Hiroyasu Furukawa, Ronald A. Smaldone, Ross S. Forgan, Youssry Y. Botros, Omar M. Yaghi, J. Fraser Stoddart. Strong and Reversible Binding of Carbon Dioxide in a Green Metal–Organic Framework. Journal of the American Chemical Society, 2011; 110913144109022 DOI: 10.1021/ja206525x

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Disclaimer: Views expressed in this article do not necessarily reflect those of ScienceDaily or its staff.

View the original article here

Edible carbon dioxide sponge: All-natural nanostructures could address pressing environmental problem

ScienceDaily (Sep. 25, 2011) — A year ago Northwestern University chemists published their recipe for a new class of nanostructures made of sugar, salt and alcohol. Now, the same team has discovered the edible compounds can efficiently detect, capture and store carbon dioxide. And the compounds themselves are carbon-neutral.

The porous crystals -- known as metal-organic frameworks (MOFs) -- are made from all-natural ingredients and are simple to prepare, giving them a huge advantage over other MOFs. Conventional MOFs, which also are effective at adsorbing carbon dioxide, are usually prepared from materials derived from crude oil and often incorporate toxic heavy metals.

Other features of the Northwestern MOFs are they turn red when completely full of carbon dioxide, and the carbon capture process is reversible.

The findings, made by scientists working in the laboratory of Sir Fraser Stoddart, Board of Trustees Professor of Chemistry in the Weinberg College of Arts and Sciences, are published in the Journal of the American Chemical Society (JACS).

"We are able to take molecules that are themselves sourced from atmospheric carbon, through photosynthesis, and use them to capture even more carbon dioxide," said Ross S. Forgan, a co-author of the study and a postdoctoral fellow in Stoddart's laboratory. "By preparing our MOFs from naturally derived ingredients, we are not only making materials that are entirely nontoxic, but we are also cutting down on the carbon dioxide emissions associated with their manufacture."

The main component, gamma-cyclodextrin, is a naturally occurring biorenewable sugar molecule that is derived from cornstarch.

The sugar molecules are held in place by metals taken from salts such as potassium benzoate or rubidium hydroxide, and it is the precise arrangement of the sugars in the crystals that is vital to their successful capture of carbon dioxide.

"It turns out that a fairly unexpected event occurs when you put that many sugars next to each other in an alkaline environment -- they start reacting with carbon dioxide in a process akin to carbon fixation, which is how sugars are made in the first place," said Jeremiah J. Gassensmith, lead author of the paper and also a postdoctoral fellow in Stoddart's laboratory. "The reaction leads to the carbon dioxide being tightly bound inside the crystals, but we can still recover it at a later date very simply."

The fact that the carbon dioxide reacts with the MOF, an unusual occurrence, led to a simple method of detecting when the crystals have reached full capacity. The researchers place an indicator molecule, which detects changes in pH by changing its color, inside each crystal. When the yellow crystals of the MOFs are full of carbon dioxide they turn red.

The simplicity of the new MOFs, allied with their low cost and green credentials, have marked them as candidates for further commercialization. Ronald A. Smaldone, also a postdoctoral fellow in Stoddart's group and a co-author of the paper, added, "I think this is a remarkable demonstration of how simple chemistry can be successfully applied to relevant problems like carbon capture and sensor technology."

The National Science Foundation, the U.S. Department of Energy, the Engineering and Physical Sciences Research Council in the U.K., the King Abdulaziz City of Science and Technology (KACST) in Saudi Arabia and the Korea Advanced Institute of Science and Technology (KAIST) in Korea supported the research.

Recommend this story on Facebook, Twitter,
and Google +1:

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Story Source:

The above story is reprinted (with editorial adaptations by ScienceDaily staff) from materials provided by Northwestern University. The original article was written by Megan Fellman.

Journal Reference:

Jeremiah J. Gassensmith, Hiroyasu Furukawa, Ronald A. Smaldone, Ross S. Forgan, Youssry Y. Botros, Omar M. Yaghi, J. Fraser Stoddart. Strong and Reversible Binding of Carbon Dioxide in a Green Metal–Organic Framework. Journal of the American Chemical Society, 2011; 110913144109022 DOI: 10.1021/ja206525x

Note: If no author is given, the source is cited instead.

Disclaimer: Views expressed in this article do not necessarily reflect those of ScienceDaily or its staff.

View the original article here