Controlled Fabrication of DNA Molecular Templates for In Situ Formation and Measurement of Ultrathin Metal Nanostructures.

Fabrication of ultrathin metal nanostructures usually requires some combination of high-vacuum deposition and postgrowth processing, which precludes access to nanostructures of ultrasmall cross sections for most materials. DNA nanowires (NWs) are versatile insulating templates with intrinsic sub-10 nm line width. Here, we demonstrate a method of DNA template fabrication with precise control over the location and orientation of the DNA NWs. We further demonstrate that this template can be used to support formation of ultrathin metal NWs for derivative nanodevices: a metal is incrementally deposited, and electrical transport measurement is performed in situ at each step. The results show a homogeneous metal NW is obtained at a thickness as small as 0.9 nm with a cross-section of only a few nm2. The high degree of control in the location, separation, and orientation of the DNA NWs affords this method great promise in fabricating complex nanodevices based on metal NWs.

Antiferroelectric Phase Transition in a Proton-Transfer Salt of Squaric Acid and 2,3-Dimethylpyrazine.

A proton-transfer reaction between squaric acid (H2sq) and 2,3-dimethylpyrazine (2,3-Me2pyz) results in crystallization of a new organic antiferroelectric (AFE), (2,3-Me2pyzH+)(Hsq-)·H2O (1), which possesses a layered structure. The structure of each layer can be described as partitioned into strips lined with methyl groups of the Me2pyzH+ cations and strips featuring extensive hydrogen bonding between the Hsq- anions and water molecules. Variable-temperature dielectric measurements and crystal structures determined through a combination of single-crystal X-ray and neutron diffraction reveal an AFE ordering at 104 K. The phase transition is driven by ordering of protons within the hydrogen-bonded strips. Considering the extent of proton transfer, the paraelectric (PE) state can be formulated as (2,3-Me2pyzH+)2(Hsq23-)(H5O2+), whereas the AFE phase can be described as (2,3-Me2pyzH+)(Hsq-)(H2O). The structural transition caused by the localization of protons results in the change in color from yellow in the PE state to colorless in the AFE state. The occurrence and mechanism of the AFE phase transition have been also confirmed by heat capacity measurements and variable-temperature infrared and Raman spectroscopy. This work demonstrates a potentially promising approach to the design of new electrically ordered materials by engineering molecule-based crystal structures in which hydrogen-bonding interactions are intentionally partitioned into quasi-one-dimensional regions.