Sheng-Chin Kung

Smaller is faster and more sensitive: the effect of wire size on the detection of hydrogen by single palladium nanowires.

Palladium nanowires prepared using the lithographically patterned nanowire electrodeposition (LPNE) method are used to detect hydrogen gas (H2). These palladium nanowires are prepared by electrodepositing palladium from EDTA-containing solutions under conditions favoring the formation of β-phase PdHx. The Pd nanowires produced by this procedure are characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. These nanowires have a mean grain diameter of 15 nm and are composed of pure Pd with no XPS-detectable bulk carbon. The four-point resistance of 50-100 μm segments of individual nanowires is used to detect H2 in N2 and air at concentrations ranging from 2 ppm to 10%. For low [H2] < 1%, the response amplitude increases by a factor of 2-3 with a reduction in the lateral dimensions of the nanowire. Smaller nanowires show accelerated response and recovery rates at all H2 concentrations from, 5 ppm to 10%. For 12 devices, response and recovery times are correlated with the surface area/volume ratio of the palladium detection element. We conclude that the kinetics of hydrogen adsorption limits the observed response rate seen for the nanowire, and that hydrogen desorption from the nanowire limits the observed recovery rate; proton diffusion within PdHx does not limit the rates of either of these processes.

20 μs Photocurrent Response from Lithographically Patterned Nanocrystalline Cadmium Selenide Nanowires

Lithographically patterned nanowire electrodeposition (LPNE) provides a method for patterning nanowires composed of nanocrystalline cadmium selenide (nc-CdSe) over wafer-scale areas. We assess the properties of (nc-CdSe) nanowires for detecting light as photoconductors. Structural characterization of these nanowires by X-ray diffraction and transmission electron microscopy reveals they are composed of stoichiometric, single phase, cubic CdSe with a mean grain diameter of 10 nm. For nc-CdSe nanowires with lengths of many millimeters, the width and height dimensions could be varied over the range from 60 to 350 nm (w) and 20 to 80 nm (h). Optical absorption and photoluminescence spectra for nc-CdSe nanowires were both dominated by band-edge transitions. The photoconductivity properties of nc-CdSe nanowire arrays containing approximately 350 nanowires were evaluated by electrically isolating 5 microm nanowire lengths using evaporated gold electrodes. Photocurrents, i(photo), of 10-100 x (i(dark)) were observed with a spectral response characterized by an onset at 1.75 eV. i(photo) response and recovery times were virtually identical and in the range from 20 to 40 micros for 60 x 200 nm nanowires.

Enhanced Thermoelectric Metrics in Ultra-long Electrodeposited PEDOT Nanowires

The Seebeck coefficient, S, and the electrical conductivity, σ, of electrodeposited poly(3,4-ethylenedioxythiophene) (PEDOT) nanowires and thin films are reported. PEDOT nanowires were prepared by electropolymerizing 3,4-ethylenedioxythiophene (EDOT) in aqueous LiClO(4) within a template prepared using the lithographically patterned nanowire electrodeposition (LPNE) process. These nanowires were 40-90 nm in thickness, 150-580 nm in width, and 200 μm in length. σ and S were measured from 190 K to 310 K by fabricating heaters and thermocouples on top of arrays of 750 PEDOT nanowires. Such PEDOT nanowire arrays consistently produced S values that were higher than those for PEDOT films: up to -122 μV/K (310 K) for nanowires and up to -57 μV/K (310 K) for films. The sample-to-sample variation in S for 14 samples of PEDOT nanowires and films, across a wide range of critical dimensions, is fully explained by variations in the carrier concentrations in accordance with the Mott equation. In spite of their higher |S| values, PEDOT nanowires also had higher σ than films, on average, because electron mobilities were greater in nanowires by a factor of 3.

Lithographically patterned nanowire electrodeposition: a method for patterning electrically continuous metal nanowires on dielectrics.

Lithographically patterned nanowire electrodeposition (LPNE) is a new method for fabricating polycrystalline metal nanowires using electrodeposition. In LPNE, a sacrificial metal (M(1)=silver or nickel) layer, 5-100 nm in thickness, is first vapor deposited onto a glass, oxidized silicon, or Kapton polymer film. A (+) photoresist (PR) layer is then deposited, photopatterned, and the exposed Ag or Ni is removed by wet etching. The etching duration is adjusted to produce an undercut approximately 300 nm in width at the edges of the exposed PR. This undercut produces a horizontal trench with a precisely defined height equal to the thickness of the M(1) layer. Within this trench, a nanowire of metal M(2) is electrodeposited (M(2)=gold, platinum, palladium, or bismuth). Finally the PR layer and M(1) layer are removed. The nanowire height and width can be independently controlled down to minimum dimensions of 5 nm (h) and 11 nm (w), for example, in the case of platinum. These nanowires can be 1 cm in total length. We measure the temperature-dependent resistance of 100 microm sections of Au and Pd wires in order to estimate an electrical grain size for comparison with measurements by X-ray diffraction and transmission electron microscopy. Nanowire arrays can be postpatterned to produce two-dimensional arrays of nanorods. Nanowire patterns can also be overlaid one on top of another by repeating the LPNE process twice in succession to produce, for example, arrays of low-impedance, nanowire-nanowire junctions.

Synthesis of PbTe Nanowire Arrays using Lithographically Patterned Nanowire Electrodeposition

We describe the preparation by electrodeposition of arrays of lead telluride (PbTe) nanowires using the lithographically patterned nanowire electrodeposition (LPNE) method. PbTe nanowires had a rectangular cross-section with adjustable width and height ranging between 60-400 nm (w) and 20-100 nm (h). The characterization of these nanowire arrays using X-ray diffraction, transmission electron microscopy and electron diffraction, scanning electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy (XPS) is reported. PbTe nanowires were electrodeposited using a cyclic electrodeposition-stripping technique that produced polycrystalline, stoichiometric, face-centered cubic PbTe with a mean grain diameter of 10-20 nm. These nanowires were more than 1 mm in length and two additional processing steps permitted their suspension across 25 microm air gaps microfabricated on these surfaces. The LPNE synthesis of lithographically patterned PbTe nanowires was carried out in unfiltered laboratory air. Nanowires with lengths of 70-100 microm showed an electrical resistivity comparable to bulk PbTe. XPS reveals that exposure of PbTe nanowires to air causes the formation on the nanowire surface of approximately one monolayer of a mixed lead oxide and tellurium oxide within a few minutes.

The surface scattering-based detection of hydrogen in air using a platinum nanowire.

The performance of a single platinum (Pt) nanowire for detecting H(2) in air is reported. A Pt nanowire shows no resistance change upon exposure to H(2) in N(2), but H(2) exposure in air causes a reversible resistance decrease for H(2) concentrations above 10 ppm. The amplitude of the resistance change induced by H(2) exposure and the time rate of change of the nanowire resistance both increased with increasing temperature from 298 to 550 K. This resistance decrease of the Pt nanowire in the presence of H(2) results from reduced electron diffuse scattering at hydrogen-covered Pt surfaces as compared with oxygen-covered platinum surfaces, we hypothesize. The properties for the detection of H(2) in air of single Pt and Pd nanowires of similar size are compared in this study. Pt nanowires have a limit-of-detection for H(2) (LOD(H(2))) of 10 ppm; 3 orders of magnitude lower than for Pd nanowires of the same size, as well as a response time that is 1/100th of Pd for [H(2)] ≈ 1%.

Tunable photoconduction sensitivity and bandwidth for lithographically patterned nanocrystalline cadmium selenide nanowires.

Nanocrystalline cadmium selenide (nc-CdSe) nanowires were prepared using the lithographically patterned nanowire electrodeposition method. Arrays of 350 linear nc-CdSe nanowires with lateral dimensions of 60 nm (h) × 200 nm (w) were patterned at 5 μm pitch on glass. nc-CdSe nanowires electrodeposited from aqueous solutions at 25 °C had a mean grain diameter, d(ave), of 5 nm. A combination of three methods was used to increase d(ave) to 10, 20, and 100 nm: (1) The deposition bath was heated to 75 °C, (2) nanowires were thermally annealed at 300 °C, and (3) nanowires were exposed to methanolic CdCl(2) followed by thermal annealing at 300 °C. The morphology, chemical composition, grain diameter, and photoconductivity of the resulting nanowires were studied as a function of d(ave). As d(ave) was increased from 10 to 100 nm, the photoconductivity response of the nanowires was modified in two ways: First, the measured photoconductive gain, G, was elevated from G = 0.017 (d(ave) = 5 nm) to ∼4.9 (100 nm), a factor of 290. Second, the photocurrent rise time was increased from 8 μs for d(ave) = 10 nm to 8 s for 100 nm, corresponding to a decrease by a factor of 1 million of the photoconduction bandwidth from 44 kHz to 44 mHz.

Wafer-Scale Patterning of Lead Telluride Nanowires: Structure, Characterization, and Electrical Properties

Nanowires of lead telluride (PbTe) were patterned on glass surfaces using lithographically patterned nanowire electrodeposition (LPNE). LPNE involved the fabrication by photolithography of a contoured nickel nanoband that is recessed by approximately 300 nm into a horizontal photoresist trench. Cubic PbTe was then electrodeposited from a basic aqueous solution containing Pb(2+) and TeO(3)(2-) at the nickel nanoband using a cyclic deposition/stripping potential program in which lead-rich PbTe was first deposited in a negative-going potential scan and excess lead was then anodically stripped from the nascent nanowire by scanning in the positive direction to produce near stoichiometric PbTe. Repeating this scanning procedure permitted PbTe nanowires 60-400 nm in width to be obtained. The wire height was controlled over the range of 20-100 nm based upon the nickel film thickness. Nanowires with lengths exceeding 1 cm were prepared in this study. We report the characterization of these nanowires using X-ray diffraction, transmission electron microscopy and electron diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy (XPS). The surface chemical composition of PbTe nanowires was monitored by XPS as a function of time during the exposure of these nanowires to laboratory air. One to two monolayers of a mixed Pb and Te oxide are formed during a 24 h exposure. The electrical conductivity of PbTe nanowires was strongly affected by air oxidation, declining from an initial value of 2.0(+/-1.5) x 10 (4) S/m by 61% (for nanowires with a 20 nm thickness), 55% (for 40 nm), and 12% (for 60 nm).

High-throughput fabrication of photoconductors with high detectivity, photosensitivity, and bandwidth.

Nanocrystalline cadmium selenide (nc-CdSe) was electrodeposited within a sub-50 nm gold nanogap, prepared by feedback-controlled electromigration, to form a photoconductive metal-semiconductor-metal nanojunction. Both gap formation and electrodeposition were rapid and automated. The electrodeposited nc-CdSe was stoichiometric, single cubic phase with a mean grain diameter of ∼7 nm. Optical absorption, photoluminescence, and the spectral photoconductivity response of the nc-CdSe were all dominated by band-edge transitions. The photoconductivity of these nc-CdSe-filled gold nanogaps was characterized by a detectivity of 6.9 × 10(10) Jones and a photosensitivity of 500. These devices also demonstrated a maximum photoconductive gain of ∼45 and response and recovery times below 2 μs, corresponding to a 3 dB bandwidth of at least 175 kHz.

A chemically-responsive nanojunction within a silver nanowire.

The formation of a nanometer-scale chemically responsive junction (CRJ) within a silver nanowire is described. A silver nanowire was first prepared on glass using the lithographically patterned nanowire electrodeposition method. A 1-5 nm gap was formed in this wire by electromigration. Finally, this gap was reconnected by applying a voltage ramp to the nanowire resulting in the formation of a resistive, ohmic CRJ. Exposure of this CRJ-containing nanowire to ammonia (NH(3)) induced a rapid (<30 s) and reversible resistance change that was as large as ΔR/R(0) = (+)138% in 7% NH(3) and observable down to 500 ppm NH(3). Exposure to water vapor produced a weaker resistance increase of ΔR/R(0,H(2)O) = (+)10-15% (for 2.3% water) while nitrogen dioxide (NO(2)) exposure induced a stronger concentration-normalized resistance decrease of ΔR/R(0,NO(2)) = (-)10-15% (for 500 ppm NO(2)). The proposed mechanism of the resistance response for a CRJ, supported by temperature-dependent measurements of the conductivity for CRJs and density functional theory calculations, is that semiconducting p-type Ag(x)O is formed within the CRJ and the binding of molecules to this Ag(x)O modulates its electrical resistance.