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A unique hydrogen sensor structure based on Pt-decorated porous gallium nitride (PGaN) was fabricated by a two-step process consisting of metal-assisted electroless etching to produce PGaN with highly anisotropic pores followed by electroless deposition of Pt in the pores from an ammoniacal PtCl(6)(2-) solution. The Pt-decorated PGaN structure contains 50-100 nm diameter nanopores which are 400 nm to 1 microm deep and filled with Pt islands. Both electroless etching and deposition steps are done in solution and allow for large-scale production. An AC four-point probe conductivity measurement was implemented at f = 1 kHz, a frequency where the impedance of Pt-PGaN is nearly entirely resistive, and the change in conductance upon H(2) exposure was measured for three sample types: PGaN with a surface sputtered layer of Pt only; unetched GaN (CGaN) with both sputtered and electrolessly deposited Pt; and PGaN with both sputtered and electrolessly deposited Pt. The hydrogen sensing performance of the Pt-filled PGaN sensor was more than an order of magnitude better than either of the other two sample types under all experimental conditions, an observation attributed to the significant increase in Pt-GaN interfacial area in the electrolessly decorated PGaN samples, exhibiting a response to H2 concentrations as low as 1 ppm. The conductance changes are ascribed to adsorption-induced changes in interfacial polarization that produce changes in band bending and thus to the width of the space charge region near the Pt-GaN interface.

Metal-assisted chemical etching is a facile method to produce micro-/nanostructures in the near-surface region of gallium nitride (GaN) and other semiconductors. Detailed studies of the production of porous GaN (PGaN) using different metal catalysts and GaN doping conditions have been performed in order to understand the mechanism by which metal-assisted chemical etching is accomplished in GaN. Patterned catalysts show increasing metal-assisted chemical etching activity to n-GaN in the order Ag < Au < Ir < Pt. In addition, the catalytic behavior of continuous films is compared to discontinuous island films. Continuous metal films strongly shield the surface, hindering metal-assisted chemical etching, an effect which can be overcome by using discontinuous films or increasing the irradiance of the light source. With increasing etch time or irradiance, PGaN morphologies change from uniform porous structures to ridge and valley structures. The doping type plays an important role, with metal-assisted chemical etching activity increasing in the order p-GaN < intrinsic GaN < n-GaN. Both the catalyst identity and the doping type effects are explained by the work functions and the related band offsets that affect the metal-assisted chemical etching process through a combination of different barriers to hole injection and the formation of hole accumulation/depletion layers at the metal-semiconductor interface.

Conductance-based chemical sensing in metal-semiconductor nanostructures and all-metal nanowires of atomic dimensions is garnering increased interest. Adsorbed gas molecules can migrate to a metal-semiconductor junction, thereby shifting the magnitude of the Schottky barrier and altering electrical impedance, whereas atomic scale metal junctions can sensitively report the presence of adsorbates through their impact on ballistic electron transport.

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