Integration of an opto-chemical detector based on group III-nitride nanowire heterostructures.

The photoluminescence intensity of group III nitrides, nanowires, and heterostructures (NWHs) strongly depends on the environmental H(2) and O(2) concentration. We used this opto-chemical transducer principle for the realization of a gas detector. To make this technology prospectively available to commercial gas-monitoring applications, a large-scale laboratory setup was miniaturized. To this end the gas-sensitive NWHs were integrated with electro-optical components for optical addressing and read out within a compact and robust sensor system. This paper covers the entire realization process of the device from its conceptual draft and optical design to its fabrication and assembly. The applied approaches are verified with intermediate results of profilometric characterizations and optical performance measurements of subsystems. Finally the gas-sensing capabilities of the integrated detector are experimentally proven and optimized.

Electrical transport properties of Ge-doped GaN nanowires.

The conductivity and charge carrier concentration of single GaN nanowires (NWs) doped with different concentrations of Ge were determined by four-point resistivity and temperature-dependent Seebeck coefficient measurements. We observed high carrier concentrations ranging from 9.1 × 10(18) to 5.5 × 10(19) cm(-3), well above the Mott density of 1.6 × 10(18) cm(-3), and conductivities up to 625 S cm(-1) almost independent of the NW diameter. The weak temperature dependence of the conductivity between 2 and 10 K could be assigned to the formation of an impurity band. For the sample with the highest conductivity metallic behaviour was found, indicated by a positive temperature coefficient of the resistivity. The near band edge emission analyzed by micro-photoluminescence spectroscopy showed only a small increase of the peak width up to 70 meV and no spectral shift for carrier concentrations up to 5.5 × 10(19) cm(-3). The latter was attributed to the simultaneous influence of band filling, band gap renormalization, and strain.

Intraband absorption in self-assembled Ge-doped GaN/AlN nanowire heterostructures.

We report the observation of transverse-magnetic-polarized infrared absorption assigned to the s-p(z) intraband transition in Ge-doped GaN/AlN nanodisks (NDs) in self-assembled GaN nanowires (NWs). The s-p(z) absorption line experiences a blue shift with increasing ND Ge concentration and a red shift with increasing ND thickness. The experimental results in terms of interband and intraband spectroscopy are compared to theoretical calculations of the band diagram and electronic structure of GaN/AlN heterostructured NWs, accounting for their three-dimensional strain distribution and the presence of surface states. From the theoretical analysis, we conclude that the formation of an AlN shell during the heterostructure growth applies a uniaxial compressive strain which blue shifts the interband optical transitions but has little influence on the intraband transitions. The presence of surface states with density levels expected for m-GaN plane charge-deplete the base of the NWs but is insufficient to screen the polarization-induced internal electric field in the heterostructures. Simulations show that the free-carrier screening of the polarization-induced internal electric field in the NDs is critical to predicting the photoluminescence behavior. The intraband transitions, on the other hand, are blue-shifted due to many-body effects, namely, the exchange interaction and depolarization shift, which exceed the red shift induced by carrier screening.

Radical formation at the gallium nitride nanowire-electrolyte interface by photoactivated charge transfer.

We investigated the transfer of photogenerated charge carriers from GaN nanowires into a surrounding electrolyte by electron paramagnetic resonance (EPR) and fluorescence spectroscopy. Using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a spin trap we find that the formation of hydroxyl radicals dominates in acidic, neutral and moderately basic environments, while in an electrolyte with a pH of 13.5 the superoxide formation becomes detectable. We explain the two processes considering the redox potentials for radical formation in the electrolyte as well as the positions of the conduction and valence bands. The role of surface band bending and surface states in the semiconductor is discussed.

Optical properties of GaN-based nanowires containing a single Al(0.14)Ga(0.86)N/GaN quantum disc.

The optical properties of wurtzite GaN nanowires containing single Al0.14Ga0.86N/GaN quantum discs of different thickness have been investigated. The dependence of the photoluminescence (PL) transition energy on the quantum disc thickness and the thickness of a lateral AlGaN shell has been simulated in the framework of a three-dimensional effective mass model, accounting for the presence of a lateral AlGaN shell, strain state and the piezoelectric and spontaneous polarization. The predicted transition energies are in good agreement with the statistics realized on more than 40 single nanowire emission spectra and PL spectra of ensembles of nanowires. The emission spectra of the single quantum discs exhibit a Lorentzian shape with a homogeneous line width as low as 3 meV. Finally, we discuss the dependence of the interband transition energy on diameter.

Electrochemical properties of GaN nanowire electrodes--influence of doping and control by external bias.

We report on the electrochemical characteristics of GaN nanowire (NW) ensembles grown by plasma-assisted molecular beam epitaxy on Si111 substrates and on the influence of Si and Mg doping. The NW electrochemical properties in terms of surface capacitance (C(S)), surface resistance (R(S)) are extracted from electrochemical impedance spectra. While Mg doping of GaN NWs does not cause a significant variation of these quantities, an increase of the Si concentration leads to an increase of C(S) and a simultaneous decrease of R(S), indicating the presence of charge carriers in the NWs. According to the extracted values for R(S) and C(S) the NWs are classified into resistive and conductive. For conductive NWs charge transfer to a ferricyanide redox couple in the electrolyte is demonstrated and the ensemble average of the flatband voltage was determined. Variation of the lateral surface potential due to application of an external bias via the electrolyte is demonstrated.

GaN nanodiscs embedded in nanowires as optochemical transducers.

The photoluminescence (PL) response of GaN/AlGaN nanowire heterostructures (NWHs) to hydrogen and oxygen between room temperature and 300 °C is reported. Exposure of Pt-coated NWHs to H2 leads to an increase of the PL intensity attributed to the suppression of surface recombination by local dipole fields of adsorbed atomic hydrogen. When exposed to O2, uncoated NWHs show a decrease in PL intensity that is assigned to enhanced non-radiative recombination. The detection limits are below 5 ppm at 150 °C.

Influence of magnetic dopants on the metal-insulator transition in semiconductors.

InSb:Mn and InSb:Ge reveal differences in their resistivity near the metal-insulator transition although both are acceptors of comparable depth. InSb:Ge shows the commonly observed behavior whereas InSb:Mn exhibits a strong enhancement of the resistivity below 10 K and pronounced negative magnetoresistance effects at 1.6 K. Both effects increase by applying hydrostatic pressure. The different behavior arises from the differences in the filling of the 3d shell, half filled 3d;{5} for Mn with a total spin of S=5/2 and entirely filled 3d;{10} for Ge with total angular momentum of J=0. The exchange interaction between the hole spin of the Mn acceptor and the S=5/2 spin of its 3d;{5} shell is the dominant correlation effect leading to the formation of an antiferromagnetic alignment of the Mn 3d;{5} spins along the percolation path which inhibits hopping of holes between neighboring Mn sites.