Surface Plasmon Hosts For Infrared Waveguides And Biosensors, And Plasmons In Gold-black Nano-structured Films

Applications of surface plasmon polaritons (SPPs) have thus far emphasized visible and near-infrared wavelengths. Extension into the long-wave infrared (LWIR) has numerous potential advantages for biosensors and waveguides, which are explored in this work. A surface plasmon resonance (SPR) biosensor that operates deep into the infrared (3-11 µm wavelengths) is potentially capable of biomolecule recognition based on both selective binding and characteristic vibrational modes. The goal is to operate such sensors at wavelengths where biological analytes are strongly differentiated by their IR absorption spectra and where the refractive index is increased by dispersion, which will provide enhanced selectivity and sensitivity. Potentially useful IR surface plasmon resonances are investigated on lamellar gratings formed from various materials with plasma frequencies in the IR wavelength range including doped semiconductors, semimetals, and conducting polymers. One outcome of this work has been the demonstration of a simple analytic formula for calculating the SPP absorption resonances in the angular reflectance spectra of gratings. It is demonstrated for Ag lamellar gratings in the 6-11 µm wavelength range. The recipe is semi-empirical, requiring knowledge of a surface-impedance modulation amplitude, which is found here by comparison to experiment as a function of the grating groove depth and the wavelength. The optimum groove depth for photon-to-SPP energy conversion was found by experiment and calculation to be ~10-15% of the wavelength. Hemicylindrical prism couplers formed from Si or Ge were investigated as IR surface plasmon couplers for the biosensor application. Strong Fabry-Perot oscillations in the angular reflectance spectra for these high index materials suggest that grating couplers will be more effective for this application in the LWIR. A variety of materials having IR plasma frequencies were investigated due to the tighter SPP mode confinement anticipated in the IR than for traditional noble metals. First doped-Si and metal silicides (Ni, Pd, Pt and Ti) were investigated due to their inherent CMOS compatibility. Rutherford backscattering spectroscopy, x-ray diffraction, scanning electron microscopy, secondary ion mass spectrometry and four point probe measurements complemented the optical characterization by ellipsometry. Calculation of propagation length and mode confinement from measured permittivities demonstrated the suitability for these materials for LWIR SPP applications. Semimetals were also investigated since their plasma frequencies are intermediate between those of doped silicon and metal silicides. The semimetal antimony, with a plasma frequency ~80 times less than that of gold was characterized. Relevant IR surface plasmon properties, including the propagation length and penetration depths for SPP fields, were determined from optical constants measured in the LWIR. Distinct resonances due to SPP generation were observed in angular reflection spectra of Sb lamellar gratings in the wavelength range of 6 to 11 µm. Though the real part of the permittivity is positive in this range, which violates the usual condition for the existence of bound SPP modes, calculations based on experimental permittivity showed that there is little to distinguish bound from unbound SPP modes for this material. The SPP mode decays exponentially away from the surface on both sides of the permittivity sign change. Water is found to broaden the IR plasmon resonances significantly at 9.25 micron wavelength where aqueous extinction is large. Much sharper resonances for water based IR SPR biosensor can be achieved in the 3.5 to 5.5 µm range. Nano-structured Au films (Au-black) were investigated as IR absorbers and possible solar cell enhancers based on surface plasmon resonance. The characteristic length scales of the structured films vary considerably as a function of deposition parameters, but the absorbance is found to be only weakly correlated with these distributions. Structured Au-black with a broad range of cluster length scales appear to be able to support multiple SPP modes with incident light coupling to the corrugated surface as seen by photoelectron emission microscopy (PEEM) and SPR experiments, supporting the hypothesis that Au-black may be a suitable material for plasmon-resonance enhancement solar-cell efficiency over the broad solar spectrum