Eugenio Calandrini

Midinfrared Plasmon-Enhanced Spectroscopy with Germanium Antennas on Silicon Substrates

Midinfrared plasmonic sensing allows the direct targeting of unique vibrational fingerprints of molecules. While gold has been used almost exclusively so far, recent research has focused on semiconductors with the potential to revolutionize plasmonic devices. We fabricate antennas out of heavily doped Ge films epitaxially grown on Si wafers and demonstrate up to 2 orders of magnitude signal enhancement for the molecules located in the antenna hot spots compared to those located on a bare silicon substrate. Our results set a new path toward integration of plasmonic sensors with the ubiquitous CMOS platform.

Group-IV midinfrared plasmonics

Abstract. The use of heavily doped semiconductors to achieve plasma frequencies in the mid-IR has been recently proposed as a promising way to obtain high-quality and tunable plasmonic materials. We introduce a plasmonic platform based on epitaxial n-type Ge grown on standard Si wafers by means of low-energy plasma-enhanced chemical vapor deposition. Due to the large carrier concentration achieved with P dopants and to the compatibility with the existing CMOS technology, SiGe plasmonics hold promises for mid-IR applications in optoelectronics, IR detection, sensing, and light harvesting. As a representative example, we show simulations of mid-IR plasmonic waveguides based on the experimentally retrieved dielectric constants of the grown materials.

Mapping the electromagnetic field confinement in the gap of germanium nanoantennas with plasma wavelength of 4.5 micrometers

We study plasmonic nanoantennas for molecular sensing in the mid-infrared made of heavily doped germanium, epitaxially grown with a bottom-up doping process and featuring free carrier density in excess of 1020 cm−3. The dielectric function of the 250 nm thick germanium film is determined, and bow-tie antennas are designed, fabricated, and embedded in a polymer. By using a near-field photoexpansion mapping technique at λ = 5.8 μm, we demonstrate the existence in the antenna gap of an electromagnetic energy density hotspot of diameter below 100 nm and confinement volume 105 times smaller than λ3.

Determination of the free carrier concentration in atomic-layer doped germanium thin films by infrared spectroscopy

Novel silicon photonics applications requiring heavy n-type doping have recently driven a great deal of interest towards the phosphorous doping of germanium. In this work we report on infrared reflectance spectroscopy measurements of the electron density in heavily n-type doped germanium layers obtained by stacking multiple phosphorous δ-layers. Here, we demonstrate that the conventional Drude model of the electrodynamic response of free carriers in metals can be adapted to describe heavily doped semiconductor thin films. Consequently, the effect of the electron density on the plasma frequency, scattering rate and complex permittivity can be investigated.

Nanoporous gold leaves: preparation, optical characterization and plasmonic behavior in the visible and mid-infrared spectral regions

A robust and reproducible preparation of self-standing nanoporous gold leaves (NPGL) is presented, with optical characterization and plasmonic behaviour analysis. Nanoporous gold (NPG) layers are tipically prepared as thin films on a bulk substrate. Here we present an alternative approach consisting in the preparation of NPGL in the form of a self-standing film. This solution leads to a perfectly symmetric configuration where the metal is immersed in a homogeneous medium and in addition can support the propagation of symmetric and antisymmetric plasmonic modes. With respect to bulk gold, NPG shows metallic behaviour at higher wavelengths, suggesting possible plasmonic applications in the near / medium infrared range. In this work the plasmonic properties in the wide wavelength range from the ultraviolet up to the mid-infrared range have been investigated. References and links 1. R. Zhang and H. 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Balk, “Evolution of structure, composition and stress in nanoporous gold thin films with grainboundary cracks” Metall. Mater. Trans. A 39, 2656-2665 (2008). 36. A. I. Maaroof, A. Gentle, G. B. Smith, and M. B. Cortie, “Bulk and Surface Plasmons in highly nanoporous gold films,” J. Phys. D: Appl. Phys. 40, 5675-5682 (2007). 37. G. B. Smith, and A. A. Earp, “Metal-in-metal localized surface plasmon resonance,” Nanotechnology 21, 015203 (2010). 38. N. W. Ashcroft and N. D. Mermin, “Solid State Physics” (Thomson Brookes – Cole, 1976). 39. D. A. G. Bruggeman, “Berechnung verschiedener physikalischer Konstanten von heterogenen substanzen,” Ann. Phys. 24, 636-679 (1935). 40. J. Homola, “Surface Plasmon Resonance Based Sensors” (Springer, 2006). 41. A. D. Rakić, A. B. Djurišic, J. M. Elazar, and M. L. Majewski, “Optical properties of metallic films for verticalcavity optoelectronic devices,” Appl. Opt. 37, 5271-5283 (1998). 42. P. Berini, “Long-range surface plasmon polaritons,” Adv. Opt. Phot. 1 (3), 484-588 (2009). 43. J. A. Dionne, L. A. Sweatlock, A. Atwater, and A. Polman, “Planar metal plasmon waveguides: frequencydependent dispersion, propagation, localization and loss beyond the free electron model,” Phys. Rev. B 72, 075405-1-10 (2005).A robust and reproducible preparation of self-standing nanoporous gold leaves (NPGL) is presented, with optical characterization and plasmonic behaviour analysis. Nanoporous gold (NPG) layers are tipically prepared as thin films on a bulk substrate. Here we present an alternative approach consisting in the preparation of NPGL in the form of a self-standing film. This solution leads to a perfectly symmetric configuration where the metal is immersed in a homogeneous medium and in addition can support the propagation of symmetric and antisymmetric plasmonic modes. With respect to bulk gold, NPG shows metallic behaviour at higher wavelengths, suggesting possible plasmonic applications in the near / medium infrared range. In this work the plasmonic properties in the wide wavelength range from the ultraviolet up to the mid-infrared range have been investigated.

Mid-infrared plasmonic platform based on heavily doped epitaxial Ge-on-Si: Retrieving the optical constants of thin Ge epilayers

The n-type Ge-on-Si epitaxial material platform enables a novel paradigm for plasmonics in the mid-infrared, prompting the future development of lab-on-a-chip and subwavelength vibrational spectroscopic sensors. In order to exploit this material, through proper electrodynamic design, it is mandatory to retrieve the dielectric constants of the thin Ge epilayers with high precision due to the difference from bulk Ge crystals. Here we discuss the procedure we have employed to extract the real and imaginary part of the dielectric constants from normal incidence reflectance measurements, by combining the standard multilayer fitting procedure based on the Drude model with Kramers-Kronig transformations of absolute reflectance data in the zero-transmission range of the thin film.

n-Ge on Si for mid-infrared plasmonic sensors

The detection and amplification of molecular absorption lines from a mustard gas simulant is demonstrated using plasmonic antennas fabricated from n-Ge epitaxially grown on Si. Approaches to integrated sensors will be presented along with a review of n-Ge compared to other mid-infrared plasmonic materials.

Controlling the Heat Dissipation in Temperature-Matched Plasmonic Nanostructures

Heat dissipation in a plasmonic nanostructure is generally assumed to be ruled only by its own optical response even though also the temperature should be considered for determining the actual energy-to-heat conversion. Indeed, temperature influences the optical response of the nanostructure by affecting its absorption efficiency. Here, we show both theoretically and experimentally how, by properly nanopatterning a metallic surface, it is possible to increase or decrease the light-to-heat conversion rate depending on the temperature of the system. In particular, by borrowing the concept of matching condition from the classical antenna theory, we first analytically demonstrate how the temperature sets a maximum value for the absorption efficiency and how this quantity can be tuned, thus leading to a temperature-controlled optical heat dissipation. In fact, we show how the nonlinear dependence of the absorption on the electron-phonon damping can be maximized at a specific temperature, depending on the system geometry. In this regard, experimental results supported by numerical calculations are presented, showing how geometrically different nanostructures can lead to opposite dependence of the heat dissipation on the temperature, hence suggesting the fascinating possibility of employing plasmonic nanostructures to tailor the light-to-heat conversion rate of the system.

Mid-infrared plasmonic resonances exploiting heavily-doped Ge on Si

We address the behavior of mid-infrared localized plasmon resonances in elongated germanium antennas integrated on silicon substrates. Calculations based on Mie theory and on the experimentally retrieved dielectric constant allow us to study the tunability and the figures of merit of plasmon resonances in heavily-doped germanium and to preliminarily compare them with those of the most established plasmonic material, gold.

Engineered/tailored nanoporous gold structures for infrared plasmonics

Nanoporous gold is a very promising and novel material platform for mid-infrared and THz plasmonics. Nanoporous gold can be formed by dealloying of Au–Ag alloys, previously grown by means of Ag-Au co-sputtering. The optical response is completely determined by the nanostructural film features, that depends on the initial alloy composition and on the preparation procedure. The behavior of the material in mid-infrared and its peculiar morphology with a very high surface/volume ratio can be applied for nanostructure fabrication, such for example nanoantennas. Here we report the design and fabrication of nanoporous antennas engineered to support resonances in the 1500-1700 cm-1 range where them can be exploited, for example, in the detection of protein conformational states. This novel paradigm points toward the development of a new class of efficient and high-selective biosensors.