Room-temperature nine-µm-wavelength photodetectors and GHz-frequency heterodyne receivers.

Room-temperature operation is essential for any optoelectronics technology that aims to provide low-cost, compact systems for widespread applications. A recent technological advance in this direction is bolometric detection for thermal imaging, which has achieved relatively high sensitivity and video rates (about 60 hertz) at room temperature. However, owing to thermally induced dark current, room-temperature operation is still a great challenge for semiconductor photodetectors targeting the wavelength band between 8 and 12 micrometres, and all relevant applications, such as imaging, environmental remote sensing and laser-based free-space communication, have been realized at low temperatures. For these devices, high sensitivity and high speed have never been compatible with high-temperature operation. Here we show that a long-wavelength (nine micrometres) infrared quantum-well photodetector fabricated from a metamaterial made of sub-wavelength metallic resonators exhibits strongly enhanced performance with respect to the state of the art up to room temperature. This occurs because the photonic collection area of each resonator is much larger than its electrical area, thus substantially reducing the dark current of the device. Furthermore, we show that our photonic architecture overcomes intrinsic limitations of the material, such as the drop of the electronic drift velocity with temperature, which constrains conventional geometries at cryogenic operation. Finally, the reduced physical area of the device and its increased responsivity allow us to take advantage of the intrinsic high-frequency response of the quantum detector at room temperature. By mixing the frequencies of two quantum-cascade lasers on the detector, which acts as a heterodyne receiver, we have measured a high-frequency signal, above four gigahertz (GHz). Therefore, these wide-band uncooled detectors could benefit technologies such as high-speed (gigabits per second) multichannel coherent data transfer and high-precision molecular spectroscopy.

Multiresonant Grating to Replace Transparent Conductive Oxide Electrode for Bias Selected Filtering of Infrared Photoresponse.

Optoelectronic devices rely on conductive layers as electrodes, but they usually introduce optical losses that are detrimental to the device performances. While the use of transparent conductive oxides is established in the visible region, these materials show high losses at longer wavelengths. Here, we demonstrate a photodiode based on a metallic grating acting as an electrode. The grating generates a multiresonant photonic structure over the diode stack and allows strong broadband absorption. The obtained device achieves the highest performances reported so far for a midwave infrared nanocrystal-based detector, with external quantum efficiency above 90%, detectivity of 7 × 1011 Jones at 80 K at 5 µm, and a sub-100 ns time response. Furthermore, we demonstrate that combining different gratings with a single diode stack can generate a bias reconfigurable response and develop new functionalities such as band rejection.

High bitrate data transmission in the 8-14 µm atmospheric window using an external Stark-effect modulator with digital equalization.

High bitrate mid-infrared links using simple (NRZ) and multi-level (PAM-4) data coding schemes have been realized in the 8 µm to 14 µm atmospheric transparency window. The free space optics system is composed of unipolar quantum optoelectronic devices, namely a continuous wave quantum cascade laser, an external Stark-effect modulator and a quantum cascade detector, all operating at room-temperature. Pre- and post-processing are implemented to get enhanced bitrates, especially for PAM-4 where inter-symbol interference and noise are particularly detrimental to symbol demodulation. By exploiting these equalization procedures, our system, with a full frequency cutoff of 2 GHz, has reached transmission bitrates of 12 Gbit/s NRZ and 11 Gbit/s PAM-4 fulfilling the 6.25 % overhead hard-decision forward error correction threshold, limited only by the low signal-to-noise ratio of our detector.

Auto-Calibrated Charge-Sensitive Infrared Phototransistor at 9.3 µm.

Charge-sensitive infrared photo-transistors (CSIP) are quantum detectors of mid-infrared radiation (λ=4 µm-14 µm) which have been reported to have outstanding figures of merit and sensitivities that allow single photon detection. The typical absorbing region of a CSIP consists of an AlxGa1-xAs quantum heterostructure, where a GaAs quantum well, where the absorption takes place, is followed by a triangular barrier with a graded x(Al) composition that connects the quantum well to a source-drain channel. Here, we report a CSIP designed to work for a 9.3 µm wavelength where the Al composition is kept constant and the triangular barrier is replaced by tunnel-coupled quantum wells. This design is thus conceptually closer to quantum cascade detectors (QCDs) which are an established technology for detection in the mid-infrared range. While previously reported structures use metal gratings in order to couple infrared radiation in the absorbing quantum well, here, we employ a 45° wedge facet coupling geometry that allows a simplified and reliable estimation of the incident photon flux Φ in the device. Remarkably, these detectors have an "auto-calibrated" nature, which enables the precise assessment of the photon flux Φ solely by measuring the electrical characteristics and from knowledge of the device geometry. We identify an operation regime where CSIP detectors can be directly compared to other unipolar quantum detectors such as quantum well infrared photodetectors (QWIPs) and QCDs and we estimate the corresponding detector figure of merit under cryogenic conditions. The maximum responsivity R = 720 A/W and a photoconductive gain G~2.7 × 104 were measured, and were an order of magnitude larger than those for QCDs and quantum well infrared photodetectors (QWIPs). We also comment on the benefit of nano-antenna concepts to increase the efficiency of CSIP in the photon-counting regime.

Metamaterial engineering for optimized photon absorption in unipolar quantum devices.

Metamaterials have played a major role in the development of optoelectronic devices due to their capability of coupling free-space radiation with active materials at the nanometer scale. In particular, unipolar photodetectors display highly improved performances when implemented into patch-antenna arrays. We study light-coupling and absorption in patch-antenna metamaterials by combining an experimental investigation, an analytical approach based on coupled mode theory and numerical simulations in order to understand how the geometrical parameters influence the electromagnetic energy transfer from the free-space to the active material. Our findings are applied to the design of optimized unipolar photodetectors with improved quantum efficiency.

Bias Tunable Spectral Response of Nanocrystal Array in a Plasmonic Cavity.

Nanocrystals (NCs) have gained considerable attention for their broadly tunable absorption from the UV to the THz range. Nevertheless, their optical features suffer from a lack of tunability once integrated into optoelectronic devices. Here, we show that bias tunable aspectral response is obtained by coupling a HgTe NC array with a plasmonic resonator. Up to 15 meV blueshift can be achieved from a 3 µm absorbing wavelength structure under a 3 V bias voltage when the NC exciton is coupled with a mode of the resonator. We demonstrate that the blueshift arises from the interplay between hopping transport and inhomogeneous absorption due to the presence of the photonic structure. The observed tunable spectral response is qualitatively reproduced in simulation by introducing a bias-dependent diffusion length in the charge transport. This work expands the realm of existing NC-based devices and paves the way toward light modulators.

Absorption Engineering in an Ultrasubwavelength Quantum System.

Many photonic and plasmonic structures have been proposed to achieve ultrasubwavelength light confinement across the electromagnetic spectrum. Notwithstanding this effort, however, the efficient funneling of external radiation into nanoscale volumes remains problematic. Here, we demonstrate a photonic concept that fulfills the seemingly incompatible requirements for both strong electromagnetic confinement and impedance matching to free space. Our architecture consists of antenna-coupled meta-atom resonators that funnel up to 90% of the incident radiation into an ultrasubwavelength semiconductor quantum well absorber of volume V = λ310-6. A significant fraction of the coupled electromagnetic energy is used to excite the electronic transitions in the quantum well, with a photon absorption efficiency 550 times larger than the intrinsic value of the electronic dipole. This system opens important perspectives for ultralow dark current quantum detectors and for the study of light-matter interaction in the extreme regimes of electronic and photonic confinement.

Quasi-static and propagating modes in three-dimensional THz circuits.

We provide an analysis of the electromagnetic modes of three-dimensional metamaterial resonators in the THz frequency range. The fundamental resonance of the structures is fully described by an analytical circuit model, which not only reproduces the resonant frequencies but also the coupling of the metamaterial with an incident THz radiation. We also demonstrate the contribution of the propagation effects, and show how they can be reduced by design. In the optimized design, the electric field energy is lumped into ultra-subwavelength (λ/100) capacitors, where we insert a semiconductor absorber based on the collective electronic excitation in a two dimensional electron gas. The optimized electric field confinement is exhibited by the observation of the ultra-strong light-matter coupling regime, and opens many possible applications for these structures in detectors, modulators and sources of THz radiation.

Semiconductor Quantum Plasmonics.

We investigate the frontier between classical and quantum plasmonics in highly doped semiconductor layers. The choice of a semiconductor platform instead of metals for our study permits an accurate description of the quantum nature of the electrons constituting the plasmonic response, which is a crucial requirement for quantum plasmonics. Our quantum model allows us to calculate the collective plasmonic resonances from the electronic states determined by an arbitrary one-dimensional potential. Our approach is corroborated with experimental spectra, realized on a single quantum well, in which higher order longitudinal plasmonic modes are present. We demonstrate that their energy depends on the plasma energy, as is also the case for metals, but also on the size confinement of the constituent electrons. This work opens the way toward the applicability of quantum engineering techniques for semiconductor plasmonics.

Fluorinated alkyl-phosphate-based electrolytes with controlled lithium-ion coordination structure.

Herein, we propose Li-ion solvation-controlled electrolytes based on non-flammable organic solvent TFEP and an LiFSA salt [TFEP: tris(2,2,2-trifluoroethyl)phosphate, LiFSA: lithium bis(fluorosulfonyl)amide] to allow Li-ion insertion into a graphite electrode for Li-ion batteries. Comprehensive structural study based on (1) infrared (IR)/Raman spectroscopy, (2) high-energy X-ray total scattering (HEXTS), and (3) molecular dynamics (MD) simulation revealed the solvation (or coordination) structures of Li ions in TFEP-based electrolytes at the molecular level. In binary LiFSA/TFEP with a Li salt concentration (cLi) < 1.0 mol dm-3, Li ions are coordinated with both TFEP and FSA components; in detail, two TFEP molecules coordinate in an O-donating monodentate manner and one FSA in an O-donating bidentate manner to form [Li(TFEP)2(bi-FSA)] as the major species. We demonstrated that adding acetonitrile (AN) to the LiFSA/TFEP electrolytes caused structural changes in the Li-ion complexes. The bi-FSA bound to the Li ion changed its coordination mode to mono-FSA, which was induced by solvating AN molecules to Li ions. The redox reaction corresponding to insertion/deinsertion of Li ions into/from the graphite electrode successfully occurred in 1.0 mol dm-3 LiFSA/TFEP with an AN electrolyte system, while there was no or reduced Li-ion insertion in the electrolyte without AN. We discussed the relationship between the structure and electrode reaction of the Li-ion complexes based on the FSA-coordination characteristics; i.e., in LiFSA/TFEP with the AN system, the mono-FSA bound to the Li ion is easier to decoordinate due to weaker Li+mono-FSA- interactions rather than the Li+bi-FSA- interactions, which mainly contribute to charge-transfer at the electrode/electrolyte interface to allow Li-ion insertion/deinsertion in the graphite anode.

Solvation-controlled lithium-ion complexes in a nonflammable solvent containing ethylene carbonate: structural and electrochemical aspects.

The structural and electrochemical properties of lithium-ion solvation complexes in a nonflammable organic solvent, tris(2,2,2-trifluoroethyl)phosphate (TFEP) containing ethylene carbonate (EC), were investigated using vibrational spectroscopic and electrochemical measurements. Based on quantitative Raman and infrared (IR) spectral analysis of the Li bis(trifluoromethanesulfonyl)amide (TFSA) salt in TFEP + EC electrolytes, we successfully evaluated the individual solvation numbers of EC (nEC), TFEP (nTFEP), and TFSA- (nTFSA) in the first solvation sphere of the Li-ion. We found that the nEC value linearly increased with increasing EC mole fraction (xEC), whereas the nTFEP and nTFSA values gradually decreased with increasing nEC. The ionic conductivity and viscosity (Walden plots) indicated that mainly Li+TFSA- ion pairs formed in neat TFEP (xEC = 0). This ion pair gradually dissociated into positively charged Li-ion complexes as xEC increased, which was consistent with the Raman/IR spectroscopy results. The redox reaction corresponding to an insertion/desertion of Li-ion into/from the graphite electrode occurred in the LiTFSA/TFEP + EC system at xEC ≥ 0.25. The same was not observed in the lower xEC cases. We discussed the relation between Li-ion solvation and electrode reaction behaviors at the molecular level and proposed that nEC plays a crucial role in the electrode reaction, particularly in terms of solid electrolyte interphase formation on the graphite electrode.

Ion-solvation structure and battery electrode characteristics of nonflammable organic electrolytes based on tris(trifluoroethyl)phosphate dissolving lithium salts.

The structure and properties of lithium salt solutions based on tris(2,2,2-trifluoroethyl)phosphate (TFEP) solvent have been studied to design a safer electrolyte system for large-sized lithium-ion battery applications. Influences of the ionic structure on the polarization behavior of the LiCoO2 (LCO) positive electrode were investigated. The ionic conductivity and viscosity of the solution consisting of lithium salts dissolved in TFEP, LiX/TFEP (X = PF6, BF4 and TFSA) (TFSA = (CF3SO2)2N), were measured. The results suggest that the ion-solvation structure greatly depends on the anionic species in the salt. Spectroscopic measurements also support the conclusion that the Li+-solvation structure varies with the lithium salts. The differences in the ionic structure of LiX/TFEP influence the electrochemical oxidation potential of the solution and the polarization behavior of the LCO electrode. The overvoltage for Li-desertion/insertion from/into LCO in LiX/TFEP, being much higher than that observed in conventional LIB electrolyte solutions, shows the order of BF4 < PF6 < TFSA. The addition of ethylene carbonate (EC) to LiX/TFEP increases the ionic conductivity, which is probably caused by changes in the Li+-solvation structure in TFEP. The overvoltage for the Li-desertion/insertion of LCO is much lowered by the addition of EC to LiX/TFEP.

Three-dimensional THz lumped-circuit resonators.

Our work describes a novel three dimensional meta-material resonator design for optoelectronic applications in the THz spectral range. In our resonant circuits, the capacitors are formed by double-metal regions cladding a dielectric core. Unlike conventional planar metamaterials, the electric field is perpendicular to the surface and totally confined in the dielectric core. Furthermore, the magnetic field, confined in the inductive part, is parallel to the electric field, ruling out coupling through propagation effects. Our geometry thus combines the benefit of double-metal structures that provide parallel plate capacitors, while maintaining the ability of meta-material resonators to adjust independently the capacitive and inductive parts. Furthermore, in our geometry, a constant bias can be applied across the dielectric, making these resonators very suitable for applications such as ultra-low dark current THz quantum detectors and amplifiers based on quantum cascade gain medium.

THz quantum gap: exploring potential approaches for generating and detecting non-classical states of THz light.

Over the past few decades, THz technology has made considerable progress, evidenced by the performance of current THz sources and detectors, as well as the emergence of several THz applications. However, in the realm of quantum technologies, the THz spectral domain is still in its infancy, unlike neighboring spectral domains that have flourished in recent years. Notably, in the microwave domain, superconducting qubits currently serve as the core of quantum computers, while quantum cryptography protocols have been successfully demonstrated in the visible and telecommunications domains through satellite links. The THz domain has lagged behind in these impressive advancements. Today, the current gap in the THz domain clearly concerns quantum technologies. Nonetheless, the emergence of quantum technologies operating at THz frequencies will potentially have a significant impact. Indeed, THz radiation holds significant promise for wireless communications with ultimate security owing to its low sensitivity to atmospheric disturbances. Moreover, it has the potential to raise the operating temperature of solid-state qubits, effectively addressing existing scalability issues. In addition, THz radiation can manipulate the quantum states of molecules, which are recognized as new platforms for quantum computation and simulation with long range interactions. Finally, its ability to penetrate generally opaque materials or its resistance to Rayleigh scattering are very appealing features for quantum sensing. In this perspective, we will discuss potential approaches that offer exciting prospects for generating and detecting non-classical states of THz light, thereby opening doors to significant breakthroughs in THz quantum technologies.

Actively tunable laser action in GeSn nanomechanical oscillators.

Mechanical forces induced by high-speed oscillations provide an elegant way to dynamically alter the fundamental properties of materials such as refractive index, absorption coefficient and gain dynamics. Although the precise control of mechanical oscillation has been well developed in the past decades, the notion of dynamic mechanical forces has not been harnessed for developing tunable lasers. Here we demonstrate actively tunable mid-infrared laser action in group-IV nanomechanical oscillators with a compact form factor. A suspended GeSn cantilever nanobeam on a Si substrate is resonantly driven by radio-frequency waves. Electrically controlled mechanical oscillation induces elastic strain that periodically varies with time in the GeSn nanobeam, enabling actively tunable lasing emission at >2 µm wavelengths. By utilizing mechanical resonances in the radio frequency as a driving mechanism, this work presents wide-range mid-infrared tunable lasers with ultralow tuning power consumption.

Electronic transport driven by collective light-matter coupled states in a quantum device.

In the majority of optoelectronic devices, emission and absorption of light are considered as perturbative phenomena. Recently, a regime of highly non-perturbative interaction, ultra-strong light-matter coupling, has attracted considerable attention, as it has led to changes in the fundamental properties of materials such as electrical conductivity, rate of chemical reactions, topological order, and non-linear susceptibility. Here, we explore a quantum infrared detector operating in the ultra-strong light-matter coupling regime driven by collective electronic excitations, where the renormalized polariton states are strongly detuned from the bare electronic transitions. Our experiments are corroborated by microscopic quantum theory that solves the problem of calculating the fermionic transport in the presence of strong collective electronic effects. These findings open a new way of conceiving optoelectronic devices based on the coherent interaction between electrons and photons allowing, for example, the optimization of quantum cascade detectors operating in the regime of strongly non-perturbative coupling with light.

Extremely sub-wavelength THz metal-dielectric wire microcavities.

We demonstrate minimal volume wire THz metal-dielectric micro-cavities, in which all but one dimension have been reduced to highly sub-wavelength values. The smallest cavity features an effective volume of 0.4 µm(3), which is ~5.10(-7) times the volume defined by the resonant vacuum wavelength (λ = 94 µm) to the cube. When combined with a doped multi-quantum well structure, such micro-cavities enter the ultra-strong light matter coupling regime, even if the total number of electrons participating to the coupling is only in the order of 10(4), thus much less than in previous studies.

Optomechanical terahertz detection with single meta-atom resonator.

Most of the common technologies for detecting terahertz photons (>1 THz) at room temperature rely on slow thermal devices. The realization of fast and sensitive detectors in this frequency range is indeed a notoriously difficult task. Here we propose a novel device consisting of a subwavelength terahertz meta-atom resonator, which integrates a nanomechanical element and allows energy exchange between the mechanical motion and the electromagnetic degrees of freedom. An incident terahertz wave thus produces a nanomechanical signal that can be read out optically with high precision. We exploit this concept to demonstrate a terahertz detector that operates at room temperature with high sensitivity and a much higher frequency response compared to standard detectors. Beyond the technological issue of terahertz detection, our architecture opens up new perspectives for fundamental science of light-matter interaction at terahertz frequencies, combining optomechanical approaches with semiconductor quantum heterostructures.

Valence determination of manganese in battery cathode materials by high-resolution Mn Kalpha1 spectra.

High-resolution the Mn Kalpha1 X-ray fluorescence spectra (HRXRF) were measured for a variety of manganese compounds, the oxidation number (valence) of which was from II to VII. Plots of the valence against the full width at half maximum (FWHM) and the chemical shift of the Kalpha1 X-ray fluorescence spectra give a curve and a liniar relation, respectively. The coefficient of correlation (R2) for the latter plot was 0.989 between valency II and VII. More excellent linearlity from III to IV was obtained with R2 = 0.995, which enabled us to determine the oxidation number of manganese atom in a nickel ion doped spinel structure, LiMn2O4 (LiNixMn(2-x)O4, with 0.2 < x < 0.42). From the valence of manganese ion obtained from HRXRF, the oxidation number of nickel ion is concluded to be divalent.

Strong near field enhancement in THz nano-antenna arrays.

A key issue in modern photonics is the ability to concentrate light into very small volumes, thus enhancing its interaction with quantum objects of sizes much smaller than the wavelength. In the microwave domain, for many years this task has been successfully performed by antennas, built from metals that can be considered almost perfect at these frequencies. Antenna-like concepts have been recently extended into the THz and up to the visible, however metal losses increase and limit their performances. In this work we experimentally study the light coupling properties of dense arrays of subwavelength THz antenna microcavities. We demonstrate that the combination of array layout with subwavelength electromagnetic confinement allows for 10(4)-fold enhancement of the electromagnetic energy density inside the cavities, despite the low quality factor of a single element. This effect is quantitatively described by an analytical model that can be applied for the optimization of any nanoantenna array.