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Electricity from thermal sources It is desirable to harvest as much energy as possible from processes that produce useful amounts of heat and convert it from waste into electrical power. Thermoelectrics and thermophotovoltaics can harness and convert heat waste but tend to operate at high temperatures. Davids et al. designed and fabricated a complementary metal-oxide semiconductor infrared photonic device that can harvest and recover energy from low-temperature thermal sources (see the Perspective by Raman). Using a new conversion mechanism, they experimentally demonstrate large thermal-to-electrical power generation in a bipolar grating-coupled tunneling device, rivaling the best thermoelectric devices. The device design could be used for energy harvesting of waste heat and the development of compact thermal batteries. Science , this issue p. 1341 ; see also p. 1301

The deeply depleted graphene-oxide-semiconductor (D2GOS) junction detector provides an effective architecture for photodetection, enabling direct readout of photogenerated charge. Because of an inh...

Controlling the permittivity of materials enables control over the amplitude, phase and polarization of light interacting with them. Tailorable and tunable transparent conducting oxides have applications in optical switching, beam steering, imaging, sensing, and spectroscopy. In this work, we experimentally demonstrate wide tailoring and tuning of the optical properties of oxides to achieve fast switching with large modulation depths. In cadmium oxide, the permittivity and the epsilon-near-zero points can be tailored via yttrium doping to achieve large, ENZ-enhanced mid-IR reflectance modulation. In zinc oxide, the permittivity is tuned by interband pumping, achieving large reflectance modulation in the telecom regime. With aluminum-doped zinc oxide, we demonstrate tailorable Berreman-type absorbers that can achieve ultrafast switching in the telecom frequencies. Our work will pave the way to practical optical switching spanning the telecom to the mid-infrared wavelength regimes.

We demonstrate significant epsilon-near-zero point shifts (11.3 pm to 5.3 pm), extraordinarily large (135%) optically-induced reflection modulation with picosecond response times, and carrier relaxation time-engineering in cadmium oxide via Yttrium doping.

Metal-Nb2O5−x-metal memdiodes exhibiting rectification, hysteresis, and capacitance are demonstrated for applications in neuromorphic circuitry. These devices do not require any post-fabrication treatments such as filament creation by electroforming that would impede circuit scalability. Instead these devices operate due to Poole-Frenkel defect controlled transport where the high defect density is inherent to the Nb2O5−x deposition rather than post-fabrication treatments. Temperature dependent measurements reveal that the dominant trap energy is 0.22 eV suggesting it results from the oxygen deficiencies in the amorphous Nb2O5−x. Rectification occurs due to a transition from thermionic emission to tunneling current and is present even in thick devices (>100 nm) due to charge trapping which controls the tunneling distance. The turn-on voltage is linearly proportional to the Schottky barrier height and, in contrast to traditional metal-insulator-metal diodes, is logarithmically proportional to the device thickness. Hysteresis in the I–V curve occurs due to the current limited filling of traps.

Nb2O5-based metal–insulator–metal (MIM) diodes are ideal for neuromorphic computing applications because they exhibit desirable rectification, hysteresis, and capacitance characteristics without electroforming. We employ capacitance-frequency measurements to evaluate the total-ionizing-dose res- ponse of these devices to avoid measurement-induced disturbance of trap distributions caused by typical gate-voltage sweeping methods. Power-law dependences are observed for the low-frequency capacitance and conductance, consistent with hopping conduction of carriers through the oxides. Despite their high oxygen-vacancy densities, the Nb2O5-based MIM diodes are radiation tolerant up to at least Mrad(SiO2) doses.

The role of stoichiometry and growth temperature in the preferential nucleation of material phases in the Li-Nb-O family are explored yielding an empirical growth phase diagram. It is shown that while single parameter variation often produces multi-phase films, combining substrate temperature control with the previously published lithium flux limited growth allows the repeatable growth of high quality single crystalline films of many different oxide phases. Higher temperatures (800-1050 {\deg}C) than normally used in MBE were necessary to achieve high quality materials. At these temperatures the desorption of surface species is shown to play an important role in film composition. Using this method single phase films of NbO, NbO$_{2}$, LiNbO$_{2}$, Li$_{3}$NbO$_{4}$, LiNbO$_{3}$, and LiNb$_{3}$O$_{8}$ have been achieved in the same growth system, all on c-plane sapphire. Finally, the future of these films in functional oxide heterostructures is briefly discussed.

Lithium niobate is a multi-functional material with wide reaching applications in acoustics, optics, and electronics. Commercial applications for lithium niobate require high crystalline quality currently limited to bulk and ion sliced material. Thin film lithium niobate is an attractive option for a variety of integrated devices, but the research effort has been stagnant due to poor material quality. Both lattice matched and mismatched lithium niobate are grown by molecular beam epitaxy (MBE) and studied to understand the role of substrate and temperature on nucleation conditions and material quality. Growth on sapphire produces partially coalesced columnar grains with atomically flat plateaus and no twin planes. A symmetric rocking curve shows a narrow linewidth with a full width at half-maximum (FWHM) of 8.6 arcsec (0.0024{\deg}) which is comparable to the 5.8 arcsec rocking curve FWHM of the substrate, while the film asymmetric rocking curve is 510 arcsec FWHM. These values indicate that the individual grains are relatively free of long-range disorder detectable by x-ray diffraction (XRD) with minimal measurable tilt and twist and represents the highest structural quality epitaxial material grown on lattice mismatched sapphire without twin planes. Lithium niobate is also grown on lithium tantalate producing high quality coalesced material without twin planes and with a symmetric rocking curve of 193 arcsec, which is nearly equal to the substrate rocking curve of 194 arcsec. The surface morphology of lithium niobate on lithium tantalate is shown to be atomically flat by atomic force microscopy (AFM).

The deeply depleted graphene-oxide-semiconductor junction $(\mathrm{D}^{2}\mathrm{GOS})$ architecture has been shown to be a highly sensitive light detector [1]. In this architecture, photogenerated charge in the depletion region of the semiconductor is separated and then directly readout by an adjacent graphene layer similarly to a photoFET. Although detection of (electrons and light) radiation using graphene has been previously demonstrated, only limited work has been conducted on other types of ionizing radiation detection with graphene [2]–[3]. In this work we demonstrate advances made in high energy (2 & 20 MeV), heavy ion (Si+) detection using the $\mathrm{D}^{2}\mathrm{GOS}$ junction, leveraging our previous experience and fabrication improvements for visible light detection using a silicon absorber substrate.

Energy harvesting from relatively low-temperature heat sources is important in applications where long-term power sources are needed such as deep space radioisotope thermoelectric generators (RTGs). Current solutions exhibit low efficiency, require exotic materials and structures, and direct contact to the heat source. While the infrared rectenna is currently low efficiency, the path exists for high-efficiency solid state devices. We have made a scalable design using standard CMOS processes, allowing for large-area fabrication. This would allow devices to be made on the wafer scale using existing fabrication technology. The rectenna has the advantage of using radiated power, thus it does not require direct contact to the hot source, but instead must only view the source. This will simplify packaging requirements and make a more robust system. The devices are monolithic and thus robust to adverse operating environments. Here we will discuss the rectenna's physics of operation, particularly light coupling into the structure. Incoming light is coupled to a metal-oxide-semiconductor (MOS) tunnel diode via a broad-area nanoantenna. The nanoantenna consists of a subwavelength metal patterning that concentrates the light into the tunnel diode where the optical signal is rectified. Both the nanoantenna and tunnel diode are distributed devices utilizing the entire area of the surface. The nanoantenna also serves as one contact of the tunnel diode. This direct integration of the nanoantenna and diode overcomes the resistive loss limitations found in prior IR rectenna concepts that resembled microwave rectenna designs scaled down to infrared sizes. We will show simulation and experimental results of fabricated devices. Simulations of the optical fields in the tunnel gap are illustrative of device operation and will be discussed. The measured infrared photocurrent is compared to simulated expectations. Far-field radiation power conversion is demonstrated using standard radiometric techniques and correlated with the rectified current response. We discuss thermal modelling of the localized heat generation within the rectenna structure to demonstrate the lack of a thermoelectric response. Lastly, we discuss future directions of work to improve power conversion efficiency.

Sputter deposition of the thin film memristor material, lithium niobite (LiNbO2) is performed by co-deposition from a lithium oxide (Li2O) and a niobium target. Crystalline films that are textured about the (101) orientation are produced under room temperature conditions. This material displays memristive hysteresis and exhibits XPS spectra similar to MBE and bulk grown LiNbO2. Various deposition parameters were investigated resulting in variations in the deposition rate, film crystallinity, oxygen to niobium ratio, and mean niobium oxidation state. The results of this study allow for the routine production of large area LiNbO2 films at low substrate temperature useful in hybrid-integration of memristor, optical, and energy storage applications.

Coupling of metasurfaces to intersubband transitions (ISTs) in semiconductor quantum wells (QWs) has been extensively studied for various applications ranging from generating giant nonlinear optical response to designing tunable metasurfaces for applications such as ultrafast spatial optical modulators and voltage tunable filters. In this work, we experimentally demonstrate a fundamentally new approach of actively controlling the coupling of ISTs in QWs to a metasurface for voltage tuning its optical response. Unlike previous approaches, we use voltage-controlled quantum tunneling to control the carrier concentration in the QWs for turning on/off the ISTs. We design a multi-quantum well structure consisting of four undoped InGaAs wells with AlInAs barriers grown on top of a highly doped InGaAs layer that acts as an electron reservoir. The heterostructure is optimized such that the first IST in all the wells is at 11µm. A complementary gold metasurface with dipole resonances at 11µm is fabricated on top of the QW structure. We designed the heterostructure such that by applying a bias of 1V, the energy bands of all the QWs get aligned simultaneously, leading to the occupation of the ground state of all the QWs via quantum tunneling of the electrons from the electron reservoir. The ISTs which were turned off due to negligible electron density gets turned on at 1V, and this leads to coupling between the ISTs and the dipoles resonances of the metasurface. The voltage induced coupling leads to reflectance modulation which we confirmed experimentally by rapid scan double modulation FTIR measurements.

Metasurfaces have been investigated for various applications ranging from beam steering, focusing, to polarization conversion. Along with passive metasurfaces, significant efforts are also being made to design metasurfaces with tunable optical response. Among various approaches, voltage tuning is of particular interest because it creates the possibility of integration with electronics. In this work, we demonstrate voltage tuning of reflectance from a complementary metasurface strongly coupled to an epsilon-near-zero (ENZ) mode in an ultrathin semiconductor layer. Our approach involves electrically controlling the carrier concentration of the ENZ layer to modulate the polaritonic coupling between the dipole resonances of the metasurface and the ENZ mode for modulating the reflectance of the metasurface. The hybrid structure we fabricate is similar to MOSCAP configuration where the complementary metasurface offers a continuous gold top layer for biasing and positive/negative bias to the metasurface leads to accumulation/depletion of carriers in the ENZ layer beneath it. We optimized our structure by using InGaAs as the ENZ material because of its high mobility and low effective mass. This allowed us to reduce the doping requirement and thereby reduce the ionized impurity scattering as well as the reverse bias required to deplete the ENZ layer. For low leakage and efficient modulation of carrier density, we used Hafnia as the gate dielectric. We further added a reflecting backplane below the ENZ layer to enhance the interaction and by applying bias, we achieved spectral shifts of 500 nm and amplitude modulation of 11% of one of the polariton branches at 14 µm.

Electrical power generation from a moderate temperature thermal source by means of direct conversion of infrared radiation is important and highly desirable for energy harvesting from waste heat and micropower applications. Here, we demonstrate direct rectified power generation from an unbiased large-area nanoantenna-coupled tunnel diode rectifier, called a rectenna. Using a vacuum radiometric measurement technique with irradiation from a temperature-stabilized thermal source, a generated power density of 8 nW/cm$^2$ is observed at a source temperature of 450C for the unbiased rectenna across an optimized load resistance. The optimized load resistance for the peak power generation for each temperature coincides with the tunnel diode resistance at zero bias and corresponds to the impedance matching condition for a rectifying antenna. Current voltage measurements of a thermally illuminated large-area rectenna show current zero crossing shifts into the second quadrant indicating rectification. Photon-assisted tunneling in the unbiased rectenna is modeled as the mechanism for the large short-circuit photocurrents observed where the photon energy serves as an effective bias across the tunnel junction. The measured current and voltage across the load resistor as a function of the thermal source temperature represents direct current electrical power generation., 8 pages, 7 figures, Journal submission

We experimentally demonstrate spectral tuning and amplitude modulation of reflectance at long infrared wavelengths using a complementary metasurface strongly coupled to an epsilon-near-zero (ENZ) mode in an ultrathin InGaAs layer with a reflecting backplane.

We demonstrate a fundamentally new approach of using voltage controlled quantum tunneling for modulating optical response of a metasurface coupled to intersubband transitions in semiconductor quantum wells.

In order to consistently grow high quality niobium oxides and lithium niobium oxides, a novel solid/liquid state oxygen source, LiClO 4 , has been implemented in a molecular beam epitaxy (MBE) system. LiClO 4 is shown to decompose into both molecular and atomic oxygen upon heating. This allows oxidation rates similar to that of molecular oxygen but at a reduced overall beam flux, quantified by in situ Auger analysis. LiClO 4 operation is decomposition limited to less than 400 °C, and other material limitations are identified. The design of a custom near-ambient NbCl 5 effusion cell is presented, which improves both short and long term stability. Films of Nb oxidation state +2, +3, and +5 are grown using these new tools, including the multi-functional sub-oxide LiNbO 2 .

Proton radiation damage and short-term annealing are investigated for lithium niobite ( ${\rm LiNbO}_{2}$ ) mixed electronic-ionic memristors. Radiation damage and short-term annealing were characterized using Electrochemical Impedance Spectroscopy (EIS) to determine changes in the device resistance and the lithium ion mobility. The radiation damage resulted in a 0.48% change in the resistance at a fluence of ${10^{14}}~\hbox{cm}^{ - 2}$ . In-situ short-term annealing at room temperature reduced the net detrimental effect of the damage with a time constant of about 9 minutes. The radiation damage mechanism is attributed predominantly to displacement damage at the niobium and oxygen sites trapping lithium ions that are responsible for induced polarization within the material. Short term annealing is attributed to room temperature thermal annealing of these defects, freeing the highly mobile lithium ions.

We examine the vacuum infrared photoresponse of a large-area nanoantenna-coupled tunnel diode rectenna resulting from thermal radiation from a temperature controlled heater. The measured infrared photocurrent is obtained as a function of the source temperature, sample distance and view factor. Far-field radiation power conversion is examined using standard radiometric techniques and correlated with the rectified current response.

The transfer Hamiltonian tunneling current is derived in a time-dependent density matrix formulation and is used to examine photon-assisted tunneling. Bardeen's tunneling expression arises as the result of first order perturbation theory in a mean-field expansion of the density matrix. Photon-assisted tunneling from confined electromagnetic fields in the forbidden barrier region occurs due to time-varying polarization and wavefunction overlap in the gap, which leads to a non-zero tunneling current in asymmetric device structures, even in an unbiased state. The photon energy is seen to act as an effective temperature dependent bias in a uniform barrier asymmetric tunneling example problem. Higher order terms in the density matrix expansion give rise to multi-photon enhanced tunneling currents that can be considered an extension of non-linear optics where the non-linear conductance plays a similar role as the non-linear susceptibilities in the continuity equations., Comment: 8 pages, 2 figures

The growth of seeded and self-nucleated LiNbO2 crystals with a simplified chemistry has been demonstrated using a liquid phase electro-epitaxy method at high temperatures (900 °C). X-ray diffraction (XRD) was used to quantify the crystal quality and confirmed that both the seeded and self-nucleated crystals grown were single-orientation; the full width at half-maximum (FWHM) for the symmetric XRD double crystal diffraction scan was 230 arcsec, while the FWHM for the XRD omega rocking curve was 19.2 arcmin and 310 arcsec for self-nucleated and seeded crystals, respectively. The LiNbO2 crystals have undetectable amounts of contamination as determined via X-ray photoelectron spectroscopy and secondary ion mass spectrometry. Finally, as-grown LiNbO2 crystals were shown to exhibit a memristive response and could be utilized in future neuromorphic computing architectures.

The effects of X-ray and proton radiation on a LiNbO2 analog memristor are investigated by I-V hysteresis, Electrochemical Impedance Spectroscopy, low-frequency AC voltage, and X-ray diffraction analysis. Both electrical and structural characterization of an irradiated memristor show that irradiation leads to an increased level of defects in the LiNbO2 crystalline lattice. These radiation-induced defects facilitate faster lithium movement as shown by electrochemical impedance spectroscopy measurements on the as-grown and irradiated memristor. X-ray radiation improves ionic motion in the bulk of the device and increases the ionic resistance at the LiNbO2-metal interface. In the case of proton radiation, the memristance response improves due to an increase in ionic motion in the bulk and at the interfaces. It is also shown by Monte Carlo simulations that proton irradiation of LiNbO2 results in structural damage, which was verified experimentally by an X-ray diffraction study.

An electronic device is introduced that exhibits rectification, hysteresis, and capacitance. These three properties replicate biological functionality useful in neuromorphic circuitry. A similar device operating on different physical mechanisms was previously demonstrated in 2013, but its fabrication required an electro-formation process that introduces difficulties scaling to high density circuitry [1]. The metal-insulator-metal (MIM) structures discussed herein exhibit rectification, hysteresis, and capacitance resulting from an intentionally high defect density as deposited with no post-fabrication treatment necessary.

The ability to control the light-matter interaction with an external stimulus is a very active area of research since it creates exciting new opportunities for designing optoelectronic devices. Recently, plasmonic metasurfaces have proven to be suitable candidates for achieving a strong light-matter interaction with various types of optical transitions, including intersubband transitions (ISTs) in semiconductor quantum wells (QWs). For voltage modulation of the light-matter interaction, plasmonic metasurfaces coupled to ISTs offer unique advantages since the parameters determining the strength of the interaction can be independently engineered. In this work, we report a proof-of-concept demonstration of a new approach to voltage-tune the coupling between ISTs in QWs and a plasmonic metasurface. In contrast to previous approaches, the IST strength is here modified via control of the electron populations in QWs located in the near field of the metasurface. By turning on and off the ISTs in the semiconductor QWs, we observe a modulation of the optical response of the IST coupled metasurface due to modulation of the coupled light-matter states. Because of the electrostatic design, our device exhibits an extremely low leakage current of ∼6 pA at a maximum operating bias of +1 V and therefore very low power dissipation. Our approach provides a new direction for designing voltage-tunable metasurface-based optical modulators.

Considering the power constrained scaling of silicon complementary metal-oxide-semiconductor technology, the use of high mobility III–V compound semiconductors such as In0.53Ga0.47As in conjunction with high-κ dielectrics is becoming a promising option for future n-type metal-oxide-semiconductor field-effect-transistors. Development of low dissipation field-effect tunable III–V based photonic devices integrated with high-κ dielectrics is therefore very appealing from a technological perspective. In this work, we present an experimental realization of a monolithically integrable, field-effect-tunable, III–V hybrid metasurface operating at long-wave-infrared spectral bands. Our device relies on strong light-matter coupling between epsilon-near-zero (ENZ) modes of an ultra-thin In0.53Ga0.47As layer and the dipole resonances of a complementary plasmonic metasurface. The tuning mechanism of our device is based on field-effect modulation, where we modulate the coupling between the ENZ mode and the metasurface by modifying the carrier density in the ENZ layer using an external bias voltage. Modulating the bias voltage between ±2 V, we deplete and accumulate carriers in the ENZ layer, which result in spectrally tuning the eigenfrequency of the upper polariton branch at 13 μm by 480 nm and modulating the reflectance by 15%, all with leakage current densities less than 1 μA/cm2. Our wavelength scalable approach demonstrates the possibility of designing on-chip voltage-tunable filters compatible with III–V based focal plane arrays at mid- and long-wave-infrared wavelengths.

The theoretically suggested band structure of the novel p-type semiconductor lithium niobite (LiNbO2), the direct coupling of photons to ion motion, and optically induced band structure modifications are investigated by temperature dependent photoluminescence. LiNbO2 has previously been used as a memristor material but is shown here to be useful as a sensor owing to the electrical, optical, and chemical ease of lithium removal and insertion. Despite the high concentration of vacancies present in lithium niobite due to the intentional removal of lithium atoms, strong photoluminescence spectra are observed even at room temperature that experimentally confirm the suggested band structure implying transitions from a flat conduction band to a degenerate valence band. Removal of small amounts of lithium significantly modifies the photoluminescence spectra including additional larger than stoichiometric-band gap features. Sufficient removal of lithium results in the elimination of the photoluminescence response supporting the predicted transition from a direct to indirect band gap semiconductor. In addition, non-thermal coupling between the incident laser and lithium ions is observed and results in modulation of the electrical impedance.

Analog memristors that exhibit an electronic conductivity change in response to ionic motion have been simulated using the finite element method. Several physical mechanisms are considered for the redistribution of dopants within the device and all result in minimal resistance changes. The mechanisms considered that result in minimal resistance changes are initial ion concentration, hole mobility dependence on acceptor concentration, and geometry. In contrast, ion extraction results in a significant change in the simulated analog memristor resistance (many orders of magnitude). It is determined that if ions can be repeatedly cycled without damage to the crystal structure, ion extraction is the optimal analog ionic memristor operation mechanism. Given this conclusion, battery technology materials known for their robustness in spite of repeated ion extraction/replacement should be considered for reliable analog memristor applications.