Design and manufacture of an all-polymeric integrated multimode interferometer for visible photonics.

This work demonstrates an integrated multimode interferometer (MMI) based on a fully polymeric platform and optimized for visible range operation. The dimensions of a 2×2 MMI are first calculated analytically and simulated using finite elements method. The devices are manufactured using two layers of negative tone photoresists. The top layer is patterned by e-beam lithography demonstrating the adaptability of this material, naturally designed to respond to UV radiation. Fabrication tolerance was smaller than 100 nm. Devices were optically characterized with a 635 nm input source and the best performance for a 3 dB power splitter was found at an interferometric cavity dimension of 10.5 × 190.68 µm. Other interferometric lengths were characterized to establish a process design kit that allows future use of this platform in more complex photonic integrated circuits architectures.

Ultrasensitive dopamine detection with graphene aptasensor multitransistor arrays.

Detecting physiological levels of neurotransmitters in biological samples can advance our understanding of brain disorders and lead to improved diagnostics and therapeutics. However, neurotransmitter sensors for real-world applications must reliably detect low concentrations of target analytes from small volume working samples. Herein, a platform for robust and ultrasensitive detection of dopamine, an essential neurotransmitter that underlies several brain disorders, based on graphene multitransistor arrays (gMTAs) functionalized with a selective DNA aptamer is presented. High-yield scalable methodologies optimized at the wafer level were employed to integrate multiple graphene transistors on small-size chips (4.5 × 4.5 mm). The multiple sensor array configuration permits independent and simultaneous replicate measurements of the same sample that produce robust average data, reducing sources of measurement variability. This procedure allowed sensitive and reproducible dopamine detection in ultra-low concentrations from small volume samples across physiological buffers and high ionic strength complex biological samples. The obtained limit-of-detection was 1 aM (10-18) with dynamic detection ranges spanning 10 orders of magnitude up to 100 µM (10-8), and a 22 mV/decade peak sensitivity in artificial cerebral spinal fluid. Dopamine detection in dopamine-depleted brain homogenates spiked with dopamine was also possible with a LOD of 1 aM, overcoming sensitivity losses typically observed in ion-sensitive sensors in complex biological samples. Furthermore, we show that our gMTAs platform can detect minimal changes in dopamine concentrations in small working volume samples (2 µL) of cerebral spinal fluid samples obtained from a mouse model of Parkinson's Disease. The platform presented in this work can lead the way to graphene-based neurotransmitter sensors suitable for real-world academic and pre-clinical pharmaceutical research as well as clinical diagnosis.

Interplay of Magnetic Properties and Doping in Epitaxial Films of h-REFeO3 Multiferroic Oxides.

Multiferroic materials demonstrating coexistence of magnetic and ferroelectric orders are promising candidates for magnetoelectric devices. While understanding the underlying mechanism of interplaying of ferroic properties is important, tailoring their properties to make them potential candidates for magnetoelectric devices is challenging. Here, the antiferromagnetic Neel ordering temperature above 200 K is realized in successfully stabilized epitaxial films of (Lu,Sc)FeO3 multiferroic oxide. The first-principles calculations show the shrinkage of in-plane lattice constants of the unit cells of the films on different substrates which corroborates well the enhancement of the Neel ordering temperature (TN ). The profound effect of lattice strain/stress at the interface due to differences of in-plane lattice constants on out of plane magnetic properties and on spin reorientation temperature in the antiferromagnetic region is further elucidated in the epitaxial films with and without buffer layer of Mn-doped LuFeO3 . Writing and reading ferroelectric domains reveal the ferroelectric response of the films at room temperature. Detailed electron microscopy shows the presence of lattice defects in atomic scale. First-principles calculations show that orbital rehybridization of rare-earth ions and oxygen is one of the main driving force of ferroelectricity along c-axis in thin films of hexagonal ferrites.

Efficient light extraction in subwavelength GaAs/AlGaAs nanopillars for nanoscale light-emitting devices.

This work reports on high extraction efficiency in subwavelength GaAs/AlGaAs semiconductor nanopillars. We achieve up to 37-fold enhancement of the photoluminescence (PL) intensity from sub-micrometer (sub-µm) pillars without requiring back reflectors, high-Q dielectric cavities, nor large 2D arrays or plasmonic effects. This is a result of a large extraction efficiency for nanopillars <500 nm width, estimated in the range of 33-57%, which is much larger than the typical low efficiency (∼2%) of micrometer pillars limited by total internal reflection. Time-resolved PL measurements allow us to estimate the nonradiative surface recombination of fabricated pillars. We conclusively show that vertical-emitting nanopillar-based LEDs, in the best case scenario of both reduced surface recombination and efficient light out-coupling, have the potential to achieve notable large external quantum efficiency (∼45%), whereas the efficiency of large µm-pillar planar LEDs, without further methods, saturates at ∼2%. These results offer a versatile method of light management in nanostructures with prospects to improve the performance of optoelectronic devices including nanoscale LEDs, nanolasers, single photon sources, photodetectors, and solar cells.

Ultra-Compact 100 × 100 µm² Footprint Hybrid Device with Spin-Valve Nanosensors.

Magnetic field mapping with micrometric spatial resolution and high sensitivity is a challenging application, and the technological solutions are usually based on large area devices integrating discrete magnetic flux guide elements. In this work we demonstrate a high performance hybrid device with improved field sensitivity levels and small footprint, consisting of a ultra-compact 2D design where nanometric spin valve sensors are inserted within the gap of thin-film magnetic flux concentrators. Pole-sensor distances down to 400 nm are demonstrated using nanofabrication techniques combined with an optimized liftoff process. These 100 × 100 µm2 pixel sensors can be integrated in modular devices for surface mapping without moving parts.

Extraction of Graphene's RF Impedance through Thru-Reflect-Line Calibration.

Graphene has unique properties that can be exploited for radiofrequency applications. Its characterization is key for the development of new graphene devices, circuits, and systems. Due to the two-dimensional nature of graphene, there are challenges in the methodology to extract relevant characteristics that are necessary for device design. In this work, the Thru-Reflect-Line (TRL) calibration was evaluated as a solution to extract graphene's electrical characteristics from 1 GHz to 65 GHz, where the calibration structures' requirements were analyzed. It was demonstrated that thick metallic contacts, a low-loss substrate, and a short and thin contact are necessary to characterize graphene. Furthermore, since graphene's properties are dependent on the polarization voltage applied, a backgate has to be included so that graphene can be characterized for different chemical potentials. Such characterization is mandatory for the design of graphene RF electronics and can be used to extract characteristics such as graphene's resistance, quantum capacitance, and kinetic inductance. Finally, the proposed structure was characterized, and graphene's resistance and quantum capacitance were extracted.

Integrated Approach from Sample-to-Answer for Grapevine Varietal Identification on a Portable Graphene Sensor Chip.

Identifying grape varieties in wine, related products, and raw materials is of great interest for enology and to ensure its authenticity. However, these matrices' complexity and low DNA content make this analysis particularly challenging. Integrating DNA analysis with 2D materials, such as graphene, offers an advantageous pathway toward ultrasensitive DNA detection. Here, we show that monolayer graphene provides an optimal test bed for nucleic acid detection with single-base resolution. Graphene's ultrathinness creates a large surface area with quantum confinement in the perpendicular direction that, upon functionalization, provides multiple sites for DNA immobilization and efficient detection. Its highly conjugated electronic structure, high carrier mobility, zero-energy band gap with the associated gating effect, and chemical inertness explain graphene's superior performance. For the first time, we present a DNA-based analytic tool for grapevine varietal discrimination using an integrated portable biosensor based on a monolayer graphene field-effect transistor array. The system comprises a wafer-scale fabricated graphene chip operated under liquid gating and connected to a miniaturized electronic readout. The platform can distinguish closely related grapevine varieties, thanks to specific DNA probes immobilized on the sensor, demonstrating high specificity even for discriminating single-nucleotide polymorphisms, which is hard to achieve with a classical end-point polymerase chain reaction or quantitative polymerase chain reaction. The sensor was operated in ultralow DNA concentrations, with a dynamic range of 1 aM to 0.1 nM and an attomolar detection limit of ∼0.19 aM. The reported biosensor provides a promising way toward developing decentralized analytical tools for tracking wine authenticity at different points of the food value chain, enabling data transmission and contributing to the digitalization of the agro-food industry.

Attomolar detection of hepatitis C virus core protein powered by molecular antenna-like effect in a graphene field-effect aptasensor.

Biosensors based on graphene field-effect transistors have become a promising tool for detecting a broad range of analytes. However, their performance is substantially affected by the functionalization protocol. In this work, we use a controlled in-vacuum physical method for the covalent functionalization of graphene to construct ultrasensitive aptamer-based biosensors (aptasensors) able to detect hepatitis C virus core protein. These devices are highly specific and robust, achieving attomolar detection of the viral protein in human blood plasma. Such an improved sensitivity is rationalized by theoretical calculations showing that induced polarization at the graphene interface, caused by the proximity of covalently bound molecular probe, modulates the charge balance at the graphene/aptamer interface. This charge balance causes a net shift of the Dirac cone providing enhanced sensitivity for the attomolar detection of the target proteins. Such an unexpected effect paves the way for using this kind of graphene-based functionalized platforms for ultrasensitive and real-time diagnostics of different diseases.

Surface Passivation of III-V GaAs Nanopillars by Low-Frequency Plasma Deposition of Silicon Nitride for Active Nanophotonic Devices.

Numerous efforts have been devoted to improve the electronic and optical properties of III-V compound materials via reduction of their nonradiative states, aiming at highly efficient III-V sub-micrometer active devices and circuits. Despite many advances, the poor reproducibility and short-term passivation effect of chemical treatments, such as sulfidation and nitridation, requires the use of protective encapsulation methods, not only to protect the surface, but also to provide electrical isolation for device manufacturing. There is still a controversial debate on which combination of chemical treatment and capping dielectric layer can best reproducibly protect the crystal surface of III-V materials while being compatible with readily available semiconductor-foundry plasma deposition methods. This work reports on a systematic experimental study on the role of sulfide ammonium chemical treatment followed by dielectric coating (either silicon oxide or nitride) in the passivation effect of GaAs/AlGaAs nanopillars. Our results conclusively show that, under ambient conditions, the best surface passivation is achieved using ammonium sulfide followed by encapsulation with a thin layer of silicon nitride by low-frequency plasma-enhanced chemical deposition. Here, the sulfurized GaAs surfaces, high level of hydrogen ions, and low-frequency (380 kHz) excitation plasma that enable intense bombardment of hydrogen, all seem to provide a combined active role in the passivation mechanism of the pillars by reducing the surface states. As a result, we observe up to a 29-fold increase of the photoluminescence (PL) integrated intensity for the best samples as compared to untreated nanopillars. X-ray photoelectron spectroscopy analysis confirms the best treatments show remarkable removal of gallium and arsenic native oxides. Time-resolved micro-PL measurements display nanosecond lifetimes resulting in a record-low surface recombination velocity of ∼1.1 × 104 cm s-1 for dry-etched GaAs nanopillars. We achieve robust, stable, and long-term passivated nanopillar surfaces, which creates expectations for remarkable high internal quantum efficiency (IQE > 0.5) in nanoscale light-emitting diodes. The enhanced performance paves the way to many other nanostructures and devices such as miniature resonators, lasers, photodetectors, and solar cells, opening remarkable prospects for GaAs active nanophotonic devices.

Optimizing PMMA solutions to suppress contamination in the transfer of CVD graphene for batch production.

Mass production and commercial adoption of graphene-based devices are held back by a few crucial technical challenges related to quality control. In the case of graphene produced by chemical vapor deposition, the transfer process represents a delicate step that can compromise device performance and reliability, thus hindering industrial production. In this context, the impact of poly(methyl methacrylate) (PMMA), the most common support material for transferring graphene from the Cu substrate to any target surface, can be decisive in obtaining reproducible sample batches. Although effective in mechanically supporting graphene during the transfer, PMMA solutions needs to be efficiently designed, deposited, and post-treated to serve their purpose while minimizing potential contaminations. Here, we prepared and tested PMMA solutions with different average molecular weight (AMW) and weight concentration in anisole, to be deposited by spin coating. Optical microscopy and Raman spectroscopy showed that the amount of PMMA residues on transferred graphene is proportional to the AMW and concentration in the solvent. At the same time, the mechanical strength of the PMMA layer is proportional to the AMW. These tests served to design an optimized PMMA solution made of a mixture of 550,000 (550k) and 15,000 (15k) AMW PMMA in anisole at 3% concentration. In this design, PMMA-550k provided suitable mechanical strength against breakage during the transfer cycles, while PMMA-15k promoted depolymerization, which allowed for a complete removal of PMMA residues without the need for any post-treatment. An XPS analysis confirmed the cleanness of the optimized process. We validated the impact of the optimized PMMA solution on the mass fabrication of arrays of electrolyte-gated graphene field-effect transistors operating as biosensors. On average, the transistor channel resistance decreased from 1860 to 690 Ω when using the optimized PMMA. Even more importantly, the vast majority of these resistance values are distributed within a narrow range (only ca. 300 Ω wide), in evident contrast with the scattered values obtained in non-optimized devices (about 30% of which showed values above 1 MΩ). These results prove that the optimized PMMA solution unlock the production of reproducible electronic devices at the batch scale, which is the key to industrial production.

Non-volatile artificial synapse based on a vortex nano-oscillator.

In this work, a new mechanism to combine a non-volatile behaviour with the spin diode detection of a vortex-based spin torque nano-oscillator (STVO) is presented. Experimentally, it is observed that the spin diode response of the oscillator depends on the vortex chirality. Consequently, fixing the frequency of the incoming signal and switching the vortex chirality results in a different rectified voltage. In this way, the chirality can be deterministically controlled via the application of electrical signals injected locally in the device, resulting in a non-volatile control of the output voltage for a given input frequency. Micromagnetic simulations corroborate the experimental results and show the main contribution of the Oersted field created by the input RF current density in defining two distinct spin diode detections for different chiralities. By using two non-identical STVOs, we show how these devices can be used as programmable non-volatile synapses in artificial neural networks.

Influence of the Electrolyte Salt Concentration on DNA Detection with Graphene Transistors.

Liquid-gated Graphene Field-Effect Transistors (GFET) are ultrasensitive bio-detection platforms carrying out the graphene's exceptional intrinsic functionalities. Buffer and dilution factor are prevalent strategies towards the optimum performance of the GFETs. However, beyond the Debye length (λD), the role of the graphene-electrolytes' ionic species interactions on the DNA behavior at the nanoscale interface is complicated. We studied the characteristics of the GFETs under different ionic strength, pH, and electrolyte type, e.g., phosphate buffer (PB), and phosphate buffer saline (PBS), in an automatic portable built-in system. The electrostatic gating and charge transfer phenomena were inferred from the field-effect measurements of the Dirac point position in single-layer graphene (SLG) transistors transfer curves. Results denote that λD is not the main factor governing the effective nanoscale screening environment. We observed that the longer λD was not the determining characteristic for sensitivity increment and limit of detection (LoD) as demonstrated by different types and ionic strengths of measuring buffers. In the DNA hybridization study, our findings show the role of the additional salts present in PBS, as compared to PB, in increasing graphene electron mobility, electrostatic shielding, intermolecular forces and DNA adsorption kinetics leading to an improved sensitivity.

Efficient ReSe2 Photodetectors with CVD Single-Crystal Graphene Contacts.

Rhenium-based 2D transition metal dichalcogenides such as ReSe2 are suitable candidates as photoactive materials for optoelectronic devices. Here, photodetectors based on mechanically exfoliated ReSe2 crystals were fabricated using chemical vapor deposited (CVD) graphene single-crystal (GSC) as lateral contacts. A "pick & place" method was adopted to transfer the desired crystals to the intended position, easing the device fabrication while reducing potential contaminations. A similar device with Au was fabricated to compare contacts' performance. Lastly, a CVD hexagonal boron nitride (hBN) substrate passivation layer was designed and introduced in the device architecture. Raman spectroscopy was carried out to evaluate the device materials' structural and electronic properties. Kelvin probe force measurements were done to calculate the materials' work function, measuring a minimal Schottky barrier height for the GSC/ReSe2 contact (0.06 eV). Regarding the electrical performance, I-V curves showed sizable currents in the GSC/ReSe2 devices in the dark and under illumination. The devices presented high photocurrent and responsivity, along with an external quantum efficiency greatly exceeding 100%, confirming the non-blocking nature of the GSC contacts at high bias voltage (above 2 V). When introducing the hBN passivation layer, the device under white light reached a photo-to-dark current ratio up to 106.

On the Importance of Joint Mitigation Strategies for Front, Bulk, and Rear Recombination in Ultrathin Cu(In,Ga)Se2 Solar Cells.

Several optoelectronic issues, such as poor optical absorption and recombination, limit the power conversion efficiency of ultrathin Cu(In,Ga)Se2 (CIGS) solar cells. To mitigate recombination losses, two combined strategies were implemented: a potassium fluoride (KF) post-deposition treatment (PDT) and a rear interface passivation strategy based on an aluminum oxide (Al2O3) point contact structure. The simultaneous implementation of both strategies is reported for the first time on ultrathin CIGS devices. Electrical measurements and 1D simulations demonstrate that in specific conditions, devices with only KF-PDT may outperform rear interface passivation based devices. By combining KF-PDT and rear interface passivation, an enhancement in an open-circuit voltage of 178 mV is reached over devices that have a rear passivation only, and of 85 mV over devices with only a KF-PDT process. Time-Resolved Photoluminescence measurements showed the beneficial effects of combining KF-PDT and the rear interface passivation at decreasing recombination losses in the studied devices, enhancing charge carrier lifetime. X-ray photoelectron spectroscopy measurements indicate the presence of an In and Se-rich layer that we linked to be a KInSe2 layer. Our results suggest that when bulk and front interface recombination values are very high, they dominate, and individual passivation strategies work poorly. Hence, this work shows that for ultrathin devices, passivation mitigation strategies need to be implemented in tandem.

Multi-beam two-photon polymerization for fast large area 3D periodic structure fabrication for bioapplications.

Two-photon polymerization (TPP) is capable of fabricating 3D structures with dimensions from sub-µm to a few hundred µm. As a direct laser writing (DLW) process, fabrication time of 3D TPP structures scale with the third order, limiting its use in large volume fabrication. Here, we report on a scalable fabrication method that cuts fabrication time to a fraction. A parallelized 9 multi-beamlets DLW process, created by a fixed diffraction optical element (DOE) and subsequent stitching are used to fabricate large periodic high aspect ratio 3D microstructured arrays with sub-micron features spanning several hundred of µm2. The wall structure in the array is designed with a minimum of traced lines and is created by a low numerical aperture (NA) microscope objective, leading to self-supporting lines omitting the need for line-hatching. The fabricated periodic arrays are applied in a cell - 3D microstructure interaction study using living HeLa cells. First indications of increased cell proliferation in the presence of 3D microstructures compared to planar surfaces are obtained. Furthermore, the cells adopt an elongated morphology when attached to the 3D microstructured surfaces. Both results constitute promising findings rendering the 3D microstructures a suited tool for cell interaction experiments, e.g. for cell migration, separation or even tissue engineering studies.

Clean-Room Lithographical Processes for the Fabrication of Graphene Biosensors.

This work is on developing clean-room processes for the fabrication of electrolyte-gate graphene field-effect transistors at the wafer scale for biosensing applications. Our fabrication process overcomes two main issues: removing surface residues after graphene patterning and the dielectric passivation of metallic contacts. A graphene residue-free transfer process is achieved by using a pre-transfer, sacrificial metallic mask that protects the entire wafer except the areas around the channel, source, and drain, onto which the graphene film is transferred and later patterned. After the dissolution of the mask, clean gate electrodes are obtained. The multilayer SiO2/SiNx dielectric passivation takes advantage of the excellent adhesion of SiO2 to graphene and the substrate materials and the superior impermeability of SiNx. It hinders native nucleation centers and breaks the propagation of defects through the layers, protecting from prolonged exposition to all common solvents found in biochemistry work, contrary to commonly used polymeric passivation. Since wet etch does not allow the required level of control over the lithographic process, a reactive ion etching process using a sacrificial metallic stopping layer is developed and used for patterning the passivation layer. The process achieves devices with high reproducibility at the wafer scale.

Attomolar Label-Free Detection of DNA Hybridization with Electrolyte-Gated Graphene Field-Effect Transistors.

In this work, we develop a field-effect transistor with a two-dimensional channel made of a single graphene layer to achieve label-free detection of DNA hybridization down to attomolar concentration, while being able to discriminate a single nucleotide polymorphism (SNP). The SNP-level target specificity is achieved by immobilization of probe DNA on the graphene surface through a pyrene-derivative heterobifunctional linker. Biorecognition events result in a positive gate voltage shift of the graphene charge neutrality point. The graphene transistor biosensor displays a sensitivity of 24 mV/dec with a detection limit of 25 aM: the lowest target DNA concentration for which the sensor can discriminate between a perfect-match target sequence and SNP-containing one.

Template-directed self-organization of colloidal PbTe nanocrystals into pillars, conformal coatings, and self-supported membranes.

We demonstrate the formation of three morphologies relevant for integration with miniaturized devices-microscale pillars, conformal coatings, and self-supported membranes-via template-directed self-organization of lead telluride (PbTe) colloidal nanocrystals (NCs). Optimizing the self-organization process towards producing one of these morphologies typically involves adjusting the surface chemistry of the particles, as a means of controlling the particle-particle and particle-template interactions. In contrast, we have produced each of the three morphologies of close-packed NCs by adjusting only the solvent and concentration of NCs, to ensure that the high quality of the ca. 10 nm PbTe NCs produced by hot-injection colloidal synthesis, which we used as model "building blocks," remains consistent across all three configurations. For the first two morphologies, the NCs were deposited as colloidal suspensions onto micropatterned silicon substrates. The microscale cuboid pillars (1 µm × 1 µm × 0.6 µm) were formed by depositing NC dispersions in toluene onto templates patterned with resist grid motifs, followed by the resist removal after the slow evaporation of toluene and formation of the micropillars. Conformal coatings were produced by switching the solvent from toluene to a faster drying hexane and pouring NC dispersions onto silicon templates with topographically patterned microstructures. In a similar process, self-supported NC membranes were formed from NC dispersions in hexane on the surface of diethylene glycol and transferred onto the micropatterned templates. The demonstrated combination of bottom-up self-organization with top-down micropatterned templates provides a scalable route for design and fabrication of NC ensembles in morphologies and form-factors that are compatible with their integration into miniaturized devices.

Scanning tunneling spectroscopy of epitaxial graphene nanoisland on Ir(111).

Scanning tunneling spectroscopy (STS) was used to measure local differential conductance (dI/dV) spectra on nanometer-size graphene islands on an Ir(111) surface. Energy resolved dI/dV maps clearly show a spatial modulation, which we ascribe to a modulated local density of states due to quantum confinement. STS near graphene edges indicates a position dependence of the dI/dV signals, which suggests a reduced density of states near the edges of graphene islands on Ir(111).

Direct observation of electron confinement in epitaxial graphene nanoislands.

One leading question for the application of graphene in nanoelectronics is how electronic properties depend on the size at the nanoscale. Direct observation of the quantized electronic states is central to conveying the relationship between electronic structures and local geometry. Scanning tunneling spectroscopy was used to measure differential conductance dI/dV patterns of nanometer-size graphene islands on an Ir(111) surface. Energy-resolved dI/dV maps clearly show a spatial modulation, indicating a modulated local density of states due to quantum confinement, which is unaffected by the edge configuration. We establish the energy dispersion relation with the quantized electron wave vector obtained from a Fourier analysis of dI/dV maps. The nanoislands preserve the Dirac Fermion properties with a reduced Fermi velocity.