Room Temperature Lattice Thermal Conductivity of GeSn Alloys.

CMOS-compatible materials for efficient energy harvesters at temperatures characteristic for on-chip operation and body temperature are the key ingredients for sustainable green computing and ultralow power Internet of Things applications. In this context, the lattice thermal conductivity (κ) of new group IV semiconductors, namely Ge1-xSnx alloys, are investigated. Layers featuring Sn contents up to 14 at.% are epitaxially grown by state-of-the-art chemical-vapor deposition on Ge buffered Si wafers. An abrupt decrease of the lattice thermal conductivity (κ) from 55 W/(m·K) for Ge to 4 W/(m·K) for Ge0.88Sn0.12 alloys is measured electrically by the differential 3ω-method. The thermal conductivity was verified to be independent of the layer thickness for strained relaxed alloys and confirms the Sn dependence observed by optical methods previously. The experimental κ values in conjunction with numerical estimations of the charge transport properties, able to capture the complex physics of this quasi-direct bandgap material system, are used to evaluate the thermoelectric figure of merit ZT for n- and p-type GeSn epitaxial layers. The results highlight the high potential of single-crystal GeSn alloys to achieve similar energy harvest capability as already present in SiGe alloys but in the 20 °C-100 °C temperature range where Si-compatible semiconductors are not available. This opens the possibility of monolithically integrated thermoelectric on the CMOS platform.

Selective Growth of GaP Crystals on CMOS-Compatible Si Nanotip Wafers by Gas Source Molecular Beam Epitaxy.

Gallium phosphide (GaP) is a III-V semiconductor with remarkable optoelectronic properties, and it has almost the same lattice constant as silicon (Si). However, to date, the monolithic and large-scale integration of GaP devices with silicon remains challenging. In this study, we present a nanoheteroepitaxy approach using gas-source molecular-beam epitaxy for selective growth of GaP islands on Si nanotips, which were fabricated using complementary metal-oxide semiconductor (CMOS) technology on a 200 mm n-type Si(001) wafer. Our results show that GaP islands with sizes on the order of hundreds of nanometers can be successfully grown on CMOS-compatible wafers. These islands exhibit a zinc-blende phase and possess optoelectronic properties similar to those of a high-quality epitaxial GaP layer. This result marks a notable advancement in the seamless integration of GaP-based devices with high scalability into Si nanotechnology and integrated optoelectronics.

Three-Dimensional Reconstruction of Interface Roughness and Alloy Disorder in Ge/GeSi Asymmetric Coupled Quantum Wells Using Electron Tomography.

Interfaces play an essential role in the performance of ever-shrinking semiconductor devices, making comprehensive determination of their three-dimensional (3D) structural properties increasingly important. This becomes even more relevant in compositional interfaces, as is the case for Ge/GeSi heterostructures, where chemical intermixing is pronounced in addition to their morphology. We use the electron tomography method to reconstruct buried interfaces and layers of asymmetric coupled Ge/Ge0.8Si0.2 multiquantum wells, which are considered a potential building block in THz quantum cascade lasers. The three-dimensional reconstruction is based on a series of high-angle annular dark-field scanning transmission electron microscopy images. It allows chemically sensitive investigation of a relatively large interfacial area of about (80 × 80) nm2 with subnanometer resolution as well as the analysis of several interfaces within the multiquantum well stack. Representing the interfaces as iso-concentration surfaces in the tomogram and converting them to topographic height maps allows the determination of their morphological roughness as well as layer thicknesses, reflecting low variations in either case. Simulation of the reconstructed tomogram intensities using a sigmoidal function provides in-plane-resolved maps of the chemical interface widths showing a relatively large spatial variation. The more detailed analysis of the intermixed region using thin slices from the reconstruction and additional iso-concentration surfaces provides an accurate picture of the chemical disorder of the alloy at the interface. Our comprehensive three-dimensional image of Ge/Ge0.8Si0.2 interfaces reveals that in the case of morphologically very smooth interfaces─depending on the scale considered─the interface alloy disorder itself determines the overall characteristics, a result that is fundamental for highly miscible material systems.

Controlling the Nucleation and Growth of Salt from Bodily Fluid for Enhanced Biosensing Applications.

Surface-enhanced Raman spectroscopy (SERS) represents a transformative tool in medical diagnostics, particularly for the early detection of key biomarkers such as small extracellular vesicles (sEVs). Its unparalleled sensitivity and compatibility with intricate biological samples make it an ideal candidate for revolutionizing noninvasive diagnostic methods. However, a significant challenge that mars its efficacy is the throughput limitation, primarily anchored in the prerequisite of hotspot and sEV colocalization within a minuscule range. This paper delves deep into this issue, introducing a never-attempted-before approach which harnesses the principles of crystallization-nucleation and growth. By synergistically coupling lasers with plasmonic resonances, we navigate the challenges associated with the analyte droplet drying method and the notorious coffee ring effect. Our method, rooted in a profound understanding of crystallization's materials science, exhibits the potential to significantly increase the areal density of accessible plasmonic hotspots and efficiently guide exosomes to defined regions. In doing so, we not only overcome the throughput challenge but also promise a paradigm shift in the arena of minimally invasive biosensing, ushering in advanced diagnostic capabilities for life-threatening diseases.

Isothermal Heteroepitaxy of Ge1-x Sn x Structures for Electronic and Photonic Applications.

Epitaxy of semiconductor-based quantum well structures is a challenging task since it requires precise control of the deposition at the submonolayer scale. In the case of Ge1-x Sn x alloys, the growth is particularly demanding since the lattice strain and the process temperature greatly impact the composition of the epitaxial layers. In this paper, the realization of high-quality pseudomorphic Ge1-x Sn x layers with Sn content ranging from 6 at. % up to 15 at. % using isothermal processes in an industry-compatible reduced-pressure chemical vapor deposition reactor is presented. The epitaxy of Ge1-x Sn x layers has been optimized for a standard process offering a high Sn concentration at a large process window. By varying the N2 carrier gas flow, isothermal heterostructure designs suitable for quantum transport and spintronic devices are obtained.

Nanoscale Mapping of the 3D Strain Tensor in a Germanium Quantum Well Hosting a Functional Spin Qubit Device.

A strained Ge quantum well, grown on a SiGe/Si virtual substrate and hosting two electrostatically defined hole spin qubits, is nondestructively investigated by synchrotron-based scanning X-ray diffraction microscopy to determine all its Bravais lattice parameters. This allows rendering the three-dimensional spatial dependence of the six strain tensor components with a lateral resolution of approximately 50 nm. Two different spatial scales governing the strain field fluctuations in proximity of the qubits are observed at <100 nm and >1 µm, respectively. The short-ranged fluctuations have a typical bandwidth of 2 × 10-4 and can be quantitatively linked to the compressive stressing action of the metal electrodes defining the qubits. By finite element mechanical simulations, it is estimated that this strain fluctuation is increased up to 6 × 10-4 at cryogenic temperature. The longer-ranged fluctuations are of the 10-3 order and are associated with misfit dislocations in the plastically relaxed virtual substrate. From this, energy variations of the light and heavy-hole energy maxima of the order of several 100 µeV and 1 meV are calculated for electrodes and dislocations, respectively. These insights over material-related inhomogeneities may feed into further modeling for optimization and design of large-scale quantum processors manufactured using the mainstream Si-based microelectronics technology.

Quantitative protein sensing with germanium THz-antennas manufactured using CMOS processes.

The development of a CMOS manufactured THz sensing platform could enable the integration of state-of-the-art sensing principles with the mixed signal electronics ecosystem in small footprint, low-cost devices. To this aim, in this work we demonstrate a label-free protein sensing platform using highly doped germanium plasmonic antennas realized on Si and SOI substrates and operating in the THz range of the electromagnetic spectrum. The antenna response to different concentrations of BSA shows in both cases a linear response with saturation above 20 mg/mL. Ge antennas on SOI substrates feature a two-fold sensitivity as compared to conventional Si substrates, reaching a value of 6 GHz/(mg/mL), which is four-fold what reported using metal-based metamaterials. We believe that this result could pave the way to a low-cost lab-on-a-chip biosensing platform.

Bio-physical mechanisms of dehydrating membranes of Acinetobacter baumannii linked to drought-resistance.

Acinetobacter baumanni, is an opportunistic nosocomial multi-drug resistant bacterium, which represents a threat for human health. This pathogen is able to persist in intensive care units thanks to its extraordinary resistance towards dehydration, whose mechanisms are unknown and enable it to easily spread through surfaces, contaminating also medical devices. In this article we reveal, with a multimodal approach, based on µ-R Spectroscopy, Gas Chromatography coupled to Mass Spectroscopy, Atomic Force Microscopy and Fluorescence Recovery After Photobleaching, the bio-physical mechanisms that the membrane of two A. baumannii strains undergoes during dehydration. Showing a substantial decoupling of the phase transition from liquid crystalline to gel phase from evidence of cell lysis. Such decoupling may be the core of the resistance of A. baumannii against dehydration and highlights the different ability to resist to drought between strains.

Three-Dimensional Interfacing of Cells with Hierarchical Silicon Nano/Microstructures for Midinfrared Interrogation of In Situ Captured Proteins.

Label-free optical detection of biomolecules is currently limited by a lack of specificity rather than sensitivity. To exploit the much more characteristic refractive index dispersion in the mid-infrared (IR) regime, we have engineered three-dimensional IR-resonant silicon micropillar arrays (Si-MPAs) for protein sensing. By exploiting the unique hierarchical nano- and microstructured design of these Si-MPAs attained by CMOS-compatible silicon-based microfabrication processes, we achieved an optimized interrogation of surface protein binding. Based on spatially resolved surface functionalization, we demonstrate controlled three-dimensional interfacing of mammalian cells with Si-MPAs. Spatially controlled surface functionalization for site-specific protein immobilization enabled efficient targeting of soluble and membrane proteins into sensing hotspots directly from cells cultured on Si-MPAs. Protein binding to Si-MPA hotspots at submonolayer level was unambiguously detected by conventional Fourier transform IR spectroscopy. The compatibility with cost-effective CMOS-based microfabrication techniques readily allows integration of this novel IR transducer into fully fledged bioanalytical microdevices for selective and sensitive protein sensing.

Growth Phase- and Desiccation-Dependent Acinetobacter baumannii Morphology: An Atomic Force Microscopy Investigation.

Acinetobacter baumannii has emerged as a major bacterial pathogen during the past three decades. The majority of the A. baumannii infections occur in hospitals and are caused by strains endowed with high desiccation tolerance, which represents an essential feature for the adaptation to the nosocomial environment. This work aims at investigating the desiccation response of the multidrug-resistant A. baumannii strain ACICU as a function of the bacterial growth phase and oxygen availability, by correlating bacterial survival with shape alterations. The three-dimensional morphological analysis of bacteria was carried out by atomic force microscopy (AFM), following the evolution of bacterial shape descriptors, such as the area, volume, roughness of individual cell membranes, and the cell cluster roughness, which exhibited peculiar and distinctive behavior as a function of the growth conditions. AFM images of A. baumannii ACICU cells revealed the prevalence of the coccoid morphology at all growth stages, with a tendency to reduce their size in the stationary phase, accompanied by a higher survival rate to air-drying. Moreover, cells harvested from the logarithmic phase featured a larger volume and resulted to be more sensitive to desiccation compared to the cells harvested at later growth stages. In addition, oxygen deprivation caused a significant decrease in cellular size and was associated with the formation of pores in the cell membrane, accompanied by a relative reduction in culturability after desiccation. Morphological plasticity and multidrug resistance may contribute to desiccation tolerance and therefore to persistence in the hospital setting.

Surface-enhanced Raman scattering (SERS)-based immunosystem for ultrasensitive detection of the 90K biomarker.

The research and the individuation of tumour markers in biological fluids are currently one of the main tools to support diagnosis, prognosis, and monitoring of the therapeutic response in oncology. Although the identification of tumour markers in asymptomatic patients is crucial for early diagnosis, its application is still limited by the relatively low sensitivity and the complexity of existing methods (i.e. ELISA, mass spectrometry). We developed an easy, fast, and ultrasensitive surface-enhanced Raman scattering (SERS)-based system, for the detection and quantitation of the LGALS3BP (90K) biomarker that was used as a model, based on the development of antibody-functionalized nanostructured gold surfaces. The detection system was effective for the ultrasensitive detection and characterization of samples of different biochemical compositions. In conclusion, this work could provide the foundation for the development of a medical diagnostic device with the highest predictive power when compared with the methods currently used in cancer diagnostics.

Ge(Sn) nano-island/Si heterostructure photodetectors with plasmonic antennas.

We report on photodetection in deep subwavelength Ge(Sn) nano-islands on Si nano-pillar substrates, in which self-aligned nano-antennas in the Al contact metal are used to enhance light absorption by means of local surface plasmon resonances. The impact of parameters such as substrate doping and device geometry on the measured responsivities are investigated and our experimental results are supported by simulations of the three-dimensional distribution of the electromagnetic fields. Comparatively high optical responsivities of about 0.1 A W-1 are observed as a consequence of the excitation of localized surface plasmons, making our nano-island photodetectors interesting for applications in which size reduction is essential.

Terahertz absorption-saturation and emission from electron-doped germanium quantum wells.

We study radiative relaxation at terahertz frequencies in n-type Ge/SiGe quantum wells, optically pumped with a terahertz free electron laser. Two wells coupled through a tunneling barrier are designed to operate as a three-level laser system with non-equilibrium population generated by optical pumping around the 1→3 intersubband transition at 10 THz. The non-equilibrium subband population dynamics are studied by absorption-saturation measurements and compared to a numerical model. In the emission spectroscopy experiment, we observed a photoluminescence peak at 4 THz, which can be attributed to the 3→2 intersubband transition with possible contribution from the 2→1 intersubband transition. These results represent a step towards silicon-based integrated terahertz emitters.

Photoluminescence from GeSn nano-heterostructures.

We investigate the distribution of Sn in GeSn nano-heteroepitaxial clusters deposited at temperatures well exceeding the eutectic temperature of the GeSn system. The 600 °C molecular beam epitaxy on Si-patterned substrates results in the selective growth of GeSn nano-clusters having a 1.4 ± 0.5 at% Sn content. These nano-clusters feature Sn droplets on their faceted surfaces. The subsequent deposition of a thin Ge cap layer induced the incorporation of the Sn atoms segregated on the surface in a thin layer wetting the nano-dots surface with 8 ± 0.5 at% Sn. The presence of this wetting layer is associated with a relatively strong photoluminescence emission that we attribute to the direct recombination occurring in the GeSn nano-dots outer region.

Advanced GeSn/SiGeSn Group IV Heterostructure Lasers.

Growth and characterization of advanced group IV semiconductor materials with CMOS-compatible applications are demonstrated, both in photonics. The investigated GeSn/SiGeSn heterostructures combine direct bandgap GeSn active layers with indirect gap ternary SiGeSn claddings, a design proven its worth already decades ago in the III-V material system. Different types of double heterostructures and multi-quantum wells (MQWs) are epitaxially grown with varying well thicknesses and barriers. The retaining high material quality of those complex structures is probed by advanced characterization methods, such as atom probe tomography and dark-field electron holography to extract composition parameters and strain, used further for band structure calculations. Special emphasis is put on the impact of carrier confinement and quantization effects, evaluated by photoluminescence and validated by theoretical calculations. As shown, particularly MQW heterostructures promise the highest potential for efficient next generation complementary metal-oxide-semiconductor (CMOS)-compatible group IV lasers.

A self-ordered, body-centered tetragonal superlattice of SiGe nanodot growth by reduced pressure CVD.

Self-ordered three-dimensional body-centered tetragonal (BCT) SiGe nanodot structures are fabricated by depositing SiGe/Si superlattice layer stacks using reduced pressure chemical vapor deposition. For high enough Ge content in the island (>30%) and deposition temperature of the Si spacer layers (T > 700 °C), we observe the formation of an ordered array with islands arranged in staggered position in adjacent layers. The in plane periodicity of the islands can be selected by a suitable choice of the annealing temperature before the Si spacer layer growth and of the SiGe dot volume, while only a weak influence of the Ge concentration is observed. Phase-field simulations are used to clarify the driving force determining the observed BCT ordering, shedding light on the competition between heteroepitaxial strain and surface-energy minimization in the presence of a non-negligible surface roughness.

In vitro biocompatibility study of sub-5 nm silica-coated magnetic iron oxide fluorescent nanoparticles for potential biomedical application.

Magnetic iron oxide nanoparticles (IONPs), for their intriguing properties, have attracted a great interest as they can be employed in many different biomedical applications. In this multidisciplinary study, we synthetized and characterized ultrafine 3 nm superparamagnetic water-dispersible nanoparticles. By a facile and inexpensive one-pot approach, nanoparticles were coated with a shell of silica and contemporarily functionalized with fluorescein isothiocyanate (FITC) dye. The obtained sub-5 nm silica-coated magnetic iron oxide fluorescent (sub-5 SIO-Fl) nanoparticles were assayed for cellular uptake, biocompatibility and cytotoxicity in a human colon cancer cellular model. By confocal microscopy analysis we demonstrated that nanoparticles as-synthesized are internalized and do not interfere with the CaCo-2 cell cytoskeletal organization nor with their cellular adhesion. We assessed that they do not exhibit cytotoxicity, providing evidence that they do not affect shape, proliferation, cellular viability, cell cycle distribution and progression. We further demonstrated at molecular level that these nanoparticles do not interfere with the expression of key differentiation markers and do not affect pro-inflammatory cytokines response in Caco-2 cells. Overall, these results showed the in vitro biocompatibility of the sub-5 SIO-Fl nanoparticles promising their safe employ for diagnostic and therapeutic biomedical applications.

Structural and optical characterization of GaAs nano-crystals selectively grown on Si nano-tips by MOVPE.

We present the nanoheteroepitaxial growth of gallium arsenide (GaAs) on nano-patterned silicon (Si) (001) substrates fabricated using a CMOS technology compatible process. The selective growth of GaAs nano-crystals (NCs) was achieved at 570 °C by MOVPE. A detailed structure and defect characterization study of the grown nano-heterostructures was performed using scanning transmission electron microscopy, x-ray diffraction, micro-Raman, and micro-photoluminescence (µ-PL) spectroscopy. The results show single-crystalline, nearly relaxed GaAs NCs on top of slightly, by the SiO2-mask compressively strained Si nano-tips (NTs). Given the limited contact area, GaAs/Si nanostructures benefit from limited intermixing in contrast to planar GaAs films on Si. Even though a few growth defects (e.g. stacking faults, micro/nano-twins, etc) especially located at the GaAs/Si interface region were detected, the nanoheterostructures show intensive light emission, as investigated by µ-PL spectroscopy. Achieving well-ordered high quality GaAs NCs on Si NTs may provide opportunities for superior electronic, photonic, or photovoltaic device performances integrated on the silicon technology platform.

Bi-modal nanoheteroepitaxy of GaAs on Si by metal organic vapor phase epitaxy.

Nano-heteroepitaxial growth of GaAs on Si(001) by metal organic vapor phase epitaxy was investigated to study emerging materials phenomena on the nano-scale of III-V/Si interaction. Arrays of Si nano-tips (NTs) embedded in a SiO2 matrix were used as substrates. The NTs had top Si openings of 50-90 nm serving as seeds for the selective growth of GaAs nano-crystals (NCs). The structural and morphological properties were investigated by high resolution scanning electron microscopy, atomic force microscopy, electron backscatter diffraction, x-ray diffraction, and high resolution scanning transmission electron microscopy. The GaAs growth led to epitaxial NCs featuring a bi-modal distribution of size and morphology. NCs of small size exhibited high structural quality and well-defined {111}-{100} faceting. Larger clusters had less regular shapes and contained twins. The present work shows that the growth of high quality GaAs NCs on Si NTs is feasible and can provide an alternate way to the integration of compound semiconductors with Si micro- and opto-electronics technology.

Selective Epitaxy of InP on Si and Rectification in Graphene/InP/Si Hybrid Structure.

The epitaxial integration of highly heterogeneous material systems with silicon (Si) is a central topic in (opto-)electronics owing to device applications. InP could open new avenues for the realization of novel devices such as high-mobility transistors in next-generation CMOS or efficient lasers in Si photonics circuitry. However, the InP/Si heteroepitaxy is highly challenging due to the lattice (∼8%), thermal expansion mismatch (∼84%), and the different lattice symmetries. Here, we demonstrate the growth of InP nanocrystals showing high structural quality and excellent optoelectronic properties on Si. Our CMOS-compatible innovative approach exploits the selective epitaxy of InP nanocrystals on Si nanometric seeds obtained by the opening of lattice-arranged Si nanotips embedded in a SiO2 matrix. A graphene/InP/Si-tip heterostructure was realized on obtained materials, revealing rectifying behavior and promising photodetection. This work presents a significant advance toward the monolithic integration of graphene/III-V based hybrid devices onto the mainstream Si technology platform.