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The unique electrical properties of silicon nitride have increased the applications in microelectronics, especially in the manufacture of integrated circuits. Silicon nitride is mainly used as a passivation barrier against water and sodium ion diffusion and as an electrical insulator between polysilicon layers in capacitors. The interface with different materials, like semiconductors and metals, through soldering may induce residual strains in the final assembly. Therefore, the dentification and quantification of strain becomes strategically important in optimizing processes to enhance the performance, duration, and reliability of devices. This work analyzes the thermomechanical local strain of semiconductor materials used to realize optoelectronic components. The strain induced in the β-Si 3 N 4 chips by the soldering process performed with AuSn pre-formed on copper substrates is investigated by Raman spectroscopy in a temperature range of -50 to 180 °C. The variation in the position of the E 1g Raman peak allows the calculation of the local stress present in the active layer, from which the strain induced during the assembly process can be determined. The main reason for the strain is attributed to the differences in thermal expansion coefficients among the various materials involved, particularly between the chip, the interconnection material, and the substrate. Micro-Raman spectroscopy allows for the assessment of how different materials and assembly processes impact the strain, enabling more informed decisions to optimize the overall device structure.

Graphyne- and graphdiyne-like model systems have attracted much attention from many structural, theoretical, and synthetic scientists because of their promising electronic, optical, and mechanical properties, which are crucially affected by the presence, abundance and distribution of triple bonds within the nanostructures. In this work, we performed the two-step bottom-up on-surface synthesis of graphyne- and graphdiyne-based molecular wires on the Au(111). We characterized their structural and chemical properties both in situ (UHV conditions) through STM and XPS and ex situ (in air) through Raman spectroscopy. By comparing the results with the well-known growth of poly( p -phenylene) wires (namely the narrowest armchair graphene nanoribbon), we were able to show how to discriminate different numbers of triple bonds within a molecule or a nanowire also containing phenyl rings. Even if the number of triple bonds can be effectively determined from the main features of STM images and confirmed by fitting the C1s peak in XPS spectra, we obtained the most relevant results from ex situ Raman spectroscopy, despite the sub-monolayer amount of molecular wires. The detailed analysis of Raman spectra, combined with density functional theory (DFT) simulations, allowed us to identify the main features related to the presence of isolated (graphyne-like systems) or at least two conjugated triple bonds (graphdiyne-like systems). Moreover, other spectral features can be exploited to understand if the chemical structure of graphyne- and graphdiyne-based nanostructures suffered unwanted reactions. As in the case of sub-monolayer graphene nanoribbons obtained by on-surface synthesis, we demonstrate that Raman spectroscopy can be used for a fast, highly sensitive and non-destructive determination of the properties, the quality and the stability of the graphyine- and graphdiyne-based nanostructures obtained by this highly promising approach.

The main challenge for solar cell devices is harvesting photons beyond the visible by reaching the red-edge (650-780 nm). Dye-sensitized solar cell (DSSC) devices combine the optical absorption and the charge separation processes by the association of a sensitizer as a light-absorbing material (dye molecules, whose absorption can be tuned and designed) with a wide band gap nanostructured semiconductor. Conformational and environmental effects (i.e., solvent, pH) can drastically influence the photophysical properties of molecular dyes. This study proposes a combined experimental and computational approach for the comprehensive investigation of the electronic and vibrational properties of a unique class of organic dye compounds belonging to the family of red-absorbing dyes, known as squaraines. Our focus lies on elucidating the intricate interplay between the molecular structure, vibrational dynamics, and optical properties of squaraines using state-of-the-art density functional theory calculations and spectroscopic techniques. Through systematic vibrational and optical analyses, we show that (i) the main absorption peak in the visible range is influenced by the conformational and protonation equilibria, (ii) the solvent polarity tunes the position of the UV-vis absorption, and (iii) the vibrational spectroscopy techniques (infrared and Raman) can be used as informative tools to distinguish between different conformations and protonation states. This comprehensive understanding offers valuable insights into the design and optimization of squaraine-based DSSCs for enhanced solar energy conversion efficiency., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

Integrated circuits are created by interfacing different materials, semiconductors, and metals, which are appropriately deposited or grown on substrates and layers soldered together. Therefore, the characteristics of starting materials and process temperatures are of great importance, as they can induce residual strains in the final assembly. Identifying and quantifying strain becomes strategically important in optimizing processes to enhance the performance, duration, and reliability of final devices. This work analyzes the thermomechanical local strain of semiconductor materials used to realize LED modules for lighting applications. Gallium Nitride active layers grown on sapphire substrates and Si chips are assembled by soldering with eutectic AuSn on copper substrates and investigated by Raman spectroscopy in a temperature range of -50 to 180 °C. From the Raman mapping of many different samples, it is concluded that one of the leading causes of strain in the GaN layer can be attributed to the differences in the thermal expansion coefficient among the various materials and, above all, among the chip, interconnection material, and substrate. These differences are responsible for forces that slightly bend the chip, causing strain in the GaN layer, which is most compressed in the central region of the chip and slightly stretched in the outer areas.

The accurate determination of the local temperature is one of the most important challenges in the field of nanotechnology and nanomedicine. For this purpose, different techniques and materials have been extensively studied in order to identify both the best-performing materials and the techniques with greatest sensitivity. In this study, the Raman technique was exploited for the determination of the local temperature as a non-contact technique and titania nanoparticles (NPs) were tested as nanothermometer Raman active material. Biocompatible titania NPs were synthesized following a combination of sol-gel and solvothermal green synthesis approaches, with the aim of obtaining pure anatase samples. In particular, the optimization of three different synthesis protocols allowed materials to be obtained with well-defined crystallite dimensions and good control over the final morphology and dispersibility. TiO 2 powders were characterized by X-ray diffraction (XRD) analyses and room-temperature Raman measurements, to confirm that the synthesized samples were single-phase anatase titania, and using SEM measurements, which clearly showed the nanometric dimension of the NPs. Stokes and anti-Stokes Raman measurements were collected, with the excitation laser at 514.5 nm (CW Ar/Kr ion laser), in the temperature range of 293-323 K, a range of interest for biological applications. The power of the laser was carefully chosen in order to avoid possible heating due to the laser irradiation. The data support the possibility of evaluating the local temperature and show that TiO 2 NPs possess high sensitivity and low uncertainty in the range of a few degrees as a Raman nanothermometer material.

This paper reports on the fabrication and characterization of a plasmonic/sol-gel sensor for the detection of aromatic molecules. The sol-gel film was engineered using polysilsesquioxanes groups to capture the analyte, through π-π interaction, and to concentrate it close to the plasmonic surface, where Raman amplification occurs. Xylene was chosen as an analyte to test the sensor. It belongs to the general class of volatile organic compounds and can be found in water or in the atmosphere as pollutants released from a variety of processes; its detection with SERS is typically challenging, due to its low affinity toward metallic surfaces. The identification of xylene was verified in comparison with that of other aromatic molecules, such as benzene and toluene. Investigations were carried out on solutions of xylene in cyclohexane, using concentrations in the range from 0 to 800 mM, to evaluate the limit of detection (LOD) of about 40 mM.