Photothermal Spectroscopy Research Articles

Photothermal Spectroscopy in Attenuated Total Internal Reflection Geometry by Polarization Rotation and Deflection

Photothermal Spectroscopy in Attenuated Total Internal Reflection Geometry by Polarization Rotation and Deflection

Hollow-Core Fiber-Based Mid-Infrared Photothermal Spectroscopy for Multi-Component Gas Sensing

Hollow-Core Fiber-Based Mid-Infrared Photothermal Spectroscopy for Multi-Component Gas Sensing

A Quartz-Enhanced Photothermal Spectroscopy for C2H2 and CH4 Detection Based on Time Division Multiplexing Technology

A Quartz-Enhanced Photothermal Spectroscopy for C₂H₂ and CH₄ Detection Based on Time Division Multiplexing Technology

Rapid Microwave Annealing for Improved Crystallinity and Morphology of Perovskite Materials

Perovskite solar cells are gaining significant attention for their remarkable power conversion efficiency, cost‐effective processing, and material abundance. This study investigates the impact of rapid microwave annealing on the crystallinity and morphology of MAPbI3 films on FTO glass substrates. Multifaceted characterization techniques, including field emission scanning electron microscopy (FESEM), X‐ray diffraction (XRD), UV–Vis spectroscopy, photothermal deflection spectroscopy (PDS), and steady‐state photoluminescence (PL) measurements are used to compare microwave‐annealed samples with traditional hotplate‐annealed samples. Microwave annealing yields significantly larger crystals in shorter processing times, suggesting enhanced crystallinity, as evidenced by SEM analysis and XRD data. UV‐Vis and PDS measurements indicate improved optical properties and reduced sub‐bandgap states, while PL results suggest diminished nonradiative recombination in microwave‐annealed samples. However, a partial film detachment has been observed at higher microwave powers, a phenomenon explained by COMSOL simulations. These findings demonstrate rapid microwave annealing as an energy‐efficient and cost‐effective alternative while highlighting the need for further optimization to address film degradation issues, which remain a significant challenge. This research supports the potential for scalable, high‐quality perovskite material production, facilitating large‐scale production and commercialization of next‐generation solar cells.

Amide groups in 3.7 billion years old liquid inclusions

Carbon with depleted d13C (down to − 25.6‰ VPDB) found in > 3.7 billion year old metamorphic sediments from the Isua Supracrustal Belt, Southwestern Greenland, has been proposed to represent the oldest remains of life on Earth. Graphitic inclusions within garnet porphyroblasts from this locality have been shown to associate with elements consistent with biogenic remains. In this report, we focus on certain liquid inclusions found in the Isua garnets, characterizing their chemical composition using atomic force microscopy, AFM-based infrared spectroscopy, optical photothermal infrared spectroscopy, Raman spectroscopy, and time-of-flight secondary ion mass spectrometry. Our results show that the liquid inclusions contain functional groups consisting of carbon, nitrogen, and oxygen in a configuration similar to amide functional groups. We suspect that the amide groups formed from N, O and C-containing volatile components that were released from the original kerogenous material enclosed in the garnets, as this was graphitized during thermal maturation. This is consistent with the observed inclusion assemblage of solid graphitic and viscous fluid inclusions alike. Our observations are compatible with the inclusions forming from biogenic precursor material, and when considered alongside previous reports on the carbonaceous material in the Isua metamorphic sediments, these and our study collectively indicate that the carbonaceous material in the Isua metasediments represents the oldest traces of life on Earth.

Deep Traps in AlN Hydride Vapor Phase Epitaxy Film on Low-Temperature AlN/Sapphire

Deep trap states were examined in c-plane, Al-polar AlN epilayers, deposited via metal organic chemical vapor deposition on 270 nm thick AlN buffer layers on sapphire substrates. Contacts were created using e-beam deposited Ni through a shadow mask, with I-V characteristics revealing a trapped limited current (TLC) regime and voltage-dependent hysteresis upon light-emitting diode illumination. Thermally stimulated current and photothermal ionization current spectroscopy measurements demonstrated a prominent trap activation energy of approximately 0.75 eV and additional trap energies of 0.6, 0.4, 0.25, 1.05, and 1.1 eV. The observed differences in photocurrent responses between forward and reverse biases suggest that forward bias induces electron trapping at deeper levels, influencing the TLC behavior. Comparisons with bulk n-type AlN crystals from previous studies show similarities in deep trap spectra, suggesting commonality in trap characteristics across different AlN samples.

O-PTIR spectroscopy for characterizing active pharmaceutical ingredient specific particle size distributions of nasal spray suspension products

Evaluation of the particle size distribution (PSD) of active pharmaceutical ingredients (APIs) in nasal suspension products is challenging due to the presence of both API and excipients. To characterize these intricate formulations, it is essential to have sophisticated analytical methods that offer high spatial resolution and the ability to chemically pinpoint and map out the presence of API particles. However, such advanced techniques have not been documented for nasal formulations yet.In this proof-of-concept study, we investigated the utility of optical photothermal infrared spectroscopy (O-PTIR) to analyze the PSD of commercially available Nasonex® and its generic Azonaire® nasal mometasone furoate (MM) suspensions. Simultaneous O-PTIR and Raman spectra, as well as IR chemical maps, were collected from the particles in both formulations. Spatially resolved spectra from the particles confirmed the presence of peaks related to MM (1727 cm−1, 1661 cm−1, and 1122 cm−1) and excipient microcrystalline cellulose (MCC) (1061 cm−1). The PSD of MM particles was characterized using chemical maps specific to MM (1661 cm−1) and automated imaging. Results confirmed that the PSD of both formulations were comparable. Spectral analysis also revealed the presence of free MM, free MCC, and particles containing co-localized MM and MCC.For suspension-based nasal products, O-PTIR enables the measurement of API PSD, which is critical for formulators in developing nasal suspension products. This approach holds potential as an innovative complimentary analytical tool that could diminish the need for extensive clinical endpoint bioequivalence studies when evaluating the comparability of generic and brand-name nasal suspension products.

Signal enhancement of the gas detection based on quartz-enhanced photothermal spectroscopy technology.

This paper presents an improved gas sensor based on the dual-excitation of quartz-enhanced photothermal spectroscopy (QEPTS) using a single quartz tuning fork (QTF) for signal detection. The silver coating on one side of the QTF was chemically etched to increase the laser power interacted with QTF for QEPTS signal excitation. By etching the silver coating on one side of QTF, the reflection structure between the silver coating of the other side of QTF and the external flat mirror was established. The device uses an absorption gas cell with an optical range length of 3 m, making the laser beam interact with the gas more completely and posing more gas concentration information. Acetylene was selected as the target gas to verify the performance of the sensor. The experimental results show that the signal amplitude with a flat mirror was 1.41 times that without a flat mirror, and 2.47 times that of traditional QEPTS sensor. The system has a minimum detection limit (MDL) of 1.10 ppmv, corresponding to a normalized noise equivalent absorption coefficient (NNEA) of 7.14 × 10-9 cm-1·W·Hz-1/2. Allan variance analysis results show that when the integration time is 700 s, the MDL of the system is 0.21 ppmv. The proposed gas sensor can play an important role on detecting trace gas in many fields.

Upgrading and Enhancement of Recycled Polyethylene Terephthalate with Chain Extenders: In-Depth Material Characterization.

Chemical chain extenders (CEs) can be used to restore the properties of recycled low-molecular-weight polyethylene terephthalate (PET). The aim of this work is to investigate the influence of the type and concentration of the CEs Joncryl and pyromellitic dianhydride (PMDA) on the viscosity and other rheological properties with a unique combination of different methods based on industrial samples originating from recycled PET bottles and trays. The resulting chain-extended thermoplastics were characterized by a combination of differential scanning calorimetry, viscometry, cone plate rheometry, pyrolysis-gas chromatography-mass spectroscopy, optical photothermal infrared spectroscopy, 13C solid-state- and 1H NMR liquid spectroscopy, and size exclusion chromatography. For a recycled PET mixture containing bottle and tray materials, our investigations have shown that a significantly better effect for chain elongation can be achieved with Joncryl compared to PMDA. This can presumably be attributed to water molecules formed during the use of PMDA, which accelerate the degradation of PET. The storage modulus values are therefore significantly higher for the samples with Joncryl compared to PMDA. The results of this study show that chain extension with Joncryl proceeds better compared to the reaction with PMDA.

Analysis of automotive paint layers on plastic substrates using chemical imaging μ-FTIR and O-PTIR microspectroscopy.

Automobile paint chips are a crucial piece of trace evidence for forensic investigators. This is because automotive paints are composed of multiple layers, including the primer, basecoat, and clearcoat, each of which has its own chemical composition that can vary by vehicle make, model, year, and manufacturing plant. Thus, Fourier-transform infrared (FTIR) spectral databases for automobile paint systems have been established to aid law enforcement in, for example, narrowing search parameters for a suspect's vehicle. Recently, car manufacturers have implemented primers on plastic substrates that are much thinner (~5 μm) than those on metal substrates, making it more difficult to manually separate for analyses. Here, we evaluated FTIR microspectroscopy (μ-FTIR) and optical photothermal infrared spectroscopy (O-PTIR) to chemically image cross sections of paint chips without manually separating the layers. For μ-FTIR, transmission and transflection modes provided the highest quality spectra compared to reflection and μ-ATR analyses. Point analysis was preferable to chemical imaging, as peaks were identified in the point (MCT) detector's lower spectral range that was below the imaging (FPA) detector's cutoff, such as those associated with titanium dioxide. Reduced spectral range can lead to a similar issue in O-PTIR analyses depending on instrument configuration. However, its complementary Raman spectra showed strong titanium dioxide peaks, providing an alternate means of identification. Both techniques are likely to become more relevant as they are non-destructive and avoid manual separation of the layers. O-PTIR is particularly well-suited for analysis of the thin primer layer due to its superior spatial resolution.

Micro quartz crystal tuning fork based photothermal spectroscopy for trace gas detection

This paper describes a micro-quartz crystal tuning fork (M-QCTF) hermetically sealed in a vacuum environment for the development of low-cost, high-sensitivity photothermal detectors. Compared with conventional QCTF-based photothermal detectors exposed to air, the M-QCTF detector with the approximate stable characteristic resonance frequency (∼32763 Hz) has a small size and high quality factor of 19840. Utilizing the M-QCTF detector and direct absorption spectroscopy (DAS) technology, a gas detection system has been successfully implemented. NO2 was selected as the target gas for evaluating the performance of the M-QCTF based gas sensor. The results indicate a strong linear relationship between the normalized absorbance amplitude of the M-QCTF and the gas concentration, achieving an optimal measurement precision of 117 ppb with an integration time of 230 s. Furthermore, the vacuum packaging structure of the M-QCTF provides advantages such as easy system integration, low cost, and robust anti-interference capability.

Micro-Ring Resonator Assisted Photothermal Spectroscopy of Water Vapor.

We demonstrated, for the first time, micro-ring resonator assisted photothermal spectroscopy measurement of a gas phase sample. The experiment used a telecoms wavelength probe laser that was coupled to a silicon nitride photonic integrated circuit using a fibre array. We excited the photothermal effect in the water vapor above the micro-ring using a 1395 nm diode laser. We measured the 1f and 2f wavelength modulation response versus excitation laser wavelength and verified the power scaling behaviour of the signal.

Characterizations of Subbandgap Optical Absorption in Undoped‐GaN and 90 nm‐Thick Al1−xInxN Thin Film on Sapphire Substrates Grown by Metal–Organic Chemical Vapor Deposition

Subbandgap optical absorption (SOA) in undoped GaN and 90 nm‐thick Al1−xInxN thin films grown on sapphire substrates is investigated using photothermal deflection spectroscopy (PDS) and photoluminescence (PL). An Al1−xInxN alloy (x = 0.17) is grown on a GaN/sapphire template by metal–organic chemical vapor deposition (MOCVD), and the SOA is observed using PDS. To develop an estimation method for the absorption coefficient (α) of SOA in GaN and Al1−xInxN thin films, the use of a thick GaN substrate is proposed, which is grown by hydride vapor‐phase epitaxy, as a converter of the PDS signal intensity to α, and the accuracies of the estimated α are discussed. Comparing the PDS and PL results, it is revealed that nonradiative recombination centers leading to the reduction of the near‐band‐edge PL intensity are not the dominant sources of SOAs in GaN. Other in‐gap states formed by impurities and/or their complexes with vacancy‐type defects are possible sources of a large SOA in the MOCVD‐grown GaN template. Considering the PDS results and reported peak reflectivity of Al1−xInxN/GaN distributed Bragg reflectors, the α value of sub‐100 nm‐thick Al1−xInxN alloy grown on GaN/sapphire template is expected to be ≈100 cm−1 or less below 3.0 eV.

Taking a Tailored Approach to Material Design: A Mechanistic Study of the Selective Localization of Phase-Separated Graphene Microdomains.

To achieve multifunctional properties using nanocomposites, selectively locating nanofillers in specific areas by tailoring a mixture of two immiscible polymers has been widely investigated. Forming a phase-separated structure from entirely miscible molecules is rarely reported, and the related mechanisms to govern the formation of assemblies from molecules have not been fully resolved. In this work, a novel method and the underlying mechanism to fabricate self-assembling, bicontinuous, biphasic structures with localized domains made up of amine-functionalized graphene nanoplatelets are presented, involving the tailoring of compositions in a liquid processable multicomponent epoxy blend. Kinetics studies were carried out to investigate the differences in reactivity of various epoxy-hardener pairs. Molecular dynamics simulations and in situ optical photothermal infrared spectroscopy measurements revealed the trajectories of different components during the early stages of polymerization, supporting the migration (phase behavior) of each component during the curing process. Confirmed by the phase structure and the correlated chemical maps down to the submicrometer level, it is believed that the bicontinuous phase separation is driven by the change of the miscibility between various building blocks forming during polymerization, leading to the formation of nanofiller domains. The proposed morphology evolution mechanism is based on combining solubility parameter calculations with kinetics studies, and preliminary experiments are performed to validate the applicability of the mechanism of selectively locating nanofillers in the phase-separated structure. This provides a simple yet sophisticated engineering model and a roadmap to a mechanism for fabricating phase-separated structures with nanofiller domains in nanocomposite films.

Advanced optical photothermal infrared spectroscopy for comprehensive characterization of microplastics from intravenous fluid delivery systems

Growing attention is being directed towards exploring the potential harmful effects of microplastic (MP) particles on human health. Previous reports on human exposure to MPs have primarily focused on inhalation, ingestion, transdermal routes, and, potentially, transplacental transfer. The intravenous transfer of MP particles in routine healthcare settings has received limited exploration in existing literature. Standard hospital IV system set up with 0.9 % NaCl in a laminar flow hood with MP contamination precautions. Various volumes of 0.9 % NaCl passed through the system, some with a volumetric pump. Fluid filtered with Anodisc filters washed with isopropyl alcohol. The IV cannula was immersed in Mili-Q water for 72 h to simulate vein conditions. Subsequently, the water was filtered and washed. Optical photothermal infrared (O-PTIR) microspectroscopy is used to examine filters for MP particles. All filters examined from the IV infusion system contained MP particles, including MPs from the polymer materials used in the manufacture of the IV delivery systems (polydimethylsiloxane, polypropylene, polystyrene, and polyvinyl chloride) and MP particles arising from plastic resin additives (epoxy resin, polyamide resin, and polysiloxane-containing MPs). The geometric mean from the extrapolated result data indicated that approximately 0.90 MP particles per mL of 0.9 % NaCl solution can be administered through a conventional IV infusion system in the absence of a volumetric pump. However, with the implementation of a pump, this value may increase to 1.57 particles per mL. Notably, over 72 h, a single cannula was found to release approximately 558 MP particles including polydimethylsiloxane, polysiloxane-containing MPs, polyamide resin, and epoxy resin. Routine IV infusion systems release microplastics. MP particles are also released around IV cannulas, suggesting transfer into the circulatory system during standard IV procedures.

Frustrated-Laser-Induced Thermal Starting Plumes in Fresh and Salt Water

The results of a photothermal spectroscopy technique that effectively images convective and conductive heat flow in liquids via a thermal lensing effect are described. Pure water; sodium chloride solutions at salinities of approximately 5, 15, 25, and 35 g/kg; and an artificial seawater of 35 g/kg were studied across a range of temperatures. This system was studied because of the importance of thermal pluming in seawater. ‘Frustrated’ thermal starting plumes were observed near the temperature of maximum density. The physical characteristics of these thermal starting plumes are reported.

Evaluation of defect density in bulk gallium nitrides by photothermal deflection spectroscopy and steady-state photocapacitance methods

Bulk GaN samples were characterized by both photothermal deflection spectroscopy (PDS) and steady-state photocapacitance (SSPC) methods. The PDS signal intensity in the bandgap was found to correlate quantitatively with the defect density estimated by the SSPC method. The defect density of GaN bulks fabricated by hydride vapor phase epitaxy (HVPE) was decreased by controlling the incorporation of carbon and silicon impurities. Differences in the reciprocal of the slope near the valence band maximum and the signal intensity in the bandgap among HVPE GaN bulks could be detected by PDS, although they had the same crystalline quality. PDS can be used to evaluate the GaN bulks that have been improved with a highly insulative property caused by Fe- doping or low carbon incorporation.

Balanced-detection interferometric cavity-assisted photothermal spectroscopy via collimating fiber-array integration

This work reports on the implementation of a fiber-array with attached microlenses in the balanced-detection Interferometric Cavity-Assisted Photothermal Spectroscopy (ICAPS) scheme, enabling a highly compact probe laser beam path. The sample probe and the reference beam were coupled into a 1-mm spaced Fabry-Perot interferometer with a parallel beam separation of only 1.25 mm. A quantum cascade laser was used to induce photothermal waves, which were detected via a sample probe beam. A reference probe beam was used to realize balanced detection, allowing for significant noise reduction. The sensor’s metrological figures of merit were evaluated by detection of nitric oxide. For the targeted absorption band centered at 1900.08 cm−1 a 1 σ minimum detection limit of 64 ppbv was achieved with a 1-second integration time. This performance corresponds to a normalized noise equivalent absorption of 5.7 ×10−8 cm−1 W Hz−1/2.

Comparison of three titanium-precursors for atomic-layer-deposited TiO2 for passivating contacts on silicon

Atomic layer-deposited (ALD) TiO2 thin films on silicon were deposited using titanium tetrachloride (TiCl4), titanium tetraisopropoxide (TTIP), and tetrakis(dimethylamino)titanium (TDMAT) together with water vapor as the oxidant at temperatures ranging between 75 and 250 °C. The Si surface passivation quality of as-deposited and isothermally annealed samples was compared using photoconductance lifetime measurements in order to calculate their effective surface recombination velocities Seff. A low Seff of 3.9 cm/s (J0s=24fA/cm2) is achieved for as-deposited TiCl4-TiO2 at 75 °C when a chemically grown (i.e., from RCA cleaning) SiOx interface layer is present. Depositing TTIP-TiO2 at 200 °C on a chemically grown SiOx interface layer yields equivalent Seff values; however, in this case, TTIP-TiO2 requires a 5–15 min postdeposition forming gas anneal at 250 °C. In contrast, TDMAT-TiO2 was not found to provide a similar level of passivation with/without a chemically grown SiOx interface layer and postdeposition anneal. Modeling of the effective lifetime curves was used to determine the magnitude of the effective charge densities Qf in the TiO2 films. In all cases, Qf was found to be of the order of ∼1011 q cm−2, meaning field-effect passivation arising from ALD TiO2 is relatively weak. By comparing the material properties of the various TiO2 films using ellipsometry, photothermal deflection spectroscopy, Raman spectroscopy, elastic recoil detection analysis, x-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy, we find experimental support for the role of Cl (in conjunction with hydrogen) playing a beneficial role in passivating dangling bond defects at the Si surface. It is concluded that low deposition temperature TiCl4 processes are advantageous, by providing the lowest Seff without any postanneal and a comparatively high growth per cycle (GPC).

Mid-Infrared Photothermal Spectroscopy for the Detection of Caffeine in Beverages.

Caffeine is the most widely consumed stimulant and is the subject of significant ongoing research and discussions due to its impact on human health. The industry's need to comply with country-specific food and beverage regulations underscores the importance of monitoring caffeine levels in commercial products. In this study, we propose an alternative technique for caffeine analysis that relies on mid-infrared laser-based photothermal spectroscopy (PTS). PTS exploits the high-power output of the quantum cascade laser (QCL) sources to enhance the sensitivity of the mid-IR measurement. The laser-induced thermal gradient in the sample scales with the analytes' absorption coefficient and concentration, thus allowing for both qualitative and quantitative assessment. We evaluated the performance of our experimental PTS spectrometer, incorporating a tunable QCL and a Mach-Zehnder interferometer, for detecting caffeine in coffee, black tea, and an energy drink. We calibrated the setup with caffeine standards (0.1-2.5 mg mL-1) and we benchmarked the setup's capabilities against gas chromatography (GC) and Fourier-transform infrared (FTIR) spectroscopy. Quantitative results aligned with GC analysis, and limits of detection matched the research-grade FTIR spectrometer, indicating an excellent performance of our custom-made instrument. This method offers an alternative to established techniques, providing a platform for fast, sensitive, and non-destructive analysis without consumables as well as with high potential for miniaturization.