An approach is described for spectrally parallel hyperspectral mid-infrared imaging with spatial resolution dictated by fluorescence imaging. Quantum cascade laser (QCL)-based dual-comb mid-infrared spectroscopy enables the acquisition of infrared spectra at high speed (<1 millisecond) through the generation of optical beat patterns and radio-frequency detection. The high-speed nature of the spectral acquisition is shown to support spectral mapping in microscopy measurements. Direct detection of the transmitted infrared beam yields high signal-to-noise spectral information, but long infrared wavelengths impose low diffraction-limited spatial resolution. The use of fluorescence detected photothermal infrared (F-PTIR) imaging provides high spatial resolution tied directly to the integrated IR absorption. Computational imaging using a multi-agent consensus equilibrium (MACE) approach combines the high spatial resolution of F-PTIR and the high spectral information of dual-comb infrared transmission in a single optimized equilibrium hyperspectral data cube.
more »
« less
Analysis of automotive paint layers on plastic substrates using chemical imaging μ‐FTIR and O‐PTIR microspectroscopy
Abstract 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.
more »
« less
- Award ID(s):
- 2116597
- PAR ID:
- 10539786
- Publisher / Repository:
- American Academy of Forensic Science
- Date Published:
- Journal Name:
- Journal of Forensic Sciences
- Volume:
- 69
- Issue:
- 5
- ISSN:
- 0022-1198
- Page Range / eLocation ID:
- 1730 to 1739
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Emerging technology combining spectroscopy with microscopy is advancing the analysis of trace evidence with the potential to revolutionize forensic microscopy and excite a new generation of forensic microscopists. In this laboratory experiment, developed for undergraduate forensic chemistry and instrumental analysis courses, students use Fourier transform infrared (micro)spectroscopy (µ-FTIR) to analyze mock forensic samples commonly encountered at crime scenes, including latent fingerprints (laced with ibuprofen to mimic an illicit drug), vehicle paint chips, and acrylic fibers. Unlike light microscopy, µ-FTIR provides information on the spatial distribution and chemical nature of the sample. Learning objectives were to reinforce key concepts covered in the classroom, including collection and preparation of trace evidence, forensic microscopy, and vibrational spectroscopy, as well as to provide students hands-on experience using a state-of-the-art instrument. Students prepared the fingerprint and fiber samples for analysis, whereas the paint chip was previously cross-sectioned to save time. The students collected and processed their own data, including generating chemical distribution maps. Student responses to the exercise were positive and reports written by the students demonstrated an increased awareness of the capabilities of FTIR microscopy and chemical imaging. Overall, the exercise helped remove the “black box” mentality, where students analyze samples without understanding the fundamentals of the technique, which is so important to recognize poor data quality and troubleshoot instruments. This report describes the laboratory exercise and student experience, and includes data and chemical images collected by students, and aspects of the experiment that could be modified to improve learning outcomes.more » « less
-
Abstract Carbon-doped silicon oxide (CDO) thin films as low dielectric constant materials were deposited on both n-type silicon (Si) (100) and indium tin oxide coated polyethylene naphthalate (ITO/PEN) substrates, using the plasma-enhanced chemical vapor deposition of tetrakis(trimethylsilyoxy)silane (TTMSS) precursor. Chemical structures of the CDO films were analyzed by using FTIR (Fourier transformation infrared) spectroscopy and XPS (X-ray photoelectron spectroscopy). The chemical bonds related with hydrocarbon and Si–O were the main characteristics of the CDO films. The prominent peaks from the FTIR spectra included Si–O–Si stretching, Si–CH3 bending, Si–(CH3)x stretching, and CHx stretching modes. XPS spectra composed of the O1s, C1s, and Si2p electron orbitals were used to quantitatively analyze the elemental composition of the CDO films. The growth mechanisms of CDO films were dependent on the substrate type. For the ITO/PEN substrate, the lack of Si atoms on the ITO surface made difficulty in forming initial Si–O bonds, resulting in insufficient Si–O–Si structure. In comparison, the CDO films could grow easily on Si substrates due to pre-existing Si–O bonds on the surface. The chemical structures of the CDO films are expected to affect electrical and mechanical performances.more » « less
-
Standoff detection based on optical spectroscopy is an attractive method for identifying materials at a distance with very high molecular selectivity. Standoff spectroscopy can be exploited in demanding practical applications such as sorting plastics for recycling. Here, we demonstrate selective and sensitive standoff detection of polymer films using bi-material cantilever-based photothermal spectroscopy. We demonstrate that the selectivity of the technique is sufficient to discriminate various polymers. We also demonstrate in situ, point detection of thin layers of polymers deposited on bi-material cantilevers using photothermal spectroscopy. Comparison of the standoff spectra with those obtained by point detection, FTIR, and FTIR-ATR show relative broadening of peaks. Exposure of polymers to UV radiation (365 nm) reveal that the spectral peaks do not change with exposure time, but results in peak broadening with an overall increase in the background cantilever response. The sensitivity of the technique can be further improved by optimizing the thermal sensitivity of the bi-material cantilever and by increasing the number of photons impinging on the cantilever.more » « less
An official website of the United States government

