Waveguide-enhanced Raman spectroscopy (WERS) efficiently collects Stokes-shifted scattering from target molecules in the evanescent field surrounding nanophotonic waveguides. By using a sorbent material as a top cladding, vapor phase analytes can be detected and identified at ambient densities as low as a few parts-per-billion. Previous demonstrations of vapor-phase WERS have used free-space optical components, such as microscope objectives and bulk Raman filters, to couple and filter light to and from the sorbent-clad waveguide. In this work we demonstrate a complete photonic integrated circuit (PIC) assembly that is packaged and fiber-coupled enabling us to measure WERS from trace vapor concentrations. The PIC comprises low-loss edge couplers from polarization maintaining single-mode optical fibers, sensing trenches with a sorbent top-cladding, and lattice filters for separation of the Stokes signal from the laser. The PICs are fabricated at AIM Photonics using the Silicon Nitride Passive PIC process with the TLX-VIS component library. Then, they are packaged into assemblies with permanent fiber-attach using fiber arrays. The sorbent is deposited in a thin, uniform layer in the sensing trench using one of two deposition techniques: nano-plotting and drip-coating. A laser wavelength of 785 nm enables the use of a compact spectrometer with a thermoelectrically-cooled silicon detector. Spectra are obtained with exposure times of a few seconds and show parts-per-billion detection limits for select vapors. This work successfully demonstrates the use of a compact Raman spectrometer integrated with a fully assembled PIC via optical fibers for the detection of low-density vapor-phase analytes.
Transitioning a technical method from the laboratory bench to the field is a challenge. Initially, the method needs to fill a technical gap to a degree that a warfighter or first responder would find additional hardware and training worth the logistical burden. Second, the method should be robust to minor deviations and interferents. Finally, the resultant end point must be easily read, understood, and provide actionable information to the user. Accomplishing all these steps is key to demonstrating the value of scientific research to the warfighter and delivering a valuable tool. Recent efforts have been focused on developing methods for easy and robust trace analyte collection and portable sample identification. The analytes of interest include explosives, pharmaceutical based agents, and drugs of abuse. The collection method involves paper modified with pressure-sensitive adhesives, i.e. yellow sticky notes, to sample various types of solid, porous, and environmental surfaces. Threat identification is performed directly from the collection substrates by mass spectrometric instrumentation with tandem capabilities to identify TNT, RDX, and HMX. The surface limits of detection (LODs) of the method ranged from sub to low microgram range. An analysis mode was created that would display a green light/red light if a sample was negative/positive, respectively, for a threat. This provides an easy-to-read, actionable result while saving the analytical spectra for future review. Finally, this methodology was combined with portable Raman analysis to provide both primary and confirmatory identification of fentanyl in simulated samples and TNT in samples both collected and analyzed in an austere location.
Waveguide-enhanced Raman spectroscopy (WERS) using nanophotonic waveguides has been used to demonstrate the detection of vapor-phase chemicals and liquid-phase biomolecules in water. The technique benefits from the fabrication processes and tolerances of CMOS foundries, but successful foundry-based WERS photonic integrated circuits (PICs) have only been demonstrated using excitation wavelengths of 1064 nm and 785 nm. Foundry-based PICS are beginning to operate with low loss at visible wavelengths, and WERS is uniquely poised to take advantage of this capability. Raman scattering cross-sections scale as λ−4, so a visible WERS platform could enable increased sensitivity, decreased exposure times, and/or decreased laser powers. However, increased fluorescence, increased waveguide loss, and decreased feature sizes make WERS in the visible challenging. Here, we demonstrate WERS using 300-mm foundry-based fabrication (AIM Photonics) with 633 nm and 785 nm laser excitation. We also show the successful operation and integration of other required components for a compact WERS system operating in the visible, including edge-couplers and lattice filters.
Drop-on-demand and inkjet printing technology continues to be a promising method of producing chemical test standards with scalability and flexibility to allow for inexpensive, high-throughput production of samples. This enabling technique provides precise, accurate and highly reproducible test coupons that mimic the hazardous chemicals encountered in various theater scenarios; critical in assessing the performance of existing and future sensors detection capabilities. Under the U.S. Army Forensics Advanced Research Program, the Spectroscopy Branch within the Research and Technology Directorate, DEVCOM CBC, along with internal and external collaborative partners are currently utilizing the Direct Color Systems 1800z flat-bed inkjet printer for deposition of various chemicals on relevant surfaces and GeSiM NP2.1 Nanoplotter for more precise and control droplet deposition to support various optical and non-optical detection objectives. The samples produced under this project are used for the evaluation of trace level energetic materials and illicit drugs of abuse within latent fingerprints, deposition of sorbent polymers onto photonic integrated circuits for vapor detection, point sensors, and more recently exploring enhanced training aids for military working dogs. This work will present results from the characterization of utilized chemical deposition techniques as well as recent experimental results from various assessed detection technologies
Recent work with B. anthracis Delta Sterne spores demonstrated that Raman spectroscopy could be used to discriminate between viable and gamma deactivated spores and provided initial insight into the probable source of discrimination found in the spores. From this previous work, we believe through Raman spectral analyses of viable and deactivated spore samples, significant changes in spectral response can be resolved and ascribed to classes of biomolecules affected by the deactivation processes. We expanded upon this study to include four different Bacillus spores (B. anthracis, B. megaterium, B. thuringiensis, and B. atrophaeus) and probe de-activation techniques to include gamma radiation UV radiation, chemical, and thermal methodologies. We used sequential Raman imaging scanning electron (RISE) microscopy to determine chemical (Raman spectral information) and physical (SEM imaging) variance between viable and deactivated spore samples. Additional use of machine learning algorithms to
Detection of threat materials is an important capability for the military and homeland security to protect soldiers and civilians. Waveguide-enhanced Raman spectroscopy (WERS), a photonic integrated circuit sensing methodology, is being developed for field detection of materials related to chemical warfare agents, explosives, and narcotic threats. Low-fluorescence silicon nitride spiral waveguides with long path lengths are used to obtain high signal levels with nearinfrared excitation (785 nm and 1064 nm). Compact single-mode-fiber-coupled spectrometers with high sensitivity are being utilized for detection of the Raman scattered light. Thermoelectrically cooled charged coupled device (CCD) or InGaAs detectors (-15 °C) provide for low-noise and high-quantum-efficiency spectral measurement. Performance comparable to that obtained with large benchtop spectrometers is observed. The spiral waveguides are coated with functionalized polymer sorbents suitable for concentrating relevant classes of threat materials in the evanescent field of the waveguide. The sorbents are deposited using piezoelectric microdispensers to allow for controlled deposition of thin films without the need for spin-coating. Raman chemical imaging microscopy is used to characterize the uniformity of the sorbent polymers on the waveguides. Library spectral matching can be used in combination with the selectivity of the sorbent materials to provide discrimination of the materials absorbed by the polymer coatings. The ultimate objective is development of a prototype handheld WERS sensor system suitable for defense and security applications in the field. WERS development and spectral measurements will be presented.
Waveguide-enhanced Raman spectroscopy (WERS) enables the detection and identification of trace concentrations of vapor-phase analytes using a functionalized chip-scale photonic circuit. Here, we show that WERS signal can be collected from part-per-billion levels of targeted analytes in a backscatter geometry, which, compared to forward-scatter, simplifies component integration and is more tolerant of waveguide loss and modal interference. In addition, we discuss our progress towards a compact Raman sensing system that incorporates a handheld spectrometer and chip-scale optical filters. We demonstrate that a handheld, thermo-electrically cooled spectrometer can be used for backscatter WERS with a comparable signal-to-noise to that of a liquid-nitrogen cooled benchtop spectrometer. Finally, we describe efforts to integrate the dichroic Raman filter on-chip using arrays of unbalanced Mach-Zehnder interferometers. Measurements show filter performance sufficient for integration with WERS: Transmission of >80% of the laser in the cross port and Stokes signal in the through port; and extinction of the laser by >20 dB in the though port and of Stokes signal by >8 dB in the cross port.
KEYWORDS: Raman spectroscopy, Hyperspectral imaging, Control systems, Imaging systems, Contamination, MATLAB, System identification, Chemical analysis, Short wave infrared radiation, Mid-IR
The detection of chemical hazards on surfaces continues to be a challenge for the sensing community. In order to minimize risk to users, a desirable configuration is a non-contact (standoff) system, which can operate a safe distance from the hazard. A conceptual solution to this challenge is the Wide-Area Mapping and Identification (WAMId) system. The WAMId prototype breadboard combines two distinct technologies, hyperspectral imaging and standoff Raman spectroscopy, operating in tandem to locate and identify anomalous areas of interest and then presumptively identify surface contaminates. In the developed configuration, a single short to mid wave infrared (SWIR/MWIR) hyperspectral camera images a scene of interest, data is processed to locate anomalous materials and the resulting coordinates from the scene are uploaded to a gimbal control which then slews an 830 nm Raman system to perform presumptive identification measurements. In this work, we present the results of the program, to include system development, and sample testing data for three chemicals.
The US Army Research, Development and Engineering Command – Chem Bio center is leading an inter-agency working group, to expand chemical inkjet printing techniques, and to fabricate surface standards in a controlled, uniform and quantifiable fashion, for the evaluation of stand-off active and passive optical systems. A CommercialOff-the-Shelf (COTS) standard inkjet printer was redesigned to deposit precise amounts of chemicals and explosive material on defense relevant surfaces, allowing for the generation of calibration test standards. RDECOM-CB is currently utilizing the inkjet techniques to support an Army forensics detection program where inkjet samples are used for detection of trace energetic materials and illicit drugs of abuse within residual latent fingerprints, as well as leading a North Atlantic Treaty Organization (NATO) Task Group (TG) to develop and recommend to NATO a reference standard methodology (or methodologies) for fabricating quantifiable surface standards for the evaluation of stand-off active and passive optical systems. QA/QC were performed on printed materials to determine accuracy and precision. Raman imaging and the Image-J software package was used to calculate particle statistics such as size distribution, average particle size, and fill factor. The software algorithm finds individual particles and calculates their area from a brightfield image montage. An approximate diameter of each particle, and the total fractional area of the surface covered are also calculated. For qualitative analysis Raman Chemical Imaging is performed to confirm the chemical make-up of the deposited samples. For the quantitative analysis, printed samples were analyzed by either Ion Chromatography with Conductivity Detection (IC-CD) for potassium chlorate based explosives analysis or LC-MS/MS for RDX analysis. We will present the results of inkjet samples produced for the Army forensics program as well as NATO benchmark exercise that consisted of printing trace amounts of inkjet explosive samples and performing QA/QC procedures to determine accuracy, precision and mass transport efficiency.
The U.S. Army Research Development Engineering Command Chemical Biological Center (RDECOM C&B) continues to develop technologies for the forensic detection of energetic materials and illicit drugs of abuse due to their recent confluence in counter terrorism operations. One specific technology developed here is the use of Raman Chemical imaging to detect these substances located concomitant with residual latent fingerprints. This study demonstrates the ability to identify threat materials non-destructively so that the fingerprint remains intact for further biometric analysis. Utilizing Raman spectroscopy, the Generation I Chemical Fingerprint Identification System (CFIS) semi-autonomously locates and identifies particles of interest found on the friction ridge of a given recovered fingerprint with minimal input from the operator. This work presents results from a collaborative effort between the U.S. Defense Forensic Science Center (DFSC) and RDECOM C&B in which two prototype CFIS systems were assessed with a variety of samples and examines additional practical considerations leading toward the development of the next generation of expeditionary systems for military forensic analysis.
Matrix assisted laser desorption ionization (MALDI) is a powerful technique that improved the mass spectrometry (MS) characterization of biological molecules. However this technique requires the mixing of matrix compound with the analyte of interest. The matrix compound used in MALDI process is not universal and usually depends heavily on the nature of analyte of interest being analyzed. As such there are many matrices that are used and without knowing the nature of your analyte it will be hard to predict which matrix is optimal for the most effective MALDI-MS analysis. Moreover, a high energy laser exposure is needed to initiate the ionization process through a charge transfer process between the matrix and analyte molecules. Recent advancement in the metalorganic framework (MOF) field introduced desirable surfaces that can be modified for various applications. Such MOFs can be synthesized with porous solid, and could have regular or predicted geometry. This project is introducing a novel idea of utilizing a modified MALDI substrate with MOF that can provide charge transfer between immobilized functionalized groups and analyte molecules that mimic the solvation process when a solution matrix is used. Begin the abstract two lines below author names and addresses.
We present the methodology and results of a standard assessment protocol to evaluate disparate SERS substrates that
were developed for the Defense Advanced Research Programs Agency (DARPA) SERS Science and Technology
Fundamentals Program. The results presented are a snapshot of a collaborative effort between the US Army Edgewood
Chemical Biological Center, and the US Army Research Laboratory-Aldelphi Laboratory Center to develop a
quantitative analytical method with spectroscopic figures of merit to unambiguously compare the sensitivity and
reproducibility of various SERS substrates submitted by the program participants. We present the design of a common
assessment protocol and the definition of a SERS enhancement value (SEV) in order to effectively compare SERS active
surfaces.
We are actively investigating the use of Raman spectroscopy for proximal standoff detection
of chemicals and explosive materials on surfaces. These studies include Raman Chemical Imaging of
contaminated fingerprints for forensic attribution and the assessments of commercial handheld or
portable Raman instruments operating with near-infrared (IR) as well as ultraviolet (UV) laser
excitation specifically developed for on-the-move reconnaissance of chemical contamination. As
part of these efforts, we have measured the Raman cross sections of chemical agents, toxic industrial
chemicals, and explosives from the UV to NIR. We have also measured and modeled the effect
interrogation angle has on the Raman return from droplets on man-made surfaces. Realistic droplet
distributions have been modeled and tested against variations in surface scan patterns and laser spot
size for determining the optimum scan characteristics for detection of relevant surface
contamination.
Ultraviolet resonance Raman spectroscopy (UVRRS) has been used to examine a variety of different isomers of
nitroaromatic molecules. Due to the large cross section enhancements possible, UVRRS has the potential to be a
sensitive means for detecting trace quantities of explosives at standoff distances. Since it probes both the electronic and
vibrational states of the molecules, it can also be a selective means for differentiating between similar molecules.
Resonance Raman spectra will be discussed, along with the different trends that are observed, for the different positional
isomers of dinitrobenzene. In addition, spectra for the common explosive 2,4,6-trinitrotoluene will be presented.
Wide-field Raman chemical imaging (RCI) has been used to detect and identify the presence of trace
explosives in contaminated fingerprints. A background subtraction routine was developed to minimize the
Raman spectral features produced by surfaces on which the fingerprint was examined. The Raman image was
analyzed with a spectral angle mapping routine to detect and identify the explosives. This study shows the
potential capability to identify explosives non-destructively so that the fingerprint remains intact for further
biometric analysis.
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