An advanced commercial Mid-InfraRed Isotope Ratio (IR2) analyzer was developed in Arrow Grand Technologies based on hollow waveguide (HWG) as the sample tube. The stable carbon isotope ratio, i.e. δ13C, was obtained by measuring the selected CO2 absorption peaks in the MIR. Combined with a GC and a combustor, it has been successfully employed to measure compound specific δ13C isotope ratios in the field. By using both the 1- pass HWG and 5-path HWG, we are able to measure δ13C isotope ratio at a broad CO2 concentration of 300 ppm-37,500 ppm. Here, we demonstrate its applications in environmental studies. The δ13C isotope ratio and concentration of CO2 exhaled by soil samples was measured in real time with the isotope analyzer. The concentration was found to change with the time. We also convert the Dissolved Inorganic Carbon (DIC) into CO2, and then measure the δ13C isotope ratio with an accuracy of better than 0.3 ‰ (1 σ) with a 6 min test time and 1 ml sample usage. Tap water, NaHCO3 solvent, coca, and even beer were tested. Lastly, the 13C isotope ratio of CO2 exhaled by human beings was obtained <10 seconds after simply blowing the exhaled CO2 into a tube with an accuracy of 0.5‰ (1 σ) without sample preconditioning. In summary, a commercial HWG isotope analyzer was demonstrated to be able to perform environmental and health studies with a high accuracy (~0.3 ‰/Hz1/2 1 σ), fast sampling rate (up to 10 Hz), low sample consumption (~1 ml), and broad CO2 concentration range (300 ppm-37,500 ppm).
The first of its kind Gas Chromatograph Infra Red Isotope Ratio (GC-IR2) instruments have been
deployed to the field to help the identification of sweet spot during the shale gas exploration. The onsite
measurement capability of the GC-IR2 along with its accuracy and speed helped the discovery of the fast
dynamics of gas release from shale cuttings. The half life of the isotope change for methane, ethane and
propane released from shale cuttings is closely related to the porosity and permeability of the specific shale
reservoir, and could be as short as a one hour to a couple of days. Initial δ13C values for methane could be
extremely fractionated toward heavy 13C species that values in the -20~<-10 per mil, which belong to
inorganic methane could be measured.
In our development of a field deployable infrared isotope ratio spectrometer (IR2) for compound
specific isotope analysis (CSIA), the IR2‘s accuracy and stability have reached a stage that small
fractionation in reference gas pulses generated as standard are observed easily and repeatedly. Such fine
fractionation is often difficult to observe in regular Isotope Ratio Mass Spectrometer (IRMS) due to
instrument drift on the order of 10s of minutes. After careful design of reference pulse sequences and long
period of data collection, such fractionations are also verified in a commercial continuous flow CSIA-IRMS.
Implications of the fractionation and observation process are discussed.
There have been limited choices of optical materials in the Mid-Infrared for polarization control and
subsequent isolation. We show several combinations of existing materials and optics that could realize
polarization control and isolation for quantum cascade lasers in the MIR. Improvements in signal to noise
ratio in MIR laser spectroscopy, as well as saturated absorption spectroscopy utilizing the isolation
achieved, will be discussed.
A field deployable Compound Specific Isotope Analyzer (CSIA) coupled with capillary
chromatogrpahy based on Quantum Cascade (QC) lasers and Hollow Waveguide (HWG) with precision
and chemical resolution matching mature Mass Spectroscopy has been achieved in our laboratory. The
system could realize 0.3 per mil accuracy for 12C/13C for a Gas Chromatography (GC) peak lasting as
short as 5 seconds with carbon molar concentration in the GC peak less than 0.5%. Spectroscopic
advantages of HWG when working with QC lasers, i.e. single mode transmission, noiseless measurement
and small sample volume, are compared with traditional free space and multipass spectroscopy methods.
To improve the Mid-Infrared (IR) chemical sensing capabilities in liquids and gases, a polymer
based waveguide that has 100% interaction with Quantum Cascade (QC) laser field is proposed and
demonstrated. The waveguide has thickness down to 10s nanometers so that chemical diffusion and
preconcentration could happen very fast; the path length is increased from several microns to over
centimeters due to the high spectral and diffraction brightness of QC lasers. Efficient prism coupling into
whispering gallery resonators' coated with submicron polymers and planar slab polymer waveguide are
demonstrated, high signal to noise ratio is obtained and potential applications discussed.
We present our results on efficient coupling of Quantum Cascade Lasers (QCLs) into Whispering
Gallery Resonators, Hollow Waveguide. We also present results of micro sensors using the unique
properties of QCLs, e.g. online sensors for Gas Chromatography (GC). We show that because of the
unique brightness properties of QCLs, we could improve GC-Infrared sensors' sensitivity to the same level
as Mass Spectrometry, and with different dimension of chemical information.
We show that QC laser could improve capillary Gas Chromatography Infrared spectroscopy
resolution significantly, i.e. both Doppler limited and Doppler free resolution could be achieved. To
achieve these goals, we report our latest efforts in characterizing the tuning and noise properties of
Quantum Cascade (QC) lasers; novel schemes on modulation to gain largest tuning range as well as on
stabilizing and locking the QC lasers are proposed, and results presented.
We show new results in modulating and modifying Quantum Cascade (QC) lasers to make them more
suitable for chemical sensing spectroscopy. Spectroscopy results using QC lasers are demonstrated with
whispering gallery mode CaF2 disc/ball, saturated absorption in hollow waveguide and direct chemical
analysis in water.
An amplifier design for broadband Mid-IR buried-hetero (BH) structure epitaxial laser is presented, and
external cavity design based on this amplifier is described. Spectroscopy results characterizing such single
frequency lasers are demonstrated with whispering gallery mode CaF2 disc/ball, saturated absorption in
hollow waveguide and direct chemical analysis in water.
Excitation of the whispering gallery modes (WGM) of a CaF2 ball resonator is demonstrated at 4.5 micron
with a pulsed Quantum Cascade laser. A prism coupling scheme for mid-infrared is described. Future
applications of WGM resonators as hyphenated inline chromatography sensors are discussed.
Gas monitoring over long distances using Frequency Modulation (FM) spectroscopy require phase insensitive detection scheme because of the severe scintillation problem. We report our effort to develop a long working distance CO2 monitoring LIDAR that uses phase insensitive Two-Tone Frequency Modulation (TTFM) spectroscopy technique. We could detect 10-4 single pass absorption, and could detect 1ppm CO2 level change in normal air.
Using CBO crystal as the final mixing nonlinear optical crystal, we generated 5mJ/pulse at 193nm. The high pulse energy at 193nm is a result of several factors. The efficiency of CBO is about three times better than that of LBO, and an order of magnitude better than BBO. Novel designs in 4th and 5th harmonic generators using readily available BBO crystals allow the stable, efficient and repetitive generation of high pulse energy at the 5th harmonic of 1064nm.
Using fast switching high power diode laser driver, we are able to push the limit of accurate timing of the laser pulses from a passive Q-switched diode pumped Nd:YAG laser. Combined with prepumping technique, we could reduce the delay between pump current pulse and the laser pulse down to 2.5 micro-second, and the jitter of the delay down to 100 nanoseconds.
A high pulse energy widely tunable UV and IR laser is demonstrated for combustion imaging, LIDAR, etc. The laser output has superior beam quality because of rotated KTP OPO cavity, and it is highly efficient thanks to intracavity doubling and mixing.
A high pulse energy widely tunable UV and IR laser is demonstrated for combustion imaging, LIDAR, etc. The laser output has superior beam quality because of rotated KTP OPO cavity, and it is highly efficient thanks to intracavity doubling and mixing.
The optical resolution limits the observation of fine features with size below diffraction limit, e.g. 500nm. We propose and demonstrate a technique that uses collimated laser scattering to characterize such features. We use a new illumination technique that let us image bio-molecules down to 50nm with optical microscopy. We observed vesicles with size down to 50nm and visualize the flow of such tiny molecules in the live cells. We could also characterize the detailed size and molecular weight of such particles.
KEYWORDS: Optical parametric oscillators, Polarization, Crystals, Mirrors, Wave plates, Prisms, Signal processing, Signal attenuation, Energy efficiency, Signal generators
For ns 355nm pumped simple type II BBO OPOs, two problems still remain even after rotated cavity design 1,2. The first problem is that the efficiency is still low. The other problem is the requirement of adjusting the waveplate inserted in the rotated cavity during the wide tuning range. Here, we propose and demonstrate a simple prism rotated cavity1, which uses both a type I and a type II BBO crystals pumped at 355nm.
With ultra-fast oscillator lasers (less than 1nJ/pulse, 80MHz repetition rate), we propose that we could fabricate features with less than 40nm inside UV transparent material such as fused silica and quartz. The low threshold property of this demonstration could lower the cost of lasers, and improve the throughput of laser machining due to the quasi-CW nature of the laser used. Our initial results shows that damages are observed with threshold as low as 1nJ before the UV objective, and then size is below 1 micron.
We use computer simulation to illustrate how thermally induced phase mismatch affect deep UV harmonic generation. A multicrystal harmonic generator that compensates for thermally include phase mismatch is then presented. We have tested this multicrystal design with a Nd:YAG lasers 4th harmonic generator based on two pieces of (beta) -BaB2O4 crystals, and our results demonstrate that it compensates for the thermally include phase mismatch, effectively increasing the interaction length of nonlinear optical crystals during harmonic generation under high loading.
We measured the two-photon absorption (TPA) cross sections inside (beta) -BBO crystal during UV harmonic generation. We found that the 2-photon absorption is dominating the absorption effect inside the BBO crystal during UV harmonic generation. Both 2 UV photons and 1 UV photon + 1 fundamental photon absorption cross sections are significant. Possible explanations are presented, and compared with other nonlinear otpical crystals. Thermal profiles inside the crystal as a result of the strong absorption processes are discussed through a computer program that simulates the heat dissipation process. We conclude that TPA is the significant factor in high power scaling of UV harmonic generation inside nonlinear optical crystals.
The design of a BBO OPO cavity based on cylindrical focusing of the pump beam in the insensitive plane of the non-linear crystal is presented and characterized. A variety of beam sizes in the sensitive plane of the BBO crystal are investigated, and in all cases this cavity design is found to significantly lower the operational threshold pulse energy of 355 nm pumped type I BBO OPOs. With optimal beam focussing parameters, the measured threshold intensity of 45 MW/cm2 is similar to that of conventional OPOs, but the threshold pulse energy of 0.4 mJ is some twenty times lower than that found in circularly symmetric pump beams. Pump pulse energies in this range can now be routinely achieved with diode-pumped Q-switched lasers, and the combination of these sources with cylindrically-focussed OPO cavities should result in a new class of all-solid-state high repetition rate and high average power non-linear light sources that can be tuned over the entire visible wavelength region.
By integrating a free running cavity and a narrow bandwidth cavity, it is possible to create a compound OPO design which possesses the most desirable properties of each. In this example, we have combined a 355 nm-pumped idler-resonator free running type I BBO OPO cavity with a grating-narrowed signal-re-injection arm using only standard, low-cost optics. The output from such an implementation retains the high efficiency and low divergence of the free-running OPO, but its bandwidth is dictated by that of the high resolution cavity.
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