Preliminary results of heterodyne detection with quantum-cascade lasers in the 9 microm region

In this paper, we describe recent results in mid-infrared heterodyne detection using quantum-cascade (QC) lasers as local oscillator (LO). In the 9 microm range, the heterodyne detection technique was first developed with CO(2) lasers and then with Pb-salt diode lasers. Quantum-cascade lasers are promising high quality tunable mid-infrared sources. We developed a quantum-cascade laser based heterodyne spectrometer. Atmospheric absorption spectra of ozone are presented.     

Quantum cascade laser-based photoacoustic spectroscopy of volatile chemicals: application to hexamethyldisilazane

The use of photoacoustic spectroscopy and mid-infrared quantum-cascade lasers (QCLs) for the detection of hexamethyldisilazane (HMDS) is reported. A detection limit of 200 parts in 10(9) is found using a Fabry-Perot QCL operated at 8.4 microm in pulsed mode and a photoacoustic cell equipped with four electret microphones. The laser multimode spectrum matches the range of the N-H bending absorption band of HMDS. Further improvements to reach lower detection limits are discussed.     

Infrared laser heterodyne systems

This paper gives a review of mid-infrared laser heterodyne systems. The advantages of using heterodyne detection are described and the different techniques corresponding to the choice of the local oscillator are presented. A thorough discussion of the gas laser heterodyne systems is followed by the presentation of tunable diode laser systems capabilities. Many experiments in the mid-infrared region are reviewed covering the astronomical and atmospheric, ground-based and airborne investigations as well as the laboratory measurements.     

THIS: a tuneable heterodyne infrared spectrometer

With the Cologne Tuneable Heterodyne Infrared Spectrometer (THIS) we present a newly developed setup of a transportable heterodyne receiver. Competitiveness with regard to sensitivity, was reached for the first time with a semiconductor laser pumped system. Frequency tuneability of the local oscillator (LO) laser over a wide range of wavelengths is thus provided. This allows a variety of molecules, e.g. O3, NH3, CH4, N2O,.... in the earth's atmosphere, in planetary atmospheres or even in interstellar space to be observed with very high frequency resolution either from aboard the Stratospheric Observatory For Infrared Astronomy (SOFIA) or other ground based telescopes. Besides the good results with tuneable lead salt laser (TDL) operation there's room to improve: the power provided by such devices is not sufficient for a sensitivity close to the quantum limit. Therefore, first tests with recently developed high power quantum-cascade lasers (QCL) were carried out and further substantial improvement of the system noise temperature seems to be in reach.     

Pulsed lasers versus continuous light sources in capillary electrophoresis and fluorescence detection studies: Photodegradation pathways and models

Pulsed lasers are widely used in capillary electrophoresis (CE) studies to provide laser induced fluorescence (LIF) detection. Unfortunately pulsed lasers do not give linear calibration curves over a wide range of concentrations. While this does not prevent their use in CE/LIF studies, the non-linear behavior must be understood. Using 7-hydroxycoumarin (7-HC) (10–5000 nM), Tamra (10–5000 nM) and tryptophan (1–200 μM) as dyes, we observe that continuous lasers and LEDs result in linear calibration curves, while pulsed lasers give polynomial ones. The effect is seen with both visible light (530 nm) and with UV light (355 nm, 266 nm). In this work we point out the formation of byproducts induced by pulsed laser upon irradiation of 7-HC. Their separation by CE using two Zeta LIF detectors clearly shows that this process is related to the first laser detection. All of these photodegradation products can be identified by an ESI-/MS investigation and correspond to at least two 7HC dimers. By using the photodegradation model proposed by Heywood and Farnsworth (2010) and by taking into account the 7-HC results and the fact that in our system we do not have a constant concentration of fluorophore, it is possible to propose a new photochemical model of fluorescence in LIF detection. The model, like the experiment, shows that it is difficult to obtain linear quantitation curves with pulsed lasers while UV-LEDs used in continuous mode have this advantage. They are a good alternative to UV pulsed lasers. An application involving the separation and linear quantification of oligosaccharides labeled with 2-aminobezoic acid is presented using HILIC and LED (365 nm) induced fluorescence.     

Narrow-Linewidth 2 μm All-Fiber Laser Amplifier with a Highly Stable and Precisely Tunable Wavelength for Gas Molecule Absorption in Photonic Crystal Hollow-Core Fibers

In recent years, mid-infrared fiber lasers based on gas-filled photonic crystal hollow-core fibers (HCFs) have attracted enormous attention. They provide a potential method for the generation of high-power mid-infrared emissions, particularly beyond 4 μm. However, there are high requirements of the pump for wavelength stability, tunability, laser linewidth, etc., due to the narrow absorption linewidth of gases. Here, we present the use of a narrow-linewidth, high-power fiber laser with a highly stable and precisely tunable wavelength at 2 μm for gas absorption. It was a master oscillator power-amplifier (MOPA) structure, consisting of a narrow-linewidth fiber seed and two stages of Thulium-doped fiber amplifiers (TDFAs). The seed wavelength was very stable and was precisely tuned from 1971.4 to 1971.8 nm by temperature. Both stages of the amplifiers were forward-pumping, and a maximum output power of 24.8 W was obtained, with a slope efficiency of about 50.5%. The measured laser linewidth was much narrower than the gas absorption linewidth and the wavelength stability was validated by HBr gas absorption in HCFs. If the seed is replaced, this MOPA laser can provide a versatile pump source for mid-infrared fiber gas lasers.     

Fundamental imaging properties of transillumination laser computed tomography based on coherent detection imaging method.

The coherent detection imaging (CDI) method uses the optical heterodyne detection technique. CW and single frequency lasers having long coherence lengths are used to exploit the maximum advantages of heterodyne detection, such as high directionality, selectivity and sensitivity. The CDI method based on optical heterodyne detection enables selective filtering of the directional coherence-retaining emergent photons, which leads to image reconstruction from projections, similar to X-ray computed tomography (CT). So far we have demonstrated the advantages and capabilities of the measurement technique for transillumination optical computed tomography in biomedicine. Here, we investigate the fundamental imaging properties of CDI method, such as its high directionality and quantitativeness, with preliminary physical phantom experiments. The results show that the CDI method satisfies the requirements for CT reconstruction under the first order approximation, and enables quantitative measurements in the sense that the relationship between estimated and actual concentration retains a satisfactory linearity.     

Thermal stability and 2.7 μm spectroscopic properties in Er3+ doped tellurite glasses

In present paper, the thermal stability and 2.7 μm spectroscopic properties in Er³⁺ doped tellurite glasses have been investigated by 980 nm laser diode pumping. Thermal analysis indicates that GeO₂ modified tellurite glass has better thermal stability and anti-crystallization ability. Judd-Ofelt intensity parameters are calculated and discussed to examine the covalency characteristics based on absorption spectra. The 2.7 μm fluorescence is obtained and the lifetime can reach 124 ± 1 μs with the quantum efficiency of 61.5% in prepared samples. Moreover, higher effective emission bandwidth (136.67 nm), emission cross sections (12.75 × 10⁻²¹ cm²) and radiative transition probability (95.66s⁻¹) at 2.7 μm are achieved. In addition, upconversion and near-infrared emission spectra are measured to elucidate energy transfer mechanism of Er³⁺. The results suggest that the present tellurite glass modified by GeO₂ might have promising applications in mid-infrared fiber lasers.     

Characterization of InAlAs/InGaAs/InP mid-infrared quantum cascade lasers

A mid-infrared laser characterization system, including a GPIB programmable I-P and I-V set-up based on direct waveform measurement with extraordinary wide pulse duration and duty cycle tuning range, in conjunction with a Fourier transform infrared spectroscopy system adapted with double modulation technique, has been developed. Based on this characterization system, the characteristics of gas source MBE grown InAlAs/InGaAs/InP quantum cascade lasers (QCL), especially their thermal property, have been evaluated. The results show that in the combination of I-P, I-V and spectral measurements at various driving pulse parameters, the thermal resistance, lasing conditions as well as spectral characteristics of the mid-infrared QCL could be deduced. This characterization system is also a useful tool for the evaluation of other types of diode lasers in the mid-infrared band.     

Photoacoustic gas detection using a cantilever microphone and III–V mid-IR LEDs

The cantilever enhanced photoacoustic trace gas detection in the mid-infrared 3–7 μm wavelength range has been combined with light emitting diode (LED) technology. Mid-IR LED output power was modulated by pulse driving current with frequency high enough to avoid acceleration and acoustical noise. Methane (CH₄), propane (C₃H₈), carbon dioxide (CO₂) and sulphur dioxide (SO₂) gases have been used for preliminary evaluation of the method sensitivity. The lowest detection limit of 6 ppm was observed for propane employing a LED with a center wavelength 3.3 μm and with 1 s sample integration time.     

New improvements in methane detection using a Helmholtz resonant photoacoustic laser sensor: a comparison between near-IR diode lasers and mid-IR quantum cascade lasers

Atmospheric methane was detected by combining a photoacoustic (PA) sensor with several lasers emitting in both the near- and mid-infrared spectral ranges to check the achievable detection limits. The PA spectrometer is based on differential Helmholtz resonance. Near-infrared telecommunication-type laser diodes of increasing power, from Sensors Unlimited Inc. and Anritsu, were first used to scan the 2 nu(3) band of CH(4) near 1.65 microm. The best achieved detection limit is 0.15 ppm of methane at atmospheric pressure and with a 1s integration time. The PA sensor was then operated in conjunction with a quantum cascade laser from Alpes Lasers emitting near 7.9 microm on the nu(4) band of CH(4). The achieved detection limit is then of 3 ppb. The dramatic improvement in the detection limit obtained with the QC laser is due to the stronger optical power as well as to the capability of reaching the fundamental bands of methane lying in the mid-infrared spectral range.     

Analysis of serotonin release from single neuron soma using capillary electrophoresis and laser-induced fluorescence with a pulsed deep-UV NeCu laser

The use of capillary electrophoresis (CE) with laser-induced fluorescence excited by ultraviolet (UV) lasers in the range 200–300 nm has been restricted by the available wavelengths and expense of UV lasers. The integration of a NeCu deep UV laser operating at 248.6 nm with a single channel CE system with post-column sheath flow detection allows detection limits for serotonin and tryptophan of 3.9×10^-8 M and 4.5×10^-8 M respectively. Single cell analysis of serotonergic metacerebral cells from the sea slug Aplysia californica yields a value of 800±85 fmol of serotonin in each cell soma. For the first time, serotonin is directly detected in electrically stimulated release from single metacerebral cell soma, with approximately 4% of the serotonin contained in the soma released from a semi-intact preparation with a 2 min electrical stimulation.     

共掺稀土离子对Er~(3+)激活中红外激光晶体光谱性能的影响

Er3+掺杂的晶体能够产生2.7~3.0μm波段中红外激光,在激光医疗、光通讯、环境探测和光电对抗等领域具有重要的应用。基于本课题组近年来开展的Er3+激活中红外激光晶体的相关工作,本文综述了共掺稀土离子对Er3+激活晶体光谱性能的影响:包括敏化离子Cr3+、Yb3+等的敏化作用增强了Er3+的特征吸收峰;退激活离子Pr3+、Ho3+等的退激活效应抑制了自终态瓶颈效应;以及共掺Nd3+所起的敏化和退激活双重作用,并对中红外激光的研究趋势和前景进行了展望。     

Photoacoustic gas detection using a cantilever microphone and III–V mid-IR LEDs

The cantilever enhanced photoacoustic trace gas detection in the mid-infrared 3–7 μm wavelength range has been combined with light emitting diode (LED) technology. Mid-IR LED output power was modulated by pulse driving current with frequency high enough to avoid acceleration and acoustical noise. Methane (CH₄), propane (C₃H₈), carbon dioxide (CO₂) and sulphur dioxide (SO₂) gases have been used for preliminary evaluation of the method sensitivity. The lowest detection limit of 6 ppm was observed for propane employing a LED with a center wavelength 3.3 μm and with 1 s sample integration time.     

Structure and spectroscopic properties of Er3+ doped germanate glass for mid-infrared application

Intense 2.7 μm emission derived from modified Er³⁺ doped germanate glass was reported. Raman spectrum analysis was carried out to grasp glass structure. Based on the absorption spectrum, the Judd–Ofelt parameters and radiative properties were calculated originated from Judd–Ofelt theory. 2.7 μm emission characteristics, stark splitting features and energy transfer processes upon excitation of a conventional 808 nm or 980 nm laser diode were carefully investigated. The prepared glass possesses high spontaneous transition probability (34.28 s⁻¹), large calculated emission cross section (13 × 10⁻²¹ cm²) and gain coefficient (5.4 cm⁻¹) for the ⁴I_11/2 → ⁴I_13/2 transition. These results indicate that Er³⁺ doped germanate glass has potential applications in mid-infrared lasers and amplifiers.     

Ultra-sensitive mid-infrared evanescent field sensors combining thin-film strip waveguides with quantum cascade lasers

We demonstrate ultra-sensitive chemical sensing in the mid-infrared spectral regime with a combination of quantum cascade lasers (QCLs) with GaAs/Al(0.2)Ga(0.8)As strip waveguides fabricated via metal-organic vapor-phase epitaxy (MOVPE) and reactive ion etching (RIE) using evanescent field absorption spectroscopy. These strip waveguides have been designed with a width of 200 μm, thereby facilitating 2-D confinement and mode-matched propagation of mid-infrared radiation emitted from a distributed feedback (DFB) QCL at a wavelength of 10.3 μm. Acetic anhydride was detected with a limit of detection (LOD) of 18 pL (19.4 ng) deposited at the waveguide surface by overlapping of the vibrational absorption of the methyl group with the emission frequency of the QCL. The obtained results indicate a remarkable enhancement in sensitivity by three orders of magnitude compared to previously reported multimode planar silver halide waveguides. Further reduction of the waveguide strip width to 50 μm resulted in an additional sensitivity enhancement yielding a calculated LOD of 0.05 pL for the exemplary analyte acetic anhydride, which is among the most sensitive evanescent field absorption measurements with a miniaturized mid-infrared sensor system reported to date.     

Imaging ultrafast dynamics of molecules with laser-induced electron diffraction

We introduce a laser-induced electron diffraction method (LIED) for imaging ultrafast dynamics of small molecules with femtosecond mid-infrared lasers. When molecules are placed in an intense laser field, both low- and high-energy photoelectrons are generated. According to quantitative rescattering (QRS) theory, high-energy electrons are produced by a rescattering process where electrons born at the early phase of the laser pulse are driven back to rescatter with the parent ion. From the high-energy electron momentum spectra, field-free elastic electron-ion scattering differential cross sections (DCS), or diffraction images, can be extracted. With mid-infrared lasers as the driving pulses, it is further shown that the DCS can be used to extract atomic positions in a molecule with sub-angstrom spatial resolution, in close analogy to the standard electron diffraction method. Since infrared lasers with pulse duration of a few to several tens of femtoseconds are already available, LIED can be used for imaging dynamics of molecules with sub-angstrom spatial and a few-femtosecond temporal resolution. The first experiment with LIED has shown that the bond length of oxygen molecules shortens by 0.1 ? in five femtoseconds after single ionization. The principle behind LIED and its future outlook as a tool for dynamic imaging of molecules are presented.     

Sum frequency generation at 365 nm by two diode lasers applied to the detection of mercury

365 nm laser light is produced by sum frequency generation in a LiIO₃ crystal using two continuous-wave single mode diode lasers. The efficiency of sum frequency generation as well as the applicability as a radiation source for the detection of mercury are discussed.     

Spectroscopic tests of a 2.3 μm tunable diode laser

A 2.3 μm near-room temperature tunable diode laser was tested for applications in high-resolution laboratory spectroscopy. It was mounted using a simple adaptor in a spectrometer usually used with lead-salt diode lasers, and was found to be electrically and optically compatible with the system. Good output power (several milliwatts) was observed, and a tuning range of 4460–4150 cm⁻¹ was achieved for laser temperatures of 210–310 K. Some spectra of N₂O and NH₃ were recorded in the 4300–4430 cm⁻¹ region. However, the laser was not generally useful due to noisy and unstable output and high sensitivity to optical feedback.     

Tunable and Passively Mode-Locking Nd0.01:Gd0.89La0.1NbO4 Picosecond Laser

A high-quality Nd_0.01:Gd_0.89La_0.1NbO₄ (Nd:GLNO) crystal is grown by the Czochralski method, demonstrating wide absorption and fluorescence spectra and advantage for producing ultrafast laser pulses. In this paper, the tunable and passively mode-locking Nd:GLNO lasers are characterized for the first time. The tuning coverage is 34.87 nm ranging from 1058.05 to 1092.92 nm with a maximum output power of 4.6 W at 1065.29 nm. A stable continuous-wave (CW) passively mode-locking Nd:GLNO laser is achieved at 1065.26 nm, delivering a pulse width of 9.1 ps and a maximum CW mode-locking output power of 0.27 W.