US20180266946A1

US20180266946A1 - Quantum Cascade Laser (QCL) Based Gas Sensing System and Method

Info

Publication number: US20180266946A1
Application number: US15/981,298
Authority: US
Inventors: Petros A. Kotidis; Erik Deutsch; Hongke Ye; Alexander Mazurenko; Anish K. Goyal; Jeffrey S. Socha
Original assignee: Block Engineering LLC
Current assignee: Block Engineering LLC
Priority date: 2015-02-06
Filing date: 2018-05-16
Publication date: 2018-09-20
Also published as: US20160231239A1; US9983126B2; WO2016127146A1

Abstract

A system and method are disclosed for gas sensing over a wide tunable wavelength range provided by one or more quantum cascade lasers. A laser beam is generated within the wide tunable wavelength range, which is given by the sum of the wavelength ranges from the individual lasers. Gas sensing or detection is achieved by obtaining an infrared absorption spectrum for a sample contained in one or more cells having different path lengths for the laser beam.

Description

RELATED APPLICATIONS

This application is a Continuation of U.S. patent application Ser. No. 15/017,610, filed on Feb. 6, 2016, which claims priority to U.S. Provisional Application No. 62/113,069, filed on Feb. 6, 2015, 62/186,067, filed on Jun. 29, 2015, and 62/262,010, filed on Dec. 2, 2015, all of which are incorporated herein by reference in their entirety.

BACKGROUND OF THE INVENTION

Quantum cascade lasers generate light in the mid- to far infrared (IR) using inter-subband transitions in a repeated stack of semiconductor multiple quantum well heterostructures. A spectroscopy system based on these tunable lasers and various applications for such a system have been discussed by Kotidis et al., in U.S. Pat. No. 8,780,347 B2, entitled “QCL Spectroscopy System and Applications Therefor”, which is herein incorporated by reference in its entirety.

SUMMARY OF THE INVENTION

Embodiments of the present principles provide a gas sensing system and method, in which one or more tunable quantum cascade lasers are configured to provide a beam in a wide tunable wavelength range in the infrared region. The laser beam is directed to one or more sample cells with at least two different path lengths for gas detection or sensing by obtaining an absorption spectrum for at least one of the gases or components.
In general, according to one aspect, the invention features a gas sensing system, which includes: at least one quantum cascade laser configured for tuning within a wavelength range and for providing a beam in the wavelength range; at least one cell for containing a sample and for receiving the beam; the at least one cell providing at least two different path lengths for the beam; and a detector system configured for obtaining at least one absorption spectrum for the sample by detecting the beam exiting the at least one cell.
In general, according to another aspect, the invention features a method for gas sensing, which includes: providing at least one quantum cascade laser configured for tuning within a wavelength range and for providing a beam in the wavelength range; directing the beam through at least one cell containing a sample; the at least one cell providing at least two different path lengths for the beam; and obtaining at least one absorption spectrum for the sample by detecting the beam exiting the at least one cell.
The at least one quantum cascade laser can be a plurality of quantum cascade lasers (QCLs) configured for providing a plurality of beams, each of the plurality of beams being in a wavelength range associated with a respective QCL. Optical components are then used to combine the plurality of beams to form a single beam and for directing the single beam through the at least one cell.
In one example, a single cell is used that has the at least two different path lengths for the beam.
In other case, a first cell and a second cell are provided, the first cell having a first path length, and the second cell having a second path length that is different from the first path length.
Multi-pass arrangements can be further be used. Pressure control can also helpful.
In general, according to another aspect, the invention features a gas sensing system. This system comprises at least one quantum cascade laser configured for tuning within a wavelength range and for providing a beam in the wavelength range, at least one cell for containing a gas sample, from a semiconductor processing operation, and for receiving the beam, and a detector system configured for obtaining at least one absorption spectrum for the sample by detecting the beam exiting the at least one cell.
In general, according to still another aspect, the invention features a method for gas sensing. This method comprises providing at least one quantum cascade laser configured for tuning within a wavelength range and for providing a beam in the wavelength range, directing the beam through at least one cell containing a sample from a semiconductor processing operation, and obtaining at least one absorption spectrum for the sample by detecting the beam exiting the at least one cell.
The above and other features of the invention including various novel details of construction and combinations of parts, and other advantages, will now be more particularly described with reference to the accompanying drawings and pointed out in the claims. It will be understood that the particular method and device embodying the invention are shown by way of illustration and not as a limitation of the invention. The principles and features of this invention may be employed in various and numerous embodiments without departing from the scope of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

In the accompanying drawings, reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale; emphasis has instead been placed upon illustrating the principles of the invention. Of the drawings:

FIG. 1A shows an overview of one embodiment of a QCL gas sensing system of the present invention;

FIG. 1B shows an alternative embodiment of the gas sensing system from FIG. 1A;

FIG. 2A is a plot of absorbance as a function of wavenumber for methane, ethane, and propane;

FIG. 2B is a plot of absorbance as a function of wavenumber for n-Butane, iso-Butane, Pentane and iso-Pentane;

FIG. 2C is a plot of absorbance as a function of wavenumber for methane, ethane, and propane;

FIG. 2D is a plot of absorbance as a function of wavenumber for n-Butane, iso-Butane, Pentane and iso-Pentane;

FIG. 3 is a block diagram of some components of a gas sensing system;

FIG. 4 shows examples of some applications for the QCL system;

FIG. 5 shows an alternative configuration of the gas sensing system with an internal reference;

FIG. 6A shows an alternative configuration of the gas sensing system with multiple detectors;

FIG. 6B shows an alternative embodiment of the system;

FIG. 7 shows an alternative configuration of the gas sensing system, in which a detector is used for real-time referencing;

FIG. 8 shows an alternative configuration of the gas sensing system, in which a single detector is used in a self-referencing scheme;

FIG. 9 shows an alternative configuration of the gas sensing system, with an open path providing a long sample length;

FIG. 10 shows an alternative configuration of the gas sensing system, in which multiple laser pulses are used for self-referencing purpose;

FIG. 11 shows an alternative configuration of the gas sensing system used for photoacoustic gas sensing;

FIG. 12 shows an alternative configuration of the gas sensing system, which has a continuous laser output spectrum;

FIG. 13 shows an alternative configuration of the gas sensing system, in which a QCL module is configured for quasi-single mode lasing;

FIG. 14 shows an alternative configuration of the gas sensing system, in which the sample cell mirrors are provided inside a sample cell;

FIG. 15 shows an alternative configuration of the gas sensing system, in which the sample cell mirrors are provided outside a sample cell.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

FIGS. 1A and 1B show an overview of two embodiments of a gas sensing system 100 of the present invention. By configuring one or more QCLs to provide rapid tuning over a wide wavelength range, the system can be used for rapid gas sensing applications, while providing sufficiently large spectral range to detect multiple gases using their IR absorption characteristics.
Multiple QCL tuner modules QCL1, QCL2, QCLn with different tunable wavelength ranges are used in order to cover the broad spectral range offered by this system in some embodiments. In one embodiment, the gas sensing system can have up to four QCL tuners, but in other embodiments, the number is not limited to four. A single QCL tuner can also be used in still other implementations.
As shown in FIG. 1A, the beams I₁, I₂, . . . , I_nfrom the multiple QCL tuner modules are combined into a single beam Ic, which is then split by beam splitter 102 into multiple beams Ic₁, Ic₂prior to entering two or more gas cells 110, 120, respectively. The gas cells 110 and 120 have different path lengths. For simplicity's sake, the optical components (e.g., folding mirror, dichroic, and partially reflecting mirrors, and so on) used for combining two or more beams I₁, I₂, . . . , I_nare not shown in FIG. 1A or 1B. Instead, details can be found in various sections of U.S. Pat. No. 8,780,347 B2. It is possible to have any combination of beams going into any combination of gas cells.
FIG. 1B shows another configuration with a single gas cell 115, which has at least two different path lengths for the incoming laser beam I_c(combined beam from one or more QCLs). In this illustration, one path length (p1) corresponds to a single pass through the cell, with beam I″_c1exiting the cell and directed to the detector system 140. A second path length (p2) corresponds to a multi-pass through the cell (after 5 passes in this illustration), with beam I″_c2exiting the cell and directed to the detector system 140. In one embodiment, the two path lengths are 10 cm and 70 cm, respectively. In general, one path length is less than 40 cm and the other is longer than 50 cm. This embodiment can make the overall system more compact than having separate gas cells. This multi-path length single cell configuration can also have other benefits such as referencing out system level differences with the only difference in optical signal being the difference in path length inside the cell.
The multiple QCL tuner modules (QCL1, QCL2, QCLn) are employed to cover a wider scan band. In one example, each of the modules generates a narrowband, tunable optical signal that scans in wavelength through a different module scanband or wavelength region. The separate modules cover different module scanbands so that the effective scanband of the system covers a wide wavelength band or region such as 5.0 to 13 micrometers in wavelength. In general, the different tunable ranges from the QCL modules do not overlap or have little spectral overlap with each other, although a certain amount of wavelength overlap can be acceptable as long as it does not adversely impact the efficiency or performance of the system.
A controller 130 (e.g., including electronic components such as a processor, memory, and so on) controls the operation of the modules to sweep their tunable optical signals sequentially through their respective module scanbands so that the entire system scanband is covered. The spectral response of the sample (i.e., IR absorption spectrum) is accumulated from the time response of the detector system 140.
In one embodiment, the detector system 140 comprises two photo detector, one photo detector for detecting each incoming beam I″_c1I″_c2.
In another embodiment, beam switches are used so that the beams I″_c1I″_c2are received at different times at a common photo detector.
In still another embodiment, the single input beam single beam Ic is pulse modulated with pulses of less than a millisecond long with less than a 50% duty cycle. Preferably the pulses are even shorter in duration such as less than a microsecond, or even less than 10 nanoseconds. The beam is then split, the two paths with the different path length provide different delays. As a result, the pulses from the different paths arrive at different times in beams I″_c1I″_c2. Thus, the detector system 140 includes, in one implementation, a single photo detector that detects the pulses in both beams I″_c1I″_c2, albeit separated in time. This is illustrated in more detail below.
One embodiment of the system includes the use of multiple gas or sample cells. The use of multiple gas cells provides the capability to simultaneously measure gases or gas concentrations that might be too absorptive for a long path cell (or long path length), as well as gases that are not very absorptive. The low absorptive gases need a long cell in order to provide enough signal for low limits of detection.
In most cases, long path lengths are provided by using a long cell or multi-pass configuration, in which the combined beam bounces back and forth several times prior to exiting the cell and reaching the detector. Short cells are typically configured for single pass. More than two gas cells can be included in the gas sensing system, depending on the type of gases that need to be monitored. In some cases, it is possible for the long cell to be single pass, for example, as in the case of a duct or pipe.
One application for the gas sensing system is real-time mudlogging analysis (the creation of a detailed record of a borehole in a drilling operation), in which C1, C2, C3, nC4, iC4, nC5 and iC5 compounds and potentially heavier hydrocarbons such as C6, etc., are simultaneously measured by the gas sensing system.
FIGS. 2A-2D show the infrared spectra of these hydrocarbons in the range of 5-13 μm or 750 to 1750 in wavenumber (cm⁻¹), which is used in one embodiment of the system. As shown, there are regions of strong and weak spectral bands, as well as areas of strong overlap in the IR absorptions of the various compounds. FIGS. 2A and 2B show the large absorption in the 5-8 μm region of the spectrum and FIGS. 2C and 2D provide expanded views to display the lower absorption in the 8-13 μm region of the spectrum. The controller 130 employs algorithms to select the proper combination of QCL ranges that take advantage of the strong absorption bands for the gases being monitored and low overlap with absorption bands from other gases or impurities.
For example, since water absorption occurs in the 5-7.5 μm range, it is desirable to select QCL ranges outside that band and still achieve low limits of detection (i.e., high detection sensitivities) for the sample gases being monitored. Thus, a proper selection of the IR wavelength region can lead to an improved detection sensitivity for a given gas while minimizing spectral interference from other gases. In other words, to enhance the detection sensitivity for a given gas in a sample or mixture, a wavelength range for the QCL laser beam can be selected so that it includes or overlaps with a strong absorption band for the given gas, but has a minimal overlap with absorption bands from another gas or impurity, thus avoiding spectral interference from at least another gas (or impurities) that may be present in the sample.
In the particular case of the C1-C5 Mudlogging monitoring, a long multi-pass cell, e.g., cell 120 or long path in the multi-path cell 150, is primarily used for the detection of the C3-C5 components, because they typically appear in low concentrations during Mudlogging. However, C1 and C2 at low enough concentrations (to avoid signal saturation) can also be measured with this multi-pass cell. The single cell, e.g., cell 110 or short path in the multi-path cell 150, is used primarily for C1 and C2, which typically appear in large concentrations. However, depending on the relative gas concentrations present, the short cell can also be used for the C3-C5 components.
Another embodiment involves the use of pressure control in the gas cells in order to improve the sensitivity of the system. By lowering the pressure in the gas cell, the infrared absorption can be reduced. The system has gas cells with solenoid valves and flow restrictors such as bleed valves and/or pressure regulators that can be used to reduce or increase the pressure of the gas inside the cells. This configuration provides an additional method of controlling the absorption of light by the sample gas or chemical in the cell. Therefore, the optimum absorption of light, i.e. avoiding too much or too low absorption, can be controlled not only by using a combination of short and long path gas cells, but also by controlling the pressure inside the cells, which reduces or increases the-light absorption by the sample gas or chemical. The pressure control is designed in such a way as to minimize the equilibration time when changing configuration.
In one example, the selection of gas cell length and pressure combination is provided in the following ways. In one case, software built-in, user-selectable, look-up tables, prescribe the selection for the desired gas and concentration of interest. For example, methane monitoring at 90% concentration could be accomplished with a short cell (or short path length) and low pressure, while 1% concentration could require the long cell (or longer path length) and higher pressure. In another case, automated software selection senses that the detector gets either saturated or not receiving enough light, in which case the controller applies the appropriate combination of gas cell and pressure automatically, using an intelligent, built-in algorithm. For example, one or more processors in the system can be programmed so that, in response to detected IR signal levels, the controller can take actions to select system parameters and conditions suitable for the specific gas being monitored. The software can also use all the data but the algorithm can weight different sections of data from the cells differently based on saturation levels.
In order to ensure that the measurements are correct, a preconditioning algorithm for the data can be used. The measured spectra are evaluated using preselected criteria, which are built into the system's operational software, and only the spectra that passed the criteria are used as inputs to the prediction model.
In another alternative configuration, the QCL tuners shown in FIG. 1 can include one or more Distributed Feedback (DFB) lasers. Under this “hybrid” configuration, both widely tunable QCL tuners (QCL1, QCL2, e.g.,) are combined with narrow band tuners (QCL3) in a single devices. The narrow band tuner QCL3 includes narrowly tunable (DFB) lasers. The purpose of this alternative configuration is to use the DFB laser tuner(s) (QCL3) to capture the spectral peaks of certain chemicals that are outside the spectral range covered by the widely tunable QCLs. DFB lasers are typically narrowly tunable, so they need to be specifically selected for each targeted gas peak. Multiple DFB lasers can be used to capture multiple gases with typically a one-to-one match, while the widely tunable QCLs can be used to detect multiple gases per laser chip or tuner.
FIG. 3 shows a block diagram of an example of a system 300 suitable for use with mud logging application. Details for various components are discussed below.
Gas cells 310, 320: The cell temperature for the one or more cells is designed to be higher than 40° C., around 50° C., which is maintained by using one or more heaters 325. This prevents condensation of hydrocarbon gases in the cell 310 or 320, as the cell body temperature is well above the n-pentane boiling point. Water entering the cell is likely to evaporate, as the water content in the lines will be determined by the equilibrium at the mud surface. Higher temperatures minimize issues with gas chemistry affecting the spectroscopy. However, the elevated temperature cannot prevent heavier hydrocarbons from contaminating cell surfaces. (To avoid contamination by heavier hydrocarbons would require operating the cell at 100-150° C., which is incompatible with operating inside an explosion proof box.) The cell windows (not shown in FIG. 3) are designed to be removable to aid in cleaning, should the cells become contaminated with high-boiling point liquids like ethylene glycol (e.g., used in drying the entering gas) or with heavier hydrocarbons (diesel) that can be present in the drilling environment. Since the operating orientation of the gas sensing instrument or sample cell may not be well-defined, it may not possible to design the gas entrance and exit orifices to be self-draining. Therefore, the orifices are placed so that the entire volume of the cell can be fully swept by the entering gas. The temperature sensor is placed so that the gas temperature can be measured. The measured temperature will be slightly lower than the cell body and will depend on the temperature and flow rate of the incoming gas.
Pump 350: A pump 350 is used for evacuating the gas cells 310 and 320, with pressure being measured by a pressure sensor 352. In one embodiment, the pump is based on the application for C1-05 measurements, but the general selection criteria would apply to other gases as well. The pump is required to draw about 5 SLPM (standard liter per minute) and provide an ultimate vacuum around 10 mbar or less. The pump is selected to fit in a minimum volume. The flow rate should be sufficiently high to obtain sampling with minimal lag between the sampling point and the gas sensing instrument. The ultimate vacuum is required to empty the cell of as much gas as possible so that an accurate reference can be taken. The ultimate vacuum of 10 mbar means that about 1% of gas remains in the cell. Under most operating conditions, this should be adequate and the prediction module accommodates effects from this that are related to water. Alternately, a pump that operates at ambient conditions can be used in conjunction with “zero” and “span” ports (not shown in FIG. 3) which can route zero air or a calibration standard via an arrangement of valves in order to take a background reference (zero) and also to verify the validity of the reading using a calibration standard (span). The wetted parts of the pump are specified according to the application, for example; a Viton® membrane diaphragm can be employed to obtain a wider operating temperature range and provide some chemical resistance to hydrocarbons. The Viton membrane diaphragm places an operating temperature range of 5-50° C. where the pump meets specifications. Below this range, there is a risk of cracking the diaphragm as it stiffens with the lower temperature.
Valve(s) Manifold 360: The valve selected is designed for natural gas service and small volume. Ideally, the valve provides total shutoff of the gas coming into the cell 310 or 320 and minimal restriction when the valve is open. A normally closed (NC) valve provides some protection to the system when the power is not applied. The interior of the valve and cell is not exposed to ambient gases or migrating particles. The primary purpose of the valve is to provide the ability to pump out the cells 310 and 320, either selectively or simultaneously, to provide a reference measurement. As such, the level of optically absorbing gas in the evacuated cell should be as low as possible. The primary sources of leaks in the system are the gas cell windows, fittings, pump, and the valve. The valve itself is sensitive to particulates, like Teflon shavings. The valve seat is made of soft nitrile. Particulate contaminants cause the valve to seat improperly, creating a leak. Removing the contaminant requires removing the valve and disassembling the valve to access the valve seat. The Teflon flake contamination normally only appears during testing or during reconditioning where pipe threads are connected and disconnected. In normal operation, particulates that the valve is exposed must pass through the steel frit that is present on the inlet side of the explosion proof case in addition to the submicron particle filter inside the system.
Flame Arresters 370: These are added to the system for additional safety in case of internal fire or explosion.
FIG. 4 shows additional applications that can be used with the QCL-based gas sensing system. These applications include: monitoring of gases (such as C1-05) in both oil and gas mudlogging operations; Standard Conditions package (or National Electrical Manufacturers Association, NEMA-type enclosures); applications requiring explosion proof enclosures; photoacoustic sensors for environmental monitoring; handheld devices for lithology and analysis of surface contaminants; and downhole applications, in which high pressure and temperature environments are encountered.
FIG. 5 describes an alternative configuration of the system shown in FIG. 1. System 500 includes an additional sample cell 550 used for internal reference purpose. Reference cell 550 contains a known combination of gases, e.g., hydrocarbons, which the system is configured to measure. By providing an internal reference to a gas-standard, variations in system wavelength, power, and/or cavity mode can be corrected on the fly, i.e., in real-time.
As shown, a portion I_c2of the light (combined beam I_c) from the QCL modules is split and directed through a gas cell 550 containing a sample at a known concentrations (“Internal Reference”), while another portion I_c1is further split by beam splitter 502 into two beams I_c11and I_c12, which are directed through the sample cells 510 and 520 and detected by detector system 540.
The reference sample in cell 550 can include one or more gases, and the IR spectrum obtained by detecting beam I′_c2at the detector 540 will be compared to a standard or known spectrum of that gas or mixture of gases, which can be retrieved, for example, from a library containing known spectra of various gases for calibration purposes. Any changes in the measured spectrum from the reference cell 550, such as wavelength drift or amplitude calibration, will be corrected by adjusting the factory calibration to match the standard spectrum. This correction can be performed either by a user or automatically at preselected times, or when certain malfunction of the system is observed by an intelligent algorithm, which is populated with a collection of troubleshooting failure modes and their characteristic manifestation on the measured spectra.
FIG. 6A shows another configuration of a system 600 in which multiple detectors 640 ₁, 640 ₂, . . . , and 640 n, are used. In this example, the combined beam I_cis split by beam splitter 602 into two portions, I_c1and I_c2, which enter the cells 610 and 620, respectively. As shown in FIG. 6A, detectors 640 ₁and 640 ₂are used for detecting IR beams exiting cells 610 and 620 in order to obtain IR absorption spectra for the respective samples. Typically two detectors are used in order to simplify the system, but more than two could be used, if needed. If more than two sample cells are used, the multiple detectors could be used to separately monitor each cell in order to further optimize the system 600. The schemes shown in other alternative configurations can also be modified for use with multiple detectors. FIG. 6B shows yet another configuration with a single gas cell 625, which has at least two different path lengths for the incoming laser beam I_c. In one embodiment, the path lengths are 10 cm and 70 cm, respectively. This dual-path single cell is similar to that shown in FIG. 1B. The two beams I″_c1and I″_c2exiting cell 625 can be detected by detectors D1 and D2, respectively.
FIG. 7 shows another configuration of a system 700 in which a second detector can be used in a real-time referencing scheme. A portion of the combined beam I_cfrom the QCL modules is split off by beam splitter 702 (prior to entering the cells 710 and 720) and directed to a reference detector 742. This signal is used in real-time to compare with the one measured by a signal detector 740. The other portion of the combined beam I_cthat passes through beam splitter 720 is further split into different portions, which are directed to the cells 710, 720 and internal reference cell 750, respectively. The configuration of cells 710, 720 and reference cell 750 is similar to that shown in FIG. 5. As an example, if a pulsed QCL is used as a source, then each pulse can be ratioed to (divided by or normalized to) its original shape, amplitude and wavelength, as recorded by the reference detector 742, which eliminates pulse-to-pulse amplitude and power fluctuations from the laser source. Moreover, the proposed reference detector 742 can be used with all the other alternative configurations listed herein.
FIG. 8 illustrate the operation in which the input beam is pulse modulated. Specifically it shows a self-referencing scheme using a single detector 840. In this example, a narrow pulse from the QCL combined beam I_cis split by beam splitter 802 into two portions, I_c1and I_c2, which are directed into a long path gas cell 820 and the detector 840, respectively. The beam exiting the cell 820 is a pulse I′_c1with a modified shape (compared to I_c1), which is also directed to the detector 840. The path length of the cell 820 is selected so that the modified pulse I′_c1has a sufficiently long time delay (Δt) with respect to pulse I_c2that it is detected as a second pulse by the detector 840, as shown in FIG. 8.
For example, using a 10-30 nanoseconds-wide pulse (feasible with current QCL modules) and a 20 m long gas cell, the delay is about 60 nanoseconds, which is sufficient for separation in time on the detector. Taking ratios of the two pulses, or carrying out other intelligent comparisons between them, such as area, match-filters, spectral composition, etc., the proposed system can provide self-referencing capability in real time.
FIG. 9 shows an alternative configuration of a system 900 (similar to system 800), except that a long open, free space path (not enclosed or confined) of many kilometers through a region can be used as the “gas cell”. In this case, the detector 904 should be configured for detection of both pulses I_c2(split off by beam splitter 902) and I′_c1after the open path, with the modified pulse I′_c1appearing at a much longer time delay (Δt) compared to pulse I_c2. Such an open path through a region configuration can be used for different applications in various environmental conditions, e.g., for monitoring samples in the atmosphere, effluent gases around industrial plants, among others.
FIG. 10 shows an alternative system 1000, in which the initial laser pulse I_c, is split into two portions: I_c1and I_c2, by beam splitter 1002. Pulse I_c1enters a long path sample cell 1120, and exits as a modified pulse I′_c1that is detected by signal detector 1140. Pulse I_c2is further split by splitter 1004 into two portions: I_c21and I_c22. Pulse I_c21is directed into detector 1140, while pulse I_c22is directed into a reference cell 1050, which has been filled with a standard or reference gas (e.g., at a known concentration). The pulse exiting reference cell 1050 (designated as pulse I′_c22) is also detected by detector 1140.
Comparisons can be made using the multiple pulses at the detector 1040, with one or more pulses delayed appropriately for even further refinement of the measurements. In that case, a train of several pulses, e.g., two or three, can be detected by the signal detector 1040. In this example, pulse I_c21(a portion of the original pulse I_c, which has not passed through any sample cell) is first detected, followed by pulse I′_c22from the reference cell 1050 (e.g., modified by the absorption of the reference gas, with time delay), and then modified pulse I′_c1from the long path cell 1020. Comparisons of these IR signal pulses can be made in real-time to provide information for self-referencing purpose or to correct for variations in one or more system parameters.
FIG. 11 shows another possible configuration of a system 1100, in which the QCLs can be used as a source for photoacoustic gas sensing. The light or beam I_cfrom the QCL is used to heat the gas sample in the cell 1120 and the acoustic waves that are generated due to the heating of the gas are detected by a sensitive microphone 1140. Special algorithms can be used to analyze the received signals and gas detection is accomplished, due to the fact that absorption of the light and acoustic propagation are characteristic to each gas.
FIG. 12 shows a configuration in which fast pulsing, slow modulation of the baseline DC current and fast cavity sweep of a QCL are used to provide an output spectrum that is continuous in wavelength. As shown in plot (a) of FIG. 12, the power spectrum of the QCL in the external cavity configuration is not continuous because the laser cavity modes are discrete. The cavity modes are generated by both the laser chip itself (internal cavity) and the external cavity. The internal cavity mode's center wavelength and the mode spacing are determined by the waveguide's refractive index and length. By applying a bias DC current, the local temperature of the waveguide can be modulated, which changes the center wavelength and mode spacing. This is illustrated in plot (b) of FIG. 12, where ΔI represents a change in the DC current (i.e., bias), and the dashed line represents the resulting mode shifting. By varying the DC bias, the internal modes can be moved back and forth in wavelength (spectrally). Plot (c) of FIG. 12 shows the mode shifting as a function of time when the bias current is varied with time (t) (I+ΔI(t). Plot (d) of FIG. 12 shows that, by averaging in time, the output power spectrum becomes continuous. If the bias DC current is lower than the threshold, it will not change the laser pulse's characteristics.
FIG. 13 shows another alternative configuration, in which quasi-single mode lasing for each laser pulse can be achieved by modulating the pumping, baseline DC current. In normal operation, the pulse width of the QCL is very wide, the line width is not transform limited, and there is still mode competition during each pulse. In the QCL in the external cavity configuration, each laser mode is an interference result from the grating dispersion (plot (a)), the external cavity modes (plot (c)), and the internal cavity modes (plot (b)). If at the peak of the grating dispersion, the external cavity mode and the internal cavity mode are perfectly overlapped at a single wavelength, the mode at that wavelength will win the mode competition and be dominant due to constructive interference, as shown in plot (d) of FIG. 13. By adjusting pulse parameters, pumping level, and temperature set point, the internal cavity mode and external cavity mode can be adjusted to align them to the peak of the grating dispersion to generate a quasi-single mode lasing for each pulse. In this operation mode, although there are still some side modes, the majority of the pulse power is concentrated in the main laser mode.
Gas Detection for the Semiconductor Industry Using Mid-Infrared Lasers
Embodiments of the gas sensing system can also be used as a gas analyzer for demanding applications in the semiconductor industry that require both high-speed and high-sensitivity analysis. The gas sensing systems are unique in that they use mid-infrared (MIR) laser technology. This enables multi-gas analysis with sensitivities at the parts-per-billion level (depending on the gas) and with measurement times of less than 1 second. The standard configuration is as an in-line process monitoring and control. The system can be customized based on user requirements.
Mid infrared spectroscopy is a well-developed and proven method for the quantification of gas concentrations. Historically, MIR spectroscopy has required Fourier-Transform Infrared (FTIR) spectrometers which use heated filaments as the source of light. To enable dramatically enhanced performance, widely tunable MIR lasers based on quantum cascade laser (QCL) technology are utilized. QCLs are highly reliable semiconductor lasers that operate over the so-called “molecular fingerprint region” from 5 to 13 microns. The gas sensing system is integrated into a miniature package that is capable very fast wavelength tuning to allow high-speed spectroscopy. The system is capable of making measurements in <0.1 s. However, measurements are typically averaged over >0.5 s to achieve high sensitivity.
The system operates by measuring the transmission spectrum through a gas cell with a heated volume (area) such as an oven. Laser-based gas analyzers have many advantages over FTIR-based systems. For example, since laser beams from the laser tuner remain collimated over long distances, very long-path gas cells can be used. Since the lower detection limit (LDL) improves with increasing length of the gas cell, laser-based systems can achieve LDLs that are more than 10-times better than with an FTIR. Furthermore, as compared to gas cells designed for use with FTIRs, those designed for use with lasers can be made to have much smaller volume. This is important in some applications, e.g., monitoring of semiconductor processing, where fast measurements are required and where the refresh-rate of the gas cell can be a limiting factor.
Table 1 gives examples of several gases along with their LDL when using the standard gas cell having a path length of 6 meters. Since gas cells with path lengths of >100 meters are available, the LDL can be further reduced by a factor of 10 below the values given in Table 1 if required.

TABLE 1

Lower Detection Limit (LDL) for a
several process gases using a gas cell. The
detection limit can be reduced up to 10× using a longer gas cell.

		Lower Detection Limit
	Gas	(measurement time = 0.5 sec)

	Silicon tetrafluoride (SiF₄)	0.04 ppm
	Carbon tetrafluoride (CF₄)	0.02 ppm
	Nitrogen trifluoride (NF₃)	0.2 ppm
	Methane (CH₄)	0.5 ppm
	Xylene (C₈H₁₀)	2.8 ppm
	Formaldehyde (CH₂O)	2.1 ppm
	Ammonia (NH₃)	0.9 ppm

A more expansive list of semiconductor process gases that can be detected with the present system is as follows: H₂O, CO, CO₂, CH₄, NH₃, plus other hydrocarbons; fluoro-carbons: CF₄, C₂F₄, C₂F₆, C₃F₆, C₃F₈, C₄F₆, C₄F₈, C₅F₈; hydro-fluoro-carbons: CH₂F₂, CH₃F, CHF₃, C₂H₃F, C₂HF₃; silicon-containing: SiF₄, SiH₄, SiCl₂H₂; other fluorine-containing: HF, SF₆, NF₃, ClF₃, OF₂, SOF₂, SO₂F₂; other chlorine-containing: CCl₄, BCl₃; nitrogen oxides: NO, N₂O, NO₂; and sulfur oxides: SO₂.
Another related application is gas purity characterization. A list of gases that can be detected for purity by the present system includes: impurities in bulk gases such as He, H₂, Ar, O₂, N₂, H₂O, CH₄, C₂H₆, NH₃, CO₂, CO; impurities in rare gases such as He, Ne, Kr, Xe, Rn; impurities in semiconductor gases such as H₂, SiH₄, SiF₄, HBr, CF₄, CCl₄, NF₃, C₂F₆, C₃F₈, N₂O, C₂H₂, C₂H₆, C₃H₄, PH₃, AsH₃, SF₆, NH₃; trace impurities in gases such as H₂, Ne, Ar, N₂, Kr, CO, CO₂, CH₄; and sulfur, sulfur compounds, H₂S.
There are two variants to the multi-pass gas cell configuration that can be used to detect the above identified gases. FIG. 14 shows a configuration that has mirrors 1420 and 1422 inside the gas cell 1410, with the IR beam exiting the gas cell being detected by detector 1440. FIG. 15 shows the other configuration with mirrors 1520 and 1522 outside the gas cell 1510, and the IR beam exiting the gas cell being detected by detector 1540.
One advantage of the QCL-based gas sensing system is its fast sample rate, with a laser source that covers the spectral range of interest, coupled to an optical cell that is in-line with the process such that there is no need to transport the sample to the monitoring instrument (thus, avoiding any loss of time).
An important feature of the in-line cell confirmation is a negligible pressure drop across the process.
One application for this technology is in the semiconductor fabrication process. Specifically, this QCL-based system can be used for detecting the endpoint of the semiconductor process, i.e., providing real-time information as quickly as possible that the “process is complete”. In one example, SiF₄is produced as a byproduct of an etching process, and once the etching is complete, the SiF₄concentration makes a small step change down (a sudden drop in concentration), which signals the process is complete. It is critical to stop the process as quickly as possible upon the drop in the SiF₄concentration. In this application, the QCL-based gas sensing system monitors the progress of the etch process and then generates a shut-off signal when this SiF₄drop is detected. Another example is chamber cleaning, in which the same byproduct (SiF₄) is produced when fluorine-containing compounds (CF₄, C₂F₆, NF₃) are injected to clean or react with silicon residues on the chamber surfaces. The chamber is “clean” when the SiF₄concentration drops off (indicating the Si is fully consumed). Here, when the QCL-based gas sensing system detects the drop in SiF₄concentration, it stops the injection of these fluorine-containing compounds as quickly as possible.
While this invention has been particularly shown and described with references to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention.

Claims

What is claimed is:

1. A gas sensing system, comprising:

at least one quantum cascade laser configured for tuning within a wavelength range and for providing a beam in the wavelength range;

at least one cell for containing a gas sample, from a semiconductor processing operation, and for receiving the beam; and

a detector system configured for obtaining at least one absorption spectrum for the sample by detecting the beam exiting the at least one cell, which optionally has a multipass cell.

2. A method for gas sensing, comprising:

providing at least one quantum cascade laser configured for tuning within a wavelength range and for providing a beam in the wavelength range;

directing the beam through at least one cell containing a sample from a semiconductor processing operation; and

obtaining at least one absorption spectrum for the sample by detecting the beam exiting the at least one cell, which optionally further comprises determining concentrations of any of the following: H₂O, CO, CO₂, CH₄, NH₃, plus other hydrocarbons; fluoro-carbons: CF₄, C₂F₄, C₂F₆, C₃F₆, C₃F₈, C₄F₆, C₄F₈, C₅F₈; hydro-fluoro-carbons: CH₂F₂, CH₃F, CHF₃, C₂H₃F, C₂HF₃; silicon-containing: SiF₄, SiH₄, SiCl₂H₂; other fluorine-containing: HF, SF₆, NF₃, ClF₃, OF₂, SOF₂, SO₂F₂; other chlorine-containing: CCl₄, BCl₃; nitrogen oxides: NO, N₂O, NO₂; and sulfur oxides: SO₂and impurities in bulk gases such as He, H₂, Ar, O₂, N₂, H₂O, CH₄, C₂H₆, NH₃, CO₂, CO; impurities in rare gases such as He, Ne, Kr, Xe, Rn; impurities in semiconductor gases such as H₂, SiH₄, SiF₄, HBr, CF₄, CCl₄, NF₃, C₂F₆, C₃F₈, N₂O, C₂H₂, C₂H₆, C₃H₄, PH₃, AsH₃, SF₆, NH₃; trace impurities in gases such as H₂, Ne, Ar, N₂, Kr, CO, CO₂, CH₄; and sulfur, sulfur compounds, H₂S.

3. A gas sensing system, comprising:

at least one quantum cascade laser configured for tuning within a wavelength range and for providing a beam in the wavelength range and generating a pulsed beam;

at least one cell for containing a sample and for receiving the beam; and

a detector system configured for obtaining at least one absorption spectrum for the sample by detecting the beam exiting the at least one cell and pulses from the quantum cascade laser, wherein the pulsed beam and the pulses are delayed relative to each other.

4. A method for gas sensing, comprising:

providing at least one quantum cascade laser configured for tuning within a wavelength range and for providing a pulsed beam in the wavelength range;

directing the pulsed beam through at least one cell containing a sample; and

obtaining at least one absorption spectrum for the sample by detecting the pulse beam exiting the at least one cell and the pulsed beam that has not passed through the cell, wherein the pulsed beam from the cell and the pulsed beam not from the cell are delayed relative to each other.