U.S. patent application number 17/136170 was filed with the patent office on 2021-07-08 for devices and methods for quartz enhanced photoacoustic spectroscopy.
The applicant listed for this patent is Pendar Technologies, LLC. Invention is credited to Romain BLANCHARD, Daryoosh VAKHSHOORI.
Application Number | 20210208108 17/136170 |
Document ID | / |
Family ID | 1000005478375 |
Filed Date | 2021-07-08 |
United States Patent
Application |
20210208108 |
Kind Code |
A1 |
BLANCHARD; Romain ; et
al. |
July 8, 2021 |
DEVICES AND METHODS FOR QUARTZ ENHANCED PHOTOACOUSTIC
SPECTROSCOPY
Abstract
In quartz-enhanced photoacoustic spectroscopy (QEPAS), an
analyte (typically in gas phase) generates a pressure wave in
response to incident laser light. A quartz tuning fork (QTF)
resonant at the frequency of the pressure wave transduces the
pressure wave into an electrical signal. Pulsing the laser briefly
reduces the amount of thermal chirp and increases the fraction of
time that the laser emits at the wavelength(s) of interest. This
increases the measurement efficiency. Pulsing the incident laser
light with bursts of short pulses at the QTF resonant frequency
increases signal strength. Exciting the sample with a two pulses at
different laser wavelengths, separated by a half QTF period yields
signal and background acoustic waves that partially cancel when
integrated by the QTF, producing a differential measurement.
Pulsing the incident laser light at a frequency faster than the gas
response cut off frequency can improve the noise performance of a
QEPAS measurement.
Inventors: |
BLANCHARD; Romain;
(Lexington, MA) ; VAKHSHOORI; Daryoosh;
(Cambridge, MA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Pendar Technologies, LLC |
Cambridge |
MA |
US |
|
|
Family ID: |
1000005478375 |
Appl. No.: |
17/136170 |
Filed: |
December 29, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
15840644 |
Dec 13, 2017 |
10908129 |
|
|
17136170 |
|
|
|
|
62433487 |
Dec 13, 2016 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
G01N 29/022 20130101;
G01N 29/348 20130101; G01N 29/2418 20130101; G01N 29/036 20130101;
G01N 2291/021 20130101 |
International
Class: |
G01N 29/24 20060101
G01N029/24; G01N 29/036 20060101 G01N029/036; G01N 29/34 20060101
G01N029/34; G01N 29/02 20060101 G01N029/02 |
Claims
1. A method of making a spectroscopic measurement of a sample, the
method comprising: emitting a sequence of pulses from a single-mode
laser; illuminating the sample with the sequence of pulses; and
detecting radiation transmitted, reflected, and/or scattered by the
sample in response to the sequence of pulses with a detection
system having a low-pass cutoff frequency less than a pulse
repetition frequency of the sequence of pulses.
2. A method of making a spectroscopic measurement of a sample, the
method comprising: modulating a single-mode laser with a repetitive
pulse sequence so as to cause the laser to emit a periodically
pulsed laser beam, each period of the repetitive pulse sequence
comprising a plurality of pulses; illuminating the sample with the
periodically pulsed laser beam; generating an electrical signal
representing radiation reflected, scattered, transmitted, and/or
emitted by the sample in response to the periodically pulsed laser
beam; and bandpass filtering the electrical signal at a band
centered on the pulse repetition frequency.
Description
CROSS-REFERENCE TO RELATED APPLICATION(S)
[0001] This application is a divisional of U.S. application Ser.
No. 15/840,644, filed on Dec. 13, 2017, which claims the priority
benefit, under 35 U.S.C. 119(e), of U.S. Application No.
62/433,487, filed on Dec. 13, 2016. Each of these applications is
incorporated herein by reference in its entirety.
BACKGROUND
[0002] Photoacoustic spectroscopy (PAS) is an analytical chemistry
method that relies on the absorption of light by an analyte
(typically in gas phase), whose subsequent collisional relaxation
generates a pressure wave, detected by a microphone.
Quartz-enhanced PAS (QEPAS) is a particular implementation of PAS
that uses an ultra-sensitive quartz tuning fork (QTF) as the
microphone. Typical modulation frequencies for QEPAS experiments
are in the 5-100 kHz range, with 32.8 kHz being a particularly
favored frequency due to the widespread availability of extremely
cheap tuning forks resonant at this frequency, typically used for
time measurement in wrist-watches.
[0003] In this case, the absorbed energy is transferred via a
pressure wave to a mechanical resonator, typically in the shape of
a tuning fork. Due to its fairly large quality factor
(.about.10,000), the mechanical resonator integrates the signal in
the analog domain, before transduction into an electrical signal,
typically using the piezoelectric properties of the tuning fork
material (e.g., quartz). This analog integration in the mechanical
domain reduces the readout noise of the electrical signal.
[0004] One advantage of QEPAS as a particular form of PAS is that
no optical detector is required since the QTF acts as an uncooled,
wavelength insensitive detector. Furthermore, PAS applications
benefit from QTF's small size (few mm.sup.3), extremely high
quality factor (.about.10,000 at atmospheric pressure), low cost
(<$1 for a standard 32 kHz QTF), and excellent repeatability. In
addition, the noise level is ultimately limited by the thermal
noise of the QTF, which is a few microvolts at room temperature.
The best results have been obtained in the mid-IR fingerprint range
where the strongest target gas absorption lines occur. A record
value of a few tens of parts-per-trillion (ppt) in volume was
obtained for sulfur hexafluoride (SF.sub.6) detection employing an
external cavity mid-IR QCL fiber coupled to the QEPAS module.
SUMMARY
[0005] We present here several devices and methods aimed at
improving QEPAS's signal strength and quality; its robustness
against unwanted background signals of electrical, mechanical, and
optical origin; and its robustness against varying environmental
conditions (e.g., humidity, temperature, and the presence of
different chemical species in the air). The devices and methods
presented can be used to obtain quantitative measurements of the
concentrations of target analytes. Furthermore, different
implementations of QEPAS sensors are presented, including QEPAS
sensors whose sources and spectrophones are integrated for low
cost, easy assembly, and scalable production.
[0006] The description below uses QEPAS as an application field,
although most of the solutions presented are not specific to the
use of a tuning fork as an acoustic detector and can thus apply to
photoacoustic spectroscopy in general. In particular, the different
modulation schemes, the use of humidity sensors, and the strategies
for electrical pick-up noise cancellation are all applicable to
general photoacoustic spectroscopy.
[0007] Embodiments of the present technology include methods of
making spectroscopic measurements of samples. Examples of these
methods include modulating a single-mode laser with a repetitive
pulse sequence so as to cause the laser to emit a periodically
pulsed laser beam. Each period of the repetitive pulse sequence
comprises a plurality of pulses. The periodically pulsed laser beam
illuminates the sample, which cases the sample to reflect, scatter,
transmit, and/or emit radiation (e.g., light or acoustic waves). A
resonant detector whose resonance frequency is equal to a pulse
repetition frequency of the periodically pulsed laser beam detects
this radiation.
[0008] In some implementations, the periodically pulsed laser beam
has a duty cycle of less than 50%. Each period of the periodically
pulsed laser beam may comprises a burst of pulses, with each pulse
in the burst of pulses spanning a bandwidth of less than 1
cm.sup.-1 or less than 0.2 cm.sup.-1. In some cases, the burst of
pulses spans less than half of the period of the periodically
pulsed laser beam.
[0009] Each period of the periodically pulsed laser beam may
comprise at least one first pulse centered at a first wavelength
and at least one second pulse centered at a second wavelength
different than the first wavelength. The second pulse is delayed
with respect to the first pulse by half the period of the
periodically pulsed laser beam. The first and second pulses may
cause the sample to reflect, scatter, transmit, and/or emit first
and second radiation. If so, the resonant detector detect
interference between the first and second radiation.
[0010] Depending on the measurement, light reflected, scattered,
and/or transmitted by the sample may excite the resonant detector.
Alternatively, the sample may emit an acoustic wave in response to
the periodically pulsed laser beam with the resonant detector. The
resonant detector detects this acoustic wave, which causes the
resonant detector to oscillate. These oscillations are converted
into electrical signals, e.g., using the piezoelectric effect.
[0011] Another example method of making a spectroscopic measurement
of a sample includes illuminating a sample with a periodically
pulsed laser beam, each period of which comprises at least one
first pulse centered at a first wavelength and at least one second
pulse centered at a second wavelength different than the first
wavelength. Again, the second pulse is delayed with respect the at
least one first pulse by half the period of the periodically pulsed
laser beam. If desired, the temperature of the single-mode laser
may be tuned between the first and second pulses so as to change
the output wavelength.
[0012] A resonant detector with a resonance frequency substantially
equal to a pulse repetition frequency of the periodically pulsed
laser beam detecting interference between first radiation
reflected, scattered, transmitted, and/or emitted by the sample in
response to the first pulse and second radiation reflected,
scattered, transmitted, and/or emitted by the sample in response to
the second pulse. Depending on the measurement, the first radiation
may represent an absorption resonance of the sample and the second
radiation may represent background absorption of the sample.
[0013] Yet another method of making a spectroscopic measurement of
a sample includes emitting a sequence of pulses from a single-mode
laser. The sequence of pulses illuminates the sample, causing the
sample to transmit, reflect, emit, and/or scatter radiation. A
detection system whose a low-pass cutoff frequency is less than a
pulse repetition frequency of the sequence of pulses detects this
radiation.
[0014] Still another a method of making a spectroscopic measurement
of a sample includes modulating a single-mode laser with a
repetitive pulse sequence so as to cause the laser to emit a
periodically pulsed laser beam. Again, each period of the
repetitive pulse sequence comprises a plurality of pulses. The
periodically pulsed laser beam illuminates the sample, which
reflects, scatters, transmits, and/or emit radiation (e.g., light
or acoustic waves) in response. A detector generates an electrical
signal representing this radiation. And a filter, lock-in
amplifier, processor, or other circuitry bandpass filters the
electrical signal at a band centered on the pulse repetition
frequency.
[0015] It should be appreciated that all combinations of the
foregoing concepts and additional concepts discussed in greater
detail below (provided such concepts are not mutually inconsistent)
are contemplated as being part of the inventive subject matter
disclosed herein. In particular, all combinations of claimed
subject matter appearing at the end of this disclosure are
contemplated as being part of the inventive subject matter
disclosed herein. It should also be appreciated that terminology
explicitly employed herein that also may appear in any disclosure
incorporated by reference should be accorded a meaning most
consistent with the particular concepts disclosed herein.
BRIEF DESCRIPTIONS OF THE DRAWINGS
[0016] The skilled artisan will understand that the drawings
primarily are for illustrative purposes and are not intended to
limit the scope of the inventive subject matter described herein.
The drawings are not necessarily to scale; in some instances,
various aspects of the inventive subject matter disclosed herein
may be shown exaggerated or enlarged in the drawings to facilitate
an understanding of different features. In the drawings, like
reference characters generally refer to like features (e.g.,
functionally similar and/or structurally similar elements).
[0017] FIG. 1A is a schematic of a system for quartz-enhanced
photoacoustic spectroscopy (QEPAS). The quartz tuning fork detector
is typically inside the gas chamber since that is where the
acoustic wave exciting the tuning fork is usually generated. A
humidity sensor is added in the gas chamber.
[0018] FIG. 1B is a schematic of a typical system for absorption
spectroscopy. The detector is in this case typically outside of the
gas cell.
[0019] FIG. 1C illustrates the different stages of signal
generation for a photoacoustic spectroscopy experiment, from the
laser driver waveform to the final detector output. This case
represents the typical case whereby a single pulse is used to
excite the acoustic wave, which in turn excites mechanical
vibrations of a mechanical resonator in the detector.
[0020] FIG. 1D illustrates the different stages of signal
generation for a photoacoustic spectroscopy experiment using a
complex pulse pattern to generate the acoustic wave, which in turn
excites mechanical vibrations of a mechanical resonator in the
detector.
[0021] illustrates a complex but periodic pulse sequence for
modulating a single-mode laser (lower trace) and the acoustic
modulation period (upper trace) generated by illuminating a sample
with the laser light emitted by the single-mode laser in response
to the periodic pulse sequence.
[0022] FIG. 2A shows a simple pulse pattern with a single pulse per
period for modulating a single-mode laser, such as a distributed
feedback (DFB) quantum cascade laser (QCL).
[0023] FIG. 2B is a plot of the time evolution of the laser light
frequency emitted by a single-mode laser in response to the simple
pulse pattern shown in FIG. 2A, within one repetition period at
32.8 kHz, assuming a single drive pulse of 300 ns starting at t=0,
and a thermal relaxation time constant for the active region of 0.8
.mu.s (this value will be used in all following examples).
[0024] FIG. 2C is a close-up of the plot in FIG. 2B showing with
shading indicating that if, for example, a gas only absorbs at
laser wavelengths between 2221.42222.6 cm.sup.-1 and 22212222.8
cm.sup.-1, then the photoacoustic signal is only generated during
<50 ns of the total 300 ns of the pulse.
[0025] FIG. 3A illustrates a pulse pattern of 6 pulses each 50 ns
in duration with a 1 .mu.s delay between pulses for modulating a
single-mode laser.
[0026] FIG. 3B illustrates temperature fluctuations in a
single-mode laser modulated with the pulse pattern of FIG. 3A.
[0027] FIG. 3C illustrates wavenumbers of the laser output
corresponding to the different temperatures shown in FIG. 3B.
[0028] FIG. 3D illustrates a pulse pattern of 15 pulses each 20 ns
in duration with a 1 .mu.s delay between pulses for modulating a
single-mode laser.
[0029] FIG. 3E illustrates temperature fluctuations in a
single-mode laser modulated with the pulse pattern of FIG. 3D.
[0030] FIG. 3F illustrates wavenumbers of the laser output
corresponding to the different temperatures shown in FIG. 3E.
[0031] FIG. 4A is a plot of experimental emission spectra obtained
for a distributed feedback QCL driven with different pulse
patterns. The bias voltage is kept constant. the repetition rate of
the modulation pattern is 32 kHz, and the sub-pulses are all
grouped into the first 15 .mu.s of the modulation period (.about.30
.mu.s).
[0032] FIG. 4B is a plot of measured increase in average power with
increasing number of sub-pulses (crosses). The line is a linear
interpolation.
[0033] FIG. 5 illustrates an example of a typical absorption
spectrum showing on-line absorption band and off-line baseline.
[0034] FIG. 6A is a schematic illustrating a pulse pattern for a
differential spectroscopic measurement using a single-mode laser.
During the first half of the period (0<t<15.2 .mu.s), a train
of 14 pulses, each 20 ns in duration and with a 1 .mu.s delay
between pulses. Then a second train of similar pulses is fired in
the second half, summed in amplitude to a single 15 .mu.s long
pulse with a tenth of the amplitude of the previous pulses.
[0035] FIG. 6B is a plot of the time evolution of the laser active
region temperature in response to the pulse pattern shown in FIG.
6A.
[0036] FIG. 6C is a plot of the time evolution of the laser
emission wavenumber in response to the pulse pattern shown in FIG.
6A.
[0037] FIG. 7A is a schematic illustrating a pulse pattern for
modulating a single-mode laser to make a differential spectroscopic
measurement (baseline subtraction). The modulation is as follows:
during the first half of each period (0<t<15.2 .mu.s) of the
32.8 kHz periodic pattern, a train of 14 pulses, each 20 ns in
duration and with a 1 us delay between pulses is used, followed by
a train of 5 pulses, each 60 ns in duration and with a 0.8 .mu.s
delay between pulses, during the second half period. All pulses
have the same amplitude.
[0038] FIG. 7B shows expected temperature fluctuations of the
laser's active region in response to the pulse pattern in FIG.
7A.
[0039] FIG. 7C shows wavenumbers corresponding to the different
temperatures in FIG. 7B.
[0040] FIG. 7D shows a few cycles of the modulation of FIG. 7A,
repeated with a 30 .mu.s period.
[0041] FIG. 8A is a schematic illustrating another pulse pattern
for a differential measurement (baseline subtraction). The
modulation is as follow: during the first half of each period
(0<t<15.2 .mu.s) of the 32.8 kHz periodic pattern, a train of
50 pulses, each 20 ns in duration and with a 280 ns delay between
pulses is used, followed by a train of 50 pulses, each 30 ns in
duration and with a 270 ns delay between pulses, during the second
half period.
[0042] FIG. 8B shows expected temperature fluctuations of the
laser's active region in response to the pulse pattern in FIG.
8A.
[0043] FIG. 8C shows wavenumbers corresponding to the different
temperatures in FIG. 8B.
[0044] FIG. 8D shows a few cycles of the modulation of FIG. 8A,
repeated with a 30 .mu.s period.
[0045] FIG. 9A shows a simulation of an acoustic waveform excited
by the absorption of a laser modulated with a single 300 ns long
pulse per period and a pulse repetition rate of 32.8 kHz
modulation, assuming a vibrational-translational relaxation time
constant for the gas analyte of 30 .mu.s.
[0046] FIG. 9B shows an acoustic waveform obtained with a laser
modulated with a train of 15 pulses, each 60 ns in duration and
fired during the first half of the modulation period for a 32.8 kHz
pulse repetition rate
[0047] FIGS. 10A-10C illustrate how a three-prong tuning fork
generates an acoustic wave in response excitation by a laser in
quartz-enhanced photoacoustic spectroscopy (QEPAS).
[0048] FIG. 11 is a schematic of a QEPAS setup using two tuning
forks wired in such a way as to subtract the electrical signals
generated by each tuning fork.
[0049] FIG. 12 is a schematic of circuitry that performs
electromagnetic pick-up noise subtraction. A switch, realized, for
example, with transistors directly defined on the semiconductor
laser chip (e.g., indium phosphide in the case of quantum cascade
lasers), can allow for the alternative drive of the laser source
and of a dummy load with similar electrical characteristic than the
laser, located in close proximity to the laser, on the same
chip.
[0050] FIG. 13 is a schematic of a QEPAS device that can use the
pulse patterns shown in the preceding figures.
[0051] FIG. 14 is a schematic showing the use of an aperture for
spatial filtering with a tuning fork for a QEPAS measurement.
[0052] FIGS. 15A-15I illustrate geometries for QEPAS devices based
on edge-emitting semiconductor lasers. All schematics show the
device seen from the top. The laser epi layers are in the plane of
the schematic. The tuning fork prongs are represented as two
crossed rectangles.
[0053] FIGS. 16A and 16B are schematics showing the use of on-chip
optical elements to image the laser facet onto a point located
between the tuning fork prongs.
[0054] FIGS. 17A-17C show different QEPAS device configurations
using surface-emitting lasers.
[0055] FIGS. 18A and 18B show side and front views, respectively,
of a laser architecture with a substrate emitting laser.
[0056] FIG. 19 shows an exploded view of an integrated QEPAS sensor
(subassembly) with a laser source, optical element, aperture and
tuning fork.
[0057] FIG. 20 illustrates a wafer-bonding process suitable for
making an integrated QEPAS sensor like the one shown in FIG. 20,
whereby the different functionalities are merged into a single
subassembly by bonding wafers with two-dimensional arrays of
lasers, lenslet arrays, apertures, and tuning forks.
[0058] FIGS. 21A-21D show a set of geometries based on
surface-emitting semiconductor lasers. All schematics show the
device seen from the side (cross section along the length of the
lasers). The tuning fork prongs are represented as two crossed
rectangles in FIGS. 21B-21D.
DETAILED DESCRIPTION
[0059] The devices and methods presented here address issues
related to the use of semiconductor lasers as a source of light for
a PAS spectrometer. For example, when using a pulsed
distributed-feedback (DFB) quantum cascade laser (QCL) emitting in
the infrared spectral range, the heating of the QCL's active region
during the pulse duration (on the scale of a few nanoseconds to a
few microseconds) leads to a change of the refractive index and
consequently a chirp of the emitted laser light (i.e., a change of
frequency versus time). For a pulse duration on the order of a few
hundred nanoseconds, that chirp is typically on the order of 1 to 3
cm.sup.-1, although this value can be made smaller or larger based
on the heat dissipated in the QCL's active region. For example, a
laser with high doping of the active region typically draws more
current and thus dissipates more heat, leading to a larger chirp
rate. The efficiency of the active region and thus the amount of
heat it generates for a given input electrical power can also be
adjusted by proper band-structure engineering.
[0060] Chirping due to temperature changes reduces the efficiency
of a PAS measurement because gas absorption lines, even at ambient
conditions of temperature and pressure, are typically narrower than
the chirp bandwidth. To see why, consider a gas line with an
absorption linewidth of .DELTA.v.sub.gas (which may be smaller than
1 cm.sup.-1) and a laser that chirps over .DELTA.v.sub.chirp during
the duration of the electrical driver pulse .tau., where we assume
that .DELTA.v.sub.chirp>.DELTA.v.sub.gas and that
.DELTA.v.sub.chirp encompasses the full absorption linewidth. The
effective time during which the laser light is absorbed by the
analyte is thus on the order of
(.DELTA.v.sub.gas/.DELTA.v.sub.chirp).tau.. In other words, only a
fraction .DELTA.v.sub.gas/.DELTA.v.sub.chirp of the laser energy
contributes to the generation of the photoacoustic signal, the
remainder being wasted.
[0061] This observation is generalizable to other spectroscopic
techniques employing slow detectors, in which an average quantity
is measured. A slow detector refers here to a detector with a time
constant larger than the typical time it takes a pulsed laser to
chirp through a gas line. For example, for infrared spectroscopy
based on pulsed quantum cascade lasers, a detector with a time
constant larger than 1 microsecond can be considered slow since
such detector may not be able to resolve the absorption dip as the
laser chirps through a gas line during a single pulse. Note that
other elements of the system (e.g., the pre-amplifier or the
digitizer) may limit the bandwidth and that the overall system
response speed should be considered. When a slow detector is used,
the quantity measured is typically the total amount of light
absorbed by the gas over the pulse duration, measured indirectly
via the amplitude of the consequently generated acoustic wave for
PAS, or directly as a transmission dip in more typical infrared
absorption spectroscopy. In these cases, only a fraction
.DELTA.v.sub.gas/.DELTA.v.sub.chirp of the laser energy contributes
to the generation of information.
[0062] Another spectroscopic technique using a slow, resonant
detector is the use of a mechanical resonator as a light detector.
A mechanical resonator, for example, a quartz tuning fork, can be
excited by photothermal effects when the radiation impinging on the
resonator material is partially absorbed by the material, leading
to a local heating of the material and consequent strain. The
photoelectric effect may also result in the creation of surface
charges when the light is impinging on the resonator material,
which may in turn strain the material if the material has a
significant piezoelectric coefficient. The techniques described
here, aimed at increasing or maximizing signal strength and
mitigating background signal and noise in QEPAS, also apply to most
techniques employing slow detectors, such as the resonant
thermomechanical technique described in this paragraph.
High Frequency Modulation
[0063] It is usually assumed by QEPAS practitioners that the
modulation frequency should be similar or slower than the analyte
vibrational-translational relaxation time, which acts as a low-pass
for the photoacoustic signal. However, there are several advantages
to using modulations faster than the analyte
vibrational-translational relaxation time:
[0064] (1) A fast modulation can be used to increase the effective
duty cycle of the measurement. As mentioned above, long laser
pulses lead to larger intra-pulse chirp range. When
.DELTA.v.sub.chirp>.DELTA.v.sub.gas, which is commonly the case,
increasing the laser pulse duration does not lead to an increase in
signal since it increases the chirp range .DELTA.v.sub.chirp. In
other words, the laser is not exciting the gas molecules during
that extra duration. Increasing the modulation frequency (i.e.,
decreasing the pulse repletion period) at constant pulse width thus
leads to a proportional increase of energy transferred to the gas
per unit of time, resulting in an increase of acoustic signal
generated per unit of time proportionally to the modulation
frequency.
[0065] (2) A fast modulation can help isolate the generated
acoustic signal from ambient noise and 1/f noise. To see how a
modulation faster than the analyte vibrational-translational
relaxation time can be used, consider a measured photoacoustic
signal S that is proportional to a(f)*P.sub.average*Q, where a(f)
is a factor representing the efficiency of the acoustic wave
generation for a modulation at frequency f, P.sub.average is the
laser average power (proportional to f if the pulse width is
fixed), and Q is the fork quality factor. The effect of the limited
V-T relaxation time is similar to that of a first order low-pass
filter, resulting in a coefficient a(f) approximately proportional
to 1/f Consequently, when increasing the modulation frequency fin
an experiment involving pulsed lasers with
.DELTA.v.sub.chirp>.DELTA.v.sub.gas, the photoacoustic signal is
approximately conserved. However, the fast frequency operation can
enable easier frequency-based filtering from ambient noise, 1/f
noise, etc.
PAS with Pulsed Semiconductor Lasers
[0066] Quantum cascade lasers (QCLs) are often used as sources of
light in QEPAS spectrometer since they can emit light in the
mid-wave and long-wave infrared regions (3-16 .mu.m) and beyond in
the terahertz spectral range. These spectral ranges are relevant
for analytical chemistry since many molecules have unique
absorption features (such as sharp absorption lines) corresponding
to the excitation of ro-vibrational modes of the molecules.
Measuring a spectrum containing these features can allow for the
identification and quantification of these molecules.
[0067] Most QEPAS experiments to date using QCLs use continuous
wave (CW) devices that emit light continuously for at least the
duration of the measurement. In contrast to pulsed QCLs, CW-QCLs
require good thermal dissipation, with design implications from the
package to the laser waveguide level, driving constraints for
system weight, size, power consumption, manufacturing cost, and
laser fabrication yield. These lasers are also usually on the order
of ten times less efficient at converting electrical power into
optical power than pulsed QCLs. It can thus be advantageous to use
pulsed QCLs in situations that benefit from small size, weight,
power, and cost. Furthermore, since the frequency tuning obtained
with the intra-pulse chirp of pulsed lasers is an intrinsic effect
that does not require additional components or control, pulsed QCLs
provide a faster, simpler and potentially more accurate solution
than the typical current or temperature ramps used in the frequency
tuning of CW lasers.
[0068] We present here processes that can be used to optimize the
amount of acoustic energy generated from the gas absorption of the
laser light, and the amplitude of the signal readout from the
piezo-electric transducer. These processes include increasing the
efficiency of acoustic signal generation by increasing the time
during which the laser is on and the frequency of its emitted light
overlaps the gas absorption line targeted by the measurement. They
also include increasing the piezoelectric signal by (1) modulating
the laser light at or close to the resonant frequency of the tuning
fork; and/or (2) reducing the energy that is lost to the excitation
of higher harmonics of the mechanical oscillator (unless these are
also measured and contribute to the acquired signal).
[0069] FIG. 1A shows a system for conducting QEPAS measurements
using inventive architectures, inventive pulsed modulation schemes,
or both. The system of FIG. 1A includes a laser driver 101 that
applies a repetitive sequence of electrical pulses to a single-mode
laser 102, such as a DFB QCL. The single-mode laser 102 emits a
repetitive sequence of optical pulses in response to the repetitive
sequence of electrical pulses. An optical system 103 comprising
lenses, mirrors, prisms, and/or other optical components shape and
direct these optical pulses to a gas cell 104 that contains a
resonant detector (e.g., a quartz tuning fork 107) and an optional
humidity detector 112.
[0070] In operation, an analyte gas flows into the gas cell 104 via
an inlet 105 and out of the gas cell 104 via an outlet 106. The
optical system 103 focuses the optical pulses between the prongs of
the tuning fork 107, which may have a resonance frequency from
about 1 kHz to several MHz (e.g., 32 kHz resonance). The focused
optical pulses heat the analyte gas between the tuning fork prongs,
which drives a pressure wave (i.e., an acoustic wave), which in
turn excites the tuning fork 107. Alternatively, the optical system
103 may focus the optical pulses onto the tuning fork 107 for
resonant thermomechanical spectroscopy measurements, which involve
exciting the tuning fork directly with the light instead of with an
acoustic wave in the gas analyte.
[0071] A pre-amplifier 108 and lock-in amplifier 109 read the
tuning fork's mechanical oscillations as an electrical signal via
the piezoelectric effect. (Alternatively, the tuning fork
oscillations can be read optically using an interferometer or
deflectometer.) An analog-to-digital converter (ADC) 110 digitizes
the output of the lock-in amplifier 109 for processing by a
computer 111, which uses the electrical signal and the humidity
sensor's output to control the laser driver 101. Lock-in detection
may also be realized in digital space: in this case, the output of
the pre-amplifier is first digitized, and algorithms (e.g. Fourier
transforms and digital filtering) may be used to extract the signal
amplitude and phase at a specific frequency (e.g. the resonance
frequency of the resonant detector).
[0072] FIG. 1B shows an inventive system for absorption
spectroscopy. It includes all of the same components shown in FIG.
1A, except that the detector 107 is outside of the gas cell 104.
The detector in the absorption spectroscopy system of FIG. 1B can
be either a resonant detector or a non-resonant detector. For
instance, the detector may be a slow detector as described above.
If desired, the lock-in amplifier 109 can bandpass filter the
electrical signal (e.g., current or voltage) generated by the
detector 107 at a band centered on the pulse repetition frequency
of the electrical signal used to modulate the laser 102. (This
bandpass filtering may also be accomplished with a separate analog
filter or in the digital domain, e.g., with a processor.) This
reduces 1/f noise and make it possible to deposit more energy in a
narrow wavelength bandwidth by emitting many short optical pulses
from the laser 102.
[0073] FIG. 1C shows the inputs and outputs in a conventional QEPAS
or absorption spectroscopy measurement using a resonant detector.
The top trace shows the laser drive voltage, which is a pulsed
modulation scheme with a single electrical pulse per repetition
period. The next trace shows the laser output power, which is also
a single optical pulse per repetition period. When focused to a
point in the gas, these optical pulses produce acoustic waves with
sharp leading edges and exponentially decaying trailing edges as
shown in the middle trace. The acoustic waves excite
quasi-sinusoidal mechanical oscillations in the resonant detector
(tuning fork) that in turn produce a quasi-sinusoidal electrical
signal as shown in the bottom two traces of FIG. 1C.
[0074] Instead of this usual method, we modulate a single-mode
laser, such as a DFB QCL, with a complex pulse pattern formed by
the periodic repetition (for example, at the tuning fork resonance
frequency) of a short sequence of pulses, with varying duration,
amplitude, and delays. The top trace in FIG. 1D shows one example
of this complex pulse pattern. The single-mode laser emits the
complex optical pulse pattern shown in the next trace in FIG. 1D
(there may not be a one-to-one correspondence between the
electrical pulses modulating the laser and the optical pulses
emitted by the laser). In a QEPAS measurement, these optical pulses
produce sawtooth-like acoustic waves (middle trace in FIG. 1D),
which cause sine-like mechanical oscillations of the tuning fork
(second-lower trace in FIG. 1D that in turn yield sine-like
electrical signals (bottom trace in FIG. 1D).
[0075] We call the repetition period of the complex pulse pattern
the "acoustic modulation period", as shown in FIG. 1D, to emphasize
the fact that it is the period at which the acoustic waves are
generated in order to excite the resonant detector used to sense
the laser light reflected, transmitted, and/or scattered by the
sample. It corresponds to the frequency that one may want to match
to the resonant frequency of the resonant detector, which may be a
tuning fork or an acoustic resonator.
[0076] The number of pulses composing this repeated pattern used to
modulate the laser is another design parameter. By synthesizing
this complex pulse sequence, it is possible to (1) shape the
temperature profile (over time, within each modulation period) of
the active region and thus the laser light frequency variation over
time, within the duration of the modulation period; and (2) shape
the frequency spectrum of the generated acoustic wave, and in
particular the energy distribution between the fundamental
modulation and its harmonics. In doing so, it is possible to
increase the energy transfer to the acoustic wave and the strength
of the signal measured by the resonant detector. Several strategies
can be employed, including but not limited to: adjusting the number
of sub-pulses, their heights, and their durations; adding sub
threshold pulses to rapidly tune the laser center frequency; and
adding a long and low amplitude pulse to the train of
sub-pulses.
[0077] If desired, the pulse sequence shown in the top trace of
FIG. 1D may be varied to slowly ramp the center frequency of the
optical pulses emitted by the laser. For example, the pulse
sequence may include a constant number of pulses per sequence
period (e.g., 20 pulses in 15 .mu.s, repeated every 30 .mu.s), but
with a slowly decreasing delay between pulses (e.g., from 0.79
.mu.s to 0.3 .mu.s). If desired, the pulse duration may vary from
about 5 ns to about 5 .mu.s. And the please pulse power may range
from about 10 mW to about 500 mW. The exact pulse sequence,
duration, delay, and amplitude may depend on the laser geometry,
laser doping, how much energy is deposited in the active region
volume, and what is the thermal conductivity of this volume. But as
described below, a steady state can be established in just a few
cycles (e.g., <5 .mu.s total time), so that even if the
temperature of the active region does not relax fully in between
pulses, the temperature range spanned by a pulse can be equal to
the one spanned by the previous pulses.
[0078] FIGS. 2A-2C show the time evolution of the modulation and
laser light frequency for a single-mode pulsed laser. FIG. 2A shows
the modulation used to drive the laser. The modulation has a pulse
repetition frequency of 32.8 kHz, which matches the resonance
frequency of readily available quartz tuning forks, and include a
single drive pulse of 300 ns starting at t=0. FIGS. 2B and 2C show
the wavelength of the laser, which has a thermal relaxation time
constant for the active region of 0.8 .mu.s (this thermal
relaxation time constant is used in all following examples). It
should be noted that the laser is only emitting light during the
downward slope of the curve, while the upward slope reflects the
cooling of the active region after the electrical driving pulse
terminates. As can be seen, the laser chirps over 1.3 m.sup.-1
during the short duration of the electrical pulse, which is
significantly larger than most gas absorption lines. A zoom-in in
FIG. 2C shows that if, for example, a gas only absorbs between
2222.6 cm.sup.-1 and 2222.8 cm.sup.-1, then the photoacoustic
signal is only generated during <50 ns of the total 300 ns of
the pulse.
[0079] FIGS. 3A-3F show similar data for a laser modulated with a
300 ns driving pulse split into 6 pulses each 50 ns in duration
(FIGS. 3A-3C) or 15 pulses each 20 ns in duration (FIGS. 3D-3F),
with a 1 .mu.s delay between pulses in both cases. This corresponds
to the same total ON time for the laser in FIGS. 2A-2C, and thus
the same energy consumption and total heat dissipation. However, by
spreading that heat deposition over half the repetition period, the
amplitude of the temperature variation of the active region, and
consequently the amplitude of the chirp in the emitted laser beam
is reduced. This enables more efficient use of the laser energy to
generate the acoustic signal, since the frequency of the emitted
laser light overlaps the analyte absorption band for a longer
fraction of the time it is turned on.
[0080] FIGS. 3A and 3D are schematics illustrating the pulse
patterns used to modulate the laser. FIGS. 3B and 3E show the
expected temperature fluctuations of the active region in response
to the pulse patterns in FIGS. 3A and 3D, respectively. (Note that
the exact temperature variations may depend on the laser design,
and in particular the laser ridge geometry, the active region
doping, the active region efficiency, etc.) Finally, FIGS. 3C and
3F show the wavenumbers corresponding to the different temperatures
in FIGS. 3B and 3E, respectively: there is a one-to-one mapping
between the laser temperature and the wavenumber of the emitted
light. Note that the laser is only lasing during the pulses, i.e.,
during the portion of the curves where the temperature increases
and the wavenumber decreases. Note that the pulse height is
indicated here and in the following figures as 15 V, as an example
of above threshold voltage. This pulse height may be adjusted to
the drive condition of the particular laser used.
[0081] FIGS. 3A-3F illustrate the increase in average power emitted
within the absorption bandwidth of a narrow-line gas absorber,
using the simulated temperature response of a QCL active region,
and the corresponding wavenumber chirp of the laser light. As can
be observed, breaking out a single long pulse into multiple shorter
pulses can reduce the wavenumber range over which the laser chirps,
thereby increasing the total power deposited within the narrow
absorption bandwidth of a gas line.
[0082] FIG. 4A reports experimentally measured emission spectra
confirming this effect using a pulsed distributed feedback quantum
cascade laser. It shows how an increase in power is obtained within
a narrow spectral bandwidth (0.5 cm.sup.-1), for a constant laser
bias, for an increasing number of short, identical sub-pulses. Each
trace represents the emission spectrum for a different number of
sub-pulses in each period of the laser modulation signal, with the
number of pulse ranging from 1 (lowest peak) to 20 (highest peak).
For this experiment, the repetition rate of the modulation pattern
was 32 kHz, and the sub-pulses were all grouped into the first 15
.mu.s of a quartz tuning fork modulation period (.about.30
.mu.s).
[0083] FIG. 4B is a plot of average power emission spectrum versus
number of sub-pulses (crosses) used to modulate single-mode power.
The line is a linear interpolation. By allowing cooling of the
active region between consecutive short pulses, the efficiency of
the laser is also increased and we can observe in FIG. 4B that the
average power scales linearly with the number of sub-pulses. This
is to be contrasted to a drive scheme with a single pulse of
increasing duration, for which typically the increase in average
power with pulse width is sub-linear, reflecting the reduction in
efficiency as the active region temperature increase during the
pulse.
Differential PAS Measurements
[0084] Several QEPAS results reported in the literature use a
so-called 2f-demodulation scheme. In this method, a CW laser is
modulated by a sine wave such that its center frequency also
follows a sine wave modulation centered on the gas absorption line.
The laser center frequency thus crosses the peak of the absorption
line twice within a period. In other words, a strong acoustic
signal is generated at twice the frequency of the laser modulation.
A lock-in set to detect that second harmonic will thus reject any
signal at the fundamental laser modulation frequency, which could
originate from a variety of sources such as electrical pick-up,
light absorption by the tuning fork if the optical beam hits the
fork, or acoustic signal generated by absorbers in the beam path,
such as optical windows. Note that for efficient excitation of the
second harmonic, the absorption line should be symmetric about its
peak and the laser center frequency (i.e., its mean frequency over
a modulation period) should match the peak absorption.
[0085] The 2f-demodulation technique cannot be implemented with
standard pulsed patterns since the laser frequency crosses the
maximum absorption only once per modulation period. However, we
present here an alternative with some of the same advantages. For
the sake of example, consider an absorption spectrum as shown in
FIG. 5, featuring a narrow absorption line and a baseline
absorption in the vicinity that is relatively featureless. The
position and width of the two bands (`absorption line` and
`baseline absorption`) are arbitrary here and in the following
figures.
[0086] FIGS. 6A-6C illustrate a differential spectroscopic
technique using a pulsed single-mode laser, such as a DFB QCL.
FIGS. 6B and 6C show the temperature of the laser's active region
and the laser wavenumber versus time, respectively, during one
modulation period at 32.8 kHz for a single-mode laser modulated
with the modulation pattern shown in FIG. 6A. During the first half
of the period (0<t<15.2 .mu.s), a train of 14 pulses, each 20
ns in duration and with a 1 .mu.s delay between pulses. Then a
second train of similar pulses is fired in the second half, summed
in amplitude to a single 15 .mu.s long pulse with a tenth of the
amplitude of the previous pulses. That long pulse allows for an
offset of the active region temperature and thus an offset in the
wavenumber of the emitted light between the two half periods.
[0087] FIG. 6C shows the result of the modulation shown in FIG. 6A:
(1) assuming the laser wavenumber overlaps the absorption line in
only the first half period, the photoacoustic signal is only
generated in the first half period, and it is modulated at 32.8
kHz, assumed to be here the resonance frequency of the tuning fork;
(2) a second out-of-phase photoacoustic signal is generated during
the second half of the modulation period. This signal is also
modulated at 32.8 kHz.
[0088] By adjusting the amplitude, width or delay between the
sub-pulses in FIG. 6A, it is possible to balance the two signals in
FIG. 6C (on-line and off-line), for example, in the absence of the
target gas analyte (e.g., during `zero-gas` calibration), to obtain
a differential measurement. Because the two signals are
out-of-phase with respect to the acoustic modulation period, they
subtract from one another in the final measured signal; (3)
Finally, a background absorption or signal (e.g., from optical
window absorption, or from the laser light hitting the tuning fork
prongs) that is frequency insensitive on the scale of the
intra-pulse laser wavenumber variations contributes to an equal
signal during both half periods. In other term, the corresponding
photoacoustic signal is modulated at 2f and thus can be rejected if
the amplitude of only the fundamental modulation is measured. Note
that this is the opposite strategy of the usual 2f-demodulation
scheme often used in QEPAS, where the useful signal is modulated at
2f and the background is modulated at f.
[0089] The modulation scheme shown in FIG. 6A has several
advantages, including but not limited to: [0090] 1) If a
differential measurement is realized this way, between on- and
off-line frequency bands, the measurement can have a reduced
sensitivity to laser power variations over time. [0091] 2) If a
strong background signal is generated (for example, if the laser
beam hits the prong of a tuning fork), it can be separated from the
useful chemically relevant signal since the background and
chemically relevant signals are modulated at different frequencies.
[0092] 3) By adjusting the amplitude, delay and width of the pulse
sub-pattern, it is possible to adjust the amount of photoacoustic
signal generated in different sections of the modulations. This can
be used to increase the amount of photoacoustic signal generated
from the absorption of the target analyte, reduce the amount of
photoacoustic signal generated by baseline or background
absorption, or balance the generation of photoacoustic in different
sections of the modulations (for example, in- and out-of-phase
signal components). [0093] 4) Any potential electrical pick-up
signal is mostly modulated at a much higher frequency than the
tuning fork resonance. Therefore, the modulation scheme can
decrease the background signal (and its associated noise) due to
electrical pick-up at the frequency at which the chemical
information is coded and measured. [0094] 5) The advantages of this
modulation scheme do not rely on a symmetry of the absorption
feature about its peak. It can be implemented for fairly broad
absorption features, assuming the laser can be tuned far
enough.
[0095] We assumed above a narrow absorption line such that the
laser center frequency can be tuned from `on-line` to `off-line` on
a time scale smaller than the acoustic modulation period, by
adjusting the complex pattern parameters (numbers of pulses, their
amplitude, duration, delay, etc . . . ). Some gases have relatively
broad absorption lines (full width at half maximum of a few
wavenumbers). For these gases, it may not be practical or even
possible to switch between on- and off-line with intra-pulse
tuning, although in the case of quantum cascade lasers, high doping
of the active region can allow for intra-pulse tuning on the scale
of 10 cm.sup.-1 per microsecond at .about.4.5 microns wavelength.
However, the modulation scheme presented here to achieve a
differential measurement can still be used to measure the
derivative (i.e., the slope) of the absorption line. A slow
temperature ramp of the submount or heat sink can be used to slowly
(i.e., at a time scale larger than the acoustic modulation period)
tune the laser center frequency over the absorption line.
[0096] FIGS. 7A-7D illustrate another differential spectroscopic
technique using a pulsed single-mode laser. FIG. 7A is a schematic
illustrating the pulse patterns. FIG. 7B shows the expected
temperature fluctuations of the single-mode laser's active region
in response to the pulse pattern shown in FIG. 7A. FIG. 7C shows
the wavenumbers of the laser output corresponding to the different
temperatures shown in FIG. 7B. FIG. 7D shows a few cycles of the
periodically pulsed laser beam, repeated with a 30 .mu.s
period.
[0097] Since it can be difficult in practice to adjust the
electrical driving pulse height at the microsecond scale, or to sum
two drive pulses as is used in FIGS. 6A-6C, we show in FIG. 7A
another possible pulse pattern obtained by adjusting only the pulse
durations and delays. In FIG. 7A, the modulation is as follow:
during the first half of each period (0<t<15.2 .mu.s) of the
32.8 kHz periodic pattern, a train of 14 pulses, each 20 ns in
duration and with a 1 .mu.s delay between pulses is used, followed
by a train of 5 pulses, each 60 ns in duration and with a 0.8 .mu.s
delay between pulses, during the second half period. All pulses
have the same height.
[0098] We note that it may be desired to tune the pulse pattern so
that the on-line and off-line signals have equal amplitudes in the
absence of analyte. This ensures zero signal in the absence of
analyte and a zero-offset differential signal in the presence of an
analyte. For example, one may adjust the number of pulses in each
sub-sequence or their duration to achieve such tuning.
[0099] FIGS. 8A-8D illustrate yet another example of differential
spectroscopic measurements using a pulsed single-mode laser. In
FIG. 8A, the modulation of the laser is as follow: during the first
half of each period (0<t<15.2 us) of the 32.8 kHz periodic
pattern, a train of 50 pulses, each 20 ns in duration and with a
280 ns delay between pulses is used, followed by a train of 50
pulses, each 30 ns in duration and with a 270 ns delay between
pulses, during the second half period. FIGS. 8B and 8C show the
temperature of the laser's active region and the wavenumber of the
laser's output, respectively, as a function of time when the laser
is modulated with the pulse pattern shown on FIG. 8A. A few periods
of the 32.8 kHz modulation are shown in FIG. 8D. Note that this
later pulse scheme has a higher duty cycle (8.2%), implying higher
heat dissipation of the laser.
[0100] The pulses pattern presented here are examples to illustrate
different degrees of freedoms that are available to the designer.
In general, we present using short burst of pulses within each
period of the overall periodic signal (usually in resonance with
the resonant detector, e.g., a tuning fork). The number, timing
(duration, delay), and amplitude of the pulses can be adjusted to
shape the active region temperature versus time, and thus the
emitted light frequency versus time, on a time scale smaller than
the acoustic modulation period. This is different from usual
modulation schemes that typically use a simple periodic modulation,
and sometimes add a slow modulation (for example, a drive current
ramp) to slowly scan the laser center frequency through an
absorption line at a time scale larger than the modulation period
used to retrieve the signal.
[0101] The photoacoustic signal generation is governed by the V-T
relaxation time of the molecules absorbing the light pulses. The
V-T relaxation time is typically on the scale of tenth to hundreds
of microseconds. By changing the pulse sub-pattern within the
periods of the modulation, it is possible to shape the acoustic
signal generated and thus the distribution of energy between the
fundamental and the harmonics of the modulation, in order to
increase or maximize the strength of the measured signal, depending
on the demodulation scheme used. For example, if a lock-in
amplifier is used to measure the amplitude of the fundamental
modulation frequency, it may be desirable to maximize this
amplitude by shaping the acoustic waveform. Alternatively, the
amplitude of a higher (n>2) harmonic may be measured, in which
case it may be desirable to increase the excitation of higher
harmonics.
[0102] FIGS. 9A and 9B show two different acoustic waveforms
obtained with two different pulse schemes: in FIG. 9A, the
modulation is a single 300 ns long pulse for each period of the
32.8 kHz modulation. In FIG. 9B, a train of 15 pulses, 60 ns in
duration each is fired during the first half of the 32.8 kHz
modulation period. As can be seen, the first scheme results in a
sawtooth acoustic waveform shape while the second scheme results in
a triangular waveform.
Integration of a Humidity Sensor
[0103] The photoacoustic signal strength is strongly impacted by
the value of the V-T relaxation time of the analyte molecules. This
time is itself a function of the gas composition (in addition to
temperature and pressure sensitivities). In particular, the
presence of water molecules has been shown to reduce the relaxation
time and thus enable the generation of stronger signals when a fast
modulation is used.
[0104] Consider a photoacoustic gas sensor measuring ambient air,
with varying humidity. An initial calibration can be realized by
measuring the effect of water concentration on the photoacoustic
signal strength, for varying analyte concentrations, thus
establishing an empirical relationship between water concentration
and photoacoustic signal strength for varying analyte
concentration. For instance, this empirical relationship may be
established by calibrating the sensor (i.e., measuring the signal
versus analyte concentration) under different humidity conditions
and using the measurements to create calibration curves
parametrized by humidity.
[0105] Then, a quantitative measurement can be obtained by (1)
integrating a humidity sensor (or other sensor determining water
vapor concentration) with the QEPAS sensor to measure the water
concentration in the analyte; (2) measuring water concentration in
the analyte at the time of measurement and using the established
empirical relationship to model the expected photoacoustic signal
strength as a function of analyte concentration; and (3) deriving
the analyte concentration from the measured signal and established
empirical relationship between water concentration and
photoacoustic signal strength.
Electrical Pick-Up Signal Cancelation
[0106] One source of noise observed in QEPAS experiments is
associated with possible electrical pick-up signal. For example,
the laser driver, especially when driving pulsed lasers with short,
high amplitude electrical pulses, can radiate electromagnetic waves
that can be picked-up by the electronic circuit between the fork
and the pre-amplifier, via electromagnetic induction. Ground loops
are also often responsible for the apparition of pick-up signals.
This problem can be exacerbated with lock-in detection, which will
amplify any signal modulated at the same frequency as the pulse
repetition rate. We presented above how the modulation scheme can
be varied to mitigate this effect by modulating such pick-up signal
at 2f and higher harmonics, while the chemically relevant signal is
modulated at f.
[0107] Embodiments of the present technology include devices where
the laser source is tightly integrated with the QEPAS fork and
related electronics. In such devices, electrical pick-up signals
can be larger because of the difficulty in electromagnetically
shielding separate components from one another. Here, we present
alternative devices and methods to mitigate this issue.
[0108] FIGS. 10A-10C shows a three-prong tuning fork where all
three prongs 1, 2, and 3 are mechanically coupled (as illustrated
by the dashed line in FIG. 10A). This tuning fork can be used as a
resonant detector in an integrated QEPAS sensor. The laser light
emitted by a single-mode laser in the QEPAS sensor is transmitted,
scattered, and/or reflected by the sample and passes in between two
prongs 1 and 2 but not through the other pair of prongs 2 and 3, as
shown in a top view of the fork in FIG. 10A.
[0109] The wiring of the tuning fork is such that a voltage V1 is
generated when the prongs 1 and 2 move symmetrically with respect
to one another, i.e., when the prongs 1 and 2 move in opposite
directions, either synchronously away from one another or closer to
each other, these two cases generating, respectively, positive and
negative voltages. This polarity is chosen arbitrarily to simplify
the discussion and could be changed without loss of generality. The
prongs 2 and 3 are wired to generate a voltage V2 of opposite
polarity, i.e., a positive voltage is generated when the prongs 2
and 3 move closer to each other. A preamplifier (not shown)
amplifies the difference between the voltages, V1-V2.
[0110] The acoustic wave generated by the relaxation of the gas
between prongs 1 and 2 excites predominantly the anti-symmetric
mode (FIG. 10C) that increases or maximizes the difference V1-V2.
Conversely, a common excitation of the prong pairs 1-2 and 2-3
excites predominantly the symmetric mode (FIG. 10B), and thus
reduces or minimizes the difference V1-V2. The electrical pick-up,
assuming the geometry of the device (i.e., wire geometry, length,
or orientation, presence of potential shielding, fork location, etc
. . . ) is chosen to increase or maximize the excitation of the
symmetric mode by the electromagnetic interference, can thus be
reduced or minimized.
[0111] In FIG. 11 we show a QEPAS setup 1100 using two forks 1101
and 1102 wired in such a way as to subtract the electrical signals
generated by each fork. A differentiating pre-amplifier circuit
1103 can be used to perform that subtraction. The laser beam
excites one fork 1101 and the second fork 1102 is positioned in
such a way as to balance the electromagnetic interference signal
picked up by the two forks. The second fork 1102 could be replaced
by another component, such as a small antenna. This QEPAS setup
1100 cancels out the common electromagnetic pick-up driving both
forks 1101 and 1102. Since the mechanical and electrical properties
of a piezoelectric tuning fork are coupled, the resonance
frequencies of the forks 1101 and 1102 may be matched to balance
the pick-up signals excited in the two forks 1101 and 1102.
[0112] To account for potential differences in electromagnetic
pick-up signal from the two forks 1101 and 1102 (or the fork and
the antenna), a factory calibration can be realized, with the
assumption that the relationship between the amplitude and phase of
the two pick up signals is constant in time.
[0113] In FIG. 12, we show a circuit 1200 for electromagnetic
pick-up noise subtraction. A switch 1210, realized here with
transistors directly defined on a semiconductor laser chip 1202
(e.g., indium phosphide in the case of quantum cascade lasers), can
allow for the alternating drive of a laser source 1220 and of a
dummy load 1230 with electrical characteristics similar to the
laser, located in close proximity to the laser 1220, e.g., on the
same chip 1202. It is expected that the two loads (the laser 1220
and the dummy load 1230) and their mostly shared drive circuits,
generate similar electromagnetic radiation when driven by current
pulses. Two modulation schemes can then be realized:
[0114] (1) If f is the acoustic modulation frequency, the switch
1210 can alternate between driving the two loads at the same
frequency f. In other words, the driver delivers pulses at a 2f
repetition frequency, alternatively to the laser source 1220 and to
the dummy load 1230 (a single pulse each per acoustic modulation
period--or in a manner similar to the one described above, a short
burst of pulses with total duration smaller than the acoustic
modulation period). The electromagnetic pick-up signal is in this
case modulated at 2f while the acoustic signal is modulated at
f.
[0115] (2) The switch 1210 can allow for the drive of the laser
source for several acoustic modulation periods, then drive the
dummy load for a similar time. The signal is digitized and the two
portions are later subtracted in digital domain.
QEPAS Integrated Implementations
[0116] We now present different device geometries to implement
QEPAS spectrometers in compact form factors. The different
geometries presented here integrate the semiconductor laser source
and QEPAS spectrophone in compact sensing platforms. The solutions
aim at simplifying the assembly process, for low-cost production.
The basic elements of a QEPAS device are: (1) a semiconductor laser
source; (2) a tuning fork transducer; (3) one or several optical
elements to image the laser facet to a point between the fork
prongs; and (4) electronics circuitry to drive the laser and
amplify and digitize the tuning fork signal. We show how several of
these elements can be integrated in an easy-to-assemble, low-cost
platform.
[0117] In FIG. 13, we present a first device 1300 using a common
patterned submount 1310 to mount a semiconductor laser chip 1320
(including a laser active region 1322 on a laser substrate 1324),
an optical element (ball lens) 1330, and a tuning fork 1340. The
optical element 1330 images the laser facet to a point in between
the tuning fork prongs. A simple optical element such as a ball
lens can be used. The submount 1310 may be pre-patterned with
structures that can be lithographically or otherwise defined. These
features can include one or several of the following: (1) a shallow
stop ridge 1312 that the laser chip can be abutted to; (2) a dimple
or v-shaped grooves 1314 to reference the position of the optics;
(3) a slit that the tuning fork can be inserted into, or a pattern
on the submount facet that the tuning fork can be received into.
These alignment patterns can be etched or machined into the
submount 1310, or can be based on the deposition of metal pads
(potentially lithographically defined) that the elements are
soldered to. A die bonder or micropositioner may be used to
assemble the different elements in an automated fashion. The
submount may be made of a range of different materials (silicon,
aluminum nitride, aluminum oxide, . . . ) that are usually employed
as submount materials for optical or electronic components. A
common heat dissipation and temperature control interface 1350 may
be used, such as a thermoelectric cooler, a passive heat sink, a
vapor chamber, a heater, etc. The laser chip 1320 may be mounted
epi-up or epi-down, depending on the desired thermal properties and
heat dissipation constraints on the laser. The optical element 1330
may be refractive or reflective.
[0118] As shown in FIG. 14, an aperture in a mask 1442 (e.g., an
iris) in close proximity to the tuning fork 1340 can be used for
spatial filtering of the beam. In particular, the wings of the beam
can be filtered out to avoid having them hit the tuning fork prongs
and generate a background signal. In all implementations discussed
here, including the device 1300 shown in FIG. 13, this feature can
be added.
[0119] FIGS. 15A-15I show top views of QEPAS based on edge-emitting
semiconductor lasers. The laser epi layers are in the plane of the
schematic. The tuning fork prongs are represented as two crossed
rectangles. The architectures shown in FIGS. 15A-15I can also be
used for resonant thermomechanical measurements by allowing the
laser light to hit the tuning fork instead of focusing the light
between the tuning fork's prongs. This enables the tuning fork to
act as a light intensity detector that measures a reduction in
transmission (intensity dip, or in other words a negative signal)
in the presence of an analyte.
[0120] In FIG. 15A, a standard edge emitting semiconductor laser
1520 with a straight waveguide is free space coupled to an optical
element 1530 (refractive or reflective) that images the laser facet
to a point between the prongs of the tuning fork 1540.
[0121] In FIG. 15B, we show that a tapered section 1522 can be used
to reduce the beam divergence in the plane of the schematic
(`in-plane`).
[0122] In FIG. 15C, we show that the tuning fork 1540 can be placed
directly in front of the laser facet, without optical elements. The
mitigations discussed above can be used to reduce any background
signal due to electromagnetic interference or due to light hitting
the fork prongs. Features on the semiconductor chip submount can be
used to facilitate alignment of the laser waveguide and tuning
fork. Such features may include: defining a slit into the submount
that the fork is inserted into, defining a pattern (groove or
solder pad) on the edge of the submount that can receive the fork
in a particular position. The laser chip itself may be aligned
precisely with the submount features (e.g., solder pad) using a die
bonding equipment.
[0123] In FIG. 15D, we show that the tapered section 1522, reducing
the in-plane beam divergence, can be used to reduce risk of light
hitting the tuning fork prongs. The geometry of the tuning fork
1540 may be such that the space between the prongs is much higher
than it is wide. The vertical (out of plane) divergence of the beam
is thus far less likely to result in a background signal.
[0124] In FIG. 15E, we show how a focusing reflective optic 1532
can be used to image the laser facet to a point between the tuning
fork prongs.
[0125] In FIG. 15F, we show that a cylindrical lens 1534 can be
used to collimate the laser beam in the out-of-plane direction,
while a reduction of divergence in the plane of the schematic is
achieved for example with a tapered waveguide section 1522 in front
of the laser. This tapered section can be active or passivated, as
discussed below.
[0126] In FIG. 15G, we show that a cylindrical lens 1534 (rotated
90 degrees about the optical axis from its orientation in FIG. 15F)
can be used to collimated the laser beam in the plane of the
schematic. The geometry of the tuning fork 1540 is such that the
spacing between the prongs is narrow and high (several millimeters
long). In other words, the dimension of the spacing between the
prongs in the direction out-of-plane of the schematic is a few
millimeters, compared to typically a few hundred micrometers for
the prong spacing in the plane of the schematic. The divergence of
the laser beam out of the schematic plane is thus less likely to
cause background signal by hitting the prongs. It may thus be left
uncollimated. This can simplify alignment and the assembly
process.
[0127] In the case of a quantum cascade laser, the substrate and
cladding materials are typically InP while the active region is
composed of InGaAs and InAlAs. The index contrast between
InGaAs/InAlAs and InP allows for vertical optical confinement
(out-of-plane). In-plane confinement is usually provided by etching
a waveguide structure. An insulator and a material contact can
further define lateral confinement. The optical losses are
dominated by free carrier absorption. Ion implantation can create
traps for the free carriers to passivate the material, making it
electrical insulating and optically low loss. Such a process can be
used to passivate the tapered section 1522 and or the optical relay
section. An integrated focusing reflector (like the optic 1532 in
FIG. 15E) can be define by etching a groove in the laser material,
followed by deposition of a reflective metal layer.
[0128] In FIGS. 15H and 15I, we show that a section of passivated
straight material 1524 or passivated tapered material 1526 can be
used to separate the active material 1520 from the tuning fork, in
case the fast temperature rise of the active region 1520 creates
acoustic waves propagating in air from the facet of the laser. Such
waves may be picked up by the tuning fork 1540 and may result in a
background signal. A short (10-500 .mu.m) section of passive
material may prevent the waveguide facet (i.e., the area where the
light is exiting the semiconductor chip) from experiencing
significant temperature variations, and thus avoid or reduce the
generation of acoustic waves. The tuning fork 1540 may thus be
placed in close proximity to the semiconductor chip edge with less
risk of picking up a background signal from temperature variations
of the laser material. The passivation can be realized as discussed
above.
[0129] In FIGS. 16A and 16B, we show that the optical relay
function achieved with external optical elements in the systems
shown in FIG. 15 (i.e., the imaging of the laser facet onto a point
located between the tuning fork prongs), can be integrated into the
semiconductor material itself. The laser may use a tapered section
1522 as shown, although this is not required. The tapered section
1522 as well as the optical relay sections of the chip may be
passivated and made transparent by ion implantation or selective
area regrowth. The vertical confinement is provided by a slab
waveguide geometry, for example, using the laser active material as
core, and the laser cladding material as cladding. The location of
the focus can be chosen to be near the semiconductor chip edge
(from a few micrometers to a few millimeters) to facilitate
assembly by bonding or otherwise mechanically registering the
tuning fork to the semiconductor chip itself, or its submount.
[0130] In FIG. 16A, the optical relay is achieved by etching a
curved (e.g., parabolic or elliptical) reflecting groove 1630 that
images the laser facet onto a point between the tuning fork
prongs.
[0131] In FIG. 16B, the optical relay is achieved by a waveguide
lens 1632, realized, for example, by etching a pattern in the
semiconductor laser top cladding to vary spatially the effective
refractive index of the guided mode. The pattern may be a
subwavelength hole of groove pattern, or it may be a single large
dimple defined by greyscale lithography. Alternatively, ion
implantation can be used to tune spatially the effective refractive
index of the guided mode.
[0132] In FIGS. 17A-17C, we show that surface emission of the
semiconductor laser (e.g., quantum cascade laser) can be obtained
by etching an angled facet at one end of the laser waveguide
1722a-1722c, so as to reflect the laser light towards the substrate
or towards the top cladding. Openings in the metallization of
either the bottom laser substrate 1724 or the top cladding
1726a-1726c allow the light to escape to air. In FIG. 17A, the
laser is more conveniently mounted epi-side up, whereas the
geometry shown in FIG. 17B is more amenable to flip-chip mounting
of the semiconductor laser chip. The angle chosen may be 45
degrees, but other angles may be used, for example for ease of
manufacturing by using wet etching along crystalline planes. Since
low laser feedback is expected at this etched facet, the laser may
include either an etched reflecting structure (such as a deep
groove) before the facet (as shown in FIG. 17C), or the laser would
be a distributed feedback laser that does not rely on facet
reflection to build up the intracavity light intensity.
[0133] In FIG. 18A a schematic of the laser 1800 is shown, with
substrate emitting laser mounted epi-side down. The laser 1800
includes an active region 1822 sandwiched between a laser substrate
1824 and a laser cladding 1826, which are sandwiched in turn
between a submount 1810 and a low-growth substrate. FIG. 18B shows
a cross-section of the device 1800, showing the InP:Fe regrowth of
the buried hetero-structure 1801, the high mobility 2D electron gas
used for back contact 1802 and the metal via 1803 connecting the
back contact 1802 and the submount 1810. This illustrates how to
route the two terminals of the laser diode to the same side of the
wafer, allowing contacting of both terminals with a single step
flip-chip bonding. This offers the advantage to allow for the use
of a low-doped (low electrical conductivity and low optical losses)
substrate, to avoid optical losses as the beam propagates through
the substrate.
[0134] In FIG. 19, we show an exploded view of an integrated QEPAS
sensor 1900 (subassembly) with laser source 1920, optical element
1930, aperture 1942, and tuning fork 1940. These components can be
assembled with a wafer-bonding type process as shown in FIG. 20,
whereby the different functionalities are merged into a single
subassembly by bonding wafers with two dimensional arrays of lasers
1920, lenslet arrays 1930, apertures 1942, and tuning forks 1940.
After dicing the bonded wafer stack (or a substack) into single
discrete assemblies, these can be die bonded to a submount. Several
subassemblies can be bonded to a single submount 1910. The submount
can be mounted onto an electronics board or other system
components, for example, with ball bonding as shown in FIG. 19.
[0135] In the device shown in FIG. 19, the laser 1920 is
substrate-emitting (i.e., the laser light is directed towards the
substrate with an angled facet) and includes an active region 1922
between a cladding 1924 and a laser substrate 1926. In the next
layer, a lenslet 1930 or other optical component compatible with
low-profile wafer-scale manufacturing (e.g., a metamaterial flat
lens) is used to image the laser facet onto a point in between the
prongs of the tuning fork 1940. The next layer can be a silicon
wafer with integrated drive circuitry and preamplifier for the
tuning fork 1940. An array of apertures 1942 in this wafer allows
the light to pass through and reach the upper wafer containing the
tuning fork 1940. This aperture 1942 can be used for spatial
filtering of the laser beam, to remove side lobes or `wings`, and
prevent generation of a background signal that would occur if some
laser light was directly hitting the prongs of the tuning fork. The
last layer contains the tuning fork 1940 and its metalized
contacts. An opening behind the fork allows the light to freely
escape without being absorbed or scattered by the tuning fork layer
material. The optics 1930 and aperture 1942 layers are optional,
depending on the level of integration desired.
[0136] In a possible assembly process, wafers containing the optics
1930 and lasers 1920 would be first aligned and bonded to one
another. The wafers containing the apertures 1942 and tuning forks
1940 would be similarly aligned and bonded. Finally, the two pairs
of bonded wafers would be aligned and bonded.
[0137] Alternatively, the optics wafer may be aligned and bonded to
the laser wafer, then the aperture wafer to the bonded optics and
laser wafers, then the tuning fork layer to the bonded aperture,
optics, and laser wafers.
[0138] Metal vias through the different wafers can enable the
routing of power and electrical signals from one layer to its
neighboring layers. Electrical connections between the sensor
subassembly and the rest of the system may be done at the bottom of
the stack (the tuning fork layer) by soldering to a metalized
submount or using wire bonds between the submounts and the top
layer, or intermediate layers provided opening in the upper layers
are defined prior to assembly.
[0139] As shown in FIG. 19, the sensor subassembly may be realized
so as to partially enclose the tuning fork 1940 in a cavity. By
selecting the materials forming the walls of this cavity, and in
particular by using electrically conductive materials (doped
semiconductor, deposition of a metal layer on the walls), a Faraday
cage may be realized to help isolate the tuning fork 1940 from
electromagnetic interferences.
[0140] The walls of the tuning fork cavity may also be coated with
chemicals for selective absorption or adsorption of target analytes
via weak reversible chemical bonds, thereby providing a
concentration function. A thin film heater may be embedded in one
of the layer (for example, the aperture layer) to trigger the
release of the analytes for immediate analysis by the sensor 1900.
That desorption may be realized with a succession of well-defined
temperatures or with well-defined temperature ramps to allow for
time-resolved desorption study. This may allow different analytes
to be measured at separate times, and thereby lowers the risk of
chemical interference in the measurement.
[0141] A heater may be embedded in a layer (for example, in the
aperture layer). For example, a thin electrical conductor may be
defined on the aperture layer such that when current flows through
the conductor, heat is deposited into the subassembly by Joule
effect. Such heater may be used to remove contaminant that may have
been deposited on the fork of the surrounding walls, potentially
affecting the measurement.
[0142] System decontamination by heating the entire system or some
subsection of the system may be evaluated by monitoring the
resonance curve of the tuning fork. To acquire such resonance
curve, a sinusoidal voltage may be applied to the tuning fork, and
its response may be monitored. A shift or change on amplitude of
the resonance peak may indicate contamination.
[0143] In FIG. 20, we show how different prefabricated wafers may
be bonded together and then diced to yield sensor subassemblies, as
discussed above with respect to FIG. 19.
[0144] In FIGS. 21A-21D, we present a set of QEPAS sensors
2100a-2100d with surface emitting semiconductor lasers 1920 that
can be modulated using any of the pulse modulation schemes
disclosed herein. All schematics show the devices 2100a-2100d seen
from the side (cross section along the length of the lasers). Each
device 2100 includes a laser active region 2122 that is between a
laser substrate 2124 and a laser cladding 2126 and that emits a
laser beam that is imaged between the prongs of a tuning fork 2140.
The tuning fork prongs 2140 are represented as two crossed
rectangles in most drawings.
[0145] In FIG. 21A, an angled facet (e.g., 45 degree) is defined at
one end of the laser waveguide 2122 to direct the light towards the
substrate 2124. The laser substrate 2124 may be thinned down to
between 50 .mu.m and 500 .mu.m to reduce optical losses.
Semi-insulating material, such as low-doped or iron doped InP, may
be used in the case of quantum cascade lasers. The light diverges
from the angled facet. At the bottom of the substrate 2124, an
optical element 2130a may be integrated, for example by (1) bonding
of a micro-optical element such as a small refractive lens; (2)
etching of a lens into the substrate material; (3) etching of a
metamaterial flat lens into the substrate material, formed for
example by a series a thin grooves; (4) deposition and patterning
of a material (dielectric or metal) to define a flat lens (Fresnel
lens, metasurface lens) onto the substrate bottom surface. This
optical component 2130a forms the image of the laser facet onto a
small spot located a short distance beneath the substrate surface
(from a few micrometers to a few millimeters). The tuning fork 2140
can be positioned at this spot, and potentially integrated into a
hollow submount 2110 as shown in FIG. 21A. The submount can have an
opening in the beam path below the tuning fork to avoid light
absorption and generation of acoustic waves.
[0146] In FIG. 21B, a reflective optical element 2130b is defined
on the bottom side of the substrate 2124 to form the image of the
laser facet on the laser side of the wafer. The optical element
2130b may be defined using the methods described above. An
anti-reflection coating (not shown) may be used to reduce
reflection at the top substrate surface where the beam emerges into
the air. This geometry may allow easier integration and alignment
of the tuning fork on the laser-side of the chip. The tuning fork
2140 may be fabricated out of the same semiconductor material as
the laser itself (e.g., InP) and thus fabricated with similar
microfabrication techniques as the laser itself (photolithography,
wet/dry etching, etc . . . ).
[0147] In FIG. 21C, the bottom substrate surface is coated by a
reflective material 2132 but is otherwise flat. Imaging of the
laser facet to a point a short distance above the wafer surface is
achieved with an optical element 2130c integrated (following any of
the methods described above) onto the top substrate surface. As in
FIG. 21B, the tuning fork 2140 may be fabricated directly from the
laser material or made from other materials including quartz
aligned and assembled a short distance (few micrometers to a few
millimeters) above the semiconductor laser chip surface.
[0148] In FIG. 21D, the angled facet is defined in such a way as to
direct the light towards the top cladding. An external optical
element 2130d may be aligned above the semiconductor laser chip to
image the laser facet to a point a short distance above the chip
surface, where a tuning fork 2140 may be aligned and attached to
the chip.
CONCLUSION
[0149] While various inventive embodiments have been described and
illustrated herein, those of ordinary skill in the art will readily
envision a variety of other means and/or structures for performing
the function and/or obtaining the results and/or one or more of the
advantages described herein, and each of such variations and/or
modifications is deemed to be within the scope of the inventive
embodiments described herein. More generally, those skilled in the
art will readily appreciate that all parameters, dimensions,
materials, and configurations described herein are meant to be
exemplary and that the actual parameters, dimensions, materials,
and/or configurations will depend upon the specific application or
applications for which the inventive teachings is/are used. Those
skilled in the art will recognize, or be able to ascertain using no
more than routine experimentation, many equivalents to the specific
inventive embodiments described herein. It is, therefore, to be
understood that the foregoing embodiments are presented by way of
example only and that inventive embodiments may be practiced
otherwise than as specifically described and claimed. Inventive
embodiments of the present disclosure are directed to each
individual feature, system, article, material, kit, and/or method
described herein. In addition, any combination of two or more such
features, systems, articles, materials, kits, and/or methods, if
such features, systems, articles, materials, kits, and/or methods
are not mutually inconsistent, is included within the inventive
scope of the present disclosure.
[0150] Also, various inventive concepts may be embodied as one or
more methods, of which an example has been provided. The acts
performed as part of the method may be ordered in any suitable way.
Accordingly, embodiments may be constructed in which acts are
performed in an order different than illustrated, which may include
performing some acts simultaneously, even though shown as
sequential acts in illustrative embodiments.
[0151] All definitions, as defined and used herein, should be
understood to control over dictionary definitions, definitions in
documents incorporated by reference, and/or ordinary meanings of
the defined terms.
[0152] The indefinite articles "a" and "an," as used herein, unless
clearly indicated to the contrary, should be understood to mean "at
least one."
[0153] The phrase "and/or," as used herein, should be understood to
mean "either or both" of the elements so conjoined, i.e., elements
that are conjunctively present in some cases and disjunctively
present in other cases. Multiple elements listed with "and/or"
should be construed in the same fashion, i.e., "one or more" of the
elements so conjoined. Other elements may optionally be present
other than the elements specifically identified by the "and/or"
clause, whether related or unrelated to those elements specifically
identified. Thus, as a non-limiting example, a reference to "A
and/or B", when used in conjunction with open-ended language such
as "comprising" can refer, in one embodiment, to A only (optionally
including elements other than B); in another embodiment, to B only
(optionally including elements other than A); in yet another
embodiment, to both A and B (optionally including other elements);
etc.
[0154] As used herein, "or" should be understood to have the same
meaning as "and/or" as defined above. For example, when separating
items in a list, "or" or "and/or" shall be interpreted as being
inclusive, i.e., the inclusion of at least one, but also including
more than one, of a number or list of elements, and, optionally,
additional unlisted items. Only terms clearly indicated to the
contrary, such as "only one of" or "exactly one of," or, when used
in any claims, "consisting of," will refer to the inclusion of
exactly one element of a number or list of elements. In general,
the term "or" as used herein shall only be interpreted as
indicating exclusive alternatives (i.e., "one or the other but not
both") when preceded by terms of exclusivity, such as "either,"
"one of," "only one of," or "exactly one of" "Consisting
essentially of," when used in any claims, shall have its ordinary
meaning as used in the field of patent law.
[0155] As used herein, the phrase "at least one," in reference to a
list of one or more elements, should be understood to mean at least
one element selected from any one or more of the elements in the
list of elements, but not necessarily including at least one of
each and every element specifically listed within the list of
elements and not excluding any combinations of elements in the list
of elements. This definition also allows that elements may
optionally be present other than the elements specifically
identified within the list of elements to which the phrase "at
least one" refers, whether related or unrelated to those elements
specifically identified. Thus, as a non-limiting example, "at least
one of A and B" (or, equivalently, "at least one of A or B," or,
equivalently "at least one of A and/or B") can refer, in one
embodiment, to at least one, optionally including more than one, A,
with no B present (and optionally including elements other than B);
in another embodiment, to at least one, optionally including more
than one, B, with no A present (and optionally including elements
other than A); in yet another embodiment, to at least one,
optionally including more than one, A, and at least one, optionally
including more than one, B (and optionally including other
elements); etc.
[0156] As used herein, all transitional phrases such as
"comprising," "including," "carrying," "having," "containing,"
"involving," "holding," "composed of," and the like are to be
understood to be open-ended, i.e., to mean including but not
limited to. Only the transitional phrases "consisting of" and
"consisting essentially of" shall be closed or semi-closed
transitional phrases, respectively, as set forth in the United
States Patent Office Manual of Patent Examining Procedures, Section
2111.03.
* * * * *