Semiconductor diode laser spectrometer arrangement and method
Abstract
A method for detecting gases using a semiconductor laser diode spectrometer, the method comprising: introducing a sample gas (13) into a non-resonant optical cell (17) with reflective elements; applying a stepped function electric pulse to the semiconductor laser diode (20) to get the laser (20) to produce a continuous chirp (pulsed modulated frequency) wave to inject it into the optical cell (17); by injecting the chirp wave using the wave variation provided by the chirp wave as a wavelength scanner, and detecting the light emitted from the cell, characterized in that the method also involves the use of a chirp wave speed so that there is a time delay between the points of the reflective elements in which the injected chirp wave is reflected enough to prevent light interference in the optical cell (17).

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27 claims: 15 independent, 12 dependent
- 1ES 2 392 834 T3 REIVINDICACIONES 1. Un método para detectar gases utilizando un espectrómetro de diodo láser semiconductor, comprendiendo el método:la introducción de un gas de muestra (13) en una célula óptica no resonante (17) con elementos reflectantes;aplicando un impulso eléctrico de función escalonada al diodo láser semiconductor (20) para conseguir que el láser (20) produzca una onda chirp (de frecuencia modulada pulsada) continua para inyectarla en la célula óptica (17);inyectando la onda chirp utilizando la variación de onda proporcionada por la onda chirp como un escáner de longitud de ondas, y detectando la luz emitida desde la célula, caracterizado porque el método también envuelve la utilización de una velocidad de onda chirp para que exista un tiempo de retardo entre los puntos de los elementos reflectantes en los que la onda chirp inyectada se refleja lo suficiente como para evitar que se produzca una interferencia de luz en la célula óptica (17).
- 2Un método de acuerdo con la reivindicación 1, en el que la duración del impulso aplicado al diodo láser semiconductor (20) es igual a o menor que un microsegundo.
- 3Un método de acuerdo con la reivindicación 1 o la reivindicación 2, en el que la duración del impulso es menor a la duración necesaria para que la energía óptica producida sea cero después de que el impulso de activación se aplique.
- 4Un método de acuerdo con cualquiera de las reivindicaciones anteriores, incluyendo también la variación de la velocidad de cambio de longitud de onda por unidad de tiempo.
- 5Un método de acuerdo con la reivindicación 4, en el que variar la velocidad de cambio de onda por unidad de tiempo implica variar la amplitud del impulso de corriente/voltaje de activación.
- 6Un método de acuerdo con cualquiera de las reivindicaciones anteriores comprendiendo el ajuste de longitud del escáner de longitud de onda.
- 7Un método de acuerdo con la reivindicación 6 en el que ajustar el escáner de longitud de onda incluye variar la duración del impulso de corriente/voltaje de activación.
- 8Un método de acuerdo con cualquiera de las reivindicaciones anteriores comprendiendo una variación de la temperatura del diodo láser semiconductor ES 2 392 834 T3
- 9Un método de acuerdo con cualquiera de las reivindicaciones anteriores, en el que el diodo láser semiconductor (20) produce una radiación con longitudes de ondas en el intervalo de 1pm a 14,0pm.
- 10Un método de acuerdo con cualquiera de las reivindicaciones anteriores, en el que el láser semiconductor (20) es un láser de cascada cuántica (20).
- 11Un método de acuerdo con cualquiera de las reivindicaciones anteriores, en el que la célula (17) es una célula Herriott.
- 12Un método de acuerdo con las reivindicaciones anteriores, en el que la cantidad de radiación absorbida se determina utilizando una medición de amplitud de la radiación transmitida a través del gas de muestra (13) y una medición de amplitud de un impulso de referencia.
- 13Un espectrómetro de diodo láser semiconductor, preferiblemente un espectrómetro de láser de cascada cuántica, para medir la absorción de radiación mediante un gas de muestra (13), el espectrómetro comprendiendo un diodo láser semiconductor (20);una célula óptica no resonante (17) para contener un gas de muestra (13) con elementos reflectantes a cada extremo de la misma, un generador de impulsos eléctricos (19) configurado para aplicar un impulso eléctrico de función escalonada al láser (20) para provocar que el láser (20) introduzca una onda chirp continua a la célula de muestra (17) y un detector (23) para detectar la luz de salida de la célula (17) y configurada para usar la variación de la longitud de onda de la longitud de la onda chirp como un escáner de longitud de onda, en el que la velocidad chirp utilizada es tal que existe un tiempo de retardo entre los puntos de los elementos reflectantes en los que la onda chirp inyectada se refleja lo suficiente como para evitar la interferencia de luz que se produce en la célula óptica (17).
- 14Un espectrómetro de acuerdo con la reivindicación 13, en el que la duración del impulso eléctrico es igual o menor a 1 microsegundo.
- 15Un espectrómetro de acuerdo con la reivindicación 13 o la reivindicación 14, en el que se proporcionan los medios para variar la tasa de cambio de la longitud de onda por unidad de tiempo de la onda chirp.
- 16Un espectrómetro de acuerdo con la reivindicación 15, en el que los medios para variar la tasa de cambio de la onda se utilizan para variar la amplitud del impulso de corriente/voltaje de activación.
- 17Un espectrómetro de acuerdo con cualquiera de las reivindicaciones de la 13 a la 16, en el que los medios se proporcionan para ajustar la longitud del escáner de longitud de onda. ES 2 392 834 T3
- 18Un espectrómetro de acuerdo con la reivindicación 17, en el que los medios para ajustar el escáner de onda se utilizan para variar la duración del impulso eléctrico.
- 19Un espectrómetro de acuerdo con cualquiera de las reivindicaciones de la 13 a la 18, en el que los medios se proporcionan para variar un punto de inicio de longitud de onda del escáner de longitud de onda.
- 20Un espectrómetro de acuerdo con la reivindicación 19, en el que los medios para variar un punto de inicio de la longitud de onda del escáner de longitud de onda se utilizan para variar la temperatura base del diodo láser semiconductor.
- 21Un espectrómetro de acuerdo con la reivindicación 20, en el que los medios para variar la temperatura del diodo láser semiconductor (20) comprende un calentador/refrigerador termoeléctrico o medios para ajustar el ciclo de trabajo o la frecuencia de repetición del impulso de los impulsos de activación de corriente/voltaje repetidos aplicados a los contactos eléctricos del diodo láser o medios para ajustar la amplitud del impulso de corriente/voltaje de activación o medios para ajustar el nivel de base DC de los impulsos de corriente/voltaje de activación aplicados a los contactos eléctricos del diodo láser.
- 22Un espectrómetro de acuerdo con las reivindicaciones de la 13 a la 21, en el que un divisor de haz (21, 29) u otro elemento parecido se proporciona para dividir la radiación de salida del láser en dos componentes, el primer componente para que atraviese la muestra y un segundo componente que no atraviesa la muestra.
- 23Un espectrómetro de acuerdo con cualquiera de las reivindicaciones de la 13 a la 22, en el que un diodo láser semiconductor (20) emite radiación con longitud de ondas en el intervalo entre 1pm y 14 pm.
- 24Un espectrómetro de acuerdo con cualquiera de las reivindicaciones de la 13 a la 23, en el que la célula (17) es una célula Herriott.
- 25Un espectrómetro de acuerdo con cualquiera de las reivindicaciones de la 13 a la 24, en el que la onda chirp tiene una frecuencia de variación de aproximadamente 60GHz.
- 26Un espectrómetro de acuerdo con cualquiera de las reivindicaciones de la 13 a la 25 en el que la duración del impulso aplicado es mayor a 150ns, en particular mayor a 200ns.
- 27Un espectrómetro de acuerdo con las reivindicaciones de la 13 a la 25, en el que el impulso aplicado tiene una duración que está en el intervalo entre 150 y 300ns, preferiblemente entre 200 y 300ns.
Independent claims27
85 paragraphs in 5 sections, as filed
392 834 T3
DESCRIPTION
CONFIGURATION OF A SEMICONDUCTOR DIODE LASER SPECTROMETER AND METHOD
[0001] The present invention relates to a semiconductor laser diode spectrometer configuration and in particular a time-resolved absorption semiconductor infrared laser diode spectrometer, in which the scale calibration of the wave number is based on a time to map the wave number / cm1.
[0002] Infrared absorption spectrometers are used to detect and measure gases. Semiconductor infrared diode lasers are largely used to provide the light to be absorbed by species measurement, as these lasers are relatively small, spectrally well defined, bright, and tunable. There are other advantages of these lasers over other lasers, some of which can be seen in spectroscopic monographs.
[0003] In remote locations and harsh environments, one of the most effective and accurate methods of detecting traces of gas uses semiconductor laser diode-based spectrometers. Although gas detection began decades ago, in many environments it is still difficult to remotely monitor trace gas components. Many of the above instruments have slow responses, are often large, unreliable, expensive, and require constant maintenance. [0004] In order to retrieve information with known technology, remote gas detection typically occurs in the near and mid-infrared region of the electromagnetic spectrum, where the chemical fingerprints of most chemical compounds are found. By the term near and mid-infrared, we mean radiation with a wavelength in the range of 1pm to 14pm. This spectral region contains high transmission windows called atmospheric windows, which owe their transparency to the low density of strong lines. <sub>to</sub>b<sub>sorc</sub>io<sub>n</sub> d<sub>and</sub> CO2 and H2O. These atmospheric windows are of great interest for spectroscopy since the absorption lines of traces of molecules with strong absorption have an intensity similar to or greater than that of the weak lines of CO.<sub>2</sub> and H<sub>2</sub>OR.
[0005] Near infrared diode lasers produce light in the wavelength range of vibration overtones from about 1pm to 3.0pm. Because the absorption coefficients of vibration overtones are much lower than those of the fundamental bands, the sensitivity of spectrometers that
ES 2 392 834 T3 use such lasers remains limited. Therefore, the sensitivity of such a gas detection apparatus rarely reaches the subpart per billion (sub-ppb) range.
[0006] Mid-infrared diode lasers produce light in the wavelength range of the fundamental rotation-vibration bands, approximately 3pm to 14pm. These lasers have not been as technologically developed as those in the near-infrared region, and therefore have low single-mode power output. Gas detection systems based on mid-infrared diodes are capable of sub-ppb sensitivity. The development of such light sources has therefore been entirely devoted to spectroscopic applications. Several disadvantages are associated with conventional mid-infrared diode lasers, mainly lead salt lasers, such as low power output, and their need to be cryogenically cooled in large and expensive operating systems to maintain this temperature.
[0007] Recently, room temperature and high power output have been achieved in the mid-infrared using quantum cascade (QC) lasers. Unlike previous lasers, QC lasers are unipolar semiconductor lasers that can be designed at any desired wavelength in the mid-infrared. The replacement of lead salt lasers with QC lasers provides the potential to improve both the detection sensitivity and spectral resolution of mid-infrared absorption spectrometers.
[0008] The spectrometer-based QC laser developed so far uses two approaches. The former uses a continuous wave (CW) QC laser acting as a pass-through replacement for a lead salt laser. The second approach is to use a pulsed QC laser in a way that mimics the use of a continuously operating laser. In some experiments conducted by Webster et al (Applied Optics LP 40, 321 (2001)), the first approach was used with one of the lead salt laser diodes in an ALIAS II spectrometer replaced by a QC laser. Test measurements made using an ER2 aircraft platform showed that the QC laser could successfully replace a lead salt laser and was less affected by temperature instability. However, the laser needed to be activated at 77K for its CW operation. The second method was originally described by Whittaker et al (Optics Letters 23,219 (1998)). In this method a very short current pulse is applied to the QC laser operating at a temperature close to room temperature to provide a reduced wavelength pulse. In this operating mode the spectral resolution is limited by the
ES 2 392 834 T3 wavelength of increased frequency chirp. Therefore, in this type of spectrometer the wavelength of the increased frequency chirp is considered detrimental to the operation of the system.
[0009] The increasing frequency wave chirp (effective emission line width) is induced by the time duration of the drive pulse current / voltage. The term "effective emission line" refers to the observable / measurable spectral width (FWHM) of the emission of a semiconductor laser diode induced by the current / voltage pulse applied to its electrical contacts. For example, if the pulse duration applied to the QC laser were of the order of 10 ns, the effective emission line width would be of the order of 700 MHz (0.024 cm<sup>-1</sup>) in the spectral domain (Optics Letters 23,219 (1998)).
In order to scan samples using a pulsed QC laser spectrometer, the effective emission line width is tuned across a spectral region using a slow DC current ramp superimposed on the pulse train. This means that the resulting spectral tuning is a quadratic function of the DC current ramp injected into the laser [Optics Letter 23,219 (1998); Applied Optics 39 6866 (2000); Applied Optics 41,573 (2002)]. One problem with this approach is that, however, an additional step is required in the data processing phase to correct for the quadratic effect. In some cases, to improve the signal-to-noise ratio (Optics Letters 23,219 (1998)) a small AC current modulation signal is added to the DC ramp in order to use a sensitive phase detection of the detected optical signal. Although adding this modulation can increase sensitivity, it also requires the use of demodulation in the detection system, making rendering the system more complicated. Another problem is that the use of modulation inherently reduces the scan frequency, since detected high speed signals are demodulated to low frequency audio signals. Therefore, prior art configurations of this type allow scanning frequencies only on the order of tens of Hertz. A system proposed by Beyer et al (Third International Conference on Tunable Diode Laser Spectroscopy July 8-12 2001, Zermatt Switzerland) uses the wavelength variation of the intrinsic chirp (frequency modulated pulsed) wavelength. However, the proposed configuration is of limited use for chemical printing.
Both the CW function laser (first method = described by Webster et al (Applied Optics LP 40, 321 (2001)) and the short pulse laser (second method), originally described by Whittaker et al (Optics Letters 23,219 ( 1998)) for a gas
ES 2 392 834 T3 with a small absorption coefficient, the simplest way to achieve an observable change in the transmitted signal is to use a wide sample length. This can be achieved through the use of resonant or non-resonant cells. Resonant cell combinations are complex and require sophisticated techniques to minimize the effects of reflected signals from the input mirror to the cell by disrupting laser operation. Non-resonant cells, such as so-called Herriot cells or Astigmatic Herriot cells, are attractive as they offer long path lengths, without the punishment of reflected signals. Furthermore, the path length is independent of the gas concentration in the cell. A major drawback associated with non-resonant cells is deformation due to partial overlap of light beams propagating through the cell. This significantly decreases the performance of the system.
[0012] WERLE P ET AL: Near and mid-infrared laser optical sensors for gas analysis (OPT. LASERS ENG. (UK), OPTICS AND LASERS IN ENGINEERING, vol.37, no. 2-3, February 2002 (2002- 02), - March 2002 (2002-03), pages 101114) describes a gas sensor using a semiconductor laser spectrometer and a Herriott type cell measurement. The DC current of a temperature stabilized DFB laser is adjusted to the selected absorption line. The laser is scanned on this line with a ramp of 1 kHz and additionally it is modulated with high frequency. The publication also indicates that when using laser diode spectroscopy, unwanted spectral characteristics can be identified due to interference fringes and others.
As can be seen, known spectrometers using semiconductor diode lasers, in particular quantum cascade (QC) lasers, have flaws, which limit their use for absorption spectroscopy in pulsed operation. Specifically prior art QC laser spectrometers, where light sources must be activated in the pulsed mode of operation to achieve room temperature operation, have the resolution of their effective emission line determined by the time duration of the pulse of the activation voltage / current applied to its electrical contacts.
US5636035 describes a method and apparatus for driving an absorption spectroscopy laser using a tunable frequency laser to pass a laser beam through a sample volume and into an optical detector. Two-step modulation is used to generate frequency components to lock the tunable laser with the absorption signal, and generate an output signal proportional to the absorption signal. The laser has the frequency
ES 2 392 834 T3 modulated to a first and a second frequency. A feedback control signal is generated based on a demodulated antisymmetric signal from the optical detector using a predetermined first harmonic of the second frequency. The tunable laser is locked to the absorption signal with the feedback control signal and an output signal proportional to the absorption signal is generated using a demodulated symmetric signal using a predetermined second harmonic of the second frequency or the triangle wave frequency. .
The invention is defined in the independent claims. Some preferable features are defined in the independent claims.
According to one aspect of the invention there is provided a deformation-free method for detecting gases using a semiconductor laser diode spectrometer. This includes the introduction of a sample gas into a non-resonant optical cell with reflective elements and the injection of light from a semiconductor laser into the cell. Light is generated by applying one or a series of stepped-function electrical pulses to a semiconductor laser diode to cause the laser to produce one or more continuous chirp waves, to inject into the optical cell. Preferably, each applied pulse has a duration greater than 150ns, in particular greater than 200ns. Preferably, each applied pulse has a duration in the range between 150 and 300ns, preferably between 200 and 300ns. This can provide a tuning range of approximately 60GHz. The chirp wave frequency is selected so that there is a delay time between the points of the reflective elements of the non-resonant cell sufficient to prevent light interference from occurring, in which the points define locations where the chirp wave injected is reflected off the cell walls. The wavelength variation provided by the same chirp wavelength is used to provide a scan of the wavelength. Therefore, there is no need to tune the effective emission line width across the spectral region using, for example, a slow DC current ramp superimposed on the pulse train. The exit light from the optical cell is detected using an appropriate detector.
[0017] Preferably, each applied pulse has a duration greater than 150ns, in particular greater than 200ns. Preferably, each detected pulse has a duration in the range between 150 and 300ns, preferably between 200 and 300ns. By preventing light interference from occurring, deformation effects are avoided. This means that the sensitivity of the method can be significantly improved.
This invention will now be described by way of example only and with
ES 2 392 834 T3 references to the attached drawings, in which:
Figure 1a to Figure 1f show computer simulated graphs of emissions versus wave number of various modes of operation of the QC laser;
Figure 1g shows a computer simulated graph of emissions versus time for a QC laser in a particular mode of operation;
Figure 1h shows an experimental graph of emissions versus time for a QC laser being activated to generate a chirp wave;
Figure 2 is a schematic diagram of a setup for characterizing a semiconductor laser using a Fourier Transform Scanning (FTS) spectrometer;
Figure 3a shows graphs of wave number versus pulse duration at several different temperatures;
Figure 3b shows graphs of wave number versus pulse duration at several different current amplitudes; Figure 4b shows a graph of dynamic obstruction of a QC laser;
Figures 4b and 4c show graphs of dissipated energy versus current of a QC laser at -10C;
Figure 5 is a graph of voltage and energy as a function of current for a QC laser operating at a temperature of -10C;
Figure 6a shows a graph of wave number versus temperature;
Figure 6b shows a graph of wave number versus duty cycle;
Figure 7 is a block diagram of a system for detecting gases that includes a QC laser and a Fourier transform spectrometer;
Figure 8 shows an absorption spectrum of 1,1 difluoroethylene, CF2CH2, recorded using the apparatus of Figure 7;
Figure 9 is a block diagram of another spectrometer; Figure 10 shows a schematic diagram of a method for detecting optical pulses using the spectrometer of Figure 9, and, for comparing a method used for a known spectrometer;
Figure 11 is a block diagram of the prior art spectrometer used for comparative measurements shown in Figure 10;
Figure 12 shows a CF2CH2 transmission spectrum reference and a spectral laser with and without absorption of CF2CH2 obtained using the spectrometer of Figure 9;
Figure 13 shows an absorption spectrum of CF2CH2 recorded using the spectrometer of Figure 9 (upper trace) and a recording of a pattern of an interference fringe of the etalon of a solid etalon Ge (lower trace);
Figure 14 shows a comparison of the absorption spectra of two different molecules (upper trace: CF2CH2; lower trace: COF2) recorded using the configuration of Figure 9;
Figure 15 shows absorption spectra for sample atmospheric gases, recorded using the configuration of Figure 9;
Figure 16 is a block diagram of a modified version of the spectrometer of Figure 9;
Figure 17a shows simulated plots of a part of a transmission spectrum of a complex molecule over part of the spectral range of the multi-longitudinal mode semiconductor laser, along with the laser profile; Figure 17b shows the output of the spectrometer after absorption;
Figure 18 shows simulated graphs of part of the transmission spectrum of a complex molecule with a spectral filter used, and Figure 19 shows simulated graphs of part of the transmission spectrum of a complex molecule with a spectral filter used and with a tuning temperature .
The spectrometer on which the invention is based advantageously uses the increasing frequency wave chirp exposed by pulse QC and semiconductor lasers to provide a wavelength scanner. Each individual laser output pulse provides a wavelength variation, eg a wavelength scan, by virtue of the increasing frequency wavelength chirp. This wave of increasing frequency chirp is induced by a heating effect that occurs during the entire duration of the applied drive current / voltage pulse. For these QC lasers, the wave of increasing frequency chirp has been shown to be continuous. More specifically, under particular conditions of the shape of the electrical activation pulse (Optics Communications 197,115 (2001)), the spectral behavior of QC pulsed lasers is characterized by the fact that this increasing wavelength chirp is almost linear with respect to the weather. It has also been shown that in pulsed operations the spectral behavior of QC lasers can be mapped to the temporal definition of the drive current / voltage pulse applied to their electrical contacts. Taking this into account, it is possible to map the behavior
ES 2 392 834 T3 of the light output of a QC laser and display it in the time domain with a photodetector.
[0020] Figures 1a to 1g show computer-simulated graphs of the time and spectral responses for single-mode and multi-mode semiconductor diode lasers when a square current / voltage signal is applied to their electrical contacts. For the purposes of this description, the time term response refers to the time required for the detection system to achieve a deviation in a range proportional to an electrical signal, in the form of a perfect stepping function, applied to its input. The temporal response is calculated using the common equation for the relationship between rise time and line width of a system, for example response time = rise time = 0.35 / line width.
Figures 1a and 1b show computer simulated results for spectral behavior at a fixed moment in time so that no chirp wave is observed in the spectral domain and so that the emission line width represented is the width intrinsic emission line. The term "intrinsic emission line width" refers to the instantaneous observable / measurable spectral width (FWHM) of the emission. The intrinsic line width of the emission from a semiconductor diode laser diode is normally much less than the effective emission line width and can be difficult to quantify in driven operation.
[0022] Figures 1c and 1d show computer simulated results obtained after the application of a well defined rectangular drive current / voltage pulse with a duration long enough that the chirp wave is observed towards a longer wavelength. As mentioned previously, this chirp wave appears from the heating effects induced by the drive pulse. The amplitude deterioration that accompanies this chirp wave is caused by the reduced efficiency of the laser action as heating increases. The effect of the chirp wavelength can be seen more clearly in Figures 1e and 1f. A computer simulation of the temporal behavior of the emission is shown in Figure 1g. Since the amplitude deterioration of the chirp wave decreases with time, the temporal response is such a mirror image in the spectral domain. Figure 1h shows experimental results for a laser pulsed in such a way that the chirp wave is generated. From a comparison of Figures 1g and 1h, it can be seen that there is a correlation between the theoretical and the simulated graphs.
ES 2 392 834 T3
[0023] Figure 2 shows a setup for characterizing the spectral output behavior of semiconductor diode lasers using a continuous infrared scanning Fourier transform spectrometer. The results of the experiments using this setup are shown in Figures 3 through 6. Figure 3a is a graph of the number of chirp waves as a function of the time duration of the applied current pulse (fixed amplitude 4.2A) for the range of substrate temperatures. The results indicate that the tuning frequency, above the investigated temperature range, is insensitive to temperature. In this graph the frequency of change of wave number as a function of time, β, can be determined empirically. To vary β, the amplitude of the current / voltage pulse must be altered, as shown in Figure 3b. From here, it can be seen that regardless of the applied current, over the range of currents used, β is almost linear in nature.
[0025] β is related to the energy dissipated inside the laser diode and the almost linear variation of β arises from the fact that the QC laser shows a dynamic decrease, as shown in figure 4a, which results in a dissipation of almost linear energy over the current range used, see figure 4b. It should be taken into account that the value of β is determined on the time interval for which the output does not show a transitory behavior, see figure 4c. The limiting values of β are defined, at the lower end, by the amplitude of current / voltage necessary to obtain a usable output power and at the upper end, by the amplitude of current / voltage that induces a reduction in the output power. , see figure 5. The initial wave number of the chirp wave number is influenced by both the substrate temperature of the QC laser and the duty cycle of the applied current / voltage pulse, as shown in Figures 6a and 6b. Therefore, by varying the substrate temperature and / or the duty cycle, the initial wave number can be altered.
As will be appreciated, the effectiveness of a gas spectrometer that uses a chirp wave to provide a wavelength variation to scan a sample depends on the actual range of wave amplitudes over which the chirp wave is spread. This wavelength interval can correspond to a frequency variation of 60GHz. Figure 7 shows a setup for measuring the upper limits of the effective line width of a QC laser. This is based on the Fourier transform spectrometer, which is adapted to generate representative spectra of the output from a simple cell into which light is injected from a QC laser. Transform spectrometers
ES 2 392 834 T3
Fourier are well known and use Michelson interferometers. To accurately measure the current supplied to the QC laser, a Rogowski coil is provided. A typical spectrum measurement using the configuration of Figure 7 is illustrated in Figure 8 which shows a high resolution absorption spectrum of 1,1 difluoroethylene, CH2CF2. In this case, the resolution of the spectrometer is 0.0015cm<sup>-</sup>1. The duration of the electrical activation pulse applied to the QC laser was 200ns, the pulse repetition frequency was 20 kHz and the activation current was 4.8A. The substrate temperature was -1.5 OC. From figure 8 it can be deduced that the upper limit of the laser line width is that established by the resolution of the instrument, for example in this case 45MHz. Furthermore, three groups can also be distinguished in the range of the chirp wavelength scanner of the QC laser, for example (i), (ii), (iii), of the easily identifiable CH2CF2 lines. This shows that the effective resolution of a pulsed QC laser spectrometer is sufficient to detect chemical fingerprints for at least some chemicals.
Due to its controllable and predictable characteristics, the nearly linear chirp decreasing wave number can be exploited for spectral measurements. In particular, the near linearity of the chirp wave number as a function of time allows the construction of a sub-microsecond high speed semiconductor absorption laser diode spectrometer. Figure 9 shows two spectrometer configurations 1a and 1b for measuring radiation absorbed by a species, for example a sample gas. At the low intensity limit, the spectrometer determines the absorption coefficient of a species by measuring the radius of intensity of the light incident on the sample gas cell, I<sub>or</sub> and that is transmitted through a sample gas cell containing the absorption species, I<sub>to</sub>. At the low intensity limit, the change in intensity of light passing through the gas is described by the Beer-Lambert law relationship, I<sub>to</sub> = I<sub>or</sub>exp (- aL), with a being the absorption coefficient and L the length of the optical path. It should be noted that a is a function of the number of waves and that it is independent of the intensity at low intensities of the incident radiation.
[0028] The spectrometer of Figure 9 uses a non-resonant optical cell configuration (confined gas) and comprises an activation current / voltage pulse generator configuration 19 that is connected to the input of a laser 20. The generator of Pulse 19 is operable to apply substantially rectangular pulses to laser 20. In this case, laser 20 is a semiconductor laser diode
Single-mode quantum cascade (QLC) ES 2 392 834 T3. Laser 20 is maintained at a controlled temperature within a Peltier module (not shown). The Peltier element is controlled by a thermoelectric controller 28. Connected to the laser module is a compressor and a pump unit 11, which is used to cool / heat and circulate that fluid within the empty housing of the laser diode module 20. This allows the laser element to operate over a higher temperature range than is possible using the Peltier element alone.
[0029] On an optical path from the output of laser 20 is a spectral filter 15, for example a small grating monochromator, which can be used to provide a single mode laser output if a multilongitudinal mode laser is used. In an optical path from the filter there are two beam splitters 21 and 29 respectively. These can be, for example, germanium detector light beams for laser radiation at wavelengths close to 10pm. However, it will be appreciated that any other type of beam splitter can be used. The first beam splitter 21 is positioned to direct at least some of the light that falls on it towards the first optical sample cell 17, which contains the sample to be detected or characterized, and transmit the rest of the light to the second beam splitter 29 . The second beam splitter is positioned to direct at least some of the light striking it to the second optical cell 18 which is a reference cell. Cells 17 and 18 have the same characteristics. Both are non-resonant optical cells. Cells 17 and 18 can be Herriot cells, both standard and astigmatic Herriot cells.
[0030] In the configuration of figure 9 the radiation emitted by the QC laser can pass through two possible optical paths, 16a and 16b, one through the sample cell 17 and one through the reference cell 18. To detect radiation transmitted through one of these cells, detectors 23 and 24 are provided at the respective outputs. Connected to each of these is a digitizer 12 and 14 respectively, each of which in turn is connected to a control and acquisition system 10, which provides full control of the spectrometer. In addition to the digitizers, the control system 10 is connected to each of the drive pulse current / voltage generators 19, the spectral filter 15, and the pump and compressor 11. As part of its functionality, the control system 10 can set the amplitude and duration of the pulse applied to the laser input and monitor the resulting outputs detected from the gas and reference cells 17 and 18 respectively. The control system 10 can also determine the radius I<sub>to</sub>/ I<sub>or</sub>. This could be carried out
ES 2 392 834 T3 using, for example, Beer Lambert's law, which can also be represented as I<sub>to</sub>/ I<sub>or</sub> = exp (-aL). Of course, anyone skilled in the art will appreciate that other techniques can be used.
The configuration of Figure 9 can be adapted for use in two separate modes: a single beam mode (SBM) or a dual beam mode (DBM). In the single beam mode only the sample cell 17 is used, so that the light only follows one path 16a. In this case the beam splitter 21 could be replaced by a mirror. For the SBM both the<sup>I</sup>or like him <sup>I</sup>a are measured using a single optical absorption cell 17. To determine Io, cell 17 is evacuated and a series of chirp pulses from the QC laser 20 pass through it. The output of the evacuated cell 17 is digitized by the digitizer 12 and stored by the control and acquisition system
10. To determine I<sub>to</sub>, cell 17 is filled with a sample of the gas under study 13, and the sampling process is repeated. For the dual beam method (DBM), the measurement of I<sub>or</sub> and I<sub>to</sub> it can be carried out at the same time using both paths 16a and 16b. In this case, the sample gas can be placed in the sample cell 17 and the reference cell would be evacuated and sealed. Beam output from gas and reference cells 17 and 18 respectively are directed to detectors 23 and 24. The detector 23 detects the absorbed light pulse output from the gas cell 17 and the detector 24 detects the back light pulse output from the reference cell 18. An advantage of the DBM scheme is that by taking simultaneous measurements, they can be minimized drift effects.
[0032] For the SBM the backlight pulse with amplitude I<sub>or</sub> and the impulse of absorbed light with amplitude I<sub>to</sub>, each one has the same distance to travel to the detection system. As long as the lengths of the optical paths associated with paths 16a and 16b are identical, as is also the case with DBM, both pulses reach detectors 23 and 24 at the same time. In either case, absorption can be detected directly through the use of radius I<sub>to</sub>/ I<sub>or</sub>.
[0033] For both modes of the spectrometer of Figure 9, ie the SBM and the DBM, the drive current / voltage pulse generator 19 generates a plurality of substantially rectangular pulses that are applied to the input of the laser 20. More specifically, generator 19 provides a train of submicrosecond fixed amplitude rectangular drive current pulses. This causes a faster heating effect and consequently an increasing continuous wavelength chirp of the radiation emitted by the semiconductor laser diode at a rate in time β. As has been discussed
ES 2 392 834 T3 above, the accelerated heating of the laser caused by the sub-microsecond rectangular current pulses is such that for each pulse emitted by the laser 20, the chirp wave is an almost linear continuous spectral variation of one wavelength from short to long. This is defined as a continuous wavelength or spectral scanner.
As noted above, the spectrometer of Figure 9 uses a non-resonant optical cell. As mentioned above, the use of non-resonant cells in conventional spectrometers causes an interference fringe, which significantly reduces the performance of the system. In order to avoid this, according to the invention, the chirp laser spectrometer of Figure 9 is adapted to control the laser diode with a chirp wave speed such that the laser wavelength at the overlapping points in the non-resonant cell, it is different enough to prevent interference from occurring. For some QC lasers, this can be done dynamically by varying the chirp wave speed. Rather, a laser with an appropriate chirp wave speed should be chosen. In practice, this can be determined empirically by trial and error. By the word dots, we mean regions of the cell's reflective elements, typically curved mirrors, of the optical cell from which light in the cavity is reflected as it bounces back and forth within the cavity. These points are distributed along the lateral walls of the cells. The variation in the location of the point arises because the light is injected into the cell at different angles, and the mirrors of the cells can themselves cause a transformation of the angles of reflection. By ensuring that the laser wavelength of the overlapping points is sufficiently different, the residual effects of the interference fringe can be suppressed. The spectrometer of Figure 9 is therefore a free gas fringe detection system, with improved absorption sensitivities. As a specific example, assuming that nearby points overlap and that the mirrors are 0.5m apart, and that the laser line width is 30 MHz, a chirp wave speed exceeding 10 MHz / ns would be sufficient to avoid interference, and therefore provides substantially fringe-free performance.
[0035] Figure 10 shows a schematic diagram of a data sampling scheme used in the spectrometer of figure 9. We will call it Method 1 from now on. To facilitate comparison, a data sampling scheme is also provided for the conventional QC laser spectrometer. From now on we will call it Method 2. Figure 11 shows the prior art spectrometer
ES 2 392 834 T3 that was used to implement Method 2. For the purposes of an accurate comparison, computer simulations of both systems were carried out using the same pulse repetition frequency (PRF) equal to 20KHz. The PRF is the frequency at which the semiconductor laser diode has a current / voltage pulse applied to its electrical contacts. The value of 20KHz was chosen, since it is the maximum frequency at which the spectrometer of figure 11 can operate (see: Applied Optics 41, 573 (2002)). It is also assumed that the spectrometer of Figure 9 uses a current / voltage duration pulse of 256ns to take advantage of the increasing wavelength chirp, and that the spectrometer of Figure 11 uses a current / voltage duration pulse of 5ns ( see: Applied Optics 41, 573 (2002)). For the spectrometer of Figure 11 the effective emission line width is approximately 0.02cm-1. To provide a wavelength scanner in this case, the pulse must be continuously tuned in a non-linear manner in a spectral range of 0.75cm-1 starting at 992.3cm-1. For a current amplitude similar to that used for the spectrometer of figure 11, the spectrometer of figure 9 should have a parameter β of approximately - 5.9x10<sup>-3</sup>cm<sup>-1</sup>/ ns. This would increase to a total nearly linear chirp increasing wavelength of 1.5cm-1 in 256ns. Each chirp wave can therefore provide a complete scan by itself.
[0036] As can be seen in figure 10, the use of the method on which the invention is based, that is, Method 1, allows the entire spectral region to be recorded within each individual or unique pulse. As shown in Figure 10, this includes sampling the detected pulse as well as its total length, thus obtaining a range of spectral elements from that single pulse. In contrast, in Method 2 only a single spectral element can be recorded during a single pulse. Therefore, if the same number of sampling points, n, is recorded, for example n = 512 which is the maximum possible number in Method 2 (see: Applied Optics 41, 573 (2002)), the theoretical improvement in the achievable signal-to-noise in Method 1 should be ^ n, which for point 512 is a factor of about 22. An advantage of Method 1 is that it does not experience pulse-to-pulse fluctuations (both amplitude and temporal) within a recorded scan as only one optical pulse is required. In Method 2, the system has been shown to undergo amplitude fluctuations of the laser diode output from pulse to pulse (see: Applied Optics 41, 573 (2002)).
Figures 12 and 13 show experimental results taken using the spectrometer of Figure 9. In the configuration of the spectrometer used in the
ES 2 392 834 T3 Figures 12 and 13, a distributed feedback single mode laser was used without a spectral filter and I<sub>or</sub> and I<sub>to</sub> were recorded using the SBM method. Figure 12 shows measurements for a sample of 1,1 difluoroethylene (CF2CH2). The CF2CH2 spectrum in the upper trace was taken using the spectrometer of Figure 7 but adapted to replace the QC laser with a black body source. The two lower traces taken using the spectrometer in Figure 9 show both I<sub>or </sub>with the evacuated cell, like <sup>I</sup>a with the 1,1 difluoroethylene sample <sup>(CF</sup>2<sup>CH</sup>2<sup>)</sup> inside the cell. Figure 13 shows results for<sup>1,1 difluoroethylene (CF</sup>2<sup>CH</sup>2<sup>) </sup>taken using the spectrometer of Figure 9. The absorbed signal I<sub>to</sub> was recorded using an average of 4096 scans. The upper trace shows I<sub>to</sub>. The bottom line is also I<sub>to</sub> but with a solid Ge etalon instead of a sample gas cell 17. This bottom trace shows the etalon fringe pattern demonstrating near-linear spectral variation of a wavelength from short to long. As can be seen in a comparison of the Fourier transform and the spectral laser diode in Figure 12 and the upper trace in Figure 13 with the Fourier transform spectrum in Figure 8, there is a strong correlation between the chemical fingerprints of the Difluoroethylene recorded using both types of spectrometer. However, the Fourier transform spectrum in Figures 8 and 12 recorded using the spectrometer of Figure 7 took more than four hours to obtain, while the laser diode spectrum in Figures 12 and 13 required less than two minutes.
[0038] The wavelength interval over which the induced scanning of the chirp wave occurs is sufficient to allow an identification of the chemical fingerprint of the gas to be recorded, see Figure 14. Figure 14 was recorded using the SBM method of the configuration of Figure 9. The upper trace in Figure 14 is for 1,1, difluoroethylene (CH<sub>2</sub>CF<sub>2</sub>) and the lower trace, in the same figure, is for carbonyl fluoride (COF2). Figure 14 shows the ease of pattern recognition (chemical fingerprint identification) within a 200ns time window using the spectrometer of Figure 9. To facilitate clarity, the transmission spectrum has been countered. The wave number calibration using a germanium (Ge) etalon with a fringe spacing of 0.0483 cm-1 and reference lines of 1.1, difluoroethylene taken from a high resolution Fourier transform spectrum using the configuration shown in Figure 7, except with a blackbody font.
[0039] In the spectrometer of Figure 9, the product of the width duration of
ES 2 392 834 T3 signal line cannot be less than a certain minimum value found in the uncertainty principle. This relationship is described in detail by Bracewell (The Fourier Transform and Its Applications, McGraw-Hill (1965)), who has shown that the product of the equivalent duration At, and the equivalent line width Av, must exceed or equal C , a constant that is determined by the shape of the impulse. For a rectangular time window AtAv> C = 0.886, and for a Gaussian time window AtAv> C = 0.441. In a short pulse spectrometer method, if the pulse duration were shortened there would be a limitation to the Fourier transform resolution, whereas if the chirp wavelength were lengthened it would be excessive. A similar analysis can be carried out for the limitations of the temporal resolution of the detection system on which the invention is based, as described below. In a time window τ the laser frequency (Av = c; λ is the wavelength, v is the frequency, c is the wave speed) will be chirp with the quantity dv / dt χ τ, so if a window The lower temporal interval used with the Fourier Av limited frequency interval would increase, while the chirp limited frequency interval would decrease. The best time opening, τ, will thus be determined by C / τ = dv / dt χ τ. If we rewrite this equation in terms of Av we get Av = dv / dt χ C / Av, where Av = (C χ dv / dt). In the restrictive case of C = 1 and a chirp wave velocity -0.0066 cm<sup>-1</sup>/ ns, or 0.015 cm<sup>-1</sup>. This would drop to 0.014 cm<sup>-1</sup> if the rectangular window function were used, since 0.01 cm<sup>-1</sup> if the Gaussian time window were adequate.
[0040] Figure 15 shows the absorption spectra recorded using an SBM method of Figure 9 for a sample atmospheric gas. An average of 64 thousand scans were used. Trace (a) shows the results for a cell pressure of 6733 Pa (50.5 Torr). Trace (b) shows the results for a cell pressure of 600 Pa (04.5 Torr). Trace (b) shows the results for a sample to which carbon dioxide (CO2) is added. In this case, the pressure was 13759 Pa (103.2 Torr). The very low absorption coefficient line, which corresponds to H2O, for example the peak on the left side of Figure 15, has almost the same absorption percentage in traces (b) and (c). However, it is evident that there has been a large increase in the percentage of absorption due to carbon dioxide in trace (c) compared to trace (b). Figures 14 and 15 show that it is possible to achieve a simultaneous gas measurement of the different species and that it is possible to identify them (compound identification). [0041] Various modifications of the spectrometer of Figure 9 can be made within the scope of the claims. For example, for the method
Dual-beam ES 2 392 834 T3, instead of having a separate reference cell being evacuated, a reference signal can pass through the sample cell itself 17. As shown in Figure 16 as configuration 1c. Here, the measurement path is 16a and the reference path is 16b. For ease of clarity, paths 16a and 16b are shown separately in Figure 16, but it can be seen that they both pass through sample cell 17. If the optical path length of the signal path, 16a is L<sub>to</sub>, and that of the reference path 16b is Lb, then in order to minimize the absorption in the reference path 16b, L<sub>to</sub> must be greater than Lb (L<sub>to</sub> >> Lb). This can be configured, for example by ensuring that the measurement beam repeatedly passes through the sample cell 17, while the reference beam either passes directly through the cell, and thus only passes once, or only performs a limited number of passes.
[0042] The modified Beer-Lambert expression required that the 1c configuration be derived as follows: for signal path I<sub>to</sub>= I<sub>or</sub>exp (-aL<sub>to</sub>) and for the reference path Ib = I<sub>or</sub>exp (-aLb). Therefore, ln (I<sub>to</sub>/ Ib) = - a (L<sub>to</sub>-Lb). In configuration 1c, the time transit difference between both pulses is chosen less than the chirp increasing wavelength time or the duration of the driving current / voltage pulse. Thus, the back light pulse reaches detector 24 prior to the arrival of the signal pulse at detector 23. The outputs of digitizers 12 and 14 are recorded, to allow the control acquisition circuit 10 to relate them to provide I.<sub>to</sub>/ Ib as previously detailed. An advantage of the spectrometer of configuration 1c of Figure 16 is that fewer optical elements are used than in the first embodiment, configuration 1b of Figure 9, without a reference cell. This reduces the overall size and weight of the spectrometer setup.
[0043] Configuration 1d of Figure 16 is a modification of configuration 1c. In this case, only a single detector is used. For this purpose, instead of being directed towards the detector 24, the reference beam is directed towards the detector 23. The difference in absorption path is identical to that of configuration 1c, specifically AL = (L<sub>to</sub>-Lb). When a pulse train is incident on the beamsplitter of Figure 16, the action of the beamsplitter is to divide each individual pulse in the pulse train into two components. Any pulse in the pulse train that follows the optical path 16a has an accompanying pulse that follows the optical path 16c. This has important consequences when considering the
ES 2 392 834 T3 Ib and I detection<sub>to</sub> in the configuration of a single detector 1d. To calculate the ratio of Ib to I<sub>to</sub> the corresponding signals with Ib and I<sub>to</sub> they must be recorded separately and then processed in the manner described for the SB operating mode in Figure 9, embodiment 1b. This means that an impulse corresponding to I<sub>to</sub> cannot reach the detector until its accompanying pulse corresponding to Ib has been digitized by digitizer 12 and recorded by acquisition and control system 10. The next pulse associated with Ib, however, cannot reach the detector, before that impulse I<sub>to </sub>above has been digitized by the digitizer 12 and recorded by the control and acquisition system 10. Therefore, the difference in the length of the optical path and consequently the transit time, between the optical path 16a and the optical path 16c, must be greater than the distance defined by a temporary pulse duration (speed of light χ tp) but less than the distance defined by the pulse repetition time (speed of light χ t<sub>re</sub>p).
[0044] Heretofore, the spectrometers on which the invention is based have been described with reference to a single mode QC laser as well as a distributed feedback QC laser (DFB). However, they could be replaced by a multi-longitudinal mode laser. Doing this brings both advantages and disadvantages. The main advantage is that it extends the effective tuning range of the spectrometer. Because the absorption spectra of many gases interesting for detection applications consist of groups of absorption characteristics separated at regular intervals, the coincidences between the emission and absorption lines occur at regular but frequent and widely separated intervals (see Infrared Vibration- Rotation Spectroscopy, Geoffrey Duxbury, Wiley 2000 Chapters 5 and 9, for a look at the details of these coincidences). This can be seen in Figures 17a and 17b. In Figure 17a, the upper trace is an absorption spectrum for a sample gas. As can be seen, this spectrum is relatively complex. The bottom trace in Figure 17a shows the emission response of the multi-mode chirp QC laser, which is used to detect the sample gas. Figure 17b shows the detected signal, from which it can be seen that there are several matches between the detection data input by the laser and the test characteristics.
[0045] In the absence of a spectral filter 15 in the spectrometer of Figures 9 and 16, all the spectra of Figure 17b would overlap. However, the use of such a filter allows both the separation of the spectra as well as the
ES 2 392 834 T3 identification of the number of waves / cm-1 in the region in which they occur, as shown schematically in Figure 18. However, if the tuning of each mode provided by the number of decreasing waves chirp was greater than the longitudinal mode spacing, then a partial overlap of the spectra would still occur. Furthermore, if the spectrum of the multilongitudinal mode laser were contaminated with the occurrence of off-axis parabola modes (OAP) of the laser it would be difficult to implement the described spectral filtering method. This is due to the tight wavenumber / cm-1 spacing between the off-axis (transverse) parabola modes, making it extremely difficult to design an appropriate and efficient broadband spectral filter.
[0046] In addition to expanding the effective tuning range of the spectrometer, another advantage of using a multimode laser is the possibility of using a combination of section mode and tuning temperature of the individual modes to achieve full tuning within the usable intensity. of the low and high modes of the wave number (gain curve) of the laser. This is shown schematically in Figure 19.
The spectrometer on which the invention is based exploits the almost linear chirp increasing wavelength of the intrinsic emission line width that occurs on a sub-microsecond time scale and is therefore capable of scanning a frequency of repetition (PRF) as high as 1MHz. This potential speed gain, which consists of an improvement of several orders of magnitude compared to the prior art, would allow the present system on which the invention is based to fully exploit the multiple advantages of capabilities by, for example, achieving measurements on time. real to study processes such as the rapid reactions of chemical substances (for example those of Free Radicals or atmospheric fluctuations in real time).
The resolution of the time resolution of the resolved spectrometer on which the invention is based is not determined by the effective line width of the laser induced by the current pulse, but by the speed of the laser chirp wave, which is the uncertainty principle, and the temporal resolution of the detection system. In terms of the temporal response of the detection system, this happens because the number of pixels (one pixel corresponds to a given time interval) in which the spectrum can be recorded within the chirp wavelength is limited by this response. The speed of this chirp wave is governed by the parameter β. The two parameters that affect the wave number resolution are the tuning speed β of the intrinsic line width of the laser 20 and the response
ES 2 392 834 T3 temporary detection system. Since the chirp wave number velocity is relatively insensitive to pulse width for this laser (see Figure 3), the only method to achieve increased spectral resolution with the laser used here is to increase detection line width (up to the limit of the uncertainty principle). In this way, the proportion of a detection system with a wide line width (500MHz) can cause a very high spectral resolution as can be seen in Figure 13.
Various modifications can be made to the described configurations within the scope of the claims. For example, it should be understood that the spectrometer configuration on which the invention is based is fully capable of utilizing an even faster than detailed detection system or / and a semiconductor laser diode exposing a lower chirp wave velocity, thus increasing the resolution available. In a further variation, the laser substrate temperature could change. This could be accomplished by varying the repetition frequency of the applied rectangular current pulse in submicrosecond. In an alternative variation the substrate temperature can vary by the base level of variation DC of the rectangular duration of the driving current pulse in sub-microseconds applied to the electrical contacts of the semiconductor diode laser. Furthermore, in the detailed embodiments, the means for splitting optical beams has been described as an optical beam splitter, however, it can also be a dichroic mirror or any other similar assembly. It should also be understood that several semiconductor laser diodes could be implemented in the spectrometer configuration on which this invention is based to achieve simultaneous measurements for different species.
Contents5
10 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10
20 members in 11 offices
Priority claims9
| Document | Office | Kind | Date |
|---|---|---|---|
| 0208100 | United Kingdom | A | |
| 0208100 | United Kingdom | A | |
| 0208100 | United Kingdom | – | |
| 0301510 | United Kingdom | W | |
| 0301510 | United Kingdom | W | |
| 0208100 | – | – | – |
| GB20020008100 | – | – | – |
| PCTGB200301510 | – | – | – |
| WO2003GB01510 | – | – | – |
Members20
| Document | Office | Kind | |
|---|---|---|---|
| GB0208100D0 | United Kingdom | D0 | |
| CA2482402A1 | Canada | A1 | |
| WO03087787A1 | World Intellectual Property Organization (WIPO) | A1 | |
| AU2003219320A1 | Australia | A1 | |
| WO03087787A8 | World Intellectual Property Organization (WIPO) | A8 | |
| EP1493017A1 | European Patent Office (EPO) | A1 | |
| KR20050003353A | Republic of Korea | A | |
| RU2004132718A | Russian Federation | A | |
| US2005157303A1 | United States of America | A1 | |
| JP2005522694A | Japan | A | |
| CN1659429A | China | A | |
| AU2003219320B2 | Australia | B2 | |
| US7283243B2 | United States of America | B2 | |
| RU2313078C2 | Russian Federation | C2 | |
| CN100561196C | China | C | |
| JP4437668B2 | Japan | B2 | |
| KR100959625B1 | Republic of Korea | B1 | |
| CA2482402C | Canada | C | |
| EP1493017B1 | European Patent Office (EPO) | B1 | |
| ES2392834T3This record | Spain | T3 |
Numbers
- Publication
- 2392834
- Publication, DOCDB
- 2392834
- Publication, EPODOC
- ES2392834T
- Application
- 3715129
- Application, DOCDB
- 03715129
- Application, EPODOC
- ES20030715129T
Titles2
- Spanish
- Configuración de un espectrómetro diodo láser semiconductor y método
- English
- Configuration of a semiconductor laser diode spectrometer and method
Classification
- CPC, 10
- G01J3/4338
- G01J3/42
- B82Y20/00
- G01N21/39
- G01N2021/399
- H01S5/3402
- H01S5/06216
- H01S5/0622
- G01N21/031
- H01S5/34
- IPC, 8
- G01J3 42
- B82Y20 00
- G01J3 433
- G01N1 00
- G01N21 03
- G01N21 39
- H01S5 00
- H01S5 34