Light source substrates, infrared imaging devices, and infrared analysis chips

Abstract

This invention provides an infrared analysis configuration and methodology that offers high spatial and temporal resolution and can be integrated onto a chip. [Solution] The light source substrate has multiple light-emitting elements arranged in an array, each emitting infrared light whose intensity is modulated at a speed of 160 Hz or higher.

Description

[Technical Field]

[0001] This invention relates to a light source substrate, an infrared imaging device, and an infrared analysis chip. [Background technology]

[0002] In the near-infrared to mid-infrared region, infrared spectroscopic analyzers known as Fourier transform infrared spectroscopy (FT-IR) have been put into practical use. Infrared spectroscopy is widely used in fields such as chemistry, biology, materials science, and physics as a technique for structural analysis, identification, qualitative analysis, and quantitative analysis of materials, from basic research to industry. Infrared spectroscopy and infrared absorption measurements require infrared light sources with a broad wavelength range, and generally, macroscopic (millimeter-order) and slow (response speed of about 100 ms) blackbody synchrotron radiation sources such as halogen lamps and ceramic light sources are used.

[0003] In the visible to near-infrared region, time-resolved spectroscopy techniques using short-pulse light sources ranging from femtoseconds to nanoseconds have advanced in recent years, making it possible to elucidate the processes of chemical reactions and structural changes that occur moment by moment.

[0004] In the visible light region, optical technologies are being applied to the bio and medical fields, and submicron-order spatial resolution is being achieved through microspectroscopy measurements using objective lenses. Bioimaging and biochip analysis using fluorescent markers in the visible light region are also being performed. In the infrared region, spectroscopic analysis and imaging techniques with high temporal and spatial resolution comparable to that of the visible light region are desired.

[0005] On the other hand, light sources using carbon nanotubes (see, for example, Patent Document 1 and Non-Patent Document 1) and light sources using graphene (see, for example, Patent Document 1) have been proposed. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Patent No. 5747334 [Patent Document 2] Patent No. 6155012 [Non-patent literature]

[0007] [Non-Patent Document 1] T. Mori, Y. Yamauchi, S. Honda, H. Maki, An electrically-driven, ultra-high-speed, on-chip light emitter based on carbon nanotubes, Nano Letters 14 (2014) 3277. [Overview of the project] [Problems that the invention aims to solve]

[0008] The light sources used in current infrared spectrometers are large in size and have slow response speeds. As a result, there are problems such as (1) the inability to obtain submicron-order spatial resolution, (2) the inability to perform high-speed time-resolved measurements like those of pulsed lasers, and (3) the inability to integrate infrared light sources onto a chip.

[0009] In other words, macroscopic light sources commonly used in FT-IR are limited by geometrical optics and diffraction limits, resulting in a spatial resolution of only about 10 μm even when using microspectroscopy techniques with objective lenses.

[0010] When performing high-speed time-resolved measurements in the infrared region, methods such as step-scanning using high-speed infrared "detectors" are employed. However, unlike in the visible light region, there are currently no detectors in the infrared region that are both "high-speed" and "high-sensitivity." Therefore, high-speed measurements are inevitably limited to low sensitivity, and conversely, high-sensitivity measurements require the use of low-speed detectors.

[0011] Furthermore, in current infrared spectroscopic analysis, high-resolution local analysis on the sub-micron order required in fields such as chemistry, medicine, and bioimaging cannot be performed, so its application to the imaging field is extremely limited. In analysis chips using microfluidic channels and the like, analysis techniques based on various principles are combined, but infrared light sources such as halogen lamps and ceramic light sources cannot be integrated on the chip. If bioimaging and biochip analysis similar to those in the visible region can be performed in the infrared region, expensive fluorescent markers will not be required, and the range of use should be greatly expanded.

[0012] An object of the present invention is to provide a configuration and method for infrared analysis having high spatial resolution and high time resolution and enabling integration on a chip.

Means for Solving the Problems

[0013] In a first aspect of the present invention, an infrared analysis apparatus includes a light source using a nanocarbon material as a luminescent material, detection means for detecting infrared light output from the light source and transmitted through or reflected by a sample, and the nanocarbon material is disposed on the surface of a substrate and emits surface light.

[0014] In a second aspect of the present invention, an infrared analysis chip is provided. The infrared analysis chip includes a substrate on which a microfluidic channel is formed, light detection / spectroscopy means integrated at a position where the microfluidic channel is formed on a first surface of the substrate, an infrared light source integrated at a position facing the light detection / spectroscopy means on a second surface of the substrate, and has.

[0015] As another configuration example, the infrared analysis chip includes a light source substrate on which a plurality of light-emitting elements that emit infrared light are arranged in an array, a probe substance fixed at a position corresponding to the plurality of light-emitting elements on the surface of the light source substrate and selectively binding to a specific substance, It may be a configuration having

[0016] In a third aspect of the present invention, an infrared imaging device is provided. The infrared imaging device a light source substrate in which a plurality of light emitting elements that emit infrared light are arranged in an array, an infrared detector arranged to face the light source substrate, has The surface of the light source substrate can mount a sample, and the infrared detector operates in synchronization with the light emission timing of the plurality of light emitting elements.

[0017] As another configuration example, the infrared imaging device an infrared light source array in which a plurality of light source elements having a nanocarbon material extending between a pair of electrodes and a gate electrode for applying a gate voltage to the nanocarbon material are arranged, a voltage control unit for controlling the gate voltage, an infrared detector arranged to face the infrared light source array, has, and the voltage control unit sweeps a hot spot along the length direction of the nanocarbon material by changing the gate voltage.

Advantages of the Invention

[0018] With the configuration and method of the present invention, infrared analysis having high spatial resolution and temporal resolution and capable of being integrated on a chip is realized.

Brief Description of the Drawings

[0019] [Figure 1A] It is a perspective view showing a basic structure of a nanocarbon light source used in an embodiment. [Figure 1B] It is a diagram showing a configuration in which a protective film is provided on the nanocarbon light source of FIG. 1. [Figure 2] It is a schematic diagram of a probe light source having a nanocarbon light source. [Figure 3] [[ID= 48]]It is an infrared camera image of the fabricated nanocarbon light source. [Figure 4]This is a schematic diagram of the infrared spectrometer of the first embodiment. [Figure 5] This figure shows local infrared measurement using a near-field. [Figure 6] This figure shows the results of infrared spectroscopy analysis of polystyrene according to the present invention using a graphene light source. [Figure 7A] This figure shows the direct intensity modulation of the nanocarbon light source according to the embodiment. [Figure 7B] This figure shows the results of infrared spectroscopic analysis of atmospheric molecules using intensity-modulated infrared light. [Figure 8] This is a schematic diagram of the infrared analyzer according to the second embodiment. [Figure 9] This figure shows an example of infrared imaging measurements using a nanocarbon light source. [Figure 10] This is a schematic diagram of the infrared analyzer according to the third embodiment, illustrating the principle of high-speed infrared spectroscopy. [Figure 11] This figure shows an example of a change in a measured substance due to chemical reaction pulse stimulation. [Figure 12] This figure shows an example of high-speed time-resolved measurement using repeated chemical reaction pulse stimulation and infrared pulse irradiation from a nanocarbon light source. [Figure 13] This figure shows short-pulse light emission from a nanocarbon light source. [Figure 14] This is a schematic diagram of the infrared analyzer according to the fourth embodiment, showing infrared measurement using a microanalysis chip having a microfluidic channel. [Figure 15] This is a schematic diagram of a microanalysis chip that integrates a nanocarbon light source and a detector on a substrate. [Figure 16] This is a diagram illustrating the principle of infrared analysis in the fifth embodiment. [Figure 17] This is a schematic diagram of an infrared light source array applied to a biochip according to the embodiment. [Figure 18A] This is a schematic diagram of an infrared light source array using matrix electrodes. [Figure 18B] Figure 18A is a circuit diagram showing an infrared light source array with a rectifying function. [Figure 19]This is a schematic diagram of the infrared analyzer 160 according to the fifth embodiment. [Figure 20] This figure shows an example of applying the infrared light source array of the sixth embodiment to imaging. [Figure 21] This is a schematic diagram of the nanocarbon light source 10A according to the seventh embodiment. [Figure 22] This figure shows an example of applying a light source array using a nanocarbon light source according to the seventh embodiment to imaging. [Figure 23] This is a schematic diagram of an infrared analyzer using the imaging device of the seventh embodiment. [Modes for carrying out the invention]

[0020] In this embodiment, (i) a new infrared spectroscopic analyzer is provided that uses submicron-order light-emitting materials such as graphene and carbon nanotubes as infrared light sources. (ii) infrared spectroscopic analysis with high spatial resolution exceeding the diffraction limit and infrared imaging using near-field light are realized. (iii) By using a nanocarbon light source that can modulate the emission intensity at high speed (approximately 100 ps), high-speed time-resolved infrared spectroscopic measurements based on a new principle are made possible. (iv) A microfluidic analyzer is provided in which a minute light-emitting element is formed on a microfluidic channel. (v) By arranging minute infrared light source elements such as nanocarbon light sources in a two-dimensional array, a biochip analysis technology using infrared absorption based on a new principle that does not use fluorescent markers is provided. (vi) By arranging minute infrared light source elements in two dimensions, high-speed infrared imaging is realized with a single infrared detector. (vii) By configuring the infrared light source elements to allow hotspot sweeping, spatial resolution in one dimension can be achieved with a single infrared light source element. Furthermore, by arranging multiple infrared light source elements capable of sweeping hotspots in a direction perpendicular to the sweep direction, wide-area infrared imaging can be achieved.

[0021] The embodiments of the invention will be described in detail below.

[0022] <First Embodiment> In the first embodiment, by using a light-emitting material of nanometer or submicron size, such as graphene or carbon nanotubes, as an infrared light source, a compact, inexpensive, high-speed, and high-spatial-resolution infrared analyzer is realized that replaces conventional infrared spectroscopic analyzers (FT-IR, etc.) that use halogen lamps or ceramic light sources.

[0023] Figure 1A is a basic configuration diagram of the nanocarbon light source 10 used in the infrared analyzer of the embodiment. A nanocarbon material 15 is placed on a substrate 11, and electrodes 12a and 12b are formed at both ends of the nanocarbon material 15. The electrodes 12a and 12b are electrically connected to the nanocarbon material 15 at both ends.

[0024] The nanocarbon light source 10 has a planar structure in which the nanocarbon material 15, which serves as a light-emitting layer, is exposed on its surface. The electrodes 12a and 12b only need to be electrically connected to the nanocarbon material 15, so they may be partially or entirely embedded in the substrate 11.

[0025] The nanocarbon material 15 can be formed on any substrate, such as a silicon substrate or a glass substrate, and the substrate 11 can be any material or type, such as a silicon substrate, glass substrate, or polymer substrate. Examples of nanocarbon materials 15 include single-walled carbon nanotubes, multi-walled carbon nanotubes, single-walled graphene, multi-walled graphene, and thin graphite. The carbon nanotube may be a single carbon nanotube or a carbon nanotube thin film formed from multiple carbon nanotubes in a sheet-like structure. Since the nanocarbon light source 10 emits light when electricity is passed through the nanocarbon material 15, the electrical properties of the nanocarbon material 15 may be metallic or semiconducting.

[0026] The nanocarbon material 15 may be exposed on the substrate 11 as shown in Figure 1A, or the surface of the light-emitting element containing the nanocarbon material 15 may be covered with a light-transmitting protective film 16 as shown in Figure 1B. As the protective film 16, an insulating thin film that is light-transmitting for the wavelength of use, such as silicon oxide or alumina, may be used.

[0027] The nanocarbon light source 10 emits light by electrically heating the nanocarbon material 15 through a pair of electrodes 12a and 12b. Electrical heating increases the temperature of the nanocarbon material 15, causing it to emit light through thermal radiation (called blackbody radiation or graybody radiation) associated with the temperature increase. The thermal radiation from the nanocarbon light source 10 has an emission spectrum described by Planck's law, a blackbody radiation equation, and exhibits a broad emission spectrum mainly in the infrared region (far-infrared to near-infrared). Furthermore, by applying a large current or by fabricating a light-emitting element with a cross-linked or membrane structure using the nanocarbon material 15, the temperature of the nanocarbon material 15 can be increased, allowing it to emit light up to the visible light region.

[0028] In this embodiment, a new infrared analysis technique is realized using a nanocarbon light source 10 as an infrared light source. Conventional infrared spectroscopy uses halogen lamps or ceramic light sources as infrared light sources, but these light sources are large in size (on the order of millimeters) and have a slow response speed of about 100 ms. As a result, problems arise such as the inability to obtain a spatial resolution of 10 μm or less due to the diffraction limit of infrared light, the inability to perform high-speed measurements, and the inability to integrate them on a chip.

[0029] In contrast, the nanocarbon light source 10 of the embodiment behaves as an infrared light source due to blackbody radiation, but unlike conventional infrared light sources, it has the following features: (i) it can be miniaturized to the order of nanometers, (ii) it can be integrated on any substrate such as silicon chips or glass, and (iii) it can emit light at high speed with a response time of 100 ps. By using the nanocarbon light source 10, it is possible to realize a high-speed, high-spatial-resolution infrared spectroscopic analysis device, and it becomes possible to develop an infrared spectrometer based on a new principle that cannot be realized with conventional infrared light sources.

[0030] Figure 2 is a schematic diagram of a probe-type light source 20 equipped with a nanocarbon light source 10. The nanocarbon light source 10 may be formed on a substrate of any shape. An emissive element formed on a flat substrate 11 as shown in Figures 1A and 1B may be used, or the nanocarbon light source 10 (or nanocarbon emissive element) may be fabricated on the tip of a convex substrate 11A processed into the shape of a protrusion or probe, as shown in Figure 2. Even if the shape of the substrate 11A is probe-type, the tip of the substrate 11A can be made flat, and the light-emitting surface of the nanocarbon light source 10 (i.e., the surface on which the nanocarbon material is placed) can be a plane with a two-dimensional extent. Furthermore, even if the tip of the substrate 11A is processed into a curved surface, the nanocarbon light source 10 can be fabricated on the curved surface.

[0031] Since both the nanocarbon light source 10 formed at the tip of the substrate 11A and the probe-type light source 20 itself are minute, measurements can be taken by irradiating the measurement target with infrared light while the nanocarbon light source 10 is close to the measurement target.

[0032] Figure 3 shows an infrared camera image of the fabricated nanocarbon light source 10. Graphene is used as the nanocarbon material 15. Figure 3(A) is an image of the device surface when the applied voltage is 0V, i.e., when no voltage is applied to electrodes 12a and 12b. The dark region between the pair of electrodes 12a and 12b is the graphene nanocarbon material 15.

[0033] Figure 3(B) shows the emission state when a voltage is applied. In this example, a voltage of 3.7V is applied to the nanocarbon material 15, and it can be seen that the graphene (G) portion is emitting light. This emission is infrared wavelength light and can be used as measurement light to illuminate the object to be measured.

[0034] Figure 4 is a schematic diagram of the infrared analyzer 100 according to the first embodiment. The infrared analyzer 100 has a nanocarbon light source 10 and spectrometers / photodetectors 110-1 and 110-2. The sample S to be measured is placed between the nanocarbon light source 10 and the spectrometers / photodetectors 110-1 and 110-2. The spectrometer / photodetector 110-1 detects reflected light L from the sample S. R , scattered light L S The spectrometer / photodetector 110-2 detects transmitted light L that has passed through the sample S. T The spectrometer / photodetector 110 does not necessarily need to be placed on both the reflective and transmitted sides of the sample S; it may be placed on only one side.

[0035] Infrared light generated from the nanocarbon light source 10 is irradiated onto a predetermined measurement area 101 on the sample S. Infrared light L irradiated from the nanocarbon light source 10 IR This is partially absorbed by infrared absorption due to molecular vibrations of sample S. This absorbed infrared light is observed by light transmitted, reflected, or scattered by sample S. Transmitted light L T , reflected light L R , scattered light L S By observing at least one of these with the spectrometer / photodetector 110, the light absorption in sample S can be measured. The spectrometer / photodetector 110 can not only measure the intensity of infrared light, but also measure the absorption spectrum by spectroscopy using a diffraction grating or Michelson interferometer.

[0036] The sample S can be a solid, liquid, or gaseous substance, and the state of the sample S, placed between the nanocarbon light source 10 and the spectrometer / photodetector 110, can be detected and analyzed by the infrared analyzer 100. Because a nanocarbon light source 10 with a minute, planar light-emitting structure is used, it is also possible to locally measure a part of the sample S by bringing the light source close to the sample S. In particular, when using a probe-type light source 20 as shown in Figure 2, local measurements can be performed by bringing the light source close to the sample surface, regardless of the shape of the sample S.

[0037] Figure 5 shows a localized infrared measurement using a near-field. The nanocarbon light source 10 of the embodiment, or the probe-type light source 20 using the nanocarbon light source 10, is of a minute size and has a planar structure in which the light-emitting layer can be exposed. By utilizing this unique light-emitting structure of nanocarbon, high spatial resolution localized area measurements are realized using a near-field generated in the vicinity of the nanocarbon light source 10.

[0038] The light emitted from the nanocarbon light source 10 can be extracted and used for measurement not only by a remote field, but also by a near-field generated near the light source. This near-field attenuates exponentially with distance from the light source and exists only in the vicinity of the light source. The near-field light 102 can be extracted and used for measurement by bringing the sample S to be measured close to the nanocarbon light source 10.

[0039] Unlike conventional far-field light, near-field light 102 is localized light whose size is determined by the size of the light source, regardless of the diffraction limit. Therefore, it becomes possible to perform ultra-high spatially resolved local infrared measurements, exceeding the diffraction limit that is a problem in conventional infrared spectroscopy.

[0040] Since the size of the nanocarbon light source 10 can be reduced to the order of nanometers, it is possible to measure an area orders of magnitude smaller than the diffraction limit of 10 μm in conventional infrared spectroscopy. The near-field generated by the nanocarbon light source 10 of this embodiment is a near-field generated in the vicinity of the light source itself, unlike near-field light that is locally generated in fine pores or on the spherical surface of the tip of a sharp probe, and is therefore completely different in principle from conventional near-field spectroscopy.

[0041] Conventional near-field measurements using pores or probes generate an electromagnetic field at the pore or probe tip by irradiating it with laser light or other external sources. The near-field measurement in this embodiment utilizes the near-field generated within the minute nanocarbon light source 10 itself, and is a new principle of near-field infrared measurement that uses the "near-field generated in the vicinity of the light source" without using external laser light or other external sources as in conventional methods.

[0042] Thus, in order to utilize the near-field generated by the light source itself, it is necessary that the light source is not only extremely small in size, but also that the light-emitting region is a planar structure that can be exposed to the outside. This can only be realized with a tiny, planar element with an exposed light-emitting layer, such as the nanocarbon light source 10 in the embodiment.

[0043] Conventional infrared light sources, such as halogen lamps, have metal filaments that form the light-emitting layer, which are on the order of millimeters in size. Furthermore, the filament is sealed in a glass tube or the like, making it impossible to bring the light-emitting layer close to the sample being measured. On the other hand, the nanocarbon light source 10 is a tiny light source that can be reduced to the order of nanometers, and it is a planar structure element in which the nanocarbon of the light-emitting layer is exposed. This makes it possible to bring the nanocarbon light-emitting layer extremely close to the sample S being measured.

[0044] In particular, since the intensity of near-field light decreases exponentially with distance from the light-emitting layer, it is necessary to bring the light-emitting layer and the sample S to be measured close together in relation to the wavelength. To utilize the near-field near the light source, a planar light source such as the nanocarbon light source 10 is required. Furthermore, since the infrared analyzer 100 uses the near-field of the tiny nanocarbon light source 10 itself, there is no need to use an expensive and large laser light source, and a low-cost, ultra-compact infrared analyzer 100 can be realized.

[0045] The nanocarbon light source 10 may have a configuration in which the nanocarbon material 15 is completely exposed, as shown in Figure 1A, or the nanocarbon material 15 may be covered with a thin protective film 16, as shown in Figure 1B. If the protective film 16 is thin, the near field can be utilized. Generally, there is no problem as long as the thickness of the protective film 16 is smaller than the wavelength of light, and the smaller the film thickness, the greater the intensity of the near field light.

[0046] Unlike conventional infrared light sources such as halogen lamps, the nanocarbon light source 10 is capable of extremely fast infrared emission with a response time on the order of 100 ps. By applying modulated voltages or currents such as pulses or rectangles to the nanocarbon light source 10, short-pulse light on the order of 100 ps and rectangular emission with a fast rise time can be obtained. Infrared light with freely modulated intensity can be obtained depending on the waveform of the applied voltage or current.

[0047] Currently, pulsed lasers are used as such high-speed light sources, and time-resolved spectroscopy measurements are performed using short-pulse light sources in the femtosecond to nanosecond range. While such short-pulse laser light sources are currently used in the ultraviolet, visible, and near-infrared regions, there are no high-speed pulsed laser light sources in the mid-infrared region. Furthermore, because laser light sources have a very narrow wavelength range, they do not possess the broad emission spectrum required for infrared spectroscopy and other applications.

[0048] In contrast, the nanocarbon light source 10 of the embodiment, despite being an extremely fast light source as described above, exhibits an emission spectrum that is extremely broad in the infrared-visible region, described by Planck's law for blackbody irradiation. Therefore, it can be used for infrared spectroscopy in the same way as conventional halogen lamps, and it enables time-resolved infrared measurements with extremely high temporal resolution on the order of 100 ps, ​​which is impossible with halogen lamps. Such an ultrafast infrared analyzer does not exist in current technology, and the infrared analyzer 100 of the embodiment is an infrared analyzer based on a new principle.

[0049] The infrared analyzer 100 of this embodiment is also capable of infrared sensing using infrared spectroscopy. In spectroscopic analysis, spectral measurements are performed using a spectrometer or the like to analyze general materials, but spectrometers are large and expensive devices. On the other hand, even without using a spectrometer, by limiting the infrared light to a specific wavelength range using a filter or the like and performing photodetection, it is possible to sense the presence, concentration, amount, and mixing ratio of specific solid, liquid, or gaseous substances. With an ultra-compact structure using a nanocarbon light source 10, sensing of various substances becomes possible, and small sensors can be fabricated. In sensing, it is possible to measure by bringing the nanocarbon light source 10 close to the sample S to be measured, or to sense solid, liquid, or gaseous substances present in the space between the nanocarbon light source 10 and the spectrometer / photodetector 110.

[0050] Figure 6 shows an example of infrared spectroscopy using a nanocarbon light source 10 with graphene. This is an example of infrared transmitted light measurement of polystyrene using the method shown in Figure 5, with a nanocarbon light source 10 having 500 μm square graphene. The lower spectrum in the figure is the measured value from the infrared analyzer 100 using the nanocarbon light source 10, and the upper spectrum is the literature value. The absorption peaks in the spectra match the literature value, indicating that the infrared analyzer 100 of this embodiment yields results similar to conventional FT-IR infrared spectroscopy. This measurement result demonstrates that infrared spectroscopy, such as vibrational spectroscopy, using the nanocarbon light source 10 is actually feasible.

[0051] The nanocarbon light source 10 of this embodiment can directly modulate its emission intensity by applying a modulated voltage or current. Since the nanocarbon light source 10 itself is capable of high-speed blinking, it is possible to perform highly sensitive measurements using direct intensity modulation of the light source, which is difficult with conventional infrared light sources. For example, by directly modulating the emission of light from the nanocarbon light source 10 and receiving this modulated light with a photodetector in synchronization, highly sensitive photodetection can be achieved through synchronized measurements such as lock-in amplifier and gate operation. Compared to analysis with conventional infrared light sources, it becomes possible to perform spectroscopy, analysis, and sensing with a highly sensitive infrared light source. In particular, when the light source is high-speed, time-resolved measurements are possible even with a low-speed detector. Since "low-speed and highly sensitive" infrared detectors can also be used, time-resolved measurements can be performed with high sensitivity regardless of the type of infrared detector.

[0052] Figure 7A shows an example of direct intensity modulation using a nanocarbon light source 10. This is an example of direct intensity modulation at 1 kHz using a nanocarbon light source 10 with a 3 μm square graphene film. Figure 7B shows the results of infrared spectroscopic analysis of atmospheric molecules using directly modulated light from a nanocarbon light source 10 directly modulated at 163 Hz and an infrared detector with a lock-in amplifier. Carbon dioxide molecules and water molecules are detected in the atmosphere over a broad wavelength range. The reason why absorption peaks are detected in different wavelength ranges for water molecules and carbon dioxide molecules is because they have different types of molecular vibrations.

[0053] As shown in Figure 7A, the nanocarbon light source 10 of this embodiment can generate not only single-pulse light by applying a single pulsed electrical signal, but also continuous pulsed light by applying a repetitive pulsed voltage. Because it can be directly modulated at very high speed, the timing of the generated pulsed light can be freely controlled. Using these characteristics, high-speed infrared analysis becomes possible when a single pulsed light is generated at a certain timing. In addition, time-resolved measurements are also possible by injecting repetitive pulsed light. In infrared analysis using repetitive pulsed light, time-resolved measurements are also possible by introducing a delay time to the generation of pulsed light, thereby enabling stroboscopic time-resolved infrared analysis.

[0054] Thus, by using a nanocarbon light source 10 that has a broad spectrum and is capable of high-speed modulation, a new analytical method can be realized with the infrared analyzer 100.

[0055] <Second Embodiment> Figure 8 is a schematic diagram of a scanning infrared analyzer 100A according to the second embodiment. In the second embodiment, infrared imaging is achieved by scanning the nanocarbon light source 10 relative to the sample S.

[0056] The infrared analyzer 100A has a probe-type light source 20 with a nanocarbon light source 10 at its tip, and spectrometers / photodetectors 110-1 and 110-2. In the probe-type light source 20, a planar nanocarbon light source 10 is provided at the tip of a substrate 11A that has been processed into a probe shape.

[0057] The sample S to be measured is placed on a light-transmitting stage 22, such as glass, and scanned while irradiating the sample S with light from a light source 20. At least one of the probe-type light source 20 and the stage 22 is connected to a three-axis manipulator (not shown), allowing movement in three axes. This allows one of the nanocarbon light source 10 and the sample S to scan the other relative to the other.

[0058] Transmitted light L from sample ST Scattered light L S Reflected light L R By detecting at least one of them with spectrometers and photodetectors 110-1 and 110-2, information such as light absorption and spectral changes generated in the sample S can be obtained. By connecting the infrared analyzer 100A to an image processing device, the detection signal can be converted into an image signal and used as an infrared imaging device.

[0059] Unlike conventional infrared light sources, the nanocarbon light source 10 is an extremely small infrared light source and has a planar structure in which the light emitting layer can be exposed on the surface. By approaching or contacting the light emitting layer with respect to the sample S to be measured and scanning the nanocarbon light source 10 one-dimensionally, two-dimensionally, or three-dimensionally, one-dimensional, two-dimensional, or three-dimensional infrared imaging becomes possible. For example, due to infrared absorption by molecular vibrations inside the sample S, etc., changes occur in the intensity and spectrum of transmitted, scattered, and reflected light, so changes in one dimension, two dimensions, or three dimensions can be observed as an image. Since the transmitted, scattered, and reflected light can be spectroscopically analyzed by a spectroscope, wavelength-dependent imaging is also possible.

[0060] The infrared analyzer 100A is suitable not only for imaging but also for analysis in a specific local region. For example, by fixing the probe-type light source 20 at a certain location of the sample S, infrared spectroscopy of that minute region is possible. Similar to the first embodiment, since the extremely small nanocarbon light source 10 is used as the light source, the nanocarbon light source 10 can be brought close to the sample S to a distance below the wavelength, and measurement using near-field light is possible. That is, imaging and spectroscopic imaging with high spatial resolution beyond the diffraction limit of light are possible. By using this principle, it becomes possible to improve the spatial resolution, which was about 10 μm at the diffraction limit in a conventional microscopic infrared spectroscopic analyzer, to the nanometer order in the near field. As the sample S to be measured, objects of any shape can be imaged, and in addition to ordinary liquids and solids, it can also be used for bioimaging of biological tissues such as cells, enabling imaging in the fields of chemistry, biology, materials, and physics.

[0061] Figure 9 shows the measurement results of infrared imaging using the infrared analyzer 100A. In this example, a sample S, which has the number "5" patterned on it and is placed on glass, is scanned on a nanocarbon light source 10 using graphene. It can be seen that an infrared image reflecting the shape of sample S has been obtained.

[0062] <Third Embodiment> Figure 10 is a schematic diagram of the infrared analyzer 100B of the third embodiment. In the third embodiment, pump-probe spectroscopy is realized using a nanocarbon light source 10. The infrared analyzer 100B has a nanocarbon light source 10, an excitation source 105, and a spectrometer / photodetector 110. The nanocarbon light source 10 is used as a probe light source, and the probe light L in the infrared region probe The output of the spectrometer / photodetector 110 may be connected to the input of the information processing device 103.

[0063] Conventional light sources, such as halogen lamps and ceramic light sources, have only slow response speeds (approximately 100 ms), making it impossible to perform high-speed infrared spectroscopy analysis or high-speed time-resolved measurements by modulating the light source. For example, it is not possible to track rapidly changing chemical reactions using infrared spectroscopy.

[0064] In contrast, the nanocarbon light source 10 has an extremely fast emission response speed on the order of 100 ps. Therefore, by using the nanocarbon light source 10 as the light source, the infrared analyzer 100B can be given an ultrafast time resolution of 100 ps. The infrared analyzer 100B can track fast chemical reactions and other phenomena using infrared spectroscopy. As described above, if the light source is fast, time-resolved measurements are possible even with a very slow detector. For this reason, an ultra-high-sensitivity photodetector can be used as the spectrometer / photodetector 110.

[0065] In the measurement system of the infrared analyzer 100B, a chemical reaction pulse stimulus P to initiate a chemical reaction is applied to the measurement area 101 of the sample S from an excitation source 105 such as a pump light source. After a delay of Δt seconds from the irradiation of the pump light, probe light L is emitted from the nanocarbon light source 10. probe The pulse is irradiated onto the measurement area 101. Since the goal is to stimulate the sample to initiate a chemical reaction, the chemical reaction pulse is not limited to light irradiation; it may also be applied as an electrochemical reaction voltage, supplied as a pulse of a reactant, or subjected to other electrical stimulation or substance supply.

[0066] In photochemical reactions, the reaction can be initiated by irradiating the sample to be measured with light. In electrochemical reactions, electrodes that induce an electrochemical reaction are formed on the sample to be measured, and an electrical signal, such as a voltage to initiate the reaction, is input to these electrodes. In reactant supply, the substance necessary for the chemical reaction is supplied through a channel or the like, and the reaction is initiated by mixing. These chemical reaction pulse stimuli may be waveform stimuli as shown in Figure 10, or rectangular stimuli supplied.

[0067] Changes within the sample caused by stimulation are detected by the spectrometer / photodetector 110 as transmitted light, scattered light, or reflected light. The detected light may be input to the information processing device 103 as, for example, infrared absorption results due to excited molecular vibrations, for signal processing, analysis, etc. The information processing device 103 may have digital signal processing functions such as a spectrum analyzer or an image signal converter.

[0068] Figure 11 shows an example of the change in a measured substance due to chemical reaction stimulation. In the measurement system shown in Figure 10, when a chemical reaction pulse stimulus is applied to the sample, the chemical reaction proceeds as shown in Figure 11, and the final product is obtained through the reaction process and intermediates. At this time, the chemical reaction pulse stimulus (L pump After a delay time Δt seconds from the application timing t1, infrared light is emitted from the nanocarbon light source 10 as probe light L probeWhen sample S is irradiated with infrared light, the reaction process and intermediate formation state of sample S are illuminated. By measuring the transmitted, scattered, and reflected light from sample S with the spectrometer / photodetector 110, it becomes possible to analyze the reaction process and intermediates using vibrational spectroscopy, etc.

[0069] By gradually changing the delay time Δt during measurement, time-dependent infrared analysis of sample S is possible. By measuring the dependence on the delay time, it is possible to track and analyze the reaction process of sample S as it progresses moment by moment using infrared analysis. Spectrometers such as grating-based spectrometers or Michelson interferometers can be used in such measurement systems. In Michelson interferometer measurements, time-resolved measurements using a step-and-scan method with a high-speed light source are also possible.

[0070] Unlike conventional methods, high-speed time-resolved measurements are achieved on the infrared light source (nanocarbon light source 10), eliminating the need for a high-speed photodetector for the time resolution of infrared spectroscopy, and allowing the use of a low-speed photodetector. Generally, high-speed photodetectors have poor light-receiving sensitivity, and high-sensitivity photodetectors are slow, resulting in a trade-off between sensitivity and speed. However, the configuration and method of this embodiment enable high-speed time-resolved measurements using high-sensitivity photodetectors that were previously unusable.

[0071] Figure 12 shows an example of a measurement system using chemical reaction pulse stimulation and repeated irradiation with probe light. By repeatedly stimulating with chemical reaction pulses from the stimulator 105 and irradiating with infrared pulsed light from the nanocarbon light source 10, more sensitive and high-speed time-resolved measurements become possible. The principle and the device configuration itself are the same as those of the infrared analyzer 100B in Figure 10.

[0072] A gas, liquid, or solid sample is placed in the measurement area 101. For example, the sample S can be supplied by a flow cell 201 or the like. In response to a chemical reaction pulse stimulus, infrared light (L) from the nanocarbon light source 10 is applied. probeThe infrared light from the carbon light source 10 is irradiated with a delay time Δt, and this is repeated. The infrared light from the carbon light source 10 is, for example, ultrashort pulse infrared light. The response due to pulse stimulation and the measurement using infrared light are measured repeatedly at high speed, and the results are integrated in the spectrometer / photodetector 110 or the information processing device 103, so that measurements can be made with high sensitivity and a high S / N ratio corresponding to the number of repetitions.

[0073] As described with reference to Figures 10 and 11, any stimulus can be used to initiate a chemical reaction as a pulsed stimulus, such as photochemical excitation light, electrochemical voltage, or pulsed supply of reactants. Various methods can be used to apply the stimulus, and by gradually changing the delay time Δt, it is possible to track and analyze the reaction process as it progresses moment by moment. Grading and Michelson interferometers can be used as spectrometers, and step-and-scan methods can also be employed. Since a low-speed, high-sensitivity photodetector can be used, highly sensitive measurements are possible.

[0074] The high-speed time-resolved measurement using the infrared analyzer 100B of the third embodiment requires precise delay time control, but is feasible because the nanocarbon light source 10 can generate ultrashort pulses of infrared light at any desired timing. This makes maximum use of the fact that the nanocarbon light source 10 is a high-speed light source that can be directly modulated.

[0075] Figure 13 shows short-pulse emission from the nanocarbon light source 10. The time resolution of the infrared analyzer 100B is determined by the response speed of emission from the nanocarbon light source 10. By using the nanocarbon light source 10, high-speed time-resolved measurements using short-pulse light on the order of 100 ps are realized, as shown in Figure 13.

[0076] <Fourth Embodiment> Figure 14 is a schematic diagram of the infrared analyzer 100C according to the fourth embodiment. In the fourth embodiment, infrared measurement is realized using a microanalysis chip having a microfluidic channel. The microanalysis chip is an example of an infrared analysis chip that efficiently performs infrared spectroscopy (or absorbance) analysis.

[0077] The infrared analyzer 100C has a nanocarbon light source 10 and a spectrometer / photodetector 110. A microanalysis chip 108 may be placed between the nanocarbon light source 10 and the spectrometer / photodetector 110. A microchannel 107 is formed in the microanalysis chip 108, and the sample S is supplied into the microchannel 107. The microanalysis chip 108 with the microchannel 107 is effectively used in trace chemical analysis, bioanalysis, medical diagnosis, etc.

[0078] In addition to being extremely small, the nanocarbon light source 10 can be formed from any inorganic or organic material, including silicon, glass, and polymers. It also has a planar structure in which the light-emitting layer can be exposed. The nanocarbon light source 10 can be positioned adjacent to the microchannel 107 of the microanalysis chip 108, and infrared light L from the nanocarbon light source 10 can be emitted. IR This enables measurement and analysis on the chip.

[0079] The micro-analysis chip 108 can be fabricated using inorganic materials such as silicon and glass, or organic materials such as polymers, to create a chip body with microchannels 107. A nanocarbon light source 10 is placed near (for example, directly below) the microchannels 107. Infrared light from the nanocarbon light source 10 is irradiated onto a sample S flowing through the microchannels 107, and the transmitted, scattered, and reflected light (Lout) from the sample S is observed by a spectrometer / photodetector 110. This enables infrared analysis or sensing of the substance flowing through the microchannels 107.

[0080] As shown in Figure 14, the nanocarbon light source 10 may be arranged on the outside of the microanalysis chip 108 by bonding or other means so as to face the microchannel 107. Since the nanocarbon light source 10 is a minute, planar light source and can be formed directly on various substrates, the nanocarbon light source 10 may be formed directly on the microanalysis chip 108 in which the microchannel 107 is formed, or within the microchannel 107. By using the nanocarbon light source 10, it is possible to realize a microanalysis chip 108 with a light source that cannot be realized with conventional infrared light sources.

[0081] As shown in Figures 10-12 (Third Embodiment), by forming a microchannel 107 to which chemical reaction pulse stimuli such as photochemical reaction excitation light, electrochemical reaction voltage, and pulse supply of reactants can be input, time-resolved measurements similar to those in the third embodiment become possible. For example, in the measurement system of Figure 14, the microchannel 107 can be irradiated with pump light for the photochemical reaction from the outside, or an electrode for the electrochemical reaction can be formed inside the microchannel 107 and electrical stimulation can be applied. Multiple microchannels 107 can be used to initiate mixing reactions by their merging or reactions at layer interfaces. By starting a chemical reaction with stimulation to the sample S and controlling the delay time Δt, which is the timing difference between the reaction stimulus and the pulse light output of the nanocarbon light source 10, high-speed time-resolved measurements can be performed.

[0082] Figure 15 is a schematic diagram of a microanalysis chip 120 in which a nanocarbon light source 10 and a detector are integrated on a substrate. A spectrometer / photodetector 110 and an optical filter 106 such as a bandpass filter may be further integrated into the microanalysis chip 120 having the nanocarbon light source 10. This integrated configuration realizes a fully on-chip type microanalysis chip 120 in which all optical components are integrated on the chip without the use of an external spectrometer or photodetector.

[0083] In the example shown in Figure 15, a microchannel 107 is formed on top of the nanocarbon light source 10 in the stacking direction, and a spectrometer / photodetector 110 is placed further above the microchannel 107. This allows for direct measurement of the reaction (infrared absorption, etc.) between the infrared light from the nanocarbon light source 10 and the sample in the microchannel 107. A microanalysis chip 120 having a microchannel 107 is also an example of an infrared analysis chip.

[0084] A microchannel reactor 123 may be constructed by branching the microchannel 107 and providing supply nozzles 125-129 in the branched channels. For example, fluid A may be supplied from supply nozzles 125 and 128, fluid B from supply nozzles 126 and 129, and fluid C from supply nozzle 127. The confluence of the channels causes the mixed fluid to flow over the nanocarbon light source 10.

[0085] By forming the optical filter 106 on the upper or lower part of the microchannel 107, it is possible to detect and analyze only specific wavelengths, perform sensing, etc. In this analysis and sensing, a single-element photodetector can be used as the spectrometer / photodetector 110, but an array of photodetectors may also be used. In this case, by arranging optical filters with different central wavelengths in an array, spectroscopic measurements can also be performed on the chip.

[0086] The nanocarbon light source 10 is very small and highly integrated, making it easy to form an array. When the nanocarbon light source 10 is arranged in an array, spectroscopy can be performed even if the spectrometer / photodetector 110 is a single element. For example, optical filters 106 with different central wavelengths may be arranged in an array facing the array of nanocarbon light sources 10. By controlling the lighting timing of each nanocarbon light source 10 arranged in the array, spectroscopy can be performed with a single-element spectrometer / photodetector 110.

[0087] The time-resolved measurement method using chemical reaction pulse stimulation in the third embodiment (Figures 10-12) can also be applied to the micro-analysis chip 120 shown in Figure 15. In this case, a highly integrated time-resolved measurement chip is realized.

[0088] <Fifth Embodiment> Figure 16 is a diagram illustrating the principle of infrared analysis in the fifth embodiment. The fifth embodiment provides an infrared analysis technique using a biochip in which a probe material is immobilized on a minute infrared light source such as a nanocarbon light source 10. The biochip used here is also an example of an infrared analysis chip. A sample for analysis is supplied onto the biochip, and the sample material is bound to the probe material immobilized on the minute infrared light source, allowing for simple and rapid infrared analysis.

[0089] Currently, one application of semiconductor microfabrication technology to the bio-field is the biochip. In a biochip, one or more immobilized probes (DNA, proteins, glycans, cells, molecules, etc.) are placed on the surface of a substrate such as a semiconductor or insulator. The immobilized probes may be arranged in a one-dimensional or two-dimensional array. Analysis is performed by utilizing the property that sample substances (DNA, proteins, glycans, cells, molecules, etc.) selectively bind to the immobilized probes on the substrate.

[0090] In typical biochip-based analysis, a "phosphor" is attached to a fragment of the sample substance, and the fluorescence pattern is analyzed to detect and analyze the sample substance. However, phosphors are extremely expensive, and the analytical equipment itself is large, making this a very costly analytical method.

[0091] In the fifth embodiment, minute infrared light sources (e.g., nanocarbon light sources) are arranged individually or in a one-dimensional or two-dimensional array on the substrate surface, and a fixed probe is placed on these minute infrared light sources. The analytical sample substance selectively bound to the fixed probe is identified, detected, and analyzed using infrared absorption of light emitted from the minute infrared light sources.

[0092] In Figure 16, a biochip 130 with an integrated light source is fabricated by placing an analytical fixed probe 131 on a minute infrared light source, such as a nanocarbon light source 10, formed on a substrate 11. The fixed probe 131 can be DNA, proteins, glycans, cells, molecules, etc. The fixed probe 131 selectively binds to specific sample substances (DNA, proteins, glycans, cells, molecules, etc.). The fixed probe 131 can be formed by directly binding to the nanocarbon light source 10 that constitutes the minute infrared light source, or a cap layer may be provided on the nanocarbon light source 10 and the fixed probe bound to the cap layer.

[0093] When a sample for analysis is introduced into a miniature infrared light source equipped with a fixed probe 131, the sample substance 135, which can selectively bind to the fixed probe 131, binds to the fixed probe 131. Because the binding between the fixed probe 131 and the sample substance 135 is selective, the fixed probe 131 can be selected so that only a specific sample substance 135 binds to the fixed probe 131. This property can be used to identify, detect, and analyze (such as determining the molecular structure) the sample substance for analysis.

[0094] After introducing the analytical sample, irradiating it with light from a micro-infrared light source causes infrared absorption in the analytical sample and any marker molecules modified on the analytical sample directly above the micro-infrared light source. By measuring the spectrum or transmittance of the infrared light transmitted through the analytical sample trapped on the micro-infrared light source, the analytical sample can be identified, detected, or analyzed based on infrared absorption due to molecular vibrations within the sample.

[0095] The method of the fifth embodiment eliminates the need for fluorescent markers required in conventional biochip analysis. In this embodiment, instead of expensive fluorescent markers, the sample substance 135 itself, or molecules modified from the sample substance 135, serve as the marker, utilizing infrared absorption such as molecular vibrations. Since it uses infrared absorption by molecules instead of fluorescent markers that emit light in the visible region, non-luminescent molecules that could not be used as markers in conventional methods can also be used as markers for biochip analysis, enabling low-cost biochip analysis.

[0096] The micro-light source may be a compound semiconductor light-emitting element operating in the infrared region or an organic light-emitting element. When the nanocarbon light source 10 is used as the micro-light source, it can also emit light in the visible light region, so a biochip 130 that utilizes visible light absorption can also be developed. Furthermore, it is possible to perform conventional analysis using phosphors by using visible light from the nanocarbon light source 10 as excitation light.

[0097] Figure 17 is a schematic diagram of an infrared light source array 140 applied to the biochip 130 of the embodiment. Biochip analysis in Figure 16 can be performed at a faster speed and with a larger volume of data by arranging minute infrared light sources in a one-dimensional or two-dimensional array. In Figure 17, a large number of nanocarbon light sources 10 are arranged in a two-dimensional array on a substrate 141. When using nanocarbon light sources 10, the infrared light source array 140 can be obtained inexpensively and easily because each light source is small yet easy to fabricate.

[0098] Since each of the nanocarbon light sources 10 has a high-speed light emission response, the nanocarbon light sources 10 arranged in an array can be independently and rapidly controlled to light up at different timings.

[0099] Figure 18A shows an infrared light source array 140A using matrix electrodes as a modified example. Figure 18B is a circuit diagram of an infrared light source array with a rectifying effect. In Figure 18A, multiple electrodes 142 extending horizontally and multiple electrodes 143 extending vertically are electrically insulated from each other and arranged to intersect. The horizontal electrodes 142 have comb-shaped electrode protrusions 142t. Each electrode protrusion 142t faces a vertical electrode 143 to form an electrode pair. Carbon nanomaterials are connected to each electrode pair to constitute a cell of one nanocarbon light source 10.

[0100] As shown in Figure 18B, a rectifying effect may be applied to each cell. In this case, for example, a rectifying element (e.g., a diode) 145 is connected in series with the resistive nanocarbon light source 10. The element 145 suppresses the path caused by reverse current flow, making it easier to emit light only from the nanocarbon light source 10 at the desired location.

[0101] For example, a high potential is applied to the selected horizontal electrode 142, and the other electrodes 142 are turned OFF. A low potential is applied to the selected vertical electrode 143, and the other electrodes 143 are turned OFF. The nanocarbon light source 10 at the position determined by the selected electrodes 142 and 143 emits light. In this configuration, the current that would otherwise bypass the light source is suppressed, thereby increasing the luminescence efficiency and suppressing malfunctions (false light emission) of other light sources.

[0102] Figure 19 is a schematic diagram of an infrared analyzer 160 according to the fifth embodiment. The infrared analyzer 160 has an infrared light source array 140 (or 140A), an integrated biochip 150, and a spectrometer / photodetector 110. The biochip 150 is also an example of an infrared analyzer chip. A focusing lens 151 may be placed between the biochip 150 and the spectrometer / photodetector 110.

[0103] In the infrared light source array 140 (or 140A) of the biochip 150, as shown in Figure 17 or Figure 18, a fixed probe 131 is formed on each of the nanocarbon light sources 10 arranged in a one-dimensional or two-dimensional array, as shown in Figure 16. When the sample substance 135 to be analyzed binds to the fixed probe 131, the infrared light 155 from the nanocarbon light source 10 is absorbed, enabling analysis based on infrared absorption. As shown in Figure 19, even when using a single spectrometer / photodetector 110, two-dimensional chip analysis is possible by controlling the emission timing of each nanocarbon light source 10 and synchronizing it with the detection timing. For example, as shown by the arrow in Figure 19, by sequentially scanning and lighting the arrayed nanocarbon light sources 10, information from each cell can be obtained with the spectrometer / photodetector 110.

[0104] Multiple types of fixed probes 131 necessary for analysis may be formed on each nanocarbon light source 10 of the biochip 150. In this case, different types of sample substances 135 can be simultaneously detected and analyzed corresponding to each of the different types of fixed probes 131. The analytical sample substance to be analyzed is introduced onto the biochip 150 and brought into contact with multiple types of fixed probes 131. Depending on the degree of binding affinity between the type of fixed probe 131 and the sample substance 135, the sample substance 135 will bind to one type of fixed probe 131, but not to another type of fixed probe 131.

[0105] In this state, the arranged nanocarbon light sources 10 are made to emit light sequentially, and infrared light 155 is detected by the spectrometer / photodetector 110 in synchronization with the light emission, thereby detecting whether or not a sample substance 135 is bound to a specific fixed probe 131.

[0106] As explained with reference to Figure 16, the sample substance 135 itself, or molecules modified from the sample substance 135, exhibit infrared absorption due to molecular vibrations, etc. By measuring the transmittance or spectrum of infrared light 155 transmitted through the sample substance 135 bound to a fixed probe 131 on the nanocarbon light source 10, the sample substance 135 can be identified, detected, and analyzed. Expensive phosphor markers are not required, and non-luminescent molecules that could not be used as markers in conventional methods can also be used as markers for biochip analysis.

[0107] Because the nanocarbon light sources 10 are arranged in an array, analyses using various types of fixed probes 131 can be performed simultaneously on the same biochip 150. The biochip 150 is inexpensive and enables high-speed and high-capacity analysis. In this biochip analysis, by using the nanocarbon light sources 10 as infrared light sources, very small light sources can be arranged in a one-dimensional or two-dimensional array. Furthermore, because the nanocarbon light sources 10 have a very fast emission response, each nanocarbon light source 10 can be individually and rapidly controlled to light up at different timings.

[0108] In biochip analysis using one-dimensional or two-dimensional arrangements, various types of fixed probes 131 can be patterned in any arrangement. The resulting infrared absorption and infrared spectral arrangement patterns reflect the molecular structure and properties of the substance in the biochip analysis. By analyzing the one-dimensional and two-dimensional patterns obtained from the measurements, highly efficient detection and analysis become possible.

[0109] Current biochips using fluorescent markers and two-dimensional sequences require capturing the expression pattern as a pattern image using a two-dimensional detector array such as an image sensor. For example, in the case of a DNA chip, the expression pattern reflecting the DNA base sequence is captured as a light image using a two-dimensional detector array such as an image sensor.

[0110] In contrast, in the infrared analyzer 160 of this embodiment, the infrared light source side using nanocarbon light sources 10 is a two-dimensional array, and each nanocarbon light source 10 can be independently controlled to light up. By sequentially emitting light from the arranged nanocarbon light sources 10, a single-channel spectrometer / photodetector 110 can be used. The configuration of the infrared analyzer 160 is simplified, and the device can be constructed at a low cost.

[0111] In infrared photodetectors, there are no high-performance two-dimensional detectors compared to visible light detectors. High-performance infrared detectors are single-channel detectors, and the method of this embodiment makes it possible to use a high-performance single-channel photodetector. By controlling the emission timing of the nanocarbon light source 10, spectroscopy becomes easier, and biochip analysis using spectroscopy also becomes possible. Furthermore, since the nanocarbon light source 10 can emit light even in visible light, it is possible to develop biochips that utilize conventional phosphor analysis or visible light absorption.

[0112] This biochip analysis technology can also be combined with the configurations and methods of the first to fourth embodiments.

[0113] <Sixth Embodiment> Figure 20 shows the application of the sixth embodiment to an imaging device. In the sixth embodiment, an array of fine infrared light-emitting elements, such as a nanocarbon light source 10, is applied to infrared imaging. The infrared imaging device has an infrared light source array 140 in which multiple infrared light-emitting elements are arranged, and a spectrometer / photodetector 110 (see Figure 19, etc.) positioned opposite the infrared light source array 140, making it possible to place a sample directly on the surface of the infrared light source array 140.

[0114] A nanocarbon light source 10 may be used as the infrared light-emitting element. Unlike conventional infrared light sources such as halogen lamps, the nanocarbon light source 10 can be integrated into an array on various substrate materials, including silicon, glass, semiconductors, insulators, and polymer substrates, and each light source element can be lit independently.

[0115] By placing the sample S to be observed on a one-dimensional or two-dimensional infrared light source array 140, imaging becomes possible using a single spectrometer / photodetector 110. The sample S includes bio-samples, biological samples, organic materials, inorganic materials, etc.

[0116] Generally, it is difficult to create low-noise, high-sensitivity array detectors for infrared photodetectors, which hinders the practical application of infrared imaging. In this invention, since the light-emitting element side, rather than the detector side, is in an array configuration, a high-performance (high-sensitivity, high-speed) detector composed of a "single element" can be used as the detector.

[0117] By synchronizing the timing of the illumination of each light-emitting element in the infrared light source array 140, such as the nanocarbon light source 10, with the detection timing of the spectrometer and photodetector, imaging of the infrared absorption rate and spectrum on each light source can be performed at high speed. Furthermore, since only a single detector is required, wavelength selection in combination with a spectrometer and filter is easy, and spectral imaging that images each wavelength can be easily realized.

[0118] This infrared imaging can be achieved by utilizing the "high-speed light source" and "miniature light source" characteristics of the nanocarbon light source 10, and is a completely new imaging method that cannot be achieved with conventional infrared analysis techniques using halogen lamps or ceramic light sources. In addition to the nanocarbon light source 10, infrared imaging may also be performed using elements that enable high-speed response and miniaturization, such as semiconductor light-emitting elements and organic light-emitting elements.

[0119] <Seventh Embodiment> Figure 21 is a schematic diagram of the nanocarbon light source 10A of the seventh embodiment. The nanocarbon light source 10A has a nanocarbon material 15 that extends elongated in a predetermined direction between a pair of electrodes 12a and 12b, and a gate electrode 19. The nanocarbon material 15 that extends elongated in the predetermined direction is, for example, one or more layers of graphene. Graphene may be grown directly on the substrate 11 by CVD or the like, or it may be formed by a transfer method or the like.

[0120] The gate electrode 19 can be a metal electrode such as a metal material, or the conductive substrate itself, such as doped silicon, can be used as the electrode. The gate electrode 19 may be formed, for example, on the back surface of the substrate 11 (the side opposite to the nanocarbon material 15) using a conductive transparent material. The gate electrode may be an electrode widely formed on the bottom of the substrate, or it may be a gate electrode formed locally only directly beneath the graphene. The substrate 11 on the gate electrode can be an insulator, and may be an insulating substrate or an insulating thin film material such as a silicon oxide thin film on silicon. By applying a voltage to the gate electrode 19, the carrier concentration in the nanocarbon material 15 can be spatially controlled, and for example, a hot spot 109 that emits bright light where the carrier concentration is low can be formed. The light emitted from the hot spot 109 is shown as "L" in the figure. emit This is indicated by "[...]."

[0121] By changing the voltage applied to the gate electrode, the position of the hot spot 109 along the length of the nanocarbon material 15 can be continuously changed. This makes it possible to fabricate a nanocarbon light source 10A in which the light emission position can be swept along the length of the nanocarbon material 15 by the gate voltage.

[0122] This configuration allows for spatial resolution in one dimension using a single nanocarbon light source 10A element. This light source can be used as a light source for one-dimensional imaging devices.

[0123] Figure 22 shows an infrared light source array 170 in which multiple nanocarbon light sources 10A from Figure 21 are arranged in a direction perpendicular to the sweep direction. By combining this infrared light source array 170 with a spectrometer / photodetector 110 and a gate voltage controller, a two-dimensional imaging device can be realized.

[0124] A sample S can be directly mounted on the surface of the infrared light source array 170. A single common gate electrode 19 may be formed on the back surface of the substrate 11, or a striped gate electrode 19 may be provided for each corresponding nanocarbon light source 10A. When a common gate electrode 19 is used, the hot spot 109 can be swept along the length of the nanocarbon material 15 by sequentially selecting a pair of electrodes 12a and 12b and changing the gate voltage for each selected nanocarbon light source 10A. When individual striped gate electrode 19s are used, the hot spot 109 can be swept simultaneously with multiple nanocarbon light sources 10A. In this case, high-speed imaging becomes possible.

[0125] While a single nanocarbon light source 10A may have limitations in terms of the length of the nanocarbon material 15 or the sweep distance of the hotspot 109, arranging the nanocarbon light sources 10A in a two-dimensional plane enables wide-area and high-speed imaging.

[0126] In Figure 22, the nanocarbon light sources 10A are arranged only in the vertical direction of the paper. However, for example, multiple nanocarbon light sources 10 may also be arranged in the horizontal direction (horizontal direction) of the paper via an insulating layer to form a two-dimensional matrix-like light source array.

[0127] Figure 23 is a schematic diagram of the imaging device 180 of the seventh embodiment. The imaging device 180 includes an infrared light source array 170, a voltage control unit 210 that controls the voltage applied to the infrared light source array 170, and infrared light (L) transmitted through the sample S. emit It has a spectrometer / photodetector 110 that detects ).

[0128] A focusing lens 151 may be placed between the infrared light source array 170 and the spectrometer / photodetector 110. An information processing device 103 (see Figure 10) including a display device may be connected to the output of the spectrometer / photodetector 110.

[0129] The voltage control unit 210 controls the voltage level applied to the gate electrode 19. Alternatively, it may sequentially select multiple nanocarbon light sources 10A and control the on / off state of the voltage applied between a pair of electrodes 12a and 12b.

[0130] By saving the output results of the spectrometer / photodetector 110 for each sweep of each nanocarbon light source 10A in the infrared light source array 170 to the information processing device 103 or external memory, sample information for one line (such as light absorption rate and spectral changes) can be obtained. By sweeping the hot spots for all nanocarbon light sources 10A, a two-dimensional distribution of the internal information of the sample S can be obtained.

[0131] <Effects of infrared analysis in the embodiment> The infrared spectroscopy of this invention uses a tiny infrared light source, such as the nanocarbon light source 10. When carbon nanotubes are used as the light-emitting material, the light source element size can be miniaturized to 1 nm square, and when graphene is used, it can be miniaturized to 100 nm square. The laser light sources used in conventional scanning near-field optical microscopes (SNOMs) are at least about 10 cm square in size. Halogen lamps and ceramic light sources used in FT-IR are also about 1 cm square in size.

[0132] In this invention, because a minute infrared light source element is used, integration (chip-based) and array-based design are possible. However, light sources used in FT-IR and SNOM cannot be integrated or chip-based. Furthermore, in this invention, high sensitivity through modulation, analysis chip-based design, and high-speed imaging using a two-dimensional array light source are possible, but these effects cannot be obtained with either SNOM or FT-IR.

[0133] Regarding the wavelength range, the infrared analysis of this invention measures over a wide wavelength range of 1 to 10 μm. FT-IR also measures over a similar wavelength range, but SNOM is limited to a single wavelength or a narrow wavelength range of the laser.

[0134] In the infrared analysis method of this invention, a high spatial resolution of 1 nm to 100 nm is achieved. While SNOM also has a high spatial resolution of 10 nm, FT-IR has a resolution of 10 μm.

[0135] While the infrared analysis method of this invention allows for high-speed time-resolved measurements of 100 ps, ​​typical FT-IR is slow at 100 ms. Time-resolved measurements are usually difficult with SNOM.

[0136] Thus, the present invention offers high spatial and temporal resolution with a minute light source size, enabling integration, high sensitivity through modulation, integration into an analysis chip, and high-speed imaging.

[0137] <Other variations> Although the structure and method of the invention have been described above based on specific embodiments, the present invention is not limited to the specific examples described above. The first to seventh embodiments may be combined with each other. For example, the biochip 130 and / or 150 of the fifth embodiment and the infrared imaging of the sixth embodiment can both be realized with a two-dimensional infrared array light source, so infrared imaging using the biochip 130 or 150 is possible. While nanocarbon light sources are one of the ideal candidates for a two-dimensionally arranged infrared light source array, any minute infrared light source can be used as long as an infrared light source array in which minute infrared light source elements are arranged in a two-dimensional array can be realized.

[0138] Currently, biochips such as DNA chips utilize visible light and fluorescent markers, but these methods are costly due to the use of expensive fluorescent markers and cameras with two-dimensional image sensors. As in the fifth and sixth embodiments, by using a two-dimensional array of light-emitting elements instead of fluorescent markers, biochip analysis such as DNA analysis can be performed with a single-channel photodetector without the need for a two-dimensional image sensor, by successively changing the light-emitting points of the light-emitting elements. As in the seventh embodiment, by sweeping the hotspot, spatial resolution in one dimension can be achieved with a single infrared light source. By arranging multiple infrared light sources capable of sweeping the hotspot in a direction perpendicular to the sweep direction, wide-area imaging becomes possible.

[0139] By controlling the light emission timing and sweep timing of light-emitting elements, it becomes possible to use spectroscopy in conjunction with biochip analysis. For example, in the analysis of two-dimensional DNA patterns, the addition of spectroscopy allows for more advanced analysis of DNA expression patterns, resulting in more detailed DNA analysis.

[0140] The biochip analysis and infrared light source array of this embodiment may be combined with conventional analysis using phosphors. In this case, it can also be applied to the analysis of fluorescent markers using light from a two-dimensionally arranged light-emitting element, or to biochip analysis using light absorption in the visible light region.

[0141] When using the nanocarbon light source 10 or 10A of the embodiment as a two-dimensionally arranged light-emitting element, biochip analysis (such as DNA analysis) can be performed based on infrared absorption patterns utilizing infrared absorption due to molecular vibrations, instead of conventional biochip analysis (such as DNA analysis) using two-dimensional fluorescence pattern images obtained with fluorescent markers. This enables sample analysis without the need for fluorescent markers, allowing analysis of the sample substance itself, which does not exhibit fluorescence, or molecules modified on the sample substance, by infrared absorption, thereby realizing inexpensive biochip and DNA analysis.

[0142] Although not shown in the diagram, the output of the spectrometer / photodetector 110 used in the infrared analyzer of the fourth and fifth embodiments may be supplied to an information processing device 103 (see Figure 10) that performs signal processing or image processing. Alternatively, the output of a single detector used in infrared imaging of the sixth embodiment may be input to the information processing device 103. In any case, high-speed, high-sensitivity infrared analysis is achieved. [Explanation of Symbols]

[0143] 10,10A Nanocarbon Light Source 11, 11A, 121, 141 circuit boards 12a, 12b electrode 15 Nanocarbon Materials 16 Protective film 20 Probe-type light sources 22 stages 100, 100A~100C, 160 Infrared analyzer 102 Near-field light 103 Information Processing Device 105 Excitation source 106 Optical Filters 107 Microfluidic 108,120 micro-analysis chips (infrared analysis chips) 110, 110-1, 110-2 Spectrometer / Photodetector (Detection means) 123 Microfluidic Reactors 130, 150 Biochip (Infrared Analysis Chip) 131 Fixed probe 140, 140A, 170 Infrared Light Source Array 180 Imaging Devices S Sample

Claims

1. A light source substrate in which multiple light-emitting elements that emit infrared light with intensity modulated at a speed of 160 Hz or higher are arranged in an array.

2. A light source substrate according to claim 1, An infrared detector is positioned opposite the light source substrate, It has, The surface of the light source substrate is capable of mounting a sample. The infrared detector is an infrared imaging device that operates in synchronization with the emission timing of the intensity-modulated infrared light from the plurality of light-emitting elements.

3. The infrared imaging device according to claim 2, wherein one of the infrared detectors detects the infrared light emitted by at least two of the plurality of light-emitting elements that has been transmitted through or reflected by the sample.

4. A light source substrate according to claim 1, A probe material is fixed on the surface of the light source substrate at positions corresponding to the plurality of light-emitting elements and selectively binds to a specific substance, An infrared analysis chip.

5. The infrared analysis chip according to claim 4, wherein different types of probe materials are provided corresponding to the plurality of light-emitting elements.

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