WO2010073770A1 - 気体モニタリング装置、燃焼状態モニタリング装置、経年変化モニタリング装置、および不純物濃度モニタリング装置 - Google Patents

気体モニタリング装置、燃焼状態モニタリング装置、経年変化モニタリング装置、および不純物濃度モニタリング装置 Download PDF

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WO2010073770A1
WO2010073770A1 PCT/JP2009/063581 JP2009063581W WO2010073770A1 WO 2010073770 A1 WO2010073770 A1 WO 2010073770A1 JP 2009063581 W JP2009063581 W JP 2009063581W WO 2010073770 A1 WO2010073770 A1 WO 2010073770A1
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light receiving
monitoring device
gas
light
layer
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French (fr)
Japanese (ja)
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博史 稲田
永井　陽一
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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Priority to US13/142,039 priority Critical patent/US8624189B2/en
Priority to CN200980152617.2A priority patent/CN102265138B/zh
Priority to EP09834576.2A priority patent/EP2372342A4/en
Publication of WO2010073770A1 publication Critical patent/WO2010073770A1/ja
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
    • G01J5/60—Radiation pyrometry, e.g. infrared or optical thermometry using determination of colour temperature
    • G01J5/602—Radiation pyrometry, e.g. infrared or optical thermometry using determination of colour temperature using selective, monochromatic or bandpass filtering
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
    • G01J5/0044—Furnaces, ovens, kilns
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F30/00—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors
    • H10F30/20—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors
    • H10F30/21—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to infrared, visible or ultraviolet radiation
    • H10F30/22—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to infrared, visible or ultraviolet radiation the devices having only one potential barrier, e.g. photodiodes
    • H10F30/221—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to infrared, visible or ultraviolet radiation the devices having only one potential barrier, e.g. photodiodes the potential barrier being a PN homojunction
    • H10F30/2215—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to infrared, visible or ultraviolet radiation the devices having only one potential barrier, e.g. photodiodes the potential barrier being a PN homojunction the devices comprising active layers made of only Group III-V materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/14—Shape of semiconductor bodies; Shapes, relative sizes or dispositions of semiconductor regions within semiconductor bodies
    • H10F77/143—Shape of semiconductor bodies; Shapes, relative sizes or dispositions of semiconductor regions within semiconductor bodies comprising quantum structures
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
    • G01J2005/0077—Imaging
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
    • G01N2021/3531—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis without instrumental source, i.e. radiometric
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/08—Optical fibres; light guides
    • G01N2201/0833—Fibre array at detector, resolving
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/08—Optical fibres; light guides
    • G01N2201/0846—Fibre interface with sample, e.g. for spatial resolution

Definitions

  • the present invention uses a semiconductor light receiving element having light receiving sensitivity to light including the near-infrared region, and uses gas components in gases (such as gas components and soot) in industrial facilities and infrastructure facilities such as waste incinerators.
  • the present invention relates to a gas monitoring device, a combustion state monitoring device, a secular change monitoring device, and an impurity concentration monitoring device.
  • the sensors are roughly classified into an electron tube type and a solid state photodiode (PD) in the near infrared region.
  • PD solid state photodiode
  • the present invention is directed to a detection apparatus for a biological component using PD.
  • the following PDs or PD arrays are used.
  • Examples of such photodiodes include germanium (Ge) -based PD, lead sulfide (PbS) -based PD, HgCdTe-based PD, or a one-dimensional array and a two-dimensional array thereof.
  • An InP-based PD having a light receiving sensitivity at a wavelength of 1.7 ⁇ m or less in the near infrared region, an InGaAs-based PD falling within the category of the InP-based PD, or an array thereof.
  • the InP-based PD refers to a PD including a light-receiving layer of a III-V compound semiconductor formed on an InP substrate, and includes an InGaAs-based PD.
  • (1) is often cooled to suppress noise, and for example, it is often operated by cooling with a liquid nitrogen temperature (77 K) or a Peltier element. For this reason, the apparatus becomes large and the apparatus cost increases. Although it can be used even at room temperature, it has a problem that the dark current is large and the detection ability is inferior in the wavelength range of 2.5 ⁇ m or less.
  • the problems of InP-based PD are (I) InGaAs lattice-matched to InP has a low dark current, but the light receiving sensitivity is limited to a wavelength region of 1.7 ⁇ m or less in the near infrared region, and ( II) In extended-InGaAs in which the wavelength range where light can be received is expanded to 2.6 ⁇ m, the dark current needs to be greatly cooled. Therefore, in InP-based PD, light of 2.0 ⁇ m or more, which is important for improving accuracy in gas monitoring, cannot be used or needs to be cooled when used.
  • Patent Documents 1 and 2 propose an apparatus for detecting the concentration of hydrogen that does not have an absorption spectrum in the infrared region, particularly due to hydrocarbon gas and diatomic molecules.
  • a light receiving element having sensitivity in a wavelength band of 1.5 to 1.6 ⁇ m is used.
  • an optical monitoring device for monitoring the combustion state has been proposed in order to suppress the generation of nitrogen oxides, soot and carbon monoxide in a combustion device such as a boiler (Patent Document 3).
  • a multi-layer light receiving element in which a silicon photodiode and a PbS photoconductive element are stacked is used.
  • a multilayer light receiving element of a combination of a silicon photodiode and a Ge photodiode or a combination of a silicon photodiode and a PbSe photoconductive element has also been proposed.
  • the silicon photodiode is used in order to receive light having a wavelength in the visible light range or a wavelength close thereto.
  • Patent Document 4 an infrared camera that captures the temperature distribution of the entire combustion furnace in a waste incinerator has been proposed (Patent Document 4).
  • the contents of the light receiving part of this infrared camera are unknown.
  • high-purity gases are used for forming an epitaxial film, but these gases contain a very small amount of moisture, which adversely affects the durability of the LSI or the like.
  • Using such a laser light source that oscillates a single wavelength in the near-infrared region for monitoring trace moisture in a gas the light transmitted through the gas is received, and a moisture concentration on the order of 0.1 to 1 ppm by lock-in detection.
  • Non-Patent Document 2 has been proposed (Non-Patent Document 2).
  • a germanium photodiode is used as the light receiving element of this device.
  • a single element or an array type such as InGaAs, PbS, Ge, HgCdTe, extended-InGaAs having a multi-step buffer layer is used. It is used.
  • the light receiving wavelength range is 1 ⁇ m to 1.8 ⁇ m, which is common to all the gas monitoring devices. However, it is recognized that the upper limit is about 2.0 ⁇ m or 2.5 ⁇ m.
  • InGaAs has a problem of increasing the light receiving sensitivity to the near-infrared long wavelength side.
  • the following measures have been proposed.
  • K1 The In composition of the InGaAs light receiving layer is increased, and the lattice mismatch with the InP substrate is absorbed by the step buffer layer inserted between them and the In composition changed stepwise (Patent Document 5).
  • K2) N is contained in the InGaAs light receiving layer to form a GaInNAs light receiving layer (Patent Document 6). Lattice matching with the InP substrate is satisfied by containing a large amount of N.
  • Non-patent Document 3 The wavelength of the light receiving region is increased by a type II multiple quantum well structure of GaAsSb and InGaAs. The lattice matching with the InP substrate is satisfied.
  • K4 Two-dimensional arraying is realized by forming wet etching of element isolation grooves between light receiving elements (pixels) (Patent Document 7). Masao Nakayama “Technology Trends of Infrared Detectors” Sensor Technology, March 1989 (Vol.9, No.3), p.61-64 Naohisa Wu et al. “Detection of trace amount of moisture in gas by semiconductor laser spectroscopy” Journal of Infrared Radiological Society of Japan, Vol.11, p.33-40 (2001) R.
  • a device using near infrared light up to 2500 nm at maximum is shown. If the light receiving sensitivity is good, it is preferable that the upper limit of the wavelength is large because more information can be obtained. However, in order to receive light exceeding a wavelength of 1.7 ⁇ m, as described above, a light receiving element using PbS, HgCdTe, or the like has a problem that the dark current is large, the detection capability is low, and the detection resolution is increased. Moreover, if it cools and uses in order to improve detection capability, a gas monitoring apparatus will become large.
  • An InGaAs light receiving element lattice-matched to an InP substrate is excellent in detection capability, but has a sensitivity of 1.7 ⁇ m or less in wavelength, and is unsuitable for detecting a gas component having a large absorption spectrum in a longer wavelength region.
  • one detection target gas component should be comprehensively detected using two or more absorption bands due to the gas component. Is desirable to improve resolution.
  • the sensitivity wavelength range of 1.7 ⁇ m or less is extremely insufficient.
  • K2 It is very difficult to obtain GaInNAs having a good crystal when N is set to about 10 at% in order to make the band gap longer wavelength while lattice matching with InP. Further, it is almost impossible to obtain GaInNAs with a thickness of about 2 ⁇ m in order to sufficiently increase the light receiving sensitivity. In short, a clear image cannot be obtained.
  • the present invention relates to a gas monitoring device capable of performing gas monitoring with high sensitivity using an InP-based photodiode that reduces dark current without a cooling mechanism and expands the light receiving sensitivity to a wavelength of 1.8 ⁇ m or more.
  • An object of the present invention is to provide a combustion state monitoring device, a secular change monitoring device, and an impurity concentration monitoring device using the above.
  • the gas monitoring device of the present invention is a device for monitoring gas using light in the near infrared region having a wavelength range of 3 ⁇ m or less.
  • This gas monitoring apparatus includes a light receiving element that receives light in the near infrared region, and the light receiving element has a light receiving layer having a multiple quantum well structure formed on an InP substrate.
  • a band gap wavelength of the light receiving layer is 1.8 ⁇ m or more and 3 ⁇ m or less, and a diffusion concentration distribution adjusting layer is provided on the opposite side of the light receiving layer from the InP substrate.
  • the band gap of the diffusion concentration distribution adjusting layer is smaller than InP, and in the light receiving element, a pn junction is formed by selective diffusion of the impurity element that reaches the light receiving layer through the diffusion concentration distribution adjusting layer.
  • the concentration of the impurity element in the light receiving layer is 5 ⁇ 10 16 / cm 3 or less.
  • the multiple quantum well structure having a band gap energy corresponding to the near-infrared region is not destroyed by reducing the impurity concentration to 5 ⁇ 10 16 cm ⁇ 3 or less, that is, the crystallinity Can be formed without impairing.
  • the impurities for forming the pn junction of the light receiving element are selectively diffused, that is, are introduced so as to be limited to the periphery in a planar manner from the periphery to be separated into individual light receiving elements. For this reason, it is easy to form each light receiving element with high accuracy, and it is not necessary to provide an element isolation groove, so that a light receiving element with a low dark current can be formed.
  • the gas monitoring device can detect these absorption bands simultaneously. Thereby, the detection accuracy can be improved.
  • the electrical resistance can be kept low even if the impurity concentration in the thickness range on the light receiving layer side of the diffusion concentration distribution adjustment layer is lowered. It can contribute to prevention of the decrease in the temperature. More specifically, the reason why the band gap of the diffusion concentration distribution adjusting layer is made smaller than the band gap of the InP substrate is as follows. (1) When a near-infrared light-receiving layer is formed of a group III-V compound semiconductor, a band gap energy larger than the band gap energy of the light-receiving layer may be used for the window layer. In view of this, the same material as the semiconductor substrate is often used.
  • the band gap energy of the diffusion concentration distribution adjusting layer is smaller than the band gap energy of the window layer and larger than the band gap energy of the light receiving layer. If the band gap energy of the light receiving layer is smaller, the diffusion concentration distribution adjusting layer absorbs the target light and reduces the light receiving sensitivity of the light receiving layer when the structure having the epitaxial layer surface as the incident surface is adopted. is there. (2) By using a material having a smaller band gap energy than a material having a large band gap energy normally used for the window layer, even if the impurity concentration is lowered, the degree of increase in electric resistance or the degree of decrease in electric conductivity is reduced. Can be small. As a result, it is possible to suppress a decrease in response speed in the voltage application state as described above.
  • detection refers to preparing a calibration curve of a predetermined component (relationship between the concentration of the predetermined component and the intensity or absorbance of light at that wavelength) in advance, and obtaining the concentration or content rate of the predetermined component. It is also possible to use a method that does not use such a calibration curve.
  • the above pn junction should be interpreted broadly as follows.
  • an impurity region referred to as an i region
  • the impurity introduced by diffusion It also includes a bond formed between the region and the i region. That is, the pn junction may be a pi junction or an ni junction, and further includes a case where the p concentration or the n concentration in the pi junction or ni junction is very low.
  • the concentration of the impurity element decreases from a high concentration of about 1 ⁇ 10 18 / cm 3 or more on the side opposite to the light receiving layer to 5 ⁇ 10 16 / cm 3 or less on the light receiving layer side. Distribution can be taken. As a result, it is possible to ensure good crystallinity of the multiple quantum well structure while suppressing the interface resistance of the electrode located on the top side of the surface or enabling ohmic contact.
  • the problem of an increase in electrical resistance or a decrease in electrical conductivity due to a low impurity concentration in the portion in the diffusion concentration distribution adjusting layer is that the band gap energy of the diffusion concentration distribution adjusting layer is set to be higher than that corresponding to InP. It can be reduced by making it smaller.
  • the above light-receiving layer can have a type II quantum well structure.
  • a transition from a high valence band layer to a low conductive band layer is possible, and it is easy to obtain light receiving sensitivity to light in a longer wavelength region.
  • the above light-receiving layer may have a (Quantum Well structure of (InGaAs / GaAsSb) or (GaInNAs (P, Sb) / GaAsSb).
  • (GaInNAs (P, Sb) / GaAsSb) means (GaInNAsP / GaAsSb), (GaInNAsSb / GaAsSb), (GaInNAsPSb / GaAsSb), or (GaInNAs / GaAsSb).
  • the above-mentioned InP substrate can be an off-angle substrate inclined from 5 ° to 20 ° in the [111] direction or the [11-1] direction from (100).
  • a stacked body including a light-receiving layer having a multiple quantum well structure with a small defect density and excellent crystallinity As a result, it is possible to obtain a light receiving layer in which dark current is suppressed and there are few dark spots.
  • the above impurity element can be zinc (Zn), and the diffusion concentration distribution adjusting layer can be formed of InGaAs.
  • the diffusion concentration distribution adjusting layer can be formed of a material that is less dependent on the impurity concentration of the electric resistance and does not increase the electric resistance so much even if the impurity concentration is low. Suppressing the increase in electrical resistance prevents response speed deterioration.
  • the impurity zinc has an abundant track record of selective diffusion so far, and a diffusion region can be formed with high accuracy. For this reason, in the diffusion concentration distribution adjusting layer, the high concentration impurity on the upper side on the diffusion introduction side is set to a lower concentration on the lower side on the light receiving layer side, and the electric resistance on the lower side can be prevented from being increased.
  • the band gap energy of InGaAs is 0.75 eV.
  • An InP window layer can be provided on the diffusion concentration distribution adjusting layer.
  • the formation of the window layer by InP does not impair the crystallinity of the internal semiconductor multilayer structure. Therefore, when a structure having the epitaxial layer as the incident surface side is adopted, absorption of near infrared light on the incident side from the light receiving layer, etc. This effectively works to suppress dark current.
  • the technology for forming a passivation film on the crystal surface of InP is more technically established than the technology for forming a passivation film on the surface of InGaAs, for example, when it is formed on another crystal surface. Current leakage can be easily suppressed.
  • Lattice matching degree (
  • the above-described light receiving element can take a structure that is arrayed in one or two dimensions.
  • the light receiving element array includes a plurality of light receiving elements, a common semiconductor stacked structure, and an impurity element is selectively diffused in the light receiving layer for each light receiving element, and is arranged one-dimensionally or two-dimensionally. According to this configuration, since the light receiving element is formed by each impurity diffusion region, it is not necessary to provide an element isolation groove. Therefore, it is possible to form a light receiving element array that can be easily formed with high accuracy and can reduce the dark current.
  • An imaging device including a two-dimensional array of the light receiving elements is provided, and an image of the concentration distribution and temperature distribution of the gas component in the gas can be formed by the imaging device. Thereby, it is possible to obtain a distribution image of the predetermined component in the object which is easy to understand sensuously.
  • the top side of the epitaxial layer opposite to the InP substrate with respect to the light receiving layer is the light incident surface, or the InP substrate side is the light incident surface, and the InP substrate is removed or A structure in which the thickness is reduced to a thickness equal to or smaller than that of the light receiving layer can be taken.
  • the InP substrate is removed or A structure in which the thickness is reduced to a thickness equal to or smaller than that of the light receiving layer can be taken.
  • the combustion state monitoring device of the present invention includes any one of the gas monitoring devices described above, and is characterized by monitoring the combustion state of substances such as fuel and dust. Thereby, generation
  • the secular change monitoring apparatus of the present invention includes any one of the above gas monitoring apparatuses, and is characterized by monitoring a gas component generated with the secular change of the apparatus. As a result, for example, it is possible to detect an aging deterioration in an OF (Oil Filled) cable for power transportation and to prevent an accident from occurring.
  • OF Operated
  • the impurity concentration monitoring device of the present invention includes any one of the gas monitoring devices described above, and monitors the gas component concentration of impurities in the gas introduced from the outside. As a result, for example, in semiconductor manufacturing using a high-purity process gas, trace harmful impurities such as moisture can be monitored and a quick response can be taken. As a result, the quality of the product can be maintained.
  • the combustion state monitoring device using the same, etc., using an InP-based light receiving element in which dark current is reduced and the light receiving sensitivity is expanded to a wavelength of 1.8 ⁇ m or more without a cooling mechanism,
  • the gas component in it can be detected with high sensitivity.
  • FIG. 1 is a cross-sectional view showing a light receiving element 10 according to an embodiment of the present invention.
  • the light receiving element 10 has a group III-V semiconductor laminated structure (epitaxial wafer) of the following configuration on the InP substrate 1.
  • the p-type impurity Zn is selectively diffused from the opening of the selective diffusion mask pattern 36 of the SiN film. Formed with. The fact that diffusion is introduced into the periphery of the light receiving element 10 in a limited manner in a planar manner can be achieved by diffusion using the selective diffusion mask pattern 36 of the SiN film.
  • a p-side electrode 11 made of AuZn is provided in the p-type region 6 and an n-side electrode 12 made of AuGeNi is provided in ohmic contact with the back surface of the InP substrate 1.
  • the InP substrate 1 is doped with n-type impurities to ensure a predetermined level of conductivity.
  • An antireflection film 35 made of SiON is provided on the back surface of the InP substrate 1 so that light can enter from the back surface side of the InP substrate.
  • a pn junction is formed at a position corresponding to the boundary front of the p-type region 6, and a reverse bias voltage is applied between the p-side electrode 11 and the n-side electrode 12.
  • a depletion layer is formed more widely on the side where the n-type impurity concentration is low (n-type impurity background).
  • the background in the light-receiving layer 3 having the multiple quantum well structure is about 5 ⁇ 10 15 / cm 3 or less in terms of n-type impurity concentration (carrier concentration).
  • the position 15 of the pn junction is determined by the intersection of the background (n-type carrier concentration) of the light-receiving layer 3 of the multiple quantum well and the concentration profile of the p-type impurity Zn. That is, the position shown in FIG.
  • the concentration of the p-type impurity selectively diffused from the surface 5 a of the InP window layer 5 sharply decreases from the high concentration region on the InP window layer side to the light receiving layer side. Therefore, in the light receiving layer 3, an impurity concentration of 5 ⁇ 10 16 / cm 3 or less can be easily realized.
  • the lower Zn concentration in the light receiving layer 3 is realized to be about 1 ⁇ 10 16 / cm 3 or lower.
  • the light receiving element 10 targeted by the present invention seeks to have light receiving sensitivity from the near infrared region to the long wavelength side, a material having a band gap energy larger than the band gap energy of the light receiving layer 3 is used for the window layer. It is preferable to use it. For this reason, InP, which is a material having a band gap energy larger than that of the light receiving layer and having a good lattice matching, is usually used for the window layer. InAlAs having substantially the same band gap energy as InP may be used.
  • the feature of this embodiment is that it is composed of the following elements. 1.
  • the concentration of the p-type impurity to be diffused and introduced is required to be 5 ⁇ 10 16 / cm 3 or less.
  • a diffusion concentration distribution adjusting layer 4 made of InGaAs is provided on the light receiving layer 3 in order to stably obtain the low p-type impurity concentration with good reproducibility in actual production.
  • the electrical conductivity in the low impurity concentration range decreases or the electrical resistance increases.
  • the electrical conductivity in the low impurity concentration range in the diffusion concentration distribution adjusting layer 4 is lowered, the responsiveness is lowered and, for example, a good moving image cannot be obtained.
  • the diffusion concentration distribution adjusting layer is formed of a material having a band gap energy smaller than the band gap energy equivalent to InP, specifically, a III-V group semiconductor material having a band gap energy of less than 1.34 eV, Even at low concentrations, the electrical conductivity is not significantly reduced.
  • the III-V semiconductor material that satisfies the requirements of the diffusion concentration distribution adjusting layer include InGaAs. The reason why the impurity concentration of the light receiving layer is 5 ⁇ 10 16 / cm 3 or less will be described in more detail.
  • the Zn concentration in the light receiving layer 3 exceeds 1 ⁇ 10 17 cm ⁇ 3 due to an increase in the selective diffusion depth of the p-type impurity (Zn) or the like, the InGaAs that constitutes the quantum well layer in the higher concentration portion exceeds it. And GaAsSb atoms enter each other and are disturbed, destroying the superlattice structure. The crystal quality of the destroyed portion is lowered, and the device characteristics are deteriorated, such as an increase in dark current.
  • the Zn concentration is usually measured by SIMS analysis (Secondary Ion Mass Spectroscopy), but it is difficult to analyze the concentration of 10 17 cm ⁇ 3 or 10 16 cm ⁇ 3. Large measurement error occurs.
  • the response speed to reverse bias voltage application or the like is considered to be determined by the CR time constant due to the capacitance and electric resistance, the response speed can be shortened by suppressing the increase in electric resistance R as described above.
  • the multiple quantum well structure is of type II.
  • the type I quantum well structure in the case of a light receiving element that has a light receiving sensitivity in the near infrared region while sandwiching a semiconductor layer having a small band gap energy between semiconductor layers having a large band gap energy, a semiconductor layer having a small band gap energy is used.
  • the upper limit wavelength (cutoff wavelength) of the light receiving sensitivity is determined by the band gap. That is, transition of electrons or holes due to light is performed in a semiconductor layer having a small band gap energy (direct transition).
  • the material for extending the cutoff wavelength to a longer wavelength region is very limited within the III-V compound semiconductor.
  • the conduction band of the first semiconductor and the valence band of the second semiconductor are obtained.
  • the upper limit of the wavelength (cutoff wavelength) of the light receiving sensitivity is determined. That is, transition of electrons or holes by light is performed between the valence band of the second semiconductor and the conduction band of the first semiconductor (indirect transition). For this reason, the energy of the valence band of the second semiconductor is made higher than that of the first semiconductor, and the energy of the conduction band of the first semiconductor is made lower than the energy of the conduction band of the second semiconductor. By doing so, it is easier to realize a longer wavelength of light receiving sensitivity than in the case of direct transition in one semiconductor.
  • the p-type impurity is diffused and introduced into the periphery from the periphery of the light receiving element in a planar manner, so that the pn junction is the light receiving element. It is not exposed on the end face of As a result, leakage of photocurrent is suppressed.
  • FIG. 3 is a sectional view showing a light receiving element array 50 in which a plurality of the light receiving elements 10 are arranged on an epitaxial wafer including a common InP substrate. It is characterized in that a plurality of light receiving elements 10 are arranged without element isolation grooves. As described in 4. above, the p-type region 6 is limited to the inside of each light receiving element, and is reliably separated from the adjacent light receiving elements.
  • the light receiving layer 3 is formed with a multiple quantum well structure, the diffusion concentration distribution adjusting layer 4 is disposed on the light receiving layer 3, and the p-type impurity concentration in the light receiving layer 3 is 5 ⁇ 10 16 / cm 3 or less. This is the same as the light receiving element 10 in FIG.
  • An InP buffer layer 2 or InGaAs buffer layer 2 having a thickness of 2 ⁇ m is formed on the n-type InP substrate 1.
  • the light receiving layer 3 having a multiple quantum well structure of (InGaAs / GaAsSb) or (GaInNAs / GaAsSb) is formed.
  • the thickness of the InGaAs layer (or GaInNAs layer) forming the unit quantum well structure is 5 nm, and the number of pairs (the number of repetitions of the unit quantum well) is 300.
  • an InGaAs layer having a thickness of 1 ⁇ m is epitaxially grown on the light receiving layer 3 as a diffusion concentration distribution adjusting layer 4 at the time of introducing Zn diffusion, and finally, an InP window layer 5 having a thickness of 1 ⁇ m is epitaxially grown.
  • Both the light receiving layer 3 and the diffusion concentration distribution adjusting layer 4 are preferably epitaxially grown by MBE (Molecular Beam Epitaxy) method.
  • the InP window layer 5 may be epitaxially grown by the MBE method, or after the diffusion concentration adjusting layer 4 is grown, the InP window layer 5 may be removed from the MBE apparatus and epitaxially grown by the MOVPE (Metal Organic Vapor Phase Epitaxy) method. .
  • the InP buffer layer 2 or the InGaAs buffer layer 2 may be non-doped, or may be doped with an n-type dopant such as Si at about 1 ⁇ 10 17 / cm 3 .
  • the InGaAs / GaAsSb (or GaInNAs / GaAsSb) multi-quantum well structure light-receiving layer 3, InGaAs diffusion concentration distribution adjusting layer 4, and InP window layer 5 are preferably non-doped, but a very small amount of n-type dopant such as Si (for example, Doping may be performed at about 2 ⁇ 10 15 / cm 3 .
  • a high-concentration n-side electrode forming layer for forming an n-side electrode doped with about 1E18 cm ⁇ 3 of an n-type dopant may be inserted between the InP substrate 1 and the buffer layer 2.
  • the InP substrate 1 may be a Fe-doped semi-insulating InP substrate.
  • an n-side electrode forming layer doped with n-type dopant of about 1 ⁇ 10 18 / cm 3 is inserted between the semi-insulating InP substrate 1 and the buffer layer 2.
  • An optical device is manufactured using a laminated structure (epitaxial wafer) including the InP substrate 1 described above.
  • a laminated structure epiaxial wafer
  • SiN mask pattern 36 formed on the surface 5a of the InP window layer 5 Zn is selectively diffused from the opening so as to reach the light receiving layer 3 having the InGaAs / GaAsSb (or GaInNAs / GaAsSb) multiple quantum well structure.
  • a p-type region 6 is formed.
  • the front tip of the p-type region 6 forms a pn junction 15.
  • a high concentration region having a Zn concentration of about 1 ⁇ 10 18 / cm 3 or more is limited to the InGaAs diffusion concentration distribution adjusting layer 4.
  • the high-concentration impurity distribution continues from the surface 5a of the InP window layer 5 in the depth direction to the InGaAs diffusion concentration distribution adjustment layer 4, and further 5 ⁇ at a deeper position in the diffusion concentration distribution adjustment layer 4. It decreases to 10 16 / cm 3 or less.
  • the Zn concentration distribution in the vicinity of the pn junction 15 is a distribution indicating an inclined junction.
  • the one-dimensional or two-dimensional array of the light-receiving elements 10, that is, the light-receiving element array shown in FIG. 3 is planarly selected so that Zn is selectively diffused without performing mesa etching for element separation (inside the peripheral edge of the light-receiving element).
  • the adjacent light receiving elements are separated from each other by diffusion limited to the periphery. That is, the Zn selective diffusion region 6 is a main part of one light receiving element 10 and forms one pixel, but a region where Zn is not diffused separates each pixel. For this reason, it is possible to suppress dark current without being damaged by crystals accompanying the mesa etching.
  • FIG. 4 is a cross-sectional view showing a light receiving element 110 in Reference Example 1 different from the present invention.
  • the light receiving element 110 of Reference Example 1 has the following laminated structure. (InP substrate 101 / InP or InGaAs buffer layer 102 / (GaInNAs / GaAsSb) light-receiving layer 103 / InP window layer 105 having a multiple quantum well structure)
  • the difference is that there is no diffusion concentration distribution adjustment layer as compared with the laminated structure in the embodiment of the present invention. That is, the light receiving layer 103 having a multiple quantum well structure is disposed immediately below the InP window layer 105.
  • the Zn concentration distribution has a high concentration up to the light receiving layer 103 having a multiple quantum well structure. That is, a high impurity concentration region of 1 ⁇ 10 18 / cm 3 exceeding 5 ⁇ 10 16 / cm 3 is formed in the multiple quantum well structure.
  • a diffusion concentration distribution adjusting layer is provided to perform selective diffusion.
  • FIG. 6 is a cross-sectional view showing the light receiving element 110 in Reference Example 2 for studying the cases (1) and (2).
  • the light receiving element 110 of the reference example 2 has substantially the same laminated structure as the light receiving element of the reference example 1, but the thickness of the InP window layer 105 is larger than that of the reference example 1, and corresponds to the case of (2) above.
  • the stacked structure of FIG. 1 In the stacked structure of FIG.
  • the Zn concentration distribution shown in FIG. 7 is obtained as a result of selective diffusion so that a high concentration region of Zn is not formed in the multiple quantum well structure 103.
  • the Zn concentration sharply decreases from a high concentration to a low concentration, and in the InP window layer 105 on the light receiving layer side, 1 ⁇ 10 16 / cm. About 3 low-concentration impurity regions are formed.
  • the InP window layer 105 When a low-concentration impurity region of about 1 ⁇ 10 16 / cm 3 is formed in the InP window layer 105, the electrical resistance increases in that region as described above, and the response speed decreases. For this reason, a material having a band gap energy that is large enough to form a window layer, specifically, the InP window layer 105 that is a typical material of the material cannot play a role of a diffusion concentration distribution adjusting layer. This is the same for the cases (1) and (2). Therefore, it is preferable to use a material having a band gap energy equal to or lower than InP, specifically, less than 1.34 eV, for the diffusion concentration adjusting layer. That is, even in a low concentration impurity region, it is necessary to use a material such as InGaAs in which the decrease in electrical conductivity is relatively small and the increase in electrical resistance is relatively small.
  • FIG. 8 is a diagram showing an outline of an imaging device (light receiving element array) for gas monitoring in Embodiment 2 of the present invention. Optical components such as a lens for focusing on a predetermined range of gas are omitted.
  • FIG. 9 is a diagram for explaining a light receiving element array of the imaging apparatus.
  • FIG. 10 is a diagram showing one light receiving element in the light receiving element array 50 of FIG. 9. In FIG. 8, in this imaging device 70, the light receiving element 10 formed on the common InP substrate 51 is so-called epi down mounted with the epitaxial layer side facing the multiplexer 71 having the function of a mounting substrate.
  • the p-side electrode 11 electrically connected to the p-type region 6 of the epitaxial layer of each light receiving element 10 and the n-side electrode 12 provided on the common n-type InP substrate 51 (1) are connected to the multiplexer 71. Then, an electrical signal is sent to the multiplexer, and the multiplexer 71 receives the electrical signal from each light receiving element and performs a process of forming an entire image for a predetermined range in which the gas is focused.
  • the n-side electrode 12 and the p-side electrode 11 are electrically connected to the multiplexer 71 via solder bumps 12b and 11b, respectively.
  • Incident light is introduced through an AR (Anti-Reflection) film 35 formed on the back surface of the InP substrate 51, and is received by a pn junction 15 that is an interface between the p-type region 6 and the light-receiving layer 3.
  • the p-type region 6 is introduced from an opening of a SiN Zn diffusion mask 36 that also serves as a protective film.
  • the Zn diffusion mask pattern 36 is left as it is together with the protective SiON film pattern 43 formed thereon.
  • the light receiving elements 10 of the light receiving element array 50 are provided on a common InP substrate 51 (1).
  • a current signal generated by receiving light in the SWIR band by each light receiving element is sent to the multiplexer 71 that also serves as a mounting board as described above, and image forming processing is performed.
  • the number of pixels is changed while changing the size and pitch of each light receiving element and the size of the array.
  • the light receiving element array 50 shown in FIG. 9 has 90,000 pixels.
  • the light receiving element 10 shown in FIG. 10 has a plurality of epitaxial films formed on the InP substrate 1, and a p-type impurity introduction diffusion mask 36 used for forming the p-type region 6 is provided. I'm leaving.
  • a p-type electrode 11 is connected to the p-type region 6 and connected to wiring of a mounting substrate such as the multiplexer 71 by solder bumps or the like.
  • FIG. 11 is a cross-sectional view for explaining an epi-up mounted light receiving element, unlike the epi-down light receiving element shown in FIG.
  • the light receiving element in the imaging apparatus may be either epi-down mounting or epi-up mounting.
  • the light receiving element 10 is formed on an n-type InP substrate 1 in order from the bottom: n-type InP buffer layer 2 / light-receiving layer 3 / diffusion concentration distribution adjusting layer 4 / InP window layer 5 / diffusion mask 36 / antireflection film (AR Membrane (Anti-Reflection) 35 is located.
  • the p-type region 6 is formed from the InP window layer 5 to the pn junction 15 in the light receiving layer 3 through the diffusion concentration distribution adjusting layer 4.
  • the n-side electrode 12 is located on the back surface of the n-type InP substrate, and the p-side electrode 11 is located on the surface of the InP window layer 5 in the p-type region 6 and is electrically connected to the wiring electrode 27.
  • the light receiving layer 3 receives light in the wavelength range of 1.0 ⁇ m to 3.0 ⁇ m.
  • the light receiving layer 3 is formed by the above-described type II multiple quantum well structure.
  • the light receiving element shown in FIG. 11 is epi-up mounted as described above, and light is incident from the epitaxial layer, that is, the InP window layer 5 side.
  • the light receiving element in the present embodiment may be either epi-up mounting or epi-down mounting.
  • the light-receiving element may be epi-down mounting and receive light from the back side of the InP substrate 1.
  • an AR film 35 is applied to the back surface of the InP substrate 1.
  • the diffusion mask 36 of SiN also serving as the diffusion concentration adjusting layer 4, the InP window layer 5, the p-side electrode 11 and the protective film is provided in the same manner as in the case of epi-up mounting.
  • the SWIR band light reaches the pn junction 15 of the light receiving layer 3 without being absorbed.
  • the light receiving layer is formed by the above-described type II multiple quantum well structure. This also applies to the following examples of the present invention unless otherwise specified.
  • the p-side electrode 11 and the n-side electrode 12 may be arranged at positions facing each other with the InP substrate 1 interposed therebetween as shown in FIG. 11, or the same side of the InP substrate 1 as shown in FIG. You may arrange
  • each light receiving element 10 of the light receiving element array 50 shown in FIG. 9 and the integrated circuit are electrically connected by flip chip mounting.
  • the light reaching the pn junction 15 is absorbed to generate a current signal, which is converted into an image of one pixel through the integrated circuit as described above.
  • the InP substrate 1 is preferably an off-angle substrate inclined from 5 to 20 degrees in the [111] direction or the [11-1] direction from (100). More preferably, the angle is inclined by 10 to 15 degrees from (100) to the [111] direction or the [11-1] direction.
  • the n-type InP buffer layer 2, the type II quantum well structure light-receiving layer 3, the InGaAs diffusion concentration distribution adjusting layer 4 and the InP window layer having a small defect density and excellent crystallinity are used. 5 can be obtained. As a result, it is possible to obtain a light receiving layer in which dark current is suppressed and there are few dark spots.
  • the action of the light receiving element formed using the off-angle substrate is particularly useful for improving the quality of an image pickup apparatus that receives and picks up space light.
  • the large off angle as described above has never been proposed for the InP substrate, and has been confirmed for the first time by the present inventors, and is important for growing a good crystalline epitaxial film on the InP substrate.
  • a compound semiconductor containing N for example, GaInNAs
  • the light-receiving layer 3 having the above-described quantum well structure which can emit and receive light in a very long wavelength region, a large off angle as described above.
  • an InP substrate is used, in practice, it is impossible to form a good epitaxial layer that can withstand practical use.
  • an InP substrate having a large off-angle as described above a compound semiconductor containing N, such as GaInNAs, suppresses dark current and does not become a light-receiving layer with reduced dark spots. As a result, a clear image cannot be obtained using weak SWIR band space light.
  • the off-angle of the InP substrate is the same in GaInNAsP and GaInNAsSb in that a large angle range as described above is necessary to obtain good crystallinity.
  • 11 and 12 includes an InGaAs diffusion concentration adjusting layer 4 and an InP window layer 5 positioned so as to cover the light receiving layer 3. Since the lattice constant of the light receiving layer 3 is the same as the lattice constant of the InP substrate 1, the InGaAs diffusion concentration adjusting layer 4 and the InP window layer 5 that are well-established by reducing the dark current are formed on the light receiving layer 3. be able to. For this reason, dark current can be suppressed and element reliability can be improved. *
  • FIG. 13 is a diagram showing the gas monitoring device 100 according to Embodiment 3 of the present invention.
  • the gas monitoring device 100 monitors the aging of an OF (Oil Filled) cable used for transmission of electric power or the like.
  • the gas monitoring device 100 detects a gas component present in the in-oil gas separation cell 40 provided in the OF cable.
  • FIG. 15 is a diagram for explaining the hydrogen sensor 45 in the waveguide in the gas monitoring device 100.
  • FIG. 16 is a diagram showing the concentrations of methane CH 4 and acetylene C 2 H 2 that are gas components in the gas-in-oil separation cell 40.
  • concentrations of methane and acetylene By detecting the concentrations of methane and acetylene, the approximate degree of degradation can be detected.
  • FIG. 16 it is divided into four groups A, B, C, and D based on the concentrations of methane and acetylene.
  • the OF cable was disassembled and the degree of deterioration was examined, and the following relationship was recognized with the above four groups.
  • Group A Destruction of cable part, etc.
  • Group B Colorless core, etc.
  • Group C Connection corona discharge trace, etc.
  • Group D Connection paper, slightly waxed, normal parts from Group D to Group A have deteriorated over time. It can be seen that the degree is increasing.
  • methane CH 4 and acetylene C 2 H 2 it is also necessary to detect hydrogen H 2 , ethene C 2 H 4 , ethane C 2 H 6 , and carbon monoxide CO in order to determine deterioration over time. It becomes.
  • the apparatus shown in FIGS. 13 to 15 is used.
  • the peak wavelength of the absorption spectrum of the above gas component in the near infrared region is as follows. Acetylene C 2 H 2 : 1.5201 ⁇ m Carbon monoxide CO: 1.5688 ⁇ m Ethene C 2 H 4 : 1.6245 ⁇ m Methane CH 4 : 1.6456 ⁇ m Ethane C 2 H 6 : 1.6816 ⁇ m Hydrogen H 2 is a diatomic molecule and does not change in dipole moment, and therefore has no absorption spectrum in the near infrared region. For this reason, in detecting hydrogen, the hydrogen sensor 45 that changes color by adsorbing hydrogen in contact with hydrogen is exposed in the gas cell 40 and disposed so that the light propagation path passes therethrough.
  • the near infrared light in the light propagation path is attenuated by the coloring of the hydrogen sensor due to the hydrogen adsorption. Accordingly, the amount of light transmitted in the near infrared region changes depending on the hydrogen concentration, so that hydrogen can be detected by this change in the amount of light.
  • a halogen lamp or the like that emits light including wavelengths in the near infrared region to the visible region can be used.
  • the light is guided from the light guide end 81 a to the optical fiber, divided into measurement light and reference light by the optical branching device 88 a, and the measurement light is guided to the optical fiber 81.
  • the reference light is guided to the optical fiber 7 c and reaches the optical path switch 8.
  • the measurement light is emitted from the emission end of the optical fiber 81 to the oil-in-gas separation cell or the gas cell 40.
  • the gas cell 40 is mixed with the above gas components containing hydrogen due to aging.
  • Light that has received absorption corresponding to the peak wavelength in the near infrared region other than hydrogen propagates through the optical fiber 82 from the light guide end.
  • the light that has propagated through the optical fiber 82 and includes the information on the absorption of the gas component is branched by the optical branching device 88b, and one of the light reaches the optical path switch 8 while containing the information.
  • the other is propagated through the hydrogen sensor 45 whose color has been changed by hydrogen, and reaches the optical path switch 8 through the optical fiber 7b.
  • FIG. 15 is a diagram showing the hydrogen sensor 45.
  • a substrate 45a made of LiNbO 3, and the optical propagation path 45b of the Ti on the substrate are formed by thermal diffusion, and WO 3 film 45c obtained by vacuum deposition of WO 3 thereon was sputtered Pd thereon
  • the Pd thin film 45d is a main component. Both ends of the light propagation path 45b are connected to the optical fiber 7b (see FIG. 13).
  • the hydrogen sensor 45 is placed in the gas cell 40 in which hydrogen is mixed, the WO 3 thin film 45c is colored using the Pd thin film 45d as a catalyst.
  • the attenuation ratio of the evanescent wave propagating through the light propagation path 45b is increased, and the transmitted light amount in the near infrared region is attenuated. This change in the amount of transmitted light includes information on the hydrogen concentration.
  • three optical fibers 7 a, 7 b and 7 c are connected to the optical path switch 8.
  • light including information on gas components other than hydrogen is emitted from the emission end 82b.
  • This light is converted into parallel light by a lens and is irradiated on the diffraction grating 91.
  • the diffraction grating 91 splits the light and emits light of each wavelength split by the light receiving element array 50 according to the emission angle.
  • the light receiving element array 50 may be a one-dimensional array or a two-dimensional array, but each light receiving element in the array is associated with a wavelength according to a position in advance.
  • an absorption spectrum including the base noise of the gas component excluding hydrogen can be obtained.
  • Such spectrum measurement is performed not only on the light passing through the optical fiber 7a but also on the reference light on the optical fiber 7c and the light transmitted through the hydrogen sensor on the optical fiber 7b.
  • Switching between the optical fibers 7a, 7b, and 7c is performed by an optical path switch 8.
  • the order in which optical fibers are measured is not limited. For example, (1) First, the spectrum of light passing through the hydrogen sensor 45 provided in the oil-in-gas separation cell 40 and passing through the optical fiber 7c is obtained. . The measurement of light passing through the hydrogen sensor 45 is performed both before and after coloring with hydrogen. Next, (2) the spectrum of the reference light of the optical fiber 7c is obtained.
  • a spectrum of light passing through the in-oil gas separation cell 40 and passing through the optical fiber 7a is obtained.
  • the concentration of each gas component can be obtained by obtaining the intensity at the absorption peak wavelength of each gas component described above based on the above spectrum.
  • For hydrogen, an appropriate wavelength in the near-infrared region is determined, and the wavelength can be obtained based on the intensity change before and after coloring of the hydrogen sensor 45.
  • the degree of coloring of the hydrogen sensor 45 may be measured directly using visible light. In that case, light including a visible region shorter than the near-infrared region is absorbed by the InP substrate. If the light receiving elements 10 are arranged in a line, as shown in FIG. 11, it is preferable to use the light receiving element 10 having the epitaxial layer top as the light incident surface (epi-up mounting) and the InP substrate as the mounting side. As for the one-dimensional array provided on the common InP substrate, it is possible to easily build the structure of the light receiving element 10 shown in FIG. 11 on one common InP substrate. However, regarding the structure of the two-dimensional array, it is difficult to provide wiring from each p-side electrode so as not to obstruct light.
  • the two-dimensional array 50 on the common InP substrate has a structure in which the epitaxial layer top is the mounting side (epi-down mounting) and the buffer layer 2 or the light receiving layer 3 side is the light incident side. It is good to do. It is preferable to remove the InP substrate or reduce the thickness to about the thickness of the light receiving layer 3 or less.
  • the InP substrate is removed.
  • the common n-side electrode 12 is connected to the ground potential electrode pad 12c of the CMOS 71 by a bonding wire 12w.
  • Each p-side electrode 11 is connected to an electrode pad 11 c provided in the protective film 43.
  • Such a light receiving element array 50 can be two-dimensionally arranged on a common InP substrate, thereby receiving light in the visible range with high sensitivity, and directly monitoring the coloration of the hydrogen sensor 9. be able to.
  • the light receiving element array 50 or the imaging device 40 as shown in FIG. 17 will be referred to also in a modification of the embodiment of the present invention and the fourth embodiment which will be described later.
  • Patent Document 2 in an OF cable secular change monitor, five laser light sources are arranged according to the absorption peak wavelength of each gas component, the concentration of each gas component is obtained, and the laser light source is modulated. The hydrogen concentration was obtained using the modulated light.
  • the five laser light sources are not required, and a modulator is not required.
  • the economic efficiency can be greatly improved and the monitoring device can be greatly simplified. Therefore, the need for maintenance in preparation for a failure is reduced, and the maintenance frequency can be reduced.
  • FIG. 18 and 19 are diagrams showing a modification of the third embodiment of the present invention.
  • the gas shown in FIG. This is the same as the monitoring device 100.
  • the difference is that the light propagating through the gas without passing through the optical fiber through the hydrogen sensor 45 is transmitted through the hydrogen sensor 45 and the spectrum of the light transmitted through the hydrogen sensor 45 is measured. That is, as shown in FIG. 17, the hydrogen sensor 45 is formed of a transparent glass substrate 45g and a catalyst thin film 45f.
  • the catalyst Pt, Pd, PdWO 3 , PtWO 3 or the like can be used.
  • the subsequent path is the same as that of the optical fiber 7a in FIG.
  • Patent Document 1 the oscillation frequency of the laser light source is matched with the absorption band of the hydrogen sensor 45, and the wavelength range of the double frequency emitted by modulating the laser light source is modulated to the absorption peak wavelength of hydrocarbon gas. To match. According to this, the hydrogen concentration and the concentrations of other gas components can be obtained without affecting each other.
  • the light receiving element 10 or the light receiving element array 50 may be the light receiving element of FIG. 11, or a one-dimensional array thereof, or the light receiving element array 50 shown in FIG. Rather, it is preferable to use the light receiving element that reduces the absorption in the short wavelength region in order to know the color change of the hydrogen sensor 45.
  • FIG. 20 is a diagram showing a gas monitoring device or combustion state monitoring 100c according to Embodiment 4 of the present invention.
  • This combustion state monitoring device 100c It is an apparatus for diagnosing the combustion state of a flame in a combustion furnace, and measures the spectrum of flame light guided from a plurality of optical probes P1, P2, etc. that receive flame light, and performs a highly accurate diagnosis.
  • combustion apparatuses such as boilers are desired not to generate nitrogen oxides, soot, and carbon monoxide.
  • a flame in which fuel and air are appropriately mixed is formed in a combustion furnace.
  • One of the devices that monitor such a combustion state is one that detects a flame emission spectrum and diagnoses the combustion state from this spectral characteristic, and corresponds to the combustion state monitoring device in the present embodiment.
  • a plurality of probes P1, P2,... Pn (or a light guide end 82a) are attached to the furnace wall of the boiler to guide the flame light to the optical fiber 82.
  • the plurality of optical fibers 82 are connected to the optical path switch 8, and only the optical fibers of the optical path selected by the optical path switch 8 are turned on and light is allowed to pass therethrough.
  • the light on the optical path in the on state is emitted from the emission end 82b of the optical fiber to the lens 87.
  • the light converted into parallel rays by the lens 87 is diffracted by the diffraction grating 91 and received by the light receiving element array 50 for each wavelength.
  • the light receiving element array 50 may be a one-dimensional or two-dimensional array manufactured on a common InP substrate, or may be one in which individual light receiving elements 10 are arranged.
  • the soot emission spectrum is in the visible range, and as described above, the individual light receiving elements 10 arranged in rows are shown in FIG.
  • the top of the epitaxial layer is preferably the light incident surface (epi-up mounting), and the InP substrate is preferably the mounting side.
  • the one-dimensional array as described above, the structure in which the light receiving elements 10 shown in FIG. 11 are arranged one-dimensionally on one common InP substrate can be easily manufactured.
  • the top of the epitaxial layer is the mounting side, and the buffer layer 2 or the light receiving layer 3 side is the light incident side (epi down). Implementation).
  • the InP substrate may be removed or reduced in thickness.
  • Patent Document 3 a multi-layer element in which a number of interference filters are attached to a turntable and a silicon photodiode and a PbS photoconductive element are stacked is used as a light receiving element.
  • the same number of multi-layer light receiving elements as the interference filters are necessary, and are also attached to the turntable.
  • the combustion state monitoring apparatus 100c shown in FIG. 20 does not require the above-described turntable, interference filter, and multilayer light receiving element, and can be greatly simplified as compared with the conventional apparatus. Such remarkable simplification improves the measurement accuracy, reduces the necessary maintenance frequency for the combustion state monitoring device, and reduces the manufacturing cost of the device.
  • FIG. 22 shows a temperature distribution measuring apparatus 100d for obtaining a temperature distribution of garbage in a garbage combustion furnace.
  • FIG. 23 is a diagram showing the temperature distribution imaging device 55.
  • carbon or hydrocarbons are in bulk and do not exist in a form suitable for fuel, so there is little soot and there is a large amount of moisture.
  • FIG. 24 shows the near-infrared spectrum in the refuse combustion furnace, and the emission spectrum wavelengths ⁇ 2 and ⁇ 3 of water are prominent.
  • the concentration and temperature of water are monitored together with the absorption spectrum of water shown in FIG. 25 using the fact that the emission spectrum of water changes with temperature.
  • the interference filter 55a is important.
  • the interference filter 55a is a filter having a transmission wavelength at each of the light emission peak wavelengths ⁇ 2 and ⁇ 3 and the plurality of absorption peak wavelengths.
  • the absorption peak wavelength has two sharp peaks M2 and M3 in the near infrared region as shown in FIG. 25, but the interference filter 55a allows light of these wavelengths to pass.
  • the interference filter 55a includes a total of four types of filters or four transmission wavelength filters in combination with the two emission peak wavelengths. It is desirable to provide an automatic selection mechanism that automatically selects these four types of interference filters by an external operation. It is preferable to provide an autofocus mechanism for automatically focusing the optical system 55c such as a lens. For example, corresponding to the above-described four types of interference filters, imaging of dust or a little above it is performed for light of four wavelengths. As a result, images of four wavelengths can be obtained. For air with the water vapor temperature and water vapor concentration changed in advance, the light intensity at the above wavelength can be obtained, and the temperature regression equation can be obtained. This temperature regression equation is stored in the microcomputer 85b of the control unit.
  • the intensity for each wavelength can be obtained at each position. If the above temperature regression equation is used, the temperature can be obtained at each position. In this way, by monitoring both the temperature and concentration of water, it is possible to accurately detect the combustion state of waste.
  • Patent Document 4 many temperature sensors have been arranged in the waste incinerator, but the number of temperature sensors can be reduced by arranging the apparatus of the present embodiment at the top or top of the incinerator. Can be reduced.
  • FIG. 26 is a diagram showing an impurity monitoring apparatus 100e in gas, which is a gas monitoring apparatus according to Embodiment 6 of the present invention.
  • This device is the device itself disclosed in Non-Patent Document 2.
  • a semiconductor laser having an oscillation wavelength of about 1371 ⁇ m (corresponding to M2 in FIG. 25) is used as the light source 73, a beam splitter 93 and a mirror 94 are used to divide the beam into two beams, and one of the sample cells into which the process gas to be measured is introduced. Through the others, cancel beams are used. For light intensity measurement, lock-in detection is performed to remove DC noise components.
  • Non-Patent Document 2 a germanium photodiode with a preamplifier is used.
  • the light receiving elements shown in FIG. 10 or FIG. 11 are used as the light receiving elements 10a and 10b.
  • not only one wavelength, but any of the absorption peak wavelengths shown in FIG. 25 can be selected. Therefore, by preparing semiconductor laser devices corresponding to M1 and M3 in FIG. 25, it is possible to monitor the moisture concentration at three wavelengths. This makes it possible to monitor the concentration of moisture, which is the most undesirable impurity in the process gas, with higher accuracy.
  • the light receiving element interval or the pixel pitch is the width of the non-opening portion of the SiN selective diffusion mask pattern 36 as shown in FIG.
  • the p-side electrode 11 was formed of AuZn
  • the n-side electrode 12 was formed of AuGeNi.
  • the n-side electrode 12 is provided in the buffer layer 2 of high concentration impurities.
  • FIG. 3 since an Fe-doped semi-insulating substrate is used for the InP substrate 1, the n-side electrode 12 is provided in the buffer layer 2 of high concentration impurities.
  • an n-side electrode When n is used, an n-side electrode may be provided on the back surface of the substrate, or an n-side electrode may be provided on the n-type semiconductor layer (for example, buffer layer 2) adjacent to the substrate on the front surface side of the substrate.
  • a dark current was measured by applying a reverse bias voltage of 5 V between the p-side electrode 11 and the n-side electrode 12 of the light receiving element array of FIG.
  • the InP window layer 5 has a thickness of 0.6 ⁇ m and 1.6 ⁇ m, and an element interval of 7 types over a range of 3 ⁇ m to 20 ⁇ m. .
  • the thickness of the diffusion concentration distribution adjusting layer 4 was 1 ⁇ m.
  • the dark current can be 1 ⁇ 10 ⁇ 10 A (ampere) even if the element interval or the pixel pitch is reduced to 5 ⁇ m.
  • the thickness of the InP window layer 5 is 1.6 ⁇ m, as described above, the diffusion of Zn in the lateral direction spreads, and it cannot be set to 1 ⁇ 10 ⁇ 10 A unless the element spacing exceeds 7 ⁇ m.
  • the element spacing could be 5 ⁇ m by reducing the thickness of the InP window layer 5 to 0.6 ⁇ m and disposing the diffusion concentration distribution adjusting layer.
  • FIG. 29 shows the concentration distribution of Zn in the depth direction.
  • the peak value of Zn pileup is suppressed to 5 ⁇ 10 16 cm ⁇ 3 or less.
  • the Zn concentration can be surely lowered, crystallinity, etc. Can be prevented.
  • the arrangement of the diffusion concentration distribution adjusting layer 4 allows the multiple quantum well structure of the light receiving layer to have its original function.
  • the present invention can perform high-accuracy inspection on existing food quality inspection apparatuses by contributing to the reliability of food by the breakthrough performance improvement of InP-based PDs.
  • FIG. 1 It is a figure which shows an example of the light receiving element of this invention suitable when the sensitivity in a visible region is required in addition to a near-infrared region. It is a figure which shows the modification of the gas monitoring apparatus (1) of FIG. It is a figure which shows the hydrogen sensor used for FIG. It is a figure which shows the combustion state monitoring apparatus of the gas monitoring apparatus (2) in Embodiment 4 of this invention. It is a figure which shows the spectrum example of flame light. It is a figure which shows the temperature distribution measuring apparatus of the gas monitoring apparatus (3) in Embodiment 5 of this invention. It is a figure which shows the imaging device in the gas monitoring apparatus (3) of FIG. It is a figure which shows the emission spectrum of water for demonstrating the principle of the gas monitoring apparatus (3) of FIG.

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PCT/JP2009/063581 2008-12-25 2009-07-30 気体モニタリング装置、燃焼状態モニタリング装置、経年変化モニタリング装置、および不純物濃度モニタリング装置 Ceased WO2010073770A1 (ja)

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US13/142,039 US8624189B2 (en) 2008-12-25 2009-07-30 Gas monitoring device, combustion state monitoring device, secular change monitoring device, and impurity concentration monitoring device
CN200980152617.2A CN102265138B (zh) 2008-12-25 2009-07-30 气体监测装置、燃烧状态监测装置、长期变化监测装置和杂质浓度监测装置
EP09834576.2A EP2372342A4 (en) 2008-12-25 2009-07-30 GAS MONITORING DEVICE, COMBUSTION STATUS MONITORING DEVICE, DAY CHANGE MONITORING DEVICE AND UNWIRED MONITORING DEVICE

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JP2008331531A JP4743453B2 (ja) 2008-12-25 2008-12-25 気体モニタリング装置、燃焼状態モニタリング装置、経年変化モニタリング装置、および不純物濃度モニタリング装置
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US8729527B2 (en) 2008-02-01 2014-05-20 Sumitomo Electric Industries, Ltd. Light-receiving element, light-receiving element array, method for manufacturing light-receiving element and method for manufacturing light-receiving element array
US20120299144A1 (en) * 2011-05-23 2012-11-29 Mitshubishi Electric Corporation Semiconductor light receiving device
CN108551503A (zh) * 2018-04-25 2018-09-18 北京小米移动软件有限公司 一种光学器件模组及移动终端
US11961863B2 (en) 2018-09-19 2024-04-16 Sony Semiconductor Solutions Corporation Imaging element, semiconductor element, and electronic apparatus

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