Optical concentration measuring method

Abstract

To provide a concentration measuring method with which the concentration of a predetermined chemical component can be accurately, quickly, and nondestructively measured down to a concentration range of an extremely small amount with a simple means, and to provide a concentration measuring method with which the concentration of a chemical component in an object to be measured can be accurately and quickly measured down to a concentration range of a nano-order extremely small amount in real time, the method having universality, i.e., the ability to be embodied in various forms and modes. Light having a first wavelength and light having a second wavelength, which have different light absorptances with respect to an object to be measured, are each radiated onto the object to be measured using a time-sharing method; the light having the first wavelength and the light having the second wavelength, optically passing through the object to be measured as a result of the irradiation with the light having the first and second wavelengths, are received with a common light receiving sensor; a differential signal between a signal related to the light having the first wavelength and a signal related to the light having the second wavelength to be output from the light receiving sensor according to the received light is formed; and the concentration of a chemical component in the object to be measured is derived on the basis of the differential signal.

Claims

1. A concentration measuring method, comprising the steps of: irradiating light having a first wavelength and light having a second wavelength onto an object to be measured using a time-sharing method, the lights having first and second wavelengths having different light absorptivities with respect to the object to be measured; receiving the light of each wavelength that optically passes through the object to be measured as a result of the irradiation of the light of each wavelength, using a common light-receiving sensor; forming a differential signal between a first signal related to the light having the first wavelength and a second signal related to the light having the second wavelength output from the light-receiving sensor in accordance with the received light; and deriving a concentration of a chemical component of the object to be measured on the basis of the differential signal, wherein T13<T12T11, where T13, T12 and T11 are respectively first, second and third periods, the first and second signals are formed by the light receiving sensor in first period T13, second period T12 is from a rise start point (t1) to a fall start point (t2) of the light-receiving sensor, and third period T11 being when the light is irradiated onto the object to be measured, first period T13 is arranged to be within second period T12, and the second period T12 is arranged to be the same as or within third period T11.

2. The concentration measuring method according to claim 1, wherein the object to be measured is in a gas state.

3. The concentration measuring method according to claim 1, wherein the object to be measured is in a liquid state.

4. The concentration measuring method according to claim 1, wherein the object to be measured is a fruit or a vegetable.

5. The concentration measuring method according to claim 1, wherein the light-emitting unit comprises a light source that emits the light having the first wavelength and a light source that emits the light having the second wavelength.

6. The concentration measuring method according to claim 1, wherein the light-emitting unit comprises a light source that emits the light having the first wavelength and the light having the second wavelength.

7. A concentration measuring method, comprising the steps of: irradiating a first light and a second light onto an object to be measured using a time-sharing method, the first and second lights having different light absorptivities with respect to the object to be measured; receiving each light that optically passes through the object to be measured by irradiation of each light onto the object to be measured, using a common light-receiving sensor; forming a differential signal between a first signal related to the first light and a second signal related to the second light output from the light-receiving sensor in accordance with the received light; and deriving a concentration of a predetermined chemical component of the object to be measured on the basis of the differential signal, wherein T13<T12T11, where T13, T12 and T11 are respectively first, second and third periods, the first and second signals are formed by the light receiving sensor in first period T13, second period T12 is from a rise start point (t1) to a fall start point (t2) of the light-receiving sensor, and third period T11 being when the light is irradiated onto the object to be measured, first period T13 is arranged to be within second period T12, and the second period T12 is arranged to be the same as or within third period T11.

8. The concentration measuring method according to claim 7, wherein irradiation using the time-sharing method is performed by propagating the light through irradiation optical paths in which the optical axes of the emitted light and received light are the same or substantially the same.

9. The concentration measuring method according to claim 7, wherein irradiation using the time-sharing method is performed by propagating the light through irradiation optical paths that are the same or substantially the same in the object to be measured.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a timing chart for explaining the principles of a concentration measuring method of the present invention.

(2) FIG. 2 is a block diagram for explaining a configuration of a preferred embodiment of an optical concentration measuring system that embodies the concentration measuring method of the present invention.

(3) FIG. 3 is a flowchart for explaining a preferred embodiment of the concentration measuring method of the present invention.

(4) FIG. 4 is a timing chart for explaining a signal output timing of the example in FIG. 3.

(5) FIG. 5 is a flowchart for finding an analytical curve.

(6) FIG. 6 is a graph of a relationship between a gas concentration GC and log(1T).

(7) FIG. 7 is an explanatory schematic configuration view for explaining a main component of a preferred embodiment of the optical concentration measuring system that embodies the concentration measuring method of the present invention.

(8) FIG. 8 is an explanatory schematic configuration view for explaining main components of another preferred embodiment of the optical concentration measuring system that embodies the concentration measuring method of the present invention.

(9) FIG. 9 is an explanatory schematic configuration view for explaining main components of yet another preferred embodiment of the optical concentration measuring system that embodies the concentration measuring method of the present invention.

(10) FIG. 10 is an explanatory schematic configuration view for explaining a main component of yet another preferred embodiment of the optical concentration measuring system that embodies the concentration measuring method of the present invention.

(11) FIG. 11 is an explanatory schematic configuration view for explaining a preferred example of a differential signal forming portion adopted in the present invention.

(12) FIG. 12 is an explanatory schematic configuration view for explaining another preferred example of the differential signal forming portion adopted in the present invention.

(13) FIG. 13 is an explanatory schematic configuration view for explaining yet another preferred example of the differential signal forming portion adopted in the present invention.

(14) FIG. 14 is an explanatory schematic configuration view for explaining yet another preferred example of the differential signal forming portion adopted in the present invention.

(15) FIG. 15 is a graph showing a relationship between an absorbance value measured with respect to a gas concentration and a value equivalent to three times a standard deviation of a noise superimposed on the measured signal.

(16) FIG. 16 is an outline external view illustrating an embodiment of a case in which the present invention is applied to a mobile terminal device.

(17) FIG. 17 is a block diagram of an internal configuration of an embodiment in a case in which the present invention is applied to a mobile terminal device.

(18) FIG. 18 is an explanatory schematic configuration view for explaining yet another preferred example of the differential signal forming portion adopted in the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

(19) FIG. 1 is a timing chart for explaining the principles of a concentration measuring method of the present invention. In the present invention, a concentration measuring device for embodying the concentration measuring method of the present invention is activated, and a signal of an absolute value of a background light in a space where the device is placed is read as a difference between outputs S20 and S10 (absolute value output X).

(20) Next, light from a light source 1 that emits light (L1) having a first wavelength is received by a light-receiving sensor, and a differential output signal (G1) of a difference between outputs S30 and S40 is read (output as a sum of the background light and the light of the light source 1).

(21) Next, light from a light source 2 that emits a light (L2) having a second wavelength is received by the same light-receiving sensor, and a differential output signal (G2) of a difference between outputs S50 and S60 is read (output as a sum of the background light and the light of the light source 2).

(22) Measurement data can be calibrated using the absolute value output X, even if a change occurs in an amount of light of the light source, an absorbance of an object to be measured as a result of a temperature change, or the like.

(23) With the light-receiving signals from the light sources 1, 2 output as differential output signals, noise of a circuit system can be removed, making it possible to achieve detection with high accuracy, even if the concentration is weak.

(24) In FIG. 1, indicates the output timing of the light-receiving sensor. While in principle the output timing includes a rise start point (t1) and a fall start point (t2) of the output of the light-receiving sensor, the output timing in FIG. 1 is the timing between the rise start point (t1) and the fall start point (t2). This is because, when one measurement ends, an electronic circuit is partially reset for the next measurement. That is, a measurement period and a reset period may overlap due to a time lag in the circuit and thus, to reliably avoid effects therefrom, the output timing is the timing between the rise start time (t1) and the fall start time (t2).

(25) FIG. 2 is a block diagram of a configuration example of an optical concentration measuring system 100 serving as a preferred embodiment that embodies the concentration measuring method of the present invention.

(26) The optical concentration measuring system 100 comprises a light source portion 101, a light-focusing optical portion 102, a light-receiving sensor portion 106, a differential signal forming portion 108, a signal storage/processing portion 110, a display unit 112, a control unit 113, and an operation portion 114.

(27) The optical concentration measuring system 100 illustrated in FIG. 2 comprises an optical gas concentration measuring sub-system 100-1 and a control/operation sub-system 100-2.

(28) The optical gas concentration measuring sub-system 100-1 comprises an optical gas concentration measuring device 100-3.

(29) The optical concentration measuring sub-system 100-1 comprises the light source portion 101, the light-focusing optical portion 102, the light-receiving sensor portion 106, the differential signal forming portion 108, the signal storage/processing portion 110, and the display unit 112.

(30) The control/operation sub-system 100-2 comprises the control unit 113 and the operation portion 114.

(31) An object 104 to be measured, subject to concentration measurement of a preferred chemical component, is arranged in a predetermined position between the light-focusing optical portion 102 and the light-receiving sensor portion 106.

(32) While the light source portion 101 illustrated in FIG. 2 comprises two light sources including a light source 101a that emits the light (L1) having the first wavelength and a light source 101b that emits the light (L2) having the second wavelength, the present invention is not limited thereto, allowing a single light source that emits the light (L1) having the first wavelength and the light (L2) having the second wavelength.

(33) A light-emitting portion capable of irradiating light having two or more different wavelengths such as described above may comprise two or more light-emitting elements, each capable of irradiating light having one type of wavelength. Furthermore, the light-emitting portion preferably comprises at least one light-emitting element capable of irradiating light having two or more different wavelengths (multiple wavelength light-emitting element). This decreases the number of light-emitting elements arranged in the device interior, making it possible to reduce the size of the device.

(34) When two light sources are adopted, disposing the two light sources as close to each other as possible so that each light can be irradiated on substantially the same optical axis increases the accuracy of the measured value, and is thus preferred.

(35) When a single light source is adopted, the light (L1) and the light (L2) are selectively separated by means such as a wavelength selecting optical filter prior to being irradiated onto the object 104 to be measured.

(36) When the lights (L1, L2) having the two wavelengths are irradiated using a single light source, the device is designed so that the light having the applicable wavelength is irradiated in accordance with an irradiation timing using an optical wavelength selecting filter such as a spectrum filter.

(37) While the light (L1) having the first wavelength and the light (L2) having the second wavelength may each be light having a single wavelength, adoption of light having multiple wavelengths, each having a bandwidth for a wavelength, is preferred, taking into consideration ease of acquisition of the light source, such as an LED, and cost. Such light preferably has a center wavelength (wavelength with a peak intensity) of 1 or 2.

(38) In the present invention, the light (L1) is light having a wavelength that has an absorbability with respect to a chemical component subject to concentration measurement. In contrast, the light (L2) is a light having a wavelength that has no or substantially no light absorbability with respect to the chemical component, or an absorbability with respect to the chemical component that is relatively lower than that of the light (L1).

(39) In the present invention, a light such as the light (L2) is preferably adopted since measurement accuracy increases when there is no absorbability with respect to the chemical component or to the extent the absorbability differs from that of the light (L1).

(40) When the concentrations of a plurality of chemical components are measured using the same object to be measured, the light (L1) is prepared in a quantity equivalent to the number of chemical components to be measured. That is, given N as the number of chemical components, the light (L1) is prepared in a quantity of n (L1n, where n is a positive integer). Among the lights (L1n, where n is a positive integer), the light selected as applicable is the light having a wavelength or a wavelength range that exhibits an absorbability with respect to the one chemical component only and no or substantially no absorbability with respect to any other chemical component. For example, when glucose and hemoglobin are measured using the same object to be measured, light (L11) that exhibits absorbability with respect to glucose but not with respect to hemoglobin, and light (L12) that does not exhibit absorbability with respect to glucose but does with respect to hemoglobin are selected.

(41) For the light (L2), light that exhibits no or substantially no absorbability with respect to either chemical component is selected.

(42) As the light source of the light source portion, needless to say, a light source that emits light according to these conditions is selected and used.

(43) The light (L1) and the light (L2) are irradiated onto the object 104 to be measured in accordance with a time-sharing method.

(44) The light (L1) and the light (L2) are preferably irradiated onto the same optical axis or substantially the same optical axis when irradiated onto the object 104 to be measured. That is, even when a chemical component subject to concentration measurement has a spotted distribution or an uneven distribution spatially or temporally in the object 104 to be measured, when the positions in which the light (L1) and the light (L2) pass through the object 104 to be measured are the same or substantially the same, the measurement period is, at the same time, extremely short, resulting in the advantage of achieving a highly accurate measurement minimally affected by measurement errors.

(45) An irradiated light 103 formed by the light (L1) or the light (L2) is irradiated onto the object 104 to be measured and, as a result, a transmitted light 105 exits from the exact opposite side of the object 104 to be measured.

(46) The transmitted light 105 enters a light-receiving surface of a light-receiving sensor located in the light-receiving sensor portion 106.

(47) The light-receiving sensor portion 106 outputs an electric signal 107 in response to the received light.

(48) The signal 107 is either a signal 107a based on the light (L1) or a signal 107b based on the light (L2).

(49) The signal 107a and the signal 107b are input to the differential signal forming portion 108 either sequentially based on a set time difference or simultaneously.

(50) When input based on a set time difference, the signal input first may, depending on the case, be held for a predetermined period in a predetermined circuit inside the differential signal forming portion 108 in accordance with a timing for forming the differential signal.

(51) A differential output signal 109 output from the differential signal forming portion 108 in accordance with the input of the signal 107 is transferred to the signal storage/processing portion 110 and stored/processed so as to output an output signal 111.

(52) The output signal 111 is transferred to the display unit 112. The display unit 112 that received the output signal 111 displays a concentration display of the measured chemical component on a display screen of the display unit 112 as a value corresponding to the output signal 111.

(53) The above series of processes is controlled by the control unit 113 in accordance with instructions from the operation portion 114.

(54) The light-receiving sensor constituting the light-receiving sensor portion 106 may be a single element such as a photodiode, or a line sensor or area sensor in which a predetermined number of light-receiving pixels is one-dimensionally or two-dimensionally disposed, respectively.

(55) When the chemical component to be measured is not uniform in the object 104 to be measured, a measurement error resulting from positional dependency may decrease the measurement accuracy, and thus adoption of a line sensor or an area sensor is preferred. In particular, adoption of an area sensor that has a light-receiving surface having a size that covers an exiting surface from which the transmitted light 105 exits, orthogonal to the optical axis of the object 104 to be measured, can significantly increase measurement accuracy, and is thus preferred.

(56) While the light (L1) and the light (L2) have each been described using a light having a single wavelength, the wavelength is not necessarily limited thereto in the present invention, and the wavelength may have a bandwidth (wavelength range). That is, in the present invention, a luminous flux having a predetermined wavelength range may be used.

(57) Next, an example of actual concentration measurement using the system 100 of FIG. 2 will be described on the basis of FIGS. 3 and 4. FIG. 3 is a flowchart for explaining a preferred embodiment of the concentration measuring method of the present invention.

(58) When a button switch of the operation portion 114, or the like, for starting measurement is pressed, concentration measurement is started (step 201).

(59) In step 202, the existence or absence of the specimen 104 serving as the object to be measured, including if the specimen 104 is appropriately placed in a predetermined position, is determined. When it is determined that the specimen 104 has been appropriately placed, the first light (L1) and the second light (L2) necessary and appropriate for measuring the concentration of a chemical component to be measured in the specimen 104 are selected in step 202.

(60) Selection of the first light (L1) and the second light (L2) is made by setting the light source 101a for the first light (L1) and the light source 101b for the second light (L2) in predetermined positions in the optical concentration measuring system 100, or dispersing the light using a spectroscope.

(61) When selection is based on the establishment of a light source, selection of the first light (L1) and the second light (L2) can be made in advance from an absorption spectrum of the chemical component to be measured in the specimen 104, allowing step 203 to be performed before step 201.

(62) Next, in step 204, acquisition of an analytical curve for deriving the concentration value of the chemical component to be measured based on measurement data is started.

(63) The analytical curve can be acquired by reading the data of an analytical curve stored in advance in a storage portion of the optical concentration measuring system 100, or by creating a new analytical curve as described in FIG. 5.

(64) Once acquisition of the analytical curve is complete, measurement of the specimen 104 is started as indicated in step 206.

(65) When measurement is started, the first light (L1) and the second light (L2) are irradiated onto the specimen 104 for a predetermined period by time-sharing at a predetermined interval.

(66) The first light (L1) and the second light (L2) that passed through the specimen 104 are received by a light-receiving sensor set in the light-receiving sensor portion 106 (step 207).

(67) When the light-receiving sensor receives each transmitted light of the first light (L1) and the second light (L2) by time-sharing, an output signal of a size corresponding to the amount of received light is output each time light is received. In accordance with this output signal, log(1T) is calculated (step 208).

(68) Next, in step 209, whether or not log(1T) is in the range of the analytical curve is determined.

(69) If log(1T) is within the range of the analytical curve, the concentration of the targeted chemical component in the specimen 104 is derived on the basis of the analytical curve data (step 210).

(70) Next, in step 209, whether or not log(1T) is in the range of the analytical curve is determined.

(71) If log(1T) is within the range of the analytical curve, the concentration of the targeted chemical component in the specimen 104 is derived on the basis of the analytical curve data (step 210).

(72) FIG. 4 is a timing chart for explaining a signal output timing of the example in FIG. 3. That is, FIG. 4 is a timing chart showing the time responses of an output OUT1 of the first light source 101a, an output OUT2 of the second light source 101b, an output OUT3 of the light-receiving sensor, an output OUT4 of the differential signal, and a gas concentration GC.

(73) Here, output of the light source is the amount of light emitted during the period that the light is on (hereinafter ON period) and, when the light has high directivity, is substantially equivalent to the amount of light received by the light-receiving sensor.

(74) In the present invention, each light from the light sources 101a, 101b can be focused by the light-focusing optical portion 102 as illustrated in FIGS. 7 to 9, or a branch-type optical fiber 801 can be adopted as illustrated in FIG. 10, and thus as long as the light sources 101a, 101b are arranged by bringing an emitting surface of the light sources 101a, 101 b near or in contact with an incident surface of the light-focusing optical portion 102 or an incident surface of the branch-type optical fiber 801, it is possible to make the amount of light emitted during the ON period of each of the light sources 101a, 101b close to or substantially equivalent to the amount of light received by the light-receiving sensor.

(75) The gas concentration GC can, for example, be measured as a change in concentration of the target gas obtained by detecting an output signal (differential signal output OUT4) at timings T1 to T4 illustrated in FIG. 4 and deriving the value from the detected output signal value and the analytical curve acquired in advance.

(76) FIG. 4 illustrates a state of the gas concentration GC increasing in stages over time.

(77) When the output OUT1 of the first light source and the output OUT2 of the second light source are output on the same axis at mutually predetermined and repeated intervals at timings such as illustrated in FIG. 4, the gas to be measured does not exist before timing T1, and thus the output OUT3 of the light-receiving sensor is output as pulses S11, S21 having the same size.

(78) During the period between timings T1 and T2, the period between timings T2 and T3, and the period between the timings T3 and T4, the pulses S12, S22, S13, S23, S14, S24 are output. While the sizes of the pulses S12, S13, S14 are the same as the size of the pulse S11, the sizes of the pulses S22, S23, S24 decrease in stages in accordance with the level of light absorption of the gas to be measured.

(79) That is, because the light from the second light source is absorbed in the gas to be measured and the amount of light received by the light-receiving sensor gradually decreases in accordance with the gas concentration, the sizes of the pulses S22, S23, S24 decrease in stages in accordance with the level of concentration of the gas to be measured.

(80) FIG. 5 explains an example of a method for acquiring an analytical curve in advance, prior to measurement of the gas concentration. FIG. 5 is a flowchart for finding the analytical curve.

(81) To acquire the analytical curve, an analytical curve acquiring device is used.

(82) When acquisition of the analytical curve is started (step ST1), whether or not an optical measuring cell has been prepared is determined in step ST2.

(83) Once the optical measuring cell has been prepared, the flow proceeds to step ST3. In step ST3, whether or not a predetermined carrier gas has been introduced into the cell interior in a predetermined unit amount is determined.

(84) When it is determined that the predetermined carrier gas has been introduced into the cell interior in a predetermined unit amount, the flow proceeds to step ST4.

(85) This step of determining whether or not the carrier gas has been introduced may be omitted, or the step may be changed to a step for determining if the cell interior has reached a predetermined degree of vacuum. This determination of whether the cell interior has reached a predetermined degree of vacuum may be omitted as well.

(86) In either case, the cell interior needs to be cleaned before proceeding to step ST4 in order to acquire a more accurate analytical curve.

(87) In step ST4, a plurality of gases subject to concentration measurement is sequentially introduced into the cell, and the absorbance of the gas of each concentration is measured.

(88) Once measurement is completed, the flow proceeds to step ST5.

(89) In step ST5, the analytical curve is created on the bases of the absorbance measurement data.

(90) FIG. 6 illustrates an example of an analytical curve created in this way.

(91) FIG. 6 is a graph showing a relationship between the gas concentration GC and log(1T).

(92) Once the analytical curve is created, the flow can transition to concentration measurement of the specimen.

(93) Next, a preferred embodiment according to the present invention illustrated in FIGS. 7 to 10 will be described. In FIGS. 7 to 10, the same components as those in FIG. 2 will be denoted using the same reference numerals.

(94) FIG. 7 is an explanatory schematic configuration view for explaining a main component 100a of a preferred embodiment of the optical concentration measuring system that embodies the concentration measuring method of the present invention. FIG. 7 is an example of concentration measurement by transmitted light.

(95) In a main component 500, the light source portion comprises the first light source 101a that emits the first light (L1) and the second light source 101b that emits the second light (L2).

(96) The first light (L1) emitted from the first light source 101a is focused on the optical axis by the light-focusing optical portion 102, passed along the optical axis as an irradiated light 103a, and irradiated onto the object 104 to be measured. The amount of the irradiated light 103a not absorbed in the object 104 to be measured exits the object 104 to be measured as a transmitted light 105a.

(97) The transmitted light 105a enters the light-receiving surface of the light-receiving sensor portion 106.

(98) When the transmitted light 105a is received by the light-receiving sensor portion 106, the electric signal 107 photoelectrically converted in accordance with the amount of the transmitted light 105a is output from the light-receiving sensor portion 106.

(99) The signal 107 output from the light-receiving sensor portion 106 is input to the differential signal forming portion 108 configured by a differential signal forming circuit.

(100) The second light (L2) emitted from the second light source 101b is passed along the optical axis as an irradiated light 103b and irradiated onto the object 104 to be measured in the same way as the first light (L1), and a transmitted light 105b exits the object 104 to be measured accordingly.

(101) In the case of the second light (L2), the light is either not absorbed in the object 104 to be measured, or absorbed with a low absorbability compared to the first light (L1). Thus, the amounts of the irradiated light 103b and the transmitted light 105b are either the same or substantially the same, or the difference thereof is less than the difference between the irradiated light 103a and the transmitted light 105a.

(102) FIG. 8 is an explanatory schematic configuration view for explaining main components of another preferred embodiment of the optical concentration measuring system that embodies the concentration measuring method of the present invention. Except for the fact that FIG. 8 is an example of measurement by reflected light while FIG. 7 is an example of measurement by transmitted light, the example in FIG. 8 is the same as that in FIG. 7, and thus a detailed description thereof will be omitted.

(103) FIG. 9 is an explanatory schematic configuration view for explaining main components of yet another preferred embodiment of the optical concentration measuring system that embodies the concentration measuring method of the present invention.

(104) Except for the fact that FIG. 9 is an example of measurement by scattered light while FIG. 7 is an example of measurement by transmitted light, the example in FIG. 9 is the same as that in FIG. 7, and thus a detailed description thereof will be omitted.

(105) FIG. 10 is an explanatory schematic configuration view for explaining a main component of yet another preferred embodiment of the optical concentration measuring system that embodies the concentration measuring method of the present invention. Except for the fact that FIG. 10 adopts a branch-type optical fiber 801 for the light-focusing optical portion 102 in the example in FIG. 7, the example in FIG. 10 is the same as that in FIG. 7, and thus a detailed description thereof will be omitted.

(106) FIG. 11 illustrates a circuit diagram for explaining a preferred example of the differential signal forming portion adopted in the present invention.

(107) A differential signal forming portion 900 comprises a (charge) integrating amplifier 902, a sample/hold circuit 903, and a differential amplifier 904.

(108) When the transmitted light, reflected light, or scattered light produced upon irradiation of light having a predetermined wavelength for concentration measurement onto the object 104 to be measured subject to concentration measurement, such as a fruit or a vegetable, is received by a photodiode 901 for light reception, an electric signal P1 corresponding to the amount of received light is output from the photodiode 901. The electric signal P1 is input to the integrating amplifier 902. The integrating amplifier 902 is provided for sensitivity enhancement so as to allow measurement down to subtle changes in gas concentration of the specimen 107.

(109) The output signal of the integrating amplifier 902 is input to the sample/hold circuit 903.

(110) A sampled/held analog signal is input to the differential amplifier 904.

(111) Gas Concentration Measurement Example Embodying Present Invention

(112) Next, an example that embodies the present invention will be described using a gas concentration measurement example.

(113) A preferred embodiment of the concentration measuring method for measuring concentration by using a plurality of lights having different wavelengths and irradiating the plurality of lights by time-sharing will now be described.

(114) In the following, a preferred embodiment of a gas concentration measurement example that uses transmitted light for measurement will be primarily described.

(115) Cases where reflected light or scattered light is used for measurement rather than transmitted light, needless to say, also fall into the category of the present invention, and are naturally within the technical field.

(116) Further, the embodiment described below, needless to say, can be easily developed even in a case where the concentration of a solution or the sugar content of a fruit or a vegetable is measured rather than the concentration of a gas.

(117) To embody the present invention as a gas concentration measuring device, the measuring device may comprise a regular light source, a light-receiving photodiode, electronic circuit components, and the like that are easily acquirable, based on a premise of compatibility with the measurement target, and thus in the following descriptions matters obvious to persons skilled in the art will be omitted and main points will be simplified.

(118) The specimen (object to be measured) is, for example, a gas that flows through a gas pipe.

(119) The gas pipe is provided with an incident surface into which light (a measured light h) used for measurement enters, and an exiting surface from which light, having passed through the gas pipe, exits to the outside.

(120) The incident surface and the exiting surface are made of a material having a transmittance of 1 or substantially 1 with respect to the measured light h.

(121) Regardless of whether the gas that flows through the gas pipe is a single type or a plurality of types of mixtures, the measuring device can measure the concentration of the target gas.

(122) In the following, the case of the single type is described using trimethylgallium (TMGa), for example, as the gas serving as the specimen.

(123) Other examples of the specimen gas type include trimethylindium (TMIn) and titanium tetrachloride (TiCl4).

(124) In the gas concentration measurement of trimethylgallium (TMGa), an LED that emits light (L1) having a center light wavelength of 500 nm is adopted as the first light source 101a, for example, and the light intensity thereof is 1.0 mW/cm.sup.2/nm.

(125) An LED that emits light (L2) having a center light wavelength of 230 nm is adopted as the second light source 101b, and the light intensity thereof is 1.0 mW/cm.sup.2/nm.

(126) In the present invention, the light (L1) 103a emitted from the first light source 101a and the light (L2) 103b emitted from the second light source 101b are transmitted through the specimen 104 at separate times (by time-sharing), and enter the light-receiving sensor of the light-receiving sensor portion 106. As the light-receiving sensor, a photodiode (S336-18BQ) manufactured by Hamamatsu Photonics K.K, for example, may be used. The received light sensitivity of the light-receiving sensor in this case is 0.26 A/W at a light wavelength of 500 nm, and 0.13 A/W at a light wavelength of 230 mm.

(127) The output signal 107 of the light-receiving sensor portion 106 is input to the differential signal forming circuit 108, and the output signal 109 is output from the differential signal forming circuit 108 accordingly.

(128) A light source that emits light having an absorbance that changes depending on the concentration of the gas of the specimen 104, and a light source that emits light having an absorbance that does not or substantially does not change depending on the concentration of the gas of the specimen 104 are adopted as the first light source 101a and the second light source 101b, respectively.

(129) While the above gas concentration measurement example has been described using the configuration in FIG. 7 that measures transmitted light, naturally the measurement can be applied to the configuration in FIG. 8 that uses a reflected light and to the configuration in FIG. 9 that uses a scattered light without having to particularly re-describe the details.

(130) Further, while an optical path of the first light source 101a and an optical path of the second light source 101b differ in the object 104 to be measured if the light-focusing optical portion 102 does not exist in the configuration illustrated in FIG. 7, preferably the first light source 101a and the second light source 101b are arranged as close to each other as possible so as to bring the optical paths as close to the same optical path as possible.

(131) Or, the optical paths can be made substantially identical when the branch-type optical fiber 801 is adopted as illustrated in FIG. 10 in place of the light-focusing optical portion 102, and thus adoption of the branch-type optical fiber 801 is preferred.

(132) FIG. 11 is a configuration diagram for explaining a configuration of a preferred example of the differential signal forming circuit.

(133) The differential signal forming circuit 900 illustrated in FIG. 11 is provided with the (charge) integrating amplifier 902 to increase sensitivity so that subtle changes in the gas concentration of the specimen 107 can be measured.

(134) The output signal of the (charge) integrating amplifier 902 is input to the sample/hold circuit 903.

(135) A sampled/held analog signal is input to an analog-digital converter (ADC) 1301.

(136) An optical signal based on the first light source, an optical signal based on the second light source, and a differential signal between these two signals are output from the ADC 1301.

(137) FIG. 4 is a timing chart showing the time responses of the output OUT1 of the first light source 101a, the output OUT2 of the second light source 101b, the output OUT3 of the light-receiving sensor, the output OUT4 of the differential signal, and the gas concentration GC, and this is as previously described.

(138) Here, output of the light source is the amount of light emitted during the ON period and, when the light has high directivity, is substantially equivalent to the amount of light received by the light-receiving sensor.

(139) In the present invention, the light from the light sources 101a, 101b can be focused by the light-focusing optical portion 102 as illustrated in FIGS. 7 to 9, or the branch-type optical fiber 801 can be adopted as illustrated in FIG. 10, and thus as long as the light sources 101a, 101b are arranged by bringing the emitting surface of the light sources 101a, 101b near or in contact with the incident surface of the light-focusing optical portion 102 or the incident surface of the branch-type optical fiber 801, it is possible to make the amount of light emitted during the ON period of the light sources 101a, 101 b close to or substantially equivalent to the amount of light received by the light-receiving sensor.

(140) In general, absorbance is given based on the following formula:
[Formula 1]
log(I/I.sub.c)=log(1T)=K (1)

(141) Here, I.sub.0 indicates the intensity of the incident light, I indicates the intensity of the transmitted light, and K indicates the gas concentration. is a coefficient and is determined by an optical path length in the specimen 104, a light absorption coefficient of the gas subject to concentration measurement in the specimen 104, and the like.

(142) Further, T indicates the absorbance difference. In this embodiment, the optical path lengths are set so that a is substantially 0 for the first light source 101a, and 2.1810-4/ppm for the second light source 101b. Given I.sub.1 as the intensity of the transmitted light of the light (L1) emitted from the first light source 101a and I.sub.2 as the intensity of the transmitted light of the light (L2) emitted from the second light source 101b, formula (1) can be modified to formula (2) when I.sub.1 uses the fact that the transmittance difference with respect to the optical wavelength of the first light source, regardless of gas concentration, is substantially 0.

(143) $\begin{array}{cc}\left[\mathrm{Formula}2\right]& \\ -\log \left(l-T\right)=-\log \left(l-\begin{array}{c}X\\ I_1\end{array}\right)=K& \left(2\right)\end{array}$

(144) Here, X is the output value of the differential signal, and is equivalent to I.sub.2I.sub.1.

(145) According to this formula, the absorbance of the specimen 104 can be measured with high accuracy using the output OUT1 of the first light source 101a having an absorptivity that changes in accordance with the gas concentration, and the output OUT2 of the second light source 101b having an absorptivity that does not change in accordance with the gas concentration.

(146) Thus, there is no need to measure gas concentrations to create an analytical curve for each measurement using known reference samples.

(147) A gas densitometer can measure changes in absorptivity in a stable manner, even if there are changes in the measurement system, gas temperature, or the like.

(148) Setup is performed so that an integrated charge (1) of the integrating amplifier 902 based on the first light source 101a and the integrating charge (2) of the integrating amplifier 902 based on the second light source 101b when the gas concentration is 0 are equal or substantially equal.

(149) Here, in this embodiment, an integration period (1) during output of the first light source 101a and an integration period (2) during output of the second light source 101b were adjusted so that the charges were 6.1109 C.

(150) The integration period (1) and the integration period (2) of this embodiment were set to 4.0 msec and 2.0 msec, respectively.

(151) FIG. 15 shows a relationship between an absorbance value measured with respect to a gas concentration and a value equivalent to three times a standard deviation of a noise superimposed on the measured signal at this time.

(152) Further, when measurement was made using this charge, the main noise component was confirmed as photon shot noise.

(153) Based on the results, when the charge value is 6.110-9 C, the effect of the photon shot noise proportional to the square root of the signal charge became relatively small, making it possible to measure an absorbance difference T up to 510-5 with 99% reliability. That is, the gas concentration could be measured to an accuracy of 0.1 ppm.

(154) Further, according to the embodiment of the present invention, output is obtained from a difference between signals based on two lights having different wavelengths, even if the temperature changes, making it possible to cancel an amount of fluctuation in a transmittance that changes according to temperature. Thus, even if there is temperature fluctuation during measurement, stable sensitivity can be achieved with high accuracy.

(155) In the present invention, a communication module for short-range communication, such as WiFi, Bluetooth (registered trademark), or Near Field Communications (NFC), or a communication module for satellite communication is incorporated in the concentration measuring device that embodies the present invention, making it possible to make the concentration measuring device function as an information terminal device on a network. For example, a patient in a hospital can measure his or her blood sugar level in the hospital bed using a non-invasive type of concentration measuring device according to the present invention when it is time for measurement or when instructed by the nurse station, and send the measurement data as is to the nurse station. This makes it possible to alleviate the labor burden of a nurse in terms of making hospital room visits for each patient and taking measurements.

(156) Furthermore, while, for example, a person at risk for diabetes, a person with a low or high blood sugar level being observed and treated at home, or the like may experience an abnormality in blood sugar level while driving a vehicle, become light-headed, no longer be able to drive or find it difficult to drive normally, and cause an accident, such a person can wear a non-invasive type concentration measuring device that comprises a communication function according to the present invention and have the device perform measurements while he or she is driving. In such a case, the device can detect an abnormality in blood sugar level, immediately send the signal indicating abnormality detection to the vehicle that the person is driving, and automatically stop the vehicle in a prompt manner or automatically guide the vehicle to a safe area such as the side of the road and stop the vehicle. Moreover, carried insulin can then be administered and recovery to normalcy achieved.

(157) Further, the data of the abnormal detection can be automatically sent along with necessary personal data of the driver to a family doctor or nearby hospital to request emergency instructions from the hospital.

(158) While FIG. 11 illustrates a preferred example of the differential signal forming circuit in the realization of the present invention, the present invention is not limited thereto, allowing adoption of the differential signal forming circuits illustrated in FIGS. 12 to 14 as preferred examples as well.

(159) In FIGS. 12 to 14, components that fulfill the same functions as those denoted with the reference numerals in FIG. 11 are denoted using the same reference numerals as FIG. 11.

(160) The configuration illustrated in FIG. 12 is the same as that in FIG. 11 except that, in addition to a circuit for a differential signal output 905, a circuit for a pre-differential signal output 1001 has been added.

(161) With the addition of the circuit for the pre-differential signal output 1001, there is the advantage that, compared to the configuration illustrated in FIG. 11, even if fluctuation occurs in the absolute value of absorbance due to temperature change or the like, or temporal fluctuation occurs in the light output of the light source, the amount of these fluctuations can be measured and calibrated.

(162) In the configuration illustrated in FIG. 13, two systems for signal transmission (sample/hold circuits 903a, 903b.fwdarw.differential amplifiers 904a, 904b) and the ADC 1301 are further provided compared to the configuration illustrated in FIG. 12.

(163) This configuration results in the advantage of being able to eliminate the offset of the integrating amplifier compared to that in FIG. 12.

(164) FIG. 14 is an example of a circuit designed in more detail than the example in FIG. 13.

(165) In FIG. 14, an integrating (accumulation) amplifier portion 1401, which is similar to the integrating amplifier 902, and a 1/10 amplifier portion 1402 are provided. In addition, the differential amplifier portions 904a, 904b are each provided with two instrumentation amplifiers for differential output.

(166) Such a configuration results in the advantage of being able to eliminate the offset of the differential amplifiers.

(167) Next, an embodiment of a preferred example of an electronic device comprising the concentration measuring function according to the present invention will be described.

(168) FIGS. 16 and 17 are outline configuration views illustrating an embodiment when the present invention is applied to a mobile terminal device.

(169) FIG. 16 is an outline external view, and FIG. 17 is a block diagram of the internal configuration.

(170) A mobile terminal device 1701 illustrated in FIGS. 16 and 17 comprises a global positioning system (GPS) positioning portion 1703, a calculation processing portion 1704, a storage device 1705, and a display unit 1706.

(171) When the device does not require GPS positioning, the GPS positioning portion 1703 is omitted.

(172) Further, the device may comprise the GPS positioning portion 1703, and an acceleration sensor 1708 and an angular velocity sensor 1709 may be omitted.

(173) Examples of the mobile terminal device 1701 include a mobile electronic device such as a mobile telephone device having a navigation function, a personal digital assistant (PDA), a tablet, or a mobile PC, a wristwatch, and a wearable article such as a scouter, a necklace, a ring, or a bracelet having an electronic device function.

(174) Examples of the mobile terminal device 1701 further include a mobile barometer or altimeter for mountain climbing, and a stopwatch.

(175) The mobile terminal device 1701 is capable of intercommunicating with a device equipped with a transceiver function such as a transceiver base, a transceiver satellite, a NAVI system mounted to a vehicle, a handheld NAVI device, a transceiver connected to a private network system, or other mobile terminal device.

(176) Description is given in the following using the example of a transceiver satellite 1702 as an example of a device equipped with a transceiver function.

(177) The GPS positioning portion 1703 functions as a first current position calculating portion that receives a position information signal sent from the transceiver satellite 1702 and identifies a current position.

(178) The calculation processing portion 1704 receives detection signals of the vertical acceleration sensor 1708 that detects a number of steps and the angular velocity sensor 1709 that detects a direction, autonomously identifies the current position based on these, and executes navigation processing.

(179) The calculation processing portion 1704 comprises a microcomputer, a central processing unit (CPU), and the like.

(180) The storage device 1705 comprises a ROM 1705a that stores a processing program executed by the calculation processing portion 1704 and stores a storage table required in calculation processing, a RAM 1705b that stores calculation results and the like required in calculation processing, and a non-volatile memory 1705c that stores the current position information when navigation processing ends.

(181) The display unit 1706 displays navigation image information output from the calculation processing portion 1704, and comprises a liquid crystal display unit, an organic EL display unit, or the like.

(182) A clock portion 1707 displays a year, month, day, and time corrected using the current time information that indicates the year, month, day, and time output from the GPS positioning portion 1703 when the GPS positioning portion 1703 is activated.

(183) The calculation processing portion 1704 receives the current position information output from the GPS positioning portion 1703, the current time information that indicates the year, month, day, and time output from the clock portion 1707, the acceleration information output from the acceleration sensor 1708 mounted on a hip position of the user that retains the mobile terminal device 1701, the angular velocity information corresponding to the direction of the walking by the user and output from the angular velocity sensor 1709, such as a gyroscope, mounted to the mobile terminal device 1701, and concentration measurement information from a concentration measuring portion 1701 according to the present invention.

(184) The concentration measuring portion 1710 comprises the optical concentration measuring system illustrated in FIGS. 7 to 10 or an optical concentration measuring device comprising the same functions as the system, and may be detachably mounted to the mobile terminal device 1701 main body or integrally configured with the main body.

(185) When the concentration measuring portion 1710 is detachably mounted to the main body, the concentration measuring portion 1710 can be removed from the main body at the time of measurement and, for example, brought into contact with the body of a person, allowing measurement of the sugar level in the blood, for example.

(186) The concentration measuring portion 1710 and the main body are both provided with a communication module for short-range communication, such as Wifi, Bluetooth (registered trademark), or NFC, making it possible to perform communication between the concentration measuring portion 1710 and the main body even when the concentration measuring portion 1710 is removed from the main body.

(187) According to the mobile terminal device 1710, concentration measurement data, position information data, and specific individual data stored in the storage device 1705 can be sent to a transmission destination. For example, when an abnormality arises in the blood sugar level of a person while driving a vehicle, a signal indicating the abnormality is sent to the vehicle, causing the vehicle to automatically stop and, at the same time, the concentration measurement data, the position information data, and specific individual data is sent to a family doctor or a hospital in which the family doctor is located, making it possible to request instructions for appropriate treatment from the doctor and, in some cases, promptly dispatch an emergency vehicle.

(188) A communication portion 1711 that performs wireless communication with an external wireless communication device is connected to the calculation processing portion 1704.

(189) The ROM 1705a stores a storage table of position information by region.

(190) Additionally, the ROM 1705a stores an autonomous positioning calculation program for performing autonomous positioning calculations, and a calculation portion selection processing program for selecting either current position information calculated by the GPS positioning portion 1703 or current position information calculated by the autonomous positioning calculation processing performed by the autonomous positioning program.

(191) The storage table of position information by region charts the names of prefectures across the country, the seat names of governments of each prefecture, and the latitude (N) and the longitude (E) of each seat of government.

(192) The calculation processing portion 1704 executes the autonomous positioning calculation processing in accordance with the autonomous positioning calculation program that performs autonomous positioning calculations.

(193) This autonomous positioning calculation processing is started when autonomous calculation processing is selected by the calculation portion selection processing and, once the previous current position identified by the GPS positioning portion 1703 is set as the initial position in the initial state, is executed as timer interrupt processing every predetermined time period (10 msec, for example) with respect to a predetermined main program.

(194) That is, first the autonomous positioning calculation processing reads an angular velocity v detected by the angular velocity sensor 1709, then integrates the angular velocity v, calculates the direction , and transitions to the next step.

(195) In the next step, the autonomous positioning calculation processing reads a vertical acceleration G detected by the acceleration sensor 1708, calculates a number of steps P from a change pattern of the vertical acceleration G, multiplies a pace width W set in advance by the calculated number of steps P to calculate a moved distance L, updates the current position information on the basis of the calculated direction and the moved distance L, displays the updated current position information on the display unit 1706 over map information, ends the timer interrupt processing, and returns to the predetermined main program.

(196) Furthermore, the calculation processing portion 1704 executes calculation portion selection processing that selects either the current position information identified by the GPS positioning portion 1703 in accordance with the calculation portion selection processing program or the current position information identified by the autonomous positioning calculation processing.

(197) According to this calculation portion selection processing, execution is started when the navigation processing is selected on the mobile terminal device 1701 after power ON.

(198) Examples of the mobile terminal device 1701 include a mobile electronic device such as a mobile telephone device having a navigation function, a personal digital assistant (PDA), a tablet, or a mobile PC, a wristwatch, and a wearable article such as a scouter, a necklace, a ring, or a bracelet having an electronic device function.

(199) While in the examples heretofore formation of the differential signal has been exemplified by formation via an electric circuit (hardware) such as a differential circuit and a differential amplification circuit, the present invention is not limited thereto, allowing formation using software of digital calculation processing.

(200) An example of a preferred embodiment will be described using FIG. 18.

(201) The embodiment illustrated in FIG. 18 comprises a differential signal forming portion 1800 and a light-receiving sensor portion 1801.

(202) The differential signal forming portion 1800 comprises an integrated circuit portion 1802, an analog-digital converting (A/D converting) portion (ADC) 1803, and a differential signal forming element portion 1804.

(203) The light-receiving sensor portion 1801 is provided with a photodiode 1805 as a light-receiving sensor for measurement. The integrated circuit portion 1802 is provided with an operational amplifier 1806, a capacitor C1, and a switch SW1.

(204) While the example of the differential signal forming portion 900 illustrated in FIG. 11 forms the differential signal 905 using an analog signal, a differential signal 1809 in the example illustrated in FIG. 18 is formed by performing digital calculation processing after analog-digital conversion (A/D conversion) of a signal 1807 output from the integrated circuit portion 1802.

(205) An output terminal of the photodiode 1805 is electrically connected with an inverting input pin of the operational amplifier 1806.

(206) The non-inverting pin of the operational amplifier 1806 is grounded.

(207) Between the integrated circuit portion 1802 and the ADC 1803, a switch SW2 is provided as necessary and a signal transmission path is formed. The signal transmission path can be formed by electrically connecting the area between the integrated circuit portion 1802 and the ADC 1803.

(208) When two lights (a first light and a second light) differing in wavelength or wavelength band are sequentially irradiated by time-sharing onto an object (specimen) to be measured, the first light and the second light that pass through the object to be measured are sequentially received by the photodiode 1805 by time-sharing in accordance with the irradiation.

(209) When the photodiode 1805 receives the light, an optical charge is produced, and the optical charge is accumulated in the capacitor C1. A signal 1807 of a voltage of a size corresponding to this accumulated charge is output from the integrated circuit portion 1802 when the switch SW2 is turned ON. The signal 1807 is input to the analog-digital conversion means (ADC) 1803, converted into a digital signal, and output from the ADC 1803 as a signal 1808. The digitized signal 1808 is input to the differential signal forming element portion 1804.

(210) Either a signal 1808a corresponding to the first light or a signal 1808b corresponding to a second light, whichever is input first, is temporarily saved in the differential signal forming element portion 1804 interior at least until the signal to be subsequently input is input.

(211) When the signals 1808a, 1808b respectively corresponding to the first light and the second light to be measured are sequentially input to the differential signal forming element portion 1804, differential signal formation processing is implemented in the differential signal forming element portion 1804 on the basis of these signals 1808a, 1808b, and the differential signal 1809 is output from the differential signal forming element portion 1804.

(212) As described above, the concentration measuring method of the present invention has universality, i.e., the ability to be embodied in various forms and modes.

DESCRIPTIONS OF REFERENCE NUMERALS

(213) 100 Optical concentration measuring system 100-1 Optical concentration measuring sub-system 100-2 Control/Operation sub-system 100-3 Optical concentration measuring device 101 Light source portion 101a, 101b Light source 102 Light-focusing optical portion 103, 103a, 103b Irradiated light 104 Object to be measured 105, 105a, 105b Transmitted light 106 Light-receiving sensor portion 107, 107a, 107b Electric signal 108 Differential signal forming portion 109 Differential output signal 110 Signal storage/processing portion 111 Output signal 112 Display unit 113 Control unit 114 Operation portion 201 to 211 Step 500, 600, 700, 800 Optical gas concentration measuring system 801 Branch-type optical fiber 801a, 801b Branch optical path 802a, 802b Irradiated light 900, 1000, 1300, 1400 Differential signal forming portion (circuit configuration) 901 Photodiode 902 Integrating amplifier 903, 903a, 903b Sample/Hold circuit 940, 904a, 904b Differential amplifier 905 Differential signal output 906 Pre-differential signal output 1101 Differential signal forming element portion 1301 ADC 1302 Signal output 1401 Integrating amplifier portion 1402 1/10 integrating amplifier portion 1701 Mobile terminal device 1703 GPS positioning portion 1704 Calculation processing portion 1705 Storage device 1706 Display unit 1708 Acceleration sensor 1709 Angular velocity sensor 1800 Differential signal forming portion 1801 Light-receiving sensor portion 1802 Integrated circuit portion 1803 Digital-analog converting portion 1804 Differential signal forming element portion 1805 Photodiode 1806 Operational amplifier 1807, 1808 Signal 1809 Differential signal L1 Light having a first wavelength L2 Light having a second wavelength