JP2006284225A - Potential measuring method and measuring instrument - Google Patents

Potential measuring method and measuring instrument Download PDF

Info

Publication number
JP2006284225A
JP2006284225A JP2005101496A JP2005101496A JP2006284225A JP 2006284225 A JP2006284225 A JP 2006284225A JP 2005101496 A JP2005101496 A JP 2005101496A JP 2005101496 A JP2005101496 A JP 2005101496A JP 2006284225 A JP2006284225 A JP 2006284225A
Authority
JP
Japan
Prior art keywords
charge
floating diffusion
potential
unit
sensing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2005101496A
Other languages
Japanese (ja)
Inventor
Susumu Mimura
享 三村
Original Assignee
Horiba Ltd
株式会社堀場製作所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Horiba Ltd, 株式会社堀場製作所 filed Critical Horiba Ltd
Priority to JP2005101496A priority Critical patent/JP2006284225A/en
Publication of JP2006284225A publication Critical patent/JP2006284225A/en
Application status is Pending legal-status Critical

Links

Images

Abstract

PROBLEM TO BE SOLVED: To quantify a minute change with excellent responsiveness by converting a physical phenomenon or a chemical phenomenon into charge information, and at the same time a wide measuring range corresponding to a measuring object or a measuring purpose. It is an object of the present invention to provide a measurement method or a measurement apparatus having high measurement accuracy capable of measuring both narrow measurement ranges with a single means.
The physical phenomenon is achieved by supplying a charge from a charge supply unit to a sensing unit, taking out the supplied charge from the sensing unit through a floating diffusion, and detecting the amount of the supplied charge. Alternatively, it is a method for measuring a potential related to a chemical phenomenon, in which a measurement range is set in accordance with the magnitude of a change in physical or chemical quantity, and the number of times the moving charge is accumulated in the floating diffusion 5 is set. The number of accumulations is controlled based on the set measurement range.
[Selection] Figure 1

Description

  The present invention relates to a measurement method and apparatus for quantifying a physical phenomenon or chemical phenomenon, and for example, a measurement method for quantifying various physical or chemical phenomena such as a two-dimensional distribution of pH, pressure, magnetic field, or temperature of a solution. And apparatus.

  Physical or chemical phenomena include various phenomena such as concentration, temperature, magnetism, pressure, acceleration, velocity, sound wave, ultrasonic wave, redox potential, reaction rate, etc. These phenomena are various electric signals (currents). , Voltage, resistance, charge capacity, potential).

  Also, for example, a method of measuring the light quantity by changing the light quantity into a charge quantity and evaluating the charge quantity, such as a photodiode, when light is irradiated, generates an electron-hole pair according to the quantity of light. In addition, there is a method for measuring physical phenomena or chemical phenomena by converting them into charge information.

  However, in other physical and chemical phenomena other than light, in most cases, instead of the amount of charge, it is converted into an electrical signal such as a voltage value, current value, resistance value, etc., so that those values are read. Accumulation and transfer, which are peculiar to electric charges, cannot be performed, and it is very difficult to simultaneously acquire information from a plurality of points and perform high-speed processing or to image measurement results.

  In recent years, there has been an increasing demand for high-speed processing or imaging of such physical or chemical phenomena in various fields including the environment and medical fields. For example, the depth corresponding to the magnitude of physical or chemical quantities. By supplying electric charge to a potential well configured to change the above, and converting the physical or chemical quantity into electric charge according to the size of the potential well, the information of a plurality of points is simultaneously captured, There has been proposed a method and an apparatus that perform storage, transfer, and the like, so that various physical phenomena or chemical phenomena can be easily imaged (see, for example, Patent Document 1). Specifically, a measurement method or apparatus using a MOS field effect transistor (MOS FET), an ion sensitive field effect transistor (ISFET), or a so-called chemical CCD is applicable as the device.

For example, as shown in FIG. 10, on the surface of a semiconductor substrate 51, an input diode portion 52 and a floating diffusion portion 53 that are diffusion regions opposite to the substrate, and an insulating film 55 between the input diode portion and the floating diffusion portion. An input gate 56 and an output gate 57 fixed above, a sensing part 59 made of an ion sensitive film fixed on an insulating film between the input / output gates, and a position connected to the other side of the floating diffusion part A reset gate 58 fixed on the insulating film, and a reset diode portion 54 having a diffusion region opposite to the substrate formed on the opposite side of the floating diffusion portion in the reset gate, and having an ion concentration that acts on the sensing portion. Ion concentration detection and salt using a FET type sensor that detects the amount of charge accumulated in the floating diffusion section according to the depth of the potential well and the number of pumps that change accordingly. FET sensor for detecting the sequences have been proposed (e.g. see Patent Document 2).
JP-A-10-332423 WO2003 / 042683

  However, recent measurement of physical or chemical phenomena requires precise measurement accuracy and faster response, and there is a strong demand for better accuracy or response to the above methods and devices. I came. At the same time, with the application to a wide range of applications, there has been a strong demand for measurement devices to expand a wide measurement range, that is, a dynamic range. In other words, it has become an important issue to be a highly sensitive measuring device that detects very minute changes and at the same time a measuring device having a wide measuring range. Note that the “measurement range set according to changes in physical or chemical quantities” herein refers to a so-called measurement range. For example, in the measurement of hydrogen ion concentration (pH), the reference value is 0 (zero). ), When the maximum value is 14, the pH is 0 to 14, and when the reference value is 7.0 and the maximum value is 7.1, the pH is 7.0-7.1.

  Specifically, for example, in the measurement of the hydrogen ion concentration (pH), in a normal measuring apparatus, the reference value is 0 (zero) and the maximum value is 14 to pH 0-14, but the reaction in the process In the case of precisely managing the state, a measuring device (for example, measuring range pH 6.8000 ± 0.0001) that can measure a change of a maximum of 0.0001 with a reference value of 6.8000 is required. Conventionally, when these measurement ranges are completely different, it has been dealt with by a plurality of measurement devices having different measurement ranges. However, in the same process, there is a large pH change at the rise, while in a stable state, the pH is stable. In many cases, it is necessary to manage such that there is no change, and the demand for tracking with the same measuring device is higher than before, and it has become a stronger demand these days.

  In addition, in the conventional method, if a detector capable of capturing a change in a small physical phenomenon or chemical phenomenon as a relatively large change in charge for a measurement with high detection sensitivity is configured, Or, if a change in chemical phenomenon occurs, an excessive charge is generated, leading to saturation of the output of the detector (saturation phenomenon) or deterioration of linearity. Conversely, if the detector is configured under conditions that can accurately detect changes in large physical or chemical phenomena, it can avoid the disadvantage that the detection accuracy for small changes in physical or chemical phenomena is greatly reduced. was difficult.

  In addition, as a method for improving the detection sensitivity, “Even in the potential well inlet adjustment type sensor, when the transfer is performed n times, the S / N ratio increases by √n times compared to the case where the time accumulation is not performed. Therefore, it is obvious that even if a change in the depth of the potential well immediately below the sensing part is very small, it can be detected reliably based on the change in the surface potential of the sensing part. It is possible to detect the change in the ion concentration based on the reaction or the binding to the ion or the change in the ion concentration based on the catalytic reaction of the fixed body with high sensitivity ”(see Patent Document 2). Although it is known that a measuring device capable of arbitrarily setting a measuring range for various objects, or a measuring device having a wide dynamic range as described above, The current was very difficult.

  Therefore, an object of the present invention is to convert a physical phenomenon or a chemical phenomenon into charge information, thereby quantifying a minute change with excellent responsiveness and at the same time corresponding to a measurement object or a measurement purpose. Another object of the present invention is to provide a measurement method or a measurement apparatus having high measurement accuracy capable of measuring both a wide measurement range and a narrow measurement range with a single means.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by the following measuring method or measuring apparatus, and have completed the present invention.

  The present invention supplies a charge from a charge supply unit to a sensing unit whose potential changes according to the magnitude of a physical or chemical quantity, and takes out the supplied charge from the sensing unit via a floating diffusion. A method for measuring a potential related to a physical phenomenon or a chemical phenomenon by detecting the amount of supplied charge, setting a measurement range in accordance with the magnitude of a change in physical or chemical amount, and moving The number of charges to be stored in the floating diffusion is set, and the number of charges is controlled based on the set measurement range.

  As described above, it is required that both a wide measurement range in normal measurement and a narrow measurement range in minute change measurement can be measured by one means corresponding to the measurement object or measurement purpose. The present invention makes use of the characteristics of semiconductor devices that use charge accumulation, such as chemical CCDs, and sets the means for setting the measurement range according to the magnitude of the change in physical or chemical quantity and sets the number of times the charge is moved. It has been found that by measuring the number of times of accumulation in accordance with the measurement range, it is possible to cover a measurement range that is greatly different in width by a single measurement means.

  In other words, when the sensitivity is low (when the measurement range is wide or when measuring high concentration), the maximum amount of charge transferred at one time increases, so the number of accumulations is reduced, and when the sensitivity is high (the measurement range is narrow). In the case of measurement or low concentration measurement), the maximum number of charges transferred at one time is reduced, so that the number of accumulation is increased. Thus, by making the control of the number of accumulations correspond to the measurement range, it is possible to provide a measurement method that can be applied to a measurement range in which the width is greatly different.

  Here, the “number of times of accumulation in the floating diffusion” is not limited to the number of times the charge transferred from the sensing unit is directly accumulated in the floating diffusion, but is a wide range, for example, charge accumulation provided between the sensing unit and the floating diffusion. The number of times of accumulation in the unit (after being transferred and accumulated a plurality of times in the charge accumulation unit, the accumulated charges for a plurality of times are collectively transferred to the floating diffusion).

  The present invention is the above-described potential measurement method, characterized in that the number of times of accumulation in the floating diffusion can be changed in conjunction with the amount of charge accumulated in the floating diffusion by a predetermined number of transfers.

  In the measurement of physical or chemical quantities, for example, the measurement range can often be estimated in advance, such as pH measurement in a chemical reaction process, and for example, the measurement range of a specific ion concentration of an unknown substance can be estimated in advance. It may be difficult to guess. In the former case, it is possible to set the number of accumulations or the range of the number of accumulations to be controlled in advance according to the measurement range. The present invention proposes a countermeasure for the latter. By controlling the number of times of accumulation in conjunction with the amount of charge accumulated in the floating diffusion by a predetermined number of transfers, the optimum number of times of accumulation or the range of the number of times of accumulation to be controlled. Setting is possible.

  The “predetermined number of transfers” here means (1) a plurality of times of transfer when the detection sensitivity, that is, the measurement range is set in advance and the charge accumulation number is automatically set. The number of times is set based on the result of measuring the charge amount accumulated by carrying out the measurement in advance before the sample measurement, and the preliminary measurement is not reflected in the final measurement result. (2) In addition, when the optimum detection sensitivity, that is, the measurement range is set for the sample condition, and the number of charge accumulations is automatically set, the transfer is a plurality of times. The number of times is set based on the results of multiple measurements performed at the beginning of sample measurement, and the measurement performed at the beginning is also reflected in the final measurement result.

  The present invention also provides a charge supply unit that supplies charges to the sensing unit, a sensing unit that changes in potential according to the magnitude of a physical or chemical amount, and a floating diffusion that extracts the charge supplied to the sensing unit. A potential measuring device having a detection unit comprising: means for setting a measurement range according to the magnitude of a change in physical or chemical quantity; means for setting the number of times a moving charge is accumulated in a floating diffusion And a control unit that can change the number of times of accumulation in the floating diffusion by controlling the operation of the barrier unit provided between the sensing unit and the floating diffusion.

  The present invention utilizes the characteristics of a semiconductor device using charge accumulation, such as a chemical CCD. Means for setting a measurement range according to the magnitude of a change in physical or chemical quantity, and the number of charges accumulated to move. It is possible to provide a measuring apparatus that can be applied to a measurement range in which the width is largely different by having a means for setting the number of times and controlling the number of accumulations to correspond to the measurement range. At this time, it is preferable that the element or part to be controlled is in the previous stage of charge transfer as much as possible. In the present invention, by controlling the operation of the barrier unit provided between the sensing unit and the floating diffusion and the reset gate, it is possible to quickly set the appropriate number of accumulations, and to achieve a suitable control effect. Obtainable. For example, this is advantageous when feedback control is performed based on the amount of charge accumulated in the floating diffusion.

  The present invention relates to a charge supply unit that supplies charges to a sensing unit, a sensing unit that changes in potential according to the magnitude of a physical or chemical amount, and a sensing charge accumulation that accumulates charges transferred from the sensing unit. Measuring device having a detection unit comprising a floating diffusion for taking out the charge supplied to the sensing charge storage unit, and setting a measurement range according to the magnitude of a change in physical or chemical quantity The number of times of accumulation in the floating diffusion can be changed by the means for setting, the means for setting the number of times the moving charge is accumulated in the floating diffusion, and the operation of the threshold portion provided between the sensing charge accumulation unit and the floating diffusion. It has a control means.

  As described above, the present invention has a means for setting a measurement range and a means for setting the number of times of accumulation of moving charges, and by making the control of the number of times of accumulation correspond to the measurement range, the measurement range in which the width varies greatly It is possible to provide a measuring apparatus applicable to the above. At this time, if the change in the potential of the sensing unit is very small, a large change in the potential of the adjacent part may affect the measurement potential of the sensing unit, and the sensing charge accumulation provided between the sensing unit and the floating diffusion And controlling the operation of the threshold unit provided between the sensing charge storage unit and the floating diffusion, it is possible to quickly set an appropriate number of accumulations and obtain a suitable control effect. This makes it possible to measure minute changes with higher accuracy.

  The present invention is a potential measuring device having at least a pair of detection systems having a detector comprising the charge supply unit, the reset gate, and the sensing charge storage unit having the same structure. The detection system A having the above-described function having a sensing part whose potential changes in accordance with the magnitude of a physical or chemical quantity, and the sensing part that does not respond to a change in physical or chemical quantity. In addition to configuring a pair of detection systems consisting of a detection system B having the same functions other than the sensing unit, the number of accumulations in the floating diffusion in the detection system A and the number of accumulations in the floating diffusion in the detection system B are changed in conjunction with each other. It is characterized by doing.

  When converting physical or chemical phenomena into charge information, it is effective to reduce components other than the amount of charge related to the measurement components in the detection system in order to obtain high measurement accuracy. The element (disturbance) needs to be reduced. In the present invention, the detection system is a dual type, one of the detection systems A detects a potential that is sensitive to measurement, the other detection system B detects a potential that is not sensitive to measurement, and obtains a potential difference between them. The potential to be detected truly can be detected. Further, by linking the number of times of accumulation in the floating diffusion in the detection system A and the number of times of accumulation in the floating diffusion in the detection system B, it is possible to prevent the potential difference between them from increasing with the increase in the number of times of accumulation. That is, by having a differential function inside the detection system, it is possible to prevent influences such as disturbances during compensation and to configure a detection system with high measurement accuracy.

  The present invention is the above-described potential measuring apparatus, wherein a charge transfer means is disposed between the sensing charge storage section and the floating diffusion, the charge transfer means being a charge coupled device, The charge in the sensing charge storage unit is transferred to one floating diffusion.

  In a semiconductor device that detects a physical phenomenon or a chemical phenomenon, the faster the charge transfer from the sensing unit to the floating diffusion, the faster the response speed of the detection system. In general, there are various methods for charge transfer in a semiconductor device, but a charge coupled device (CCD) has excellent characteristics in terms of high S / N ratio, transfer speed, transfer efficiency, and operability. is doing. The present invention makes use of these characteristics to improve the response speed by providing a charge transfer unit in the middle of the floating diffusion from the sensing unit, and to a plurality of sensing units (more than one floating diffusion via the charge transfer unit). Specifically, by having a CCD function for sequentially moving charges from the sensing charge storage unit), it is possible to easily image a one-dimensional distribution or two-dimensional distribution of a physical or chemical phenomenon.

  As described above, according to the method or apparatus for measuring a physical phenomenon or chemical phenomenon of the present invention, it is possible to amplify electric charges associated with the target physical phenomenon or chemical phenomenon or the output generated thereby, and excellent responsiveness. It is possible to quantify minute changes at the same time, and at the same time, ensure high measurement accuracy that can measure both wide and narrow measurement ranges with a single method, depending on the measurement object or measurement purpose. be able to.

  In particular, by making the detection system dual type and interlocking the number of times of accumulation in the floating diffusion, the amount of charge transferred to the floating diffusion is converted into charge information that truly corresponds to a physical or chemical phenomenon. Accuracy and speed can be improved. Further, by using a CCD or the like, a two-dimensional distribution of physical or chemical phenomena can be easily imaged.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

<Basic configuration of potential measurement device>
FIG. 1 illustrates a basic configuration (first configuration example) of a physical phenomenon or chemical phenomenon measuring apparatus according to the present invention.

  In FIG. 1, B is a semiconductor substrate made of, for example, p-type Si (silicon), and has a thickness of about 500 μm. The semiconductor substrate B has an insulating film P made of, for example, a silicon oxide film. The charge supply unit 1, the charge supply adjustment unit 2, the sensing unit 3, the barrier unit 4, the floating diffusion 5, the reset gate 6, and the reset drain are sandwiched therebetween. 7 is formed. The semiconductor substrate B is made resistant to the solution sample by applying a resin mold or the like. For example, an output transistor (not shown) is formed in the floating diffusion 5, and its output is introduced into the control means (control unit) 8.

The specific formation of the detection system is performed as follows, for example.
(1) The p-type Si substrate B is thermally oxidized to form an oxide film (SiO 2 ).
(2) The part is etched and the part is selectively oxidized. Thereafter, the selectively oxidized portion of SiO 2 is etched and further thermally oxidized to form a gate oxide film P. The thickness of this gate oxide film is about 500 mm.
(3) Phosphorous-doped low-resistance polysilicon is deposited on portions corresponding to the charge supply adjusting portion 2 and the barrier portion 4 on the upper surface to form electrodes. The thickness of this electrode is about 3000 mm, and after being deposited, it is thermally oxidized by about 1000 mm.
(4) Thereafter, phosphorus-doped low-resistance polysilicon is deposited again, and an electrode is formed on the upper surface of the sensing charge storage unit 9. The electrode is deposited to the same thickness as that of the electrode and then thermally oxidized by about 1000 mm. By oxidizing in this way, insulation between the electrodes is maintained.
(5) Thereafter, Si 3 N 4 (Ta 2 O 5 or Al 2 O 3 may be used) is deposited in a thickness of about 700 to form the sensing unit 3.

  In the measurement, a pulse voltage is applied to the charge supply unit 1, the barrier unit 4, and the reset gate 6, a DC voltage is applied to other parts, and a positive voltage is applied in a MOS structure using a p-type semiconductor. A potential state in the vicinity of the semiconductor-insulating film interface can be formed. The number of times or timing of application of the pulse voltage to the charge supply unit 1, the barrier unit 4, and the reset gate 6 is controlled by the control unit 8.

  The sensing unit 3 is a measurement site where the potential changes according to the magnitude of a physical or chemical quantity. For example, in the case of pH measurement, a cell for introducing an aqueous solution or a measurement object is provided. An electrode part is formed and a potential corresponding to the pH in the sample is generated. Such a potential or a change in the potential is converted into a charge, and the change in the charge in the detection unit is output-converted by an output transistor having a MOS structure.

  Here, the number of charge supply units 1 is not limited to one for one sensing unit 3, and a plurality of charge supply units 1 may be provided. As described above, the quantity, shape, or arrangement relationship of the sensing unit 3 may be uniquely determined depending on the measurement object or application, and when it is necessary to quickly supply charges to the entire sensing unit 3 The charge supply load to the sensing unit 3 is preferably distributed to the plurality of charge supply units 1.

  In addition, the size of the floating diffusion 5 is set based on the contact portion with the sensing unit 3 because the charge of the sensing unit 3 is transferred. The shape is not limited, but a trapezoidal shape or the like can be formed as shown in FIG. 1 in order to reduce the area.

  The measuring method in the measuring apparatus as described above will be described in the order of (1) basic measuring method and (2) a method of measuring pH as a specific measuring method.

(1) Basic measurement method A basic measurement method will be described with reference to the potential diagram shown in FIG.
(1-1) Initial Potential State Initially, the potential of the charge supply unit 1 is set high (the arrow direction is high), and no charge is supplied to the sensing unit 3.
(1-2) Supply of Charge Charge is supplied to the sensing unit 3 by lowering the potential of the charge supply unit 1.
(1-3) Accumulation of Charge By raising the potential of the charge supply unit 1, a part of the supplied charge overflows and the amount of charge limited by the charge supply adjustment unit 2 is accumulated in the sensing unit 3.
(1-4) Transfer of Charge By increasing the potential of the barrier unit 4, the charge accumulated in the sensing unit 3 is transferred to the floating diffusion 5, and the potential of the barrier unit 4 is decreased.
(1-5) Accumulation cycle The above (1-2) to (1-4) are repeated until a predetermined amount of electric charge is accumulated in the floating diffusion 5. Such repetition is the “accumulation frequency” in the present configuration example, which is a substantial amplification degree in the detection system, and the detection sensitivity is determined. The exact notation of amplification will be described later.
(1-6) Measurement of charge At this stage, the potential of the floating diffusion 5 is determined by the amount of transferred charge, and this potential is measured by an output transistor having a MOS structure.
(1-7) Reset After reading the potential of the floating diffusion 5, the reset gate 6 is turned on to supply charges from the reset drain 7, and the potential of the floating diffusion 5 is reset to the potential of the reset drain 7.
(1-8) Detection cycle By the above reset, the state returns to the same state as (1-1) again. That is, the detection cycle refers to repeating the operations (1-1) to (1-7) as described above, and thereby, the charge amount corresponding to the potential state in the sensing unit 3 is sequentially output. be able to.

  As described above, in this measuring apparatus, the sensing unit 3 configured to change the potential corresponding to the magnitude of a physical or chemical amount is formed on the semiconductor substrate B, and the sensing unit 3 A charge conversion mechanism is used in which charges are supplied to convert the physical or chemical quantities into charges corresponding to the size of the sensing unit.

The amplification degree A in the above measurement can be expressed accurately by the following formula 1.
[Formula 1]

Where Q [C]: the amount of charge transferred to the floating diffusion at one time
n [times]: Number of times of accumulation
C FD [F]: Charge capacity of floating diffusion
ΔVs: Potential change of the sensing unit.

  The number of times of accumulation is set corresponding to the charge accumulated in the preset measurement range or floating diffusion while adjusting the detection sensitivity. Note that by repeating detection in the same potential state in the sensing unit 3, noise such as disturbance can be averaged, and random noise can be substantially reduced.

(2) Specific Measurement Method As an actual measurement example based on the above basic measurement method, characteristics when measuring pH 0 to 14 and measuring pH 6.8000 ± 0.0001 will be described.

(2-1) pH measurement method Generally, in pH measurement, a pH standard solution (usually pH 1.68, 4.01, 6.86, 7.413 is used) is contacted with the sensing unit 3; After setting the reference potential of the sensing unit 3 with the reference electrode immersed in the solution, the measurement operation is performed. At this time, the change in surface potential due to the change in pH is known to be 59.16 mV / pH (25 ° C.) from the Nernst equation. Therefore, for example, when measuring pH 0 to 14, the potential change is about 840 mV, and it is necessary to capture the potential change of about 840 mV as the dynamic range in the sensing unit 3. On the other hand, when measuring pH 6.8000 ± 0.0001, that is, when obtaining a resolution of 0.0001 pH, a resolution of 5.9 μV is required.

  Therefore, for example, as a physicochemical phenomenon measurement sensor exhibiting the same characteristics as described above, FIG. 3A shows typical characteristics when it is assumed that the detection sensitivity can be amplified by 8 times per one accumulation. The applied voltage of the reference electrode is changed in a simulated manner instead of the change of the solution pH, and the sensor output at that time is represented. The change of the output voltage of about 6.8 V per change of the applied voltage of 1 V to the comparative electrode is shown. Has been obtained. Since the saturation output voltage is about 6.8V and the sensitivity is 8 times, the dynamic range is 6.8V (output) / 8 times (sensitivity) = 850 mV (input).

  Here, assuming that the dynamic range in the sensing unit 3 when measuring pH 0 to 14 derived from the Nernst equation is about 800 mV, the number of accumulations is increased in order to measure with high sensitivity using this sensor. For example, when accumulation is performed 10 times, a change of 8 V is obtained per 100 mV of voltage applied to the reference electrode, and a change of 10 μV can be regarded as a change of 0.8 mV. That is, by setting the number of accumulations to 10 times or more, a dynamic range for obtaining a resolution of 0.0001 pH with maximum sensitivity is obtained. Thus, it can set by changing the frequency | count of accumulation | storage into the dynamic range according to the measurement precision. FIG. 3B shows the difference between the sensor characteristics when the number of accumulations is 10 and the sensor characteristics when the number of accumulations is one.

(2-2) When measuring pH 0-14 As shown to FIG. 4 (A), when the measurement range is pH 0-14, the electric potential of the sensing part 3 changes about 840 mV. Accordingly, charges corresponding to a maximum of 840 mV are injected into the sensing unit 3 and transferred to the floating diffusion 5 through the barrier unit 4.

  At this time, it is necessary to set the potential of the charge supply adjusting unit 2 to a potential of pH 0. However, in practice, it is preferable to set the potential to a low value in consideration of variations in characteristics of the sensing unit 3. At pH 0, the charge injected into the sensing unit 3 is almost zero, and charges corresponding to the potential increase due to the increase in pH are injected, and when the pH is 14, the charge injection amount is the largest. Therefore, the floating diffusion 5 requires a charge capacity that can tolerate this maximum amount, and a single charge is sufficient for a sufficient amount of charge.

  In addition, the amount of charge to be moved is large, and a predetermined movement time is required until there is no remaining amount at the time of transfer from the sensing 3 or at the time of transfer from the floating diffusion 5 to the reset drain 7, which is required for one measurement. The transfer rate is a predetermined value.

  Further, in actual pH measurement, a standard solution of pH (usually pH 1.68, 4.01, 6.86, 7.413 is used) is contacted with the sensing unit 3 and is immersed in the solution by a reference electrode. In addition to setting the reference potential of the sensing unit 3, calibration as a sensor can be performed based on the potential of each liquid at this time, and variations in the sensor can be corrected.

(2-3) When measuring pH 6.8000 ± 0.0001 When the measurement range is pH pH 6.8000 ± 0.0001, the potential of the sensing unit 3 changes ±± 5.9 μV. At this time, it is preferable that the setting of the potential of the charge supply adjusting unit 2 is changed depending on the measurement range. That is, when the potential of the charge supply adjusting unit 2 is set to the potential of pH 0 as in the case where the measurement range is pH 0 to 14, the charge corresponding to about 400 mV that is the amount of change in the potential of the sensing unit 3 is transferred. Therefore, it is practically impossible to detect a charge corresponding to a 5.9 μV change therein. Therefore, as shown in FIG. 4B, by setting the electric potential of the charge supply adjusting unit 2 in the vicinity of the electric potential of pH 6.8 (in practice, it is preferable to set the electric potential to a lower value as described above). A charge close to the pH change width of the measurement range is injected. In this way, by adjusting the potential of the charge supply adjusting unit 2, it is possible to reduce a charge amount that is a so-called offset, and to secure a charge transfer rate corresponding to the measurement range. For example, taking pH measurement in a chemical reaction process as an example, it may be in a strong acid region at the start of the process and may gradually reach a weak alkali region via a neutral region as the reaction proceeds. In the case of tracking such changes, the dynamic range in the present invention is selectively used, and the potential of the charge supply adjusting unit 2 is adjusted in accordance with the progress of the reaction, thereby performing highly accurate process control that has not been conventionally achieved. Is possible.

  However, when detecting pH ± 0.0001, the amount of charge transferred is very small and it is difficult to ensure sufficient detection sensitivity. In other words, in a single accumulation amount, electric charge corresponding to a change of 5.9 μV is injected into the sensing unit 3 and only transferred to the floating diffusion 5 through the barrier unit 4. Therefore, as described above, by setting the number of accumulations to 10 times or more, the resolution of the dynamic range necessary to obtain the resolution of 0.0001 pH can be obtained. For example, a change of about 6 μV can be regarded as a change of 0.5 mV.

  In addition, although the travel time required for one accumulation is very short, the total transfer rate similarly becomes a predetermined value because the accumulation frequency is large.

  In addition, as for the number of accumulations, for example, when the measurement range can be estimated in advance as in the case of pH measurement in a chemical reaction process, the number of accumulations or the range of the accumulation number to be controlled is set in the control unit 8 according to the measurement range. It is possible to control automatically by setting. The control unit 8 can incorporate a means for setting a measurement range and a means for setting the number of accumulations, and each function or program can be incorporated in a personal computer or the like.

  For example, when it is difficult to estimate the measurement range in advance, such as when measuring the specific ion concentration of an unknown substance, the amount of charge accumulated in the floating diffusion 5 by a predetermined number of transfers (about once to several times). Is input to the control unit 8 to control the number of accumulations based on a preset charge amount-accumulation number association table or function, thereby setting the optimum number of accumulations or the range of accumulation times to be controlled. Is possible. At this time, the number of times of accumulation is not set at the start of measurement, and a signal for detecting the amount of charge accumulated in the floating diffusion 5 is feedback controlled at any time, and the number of times of accumulation is arbitrarily set. It becomes possible to detect with high accuracy.

<Other Configuration Example of Potential Measuring Device (Second Configuration Example)>
FIG. 5 shows another configuration example (second configuration example) of the physical phenomenon or chemical phenomenon measurement apparatus according to the present invention.

  The formation of the semiconductor substrate B and the semiconductor substrate B is the same as in the first configuration example. As shown in FIG. 5, the charge supply unit 1, the charge supply adjustment unit 2, the sensing unit 3, the barrier unit 4, and the sensing charge storage unit 9, the dam portion 10, the floating diffusion 5, the reset gate 6 and the reset drain 7 are formed.

  In the measurement, a pulse voltage is applied to the charge supply unit 1, the barrier unit 4, the dam unit 10, and the reset gate 6, a DC voltage is applied to other parts, and a positive voltage is applied in a MOS structure using a p-type semiconductor. Is added to form a potential state in the vicinity of the semiconductor-insulating film interface. The number of times or the timing of application of the pulse voltage to the charge supply unit 1, the barrier unit 4, the weir unit 10, and the reset gate 6 is controlled by the control unit 8.

  The sensing charge storage unit 9 is set according to the shape of the sensing unit 3 or the charge-capacitance ratio between the sensing unit 3 and the sensing charge storage unit 9, but in FIG. In order to reduce the area of the charge storage unit 9, a trapezoidal shape is formed.

A measuring method in the above measuring apparatus will be described with reference to the potential diagram shown in FIG.
(1) Initial Potential State Initially, the potential of the charge supply unit 1 is set high, and no charge is supplied to the sensing unit 3.
(2) Supply of charge Charge is supplied to the sensing unit 3 by lowering the potential of the charge supply unit 1.
(3) Accumulation of Charge By raising the potential of the charge supply unit 1, a part of the supplied charge overflows and an amount of charge limited by the charge supply adjustment unit 2 is accumulated in the sensing unit 3.
(4) Charge transfer 1
By increasing the potential of the barrier unit 4, the charge accumulated in the sensing unit 3 is transferred to the sensing charge accumulation unit 9.
(5) Charge transfer 2
A part of the charges accumulated in the sensing charge accumulation unit 9 is transferred to the floating diffusion 5 by lowering the potential of the barrier unit 4 and raising the potential of the weir unit 10.
However, the electric charge accumulated in the sensing charge accumulating part 9 is transferred to the floating diffusion 5 by keeping the electric potential of the dam part 10 constant and repeating the accumulation a predetermined number of times and then increasing the electric potential of the dam part 10. Is also possible.
(6) Accumulation cycle The above (2) to (5) are repeated until a predetermined amount of electric charge is accumulated in the floating diffusion 5. By such repetition, noise such as disturbance can be averaged, and so-called random noise can be substantially reduced. The number of repetitions is a substantial amplification degree in the detection system.
(7) Charge measurement When a predetermined amount of charge is accumulated in the floating diffusion 5 or (6) when the accumulation cycle reaches a preset number of times, the potential of the weir 10 is lowered and closed to stop the inflow of charges. . At this stage, since the potential of the floating diffusion 5 is determined by the amount of transferred charges, this potential is measured by an output transistor having a MOS structure.
(8) Reset After reading the potential of the floating diffusion 5, the reset gate 6 is turned on to supply charges from the reset drain 7, and the potential of the floating diffusion 5 is reset to the potential of the reset drain 7.
(9) Detection cycle By the above resetting, the same state as (1) is restored. That is, the detection cycle means that the operations (1) to (8) are repeated in this way, whereby the charge amount corresponding to the potential state in the sensing unit 3 can be sequentially output.

  As described above, electric charges are supplied to the sensing unit 3 configured to change the potential in accordance with the magnitude of the physical or chemical quantity, and the physical or chemical quantity is supplied to the sensing unit. A charge conversion mechanism is used that converts the charge into a charge corresponding to the magnitude of. At this time, by providing the sensing charge accumulating unit 9, it is possible to measure the minute change with higher accuracy by reducing the influence on the measurement potential of the sensing unit.

  In the present invention, it is preferable that the charge capacity of the sensing unit 3 exceeds the charge capacity of the floating diffusion 5. For example, by repeating the above detection cycle and measuring the charge after a certain amount of charge is accumulated in the floating diffusion 5, it is possible to increase the detection sensitivity, but the response time is equivalent to the accumulation time. Becomes slower. By increasing the charge capacity of the sensing unit 3 and increasing the accumulated charge, the rate of change in potential in the floating diffusion 5 when transferred to the floating diffusion 5 having a small charge capacity can be increased. By detecting the rate of change, accurate and sensitive measurement is possible. That is, by providing a charge capacity difference between the sensing unit 3 and the floating diffusion 5 that is a charge transfer means, the potential change in the sensing unit 3 is substantially amplified.

  Specifically, to increase the charge capacity of the sensing unit 3, (1) increase the area on the plane, (2) use a plurality of sensing units 3, (3) increase the potential, (4) charge There are means for increasing the density and the like, and it is possible to select according to the property or concentration of the sample to be subjected to a physical or chemical phenomenon.

<Basic configuration of a dual type physical or chemical measurement device>
Next, a dual type measuring apparatus to which the basic measuring apparatus for physical phenomena or chemical phenomena is applied will be described. FIG. 8 illustrates a basic configuration (third configuration example) of a dual-type physical phenomenon or chemical phenomenon measurement apparatus.

  Basically, two detection systems having the detection unit of the above-described configuration example are configured in parallel, and the detection having the above-described function including the sensing unit in which the potential changes in accordance with the magnitude of a physical or chemical quantity. The system A and a detection system B having a sensing unit that is not sensitive to changes in physical or chemical quantities and having the same function as the sensing unit are configured, and a floating diffusion in the detection system A is formed. And the number of times of accumulation in the floating diffusion in the detection system B can be changed in conjunction with each other. The detection system A is composed of two detection systems sharing one charge supply unit 1 and charge supply adjustment unit 2, and one detection system A includes a sensing unit 3a, a barrier unit 4a, a potential of which changes according to a physical phenomenon or a chemical phenomenon, It consists of a floating diffusion 5a, a reset gate 6a, and a reset drain 7a. The other detection system B includes a sensing unit 3b, a barrier unit 4b, a floating diffusion 5b, a reset gate 6b, and a reset drain 7b that are not sensitive to physical or chemical phenomena.

  The number of times or timing of application of the pulse voltage to the charge supply unit 1, the barrier units 4a and 4b, and the reset gates 6a and 6b is controlled by the control unit 8. In the present configuration example, the accumulation cycle is controlled in conjunction with the detection system A and the detection system B in accordance with the number of accumulations set corresponding to the measurement range. The term “interlocking” as used herein basically means that voltage is simultaneously applied to the barrier portions 4a and 4b and the reset gates 6a and 6b. However, when the dynamic range is large, the transfer charge in the detection system is small. Is preferable, it is possible to improve the stability of the entire sensor by changing the transfer speeds of the detection systems A and B or alternately transferring charges.

  At this time, it is preferable that the sensing units 3a and 3b are basically provided with a film or a part having a similar structure and having different sensitivity characteristics with respect to a physical phenomenon or a chemical phenomenon. This is because the compensation function of the detection system B can be enhanced by causing a similar change to the offset charge or disturbance component.

  In the measurement, the charge signal of the detection system A corresponds to “detection signal + offset signal + disturbance signal”, and the charge signal of the detection system B corresponds to “offset signal + disturbance signal”. Therefore, by obtaining the difference between the two, it is possible to effectively extract only the detection signal that is truly necessary by making effective use of the compensation function of the detection system B.

<Chemical CCD system configuration example (fourth configuration example)>
Furthermore, by having a CCD function that sequentially moves charges from a plurality of sensor units via a charge transfer unit for one floating diffusion, one-dimensional distribution or two-dimensional distribution of a physical or chemical phenomenon can be easily performed. Can be imaged. In the present invention, not only the operation of each charge supply unit and barrier unit in a plurality of sensor units, but also the charge transfer unit is controlled to set the number of times of accumulation corresponding to the detection signal in each sensor unit. It is also possible to do this. In particular, when high accuracy is required locally in the measurement of a two-dimensional distribution, it is possible to obtain weighted two-dimensional information of a physical or chemical phenomenon by setting the number of accumulations for each sensor. It becomes possible.

  Specifically, a fourth configuration example illustrated in FIG. 8 is possible. That is, the plurality of sensor units 12 (a, a), 12 (a, b),..., The charge transfer unit 13 that transfers the charges converted in each sensor unit in the direction of the arrow, and the transferred charges Are further transferred to the floating diffusion 5 and an output transistor 11 for converting the transferred charge into an output signal.

  The sensor units 12 (a, a), 12 (a, b),... Are arranged one-dimensionally or two-dimensionally to form an array, so that information on a plurality of points can be simultaneously captured, and the charge transfer unit 13 and The output transistor 11 can process signals at a plurality of points in an orderly manner. The output signal can be directly input to an image output device (not shown) such as a CRT to output an image, or the output signal can be AD converted and input to a computer.

  That is, the accumulated charges are supplied by sequentially opening the gates at the junctions of the sensor units 12 (a, a), 12 (a, b),... It is transferred via the transfer path of the charge transfer unit 13 by turning on and off. At this time, the drive of the CCD in the charge transfer unit 13 can be appropriately selected according to the amount of charge to be transferred, such as one-phase drive, two-phase drive, or four-phase drive. As the number of sensor units 12 increases, transfer efficiency becomes a big problem. In this case, it is preferable to use a bulk channel with high transfer efficiency as a transfer path. The transferred potential is transferred to the floating diffusion 5 and the potential of the floating diffusion 5 is changed. This change in potential is input to the gate of the output transistor 11 and used as a detection output.

  The CCD has excellent characteristics in terms of high S / N ratio, transfer speed, transfer efficiency, and operability, and is very useful when operating a plurality of electrodes. That is, the plurality of electrodes constituting the CCD can perform the functions of the sensing charge storage unit 9 or the barrier unit 4 or the weir unit 10 and is advantageous in that the transfer can be speeded up. . Furthermore, since it is not necessary to provide a difference in the voltage applied to each electrode, it is useful in that it is not necessary to limit the potential difference between the sensing unit 3 and the floating diffusion 5 or to limit the number of electrodes. In addition, the CCD can transfer charges under optimum conditions by changing the number of electrodes that are simultaneously operated during charge transfer according to the amount of charge accumulated in the sensing unit 3. That is, when the amount of charge to be transferred is large, non-transfer of charges can be eliminated by operating a plurality of electrodes. Furthermore, when the amount of charge to be transferred is small, by operating one electrode, it is possible to eliminate the residual charge in the electrode section and eliminate the measurement error factor.

In the above, the functions formed by the invention according to each claim have been described with reference to a configuration example in which a part of the functions is combined. However, the present invention is not limited to this, and other combinations, or the present application is included. It goes without saying that any combination with the matters described is possible.
<Application of measuring apparatus according to the present invention>
The measuring method or measuring apparatus according to the present invention can actually be used as a measuring apparatus or an evaluation apparatus as exemplified in FIG. The output from the measuring device using the sensor device 14 as a measuring means as described above is input to the personal computer 16 as the evaluation device 15 for performing reaction evaluation, for example, and displayed on the software screen 17 as data and images by performing arithmetic processing. Thus, it is possible to quantitatively grasp the physical phenomenon or chemical phenomenon of the sample. In addition, when a CCD is used as the sensor device 14, a two-dimensional tracking of a physical phenomenon or a chemical phenomenon can be performed by a two-dimensional image displayed on the software screen 17.

As described above, the present invention can be widely used for measuring the two-dimensional distribution of the ion concentration of a sample such as a solution, and can also be applied to the following fields.
(1) Chemical microscope application fields / chemistry; ion concentration measurement / electrochemical field, gas distribution measurement field / two-dimensional dynamic observation and analysis of titration (2) environmental measurement / environment; application to bioremediation ( 3) Food inspection / food, microorganisms (4) ME field / medicine / ecological tissue; surface ion concentration measurement of tissue cells, cell surface potential measurement, DNA measurement (5) bio field (6) animal and plant field / plant; callus surface Potential distribution measurement, organisms, front view animals (7) Corrosion measurement field, metal; metal corrosion and coating, coating (8) Surface analysis such as zeta potential, zeta potential of powder and ceramics.

  In addition, the measurement target (sample) may be any of gas, liquid, solid, and powder. Chemical fluctuation that reacts selectively by the specific sensitive layer of the sensor part and the charge fluctuation due to the interface phenomenon due to physical contact For example, the distribution of a liquid flow or transient chemical reaction transients can be obtained as a high-sensitivity, high-quality chemical image. Furthermore, it is useful for real-time imaging of titration phenomena to other types of analysis and display using image software, and is also effective for portable cameras.

Explanatory drawing which shows the basic structure (1st structural example) of the detection part which concerns on this invention. Explanatory drawing which illustrates the change of 1 electric potential which concerns on the 1st structural example of this invention. Explanatory drawing which illustrates the output characteristic which concerns on the 1st structural example of this invention. Explanatory drawing which illustrates the change of the other electric potential which concerns on the 1st structural example of this invention. Explanatory drawing which shows the 2nd structural example which concerns on this invention. Explanatory drawing which illustrates the change of one electric potential concerning the measuring method of the 2nd example of composition. Explanatory drawing which shows the 3rd structural example which concerns on this invention. Explanatory drawing which shows the 4th structural example which concerns on this invention. Explanatory drawing which illustrates the outline | summary of the measuring apparatus which concerns on this invention. Explanatory drawing which shows the structural example which concerns on a prior art.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Charge supply part 2 Charge supply adjustment part 3, 3a, 3b Sensing part 4, 4a, 4b Barrier part 5, 5a, 5b, Floating diffusion 6, 6a, 6b Reset gate 7, 7a, 7b Reset drain 8 Control means (control Part)
9 Sensing Charge Storage Unit 10 Weir Unit 13 Charge Transfer Unit B Semiconductor Substrate P Insulating Film

Claims (6)

  1. Charge is supplied from the charge supply unit to the sensing unit whose potential changes according to the physical or chemical quantity, and the supplied charge is taken out from the sensing unit via the floating diffusion and supplied. A method of measuring a potential related to the physical phenomenon or chemical phenomenon by detecting a charge amount,
    Set the measurement range according to the magnitude of the change in physical or chemical quantity, set the number of times that the moving charge is accumulated in the floating diffusion, and control the number of times of accumulation based on the set measurement range A potential measurement method characterized by
  2.   2. The potential measuring method according to claim 1, wherein the number of times of accumulation in the floating diffusion can be changed in conjunction with the amount of charge accumulated in the floating diffusion by a predetermined number of transfers.
  3. A charge supply unit that supplies charge to the sensing unit; a sensing unit that changes in potential according to a physical or chemical quantity; and a detection unit that includes a floating diffusion that extracts the charge supplied to the sensing unit. A measuring device,
    A means for setting a measurement range according to the magnitude of a change in physical or chemical quantity, a means for setting the number of times the moving charge is accumulated in the floating diffusion, and an intermediate between the sensing unit and the floating diffusion. An apparatus for measuring a potential, comprising: a control unit that can change the number of times of accumulation in the floating diffusion by controlling the operation of the barrier portion.
  4. A charge supply unit that supplies charges to the sensing unit; a sensing unit that changes in potential according to a physical or chemical quantity; a sensing charge storage unit that accumulates charges transferred from the sensing unit; and the sensing A measuring device having a detection unit comprising a floating diffusion for taking out the charge supplied to the charge storage unit,
    A means for setting a measurement range according to the magnitude of a change in physical or chemical quantity, a means for setting the number of times a moving charge is accumulated in a floating diffusion, and an intermediate between the sensing charge accumulation section and the floating diffusion An apparatus for measuring a potential, comprising: a control unit that can change the number of times of accumulation in the floating diffusion by the operation of the threshold portion.
  5. A measuring device having at least a pair of detection systems having a detector comprising the charge supply unit, the reset gate, and the sensing charge storage unit having the same structure, the sensing charge storage unit;
    Detection system A having the above-described function having a sensing unit whose potential changes corresponding to the magnitude of a physical or chemical quantity, and a sensing unit having a sensing part that is insensitive to changes in physical or chemical quantity A pair of detection systems consisting of the detection system B having the same functions other than the above are configured, and the number of accumulations in the floating diffusion in the detection system A and the number of accumulations in the floating diffusion in the detection system B are changed in conjunction with each other. 5. The apparatus for measuring a potential according to claim 3 or 4, characterized in that:
  6.   A measuring apparatus in which a charge transfer means is disposed between the sensing charge storage section and the floating diffusion, wherein the charge transfer means is a charge coupled device, and charges of a plurality of sensing charge storage sections are converted into one floating diffusion. The potential measuring device according to claim 3, wherein the potential measuring device is transferred.
JP2005101496A 2005-03-31 2005-03-31 Potential measuring method and measuring instrument Pending JP2006284225A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005101496A JP2006284225A (en) 2005-03-31 2005-03-31 Potential measuring method and measuring instrument

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2005101496A JP2006284225A (en) 2005-03-31 2005-03-31 Potential measuring method and measuring instrument

Publications (1)

Publication Number Publication Date
JP2006284225A true JP2006284225A (en) 2006-10-19

Family

ID=37406319

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2005101496A Pending JP2006284225A (en) 2005-03-31 2005-03-31 Potential measuring method and measuring instrument

Country Status (1)

Country Link
JP (1) JP2006284225A (en)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009236502A (en) * 2008-03-25 2009-10-15 Toyohashi Univ Of Technology Chemical or physical phenomenon detection device, and control method therefor
WO2013024791A1 (en) * 2011-08-12 2013-02-21 国立大学法人豊橋技術科学大学 Device and method for detecting chemical and physical phenomena
JP2013533482A (en) * 2010-06-30 2013-08-22 ライフ テクノロジーズ コーポレーション Ion-sensitive charge storage circuit and method
US9110015B2 (en) 2010-09-24 2015-08-18 Life Technologies Corporation Method and system for delta double sampling
US9270264B2 (en) 2012-05-29 2016-02-23 Life Technologies Corporation System for reducing noise in a chemical sensor array
US9269708B2 (en) 2006-12-14 2016-02-23 Life Technologies Corporation Methods and apparatus for measuring analytes using large scale FET arrays
JP2016080601A (en) * 2014-10-20 2016-05-16 シャープ株式会社 Chemical-physical phenomenon detection device and manufacturing method therefor
US9404920B2 (en) 2006-12-14 2016-08-02 Life Technologies Corporation Methods and apparatus for detecting molecular interactions using FET arrays
US9618475B2 (en) 2010-09-15 2017-04-11 Life Technologies Corporation Methods and apparatus for measuring analytes
US9671363B2 (en) 2013-03-15 2017-06-06 Life Technologies Corporation Chemical sensor with consistent sensor surface areas
US9823217B2 (en) 2013-03-15 2017-11-21 Life Technologies Corporation Chemical device with thin conductive element
US9835585B2 (en) 2013-03-15 2017-12-05 Life Technologies Corporation Chemical sensor with protruded sensor surface
US9841398B2 (en) 2013-01-08 2017-12-12 Life Technologies Corporation Methods for manufacturing well structures for low-noise chemical sensors
US9852919B2 (en) 2013-01-04 2017-12-26 Life Technologies Corporation Methods and systems for point of use removal of sacrificial material
US9927393B2 (en) 2009-05-29 2018-03-27 Life Technologies Corporation Methods and apparatus for measuring analytes
US9951382B2 (en) 2006-12-14 2018-04-24 Life Technologies Corporation Methods and apparatus for measuring analytes using large scale FET arrays
US9960253B2 (en) 2010-07-03 2018-05-01 Life Technologies Corporation Chemically sensitive sensor with lightly doped drains
US9964515B2 (en) 2008-10-22 2018-05-08 Life Technologies Corporation Integrated sensor arrays for biological and chemical analysis
US9970984B2 (en) 2011-12-01 2018-05-15 Life Technologies Corporation Method and apparatus for identifying defects in a chemical sensor array
US9995708B2 (en) 2013-03-13 2018-06-12 Life Technologies Corporation Chemical sensor with sidewall spacer sensor surface
US10077472B2 (en) 2014-12-18 2018-09-18 Life Technologies Corporation High data rate integrated circuit with power management
US10100357B2 (en) 2013-05-09 2018-10-16 Life Technologies Corporation Windowed sequencing
US10379051B2 (en) 2015-09-14 2019-08-13 Kabushiki Kaisha Toshiba Illumination device and bio-information measurement device having the same
US10379079B2 (en) 2014-12-18 2019-08-13 Life Technologies Corporation Methods and apparatus for measuring analytes using large scale FET arrays
US10451585B2 (en) 2009-05-29 2019-10-22 Life Technologies Corporation Methods and apparatus for measuring analytes
US10458942B2 (en) 2013-06-10 2019-10-29 Life Technologies Corporation Chemical sensor array having multiple sensors per well

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08170952A (en) * 1994-12-19 1996-07-02 Nichimen Denshi R & D Kk Ozone sensor having temperature correcting function
JP2002175150A (en) * 2000-12-06 2002-06-21 Canon Inc Light detecting device, light receiving position detecting device, coordinate input device, coordinate input and output device, and light detecting method
JP2003014691A (en) * 2001-06-29 2003-01-15 Horiba Ltd Ccd sensor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08170952A (en) * 1994-12-19 1996-07-02 Nichimen Denshi R & D Kk Ozone sensor having temperature correcting function
JP2002175150A (en) * 2000-12-06 2002-06-21 Canon Inc Light detecting device, light receiving position detecting device, coordinate input device, coordinate input and output device, and light detecting method
JP2003014691A (en) * 2001-06-29 2003-01-15 Horiba Ltd Ccd sensor

Cited By (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9989489B2 (en) 2006-12-14 2018-06-05 Life Technnologies Corporation Methods for calibrating an array of chemically-sensitive sensors
US9269708B2 (en) 2006-12-14 2016-02-23 Life Technologies Corporation Methods and apparatus for measuring analytes using large scale FET arrays
US10203300B2 (en) 2006-12-14 2019-02-12 Life Technologies Corporation Methods and apparatus for measuring analytes using large scale FET arrays
US9951382B2 (en) 2006-12-14 2018-04-24 Life Technologies Corporation Methods and apparatus for measuring analytes using large scale FET arrays
US10415079B2 (en) 2006-12-14 2019-09-17 Life Technologies Corporation Methods and apparatus for detecting molecular interactions using FET arrays
US9404920B2 (en) 2006-12-14 2016-08-02 Life Technologies Corporation Methods and apparatus for detecting molecular interactions using FET arrays
US10502708B2 (en) 2006-12-14 2019-12-10 Life Technologies Corporation Chemically-sensitive sensor array calibration circuitry
JP2009236502A (en) * 2008-03-25 2009-10-15 Toyohashi Univ Of Technology Chemical or physical phenomenon detection device, and control method therefor
US9964515B2 (en) 2008-10-22 2018-05-08 Life Technologies Corporation Integrated sensor arrays for biological and chemical analysis
US10451585B2 (en) 2009-05-29 2019-10-22 Life Technologies Corporation Methods and apparatus for measuring analytes
US9927393B2 (en) 2009-05-29 2018-03-27 Life Technologies Corporation Methods and apparatus for measuring analytes
US9239313B2 (en) 2010-06-30 2016-01-19 Life Technologies Corporation Ion-sensing charge-accumulation circuits and methods
US10481123B2 (en) 2010-06-30 2019-11-19 Life Technologies Corporation Ion-sensing charge-accumulation circuits and methods
JP2013533482A (en) * 2010-06-30 2013-08-22 ライフ テクノロジーズ コーポレーション Ion-sensitive charge storage circuit and method
JP2018109654A (en) * 2010-06-30 2018-07-12 ライフ テクノロジーズ コーポレーション Ion-sensing charge-accumulation circuits and methods
JP2016128841A (en) * 2010-06-30 2016-07-14 ライフ テクノロジーズ コーポレーション Ion-sensing charge-accumulation circuits and methods
US9960253B2 (en) 2010-07-03 2018-05-01 Life Technologies Corporation Chemically sensitive sensor with lightly doped drains
US9958414B2 (en) 2010-09-15 2018-05-01 Life Technologies Corporation Apparatus for measuring analytes including chemical sensor array
US9958415B2 (en) 2010-09-15 2018-05-01 Life Technologies Corporation ChemFET sensor including floating gate
US9618475B2 (en) 2010-09-15 2017-04-11 Life Technologies Corporation Methods and apparatus for measuring analytes
US9110015B2 (en) 2010-09-24 2015-08-18 Life Technologies Corporation Method and system for delta double sampling
US9482641B2 (en) 2011-08-12 2016-11-01 National University Corporation Toyohashi University Of Technology Device and method for detecting chemical and physical phenomena
JPWO2013024791A1 (en) * 2011-08-12 2015-03-05 国立大学法人豊橋技術科学大学 Chemical / physical phenomenon detection apparatus and detection method
WO2013024791A1 (en) * 2011-08-12 2013-02-21 国立大学法人豊橋技術科学大学 Device and method for detecting chemical and physical phenomena
US9970984B2 (en) 2011-12-01 2018-05-15 Life Technologies Corporation Method and apparatus for identifying defects in a chemical sensor array
US10365321B2 (en) 2011-12-01 2019-07-30 Life Technologies Corporation Method and apparatus for identifying defects in a chemical sensor array
US9985624B2 (en) 2012-05-29 2018-05-29 Life Technologies Corporation System for reducing noise in a chemical sensor array
US9270264B2 (en) 2012-05-29 2016-02-23 Life Technologies Corporation System for reducing noise in a chemical sensor array
US10404249B2 (en) 2012-05-29 2019-09-03 Life Technologies Corporation System for reducing noise in a chemical sensor array
US9852919B2 (en) 2013-01-04 2017-12-26 Life Technologies Corporation Methods and systems for point of use removal of sacrificial material
US9841398B2 (en) 2013-01-08 2017-12-12 Life Technologies Corporation Methods for manufacturing well structures for low-noise chemical sensors
US10436742B2 (en) 2013-01-08 2019-10-08 Life Technologies Corporation Methods for manufacturing well structures for low-noise chemical sensors
US9995708B2 (en) 2013-03-13 2018-06-12 Life Technologies Corporation Chemical sensor with sidewall spacer sensor surface
US9823217B2 (en) 2013-03-15 2017-11-21 Life Technologies Corporation Chemical device with thin conductive element
US9835585B2 (en) 2013-03-15 2017-12-05 Life Technologies Corporation Chemical sensor with protruded sensor surface
US9671363B2 (en) 2013-03-15 2017-06-06 Life Technologies Corporation Chemical sensor with consistent sensor surface areas
US10422767B2 (en) 2013-03-15 2019-09-24 Life Technologies Corporation Chemical sensor with consistent sensor surface areas
US10100357B2 (en) 2013-05-09 2018-10-16 Life Technologies Corporation Windowed sequencing
US10458942B2 (en) 2013-06-10 2019-10-29 Life Technologies Corporation Chemical sensor array having multiple sensors per well
US10031101B2 (en) 2014-10-20 2018-07-24 Sharp Kabushiki Kaisha Chemical/physical phenomenon detecting device and method of producing the same
JP2016080601A (en) * 2014-10-20 2016-05-16 シャープ株式会社 Chemical-physical phenomenon detection device and manufacturing method therefor
US10077472B2 (en) 2014-12-18 2018-09-18 Life Technologies Corporation High data rate integrated circuit with power management
US10379079B2 (en) 2014-12-18 2019-08-13 Life Technologies Corporation Methods and apparatus for measuring analytes using large scale FET arrays
US10379051B2 (en) 2015-09-14 2019-08-13 Kabushiki Kaisha Toshiba Illumination device and bio-information measurement device having the same

Similar Documents

Publication Publication Date Title
Barbaro et al. A charge-modulated FET for detection of biomolecular processes: conception, modeling, and simulation
US8415177B2 (en) Two-transistor pixel array
EP1272860B1 (en) Sensor array and method for detecting the condition of a transistor in a sensor array
US9960253B2 (en) Chemically sensitive sensor with lightly doped drains
Shan et al. Imaging local electrochemical current via surface plasmon resonance
US8796036B2 (en) Method and system for delta double sampling
Chi et al. Study on extended gate field effect transistor with tin oxide sensing membrane
EP1554569B1 (en) Sensor arrangement and method for operating a sensor arrangement
TWI245073B (en) Biological identification system with integrated sensor chip
TW586228B (en) Method for fabricating a titanium nitride sensing membrane on an EGFET
Bartic et al. Monitoring pH with organic-based field-effect transistors
ES2674618T3 (en) Digital signal processing circuit comprising an ion-sensitive field effect transistor and method of monitoring a property of a fluid
US8786331B2 (en) System for reducing noise in a chemical sensor array
DE19857851B4 (en) Detection device for physical and / or chemical quantities
US7794584B2 (en) pH-change sensor and method
US20130190211A1 (en) Titanium nitride as sensing layer for microwell structure
CN102132153B (en) Reducing capacitive charging in electronic devices
Sawada et al. Novel fused sensor for photo and ion sensing
CN100429509C (en) FET type sensor, ion density detecting method comprising this sensor, and base sequence detecting method
US20190033363A1 (en) Methods and apparatus for testing isfet arrays
TWI422818B (en) Hydrogen ion sensitive field effect transistor and manufacturing method thereof
ES2554128T3 (en) ISFET device
CN103154718B (en) The electric charge accumulation circuit of sensing ion and method
Milgrew et al. A 16× 16 CMOS proton camera array for direct extracellular imaging of hydrogen-ion activity
EP1870703B1 (en) Cumulative chemical or physical phenomenon detecting apparatus

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20071015

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20100402

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20100527

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20101102