JPS6049254A - Chemical analysis device using semiconductor chemical sensor - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a chemical analysis device that uses a semiconductor chemical sensor to determine the concentration or partial pressure of a specific chemical substance in a solution.

[Background of the invention]

Conventionally, when measuring the concentration of a specific chemical substance in a solution, 1
In many cases, each item is measured using one sensor and the concentration is displayed based on the value measured only once, but it is difficult for the measurer to accurately estimate the error in the mixture of the measured values based on the value measured once. If this was not possible, measurements were repeated several times to obtain reproducibility and reliability of the measured values. Performing repeated measurements several times requires a larger amount of sample and more time, and is particularly unsuitable for clinical tests such as blood, which require a small amount of sample and rapid measurement. .

[Purpose of the invention]

An object of the present invention is to obtain a chemical analysis device using a semiconductor chemical processor that enables quantitative statistical processing of the accuracy and precision of measured values through a single measurement.

[Summary of the Invention] In order to achieve the above object, a chemical analysis device using a semiconductor chemical sensor according to the present invention has a sensor section equipped with a plurality of semiconductor chemical sensors having the same function, preferably 10 or more. , a detection section that amplifies or converts the signal from the sensor section, an arithmetic processing section that statistically processes the signal from the detection section, and a display section that displays the statistically processed measured value of the measured component in the test sample. This makes it possible to perform subsequent processing to quantitatively determine the accuracy and precision of measured values through a single measurement. In statistical processing of measured values, the accuracy of the average value is always better than the accuracy of a single measured value, and the accuracy improves as the number of measured values increases.
In order to obtain high accuracy in one measurement, it is necessary to use many sensors having the same function. In order to perform statistical processing, six or more semiconductor chemical sensors with the same function are required, and in order to further increase the accuracy and precision of measured values, it is desirable to use at least two semiconductor chemical sensors. .

It is known that conventional processors other than semiconductors have the same 411 properties, but semiconductor chemical sensors are very easy to form multiple processors on the same substrate at the same time. It is preferable that semiconductor chemical sensors with the same function used for measurement be formed on the same substrate, since the semiconductor chemical sensors formed thereon have uniform characteristics.

By using multiple semiconductor chemical sensors with almost the same operating characteristics formed on the same substrate, it is possible to obtain multiple actual values in one measurement. Even if an abnormal value appears due to film peeling on the surface, adhesion of foreign matter, etc., it is possible to detect the occurrence of an abnormality in the semiconductor chemical processor by knowing the size of its standard deviation.

In order to keep the number of digits displayed as measurement results of this chemical analyzer constant, the standard deviation obtained by measuring a sample must be within at least 20 times the final unit of this display. Let's do it like this. If this value is exceeded, it is assumed that an abnormality has occurred in the semiconductor chemical sensor, and the measurement is performed again, or the semiconductor chemical sensor that outputs the output value that is farthest from the average value among the single measurement values is excluded. Find the average value and standard deviation again and repeat this until the required conditions are met.

The limit on the number of semiconductor chemical processors to be excluded shall be within 50%. Preferably it is within 10%, and if it exceeds this percentage, the semiconductor chemical sensor should be replaced. The average value thus determined, or the average value plus the standard deviation as an error, is displayed as the measurement result of this chemical analyzer.

[Embodiments of the invention]

Next, embodiments of the present invention will be explained with reference to the drawings.

FIG. 1 is an explanatory diagram showing the configuration of a chemical analyzer using a semiconductor chemical processor according to the present invention, FIG. 2 is a perspective view of a Tough flow cell equipped with a semiconductor chemical processor in the chemical analyzer, and FIG. 6 is a flow cell described in "2". Figure 4 is a cross-sectional view showing the contact state between the semiconductor chemical sensor and the solution to be measured.
FIG. 5 is a diagram showing a first embodiment of the measurement system of the chemical analyzer described above; FIG. The figure shows one semiconductor chemical sensor for K measurement.
Figure 7 is a correlation diagram between the concentration measurement results and the 10 repetitions K by the flame photometry. The correlation diagram with the concentration measurement results, Figure 8, shows the second method using multiple semiconductor chemical sensors each having different functions.
FIG. 3 is a diagram showing a chip formed on the measurement system of the second embodiment, which is provided for each measurement capability of the embodiment.

As shown in FIG. 1, a chemical analysis apparatus using a semiconductor chemical sensor according to the present invention is constructed by using a peristaltic pump 1 to feed a carrier solution B through a flow cell 2.6.4.5 equipped with a semiconductor chemical sensor from a sampler 7. Another peristaltic pump 8 injects the solution to be measured flowing through the liquid sample channel 9 to the sample injection valve 1o, and the carrier solution O is used for measurement by the semiconductor chemical sensor attached to each tube. Each output of these semiconductor chemical sensors passes through a signal detection section 11 consisting of a multiplexer, a sample hold, and an A/D converter, and is read into a microcomputer 12, which is an arithmetic processing section, and subjected to statistical processing, and the results are used as measurement results. Microcomputer 12 display or printer 1
Display on 6. The flow cell in the above chemical analyzer has a liquid sample channel 9 through which the solution to be measured flows, as shown in Fig. 2.
The semiconductor chemical sensor 14 is brought into contact with a part of the semiconductor chemical sensor 14. This contact is achieved by opening a window in a part of the liquid sample channel 9 and inserting the gate part of the semiconductor chemical sensor 14 into the window as shown in FIG. The solution to be measured 15 is made to come into direct contact with the above-mentioned C) M, and the same part of the window is hardened with epoxy resin 16 so that the solution to be measured 15 does not leak outside. A bonding panode 17 is provided as an electrode of the semiconductor chemical sensor chip, and a bonding panode 17 is provided as an electrode of the semiconductor chemical sensor chip, and a
11! It is connected by a wire 19. Both 20 in FIG. 1 above are drain reservoirs.

The first embodiment of the present invention shown in FIG.
At the same time, N semiconductor chemical samples for measurement were formed on the same substrate, and the sensor part was immersed in the solution to be measured. A multiplexer 22 that sequentially takes out signals from the outputs of the N measurement semiconductor chemistry cells 21.
, a sample hold 26 that keeps the extracted signal unchanged for a certain period of time as required, and an A/D converter 24
The signal is read into a microcomputer 12, which is a signal processing section, through a signal detection section 11 consisting of a signal detection section 11, which performs statistical processing, and displays the results. In addition to this configuration, it is also possible to add an A/D converter 24 to each of the semiconductor chemical sensors 21 for measurement, switch the signal from the A/D converter 24 with a multiplexer 22, and statistically process it with the microcomputer 12. It will be done. The above-mentioned N 1s (1 digits measured by the measurement semiconductor chemical sensor 21
Let each concentration value be ~I-IN, and calculate the average value from this value (calculate the statistical value that is the deviation).

/F1] Here, the estimated value of the measurement solution is set to 1-1, and it is assumed to be the measurement result of the chemical analyzer using this semiconductor chemical sensor for K'' measurement.The above estimated value 1[ is somewhat deviated from the true value. In some cases, especially in the actual measurement of blood, etc., due to adhesion of blood cells, protein, etc. to the sensor surface, or deterioration of the water resistance of the sensor itself, the true value of 1 (a value that is far from the concentration) may be output. Abnormality detection of the semiconductor chemical sensor in such cases was carried out as follows.As soon as the significant figures of the measurement results in this chemical analyzer are displayed to the second decimal place, it is 1/4 of the standard deviation. is rounded to a divisor of 10, and when this number becomes a large number greater than or equal to 0.1, only the first decimal place has meaning as a significant figure, so it is invalid.For example, standard Deviation is 0.
When it becomes 5, 1/4 of it is 0.125, and the nearest divisor of 10 is 0.1, so the output result at this time is invalidated. If invalidated like this, the estimated value is 1−
The semiconductor chemical sensor exhibiting the value farthest from 1 is regarded as a failure, and the average value and standard deviation of the 1< concentration from the other sensors are determined again. Continue until the divisor of 10 closest to 1/4 of the next standard deviation becomes 0.01 or less. From the next measurement onward, measurements will be performed using other semiconductor chemical sensors, excluding the semiconductor chemical sensor that has been deemed to be faulty. If more than 10% of the semiconductor chemical sensors are broken, the entire semiconductor chemical sensor is replaced with a new one. However, the proportion of failed processors at the time of replacement shall be 50% or less. It can be applied to all Sen-9-v semiconductor chemical processors used for the above measurements.For example, 'Pa205
Semiconductor chemical sensor for pT-1 measurement equipped with a membrane, F 1
．． It can also be applied to gas sensors, enzyme sensors, and microbial sensors that combine IT or half-barrel shaped polarographic sensors with gas permeable membranes, immobilized enzyme membranes, or immobilized microbial membranes. FIG. 5 shows a plurality of semiconductor chemical processors 21 having the same function as described above on one 81 substrate 25.
”2 shows the formed chip. In this way, the same board 25
A plurality of semiconductor chemical sensors 21 formed simultaneously in
A semiconductor chemical sensor with well-matched characteristics and optimal for this chemical analyzer that performs statistical processing of measured values can be obtained.

Figure 6 shows the measured values obtained by repeatedly measuring solutions with various K concentrations by flame photometry 10 times, and 1 (
■ (measured using one semiconductor chemical sensor for concentration measurement)
This is a diagram showing the correlation with the measured concentration value, and the correlation coefficient is γ = 0.
．． It became 980. Figure 7 + shows the correlation between the measured concentration value of the first embodiment using 10 semiconductor sensors for concentration measurement and the constant value of concentration 1flll after each repetition of 10 times using the flame photometry method. In the figure shown, the correlation coefficient is γ-0999, which is clear when compared with the results shown in Figure 6 above.
The measurement accuracy of the measurement results using this chemical analyzer was significantly improved regardless of the single measurement.

→- The second embodiment is a chemical analyzer that uses only one type of semiconductor chemical sensor 21 for I< measurement in the first embodiment, whereas the second embodiment is In addition to the semiconductor chemistry sensor 21 for measurement, for example, the semiconductor chemistry sensor 26 for pl-1 measurement and the semiconductor chemistry sensor 27 for Na measurement.
A chip 28.2 in which several types of semiconductor chemical processors are formed on the same Si substrate, each having a plurality of each type.
9.60 is used to measure the specific chemical substance in the solution to be measured, and the multiplexer 22 is
, sample hold 2, A/D converter 24, microphone [This is a chemical analyzer that performs statistical processing with a cocon beater 12, and the statistical processing for each specific chemical substance is the same as in the first embodiment above. However, the concentration and partial pressure of various specific chemical substances can be determined in one measurement! Each specific chemical substance can be determined accurately and accurately.

FIG. 9 shows a depth 28, 29 in which a plurality of semiconductor chemical processors 21, 26, 27 of several types in the second embodiment are formed on the same S+ substrate.
．． 5 is a diagram showing a measurement system of a chemical analyzer using a chemical analyzer 30. Similar to the example shown in FIG. 5, the characteristics of each of a plurality of semiconductor chemical sensors can be made uniform.

The sixth embodiment is a chemical analysis device that uses a plurality of semiconductor chemical sensors of different types formed on one Si substrate 61 as shown in FIG. The characteristics of each semiconductor chemical sensor are well matched, and the work of attaching and sealing it to the fluid sample channel 9 within the flow cell of the chemical analyzer is easy, and accurate and precise measurements can be performed in a short time.

〔Effect of the invention〕

As described above, a chemical analysis apparatus using a semiconductor chemical processor according to the present invention includes a plurality of semiconductor chemical processors having the same function, preferably 10 or more. Alternatively, by being equipped with a detection section for conversion, an arithmetic processing section for statistically processing the signal from the detection section, and a display section for displaying the measured value of the component to be measured in the test sample after statistical processing, it is possible to This makes it possible to quantitatively evaluate the accuracy and precision of measured values through the measurement of can be displayed. If there is a failure among multiple semiconductor chemical sensors, a large difference in output value will occur between the semiconductor chemical sensors, so it is possible to detect the occurrence of a failure in the semiconductor chemical sensor. Furthermore, when using multiple sensors other than semiconductors, costs are required depending on the number of sensors used, but the chemical analyzer according to the present invention has multiple sensors with the same characteristics &! Since semiconductor chemical sensors are used, there is an effect that even if the number of semiconductor chemical sensors is increased, the cost will hardly change when forming semiconductor chemical sensor elements on the same substrate.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram showing the configuration of a chemical analysis device using a semiconductor chemical sensor according to the present invention, FIG. 2 is a perspective view of a flow cell as a semiconductor chemical sensor in the chemical analysis device, and FIG. "A cross-sectional view showing the contact state between the semiconductor chemical sensor and the solution to be measured in the cosel, FIG. 4 is a diagram showing the first embodiment of the measurement system of the chemical analyzer, and FIG. 5 is the second embodiment. Figure 6 shows the correlation between the values measured 10 times by flame photometry and the values measured by one semiconductor chemical sensor (with respect to concentration). figure,
Fig. 7 is a correlation diagram between the measured values of the above flame photometry method and the measured values of this chemical analyzer, and Fig. 8 shows the measurement of the second embodiment using a plurality of semiconductor chemical sensors each having different functions. 9 is a diagram showing the measurement system of the second embodiment described above, in which a substrate on which a plurality of semiconductor chemical processors having the same function are formed is provided for each function, and FIG. FIG. 2 is a diagram showing a chip in which semiconductor chemical processors having the same functions are formed on the same substrate for each function. 2, 3.4.5 ・Flow cell (sensor part) 11 ・
Signal detection unit 12° microconometry (nt calculation processing unit) 21.2
6.27 ・Semiconductor chemistry center 22...Multiplexer 26...The/Pull hold 24...A/1] Converter 25.28.29.30.31...Substrate representative patent attorney Junnosuke Nakatoshi

Claims (5)

[Claims] (1) A chemical analyzer that uses a semiconductor chemical sensor once a month to measure the concentration of a specific chemical component, partial pressure, etc. in a test sample, and a sensor that has multiple semiconductor chemical sensors with the same function. a detection section for amplifying or converting the signal from the sensor section, an arithmetic processing section for processing the I/H signal from the detection section, and a display for displaying the side>i value of the component to be measured that has undergone statistical processing. It is considered heavy equipment to be equipped with a section! A chemical analysis device using a conductor chemistry sensor. (2) A chemical analysis device using a semiconductor chemical sensor according to claim 1, wherein the semiconductor chemical sensor has a plurality of chemical sensors each having a different function. (3) A chemical analysis device using the semiconductor chemical sensor according to claim 1 or 2, wherein the semiconductor chemical sensor is formed on the same substrate. (4)-J, the semiconductor chemical sensor mentioned above is selected from 4), or a combination thereof, from among F E7p ion sensors, FETs, or gas sensors and O/enzyme sensors using semiconductor polarographic electrodes. A chemical analysis device using the semiconductor chemical sensor according to claim 1 or 2. (5) The arithmetic processing unit has a function of calculating the average value and standard deviation of the measured values corresponding to the outputs from each semiconductor sensor through statistical processing. A chemical analysis device using a semiconductor chemistry center/-9-.