JPH1068713A - Optical scanning type two-dimensional concentration distribution measuring device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To measure two-dimensional distribution of the density of a substance in time series by irradiating a semiconductor substrate with a probe light at high speed. SOLUTION: A DC current from a potentiostat 13 is applied across a reference electrode RE and an ohmic electrode OC so as to generate a depletion layer in a semiconductor substrate 5 and a prescribed bias voltage is applied on the semiconductor substrate 5. A probe light 3 of several kHz is intermittently applied on the semiconductor substrate 5 and an AC photoelectriccurrent is generated on the semiconductor substrate 5. The intermittent irradiation is generated by a control signal of a computer 18 via an interface board 14. An XY stage 10 moves a sensor 2 in the X, Y directions so that the probe light 3 is applied on the semiconductor substrate 5 to scan it two-dimensionally and a two-dimensional image expressing pH is displayed on a scope of a display 18B based on a position signal (X, Y) in solution 9 and an AC photoelectriccurrent value observed at the spot.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical scanning type two-dimensional concentration distribution measuring apparatus capable of two-dimensionally measuring ion concentration and the like in a sample such as a solution.

[0002]

2. Description of the Related Art Conventionally, when examining the pH value of a solution, for example, a pH sensor having a composite type electrode portion comprising a pH measuring electrode and a reference electrode liquid junction is used.
The composite electrode part of the H sensor is immersed in the solution. In this case, it is assumed that the solution as the sample is homogeneous, and only the temporal change of the pH value at one measurement point can be measured.

On the other hand, it has been almost impossible to measure a two-dimensional distribution time-series having a resolution on the order of sub-millimeters by using a large number of measuring probes and using many of them.

SUMMARY OF THE INVENTION The present invention has been made in consideration of the above-mentioned circumstances, and an object of the present invention is to provide an optical scanning type two-dimensional density distribution measuring apparatus capable of performing two-dimensional density distribution in time series. is there.

[0005]

In order to achieve the above object, an optical scanning type two-dimensional concentration distribution measuring apparatus according to the present invention has a sensor surface on one surface of a semiconductor substrate and a light source for the semiconductor substrate. In addition to the configuration in which light from the light source is irradiated two-dimensionally as probe light, time-series measurement is performed by irradiating the probe light at high speed.

According to the optical scanning type two-dimensional concentration distribution measuring device having the above configuration, the two-dimensional distribution of the substance concentration can be measured in time series. Then, by combining with an image output device such as a computer, a temporal change of the two-dimensional distribution of the substance concentration can be displayed as a continuous visible image. In this case, the change may be enlarged or reduced with respect to the time axis and displayed. Further, the concentration change at a certain point in the area where the two-dimensional distribution measurement of the substance concentration is performed may be displayed as a continuous visible image.

As a method of two-dimensionally irradiating the semiconductor substrate with probe light, the light source side is fixed, and the semiconductor substrate is two-dimensionally scanned.
A method of irradiating the semiconductor substrate while scanning the light from the light source two-dimensionally, or fixing the semiconductor substrate and scanning the light from the light source in the two-dimensional direction using a galvanometer mirror or an acousto-optic device. A method of irradiating a semiconductor substrate while fixing the semiconductor substrate, and a method of scanning a light source for irradiating the semiconductor substrate with probe light in a two-dimensional direction using a hypotrochoid or hypocycloid curve drawing mechanism. There is a method of using a flat light source array as a light source and irradiating the semiconductor substrate with light from the light source array while scanning the semiconductor substrate in a two-dimensional direction.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 shows an outline of an optical scanning type two-dimensional density distribution measuring apparatus according to the present invention. In FIG. 1, reference numeral 1 denotes a sensor unit, and a sensor 2 and a light for irradiating the sensor 2 with probe light 3. And an irradiation unit 4.

[0010] The sensor 2 is composed of a substrate 5 made of a semiconductor such as silicon on one surface (upper surface in the illustrated example) of SiO _2.
Thermal oxidation of layer 6 and Si ₃ N ₄ layer 7 as sensor surface, CV
The sensor surface 7 is formed so as to respond to various ions.
Reference numeral 8 denotes a cell which faces the sensor surface 7 and is provided so as to surround the periphery.

CE and RE are a counter electrode and a reference electrode provided so as to come into contact with a sample 9 arranged so as to come into contact with the sensor surface 7. These counter electrode CE and reference electrode RE are provided.
Are connected to a stabilizing bias circuit 15 of the potentiostat 13 described later. Further, OC is an ohmic electrode for taking out a current signal provided on the semiconductor substrate 5, and is connected to the stabilizing bias circuit 15 via a current-voltage converter 16 and an operational amplifier circuit 17, which will be described later.

Reference numeral 10 denotes a transmission as a sensor scanning mechanism for scanning the sensor 2 in a two-dimensional direction, that is, an X direction (a left-right direction in the illustrated example) and a Y direction (a direction perpendicular to the paper surface in the illustrated example). Type XY stage, scanning control device 11
Is controlled by

The light irradiating section 4 is made of, for example, a semiconductor laser, and is provided on the lower surface side of the semiconductor substrate 5 (opposite to the sensor surface 7). Computer 1
The probe light 3 which emits intermittent light in response to a control signal from the sensor 8 (to be described later) and which is adjusted so as to have an optimum beam diameter with respect to the semiconductor substrate 5 of the sensor 2 scanned in two-dimensional directions by the XY stage 10. Is irradiated.

Reference numeral 12 denotes a control box for controlling the sensor unit 1. The control box 12 applies an appropriate bias voltage to the semiconductor substrate 5, and takes out a signal obtained at that time as a current signal, and a potentiostat 13; And an interface board 14 for transmitting and receiving signals to and from the scanning controller 11 and outputting control signals to the light irradiation unit 4. And the potentiostat 13
A current-voltage converter 16 for converting a current signal taken out from the stabilizing bias circuit 15 and the ohmic electrode OC formed on the semiconductor substrate 6 into a voltage signal, and an operational amplifier to which a signal from the current-voltage converter 16 is input And a circuit 17.

Numeral 18 performs various controls and calculations,
A computer as an image output device having image processing and output functions; 18A, an input device such as a keyboard; 18B, a display device such as a color display;
C is a memory device.

The case where the hydrogen ion concentration (pH) of a solution is measured by using the optical scanning type two-dimensional concentration distribution measuring apparatus having the above-described configuration will be described. A solution as a sample 9 is placed in a cell 8. Thus, the solution 9 comes into contact with the sensor surface 7. Then, the counter electrode CE and the reference electrode RE are immersed in the solution 9.

In the above state, a DC voltage from the potentiostat 13 is applied between the reference electrode RE and the ohmic electrode OC so that a depletion layer is generated in the semiconductor substrate 5, and a predetermined bias is applied to the semiconductor substrate 5. Apply voltage. In this state, the probe light 3 is applied to the semiconductor substrate 5 by several kHz.
AC light current is generated in the semiconductor substrate 5 by intermittently irradiating with the frequency of. The intermittent irradiation of the probe light 3 is performed by inputting a control signal of the computer 18 through the interface board 14. The photocurrent is a value reflecting the pH of the solution 9 in contact with the sensor surface 7 at a point facing the irradiation point of the semiconductor substrate 6, and by measuring the value, the pH value at this portion is calculated. You can know.

Further, by moving the sensor 2 in the X and Y directions by the XY stage 10, the semiconductor substrate 5 is irradiated with the probe light 3 so as to be scanned in a two-dimensional direction, and the position signal in the solution 9 is obtained. Based on (X, Y) and the AC photocurrent value observed at that location, the display device 18
A two-dimensional image representing pH is displayed on the screen of B.

In the optical scanning type two-dimensional concentration distribution measuring device, the reference electrode RE may be omitted and a bias voltage may be applied via the counter electrode CE. However, the bias voltage can be more stably applied to the semiconductor substrate 5 when the comparative electrode RE is provided.

In the optical scanning type two-dimensional density distribution measuring device, the probe light 3 from the light irradiating section 4 may be irradiated from the sensor surface 7 of the semiconductor substrate 5.

Next, a more specific embodiment of the optical scanning type two-dimensional density distribution measuring apparatus will be described as a first embodiment with reference to FIGS.

First, FIG. 2 shows a specific configuration of an optical scanning type two-dimensional density distribution measuring apparatus.
The sensor unit includes a sensor 21, an XY stage 22 that scans the sensor 21 in a two-dimensional direction, and a light source 23 that irradiates light to, for example, the back side of the sensor 21.

The sensor 21 is a sensor 2 shown in FIG.
It is configured similarly to. The photocurrent from the sensor 21 is converted into a DC current proportional to the amplitude of the AC photocurrent via the operational amplifier circuit 25 of the signal processing unit 24.
The digital signal is converted into a 12-bit (bit) digital signal by the / D converter 26, and is taken in by a first personal computer (hereinafter, referred to as a first personal computer) 29 responsible for measurement control via a first board 28 of an interface board 27. .

The XY stage 22 is, for example, a high-speed and high-precision light transmission type X driven by a pulse motor (not shown).
It consists of a Y stage and has a maximum speed of 12,500 pps (12.5 mm / s) in 1 μm / 1 step. The XY stage 22 is connected via the second board 30 of the interface board 27 and the driver unit 31 to
It is controlled by the first personal computer 29.

The light source 23 has a wavelength of 780 nm and an output of 5.
It consists of a mW semiconductor laser. The laser light from the light source 23 is frequency-modulated at, for example, 5 kHz. A clock circuit 32 is provided in the signal processing unit 24 to synchronize the timing of capturing the output of the sensor 21 into the first personal computer 29 and the frequency of modulation of the laser light, and controls the A / D converter 26 and the laser output. It is carried out. 33 is a controller.

Reference numerals 34 and 35 denote a potentiostat and a D / A converter provided in the signal processing section 24, respectively.

Reference numeral 36 denotes a second personal computer for controlling the image processing, which is provided to dedicate the first personal computer 29 connected to the signal processing unit 24 to measurement control. Both 29,
The connection of 36 is performed by TCP / IP, and when data from one measurement is stored in the first personal computer 29, the data is automatically transmitted to the second personal computer 36, and the next measurement is possible. It is configured to be. And
The second personal computer 36 processes the photocurrent value at each irradiation point according to the coordinates of the irradiation point, and converts it into a two-dimensional image. At the time of this image conversion, the photocurrent value is converted into 8-bit gray scale data, and further, if necessary, pseudo color conversion can be performed.

Next, FIGS. 3 and 4 show the case where the process of releasing hydrogen ions from the ion exchange resin was measured using the optical scanning type two-dimensional concentration distribution measuring apparatus of the first embodiment.
This will be described with reference to FIG.

A sufficiently washed and dried cation exchange resin is prepared as an ion exchanger. The washing and drying may be performed, for example, by the method described in “Analytical Chemistry” (Kozo Nagashima, Isao Tomita, Shokabo), pp. 255-256. Then, the cell 8 (see FIG. 1) of the optical scanning type two-dimensional concentration distribution measuring device is filled with a 0.1 M KCl solution, and one cation exchange resin is put therein.

Immediately after immersing the cation exchange resin,
A two-dimensional pH distribution image of the KCl solution near the cation exchange resin A is measured by an optical scanning type two-dimensional concentration distribution measuring device. In this case, the number of pixels of the image is 64 × 64
The pixel size is set to 0.1 mm square so as to become a point.

Then, at two-minute intervals, two-dimensional pH images were measured in time series. The image sent from the first personal computer 29 to the second personal computer 36 is converted into 8-bit gray scale data by the image processing software in the personal computer 36, and is further converted into a pseudo color. The measurement is performed continuously for one hour, the above-described processing is performed on all the obtained 30 images, and the image is stored as image data on the hard disk of the second personal computer 36. If necessary, detailed analysis can be performed by displaying the image as a moving image using software capable of displaying the image in chronological order or displaying all pH profiles in a certain cross section.

That is, the two-dimensional p
The H distribution image is measured, and a series of images 37a to 37n are sequentially displayed on the display 36A of the second personal computer 36 during the measurement, as shown in FIG.
6 is stored as image data on the hard disk. Then, as shown in FIG.
37 to 37n may be displayed side by side on the display 36A, may be sequentially displayed as a moving image as shown in FIG. 3C, or may be displayed as a difference as shown in FIG. Here, the difference display means, for example, the image 37
b and the data in the image 37a are subtracted to obtain the image 37b
a.

The stored series of image data can be arbitrarily displayed on the display 36A by reading a part or all of the series of image data as needed.

As for the analysis, as shown in FIG. 4A, for a series of displayed images or a part of the images, a substance derived from the number, area, density, or density of points or areas of interest. Qualitative information can be obtained on the quantity. In addition, these values can be calculated to obtain quantitative information. FIG. 4A shows an example of a change in the area of the region of interest 38, and this area is calculated. FIG. 7B shows a change in the number of the regions of interest 39, and the number of regions is calculated.

In addition, qualitative or quantitative information can be obtained for the fluctuation of the value at each measurement timing.

Further, the change may be displayed while being enlarged or reduced with respect to a time axis.

At the time of measurement, initial data at the start of measurement when the sample is provided so as to be in contact with the sensor surface is collected, and the initial data is subtracted from the measured data after a lapse of a certain time from the start of measurement. In such a case, the influence of the background can be removed, and the true state of the measurement sample can be verified.

Further, when the measurement data after different time lapses from the start of the measurement when the sample is provided so as to be in contact with the sensor surface is subtracted, even if it is a minute change with time, Since it is possible to obtain transient information, it is possible to analyze the state of change more precisely.

In the above-described embodiment, the probe light 3 is irradiated on the semiconductor substrate 5 from the side opposite to the sensor surface 7 (lower surface side).
Irradiation may be performed from the same side as the sensor surface 7.

In the first embodiment, the light source 23 is fixed, and the semiconductor substrate 5 (sensor 21) is moved to the XY stage 22.
Is scanned two-dimensionally in the X and Y directions, whereby the semiconductor substrate 5 is scanned while the light 3 from the light source 23 is two-dimensionally scanned.
However, as shown in FIG. 5, the transmission type XY stage is not provided, the semiconductor substrate 5 (the sensor 2) is fixed, and the light 3 from the light source 4 is two-dimensionally irradiated by the light scanning mechanism 40. May be scanned. In FIG. 5, reference numeral 41 denotes a scanning control device for controlling the optical scanning mechanism 40. Hereinafter, such an optical scanning type two-dimensional density distribution measuring apparatus will be described as a second and a third embodiment with reference to FIGS.
This will be described with reference to FIG.

FIG. 6 shows a second embodiment, in which the optical scanning mechanism 40 is constituted by a galvanomirror. That is, in FIG. 6, reference numerals 42 and 43 denote galvanometer mirrors for scanning the light 3 from the light source 4 in the X direction and the Y direction, respectively, and reference numerals 44 and 45 denote galvanometers for driving these 42 and 43. Galvanometer 44, 4
5, a scanning control signal is input from a scanning control device (not shown). 46 is a condenser lens.

In the optical scanning mechanism 40 configured as described above, when the scanning control signals are input to the galvanometers 44 and 45, the galvanometer mirrors 42 and 43 swing their reflecting surfaces. Thus, the light 3 from the light source 4 is scanned in the X and Y directions, respectively,
This is irradiated while the semiconductor substrate 5 is two-dimensionally scanned through 6.

FIG. 7 shows a third embodiment, in which the optical scanning mechanism 40 is constituted by an acousto-optic element (AO element). That is, in FIG. 7, reference numerals 47 and 48 denote acousto-optical elements for scanning the light 3 from the light source 4 in the X and Y directions, respectively.
8 is a holding member for holding each of them. Acousto-optic element 4
Scan control signals are input to 9 and 50 from a scan control device (not shown).

In the optical scanning mechanism 40 configured as described above, the light 3 from the light source 4 is applied to the acousto-optic devices 47 and 4.
When a scanning control signal is input to the light 8, the light 3 incident thereon is deflected by a predetermined angle and emitted, whereby the light 3 from the light source 4 is scanned in the X and Y directions, and collected. This is irradiated while scanning the semiconductor substrate 5 two-dimensionally via the optical lens 46.

Light scanning mechanism 4 shown in second and third embodiments
The operation when 0 is used is the same as that of the first embodiment, and a description thereof will be omitted. In the optical scanning type two-dimensional density distribution measuring device according to the second and third embodiments, measurement of one screen can be performed in a few seconds.
Very fast. Therefore, the efficiency of the measurement is improved.

In the above-described second and third embodiments,
The optical scanning mechanism 40 is constituted by the two galvanometer mirrors 42 and 43 or the two acousto-optic elements 47 and 48. Instead, the optical scanning mechanism 40 is replaced by one galvanomirror and one acousto-optic element. May be combined.

Also, in the second and third embodiments,
Although the probe light 3 is irradiated on the semiconductor substrate 5 from the side opposite to the sensor surface 7 (lower surface side), the probe light 3 may be irradiated from the same side as the sensor surface 7 instead.

In the first to third embodiments, the light source 4 for irradiating the semiconductor substrate 5 is fixed, the XY stage 10 is provided on the semiconductor substrate 5, and the semiconductor substrate 5 is scanned in the two-dimensional direction. Embodiment 1) An optical scanning mechanism 40 is provided between the light source 4 and the semiconductor substrate 5 to scan the light 3 from the light source 4 in a two-dimensional direction. The light source 4 for irradiating 3 may be two-dimensionally scanned by using a hypotrochoid or hypocycloid curve drawing mechanism. Hereinafter, this will be described as a fourth embodiment with reference to FIGS.

First, in FIG. 8, reference numeral 51 denotes a frame made of an appropriate material. The sensor 2 is provided on the upper portion of the frame 51. The lower portion of the frame 51, more specifically, the lower portion of the sensor 2, Is provided with a two-dimensional light irradiation unit 52.

The two-dimensional light irradiating section 52 is configured as follows, for example. That is, in FIGS. 8 and 9, reference numeral 53 denotes a pulse motor attached to the base member 54 via an appropriate member, and is provided in a vertical direction so that the output shaft 55 protrudes from the upper surface of the base member 54. A driving gear 56 is horizontally fixed to the output shaft 55. The pulse motor 53 is controlled by a computer (not shown) via the interface board 14.

Reference numeral 57 denotes a driven gear that meshes with the driving gear 56, and a rotating shaft 58 of the driven gear 57 is vertically provided on the base member 54 via a bearing member 59. Reference numeral 60 denotes a sun gear having a rotation center on the same axis as the driven gear 57, and a plurality of teeth are provided on the inner circumference.

Reference numeral 61 denotes a planetary gear which is rotatably supported by a pin member 62 which is provided on the driven gear 57 at a position appropriately distant from the rotation center 58, and which always rotates while inscribed in the sun gear 60.

Reference numeral 63 denotes a functional element installation section provided on the planetary gear 61 at a position distant from the center of rotation 62 of the planetary gear 61. The functional element installation section 63 includes a laser light source 64 as a light source and a condenser lens. A light source unit 66 including a light source unit 65 is provided. The light source 66 irradiates the semiconductor substrate 5 of the sensor 2 with the probe light 67, and is provided so that the condenser lens 65 does not contact the lower surface of the semiconductor substrate 5.

Reference numeral 68 denotes a plate-shaped member connected to the functional element installation portion 63, which is provided with an elongated hole 69 having a length which can cope with the movement of the planetary gear 61.
The pin member 71 erected at 0 is inserted therethrough. Although not shown in detail, a power cable for supplying power to the light source 64 is provided along the plate member 68.

The device consisting of the members denoted by reference numerals 53 to 63 is called a hypotrochoid or hypocycloid curve drawing mechanism, and is denoted by reference numeral 72.

Here, a drawing equation for irradiating the semiconductor substrate 5 with the probe light 67 while scanning it two-dimensionally by the two-dimensional light irradiation unit 52 will be described with reference to FIG.

In FIG. 10, L is a great circle (corresponding to the sun gear 60), and S is a small circle (corresponding to the planetary gear 61) that rotates inscribed therein. In addition, L _r: great circle L of radius O _L: the center of the large circle L S _r: radius O _S of the small circle S: center of the small circle S Q: point were separated by a distance r from the center of the small circle S A: large A position on the great circle L when the circle L and the small circle S are in contact in the initial state B: A position on the small circle S when the circle L and the small circle S are in contact in the initial state C: Small circle S is the angle theta _L (radian) contact position between the large circle L and the small circles S in when rotated theta _10: a line segment CO _s and the line segment O _S B and the angle (in radians).

The coordinates of the point C are (L _r · cos θ _L , L _r
Sin θ _L ). The great circle L, with the rotation in the arrow direction of the small circles S, although both the contacts are moved, the movement length in both are equal to each other, because it is arc AC = arc _{BC, θ L · L r =} θ _S · S _r (1) holds.

With the rotation of the small circle S, the center O _S of the small circle S moves on the circumference of a circle (indicated by an imaginary line in the figure) having a radius (L _r −S _r ), and its coordinates are ｛(L _r −S _r ) · cos
θ _L , (L _r −S _r ) · sin θ _L ).

The coordinates (X _Q , Y _Q ) of the point Q are expressed as follows. That is, X _Q = (L _r −S _r ) · cos θ _L −r · cos (θ _L −θ _S ) (2) Y _Q = (L _r −S _r ) · sin θ _L −r · sin (θ _L− θ _S ) (3)

Incidentally, as described above, arc AC = arc B
Since C, from equation (1), θ _S = L _r · θ _L / S _r (4) is obtained. By substituting this into the above equations (2) and (3), X _P = ( L _r −S _r ) · cos θ _L −r · cos ｛θ _L • (S _r −L _r ) / S _r … (5) Y _p = (L _r −S _r ) · sin θ _L −r · sin ｛Θ _L · (S _r -L _r ) / S _r … …… (6)

The locus drawn by the point Q is the center O of the great circle L.
If through _L, and the because it is _r = L r -S r, (5)
_, (6) _{Equation, X P = r · {cosθ} L + cos (θ L · r / S r)} ...... (7) Y p = r · {sinθ L + sin (θ L · r / S r)} (8)

A program having the above-described drawing equation is provided in the computer, and the two-dimensional light irradiation unit 5
2 is controlled based on this program.

Now, the modules of the driving gear 56, the driven gear 57, the sun gear 60 and the planetary gear 61, and the pitch of the number of teeth used in the present invention are as shown in Table 1 below, for example.
It is assumed that the center of the planetary gear 61 is located at a position ３ of the radius of the driven gear 57 and the point Q, that is, the locus drawn by the light source 66 passes through the center 58 of the sun gear 60.

[0065]

[Table 1]

The two-dimensional plane scanning method by the two-dimensional light irradiation unit 52 will be described with reference to FIGS. 8 to 11. By rotating the pulse motor 53, the driving gear 56 is moved in the direction of an arrow 73 in FIG. Rotate to
Accordingly, the driven gear 57 is moved in the direction indicated by the arrow 74 in FIG.
The sun gear 60 also rotates in the direction of arrow 75.

When the driving gear 56 makes one rotation, the planetary gear 61 is inscribed in the sun gear 60 at a predetermined rotation speed (6
05/403) in the direction of arrow 76,
Revolve once and return to the original position.

When the planetary gear 61 is rotated, for example, 605 times, the planetary gear 61 returns to its original position. With this rotation, the light source unit 66 draws a locus represented by a curve 77 and draws a two-dimensional plane in one stroke. Go to Thus, the two-dimensional plane is scanned by the light source unit 66 as shown in FIG.

Here, assuming that a frame until the trajectory (specific trajectory) drawn by the light source unit 66 is completed is one frame, this one frame scans all the specific two-dimensional areas around the rotation center 58 of the sun gear 60. Trajectory. This trajectory
This is exactly the locus drawn by the point Q (see FIG. 10) described above.
From the equation of the trajectory, the position information of the X axis and the Y axis is calculated in advance, and the rotation start point and the origin are determined in advance. Then, the light source unit 66 can be continuously moved to a specific position by determining the X coordinate and the Y coordinate according to the time from the start of movement based on the origin.

When the driving gear 56 is continuously rotated to cause the light source section 66 to draw a trajectory of one frame on a two-dimensional plane, the X-axis and the Y-axis on the frame plane represent the two-dimensional plane. Select a specific position or its vicinity (within the error range) in advance, calculate the position and return to origin time (time zero)
Trajectory is drawn such that the light source 66 follows a large number of X and Y positions representing two dimensions at every specific time.

The operation of the optical scanning type two-dimensional density distribution measuring apparatus of the fourth embodiment is the same as that of the first embodiment, and the description is omitted. In the optical scanning type two-dimensional density distribution measuring apparatus according to the fourth embodiment, measurement of one screen can be performed in 30 seconds or less, which is very fast. Therefore, the efficiency of the measurement is improved.

By the way, also in the above-mentioned fourth embodiment,
Although the probe light 33 is irradiated on the semiconductor substrate 5 from the side opposite to the sensor surface 7 (lower surface side), the probe light 33 may be irradiated from the same side as the sensor surface 7 instead.

Then, a servo motor may be used instead of the pulse motor 53.

In the above-described embodiment, the trajectory drawn by the light source 66 provided on the functional element installation section 63 passes through the center 58 of the sun gear 60. The installation position is arbitrary on the planetary gear 61 and other than the rotation center 62 thereof. In this case, the trajectory drawn by the functional element installation section 63, that is, the light source section 66 does not necessarily pass through the center 58 of the sun gear 60, but various trajectories can be obtained.

In the above embodiment, the planetary gear 61 is provided so as to rotate while always inscribed in the sun gear 60. Instead, however, the planetary gear 61 is provided so as to rotate while always inscribed in the sun. Is also good. Even in this case, it is possible to cause the functional element installation section 63 to draw various trajectories.

In the first to fourth embodiments, a single light source is used. However, a plurality of light sources may be used. That is, a plurality of light sources are two-dimensionally arranged to form a light source array, and the light source elements in the light source array are sequentially two-dimensionally scanned and turned on, and the semiconductor substrate 5 is irradiated while being two-dimensionally scanned. . Hereinafter, such an optical scanning type two-dimensional density distribution measuring apparatus will be described as fifth and sixth embodiments with reference to FIGS.

FIG. 13 shows an example of an optical scanning type two-dimensional density distribution measuring apparatus according to the fifth embodiment. In this figure, reference numeral 78 denotes a light source array for irradiating the semiconductor substrate 5 two-dimensionally. is there. As shown in FIG. 14, the light source array 78 includes a light emitting substrate 80 in which a plurality of LEDs 79 are formed at equal intervals in the X and Y directions, for example.
And the LED 7 while holding the luminous body substrate 80.
Shift register 81 which controls so as to sequentially turn on 9
Printed circuit board 8 as scanning control unit provided with X, 81Y
Consists of two.

The light source array 78 is formed separately from the sensor 2, for example, and is formed on the surface opposite to the sensor surface 7 of the sensor 2 by using an appropriate adhesive, anodic bonding or direct bonding. The luminous body substrates 80 are joined so as to be in direct contact with each other, thereby forming an optical scanning type two-dimensional concentration distribution measuring device having a composite structure (hybrid structure).

The operation of the optical scanning type two-dimensional density distribution measuring apparatus of the fifth embodiment is the same as that of the first embodiment, and the description is omitted. According to the optical scanning type two-dimensional density distribution measuring device, one pixel size is 500 μm.
It is as follows, and one screen can be measured in a few seconds.

Although not shown, a plurality of microlenses are interposed between the sensor 2 and the light source array 78 so as to correspond to the plurality of LEDs 79, respectively.
The probe light 3 from D79 may be focused on a predetermined position on the semiconductor substrate 5.

In the fifth embodiment, the optical scanning type two-dimensional concentration distribution measuring apparatus has a hybrid structure. However, as shown in FIG. 15, the apparatus may be configured as an integral structure (monolithic structure). That is, FIG. 15 shows an optical scanning type two-dimensional concentration distribution measuring apparatus according to the sixth embodiment. In this figure, reference numeral 83 denotes a GaAs formed on the surface of the semiconductor substrate 5 opposite to the sensor surface 7. Layer 84 is the GaAs layer 83
A Ge layer 85 formed on the Ge layer 84 is a Si layer formed on the Ge layer 84, and a plurality of LCDs (liquid crystals) spread in the X and Y directions as shown in FIG.
A light source array 78 composed of 86 is formed. Note that 87
Is an address decoder as a control unit for appropriately controlling the opening and closing of the shutters of the plurality of LCDs 86.

The operation of the optical scanning type two-dimensional density distribution measuring apparatus having a monolithic structure according to the sixth embodiment is the same as that of the optical scanning type two-dimensional density distribution measuring apparatus according to the fifth embodiment. Detailed description is omitted. In the optical scanning type two-dimensional concentration distribution measuring apparatus having a monolithic structure as described above, in addition to the effect of the hybrid configuration, it is possible to measure even a minute portion and to have a high resolution, Is possible.

The light source array 78 includes LEDs,
In addition to the LCD, an EL (electroluminescence), a solid-state laser, or the like can be used.

In the fifth and sixth embodiments, there is no mechanical part in the mechanism for irradiating the semiconductor substrate 5 with the probe light 3, so that the structure is simple and the configuration is simple, and the position information is fixed. , Works stably.

According to the fifth and sixth embodiments, a conventional semiconductor manufacturing process can be applied.
Therefore, it can be mass-produced.

According to the present invention, not only the above-described pH measurement of the solution but also a two-dimensional measurement of the pH of a solution contained in a substance such as an apple can be performed. That is, the apple is cut in half, the cut surface is brought into contact with the sensor surface 7, the counter electrode CE and the reference electrode RE are inserted into the apple, and a bias voltage is applied by the potentiostat 13 in this state. The light 3 is applied to the semiconductor substrate 5.

In each of the above embodiments, the measurement of pH was performed. However, the present invention is not limited to this, and can be applied to the case of measuring potassium ion or chloride ion. it can. In this case, it is necessary to modify the sensor surface 7 of the optical scanning type two-dimensional concentration distribution measuring device with a substance which responds to potassium ions and chloride ions, respectively. For example, substances that respond to potassium ions include:
Substances such as valinomycin and crown ether which respond to chloride ions include quaternary ammonium, and the sensor surface 7 is modified with these substances. Further, by modifying the sensor surface 7 with an appropriate responding substance and appropriately selecting a solution to be used, it is possible to cope with the measurement of other ions.

Further, the probe light 3 radiated from the light source 4 to the semiconductor substrate 5 can be appropriately selected from various rays such as infrared rays, ultraviolet rays, and visible rays.

[0089]

The present invention is embodied in the above-described embodiment and has the following effects.

The optical scanning type two-dimensional concentration distribution measuring apparatus of the present invention has a sensor surface on one surface of a semiconductor substrate, and two-dimensionally irradiates the semiconductor substrate with light from a light source as probe light. With such a configuration, the time series measurement is performed by irradiating the probe light at high speed, so that the two-dimensional distribution of the concentration of various substances can be measured in time series.

By combining this with an image output device such as a computer, a temporal change in the two-dimensional distribution of the substance concentration can be displayed as a continuous visible image.
Further, the change can be displayed by being enlarged or reduced with respect to a time axis, and furthermore, a concentration change at a certain point in a region where the two-dimensional distribution measurement of the substance concentration is performed is displayed as a continuous visible image. You can also.

[Brief description of the drawings]

FIG. 1 is a diagram showing an outline of an optical scanning type two-dimensional density distribution measuring device of the present invention.

FIG. 2 is a block diagram showing a specific configuration of the optical scanning type two-dimensional density distribution measuring device of the first embodiment.

FIG. 3 is an operation explanatory diagram of the first embodiment.

FIG. 4 is an operation explanatory diagram of the first embodiment.

FIG. 5 is a diagram comprehensively showing the second and third embodiments.

FIG. 6 is a diagram showing a main part of a second embodiment.

FIG. 7 is a diagram showing a main part of a third embodiment.

FIG. 8 is a diagram showing a specific configuration of an optical scanning type two-dimensional density distribution measuring device of a fourth embodiment.

FIG. 9 is a perspective view showing an example of a curve drawing mechanism used in a fourth embodiment.

FIG. 10 is a diagram for explaining the operation principle of the curve drawing mechanism.

FIG. 11 is a diagram illustrating the operation of the curve drawing mechanism.

FIG. 12 is a diagram showing an example of a locus drawn by the curve drawing mechanism.

FIG. 13 is a diagram showing a specific configuration of an optical scanning type two-dimensional density distribution measuring device according to a fifth embodiment.

FIG. 14 is a diagram schematically showing an example of a light source array used in the fifth embodiment.

FIG. 15 is a diagram showing a specific configuration of an optical scanning type two-dimensional density distribution measuring device of a sixth embodiment.

[Explanation of symbols]

3 light source, 4 probe light, 5 semiconductor substrate, 7 sensor surface, 10 XY stage, 18 image output device, 4
2, 43: galvanomirror, 48, 49: acousto-optical element, 72: curve drawing mechanism, 78: flat light source array.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Motoi Nakao 2 Higashicho, Kichijoin-gu, Minami-ku, Kyoto, Kyoto Inside Horiba, Ltd.

Claims (6)

[Claims] 1. A semiconductor substrate having a sensor surface on one surface, configured to irradiate the semiconductor substrate with light from a light source as probe light while scanning the probe light two-dimensionally, and the probe light 2. An optical scanning type two-dimensional density distribution measuring device, wherein time series measurement is performed by performing high-speed irradiation of light. 2. The method according to claim 1, wherein a temporal change of the two-dimensional distribution of the substance concentration obtained by performing the time series measurement can be displayed as a continuous visible image by combining with an image output device such as a computer. Optical scanning type two-dimensional concentration distribution measuring device. 3. The optical scanning type two-dimensional density distribution measuring apparatus according to claim 1, wherein an XY stage for scanning the semiconductor substrate in a two-dimensional direction is provided on a side of the semiconductor substrate opposite to the sensor surface. 4. Light from a light source is applied to a semiconductor substrate.
The optical scanning type two-dimensional density distribution measuring device according to claim 1, wherein irradiation is performed while scanning in a two-dimensional direction using a galvanomirror and / or an acousto-optic device. 5. The light according to claim 1, wherein a light source for irradiating the semiconductor substrate with probe light is scanned two-dimensionally using a hypotrochoid or hypocycloid curve drawing mechanism. Scanning two-dimensional concentration distribution measuring device. 6. A flat light source array as a light source, and irradiates the semiconductor substrate with light from the light source array while scanning the semiconductor substrate in a two-dimensional direction.
2. The optical scanning type two-dimensional concentration distribution measuring device according to 1.