JP2002303662A - Electron spin resonance device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To automatically set parameters of ESR to optimum values. SOLUTION: While magnetic field modulation width is sequentially varied, the absorption quantity of a peak is detected and the magnetic field variation width right before the proportional relation between the absorption quantity corresponding to last magnetic field modulation width and the absorption quantity corresponding to current magnetic field modulation width is lost is set as an optimum value. While microwave output is sequentially varied, the maximum value of the absorption quantity of the peak is detected and the microwave output right before the proportional relation between the absorption quantity corresponding to last microwave output and the absorption quantity corresponding to current microwave output is lost is set as an optimum value. As for a response time, while the time constant of a circuit behind a detector is varied in specific steps, the half-value width of a couple of peaks is detected and the time constant right before the half-value width exits from its fixed- value state is set as a time constant which gives an optimum response time. While a magnetic field sweep time is sequentially varied, the magnetic field intensity position of the peak is detected and the magnetic sweep time right before the magnetic field intensity position exits from its fixed state is set as an optimum value.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electron spin resonance apparatus (hereinafter, referred to as ESR (electron spin resonance)), and more particularly to a magnetic field sweep range, a magnetic field modulation width, and a magnetic field modulation width required for ESR measurement. The present invention relates to an ESR that automatically sets five parameters of microwave output, response time of a circuit subsequent to a detector (hereinafter simply referred to as response time), and magnetic field sweep time to optimum values.

[0002]

2. Description of the Related Art Although the structure of an ESR is well known, FIG.
1 shows a schematic configuration of an ESR. In the figure, 1 is a sample tube, 2 is a cavity resonator, 3 is an electromagnet, 4 is a microwave generator, 5 is a magnetic field modulation / sweep device, 6 is a detector, 7 is an amplifier, 8 is a noise filter, and 9 is control. The device is shown.

A sample is placed in a sample tube 1 and a cavity resonator 2
Is located inside. The microwave generated by the microwave generator 4 is guided into the cavity resonator 2 by a waveguide. An electromagnet 3 is arranged outside the cavity resonator 2, and its magnetic field is modulated by a magnetic field modulation / sweep device 5, and the magnetic field intensity is swept. The signal detected by the detector 6 is digitized by an A / D converter (not shown) via an amplifier 7 and a noise filter 8 for cutting noise, is taken into a control device 9, and is stored in a hard disk or the like. It is stored in a device (not shown). Thereafter, by outputting the data to a monitor or a plotter (neither is shown), the operator can observe the measured spectrum. In FIG. 6, the amplifier 7 and the noise filter 8 are separate, but it is also possible to configure the amplifier to have a noise filter mechanism.

It is known that a spectrum obtained by ESR is a first-order differential waveform in which peaks appear above and below a base line BL, as shown in FIG. The horizontal axis of the spectrum is the magnetic field strength, and the vertical axis is the amount of microwave absorption (hereinafter, referred to as
Simply referred to as absorption amount). Then, a peak appearing above the base line BL as a left peak in FIG. 7 is referred to as a positive peak, and a peak appearing below the base line BL as a right peak in FIG. 7 is referred to as a negative peak. 7, the width of the magnetic field intensity between the local maximum value of the positive peak and the local minimum value of the negative peak, which is indicated by ΔH in FIG.

[0005]

When measuring by ESR, five parameters of a magnetic field sweep range, a magnetic field modulation width, a microwave output, a response time, and a magnetic field sweep time are required to obtain a good spectrum. It must be set optimally. That is, it is natural that all positive and negative peaks obtained from the sample must be able to be obtained. Therefore, if the magnetic field sweep range is set narrow, there is a possibility that not all peaks can be obtained. On the other hand, if the magnetic field is swept over a very wide range, all the peaks can be obtained, but the measurement time is unnecessarily long. Therefore, in order to measure efficiently, it is necessary to optimally set the magnetic field sweep range.

It is known that the sensitivity is improved as the magnetic field modulation width is increased, and the positive and negative peaks of the spectrum are strong and clearly appear. Therefore, it is desired to set the magnetic field modulation width as large as possible without distorting the spectrum.

[0007] Similarly to the magnetic field modulation width, the microwave output is higher in sensitivity as the microwave output is increased, and the positive and negative peaks of the spectrum are strong and clearly appear. ing. Therefore, it is desired that the microwave output is set to be large as long as the spectrum is not distorted.

It is desirable that the response time of the amplifier 7 and the noise filter 8 downstream of the detector be short. This is because if the response time is short, it can respond to a signal having a sharp spike waveform. However, if the response time is too short, it will also respond to spike-like noise. However, it is known that if the response time is too long, the waveform of the positive and negative peaks of the spectrum becomes dull. Therefore, it is desired that the response time of the circuit be set so that it does not respond to spike noise and that the waveform of the peak of the spectrum is not distorted.

Further, when the above-described magnetic field sweep range is set, it becomes a problem how long the magnetic field sweep range is swept. Of course, a good spectrum can be obtained by slowly sweeping the set magnetic field sweep range over time. However, in view of work efficiency, it is desirable to perform the magnetic field sweep in as short a time as possible. However, it is known that if the magnetic field sweep is performed in a very short time, the position of the magnetic field strength at which the spectrum peak appears changes. Therefore,
It is desirable that the magnetic field sweep time be as short as possible within a range where the position of the magnetic field strength at the peak of the spectrum does not change.

As described above, in order to obtain a good spectrum without distortion of the peak waveform and to improve the working efficiency, the magnetic field sweep range, the magnetic field modulation width, the microwave output, the response time, and the magnetic field sweep time are required. It is necessary to optimally set the five parameters. Conventionally, using a sample to be measured, the operator actually measures several times while appropriately changing the values of these parameters.
Observing the obtained spectrum and determining the optimal parameter values based on experience, it required skill.

Therefore, the present invention provides an electron spin resonance apparatus capable of automatically and optimally setting five parameter values of a magnetic field sweep range, a magnetic field modulation width, a microwave output, a response time, and a magnetic field sweep time. It is intended to provide.

[0012]

In order to achieve the above object, an electron spin resonance apparatus according to claim 1 comprises at least a sweep range of a magnetic field, a modulation width of a magnetic field, a microwave output,
It is characterized by comprising means for performing processing for automatically setting the five parameters of the response time of the circuit subsequent to the detector and the sweep time of the magnetic field sweep to optimal values. An electron spin resonance apparatus according to claim 2, wherein the number of positive or negative peaks is detected based on a signal obtained when a sufficiently wide magnetic field intensity range is swept, and the number of positive or negative peaks is even. The magnetic field sweep range is set based on the magnetic field strength position of the positive peak of the smallest magnetic field strength and the magnetic field strength position of the negative peak at the largest magnetic field strength, and the number of positive or negative peaks is odd. In this case, the position of the maximum value of the middle positive peak and the position of the minimum value of the negative peak paired with the positive peak are obtained, and the position of the maximum value position and the center position of the minimum value position are obtained. Is a central magnetic field, and means for performing a process of setting a range obtained by multiplying the half value width of the positive and negative peaks forming the middle pair by a predetermined multiple as the magnetic field sweeping range from the central magnetic field to the larger and smaller magnetic field intensities, respectively. at least Characterized in that it obtain. The electron spin resonance apparatus according to claim 3 focuses on one peak, detects the absorption amount of the peak while sequentially changing the magnetic field modulation width, and detects the absorption amount at the previous magnetic field modulation width and the current magnetic field modulation width. It is characterized in that at least means is provided for determining whether or not the amount of absorption at the time of the modulation width is in a proportional relationship, and performing processing for setting the magnetic field modulation width immediately before the proportional relationship no longer holds as an optimum value. The electron spin resonance apparatus according to claim 4 focuses on one peak, detects the maximum value of the absorption amount of the peak while sequentially changing the microwave output, and detects the absorption amount at the time of the previous microwave output, It is characterized by comprising at least means for determining whether or not the amount of absorption at the time of this microwave output is in a proportional relationship, and setting a microwave output immediately before the proportional relationship is no longer established as an optimum value. . The electron spin resonance apparatus according to claim 5 focuses on a pair of positive and negative peaks, detects a half width of a peak of the pair while changing a time constant of a circuit subsequent to the detector in a predetermined step, and At least means for performing processing for setting a time constant immediately before departure from a state where the value width is constant as giving an optimum response time is provided. The electron spin resonance apparatus according to claim 6, paying attention to one peak, detects the magnetic field intensity position of the peak while sequentially changing the magnetic field sweep time, and detects the magnetic field intensity position at the time of the previous magnetic field sweep time and this time. Determine whether the magnetic field intensity position at the time of the magnetic field sweep time is the same within the range of the error, and optimize the magnetic field sweep time immediately before the magnetic field intensity position of the peak deviates from the state where it is constant within the range of the error. It is characterized by comprising at least means for performing a process of setting as a value. The electron spin resonance apparatus according to claim 7 focuses on the pair of positive and negative peaks, detects the half-width of the pair of peaks while sequentially changing the magnetic field sweep time, and detects the half-width immediately before the half-width deviates from a constant state. At least means for performing a process of setting the magnetic field sweep time as an optimum value is provided.

[0013]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows an ESR according to the present invention.
FIG. 1 is a diagram illustrating a configuration of one embodiment, in which reference numeral 10 denotes an input device including a keyboard, a pointing device, an operation panel, and the like. In FIG. 1, the same components as those shown in FIG. 6 are denoted by the same reference numerals.

In this ESR, the microwave generator 4,
The microwave output, amplification factor, and time constant of the magnetic field modulation / sweep device 5, the amplifier 7, and the noise filter 8 can be controlled by control signals from the control device 9, respectively.
In addition, the control device 9 controls a magnetic field sweep range described below,
Software for automatically and optimally setting the five parameter values of the magnetic field modulation width, the microwave output, the response time, and the magnetic field sweep time is installed.

In the following description, the response time is determined by adjusting the time constant of the noise filter 8. However, the response time may be adjusted by adjusting the time constant of the filters of the detector 6 and the amplifier 7. Good. In short, the detector 6
This can be achieved by adjusting the time constant of a circuit at a later stage.

The operation will be described below. When measuring a certain sample, the operator places the sample in the sample tube 1 and sets it inside the cavity resonator 2, operates the input device 10, and selects a parameter setting menu. Thereby, the control device 9 starts an operation of automatically setting the five parameter values. The setting order of the five parameters can be arbitrarily determined. Here, the control device 9 controls the magnetic field sweep range, the magnetic field modulation width, the microwave output, the response time,
The operation of setting the optimum value in the order of the magnetic field sweep time is performed.

(1) Operation for Setting Magnetic Field Sweep Range When the control device 9 detects that the parameter setting menu is selected, the control device 9 instructs the magnetic field modulation / sweep device 5 to perform a predetermined sweep time and modulation width. , A control signal for sweeping a predetermined range of the magnetic field strength is notified. The magnetic field strength range to be swept at this time may be set in the control device 9 in advance to be a sufficiently wide range, for example, the entire magnetic field strength range measurable by the ESR. At this time, the control device 9 controls the microwave generation device 4 to output a control signal for obtaining a predetermined microwave output, and controls the amplifier 7 to output a control signal for obtaining a predetermined amplification factor. A signal is transmitted to the noise filter 8 with a control signal having a predetermined time constant.

The magnetic field modulation / sweep device 5 generates a current for sweeping the specified magnetic field intensity range with the specified sweep time and modulation width based on the control signal, and supplies the current to the electromagnet 3. At this time, the control device 9 takes in the signal detected by the detector 6 and digitized via the amplifier 7 and the noise filter 8. Then, the control device 9 obtains a positive peak and a negative peak in the acquired signal. In the process of obtaining the positive and negative peaks, for example, an average value and a standard deviation of the values of the sample points of the acquired signal are obtained, and a signal within three times the standard deviation in the positive and negative directions from the average value is regarded as noise. Only a signal having a value exceeding the value and a value below the value may be made valid, and the maximum value in the valid signal may be a positive peak, and the minimum value may be a negative peak. When the positive and negative peaks are detected in this manner, the control device 9 next counts the number of positive or negative peaks and determines the range of the magnetic field intensity to be swept according to whether the peak is even or odd.
Here, the number of positive peaks is counted.

If the number of the positive peaks is even, for the positive peak at the smallest magnetic field strength, the position of the effective signal having the smallest value on the side with the smaller magnetic field strength is obtained, and the magnetic field is determined from the position. A predetermined margin width is added in the direction in which the intensity decreases, and the position of the magnetic field intensity having the smaller magnetic field intensity of the margin width is set as one end point of the magnetic field sweep. FIG. 2A is a diagram for explaining the above-described processing, wherein P _min indicates a positive peak at the smallest magnetic field strength, and A indicates the largest value at which the magnetic field strength of the peak P _min is smaller. M indicates a position of a small effective signal, M indicates a margin width, and S indicates a position of a magnetic field intensity having a smaller magnetic field intensity of the margin width M, and indicates a position to be one end point of the magnetic field sweep. Note that the margin width M may be set to an appropriate value based on experiments and experiences. Further, the control device 9 obtains the position of the effective signal having the largest value on the side where the magnetic field strength is large with respect to the negative peak at the largest magnetic field strength, and from the position, the predetermined position in the direction in which the magnetic field strength becomes large. A margin width is added, and the position of the magnetic field strength having the larger magnetic field strength of the margin width is set as the other end point of the magnetic field sweep. FIG. 2B is a diagram for explaining the above-described processing, where P _max indicates a negative peak at the largest magnetic field intensity, and B indicates the largest value at the peak P _{max in} the direction of increasing magnetic field intensity. M indicates a position of a large effective signal, M indicates a margin width, E indicates a position of a magnetic field intensity having a larger magnetic field intensity of the margin width M, and indicates a position to be the other end point of the magnetic field sweep. . Then, the controller 9 optimally sweeps the range of the two end points obtained by the above-described processing, that is, the range from the position indicated by S in FIG. 2A to the position indicated by E in FIG. Set as a range.

The above description is for the case where the number of positive peaks is an even number. When the number of positive peaks is an odd number, the magnetic field sweeping range can be set by the same processing. However, another processing will be described here. I do.

The controller 9 first finds the position of the maximum value of the middle positive peak and the position of the minimum value of the negative peak paired with the positive peak, and further determines the position of the maximum value and the minimum value. The central position of the position is defined as the central magnetic field. Then, from the center magnetic field, the half value width of the positive and negative peaks forming the middle pair is multiplied by a first predetermined multiple, and the width obtained by multiplying the half value width by a first predetermined multiple is defined as the smaller magnetic field intensity from the central magnetic field. Each is taken in the larger direction, and it is determined whether all positive and negative peaks fall within the magnetic field strength range. If all the positive and negative peaks fall within the magnetic field strength range, the magnetic field strength range is set as the magnetic field sweep range.If not, the half width is multiplied by a second predetermined multiple, and Take the width from the central magnetic field to the smaller and larger magnetic field strengths respectively,
The process of determining whether or not all the positive and negative peaks fall within the magnetic field strength range is repeated. When the range in which all the positive and negative peaks fall is determined, the magnetic field strength range is set as the optimum magnetic field sweep range. The first predetermined multiple is, for example, 10 times, the second predetermined multiple is 11 times, and the third predetermined multiple is 12 times. I just need.

FIG. 3 shows the concept of the above processing. In FIG. 3, P is the middle positive peak, P 'is the negative peak paired with the positive peak P, _Pmax is the negative peak at the highest magnetic field strength, and _Pmin is the positive peak at the lowest magnetic field strength. T indicates the position of the central magnetic field which is the center position between the position of the maximum value of the positive peak P and the position of the minimum value of the negative peak P ′, and ΔH indicates the position of the central positive peak P And the half width of the negative peak P '. In this state, half width △
When H is multiplied by m and the magnetic field strength width mx △ H is shifted from the central magnetic field T to the larger and smaller magnetic field strengths, S
All the positive and negative peaks from the positive peak P _{min at} the lowest magnetic field strength to the negative peak P _max at the highest magnetic field strength are within the range of the magnetic field strength of T ± m × △ H from to E. If it is included, the control device 9 sets the magnetic field strength range from S to E in FIG. 3 as the optimum magnetic field sweep range.

By the above processing, the optimum magnetic field sweep range is automatically set regardless of whether the number of the positive peaks is even or the number of the positive peaks. Then, the control device 9 sets and stores the optimum magnetic field sweep range by the above processing.
The magnetic field intensity position of the positive peak having the maximum absorption amount and the magnetic field intensity position of the negative peak paired with the positive peak are detected and stored. These are used for optimal setting of parameters described later.

(2) Operation for Setting Magnetic Field Modulation Width When the controller 9 finishes setting the magnetic field sweep range, it performs an operation for setting the magnetic field modulation width. In ESR, it is known that the amount of absorption appearing in the spectrum has a relationship with the magnetic field modulation width. As shown in FIG. 4, when the magnetic field modulation width is small, the absorption amount has a linear relationship with the magnetic field modulation width. It is known that as the magnetic field modulation width increases, the linearity of the absorption amount and the magnetic field modulation width deteriorates. That is, in the range where the magnetic field modulation width is small, if the magnetic field modulation width is multiplied by n, the absorption amount is also multiplied by n.

In the case where the absorption amount and the magnetic field modulation width have the relationship shown in FIG. 4, it is desirable that the output signal of the detector 6 be large in consideration of how the magnetic field modulation width is desired. If the output signal of the detector 6 is large, the positive and negative peaks of the spectrum are large, so that the spectrum is easy to see and is not easily affected by noise. Therefore, it is desirable that the magnetic field modulation width be as large as possible, but it is not desirable that the relationship between the absorption amount and the magnetic field modulation width be non-linear. Therefore, here, as shown by A in FIG. 4, the magnetic field modulation width immediately before the linearity between the absorption amount and the magnetic field modulation width is broken is set as the optimum magnetic field modulation width.

As a method for automatically finding the magnetic field modulation width immediately before the linearity between the absorption amount and the magnetic field modulation width is broken, attention is paid to one peak, and the magnetic field modulation width is sequentially changed. While detecting the absorption amount of the relevant peak, it is determined whether the absorption amount at the time of the previous magnetic field modulation width and the absorption amount at the current magnetic field modulation width are in a proportional relationship, and immediately before the proportional relationship does not hold. The technique of setting the magnetic field modulation width as an optimum value is used.

At this time, the positive peak having the largest absorption amount may be used as the peak of interest in order to avoid the influence of noise and the like. Therefore, when setting the magnetic field sweep range as described above, the magnetic field intensity position of the positive peak where the amount of absorption is the maximum is stored.However, when setting the magnetic field modulation width, It goes without saying that the optimum magnetic field sweep range determined by the setting of the magnetic field sweep range may be swept to search for the positive peak having the largest absorption amount.

The control device 9 instructs the magnetic field modulation / sweep device 5 to set the magnetic field modulation width to a predetermined first magnetic field modulation width by a control signal. This first
Is a small value. At this time, the magnetic field sweep range only needs to be a predetermined range including the maximum value of the positive peak having the maximum absorption amount. Specifically, only a predetermined magnetic field strength width is required on both sides of the smaller and larger magnetic field strengths from the magnetic field strength position of the maximum value of the positive peak. Further, the sweep time may be set appropriately. Such a control signal is subjected to magnetic field modulation /
That is, the sweep device 5 is notified. Further, at this time, the control device 9 controls the microwave generation device 4 to output a control signal for obtaining a predetermined microwave output, and controls the amplifier 7 to output a control signal for obtaining a predetermined amplification factor. A signal is transmitted to the noise filter 8 with a control signal having a predetermined time constant. In the process of setting the magnetic field modulation width, the magnetic field sweep range, the sweep time, the microwave output, and the time constant of the noise filter 8 are maintained at constant values.

Then, the control device 9 instructs the magnetic field modulation / sweep device 5 to perform a magnetic field sweep. As a result, the magnetic field sweep is performed in a predetermined range including the maximum value of the peak. The control device 9 stores the maximum value of the peak captured at this time. This is the first measurement.
Next, the control device 9 controls the magnetic field modulation / sweep device 5 to
The control signal instructs the magnetic field modulation width to be n times the previous first magnetic field modulation width (n is a positive real number),
A control signal for setting the amplification factor to 1 / n times the previous one is notified to the amplifier 7. Then, the control device 9 instructs the magnetic field modulation / sweep device 5 to perform a magnetic field sweep. Thereby, the magnetic field sweep is performed in a predetermined range including the maximum value of the peak,
The control device 9 stores the maximum value of the peak taken in at this time. This is the second measurement.

Then, it is determined whether or not the maximum value of the absorption amount of the peak has a linear relationship between the first time and the second time. This is because the maximum value of the absorption amount of the peak at the time of the previous magnetic field modulation width is I0, and the current magnetic field modulation width is the maximum value of the absorption amount, that is, the magnetic field modulation width is n times the previous magnetic field modulation width. When the maximum value of the amount of absorption is I1, and the error range is δ, and I0−δ ≦ I1 ≦ I0 + δ (1) is satisfied, it is determined that the magnetic field modulation width and the amount of absorption have a linear relationship. What should I do? The value of the error range δ may be determined based on experiments and experiences.

When the control device 9 determines that the maximum value of the absorption amount of the peak has a linear relationship between the previous time and the current time, the control device 9 then controls the magnetic field modulation / sweep device 5 to change the magnetic field modulation width for the second time. And instructs the amplifier 7 to perform a magnetic field sweep, and sets the amplification factor to the amplifier 7 for the second 1 /
A control signal for n times is notified. As a result, the magnetic field is swept over a predetermined range including the maximum value of the peak, and the control device 9 stores the maximum value of the peak captured at this time. This is the third measurement.

Then, the control device 9 calculates 2
It is determined whether or not the maximum value of the absorption amount of the peak has a linear relationship between the third time and the third time. Since I0 in equation (1) is the maximum value of the absorption amount of the peak in the previous measurement, in this case, I0 is the absorption amount in the second measurement, and I1 is the absorption amount in the third measurement. Naturally, it becomes the absorption amount.

In this manner, the maximum value of the absorption amount of the positive peak to be focused on is determined by assuming that the magnetic field modulation width is n times and the amplification factor of the amplifier 7 is 1 / n times every measurement. It is determined whether or not the maximum value of the absorption amount and the maximum value of the absorption amount at the time of this measurement have a linear relationship. And m
When the maximum value of the absorption amount at the time of the second measurement and the maximum value of the absorption amount at the time of the (m-1) th measurement do not satisfy the expression (1), the control device 9 determines that the linearity has been lost. It is determined that the modulation width of the magnetic field at the time of the previous measurement, that is, (m
-1) The magnetic field modulation width at the time of the first measurement is set as an optimum value, and the process of setting the magnetic field modulation width is completed.

By the way, in the above processing, the magnetic field modulation width is made n times and the amplification factor of the amplifier 7 is made 1 / n times for each measurement for the following reason. As shown in FIG. 4, in a certain range of the magnetic field modulation width, the magnetic field modulation width and the absorption amount have a linear relationship, that is, are proportional. Therefore, in the linear relationship range, the magnetic field modulation width is determined by the previous measurement. If it is n times, the absorption amount will be n times. Therefore, if I0 and I1 are defined as the same as in the equation (1), if the amplification factor of the amplifier 7 is fixed, then if the following holds, then the magnetic field modulation width and the absorption can be obtained if I0-δ ≦ n × I1 ≦ I0 + δ. The quantity can be determined to be in a linear relationship. However, it is troublesome to multiply the maximum value of the absorption amount by n each time the measurement is performed and to compare the maximum value of the absorption amount with the previous maximum value of the absorption amount.
Is multiplied by 1 / n. In practice, n =
It should be 2.

In each of the above measurements, if the value of the data of the amount of absorption obtained by the magnetic field sweep is used as it is, it may be affected by noise when judging whether or not the equation (1) holds. Conceivable. Therefore, after performing an appropriate process such as a smoothing process on the data of the absorption amount obtained in advance to eliminate the influence of noise, (1)
The presence / absence of a linear relationship between the magnetic field modulation width and the absorption amount may be determined by the equation, thereby improving accuracy and reliability. Since the smoothing process is well known, a detailed description thereof will be omitted.

In the above description, the magnetic field modulation width is changed from a smaller one to a larger one. However, the modulation width may be changed from a larger one to a smaller one. In this case, the magnetic field modulation width is multiplied by 1 / n and the amplification factor of the amplifier 7 by n each time the measurement is performed. Should be set. As described above, according to this ESR, the magnetic field modulation width is automatically set to an optimum value.

(3) Operation for Setting Microwave Output When the setting of the magnetic field modulation width is completed, the control device 9 performs an operation for setting the microwave output. By the way, in ESR, it is known that the amount of absorption appearing in the spectrum is related to the microwave output. As shown in FIG. 5, the square root of the amount of absorption and the microwave output are small. By the way, it is known that there is a linear relationship, and as the microwave output increases, the linear relationship between the square root of the amount of absorption and the microwave output collapses. That is, in a range where the microwave output is small, if the microwave output is multiplied by n ² , the absorption amount is increased by n times.

In the case where the amount of absorption and the microwave output have a relationship as shown in FIG. 5, it is desirable that the output signal of the detector 6 be larger in consideration of how the microwave output is desired. Is as described above. Therefore,
It is desirable that the microwave output be as large as possible, but it is not desirable that the relationship between the amount of absorption and the microwave output be non-linear. Therefore, here, as shown by B in FIG. 5, the microwave output immediately before the linearity between the absorption amount and the microwave output is broken is set as the optimum microwave output.

Therefore, here, the microwave output immediately before the linearity between the square root of the absorption amount and the microwave output is broken is determined as the optimum microwave output. For that purpose, focusing on one peak, the maximum value of the absorption amount of the peak is detected while sequentially changing the microwave output, and the absorption amount at the time of the previous microwave output and the current time of the microwave output are detected. A method is used in which it is determined whether or not the absorption amount is in a proportional relationship, and the microwave output immediately before the proportional relationship no longer holds is set as an optimum value.

At this time, as the peak of interest, a positive peak having the maximum absorption amount may be used in order to avoid the influence of noise and the like. Therefore, as described above, when setting the magnetic field sweep range, the magnetic field intensity position of the positive peak where the absorption amount is the maximum is stored.When setting the microwave output, It goes without saying that the optimum magnetic field sweep range determined by the setting of the magnetic field sweep range may be swept to search for the positive peak having the largest absorption amount.

The control device 9 instructs the microwave generation device 4 to use a control signal to set the first output to a predetermined value. This first output is a small value. Further, for the magnetic field modulation / sweep device 5, the magnetic field modulation width is the optimum magnetic field modulation width obtained in the above-described processing of setting the magnetic field modulation width, and a proper sweep time is set to a positive magnetic field having the maximum absorption amount. The control signal instructs to sweep the magnetic field intensity range including the maximum value of the peak. This magnetic field sweep range may be the same range as in the case of setting the magnetic field modulation width. Further, the control device 9
Notifies a control signal for setting a predetermined amplification factor to the amplifier 7 and a control signal for setting a predetermined time constant to the noise filter 8. In the process of setting the magnetic field modulation width, the magnetic field modulation width, the magnetic field sweep range, the sweep time, and the time constant of the noise filter 8 are maintained at constant values.

Then, the control device 9 instructs the magnetic field modulation / sweep device 5 to perform a magnetic field sweep. As a result, the magnetic field sweep is performed in a predetermined range including the maximum value of the peak. The control device 9 stores the maximum value of the peak captured at this time. This is the first measurement. Next, the control device 9 instructs the microwave generation device 4 to set the output to n ² times (n is a positive real number) of the previous first output by the control signal, and also controls the amplifier 7. Is notified of a control signal for setting the amplification factor to 1 / n times the previous one. Then, the control device 9 instructs the magnetic field modulation / sweep device 9 to perform a magnetic field sweep. As a result, the magnetic field sweep is performed in a predetermined range including the maximum value of the peak, and the control device 9
Stores the maximum value of the peak taken in at this time. This is the second measurement.

Then, it is determined whether or not the maximum value of the absorption amount of the peak is in a proportional relationship between the first time and the second time. This is the peak when the maximum value of the absorption amount of the peak when the previous microwave output I0, when this microwave output, i.e. that the microwave output and n ² times the previous microwave power Assuming that the maximum value of the absorption amount is I1, the error range is δ, and if the above expression (1) is satisfied, it is determined that the microwave output and the square root of the absorption amount have a linear relationship. I just need. The error range δ in this case may be determined based on experiments and experiences.

When the control device 9 determines that the maximum value of the absorption amount of the peak in the previous time and the current time is in a proportional relationship, that is, a linear relationship, the microwave then outputs 2 outputs to the device 4. A control signal for n ² times of the ^second time is notified, and a control signal for increasing the amplification factor to 1 / n times of the second time is notified to the amplifier 7. Then, it instructs the magnetic field modulation / sweep device 5 to perform a magnetic field sweep. As a result, the magnetic field is swept over a predetermined range including the maximum value of the peak, and the control device 9 stores the maximum value of the peak captured at this time. This is the third measurement.

Then, the control device 9 calculates 2
It is determined whether or not the maximum value of the absorption amount of the peak has a linear relationship between the third time and the third time. Since I0 in equation (1) is the maximum value of the absorption amount of the peak in the previous measurement, in this case, I0 is the absorption amount in the second measurement, and I1 is the absorption amount in the third measurement. Naturally, it becomes the absorption amount.

In this manner, the maximum value of the absorption amount of the positive peak of interest is determined every time the measurement is performed, where the microwave output is n ² times and the amplification factor of the amplifier 7 is 1 / n times. Then, it is determined whether or not the maximum value of the absorption amount at the time of measurement and the maximum value of the absorption amount at the time of this measurement are in a linear relationship. When the maximum value of the absorption amount at the m-th measurement and the maximum value of the absorption amount at the (m-1) -th measurement do not satisfy the expression (1), the control device 9 determines the linearity. Is determined to have collapsed, and the microwave output at the previous measurement, that is, the microwave output at the (m-1) -th measurement is set as the optimum value, and the setting of the microwave output is set. The process ends.

In the above processing, the microwave output is set to n ² times and the amplification factor of the amplifier 7 is set to 1 / n times for each measurement for the following reason. As shown in FIG. 5, in a certain range of the microwave output, the microwave output and the square root of the absorption amount have a linear relationship, and in the range of the linear relationship, the microwave output is n ² times the previous measurement. , The absorption amount becomes n times. Therefore, if I0 and I1 are defined as the same as the equations (1), when the amplification rate of the amplifier 7 is fixed, if the above equation (2) is satisfied, the microwave output and the square root of the absorption amount have a linear relationship. It can be determined that there is. However, it is troublesome to multiply the maximum value of the absorption amount by n each time the measurement is performed and compare it with the previous maximum value of the absorption amount. It is doubling. Actually, it is sufficient to set n = 2.

In each of the above measurements, if the value of the data of the amount of absorption obtained by the magnetic field sweep is used as it is, it may be affected by noise when determining whether or not the equation (1) is satisfied. Conceivable. Therefore, after performing an appropriate process such as a smoothing process on the data of the absorption amount obtained in advance to eliminate the influence of noise, (1)
The presence / absence of a linear relationship between the magnetic field modulation width and the absorption amount may be determined by the equation, thereby improving accuracy and reliability.

In the above description, the microwave output is changed from a smaller one to a larger one. However, the microwave output may be changed from a larger one to a smaller one. In that case, the microwave output is reduced by 1 /
n ² times, multiply the amplification factor of the amplifier 7 by n times, first (1)
What is necessary is just to set the value of the microwave output that satisfies the equation as the optimum value. As described above, according to this ESR, the microwave output is automatically set to an optimum value.

(4) Operation for setting response time As described above, the response time is set to the noise filter 8 here.
Is determined by the time constant of The response time increases as the time constant of the noise filter 8 increases, and the response time decreases as the time constant decreases. When the response time is shortened, the output signal strength of the detector 6 increases, but the noise also increases. On the other hand, if the response time is increased, the waveform of the positive and negative peaks of the spectrum is distorted. Therefore, there is an optimum value of the time constant of the noise filter 8, that is, an optimum value of the response time.

In order to find the optimum response time, attention is paid here to the half width of a pair of positive and negative peaks. That is, in the range where the response time is short, the output signal of the detector 6 can sufficiently follow, and the half width of the peak of the pair is constant. It is considered that the half-width of the peak of the pair gradually becomes narrower because the output signal of the detector 6 cannot be followed gradually.

Therefore, here, paying attention to a pair of positive and negative peaks, the half width of the peak of the pair is detected while changing the time constant of the noise filter 8 in predetermined steps, and the half width is constant. A method is used in which the time constant of the noise filter 8 immediately before the state deviates from the state is set so as to give an optimum response time.

At this time, a pair of positive and negative peaks of interest may use a positive peak having the largest absorption amount and a negative peak paired with the positive peak in order to avoid the influence of noise. Therefore, when setting the magnetic field sweep range as described above, the magnetic field intensity position of the positive peak where the amount of absorption is the maximum, and the magnetic field intensity position of the negative peak paired with the positive peak are stored. However, when setting this response time, the optimum magnetic field sweep range determined by the above-described magnetic field sweep range setting is swept, and the positive peak having the largest absorption amount and the negative peak paired therewith are swept. Needless to say, the search may be performed.

After completing the setting of the microwave output, the control device 9 performs an operation of setting the response time. First, the control device 9 notifies the noise filter 8 of a control signal for setting the time constant to a predetermined first time constant. This first time constant is a small value. Further, for the magnetic field modulation / sweep device 5, the magnetic field modulation width is the optimum magnetic field modulation width obtained in the above-described processing of setting the magnetic field modulation width, and a proper sweep time is set to a positive magnetic field having the maximum absorption amount. The control signal instructs to sweep the magnetic field intensity range including the maximum value of the peak and the minimum value of the negative peak paired with the positive peak. Furthermore,
The control device 9 controls the microwave generation device 4 to set the optimum microwave output obtained by the above-described process of setting the microwave output, and controls the amplifier 7 to set a predetermined amplification factor. Signal the signal. In the process of setting the response time, the magnetic field modulation width, the magnetic field sweep range, the sweep time, and the microwave output are maintained at constant values.

Then, the control device 9 instructs the magnetic field modulation / sweep device 5 to perform a magnetic field sweep. As a result, the magnetic field sweep is performed in a predetermined range including the maximum value and the minimum value of the peak of the pair, but the control device 9 sets the magnetic field intensity position and the minimum value of the maximum value of the peak of the pair captured at this time. And the half-width value is obtained from the position of the magnetic field strength, and the value of this half-width value is stored. This is the first measurement. Next, the control device 9 sends a control signal to the noise filter 8 according to a control signal.
The time constant is set to a predetermined step Δs from the previous first time constant.
And instructs the magnetic field modulation / sweep device 5 to sweep the magnetic field. Thereby, the magnetic field sweep is performed in a predetermined range including the local maximum value and the local minimum value of the peak of the pair, and the control device 9 determines the magnetic field intensity position of the local maximum value of the peak of the pair and the local minimum value And the half-width value is obtained from the position of the magnetic field strength, and the value of this half-width value is stored. This is the second measurement.

Then, it is determined whether the half width of the peak of the pair is the same within the range of the error in the first time and the second time. This is the half-width of the peak of the pair at the time of the previous time constant.
When H0 is the current time constant, that is, when the time constant of the noise filter 8 is larger than the previous time constant by a predetermined step Δs, and the half width of the peak of the pair is ΔH1, the error range is When ΔH0−δ ≦ ΔH1 ≦ ΔH0 + δ (3) is satisfied, the half widths of the two may be determined to be the same within the range of the error. The value of the error range δ may be determined based on experiments and experiences.

When the control device 9 determines that the half width of the peak of the pair is the same within the range of the error between the previous time and the current time, the control device 9 next sets the time constant to 2 for the noise filter 8.
A control signal having a value larger than the first time constant by Δs is notified, and the magnetic field modulation / sweep device 5 is instructed to perform a magnetic field sweep. Thereby, the magnetic field sweep is performed in a predetermined range including the local maximum value and the local minimum value of the peak of the pair, and the control device 9 controls the magnetic field intensity position of the local maximum value and the local minimum value of the peak of the pair captured at this time. The half width is obtained from the magnetic field strength position and stored. This is the third measurement.

Then, the control device 9 obtains 2
It is determined whether the half width of the peak of the pair is the same within the range of the error between the third time and the third time. Since △ H0 in equation (3) is the half-width of the peak of the pair in the previous measurement, in this case, △ H0 is the half-width at the second measurement, and △ H1
Is naturally the half width at the time of the third measurement this time.

In this way, while increasing the time constant of the noise filter 8 by a predetermined step ΔS every time the measurement is performed, the half width of the peak of the pair of interest is determined, and the half width at the time of the previous measurement is obtained. Then, it is determined whether or not the half width at the time of this measurement is the same within the range of the error. And
If the half-width at the m-th measurement and the half-width at the (m-1) -th measurement do not satisfy the expression (3), the control device 9 determines that the half-width has shifted, and , The time constant of the noise filter 8 at the time of measurement, that is, (m
-1) The time constant at the time of the first measurement is set to give the optimum response time, and the processing of setting the response time is completed.

In each of the above measurements, if the value of the data of the amount of absorption obtained by the magnetic field sweep is used as it is, it may be affected by noise when judging whether or not the equation (3) holds. Therefore, it is desirable to perform an appropriate process such as a smoothing process as described above to eliminate the influence of noise. Thereby, accuracy and reliability can be improved.

In the above description, the time constant of the noise filter 8 is changed from the smaller one to the larger one. However, the time constant may be changed from the larger one to the smaller one. In this case, the time constant is reduced by a predetermined step every measurement, and the time constant when the half-value width 値 H0 when Equation (3) is first obtained is determined by the optimal response. What is necessary is just to set as what gives time.

The processing for automatically setting the response time by the control device 9 has been described above. However, since the above processing requires a certain amount of time, the time may not be desirable for a skilled operator in terms of work efficiency. . This is because a skilled operator can set the amplification factor of the amplifier 7 and the time constant of the noise filter 8, that is, the response time, by observing spectra obtained by measuring under various conditions. Therefore, it is desirable to provide a function for easily setting a desired response time. Hereinafter, the configuration for that will be described.

The response time is a parameter having a function of adjusting a noise component in the output signal of the detector 6, and the noise component is related to the amplification factor of the amplifier 7. Therefore, for the amplification factor in a predetermined range, an optimal time constant of the noise filter 8 for the amplification factor for each predetermined step is obtained by an experiment. Then, for example, a table is created in which the respective amplification factors correspond to the optimum time constant of the noise filter 8 for each amplification factor, and registered in the control device 9 in advance. When the amplification factor is input from the input device 10, a time constant corresponding to the input amplification factor is obtained from the table, the input amplification factor is instructed to the amplifier 7, and the obtained time constant is determined. To the noise filter 8
Should be instructed. When the input amplification factor is registered in the table, the time constant written corresponding to the amplification factor may be read, and when the input amplification factor is not registered in the table. Can be obtained by obtaining two amplification factors sandwiching the input amplification factor and a time constant corresponding to the amplification factor, and obtaining a time constant corresponding to the input amplification factor by appropriate interpolation calculation. Good.

As described above, according to this ESR, the response time is automatically set to an optimum value. It is also possible to easily set a response time that is considered optimal for a skilled operator manually.

(5) Operation of setting magnetic field sweep time In ESR, if the magnetic field sweep time is increased, the detector 6
Since the circuit at a later stage can follow the output signal of the detector 6, the position of the magnetic field strength at each of the positive and negative peaks is accurate, but the measurement time becomes long, which is not desirable in terms of work efficiency. On the other hand, although shortening the magnetic field sweeping time is desirable in terms of work efficiency, the circuits subsequent to the detector 6 cannot follow the output signal of the detector 6 and the waveform of the positive and negative peaks of the spectrum is distorted. Therefore, there is no problem in work efficiency, and there is an optimum value of the magnetic field sweeping time to prevent distortion of the peak waveform of the spectrum.

In order to automatically find the optimum magnetic field sweep time, here, focusing on one peak, the magnetic field intensity position of the peak is detected while sequentially changing the magnetic field sweep time, and the previous magnetic field sweep time is detected. Judge whether the magnetic field intensity position at the time of the sweep time and the magnetic field intensity position at the time of the current magnetic field sweep time are the same within an error range, and the magnetic field intensity position of the peak is constant within the error range. A technique of setting the magnetic field sweep time immediately before the state deviates from the state as an optimum value is used.

The reason for this is that, as described above, the waveform of the peak of the spectrum is distorted as the magnetic field sweeping time is shortened. At this time, however, it is considered that the magnetic field intensity position of the peak is shifted. .

At this time, the peak to be focused on may be a positive peak having the largest absorption amount in order to avoid the influence of noise and the like. Therefore, when setting the magnetic field sweep range as described above, the magnetic field intensity position of the positive peak where the amount of absorption is the maximum is stored, but when setting the magnetic field sweep time, It goes without saying that the optimum magnetic field sweep range determined by the setting of the magnetic field sweep range may be swept to search for the positive peak having the largest absorption amount.

When the setting of the response time is completed, the control device 9 performs the operation of setting the magnetic field sweeping time. First, the control device 9 notifies the magnetic field modulation / sweep device 5 of a control signal for a predetermined first sweep time. The first sweep time is set to a large value. For the magnetic field modulation / sweep device 5, the magnetic field modulation width is the optimum magnetic field modulation width obtained in the above-described processing of setting the magnetic field modulation width, and the magnetic field sweep range is a positive magnetic field having the maximum absorption amount. Indicate the magnetic field strength range that includes the peak maximum. Further, the control device 9 notifies the microwave generation device 4 of a control signal for setting the optimum output obtained in the processing of setting the microwave output,
The amplifier 7 is notified of a control signal for setting a predetermined amplification factor, and the noise filter 8 is notified of a control signal for setting the optimum time constant obtained in the above-described processing of setting the response time. . In the process of setting the magnetic field sweep time, the magnetic field modulation width, the magnetic field sweep range, the microwave output, and the time constant of the noise filter 8 are maintained at constant values.

Then, the control device 9 instructs the magnetic field modulation / sweep device 5 to perform a magnetic field sweep. As a result, the magnetic field is swept over a predetermined range including the maximum value of the peak. The control device 9 stores the magnetic field intensity position of the maximum value of the peak acquired at this time. This is the first measurement. Next, the control device 9 instructs the magnetic field modulation / sweep device 5 to set the magnetic field sweep time to a value shorter by a predetermined time step width Δt by a control signal. Then, a magnetic field sweep is instructed. As a result, the magnetic field is swept over a predetermined range including the local maximum value of the peak, and the control device 9 stores the magnetic field intensity position of the local maximum value of the peak taken in at this time. This is the second measurement.

Then, it is determined whether or not the magnetic field intensity position of the peak is the same within the range of the error between the first time and the second time. This is because when the magnetic field intensity position of the maximum value of the peak at the time of the previous magnetic field sweep time is ΔG 0, and at the current magnetic field sweep time, that is, when the magnetic field sweep time is shorter than the previous time by a predetermined time step width Δt. When the magnetic field intensity position of the maximum value of the peak is ΔG 1, the error range is δ, and when ΔG 0 −δ ≦ ΔG 1 ≦ ΔG 0 + δ (4) is satisfied, both magnetic field intensity positions May be determined to be the same within the range of the error. The value of the error range δ may be determined based on experiments and experiences.

When the control device 9 determines that the magnetic field intensity position of the maximum value of the peak is the same within the range of the error between the previous time and the current time, the control device 9 sends the magnetic field modulation / sweep device 5 a magnetic field Sweep time is Δt longer than the second magnetic field sweep time
The control signal is set to a shorter value, and a magnetic field sweep is instructed to the magnetic field modulation / sweep device 5. Thereby, the magnetic field sweep is performed in a predetermined range including the maximum value of the peak,
The control device 9 obtains the maximum magnetic field intensity position of the peak taken in at this time and stores it. This is the third measurement.

Then, the control device 9 obtains 2
It is determined whether the maximum magnetic field intensity position of the peak is the same within the range of the error between the third time and the third time. △ G0 in equation (4)
Is the magnetic field intensity position of the maximum value of the peak in the previous measurement. In this case, ΔG0 is the magnetic field intensity position in the second measurement, and ΔG1 is the magnetic field intensity in the third measurement this time. It is natural that it is a position.

In this manner, the magnetic field sweeping time is reduced by a predetermined time step width Δt from the previous measurement every time the measurement is performed, and the maximum magnetic field intensity position of the peak of interest is obtained. It is determined whether or not the magnetic field intensity position at the time of the previous measurement and the magnetic field intensity position at the time of the current measurement are the same within an error range. When the expression (4) does not hold between the magnetic field intensity position at the m-th measurement and the magnetic field intensity position at the (m-1) -th measurement, the control device 9 determines that the magnetic field intensity position has shifted. Judgment is made, and the magnetic field sweep time at the previous measurement, that is, the magnetic field sweep time at the (m-1) -th measurement is set as an optimum value, and the process of setting the magnetic field sweep time is completed. I do.

At the time of each of the above measurements, if the value of the data of the amount of absorption obtained by the magnetic field sweep is used as it is, it may be affected by noise when determining whether or not Expression (4) holds. Therefore, it is desirable to perform an appropriate process such as a smoothing process as described above to eliminate the influence of noise. Thereby, accuracy and reliability can be improved.

In the above description, the magnetic field sweeping time is changed from a longer one to a shorter one. However, it is also possible to change the magnetic field sweeping time from a shorter one to a longer one. In this case, the magnetic field sweep time is increased by a predetermined time step width at each measurement, and the magnetic field sweep time when the magnetic field intensity position △ G0 when Equation (4) is first obtained is obtained. May be set as an optimal value.

The processing for automatically setting the optimum magnetic field sweeping time by paying attention to the magnetic field position of the maximum value of one positive peak has been described above. Another processing will be described below. As described above in the processing for setting the response time, the distortion of the waveform of the spectrum peak also appears in the half width of the paired positive and negative peaks. Therefore, paying attention to the half value width of a pair of positive and negative peaks, the magnetic field sweep time is shortened by a predetermined time step width Δt from the time of the previous measurement for each measurement, and the peak of the pair of interest is measured. The optimum magnetic field sweep time can also be determined by determining the half width and determining whether the half width at the previous measurement and the half width at the current measurement are the same within the range of the error. Can be found. This process is the same as the above-described process of setting the response time, and thus the details are omitted. However, in the above-described processing of setting the response time, the half-value width of the peak of the pair of interest is compared while changing the time constant of the noise filter 8 by a predetermined step Δs. Is to compare the half widths of the peaks of a pair of interest while changing the magnetic field sweep time by a predetermined time step width Δt. And the half width at the m-th measurement,
When the expression (3) does not hold with the half width at the time of the (m-1) -th measurement, the control device 9 determines that the half width has deviated, and optimizes the magnetic field sweep time at the previous measurement. Set the value. In this case as well, it goes without saying that the magnetic field sweeping time can be sequentially changed from the shorter one to the longer one. As described above, this E
According to SR, the magnetic field sweep time can be automatically set to an optimal value.

Then, the control device 9 sets 5
When the values of the two parameters are set, the set magnetic field sweep range, the magnetic field modulation width, and the magnetic field sweep time are notified to the magnetic field modulation / sweep device 5 by a control signal. The wave output is notified by the control signal, and the set time constant is notified to the noise filter 8 by the control signal. As a result, the ESR becomes
Optimal conditions are set for the sample, and actual measurement is performed in that state, so that good measurement can be performed.

Although the embodiment of the present invention has been described above, the present invention is not limited to the above embodiment, and various modifications are possible. For example, in the above description,
In the process of setting the magnetic field modulation width, the microwave output, and the magnetic field sweep time, a positive peak is used, but a negative peak may be used. In that case, the maximum value in the above description may be read as the minimum value.

[0080]

As described above, according to the present invention, the values of the five parameters of the magnetic field sweep range, the magnetic field modulation width, the microwave output, the response time, and the magnetic field sweep time are automatically optimized. Can be set to Therefore,
Good measurement can be easily performed even by a non-expert. In addition, it can assist unmanned automatic measurement.

[Brief description of the drawings]

FIG. 1 is a diagram showing a configuration of an embodiment of an ESR according to the present invention.

FIG. 2 is a diagram for explaining an example of processing for setting a magnetic field sweep range when the number of peaks is an even number;

FIG. 3 is a diagram for explaining an example of processing for setting a magnetic field sweep range when the number of peaks is an odd number;

FIG. 4 is a diagram for explaining an optimum magnetic field modulation width.

FIG. 5 is a diagram for explaining an optimal microwave output.

FIG. 6 is a diagram showing a schematic configuration of an ESR.

FIG. 7 is a diagram illustrating a spectrum obtained by ESR.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Sample tube, 2 ... Cavity resonator, 3 ... Electromagnet, 4 ... Microwave generator, 5 ... Magnetic field modulation / sweep device, 6 ... Detector,
7 ... amplifier, 8 ... noise filter, 9 ... control device, 10
... input device.

Claims (7)

[Claims] 1. Automatically setting at least five parameters of a magnetic field sweep range, a magnetic field modulation width, a microwave output, a response time of a circuit subsequent to a detector, and a magnetic field sweep time to optimal values. An electron spin resonance apparatus, comprising: means for performing the above-mentioned processing. 2. The method according to claim 1, wherein the number of positive or negative peaks is detected based on a signal obtained when a sufficiently wide magnetic field intensity range is swept. The magnetic field sweep range is set based on the magnetic field strength position of the positive peak and the magnetic field strength position of the negative peak at the highest magnetic field strength.If the number of positive or negative peaks is odd, the middle The position of the maximum value of the positive peak and the position of the minimum value of the negative peak paired with the positive peak are obtained, and the central position between the position of the maximum value and the position of the minimum value is defined as the central magnetic field. From the central magnetic field to the larger and smaller magnetic field strengths, respectively, at least means for performing a process of setting a range obtained by multiplying the half width of the positive and negative peaks forming the middle pair by a predetermined multiple as the magnetic field sweeping range. Electric Spin resonance apparatus. 3. Focusing on one peak, the absorption amount of the peak is detected while sequentially changing the magnetic field modulation width, and the absorption amount at the previous magnetic field modulation width and the absorption amount at the current magnetic field modulation width are detected. An electron spin resonance apparatus comprising at least means for determining whether or not the quantities are in a proportional relationship, and performing a process of setting a magnetic field modulation width immediately before the proportional relationship no longer holds as an optimum value. 4. Focusing on one peak, detecting the maximum value of the absorption amount of the peak while sequentially changing the microwave output, and detecting the absorption amount at the time of the previous microwave output and the current microwave output. An electron spin resonance apparatus comprising at least means for judging whether or not absorption amounts at the time are in a proportional relationship, and setting a microwave output immediately before the proportional relationship no longer holds as an optimum value. 5. A state in which the half width of a pair of peaks is detected while paying attention to a pair of positive and negative peaks and changing the time constant of a circuit subsequent to the detector in predetermined steps. An electron spin resonance apparatus comprising at least means for performing a process of setting a time constant immediately before deviating from the value so as to give an optimum response time. 6. Focusing on one peak, detecting a magnetic field intensity position of the peak while sequentially changing a magnetic field sweep time,
It is determined whether the magnetic field intensity position at the time of the previous magnetic field sweep time and the magnetic field intensity position at the current magnetic field sweep time are the same within an error range, and the magnetic field intensity position of the peak is within the error range. An electron spin resonance apparatus comprising at least means for performing processing for setting a magnetic field sweep time immediately before deviating from a constant state as an optimum value. 7. Focusing on a pair of positive and negative peaks, detecting the half-width of the pair of peaks while sequentially changing the magnetic-field sweep time, and determining the magnetic-field sweep time immediately before the half-width deviates from a constant state. An electron spin resonance apparatus comprising at least means for performing a process of setting a value.