JPH0378946B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electron spin resonance apparatus, and more particularly to an electron spin resonance apparatus in which an electromagnetic horn is used instead of a cavity resonator to apply microwaves to a sample.

Generally, in an electron spin resonance apparatus, a sample is inserted into a cavity resonator to perform measurements. Although this method has the great feature of high measurement sensitivity, (a) there are limitations on the shape and size of the sample due to the fact that the sample is placed inside the cavity (conventional equipment has a maximum of 10 mm);
(b) Due to the resonance condition, the frequency of the microwave applied to the sample cannot be arbitrarily selected.

In order to eliminate this drawback, an electron spin resonance apparatus having the basic configuration shown in FIG. 1 without using a cavity resonator has been proposed in Japanese Patent Application No. 57-215075 (Japanese Patent Application Laid-open No. 59-105551). In the figure, numerals 1 and 2 are fan-shaped electromagnetic horns arranged opposite to each other. Microwaves generated by a microwave oscillator (not shown) and guided through a waveguide are radiated from an electromagnetic horn 1 toward an electromagnetic horn 2. A test sample 3 such as a sample tube containing a sample or a wafer-shaped sample is placed between these two electromagnetic horns, and a DC magnetic field is applied, for example, in the direction indicated by the arrow in the figure. When a sample absorbs microwaves due to electron spin resonance,
Since the microwave power incident on the electromagnetic horn 2 changes, the electron spin resonance of the sample can be detected based on the change.

According to this device, the sample can be placed in a relatively large space between the two horns, so
Electron spin resonance measurements can be performed on samples of any shape and size, and for example, large wafers such as semiconductor wafers, amorphous silicon wafers, and bubble memory wafers can be measured without being destroyed. Effects can be obtained. Furthermore, since there is no resonator, it is possible to arbitrarily select the microwave frequency.

By the way, in this device, the electromagnetic horn 1
Almost all of the microwaves emitted from the sample and applied to the sample are received by the electromagnetic horn 2.
The detection diode used as a receiver has at most
It can only tolerate microwave power of about 10mW.
Therefore, the power of the microwave applied to the sample from the electromagnetic horn 1 has to be set at a low level commensurate with the allowable power, and therefore high-power microwaves are applied to the sample to perform sensitive measurements. It was difficult.

Further, this device requires two electromagnetic horns, one for transmitting and one for receiving, and there is also a problem that the device configuration becomes complicated.

The present invention has been made in view of the above-mentioned points, and it simplifies the device configuration by transmitting and receiving microwaves using a single electromagnetic horn, and also applies high-power microwaves to a sample. The object of the present invention is to provide an electron spin resonance apparatus that can perform measurements with high sensitivity.

An electron spin resonance apparatus according to the present invention includes: a means for generating a magnetic field to be applied to a sample; a means for generating microwaves to be applied to the sample; an electromagnetic horn for emitting the microwaves toward the sample; a microwave detector for detecting microwaves reflected from the sample; a microwave detector for transmitting the microwaves from the generating means to the electromagnetic horn and receiving the reflected microwaves from the sample received by the electromagnetic horn to the detector; It is characterized by consisting of a microwave circuit that transmits. Hereinafter, the present invention will be explained in detail using the drawings.

FIG. 2 shows the configuration of an embodiment of the present invention, and in the figure, 5 is a magnet. An electromagnetic horn 1 is arranged within the magnet 5, and a sample 3 is placed in front of it. A modulation coil 6 for magnetic field modulation is installed inside the magnet 5, and a modulation current having a frequency of, for example, about 100 KHz is supplied from an oscillator 8 via an amplifier 7 to the coil 6.

Microwaves generated from a microwave oscillator 9 such as a gun oscillator are sent to the electromagnetic horn 1 via an isolator 10, an attenuator 11, and a magic tie 12, and are reflected toward the sample 3. The microwave reflected by the sample is incident on the electromagnetic horn 1, and sent via the magic tie 12 to the detection diode 13 where it is detected. In this embodiment, in order to set the operating point of the detection diode at an appropriate level, a directional coupler 14 extracts microwaves at an appropriate level from the transmitting system, and a directional coupler 15 sends the microwaves to the receiving system. There is. 16
is a phase shifter for adjusting the phase. The detection signal obtained from the diode 13 is sent via an amplifier 17 to a demodulator (eg phase sensitive detector) 18 . A modulation signal from the oscillator 8 is supplied to the demodulator 18 via a phase shifter 19, and the detection signal is demodulated based on the modulation signal. The demodulated detection signal is sent to a recorder 21 such as a recorder via an amplifier 20, and is recorded in relation to the magnetic field sweep by the excitation power source 22 that excites the magnet 4. Reference numeral 23 denotes an impedance converter connected to one arm of the magic tie 12, which is composed of, for example, a movable termination plate that terminates the arm and a pin whose insertion amount into the waveguide is variable.

In the above configuration, the microwave generated from the oscillator 9 is sent to the electromagnetic horn 1 via the magic tie 12, and the electromagnetic horn 1 generates hardly any reflected waves and has efficient and sharp directivity. is emitted towards the sample. If this sample has a large dielectric loss (e.g. spin-labeled skin or organs), the microwave will not pass through the sample;
Absorbed and reflected. This reflected microwave returns to the electromagnetic horn 1, enters the electromagnetic horn 1, and travels to the detection diode 13 via the magic tie 12. At this time, if the impedance converter 23 is adjusted appropriately to create a reflected wave with the opposite phase and the same intensity as the microwave reflected by the sample and send it to the detection diode 13, the two reflected waves cancel each other out. It is possible to achieve balance so that the microwave disappears and the microwave is not sent from the magic tie 12 to the detection diode 13. However, when the magnetic field strength reaches a value that satisfies the resonance condition due to the sweeping by the power supply 22, and electron spin resonance occurs and the microwave energy is absorbed by the sample, the balance is disrupted and the reflected microwaves are detected by the magic tie 12. Since the signal is sent to diode 13, the diode 1
A change appears in the output of 3, and the change is recorded as an ESR spectrum in the recorder 21.

In this way, in the present invention, unlike the proposed device, all the microwaves reflected from the transmitting electromagnetic horn are not constantly incident on the receiving horn and sent to the receiving diode. Even if the intensity of the microwave applied to the sample is increased, the receiving diode will not be destroyed.
Therefore, it is possible to dramatically increase measurement sensitivity.

Further, in the present invention, since one electromagnetic horn is used for both transmission and reception, the device configuration is simplified.

FIG. 3 shows the configuration of another embodiment of the present invention. In this embodiment, a circulator 24 is used in place of the magic tie, and an impedance converter 23 is arranged between the circulator 24 and the electromagnetic horn 1. . Adjust the impedance converter 23,
The phase and intensity of the microwave reflected from the converter 23 to the circulator 24, and the microwave that passed through the converter 23, was sent to the electromagnetic horn 1, was reflected by the sample, and returned to the converter 23. By combining, canceling and extinguishing,
Similar to the embodiment shown in FIG. 2, balance can be achieved so that the microwave is not sent from the circulator 24 to the detection diode 13. When electron spin resonance occurs and microwave energy is absorbed by the sample, the balance is disrupted and the reflected microwaves are sent from the circulator 24 to the detection diode 13, resulting in an ESR spectrum similar to the embodiment shown in FIG. can be obtained.

In addition to the above-mentioned structure, impedance converters can be used as long as they are capable of varying the phase and intensity of microwaves, such as those that vary both the length and position of the pin inserted into the waveguide. , you can use anything.

[Brief explanation of drawings]

FIG. 1 is a diagram for explaining the proposed device, FIG. 2 is a diagram showing the configuration of one embodiment of the present invention, and FIG. 3 is a diagram showing the configuration of another embodiment of the present invention. 1: Electromagnetic horn, 3: Sample, 4: Magnet, 9: Microwave oscillator, 12: Magic tie, 13: Detection diode, 23: Impedance converter, 2
4: Circulator.

Claims (1)

[Claims] 1. A means for generating a magnetic field to be applied to the sample, a means for generating microwaves to be applied to the sample, an electromagnetic horn for emitting the microwaves toward the sample, and a means for generating microwaves reflected from the sample. a microwave detector for detecting microwaves coming from the electromagnetic horn; and a microwave for transmitting the microwaves from the generating means to the electromagnetic horn and for transmitting the microwaves reflected from the sample received by the electromagnetic horn to the detector. An electron spin resonance device consisting of a circuit. 2. The electron spin resonance apparatus according to claim 1, wherein the microwave circuit is a magic tie. 3. The electron spin resonance apparatus according to claim 1, wherein the microwave circuit is a circulator.