The present invention relates to relaxor ferroelectric substances which are useful in the field of optical mechatronics and applicable, for example, to information devices (IT devices) such as cell phones. Also, it relates to optical devices and ferroelectric devices which use such a relaxor ferroelectric substance as well as a method of using these devices.
Relaxor ferroelectric substances have been used as capacitor materials because of their high permittivity as well as because of low temperature dependence and low electric-field dependence of their permittivity. Also, they have been used as piezoelectric/electrostrictive material to take full advantage of their excellent electromechanical coupling factor. Furthermore, their excellent piezoelectric characteristics have been used, for example, for ultrasonic transducers (e.g., Patent Document 1).
Patent Document 1: Japanese National Phase Laid-Open Patent Publication No. 2001-509312
The present invention is based on optical characteristics and dielectric characteristics of a relaxor ferroelectric solid solution single crystal newly found by the inventors and an objective of the present invention is to provide a relaxor ferroelectric solid solution single crystal which has unique optical characteristics and dielectric characteristics. Another objective of the present invention is to provide a device which uses the relaxor ferroelectric solid solution single crystal as well as to provide a method of using the device.
To achieve the above objectives, according to one aspect of the present invention, there is provided a relaxor ferroelectric solid solution single crystal. The relaxor ferroelectric solid solution single crystal is capable of making transitions, at temperatures below the Curie temperature, between a first state which has a high permittivity and blocks optical transmission and a second state which has a low permittivity and allows optical transmission. The relaxor ferroelectric solid solution single crystal undergoes a transition to the second state if an electric field above a threshold is applied in the first state.
Preferably, the relaxor ferroelectric solid solution single crystal undergoes a transition to the first state if heated to or above the Curie temperature in the second state. Then, the relaxor ferroelectric solid solution single crystal provided by the present invention will be capable of making transitions between the first state and second state reversibly.
Preferably, the relaxor ferroelectric solid solution single crystal is made of a lead-based complex perovskite compound. The lead-based complex perovskite compound may be expressed as any of (1-x)Pb(Mg1/3Nb2/3)O3·xPbTiO3, (1-x)Pb(Zn1/3Nb2/3)O3·xPbTiO3, and (1-x)Pb(In1/2Nb1/2)O3·xPbTiO3, where x represents a composition ratio of PbTiO3 in the lead-based complex perovskite compound. Hereinafter (1-x) Pb(Mg1/3Nb2/3)O3·xPbTiO3 will be abbreviated to PMN-PT, (1-x)Pb(Zn1/3Nb2/3)O3·xPbTiO3 to PZN-PT, and (1-x) Pb (In1/2Nb1/2) O3·xPbTiO3 to PIN-PT. The PMN-PT, PZN-PT and PIN-PT are capable of making transitions between the first state and second state within a range of the composition ratio x of between 0.1 and 0.2 (exclusive) by the application of an electric field.
Variations in characteristics of a lead-based complex perovskite compound due to differences in the composition ratio x will be described below by citing PMN-PT, and the same applies to PZN-PT and PIN-PT.
As can be seen from
FIGS. 3(a) and 3(b) are phase diagrams of a PMN-PT solid solution single crystal, where
The PMN-PT solid solution single crystal in the cubic phase has light blocking properties. That is, the PMN-PT solid solution single crystal blocks optical transmission regardless of its composition ratio x when its temperature is equal to or higher than the Curie temperature. On the other hand, when its temperature is below the Curie temperature, the PMN-PT solid solution single crystal allows optical transmission at least partially if its composition ratio x is 0.2 or higher.
The PMN-PT solid solution single crystal in the pseudocubic/rhombohedral phase exhibits electric field hysteresis when its composition ratio x is larger than 0.1 and smaller than 0.2. The PMN-PT solid solution single crystal with its composition ratio x being larger than 0.1 and smaller than 0.2 is capable of making transitions between a first state which has a high permittivity and blocks optical transmission and a second state which has a low permittivity and allows optical transmission. Also, the PMN-PT solid solution single crystal with its composition ratio x being larger than 0.1 and smaller than 0.2 has a memory effect. The memory effect consists in that at a temperature below the Curie temperature, once an electric field above a threshold is applied to the PMN-PT solid solution single crystal, even if the magnitude of the electric field is increased or decreased subsequently, the PMN-PT solid solution single crystal does not make a transition from the second state to the first state.
As shown in
Preferably a lead-based complex perovskite compound of the relaxor ferroelectric solid solution single crystal is a pseudocubic/rhombohedral phase (001) plate. In the pseudocubic/rhombohedral phase (001) plate, an engineered domain structure called an oblique field prevents movement of domain walls caused by the application of an electric field. Consequently, the relaxor ferroelectric solid solution single crystal exhibits not only unique optical characteristics and ferroelectric characteristics, but also good actuator characteristics due to a high electromechanical coupling factor and good mechanical strain characteristics of the pseudocubic/rhombohedral phase (001) plate.
According to another aspect of the present invention, there is provided a device which uses the relaxor ferroelectric solid solution single crystal. Preferably the device uses at least optical characteristics of the relaxor ferroelectric solid solution single crystal. Alternatively, the device may use not only the optical characteristics, but also changes in dielectric characteristics of the relaxor ferroelectric solid solution single crystal taking place with changes in the optical characteristics.
According to still another aspect of the present invention, there is provided a method of using a device that incorporates the relaxor ferroelectric solid solution single crystal. The method includes: applying an electric field above a threshold to the relaxor ferroelectric solid solution single crystal in the device to cause the relaxor ferroelectric solid solution single crystal to make a transition from the first state to the second state; and heating the relaxor ferroelectric solid solution single crystal in the device to or above the Curie temperature to cause the relaxor ferroelectric solid solution single crystal to make a transition from the second state to the first state.
FIGS. 3(a) and 3(b) are phase diagrams of a PMN-PT solid solution single crystal;
FIGS. 4(a) to 4(c) are polarized photomicrographs taken of device bodies of optical devices according to example 1 and comparative examples 1 and 2 with no electric field being applied;
FIGS. 5(a) to 5(c) are polarized photomicrographs taken of a device body of an optical device according to comparative example 3;
FIGS. 7(a) to 7(d) are polarizing microscopes taken of the device body in the optical device according to example 1 with an electric field which changes unidirectionally from 0 kV/cm to 8.2 kV/cm being applied to the optical device;
FIGS. 9(a) and 9(b) are polarized photomicrographs taken of the device body in the optical device according to example 1 with an electric field which changes unidirectionally from 8.2 kV/cm to 0 kV/cm being applied to the optical device;
FIGS. 10(a) to 10(d) are polarized photomicrographs taken of the device body in the optical device according to example 1 with an electric field which changes unidirectionally from 0 kV/cm to −8.2 kV/cm being applied to, the optical device;
FIGS. 11(a) to 11(c) are polarized photomicrographs taken of the device body in the optical device according to example 1 with no electric field being applied;
FIGS. 14(a) to 14(c) are polarized photomicrographs taken of the device body in the optical device according to example 1 with no electric field being applied after the optical device is heated to or above the Curie temperature;
FIGS. 17(a) to 17(d) are polarizing microscopes taken of the device body in the optical device according to example 2 by applying an electric field which changes unidirectionally from 0 kV/cm to 11.7 kV/cm and then unidirectionally from 11.7 kV/cm to 0 kV/cm.
An embodiment of the present invention will be described below.
An optical device 10 according to the embodiment shown in
Optical characteristics of the optical device 10 were observed under a polarizing microscope. More specifically, as shown in
The transparent electrodes 30 and 40 are connected to a DC power supply (not shown) via lead wires and variable resisters (not shown). Voltage of different values can be applied between the transparent electrodes 30 and 40. A switching circuit (not shown) is attached to the lead wires. A positive or negative voltage can be applied between the transparent electrodes 30 and 40 through operation of the switching circuit. The transparent electrodes 30 and 40 also function as electrodes for use to measure the permittivity of the device body 20 (PMN-PT). Besides, they are also used as capacitor output terminals when the optical device 10 is not only used as a device which utilizes the optical characteristics of the PMN-PT, but also used in the manner of an electronic circuit as a device which utilizes changes in the dielectric characteristics of the PMN-PT taking place with changes in the optical characteristics.
Examples and comparative examples of the present invention will be described below. Incidentally, observations and measurements were conducted at room temperature (25° C.) unless otherwise stated.
Optical devices according to examples 1 and 2 and comparative examples 1 to 4 were created using a 122-μm thick device body made of a PMN-PT (001) plate. The composition ratio x of PbTiO3 in the PMN-PT was 0.15 in example 1, 0.13 in example 2, 0.2 in comparative example 1, 0.28 in comparative example 2, 0.1 in comparative example 3, and 0.06 in comparative example 4.
FIGS. 4(a) to 4(c) show results obtained by observing the device bodies of the optical devices according to example 1 and comparative examples 1 and 2 through crossed Nicol prisms under the polarizing microscope with no electric field being applied.
FIGS. 11(a) to 11(c) show results obtained by observing the device body of the optical device according to example 1 through crossed Nicol prisms under the polarizing microscope with no electric field being applied, as in the case of
It is probably due to disorderly domain arrangement or small domain size that in FIGS. 11(a) to 11(c), the PMN-PT in the optical device according to example 1 does not allow optical transmission when no electric field is applied. In the optical device according to example 1, when no electric field is applied, the PMN-PT has a relative permittivity as high as around 9,500 (9,000 to 10,000), as shown in
The polarizing microscope observations described above and below employ a halogen light source with a wavelength range of 400 to 600 nm centered around 540 nm. In drawings which show results of the polarizing microscope observations, reference numeral A denotes an analyzer and P denotes a polarizer. Also, drawings which show results of polarizing microscope observations carried out by applying an electric field also contain a symbol which indicates the direction of application of the electric field. Under crossed Nicol prisms, the analyzer A and polarizer P are used by being arranged perpendicular to each other with a specimen placed between them. If the specimen is optically isotropic, the observation under the polarizing microscope results in a dark field. If the specimen is optically anisotropic, the observation results in a bright field. Generally, a ferroelectric specimen is an anisotropic body, but if the polarizer P is set in the direction of polarization, the observation results in a dark field. This phenomenon is known as extinction. The crystal phase of the PMN-PT in the optical device according to example 1 is a rhombohedral phase at room temperature (25° C.) and the polarization direction of the PMN-PT (001) plate in a rhombohedral phase coincides with a direction of <110>. Thus, a dark field appears at a position inclined at 45° from the x axis and a bright field appears at a position inclined at 60° or 30° from the x axis. The brightest position is known as a diagonal position. In a plate in a rhombohedral phase (001), the diagonal position appears on the x or y axis.
Incidentally, to obtain observation results shown in
FIGS. 5(a) to 5(c) show results obtained by observing a device body of an optical device according to comparative example 3 through crossed Nicol prisms under the polarizing microscope.
It can be seen from the results shown in FIGS. 5(a) to 5(c) and
FIGS. 7(a) to 7(d) show results obtained by observing the device body of the optical device according to example 1 through crossed Nicol prisms under the polarizing microscope with an electric field which changes unidirectionally from 0 kV/cm to 8.2 kV/cm being applied to the optical device.
When an electric field above a threshold (2 kV/cm, in example 1) is applied, the PMN-PT in the device body makes a transition from a state in which it blocks optical transmission to a state in which it allows optical transmission as shown in FIGS. 7(c) and 7(d). At the same time, the relative permittivity of the PMN-PT is approximately halved to 6,000 (5,000 to 7,000) as shown in
FIGS. 9(a) and 9(b) show results obtained by observing the device body of the optical device according to example 1 through crossed Nicol prisms under the polarizing microscope with an electric field which changes unidirectionally from 8.2 kV/cm to 0 kV/cm being applied to the optical device.
FIGS. 10(a) to 10(d) show results obtained by observing the device body of the optical device according to example 1 through crossed Nicol prisms under the polarizing microscope with an electric field which changes unidirectionally from 0 kV/cm to −8.2 kV/cm being applied to the optical device.
When an electric field which changes unidirectionally from 0 kV/cm to −8.2 kV/cm is applied in this way, a dielectric anomaly occurs when the electric field exceeds a predetermined dielectric anomaly threshold (−0.8 kV/cm, in example 1), resulting in a polarization switching. The domain structure of the PMN-PT changes accordingly. The dielectric anomaly caused by an electric field of −0.8 kV/cm can be observed from the graph in
In this way, even if the strength of the applied electric field is increased or decreased, the state which has a low permittivity and allows optical transmission is maintained. In order for the PMN-PT to make a transition from the state which has a low permittivity and allows optical transmission to the initial state which has a high permittivity and blocks optical transmission, it is necessary to heat the device body to or above the Curie temperature.
FIGS. 14(a) to 14(c) show results obtained by observing the device body of the optical device according to example 1 through crossed Nicol prisms under the polarizing microscope with no electric field being applied after the optical device is heated to or above the Curie temperature.
The device body of the optical device according to example 2 was observed through crossed Nicol prisms under the polarizing microscope with no electric field being applied. Although not shown, it was confirmed that in the optical device according to example 2, the PMN-PT was in a state in which it blocked optical transmission.
FIGS. 17(a) to 17(d) show results obtained by observing the device body of the optical device according to example 2 through crossed Nicol prisms under the polarizing microscope by applying an electric field which changes unidirectionally from 0 kV/cm to 11.7 kV/cm and then unidirectionally from 11.7 kV/cm to 0 kV/cm.
When an electric field above a threshold (3 kV/cm, in example 2) is applied, the PMN-PT in the device body makes a transition from a state in which it blocks optical transmission to a state in which it allows optical transmission as shown in FIGS. 17(b) to 17(d). At the same time, the PMN-PT exhibits a low relative permittivity (permittivity) as shown in
When an electric field which changes unidirectionally from 11.7 kV/cm to 0 kV/cm is applied to the optical device according to example 2, the relative permittivity is kept at as low as approximately 7,000 as shown in
The threshold at which the PMN-PT makes a transition from a state which has a high permittivity and blocks optical transmission to a state which has a low permittivity and allows optical transmission varies between examples 1 and 2: 2 kV/cm in example 1 and 3 kV/cm in example 2. Generally, the threshold increases with decreases in the composition ratio of PbTiO3 in the PMN-PT.
The embodiment described above may be changed as follows.
The optical device 10 may be embodied as an optical memory. In that case, the optical memory stores information as a binary signal of a state which allows optical transmission or a state which blocks optical transmission. The device body 20 exhibits a low permittivity when it is in a state in which it allows optical transmission, and a high permittivity when it is in a state in which it blocks optical transmission. Consequently, by detecting differences in the permittivity as voltage changes, it is possible to read stored contents easily.
Conventional techniques which use light to store information include a magneto-optical disk. The magneto-optical disk stores information as a binary signal in a specific area on the medium by irradiating the specific area with a laser beam, thereby heating the irradiated specific area to or above the Curie temperature, and then applying an external magnetic field when holding power of the specific area lowers, thereby magnetizing the specific area upward or downward. In this way, with the magneto-optical disk, the magnetic field must be applied upward or downward distinctively after heating the specific area to or above the Curie temperature by irradiating it with a laser beam. On the other hand, if the optical device 10 is embodied as an optical memory, it is possible to switch between a state (ON) which allows optical transmission through a specific area and a state (OFF) which blocks optical transmission, depending on whether or not the optical device 10 is heated to or above the Curie temperature.
The optical device 10 may be embodied as a light valve. In that case, the light valve controls entering light and outgoing light by switching between a state which allows optical transmission and a state which blocks optical transmission. The device body 20 exhibits a low permittivity when it is in a state in which it allows optical transmission, and a high permittivity when it is in a state in which it blocks optical transmission. Consequently, by detecting differences in the permittivity as voltage changes, it is possible to detect operation of the light valve.
The device body 20 of the optical device 10 may be formed of PZN-PT or PIN-PT instead of PMN-PT.
The optical device 10 may be used as an actuator which utilizes piezoelectric characteristics of PMN-PT in addition to the optical characteristics and dielectric characteristics of the PMN-PT.
Number | Date | Country | Kind |
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2004-023603 | Jan 2004 | JP | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/JP05/01275 | 1/28/2005 | WO | 7/28/2006 |