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JPS4895155

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DESCRIPTION JPS4895155
3 Patent applicant address Osaka Prefecture Kadoma city Ogata Kadoma name 1006 (582)
Representative Matsushita Electric Industrial Co., Ltd. Representative Matsushita Shoji 4 agent 〒
517 Kadoma city Osaka Bold Kadoma city address 1006 Matsu [Electronics Industry Co., Ltd. 5
List of attached documents ■ Japan Patent Office Open Patent Publication ■ Japanese Patent
Application '8'95155. Examination request not requested (all 5 pages) Office internal number 1 o
Japan classification "乙 θ 6 I, ga ♂ 0♂! Description 1, title of the invention
Delay material
3, detailed description of the invention. The present invention relates to a retarding material
having a long delay time utilizing the phenomenon of cubic to tetragonal phase transition of
spinel-type oxide crystals having the Jahn-Teller effect (GJahn-Teller). The Jahn-Teller effect of
spinel-type oxide crystals is that the dg-electron orbital extending in the direction of oxygen ions
of iron group ions occupying a position surrounded by a regular tetrahedron with oxygen ions is
When the tetrahedron has cubic symmetry and is at a high energy level of five-fold degeneracy
by a group a of iron group ions, the symmetry of the crystal is lowered to 31 degeneracy t1 and
double states of the electron orbit Separate the crystal structure from high symmetry cubic to
low symmetry company's tetragonal phase transition fz to stabilize the electronic energy state.
The new phase transition is called the Yarn-Teller effect. The phase transition with a crystal
occurs as the directions of deformation of individual tetrahedrons align as axes of deformation as
a cooperative phenomenon. In the present invention, the acoustic wave 4 of the crystal which
accompanies the phenomenon of phase transition of the spinel oxide crystal having the step-andtailer effect! Providing a retarding material applying a change in sex. The present invention uses
a spinel type oxide single crystal having a Yarn-Teller effect as a retarding material, and the
velocity of the transverse wave traveling in the single crystal is Vs, and the distance the
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transverse wave travels in the single crystal is 8. Assuming that the time until the transverse
wave comes into the crystal is t, it can be expressed by the relational expression 8 mV st (1). The
spinel m oxide single crystal having the Jahn-Teller effect is subject to phase transition due to the
Jahn-Teller effect and it is confirmed by the present inventor that the * a constant of the single
crystal or the phase transition-temperature changes significantly. The EndPage: elastic constant
of cubic system, CuvQa, elasticity corresponding to crystal deformation from cubic system to
tetragonal system among “n-011e”, constant is (Cu′-Cn), and phase transition of crystal The
corresponding change is very large. This elastic constant (I-C) is 1 l-Qs its velocity of sound Vs
and Vs 冨-when the shear wave ultrasonic wave travels in the direction of 11o in the crystal and
is deflected in the direction of <I10>. There is a relationship of-(2) ρ. Here, ρ is the density of
crystals. Assuming that the length of the single crystal is L, the distance S in which the transverse
wave travels back and forth in the single crystal is j9sw2T, so a crystal of spinel structure
showing a phase transition due to the yarn chiller effect is (1) and (2) Since the elastic constant
rapidly decreases at the phase transition temperature, from equation (3), the time t for the
transverse wave to enter and come out of the crystal becomes long.
I got into the crystal. No. 6 comes out delayed in the crystal. The present invention can take
advantage of this phenomenon to obtain delay materials having any delay time. Table 1 is a
typical material known to cause a phase transition from an orthorhombic phase to a cubic phase
by the Jahn-Teller effect in a crystalline structure made of spinel. Table 1 10uFe 204A + (1)
"1.0'6'j 360 DEG C. Yarn tera-effect has been found with many other materials. The crystal axial
ratio c / a indicates that the axial ratio when the major axis of the crystal axis is C and the minor
axis is a, the larger the value of i, the larger the deformation amount as tetragonal. The spineltype oxide having the Yarn-Teller effect shown in Table 1 is effective as the delay material of the
present invention, but mixed crystals with N10r204 and other spinel-type oxides are used in the
crucible. The degree of utilization is high, that is, the transition temperature of the N1 · r04
crystal is 27 ° C. and normal temperature, and by using mixed crystals with other spinel type
oxides, the transition temperature can be arbitrarily selected around normal temperature
Therefore, when incorporated in a circuit or the like, an extra device such as heating becomes
unnecessary. Using mixed crystals of spinel type oxide having a Yarn-Teller effect and Yar 7e
Tiller effect but using an oxide of spinel structure, changing the composition ratio of mixed
crystals at any temperature Delay materials can be obtained that exhibit arbitrary delay times.
FIG. 2 is a characteristic curve showing the change of the velocity of sound Vs propagating in the
crystal with respect to the temperature change of N1 □ Zn, −2Or @ C4 single crystal. As
apparent from the figure, the temperature of the crystal is lowered, and as the phase transition @
degree is approached, the sound velocity Vs propagating in the crystal is delayed. Also, when the
composition ratio 2 of the N1 ZZ n knee zcr, 04 single crystal decreases, that is, as the amount of
NiO in the crystal decreases, the phase transition m degree shifts to the low temperature side,
and the sound velocity Vs propagating in the crystal becomes faster. In the curve of FIG. 2, NOj is
N1 °. 4Zn、。 6Or, 04, NO2 is a characteristic curve of N1avszno, tsCrt ○, and Nvs are Ni,
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4Zn,. As a result of measuring each delay time at 500 ° K, the result N ○ 1 is 16 μsec ^ NO2 is
7 μl 5 eO / 1 meNO5 is 4. EJ8e01011gでhった。 The crystal structure of the splay
ice type Ni0r, 04 is the lower temperature region of cubic crystals in the region of 27 ° C., XJll
high temperature region due to the Yarn-Teller effect of N ions + ion occupying tetrahedral
position. In the phase transition to the tetragonal crystal structure.
The amount of deformation is very large, and at low temperatures, the ratio of C-axis and a-axis
lengths reaches 496, and at the phase transition temperature, the axial ratio 296 suddenly
deforms as a thermodynamic first-order transition. FIG. 3 shows Ni0 r20. As an example of the
delay material of the present invention. A−? 0 shows an O-phase diagram of mixed crystal
system with ZnCr and 04 which does not show the Bon-Teller effect, the composition ratio Z of
the mixed crystal on the X axis and the absolute temperature on the Y axis. 0 curved edge
TtFiNizZnl-2or It is a transition curve of transformation of a crystal deformation with a
transformation of composition ratio 2 of 0 04 mixed crystal to a direct change curve, and the
transitional opacity shifts to lower-side EndPage: 2 as the amount of Z in the mixed crystal
increases. ing. At the same time, the amount of deformation-is small. In general, it is extremely
difficult to grow a single product of spinel type oxide exhibiting a phase transition due to the
Yarn-Teller effect, or a solid solution of an oxide of the present invention and another oxide not
exhibiting the Yarn-Teller effect. . For example, since CuFe, O, is thermally decomposed to G'u, O,
Fe, O, 0 uFqO ,, Ouo, F @ ,, C5 in a temperature range exceeding 900 ° C., a single crystal is
grown. It is difficult to do. In addition, Mn5o4 is unstable at high temperature of the Mn & apos;
s & apos; s of Yarn-Teller ion, and waves into stable Mn & quot; + ions, so that a good crystal can
not be obtained. Furthermore, since Ni0r, O, and Fe0rlC have a very high melting point of 2000
° C. or more, it is difficult to grow a single crystal. The following Ni0r, 04-Zn0r4. An
embodiment of the method for growing a single crystal of O, solid solution is shown. In a
platinum crucible, put Ni0r, O, and Zn0r, (,, as a powder and a solvent of (, Bi, O) at a weight ratio
of 1: 6, and hold at 1.500 ° C. for 24 hours, 0.86 F: Slowly cool to 8 "room temperature with a
temperature gradient between f / R. i、500°CでNi0rl04、’ZnC! The powder
of r, 04 is dissolved in the solvent of Bi ,, “,”, and is gradually cooled down to 150 ° C. (Cd)
(NiZ =) □ Or, solid solution type single crystal of O, , Deposit on the bottom of the platinum
crucible. The single crystal placed in the solvent BitCB can be taken out by boiling in a 30 to 2 o%
nitric acid solution and dissolving the solvent Bl, (:,). The obtained single crystal has a regular
octahedral crystal structure. Generally, crystal growth was performed by the flux method. The
obtained crystals have thin cracks and can not avoid mixing of solvent in layers inside the single
crystal. Even in the single crystal grown by the present inventors, cracking and mixing of the
solvent were remarkable at the initial stage of the growth, but as the crystal growth progressed, a
single crystal in a good crystalline state was obtained.
Hereinafter, measurement examples of the delay 4I properties of J.sub.4 mixed crystals (N.pi.Zx :,
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-2Or, (J4 mixed crystal as the delay material of the present invention will be shown). N1 z Zn 1-g
obtained by the above-mentioned 7 lattices; r, Oa9 ,. From the good part of the mixed crystal
state, single crystals are cut out in a prismatic shape having a length of 7 rom and a cross section
of 812-tm) 2 mm in the <110) crystal direction from the good crystalline state. As shown in Fig.
1 on the mirror-polished both f4 base of single crystal 1, AC cut? Attach the water crystal
oscillator 2 for OMH2. Measurement of the sound velocity Vs of the transverse wave traveling in
the crystal was performed by the swing around (Sing Hachiro to zd) method. According to this
method, it is possible to accurately measure the change in the velocity of sound in the crystal
relative to the change of the order of 1.0- '. As described above, according to the present
invention, a spinel-type oxide having a yarn-Teller effect or a mixed crystal of the oxide and an
oxide having a spinel-type structure but not having a yarn-Teller effect is used as a delay
material. While the delay time of the conventional quartz crystal is 2-3 μsec / am, the delay
material of the present invention can increase the delay time by 2 to jO times and control the
aale of one element t. The delay time can be reduced to one. Furthermore, by changing the
composition ratio of the in crystal, it is possible to obtain a desired delay material with a delay
time of 10.times .. The present invention is based on NiO'l ', a as a spinel oxide having Yar 7φ
teller effect. Or 虻 Ni0r, O. And Yarn-Teller effect is described in detail in terms of N1zZn1-χr r ',
O, with □ 1/1 being a liI product with a spinel-type oxide, but the present invention is limited
thereto It is needless to say that it is effective if the crystal contains at least a spinel type oxide
having a Yarn-Teller effect, not a crystal. 2. In addition, the material of the present invention
can be used to measure the delay time by measuring the delay time, etc. at the same time, or to
measure the delay time. It's too late.
4. Brief description of the drawings. FIG. 1 is a perspective view showing an embodiment of the
delay element using the material 'jp + of the present invention, FIG. 2 and FIG. 3 are
characteristic surfaces of the delay material of the present invention. . Mr. Toshiro Nakao, who is
full name 9PR keeper, has 1 person EndPage: 3 1st I! El。 EndPage: 4 Third
WJZnCr204NiCr2046 Agent address other than Osaka Prefecture Kadoma City Oji Kadoma
address 1006 Matsushita Electric Industrial Co., Ltd. Name (6152) Patent Attorney Shigetaka
Shigeno EndPage: 5
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