JPS59195509A - Amorphous tellurium-tantalum compound material and its manufacture - Google Patents

Abstract

PURPOSE:To manufacture a novel amorphous Te-Ta compound material by mixing tellurium dioxide with tantalum oxide so as to provide a composition having a specified ratio, melting the mixture by heating, and cooling the melt very rapidly. CONSTITUTION:TeO2 is mixed with Ta2O5 so as to provide a composition represented by a formula (TeO2)1-x.(Ta2O5)x (where 0.30>=x>0), and the mixture is heated at a temp. by about 50-120 deg.C above the melting temp. The heating is usually carried out in the air. The resulting melt is very rapidly cooled at about 10<4>-10<6> deg.C/sec cooling rate to obtain a novel amorphous compound. This compound can be converted into an oriented polycrystalline thin film material by heat treating the compound at a temp. below the crystallization temp. for a prescribed time.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a variety of tellurium-cuntal amorphous compound materials and a method for producing the same.

In recent years, with the development of electronics and related technologies, research on oxide ceramics based on tellurium dioxide (Te 02 ) and their single crystals has been actively conducted, especially in photo-electrical, audio-electrical, A stable compound of Te 02 and Ta 205 that is being researched as a conversion element material in fields such as magnetism, optical polarization, and X-ray spectroscopy, as well as as a catalyst material and magnetic material. However, only a few types of crystalline compounds have been described in a few documents, and although research into single crystallization of these compounds has been actively conducted, no research has been conducted on amorphous compounds. Not yet.

The present invention provides a tellurium-tantalum based amorphous oxide which has been completely unknown heretofore. That is, the present invention provides (
A novel tellurium-tantalum based amorphous compound material having a composition of
” A method for producing a tellurium-tantalum based amorphous compound material, which comprises heating and melting a mixture of tellurium dioxide and tantalum oxide corresponding to Ta203)X (where X is the same as above) and then ultra-quenching the mixture. This is related.

The tellurium-tantalum amorphous oxide of the present invention can be used for magnetic materials, photoresponsive magnetic elements, temperature-responsive magnetic elements, magnetic memory materials, ion conductive materials, magnetic tapes, catalysts, light-transparent conductive materials, and dielectric materials. Materials, opto-electric switching elements, heat
It is useful as an electrical switching element, etc.

The present invention further provides (Te o2) I
203)2. (However, 0.80.x)0) A method for producing an oriented polycrystalline thin film material is also provided, which comprises heat-treating a tellurium-tantalum based amorphous compound material having a composition below its crystallization temperature. This is what we provide.

The oriented polycrystalline thin film material obtained in this way can be used for optical memory materials, magnetic memory materials, electrochromic materials, optical switches, optical variable devices, pyroelectric devices, photoacoustic devices, optical waveguide devices, optical mirrors, and surfaces. Wave devices, piezoelectric transducers, chemical sensors, temperature and humidity sensors,
Useful as a catalyst.

In the present invention, the term ``tellurium-tantalum amorphous compound'' includes not only the case where the compound is amorphous alone but also the case where the amorphous compound contains a polycrystalline phase.

The tellurium-cuntal amorphous @ oxide of the present invention is produced as follows.

The raw material used in the present invention is a mixture of tellurium dioxide and tantalum oxide, and the composition ratio is (Te
02) 1. x ・CTa2u6 ) x (However, 0,80≧x>0). A raw material mixture having the above composition ratio is heated and melted, and then cooled extremely rapidly. The heating and melting may be carried out at a temperature higher than the temperature at which these raw material mixtures are sufficiently melted, preferably in a temperature range of 50 to 200°C higher than the melting temperature, particularly preferably in a temperature range of 80 to 150°C higher. There are no particular restrictions on the atmosphere during heating.
Usually done in air. Next, the melt of the raw material mixture is ultra-quenched. Ultra-quenching is an essential requirement for the method of the present invention, and only through this is it possible to obtain an amorphous Shinji compound. Ultra-quenching is usually carried out at a cooling rate of about 10' to 106°C/sec. This ultra-rapid cooling can be carried out by a wide variety of methods as long as it can be cooled at the above-mentioned cooling rate.The melt of the raw material mixture is ejected onto the surface of the roll rotating at high speed and solidified in the atomic arrangement of the liquid state. A typical example is the method of forcing people to do something.

An example of a quenching apparatus for a molten raw material mixture used in carrying out the method of the present invention will be described below with reference to the drawings.

Figure 1 shows the main body of the rapid cooling device (
3) shows a front view. The quenching device uses a dielectric heating coil (
6), (5)..., raw material heating tube (7),
The support (9) of the tube (7), the nozzle (11) for spouting the molten raw material, the quenching roll (13L), the nozzle (11)
) Cooling nozzle fib) hYh flow prevention air nozzle (
17), Nozzle (ll) fine adjustment machine + Mff (I9)
, air cylinder cylinder), and a box (2) to receive the cooled material.
3), the cooling material outlet (25), etc. are the main components. By installing a fan for cooling the roll inside the cooling roll (131) and providing an air blowing port at the end of the roll surface, the molten raw material can be rapidly cooled stably. , details of the support (9) are shown.

In FIG. 2, the support body (9) has valves (cooling water inlet channel (2) with two forces, cooling water outlet channel (31), and blow air inlet channel (C) with a needle valve (33). Fine adjustment of the distance between the surface of the roll (+a) and the nozzle (II) 4
Rectifying perforated plate (39
).

When carrying out the method of the present invention using the quenching device (3) shown in FIGS. 1 and 2, first, a raw material mixture of a predetermined composition is stored in a tube (7) having a nozzle Q+ for blowing out the melt. . This tube (7) is sufficient in high temperature oxidizing atmosphere! Preferably, it is made of a durable material, such as platinum, platinum-rhodium, iridium, silicon nitride, boron nitride, or the like.

Note that the material of the portion not in direct contact with the raw material melt may be high melting point ceramics, glass, or metal. The shape of the nozzle opening is appropriately determined depending on the target product; for example, a round shape is used for a thin linear material, and a slit-like shape is used for a wide product. The shape of the nozzle opening may be oval or other shapes. The raw material mixture housed in the tube (7) is then heated to a temperature higher than its melting point to become a melt, and then passed from the mouth of the nozzle 01) onto the surface of the roll 0□□□ which is rotating at high speed. The gas is then blown out at a constant gas pressure and rapidly cooled on the roll surface. The blowing angle of the raw material melt between the nozzle opening and the roll direction may be perpendicular to the roll surface if the target compound is about 8 mm or less in width, and perpendicular to the roll surface if the width is about 67 nni or more. is θ°・−45°. Although these blow-out angle adjusting cedar machine columns can be incorporated into the device itself as a foam that can set a predetermined angle, it is preferable to process the nozzle itself.

The method of heating the raw material mixture is not particularly limited.

It is usually carried out in a furnace with a heating element, a dielectric heating furnace or a J5 light heating furnace. The temperature of the raw material melt is 50 to 200 degrees below its melting point.
The temperature should preferably be about 80 to 150 degrees Celsius.If the temperature is too close to the melting point, the melt may be blown out onto the roll, causing it to cool and solidify near the nozzle. If the temperature rises too high, quenching on the roll surface tends to become difficult.

An inert gas is preferable as the neutral pressure gas used to blow out the melt onto the roll surface, such as argon,
Although nitrogen, helium, etc. may be used, dry compressed air is preferable in order to maintain the melt raw material in an oxidized state. The gas pressure is 1 to 2.0 kf, depending on the size of the nozzle opening.
/cm preferably 0.5-1. Oky/cm”
That's about it. In addition, the distance between the nozzle opening and the roll surface when blowing out the raw material melt is preferably about 0.01 to 1.0 mm, more preferably 0.05 to Q, 5 mtn 771
degree. If it is smaller than 0.01 mrn, the puddle amount will be very small and a homogeneous material cannot be obtained;
．． If the thickness is larger than 0 mm, the amount of puddles becomes excessive, and if the thickness exceeds the puddle thickness formed by the interfacial tension of the composition melt, it may be difficult to form puddles.

The material of the roll includes copper and its alloy with good thermal conductivity, the above-mentioned materials having a hard chromium plating layer, steel, stainless steel, and the like. Change the circumferential speed of the roll to 5WL/sec~
By rapidly cooling the raw material melt at a speed of 85 m/sec, preferably 1077 z/sec to 20 m/sec, the desired amorphous compound material of good quality can be obtained. At this time, the roll circumferential speed is 5 m.
/second or less is not very preferable because it tends to be difficult to become amorphous. When the peripheral speed of the roll is higher than 8577 Z/sec, the shape of the obtained target material becomes very thin and becomes scaly or fine powder, but the material structure is still the same as the amorphous compound material of the present invention. It is.

When producing the compound of the present invention under reduced pressure or high vacuum, or in an inert gas atmosphere, reduction of the raw material melt occurs at high temperatures. However, the number of acid atoms in the composition atoms decreases, and the resulting material becomes colored purple or black. However, this colored product is also a compound of the present invention physically and can be used in a colored state.

When heating and melting the raw material mixture in a tube, it is necessary to completely melt the mixture. However, before the mixture is completely molten, some of the molten material may flow out from the nozzle tip, so the nozzle tip is locally cooled to prevent the melt from flowing out. It is preferable to do so. A typical means for locally cooling the nozzle is to blow a cooling gas onto the tip of the nozzle, and the gas may be an inert gas such as argon, helium, nitrogen, etc., but dry, cold compressed air is more preferable.

The novel amorphous compound material according to the present invention usually has a
It has a thickness of about 10 μm and is a very brittle material.

For this reason, after the material is rapidly cooled and solidified on the roll surface, it is preferable that stress is not applied to the material as much as possible. One of the causes of stress addition is the large turbulent flow in the air layer on the roll surface caused by the wind phenomenon caused by roll rotation in the atmosphere. In order to prevent this turbulent flow and to improve the adhesion between the molten raw material mixture to be rapidly cooled and the roll surface, a countercurrent blowing nozzle for preventing wind blowing, that is, a first
Install an anti-eddy air nozzle (I7) as shown in the figure, or install a fan fixedly inside the roll.

In the latter case, the turbulent flow generated inside the roll is absorbed from the rotation speed of the roll through a variable-diameter gust inlet provided at the end of the roll surface, and is then discharged from the front of the roll. The molten material is moved into the inside of the roll, thereby making the molten material more tightly adhered to the roll surface, and furthermore, the roll itself can be air-cooled by the air blowing movement. Further, in order to maintain the dimensional uniformity of the obtained material, if grooves for cutting the material are provided on the roll surface at right angles to the rotation direction, the material can be cut to a constant size.

The atomic arrangement structure of the tellurium-tantalum compound of the present invention changes greatly depending on the mixing ratio of raw materials, and specifically, it can be roughly classified as follows. First, when 0.20≧x)0, an amorphous compound ioo% is obtained, and 0.8
In the range of 0≧x)0.20, an oriented polycrystalline mixed amorphous compound containing a Ta 205 crystal phase is obtained;
80, a material mainly consisting of Ta205 crystal phase is obtained. FIG. 8 shows the production range of the material of the present invention.

The peripheral speed of the quenching roll of the quenching device used is 57yz
Within the range of m/sec to 85 m/sec, no major changes are observed in the structure of the material obtained in each composition range.

The oriented polycrystalline thin film material of the present invention has (Teo2) 1-x (Ta205) x obtained as described above.
(However, 0.30≧x〉0) A tellurium-tantalum amorphous compound material with a composition of
After determining Tc), the compound material is heat-treated at a temperature below the crystallization temperature for a predetermined period of time. In addition, if the heat treatment time is too long even below the crystallization temperature,
Since the result is a non-oriented polycrystal, care must be taken in this regard.

For example, (T'e 02 ) 1 y, ・(Ta20
5) The crystallization temperature of the tellurium-tantalum amorphous compound material where X is X...0.15 is 609°C, and when this is heat-treated in the air, the following materials can be obtained depending on the conditions.

1.605℃XIO min; oriented polycrystalline 2.605℃×
30 minutes; polycrystalline material 3.570°C x 10 minutes; amorphous material 4.570°C x 80 minutes; oriented polycrystalline material 5, 57 (M
cx 60 minutes; To identify the polycrystalline orientation and Tatsuzou of the material of the present invention, the presence or absence of crystallinity was confirmed using X-ray diffraction and a polarizing microscope, and Tachibana analysis was performed, and a very small portion was observed using a scanning electron microscope. Ta.

The following examples will further clarify the features of the present invention.

Example I Te 02 (purity 99.9%) and Ta203 (purity 99.9 (7'D)) were blended in a predetermined composition, mixed uniformly, and then calcined at 850°C for 30 minutes to obtain a composition raw material. And so.

The obtained composition raw material was transferred to a platinum tube (diameter 10 tnm).
× Length L50mtn) and put 6 in the dielectric heating coil.
t'F1, oscillation tube fiber voltage 13■, anode voltage 10K
V, grid current 120-150 mA, anode current 1.2-
Dielectric heating was performed under the condition of 1.8A. Dry compressed air was blown onto the surface of the completely melted raw material number quenching rotating roll to quench it.

Tables 1 and 2 show the composition and manufacturing conditions. Samples Nos. 1 to 20.25 and 29 in Tables 1 and 2 show ribbon-like, completely clear amorphous oxide materials. or,
No. 24 is a thin piece because the roll rotation speed is high, but it can be used in fields such as catalysts where there are no restrictions on shape.

In addition, nozzle shape A is 0.2 mm x 4 m.
The nozzle shape °B indicates a circular nozzle with a diameter of 0.2 mm.

Reference example 1 (TeO2), -E・(Ta20.)x=0
．． Sample No. 8.10 of the above Example 1 corresponding to No. 15.
The X-ray diffraction results for 12.18 and 15 are shown in FIG. The peripheral speed of the quenching roll is 5.18 tn/sec (N
It is clear that there is no significant change in the atomic arrangement structure of the material obtained within the range of 84.54 m/s (No, 15) from O38).

Reference Example 2 Sample N099 of Example 1 above, which corresponds to X=0.15 in (TeO2) 1x ・(Ta205) x
The differential thermal analysis results are shown in Figure 5.

In FIG. 5 1, Tc indicates the crystallization temperature, Tno indicates the glass transition point, and 7+11) indicates the melting point. , Reference example 3 In ('reO2)1-X・(Ta205)x, x=
A photograph showing the appearance of sample N017 of Example 1, which corresponds to 0.10, is shown as Reference 1 side I.

Reference Example 4 Scanning electron micrograph of sample No. 7 of Example 1 above (
20000x and 1500x) reference drawings ■ and 1, respectively.
Shown as ■.

Reference Example 5 Sample No. 8 of the above Example 1 corresponding to x-0,10 in (Te a.) 1 x ・(Ta2O,)
The infrared absorption spectrum of is shown in FIG.

Sample No. 6 of the above Example 1 corresponding to x=0.10 in (Te 02 ) 1-x-(Ta205 ) X,
Figure 7 shows the DC electrical conductivity of No. 8 at 18.7°C, and Figure 8 shows the dielectric constant (N) and qualified loss (Br) at 18.3°C with respect to frequency. ．．
0011C771 and the electrical area is 0.0491 cm
And so.

Example 2 Sample No. 9 of Example 1 was heat-treated in air at 570°C for 30 minutes, and then subjected to X-ray diffraction. As a result, the diffraction angle (2θ
) A single sharp diffraction peak was observed, confirming a change from an amorphous structure to an oriented polycrystalline structure.

In addition, the electrical properties before and after heat treatment (frequency I KH
z) was as follows.

Before heat treatment After heat treatment Dielectric constant (ε) 52 165 Dielectric loss (tan δJ 5j5 0.60

[Brief explanation of the drawing]

FIG. 1 is a front view of an example of a quenching device for molten raw materials used in the method of the present invention, FIG. 2 is a partially enlarged detailed drawing of the quenching device in FIG. 1, and FIG. Drawings showing the composition range; FIG. 4 is an X-ray diffraction diagram of some of the materials of the present invention; FIG. 5 is a differential thermal analysis diagram of some materials according to the present invention; FIG.
The figure is an infrared absorption spectrum of another part of the material according to the present invention, FIG. Graphs showing the dielectric constant and reading loss versus the frequency l of the material are shown, respectively. fl) is the stand, (3) is the quenching device main body, (
5), (5) is a dielectric heating coil, (7) is a raw material heating tube, (9) is a support for the raw material heating tube, (3t) is a nozzle for blowing out the molten raw material, and the end is a quenching roll, Cl5 ) Cooling nozzle for Han nozzle (11), (17)
is the disaster prevention air nozzle (191 is in front of the nozzle (lt) fine adjustment machine, el) is the air cylinder, (23) is the box for receiving the cooled material, (25) is the cooling material outlet, 12η is the valve, (29
) is the cooling water passageway, iri is the cooling water discharge passageway, (33)
is the needle valve, (3 is the blow air introduction path, (3 is the blow air introduction path,
7) is a mechanism for finely adjusting the distance between the roll and the nozzle (liJ), and (89) is a perforated plate for rectification.
Above) Figure 1, Figure 3 1-? 1 hour (Continued from Bonn page 1 ■Applicant Kenji Masumoto 3-8-22 Uesugi, Sendai City ■Applicant Kenji Suzuki 11-12-11 Shokan, Izumi City ■Applicant Shuji Masuda Itano, Tokushima Prefecture 27-8 Miyanomoto, Ejiri, Kitajima-machi, District ■Applicant: Oita Oikei 86, Higashinakatomi, Aizumi-machi, Itano-gun, Tokushima Prefecture

Claims (1)

[Claims] ■ (Te 02 ) 1x ・(, Ta206 )
Tellurium-tantalum amorphous compound material 1 having a composition of X (0.30≧X20), (2) 0.20. The tellurium-tantalum amorphous compound material according to claim 1, wherein ≧x)o. (2) The tellurium-tancle type amorphous compound material according to claim 1, wherein 0.30λ';X>0.20. ■ It is characterized by heating and melting a mixture of tellurium oxide and tantalum 0ide, and then ultra-quenching the melt (TeO
□)1 x・(Ta205)'x (However, 0.305
≧x>0) A method for producing a tellurium-tantalum amorphous compound material having a composition. (104-b) A method for producing a tellurium-tantalum amorphous compound material according to claim 4. (2) A method for producing a tellurium-tantalum amorphous compound material according to claim 4 or 5, wherein the raw material melt is ultra-quenched by contacting it with a solid. ■ The raw material mixture is put into a heating tube equipped with a nozzle equipped with a slit-shaped, circular, or elliptical outlet, and after heating and melting at a temperature 50 to 200 degrees Celsius higher than the melting point of the mixture, the mixture is heated at 5 tyx/sec. The tellurium-tantalum amorphous crystal according to any one of claims 4 to 6, wherein the melt is blown out through the nozzle onto the surface of a roll rotating at a circumferential speed of ~85 ni/sec for ultra-quenching. method for producing quality compound materials. ■ (Te 02 ) I X・(Ta205) X
A method for producing an oriented polycrystalline R8 material, characterized in that a tellurium-tantalum amorphous compound material having a composition of (0.80x)0) is heat-treated at a temperature below its crystallization temperature.