JPH0571124B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an amorphous ferromagnetic oxide thin film and a method for producing the same.

(Prior Art) Conventionally, ferromagnetic oxide thin films have been produced by vacuum evaporation using the following two methods.
One method is to oxidize the thin film by depositing a magnetic metal or alloy and then heating it in air to a temperature of about 600° C. or higher. The other one is 10 ^-2 inside the vacuum bell jar.
This method involves depositing a ferromagnetic oxide thin film on a substrate by heating and evaporating the metal in a reduced pressure of about forr. The thin film produced in this way has many defects such as grain boundaries, cracks, and holes, and is easily peeled off from the substrate. Furthermore, since all of the thin films obtained by the above-mentioned manufacturing method are polycrystalline, their crystal grain boundaries and relatively large number of defects are serious disadvantages when used in magneto-optical materials.

(Problems to be Solved by the Invention) Attempts have been made to produce single-crystal oxide thin films in order to eliminate the disadvantages of the polycrystalline oxide thin films described above. Single-crystal oxide thin films do not have grain boundaries, but they often have some defects. Moreover, a major problem in producing this single-crystal thin film is the matching of the lattice constants of the substrate and the single-crystal thin film. If the matching of the lattice constants of the two is out of the permissible range, distortion will occur between the substrate and the single crystal thin film, which will have various adverse effects on the magnetic and optical properties.

(Means for Solving the Problems) The present invention provides a method for easily producing an amorphous oxide thin film of uniform quality and without the drawbacks of conventional thin films produced by vapor deposition. It depends.

That is, the amorphous oxide thin film of the present invention has no grain boundaries and has excellent uniformity of quality like a single crystal. Furthermore, the manufacturing process is relatively simple, and there is an advantage that the type of substrate material does not matter.

The present invention contains 48 to 36% by weight of ferric oxide (Fe ₂ O ₃ ), ferrous oxide (FeO), nickel oxide (NiO),
32 to 16% by weight of one or more oxides selected from manganese oxide (MnO), copper oxide (Cuo), and magnesium oxide (MgO), the balance being phosphorus pentoxide (P ₂ O ₅ ) contains 20-48% by weight,
The present invention relates to an amorphous ferromagnetic oxide thin film having a magnetic saturation value of 60 to 20 emn/g.

In another aspect of the present invention, 10% by weight or less of the composition range of phosphorus pentoxide is arsenic trioxide (As ₂ O ₃ ), selenium oxide (SeO ₂ ), tellurium oxide (TeO ₂ ). It is an amorphous ferromagnetic oxide thin film substituted with one or more oxides selected from the following.

Still another object of the present invention is to use one or more metals among iron, nickel, copper, manganese, and magnesium as the evaporation source A, and to use phosphorus pentoxide or a part thereof as arsenic trioxide, selenium oxide, etc. , an oxide substituted with one or more selected from tellurium oxide is used as the B evaporation source, and the initial degree of vacuum is set to 5.
After reducing the pressure to below ×10 ^-5 torr, the temperature of the A evaporation source is 1700℃ to 2000℃, and the B evaporation source is 300℃.
Amorphous ferromagnetic oxide can be produced by simultaneously evaporating the metal and oxide by maintaining the degree of vacuum at 1 to 10×10 ^-3 torr while varying the temperature range from ℃ to 700℃, and then depositing it on the substrate. The present invention relates to a method of manufacturing an amorphous ferromagnetic oxide thin film to form a thin film.

Still another object of the present invention is that when the amorphous ferromagnetic oxide thin film obtained by the method of the present invention is heat-treated at a temperature below the crystallization temperature, the normal force-rotation angle increases to 0.6 degrees or more. An amorphous ferromagnetic oxide thin film is obtained.

(Function) The thin film obtained by the method of the present invention contains 48 to 36% by weight of ferric oxide (Fe ₂ O ₃ ), ferrous oxide (FeO),
Nickel oxide (NiO), manganese oxide (MnO),
32 to 16% by weight of one or more oxides selected from copper oxide (CuO) and magnesium oxide (MgO), and the balance is phosphorus pentoxide (P ₂ O ₅ ).
When an amorphous ferromagnetic oxide thin film containing 20 to 48% by weight is heated below the crystallization temperature, the normal force-rotation angle can be increased to 0.6 degrees or more.

The amorphous oxide thin film of the present invention contains arsenic trioxide (As ₂ O ₃ ), selenium oxide (SeO ₂ ), tellurium oxide (TeO ₂ ) can be substituted with one or more oxides selected from the group consisting of:

In the present invention, it is not preferable to limit the content of ferric oxide to 48 to 36% by weight because if the content of ferric oxide is less than 36% by weight, the obtained thin film will not exhibit ferromagnetism. Furthermore, if 48% by weight or more of ferric oxide is added, it is not preferable because the magnetism is lowered due to the small content of other oxides such as phosphorus pentoxide. For the above reasons, the content of ferric oxide was determined to be 48 to 36% by weight.

Next, the reason for limiting phosphorus pentoxide to 20 to 48% by weight is that if the thin film contains more than 48% by weight, the surface of the thin film will lose its gloss and its adhesion to the substrate will deteriorate, making it impractical for practical use. It will be appropriate. Further, if the phosphorus pentoxide content is less than 20% by weight, the magnetism decreases and initial ferromagnetism cannot be obtained, which is not preferable. Ferrous oxide (FeO), nickel oxide, manganese oxide, copper oxide,
The reason why the content of one or more of the magnesium oxides is limited to 32 to 16% by weight is undesirable because if the content of these oxides is less than 16% by weight, the magnetism decreases and ferromagnetism is not exhibited. Furthermore, if these oxides are added in an amount of 32% by weight or more, ferric oxide cannot be contained in an amount of 48% by weight, and P ₂ O ₅ cannot be added in an amount up to 20% by weight, resulting in a decrease in magnetism. Furthermore, if the divalent metal oxide is less than 16% by weight, the amount of P ₂ O ₅ or Fe ₂ O ₃ added exceeds the upper limit of 48% by weight, which is also undesirable because the magnetism decreases. Therefore, the composition range of these divalent oxides was limited to 32 to 16% by weight.

In the thin film manufacturing method of the present invention, the initial vacuum level is reduced to 5×10 ^-5 torr or less before vapor deposition in order to remove impurities in the sputtering chamber. The purpose of removing impurities is achieved by creating a vacuum of ×10 ^-5 torr or less.

In addition, the heating temperature of the A evaporation source (alloy) was set in the range of 1700°C to 2000°C, and the degree of vacuum was changed to 1 while varying the heating temperature of the B evaporation source (oxide) from 300°C to 700°C.
The reason for simultaneous evaporation of metal and oxide by maintaining the temperature at ~10×10 ^-3 torr is that the heating temperature of the alloy A evaporation source is
If the temperature is higher than 2000°C, a polycrystalline thin film will be produced, which is not preferable. The heating temperature of the alloy of A evaporation source is
At temperatures below 1700°C, the alloy is hardly evaporated and no thin film is formed. On the other hand, when the temperature of the A evaporation source is set to 1700 DEG C. to 2000 DEG C., the alloy evaporates well and a high-quality amorphous oxide thin film can be obtained.

Next, when the heating temperature of the oxide of the B evaporation source is set to 300° C. or lower, the oxide hardly evaporates. Furthermore, when heated above 7000°C, the oxide evaporates instantaneously, making it difficult to control thin film formation and impractical. On the other hand, it is possible to obtain a homogeneous amorphous substance by heating the oxide of the B evaporation source at a temperature of 300 to 700°C. Limited. Here, the degree of vacuum is maintained at 1 to 10 × 10 ^-3 torr because when the A evaporation source is heated to 1700°C to 2000°C to evaporate the metal, the degree of vacuum in the bell jar (sputtering chamber) is 1 to 1. ×
When it becomes smaller than 10 ^-4 torr, the metal does not oxidize and forms a film, so the film becomes an alloy film.
Does not become an amorphous film. Also, the degree of vacuum is 1 to 10×10 ^-4
In the torr range, a thin film containing a mixture of polycrystalline and amorphous materials can be obtained, but a pure amorphous thin film cannot be obtained.

However, when the degree of vacuum is 1 x 10 x 10 ^-3 torr, there will be a moderate amount of oxygen in the sputtering atmosphere, and the metal or alloy heated in the A evaporation source will be moderately oxidized during sputtering, resulting in polycrystalline formation. This results in a highly pure amorphous thin film that is free from contamination with particles and the like.

However, when the degree of vacuum becomes as low as 10 ^-2 torr, the success rate of thin film formation decreases significantly, and although an oxide film is formed, it becomes difficult for the cations in the oxide to be included in the film, and the oxide becomes an impurity. No solid, high-quality amorphous material is formed. For the above reasons, the degree of vacuum should be increased to 1 to 10×.
It was limited to 10 ^-3 torr.

The method for producing the amorphous ferromagnetic oxide thin film of the present invention will be described in detail below. Figure 1 shows the vacuum evaporation apparatus used in the production method of the present invention, and there is one evaporation source.
A tungsten board 3 containing alloy sample 1 is placed in one evaporation source A, and the other tungsten board 3 containing oxide sample 2 is placed in the other evaporation source B, and both are separated by a shielding plate 11. The tungsten boards 3, 3 of both the evaporation sources A, B are respectively supported on the base plate 6 by the pillars 4 and the insulating plate 5, and the tungsten boards 3, 3 are respectively shielded.
3 is insulated from the base plate 6 and connected to the respective AC power sources 7, 7 via an ammeter 9 and a transformer 8. Reference numeral 10 denotes a vacuum exhaust port, in which a glass substrate 13 supported by a rotating shaft 12 is arranged in opposing directions at a midpoint between both evaporation sources A and B, and the glass substrate 13 is evaporated from both evaporation sources A and B. A vapor phase synthesis reaction takes place on 13 to produce an amorphous thin film 14.

That is, one evaporation source A of the two evaporation sources A and B
The alloy sample 1 is put therein, and the oxide sample 2 of another evaporation source B is put therein, and the tungsten boards 3, 3 serving as respective saucers are resistance heated by respective power supplies to evaporate each sample. The heating temperature of these tungsten boards 3, 3 is controlled by external AC power sources 7, 7, so that the tungsten boards 3, 3 are heated to their respective optimum evaporation temperatures. Here, the heating temperature of the alloy evaporation source A is an appropriate temperature selected from 1700°C to 2000°C,
The temperature of the oxide evaporation source B is appropriately selected from the range of 300°C to 700°C. The glass substrate 13 was rotated arbitrarily at 0 to 10 revolutions per minute or kept stationary, and both evaporation sources A and B were separated by a shielding plate 11, so that evaporation from both evaporation sources A and B was performed. The alloy evaporated body and the oxide evaporated body are prevented from contacting and reacting in the space between them, and both evaporated bodies meet on the glass substrate 13, where a gas phase reaction occurs and is deposited on the substrate and becomes amorphous. As a result, a thin ferromagnetic oxide film 14 is formed.

Conventionally, it is known that a polycrystalline oxide thin film is produced on a substrate by vapor depositing a metal or alloy under reduced pressure. There is no known method for manufacturing it in a pure manner so that it does not contain. The present inventors sought conditions for obtaining a thin film in an amorphous state by simultaneously depositing an alloy with a high evaporation temperature and an oxide with a low evaporation temperature in vacuum. First, it became clear that the type of oxide that is evaporated together with the alloy is important. That is, oxides that have a relatively low melting point, a low temperature at which the equilibrium vapor pressure is reached, and are particularly easily elevated are suitable.

A study of oxides that meet these conditions revealed that they were phosphorus pentoxide (P ₂ O ₅ ), arsenic trioxide (As ₂ O ₃ ), selenium oxide (SeO ₂ ), and tellurium oxide (TeO ₂ ). Ta. Lead oxide (PbO ₂ ) and bismuth oxide (Bi ₂ O ₃ ) have low equilibrium vapor pressure and relatively low melting points.
is easily reduced under reduced pressure, and boron oxide (B ₂ O ₃ ), silicon oxide (SiO ₂ ), and germanium oxide (GeO ₂ ) have high equilibrium pressures, making them difficult to evaporate and making them unsuitable oxides. It was hot.

Next, an important point in the production method of the present invention is how to evaporate both the alloy and the oxide at the same time. When the alloy was evaporated first and the oxide was evaporated later, the resulting thin film had two layers: an alloy film and an oxide film. Furthermore, when the oxide was evaporated first and the alloy was evaporated later, not only was the success rate of thin film formation extremely low, but also an excessively oxidized thin film was formed. When an alloy and an oxide are evaporated at the same time under certain appropriate conditions, they collide during evaporation, react in the gas phase, and react even after being deposited on the substrate, forming a homogeneous oxide thin film. It was done.

It is very important to evaporate the alloy and oxide simultaneously as described above, and the conditions for this are to adjust the degree of vacuum in the bell jar to an appropriate value of 1 to 10 x 10 ^-3 torr. An alloy film is formed when the degree of vacuum is 1×10 ^-4 torr or less;
In the range of ~10×10 ^-4 torr, a thin film containing a mixture of polycrystalline and amorphous materials is obtained.

When the degree of vacuum is lower than 10 ^-2 torr, the success rate of film formation decreases significantly, and an oxide film is formed, but the cations in the oxide are difficult to contain in the film, and an amorphous film is still formed. Not formed.

As a result of repeating many experiments, 1 to 10×10 ^-3
It has been found that a pure amorphous thin film free of impurities can be obtained by vapor deposition while controlling the heating temperature of the oxide (the evaporation source of B) within the temperature range of 300 to 700° C. within the range of torr. Also, increase the evaporation rate of the alloy, in other words, increase the heating temperature of the alloy to 2000
When the temperature is above 0.degree. C., a polycrystalline film is produced. However, when the temperature of the evaporation source of A was set to 1700°C to 2000°C, a good quality amorphous oxide thin film was obtained. When the temperature of the evaporation source A is below 1700°C, the alloy hardly evaporates and no thin film is formed.

The oxide that serves as the B evaporation source does not evaporate at heating temperatures below 300°C. Also, when heated above 700℃, it evaporates instantly. Therefore, in order to obtain a homogeneous amorphous film, it is necessary to limit the heating temperature to 300°C to 700°C.

The amorphous ferromagnetic oxide thin film produced by the method of the present invention described above had good uniformity and had extremely few defects.

Next, we will discuss the magnetic properties of the amorphous ferromagnetic oxide thin film and the wavelength dependence of normal force-rotation angle.

FIG. 2 shows the relationship between the content of phosphorus pentoxide in a thin film prepared from NiFe ₂ alloy powder and phosphorus pentoxide and the magnetic saturation value at room temperature. As the phosphorus pentoxide content increases, the magnetic saturation value tends to decrease.
In addition, crystalline regions () and amorphous regions () are shown in the figure.
The boundaries are also shown. Phosphorus pentoxide content is approximately 20
If it exceeds % by weight, it becomes amorphous. The magnetic saturation value in this amorphous region is approximately 60 to 20 emu/g.
However, if the thin film contains 48% by weight or more of phosphorus pentoxide, the surface of the thin film will lose its luster, and its adhesion to the substrate will be poor, making it unsuitable for practical use.

In addition, a portion of phosphorus pentoxide less than 10% by weight can be mixed with other oxides.
The magnetic saturation values of amorphous ferromagnetic oxide thin films prepared by substitution with As ₂ O ₃ , SeO _{2 , and} TeO 2 are also approximately the same as shown in FIG. 2.

Figure 3 shows the wavelength dependence of the normal force-rotation angle (2θk) for each sample (a), (b), (c), and (d) shown in Figure 2. (a) and (b) are crystalline substances, and their spectra change relatively monotonically. (c) is a sample near the boundary between crystalline and amorphous bodies, and its spectrum exhibits frequent changes in positive and negative polarity. At the same time, the maximum value of the 2θk value increases to about 21 minutes in a limited wavelength range, and the amorphous ferromagnetic oxide thin film shows a larger value than the crystalline material.

(Example) Next, an example will be described to explain the content of the present invention in further detail.

Example 1 An alloy consisting of 0.6 g of Fe and 0.4 g of Mn was placed in one tungsten boat, and 0.2 g of phosphorus pentoxide and tellurium oxide were placed in the other tungsten boat.
0.08g and 0.08g of selenium oxide were added. 1×
After reducing the pressure inside the bell jar to 10 ^-5 torr, adjust the temperature of the boat on the alloy side (A evaporation source) to about 1700 to 1750°C, and add oxide to maintain the vacuum level at 1 x 10 x 10 ^-3 torr. 300~500 side boat (B evaporation source)
℃ and simultaneously heated and evaporated to form a thin film on a glass substrate by vapor phase synthesis and reaction on the substrate. The film thickness was about 4000 Å. iron-manganese alloy, phosphorus pentoxide and tellurium oxide,
The content of selenium oxide was determined by fluorescent X-ray analysis. As a result, ferric oxide in the film was 48% by weight, manganese oxide was 32% by weight, phosphorus pentoxide was 15% by weight,
Tellurium oxide was 3% by weight, and selenium oxide was 2% by weight. This sample was also confirmed to be amorphous by X-ray diffraction. The produced amorphous ferromagnetic oxide thin film had a magnetic saturation value of 48 emn/g. The vertical force-rotation angle (2θk) showed maximum values of +20 minutes at 500-600 nm and -24 minutes at around 700-800 m.

A similar experiment was also conducted using the above starting material composition with 0.1 g of arsenic oxide added instead of selenium oxide. An amorphous ferromagnetic oxide film was obtained, and the composition of the film was 2% by weight of arsenic oxide, and the contents of other elements were the same.

Example 2 NiFe ₂ alloy powder and phosphorus pentoxide (P ₂ O ₅ ) powder were put into the evaporation sources A and B of two tungsten boats, and after reducing the pressure inside the bell gear to 1.5×10 ^-5 torr, the metal The side board was heated between 1750-1800°C while the oxide side board was heated at 400-500°C. In order to keep the evaporation rate constant, the heating temperature of both boats was finely adjusted by the applied voltage, and the degree of vacuum during deposition was maintained at 1 × 10 × 10 ^-3 torr to form an amorphous ferromagnetic oxide thin film. Created. The composition of the thin film determined by X-ray fluorescence analysis shows that the phosphorus pentoxide content is 22% by weight.
51% by weight of ferric oxide, 27% by weight of nickel oxide
It was hot. Moreover, the magnetic saturation value was 40 emu/g.

FIG. 4 shows the wavelength dependence spectrum of normal force-rotation angle when the thin film thus obtained was heat-treated in air. In the figure, the sample immediately after fabrication,
and 3 times at 200℃, 225℃, and 250℃ respectively.
The spectrum measured after sintering in air for an hour is shown. As the heating temperature increases, the maximum value of vertical force-rotation angle increases,
When heated at 225℃, it reaches about 36 minutes at around 670nm. However, when heated at a temperature higher than that, it tends to decrease on the contrary. When this thin film was heated at 300°C and 350°C, where it crystallized, the normal force-rotation angle decreased significantly.

Example 3 Purpose An Fe-P amorphous oxide thin film (film thickness 2000-4000 Å) produced by a two-source vacuum evaporation method using Fe and P ₂ O ₅ as evaporation sources has excellent thermal stability, magneto-optical properties, etc. It exhibits characteristics different from amorphous metal thin films. These characteristics are considered to be due to the action of P ions present in the oxide thin film. Therefore, in this experiment, thin films with different P ion contents were prepared, and their basic properties such as crystal phase, magnetic saturation value, and Curie temperature were investigated, and their magneto-optical properties were measured.

Experimental method Fe powder and dried P ₂ O ₅ were placed in separate tungsten boats, and after reducing the pressure inside the bell gear to 1 × 10 ^-5 torr, the metal side boat (A
After adjusting the temperature of the evaporation source (evaporation source) to approximately 1700 to 1750°C and reducing the degree of vacuum to 10 ^-3 torr, the boat was heated to simultaneously evaporate Fe and P ₂ O ₅ to create a thin film on a glass substrate. . Thin films with different composition ratios of Fe and P ₂ O ₅ can be arbitrarily produced from metal films to oxide films by controlling the heating temperature of each boat. The glass substrate was rotated 8 times per minute to obtain a uniform film. The film formation rate is slow and the efficiency is poor.

Experimental Results Figure 5 shows changes in the magnetic saturation value (σs) and the Curie temperature depending on the P ₂ O ₅ content. _P2
When the O ₅ content is less than 20wt%, it is a crystalline substance, and P ₂
When the content of O ₅ is 20% by weight or more, it becomes an amorphous body.
As shown in the figure, σs rapidly decreases as the P ₂ O ₅ content increases, and an amorphous film is obtained when the content is 44 emu/g or less. With σs of this magnitude, there is a possibility of application as a magneto-optical material. Furthermore, the Curie temperature (Tc) tends to decrease as the P ₂ O ₅ content increases. This is presumed to be due to P ₂ O ₅ being involved in the Fe-O-Fe superexchange interaction. The crystallization temperature also shows a tendency to gradually decrease from about 300°C to about 250°C as the P ₂ O ₅ content increases.

FIG. 6 shows the wavelength dependence of normal force-rotation angle (2θk) for six types of samples with different P ₂ O ₅ contents. In the figure, a, b, c, e, d, f are a,
It corresponds to b,...f. a, which is a crystalline substance;
The spectrum of b and c gradually changes from a simple type to a more complex type. c is in an intermediate state between an oxide and a crystalline state. d, e, and f are amorphous bodies, and the peaks corresponding to each wavelength shift toward shorter wavelengths as the P ion content increases. This is thought to be due to the amount of P ions present, but the details are not yet clear. e has a large σ _s of 44emu/g,
2θk also shows a large value of ±21min. f is performed σ _s
also becomes smaller, and the change in 2θk with respect to wavelength is also drastic. To summarize the above, the role of P ions is extremely important in amorphous amorphous oxide thin films, and as the content of P ions increases, σ _s ,
Tcrys and Tc both decrease, but 2θk increases, and the peak tends to shift toward shorter wavelengths.

Example 4 Purpose Following the production of an Fe-P-based amorphous oxide thin film, part of it was replaced with Ni ions.
A Ni-Fe-P amorphous oxide thin film was produced. The reason for replacing Fe ions with Ni ions is
This is because the valence of Ni ions is stable and preferentially occupies regular octahedral coordination, so it is thought that a clear change occurs. This research is based on Ni−
The magnetic and magneto-optical properties of Fe-P-based amorphous oxide thin films were investigated.

Experimental method Nix Fe ₃ −x (x=0, 0.25, 0.5,
0.75, 1.0) and _P2
O ₅ and two evaporation sources (tungsten boat)
After reducing the pressure inside the bell jar to 1×10 ^-5 torr, the boat on the metal side (evaporation source A) was heated to about 1,700 torr.
After adjusting the temperature to ~1750°C and reducing the degree of vacuum to 10 ^-3 torr, a thin film was formed on the glass substrate while controlling the heating temperature of the evaporation source. The P ion content in the thin film can be adjusted by the heating temperature of the evaporation source on the P ₂ O ₅ side. When producing a thick film, repeated vapor deposition is performed.

Experimental Results First, we investigated changes in the crystal phase, magnetic saturation value (σ _s ), and electrical resistivity of thin films made from NiFe ₂ (x=0.5) alloy and P ₂ O ₅ with different P ion contents. As the P ion content in the thin film increases, σ _s
decreased and electrical resistivity increased. That is,
The oxidative nature becomes stronger with increasing P ion content. Figure 7 shows the wavelength dependence of normal force-rotation angle (2θk) for samples with different σs. a(σ _s =
150emu/g), b (σ _s =85), and c (σ _s =57) are crystalline, and d (σ _s =32) is amorphous. These spectra show changes similar to those of Fe--P based amorphous oxide thin films. It was also confirmed that the manufacturing conditions could be the same.

Example 5 Fe and Mn mixed powder and phosphorus pentoxide (P ₂ O ₅ ) powder were placed in two tungsten boats, and 1
After reducing the pressure inside the bell gear to ×10 ^-5 torr, adjust the metal side boat (A evaporation source) to approximately 1700 to 1750°C, and PO in an atmosphere with the degree of vacuum reduced to 3 × 10 ^-3 torr. ₂ was deposited on a slide substrate to obtain a thin film. It was confirmed using an X-ray diffraction apparatus that the produced thin film became amorphous when P ₂ O ₅ was 20% by weight or more. When the magnetic properties were measured using a vibrating sample magnetometer,
It showed a relatively high value of 45 emu/g. The magnetic characteristic of this amorphous oxide thin film is that it has a small coercive force of 20 oersteds. The reason for this is that the magnetocrystalline anisotropy is reduced by making the manganese ferrite, which originally exhibits soft magnetism, further amorphous. Therefore, this amorphous film is useful as a soft magnetic material.

Example 6 Put Fe and Cu powder into one tungsten boat, reduce the pressure inside the bell gear to 1×10 ^-5 torr, and then reduce the pressure of the metal side boat (A evaporation source) to about 1700 to 1750 torr.
℃ and the other tungsten boat has P ₂
After adding O ₅ and reducing the vacuum to 10 ^-3 torr, the boat was heated at the same time to co-evaporate Fe and P ₂ O ₅ ,
Amorphous oxide thin films were fabricated by vapor phase reaction on glass metal. There is a large difference in the evaporation start temperature of Fe and Cu, and in order to match the evaporation start temperature of Cu with that of Fe, a small piece of tungsten was placed in a part of the tungsten boat, and Cu was placed on top of it.
This amorphous oxide thin film became amorphous even when the P ₂ O ₅ content was small, and the content was 20% by weight or more. Because the magnetic moment of Cu ions is small,
The magnetic subtraction value of the obtained amorphous oxide thin film is 25~
It was 30 emu/g.

Example 7 Mg and Fe mixed powder and P ₂ O ₅ were placed in two tungsten boats, and after reducing the pressure inside the bell jar to 1×10 ^-5 torr, the metal side boat (A evaporation source) was heated to about 1700 ~ After adjusting the temperature to 1750° C. and reducing the degree of vacuum to 10 ⁻³ torr, the mixture was simultaneously heated to evaporate to form a thin film on the slide glass substrate by a gas phase reaction. Since Mg ions are difficult to form a solid solution, 20% by weight of P ₂ O ₅ was required to make the material amorphous. The magnetization value of the obtained amorphous oxide thin film is
It was small at 20 emu/g and had a coercive force of 350 oersted, exhibiting semi-hard magnetism.

FIG. 8 shows the wavelength dependence of 2θk of a (Nix Fe ₃ -x)-P-based amorphous oxide thin film. Sample O,
P, Q, R, S are x=0, 0.25, 0.75, respectively.
Compatible with 1.0. A characteristic feature is that as the Ni ion content increases, the positive and negative peaks shift toward longer wavelengths. In addition, the spectrum changes significantly between 250 nm and 350 nm as the amount of Ni ion substitution changes, but in the spectrum of single crystal Ni ferrite reported by Kahn et al., no transition of Ni ⁺² ions in this vicinity was reported, and there is no It may be unique to crystalloids. In addition, compared to the spectra of Ni, Co, and Mg ferrites reported by other authors, this amorphous thin film shows a remarkable change in the curve, especially between 250 and 600 nm, which is due to the influence of P ions. considered to be a thing. This can also be inferred from the fact that the spectrum of the crystallized sample is extremely flat over this wavelength range. To summarize the above results, the 2θk spectrum of an amorphous amorphous oxide thin film in which Fe ions are replaced with Ni ions tends to shift toward higher wavelengths.

The 2θk spectrum of this thin film is that of single crystal Ni,
It is different from those of Co, Mg ferrite, etc., and this difference is thought to be due to the influence of P ions.

(Effects of the Invention) As described above, the amorphous ferromagnetic oxide thin film of the present invention and its manufacturing method are a completely new magnetic thin film and a new manufacturing method. Furthermore, the magnetic and magneto-optical properties of the thin film are novel and superior to those of conventionally known oxide thin films, making the present invention extremely useful industrially.

[Brief explanation of the drawing]

Figure 1: A diagram showing an example of the amorphous amorphous oxide thin film manufacturing apparatus used in the experiments of the present invention; Figure 2:
Figure 3 is a characteristic diagram showing the relationship between the content of phosphorus pentoxide in the amorphous ferromagnetic oxide thin film of the present invention prepared from NiFe ₂ alloy powder and phosphorus pentoxide and the magnetic saturation value at room temperature. Figure 4 is a characteristic diagram showing the wavelength dependence of normal force-rotation angle (2θk) of various thin films with different phosphorus pentoxide contents shown in Figure 2.
A characteristic diagram showing the wavelength dependence of normal force-rotation angle when an amorphous ferromagnetic oxide thin film made from NiFe ₂ alloy powder and phosphorus pentoxide is heated.
A characteristic diagram showing changes in magnetic saturation value and Curie temperature depending on the phosphorus content of an amorphous ferromagnetic oxide thin film prepared using P ₂ O ₅ as an evaporation source.
Figure 7 is a characteristic diagram showing the dependence of normal force on the rotation angle of a P-based amorphous aqueous oxide thin film, and Figure 8 is a characteristic diagram showing the wavelength dependence of the normal force on the rotation angle of NiFe ₂ -P-based amorphous aqueous oxide. is a characteristic diagram showing the wavelength dependence of normal force-rotation angle of a Nix-Fe _(1-X) -P amorphous oxide thin film. 1... Alloy sample, 2... Oxide sample, 3... Tungsten board, 4... Support column, 5... Insulator, 6... Base plate, 7... AC power supply, 8
...Transformer, 9...Ammeter, 10...Exhaust system,
11... Shielding plate, 12... Rotating shaft, 13... Glass substrate, 14... Produced amorphous thin film, 15...
Bergiyah.

Claims (1)

[Claims] 1 48 to 36% by weight of ferric oxide (Fe ₂ O ₃ ), ferrous oxide (FeO), nickel oxide (NiO), manganese oxide (MnO), copper oxide (CuO), It contains 32 to 16% by weight of one or more oxides selected from magnesium oxide (MgO), and the balance is 20 to 48% by weight of phosphorus pentoxide (P ₂ O ₅ ). An amorphous ferromagnetic oxide thin film having a saturation value of 60 to 20 emu/g. 2 Part of the composition range of phosphorus pentoxide mentioned above10
A patent characterized in that less than % by weight is replaced with one or more oxides selected from arsenic trioxide (As ₂ O ₃ ), selenium oxide (SeO ₂ ), and tellurium oxide (TeO ₂ ). An amorphous ferromagnetic oxide thin film according to claim 1. 3 One or more metals among iron, nickel, copper, manganese, and magnesium are used as A evaporation source, and phosphorus pentoxide or a part thereof is used as arsenic trioxide,
An oxide substituted with one or more selected from selenium oxide and tellurium oxide is used as the B evaporation source, and after reducing the initial degree of vacuum to 5 × 10 ^-5 torr or less, the A evaporation source is used. The metal and oxide are simultaneously evaporated by maintaining the degree of vacuum in the range of 1 to 10 × 10 ^-3 torr while varying the temperature range of 1700°C to 2000°C and the B evaporation source in the range of 300°C to 700°C, and A method for producing an amorphous ferromagnetic oxide thin film, the method comprising forming an amorphous ferromagnetic oxide thin film by vapor deposition on a substrate. 4 48 to 36% by weight of ferric oxide (Fe ₂ O ₃ ), ferrous oxide (FeO), nickel oxide (NiO), manganese oxide (MnO), copper oxide (CuO), magnesium oxide (MgO) An amorphous ferromagnetic oxide thin film containing 32 to 16% by weight of one or more oxides selected from the above, and the balance being 20 to 48% by weight of phosphorus pentoxide (P ₂ O ₅ ). 4. The method for producing an amorphous ferromagnetic oxide thin film according to claim 3, wherein the normal force-rotation angle is improved to 0.6 degrees or more by heating the amorphous ferromagnetic oxide thin film below the crystallization temperature. 5 The amorphous oxide thin film contains 10% by weight or less of a part of the composition range of phosphorus pentoxide such as arsenic trioxide (As ₂ O ₃ ), selenium oxide (SeO ₂ ), and tellurium oxide (TeO ₂ ). 4. The method for producing an amorphous ferromagnetic oxide thin film according to claim 3, which is substituted with one or more oxides selected from the following.