JPH0234536A - Amorphous material - Google Patents

Abstract

PURPOSE:To obtain the title amorphous material having excellent corrosion resistance, etc., with good productivity by incorporating a (semi)metal, the carbide and/or silicide of a (semi)metal, and amorphous carbon and/or amorphous silicon into the material. CONSTITUTION:A container 1 contg. a metal (e.g., iron) or a semimetal and a container 2 contg. a polymer (e.g., PE) are arranged in the vacuum vessel 6 of a vacuum deposition device. The metal or semimetal and the polymer are then simultaneously vacuum-deposited to form a vapor-deposited film of a (semi)metal-polymer alloy on a substrate 3. By this method, an amorphous material contg. at least one kind of component selected from a metal and/or a semimetal, a metal carbide, a metal silicide, a semimetal carbide, and a semimetal silicide and amorphous carbon and/or amorphous silicon and useful as magnetic film material, etc., is produced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to amorphous materials. More particularly, the present invention relates to novel amorphous materials made from metals or metalloids and polymers.

[Prior Art] The existence of so-called amorphous metals in which the arrangement of atoms is irregular is well known.

Most metals have crystalline structures in which atoms are arranged in an orderly manner, but when melted at high temperatures, the atomic arrangement of any metal breaks down and it becomes amorphous. When it is cooled for 30 minutes, it returns to its original crystalline structure, but when some metals are rapidly cooled, they remain amorphous and solidify. This is an amorphous metal.

This amorphous metal is currently being applied in various fields. For example, amorphous Si films are used as solar cells. In addition, amorphous Fe5iB soft magnetic films are being developed as magnetic cores for power transformers, and Go-Zr amorphous soft magnetic films are being developed as magnetic film materials for magnetic heads for magnetic recording. used in the department.

[Problems to be Solved by the Invention] Since it is difficult for an amorphous metal film to become amorphous if it is a single metal, it is difficult to make it amorphous if it is a single metal. Obtained by mixing and rapidly cooling. The characteristics of the obtained metal amorphous film were determined by the added metalloid element or Zrs.
It varies greatly depending on the concentration of metals such as Ta1Hf.

These alloys have improved corrosion resistance and mechanical strength compared to crystalline metals, but like the Co-Cr magnetic material, they do not contain the metalloid elements mentioned above or amorphous materials such as Z r + Ta * Hf. Even if mixed with
In some cases, sufficiently satisfactory corrosion resistance cannot be obtained.

In particular, the corrosion resistance of Fe-C based amorphous materials is poor. Corrosion resistance is improved by adding % P + Mo + Cr as a third element. However, there is a problem in that the addition of these third elements reduces the saturation magnetic flux density.

The purpose of the present invention is to solve the various drawbacks of conventional amorphous films as described above, and to provide a new amorphous material with excellent mass productivity and corrosion resistance.

[Means for Solving the Problems] As a means for achieving the above object, the present invention provides a method for simultaneously depositing a metal and/or metalloid and a polymer on paper at a predetermined vapor deposition rate ratio from separate crucibles or hearths. By depositing, at least (
a) a metal and/or a metalloid; and (b) at least one component selected from the group consisting of a metal carbide, a metal silicide, a metal carbide, and a metalloid silicide, and (c) amorphous carbon and/or amorphous silicon; and/or (
d) A novel amorphous material containing a hydrocarbon compound and/or an organosilicon compound is provided.

In particular, when measuring the Mössbauer effect of an amorphous material in which the metal is iron or an iron alloy, the main absorption peaks are 2 or 3, and this iron-based amorphous material exhibits soft magnetism and corrosion resistance. Excellent in

In the Mössbauer spectrum of an iron-based amorphous material, if there are two main absorption peaks, the absorption peaks are mainly located at -3 to -1 mm/see and 1 to 3 am/see from the center of gravity of the absorption spectrum. In the case of 3 trees, -3 to -1m/sec+-1 to 1-
s/sec, one main peak appears at 1 to 3 am/sec, and the center of gravity of the spectrum is located at 11 am/sec.
It was found that those having a corrosion rate of ~lIl/sec are excellent in corrosion resistance.

In the Mössbauer spectrum of iron-based amorphous materials, 2
In addition to three to three large absorption peaks, α-Fe and Fe3C peaks may be observed as secondary peaks.

[Function] The exact mechanism by which the iron-based amorphous film obtained by simultaneously vapor-depositing Fe or Fe alloy and polymer has particularly excellent corrosion resistance has not yet been elucidated and is only a matter of speculation. is covalently bonded with a carbon atom (c) derived from a polymer to form a Fe-C based compound, and between this Fe-C based compound or between iron atoms, amorphous carbon or amorphous silicon derived from the polymer is formed. and the original polymer and/or
Alternatively, it is considered that hydrocarbon compounds or organic silicon compounds produced by cutting or splitting the polymer are mixed together in a harmonious manner. Whether it is carbon-based or silicon-based is determined by the polymer used. Hydrocarbon compounds are probably -(cH2)n- (where 1≦n:
It seems to contain a chain of alooo). Further, it is thought that specific side chains are included depending on the polymer used.

It is thought that in the conventional iron-carbon (pellet) based amorphous film produced by sputtering, carbon atoms are randomly inserted between Fe atoms. This assumption is based on conventional iron-
This is confirmed by measuring the same Mössbauer effect as described above for a carbon (pellet)-based amorphous film. A conventional amorphous film made from iron and pelletized carbon by a sputtering method has four to six main absorption peaks and exhibits a Mössbauer spectrum that is different from the spectrum obtained from the present invention.

Furthermore, in the present invention, the spectra of Fe--C and pure iron may be mixed to some extent in the spectrum due to non-uniform composition, but this does not affect the corrosion resistance much. Furthermore, each of the two to three spectra in the spectrum described in the present invention may be split into two with a width of about 0.5 + n/see. This is due to the four-electrode electric field in the film, and this also does not affect the corrosion resistance much.

The exact mechanism by which an amorphous material is produced when a metal or semimetal and a polymer are simultaneously paper-deposited has not yet been elucidated and is therefore a matter of speculation; however, in the amorphous material of the present invention, , the polymer is distributed at very close distances in the metal or metalloid, and the carbon or silicon in the polymer and the metal or metalloid form a carbide or silicide, and the relationship between the carbide, silicide, metal, and metalloid. The presence of amorphous carbon, amorphous silicon, a hydrocarbon compound, an organic silicon compound, or a part or both of them inhibits the crystallization of the metal or semimetal, causing it to become amorphous. It seems to be. At this time, whether it is a carbide or a silicone is determined by the polymer used.

In the case of columnar metal particles, the outer surface of the particle may be coated with a polymer, but within each metal column, the crystallization of the metal or metalloid is inhibited by the above mechanism, and it becomes amorphous. It will be done.

The situation seems to be roughly the same in the case of granular metals.

Japanese Patent Publication No. 57-3137 discloses a method for manufacturing a magnetic recording medium in which a magnetic recording layer is formed by simultaneously depositing a ferromagnetic material and a polymer on a support by a vapor deposition method.

However, the purpose of this invention is to eliminate the drawbacks of conventional non-binder type ferromagnetic metal thin films, such as the generation of sawtooth magnetization transition regions, noise generation due to eddy currents, and decrease in recorded magnetization. .

According to the present invention, since the ferromagnetic particles are embedded in the polymer and dispersed appropriately, they behave like single-domain particles, improving magnetic properties, and solving the conventional drawbacks.

Therefore, the polymer in this invention merely functions as an insulating material, and does not form an amorphous material as in the present invention.

According to the simultaneous vapor deposition method disclosed in the above-mentioned publication, a magnetic layer is formed in which metal layers and polymer layers are alternately laminated, and the polymers in the metal are relatively uniformly spaced very close to each other as in the present invention. It is not possible to create a cane state that is distributed in

In any case, an amorphous material containing a polymer in a metal or metalloid has not been disclosed in any known literature and is new.

In this specification, the term "amorphous material" is used to refer to completely amorphous materials as well as materials containing some crystalline parts in the amorphous state and X-ray This is to include materials that are aggregates of microcrystals that cannot be detected by diffraction.

In fact, it could not have occurred to any person skilled in the art that a polymer would render a metal or metalloid amorphous until the present invention was completed. Even if a metal or metalloid is vacuum-deposited alone without using a polymer, the metal or metalloid rarely becomes amorphous.

Quite unexpectedly, the amorphous nature of the films formed by co-depositing metals or metalloids with polymers in accordance with the present invention, compared to conventional films obtained by vacuum-depositing metals or metalloids alone. It has been discovered that the membrane is significantly superior in terms of corrosion resistance and mechanical durability. The exact reason or mechanism by which the corrosion resistance and mechanical durability of a film are improved by making it amorphous by combining polymers has not yet been elucidated.

The iron-based amorphous film of the present invention is particularly desirable as a head material having a high saturation magnetic flux density that allows sufficient recording on high coercive force media.

Although the amorphous material of the present invention can be formed as a film on a substrate, it can be scraped off from the substrate to form a powder.
It can also be used in combination with liquid or solid materials such as suitable vehicles and binders. If you do this, you can apply it at the desired time and place.

Molded articles of various shapes can be manufactured by any means such as spraying or molding.

Therefore, the novel amorphous material of the present invention can be used not only as a magnetic material, a solar cell, and a power transformer core, but also as a metal for hydrogen absorption and desorption. By amorphizing the metal that absorbs and removes hydrogen according to the present invention, a power storage system (i.e., a system that creates hydrogen using surplus electricity, stores it in the metal that absorbs and desorbs hydrogen, and extracts the hydrogen when necessary and converts it into electricity) can be created. It is also possible to construct a highly efficient power source that utilizes changes in hydrogen pressure, or an efficient thermal storage system that utilizes the radiation and absorption of heat during hydrogen adsorption and desorption.

The amorphous material of the present invention can be used for other applications other than those described above (e.g., amorphous devices, solid-state imaging devices, etc.), or can be used in various applications in which it is preferable to use an amorphous material in the film. It can also be used for other applications (such as superconducting materials).

As described above, according to the present invention, many metals or metalloids can be made amorphous very easily simply by simultaneously depositing metals or metalloids and polymers using a paper deposition method.

"Paper deposition method" means a method in which a substance or compound to be deposited is deposited on a gas as vapor or ionized vapor in a gas or vacuum space. This method includes a vacuum M deposition method, an ion blating method, a high frequency ion brating method, an ion cluster beam method, an ion beam deposition method, a sputtering method, a CVD method, and the like.

Therefore, the method for manufacturing an amorphous material of the present invention is simpler in structure than any of the conventional methods described above, the apparatus itself is extremely simple, and it is easy to implement and operate.

Metals that can be used to form the amorphous materials of the invention include, for example, metals classified as metallic elements in the periodic table.
They are elements of periods 2.3, 4.5 and 6. These can be used in the form of single alloys or compounds.

Metalloids that can be used to form the amorphous materials of the present invention include specifically A S+ S el S bt S r +
They are GetSn, Te, and Bi. These are also lli body 1
It can be used in the form of alloys or compounds. If desired, it can be used in combination with the above metals.

Polymers that can be used to form the amorphous materials of the invention have carbon atoms of 10 to 1000, preferably 30 to 500.
, preferably a linear or network polymer with a molecular weight in the range of 70 to 200. Specifically, polyethylene, polyethylene terephthalate, polypropylene, polystyrene, polytetrafluoroethylene, polybutadiene, polycarbonate, polyamide, polyimide, polyurethane,
Examples include polyvinyl chloride, polyvinyl acetate, and silicone polymers. The polymer has gold 1 on the side chain of the alkyl chain.
1. It can also have other functional groups such as OH, halogen, and alkyl. Moreover, the polymer can also be introduced after being gasified.

The mixing ratio of the metal or metalloid and the polymer is - 5 volX or more of polymer in the membrane, preferably 10 vol.
% or more, more preferably 12VO1% or more, 40vo
The amount is 1% or less. If the polymer content is less than 5 vol%, the metal or metalloid cannot be made amorphous. Further, if the amount of polymer exceeds 4Qvo1%, separation of metal or metalloid particles by the polymer becomes large, and the magnetic properties gradually become hard, which is not preferable.

[Embodiments] Hereinafter, embodiments of the present invention will be described in more detail with reference to the drawings.

An iron-based amorphous film was produced by simultaneously vacuum-depositing iron and polyethylene under the conditions shown below using a batch-type vacuum deposition apparatus as shown in FIG.

(1) Vapor deposition material: iron, polyethylene (average molecular weight (2)
Vapor deposition method and deposition rate Iron (electron gun heating) 20 people/see Polyethylene (resistance heating) 5 people/5ee (3) Substrate glass (4) Substrate temperature: 150°C (5) Vacuum degree: 1.0XIO-5Torr (G ) Film thickness: 1.6 μm The Fe-polyethylene co-deposited film obtained as described above was analyzed by XPS. Carbon in the Fe-polyethylene co-deposited film is (1) Fe-C, (11) Amo/L/7
y carbon and (111)-(cH2)
It existed as n-, and the respective constituent ratios were 72.6:18.8:8.8 in terms of carbon number ratio. From this analysis result, Fe and C in the Fe-polyethylene co-deposited film
It is thought that most of them are combined to form Fe-C compounds.

The Mössbauer spectrum of this Fe-polyethylene co-deposited film was observed. The results are shown in FIG.

From this spectrum, the absorption peaks are main peak 1 located at -3 to -1 mm/see, main peak 2 located at -1 to 1 mm/see, and main peak 2 located at 1 to 3 A main peak 3, a sub-peak 4 and a sub-peak 5 are observed at /sec, and the presence of these peaks 1 and 3 indicates that this Fe-polyethylene co-deposited film has magnetism, and the peaks 4 and 5 indicate that α -Fe or F
Indicates that it contains e3C.

Note that the "center of gravity position" used here refers to a speed at which the Mössbauer spectrum is approximately symmetrical about a straight line drawn at a certain speed.

Using an RF sputtering apparatus as shown in FIG. 8, an Fe-c sputtered film was produced under the conditions shown below.

1u1 (1) Target: Fe5G target (2) Ar gas pressure: l OwTorr (3) Substrate glass (4) Substrate temperature two to room temperature (5) Film thickness: 1.5 μm Obtained in Example 1 and Comparative Example 1 When the crystallinity of the samples was examined by X-ray diffraction, both showed only a halo pattern.
It was confirmed that it was amorphous.

When XPS analysis of this Fe-C sputtered film was performed,
Carbon in the film was present only as Fe-C.

The saturation magnetic flux density (Bs), coercive force (Hc), and anisotropic magnetic field (I
ik) was measured. The results are summarized in Table 1 below.

As is clear from the above results, the Fe-polyethylene co-deposited film of the present invention is a soft magnetic film like the conventional Fe-C sputtered film.

FIG. 10 shows the Mössbauer spectrum of the Fe--C sputtered film produced in the comparative example.

As is clear from a comparison between FIG. 9, which is the Mössbauer spectrum of the Fe-polyethylene co-deposited film of the present invention, and this FIG. .2.3, whereas the Mössbauer spectrum of the Fe-C sputtered film of the comparative example has the symbols (a), (b), and (
c), (d).

It has six main peaks: (ne) and (e). It is understood from this fact that the deposited film of the present invention has a structure different from that of conventional iron-based amorphous films.

The samples obtained in Example 1 and Comparative Example 1 were subjected to high temperature and high humidity (
The rate of change in saturation magnetization (No-M/No; Mo = initial saturation magnetization,
Corrosion resistance was compared by measuring M=saturation magnetization after standing. The measurement results are shown in FIG.

From the results shown in FIG. 9 and FIG. 11, the Fe-polyethylene co-deposited film of the present invention, which has three main peaks in the Mössbauer spectrum, has a structural upper limit with that of the conventional Fe-C sputtered film, and has good corrosion resistance. This is considered to be an indication.

F e @Aλ and polypropylene were simultaneously vacuum-deposited under the conditions shown below to produce an iron-based amorphous film using a batch-type vacuum evaporation apparatus as shown in FIG.

(1) Vapor deposition substance: Fe3AJ *Polypropylene (average molecular weight: 500) (2) Vapor deposition method and vapor deposition rate Fe-AJ! (Electron gun heating) 20 people/sec Polypropylene (resistance heating) 5A/5ec (3) Substrate glass (4) Substrate temperature: 150°C (5) Vacuum degree: 1.0XIO-5Torr (8) Film thickness:
1.5 μm The FeAJ-polypropylene co-deposited film obtained as described above was subjected to XPS analysis. Carbon in the FeAλ-polypropylene co-deposited film is (1) FeAJt -C,
(++) Exists as amorphous carbon, and the composition ratio of each is 71.5:28 in terms of carbon number ratio.
It was 5.

Further, in the Mössbauer spectrum of this FeAJ-polypropylene co-deposited film, only two peaks 1 and 3 among the main peaks shown in the Mössbauer spectrum of the Fe-polyethylene co-deposited film obtained in Example 1 were observed.

Chigoko 1 Using a continuous evaporation apparatus as shown in FIG. 5, an amorphous thin film was produced by simultaneous vacuum evaporation of metal and polymer under the conditions shown below.

1. Metal 200 2. Polymer: polyethylene (average molecular weight: 500) 3. Substrate: polyimide film (film thickness 50 μm) 4. Substrate temperature: 100°C 5. Vapor deposition rate: Co 500 people/sec
Polymer 150 people/5ee 6, degree of vacuum: 2.0xlO-5 Torr Metals were vacuum deposited by heating with an electron gun, and organic polymers were vacuum deposited by resistance heating. The thickness of the deposited film was 10 μm. A 100 m long polyimide film was used, and an amorphous film was deposited over the entire length of the film. A 100 m film sample with an amorphous membrane made of CO-polyethylene was prepared.

In order to investigate whether the long co-deposited thin film made of Co-polyethylene was amorphous,
Samples were cut out at intervals to obtain 100 specimens for each membrane. When all of these 100 specimens were examined by X-ray diffraction, the diffraction angle 2θ = 20 for all specimens.
It was found that no peak was observed in the range of 100° to 100°, indicating that the film had become amorphous.

In addition, XPS analysis was performed on 100 samples subjected to X-ray diffraction, and it was found that carbon in this Co-polyethylene co-deposited film exists as (1) Co C-(Ii) amorphous carbon; The ratio is 74.0:2B in terms of carbon number ratio.

It was 0.

We also investigated the magnetic properties of the film using the same sample. The measurement method was almost the same as that described in Example 1.

The measurement results are summarized in Table 2 below.

The value labeled ``%'' is the average value of the measured values obtained for 100 specimens.

As is clear from the above results, the Co-polyethylene amorphous film according to the present invention exhibits soft magnetic properties. This characteristic is ±5% for Bs and ±20% for He over a length of 100m.
% and Hk are extremely stable at ±15%.

In addition, the h limit of the vapor deposition rate in the co-polyethylene system is
It is preferable that the polyethylene deposition rate/CO deposition rate≦0.4. If it exceeds 0.4, the separation of Co particles due to polyethylene becomes large, and the magnetic properties gradually become hard, resulting in an unfavorable result.

As described above, by the simultaneous vacuum deposition method of ferromagnetic metal and organic polymer of the present invention, an amorphous soft magnetic thin film can be produced with almost 100% probability at a high deposition rate that cannot be obtained by conventional sputtering method. was gotten.

An amorphous film was produced by simultaneous vacuum deposition of Co*Cr and polyethylene under the conditions shown below using a batch type vacuum deposition apparatus as shown in FIG.

■, Gold metal: CoCr 2, Polymer: polyethylene (average molecular weight: 20.0O) 3, Substrate: polyimide film (film thickness 50 μm) 4, Substrate temperature: 150°C 5, Vapor deposition rate: Co*Cr 15 people/sec polyethylene 4.5 people/5ee 6. Degree of vacuum: 1 to 2xlO-5TorrCO.Cr was deposited by electron gun heating, and polyethylene was vacuum deposited by resistance heating. The thickness of the deposited film was 0.16 μm. The degree of Cr relative to Co in the obtained deposited film was 18vt%.
Met.

For comparison, a single CoCr film was also produced under the same conditions. (
However, the degree of vacuum was set at 1 to 2×10 −8 Torr. ) In order to investigate whether the CoCr-polyethylene co-deposited film of the present invention obtained as described above is amorphous, X-ray and electron diffraction were carried out, and it was found that 2θ = 20° in X-ray diffraction. No peak was observed in the range of ~100°, and electron beam diffraction revealed only two halo rings, indicating that the material was amorphous.

On the other hand, in the CoCr single film, 2θ=44.2' hcl)
There is a sharp peak due to the (002) plane of the structure, and in electron beam diffraction, a diffraction pattern is obtained due to the hcp structure,
It was found that CoCr alone is crystalline.

The electron beam diffraction images of the CoCr-polyethylene co-deposited film of Example 4 and the CoCr single film of the control example are shown in Figure 2 (a) and (
Shown in b). As is clear from these figures, Example 4
The CoCr-polyethylene co-deposited film is amorphous, but the C0Cr single film of the control example remains crystalline.

The magnetic properties of the CoCr-polyethylene co-deposited film of Example 4 and the CoCrli body film of the control example were measured by the same method as described in Example 1. The measurement results are shown in Table 3 below.

In Table 1, the values for the CoCr-polyethylene co-deposited film are measured values in the plane of the substrate surface, and the values for the CoCr film are measured values in the direction perpendicular to the substrate surface.

As is clear from the results shown in Table 3, C of Example 4
The oCr-polyethylene co-deposited film has soft magnetic properties.

Next, this CoCr-polyethylene co-deposited film was subjected to XPS analysis. The carbon in this CoCr-polyethylene co-deposited film is (1) CoCr-C, (th)-(cH2)n-
, and the composition ratio of each is converted into carbon number ratio? 3,2:2B,8.

Furthermore, the corrosion resistance and mechanical durability of the CoCr-polyethylene co-deposited film of Example 4 and the CoCr single film of the control example were measured.

The CoCr-polyethylene co-deposited film of Example 4 and the CoCr single film of the control example were left for 10 days in a high temperature and high humidity atmosphere of 60°C and 90% RH, and the deterioration rate of saturation magnetic flux density (Bs'
/Bso) to examine the corrosion resistance. Bs□
is the saturation magnetic flux density before exposure to a high temperature and high humidity atmosphere, and B s ' is the saturation magnetic flux density after exposure to a high temperature and high humidity atmosphere. The saturation magnetic flux density was measured using a sample vibrating magnetometer. The measurement results are summarized in Figure 3.

As is clear from this graph, control example C.

It is understood that the CoCr-polyethylene co-deposited film of Example 4 is hardly corroded even when exposed to a high temperature and high humidity atmosphere for a long period of time, and has excellent corrosion resistance, compared to a Cr single film.

A sample was cut into a 1 On+m x 50+ am strip and pasted on a slide glass, and a diamond needle (radius of curvature at the tip: 50 μmR) was used to reciprocate over the sample surface at a running speed of 0.14 m/sin with a load of 5 gf. Mechanical durability was measured by observing scratches generated on the sample surface using a microscope. Figure 4 summarizes the changes in the width of scratches on the sample surface depending on the number of runs.

As is clear from FIG. 4, the CoCr-polyethylene co-deposited film of Example 4 has a smaller scratch width and superior mechanical durability than the CoCr single film of the control example.

Mitsutane LIL In order to investigate how the degree of amorphousness of the CollCr-polyethylene co-evaporated M film and the magnetic properties of the film change when the deposition rate of polyethylene on Co*Cr is changed, CO・Cr Samples were prepared in which the ratio of the deposition rate of polyethylene to the deposition rate of polyethylene was varied from 0 to 0.19. The deposition conditions other than the deposition rate were almost the same as those used in Example 1. (The Cr degree with respect to co was 24 wt%.) The peak of the (002) plane in the X-ray diffraction of Co*Cr when the polyethylene deposition rate relative to the Co/Cr deposition rate was changed from O to 0.19. FIG. 6 shows the change in , and FIG. 7 shows the change in in-plane coercive force.

From these results, the ratio of the deposition rate of polyethylene to the deposition rate of Co@Cr is 0 from the point of view of magnetic properties.
．． 1 or more, and 0.0 from the crystal quality by X-ray diffraction
It is desirable that it is 5 or more.

X-ray diffraction and coercivity were investigated. Also, each C.

XPS analysis was performed on the Cr-polyethylene co-deposited film. Carbon in each CoCr-polyethylene co-deposited film is (1
)CoCr-C, (cH2)n-, and the composition ratio of each does not depend much on the deposition rate.
The carbon number ratio was approximately 73:27.

[Effects of the Invention] As explained above, according to the present invention, a useful amorphous material can be easily and extremely inexpensively mass-produced by co-evaporating a metal or metalloid and a polymer. Is possible.

In particular, since the iron-based amorphous film of the present invention has excellent corrosion resistance, it is particularly promising as a head material having a high saturation magnetic flux density that allows sufficient recording on high coercive force media.

The novel amorphous material of the present invention can be formed not only into a film but also into molded articles of various shapes, so it can be used for an extremely wide range of applications compared to conventional amorphous materials made only of metal. be able to.

Such an amorphous material can be obtained by a novel manufacturing method in which a metal or f-metal and a polymer are simultaneously vacuum-deposited at a predetermined deposition rate ratio.

Compared to various conventional methods for producing amorphous metals, the method of the present invention allows useful amorphous materials to be easily mass-produced at high yields and at extremely low cost.

[Brief explanation of the drawing]

FIGS. 1 and 5 are schematic diagrams showing examples of batch type and continuous vacuum evaporation equipment used for manufacturing the amorphous film of the present invention, and FIG. FIG. 2(b) is an electron diffraction photograph showing the crystal structure of the obtained amorphous film of the present invention, FIG. Figure 4 is a characteristic diagram showing the change in the deterioration rate of the saturation magnetic flux density with respect to the number of days of storage in a high temperature and high humidity atmosphere, and Figure 4 is a characteristic diagram showing the change in the width of the scratch that enters the sample surface depending on the number of times the diamond needle runs. Figure 6 is a characteristic diagram showing the change in the peak of the (002) plane by X-ray diffraction of Co-Cr when the polyethylene deposition rate relative to the Co*Cr deposition rate is varied from 0 to 0°19. , FIG. 7 is a characteristic diagram showing changes in in-plane coercive force, and FIG. 8 is a schematic diagram showing an example of an RF sputtering apparatus used for producing an Fe-C amorphous film. FIG. 9 is a characteristic diagram showing the Mössbauer spectrum of the iron-based amorphous film of the present invention obtained in Example 1;
Figure 0 is a characteristic diagram showing the Mossbauer spectrum of the Fe-C amorphous film obtained in Comparative Example 1, and Figure 11 is a characteristic diagram showing the Mossbauer spectrum of the Fe-C amorphous film obtained in Comparative Example 1.
FIG. 2 is a characteristic diagram showing the rate of change in saturation magnetization of the amorphous film obtained in Comparative Example 1 under high temperature and high humidity. ■ and 8...metal crucible, 2 and 9...polymer crucible, 3...substrate, 4...substrate holder, 5...
...Substrate heating heater, 6 and 15...Vacuum chamber. 7 and 16...Evacuation system, 10...Substrate film. 11... Can roll, 12... Delivery roll, 13
... Winding roll, 14... Mask, 21... Target. 22... Substrate, 23... Substrate side electrode, 24... High frequency power supply, 25... Blocking capacitor, 26...
... Valve, 27... Ar inlet, 28... Vacuum chamber, 29... Vacuum exhaust system

Claims (1)

[Scope of Claims] (1) At least: (a) a metal and/or a metalloid; (b) a metal carbide, a metal silicide, a metalloid carbide, and a metalloid silicide; An amorphous material characterized by containing at least one component; and (c) amorphous carbon and/or amorphous silicon. (2) The metal is selected from the group consisting of the elements of periods 2, 3, 4, 5 and 6 classified as metallic elements in the periodic table, and the metalloid is As, Se, Sb, Si.
, Ge, Te, Bi and Sn, and the metal or metalloid is used in the form of a single substance, an alloy or a compound, and the metal and metalloid can also be used in combination. Crystalline material. (3) The amorphous material according to claim 1 or 2, wherein the metal is iron or an iron alloy. (4) In the measurement of the Mössbauer effect, the absorption peak is -3 to -1 mm/se from the center of gravity of the absorption spectrum.
4. The amorphous material according to claim 3, wherein two main peaks appear, one each in the range of 1 to 3 mm/sec. (5) In the measurement of the Mössbauer effect, the absorption peak is -3 to -1 mm/se from the center of gravity of the absorption spectrum.
4. The amorphous material according to claim 3, wherein three main peaks appear, one each at -1 to 1 mm/sec and 1 to 3 mm/sec. (6) The amorphous material according to claim 3, characterized in that in addition to the two or three large absorption peaks, α-Fe and Fe_3C peaks appear as sub-peaks. (7) The amorphous material according to claim 3, wherein the center of gravity of the absorption spectrum is within the range of -1 to 1 mm/sec compared to the spectrum of α-Fe. (8) At least one component selected from the group consisting of (a) a metal and/or a metalloid; (b) a metal carbide, a metal silicide, a metalloid carbide, and a metalloid silicide; and (c) an amorphous material containing a hydrocarbon compound and/or an organic silicon compound. (3) The metal is selected from the group consisting of the elements of periods 2, 3, 4, 5 and 6 classified as metallic elements in the periodic table, and the metalloid is As, Se, Sb, Si.
, Ge, Te, Bi and Sn, and the metal or metalloid is used in the form of a single substance, an alloy or a compound, and the metal and metalloid can also be used together. Crystalline material. (10) Claim 8 or 9 wherein the metal is iron or an iron alloy.
The amorphous material described. (11) In the measurement of the Mössbauer effect, the absorption peak is -3 to -1 mm/s from the center of gravity of the absorption spectrum.
11. The amorphous material according to claim 10, wherein two main peaks, one each, appear in the range of ec, 1 to 3 mm/sec. (12) In the measurement of the Mössbauer effect, the absorption peak is -3 to -1 mm/s from the center of gravity of the absorption spectrum.
11. The amorphous material according to claim 10, wherein three main peaks appear, one each at ec, -1 to 1 mm/sec and 1 to 3 mm/sec. (13) The amorphous material according to claim 10, characterized in that, in addition to two or three large absorption peaks, α-Fe and Fe_3C peaks appear as sub-peaks. (14) The amorphous material according to claim 10, wherein the center of gravity of the absorption spectrum is within a range of -1 to 1 mm/sec compared to the spectrum of α-Fe. (15) At least one component selected from the group consisting of (a) metals and/or metalloids; (b) metal carbides, metal silicides, metalloid carbides, and metalloid silicides; (c) amorphous carbon and/or amorphous silicon; and (d) an amorphous material characterized by containing a hydrocarbon compound and/or an organic silicon compound. (16) The metal is selected from the group consisting of the elements of periods 2, 3, 4, 5 and 6 classified as metallic elements in the periodic table, and the metalloids are As, Se, Sb, S
16. The metal or semimetal is selected from the group consisting of i, Ge, Te, Bi, and Sn, and the metal or semimetal is used alone, in an alloy, or in the form of a compound, and the metal and semimetal can also be used together. Amorphous material. (17) The amorphous material according to claim 15 or 16, wherein the metal is iron or an iron alloy. (18) In the measurement of the Mössbauer effect, the absorption peak is -3 to -1 mm/s from the center of gravity of the absorption spectrum.
18. The amorphous material according to claim 17, wherein two main peaks, one each, appear in the range of ec, 1 to 3 mm/sec. (19) In the measurement of the Mössbauer effect, the absorption peak is -3 to -1 mm/s from the center of gravity of the absorption spectrum.
18. The amorphous material according to claim 17, wherein three main peaks appear, one each at ec, -1 to 1 mm/sec and 1 to 3 mm/sec. (20) The amorphous material according to claim 17, characterized in that, in addition to two or three large absorption peaks, α-Fe and Fe_3C peaks appear as sub-peaks. (21) The amorphous material according to claim 17, wherein the center of gravity of the absorption spectrum is within the range of -1 to 1 mm/sec compared to the spectrum of α-Fe.