JPS5827941A - Manufacture of amorphous thin film - Google Patents

Abstract

PURPOSE:To obtain an amorphous thin film with low coercive force and high initial permeability by sputtering or vapor-depositing an alloy consisting of a nonmetallic element and a rare earth element replaced partially by a metallic element such as Ti, Zr or Hf and the balance essentially transition metallic element. CONSTITUTION:An alloy expressed by a formula MaTbXcZd is prepared. In the formula M is >=1 kind of element selected from Fe, Ni and Co, T is >=1 kind of element selected from Mn, Cr, W, etc., X is >=1 kind of element selected from Zr, Ti, Y, etc., Z is >=1 kind of element selected from P, B, C, etc., a+b+c+d= 100, 0<=b<=95, 30<=a+b<=95, 0<=c<=70and 0<=d<=30. The alloy is sputtered or vapor-deposited to manufacture an amorphous thin film. This film is different from a conventional amorphous thin film in alloy composition and has high thermal stability. when the film is magnetized, it shows superior magnetic characteristics, that is, low coercive force and high permeability.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on metal elements such as Zr, Ti, and T-1f that exhibit high thermal stability and are produced by sputter deposition.

This invention relates to an amorphous thin film with an alloy composition consisting essentially of transition metals and non-metallic elements and with low magnetostriction. More specifically, the thin film is sputter-deposited in a rotating magnetic field, and the sputter-deposited film is deposited at the temperature of the thin film.

Heat treatment below the crystallization temperature or rotating magnetic field.

Low coercive force and high initial permeability due to heat treatment inside.

The present invention provides a highly amorphous thin film.

By sputter depositing 11 certain metals or alloys, it is possible to obtain an amorphous structure with no long-range order in the atomic structure. Conventional amorphous thin films obtained by this method are mainly metal-nonmetal alloys based on nonmetallic elements such as 13, C, and Si, and rare earth alloys useful for bubble magnetic materials and magneto-optical magnetic materials. It consists of an alloy system based on elements. But this.

Their amorphous alloy system has excellent mechanical, magnetic, and electrical properties.

Thermal stability, which causes deterioration, is still insufficient for practical use.

I can't say that. Further 13. Based on nonmetallic elements such as C and Si.

Metal-nonmetallic alloys are sputter-deposited, especially in conductors, and have high coercivity and low permeability due to their magnetic anisotropy.

This is a practical problem.

In order to solve the above-mentioned problems, the present invention replaces at least -11) parts of the non-metallic elements and rare earth elements that are constituent elements of conventional amorphous alloy systems with Ti.
, Zr, Hf, Y, Ge, sb, B15Te
etc.

Replaced with metal elements, others are mainly transition metal elements.

The main component is P, 13, C, Si, as necessary.

By adding small amounts of elements such as N, span.

The aim is to improve thermal stability as well as to facilitate the production of amorphous alloy thin films by evening evaporation.

Furthermore, in metal-nonmetal alloys, ferromagnetic elements Fe, Ni,
Adjust the values of magnetostriction and saturation magnetization with Co, and adjust the values of V, Cr, Mn,
By adding small amounts of Nb, Mo, W, and rare earth elements to improve the crystallization temperature and hardness, the magnetostriction is small and the thermal stability and wear resistance are improved. Additionally, amorphous thin films exhibit ferromagnetism.

In the case of sputter deposition in a rotating magnetic field, or

After obtaining the amorphous magnetic thin film by sputter deposition.

By heat-treating the film at temperatures above its Giel temperature and below its crystallization temperature, a magnetic thin film with small magnetic anisotropy, low coercive force, and high magnetic permeability can be obtained.

It was made by sea urchin.

Hereinafter, the present invention will be explained in detail with reference to Examples.・Example 1. The alloy composition is C0TIZrCoZr1Co8o.

79 13 8 paper 8416 T113FeZr1Co81Mo78m2Zr1o (C
oo, 3゜18 2 % 90 10 Fe o, 7) 90 T I 2 Z r a, P
The mother alloy of e so N I i o Z r 1o is a.

- Produced by melting, diameter 5Qmm, thickness approximately 1mm
A target was created. Thin film production was performed using a two-pole height 1° frequency sputtering device under an argon pressure of approximately 1 to 5 m Torr, with a distance between the target and the substrate of 5 to 10 cm.
A thin film with a thickness of several μm or less was prepared as follows. All the diffraction curves of the obtained thin films measured with an X-ray diffractometer showed diffraction curves characteristic of an amorphous structure consisting of a gentle main peak and a few sub-peaks, indicating that an amorphous thin film was obtained. To be there.

confirmed.

Example 2゜Composition is COas, s MOs Z r 9 , s
, CO82MQ a, s Z r 9. s,
'C075,5Mo2S Zr9.5,
l'vfo, Zr on a cobalt disk with a diameter of 5Qmm
An amorphous thin film was fabricated by simultaneous sputter deposition and sequential deposition under the conditions of Example 1 using a composite target in which small lumps were uniformly arranged. The crystallization temperature of the obtained amorphous thin film (determined by electrical resistance measurement using Nishiendi method 10) was as high as approximately 500°C.

Electrical resistance value even after heat treatment at 100℃ for 100 hours.

remains almost unchanged, indicating high thermal stability. It's a trench.

The saturation magnetization decreases to about 6 Qemu as the amount of MO decreases.

It varied from 7g to 100 emu 7g, and a high value was obtained.

I found out that it was Rokoto. The coercivity of these films is approximately 1-50e
Met. COs2 MOa, s exhibiting a low magnetostriction of 18X10 (measured using a semiconductor strain cage)
.

Z r q, 5 An external magnet of 2 kG is applied to the amorphous thin film in the in-plane direction.

Applying a field and rotating at a rotation speed of 1200 r, I), m, and heat treatment at 400 °C for 20 minutes, the coercive force was 83
m0e, initial permeability (20kllZ) of approximately 6000.

Soft magnetic properties were obtained.

Example 6゜Alloy composition is (COO, 3Fe o, 7)91 ZI''
9, (Re 0.7'Ni)Z
r Co Ni Fe Zr (Coo
, 72.

0, ro 90 10' 72 16
2 10+N Io, 1b Peo,
02 Zro, 1) 98 B2, C085
Cr4RL12 Zrq 'CoWZr (Co
Mo Zr8659・0.82 0.08
A non-10 quality thin film was produced by sputter deposition using a sintered body of 53 mm in diameter of 5 0.095 ) 98132 as a target under the same manufacturing conditions as in Example 1. (C.O.
O,3Fe0.7 )91 Z'9' -(Fe0
．． 7”0.3) Saturation magnetization of an amorphous thin film of 90Zr10.

are 160 emu/g and 120 emu/g, respectively.
That's high.

The value was 17. On the other hand, CO72N I 1 b P e
2 Zr io amorphous thin.

In the film, the magnetostriction λ8 is almost 0, and the saturation magnetization σ5110emu/1
゜"(COO,72"0.16FeO,02Z'0
．． 1) 98B2 In an amorphous thin film, λ is approximately O+'
105 e””/ g + Co65 Cr45 Ru2Zr, in an amorphous thin film, λ8 is approximately Q, σ, 9
6 emu.

Zero magnetostrictive materials with a high saturation magnetization of 7g were obtained in each case.

0 ・ 7 ・ Example 4゜"75.5 Mo2S produced under the conditions of Example 1
Z r cp , s When the amorphous thin film was heat-treated at a temperature above its key temperature (approximately 400°C) and below its crystallization temperature (505°C), it was water-cooled and had a coercive force of 53 m.
0e, initial 5 magnetic permeability (5kHz) 10000, small magnetic anisotropy.

Excellent soft magnetic properties were obtained.

Example 5 An alloy having the composition COao MO9Z r 11 was melted by arc melting.

Targeno 10 with a diameter of 5Qmm and a thickness of about 1mm
1. was produced. Approximately 3m using this target.

5QOe or more parallel to the substrate surface under A, r pressure of Torr.

While applying a magnetic field and rotating the substrate, sputter the group.

An amorphous thin film was prepared by depositing the same. Obtained.

The magnetic properties of the amorphous thin film vary by 1 degree depending on the film, but the coercive force is less than 0.10e, and the initial permeability (.

At 20 kHz), magnetic properties suitable for practical use of 6100 or higher were obtained. This seems to indicate that the induced magnetic anisotropy was reduced by this manufacturing method.

・ 8 ・ Example 6゜Alloy composition is (COO,96FeO,04)73Cr2
""10B15'.

(Co Pe ) Mn Si B ,
(Coo,,6Feo,.QO,960,047321
015 )73 N1]2 S'10 B15' C045
,9Fe10.1 ``24 ''''2 Mother of B18.

The alloy was produced by arc melting, and a target with a diameter of 5Qmm and a thickness of about 1mm was produced.Thin film production.

using a two-pole high-frequency sputtering device, approximately 1 to 5 m'T
target and substrate under argon pressure of orr.

A non-woven fabric with a thickness of several μmη or less with an interval of 5 to 13 cm.

A crystalline thin film was prepared. A semi-conductor strain gauge was attached to the surface of the obtained thin film and magnetized with an external magnetic field of 4 kG.

When I measured the strain, it was C045,9Fe10.1”
24S'21318' exhibited a low magnetostriction value of +1X10, and those of other alloy compositions exhibited a low magnetostriction value of 10-7 degrees. As made.

The coercive force of the thin film was 0.5-10e. 1
゜Example 7゜(COo,,6Feo,.4)73Cr obtained in Example 6
2S11oB15° Crystallization temperature of amorphous magnetic thin film (four-terminal electrical resistance).

The temperature (determined by measurement) is approximately 510°C, the key temperature (.

(measured using a magnetic balance) is approximately 440°C, and the saturation magnetization is approximately 440°C. .

It was 3Qemu/g. When this amorphous thin film is heat treated in vacuum at 470°C for 10 minutes and then cooled with water, the coercive force Q decreases from 50e to 7QmOe, resulting in a smooth 13
-H curve was obtained. The initial permeability at that time was 20゜kHz
It showed a high value of 9000 in z.

Example 8゜Alloy composition strength "C00,96FeO,04)77"2
A "10 B11" amorphous thin film was produced under the same conditions as in Example 6.

The crystallization temperature of the amorphous thin film is 450℃, and the saturation magnetization is 1.
00 emu/g, the coercive force was approximately B) Oe. The amorphous thin film obtained in the form of a disk (10 mm in diameter) was placed in a static magnetic field of 4° kG so that the film surface became parallel to the direction of the magnetic field.

Rotate it at a speed of 720 r, p, m.

while keeping the temperature increase and quenching rate at 20°C/min.

Then, heat treatment was performed at 400° C. for 20 minutes. heat,.

The coercive force of this amorphous thin film after treatment is as low as 63m0e.

A high magnetic permeability of approximately 8000 was obtained at 2[]kHz. These improvements in soft magnetic properties are due to magnetic anisotropy.

This is thought to be due to the removal of internal stress.

Example 9.2゜Alloy composition is (C00,96FeO,04)77 Mn2
S'40 B11 ゛diameter 5Qn1m, thickness about i
Using a target of mm: approximately parallel to the substrate plane under an argon pressure of approximately 3 mTorr.

An amorphous thin film 5 having the above composition was fabricated by applying a magnetic field of 1000 e and performing sweeper deposition without rotating the substrate. The obtained amorphous magnetic thin film had a low coercive force of 9 QmOe and a magnetic permeability of 7000 at 1 kHz.

A significantly higher value was obtained, and a remarkable difference was observed compared to the conventional production method.

As is clear from the above description, the alloy composition of the amorphous 10-based thin film of the present invention is different from that of conventional amorphous alloy thin films.

High thermal stability due to different new alloy composition.

It has excellent magnetism among magnetic thin films.

Electroacoustic transducer materials, magnetostrictive elements, such as magnetic core materials, exhibiting characteristics, namely low coercive force and high magnetic permeability.

Effectively used for materials such as Invar and Elinvar.

I can do that.

Representative Patent Attorney Junnosuke Nakamura

Claims (1)

[Claims] (1) The compositional formula is Ma Tl)XCZd, and M is at least one selected from the group of Fe, Ni, and CO.
Seed element, T is MOlCr, W, V, Nl), Ta, M
n, 'A-1, Cu, Zn, ■)1], 8n, P
d, Pt, Au, Ag・, Ru, Os, R,
h, Ir, Be, Mg, La 1Nd,
5ITI-1Eu, Gd, 'rb, Dy, E
r5yb, Lu At least one element selected from the O group 11), X is Zr, Ti, Y, Hf,
Select from the group Ge, Sb, 13i, Te (7). Z is P, B, C1. At least one species selected from the group of Si and N. element, and under the 1° condition where a+b+c+d=100, 0≦b≦95.60≦a+1)≦95.0°≦C
A predominantly amorphous amorphous thin film satisfying ≦70.0≦d≦60 is formed by sputter deposition. In the transfer method, the above C and d are each 5≦゛C≦
It is characterized in that 50.0≦d≦10. A method for producing an amorphous thin film. (b) The compositional formula is MaTl)XcZd, and M is Fe.
,. N1, at least one five elements selected from the group of CO, T, Mo, Cr, Mn, W, V
, Nb, La,. Nd, Sm, Bu, Gd1'rb, Dy,
At least one element selected from the group of Er, Yl), Lu', and X is Zr, TI, Hf,
Y, at least one element selected from the Ge0 group, Z is P%13, C, Si, 1°S, N, kl
At least 1° element selected from the group of
And a+b+c=100. 1≦1]≦20.5≦C≦20.0≦d≦. Amorphous magnetic thin film that is predominantly amorphous. 1. A method for producing an amorphous thin film with a temperature of 1° by sputter deposition. (4) The compositional formula is shown as COeFefNigTbZd, where T is Mo, Cr, W, V%Mn, klSLa, Nd,
sm. IE: u, Gd, TI), DY, Er,
At least one selected from the yb, Lu O group
The seed element, Z, is at least one element selected from the group of 13, C1Sl, and e 10f +
g ten b -) - d = i Q Q Naro. Under the conditions, 25≦e≦9012≦f≦20.0≦. satisfies g≦50.0≦1)≦10.5≦d≦60: predominantly amorphous with saturation magnetic flux density of 71 (6 or more, magnetostriction of 16×10−65 to +6×10); A method for producing an amorphous thin film, characterized in that a crystalline magnetic thin film is produced by a sputter deposition method. (5) The amorphous thin film according to claim 6. A method for producing an amorphous thin film, characterized in that the sputter deposition is performed while applying a magnetic field of 1000 degrees or more that rotates parallel to the thin film surface to the amorphous thin film at 1°. (6) Claim 6 or 4 provides a method for producing an amorphous thin film, wherein the amorphous magnetic thin film obtained by the above method is heated to a temperature higher than the Keeling temperature of the thin film to crystallize the thin film. (7) In the method for producing an amorphous thin film according to claim 6 or 4, the method The amorphous magnetic (9-thin film) rotated parallel to the plane of the thin film (11) while applying a magnetic field of 6 or more and heat-treated at a temperature of 200° C. or higher and below the crystallization temperature of the thin film. A method for producing an amorphous thin film.゛