JP2002319722A - Magnetoresistance effect element and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a magnetoresistance effect element having a new intermediate layer, realizing superior characteristics. SOLUTION: The magnetoresistance effect element comprises an intermediate layer and a pair of magnetic layers which sandwich the intermediate layer. In this case, the intermediate layer contains at least three types of elements selected from among a group consisting of group II to group XVII elements, and the element is at least one type selected from among a group consisting of F, O, N, C and B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnetoresistive element and a method for manufacturing the same.

[0002]

2. Description of the Related Art Magnetic material / tunnel insulating layer (tunnel layer)
/ Since it was shown that a high magnetoresistance ratio (MR ratio) can be realized with a TMR element having a magnetic material as a basic configuration,
Active research has been conducted on TMR elements for applications such as magnetic heads and MRAMs.

[0003] The TMR element utilizes the fact that the tunneling probability between magnetic bodies changes depending on the relative angle of magnetization of two magnetic bodies sandwiching the tunnel layer. Aluminum oxide is mainly used for the tunnel layer. Generally, aluminum oxide is formed by oxidizing a metal aluminum film formed on a magnetic material. As an exception, there has been reported an example in which a TMR element made of boron nitride (BN) is made of aluminum oxide or more (Japanese Patent Application Laid-Open No. Hei 4-103003). , Aluminum oxide is considered to exhibit the largest MR.

[0004]

In order to use a TMR element in a magnetic device such as a magnetic head and an MRAM, it is desired to reduce the element size in order to improve the magnetic recording density and the memory mounting density. Since the tunnel junction resistance increases as the element size decreases, the smaller the junction resistance per unit area, the better. One effective method for reducing the junction resistance is to reduce the thickness of the tunnel layer. However, as the metal aluminum film becomes thinner,
Aluminum is formed in an island shape, and the thickness of the tunnel layer varies greatly, and eventually, it becomes difficult to form a film.

As the thickness of the tunnel layer is reduced, the MR
The ratio also decreases. This is because as the tunnel layer becomes thinner, the magnetostatic coupling and the tunnel exchange coupling between the magnetic layers via the tunnel layer become stronger due to the so-called orange peel effect, so that a preferable relative magnetization angle between the magnetic layers cannot be obtained or the leakage current becomes smaller. It is thought to increase.

In view of the above circumstances, an object of the present invention is to provide a new intermediate layer and a new method of manufacturing the intermediate layer.

[0007]

According to the present invention, there is provided a magnetoresistance effect element comprising an intermediate layer and a pair of magnetic layers sandwiching the intermediate layer, wherein the intermediate layer is at least one selected from the group 2-17. It contains three kinds of elements, and this element contains at least one kind selected from F, O, N, C and B.

[0008] Groups 2 to 17 correspond to groups IIA to VIII and IB to VIIB according to the old IUPAC nomenclature. Two
Group 17 includes all elements except Groups 1 and 18, for example, atomic numbers 57 to 7 called lanthanoids.
1 element is also included.

The present invention also provides a method for manufacturing a magnetoresistive element having an intermediate layer and a pair of magnetic layers sandwiching the intermediate layer. This production method comprises the steps of: forming a precursor of an intermediate layer; and reacting the precursor with the reactive species in a reaction atmosphere containing a reactive species containing at least one selected from an oxygen atom, a nitrogen atom and a carbon atom. Reacting to form at least a part of the intermediate layer. In this manufacturing method, as described later, it is preferable to form the precursor in a plurality of times. In this case, the precursor formed previously may be changed to a part of the intermediate layer, and then another precursor may be formed.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below.

F, O, N, C and B contained in the intermediate layer
At least one element selected from the above is effective in improving the heat resistance of the device. Improvement in heat resistance leads to improvement in MR ratio. The above elements simultaneously increase the barrier height,
In the present invention, by including at least three kinds of elements including this element in the intermediate layer, the barrier height (barrier height) is increased.
Was moderately low. Therefore, a high MR ratio and a low junction resistance can be realized.

The intermediate layer functions as an insulator or a semiconductor in the thickness direction, and further functions as a tunnel layer or a hot electron conductive layer. The intermediate layer may be used as a layer that further interacts with the spin by forming a quantum level or forming a hybrid orbit with a conduction spin near the interface with the magnetic layer or inside the intermediate layer.

The intermediate layer may contain a metal element other than Al, and preferably contains Al together with this metal element. In another preferred form, the intermediate layer is F,
It contains at least two types of elements other than O, C, N and B and selected from Groups 2 to 17.

The intermediate layer is made of Al, at least one selected from O and N, at least one selected from Al, O and N, and 2 to 1 other than Al, O and N.
At least one element selected from Group 7 may be included.

[0015] In another preferred form, the intermediate layer comprises B,
N and at least one element other than B and N and selected from Groups 2 to 17 are included.

The intermediate layer preferably contains at least two kinds selected from B, Al, Ga and In, and N. In this intermediate layer, the amount of nitrogen is easily adjusted stoichiometrically. Therefore, a tunnel junction having a uniform film quality can be easily realized.

The composition of the intermediate layer may change along the thickness direction. The intermediate layer may be a single-layer film or a multilayer film. The composition modulation of the intermediate layer may be introduced into the single layer film due to a change in the reaction atmosphere or the like, or may be introduced by a multilayer structure of films having mutually different compositions. In the case of having a multilayer structure, each of the above elements may be contained in at least one film constituting the intermediate layer.

When an intermediate layer having a composition modulation or a multilayer structure is used, a decrease in MR ratio due to an increase in bias current is suppressed.

In a preferred embodiment of the present invention, the intermediate layer includes two films having different barrier heights. When the intermediate layer includes a first intermediate film in contact with one of the pair of magnetic layers, a second intermediate film in contact with the other of the pair of magnetic layers, and a third intermediate film sandwiched between these intermediate films The barrier height of the third intermediate film may be set lower than at least one selected from the barrier height of the first intermediate film and the barrier height of the second intermediate film. In other words, it is preferable that a material having a relatively high barrier height is disposed at the interface with the magnetic layer, and a material having a relatively low barrier height is disposed inside the intermediate layer. If this preferred arrangement can be realized, the number of films constituting the layers is not limited.

In the case where the intermediate layer is a multilayer film, preferred examples of the intermediate layer include a first film having a relatively high barrier height and made of at least one selected from AlN, AlON, Al ₂ O ₃ and BN. , A combination with the second film having a relatively lower barrier height than the first film. High barrier film / Low barrier film /
The three-layer structure of the high barrier film is particularly preferable. In this case, discrete tunnel levels are formed in the low barrier film, and this level is considered to contribute to improvement of the MR ratio.

The intermediate layer may include a magnetic film. In this case, at least one non-magnetic film is preferably interposed between the magnetic film and a pair of magnetic layers sandwiching the intermediate layer. As the magnetic film, a material having a high polarizability (for example, a material having a higher polarizability than the material forming the pair of magnetic layers) is preferable, and specifically, a half metal, for example, XMnSb (X is Ni, Cu and Pt) LaSrMnO, CrO
₂ , Fe ₃ O _{4 and the} like are preferable.

The intermediate layer may include a non-magnetic metal film. A preferred film configuration of the intermediate layer includes a multilayer film including a nonmagnetic metal film and a dielectric.

The thickness of the intermediate layer is not particularly limited.
The thickness is preferably 0.5 nm or more and 5 nm or less. If the thickness is less than 0.5 nm, the magnetic coupling between the magnetic layers sandwiching the intermediate layer becomes too strong, and the MR value decreases. If it exceeds 5 nm,
Tunnel probability decreases and junction resistance becomes too large.

The intermediate layer may include any of a single crystal film, a polycrystalline film, and an amorphous film. When a single crystal film is used, the potential in the layer becomes uniform, and uniform tunnel conduction easily occurs. When an amorphous film is used, stress between the film and the magnetic layer can be reduced.

Conventionally used materials can be used for the magnetic layer without any particular limitation. However, it is preferable that at least one of the pair of magnetic layers contains at least one selected from F, O, N, C and B. preferable. This is because the interface energy between the magnetic layer and the intermediate layer is reduced, so that a stable film can be easily formed even when the magnetic layer is thinned.

A ferromagnetic material may be interposed between at least one of the pair of magnetic layers and the intermediate layer. This ferromagnetic material is preferably a ferromagnetic film having a thickness of 0.5 nm or less.
This ferromagnetic layer may be formed as a film having a thickness of, for example, 0.1 nm or more, but need not necessarily be formed as a film.
It may be dispersed as fine particles at the interface with the intermediate layer.

The ferromagnetic material interposed at the interface with the intermediate layer is preferably a ferromagnetic material containing at least one element selected from Fe, Co and Ni, or a half metal. Preferred examples of the half metal include XMnSb,
LaSrMnO, LaSrMnO, CrO ₂ , Fe ₃ O ₄
And half metal ferromagnetic materials such as FeCr.

For the magnetic layer in contact with the ferromagnetic material on the side opposite to the intermediate layer, a ferromagnetic material containing at least one element selected from Fe, Co and Ni in an amount of 70 atomic% or more is preferable. The Curie temperature of the ferromagnetic material is preferably 200 ° C. or higher. In order to keep the Curie temperature high, this magnetic layer should be thicker than 0.5 nm. This improves the temperature stability of the element, particularly when the intervening ferromagnetic material is a half metal.

Next, a preferred embodiment of the production method of the present invention will be described. In this method, the precursor is converted to an oxygen atom,
The film may be formed in a reaction atmosphere containing at least one reactive species selected from a nitrogen atom and a carbon atom.
The precursor may be formed a plurality of times. In this case, a step of forming a first precursor under a first reaction atmosphere;
A step of using the first precursor as a first intermediate film that becomes a part of the intermediate layer; a step of forming a second precursor on the first intermediate film under a second reaction atmosphere; A second part of the middle layer
The second reaction atmosphere has a higher reactivity than the first reaction atmosphere, in other words, “strong”.
Preferably, the method is an atmosphere.

In another preferred embodiment, the present invention comprises a step of forming a first precursor and a step of forming the first precursor into a first intermediate film which becomes a part of an intermediate layer in a first reaction atmosphere. Forming a second precursor on the first intermediate film, and forming the second precursor into a second intermediate film that becomes a part of the intermediate layer under a second reaction atmosphere. The atmosphere is used as a method having higher reactivity than the first reaction atmosphere.

The reactive species acting on the precursor may affect the film (eg, magnetic layer) supporting the precursor. Therefore, when strong reaction conditions are applied, the magnetic layer may be deteriorated by oxidation or the like. However, if a film covering the magnetic layer is formed by applying relatively weak conditions first,
Reactive species hardly deteriorate the magnetic layer. If the intermediate layer is formed while changing the reaction conditions, a desired intermediate layer can be efficiently obtained while suppressing deterioration of the magnetic layer.

The "strength" of the reaction atmosphere, that is, the ability to promote the reaction with the precursor may be controlled by the temperature, the activated state of the reactive species, the partial pressure of the reactive species, and the like. The partial pressure of the reactive species is
This is one of the conditions that can be easily controlled. A preferred embodiment of the present invention includes a method in which the partial pressure of the reactive species in the reaction atmosphere applied to the second precursor is higher than the partial pressure of the reactive species in the reaction atmosphere applied to the first precursor.

In a preferred form of the invention, a "weak" reaction atmosphere is used followed by a "strong" reaction atmosphere. Here, the “weak” reaction atmosphere is preferably an atmosphere in which the precursor is reacted to a state having less than 80% of the stoichiometric value of the reactive species (eg, F, O, N and C). A "strong" reaction atmosphere is preferably an atmosphere that allows the precursor to react to a state in which the reactive species is present at 80% or more, preferably 99% or more of the stoichiometric value.

The step of forming the intermediate layer may be performed three or more times. In this case, the first precursor and the second precursor do not necessarily need to be formed continuously.

In the case where the precursor is formed n times in order to form the intermediate layer, the reaction atmosphere applied to the precursor to be formed in the m-th process is the same as that in the (m-1) -th process. It is preferable to adjust so as to have a higher reactivity than the reaction atmosphere applied to. Here, n is an integer of 2 or more, and m is an integer selected from n. In order to realize good bonding by the intermediate layer, it may be necessary to oxidize the precursor over a relatively long reaction time.
If the conditions are gradually increased, a good intermediate layer can be formed in a short reaction time.

The next precursor may be stacked while a part of the precursor formed first is intentionally left unreacted. According to this preferred example, a portion of the unreacted precursor can be reacted with an element contained in the magnetic layer (underlying magnetic layer) serving as a base of the intermediate layer by heating thereafter. . The heating temperature is not particularly limited,
A temperature of about 400 ° C. is preferable. This heating may be used also as a heat treatment step required for manufacturing the device.

Elements serving as reactive species (for example, at least one selected from O, N and C) mixed in the magnetic layer are as follows:
The properties of the magnetic layer may be degraded. If these elements are reacted with unreacted portions of the precursor and removed, deterioration of the magnetic layer can be suppressed. The unreacted precursor also has a role of protecting the underlying magnetic layer from oxidation and the like performed thereafter. In order to leave a part of the precursor unreacted, it is preferable to control the thickness of the precursor so that all of the precursor does not react under the reaction conditions in which the film thickness is applied.

Further, the present inventors have found that, particularly when the precursor contains an element other than Al, the volume ratio between the precursor and the intermediate layer formed therefrom has a great influence on the characteristics of the intermediate layer. Was found.

That is, in a preferred embodiment of the present invention, there is provided a method in which the ratio of the volume Va of the film formed from the precursor to the volume Vb of the precursor (Va / Vb) is 1.05 or more and 2.0 or less. included.

The precursor is usually formed by a vacuum film forming method such as a sputtering method. The precursor formed by this method generally has a density of about 60 to 99.9% of the theoretical density. The precursor in a so-called "nested" state increases or decreases in volume as it reacts with the reactive species. At this time, if Va / Vb is less than 1.05,
A large leak current may occur between a pair of magnetic layers sandwiching a very thin intermediate layer. On the other hand, if Va / Vb exceeds 2.0, the intermediate layer becomes non-uniform and the resistance value tends to vary, and in extreme cases, cracks occur due to volume expansion.

The intermediate layer is more preferably formed by reacting a precursor having a density of 90% or more of the theoretical density with a reactive species so that Va / Vb becomes 1.1 or more and 1.5 or less. This preferred manufacturing method is advantageous for achieving both low junction resistance and high MR value.

As described above, to reduce the resistance of the intermediate layer,
It is better to include a plurality of elements. Therefore, in each of the methods described above, it is preferable that the intermediate layer precursor after the reaction with the reactive species contains at least three elements selected from Groups 2 to 17.

The reactive species is not particularly limited as long as it reacts with the precursor. For example, if the reactive species contains at least one selected from oxygen atom, nitrogen atom and carbon atom, and preferably contains oxygen atom and / or nitrogen atom, Good. An atmosphere containing oxygen and nitrogen atoms is particularly suitable. More specifically, at least one selected from ozone, oxygen plasma, nitrogen plasma, oxygen radicals and nitrogen radicals
A reaction atmosphere containing the seed is preferred. In the present specification, there is no particular limitation on the state in which “atoms” are included, and they may exist as molecules, plasma, radicals, or the like.

The atmosphere used for the reaction of the precursor includes at least one selected from Kr atoms and Xe atoms.
It is good to include seeds. These inert gases homogenize the energy state of at least one plasma or radical selected from oxygen and nitrogen, or ozone. Ar atoms may be contained together with these inert gases.

The precursor is brought into contact with a first atmosphere containing at least one selected from the group consisting of Ar atoms and nitrogen atoms, and then the precursor is mixed with at least one of the atoms selected from Ar atoms and nitrogen atoms.
You may contact with the 2nd atmosphere containing a seed and an oxygen atom. The pressure of the first atmosphere is preferably 100 mTorr or more, and the pressure of the second atmosphere is preferably 1 to 100 mTorr. First with low reactivity
Oxidation by the second atmosphere after increasing the pressure in the reaction chamber by introducing an atmosphere can suppress deterioration of the intermediate layer due to impurities easily introduced together with oxygen.

The precursor may be appropriately selected according to the desired intermediate layer. For example, to form Al ₂ O ₃ as the intermediate layer, metallic aluminum (Al) or aluminum oxide (AlOx (x <1.5)) is used.

The precursor may include an amorphous phase. The amorphous precursor tends to cover the magnetic layer uniformly. For the amorphization, for example, a precursor containing two or more transition metals, or at least one transition metal and B,
A precursor containing at least one selected from C, Si and P is suitable. With these combinations,
The difference between the freezing point and the glass transition point becomes small, and crystallization hardly occurs.

In a preferred embodiment of the present invention, a step of forming a first magnetic layer on at least two substrates, a step of forming a precursor on the first magnetic layer in the same film forming chamber, respectively, Transferring at least two substrates from the film formation chamber to the reaction chamber, making the precursor at least part of an intermediate layer under the same reaction atmosphere in the reaction chamber, Forming a second magnetic layer. The characteristics of the intermediate layer are likely to be affected by various conditions of the formation process. By forming the intermediate layer on a plurality of substrates at a time as described above, variation in element characteristics between the substrates can be suppressed. This method
For example, as shown in FIG. 1 and FIG.
31a, 31b and reaction chambers (load lock chambers) 22, 32
Are vacuum transfer chambers 23 and 33 and gate valves 25 and 3
5 can be carried out using a device connected via the control unit 5. When this apparatus is used, the substrates 24 and 34 can move between the film formation chamber and the reaction chamber while maintaining a vacuum state. When the reaction chamber and the load lock chamber are used as described above, the size of the apparatus can be reduced. On the other hand, when a load lock chamber is provided separately from the film formation chamber and the reaction chamber, and a vacuum transfer chamber is arranged so as to connect them, productivity can be improved.

FIG. 3 is a cross section of an example of the magnetoresistive element of the present invention. The magnetoresistive element 10 includes a first magnetic layer 1, an intermediate layer 2, and a second magnetic layer 3 as basic films. In this element, the electrical resistance between the magnetic layers 1 and 3 via the intermediate layer 2 changes by changing the relative magnetization angle of the magnetic layers 1 and 3 according to the external magnetic field. This change in electrical resistance is
It is detected by the current flowing between 1 and 13. The region other than the element between the two electrodes is insulated by the interlayer insulating film 12. The multilayer film including these members may be formed on the substrate 14 by a sputtering method or the like.

The magnetization of one of the magnetic layers 1 and 3 is fixed, and the rotation of the magnetization of the other magnetic layer (free magnetic layer) is performed.
A change in resistance may be caused. It is preferable to arrange a magnetization rotation suppressing layer on the surface opposite to the intermediate layer in the magnetic layer for fixing the magnetization (fixed magnetic layer). Examples of the magnetization rotation suppressing layer include a high coercive force magnetic material, an antiferromagnetic material, and a laminated ferrimagnetic material. As the magnetization rotation suppressing layer, a multilayer film such as a laminated ferrimagnetic / antiferromagnetic material, a laminated ferrimagnetic / high coercive force magnetic material may be used. The laminated ferrimagnetic material itself may be used as the fixed magnetic layer.

As the high coercivity magnetic material, FePt, Co
Pt, CoPtTa, CoCrPtB and the like are preferable. The laminated ferri structure may have a laminated structure of at least two magnetic layers MT and at least one nonmagnetic layer X. In the laminated ferrimagnetic layer, two magnetic layers are antiferromagnetically coupled via a nonmagnetic layer, and function to increase the fixed magnetic field of the fixed layer. X
May be Cu, Ag, or Au, but is preferably Ru, Rh, Ir, or Re from the viewpoint of the thermal stability of the interface.
u is excellent. The preferable thickness of Ru is 0.6 to 0.5.
It is about 8 nm. As the MT, a ferromagnetic material containing at least 70 atomic% of at least one magnetic metal selected from Fe, Co and Ni is suitable. The preferred thickness of this layer is 0.5
５5 nm. As the antiferromagnetic material, in addition to Cr alone, Ru, Re, Ir, Rh. An alloy of Mn and / or Cr with at least one element selected from Pt and Pd is preferable. The preferred thickness of the antiferromagnetic material is 1-1.
It is about 00 nm. In order to improve the characteristics of the antiferromagnetic material or to prevent thermal diffusion between the antiferromagnetic material and a non-magnetic material (eg, an electrode) in contact with the antiferromagnetic material, Hf, Ta, NiFe, NiFeC
A base layer of r, Cr, or the like or a diffusion prevention layer may be formed.

As described above, known materials can be used for the magnetic layers 1 and 3 without any particular limitation. The magnetic layer has a thickness of at least 0.1 nm from the vicinity of the interface between the intermediate layer and Fe.
A magnetic material containing at least 50 atomic% of at least one metal magnetic element selected from Co and Ni is preferable. Materials that satisfy this condition include F ₂₅ Co ₇₅ and Fe ₅₀ Co ₅₀
eCo alloys, NiFe such as Ni ₄₀ Fe ₆₀ , Ni ₈₁ Fe ₁₉
Alloys, NiFeCo alloys, and FeCr, Fe
SiAl, FeSi, FeAl, FeCoSi, FeC
oAl, FeCoSiAl, FeCoTi, Fe (N
i) (Co) Pt, Fe (Ni) (Co) Pd, Fe
(Ni) (Co) Rh, Fe (Ni) (Co) Ir, F
An alloy of a non-magnetic element such as e (Ni) (Co) Ru and a magnetic element is included. As the magnetic material, FeN, FeTi
N, FeAlN, FeSiN, FeTaN, FeCo
N, FeCoTiN, FeCoAlN, FeCoSi
N, nitrides such as FeCoTaN, oxides such as Fe ₃ O ₄ , MnZn ferrite, NiZn ferrite, CoNbZ
r, an amorphous magnetic material such as CoTaNbZr may be used. XMnSb, LaSrM as the magnetic material
A half metal (half metallic ferromagnetic material) such as nO, LaCaSrMnO, or CrO ₂ may be used. The half metal is preferably contained in an amount of 50 atomic% or more.
A magnetic semiconductor doped with an element selected from V, Cr, Fe, Co and Ni in ZnO may be used.

The magnetic layers 1 and 3 do not have to have a uniform composition. In order to increase soft polarizability, hard magnetizability, high spin polarizability near the Fermi surface at the interface of the intermediate layer, or increase in spin polarizability due to formation of artificial lattice or quantum level, multiple compounds with different compositions and crystal structures from each other A magnetic material may be laminated and used, or a magnetic material and a non-magnetic material may be laminated and used.

[0054]

EXAMPLES In the following examples, elements that have not been subjected to composition analysis are described without elements by arranging elements.

(Embodiment 1) In this embodiment, a film forming chamber (attained vacuum degree of 5 × 10 ^-9 To
rr) and a load lock chamber capable of reverse sputtering, capable of introducing nitrogen radicals, oxygen and oxygen radicals, and capable of heating a substrate by a lamp, has a configuration similar to that of FIG. A multi-layer film forming apparatus was used. In a film forming chamber of this apparatus, the following films were formed on a 6-inch silicon substrate provided with a thermal oxide film.

Ta (3) / Cu (750) / Ta (3) / PtMn (30) / Co ₉₀ Fe
₁₀ (3) / Ru (0.7) / Co ₉₀ Fe ₁₀ (2) / Co ₅₀ Fe ₅₀ (1) / interlayer / Co ₅₀ F
e ₅₀ (1) / NiFe (2) / Ru (0.7) / NiFe (2) / Ta (5) However, the above shows each film in order from the substrate side, and the thickness in parentheses indicates the film thickness ( The unit is nm; the same applies hereinafter).

This multilayer film is composed of a base film, a lower electrode, a base film, an antiferromagnetic material, a laminated ferrimagnetic layer, a fixed magnetic layer, an intermediate layer, a free magnetic layer, and a protective layer. Here, in Co ₅₀ Fe ₅₀ (1) / NiFe (2) / Ru (0.7) / NiFe (2) corresponding to the free magnetic layer,
Soft laminated ferrimagnetic across the ru NiFe is bound by exchange coupling, which simplifies the magnetic domain structure of Co ₅₀ Fe _50.

Next, uniaxial anisotropy is imparted to the fixed magnetic layer.
For this purpose, the substrate on which the multilayer film is formed
The heat treatment was performed by applying a magnetic field of 5 kOe. This membrane
As shown in FIG. 3, it is processed into a mesa shape, and further an interlayer insulating film is formed.
An upper electrode was formed. The element cross section of the intermediate layer is 0.5 μm
^TwoAnd 300 nm thick Al as the interlayer insulating film_TwoO
_ThreeThe upper electrode is made of Ta having a thickness of 5 nm and a thickness of 750.
A laminate with Cu of nm was used.

The method for forming the intermediate layer will be described below. First, an intermediate layer precursor was produced by discharging a target composed of elements obtained by removing oxygen and nitrogen from the elements constituting each compound (see Table 1) in Ar gas. The thickness of this precursor was 0.3 to 0.4 nm. However, when the above elements other than oxygen and nitrogen contained carbon, a carbide target was used. If there are multiple elements except oxygen, nitrogen and carbon, prepare a target for each of those elements,
These targets were discharged simultaneously.

Next, the substrate was transferred from the film forming chamber to the load lock chamber, and the precursor was oxidized and / or nitrided.
Oxidation was performed by introducing oxygen at 10 to 600 Torr and reacting for 10 seconds to 6 hours. Nitriding converts nitrogen radicals into 3 ~
It was produced by introducing for 900 seconds. Oxynitridation was produced by performing oxidation and nitridation in this order in the same manner as described above. In addition, it was confirmed that oxynitriding or nitriding could be performed by reverse sputtering RF discharge in an atmosphere in which nitrogen gas was introduced instead of introducing nitrogen radicals.

Subsequently, the same intermediate layer precursor as above was added in an amount of 0.2%.
A film was formed to have a thickness of about 0.3 nm, and oxidation, nitridation, or oxynitridation in the load lock chamber was repeated.

A current was applied between the upper electrode and the lower electrode of the magnetoresistive element thus manufactured, and the rate of change in resistance between the electrodes, which was changed by an external magnetic field, was measured. Also,
The junction resistance (R) per unit area (1 μm ² ) of the intermediate layer
A) was measured. The results are shown in Table 1 together with the composition of the intermediate layer.

Although the stoichiometric composition is shown in Table 1 for convenience, the intermediate layer formed here does not always have the same composition. For example, Al ₂ O ₃
Ox (x = about 1.1 to 1.5). in this way,
The indication of each intermediate layer also includes a composition deviating from the stoichiometric composition by about 20 to 30%. In addition, in the intermediate layer in which a plurality of compounds are shown, the ratio of each compound was adjusted with a target of 1: 1. However, since the ratio has not been confirmed, the ratio may deviate from this ratio. Compound to be added to the intermediate layer (Al ₂ O _3.
The effect of MgO on MgO has been confirmed in a wide range of 5 to 95% by weight.

With respect to the Al ₂ O ₃ layer, in order to reduce RA, a sample in which the thickness of the intermediate layer precursor was gradually reduced from that described above was prepared, and the same measurement was performed. In Table 1, the sample marked with * is an intermediate layer obtained by the same operation as the samples of other materials.

(Table 1-1) Intermediate layer MR (%) RA ―――――――――――――――――――――――――――――――― (Ωμm ² ) ―――――――――――――――――――――――――――――――― Al ₂ O ₃ 3 1 Al ₂ O ₃ 8 5 _{Al 2 O 3 15 10 Al 2} O 3 21 15 Al 2 O 3 28 20 * Al 2 O 3 38 30 Al 2 O 3 · MgO 31 15 Al 2 O 3 · SrTiO 3 35 18 Al 2 O 3 · Y 2 O _{3 37 14 Al 2 O 3 ·} CeO 2 33 13 Al 2 O 3 · TiO 2 36 12 Al 2 O 3 · ZrO 2 35 14 Al 2 O 3 · HfO 2 37 18 Al 2 O 3 · V 2 O 5 33 16 Al ₂ O ₃ .Nb ₂ O ₅ 34 17 Al ₂ O ₃ .Ta ₂ O ₅ 3818 Al ₂ O ₃ .Cr ₂ O ₃ 35 16 Al ₂ O ₃ .MnO 30 12 Al ₂ O _{3. Cu 2 O 37 10 Al 2 O} 3 · ZnO 30 14 Al 2 O 3 · Ga 2 O 3 33 16 Al 2 O 3 · SiO 2 34 12 Al 2 O 3 · AlF 3 31 15 Al 2 O 3 · Al 4 C ₃ 28 10 Al ₂ O ₃ .AlN 26 10 ――――――――――――――――――――――――――――――――

(Table 1-2) Intermediate layer MR (%) RA ―――――――――――――――――――――――――――――――― (Ωμm ² ) ―――――――――――――――――――――――――――――――― AlN 24 18 AlN · HfN 258 AlN · ZrN 24 7 AlN · TiN 23 6 AlN · TaN 25 5 AlN · NbN 26 6 AlN · VN 24 7 AlN · BN 31 5 AlN · GaN 28 3 AlN · InN 26 3 AlN · Al 4 C 3 20 3 ------ ――――――――――――――――――――――――――――

(Table 1-3) ―――――――――――――――――――――――――――――――― Middle layer MR (%) RA (Ωμm ² ) ―――――――――――――――――――――――――――――――― BN 18 12 BN / HfN 22 2 BN / ZrN 19 1 BN / TiN 183 BN / TaN 192 BN / NbN 182 BN / VN 161 BN / GaN 201 1 BN / InN 19 1 ------ ―――――――――――――――

[0068] From Table 1, simply decreasing the RA by decreasing the thickness of the Al ₂ O ₃ film, MR ratio is also reduced at the same time. In contrast, other and in the intermediate layer adding an element to the Al ₂ O _3, as long as MR ratio is the same, RA was lower than the case where only Al ₂ O _3. Similarly, a relatively low RA was obtained at the same MR ratio in the intermediate layer obtained by adding other elements to AlN and BN. In particular, when at least one kind of nitride selected from Al, B, Ga, and In is used as the material of the intermediate layer, a low RA can be realized while ensuring an MR ratio.

When an intermediate layer whose composition was modulated in the film thickness direction was produced, a high MR and a low RA could both be achieved in the same manner as described above. The composition modulation can be performed by forming a multilayer film in which films containing any one of the two compounds described in the table are stacked, adjusting voltages applied to a plurality of targets, adjusting oxygen and nitrogen as reactive species, and the like. it can. Even if the plurality of elements are not uniformly contained in the intermediate layer, the effect of adding the elements can be obtained.

Further, regarding the relationship between the thickness of each intermediate layer and RA, it was confirmed that RA increased exponentially with respect to the thickness of the intermediate layer. Based on this, the resistance value of the intermediate layer may be adjusted according to the target device.

(Example 2) A film forming chamber for magnetron sputtering (attained vacuum of 5 × 10 ^-9 Torr), a film forming chamber for IBD (ion beam deposition; ultimate vacuum of 5 × 10 ^-9 Torr), and A multi-layer film forming apparatus having a configuration similar to that of FIG. 2 in which the load lock chambers were connected to each other by a vacuum transfer chamber was prepared. Using this apparatus, the following films were formed on a 6-inch silicon substrate with a thermal oxide film.

Ta (3) / Cu (500) / Ta (3) / MnRh (30) / Co90Fe10
(3) / Ru (0.7) / Co90Fe10 (2) / Co75Fe25 (1) / Intermediate layer / Co75Fe2
The precursor for forming the 5 (1) / NiFe (5) / Ta (5) intermediate layer was formed by IBD, and the other layers were formed by magnetron sputtering. This multilayer film is composed of a base film / lower electrode / base film / antiferromagnetic material / stacked ferri / fixed magnetic layer / intermediate layer / free magnetic layer / protective layer.

Next, in order to impart uniaxial anisotropy to the fixed magnetic layer, a heat treatment was performed in a vacuum at 250 ° C. by applying a magnetic field of 5 kOe. This film was subjected to mesa processing so that the element area became 0.5 μm ² as shown in FIG. 3, and Cu (500) was formed as an upper electrode.

Here, the thickness of the intermediate layer is 1.5 nm.
An Al ₂ O ₃ film, a non-magnetic element film having a thickness of 0.25 nm,
Were formed in this order. Further, an intermediate layer of a multilayer film in which an Al ₂ O ₃ film having a thickness of 1.5 nm was sandwiched between a pair of nonmagnetic elements having a thickness of 0.25 nm was also prepared.

Table 2 shows the film configuration of this multilayer film. The MR ratio of the fabricated device was measured with measurement biases of -0.5 V and 0.5 V.

(Table 2) ―――――――――――――――――――――――――――――――― Middle layer MR (%) MR reduction rate (%) ―――――――――――――――――――――――――――――――― Al ₂ O ₃ 15/15 50 Al ₂ O ₃ / _{Cu -3/3 -20 Al 2 O 3 /} Ag -0.1 / 0.5 -30 Al 2 O 3 / Au -2/2 -10 Al 2 O 3 / Ru -2/2 -15 Ru / Al _{2 O 3 / Ru -3/5 -20 Al} 2 O 3 / Rh -1/2 -5 Al 2 O 3 / Ir -1/2 -10 Al 2 O 3 / Re -2/3 -10 Al 2 O ₃ / Pt 12/18 30 Al ₂ O ₃ / Pd 15/18 40 Al ₂ O ₃ / Ti 11/21 20 Al ₂ O ₃ / Zr 11/16 30 Al ₂ O ₃ / Hf 12/17 40 Al ₂ O ₃ / V 11 / 18 30 Al ₂ O ₃ / Nb 13/19 20 Al ₂ O ₃ / Ta 15/20 30 Al ₂ O ₃ / Cr 13/23 20 Al ₂ O ₃ / Mo 11/15 10 Al ₂ O ₃ / W 13 / 15 20 ――――――――――――――――――――――――――――――――――

In the MR ratio in Table 2, values when positive and negative biases are applied are shown such that a relatively small value is on the left side. In addition, the MR reduction rate is defined as an MR ratio (a relatively large M
R ratio). A negative decrease rate indicates an increase in the MR ratio due to bias application.

As shown in Table 2, Cu, Ag, Au,
When Ru, Rh, Ir, and Re were laminated, a negative MR ratio was observed. An element exhibiting a negative MR ratio can be used as an element for determining the sign of a bias by combining a comparator or the like for comparing with a standard resistance value. In addition, when a non-magnetic film is stacked, the rate of decrease when bias is applied is reduced, and the MR ratio may be increased. Strong asymmetry is useful for devices that require high power to increase the S / N of the MR change.

The above phenomenon is caused by the fact that Al ₂ O ₃ is used instead of Al ₂ O _3.
It is also expressed when N and BN are used. In addition, asymmetry shows different bias dependence depending on the thickness of the nonmagnetic layer in the range of 0.1 to 1 nm, but almost no MR is observed when the thickness exceeds 1 nm.

Example 3 Using the multi-layer film forming apparatus used in Example 2, the following films were formed on a 6-inch silicon substrate with a thermal oxide film.

Ta (3) / Cu (500) / Ta (3) / PtMn (30) / Co (3) / Ru
(0.7) / Co (2) / Co50Fe50 (1) / Intermediate layer / Co74Fe26 (1) / NiFe (5)
The precursor for forming the / Ta (5) intermediate layer and Co74Fe26 were formed by IBD, and the other layers were formed by magnetron sputtering. This film is composed of an underlayer, a lower electrode layer, an underlayer, an antiferromagnetic material, a laminated ferrimagnetic layer, a fixed magnetic layer, an intermediate layer, a free magnetic layer, and a protective layer. Next, in the same manner as in Example 2, heat treatment, mesa processing, and formation of an upper electrode were performed.

As the intermediate layer, a film configuration shown in Table 3 was employed. The Al ₂ O ₃ films at both ends of the three-layer film were formed by forming an Al film having a thickness of 0.3 nm, and then oxidizing at 20 ° C. for 1 minute in a 20 Torr oxygen atmosphere and for 1 minute in a 200 Torr oxygen atmosphere. A film of Al having a thickness of 0.2 nm is formed at 200 Torr.
For 3 minutes in an oxygen atmosphere. Single layer of Al ₂ O ₃
The film was formed by repeating the above steps so that the total thickness of the Al thickness before oxidation was 1 nm.

The AlN film at both ends of the three-layer film is formed by depositing 0.5 nm of Al, and then performing reverse sputtering in an Ar + N ₂ atmosphere for 10 minutes.
Seconds and formed.

The AlN film and BN film at the center of the three-layer film
While assisting with nitrogen plasma,
And a BN target to form a film having a thickness of 0.2 nm. Other compound films similarly arranged at the center were formed to a film thickness of 0.2 nm using targets of each compound.

For the device fabricated as described above,
The MR ratio was measured. Table 3 shows the results together with the composition of the intermediate layer.
Shown in In Table 3, the whistler alloy (NiMnS
b, CuMnSb, PtMnSb) show only the components because the compositional deviation due to sputtering is large. However, in the film shown, the same effect can be obtained even if the composition deviation from the stoichiometric ratio is about 10%.

(Table 3) ――――――――――――――――――――――――――――― Middle class MR (%) ―――――――― ――――――――――――――――――――― Al ₂ O ₃ 40 ―――――――――――――――――――――――― ------ Al ₂ O ₃ / Fe ₃ O ₄ / Al ₂ O ₃ 49 Al ₂ O ₃ / NiMnSb / Al ₂ O ₃ 52 Al ₂ O ₃ / CuMnSb / Al ₂ O ₃ 53 Al ₂ O ₃ / PtMnSb / Al ₂ O ₃ 55 Al ₂ O ₃ / LaSrMnO / Al ₂ O ₃ 51 Al ₂ O ₃ / CrO ₂ / Al ₂ O ₃ 55 ――――――――――――――――――― ―――――――――― Al ₂ O ₃ / AlN / Al ₂ O ₃ 46 Al ₂ O ₃ / BN / Al ₂ O ₃ 45 AlN / BN / AlN 45 ―――――――――― ――――――――――――― ――――――

As shown in Table 3, a higher MR ratio was obtained from the element using the _three- layered intermediate layer than from the element using the Al ₂ O ₃ single-layered intermediate layer.

Further, while limiting the total thickness of the intermediate layer having a three-layer structure to a thickness of 0.1 to 2 nm, the thickness of the central layer is changed in a range of 0.1 to 1.2 nm. Where
A higher MR ratio was obtained.

Further, when the thickness of the center layer was set to 0.2 nm and the thicknesses of the Al ₂ O ₃ film and the AlN film as the both end layers were changed, the total thickness of the intermediate layer was 0.5 nm to 5
A high MR ratio was obtained in the range of nm.

Next, while maintaining the same thickness ratio of each layer constituting the intermediate layer, the stability of the intermediate layer was examined by changing the total thickness of the intermediate layer.

Here, Ta (3) / Cu (500) / Cr (2.2) / Co (3) /
An element having a film configuration of Ru (0.7) / Co (2) / Fe (1) / intermediate layer / Fe (1) / NiFe (5) / Ta (5), and in this film configuration, the Fe layer is made of Fe
N, FeHfC, FeTaC, FeTaN, FeHf
N, FeZrN, FeNbB, FeAlO, FeSiO
Alternatively, an element substituted with FeAlF was produced. When the applied magnetic field was measured at 600 Oe, the fabricated element was
In any case, a spin-valve MR without using an antiferromagnetic material
The curves are shown. However, as the intermediate layer becomes thinner, Fe
Cannot be observed in the element having a magnetic layer. On the other hand, when the above magnetic material containing at least one selected from F, O, C and N was used as the intermediate layer, it was confirmed that MR was exhibited when the thickness of the intermediate layer was about 0.5 nm or more. .

Example 4 Using the multi-layer film forming apparatus used in Example 2, the following films were formed on a 6-inch silicon substrate with a thermal oxide film.

Ta (3) / Cu (500) / Ta (3) / PtPdMn (30) / Co (3) / R
u (0.7) / Co (2) / Fe24Co76 (1) / AlON / free magnetic layer / Ta (5) The first magnetic film constituting the free magnetic layer was formed by IBD, and the other layers were formed by magnetron sputtering. This multilayer film is composed of an underlayer, a lower electrode layer, an underlayer, an antiferromagnetic material, a laminated ferrimagnetic layer, a fixed magnetic layer, an intermediate layer, a free magnetic layer, and a protective film.

Here, the AlON intermediate layer was formed by introducing an oxygen / nitrogen mixed radical after forming Al. The free magnetic layer has a two-layer structure of a first magnetic film and a second magnetic film from the intermediate layer side. The first magnetic film uses the magnetic layers shown in Table 4, and the second magnetic film has a thickness of 5 nm. of
Fe50Co50 was used.

Next, in order to impart uniaxial anisotropy to the fixed layer, a heat treatment was performed in a vacuum at 250 ° C. by applying a magnetic field of 5 kOe. This film is subjected to mesa processing so that the element area becomes 0.5 μm ^2, and Cu (500) is formed as an upper electrode,
The MR ratio was measured. Table 4 shows the results.

(Table 4) First magnetic film (thickness; unit: nm) MR (% ) ――――――――――――――――――――――――――――― None 40 Fe ₃ O ₄ (0.1) 43 Fe ₃ O ₄ (0.25) ) 48 Fe ₃ O ₄ (0.5) 46 Fe ₃ O ₄ (1) 40 NiMnSb (0.1) 45 NiMnSb (0.25) 47 NiMnSb (0.5) 45 NiMnSb (1.0) 40 CuMnSb ( 0.25) 46 PtMnSb (0.25) 45 LaSrMnO (0.25) 45 CrO 2 (0.25) 48 FeCr (0.25) 49 Co 75 Fe 25 (0.25) 49 Co 80 Fe 20 (0 .25) 49 ―――――――――――――――――――――――――――――

From Table 4, it can be confirmed that when a ferromagnetic material having a thickness of 0.1 to 0.5 nm is interposed between the magnetic layer and the intermediate layer, the MR ratio is increased.

(Embodiment 5) In this embodiment, the magnetron sputtering film forming chamber (attained vacuum degree of 5 × 10 ^-9 Torr) and the reaction chamber / load lock chamber (attained vacuum degree of 8 × 10 ^-8 Torr) are each evacuated. A multi-layer film forming apparatus (see a simplified diagram in FIG. 1) connected to a transfer chamber (a degree of ultimate vacuum of 1 × 10 ⁻⁸ Torr) through a gate valve was used. Twelve 6 inch diameter silicon substrates with a thermal oxide film (substrate S)
1 to S12).

First, the substrate S1 was transported to the film forming chamber, where the following multilayer film was formed, and returned to the load lock chamber.

Ta (3) / Cu (500) / Ta (3) / PtMn (30) / Co90Fe10
(3) / Ru (0.7) / Co90Fe10 (3) / Al (0.4) This film is composed of underlayer / lower electrode layer / underlayer / antiferromagnet / pinned magnetic layer (stacked ferri) / interlayer precursor. ing.

Similarly, with respect to the substrates S2 to S12, the above-mentioned multilayer films were sequentially formed and transported again to the load lock chamber.

Next, the exhaust of the load lock chamber is stopped, and O
_{The two} gases were reacted at a partial pressure of 150 Torr for 1 minute to oxidize the intermediate layer precursors on the 12 substrates at once. After that, the load lock chamber is evacuated again, and the 12 substrates are transported again into the film formation chamber, where the thickness of the intermediate layer precursor becomes 0.3 n.
m of Al was deposited. Further, the twelve substrates were transported again to the load lock chamber, and the precursors were oxidized at once under the same conditions as described above.

Subsequently, the twelve substrates were transported to the film formation chamber, and Co90Fe10 (1) / NiFe was further placed on the intermediate layer (Al ₂ O ₃ ).
(3) / Ta (15) was deposited. Co90Fe10 (1) / NiFe (3) is a free magnetic layer.

In order to impart uniaxial anisotropy to the fixed magnetic layer, a heat treatment was performed by applying a magnetic field of 280 ° C. and 5 kOe in a vacuum. This film was subjected to mesa processing so that the element cross-sectional area became 2 μm ^2, and Cu (500) / Ta (5) was formed as an upper electrode.

The MR of each of the fabricated substrates 1 to 12 was measured. As a result, an MR ratio of about 33% was obtained with RA = 30 Ωμm ² . Variation in MR ratio between substrates is 5%
Was within.

By applying the batch oxidation method as described above, the time required for oxidation can be greatly reduced. As a result, the formation time of the entire multilayer film could be reduced to about 1/3 as compared with the case of individually oxidizing.

Further, devices were fabricated by variously changing the oxygen partial pressure in the load lock chamber, the reaction time, and the substrate heating temperature by radiant heat, and several types of oxidation conditions for obtaining an MR ratio of about 30% or more were obtained. For the same sample, the oxidation conditions of the precursor to be formed into the film twice were the same.

A 0.3-nm thick Al film was directly formed on the substrate.
Was formed, and this Al film was oxidized by applying the oxidation conditions determined above. This process was repeated to obtain an aluminum oxide (AlOx) film having a thickness of 50 nm. When this film was analyzed by the RBS method, it was confirmed that the value of X at which an MR ratio of 30% or more was obtained was 1.2 to 1.5.

A similar experiment was conducted using aluminum nitride (AlN).
About x), it carried out by changing the partial pressure of nitrogen radical, the reaction time, and the conditions of substrate heating. As a result, MR of 30% or more
X obtained was 0.8-1.

(Embodiment 6) In this embodiment, the reactive magnet
First film forming chamber for tron sputtering (attainable vacuum of 5 × 10^-9
Torr) and a second film forming chamber (for
Ultimate vacuum 5 × 10 ^-9Torr) and reaction chamber and load lock
Chamber (attained vacuum of 8 × 10^-8Torr) is the vacuum transfer chamber
(Degree of ultimate vacuum 1 × 10^-8Torr) through the gate valve
A multi-layer film forming apparatus having the same configuration as that of FIG.
Was. Twelve sheets are placed in the reaction chamber and load lock chamber of this device.
6 inch diameter silicon substrate with thermal oxide film (substrates S1-S
12) was attached.

The substrate S1 was transferred from the transfer chamber to the second film formation chamber, and a multilayer film having the following structure was formed.

Ta (3) / Cu (500) / Ta (3) / PtPdMn (30) / Co90Fe1
0 (3) / Ru (0.7) / Co90Fe10 (3) This multilayer film is composed of an underlayer, a lower electrode layer, an underlayer, an antiferromagnetic material,
It has a fixed magnetic layer film configuration.

Next, the substrate S1 is transported to a first film forming chamber, where the first intermediate layer precursor having a thickness of 0.1 mm is formed as a first intermediate layer precursor by reactive sputtering in an atmosphere in which an oxygen gas is added to an Ar gas.
A 3 nm Al-O film was formed. Thereafter, the substrate was transported to the load lock chamber again.

Similarly, after forming a multilayer film on the substrates S2 to S12, the transfer to the load lock chamber was repeated.

After the 12 substrates after film formation were transferred to the load lock chamber, the exhaust of the load lock chamber was stopped, and the pressure was reduced to 60 Torr.
Twelve substrates were collectively oxidized under the condition of one minute. After evacuating the load lock chamber again, the oxidized 12
The two substrates are sequentially transported again to the first film forming chamber, and 0.2-nm thick Al—O is formed as the second intermediate layer precursor under the same oxygen partial pressure as the first intermediate layer precursor. Filmed. After the precursor was formed for each substrate, the intermediate layer precursor was oxidized at once in the load lock chamber under the same conditions as above.

On the intermediate layer thus produced, Co90 was further added.
A film of Fe10 (1) / NiFe (3) / Ta (15) was formed. Then, in order to impart uniaxial anisotropy to the fixed magnetic layer, 260 ° C. in vacuum,
The heat treatment was performed by applying a magnetic field of 5 kOe. This film is subjected to mesa processing so that the element area becomes 0.5 μm ² . Further, Cu (500) / Ta (5) was formed as an upper electrode.

Under the above conditions, when the oxygen flow ratio O ₂ / (Ar + O ₂ ) during the Al—O film formation is changed from 0% to 2%, the respective MR ratios (%) and the normalized resistance RA (Ωμm ² ) was measured. Table 5 shows the results.

When the MR of the fabricated substrates 1 to 12 was measured, the variation among the substrates fabricated under the same conditions was within 5%.

(Table 5) ―――――――――――――――――――――――――― Oxygen flow ratio (%) RA (Ωμm ² ) MR ( %) ―――――――――――――――――――――――――――――― 0 8 5 0.05 8 14 0.1 8 16 0.5 9 15 1.0 10 14 2.0 11 5 ―――――――――――――――――――――――――――― Oxygen flow ratio is the first precursor, Common to the second precursor

From Table 5, it can be confirmed that in the sample in which the intermediate layer precursor was produced while flowing 0.05 to 1% of oxygen during the Al film formation, both low RA and high MR were compatible. However, RA increases with an increase in oxygen flow rate, and 2%
At the above flow rates, the MR decreased. In addition, when the Al—O film formed to have a thickness of 100 nm directly on the substrate while changing the oxygen flow ratio was examined by XRD, as the oxygen flow ratio increased, the crystal grains became finer, At a flow rate of 0.5% or more, it was confirmed that an amorphous phase was contained.

The resistivity of this Al—O film was determined by the four-terminal method and the bridge method.
%, The film was conductive. This is A
This indicates that the l-O film is not completely stoichiometric oxide. Al- produced at an oxygen flow rate ratio of 2%
When an O film was formed on a carbon substrate and measured by RBS, x was about 1.18 in AlOx.

The effect of making the crystal grains fine is that, in addition to oxygen,
Nitrogen, ammonia gas, etc. were also confirmed.

Next, in the above method, the oxygen flow rate when forming the second intermediate layer precursor was set to 2%, and the oxygen flow rate when forming the first intermediate layer precursor was set to 0 to 1%. %, An element was produced. Table 6 shows the measured MR ratio and RA of the device.
Shown in

(Table 6) ―――――――――――――――――――――――――――― Oxygen flow rate ratio (%) RA (Ωμm ² ) MR ( %) ―――――――――――――――――――――――――――― 0 9 12 0.05 9 16 0.1 9 18 0.5 9 17 1.0 10 16 ―――――――――――――――――――――――――――― * Oxygen flow rate applies to the first precursor, the second precursor Body oxygen flow ratio is 2%

From Table 6, it was confirmed that MR was improved when the first intermediate layer precursor was formed in an atmosphere having lower reactivity than the second intermediate layer precursor. A similar phenomenon occurs when Al-
Measurement was also possible during the production of nitrides and carbides such as N and Si-C.

(Example 7) A multilayer film having the following structure was formed on a silicon substrate with a thermal oxide film having a diameter of 6 inches.

Ta (3) / Cu (500) / Ta (3) / PtMn (30) / Co90e10
(3) / Ru (0.7) / Co90Fe10 (3) Then, as a first intermediate layer precursor, a 0.3 nm thick Al
Was held in an atmosphere having an oxygen partial pressure of 0.2 Torr for 3 minutes, and then held in an atmosphere having an oxygen partial pressure of 60 Torr for 30 seconds. Subsequently, as a second intermediate layer precursor, a film thickness of 0.3 nm
Was deposited in an atmosphere having an oxygen partial pressure of 0.2 Torr for 3 minutes, and then held in an atmosphere having an oxygen partial pressure of 60 Torr for 30 seconds. Oxidation of the precursor was performed by introducing a mixed gas of Ar and oxygen into the load lock chamber as in each of the above embodiments.

Subsequently, Co90Fe10 (1) / NiFe
(5) / Ta (15) was formed and heat-treated at 280 ° C. in a magnetic field. Furthermore, using a stepper, the bonding area is 0.2 to
Mesa processing was performed so as to have a thickness of 4 μm ^2, and an upper electrode was laminated to produce an MR element. Thus, the device of Sample a was obtained.

For comparison, an element (sample b) in which the first and second intermediate layer precursors were both oxidized by holding them in an atmosphere having an oxygen partial pressure of 0.2 Torr for 3 minutes, and an oxygen partial pressure of 60
An oxidized element (sample c) was produced by holding the atmosphere for 30 seconds in an atmosphere of rr.

When the MR ratio and RA of each sample were measured, the sample a had an MR ratio of 10% and RA of 7 Ωμm ²
was gotten. On the other hand, in sample b, no change in MR was observed, and RA was 0.1 Ωμm ² or less. Sample c
Then, the MR ratio was only about 5%.

As shown in sample a, various thicknesses of Al
Is oxidized in advance in an atmosphere where the oxygen partial pressure is relatively low and then oxidized in an atmosphere where the relative partial pressure is relatively high,
An intermediate layer was produced.

FIG. 4 shows RA with respect to the total axis of the Al film thickness on the horizontal axis.
FIG. 5 shows the MR ratio with respect to the total thickness of Al. FIG. 4 shows that RA increases exponentially with respect to the total thickness of Al. This is the Al
This shows that the Ox intermediate layer acts as a tunnel resistor, and that the film quality is uniform regardless of the thickness of the intermediate layer from RA of several Ω to close to several MΩ. Also, referring to FIG. 5, it can be confirmed that high MR is obtained in a wide range of RA.

In the case where a plurality of elements were formed on one silicon substrate, the variation of the MR ratio in the substrate was within 5% according to the above method. For comparison, the same measurement was performed on an element formed as an intermediate layer by forming an Al film having a thickness of 1 nm by plasma oxidation.
The variation of the MR ratio was about 10%.

The intermediate layer of nitride or carbide is also formed by exposing the precursor of the intermediate layer to a weak reaction atmosphere and then to a strong reaction atmosphere, so that the dispersion is small, and from the low junction resistance to the high junction resistance. An element having a high MR ratio can be manufactured.

Example 8 The following multilayer film was formed on a silicon substrate provided with a thermal oxide film.

Ta (3) / Cu (500) / Ta (2) / NiFeCr (3) / PtMn (30)
/Co75Fe25(3)/Ru(0.7)/Co75Fe25(3) Further, after forming an Al film as an intermediate layer precursor, a step of nitriding this precursor in radical nitrogen was repeated three times to obtain an AlNx as an intermediate layer. Was formed. The thickness of the precursor and the degree of nitriding were varied as shown in Table 7. In the table, for example
(0.3, 1.0) means a precursor (Al) having a thickness of 0.3 nm
Is nitrided under the condition that x in AlNx becomes 1.0. Note that x under a predetermined condition is a film thickness 100 formed by repeatedly forming an Al film having a predetermined thickness on a carbon substrate and nitriding it under the predetermined condition.
The composition of AlNx in nm was estimated by the average value obtained by RBS.

Further, Co75Fe25 (1) / NiFe
(3) / Ta (5) was deposited and heat-treated in a magnetic field at 280 ° C., followed by mesa processing, and an upper electrode was provided to produce an MR element. MR and RA were measured for each MR element. Table 7 shows the results.

(Table 7) ――――――――――――――――――――――――――――― Intermediate layer preparation conditions MR RA (1st time / 2nd time / 3 (Time) (%) (Ωμm ² ) ――――――――――――――――――――――――――――― (0.3, 0.7) / (0.3, 0.7) / (0.3, 0.7) 540 (0.3, 1.0) / (0.3, 1.0) / (0.3, 1.0) 22 430 (0.3, 1.0) / (0.3, 0.7) / (0.3, 0.5) 6 130 (0.3, 0.5) /(0.3, 0.7) / (0.3, 1.0) 47 300 (0.3, 0.7) / (0.3, 0.9) / (0.3, 1.0) 49 320 ――――――――――――――――――― ――――――――――――

From Table 7, it can be seen that when the intermediate layer is formed n times (n is an integer of 2 or more), a high MR can be obtained by increasing the reaction conditions as n increases. Understand.
The reaction conditions applied to the intermediate layer precursor prepared for the nth time are as follows:
It is preferable that the reaction conditions be stronger than the reaction conditions applied to the intermediate layer precursor prepared in the (n-1) time.

The setting of such reaction conditions is not limited to nitrides, but includes oxidation of AlOx, SiOx, TaOx, etc., SiC
The same effect can be obtained in the diamond conversion reaction of carbides such as graphite.

(Embodiment 9) A film forming chamber (attainable vacuum of 5 × 10 ⁻⁹ Torr) capable of magnetron sputtering, reverse sputtering is possible, nitrogen radicals, oxygen and oxygen radicals can be introduced, and lamp heating is performed. Using a multi-layer film forming apparatus in which a reaction chamber capable of heating substrates by
The following multilayer film was formed on a silicon substrate with a thermal oxide film having a diameter of 3 inches.

Ta (3) / Cu (750) / Ta (3) / NiFeCr (4) / PtMn (30)
/Co90Fe10(3)/Ru(0.9)/Co90Fe10(3)/interlayer/Ni60Fe40
(4) / Ru (0.9) / NiFe (4) / Ta (5) Then, the fixed magnetic layer (Co90Fe10 (3) / Ru (0.
9) / Co90Fe10 (3)) in order to give uniaxial anisotropy, a magnetic field of 5 kOe was applied at 350 ° C. in vacuum. This multilayer film was processed into a mesa shape using a resist pattern so that the element area in the intermediate layer became 0.5 μm ² , and an interlayer insulating film and an upper electrode were further provided. A 300-nm-thick alumina was used as the interlayer insulating film, and Ta (ion) was ion-milled on the upper electrode, and then Cu (750) was formed.

The intermediate layer was prepared by using the compounds shown in Table 8 in the following procedure. First, using a target having a composition excluding oxygen and nitrogen, in an Ar gas atmosphere,
The intermediate layer precursor was formed to have a thickness of 0.3 to 0.4 nm. Next, when the intermediate layer is an oxide, this precursor is transported to a load lock chamber, where oxygen is added to the load lock chamber for 10 to 6 hours.
The precursor was oxidized by introducing 00 Torr and reacting for about 10 seconds to 6 hours. When the intermediate layer was an oxynitride, the intermediate layer was oxidized in the same manner, and was further manufactured by introducing nitrogen radicals into the load lock chamber for 3 to 900 seconds.

Further, the same intermediate layer precursor was used in a thickness of 0.2
A film was formed to have a thickness of about 0.3 nm, and this was oxidized (oxynitrided) in a load lock chamber in the same manner as described above.

The MR of each fabricated device was measured. Further, the volume change rate of the intermediate layer precursor due to oxidation (oxynitridation) was measured. Here, the volume change rate was a ratio of the thickness of the intermediate layer after the reaction to the thickness of the unreacted intermediate layer precursor. The ratio of the film thickness was measured using a transmission electron microscope (TEM).

Table 8 shows the volume change rate and MR.

(Table 8) ――――――――――――――――――――――――――― Middle layer Volume change rate (%) MR (%) ―― ――――――――――――――――――――――――――― MgO 0.8 10 CaO 0.61 FeO 2.10 WO ₃ 3.50 Cr ₂ O ₃ 2.1 1 ――――――――――――――――――――――――――――― MgO ・ Cr ₂ O ₃ 1.05 25 Al ₂ O ₃・Cu ₂ O 1.427 Al ₂ O ₃ · MgO 1.132 Al ₂ O ₃ · FeO 1.537 Al ₂ O ₃ · WO ₃ 2.110 Al ₂ O ₃ · Cr ₂ O ₃ 2.0 21 Al ₂ O ₃ · AlN 1.2 35 ―――――――――――――――――――――――――――――

From Table 8, it can be seen that the volume change rate is 1.05 to 2.
It can be seen that the MR increases in the range of 0, especially in the range of 1.1 to 1.5. When the respective leak currents were evaluated, the oxynitrided Al ₂ O ₃ .AlN showed the lowest leak current characteristics.

Example 10 A multi-layer film having the following structure was formed on a silicon substrate having a 6-inch diameter thermal oxide film using a multi-layer film forming apparatus using magnetron sputtering.

Ta (3) / Cu (750) / Ta (3) / Ni60Fe40 (4) / intermediate layer
/Co76Fe24(3)/Ru(0.9)/Co76Fe24(1)/N80iFe20(3)/PtMn
(30) / Ta (5) Fixed magnetic layer of this multilayer film (Co76Fe24 (3) / Ru (0.9) / Co76Fe
24 (1)) in vacuum to give uniaxial anisotropy
A magnetic field of 50 ° C. and 5 kOe was applied.

It should be noted that Ni80Fe20 is made of Pt formed thereon.
It is formed to increase the crystal orientation of Mn to the (111) plane. When the crystal orientation of PtMn is increased, the unidirectional anisotropy Hua is improved, and the diffusion of Mn during heat treatment can be suppressed.

Then, the intermediate layer was processed into a mesa shape using a resist pattern so that the element area became 1 μm ² , and an interlayer insulating film and an upper electrode were further provided. Alumina is 300 nm as an interlayer insulating film, and Ta is
Was subjected to ion milling to form Cu (750).

As an intermediate layer, P1 to P3 shown in Table 9 were sequentially applied to form an Al oxide or an Al oxynitride.

P1 is a step of oxidizing or nitriding the surface of Ni60Fe40, which is the underlying magnetic layer. P2 is an oxidation condition of the Al film (0.4 nm in film thickness) formed by evacuation. P3 is an Al film (thickness 0.3) formed by evacuation.
nm) oxidation conditions.

In P1 to P3 in Table 9, the types of gases and their pressures are displayed in this order. For example, O ₂ / 10T
Corresponds to a reaction atmosphere of 10 Torr of oxygen gas. The time kept in the atmosphere was 1 minute. MR of fabricated device
And RA are shown in Table 9.

(Table 9) ―――――――――――――――――――――――――――――――― Sample P1 P2 P3 RA MR (Ωμm ² ) (%) ―――――――――――――――――――――――――――――――― S1 None O ₂ / 10T O ₂ / 10T 30 25 _{S2 N 2 / 10T O 2 /} 10T O 2 / 10T 30 38 S3 O 2 / 10T O 2 / 10T O 2 / 10T 45 40 S4 No _{O 2 / 10T O 2 / 100T} 35 26 S5 N 2 / 10T O 2 / 10T O ₂ / 1T 30 41 S6 O ₂ / 10T O ₂ / 10T O ₂ / 1T 45 42 ―――――――――――――――――――――――――――― ――――――

Table 9 shows that a high MR can be obtained by performing P1 for nitriding or oxidizing Ni60Fe40 as the underlying magnetic layer. However, if the oxidation or nitridation conditions at P1 are too strong, the underlying magnetic layer undergoes magnetic deterioration, and the MR decreases.

(Example 11) A film forming chamber capable of magnetron sputtering (attained vacuum of 5 × 10 ^-9 Torr), reverse sputtering was possible, nitrogen radicals, oxygen and oxygen radicals could be introduced, and the substrate was heated by a lamp. A multi-layer film forming apparatus in which a reaction chamber capable of heating was connected by a vacuum transfer chamber was used. Using this apparatus, the following multilayer film was formed on a silicon substrate with a thermal oxide film having a diameter of 3 inches.

Ta (3) / Cu (750) / Ta (3) / NiFeCr (4) / PtMn (30)
/Co91Zr5Ta4(3)/Ru(0.9)/CoZrTa(1.5)/Co75Fe25(1)/Interlayer/Ni60Fe40(4)/Ru(0.9)/NiFe(3)/Ru(0.9)/NiFe(2)/T
a (5) In this multilayer film, the NiFe / Ru / NiFe / Ru / NiFe layer is a laminated ferrimagnetic free magnetic layer. When a laminated ferrimagnetic layer is used, the thermal stability of the free magnetic layer increases. NiFeCr suppresses the diffusion of Mn between layers by increasing the crystallinity of PtMn,
Improve the heat resistance of the element. Since Co91Zr5Ta4 is amorphous, it has the same effect.

In order to impart uniaxial anisotropy to the fixed magnetic layer of the multilayer film, a magnetic field of 5 kOe was applied at 350 ° C. in a vacuum. Next, using a resist pattern so that the element area of the intermediate layer is 0.01 μm ² , processing into a mesa shape,
Further, an interlayer insulating film and an upper electrode were provided. 300 nm of alumina was used as an interlayer insulating film, and Ta (ion) was ion-milled on the upper electrode, and then Cu (750) was formed.

As the intermediate layer, an Al film having a thickness of 0.7 nm was formed as shown in Table 1.
It was made by reacting with a radical of a mixed gas shown in FIG. The reaction time is M under each mixed gas condition.
Optimized to maximize the R value.

(Table 10) ―――――――――――――――――――――――――――― Gas type RA MR (Ωμm ² ) (%) ―――――――――――――――――――――――――――― Ar + O ₂ 120 28 Kr + O ₂ 110 42 Xe + O ₂ 110 40 ―――――――――― ―――――――――――――――――――― Ar + Kr + O ₂ 110 37 Ar + Xe + O ₂ 110 36 ―――――――――――――――――――――― ―――――――― Ar + N ₂ 100 32 Ar + Kr + N ₂ 100 37 Ar + Xe + N ₂ 100 35 ―――――――――――――――――――――――――――――― Ar + Kr + N ₂ + O ₂ 110 43 Ar + Xe + N ₂ + O ₂ 110 41 ――――――――――――――――――――――― ――――――― Kr + N ₂ + O ₂ 110 45 Xe + N ₂ + O ₂ 110 43 ――――――――――――――――――――――――――――――

As shown in Table 10, when the precursor was reacted with oxygen and / or nitrogen in an atmosphere containing Kr or Xe, M
R increased. An atmosphere containing oxygen and nitrogen, particularly a mixed gas obtained by adding Kr to this atmosphere was optimal.

Example 12 A film formation chamber (attainable vacuum of 5 × 10 ⁻⁹ Torr) capable of magnetron sputtering, reverse sputtering was possible, nitrogen radicals, oxygen and oxygen radicals could be introduced, and the substrate was heated by lamp heating. A multi-layer film forming apparatus in which a reaction chamber capable of heating was connected by a vacuum transfer chamber was used. Using this apparatus, the following multilayer film was formed on a silicon substrate having a thermal oxide film having a diameter of 3 inches.

Ta (3) / Cu (750) / Ta (3) / NiFeCr (4) / PtMn (30)
/ Co75Fe25 (3) / first intermediate layer / Fe (4) / second intermediate layer / Cu (10) / Ta
(5) The first intermediate layer is a tunnel insulating layer, and the second intermediate layer is an insulating layer that conducts hot electrons. This multilayer film was processed into a mesa shape so that the element area of the intermediate layer was 1 μm ² , and an interlayer insulating film and an upper electrode were further provided.
300 nm of alumina was used as an interlayer insulating film, and Ta (ion) was ion-milled on the upper electrode, and then Cu (750) was formed.

[0166] In sample A, the first intermediate layer had a thickness of 0.1 mm.
A layer obtained by oxidizing the Al film formed in three steps of 3 nm, 0.2 nm and 0.2 nm, respectively, is used as a second intermediate layer to form an Al film formed in four steps so as to have a total thickness of 1 nm. Each oxidized layer was used.

In sample B, the first intermediate layer was
A layer formed in the same manner as described above is formed as a second intermediate layer in four times so that the total film thickness becomes 1 nm.
When the MR was examined from the change in potential between the magnetic layers sandwiching the first intermediate layer when an external magnetic field using the layers was applied by oxidizing the alloy, Sample B showed a higher MR. Although the details of this reason are unknown, it is considered that the third element (Mg) of the second intermediate layer contributes.

Example 13 The following multilayer film was formed on a silicon substrate having a 6-inch diameter thermal oxide film using a multi-layer film forming apparatus using magnetron sputtering.

Ta (3) / Cu (750) / Ta (3) / NiFeCr (4) / PtMn (30)
/ Co75Fe25 (4) / First intermediate layer / Ni60Fe40 (4) / Ru (0.9) / Ni60Fe
40 (4) / Ru (0.9) / Ni60Fe40 (4) / second intermediate layer / Co75Fe25 (4) / P
tMn (30) / Ta (5) A magnetic field of 280 ° C. and 5 kOe was applied in vacuum to impart uniaxial anisotropy to the fixed magnetic layer of the multilayer film. In this device, a pair of fixed magnetic layers (Co75Fe25) are arranged so as to sandwich a free magnetic layer (NiFe / Ru / NiFe / Ru / NiFe). The first intermediate layer and the first intermediate layer are both tunnel insulating layers. This multilayer film was processed into a mesa shape using a resist pattern so that the element area of each of the two intermediate layers was 0.5 μm ² , and an interlayer insulating film and an upper electrode were provided. 300 nm of alumina as an interlayer insulating film,
Also, after ion milling Ta on the upper electrode, Cu
(750) was formed.

The first intermediate layer and the second intermediate layer were made of Al oxide or Al by the procedures of P1 to P3 shown in Table 11.
An oxynitride was formed.

P1 is the type and pressure of the gas introduced into the 0.4-nm thick Al film formed on the surface of Co75Fe25 after being evacuated to a vacuum. P2 indicates the gas type and gas pressure when oxygen is introduced at 100 Torr after P1. P3 is an oxidation condition for a 0.3-nm-thick Al film formed after evacuating to vacuum.

Here, in P1 to P3, the type of gas and the gas pressure are described in this order. For example, O ₂ / 100T
Indicates a reaction atmosphere of 100 Torr of oxygen gas. P2 is
The total gas pressure with the gas introduced at P1 is displayed. The holding time in the atmosphere was 1 minute for each of P1 to P3. Table 11 shows the MR and RA of the fabricated films.

(Table 11) ―――――――――――――――――――――――――――――――― Sample P1 P2 P3 RA MR (Ωμm ² ) (%) ―――――――――――――――――――――――――――――――― S1 None O ₂ / 100T O ₂ / 100T 60 32 S2 N ₂ / 100T O ₂ + N ₂ / 200T O ₂ / 100T 30 39 S3 Ar / 100T O ₂ + Ar / 200T O ₂ / 100T 45 38 S4 Ar + N ₂ / 100T O ₂ + N ₂ + Ar / 10T O ₂ / 100T 35 38 ――――――――――――――――――――――――――――――――――

[0174] From Table 11, the film-formed Al film, the sample S2~S4 held in an atmosphere containing at least one selected from Ar and N _2, it can be seen that excellent MR characteristics can be obtained.

[0175]

According to the present invention, a magnetoresistive element having a new intermediate layer can be provided. This magnetoresistive effect element realizes characteristics superior to the conventional element, for example, a high M
It is suitable for achieving both the R ratio and a low junction resistance (RA).

[Brief description of the drawings]

FIG. 1 is a diagram illustrating a configuration example of an apparatus for performing a method of the present invention.

FIG. 2 is a diagram showing another configuration example of an apparatus for performing the method of the present invention.

FIG. 3 is a cross-sectional view showing one example of a magnetoresistive element of the present invention.

FIG. 4 is a normalized resistance value (RA) with respect to the thickness of an Al film.
It is a figure showing an example of change of.

FIG. 5 is a diagram showing an example of a change in MR value with respect to the thickness of an Al film.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01F 41/32 H01L 43/12 H01L 43/12 G01R 33/06 R (72) Inventor Nozomi Matsukawa Kazuma, Osaka Matsushita Electric Industrial Co., Ltd. (72) Inventor Kenji Iijima 1006 Ojimon Kadoma, Kadoma City, Osaka Pref. Matsushita Electric Industrial Co., Ltd. F term (for reference) 2G017 AD55 AD63 AD65 5D034 BA03 BA15 DA07 5E049 BA12 CB02 DB12

Claims (24)

[Claims] 1. An intermediate layer comprising: an intermediate layer; and a pair of magnetic layers sandwiching the intermediate layer, wherein the intermediate layer includes at least three kinds of elements selected from Groups 2 to 17, wherein the elements are F, O ,
A magnetoresistive element including at least one selected from N, C and B. 2. The magnetoresistive element according to claim 1, which contains a metal element other than Al. 3. The magnetoresistive element according to claim 1, wherein the intermediate layer contains at least two kinds of elements other than F, O, C, N and B and selected from Groups 2 to 17. 4. The magnetoresistive element according to claim 1, wherein the intermediate layer contains at least two elements selected from B, Al, Ga and In, and N. 5. The magnetoresistive element according to claim 1, wherein the composition of the intermediate layer changes along the thickness direction. 6. The magnetoresistive element according to claim 1, wherein the intermediate layer has a multilayer structure. 7. The magnetoresistive element according to claim 6, wherein the intermediate layer includes two films having different barrier heights. 8. A first intermediate film in which the intermediate layer is in contact with one of the pair of magnetic layers, a second intermediate film in contact with the other of the pair of magnetic layers, the first intermediate film and the second intermediate film. And a third intermediate film sandwiched between the first and second intermediate films, wherein a barrier height of the third intermediate film is lower than at least one selected from a barrier height of the first intermediate film and a barrier height of the second intermediate film. Claim 7
3. The magnetoresistive effect element according to 1. 9. The magnetoresistance effect according to claim 6, wherein the intermediate layer includes a magnetic film, and at least one nonmagnetic film is interposed between the magnetic film and the pair of magnetic layers. element. 10. The intermediate layer includes a non-magnetic metal film.
3. The magnetoresistive effect element according to 1. 11. At least one of the pair of magnetic layers is
2. The magnetoresistance effect element according to claim 1, comprising at least one selected from F, O, N, C and B. 12. The magnetoresistive element according to claim 1, wherein a ferromagnetic material having a thickness of 0.5 nm or less is interposed between at least one of the pair of magnetic layers and the intermediate layer. 13. The intermediate layer has a thickness of 0.5 nm or more and 5 n or more.
The magnetoresistive element according to claim 1, wherein m is equal to or less than m. 14. A method of manufacturing a magnetoresistive element having an intermediate layer and a pair of magnetic layers sandwiching the intermediate layer, wherein a step of forming a precursor is performed, and wherein an oxygen atom, a nitrogen atom, and a carbon atom are formed. Reacting the precursor with the reactive species in a reaction atmosphere containing at least one reactive species selected from the group consisting of at least one reactive species to form at least a part of the intermediate layer. 15. The method according to claim 14, wherein the precursor is formed in a reaction atmosphere containing at least one reactive species selected from an oxygen atom, a nitrogen atom, and a carbon atom. 16. A step of forming a first precursor in a first reaction atmosphere, a step of forming the first precursor into a first intermediate film that becomes a part of the intermediate layer, and a step of forming the first intermediate film. A step of forming a second precursor film under a second reaction atmosphere, and a step of forming the second precursor into a second intermediate film that becomes a part of the intermediate layer, wherein the second reaction atmosphere The method of manufacturing a magnetoresistive effect element according to claim 15, wherein the first element has a higher reactivity than the first reaction atmosphere. 17. A step of forming a first precursor, a step of forming the first precursor into a first intermediate film that becomes a part of the intermediate layer in a first reaction atmosphere, and a step of forming the first intermediate film. Forming a second precursor thereon, and forming the second precursor into a second intermediate film that becomes a part of the intermediate layer in a second reaction atmosphere, wherein the second reaction atmosphere is The method for manufacturing a magnetoresistive element according to claim 14, wherein the method has a higher reactivity than the first reaction atmosphere. 18. The ratio of the volume Va of the film formed from the precursor to the volume Vb of the precursor is 1.05 or more.
The method of manufacturing a magnetoresistive element according to claim 14, wherein the value is 0 or less. 19. The method according to claim 18, wherein the precursor contains a metal element other than Al. 20. The method according to claim 14, wherein the reaction atmosphere contains at least oxygen atoms and nitrogen atoms. 21. The method according to claim 14, wherein the reaction atmosphere contains at least one kind selected from Kr atoms and Xe atoms. 22. A second atmosphere containing at least one selected from Ar and nitrogen atoms and an oxygen atom after contacting the precursor with a first atmosphere containing at least one selected from Ar atoms and nitrogen atoms. The method for manufacturing a magnetoresistive element according to claim 14, wherein 23. The method according to claim 14, wherein the intermediate layer precursor contains an amorphous phase. 24. A step of forming a first magnetic layer on each of at least two substrates; a step of forming a precursor on each of the first magnetic layers in the same film forming chamber; Transferring the substrate from the film forming chamber to the reaction chamber, making the precursor at least part of an intermediate layer in the reaction chamber under the same reaction atmosphere, and forming a second magnetic layer on the intermediate layer, respectively. The method for manufacturing a magnetoresistive element according to claim 14, comprising a step of forming a layer.