Magneto-resistive devices

[0001] 1. Field of the Invention

[0002] The present invention relates to a magneto-resistive device and any of a magnetic head, a magnetic recording device, and a magnetic memory, which is provided with said magneto-resistive device.

[0003] 2. Description of Related Art

[0004] Magnetic recording-reproducing devices have recently shown a significant improvement in recoding density. They are provided with a magnetic recording-reproducing head which needs both high recording performance and high reproducing performance.

[0005] What is particularly required of magnetic recording heads is technical innovation for (1) higher sensitivity, (2) smaller track width, and (3) smaller reproducing gap.

[0006] Higher sensitivity leads to higher recording density. A recording density of the order of 1-10 Gb/in² relies on the anisotropic magneto-resistive effect (AMR), and a recording density of the order of 10-20 Gb/in² relies on the giant magneto-resistive effect (GMR) which gives a higher sensitivity. Moreover, it is expected that a much higher recording density of the order of 20-50 Gb/in² will be attained with the help of the advanced GMR, such as specular GMR and NOL-GMR (nano-oxide layer type GMR), which has a highly polarized material or an oxide layer interposed between the interfaces of GMR structure for an increased output through the multiple reflection effect of electron spin.

[0007] A magnetic head relying on GMR is disclosed in JP-A No. 358310/1992. This magnetic head, which is of spin valve structure, consists of a pinned layer, a non-magnetic thin film (spacer), a free layer, and amagneto-resistive device. The pinned layer is a magnetic body whose magnetization is fixed in a specific direction by an antiferromagnetic layer. The non-magnetic thin film is laminated on the pinned layer. The free layer is a magnetic film which is laminated on the non-magnetic thin film. The magneto-resistive device changes in electric resistance depending on the relative angle of magnetization of the pinned layer and the free layer.

[0008] The higher recording density expected in the future needs a reproducing system which is much more sensitive than before. A recording density of the order of 70-150 Gb/in² will rely on the tunneling magneto-resistive effect (TMR) with an extremely high MR ratio because of its high sensitivity. A higher recording density exceeding 150 Gb/in² will rely mainly on CPP-GMR (current perpendicular to plane geometry GMR) which works with a detecting current flowing in the direction perpendicular to the film surface. The basic technology of TMR is disclosed in P03-154217 and JP-A 91925/1998. Unfortunately, it needs further improvement in breakdown by static voltage (due to the very thin insulator important for the characteristic properties), reduced resistance for better S/N ratio, and increased bias.

[0009] The conventional CIP-GMR (current-in-plane GMR, in which the detecting current flows in the in-plane direction of the film) has the following disadvantages. For a high linear recording density, a smaller space is necessary between the GMR device and each of the magnetic shield films arranged above and below it. This results in a thinner insulator between the GMR device and the shield film, which does not provide sufficient insulation. Moreover, the reduced reproducing track width makes magnetic domain control difficult and produces asymmetric output signals.

[0010] By contrast, in the case of CPP-GMR, insulation between shield films is not important because both sides of the device function as the electrodes. Therefore, CPP-GMR will be considerably free from thermal breakdown due to current and non-linearity caused by magnetic field. Moreover, it is promising for high recording densities because it will increase in output as the device area decreases. Much has been reported about CPP-GMR, typically, in JP (PCT) No. 509956/1999 and JP-A No. 221363/1995.

[0011] Among the promising magnetic reproducing devices is a highly sensitive magneto-resistive sensor in which current flows in the thickness direction of the magneto-resistive device. It typically includes CPP-GMR (current-perpendicular to plane GMR) and TMR (tunneling magneto-resistive effect). These magneto-resistive sensors are basically so constructed as to work with the sensing current flowing perpendicularly to the film surface. This leads us to anticipate that the future magnetic reproducing device will be the one which uses the sensing current of CPP type.

[0012] The TMR device is one which has a pair of magnetic films holding an insulating barrier film between them and causes the sensing current to flow in the thickness direction of the these films. Conduction through the insulating barrier layer presents a high resistance. This poses some problems (such as noise and reduced S/N ratio) when it is used for the reproducing head or the magnetic field sensor. To address these problems, active investigations are going on regarding how to reduce resistance through the thinning of the insulating barrier layer. Unfortunately, reduction in resistance is accompanied by reduction in output. Another problem with the TMR device is that it increases in resistance according as its surface area decreases.

[0013] Unlike the TMR device, the CPP-GMR is constructed such that a pair of magnetic films hold a non-magnetic film and the current flows in the thickness direction of the films. CPP-GMR (with current flowing in the thickness direction of the film) has a shorter current pass than CIP-GMR (with current flowing perpendicularly the thickness direction of the film). Therefore, the conventional GMR film has a resistance as low as milliohms even in the case of a device with a surface area of 1 m². In other words, CPP-GMR has too low a resistance to be applied to the magnetic reproducing device. Moreover, the conventional GMR film has a high ratio of resistance change (several percent) in the CPP direction but has a very small output on account of the excessively low resistance.

[0014] The foregoing has aroused a demand for a new material which has a proper degree of resistivity and a large GMR output.

[0015] There are important problems involved with CPP-GMR as follows.

[0016] (1) Anew process for manufacturing devices in smaller size.

[0017] (2) A new material and a new film structure which will increase the ratio of change in the magnetic resistance of the device.

[0018] (3) A new film structure to control the electric resistance of the device.

[0019] The first problem has arisen from the fact that about 0.30.3 m is the minimum size of the device that can be manufactured by the current photo-lithography technique which employs an aligner or stepper. In the case where an ordinary GMR film is used for the device of CPP-GMR type, this size (or device area) has such a low resistance that its output is as small as the limit of measurement. This is because the GMR film is a multi-layered metal film with a thickness of tens of nanometers (which produces an excessively small resistance). Therefore, in the case of CPP-GMR, the device should be smaller than 0.10.1 m or should be manufactured from a new material which produces an adequate resistance for a certain device area. Reduction in the device area may be accomplished by lithography using the technique of atomic force microcopy or by electron beam lithography. These technologies, however, are still incapable of manufacturing devices smaller than 0.10.1 m.

[0020] It is an object of the present invention to provide a magneto-resistive device and any of a magnetic head, a magnetic recording device, and a magnetic memory, which is provided with said magneto-resistive device. This magneto-resistive device has a high ratio of change in resistance by applied magnetic field, an adequately controlled electric resistance, and an increased reproducing output on account of the adequate selection of materials and film structure, which solve the above-mentioned problems (2) and (3), with the device size being reduced as far as possible by using the existing technology.

[0021] The first aspect of the present invention resides in a magneto-resistive device having a first magnetic layer, a second magnetic layer, and a non-magnetic spacer formed between said first and second magnetic layers, wherein said first magnetic layer contains a magnetic material whose conduction electrons belong to a first energy band and said second magnetic layer contains a magnetic material whose conduction electrons belong to a second energy band, with said first and second energy bands being attributable to orbitals of the same kind.

[0022] The second aspect of the present invention resides in a magneto-resistive device having a first magnetic layer, a second magnetic layer, and a non-magnetic spacer formed between said first and second magnetic layers, wherein at least either of said first magnetic layer and said second magnetic layer contains a magnetic material whose conduction electrons belong to a first energy band and said non-magnetic spacer contains a non-magnetic material whose conduction electrons belong to a second energy band, with said first and second energy bands being attributable to orbitals of the same kind.

[0023] The third aspect of the present invention resides in a magneto-resistive device having a first magnetic layer, a second magnetic layer, and a non-magnetic spacer formed between said first and second magnetic layers, wherein said first magnetic layer and said second magnetic layer contain a half-metallic ferromagnetic material or a highly polarized magnetic material.

[0024] The fourth aspect of the present invention resides in any of a magnetic head, a magnetic recording device, and a magnetic memory, which is provided with said magneto-resistive device.

[0025] The above-mentioned magneto-resistive device, magnetic head, magnetic recording device, and magnetic memory are characterized by a high ratio of change in resistance by applied magnetic field, an adequately controlled electric resistance, and an increased output which result from the adequate film structure and adequate material selection for the magneto-resistive device.

[0026] FIG. 1 is a schematic diagram showing the state of electron density (DOS);

[0027] FIG. 2 is a diagram showing the dependence on temperature of the saturation magnetization of Fe₃O₄ film formed on a noble metal film (Au);

[0028] FIG. 3 is a diagram showing the dependence on film thickness of the X-ray diffraction pattern of Fe₃O₄ film formed on a noble metal film (Au);

[0029] FIG. 4 is a diagram showing the dependence on film thickness of the saturation magnetization of Fe₃O₄ film formed on a noble metal film (Au);

[0030] FIG. 5 is a diagram which visualizes the model of the device structure used to calculate the ratio of change in resistance;

[0031] FIG. 6 is a diagram modeling the electron state in each layer which was used to calculate the ratio of change in resistance;

[0032] FIG. 7 is a schematic diagram showing a magneto-resistive device for which calculations were performed according to the present invention;

[0033] FIG. 8 is a schematic diagram showing a magneto-resistive device for which calculations were performed according to the present invention;

[0034] FIG. 9 is a schematic diagram showing a magneto-resistive device for which calculations were performed according to the present invention;

[0035] FIG. 10 is a schematic diagram showing a magneto-resistive device for which calculations were performed according to the present invention;

[0036] FIG. 11 is a schematic diagram showing a magneto-resistive device for which calculations were performed according to the present invention;

[0037] FIG. 12 is a schematic diagram showing a magneto-resistive device for which calculations were performed according to the present invention;

[0038] FIG. 13 is a schematic diagram showing the magneto-resistive device of the present invention and also showing the result of calculations;

[0039] FIG. 14 is a schematic diagram showing the magneto-resistive device of the present invention and also showing the result of calculations;

[0040] FIG. 15 is a schematic diagram showing a magneto-resistive device for which calculations were performed according to the present invention;

[0041] FIG. 16 is a schematic diagram showing the basic structure of the magneto-resistive device;

[0042] FIG. 17 is a diagram showing the result of the measurements carried out for the magneto-resistive device of the present invention;

[0043] FIG. 18 is a diagram showing the structure of the CPP-GMR to which the present invention is applied;

[0044] FIG. 19 is a diagram showing the result of the measurements carried out for the magneto-resistive device of the present invention;

[0045] FIG. 20 is a schematic diagram showing the magneto-resistive device to which the present invention is applied;

[0046] FIG. 21 is a schematic diagram showing the magneto-resistive device to which the present invention is applied;

[0047] FIG. 22 is a sectional view of the CPP-GMR reproducing head of in-gap type to which the present invention is applied (as viewed from the side facing the recording medium);

[0048] FIG. 23 is a schematic diagram showing the magneto-resistive device to which the present invention is applied;

[0049] FIG. 24 is a sectional view of the CPP-GMR reproducing head of in-gap type to which the present invention is applied (as viewed from the side facing the recording medium);

[0050] FIG. 25 is a schematic diagram showing how the yoke is positioned relative to the magneto-resistive device to which the present invention is applied;

[0051] FIG. 26 is a schematic diagram showing how the yoke is positioned relative to the magneto-resistive device to which the present invention is applied;

[0052] FIG. 27 is a schematic diagram showing the magnetic recording-reproducing unit to which the present invention is applied;

[0053] FIG. 28 is a schematic diagram showing the magnetic memory to which the present invention is applied;

[0054] FIG. 29 is a schematic diagram showing the magnetic memory to which the present invention is applied;

[0055] FIG. 30 is a schematic diagram showing the magnetic memory to which the present invention is applied; and

[0056] FIG. 31 is a schematic diagram showing the magnetic memory to which the present invention is applied.

[0057] The following is a detailed description of the magneto-resistive device, magnetic head, magnetic recording unit, and magnetic memory to which the present invention is favorably applied.

[0058] The magnetic head according to the present invention is provided with a magneto-resistive device having a first magnetic layer (free layer), a second magnetic layer (pinned layer), and a spacer interposed between said first and second magnetic layers.

[0059] The magneto-resistive device may be one which has an antiferromagnetic layer, a soft magnetic layer, and a noble metal layer, said antiferromagnetic layer being formed on the surface opposite to that surface facing the spacer of the second magnetic layer, said soft magnetic layer being formed between the pinned layer and said antiferromagnetic layer, and said noble metal layer being formed between the pinned layer and said soft magnetic layer.

[0060] The pinned layer and free layer each contain at least one species of Heusler alloys and half-metals (any of Fe₃O₄, CrO₂, and ZnO which is incorporated with a transition metal). The first feature of this magneto-resistive device is that its spacer has half-metal arranged on both sides thereof.

[0061] Half-metal is a material which is characterized by its electron structure as shown in part (a) of FIG. 1. The electron structure will be briefly described in the following. Incidentally, parts (a), (b), and (c) of FIG. 1 show the electron density state of half-metal magnetic material, non-magnetic metal, and magnetic metal, respectively.

[0062] In general, metal (non-magnetic) takes on the electron structure as shown in part (b) of FIG. 1. This diagram shows that the energy level changes from the low (stable) state to the high state in going upward. The horizontal axis represents the electron density, with the center being zero. The right-hand and left-hand sides separated by the center line indicate that electrons have two kinds of electron spin. For convenience's sake, the right-hand side denotes up spin () and the left-hand side denotes down spin ().

[0063] The energy level E_F in the diagram denotes the Fermi surface, electrons in which are largely responsible for electric conduction. Metal has the electron density in the Fermi surface, in which there are free electrons which conduct electricity. Half-metal is a substance characterized in that electrons in the Fermi surface have either up spin or down spin.

[0064] The electron spin closely relates to the magnetic properties. A magnetic material is characterized by that the total number of electrons in the band under the Fermi surface greatly varies depending on whether electrons are those of up spin or down spin. By contrast, a half-metal material is characterized by that all electrons in the Fermi surface are those of polarized spin.

[0065] Consequently, there really exists materials which behave as both half-metal and ferromagnet. They are commonly called half-metal magnetic material; however, they are collectively referred to as half-metal hereinafter because many half-metals are magnetic materials. The deviation of spin is referred to as polarizability (P). It is represented by the formula (1) below, wherein n denotes the number of up spin electrons at the Fermi surface and n denotes the number of down spin electrons at the Fermi surface.

[0066] What occurs in half-metal under application of current is that those electrons having the same spin components as the direction of electron spin of half-metal conduct through the half-metal but those electrons having spin in the opposite direction do not conduct due to repulsion force. This suggests that the spin valve structure consisting of a half-metal magnetic material and a metal magnetic material joined together, with a non-magnetic metal interposed between them, would greatly change in resistance by applied magnetic field when the magnetization of the metal magnetic film is reversed by an external magnetic field, if the metal magnetic material is formed from a soft magnetic material.

[0067] It is considered in principle that the spin valve structure as mentioned above will change in resistance infinitely if the half-metal magnetic material has a 100% polarizability. Therefore, it is expected that a spin valve structure with a half-metal magnetic material will give an increased output owing to an increased ratio of change in resistance.

[0068] Actually, change in resistance is finite because the band to which electrons existing on the Fermi surface governs the efficiency of electron conduction to other substances. To be concrete, electrons divide into some groups according to their angular momenta and orbitals (such as 1 s, 2 p, and 3 d), each group being referred to as band. When two materials are joined together, electron conduction does not take place efficiently if they have s-electrons and d-electrons, respectively, at the Fermi surface, because the spin information passes from s-electrons to d-electrons through a few s-electrons and other complex routes (with reflection) rather than directly. In addition, if the two materials extremely differ in resistance, an appreciable loss due to reflection occurs because the flow of electrons is inhibited.

[0069] The film structure with an interface is identical with that of GMR film. If a combination of adequate materials is made such that electron conduction is maximum at the interface between the pinned layer and the space or at the interface between the spacer and the free layer, then an increased ratio of change in resistance will be expected.

[0070] The above-mentioned half-metal magnetic materials fall under three major categories: magnetic semiconductors, part of oxide magnetic materials, and Heusler alloys.

[0071] Magnetic semiconductors include CrAs, CrSb, and dilute magnetic semiconductors (such as InMaAs and GaMnAs) The last one is formed from a III-V compound semiconductor with a crystal structure of zinc blende type by doping with a magnetic material such as Mn. They are prepared in single-crystal form by molecular beam epitaxy (MBE).

[0072] Magnetic semiconductors usually behave like half-metal at low temperatures (below 10K). However, those of ZnO and GaN doped with a transition metal and those having a crystal structure of zinc blende type exhibit the ferromagnetic properties at room temperature. They belong to the category of half-metal. There are some exceptions; for example, CrSb and CrAs exhibit magnetic properties at high temperatures (350K and Tc>1000K, respectively).

[0073] A well-known example of oxide magnetic materials is Fe₃O₄. Other examples include CrO₂ and LaSrMnO, which can be used as half-metal materials. Fe₃O₄ is important because it exhibits half-metal characteristics at room temperature and it is a soft magnetic material capable of significant magnetization. Nevertheless, it has never been put to practical use because it needs high temperatures (exceeding 500 C.) if it is to be obtained in the form of single-layer film on a single crystal substrate.

[0074] Oxide half-metal magnetic materials have never been made into an actual magnetic head (or other devices) because they have to be processed at high temperatures. In addition, Fe₃O₄ tends to form a multiple phase with Fe₂O₃ and Fe. The former is stable and similar to Fe₃O₄ in composition but is not half-metal with a weak tendency toward magnetization. CrO₂ also readily mixes with Cr₂O₃, which is an insulating material, and hence needs a special process at high temperatures in an oxygen atmosphere.

[0075] It is possible to form a single phase of Fe₃O₄ by controlling its growing energy. All that is required to achieve this object is to form a noble metal film on a substrate by RF sputtering and then form Fe₃O₄ on it. This process gives rise to a film on a substrate kept at 300 C. The resulting film is known to be a single layer of Fe₃O₄ from its X-ray diffraction pattern. Its saturation magnetization at room temperature is 0.55-0.6 tesla, which is similar to that of bulk Fe₃O₄ (0.5-0.6 tesla). It also exhibits Verwey transition (anomalous temperature dependence of saturation magnetization at about 120K) which is characteristic of Fe₃O₄. Almost the same phenomena as mentioned above are noticed in the film formed on a substrate at 250 C. or above. Any film formed on a substrate at 150-200 C. exhibits saturation magnetization greater than 0.5 tesla. These facts suggest that the above-mentioned process can yield a single-phase film of Fe₃O₄ which is as thin as several nanometers.

[0076] Heusler alloy is unique in its structure represented by Cu₂MnAl. It is renowned for its ferromagnetism resulting from localized magnetic moment in regularly arranged Mn atoms. In general, it exhibits its high ferromagnetism and high Tc when its component is partly replaced. For example, replacement of Cu gives (MMn)₂Al₂ (where M denotes Cu, Ni, Co, or Fe) and replacement of Al by Si, Sn, or Ge gives Cu₂MnSi or the like. Its magnetism arises from d-electrons of Mn and its conductivity is attributable to s-electrons and d-electrons. It is completely polarized by the long-range mutual action by d-electrons of Mn. This is a probable reason why it behaves as half-metal. The above-mentioned materials can be formed by molecular beam epitaxy or sputtering on a substrate at 300 C. The resulting product can be made completely regular by prolonged heat treatment at 500-800 C.

[0077] What is important here is the comparison of magnetoresistive effect between two different structures. One structure is formed by joining together a magnetic film containing a half-metal magnetic material and a magnetic film containing a magnetic material containing a half-metal, with a spacer interposed between them. The other structure is formed by joining together a magnetic film containing a half-metal magnetic material and a magnetic film containing another magnetic material, with a spacer interposed between them. Calculations were carried out in consideration of bonding and electron transport at the interface. The results are as follows.

[0078] (1) Change in resistance by applied magnetic field is positive or negative, if one magnetic film has CPP-GMR structure of d-electron half-metal, the spacer has s-electrons, and the other magnetic film has s-electrons.

[0079] (2) Change in resistance by applied magnetic field is positive, if one magnetic film has CPP-GMR structure of d-electron half-metal, the spacer has d-electrons, and the other magnetic film has s-electrons.

[0080] (3) Change in resistance by applied magnetic field is positive (nearly 100%), if one magnetic film has CPP-GMR structure of d-electron half-metal, the spacer has s-electrons, and the other magnetic film has d-electrons. However, loss due to reflection and scattering is large because of a small number of electrons.

[0081] (4) Change in resistance by applied magnetic field is small, or the balance between (1) and (3), if one magnetic film has CPP-GMR structure of d-electron half-metal, the spacer has s-electrons, and the other magnetic film has s-electrons and d-electrons.

[0082] (5) Change in resistance by applied magnetic field is equal to the balance between (1) and (2), if one magnetic film has CPP-GMR structure of d-electron half-metal, the spacer has s-electrons and d-electrons, and the other magnetic film has s-electrons.

[0083] (6) Change in resistance by applied magnetic field is nearly 100%, if one magnetic film has CPP-GMR structure of d-electron half-metal, the spacer has d-electrons and the other magnetic film has d-electrons.

[0084] The foregoing suggests that the spacer and free layer will have the optimal electron state if adequate materials are specified on the basis of electron species at the Fermi surface.

[0085] In the case of ordinary Fe₃O₄/Au/NiFe structure, the Fe₃O₄ layer has d-electrons constituting the Fermi surface, the Au layer has s-electrons, and NiFe layer has s-electrons and d-electrons which are mixed up. This structure corresponds to the one (4) mentioned above, and it gives a small ratio of change in resistance by applied magnetic field (R/R).

[0086] By contrast, there is another possible structure in which the free layer is formed from Fe in place of NiFe. Since Fe has a large d-electron density at the Fermi surface, this structure is similar to the one (2) mentioned above, and it gives a higher R/R. Moreover, another structure, in which the free layer is formed from Fe₃O₄ (half-metal having 100% d-electrons) in place of NiFe, also gives a higher R/R.

[0087] Further another structure in which Au for the spacer is replaced by Pt having d-electrons at the Fermi surface is also expected to give a higher R/R. Moreover, there is another possible structure in which Au for the spacer is replaced by an oxide semiconductor (such as TiO₂) having d-electrons at the Fermi surface. This structure corresponds to the one (6) mentioned above, and it will give a very high R/R. The device with this structure is composed of layers each having almost the same resistivity and hence it will suffer a minimum reflection loss due to impedance mismatch.

[0088] In a magnetoresistive device, the half-metal magnetic material constitutes the magnetic film adjacent to the free layer and the pinned layer. The pinned layer has its magnetization fixed by the antiferromagnetic coupling which is applied to the ordinary GMR reproducing head. In this case, the antiferromagnetic film should be formed on a metal magnetic film of NiFe or the like as an underlying layer. If a metal magnetic film or an antiferromagnetic film is formed on an oxide magnetic film, oxygen diffuses into the metal magnetic film from the oxide magnetic material (half-metal magnetic material). This oxygen diffusion deteriorates the half-metal and metal magnetic film, thereby decreasing reliability.

[0089] The present inventors adopted, instead of the conventional structure mentioned above, a new structure in which an antiferromagnetic film and an oxide magnetic film (half-metal) are bonded together with a synthetic ferromagnetic structure interposed between them. This new structure greatly improves reliability because the ferromagnetic spacer (noble metal film) prevents oxidation regardless of whether it is above or below the antiferromagnetic film. This structure is new in that the synthetic ferromagnetic bond is formed between a metal magnetic film and an oxide magnetic film.

[0090] Incidentally, the antiferromagnetic film may be formed from such material as MnPt, CrMnPt, PdMnPt, and MnIr.

[0091] A promising way to control magnetic domains is to use the closed flux structure (CFS) or hard bias structure. The former consists of a free layer, a non-magnetic spacer, a soft magnetic film, and an antiferromagnetic film, which are formed sequentially one over the other. (The non-magnetic spacer is formed on that surface of the free layer which is opposite to the surface in contact with the spacer.) A device in this structure prevents occurrence of magnetic domains because the magnetic pole appearing at the end of the soft magnetic film and the magnetic pole appearing at the end of the free layer cancel out each other through static magnetic coupling. This effect becomes more salient as the device area decreases. (Devices with a large area are affected by in-plane coupling.) The hard bias structure is provided with a permanent magnet such that the magnetic pole at the end of the permanent magnet prevents magnetic domains from occurring in the free layer. (The permanent magnet is arranged such that it is in contact with the device in its section cut in the track width direction of the device.) This structure has been in practical use to a certain extent. A problem involved in this structure is that the permanent magnet should be in contact with the device accurately and symmetrically. It is difficult to maintain accuracy and control magnetic domains as the device area decreases.

[0092] A magnetic film containing Fe₃O₄ as half-metal magnetic material was formed by RF sputtering on a substrate of glass, magnesium oxide, GaAs, AlTiC, SiC, Al₂O₃, SiO₂, or the like.

[0093] The RF sputtering was carried out under the following conditions.

[0094] Target: sintered body of Fe₃O₄

[0095] Atmosphere: argon at about 1-0.1 Pa

[0096] Power: 50-150 W

[0097] Maximum degree of vacuum achieved: lower than 510³ Pa

[0098] Rate of film growth: less than 0.1 /s

[0099] It was found that the Fe₃O₄ film can also be formed very slowly at a growth rate of 0.1-0.01 /s by molecular beam epitaxy (MBE), with oxygen being admitted into the atmosphere while Fe is being deposited.

[0100] The Fe₃O₄ film formed directly on the above-mentioned substrate varies in saturation magnetization depending on the substrate temperate, from less than 0.1 tesla (at room temperature) to 0.2-0.3 tesla (at 400 C.). These values are rather low for the single layer of Fe₃O₄.

[0101] The Fe₃O₄ film formed in this manner was found to be strongly amorphous. In order to make the amorphous film into a nearly complete single-layer film, it is usually necessary to raise the substrate temperature above 540 C. to promote crystallization. However, the present inventors succeeded in forming a Fe₃O₄ film (10-50 nm thick) having saturation magnetization higher than 0.4 tesla on a single-crystal substrate at 250 C. or above by a newly developed sputtering method. This method is characterized by a reduced H₂O fraction ratio in the sputtering chamber and a low growth rate and a low energy.

[0102] The resulting film exhibited the temperature dependence of resistance, which is similar to that of semiconductor at high temperatures above 120K, as shown in FIG. 2. The curve indicates the Verwey transition in the vicinity of 120K, which is a phenomenon characteristic of Fe₃O₄ (transition into an insulator). Moreover, the resulting film gave X-ray diffraction patterns as shown FIG. 3, which are attributable to Fe₃O₄. The Fe₃O₄ obtained in this manner is known to have half-metallic characteristics theoretically and from the past spectroscopic analyses. It has been confirmed that this material remains crystalline until the film thickness reaches 5 nm.

[0103] The Fe₃O₄ film has the thickness dependence of saturation magnetization as shown in FIG. 4. It is noted from FIG. 4 that saturation magnetization tends to decrease rapidly as the film thickness decreases. However, a film as thin as about 1 nm still remains magnetized. Saturation magnetization decreased from about 0.5 tesla (for the film thickness larger than 10 nm) to about 0.4 tesla (for the film thickness smaller than 0.8 nm). This suggests that even such a thin film still keeps the ferromagnetic properties characteristic of magnetite. An excessively thin film does not suit the magnetic reproducing head because it abruptly changes in characteristic properties.

[0104] A magnetic film containing half-metal Fe₃O₄ was formed on a substrate, with an underlying layer of noble metal interposed between them.

[0105] If half-metal Fe₃O₄ is to be applied to the magneto-resistive device of the magnetic reproducing head, it is necessary to provide a conductive film (which functions as both an electrode and an underlying layer) to the lower part of the device. An adequate underlying film is expected to lower the growth temperature. So, a noble metal film, 2 nm thick, was formed on the above-mentioned substrate from each of Pt, Pd, Rh, Ru, Ir, Au, Ag, and Cu. On the noble metal film was formed a Fe₃O₄ film, 50 nm thick, by the above-mentioned method. The resulting sample was tested for the temperature dependence of magnetic properties. All the samples were found to be satisfactory. Particularly, the Fe₃O₄ film formed on the underlying film of Au, Pd, or Pt gave saturation magnetization of about 0.5 tesla even though the substrate temperature is as low as 200 C. In addition, this Fe₃O₄ film has a coercive force of about 1 A/m which proves it to be a good soft magnetic film.

[0106] The underlying noble metal film may be made thicker (50-100 nm) than mentioned above. In this case the same value mentioned above can be obtained if the surface roughness (Ra) is reduced to 0.4 nm or below. Moreover, it is also possible to form the noble metal layer on an underlying layer of Cr or Ta (about 5-50 nm thick). This underlying layer smoothens the noble metal layer formed thereon, and the smooth surface helps the Fe₃O₄ film to grow thereon.

[0107] The half-metal film to be applied to the reproducing head should exhibit the above-mentioned characteristic properties when it is about 1 nm thick. The problem with reduction in film thickness is that thermal energy dominates over magnetic energy due to magnetic spin in magnetic particles constituting the film. Thus the film becomes super-paramagnetic, with random directions of magnetization. Therefore, the half-metal film should be thicker than the critical thickness at which it becomes super-paramagnetic. The pinned layer may maintain its magnetization characteristics if the thin half-metal layer is magnetized by an antiferromagnetic film or a ferromagnetic film in contact therewith.

[0108] A film of oxide half-metal was grown from CrO₂, ZnO, or GaN (in place of Fe₃O₄) on an underlying noble metal film in the same way as mentioned above. It was found that a single-layer film grew even on a substrate at 250 C. ZnO behaves like ferromagnetic half-metal when it is doped with a ferromagnetic metal, such as V, Cr, Fe, Co, and Ni, as much as 25%. Likewise, GaN also behaves like ferromagnetic half-metal when it is doped with Mn, as much as 25%. These materials can also be made into a film on an underlying noble metal film.

[0109] Heusler alloy is a material which has a characteristic structure of Cu₂MnAl. It is renowned for ferromagnetism due to magnetic moment localized in Mn atoms in its regular state. It is usually used in a substituted form such as (MMn)₂Al₂ (where M denotes Cu, Ni, Co, or Fe) and Cu₂MnSi (with Al replaced by Si, Sn, or Ge). The substituted one has a high Tc and exhibits strong magnetism. This magnetism is due to d-electrons of Mn. Conduction electrons are s-electrons and p-electrons. They are completely polarized by the long-range mutual action by d-electrons of Mn. This is a probable reason why it behaves like half-metal. The substituted Heusler alloy can be made into film on a substrate at 200-300 C. by MBE or sputtering. The resulting film can be made completely regular by prolonged heat treatment at 500-800 C.

[0110] It is important to see if an improvement is made over the conventional GMR in magnetoresistance effect when a half-metal material is bonded to another magnetic material, with a spacer interposed between them. This problem was attacked by calculating the bond at the interface with the help of a model based on electron transport. As shown in FIG. 5, the model consists of Fe₃O₄ (502), spacer (503), and CoFe (504) in consideration of the fact that electrons greatly transmit from one electron orbital to another. (In this model, s-electrons are assumed for 503 and 504.) The interface state density D_L(R) in the left (right) electrode is represented by the formula (2) below in which C denotes conductance and T denotes transmission rate.

[0111] In this model, the electron state is assumed to have the junction of electron density distribution as shown in FIG. 6. This electron density distribution is based on the simplified result obtained from band calculations by the first principle and local density functional formalism. The results are as follows.

[0112] (1) Change in resistance by applied magnetic field is positive or negative in the case of a model consisting of one magnetic film of CPP-GMR structure of d-electron conductive half-metal (701), an s-electron conductive spacer (702), and another magnetic film of s-electron conductive half-metal (703), as shown in FIG. 7.

[0113] (2) Change in resistance by applied magnetic field is positive in the case of a model consisting of one magnetic film of CPP-GMR structure of d-electron conductive half-metal (801), a d-electron conductive spacer (802), and another magnetic film of s-electron conductive half-metal (803), as shown in FIG. 8.

[0114] (3) Change in resistance by applied magnetic field is positive (nearly 100%) in the case of a model consisting of one magnetic film of CPP-GMR structure of d-electron conductive half-metal (901), an s-electron conductive spacer (902), and another magnetic film of d-electron conductive half-metal (903), as shown in FIG. 9. However, loss due to reflection and scattering is large because of a small number of electrons.

[0115] (4) Change in resistance by applied magnetic field is small, or the balance between (1) and (3), in the case of a model consisting of one magnetic film of CPP-GMR structure of d-electron conductive half-metal (1001), an s-electron conductive spacer (1002), and another magnetic film of sand d-electron conductive half-metal (1003) (in which there are both s-electrons and d-electrons), as shown in FIG. 10.

[0116] (5) Change in resistance by applied magnetic field is small, or the balance between (1) and (2), in the case of a model consisting of one magnetic film of CPP-GMR structure of d-electron conductive half-metal (1101), an s- and d-electron conductive spacer (1102), and another magnetic film of s-electron conductive half-metal (1103), as shown in FIG. 11.

[0117] (6) Change in resistance by applied magnetic field is nearly 100% in the case of a model consisting of one magnetic film of CPP-GMR structure of d-electron conductive half-metal (1201), a d-electron conductive spacer (1202), and another magnetic film of d-electron conductive half-metal (1203), as shown in FIG. 12.

[0118] To be concrete, in the case of (1), a change in magnetoresistance is expected which corresponds to the curve representing the s-electron conductive spacer, as shown in FIG. 13. This change fluctuates in the positive or negative direction depending on the thickness of the spacer. Calculated ratios of change in magnetoresistance are also as low as about 30%.

[0119] By contrast, in the case of (2), a change in magnetoresistance is positive which corresponds to the curve representing the d-electron conductive spacer, as shown in FIG. 13. The ratio of change in magnetoresistance is close to 90%. The actual value, however, is smaller than this but is still large, because the electron density of the spacer is low and there is impedance between the magnetic film and the spacer.

[0120] The structure in (3) exhibits a high GMR even though it consists of d-electron half-metal film, s-electron spacer, and d-electron film, as shown in FIG. 14. The actual value, however, is smaller than this owing to impedance.

[0121] Each of (4) and (5) is a hybrid of (1) and (2) or a hybrid of (1) and (3). Calculated values suggest that these structures also give a higher ratio of change in magnetoresistance than the conventional ones. The actual ratio of change in magnetoresistance will be smaller than the calculated one because it is strongly affected by s-electrons in many cases and it is the balance between respective values or smaller than them.

[0122] The structure of (6), which consists of a d-electron half-metal film, a d-electron spacer, and a d-electron film, which are bonded together by d-electrons, gives a high ratio of change in magnetoresistance (nearly 100%) as indicated by the curve representing the d-electron conductive spacer, as shown in FIG. 14. In this situation, the cross between the spacer and the Fermi surface is large, and the electron density is high. In addition, the d-electron conductor is usually a high-resistance material like an oxide semiconductor; this leads to good impedance coupling and low reflection loss. Therefore, this structure is most adequate. The foregoing suggests that the electron state in the spacer and free layer may be optimized if an adequate material is specified on the basis of electron species at the Fermi surface.

[0123] It is concluded from the foregoing that half-metal, such as Fe₃O₄ which has d-electrons in the electron state of the Fermi surface, should be used in such a way that (A) the counter magnetic material is that of d-electrons (or the counter magnetic material is the one in which d-electrons are major conduction electrons) or (B) the spacer is replaced by a d-electron conductive material.

[0124] The d-electron material designated by (A) above possibly includes, as ordinary magnetic materials, Fe and Fe-containing 3 d ferromagnetic compound FeX (where X is at least any one of Ni, Co, C, N, and O) with an Fe content being more than 50%. Fe is characterized by that 3 d-electrons and s-electrons are hybridized at the Fermi surface, whereas the compound in which Ni and Co predominate is characterized by that 3 d-electrons and s-electrons have spin in the mutually opposite direction and d-electrons have spin in the downward direction. This leads to a low magnetoresistance.

[0125] Fe₃O₄, CrO₂, or LaSrMnO as a d-electron half-metal material is a d-electron half-metal magnetic material. Such half metal relies conduction for 100% polarized electrons and is useful as the material designated by (A) above. It is known that Fe₃O₄ has downward d-electrons constituting the Fermi surface.

[0126] Heusler alloys as half-metal other than mentioned above does not produce a good effect expected from a d-electron material because it has s-electrons and p-electrons which coupled at the Fermi surface. A magnetic semiconductor such as CrAs is effective because it has d-electrons as major electrons at the Fermi surface. Dilute magnetic semiconductor (such as GaMnAs) and ZnO, in which d-electrons and p-electrons are hybridized at the Fermi level, is expected to produce an effect at the part which is bonded with d-electrons.

[0127] A noble metal, such as Pt, Au, Pd, Ag, Cu, Rh, and Ru, used for the spacer relies conduction on s-electrons, but is useful for the s-electron spacers other than that mentioned in (5) above. Such a noble metal as Pt, Pd, and Ag has a large number of d-electron states in the vicinity of the Fermi surface and hence it readily forms d-electron bond. Thus, it is expected to produce an effect as the d-electron spacer. Other spacer materials, such as SrTiO (perovskite-type oxide) and TiO₂ (rutile-type oxide) have a high d-electron density as the electron state at the Fermi surface. It is known from calculations and actual measurement by photoelectron spectrum that TiO₂ has the d orbital appearing at the Fermi surface. The fact that SrTiO also relies conduction on d-electrons is known from its behavior (change in polarity) which is observed when it is used as the spacer of TMR.

[0128] FIG. 15 shows the structure in which the first magnetic layer is formed from s-electron half-metal (1501). The one in which the spacer (1502) and magnetic layer (1503) are joined together with an s-electron conductor is effective. Heusler alloy or a material containing Ni or Co in a large amount is effective for the second magnetic layer, and a noble metal s-electron conductive material (such as Pt, Au, Pd, Ag, Cu, Rh, and Ru) is effective for the spacer.

[0129] The conventional GMR device of spin valve type has the multi-layered structure which consists of at least a free layer (1601), a spacer (1602), and a pinned layer (1603), as shown in FIG. 16.

[0130] FIG. 17 shows the state of CIP-GMR composed of Fe₃O₄ (40 nm), Au (5 nm), and NiFe (5 nm) sequentially formed on a substrate. It is noted that the substrate/Fe₃O₄/Pt/NiFe produces a downwardly convex negative GMR. The ordinary substrate/CoFe/Cu/CoFe structure produces a positive GMR. This polarity relates with conduction electrons in the magnetic layer and spacer. Fe₃O₄ is a d-electron conductive material, Au is an s-electron conductive material, and NiFe is a material in which s-electrons and d-electrons are hybridized. It is anticipated that the combination of d/s/sd will become a mixture of positive GMR and negative GMR. This anticipation has been proved by actual results. The substrate/CoFe/Cu/CoFe structure (which is a combination of s/s/s) produces the positive GMR. If the spacer is formed from Pt, the resulting structure produces positive GMR because Pt has more d-electron states than Au and hence relies conduction more on d-electrons, with the result that components due to combination of d/s/sd appears. Likewise, the substrate/Fe₃O₄/Pt/NiFe structure is almost twice as large as the substrate/Fe₃O₄/Au/NiFe structure in GMR values.

[0131] On the other hand, CPP-GMR is composed of a substrate (1801), a lower electrode (1802), a pinned layer (1803), a spacer (1804), a free layer (1805), a protective film (1806), and electrodes (1808), as shown in FIG. 18. The upper electrode and the lower electrode are isolated from each other by an insulating film (1807). The pinned layer (1803), spacer (1804), and free layer (1805) may be positioned such that the antiferromagnetic film is either above or below in the structure of GMR device mentioned later. The lower electrode (1802) is formed from a material containing at least any one of Au, Cu, NiFe, Cr, and Ru. The structure composed of a substrate, Au (100 nm), Fe₃O₄ (40 nm), Au (5 nm), and NiFe (5 nm) produces the CPP-GMR characteristics as shown in FIG. 19.

[0132] If the counter free layer is formed from Fe in place of NiFe, then the film structure is similar to that shown in FIG. 8. The structure composed of a substrate, Au, Fe₃O₄ (40 nm), Au (5 nm), and Fe (2.5 nm) produces a ratio of change in CPP-GMR greater than 0.2%, which is more than twice as large as that of the structure composed of substrate, Au, Fe₃O₄, Au, and NiFe. Also, the structure composed of a substrate, Fe₃O₄ (40 nm), Au (5 nm), and Fe₃O₄ (10 nm) produces an improved GMR (greater than twice). The structure composed of a substrate, Fe₃O₄ (40 nm), Pt (5 nm), Fe₃O₄ (10 nm), in which the material for the spacer is changed and the upper and lower magnetic films are the same half-metal, produced an output (1%) which is three to ten times larger.

[0133] The structure as shown in FIG. 12 may be formed from a substrate, Fe₃O₄ (40 nm), TiO₂ (5 nm), and Fe₃O₄ (10 nm), with TiO₂ being the spacer. This structure is expected to give a ratio of change in magnetoresistance (exceeding 10%) which is much larger than that of the structure composed of a substrate, Fe₃O₄, Au, and NiFe.

[0134] The film of GMR structure mentioned above may be applied to a magnetic reproducing head or a GMR sensor. In this case, the pinned layer may be the one which utilizes the difference in coercive force between the pinned layer and the free layer. However, for the maximum use of magnetic characteristics, the pinned layer should preferably be of such a type that it is in contact with the antiferromagnetic film so that its magnetization is pinned by the exchange bonding magnetic field.

[0135] In the conventional GMR, one way to reduce the thickness of the pinned layer was to laminate Ru film, metal soft magnetic film, and antiferromagnetic film to that side of the pinned layer which is opposite to the spacer. In this case, the thickness of Ru film is controlled so that the pinned layer and the metal soft magnetic film make an antiferromagnetic bond. The resulting structure is called laminated ferri structure. This structure is a common one.

[0136] This is applied to the CPP structure with the GMR structure mentioned above. A mention is made below of the structure (in which the magnetization of the pinned layer is antiferromagnetically bonded) and its characteristic properties. FIG. 20 shows an example of the structure in which an antiferromagnetic film (AF film) is at the lower side. Samples were prepared by sequentially laminating on a substrate an underlying film containing Cr, an antiferromagnetic layer 2003 (12 nm thick), a soft magnetic layer 2004 (nm), a noble metal layer 2005 (nm), a pinned layer 2006 (nm), a GMR spacer 2007 (2 nm thick), and a free layer 2008 (3 nm thick). The pinned layer 2006 magnetizes differently depending on the material and thickness of the noble metal layer 2005 thereunder. That is, the magnetization of the pinned layer 2006 combines with the magnetization of the soft magnetic layer 2004 (which is magnetized because magnetization is pinned by the antiferromagnetic layer 2004), and the combined magnetic fields cause the magnetic loop to shift, resulting in the behavior of spin valve. It was found that an antiferromagnetic bond called laminate ferri structure results if the laminate structure is formed from an antiferromagnetic layer 2003, a soft magnetic layer 2004 which contains a metal magnetic material (NiFe), a noble metal layer 2005 (about 0.8-1.2 nm thick) containing Ru as noble metal, and a pinned layer 2006 containing oxide magnetic material (Fe₃O₄). The antiferromagnetic bond was obtained when the noble metal layer is formed from any one of Pt, Pd, Rh, Ru, Ir, Au, and Ag, and has a thickness of 0-1.8 nm. In actual, this effect is produced even though the noble metal layer is absent; however, a better effect is produced when the noble metal layer is present.

[0137] Among the antiferromagnetic materials having a high coupling factor are CrMnPt and MnPt. (They need heat treatment.) Other materials, such as PdMnPt, MnIr, MnRh, NiO, and antiferromagnetic materials containing any one of them, are also effective if they have a low coercive force. MnIr is particularly useful because it provides coupling at room temperature. CrMnPt or MnPt produces the maximum coupled magnetic field of about 900 Oe and MnIr produces the maximum coupled magnetic field of about 550 Oe when the Fe₃O₄ layer is 5 nm thick.

[0138] The foregoing suggests the possibility of obtaining a magnetoresistive effect film which gives a high ratio of change in magnetoresistance as an output of the CPP-GMR structure. The above-mentioned structure is also effective for the magnetoresistive effect film in which the pinned layer is formed from a half-metal oxide magnetic material other than Fe₃O₄.

[0139] There are other structures which differ from those mentioned above in that the soft magnetic layer 2004 is formed from a soft magnetic metal typified by Ni₈₀Fe₂₀ and Co₉₀Fe₁₀.

[0140] FIG. 21 shows an example of the structure in which an antiferromagnetic film is at the upper side. Samples were prepared by sequentially laminating on a substrate 2101 an underlying layer 2102 containing Cr, a free layer 2103 containing CoFe, a GMR spacer 2104 (2.1 nm), a Fe₃O₄ pinned layer 2105 (2 nm), a noble metal layer 2106 (0 to 1 nm), a soft magnetic layer 2107 (3 nm) containing NiFe, an antiferromagnetic layer 2108 (12 nm) containing MnPt, and a protective layer 2109 (3 nm) containing Ta. These samples were also found to produce the magnetoresistive effect in the same way as mentioned above. Each component is identical with that mentioned above.

[0141] Samples of magnetoresistive devices of CPP-GMR structure composed of layers as shown in FIGS. 20 and 21 were prepared. The layer is made up of materials shown in FIGS. 8, 9, 10, 11, 12, and 15. Characteristic properties required of the PP-GMR film are:

[0142] (a) Sheet resistivity and area product RA no higher than 1 m² (depending on the device area).

[0143] (b) Ratio of change in magnetoresistance no lower than 2%.

[0144] (c) Coercive force of magnetic material.

[0145] The sheet resistivity and area product (RA) is calculated for the device measuring 120120 nm in which oxide magnetic material (such as Fe₃O₄) is used as half-metal. A layer structure is assumed which consists of a noble metal layer (2005, 2106), a pinned layer (2006, 2105) containing oxide half-metal, a spacer (2007, 2104) containing noble metal, and a free layer (2008, 2103). The sample has the layer structure of Pt (10 nm), Fe₃O₄ (varied), Au (3 nm), and Fe₃O₄ (5 nm). The resistivity of Fe₃O₄, Pt, and Au were 3500-35000, -cm, 30 -cm, and 2 -cm, respectively.

[0146] When the Fe₃O₄ film is 20 nm thick or 10 nm thick, the device resistance is about 73 and the sheet resistivity is 1.05 m², assuming that the resistivity of Fe₃O₄ is 3500 -cm. Also, when the Fe₃O₄ film is 10 nm thick or 5 nm thick, the device resistance is about 36 and the area resistivity product is 0.5 m². When the Fe₃O₄ film is 5 nm thick or 2.5 nm thick, the device resistance is about 18 and the resistivity area product is 0.25 m².

[0147] The reproducing head for a recording density of 140 Gb/in² should have the CPP-GMR characteristics which meet the requirement that the film thickness of Fe₃O₄ is no larger than 30 nm and the area is no larger than 10 m². This requirement can be achieved because the sheet resistivity is no larger than 1 m². The sheet resistivity may be reduced further if a 3 d metal material (such as Fe) is used for the counter magnetic material.

[0148] If the Fe₃O₄ film is 30 nm thick, a device measuring 250250 nm has a device resistance of about 18 . If the Fe₃O₄ film is 50 nm thick, the same device as above has a device resistance of about 30 and a sheet resistivity of 1.75 m². In actual, however, the resistance could be ten times (at maximum) as high as the value given above because Fe₃O₄ varies in resistivity depending on its manufacturing process. Even in that case, it is possible to produce a magnetoresistive film that realizes a device resistance of 20-200 .

[0149] A device measuring 120120 nm is usable satisfactorily if the total film thickness is about 30 nm in view of the fact that TiO₂ in the Fe₃O₄/TiO₂/Fe₃O₄ structure has a resistivity of about 10000 -cm. With a R/R of 5%, the a real output (AR) would be about 50 mm². Therefore, the device measuring 120120 nm will have a R of about 5 which is sufficiently large output. This value is much larger than that of the conventional film composed of Ta (1 nm), NiFe (3 nm), MnPt (15 nm), CoFe (3.5 nm), Cu (3 nm), CoFe (3 nm), and Ta (1 nm). This conventional film, with a reduced size of 0.10.1 m, has a resistance (R) of about 0.5 and hence merely gives an output (R) as small as about 0.01 even though the R/R is 2%.

[0150] This example demonstrates an application of the present invention to a magnetic head. The magnetoresistive device has the CPP-GMR film constructed as shown in FIGS. 20 and 21 (which was mentioned in Example 2). The film is composed of the materials shown in FIGS. 8, 9, 10, 11, 12, and 15. The magnetoresistive device may be applied to the magnetic head of in-gap type structure or yoke type structure.

[0151] The magnetic head of in-gap type structure is constructed such that a magnetic sensor film is held between a pair of shields and its cross section facing the recording medium is exposed. The magnetic head of yoke type structure is constructed such that a magnetic sensor is not exposed at the surface facing the recording medium but it is arranged deep in the yoke film which is a soft magnetic body resembling the character C. This structure causes the electrode to function also as the shield and provides the domain control mechanism. However, if the device size is sufficiently small, no domain walls occur in the device. In this case the domain control mechanisms in this structure may not be necessary.

[0152] FIG. 22 is a schematic diagram of the reproducing head of in-gap type in which the electrode functions also as the shield, as viewed from the surface facing the recording medium. This reproducing head is formed in the following manner. First, the surface of the part 2201 (which functions as the bottom shield and the bottom electrode) is coated with a lift-off material. The film of the lift-off material is patterned such that the part 2205 (which becomes the magnetic sensor) is left. The magnetoresistive film 2205 is etched by ion milling. After etching, the domain control film 2203 is formed from a hard magnetic material such as CoCrPt and CoCrPtZrO₂ in such a way that it is held between the insulators 2204 and 2202. This domain control film eliminates noise due to domain behavior in the CPP-GMR sensor film, thereby improving accuracy in measurement of magnetic field. The domain control film 2203 is more effective if it is formed on an underlying film of Cr or Ta. The magnetoresistive device may dispense with the domain control film if it is sufficiently small and it generates no magnetic walls therein.

[0153] After the magnetic domain control film 2203 and the insulator 2204 have been formed, the lift-off mask is removed. Then the part 2207 (which functions as the top shield and electrode) is formed. Finally, the top surface is covered with a protective insulating film 2208 thicker than 100 nm which is composed of Al₂O₃ and SiO₂.

[0154] The sensor film needs change in its structure if magnetic domains are to be controlled by the closed flux structure (CFS). FIG. 23 shows the structure of the sensor film which has been modified due to introduction of CFS. The layer structure shown in FIG. 20 is modified by additional three layers (non-magnetic metal film 2307, soft magnetic film 2308, and antiferromagnetic film 2308) on the free layer, as shown in part (a) of FIG. 23. The non-magnetic metal film 2307 is about 3-10 nm thick, which is thicker than the noble metal film for antiferromagnetic coupling. Consequently, the free layer is affected only by the magnetic field from the end of the soft magnetic film. This is the way to control magnetic domains. The same effect as above is produced in the film structure shown in part (b) of FIG. 23. In this film structure, the antiferromagnetic film is placed on the soft magnetic film. This film structure also permits domain control satisfactorily so long as the device has a small surface area.

[0155] The modified film structure also needs change in the head structure. The head shown in FIG. 24 does not have the hard bias structure mentioned above. In other words, it consists of a bottom shieldelectrode 2401, a GMR sensor film 2405, and a top electrode 2407, such that the GMR sensor film 2405 is held between insulators.

[0156] FIG. 25 is a schematic three-dimensional diagram showing a typical yoke structure and a magnetic domain control film. Three directions are indicated by 2509 (track width) 2510 (film thickness), and 2511 (sensor height). This structure prevents the sensor film 2505 from exposing at the surface facing the recording medium. A sample of the structure shown in FIG. 25 was prepared and tested for its performance. This structure has yoke films 2506 and 2507 of soft magnetic material which are held between the bottom magnetic shield 2503 and the top magnetic shield 2507, both formed from Ni₈₁Fe₁₉. In FIG. 26, the upper yoke film 2506 and the lower yoke film 2502 form a C-shaped ring, with an insulator interposed between them. The upper yoke is in contact with the upper surface of the sensor and sends signals to the electrode of the top shield. The lower yoke is in contact with the lower surface of the sensor and communicates with the electrode of the bottom shield. The above-mentioned structure may be modified such that the lower yoke 2506 is tapered in the track width direction near the surface of the recording medium, the yoke is made thicker, or the yoke is discontinuous under the magnetic sensor. The magnetic domain control film 2501 is shown in FIG. 25. It controls magnetic domains in the lower yoke 2502 and the magnetoresistive sensor film. There is no diversion in the surrounding. The magnetic domain control film may be constructed such that it controls the upper and lower yokes and magnetoresistive sensor film altogether or individually. It was found that either way achieves satisfactory magnetic domain control.

[0157] The structure shown in FIG. 25 may be changed into the one shown in FIG. 26 in order to increase the amount of magnetic flux to be detected by the magnetoresistive sensor. In the changed version, that part of the yoke which is in contact with the magnetic sensor film is discontinuous. The magnetic domain control film in this structure is also effective if it is formed from a high-resistance material. The magnetic sensor detects the magnetic field of the recording medium more sensitively than the semiconductor sensor film because it has a permeability as high as about 1000 times.

[0158] The magnetic sensor of this structure detects the magnetic field applied perpendicularly to the film surface. Therefore, it detects the magnetic field leaking from the recording medium, or in the case of longitudinal recording, it detects the magnetic flux leaking from the record end.

[0159] The magnetoresistive sensor mentioned in this example did not deteriorate in reproducing properties due to conduction from the magnetoresistive changing film to the magnetic domain control film even though the gap between the reproducing shields is smaller than 80 nm.

[0160] The above-mentioned reproducing head was modified by adding an insulating film on the top magnetic shield and a recording head mechanism thereon. The resulting sample worked well for both recording and reproduction.

[0161] FIG. 27 shows a magnetic disk drive provided with the head of the present invention. The magnetic disk drive consists of the following components.

[0162] Magnetic disk 2701 as a discoid magnetic recording medium, which is designed to record data in the concentric circular recording area called tracks.

[0163] Magnetic head 2710 (as defined in the present invention) to write and read data.

[0164] Actuator 2711 to move the magnetic head 2706 to a prescribed position on the magnetic disk 2701.

[0165] Means to control transmission and reception of data written and read by the magnetic head and to control the movement of the actuator.

[0166] The construction and action of the magnetic disk drive are explained below. At least one rotatable magnetic disk 2701 is supported by a revolving shaft 2702 and turned by a drive motor 2703. At least one slider 2706 is placed on the magnetic disk 2701. The slider 2706 supports the magnetic head 2710 of the present invention which performs reading and writing.

[0167] As the magnetic disk 2701 turns, the slider 2706 moves on the disk surface to access a prescribed position where desired data are recorded. The slider 2706 is attached to the arm 2708 through the suspension 2707. The suspension 2707 brings the slider 2706 into close contact with the magnetic disk 2701 by its slight elastic force. The arm 2708 is attached to the actuator 2711.

[0168] The actuator 2711 is a voice coil motor (VCM), which has a movable coil placed in a stationary magnetic field. The coil has its moving direction and moving rate controlled by electric signals that come through the line 2704 from the control unit 2712. Therefore, the actuator in this example consists of the slider 2706, suspension 2707, arm 2708, actuator 2711, and line 2704.

[0169] The rotating magnetic disk 2701 creates an air flow (air bearing) between the slider 2706 and the disk surface. This air bearing lifts the slider 27056 above the surface of the magnetic disk 2701. Therefore, while the magnetic disk is running, the air bearing balances with the slight elastic force of the suspension 2707. Thus the slider 2706 floats, keeping a certain distance from the magnetic disk 2701, without coming into contact with the surface of the magnetic disk.

[0170] The control unit 2712 is usually composed of logic circuits, memory, microprocessor, etc. The control unit 2712 receives and transmits control signals through lines and controls the various components of the magnetic disk drive. For example, the motor 2703 is controlled by motor control signals transmitted through the line 2704.

[0171] The actuator 2711 moves the selected slider 2706 to a desired data track on the magnetic disk 2701 in response to head position control signals and seek control signals received through the line 2704.

[0172] The magnetic head 2710 reads data from the magnetic disk 2701 and converts them into electric signals. The control signals receive the electric signals through the line 2704 and decode them. The control signals also transmit electric signals to the magnetic head 2710 through the line 2704 so that the magnetic head 2710 writes data on the magnetic disk 2701. In other words, the control unit 2712 controls transmitting and receiving the information which the magnetic head 2710 reads and writes.

[0173] Signals for reading and writing may be transmitted directly from the magnetic head 2710. Control signals include access control signals and clock signals. In addition, the magnetic disk unit may have a plurality of magnetic disks and actuators, and the actuator may have a plurality of magnetic heads.

[0174] It is possible to build up a so-called disk array unit by combining the above-mentioned mechanisms. The magnetic recording unit provided with the magnetoresistive device of the present invention is capable of recording and reproducing data with a recoding density in excess of 150 Gb/in².

[0175] FIG. 28 shows another example of the present invention.

[0176] There is shown a substrate 2801, on which a 100% polarized spin injection layer 2802 is formed and a GMR structure 2814 is arranged, with a barrier layer 2803 placed thereunder. The GMR structure 1814 is composed of a ferromagnetic free layer 2804, a non-magnetic electron conductive layer 2805, a ferromagnetic pinned layer 2806, and an antiferromagnetic layer 2807, which are sequentially laminated one over the other. The ferromagnetic free layer 2804 has its magnetization freely rotated by the external magnetic field (H). Electric resistance changes in response to the angle of rotation, thereby producing the magnetoresistive effect. The GMR structure in this example is that shown in FIGS. 20 and 21, which has the layer structure as shown in FIGS. 8, 9, 10, 11, 12, and 15.

[0177] The GMR structure 2814 has at its ends the insulators 2813 which prevent electric leakage across the electrode 2808 and the electrode 2810.

[0178] The electrode 2808 is arranged on the antiferromagnetic layer 2807, the electrodes 2810 and 2811 are arranged on the ferromagnetic free layer 2804, and the electrodes 2809 and 2812 are arranged on the 100% polarized spin injection layer 2802. Current is applied across the electrodes 2810 and 2812 and the ratio of change in resistance across the electrodes 2808 and 2810 is regarded as the output of the GMR structure 2814.

[0179] A mentioned is made below of the process and materials used to produce the above-mentioned magnetoresistive sensor. On the silicon substrate 2801 is formed the 100% polarized spin injection layer 2802, which is a dual layered film composed of Co (5 nm thick) and Cu (2 nm thick). The following layers are sequentially formed by RF sputtering.

[0180] barrier layer 2803 of Al₂O₃ (2 nm thick),

[0181] ferromagnetic free layer 2804 of, Fe₃O₄ (10 nm thick),

[0182] non-magnetic electron conductive layer 2805 of Pt (2.2 nm thick),

[0183] ferromagnetic pinned layer 2806 of Fe₃O₄ (2 nm thick), and

[0184] antiferromagnetic layer 2807 of Ru/CoFe/PtMn (PtMn 12 nm thick).

[0185] These layers are patterned into a desired shape. Al₂O₃ is formed by natural oxidation from an Al film, 1.5 nm thick. Natural oxidation may be replaced by plasma oxidation. The patterned surface is coated with a photoresist. The photoresist is patterned into a desired shape by photolithography. After patterning, the area of the ferromagnetic free layer 2804 is 2020 m and the area of the antiferromagnetic layer 2807 is 55 m. The electrode 2808 is fabricated into a desired shape. The electrodes 2810 and 2811 are fabricated so that they are arranged on the ferromagnetic free layer 2804. The electrodes 2809 and 2812 are fabricated so that they are arranged on the 100% polarized spin injection layer 2802.

[0186] The thus obtained magnetoresistive device of three-terminal type gave a ratio of change in resistance as high as 200%. This value is about 7 times as large as the one (30%) in the case of conventional giant magnetoresistive device. This good result is due to the fact that the s-electron band of Cu formed in the 100% polarized spin injection layer is completely polarized in the vicinity of the Fermi level and only up spin flows into the GMR structure 2814, thereby increasing the output.

[0187] In this example, the barrier layer 1803 is formed from Al₂O₃; however, it may also be formed from any one of MgO, SrTiO₃, HfO₂, TaO, NbO, and MoO.

[0188] Incidentally, the above-mentioned polarized spin injection layer may be formed from half-metal ferromagnetic material such as Sr₂FeMoO₇, La_0.7Sr_0.3MnO₃, MnSb, CrO₂, MnAs, CoTiO₂, and CrAs. It may also be a dual layered film composed of a ferromagnetic layer and a non-magnetic layer, the former being formed from Mn, Co, Ni, or Fe in the form of simple substance or intermetallic compound thereof, the latter being formed from Au, Ag, Pt, Pd, Ir, Cr, or Ru.

[0189] The magnetoresistive device mentioned above is used to produce a magnetic head having an very high output.

[0190] FIG. 29 shows an example of the magnetic memory based on the magnetoresistive device of the present invention. The GMR structure used in this magnetic memory is composed of the materials shown in FIGS. 8, 9, 10, 11, and 12. The GMR structure shown in FIGS. 20 and 21 is used. The magnetoresistive device has a bit line 2905 and a word line 2906 which are in contact with it.

[0191] FIG. 30 shows a typical structure of the magnetic memory, or so-called MRAM. The substrate 3001 is a CMOS which is a transistor having terminals called emitter 3003, base 3010, and collector 3002. The diffused layer 3004 which is formed on the semiconductor substrate permits conduction of electrons.

[0192] The magnetic memory device consists of a plurality of cells arranged in parallel, each cell having a magnetic sensor 3009 for information recording, an MR sensor film 3006 including electrodes holding 3009 between them, a bit wire 3007 connected to said sensor and supplies current to the device, a word line 3005 (which holds the MR sensor film 3006 and is opposite to said bit line 3007 and is away from the MR sensor film 3006 and crosses said bit line at right angle and performs recording action on the magnetic sensor film), an amplifier system to amplify recorded signals, and a read word lines to switch reading and writing. The magnetic sensor 3009 in this magnetic memory device is the one which contains a magnetic material as shown in Examples 1, 2, 3, and 4 of the present invention. Current flows in the direction perpendicular to the film surface or in one direction of the film surface; therefore, it is used as the magnetic sensor.

[0193] Also, the magnetic sensor 3009 is a square with each side measuring 0.1-0.25 m. It is fabricated by electron beam writing. The magnetic sensor 3009 has the film structure as shown in FIG. 20 or FIG. 21. The surrounding of the magnetic sensor is covered with insulting film. The shape of the device may be square, polygon, or circle so that current flow in the perpendicular direction. The magnetic sensor magnetizes in the direction of current flowing through the word line 3005 and the bit line 3007. The direction of magnetization rotates as the direction of combined magnetic field changes in the magnetic sensor. When the direction of magnetization of the free layer of the magnetic sensor rotates, magnetic domains occur in the free layer. Such magnetic domains fluctuate resistance induced by the magnetic field and lower the S/N ratio. This disables memory reading. This necessitates the magnetic domain control film for better control. Thus, the magnetic domain control film 3006 is arranged at both ends of the magnetic sensor. In this way it is possible to control magnetic domains without loss due to diversion to the magnetic domain control film.

[0194] FIG. 31 shows an example of the integrated circuit in which the magnetoresistive device shown in FIGS. 29 and 30 functions as each cell. The magnetoresistive device is placed at the intersection of the bit line 2905 and the word line 2906. The reading and writing of information are accomplished by selecting the bit line and word line which intersect at the desired cell.

[0195] It is possible to reduce the area of the memory cell and achieve integration of large capacity by incorporating the device into the magnetic memory.

[0196] Additional examples are given below.

[0197] (1) A magnetic head having the magneto-resistive device mentioned above.

[0198] (2) A magnetic head which has the magneto-resistive device mentioned above, an electrode to supply current to said magneto-resistive device, and a 100% polarized spin injection layer which is connected to said magneto-resistive device through a barrier layer.

[0199] (3) A magnetic recording unit consisting of a magnetic recording medium having a magnetic recording layer, a drive unit to drive the magnetic recording medium, a magnetic head having the magneto-resistive device mentioned above, an actuator to move the magnetic heat to a desired position on the magnetic recording medium, and a signal processing means to reproduce output signals from the magnetic head.

[0200] (4) The magnetic recording unit mentioned above in which the magnetic head has a recording part and a reproducing part.

[0201] (5) A magnetic memory which consists of a magnetic sensor having the magneto-resistive device mentioned above, a bit line which is connected to the magnetic sensor and supplies current to the device, a word line which intersects said bit line at right angle and performs recording action on said magnetic sensor film, said word line being at a position away from said magnetic sensor film at the position opposite to said bit line with said magnetic sensor film interposed, an amplifying system to amplify recording signals, and a plurality of cells arranged in parallel which are provided with word lines to perform the switching of reading and writing.

[0202] As mentioned above, the magnetoresistive device pertaining to the present invention is a sensor film for CPP-GMR which utilizes a half-metal magnetic material (oxide magnetic material) and a metal magnetic material in combination. It gives a high ratio of change in resistance by applied magnetic field and a high electric resistance and produces a large GMR output.

[0203] In addition, the magnetic recording unit provided with the magnetoresistive device can be used in combination with a magnetic recording medium having an a real recording density in excess of 200 Gb/in². Moreover, the magnetic memory provided with the magnetoresistive device will have a higher density than the current memory.