1. Field of the Invention
The present invention relates to a magnetic reproducing head of a magnetic disk drive apparatus, a memory element of a magnetic random access memory and a magnetic sensor.
2. Related Background Art
A tunnel magnetic resistive element with crystalline MgO as a tunnel barrier layer obtains a huge MR ratio (percentage of magnetic resistive change) of 200% or more at the room temperature. Consequently, applications to a reproducing or read-out head of a magnetic disk drive apparatus, a memory element of magnetic random access memory (MRAM) and a magnetic sensor are being expected. In the case of a conventional tunnel magnetic resistive element obtained by adopting a tunnel barrier layer made of MgO, an RF magnetron sputtering method using an MgO sintering target is used for film formation of the MgO tunnel barrier layer (Patent Document 1, Non-Patent Documents 1 to 5). However, the MgO formation method by the RF magnetron sputtering using the MgO sintering target gives rise to a problem that dispersion is likely to occur in normalized tunnel resistive value (RA) and there is a risk to remarkably deteriorate the yield factor at the time of device fabrication.
In order to avoid such problems, alternative methods of forming the MgO tunnel barrier layer without using the MgO sintering target are known.
Tsann et al. have proposed a method of film formation of the MgO tunnel barrier layer in three steps of firstly carrying out film formation of a metal Mg layer, secondly stacking oxygen-doped metal Mg layers and thirdly bringing the laminated body into an oxidation process (Patent Document 2). Fu et al. have proposed a method of film formation of the MgO tunnel barrier layer in three steps of carrying out film formation of a first Mg layer, carrying out natural oxidation method on the first Mg layer to obtain an MgO layer and carrying out film formation of a second Mg layer on the MgO layer and a method of film formation in three steps of carrying out film formation of a first Mg layer, carrying out film formation of an MgO layer on the first Mg layer by reactive sputtering and carrying out film formation of a second Mg layer on the MgO layer (Patent Document 3).
Koh et al. have proposed a method of film formation of the MgO tunnel barrier layer in five steps of carrying out film formation of a first Mg layer, carrying out radical oxidation on the first Mg layer to obtain a first MgO layer, annealing the first MgO layer to provide (001) crystalline orientation, carrying out film formation of a second Mg layer on the first MgO layer and carrying out natural oxidation on the second Mg layer to obtain a second MgO layer. Koh et al. have also proposed a method of forming in five steps of carrying out film formation of a first Mg layer, carrying out radical oxidation on the first Mg layer to obtain a first MgO layer, carrying out film formation of a second Mg layer on the first MgO layer, carrying out radical oxidation on the second Mg layer to obtain a second MgO layer and film formation of a third Mg layer on the second MgO layer (Patent Document 4).
Miura et al. have proposed a method of film formation of the MgO tunnel barrier layer in four steps of carrying out film formation of a first Mg layer, carrying out natural oxidation on the first Mg layer, carrying out film formation of a second Mg layer on the first Mg layer and carrying out natural oxidation on the second Mg layer at oxygen pressure lower than at the time of oxidizing the first Mg layer (Patent Document 5).
Dave et al. have proposed a method of film formation of the MgO tunnel barrier layer consisting of four kinds of methods, that is, a method of bringing metal Mg into plasma oxidation, a method of bringing metal Mg into radical oxidation, reactive sputtering with proportion of Ar to oxygen being 5:3 and RF sputtering with an MgO sintering target (non-Patent Document 6). Oh et al. have also proposed a method of bringing metal Mg into radical oxidation as a method of film formation of the MgO tunnel barrier layer (non-Patent Document 7).
Patent Document 1: Japanese Patent Application Laid-Open No. 2006-080116
Patent Document 2: U.S. Pat. No. 6,841,395
Patent Document 3: Japanese Patent Application Laid-Open No. 2007-142424
Patent Document 4: Japanese Patent Application Laid-Open No. 2007-173843
Patent Document 5: Japanese Patent Application Laid-Open No. 2007-305768
Non-Patent Document 1: D. D. Djayaprawira et al., “Applied Physics Letter”, 86, 092502 (2005)
Non-Patent Document 2: J. Hayakawa et al. “Japanese Journal of Applied Physics”, L587, 44 (2005)
Non-Patent Document 3: K. Tsunekawa et al. “Applied Physics Letter”, 87, 072503 (2005)
Non-Patent Document 4: S. Ikeda et al. “Japanese Journal of Applied Physics”, L1442, 44 (2005)
Non-Patent Document 5: Y. Nagamine et al. “Applied Physics Letter”, 89, 162507 (2006)
Non-Patent Document 6: R. W. Dave et al. “IEEE Transactions on Magnetics”, 42, 1935 (2006)
Non-Patent Document 7: S. C. Oh et al. “IEEE Transactions on Magnetics”, 42, 2642 (2006)
In an attempt to form an MgO tunnel barrier layer just by oxidizing metal Mg, it is difficult to obtain RA less than or equal to several 100 Ω·μm2 as introduced in the non-Patent Document 6 and the non-Patent Document 7. The reason hereof is considered that, metal Mg is exposed to the oxygen atmosphere and then passivation film is formed on its surface so that further deeper oxidation hardly becomes likely to progress.
Therefore, a method of solving the problem described above by repeating film formation and oxidation of metal Mg twice is proposed in the Patent Document 4 and the Patent Document 5. However, the method of repeating film formation and oxidation of metal Mg twice gives rise to a problem that shuttling between a film formation chamber and an oxidation processing chamber remarkably decreases throughput of production. Or a method of providing two chambers of a film formation chamber and an oxidation processing chamber for metal Mg each in order to avoid decrease of throughput due to repeated conveyance can be considered. However, that case gives rise to a problem of increase of production costs for devices due to increase of the cost for apparatuses and increase of the area for installation and the like.
The methods in the Patent Document 2 and the Patent Document 3 require a smaller number of steps comparatively so that the problems on the throughput and the production cost are resolved. However, with the MR ratio in the low RA region being not more than 40%, performance of the tunnel magnetic resistive element with a MgO tunnel barrier layer is not sufficient. In addition, due to unavailability of any example on dispersion of the RA that affects the yield factor significantly, it is uncertain whether or not the process is appropriate for production.
An object of the present invention is to provide a method and an apparatus of fabricating a tunnel magnetic resistive element requiring comparatively few numbers of steps, provided with excellent property in uniformity of RA and capable of obtaining a high MR ratio at a low RA.
First aspect of the present invention is a method of fabricating a tunnel magnetic resistive element including a first ferromagnetic layer, a tunnel barrier layer and a second ferromagnetic layer, comprising a step of making the tunnel barrier layer, comprising the step of making the tunnel barrier layer includes the steps of: forming a first layer on the first ferromagnetic layer by applying DC power to a metal target and introducing sputtering gas without introducing oxygen gas in a sputtering chamber; and forming a second layer on the first layer by applying DC power to the metal target and introducing the sputtering gas and oxygen gas with the DC power to be applied to the metal target from the step of forming the first layer in the sputtering chamber, wherein the second layer is oxygen-doped.
Second aspect of the present invention is a method of fabricating a tunnel magnetic resistive element including a first ferromagnetic layer, a tunnel barrier layer and a second ferromagnetic layer, comprising a step of making the tunnel barrier layer, comprising the step of making the tunnel barrier layer includes: forming a lower part layer of a first metal layer on the first ferromagnetic layer by applying DC power to a metal target and introducing sputtering gas without introducing oxygen gas in a sputtering chamber; forming a upper layer of the first metal layer on the lower part layer by applying DC power to the metal target and introducing the sputtering gas and oxygen gas with the DC power to be applied to the metal target from the step of forming the lower part layer in the sputtering chamber; performing an oxidation process on the first metal layer including the lower part layer and the upper layer with an oxygen gas introduced; and forming a second metal layer on the upper layer of the first metal layer on which the oxidation process has been performed.
According to the present invention, a method and an apparatus of fabricating a tunnel magnetic resistive element which does not show much dispersion in RA and capable of obtaining a high MR ratio in a low RA can be provided.
Embodiments of the present invention will be described with the drawings.
A substrate for forming spin-valve type tunnel magnetic resistive thin film is arranged in the load lock chamber 27 which is initially set at the atmosphere pressure and is conveyed to a desired vacuum chamber with the vacuum conveyance robot 28 after the load lock chamber 27 is pumped down to attain the vacuum.
As an example, a case of fabricating a spin valve type—magnetic tunnel junction of a bottom type including a synthetic antiferromagnet layer as a magnetization fixed layer produced in an example to be described later will be described. In the present specification, a synthetic antiferromagnet layer (SAF) stands for any stack including two ferromagnetic layers separated by a non-magnetic spacer and with their magnetizations anti-parallel to each other. These magnetizations for two ferromagnetic layers can be the same or different.
Specific configurations of the respective layers will be described with reference to
The PtMn layer is formed to attain the Pt content of 47 to 51 (atomic %) by adjusting composition of the sputtering target and film formation conditions (gaseous species, gas pressure and input power supply) so that the PtMn layer is ordered by annealing to induce antiferromagnetic properties.
In order to carry out film formation of a film configuration as described above efficiently, sputtering targets are arranged in each sputtering chamber as follows. Respectively as sputtering targets 21a to 21b and 22a to 22d and 23a, Ta (tantalum) and Cu (copper) are arranged in the sputtering chamber 21; Co70Fe30 (cobalt-iron), PtMn (platinum-manganese), Ru (ruthenium) and Co60Fe20B20 (cobalt-iron-boron) are arranged in the sputtering chamber 22; Mg is arranged in the sputtering chamber 23. In addition, Ta, Co60Fe20B20, Mg, Ru and Cu are arranged in the sputtering chamber 24 as sputtering targets 24a to 24e.
In the present invention, spin valve type-magnetic tunnel junctions including a synthetic antiferromagnet structure and being the most complicated film configuration in the present invention are formed as follows. At first, the substrate 1 is conveyed to the substrate pre-processing chamber 25 and approximately 2 nm thickness on the surface layer contaminated in the atmosphere is physically removed by reverse sputter etching. Thereafter, the substrate 1 is conveyed to the sputtering chamber 21 to carry out film formation of the lower part electrode layer 2 consisting of laminated structure of Ta/CuN/Ta/CuN/Ta. At that time, at the time of film formation of CuN, a Cu target is used. A tiny amount of nitrogen is added besides Ar as sputtering gas to, thereby, form CuN. Thereafter, the substrate is moved to the sputtering chamber 22 to carry out film formation of an antiferromagnetic layer 3 consisting of PtMn/CoFe/Ru and a magnetization fixed layer 4 (first ferromagnetic layer) made of CoFeB. Here, instead of PtMn as the antiferromagnetic layer 3, IrMn (iridium-manganese) can be used. In that case, an Ru layer is preferably used as a buffer layer 9 of the IrMn layer. In such a case, the film to undergo film formation at the sputtering chamber 22 will be Ru/IrMn/CoFe/Ru/CoFeB.
Next, a method of forming the tunnel barrier layer will be described. After formation of the films up to CoFeB, the substrate 1 is moved to the sputtering chamber 23 so that metal Mg undergoes film formation with oxygen doping. As an example of a method of oxygen doping, Ar and oxygen are used as sputtering gas. Here, the oxygen gas to be mixed in is preferably not more than 30% of the sputtering gas. The reason hereof is that surface oxidation of the Mg target is suppressed.
The vacuum chamber is provided with respectively individual gas introducing entrance. Gas is introduced while individually controlling flow of Ar and oxygen. The timing for introducing oxygen gas at the time of oxygen doping does not necessarily have to be the same as the timing of introducing Ar being the sputtering gas, but can be later than the timing of introducing Ar or earlier than the timing of stopping Ar supply.
Next, the substrate 1 is moved to the oxidation processing chamber 26 to undergo an oxidation process. As a method of the oxidation process, any of natural oxidation and radical oxidation can be used. In the case of the natural oxidation, the pressure of the oxygen atmosphere is maintained at 0.01 to 10 Torr and the substrate is left for a predetermined time. In the case of radical oxidation, oxygen plasma is caused to occur by applying high frequency to the electrode in the oxygen atmosphere. The substrate is placed below a shower plate in which a plurality of holes with length of around 10 mm and diameter of around 1 mm are opened and through which particles (radical oxygen species and oxygen) besides charged particles in the plasma can flow and irradiate the substrate.
Subsequently, the substrate 1 is moved to the sputtering chamber 24 to carry out film formation of Mg/CoFeB/Ta/Cu/Ta/Ru. Mg film thickness is preferably not less than 0.1 nm and not more than 0.6 nm. Thereby, as described later with
Hereafter, the produced magnetic tunnel junctions are placed into an annealing furnace in which a magnetic field is applied. While a unidirectional parallel magnetic field with intensity of more than or equal to 8 kOe is applied, an anneal process is carried out at a desired temperature and for desired time in the vacuum. Experimentally, not less than 250° C. and not more than 360° C. is adopted. In the case of a low temperature, long time of not less than 5 hours is preferable and in the case of a high temperature, short time of not more than 2 hours is preferable.
Here, the above described embodiment adopted Ar (argon) as the principal component for the sputtering gas, but, will not be limited hereto. For example, sputtering gas with at least one of He (helium), Ne (neon), Kr (krypton) and Xe (xenon) as the principal component can be used.
Next, examples of the present invention will be described with the drawings.
With reference to
The present tunnel magnetic resistive element is put into an annealing furnace in a magnetic field to carry out an anneal process in a magnetic field of 1 T at 360° C. for 2 hours under vacuum.
Here, the MR ratio and the RA was measured by Current-In-Plane-Tunneling (CIPT) method with 12-terminal probe. The measurement principle of the CIPT method is described in D. C. Worledge and P. L. Trouilloud, “Applied Physics Letters”, 83 (2003), 84-86.
With reference to
The step S603 described above will be described in further detail as follows. At first, film formation of metal Mg (first metal layer) of 1.2 nm is carried out on a CoFeB layer to become the first ferromagnetic layer in the sputtering chamber 23.
Next, the shutter is opened so that film formation starts. When film thickness reaches 0.6 nm (corresponding to a lower part layer of the first metal layer), oxygen gas at 5 sccm (oxygen concentration=4.76%) is introduced so that the Mg layer undergoes doping with a tiny amount of oxygen. When the film thickness of the Mg layer reaches 1.0 nm (corresponding to a middle layer of the first metal layer), introduction of oxygen is halted. Continuously, film formation of the remaining Mg layer of 0.2 nm is carried out in the Ar atmosphere (corresponding to an upper part layer of the first metal layer) so that film formation of the first metal layer of 1.2 nm is finalized. During the above process, gas exhaust from the chamber is continuously conducted with the gas introduction. Accordingly, after the introduction of oxygen gas has been halted, the amount of oxygen is gradually decreased in the atmosphere so that the atmosphere is substantially in Ar atmosphere.
Here, in the present example, film formation of the first metal layer was carried out in the Ar atmosphere at the initial stage of the film formation and at the final stage of the film formation of the first metal layer without introducing oxygen and, however, does not necessarily have to be carried out in the both stages. A method of film formation of the first metal layer in the Ar atmosphere without introducing oxygen only at any one of the film forming stages can be adopted.
Next, in a step S605, the substrate is moved to the oxidation processing chamber 26 to undergo radical oxidation. At the time of radical oxidation, oxygen gas at 700 sccm was introduced to inside the vacuum chamber and RF power of 300 W was applied to electrodes. The oxidation time was 10 seconds.
At last, in a step S607, the substrate is moved to the sputtering chamber 24 to carry out film formation of metal Mg (corresponding to the second metal layer) of 0.3 nm. Subsequently, in a step S609, film formation of the second ferromagnetic layer and succeeding layers was carried out as described in the above embodiment.
In the Example 2, the upper part layer of the first metal layer may not be formed. In the present example, when the tunnel barrier layer is formed on the first ferromagnetic layer, while the DC power is applied to the Mg target (that is, while sputtering is continued), a first layer included in the tunnel barrier layer is formed in a OFF state of the introduction of oxygen, and then, a second layer included in the tunnel barrier layer is formed in a ON state of the introduction of oxygen. Note that a third layer (corresponding to the upper part layer of the Example 2) may be formed on the second layer.
The flow of forming the tunnel barrier layer of the present example will be described below. In first step, Mg layer as the first layer is formed on the first ferromagnetic layer by applying DC power to a Mg metal target and introducing sputtering gas without introducing oxygen gas in the sputtering chamber 23. Then, in second step, a oxygen-doped Mg layer as a second layer is formed on the Mg layer by applying DC power to the same target (Mg target) as the first step and introducing the sputtering gas and oxygen gas while the DC power is applied to the same target as the first step from the first step in the sputtering chamber 23. Note that the first step and the second step may be performed like step S603 except for forming the upper part layer.
Then, in third step, oxidation process is performed on the oxygen-doped Mg layer with the oxygen gas introduced, like step S605 of
As one example, when in the tunnel barrier layer having a first metal layer and a second metal layer, the first metal layer has two layers, the first layer corresponds to a lower part layer of the first metal layer, and the second layer corresponds to a upper layer of the first metal layer.
In the second step, the oxygen gas may be introduced so that the Mg layer undergoes doping with a tiny amount of oxygen, or may be introduced to the extent that the Mg layer is oxidized.
This application is a continuation-in-part of U.S. patent application Ser. No. 12/190,864 filed on Aug. 13, 2008, which is a continuation of International Application No. PCT/JP2008/061554, filed Jun. 25, 2008.
Number | Date | Country | |
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Parent | PCT/JP2008/061554 | Jun 2008 | US |
Child | 12190864 | US |
Number | Date | Country | |
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Parent | 12190864 | Aug 2008 | US |
Child | 13728448 | US |