CROSS-REFERENCE TO RELATED APPLICATIONS 
       [0001]    This application is a divisional of U.S. application Ser. No. 11/161,675, filed on Aug. 11, 2005, which claims priority to Japanese Application No. 2004-240838, filed on Aug. 20, 2004, the entire contents of which are incorporated herein by reference. 
     
    
     BACKGROUND OF THE INVENTION 
       [0002]    1. Field of the Invention 
         [0003]    The present invention relates to a method of production of a magnetoresistance effect device, more particularly, relates to a method of production of a magnetoresistance effect device suitable for preventing a drop in a magnetoresistance ratio. 
         [0004]    2. Description of the Related Art 
         [0005]    Magnetic random access memories (MRAMs) are integrated circuit magnetic memories that is now paid attention as memories having integration densities on a par with dynamic random access memories (DRAMs), featuring high speed performance on a par with static random access memories (SRAMs), and enabling unlimited rewriting. The magnetic random access memories and magnetic heads are mainly comprised of layers of nonmagnetic or magnetic thin films of several nm (nanometer) thickness giving a tunneling magnetoresistive (TMR) effect. This configuration with the TMR effect is hereinafter referred to as “TMR devices”. 
         [0006]    Further, each of the plurality of magnetic films forming a TMR device is formed by sputtering. The insulation layer is formed utilizing an oxidation reaction of a metal. 
         [0007]    The basic structure of a TMR device is shown in  FIG. 5 . A TMR device  101  is basically comprised, as explained above, of an insulation layer  102  sandwiched at its two sides by ferromagnetic layers  103  and  104 . Arrows  103   a  and  104   a  show the directions of magnetization of the ferromagnetic layers  103  and  104 , respectively.  FIGS. 6A and 6B  are used for explaining the state of resistance in the TMR device  101  when applying a voltage V to the TMR device  101  by a DC power source  105 . The TMR device  101  has the feature of changing in resistance in accordance with the states of magnetization of the ferromagnetic layers  103  and  104  due to the DC voltage V applied from the DC power source  105 . Further, as shown in  FIG. 6A , when the directions of magnetization of the ferromagnetic layers  103  and  104  are the same, the resistance value of the TMR device  101  becomes minimum, while as shown in  FIG. 6B , when the directions of magnetization of the ferromagnetic layers  103  and  104  are opposite, the resistance value of the TMR device becomes maximum. The minimum resistance of the TMR device is indicated by “R min ”, while the maximum resistance of the TMR device  101  is indicated by “R max ”. Here, in general, there are a “current-in-plane” (CIP) structure sending a sense current in parallel to the plane of the device film and a “current perpendicular to plane” (CPP) type sending a sense current in a direction perpendicular to the plane of the device film.  FIG. 5  and  FIGS. 6A and 6B  show an example of a CPP type magnetoresistance effect device. 
         [0008]    A “MR ratio (magnetoresistance ratio)” is defined for the above TMR device  101  as follows: 
         [0000]      MR ratio=( R   max   −R   min )/ R   min   (1) 
         [0009]    Next, the conventional method of production and problems of a TMR device having the above multilayer structure and resistance characteristics will be explained from the viewpoint of the deterioration of the MR ratio. 
         [0010]    A magnetoresistance effect device like a TMR device built into an MRAM or magnetic head is microprocessed in the process of production. For example, when etching the magnetic layers forming the TMR device, an etching gas of a mixed gas of carbon monoxide and a nitrogen compound (for example, NH 3 : ammonia) (CO+NH 3 ) or an alcohol-based etching gas including hydroxy groups (CH 3 OH) etc. is used. At this time, if using a resist mask made of an organic material for the etching, no selectivity can be obtained and microprocessing is not possible, so the practice has been to use tantalum (Ta), titanium (Ti), etc. giving selectivity with respect to the magnetic layers as a hard mask and etch by reactive ion etching (RIE) etc. In particular, Ta is originally used as a thin film material forming part of a TMR device and has the advantage that it can be deposited by the sputtering method in the same step as another magnetic material (see Japanese Patent No. 3131595, Japanese Patent Publication (A) No. 2002-38285, and Japanese Patent Publication (A) No. 2001-274144). 
         [0011]    However, if using Ta, Ti, etc. as a hard mask for etching by the above-mentioned gases, the oxygen contained in the gases reacts with the surface of the hard mask to form oxide films at the surface-most layer of the hard mask. This state will be explained with reference to  FIGS. 7A to 7C .  FIGS. 7A to 7C  show the conventional process of dry etching of the TMR device  101  provided with a Ta layer  111  as the layer forming the hard mask. In the TMR device  101 , in particular reference numeral  112  shows a substrate and  113  a bottom electrode. 
         [0012]    In  FIGS. 7A to 7C , the resist  114  is used to etch the Ta layer  111  to form a hard mask of the Ta layer  111 . In the state of  FIG. 7B , as a result, a hard mask  111   a  made of the Ta layer  111  is formed. In  FIG. 7B , the hard mask  111   a  of the Ta layer  111  is used for etching the layers forming the TMR device. At this time, the above-mentioned gases are used. In  FIG. 7C , an example of the state where the TMR device  101  is etched using the hard mask  111   a  of the Ta layer  111  is shown. In this example, the free layer  115  and barrier layer  116  are etched and the hard mask  111   a  of the Ta layer  111  is left at a thickness of tens of Å on the free layer  115 . 
         [0013]    In the conventional dry etching method explained above, finally the hard mask  111   a  of the Ta layer  111  is left as a surface layer at the topmost layer of the TMR device  101 . After this, the TMR device  101  finished being microprocessed in the vacuum dry etching apparatus is taken out of the dry etching apparatus, that is, is exposed to the air. Therefore, the TMR device  101  is placed in an environment in contact with oxygen contained in the air. Accordingly, by not removing all of the Ta layer used as the hard mask in the etching, but leaving some of it, this is given the role of a protective layer protecting the magnetic layers from oxidation etc. As a result, the surface-most layer of the remaining hard mask  111   a  of the Ta layer  111  inevitably reacts with the oxygen in the air in the step of transfer from the vacuum microprocessing to the air, even if not using an etching gas containing oxygen atoms as explained above, and forms an oxide film (or oxide layer)  117  at the surface-most layer where the hard mask contacts the oxygen. 
         [0014]    However, if the oxide film  117  is formed at the surface-most layer of the hard mask  111   a  of the Ta layer  111 , the oxide film  117  becomes an insulation layer. If the insulation layer is formed at the surface-most layer of the TMR device  101 , a parasitic resistance ends up being formed, so the above-mentioned MR ratio falls. This drop in the MR ratio is more striking with a TMR device of the CPP type, that is, the type shown in  FIGS. 7A to 7C , sending a sense current in a direction perpendicular to the plane of the device film, compared with the CIP type sending a sense current in a direction parallel to the plane of the device film. Therefore, it is necessary to remove the oxide film  117  at the surface-most layer of the hard layer  111   a  of the Ta layer  111  to prevent a drop in the MR ratio, but as explained above, it is necessary to protect the free layer  115  from oxygen in the air when transferring the TMR device finished being microprocessed by etching to the outside of the dry etching apparatus. This problem similarly occurs when using Ti as a hard mask instead of Ta. 
         [0015]    The TMR device after microprocessing is exposed once to the air, then transferred to the next step of production for forming electrodes etc. 
         [0016]    Further, as related art of the present invention, there are the thin film device and method of production of the same disclosed in Japanese Patent Publication (A) No. 2001-28442. The thin film device and method of production of this publication relate to a magnetic head and a method of production of a magnetic head and mainly has as its object formation of lead electrodes by highly selective dry etching without damaging (etching) the GMR. 
       OBJECTS AND SUMMARY 
       [0017]    It is an object of the present invention to prevent the hard mask left as the protective layer after the microprocessing by dry etching from being oxidized in the conventional method of production of a TMR device or other magnetoresistance effect device and as a result an insulation layer being formed and a drop and deterioration of the MR ratio being caused. 
         [0018]    An object of the present invention is to provide a method of production of a magnetoresistance effect device able to prevent or minimize a drop in the MR ratio and maintain the high performance of the magnetoresistance effect device even if forming an oxide layer as a surface-most layer constituting a protective layer by the oxidation process inevitably included in the process of production of microprocessing of dry etching performed in a vacuum, without making any special changes to the process of production, by doubly piling up two mask layers used for microprocessing. That is, an object of the present invention is to provide a method of production of a magnetoresistance effect device capable of positively utilizing the protective layer with the oxide layer formed through the production process as a layer formed by conductive oxide substance. 
         [0019]    A method of production of a magnetoresistance effect device is configured as follows for achieving the above object. 
         [0020]    The method of production of the magnetoresistance effect device is a method of dry etching used for production of a magnetoresistance effect device comprised of a magnetic multilayer film including at least two magnetic layers. This method comprises a step of providing under a first mask material comprised of a nonorganic material a second mask material able to react with other atoms to form a conductive substance so that the first and second mask materials make layers which are doubly piled up. 
         [0021]    Among the above-mentioned magnetoresistance effect devices, in a TMR device sending a sense current in a direction perpendicular to the plane of the device film, when the surface-most layer of the protective layer reacts with for example oxygen atoms in the process of microprocessing by this dry etching apparatus, by using a material which does not form an insulator, but can form a conductor so as to form a protective layer, it is possible to prevent or minimize a drop in the MR ratio and for example maintain the high performance of the MRAM, magnetic head, etc. formed by the TMR device. 
         [0022]    Preferably, the second mask material is a material able to react with oxygen atoms to form a conductive oxide. 
         [0023]    More preferably, the second mask material able to form a conductive oxide is one of Ru (ruthenium), Rh (rhodium), Os (osmium), Nb (niobium), Ir (iridium), and Re (rhenium). 
         [0024]    Still more preferably, the method further comprises a step of removing the first mask material by an etching gas including oxygen atoms to change the surface of the second mask material to the conductive oxide, and leaving the second mask material to form an electrode. 
         [0025]    Still more preferably, the etching gas including oxygen atoms is a mixed gas of carbon monoxide and a nitrogen compound or an alcohol-based gas including at least one hydroxy group. 
         [0026]    An embodiment of the present invention takes effect as follows. When microprocessing a TMR device or other magnetoresistance effect device used as a MRAM or magnetic head etc. by dry etching, since the second mask layer is a material which can form a conductive substance, the second mask layer not completely removed, but remains after the first mask material is completely etched away and forms an electrode serving also as a protective layer, so a good sense current is obtained and a high MR ratio can be obtained. 
         [0027]    Further, according to an embodiment of the present invention, by forming the second mask material by Ru or another material able to form a conductive oxide, it is possible to completely remove the first mask material in microprocessing by reactive ion etching (RIE) using a predetermined etching gas and not completely remove the second mask material under it but leave it as a protective layer and thereby make the surface-most layer a conductive oxide. It is possible to use this as it is as an electrode. Due to this, it is possible to eliminate the film-forming step of again forming an electrode after microprocessing the magnetic material forming the magnetoresistance effect device. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0028]    These and other objects and features of the present invention will become clearer from the following description of the preferred embodiments given with reference to the attached drawings, wherein: 
           [0029]      FIG. 1A  is a structural view of a multilayer film showing an example of the structure of a conventional magnetoresistance effect device; 
           [0030]      FIG. 1B  is a structural view of a multilayer film showing an example of the structure of a magnetoresistance effect device according to an embodiment of the present invention; 
           [0031]      FIGS. 2A to 2C  are transition diagrams showing a dry etching process in a process of production of a magnetoresistance effect device according to an embodiment of the present invention; 
           [0032]      FIG. 3A  shows a table showing the resistivities of conductive oxides; 
           [0033]      FIG. 3B  shows a table showing the resistivities of single metals; 
           [0034]      FIG. 4  is a view, obtained by experimental results, comparing the MR ratio between the case of using a protective layer of Ru of an embodiment of the present invention and the case of using Ta of the related art; 
           [0035]      FIG. 5  is a longitudinal cross-sectional view showing the basic structure of a TMR device of related art; 
           [0036]      FIG. 6A  is a view explaining the change of resistivity in the conventional TMR device; 
           [0037]      FIG. 6B  is a view explaining the change of resistivity in a conventional TMR device; and 
           [0038]      FIGS. 7A to 7C  are transition diagrams showing a dry etching process in a process of production of a magnetoresistance effect device according to the related art and explaining problems in the same. 
       
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
       [0039]    Hereinafter, preferred embodiments of the present invention will be explained in accordance with the attached drawings. 
         [0040]      FIG. 1A  shows an example of the structure of a magnetoresistance effect device (TMR device) in a conventional production process (microprocessing step), and  FIG. 1B  shows, in comparison, an example of the structure according to an embodiment of the present invention. 
         [0041]    In the example of the structure of a conventional magnetoresistance effect device (TMR device)  10  shown in FIG.  1 A, a substrate  11  is formed with a bottom electrode  12 . The bottom electrode  12  is formed with a multilayer film comprised of eight layers forming the magnetoresistance effect device. This eight-layer multilayer film is comprised, from the bottommost first layer to the topmost eighth layer, magnetic layers piled up or deposited in the order of “Ta”, “PtMn”, “a pinned layer”, “Ru”, “another pinned layer”, “a barrier layer”, “a free layer”, and “Ta”. The first layer (Ta) is the bottom layer, the second layer (PtMn) is an antiferromagnetic layer, the third layer to the fifth layer (pinned layer, Ru, and pinned layer) are pinned magnetization layers, the sixth layer (barrier layer) is an insulation layer, the seventh layer (free layer) is free magnetization layer, and the eighth layer (Ta) is a hard mask forming a protective layer. The pinned magnetization layers, the insulation layer, and the free layer form an MR device portion  13 . 
         [0042]    In the example of the structure of a magnetoresistance effect device  20  according to an embodiment of the present invention ( FIG. 1B ), a substrate  11  is formed with a bottom electrode  12 . The bottom electrode  12  is formed with a multilayer film comprised of nine layers forming a magnetoresistance effect device. This nine-layer multilayer film is comprised, from the bottommost first layer to the topmost ninth layer, of magnetic layers piled up or deposited in the order of “Ta”, “PtMn”, “a pinned layer”, “Ru”, “a pinned layer”, “a barrier layer”, “a free layer”, “Ru (200 Å)”, and “Ta”. The first layer to the seventh layer and the ninth layer are the same in configuration as in the multilayer structure of the conventional magnetoresistance effect device ( FIG. 1A ) explained above. That is, the first layer (Ta) is the primer layer, the second layer (PtMn) is an antiferromagnetic layer, the third layer to the fifth layer (pinned layer, Ru, and pinned layer) are pinned magnetization layers, the sixth layer (barrier layer) is an insulation layer, the seventh layer (free layer) is a free magnetization layer, and the ninth layer (Ta) is a hard mask forming a protective layer. In this magnetoresistance effect device, the Ta of the topmost ninth layer is used as a hard mask, a TMR device portion  13  is formed by the pinned magnetizations, insulation layer and free layer, and a magnetic head cap  14  is formed by the eighth layer (Ru) and ninth layer (Ta). The magnetoresistance effect device of this embodiment of the present invention includes the insertion, between the seventh layer (free layer) and ninth layer (Ta), of the Ru (ruthenium) layer  15  as a protective layer able to be used as an electrode. The thickness of the Ru layer of the protective layer  15  is 200 Å, for example. 
         [0043]    Next, the dry etching process performed in a vacuum in the process of production of the magnetoresistance effect device  20  shown in  FIG. 1B  will be explained with reference to  FIGS. 2A to 2C . As the etching apparatus, an ICP plasma apparatus having a one-turn antenna is used, the antenna is connected to a plasma high frequency power source for the supply of high frequency power (hereinafter referred to as “source power”), and the object being etched, that is, the wafer on which the TMR device portion is patterned, is supplied with a self bias voltage (hereinafter referred to as the “bias power”). 
         [0044]    In the state shown in  FIG. 2A , the topmost layer of the Ta layer  22  is etched using the resist  21  as a mask so as to create a hard mask (first mask material) of the Ta layer  22 . The etching conditions include an internal pressure of the vacuum vessel of the processing chamber of 0.8 Pa, a source power of 500 W, a bias power of 70 W, an etching gas of CF 4 , and a flow rate of 50 sccm (326 mg/min). In the state shown in  FIG. 2B , as a result, a first mask layer of a Ta layer constituting the hard mask  23  is formed. In  FIG. 2B , next, the Ta layer of the hard mask  23  is used to etch part of the TMR device  13  for example. At this time, as the etching gas, for example, a mixed gas of carbon monoxide and a nitrogen compound (CO+NH 3 ) or an alcohol-based etching gas including a hydroxy group (CH 3 OH) is used. The etching conditions when using a mixed gas of CO and NH 3  as an etching gas include an internal pressure of the vacuum vessel of the processing chamber of 0.6 Pa, a source power of 1000 W, a bias power of 300 W, a flow rate of CO gas as the etching gas of 25 sccm (31.25 mg/min), and a flow rate of NH 3  gas of 75 sccm (57.0 mg/min). When using CH 3 OH gas as the etching gas, the conditions include an internal pressure of the vacuum vessel of the processing chamber of 0.4 Pa, a source power of 1000 W, a bias power of 200 W, and a flow rate of etching gas of 15 sccm (18.75 mg/min). In  FIG. 2C , an example is shown of the state in which the TMR device portion  13  has been etched. In this example, after the free layer  24  and insulator (barrier layer)  25  are etched and the TMR device is etched, or when the TMR device is etched, the hard mask  23  of Ta is removed. Thereby, the Ru layer  15  is exposed as the surface-most layer on the free layer  24 . 
         [0045]    That is, since the selectivity of Ru with respect to Ta is about 10, when the thickness of the Ru layer of the protective layer  15  is for example 200 Å, the Ta (hard mask) of the first layer is made about 20 Å so as not to leave the hard mask (Ta) when continuing etching using the Ru layer as the second mask material. The dry etching process is ended leaving a thickness of the Ru layer  15  of tens of Å required for functioning as a protective layer. 
         [0046]    Note that in accordance with the above dry etching process, in the process of the states shown in  FIG. 2B  to  FIG. 2C , the above etching process is sometimes performed down to the layer of Ta on the bottom electrode  12  (selectivity with respect to Ru free layer, barrier layer, and pinned layers is about 1 to 4). 
         [0047]    Here, in the dry etching process from the state of  FIG. 2B  to the state of  FIG. 2C , there are two methods for removing the hard mask  23  of Ta. The first method of removal is the method of preadjusting the thickness of the hard mask  23  so that the hard mask  23  is completely removed when the etching ends when etching the TMR device as explained above. The second method of removal is a method of not adjusting the thickness, but performing the processing for completely removing the hard mask  23  after ending the etching of the TMR device. 
         [0048]    In the process of production of the magnetoresistance effect device  20 , after the dry etching process introducing oxygen into the etching gases shown in  FIGS. 2A to 2C , the magnetoresistance effect device  20  is exposed to the air, and the oxygen atoms in the air react with the surface of the layer of Ru of the second mask material  15  to form the layer of the oxide  26  (oxide film). This oxide  26  becomes a conductive oxide due to the characteristics of the Ru. 
         [0049]    The tables of  FIG. 3A  and  FIG. 3B  show respectively the resistivities (Ωm) of the conductive oxides and the resistivities (Ωm) of metals alone. As shown in  FIGS. 3A and 3B , the conductive oxide of Ru, that is, RuO 2 , has a resistivity substantially the same as the metal Ta alone. 
         [0050]    Therefore, if using Ru as the second mask material  15  in the dry etching process of the TMR device of the magnetoresistance effect device  20  and finally completely removing the Ta of the first mask  23 , there is the advantage that a layer of a conductive insulator  26  is formed at the surface-most layer in the process of production and the cause of the drop in the MR ratio explained above can be removed.  FIG. 4  shows a comparison of the MR ratio characteristic when using magnetoresistance effect devices of the same configuration from the substrate to the TMR device as in  FIGS. 1A and 1B  between the case of using Ta for the surface-most layer becoming the protective layer after etching and the case of making the Ru become the protective layer after etching as in the embodiment of the present invention. The etching conditions, as explained in the embodiment of  FIGS. 2A to 2C , may be the conditions of the case of use of either a mixed gas of carbon monoxide and a nitrogen compound (CO+NH 3 ) or an alcohol-based etching gas including a hydroxy group (CH 3 OH), but they are made so that after etching, the thicknesses of the Ta and Ru remaining as the “free layer” protective layer on the TMR device become substantially the same (here 20-30 Å). As being clear by the comparison table shown in  FIG. 4 , the MR ratio when using the Ru of the second mask material as the protective layer is about three times as many as the MR ratio when using the Ta instead. 
         [0051]    Further, by finally completely removing the Ta of the first mask material  23  in the dry etching process of the TMR device of the magnetoresistance effect device  20 , a layer of a conductive oxide  26  is formed at the surface-most layer in the process of production, so the layer of the conductive oxide  26  can be used as a top electrode. Therefore, there is the advantage that it is no longer required to provide a step for forming the top electrode, which was required in the conventional production process. 
         [0052]    As explained above, in the dry etching process of a TMR device in the process of production of the magnetoresistance effect device  20 , the second mask material  15  of the magnetic head used is the material Ru able to react with oxygen atoms to form a conductive oxide, so the technical effect is exhibited of preventing or minimizing the drop in the MR ratio and enabling the top electrode to be replaced with a conductive oxide. 
         [0053]    As other materials having similar characteristics as the above Ru, Rh (rhodium), Os (osmium), Nb (niobium), Ir (iridium), and Re (rhenium) may be mentioned. As described in the second row on of the table of  FIG. 3A , the oxides Rh, Os, Nb, Ir, and Re, that is, RhO 2 , OsO 2 , NbO, IrO 2 , and ReO 3  also have sufficient conductivity. Note that  FIG. 3B  shows a table of the resistivities of metals having conductivity for comparison. 
         [0054]    Note that in the explanation of the above embodiment, an example of a material able to react with oxygen atoms to form a conductive oxide was explained, but of course it is also possible to similarly apply the basic thinking of the present invention to a material able to form a nitride or carbide having conductivity. 
         [0055]    The configurations, shapes, sizes (thicknesses), and layouts explained in the above embodiments are only shown schematically to an extent enabling the present invention to be understood and worked. Further, the numerical values and compositions (materials) are only shown for illustration. Therefore, the present invention is not limited to the explained embodiments and can be changed in various ways within the scope of the technical idea shown in the claims. 
         [0056]    Further, as the etching apparatus, a helicon type apparatus called a “high density plasma source”, a two-frequency excitation parallel plate type plasma apparatus, a microwave type plasma apparatus, etc. may be utilized. 
         [0057]    One object of the present invention is to prevent or minimize a drop in the MR ratio in the production of a TMR device or other magnetoresistance effect device. 
         [0058]    The present disclosure relates to subject matter contained in Japanese Patent Application No. 2004-240838 filed on Aug. 20, 2004, the disclosure of which is expressly incorporated herein by reference in its entirety. 
         [0059]    Although only preferred embodiments are specifically illustrated and described herein, it will be appreciated that many modifications and variations of the present invention are possible in light of the above teachings and within the purview of the appended claims without departing from the spirit and intended scope of the invention.
A method of production of a magnetoresistance effect device is able to prevent or minimize a drop in the MR ratio and maintain the high performance of the magnetoresistance effect device even if forming an oxide layer as a surface-most layer constituting a protective layer by the oxidation process inevitably included in the process of production of microprocessing by dry etching performed in a vacuum. Two mask layers used for microprocessing are doubly piled up. This method of production of a magnetoresistivity effect device including a magnetic multilayer film including at least two magnetic layers includes a step of providing under a first mask material that is a nonorganic material a second mask material able to react with other atoms to form a conductive substance, and a device made according to the method.