1. Field of the Invention
This invention relates generally to a method for deposition of an ultra-thin metal oxide film onto a film of a metal different from the metal in the metal oxide film.
2. Description of the Related Art
Ultra-thin metal oxide films have application in nanotechnology devices. The deposition of these films to ultra-thin thicknesses, e.g., less than approximately 100 Å, is especially difficult when the film onto which the metal oxide film is to be deposited is also a metal, but a metal different from the metal in the metal oxide. In addition there are applications where it is important to be able to deposit the metal oxide film while minimizing the oxidation of the underlying metal.
One application of such ultra-thin metal oxide films is as capping layers in giant magnetoresistive (GMR) sensors, which are widely used as magnetoresistive read heads in magnetic recording disk drives. Nonmagnetic metal oxides, e.g. TaOx or AlOx, have been proposed to cap the free ferromagnetic layer in GMR spin-valve read heads. The nonmagnetic metal oxide capping layers are sometimes called “specular reflection” layers because they act to confine electrons and thus increase the occurrence of spin-dependent scattering of electrons at the interface of the spacer layer and the free ferromagnetic layer. GMR read heads with nonmagnetic metal oxide capping layers are described in published patent application U.S. 2002/0196589 A1 and U.S. Pat. No. 6,709,767.
Another application for such ultra-thin metal oxide films is in magnetic tunnel junction (MTJ) devices. A MTJ is comprised of two ferromagnetic metal layers separated by an ultra-thin insulating metal oxide tunnel barrier. The various MTJ devices being developed include a nonvolatile magnetic random access memory (MRAM) with MTJ memory cells, as described in U.S. Pat. No. 5,640,343; a magnetic tunnel transistor (MTT), as described by S. van Dijken, X. Jiang, and S. S. P. Parkin, “Room Temperature Operation of a High Output Magnetic Tunnel Transistor”, Appl. Phys. Lett. 80, 3364 (2002); and a MTJ magnetic field sensor, such as a magnetoresistive read head for use in a magnetic recording disk drive as described in U.S. Pat. No. 5,729,410.
An important property for a MTJ device is the signal-to-noise ratio (SNR). The magnitude of the signal is dependent upon the tunneling magnetoresistance (TMR), i.e., the change in resistance divided by the resistance (ΔR/R). However, the noise exhibited by the MTJ device is determined, in large part, by the resistance R of the device. Thus an MTJ device should have high TMR and low R. The resistance R of a MTJ is largely determined by the resistance of the insulating tunnel barrier for a device of given dimensions since the resistance of the electrical leads and the two ferromagnetic metal layers contribute little to the resistance.
The most common MTJ tunnel barrier is an amorphous aluminum oxide (Al2O3) film made by vacuum deposition of an aluminum layer followed by plasma or natural oxidation. For Al2O3 tunnel barriers it has been found that as the thickness is reduced to reduce the resistance R, the TMR is also typically reduced, most likely because of the formation of pin holes in the ultra-thin tunnel barriers.
More recently, MTJs with epitaxial tunnel barriers of magnesium oxide (MgO) have been investigated. See M. Bowen et al., “Large magnetoresistance in Fe/MgO/FeCo (001) epitaxial tunnel junctions”, Appl. Phys. Lett. 79, 1655 (2001); and S. Mitani et al., “Fe/MgO/Fe(100) epitaxial magnetic tunnel junctions prepared by using in situ plasma oxidation”, J. Appl. Phys. 90, 8041 (2003). These MgO tunnel barriers have been prepared by laser ablation, molecular beam epitaxy, and by the method used for amorphous Al2O3 tunnel barriers, i.e., conventional vacuum deposition followed by in situ plasma oxidation.
Metal oxide films formed from other than Al and Mg have also been proposed for MTJ tunnel barriers. These include oxides of Ti, Ta, Y, Ga and In, and oxides of these metals alloyed with Al and/or Mg, as described in U.S. Pat. Nos. 6,359,289 and 6,756,128. The most widely described method for the deposition of these metal oxide films is also by conventional vacuum deposition followed by in situ plasma or natural oxidation.
The conventional method of forming the metal oxide tunnel barrier metal by vacuum deposition of the metal followed by oxidation is very delicate and must be re-optimized for every deposited metal thickness. This method can also be very slow due to the post-deposition oxidation step. Too little oxidation leaves behind under-oxidized metal, while too much oxidation attacks the underlying film. In both the under-oxidized and over-oxidized cases the MTJ performance can be severely degraded.
Thus, it is desirable to develop a process for forming an ultra-thin metal oxide film onto a film of a metal different from the metal in the metal oxide that does not suffer from the problems associated with the prior art processes, and that will enable the fabrication of MTJ devices with high TMR and low R.
The invention is a method for reactive sputter deposition of an ultra-thin film of an oxide of a first metal onto a film of a second metal in which oxidation of the second metal is minimized. The method can be part of the fabrication of a GMR sensor with a metal oxide capping layer to increase specular conductance, or part of the fabrication of a MTJ with the metal oxide film becoming the tunnel barrier of the MTJ. The metal oxide film is reactively sputter deposited in the presence of reactive oxygen (O2) gas from a target consisting essentially of the first metal, with the sputtering occurring in the “high-voltage” state to assure that deposition occurs with the target in its metallic mode, i.e., no or minimal oxidation. When the metal oxide film is for a MTJ tunnel barrier, then the target is formed of a metal consisting essentially of Al, Ti, Ta, Y, Ga or In; or an alloy of two or more of these metals; or an alloy of one or more of these metals with Mg; and the film of the second metal is an iron-containing film, typically a film of Fe or a CoFe alloy.
The walls of the sputter deposition chamber are first conditioned by applying power to activate the target in the presence of the argon (Ar) inert sputtering gas while the film of the second metal is protected by a movable shutter. This conditioning step coats the chamber walls with the first metal, and thus removes any “memory” of prior oxygen processes in the chamber, which is important for a repeatable reactive deposition process. With the shutter still protecting the film of the second metal, the reactive O2 gas is introduced into the chamber at a predetermined flow rate. After the O2 flow has stabilized, the shutter is opened and the target is activated for a specific time to achieve the desired tunnel barrier thickness. The specific time has been previously determined, from the known O2 flow rate, to assure that the sputter deposition occurs while there is minimal oxidation of the target.
Because the metallic mode of the target has a finite lifetime, a set of O2 flow rates and associated sputter deposition times are established, with each flow rate and deposition time assuring that deposition occurs with the target in the metallic mode and resulting in a known tunnel barrier thickness. The commencement of target oxidation is associated with a decrease in target voltage, so the sputtering can also be terminated by monitoring the target voltage and terminating application of power to the target when the voltage reaches a predetermined value.
Since deposition should occur only while the target is in its metallic mode, the tunnel barrier must be completed while the target is still metallic. This if a thicker tunnel barrier is required it is deposited in several layers, with the process described above repeated for each layer. Also, if a multilayer tunnel barrier with different metal oxide or metal-alloy oxide layers is desired, the process described above is repeated for each layer, but with a different target made of the desired metal or metal alloy.
As an optional final step, after the sputtering has terminated, the deposited metal oxide tunnel barrier can be exposed to O2 in the chamber as a “natural oxidation” to encourage the metal oxide tunnel barrier to achieve its natural stoichiometry.
For a fuller understanding of the nature and advantages of the present invention, reference should be made to the following detailed description taken together with the accompanying figures.
Prior Art
The method of this invention has application to the formation of the tunnel barrier required for a MTJ read head. However, the method is fully applicable to forming tunnel barriers for other MTJ devices, as well as for the more general application of forming an ultra-thin (less than approximately 100 Å) metal oxide film on a film of a different metal.
Because the MTJ read head has application for use in a magnetic recording disk drive, the operation of a conventional hard disk drive (HDD) will be briefly described with reference to
Located between the lower shield layer S1 and the MTJ are the bottom electrode or electrical lead 126 and a seed layer 125. The seed layer 125 facilitates the deposition of the antiferromagnetic layer 124. Located between the MTJ and the upper shield layer S2 are a capping layer 112 and the top electrode or electrical lead 113.
In the presence of an external magnetic field in the range of interest, i.e., magnetic fields from recorded data on the disk 12, the magnetization direction 111 of free layer 110 will rotate while the magnetization direction 121 of reference layer 120 will remain fixed and not rotate. Thus when a sense current IS is applied from top lead 113 perpendicularly through the stack to bottom lead 126, the magnetic fields from the recorded data on the disk will cause rotation of the free-layer magnetization 111 relative to the pinned-layer magnetization 121, which is detectable as a change in electrical resistance.
The leads 126, 113 are typically Ta. They are optional and used to adjust the shield-to-shield spacing. The seed layer 125 is typically one or more layers of NiFeCr, NiFe, Ta or Ru. The antiferromagnetic layer 124 is typically a Mn alloy, e.g., PtMn, NiMn, FeMn, IrMn, PdMn, PtPdMn or RhMn. The capping layer 112 provides corrosion protection and is typically formed of Ru or Ta. A hard magnetic layer (not shown) may also be included in the stack for magnetic stabilization of the free ferromagnetic layer 110.
The ferromagnetic layers 123, 120, 110 are typically formed of an alloy of one or more of Co, Fe and Ni, or a bilayer of two alloys, such as a CoFe—NiFe bilayer. For example, reference ferromagnetic layer 120 may be a CoFe alloy, typically 10 to 30 Å thick, and the free ferromagnetic layer 110 may be a bilayer of a CoFe alloy, typically 10-15 Å thick and formed on the tunnel barrier 130, with a NiFe alloy, typically 10-30 Å thick, formed on the CoFe layer of the bilayer.
The Invention
The invention will be explained with respect to forming a magnesium oxide (MgO) tunnel barrier on an iron-containing film, more particularly a CoFe alloy ferromagnetic film. Thus in this example the first metal is Mg and the second metal is Fe or an Fe alloy. It is understand, however, that the method is applicable for forming any ultra-thin metal oxide film on a film of a different metal.
The process will be described for depositing an ultra-thin (approximately 5-20 Å) MgO tunnel barrier on an iron-containing metallic film, e.g., a Co90Fe10 ferromagnetic film. The MgO tunnel barrier is tunnel barrier 130, the CO90Fe10 film is reference ferromagnetic layer 120, and the substrate is the polished shield layer S1, as described above with reference to
The method of this invention can be understood with reference to
The poisoned state would appear to be the preferred state to perform the reactive deposition of the MgO film because it is easier to control, it deposits the MgO at a much lower rate than the high-voltage state, and the deposited MgO film is reliably well oxidized. However, as part of the development of the process of this invention it has been discovered that reactive deposition of MgO in the low-voltage or poisoned state is very aggressive to the underlying iron-containing metallic film on which the MgO is deposited. This results in a loss of magnetic moment at the interface of the CoFe ferromagnetic film and the MgO tunnel barrier. The MTJs fabricated in this state thus have undesirable high resistance (R) and low tunneling magnetoresistance (TMR).
The method of this invention reactively sputter deposits the MgO tunnel barrier in the high-voltage state. The reactive gas flow rate and sputter time are controlled to assure there is no substantial oxidation of the Mg target.
As an initial optional step in the inventive process, the target shutter 230 and substrate shutter 240 are both closed and pure Ar is introduced to the vacuum chamber 202. The target 210 is then activated and sputtered in the presence of pure Ar to eliminate any oxidized material from the target.
Next, with the target shutter 230 open and the substrate shutter 240 closed, the target 210 is again sputtered in pure Ar at sufficiently high power, e.g., 3 W/sqcm. This step conditions the chamber 202 by coating the chamber walls with the Mg metal. Because the chamber walls are metallic and an active oxygen-gettering surface, they provide additional O2 pumping, thus delaying the onset of target oxidation. The coating of the walls with Mg removes any “memory” of prior oxygen processes in the chamber, which is important for a repeatable reactive deposition process. The substrate shutter 240 protects the CoFe metallic film on the substrate from exposure to the sputtered Mg atoms during this chamber conditioning step.
Next, with the target shutter 230 still open and the substrate shutter 240 still closed, the oxygen gas is introduced into the chamber at the desired flow rate. After the O2 flow has stabilized, the substrate shutter 240 is opened while the desired power is applied to the Mg target 210 to begin the reactive deposition of the tunnel barrier. The power is applied for a time required to achieve the desired deposited thickness. It has been previously determined that sputter deposition occurs while there is minimal oxidation of the Mg target, at the desired O2 flow rate.
An important aspect of the process is that for each O2 flow rate, the metallic mode of the Mg target has a finite lifetime. This is illustrated in
Thus the data of
Instead of reactively sputter depositing a MgO tunnel barrier, other metal oxide tunnel barriers may be formed from other targets with the method of this invention. Thus oxides of Al, Ti, Ta, Y, Ga or In may be formed as tunnel barriers by use of a target made of the desired metal. Also, the tunnel barrier may be made of an oxide of a metal alloy of two or more of these metals, or an oxide of one or more of these metals alloyed with Mg, by use of the desired metal alloy as the target.
The method of this invention also enables the fabrication of multilayer tunnel barriers, such as proposed in U.S. Pat. No. 6,347,049. These tunnel barriers have at least two of the tunnel barrier layers in the multilayer formed from different metal oxides or metal-alloy oxides. Examples include Al2O3/MgO or MgO/Al2O3 bilayers and MgO/Al2O3/MgO or Al2O3/MgO/Al2O3 trilayers. Thus to form a multilayer metal oxide or metal-alloy oxide tunnel barrier layer according to this invention, the process described above is repeated for each layer, but with a different target made of the desired metal or metal alloy.
While depositing in the metallic mode is very beneficial, the resulting MgO film must be well-oxidized. This requirement leads toward higher oxygen flow rates and thus toward a shorter metallic mode lifetime. This situation can be mitigated by the use of an optional final step of exposing the deposited MgO tunnel barrier to O2 in the chamber. For example, an O2 exposure of 100 mTorr for approximately 60 seconds is a “natural oxidation” step that encourages the tunnel barrier to achieve its natural MgO stoichiometry, and allows the use of lower O2 flows during the reactive sputtering.
A second iron-containing film can then be sputter deposited directly on the tunnel barrier to form the top ferromagnetic layer of the MTJ. If the MTJ is to be used in the MTJ read head described above the second iron-containing film can be a CoFe free ferromagnetic layer 110 (
The MTJs made with the method of this invention have TMR and resistance-area product (RA) values significantly improved over previously reported MTJs with MgO tunnel barriers. Two typical MTJs made according to the method of this invention have a TMR of approximately 35% with a RA of approximately 3.5 Ω-(μM)2 and a TMR of approximately 40% with a RA of approximately 5 Ω-(μm)2. In addition, the method of this invention minimizes oxidation of the underlying second metal. In the case of an MTJ a “clean” interface of CoFe/MgO, i.e., substantially no oxides of Co or Fe at the interface, is believed to lead to improved magnetoresistance.
While the method of this invention has been described for fabricating a MTJ read head, the method is fully applicable to fabricate other MTJ devices, including MTJ memory cells and MTTs. In addition the method has application to the fabrication of other nanotechnology devices, such as giant magnetoresistive (GMR) sensors where the metal oxide layer is used to increase specular conductance.
While the present invention has been particularly shown and described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made without departing from the spirit and scope of the invention. Accordingly, the disclosed invention is to be considered merely as illustrative and limited in scope only as specified in the appended claims.
This application is related to concurrently filed application Ser. No. ______ filed ______, 2004 and titled “METHOD FOR REACTIVE SPUTTER DEPOSITION OF A MAGNESIUM OXIDE (MgO) TUNNEL BARRIER IN A MAGNETIC TUNNEL JUNCTION” (Attorney Docket No. HSJ920040148US1).