Magnetic element with perpendicular magnetic anisotropy (PMA) and improved coercivity field (Hc)/switching current ratio
11264566 · 2022-03-01
Assignee
Inventors
- Santiago Serrano Guisan (San Jose, CA, US)
- Luc Thomas (San Jose, CA, US)
- Jodi Mari Iwata (San Carlos, CA, US)
- Guenole Jan (San Jose, CA, US)
- Ru-Ying Tong (Los Gatos, CA)
Cpc classification
G11C11/161
PHYSICS
International classification
G11C11/16
PHYSICS
Abstract
A perpendicular magnetic tunnel junction is disclosed wherein a metal insertion (MIS) layer is formed within a free layer (FL), a partially oxidized Hk enhancing layer is on the FL, and a nitride capping layer having a buffer layer/nitride layer (NL) is on the Hk enhancing layer to provide an improved coercivity (Hc)/switching current (Jc) ratio for spintronic applications. Magnetoresistive ratio is maintained above 100%, resistance×area (RA) product is below 5 ohm/μm.sup.2, and thermal stability to 400° C. is realized. The FL comprises two or more sub-layers, and the MIS layer may be formed within at least one sub-layer or between sub-layers. The buffer layer is used to prevent oxygen diffusion to the NL, and nitrogen diffusion from the NL to the FL. FL thickness is from 11 Angstroms to 25 Angstroms while MIS layer thickness is preferably from 0.5 Angstroms to 4 Angstroms.
Claims
1. A perpendicular magnetic tunnel junction (p-MTJ) structure, comprising: (a) a pinned layer (PL); (b) a tunnel barrier layer with a first surface that adjoins the PL, and a second surface that contacts a free layer (FL) and forms a first interface with the FL; (c) the FL that has a FL1/MIS/FL2 configuration wherein a metal insertion (MIS) layer is formed between a first FL sub-layer (FL1) and a second FL sub-layer (FL2), and wherein FL1 has perpendicular magnetic anisotropy (PMA) as a result of the first interface, and FL2 has PMA as a result of a second interface with a Hk enhancing layer; (d) the Hk enhancing layer having a non-stoichiometric oxidation condition, and that adjoins the FL to form the second interface on a side of the FL that is opposite to the first interface; and (e) a nitride capping layer (NCL), comprising: (1) a nitride layer (NL) that is a metal nitride or metal oxynitride; and (2) a buffer layer that is a single layer or multilayer that is one or more of Co, Fe, CoFe, and CoFeNi, or one or more of Mo, W, Ru, Nb, Ta, Cr, Pt, Cu, Au, Ag, Zn, V, Cd, Sn, Ir, Mn, and Rh that adjoins the NL and contacts the Hk enhancing layer on a side thereof that is opposite to the second interface, wherein the buffer layer prevents oxygen diffusion from the Hk enhancing layer to the NL, and blocks nitrogen diffusion from the NL to the FL.
2. The p-MTJ of claim 1 wherein the MIS layer is a continuous layer, a multilayer, a discontinuous layer, or is a plurality of metal particles, or metal clusters.
3. The p-MTJ of claim 1 wherein the MIS layer has a thickness from 0.5 Angstroms to 4 Angstroms.
4. The p-MTJ of claim 1 wherein the MIS layer is a single layer or multilayer of one or more of Nb, Mo, Ta, W, Re, Ti, V, Cr, Zr, Hf, Ru, Rh, Os, Ir, Cu, Zn, Pt, Au, Ag, Pd, Al, B, Ga, Si, and Ge.
5. The p-MTJ of claim 1 wherein one or both of FL1 and FL2 is one or more of Co, Fe, CoFe, CoFeB, CoB, FeB, CoFeNi, and CoFeNiB.
6. The p-MTJ of claim 1 wherein one or both of FL1 and FL2 is comprised of a high Ku material having inherent PMA which is a Heusler alloy that is Ni.sub.2MnZ, Pd.sub.2MnZ, Co.sub.2MnZ, Fe.sub.2MnZ, Co.sub.2FeZ, Mn.sub.3Ge, or Mn.sub.2Ga where Z is one of Si, Ge, Al, Ga, In, Sn, and Sb, or an ordered L1.sub.0 or L1.sub.1 material with a composition that is one of MnAl, MnGa, or RT wherein R is Rh, Pd, Pt, Ir, or an alloy thereof, and T is Fe, Co, Ni, or an alloy thereof, or a rare-earth alloy with a TbFeCo, GdCoFe, FeNdB, or SmCo composition.
7. The p-MTJ of claim 1 where FL1 has a thickness t1, and FL2 has a thickness t2 where a sum of t1 and t2 is from 11 Angstroms to 25 Angstroms.
8. The p-MTJ of claim 1 wherein the Hk enhancing layer is a single layer or a laminate comprised of an oxide or oxynitride of one or more of Mg, Si, Sr, Ti, Ba, Ca, La, Al, Mn, V, and Hf, and has a resistance×area (RA) product less than a RA product of the tunnel barrier layer.
9. The p-MTJ of claim 1 further comprising a seed layer formed on a substrate, to yield a seed layer/PL/tunnel barrier layer/FL/Hk enhancing layer/NCL stack in a bottom spin valve configuration.
10. The p-MTJ of claim 1 further comprising a seed layer formed on a substrate, and a capping layer (CL) on the PL to yield a seed layer/NCL/Hk enhancing layer/FL/tunnel barrier layer/PL/CL stack in a top spin valve configuration.
11. The p-MTJ of claim 1 wherein the p-MTJ is incorporated in a magnetic random access memory (MRAM), spin transfer torque (STT)-MRAM, spin orbit torque (SOT)-MRAM, spin torque oscillator, Spin Hall Effect device, magnetic sensor, or a biosensor.
12. The p-MTJ of claim 1 wherein the NL is comprised of a metal nitride (M1N) or metal oxynitride (M1ON) where M1 is one or more of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W, and Si.
13. The p-MTJ of claim 1 wherein the NL has a M2M3N or M2M3ON composition where M2 is one of B, Al, Si, Ga, In, and TI, and M3 is one or more of Pt, Au, Ag, Mg, Ca, Sr, Ba, Sc, Y, La, Co, Fe, Mn, Ru, Rh, Ir, Ni, Pd, Zn, Cu, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W such that the NL is a conductive alloy layer, or has M3 conductive channels formed in a M2N or M2ON insulating matrix.
14. The p-MTJ of claim 1 wherein the buffer layer is a single layer or multilayer that is one or more of Mo, W, Ru, Nb, Ta, Cr, Pt, Cu, Au, Ag, Zn, V, Cd, Sn, Ir, Mn, Rh, Co, Fe, CoFe, CoB, FeB, CoFeNi, and CoFeNiB.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
(22) The present disclosure is a p-MTJ wherein a MIS layer is formed within a free layer, and the overlying Hk enhancing layer/NCL stack is optimized to provide a lower Hc/Jc ratio than the prior art while maintaining a DRR of at least 100%, a RA <5 ohm-μm.sup.2, and acceptable thermal stability to 400° C. for a plurality of hours in a STT-MRAM for LLC applications. Although the exemplary embodiments depict p-MTJ stacks with bottom spin valve and top spin valve configurations, the present disclosure also encompasses a p-MTJ having a dual spin valve structure as appreciated by those skilled in the art. The p-MTJ may be incorporated in a MRAM, STT-MRAM, spin orbit torque (SOT)-MRAM, and other spintronic devices such as a spin torque oscillator, Spin Hall Effect device, magnetic sensor, or a biosensor. The p-MTJ layers in the drawings are not necessary drawn to size. In particular, the FL may appear thicker than the pinned layer in order to clearly show multiple FL sub-layers. The term “partially oxidized” when referring to a metal oxide layer means that the metal oxide lattice has a plurality of vacant sites between metal atoms that are not occupied by oxygen atoms. In other words, partial oxidation of a metal layer leads to a non-stoichiometric oxidation state where a plurality of metal atoms is not oxidized.
(23) Previously, we have disclosed various methods of improving magnetic properties in a p-MTJ that involve optimization of one or more of the FL, Hk enhancing layer, and NCL. In related U.S. Pat. No. 8,592,927, one or more elements including Mg and Ta are inserted as a MIS layer between FL1 and FL2 to reduce the perpendicular demagnetizing field thereby lowering the RA product and yielding higher thermal stability. Related U.S. Pat. No. 9,966,529 discloses that formation of metal oxide clusters or a discontinuous metal oxide layer within the FL is advantageous in enhancing PMA and thermal stability while maintaining RA at an acceptable level. Related U.S. patent application Ser. Nos. 15/881,035, and 16/275,381 describe an improved NCL having a buffer layer/NL stack, and an L2/L1/NL stack, respectively, where L2 blocks oxygen diffusion from the adjoining Hk enhancing layer that has a RA product less than that of the tunnel barrier, and L1 prevents nitrogen diffusion from the NL to the FL.
(24) Now we have discovered a further improvement in p-MTJ performance where a combination of a MIS layer in the FL, a Hk enhancing layer with a non-stoichiometric oxidation state, and a NCL enables a lower Hc/Jc ratio than previously achieved while maintaining acceptable properties for DRR, RA product, and thermal stability. Improved p-MTJ performance is realized by including at least one MIS layer within a FL stack having a FL1/FL2 configuration. It should be understood that the present disclosure also encompasses other embodiments, (not shown) where the FL has three or more layers as in a FL1/FL2/FL3 stack, for example, and at least one of FL1, FL2, and FL3 contains the MIS layer, or the at least one MIS layer is formed between two of FL1, FL2, and FL3. In all embodiments described herein, the FL has a thickness ≥11 Angstroms in order to guarantee sufficient PMA so that a switching current applied perpendicular to the planes of the p-MTJ is able to switch the FL magnetization direction. The present disclosure anticipates that the MIS layer is sufficiently thin, and preferably between 0.5 Angstrom and 4 Angstroms, to avoid a significant decrease in DRR.
(25) Referring to
(26) Seed layer 31 is typically a single layer or multilayer made of one or more metals or alloys that promote a uniform thickness in overlying layers. When the reference layer 32 has PMA, a seed layer is chosen that also enhances PMA in the reference layer. In some embodiments, the reference layer is a single magnetic layer that is one or more of Co and Fe that may be alloyed with one or both of B and Ni. Alternatively, the reference layer may have a synthetic antiferromagnetic (SyAF) configuration represented by AP2/coupling layer/AP1 where AP2 is a first magnetic layer on the seed layer, or formed on an optional antiferromagnetic (AFM) layer (not shown), and AP1 is a second magnetic layer that is antiferromagnetically (AF) coupled to AP2 through a metal coupling layer that is Ru or the like. In other embodiments, the reference layer, or one or both of AP2 and AP1 in a SyAF configuration is a laminated stack of layers such as (Co/Ni).sub.n, (CoFe/Ni).sub.n, (CoFe/NiCo).sub.n, (CoFe/NiFe).sub.n, or the like having inherent PMA and where n is an integer representing the lamination number. There may be a transition layer (not shown) that is one of Co, Fe, CoFe, and CoFeB between the uppermost layer in the laminated stack and the tunnel barrier layer 33.
(27) In a preferred embodiment, tunnel barrier layer 33 is MgO that is formed by sputter depositing a MgO target, or by depositing one or more Mg layers and then oxidizing one or more Mg layers with a known radical oxidation (ROX) or natural oxidation (NOX) method. However, other metal oxides, metal nitrides, or metal oxynitrides known in the art may be employed instead of MgO. It should be understood that the interface of a MgO layer with a magnetic layer that is CoFeB, for example, provides higher interfacial perpendicular anisotropy and a greater magnitude of PMA in the magnetic layer than an interface with other metal oxides.
(28) One or both of FL1 34a and FL2 34b is a single layer or multilayer of one or more of Co, Fe, CoFe, CoFeB, CoB, FeB, CoFeNi, or CoFeNiB. Optionally, one or both of FL1 and FL2 is a Heusler alloy including Ni.sub.2MnZ, Pd.sub.2MnZ, Co.sub.2MnZ, Fe.sub.2MnZ, Co.sub.2FeZ, Mn.sub.3Ge, Mn.sub.2Ga, and the like where Z is one of Si, Ge, Al, Ga, In, Sn, and Sb. In other embodiments, one or both of FL1 and FL2 is an ordered L1.sub.0 or L1.sub.1 material such as MnAl, MnGa, and RT wherein R is Rh, Pd, Pt, Ir, or an alloy thereof, and T is Fe, Co, Ni or an alloy thereof. In yet another embodiment, one or both of FL1 and FL2 is a rare-earth alloy including but not limited to TbFeCo, GdCoFe, FeNdB, and SmCo. FL1 has a thickness t1, and FL2 has a thickness t2 where (t1+t2) is preferably from 11 Angstroms to 25 Angstroms.
(29) The MIS layer 41 is one or more of Nb, Mo, Ta, W, Re, Ti, V, Cr, Zr, Hf, Ru, Rh, Os, Ir, Cu, Zn, Pt, Au, Ag, Pd, Al, B, Ga, Si, and Ge, and preferably has a thickness from 0.5 Angstrom to 4 Angstroms. FL1 34a, the MIS layer, and FL2 34b are typically sputter deposited in succession. The MIS layer is relied upon to reduce Ms in the FL, and getter oxygen that diffuses into one or both of FL1 and FL2 from the tunnel barrier layer 33 and from the Hk enhancing layer 35. It is believed that at least a portion of the MIS layer reacts with diffused oxygen to form a metal oxide that introduces additional FL/metal oxide interfaces to further enhance PMA. Moreover, the MIS layer serves as a boron sink by attracting boron thereby enabling a CoFeB FL, for example, to crystallize in the required (001) body centered cubic orientation for optimum magnetic properties.
(30) The Hk enhancing layer 35 is made of a material that provides interfacial perpendicular anisotropy at interface 51 by contacting a surface of the free layer. According to one preferred embodiment, the Hk enhancing layer is comprised of MgO having a thickness and oxidation state that are controlled to give a resistance×area (RA) product smaller than that of the MgO layer in the tunnel barrier layer 33 in order to minimize a total RA (RA.sub.TOTAL) for the p-MTJ, and avoid a significant decrease in the DRR because of the parasitic resistance effect previously mentioned with regard to equation (2). In an alternative embodiment, the Hk enhancing layer may be an oxide or oxynitride comprised of one or more of Si, Sr, Ti, Ba, Ca, La, Al, Mn, V, and Hf. Moreover, the Hk enhancing layer may be embedded with conductive particles made of one or more of Fe, Co, Ni, Ru, Cr, Au, Ag, and Cu to lower the resistivity therein. For instance, the conductive particles may be 20% to 45% by weight of the Hk enhancing layer.
(31) The Hk enhancing layer is formed by first depositing one or more of the aforementioned metals on the FL, and then performing a well known natural oxidation (NOX) or oxynitridation process. The Hk enhancing layer preferably has a non-stoichiometric oxygen content where a substantial number of sites in the metal lattice remain vacant (unoccupied by oxygen atoms) or are filled with other atoms such as N in order to minimize the RA.sub.HK contribution to RA.sub.TOTAL for p-MTJ 1 in the equation RA.sub.TOTAL=RA.sub.barrier+RA.sub.Hk+RA.sub.NCL where RA.sub.barrier+RA.sub.Hk+RA.sub.NCL are the RA products for the tunnel barrier layer 33, Hk enhancing layer 35, and NCL 38, respectively. Preferably, RA.sub.TOTAL is <5 ohm-μm.sup.2. The extent of oxidation during the NOX process is usually controlled with one or both of the oxygen flow rate and the duration of the oxygen flow within an oxidation chamber.
(32) The uppermost layer in p-MTJ 1 is NCL 38 with a thickness from 4 Angstroms to 500 Angstroms, and in one preferred embodiment has a lower buffer layer 36 and an upper NL 37 where the buffer layer is relied on to block oxygen diffusion from the Hk enhancing layer to the NL, and to prevent nitrogen diffusion from the NL to the Hk enhancing layer 35 and FL 42. In one preferred embodiment, the buffer layer is a single layer or multilayer that is one or more of Mo, W, Ru, Nb, Ta, Cr, Pt, Cu, Au, Ag, Zn, V, Cd, Sn, Ir, Mn, Rh, Co, Fe, CoFe, CoB, FeB, CoFeNi, and CoFeNiB. In some embodiments, the buffer layer has a bilayer stack L2/L1 (not shown) where L2 is formed on the Hk enhancing layer and is responsible for blocking oxygen diffusion, and L1 adjoins a bottom surface of the NL and prevents nitrogen diffusion, and L2 is less easily oxidized than L1. L1 and L2 compositions are described in more detail in related U.S. patent application Ser. No. 16/275,381.
(33) NL 37 is comprised of a metal or alloy (M1) where M1 is preferably one or more of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, Mg, and W to afford a conductive nitride (M1N) or oxynitride (M1ON) to minimize the RA.sub.NCL contribution to RA.sub.TOTAL. In other embodiments, the NL is an insulating metal (M2) nitride or oxynitride where M2 is one of B, Al, Si, Ga, In, or TI that is alloyed with a conductive metal or alloy (M3) selected from one or more of Pt, Au, Ag, Mg, Ca, Sr, Ba, Sc, Y, La, Co, Fe, Mn, Ru, Rh, Ir, Ni, Pd, Zn, Cu, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W to impart conductivity to the resulting M2M3 nitride (M2M3N), or M2M3 oxynitride (M2M3ON). The M2M3N or M2M3ON layers may be formed by sputter depositing M2 and M3 targets in reaction chamber with a plasma generated using a flow of N.sub.2 and RIE conditions, or by sputtering a M2M3 alloy, if available, in the presence of nitrogen plasma. The present disclosure also encompasses an embodiment where M3 forms conductive channels in an insulator M2N or M2ON matrix.
(34) We find that a NCL has improved performance over a metal capping layer (MCL) such as Ta/Ru in terms of providing higher thermal stability to the p-MTJ, and enabling a higher Hc/Jc ratio. As indicated later, Hc in a p-MTJ with a MCL is dramatically lower than for p-MTJ 1 with NCL 38 because Hc is significantly lower at a given Jc when FL thickness approaches 11 Angstroms for a p-MTJ with an uppermost MCL. On the other hand, we observe that RA.sub.NCL is up to 1.5 times larger than RA.sub.MCL. Therefore, optimization of the Hk enhancing layer is necessary to maintain RA.sub.TOTAL<5 ohm-μm.sup.2 for p-MTJ 1 so that there are no trade-offs when achieving the advantage of a substantially larger Hc/Jc than in the prior art.
(35) Magnetic properties including Hk, Hc, RA, and DRR that are reported herein were obtained with ferromagnetic resonance measurements as disclosed in related U.S. patent application Ser. No. 16/056,783, and with Vibrating Sample Magnetometry (VSM) and current-in-plane tunneling (CIPT) measurements.
(36) Referring to
(37) In
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(42) Referring to
(43) Referring to
(44) With regard to
(45) The first embodiment of the present disclosure also encompasses a p-MTJ 2 with a top spin valve structure as shown in
(46) According to a second embodiment shown in
(47) Referring to
(48) A third embodiment of the present disclosure is illustrated in
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(50) A fourth embodiment is depicted in
(51) An alternative fourth embodiment is illustrated in
(52) In all embodiments described herein, the advantage of a higher Hc/Jc ratio for better FL switching is realized for spintronic applications including STT-MRAM than in the prior art. Furthermore, other p-MTJ properties such as RA, DRR, and thermal stability are maintained for an overall improvement in p-MTJ performance.
(53) The present disclosure also encompasses a method of forming p-MTJ 1 on substrate 30. All layers in the embodiments illustrated herein may be formed in an Anelva C-7100 thin film sputtering system or the like which typically includes three physical vapor deposition (PVD) chambers each having five targets, an oxidation chamber, and a sputter etching chamber. Usually, the sputter deposition process comprises a noble gas such as argon, and oxygen is excluded unless required for tunnel barrier or Hk enhancing layer formation in the oxidation chamber.
(54) Referring to
(55) Thereafter, as depicted in
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(57) All of the embodiments described herein may be incorporated in a manufacturing scheme with standard tools and processes. A substantial improvement in the Hc/Jc ratio is achieved through a combination of metal insertion in the FL, a partially oxidized Hk enhancing layer, and a NCL with a buffer layer/NL configuration where the buffer layer prevents oxygen migration to the NL, and blocks nitrogen diffusion from the NL to the FL and Hk enhancing layer. The p-MTJ embodiments described herein are especially effective for a FL thickness from about 11 Angstroms to 25 Angstroms, and when the MIS thickness is in the range of 0.5 Angstrom to 4 Angstroms.
(58) While the present disclosure has been particularly shown and described with reference to, the preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made without departing from the spirit and scope of this disclosure.