Maintaining coercive field after high temperature anneal for magnetic device applications with perpendicular magnetic anistropy
11569441 · 2023-01-31
Assignee
Inventors
- Huanlong Liu (Sunnyvale, CA, US)
- Yuan-Jen Lee (Fremont, CA, US)
- Jian Zhu (San Jose, CA, US)
- Guenole Jan (San Jose, CA, US)
- Luc Thomas (San Jose, CA, US)
- Po-Kang Wang (Los Altos, CA)
- Ru-Ying Tong (Los Gatos, CA)
- Jodi Iwata (San Carlos, CA, US)
Cpc classification
H01F10/32
ELECTRICITY
G11C11/161
PHYSICS
International classification
Abstract
A magnetic tunnel junction with perpendicular magnetic anisotropy (PMA MTJ) is disclosed wherein a free layer interfaces with a tunnel barrier and has a second interface with an oxide layer. A lattice-matching layer adjoins an opposite side of the oxide layer with respect to the free layer and is comprised of Co.sub.XFe.sub.YNi.sub.ZL.sub.WM.sub.V or an oxide or nitride of Ru, Ta, Ti, or Si, wherein L is one of B, Zr, Nb, Hf, Mo, Cu, Cr, Mg, Ta, Ti, Au, Ag, or P, and M is one of Mo, Mg, Ta, Cr, W, or V, (x+y+z+w+v)=100 atomic %, x+y>0, and each of v and w are >0. The lattice-matching layer grows a BCC structure during annealing thereby promoting BCC structure growth in the oxide layer that results in enhanced free layer PMA and improved thermal stability.
Claims
1. A method comprising: providing a stack of layers that includes a reference layer, a tunnel barrier, and a free layer; forming an oxide layer on the free layer; forming a lattice-matching layer on the oxide layer; forming a hard mask on the first lattice-matching layer; and annealing the lattice-matching layer so that the lattice-matching layer grows a body centered cubic (BCC) structure.
2. The method of claim 1, wherein the lattice-matching layer includes non-magnetic metals or alloys.
3. The method of claim 1, wherein the lattice-matching layer includes non-magnetic metals or alloys of M, and wherein M is selected from the group consisting of Mo, Mg, Ta, Cr, W, Ru and V.
4. The method of claim 1, wherein the lattice-matching layer includes a material having a composition denoted as Co.sub.XFe.sub.YNi.sub.ZL.sub.W, wherein (x+y) is greater than zero, wherein w is greater than zero, and wherein (x+y+z+w) is equal to 100 atomic %, and wherein L is a material selected from the group consisting of B, Zr, Nb, Hf, Mo, Cu, Cr, Mg, Ta, Ti, Au, Ag, and P.
5. The method of claim 1, wherein the lattice-matching layer includes a material having a composition denoted as Co.sub.XFe.sub.YNi.sub.ZL.sub.WM.sub.V, wherein (x+y) is greater than zero, wherein each of v and w is greater than zero, and wherein (x+y+z+w+v) is equal to 100 atomic %, wherein M is material selected from the group consisting of Mo, Mg, Ta, Cr, W, Ru, and V, and wherein L is a material selected from the group consisting of B, Zr, Nb, Hf, Mo, Cu, Cr, Mg, Ta, Ti, Au, Ag and P.
6. The method of claim 1, wherein the oxide layer includes a material selected from the group consisting of MgTaOx, MgO, SiOx, SrTiOx, BaTiOx, CaTiOx, LaAlOx, MnOx, VOx, Al.sub.2O.sub.3, TiOx, BOx, and HfOx.
7. The method of claim 1, wherein the lattice-matching layer includes a material that is an oxide or nitride of Ru, Ta, Ti, or Si.
8. A method comprising: forming a lattice-matching layer on a substrate; forming an oxide layer on the substrate; forming a free layer on the substrate, the free layer interfacing with the oxide layer; forming a tunnel barrier layer on the substrate, the tunnel barrier layer interfacing with the free layer; forming a reference layer on the on the substrate, the reference layer interfacing with the tunnel barrier layer; forming a hard mask layer on the substrate to form a stack of layers that includes the hard mask layer, the reference layer, the tunnel barrier layer, the free layer, the oxide layer and the lattice-matching layer; and annealing the stack of layers so that the lattice-matching layer grows a body centered cubic (BCC) structure.
9. The method of claim 8, wherein the lattice-matching layer includes non-magnetic metals or alloys of M, and wherein M is selected from the group consisting of Mo, Mg, Ta, Cr, W, Ru and V.
10. The method of claim 8, wherein the lattice-matching layer includes a material having a composition denoted as Co.sub.XFe.sub.YNi.sub.ZL.sub.W, wherein (x+y) is greater than zero, wherein w is greater than zero, and wherein (x+y+z+w) is equal to 100 atomic %, and wherein L is a material selected from the group consisting of B, Zr, Nb, Hf, Mo, Cu, Cr, Mg, Ta, Ti, Au, Ag, and P.
11. The method of claim 8, wherein the lattice-matching layer includes a material having a composition denoted as Co.sub.XFe.sub.YNi.sub.ZL.sub.WM.sub.V, wherein (x+y) is greater than zero, wherein each of v and w is greater than zero, and wherein (x+y+z+w+v) is equal to 100 atomic %, wherein M is material selected from the group consisting of Mo, Mg, Ta, Cr, W, Ru, and V, and wherein L is a material selected from the group consisting of B, Zr, Nb, Hf, Mo, Cu, Cr, Mg, Ta, Ti, Au, Ag and P.
12. The method of claim 8, further comprising forming a seed layer on the substrate, and wherein forming the lattice-matching layer on the substrate includes forming the lattice-matching layer directly on the seed layer such that the lattice-matching layer interfaces with the seed layer.
13. The method of claim 8, wherein forming the oxide layer on the lattice-matching layer includes forming the oxide layer directly on the lattice-matching layer.
14. The method of claim 8, wherein annealing the stack of layers includes annealing at a temperature of about 400° C.
15. A method comprising: forming a stack of layers on a substrate, the stack of layers including a reference layer, a tunnel barrier layer, a free layer, an oxide layer and a lattice-matching layer; annealing the stack of layers so that the lattice-matching layer grows a body centered cubic (BCC) structure; and patterning the stack of layers to form a magnetic tunnel junction (MTJ) structure.
16. The method of claim 15, wherein the lattice-matching layer includes a first layer having a first material composition and a second layer having a second material composition that is different from the first material composition.
17. The method of claim 16, wherein the lattice-matching layer further includes a third layer having a third material composition that is different from the second material composition.
18. The method of claim 15, wherein annealing the stack of layers includes annealing at a temperature of about 400° C.
19. The method of claim 15, wherein the lattice-matching layer includes a material selected from the group consisting of FeL and CoL, and wherein L is a material selected from the group consisting of B, Zr, Nb, Hf, Mo, Cu, Cr, Mg, Ta, Ti, Au, Ag, and P.
20. The method of claim 15, further comprising: forming an insulting layer on the MTJ structure; and forming an electrode layer on the MTJ structure.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
(11) The present disclosure is a PMA MTJ element wherein a free layer has thermal stability to at least 400° C. because of perpendicular magnetic anisotropy (PMA) therein that is established by interfaces with a tunnel barrier and an oxide layer, and wherein a lattice-matching layer enables the oxide layer to transform to a BCC structure in order to match the BCC structure formed in the free layer. The PMA MTJ element may be employed in magnetic memory devices such as MRAM and spin-torque MRAM, and in spintronic devices such as microwave assisted magnetic recording (MAMR), spin torque oscillator (STO), magnetic sensors, and biosensors. The PMA MTJ may have a bottom spin valve, top spin valve, or dual spin valve design as appreciated by those skilled in the art. Although a plurality of PMA MTJ elements is typically formed on a substrate during the fabrication of a memory device, only one PMA MTJ is depicted in the exemplary embodiments in order to simplify the drawings. The terms “Hk enhancing layer” and “cap layer” may be used interchangeably when referring to an oxide layer that induces PMA in an adjoining free layer. A cap layer as defined herein has a position above the free layer in a PMA MTJ stack, and a Hk enhancing layer may contact either a bottom surface of the free layer in a top spin valve, or the top surface of the free layer in a bottom spin valve design.
(12) In related U.S. Pat. No. 9,147,833, we disclosed the use of a laminated Hk enhancing layer to achieve high coercivity in PMA MTJ elements after 400° C. annealing. In U.S. Pat. No. 9,425,387, we disclosed a PMA MTJ in which a diffusion barrier is inserted between the Hk enhancing layer and overlying hard mask in order to prevent metals in the hard mask from migrating into the Hk enhancing layer and diluting the interfacial PMA established at the free layer/Hk enhancing layer interface. In other words, high oxygen content is maintained in the Hk enhancing layer by blocking metals from entering therein. Accordingly, better coercivity and higher thermal stability are realized.
(13) Now we have found that coercivity (Hc) in a PMA MTJ with a tunnel barrier/free layer/metal oxide stack of layers is further improved with a layer hereafter called the lattice-matching layer that adjoins the oxide layer on a side facing away from the free barrier, and has a key feature of ensuring that the oxide layer will be completely transformed from an amorphous state to a body-centered cubic (BCC) structure. It should be understood that a tunnel barrier such as MgO is transformed into a BCC layer during annealing and thereby assists the adjoining free layer in achieving a BCC structure through a first interface. The growth of a BCC structure in both of the free layer and lattice-matching layer will influence a similar BCC growth in the oxide layer during high temperature annealing or processing at about 400° C. As a result of BCC lattice matching between the tunnel barrier and free layer, and between the free layer and oxide layer, a greater level of PMA is achieved and maintained in the free layer. The oxide layer may be a cap layer formed between the free layer and overlying hard mask in embodiments depicted in
(14) Referring to
(15) Preferably, seed layer 11 is employed to maintain or enhance PMA in reference layer 12 and facilitates smooth and uniform crystalline growth in the overlying PMA MTJ layers. The seed layer may be one or more of NiCr, NiFeCr, Pd, Pt, Ta, Ru, Mg, Ti, Mo, or other metals or alloys used in the art.
(16) Reference layer 12 preferably is a SyAP stack of layers having an AP2/coupling layer/AP1 configuration wherein the AP1 layer has an interface with the tunnel barrier, and each of AP1 and AP2 are one or more of Co, Fe, CoFe, or alloys thereof that may have an additional element including one or both of Ni and B. AP1 and AP2 layers have magnetic moments in opposite directions because of antiferromagnetic (AFM) coupling provided by a Ru, Rh, Ir or another AFM coupling layer. PMA is induced or enhanced in the reference layer 12 through an interface with tunnel barrier 13. In another embodiment, one or both of the AP1 and AP2 layers are a laminated structure that is one of (Co/Ni).sub.n, (Co/Pd).sub.n, (Co/Pt).sub.n, (CoFe/Ni).sub.n, (Co/NiFe).sub.n, (Co/NiCo).sub.n, or other laminated stacks exhibiting intrinsic PMA where n is between 2 and 30. Preferably, each Co or Co alloy layer in the laminated structure has a thickness between 0.5 and 5 Angstroms while each Pd, Pt, Ni, or Ni alloy layer has a thickness from 2 to 10 Angstroms. The Co or Co alloy layer is generally thinner than the Ni, Ni alloy, Pt, or Pd layer.
(17) When the AP1 layer comprises one of the aforementioned laminated structures, a transition layer that is Co, CoFe, or CoFeB may be inserted as the uppermost layer in the AP1 stack. In some embodiments, a CoFeB/Co transition layer may be formed in which the CoFeB portion is from 4 to 8 Angstroms thick while the Co layer portion has a thickness from 3 to 5 Angstroms. Co is often used as the uppermost layer in the reference layer stack to form an interface with the tunnel barrier layer since Co is more resistant to oxidation than a CoFeB (or CoFe) layer. In other words, oxygen is able to migrate out of a MgO tunnel barrier layer into a reference layer during annealing thereby causing partial oxidation of CoFeB, for example, which leads to a degradation in the TMR ratio.
(18) The tunnel barrier layer 13 may be any metal oxide layer that induces a spin dependent tunneling effect between the reference layer and free layer. Although MgO is often preferred since it provides an optimum TMR ratio, other materials including MgN, MgON, and oxides, nitrides, or oxynitrides of Al, Ti, Zn, Hf, AlTi, MgZn, MgTa, or Ta may be employed as the tunnel barrier. Furthermore, laminations of one or more of the aforementioned materials may be selected as the tunnel barrier.
(19) The free layer 14 adjoins a top surface of the tunnel barrier 13 in a bottom spin valve design, and according to one embodiment is a single layer that is one of Co, Fe, CoFe, or alloys thereof with an optional additional element including one or both of Ni and B. However, the free layer may have a bilayer or trilayer configuration represented by FL1/FL2 or FL1/FL2/FL3 where each of FL1, FL2, and FL3 are magnetic layers made of Co, Fe, CoFe or alloys thereof wherein magnetic moments of all the two or three layers are aligned in the same direction through ferromagnetic coupling. The alloys may include one or both of Ni, B, and transition metal elements including Ta, Zr, Hf, Mg, Mo, and Nb. In other embodiments, the free layer has a FL1/Ru/FL2 configuration wherein FL1 and FL2 layers are antiferromagnetically coupled. In yet another embodiment, the free layer is one of the laminated structures described previously with respect to reference layer composition. A laminated structure that is (Co/Ni).sub.n or the like is considered to have intrinsic PMA.
(20) In some embodiments, the free layer 14 has a FL1/A/FL2 stack in which A is layer with a thickness from 5 to 10 Angstroms and is made of a non-magnetic element such as Ta, Ti, W, Zr, Hf, Nb, Mo, V, Mg, or Cr that provides a moment dilution effect. The FL1 and FL2 layers are ferromagnetically coupled through the A layer. In other words, for a fixed free layer thickness d, a FL1/A/FL2 configuration will have a smaller in-plane magnetization component than a FL1/FL2 stack. It follows that interfacial perpendicular anisotropy at the interface 20 between the tunnel barrier and free layer, and at the interface 21 between the free layer and cap layer more easily overcomes the shape anisotropy field and generates substantial PMA in the free layer with a FL1/A/FL2 configuration.
(21) PMA in the free layer is induced or enhanced by interfacial perpendicular anisotropy generated in a portion thereof adjacent to a first interface 20 with the tunnel barrier layer 13, and in a portion adjacent to a second interface 21 with an Hk enhancing layer also known in bottom spin valve designs as cap layer 15. Preferably, interfacial (surface) perpendicular anisotropy exceeds the shape anisotropy field for the free layer to provide PMA and a net magnetization direction that is perpendicular to the two interfaces. As a result, the free layer will have greater thermal stability, and higher Hc after high temperature processing up to about 400° C. than a free layer with in-plane magnetization. Note that the thickness of free layer 14 is represented by “d” in equation (4) presented previously. Thus, as the value for “d” is reduced, the perpendicular anisotropy field increases. We have found that PMA is established in the free layer by maintaining thickness d in
(22) Cap layer 15 is formed on the free layer 14 and is preferably comprised of an oxide that is one of MgTaOx, MgO, SiOx, SrTiOx, BaTiOx, CaTiOx, LaAlOx, MnOx, VOx, Al.sub.2O.sub.3, TiOx, BOx, and HfOx. In some embodiments, the cap layer is a lamination of one or more of the aforementioned oxides. Preferably, the cap layer is MgO having a non-stoichiometric oxidation state wherein a certain number of Mg atoms remain unoxidized in order to achieve a RA value therein that is less than about 1 ohm-μm.sup.2, which is substantially less than the RA value of the tunnel barrier. In some cases, the total RA for the PMA MTJ represented by the sum (RA.sub.tunnel barrier+RA.sub.cap layer) is <5 ohm-μm.sup.2 while in other embodiments, the total RA value is below 20 ohm-μm.sup.2. The cap layer may be formed by a process similar to the one used in tunnel barrier formation in which a metal or alloy layer is deposited and is then oxidized to a stoichiometric or non-stoichiometric oxidation state by a radical oxidation (ROX) or natural oxidation (NOX) process. Since the oxide cap layer contributes to resistance x area (RA) value for the PMA MTJ but does not increase the TMR ratio, the thickness of the cap layer is preferably minimized to a value of 2 to 20 Angstroms to avoid an unacceptably high total RA value.
(23) A key feature of the present disclosure is a lattice-matching layer 16 formed between the cap layer and an overlying hard mask 17. The lattice-matching layer serves to block the structural influence of the hard mask during subsequent high temperature processing including annealing at 400° C. for a plurality of hours. As a result, the cap layer is transformed from an amorphous character to a BCC structure while the free layer grows a BCC structure during 400° C. processing. Accordingly, higher PMA is achieved in the free layer due to lattice matching with the cap layer. In the prior art, the hard mask metal or alloy is in contact with the oxide cap layer and has a tendency to prevent some or the entire cap layer from forming a BCC structure, and thereby limiting PMA in the free layer.
(24) In the first embodiment, the lattice-matching layer 16-1 has a bilayer structure with a lower layer 16a made of a magnetic material and a thickness of 2 to 10 Angstroms, and an upper layer 16b that is a single layer or multilayer stack comprised of one or more non-magnetic metals or alloys of M elements where M is one or more of Mo, Mg, Ta, Cr, W, Ru, or V. The upper layer serves to effectively eliminate a magnetic influence of the lower layer on the free layer so that the lower layer does not affect switching behavior in the free layer. The lower layer preferably has a Co.sub.XFe.sub.YNi.sub.ZL.sub.W composition wherein L is one of B, Zr, Nb, Hf, Mo, Cu, Cr, Mg, Ta, Ti, Au, Ag, or P, and (x+y+z+w)=100 atomic %, x+y>0, and w>0. Lower layer 16a has a finite magnetic moment after the aforementioned 400° C. annealing process. Moreover, “x” and “z” may be zero to yield a FeL lower layer, or “y” and “z” may be zero to give a CoL lower layer. The L content is relied on to provide an amorphous character in the deposited lower layer, and enables BCC growth in the lower layer during 400° C. annealing.
(25) Since the cap layer is thin as described earlier, the lower layer's magnetic moment is proximate to the free layer and would normally affect the PMA MTJ through either a magnetic dipole field or spin polarization under electric current. However, forming the M layer with a thickness of 2 to 10 Angstroms on a top surface of the lower layer removes any undesirable influence of the lower layer on the free layer. During annealing, the CoFeNiL layer grows a BCC structure and thereby induces a similar BCC growth in cap layer 15 through interface 22. BCC crystal growth is usually complete after 30 minutes at a temperature proximate to 400° C. However, as the non-magnetic element L content increases, the time required for the transformation from amorphous to a BCC structure may increase.
(26) Above the lattice-matching layer 16-1 is a hard mask 17 with a thickness in the range of about 50 to 300 Angstroms, and having a top surface 17t. The hard mask acts as a protective layer to underlying PMA MTJ layers during subsequent processing including photoresist patterning and etching (
(27) According to a second embodiment shown in
(28) In a third embodiment shown in
(29) The present disclosure also encompasses a fourth embodiment depicted in
(30) A fifth embodiment of the present disclosure is shown in
(31)
(32) The present disclosure also anticipates a seventh embodiment with a top spin valve configuration as illustrated for PMA MTJ 1′ with sidewall 1s in
(33) In another top spin valve embodiment depicted as PMA MTJ 2 with sidewall 2s in
(34) According to a ninth embodiment of the present disclosure illustrated in
(35) Referring to
(36) The present disclosure also encompasses a method of forming a PMA MTJ element having a configuration disclosed in one of the embodiments shown in
(37) Referring to
(38) Referring to
(39) Thereafter in
(40) Formation of a PMA MTJ with a top spin valve design such as one depicted in
(41) To demonstrate the benefits of a lattice-matching layer according to the present disclosure, patterned PMA MTJ nanopillars were fabricated as circular 90-100 nm MRAM devices and the Hc field for each was measured. Reference PMA MTJ A has a seed layer/reference layer/MgO tunnel barrier/free layer/MgO cap layer/Ru/Ta/TiN configuration wherein the reference layer and free layer are CoFeB based materials, the tunnel barrier and cap layer are MgO, and the hard mask is a Ru/Ta/TiN stack. PMA MTJ B is formed according to an embodiment of the present disclosure and differs from the reference only by including a lattice-matching layer having a CoFeB/Mo configuration between the cap layer and hard mask. All structures were deposited at room temperature and subjected to a first anneal at 330° C. for 30 minutes. A baseline coercivity measurement indicated Hc=3200 Oe for both samples. Then a second anneal was performed at 400° C. for 151 minutes before a second coercivity measurement was taken. As shown in Table 1, Hc for MTJ A is undesirably reduced to 1600 Oe after the second anneal while PMA MTJ B has a Hc of 3200 Oe that is essentially unchanged compared with the first measurement. In some applications, a minimum Hc of ≥3200 Oe is required after high temperature anneal. In addition, it is important that Hc should be maintained for at least two hours during a 400° C. anneal. Note that 400° C. is an industry standard for semiconductor manufacturing to reduce the defect rate of the product and therefore becomes a requirement for embedded MRAM applications.
(42) TABLE-US-00001 TABLE 1 Results for PMA MTJs with CoFeB/MgO/CoFeB/cap layer/LM/hard mask configurations Fail rate He (Oe) Lattice- Lattice- after after Cap matching matching 260° C., 400° C., MTJ layer (LM) layer 1 (LM) layer 2 90 sec. 151 sec A MgO None None 50% 1600 B MgO CoFeB (5 Mo (5 1 ppm 3200 Angs.) Angstroms)
(43) The benefits of the present disclosure are improved PMA (Hc and Hk) for a free layer in a magnetic device that will increase the retention time for a memory element such as a PMA MTJ following high temperature processing up to 400° C. that is required for MRAM or STT-MRAM devices integrated in CMOS structures. Furthermore, the processes and materials described herein are compatible with the design and processing requirements of magnetic devices. The fabrication of a MTJ according to an embodiment of this disclosure is not expected to significantly impact the manufacturing cost.
(44) While this disclosure has been particularly shown and described with reference to, the preferred embodiment 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.