METHOD OF MANUFACTURING A MAGNETIC MEMORY DEVICE HAVING BUFFER LAYER

Abstract

The disclosed technology generally relates to magnetic memory devices, and more particularly to spin transfer torque magnetic random access memory (STT-MRAM) devices having a magnetic tunnel junction (MTJ), and further relates to methods of fabricating the STT-MRAM devices. In an aspect, a magnetoresistive random access memory (MRAM) device has a magnetic tunnel junction (MTJ). The MTJ includes a magnetic reference layer comprising CoFeB, a magnetic free layer comprising CoFeB, and a barrier layer comprising MgO. The barrier layer is interposed between the magnetic reference layer and the magnetic free layer. The barrier layer has a thickness adapted to tunnel electrons between the magnetic reference layer and the magnetic free layer sufficient to cause a change in the magnetization direction of the variable magnetization under a bias. The MTJ further comprises a buffer layer comprising one or more of Co, Fe, CoFe and CoFeB, where the buffer layer is doped with one or both of C and N.

Claims

1. A method of manufacturing a magnetoresistive random access memory (MRAM), the MRAM having a magnetic tunnel junction (MTJ), the method comprising: forming a magnetic reference layer comprising CoFeB and having a fixed magnetization direction; forming a barrier layer, comprising MgO, on the magnetic reference layer; forming a magnetic free layer, comprising CoFeB, on the barrier layer, wherein the magnetic free layer has a variable magnetization direction that changes under a write bias, wherein the barrier layer is interposed between the magnetic reference layer and the magnetic free layer, wherein the barrier layer has a thickness adapted to tunnel electrons between the magnetic reference layer and the magnetic free layer at a current density sufficient to cause a magnetization direction of the magnetic free layer to change under a write bias; and forming one or more buffer layers over one or both of opposing surfaces of the barrier layer, wherein each of the one or more buffer layers comprises one or more of Co, Fe, CoFe and CoFeB, and is doped with one or both of C and N.

2. The method according to claim 1, wherein each of the one or more buffer layers is doped with the one or both of C and N at a concentration of 1 to 8 atomic percent.

3. The method according to claim 1, wherein forming the one or more buffer layers comprises forming one of the one or more buffer layers adjacent to and on a same side of the barrier layer as the magnetic reference layer.

4. The method according to claim 3, wherein the one of the one or more buffer layers is interposed between the barrier layer and the magnetic reference layer.

5. The method according to claim 3, wherein the magnetic reference layer comprises a plurality of layers, wherein one of the plurality of layers is the one of the one or more buffer layers.

6. The method according to claim 3, wherein forming the one or more buffer layers further comprises forming another one of the one or more buffer layers adjacent to and on a same side of the barrier layer as the magnetic free layer.

7. The method according to claim 1, wherein forming the one or more buffer layers comprises forming one of the one or more buffer layers adjacent to and on a same side of the barrier layer as the magnetic free layer.

8. The method according to claim 7, wherein the one of the one or more buffer layers is interposed between the barrier layer and the magnetic free layer.

9. The method according to claim 7, wherein the magnetic free layer comprises a plurality of layers, wherein one of the plurality of layers is the one of the one or more buffer layers.

10. The method according to claim 1, further comprising annealing the MTJ at a temperature sufficient to cause one or more of the barrier layer, the magnetic reference layer and the magnetic free layer to crystallize into a body-centered cubic structure.

11. The method according to claim 10, wherein annealing the MTJ comprises causing crystallization of the magnetic reference layer and/or the magnetic free layer to initiate subsequent to initiation of crystallization of the barrier layer.

12. The method according to claim 1, wherein the one or more buffer layers serve as a diffusion barrier, such that one or both of the magnetic free layer and the magnetic reference layer are substantially free of atomic elements diffused from the barrier layer, and that the barrier layer is substantially free of atomic elements diffused from the one or both of the magnetic reference layer and the magnetic free layer.

13. A method of manufacturing a magnetoresistive random access memory (MRAM) device, the method comprising: forming a magnetic tunnel junction (MTJ) comprising a magnetic reference layer and a magnetic free layer interposed by a barrier layer, wherein forming the MTJ further comprises forming one or more buffer layers over one or both opposing surfaces of the barrier layer, wherein each of the one or more buffer layers comprises one or more of Co, Fe, CoFe and CoFeB, and is doped with one or both of C and N.

14. The method according to claim 13, wherein each of the one or more buffer layers is doped with one or both of C and N at a concentration of 1 to 8 atomic percent.

15. The method according to claim 13, wherein each of the one or more buffer layers has a thickness of 0.2 nm-2 nm.

16. The method according to claim 13, further comprising annealing the MTJ at a temperature sufficient to cause one or more of the barrier layer, the magnetic reference layer and the magnetic free layer that are amorphous as-deposited to crystallize.

17. The method according to claim 13, wherein the one or more buffer layers serve as a diffusion barrier, such that one or both of the magnetic free layer and the magnetic reference layer are substantially free of atomic elements diffused from the barrier layer, and the barrier layer is substantially free of atomic elements diffused from the one or both of the magnetic reference layer and the magnetic free layer.

18. The method according to claim 17, wherein the magnetic reference layer and the magnetic free layer comprise boron (B), and wherein the one or more buffer layers are adapted to impede diffusion therethrough of at least boron (B), such that after annealing, a concentration of B in the barrier layer is less than 10% of B in the magnetic reference layer and the magnetic free layer.

19. The method according to claim 17, wherein the barrier layer comprises an oxide, and wherein the one or more buffer layers are adapted to impede diffusion therethrough of at least oxygen (O), such that after annealing, a concentration O in one or both of the magnetic reference layer and the magnetic free layer is less than 10% of O in the barrier layer.

20. The method according to claim 13, wherein one or both of the magnetic reference layer and the magnetic free layer comprises a plurality of layers, and wherein one of the plurality of layers is one of the one or more buffer layers.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The above, as well as additional objects, features and advantages of the present invention, will be better understood through the following illustrative and non-limiting detailed description of preferred embodiments of the present invention, with reference to the appended drawings, in which:

[0027] FIG. 1 schematically illustrates a magnetic tunnel junction (MTJ) of an MRAM device according to some embodiments;

[0028] FIG. 2 schematically illustrates a magnetic tunnel junction (MTJ) of an MRAM device according to some other embodiments;

[0029] FIG. 3 schematically illustrates a magnetic tunnel junction (MTJ) of an MRAM device according to some other embodiments;

[0030] FIG. 4 is a graph illustrating measurements of tunnel magneto-resistance ratio (TMR) of MRAM devices having a buffer layer according to embodiments in comparison with a reference MRAM device not having a buffer layer;

[0031] FIG. 5 is a graph illustrating measurements of the resistance-area product (RA) of the MRAM devices of FIG. 4;

[0032] FIG. 6 is a graph illustrating measurements of the magnetic moment of the MRAM devices of FIGS. 4 and 5; and

[0033] FIG. 7 is a flow chart illustrating a method of manufacturing an MRAM device according to embodiments.

[0034] All the Figures are schematic, not necessarily to scale, and generally only show parts which are necessary to elucidate the embodiments of the disclosed technology, wherein other parts may be omitted or merely suggested.

DETAILED DESCRIPTION OF CERTAIN ILLUSTRATIVE EMBODIMENTS

[0035] The disclosed technology will now be described more fully hereinafter with reference to the accompanying drawings, in which exemplifying embodiments of the disclosed technology are shown. The disclosed technology may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided by way of example so that this disclosure will convey the scope of the invention to those skilled in the art. Furthermore, like numbers refer to the same or similar elements or components throughout.

[0036] As discussed above, MRAM is emerging as an alternative to many conventional semiconductor memories. There is a particularly growing interest in configuring STT-MRAMs as replacements for embedded static random-access memories (SRAMs), where non-volatile storage of data is enabled in part by magnetic tunnel junctions (MTJs). An MTJ comprises a magnetic reference layer, or pinned layer, and a magnetic free layer separated by a dielectric barrier layer, wherein the relative magnetic orientation of the reference layer and the free layer determines an electric resistance of the MTJ. The MTJ has a relatively low resistance when the magnetization of the reference layer and the free layer are aligned in parallel, while having a relatively high resistance when the magnetization of the reference layer and the free layer, respectively, are anti-parallel.

[0037] As described herein, tunnel magneto-resistance ratio (TMR) is a measure of the difference in electric resistance of the anti-parallel state and the parallel state. The TMR ratio is determined, inter alia, by the crystallographic texture of the MTJ, which in turn depends on e.g. annealing temperatures and diffusion processes within the MTJ.

[0038] According to various embodiments, the MTJ may have a free layer and/or the reference layer that may be formed of a ferromagnetic material such as Fe, Co, Ni and their alloys like but not limited to CoFe, NiFe, CoFeNi, CoFeB, CoZrTa, CoZrNr, FeN, CoFeN, and CoFeAl, among other ferromagnetic materials.

[0039] According to various embodiments, the MTJ includes a barrier layer, which can be a tunneling layer, formed between the free layer and the reference layer and comprising a dielectric material, e.g., MgO, Al.sub.2O.sub.3, SiO.sub.2, TiO.sub.2, Ta.sub.2O.sub.5 and HfO.sub.2, among others.

[0040] In some embodiments of MTJs, the reference layer and the free layer comprise CoFe and the barrier layer MgO. Further, B may be added to the CoFe so as to delay the crystallization of CoFe and thereby allow MgO to crystallize first and transfer its 001 texture to the CoFe.

[0041] Although MTJs based on CoFe/MgO junctions may provide a relatively high TMR, there is still a need for MRAM devices having an increased TMR and while being relatively easy to fabricate.

[0042] With reference to FIG. 1, there is shown an MTJ 110 of an MRAM device according to an embodiment of the disclosed technology. The MTJ 110 may comprise of a stack of multiple layers, having e.g. a seed layer 160 in the bottom, and then layers in the following order: a magnetic reference or pinned layer 120, a barrier layer 140, a buffer layer 150, a magnetic free layer 130 and a cap layer 170. It should be noted the position of the buffer layer 150 is merely an example of one of several possible positions in the stack. Further, the order of the magnetic reference layer 120 and the free layer 130 may be reversed such that the magnetic reference layer 120 is arranged above the magnetic free layer 130. The magnetic reference layer 120 and the magnetic free layer 130 may have a perpendicular magnetic anisotropy with a direction that can be altered between e.g. two mutually opposing direction in the magnetic free layer 130. As described herein, a perpendicular magnetic anisotropy refers to a magnetic anisotropy direction being perpendicular to the plane of the magnetic layers.

[0043] The reference layer 120 and the free layer 130 may each be formed of, or at least comprise, CoFe or CoFeB. The CoFeB may e.g. be arranged in one or several layers in the reference layer 120 and/or the free layer. The barrier layer 140 may be formed of, or at least comprise, MgO configured to allow electrons to tunnel between the reference layer 120 and the free layer 130. According to various embodiments, the barrier layer 140 has a thickness adapted to tunnel electrons, e.g., quantum mechanically directly tunnel, between the magnetic reference layer 120 and the magnetic free layer 130 at a current density sufficient to cause a change in the magnetization direction of the variable magnetization under a bias, e.g., a write bias. For example, the thickness may be between about 2 nm and about 0.5 nm, between about 1.5 nm and about 0.5 nm, or between about 1.0 nm and about 0.5 nm. The write bias may be, e.g., between about 0.1V and 3V, between about 0.3V and 2V, between about 0.5V and 1.5V or between about 0.5V and 1V. The current density sufficient to cause the change in the magnetization direction may be, e.g., greater than 110.sup.5/cm.sup.2, greater than 510.sup.5/cm.sup.2 or greater than 110.sup.6/cm.sup.2. It will be appreciated that the current density is at least partially spin-polarized or spin-filtered due to the presence of the batter layer 140 comprising MgO.

[0044] The buffer layer 150 may, as already mentioned, be provided as an integral part of the magnetic free layer 130 or at the interface between the magnetic free layer 130 and the barrier layer 140. The buffer layer 150 may be formed of CoFe and a dopant such as e.g. C or N at a concentration that may be less than 8 at. %, such as e.g., less than 4 at. %. Without being bound to any theory, advantageous effects of adding the dopant may originate from a vertical strain that is induced in the buffer layer and/or from diffusion of atoms, e.g., B, being impeded or blocked through the buffer layer 150. Without being bound to any theory, the vertical strain may be compressive strain which may be caused, e.g., by volumetric expansion of the dopant atoms. The vertical strain may in turn increase the perpendicular magnetic anisotropy and/or result in an increased tunnel-magneto resistance ratio (TMR) of the MTJ. Impeding or controlling the diffusion of atoms, e.g., B, may desirably delay the crystallization of the CoFe or CoFeB (as compared to the crystallization of the MgO), e.g., during anneal and further reduce the risk of degradation of the interface between CoFe or CoFeB and MgO.

[0045] In FIG. 2, an MTJ 110 is shown that may be similarly configured as the MTJ described with reference to FIG. 1, according to other embodiments. Unlike FIG. 1, as shown in FIG. 2, a first buffer layer 152 may be formed as an integral part of the reference layer 120 or arranged at the interface between the reference layer 120 and the barrier layer 140. Alternatively, or additionally, a second buffer layer 154 may be arranged as an integral part of the free layer 130 or arrange at the interface between the free layer 130 and the barrier layer 140. Further, an electrode 180 is shown that may be arranged between the reference layer 120 and the underlying seed layer 160.

[0046] It will be appreciated that when formed as an integral part of the free layer 130 and/or the reference layer 120, the buffer layer 150 (FIG. 1) or buffer layers 152, 154 (FIG. 2) may form a region or regions having locally different composition(s) without forming a distinct interface between the buffer layer and the respective layer having the buffer layer as part thereof.

[0047] In various embodiments described herein, the buffer layer (150, FIG. 1; 152, 154 FIG. 2) may have an average thickness of 0.2 nm-2 nm, 0.2 nm-1.5 nm, or 0.2 nm-1.0 nm, for instance about 0.3 nm or about 0.5 nm (see the MRAM device measured for experimental results described with respect to FIGS. 4-6). In various embodiments, the ratio between thicknesses of the buffer layer and the adjacent layer (magnetic free layer 130, FIG. 1; magnetic free layer 130 and/or magnetic reference layer 120, FIG. 2) can be between about 0.1 and about 0.7, between about 0.2 and about 0.6, or between about 0.2 and about 0.5, for instance about 0.27 or about 0.46 nm (see the MRAM device measured for experimental results described with respect to FIGS. 4-6). These thicknesses and ratios can be critical in combination with various other structural parameters described throughout the specification, as evident in the description below with respect to experimental results illustrated in FIGS. 4-6.

[0048] As described herein, when the buffer layer 150, 152, 154 serves as a diffusion barrier or a diffusion buffer layer, the intermixing of elements between layers interposed by the buffer layer is suppressed, as indicated in the final device. The concentrations of elements in the magnetic free layer 130 are minimized to be substantially free thereof in the barrier layer 140, and the concentrations of elements in the barrier layer 140 are minimized to be substantially free thereof in the magnetic free layer 130. For example, B in the barrier layer 140 originating from the magnetic free layer 130 or the magnetic reference layer 120, or the O in the magnetic free layer 130 or the magnetic reference layer 120 originating from the barrier layer 140, may be substantially not present (e.g., less than 10%, less than 5%, less than 3% or less than 1%), after being subject to a temperature exceeding, e.g., 250 C. or 300 C., for instance 350 C. or 375 C. As a result, various device performance indicators are improved compared to devices that do not have the barrier layer 150, as described below with respect to experimental results illustrated in FIGS. 4-6.

[0049] It will be appreciated that the free layer 130 and/or the reference layer 120 of the MRAM device may comprise a plurality of layers. As indicated in FIG. 3, which shows an embodiment that may be similarly configured as the embodiments shown in FIGS. 1 and 2, the reference layer 120 may be provided with e.g. a tri-layer design. The reference layer 120 may e.g. be formed of a stack of a Co layer 122, a CoFeBTa layer 124 and a CoFeB layer 126. The Co layer 122 may e.g. be provided on an electrode 180 that e.g. may comprise Ru, whereas the CoFeB layer 126 may be arranged closer, or adjacent, to the barrier layer 140.

[0050] Similarly, the free layer 130 may be formed of a stack of a buffer layer 150, e.g. comprising CoFeC, a CoFeB layer 132, a layer 134 comprising e.g. Mg and/or Ta, and a further CoFeB layer 136. As indicated in the example in FIG. 3, the buffer layer may be arranged on or adjacent to the barrier layer 140 whereas the further CoFeB layer 136 may be arranged on the top of the stack, adjacent to the cap layer 170. The cap layer may be formed of an additional MgO layer 172 and a metal cap layer 174.

[0051] The MRAM device as described above may further comprise a hard layer 190, which may comprise e.g. Co and/or Ni, and a seed layer 160 comprising e.g. Ni, Cr and/or Hf. The hard layer 190 may be arranged between the seed layer 160 and the electrode layer 180.

[0052] In the following, an experiment will be described which was performed to determine the performance of an MRAM device wherein a part of the CoFeB layer of the free layer was replaced by a buffer layer according to embodiments of the disclosed technology.

[0053] FIG. 4 is a diagram illustrating the results of an experiment wherein the TMR of three different MRAM devices was measured at 350 C. and 375 C. The third MRAM device is used as a reference device, having a free layer comprising an 11 thick layer of CoFeB. In the first and the second MRAM devices, a part of the 11 thick CoFeB layer has been replaced by a buffer layer of CoFeC according to embodiments of the disclosed technology (which may be similarly configured as the embodiments described with reference to FIGS. 1 to 3).

[0054] In the first MRAM device, the free layer comprises a 3 thick layer of CoFeC that is arranged on the barrier layer, and an 8 thick layer of CoFeB formed on the CoFeC layer. In the second MRAM device, the free layer has a twice as thick CoFeC layer as compared to the free layer of the first device, i.e., a 6 thick layer of CoFeC, onto which a 5 thick CoFeB layer is arranged.

[0055] As shown in the diagram in FIG. 4, no substantial difference in TMR was observed for the first and second MRAM device. The TMR was determined to be about 130% for both MRAM devices and for both 350 C. and 375 C. The third MRAM device, i.e., the reference MRAM device without any buffer layer, however showed a lower TMR at both temperatures. The TMR was determined to be just below 120% at 350 C. and about 125% at 375 C. The introduction of a buffer layer according to the disclosed technology hence allows for a higher TMR as compared to MRAM devices not having the buffer layer.

[0056] FIG. 5 is a diagram illustrating the results of measurements of the resistance-area product (RA) of the MRAM devices discussed with reference to FIG. 4. The RA is measured as at the same temperatures as above, i.e., at 350 C. and 375 C. As shown in FIG. 5, no substantial difference in RA is determined between any of the MRAM devices for a given temperature. Thus, by introducing the buffer layer according to embodiments of the invention to the free layer of the MTJ, the TMR may be increased without increasing the RA.

[0057] FIG. 6 is a diagram illustrating the results of measurements of the magnetic moment of the first MRAM device and the third MRAM device discussed with reference to FIG. 4. In the present study, the magnetic moment of the MRAM devices was studied as a function of an applied magnetic field. As indicated in the present Figure, no substantial difference in magnetic moment was observed for the first MRAM (having a buffer layer according to an embodiment of the invention) and the third MRAM device (having no buffer layer). Both MRAM devices in the study showed a switch from zero to about 350 micro emu/cm.sup.2 at about +50 Oe, and back to zero at about 50 Oe. Thus, the introduction of the buffer layer according to embodiments of the disclosed technology to the free layer may provide for an increased TMR without substantially reducing the magnetic moment of the MRAM device.

[0058] FIG. 7 schematically depicts a method of manufacturing an MRAM device according to an embodiment of the present invention. The MRAM device may be similarly configured as the embodiments described with reference to FIGS. 1 to 6. In the method, a barrier layer comprising MgO may be formed 710 on a magnetic reference layer comprising CoFeB. Further, a magnetic free layer comprising CoFeB may be formed 720 on the barrier layer. Additionally, a buffer layer may be formed 730 which may comprise at least one of Co, Fe and CoFe and may be doped with C and/or N. The buffer layer may e.g. be formed between the barrier layer and the free layer. Further, the method may comprise a step of anneal 740 wherein the MTJ is subject to a temperature exceeding, e.g., 250 C. or 300 C., for instance 350 C. or 375 C., to allow one or more of the barrier layer, the magnetic reference layer and the magnetic free layer to crystallize, e.g., into a body-centered cubic (BCC) crystal structure.

[0059] In conclusion, an MRAM device is disclosed wherein a buffer layer of at least one of Co, Fe and CoFe, which is doped with C and/or N, is added to the stack forming the MTJ. The buffer layer may be used for controlling diffusion within layers of the stack so as to control the crystallization rate of the reference layer and/or the free layer and to reduce the risk of interface degradation at the interface between e.g. the reference/free layer and the barrier layer. Further, the buffer layer may be used for inducing strain in the MTJ stack and thereby increasing the PMA and/or TMR of the MTJ.

[0060] While the present invention has been illustrated and described in detail in the appended drawings and the foregoing description, such illustration and description are to be considered illustrative or exemplifying and not restrictive; the present invention is not limited to the disclosed embodiments. Other variations to the disclosed embodiments can be understood and effected by those skilled in the art in practicing the claimed invention, from a study of the drawings, the disclosure, and the appended claims. The mere fact that certain measures or features are recited in mutually different dependent claims does not indicate that a combination of these measures or features cannot be used to advantage. Any reference signs in the claims should not be construed as limiting the scope.