KR101849599B1 - Magnetic Memory Device Having Extrinsic Perpendicular Magnetization Structure And Method Of Fabricating The Same - Google Patents

Abstract

There is provided a magnetic memory device having an extrinsic perpendicular magnetization structure and a method of manufacturing the same. The apparatus includes a magnetic tunnel junction having a tunnel barrier and an extrinsic perpendicular magnetization structure, wherein the extrinsic perpendicular magnetization structure comprises a vertical magnetization preservation film, a magnetic film between the vertical magnetization preservation film and the tunnel barrier, And the vertical magnetization preservation film may be formed of at least one of materials having a smaller oxygen affinity than the metal constituting the perpendicular magnetization induction film.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnetic memory device having an extrinsic perpendicular magnetization structure,

The present invention relates to a semiconductor memory device, and more particularly, to a magnetic memory device having an extrinsic perpendicular magnetization structure and a method of manufacturing the same.

As portable computing devices and wireless communication devices are widely adopted, there is a need for memory devices with high density, low power and non-volatile characteristics. Because magnetic memory devices are expected to meet these technical requirements, research has been actively conducted.

In particular, the tunnel magnetoresistance (TMR) effect seen in a magnetic tunnel junction (MTJ) has attracted attention as a data storage mechanism in a magnetic memory device. In the 2000s, several hundreds to several thousands of% [0004] As visible magnetic tunnel junctions (MTJs) have been reported, magnetic memory devices with such magnetic tunnel junctions have been actively studied recently. However, due to the reduction of the pattern size for increasing the memory capacity, it is becoming difficult to secure thermal stability in the magnetic tunnel junction.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a magnetic memory device having increased thermal stability.

SUMMARY OF THE INVENTION The present invention provides a method of manufacturing a magnetic memory device having increased thermal stability.

There is provided a magnetic memory device having an extrinsic perpendicular magnetization structure. The apparatus includes a tunnel barrier and a magnetic tunnel junction having an extrinsic perpendicular magnetization structure, wherein the extrinsic perpendicular magnetization structure comprises a vertical magnetization preservation film, a magnetic film between the perpendicular magnetization preservation film and the tunnel barrier, And a perpendicular magnetization induction film between the film and the magnetic film. The vertical magnetization preservation film may be formed of at least one material having an oxygen affinity lower than that of the metal constituting the perpendicular magnetization induction film.

According to some embodiments, the magnetic film includes a magnetic material having an oxygen affinity lower than that of the metal constituting the perpendicular magnetization induction film, and the perpendicular magnetization preservation film includes a metal material having an oxygen affinity lower than that of the magnetic film can do.

According to some embodiments, the perpendicular magnetization preservation film may be formed of at least one of noble metal or copper.

According to some embodiments, the magnetic film is formed of an inherent horizontal magnetic material, and may have vertical magnetization characteristics through bonding with oxygen atoms contained in the perpendicular magnetization induction film.

According to some embodiments, the extrinsic perpendicular magnetization structure may further include a transition region interposed between the magnetic film and the perpendicular magnetization induction film. The transition region may be lower than the perpendicular magnetization induction film and have an oxygen content higher than the magnetic film.

According to some embodiments, the thickness of the magnetic film may be from 3 angstroms to 17 angstroms.

According to some embodiments, the magnetic film is formed of at least one of ferromagnetic materials, the perpendicular magnetization inducing film is formed of one of metal oxides, and the perpendicular magnetization preservation film is formed of a metal having a smaller oxygen affinity than tantalum and titanium And may be formed as at least one.

According to some embodiments, the magnetic tunnel junction comprises a first structure comprising a pinned layer, a second structure comprising a free layer, and a second structure including a free layer, The tunnel barriers may include a plurality of tunnel barriers. The extrinsic perpendicular magnetization structure constitutes a part of at least one of the first and second structures, and the magnetic film of the extrinsic perpendicular magnetization structure may be used as at least one of the protective film and the free film.

According to some embodiments, the apparatus may further comprise a substrate. One of the first and second structures may be interposed between the substrate and the other of the first and second structures.

According to some embodiments, the extrinsic perpendicular magnetization structure may be included as part of the first structure, and the first structure may further include a pinning layer that fixes the magnetization direction of the support film .

According to some embodiments, the extrinsic perpendicular magnetization structure may be included as part of the second structure.

According to some embodiments, the extrinsic perpendicular magnetization structure may be included as part of both the first and second structures.

According to some embodiments, the first structure may further include a pinning layer that fixes the magnetization direction of the fixed film, and the fixed film may be interposed between the fixed film and the tunnel barrier. have.

According to some embodiments, one of the protective film and the free film may be formed of an intrinsic perpendicular magnetic film.

According to some embodiments, the magnetic tunnel junction may further include a conductive film covering the perpendicular magnetization preservation film. In this case, the perpendicular magnetization preservation film may be interposed between the perpendicular magnetization induction film and the conductive film, and the conductive film may be formed of a material having an oxygen affinity that is smaller than or equal to that of the perpendicular magnetization preservation film.

According to some embodiments, the oxygen content of the perpendicular magnetization induction film may be higher in the region adjacent to the perpendicular magnetization preservation film than in the region adjacent to the magnetic film.

There is provided a magnetic memory device including a vertical magnetization induction film. The apparatus includes a tunnel barrier interposed between first and second structures, wherein each of the first and second structures comprises a metal film and a magnetic film, at least one of the first and second structures And a vertical magnetization induction film in contact with the metal film and the magnetic film. The metal film in contact with the perpendicular magnetization induction film may have an oxygen affinity lower than that of the metal constituting the perpendicular magnetization induction film.

According to some embodiments, the magnetic film in contact with the perpendicular magnetization induction film includes a magnetic material having an oxygen affinity lower than that of the metal constituting the perpendicular magnetization induction film, and the metal film, which is in contact with the perpendicular magnetization induction film, And a metal material having an oxygen affinity smaller than that of the magnetic film in contact with the magnetization inducing film.

According to some embodiments, the metal film in contact with the vertical magnetization induction film may be formed of at least one of noble metal or copper.

According to some embodiments, the magnetic film in contact with the perpendicular magnetization induction film may be formed of an inherent horizontal magnetic material, and has vertical magnetization characteristics through bonding with oxygen atoms contained in the perpendicular magnetization induction film.

According to some embodiments, the apparatus may further include a transition region interposed between the magnetic film and the perpendicular magnetization induction film. The transition region may have an oxygen content lower than that of the perpendicular magnetization induction film and higher than that of the magnetic film in contact with the perpendicular magnetization induction film.

According to some embodiments, the thickness of the magnetic film in contact with the perpendicular magnetization induction film may be between 3 angstroms and 17 angstroms.

According to some embodiments, the magnetic film in contact with the perpendicular magnetization induction film is formed of at least one of ferromagnetic materials, the perpendicular magnetization induction film is formed of one of metal oxides, and the metal film in contact with the perpendicular magnetization induction film is tantalum And metals having oxygen affinity lower than titanium.

According to some embodiments, one of the first and second structures may further include a fixing film included therein, which fixes the magnetization direction of the magnetic film.

According to some embodiments, one of the metal films of the first and second structures may be formed of an intrinsic perpendicular magnetic film.

According to some embodiments, at least one of the first and second structures may further include a conductive film covering the metal film. The metal film may be interposed between the perpendicular magnetization induction film and the conductive film, and the conductive film may be formed of a material having an oxygen affinity smaller than or equal to that of the metal film.

According to some embodiments, the oxygen content of the perpendicular magnetization induction film may be higher in a region adjacent to the metal film than in an area adjacent to the magnetic film.

A method of manufacturing a magnetic memory device including a vertical magnetization induction film is provided. The method may include forming an extrinsic perpendicular magnetization structure including a magnetic film, a perpendicular magnetization preservation film, and a perpendicular magnetization induction film therebetween. Wherein the magnetic film is formed of an inherent horizontal magnetic material having a perpendicular magnetization characteristic through bonding with oxygen atoms included in the perpendicular magnetization induction film, and the perpendicular magnetization preservation film is formed of oxygen It can be formed of a material having affinity to prevent outflow of oxygen atoms from the perpendicular magnetization induction film.

According to some embodiments, the magnetic film is formed of at least one of ferromagnetic materials, the perpendicular magnetization inducing film is formed of one of metal oxides, and the perpendicular magnetization preservation film is formed of a metal having a smaller oxygen affinity than tantalum and titanium And may be formed as at least one.

According to some embodiments, the step of forming the extrinsic structure includes sequentially forming a metal film and the perpendicular magnetization preservation film on the magnetic film, and performing an oxygen supply process to remove oxygen atoms in the perpendicular magnetization preservation film And a step of heat treating the resultant product having the vertical magnetization preserving film formed thereon. At this time, the metal film may react with oxygen atoms diffused from the perpendicular magnetization preservation film during the heat treatment step to form an oxide functioning as the perpendicular magnetization induction film.

According to some embodiments, the method may further include forming a conductive film covering the vertical magnetization preservation film after performing the oxygen supply process, wherein the conductive film is formed before or after the heat treatment step .

According to some embodiments, the conductive film may be formed of a material having an oxygen affinity that is less than or equal to metal atoms constituting the perpendicular magnetization preservation film.

According to some embodiments, the metal film may be substantially oxygen-free material prior to performing the oxygen supply process.

According to some embodiments, the step of forming the extrinsic structure includes the steps of forming the vertical magnetization preservation film, supplying oxygen atoms into the vertical magnetization preservation film by performing an oxygen supply process, Forming a metal film and the magnetic film on the vertical magnetization preserving film, and heat treating the resultant product having the magnetic film formed thereon. The metal film reacts with oxygen atoms diffused from the perpendicular magnetization preservation film during the heat treatment step to form an oxide functioning as the perpendicular magnetization induction film.

According to some embodiments, before forming the perpendicular magnetization preservation film, the method may further include forming a conductive film covered by the perpendicular magnetization preservation film.

According to some embodiments, the conductive film may be formed of a material having an oxygen affinity that is less than or equal to metal atoms constituting the perpendicular magnetization preservation film.

According to some embodiments, the metal film may be substantially oxygen-free material prior to performing the heat treatment step.

A magnetic memory device comprising a metal oxide film is provided. The apparatus includes a magnetic tunnel junction having a first structure including a pinned layer, a second structure including a free layer, and a tunnel barrier interposed between the first and second structures can do. Wherein at least one of the first and second structures is configured to have an extrinsic perpendicular magnetization structure, wherein the extrinsic perpendicular magnetization structure comprises a ferromagnetic film and a ruthenium film facing each other, and a metal oxide film interposed between the ferromagnetic film and the ruthenium film . ≪ / RTI > The thickness of the ferromagnetic film is 3 angstroms to 17 angstroms, and the metal oxide film may be directly coated on one surface of the ferromagnetic film and one surface of the ruthenium film facing the ferromagnetic film.

The magnetic tunnel junction according to the present invention is configured to include an extrinsic perpendicular magnetization structure, wherein the extrinsic perpendicular magnetization structure includes a magnetic film, a perpendicular magnetization preservation film, and a perpendicular magnetization induction film therebetween. The perpendicular magnetization preservation film is formed of a material having a low oxygen affinity, thereby preventing a technical difficulty that the perpendicular anisotropy of the magnetization direction in the magnetic film is deteriorated by a subsequent thermal process.

1 is a circuit diagram exemplarily showing a unit cell of a magnetic memory device according to embodiments of the present invention.
Figures 2 to 6 are circuit diagrams illustrating exemplary selection devices according to embodiments of the present invention.
Figure 7 is a schematic diagram illustrating a first type of magnetic tunnel junction in accordance with embodiments of the present invention.
Figure 8 is a schematic diagram illustrating a second type of magnetic tunnel junction in accordance with embodiments of the present invention.
9 is a perspective view exemplarily showing an extrinsic perpendicular magnetization structure that forms part of a magnetic tunnel junction according to embodiments of the present invention.
10A and 10B are graphs showing one aspect of the extrinsic perpendicular magnetization structure according to embodiments of the present invention.
Figure 11 is a graph illustrating another aspect of the extrinsic vertical magnetization structure in accordance with embodiments of the present invention.
12 is a graph showing another aspect of the extrinsic vertical magnetization structure according to embodiments of the present invention.
13 is an exemplary table of lower or upper structures according to embodiments of the present invention.
Figs. 14-17 are cross-sectional views illustratively illustrating substructures according to embodiments of the present invention. Fig.
Figs. 18-21 are cross-sectional views illustratively showing superstructures according to embodiments of the present invention. Fig.
22 is an exemplary table of magnetic tunnel junctions of a first type according to embodiments of the present invention.
Figures 23-25 are cross-sectional views illustrating exemplary first type magnetic tunnel junctions in accordance with embodiments of the present invention.
26 is an exemplary table of magnetic tunnel junctions of a second type according to embodiments of the present invention.
Figures 27-29 are cross-sectional views illustratively illustrating a second type of magnetic tunnel junctions in accordance with embodiments of the present invention.
30 is a circuit diagram exemplarily showing a unit cell of a magnetic memory element according to a modified embodiment of the present invention.
31 is a flow chart illustrating methods of fabricating a magnetic tunnel junction in accordance with some embodiments of the present invention.
32 is a graph showing one side of the magnetic tunnel junction fabricated by the manufacturing method of FIG. 31;
33 is a flow chart illustrating methods of fabricating a magnetic tunnel junction according to other embodiments of the present invention.
34 is a graph showing an aspect of a magnetic tunnel junction fabricated by the manufacturing method of FIG. 33;
35 is an experimental graph illustrating an exemplary aspect of the magnetic properties of a magnetic tunnel junction according to the present invention.
Figure 36 is an experimental graph illustrating another aspect of the magnetic properties of a magnetic tunnel junction according to the present invention.
37 and 38 are diagrams for schematically explaining electronic devices including a semiconductor device according to embodiments of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features, and advantages of the present invention will become more readily apparent from the following description of preferred embodiments with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, the embodiments disclosed herein are provided so that the disclosure can be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

In this specification, when it is mentioned that a film is on another film or substrate, it means that it may be formed directly on another film or substrate, or a third film may be interposed therebetween. Further, in the drawings, the thicknesses of the films and regions are exaggerated for an effective explanation of the technical content. Also, while the terms first, second, third, etc. in various embodiments of the present disclosure are used to describe various regions, films, etc., these regions and films should not be limited by these terms . These terms are only used to distinguish any given region or film from another region or film. Thus, the membrane referred to as the first membrane in one embodiment may be referred to as the second membrane in another embodiment. Each embodiment described and exemplified herein also includes its complementary embodiment.

1 is a circuit diagram exemplarily showing a unit cell of a magnetic memory device according to embodiments of the present invention.

Referring to FIG. 1, the unit cells 100 connect the first wires 10 and the second wires 20 that intersect with each other. The unit cell 100 may include a selection device 30 and a magnetic tunnel junction (MTJ). The selection element 30 and the magnetic tunnel junction (MTJ) may be electrically connected in series. One of the first and second wirings 10 and 20 may be used as a word line and the other as a bit line.

The selection element 30 may be configured to selectively control the flow of charge across the magnetic tunnel junction (MTJ). For example, the selection device 30 may be one of a diode, a pn-bipolar transistor, an epitaxial bipolar transistor, an emmos field effect transistor, and a pmos field effect transistor as shown in Figs. 2 to 6. When the selection element 30 is a bipolar transistor or a MOS field effect transistor, which is a three-terminal element, additional wiring (not shown) may be connected to the selection element 30.

The magnetic tunnel junction (MTJ) may include a lower structure 41, a superstructure 42, and a tunnel barrier 50 therebetween. Each of the first and the upper structures 41 and 42 may include at least one magnetic film formed of a magnetic material.

The magnetization direction of one of the magnetic films is fixed regardless of an external magnetic field under a normal use environment. Hereinafter, the magnetic film having such fixed magnetization characteristics will be referred to as a pinned layer (PL). On the other hand, the magnetization of the other one of the magnetic films can be switched by an external magnetic field applied thereto. Hereinafter, the magnetic film having such variable magnetization characteristics will be referred to as a free layer (FRL). 7 and 8, the magnetic tunnel junction MTJ includes at least one free film FRL and at least one of the protection films PL separated by the tunnel barrier 50, .

The electrical resistance of the magnetic tunnel junction (MTJ) may be dependent on the magnetization directions of the free layer (FRL) and the protection film (PL). For example, the electrical resistance of the magnetic tunnel junction (MTJ) can be much larger when they are antiparallel compared to the case where the magnetization directions of the free layer FRL and the protection film PL are parallel . As a result, the electrical resistance of the magnetic tunnel junction (MTJ) can be adjusted by changing the magnetization direction of the free layer (FRL), which can be used as a data storage principle in the magnetic memory device according to the present invention.

The lower and upper structures 41 and 42 of the magnetic tunnel junction MTJ may be sequentially formed on a predetermined substrate sub as shown in FIGS. In this case, the magnetic tunnel junction (MTJ) is divided into two types according to the relative arrangement between the free film FRL and the substrate sub or the formation order of the free film FRL and the protection film PL, . 7, the lower structure 41 and the upper structure 42 may be formed of a material containing the protective film PL and the free film FRL, respectively, (MTJ1), or the lower structure 41 and the upper structure 42 may be formed of a first type of magnetic tunnel junction MTJ1 or a second type of magnetic tunnel junction MTJ2 of the second type including the free film FRL and the protection film PL, Type magnetic tunnel junction (MTJ2).

FIG. 9 is a perspective view exemplarily showing an extrinsic perpendicular magnetization structure constituting a part of a magnetic tunnel junction according to embodiments of the present invention, and FIGS. 10A and 10B are cross- FIG. 2 is a graph showing one aspect of the extrinsic perpendicular magnetization structure according to the present invention. FIG.

According to an aspect of the present invention, at least one of the lower structure 41 and the upper structure 42 may constitute an extrinsic perpendicular magnetization structure (EPMS). According to some embodiments, the extrinsic perpendicular magnetization structure (EPMS) may include a magnetic film (MGL), a perpendicular magnetization preserving layer (PMP), and the magnetic film (MGL) And a perpendicular magnetization inducing layer (PMI) interposed between the vertical magnetization preservation films (PMP). The magnetic film (MGL) of the extrinsic perpendicular magnetization structure (EPMS) may be the magnetic film included in the lower structure 41 and the upper structure 42. That is, the free layer FRL or the protection film PL may be used as the magnetic film MGL of the extrinsic perpendicular magnetization structure (EPMS).

The magnetic layer (MGL) may be a ferromagnetic material. For example, the magnetic layer (MGL) may be formed of a metal such as cobalt iron boron (CoFeB), cobalt iron (CoFe), nickel iron (NiFe), cobalt iron platinum (CoFePt), cobalt iron palladium (CoFePd), cobalt iron chromium , Cobalt iron terbium (CoFeTb), cobalt iron gadolinium (CoFeGd), or cobalt iron nickel (CoFeNi). In addition, the magnetic film (MGL) can be formed in the form of a thin film whose thickness is relatively small compared to its horizontal length. For example, the thickness of the magnetic layer (MGL) may be from about 1 angstrom to about 30 angstroms, and more specifically from about 3 angstroms to about 17 angstroms. In this case, the magnetic layer MGL may be an intrinsic horizontal magnetic layer having an intrinsic horizontal magnetization property. That is, the magnetization direction of the magnetic film MGL may have a direction parallel to a horizontal plane (that is, an xy plane) due to the magnetic anisotropy according to the thin film shape.

Meanwhile, according to the modified embodiments of the present invention, the magnetic layer (MGL) may be an intrinsic perpendicular magnetic layer having an intrinsic perpendicular magnetization property. That is, the magnetization direction of the magnetic film MGL may be spontaneously perpendicular to its horizontal plane (i.e., the xy plane). For example, the magnetic film (MGL) may include a) cobalt iron (CoFeTb) having a content ratio of at least 10% of tb, b) cobalt iron gadolinium (CoFeGd) having a content ratio of gadolinium (Gd) C) FePt of L1 ₀ structure, e) FePd of L1 ₀ structure, f) CoPd of L1 ₀ structure, g) CoPt of L1 ₀ structure, h) Hexagonal Close Packed Lattice ) Structure of CoPt, i) alloys comprising at least one of the materials of a) to h) described above, or j) one of alternating and repetitively stacked layers of magnetic and non-magnetic layers. The structure in which the magnetic layers and the non-magnetic layers are alternately and repeatedly stacked includes (Co / Pt) n, (CoFe / Pt) n, (CoFe / Pd) n, , (CoNi / Pt) n, (CoCr / Pt) n, or (CoCr / Pd) n (n is the number of lamination).

The perpendicular magnetization induction film PMI is formed to be in direct contact with the magnetic film MGL and the direct contact may be made such that the magnetization direction of the magnetic film MGL is parallel to the thickness direction z of the magnetic film MGL . That is, the vertical magnetization induction layer PMI may provide an external factor to make the magnetic layer MGL have vertical magnetization characteristics. For this reason, the perpendicular magnetization induction film (PMI) and the magnetic film (MGL) which are in contact with each other can form a structure having an extrinsic perpendicular magnetization property (hereinafter, an extrinsic perpendicular magnetization structure). Hereinafter, the magnetic film (MGL) constituting the extrinsic perpendicular magnetization structure may be referred to as an extrinsic perpendicular magnetic film.

The vertical magnetization induction layer (PMI) may be a material containing oxygen atoms. According to some embodiments, the perpendicular magnetization induction layer (PMI) may be at least one of the metal oxides. For example, the perpendicular magnetization induction film (PMI) may be at least one of magnesium oxide, tantalum oxide, titanium oxide, aluminum oxide, magnesium zinc oxide, hafnium oxide, or magnesium boron oxide. Meanwhile, the vertical magnetization induction layer PMI may have a higher resistivity than the magnetic layer MGL or the perpendicular magnetic layer PMP. In this case, the electrical resistance of the magnetic tunnel junction (MTJ) may be highly dependent on the resistance of the perpendicular magnetization induction film (PMI). In order to reduce such dependence, the vertical magnetization induction film (PMI) may be formed to have a small thickness. For example, the perpendicular magnetization induction film PMI may be thinner than the magnetic film MGL or the vertical magnetization preservation film PMP.

The vertical magnetization PMP may be formed of a material having a resistivity lower than that of the vertical magnetization induction layer PMI. For example, the vertical magnetization preservation film (PMP) may be at least one of noble metal (such as ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold) or copper. According to some embodiments of the present invention, the perpendicular magnetization preservation film (PMP) may be one of materials having a lower specific resistance than tantalum or titanium.

In addition, according to one aspect of the present invention, the portion of the perpendicular magnetization preservation film (PMP) that contacts at least the perpendicular magnetization inductive film (PMI) may be formed of a material difficult to react with oxygen atoms. The above-mentioned noble metal or copper can be selected as a material that satisfies this condition for the vertical magnetization preserving film (PMP). According to some embodiments, the perpendicular magnetization preservation film (PMP) can be a material that can substantially completely block the reaction with oxygen atoms even in a subsequent process or under the normal usage environment of the user.

For example, as shown in FIG. 10A, the perpendicular magnetization preservation film (PMP) may be a material having a lower oxygen affinity than the metal constituting the perpendicular magnetization induction film (PMI). Alternatively, the oxygen affinity can be determined by the standard heat of formation of the metal oxide (? H ⁰ _f (Unit: kJ / mole Oxygen), and as shown in FIG. 10B, ΔH ⁰ _f of the vertical magnetization induction layer PMI may be less than approximately -500 [kJ / mole Oxygen] The? H ⁰ _f of the metal material constituting the perpendicular magnetization preservation film (PMP) may be larger than -300 [kJ / mole Oxygen]. That is, the standard reaction enthalpy may be larger in the absolute value than in the case of the perpendicular magnetization protection film (PMP) in the case of the perpendicular magnetization induction film (PMI). For example, the metal constituting the vertical magnetization induction film PMI may be at least one of Ta, Ti, U, Ba, Zr, Al, Sr, Hf, La, Ce, Sm, Mg, And the vertical magnetization preserving film PMP may include at least one of Au, Ag, Pt, Pd, Rh, Ru, Cu, Re, and Pb. The magnetic film MGL may be a material having a smaller oxygen affinity than the metal constituting the perpendicular magnetization induction film PMI as shown in FIG. 10A or 10B, It may be a substance having a large oxygen affinity. On the other hand, the reaction with oxygen can be quantitatively expressed through various physical quantities. For example, in addition to the oxygen affinity described above, the oxidation potential or the free energy in the oxidation reaction can be used to quantitatively express the ease of reaction with such oxygen.

11, the magnetic film (MGL) having the above-described extrinsic perpendicular magnetization characteristics can be obtained by chemical bonding (bonding) between atoms of the magnetic film (MGL) and oxygen atoms constituting the perpendicular magnetization induction film ≪ / RTI > 11, an oxygen content higher than the magnetic film (MGL) and lower than the perpendicular magnetization induction film (PMI) is formed between the magnetic film (MGL) and the perpendicular magnetization induction film (PMI) A transition region TR can be formed. There is no reason why the oxygen content in the transition region TR is linear. For example, as shown in FIG. 11, the oxygen content in the transition region TR may vary monotonically within a predetermined envelope (ENV).

Alternatively, the vertical magnetization preservation film (PMP) may be a material which does not react with oxygen atoms in a subsequent process or under a normal use environment of the user as described above. As shown in FIG. 11, the perpendicular magnetization inductive film PMI has a finite size of oxygen content, but according to some embodiments, the vertical magnetization preservation film PMP has substantially infinitesimal oxygen content Lt; / RTI > In some embodiments, the oxygen content may abruptly change at the interface between the perpendicular magnetization inductive film (PMI) and the vertical magnetization preserving film (PMP). That is, the absolute value of the rate of change of the oxygen content may be larger at the interface between the vertical magnetization induction film (PMI) and the vertical magnetization preservation film (PMP) than in the transition region TR.

According to other embodiments, the transition region TR may be formed throughout the vertical magnetization induction layer (PMI). 11, the rate of change of the oxygen content of the perpendicular magnetization induction film PMI in the z direction may have a finite size in the entire region between the magnetic film MGL and the perpendicular magnetization induction film PMI. have. According to some embodiments, the oxygen content of the perpendicular magnetization induction layer (PMI) may be higher in a region adjacent to the vertical magnetization induction layer (PMI) than in a region adjacent to the magnetic layer (MGL).

12 is a graph showing another aspect of the extrinsic vertical magnetization structure according to embodiments of the present invention.

In order to manufacture the magnetic memory device according to the present invention, predetermined process steps are additionally performed even after the vertical magnetization induction film (PMI) and the vertical magnetization preservation film (PMP) are formed. (E.g., a heat treatment step or a wiring formation step, etc.). The vertical magnetization induction film PMI can be formed by thermal energy during such subsequent process steps as shown in FIG. 12 or during product use by a user after product sale Can be supplied. This thermal energy can lead to the separation of oxygen atoms from the vertical magnetization induction film (PMI).

However, in the presence of the vertical magnetization preservation film (PMP) formed of a material having a low oxygen affinity, diffusion of the separated oxygen atoms and hence oxygen escape from the perpendicular magnetization induction film (PMI) have. Specifically, when the vertical magnetization preservation film (PMP) is formed of a material having a low oxygen affinity as described above, when the supply of thermal energy is stopped and the separated oxygen atoms return to a chemically stable state, The oxygen atoms recombine with the metal atoms constituting the vertical magnetization induction film (PMI), not the vertical magnetization preservation film (PMP). That is, the vertical magnetization induction layer PMI may be restored to a state before the supply of the thermal energy.

Each of the lower and upper structures 41 and 42 may include a magnetic film, as described with reference to FIG. At this time, the magnetic film may be divided into a free layer (FRL) or a protection film (PL) according to its function as described with reference to FIGS. In addition, the magnetic film can be used as part of an extrinsic perpendicular magnetization structure (EPMS) having vertical magnetization characteristics by an external factor (for example, the vertical magnetization induction film PMI) as described with reference to FIG. 9 .

On the other hand, according to some embodiments of the present invention, the above-described intrinsic perpendicular magnetic film having the inherent vertical magnetization characteristic can be used as one of the magnetic films included in the lower and upper structures 41 and 42. [ That is, in some embodiments, one of the magnetic layers included in the lower and upper structures 41 and 42 may include an external factor such as the perpendicular magnetization induction layer (PMI) of the extrinsic perpendicular magnetization structure (EPMS) It is possible to have vertical magnetization characteristics spontaneously. For example, the intrinsic perpendicular magnetic film is formed of a) cobalt iron (CoFeTb) having a content ratio of at least 10% of a terbium (Tb), b) cobalt iron gadolinium (CoFeGd) having a content ratio of gadolinium (Gd) Iron dysprosium (CoFeDy), d) FePt of L1 ₀ structure, e) FePd of L1 ₀ structure, f) CoPd of L1 ₀ structure, g) CoPt of L1 ₀ structure, h) Hexagonal Close Packed Lattice structure Of CoPt, i) alloys comprising at least one of the materials of a) to h) described above, or j) one of alternating and repetitively stacked layers of magnetic and nonmagnetic layers. The structure in which the magnetic layers and the nonmagnetic layers are alternately and repeatedly stacked includes (Co / Pt) n, (CoFe / Pt) n, (CoFe / Pd) n, ) n, (CoNi / Pt) n, (CoCr / Pt) n or (CoCr / Pd) n (n is the number of lamination).

As a result, each of the magnetic films constituting the magnetic tunnel junction (MTJ) may be variously varied as illustrated in FIG. 13, depending on the cause of the perpendicularity of its position, function and magnetization direction Lt; / RTI > Figs. 14 to 21 are sectional views exemplifying the lower structure 41 or the upper structure 42 including the magnetic film according to this classification.

Referring to FIG. 13, according to the positional classification, each of the magnetic films constituting the magnetic tunnel junction (MTJ) includes magnetic layers 210, 215 or the magnetic layers 310 and 315 included in the upper structure 42 as shown in FIGS. That is, the lower structure 41 may be one of the first to fourth lower structures 201, 202, 203, 204 shown in FIGS. 14 to 17, May be one of the first to fourth superstructures 301, 302, 303, 304 shown in Fig.

Also, according to the functional classification, the magnetic films 210, 215, 310, and 315 may include a free layer (FRL) having variable magnetization characteristics as exemplarily shown in FIGS. 14, 16, 18, Or as a protective film PL having fixed magnetization properties as exemplarily shown in Figs. 15, 17, 19 and 21. That is, the first lower and upper structures 201 and 301 and the third lower and upper structures 203 and 303 may be a structure including a free layer (FRL) And the fourth lower and upper structures 204 and 304 may be structures including a protection film PL.

15, 17, 19, and 21, when the magnetic layers 210, 215, 310, and 315 are used as a protective layer PL, the lower or upper structures 41 or 42 And pinning layers 240 and 340 for fixing the magnetization directions of the magnetic layers 210, 215, 310, and 315. That is, the second lower and upper structures 202 and 302 and the fourth lower and upper structures 204 and 304 may further include the fixing films 240 and 340.

According to some embodiments, the immobilizing films 240 and 340 may be configured to have a synthetic antiferromagnetic structure. For example, the fixed films 240 and 340 may be configured to include a pair of intrinsic horizontal magnetic layers and an exchange coupling layer interposed therebetween. The exchange coupling layer may be formed of one of the noble metals.

15 and 19, the fixing films 240 and 340 may include a first fixing film 241 and 341 and a second fixing film 242 and 342. In other embodiments, As shown in FIG. According to some embodiments, the first immobilizing films 241 and 341 may be configured to have the synthetic antiferromagnetic structure described above, and the second immobilizing films 242 and 342 may be the intrinsic perpendicular magnetic film described above.

Referring again to FIG. 13, according to the classification based on the cause of the perpendicular magnetization, each of the magnetic films used as the free film (FRL) or the fixed film (PL) has an extrinsic vertical The films may be the films 210 and 310, or may be the inherent vertical magnetic films 215 and 315 having spontaneous vertical magnetization characteristics without external factors. As shown in FIGS. 14, 15, 18, and 19, the extrinsic perpendicular magnetic layers 210 and 310 may include perpendicular magnetization inducing layers 220 and 320, As shown in Fig. The perpendicular magnetization induction films 220 and 320 may have the same technical characteristics as the perpendicular magnetization induction film PMI described with reference to FIG. Accordingly, the extrinsic perpendicular magnetic layers 210 and 310 and the perpendicular magnetization induction layers 220 and 320 may constitute the extrinsic perpendicular magnetization structure (EPMS) described with reference to FIG.

When the magnetic film is the extrinsic perpendicular magnetic film 210 constituting the lower structure 41, as shown in FIGS. 14 and 15, the perpendicular magnetization preservation film 230 is formed on the extrinsic perpendicular magnetic film 210 And may be disposed below the vertical magnetization induction layer 220. That is, the vertical magnetization induction layer 220 and the extrinsic vertical magnetic layer 210 may be sequentially stacked on the perpendicular magnetization storage layer 230. 18 and 19, when the magnetic film is the extrinsic perpendicular magnetic film 310 constituting the upper structure 42, the perpendicular magnetization preserving film 330 is formed on the extrinsic perpendicular magnetic film 310 And the vertical magnetization induction layer 320 may be interposed between the upper and lower layers. That is, the vertical magnetization induction layer 320 and the vertical magnetization preservation layer 330 may be sequentially stacked on the extrinsic perpendicular magnetic layer 310.

The vertical magnetization preserving films 230 and 330 may be formed of a material difficult to react with oxygen atoms. For example, the perpendicular magnetization storage layers 230 and 330 may be materials having lower oxygen affinity than the metal constituting the perpendicular magnetization induction layer (PMI). (For example, the perpendicular magnetization preservation films 230 and 330 have a standard reaction enthalpy less than -300 [kJ / mole Oxygen], and the metals constituting the perpendicular magnetization induction film PMI are -300 [kJ / mole Oxygen].

The vertical magnetization preserving films 230 and 330 may be formed on the extrinsic perpendicular magnetic films 210 and 310 and the perpendicular magnetization inducing films 220 and 320, (EPMS). According to some embodiments, the perpendicular magnetization preserving films 230 and 330 may be formed of at least one of noble metal or copper.

On the other hand, when the fixing films 240 and 340 include the second fixing films 242 and 342 as illustrated in FIGS. 15 and 19, the second fixing films 242 and 342 May be disposed closer to the perpendicular magnetic storage layers 230 and 330 than the first fixed layers 241 and 341. In these embodiments, the perpendicular magnetization preserving films 230 and 330 may be formed of materials that allow exchange coupling between the extrinsic perpendicular magnetic films 210 and 310 and the second immobilization films 242 and 342, At least one. In this case, the extrinsic perpendicular magnetic films 210 and 310 and the second fixing films 242 and 342 may have anti-parallel or mutually parallel magnetization directions.

Such exchange coupling can be realized by using a part of the noble metals exemplified above as the material for the vertical magnetization preserving films 230 and 330. For example, the vertical magnetization preserving films 230 and 330 may include at least one of ruthenium (Ru), iridium (Ir), and rhodium (Rh). According to other embodiments, the perpendicular magnetization storage layers 230 and 330 may be formed of at least one of a non-magnetic metal such as titanium, tantalum, or magnesium, oxides thereof, or nitrides thereof.

As shown in FIGS. 16 and 20, the magnetic film may be used as the free magnetic layer (FRL) in the functional aspects as the intrinsic perpendicular magnetic films 215 and 315. According to these embodiments, the lower film 235 or the upper film 335 may be disposed on the lower or upper portion of the intrinsic vertical magnetic film 215, 315, respectively. The lower film 235 and the upper film 335 may be formed of at least one of metals. For example, the upper film 335 and the lower film 235 may be formed of Ru, tantalum, palladium (Pd), titanium (Ti), platinum (Pt), silver (Ag) Au) or copper (Cu).

According to some embodiments, the bottom film 235 may function as a seed layer for growth of the im- mediate vertical magnetic film 215 located on top of it. For example, when the intrinsic perpendicular magnetic film 215 has an L1 ₀ structure, the lower film 235 may be formed of a conductive metal nitride having a sodium chloride lattice structure, such as titanium nitride, tantalum nitride, chromium nitride, . In addition, the top film 335 can be used as a capping layer to protect the underlying vertical magnetic film 315 underlying it.

The first through fourth sub structures 201, 202, 203, and 204 and the first through fourth super structures 301, 302, 303, and 304 correspond to the sub- May be used to implement a magnetic tunnel junction (MTJ). More specifically, the magnetic tunnel junction (MTJ) according to the present invention includes the lower structure 41, the tunnel barrier 50, and the upper structure 42, which are sequentially stacked, as described with reference to FIG. And may be the first type of magnetic tunnel junction (MTJ1) described with reference to FIG. 7 or the second type of magnetic tunnel junction (MTJ2) described with reference to FIG.

22, the first type of magnetic tunnel junction MTJ1 is formed of the lower structure 41 including the protection film PL and the upper structure including the free film FRL 42). The lower structure 41 including the protective film PL may be the second substructure 202 shown in Figs. 23 and 24 or the fourth substructure 204 shown in Fig. The upper structure 42 including the free film FRL may be the first upper structure 301 shown in FIGS. 23 and 25 or the third upper structure 303 shown in FIG.

26, the second type of magnetic tunnel junction MTJ2 includes the lower structure 41 including the free film FRL and the upper structure including the protection film PL 42). The lower structure 41 including the free film FRL may be the first substructure 201 shown in FIGS. 27 and 28 or the third substructure 203 shown in FIG. The upper structure 42 including the protective film PL may be the second super structure 302 shown in FIGS. 27 and 29 or the fourth super structure 304 shown in FIG.

30 is a circuit diagram exemplarily showing a unit cell of a magnetic memory element according to a modified embodiment of the present invention.

Referring to FIG. 30, a magnetic tunnel junction MTJ according to this embodiment includes a lower electrode structure 61 disposed below the lower structure 41, and a lower electrode structure 61 disposed on the upper structure 42, (62). That is, the lower electrode structure 61 may be disposed between the first wiring 10 and the lower structure 41, or between the selection device 30 and the lower structure 41, (62) may be disposed between the second wiring (20) and the upper structure (42).

Each of the lower and upper electrode structures 61 and 62 may be a single layer structure or a multi-layer structure. In addition, the lower and upper electrode structures 61 and 62 may be formed of a conductive material (more specifically, a metal). For example, at least one conductive film constituting the upper electrode structure 62 may be the third capping film CL3 described with reference to FIGS. 31 and 32, and the lower electrode structure 61 The at least one conductive film may be the first seed film SL1 described with reference to FIGS. However, according to another modified embodiment, the predetermined magnetic tunnel junction (MTJ) may be a structure that does not include one of the lower and upper electrode structures 61 and 62.

Figure 31 is a flow chart illustrating methods of fabricating a magnetic tunnel junction in accordance with some embodiments of the present invention, and Figure 32 is a graph showing one aspect of a magnetic tunnel junction according to these embodiments. Specifically, FIG. 32 illustratively illustrates a temporal change in the oxygen content of the films making up the magnetic tunnel junction, with the horizontal and vertical axes respectively showing the positions and oxygen content of the films making up the magnetic tunnel junction. To reduce the complexity in the figures and for a better understanding of the temporal variation of the oxygen content, FIG. 32 is configured to represent the oxygen contents in some of the steps described with reference to FIG.

31 and 32, a magnetic film MGL is formed (S10). The magnetic layer (MGL) may be a ferromagnetic material or an intrinsic perpendicular magnetic layer having an intrinsic perpendicular magnetization property.

Subsequently, a first capping layer CL1 and a second capping layer CL2 are sequentially formed on the magnetic layer MGL (S20 and S30). The first capping layer CL1 may be a material having an oxygen affinity higher than that of the magnetic layer MGL and / or the second capping layer CL2. According to some embodiments, the first capping layer CL1 may be at least one of magnesium, tantalum, titanium, aluminum, magnesium zinc, hafnium or magnesium boron, and the second capping layer CL2 may be at least one of ruthenium, And may be at least one of noble metal or copper (e.g., rhodium, palladium, silver, osmium, iridium, platinum, gold). The thickness of the first capping layer CL1 may be one to three times the thickness of the single layer. (Where the single film thickness may mean the thickness of one atom or molecule constituting it).

32, up to this point, the magnetic film (MGL), the first capping film CL1 and the second capping film CL2 are substantially free of oxygen . For example, the wafer may be exposed to an external atmosphere containing oxygen during the transfer process and / or the waiting process outside the deposition chamber, and the wafer may be exposed to the outside atmosphere including the magnetic film (MGL), the first capping film (CL1) Each of the second capping films CL2 may have an oxygen content that is less than or equal to a value due to oxygen penetration (hereinafter natural oxygen content) that can occur during the transfer / waiting process of such a wafer.

An oxidation process is performed on the second capping layer CL2 (S40). The oxidation treatment step S40 may be performed to oxidize at least a part of the exposed surface of the second capping layer CL2. For example, the oxidation treatment step (S40) may include supplying oxygen-containing gas under a temperature condition of room temperature to 500 degrees Celsius and a pressure condition of 0.1 mT to 1 T. According to some embodiments, the gas supplied in the oxidation treatment step (S40) may comprise at least one of oxygen or ozone.

By the oxidation treatment step (S40), the second capping film (CL2) may have an increased oxygen content as compared to before the oxidation treatment step (S40) as shown in Fig. For example, at least a portion of the oxidized second capping layer CL2 may be a noble metal (such as ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold) And may be copper containing oxygen atoms. According to some embodiments, the oxygen content of the oxidized second capping layer CL2 may decrease from its exposed surface (i.e., the top surface) towards the magnetic layer (MGL). However, the technical idea of the present invention is not limited thereto. For example, in the second capping film CL2, the positional difference of the oxygen content is determined by the process conditions in the oxidation process (S40) and the material or structure of the second capping film CL2 It can be diversified.

According to some embodiments, after the oxidation process S40 is completed, the second capping layer CL2 may include a stoichiometric oxide. For example, the second capping layer CL2 may be a ruthenium layer before the oxidation process S40, but may include ruthenium oxide after the oxidation process S40. According to other embodiments, after the oxidation process S40 is completed, the second capping layer CL2 may include a non-stoichiometric oxide. For example, after the oxidation treatment step (S40), at least a portion of the second capping layer CL2 may have an oxygen content that is smaller or larger than the stoichiometric oxide.

According to still another embodiment, after the oxidation process S40 is completed, oxygen atoms may be heterogeneously distributed within the second capping layer CL2. That is, the second capping layer CL2 may include a first portion (s) having a predetermined oxygen content and a second portion (s) having a higher oxygen content than the first portion. For example, as exemplarily shown in FIG. 32, the oxygen content of the oxidized second capping film CL2 decreases from its exposed surface (i.e., upper surface) toward the magnetic film (MGL) Can be reduced. Alternatively, after the oxidation treatment step (S40) is completed, the oxygen atoms may be distributed substantially uniformly within the second capping layer (CL2).

On the other hand, according to the modified embodiments, the second capping layer CL2 has a smaller oxygen affinity than the first capping layer CL1 when the oxidation process S40 is not performed, And may have a larger oxygen content than the first capping layer CL1. For example, the second capping layer CL2 may be formed to have an oxygen content substantially higher than the natural oxygen content. In this case, the oxidation step S40 may be omitted.

According to other modified embodiments, the first capping layer CL1 may be formed to have an oxygen content higher than the natural oxygen content when the oxidation treatment step S40 is not performed. For example, the step of forming the first capping layer CL1 may include forming the first capping layer CL1 under an oxygen atmosphere.

According to still other modified embodiments, a step of oxidizing at least a part of the exposed surface of the first capping layer CL1 may be performed before forming the second capping layer CL2. In this case, the oxidation step S40 may be omitted.

Referring again to FIG. 31, after the oxidation process S40, a third capping layer CL3 is formed (S50). The third capping layer CL3 may be formed of a conductive material. According to some embodiments, the third capping layer CL3 is formed of a conductive material having an oxygen affinity that is smaller than or equal to that of the second capping layer CL2 before the oxidation treatment step S40 is performed . However, the technical idea of the present invention is not limited thereto. For example, the third capping layer CL3 may be formed of a material having an oxygen affinity higher than that of the second capping layer CL2 before the oxidation treatment step S40 is performed.

A heat treatment step may be performed on the resultant product in which the third capping layer CL3 is formed (S60). According to some embodiments, the heat treatment step (S60) may be carried out for a time of from 1 second to 10000 seconds under a temperature condition of from room temperature to 500 degrees Celsius and a pressure condition of from 0.1 mT to 1 T. According to some embodiments, during the heat treatment step (S60), at least one of nitrogen or inert gases may be supplied as the atmosphere gas. However, the technical idea of the present invention is not limited thereto. For example, the process conditions of the heat treatment step S60 may be variously modified depending on materials, structure and oxygen content of the first and second capping films CL1 and CL2.

During the heat treatment step S60, the oxygen atoms included in the second capping layer CL2 may diffuse downward to participate in the oxidation reaction of the atoms of the first capping layer CL1. For example, the metal atoms of the first capping layer CL1 may react with oxygen atoms supplied from the second capping layer CL2 during the heat treatment step S60 to form a metal oxide. 32, the oxygen content of the first capping film CL1 is larger than the oxygen content of the surface adjacent to the second capping film CL2 on the surface adjacent to the magnetic film MGL, Can be higher. This difference in oxygen content may be because most of the oxygen contained in the first capping layer CL1 is originated from the diffusion of the oxygen atoms contained in the second capping layer CL2.

According to some modified embodiments, the step of forming the third capping layer CL3 may be omitted. For example, the heat treatment step S60 may be performed after the oxidation treatment step S40 or during the oxidation treatment step S40. According to other modified embodiments, the step of forming the third capping layer CL3 may be performed after the heat treatment step S60.

31 and 32, the magnetic layer MGL, the first capping layer CL1, and the second capping layer CL2 are formed on the external extrinsic perpendicular magnetization structure (MGL), the vertical magnetization induction film (PMI), and the vertical magnetization preservation film (PMP) in the EPMS.

Figure 33 is a flow chart illustrating methods of fabricating a magnetic tunnel junction according to other embodiments of the present invention, and Figure 34 is a graph showing one aspect of a magnetic tunnel junction according to these embodiments. Specifically, FIG. 34 illustratively illustrates a temporal change in the oxygen content of the films making up the magnetic tunnel junction, wherein the horizontal and vertical axes respectively show the position and oxygen content of the films making up the magnetic tunnel junction. To reduce complexity in the figures and for a better understanding of the temporal variation of oxygen content, Figure 34 was configured to represent the oxygen contents in some of the steps described with reference to Figure 33. [

33 and 34, a first seed layer SL1 and a second seed layer SL2 are sequentially formed (S15 and S25). The first seed layer SL1 may be a conductive material and the second seed layer SL2 may be a material having lower oxygen affinity than tantalum. For example, the second seed layer SL2 may be at least one of noble metal (such as ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold) or copper. According to some embodiments, the first seed layer SL1 may be formed of a conductive material having an oxygen affinity that is less than or equal to that of the second seed layer SL2. However, the technical idea of the present invention is not limited thereto. For example, the first seed layer SL1 may be formed of a material having an oxygen affinity higher than that of the second seed layer SL2. According to other embodiments, the step of forming the first seed layer SL1 may be omitted.

Oxidation treatment is performed on the second seed film SL2 (S35). The oxidation treatment step S35 may be performed to oxidize the exposed surface of the second seed layer SL2. For example, the oxidation treatment step (S35) may include supplying oxygen-containing gas under a temperature condition of room temperature to 500 degrees Celsius and a pressure condition of 0.1 mT to 1 T. According to some embodiments, the gas supplied in the oxidation treatment step S35 may comprise at least one of oxygen or ozone.

By the oxidation treatment step (S35), the second seed layer (SL2) can have an increased oxygen content as compared to before the oxidation treatment step (S35) as shown in Fig. For example, at least a portion of the oxidized second seed film SL2 may be a noble metal (such as ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold) And may be copper containing oxygen atoms. According to some embodiments, the oxygen content of the oxidized second seed film SL2 can be reduced from its exposed surface (i.e., upper surface) toward the first seed film SL1. However, the technical idea of the present invention is not limited thereto. For example, the positional difference of the oxygen content in the second seed film (SL2) may be determined by the process conditions at the oxidation treatment step (S35) and the material or structure of the second seed film (SL2) It can be diversified.

According to some embodiments, after the oxidation process S35 is completed, the second seed layer SL2 may include a stoichiometric oxide. For example, the second seed layer SL2 may be a ruthenium layer before the oxidation process S35, but may include ruthenium oxide after the oxidation process S35. According to other embodiments, after the oxidation treatment step S35 is completed, the second seed layer SL2 may include a non-stoichiometric oxide. For example, after the oxidation treatment step (S35), at least a portion of the second seed layer (SL2) may have an oxygen content that is smaller or larger than the stoichiometric oxide.

According to another embodiment, after the oxidation treatment step S35 is completed, the oxygen atoms may be heterogeneously distributed within the second seed film SL2. That is, the second seed layer SL2 may include a first portion (s) having a predetermined oxygen content and a second portion (s) having a higher oxygen content than the first portion. For example, as exemplarily shown in FIG. 34, the oxygen content of the oxidized second seed film SL2 may be adjusted such that the first seed film SL1 is removed from its exposed surface (i.e., It can be reduced toward the end. Alternatively, after the oxidation treatment step (S35) is completed, the oxygen atoms may be substantially uniformly distributed within the second seed layer (SL2).

Referring again to FIG. 33, after the oxidation process S35, the third seed layer SL3 and the magnetic layer MGL are formed in sequence (S45 and S55). The third seed layer SL3 may be a material having an oxygen affinity higher than that of the magnetic layer MGL and / or the second seed layer SL2. According to some embodiments, the magnetic layer (MGL) may be a ferromagnetic material or an intrinsic perpendicular magnetic layer having an intrinsic perpendicular magnetization property, and the third The seed film SL3 may be a metal film having an oxygen affinity higher than that of the second seed film SL2. For example, the third seed layer SL3 may be formed of at least one of magnesium, tantalum, titanium, aluminum, magnesium zinc, hafnium, or magnesium boron. The thickness of the third seed layer SL3 may be one to three times the thickness of the single seed layer SL3. (Where the single film thickness may mean the thickness of one atom or molecule constituting it).

Meanwhile, according to some embodiments, the second seed layer SL2 has a smaller oxygen affinity than the third seed layer SL3 when the oxidation treatment step S35 is not performed, It may be a material having an oxygen content higher than that of the first seed film SL3. For example, the second seed film SL2 may be formed to have an oxygen content substantially higher than the natural oxygen content. In this case, the oxidation step S35 may be omitted.

A heat treatment step may be performed on the resultant product in which the magnetic layer (MGL) is formed (S65). According to some embodiments, the heat treatment step (S65) may be carried out for a time of from 1 second to 10000 seconds under a temperature condition of from room temperature to 500 degrees Celsius and a pressure condition of from 0.1 mT to 1 T. According to some embodiments, during the heat treatment step S65, at least one of nitrogen or inert gases may be supplied as the atmosphere gas. However, the technical idea of the present invention is not limited thereto. For example, the process conditions of the heat treatment step S65 may be variously modified depending on materials, structure, oxygen content, etc. of the second and third seed layers SL2 and SL3. According to the modified embodiments, the heat treatment step S65 may be performed between the steps of forming the magnetic layer MGL and the third seed layer SL3.

During the heat treatment step S65, the oxygen atoms included in the second seed layer SL2 may diffuse upward to participate in the oxidation of the atoms of the third seed layer SL3. For example, the metal atoms of the third seed layer SL3 may react with oxygen atoms supplied from the second seed layer SL2 during the heat treatment step S65 to form a metal oxide. 34, the oxygen content of the third seed film SL3 is larger than the oxygen content of the surface adjacent to the second seed film SL2 on the surface adjacent to the magnetic film MGL, Can be higher. This difference in oxygen content may be due to the fact that most of the oxygen contained in the third seed layer SL3 originates from the diffusion of the oxygen atoms contained in the second seed layer SL2.

33 and 34, the magnetic film MGL, the third seed film SL3, and the second seed film SL2 are formed by using the extrinsic perpendicular magnetization structure (EPMS) described above, (MGL), the vertical magnetization induction film (PMI), and the vertical magnetization preservation film (PMP) in the first embodiment.

35 is an experimental graph illustrating an exemplary aspect of the magnetic properties of a magnetic tunnel junction according to the present invention.

18, the external magnetization perpendicular magnetic film 310, the perpendicular magnetization induction film 320, and the perpendicular magnetization preservation film 330 shown in FIG. 18 are formed on the tunnel barrier 50 of magnesium oxide (MgO) A structure in which the first upper structure 301 is formed is used. The perpendicular magnetization film 310 and the perpendicular magnetization induction film 320 are made of cobalt iron (CoFeB) and magnesium oxide (MgO), and the perpendicular magnetization preserving film 330 is made of ruthenium (Ru) and titanium (Ti) Respectively. In FIG. 35, curves C1 and C2 show the results of using ruthenium (Ru) and titanium (Ti) as the perpendicular magnetization preserving film 330, respectively. The other conditions of the experiment were substantially the same.

In the graph, the horizontal axis represents the intensity of a perpendicular magnetic field applied from the outside, and the vertical axis represents a perpendicular magnetic moment measured from the extrinsic vertical magnetic layer 310.

Referring to curve C1 of FIG. 35, the perpendicular magnetic moment has a similar magnitude at a state where there is no external perpendicular magnetic field (i.e., x = 0) and at a state where an external vertical magnetic field is applied (e.g., 4000 Oe). Conversely, referring to curve C2 of FIG. 35, the perpendicular magnetic moment is vanish in the absence of an external vertical magnetic field (i.e., x = 0). From this, it can be seen that when the ruthenium (Ru) is used as compared with the case where titanium (Ti) is used as the vertical magnetization preserving film 330, the extrinsic perpendicular magnetic film 310 has better vertical magnetic moment characteristics .

Figure 36 is an experimental graph illustrating another aspect of the magnetic properties of a magnetic tunnel junction according to the present invention.

In the experiment, samples of the first structure prepared with the structure of the extrinsic perpendicular magnetization structure (EPMS) of FIG. 9 and samples of the second structure having no structure of the extrinsic perpendicular magnetization structure (EPMS) were used. Specifically, the specimen of the first structure was a structure in which cobalt iron boron (CoFeB), magnesium oxide (MgO) and ruthenium (Ru) were sequentially stacked on the magnesium oxide film as the tunnel barrier 50, The samples were a structure in which cobalt iron boron (CoFeB) and tantalum (Ta) were sequentially stacked on the magnesium oxide film as the tunnel barrier 50.

In the experiment, the perpendicular anisotropic energy density in the magnetic film with respect to the film thickness of the magnetic film (i.e., CoFeB) was obtained from the samples of the first and second structures. In FIG. 36, the abscissa represents the film thickness of the magnetic film, the ordinate represents the perpendicular anisotropy energy density in the magnetic film, and the curves C3 and C4 represent the results obtained from the samples of the first and second structures, respectively.

Referring to curve C3 in FIG. 36, when cobalt iron boron (CoFeB) was approximately 8, 10 and 14 angstroms, the perpendicular anisotropic energy density had a positive value. That is, in the extrinsic perpendicular magnetization structure (EPMS) (or the first structure) of FIG. 9, the magnetic film had perpendicular anisotropy within a predetermined thickness range t. For example, from the interpolated curve C3, it can be seen that the magnetic film in the first structure has perpendicular anisotropy in the thickness of the magnetic film in the range of approximately 3 angstroms to 17 angstroms. On the other hand, referring to the curve C4 in FIG. 36, the perpendicular anisotropic energy density in the magnetic film in all of the samples was negative. That is, the magnetic film in the second structure has no perpendicular anisotropy.

37 and 38 are diagrams for schematically explaining electronic devices including a semiconductor device according to embodiments of the present invention.

37, an electronic device 1300 including a semiconductor device according to embodiments of the present invention may be a PDA, a laptop computer, a portable computer, a web tablet, a cordless telephone, a mobile phone, A digital music player, a wired or wireless electronic device, or a composite electronic device including at least two of them. The electronic device 1300 may include an input and output device 1320 such as a controller 1310, a keypad, a keyboard, a display, a memory 1330, and a wireless interface 1340 coupled together via a bus 1350. Controller 1310 may include, for example, one or more microprocessors, digital signal processors, microcontrollers, or the like. Memory 1330 may be used, for example, to store instructions executed by controller 1310. [ The memory 1330 may be used to store user data and may include a semiconductor device according to embodiments of the present invention described above. The electronic device 1300 may use the wireless interface 1340 to transmit data to or receive data from a wireless communication network that communicates with an RF signal. For example, the wireless interface 1340 may include an antenna, a wireless transceiver, and the like. Electronic device 1300 may be used in communication interface protocols such as third generation communication systems such as CDMA, GSM, NADC, E-TDMA, WCDAM, CDMA2000.

Referring to FIG. 38, semiconductor devices according to embodiments of the present invention can be used to implement a memory system. The memory system 1400 may include a memory device 1410 and a memory controller 1420 for storing large amounts of data. Memory controller 1420 controls memory device 1410 to read or write the stored data from memory device 1410 in response to a read / write request of host 1430. The memory controller 1420 may configure an address mapping table for mapping an address provided by the host 1430, e.g., a mobile device or a computer system, to the physical address of the memory device 1410. The memory element 1410 may include a semiconductor device according to the above-described embodiments of the present invention.

The semiconductor devices disclosed in the above embodiments can be implemented in various types of semiconductor packages. For example, the semiconductor devices according to the embodiments of the present invention may be used in a package on package (PoP), ball grid arrays (BGAs), chip scale packages (CSPs), plastic leaded chip carriers (PDIP), Die in Waffle Pack, Die in Wafer Form, Chip On Board (COB), Ceramic Dual In-Line Package (CERDIP), Plastic Metric Quad Flat Pack (MQFP), Thin Quad Flatpack (TQFP) SOIC), Shrink Small Outline Package (SSOP), Thin Small Outline (TSOP), Thin Quad Flatpack (TQFP), System In Package (SIP), Multi Chip Package (MCP), Wafer-level Fabricated Package Level Processed Stack Package (WSP) or the like.

The package on which the semiconductor device according to the embodiments of the present invention is mounted may further include a controller and / or a logic element for controlling the semiconductor device.

It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit of the invention. The appended claims should be construed to include other embodiments.

10, 20: first and second wirings 30:
41: Lower structure 201 to 204: First to fourth lower structure
42: upper structure 301 to 304: first to fourth upper structure
50: Tunnel barrier 100: Unit cell
61: lower electrode structure 62: upper electrode structure
210, 310: extrinsic perpendicular magnetic film 215, 315: intrinsic perpendicular magnetic film
220, 320, PMI: vertical magnetization induction film 230, 330, PMP: perpendicular magnetization storage film
235: lower film 335: upper film
FRL: free film PL: defective film
240, 340: Fixing film

Claims (38)

A stationary magnetic structure;
Free magnetic structure; And
And a tunnel barrier between the fixed magnetic structure and the free magnetic structure,
Wherein at least one of the fixed magnetic structure and the free magnetic structure includes an extrinsic perpendicular magnetization structure,
The extrinsic vertical magnetization structure
Vertical magnetization preservation film;
A magnetic film between the perpendicular magnetization storage film and the tunnel barrier; And
And a vertical magnetization induction film between the vertical magnetization preservation film and the magnetic film,
Wherein the perpendicular magnetization storage film is formed of at least one of materials having an oxygen affinity lower than that of the metal constituting the perpendicular magnetization induction film. The method according to claim 1,
Wherein the magnetic film includes a magnetic material having an oxygen affinity lower than that of the metal constituting the perpendicular magnetization induction film,
Wherein the vertical magnetization preservation film comprises a metal material having an oxygen affinity lower than that of the magnetic film. The method according to claim 1,
Wherein the vertical magnetization preservation film is formed of at least one of noble metal or copper. The method according to claim 1,
Wherein the magnetic film is formed of an inherent horizontal magnetic material and has vertical magnetization characteristics through bonding with oxygen atoms contained in the perpendicular magnetization induction film. The method according to claim 1,
And a transition region interposed between the magnetic film and the perpendicular magnetization induction film, wherein the transition region is lower than the perpendicular magnetization induction film and has an oxygen content higher than that of the magnetic film. delete The method according to claim 1,
Wherein the magnetic film is formed of at least one of ferromagnetic materials,
Wherein the perpendicular magnetization induction film is formed of one of metal oxides,
Wherein the perpendicular magnetization storage film is formed of at least one of metals having oxygen affinity lower than that of tantalum and titanium. delete delete delete delete delete delete delete The method according to claim 1,
And a conductive film covering the vertical magnetization preservation film,
Wherein the vertical magnetization preservation film is interposed between the perpendicular magnetization induction film and the conductive film, and the conductive film is formed of a material having an oxygen affinity that is smaller than or equal to that of the perpendicular magnetization preservation film. The method according to claim 1,
Wherein an oxygen content of the vertical magnetization induction film is higher in an area adjacent to the vertical magnetization preservation film than in an area adjacent to the magnetic film. A tunnel barrier interposed between the first and second structures,
Wherein each of the first and second structures includes a metal film and a magnetic film,
Wherein at least one of the first and second structures further comprises a perpendicular magnetization induction film between the metal film and the magnetic film,
Wherein the metal film in contact with the perpendicular magnetization induction film has an oxygen affinity lower than that of the metal constituting the perpendicular magnetization induction film. 18. The method of claim 17,
Wherein the magnetic film in contact with the perpendicular magnetization induction film includes a magnetic material having an oxygen affinity lower than that of the metal constituting the perpendicular magnetization induction film,
Wherein the metal film in contact with the perpendicular magnetization induction film comprises a metal material having an oxygen affinity lower than that of the magnetic film in contact with the perpendicular magnetization induction film. 18. The method of claim 17,
Wherein the metal film in contact with the vertical magnetization induction film is formed of at least one of noble metal or copper. 18. The method of claim 17,
Wherein the magnetic film in contact with the perpendicular magnetization induction film is formed of an inherent horizontal magnetic material and has vertical magnetization characteristics through bonding with oxygen atoms contained in the perpendicular magnetization induction film. 18. The method of claim 17,
And a transition region interposed between the magnetic film and the perpendicular magnetization induction film, wherein the transition region is lower than the perpendicular magnetization induction film and has a higher oxygen content than the magnetic film contacting the perpendicular magnetization induction film, . 18. The method of claim 17,
And the thickness of the magnetic film in contact with the perpendicular magnetization induction film is 3 angstroms to 17 angstroms. 18. The method of claim 17,
Wherein the magnetic film in contact with the perpendicular magnetization induction film is formed of at least one of ferromagnetic materials,
Wherein the perpendicular magnetization induction film is formed of one of metal oxides,
Wherein the metal film in contact with the vertical magnetization induction film is at least one of metals having oxygen affinity lower than that of tantalum and titanium. 18. The method of claim 17,
Wherein one of said first and second structures further comprises a fixed film included therein for fixing a magnetization direction of said magnetic film. 18. The method of claim 17,
Wherein one of the metal films of the first and second structures is formed of an intrinsic perpendicular magnetic film. 18. The method of claim 17,
Wherein at least one of the first and second structures further comprises a conductive film covering the metal film,
Wherein the metal film is sandwiched between the perpendicular magnetization induction film and the conductive film,
Wherein the conductive film is formed of a material having an oxygen affinity that is less than or equal to that of the metal film. 18. The method of claim 17,
Wherein an oxygen content of the perpendicular magnetization induction film is higher in an area adjacent to the metal film than in an area adjacent to the magnetic film. delete delete delete delete delete delete delete delete delete delete delete

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