MULTILAYER THIN FILMS EXHIBITING PERPENDICULAR MAGNETIC ANISOTROPY
20180166627 ยท 2018-06-14
Inventors
Cpc classification
H01F10/3236
ELECTRICITY
H01F10/3272
ELECTRICITY
H01F10/3286
ELECTRICITY
International classification
C23C14/16
CHEMISTRY; METALLURGY
Abstract
A method for forming a multilayer thin film exhibiting perpendicular magnetic anisotropy includes alternately sputtering a CoFeSiB target and a Pd target inside a vacuum chamber to form a [CoFeSiB/Pd] multilayer thin film on a substrate disposed inside the vacuum chamber. The number of times the [CoFeSiB/Pd] multilayer thin film is stacked may be 3 or more.
Claims
1. A method for forming a CoFeSiB/Pd multilayer thin film exhibiting perpendicular magnetic anisotropy, the method comprising: alternate sputtering a CoFeSiB target and a Pd target inside a vacuum chamber to form the [CoFeSiB/Pd] multilayer thin film on a substrate disposed inside the vacuum chamber, wherein a number of times the [CoFeSiB/Pd] multilayer thin film is stacked is 3 or more.
2. The method as set forth in claim 1, further comprising: forming a buffer layer before forming the [CoFeSiB/Pd] multilayer thin film.
3. The method as set forth in claim 2, further comprising: forming a seed layer before forming the buffer layer; and forming a capping layer after forming the [CoFeSiB/Pd] multilayer thin film.
4. The method as set forth in claim 1, wherein the [CoFeSiB/Pd] multilayer thin film is formed by dc sputtering using the CoFeSiB target and the Pd target.
5. The method as set forth in claim 4, wherein a composition ratio of the CoFeSiB target is Co.sub.xFe.sub.ySi.sub.15B.sub.10 (atomic percent), and x=70.5?75 and y=4.5?0.
6. The method as set forth in claim 4, wherein the [CoFeSiB/Pd] multilayer thin film is deposited under an atmosphere of argon and an atmosphere of 1 mTorr to 10 mTorr.
7. The method as set forth in claim 4, wherein a ratio of a thickness of CoFeSiB to a thickness of Pd is 1:1.6 to 1:7.
8. The method as set forth in claim 1, wherein a squareness of the [CoFeSiB/Pd] multilayer thin film is 90 percent or more, saturation magnetization of the [CoFeSiB/Pd] multilayer thin film is 200 emu/cm.sup.3 or more, and effective magnetic anisotropy energy is 1.0?10.sup.6 erg/cm.sup.3 or more.
9. A method for forming a CoSiB/Pd multilayer thin film, the method comprising: alternate sputtering a CoSiB target and a Pd target inside a vacuum chamber to form the [CoSiB/Pd] multilayer thin film on a substrate disposed inside the vacuum chamber, wherein a number of times the [CoSiB/Pd] multilayer thin film is stacked is 3 or more.
10. The method as set forth in claim 9, further comprising: forming a buffer layer before forming the [CoSiB/Pd] multilayer thin film.
11. The method as set forth in claim 10, further comprising: forming a seed layer before forming the buffer layer; and forming a capping layer after forming the [CoSiB/Pd] multilayer thin film.
12. The method as set forth in claim 9, wherein the [CoSiB/Pd] multilayer thin film is formed by dc sputtering using the CoSiB target and the Pd target.
13. The method as set forth in claim 12, wherein the [CoSiB/Pd] multilayer thin film is deposited under an atmosphere of argon and an atmosphere of 1 mTorr to 10 mTorr.
14. The method as set forth in claim 9, wherein a composition ratio of the CoSiB target is Co.sub.75Si.sub.15B.sub.10 (atomic percent).
15. The method as set forth in claim 9, wherein a ratio of a thickness of the CoSiB to a thickness of the Pd is 1:1.6 to 1:7.
16. A CoFeSiB/Pd multilayer thin film exhibiting perpendicular magnetic anisotropy, the CoFeSiB/Pd multilayer thin film comprising: a [CoFeSiB/Pd] multilayer thin film disposed on a substrate, wherein a number of times the [CoFeSiB/Pd] multilayer thin film is stacked is 3 or more.
17. The CoFeSiB/Pd multilayer thin film as set forth in claim 16, wherein a squareness of the [CoFeSiB/Pd] multilayer thin film is 90 percent or more, saturation magnetization of the [CoFeSiB/Pd] multilayer thin film is 200 emu/cm.sup.3 or more, and effective magnetic anisotropy energy is 1.0?10.sup.6 erg/cm.sup.3 or more.
18. The CoFeSiB/Pd multilayer thin film as set forth in claim 16, wherein a thickness of the [CoFeSiB/Pd] multilayer thin film is between 9.5 and 20 nm, and a ratio of a thickness of CoFeSiB to a thickness of Pd is 1:1.6 to 1:7.
19. The CoFeSiB/Pd multilayer thin film as set forth in claim 16, further comprising: a buffer layer below the [CoFeSiB/Pd] multilayer thin film; and a seed layer below the buffer layer, wherein the buffer layer is Pd and has a thickness of 3 nm or more, and the seed layer is Ta.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0042] The present disclosure will become more apparent in view of the attached example drawings and accompanying detailed description. The embodiments depicted therein are provided by way of example, not by way of limitation, wherein like reference numerals refer to the same or similar elements. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating aspects of the present disclosure.
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DETAILED DESCRIPTION
[0058] A magnetic tunnel junction (MTJ) makes a low-current-density operation having high bit stability possible. Thus, magnetic tunnel junctions (MTJs) having perpendicular magnetic anisotropy (PMA) may be used in a nonvolatile magnetic random access memory.
[0059] Conventionally, an MTJ device with PMA (pMTJ) requires TMR of 100 percent or higher, writing stability of 60 or more, and low critical current required for magnetization reversal.
[0060] Moreover, a magnetic tunnel junction should endure a back-end-of-line (BEOL) integrated circuit process including a high temperature of about 400 degrees Celsius. Accordingly, when the magnetic tunnel junction is exposed to a high temperature, degradation in perpendicular magnetic anisotropy is problematic. As a result, it is important to search a material which can endure high-temperature annealing while maintaining desired magnetic properties such as perpendicular magnetic anisotropy.
[0061] Conventionally, a multilayer thin film structure exhibits perpendicular magnetic anisotropy before annealing. However, to secure a back-end-of-line (BEOL) thermal resistance, a key point of the multilayer thin film structure is to continuously maintain perpendicular magnetic anisotropy even after post-deposition annealing.
[0062] Several ferromagnetic systems including rare-earth transition-metal alloys such as TbFeCo and GdFeCo exhibit perpendicular magnetic anisotropy properties.
[0063] However, a magnetic tunnel junction including these alloys loses the perpendicular magnetic anisotropy after post-deposition annealing of 200 degrees Celsius or higher.
[0064] Another system includes L1.sub.0 ordered alloys such as FePd and FePt. The ordered alloys provide large uniaxial anisotropy constant (K.sub.u) values in the range of 10.sup.7 erg/cm.sup.3. However, since the ordered alloys require a high-temperature treatment of 500 degrees centigrade or higher during deposition of a thin film, it is difficult to achieve chemical ordering.
[0065] Another system having perpendicular magnetic anisotropy is a well-known cobalt-based multiplayer thin film such as Co/Pd, Co/Pt, CoFe/Pd or CoFe/Pt. Important magnetic properties such as saturation magnetization (M.sub.s) and uniaxial anisotropy constant (K.sub.u) may be adjusted by changing thicknesses of a ferromagnetic layer and a non-magnetic layer and the number of bilayers.
[0066] A thickness of a pinned layer constituting a cobalt-based multilayer thin film ranges from 5 nm to 20 nm. The number (n) of repeated bilayers may vary from 5 to 10. A cause of perpendicular magnetic anisotropy with respect to a Co/Pd multilayer thin film is known as an interfacial effect resulting from lowered symmetry at the interface or stressed interfacial alloying between a ferromagnetic layer and a non-magnetic layer.
[0067] Additionally, it is known that the perpendicular magnetic anisotropy is degraded at a cobalt-based multilayer thin film during annealing of 300 degrees Celsius or higher due to CoPd interdiffusion or Pd diffusion at Co/Pd interface. It is known that perpendicular magnetic anisotropy materials used in a conventional MTJ are significantly affected by a fine structure and interface change of a deposited layer.
[0068] In the present disclosure, we investigated perpendicular magnetic anisotropy characteristics at a [CoFeSiB/Pd] multilayer thin film (or a [CoSiB/Pd] multilayer thin film). The [CoFeSiB/Pd] multilayer thin film (or the [CoSiB/Pd] multilayer thin film) maintained magnetic anisotropy even when being exposed to annealing at a temperature of about 500 degrees Celsius.
[0069] An example embodiment of the present disclosure provides a magnetic multilayer thin film which maintains perpendicular magnetic anisotropy even after an annealing process of 300 degrees Celsius or higher. The multilayer thin film may be used as a pinned layer or a free layer of a magnetic tunnel junction.
[0070] A multilayer thin film according to an example embodiment of the present disclosure may be applied to a magnetic tunnel junction having a CoFeB (free layer)/MgO (tunnel barrier)/CoFeB (pinned layer) structure which causes a high tunnel magnetic resistance (TMR). More specifically, the multilayer thin film may be applied to Pd/[CoFeSiB/Pd]n/W (or Ta)/CoFeB/MgO (tunnel barrier)/CoFeB. Thus, high annealing stability of the level of 400 degrees Celsius may be secured while having a high TMR value.
[0071] Example embodiments will now be described more fully with reference to the accompanying drawings, in which some example embodiments are shown. Example embodiments may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein; rather, these example embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of example embodiments of inventive concepts to those of ordinary skill in the art. In the drawings, the thicknesses of layers and regions are exaggerated for clarity. Like reference characters and/or numerals in the drawings denote like elements, and thus their description may be omitted.
[0072]
[0073] Referring to
[0074] A seed layer 112, a buffer layer 114, a [CoFeSiB/Pd] multilayer thin film 117, and a capping layer 118 may be sequentially stacked on a silicon substrate 102. The seed layer 112 may be Ta of 5 nm, the buffer layer 114 may be Pd of 10 nm, the number of times (n) the [CoFeSiB/Pd] multilayer thin film 117 is stacked may be 10, a CoFeSiB layer 115a to 115n may be 0.5 nm, and a Pd layer 116a to 116n may be 1.4 nm. The capping layer 118 may be Ta of 5 nm.
[0075] A perpendicular magnetic anisotropy thin film specimen according to an example embodiment of the present disclosure was prepared as follows. The perpendicular magnetic anisotropy thin film 110 may be silicon substrate/silicon oxide/Ta 5/Pd 10/[CoFeSiB 0.5/Pd 1.4].sub.10/Ta 5 (thickness unit: nm). The silicon substrate is single crystalline, the silicon oxide is silicon oxide having a thickness of 300 nm formed on the silicon substrate, the Ta is a seed layer, and the Pd is a buffer layer. The other Ta is a capping layer. The [CoFeSiB/Pd] multilayer thin film 117 is a multilayer thin film deposited by sputtering. The [CoFeSiB/Pd] multilayer thin film 117 is formed by alternately depositing CoFeSiB having a thickness of 0.5 nm and Pd having a thickness of 1.4 nm. Thus, the total thickness of the [CoFeSiB/Pd] multilayer thin film 117 is 19 nm.
[0076] According to an example embodiment of the present disclosure, a [CoFeSiB 0.5/Pd 1.4] multilayer thin film is formed by dc magnetron sputtering. A magnetron sputtering system has a base pressure of 5?10.sup.?9 Torr or less. A thickness of a thin film may be adjusted through deposition time and sputtering power. The magnetron sputtering system includes a CoFeSiB target and a Pd target. A composition ratio of the CoFeSiB target is Co.sub.70.5Fe.sub.4.5Si.sub.15B.sub.10 (each number being atomic percent). The [CoFeSiB 0.5/Pd 1.4] multilayer thin film in the as-deposited state exhibits perpendicular magnetic anisotropy.
[0077] For example, to deposit a thin film, a dc power density may be 2.5 W/cm.sup.2 and a pure argon pressure may be maintained at about 2 mTorr. Deposition rates of CoFeSiB and Pd may be 0.0298 nm/s and 0.127 nm/s, respectively. The deposition rates may be controlled by adjusting power applied to a target. A structure of the thin film is Si/SiO.sub.2/Ta (seed layer) 5/Pd (buffer layer) 10/[CoFeSiB0.5/Pd 1.4].sub.10/Ta (capping layer) 5 (unit: nm). The seed layer is Ta and functions as an adhesion layer. The capping layer is Ta and functions as a protection layer. The deposited [CoFeSiB/Pd] multilayer thin film 117 is in an amorphous state and exhibits perpendicular magnetic anisotropy.
[0078] [Post-Deposition Annealing Stability of Thin Film]
[0079] After formation of the [CoFeSiB/Pd] multilayer thin film 117, the silicon substrate 102 was annealed in a heat treating furnace. Samples were annealed at temperatures of 300 degrees Celsius, 400 degrees Celsius, and 500 degrees Celsius for an hour after deposition of the thin film, respectively. The annealing was performed for an hour under 10.sup.?6 Torr vacuum with an applied external magnetic field of 6 kOe. After the subsequent annealing, the [CoFeSiB 0.5/Pd 1.4] multilayer thin film 117 maintained perpendicular magnetic anisotropy.
[0080]
[0081] Referring to
[0082] The first sample exhibits low coercivity of about 500 oersteds (Oe) when annealing is not performed, exhibits coercivity of about 1 kOe when annealing of 500 degrees Celsius is performed for an hour, and exhibits coercivity of about 5 kOe when annealing of 500 degrees Celsius is performed for an hour.
[0083]
[0084] Referring to
[0085] Referring to
[0086] Referring to
[0087] Referring to
[0088]
[0089]
[0090]
[0091] Referring to
[0092] A [CoFeSiB/Pd] multilayer thin film and a buffer layer are clearly distinguished from each other before annealing, and it can be confirmed that Pd elements of the buffer layer are diffused to the [CoFeSiB/Pd] multilayer thin film as the annealing is performed. Most boron (B) elements move to the buffer layer when annealing of 300 degrees Celsius is performed and move to the capping layer 118 and the seed layer 112 when annealing of 500 degrees Celsius is performed.
[0093]
[0094] Referring to
[0095] After the annealing of 500 degrees Celsius, an XRD peak position of the [CoFeSiB/Pd] multilayer thin film is 41.2 degrees. The peak is very close to peaks of CoPd (41.0 degrees) and CoPd.sub.3 (40.9 degrees) oriented in a (111) direction.
[0096] Compositions of Co and Pd that are two main components of the multilayer thin film are 19 at. % and 81 at. %, respectively. Although the [CoFeSiB/Pd] multilayer thin film is not a pure binary CoPd system, main components are Co and Pd and the amounts of the other components are small. Thus, an alloy formed after annealing can be regarded as a Pd-rich CoPd alloy. Although the perpendicular magnetic anisotropy of the [CoFeSiB/Pd] multilayer thin film in the as-deposited state can be attributed to an interfacial effect, the main origin of the perpendicular magnetic anisotropy of both the [CoFeSiB/Pd] multilayer thin film that underwent high-temperature annealing is thought to result from a bulk effect.
[0097]
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[0099] The second sample does not exhibit sufficient post-annealing coercivity even before annealing, and the third sample does not exhibit sufficient post-annealing coercivity even before annealing. Thus, a [CoFeSiB/Pd]n multilayer thin film needs to include a buffer layer of at least 3 nm to be used as a magnetic layer of a magnetic tunnel junction.
[0100]
[0101] Referring to
[0102]
[0103] Referring to
[0104]
[0105] Referring to
[0106] When the thickness of the Pd layer increases compared with the thickness of the CoFeSiB layer, saturation magnetization may decrease and coercivity may increase. A ratio of the thickness of the CoFeSiB layer to the thickness of the Pd layer may be 1:1.6 to 1:7. Thus, the ratio of the thickness of the CoFeSiB layer to the thickness of the Pd layer may be selected to achieve suitable coercivity, saturation magnetization, squareness or perpendicular anisotropy energy. The perpendicular magnetic anisotropy is maintained even after annealing of 500 degrees Celsius. A thickness of the [CoFeSiB/Pd] multilayer thin film may be preferably between 9.5 and 20 nm.
[0107]
[0108] Referring to
[0109]
[0110]
[0111] Referring to
[0112] A method for forming a perpendicular magnetic anisotropy multilayer thin film includes alternately sputtering a CoSiB target and a Pd target inside a vacuum chamber to form a [CoSiB/Pd] multilayer thin film on a substrate 102 disposed inside the vacuum chamber. A buffer layer 114 may be formed before the [CoSiB/Pd] multilayer thin film 217 is formed. A seed layer 112 may be formed before the buffer layer 114 is formed. A capping layer 118 may be formed after the [CoSiB/Pd] multilayer thin film 217 is formed. The [CoSiB/Pd] multilayer thin film 217 may be formed by dc sputtering method using the CoSiB target and the Pd target. A composition ratio of the CoSiB target may be Co.sub.75Si.sub.15B.sub.10 (atomic percent). The [CoSiB/Pd] multilayer thin film 217 may be deposited under an atmosphere of argon and an atmosphere of 1 mTorr to 10 mTorr. A ratio of a thickness of CoSiB to a thickness of Pd may be 1:1.6 to 1:7. The total thickness of the [CoSiB/Pd] multilayer thin film 217 may be between 9.5 and 20 nm.
[0113] The perpendicular magnetic anisotropy thin film 210 may maintain perpendicular magnetic anisotropy even after annealing of 300 to 500 degrees Celsius for an hour.
[0114]
[0115] Referring to
[0116] The selection transistor 104 may include a gate insulating layer 104b disposed on a substrate, a gate electrode 104c disposed on the gate insulating layer 104b, and impurity regions 104a formed at opposite sides adjacent to the gate insulating layer 104b. The impurity region 104a of the selection transistor 104 may be electrically connected to the magnetic tunnel junction 301. A conductivity type of the impurity region 104a may be opposite to that of a channel region below the gate insulating layer 104b. A first interlayer dielectric 106 is disposed to cover the selection transistor 104. The impurity region 104a may provide a source and a drain. A contact plug 106 may be disposed to be in contact with the impurity region 104a through the first interlayer dielectric 106. A magnetic tunnel junction may be disposed on the contact plug 104.
[0117] The magnetic tunnel junction 301 may include a pinned layer 310, a tunnel insulating layer 320, and a free layer 330 that are sequentially stacked. The pinned layer 310 may include a seed layer 312, a buffer layer 314, and a first pinned layer 317 that are sequentially stacked. The seed layer 312 may be Ta, the buffer layer 314 may be Pd, and the first pinned layer 317 may include a multilayer thin film of [CoFeSiB/Pd] or [CoSiB/Pd] that are alternately deposited. The number of times the multilayer thin film of [CoFeSiB/Pd] or [CoSiB/Pd] is stacked may be 3 or more. The first pinned layer 317 may maintain perpendicular magnetic anisotropy even after annealing of a temperature higher than 300 degrees Celsius and lower than 600 degrees Celsius.
[0118] A tunnel insulating layer 220 may be disposed on the pinned layer 310. The tunnel insulating layer 320 may be deposited in a crystalline state by sputtering an MgO target.
[0119] A free layer 330 may be disposed on the tunnel insulating layer 320. The free layer 330 may a [CoFeSiB/Pd] multilayer thin film or a [CoSiB/Pd] multilayer thin film formed by DC sputtering. The free layer may exhibit perpendicular magnetic anisotropy during deposition. Magnetic characteristics of the free layer 330 may be different from those of the pinned layer 317. More specifically, saturation magnetization of the first pinned layer 317 may be greater than that of the free layer 330. In addition, coercivity of the first pinned layer 317 may be greater than that of the free layer 330.
[0120] According to a modified embodiment of the present disclosure, the free layer 300 may be transformed into another material having perpendicular magnetic anisotropy.
[0121] A conductive pattern 340 may be disposed on the free layer 330. The free layer 330 contacting the conductive pattern 340 may be switched by a spin-transfer torque caused by current flowing through the magnetic tunnel junction 301. Alternatively, the free layer 330 may be switched by a spin-transfer torque or a spin-orbit torque.
[0122] In the magnetic memory device 300 according to the example embodiment, the first interlayer dielectric 107 is deposited after the selection transistor 104 is formed on the substrate 102. A top surface of the first interlayer dielectric 107 may be planarized. A contact hole in which the contact plug 106 is to be disposed is formed by performing a patterning process on the first interlayer dielectric 107. After a conductor filling the contact hole is buried in the substrate 102 where the contact hole is formed, a contact plug 106 may be formed by an etch-back process.
[0123] A pinned layer 310, a tunnel insulating layer 320, and a free layer 330 are sequentially formed on the first interlayer dielectric 107. The pinned layer 310, the tunnel insulating layer 320, and the free layer 330 are patterned by a patterning process to form a magnetic tunnel junction 301.
[0124]
[0125] Referring to
[0126] Conventionally, in the case where amorphous CoFeB is used as a magnetic layer, when annealing of 300 degrees Celsius or more is performed to exhibit perpendicular magnetic anisotropy, the amorphous CoFeB is crystallized. If annealing of 400 degree Celsius or more is performed, the crystallized CoFeB loses the perpendicular magnetic anisotropy.
[0127] However, in the case where a structure including the first pinned layer 317, the non-magnetic conductive layer 418, and the second pinned layer 419 is used, when annealing of 300 to 600 degrees Celsius is performed, the first pinned layer 317 (or [CoSiB/Pd] multilayer thin film) maintains perpendicular magnetic anisotropy and the second pinned layer 419 (or CoFeB) also maintains perpendicular magnetic anisotropy.
[0128] A tunnel insulating layer 220 may be disposed on the second pinned layer 419. The tunnel insulating layer 320 may be formed by sputter-deposition and may be MgO of about 1 nm having crystallinity in the as-deposited state.
[0129] A free layer 430 is disposed on the tunnel insulating layer 220. The free layer 430 may be CoFeB. Thus, the magnetic tunnel junction 401 may maintain a high TMR value caused by a CoFeB/MgO/CoFeB structure.
[0130] According to an example embodiment of the present disclosure, after the first pinned layer 317, the second pinned layer 419, the tunnel insulating layer 320, and the free layer 430 are formed, they may be annealed. Thus, after the free layer 430 is formed, separate auxiliary annealing may be performed for the free layer 430 that is in the amorphous state. A temperature of the auxiliary annealing may be lower than that of annealing for providing perpendicular magnetic anisotropy to the first pinned layer 216.
[0131] As described above, a magnetic layer according to an example embodiment of the present disclosure may easily implement perpendicular magnetic anisotropy by using a [CoFeSiB/Pd] multilayer thin film or a [CoSiB/Pd] multilayer thin film. The [CoFeSiB/Pd] multilayer thin film or the [CoSiB/Pd] multilayer thin film may maintain perpendicular magnetic anisotropy even after annealing and may exhibit constant saturation magnetization irrespective of high squareness, high perpendicular anisotropy energy, and annealing temperature.
[0132] Although the present disclosure and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the disclosure as defined by the following claims.