U.S. patent application number 16/692965 was filed with the patent office on 2021-05-27 for magnetoresistive memory device including a high dielectric constant capping layer and methods of making the same.
The applicant listed for this patent is WESTERN DIGITAL TECHNOLOGIES, INC.. Invention is credited to Matthew Carey, Alan Kalitsov, Bhagwati PRASAD, Bruce Terris.
Application Number | 20210159391 16/692965 |
Document ID | / |
Family ID | 1000005579953 |
Filed Date | 2021-05-27 |
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United States Patent
Application |
20210159391 |
Kind Code |
A1 |
PRASAD; Bhagwati ; et
al. |
May 27, 2021 |
MAGNETORESISTIVE MEMORY DEVICE INCLUDING A HIGH DIELECTRIC CONSTANT
CAPPING LAYER AND METHODS OF MAKING THE SAME
Abstract
Magnetoelectric or magnetoresistive memory cells include at
least one of a high dielectric constant dielectric capping layer
and/or a nonmagnetic metal dust layer located between the free
layer and the dielectric capping layer.
Inventors: |
PRASAD; Bhagwati; (San Jose,
CA) ; Carey; Matthew; (San Jose, CA) ;
Kalitsov; Alan; (San Jose, CA) ; Terris; Bruce;
(Sunnyvale, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
WESTERN DIGITAL TECHNOLOGIES, INC., |
San Jose |
CA |
US |
|
|
Family ID: |
1000005579953 |
Appl. No.: |
16/692965 |
Filed: |
November 22, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L 27/222 20130101;
G11C 11/1673 20130101; G11C 11/161 20130101; H01L 43/08 20130101;
H01F 10/3286 20130101; H01L 43/02 20130101; H01F 10/329 20130101;
G11C 11/1675 20130101; H01F 10/3259 20130101; H01L 43/10
20130101 |
International
Class: |
H01L 43/02 20060101
H01L043/02; H01L 43/10 20060101 H01L043/10; H01F 10/32 20060101
H01F010/32; H01L 27/22 20060101 H01L027/22; G11C 11/16 20060101
G11C011/16 |
Claims
1-18. (canceled)
19. The method of claim 18, A method of operating a
magnetoresistive memory device comprising: providing a memory
device, comprising: a first electrode; a second electrode; a
magnetic tunnel junction located between the first electrode and
the second electrode, the magnetic tunnel junction comprising a
reference layer, a free layer, and a nonmagnetic tunnel barrier
layer located between the reference layer and the free layer; a
dielectric capping layer located between the second electrode and
the free layer; and a nonmagnetic metal dust layer contacting the
dielectric capping layer and the free layer, wherein the memory
device comprises a spin-transfer torque (STT) magnetoresistive
random access memory (MRAM) cell; programming the MRAM cell into a
first programmed state by applying a programming voltage of a first
polarity such that a spin orientation in the free layer is parallel
to a spin orientation of the reference layer; programming the MRAM
cell into a second programmed state by applying a programming
voltage of a second polarity such that the spin orientation in the
free layer is antiparallel to the spin orientation of the reference
layer; and applying a sensing voltage to the first electrode
relative to the second electrode, and determining a magnitude of
electrical current that tunnels through the magnetic tunnel
junction, wherein each of the positive programming voltage and the
negative programming voltage has a magnitude in a range from 100 mV
to 1000 mV.
20. The method of claim 19, wherein the sensing voltage is in a
range from 50 mV to 300 mV.
21. The method of claim 19, wherein the nonmagnetic metal dust
layer increases perpendicular magnetic anisotropy of the free
layer.
22. The method of claim 19, wherein the nonmagnetic metal dust
layer consists essentially of at least one elemental metal.
23. The method of claim 22, wherein the at least one elemental
metal is selected from Ir, Pd, Mg, Pt, W, Ta, Hf, Pd, Ru, or
Rh.
24. The method of claim 22, wherein the at least one elemental
metal is selected from Ir, Pd, Pt, W, Ta, Hf, Pd, Ru, or Rh.
25. The method of claim 22, wherein the at least one elemental
metal consists essentially of iridium.
26. The method of claim 22, wherein the nonmagnetic metal dust
layer has a thickness less than 5 monolayers of the at least one
elemental metal.
27. The method of claim 19, wherein the nonmagnetic metal dust
layer is discontinuous and has sub-monolayer thickness.
28. The method of claim 19, wherein the dielectric capping layer
comprises a dielectric material selected from magnesium oxide,
hafnium oxide or a ternary dielectric oxide material including at
least two metal elements.
29. The method of claim 28, wherein the dielectric capping layer
consists essentially of magnesium oxide.
30. The method of claim 19, wherein: the dielectric capping layer
has a thickness in a range from 0.2 nm to 1 nm; and the nonmagnetic
tunnel barrier layer comprises magnesium oxide and has a thickness
in a range from 0.5 nm to 1.5 nm.
Description
FIELD
[0001] The present disclosure relates generally to the field of
magnetic memory devices and specifically to magnetoresistive memory
devices including a high dielectric constant dielectric capping
layer and/or a nonmagnetic metal dust layer.
BACKGROUND
[0002] Spin-transfer torque (STT) refers to an effect in which the
orientation of a magnetic layer in a magnetic tunnel junction or
spin valve is modified by a spin-polarized current. Generally,
electric current is unpolarized with electrons having random spin
orientations. A spin polarized current is one in which electrons
have a net non-zero spin due to a preferential spin orientation
distribution. A spin-polarized current can be generated by passing
electrical current through a magnetic polarizer layer. When the
spin-polarized current flows through a free layer of a magnetic
tunnel junction or a spin valve, the electrons in the
spin-polarized current can transfer at least some of their angular
momentum to the free layer, thereby producing a torque on the
magnetization of the free layer. When a sufficient amount of
spin-polarized current passes through the free layer, spin-transfer
torque can be employed to flip the orientation of the spin (e.g.,
change the magnetization) in the free layer. A resistance
differential of a magnetic tunnel junction between different
magnetization states of the free layer can be employed to store
data within the magnetoresistive random access memory (MRAM) cell
depending if the magnetization of the free layer is parallel or
antiparallel to the magnetization of the polarizer layer, also
known as a reference layer.
SUMMARY
[0003] In a first embodiment, a voltage controlled magnetic
anisotropy (VCMA) magnetoelectric memory device comprising a VCMA
magnetoelectric memory cell is provided, wherein the VCMA
magnetoelectric memory cell comprises a first electrode, a second
electrode that is spaced from the first electrode, a magnetic
tunnel junction located between the first electrode and the second
electrode, the magnetic tunnel junction comprising a reference
layer having a fixed magnetization direction, a free layer, and a
nonmagnetic tunnel barrier layer located between the reference
layer and the free layer, and a voltage controlled magnetic
anisotropy (VCMA) dielectric capping layer having a dielectric
constant greater than 10 and located between the free layer and the
second electrode.
[0004] In one aspect of the first embodiment, a method of
programming the VCMA magnetoelectric memory device comprises
applying a first programming voltage of a first polarity between
the first and the second electrodes to switch a first magnetization
state of the free layer in which the free layer and the reference
layer have parallel magnetization directions to a second
magnetization state of the free layer in which the free layer and
the reference layer have antiparallel magnetization directions.
[0005] In a second embodiment, a memory device comprises a first
electrode, a second electrode, a magnetic tunnel junction located
between the first electrode and the second electrode, the magnetic
tunnel junction comprising a reference layer, a free layer, and a
nonmagnetic tunnel barrier layer located between the reference
layer and the free layer, a dielectric capping layer located
between the second electrode and the free layer, and a nonmagnetic
metal dust layer contacting the dielectric capping layer and the
free layer.
[0006] In the fourth embodiment, a magnetoresistive memory device
comprises a first electrode, a second electrode, a magnetic tunnel
junction located between the first electrode and the second
electrode, the magnetic tunnel junction comprising a reference
layer, a free layer, and a nonmagnetic tunnel barrier layer located
between the reference layer and the free layer, and a hafnium oxide
layer located between the second electrode and the free layer.
[0007] In one aspect of the fourth embodiment, a method of
operating an MRAM cell of the magnetoresistive memory includes
programming the MRAM cell into a first programmed state by applying
a positive programming voltage to the second electrode relative to
the first electrode, such that a magnetization direction of the
free layer is parallel to a magnetization direction of the
reference layer; and programming the MRAM cell into a second
programmed state by applying a negative programming voltage to the
second electrode relative to the first electrode, such that the
magnetization direction in the free layer is antiparallel to the
magnetization direction of the reference layer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 is a schematic diagram of a memory device including
an array of magnetoresistive or magnetoelectric memory cells
according to an embodiment of the present disclosure.
[0009] FIG. 2 illustrates a first exemplary a voltage-controlled
magnetic anisotropy (VCMA) memory device including a
voltage-controlled magnetic anisotropy dielectric capping layer
according to a first embodiment of the present disclosure.
[0010] FIG. 3A illustrates a first exemplary programming pulse
pattern for switching a magnetization state of a free layer from a
parallel state to an antiparallel state according to the first
embodiment of the present disclosure.
[0011] FIG. 3B illustrates a second exemplary programming pulse
pattern for switching a magnetization state of a free layer from an
antiparallel state to a parallel state according to the first
embodiment of the present disclosure.
[0012] FIG. 4 illustrates a first configuration of a second
exemplary memory device including a nonmagnetic metal dust layer
according to a second embodiment of the present disclosure.
[0013] FIG. 5 illustrates a second configuration of the third
exemplary memory device including a nonmagnetic metal dust layer
according to a third embodiment of the present disclosure.
[0014] FIG. 6 illustrates the hard-axis in-plane magnetization vs.
magnetic field loops of a free layer in a test structure according
to the third exemplary memory device, and the hard-axis in-plane
magnetization of a free layer in another test structure according
to a first comparative exemplary memory device without a
nonmagnetic metal dust layer as a function of an in-plane external
magnetic field.
[0015] FIG. 7 illustrates a fourth exemplary memory device
including a hafnium oxide capping layer according to a fourth
embodiment of the present disclosure.
[0016] FIG. 8 illustrates the hard-axis in-plane magnetization vs.
magnetic field loops of a free layer in a test structure according
to the fourth exemplary memory device, and the in-plane
magnetization of a free layer in another test structure according
to a second comparative exemplary memory device employing a
magnesium oxide capping layer as a function of an in-plane external
magnetic field.
DETAILED DESCRIPTION
[0017] As discussed above, the present disclosure is directed to
magnetoresistive or magnetoelectric memory devices including a high
dielectric constant dielectric capping layer and/or a nonmagnetic
metal dust layer between the free layer and the dielectric capping
layer, and methods of making and programming the same, the various
aspects of which are described below.
[0018] The drawings are not drawn to scale. Multiple instances of
an element may be duplicated where a single instance of the element
is illustrated, unless absence of duplication of elements is
expressly described or clearly indicated otherwise. Same reference
numerals refer to the same element or to a similar element.
Elements having the same reference numerals are presumed to have
the same material composition unless expressly stated otherwise.
Ordinals such as "first," "second," and "third" are employed merely
to identify similar elements, and different ordinals may be
employed across the specification and the claims of the instant
disclosure. As used herein, a first element located "on" a second
element can be located on the exterior side of a surface of the
second element or on the interior side of the second element. As
used herein, a first element is located "directly on" a second
element if there exist a physical contact between a surface of the
first element and a surface of the second element. As used herein,
an "in-process" structure or a "transient" structure refers to a
structure that is subsequently modified.
[0019] As used herein, a "layer" refers to a material portion
including a region having a thickness. A layer may extend over the
entirety of an underlying or overlying structure, or may have an
extent less than the extent of an underlying or overlying
structure. Further, a layer may be a region of a homogeneous or
inhomogeneous continuous structure that has a thickness less than
the thickness of the continuous structure. For example, a layer may
be located between any pair of horizontal planes between, or at, a
top surface and a bottom surface of the continuous structure. A
layer may extend horizontally, vertically, and/or along a tapered
surface. A substrate may be a layer, may include one or more layers
therein, and/or may have one or more layer thereupon, thereabove,
and/or therebelow.
[0020] As used herein, a "layer stack" refers to a stack of layers.
As used herein, a "line" refers to a layer that has a predominant
direction of extension, i.e., having a direction along which the
layer extends the most.
[0021] Referring to FIG. 1, a schematic diagram is shown for a
magnetoresistive or magnetoelectric random access memory (RAM)
device 500 including memory cells 180 of any embodiment of the
present disclosure in an array configuration. The RAM device 500
includes an array of memory cells 180, which may be configured as a
two-dimensional array or as a three-dimensional array. As used
herein, a "random access memory" (RAM) refers to a memory device
containing memory cells that allow random access, e.g., access to
any selected memory cell upon a command for reading the contents of
the selected memory cell. The RAM device 500 of the embodiment of
the present disclosure is a random access memory device including a
magnetoresistive or magnetoelectric memory element within each
memory cell.
[0022] The RAM device 500 of an embodiment of the present
disclosure includes a memory array region 550 containing an array
of memory cells 180 located at the intersection of the respective
word lines (which may comprise electrically conductive lines 30 as
illustrated or as second electrically conductive lines 90 in an
alternate configuration) and bit lines (which may comprise second
electrically conductive lines 90 as illustrated or as first
electrically conductive lines 30 in an alternate configuration).
Each of the memory cells 180 can be a two terminal memory cell
including a respective first electrode and a respective second
electrode. In one embodiment, the first electrodes can be connected
to the first electrically conductive lines 30, and the second
electrodes can be connected to the second electrically conductive
lines 90. Alternatively, the first electrodes can be connected to
the second electrically conductive lines 90, and the first
electrodes can be connected to the first electrically conductive
lines 30.
[0023] The RAM device 500 may also contain a row decoder 560
connected to the word lines, a sense circuitry 570 (e.g., a sense
amplifier and other bit line control circuitry) connected to the
bit lines, a column decoder 580 connected to the bit lines, and a
data buffer 590 connected to the sense circuitry. Multiple
instances of the memory cells 180 are provided in an array
configuration that forms the RAM device 500. It should be noted
that the location and interconnection of elements are schematic and
the elements may be arranged in a different configuration. Further,
a memory cell 180 may be manufactured as a discrete device, i.e., a
single isolated device.
[0024] Each memory cell 180 includes a magnetic tunnel junction
having at least two different resistive states depending on the
alignment of magnetizations of different magnetic material layers.
The magnetic tunnel junction is provided between a first electrode
and a second electrode within each memory cell 180 In the first and
second embodiments, the RAM device 500 comprises a VCMA
magnetoelectric RAM ("MeRAM") device, and each memory cell 180 can
be a voltage controlled magnetic anisotropy (VCMA) magnetoelectric
memory cell in which the magnetization of the free layer can be
controlled by an applied voltage. The magnetization may be
programmed non-deterministically by timing the duration of a
unipolar voltage pulse that induces precession in the free layer,
and stopping the voltage pulse when the desired magnetization
direction is achieved during the precession.
[0025] In the third and fourth embodiments, the RAM device 500
comprises a magnetoresistive RAM ("MRAM") device, and each memory
cell 180 can be a spin-transfer torque (STT) magnetoresistive
memory cell in which the magnetization of the free layer can be
programmed deterministically by bidirectional spin-polarized
current that tunnels through a magnetic tunnel junction.
[0026] The memory cells 180 of the embodiments present disclosure
employ at least one of a voltage controlled magnetic anisotropy
(VCMA) dielectric capping layer in a VCMA MeRAM, a nonmagnetic
metal dust layer located between a dielectric capping layer and the
free layer in a VCMA MeRAM or an STT-MRAM, and/or a hafnium oxide
capping layer in a STT-MRAM.
[0027] In a first embodiment, the VCMA dielectric capping layer
includes a dielectric material having a dielectric constant greater
than 10, such as 25 and greater, and the memory cell 180 includes a
VCMA magnetoelectric memory cell. Preferably, the VCMA dielectric
capping layer is thicker than the tunnel barrier layer and has a
higher dielectric constant than the tunnel barrier layer. Thus, the
VCMA dielectric capping layer moves the VCMA effect (i.e., the
voltage induced electric field) to interface between the VCMA
dielectric capping layer and the free layer, which enables the MgO
tunnel barrier layer to remain relatively thin. Therefore, the VCMA
dielectric capping layer enhances the VCMA effect in the MeRAM
device without deteriorating the interface between the free layer
and the tunnel barrier layer, and thus without degrading the tunnel
magnetoresistance (TMR) of the MeRAM device.
[0028] In a second embodiment, a nonmagnetic metal dust layer
located between the free layer and the dielectric capping layer can
be used in a MeRAM device containing a VCMA magnetoelectric memory
cell to enhance perpendicular magnetic anisotropy of free layer and
to enhance the exchange coupling. The combination of a nonmagnetic
metal dust layer and a VCMA dielectric capping layer may enhance
the VCMA effect more than a standalone VCMA dielectric capping
layer.
[0029] In a third embodiment, a nonmagnetic metal dust layer
located between the free layer and the dielectric capping layer can
be used in an MRAM device containing a spin-transfer torque (STT)
magnetoresistive memory cell to enhance perpendicular magnetic
anisotropy of free layer and to enhance the thermal stability of
the STT magnetoresistive memory device.
[0030] In a fourth embodiment, a hafnium oxide layer can be used as
a dielectric capping layer in an STT magnetoresistive memory cell.
The hafnium oxide layer enhances the perpendicular magnetic
anisotropy (PMA) of the free layer and hence to enhance thermal
stability (which is known as delta in the art). The various
embodiments of the present disclosure are described in further
detail herebelow.
[0031] Referring to FIG. 2, a first exemplary magnetoelectric
memory device according to a first embodiment of the present
disclosure is illustrated, which comprises a magnetoelectric memory
cell. The magnetoelectric memory cell may be employed as a memory
cell 180 within the MRAM device 500 illustrated in FIG. 1.
According to the embodiment of the present disclosure, the
magnetoelectric memory cell of the first embodiment of the present
disclosure may be a voltage controlled magnetic anisotropy (VCMA)
magnetoelectric memory cell. The memory cell 180 can be formed on
an insulating support 20 (which may include a silicon oxide layer),
and can include a first electrode 32 that may be electrically
connected to, or comprises, a portion of a first electrically
conductive line 30 (such as a word line or a bit line) and a second
electrode 92 that may be electrically connected to, or comprises, a
portion of a second electrically conductive line 90 (such as a bit
line or a word line).
[0032] The first exemplary magnetoelectric memory cell 180 includes
a magnetic tunnel junction (MTJ) 140. The magnetic tunnel junction
140 includes a reference layer 132 (which may also be referred to
as a "pinned" layer) having a fixed vertical magnetization, a
nonmagnetic tunnel barrier layer 134, and the free layer 136 (which
may also be referred to as a "storage" layer) having a
magnetization direction that can be programmed. The reference layer
132 and the free layer 136 can be separated by the nonmagnetic
tunnel barrier layer 134 (such as an MgO layer), and have a
magnetization direction perpendicular to the interface between the
free layer 136 and the nonmagnetic tunnel barrier layer 134.
[0033] In one embodiment, the reference layer 132 is located below
the nonmagnetic tunnel barrier layer 134, while the free layer 136
is located above the nonmagnetic tunnel barrier layer 134. A
voltage controlled magnetic anisotropy (VCMA) dielectric capping
layer 148 may be formed on top of the free layer 136. However, in
other embodiments, the reference layer 132 is located above the
nonmagnetic tunnel barrier layer 134, while the free layer 136 is
located below the nonmagnetic tunnel barrier layer 134, or the
reference layer 132 and the free layer 136 may be located on
opposite side of the nonmagnetic tunnel barrier layer 134. The free
layer 136 may be programmed into a first magnetization (e.g.,
magnetization direction) that is parallel to the fixed vertical
magnetization (e.g., magnetization direction) of the reference
layer 132, and a second magnetization (e.g., magnetization
direction) that is antiparallel to the fixed vertical magnetization
(e.g., magnetization direction) of the reference layer 132.
[0034] The reference layer 132 can include either a Co/Ni or Co/Pt
multilayer structure or any other material that have larger
perpendicular magnetic anisotropy than the free layer 136. In one
embodiment, the reference layer 132 can additionally include a thin
non-magnetic layer comprised of tantalum or tungsten having a
thickness in a range from 0.2 nm to 0.5 nm and a thin CoFeB layer
(having a thickness in a range from 0.5 nm to 3 nm).
[0035] The nonmagnetic tunnel barrier layer 134 can include any
tunneling barrier material such as an electrically insulating
material, for example magnesium oxide. In one embodiment, the
nonmagnetic tunnel barrier layer 134 comprises, and/or consists
essentially of, magnesium oxide and has a thickness in a range from
0.5 nm to 1.5 nm, such as 0.8 nm to 1 nm.
[0036] In one embodiment, the reference layer 132 may be provided
as a component within a synthetic antiferromagnetic structure (SAF
structure) 120. The SAF structure 120 can include a hard (i.e.,
fixed) ferromagnetic layer 112 with fixed magnetization along a
vertical direction, an antiferromagnetic coupling layer 114, and
the reference layer 132 which remains adjacent to the nonmagnetic
tunnel barrier layer 134. The antiferromagnetic coupling layer 114
has a thickness that induces a strong antiferromagnetic coupling
between the reference layer 132 and the hard ferromagnetic layer
112, such that the antiferromagnetic coupling layer 114 can "lock
in" the antiparallel alignment between the hard ferromagnetic layer
112 and the reference layer 132, which in turn "locks in" a
particular (fixed) vertical direction of the magnetization of the
reference layer 132. In one embodiment, the antiferromagnetic
coupling layer can include ruthenium, iridium, or chromium, and can
have a thickness in a range from 0.3 nm to 1 nm.
[0037] The free layer 136 includes a ferromagnetic material such as
CoFeB, CoFe, Co, Ni, NiFe, or a combination thereof. If a CoFeB
alloy is included in the free layer 136, then the atomic
concentration of boron atoms within the CoFeB alloy may be in a
range from 10% to 30% (such as 20%), the atomic concentration of
cobalt atoms within the CoFeB alloy may be in a range from 10% to
40% (such as 15%), and the atomic concentration of Fe in the CoFeB
layer may be in a range from 50% to 90% (such as 65%). Any impurity
atom in the CoFeB alloy, if present, has an atomic concentration
less than 1 parts per million. The CoFeB alloy may be deposited in
the amorphous state on a crystalline MgO nonmagnetic tunnel barrier
layer 134 which has a rocksalt crystal structure. During a
subsequent anneal of the device, the CoFeB alloy crystallizes into
a body-centered cubic crystal structure using the MgO layer as a
crystallization template, while some or all of the boron atoms
diffuse away from the interface with the MgO layer. Thus, a
proximal portion of the free layer 136 that contacts the
nonmagnetic tunnel barrier layer 134 may comprise a CoFe alloy or a
CoFeB alloy having a body-centered cubic crystal structure, and may
provide a coherent interface with the nonmagnetic tunnel barrier
layer 134, particularly with MgO and a higher TMR. The thickness of
the free layer 136 can be in a range from 0.5 nm to 2 nm, although
lesser and greater thicknesses can also be employed.
[0038] As used herein, a "thickness" of any deposited film having a
thickness less than 10 nm is the product of the deposition time and
the deposition rate as measured by deposition of a thicker film
that can be physically measured by optical methods or by scanning
electron microscopy. The deposition rate can be calibrated
independently on thicker films for each material. A single
monolayer of a material has an equivalent thickness of the
monolayer of the material. A material that forms a fraction of a
monolayer has an equivalent thickness of the fraction times the
thickness of the monolayer of the material. If the fraction is less
than one, then the material is a discontinuous layer in which the
equivalent thickness can be less than the thickness of the
monolayer of the material. As used herein, a "sub-monolayer" refers
to a film having an average thickness less than one monolayer
(e.g., less than 0.5 nm thick). In embodiments of the present
disclosure, a sub-monolayer film can be a discontinuous layer
having openings therethrough or can be a collection of individual
atoms or clusters of atoms that do not form a continuous layer
depending on the fractional number of an atomic layer that is
present therein.
[0039] An interface between a magnetic film and a nonmagnetic film
can be magnetoelectric, i.e., can exhibit a magnetic property that
is sensitive to the electric field in the nonmagnetic film. When
some dielectric materials are in contact with, or in close
proximity with, a ferromagnetic material, may cause the
ferromagnetic material to exhibit the voltage controlled magnetic
anisotropy (VCMA) effect within the ferromagnetic material. The
VCMA effect refers to an effect in which the magnetic anisotropy of
a ferromagnetic material depends on the electric field within a
dielectric material in direct contact with, or in close proximity
to, the ferromagnetic material. Generally, the VCMA effect is
believed to be due to spin-dependent charge screening and electric
field-induced modulation of the relative occupancy of d orbitals at
an interface between a ferromagnetic material and a dielectric
material.
[0040] According to the first embodiment of the present disclosure,
a voltage controlled magnetic anisotropy (VCMA) dielectric capping
layer 148 can be formed on the free layer 136. In one configuration
of the first embodiment, the VCMA dielectric capping layer 148 is
deposited directly on the free layer 136 and directly physically
contacts the free layer 136 without any intervening layer in
between. The VCMA dielectric capping layer 148 is a dielectric
material layer that decreases the magnetic anisotropy in the free
layer 136 when electrical field is present therein along a
direction perpendicular to an interface with the free layer 136. In
one embodiment, the VCMA dielectric capping layer 148 has a
dielectric constant of greater than 10, such as 25 or more, such as
25 to 80,000, for example 25 to 150, to enhance the VCMA effect in
the memory cell 180. The thickness of the VCMA dielectric capping
layer 148 can be in a range from 1 nm to 10 nm, such as from 1.5 nm
to 3 nm. In one configuration, the VCMA dielectric capping layer
148 can contact the free layer 136, i.e., can be in physical
contact with a surface of the free layer 136.
[0041] Preferably, the VCMA dielectric capping layer 148 is thicker
than the tunnel barrier layer 134, and has a higher dielectric
constant than the tunnel barrier layer 134. This shifts the VCMA
effect which controls the magnetization direction of the free layer
from the interface between the free layer 136 and the tunnel
barrier layer 134 to the interface between the free layer 136 and
the VCMA dielectric capping layer 148. Thus, the TMR of the memory
cell 180 may be maintained because the interface between the free
layer 136 and the magnesium oxide tunnel barrier layer 134 is not
degraded, while the VCMA effect in enhanced due to the higher
dielectric constant of the VCMA dielectric capping layer 148.
[0042] According to an embodiment of the present disclosure, the
dielectric material of the VCMA dielectric capping layer 148
includes a dielectric material having a dielectric constant of 10
or greater, such as 25 or greater, when having a thickness of 10 nm
or less, such as 1 nm to 5 nm. While many dielectric materials
provide a dielectric constant greater than 10 in a bulk state, some
dielectric materials have a lower or higher dielectric constant in
a thin film having a thickness of 10 nm or less. In one embodiment,
the dielectric material of the VCMA dielectric capping layer 148
can be selected such that the dielectric material has a dielectric
constant is 10 or greater when the VCMA dielectric capping layer
148 a thickness of 10 nm or less, such as a thickness in range from
1 nm to 5 nm.
[0043] According to an embodiment of the present disclosure, the
dielectric material of the VCMA dielectric capping layer 148 can
include, and/or can consist essentially of at least one
transition-metal-containing dielectric metal oxide material. Such
transition-metal-containing dielectric metal oxide materials tend
to provide a dielectric constant greater than 10 at a thickness
less than 10 nm. In one embodiment, the at least one
transition-metal-containing dielectric metal oxide material
includes a single material that is selected from, or a plurality of
materials that are selected from, hafnium oxide, zirconium oxide,
tantalum pentoxide, yttrium oxide, aluminum oxide, strontium
titanate, barium titanate, barium strontium titanate, lead
zirconate titante, lead lanthanum titanate, lead lanthanum titanate
zirconate, lead lanthanum zirconate, bismuth ferrite, and calcium
copper titanate. In one embodiment, the at least one
transition-metal-containing dielectric metal oxide material
comprises at least one ternary dielectric oxide material including
two metallic elements. In one embodiment, the at least one ternary
dielectric oxide material including two metallic elements comprises
at least one dielectric material selected from SrTiO.sub.3,
BaTiO.sub.3, and BiFeO.sub.3.
[0044] In one embodiment, the dielectric material of the VCMA
dielectric capping layer 148 can comprise, and/or can consist
essentially of, a material that has a dielectric constant of 25 and
higher, such strontium titanate, barium titanate, barium strontium
titanate, lead zirconate titante, lead lanthanum titanate, lead
lanthanum titanate zirconate, lead lanthanum zirconate, bismuth
ferrite or calcium copper titanate (which is reported to have a
dielectric constant of about 80,000). These materials may be
stoichiometric (e.g., SrTiO.sub.3, BaTiO.sub.3,
(Sr.sub.1-xBa.sub.x)TiO.sub.3, BiFeO.sub.3,
CaCu.sub.3Ti.sub.4O.sub.12, etc.) or non-stoichiometric and may
optionally include dopants. Generally, the dielectric material of
the VCMA dielectric capping layer 148 can be selected such that the
dielectric material produces the VCMA effect at the interface with
the free layer 136 and has a dielectric constant of 10 or greater,
such as 25 or greater in a film form in a thickness range from 1.2
nm to 10 nm, such as 2 nm to 5 nm.
[0045] In one embodiment, the voltage drop across the VCMA
dielectric capping layer 148 can be greater than the voltage drop
across the nonmagnetic tunnel barrier layer 134 during programming,
i.e., writing. Ignoring the effect of the tunneling current, the
ratio of the voltage drop across the VCMA dielectric capping layer
148 to the voltage drop across the nonmagnetic tunnel barrier layer
134 is approximately the same as the ratio of the
thickness-to-dielectric constant ratio for the VCMA dielectric
capping layer 148 to the thickness-to-dielectric constant ratio for
the nonmagnetic tunnel barrier layer 134. A thickness-to-dielectric
constant ratio refers to the ratio of the thickness of a dielectric
layer to the dielectric constant of the dielectric layer. Thus, the
thickness-to-dielectric constant ratio for the VCMA dielectric
capping layer 148 can be greater than the thickness-to-dielectric
constant ratio for the nonmagnetic tunnel barrier layer 134.
[0046] A nonmagnetic metallic material can be provided on the side
of the VCMA dielectric capping layer 148 that faces away from the
free layer 136. For example, a nonmagnetic conductive capping layer
170 can be formed directly on the VCMA dielectric capping layer
148. The nonmagnetic conductive capping layer 170 includes at least
one non-magnetic electrically conductive material such as tantalum,
ruthenium, tantalum nitride, copper, and/or copper nitride. For
example, the nonmagnetic conductive capping layer 170 can comprise
a single layer, such as a single ruthenium layer, or a layer stack
including, from one side to another, a first ruthenium layer, a
tantalum layer, and a second ruthenium layer. For example, the
first ruthenium layer can have a thickness in a range from 0.5 nm
to 1.5 nm, the tantalum layer can have a thickness in a range from
1 nm to 3 nm, and the second ruthenium layer can have a thickness
in a range from 0.5 nm to 1.5 nm. Optionally, the nonmagnetic
conductive capping layer 170 may include an additional non-magnetic
electrically conductive material, such as W, Ti, Ta, WN, TiN, TaN,
Ru, and Cu. The thickness of such an additional non-magnetic
electrically conductive material can be in a range from 1 nm to 30
nm, although lesser and greater thicknesses can also be employed.
The second electrode 92 can be formed over the nonmagnetic
conductive capping layer 170 as a portion of a second electrically
conductive line 90.
[0047] The layer stack including the SAF structure 120, the
magnetic tunnel junction 140, the VCMA dielectric capping layer
148, and the nonmagnetic conductive capping layer 170 can be
annealed to induce crystallographic alignment between the
crystalline structure of the nonmagnetic tunnel barrier layer 134
(which may include crystalline MgO having a rock salt crystal
structure) and the crystalline structure of the free layer 136.
[0048] The location of the first electrode 32 and the second
electrode 92 may be switched such that the second electrode 92 is
electrically connected to the SAF structure 120 and the first
electrode 32 is electrically connected to the nonmagnetic
conductive capping layer 170. The layer stack including the
material layers from the SAF structure 120 to the nonmagnetic
conductive capping layer 170 can be deposited in reverse order,
i.e., from the SAF structure 120 toward the nonmagnetic conductive
capping layer 170 or from the nonmagnetic conductive capping layer
170 toward the SAF structure 120. The layer stack can be formed as
a stack of continuous layers, and can be subsequently patterned
into discrete patterned layer stacks for each memory cell 180.
[0049] Optionally, each memory cell 180 can include a dedicated
steering device, such an access transistor (not shown) or a diode
configured to activate a respective discrete patterned layer stack
(120, 140, 148, 170) upon application of a suitable voltage to the
steering device. The steering device may be electrically connected
between the patterned layer stack and one of the first electrically
conductive lines 30 or one of the second electrically conductive
lines 90.
[0050] In one embodiment, the reference layer 132 has a fixed
vertical magnetization that is perpendicular to an interface
between the reference layer 132 and the nonmagnetic tunnel barrier
layer 134. The free layer 136 has perpendicular magnetic anisotropy
to provide bistable magnetization states that include a parallel
state having a magnetization that is parallel to the fixed vertical
magnetization and an antiparallel state having a magnetization that
is antiparallel to the fixed vertical magnetization.
[0051] The memory cell 180 can be programmed employing the voltage
controlled magnetic anisotropy (VCMA) effect. Thus, the memory cell
180 can be programmed employing an electrical voltage that is
applied in one direction. In other words, a voltage is applied
between a selected word line and a selected bit line, and the
memory cell 180 can be toggled back and forth between the parallel
and anti-parallel states by pulsing a voltage in one direction
(e.g., in forward bias mode). In one embodiment, a very small
current may flow between the free layer 136 and the reference layer
132 during the writing step. However, the current is typically so
small that spin-transfer torque (STT) effects can be ignored, and
Ohmic dissipation should be minimal which reduces the write power.
Optionally, an in-plane ancillary magnetic field may be provided by
an external field source 60 configured to apply an in-plane
ancillary magnetic field to the free layer 136.
[0052] A control circuit 401 provides a unipolar voltage between
the first electrode 32 and the second electrode 92. The control
circuit 401 may include one or more of, or all of, the various
elements 560, 570, 580 and/or 590 shown in FIG. 1. The control
circuit 401 can have two nodes that are connected to a respective
one of the first electrode 32 and the second electrode 92 via a
respective first electrically conductive line 30 and a respective
second electrically conductive line 90.
[0053] Generally, the control circuit 401 can be configured to
perform a programming operation by applying a programming pulse to
a selected VCMA magnetoelectric memory cell within the VCMA
magnetoelectric memory device. The programming pulse has a same
polarity (i.e., the first polarity) for a first magnetization state
(i.e., a parallel alignment state) in which a free layer 136 and a
reference layer 132 in the selected VCMA magnetoelectric memory
cell have parallel magnetization directions, and for a second
magnetization state (i.e., an antiparallel alignment state) in
which the free layer 136 and the reference layer 132 in the
selected VCMA magnetoelectric memory cell have antiparallel
magnetization directions. The control circuit 401 can be configured
to select a target VCMA magnetoelectric memory cell to be
programmed within the VCMA magnetoelectric memory device, to
determine an alignment state of magnetization of a free layer 136
(e.g., by reading the memory cell) and to apply a programming pulse
if the alignment state of the target VCMA magnetoelectric memory
cell is opposite to a target alignment configuration for the target
VCMA magnetoelectric memory cell (thus, necessitating flipping of
the magnetization of the free layer 136), and not to apply any
programming pulse if the alignment state of the target VCMA
magnetoelectric memory cell is in the target alignment
configuration for the target VCMA magnetoelectric memory cell.
[0054] The programming pulse generates an electric field in the
VCMA capping dielectric layer 148 and induces precession of a
magnetization of a free layer 136 around an axis determined by
magnetostatic interactions of various magnetic layers and the
external magnetic field. In one embodiment, the programming pulse
can be terminated when the polar angle is within a range from 0
radian to .pi./20 or when the polar angle is within a range from
19.pi./20 to .pi..
[0055] Referring to FIG. 3A, an example of a programming step is
illustrated, in which a selected VCMA magnetoelectric memory cell
180 in a parallel alignment state is programmed into an
antiparallel alignment state by a programming pulse of the first
polarity that terminates when the polar angle between the
magnetization direction of the free layer 136 with respect to the
fixed magnetization direction of the reference layer 132 is within
a range from 19.pi./20 to .pi.. The duration of the programming
pulse may be in range from 0.02 ns to 0.5 ns, although lesser and
greater duration of the programming pulse can also be employed.
[0056] Referring to FIG. 3B, an example of a programming step is
illustrated, in which a selected VCMA magnetoelectric memory cell
in an antiparallel alignment state is programmed into a parallel
alignment state by a programming pulse of the first polarity that
terminates when the polar angle between the magnetization direction
of the free layer 136 with respect to the fixed magnetization
direction of the reference layer 132 is within a range from 0 to
.pi./20.
[0057] Thus, the control circuit 401 is configured to perform a
programming operation by applying a programming voltage between the
first electrode 32 and the second electrode 92, wherein the
programming voltage has a same polarity for a first magnetization
state in which the free layer 136 and the reference layer 132 have
parallel magnetization directions and for a second magnetization
state in which the free layer and the reference layer have
antiparallel magnetization directions. The magnitude of the
programming voltage may be in a range from 500 mV to 3 V. The
control circuit 401 is also configured to perform a sensing (i.e.,
reading) operation by applying a voltage between 100 mV and 1.5 V
between the first and second electrodes.
[0058] A method of operating the memory cell 180 of the first
embodiment comprises applying a first programming voltage of a
first polarity between the first and the second electrodes (32, 92)
to switch a first magnetization state of the free layer 136 in
which the free layer and the reference layer 132 have parallel
magnetization directions to a second magnetization state of the
free layer in which the free layer and the reference layer have
antiparallel magnetization directions. The method further comprises
applying a second programming voltage of the first polarity between
the first and the second electrodes to switch the second
magnetization state of the free layer to the first magnetization
state of the free layer. The first programming voltage and the
second programming voltage generate an electric field in the VCMA
dielectric capping layer which induces precession in the free layer
136. As shown in FIGS. 3A and 3B, the method includes terminating
the first programming voltage when the free layer has the first
magnetization direction, and terminating the second programming
voltage when the free layer has the second magnetization direction.
In one embodiment, an external magnetic field is optionally applied
by source 60 during the step of applying the first programming
voltage.
[0059] The magnetoelectric memory device of FIG. 2 can be
manufactured by forming a layer stack including, from one side to
another, a first electrode 32, a reference layer 132, a nonmagnetic
tunnel barrier layer 134, a free layer 136, a voltage controlled
magnetic anisotropy (VCMA) dielectric capping layer 148 having a
dielectric constant greater than 10, and a second electrode 92 in a
forward order or in a reverse order. A control circuit 401 can be
formed, and the first electrode 32 and the second electrode 92 can
be connected to a respective node of the control circuit 401. The
reference layer 132 has a fixed magnetization direction, and the
free layer 136 has magnetic anisotropy that provides magnetization
directions that are parallel or antiparallel to the fixed
magnetization direction.
[0060] The high dielectric constant of the VCMA dielectric capping
layer 148 enhances VCMA effect, which is measured in terms of a
VCMA coefficient.
[0061] Referring to FIG. 4, a second exemplary memory device
according to a second embodiment of the present disclosure is
illustrated, which comprises a magnetoelectric memory cell, which
may be a MeRAM cell, such as a VCMA MeRAM cell. The memory cell of
the second embodiment may be employed as a memory cell 180 within
the RAM device 500 illustrated in FIG. 1. The second exemplary
memory cell of the second embodiment can be derived from the
magnetoelectric memory cell of the first embodiment illustrated in
FIG. 2 by replacing the VCMA dielectric capping layer 148 with a
combination of a nonmagnetic metal dust layer 146 and a VCMA
dielectric capping layer 248. The nonmagnetic metal dust layer 146
is located between the free layer 136 and the VCMA dielectric
capping layer 248. The nonmagnetic metal dust layer 146 can be in
contact with the surface of the free layer 136 which faces away
from the nonmagnetic tunnel barrier layer 134, i.e., the surface of
the free layer 136 that faces toward the second electrode 92.
[0062] In the second embodiment, any suitable dielectric capping
material can be employed for the VCMA dielectric capping layer 248.
The VCMA dielectric capping layer 248 may comprise any material
that can be employed for the VCMA dielectric capping layer 148 of
the first embodiment, or it may comprise a conventional VCMA
dielectric capping layer, such as a magnesium oxide capping layer
(which has a dielectric constant in a range from 6.8 to 9.8), or an
aluminum oxide capping layer or even any
insulating/semiconducting/dirty metallic layer. Thus, the
nonmagnetic metal dust layer 146 may be located between the VCMA
dielectric capping layer 248 and the free layer 136. The
nonmagnetic metal dust layer 146 can contact the free layer 136 and
the VCMA dielectric capping layer 248, and the VCMA dielectric
capping layer 248 can contact the nonmagnetic conductive capping
layer 170.
[0063] As used herein, a dust layer refers to a continuous layer or
a non-continuous layer formed by deposition of at least one metal
(e.g., nonmagnetic elemental metal) such that the thickness of the
deposited metal does not exceed the thickness of five monolayers of
the metal. In one embodiment, the dust layer of the second
embodiment of the present disclosure is a sub-monolayer film having
a thickness of less than one monolayer as described above. The
nonmagnetic metal dust layer 146 of the second embodiment of the
present disclosure can be deposited, for example, by physical vapor
deposition of at least one nonmagnetic elemental metal. The
nonmagnetic metal dust layer 146 of the second embodiment of the
present disclosure can consist essentially of at least one
elemental metal, i.e., a metallic element in an elemental form.
[0064] It is noted that the nonmagnetic metal dust layer 146 is
formed on the side of the free layer 136 that faces away from the
nonmagnetic tunnel barrier layer 134. Thus, the nonmagnetic metal
dust layer 146 does not affect the tunneling characteristics of the
magnetic tunnel junction 140. Instead, the nonmagnetic metal dust
layer 146 is interposed between the free layer 136 and the VCMA
dielectric capping layer 248. The nonmagnetic metal dust layer 146
provides the function of enhancing the VCMA effect.
[0065] In one embodiment, the material of the nonmagnetic metal
dust layer 146 is selected such that the metal increases
perpendicular magnetic anisotropy of the ferromagnetic alloy of the
free layer 136. In one embodiment, the nonmagnetic metal dust layer
146 consists essentially of the at least one elemental metal, and
the at least one elemental metal can be selected from Ir, Pd, Mg,
Pt, W, Ta, Hf, Pd, Ru, or Rh. In one embodiment, the nonmagnetic
metal dust layer 146 may consist essentially of single metal such
as Ir, Pd, Mg, Pt, W, Ta, Hf, Pd, Ru, or Rh. In one embodiment, the
nonmagnetic metal dust layer 146 may consist essentially of a
single transition metal element such as Ir, Pd, Pt, W, Ta, Hf, Pd,
Ru, or Rh. In another embodiment, the nonmagnetic metal dust layer
146 may consist essentially of Mg. The nonmagnetic metal dust layer
146 may be formed by physical vapor deposition (i.e., sputtering).
The thickness of the nonmagnetic metal dust layer 146 can be less
than 5 monolayers of the at least one elemental metal. In one
embodiment, the thickness of the nonmagnetic metal dust layer 146
can be in a range from 0.1 nm to 1.2 nm, such as from 0.1 nm to 0.8
nm, and/or from 0.2 nm to 0.5 nm. In one embodiment, the
nonmagnetic metal dust layer 146 has a sub-monolayer thickness and
includes openings therethrough. In one embodiment, the nonmagnetic
metal dust layer 146 is discontinuous, i.e., includes multiple
clusters that do not contact one another. The number of metal atoms
in each cluster may be in a range from 1 to 100. In this case, the
thickness of the nonmagnetic metal dust layer 146 may be in a range
from 0.1 nm to 0.2 nm. Alternatively, the nonmagnetic metal dust
layer 146 can have a thickness in a range from 1 monolayer of the
at least one elemental metal and 5 monolayers of the at least one
elemental metal.
[0066] The second exemplary memory device of the second embodiment
of the present disclosure includes a magnetoelectric memory device.
The operational principle of the second exemplary memory device can
be the same as the operational principle of the first exemplary
memory device. Depending on the defect density and the leakage
current level through the VCMA dielectric capping layer 248, the
thickness of the VCMA dielectric capping layer 248 can be in a
range from 1 nm to 5 nm, such as from 1 nm to 2.5 nm. The VCMA
dielectric capping layer 248 can contact the nonmagnetic metal dust
layer 146, i.e., can be in physical contact with a surface of the
nonmagnetic metal dust layer 146.
[0067] The dielectric oxide materials that can be used for the VCMA
dielectric capping layer 248 include, but are not limited to,
magnesium oxide, aluminum oxide, or any of the materials of the
VCMA dielectric capping layer 148.
[0068] In one embodiment, the VCMA dielectric capping layer 248 can
include magnesium oxide. In another embodiment, the VCMA dielectric
capping layer 248 can include aluminum oxide or a transition metal
oxide, such as tantalum oxide. In one embodiment, the VCMA
dielectric capping layer 248 comprises, and/or consists essentially
of, a dielectric material that can be used for the VCMA dielectric
capping layer 148 of the first embodiment. In this case, the
dielectric material of the VCMA dielectric capping layer 248 can be
selected from hafnium oxide and a ternary dielectric oxide material
including at least two metal elements. In one embodiment, the VCMA
dielectric capping layer 248 consists essentially of hafnium oxide.
In one embodiment, the VCMA dielectric capping layer 248 consists
essentially of a material selected from SrTiO.sub.3, BaTiO.sub.3,
or BiFeO.sub.3.
[0069] In one embodiment, the VCMA dielectric capping layer 248 can
have a thickness in a range from 1.0 nm to 5.0 nm, and the
nonmagnetic tunnel barrier layer 134 comprises, and/or consists
essentially of, magnesium oxide and has a thickness in a range from
0.6 nm to 1.2 nm. In one embodiment, the VCMA dielectric capping
layer 248 has a dielectric constant greater than 10 within a
thickness range from 1.0 nm to 5.0 nm.
[0070] A nonmagnetic metallic material can be provided on the side
of the dielectric capping layer 348 that faces away from the free
layer 136. For example, a nonmagnetic conductive capping layer 170
can be formed on the VCMA dielectric capping layer 248. The
nonmagnetic conductive capping layer 170 can have the same material
composition and/or the same thickness as in the first embodiment.
The second electrode 92 can be formed over the nonmagnetic
conductive capping layer 170 as a portion of a second electrically
conductive line 90.
[0071] The layer stack including the SAF structure 120, the
magnetic tunnel junction 140, the VCMA dielectric capping layer
248, and the nonmagnetic conductive capping layer 170 can be
annealed to induce crystallographic alignment between the
crystalline structure of the nonmagnetic tunnel barrier layer 134
(which may include crystalline MgO having a rock salt crystal
structure) and the crystalline structure of the free layer 136.
[0072] As in the first embodiment, the location of the first
electrode 32 and the second electrode 92 may be switched such that
the second electrode 92 is electrically connected to the SAF
structure 120 and the first electrode 32 is electrically connected
to the nonmagnetic conductive capping layer 170. The layer stack
including the material layers from the SAF structure 120 to the
nonmagnetic conductive capping layer 170 can be deposited in
reverse order, i.e., from the SAF structure 120 toward the
nonmagnetic conductive capping layer 170 or from the nonmagnetic
conductive capping layer 170 toward the SAF structure 120. The
layer stack can be formed as a stack of continuous layers, and can
be subsequently patterned into discrete patterned layer stacks for
each memory cell 180.
[0073] Optionally, each memory cell 180 can include a dedicated
steering device, such an access transistor (not shown) or a diode
configured to activate a respective discrete patterned layer stack
(120, 140, 136, 248, 170) upon application of a suitable voltage to
the steering device. The steering device may be electrically
connected between the patterned layer stack and one of the first
electrically conductive lines 30 or one of the second electrically
conductive lines 90.
[0074] A control circuit 401 can be provided to generate the
bidirectional current flow between the first electrode 32 and the
second electrode 92. The control circuit 401 can have the same
functionality as in the first embodiment.
[0075] The second exemplary structure comprises magnetoelectric
memory device. The magnetoelectric memory device comprises a first
electrode 32, a second electrode 92, and a magnetic tunnel junction
140 located between the first electrode 32 and the second electrode
92. The magnetic tunnel junction 140 comprises a reference layer
132 having a fixed magnetization direction (which is one of the up
direction and the down direction), a free layer 136 having magnetic
anisotropy that provide bistable magnetization directions that are
parallel or antiparallel to the fixed magnetization direction, and
a nonmagnetic tunnel barrier layer 134 located between the
reference layer 132 and the free layer 136. The magnetoelectric
memory device also comprises a VCMA dielectric capping layer 248
located between the second electrode 92 and the free layer 136, and
a nonmagnetic metal dust layer 146 contacting the dielectric
capping layer 248 and the free layer 136.
[0076] The nonmagnetic metal dust layer 146 may consist essentially
of the at least one elemental metal. In one embodiment, the at
least one elemental metal can be selected from Ir, Pd, Mg, Pt, W,
Ta, Hf, Pd, Ru, or Rh. In one embodiment, the nonmagnetic metal
dust layer 146 can consist essentially of a single elemental metal
selected from Ir, Pd, Mg, Pt, W, Ta, Hf, Pd, Ru, or Rh, for example
Ir.
[0077] In one embodiment, the magnetoelectric memory device can
comprise a synthetic antiferromagnet structure 120 comprising a
hard ferromagnetic layer 112, an antiferromagnetic coupling layer
114, and the reference layer 132. The antiferromagnetic coupling
layer 114 provides antiferromagnetic coupling between magnetization
of the hard ferromagnetic layer 112 and magnetization of the
reference layer 132. The hard ferromagnetic layer 112 can contact
the first electrode 32.
[0078] In one embodiment, the nonmagnetic metal dust layer 146 has
a thickness less than 5 monolayers of the at least one elemental
metal. In one embodiment, the nonmagnetic metal dust layer 146 is
discontinuous and has sub-monolayer thickness.
[0079] In one embodiment, the VCMA dielectric capping layer 248
comprises, and/or consists essentially of, a dielectric material
selected from magnesium oxide, aluminum oxide, or a dielectric
oxide of at least one transition metal. In another embodiment, the
VCMA dielectric capping layer 248 comprises, and/or consists
essentially of the voltage controlled magnetic anisotropy (VCMA)
dielectric capping layer 148 of the first embodiment having a
dielectric constant of 10 or greater, such as 25 or greater. The
VCMA dielectric capping layer 248 has a thickness in a range from 1
nm to 10 nm, and the nonmagnetic tunnel barrier layer 134 comprises
magnesium oxide and has a thickness in a range from 0.5 nm to 1.5
nm.
[0080] The magnetoelectric memory device of FIG. 4 can be
manufactured by forming a layer stack including, from one side to
another, a first electrode 32, a reference layer 132, a nonmagnetic
tunnel barrier layer 134, a free layer 136, a nonmagnetic metal
dust layer 146, a VCMA dielectric capping layer 248, and a second
electrode 92 in a forward order or in a reverse order. A control
circuit 401 can be formed, and the first electrode 32 and the
second electrode 92 can be connected to a respective node of the
control circuit 401.
[0081] The nonmagnetic metal dust layer 146 enhances VCMA effect,
which is measured in terms of a VCMA coefficient.
[0082] Referring to FIG. 5, a third exemplary memory device
according to a third embodiment of the present disclosure is
illustrated, which comprises a magnetoresistive memory cell, such
as an STT-MRAM cell. The memory cell of the third embodiment may be
employed as a memory cell 180 within the RAM device 500 illustrated
in FIG. 1. The third exemplary memory cell of the third embodiment
can be derived from the magnetoelectric memory cell of the first
embodiment illustrated in FIG. 2 by replacing the VCMA dielectric
capping layer 148 with a combination of a nonmagnetic metal dust
layer 146 and a dielectric capping layer 348. The nonmagnetic metal
dust layer 146 can be in contact with the surface of the free layer
136 which faces away from the nonmagnetic tunnel barrier layer 134,
i.e., the surface of the free layer 136 that faces toward the
second electrode 92. In contrast, in prior art spin-transfer torque
magnetoresistive memory cells, a nonmagnetic metal dust layer is
located between the free layer 136 and the nonmagnetic tunnel
barrier layer 134.
[0083] In the third embodiment, any suitable dielectric capping
layer 348 may be used. The dielectric capping layer 348 may
comprise the same material as the dielectric capping layer 148 of
the first embodiment (but having a smaller thickness), or it may
comprise a conventional dielectric capping layer, such as a
magnesium oxide capping layer (which has a dielectric constant in a
range from 6.8 to 9.8), or an aluminum oxide capping layer or even
any insulating/semiconducting/dirty metallic layer. Thus, the
nonmagnetic metal dust layer 146 may be located between the
dielectric capping layer 348 and the free layer 136. The
nonmagnetic metal dust layer 146 can contact the free layer 136 and
the dielectric capping layer 348, and the dielectric capping layer
348 can contact the nonmagnetic conductive capping layer 170.
[0084] It is noted that the nonmagnetic metal dust layer 146 is
formed on the side of the free layer 136 that faces away from the
nonmagnetic tunnel barrier layer 134. Thus, the nonmagnetic metal
dust layer 146 does not affect the tunneling characteristics of the
magnetic tunnel junction 140. Instead, the nonmagnetic metal dust
layer 146 is interposed between the free layer 136 and the
dielectric capping layer 348. The nonmagnetic metal dust layer 146
provides the function of enhancing the perpendicular magnetic
anisotropy (PMA) of the free layer 136 in the STT MRAM device.
[0085] In one embodiment, the material of the nonmagnetic metal
dust layer 146 is selected such that the metal increases
perpendicular magnetic anisotropy of the ferromagnetic alloy of the
free layer 136. In one embodiment, the nonmagnetic metal dust layer
146 consists essentially of the at least one elemental metal, and
the at least one elemental metal can be selected from Ir, Pd, Mg,
Pt, W, Ta, Hf, Pd, Ru, or Rh. In one embodiment, the nonmagnetic
metal dust layer 146 may consist essentially of single metal such
as Ir, Pd, Mg, Pt, W, Ta, Hf, Pd, Ru, or Rh. In one embodiment, the
nonmagnetic metal dust layer 146 may consist essentially of a
single transition metal element such as Ir, Pd, Pt, W, Ta, Hf, Pd,
Ru, or Rh. In another embodiment, the nonmagnetic metal dust layer
146 may consist essentially of Mg. The nonmagnetic metal dust layer
146 may be formed by physical vapor deposition (i.e., sputtering).
The thickness of the nonmagnetic metal dust layer 146 can be less
than 5 monolayers of the at least one elemental metal. In one
embodiment, the thickness of the nonmagnetic metal dust layer 146
can be in a range from 0.1 nm to 1.2 nm, such as from 0.1 nm to 0.8
nm, and/or from 0.2 nm to 0.5 nm. In one embodiment, the
nonmagnetic metal dust layer 146 has a sub-monolayer thickness and
includes openings therethrough. In one embodiment, the nonmagnetic
metal dust layer 146 is discontinuous, i.e., includes multiple
clusters that do not contact one another. The number of metal atoms
in each cluster may be in a range from 1 to 100. In this case, the
thickness of the nonmagnetic metal dust layer 146 may be in a range
from 0.1 nm to 0.2 nm. Alternatively, the nonmagnetic metal dust
layer 146 can have a thickness in a range from 1 monolayer of the
at least one elemental metal and 5 monolayers of the at least one
elemental metal.
[0086] The third exemplary memory device of the third embodiment of
the present disclosure includes a STT magnetoresistive memory
device in which electrical current flows between the first
electrode 32 and the second electrode 92 during programming. Thus,
the thickness of the dielectric capping layer 348 is within a range
that allows tunneling of electrical current through the dielectric
capping layer 348. Depending on the defect density and the leakage
current level through the dielectric capping layer 348, the
thickness of the dielectric capping layer 348 can be in a range
from 0.2 nm to 1 nm. The dielectric capping layer 348 can contact
the nonmagnetic metal dust layer 146, i.e., can be in physical
contact with a surface of the nonmagnetic metal dust layer 146.
[0087] The dielectric oxide materials that can be used for the
dielectric capping layer 348 include, but are not limited to,
magnesium oxide, aluminum oxide, or any of the materials of the
VCMA dielectric capping layer 148. The thickness of the dielectric
capping layer 348 can be selected so that sufficient tunneling
current flows through the dielectric capping layer 348 while
tunneling current flows through the magnetic tunnel junction 140
during a programming operation or during a sensing (i.e., reading)
operation.
[0088] In one embodiment, the dielectric capping layer 348 can
include magnesium oxide. In another embodiment, the dielectric
capping layer 348 can include aluminum oxide or a transition metal
oxide, such as tantalum oxide. In one embodiment, the dielectric
capping layer 348 comprises, and/or consists essentially of, a
dielectric material that can be used for the VCMA dielectric
capping layer 148 of the first embodiment. In this case, the
dielectric material of the dielectric capping layer 348 can be
selected from hafnium oxide or a ternary dielectric oxide material
including at least two metal elements. In one embodiment, the
dielectric capping layer 348 consists essentially of hafnium oxide.
In one embodiment, the dielectric capping layer 348 consists
essentially of a material selected from SrTiO.sub.3, BaTiO.sub.3,
or BiFeO.sub.3.
[0089] In one embodiment, the dielectric capping layer 348 can have
a thickness in a range from 0.2 nm to 1 nm, and the nonmagnetic
tunnel barrier layer 134 comprises, and/or consists essentially of,
magnesium oxide and has a greater thickness in a range from 0.6 nm
to 1.2 nm.
[0090] A nonmagnetic metallic material can be provided on the side
of the dielectric capping layer 348 that faces away from the free
layer 136. For example, a nonmagnetic conductive capping layer 170
can be formed on the dielectric capping layer 348. The nonmagnetic
conductive capping layer 170 can have the same material composition
and/or the same thickness as in the first embodiment. The second
electrode 92 can be formed over the nonmagnetic conductive capping
layer 170 as a portion of a second electrically conductive line
90.
[0091] The layer stack including the SAF structure 120, the
magnetic tunnel junction 140, the dielectric capping layer 348, and
the nonmagnetic conductive capping layer 170 can be annealed to
induce crystallographic alignment between the crystalline structure
of the nonmagnetic tunnel barrier layer 134 (which may include
crystalline MgO having a rock salt crystal structure) and the
crystalline structure of the free layer 136.
[0092] As in the first embodiment, the location of the first
electrode 32 and the second electrode 92 may be switched such that
the second electrode 92 is electrically connected to the SAF
structure 120 and the first electrode 32 is electrically connected
to the nonmagnetic conductive capping layer 170. The layer stack
including the material layers from the SAF structure 120 to the
nonmagnetic conductive capping layer 170 can be deposited in
reverse order, i.e., from the SAF structure 120 toward the
nonmagnetic conductive capping layer 170 or from the nonmagnetic
conductive capping layer 170 toward the SAF structure 120. The
layer stack can be formed as a stack of continuous layers, and can
be subsequently patterned into discrete patterned layer stacks for
each memory cell 180.
[0093] Optionally, each memory cell 180 can include a dedicated
steering device, such an access transistor (not shown) or a diode
configured to activate a respective discrete patterned layer stack
(120, 140, 136, 348, 170) upon application of a suitable voltage to
the steering device. The steering device may be electrically
connected between the patterned layer stack and one of the first
electrically conductive lines 30 or one of the second electrically
conductive lines 90.
[0094] The magnetoresistive memory device of the third embodiment
may comprise a spin-transfer torque (STT) magnetoresistive memory
device configured to flow electrical current bidirectionally (i.e.,
in opposite direction) between the first electrode 32 and the
second electrode 92 to deterministically program the memory cell
180 into two different resistivity states.
[0095] A control circuit 402 can be provided to generate the
bidirectional current flow between the first electrode 32 and the
second electrode 92. The control circuit 402 can have two nodes
that are connected to a respective one of the first electrode 32
and the second electrode 92 via a respective first electrically
conductive line 30 and a respective second electrically conductive
line 90. Thus, the control circuit 402 can be configured to provide
a positive programming voltage to the first electrode 32 relative
to the second electrode 92, and to provide a negative programming
voltage to the first electrode 32 relative to the second electrode
92.
[0096] In some embodiments, current flow from the reference layer
132 through the nonmagnetic tunnel barrier layer 134 and into the
free layer 136 causes the magnetization of the free layer 136 to
become parallel to the magnetization of the reference layer 132,
and current flow from the free layer 136 through the nonmagnetic
tunnel barrier layer 134 and into the reference layer 132 causes
the magnetization of the free layer 136 to become antiparallel to
the magnetization of the reference layer 132. In some other
embodiments, the correlation between the current flow direction and
the spin transfer direction may be the opposite.
[0097] The nonmagnetic metal dust layer 146 increases the
perpendicular magnetic anisotropy of the free layer 136, and
increases the thermal stability of the magnetization of the free
layer 136.
[0098] Referring to FIG. 6, measurement data for in-plane
magnetization of a free layer 136 along a horizontal direction
(i.e., an in-plane direction that is perpendicular to the interface
between the free layer 136 and the nonmagnetic tunnel barrier layer
134) under an applied external magnetic field along the horizontal
direction is shown for a test sample implementing an embodiment of
the present disclosure illustrated in FIG. 5 in which the
nonmagnetic metal dust layer 146 includes an iridium layer and the
dielectric capping layer 348 includes a magnesium oxide, and for a
comparative sample which is derived from the embodiment of the
present disclosure in FIG. 5 by omitting the nonmagnetic metal dust
layer 146 and by a magnesium oxide layer of the same thickness as
the dielectric capping layer 348. The measurement data for the
comparative sample is represented by a first curve 610. The
measurement data for the test sample is represented by a second
curve 620.
[0099] The first curve 610 shows a first critical magnetic field
Hk1 of about 1,400 Oersted. The second curve 620 shows a second
critical magnetic field Hk2 of about 6,200 Oersted. In the
illustrated example, the nonmagnetic metal dust layer 146 of the
second embodiment of the present disclosure can provide an
enhancement in the critical magnetic field (Hk) for aligning the
magnetization of the free layer 136 along an in-plane direction by
a factor of 4 or greater, such as about
6,200/1,400.apprxeq.4.43.
[0100] The magnitude of the critical magnetic field for aligning
the magnetization of the free layer 136 along an in-plane direction
is a measure of the perpendicular magnetic anisotropy of the free
layer. As the test data in FIG. 6 illustrates, the nonmagnetic
metal dust layer 146 of the second embodiment of the present
disclosure that employs an iridium layer provides significant
enhancement in the perpendicular magnetic anisotropy of the free
layer 136 relative to the comparative example.
[0101] Referring back to FIG. 5, a magnetoresistive memory device
is provided according to the third embodiment of the present
disclosure. The magnetoresistive memory device comprises a first
electrode 32, a second electrode 92, and a magnetic tunnel junction
140 located between the first electrode 32 and the second electrode
92.
[0102] The magnetic tunnel junction 140 comprises a reference layer
132 having a fixed magnetization direction (which is one of the up
direction and the down direction), a free layer 136 having magnetic
anisotropy that provide bistable magnetization directions that are
parallel or antiparallel to the fixed magnetization direction, and
a nonmagnetic tunnel barrier layer 134 located between the
reference layer 132 and the free layer 136. The magnetoresistive
memory device also comprises a dielectric capping layer 348 located
between the second electrode 92 and the free layer 136, and a
nonmagnetic metal dust layer 146 contacting the dielectric capping
layer 348 and the free layer 136.
[0103] In one embodiment, the nonmagnetic metal dust layer 146
increases perpendicular magnetic anisotropy of the ferromagnetic
material of the free layer 136. In one embodiment, the nonmagnetic
metal dust layer 146 consists essentially of the at least one
elemental metal. In one embodiment, the at least one elemental
metal can be selected from Ir, Pd, Mg, Pt, W, Ta, Hf, Pd, Ru, or
Rh. In one embodiment, the nonmagnetic metal dust layer 146 can
consist essentially of a single elemental metal selected from Ir,
Pd, Mg, Pt, W, Ta, Hf, Pd, Ru, or Rh, for example Ir.
[0104] In one embodiment, the magnetoresistive memory device can
comprise a synthetic antiferromagnet structure 120 comprising a
hard ferromagnetic layer 112, an antiferromagnetic coupling layer
114, and the reference layer 132. The antiferromagnetic coupling
layer 114 provides antiferromagnetic coupling between magnetization
of the hard ferromagnetic layer 112 and magnetization of the
reference layer 132. The hard ferromagnetic layer 112 can contact
the first electrode 32.
[0105] In one embodiment, the nonmagnetic metal dust layer 146 has
a thickness less than 5 monolayers of the at least one elemental
metal. In one embodiment, the nonmagnetic metal dust layer 146 is
discontinuous and has sub-monolayer thickness.
[0106] In one embodiment, the dielectric capping layer 348
comprises, and/or consists essentially of, a dielectric material
selected from magnesium oxide, aluminum oxide, or a dielectric
oxide of at least one transition metal. In another embodiment, the
dielectric capping layer 348 comprises, and/or consists essentially
of the material of the voltage controlled magnetic anisotropy
(VCMA) dielectric capping layer 148 of the first embodiment having
a dielectric constant of 10 or greater, such as 25 or greater, but
a smaller thickness. The dielectric capping layer 348 has a
thickness in a range from 0.2 nm to 1 nm, and the nonmagnetic
tunnel barrier layer comprises magnesium oxide and has a thickness
in a range from 0.5 nm to 1.5 nm. Thus, the memory device comprises
a spin-transfer torque (STT) magnetoresistive random access memory
(MRAM) cell, in which the dielectric capping layer 348 has a
thickness in a range from 0.2 nm to 1 nm, and the nonmagnetic
tunnel barrier layer 134 comprises magnesium oxide and has a
greater thickness in a range from 0.6 nm to 1.2 nm than the
thickness of the dielectric capping layer 348.
[0107] The magnetoresistive memory device of FIG. 5 can be
manufactured by forming a layer stack including, from one side to
another, a first electrode 32, a reference layer 132, a nonmagnetic
tunnel barrier layer 134, a free layer 136, a nonmagnetic metal
dust layer 146, a dielectric capping layer 348, and a second
electrode 92 in a forward order or in a reverse order. A control
circuit 402 can be formed, and the first electrode 32 and the
second electrode 92 can be connected to a respective node of the
control circuit 402. The at least one elemental metal of the
nonmagnetic metal dust layer 146 increases magnetic anisotropy of a
ferromagnetic material within the free layer 136.
[0108] The nonmagnetic metal dust layer 146 enhances the
perpendicular magnetic anisotropy in the free layer 136, which
enhances thermal stability of the resistive states of the
spin-transfer torque (STT) magnetoresistive memory device. The
enhancement in the thermal stability of the resistive states is
commonly referred to as delta in the art of magnetoresistive memory
devices.
[0109] Referring to FIG. 7, a fourth exemplary memory device
according to a fourth embodiment of the present disclosure is
illustrated, which includes an STT magnetoresistive memory cell 180
that may be located within the RAM device 500 illustrated in FIG.
1. The fourth exemplary memory device can include an insulating
support 20, such as a silicon oxide layer, a first electrode 32
that may be electrically connected to, or comprises, a portion of a
first electrically conductive line 30 (such as a word line or a bit
line) and a second electrode 92 that may be electrically connected
to, or comprises, a portion of a second electrically conductive
line 90 (such as a bit line or a word line).
[0110] The memory cell 180 of the fourth exemplary structure can be
derived from the memory cell 180 of the second exemplary structure
by replacing a combination of a nonmagnetic metal dust layer 146
and a dielectric capping layer 348 with a hafnium oxide layer
(i.e., hafnium oxide dielectric capping layer) 448, or from the
first exemplary structure by replacing the VCMA dielectric capping
layer 148 with the hafnium oxide layer 448.
[0111] However, in this embodiment, the hafnium oxide layer 448 is
preferably thinner than the magnesium oxide nonmagnetic tunnel
barrier layer 134 such that the memory cell 180 is programmed by
the STT effect by flowing a spin polarized tunnel current through
both layers 134 and 448 in opposite direction. The control circuit
402 in the fourth exemplary structure can be the same as the
control circuit 402 of the second embodiment. The external magnetic
field source 60 is preferably omitted.
[0112] The fourth exemplary memory cell 180 includes a magnetic
tunnel junction (MTJ) 140. The magnetic tunnel junction 140
includes a reference layer 132 (which may also be referred to as a
"pinned" layer) having a fixed vertical magnetization, a
nonmagnetic tunnel barrier layer 134, and the free layer 136 (which
may also be referred to as a "storage" layer) having a
magnetization direction that can be programmed. The reference layer
132 and the free layer 136 can be separated by the nonmagnetic
tunnel barrier layer 134 (such as an MgO layer), and have a
magnetization direction perpendicular to the interface between the
free layer 136 and the nonmagnetic tunnel barrier layer 134.
[0113] In one embodiment, the reference layer 132 is located below
the nonmagnetic tunnel barrier layer 134, and the free layer 136 is
located above the nonmagnetic tunnel barrier layer 134. The hafnium
oxide layer 448 can be formed on top of the free layer 136 in order
to provide additional perpendicular anisotropy. Alternatively, the
reference layer 132 is located above the nonmagnetic tunnel barrier
layer 134, and the free layer 136 is located below the nonmagnetic
tunnel barrier layer 134. Generally, the reference layer 132 and
the free layer 136 may be located on opposite side of the
nonmagnetic tunnel barrier layer 134. In one embodiment, the
reference layer 132 and the free layer 136 have respective positive
uniaxial magnetic anisotropy.
[0114] The configuration in which the reference layer 132 and the
free layer 136 have respective perpendicular magnetic anisotropy
provides bistable magnetization states for the free layer 136. The
bistable magnetization states include a parallel state in which the
free layer 136 has a magnetization (e.g., magnetization direction)
that is parallel to the fixed vertical magnetization (e.g.,
magnetization direction) of the reference layer 132, and an
antiparallel state in which the free layer 136 has a magnetization
(e.g., magnetization direction) that is antiparallel to the fixed
vertical magnetization (e.g., magnetization direction) of the
reference layer 132.
[0115] A data bit can be written in the STT magnetoresistive memory
cell by passing high enough electrical current through the
reference layer 132 and the free layer 136 in a programming
operation so that spin-transfer torque can set or reset the
magnetization state of the free layer 136. The direction of the
magnetization of the free layer 136 after the programming operation
depends on the current polarity with respect to magnetization
direction of the reference layer 132. The data bit can be read by
passing smaller electrical current through the STT magnetoresistive
memory cell and measuring the resistance of the STT
magnetoresistive memory cell. The data bit "0" and the data bit "1"
correspond to low and high resistance states of the STT
magnetoresistive memory cell (or vice versa), which are provided by
parallel or antiparallel alignment of the magnetization directions
of the free layer 136 and the reference layer 132, respectively.
The fractional resistance change between parallel (P) and
antiparallel (AP) alignment (i.e., orientation) of the
magnetization direction is called tunnel magnetoresistance (TMR),
i.e., TMR=(R.sub.AP-R.sub.P)/R.sub.P.
[0116] The reference layer 132 can include either a Co/Ni or Co/Pt
multilayer structure or any other material that have larger
perpendicular magnetic anisotropy than free layer. In one
embodiment, the reference layer 132 can additionally include a thin
non-magnetic layer comprised of tantalum or tungsten having a
thickness in a range from 0.2 nm to 0.5 nm and a thin CoFeB layer
(having a thickness in a range from 0.5 nm to 3 nm).
[0117] The nonmagnetic tunnel barrier layer 134 can include any
tunneling barrier material such as an electrically insulating
material, for example magnesium oxide. In one embodiment, the
nonmagnetic tunnel barrier layer 134 comprises, and/or consists
essentially of, magnesium oxide and has a thickness in a range from
0.6 nm to 1.2 nm, such as 0.8 nm to 1 nm. Generally, the thickness
of a magnesium oxide layer as a nonmagnetic tunnel barrier layer
134 is sufficiently thin (e.g., below 1.2 nm) in order to permit
electron tunneling therethrough during a program operation.
[0118] In one embodiment, the reference layer 132 may be provided
as a component within a synthetic antiferromagnetic structure (SAF
structure) 120. The SAF structure 120 can include a hard (i.e.,
fixed) ferromagnetic layer 112 with fixed magnetization along a
vertical direction, an antiferromagnetic coupling layer 114, and
the reference layer 132 which remains adjacent to the nonmagnetic
tunnel barrier layer 134. The antiferromagnetic coupling layer 114
has a thickness that induces a strong antiferromagnetic coupling
between the reference layer 132 and the hard ferromagnetic layer
112, such that the antiferromagnetic coupling layer 114 can "lock
in" the antiparallel alignment between the hard ferromagnetic layer
112 and the reference layer 132, which in turn "locks in" a
particular (fixed) vertical direction of the magnetization of the
reference layer 132. In one embodiment, the antiferromagnetic
coupling layer can include ruthenium, iridium, or chromium, and can
have a thickness in a range from 0.3 nm to 1 nm.
[0119] The free layer 136 includes a ferromagnetic material such as
CoFeB, CoFe, Co, Ni, NiFe, or a combination thereof. If a CoFeB
alloy is included in the free layer 136, then the atomic
concentration of boron atoms within the CoFeB alloy may be in a
range from 10% to 30% (such as 20%), the atomic concentration of
cobalt atoms within the CoFeB alloy may be in a range from 10% to
40% (such as 15%), and the atomic concentration of Fe in the CoFeB
layer may be in a range from 50% to 90% (such as 65%). Any impurity
atom in the CoFeB alloy, if present, has an atomic concentration
less than 1 parts per million. The CoFeB alloy may be deposited in
the amorphous state on the nonmagnetic tunnel barrier layer 134
including crystalline MgO, which has a rocksalt crystal structure.
During a subsequent anneal of the device, the CoFeB alloy
crystallizes into a body-centered cubic crystal structure using the
MgO layer as a crystallization template, while some or all of the
boron atoms diffuse away from the interface with the MgO layer.
[0120] Thus, a proximal portion of the free layer 136 that contacts
the nonmagnetic tunnel barrier layer 134 may comprise a CoFe alloy
or a CoFeB alloy having a body-centered cubic crystal structure,
and may provide a coherent interface with the nonmagnetic tunnel
barrier layer 134 and a higher TMR. The thickness of the free layer
136 can be in a range from 0.6 nm to 1.5 nm, although lesser and
greater thicknesses can also be employed.
[0121] The hafnium oxide layer 448 can be formed on the free layer
136. In one configuration of the fourth embodiment, the hafnium
oxide layer 448 is deposited directly on the free layer 136 and
directly physically contacts the free layer 136 without any
intervening layer in between. Thus, the hafnium oxide layer 448 can
be in direct contact with the free layer 136 and can increase
perpendicular magnetic anisotropy of the free layer 136. The
hafnium oxide layer 448 can be deposited, for example, by physical
vapor deposition, chemical vapor deposition, or atomic layer
deposition. Alternatively, the nonmagnetic metal dust layer of the
third embodiment may be located between the hafnium oxide layer 448
and the free layer 136.
[0122] In one embodiment, hafnium oxide layer consists essentially
of hafnium oxide, such as undoped stoichiometric hafnium oxide. In
another embodiment, the hafnium oxide layer 448 consists
essentially of a doped hafnium oxide material including dopants at
an atomic concentration less than 3%. The dopants may include at
least one transition metal element such as Zr, Ti, Ta, Nb, or
V.
[0123] The fourth exemplary memory device of the fourth embodiment
of the present disclosure includes a STT magnetoresistive memory
device in which electrical current flows between the first
electrode 32 and the second electrode 92 through the nonmagnetic
tunnel barrier layer 134 during a program operation. Thus, the
thickness of the hafnium oxide layer 448 is within a range that
allows tunneling of electrical current through the hafnium oxide
layer 448.
[0124] Depending on the defect density and the leakage current
level through the hafnium oxide layer 448, the thickness of the
hafnium oxide layer 448 can be in a range from 0.2 nm to 1 nm, such
as from 0.2 nm to 0.6 nm. In one configuration, the hafnium oxide
layer 448 can contact the free layer 136, i.e., can be in physical
contact with a surface of the free layer 136.
[0125] The nonmagnetic tunnel barrier layer 134 can comprise
magnesium oxide having a thickness in a range from 0.5 nm to 1.5
nm. In one embodiment, the thickness of the hafnium oxide layer 448
can be less than the thickness of the nonmagnetic tunnel barrier
layer 134. In one embodiment, the thickness-to-dielectric constant
ratio of the hafnium oxide layer 448 can be less than the
thickness-to-dielectric constant ratio of the nonmagnetic tunnel
barrier layer 134. In other words, the ratio of the
thickness-to-dielectric constant ratio of the hafnium oxide layer
448 to the thickness-to-dielectric constant ratio of the
nonmagnetic tunnel barrier layer 134 can be less than 1.0. Ignoring
the tunneling effects, the ratio of the voltage drop across the
hafnium oxide layer 448 to the voltage drop across the nonmagnetic
tunnel barrier layer 134 can be the same as the ratio of the
thickness-to-dielectric constant ratio of the hafnium oxide layer
448 to the thickness-to-dielectric constant ratio of the
nonmagnetic tunnel barrier layer 134. Thus, a greater voltage drop
can be present across the nonmagnetic tunnel barrier layer 134 than
across the hafnium oxide layer 448 during programming and sensing.
In one embodiment, the ratio of the thickness-to-dielectric
constant ratio of the hafnium oxide layer 448 to the
thickness-to-dielectric constant ratio of the nonmagnetic tunnel
barrier layer 134 may be in a range from 0.04 to 0.8, such as from
0.1 to 0.5. In one embodiment, the thickness of the hafnium oxide
layer 448 can be less than the thickness of a monolayer of hafnium
oxide, and may be in a range from one half of the thickness of a
monolayer of hafnium oxide to the thickness of the monolayer of
hafnium oxide. In this case, the hafnium oxide layer 448 can be
discontinuous or formed with openings therethrough, and may form a
porous framework including a plurality of openings therethrough. In
another embodiment, the thickness of the hafnium oxide layer 448
can have a thickness greater than the thickness of a monolayer of
hafnium oxide, and can be formed as a continuous material layer
without openings therethrough or with openings having a total area
that is less than 5% of the total area of the hafnium oxide layer
448.
[0126] A nonmagnetic metallic material can be provided on the side
of the hafnium oxide layer 448 that faces away from the free layer
136. For example, a nonmagnetic conductive capping layer 170 can be
formed directly on the hafnium oxide layer 448. The nonmagnetic
conductive capping layer 170 includes at least one non-magnetic
electrically conductive material such as tantalum, ruthenium,
tantalum nitride, copper, and/or copper nitride. For example, the
nonmagnetic conductive capping layer 170 can comprise a single
layer, such as a single ruthenium layer, or a layer stack
including, from one side to another, a first ruthenium layer, a
tantalum layer, and a second ruthenium layer. For example, the
first ruthenium layer can have a thickness in a range from 0.5 nm
to 1.5 nm, the tantalum layer can have a thickness in a range from
1 nm to 3 nm, and the second ruthenium layer can have a thickness
in a range from 0.5 nm to 1.5 nm. Optionally, the nonmagnetic
conductive capping layer 170 may include an additional non-magnetic
electrically conductive material, such as W, Ti, Ta, WN, TiN, TaN,
Ru, and Cu. The thickness of such an additional non-magnetic
electrically conductive material can be in a range from 1 nm to 30
nm, although lesser and greater thicknesses can also be employed.
The second electrode 92 can be formed over the nonmagnetic
conductive capping layer 170 as a portion of a second electrically
conductive line 90.
[0127] The layer stack including the SAF structure 120, the
magnetic tunnel junction 140, the hafnium oxide layer 448, and the
nonmagnetic conductive capping layer 170 can be annealed to induce
crystallographic alignment between the crystalline structure of the
nonmagnetic tunnel barrier layer 134 (which may include crystalline
MgO having a rock salt crystal structure) and the crystalline
structure of the free layer 136.
[0128] The location of the first electrode 32 and the second
electrode 92 may be switched such that the second electrode 92 is
electrically connected to the SAF structure 120 and the first
electrode 32 is electrically connected to the nonmagnetic
conductive capping layer 170. The layer stack including the
material layers from the SAF structure 120 to the nonmagnetic
conductive capping layer 170 can be deposited in reverse order,
i.e., from the SAF structure 120 toward the nonmagnetic conductive
capping layer 170 or from the nonmagnetic conductive capping layer
170 toward the SAF structure 120. The layer stack can be formed as
a stack of continuous layers, and can be subsequently patterned
into discrete patterned layer stacks for each memory cell 180.
[0129] Optionally, each memory cell 180 can include a dedicated
steering device, such an access transistor (not shown) or a diode
configured to activate a respective discrete patterned layer stack
(120, 140, 448, 170) upon application of a suitable voltage to the
steering device. The steering device may be electrically connected
between the patterned layer stack and one of the first electrically
conductive lines 30 or one of the second electrically conductive
lines 90.
[0130] In one embodiment, the magnetoresistive memory device of the
fourth exemplary structure comprises a spin-transfer torque (STT)
magnetoresistive memory device (e.g., a STT MRAM cell 180)
configured to flow electrical current bidirectionally between the
first electrode 32 and the second electrode 92.
[0131] In one embodiment, the reference layer 132 has a fixed
vertical magnetization that is perpendicular to an interface
between the reference layer 132 and the nonmagnetic tunnel barrier
layer 134. The free layer 136 has perpendicular magnetic anisotropy
to provide bistable magnetization states that include a parallel
state having a magnetization that is parallel to the fixed vertical
magnetization and an antiparallel state having a magnetization that
is antiparallel to the fixed vertical magnetization. For the
purpose of programming, the polarity of the voltage applied to the
first electrode 32 with respect to the second electrode 92 can be
selected depending on the target magnetization state of the free
layer 136. For example, a voltage of a first polarity can be
applied to the first electrode 32 (with respect to the second
electrode 92) during a transition from an antiparallel state to a
parallel state, and a voltage of a second polarity (which is the
opposite of the first polarity) can be applied to the first
electrode 32 during a transition from a parallel state to an
antiparallel state.
[0132] A control circuit 402 can provide the bidirectional current
flow between the first electrode 32 and the second electrode 92.
The control circuit 402 may include one or more elements 560, 570,
580 and/or 590 shown in FIG. 1. The control circuit 402 can have
two nodes that are connected to a respective one of the first
electrode 32 and the second electrode 92 via a respective first
electrically conductive line 30 and a respective second
electrically conductive line 90. Thus, the control circuit 402 can
be configured to provide a positive programming voltage to the
first electrode 32 relative to the second electrode 92, and to
provide a negative programming voltage to the first electrode 32
relative to the second electrode 92. Current flow from the
reference layer 132 through the nonmagnetic tunnel barrier layer
134 and into the free layer 136 causes the magnetization of the
free layer 136 to become parallel to the magnetization of the
reference layer 132, and current flow from the free layer 136
through the nonmagnetic tunnel barrier layer 134 and into the
reference layer 132 causes the magnetization of the free layer 136
to become antiparallel to the magnetization of the reference layer
132. In other words, a positive voltage applied to the second
electrode 92 programs the free layer 136 into the parallel
magnetization state, while a negative voltage applied to the second
electrode 92 programs the free layer 136 into the antiparallel
magnetization state. Thus, the alignment of the magnetization of
the free layer 136 relative to the magnetization of the reference
layer 132 during programming is deterministic, i.e., depends only
on the polarity of the applied voltage to the first electrode 32
relative to the second electrode 92, and does not depend on the
duration of the programming pulse.
[0133] In one embodiment, the control circuit 402 can be configured
to apply a sensing voltage (i.e., read voltage) between the first
electrode 32 and the second electrode 92. The sensing voltage may
be positive or negative. The sensing voltage is selected such that
flipping of the magnetization of the free layer 136 does not occur
upon application of the sensing voltage. Thus, the sensing voltage
has a magnitude that is less than a magnitude of the positive
programming voltage and is less than a magnitude of the negative
programming voltage. In one embodiment, the sensing voltage may be
in a range from 50 mV to 500 mV, such as from 100 mV to 300 mV,
although lesser and greater magnitudes can also be employed for the
sensing voltage. In a non-limiting example, each of the positive
programming voltage and the negative programming voltage can have a
magnitude in a range from 100 mV to 1,500 mV, such as from 600 mV
to 1,000 mV, and the sensing voltage can be in a range from 50 mV
to 300 mV, such as from 100 mV to 200 mV.
[0134] The method of operating the STT MRAM cell 180 includes
programming the MRAM cell into a first programmed state by applying
a positive programming voltage to the second electrode relative to
the first electrode, such that a magnetization direction of the
free layer is parallel to a magnetization direction of the
reference layer, and programming the MRAM cell into a second
programmed state by applying a negative programming voltage to the
second electrode relative to the first electrode, such that the
magnetization direction in the free layer is antiparallel to the
magnetization direction of the reference layer. The method further
includes applying a sensing voltage to the first electrode relative
to the second electrode, and determining a magnitude of electrical
current that tunnels through the magnetic tunnel junction.
[0135] The hafnium oxide layer 448 enhances the perpendicular
magnetic anisotropy in the free layer 136, which enhances thermal
stability of the resistive states of the spin-transfer torque (STT)
magnetoresistive memory device. The enhancement in the thermal
stability of the resistive states is commonly referred to as delta
in the art of magnetoresistive memory devices.
[0136] Referring to FIG. 8, in-plane magnetization of a free layer
136 along a horizontal direction (i.e., an in-plane direction that
is perpendicular to the interface between the free layer 136 and
the nonmagnetic tunnel barrier layer 134) under an applied external
magnetic field along the horizontal direction is shown for a test
sample implementing an embodiment of the present disclosure
illustrated in FIG. 7 in which the dielectric capping layer is the
hafnium oxide layer 448, and for a comparative sample which is
derived from the fourth embodiment of the present disclosure in
FIG. 7 by replacing the hafnium oxide layer 448 with a magnesium
oxide dielectric capping layer having the same thickness. The
measurement data for the comparative exemplary test is represented
by a first curve 810. The measurement data for the test sample
implementing an embodiment of the present disclosure illustrated in
FIG. 7 is represented by a second curve 820.
[0137] The in-plane magnetization of a ferromagnetic film (such as
a free layer 136) having perpendicular magnetic anisotropy is zero
in the absence of any external in-plane magnetic field because the
magnetization of the ferromagnetic film is along the vertical
direction, i.e., the direction that is perpendicular to the major
surfaces of the ferromagnetic film (such as an interface of the
free layer 136 with a nonmagnetic tunnel barrier layer 134). As the
magnitude of the in-plane external magnetic field increases, the
angle between the magnetization of the magnetic film and the
vertical direction gradually increases from 0 degree to a finite
angle, and eventually becomes 90 degrees, which corresponds to the
plateau regions in the graph of FIG. 8. The faster the increase
(represented by a steep slope in the graph of FIG. 8) of the angle
is with the magnitude of the in-plane external magnetic field, the
less the magnetic anisotropy of the magnetic film, i.e., the
magnetic film becomes easily disoriented from the preferred
vertical magnetization directions even under a weak in-plane
external magnetic field. In contrast, the more gradual the increase
(represented by a smaller slope in the graph of FIG. 8) of the
angle with the magnitude of the in-plane external magnetic field,
the greater the magnetic anisotropy of the magnetic film, and the
magnetic film remains aligned to a preferred vertical magnetization
direction until strong external in-plane magnetic field is
applied.
[0138] The first curve 810 shows a first critical magnetic field
Hk1', which is the magnitude of the in-plane external magnetic
field that needs to be applied to align the magnetization of the
free layer along an in-plane direction (i.e., within a plane that
is parallel to the interface between the free layer and the
nonmagnetic tunnel barrier layer) in the comparative sample. Due to
the asymptotic nature of the alignment of the magnetization of the
free layer to the external magnetic field, the critical magnetic
fields are estimated by determining an intersection point of two
tangents from a flat portion and an adjoining sloped portion of a
respective curve in FIG. 8. The first critical magnetic field Hk1'
is about 1,600 Oersted. The second curve 820 shows a second
critical magnetic field Hk2', which is the magnitude of the
in-plane external magnetic field that needs to be applied to align
the magnetization of the free layer along an in-plane direction in
the test sample. The second critical magnetic field Hk2' is about
7,300 Oersted, which is more than three times greater than that of
the comparative sample. The hafnium oxide layer 448 of the
embodiment of the present disclosure can increase the critical
magnetic field for aligning the magnetization of the free layer 136
along an in-plane direction by a factor which is greater than the
ratio of the dielectric constant of the hafnium oxide layer 448
(which is about 25 to 30 for hafnium oxide depending on the quality
and the thickness of the film) to the dielectric constant of
magnesium oxide (which is in a range from 6.8 to 9.8 depending on
the quality and the thickness of a magnesium oxide film). In the
illustrated example, the factor can be about
7,300/1,600.apprxeq.4.56.
[0139] The magnitude of the critical magnetic field for aligning
the magnetization of the free layer 136 along an in-plane direction
is a measure of the perpendicular magnetic anisotropy of the free
layer as provided within a respective film stack of the test sample
implementing an embodiment of the present disclosure or as provided
within the comparative film stack. As the test data in FIG. 8
illustrates, the hafnium oxide layer 448 of the embodiment of the
present disclosure provides significant enhancement in the
perpendicular magnetic anisotropy of the free layer 136 (and thus,
the exchange energy) compared to a magnesium oxide dielectric
capping layer, without degrading the TMR of the STT MRAM cell 180.
Specifically, the interface between the free layer 136 and the MgO
tunneling barrier layer 134 is not degraded or altered in the
fourth embodiment. Furthermore, the hafnium oxide dielectric
capping layer 448 provides a better electric breakdown than a
comparable magnesium oxide dielectric capping layer.
[0140] Without wishing to be bound by a particular theory, it is
believed that during the application of a voltage across the
hafnium oxide layer 448, the 2p orbitals of the oxygen atoms in
hafnium oxide in contact with or in close proximity to a
ferromagnetic iron alloy (such as a CoFeB alloy, a CoFe alloy, or a
NiFe alloy) of the free layer 136, can hybridize with the 3d
orbitals of the iron atoms to generate hybridized orbitals at the
interface between the free layer 136 and the hafnium oxide layer
448. It is believed that this may induce precession in the
ferromagnetic iron alloy of the free layer 136, and thus improve
the PMA without degrading TMR.
[0141] The magnetoresistive memory device of FIG. 7 can be
manufactured by forming on a semiconductor substrate a layer stack
including, from one side to another, a first electrode 32, a
reference layer 132, a nonmagnetic tunnel barrier layer 134, a free
layer 136, a hafnium oxide layer 448, and a second electrode 92.
The hafnium oxide layer 448 may be in direct contact with the free
layer 136 and increases perpendicular magnetic anisotropy of the
free layer 136. Alternatively, the nonmagnetic metal dust layer of
the second embodiment may be formed between the free layer 136 and
the hafnium oxide layer 448 to further improve the PMA.
[0142] A control circuit 402 can be formed, and the first electrode
32 and the second electrode 92 can be connected to a respective
node of the control circuit 402. The control circuit 402 can be
configured to provide a positive programming voltage to the first
electrode 32 relative to the second electrode 92 to provide a first
programmed state for the magnetoresistive memory device, to provide
a negative programming voltage to the first electrode 32 relative
to the second electrode 92 to provide a second programmed state for
the magnetoresistive memory device, and to provide a sensing
voltage to the first electrode 32 relative to the second electrode
92. The sensing voltage has a magnitude that is less than a
magnitude of the positive programming voltage and is less than a
magnitude of the negative programming voltage.
[0143] Although the foregoing refers to particular preferred
embodiments, it will be understood that the disclosure is not so
limited. It will occur to those of ordinary skill in the art that
various modifications may be made to the disclosed embodiments and
that such modifications are intended to be within the scope of the
disclosure. Where an embodiment employing a particular structure
and/or configuration is illustrated in the present disclosure, it
is understood that the present disclosure may be practiced with any
other compatible structures and/or configurations that are
functionally equivalent provided that such substitutions are not
explicitly forbidden or otherwise known to be impossible to one of
ordinary skill in the art. All of the publications, patent
applications and patents cited herein are incorporated herein by
reference in their entirety.
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