This disclosure relates to circuits and methods for fabricating and/or utilizing ferroelectric materials to form electronic devices.
In a computing device, which may include devices such as general-purpose hand-held computers, gaming devices, communications devices, smart phones, embedded or special-purpose computing systems, memory devices may be utilized to store instructions, for example, for use by one or more processors of the computing device. Such computing devices may utilize various memory technologies, such as random-access memory (RAM), to store instructions executable by a processor and/or to store any results of such execution. In such memory devices, a binary logic value of “1,” or a binary logic value of “0,” may be determined at a bit line of a RAM cell in response to a voltage being applied to the gate of one or more access transistors of a cell of a RAM.
Other types of memory that may be utilized in computing devices may include, for example, ferroelectric memories, in which polarization of a ferroelectric material may be utilized to store a binary logic value of “1” or a binary logic value of “0.” To bring about storage of binary logic values, a memory cell that includes a ferroelectric material may be polarized in a first orientation, which may give rise to storage of a first binary logic value, while polarization of the ferroelectric material in a second orientation may bring about storage of a second binary logic value.
However, for at least some memory applications, as well as applications involving sensors that utilize ferroelectric capacitors, certain ferroelectric materials may be subject to instability. Such instability may be especially evident when utilizing sensors of reduced dimensions, such as sensors comprising one or more submicron dimensions. In addition, over time, performance of certain ferroelectric materials may begin to degrade. Such degradation may be exhibited as loss of remanent polarization and/or other figures-of-merit of ferroelectric devices. Thus, although the technology of ferroelectric devices continues to advance, instability and/or lack of endurance of ferroelectric devices, particularly as such devices continue to be reduced in size, may limit the magnitude of such advances. For these reasons, and others, stabilization of ferroelectric materials continues to be an active area of investigation.
The present technique(s) will be described further, by way of example, with reference to embodiments thereof as illustrated in the accompanying drawings. It should be understood, however, that the accompanying drawings illustrate only the various implementations described herein and are not meant to limit the scope of various techniques, methods, systems, or apparatuses described herein.
for a ferroelectric device according to an embodiment;
Reference is made in the following detailed description to accompanying drawings, which form a part hereof, wherein like numerals may designate like parts throughout that are corresponding and/or analogous. It will be appreciated that the figures have not necessarily been drawn to scale, such as for simplicity and/or clarity of illustration. For example, dimensions of some aspects may be exaggerated relative to others. Further, it is to be understood that other embodiments may be utilized. Furthermore, structural and/or other changes may be made without departing from claimed subject matter. References throughout this specification to “claimed subject matter” refer to subject matter intended to be covered by one or more claims, or any portion thereof, and are not necessarily intended to refer to a complete claim set, to a particular combination of claim sets (e.g., method claims, apparatus claims, etc.), or to a particular claim. It should also be noted that directions and/or references, for example, such as up, down, top, bottom, and so on, may be used to facilitate discussion of drawings and are not intended to restrict application of claimed subject matter. Therefore, the following detailed description is not to be taken to limit claimed subject matter and/or equivalents.
As previously mentioned, in a computing device, such as a general-purpose hand-held computer, a gaming device, or the like, memory devices may be utilized to store instruction for execution by one or more processors of the computing device and/or to store any results of such execution. In such memory devices, a binary logic value of “1,” or a binary logic value of “0,” may be determined at a bit line of a RAM cell in response to a voltage being applied to the gate of one or more access transistors of a bit cell of a RAM. A particular type of RAM, which may utilize ferroelectric materials, may be polarized along a first orientation to bring about storage of a first binary logic value. Polarizing a ferroelectric material along a second axis, such as an axis oriented in a direction opposite to the first axis, may bring about storage of a second binary logic value. Polarization of ferroelectric memory cells may be controlled, for example, via applying a voltage to the memory cell to change (e.g., to reverse) a polarization state of the memory cell.
Accordingly, it may be appreciated that it may be beneficial for polarization voltages to correspond to voltages that are already present, for example, in a memory controller of the computing device. Otherwise, a memory controller of the computing device may require a separate voltage source, which may increase complexity of a ferroelectric-based memory system. To bring about switching of a polarization state of a ferroelectric memory cell in response to applying an available voltage, it may be desirable to limit a thickness dimension of a film used to form a ferroelectric memory cell. By way of limiting a thickness dimension (t) of a ferroelectric memory cell, an electric field (Ep) having sufficient magnitude may be generated so as to polarize the ferroelectric memory cell without exceeding an available voltage (V). This may be summarized substantially in accordance with expression (1) below:
V=t·E
p (1)
Expression (1) indicates that a voltage required to generate an electric field (EP) of a magnitude sufficient to polarize a ferroelectric memory cell is directly proportional to a thickness dimension (t) of the ferroelectric film. Accordingly, it may be appreciated that for ferroelectric films having increased thickness (t), a proportionally-increased voltage may be utilized to bring about polarization switching of the ferroelectric film. Such voltages may be greater than a voltage available on a controller, for example, utilized to perform read and write operations to/from ferroelectric memory devices.
For other types of ferroelectric devices, such as imaging sensors utilizing ferroelectric materials, for example, an ability to decrease thickness (t) of a ferroelectric memory cell may bring about an increase in sensitivity. In one example, a ferroelectric-based imaging sensor, which utilizes measurement of a capacitance to determine presence of received signal, may benefit from a ferroelectric memory cell of a decreasing thickness (t), substantially in accordance with expression (2), below:
C=ε
o
A/t (2)
wherein expression (2) indicates that, for a given area (A), capacitance (C) may be increased by way of decreasing thickness between electrodes of the capacitor.
In computer memory applications and/or sensor applications, ferroelectric memory cells may experience fatigue over device lifetimes. For example, in at least some types of ferroelectric devices, noticeable degradation in device polarization as a function of an applied voltage may occur after, perhaps, 100,000 polarization reversals in connection with storage of binary digital values. In other instances, remanent polarization of a ferroelectric device may begin to degrade, which may affect ability of a memory controller to determine a polarization state of a memory material. Such degradation may bring about an increased number of memory write errors, decreased sensor sensitivity, and/or may bring about other undesirable effects.
Accordingly, particular embodiments of claimed subject matter provide a stabilizing dopant for ferroelectric materials comprising at least 75.0%, for example, of hafnium oxide or hafnium zirconium oxide. In particular embodiments of claimed subject matter, a ferroelectric material may comprise transition metal oxides or transition metal compounds other than hafnium oxide and hafnium zirconium oxide, such as transition metal oxides or transition metal compounds comprising a significant percentage, such as at least 75.0%, of scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), rutherfordium (Rf), dubnium (Db), seaborgium (Sg), bohrium (Bh), hassium (Hs), meitnerium (Mt), darmstadtium (Ds), roentgenium (Rg), copernicium (Cn), or any combination thereof. In addition, claimed subject matter may provide a stabilizing dopant for post transition metal oxides or post transition metal compounds and post transition metal oxides, such as gallium (Ga), indium (In), tin (Sn), thalium (Tl), lead (Pb), or any combination thereof.
Thus, particular embodiments of claimed subject matter may utilize the above-identified transition metal oxides and post transition metal oxides, which may utilize a bismuth dopant, such as an oxide of bismuth, (e.g., Bi2O3), or bismuth aluminum oxide (e.g., (BixAl1−x)2O3, wherein 0.01<x<0.99). Before discussing various embodiments in reference to the accompanying figures, a brief description of various nonlimiting embodiments is provided in the following paragraphs. In particular embodiments, ferroelectric memory cells comprising HfO2 or HfZrO2 may be designed with bismuth or a bismuth-containing compound to yield stability and to reduce fatigue such as in connection with repeated read and write memory operations.
For example, particular embodiments may be directed to a device, having a conductive substrate and one or more layers of ferroelectric material formed over the conductive substrate. The one or more layers of the ferroelectric material may be formed from a transition metal oxide, or a post transition metal oxide, having a concentration of at least about 75.0%. The one or more layers of the ferroelectric material may include a dopant species of bismuth in a concentration of between about 0.001% to about 25.0%. In one embodiment, the dopant species of bismuth may include Bi2O3 in a concentration of 0.001% to about 25.0%, or may include (BixAl1−x)2O3, wherein 0.01<x<0.99, in a concentration of about 0.001% to about 25.0%. In one embodiment, the concentration of the bismuth dopant species may induce a chemical strain to achieve between 50.0% and 100.0% of a theoretical maximum polarization of the c-axis orthorhombic phase as computed from the polarization of HfxZr(1−x)O2, wherein 0.01<x<0.99, in the ferroelectric material. In an embodiment, the one or more layers of the ferroelectric material may comprise a thickness of between 2.0 nm and about 30.0 nm. In one embodiment, the above-described device may be configured to operate as a two-terminal device. In one embodiment, the above-described device may be configured to operate as a three-terminal device.
In one embodiment, the one or more layers of ferroelectric material of the above-described device may be formed from a transition metal oxide, wherein the transition metal oxide includes (HfO2) or includes hafnium zirconium oxide (HfxZr(1−x)O2, wherein 0.01<x<0.99). In one embodiment, one or more layers of the ferroelectric material of the above-described device may include a dopant species of Bi2O3 or (BixAl1−x)2O3, wherein 0.01<x<0.99. In particular embodiments, the above-described device may further comprise a conductive overlay positioned over the one or more layers of the ferroelectric material, in which at least one of the conductive substrate and the conductive overlay include a concentration of at least 50.0% tantalum nitride. In one embodiment, the concentration of the bismuth dopant species may induce chemical strain to achieve between 50.0% and 100.0% of a theoretical maximum polarization of the c-axis orthorhombic phase as computed from polarization of HfxZr(1−x)O2, wherein 0.01<x<0.99, in the ferroelectric material. In an embodiment, the above-described device may further comprise a conductive overlay positioned over the one or more layers of the ferroelectric material, wherein at least one of the conductive substrate and the conductive overlay include a concentration of at least 50.0% titanium nitride (TiN). In an embodiment, the above-described device may further comprise a conductive overlay positioned over the one or more layers of the ferroelectric material, wherein at least one of the conductive substrate and the conductive overlay include a concentration of at least 50.0% tantalum nitride (TaN). In an embodiment, the above-described device may further comprise a conductive overlay positioned over the one or more layers of the ferroelectric material, wherein at least one of the conductive substrate and the conductive overlay include a concentration of at least 50.0% platinum (Pt).
Various embodiments may be directed to a device, having a conductive substrate and one or more layers of ferroelectric material formed over the conductive substrate. In such a device, the one or more layers of ferroelectric material may be formed from a material having a chemical formula of AxB(1−x)Bi(y)(L)2+δ:L′, wherein A and B correspond to transition metals or post transition metals, and wherein L corresponds to oxygen (O), sulfur (S), selenium (Se), or tellurium (Te), and wherein L′ may correspond to molecular oxygen (O2), iodine (I), bromine (Br), sulfur S, thiocyanate (SCN), chlorine (Cl), azide (N3), trifluoride (F3), cyanate (NCO), hydroxide (OH), ethylene (C2H4), water (H2O), NCS (N-bonded), acetonitrile CH3CN, glycine, pyridine, ammonia (NH3), ethylene diamine, 2,2′bipyridine, phen(1,10-phenanthroline), nitrogen dioxide (NO2), PPh3 (triphenylphosphine), cyanide (CN), or carbon monoxide (CO). In the chemical formula AxB(1−x)Bi(y)(L)2+δ:L′, y=⅔δ. In particular embodiments, y is equal to a function of x, where x is the solid-solution stoichiometry parameter of the dominant phase (e.g., the ratio Hf/Zr).
The above-described device may comprise a conductive overlay positioned over the one or more layers of the ferroelectric material, wherein at least one of the conductive substrate and the conductive overlay include a concentration of at least 50.0% TaN, at least 50.0% TiN, or at least 50.0% Pt. In one embodiment, one or more layers of a ferroelectric material of the above-described device may comprise a thickness of between about 2.0 nm and about 30.0 nm. In one embodiment, the above-described device may be coupled to a gate portion of a field-effect transistor, wherein a polarization state of the device is configured to control at least a portion of a channel region of the field-effect transistor. The one or more layers of the ferroelectric material of the above-described device may be deposited during a back-end-of-line process, wherein ferroelectricity is conveyed to a gate portion of the field-effect transistor by way of a via.
Various embodiments may be directed to a method including forming, in a chamber, a conductive substrate and forming, over the conductive substrate, one or more layers of a ferroelectric material. The one or more layers of the ferroelectric material may be formed from a transition metal oxide, or a post transition metal oxide, having a concentration of at least about 75.0%. The one or more layers of the ferroelectric material may include a dopant species of bismuth in a concentration of between about 0.001% to about 25.0%. The above-described method may further include forming a conductive overlay on the one or more layers of ferroelectric material, in which at least one of the conductive substrate and the conductive overlay are formed from a material that includes at least 50.0% TaN, at least 50.0% TiN, or at least 50.0% Pt.
Particular embodiments will now be described with reference to the figures, such as
In the device of
In various embodiments, ferroelectric material 110 may comprise any transition metal oxide or any post transition metal oxide. In one aspect, ferroelectric material 110 may include one or more layers doped with bismuth and/or bismuth-containing substitutional ligands so as to form a material having a chemical formula of AxB(1−x)Bi(y)(L)2+δ:L′, wherein A and B correspond to transition metals or post transition metals, and wherein L corresponds to oxygen (O), sulfur (S), selenium (Se), or tellurium (Te), and wherein L′ may correspond to molecular oxygen (O2), iodine (I), bromine (Br), sulfur S, thiocyanate (SCN), chlorine (Cl), azide (N3), trifluoride (F3), cyanate (NCO), hydroxide (OH), ethylene (C2H4), water (H2O), NCS (N-bonded), acetonitrile CH3CN, glycine, pyridine, ammonia (NH3), ethylene diamine, 2,2′bipyridine, phen(1,10-phenanthroline), nitrogen dioxide (NO2), PPh3 (triphenylphosphine), cyanide (CN), or carbon monoxide (CO) and others. In the chemical formula AxB(1−x)Bi(y)(L)2+δ:L′, y=⅔δ. In particular embodiments, y is equal to a function of x, where x is the solid-solution stoichiometry parameter of the dominant phase (e.g., the ratio Hf/Zr).
Ferroelectric material 110 may comprise bismuth or bismuth-containing dopant in a concentration (e.g., an atomic or molecular concentration) of between about 0.001% and about 25.0%. In particular embodiments, atomic concentrations of a bismuth dopant species, such as is Bi2O3 or (BixAl1−x)2O3 (wherein 0.01<x<0.99), may comprise a more limited range of or molecular concentrations such as, for example, between approximately 1.0% and 10.0%. However, claimed subject matter is not necessarily limited to the above-identified dopants and/or concentrations. It should be noted that claimed subject matter is intended to embrace ferroelectric materials comprising any concentration of dopants utilized in atomic layer deposition, chemical vapor deposition, plasma chemical vapor deposition, sputter deposition, physical vapor deposition, hot wire chemical vapor deposition, laser enhanced chemical vapor deposition, laser enhanced atomic layer deposition, rapid thermal chemical vapor deposition, spin on deposition, gas cluster ion beam deposition, or the like, utilized in fabrication of ferroelectric devices from transition metal oxide or post transition metal oxide materials.
In particular embodiments, formed ferroelectric materials may be strain-quenched via rapid thermal annealing comprising exposure of a formed ferroelectric material to a temperature range of between about 375.0° C. to about 475.0° C. for a duration of between 5.0 and 15.0 seconds. In one particular embodiment, strain-quenching may comprise rapid thermal annealing of a ferroelectric material via exposure of the ferroelectric material to an elevated temperature, such as a temperature within range of between about 400.0° C. to about 450.0° C. for a duration of about 10.0 seconds. Strain-quenching may be performed in a chamber utilizing a pressure, for example, of between 1.0 atm and 10.0 atm utilizing an ambient nitrogen environment. Such strain-quenching may operate to control (e.g., to reduce) vacancies within the lattice of a ferroelectric material. In embodiments, a formed ferroelectric material may be exposed to an additional annealing process, such as utilizing a chamber, via exposure to an oxygen environment for a duration of between about 5.0 seconds and about 10.0 seconds at an elevated temperature of about 300.0° C. to about 450.0° C. In particular embodiments, such additional annealing may take place before or after forming a top electrode, such as a conductive overlay, which may be deposited on or over one or more layers of a ferroelectric material. Annealing may comprise an optimized process, in which variables of temperature, duration, and pressure may be adjusted so as to activate strain fields while permitting distribution of bismuth, for example, within grain boundaries of a polycrystalline ferroelectric material.
It should be noted that although hysteresis graph 142 of
In addition, after attaining such polarization saturation, when switch 252 is opened, residual (or remanent) polarization of ferroelectric material 210 may continue to exert control over the width of depletion region 264 of field-effect transistor 250. Thus, it may be appreciated that, as shown in
It may be appreciated that stress versus strain relationships that bring about ferroelectric properties in materials comprising transition metal oxides and post transition metal oxides, such as described with reference to
To illustrate stress/strain relations that bring about ferroelectric behavior,
wherein in expression (3) the quantity α11 comprises parallel displacement after strain, and wherein α0 comprises original lattice spacing without strain. Also with
wherein expression (4) introduces α⊥ to denote perpendicular displacement after strain.
As previously discussed herein, HfO2 among other transition metal oxides, such as HfxZr(1−x)O2 (wherein 0.01<x<0.99) may be doped with bismuth (or a bismuth-containing molecule) give rise to a dopant concentration of between about 0.001% and about 25.0%, thereby obtaining in ferroelectric behavior. A model may be developed to relate “x” from the expression HfxBi(1−x)O2±δ and HfxZr(1−x)BiyO2±δ with “y” as a function of “x” to express maximum ferroelectric polarization (wherein y=⅔δ). In such a model, “x” may be proportional to the strain at the molecular level, which may be brought about by a dopant, such as bismuth. Such a model may additionally consider coupling of material strain to strain created responsive to one or more of conductive overlay 115 and conductive substrate 105 comprising TiN, TaN, or Pt. Accordingly, in at least particular embodiments of claimed subject matter, a dopant, such as bismuth, or any other atom having a small atomic radius in relation to other atoms of the lattice. A transition metal oxide, such as HfO2 or HfxZr(1−x)O2 (or a post transition metal oxide) may be selected so as to introduce appropriate strain when bismuth, or other element having a relatively small atomic radius. With this in mind, a polarization expression (P(x)) may be derived to determine polarization with respect to “x” in conjunction with electrode-induced strain (e.g., strain introduced by a conductive overlay/conductive substrate comprising TiN, TaN, or Pt). In certain embodiments, such an addition of a bismuth-containing dopant to an active material, such as active material 110 of
Accordingly, to optimize a material system to bring about a level of polarization in a ferroelectric material, three quantities, such as bulk modulus (K), Poisson's ratio (μ), and shear stress (γ) are to be evaluated. Bulk modulus may be expressed substantially in accordance with expression (5), below:
wherein V=volume,
corresponds to a change in pressure per unit volume
In this context, stress may operate much in the same way as pressure. In addition, density (ρ) may be expressed substantially in accordance with expression (6), below:
wherein σ corresponds to the overall applied to representative material, such as representative material 301 of
Shear strain may be expressed substantially in accordance with expression (7A), below:
wherein α0 corresponds to the lattice constant of active layer 440, and wherein α11 corresponds to in-plane strain the lattice constant for the xy plane shown in
wherein in expression (9), μi=αi correspond to dipole moments in which:
Expression 10 can be rewritten substantially in accordance with expression (11), in which:
Multiplication of expression (11) by
gives rise to
In expression (12) the quantity
may be recognized as ϵXX, ϵYY=ϵPLANE and the quantity
may be recognized as ϵZZ. Thus, expression (12) may be rewritten to form expression (13):
In expression (13), ϵPLANE may be substituted for ϵ.
From expression (13) it may be noticed that ϵZZ is electrode dominant (e.g., at least partially dependent on thickness of a transition metal oxide or post transition metal oxide material) and ϵPLANE is at least partially dependent on strain introduced by doping of a transition metal oxide or post transition metal oxide. However, both electrode-induced and chemically-induced strain can be combined by way of expression (13). Expression (13) can be rewritten as expression (14):
Multiplying expression (14) by
=gives:
then
Thus expression (15), below, may result:
Wherein expression (15) may be rewritten as expression (16):
Taking expression (16) and rewriting results in expression (17):
brings about expression (18):
Taking the derivative of
then cancelling α11 yields:
which indicates that the slope of P(x) as a function of x is positive and depends on the out-of-plane strain (α⊥). The out-of-plane strain occurs, at least in part, responsive to the electrode metal, which may comprise at least a substantial portion (e.g., at least 50.0%) of TiN, TaN, or Pt. Thus, considering a lattice with perpendicular compression, this implies that α⊥ is proportional to (γ1RDOPANT−γ⊥R0), wherein R0=radius of an Hf atom. Returning to the expression for
the quantity can be rewritten as expression (19) below:
can be rewritten as expression (20):
Expression (20) indicates that α⊥=γE(γ1RBi−γ2RHF). With this in mind,
can be rewritten as expression (21):
Making the substitution
since
and letting
this results in expression (22) below:
Integrating expression (22) from 0 to P, as shown in expression (23) provides:
Performing the integration of expression (23) provides expression (24):
Since x<1, ln(1−x)<0,
Thus, expression (24) can be rewritten as:
Considering that the electrodes (e.g., conductive overlay 115 and conductive substrate 105) exert a compressive force, γE comprises a negative value, expression (25) can be rewritten as:
A quadratic approximation may be made to expression (26), which yields expression (27):
wherein RDOPANT of expression (27) corresponds to the atomic radius of a bismuth atom.
With expression (27) in mind,
For the embodiment of bismuth-doped HfO2, to yield a ferroelectric material of HfxBi(1−x)O2, then:
This implies that making the substitution for
yields expression (28) below:
J=∫0τdt≅∫−P
wherein V420 corresponds to the magnitude of the voltage pulse generated by signal generator 420, and wherein VC corresponds to a voltage measured across ferroelectric device 425, and wherein VR corresponds to the voltage measured between resistor 430 and a reference (e.g., ground) of the test circuit of
In another embodiment, the approach of
wherein:
As shown in
Which indicates that a measured value of capacitance may increase as dopant concentration (x) is also increased.
It may thus be appreciated that at least in particular embodiments, maximum polarization (P(x)) may be expressed in expression (32) below:
wherein, at least in particular embodiments, RDOPANT>RHf and RZr. It may also be appreciated that
and that
The latter expression implies that for an electrode, such as either a conductive overlay or a conductive substrate,
wherein the quantity γE
Expression (33) implies that
which provides an optimized equation for electrodes (such as conductive substrate 105 and conductive overlay 115 of
As shown in
for a ferroelectric device, capacitance may represent a beneficial approach to optimize capacitance of a ferroelectric device since, at an applied voltage substantially equal to 0.0, CBI=C (VBI).
Accordingly, Pr provides residual (or remanent) polarization, along a plane that is perpendicular to the surface of the ferroelectric material, such as ferroelectric material 140 of
As shown in
Although illustrative embodiments of the invention have been described in detail herein with reference to the accompanying drawings, it is to be understood that the invention is not limited to those precise embodiments, and that various changes, additions and modifications can be effected therein by one skilled in the art without departing from the scope of the invention as defined by the appended claims. For example, various combinations of the features of the dependent claims could be made with the features of the independent claims without departing from the scope of the present invention.