Electrical-current control of structural and physical properties via strong spin-orbit interactions in canted antiferromagnetic Mott insulators
11765989 · 2023-09-19
Assignee
Inventors
Cpc classification
H10N70/235
ELECTRICITY
G11C13/0007
PHYSICS
H01F10/002
ELECTRICITY
G11C2213/31
PHYSICS
H01F41/32
ELECTRICITY
H01F10/3218
ELECTRICITY
H10N99/03
ELECTRICITY
International classification
G11C13/00
PHYSICS
H01F10/32
ELECTRICITY
H01F41/32
ELECTRICITY
Abstract
A composition of matter consisting primarily of a stabilizing element and a transition metal oxide, wherein the transition metal oxide is an anti-ferromagnetic Mott insulator with strong spin orbit interactions, and the composition of matter has a canted crystal structure.
Claims
1. A composition of matter consisting primarily of a stabilizing element and a transition metal oxide, wherein the transition metal oxide is an anti-ferromagnetic Mott insulator with strong spin orbit interactions, and the composition of matter has a canted crystal structure.
2. The composition of matter of claim 1, wherein the transition metal oxide is a 4d or 5d transition metal oxide.
3. The composition of matter of claim 1, wherein the transition metal oxide is Iridium Oxide or Ruthenium Oxide.
4. The composition of matter of claim 1, wherein the anti-ferromagnetic Mott insulator has spin orbit interactions between 0.15 eV and 0.5 eV.
5. The composition of matter of claim 1, wherein the stabilizing element is selected from the group of Strontium, Barium, and Calcium.
6. The composition of matter of claim 1, wherein the composition of matter is a single crystal grown using a self-flux method.
7. The composition of matter of claim 1, wherein the composition of matter is selected from the group comprising: Sr.sub.2IrO.sub.4, Sr.sub.2Ir.sub.0.97Tb.sub.0.03O.sub.4, Sr.sub.3Ir.sub.2O.sub.7, BaIrO.sub.3, Ca.sub.3Ru.sub.2O.sub.7, and doped Ca.sub.2RuO.sub.4.
8. A method for electrical-current control of structural and physical properties of a material, the method comprising: applying current along a first dimension of the material, wherein the material consists of a stabilizing element and a transition metal oxide, wherein the transition metal oxide is an anti-ferromagnetic Mott insulator with strong spin orbit interactions, and the composition of matter has a canted crystal structure; and wherein applying current along a first dimension of the material results in a change in size and resistivity of the material along a second dimension.
9. The method of claim 8, wherein the applied current is between 50 mA and 150 mA.
10. The method of claim 8, wherein the material is maintained at a temperature between 50 K and 300 K.
11. The method of claim 8, where in applying current along a first dimension of the material results in the material having a negative differential resistance.
12. The method of claim 8, wherein the applied current is ramped from 0 mA to a desired current.
13. The method of claim 8, wherein the applied current is abruptly applied to the material.
14. The method of claim 8, wherein the transition metal oxide is a 4d or 5d transition metal oxide.
15. The method of claim 8, wherein the transition metal oxide is Iridium Oxide or Ruthenium Oxide.
16. The method of claim 8, wherein anti-ferromagnetic Mott insulator has spin orbit interactions between 0.15 eV and 0.5 eV.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)
(18)
(19)
(20)
(21)
(22)
(23)
(24)
(25)
(26)
(27)
(28)
(29)
(30)
(31)
(32)
(33)
(34)
(35)
(36)
(37)
DETAILED DESCRIPTION
(38) The following description and associated drawings teach the best mode of the invention. For the purpose of leaching inventive principles, some conventional aspects of the best mode may be simplified or omitted. The following claims specify the scope of the invention. Some aspects of the best mode may not fall within the scope of the invention as specified by the claims. Thus, those skilled in the art will appreciate variations from the best mode that fall within the scope of the invention. Those skilled in the art will appreciate that the features described below can be combined in various ways to form multiple variations of the invention. As a result, the invention is not limited to the specific examples described below, but only by claims and their equivalents.
(39) Electrical control of structural and physical properties is a long-sought, but elusive goal of contemporary science and technology. Various embodiments of the present technology demonstrate that an otherwise unremarkable combination of strong spin-orbit interactions (SOI) and a canted antiferromagnetic (AFM) Mott state is sufficient to attain that goal. The AFM insulator Sr.sub.2IrO.sub.4 provides a model system in which strong SOI lock canted Ir magnetic moments to IrO.sub.6-octahedra, causing them to rigidly rotate together. A novel coupling between an applied electrical current and the canting angle reduces the Néel temperature and drives a large, non-linear lattice expansion that closely tracks the magnetization, increases the electron mobility, and precipitates a unique resistive switching effect. Various embodiments of the present technology open new avenues for understanding fundamental physics driven by strong SOI in condensed matter, and provide a new paradigm for functional materials and devices.
(40) A unique competition between spin-orbit interactions (SOI) and Coulomb correlations, U, in 4d- and 5d-elements and their compounds drives unusual physical behaviors that markedly differ from those of their 3d counterparts. The 5d-based iridates display particularly strong and surprising influences of SOI on their physical properties. Early studies indicated iridates exhibit a preference for magnetic, insulating ground states, a trend now recognized as a consequence of a combined effect of U and strong SOI. An important example of this effect is the J.sub.eff=½ Mott state identified in Sr.sub.2IrO.sub.4, whose defining characteristic is the strong locking of the lattice and Ir magnetic moments.
(41) Various embodiments of the present technology provide a new study of Sr.sub.2IrO.sub.4 that centers on unconventional, single-crystal x-ray diffraction measurements with simultaneous application of electrical current to diffracted samples as well as the I-V characteristics, electrical resistivity and magnetization as functions of temperature, electrical current and magnetic field. Various embodiments of the present technology show that application of electrical current causes the a-axis lattice parameter to expand by 1% that, in turn, precipitates profound changes in physical properties. The current-controlled lattice expansion closely tracks the long-range magnetic order, causing a considerable decrease in both the Néel temperature (T.sub.N) and magnetization, due to the strong SOI that rigidly locks the Ir moments to the lattice. The current-dependence of the a-axis expansion is highly non-linear, which induces the novel I-V characteristics of Sr.sub.2IrO.sub.4.
(42) Simultaneous control of structural and physical properties via electrical current is a rare, but extremely desirable goal of contemporary condensed matter research because of its great technological potential. The various embodiments of the present technology that show such behavior in Sr.sub.2IrO.sub.4 open new avenues for understanding the fundamental consequences of strong SOI in crystalline solids, and provide a new paradigm for development of functional materials and devices.
(43) Sr.sub.2IrO.sub.4 is the archetype, SOI-driven insulator with T.sub.N=240 K, and an electronic energy gap Δ≤0.62 eV. It crystallizes in a tetragonal structure with space-group I4.sub.1/acd (No. 142) with a=b=5.4846 Å and c=25.804 Å at 13K. Recent studies suggest a further reduced space group I4.sub.1/a (No. 88) for Sr.sub.2IrO.sub.4. Two signature characteristics of Sr.sub.2IrO.sub.4 are essential for understanding the results of this study: (1) Rotation of the IrO.sub.6-octahedra about the c-axis by approximately 12°, which corresponds to a distorted in-plane Ir1-O2-Ir1 bond angle θ, has a critical effect on the ground state. (2) The magnetic structure is composed of ordered moments (0.208(3) μ.sub.B/Ir) canted within the basal plane. The 13° canting of the moments away from the a-axis closely tracks the staggered rotation of the IrO.sub.6 octahedra, which sharply contrasts the behavior of 3d oxides.
(44)
(45) A representative diffraction pattern taken with the basal plane of Sr.sub.2IrO.sub.4 nearly perpendicular to the incident x-ray beam is shown in
(46) The current-controlled changes in the a- and c-axis were quantitatively characterized by x-ray diffraction for current applied either to the basal plane or along the c-axis. The lattice responds more strongly to current in the basal plane than along the c-axis, which suggests that the orientation of the Ir moments is important, and that Joule heating is not affecting the data.
(47)
(48) Focusing on normalized changes in the a- and c-axis lattice parameters Δa/a and Δc/c with basal-plane I, where Δa/a=[a(I)−a(0)]/a(0), and 0 mA≤I≤105 mA; Δc/c is similarly defined.
(49) The current-controlled a-axis expansion is strongly associated with long-range AFM order. A parallel study of Sr.sub.2Ir.sub.0.97Tb.sub.0.03O.sub.4 shows that a 3% replacement of Ir.sup.4+ by Tb.sup.4+ leads to a disappearance of T.sub.N, but conveniently retains the insulating state and the original crystal structure. The absolute values of Δa/a and Δc/c for Sr.sub.2Ir.sub.0.97Tb.sub.0.03O.sub.4 for I=105 mA are small (<0.2%) and weakly temperature-dependent in the absence of AFM order (
(50) The conventional thermal expansion of Sr.sub.2IrO.sub.4 was also measured without application of current. The temperature dependence of the a- and c-axis and their corresponding changes δa/a and δc/c due to pure thermal expansion (δa/a=[a(T)−a(90K)]/a(90K) and δc/c is similarly defined) shows that the a-axis expands linearly and only slightly (˜0.1%) from 90 K to 300 K (
(51)
(52) Significant changes in the a-axis magnetic susceptibility χ.sub.a(T) and the a-axis magnetization M.sub.a are seen when current is applied (
(53) Another prominent consequence of the current-controlled lattice expansion is non-Ohmic behavior that features a negative differential resistance (NDR). NDR is a nonlinear phenomenon with a ratio of voltage to current ΔVΔ/I<0, contrary to Ohm's law, which describes a linear relationship between voltage and current, thereby a positive resistance or ΔVΔ/I>0. The phenomenon is in general attributed to either an “electrothermal” effect or a “transferred carrier” effect. The more common form of NDR is manifest in “N”-shaped I-V characteristics. Alternatively, an “S”-shaped NDR has been observed in various memory devices and a few hulk materials such as VO.sub.2, CuIr.sub.2S.sub.4-xSe.sub.x, Ca.sub.3Ru.sub.2O.sub.7 and 1T-TaS.sub.2. These bulk materials are characterized by a first-order metal-insulator transition (MIT) and, except for Ca.sub.3Ru.sub.2O.sub.7, are without an AFM state. The “S”-shaped NDR in these materials is closely associated with the first-order MIT, and attributed to drastic differences in crystal and electronic structures below and above MIT.
(54)
(55)
(56) Contrasting the above materials, Sr.sub.2IrO.sub.4 features a prominent AFM order and a Mott insulating state that persists up to at least 600 K without a MIT, indicating a different mechanism that drives the NDR. The “S”-shaped NDR was observed in an earlier study of Sr.sub.2IrO.sub.4 but the underlying mechanism remained unclear up to now. The I-V curves for current applied along either the a- or c-axis at a few temperatures are presented in
(57) A plot of V.sub.th as a function of temperature displays a pronounced slope change near 100 K, where an anomaly in M.sub.a occurs (
(58) The NDR behavior exhibited by Sr.sub.2IrO.sub.4 reflects a novel mechanism that fundamentally differs from that operating in other materials. This is based on constructing a picture that self-consistently explains the complex NDR behavior, and the current-controlled expansion and magnetization data. Note that the a-axis resistivity ρ.sub.a that drops by nearly three orders of magnitude at low temperatures (
(59)
(60) Corresponding I-V curves at 100 K feature a sharp switching point (V.sub.th) at I.sub.C1 and a broader turning point near I.sub.C2 (
(61) Fundamentally, the formation of the Mott insulating state with canted IrO.sub.6-octahedra and canted moments is caused by a cooperative transition in which the electronic structure gaps, thereby lowering its energy relative to the paramagnetic metallic state. The gapping mechanism involves electronic correlations that involve both spin-orbit coupling and scattering through the magnetic reciprocal lattice vector. The electronic correlation is expected to manifest itself in the unoccupied states (electron-carrier) and in the occupied (hole-carrier) states. The momentum shift associated with a finite current is usually negligible in uncorrelated systems but, in correlated systems close to quantum critical points, theory shows that relatively small changes in the low-energy electronic structure can cause large (non-linear) changes in the ordered structure. In short, a slight modification of the electronic structure induced by current may result in strong modifications of the electronic correlations. The NDR data is interpreted in terms of a reduction in the gapping, as suggested in
(62) A combination of strong SOI and canted AFM order can lead to a highly desirable paradigm for simultaneous electrical control of the crystal structure and physical properties of Sr.sub.2IrO.sub.4: (1) Strong SOI lock canted Jr moments to the IrO.sub.6-octahedra, which rigidly rotate together (
(63) In an example embodiment of the present technology, single crystals of Sr.sub.2IrO.sub.4 and Sr.sub.2Ir.sub.0.97Tb.sub.0.03O.sub.4 were grown using a self-flux method from off-stoichiometric quantities of IrO.sub.2, SrCO.sub.3, SrCl.sub.2 and Tb.sub.4O.sub.7. Measurements of crystal structures were performed using a Bruker D8 Quest ECO single-crystal diffractometer that features the PHOTON 50 CMOS detector, and is capable of high-speed data collection in shutterless operation mode ensuring excellent quality of data. It is also equipped with an Oxford Cryosystem that creates sample temperature environments ranging over 90 K to 300 K during x-ray diffraction measurements. Single crystals used in x-ray diffraction measurements under applied electrical current had typical dimensions 0.8×0.8×0.2 mm.sup.3. The electrical current was applied via two electrical leads (0.001-inch diameter gold wires) that were mounted on the basal plane, or along the c-axis of a single-crystal, which was then mounted on the tip of the sample holder for x-ray diffraction measurements (see
(64) A Keithley 6220 Precision Current Source provided electrical currents up to 105 mA to the sample while x-ray diffraction data were collected. The structural analysis was performed using APEX3 (v2016.9). The shifts in Bragg peaks are reversible in current cycling. No structural phase transition is discerned, as no new peaks emerge, and no existing peaks completely vanish. In addition, the lattice responds strongly to current in the basal plane, but remains essentially unchanged when current is applied along the c-axis, which suggests that the orientation of the magnetic moments, which lie in the basal plane, is important, and that Joule heating is not affecting the data. The latter conclusion is confirmed by the lack of differences between data taken by either slowly (ramping rate at 5 mA/step), or quickly (105 mA/step) increasing, current from zero to 105 mA.
(65) Standard four-lead measurements of the electrical resistivity and I-V curves were carried out using a Quantum Design Dynacool PPMS System equipped with a 14-Tesla magnet. The differential resistance, dV/dI, was also measured as a function of bias current using a technique offered by the Quantum Design Dynacool PPMS System. Magnetic properties were measured using a Quantum Design MPMS-7 SQUID Magnetometer; the sample was mounted on a probe that has electrical leads. The background of the probe with the leads and corresponding current was subtracted in each set of the magnetic data. The current source was also provided by the Keithley 6220 Precision Current Source. For these magnetic measurements, the applied magnetic field (H) and electrical current (I) were always parallel to the a-axis of the crystal.
(66) A Joule Heating Effect Is Eliminated by the Following Observations and Facts: (1) Joule heating is a local effect whereas the current-induced Δa/a is a bulk or global effect. (2) Current-induced Δa/a and Δc/c are anisotropic (
(67) The lattice changes due to applied current are also accompanied by a subtle color and size change of the sample, as seen under a polarizing microscope. A single-crystal Sr.sub.2IrO.sub.4 with two electrical leads were examined under an Olympus polarizing microscope with a CCD camera. A Keithley 6220 Precision Current Source provided the current source. The reflectivity change, which is subtle, signals a change in electronic structure due to the current.
(68) Novel materials, which often exhibit surprising or even revolutionary physical properties, are necessary for critical advances in technologies that affect the everyday lives of people. Transition metal oxides are currently the subject of enormous activity within both the applied and basic science communities. The overwhelming balance of interest was devoted to 3d-elements and their compounds for many decades, and the heavier 4d- and 5d-elements and their oxides have received increased attention only recently. Although strong spin-orbit interactions (SOI), which are proportional to the square of atomic number, Z.sup.2 (often Z.sup.4 in the literature) has been known for many decades to have fundamental and technological importance in the case of the 4f lanthanides and 5f actinides, they were justifiably ignored in studies of 3d-electron materials. What has not been widely appreciated is that 4d- and 5d-elements and their compounds exhibit a unique competition between fundamental Coulomb correlations, crystalline electric field and SOI, which results in unusual physical behaviors and interesting empirical trends that markedly differ from their 3d counterparts.
(69) The 4d and 5d materials such as ruthenates and iridates exhibit particularly strong and surprising influences of SOI on their physical properties. A unique interplay of on-site Coulomb repulsion, U, and strong SOT has intriguing consequences in 5d-based iridates. An early, important manifestation of this interplay is the J.sub.eff=½ Mott state identified in Sr.sub.2IrO.sub.4, whose defining characteristic is that the SOI can rigidly lock magnetic moments to the lattice, leading to novel magnetic and electronic behavior.
(70) Electrical-current control of structural and physical properties is a long-sought, but elusive goal of contemporary science and technology. Various embodiments of the present technology demonstrate that a combination of strong SOI and a canted antiferromagnetic (AFM) Mott state is sufficient to attain this important goal. The AFM insulator Sr.sub.2IrO.sub.4 provides a model system in which intrinsically strong SOI locks canted Ir magnetic moments to IrO.sub.6-octahedra, causing them to rigidly rotate together. A novel coupling between an applied electrical current and the canting angle reduces the Néel temperature and drives a large, non-linear lattice expansion that closely tracks the magnetization, increases the electron mobility, and precipitates a unique resistive switching effect. Various embodiments of the present technology suggest that similar current-controlled behavior may be widespread and present in other antiferromagnetic Mott insulators having strong SOI.
(71) Simultaneous control of structural and physical properties via electrical current is a rare, but extremely desirable contemporary goal because of its great technological potential. In particular, the technical effect of the present technology may be relevant to memory technologies. Traditional memory technologies based on charge storage along with magnetic and ferroelectric random-access memories are rapidly approaching physical or miniaturization limits. As memory technologies based on charge storage shrink, they approach a limit where they become too small to hold sufficient charge to operate as a memory. Alternatively, nonvolatile memory (NVM) concepts can be based on electrically switchable resistance, such as those demonstrated by various embodiments of the present technology, rather than charge storage; and NVMs utilizing resistive switching effects constitute a promising alternative as resistance random access memory or RRAM.
(72) In short, various technical effects of the present technology open new avenues for understanding the fundamental physics of strong SOI in condensed matter, and, equally importantly, provide a new paradigm for the development of an entire class of current-controlled materials to underpin functional devices. For example, computing devices using current-controlled materials for storage, such as those demonstrated by various embodiments of the present technology, may be much smaller than current charge-based memory technologies. Many other electronic devices may be constructed using the present technology to implement many different computing and/or other electrical, mechanical, and magnetic functions, including sensors, actuators, and the like.
(73) Sr.sub.2IrO.sub.4 is the archetype, SOI-driven insulator with T.sub.N=240 K, and an electronic energy gap Δ≤0.62 eV. It crystallizes in a tetragonal structure with space-group I4.sub.1/acd (No. 142) with a=b=5.4846 Å and c=25.804 Å at 13K. Recent studies suggest a further reduced space group I4.sub.1/a (No. 88) for Sr.sub.2IrO.sub.4. Two signature characteristics of Sr.sub.2IrO.sub.4 are essential for understanding the results presented here: (1) Rotation of the IrO.sub.6-octahedra about the c-axis by approximately 12°, which corresponds to a distorted in-plane Ir1-O2-Ir1 bond angle θ, has a critical effect on the ground state. (2) The magnetic structure is composed of ordered moments (0.208 μ.sub.B/Ir) canted within the basal plane. The 13° canting of the moments away from the a-axis closely tracks the staggered rotation of the IrO.sub.6 octahedra (see
(74)
(75) The relationship between the rotation of the IrO.sub.6 octahedra and magnetic moment canting in the iridates was first discussed in an earlier reference, in which a theoretical model proposed a strong magnetoelastic coupling in Sr.sub.2IrO.sub.4, and a close association between the magnetic moment canting and the ratio of the lattice parameter of the c-axis to the a-axis, as a consequence of the strong SOI. Indeed, the strong locking of the moment canting to the IrO.sub.6-rotation (by 11.8°) is experimentally manifest in studies of x-ray resonant scattering and SHG. In particular, the SHG study indicates that the I41/a space group requires a staggering of the sign of the tetragonal distortion (Δ.sub.1 and Δ.sub.2), which helps explain the magnetoelastic locking, as illustrated in
(76)
(77) A representative diffraction pattern taken with the basal plane of Sr.sub.2IrO.sub.4 nearly perpendicular to the incident x-ray beam is shown in
(78) The current-controlled changes in the a- and c-axis were quantitatively characterized by x-ray diffraction for current applied either to the basal plane or along the c-axis. The lattice responds more strongly to current in the basal plane than along the c-axis, which suggests that the orientation of the Ir moments is important, and that Joule heating is not affecting the data.
(79) Focusing on normalized changes in the a- and c-axis lattice parameters Δa/a and δc/c with basal-plane I, where Δa/a=[a(I)−a(0)]/a(0), and 0 mA≤I≤105 mA; Δc/c is similarly defined.
(80) The current-controlled a-axis expansion is expected to be strongly associated with long-range AFM order. A parallel study of Sr.sub.2Ir.sub.0.97Tb.sub.0.03O.sub.4 shows that a 3% replacement of Ir.sup.4+ by Tb.sup.4+ leads to a disappearance of T.sub.N, but conveniently retains the insulating state and the original crystal structure. The absolute values of Δa/a and Δc/c for Sr.sub.2Ir.sub.0.97Tb.sub.0.03O.sub.4 for I=105 mA are small (<0.2%) and weakly temperature-dependent in the absence of AFM order (
(81) The conventional thermal expansion of Sr.sub.2IrO.sub.4 was also measured without application of current. The temperature dependence of the a- and c-axis and their corresponding changes δa/a and δc/c due to pure thermal expansion (δa/a=[a(T)−a(90K)]/a(90K) and δc/c is similarly defined) shows that the a-axis expands linearly and only slightly (˜0.1%) from 90 K to 300 K (
(82) Significant changes in the a-axis magnetic susceptibility χ.sub.a(T) and the a-axis magnetization M.sub.a are also observed when current is applied (
(83) Another prominent consequence of the current-controlled lattice expansion is non-Ohmic behavior that features a negative differential resistance (NDR). NDR is a nonlinear phenomenon with a ratio of voltage to current ΔVΔ/I<0, contrary to Ohm's law, which describes a linear relationship between V and I, thereby a positive resistance or ΔVΔ/I>0. The phenomenon is in general attributed to either an “electrothermal” effect or a “transferred carrier” effect. The more common form of NDR is manifest in “N”-shaped I-V characteristics. Alternatively, an “S”-shaped NDR has been observed in various memory devices and a few bulk materials such as VO.sub.2, CuIr.sub.2S.sub.4-xSe.sub.x, Ca.sub.3Ru.sub.2O.sub.7 and 1T-TaS.sub.2. These bulk materials are characterized by a first-order metal-insulator transition (MIT) and, except for Ca.sub.3Ru.sub.2O.sub.7, are without an AFM state. The “S”-shaped NDR in these materials is closely associated with the first-order MIT, and attributed to drastic differences in crystal and electronic structures below and above MIT.
(84) Contrasting the above materials, Sr.sub.2IrO.sub.4 features a prominent AFM order and a Mott insulating state that persists up to at least 600 K without a MIT, indicating a different mechanism that drives the NDR. The “S”-shaped NDR was observed in an earlier study of Sr.sub.2IrO.sub.4 but the underlying mechanism remained unclear up to now. The I-V curves for current applied along either the a- or c-axis at a few temperatures are presented in
(85) A plot of V.sub.th as a function of temperature displays a pronounced slope change near 100 K, where an anomaly in M.sub.a occurs (
(86) The NDR behavior exhibited by Sr.sub.2IrO.sub.4 reflects a novel mechanism that fundamentally differs from that operating in other materials. This is based on constructing a picture that self-consistently explains the complex NDR behavior, and the current-controlled expansion and magnetization data. Begin by examining the a-axis resistivity ρ.sub.a that drops by nearly three orders of magnitude at low temperatures (
(87) Corresponding I-V curves at 100 K feature a sharp switching point (V.sub.th) at I.sub.C1 and a broader turning point near I.sub.C2 (
(88) Fundamentally, the formation of the Mott insulating state with canted IrO.sub.6-octahedra and canted moments is caused by a cooperative transition in which the electronic structure gaps, thereby lowering its energy relative to the paramagnetic metallic state. The gapping mechanism involves electronic correlations that involve both spin-orbit coupling and scattering through the magnetic reciprocal lattice vector. The electronic correlation is expected to manifest itself in the unoccupied states (electron-carrier) and in the occupied (hole-carrier) states. The momentum shift associated with a finite current is usually negligible in uncorrelated systems but, in correlated systems close to quantum critical points, theory shows that relatively small changes in the low-energy electronic structure can cause large (non-linear) changes in the ordered structure. In short, a slight modification of the electronic structure induced by current may result in strong modifications of the electronic correlations. The NDR data is interpreted in terms of a reduction in the gapping, as suggested in
(89) A combination of strong SOI and canted AFM order can lead to a highly desirable paradigm for simultaneous electrical control of the crystal structure and physical properties of Sr.sub.2IrO.sub.4: (1) Strong SOI lock canted Ir moments to the IrO.sub.6-octahedra, which rigidly rotate together (
(90) Various embodiments of the present technology demonstrate that electrical control of both crystal structures and collective electron states, which is extremely rare but long-sought in contemporary condensed matter research because of the great technological importance, can be achieved in materials that possess two key elements: strong SOI and a canted AFM Mott state. It is particularly encouraging that these two key elements are commonplace in a large number of heavy transition metal oxides.
(91) Various embodiments of the current-controlled material must possess the following two characteristics simultaneously: (1) Relatively strong SOI; and (2) Canted AFM Mott insulators.
(92) The strong SOI makes a strong locking of magnetic moments and TO.sub.6-octahedra (T=4d or 5d transition metal element) possible. A canted AFM state allows room for rotations of the canted moments. Applied electrical current (I) couples to the canted magnetic moments. Because of the strong locking of canted magnetic moments and TO.sub.6-octahedra due to SOI, and current can cause them to rigidly rotate together, or effectively tune the T-O-T bond angle θ, thus physical properties. These two essential requirements for current-controlled materials are also summarized in the Table 1.
(93) TABLE-US-00001 TABLE 1 Two Essential Requirements for Current-Controlled Behavior Exemplary Essentials Specifics Materials Relatively 0.15 eV-0.5 eV (4d-5d) Sr.sub.2IrO.sub.4, BaIrO.sub.3, Strong SOI Ca.sub.3Ru.sub.2O.sub.7 and Canted AFM Canted moments track doped Ca.sub.2RuO.sub.4 Insulator distorted bond angle θ
(94)
(95) Sr.sub.3Ir.sub.2O.sub.7 is a sister compound of Sr.sub.2IrO.sub.4, the model system. It is an AFM insulator with T.sub.N=285 K and equally strong SOI and similar IrO.sub.6 octahedral rotation to that in Sr.sub.2IrO.sub.4 but the magnetic moments in Sr.sub.3Ir.sub.2O.sub.7 are aligned along the c-axis, rather than within the basal plane where the octahedral rotation occurs (see
(96) It is emphasized that both conditions described above must be met simultaneously otherwise current control cannot be established. Sr.sub.3Ir.sub.2O.sub.7 serves an excellent example: It is an AFM insulator with the equally strong SOI and similar IrO.sub.6 octahedral rotation to that in Sr.sub.2IrO.sub.4 (
(97) Various embodiments of the present technology provide for a number of promising candidate materials besides Sr.sub.2IrO.sub.4.
(98) Iridate BaIrO.sub.3. BaIrO.sub.3 with space group of C2/m features three face-sharing IrO.sub.6 octahedra forming Ir.sub.3O.sub.12 clusters that are vertex-linked via IrO.sub.6 octahedra to construct one-dimensional (1D) chains along the c-axis (see
(99)
(100) It adopts a monoclinic distortion generating twisting and buckling of the cluster trimers that are titled (˜12° relative to each other) and give rise to two 1D zigzag chains along the c-axis and a layer of corner sharing IrO.sub.6 octahedra in the ab-plane, bringing about both 1D and 2D structural characteristics. BaIrO.sub.3 is a canted AFM system with T.sub.N=182 K and charge energy gap of 0.1 eV. The underlying structural, magnetic and transport properties, as illustrated in
(101)
(102) The distortions favor a canted magnetic structure in which magnetic moments are primarily aligned along the c-axis, and tracks distorted cluster trimers. This crucial feature along with the strong SOI, as discussed above, makes BaIrO.sub.3 a very promising candidate for current-controlled behavior. Indeed, applied current along the c-axis systematically and effectively suppresses both the magnitude of the c-axis magnetization M.sub.c(T) and T.sub.N (see
(103)
(104) A comparison drawn between BaIrO.sub.3 and Sr.sub.2IrO.sub.4 indicates that T.sub.N decreases with current remarkably more rapidly in BaIrO.sub.3 than in Sr.sub.2IrO.sub.4, as illustrated in
(105)
(106) The S-shaped I-V characteristic in BaIrO.sub.3 is strong at low temperatures, and significantly weakens with increasing temperature and vanishes near T.sub.N; the Ohmic behavior is eventually recovered about T.sub.N. This is illustrated in
(107) Ruthenate Ca.sub.2RuO.sub.4 and its derivatives. Some layered 4d-transition metal oxides can be promising candidate materials. The comparable magnitudes of their intra-atomic Coulomb interaction (U) and 4d-bandwidth (W) can leave them precariously balanced on the border between metallic and insulating behavior, and/or on the verge of long-range magnetic order. Therefore, moderately strong SOI, as well as weaker perturbations such as slight changes in lattice parameters, can induce drastic changes in the character of their electronic ground states.
(108) Extensive investigations of Ca.sub.2RuO.sub.4 have established that a strong cooperative Jahn-Teller distortion removes the degeneracy of the three Ru t.sub.2g orbitals (d.sub.xy, d.sub.yz, d.sub.zx) via a transition to orbital order that, in turn, drives a metal-insulator (MI) transition at T.sub.MI=357 K. However, Ca.sub.2RuO.sub.4 undergoes AFM order at T.sub.N=110 K<<T.sub.MI. Ca.sub.2RuO.sub.4 and its derivatives are highly sensitive to the lattice degrees of freedom, and chemical substitutions for Ru can effectively increase or decrease the MI transition. One signature feature that is relevant to this study is that Ca.sub.2Ru.sub.1-xM.sub.xO.sub.4 (M=Cr, Mn and Fe) exhibits a large negative volume thermal expansion via magnetic and orbital orders.
(109) Nevertheless, these structural and physical properties apparently facilitate the occurrence of the S-shaped I-V characteristics. Ca.sub.2Ru.sub.0.9Mn.sub.0.1O.sub.4 as an example is illustrated in
(110) Simultaneous control of structural and physical properties via applied electrical current poses a key, new research topic and technological significance. Various embodiments of the present technology study the spin-orbit-coupled antiferromagnet Ca.sub.2RuO.sub.4, and its derivative with 3% Mn doping to alleviate the violent first-order transition at 357 K for more robust measurements, illustrating that a small applied electrical current couples to the lattice by significantly reducing its orthorhombicity and octahedral rotations, concurrently diminishing the 125 K-antiferromagnetic transition and inducing a new, orbital order below 80 K. An example embodiment of the present technology to establish a phase diagram reveals a critical regime near a current density of 0.15 A/cm.sup.2 that separates the vanishing antiferromagnetic order and the new orbital order. Further increasing current density (>1 A/cm.sup.2) enhances competitions between relevant interactions in a metastable manner, leading to a peculiar glassy behavior above 80 K. The coupling between the lattice and nonequilibrium driven current is interpreted theoretically in terms of t.sub.2g orbital occupancies. The current-controlled lattice is the driving force of the observed novel phenomena. Finally, note that current-induced diamagnetism is not discerned in pure and slightly doped Ca.sub.2RuO.sub.4.
(111) 4d/5d-electron based oxides with inherent strong spin-orbit interactions (SOI) and significant electronic correlations create an entirely new hierarchy of energy scales and unique competitions between fundamental interactions, which leaves these materials precariously balanced on the border between metallic and insulating behavior, and/or on the verge of long-range magnetic order. As a result, exotic quantum states arise whenever subtle interactions conspire to generate large susceptibilities to small, external stimuli.
(112) The antiferromagnetic (AFM) insulator Ca.sub.2RuO.sub.4 is a good example. With Ru.sup.4+(4d.sup.4) ions, it exhibits a metal-insulator transition at T.sub.MI=357 K, which marks a concomitant and particularly violent structural transition with a severe rotation and tilting of RuO.sub.6, which governs physical properties of Ca.sub.2RuO.sub.4. This transition removes the t.sub.2g orbital degeneracy (d.sub.xy, d.sub.yz, d.sub.zx) and leads to orbital order that, in turn, drives the metal-insulator transition at T.sub.MI. An abrupt AFM transition occurs only at a considerably lower Neel temperature T.sub.N=110 K, highlighting its close association with a further distorted crystal structure. Extensive investigations of this system have established that quantum effects are intimately coupled to external stimuli in general and extremely sensitive to lattice perturbations in particular.
(113) Electronic properties of Ca.sub.2RuO.sub.4 are sensitive to applied electrical current. More recent investigations report current-induced diamagnetism and current-induced non-equilibrium state. Indeed, it has become increasingly clear that electrical current, which joins magnetic field, pressure, electric field, light, etc. as a new stimulus/probe, controls quantum states in an unprecedented fashion. This is certainly manifest in another embodiment of the present technology that demonstrates simultaneous current-control of structural and physical properties in Sr.sub.2IrO.sub.4 featuring strong SOI and a canted AFM state.
(114) Various embodiments of the present technology illustrate structural, magnetic and transport properties as a function of electrical current and temperature in 3% Mn doped Ca.sub.2RuO.sub.4, and, for comparison, in pure Ca.sub.2RuO.sub.4 and 9% Mn doped Ca.sub.2RuO.sub.4. It is emphasized that the dilute Mn doping for Ru preserves essential structural and physical properties of Ca.sub.2RuO.sub.4 but weakens the often pulverizing first-order structural phase transition at 357 K, making the single crystals more robust to sustain thermal cycling needed for thorough measurements. Various embodiments of the present technology reveal that a novel coupling between small applied electrical current and the lattice critically reduces the orthorhombicity and the octahedral rotation that in turn precipitously suppress the AFM state and subsequently induce a new orbital order below 80 K at a current density ≥0.15 A/cm.sup.2 in pure and Mn doped Ca.sub.2RuO.sub.4. Further increasing current density (>1 A/cm.sup.2) causes a metastable effect, thus an exotic glassy behavior featuring unusual sample-history dependence above 80 K. Various aspects of the present technology illustrate that nonequilibrium electron occupancies of the t.sub.2g orbitals stabilized by applied current drive the critical lattice changes, thus the novel phenomena in this correlated, spin-orbit-coupled system. Various embodiments of the present technology also emphasize the conspicuous absence of current-induced diamagnetism, which is reported to exist in Ca.sub.2RuO.sub.4.
(115) The single crystals utilized in various embodiments of the present technology are grown using floating-zone technique. The lattice parameters are measured as functions of electrical current and temperature using both neutron and x-ray diffraction. In order to avoid any spurious data due to background signals, Joule heating etc., a probe equipped with a set of Keithley meters and the Quantum Design MPMS XL magnetometer is specially made for simultaneous measurements of magnetization and electrical resistivity of the sample as a function of electrical current and temperature. All measurements are painstakingly repeated and verified on several single crystals for a few dozen times to ensure consistence.
(116)
(117) The crystal structure of the central compound of one exemplary embodiment of the present technology, Ca.sub.2Ru.sub.0.97Mn.sub.0.03O.sub.4, which retains the low-temperature orthorhombic symmetry (Pbca, No.61), is found extraordinarily susceptible to applied current for the studied temperature range of 80-400 K. The crystal for neutron diffraction with applied current is shown in
(118)
(119) Focus now on the structural data at 100 K culled via neutron diffraction as a function of current density, J, applied within the basal plane. As illustrated in
(120)
(121)
(122) The magnetization along the a- and b-axis, M.sub.a and M.sub.b, sensitively responds to applied current along the b-axis. As illustrated in
(123)
(124) A new, distinct phase emerges as the AFM state vanishes. The following example of the present technology focuses on M.sub.a at higher J as M.sub.b behaves similarly. Immediately following the disappearance of the AFM, a pronounced anomaly marked by T.sub.O precipitates near J.sub.c, as shown in
(125) It is conspicuous that current-induced diamagnetism, which is reported to exist in pure Ca.sub.2RuO.sub.4, is absent in not only Ca.sub.2Ru.sub.0.97Mn.sub.0.03O.sub.4 but also pure Ca.sub.2RuO.sub.4. For comparison and more clarification, the same measurements are conducted on pure Ca.sub.2RuO.sub.4 and 9% Mn doped Ca.sub.2RuO.sub.4. M.sub.a (and ρ.sub.b, not shown) for pure Ca.sub.2RuO.sub.4 (
(126) With the above confirmation, return now to a central compound of this technology, 3% Mn doped Ca.sub.2RuO.sub.4. At higher J (>1 A/cm.sup.2), the magnetization and the resistivity become peculiarly history-dependent at T>T.sub.O. This behavior is observed when the same samples are measured in two different ways, respectively: (1) the samples are measured when J gradually increases from 0 to 2.8 A/cm.sup.2; i.e., M and ρ for a smaller J is always measured before M and ρ for a larger J. The samples measured in this sequential fashion are denoted as “Trained”. (2) The same samples are then taken out of the measurement system, subsequently reinstalled and measured again; but unlike the trained samples, they are measured at a larger J, e.g., 1.4 A/cm.sup.2, at once without any prior measurements at smaller J. The samples measured in such a nonsequential, abrupt manner are denoted as “Untrained”. The data presented in
(127)
(128) M.sub.a at 1.4 A/cm.sup.2 for the untrained sample shows a much stronger anomaly occurring at 90 K rather than T.sub.O but remains essentially unchanged below T.sub.O (
(129)
(130)
(131) It is clear that small current as a new external stimulus effectively suppresses the AFM state and precipitates the new, intriguing phases below and above T.sub.O, as illustrated in
(132) The overall response of the crystal structure, resistivity and magnetism to applied in-plane electrical current can be understood theoretically in a tight-binding picture as follows. A tight-binding picture based on local orbitals is appropriate here since the metallic state is a current-driven instability of an insulating state that is captured by local orbital occupancies. The experimental feature to explain (see
(133) Without applied current, Ru.sup.4+ ions nominally have 2 holes in the t.sub.2g orbitals but x-ray spectroscopy studies suggest that a ½-hole is transferred to the oxygen. At high temperatures, in the metallic state, the remaining 3/2 hole is equally split in a 1:1 ratio between the d.sub.xy orbital and the manifold of d.sub.xz/d.sub.xz orbitals (giving an electron occupancy roughly ˜d.sub.xy.sup.1.2d.sub.xz.sup.1.6d.sub.yz.sup.1.6). At T<T.sub.MI, the first-order structural transition at T.sub.MI=357 K leads to the lattice distortions and the rotation, tilting and flattening of RuO.sub.6, which transfers more holes from d.sub.xy to d.sub.xz/d.sub.yz, leading to a 1:2 ratio of hole occupancies in d.sub.xy vs d.sub.xz/d.sub.yz (giving an electron occupancy roughly ˜d.sub.xy.sup.1.5d.sub.xz.sup.1.5d.sub.yz.sup.1.5). The insulating state below T.sub.MI thus has each orbital at exactly ¾ electron filling (or ¼-hole filling). In contrast, the metallic state above T.sub.MI has unequal filling, with a nearly filled d.sub.xz/d.sub.yz manifold (fewer holes) and, importantly, a nearly half-filled d.sub.xy orbital (more holes). This analysis suggests that the conductivity in the metallic phase above T.sub.MI is primarily enhanced by the d, orbitals.
(134) Now consider the nonequilibrium electron occupancies stabilized with an applied electric current. Within the d.sub.xy band, the electrons have large hopping amplitude from each Ru ion to each 4 of its neighbors, via the p.sub.x and p.sub.y orbitals on the four surrounding oxygens. This is not true for the d.sub.xz or d.sub.yz hands. So half-filling the d.sub.xy hand is far more favorable for the conductivity than half filling either the d.sub.xz or d.sub.yz bands or uniformly quarter-filling the entire multi-band manifold.
(135) Driving an in-plane current forces a metallic state to persist which, based on this theoretical picture, should lead to two effects: (1) the applied current minimizes crystalline distortions in the basal plane, so as to maximize interorbital hopping for in-plane conductivity; and (2) applying a current keeps the d.sub.xy band as close to half filling as possible, hence also avoiding the crystal distortions that are known (from the metal-insulator transition at zero applied current) to force d.sub.xy away from half filling. These two effects (
(136) Clearly, at the heart of the current-driven phenomena are the critical lattice modifications via current-driven nonequilibrium electron populations of the t.sub.2g orbitals, particularly the d.sub.xy orbital.
(137) The following claims specify the scope of the invention. Note that some aspects of the best mode may not fall within the scope of the invention as specified by the claims. Those skilled in the art will appreciate that the features described above can be combined in various ways to form multiple variations of the invention. As a result, the invention is not limited to the specific embodiments described above, but only by the following claims and their equivalents.