Synthetic antiferromagnet disk-shaped particle and suspension comprising such particles
12400775 · 2025-08-26
Assignee
Inventors
Cpc classification
B82Y5/00
PERFORMING OPERATIONS; TRANSPORTING
H01F1/0054
ELECTRICITY
B82Y25/00
PERFORMING OPERATIONS; TRANSPORTING
H01F10/3272
ELECTRICITY
A61N1/406
HUMAN NECESSITIES
International classification
H01F1/00
ELECTRICITY
Abstract
The synthetic antiferromagnet disk-shaped particle comprises a first ferromagnetic layer, a second ferromagnetic layer and a non-magnetic interlayer arranged between the first and the second ferromagnetic layer, wherein each of the first and the second ferromagnetic layer comprises a uniaxial magnetic anisotropy in the plane of the ferromagnetic layers such that the switching fields from an antiferromagnetic alignment of the first and the second ferromagnetic layer to a ferromagnetic alignment (H.sub.AF.fwdarw.F) and from the ferromagnetic alignment to the antiferromagnetic alignment (H.sub.F.fwdarw.AF) fulfill the condition
Claims
1. A synthetic antiferromagnet disk-shaped particle comprising a first ferromagnetic layer, a second ferromagnetic layer, a non-magnetic interlayer arranged between the first and the second ferromagnetic layer, wherein each of the first and the second ferromagnetic layer comprises a uniaxial magnetic anisotropy in the plane of the ferromagnetic layers such that the switching fields from an antiferromagnetic alignment of the first and the second ferromagnetic layer to a ferromagnetic alignment (H.sub.AF.fwdarw.F) and from the ferromagnetic alignment to the antiferromagnetic alignment (H.sub.F.fwdarw.AF) fulfill the condition H.sub.AF.fwdarw.FH.sub.F.fwdarw.AF>.Math.H.sub.AF.fwdarw.F; wherein the uniaxial magnetic anisotropy in the plane of the ferromagnetic layers is larger than 5000 Joule per cubic meter; and wherein the synthetic antiferromagnet disk-shaped particle is characterized by a magnetic easy axis hysteresis loop in externally applied magnetic fields of 140 Millitesla or smaller.
2. The synthetic antiferromagnet disk-shaped particle according to claim 1, wherein an easy axis magnetic hysteresis loop has a substantially rectangular shape in the first and third quadrant of a coordinate system of magnetization versus magnetic field.
3. The synthetic antiferromagnet disk-shaped particle according to claim 1, wherein a ferromagnetic alignment of the first and the second ferromagnetic layers remains after the externally applied magnetic field is removed, but then decays back into an antiferromagnetically aligned ground state by thermal activation occurring at room temperature within a time period shorter than ten seconds; or the antiferromagnetically aligned ground state is re-established by application of an oscillatory magnetic field with a decaying field amplitude.
4. The synthetic antiferromagnet disk-shaped particle according to claim 1, wherein any one of the first or second ferromagnetic layer comprises Fe, Co, or Ni.
5. The synthetic antiferromagnet disk-shaped particle according to claim 4, wherein any one of the first or second ferromagnetic layer comprises an alloy comprising Fe, Co or Ni.
6. The synthetic antiferromagnet disk-shaped particle according to claim 5, wherein any one of the first or second ferromagnetic layer further comprises a rare earth element.
7. The synthetic antiferromagnet disk-shaped particle according to claim 6, wherein the rare earth element is samarium.
8. The synthetic antiferromagnet disk-shaped particle according to claim 4, wherein any one of the first or second ferromagnetic layer further comprises a rare earth element.
9. The synthetic antiferromagnet disk-shaped particle according to claim 8, wherein the rare earth element is samarium.
10. The synthetic antiferromagnet disk-shaped particle according to claim 1, wherein a diameter of the particle is between 10 nanometers and 5000 nanometers.
11. The synthetic antiferromagnetic disk-shaped particle according to claim 1, wherein a thickness of the particle is between 5 nanometers and 1000 nanometers.
12. The synthetic antiferromagnet disk-shaped particle according to claim 1, wherein the interlayer promotes an RKKY coupling between the first and the second ferromagnetic layer, thereby weakening the antiferromagnetic coupling between the first and the second ferromagnetic layer caused by magnetic stray fields of the first and second ferromagnetic layers.
13. The synthetic antiferromagnet disk-shaped particle according to claim 1, wherein the interlayer comprises platinum (Pt), iridium (Ir) or a PtIr alloy.
14. The synthetic antiferromagnet disk-shaped particle according to claim 13, wherein the interlayer comprises a Pt.sub.1-xIr.sub.x alloy.
15. The synthetic antiferromagnet disk-shaped particle according to claim 1, further comprising an additional layer capable of performing at least one of: oxidation protection of the first and the second ferromagnetic layer; chemical functionalization to obtain colloidal stability of the particle in liquids; biomedical functionalization; prevention of uptake of the particle by macrophages; release or reaction of a chemical substance comprised in the particle; and/or separation of the particle structure microfabricated on a substrate from the substrate.
16. The synthetic antiferromagnet disk-shaped particle according to claim 1, wherein the uniaxial magnetic anisotropy in the plane of the first ferromagnetic layer is generated through deposition of the first ferromagnetic layer onto an obliquely sputtered tantalum layer or through alloying the first ferromagnetic layer with a rare earth element.
Description
(1) The invention is further described with regard to examples, which are illustrated by means of the following drawings, wherein:
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(11) Arrows 20, 21 indicate the orientation of the magnetic moments of the first and the second ferromagnetic layers 10, 11 according to their uniaxial anisotropy K.sub.u in the plane of the ferromagnetic layers 10, 11. The arrows 20, 21 directing in opposite directions also indicate the antiferromagnetic alignment of the magnetic moments of the first and the second ferromagnetic layers 10, 11. The antiferromagnetic coupling may be obtained by the magnetic stray field of the first and second layers, which stray field is indicated by arrows 30.
(12) Dotted line 400 indicates the easy magnetization axis of both ferromagnetic layers 10, 11 of the particle 1. The magnetization is arranged in the planes of the ferromagnetic layers 10, 11. Dashed line 410 indicates the hard magnetization axis of both ferromagnetic layers 10, 11 of the particle 1. The hard magnetization axis is arranged perpendicular to the easy magnetization axis.
(13) The diameter 18 of the particle 1 may, for example, be about 500 nm. The height of the particle 1 may, for example, be about 14 nm. Thereby, the thicknesses of the first and second ferromagnetic layer 10, 11 may be about 6 nm and the thickness of the interlayer 12 may be about 2 nm.
(14) The first and second ferromagnetic layer 10, 11 are preferably made of Co, Fe, CoFe-alloy, FeB-alloy, CoB-alloy or FeCoB-alloy, possibly comprising, for example Ni. Preferably, the first and second ferromagnetic layers 10, 11 are CoFeB layers having a uniaxial anisotropy in the plane of each ferromagnetic layers of 20 kJ/m.sup.3 and a saturation magnetization of M.sub.s>1200 kA/m.
(15) The material of the interlayer preferably is Ta.
(16) In the M(H)-coordinate system shown in
(17) When the externally applied magnetic field reaches the saturation field H.sub.s of the ferromagnetic layer, the magnetic moments in the ferromagnetic layer are oriented into the direction of the magnetic field and the saturation magnetization M.sub.s is reached.
(18) In the first quadrant 450 of the M(H)-coordinate system the hysteresis loop for positive magnetic fields and positive magnetization values is shown. In the third quadrant 452 of the M(H)-coordinate system the hysteresis loop for negative magnetic fields and negative magnetization values is shown. For negative fields, the same magnetization process occurs for the other ferromagnetic layer such that a hysteresis loop occurs for the equivalent negative fields, and negative magnetization values.
(19) At zero magnetic field the particle represented in
(20) In real particles, preferably, the saturation magnetization is substantially reached and the hysteresis loops have a substantially rectangular shape. Thus, preferably, for a field H>H.sub.AF.fwdarw.F>0 applied along the uniaxial anisotropy axis in the plane of the ferromagnetic layers, the alignment of the magnetizations of the first and the second ferromagnetic layer 10, 11 is substantially parallel, for example larger than 80 percent of the saturation magnetization (0.8.Math.M.sub.s). Preferably, the magnetization is even larger than 90 percent of the saturation magnetization (0.9.Math.M.sub.s).
(21) In the antiferromagnet disk-shaped particle according to the present invention, a hard axis magnetic saturation field of the particle is larger than an easy axis magnetic saturation field of the particle.
(22) The saturation field H.sub.s is the field required to align the magnetization of the ferromagnetic layers parallel to a field applied in the plane of the layer, perpendicular to the uniaxial anisotropy axis (hard axis magnetization process) This magnetization process is illustrated by the dashed line 41, showing no hysteresis losses.
(23) The particles of the present invention have ferromagnetic layers with a significant uniaxial anisotropy in the plane of the ferromagnetic layers.
(24) For a field aligned along this uniaxial anisotropy axis the ferromagnetic layer with a magnetization opposite to the direction of the applied field switches at a switching field H.sub.AF.fwdarw.F (0<H.sub.AF.fwdarw.F<H.sub.s and reaches a preferred magnetization M>0.9.Math.M.sub.3 within a small field interval HH.sub.AF.fwdarw.F when the field is increased. For a decreasing field the magnetization of the ferromagnetic layer remains close to the saturation value, preferably at M>0.8.Math.M.sub.s and switches back to antiferromagnetic alignment abruptly at a field H.sub.F.fwdarw.AF>0, which field is close to 0, within a field interval H<H.sub.F.fwdarw.AF, such that the area of the partial hysteresis loop is maximized.
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(26) The same reference numbers are used for the same or similar elements.
(27) The hysteresis loops extend over all four quadrants 450, 451, 452, 453 of the M(H)-coordinate system.
(28) The particle and its hysteresis loop is designed such that the antiferromagnetic coupling of the first and second antiferromagnetic layer 10, 11 is too weak to return the particle into its antiferromagnetic ground state when the external magnetic field H is turned to zero.
(29) The particle shown in the example of
(30) Alternatively, an oscillatory magnetic field with a decaying field magnitude may be applied to the particle to return the particle into the antiferromagnetic ground state.
(31) For hyperthermia applications or also other applications, where the synthetic antiferromagnet particle is heated through hysteretic losses, preferably, a sequence of a magnetic alignment field and a magnetic oscillatory field is applied to the particle.
(32) This is outlined in more detail in
(33) In suspensions comprising a plurality of synthetic antiferromagnet particles, for example as shown in
(34) In order to obtain the highest magnetic losses when applying oscillatory magnetic fields, the particles must be forced to align their easy magnetization axis with the uniaxial direction of the applied external field. Such an alignment is achieved by application of a magnetic field with a magnitude larger than the easy axis saturation field but smaller than the hard axis saturation field over a time duration t.sub.a longer than the Brown relaxation time of the particles.
(35) Thus, if an alignment field H.sub.a with H.sub.AF.fwdarw.F<H.sub.a<H.sub.s is applied for a time duration 52 of t.sub.a>.sub.B, the easy-axes of all particles align with the field (
(36) Subsequently, an oscillatory field H.sub.osc with a magnitude larger than H.sub.AF.fwdarw.F to drive the magnetization of the particles through their easy-axis hysteresis loop is applied, preferably over a time duration 53 of t.sub.osc shorter than the Brown relaxation time of the particles.
(37) Afterwards, the particles are re-aligned again before the oscillatory field is again applied.
(38) In
(39) The alignment field is applied to the particle 1 to achieve an alignment of, for example M>0.8M.sub.s, of the particle's easy magnetization axes along the alignment field. The oscillatory field with amplitude H.sub.osc and frequency f.sub.osc is applied during the time period t.sub.osc to drive the particles N=t.sub.osc.Math.f.sub.osc times through the easy axis hysteresis loop for heat generation before the particle returns to the antiferromagnetic ground state or is made to return to the antiferromagnetic ground state.
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(41) The diameter of the synthetic antiferromagnet disk-shaped particles may be rather large, e.g. 500 nm, compared to superparamagnetic particles (<20 nm) commonly used for hyperthermia applications. Accordingly, the Brownian relaxation time may be rather large until the particles rotate back to an antiparallel ground state and random orientation in a liquid. Accordingly, there is plenty of time to drive the particles several times through their easy axis hysteresis loop in an applied oscillating field.
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(43) The ferromagnetic state of the particle occurs after application of a magnetic field of slightly less than 50 mT along the easy axis. As may be seen in the drawing, the easy axis hysteresis loop has an almost rectangular shape in the first and the third quadrant of the M(H)-coordinate system and comprises slightly rounded edges close to the saturation magnetization.
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(45) The ferromagnetic state is shown in
(46) In
(47) The hysteresis loops for RKKY interaction for two different strengths of the interaction is shown. The dark line shows the hysteresis loop for the particle having a RKKY interaction of J.sub.FM.=0.35 mJ/m.sup.2. The light line shows the hysteresis loop for the particle having a RKKY interaction of J.sub.FM.=0.39 mJ/m.sup.2.
(48) At zero field a remanent magnetization nearly equal to the saturation magnetization is observed and the particle remains locked in the ferromagnetic state. The ferromagnetic state is less stable than the antiferromagnetic state and because of the partial compensation of the antiferromagnetic coupling from the stray field by the ferromagnetic RKKY exchange, the energy barrier between the states is sufficiently small to allow a thermal decay to the antiferromagnetic ground state within about 1 s.
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(50) The further layers arewhen seen from bottom to top: a first or bottom functionalization layer 19 on top of the sacrificial layer 14, a seed layer 16, a first ferromagnetic layer 10, a non-magnetic interlayer 12, a second ferromagnetic layer 11 and a second or top functionalization layer 17.
(51) The seed layer 16 is, for example, a 2 nm to 6 nm thick layer, for example comprising or being made of Ta. The seed layer 16 is provided to promote an appropriate growth of the first ferromagnetic layer 10 and to obtain specific magnetic properties. Such specific magnetic properties, may, for example, be a sufficiently small or absent perpendicular magnetic anisotropy to keep the magnetization of the ferromagnetic layers 10, 11 in the plane, and an in-plane uniaxial magnetic anisotropy K.sub.u, in the ferromagnetic layer plane, to align the magnetization along this direction, to obtain a single-domain state, and to design switching fields H.sub.AF.fwdarw.F and H.sub.F.fwdarw.AF optimized to obtain largest magnetization loss within the boundaries defined by the biological discomfort level for oscillatory fields.
(52) The seed layer 16 may be deposited, for example by sputtering under an oblique angle, to give the seed layer 16 a specific structure. The seed layer 16 may, for example, be a nano-crystalline tantalum layer.
(53) The first ferromagnetic layer 10 grown on or deposited onto such a structured seed layer 16 then shows a uniaxial anisotropy in the plane of the first ferromagnetic layer.
(54) During deposition of the first and of the second ferromagnetic layers 10, 11 a uniaxial magnetic field may be applied. The strength of this applied magnetic field is sufficiently strong to align the magnetic moments during the deposition along the field direction to obtain an induced uniaxial anisotropy in the layer plane in the ferromagnetic layers 10, 11. During the deposition of the second ferromagnetic layer 11, the applied field must be sufficiently strong to align the magnetization of the second ferromagnetic layer 11 during its growth in the presence of the stray field of the first ferromagnetic layer 10.
(55) The first and second ferromagnetic layers 10, 11 are, for example, 6 nm thick, for example comprising an Fe-alloy, Co-alloy or a CoFe alloy, for example CoFeB, CoFe, FeB, CoB.
(56) In order to further increase the magnetic anisotropy induced, for example, by a magnetic field applied during sputtering of the ferromagnetic layers 10, 11, for example a CoFeB layer is alloyed with a rare earth metal, in particular Sm. Amorphous Sm (20%) Co (80%) layer can develop a significant uniaxial anisotropy in the layer plane induced by an applied field during layer growth or by an annealing process in a field following the deposition. An amorphous structure of the ferromagnetic layers arises from the Sm in the Sm(20%)Co(80%) alloy. Thus, the obtainable anisotropy in the plane of the ferromagnetic layers may be tuned by selecting the Sm/B-ratio in the CoFeBSm alloy or also in a Sm/CoFe ratio in an CoFeSm alloy. A uniaxial anisotropy in the layer plane of 50 kJ/m.sup.3 may be obtained in amorphous CoSm or CoFeSm or CoFeBSm layers of e.g. 6 nm thickness.
(57) The non-magnetic interlayer 12 may have a thickness of e.g. 2 nm and is made, for example, of Ta, Ta.sub.1-xPt.sub.x, Ir.sub.1-xPt.sub.x.
(58) The bottom functionalization layer 19 and the top functionalization layer 17 may protect the particle layer construction, from for example oxidation. More particularly, the two functionalization layers 17, 19 are layers permitting a biological, biomedical, physical or chemical functionalization of the particle, i.e. the binding of specific molecules to these layers, for example to obtain colloidal stability of the particle in liquids, to provide attachment capability of the particle to specific cells, to prevent uptake of the particle by macrophages, to enable release or reaction of a chemical substance comprised in the particle, for example a drug, upon heating of the particle. Functionalization layers may have a thickness of, for example, 2 nm to 10 nm. Materials for functionalization layers are, for example, Au, C, Ti-oxide, Ta, Si-oxide. The bottom and the top functionalization layer 17, 19 may be identical or may be different. The bottom and the top functionalization layer 17, 19 may be designed and chosen depending on the desired function of the synthetic antiferromagnet particle.
(59) A chemical or biochemical functionalization is preferably obtained after dissolution of the particle from the wafer by adding specific molecules to the functionalization layers 17 or 19 that are comprised of materials to obtain a suitable bonding to the molecules.
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(61) The typical specific power losses (SLP) for typical superparamagnetic particles (MNP) is indicated by the dashed area 21. The horizontal line 22 shows the SLP for hypothetical (best) CoFe nanoparticles exhibiting a rectangular hysteresis loop operated at the biological discomfort level Hf=5.Math.10.sup.9 Am.sup.1s.sup.1 providing about 5900 W/g. Thus, also tumors of very small sizes are available for hyperthermia treatment with these particles.
(62) The shaded rectangle 23 indicates tumors with a diameter of about 1 mm that can be treated with best CoFe nanoparticles with a particle concentration of 100 mg/cm.sup.3 that can be obtained by direct injection of the particles into the tumor. Magnetic nanoparticle concentrations of 10-100 mg/cm.sup.3 per tumor tissue are practicable. The shaded area 24 highlights the minimal diameter of tumors accessible with particle concentrations of 1 mg/cm.sup.3 of the best CoFe particles that can be expected for an antibody-targeted approach.