CN111235423B - Room-temperature high-spin Hall-angle platinum-rare earth thin film material and preparation method and application thereof - Google Patents

Room-temperature high-spin Hall-angle platinum-rare earth thin film material and preparation method and application thereof Download PDF

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CN111235423B
CN111235423B CN202010041791.8A CN202010041791A CN111235423B CN 111235423 B CN111235423 B CN 111235423B CN 202010041791 A CN202010041791 A CN 202010041791A CN 111235423 B CN111235423 B CN 111235423B
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rare earth
platinum
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CN111235423A (en
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金立川
朱虹宇
张怀武
唐晓莉
钟智勇
向全军
白飞明
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University of Electronic Science and Technology of China
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10N50/00—Galvanomagnetic devices
    • H10N50/80—Constructional details
    • H10N50/85—Magnetic active materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10N52/00—Hall-effect devices
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    • H10N52/00—Hall-effect devices
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Abstract

A room temperature high spin Hall angle platinum-rare earth film material belongs to the technical field of new spin electron materials. The film material is a platinum-rare earth alloy film which grows on the surface of the substrate, and in the platinum-rare earth alloy film, the mole percentage of rare earth elements is 1-60 mol%, and the mole percentage of platinum is 40-99 mol%. The room-temperature high-spin Hall angle platinum-rare earth film material and the preparation method thereof provided by the invention are simple and feasible, the spin Hall angle of the prepared platinum-rare earth film at room temperature is obviously increased relative to a pure platinum film, and the room-temperature spin diffusion length is reduced; compared with the spin Hall effect of pure platinum materials, the spin Hall effect has the advantages of increased spin current generation efficiency, reduced cost, realization of uniform preparation on a large-area semiconductor wafer, and provision of a new method for large-area preparation and research of giant spin Hall materials.

Description

Room-temperature high-spin Hall-angle platinum-rare earth thin film material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of new spintronic materials, and particularly relates to a platinum-rare earth film material with a very high room temperature spin Hall angle, and a preparation method and application thereof.
Background
With the rapid development of information technology, the miniaturization and low power consumption of electronic devices face a severe bottleneck due to the existence of joule heat in the conventional electronic devices. Electron spin is another property of electrons other than charge that can be used to transmit and manipulate information, i.e., Spintronics (Spintronics) has been born. The spin electron transmission information has extremely low power consumption, can even complete the processing and storage of quantum information, and is an ideal medium for constructing a quantum information chip. The Spin Hall Effect (Spin Hall Effect) is an Effect of generating longitudinal Spin current under the action of applying transverse current under the action of Spin-orbit coupling, and the Spin current can not be accompanied with the movement of charges, so that a non-dissipation process is realized, and the sample does not generate joule heat. In contrast, the Inverse spin Hall effect (Inverse Spi)n Hall Effect) refers to the process of converting spin current into current, which can be used to test the magnitude of spin current. The strength of the spin Hall effect is represented by the magnitude of the current-to-spin current conversion efficiency, which is expressed by the spin Hall angle (theta)SH) And (4) showing. Currently, spin hall effect research is usually performed in a "magnetic/nonmagnetic heavy metal" heterojunction system, however, the spin hall effect of a single nonmagnetic heavy metal is weak, the spin hall angle of the most commonly used heavy metal platinum (Pt) is about 0.15, and the spin hall angle of an alloyed or doped heavy metal material is significantly increased, for example, the spin hall angle of a copper bismuth (CuBi) alloy at a low temperature can reach 0.24, the spin hall angle of a bismuth platinum (BiPt) alloy at a room temperature can reach 0.23, the spin hall angle of a beta-W doped small amount of oxygen can reach-0.45, and the like. However, none of the existing alloy materials can meet the urgent requirement of obtaining a material with stronger spin hall effect, and people are in topological insulator (Bi)2Se3) And topological semi-metallic materials (TaAs, W)3Ta, etc.), but the growth process of the topological material is very expensive and difficult to produce in quantity, an ultrahigh vacuum molecular beam epitaxy system is usually needed or a small-area single crystal material is prepared at high temperature, and large-area preparation and application of magnetron sputtering cannot be realized.
Disclosure of Invention
The invention aims to provide a room-temperature high-spin Hall angle platinum-rare earth thin film material, and a preparation method and application thereof, aiming at the defects in the background technology. The platinum-rare earth film material has a high spin Hall angle at room temperature and is low in preparation cost.
In order to achieve the purpose, the invention adopts the technical scheme that:
the room-temperature high-spin Hall angle platinum-rare earth thin film material is characterized in that the thin film material is platinum-Rare Earth (RE) grown on the surface of a substratexPt100-x) An alloy thin film, the composition of the platinum-rare earth alloy thin film is RExPt100-x(RE is Gd, La, Sm, Nd, Ce, etc.), and the content x of the rare earth element RE is 1-60, namely, in the platinum-rare earth alloy film, the mole percentage of the rare earth element is 1-60 mol%, and the mole percentage of platinum is platinum40 to 99mol percent.
Preferably, the mole percentage of the rare earth element is 1 mol% to 40 mol%.
Further, the rare earth element may be Gd, La, Sm, Nd, Ce, or the like.
Further, the substrate is semiconductor silicon or the like; the platinum-rare earth alloy film is formed on the substrate by adopting methods such as physical vapor deposition, magnetron sputtering and the like; the thickness of the platinum-rare earth alloy film is 1-30 nm.
Further, the platinum-rare earth alloy thin film has a room-temperature spin Hall angle of more than 0.5, the numerical value of the spin Hall angle is related to the type and proportion of rare earth elements, the maximum room-temperature spin Hall angle of the platinum-rare earth alloy thin film exceeds 1 (approximately 1 order of magnitude higher than that of pure platinum), and meanwhile, the room-temperature spin diffusion length is reduced compared with that of the pure platinum.
Furthermore, the content of rare earth elements of the platinum-rare earth alloy film is controlled by attaching a high-purity Rare Earth (RE) metal sheet on a platinum target material or a platinum-rare earth alloy target material.
Further, non-magnetic platinum-Rare Earth (RE) of various thicknesses was tested by generating spin current by spin pumping and injecting it into a platinum-rare earth alloy thin filmxPt100-x) Room temperature inverse spin hall voltage (V) of alloy film/magnetic filmISHE) Testing of non-magnetic platinum-Rare Earth (RE)xPt100-x) And (3) fitting the resistivity of the alloy film to obtain the room-temperature spin Hall angle and the spin diffusion length of the platinum-rare earth alloy film.
Further, the room-temperature high-spin Hall angle platinum-rare earth thin film material is prepared by adopting a magnetron sputtering method, the target material is a platinum target material adhered with a rare earth metal sheet, a rare earth target material adhered with a platinum sheet or a platinum-rare earth alloy target material, and the specific process comprises the following steps: at 10-5Introducing 10-30 SCCM argon flow into a vacuum chamber under a vacuum environment with the Pa magnitude, and keeping the background vacuum degree at 0.26-0.5 Pa after the air pressure is stable; under the air pressure environment of 0.26-0.5 Pa, turning on a magnetron sputtering power supply, performing pre-sputtering on the target material with direct current power of 20-50W, and bombarding and cleaning the surface of the target material by argon ions; opening the baffle of the target material, and homogenizing at a rotating speed of 0.1 r/sAnd (3) rapidly rotating the substrate, and closing a sputtering power supply and a target baffle after the preset growth time is reached to obtain the platinum-rare earth film material.
A spin torque driving magnetic moment overturning device is characterized by comprising a substrate, a platinum-rare earth alloy film formed on the substrate and a magnetic film formed on the platinum-rare earth alloy film, wherein in the platinum-rare earth alloy film, the mole percentage of rare earth elements is 1-60 mol%, and the mole percentage of platinum is 40-99 mol%.
Further, the magnetic film is an Yttrium Iron Garnet (YIG) film, a nickel iron (NiFe) film, a cobalt iron boron (CoFeB) film, or the like.
Further, the thickness of the platinum-rare earth alloy film is 1-30 nm.
Furthermore, the content of rare earth elements of the platinum-rare earth alloy film is controlled by attaching a high-purity Rare Earth (RE) metal sheet, a platinum sheet-attached rare earth target or a platinum-rare earth alloy target on a platinum target.
Furthermore, the platinum target material adhered with the rare earth metal sheet is prepared by adhering at least one high-purity rare earth (more than 99.999 wt%) sheet to a sputtering track on the surface of the platinum target by taking the high-purity (more than 99.99 wt%) platinum target material as a matrix, and the molar ratio of rare earth elements in the target material is controlled between 1 mol% and 60 mol%.
Furthermore, the rare earth target material pasted with the platinum sheets is prepared by taking a high-purity (higher than 99.99 wt%) rare earth target material as a matrix and attaching at least one high-purity (higher than 99.999 wt%) platinum sheet on a sputtering track on the surface of the rare earth target material, wherein the molar ratio of rare earth elements in the target material is controlled between 1 mol% and 60 mol%.
Furthermore, the platinum-rare earth alloy target is a high-purity platinum-rare earth alloy target prepared by melting, and the molar ratio of rare earth elements in the target is controlled between 1 mol% and 60 mol%.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
the room-temperature high-spin Hall angle platinum-rare earth film material and the preparation method thereof provided by the invention are simple and feasible, the spin Hall angle of the prepared platinum-rare earth film at room temperature is obviously increased (the room-temperature spin Hall angle of the platinum-rare earth film can be more than 1 at most) relative to that of a pure platinum film, and the room-temperature spin diffusion length is reduced; compared with the spin Hall effect of pure platinum materials, the spin current generation efficiency is increased (specific experimental data are described in specific embodiments), the cost is reduced, uniform preparation on large-area (8-inch and 12-inch) semiconductor wafers can be realized, a new method is provided for large-area preparation and research of giant spin Hall materials, and the method has wide application prospects in a plurality of fields such as current-driven magnetic moment overturning, spin orbit torque magnetic tunnel junction memories (SOT-MRAM), spin sensors, low-power-consumption logic devices and the like in spintronics.
Drawings
FIG. 1 is a schematic diagram of spin pumping effect of room temperature high spin Hall angle Pt-RE film material according to the present invention;
FIG. 2 shows YIG (200nm)/Gd18Pt82(dGd18Pt82) System and YIG (200nm)/Gd7Pt93(dGd7Pt93) Fitting a spin Hall angle and spin diffusion length curve;
FIG. 3 shows YIG (200nm)/Pt and YIG (200nm)/Gd18Pt82And the ferromagnetic resonance line width delta H of the system is a relational graph of the frequency f, and the method is used for extracting the interface spin mixing conductance.
Detailed Description
The technical solution of the present invention will be described in detail with reference to specific examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
The room-temperature high-spin Hall angle platinum-rare earth thin film material is characterized in that the thin film material is platinum-Rare Earth (RE) grown on the surface of a substratexPt100-x) An alloy thin film, the composition of the platinum-rare earth alloy thin film is RExPt100-x(RE is Gd, La, Sm, Nd, Ce, etc.), and the content x of the rare earth element RE is 1-60, namely, the mole percentage of the rare earth element in the platinum-rare earth alloy film is 1 mol%60mol percent, and the mol percent of platinum is 40mol percent to 99mol percent; the thickness of the platinum-rare earth alloy film is 1-30 nm. The spin current generated by spin pumping in the ferromagnetic film is injected into the platinum-rare earth alloy film to test the inverse spin Hall voltage (V)ISHE) And obtaining the spin Hall angle of the platinum-rare earth alloy film, wherein the spin Hall angle of the platinum-rare earth alloy film is over 0.5 at room temperature, the numerical value of the spin Hall angle is related to the type and proportion of rare earth elements, the maximum spin Hall angle at room temperature is over 1 (approximately 1 order of magnitude higher than that of pure platinum), and the spin diffusion length at room temperature is reduced compared with that of pure platinum.
Example 1
A method for preparing a room-temperature high-spin Hall angle platinum-rare earth thin film material comprises the following steps:
s1, selecting a platinum target material adhered with rare earth gadolinium (Gd) as a sputtering target material, wherein the platinum target material adhered with rare earth gadolinium (Gd) is a target material prepared by adhering two square sheets of high-purity gadolinium (higher than 99.999 wt%) to a sputtering track on the surface of a platinum target by taking the platinum target material with high purity (higher than 99.99 wt%) as a matrix, and the molar ratio of gadolinium in the target material is 7 mol%;
s2, mounting the platinum target material pasted with rare earth gadolinium (Gd) in the step S1 at a target position of a cavity of a magnetron sputtering device;
s3, using the Si substrate as a substrate, cleaning the substrate by acetone, alcohol and deionized water, and drying the substrate by nitrogen to ensure that the surface of the Si substrate is clean;
s4, putting the substrate cleaned in the step S3 into a magnetron sputtering device to grow Gd7Pt93An alloy thin film; the specific process is as follows:
(1) at 10-5Introducing argon flow of 10SCCM into the vacuum chamber under a vacuum environment of Pa magnitude, and keeping the vacuum degree of the back bottom at 0.26Pa after the air pressure is stable;
(2) under the air pressure environment of 0.26Pa, a magnetron sputtering power supply is turned on, the target is pre-sputtered at the direct current power of 20W, and the surface of the target is bombarded and cleaned by argon ions;
(3) opening a baffle of the target, rotating the substrate at a constant speed of 0.1 r/s, and closing a sputtering power supply and the target baffle after the set growth time is reached to obtain a platinum-gadolinium film with the thickness of 10 nm;
s5 preparation of platinum gadolinium thin film (Gd)7Pt93Alloy film) was grown to a thickness of 200nm of Yttrium Iron Garnet (YIG) film.
Magnetic YIG thin film for spin current injection into Gd7Pt93In the alloy film, a reverse spin Hall voltage is generated by a reverse spin Hall effect to obtain Gd7Pt93The spin Hall angle of the alloy film. As shown in FIG. 2, the anti-spin Hall voltage (V) was testedISHE) About 20.2 microvolts, Gd to obtain giant spin Hall effect7Pt93The room temperature spin Hall angle of the alloy thin film is 0.52, and the room temperature spin diffusion length is 3.5 nm.
Example 2
This example is different from example 1 in that: in step S1, a platinum target material with rare earth gadolinium (Gd) attached is selected as a sputtering target material, the platinum target material with rare earth gadolinium (Gd) attached is a target material prepared by attaching five square sheets of high-purity gadolinium (higher than 99.999 wt%) to a sputtering track on the surface of a platinum target with a high-purity (higher than 99.99 wt%) platinum target material as a matrix, and the molar ratio of gadolinium element in the target material is 18 mol%. The rest of the procedure was the same as in example 1.
FIG. 1 is a schematic diagram showing spin pumping effect of room temperature high spin Hall angle Pt-RE thin film material; magnetic thin film spin current injection into Gd18Pt82In the alloy film, a reverse spin Hall voltage is generated by a reverse spin Hall effect to obtain Gd18Pt82The spin Hall angle of the alloy film. As shown in FIG. 2, the anti-spin Hall voltage (V) was testedISHE) About 28 microvolts, Gd giving a giant spin Hall effect18Pt82The spin Hall angle of the alloy thin film is 1.1, and the room-temperature spin diffusion length is 2.2 nm.
Comparative example
By the same procedure as in example 1, high purity platinum was selected as a target, Pt of 10nm was grown, and then an Yttrium Iron Garnet (YIG) film of 200nm in thickness was grown on the Pt (10nm) film, thereby obtaining a Pt (10nm)/YIG (200nm) film.
The Pt (10nm)/YIG (200nm) thin films obtained in the comparative example and the Pt obtained in example 2 were tested using ferromagnetic resonance and inverse spin Hall techniques82Gd18Inverse spin Hall voltage (V) of (10nm)/YIG (200nm) systemISHE) Curve and interface spinning mixed conductance to complete the fitting extraction of spinning Hall angle and spinning diffusion length, and Pt is used at room temperature82Gd18The spin Hall angle of the alloy reaches 1.1, which is 1800% higher than the spin Hall angle of pure Pt, which is 0.06%.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.

Claims (6)

1. The room-temperature high-spin Hall angle platinum-rare earth film material is characterized in that the film material is a platinum-rare earth alloy film growing on the surface of a substrate, and in the platinum-rare earth alloy film, the mole percentage of rare earth elements is 1-60 mol%, and the mole percentage of platinum is 40-99 mol%; the rare earth element is Gd, La, Sm, Nd or Ce; the platinum-rare earth alloy film is formed on the substrate by adopting a physical vapor deposition or magnetron sputtering method, and the thickness of the platinum-rare earth alloy film is 1-30 nm.
2. The room temperature high spin hall angle pt-rare earth thin film material of claim 1, wherein the mole percentage of the rare earth element is 1 mol% to 40 mol%.
3. The room temperature high spin hall angle platinum-rare earth thin film material of claim 1, wherein the room temperature high spin hall angle platinum-rare earth thin film materialThe high-spin Hall angle platinum-rare earth film material is prepared by adopting a magnetron sputtering method, the target material is a platinum target material adhered with a rare earth metal sheet, a rare earth target material adhered with a platinum sheet or a platinum-rare earth alloy target material, and the specific process comprises the following steps: at 10-5Introducing 10-30 SCCM argon flow into a vacuum chamber under a vacuum environment with the Pa magnitude, and keeping the background vacuum degree at 0.26-0.5 Pa after the air pressure is stable; under the air pressure environment of 0.26-0.5 Pa, turning on a magnetron sputtering power supply, performing pre-sputtering on the target material with direct current power of 20-50W, and bombarding and cleaning the surface of the target material by argon ions; and opening a baffle of the target, rotating the substrate at a constant speed of 0.1 r/s, and closing a sputtering power supply and the target baffle after the set growth time is reached to obtain the platinum-rare earth film material.
4. A spin torque driving magnetic moment overturning device is characterized by comprising a substrate, a platinum-rare earth alloy film formed on the substrate and a magnetic film formed on the platinum-rare earth alloy film, wherein in the platinum-rare earth alloy film, the mole percentage of rare earth elements is 1-60 mol%, and the mole percentage of platinum is 40-99 mol%.
5. The spin torque driven magnetic moment flipping device of claim 4, wherein the magnetic thin film is a yttrium iron garnet thin film, a nickel iron thin film, or a cobalt iron boron thin film.
6. The spin torque-driven magnetic moment flipping device of claim 4, wherein the platinum-rare earth alloy thin film controls the content of rare earth elements by attaching a rare earth metal foil, a platinum foil-attached rare earth target, or a platinum-rare earth alloy target to a platinum target.
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