CN110970549B - Ruthenium oxide containing hydrogen, electronic device, and method for controlling physical properties of ruthenium oxide - Google Patents

Ruthenium oxide containing hydrogen, electronic device, and method for controlling physical properties of ruthenium oxide Download PDF

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CN110970549B
CN110970549B CN201811161233.4A CN201811161233A CN110970549B CN 110970549 B CN110970549 B CN 110970549B CN 201811161233 A CN201811161233 A CN 201811161233A CN 110970549 B CN110970549 B CN 110970549B
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ruthenium
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于浦
李卓璐
沈胜春
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Tsinghua University
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Abstract

The application provides a method for regulating and controlling physical properties of ruthenium oxide containing hydrogen, an electronic device and ruthenium oxide. The hydrogen-containing ruthenium oxide is prepared by a method for regulating and controlling the physical properties of the ruthenium oxide. The structural formula of the ruthenium oxide containing hydrogen is shown in the specification
Figure DDA0001820089470000011
Wherein A is one or more of alkali metal element, alkaline earth metal element and rare earth metal element, B is Ru or metal adulterant of Ru, wherein the metal adulterant of Ru can be Ru, Ti, Mn, Cr, Fe, Ni, Mo,W, Ir, V, Co, Rh, Al, Sc, Zn or Cu, pm + qn + y is 2x, m is not less than 0, n is more than 0, x is more than 0, y is more than 0, p is not less than 1 and not more than 3, and q is not less than 2 and not more than 8. The hydrogen-containing ruthenium oxide greatly changes the property of the ruthenium oxide and widens the application prospect of the ruthenium oxide.

Description

Ruthenium oxide containing hydrogen, electronic device, and method for controlling physical properties of ruthenium oxide
Technical Field
The application relates to the field of material science, in particular to a method for regulating and controlling physical properties of ruthenium oxide containing hydrogen, an electronic device and ruthenium oxide.
Background
Transition metal ruthenium oxides belong to a strongly-associated system, and the oxides have abundant physical properties. For example, SrRuO3Sr as an additive having ferromagnetism, abnormal Hall effect and magnetostriction2RuO4Has superconducting effect. In addition, in the application, ruthenium oxides such as SrRuO3Has excellent metallicity, and can be epitaxially grown on most oxide materials while maintaining an atomically flat surface, and thus is considered to be a good electrode material.
SrRuO3And may also function as a catalyst in an electrochemical reaction, such as an oxygen evolution reaction.
At present, the methods for preparing new materials by using ruthenium oxide as a matrix and regulating and controlling corresponding properties mainly comprise metal doping and oxygen vacancy regulation and control. The metal doping method requires a complicated manufacturing process, is not favorable for large-scale production application, and the doping component is limited to metal cations. The components which can be changed by the regulation method of the oxygen vacancy are limited to oxygen ions and have smaller regulation degree.
Disclosure of Invention
In view of the above, it is necessary to provide a method for controlling physical properties of a ruthenium oxide-containing material, an electronic device, and a ruthenium oxide, in order to solve the problems that the preparation process of a new material using ruthenium oxide as a matrix is complicated and the change of components is limited.
The structural formula of the oxide containing the hydrogen ruthenium is shown in the specification
Figure BDA0001820089450000011
Wherein the content of the first and second substances,
a is one or more of alkali metal elements, alkaline earth metal elements and rare earth metal elements;
b is Ru or a metal dopant of Ru, wherein the metal dopant of Ru can be one or more of Ru and Ti, Mn, Cr, Fe, Ni, Mo, W, Ir, V, Co, Rh, Al, Sc, Zn or Cu; pm + qn + y is 2x, m is more than or equal to 0, n is more than 0, x is more than 0, y is more than 0, p is more than or equal to 1 and less than or equal to 3, and q is more than 2 and less than or equal to 8.
In one embodiment, the ruthenium hydroxide is 2 < q.ltoreq.4.
In one embodiment, the hydrogen-containing ruthenium oxide has the structure that y is more than 0 and less than or equal to 2 n.
In one embodiment, the hydrogen-containing ruthenium oxide has the structure that y is more than 0 and less than or equal to n.
In one embodiment, the hydrogen-containing ruthenium oxide, the alkali metal element is one or more of Li, Na, K;
the alkaline earth metal element is one or more of Be, Mg, Ca, Sr and Ba;
the rare earth metal elements are one or more of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc.
In one embodiment, the ruthenium hydroxide is ARuO3HyWherein y is more than 0 and less than or equal to 1.
In one embodiment, the ruthenium hydroxide containing component is A2RuO4HyWherein y is more than 0 and less than or equal to 1.
A method for regulating and controlling physical properties of ruthenium oxide comprises the following steps:
s102, providing a structural formula AmBnOxWherein m is more than or equal to 0, n is more than 0, x is more than 0, A is one or more of alkali metal elements, alkaline earth metal elements and rare earth metal elements, B is Ru or a metal dopant of Ru, wherein the metal dopant of Ru can be one or more of Ru and Ti, Mn, Cr, Fe, Ni, Mo, W, Ir, V, Co, Rh, Al, Sc, Zn or Cu;
s104, providing an ionic liquid, wherein the ionic liquid comprises hydrogen ions and oxygen ions, and placing the oxide in the ionic liquid;
s106, applying an electric field to the ionic liquid so as to enable hydrogen ions in the ionic liquid to be insertedThe oxide to form a structural formula
Figure BDA0001820089450000021
The hydrogen-containing ruthenium oxide is characterized in that pm + qn + y is 2x, y is more than 0, p is more than or equal to 1 and less than or equal to 3, and q is more than 2 and less than or equal to 8.
A method for regulating and controlling physical properties of ruthenium oxide comprises the following steps:
s202, providing a structural formula AmBnOxWherein m is more than or equal to 0, n is more than 0, x is more than 0, A is one or more of alkali metal elements, alkaline earth metal elements and rare earth metal elements, B is Ru or a metal dopant of Ru, wherein the metal dopant of Ru can be one or more of Ru and Ti, Mn, Cr, Fe, Ni, Mo, W, Ir, V, Co, Rh, Al, Sc, Zn or Cu;
s204, providing a metal catalyst and a hydrogen-containing reaction gas;
s206, heating to 20-200 ℃ to enable the hydrogen-containing reaction gas to generate hydrogen atoms under the action of the metal catalyst, wherein the hydrogen atoms are diffused and inserted into the oxide to form a structural formula
Figure BDA0001820089450000031
The hydrogen-containing ruthenium oxide is characterized in that pm + qn + y is 2x, y is more than 0, p is more than or equal to 1 and less than or equal to 3, and q is more than 2 and less than or equal to 8.
An electronic device comprising the ruthenium hydroxide according to any of the above.
The application provides a method for regulating and controlling physical properties of ruthenium oxide containing hydrogen, an electronic device and ruthenium oxide. The hydrogen-containing ruthenium oxide is prepared by a method for regulating and controlling the physical properties of the ruthenium oxide. The structural formula of the ruthenium oxide containing hydrogen is shown in the specification
Figure BDA0001820089450000032
Wherein A is one or more of alkali metal elements, alkaline earth metal elements and rare earth metal elements, B is Ru or a metal dopant of Ru, wherein the metal dopant of Ru can be one or more of Ru, Ti, Mn, Cr, Fe, Ni, Mo, W, Ir, V, Co, Rh, Al, Sc, Zn or Cu,pm + qn + y is 2x, m is more than or equal to 0, n is more than 0, x is more than 0, y is more than 0, p is more than or equal to 1 and less than or equal to 3, and q is more than 2 and less than or equal to 8. The hydrogen-containing ruthenium oxide greatly changes the property of the ruthenium oxide and widens the application prospect of the ruthenium oxide.
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FIG. 1 is a flow chart of a method for controlling the physical properties of ruthenium oxide according to one embodiment of the present disclosure;
FIG. 2 is a flow chart of a method for controlling the physical properties of ruthenium oxide according to one embodiment of the present disclosure;
fig. 3 is SrRuO provided in an embodiment of the present application3An X-ray diffraction pattern of the thin film structure;
FIG. 4 shows SrRuO under regulation of ionic liquid provided in one embodiment of the present application3X-ray diffraction patterns of changes in film structure;
FIG. 5 shows SrRuO under regulation of ionic liquid according to one embodiment of the present application3Hard X-ray absorption spectrum of Ru in thin film;
FIG. 6 shows SrRuO under regulation of ionic liquid according to one embodiment of the present application3X-ray diffraction patterns of changes in film structure;
FIG. 7 shows SrRuO before and after regulation by ionic liquid according to an embodiment of the present application3HySchematic diagram of variation of medium H content;
FIG. 8 is a schematic representation of a preferred embodiment of the present application1818Before and after regulation of ionic liquid in atmosphere SrRuO3HyMiddle O18A schematic diagram of the variation of the content;
FIG. 9 shows CaRuO under regulation of ionic liquid according to one embodiment of the present application3X-ray diffraction patterns of changes in film structure;
FIG. 10 shows CaRuO catalyzed by hydrogen atmosphere according to one embodiment of the present application3X-ray diffraction patterns of changes in film structure;
FIG. 11 shows an example of an ionic liquid modulated process Sr2RuO4HyX-ray diffraction pattern of (a);
FIG. 12 shows SrRuO in an ionic liquid hydrogenation process provided by an embodiment of the present application3With the ferromagnetic state of HA schematic representation of the content change;
FIG. 13 is a graphical illustration of hydrogen content of a sample with a topological Hall effect provided in accordance with an embodiment of the present application;
fig. 14 is SrRuO provided in an embodiment of the present application3A schematic diagram of realizing ferromagnetic state and paramagnetic state switching in a hydrogenation process;
fig. 15 is a schematic diagram of topological hall changes at different voltages according to an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more clearly understood, the methods for controlling physical properties of the ruthenium hydroxide, the electronic devices and the ruthenium oxide provided by the present application are further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In one embodiment, the present application provides a ruthenium hydroxide having a formula
Figure BDA0001820089450000041
Wherein the content of the first and second substances,
a is one or more of alkali metal elements, alkaline earth metal elements and rare earth metal elements;
b is Ru or a metal dopant of Ru, wherein the metal dopant of Ru can be one or more of Ru and Ti, Mn, Cr, Fe, Ni, Mo, W, Ir, V, Co, Rh, Al, Sc, Zn or Cu;
pm+qn+y＝2x，m≥0，n＞0，x＞0，y＞0，1≤p≤3，2＜q≤8。
in this embodiment, the hydrogen-containing ruthenium oxide may be provided in various structural forms. For example, the ruthenium hydroxide may be
Figure BDA0001820089450000042
Wherein the valence of the ruthenium element can be from greater than +2 to + 8. With the continuous insertion of hydrogen element into the original ruthenium oxide, the valence state of the ruthenium element in the ruthenium oxide containing hydrogen is reduced, and the final formed structural formula is shown in the specification
Figure BDA0001820089450000043
The hydrogen-containing ruthenium oxide of (1).
In one embodiment, the ruthenium hydroxide contains 2 < q ≦ 4.
In one embodiment, the hydrogen-containing ruthenium oxide has 0 < y ≦ 2 n. In one embodiment, the ruthenium hydroxide contains 0 < y ≦ n. It is understood that a range of 0 < y ≦ 3n may also be set.
In one embodiment, the alkali metal element is one or more of Li, Na, K. The alkaline earth metal element is one or more of Be, Mg, Ca, Sr and Ba. The rare earth metal elements are one or more of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc. A may be an alloy consisting of one or more of the alkaline earth metal elements or the rare earth metal elements. For example, the ruthenium hydroxide
Figure BDA0001820089450000051
Can be (SrLa)
,RuO3Hy、Sr(Mn,Ru)O3Hy、Ca(Rh,Ru)O3Hy、Ba(Ti,Ru)O3Hy、Li(Co,Ru)O3Hy、La(Ni,Ru)O3Hy、Sr(Ru,Al)O3Hy、Ho(Mn,Ru)O3Hy、(Dy,Nd)(Ru,Sc)O3Hy、Mg(Ru,Mo)O3Hy、Ca(Ru,Ni)O3Hy、Tb(Ru,W)O3Hy、(Na,Lu)(Fe,Ru)O3Hy、(Sm,Eu)(Ru,Ti)O3Hy、Sr2(Ru,Ir)O4Hy、Sr3Ru2O7Hy、(Ca,Ba)3(Mn,Ti)2O7Hy、Y3(Ru,Fe)5O12Hy、Mg(Ru,Fe)12O19Hy、Mg(Fe,Ru)2O4Hy. In one embodiment, the ruthenium hydroxide is ARuO3HyWherein y is more than 0 and less than or equal to 1. In one specific embodiment, the ruthenium hydroxide is SrRuO3HySaid hydrogen-containing ruthenium oxide SrRuO3HyOut-of-plane lattice constant ratio SrRuO of thin film3Is 0 to 3.3% larger than the in-plane lattice constant of (a). In this example, A is Sr element. In the present embodiment, when y is a different value from 0 to 1, SrRuO3The out-of-plane lattice constant of Hy can be of different values, the greater the value of y, SrRuO3HyThe larger the out-of-plane lattice constant, the SrRuO3HyCan reach the maximum out-of-plane lattice constant ratio SrRuO3The out-of-plane lattice constant of (a) is 3.3% greater.
In one embodiment, the ruthenium hydroxide is SrRuO3HyWherein y is more than or equal to 0.2 and less than or equal to 1. In the embodiment, the hydrogen-containing ruthenium oxide SrRuO with y being in the range of 0.2-1 can be obtained by different regulation and control methods3Hy。
In one embodiment, the ruthenium hydroxide containing is A2RuO4HyWherein y is more than 0 and less than or equal to 1. In this embodiment, a may be one of an alkali metal element, an alkaline earth metal element, and a rare earth metal element, or an alloy of two or more of them.
In one embodiment, a method for controlling physical properties of ruthenium oxide is provided. The method for controlling the physical properties of the ruthenium oxide involves a method for inserting or extracting particles. The method for regulating and controlling the physical properties of the ruthenium oxide comprises the following steps:
s102, providing a structural formula AmBnOxWherein a is one or more of an alkali metal element, an alkaline earth metal element, and a rare earth metal element. B is Ru or a metal dopant of Ru, wherein the metal dopant of Ru can be Ru and one or more of Ti, Mn, Cr, Fe, Ni, Mo, W, Ir, V, Co, Rh, Al, Sc, Zn or Cu.
In this step, the compound of formula A can be directly providedmBnOxThe oxide of (1). Or preparing the structural formula A through corresponding process stepsmRunOxThe oxide of (1). The specific structure of the ruthenium oxide is not particularly limited, and the element a may be one of an alkali metal element, an alkaline earth metal element, and a rare earth metal element. A may also be a multielement. Such as the oxide AmRunOxMay be (Sr, La) RuO3、(Na,Lu)(Fe,Ru)O3、(Ca,Ba)3(Mn,Ti)2O7、(Dy,Nd)(Ru,Sc)O3Or (Sm, Eu) (Ru, Ti) O3。
S104, providing an ionic liquid, wherein the ionic liquid comprises hydrogen ions and oxygen ions, and placing the oxide in the ionic liquid.
The type of ionic liquid may be varied as long as the desired hydrogen ions can be provided by hydrolysis or other means. Structural formula is AmRunOxMay be immersed in the ionic liquid. Thus enlarging the structural formula AmRunOxThe contact area of the oxide and the ionic liquid 202 is convenient for the ions in the ionic liquid to diffuse into the ionic liquid with the structural formula AmRunOxThe oxide of (1).
S106, applying an electric field to the ionic liquid, so that hydrogen ions in the ionic liquid are inserted into the oxide to form a compound with a structural formula of
Figure BDA0001820089450000061
The hydrogen-containing ruthenium oxide is characterized in that pm + qn + y is 2x, m is more than or equal to 0, n is more than 0, x is more than 0, y is more than 0, p is more than or equal to 1 and less than or equal to 3, and q is more than 2 and less than or equal to 8.
In this step, various methods may be used to apply an electric field to the ionic liquid. In one embodiment, a power source and two electrodes are provided. And the two electrodes are arranged at intervals and are respectively electrically connected with the power supply. The two electrodes are not limited in shape and can be parallel plate electrodes, rod electrodes and metal mesh electrodes. In one embodiment, the two electrodes are electrodes of spring-like wire. The power supply can be various direct current power supplies, alternating current power supplies and the like. The voltage of the power supply is adjustable, and can be used for controlling the reaction time. A directional electric field may be formed between the two electrodes arranged at a distance. The connection mode of the two electrodes and the power supply is not limited, and the voltage can be applied to the two electrodes through switch control. The direction of the applied electric field can also be controlled by the connection of the power supply to the two electrodes.
In this embodiment, the insertion or extraction of H ions or the insertion or extraction of H atoms is realized by applying an electric field to the ionic liquid. When the ionic liquid is at high potential, the structural formula is AmRunOxIs at a low potential. Positively charged hydrogen ions diffuse from the high potential region into the low potential region. Negatively charged oxygen ions diffuse from the low potential region into the high potential region. Structural formula is AmRunOxThe oxide of (2) is intercalated with hydrogen ions, and it is possible to appropriately extract oxygen ions. In this example, the structural formula formed by the method for controlling the physical properties of ruthenium oxide is shown in the following
Figure BDA0001820089450000071
The out-of-plane lattice constant of the ruthenium hydroxide containing compound increases. Similarly, the ruthenium hydroxide
Figure BDA0001820089450000072
The process of extracting H ions or H atoms in (1) is reverse to the process of inserting H ions or H atoms described above. The insertion process or extraction process of specific H ions or H atoms can be changed by setting the direction of the applied electric field.
In one embodiment, a method for controlling physical properties of ruthenium oxide comprises the following steps:
s202, providing a structural formula AmBnOxWherein a is one or more of an alkali metal element, an alkaline earth metal element, and a rare earth metal element. B is Ru or a metal dopant of Ru, wherein the metal dopant of Ru can be Ru and one or more of Ti, Mn, Cr, Fe, Ni, Mo, W, Ir, V, Co, Rh, Al, Sc, Zn or Cu.
This stepIn the process, the compound of formula A can be directly providedmBnOxThe oxide of (1). Or preparing the structural formula A through corresponding process stepsmRunOxThe oxide of (1). The specific structure of the ruthenium oxide is not particularly limited, and the element a may be one of an alkali metal element, an alkaline earth metal element, and a rare earth metal element. A may also be a multielement. Such as the oxide AmRunOxMay be (Sr, La) RuO3、(Na,Lu)(Fe,Ru)O3、(Ca,Ba)3(Mn,Ti)2O7、(Dy,Nd)(Ru,Sc)O3Or (Sm, Eu) (Ru, Ti) O3。
S204, providing a metal catalyst and a hydrogen-containing reaction gas.
In this step, the metal catalyst is not particularly limited as long as it can catalyze the decomposition of hydrogen gas to generate hydrogen ions. The material of the metal catalyst can be various metals, such as platinum, palladium, gold, and the like. Preferably, the metal catalyst may be platinum or palladium. The structure of the metal catalyst can be a metal nano-film, nano-particle or strip electrode. It is understood that the metal catalyst may also be combined with a compound of formula AmRunOxTo promote the insertion of the hydrogen ions into the oxide of formula AmRunOxThe oxide of (1).
S206, heating to raise the temperature from 20 ℃ to 200 ℃ to enable the hydrogen-containing reaction gas to generate hydrogen atoms under the action of the metal catalyst, wherein the hydrogen atoms are diffused and inserted into the oxide to form the hydrogen-containing ruthenium oxide,
Figure BDA0001820089450000073
wherein y is more than 0 and less than or equal to 1.
In the step, proper reaction conditions are set so that hydrogen atoms are diffused and inserted into the structural formula AmBnOxIn the oxide of (a) to form a structural formula of
Figure BDA0001820089450000074
The hydrogen-containing ruthenium oxide of (1). The metal catalyst can be combined with a structural formula A in advancemRunOxThe oxides of (a) are mixed. In the heating and temperature rising process, the hydrogen-containing reaction gas generates hydrogen atoms under the action of the metal catalyst. The hydrogen atom diffusion insertion structural formula is AmRunOxIn the oxide of (1). Generally, the transition metal oxide can be hydrogenated by hydrogen at room temperature under the action of a catalyst. However, in order to accelerate the hydrogenation rate, the system is generally heated at a low temperature. Heating the reaction chamber to raise the temperature of the hydrogen atmosphere. The temperature raising process is not particularly limited as long as the generation of the hydrogen atoms is promoted. In one embodiment, the temperature of the hydrogen atmosphere ranges from 20 degrees celsius to 200 degrees celsius. Preferably, the temperature of the hydrogen atmosphere is 150 degrees celsius.
In this embodiment, the method for controlling the physical property of the ruthenium oxide is a method for hydrogenating a metal catalyst, and can be performed in a reaction chamber. The specific form of the reaction chamber is not limited. In one embodiment, the reaction chamber is a sphere having an opening for receiving a test sample. The reaction cavity is also provided with an air charging port, an air discharging port, an observation window, a heating device and a vacuumizing device. And filling the hydrogen-containing reaction gas into the reaction cavity. The reaction chamber may be maintained at a dynamically balanced pressure. The hydrogen-containing reaction gas may be pure hydrogen. A slow release gas may be mixed with hydrogen gas for safety and to exclude oxygen from the air. Therefore, the introduced hydrogen gas may be a mixed gas of hydrogen gas and a release gas in different proportions. The slow release gas can be nitrogen, helium, neon, argon, krypton, xenon or radon. In the mixed gas of the hydrogen and the slow-release gas, the volume content of the hydrogen is 3-100%. In one embodiment, the slow release gas is argon. Preferably, the volume ratio of hydrogen to argon is 5: 95 of the mixed gas.
In this example, the insertion or extraction of particles was achieved by hydrogenation using a metal catalyst. The structural formula is AmRunOxThe oxide is hydrogenated by a metal catalyst to realize the structural formula AmRunOxInsertion or extraction of hydrogen atoms in the oxide of (1). In the structural formula AmRunOxThe insertion or extraction of a hydrogen atom in the oxide of (A) changes the structural formula to AmRunOxTo form a lattice of said oxide of formula
Figure BDA0001820089450000081
The hydrogen-containing ruthenium oxide of (1).
In one embodiment, the provided structural formula is AmRunOxWherein a is one or more of an alkali metal element, an alkaline earth metal element, and a rare earth metal element, the steps including:
s101, providing a substrate, wherein the substrate comprises a ceramic substrate, a glass substrate, a metal substrate or a polymer substrate. S103, depositing a structural formula A on the surface of the substratemRunOxThe oxide thin film of (1).
In this example, a compound of formula A is providedmRunOxThe method for producing the oxide thin film of (1). It will of course be appreciated that the formula is AmRunOxThe oxide film can be prepared by other process methods.
Specifically, the ruthenium hydroxide contained in the present application
Figure BDA0001820089450000091
The regulation and control method can be simply summarized as follows:
firstly, preparing a compound with a structural formula of AmRunOxWherein a is one or more of an alkali metal element, an alkaline earth metal element, and a rare earth metal element. The method of ion sputtering, pulse laser deposition, magnetron sputtering, molecular beam epitaxy, chemical vapor deposition and sol-gel can be adopted to prepare the structural formula A on the substratemRunOxThe oxide of (1). What is needed isThe substrate is not limited as long as the substrate can be formed to have a structural formula of AmRunOxThe oxide of (1) may be mentioned. The substrate may be a ceramic material, a glass material, a metallic material, or a polymer material. For example, the substrate may be Si, SrTiO3，LaAlO3Or Al2O3。
Next, the ruthenium hydroxide is prepared. The structural formula of the ruthenium oxide containing hydrogen is shown in the specification
Figure BDA0001820089450000092
Wherein y is more than 0 and less than or equal to 1. The oxide A can be subjected to catalytic hydrogenation by hydrogen or hydrogenation by ionic liquidmRumOxTo insert hydrogen ions.
Finally, the ruthenium hydroxide containing compounds are given in the different examples
Figure BDA0001820089450000093
Wherein y is more than 0 and less than or equal to 1, and the characterization of related performance.
In one embodiment, the ruthenium hydroxide comprises
Figure BDA0001820089450000094
Can be SrRuO3Hy，CaRuO3Hy，Sr2RuO4HyIn the form of (1).
The first embodiment is as follows: structural formula is SrRuO3HyPreparation and characterization of the ruthenium hydroxide.
In this example, SrRuO was sputtered by pulsed laser deposition3Target material in SrTiO3Deposition growth of SrRuO3A film. SrRuO3The structure of the film is characterized by means of an X-ray diffractometer (XRD for X-ray diffraction). By the reaction of SrRuO3And analyzing the film diffraction pattern to obtain the composition and structure information of the material. The XRD measurements are shown in fig. 3. In FIG. 3, the SrTiO substrate is marked with an asterisk3Characteristic peaks (001) and (002) of XRD of (A). The peak indicated by an arrow on the left side of the characteristic peak of the substrate is SrRuO3Characteristic peaks (001) and (002) of the film.
Positive voltage is applied to the Pt electrode in an ionic liquid regulation mode, so that SrRuO3The surface electrode of the film is at a low potential, and H ions are inserted into SrRuO3In the film. In the regulation and control process of the ionic liquid, in-situ measurement is carried out on SrTiO substrate3(002) Nearby XRD pattern and monitoring SrRuO3The structure of the film was changed as shown in fig. 4. H ion will insert into SrRuO3The film can realize SrRuO3HyY is more than 0 and less than or equal to 1, and can be inserted into SrRuO by applying different voltage changes3Content of H ions in the film.
The shades of black and white in figure 4 represent the intensity of the XRD peaks, with lighter colors giving higher XRD peak intensities. From FIG. 4, it is found that SrRuO increases with voltage3The characteristic peak of the film (002) is shifted in a direction of a smaller angle. When the applied voltage is higher than 1.8V, SrRuO3The characteristic peak of the film (002) was clearly shifted toward a smaller angle. This indicates SrRuO3There is a significant increase in the out-of-plane lattice constant of the film. Finally, SrRuO when the voltage reaches 2.5V3The characteristic peak of the film (002) does not move any more. At a voltage of 2.5V or more, SrRuO3The maximum hydrogenated state was reached, at which time XRD showed an expansion of the out-of-plane lattice constant of 3.3%.
Referring to FIG. 5, SrRuO is measured in situ during the regulation of the ionic liquid3Hard X-ray spectrum of Ru in the film. As shown in FIG. 5, it can be seen that the K-edge spectral line of Ru moves to the left under the regulation of the ionic liquid, the final Ru state reduces the valence of 1, and SrRuO under the regulation of the ionic liquid is reflected3The film undergoes an electrochemical reaction. SrRuO can be found when the voltage is removed3The characteristic peak of the film moves from 2 theta to the initial direction (to the right), see fig. 6. When the change of the pull-out voltage is stabilized, SrRuO can be found3The peak position of the SrRuO is still left compared with the initial state, namely the SrRuO is regulated and controlled by the ionic liquid3Film out-of-plane lattice constant ratio to original SrRuO3The film is larger. At this point, further measurement of SrRuO after voltage removal3Dichromatic ion mass spectrometry (SIMS) of the thin film to obtainSee FIG. 7 for results. The two lines on the left in FIG. 7 represent SrRuO3HyThe H content in (A) proves that about 0.2H remains in SrRuO after the ionic liquid regulation is carried out for 30 minutes under the condition of applying the voltage of 3.5V and the voltage is removed3In the unit primitive cell, H ions are involved in the electrochemical reaction regulated by the ionic liquid.
In addition, in order to verify whether the ionic liquid regulates and controls oxygen ions to participate in the electrochemical reaction process, O can be used18Regulating and controlling ionic liquid in atmosphere, and measuring SrRuO after regulating and controlling voltage is removed3O in thin film18See fig. 8 for the content variation. As shown in FIG. 8, SrRuO after ionic liquid regulation3HyMiddle O18Content and initial SrRuO3The film was unchanged. This indicates that O ions do not participate in the ionic liquid mediated electrochemical reaction. It is understood that O is defined herein18Is O16When the voltage is regulated and controlled by the ionic liquid, the isotope of (2) can also cause the change of the content of O. If there is a change in the O content of the process, the process is carried out with O18Of composition O2In the (oxygen) atmosphere, oxygen is fused into the ionic liquid and exchanges with oxygen in the material. Especially, the voltage is applied and removed in a repeated process, so if oxygen changes in the regulation process, O in the material after the ionic liquid regulation is observed18The content should be increased significantly without actually seeing O in the material18The amount of the compound is changed. Thus proving that the regulation and control process of the ionic liquid is simple towards SrRuO3The process of adding H. Furthermore, in combination with the results of the K-edge X-ray absorption spectrum of Ru, it was confirmed that the final state of hydrogenation was SrRuO3H。
In this embodiment, SrRuO can also be reflected in fig. 4 and 63The degree of hydrogenation is voltage and time dependent, so we achieved SrRuO by controlling the voltage and regulating the time3HyAnd a hydrogen content parameter y in the structure varies from 0 to 1. FIG. 5 shows a graph of SrRuO3When H is added to the film to the maximum, the valence of Ru is reduced by 1, and SrRuO3Lattice expansion of the structure, SrRuO3The reaction is carried out to generate new material SrRuO3HyY is more than 0 and less than or equal to 1. FIG. 6 may illustrate SrRuO when the applied voltage is removed3The H added in (1) is partially released, but also partially remains. As can be seen in FIG. 7, the resulting SrRuO is after the applied voltage is removed3HyWith residual H. Combining FIG. 5 with FIG. 7, SrRuO is fully demonstrated3Insertion of H in the structure, and SrRuO3The maximum H-addition state of the structure is 1H added. With reference to FIG. 6, SrRuO can be continuously adjusted3HyThe H content of (a) is continuously varied from 0 to 1, and the H content can be repeatedly adjusted between 0.2 and 1 by controlling the applied voltage. If it is desired to obtain a lower hydrogen content, a heat treatment can be used to obtain SrRuO with a lower hydrogen content3Hy. The heat treatment can be selected from annealing at 300 deg.C in ozone for 30min or reducing the temperature of oxygen at 700 deg.C and near one atmosphere to room temperature at 10 deg.C/min to obtain initial SrRuO without H3。
In this example, SrRuO can be prepared3HyWherein the content of H can be continuously adjusted from 0 to 1. And the content of H in the ionic liquid can be controlled between 0.2 and 1 by changing the input magnitude of the electric field, and the content of H can be returned to 0 by heat treatment. With the addition of H, SrRuO3HyOut-of-plane lattice constant ratio SrRuO3Increase by a maximum increment of 3.3%. To obtain SrRuO3HyIn the process, the ruthenium oxide with the valence less than 4 is obtained, and the lowest valence state of the ruthenium element is 3.
Example two: structural formula is CaRuO3HyThe preparation and characterization of the ruthenium hydroxide containing compounds of (1).
In this example, in (La)0.3Sr0.7)(Al0.6Ta0.35)O3(LSAT for short) (001) substrate sputtering of CaRuO by laser pulse deposition3Obtaining the CaRuO from the target material3A film. Then the CaRuO is regulated and controlled by the ionic liquid3The film was charged with H. Referring to FIG. 9, during the H addition control, the CaRuO was measured in situ3The film is attached at (002) angleThe near peak position changes. As shown in FIG. 9, during the addition of H, CaRuO3The out-of-plane lattice constant of the film expands under the regulation and control of the ionic liquid, and the electrochemical reaction of H insertion occurs. The measuring time of each curve is fixed to be 10 minutes, namely CaRuO can be obtained by adding a positive voltage of more than 3.5V to the ionic liquid for 10 minutes3HyThe saturated state of hydrogenation, during which different hydrogen contents can be achieved by controlling the voltage and regulating the time.
In addition, the CaRuO can be realized by adopting a hydrogen atmosphere reduction mode3And (4) hydrogenation. See FIG. 10, by CaRuO3XRD pattern of the film, providing CaRuO during the experiment3HyAnd (3) continuously hydrogenating. In the specific test process, a metal catalyst Pt and a hydrogen-containing reaction gas can be provided, and the metal catalyst Pt and the hydrogen-containing reaction gas can react with the CaRuO3The films are in full contact, and the hydrogen-containing reaction gas can generate hydrogen atoms under the action of the metal catalyst at room temperature of 25 ℃, and the hydrogen atoms are inserted into the oxide CaRuO in a diffusion mode3To form said ruthenium hydroxide containing CaRuO3HyWherein y is more than 0 and less than or equal to 1.
As shown in fig. 10, the time interval measured between each adjacent two curves in the graph is 2 minutes. Namely said oxide CaRuO3The formation of the hydrogenous ruthenium oxide, CaRuO, reached the saturation level of hydrogenation over 12 minutes3H. It will be appreciated that different degrees of hydrogenation of CaRuO are desired3Hy(different values of y) can be achieved by adjusting the time of the hydrogenation reaction.
Example three: structural formula is Sr2RuO4HyThe preparation and characterization of the ruthenium hydroxide containing compounds of (1).
In this example, Sr was sputtered by pulsed laser deposition2RuO4Target material is in LaSrAlO4(100) Preparing epitaxially grown Sr on oriented substrate2RuO4A film. And prepares Sr by the regulation and control mode of ionic liquid2RuO4Hy. Referring to FIG. 11, the process of ionic liquid regulation is shown, where the interval between each curve is 10 minutes, and when a positive voltage of 3.5V is applied for more than 10 minutesCan obtain Sr2RuO4HyIn the saturated state.
The Sr with different hydrogen contents can be realized by controlling the applied voltage and the regulation time in the regulation of the ionic liquid in the same way2RuO4HyAnd the regulated hydrogen content can be maintained after the applied voltage is removed. Besides, Sr can be realized by adopting a hydrogen atmosphere reduction mode2RuO4For the hydrogenation process, reference may be made to the above-mentioned methods, which are not described herein again.
The application of the hydrogen-containing ruthenium oxide comprises the following steps:
with SrRuO3HyFor example, SrRuO3Is a ferromagnetic metal, Tc150K, SrRuO in the hydrogenation of ionic liquid3The ferromagnetic state of (A) is rich in variation with the H content. As shown in FIG. 12, SrRuO was measured at 2K temperature at different hydrogen contents (different regulation voltage implementation)3HyThe hall resistance of (2) varies with the magnetic field strength. The hall effect is an effect in which when a current passes through a conductor perpendicular to an external magnetic field, carriers are deflected, and an additional electric field is generated in a direction perpendicular to the current and the magnetic field, thereby generating a potential difference between both ends of the conductor. This potential difference is also referred to as hall potential difference.
SrRuO3The Hall resistance (regulated voltage of 0V) is composed of both normal Hall and abnormal Hall peculiar to ferromagnetic material, and it can be seen that SrRuO increases with increasing hydrogen content (regulated voltage is increased)3HyThe abnormal Hall effect of (1.8V) is reduced, and at the same time, SrRuO is in a transition state during hydrogenation3HyThe transport behavior of (2) superimposes the contribution of additional topological hall in addition to the normal hall and the abnormal hall, which reflects SrRuO3During the hydrogenation, polar structures with a loss of symmetry occur, which likewise form non-trivial spin structures. As shown in fig. 13, when the control voltage is directly removed under the voltage value with the topological hall effect, and SIMS is measured, the sample has a significant H content, and the H content has a more significant depth-dependent distribution gradient than the H content after the voltage is removed in the fully hydrogenated state. This illustrates SrRuO3HyThe H concentration varies significantly with depth in the transition state, which is responsible for the lack of symmetry and ultimately the appearance of the topological hall effect.
In addition, when the regulation voltage was increased to 2.5V, the hydrogen content reached saturation, at which point the abnormal hall contribution completely disappeared, demonstrating SrRuO3From a ferromagnetic state to a paramagnetic state. As can be seen from FIG. 14, SrRuO3HySwitching between H-added multi-state and H-added less state can be achieved by controlling the voltage switch, and switching between ferromagnetic and paramagnetic states can be achieved at the same time, as shown in fig. 14 (here, paramagnetic state is achieved at 1.8V due to higher electrode voltage division on the surface of the thin film due to larger positive electrode area).
In addition, the hydrogen-containing ruthenium oxide has great potential application value in spintronics, topological quantum computing, topological quantum transportation and topological memory devices. Non-trivial magnetic structures such as topological hall effect reactions may be the presence of a siganus (in SrRuO)3HyWith possible presence of sigramite). The freely movable Sjgren is used as an information carrier, and the working read-write current of the freely movable Sjgren is only one ten thousandth of that of the traditional spintronics, so the hydrogen-containing ruthenium oxide can be used for manufacturing a low-energy-consumption non-volatile spin memory device.
The ruthenium hydroxide can be prepared
Figure BDA0001820089450000131
Wherein pm + qn + y is 2x, m is more than or equal to 0, n is more than 0, x is more than 0, y is more than 0, p is more than or equal to 1 and is less than or equal to 3, q is more than 2 and is less than or equal to 8, and the distribution of the hydrogen-containing ruthenium oxide H can be controlled to have larger gradient, so that symmetry break is induced in a nonpolar structure (without topology Hall effect) which does not have symmetry break originally, and the structure has topology Hall effect. At present, the materials with the topological Hall effect are found to be very few, and in addition, the structure of obtaining the topological Hall effect through an interface is also very limited. The ruthenium hydroxide-containing oxide in the present application
Figure BDA0001820089450000132
The regulation and control method of (2) can change the H content. To pairThe topological Hall effect induced by H can be controlled by temperature and magnetic field, and can be adjusted by a certain H content. That is, the topological hall effect can be further altered by changing the applied voltage to change the H content of the ruthenium hydroxide-containing oxide. Fig. 15 shows the topological hall variation at different voltages.
In one embodiment, there is provided an electronic device comprising the ruthenium hydroxide containing oxide as described in any of the above. The electronic device can be an electric control switch, a magnetic control switch, a logic unit, a topological quantum calculator, a spinning electronic device and a non-volatile spinning storage device.
In this embodiment, the application of the device for electrically controlling magnetism can be realized by controlling the ferromagnetic-paramagnetic phase change of the hydrogen-containing ruthenium oxide by using an electric field. The magnetic ground state (ferromagnetic and paramagnetic) of the hydrogenruthenium oxide can also be changed repeatedly to serve as a magnetic switch or logic cell. In addition, the hydrogen-containing ruthenium oxide and the regulation and control method thereof realize the hydrogenation of ruthenium oxide by applying an electric field, the regulation and control method is simple and easy to implement, and the regulation and control degree in the preparation process is larger (SrRuO)3With a maximum of 1H insertion). There is also much room for study of the performance of the ruthenium hydroxide formed in examples two and three in this application. Subsequent research can further expand the application value of the ruthenium hydroxide based on the hydrogen-containing oxide provided by the application.
The above-mentioned embodiments only express several embodiments of the present application, and are described in detail and concrete, but not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (11)

1. The hydrogen-containing ruthenium oxide is characterized in that the structural formula of the hydrogen-containing ruthenium oxide is shown in the specification
Figure RE-DEST_PATH_IMAGE001
Wherein, in the step (A),
a is one or more of alkali metal elements, alkaline earth metal elements and rare earth metal elements;
b is Ru or a metal dopant of Ru, wherein the metal dopant of Ru can be one or more of Ru and Ti, Mn, Cr, Fe, Ni, Mo, W, Ir, V, Co, Rh, Al, Sc, Zn or Cu;
Figure RE-358180DEST_PATH_IMAGE004
m≥0，n＞0，x＞0，y＞0，1≤p≤3，2＜q≤4。
2. the ruthenium hydroxide according to claim 1, wherein 0 <y≤2n。
3. The ruthenium hydroxide according to claim 1, wherein 0 <y≤n。
4. The ruthenium hydride-containing oxide according to any one of claims 1 to 3, wherein the alkali metal element is one or more of Li, Na, K;
the alkaline earth metal element is one or more of Be, Mg, Ca, Sr and Ba;
the rare earth metal elements are one or more of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc.
5. The ruthenium hydroxide according to claim 1, wherein the ruthenium hydroxide is ARuO3HyWherein y is more than 0 and less than or equal to 1.
6. The ruthenium hydrogencontaining oxide according to claim 3, wherein the ruthenium hydrogencontaining oxide is A2RuO4HyWherein y is more than 0 and less than or equal to 1.
7. A method for controlling the physical properties of ruthenium oxide is characterized by comprising the following steps:
s102, providing a structural formula
Figure RE-DEST_PATH_IMAGE005
Wherein m is more than or equal to 0, n is more than 0, x is more than 0, A is one or more of alkali metal elements, alkaline earth metal elements and rare earth metal elements, B is Ru or a metal dopant of Ru, wherein the metal dopant of Ru can be one or more of Ru and Ti, Mn, Cr, Fe, Ni, Mo, W, Ir, V, Co, Rh, Al, Sc, Zn or Cu;
s104, providing an ionic liquid, wherein the ionic liquid comprises hydrogen ions and oxygen ions, and placing the oxide in the ionic liquid;
s106, applying an electric field to the ionic liquid, so that hydrogen ions in the ionic liquid are inserted into the oxide to form a compound with a structural formula of
Figure RE-635708DEST_PATH_IMAGE001
The hydrogen-containing ruthenium oxide according to (1), wherein,
Figure RE-835746DEST_PATH_IMAGE006
m≥0，n＞0，x＞0，y＞0，1≤p≤3，2＜q≤4。
8. the method for controlling physical properties of ruthenium oxide according to claim 7, wherein the structural formula is
Figure RE-360268DEST_PATH_IMAGE005
The oxide of (a) is obtained by means of pulsed laser deposition.
9. A method for controlling the physical properties of ruthenium oxide is characterized by comprising the following steps:
s202, providing a structural formula
Figure RE-691761DEST_PATH_IMAGE005
Wherein m is more than or equal to 0, n is more than 0, x is more than 0, A is one or more of alkali metal elements, alkaline earth metal elements and rare earth metal elements, B is Ru or a metal dopant of Ru, wherein the metal dopant of Ru can be one or more of Ru and Ti, Mn, Cr, Fe, Ni, Mo, W, Ir, V, Co, Rh, Al, Sc, Zn or Cu;
s204, providing a metal catalyst and a hydrogen-containing reaction gas;
s206, heating to 20-200 ℃ to enable the hydrogen-containing reaction gas to generate hydrogen atoms under the action of the metal catalyst, wherein the hydrogen atoms are diffused and inserted into the oxide to form a structural formula
Figure RE-959931DEST_PATH_IMAGE001
The hydrogen-containing ruthenium oxide according to (1), wherein,
Figure RE-14475DEST_PATH_IMAGE006
m≥0，n＞0，x＞0，y＞0，1≤p≤3，2＜q≤4。
10. the method for controlling physical properties of ruthenium oxide according to claim 9, wherein the structural formula is
Figure RE-991789DEST_PATH_IMAGE005
The oxide of (a) is obtained by means of pulsed laser deposition.
11. An electronic device comprising the ruthenium hydroxide according to any one of claims 1 to 6.
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