WO2018161643A1

WO2018161643A1 - Stress control method

Info

Publication number: WO2018161643A1
Application number: PCT/CN2017/113206
Authority: WO
Inventors: 于浦; 李卓璐
Original assignee: 清华大学
Priority date: 2017-03-06
Filing date: 2017-11-27
Publication date: 2018-09-13
Also published as: CN108525609B; CN108525609A

Abstract

The present application relates to a stress control method, comprising: providing a first material (110), wherein a chemical formula of the first material (110) is ABOxHy, wherein A represents one or more of alkaline earth metal elements and rare earth metal elements, B represents one or more of transitional metal elements, x ranges from 1 to 3, and y ranges from 0 to 3; providing a second material (120), wherein the second material (120) and the first material (110) are in contact with each other and form a contact interface; performing insertion or extraction of ions or atoms on the first material (110) to change a lattice constant of the first material (110); and effectively controlling stress of the second material (120) by means of the contact interface. The stress control method can apply greater lasting stress to the second material (120).

Description

Stress control method

Related application

The present application claims the benefit of priority to the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the present disclosure.

Technical field

The present application relates to the field of material technology, and in particular to a stress control method.

Background technique

Stress is an internal force that creates an interaction between parts of an object when it is deformed by external factors (force, humidity, temperature field changes, etc.). Stress regulation changes the stress of an object, and it can apply stress or release stress. The internal structure of a substance changes under stress control, and a series of physical properties of the substance (such as electromagnetic properties, transport properties, dielectric properties, etc.) also change.

A conventional method of applying integral stress is to apply pressure to a sample in a sample chamber through a pressure transmitting medium using a diamond to thimble. The stress applied by the method of diamond to thimble can reach the order of 100 Gpa. A conventional method of applying biaxial stress is to deposit a film material on a substrate PMN-PT using 0.67 Pb (Mg _1/3 Nb _2/3 )O ₃ -0.33 PbTiO ₃ (PMN-PT) as a substrate. The substrate PMN-PT deforms under an applied electric field, thereby providing biaxial stress to the upper film. When the applied electric field strength of PMN-PT is 10kV/cm, the in-plane stress can reach 0.63%. The traditional method of applying uniaxial stress is to use a ZnO ₂ piston to the top sample. The stress that can be achieved by the method of using the ZnO ₂ piston to the top sample reaches the order of 100 MPa. According to the 1Gpa approximation, the 1% stress can be equivalent, and the traditional method of applying uniaxial stress can achieve stress regulation of no more than 1%. It can be seen that the uniaxial and biaxial stress-applying methods in the conventional scheme cannot apply large stresses. In addition, once all of the above methods of applying stress are removed, the sample is restored to the state where it is initially unstressed, and the stress state cannot be effectively maintained.

Summary of the invention

Based on this, it is necessary to apply a large stress to the uniaxial and biaxial stress-applying methods, and all conventional stress-applying methods provide a stress-regulating method once the defects that cannot maintain the sample in the stress state are removed.

A stress control method comprising: S10, providing a first material having a structural formula of ABO _x H _y , wherein A is one or more of an alkaline earth metal element and a rare earth metal element, and B is a transition metal element Or multiple, x ranges from 1-3, and y ranges from 0 to 3;

S20, providing a second material, contacting the first material with the second material and forming a contact interface between the first material and the second material;

S30, inserting or extracting particles into the first material, changing a lattice constant of the first material, and realizing stress regulation on the second material, the particles including one or more of ions and atoms.

In one embodiment, the ions include hydrogen ions, lithium ions, sodium ions, potassium ions, barium ions, barium ions, magnesium ions, calcium ions, barium ions, barium ions, nitrogen ions, phosphorus ions, oxygen ions, sulfur. One or more of ions, selenium ions, and fluoride ions;

The atom includes a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, a helium atom, a helium atom, a magnesium atom, a calcium atom, a helium atom, a helium atom, a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom, a selenium atom, and fluorine. One or more of the atoms.

In one embodiment, the second material comprises one or more of a metal element, a metal oxide, an alloy.

In one embodiment, the second material comprises a nano material comprising zero-dimensional clusters, artificial atoms, nanoparticles; one-dimensional nanowires, nanotubes, nanorods, nanofibers; two-dimensional Nanobelts, ultrathin films, multilayer films.

In one embodiment, the second material comprises an organic functional material including an organic material having mechanical functions, an organic material having chemical functions, an organic material having physicochemical functions, and an organic having biochemical functions. Materials, organic materials with electrical functions.

In one embodiment, the S30 includes:

S301, providing an ionic liquid, wherein the ionic liquid contains hydrogen ions and oxygen ions, and the first material and the second material are disposed in the ionic liquid;

S303, applying an electric field to the ionic liquid such that hydrogen ions or oxygen ions in the ionic liquid are inserted into the first material, or hydrogen ions or oxygen ions are extracted from the first material.

In one embodiment, in S303, the ionic liquid is at a high potential, the first material is at a low potential, and hydrogen ions in the ionic liquid are inserted into the first material or oxygen ions from the first The material is extracted such that the out-of-plane lattice constant of the first material is increased to apply a tensile stress to the second material to effect stress regulation of the second material.

In one embodiment, in S303, the ionic liquid is at a low potential, the first material is at a high potential, and oxygen ions in the ionic liquid are inserted into the first material or hydrogen ions from the first The material is extracted such that the out-of-plane lattice constant of the first material is reduced, thereby applying a compressive stress to the second material to effect stress regulation of the second material.

In one embodiment, the S30 includes:

S302, providing a metal catalyst and a hydrogen-containing reaction gas;

S304, heating and heating to 20 degrees Celsius to 200 degrees Celsius, causing the hydrogen-containing reaction gas to generate hydrogen atoms under the action of the metal catalyst, the hydrogen atoms being diffused into the first material to make the first material The lattice constant changes.

In one embodiment, the S30 includes:

S305, providing an oxygen-containing reaction gas;

S307, heating the first material and the second material to a temperature of 200 degrees Celsius to 400 degrees Celsius, wherein the first material is oxidized by an oxygen-containing reaction gas, and oxygen is diffused into the first material in the form of oxygen atoms. Medium to change the lattice constant of the first material.

The stress control method provided by the present application provides a first material and a second material. The structural formula of the first material is ABO _x H _y . Wherein A is one or more of an alkaline earth metal element and a rare earth metal element. B is one or more of transition metal elements. The value of x ranges from 1-3, and the range of y ranges from 0 to 3. The first material is contacted with the second material. And forming a contact interface between the first material and the second material. The lattice constant of the first material is changed by the insertion or extraction of particles. Stress regulation of the second material is achieved by a change in the lattice constant of the first material. The stress control method provided by the present application, the first material can apply a permanent and large stress to the second material through the contact interface.

DRAWINGS

1 is a flow chart of a stress control method according to an embodiment of the present application;

2a is a schematic structural view of a first material and a second material having a 2-2 type structure in a stress control method according to an embodiment of the present application;

2b is a schematic structural view of a first material and a second material having a 0-0 type structure in a stress control method according to an embodiment of the present application;

2c is a schematic structural view of a first material and a second material having a 1-3 type structure in a stress control method according to an embodiment of the present application;

2d is a schematic structural view of a first material and a second material having a 0-3 type structure in a stress control method according to an embodiment of the present application;

3 is a schematic diagram of a process for inserting or extracting particles by using an ionic liquid plus electric field method in a stress control method according to an embodiment of the present application;

4 is a schematic view showing a process of inserting or extracting particles by using a method of hydrogenating a metal catalyst in a stress control method according to an embodiment of the present application;

5 is a schematic diagram of a process for inserting or extracting particles by using an ozone annealing method in a stress control method according to an embodiment of the present application;

6 is an X-ray diffraction diagram of a first material before and after stress control according to another embodiment of the present application;

7 is a partial enlarged view of an X-ray diffraction pattern of a first material before and after stress control according to another embodiment of the present application;

8 is an X-ray diffraction diagram of a first material before and after stress control according to another embodiment of the present application;

9 is a partial enlarged view of an X-ray diffraction pattern of a first material before and after stress control according to another embodiment of the present application;

10 is a topographical view of a first material and a second material provided by another embodiment of the present application;

Figure 11 is an X-ray diffraction diagram of a first material and a second material provided in still another embodiment of the present application;

12 is an in-situ X-ray diffraction pattern of a first material and a second material stress regulation process according to still another embodiment of the present application.

detailed description

In order to make the objects, technical solutions and advantages of the present application more clear, the stress control method of the present application will be further described in detail below with reference to the accompanying drawings and embodiments. It is understood that the specific embodiments described herein are merely illustrative of the application and are not intended to be limiting.

Referring to FIG. 1 , a stress control method provided by the present application includes:

S10, providing a first material 110 of the formula ABO _x H _y . Wherein A is one or more of an alkaline earth metal element and a rare earth metal element. B is one or more of transition metal elements. The value of x ranges from 1-3, and the range of y ranges from 0 to 3.

In the ABO _x H _y , A is one or more of an alkaline earth metal element and a rare earth metal element. B is one or more of transition metal elements. The value of x ranges from 1-3, and the range of y ranges from 0 to 3. In one embodiment, the value of x ranges from 1-3, and the range of y ranges from greater than 0 to less than or equal to 3. Specifically, the ratio of A and B in ABO _x H _y is not necessarily strictly 1:1. The ratio of the A and B, which because of vacancy and interstitial atom and the like in the ABO _x H _y departing generated. Therefore, it can be understood that all of the ABO _x H _y whose ratio of A to B is close to 1:1 are within the scope of the present application. The alkaline earth metal may include one or more of Be, Mg, Ca, Sr, Ba. The rare earth metal element may include one or more of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb. The transition group element may include one or more of Co, Cr, Fe, Mn, Ni, Cu, Ti, Zn, Sc, and V. It can be understood that A can also be a mixture of an alkaline earth metal and a rare earth metal. B may also be a mixture of a transition metal and a main group metal. In one embodiment, the first material 110 may be a hydrogen-containing transition metal oxide of the formula ABO _x H _y .

S20, providing a second material 120, contacting the first material 110 with the second material 120. And forming a contact interface between the first material 110 and the second material 120.

The contact interface is a contact surface of the first material 110 and the second material 120. Specifically, the size and shape of the contact interface are not specifically limited. The contact interface may be a regular shape or an irregular shape. The shape of the contact interface may be determined according to different configurations of the first material 110 and the second material 120. For example, the first material 110 and the second material 120 are alternately layered, and the contact interface is a boundary where the two materials contact each other. The atoms of the first material 110 and the second material 120 at the contact interface are tightly connected at together. When the lattice constant of the first material 110 changes, the arrangement of atoms at the contact interface changes. The atomic arrangement of the second material 120 also varies. Thereby a stress is applied to the second material 120. Through the contact interface, the first material 110 can regulate the magnitude of the stress received by the second material 120 by inserting or extracting particles.

S30, inserting particles into the first material 110 to change a lattice constant of the first material 110 to achieve stress regulation on the second material 120. The particles include one or more of ions and atoms.

Inserting particles into the first material 110, insertion can be understood as combining with the first material 110 to form a new structure. The lattice constant of the new structure formed is different from the lattice constant of the first material 110. The particles include one or more of ions and atoms. Insertion or extraction of one or more particles, insertion or extraction of one or more ions, and insertion or extraction of one or more atoms can also be achieved.

The methods of inserting or extracting particles include: an ionic liquid plus electric field method, a different gas atmosphere catalysis method, a different gas atmosphere annealing method, or an electrolyte insertion method. The above series of methods for providing insertion or extraction of particles are merely examples, and the specific method of providing ions or atoms is not limited as long as the insertion or extraction of particles can be achieved.

In the stress control method in this embodiment, the stress of the second material 120 is adjusted by changing the lattice constant of the first material 110. The lattice constant of the first material 110 can be effectively adjusted by the insertion or extraction of particles. After the lattice constant of the first material 110 is changed, the lattice constant of the second material 120 is further changed by the coupling effect of the interface. Effective regulation of the magnitude of the stress of the second material 120 is achieved. In the stress control method provided by the present application, the first material 110 can apply a permanent stress to the second material 120 through the contact interface. The lattice constant of the first material 110 is changed, and stress may be applied to the second material 120. The change in the lattice constant of the first material 110 also causes a change in the lattice constant of the second material 120. The change in the lattice constant of the second material 120 also brings about a change in the stress state of the second material 120. And the stress control method provided by the present application is more stress applied than the conventional method. Specifically, the tensile stress applied by the stress control method provided by the present application can reach 6% or even higher, and the compressive stress applied by the stress control method provided by the present application can be 3.5% or even higher.

In this embodiment, the insertion or extraction of the particles can be achieved by an electrolyte insertion method. For the insertion or extraction of a positively charged cation such as a lithium ion, a sodium ion, a potassium ion, a cesium ion, a strontium ion, a magnesium ion, a calcium ion, a strontium ion or a strontium ion, an electrode may be provided in the electrolyte containing the cation described above. A sample to be inserted or withdrawn from the particles is disposed in the electrolyte. Then, the above cation is inserted into the sample by applying a potential higher than the sample to the electrode. Alternatively, it is also possible to apply a potential lower than the sample to the electrode to extract the above cation from the sample. The sample is composed of the first material 110 and the second material 120, the first material 110 and the second material 120 are in contact and form a contact between the first material 110 and the second material 120 interface. The above cation insertion or extraction changes the lattice constant of the first material 110. Different degrees of stress are applied to the second material 120 by the first material 110. For example, a cationic conductor electrolyte, Na-β-Al ₂ O ₃ , can be provided. The Na-β-Al ₂ O _{3 is} substantially NaAl ₁₁ O ₁₇ , and the electrolyte NaAl ₁₁ O ₁₇ can generate sodium ions, in which sodium ions can move, and is inserted into the first material under the drive of an applied electric field. 110, or extracted from the first material 110.

For negatively charged anions such as nitrogen ions, fluoride ions, phosphorus ions, sulfur ions, selenium ions, etc., it is possible to insert the above anions by applying a potential lower than the sample on the counter electrode in the electrolyte containing the above anions. Similarly, the sample is provided in the electrolyte containing the above anion. Alternatively, a high potential is applied to the electrode to extract the anion. For example, an anion conductor electrolyte, lead fluoride PbF ₂ can be provided. The electrolyte lead fluoride PbF ₂ may generate fluorine ions in which fluorine ions may freely move and are inserted into or withdrawn from the first material 110 by an applied electric field. Similar fluoride ion conductors may also be CaF ₂ , SrF ₂ , BaF ₂ and materials having a fluoranthene and YF ₃ structure. An oxygen ion conductor electrolyte can also be provided to effect insertion or extraction of oxygen ions, such as Zr(Y)O ₂ .

The insertion and extraction of atoms can be similarly taught by providing the above atoms through the material, and the difference in atomic concentration produces a gradient potential that causes the atoms to diffuse from a high concentration to a low concentration. A lithium atom, a sodium atom, a potassium atom, a ruthenium atom, a ruthenium atom, a magnesium atom, a calcium atom, a ruthenium atom, a ruthenium atom, a nitrogen atom, a phosphorus atom, a sulfur atom, or a selenium atom can be inserted or extracted in a manner similar to the foregoing. The atoms diffused into the first material 110 may be in a free form in the first material 110, and may also react with the first material 110 to form a bond. For example, the insertion or extraction of fluorine atoms can also be achieved by fluorine-containing organic or fluorine-containing nanomaterials. Specifically, it can be spin-coated to the first material by a vinylidene fluoride (PVDF) solution. The surface of the 110 further anneals the first material 110 to promote diffusion of fluorine atoms into the first material 110 and react with the first material 110 to form fluoride.

It can be understood that other methods can be used for inserting or extracting particles. A method of achieving stress regulation by changing the lattice constant of the first material 110 is within the scope of the present application.

In one embodiment, the second material 120 comprises one or more of a metal element, a metal oxide, an alloy.

In one embodiment, the second material 120 is a simple substance of metal. The metal element includes one or more of potassium, calcium, sodium, magnesium, aluminum, zinc, iron, copper, lead, and nickel. It can be understood that the metal element can be any metal element.

In one embodiment, the second material 120 is a simple substance of metal. The properties of the second material 120 can be effectively changed by changing the lattice constant of the first material 110 in this embodiment. For example, a tensile stress or a compressive stress is applied to the metal element by changing the lattice constant of the first material 110. After the stress of the metal element is changed, the ductility, electrical conductivity and thermal conductivity of the metal element are correspondingly changed.

In one embodiment, the second material 120 is a metal oxide. The metal oxide is a binary compound composed of an oxygen element and another metal chemical element such as iron oxide (Fe ₂ O ₃ ), nickel oxide (NiO), or the like. An important role of the metal oxide is as a catalyst, which plays an important role in different reactions. In this embodiment, the first material 110 is the hydrogen-containing transition metal oxide, and the second material 120 is a metal oxide. A tensile stress or a compressive stress is applied to the metal oxide by changing the lattice constant of the first material 110, thereby further changing the catalytic properties of the metal oxide, and improving the catalytic efficiency of the metal oxide.

In one embodiment, the second material 120 is an alloy. The alloy is a material having metal characteristics synthesized by a certain method from two or more metals and metals or nonmetals. Alloys can be divided into: mixture alloys (eutectic mixtures), solid solution alloys, and intermetallic compounds. The alloy of the mixture (co-melting mixture) is an alloy formed by crystallizing the components of the alloy when the liquid alloy is solidified, such as solder, cadmium-cadmium alloy or the like. The solid solution alloy is an alloy that forms a solid solution when the liquid alloy solidifies, such as a gold-silver alloy or the like. The intermetallic compound, that is, an alloy in which the components form a compound with each other, such as brass composed of copper or zinc (β-brass, γ-brass, and ε-brass). In this embodiment, the first material 110 is the hydrogen-containing transition metal oxide, and the second material 120 is an alloy. By changing the lattice constant of the first material 110, tensile stress or compressive stress is applied to the alloy, thereby further changing the electrical conductivity, thermal conductivity, corrosion resistance of the alloy, and improving the application value of the alloy. .

In one embodiment, the second material 120 comprises a nanomaterial. The nanomaterial is based on a nanoscale material unit, and a new system is constructed or assembled according to a certain rule. The nanomaterials can be divided into blocks, films, multilayer films, and nanostructures. The basic constituent units of the nano material are zero-dimensional nano materials, one-dimensional nano materials, and two-dimensional nano materials. Zero-dimensional nanomaterials can be clusters, artificial atoms, and nanoparticles. One-dimensional nanomaterials can be nanowires, nanotubes, nanorods, and nanofibers. The two-dimensional nano material can be a nanobelt, an ultrathin film, or a multilayer film. The nanostructures are in contact with the hydrogen-containing transition metal oxide, and the interatomic interactions at the interface cause the atoms to be tightly coupled together. When the lattice constant of the hydrogen-containing transition metal oxide changes, tensile stress or compressive stress is applied to the nanomaterial. After the nanomaterial is subjected to stress adjustment, its crystal structure changes. Because some properties of nanomaterials, such as the energy level structure, depend on the specific lattice structure and applied stress of the material itself. Therefore, when the lattice constant of the first material 110 is changed, the lattice constant of the second material 120 also changes. The lattice constant of the second material 120 is changed to affect the energy level structure of the second material 120, so that the second material 120 exhibits superior performance. For example, high nonlinear optical effects, light absorption, light reflection and light transport properties, specific catalytic properties, strong oxidative properties and reducibility. The nanomaterials may include graphene and carbon nanotubes.

In one embodiment, the second material 120 comprises an organic functional material. The organic functional material refers to organic small molecules, supramolecular and polymeric materials having unique physical and chemical properties (functions). The main functional types of the organic functional materials are: mechanical function, chemical function, physical and chemical function, biochemical function, and electrical function. The organic functional materials are: liquid crystal materials, laser dyes, photochromic materials, photoconductive materials, solar cell materials, organic dielectric materials. The organic dielectric material, such as polyvinylidene fluoride (PVDF), has a change in dielectric properties under applied stress. In one embodiment, the first material 110 is the hydrogen-containing transition metal oxide ABO _x H _y and the second material 120 is an organic dielectric material PVDF. A tensile stress or a compressive stress is applied to the organic dielectric material PVDF by changing a lattice constant of the first material 110, thereby further changing the dielectric properties of the organic dielectric material PVDF.

Referring to Figures 2a, 2b, 2c and 2d, the above figures show four different configurations of the first material 110 and the second material 120. The regulation of the stress of the second material 120 in the above four configurations can be achieved by the control method of the present application. The four different configurations in the figures can be deposited on the substrate 140 or form an individual support structure.

Referring to FIG. 2a, in one embodiment, the first material 110 and the second material 120 are alternately layered. When the first material 110 and the second material 120 are alternately layered, the thickness of the layer is not limited. Can root The thickness of each layer is set according to the size and uniformity of the stress to be regulated.

Referring to FIG. 2b, in one embodiment, the first materials 110 are distributed in a block-like interval. The second material 120 is the same shape as the first material 110. The second material 120 and the first material 110 are alternately layered in a vertical direction. In this embodiment, a third material 130 may also be included. The third material 130 is distributed in a block array formed by the first material 110 and the second material 120. It can be understood that the first material 110 and the second material 120 are alternately layered in the vertical direction. In the vertical direction, alternating layers are added upwards. And spaced apart in the horizontal direction, that is, the first material 110 and the second material 120 constitute a layered array. A gap is formed between one of the layered arrays and the other of the layered arrays. A third material 130 is distributed at the interval formed by the first material 110 and the second material 120. Specifically, a third material 130 is distributed between the adjacent first materials 110 and between the adjacent second materials 120. The adjustment of the stress magnitude of the second material 120 and the third material 130 can be simultaneously achieved by the change in the lattice constant of the first material 110. For example, the first material 110 is the hydrogen-containing transition metal oxide, and the second material 120 is a magnetostrictive material. The lattice constant of the first material 110 is changed by an ionic liquid plus electric field method, thereby achieving a change in the stress magnitude of the magnetostrictive material. That is, magnetoelectric coupling is achieved. At this time, the third material 130 is selected as a photostrictive material, lead zirconate titanate (PLZT) ceramic. The change in the magnitude of the stress of the photostrictive material is achieved by varying the lattice constant of the first material 110. That is, the regulation of three physical properties of light, magnetism and electricity can be realized.

In one embodiment, the third material 130 may be selected from the material of the second material 120 and different from the material of the second material 120. Specifically, the third material 130 may be a conductive material in a metal oxide, such as SrRuO ₃ . After the conductive material SrRuO ₃ is added at the interval formed by the first material 110 and the second material 120, an ionic liquid is further applied to effect insertion or extraction of ions. During the insertion or extraction of ions, the lattice constant of the first material 110 is changed, thereby regulating the stress level of the second material 120 and the third material SrRuO ₃ .

In one embodiment, the first material 110 is brought into contact with the second material 120. The step of forming the contact interface is specifically such that one of the first material 110 and the second material 120 is wrapped by another material. In one embodiment, one of the first material 110 and the second material 120 is wrapped by another material. Specifically, the second material 120 may wrap the first material 110. It is also possible that the first material 110 wraps the second material 120.

In one embodiment, the first material 110 is dispersed in the second material 120 in a dot shape, a line shape, a surface shape or a body shape. It can be understood that the first material 110 is dispersed in the second material 120 in different shapes. The shape and configuration of the first material 110 are not specifically limited. The first material 110 and the second material 120 have a contact interface that enables the second material 120 to vary depending on the change of the first material 110.

Referring to FIG. 2c, in one embodiment, the first materials 110 form an array. The second material 120 wraps the first material 110, and the array includes the first material 110 in a columnar shape. In this embodiment, the first material 110 is an intermediate columnar array. The first material 110 is the hydrogen-containing transition metal oxide. The second material 120 is in contact with the first material 110. The first material 110 and the second material 120 have a contact interface. The lattice constant of the first material 110 is changed by insertion or extraction of ions or insertion or extraction of atoms. The regulation of different stress levels of the second material 120 is achieved by the contact interface.

Referring to FIG. 2d, in one embodiment, the first material 110 forms an array and the second material 120 wraps the first material 110. The array includes the first material 110 in a block shape. In this embodiment, the first material 110 is an intermediate block array, and the first material 110 is the hydrogen-containing transition metal oxide. The second material 120 is in contact with the first material 110. The first material 110 and the second material 120 have a contact interface. In this embodiment, the contact interface between the first material 110 and the second material 120 is relatively large, and the corresponding stress control capability is relatively strong. It can be understood that, in a specific application process, any of the first material 110 and the second material 120 adopting four configurations may be further determined according to different requirements.

Please refer to FIG. 3 , which is a schematic diagram of a process for inserting or extracting particles by using an ionic liquid plus electric field method in the stress control method provided by the present application. A first material 110 and a second material 120 are deposited on the substrate 140 in FIG.

In one embodiment, the S30 includes:

S301, an ionic liquid 202 is provided. The ionic liquid 202 contains hydrogen ions and oxygen ions, and the first material 110 and the second material 120 are disposed in the ionic liquid 202.

The ionic liquid 202 contains hydrogen ions and oxygen ions. The type of the ionic liquid 202 may be various as long as the desired hydrogen ions and oxygen ions can be supplied by hydrolysis or other means. The first material 110 and the second material 120 may be immersed in the ionic liquid 202. This enlarges the contact area of the first material 110 and the second material 120 with the ionic liquid 202. Ions in the ionic liquid 202 are facilitated to diffuse into the first material 110.

S303, an electric field is applied to the ionic liquid 202 such that hydrogen ions or oxygen ions in the ionic liquid 202 are inserted into the first material 110, or hydrogen ions or oxygen ions are extracted from the first material 110.

It can be understood that there are various methods for applying an electric field to the first material 110. In one embodiment, the first electrode 210 may be formed on the surface of the first material 110 and the second material 120. The shape of the first electrode 210 is not limited and may be a parallel plate electrode, a rod electrode, or a metal mesh electrode. Hydrogen ion insertion and oxygen ion extraction in the ionic liquid 202 are controlled by the direction of the electric field to extract the first material 110, or oxygen ion insertion and hydrogen ion extraction of the first material 110. Hydrogen ions and oxygen ions are derived from water in the ionic liquid 202. In the ionic liquid 202, the content of water is not limited. Experiments have confirmed that the diffusion of hydrogen ions and oxygen ions described above can be achieved as long as the ionic liquid 202 has a small amount of water (>100 ppm).

In one embodiment, the S303 further includes: providing the second electrode 220 and the power source 230. The second electrode 220 is spaced apart from the first electrode 210 and electrically connected to the power source 230, respectively. The shape of the second electrode 220 is not limited, and may be a parallel plate electrode, a rod electrode, or a metal mesh electrode. In one embodiment, the second electrode 220 is an electrode composed of a spring-like wire. The power source 230 can be various DC, AC power sources 230, and the like. The voltage of the power source 230 is adjustable and can be used to control the reaction time.

In one embodiment, the second electrode 220 is spaced apart from the first electrode 210. An oriented electric field is formed between the second electrode 220 and the first electrode 210. The second electrode 220 and the first electrode 210 are connected to the DC power source 230 in an unrestricted manner, and a voltage may be applied to the second electrode 220 and the second electrode 220 by switch control. The direction in which the electric field is applied can be controlled by the manner in which the power source 230 is connected to the first electrode 210 and the second electrode 220.

In the present embodiment, the insertion or extraction of ions or the insertion or extraction of atoms is carried out by means of an ionic liquid plus an electric field. When the ionic liquid 202 is at a high potential, the first material 110 is at a low potential. The 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. Hydrogen ions are inserted into the first material 110 while oxygen ions are extracted. The out-of-plane lattice constant of the first material 110 is increased. A tensile stress is applied to the second material 120 through the contact interface. When the ionic liquid 202 is at a low potential, the first material 110 is at a high potential. The 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. Oxygen ions are inserted into the first material 110 while hydrogen ions are extracted. The first material 110 The out-of-plane lattice constant is reduced. A compressive stress is applied to the second material 120 through the contact interface.

Please refer to FIG. 4 . FIG. 4 is a schematic diagram of a process for inserting or extracting particles by using a method for hydrogenating a metal catalyst in a stress control method according to an embodiment of the present application. The first material 110 and the second material 120 are deposited on the substrate 140 in FIG.

In one embodiment, the S30 includes:

S302, providing a metal catalyst 201 and a hydrogen-containing reaction gas.

In one embodiment, the metal catalyst 201 is not limited as long as it can catalyze the decomposition of hydrogen to generate hydrogen ions. The material of the metal catalyst 201 may be various metals such as platinum, palladium, gold, or the like. Preferably, the metal catalyst 201 may be platinum or palladium. The structure of the metal catalyst 201 may be a nano thin film of a metal, a nanoparticle or a strip electrode. It can be understood that the metal catalyst 201 can also be in contact with the surface of the first material 110 to facilitate the insertion of the hydrogen ions into the first material 110.

S304, heating and heating up to 20 degrees Celsius to 200 degrees Celsius, so that the hydrogen-containing reaction gas generates hydrogen atoms under the action of the metal catalyst 201. The hydrogen atoms are diffused into the first material 110 to change a lattice constant of the first material 110.

The method of hydrogenating the metal catalyst of this embodiment can be carried out 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 taking a test sample. The reaction chamber also has a charging and discharging port, an observation window, a heating device and a vacuuming device. The hydrogen-containing reaction gas is charged into the reaction chamber. The reaction chamber can maintain a dynamically balanced pressure. The hydrogen-containing reaction gas may be pure hydrogen. For safety reasons and to isolate oxygen from the air, a slow release gas can be mixed in the hydrogen. Therefore, the hydrogen gas that is introduced may also be a mixed gas of different ratios of hydrogen gas and slow-release gas. The sustained release gas may be nitrogen, helium, neon, argon, helium, neon or xenon. In the mixed gas of the hydrogen gas and the sustained-release gas, the volume content of the hydrogen gas is 3% to 100%. In one embodiment, the sustained release gas is selected from argon. Preferably, a mixed gas of hydrogen gas and argon in a volume ratio of 5:95 is used.

It can be understood that in the embodiment, the metal catalyst 201 can be mixed with the first material 110 and the second material 120 in advance. The hydrogen-containing reaction gas generates hydrogen atoms under the action of the metal catalyst 201 during heating and heating. The hydrogen atoms are diffused into the first material 110. The transition metal oxide can be hydrogenated under the action of a catalyst at room temperature. However, in order to accelerate the hydrogenation rate, the system is generally subjected to low temperature heating. Heating the said The reaction chamber is raised to raise the temperature of the hydrogen atmosphere. In the temperature rising process, the heating temperature is not particularly limited as long as the generation of the hydrogen atoms can be promoted. In one embodiment, the hydrogen atmosphere has a temperature ranging from 20 degrees Celsius to 200 degrees Celsius. Preferably, the temperature of the hydrogen atmosphere is 150 degrees Celsius.

In this embodiment, the insertion or extraction of particles is achieved by a method of hydrogenating a metal catalyst. The first material 110 and the second secondary material 120 are subjected to hydrogenation of a metal catalyst to effect insertion or extraction of hydrogen atoms in the first material 110. Insertion or extraction of hydrogen atoms in the first material 110 changes the lattice constant of the first material 110. The regulation of the stress level of the second material 120 is achieved by the contact interface.

Please refer to FIG. 5. FIG. 5 is a schematic diagram of inserting or extracting particles by using an ozone annealing method in a stress control method according to an embodiment of the present application. A first material 110 and a second material 120 are deposited on the substrate 140 in FIG.

In one embodiment, the S30 includes: S305, providing an oxygen-containing reactive gas.

In one embodiment, the oxygen-containing reaction gas is ozone, which is very unstable and capable of decomposing into oxygen molecules and oxygen atoms. The decomposed oxygen atoms are inserted into the first material 110 by diffusion. It can be understood that the oxygen-containing reaction gas can also be other gases capable of providing oxygen atoms, or other mixed gases.

S307, annealing the first material 110 and the second material 120 in the oxygen-containing reaction gas to change a lattice constant of the first material 110.

In one embodiment, oxygen atoms are inserted or extracted in the first material 110 by an annealing process.

In one embodiment, the S307 includes: S307a, in the oxygen-containing reaction gas, heating the first material 110 and the second material 120 to a first temperature. The oxygen-containing reaction gas generates an oxygen atom. The oxygen atoms are diffused into the first material 110.

In one embodiment, the first material 110 and the second material 120 are heated to increase the diffusion of oxygen atoms in the first material 110. The oxygen atoms are diffused into the first material 110 to change the lattice constant of the first material 110. In one embodiment, the first temperature is between 200 degrees Celsius and 400 degrees Celsius. Preferably, the first temperature is 300 degrees Celsius.

S307b, the first material 110 and the second material 120 are maintained at 200 degrees Celsius to 400 degrees Celsius for 15 minutes to 60 minutes.

In one embodiment, the first time is from 15 minutes to 60 minutes. Preferably, the first time is 30 minutes bell. The first time is maintained to enable oxygen atoms to sufficiently enter the first material 110. The lattice constant of the first material 110 can change the composition, and the stress of the second material 120 can be sufficiently regulated.

In this embodiment, the insertion or extraction of oxygen atoms is achieved by an ozone annealing method. The first material 110 and the second material 120 are placed in an oxygen-containing reaction gas. The oxygen-containing reaction gas provides an oxygen atom. Oxygen atoms diffuse into the first material 110, causing a change in the lattice constant of the first material 110. The regulation of the stress level of the second material 120 is achieved by the contact interface.

Specific embodiments for adjusting the stress level of the second material 120 using the stress control method provided by the present application are given below. Example 1: This example provides an example of SrCoO _2.5 -CoFe ₂ O ₄ . Wherein, SrCoO _2.5 is the first material 110, and CoFe ₂ O ₄ is the second material 120. The following describes the magnitude of the stress _{2.5 -CoFe} ₂ O ₄ changes of the sample under the SrCoO SrCoO _{2.5 -CoFe} ₂ O ₄ Structural Characterization stress-control method of the present application and samples.

Please refer to FIG. 6. FIG. 6 is an X-ray diffraction pattern of the SrCoO _2.5 -CoFe ₂ O ₄ sample before and after annealing in ozone. The lower curve in Fig. 6 is an X-ray diffraction pattern of the SrCoO _2.5 -CoFe ₂ O ₄ sample before annealing. The upper curve in Fig. 6 is an X-ray diffraction pattern of the SrCoO _2.5 -CoFe ₂ O ₄ sample after ozone annealing. In FIG. 6, No. triangular peaks are indicated characteristic peaks SrCoO _2.5, dot marked peaks are characteristic peaks CoFe ₂ O _4, asterisks substrate 140 peaks. This indicates that SrCoO _2.5 becomes SrCoO _3-δ after ozone annealing, and the hollow triangle number indicates SrCoO _3-δ . The phase change of SrCoO _2.5 in Fig. 6 to the SrCoO _3-δ phase proves that the lattice constant of the first material 110 has changed. In order to clearly recognize the change in the lattice constant of the first material 110, the spectral line at 40°-50° in Fig. 6 is enlarged to obtain Fig. 7. Figure 7 is a line enlarged of the SrCoO _2.5 -CoFe ₂ O ₄ sample at 40 ° - 50 °. The change in peak value after SrCoO _2.5 stress regulation can be seen in Fig. 7, so that the out-of-plane lattice constant of the first material 110SrCoO _2.5 is calculated to be reduced by 3.53%. That is, the first material 110SrCoO _2.5 provides a crush stress of 3.53%. It can also be seen in Fig. 7 that the peak position of the second material 120CoFe ₂ O ₄ is shifted to the right, and the lattice constant of the second material 120CoFe ₂ O ₄ is calculated to be 0.97%. It can be seen that the stress control method provided by the present application can apply a compressive stress of 3.53% to the second material, thereby changing the lattice constant of the second material.

Please refer to FIG. 8. FIG. 8 is an X-ray diffraction spectrum of the SrCoO _2.5 -CoFe ₂ O ₄ sample before and after hydrogenation of the metal catalyst 201. In Fig. 8, the peak indicated by the solid triangle is a characteristic peak of SrCoO _2.5 . The dots indicate the peak of CoFe ₂ O ₄ . The asterisk is the peak of the substrate 140. The hollow triangle number indicates SrCoO _2.5 H. As shown in Fig. 8, a curve below is an X-ray diffraction pattern of the SrCoO _2.5 -CoFe ₂ O ₄ sample grown by the exchange method. The upper curve in Fig. 8 is an X-ray diffraction pattern of the SrCoO _2.5 -CoFe ₂ O ₄ sample after hydrogen ion insertion by a method of hydrogenation of a metal catalyst. It can be seen from the two curves varying in Fig. 8 that the overall structure of the SrCoO _2.5 -CoFe ₂ O ₄ sample has changed. The change in the overall structure is mainly reflected in the change of the lattice constant in the out-of-plane direction. In order to clearly recognize the change in the overall structure of the SrCoO _2.5 -CoFe ₂ O ₄ sample, part of the line in Fig. 8 was enlarged. Figure 9 is a magnified line of the SrCoO _2.5 -CoFe ₂ O ₄ sample at 40 ° - 50 ° in Figure 8. It is clear in Fig. 9 that the peak variation of SrCoO _2.5 can be seen, so that the out-of-plane lattice constant of the first material 110SrCoO _2.5 is calculated to increase by 6.22%. That is, the first material 110SrCoO _2.5 provides a tensile stress of 6.22%. The peak position of the second material 120CoFe ₂ O ₄ is shifted to the left, and the lattice constant of the second material 120CoFe ₂ O ₄ is calculated to be increased by 0.40%. It can be seen that the stress control method provided by the present application can apply a 6.22% tensile stress to the second material 120, thereby changing the lattice constant of the second material 120.

Example 2: This example provides an example of a NiFe ₂ O ₄ -SrCoO _2.5 sample. Wherein, SrCoO _2.5 is the first material 110, and NiFe ₂ O ₄ is the second material 120. The following describes the structural characterization of stress changes in the size of the NiFe ₂ O ₄ -SrCoO _2.5 sample and the method of the present application is the stress regulation of NiFe ₂ O ₄ -SrCoO _2.5 Sample conditions:

In this embodiment, the NiFe ₂ O ₄ -SrCoO _2.5 sample has a 1-3 configuration. The growth ratio of SrCoO _2.5 to the NiFe ₂ O ₄ was 4:1. Figure 10 is a representation of the surface topography of the NiFe ₂ O ₄ -SrCoO _2.5 sample. The light and dark in Fig. 10 indicates the height of the surface of the sample, which is high in brightness and low in dark. The bright portion in Fig. 10 and formed into a rectangle is NiFe ₂ O ₄ . The dark and flat place in Figure 10 is SrCoO _2.5 .

Figure 11 is an X-ray diffraction pattern of the NiFe ₂ O ₄ -SrCoO _2.5 sample. It can be seen in Fig. 11 that the peak indicated by the rice character is the peak of the substrate 140SrTiO ₃ (002). The number of substrate 140 left triangular peaks are marked 110SrCoO _2.5 peak of the first material. The peak marked with a circle is the peak of the second material 120NiFe ₂ O ₄ .

The stress of the NiFe ₂ O ₄ -SrCoO _2.5 sample was adjusted by an ionic liquid plus electric field method. Figure 12 is a graph showing the structural change of the NiFe ₂ O ₄ -SrCoO _2.5 sample by in-situ X-ray diffraction. As can be seen from Fig. 12, when a positive voltage is applied to the NiFe ₂ O ₄ -SrCoO _2.5 sample, the ionic liquid 202 regulates the insertion of hydrogen ions and extracts oxygen ions. The NiFe ₂ O ₄ -SrCoO _2.5 sample NiFe ₂ O ₄ with the lattice constant of the outer surface of the sample increases SrCoO _2.5. The positive voltage, i.e., the ionic liquid 202, is at a high potential and the first material 110 is at a low potential. Hydrogen ions are inserted into the first material 110 and oxygen ions are extracted, thereby increasing the out-of-plane lattice constant of the first material 110. At this time, the first material 110 applies a tensile stress to the second material 120. When a negative voltage is applied to the NiFe ₂ O ₄ -SrCoO _2.5 sample, the ionic liquid 202 regulates the extraction of hydrogen ions and inserts oxygen ions. The NiFe ₂ O ₄ -SrCoO _2.5 sample NiFe ₂ O ₄ with the outer surface of the lattice SrCoO _2.5 decreases decreases. The negative voltage, i.e., the ionic liquid 202, is at a low potential and the first material 110 is at a high potential. Oxygen ions are inserted into the first material 110 and hydrogen ions are extracted, thereby reducing the out-of-plane lattice constant of the first material 110 and applying a compressive stress to the second material 120. Experiments have confirmed that the out-of-plane lattice constants of the first material 110 and the second material 120 can all return to the original when a positive voltage is applied. It shows that the stress control process can be repeated. During the regulation of the entire ionic liquid plus electric field, the X-ray diffraction peak position of the first material 110SrCoO _2.5 is changed from the initial 46.2° to 44.2° and then to 47.8°. The lattice constant of the first material 110SrCoO _2.5 was stretched by 3.1% from the initial state and then by 4.3% with respect to the initial state. Correspondingly, when the ionic liquid 202 is applied with a positive voltage, the first material 110 applies a tensile stress of 3.1% to the second material 120. When the ionic liquid 202 is applied with a negative voltage, the first material 110 applies a compressive stress of 4.3% to the second material 120. When the sample is applied with a forward voltage, the lattice constant of the second material 120 relative to the single crystal material of the second material 120 is increased by 0.42% due to a change in the first material 110. When the sample is applied with a reverse voltage, the lattice constant of the second material 120 relative to the single crystal material of the second material 120 is reduced by 1.51%. That is, the overall variation of the lattice constant of the second material 120 can reach 1.93%.

The embodiment of the present application provides a method of stress regulation, and it is not possible to exhaust all of the embodiments herein. It will be understood that the method of changing the lattice constant of one material by the method of inserting or extracting particles to change the stress of the other material is within the scope of the present application. The change of the lattice constant of the material is extremely important and the change of the root source. The change will significantly affect the structure and properties of the material, and also bring about various changes in the electronic structure and the coordination environment.

The technical features of the above-described embodiments may be combined in any combination. For the sake of brevity of description, all possible combinations of the technical features in the above embodiments are not described, but as long as there is no contradiction in the combination of these technical features, It should be considered as the scope of this manual.

The above-mentioned embodiments are merely illustrative of several embodiments of the present application, and the description thereof is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the present application. Therefore, the scope of the invention should be determined by the appended claims.

Claims

A stress control method, comprising:

S10, providing a first material of the structural formula ABO x H y , wherein A is one or more of an alkaline earth metal element and a rare earth metal element, and B is one or more of transition metal elements, and the value of x The range is 1-3, and the range of y is 0-3;

S20, providing a second material, contacting the first material with the second material and forming a contact interface between the first material and the second material;

S30, inserting or extracting particles into the first material, changing a lattice constant of the first material, and realizing stress regulation on the second material, the particles including one or more of ions and atoms.
The stress control method according to claim 1, wherein the ions include hydrogen ions, lithium ions, sodium ions, potassium ions, barium ions, barium ions, magnesium ions, calcium ions, barium ions, barium ions, nitrogen. One or more of ions, phosphorus ions, oxygen ions, sulfur ions, selenium ions, and fluoride ions;

The atom includes a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, a helium atom, a helium atom, a magnesium atom, a calcium atom, a helium atom, a helium atom, a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom, a selenium atom, and fluorine. One or more of the atoms.
The stress control method according to claim 1, wherein the second material comprises one or more of a simple substance of a metal, a metal oxide, and an alloy.
The stress control method according to claim 1, wherein the second material comprises a nano material comprising zero-dimensional clusters, artificial atoms, nanoparticles; one-dimensional nanowires, nanotubes, Nanorods, nanofibers; two-dimensional nanobelts, ultrathin films, multilayer films.
The stress control method according to claim 1, wherein the second material comprises an organic functional material, the organic functional material comprising an organic material having a mechanical function, an organic material having a chemical function, and a physicochemical function. Organic materials, organic materials with biochemical functions, and organic materials with electrical functions.
The stress control method according to claim 1, wherein the S30 comprises:

S301, providing an ionic liquid, wherein the ionic liquid contains hydrogen ions and oxygen ions, and the first material and the second material are disposed in the ionic liquid;

S303, applying an electric field to the ionic liquid such that hydrogen ions or oxygen ions in the ionic liquid are inserted into the first material, or hydrogen ions or oxygen ions are extracted from the first material.
The stress control method according to claim 6, wherein in the S303, the ionic liquid is at a high potential, the first material is at a low potential, and hydrogen ions in the ionic liquid are inserted into the first Extracting material or oxygen ions from the first material such that an out-of-plane lattice constant of the first material is increased to apply tensile stress to the second material to effect stress regulation on the second material .
The stress control method according to claim 6, wherein in the S303, the ionic liquid is at a low potential, the first material is at a high potential, and oxygen ions in the ionic liquid are inserted into the first Extracting material or hydrogen ions from the first material such that an out-of-plane lattice constant of the first material is reduced, thereby applying a compressive stress to the second material to effect stress regulation on the second material .
The stress control method according to claim 1, wherein said S30 comprises:

S302, providing a metal catalyst and a hydrogen-containing reaction gas;

S304, heating and heating to 20 degrees Celsius to 200 degrees Celsius, causing the hydrogen-containing reaction gas to generate hydrogen atoms under the action of the metal catalyst, the hydrogen atoms being diffused into the first material to make the first material The lattice constant changes.
The stress control method according to claim 1, wherein said S30 comprises:

S305, providing an oxygen-containing reaction gas;

S307, heating the first material and the second material to a temperature of 200 degrees Celsius to 400 degrees Celsius, wherein the first material is oxidized by an oxygen-containing reaction gas, and oxygen is diffused into the first material in the form of oxygen atoms. Medium to change the lattice constant of the first material.