Growth method of germanium-based rare earth nickel-based oxide electronic phase change material

Abstract

The invention discloses a growth method of a germanium-based rare earth nickel-based oxide electronic phase change material. A germanium dioxide high oxygen pressure phase is used as a lattice template, and a nucleation site triggers a rare earth nickel-based oxide in a thermodynamic metastable phase to grow in a non-uniform nucleation mode; preparing powder with a rare earth nickel-based oxide / germanium dioxide high oxygen pressure phase coating structure, a rare earth nickel-based oxide polycrystalline film / germanium dioxide high oxygen pressure phase transition layer / single crystal germanium heterojunction and a rare earth nickel-based oxide pseudo-single crystal film / germanium dioxide high oxygen pressure phase transition layer / single crystal silicon heterojunction; the prepared material has the functional characteristics of metal insulator phase change under temperature triggering and proton-triggered hydrogen-induced electron phase change. The growth of the rare earth nickel-based oxide in a thermodynamic metastable phase on a silicon and germanium group IV semiconductor substrate can be realized, and the compatibility of a subsequent device preparation process and a traditional silicon-based semiconductor technology is realized. The prepared material has potential application value in the aspects of nerve components, abrupt change type thermistors, infrared camouflage and laser weapon protection.

Description

Technical Field

[0001] The invention belongs to the field of semiconductor technology and functional materials, and in particular relates to a method for growing germanium-based rare earth nickel-based oxide electronic phase change materials. Background Art

[0002] Rare earth nickel-based oxides include 113-type distorted perovskite structure (ReNiO3, Re is a rare earth element other than La) and Ruddlesden-Popper phase layered perovskite structure (Re 1-x Ae x ) n+1 Ni n O 3n+1 , Re is a rare earth element, Ae is an alkaline earth element), at the characteristic temperature (T MIT ) can trigger its metal-insulator transition, from a low-temperature insulating phase to a high-temperature metallic phase, accompanied by a change in the crystal structure, which in turn causes a sudden change in its physical properties [1-3]. As the radius of the rare earth ions decreases, the degree of distortion of the NiO6 octahedron in the rare earth nickel-based oxide gradually increases, and the stability of the insulating phase relative to the metallic phase increases, resulting in T MIT Gradually increases [4]. Therefore, the T MIT Flexible regulation in a wide range of 100-600 K [5]. In addition, the electronic phase transition can be triggered by polarization electric field, characteristic pressure or chemical / electrochemical hydrogenation, thereby causing a sudden change in resistivity [6-7]. Therefore, rare earth nickel-based oxides have potential application prospects in the fields of neuron devices, mutant thermistors, infrared camouflage and laser weapon protection [8-10].

[0003] However, the compatibility of rare earth nickel-based oxide materials with silicon-based technology is a technical barrier that currently limits the research and application of this material in the field of electronic devices. Rare earth nickel-based oxides are in a thermodynamically metastable phase and have a positive Gibbs formation free energy at high temperatures. They are difficult to synthesize through conventional solid-phase reactions. Moreover, as the radius of the rare earth ion decreases, its positive Gibbs formation free energy gradually increases, increasing the difficulty of synthesizing this material

[11] . The template effect of the single crystal substrate is used to reduce the Gibbs formation free energy, and the epitaxial growth of this material can be achieved through vacuum technologies such as pulsed laser deposition or magnetron sputtering. However, since the Si surface oxide layer and the rare earth nickel-based oxide do not have a coherent relationship, it is difficult to achieve high-quality growth on Group IV semiconductor materials, which is manifested in the extremely low degree of resistivity mutation before and after the metal insulating phase transition [12-14].

[0004] In summary, the field currently lacks an effective method for achieving high-quality growth of rare earth nickel-based oxide electronic phase change materials on Group IV semiconductors represented by silicon, germanium, germanium silicon, and silicon carbide. This makes it impossible to combine the application of this material in neuron devices, mutant thermistors, infrared camouflage, and laser weapon protection with existing silicon semiconductor processes, and its related applications are difficult to promote on a large scale.

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[0011] 【7】Yuan Y F, Kotiuga M, Park T J, et al. Hydrogen-induced tunableremanent polarization in a perovskite nickelate [J]. Nature Communications,2024, 15: 4717.

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[0013] 【9】Chen J K, Li Z A, Dong H L, et al. Pressure induced unstableelectronic states upon correlated nickelates metastable perovskites as batchsynthesized via heterogeneous nucleation [J]. Advanced Functional Materials,2020, 30 (23): 2000987.

[0014]

[10] Shahsafi A, Roney P, Zhou Y, et al. Temperature-independentthermal radiation [J]. Proceedings of the National Academy of Sciences of theUnited States of America, 2019, 116 (52): 26402.

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[11] Zhang Z, Schwanz D, Narayanan B, et al. Perovskite nickelates aselectric-field sensors in salt water [J]. Nature, 2018, 553: 68-72.

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[13] Conchon F, Boulle A, Guinebreitiere R, et al. Effect of tensileand compressive strains on the transport properties of SmNiO3 layersepitaxially grown on (001) SrTiO3 and LaAlO3 substrates [J]. Applied PhysicsLetters, 2007, 91: 192110.

[0018]

[14] Li J R, Green R J, Zhang Z, et al. Sudden Collapse of MagneticOrder in Oxygen-Deficient Nickelate Films [J]. Physical Review Letters, 2021,126: 187602. Summary of the invention

[0019] The present invention provides a method for growing a germanium-based rare earth nickel-based oxide electronic phase change material, the main idea of ​​which is: based on the coherent matching relationship between stable germanium dioxide and rare earth nickel-based oxide under high oxygen pressure, by introducing a germanium dioxide high oxygen pressure phase as a lattice template and nucleation site, the forward Gibbs formation free energy of the reaction is reduced, and the non-uniform nucleation and growth of the rare earth nickel-based oxide in a thermodynamic metastable phase on its surface are triggered, thereby improving the growth quality and electronic phase change characteristics of the rare earth nickel-based oxide electronic phase change material. According to the method provided by the present invention, a rare earth nickel-based oxide / germanium dioxide high oxygen pressure phase coated structure powder, a rare earth nickel-based oxide film / germanium dioxide high oxygen pressure phase transition layer / single crystal germanium substrate heterojunction, and a rare earth nickel-based oxide film / germanium dioxide high oxygen pressure phase transition layer / single crystal silicon heterojunction can be prepared, and the metal insulator phase transition under temperature triggering and the functional characteristics of proton-triggered hydrogen-induced electronic phase transition can be realized. The technology provided by the present invention can realize the growth of rare earth nickel-based oxides with metastable phase structure on traditional IV semiconductor substrates represented by silicon and germanium, thereby achieving compatibility of subsequent device preparation processes with traditional silicon-based semiconductor technology. The prepared materials have potential application value in neuron devices, mutant thermistors, infrared camouflage, and laser weapon protection.

[0020] A method for growing germanium-based rare earth nickel-based oxide electronic phase change materials, characterized in that a germanium dioxide high oxygen pressure phase that has a lattice matching relationship with a rare earth nickel-based oxide electronic phase change semiconductor material in a thermodynamically metastable phase and is stable in the same high oxygen pressure range is introduced as a seed or transition layer, thereby effectively growing a composite powder of rare earth nickel-based oxide coated with germanium dioxide high oxygen pressure phase, a rare earth nickel-based oxide / germanium dioxide high oxygen pressure phase / germanium substrate heterojunction, and a rare earth nickel-based oxide / germanium dioxide high oxygen pressure phase / silicon substrate heterojunction; through the growth of the above-mentioned rare earth nickel-based oxide material on silicon-based and germanium-based substrates, it is compatible with traditional silicon-based semiconductor micromachining and device preparation processes, thereby realizing the application of neuron devices, mutation thermistors, infrared camouflage devices, and laser weapon protection layers.

[0021] Furthermore, the seed crystal or transition layer is a germanium dioxide high oxygen pressure phase, which has a similar lattice constant to the rare earth nickel-based oxide, and is in a thermodynamically stable state under the high oxygen pressure conditions required for the growth of the rare earth nickel-based oxide; the rare earth nickel-based oxide can be directly coated on the germanium dioxide high oxygen pressure phase powder by high oxygen pressure molten salt reaction and hydrothermal reaction to prepare a composite powder; or first grow a germanium dioxide high oxygen pressure phase transition layer on a substrate, and then use spin coating, pulsed laser deposition, magnetron sputtering process deposition and molten salt assisted method to grow a rare earth nickel-based oxide film precursor and anneal under high oxygen pressure to prepare a rare earth nickel-based oxide / germanium dioxide / substrate heterojunction film; or first grow a Ge transition layer on a substrate and anneal at a high oxygen pressure of 0.2-500 MPa at 50-1500 ºC, and in an ozone atmosphere for 20-300 ºC oxidation and oxygen plasma oxidation to generate germanium dioxide high oxygen pressure phase, and then use spin coating, pulsed laser deposition, magnetron sputtering deposition and molten salt assisted method to grow rare earth nickel-based oxide film precursor and anneal under high oxygen pressure to prepare rare earth nickel-based oxide / germanium dioxide / substrate heterojunction film; in the above-mentioned germanium dioxide and germanium oxidation process at high oxygen pressure and ozone, the stoichiometric ratio and crystal structure of the generated germanium dioxide high oxygen pressure phase transition layer and the silicon-based substrate and rare earth nickel-based oxide interface can be reduced by adjusting the oxidation process parameters to reduce the lattice mismatch.

[0022] Furthermore, the rare earth nickel-based oxide electronic phase change material prepared has a 113-type twisted perovskite structure, and its chemical formula is ReNiO3, wherein Re is a single rare earth or a combination of multiple rare earth elements except lanthanum, including praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y) and scandium (Sc); The design can achieve the regulation of the electronic structure of rare earth nickel-based oxides, thereby adjusting their metal-insulator transition characteristics and hydrogen-induced electronic phase change characteristics; the method for synthesizing rare earth nickel-based oxide materials includes pulsed laser deposition technology, magnetron sputtering, hydrothermal method, wet chemical spin coating method, sol-gel method and molten salt method; by changing the synthesis process, the orientation and thickness of the rare earth nickel-based oxide electronic phase change material can be regulated; in a preferred embodiment, the magnetron sputtering method is used to introduce the Si of the germanium dioxide high oxygen pressure phase transition layer 0.5 Ge 0.5 The PrNiO3 material grown on the substrate is a 40 nm thick polycrystalline film with a phase transition temperature of 120 K. In another preferred embodiment, the EuNiO3 material grown on a single crystal Si substrate with a germanium dioxide high oxygen pressure phase transition layer introduced by wet chemical spin coating is a 80 nm thick quasi-single crystal film with a phase transition temperature of 475 K.

[0023] Furthermore, the rare earth nickel-based oxide electronic phase change material prepared also has a Ruddlesden-Popper phase layered perovskite structure, and its chemical formula is (Re 1-x Ae x ) n+1 Ni n O 3n+1 , the structural feature is a single-layer rock salt layer structure (Re 1-x Ae x )O and n-layer perovskite structure (Re 1-x Ae x )NiO3 are arranged alternately; Re is a single rare earth or a combination of multiple rare earth elements, including lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), Ae is an alkaline earth element; n is 1, 2, 3, corresponding to (Re 1-x Ae x )2NiO4、(Re 1-x Ae x )3Ni2O7、(Re 1-x Ae x )4Ni3O 10 In a preferred embodiment, La is grown on a Ge substrate with a germanium dioxide high oxygen pressure phase transition layer by pulsed laser deposition technology. 1.99 Sr 0.01 NiO4 is a 30 nm thick polycrystalline film that can be used as an oxygen evolution reaction catalyst; in another preferred embodiment, Nd grown on a single crystal Si substrate with a germanium dioxide high oxygen pressure phase transition layer by wet chemical spin coating 2.95 Ca 0.05 The Ni2O7 material is a quasi-single-crystalline film with a thickness of 40 nm, which can be used for smart windows. In another preferred embodiment, Sm2Nd2Ni3O is grown on the surface of a germanium dioxide high oxygen pressure phase seed by a hydrothermal method. 10 Polycrystalline powder, the coating structure can be used for sewage treatment.

[0024] Furthermore, in order to synthesize germanium dioxide high oxygen pressure phase powder coated with rare earth nickel-based oxide, commercial germanium dioxide can be used as a precursor to be oxidized under high oxygen pressure or ozone atmosphere to obtain germanium dioxide high oxygen pressure phase, and germanium powder can also be used as a precursor to be oxidized under high oxygen pressure or ozone atmosphere to obtain germanium dioxide high oxygen pressure phase; the germanium dioxide high oxygen pressure phase powder has a curved surface shape including spherical, ellipsoidal, and cylindrical, and its size range is 0.1 μm-1 cm; it is characterized in that its surface has an adsorption effect on rare earth element oxides and nickel element oxide precursors in a molten flux, and has a lattice matching relationship with the fitted rare earth nickel-based oxide, thereby promoting the non-uniform nucleation and growth of rare earth nickel-based oxide on its surface to form a coating structure; in a preferred embodiment, spherical commercial germanium dioxide microspheres with a particle size of 100 nm are used as the core material, and NdNiO3 polycrystalline powder is grown on its surface by a molten salt method after high oxygen pressure annealing, and its phase transition temperature is 200 K; in another preferred embodiment, germanium powder with a particle size of 50 nm is used as a precursor, and a germanium dioxide high oxygen pressure phase seed material is obtained after annealing in an ozone atmosphere, and a SmNiO3 polycrystalline coating layer is grown on its surface by a hydrothermal reaction, and its phase transition temperature is 410 K.

[0025] Furthermore, in order to synthesize a polycrystalline rare earth nickel-based oxide / germanium dioxide high oxygen pressure phase / germanium substrate heterojunction, the germanium substrate is first annealed under MPa-level high oxygen pressure, annealed in an ozone atmosphere, or oxidized in an oxygen plasma to generate a germanium dioxide high oxygen pressure phase transition layer. By adjusting the thickness of the transition layer and the rare earth nickel-based oxide growth process, the preferred orientation of the rare earth nickel-based oxide polycrystalline film can be controlled, and its thickness ranges from 1 to 1000 nm. Glass, quartz, mica, silicon carbide, Si 1-x Ge x The substrate replaces the germanium substrate, and the germanium is further oxidized by plasma sputtering or directly sputtered by oxygen plasma to generate a germanium dioxide high oxygen pressure phase, so that the rare earth nickel-based oxide can be non-uniformly nucleated on the surface of the germanium dioxide high oxygen pressure phase transition layer and grow into a polycrystalline film with a preferred orientation; in a preferred embodiment, the single crystal germanium substrate is annealed at an oxygen pressure of 10 MPa to obtain a 50 nm thick germanium dioxide high oxygen pressure phase transition layer, and then the Nd 0.5 Sm 0.5 The phase transition temperature of NiO3 polycrystalline film is 280 K. In another preferred embodiment, a 100 nm thick germanium dioxide high oxygen pressure phase transition layer is sputtered on a silicon carbide substrate by magnetron sputtering, and then Nd 0.7 Sm 0.3 NiO3 polycrystalline thin film, its phase transition temperature is 300 K.

[0026] Furthermore, in order to synthesize a rare earth nickel-based oxide quasi-single crystal film / germanium dioxide high oxygen pressure / silicon substrate heterojunction, germanium is further oxidized by plasma sputtering or directly sputtered by oxygen plasma to obtain a germanium dioxide high oxygen pressure phase transition layer; the germanium dioxide high oxygen pressure phase / silicon substrate heterojunction has a specific coherent matching relationship with the rare earth nickel-based oxide, thereby reducing the Gibbs synthesis free energy of the rare earth nickel-based oxide and promoting its epitaxial growth; by adjusting the thickness of the transition layer and the rare earth nickel-based oxide deposition process, the growth of a rare earth nickel-based oxide quasi-single crystal film can be achieved, and the thickness of the transition layer ranges from 1 to 1000 nm; in a preferred example, Ge is sputtered on the Si surface by magnetron sputtering, and then annealed in an ozone flow to obtain an 80 nm thick germanium dioxide high oxygen pressure phase polycrystalline transition layer, and then pulsed laser deposition is used to prepare a GdNiO3 quasi-single crystal film, and its phase transition temperature is 520 K. In another preferred embodiment, a 30 nm thick germanium dioxide high oxygen pressure phase is sputtered on a Si substrate by magnetron sputtering, and then Pr 0.1 Nd 0.9 NiO3 quasi-single crystal thin film, its phase transition temperature is 140K.

[0027] Furthermore, the rare earth nickel-based oxide / germanium dioxide high oxygen pressure phase / silicon substrate heterojunction prepared by the present invention can be connected to the existing silicon-based semiconductor device process, and further prepared into proton-regulated neuron devices and strongly correlated electronic devices based on electric field and temperature-triggered metal-insulator phase transition; in a preferred example, a NdNiO3 quasi-single-crystalline thin film grown on a Si substrate with a germanium dioxide high oxygen pressure phase transition layer introduced is deposited with a discontinuous Pt electrode and then embedded in an integrated circuit, and the synaptic structure of human brain neurons is simulated by controlling the electric pulse and hydrogen ion gradient distribution, so as to construct an adaptive dynamic neuron network and greatly reduce computing energy consumption; in another preferred example, a PrNiO3 quasi-single-crystalline thin film is grown on a Si substrate with a germanium dioxide high oxygen pressure phase transition layer introduced, and Au electrodes are introduced by laser direct writing, and then further arranged into a specific array and embedded in an integrated circuit to realize the temperature alarm function in the liquid nitrogen temperature zone.

[0028] Furthermore, based on the sudden change of infrared optical properties triggered by rare earth nickel-based oxide at characteristic temperature, the rare earth nickel-based oxide / germanium dioxide high oxygen pressure / germanium substrate heterojunction grown by the present invention can be prepared into laser weapon protective coating and infrared camouflage device; in a preferred embodiment, the Nd grown on the Ge substrate with germanium dioxide high oxygen pressure phase transition layer is introduced. 0.5 Sm 0.5 The NiO3 polycrystalline thin film is arranged into a large-area array, which is transparent under visible light irradiation and undergoes a metal-insulator transition under laser irradiation, thereby causing its transmittance to drop significantly and its reflectivity to increase significantly, thereby achieving a protective effect against laser weapons; in another preferred embodiment, Nd grown on a Ge substrate with a germanium dioxide high oxygen pressure phase transition layer0.3 Sm 0.7 NiO3 polycrystalline thin films are arranged into a large-area array. When the human body temperature triggers its electronic phase change, the infrared emissivity changes suddenly, thus achieving the effect of infrared camouflage near body temperature.

[0029] The present invention uses the germanium dioxide high oxygen pressure phase as a lattice template and nucleation site to trigger the rare earth nickel-based oxide in a thermodynamically metastable phase to grow in a non-uniform nucleation manner, thereby preparing rare earth nickel-based oxide / germanium dioxide high oxygen pressure phase coating structure powder, rare earth nickel-based oxide polycrystalline film / germanium dioxide high oxygen pressure phase transition layer / single crystal germanium heterojunction, rare earth nickel-based oxide quasi-single crystal film / germanium dioxide high oxygen pressure phase transition layer / single crystal silicon heterojunction, and the prepared material has the functional characteristics of metal insulator phase transition under temperature triggering and proton triggered hydrogen-induced electronic phase transition. The technology provided by the present invention can realize the growth of rare earth nickel-based oxide in a thermodynamically metastable phase on a traditional IV group semiconductor substrate represented by silicon and germanium, thereby achieving compatibility of subsequent device preparation processes with traditional silicon-based semiconductor technology. The prepared material has potential application value in neuron devices, mutation thermistors, infrared camouflage, and laser weapon protection.

[0030] After extensive and in-depth research, the present invention has obtained a method for growing germanium-based rare earth nickel-based oxide electronic phase change materials. The present invention introduces a germanium dioxide high oxygen pressure phase that matches the lattice of rare earth nickel-based oxides as a seed or buffer layer to achieve the growth of rare earth nickel-based oxides on traditional Group IV semiconductor substrates represented by silicon and germanium, thereby achieving compatibility of subsequent device preparation processes with traditional silicon-based semiconductor technology, and further achieving brain-like neuron computing, mutant thermistors, infrared camouflage or laser weapon protection functions. Compared with traditional synthesis processes, this method breaks through the barriers of compatibility between rare earth nickel-based oxide electronic phase change materials and silicon-based technology, and the functional characteristics can be synergistically regulated by the germanium dioxide high oxygen pressure phase structure and rare earth element components. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The present invention provides a grazing incidence X-ray diffraction spectrum of NdNiO3 epitaxially grown on a Ge substrate into which a germanium dioxide high oxygen pressure phase is introduced using the method of the present invention.

[0032] Figure 2 The resistance-temperature relationship curve of epitaxially growing NdNiO3 on a Ge substrate into which a germanium dioxide high oxygen pressure phase is introduced is proposed by the method of the present invention.

[0033] Figure 3 This is a schematic diagram of the principle of 113-type rare earth nickel-based oxide polycrystalline film / germanium dioxide high oxygen pressure phase transition layer / single crystal germanium substrate synthesized by the method of the present invention.

[0034] Figure 4This is a schematic diagram of the principle of the 113-type rare earth nickel-based oxide / germanium dioxide high oxygen pressure phase coating structure synthesized by the method of the present invention.

[0035] Figure 5 This is a schematic diagram of the principle of 113-type rare earth nickel-based oxide quasi-single crystal film / germanium dioxide high oxygen pressure phase transition layer / single crystal silicon substrate synthesized by the method of the present invention.

[0036] Figure 6 The schematic diagram of the Ruddlesden-Popper type rare earth nickel-based oxide polycrystalline film / germanium dioxide high oxygen pressure phase transition layer / single crystal germanium substrate synthesized by the method of the present invention. DETAILED DESCRIPTION

[0037] Unless otherwise specified, the various raw materials of the present invention can be obtained by commercially available or by conventional methods in the art. Unless otherwise defined or specified, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to those described herein can be applied to the method of the present invention.

[0038] Other aspects of the present invention will be apparent to those skilled in the art in view of the disclosure herein.

[0039] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples without specifying specific conditions are usually carried out under conventional conditions or under conditions recommended by the manufacturer.

[0040] Test method: XRD and PPMS were used to characterize the prepared materials. The characterization method was carried out according to the general standards in the field.

[0041] Example 1: A single crystal Ge substrate was placed in an oxygen pressure of 10 MPa and 550 °C for annealing for 2 h. The resulting single crystal germanium dioxide transition layer thickness was about 10 nm. Then nickel oxide and neodymium oxide were used as precursors, potassium chloride was used as molten salt, and annealed at 7 MPa oxygen pressure and 800 °C for 24 h before being taken out. The resulting NdNiO3 grazing incidence X-ray diffraction spectrum is as follows: Figure 1 As shown, the resistance-temperature relationship is as follows Figure 2 As shown. NdNiO3 thin film with perovskite structure exhibits metal-insulator phase transition behavior at 187 K. The principle is as follows Figure 3As shown in the figure, the lattice matching relationship between 113-type rare earth nickel-based oxide and germanium dioxide high oxygen pressure phase is used to reduce the Gibbs formation free energy, thereby realizing the non-uniform nucleation and growth of rare earth nickel-based oxide. A discontinuous Pt electrode is deposited on the surface of NdNiO3 film, and placed in a mixture of hydrogen (10%) and argon (90%) at 100 °C for 2 h. After hydrogenation, its resistivity increases by 3 orders of magnitude. The NdNiO3 film prepared above is combined with a flexible black body background such as a carbon tube network, and the proton spatial distribution is regulated by applying an external electric field to change the local infrared emission characteristics, thereby making an erasable infrared coding device that can be used for optical anti-counterfeiting and smart display.

[0042] Example 2: Spherical commercial germanium dioxide microspheres with a particle size of 500 nm were used as the core material, annealed at 6 MPa oxygen pressure and 500 °C for 12 h, and then taken out. Nickel oxide and neodymium oxide were used as precursors, and potassium carbonate was used as molten salt. They were annealed at 7 MPa oxygen pressure and 800 °C for 24 h, and then taken out. After washing and drying, NdNiO3 / germanium dioxide high oxygen pressure phase-coated structure powder was obtained, and its phase transition temperature was 200 K; its principle is as follows Figure 4 As shown, the surface of the germanium dioxide seed crystal has an adsorption effect on the 113-type rare earth element oxide and nickel element oxide precursor in the molten flux, and has a lattice matching relationship with the fitted rare earth nickel-based oxide, thereby promoting the non-uniform nucleation and growth of the rare earth nickel-based oxide on its surface to form a coating structure. The above-prepared NdNiO3 / germanium dioxide high oxygen pressure phase coated powder is dispersed on a PMN-PT substrate, and after being processed into a specific pattern by photolithography, it can identify the changes in electrical signals caused by phase change after applying an electric pulse, and can be used in the field of intelligent digital technology.

[0043] Example 3: First, Ge is sputtered on a single crystal Si substrate by magnetron sputtering, with a substrate temperature of 400 °C, an argon pressure of 1Pa, a sputtering power of 85 W, and a sputtering time of 2 h, and then annealed at 500 °C in an ozone flow for 2 h to obtain a preferentially grown germanium dioxide high oxygen pressure phase transition layer. Using gadolinium nitrate and nickel acetate as solutes and ethylene glycol methyl ether as solvent, a precursor solution is prepared and spin-coated on a Si substrate with a germanium dioxide high oxygen pressure phase introduced, and reacted at 10 MPa oxygen pressure and 1000 °C for 24 h. The resulting 80 nm thick GdNiO3 quasi-single crystal film has a phase transition temperature of 520 K; its principle is as follows Figure 5 As shown, the germanium dioxide high oxygen pressure phase / silicon substrate heterojunction has a specific coherent matching relationship with the 113-type rare earth nickel-based oxide, thereby reducing the Gibbs synthesis free energy of the rare earth nickel-based oxide and promoting its epitaxial growth. The GdNiO3 quasi-single crystal film prepared above is applied with an electric pulse to trigger the metal-insulator transition, and the plasticity of the peak time to the intensity and time of the electric pulse is utilized to realize low-power bionic edge computing.

[0044] Example 4: Taking germanium powder with a particle size of 50 nm as a precursor, annealing at 500 ° C in an ozone atmosphere for 12 h, taking out the germanium dioxide high oxygen pressure phase seed material, using samarium nitrate, nickel nitrate, and PVP as solutes, and water and ethanol as solvents to prepare a precursor solution, placing the germanium dioxide high oxygen pressure phase seed material and the precursor solution in a polytetrafluoroethylene reactor, placing it in a vacuum oven at 120 ° C for 12 h, washing and drying, and calcining at 800 ° C for 6 h to obtain SmNiO3 / germanium dioxide high oxygen pressure phase coated structure powder, whose phase transition temperature is 410 K. The prepared SmNiO3 / germanium dioxide high oxygen pressure phase coated powder is dispersed in a flexible mica substrate, and arranged into a photonic crystal with a random dynamic optical resonant cavity structure through a specific structure, which can realize the function of regulating the transmittance and emissivity of infrared radiation through metal insulator transition within the atmospheric window range.

[0045] Example 5: First, a germanium dioxide high oxygen pressure phase transition layer was grown on a single crystal Ge substrate by magnetron sputtering, with a substrate temperature of 500 °C, a background gas of argon (97%) and oxygen (3%), a pressure of 100 Pa, a sputtering power of 90 W, a sputtering time of 2 h, and then annealed at 500 °C at 5 MPa oxygen pressure for 5 h. La was grown on a Ge substrate with a germanium dioxide high oxygen pressure phase introduced by pulsed laser technology. 1.99 Sr 0.01 NiO4 film, target material is La 1.99 Sr 0.01 NiO4, substrate temperature 600 ℃, oxygen pressure 1 Pa, laser frequency 5Hz, deposition time 10 min, a polycrystalline film with a thickness of 30 nm was obtained. Figure 6 As shown, the germanium dioxide high oxygen pressure phase / germanium substrate heterojunction has a specific coherent matching relationship with the rare earth nickel-based oxide with Ruddlesden-Popper phase layered perovskite structure, thereby reducing the Gibbs synthesis free energy of the metastable oxide and promoting its growth on the surface in a non-uniform nucleation manner. When the polycrystalline film is placed in a KOH solution with a concentration of 1 mol / L, a significant reduction in the overpotential of the oxygen evolution reaction is observed, and it can be used as a catalyst for electrolysis of water to produce oxygen.

[0046] Example 6: Magnetron sputtering on Si 0.3 Ge 0.7 Ge was sputtered on the substrate at a substrate temperature of 300 °C, an argon pressure of 0.5 Pa, a sputtering power of 70 W, and a sputtering time of 1.5 h. The substrate was then placed in a 90 MPa oxygen gas flow and annealed at 600 °C for 1 h to obtain a preferentially grown polycrystalline layer of high oxygen pressure phase of germanium dioxide. Using gadolinium octanoate and nickel octanoate as solutes and xylene as solvent, a precursor solution was prepared and then spin-coated on the Si substrate with a germanium dioxide high oxygen pressure phase transition layer introduced. 0.3 Ge 0.7On the substrate, the reaction was carried out at 12 MPa oxygen pressure and 900 °C for 36 h. The interface between GdNiO3 and the high oxygen pressure phase of germanium dioxide was the Ruddlesden-Popper phase Gd2NiO4, which reduced the lattice mismatch caused by the reduction of the rare earth ion radius. The phase transition temperature of the obtained GdNiO3 polycrystalline film was 500 K. Under the stimulation of external electric field, electrochemical field and cyclic temperature field, the prepared GdNiO3 polycrystalline film undergoes a metal-insulator transition on a very small time scale, has a non-volatile resistance switching function, and can be used in integrated memory devices.

[0047] Example 7: Magnetron sputtering on Si 0.5 Ge 0.5 The germanium dioxide transition layer was grown on the substrate at a substrate temperature of 600 °C, a background gas of argon (97%) and oxygen (3%), a pressure of 80 Pa, a sputtering power of 80 W, a sputtering time of 1 h, and then annealed in an ozone flow at 200 °C for 20 h. 0.5 Ge 0.5 The PrNiO3 polycrystalline film grown on the substrate has a substrate temperature of 500 °C, a background gas of argon (97%) and oxygen (3%), a sputtering pressure of 20 Pa, a sputtering power of 100 W, a sputtering time of 15 min, and a phase transition temperature of 100 K. In order to prepare neuron electronic devices, a discontinuous Pt-Au electrode pair is introduced on the surface of the PrNiO3 film, which is placed in a mixture of hydrogen (10%) and argon (90%) at 100 °C for reaction. The hydrogen ion gradient is established by controlling the hydrogenation time, and an electric pulse is applied to monitor the resistance change in real time, to construct an adaptive dynamic neuron network, simulate the synaptic structure of human brain neurons, and realize the low-energy storage and computing integration function.

[0048] Example 8: A polycrystalline Ge substrate was placed in an ozone flow at 350 °C for annealing for 1 h to obtain a preferentially grown germanium dioxide high oxygen pressure phase polycrystalline layer, and a precursor solution was prepared using samarium nitrate and neodymium nitrate as solutes and ethylene glycol methyl ether as solvent. The precursor solution was then spin-coated on a Ge substrate with a preferentially oriented germanium dioxide high oxygen pressure phase polycrystalline layer, and then placed in an ozone flow at 800 °C for annealing for 12 h to obtain Nd 0.3 Sm 0.7 NiO3 thin film, its phase transition temperature is 300 K. In order to prepare infrared camouflage devices near body temperature, a series of Nd 0.3 Sm 0.7NiO3 thin films are arranged in a large-area array to obtain an infrared camouflage device. When the device is placed on human skin, the infrared emissivity changes suddenly after the body temperature triggers its electronic phase change. The image contrast under the infrared camera is consistent with the environment, thus achieving the effect of infrared camouflage. By changing the rare earth element composition, the characteristic temperature of the infrared camouflage device can be controlled over a wide range.

[0049] Example 9: A single crystal Ge substrate was annealed at 5 MPa oxygen pressure and 350 °C for 1 h, yttrium isobutyrate and nickel isobutyrate were used as solutes, and xylene was used as solvent. The precursor solution was prepared and then spin-coated on the Ge substrate with the germanium dioxide high oxygen pressure phase introduced, and then annealed at 10 MPa oxygen pressure and 600 °C for 24 h to obtain a YNiO3 film. The interface between YNiO3 and the germanium dioxide high oxygen pressure phase is the Ruddlesden-Popper phase Y3Ni2O7, which reduces the lattice mismatch caused by the reduction of the rare earth ion radius. With the increase of the rare earth atomic number, its phase transition temperature gradually increases. By changing the rare earth element composition, the phase transition temperature can be flexibly controlled in a wide range. Therefore, the abrupt thermistor device prepared by this material can meet the needs of different application scenarios.

[0050] Embodiment 10: First, magnetron sputtering is performed on Si 0.2 Ge 0.8 The germanium dioxide transition layer was grown on the substrate at a substrate temperature of 300 °C, with background gas of argon (97%) and oxygen (3%), pressure of 60 Pa, sputtering power of 95 W, sputtering time of 1 h, and then annealed at 400 °C in an ozone flow for 5 h. 0.2 Ge 0.8 ScNiO3 thin film is grown on the substrate, the target material is ScNiO3, the substrate temperature is 700 ℃, the oxygen pressure is 25 Pa, the laser frequency is 5 Hz, the deposition time is 10 min, and its phase transition temperature is 600 K. After the prepared ScNiO3 thin film absorbs microwaves and generates heat, the temperature rises above the phase transition temperature, and it changes from an insulating phase to a metallic phase, and the reflectivity to microwaves increases, which can be used for intelligent microwave protection.

[0051] Example 11: The single crystal Ge substrate was annealed at 8 MPa oxygen pressure and 400 °C for 2.5 h, and then nickel oxide and dysprosium oxide were used as precursors, potassium chloride and lithium chloride were used as molten salts, and annealed at 7 MPa oxygen pressure and 850 °C for 48 h before being taken out. The phase transition temperature of the obtained DyNiO3 polycrystalline film is 550 K. Further introducing a dielectric layer and an electrode on its surface can imitate the organ structure of insect antennae or reptile cheek pits, realize the electrical response function of thermal infrared signals, and can be used for micro fire hazard inspection, night detection, etc.

[0052] Example 12: Magnetron sputtering on Si 0.9Ge 0.1 Ge was grown on the substrate at a substrate temperature of 400 °C, an argon pressure of 10 Pa, a sputtering power of 120 W, and a sputtering time of 3 h, followed by annealing at 240 °C in an ozone flow for 14 h. The precursor solution was prepared using neodymium n-butyrate and nickel n-butyrate as solutes and toluene as solvent, and then spin-coated on the Si with the germanium dioxide high oxygen pressure phase introduced. 0.9 Ge 0.1 On the substrate, it was placed in 8 MPa oxygen pressure and annealed at 700 °C for 36 h to obtain NdNiO3 thin film. A discontinuous Pd electrode was introduced on the surface of the NdNiO3 film, and it was placed in a mixture of hydrogen (10%) and argon (90%) at 100 °C for 3 h. After hydrogenation, the resistivity increased by 7 orders of magnitude. Combined with the bionic design of the shark ampulla structure, it can be used for precise detection of seawater electric fields in deep-sea environments.

[0053] Example 13: The polycrystalline Ge substrate was placed in an oxygen pressure of 7 MPa and annealed at 600 °C for 1.5 h. The resulting germanium dioxide high oxygen pressure phase transition layer thickness was about 50 nm. Nickel oxide, neodymium oxide and samarium oxide were used as precursors, sodium chloride was used as molten salt, and annealed at 7 MPa oxygen atmosphere at 800 °C for 6 h. The resulting Nd 0.5 Sm 0.5 NiO3 is a preferentially grown polycrystalline film with a phase transition temperature of 280 K. It is transparent under visible light and Nd 0.5 Sm 0.5 The NiO3 film undergoes a metal-insulator transformation, which causes its transmittance to drop significantly and its reflectivity to increase significantly, thereby achieving a protective effect against laser weapons.

[0054] Example 14: Ge was first sputtered on a Si wafer by magnetron sputtering, with a substrate temperature of 250 °C, an argon pressure of 3Pa, a sputtering power of 70 W, and a sputtering time of 1.5 h, and then annealed at 350 °C in a 60 MPa oxygen atmosphere for 3 h to obtain a single-crystalline germanium dioxide high oxygen pressure phase with a thickness of 200 nm. Using holmium oxide and nickel oxide as precursors, potassium chloride and lithium chloride as molten salts, the reaction was carried out at 700 °C under 10 MPa oxygen pressure for 12 h, and the resulting HoNiO3 was a quasi-single-crystalline film with a phase transition temperature of 550 K. Based on its sensitivity to protons, it realizes the contact response of Lewis acids and other substances, and imitates the interface receptor structure of biological glutamate channels to realize the active transport function of biomass, which can be used for biomimetic intelligent sensing, semipermeable membrane valve control, etc.

[0055] Example 15: First, germanium dioxide is sputtered on a SiC substrate by magnetron sputtering, the substrate temperature is 300 °C, the background gas is argon (97%) and oxygen (3%), the pressure is 20 Pa, the sputtering power is 100 W, and the sputtering time is 1 h, to obtain a single crystal germanium dioxide high oxygen pressure phase with a thickness of 100 nm. Using samarium nitrate and nickel acetate as solutes, ethylene glycol methyl ether as solvent, and ethanolamine as thickener, a precursor solution is prepared and spin-coated on the SiC substrate with the germanium dioxide high oxygen pressure phase introduced, and reacted at 7 MPa oxygen pressure and 800 °C for 24 h. The obtained SmNiO3 is a polycrystalline film with a phase transition temperature of 400 K. The material is introduced into an electrode and processed into a micro sensor chip, which is combined with biocompatible fabrics to make smart underwear, etc., which can realize 24-hour continuous monitoring of human body temperature and intelligent feedback functions, and can be used for fertility cycle management, intelligent care, etc.

[0056] Example 16: The polished Ge wafer was placed at 5 MPa oxygen pressure and 700 °C for annealing for 2.5 h, and then annealed in ozone gas flow at 500 °C for 0.5 h to obtain a single crystal germanium dioxide transition layer with a thickness of 10 nm. DyNiO3 thin film was grown on the Ge wafer with the high oxygen pressure phase of germanium dioxide by pulsed laser technology. The target material was DyNiO3, the substrate temperature was 600 °C, the oxygen pressure was 50 Pa, the laser frequency was 3 Hz, and the deposition time was 30 min. The phase transition temperature of the obtained DyNiO3 thin film was 520 K. The material was introduced into electrodes and processed into a specific superstructure to achieve surface plasma resonance to change the transmittance and reflectivity of electromagnetic waves in a specific wavelength range, which can be used for wide-range infrared camouflage, bionic light-sensitive cells, etc.

[0057] Example 17: GeO2 was first sputtered on a single crystal Ge substrate by magnetron sputtering, the substrate temperature was 300 °C, the background gas was argon (97%) and oxygen (3%), the pressure was 10 Pa, the sputtering power was 40 W, the sputtering time was 15 min, and then annealed at 6 MPa oxygen pressure and 550 °C for 30 min to obtain a germanium dioxide high oxygen pressure phase transition layer with a thickness of 20 nm. Using europium nitrate and nickel nitrate as solutes, n-butyl acetate as solvent, and acetic anhydride as a desiccant, a precursor solution was prepared and spin-coated on a single crystal Si substrate with a germanium dioxide high oxygen pressure phase introduced, and reacted at 9 MPa oxygen pressure and 750 °C for 3 h. The resulting EuNiO3 was a polycrystalline film with a preferred orientation, and its phase transition temperature was 450 K. Cover it on the engine cover of a drone. When in operation, the heat drives the EuNiO3 film to undergo a metal-insulator transformation, which in turn causes a sudden change in its infrared emissivity. The imaging contrast under an infrared camera is consistent with the atmospheric background, thus achieving infrared camouflage function.

[0058] Example 18: First, a single crystal Ge substrate is placed in a 10 MPa oxygen atmosphere at 650 °C for annealing for 1 h to obtain a single crystal germanium dioxide high oxygen pressure phase with a thickness of 500 nm. Using thulium oxide and nickel oxide as precursors, potassium chloride and lithium chloride as molten salts, react at 15 MPa oxygen pressure and 600 °C for 4 h, the resulting TmNiO3 is a polycrystalline film with preferential orientation, and its phase transition temperature is 600K. A discontinuous Pt electrode is introduced on the surface of the obtained film and placed on a polymer substrate. When no electric field is applied, the TmNiO3 film is in a high emission state and has a temperature contrast under an infrared camera; when a polarization electric field is applied, the TmNiO3 film undergoes a metal-insulator transition and transforms into a low emission state. The imaging contrast under an infrared camera is consistent with the atmospheric background, thereby achieving an infrared camouflage effect.

[0059] Example 19: First, a polycrystalline Ge substrate was annealed at 800 °C in an ozone flow for 30 min to obtain a germanium dioxide high oxygen pressure phase transition layer with a thickness of 50 nm. ErNiO3 thin film was grown on a polycrystalline Ge substrate with a germanium dioxide high oxygen pressure phase by pulsed laser deposition technology. The target material was ErNiO3, the substrate temperature was 500 °C, the oxygen pressure was 70 Pa, the laser frequency was 2 Hz, and the deposition time was 1 h. A preferentially grown polycrystalline ErNiO3 thin film was obtained, and its phase transition temperature was 570 K. A discontinuous Pt-Pd electrode pair was introduced on the surface of the ErNiO3 film, and it was placed in a hydrogen (20%) and nitrogen (80%) mixed gas at 120 °C for 1.5 h. After hydrogenation, the resistivity increased by 4 orders of magnitude. In the proton pre-doped state, the material can absorb protons in the solution environment or release protons to neutralize other ions in the solution environment after applying an electric field, realizing a resistive sensitivity response to different solutes, and can be used for taste sensors.

[0060] Example 20: First, Ge was sputtered on a Si wafer by magnetron sputtering, with a substrate temperature of 350 °C, an argon pressure of 5 Pa, a sputtering power of 40 W, and a sputtering time of 0.5 h. Then, the wafer was placed in a 50 MPa oxygen atmosphere and annealed at 150 °C for 0.5 h to obtain a single crystal germanium dioxide high oxygen pressure phase with a thickness of 10 nm. Lanthanum nitrate, neodymium nitrate and nickel oxalate were used as solutes, and ethylene glycol methyl ether was used as a solvent to prepare a precursor solution and spin-coated it on a Si wafer with a germanium dioxide high oxygen pressure phase introduced. The solution was reacted at 800 °C at 5 MPa oxygen pressure for 3 h. The resulting (La 0.1 Nd 0.9 )NiO3 is an epitaxially grown quasi-single-crystalline thin film with a phase transition temperature of 100 K. It is processed into a specific pattern through laser direct writing technology and introduced into a comparison circuit. It is placed in a liquid nitrogen environment to trigger its metal-insulator transition. After detecting the drastic change in the electrical signal, an alarm message is output. Therefore, it can be used for deep space temperature alarm.

[0061] Example 21: A germanium powder with a particle size of 80 nm was used as a precursor, and after annealing at 500 °C in an ozone atmosphere for 12 h, a germanium dioxide high oxygen pressure phase seed material was obtained. Samarium nitrate, neodymium nitrate, nickel nitrate, and PVP were used as solutes, and ethanol was used as a solvent to prepare a precursor solution. The germanium dioxide high oxygen pressure phase seed material and the precursor solution were placed in a polytetrafluoroethylene reactor, placed in a vacuum oven at 150 °C for reaction for 12 h, washed and dried, and then calcined at 800 °C for 6 h to obtain Sm2Nd2Ni3O 10 / Germanium dioxide high oxygen pressure phase coated structure powder. By using the active oxygen physically adsorbed on the surface of the material, the material is placed in industrial sewage, and the polluted organic matter is oxidized into harmless inorganic matter, thereby achieving the function of low-cost sewage purification.

[0062] Example 22: First, a germanium dioxide high oxygen pressure phase transition layer was grown on a single crystal Si substrate by magnetron sputtering, with a substrate temperature of 500 °C, a background gas of argon (97%) and oxygen (3%), a pressure of 100 Pa, a sputtering power of 90 W, a sputtering time of 2 h, and then annealed at 500 °C at 5 MPa oxygen pressure for 5 h. A precursor solution was prepared using neodymium nitrate, calcium nitrate and nickel acetate as solutes and ethylene glycol methyl ether as solvent and spin-coated on the Si substrate with the germanium dioxide high oxygen pressure phase introduced, and reacted at 700 °C at 5 MPa oxygen pressure for 5 h. The resulting Nd 2.95 Ca 0.05 The Ni2O7 material is a 40 nm thick quasi-single-crystalline thin film. After a transparent conductive oxide and a highly reflective metal functional layer are sputtered on its surface, it can controllably collect and release indoor heat, thereby realizing an adjustable infrared radiation cooling function, which can be used for seasonal smart windows.

Claims

1. A method for growing germanium-based rare earth nickel-based oxide electronic phase change materials, characterized in that: A germanium dioxide high oxygen pressure phase that has a lattice matching relationship with the rare earth nickel-based oxide electronic phase change semiconductor material in a thermodynamically metastable phase and is stable in the same high oxygen pressure range is introduced as a seed or transition layer, thereby effectively growing a composite powder of rare earth nickel-based oxide coated with germanium dioxide high oxygen pressure phase, a rare earth nickel-based oxide / germanium dioxide high oxygen pressure phase / germanium substrate heterojunction, and a rare earth nickel-based oxide / germanium dioxide high oxygen pressure phase / silicon substrate heterojunction; through the growth of the above-mentioned rare earth nickel-based oxide material on silicon-based and germanium-based substrates, it is compatible with traditional silicon-based semiconductor micromachining and device preparation processes, thereby realizing the application of neuron devices, mutant thermistors, infrared camouflage devices, and laser weapon protection layers.

2. The method for growing germanium-based rare earth nickel-based oxide electronic phase change material according to claim 1, characterized in that: The seed crystal or transition layer is a germanium dioxide high oxygen pressure phase, has a similar lattice constant to the rare earth nickel-based oxide, and is in a thermodynamically stable state under the high oxygen pressure conditions required for the growth of the rare earth nickel-based oxide; the rare earth nickel-based oxide can be directly coated on the germanium dioxide high oxygen pressure phase powder by a high oxygen pressure molten salt reaction and a hydrothermal reaction method to prepare a composite powder; or firstly grow a germanium dioxide high oxygen pressure phase transition layer on a substrate, then use spin coating, pulsed laser deposition, magnetron sputtering deposition and molten salt assisted method to grow a rare earth nickel-based oxide film precursor and anneal under high oxygen pressure to prepare a rare earth nickel-based oxide / germanium dioxide / substrate heterojunction film; or firstly grow a Ge transition layer on a substrate and anneal at a high oxygen pressure of 0.2-500 MPa at 50-1500 ºC, 20-300 in an ozone atmosphere, ºC oxidation and oxygen plasma oxidation to generate germanium dioxide high oxygen pressure phase, and then use spin coating, pulsed laser deposition, magnetron sputtering deposition and molten salt assisted method to grow rare earth nickel-based oxide film precursor and anneal under high oxygen pressure to prepare rare earth nickel-based oxide / germanium dioxide / substrate heterojunction film; in the above-mentioned germanium dioxide and germanium oxidation process at high oxygen pressure and ozone, the stoichiometric ratio and crystal structure of the generated germanium dioxide high oxygen pressure phase transition layer and the silicon-based substrate and rare earth nickel-based oxide interface can be reduced by adjusting the oxidation process parameters to reduce the lattice mismatch.

3. The method for growing germanium-based rare earth nickel-based oxide electronic phase change material according to claim 1, characterized in that: The synthesized rare earth nickel-based oxide electronic phase change material has a 113-type distorted perovskite structure, and its chemical formula is ReNiO3, wherein Re is a single rare earth or a combination of multiple rare earth elements except lanthanum, including praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y) and scandium (Sc); the electronic structure of the rare earth nickel-based oxide can be regulated by the design of rare earth element components, thereby adjusting its metal-insulator transition characteristics and hydrogen-induced electronic phase change characteristics; the method for synthesizing the rare earth nickel-based oxide material includes pulsed laser deposition technology, magnetron sputtering method, hydrothermal method, wet chemical spin coating method, sol-gel method and molten salt method; the orientation and thickness of the rare earth nickel-based oxide electronic phase change material can be regulated by changing the synthesis process.

4. The method for growing germanium-based rare earth nickel-based oxide electronic phase change material according to claim 1, characterized in that: The rare earth nickel-based oxide electronic phase change material prepared also has a Ruddlesden-Popper phase layered perovskite structure, and its chemical formula is (Re 1-x Ae x ) n+1 Ni n O 3n+1 , the structural feature is a single-layer rock salt layer structure (Re 1-x Ae x )O and n-layer perovskite structure (Re 1-x Ae x )NiO3 are arranged alternately; Re is a single rare earth or a combination of multiple rare earth elements, including lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), Ae is an alkaline earth element; n is 1, 2, 3, corresponding to (Re 1-x Ae x )2NiO4、(Re 1-x Ae x )3Ni2O7、(Re 1- x Ae x )4Ni3O 10 .

5. The method for growing germanium-based rare earth nickel-based oxide electronic phase change material according to claim 1, characterized in that: In order to synthesize germanium dioxide high oxygen pressure phase powder coated with rare earth nickel-based oxide, commercial germanium dioxide can be used as a precursor to be oxidized in a high oxygen pressure or ozone atmosphere to obtain the germanium dioxide high oxygen pressure phase, and germanium powder can also be used as a precursor to be oxidized in a high oxygen pressure or ozone atmosphere to obtain the germanium dioxide high oxygen pressure phase; the germanium dioxide high oxygen pressure phase powder has a curved surface shape including sphere, ellipsoid, and cylinder, and its size range is 0.1 μm-1 cm; the surface of the germanium dioxide high oxygen pressure phase powder has an adsorption effect on rare earth element oxides and nickel element oxide precursors in a molten flux, and has a lattice matching relationship with the fitted rare earth nickel-based oxide, thereby promoting the non-uniform nucleation and growth of the rare earth nickel-based oxide on its surface to form a coating structure.

6. The method for growing germanium-based rare earth nickel-based oxide electronic phase change material according to claim 1, characterized in that: In order to synthesize polycrystalline rare earth nickel-based oxide / germanium dioxide high oxygen pressure phase / germanium substrate heterojunction, the germanium substrate is first annealed under MPa-level high oxygen pressure, annealed in ozone atmosphere or oxidized in oxygen plasma to generate a germanium dioxide high oxygen pressure phase transition layer. By adjusting the thickness of the transition layer and the rare earth nickel-based oxide growth process, the preferred orientation of the rare earth nickel-based oxide polycrystalline film can be controlled, and its thickness ranges from 1 to 1000 nm; or glass, quartz, mica, silicon carbide, Si 1-x Ge x The substrate replaces the germanium substrate, and the germanium is further oxidized by plasma sputtering or directly sputtered by oxygen plasma to generate a germanium dioxide high oxygen pressure phase, so as to achieve heterogeneous nucleation of rare earth nickel-based oxides on the surface of the germanium dioxide high oxygen pressure phase transition layer and grow into a polycrystalline film with preferred orientation.

7. The method for growing germanium-based rare earth nickel-based oxide electronic phase change material according to claim 1, characterized in that: In order to synthesize a rare earth nickel-based oxide quasi-single crystal film / germanium dioxide high oxygen pressure / silicon substrate heterojunction, a germanium dioxide high oxygen pressure phase transition layer is obtained by plasma sputtering germanium and then further oxidizing it or by direct sputtering of oxygen plasma; the germanium dioxide high oxygen pressure phase / silicon substrate heterojunction has a specific coherent matching relationship with the rare earth nickel-based oxide, thereby reducing the Gibbs synthesis free energy of the rare earth nickel-based oxide and promoting its epitaxial growth; by adjusting the thickness of the transition layer and the rare earth nickel-based oxide deposition process, the growth of a rare earth nickel-based oxide quasi-single crystal film can be achieved, and the thickness of the transition layer ranges from 1 to 1000 nm.

8. The method for growing germanium-based rare earth nickel-based oxide electronic phase change material according to claim 1, characterized in that: The prepared rare earth nickel-based oxide / germanium dioxide high oxygen pressure phase / silicon substrate heterojunction can be connected to the existing silicon-based semiconductor device process and further prepared into proton-regulated neuron devices and strongly correlated electronic devices based on electric field and temperature-triggered metal-insulator phase transitions.

9. The method for growing germanium-based rare earth nickel-based oxide electronic phase change material according to claim 1, characterized in that: Based on the sudden change of infrared optical properties triggered by rare earth nickel-based oxide at characteristic temperature, laser weapon protective coatings and infrared camouflage devices can be prepared using the rare earth nickel-based oxide / germanium dioxide high oxygen pressure / germanium substrate heterojunction grown by the present invention.

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