CN107425053B - Method for constructing concentric core-shell three-dimensional nano multiferroic heterojunction array by using ALD (atomic layer deposition) - Google Patents
Method for constructing concentric core-shell three-dimensional nano multiferroic heterojunction array by using ALD (atomic layer deposition) Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/06—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions
- H01L29/0684—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions characterised by the shape, relative sizes or dispositions of the semiconductor regions or junctions between the regions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/34—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
Abstract
The invention discloses a method for constructing a concentric core-shell three-dimensional nano multiferroic heterojunction array by ALD, which comprises the steps of firstly growing a ZnO nanowire array on conductive glass, then utilizing the ZnO nanowire array as a template, adopting an atomic layer deposition method ALD to sequentially deposit a ferroelectric film and a magnetic film, sputtering a layer of metal electrode on the top of the ZnO nanowire array after etching the ferroelectric film and the magnetic film on the top of the ZnO nanowire array to obtain the three-dimensional nano multiferroic heterojunction array with a concentric core-shell structure, solving the technical problems that the existing multiferroic heterojunction still stays in a planar structure and can not realize miniaturization, being compatible with the existing mainstream three-dimensional microelectronic device process, being simple in operation, low in price, safe, nontoxic, pollution-free and beneficial to quantity, and realizing the transition of the multiferroic heterojunction from the planar structure to the three-dimensional structure by an effective technical route and a solution, a bottleneck breakthrough is realized for the transition from macroscopic size to microscopic size.
Description
Technical Field
The invention belongs to the technical field of multiferroic heterojunction, and particularly relates to a method for constructing a concentric core-shell three-dimensional nano multiferroic heterojunction array by using ALD (atomic layer deposition).
Background
With the rapid development of microelectronics and semiconductor technologies, three-dimensionality, miniaturization, adjustability and multi-functionalization have become new trends in the design and development of current electronic components. The exploration and development of novel intelligent multi-scale materials related to the material, in particular to a multiferroic material which integrates the electrical property and the magnetism and permeates into various fields of modern technology, has become a research hotspot in the last decade. The multiferroic material not only has two or three single ferroicity (such as ferroelectricity, ferromagnetism and ferroelasticity), but also can generate some new functions through the coupling synergistic action of the ferroelectricity, for example, the magnetoelectric coupling effect exists between the ferroelectricity and the ferromagnetism, so that the electric control of magnetism or magnetic control electricity becomes possible. In addition, the multiferroic material can also realize the regulation and control effect of a magnetic field on dielectric constant or capacitance. At present, although many single-phase multiferroic materials are discovered by researchers, compared with the weak magnetoelectric coupling effect of the single-phase multiferroic material at room temperature, the artificially constructed laminated multiferroic heterojunction has better selectivity and flexibility in material combination and structure design, can realize stronger magnetoelectric coupling effect and generate novel physical phenomena and regulation mechanisms, particularly complex interaction exists among electron spin, charge, orbit and crystal lattice at an interface, can cause a plurality of new magnetoelectric physical phenomena, is expected to realize a new generation of multifunctional devices integrating magnetoelectric in one body, and has important application prospects in the fields of new generation of memories, sensors, microwave devices and the like. Therefore, the limitation of the existing preparation technology needs to be broken through, and a three-dimensional multiferroic heterojunction is designed and constructed, so that the method has important significance for solving key problems such as integration, technical connection and the like of the multiferroic heterojunction and a microelectronic device. Therefore, how to build the multiferroic heterojunction with the three-dimensional layer nano-composite structure is the core of the invention from the structural design and functional requirements of the device. However, to date, the following methods have been mainly used for preparing a thin film: (1) the method has long history, simple required equipment and low cost, but has poor film forming quality, high content of defects and impurities in the film and poor controllability of the thickness and uniformity of the film. (3) The Pulse Laser Deposition (PLD) method has simple process, good crystallization quality of the film, but poor large-area uniformity and film thickness accuracy controllability, and can not realize three-dimensional uniform conformal coverage. (4) Magnetron sputtering is the most commonly used method for growing magnetic oxide films, which has better plane uniformity and film-forming quality, but can not realize sub-nanometer precise control in the aspect of precise control of film thickness, and especially can not realize three-dimensional uniform conformal coverage on a substrate with a complex three-dimensional nano structure. (5) Thin films with certain three-dimensional uniformity can be prepared by Chemical Vapor Deposition (CVD), but CVD still does not allow precise control of film thickness and uniform and conformal thin films to be deposited on three-dimensional structures with large aspect ratios. In summary, the conventional methods for preparing thin films all have the bottleneck problems that the film thickness cannot be precisely controlled and three-dimensional uniform conformal coverage cannot be realized. The most key problem for constructing the three-dimensional multiferroic heterojunction is to realize conformal growth of a magnetic film and a ferroelectric film on a three-dimensional structure, so that the limitation of the traditional technologies such as pulse laser deposition, chemical vapor deposition and magnetron sputtering at present can be broken through only by developing a new technology with 100% of three-dimensional uniformity, and the three-dimensional multiferroic heterojunction can be constructed. Considering three-dimensional uniformity and compatibility, the atomic layer deposition technology becomes the preferred technology for constructing the three-dimensional laminated multiferroic heterojunction.
The Atomic Layer Deposition (ALD) thin film Deposition technique is a self-limiting (self-limiting) surface growth method, and has very good three-dimensional uniformity. ALD has been a key technology in the microelectronics field for the fabrication of high quality dielectric layers and CMOS transistor high-k layers for Dynamic Random Access Memory (DRAMs) trench capacitors. ALD is a self-limiting thin film deposition technology capable of realizing the layer-by-layer growth of a monoatomic layer, and is characterized in that a 100% uniform conformal thin film with accurately controllable thickness can be deposited on a three-dimensional structure with any shape, so that the urgent need of preparing a three-dimensional microelectronic device is met.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for constructing a concentric core-shell three-dimensional nano multiferroic heterojunction array by using ALD (atomic layer deposition), and solves the technical problems that the conventional multiferroic heterojunction still stays in a planar structure and cannot be miniaturized.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the method comprises the following steps:
1) growing a ZnO nanowire array on the conductive glass;
2) depositing a uniform and conformal ferroelectric film on the ZnO nanowire array by utilizing an organic metal precursor source and an oxygen source;
3) depositing a uniform and conformal magnetic film on the ZnO nanowire array deposited with the ferroelectric film by using an iron source and an oxygen source;
4) etching the ferroelectric film and the magnetic film on the top of the ZnO nanowire array to expose the top of the ZnO nanowire array;
5) and sputtering a layer of metal electrode on the top of the ZnO nanowire array by using a magnetron sputtering method to obtain the three-dimensional nano multiferroic heterojunction array with the concentric core-shell structure.
In the step 1), a hydrothermal method is adopted to grow the ZnO single crystal nanowire array on the conductive glass, and the surface of the ZnO single crystal nanowire array is cleaned by blowing dry nitrogen.
Heating the conductive glass to 200-300 ℃ before depositing the ferroelectric film in the step 2).
In the step 2), the organic metal precursor source is cyclopentadiene grade Ba or a mixture of bis (2,2,6,6, -tetramethyl-3, 5-heptanedionate) lead, titanium tetraisopropoxide and tetrakis (ethylmethylamino) zirconium, and the oxygen source is deionized water.
The step 2) of depositing the ferroelectric thin film comprises a plurality of atomic layer deposition cycles, and each atomic layer deposition cycle comprises: firstly, performing oxygen source pulse for 1-4 seconds, then performing nitrogen cleaning pulse for 3-8 seconds, then performing organic metal precursor source pulse for 0.1-04 seconds, and finally performing nitrogen cleaning pulse for 6-16 seconds.
Heating the conductive glass to 350-450 ℃ before depositing the magnetic film in the step 3).
In the step 3), the iron source is ferrocene steam, and the oxygen source is oxygen.
The process of depositing the magnetic thin film in the step 3) comprises a plurality of atomic layer deposition cycles, and each atomic layer deposition cycle comprises: firstly, performing oxygen source pulse for 1-4 s; then cleaning for 6-16s by using nitrogen; secondly, performing ferrocene source pulse for 0.1-0.4 s; and finally, cleaning for 6-16s by using nitrogen.
And 4) etching the ferroelectric film and the magnetic film on the top of the ZnO nanowire array by adopting inductively coupled plasma, wherein the plasma adopts argon plasma.
The metal electrode in the step 5) is Pt or Au.
The conductive glass is FTO or ITO conductive glass.
After the metal electrode is sputtered on the top of the ZnO nanowire in the step 5), the conductive glass of the three-dimensional nano multiferroic heterojunction array with the concentric core-shell structure is placed into a tubular atmosphere furnace, and N is carried out2And H2Annealing in a mixed reducing atmosphere of H2And N2The mixed gas is mixed according to the volume ratio of 1: 9-1: 15, the annealing temperature is 300-400 ℃, and the annealing time is 1-3 hours.
Compared with the prior art, the method has the advantages that the ZnO nanowire array is firstly grown on the conductive glass, then the ZnO nanowire array is used as the template, the ferroelectric film and the magnetic film are sequentially deposited by adopting the atomic layer deposition method ALD, after the ferroelectric film and the magnetic film on the top of the ZnO nanowire array are etched, a layer of metal electrode is sputtered on the top of the ZnO nanowire array, and the three-dimensional nano multiferroic heterojunction array with the concentric core-shell structure is obtained. In addition, the transition from the plane to the three-dimension of the multiferroic heterojunction is realized, the transition from the existing millimeter macroscopic scale to the microscopic nanometer scale of the conventional multiferroic heterojunction can be realized, and the integration level of related devices based on the multiferroic heterojunction can be greatly improved. The invention solves the technical problems that the existing multiferroic heterojunction still stays in a planar structure and can not realize miniaturization, is compatible with the existing mainstream three-dimensional microelectronic device process, has simple operation, low price, safety, no toxicity, no pollution and favorable quantity, realizes the transition of the multiferroic heterojunction from the planar structure to the three-dimensional structure by an effective technical route and a solution, and realizes the bottleneck breakthrough of the transition from the macroscopic size to the microscopic size.
Drawings
FIG. 1 is a method roadmap of the present invention.
Detailed Description
The invention is further explained below with reference to specific embodiments and the drawing of the description.
Referring to fig. 1, the present invention comprises the steps of:
1) growing a ZnO nanowire array on the conductive glass;
2) depositing a uniform and conformal ferroelectric film on the ZnO nanowire array by utilizing an organic metal precursor source and an oxygen source;
3) depositing a uniform and conformal magnetic film on the ZnO nanowire array deposited with the ferroelectric film by using an iron source and an oxygen source;
4) etching the ferroelectric film and the magnetic film on the top of the ZnO nanowire array to expose the top of the ZnO nanowire array;
5) and sputtering a layer of metal electrode on the top of the ZnO nanowire array by using a magnetron sputtering method to obtain the three-dimensional nano multiferroic heterojunction array with the concentric core-shell structure.
Example 1
The method comprises the following steps:
1) a ZnO monocrystal nanowire array grown on FTO or ITO conductive glass by a hydrothermal method is washed by dry nitrogen for later use;
2) feeding the ZnO nanowire array grown on the conductive glass in the step 1) into an atomic layer deposition system through a vacuum loading mechanical arm of the atomic layer deposition system, and heating to 200-300 ℃ to prepare for depositing a ferroelectric thin film material;
3) adopting cyclopentadiene grade Ba [ (cp-Ba) -type on the basis of the step 2)]And deionized water (H)2O) are respectively used as Ba precursor source and O precursor source, and ALD technology is utilized to deposit uniform and conformal BaTiO on the surface of the ZnO nanowire3Film-forming BaTiO3a/ZnO core-shell structure; or using lead [ P ] bis (2,2,6,6, -tetramethyl-3, 5-heptanedionate)b(DPM2)]Titanium tetraisopropoxide [ Ti (Oi-Pr)4]Tetrakis (ethylmethylamino) zirconium (Zr (DIBM)4) And deionized water as precursor sources of Pb, Ti, Zr and O respectively, and uniformly and conformally depositing Pb (Zr) on the ZnO nanowire arrayx,Ti1-x)O3Film formation of Pb (Zr)x,Ti1-x)O3a/ZnO core-shell structure;
the atomic layer deposition of the ferroelectric film is implemented by the following steps: loading the ZnO nanowire array substrate into an ALD reaction cavity through a vacuum manipulator, heating the ZnO nanowire array substrate, and ensuring that pure N is in the reaction cavity2Before heating, the ALD system performs ventilation on the reaction cavity for 1 time by utilizing the ventilation function of the ALD system, and the specific implementation process is that the system automatically ventilates N of each source pipeline2The flow rate of the carrier gas is set to 2000sccm, the vacuum pumping system of the reaction cavity is closed at the same time, and the system automatically closes the carrier gas and opens the V after the pressure of the reaction cavity reaches one atmospheric pressure6The air extraction valve is used for extracting the gas in the reaction cavity, so that the pure N in the reaction cavity can be ensured2And additionally, N of 50sccm per source line is maintained during heating2And gas flow is carried out to ensure that the pressure of the reaction cavity is maintained at about 1000Pa, the temperature of a furnace wire is set to 600 ℃ in the heating process, the temperature of the substrate is set to 400 ℃, and after the temperature of the substrate is stabilized to 400 ℃, the set ALD film deposition program can be executed, and the specific program is as follows: the first pulse is oxygen source pulse, the oxygen source pulse time is 1.0-4.0 seconds, and the nitrogen cleaning pulse of 3.0-8.0 seconds follows after the pulse; the second pulse is 0.1-04 seconds of cyclopentadiene grade Ba [ (cp-Ba) -type]Bis (2,2,6,6, -tetramethyl-3, 5-heptanedionato) lead [ P ]b(DPM2)]Titanium tetraisopropoxide [ Ti (Oi-Pr)4]And tetrakis (ethylmethylamino) zirconium (Zr (DIBM)4Pulse, nitrogen cleaning pulse of 6-16 seconds after pulse, N as carrier gas of organic metal precursor source and oxygen source2The flow rates of gas and gas are respectively 100-2The carrier gas flow is set to be 80 sccm;
4) the specific process of depositing the uniform and conformal magnetic film on the surface of the ZnO nanowire array deposited with the ferroelectric film by ALD (atomic layer deposition) again to construct the concentric core-shell structure three-dimensional nano multiferroic heterojunction array comprises the following steps: the substrate is sent into a vacuum reaction cavity and heated to 350 ℃ in the inert atmosphere in the vacuum reaction cavityAt 450 ℃, taking ferrocene as an iron source and oxygen as an oxygen source, pulsing ferrocene steam and oxygen into a carrier gas system of the atomic layer deposition equipment, then sending the gas system into a vacuum reaction cavity, and carrying out atomic layer deposition circulation in an inert gas atmosphere until uniform and conformal Fe is deposited on the surface of the substrate3O4Thin film in which Fe is atomic layer deposited3O4The specific cycle of the film comprises the following steps: firstly, performing oxygen source pulse for 1-4 seconds; then cleaning for 6-16 seconds by using nitrogen; secondly, performing ferrocene source pulse for 0.1-0.4 seconds; finally, cleaning for 6-16 seconds by using nitrogen, and finally forming a concentric core-shell structure three-dimensional nano multiferroic heterojunction array;
5) putting the substrate obtained in the step 4) into an inductively coupled plasma etching machine, etching the ferroelectric film and the ferromagnetic film on the top of the ZnO nanowire array by using inductively coupled plasma, and exposing the top of the ZnO nanowire array, wherein the used plasma is argon plasma;
6) putting the substrate obtained in the step 5) into a magnetron sputtering system, sputtering a layer of Pt or Au noble metal on the top of the concentric core-shell structure three-dimensional nano multiferroic heterojunction array at room temperature by using magnetron sputtering to serve as a top electrode for testing the magnetoelectric coupling of the three-dimensional nano multiferroic heterojunction array, wherein the bottom electrode is served as an FTO or ITO conductive film on conductive glass used for growing the ZnO nanowire array.
Example 2
The method comprises the following steps:
1) ZnO single crystal nanowire arrays grown on FTO or ITO conductive glass by a hydrothermal method are washed on the surfaces of the ZnO single crystal nanowire arrays by dry nitrogen blow washing for standby.
2) And (2) conveying the ZnO nanowire array substrate grown on the conductive glass in the step (1) into an atomic layer deposition system through a vacuum loading mechanical arm of the atomic layer deposition system, and heating to 200-300 ℃ to prepare for depositing a ferroelectric thin film material.
3) Adopting cyclopentadiene grade Ba [ (cp-Ba) -type on the basis of the step 2)]And deionized water (H)2O) are respectively used as Ba precursor source and O precursor source, and ALD technology is utilized to form ZnO nanowire surfaceDepositing uniform and conformal BaTiO3Film-forming BaTiO3a/ZnO core-shell structure; or using lead [ P ] bis (2,2,6,6, -tetramethyl-3, 5-heptanedionate)b(DPM2)]Titanium tetraisopropoxide [ Ti (Oi-Pr)4]Tetrakis (ethylmethylamino) zirconium (Zr (DIBM)4) And deionized water as precursor sources of Pb, Ti, Zr and O respectively, and uniformly and conformally depositing Pb (Zr) on the ZnO nanowire arrayx,Ti1-x)O3Film formation of Pb (Zr)x,Ti1-x)O3a/ZnO structure;
the atomic layer deposition of the ferroelectric film is implemented by the following steps: the ZnO nanowire array substrate is loaded and sent into the ALD reaction cavity through the vacuum manipulator, and then the ZnO nanowire array substrate starts to be heated, so that pure N is arranged in the reaction cavity2Before heating, the ALD system performs ventilation on the reaction cavity for 1 time by utilizing the ventilation function of the ALD system, and the specific implementation process is that the system automatically ventilates N of each source pipeline2The carrier gas flow is set to 2000 sccm; and simultaneously closing the vacuum pumping system of the reaction cavity, automatically closing the carrier gas and opening the V6 pumping valve after the pressure of the reaction cavity reaches one atmosphere, and pumping away the gas in the reaction cavity, thereby ensuring that the inside of the reaction cavity is relatively pure N2Furthermore, we maintain N at 50sccm per source line during heating2And the gas flow is adopted to ensure that the pressure of the reaction cavity is maintained at about 1000 Pa. After the substrate temperature is stabilized to 400 ℃ such as the furnace wire temperature is set to 600 ℃ and the substrate temperature is set to 400 ℃ in the heating process, the set ALD thin film deposition program can be executed, and the specific program is as follows: the first pulse is oxygen source pulse, the oxygen source pulse time is 1-4 seconds, and 3-8 seconds of nitrogen cleaning pulse is followed after the pulse; the second pulse is 0.1-04 seconds of cyclopentadiene grade Ba [ (cp-Ba) -type]Bis (2,2,6,6, -tetramethyl-3, 5-heptanedionato) lead [ P ]b(DPM2)]Titanium tetraisopropoxide [ Ti (Oi-Pr)4]Or tetrakis (ethylmethylamino) zirconium (Zr (DIBM)4Pulse, 6-16 seconds of nitrogen cleaning pulse nitrogen cleaning is carried out after the pulse is finished, and carrier gases of the organic metal precursor source and the oxygen source are both N2The flow rate of gas is 100-50-200sccm, N of other source lines2The carrier gas flow is set to be 80 sccm;
4) the specific process of depositing the uniform and conformal magnetic film on the surface of the ZnO nanowire array deposited with the ferroelectric film by ALD again to form the concentric core-shell structure three-dimensional nano multiferroic heterojunction array comprises the following steps: conveying the substrate into a vacuum reaction cavity, heating to 350-450 ℃ under the inert gas atmosphere in the vacuum reaction cavity, introducing ferrocene steam and oxygen into a carrier gas system of atomic layer deposition equipment by taking ferrocene as an iron source and oxygen as an oxygen source, conveying the ferrocene steam and the oxygen into the vacuum reaction cavity through the carrier gas system, and performing atomic layer deposition circulation in the inert gas atmosphere until uniform and conformal Fe is deposited on the surface of the substrate obtained in the step 3)3O4A thin film, atomic layer deposition cycle comprising the steps of: firstly, performing oxygen source pulse for 1-4 s; then cleaning for 6-16s by using nitrogen; secondly, performing ferrocene source pulse for 0.1-0.4 s; finally, cleaning for 6-16 seconds by using nitrogen, and finally forming a concentric core-shell structure three-dimensional nano multiferroic heterojunction array;
5) putting the substrate obtained in the step 4) into an inductively coupled plasma etching machine, etching the ferroelectric film and the ferromagnetic film on the top of the ZnO nanowire array by using inductively coupled plasma, and exposing the top of the ZnO nanowire array, wherein the used plasma is argon plasma;
6) putting the substrate obtained in the step 5) into a magnetron sputtering system, sputtering a layer of Pt or Au noble metal on the top of the concentric core-shell structure three-dimensional nano multiferroic heterojunction array at room temperature by utilizing magnetron sputtering to serve as a top electrode for testing the magnetoelectric coupling of the three-dimensional nano multiferroic heterojunction array, wherein the bottom electrode is served as an FTO or ITO conductive film on conductive glass used for growing the ZnO nanowire array;
7) putting the concentric core-shell structure three-dimensional nano multiferroic heterojunction array structure prepared in situ in the step 6) into a tubular atmosphere furnace, and putting the structure in N2And H2Annealing in a mixed reducing atmosphere of (1), the reducing atmosphere being H2And N2The mixed gas is mixed according to the volume ratio of 1: 9-1: 15, the annealing temperature is 300-400 ℃, and the annealing time is 1-3 hours.
By comparing example 1 with example 2, it is found that the concentric core-shell structure three-dimensional nano multiferroic heterojunction array prepared in situ in example 1 has three-dimensional superparamagnetism, while the concentric core-shell structure three-dimensional nano multiferroic heterojunction array prepared in example 2 shows ferrimagnetism, the magnetism of the two can be regulated and controlled through magnetoelectric coupling in a ferroelectric phase and a ferromagnetic phase, and the concentric core-shell structure three-dimensional nano multiferroic heterojunction array prepared in example 2 has larger magnetoelectric regulation and control performance.
In conclusion, the method utilizes the existing mature ALD and ZnO nanowire array template to prepare the concentric core-shell structure three-dimensional nano multiferroic heterojunction array, breaks through the limitation that the existing multiferroic heterojunction still stays in a planar structure and has macroscopic size, and has important significance for the step-to-three-dimension, miniaturization and compatibility with the existing mainstream microelectronic device of the multiferroic heterojunction. The method is simple and easy in preparation process, is compatible with the existing semiconductor preparation process, and can prepare the high-quality concentric core-shell structure three-dimensional nano multiferroic heterojunction array.
Claims (7)
1. A method for constructing a concentric core-shell three-dimensional nano multiferroic heterojunction array by using ALD (atomic layer deposition), is characterized by comprising the following steps:
1) growing a ZnO nanowire array on the conductive glass;
2) depositing a uniform and conformal ferroelectric film on the ZnO nanowire array by utilizing an organic metal precursor source and an oxygen source;
3) depositing a uniform and conformal magnetic film on the ZnO nanowire array deposited with the ferroelectric film by using an iron source and an oxygen source;
4) etching the ferroelectric film and the magnetic film on the top of the ZnO nanowire array to expose the top of the ZnO nanowire array;
5) sputtering a layer of metal electrode on the top of the ZnO nanowire array by using a magnetron sputtering method to obtain a three-dimensional nano multiferroic heterojunction array with a concentric core-shell structure;
growing a ZnO monocrystal nanowire array on conductive glass by adopting a hydrothermal method in the step 1), and purging with dry nitrogen to clean the surface of the ZnO monocrystal nanowire array;
heating the conductive glass to 350-450 ℃ before depositing the magnetic film in the step 3);
in the step 3), the iron source is ferrocene steam, and the oxygen source is oxygen.
2. The method for constructing the concentric core-shell three-dimensional nano multiferroic heterojunction array by using ALD (atomic layer deposition) as claimed in claim 1, wherein the conductive glass is heated to 200-300 ℃ before the ferroelectric thin film is deposited in the step 2).
3. The method for constructing the concentric core-shell three-dimensional nano multiferroic heterojunction array by using ALD (atomic layer deposition) as claimed in claim 2, wherein the organic metal precursor source in the step 2) is cyclopentadiene-grade Ba or a mixture of bis (2,2,6,6, -tetramethyl-3, 5-heptanedionate) lead, titanium tetraisopropoxide and tetrakis (ethylmethylamino) zirconium, and the oxygen source is deionized water.
4. The method for constructing the concentric core-shell three-dimensional nano-multiferroic heterojunction array by ALD (atomic layer deposition) according to claim 3, wherein the step 2) of depositing the ferroelectric thin film comprises a plurality of atomic layer deposition cycles, and each atomic layer deposition cycle comprises: firstly, performing oxygen source pulse for 1-4 seconds, then performing nitrogen cleaning pulse for 3-8 seconds, then performing organic metal precursor source pulse for 0.1-04 seconds, and finally performing nitrogen cleaning pulse for 6-16 seconds.
5. The method for constructing the concentric core-shell three-dimensional nano-multiferroic heterojunction array by using ALD (atomic layer deposition) as claimed in claim 1, wherein the step 3) of depositing the magnetic thin film comprises a plurality of atomic layer deposition cycles, and each atomic layer deposition cycle comprises: firstly, performing oxygen source pulse for 1-4 s; then cleaning for 6-16s by using nitrogen; secondly, performing ferrocene source pulse for 0.1-0.4 s; and finally, cleaning for 6-16s by using nitrogen.
6. The method for constructing the concentric core-shell three-dimensional nano multiferroic heterojunction array by using ALD (atomic layer deposition) as claimed in claim 1, wherein in the step 4), the ferroelectric film and the magnetic film on the top of the ZnO nanowire array are etched by using inductively coupled plasma, and argon plasma is used as the plasma.
7. The method for constructing the concentric core-shell three-dimensional nano multiferroic heterojunction array by using ALD (atomic layer deposition) as claimed in claim 1, wherein the metal electrode in the step 5) is Pt or Au, and after the metal electrode is sputtered on the top of the ZnO nanowire in the step 5), the conductive glass with the concentric core-shell three-dimensional nano multiferroic heterojunction array is placed in a tubular atmosphere furnace, and N is added2And H2Annealing in a mixed reducing atmosphere of H2And N2The mixed gas is mixed according to the volume ratio of 1: 9-1: 15, the annealing temperature is 300-400 ℃, and the annealing time is 1-3 hours.
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