CN112151671B - Organic spin valve device based on two-dimensional metal organic framework thin film material and preparation method - Google Patents
Organic spin valve device based on two-dimensional metal organic framework thin film material and preparation method Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 38
- 239000010409 thin film Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 52
- 239000010408 film Substances 0.000 claims abstract description 51
- PIRUAZLFEUQMTG-UHFFFAOYSA-N lanthanum;oxomanganese;strontium Chemical compound [Sr].[La].[Mn]=O PIRUAZLFEUQMTG-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000002791 soaking Methods 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 239000013110 organic ligand Substances 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 12
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052737 gold Inorganic materials 0.000 claims abstract description 10
- 239000010931 gold Substances 0.000 claims abstract description 10
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims abstract description 9
- 239000011241 protective layer Substances 0.000 claims abstract description 8
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 3
- 150000001879 copper Chemical class 0.000 claims abstract description 3
- 150000002815 nickel Chemical class 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 70
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000004544 sputter deposition Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000013077 target material Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- -1 lanthanum aluminate Chemical class 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 16
- 238000012512 characterization method Methods 0.000 description 8
- 230000005294 ferromagnetic effect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QMLILIIMKSKLES-UHFFFAOYSA-N triphenylene-2,3,6,7,10,11-hexol Chemical compound C12=CC(O)=C(O)C=C2C2=CC(O)=C(O)C=C2C2=C1C=C(O)C(O)=C2 QMLILIIMKSKLES-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
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Abstract
The invention discloses an organic spin valve device based on a two-dimensional metal organic framework thin film material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) preparing a strip-shaped lanthanum strontium manganese oxygen bottom electrode on a substrate by a magnetron sputtering method to obtain the substrate with the strip-shaped lanthanum strontium manganese oxygen bottom electrode; (2) immersing the substrate in the step (1) into an aminosilane solution for reaction, taking out, washing and drying; (3) dissolving copper salt, nickel salt or cobalt salt to prepare solution A, and preparing organic ligand to prepare solution B; (4) sequentially soaking the product obtained in the step (2) in the solution A and the solution B; (5) drying; and (4) evaporating a layer of metal cobalt film as a top electrode on the upper surface of the product obtained in the step (5) through a strip-shaped mask plate, and evaporating a gold film as a protective layer to obtain the composite material. The method disclosed by the invention can effectively solve the problems that the two-dimensional metal organic framework material is difficult to dissolve and form a film, is simple, low in cost and low in requirement on equipment, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of spinning electronics, and relates to a two-dimensional metal organic framework film material and an organic spin valve with the two-dimensional metal organic framework film material as an intermediate layer.
Technical Field
The metal organic framework is a nano porous material with crystallinity, and inorganic metal ions and organic ligands are combined together through coordination. By changing metal nodes and various types of organic ligands, researchers have constructed a series of novel metal-organic framework structures with one-dimensional, two-dimensional and three-dimensional characteristics so far. Metal organic frameworks have found applications in many areas, such as gas storage, gas separation and catalysis. The conductive two-dimensional metal organic framework material is a new material emerging in recent years, and has high conductivity and mobility due to the d-pi conjugation, and the material has excellent properties in the fields of electrocatalysis, energy storage, photoelectric devices, gas electrochemical sensing and the like. However, most of these materials are insoluble polycrystalline powders synthesized by hydrothermal reaction, and it is difficult to form films by thermal evaporation, spin coating, etc., and the application of these materials in the field of spintronics is limited. Organic spintronics is a new field, fully considers the spin characteristics of electrons in devices, modulates the spin state of the electrons through an electric field and a magnetic field, and has many applications in the fields of read heads, magnetoresistive sensors, information storage and the like. Organic spintronics organic spin valve devices are an important direction of research in the field of organic electronics. Organic spin valve devices typically employ a sandwich structure of the ferromagnetic electrode (FM 1)/organic material/ferromagnetic electrode (FM2) type, where the two ferromagnetic electrodes serve as the top and bottom electrodes, respectively, and the organic material serves as the spin-transporting interlayer. Under the action of an external magnetic field, the ferromagnetic electrodes are in a parallel state or an antiparallel state by utilizing the difference of coercive forces of the two ferromagnetic electrodes, so that the resistance of the organic spin valve is changed. However, the current organic spin valve device has strict preparation process, insufficient and expensive material system, needs to prepare a good interface, and is not beneficial to industrialization.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an organic spin valve device based on a two-dimensional metal organic framework thin film material.
The second purpose of the invention is to provide a preparation method of an organic spin valve device based on a two-dimensional metal organic framework thin film material.
The technical scheme of the invention is summarized as follows:
the preparation method of the organic spin valve device based on the two-dimensional metal organic framework film material comprises the following steps:
(1) preparing a strip-shaped lanthanum strontium manganese oxygen bottom electrode on a substrate by a magnetron sputtering method to obtain the substrate with the strip-shaped lanthanum strontium manganese oxygen bottom electrode;
(2) sequentially immersing the substrate with the strip-shaped lanthanum strontium manganese oxygen bottom electrode into deionized water and a first organic solvent for ultrasonic washing and drying; then soaking the mixture into a mixed solvent for 15-60 minutes at 25-100 ℃, taking out, washing with deionized water, and drying; immersing into 0.2-5% of aminosilane solution by volume percentage concentration, wherein the solvent of the aminosilane solution is anhydrous n-octanol, ethanol or toluene, heating and refluxing for 0.25-24 hours, taking out, washing with anhydrous ethanol, and drying; the mixed solvent is prepared by mixing the following components in a volume ratio of 1: 1-2: 2-7 is composed of H 2 O 2 、NH 4 OH and H 2 O composition;
(3) dissolving copper salt, nickel salt or cobalt salt in a second organic solvent to obtain a solution A with the concentration of 0.02-10 mM, and dissolving an organic ligand in the second organic solvent to obtain a solution B with the concentration of 0.01-10 mM;
(4) sequentially soaking the products obtained in the step (2) in the solution A for 5-60 minutes, and taking out; soaking in ethanol for 5-60 min, and taking out; soaking in the solution B for 5-60 min, and taking out; soaking in ethanol for 5-60 min, and taking out;
(5) repeating the step (4) for 1-200 times, and performing vacuum drying to obtain a substrate with a strip-shaped lanthanum strontium manganese oxygen bottom electrode, the surface of which is modified with a two-dimensional metal organic framework film;
(6) and (3) evaporating a layer of metal cobalt film as a top electrode on the upper surface of the product obtained in the step (5) through a strip-shaped mask plate to enable the positions of the top electrode and the bottom electrode to be crossed, and evaporating a gold film on the top electrode to be used as a protective layer to obtain the organic spin valve device based on the two-dimensional metal organic framework film material.
The method for preparing the strip-shaped lanthanum strontium manganese oxygen bottom electrode on the substrate by using the magnetron sputtering method comprises the following steps: will be provided withFixing the strip-shaped mask plate on a substrate to obtain the substrate with the strip-shaped mask plate, fixing the substrate with the strip-shaped mask plate on a sample holder in a magnetron sputtering instrument, and vacuumizing until the vacuum degree reaches 5 multiplied by 10 -5 Pa or above; heating to 550-800 ℃, adjusting the flow of high-purity argon gas to 5-15sccm and the flow of oxygen to 3-9sccm, adjusting the air pressure to 0.3-0.8Pa, turning on a sputtering switch, adjusting the radio frequency power to 60-150W, sputtering the lanthanum strontium manganese oxygen target material at the deposition speed of 0.8-1.5nm/min, and obtaining the substrate with the strip-shaped lanthanum strontium manganese oxygen bottom electrode deposition thickness of 40-80 nm.
The material of the substrate is preferably amorphous quartz, silica/silicon (001), magnesium oxide (001), strontium titanate (001), or lanthanum aluminate (001).
The first organic solvent is ethanol, acetone or isopropanol.
The aminosilane is (3-aminopropyl) trimethoxysilane or (3-aminopropyl) triethoxysilane.
The second organic solvent is at least one of tetrahydrofuran, methanol, ethanol, N-dimethylformamide and N, N-dimethylacetamide;
the organic ligand is a benzene ring conjugated molecule containing a hydroxyl functional group, and the structural formula is shown as (I), (II), (III) or (IV):
the thickness of the metallic cobalt film is 40-80 nm.
The thickness of the gold film is 40-80 nm.
The organic spin valve device based on the two-dimensional metal organic framework thin film material prepared by the method.
Advantageous effects
(1) The method disclosed by the invention can effectively solve the problems that the two-dimensional metal organic framework material is difficult to dissolve and form a film, is simple, low in cost and low in requirement on equipment, and is suitable for large-scale production.
(2) The invention realizes the controllable preparation of the two-dimensional metal organic framework film and can effectively regulate and control the thickness of the film.
(3) The two-dimensional metal organic framework is applied to the organic spin valve, the conductive two-dimensional metal organic framework is an organic spin valve organic layer material, and by changing metal nodes and organic ligands, more possibilities are provided for the selection of the organic layer material in the organic spin valve, and the difficulty and complexity of synthesis are reduced; meanwhile, the application of the conductive two-dimensional MOFs in the field of spintronics is expanded.
Drawings
Fig. 1 is an SEM photograph of the two-dimensional metal organic framework thin film prepared in example 1.
Fig. 2 is a TEM photograph of the two-dimensional metal organic framework thin film prepared in example 1, and (b) is an enlarged view of (a).
Fig. 3 is an XPS spectrum of the two-dimensional metal-organic framework thin film prepared in example 1.
Fig. 4 is an XRD spectrum of the two-dimensional metal organic framework thin film prepared in example 1.
FIG. 5 is a schematic structural diagram of an organic spin valve device based on a two-dimensional metal-organic framework thin film material prepared in example 2, wherein: 1 is a substrate, 2 is a strip-shaped lanthanum strontium manganese oxygen bottom electrode, 3 is a two-dimensional metal organic framework film, 4 is a top electrode cobalt film, and 5 is a gold film protective layer.
FIG. 6 is a magnetoresistive curve at 5K for the organic spin valve prepared in example 2.
FIG. 7 is a magnetoresistive curve at 5K for the organic spin valve prepared in example 3.
FIG. 8 is a magnetoresistive curve at 5K for the organic spin valve prepared in example 4.
Detailed Description
The present invention will be further described with reference to the following examples.
The organic ligand used in the examples is a benzene ring conjugated molecule containing hydroxyl functional groups, and the structural formula is shown as I, II, III or IV:
compound I is purchased, II, III, IV, and can be synthesized by one skilled in the art according to the structure.
Example 1
The method for preparing the two-dimensional metal organic framework film material on the glass substrate (for testing the property of the two-dimensional metal organic framework film material, the two-dimensional metal organic framework film material is prepared on the glass substrate) comprises the following steps:
(1) sequentially immersing the glass substrate into deionized water and ethanol for ultrasonic washing and drying; then immersing into a mixed solvent (for adapting to a glass substrate, the mixed solvent is H according to the volume ratio of 7: 3 2 SO 4 And H 2 O 2 Composition), soaking at 85 deg.C for 30 min, taking out, washing with deionized water, and drying; immersing in a (3-aminopropyl) trimethoxy silane solution with the volume percentage concentration of 1%, wherein the solvent of the silane solution is anhydrous n-octanol, heating and refluxing for 0.25 h, taking out, washing with anhydrous ethanol, and drying;
(2) dissolving copper acetate monohydrate in absolute ethanol to obtain 0.1mM solution A, and dissolving organic ligand (benzene ring conjugated molecule containing hydroxyl functional group (formula I: triphenylene-2, 3,6,7,10, 11-hexaol)) in absolute ethanol to obtain 0.01mM solution B;
(3) sequentially soaking the products obtained in the step (1) in the solution A for 20 minutes, and taking out; soaking in ethanol for 5 min, and taking out; soaking in the solution B for 40 minutes, and taking out; soaking in ethanol for 5 min, and taking out;
(4) repeating the step (3) for 20 times, and performing vacuum drying to obtain the glass substrate with the surface modified with the two-dimensional metal organic frame film;
and (5) performing scanning electron microscope characterization on the product obtained in the step (4), wherein the characterization result is shown in figure 1, and the obtained two-dimensional metal organic framework film is proved to be compact and continuous.
And (3) stripping the product obtained in the step (5) to obtain the two-dimensional metal organic framework film, and performing transmission electron microscope characterization, wherein the characterization result is shown in fig. 2, which proves that the obtained two-dimensional metal organic framework film has certain crystallinity, and the existence of a porous structure can be seen from the picture.
The obtained two-dimensional metal organic framework film is subjected to X-ray photoelectron spectrum characterization, and the characterization result is shown in figure 3, so that the obtained film is proved to contain three elements of copper, carbon and oxygen at the same time, and the successful coordination of triphenylene-2, 3,6,7,10, 11-hexaol (formula I) and copper acetate monohydrate is proved.
The obtained two-dimensional metal organic framework film is subjected to X-ray diffraction characterization, the characterization result is shown in figure 4, the film can be judged to be a honeycomb-shaped hexagonal pore structure according to the simulation of the peak position, see formula V, the obtained two-dimensional metal organic framework film shows the growth orientation of a (001) crystal face, and the oriented growth is proved to be realized.
Example 2
The preparation method of the organic spin valve device based on the two-dimensional metal organic framework film material comprises the following steps:
(1) cutting strontium titanate (001) substrate into 0.5 × 0.5cm pieces 2 Fixing a 200-micron-4-mm strip-shaped mask plate on a substrate to obtain the substrate provided with the strip-shaped mask plate, fixing the substrate provided with the strip-shaped mask plate on a sample holder in a magnetron sputtering instrument, and vacuumizing until the vacuum degree reaches 5 x 10 -5 Pa is above; heating to 770 ℃, adjusting the flow of high-purity argon gas to 10sccm and the flow of oxygen to 6sccm, adjusting the air pressure to 0.5Pa, turning on a sputtering switch, adjusting the radio frequency power to 120W, sputtering a lanthanum strontium manganese oxygen target material, and obtaining a strontium titanate substrate with a strip-shaped lanthanum strontium manganese oxygen bottom electrode deposition thickness of 50nm, wherein the deposition speed is 0.8 nm/min;
(2) sequentially immersing the substrate with the strip-shaped lanthanum strontium manganese oxygen bottom electrode into deionized water and ethanol for ultrasonic washing, and drying; then soaking the mixture in a mixed solvent at 85 ℃ for 30 minutes, taking out, washing with deionized water and drying; immersing in a (3-aminopropyl) trimethoxy silane solution with the volume percentage concentration of 1%, wherein the solvent of the silane solution is anhydrous n-octanol, heating and refluxing for 0.25 h, taking out, washing with anhydrous ethanol, and drying; the mixed solvent is prepared by mixing the following components in a volume ratio of 1: 1: 5From H 2 O 2 、NH 4 OH and H 2 O composition;
(3) dissolving copper acetate monohydrate in absolute ethyl alcohol to obtain 0.1mM solution A, and dissolving organic ligand (formula I) in absolute ethyl alcohol to obtain 0.01mM solution B;
(4) sequentially soaking the products obtained in the step (2) in the solution A for 20 minutes, and taking out; soaking in ethanol for 5 min, and taking out; soaking in the solution B for 40 minutes, and taking out; soaking in ethanol for 5 min, and taking out;
(5) repeating the step (4) for 20 times, and performing vacuum drying to obtain a substrate with a strip-shaped lanthanum strontium manganese oxygen bottom electrode, the surface of which is modified with a two-dimensional metal organic framework film;
(6) evaporating a layer of 50nm thick metal cobalt film as a top electrode on the upper surface of the product obtained in the step (5) through a 200-micron-4 mm strip-shaped mask plate to enable the positions of the top electrode and the bottom electrode to be crossed, and evaporating a 50nm thick gold film as a protective layer on the top electrode to obtain the organic spin valve device based on the two-dimensional metal organic framework film material;
as shown in fig. 5: an organic spin valve device based on two-dimensional metal organic framework thin film materials: the electrode structure comprises a substrate 1, a bottom electrode 2, a middle layer 3, a top electrode 4, a metal cobalt film and a gold film protective layer 5, wherein the substrate is a lanthanum strontium manganese oxygen film, the middle layer 3 is a two-dimensional metal organic framework film, and the two-dimensional metal organic framework film at two ends of the lanthanum strontium manganese oxygen film on the strontium titanate substrate is wiped off to connect with a lead wire during testing.
In the organic spin valve prepared in this example, a magnetoresistive curve as shown in FIG. 6 was obtained, indicating that the organic spin valve exhibits a magnetoresistive effect of 24% at a temperature of 5K.
Example 3
The preparation method of the organic spin valve device based on the two-dimensional metal organic framework film material comprises the following steps:
(1) cutting strontium titanate (001) substrate into 0.5 × 0.5cm pieces 2 Fixing a 200-micron 4mm strip-shaped mask plate on a substrate to obtain the substrate provided with the strip-shaped mask plate, and fixing the substrate provided with the strip-shaped mask plate on a sample support in a magnetron sputtering instrumentVacuumizing to 5X 10 of vacuum degree -5 Pa is above; heating to 800 ℃, adjusting the flow of high-purity argon gas to 15sccm and the flow of oxygen to 9sccm, adjusting the air pressure to 0.8Pa, turning on a sputtering switch, adjusting the radio frequency power to 150W, sputtering a lanthanum strontium manganese oxygen target material, and obtaining a strontium titanate substrate with a strip-shaped lanthanum strontium manganese oxygen bottom electrode deposition thickness of 40nm, wherein the deposition speed is 0.8 nm/min;
(2) sequentially immersing the substrate with the strip-shaped lanthanum strontium manganese oxygen bottom electrode into deionized water and acetone for ultrasonic washing and drying; then soaking the mixture in a mixed solvent for 15 minutes at 100 ℃, taking out, washing with deionized water and drying; immersing in 5 vol% (3-aminopropyl) trimethoxy silane solution, wherein the solvent of the silane solution is toluene, heating and refluxing for 24 hours, taking out, washing with absolute ethyl alcohol, and drying; the mixed solvent is prepared by mixing the following components in a volume ratio of 1: 1: 7 is composed of H 2 O 2 、NH 4 OH and H 2 O composition;
(3) dissolving nickel acetate in tetrahydrofuran to obtain 0.02mM solution A, and dissolving organic ligand (formula I) in tetrahydrofuran to obtain 0.01mM solution B;
(4) sequentially soaking the products obtained in the step (2) in the solution A for 5 minutes, and taking out; soaking in ethanol for 5 min, and taking out; soaking in the solution B for 5 minutes, and taking out; soaking in ethanol for 5 min, and taking out;
(5) repeating the step (4) for 200 times, and performing vacuum drying to obtain a substrate with a strip-shaped lanthanum strontium manganese oxygen bottom electrode, the surface of which is modified with a two-dimensional metal organic framework film;
(6) evaporating a layer of metal cobalt thin film with the thickness of 40nm as a top electrode on the upper surface of the product obtained in the step (5) through a strip-shaped mask plate with the thickness of 200 mu m multiplied by 4mm, enabling the positions of the top electrode and the bottom electrode to be crossed, evaporating a gold thin film with the thickness of 40nm as a protective layer on the top electrode, and obtaining the organic spin valve device based on the two-dimensional metal organic framework thin film material,
in the organic spin valve prepared in this example, a magnetoresistive curve as shown in FIG. 7 was obtained, indicating that the organic spin valve exhibited a magnetoresistive effect of 6% at a temperature of 5K.
Example 4
The preparation method of the organic spin valve device based on the two-dimensional metal organic framework film material comprises the following steps:
(1) cutting strontium titanate (001) substrate into 0.5 × 0.5cm pieces 2 Fixing a 200-micron-4-mm strip-shaped mask plate on a substrate to obtain a substrate provided with the strip-shaped mask plate, fixing the substrate provided with the strip-shaped mask plate on a sample holder in a magnetron sputtering instrument, and vacuumizing until the vacuum degree reaches 5 x 10 -5 Pa is above; heating to 550 ℃, adjusting the flow of high-purity argon gas to be 5sccm and the flow of oxygen to be 3sccm, adjusting the air pressure to be 0.3Pa, turning on a sputtering switch, adjusting the radio frequency power to be 60W, sputtering a lanthanum strontium manganese oxygen target material, and obtaining a strontium titanate substrate with a strip-shaped lanthanum strontium manganese oxygen bottom electrode deposition thickness of 80nm, wherein the deposition speed is 1.5 nm/min;
(2) sequentially immersing the substrate with the strip-shaped lanthanum strontium manganese oxygen bottom electrode into deionized water and isopropanol for ultrasonic washing, and drying; then soaking the mixture in a mixed solvent for 60 minutes at 25 ℃, taking out, washing with deionized water and drying; immersing in (3-aminopropyl) triethoxysilane solution with volume percentage concentration of 0.2%, the solvent of the silane solution is ethanol, heating and refluxing for 0.25 hr, taking out, washing with absolute ethanol, and drying; the mixed solvent is prepared by mixing the following components in a volume ratio of 1: 2: 2 is formed by H 2 O 2 、NH 4 OH and H 2 O composition;
(3) dissolving cobalt acetate tetrahydrate in a second organic solvent (methanol and N, N-dimethylformamide in a volume ratio of 1: 1) to obtain a 10mM solution A, and dissolving an organic ligand (formula I) in the second organic solvent to obtain a 10mM solution B;
(4) sequentially soaking the products obtained in the step (2) in the solution A for 60 minutes, and taking out; soaking in ethanol for 60 min, and taking out; soaking in the solution B for 60 minutes, and taking out; soaking in ethanol for 60 min, and taking out;
(5) repeating the step (4) for 1 time, and performing vacuum drying to obtain a substrate which is decorated with a two-dimensional metal organic framework film and is provided with a strip-shaped lanthanum strontium manganese oxygen bottom electrode;
(6) evaporating a layer of metal cobalt thin film with the thickness of 80nm as a top electrode on the upper surface of the product obtained in the step (5) through a strip-shaped mask plate with the thickness of 200 mu m multiplied by 4mm, enabling the positions of the top electrode and the bottom electrode to be crossed, evaporating a gold thin film with the thickness of 80nm as a protective layer on the top electrode, and obtaining the organic spin valve device based on the two-dimensional metal organic framework thin film material,
in the organic spin valve prepared in this example, a magnetoresistive curve as shown in FIG. 8 was obtained, indicating that the organic spin valve exhibits a magnetoresistive effect of 15% at a temperature of 5K.
The N, N-dimethyl formamide of the embodiment is replaced by N, N-dimethyl acetamide, and other embodiments are the same as the embodiment, so that the organic spin valve device based on the two-dimensional metal organic framework thin film material can be obtained.
Experiments have shown that, by replacing strontium titanate (001) in this example with amorphous quartz, silica/silicon (001), magnesium oxide (001) or lanthanum aluminate (001), other examples can produce organic spin valve devices based on two-dimensional metal-organic framework thin film materials with properties similar to those of the example.
Experiments prove that the organic spin valve device based on the two-dimensional metal organic framework thin film material similar to the embodiment is prepared by using the compound shown in the formula II, the formula III or the formula IV to replace the compound shown in the formula I in the embodiment and other embodiments.
The above embodiments are illustrative of the embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention are included in the scope of the present invention.
Claims (10)
1. The preparation method of the organic spin valve device based on the two-dimensional metal organic framework film material is characterized by comprising the following steps of:
(1) preparing a strip-shaped lanthanum strontium manganese oxygen bottom electrode on a substrate by a magnetron sputtering method to obtain the substrate with the strip-shaped lanthanum strontium manganese oxygen bottom electrode;
(2) sequentially immersing the substrate with the strip-shaped lanthanum strontium manganese oxygen bottom electrode into deionized water and a first organic solvent for ultrasonic washing and drying; then immersed in the mixed solvent at 2Soaking for 15-60 minutes at 5-100 ℃, taking out, washing with deionized water, and drying; immersing into 0.2-5% of aminosilane solution by volume percentage concentration, wherein the solvent of the aminosilane solution is anhydrous n-octanol, ethanol or toluene, heating and refluxing for 0.25-24 hours, taking out, washing with anhydrous ethanol, and drying; the mixed solvent is prepared by mixing the following components in a volume ratio of 1: 1-2: 2-7 is composed of H 2 O 2 、NH 4 OH and H 2 O composition;
(3) dissolving copper salt, nickel salt or cobalt salt in a second organic solvent to obtain a solution A with the concentration of 0.02-10 mM, and dissolving an organic ligand in the second organic solvent to obtain a solution B with the concentration of 0.01-10 mM;
(4) sequentially soaking the products obtained in the step (2) in the solution A for 5-60 minutes, and taking out; soaking in ethanol for 5-60 min, and taking out; soaking in the solution B for 5-60 min, and taking out; soaking in ethanol for 5-60 min, and taking out;
(5) repeating the step (4) for 1-200 times, and performing vacuum drying to obtain a substrate with a strip-shaped lanthanum strontium manganese oxygen bottom electrode, the surface of which is modified with a two-dimensional metal organic framework film;
(6) and (3) evaporating a layer of metal cobalt film as a top electrode on the upper surface of the product obtained in the step (5) through a strip-shaped mask plate to enable the positions of the top electrode and the bottom electrode to be crossed, and evaporating a gold film on the top electrode to be used as a protective layer to obtain the organic spin valve device based on the two-dimensional metal organic framework film material.
2. The method as set forth in claim 1, wherein the step (1) of preparing the strip-shaped lanthanum strontium manganese oxygen bottom electrode on the substrate by the magnetron sputtering method comprises: fixing a strip-shaped mask plate on a substrate to obtain the substrate provided with the strip-shaped mask plate, fixing the substrate provided with the strip-shaped mask plate on a sample support in a magnetron sputtering instrument, and vacuumizing until the vacuum degree reaches 5 multiplied by 10 -5 Pa or above; heating to 550-800 ℃, adjusting the flow of high-purity argon gas to 5-15sccm and the flow of oxygen to 3-9sccm, adjusting the air pressure to 0.3-0.8Pa, opening a sputtering switch, adjusting the radio frequency power to 60-150W, sputtering the lanthanum strontium manganese oxygen target material at the deposition speed of 0.8-1.5nm/min to obtain the deposited thick electrode with the bar-shaped lanthanum strontium manganese oxygen bottom electrodeAnd the degree is 40-80 nm.
3. The method according to claim 1 or 2, wherein the substrate is made of amorphous quartz, silica/silicon (001), magnesium oxide (001), strontium titanate (001) or lanthanum aluminate (001).
4. The method as set forth in claim 1, wherein the first organic solvent is ethanol, acetone or isopropanol.
5. The process as claimed in claim 1, wherein the aminosilane is (3-aminopropyl) trimethoxysilane or (3-aminopropyl) triethoxysilane.
6. The method as set forth in claim 1, wherein the second organic solvent is at least one of tetrahydrofuran, methanol, ethanol, N-dimethylformamide and N, N-dimethylacetamide.
7. The method of claim 1, wherein the organic ligand is a benzene ring conjugated molecule containing hydroxyl functional groups, and the structural formula is shown as (I), (II), (III) or (IV):
8. the method as claimed in claim 1, wherein the thickness of the metallic cobalt thin film is 40-80 nm.
9. The method of claim 1, wherein the gold thin film has a thickness of 40 to 80 nm.
10. An organic spin valve device based on a two-dimensional metal organic framework thin film material prepared by the method of any one of claims 1 to 9.
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