CN103526263A - Preparation method of Cr-doped TiO2 nanometer magnetic film with room-temperature ferromagnetic effect - Google Patents

Preparation method of Cr-doped TiO2 nanometer magnetic film with room-temperature ferromagnetic effect Download PDF

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CN103526263A
CN103526263A CN201310494834.8A CN201310494834A CN103526263A CN 103526263 A CN103526263 A CN 103526263A CN 201310494834 A CN201310494834 A CN 201310494834A CN 103526263 A CN103526263 A CN 103526263A
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tio
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CN103526263B (en
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廖宇龙
张怀武
白飞明
钟智勇
贾利军
李颉
周廷川
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University of Electronic Science and Technology of China
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Abstract

The invention relates to a preparation method of a Cr-doped TiO2 nanometer magnetic film with a room-temperature ferromagnetic effect, belonging to the technical field of a functionalized material. The preparation method comprises the steps of: by taking a TiO2 nanotube array thin film, prepared by but not limited to electrochemical anode oxidization technology, as a starting material, firstly carrying out CrNO3 aqueous solution soaked novel homogeneous-phase low-temperature Cr doping, then carrying out high-temperature annealing treatment, introducing composite vacancy and oxygen vacancy defects into the TiO2 nanotube array thin film, to obtain the TiO2 nanometer magnetic film which is high in room-temperature ferromagnetic property and controllability, low in cost, good in repeatability and can be manufactured in large scale. The preparation method has the characteristics of simple technology, low cost and good controllability and is suitable for mass production.

Description

The Cr doped Ti O with room temperature ferromagnetic effect 2the preparation method of nano-magnetic thin films
Technical field
The invention belongs to technical field of function materials, relate to magnetic membrane material and technology of preparing thereof, be specifically related to a kind of room temperature ferromagnetic effect TiO that has 2the method of nano-magnetic thin films.
Technical background
Dilute magnetic semiconductor (diluted magnetic semiconductors, is abbreviated as DMSs), owing to having characteristic of semiconductor and ferromegnetism simultaneously, has very wide application prospect in fields such as spintronics, magnetics and microtronics.It typically refers to a formed class novel semiconductor material after magnetic ion partly replaces the positively charged ion in semi-conductor.Relatively for common magnetic semiconductor, the contained magnetic ion of dilute magnetic semiconductor is fewer, and the distribution of magnetic ion is unordered, and it has ferromagnetic material and semi-conductive bulk properties.And preparation to have the ferromagnetic room-temperature diluted magnetic semiconductor of intrinsic be the key point that realizes spin electric device.
On calendar year 2001 " Science " magazine, reported the TiO of Curie temperature (300K) Co doping more than room temperature 2since normal temperature ferromegnetism, make to have the ferromagnetic oxide compound diluted magnetic semiconductor of normal temperature and there is possibility in spintronics application aspect, caused the very big concern of magnetics technical field circle.About the research of oxide lanthanon magnetic semiconductor, no matter be just orderly developments all in theory or experimentally.To the research of oxide lanthanon magnetic semiconductor also from initial TiO 2, expand to In 2o 3, CeO 2, SnO 2, a series of oxide compounds such as ZnO, by containing transition metal ion or rare earth ion, obtained various room temperature ferromagnetic characteristics.Wherein, due to TiO 2there is excellent physical chemical stability, with TiO 2containing transition metal ion obtains room temperature ferromagnetic performance and remains one of main research direction.Prepare at present TiO 2the main method of rare magnetic thin film material comprises: sputtering method, ion implantation, pulsed laser deposition, sol-gel method, chemical vapour deposition etc.
Yet, in practice, find the TiO that part adopts above technology to prepare 2in rare magnetic thin film material, there is the segregation of magnetic ion, and formed the magnetic aggregate of tool or second-phase (as simple substance Co and CoTiO 3deng), caused that the Inner of room-temperature ferromagnetic reports the very big dispute of attribute.And adopt, do not have magnetic transition metal ion, for example Cr element, mixes TiO by a kind of rational method 2among, can effectively avoid the segregation of magnetic atom and the interference of reuniting its room-temperature ferromagnetic being caused.Therefore preparation does not contain the TiO of magnetic transition metal ion doping 2rare magnetic thin film material, not only the realization for spin electric device has important realistic meaning, to helping and understanding TiO 2the magnetic origin of rare magnetic material also has great role.
Summary of the invention
The invention provides a kind of Cr doped Ti O with room temperature ferromagnetic effect 2the preparation method of nano-magnetic thin films, the method is with TiO 2nano-tube film is precursor, passes through CrNO 3aqueous solution soaking mode is mixed Cr element, then through the high temperature anneal, obtains the TiO that nonmagnetic elements is adulterated and had room temperature ferromagnetic performance 2nano-magnetic thin films.
For achieving the above object, the technical solution used in the present invention is:
The Cr doped Ti O with room temperature ferromagnetic effect 2the preparation method of nano-magnetic thin films, as shown in Figure 1, comprises the steps:
Step 1: preparation TiO 2nano-tube film.Described TiO 2nano-tube film adopts electrochemical anodic oxidation technique but is not limited to anode oxidation process preparation.
Step 2: adopt CrNO 3the TiO of the aqueous solution to step 1 preparation 2nano-tube film carries out immersion treatment, the TiO after immersion treatment 2nano-tube film naturally dries after deionized water rinsing, obtains Cr doped Ti O 2nano-tube film.
Step 3: by step 2 gained Cr doped Ti O 2nano-tube film carries out obtaining having after the high temperature anneal the Cr doped Ti O of room-temperature ferromagnetic 2nano-magnetic thin films.Wherein annealing temperature is 450～600 ℃, and annealing time is 1～4 hour, and annealing atmosphere is air, nitrogen, oxygen or argon gas.
Further, step 1 adopts electrochemical anodic oxidation technique to prepare TiO 2nano-tube film comprises the steps:
Step 1-1: take Neutral ammonium fluoride as solute, the ethylene glycol that volume ratio is 294:6 and deionized water mixing solutions are solvent, preparation Neutral ammonium fluoride mass percent concentration is 2.4 * 10 -3-3.6 * 10 -3the organic fluoride-containing electrolytic solution of %;
Step 1-2: metal titanium sheet is adopted after acetone, dehydrated alcohol and deionized water ultrasonic cleaning successively, naturally dry stand-by;
Step 1-3: in the organic fluoride-containing electrolytic solution that the metal titanium sheet immersion step 1-1 after step 1-2 processes is prepared, take metal titanium sheet as anode, be negative electrode with the platinum electrode of the parallel placement of anode, distance between negative and positive two electrodes is controlled at 2.5～3 centimetres, then control the temperature of organic fluoride-containing electrolytic solution between 15～45 ℃, the oxide treatment that adopts the volts DS antianode metal titanium sheet of 60 volts to carry out 1～3 hour, finally obtains the TiO of unformed shape on metal titanium sheet surface 2nano-tube film.
Further, step 2 adopts CrNO 3the TiO of the aqueous solution to step 1 preparation 2when nano-tube film carries out immersion treatment, first soak at normal temperatures 30～60 minutes, reheat afterwards at 70～95 ℃ and continue to soak 3～6 hours; Wherein said CrNO 3the concentration of the aqueous solution is 0.05-0.25M.
Beneficial effect of the present invention is:
The present invention adopts CrNO 3aqueous solution soaking TiO 2the mode of nano-tube film is to TiO 2nano-tube film carries out novel homogeneous phase low temperature Cr doping, then in conjunction with the high temperature anneal, at TiO 2nano-pipe array thin film is introduced compound room and oxygen vacancy defect, obtains having room temperature ferromagnetic performance, controllability is high, with low cost, reproducible and the TiO that can manufacture on a large scale 2nano-magnetic thin films.The present invention has the advantages that technique is simple, cost is low, controllability is good and be suitable for producing in enormous quantities.
Accompanying drawing explanation
Fig. 1 is schematic flow sheet of the present invention.
TiO after Fig. 2 Cr doping 2nano-pipe array thin film scanning electronic microscope vertical view (a) and side elevational view (c, d), and the TiO after this Cr doping 2nanotube transmissioning electric mirror test figure (b).
TiO after Fig. 3 (a) Cr doping 2nano-pipe array thin film surface-element distribution plan (energy dispersion X ray spectrum), and (b) along the distributing line of element shown in dotted line scintigram.
The Cr doped Ti O annealing under Fig. 4 different atmosphere condition 2the XRD figure of nano-pipe array thin film.
The Cr doped Ti O annealing under Fig. 5 different atmosphere condition 2the magnetic hysteresis loop figure of nano-pipe array thin film.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment 1
1) Neutral ammonium fluoride of certain mass is dissolved in in ethylene glycol that volume ratio is 294:6 and deionized water mixing solutions, to make Neutral ammonium fluoride mass percent be 2.4 * 10 -3organic fluoride-containing electrolytic solution;
2) by metal titanium sheet successively with acetone, dehydrated alcohol and deionized water respectively ultrasonic cleaning after 10 minutes, naturally dry stand-by;
3) the titanium sheet after cleaning grips as anode again, and platinum electrode placement in parallel, as negative electrode, forms electrode system, and the distance between them is 2.5cm;
4) electrode system assembling as step 3) is immersed as in the electrolytic solution of step 1), using DC constant voltage source as power supply, open circuit voltage is directly adjusted to 60V from 0V, and temperature of reaction is controlled at 15 ℃, through reaction in 3 hours, obtains the TiO of unformed shape on metal titanium sheet surface 2nano-tube film.
5) by the CrNO of certain mass 3be dissolved in deionized water, make the CrNO that concentration is 0.05M 3the aqueous solution.
6) will obtain TiO as step 4) 2nano-tube film immerses the CrNO obtaining as step 5) 3in the aqueous solution, first soak at normal temperatures 60 minutes, reheat to continue to soak after 6 hours at 70 ℃ and take out, adopt a large amount of deionized waters to rinse and naturally dry afterwards, obtained the TiO of Cr doping 2nano-tube film.
7) by the TiO of this Cr doping 2nano-tube film carries out the high temperature anneal in air, and annealing temperature is 450 ℃, and annealing time is 4 hours, finally obtains having the Cr doped Ti O of room-temperature ferromagnetic 2nano-magnetic thin films.
Embodiment 2
1) Neutral ammonium fluoride of certain mass is dissolved in in ethylene glycol that volume ratio is 294:6 and deionized water mixing solutions, to make Neutral ammonium fluoride mass percent be 3.6 * 10 -3the organic fluoride-containing electrolytic solution of %;
2) by metal titanium sheet successively with acetone, dehydrated alcohol and deionized water respectively ultrasonic cleaning after 10 minutes, naturally dry stand-by;
3) the titanium sheet after cleaning grips as anode again, and platinum electrode placement in parallel, as negative electrode, forms electrode system, and the distance between them is 3cm;
4) electrode system assembling as step 3) is immersed as in the electrolytic solution of step 1), using DC constant voltage source as power supply, open circuit voltage is directly adjusted to 60V from 0V, and temperature of reaction is controlled at 45 ℃, through reaction in 1 hour, obtains the TiO of unformed shape on metal titanium sheet surface 2nano-tube film.
5) by the CrNO of certain mass 3be dissolved in deionized water, make the CrNO that concentration is 0.25M 3the aqueous solution.
6) will obtain TiO as step 4) 2nano-tube film immerses the CrNO obtaining as step 5) 3in the aqueous solution, first soak at normal temperatures 60 minutes, reheat to continue to soak after 3 hours at 95 ℃ and take out, adopt a large amount of deionized waters to rinse and naturally dry afterwards, obtained the TiO of Cr doping 2nano-tube film.
7) by the TiO of this Cr doping 2nano-tube film carries out the high temperature anneal in argon gas, and annealing temperature is 600 ℃, and annealing time is 1 hour, finally obtains having the Cr doped Ti O of room-temperature ferromagnetic 2nano-magnetic thin films.
Embodiment 3
1) Neutral ammonium fluoride of certain mass is dissolved in in ethylene glycol that volume ratio is 294:6 and deionized water mixing solutions, to make Neutral ammonium fluoride mass percent be 2.6 * 10 -3the organic fluoride-containing electrolytic solution of %;
2) by metal titanium sheet successively with acetone, dehydrated alcohol and deionized water respectively ultrasonic cleaning after 10 minutes, naturally dry stand-by;
3) the titanium sheet after cleaning grips as anode again, and platinum electrode placement in parallel, as negative electrode, forms electrode system, and the distance between them is 2.5cm;
4) electrode system assembling as step 3) is immersed as in the electrolytic solution of step 1), using DC constant voltage source as power supply, open circuit voltage is directly adjusted to 60V from 0V, and temperature of reaction is controlled at 25 ℃, through reaction in 3 hours, obtains the TiO of unformed shape on metal titanium sheet surface 2nano-tube film.
5) by the CrNO of certain mass 3be dissolved in deionized water, make the CrNO that concentration is 0.2M 3the aqueous solution.
6) will obtain TiO as step 4) 2nano-tube film immerses the CrNO obtaining as step 5) 3in the aqueous solution, first soak at normal temperatures 30 minutes, reheat to continue to soak after 3 hours at 90 ℃ and take out, adopt a large amount of deionized waters to rinse and naturally dry afterwards, obtained the TiO of Cr doping 2nano-tube film.
7) by the TiO of this Cr doping 2nano-tube film precursor carries out the high temperature anneal in air, and annealing temperature is 450 ℃, and annealing time is 3 hours, finally obtains having the Cr doped Ti O of room-temperature ferromagnetic 2nano-magnetic thin films.
Embodiment 4
1) Neutral ammonium fluoride of certain mass is dissolved in in ethylene glycol that volume ratio is 294:6 and deionized water mixing solutions, to make Neutral ammonium fluoride mass percent be 2.6 * 10 -3the organic fluoride-containing electrolytic solution of %;
2) by metal titanium sheet successively with acetone, dehydrated alcohol and deionized water respectively ultrasonic cleaning after 10 minutes, naturally dry stand-by;
3) the titanium sheet after cleaning grips as anode again, and platinum electrode placement in parallel, as negative electrode, forms electrode system, and the distance between them is 2.5cm;
4) electrode system assembling as step 3) is immersed as in the electrolytic solution of step 1), using DC constant voltage source as power supply, open circuit voltage is directly adjusted to 60V from 0V, and temperature of reaction is controlled at 25 ℃, through reaction in 3 hours, obtains the TiO of unformed shape on metal titanium sheet surface 2nano-tube film.
5) by the CrNO of certain mass 3be dissolved in deionized water, make the CrNO that concentration is 0.2M 3the aqueous solution.
6) will obtain TiO as step 4) 2nano-tube film immerses the CrNO obtaining as step 5) 3in the aqueous solution, first soak at normal temperatures 30 minutes, reheat to continue to soak after 3 hours at 90 ℃ and take out, adopt a large amount of deionized waters to rinse and naturally dry afterwards, obtained the TiO of Cr doping 2nano-tube film.
7) by the TiO of this Cr doping 2nano-tube film precursor carries out the high temperature anneal in argon gas, and annealing temperature is 450 ℃, and annealing time is 3 hours, finally obtains having the Cr doped Ti O of room-temperature ferromagnetic 2nano-magnetic thin films.
Embodiment 5
1) Neutral ammonium fluoride of certain mass is dissolved in in ethylene glycol that volume ratio is 294:6 and deionized water mixing solutions, to make Neutral ammonium fluoride mass percent be 2.6 * 10 -3the organic fluoride-containing electrolytic solution of %;
2) by metal titanium sheet successively with acetone, dehydrated alcohol and deionized water respectively ultrasonic cleaning after 10 minutes, naturally dry stand-by;
3) the titanium sheet after cleaning grips as anode again, and platinum electrode placement in parallel, as negative electrode, forms electrode system, and the distance between them is 2.5cm;
4) electrode system assembling as step 3) is immersed as in the electrolytic solution of step 1), using DC constant voltage source as power supply, open circuit voltage is directly adjusted to 60V from 0V, and temperature of reaction is controlled at 25 ℃, through reaction in 3 hours, obtains the TiO of unformed shape on metal titanium sheet surface 2nano-tube film.
5) by the CrNO of certain mass 3be dissolved in deionized water, make the CrNO that concentration is 0.2M 3the aqueous solution.
6) will obtain TiO as step 4) 2nano-tube film immerses the CrNO obtaining as step 5) 3in the aqueous solution, first soak at normal temperatures 30 minutes, reheat to continue to soak after 3 hours at 90 ℃ and take out, adopt a large amount of deionized waters to rinse and naturally dry afterwards, obtained the TiO of Cr doping 2nano-tube film.
7) by the TiO of this Cr doping 2nano-tube film precursor carries out the high temperature anneal in nitrogen, and annealing temperature is 450 ℃, and annealing time is 3 hours, finally obtains having the Cr doped Ti O of room-temperature ferromagnetic 2nano-magnetic thin films.
Embodiment 6
1) Neutral ammonium fluoride of certain mass is dissolved in in ethylene glycol that volume ratio is 294:6 and deionized water mixing solutions, to make Neutral ammonium fluoride mass percent be 2.6 * 10 -3the organic fluoride-containing electrolytic solution of %;
2) by metal titanium sheet successively with acetone, dehydrated alcohol and deionized water respectively ultrasonic cleaning after 10 minutes, naturally dry stand-by;
3) the titanium sheet after cleaning grips as anode again, and platinum electrode placement in parallel, as negative electrode, forms electrode system, and the distance between them is 2.5cm;
4) electrode system assembling as step 3) is immersed as in the electrolytic solution of step 1), using DC constant voltage source as power supply, open circuit voltage is directly adjusted to 60V from 0V, and temperature of reaction is controlled at 25 ℃, through reaction in 3 hours, obtains the TiO of unformed shape on metal titanium sheet surface 2nano-tube film.
5) by the CrNO of certain mass 3be dissolved in deionized water, make the CrNO that concentration is 0.2M 3the aqueous solution.
6) will obtain TiO as step 4) 2nano-tube film immerses the CrNO obtaining as step 5) 3in the aqueous solution, first soak at normal temperatures 30 minutes, reheat afterwards to continue to soak after 3 hours at 90 ℃ and take out, adopt a large amount of deionized waters to rinse and naturally dry afterwards, obtained the TiO of Cr doping 2nano-tube film.
7) by the TiO of this Cr doping 2nano-tube film precursor carries out the high temperature anneal in oxygen, and annealing temperature is 450 ℃, and annealing time is 3 hours, finally obtains having the Cr doped Ti O of room-temperature ferromagnetic 2nano-magnetic thin films.
Fig. 2 is the Cr doped Ti O obtaining in embodiment 3 2nano-pipe array thin film scanning electronic microscope vertical view (a) and side elevational view (c, d), and the TiO of this Cr doping 2nanotube transmissioning electric mirror test figure (b).Can see the TiO after Cr doping 2nano-tube array still keeps the nano-pipe array thin film structure of high-sequential, illustrates that the later subsequent heat treatment of Cr doping can not affect TiO 2nano tube structure.
Fig. 3 (a) is the TiO after the Cr doping obtaining in embodiment 4 2nano-pipe array thin film surface-element distribution plan (energy dispersion X ray spectrum), Fig. 3 (b) is along the distributing line of element shown in dotted line scintigram.Result shows that film surface contains Cr element, O element and Ti element, illustrates that Cr element is successfully incorporated into TiO 2among nano-pipe array thin film, Cr element is evenly distributed, and does not occur cluster or the segregation of enrichment of element.
Fig. 4 is the Cr doped Ti O annealing under the different atmosphere condition obtaining in embodiment 3, embodiment 4, embodiment 5 and embodiment 6 2the XRD figure of nano-pipe array thin film, can see all samples all crystallization be anatase octahedrite pure phase, annealing atmosphere does not affect its crystalline structure.
Fig. 5 is the Cr doped Ti O annealing under the different atmosphere condition obtaining in embodiment 3, embodiment 4, embodiment 5 and embodiment 6 2the magnetic hysteresis loop figure of nano-pipe array thin film, can be clearly seen that all samples has obvious room temperature ferromagnetic performance, and Cr ion doping has significantly improved prepared TiO 2the room temperature ferromagnetic performance index of nano-pipe array thin film.
Table 1 is embodiment 3, and embodiment 4, and embodiment 5, the Cr doped Ti O annealing under the different atmosphere condition obtaining in embodiment 6 2the crystalline structure of nano-pipe array thin film and saturation magnetization and coercive force, can see that the defect of being introduced by Cr doping has improved TiO significantly 2nano-pipe array thin film saturation magnetization, can see the Cr doped Ti O that is obtained annealing in oxygen by embodiment 6 simultaneously 2nano-pipe array thin film has minimum saturation magnetization 0.39531emu/g, and the Cr doped Ti O that embodiment 4 obtains annealing in argon gas 2nano-pipe array thin film has maximum saturation specific magnetising moment 0.44190emu/g, shows oxygen double-void Cr doped Ti O 2the room temperature ferromagnetic of nano-pipe array thin film newly can also have contribution.
The Cr doped Ti O annealing under table 1 different atmosphere condition 2the crystalline structure of nano-pipe array thin film and saturation magnetization and coercive force
Figure BDA0000399079810000071
In sum, the TiO that the present invention has prepared and can obtain having room temperature ferromagnetic performance, controllability is high, with low cost, reproducible and can manufacture on a large scale 2nano-magnetic thin films.

Claims (3)

1. the Cr doped Ti O with room temperature ferromagnetic effect 2the preparation method of nano-magnetic thin films, comprises the steps:
Step 1: preparation TiO 2nano-tube film; Described TiO 2nano-tube film adopts electrochemical anodic oxidation technique but is not limited to anode oxidation process preparation;
Step 2: adopt CrNO 3the TiO of the aqueous solution to step 1 preparation 2nano-tube film carries out immersion treatment, the TiO after immersion treatment 2nano-tube film naturally dries after deionized water rinsing, obtains Cr doped Ti O 2nano-tube film;
Step 3: by step 2 gained Cr doped Ti O 2nano-tube film carries out obtaining having after the high temperature anneal the Cr doped Ti O of room-temperature ferromagnetic 2nano-magnetic thin films; Wherein annealing temperature is 450～600 ℃, and annealing time is 1～4 hour, and annealing atmosphere is air, nitrogen, oxygen or argon gas.
2. the Cr doped Ti O with room temperature ferromagnetic effect according to claim 1 2the preparation method of nano-magnetic thin films, is characterized in that, step 1 adopts electrochemical anodic oxidation technique to prepare TiO 2nano-tube film comprises the steps:
Step 1-1: take Neutral ammonium fluoride as solute, the ethylene glycol that volume ratio is 294:6 and deionized water mixing solutions are solvent, preparation Neutral ammonium fluoride mass percent concentration is 2.4 * 10 -3-3.6 * 10 -3the organic fluoride-containing electrolytic solution of %;
Step 1-2: metal titanium sheet is adopted after acetone, dehydrated alcohol and deionized water ultrasonic cleaning successively, naturally dry stand-by;
Step 1-3: in the organic fluoride-containing electrolytic solution that the metal titanium sheet immersion step 1-1 after step 1-2 processes is prepared, take metal titanium sheet as anode, be negative electrode with the platinum electrode of the parallel placement of anode, distance between negative and positive two electrodes is controlled at 2.5～3 centimetres, then control the temperature of organic fluoride-containing electrolytic solution between 15～45 ℃, the oxide treatment that adopts the volts DS antianode metal titanium sheet of 60 volts to carry out 1～3 hour, finally obtains the TiO of unformed shape on metal titanium sheet surface 2nano-tube film.
3. the Cr doped Ti O with room temperature ferromagnetic effect according to claim 1 2the preparation method of nano-magnetic thin films, is characterized in that, step 2 adopts CrNO 3the TiO of the aqueous solution to step 1 preparation 2when nano-tube film carries out immersion treatment, first soak at normal temperatures 30～60 minutes, reheat afterwards at 70～95 ℃ and continue to soak 3～6 hours; Wherein said CrNO 3the concentration of the aqueous solution is 0.05-0.25M.
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CN108149300A (en) * 2018-01-08 2018-06-12 电子科技大学 A kind of CeO2Nano particle/TiO2The preparation method of nano-tube array composite heterogenous junction film
CN108179455A (en) * 2018-01-08 2018-06-19 电子科技大学 A kind of Cu2O nano particles/TiO2The preparation method of nano-tube array composite heterogenous junction film
CN111148425A (en) * 2019-12-31 2020-05-12 浙江大学 Method for realizing magnetoelectric integrated regulation and control of transition metal oxygen/sulfide by doping

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Publication number Priority date Publication date Assignee Title
CN106312049A (en) * 2016-09-22 2017-01-11 安徽大学 Electrochemical control method for thickness of shell layer of Fe/Fe2O3 core/shell structure
CN108149300A (en) * 2018-01-08 2018-06-12 电子科技大学 A kind of CeO2Nano particle/TiO2The preparation method of nano-tube array composite heterogenous junction film
CN108179455A (en) * 2018-01-08 2018-06-19 电子科技大学 A kind of Cu2O nano particles/TiO2The preparation method of nano-tube array composite heterogenous junction film
CN108149300B (en) * 2018-01-08 2019-11-05 电子科技大学 A kind of CeO2Nano particle/TiO2The preparation method of nano-tube array composite heterogenous junction film
CN111148425A (en) * 2019-12-31 2020-05-12 浙江大学 Method for realizing magnetoelectric integrated regulation and control of transition metal oxygen/sulfide by doping
CN111148425B (en) * 2019-12-31 2021-06-08 浙江大学 Method for realizing magnetoelectric integrated regulation and control of transition metal oxygen/sulfide by doping

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