CN100384780C - Method of preparing high temperature ferromagnetism ZnO:(Co,Al) nano-material using sol-gel method - Google Patents
Method of preparing high temperature ferromagnetism ZnO:(Co,Al) nano-material using sol-gel method Download PDFInfo
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- CN100384780C CN100384780C CNB2006101165079A CN200610116507A CN100384780C CN 100384780 C CN100384780 C CN 100384780C CN B2006101165079 A CNB2006101165079 A CN B2006101165079A CN 200610116507 A CN200610116507 A CN 200610116507A CN 100384780 C CN100384780 C CN 100384780C
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Abstract
The present invention relates to a sol-gel method for preparing ZnO:(Co, Al) nano powder body and film with ferromagnetism, its Curie point is above 360 K. Said sol-gel method includes the following steps: firstly, preparing Co and Al codoped ZnO colloid solution, drop-adding colloid on the precleaned Si chip or other substrate (quartz glass, sapphire and SiC, etc.), utilizing the mode of rotating substrate to make the colloid solution be uniformly coated on the substrate surface, preheating said substrate on which the colloid solution is uniformly coated for a period of time, making heat treatment at 300-350 deg.C, then making annealing treatment at 600-800 deg.C under the condition of argon atmosphere so as to obtain the invented product.
Description
Technical field
The present invention relates to a kind of technology of preparing that obtains high temperature ferromagnetism zno-based rare magnetic semiconductor nano material, mainly is zno-based diluted magnetic semiconductor nano film and the powder that adopts sol-gel method and be higher than the greenhouse in conjunction with codoped approach (as Co and Al codoped) preparation Curie temperature.
Background technology
Enter 21 century, the mankind have strided forward highly electronization, informationalized society, information transmission, processing and storage will require unprecedented scale and speed, how realize the leap of above-mentioned electronic information technology, one of great problem in science that has become the beginning of this century and faced.The electric charge of electronics and spin are two most important physical quantitys of its characteristic of sign, semi-conductor and magnetic substance based on it is most important two research fields in the physics respectively, also becomes the most important foundation stone of world today's high-tech information electronic industry respectively in the achievement in research of this basic science aspect two.Yet people are parallel developments for the research and the application of elementary charge and spin attribute, and are separate each other.Dilute magnetic semiconductor (Diluted MagneticSemiconductors as spin electric device propping material of new generation, DMS), can utilize the electric charge attribute and the spin attribute of electronics simultaneously, have performances such as excellent magnetic, magneto-optic, magnetoelectricity, very likely realize Spin Valve (Spin Valve), spin fet (Spin-FET), the spinning LED devices of novel photoelectric such as (Spin-LED).In addition, the DMS material also has broad application prospects in fields such as high-density nonvolatile memory, magnetic inductor, optoisolator, semiconductor laser and spin quantum computers, has become the focus in the current investigation of materials field.
From DMS material point of practical use, require DMS to have the intrinsic ferromegnetism, and its Curie temperature (T
c) reach or be higher than room temperature.At present, the research focus is how to prepare to have the ferromagnetic DMS material of intrinsic.ZnO is a kind of direct band gap compound semiconductor materials with good piezoelectricity, photoelectricity, air-sensitive and character such as pressure-sensitive.In addition, ZnO have also that raw material resources are abundant, cheap, preparation process environmentally safe, preparation condition advantage such as gentleness relatively.Of paramount importance is that theory is foretold the T of transient metal doped zno-based dilute magnetic semiconductor material
cCan reach more than the room temperature.Yet people do not obtain the result consistent with Theoretical Calculation in experiment.For the block materials of ZnO:Co, people have generally obtained antiferromagnetism or paramagnetic material, rarely have the report of room-temperature ferromagnetic.In the thin film system of ZnO:Co, part Study group has obtained ferromegnetism, but T
cLower, can not satisfy the requirement of device; Also have the researchist to obtain the film of room-temperature ferromagnetic, but to its magnetic source can not get rid of metal Co bunch may, and the repetition rate of film is not high.Adopt different methods, even why the ZnO:Co material that identical preparation method obtains presenting so big difference, is because the Co that mixes and introduce
2+Between ferromegnetism coupling exchange interaction relevant with carrier concentration and defective among the ZnO.Al and Co codope ZnO can significantly improve the concentration of current carrier (electronics), and play the stable Co that mixes
2+Effect.
In ZnO thin film doped preparation, mainly contain following several method at present, pulsed laser deposition (PLD), molecular beam epitaxy (MBE), metal organic vapor phase epitaxy (MOCVD) and rf magnetron sputtering (RF magnetron sputtering) and ultrasonic spray pyrolysis (USP) and sol-gel (Sol-Gel) method etc.The Sol-Gel method prepares adulterated ZnO, compare with traditional methods such as PLD, MBE, MOCVD and rf magnetron sputtering, it is simple to have the preparation method, needing no vacuum equipment, realize easily evenly mixing, can on various substrates, prepare big face and the complicated film of forming.
Summary of the invention
Adopt the Sol-Gel method and prepare dilute magnetic semiconductor material, and Curie temperature is increased to more than the room temperature with ferromegnetism feature in conjunction with codoped approach (Co and Al codope ZnO).On structure, the doping content of control Co and Al is in certain scope, and the doping ZnO that obtains still has hexagonal wurtzite structure, and does not produce not phase-splitting.
With zinc acetate (Zn (CH
3COO)
22H
2O), cobaltous acetate (Co (CH
3COO)
24H
2O) and aluminum chloride (AlCl
36H
2O) be solute, ethylene glycol monomethyl ether is a solvent, and thanomin is a stablizer.Take by weighing solute by certain molar ratio example (Co:0.01～8%, Al:0.01～2%) and add in the ethylene glycol monomethyl ether, add and the equimolar thanomin of metallic cation then, the concentration of configuration solution is 0.6 ~ 0.8mol/l.At room temperature be stirred to fully and melt, stir up to obtaining even, transparent colloidal sol at 60～80 ℃ of water-bath lower magnetic forces then.Colloidal sol was placed 1～2 day and was not produced precipitation, go up dropping colloidal solution at cleaned in advance Si sheet or other substrates (silica glass, sapphire, SiC etc.), in the mode of rotating substrate colloid evenly being covered is coated with, place preheating under 125～150 ℃ the baking oven then, again through 300～350 ℃ thermal treatment, repeat the film that above step can obtain different thickness, final sample is anneal under 600～800 ℃ of argon gas atmosphere.Process at the preparation nano-powder only need be omitted the spin coating process, to alumina crucible, takes same heat-treat condition can obtain absinthe-green nano-powder (embodiment is example with the film) colloidal sol.
The present invention adopts the Sol-Gel method to possess skills simply, expends lowly, is easy to obtain advantages such as large-area film.Because colloid obtains by solution, chemical ingredients is just the same in the micelle and between micelle, can prepare the even hotchpotch of polycomponent (degree of uniformity can reach the molecular level level), and can prepare that some traditional methods are difficult to obtain or unavailable at all product.
In the present invention, sol-gel method makes in Co and the even doping ZnO of Al ion, the Al ionic is introduced the carrier concentration that can significantly improve among the ZnO, regulate the interionic ferromagnetic coupling exchange of Co effectively, make ZnO:(Co, Al) powder and thin-film material all show as ferromegnetism, and its Curie temperature is up to 360K, coercive force ~ 350 Oe.
ZnO:(Co with high-curie temperature, the Al) preparation of material is for spin appliance device (Spin-LED, Spin-FET, Spin Valve etc.) research and development provide good materials for support.
Description of drawings
Fig. 1 Zn
0.94Co
0.05Al
0.01The O sample obviously shows as ferromagnetic feature at the magnetic hysteresis loop of 360K, and coercive force is 350 Oe.
Fig. 2 analyzes based on the x ray absorption near edge structure (XANES) that synchrotron radiation test characterizes, and this technology can be used for characterizing effectively the valence state of specific essence.Figure is Zn
0.94Co
0.05Al
0.01O sample and Co and CoO standard specimen XANES collection of illustrative plates, as can be seen from the figure, the Co in the sample is+divalent.
Fig. 3 Zn
0.94Co
0.05Al
0.01The expansion X ray of O sample and ZnO and Co standard specimen absorbs fine structure (EXAFS) collection of illustrative plates, and this technology can be used to characterize effectively the neighbour of specific atoms in conjunction with situation.Co as can be seen from the radial distribution collection of illustrative plates
2+Environment on every side and the Zn among the ZnO
2+Close, show Co
2+Replaced Zn
2+And and do not change the hexagonal wurtzite structure of ZnO.
Embodiment
Preparation ZnO:(Co, Al) colloidal solution.With the routine in molar ratio Zn of analytical pure zinc acetate, cobaltous acetate and aluminum chloride: Co: Al=94: be dissolved in ethylene glycol monomethyl ether at 5: 1.Add and the equimolar thanomin of metallic cation then, the concentration of configuration solution is 0.7mol/l.At room temperature be stirred to solute and melt fully, stirred 2 hours at 60 ℃ of water-bath lower magnetic forces then, obtain even, transparent colloidal sol at last.Colloidal sol was placed 48 hours and was not produced precipitation.
Go up several colloidal solution of dropping at cleaned in advance Si sheet or other substrates (silica glass, sapphire, SiC etc.), rotated substrates 25 seconds, make colloidal solution evenly cover and be coated on the Si sheet with 2500 revolutions per seconds speed.
Film was placed in 125 ℃ the baking oven 20 minutes, 300 ℃ of thermal treatment is 15 minutes then.
Repeating step 2 and 3 for several times obtains the film of different thickness, 800 ℃ of thermal treatment 1 hour under argon gas atmosphere at last.
Change the doping content (Zn of Co and Al
0.96Co
0.03Al
0.01O, Zn
0.90Co
0.08Al
0.02O), other conditions constant can prepare different levels of doping film.
Finally, obtained to have the ZnO:(Co of C axle preferrel orientation, Al) film, and successfully realized ferromegnetism under the 360K temperature, and as shown in Figure 1, coercive force～3500e.Hall test surfaces film conduction type is the n type, and electron density is 10
20Cm
-3More than, resistivity 10
-2～10
-1Ω cm.Utilize X ray to absorb valence state and residing position that fine structure has been studied Co, near side (ns) X ray absorbing structure (XANES) shows that the Co that mixes is+divalent, as shown in Figure 2; The expansion X ray absorbs fine structure (EXAFS) and shows Co
2+Surrounding environment and Zn
2+Identical, as shown in Figure 3.By analysis explanation Co to structure
2+Replaced Zn
2+And do not change the structure of ZnO, get rid of possibility that has metal Co bunch in the sample, illustrated that also above-mentioned ferromegnetism is an intrinsic simultaneously, but not second mutually extremely.
Claims (3)
1. sol-gel method prepares the ZnO:(Co of high temperature ferromagnetism, and Al) method of nano material mainly comprises the steps:
(1) selecting zinc acetate, cobaltous acetate, aluminum chloride for use is solute, and ethylene glycol monomethyl ether is a solvent, and thanomin is a stablizer;
(2) be 0.01～8% by accounting for solute molar percentage Co, Al 0.01～2% takes by weighing solute, zinc acetate, cobaltous acetate, cobalt chloride solute are added in the ethylene glycol monomethyl ether, add and the equimolar thanomin of metallic cation then, the concentration of configuration solution is 0.6～0.8mol/l;
(3) at room temperature be stirred to dissolving fully, stir up to obtaining even, transparent colloidal sol at 60～80 ℃ of water-bath lower magnetic forces then;
(4) drip colloidal solution on cleaned in advance Si sheet or silica glass, sapphire, SiC substrate, in the mode of rotation substrate colloid is evenly covered and be coated with, then through preheating, the thermal treatment after annealing is handled.
2. the ZnO:(Co for preparing high temperature ferromagnetism by the described sol-gel method of claim 1, the Al) method of nano material is characterized in that heat treated temperature is 300～350 ℃
3. the ZnO:(Co for preparing high temperature ferromagnetism by claim 1 or 2 described sol-gel methodes, the Al) method of nano material is characterized in that annealing conditions is under 600～800 ℃ and argon gas atmosphere.
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| CN101629284B (en) * | 2009-08-03 | 2011-01-26 | 北京航空航天大学 | Method for preparing aluminium-doped zinc oxide transparent conductive film by solvent thermal process |
| CN102311671B (en) * | 2011-08-30 | 2014-07-30 | 河南华美新材料科技有限公司 | AZO transparent conductive film paint, glass plated with the paint and preparation method thereof |
| CN103132063A (en) * | 2011-11-24 | 2013-06-05 | 长春工程学院 | Method for preparing p-type Cu-Co-codoped zinc oxide film |
| CN103485165A (en) * | 2013-09-11 | 2014-01-01 | 昆山市万丰制衣有限责任公司 | Preparation method of nanometer zinc oxide-ferric oxide mixed sol |
| CN105314672B (en) * | 2015-10-15 | 2017-04-05 | 西安工业大学 | A kind of sol-gel process for preparing of Co-doped ZnO nanometer rods |
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| CN110697759A (en) * | 2019-09-25 | 2020-01-17 | 安徽省含山县锦华氧化锌厂 | Ultraviolet-absorbing nano zinc oxide |
| CN116180067B (en) * | 2022-10-27 | 2024-03-12 | 北京科技大学 | Preparation method of high-temperature ferromagnetic aluminum cobalt oxide parallel orientation nano-sheet array material |
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