CN103074576B - Zno-based diluted semi-conductor thin-film and preparation method thereof - Google Patents
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Abstract
The invention discloses a kind of zno-based diluted semi-conductor thin-film and preparation method thereof. Method one is taking analytically pure metal nitrate as raw material, obtain the ZnO powder of doping by aqueous solution coprecipitation, then adopt solid phase method sintering to obtain ceramic target, be prepared into again the dilute magnetic semiconductor ZnO film of doping by pulsed laser deposition (PLD), or equally taking analytically pure metal nitrate as raw material, by sol-gal process, through preparation colloidal sol---whirl coating---process of thermal treatment flow process, be prepared into the zno-based diluted semi-conductor thin-film of doping. So the energy gap of the zno-based film of preparation can be regulated and controled by the doping of Mg and Cd, and then regulates and controls its ferromagnetism. Mix and in the rare magnetic thin film of zno-based of Co or Mn, mix altogether Cd and can make band gap reduce, the room temperature saturation magnetization of film increases, and can make band gap increase and mix altogether Mg, and film room temperature saturation magnetization reduces.
Description
Technical field
The invention belongs to material science, particularly relate to a kind of zno-based diluted semi-conductor thin-film and preparation method thereof.
Background technology
In present information industry, in semi-conducting material, conventionally utilize this single-degree-of-freedom work of electric charge of electronics, and electronics alsoThere is one degree of freedom to spin exactly. Electronics is directed movement in semiconductor, and a large amount of information has also been carried in its spin. AsFruit can obtain the electric current that spin-polarized degree is higher in semi-conducting material, and semi-conductive electric property can be subject to magneticThe regulation and control of field. Based on this, can design the spintronics device of many Multifunctions, and develop newElectronic signal process mode, improves the treatment effeciency of electronic information greatly. How Semiconductor Spintronics is studied exactlyUtilize the science of this single-degree-of-freedom of electron spin in semiconductor, and its basis is just how to obtain the electric current of spin polarization.In semiconductor, mix a small amount of magnetic ion, make magnetic ion replace at random the cation in lattice and form rare magnetic halfConductor (DilutedMagneticSemiconductors is called for short DMSs), can make the magnetic moment impact half of magnetic ionThe spin polarization of conductor current, reaches the effect that spin polarized current injects. Because dilute magnetic semiconductor can adopt researchThe method that the material system of comparative maturity mixes magnetic ion obtains, and more easily drops into practical application, so rare magnetic is partly ledBody becomes an important research object of Semiconductor Spintronics. The local magnetic of magnetic ion in dilute magnetic semiconductorBetween square and carrier and defect, have very strong Spin exchange interaction, this exchange interaction can make the electricity of semi-conducting material, optical parametric are subject to the impact of external magnetic field variation and correspondingly change, and can change rare magnetic half by changing external magnetic fieldThe physical property of conductor. Dilute magnetic semiconductor material has many special physical propertys, and for example huge magneto-optic effect, hugeNegative magnetoresistance effect, insulator-Metal Phase Transition of magnetic field induction etc.
ZnO is almost that Recent study is maximum, the semi-conducting material that performance is enriched the most. Its room temperature structure is buergeriteStructure, is direct band-gap semicondictor, has good chemical stability and heat endurance. ZnO is not only applied to halfConductor field, it is at acoustics, and the application in the fields such as optics is also widely studied, as is applied in ultra violet light emitter, soundSurface wave device, transparent high power electronic device, window material of piezoelectric transducer and solar cell etc. ZnOThe research of based diluted magnetic semiconductor also becomes focus in recent years, because transient metal doped ZnO is rare can demonstrationThe dilute magnetic semiconductor of room-temperature ferromagnetic. Carry out device design and nanoscale research owing to being more convenient for, people usually studyZnO diluted semi-conductor thin-film. The preparation method of the film adopting mainly comprise sol-gal process, magnetron sputtering method,Pulsed laser deposition (PLD) method, molecular beam epitaxy (MBE) method etc. Different experiment groups also attempts changing eachPlant doping and preparation condition and regulate and control its room-temperature ferromagnetic, such as changing the kind of magnetic ion, the concentration of magnetic ion,The kind of substrate, the partial pressure of oxygen of growing film, etc.
Energy gap (abbreviation band gap) is an important parameter of semi-conducting material, and its definition is semiconductor conduction band bottomTo the energy difference at valence band top. Different semiconductor band gap have very big-difference, such as the energy gap of silicon is 1.12eV,The band gap of ZnO is 3.37eV etc. Energy band engineering (BandgapEngineering) refers to by mixing in semiconductorDifferent components, changes semi-conductive band gap, thereby changes semi-conductive photoelectric property. Taking ZnO as example, ZnO doesFor a kind of wide band gap semiconducter of excellent performance, aspect ultra-violet light-emitting device, having great application prospect, so,The means of finding its band gap of regulation and control become very important. Much research has all reported that the different component of adulterating is to ZnO band gapRegulating and controlling effect. As the people such as Makino have just found the method for ZnO system being carried out to band gap regulation and control: mix Mg and makeThe band gap of ZnO broadens, and mixes Cd and makes ZnO band gap narrow [MakinoT, SegawaY.BandgapengineeringbasedonMgxZn1-xOandCdyZn1-yOternaryalloyfilms.AppliedPhysicsLetters，2001，78：1237-1239.]. But also do not report that so far research is by regulating the physics of band gap regulation and control zno-based dilute magnetic semiconductorCharacter.
Summary of the invention
The object of this invention is to provide a kind of zno-based diluted semi-conductor thin-film, it consists of Zn0.9M0.05R0.05O orZn0.95M0.05O；
Wherein, M represents the transition metal mixing in dilute magnetic semiconductor, is Co or Mn, and R representative is for regulation and controlThe element of ZnO band gap is Mg or Cd.
Described zno-based diluted semi-conductor thin-film is the wurtzite structure of (002) orientation; The thickness of film is40nm-50nm。
Above-mentioned zno-based diluted semi-conductor thin-film also can be the product of preparing by the following method and obtain.
The method of the described zno-based diluted semi-conductor thin-film of preparation provided by the invention, comprises the steps:
1) with ammoniacal liquor by NH4HCO3After being adjusted to 7.6-9.5, the pH value of the aqueous solution is precipitated agent;
2) by the aqueous solution of zinc salt, M (NO3)2The aqueous solution and R (NO3)2The aqueous solution according to Zn wherein2+、M2+And R2+The mol ratio ratio of 0.9: 0.05: 0.05, with step 1) gained precipitating reagent carries out coprecipitation reaction, anti-Should precipitate by complete collection gained, dry and obtain precursor powder I;
Or, by the aqueous solution of zinc salt and M (NO3)2The aqueous solution according to Zn wherein2+With M2+Mol ratio 0.95:0.05 ratio, with step 1) gained precipitating reagent carries out coprecipitation reaction, reacts complete collection gained precipitation, dryObtain precursor powder II;
Described M (NO3)2And R (NO3)2In, the definition of M and R is as hereinbefore;
3) by step 2) carry out successively granulation, compressing tablet and sintering after gained precursor powder I or II calcining, obtain respectivelyCeramic target I or II;
4) taking step 3) gained ceramic target I or II be target, at Si (100) substrate or Si (100)/Pt (111)On substrate, use pulsed laser deposition deposit film, obtain respectively consisting of Zn0.9M0.05R0.05The described zno-based of O is rareMagnetic semiconductor film and consist of Zn0.95M0.05The described zno-based diluted semi-conductor thin-film of O.
The described step 1 of said method) in, the mass percentage concentration of ammoniacal liquor is 25-28%, is specially 28%;
Described NH4HCO3Mole dosage and step 2) in the ratio of mole total consumption of metal ion be 2.3-2.6:1, be specially 2.4: 1;
Described step 2) in, described zinc salt is specially Zn (NO3)2·6H2O；
The aqueous solution of described zinc salt, M (NO3)2The aqueous solution and R (NO3)2The concentration of the aqueous solution be 0.5-1mol/L;
In described coprecipitation reaction step, mode of heating is heating water bath, and temperature is 40-60 DEG C, is specially 50 DEG C,Time is 0.5-1 hour, is specially 1 hour;
Described step 3) in calcining step, temperature is 300-400 DEG C, is specially 400 DEG C, and the time is 1-1.5Hour, be specially 1 hour;
In sintering step, temperature is 1000-1300 DEG C, is specially 1300 DEG C, and the time is 3-4 hour, concreteIt is 4 hours; The speed that is risen to sintering temperature by room temperature is 3-5 DEG C/min, is specially 3 DEG C/min;
Described step 4) in deposition step, pulsed laser energy 320-350mJ, is specially 335mJ, and temperature is500-600 DEG C, is specially 520 DEG C.
The method of the zno-based diluted semi-conductor thin-film that the described M of preparation provided by the invention is Co, comprises the steps:
1) by zinc salt, Co (NO3)2And R (NO3)2According to Zn wherein2+、M2+And R2+Mol ratio 0.9: 0.05: 0.05Ratio, in the only methyl ether of solvent ethylene glycol, obtain colloidal sol I with complexing agent mixed dissolution;
By zinc salt and Co (NO3)2According to Zn wherein2+With M2+The mol ratio ratio of 0.95: 0.05, molten with complexing agentSolution obtains colloidal sol II in the only methyl ether of solvent ethylene glycol;
Described R (NO3)2In, the definition of R is as hereinbefore;
2) by step 1) gained colloidal sol I or II spin-coated thin film on Si (100)/Pt (111) substrate, move back after oven dryFire, obtains respectively consisting of Zn0.9Co0.05R0.05The described zno-based diluted semi-conductor thin-film of O and consisting ofZn0.95Co0.05The described zno-based diluted semi-conductor thin-film of O.
The described step 1 of said method) in, solvent is ethylene glycol monoemethyl ether;
Complexing agent is citric acid;
Described zinc salt is Zn (NO3)2·6H2O；
Described complexing agent and step 1) in the ratio of mole total consumption of metal ion be 1-1.5: 1, be specially 1: 1；
Described step 2) in, in spin coating step, rotating speed is 3000-4000rpm, is specially 3000rpm, rotation halfFootpath is 2.5-5mm, is specially 5mm;
In described heat treatment step, temperature is 350-400 DEG C, is specially 350 DEG C, and the time is 3-5 minute, is specially5 minutes;
In described annealing steps, temperature is 550-600 DEG C, is specially 600 DEG C, and the time is 10-15 minute, is specially15 minutes.
The method of the zno-based diluted semi-conductor thin-film that the described M of preparation provided by the invention is Mn, comprises following stepRapid:
1) by Mn (NO3)2The aqueous solution, zinc salt and R (NO3)2According to Mn wherein2+、Zn2+And R2+Mol ratioThe ratio of 0.05: 0.9: 0.05 obtains colloidal sol III with complexing agent mixed dissolution in the only methyl ether of solvent ethylene glycol;
By Mn (NO3)2The aqueous solution, zinc salt according to M wherein2+With Zn2+The mol ratio ratio of 0.05: 0.95, withComplexing agent is dissolved in the only methyl ether of solvent ethylene glycol and obtains colloidal sol IV;
Described R (NO3)2In, the definition of R is as hereinbefore;
2) by step 1) gained colloidal sol III or IV spin-coated thin film on Si (100)/Pt (111) substrate, carry out after oven dryAnnealing, obtains respectively consisting of Zn0.9Mn0.05R0.05The described zno-based diluted semi-conductor thin-film of O and consisting ofZn0.95Mn0.05The described zno-based diluted semi-conductor thin-film of O.
The described step 1 of said method) in, solvent is ethylene glycol monoemethyl ether;
Complexing agent is citric acid;
Described zinc salt is Zn (NO3)2·6H2O；
Described Mn (NO3)2The mass percentage concentration of the aqueous solution be 40-60%, be specially 50%;
Described complexing agent and step 1) in the ratio of mole total consumption of metal ion be 1-1.5: 1, be specially 1: 1；
Described step 2) in, in spin coating step, rotating speed is 3000-4000rpm, is specially 3000rpm, rotation halfFootpath is 2.5-5mm, is specially 5mm;
In described heat treatment step, temperature is 350-400 DEG C, is specially 350 DEG C, and the time is 3-5 minute, is specially5 minutes;
In annealing steps, temperature is 550-600 DEG C, is specially 600 DEG C, and the time is 10-15 minute, is specially 15Minute.
In addition, the application of the zno-based diluted semi-conductor thin-film that the invention described above provides in preparation room temperature ferrimagnetAnd the room-temperature ferromagnetic material that contains described zno-based diluted semi-conductor thin-film, also belong to protection scope of the present invention.
The invention provides the method for two kinds of making ZnO based diluted magnetic semiconductor thin films, method one is with analytically pure metal nitreHydrochlorate is raw material, obtains the ZnO powder of doping by aqueous solution coprecipitation, then adopts solid phase method sintering to obtainCeramic target, then be prepared into the dilute magnetic semiconductor ZnO film of doping by pulsed laser deposition (PLD), orEqually taking analytically pure metal nitrate as raw material, by sol-gal process, through preparation colloidal sol---whirl coating---Process of thermal treatment flow process, is prepared into the zno-based diluted semi-conductor thin-film of doping. So zno-based film of preparationEnergy gap can be regulated and controled by the doping of Mg and Cd, and then regulate and control its ferromagnetism. Mix the ZnO of Co or MnIn the rare magnetic thin film of base, mix altogether Cd and can make band gap reduce, the room temperature saturation magnetization of film increases, and mixes altogether MgCan make band gap increase, film room temperature saturation magnetization reduces. Pulsed laser deposition preparation provided by the present inventionThe method of film, quality of forming film is high, can be used for growing epitaxial film; Sol-gal process technique is simple, and equipment is cheap,Prepare the reproducible of film, be applicable to preparation in batches.
Brief description of the drawings
Fig. 1 is the XRD collection of illustrative plates of the film of preparation in embodiment 1.
Fig. 2 is the room temperature M-H curve of the film of preparation in embodiment 1.
Fig. 3 is the XRD collection of illustrative plates of the film of preparation in embodiment 2.
Fig. 4 is the ultraviolet-ray visible absorbing spectrum of the film of preparation in embodiment 2.
Fig. 5 is the room temperature M-H curve of the film of preparation in embodiment 2.
Fig. 6 is the XRD collection of illustrative plates of the film of preparation in embodiment 3.
Fig. 7 is the ultraviolet-ray visible absorbing spectrum of the film of preparation in embodiment 3.
Fig. 8 is the room temperature M-H curve of the film of preparation in embodiment 3.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples. InstituteThe method of stating is conventional method if no special instructions. Described raw material if no special instructions all can be from open commercial sources and, and it is pure to be analysis.
Embodiment 1
1) ammoniacal liquor that is 28% by mass percentage concentration regulates the pH value of the ammonium bicarbonate soln of 600mL1mol/LTo 8.7, be precipitated agent, in water-bath, be heated to 50 DEG C;
2) by the Zn (NO of 475mL0.5mol/L3)2·6H2Co (the NO of the aqueous solution of O and 25mL0.5mol/L3)2Mix, this mixed liquor joined to step 1 with dropper) in gained precipitating reagent, carry out coprecipitation reaction 1 in 50 DEG C littleShi Hou, produces pale pink precipitation, collects gained precipitation, and precipitation is carried out to suction filtration, oven dry, obtains precursor powder II;
3) by step 2) gained precursor powder II obtains ceramic powder in 400 DEG C of calcinings after 1 hour, to ceramic powderCarry out granulation, compressing tablet with PVA, control programming rate at 3 DEG C/min, sintering 4h Low fire ceramic target at 1300 DEG CMaterial II;
4) taking step 3) gained ceramic target II is target, heavy with pulsed laser deposition on Si (100) substrateLong-pending film (pulsed laser energy 335mJ), 520 DEG C of depositing temperatures, obtain consisting of Zn0.95Co0.05The zno-based of ODiluted semi-conductor thin-film.
According to upper identical method, only replace respective reaction thing according to product composition, and in described step 2) coprecipitatedForm sediment before reaction, to the magnesium nitrate hexahydrate (Mg (NO that adds again 25mL0.5mol/L in system3)2·6H2O) water-solubleThe four water cadmium nitrate Cd (NO of liquid or 25mL0.5mol/L3)2·4H2O) the aqueous solution, is consisted of respectivelyZn0.90Co0.05Mg0.05O or Zn0.90Co0.05Cd0.05The zno-based diluted semi-conductor thin-film of O.
X-ray diffraction analysis (XRD) test result shows, three kinds of films are the wurtzite structure oxidation of (002) orientationZinc, orientation better and is not found other dephasigns. Film thickness is 40nm. X-ray photoelectron spectroscopic analysis showsFilm composition is consistent with actual proportioning.
With respect to the ZnO film of the Co that only adulterates, the film room temperature ferromagnetism of codope Mg a little less than, codope CdFilm room temperature ferromagnetism stronger, as shown in Figure 1 and Figure 2.
Embodiment 2
1) with analytically pure zinc nitrate hexahydrate (Zn (NO3)2·6H2And cobalt nitrate hexahydrate (Co (NO O)3)2·6H2O) beRaw material, citric acid is complexing agent, is dissolved in the only methyl ether of 30mL solvent ethylene glycol, makes its concentration be 0.2mol/L,Under normal temperature, stir and within 4 hours, obtain colloidal sol II.
2) by step 1) gained colloidal sol II spin-coated thin film on Si (100)/Pt (111) substrate, rotating speed is 3000rpm,Radius of turn is 5mm, after heat treatment 5min, repeats said process until film reaches desired thickness at 350 DEG C,Finally in rapid heat-treatment furnace 600 DEG C annealing 15 minutes, obtain consisting of Zn0.95Co0.05The rare magnetic of zno-based of OSemiconductive thin film.
According to upper identical method, only replace respective reaction thing according to product composition, and in described step 1) dissolveBefore step, in system, add again the magnesium nitrate hexahydrate identical with the mole dosage of cobalt nitrate hexahydrate(Mg(NO3)2·6H2O) or four water cadmium nitrate (Cd (NO3)2·4H2O), consisted of respectivelyZn0.90Co0.05Mg0.05O and Zn0.90Co0.05Cd0.05The zno-based diluted semi-conductor thin-film of O.
X-ray diffraction analysis (XRD) test result shows, three kinds of films are the wurtzite structure oxidation of (002) orientationZinc, does not find other dephasigns. Film thickness is 50nm. X-ray photoelectron spectroscopic analysis show film composition withActual proportioning is consistent. With respect to the ZnO film of the Co that only adulterates, the Thin Films UV-vis absorption spectra of codope MgMiddle ABSORPTION EDGE blue shift, band gap broadens, and room-temperature ferromagnetic dies down, and in the Thin Films UV-vis absorption spectra of codope Cd, inhalesReceive limit red shift, band gap narrows, room-temperature ferromagnetic grow. As shown in Fig. 3, Fig. 4 and Fig. 5.
Embodiment 3:
1) with analytically pure zinc nitrate hexahydrate (Zn (NO3)2·6H2And the mass percentage concentration manganese nitrate water that is 50% O)Solution is raw material, and citric acid is complexing agent, is dissolved in the only methyl ether of 30mL solvent ethylene glycol Zn2+Concentration be0.2mol/L stirs and within 4 hours, obtains colloidal sol III under normal temperature.
2) by step 1) gained colloidal sol III spin-coated thin film on Si (100)/Pt (111) substrate, rotating speed is 3000rpm,Radius of turn is 5mm, after heat treatment 5min, repeats said process until film reaches desired thickness at 350 DEG C,Finally in rapid heat-treatment furnace 600 DEG C annealing 15 minutes, obtain consisting of Zn0.95Mn0.05The rare magnetic of zno-based of OSemiconductive thin film.
According to upper identical method, only replace respective reaction thing according to product composition, and in described step 1) dissolveBefore step, in system, add again the magnesium nitrate hexahydrate identical with the mole dosage of cobalt nitrate hexahydrate(Mg(NO3)2·6H2O) or four water cadmium nitrate (Cd (NO3)2·4H2O), consisted of respectivelyZn0.90Mn0.05Mg0.05O and Zn0.90Mn0.05Cd0.05The zno-based diluted semi-conductor thin-film of O.
X-ray diffraction analysis (XRD) test result shows, three kinds of films are the wurtzite structure oxidation of (002) orientationZinc, does not find other dephasigns. Film thickness is 50nm. X-ray photoelectron spectroscopic analysis show film composition withActual proportioning is consistent. With respect to the ZnO film of a doped with Mn, the Thin Films UV-vis absorption spectra of codope MgMiddle ABSORPTION EDGE blue shift, band gap broadens, and room-temperature ferromagnetic dies down, and in the Thin Films UV-vis absorption spectra of codope Cd, inhalesReceive limit red shift, band gap narrows, and room-temperature ferromagnetic grow, as shown in Fig. 6, Fig. 7 and Fig. 8.
Claims (9)
1. a zno-based diluted semi-conductor thin-film, it consists of Zn0.9M0.05R0.05O；
Wherein, M is Co, and R is Cd;
M is Mn, and R is Mg or Cd; Described zno-based diluted semi-conductor thin-film is the buergerite of (002) orientationStructure; The thickness of described film is 40-50nm.
2. a method of preparing zno-based diluted semi-conductor thin-film described in claim 1, comprises the steps:
1) with ammoniacal liquor by NH4HCO3After being adjusted to 7.6-9.5, the pH value of the aqueous solution is precipitated agent;
2) by the aqueous solution of zinc salt, M (NO3)2The aqueous solution and R (NO3)2The aqueous solution according to Zn wherein2+、M2+And R2+The ratio of mol ratio 0.9:0.05:0.05, with step 1) gained precipitating reagent carries out coprecipitation reaction, anti-Should precipitate by complete collection gained, dry and obtain precursor powder I;
Described M (NO3)2And R (NO3)2In, the definition of M and R is identical with claim 1;
3) by step 2) carry out successively granulation, compressing tablet and sintering after gained precursor powder I calcining, obtain respectively potteryTarget I;
4) taking step 3) gained ceramic target I is target, on Si (100) substrate or Si (100)/Pt (111) substrateUse pulsed laser deposition deposit film, obtain consisting of Zn0.9M0.05R0.05The described zno-based dilute magnetic semiconductor of O is thinFilm.
3. method according to claim 2, is characterized in that: described step 1) in, the quality percentage of ammoniacal liquorConcentration is 25-28%, or,
Described NH4HCO3Mole dosage and step 2) in the ratio of mole total consumption of metal ion be 2.3-2.6:1; Or,
Described step 2) in, described zinc salt is specially Zn (NO3)2·6H2O; Or,
The aqueous solution of described zinc salt, M (NO3)2The aqueous solution and R (NO3)2The concentration of the aqueous solution be 0.5-1mol/L;Or,
In described coprecipitation reaction step, mode of heating is heating water bath, and temperature is 40-60 DEG C, and the time is0.5-1 hour; Or,
Described step 3) in calcining step, temperature is 300-400 DEG C, and the time is 1-1.5 hour; Or,
In sintering step, temperature is 1000-1300 DEG C, and the time is 3-4 hour; Rise to sintering temperature by room temperatureSpeed is 3-5 DEG C/min; Or,
Described step 4) in deposition step, pulsed laser energy 320-350mJ, temperature is 500-600 DEG C.
4. prepare a method for the zno-based diluted semi-conductor thin-film that M is Co described in claim 1, comprise asLower step:
1) by zinc salt, Co (NO3)2And R (NO3)2According to Zn wherein2+、M2+And R2+Mol ratio 0.9:0.05:0.05Ratio, in the only methyl ether of solvent ethylene glycol, obtain colloidal sol I with complexing agent mixed dissolution;
Described R (NO3)2In, the definition of R is identical with claim 1;
2) by step 1) gained colloidal sol I spin-coated thin film on Si (100)/Pt (111) substrate, after oven dry, anneal,Obtain consisting of Zn0.9Co0.05R0.05The described zno-based diluted semi-conductor thin-film of O.
5. method according to claim 4, is characterized in that: described step 1) in, solvent is that ethylene glycol is onlyMethyl ether; Or,
Complexing agent is citric acid; Or,
Described zinc salt is Zn (NO3)2·6H2O; Or,
Described complexing agent and step 1) in the ratio of mole total consumption of metal ion be 1-1.5:1; Or,
Described step 2) in, in spin coating step, rotating speed is 3000-4000rpm, radius of turn is 2.5-5mm; Or,
In described annealing steps, temperature is 550-600 DEG C, and the time is 10-15 minute.
6. prepare a method for the zno-based diluted semi-conductor thin-film that M is Mn described in claim 1, comprise asLower step:
1) by Mn (NO3)2The aqueous solution, zinc salt and R (NO3)2According to Mn wherein2+、Zn2+And R2+Mol ratioThe ratio of 0.05:0.9:0.05 obtains colloidal sol III with complexing agent mixed dissolution in the only methyl ether of solvent ethylene glycol;
Described R (NO3)2In, the definition of R is identical with claim 1;
2) by step 1) gained colloidal sol III spin-coated thin film on Si (100)/Pt (111) substrate, after oven dry, anneal,Obtain consisting of Zn0.9Mn0.05R0.05The described zno-based diluted semi-conductor thin-film of O.
7. method according to claim 6, is characterized in that: described step 1) in, solvent is that ethylene glycol is onlyMethyl ether; Or,
Complexing agent is citric acid; Or,
Described zinc salt is Zn (NO3)2·6H2O; Or,
Described Mn (NO3)2The mass percentage concentration of the aqueous solution be 40-60%; Or,
Described complexing agent and step 1) in the ratio of mole total consumption of metal ion be 1-1.5:1;
Described step 2) in, in spin coating step, rotating speed is 3000-4000rpm, radius of turn is 2.5-5mm; Or,
In annealing steps, temperature is 550-600 DEG C, and the time is 10-15 minute.
8. the application of zno-based diluted semi-conductor thin-film in preparation room temperature ferrimagnet described in claim 1.
9. contain the room-temperature ferromagnetic material of zno-based diluted semi-conductor thin-film described in claim 1.
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