CN103194798B - Ferromagnetic polycrystal film of a kind of transient metal doped zno-based and preparation method thereof - Google Patents

Ferromagnetic polycrystal film of a kind of transient metal doped zno-based and preparation method thereof Download PDF

Info

Publication number
CN103194798B
CN103194798B CN201310113963.8A CN201310113963A CN103194798B CN 103194798 B CN103194798 B CN 103194798B CN 201310113963 A CN201310113963 A CN 201310113963A CN 103194798 B CN103194798 B CN 103194798B
Authority
CN
China
Prior art keywords
ferromagnetic
polycrystal film
zno
doping
coo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201310113963.8A
Other languages
Chinese (zh)
Other versions
CN103194798A (en
Inventor
朱丽萍
胡亮
陈文丰
何海平
叶志镇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CN201310113963.8A priority Critical patent/CN103194798B/en
Publication of CN103194798A publication Critical patent/CN103194798A/en
Application granted granted Critical
Publication of CN103194798B publication Critical patent/CN103194798B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The present invention discloses the ferromagnetic polycrystal film of a kind of transient metal doped zno-based, and the material forming this ferromagnetic polycrystal film is Zn 1-x(TM) xo; Wherein, TM is transition metal Cu, Co or Mn, and for Cu, 0 < x < 0.03; For Co and Mn, 0 < x < 0.08.The invention also discloses the preparation method of the ferromagnetic polycrystal film of above-mentioned transient metal doped zno-based, TM doping zinc oxide nanometer crystalline substance precipitation is prepared by the acetate precursor solution of transition metal and zinc, then the ferromagnetic polycrystal film of transient metal doped zno-based is obtained through dispersion, spin coating, for strengthening the ferromagnetic stability of polycrystal film, improve transport property, also carry out the optimization process of hydrogen plasma.The method technique is simple, with low cost, can regulate doping content, the polycrystal film densification obtained is smooth, tack is good, all show obvious magnetic hysteresis loop, can be applicable in Quantum Spin device under room temperature in a big way.

Description

Ferromagnetic polycrystal film of a kind of transient metal doped zno-based and preparation method thereof
Technical field
The present invention relates to the preparation field of dilute magnetic semiconductor polycrystal film, particularly relate to ferromagnetic polycrystal film of a kind of transient metal doped zno-based and preparation method thereof.
Background technology
Transition metal (TM) doped ZnO-based diluted magnetic semiconductor is after GaAs, and another is placed high hopes by the external world, have the compound semiconductor materials of conduction and spin properties concurrently.The people such as T.Dietl predict the Curie temperature that this system will have higher than room temperature, be expected to be applied in (T.Dietl in semiconductor spin device, H.Ohno, F.Matsukura, J.Cibert, and D.Ferrand, Zener ModelDescription of Ferromagnetism in Zinc-Blende Magnetic Semiconductors, Science, 2000 (287): 1019-1022).Be limited to the deficiency in ZnO material cognition, the puzzlement of numerous defect structures (mainly point defect) and p-type doping, hinders the process of its application development.
As the applicable importance of ZnO merit, the bottleneck of its magnetic research is also quite give prominence to, as obtain magnetism characteristic be difficult to reappear, magnetic moment value less and lack confidence level, be difficult to possess low resistance and high magnetic moment feature simultaneously.Most typical situation is exactly, and the TM adopting conventional equipment (pulsed laser deposition, magnetron sputtering) to grow is ZnO thin film doped, and because crystal boundary scattering ratio is comparatively serious, resistivity is comparatively large, is difficult to be applied to further in self-spining device; And the ferromagnetic exchange mechanism of dilute concentration doping induction lacks a large amount of fact basis (needing a large amount of current carriers), this is also one of reason of ferrimagnetism instability.
With the propelling of ZnO defect project, everybody recognizes that vacancy-like defects (Lacking oxygen, Zinc vacancies) and clearance type defect (zinc gap) also can assist magnetic moments parallel to arrange gradually, and the theory from the auxiliary ferromagnetic origin of third party's (except TM ion, current carrier) is also quietly being risen.Due to primary point defect extremely unstable, the ferromagnetic stability making defect auxiliary and repeatability need further research, people in the urgent need to find a kind of efficiently, the doping agent of ferromagnetic double exchange can be induced.
Hydrogen is ubiquitous element in semi-conductor, often because the contamination of growing environment is by involuntary introducing.According to the difference of residing environment, hydrogen often plays diversified role, for ZnO material, when it is distributed in gap digit, contribute N-shaped to conduct electricity usually used as shallow donor, if be distributed near defect, intrinsic alms giver can be compensated again, key and defect state are hanged in passivation, and these character are confirmed by academia mostly.Nearest research shows, protium can strengthen the interionic spin coupling of TM by the mode of bridging, the theoretical investigation of ZnMnO, ZnCoO ferromagnetic exchange is assisted to have been reported (C.H.Park andD.J.Chadi about hydrogen, Hydrogen-mediated spin-spin interaction in ZnCoO, PhysicalReview Letters, 2005 (94): 127204).Although the experimental study of correspondence is carried out, the research of H process related process parameters is also very few, particularly to the ZnO polycrystal film system of TM doping.
It is generally acknowledged, the thermostability of hydrogen atom in ZnO film is poor, and high temperature easily therefrom overflows, and this is the major cause of hydrogen doping ZnO conductivity instability.After introducing TM element in ZnO system, hydrogen atom closely can be strapped in the TM ion pair (occupying Zn position) of neighbour around usually, plays the effect of rock steady structure.The method that current protium deliberately adulterates mainly contains three kinds: hydrogen environment annealing, Hydrogen implantation and hydrogen plasma process.The protium poor heat stability that first two method is introduced, the protium adopting capacitively coupled plasma reactor device to produce then can many (the P.F.Cai and J.B.You of efficient stable, Enhancement of conductivity and transmittanceof ZnO films by post hydrogen plasma treatment, Journal of Applied Physics, 2009 (105): 104-112).
In addition, the brilliant uniform component of doping zinc oxide nanometer prepared by colloid chemistry methods, be compatible with InkJet printing processes, make the smooth densification of the material after film forming, defect kind is single, polycrystalline structure makes the protium part introduced be distributed near crystal boundary, compensation point defect, improve conductance (W.M.Kim, Y.H.Kim, J.S.Kim, J.Jeong, Y-J Baik, J-K Park, K.S.Lee, and T-Y Seong, Hydrogen in polycrystalline ZnO thin films, Journal of Physics D:AppliedPhysics, 2010 (43): 365406), another part TM ion that then can be coupled produces ferromagnetic double exchange.Also rarely have report about hydrogen plasma process TM doping ZnO polycrystal film, the experiment that strengthens ferromagnetic stability, therefore, the systematic study carrying out this respect will be that compacting is theoretical, the work of strengthened research.
Summary of the invention
The resistivity ZnO thin film doped for TM in prior art is larger, be difficult to be applied in self-spining device, and there is the problem of ferrimagnetism instability, the invention provides the transient metal doped zno-based polycrystalline ferromagnetic thin film that a kind of optical property is good, magnetic performance is stable.
The ferromagnetic polycrystal film of a kind of transient metal doped zno-based, the material forming described ferromagnetic polycrystal film is Zn 1-x(TM) xo; Wherein, TM is transition metal Cu, Co or Mn, and for Cu, 0 < x < 0.03; For Co or Mn, 0 < x < 0.08.
The invention also discloses the preparation method of the described ferromagnetic polycrystal film of transient metal doped zno-based, TM doping zinc oxide nanometer crystalline substance precipitation is prepared by the acetate precursor solution of transition metal and zinc, then colloid nanocrystalline solution is obtained through dispersion, brilliant for TM doping zinc oxide nanometer solution is obtained the final ferromagnetic polycrystal film of transient metal doped zno-based through spin coating technique, for strengthening the ferromagnetic stability of polycrystal film, also the optimization process of hydrogen plasma is carried out to polycrystal film.
A preparation method for the ferromagnetic polycrystal film of transient metal doped zno-based, comprises the steps:
(1) by TM (CH 3cOO) 2with Zn (CH 3cOO) 2be dissolved in respectively in proportion in methyl alcohol, at 70 ~ 90 DEG C, water-bath backflow 60 ~ 120 minutes, obtains TM (CH respectively 3cOO) 2and Zn (CH 3cOO) 2acetate precursor solution;
(2) the KOH methanol solution of 0.1 ~ 0.4mol/L is dropped to the Zn (CH that step 1) obtains 3cOO) 2in precursor solution, Zn (CH 3cOO) 2be 1:1.67 ~ 1:2 with the mol ratio of KOH, water-bath 15 ~ 40 minutes at 70 ~ 90 DEG C;
(3) again to step 2) reaction solution in inject TM (CH 3cOO) 2precursor solution, after temperature is down to 50 ~ 60 DEG C, add and step 2) the KOH methanol solution of 0.1 ~ 0.4mol/L of moderate, 50 ~ 60 DEG C of isothermal reactions 120 ~ 210 minutes, obtain TM doping zinc oxide nanometer crystalline substance precipitation;
(4) the brilliant deposition and purification of TM doping zinc oxide nanometer step (3) obtained;
(5) TM doping zinc oxide nanometer crystalline substance precipitation step (4) obtained fully is dissolved in trichloromethane, obtains the ZnO colloid nanocrystalline solution of TM doping;
(6) the ZnO colloid nanocrystalline solution of the TM doping obtained by trichloromethane dilution step (5) also filters, and is spin-coated on cleaned substrate, is no more than the process of 100 DEG C of prebake after annealings, obtain the ferromagnetic polycrystal film of zno-based of TM doping;
(7) H plasma treatment is carried out to the ferromagnetic polycrystal film of zno-based of the TM doping that step (6) obtains.
According to target product Zn 1-x(TM) xthe chemical constitution of O is known, prepares in the acetate precursor solution process of transition metal and zinc, TM (CH in step (1) 3cOO) 2with Zn (CH 3cOO) 2molar ratio should be x:(1-x), wherein for Cu, 0 < x < 0.03; For Co and Mn, 0 < x < 0.08, is dissolved in methyl alcohol respectively with this ratio, obtains TM (CH respectively through water-bath backflow 3cOO) 2and Zn (CH 3cOO) 2acetate precursor solution.
Prepare in the process of TM doping zinc oxide nanometer crystalline substance precipitation owing to utilizing the acetate precursor solution of transition metal and zinc and can there is reactant residue, therefore also need to carry out washing purifying, as preferably, in step (4), the purge process of TM doping zinc oxide nanometer crystalline substance precipitation is first with frozen water cooling, then washs by methyl alcohol and n-octyl amine.
Rotating speed due to spin coating process directly can affect the planeness of film surface, and therefore in order to obtain, densification is smooth, tack good and the much higher brilliant film of transparence, and the present invention is preferred, and in step (6), the rotating speed of spin coating process is 2000 ~ 4000 revs/min.
As preferably, the substrate described in step (6) is silicon chip or quartz.
The polycrystal film obtained through spin coating technique also needs annealed process, makes the structure of film finer and close, and as preferably, in step (6), the condition of annealing is: anneal 1 ~ 2 hour in Ar atmosphere at 600 ~ 900 DEG C.
When being distributed in the gap digit of ZnO material due to protium, N-shaped is contributed to conduct electricity usually used as shallow donor, if be distributed near defect, intrinsic alms giver can be compensated again, key and defect state are hanged in passivation, strengthen ferromagnetic stability, therefore the present invention's polycrystal film of adopting H plasma treatment to obtain.As preferably, in step (7), the condition of H plasma treatment is: background air pressure is lower than 5 × 10 -6torr, operating air pressure is 10 ~ 30mTorr, and the power of radio-frequency power supply is 10 ~ 20W, and substrate temperature is room temperature to 150 DEG C, and the treatment time is 10 ~ 50 minutes.
The present invention is by regulating the parameter such as raw material type, ratio, temperature, time can controlled doping is nanocrystalline preferably size and pattern, optimize spin coating proceeding, annealing time and H plasma treatment parameter, the doped ZnO-based polycrystalline ferromagnetic thin film of TM that thickness is adjustable, densification is smooth, optical property is good, magnetic performance is stable can be obtained.
Compared with prior art, the present invention has following beneficial effect:
1) use comparatively simple solution method to prepare the ferromagnetic polycrystal film of ZnO of TM doping, technique is simple, with low cost, is fully compatible with planographic technique, can regulate doping content in a big way, there is no phase-splitting situation and occurs;
2) nano-crystal film of spin coating is after anneal, and compact structure is smooth, tack is good, thickness is controlled, transparence is higher, all shows obvious magnetic hysteresis loop under room temperature;
3) polycrystal film after hydrogen process, electric conductivity can reduce by 5 ~ 6 orders of magnitude, not only increases carrier concentration, also improves the mobility of film, and material resistance transformation from high to low confirms the improvement of electrology characteristic;
4) the TM doping ZnO polycrystal film after hydrogen process, good thermal stability, Absorbable organic halogens without phase-splitting, not only stable for the defect structure in system to about 600 DEG C, and under avoiding high temperature, protium spreads the conductance losses caused;
5) had before the polycrystal film magnetic moment size after hydrogen process comparatively processes and increased substantially, some has even exceeded theoretical magnetic moment of atom value (as Cu doping), confirms that protium plays keying action on the efficiency utilization of magnetic moment;
6) present method is simple to material final treatment techniques, only needs a rf magnetron sputtering equipment just can realize the batch processing of film, is applicable to large-scale industrial production;
7) the zno-based high magnetic moment polycrystal film that the present invention obtains can not only be applied on Quantum Spin device, and preparation cost is lower, and the design for more device architectures provides a kind of pervasive method.
Accompanying drawing explanation
Fig. 1 (a) is the atomic force microscopy of the Cu doping ZnO polycrystal film in embodiment 1 after hydrogen plasma process;
Fig. 1 (b) is the atomic force microscopy of the Co doping ZnO polycrystal film in embodiment 2 after hydrogen plasma process;
Fig. 1 (c) is the atomic force microscopy of the Mn doping ZnO polycrystal film in embodiment 3 after hydrogen plasma process;
Fig. 2 (a) is TM(Cu, Co or Mn before H plasma treatment) doping ZnO polycrystal film I-V rational curve;
Fig. 2 (b) is TM(Cu, Co or Mn after H plasma treatment) doping ZnO polycrystal film I-V rational curve;
Fig. 3 is the section sims analysis curve of Cu doping ZnO polycrystal film after hydrogen plasma process;
Fig. 4 is TM(Cu, Co or Mn after H plasma treatment) contrast of the room temperature magnetic hysteresis loop of doping ZnO polycrystal film;
Fig. 5 is TM(Cu, Co or Mn after H plasma treatment) doping ZnO polycrystal film magnetic moment varies with temperature the curve of (M-T);
Fig. 6 is 1.0%, 2.0%, 4.0%Cu ZnO thin film doped room temperature magnetic hysteresis loop after H plasma treatment;
Fig. 7 is the room temperature PL spectrum comparison diagram of ZnO:Cu polycrystal film before and after H plasma treatment.
Embodiment
In the present invention, raw materials used pureness specifications respectively: Zn (CH 3cOO) 2(99.99%), Cu (CH 3cOO) 2(99.99%), Mn (CH 3cOO) 2(98+%), Co (CH 3cOO) 2(99.995%), KOH particle (85+%), deionized water (R=18.2M Ω), n-octyl amine (99+%), trichloromethane (chromatographically pure), methyl alcohol (analytical pure).Substrate can be the obvious material of the diamagnetic signal such as silicon chip, quartz plate.
Embodiment 1
1) by 0.4914g Zn (CH 3cOO) 2, 0.0103g Cu (CH 3cOO) 2powder is dissolved in the methanol solution of 30mL and 20mL respectively, and all at 80 DEG C, water-bath refluxes 60 minutes, obtains Zn (CH 3cOO) 2with Cu (CH 3cOO) 2precursor solution;
2) the KOH methanol solution of 10mL0.2mol/L is dropped to the Zn (CH of step 1) 3cOO) 2in precursor solution, 80 DEG C of water-baths, after 15 minutes, continue to add Cu (CH 3cOO) 2precursor solution in above-mentioned solution, after temperature is down to 60 DEG C, then add the KOH methanol solution of 10mL0.235mol/L, in 60 DEG C of insulation reaction 120 minutes, obtain the brilliant product of 2.0%Cu doping zinc oxide nanometer;
3) cool termination reaction with frozen water, the centrifugal pre-wash of methyl alcohol 3 times, then precipitation to be dispersed in 20mL n-octyl amine 50 DEG C of amine bath process 60 minutes, centrifugally obtain the Cu doping zinc oxide nanometer crystalline substance precipitation after purifying;
4) in above-mentioned obtained nanocrystalline precipitation, adding 10mL trichloromethane makes it fully dissolve, and then uses the PTFE metre filter in 0.22 μm of aperture, obtains the TM doping ZnO colloid nanocrystalline solution that optical transmission is good;
5) monocrystalline silicon piece is used successively alcohol, acetone, deionized water ultrasonic cleaning 15 minutes, then with nitrogen by cleaning after silicon wafer blow-drying, with the rotating speed of 3000 revs/min, nanocrystal solution is spun in cleaned silicon chip substrate, thickness is about 500nm, after 60 DEG C of prebakes, anneal 1 hour in Ar atmosphere at 900 DEG C, obtain Cu doping ZnO polycrystal film;
6) film after anneal is placed in rf magnetron sputtering cavity, is evacuated to vacuum tightness and reaches 5 × 10 -6torr, then at room temperature hydrogen is passed into, operating air pressure is made to reach 10mTorr, open substrate power supply, setting power is 10W, produces hydrogen aura, exposes 10 minutes in hydrogen gas plasma, the Cu doping ZnO polycrystalline ferromagnetic thin film that obtained H plasma treatment is crossed, surface topography is shown in the atomic force microscopy of Cu doping ZnO polycrystalline ferromagnetic thin film in Fig. 1 (a).
In order to intuitively grasp the changing conditions of resistance before and after the process of film hydrogen, we have carried out I-V characteristic test to film, before this, adopt electron beam evaporation evaporation one deck Ti/Au electrode to ensure ohmic contact, concrete outcome is shown in Fig. 2 (a) and Fig. 2 (b) (in Fig. 2 (a), the I-V curve of ZnO:Mn and ZnO:Cu almost overlaps, and in Fig. 2 (b), the I-V curve of ZnO:Mn and ZnO:Co almost overlaps); Second ion mass spectroscopy (SIMS) test shows that protium is evenly distributed on the inner (see figure 3) of film; Polycrystal film at room temperature has saturated magnetic hysteresis loop, see ZnO:Cu curve in Fig. 4, magnetic moment varies with temperature curve, see ZnO:Cu curve in Fig. 5, showing that the magnetic of all samples originates from further is all intrinsic, there is no the interference of two-phase impurity, illustrate that hydrogen plasma process can significantly improve the structural stability of doping system, and reduce the resistivity of polycrystal film.
Embodiment 2
1) by 0.4914g Zn (CH 3cOO) 2, 0.0396g Co (CH 3cOO) 2powder is dissolved in the methanol solution of 20mL and 10mL respectively, and all at 65 DEG C, water-bath refluxes 120 minutes, obtains Zn (CH 3cOO) 2with Co (CH 3cOO) 2precursor solution;
2) the KOH methanol solution of 20mL0.4mol/L is dropped to the Zn (CH of step 1) 3cOO) 2in precursor solution, 65 DEG C of water-baths, after 40 minutes, continue to add Co (CH 3cOO) 2precursor solution in above-mentioned solution, after temperature is down to 50 DEG C, then add the KOH methanol solution of 20mL0.4mol/L, in 50 DEG C of insulation reaction 210 minutes, obtain the brilliant product of 6.0%Co doping zinc oxide nanometer;
3) cool termination reaction with frozen water, the centrifugal pre-wash of methyl alcohol 5 times, then precipitation to be dispersed in 30mL n-octyl amine 50 DEG C of amine bath process 90 minutes, centrifugally obtain the Co doping zinc oxide nanometer crystalline substance precipitation after purifying;
4) in above-mentioned obtained nanocrystalline precipitation, adding 15mL trichloromethane makes it fully dissolve, and then uses the PTFE metre filter in 0.22 μm of aperture, obtains the Co doping ZnO colloid nanocrystalline solution that optical transmission is good;
5) monocrystalline silicon piece is used successively alcohol, acetone, deionized water ultrasonic cleaning 15 minutes, then with nitrogen by cleaning after silicon wafer blow-drying, with the rotating speed of 2000 revs/min, nanocrystal solution is spun in cleaned silicon chip substrate, thickness is about 300nm, after 80 DEG C of prebakes, anneal 2 hours in Ar atmosphere at 600 DEG C, obtain Co doping ZnO polycrystal film;
6) film after anneal is placed in rf magnetron sputtering cavity, is evacuated to vacuum tightness and reaches 5 × 10 -6torr, then at room temperature hydrogen is passed into, operating air pressure is made to reach 10mTorr, open substrate power supply, setting power is 10W, produces hydrogen aura, exposes 20 minutes in hydrogen gas plasma, the Co doping ZnO polycrystalline ferromagnetic thin film that obtained H plasma treatment is crossed, surface topography is shown in the atomic force microscopy of Co doping ZnO polycrystalline ferromagnetic thin film in Fig. 1 (b).
Corresponding I-V characteristic and Magnetic Test at room temperature have saturated magnetic hysteresis loop the results detailed in Fig. 2 (a), Fig. 2 (b), polycrystal film, see ZnO:Co curve in Fig. 4, magnetic moment varies with temperature curve, sees ZnO:Co curve in Fig. 5.
Embodiment 3
1) by 0.4914g Zn (CH 3cOO) 2, 0.0194g Mn (CH 3cOO) 2powder is dissolved in the methanol solution of 20mL and 10mL respectively, and all at 70 DEG C, water-bath refluxes 80 minutes, obtains Zn (CH 3cOO) 2with Mn (CH 3cOO) 2precursor solution;
2) the KOH methanol solution of 20mL0.3mol/L is dropped to the Zn (CH of step 1) 3cOO) 2in precursor solution, 70 DEG C of water-baths, after 30 minutes, continue to add Mn (CH 3cOO) 2precursor solution in above-mentioned solution, after temperature is down to 50 DEG C, then add the KOH methanol solution of 20mL0.3mol/L, in 50 DEG C of insulation reaction 150 minutes, obtain the brilliant product of 4.0%Mn doping zinc oxide nanometer;
3) cool termination reaction with frozen water, the centrifugal pre-wash of methyl alcohol 5 times, then precipitation to be dispersed in 20mL n-octyl amine 50 DEG C of amine bath process 60 minutes, centrifugally obtain the Mn doping zinc oxide nanometer crystalline substance precipitation after purifying;
4) in above-mentioned obtained nanocrystalline precipitation, adding 10mL trichloromethane makes it fully dissolve, and then uses the PTFE metre filter in 0.22 μm of aperture, obtains the Co doping ZnO colloid nanocrystalline solution that optical transmission is good;
5) monocrystalline silicon piece is used successively alcohol, acetone, deionized water ultrasonic cleaning 15 minutes, then with nitrogen by cleaning after silicon wafer blow-drying, with the rotating speed of 2500 revs/min, nanocrystal solution is spun in cleaned silicon chip substrate, thickness is about 500nm, after 80 DEG C of prebakes, anneal 1.5 hours in Ar atmosphere at 750 DEG C, obtain Mn doping ZnO polycrystal film;
6) film after anneal is placed in rf magnetron sputtering cavity, is evacuated to vacuum tightness and reaches 5 × 10 -6torr, then at room temperature hydrogen is passed into, operating air pressure is made to reach 10mTorr, open substrate power supply, setting power is 15W, produces hydrogen aura, exposes 30 minutes in hydrogen gas plasma, the Mn doping ZnO polycrystalline ferromagnetic thin film that obtained H plasma treatment is crossed, surface topography is shown in the atomic force microscopy of Mn doping ZnO polycrystalline ferromagnetic thin film in Fig. 1 (c).
Corresponding I-V characteristic and Magnetic Test at room temperature have saturated magnetic hysteresis loop the results detailed in Fig. 2 (a), Fig. 2 (b), polycrystal film, see ZnO:Mn curve in Fig. 4, magnetic moment varies with temperature curve, sees ZnO:Mn curve in Fig. 5.
Embodiment 4
1) by 0.4914g Zn (CH 3cOO) 2powder is dissolved in the methanol solution of 30mL, and 0.0051g, 0.0103g and 0.0206g Cu (CH 3cOO) 2then be dissolved in respectively in the methanol solution of 20mL, above-mentioned all solution all at 80 DEG C water-bath reflux 120 minutes, obtain four kinds of precursor solutions;
2) the KOH methanol solution of 10mL0.235mol/L is dropped to the Zn (CH of step 1) 3cOO) 2in precursor solution, 80 DEG C of water-baths, after 15 minutes, continue to add remaining three kinds of Cu (CH 3cOO) 2in one in presoma to above-mentioned solution, after temperature is down to 60 DEG C, add the KOH methanol solution of 10mL0.235mol/L again, in 60 DEG C of insulation reaction 120 minutes, can obtain theoretical doping content respectively by the transition metal Cu acetate precursor solution adding above-mentioned different concns is 1.0%, 2.0% and the brilliant product of 4.0%Cu doping zinc oxide nanometer;
3) cool termination reaction with frozen water, the centrifugal pre-wash of methyl alcohol 3 times, then precipitation to be dispersed in 20mL n-octyl amine 50 DEG C of amine bath process 60 minutes, centrifugally obtain the Cu ion doping ZnO nano crystalline substance precipitation after purifying;
4) in above-mentioned obtained various nanocrystalline precipitation, adding 10mL trichloromethane respectively makes it fully dissolve, and then uses the PTFE metre filter in 0.22 μm of aperture successively, obtains the Cu doping ZnO colloid nanocrystalline solution that optical transmission is good;
5) monocrystalline silicon piece is used successively alcohol, acetone, deionized water ultrasonic cleaning 15 minutes, then with nitrogen by cleaning after silicon wafer blow-drying, with the rotating speed of 3000 revs/min, nanocrystal solution is spun in cleaned silicon chip substrate, thickness is about 200nm, after 80 DEG C of prebakes, anneal 2 hours in Ar atmosphere at 600 DEG C, obtain Cu doping ZnO polycrystal film;
6) film after anneal is placed in rf magnetron sputtering cavity, is evacuated to vacuum tightness and reaches 5 × 10 -6torr, then at room temperature passes into hydrogen, makes operating air pressure reach 10mTorr, open substrate power supply, setting power is 10W, produces hydrogen aura, exposure 20 minutes in hydrogen gas plasma, the Cu doping ZnO polycrystalline ferromagnetic thin film that obtained one group of doping content is adjustable, H plasma treatment is crossed.
As can be seen from the room temperature magnetic hysteresis loop of Fig. 6, the Cu plasma treated for H is ZnO thin film doped, magnetic moment size is optimized by the adjustment of doping, the intrinsic ferromagnetic characteristic of equally alternatively Cu doping in bright ZnO, and optimum doping content is about ~ 2.0%; The existence of H element does not suppress the deep level emission of Cu, strengthens the nearly band-edge emission of ZnO on the contrary, suppresses the point defect near crystal boundary, see Fig. 7.

Claims (2)

1. a preparation method for the ferromagnetic polycrystal film of transient metal doped zno-based, is characterized in that, the material forming described ferromagnetic polycrystal film is Zn 1-x(TM) xo; Wherein, TM is transition metal Cu, Co or Mn, and for Cu, 0 < x < 0.03; For Co or Mn, 0 < x < 0.08;
The preparation method of the described ferromagnetic polycrystal film of transient metal doped zno-based, comprises the steps:
(1) by TM (CH 3cOO) 2with Zn (CH 3cOO) 2be dissolved in respectively in proportion in methyl alcohol, at 70 ~ 90 DEG C, water-bath backflow 60 ~ 120 minutes, obtains TM (CH respectively 3cOO) 2and Zn (CH 3cOO) 2acetate precursor solution;
(2) the KOH methanol solution of 0.1 ~ 0.4mol/L is dropped to step 1) Zn (CH that obtains 3cOO) 2in precursor solution, Zn (CH 3cOO) 2be 1:1.67 ~ 1:2 with the mol ratio of KOH, water-bath 15 ~ 40 minutes at 70 ~ 90 DEG C;
(3) again to step 2) reaction solution in inject TM (CH 3cOO) 2precursor solution, after temperature is down to 50 ~ 60 DEG C, add and step 2) the KOH methanol solution of 0.1 ~ 0.4mol/L of moderate, 50 ~ 60 DEG C of isothermal reactions 120 ~ 210 minutes, obtain TM doping zinc oxide nanometer crystalline substance precipitation;
(4) the brilliant deposition and purification of TM doping zinc oxide nanometer step (3) obtained; The purge process of TM doping zinc oxide nanometer crystalline substance precipitation is first with frozen water cooling, then washs by methyl alcohol and n-octyl amine;
(5) TM doping zinc oxide nanometer crystalline substance precipitation step (4) obtained fully is dissolved in trichloromethane, obtains the ZnO colloid nanocrystalline solution of TM doping;
(6) the ZnO colloid nanocrystalline solution of the TM doping obtained by trichloromethane dilution step (5) also filters, and is spin-coated on cleaned substrate, the process of 60 ~ 100 DEG C of prebake after annealings, obtains the ferromagnetic polycrystal film of zno-based of TM doping;
The rotating speed of spin coating process is 2000 ~ 4000 revs/min;
The condition of annealing is: anneal 1 ~ 2 hour in Ar atmosphere at 600 ~ 900 DEG C;
(7) H plasma treatment is carried out to the ferromagnetic polycrystal film of zno-based of the TM doping that step (6) obtains; The condition of H plasma treatment is: background air pressure is lower than 5 × 10 -6torr, operating air pressure is 10 ~ 30mTorr, and the power of radio-frequency power supply is 10 ~ 20W, and substrate temperature is room temperature to 150 DEG C, and the treatment time is 10 ~ 50 minutes.
2. the preparation method of the ferromagnetic polycrystal film of transient metal doped zno-based according to claim 1, is characterized in that, the substrate described in step (6) is silicon chip or quartz.
CN201310113963.8A 2013-04-02 2013-04-02 Ferromagnetic polycrystal film of a kind of transient metal doped zno-based and preparation method thereof Expired - Fee Related CN103194798B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310113963.8A CN103194798B (en) 2013-04-02 2013-04-02 Ferromagnetic polycrystal film of a kind of transient metal doped zno-based and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310113963.8A CN103194798B (en) 2013-04-02 2013-04-02 Ferromagnetic polycrystal film of a kind of transient metal doped zno-based and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103194798A CN103194798A (en) 2013-07-10
CN103194798B true CN103194798B (en) 2015-08-26

Family

ID=48717610

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310113963.8A Expired - Fee Related CN103194798B (en) 2013-04-02 2013-04-02 Ferromagnetic polycrystal film of a kind of transient metal doped zno-based and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103194798B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108083322B (en) * 2018-01-29 2020-03-27 首凯汽车零部件（江苏）有限公司 Preparation method of ZnO nanocrystalline solution and film-forming aggregation state regulation method thereof
CN111809158A (en) * 2020-07-22 2020-10-23 延安大学 Transition metal doped ZnO nanowire array, preparation method and application thereof
CN115312610B (en) * 2022-08-11 2023-04-07 哈尔滨工业大学 Doped zinc oxide ferroelectric photovoltaic film with adjustable band gap and high filling factor and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5082749A (en) * 1990-03-15 1992-01-21 E. I. Du Pont De Nemours And Company Platinum or palladium/cobalt multilayer on a zinc oxide or indium oxide layer for magneto-optical recording
WO2004069767A1 (en) * 2003-02-06 2004-08-19 Nm Spintronics Ab Ferromagnetic material
CN1725446A (en) * 2005-06-15 2006-01-25 浙江大学 Zn1-x CoxO rare magnetic semiconductor film and its preparation technology
CN101045991A (en) * 2007-04-30 2007-10-03 四川大学 Transition metal salt dopping process for preparing magnetic nanometic zinc oxide rod array film
CN101086060A (en) * 2007-07-17 2007-12-12 湘潭大学 Method for preparing dilute magnetic semiconductor film based on zinc oxide possessing room temperature ferromagnetism
CN102544123A (en) * 2012-02-20 2012-07-04 江苏大学 Automatic control solar thin-film battery based on copper zinc oxide (Cu-ZnO) thin film

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5082749A (en) * 1990-03-15 1992-01-21 E. I. Du Pont De Nemours And Company Platinum or palladium/cobalt multilayer on a zinc oxide or indium oxide layer for magneto-optical recording
WO2004069767A1 (en) * 2003-02-06 2004-08-19 Nm Spintronics Ab Ferromagnetic material
CN1725446A (en) * 2005-06-15 2006-01-25 浙江大学 Zn1-x CoxO rare magnetic semiconductor film and its preparation technology
CN101045991A (en) * 2007-04-30 2007-10-03 四川大学 Transition metal salt dopping process for preparing magnetic nanometic zinc oxide rod array film
CN101086060A (en) * 2007-07-17 2007-12-12 湘潭大学 Method for preparing dilute magnetic semiconductor film based on zinc oxide possessing room temperature ferromagnetism
CN102544123A (en) * 2012-02-20 2012-07-04 江苏大学 Automatic control solar thin-film battery based on copper zinc oxide (Cu-ZnO) thin film

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
叶志高,等.脉冲激光沉积法(PLD)生长Co掺杂ZnO薄膜及其磁学性能.《发光学报》.2008, *
董清臣.铜掺杂氧化锌薄膜的阻变特性和光致发光研究.《河南大学硕士学位论文》.2011, *

Also Published As

Publication number Publication date
CN103194798A (en) 2013-07-10

Similar Documents

Publication Publication Date Title
KR100825765B1 (en) Method of forming oxide-based nano-structured material
CN105714379A (en) Preparation method for directly growing highly-doped yttrium iron garnet film on silicon
CN103077963B (en) A kind of Ohm contact electrode, its preparation method and comprise the semiconductor element of this Ohm contact electrode
CN103194798B (en) Ferromagnetic polycrystal film of a kind of transient metal doped zno-based and preparation method thereof
CN109411328B (en) Preparation method of gallium oxide film with crystallization temperature reduced by doping iron
CN110854013A (en) Large-area continuous ultrathin two-dimensional Ga2O3Preparation method and application of amorphous film
CN111341839A (en) P-type nitrogen-doped gallium oxide film and preparation method thereof
CN108588693A (en) Method and the application of doped yttrium hafnium oxide ferroelectric thin film are prepared using full-inorganic precursor solution
CN100424233C (en) Prepn process of polycrystalline Zinc oxide film material
CN114141909B (en) Method for growing gallium oxide films with different crystal orientations on sapphire substrate and preparation method of ultraviolet light detector based on film
CN101866860A (en) Preparation method of ZnO thin film field-effect transistor
CN102263166B (en) Method for improving performances of AlGaN-based detector by using nano particles
CN105097452A (en) Method for preparing silicon carbide film with micron, submicron and nanometer multilevel structure
CN109378275A (en) A kind of doping gallium oxide film and preparation method thereof based on MgO substrate
CN110890280B (en) Method for preparing oxide semiconductor Schottky diode by using palladium/palladium oxide double-layer Schottky electrode
TWI698397B (en) Method of purifying silicon carbide powder
CN104176766A (en) Praseodymium-doped zinc oxide nanowire and preparation method thereof
CN101698932B (en) Method for preparing P type cobalt-doped zinc oxide film
CN110804727A (en) Strain thin film heterojunction, preparation method and application
CN114150296B (en) Preparation method of rare earth manganese oxide film for near-room-temperature infrared imaging
CN105154826A (en) Cu-doped-ZnO nano columnar crystal film with room-temperature ferromagnetism and preparing method of Cu-doped-ZnO nano columnar crystal film
CN115312610B (en) Doped zinc oxide ferroelectric photovoltaic film with adjustable band gap and high filling factor and preparation method thereof
Pratheek et al. Ultrathin single-crystalline perovskites: Toward large area wafers
CN113097055B (en) High-quality p-type gallium oxide nano columnar structure film and preparation method thereof
CN113540254B (en) Neodymium-doped zirconia thin film transistor and preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20150826

Termination date: 20200402