CN1908250A - Method of preparing room temperature ferromagnetism Zn(1-X)Mn(X)O diluted magnetic semiconductor nano-line - Google Patents
Method of preparing room temperature ferromagnetism Zn(1-X)Mn(X)O diluted magnetic semiconductor nano-line Download PDFInfo
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- CN1908250A CN1908250A CN 200610088915 CN200610088915A CN1908250A CN 1908250 A CN1908250 A CN 1908250A CN 200610088915 CN200610088915 CN 200610088915 CN 200610088915 A CN200610088915 A CN 200610088915A CN 1908250 A CN1908250 A CN 1908250A
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Abstract
the invention discloses a preparing method of indoor-temperature magnetic Zn1-xMnxO nanometer line in the rare-magnetic semiconductor nanometer material preparing domain, which comprises the following steps: cleaning silicate through HCl and acetone; adopting Zn powder and MnCl2 powder and evaporating source in the adjacent quartz ship; making silicate as receiving substrate at intersecting part of two evaporating source vertically; setting the vertical distance between silicate and evaporating source at 6-8 mm; placing quartz ship in the pipe-typed furnace; aerating gas in the system inlet; conducting gas in the water through rubber conduct; aerating argon gas at 300-400ml/min for 5-8 min; changing the flow of argon gas at 30-50 ml/min; heating the pipe-typed furnace at 800-830 deg.c; maintaining the system pressure at atmospheric condition; keeping temperature for 120-150 min; cooling to indoor temperature naturally to obtain the even-distributing Zn1-xMnxO nanometer line.
Description
Technical field
The invention belongs to the rare magnetic semiconductor nano material preparation field, particularly provide a kind of vapour deposition to prepare room-temperature ferromagnetic Zn
1-xMn
xThe method of O diluted magnetic semiconductor nano-line.
Background technology
Electronics in the solid is the carrier of electric charge, is again carrier and spin.Spin-electronic material provides and has utilized the electric charge of electronics and the possibility of spin characters simultaneously, utilizes spin-electronic material will realize the significantly lifting of memory data output and processing speed so.(Diluted Magnetic Semiconductor DMS) introduces magnetic ion semiconductor material to dilute magnetic semiconductor, has successfully realized the combination of magneticsubstance and semiconductor material, is one of ideal material of preparation spin electric device.But can DMS at room temperature still keep ferromegnetism is to determine whether it has the key factor of practicality.The basic DMS of broad stopband oxide semiconductor zinc oxide (ZnO) is expected to become the elite clone of modern optoelectronic devices demand for development.ZnO has from blue light to the good optical property of UV-light wave band, and the theoretical doping content that dopes Mn among the p type ZnO again reaches at 5% o'clock and can have the Curie temperature that is higher than room temperature, makes the research of zno-based DMS start unprecedented climax.But, obtain the Zn of high quality room-temperature ferromagnetic at present
1-xMn
xThe O nanostructure is still relatively more difficult technically.People such as Zheng have realized the magnetic-doped of ZnO nanostructure under Mn heat of steam treatment condition, but phase [R.K.Zheng, H.Liu, X.X.Zhang, V.A.L.Roy, A.B. have occurred being mingled with on the surface
Exchange bias and the origin of magnetism inMn-doped ZnO tetrapods, Appl.Phys.Lett., 85 (2004) 2589～2591]; People such as Liu adopt CVD (Chemical Vapor Deposition) method to prepare Zn
1-xMn
xThe O nano-array, but the doping content of Mn is on the low side, 1.7%[J.J.Liu only has an appointment, M.H.Yu, W.L.Zhou, Well-aligned Mn-doped ZnO nanowires synthesized by a chemicalvapor deposition method, Appl.Phys.Lett., 87 (2005) 172505-1～3].People such as Philipose prepare the Zn of room-temperature ferromagnetic
1-xMn
xThe O nano wire, but their preparation method has introduced golden impurity element, and the surface imperfection attitude is than higher [U.Philipose, Selvakumar V.Nair, Simon Trudel, C.F.de Souza, S.Aouba, Ross H.Hill, Harry E.Ruda, High-temperature ferromagnetism in Mn-doped ZnOnanowires, Appl.Phys.Lett.88 (2006) 263101～3].Thereby be necessary to seek a kind of suitable method and obtain highly purified Zn
1-xMn
xO nano wire, and nano wire has room-temperature ferromagnetic, thus material foundation provided for the practicability of spin electric device.
Summary of the invention
The object of the present invention is to provide a kind of room-temperature ferromagnetic Zn
1-xMn
xThe preparation method of O diluted magnetic semiconductor nano-line.Solved the problem of in semi-conductor ZnO nano wire, rationally mixing magnetic element Mn.The Zn of preparation
1-xMn
xThe O nano wire has very strong ferromegnetism, and Curie temperature is higher than room temperature.
The present invention adopts the high and labile MnCl of vapour pressure
2Powder is as the source of magnetic element Mn, carries out in-situ dopedly in ZnO nano wire preparation process, and the Mn back of mixing forms sosoloid in the mode of displacement Zn position, and the Zn that obtains
1-xMn
xThe O nano wire has room-temperature ferromagnetic.
Zn of the present invention
1-xMn
xThe O nano wire adopts the method preparation of vapour deposition, and the product of acquisition is Zn
1-xMn
xO single phase solid solution material.Concrete preparation technology is as follows:
1, silicon chip is adopted hydrochloric acid clean the back and rinse well, and then clean, rinse well with deionized water at last with acetone with deionized water.
2, with Zn powder and MnCl
2Powder is placed next to each other in the quartz boat as evaporation source, and silicon chip vertically is placed on the intersection of two kinds of evaporation sources as receiving substrate, and the vertical range of silicon chip and evaporation source is 6～8mm.
3, quartz boat is put into tube furnace, the system entry place can feed gas, and gas imports in the water with rubber hose in the exit.System feeds the argon gas of 300～400 ml/min, behind 5～8min argon flow amount is changed into 30～50 ml/min.Tube furnace is heated to 800～830 ℃, and system pressure maintains atmospheric pressure state, naturally cools to room temperature behind insulation 120～150min, can obtain the Zn that big area is evenly distributed
1-xMn
xThe O nano wire.
The span of Mn content of the present invention is 1.5～23 atom %.Zn
1-xMn
xThe diameter of O nano wire is 30～150nm, and length is 5～22 μ m.
Advantage of the present invention:
Adopt the method for vapour deposition to realize the in-situ doped of magnetic element Mn in the ZnO nano wire, its doping content is controlled.And do not produce in the back parent that mixes and be mingled with phase, can realize large-area preparation.
The doping content of magnetic element can be controlled by adjusting synthesis temperature, constituent element stoicheiometry and carrier gas flux, and can regulate and control the magnetic and the Curie temperature of nano wire by the doping content of adjusting magnetic element Mn.The diameter of nano wire also can be controlled effectively by adjusting synthesis temperature and gas flow.
Preparation temperature of the present invention is low; The equipment that the preparation method requires simple (tube furnace), the raw material cheapness, simple for process, cost is very low, and reaction conditions is controlled, environmentally safe; The product purity height, output is big.
Zn
1-xMn
xThe one-dimension transport and the magneto-optical property of O nano wire uniqueness make it have important effect in the nanometer spin electric device in future.
The Zn that obtains
1-xMn
xThe O nano wire is a monocrystalline, and crystalline quality is very high, and has room-temperature ferromagnetic.The present invention has the potential commercial application prospect in spin fet, spinning LED, spin resonance tunnelling device, spin-filter isospin electron device.
Description of drawings
Fig. 1 Zn
1-xMn
xThe XRD spectrum of O nano wire.
Fig. 2 Zn
1-xMn
xThe stereoscan photograph of O nano wire shows that product is made up of nano wire.
Fig. 3 Zn
1-xMn
xThe high-resolution-ration transmission electric-lens photo of O nano wire, lattice image is very clear, shows that nano wire is a monocrystalline, does not observe the impurity phase.
Zn under Fig. 4 room temperature condition
1-xMn
xThe M-H curve of O shows that product at room temperature has ferromegnetism.
Embodiment
Embodiment 1
Adopt hydrochloric acid to clean the back silicon chip and rinse well, and then clean, rinse well with deionized water at last with acetone with deionized water.With Zn powder and MnCl
2Powder is placed next to each other in the middle part of quartz boat, and silicon chip covers the intersection of two kinds of evaporation sources, with the vertical range of evaporation source be 7mm.Quartz boat is put into tube furnace, and the system entry place can feed gas, and gas imports in the water with rubber hose in the exit.System feeds the argon gas of 300 ml/min, behind the 8min argon flow amount is changed into 30 ml/min.Tube furnace is heated to 810 ℃, and system pressure maintains atmospheric pressure state, naturally cools to room temperature behind the insulation 120min, can obtain Zn
1-xMn
xO (x=10%) nano wire.The diameter of nano wire is 30～100nm, and length is 7～18 μ m.
Adopt the structure of X-ray diffractometer assay products, its diffracting spectrum shows that product is the ZnO Wurzite structure as shown in Figure 1.Do not observe the diffraction peak of other impurity such as Mn or its oxide compound, show that magnetic element Mn solid solution goes in the ZnO crystalline network, do not form second phase.Adopt the surface topography of scanning electron microscopic observation product, the result as shown in Figure 2, silicon chip surface has covered one deck nano wire, illustrates that this preparation method can obtain the equally distributed product of big area.Adopt high-resolution transmission electron microscope further the microstructure of product to be analyzed, the discovery nano wire is a monocrystalline, crystalline quality very high (Fig. 3).Magnetic Measurement shows that nano wire has room-temperature ferromagnetic, and its Curie temperature is higher than room temperature.Accompanying drawing 4 is Zn
1-xMn
xO (x=10%) M-H curve at room temperature, it shows that sample at room temperature still has tangible magnetic hysteresis loop, and coercive force reaches 153Oe, and interpret sample at room temperature still is a ferrimagnetic state.
Embodiment 2
Adopt hydrochloric acid to clean the back silicon chip and rinse well, and then clean, rinse well with deionized water at last with acetone with deionized water.With Zn powder and MnCl
2Powder is placed next to each other in the middle part of quartz boat, and silicon chip covers the intersection of two kinds of evaporation sources, with the vertical range of evaporation source be 7mm.Quartz boat is put into tube furnace, and the system entry place can feed gas, and gas imports in the water with rubber hose in the exit.System feeds the argon gas of 400 ml/min, behind the 5min argon flow amount is changed into 50 ml/min.Tube furnace is heated to 830 ℃, and system pressure maintains atmospheric pressure state, naturally cools to room temperature behind the insulation 150min, can obtain Zn
1-xMn
xO (x=20%) nano wire.The diameter of nano wire is 60～150nm, and length is 10～22 μ m.
Embodiment 3
Adopt hydrochloric acid to clean the back silicon chip and rinse well, and then clean, rinse well with deionized water at last with acetone with deionized water.With Zn powder and MnCl
2Powder is placed next to each other in the middle part of quartz boat, and silicon chip covers the intersection of two kinds of evaporation sources, with the vertical range of evaporation source be 8mm.Quartz boat is put into tube furnace, and the system entry place can feed gas, and gas imports in the water with rubber hose in the exit.System feeds the argon gas of 340 ml/min, behind the 7min argon flow amount is changed into 40 ml/min.Tube furnace is heated to 805 ℃, and system pressure maintains atmospheric pressure state, naturally cools to room temperature behind the insulation 140min, can obtain Zn
1-xMn
xO (x=3.5%) nano wire.The diameter of nano wire is 30～80nm, and length is 5～14 μ m.
Claims (1)
1, a kind of preparation room-temperature ferromagnetic Zn
1-xMn
xThe method of O nano wire is characterized in that: technology is:
A, adopt hydrochloric acid to clean the back silicon chip to rinse well, and then clean, rinse well with deionized water at last with acetone with deionized water;
B, with Zn powder and MnCl
2Powder is placed next to each other in the quartz boat as evaporation source, and silicon chip vertically is placed on the intersection of two kinds of evaporation sources as receiving substrate, and the vertical range of silicon chip and evaporation source is 6～8mm;
C, quartz boat is put into tube furnace, the system entry place feeds gas, and gas imports in the water with rubber hose in the exit; System feeds the argon gas of 300～400 ml/min, behind 5～8min argon flow amount is changed into 30～50 ml/min; Tube furnace is heated to 800～830 ℃, and system pressure maintains atmospheric pressure state, naturally cools to room temperature behind insulation 120～150min, obtains the Zn that big area is evenly distributed
1-xMn
xThe O nano wire; The span of Mn content is 1.5～23 atom %, Zn
1-xMn
xThe diameter of O nano wire is 30～150nm, and length is 5～22 μ m.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559920B (en) * | 2009-05-21 | 2011-04-27 | 东华大学 | One-step method for preparing butterfly pattern ZnSe/GeSe grade heterojunction nano-wire |
| CN102719249A (en) * | 2012-04-04 | 2012-10-10 | 河北联合大学 | Synthetic method of luminous ion doped zinc oxide microtube material |
| CN115148445A (en) * | 2022-06-30 | 2022-10-04 | 成都海威华芯科技有限公司 | Iodine-containing diluted magnetic semiconductor (Zn) 90% ,Cr 10% ) Te: N thin film material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002093140A1 (en) * | 2001-05-14 | 2002-11-21 | Johns Hopkins University | Multifunctional magnetic nanowires |
| CN1239395C (en) * | 2002-01-22 | 2006-02-01 | 大连三科科技发展有限公司 | Process for preparing nano zinc oxide material |
| KR100499274B1 (en) * | 2002-02-06 | 2005-07-01 | 학교법인 포항공과대학교 | Manufacturing method for ZnO based hetero-structure nanowires |
| KR100458162B1 (en) * | 2002-03-02 | 2004-11-26 | 학교법인 포항공과대학교 | ZnO based quantum well and/or superlattice nanowires |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559920B (en) * | 2009-05-21 | 2011-04-27 | 东华大学 | One-step method for preparing butterfly pattern ZnSe/GeSe grade heterojunction nano-wire |
| CN102719249A (en) * | 2012-04-04 | 2012-10-10 | 河北联合大学 | Synthetic method of luminous ion doped zinc oxide microtube material |
| CN102719249B (en) * | 2012-04-04 | 2014-02-12 | 河北联合大学 | Synthetic method of luminous ion doped zinc oxide microtube material |
| CN115148445A (en) * | 2022-06-30 | 2022-10-04 | 成都海威华芯科技有限公司 | Iodine-containing diluted magnetic semiconductor (Zn) 90% ,Cr 10% ) Te: N thin film material and preparation method thereof |
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