CN101328611B - Low field super large magnetoresistance manganese oxide epitaxial film and preparation thereof - Google Patents
Low field super large magnetoresistance manganese oxide epitaxial film and preparation thereof Download PDFInfo
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- CN101328611B CN101328611B CN2008101176157A CN200810117615A CN101328611B CN 101328611 B CN101328611 B CN 101328611B CN 2008101176157 A CN2008101176157 A CN 2008101176157A CN 200810117615 A CN200810117615 A CN 200810117615A CN 101328611 B CN101328611 B CN 101328611B
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Abstract
一种低场超大磁致电阻锰氧化物外延膜，包括La0.67Ca0.33MnO3外延膜和NdGaO3单晶基片，其特征在于：在边长为3-5mm，厚度为0.3-0.5mm的(001)取向NdGaO3单晶基片上是一层厚度为4-70nm的La0.67Ca0.33MnO3外延膜；其制备方法包括以下几个步骤：(1)选用传统固相反应法制备出的La0.67Ca0.33MnO3多晶做靶材；(2)选择单晶基片NdGaO3；(3)利用激光脉冲沉积系统在NdGaO3单晶基片上面生长外延的La0.67Ca0.33MnO3薄膜；(4)将原位制得的La0.67Ca0.33MnO3/NdGaO3置于管式炉中进行退火处理；本发明所述外延膜从低场磁致电阻和温度的敏感性方面，都适合自旋电子器件的实际应用；且本发明所采用的制备方法第一次实现了通过选择NdGaO3单晶基片的方向，来实现对薄膜的剪切应力控制，从而实现了对低场超大磁致电阻锰氧化物薄膜材料物理性能的人工调控。
A low-field ultra-large magnetoresistance manganese oxide epitaxial film, including La 0.67 Ca 0.33 MnO 3 epitaxial film and NdGaO 3 single crystal substrate, is characterized in that: the side length is 3-5mm, the thickness is 0.3-0.5mm On the (001) oriented NdGaO 3 single crystal substrate is a layer of La 0.67 Ca 0.33 MnO 3 epitaxial film with a thickness of 4-70nm; its preparation method includes the following steps: (1) La 0.67 Ca 0.33 MnO 3 polycrystalline as target material; (2) select single crystal substrate NdGaO 3 ; (3) use laser pulse deposition system to grow epitaxial La 0.67 Ca 0.33 MnO 3 film on NdGaO 3 single crystal substrate; ( 4) The La 0.67 Ca 0.33 MnO 3 /NdGaO 3 prepared in situ is placed in a tube furnace for annealing; the epitaxial film of the present invention is suitable for spin in terms of low-field magnetoresistance and temperature sensitivity The practical application of electronic devices; and the preparation method adopted in the present invention realizes for the first time by selecting the direction of the NdGaO3 single crystal substrate to realize the shear stress control of the film, thereby realizing the ultra-large magnetoresistance to the low field Artificial regulation of physical properties of manganese oxide thin film materials.
Description
Technical field
The present invention relates to a kind of low field super large magnetoresistance; Be particularly related to a kind of low field super large magnetoresistance manganese oxide epitaxial film and preparation method thereof.
Background technology
Adulterated perovskite structure Mn oxide is the strong interconnected system of a kind of important electron, has novel electronics-spin transport characteristic.Because they are at Curie temperature T
CNear have significant magnetoresistance effect, this peculiar performance makes them have deep and broad potential using value in the magnetoelectronic devices field.Yet also there are following two shortcomings in manganese oxide epitaxial film in the use of present stage:
On the one hand, this dvimanganese sull only under very high magnetic field, just can demonstrate magnetoresistance effect (magneto-resistor is defined as MR=[ρ (0)-ρ (H) here]/ρ (0), wherein, ρ (0) and ρ (H) are respectively under the null field and the resistivity under the magnetic field condition), such performance can't satisfy the demand of practical devices application at all.For example 1994 described in the document of U.S.'s " Applied Physics wall bulletin " magazine the 65th volume the 2108th page to 2110 pages (APL 65,2108 (1994)), for typical calcium titanium ore manganose oxide La
1-xSr
xMnO
3Epitaxial film, adding under the high-intensity magnetic field of 5 teslas, near Curie temperature, its magnetoresistivity is the highest also has only 60%.Such performance and practical devices demand differ greatly.But this shortcoming is to improve to some extent in the orderly Mn oxide of electric charge in ground state, for example reports Pr in 1997 in the document of the U.S. " physical comment B " magazine the 56th volume the 13666th page to 13668 pages (PRB 56,13666 (1997))
0.65Ba
0.05Ca
0.3Mn
3-δEpitaxial film, under the externally-applied magnetic field of 0.5 tesla, its magnetoresistivity is the highest can to reach 99%.But the ground state of this oxide epitaxial film is the electric charge ordered phase, and as mentioned below, and its magnetoresistance effect has very strong dependency to temperature.
On the other hand, the magnetoresistance effect in this class Mn oxide shows very strong temperature sensitivity; Just may show bigger magnetoresistance effect in extremely limited temperature range, along with temperature raises or reduces, this magnetoresistance effect can reduce rapidly up to being zero.For example, for the Mn oxide La of the above-mentioned ferromagnetic ground state of standard
1-xSr
xMnO
3Film, its magnetoresistance only is higher than 50% in the about 200K-250K scope far below his Curie temperature.And to above-mentioned Pr
0.65Ba
0.05Ca
0.3Mn
3-δFilm, though his magnetoresistance maximum can reach 99%, when temperature rises to 150K when above, magnetoresistivity can reduce rapidly, until disappearance.The magnetoresistance effect of this class film is another key factor of its practical application of restriction to the susceptibility of temperature.
Therefore, improving low magnetoresistance of huge magnetic impedance Mn oxide film itself and reducing its susceptibility to temperature is two the most key problems that the scientific research technician faces, and the final purpose that addresses this problem is exactly to obtain to hang down enough big after the match magnetoresistance and temperature stability thereof Mn oxide film preferably.Therefore, the way of seeking these two problems of new solution is that the application of the magnetic electron device of base has extremely important realistic meaning for realizing with adulterated calcium titanium ore manganose oxide.
Summary of the invention
The technical problem to be solved in the present invention is: for overcoming the deficiencies in the prior art; Improve low magnetoresistance of ferromagnetic ground state manganese oxide epitaxial film and reduce its susceptibility, the invention provides a kind of low field super large magnetoresistance manganese oxide epitaxial film and preparation method thereof temperature.
The technical solution adopted for the present invention to solve the technical problems is: a kind of low field super large magnetoresistance manganese oxide epitaxial film comprises La
0.67Ca
0.33MnO
3Epitaxial film and NdGaO
3Monocrystal chip is characterized in that: in the length of side is 3-5mm, and thickness is the NdGaO of 0.3-0.5mm
3Be that a layer thickness is the La of 4-70nm on (001) orientation of monocrystal chip
0.67Ca
0.33MnO
3Epitaxial film.
The preparation method of aforesaid a kind of low field super large magnetoresistance manganese oxide epitaxial film is characterized in that:
(1) La that selects for use traditional solid reaction process to prepare
0.67Ca
0.33MnO
3Polycrystalline is done target;
(2) select monocrystal chip NdGaO
3
(3) utilize the pulsed laser deposition system at NdGaO
3The La of growing epitaxial above the monocrystal chip
0.67Ca
0.33MnO
3Film;
(4) La that original position is made
0.67Ca
0.33MnO
3/ NdGaO
3Heterogeneous membrane places tube furnace to carry out anneal.
The selected monocrystal chip NdGaO of described step (2)
3And the La of step (1) preparation
0.67Ca
0.33MnO
3No length mismatch but have than the wide-angle mismatch.
La in the described step (3)
0.67Ca
0.33MnO
3Film is at NdGaO
3Aufwuchsplate above the monocrystal chip is got (001) direction.
The energy region of the selected laser of pulsed laser deposition in the described step (3) is 170-210mJ.
The selected deposition atmosphere of pulsed laser deposition in the described step (3) is an oxygen.
The selected deposition pressure of pulsed laser deposition in the described step (3) is 10-60Pa.
The selected depositing temperature of pulsed laser deposition in the described step (3) is 680-750 ℃.
Selected annealing temperature is 650-850 ℃ in the described step (4), and the time length is 180-300 minute.
Be filled with mobile oxygen in the tube furnace in the described step (4).
The advantage that the present invention is compared with prior art had: comparing in the magnetoresistance effect in this low the magnetoresistance film of the present invention and the traditional Mn oxide film, no matter be size from a low magnetoresistance, still the susceptibility aspect of temperature all is more suitable for the practical application in spin electric device; Preparation method of the present invention has realized for the first time by selecting NdGaO
3The direction of monocrystal chip realizes the shear-stress control to film, thereby has realized the artificial regulatory to low field super large magnetoresistance manganese oxide thin-film material physicals.
Description of drawings
Fig. 1 La
0.67Ca
0.33MnO
33/ NdGaO
3The structural representation of heteroepitaxial film;
Fig. 2 La
0.67Ca
0.33MnO
33/ NdGaO
3Fall space pattern;
Fig. 3 different thickness La
0.67Ca
0.33MnO
3/ NdGaO
3The resistance temperature curve of film under different magnetic field;
Fig. 4 different thickness La
0.67Ca
0.33MnO
3/ NdGaO
3The magnetoresistance temperature curve of film under different magnetic field.
Embodiment
Introduce the present invention in detail below in conjunction with the drawings and the specific embodiments; But following embodiment only limits to explain the present invention, and protection scope of the present invention should comprise the full content of claim, and promptly can realize the full content of claim of the present invention by following examples those skilled in the art.
A kind of low field super large magnetoresistance manganese oxide epitaxial film of present embodiment comprises La
0.67Ca
0.33MnO
3 Epitaxial film 1 and NdGaO
3 Monocrystal chip 2 is 4mm in the length of side, and thickness is the NdGaO of 0.4mm
3On the face of (001) orientation of monocrystal chip 2 is that a layer thickness is the La of 12nm
0.67Ca
0.33MnO
3 Epitaxial film 1, as shown in Figure 1.
Below by the NdGaO of pulsed laser deposition method in orthohormbic structure
3(001) lanthanum manganate (La that mixes calcium of growth optimum doping on the single crystalline substrate
0.67Ca
0.33MnO
3) the oxide monocrystal film.
At first, prepare La by the standard solid-phase sintering process
0.67Ca
0.33MnO
3Target material; CaO (purity 〉=98.0%), La
2O
3(purity 〉=99.99%), MnO
2(purity 〉=99.5%) powder is according to La
0.67Ca
0.33MnO
3Chemical formula carries out proportioning, then in the high temperature muffle furnace, respectively at 1100 ℃, 1250 ℃, repeats fully to grind calcining in the air atmosphere, at last the round target that depresses at 40MPa pressure at 1350 ℃, thereby sinter molding obtains La in the air atmosphere
0.67Ca
0.33MnO
3The polycrystalline ceramics target material.
Then, by pulsed laser deposition (PLD) system at NdGaO
3La grows on (001) direction of monocrystal chip
0.67Ca
0.33MnO
3Monocrystal epitaxial film; Monocrystal chip NdGaO wherein
3And La
0.67Ca
0.33MnO
3No length mismatch but have than the wide-angle mismatch; Used laser apparatus is star (thin-film star) the KrF laser apparatus of the film of Tuilaser company production, and optical maser wavelength is 248nm, and the laser energy density of beating on the target that rotates is 3J/cm
2, laser frequency is selected 5Hz for use, controls film thickness by the control depositing time; Selected growth La
0.67Ca
0.33MnO
3The growth conditions of single crystal film is: deposition oxygen is pressed 45Pa, 735 ℃ of growth temperatures.After thin film deposition finishes, make film in position preparation temperature, preparation oxygen depress annealing 15 minutes, depress at 1000Pa oxygen subsequently and slowly be cooled to room temperature;
At last, the La that original position is made
0.67Ca
0.33MnO
3/ NdGaO
3(001) heterogeneous membrane places tube furnace to carry out anneal at mobile oxygen, 750 ℃ of annealing temperatures, and 240 minutes time length, annealing makes the tube furnace temperature slowly reduce to room temperature after finishing.
By said process, utilize impulse laser deposition system at NdGaO
3(001) ground state that has made the optimum doping proportioning on the substrate is the La of ferromagnetic metal state
0.67Ca
0.33MnO
3Film.High resolution X-ray structure analysis per sample, as shown in Figure 2; La can be described under preparation of selecting and annealing conditions
0.67Ca
0.33MnO
3Film (has omitted the following thickness sample of 20nm reciprocal space figure) at NdGaO from 60nm to 8nm
3Has good epitaxial structure along (001) direction on the substrate.Different thickness La by the inventive method gained
0.67Ca
0.33MnO
3/ NdGaO
3(001) resistance temperature curve of film under different magnetic field as shown in Figure 3, is respectively 8nm, 12nm, 16nm with thickness here, the La of 20nm, 24nm
0.67Ca
0.33MnO
3/ NdGaO
3(001) film is an example, according to the measuring result of electronic transport, from different thickness La
0.67Ca
0.33MnO
3The resistivity of film can see that in the sample of thickness bigger (for example 24nm), from high temperature to low temperature, sheet resistance presents good semiconductor alloy and changes behavior; Along with thickness reduces, La
0.67Ca
0.33MnO
3Near the resistivity of film 140K increases gradually, and presenting electric charge near this temperature has sequence characteristics, and thickness thin more (as 12nm and 8nm), and this specific character is obvious more.Different thickness La by the inventive method gained
0.67Ca
0.33MnO
3/ NdGaO
3(001) the magnetoresistance temperature curve of film under different magnetic field as shown in Figure 4, is respectively 8nm, 12nm, 16nm with thickness here, the La of 20nm, 24nm
0.67Ca
0.33MnO
3/ NdGaO
3(001) film is an example, transports behavior measure according to magnetic and shows, La
0.67Ca
0.33MnO
3/ NdGaO
3(001) this electric charge ordered pair externally-applied magnetic field in the film is very responsive, and under very little externally-applied magnetic field 0.2T effect, it is very high that the magnetoresistance of film just can reach, for example, for the film of 12nm, when externally-applied magnetic field was 0.2T, the magnetoresistance of film just can reach more than 99%; Simultaneously, this magnetoresistance has excellent temperature stability, for example, to the 16nm film, under the situation that adds 0.2T magnetic field, in the 50K-210K temperature range, magnetic resistance can stably be in more than 70%, and for the film of 12nm and 8nm, such temperature-stable scope also can be wideer.
In sum, at NdGaO
3The ground state that single crystalline substrate upper edge (001) direction epitaxy goes out the optimum chemical proportioning is the La of ferromagnetic metal state
0.67Ca
0.33MnO
3Single crystal film, by structural analysis, resistance and magnetic transport property energy measurement as can be seen, La
0.67Ca
0.33MnO
3/ NdGaO
3(001) film has good epitaxial structure, and in the certain thickness scope (less than 20nm), along with temperature reduces, the sheet resistance behavior carries out the transition to metallic state gradually from the semiconducting insulation attitude earlier, and then carries out the transition to the orderly high-impedance state of electric charge.Magnetic transport property energy measurement shows that the orderly high-impedance state of this electric charge is very easy to by externally-applied magnetic field " thawing ", thereby obtains very large low magnetoresistance.Because at NdGaO
3(001) La for preparing on the substrate
0.67Ca
0.33MnO
3Film just has very high (greater than 97%) magnetoresistance effect under the externally-applied magnetic field of 0.2T, and has excellent temperature stability, so it is well suited for being applied in the research and new functional oxide thin-film device of some spin electric devices.
Claims (5)
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| CN101775644B (en) * | 2010-02-10 | 2012-10-03 | 中国科学技术大学 | Manganese oxide epitaxial film with anisotropic magnetoresistivity and preparation method and application thereof |
| CN103834992A (en) * | 2014-03-04 | 2014-06-04 | 中国科学技术大学 | A kind of CaRuO3/La2/3Ca1/3MnO3/CaRuO3 sandwich structure epitaxial film and its preparation method and application |
| CN105172255B (en) * | 2015-07-17 | 2017-04-12 | 中国科学技术大学 | Magnetic multilayer film with antiferromagnetc interlayer coupling, and production method thereof |
| CN110212084B (en) * | 2019-05-24 | 2020-09-08 | 北京大学 | A method for measuring the layered magnetic structure of weakly magnetic La1-xSrxMnO3 epitaxial thin films |
Citations (5)
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| US5792569A (en) * | 1996-03-19 | 1998-08-11 | International Business Machines Corporation | Magnetic devices and sensors based on perovskite manganese oxide materials |
| US6128178A (en) * | 1998-07-20 | 2000-10-03 | International Business Machines Corporation | Very thin film capacitor for dynamic random access memory (DRAM) |
| CN2574226Y (en) * | 2002-09-27 | 2003-09-17 | 中国科学院物理研究所 | Doped strontium titanate and doped La-Mn-O huge magnetoresistance device |
| CN1485934A (en) * | 2002-09-27 | 2004-03-31 | �й���ѧԺ�����о��� | Doped barium titanate giant magnetoresistance device and preparation method |
| CN1722390A (en) * | 2004-07-13 | 2006-01-18 | 中国科学院物理研究所 | Epitaxial growth iron-based alloy thin films and heterojunction materials and preparation method on silicon chip |
-
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Patent Citations (5)
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|---|---|---|---|---|
| US5792569A (en) * | 1996-03-19 | 1998-08-11 | International Business Machines Corporation | Magnetic devices and sensors based on perovskite manganese oxide materials |
| US6128178A (en) * | 1998-07-20 | 2000-10-03 | International Business Machines Corporation | Very thin film capacitor for dynamic random access memory (DRAM) |
| CN2574226Y (en) * | 2002-09-27 | 2003-09-17 | 中国科学院物理研究所 | Doped strontium titanate and doped La-Mn-O huge magnetoresistance device |
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Non-Patent Citations (2)
| Title |
|---|
| Zhao Kun等.Thickness Effect on Electronic Transport in Single Crystal La0.67Ca0.33MnO3 Thin Films.《Journal of Rare Earths》.2005,第23卷(第6期),721-723. * |
| 曾宪庭等.用对向靶溅射法外延生长La-Ca-Mn-O巨磁阻单晶薄膜.《中国科学A辑》.1996,第26卷(第1期),55-59. * |
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