CN101354945A - Magnetic composite organic nanometer granule film with magnetoresistance effect and preparation method thereof - Google Patents
Magnetic composite organic nanometer granule film with magnetoresistance effect and preparation method thereof Download PDFInfo
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- CN101354945A CN101354945A CNA2008100377479A CN200810037747A CN101354945A CN 101354945 A CN101354945 A CN 101354945A CN A2008100377479 A CNA2008100377479 A CN A2008100377479A CN 200810037747 A CN200810037747 A CN 200810037747A CN 101354945 A CN101354945 A CN 101354945A
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Abstract
The invention belongs to the technical field of a magnetic film material, in particular to a magnetic composite organic nanometer granular film with giant magnetic resistance effect and a method for preparing the same. The film material is prepared and obtained from a magnetic metal material and an organic semiconductor material by a co-evaporation method; the nanometer granules of the magnetic metal material are evenly embedded in an organic semiconductor substrate and expressed as: (A)x(B)1-x, x is more than 0.28 and less than 0.56, wherein A is the magnetic metal material; and B is the organic semiconductor material. The film material can be widely used for a magnetic sensor, a magnetic memory, a temperature sensor and other element devices.
Description
Technical field
The invention belongs to the magnetic thin film technical field, be specifically related to compound membrana granulosa of a kind of metal and organic semiconductor and preparation method thereof.
Background technology
Giant magnetoresistance effect has obtained extensive use in Magnetic Sensor and magnetic storage field.But the at present most widely used magnetic multilayer film structure (Spin Valve) and the membrana granulosa structure that also are based on inorganic body system.Utilize the function element of the structure preparation of this inorganic system, although bigger giant magnetoresistance effect is arranged, its preparation technology's more complicated, cost is relatively also higher.
Simultaneously, because organic material has unique superiority comparing inorganic material aspect physics, chemical characteristic and the preparation technology, begun to be paid close attention to widely in academia at present.We prepare and have studied a series of magnetic metals and the compound nano-particular film of organic semiconductor based on above-mentioned consideration, and concurrent also have giant magnetoresistance effect in this kind material now, can be applicable to association area.
Summary of the invention
The object of the present invention is to provide a kind of new material system that possesses giant magnetoresistance effect---magnetic composite organic nanometer granule film, and the method for this film of preparation is provided.
Magnetic composite organic nanometer granule film provided by the invention, be to prepare by magnetic metal material (FM) and organic semiconducting materials (OSC) method by coevaporation, be designated as FM/OSC, be embedded in the organic semiconductor substrate by magnetic metal material nano uniform particles and form, be expressed as (A)
x(B)
1-x, x represents the quality share parameter of material, 0.28＜x＜0.56, and wherein A is the magnetic metal material, B is an organic semiconducting materials.
Magnetic metal material (FM) can select Fe, and Co or Ni etc. perhaps select for use alloy as FeNi or FeCo etc.
Organic semiconducting materials (OSC) can select to be fit to the small molecule material of the method preparation of evaporation as:
Three (oxine) aluminium (Alq
3), N, N '-diphenyl-N, N '-two (3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines (TPD), N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4,4 '-diamines (NPB) etc.
Composite nanometer film of the present invention has following characteristic:
(1), analyzes it and be the magnetic nanoparticle membrane structure by micro-structural and magnetic test;
(2) along with the reduction of temperature, the corresponding increase of resistivity;
(3) have negative giant magnetoresistance effect, and strengthen along with temperature reduces magneto-resistance effect;
(4) magneto-resistance effect and magnetic metal content tight association can regulate and control its size by changing content, and under the situation of a certain suitable metal score, peak value appear in the magneto-resistance effect meeting.
The preparation method of the magnetic composite organic nanometer granule film that the present invention proposes is as follows:
Adopt the technology of vacuum thermal evaporation plated film, vacuum degree about 1 * 10
-3Pa--1 * 10
-4Pa.With magnetic metal material and organic semiconducting materials codeposition on the dielectric substrate that cleans up as: glass forms the magnetic organic semiconductor membrana granulosa of 20-1000nm thickness.Volume ratio by two kinds of compositions in the evaporation rate may command film of regulating two kinds of materials.Wherein, the evaporation speed of generally controlling the magnetic metal material is
Between, control organic semi-conductor evaporation speed is
Between.
The invention provides new magnetic functional material---magnetic composite organic nanometer granule film, this material has giant magnetoresistance effect, and its resistivity increases along with temperature reduces sharply, and the method for preparing this film is provided.Method by coevaporation on substrate, forms the membrana granulosa structure with magnetic metal and organic semiconductor evaporation.The Magnetic Sensor and the magnetic storage components and parts that utilize this kind thin-film material to make, its technology is greatly simplified with respect to the material of inorganic system, and cost reduces, and can be used for Magnetic Sensor and magnetic storage components and parts or temperature sensor, has broad application prospects.
Description of drawings
Fig. 1: Co
044(Alq
3)
0.56The magneto-resistance effect of membrana granulosa.
The Co of Fig. 2: x=0.44
x(Alq
3)
1-xThe resistance of sample and temperature relation figure.
The Co of Fig. 3: x=0.44
x(Alq
3)
1-xThe HRTEM figure of membrana granulosa sample.
Embodiment
Further specify technology of preparing scheme of the present invention below by embodiment, so that understand content of the present invention better.
Co/Alq
3The preparation of nano-particular film:
A, the substrate that is used to deposit adopt slide, dry after cleaning, and insert in the vacuum chamber.
B, with mechanical pump and molecular pump vacuum chamber is evacuated to high vacuum, about 5 * 10
-4Pa.
C, the configuration of vacuum chamber bottom two evaporation sources---organic semiconductor source and magnetic metal material source.By regulation and control to heating voltage and temperature, and the real-time monitoring of film thickness gauge, be controlled to membrane process.The evaporation rate of magnetic metal is controlled at
Between, the rate controlled of organic material exists
Between, and control film composition by its relative speed.
D, utilize physical characteristic test macro (PPMS) this sample to be carried out the test of magneto-resistor, find that magnetic composite organic nanometer granule film is along with the increase of x (metal volume score) at low temperatures, magneto-resistance effect increases afterwards earlier and reduces, apparent in view giant magnetoresistance effect is arranged in the sample of x=0.3-0.5, simultaneously, in the x=0.44 sample, reach maximum,-5.3% (T=30K) sees Fig. 1.
E, along with the rising magneto-resistance effect of temperature reduces gradually, 0.3% magneto-resistance effect is at room temperature arranged approximately.In addition, along with the reduction of temperature, its resistivity sharply increases, as Fig. 2.
F, utilize the high resolution electron microscope of Jeol JEM-2010 that sample is observed, find exemplary particles film feature, as Fig. 3.
G, utilize its magnetoresistance characteristics, can be used for Magnetic Sensor and magnetic storage components and parts.Utilize the temperature characterisitic of its resistance, can be used for temperature sensor.
The preparation of Co/TPD nano-particular film:
A, the substrate that is used to deposit adopt slide, dry after cleaning, and insert in the vacuum chamber.
B, with mechanical pump and molecular pump vacuum chamber is evacuated to high vacuum, about 5 * 10
-4Pa.
C, the configuration of vacuum chamber bottom two evaporation sources---organic source and source metal.By regulation and control to heating voltage and temperature, and the real-time monitoring of film thickness gauge, be controlled to membrane process.The evaporation rate of magnetic metal is controlled at
Between, the rate controlled of organic material exists
Between, and control film composition by its relative speed.
D, utilize physical characteristic test macro (PPMS) that this sample is carried out the test of magneto-resistor, giant magnetoresistance effect reaches-1.1% (T=4.2K) in the sample of x=0.28.
E, along with the rising magneto-resistance effect of temperature reduces gradually, in addition, along with the reduction of temperature, its resistivity sharply increases.
This film can be used for Magnetic Sensor and magnetic storage components and parts equally.
Embodiment 3
Fe/Alq
3The preparation of nano-particular film:
A, the substrate that is used to deposit adopt slide, dry after cleaning, and insert in the vacuum chamber.
B, with mechanical pump and molecular pump vacuum chamber is evacuated to high vacuum, about 5 * 10
-4Pa.
C, the configuration of vacuum chamber bottom two evaporation sources---organic source and source metal.By regulation and control to heating voltage and temperature, and the real-time monitoring of film thickness gauge, be controlled to membrane process.The evaporation rate of magnetic metal is controlled at
Between, the rate controlled of organic material exists
Between, and control film composition by its relative speed.
D, utilize physical characteristic test macro (PPMS) that this sample is carried out the test of magneto-resistor, giant magnetoresistance effect reaches-0.13% (T=30K) in the sample of x=0.56.
E, along with the rising magneto-resistance effect of temperature reduces gradually, in addition, along with the reduction of temperature, its resistivity sharply increases.
This film can be used for Magnetic Sensor and magnetic storage components and parts equally.
Claims (3)
1, a kind of magnetic composite organic nanometer granule film with magneto-resistance effect, it is characterized in that it being to prepare by magnetic metal material and organic semiconducting materials method by coevaporation, be embedded in the organic semiconductor substrate by magnetic metal material nano uniform particles, be expressed as (A)
x(B)
1-x, 0.28＜x＜0.56, wherein A is the magnetic metal material, B is an organic semiconducting materials.
2, the magnetic composite organic nanometer granule film with magneto-resistance effect according to claim 1 is characterized in that described magnetic metal material is selected from Fe, Co or Ni, perhaps is selected from alloy FeNi or FeCo; Organic semiconducting materials is selected from three (oxine) aluminium, N, N '-diphenyl-N, N '-two (3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines, N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4,4 '-diamines.
3, a kind of preparation method with magnetic composite organic nanometer granule film of magneto-resistance effect as claimed in claim 1 is characterized in that concrete steps are as follows:
Adopt the technology of vacuum thermal evaporation plated film, vacuum degree is 1 * 10
-3Pa--1 * 10
-4Pa; Magnetic metal material and organic semiconducting materials codeposition on the dielectric substrate that cleans up, are formed the magnetic organic semiconductor membrana granulosa of 20-1000nm thickness; Wherein, the evaporation speed of control magnetic metal material is
Control organic semi-conductor evaporation speed is
Between.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101814582A (en) * | 2010-04-01 | 2010-08-25 | 复旦大学 | Inorganic-organic semiconductor combined element having transverse photovoltaic effect and preparation method thereof |
| CN101858961A (en) * | 2010-05-04 | 2010-10-13 | 西南大学 | Double-parameter and high-sensitivity organic small molecular semiconductor film magnetic sensor |
| CN101847479B (en) * | 2009-03-24 | 2012-08-15 | 中国科学院物理研究所 | Microwave composite material and preparation method thereof |
| CN104009153A (en) * | 2014-05-30 | 2014-08-27 | 南开大学 | Novel particle film magneto-resistance device and preparation method thereof |
| CN104009152A (en) * | 2014-05-30 | 2014-08-27 | 南开大学 | Novel Fe/P3HT particle film magneto-resistance device and preparation method thereof |
| CN111175675A (en) * | 2019-12-30 | 2020-05-19 | 电子科技大学 | Magnetic field sensor based on organic field effect transistor and preparation method thereof |
| CN114622168A (en) * | 2020-12-14 | 2022-06-14 | 中国地质大学（北京） | Magnetic composite film with low hysteresis loss and preparation method thereof |
-
2008
- 2008-05-21 CN CNA2008100377479A patent/CN101354945A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101847479B (en) * | 2009-03-24 | 2012-08-15 | 中国科学院物理研究所 | Microwave composite material and preparation method thereof |
| CN101814582A (en) * | 2010-04-01 | 2010-08-25 | 复旦大学 | Inorganic-organic semiconductor combined element having transverse photovoltaic effect and preparation method thereof |
| CN101858961A (en) * | 2010-05-04 | 2010-10-13 | 西南大学 | Double-parameter and high-sensitivity organic small molecular semiconductor film magnetic sensor |
| CN104009153A (en) * | 2014-05-30 | 2014-08-27 | 南开大学 | Novel particle film magneto-resistance device and preparation method thereof |
| CN104009152A (en) * | 2014-05-30 | 2014-08-27 | 南开大学 | Novel Fe/P3HT particle film magneto-resistance device and preparation method thereof |
| CN104009153B (en) * | 2014-05-30 | 2017-01-18 | 南开大学 | Particle film magneto-resistance device and preparation method thereof |
| CN104009152B (en) * | 2014-05-30 | 2017-01-18 | 南开大学 | Fe/P3HT particle film magneto-resistance device and preparation method thereof |
| CN111175675A (en) * | 2019-12-30 | 2020-05-19 | 电子科技大学 | Magnetic field sensor based on organic field effect transistor and preparation method thereof |
| CN114622168A (en) * | 2020-12-14 | 2022-06-14 | 中国地质大学（北京） | Magnetic composite film with low hysteresis loss and preparation method thereof |
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