CN113257993B - Organic semiconductor magnetic resistance device with carbon film protective layer and preparation method and application thereof - Google Patents
Organic semiconductor magnetic resistance device with carbon film protective layer and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an organic semiconductor magnetic resistance device with a carbon film protection layer, a preparation method and application thereof, wherein the organic semiconductor magnetic resistance device is of a vertical lamination structure which is sequentially formed by a substrate, a first conductive layer, an organic semiconductor layer, the carbon film protection layer and a second conductive layer from bottom to top, the carbon film protection layer is carbon, the structure of the first conductive layer comprises a plurality of first cuboids which are arranged in parallel, the structure of the second conductive layer comprises a plurality of second cuboids which are arranged in parallel, the first cuboid is arranged right above the second cuboid, the length direction of the second cuboid is vertical to the length direction of the first cuboid, and the cross section shape of the carbon film protection layer on a horizontal plane is the same as the cross section shape of the second conductive layer on the horizontal plane. The method effectively solves the pollution and damage problem of heat radiation and metal particle penetration to the organic semiconductor layer in the preparation method of the second conductive layer in the traditional organic semiconductor magnetic resistance device.
Description
Technical Field
The invention belongs to the technical field of organic electronic devices, and particularly relates to an organic semiconductor magnetic resistance device with a carbon film protective layer, and a preparation method and application thereof.
Background
In recent years, organic spintronics (Organic spintronics) has received a great deal of attention in the scientific field. Organic spintronics combines two disciplines of organic electronics and spintronics, and is an emerging field of research in which organic semiconductor materials are used to conduct or control spin-related signals. On one hand, the organic semiconductor material has the advantages of low price, light weight, excellent flexibility and capability of being chemically modified according to the needs, and has been widely applied to the fields of organic electroluminescent devices, photovoltaic cells, field effect transistors and the like; on the other hand, research in spintronics has made possible the application of nonvolatile devices in which functions of logic operation, storage, communication, and the like can be simultaneously combined. Meanwhile, since the related energy scale of spin dynamics is much smaller than that of manipulating charges, the spin device has great advantages in terms of operation speed and energy consumption compared with the conventional electronic device. It is expected that the successful combination of the two will greatly drive the development and application of the next generation organic flexible functional memory device.
With the vigorous development of organic electronics, the understanding of the conduction mechanism of organic semiconductor materials is more in depth, and in addition to focusing on the charge transport properties of carriers in organic materials, the influence of spin degrees of freedom is also being sought. In particular, in 2004, the successful fabrication and measurement of vertical organic spin valve devices based on aluminum octahydroxyquinoline and vertical organic magnetoresistance devices based on polyfluorene has greatly led researchers to interest in the research of organic semiconductor materials in the field of magnetoresistance. Currently, research on organic spintronics phenomena is mainly focused on three aspects: (1) A magnetic field effect in an organic-like electroluminescent diode structure, wherein the interconversion of spin singlet polaron pairs and spin triplet polaron pairs can be affected by an externally applied magnetic field, resulting in an organic magneto-resistive (OMAR) effect; (2) Magnetoresistive (MR) effects in Organic Spin Valve (OSV) devices, where spin signal injection, transmission, manipulation and detection are mainly involved; (3) A magneto-electroluminescent (MEL) bipolar organic spin valve device or a spin-organic electroluminescent diode device in which spin-polarized electrons and holes are simultaneously injected into an organic semiconductor layer to be combined to emit light, the intensity of the electroluminescence depending on the relative magnetization direction of ferromagnetic electrodes.
Among them, in the organic spin valve device represented by the sandwich structure of the ferromagnetic electrode layer/the organic semiconductor layer/the ferromagnetic electrode layer and the organic magneto-resistive (OMAR) device represented by the sandwich structure of the non-magnetic metal electrode layer/the organic semiconductor layer/the non-magnetic metal electrode layer, the upper electrode (the ferromagnetic electrode layer and the non-magnetic metal electrode layer) positioned at the topmost end of the device is generally prepared by depositing the upper electrode on the organic semiconductor layer by a conventional vacuum deposition process. In the prior art, the working voltage of the device is required to be reduced as much as possible under the premise of keeping the stability and working performance of the device so as to reduce the energy consumption, and the operation of reducing the working voltage is to reduce the thickness of the organic semiconductor layer, however, multiple experiments show that the thinner the thickness of the organic semiconductor layer is, the more likely the organic semiconductor layer is damaged by heat radiation in the process of vacuum depositing an upper electrode on the organic semiconductor layer, and meanwhile, the upper electrode metal particles penetrating into the organic semiconductor layer can cause the generation of a dead layer, so that the stability of the device is seriously damaged, the performance of the device is greatly reduced, and the defects of poor uniformity, low yield and the like when the device is prepared in a large area are caused (see comparative example 2).
Therefore, how to reduce the damage of the upper electrode to the organic semiconductor layer during the vacuum deposition process in the fabrication of the organic semiconductor magnetoresistive device is a critical issue to be solved.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide an organic semiconductor magnetic resistance device with a carbon film protection layer, wherein the carbon film protection layer is pre-deposited in the organic semiconductor magnetic resistance device, and the organic semiconductor layer and a second conductive layer (namely an upper electrode in the background art) are isolated by utilizing the carbon film protection layer which has good compatibility with the organic semiconductor layer, so that the pollution and damage to the organic semiconductor layer caused by heat radiation and metal particle permeation in the preparation process of the second conductive layer are greatly reduced.
Another object of the present invention is to provide a method for manufacturing the above-mentioned organic semiconductor magnetoresistive device, which is simple and efficient, making it possible to controllably prepare a large area of the organic semiconductor magnetoresistive device.
The aim of the invention is achieved by the following technical scheme.
An organic semiconductor magnetic resistance device with a carbon film protection layer, wherein the organic semiconductor magnetic resistance device is of a vertical laminated structure which is formed by a substrate, a first conductive layer, an organic semiconductor layer, the carbon film protection layer and a second conductive layer from bottom to top in sequence, the carbon film protection layer is carbon, the structure of the first conductive layer comprises a plurality of first cuboids which are arranged in parallel, the structure of the second conductive layer comprises a plurality of second cuboids which are arranged in parallel, the first cuboids are arranged right above the second cuboids, the length direction of the second cuboids is perpendicular to the length direction of the first cuboids, and the cross section shape of the carbon film protection layer on a horizontal plane is identical to the cross section shape of the second conductive layer on the horizontal plane. In the above technical solution, the thickness of the first conductive layer is 1 to 1000nm, preferably 5 to 100nm; the thickness of the organic semiconductor layer is 1 to 2000nm, preferably 20 to 300nm, more preferably 50 to 200nm; the thickness of the carbon film protective layer is 1-100 nm; the thickness of the second conductive layer is 1 to 1000nm, preferably 5 to 100nm.
In the above technical scheme, the first conductive layer is a first ferromagnetic electrode material, the second conductive layer is a second ferromagnetic electrode material, and the first ferromagnetic electrode material is Lanthanum Strontium Manganese Oxide (LSMO) or Fe 3 O 4 One or more than two of Co, niFe, fe and CoFeB, the second ferromagnetic electrode material is Lanthanum Strontium Manganese Oxide (LSMO) or Fe 3 O 4 One or more than two of Co, niFe, fe and CoFeB, wherein the substrate is Strontium Titanate (STO), magnesium oxide (MgO), silicon wafer, glass, sapphire, PDMS or PET.
In the above technical scheme, the first conductive layer is a first non-magnetic metal electrode material, the second conductive layer is a second non-magnetic metal electrode material, and the first non-magnetic metal electrode material is Pt, ITO, FTO, al, au, ag, cu, ca, ni, ti, graphene and PEDOT: one or a mixture of more than two of PSS, wherein the second non-magnetic metal electrode material is Pt, ITO, FTO, al, au, ag, cu, ca, ni, ti, graphene and PEDOT: and one or more than two of PSS are mixed, and the substrate is silicon wafer, glass, sapphire, PDMS or PET.
In the above technical solution, the organic semiconductor layer is one or a mixture of a polymer material, a small molecular material and an organic semiconductor single crystal micro/nano material.
The preparation method of the organic semiconductor magnetic resistance device comprises the following steps:
1) Preparing a substrate and a first conductive layer on the substrate as a bottom electrode;
in the step 1), the method for obtaining the bottom electrode comprises the following steps: placing a first mask plate for forming the first cuboid on the substrate, depositing the first conductive layer on the substrate, and taking down the first mask plate, wherein the method for depositing the first conductive layer on the substrate comprises the following steps: vacuum thermal evaporation, vacuum vapor deposition, pulsed laser deposition, magnetron sputtering, plasma sputtering, molecular beam external grinding, spraying or printing;
2) Depositing the organic semiconductor layer on the first conductive layer, wherein the method for depositing the organic semiconductor layer is spin coating, evaporation coating or transfer method;
3) Placing a second mask plate for forming the second cuboid on the organic semiconductor layer, and spraying carbon on the organic semiconductor layer to form the carbon film protective layer, wherein the rate of depositing the carbon film protective layer is 0.05-5 nm/pulse;
in the step 3), the background vacuum degree is less than 10 -3 The carbon spraying is carried out at mbar.
In said step 3), said carbon spraying is performed by means of a carbon spraying instrument in a scanning tunneling microscope (SEM) technique.
4) Depositing the second conductive layer on the carbon film protective layer, and taking down the second mask, wherein the method for depositing the second conductive layer comprises the following steps: vacuum thermal evaporation, vacuum vapor deposition, pulsed laser deposition, magnetron sputtering, plasma sputtering, molecular beam external grinding, spraying or printing.
In the above technical scheme, the first mask and the second mask are patterned metal foils.
The application of the organic semiconductor magnetic resistance device in reducing the probability of short circuit of the device is provided.
The beneficial effects of the invention are as follows:
1. the carbon film protective layer for the organic semiconductor magnetic resistance device has the following advantages:
1) The problems of pollution and damage to the organic semiconductor layer caused by heat radiation and metal particle permeation in the preparation method of the second conductive layer in the traditional organic semiconductor magnetic resistance device are effectively solved;
2) The preparation method is relatively simple, has strong universality, good repeatability and high yield, and provides an improved method for constructing the second conductive layer of the organic semiconductor magnetic resistance device;
3) The carbon film protective layer is a transparent conductive layer with controllable thickness, has small resistance and smooth surface, hardly changes the background roughness of the original organic semiconductor layer, has negligible weak magnetic response back because of no hydrogen atoms, and cannot influence the signal of the organic semiconductor magnetic resistance device;
4) The preparation difficulty of the organic semiconductor magnetic resistance device is reduced, the device quality is controllable, and the mass production can be realized.
2. The organic semiconductor magnetic resistance device with the carbon film protective layer can change the resistance of the device under the action of an external magnetic field, and the magnetic resistance change has the characteristic of being highly symmetrical relative to a positive magnetic field and a negative magnetic field. Compared with the organic semiconductor magnetic resistance device directly prepared by the traditional vacuum deposition method, the organic semiconductor magnetic resistance device with the carbon film protective layer has great advantages in the aspect of reducing the working voltage of the device and further reducing the energy consumption because the pollution and damage problem of the second conductive layer to the organic semiconductor layer can be effectively avoided, and the device cannot be short-circuited and fail when the thinner organic semiconductor layer is processed.
3. The invention can furthest reduce the influence of defects, metal impurities and other adverse factors by developing the preparation process of the second conductive layer based on the carbon film protective layer and the application of the second conductive layer in the organic semiconductor magnetic resistance device, and provides an effective solution for large-area controllable preparation of the organic semiconductor magnetic resistance device. By reducing the thickness under the precondition of ensuring the quality of the organic semiconductor layer, the stability and the working performance of the device can be further improved while the energy consumption is reduced.
Drawings
FIG. 1 is a schematic diagram of the structure of an organic semiconductor magnetoresistive device according to the present invention;
FIG. 2 is a graph showing the roughness and surface morphology of the surface of the carbon film protective layer and the surface of the organic semiconductor layer without the carbon film protective layer of the organic semiconductor magnetoresistive device obtained in example 1, wherein a is the surface of the organic semiconductor layer without the carbon film protective layer, and b is the surface of the carbon film protective layer;
FIG. 3 is a graph showing the resistance of the organic semiconductor magnetoresistive device obtained in example 1 as a function of temperature;
FIG. 4 is a graph showing the resistance of the organic semiconductor magnetoresistive device obtained in example 1 as a function of magnetic field;
FIG. 5 is a graph showing the resistance of the device obtained in comparative example 1 as a function of temperature;
FIG. 6 is a graph showing the resistance of the device obtained in comparative example 1 as a function of magnetic field;
FIG. 7 is a graph showing the resistance of the device obtained in comparative example 2 as a function of temperature;
FIG. 8 is a graph showing the resistance of the device obtained in comparative example 2 as a function of magnetic field.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
Poly (3-hexylthiophene-2, 5-diyl) was purchased from taiwanese (Shanghai) chemical industry development limited, product code: p2513, its structural formula is:
example 1
An organic semiconductor magnetic resistance device with a carbon film protection layer is shown in fig. 1, the organic semiconductor magnetic resistance device is of a vertical laminated structure which is formed by a substrate, a first conductive layer, an organic semiconductor layer, the carbon film protection layer and a second conductive layer from bottom to top, the carbon film protection layer is carbon, the structure of the first conductive layer comprises a plurality of first cuboids (the width of the first cuboids is 1 cm) which are arranged in parallel, the structure of the second conductive layer comprises a plurality of second cuboids (the width of the second cuboids is 1 cm) which are arranged in parallel, the first cuboids are arranged right above the second cuboids, the length direction of the second cuboids is perpendicular to the length direction of the first cuboids, a junction (joint) is formed by the overlapped part of the second cuboids and the first cuboids and the organic semiconductor layer corresponding to the overlapped part, and the cross section shape of the carbon film protection layer on the horizontal plane is the same as the cross section shape of the second conductive layer on the horizontal plane. The carbon film protective layer, the organic semiconductor layer and the substrate are all in a complete cuboid shape, and the thickness of the first conductive layer is about 100nm; the thickness of the organic semiconductor layer is 20-30nm; the thickness of the carbon film protective layer is 10nm; the thickness of the second conductive layer was 30nm. The thickness of the substrate was 0.7mm.
The first conductive layer is made of a first non-magnetic metal electrode material, the second conductive layer is made of a second non-magnetic metal electrode material, the first non-magnetic metal electrode material is ITO, the second non-magnetic metal electrode material is Au, and the substrate is glass. The organic semiconductor layer is poly (3-hexylthiophene-2, 5-diyl) (P3 HT).
The preparation method of the organic semiconductor magnetic resistance device comprises the following steps:
1) Preparing ITO glass as a bottom electrode, wherein an ITO layer on the ITO glass is of a strip-shaped structure with the width of 1mm and is used as a first cuboid, sequentially and ultrasonically cleaning with soapy water and deionized water for 10 minutes, then putting a mixed solution of hydrogen peroxide and concentrated sulfuric acid with the volume ratio of 1:2 into the solution, heating and boiling for 5 minutes, sequentially and ultrasonically drying the surface residual solution in deionized water and isopropanol for about 10 minutes, and finally utilizing nitrogen to rapidly blow the surface residual solution for later use.
2) Depositing an organic semiconductor layer on the first conductive layer, wherein the method for depositing the organic semiconductor layer is spin coating; the specific practice is to dissolve 10mg of poly (3-hexylthiophene-2, 5-diyl) in 1mL of o-dichlorobenzene, stir with a magnetic stirrer (model: MS-H-Pro+) at 60℃for 30min, spin-coat on ITO glass with a spin coater (model: KW-4A) at 1000 rpm. And after spin coating, performing annealing treatment on a hot stage (model number digital hotplate SD) to remove the redundant o-dichlorobenzene, wherein the annealing temperature is 120 ℃ and the annealing time is 30min.
3) Placing a second mask plate for forming the second cuboid on the organic semiconductor layer, and fixing the second mask plate, wherein the second mask plate is formed by a carbon spraying instrument (model: leica EM ACE 600) spraying carbon onto the organic semiconductor layer to form carbonA film protective layer, wherein the rate of depositing the carbon film protective layer is 0.2nm/pulse; at a background vacuum of less than 10 - 4 Carbon spraying is carried out in mbar. The surface of the carbon film protective layer and the surface of the organic semiconductor layer on which the carbon film protective layer was not deposited were characterized by Atomic Force Microscopy (AFM), and as shown in fig. 2, it was found that the carbon film protective layer hardly changed the surface morphology and roughness of the organic semiconductor layer.
4) Keeping the second mask plate motionless, placing the substrate in the vacuum coating machine again, depositing a second conductive layer on the carbon film protective layer, and taking down the second mask plate, wherein the method for depositing the second conductive layer comprises the following steps: vacuum thermal evaporation method.
The second mask is a patterned metal foil.
The organic semiconductor magnetoresistive device obtained in example 1 was tested:
1) Characterization of electrical properties:
the organic semiconductor magneto-resistive device prepared above was subjected to resistance temperature-dependent test using a Physical Property Measurement System (PPMS) from quantium Design company, in which an ITO layer was used as an electrode positive electrode and a second conductive layer (Au) was used as an electrode negative electrode. The obtained temperature-resistance change curve is shown in fig. 3, and the resistance of the organic semiconductor magnetic resistance device is increased from 2000 ohms to 15000 ohms in the cooling process of 300K to 2K, so that the organic semiconductor is proved to have good performance, and the carbon film protective layer has a protective effect on the organic semiconductor.
2) Characterization of magnetoresistive properties:
the organic semiconductor magnetic resistance device prepared by the method is subjected to resistance change test along with a magnetic field at the temperature of 100K by using a Physical Property Measurement System (PPMS) of Quantum Design company, an external magnetic field is applied from +2000Oe to-2000 Oe, the obtained magnetic field-resistance change curve is shown as shown in figure 4, the device is found to show good magnetic resistance response behavior, the resistance of the organic semiconductor magnetic resistance device is changed under the external magnetic field, the average value of the organic semiconductor magnetic resistance device is about 5260 ohms when the external magnetic field is not 0, and the external magnetic field is about 5240 ohms when the external magnetic field is 0, so that the organic semiconductor magnetic resistance device has the magneto resistance characteristic of being highly symmetrical relative to positive and negative magnetic fields.
Comparative example 1
In order to further demonstrate the protective effect of the carbon film protective layer on the organic semiconductor layer in the technical scheme of the present invention, particularly the necessity of the existence of the carbon film protective layer when the organic semiconductor layer is thin, a device without the carbon film protective layer was designed as comparative example 1.
The device is a vertical laminated structure which is formed by a substrate, a first conductive layer, an organic semiconductor layer and a second conductive layer from bottom to top in sequence. The structure of first conducting layer includes a plurality of parallel arrangement's first cuboid (the width of first cuboid is 1 cm), and the structure of second conducting layer includes a plurality of parallel arrangement's second cuboid (the width of second cuboid is 1 cm), has first cuboid directly over the second cuboid, and the length direction of second cuboid is perpendicular with the length direction of first cuboid. The thickness of the first conductive layer is about 100nm; the thickness of the organic semiconductor layer is 20-30nm; the thickness of the second conductive layer was 30nm. The thickness of the substrate was 0.7mm.
The first conductive layer is made of a first non-magnetic metal electrode material, the second conductive layer is made of a second non-magnetic metal electrode material, the first non-magnetic metal electrode material is ITO, the second non-magnetic metal electrode material is Au, and the substrate is glass. The organic semiconductor layer is poly (3-hexylthiophene-2, 5-diyl) (P3 HT).
The preparation method of the device comprises the following steps:
1) Preparing ITO glass as a bottom electrode, wherein an ITO layer on the ITO glass is of a strip-shaped structure with the width of 1mm and is used as a first cuboid, sequentially and ultrasonically cleaning with soapy water and deionized water for 10 minutes, then putting a mixed solution of hydrogen peroxide and concentrated sulfuric acid with the volume ratio of 1:2 into the solution, heating and boiling for 5 minutes, sequentially and ultrasonically drying the surface residual solution in deionized water and isopropanol for about 10 minutes, and finally utilizing nitrogen to rapidly blow the surface residual solution for later use.
2) Depositing an organic semiconductor layer on the first conductive layer, wherein the method for depositing the organic semiconductor layer is spin coating; the specific practice is to dissolve 10mg of poly (3-hexylthiophene-2, 5-diyl) in 1mL of o-dichlorobenzene, stir with a magnetic stirrer (model: MS-H-Pro+) at 60℃for 30min, spin-coat on ITO glass with a spin coater (model: KW-4A) at 1000 rpm. And after spin coating, performing annealing treatment on a hot stage (model number digital hotplate SD) to remove the redundant o-dichlorobenzene, wherein the annealing temperature is 120 ℃ and the annealing time is 30min.
3) Placing a second mask plate for forming the second cuboid on the organic semiconductor layer, placing the substrate in a vacuum coating machine again, depositing a second conductive layer on the organic semiconductor layer, and taking down the second mask plate, wherein the method for depositing the second conductive layer comprises the following steps: vacuum thermal evaporation method.
The second mask is a patterned metal foil.
The device obtained in comparative example 1 was tested:
1) Characterization of electrical properties:
the device prepared above was subjected to resistance temperature-dependent test using a Physical Property Measurement System (PPMS) from Quantum Design company, in which an ITO layer was used as the positive electrode and Au was used as the negative electrode. The resulting temperature-resistance change curve is shown in fig. 5, and it was found that when the temperature was lowered from 300K to 100K, the resistance of the device was lowered from 180 ohms to 90 ohms and then raised to 110 ohms, and this phase of the decrease in resistance with the decrease in temperature was a demonstration that the device had a metallic behavior, indicating that when a magnetoresistive device having a thinner organic semiconductor layer was produced using the conventional method, the organic semiconductor layer was destroyed by infiltration of metal particles and heat radiation during the deposition of the second conductive layer, so that the second conductive layer formed minute metal conductive wires through the organic semiconductor layer to be in contact with the first conductive layer portion, demonstrating that example 1 was able to protect the organic semiconductor layer using the carbon film protective layer.
2) Characterization of magnetoresistive properties:
the device prepared above was tested for resistance change with magnetic field at 100K using a Physical Property Measurement System (PPMS) from quantium Design company, and the applied magnetic field was applied from +2000Oe to-2000 Oe, and the resulting magnetic field-resistance change curve was shown in fig. 6, which shows that the device resistance was changed but the magneto-resistance characteristic highly symmetrical with respect to the positive and negative magnetic fields was lost, and the device performance was destroyed, proving the necessity of protecting the organic semiconductor material using a carbon film protective layer.
Comparative example 2
In order to demonstrate that the carbon film protective layer has good light transmittance and conductivity, and does not affect the organic semiconductor layer body due to a magnetic field response signal generated by itself in the test of the organic semiconductor magnetoresistive device, a device without an organic semiconductor layer was designed as comparative example 2.
The utility model provides a device, the device is by the perpendicular lamination that constitutes in proper order from bottom to top of substrate, first conducting layer, carbon film protective layer and second conducting layer, carbon film protective layer is carbon, the structure of first conducting layer includes a plurality of parallel arrangement's first cuboid (the width of first cuboid is 1 cm), the structure of second conducting layer includes a plurality of parallel arrangement's second cuboid (the width of second cuboid is 1 cm), there is first cuboid and the length direction of second cuboid and the length direction of first cuboid right above the second cuboid is perpendicular, the cross section shape of carbon film protective layer on the horizontal plane is the same with the cross section shape of second conducting layer on the horizontal plane. The thickness of the first conductive layer is about 100nm; the thickness of the carbon film protective layer is 10nm; the thickness of the second conductive layer was 30nm. The thickness of the substrate was 0.7mm.
The first conductive layer is made of a first non-magnetic metal electrode material, the second conductive layer is made of a second non-magnetic metal electrode material, the first non-magnetic metal electrode material is ITO, the second non-magnetic metal electrode material is Au, and the substrate is glass.
The preparation method of the device comprises the following steps:
1) Preparing ITO glass as a bottom electrode, wherein an ITO layer on the ITO glass is of a strip-shaped structure with the width of 1mm and is used as a first cuboid, sequentially and ultrasonically cleaning with soapy water and deionized water for 10 minutes, then putting a mixed solution of hydrogen peroxide and concentrated sulfuric acid with the volume ratio of 1:2 into the solution, heating and boiling for 5 minutes, sequentially and ultrasonically drying the surface residual solution in deionized water and isopropanol for about 10 minutes, and finally utilizing nitrogen to rapidly blow the surface residual solution for later use.
2)Placing a second mask plate for forming the second cuboid on the ITO layer, fixing, and spraying carbon on the ITO layer through a carbon spraying instrument (model: leica EM ACE 600) in a scanning tunneling microscope (SEM) technology to form a carbon film protective layer, wherein the speed of depositing the carbon film protective layer is 0.2nm/pulse; at a background vacuum of less than 10 -4 Carbon spraying is carried out in mbar. The carbon film protective layer deposited on the ITO layer is observed under an optical microscope, and the surface is quite smooth; compared with the ITO layer without the carbon film protective layer at the mask, the carbon film protective layer is a colorless transparent film, and has good light transmittance.
3) Keeping the second mask plate motionless, placing the substrate in the vacuum coating machine again, depositing a second conductive layer on the carbon film protective layer, and taking down the second mask plate, wherein the method for depositing the second conductive layer comprises the following steps: vacuum thermal evaporation method.
The second mask is a patterned metal foil.
The device obtained in comparative example 2 was tested:
1) Characterization of electrical properties:
the device was subjected to a resistance change with temperature test using a Physical Properties Measurement System (PPMS) from quantium design company, in which an ITO layer was used as an electrode positive electrode and Au was used as an electrode negative electrode. The obtained temperature-resistance change curve is shown in fig. 7, and it was found that the resistance remained in the order of hundred ohms in the temperature range of 100K to 300K, and it was confirmed that the conductivity of the carbon film protective layer itself was good, and the partial pressure of the carbon film protective layer itself was negligible when the organic semiconductor magnetoresistive device was constructed as the protective layer, compared with the organic semiconductor magnetoresistive device having the carbon film protective layer shown in fig. 3.
2) Characterization of magnetoresistive properties:
the device is tested for resistance change along with a magnetic field by using a Physical Property Measurement System (PPMS) of Quantum Design company at a temperature of 100K, an external magnetic field is applied from +2000Oe to-2000 Oe, the obtained magnetic field-resistance change curve is shown in figure 8, the resistance change along with the magnetic field of the device is found to be negligible, and the introduction of a carbon film protective layer is proved to not interfere with the magnetic response signal of the organic semiconductor magnetoresistive device.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (8)
1. The organic semiconductor magnetic resistance device is of a vertical laminated structure which is formed by a substrate, a first conductive layer, an organic semiconductor layer, a carbon film protective layer and a second conductive layer from bottom to top in sequence, wherein the carbon film protective layer is carbon, the structure of the first conductive layer comprises a plurality of first cuboids which are arranged in parallel, the structure of the second conductive layer comprises a plurality of second cuboids which are arranged in parallel, the first cuboid is arranged right below the second cuboid, the length direction of the second cuboid is vertical to the length direction of the first cuboid, and the cross section shape of the carbon film protective layer on a horizontal plane is the same as the cross section shape of the second conductive layer on the horizontal plane; the first conductive layer is made of a first non-magnetic metal electrode material, the second conductive layer is made of a second non-magnetic metal electrode material, and the first non-magnetic metal electrode material is Pt, ITO, FTO, al, au, ag, cu, ca, ni, ti, graphene and PEDOT: one or a mixture of more than two of PSS, wherein the second non-magnetic metal electrode material is Pt, ITO, FTO, al, au, ag, cu, ca, ni, ti, graphene and PEDOT: and one or more than two of PSS are mixed, and the substrate is silicon wafer, glass, sapphire, PDMS or PET.
2. The organic semiconductor magnetoresistive device according to claim 1, the first conductive layer is characterized in that the thickness of the first conductive layer is 1-1000 nm; the thickness of the organic semiconductor layer is 1-2000 nm; the thickness of the carbon film protective layer is 1-100 nm; the thickness of the second conductive layer is 1-1000 nm.
3. The organic semiconductor magnetoresistive device according to claim 2, wherein the thickness of the first conductive layer is 5-100 nm; the thickness of the organic semiconductor layer is 20-300 nm; the thickness of the second conductive layer is 5-100 nm.
4. The organic semiconductor magnetoresistive device according to claim 1, wherein the organic semiconductor layer is a mixture of one or more of a polymer material, a small molecule material, and an organic semiconductor single crystal micro/nano material.
5. A method for producing the organic semiconductor magnetoresistive device according to claim 1, characterized by comprising the steps of:
1) Preparing a substrate and a first conductive layer positioned on the substrate, wherein the first conductive layer is used as a bottom electrode;
2) Depositing the organic semiconductor layer on the first conductive layer, wherein the method for depositing the organic semiconductor layer is spin coating, evaporation coating or transfer method;
3) Placing a second mask plate for forming the second cuboid on the organic semiconductor layer, and spraying carbon on the organic semiconductor layer to form the carbon film protective layer, wherein the speed of depositing the carbon film protective layer is 0.05-5 nm/pulse;
4) Depositing the second conductive layer on the carbon film protective layer, and taking down the second mask, wherein the method for depositing the second conductive layer comprises the following steps: vacuum thermal evaporation, vacuum vapor deposition, pulsed laser deposition, magnetron sputtering, plasma sputtering, molecular beam external grinding, spraying or printing.
6. The method according to claim 5, wherein in the step 1), the bottom electrode is obtained by: placing a first mask plate for forming the first cuboid on the substrate, depositing the first conductive layer on the substrate, and taking down the first mask plate, wherein the method for depositing the first conductive layer on the substrate comprises the following steps: vacuum thermal evaporation, vacuum vapor deposition, pulsed laser deposition, magnetron sputtering, plasma sputtering, molecular beam external grinding, spraying or printing.
7. The method according to claim 5, wherein in the step 3), the carbon spraying is performed at a vacuum of less than 10 "3 mbar;
in the step 3), the carbon spraying is performed by a carbon spraying instrument in a scanning tunnel microscope technology.
8. The method of claim 6, wherein the first reticle and the second reticle are patterned metal foils.
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