CN117166059A - Spontaneous exchange bias effect monocrystalline ferromagnetic film and preparation method thereof - Google Patents
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Abstract
The application discloses a spontaneous exchange bias effect monocrystalline ferromagnetic film, which is prepared from Ti 0.5 Cr 0.5 The application also discloses a preparation method of the single-crystal ferromagnetic film with the spontaneous exchange bias effect, which comprises the following steps compared with the prior art: the single-crystal ferromagnetic film with the spontaneous exchange bias effect is obtained by the magnetron sputtering technology, has simple preparation process and wide application range, is tightly combined with industries such as electronics, information storage and the like, and has great application value in the fields of superconducting quantum devices, novel information storages, spin electronic devices and the like.
Description
Technical Field
The application belongs to the field of new transition metal nitride materials, and particularly relates to a single-crystal ferromagnetic film with a spontaneous exchange bias effect and a preparation method thereof.
Background
Nitride materials are ideal materials for fabricating optoelectronic devices, particularly LEDs. The light source has wide application prospect and huge market potential in the aspects of high-density optical information storage, high-speed laser printing, full-color dynamic high-brightness optical display, solid illumination light source, high-brightness signal detection, communication and the like. In addition, the nitride semiconductor material is also an ideal material for manufacturing high-temperature, high-frequency and high-power devices.
Transition metal nitrides are a class of intermetallic compounds having covalent, ionic, and transition metal properties. Titanium nitride (TiN) and chromium nitride (CrN) have been successfully used for the past decades with their excellent properties. The TiN metal gate electrode can effectively shield phonon scattering in the high dielectric material, so that electron mobility of a channel is improved. Titanium nitride films with high dynamic inductance have found wide application in superconducting devices, including high quality factor electromagnetic radiation detectors. CrN has higher mechanical properties than titanium nitride coatings, plays an important role in multilayer coatings, and is applied as a support material in place of carbon in fuel cell type gas sensors. Ternary nitride films such as TiCrN, tiAIN, tiSiN not only combine the good properties of both, but their properties can also be controlled by metal dopants. For example, doping Ti in CrN may change its antiferromagnet into a ferromagnetic body.
The magnetic material is magnetized and saturated under the action of external magnetic field, and its magnetic susceptibility value can be up to 10-10 6 An order of magnitude and whose relationship between magnetization M and magnetic field strength H is a nonlinear complex functional relationship. The ferromagnetic material is tightly combined with industries such as electronics and information storage, has great application value in the fields of superconducting quantum devices, novel information storages, spin electronic devices and the like, but the technology for preparing the ferromagnetic film in the prior art is complex, and the preparation cost is high.
Disclosure of Invention
The application aims to provide a preparation method of a spontaneous exchange bias effect monocrystalline ferromagnetic film, and the preparation method is applied to the fields of superconducting quantum devices, novel information storages, spin electronic devices and the like.
In order to achieve the above purpose, the application adopts the following technical scheme: a single-crystal ferromagnetic film with spontaneous exchange bias effect is prepared from Ti 0.5 Cr 0.5 N structure withThere is a face centered cubic rock salt structure.
The preparation of the single-crystal ferromagnetic material in the application is based on TiN and CrN, both of which have the same face-centered cubic structure, so that the TiN and the CrN can easily form solid solution. In addition, crN has antiferromagnetic property at a Neel temperature of 273-286K, and part of CrN can be in solid solution with TiN to show ferromagnetism. The Ti dilution has a more pronounced weakening effect on the Cr-Cr antiferromagnetically related double exchange interaction than the ferromagnetically related superexchange interaction of Cr-N-Cr, thus yielding Ti 0.5 Cr 0.5 N single crystal ferromagnetic material.
Preferably, the ferromagnetic curie temperature of the single-crystal ferromagnetic thin film is 95K.
The application also aims to provide a preparation method of the spontaneous exchange bias effect single-crystal ferromagnetic film, which specifically comprises the following steps:
s1, cleaning a monocrystalline substrate and then sending the monocrystalline substrate into a sputtering chamber;
s2, vacuumizing a sputtering chamber, and then heating the monocrystalline substrate in the step S1 to a sputtering temperature and keeping constant;
s3, introducing nitrogen into the sputtering chamber for gas washing treatment;
s4, taking raw materials of Ti: cr=1:1 as a target material, taking nitrogen as sputtering gas, closing a heat table baffle, performing pre-sputtering treatment, and opening the heat table baffle after the pre-sputtering treatment is finished.
S5, turning off the radio frequency power supply, keeping the nitrogen pressure unchanged, and cooling to obtain the spontaneous exchange bias effect monocrystal ferromagnetic film.
Titanium nitride has a value of 10 -5 The low resistivity of Ω·cm and the superconducting properties below 5K are interesting for the application of titanium-based materials in spintronics devices, since titanium nitride is compatible with semiconductor silicon. For this reason, it is necessary to add a three-dimensional transition metal element to titanium nitride, and since titanium nitride is nonmagnetic, spin-polarized carriers are required to be introduced. Among the three-dimensional transition metal elements, cr is the optimal choice as a dopant, crN is an antiferromagnetic material with a paramagnetic to antiferromagnetic magnetic transition at a Neel temperature of 280K. Ti (Ti) 0.5 Cr 0.5 The ferromagnetism of the N film may be brought by Cr ions. In the nearest neighbor Cr-Cr and Cr t 2g Antiferromagnetic (AFM) interactions of orbitals and Cr-E related controlled by Cr-N-Cr double exchange g And the Ferromagnetic (FM) interactions of the N p track. The FM coupling of Cr-N-Cr in CrN is weaker than the direct AFM coupling of Cr-Cr. The charge redistribution from Ti to Cr and N occurs when Ti replaces Cr. This variation enhances the FM double exchange effect. Ti (Ti) 0.5 Cr 0.5 The Ti atomic fraction of the N film was 50%. At this time Cr t 2g The occupancy of the state is smaller, and the Hall is filled with Cr t 2g AFM interaction caused by state overlap is weak, cr e g The occupancy of the state is higher, the FM interaction is dominant, ti 0.5 Cr 0.5 The N film samples exhibited ferromagnetism.
Preferably, in the step S1, the cleaning treatment of the single crystal substrate specifically includes: and placing the monocrystalline substrate into an acetone and ethanol solution for ultrasonic cleaning for 5-15min, and drying. The application removes the pollutant on the surface of the substrate by ultrasonic cleaning, and the substrate cleaning result can influence the uniformity, compactness and performance of the film, and then the performance and reliability of the electronic device prepared by the film.
Preferably, in the step S1, the substrate is MgAl with (001) and (111) orientation 2 O 4 A monocrystalline substrate.
Preferably, the specific operation of the step S2 is as follows: firstly, the back bottom of the sputtering chamber is vacuumized to 10 -7 Torr, then the single crystal substrate of step S1 is heated to a sputtering temperature of 1100 ℃. The application heats the monocrystalline substrate to 1100 ℃, can not only effectively remove the organic reagent remained on the monocrystalline substrate in the temperature range, desorbs the impurity gas on the monocrystalline substrate, and provides a substrate with high cleanliness for the growth of Ti0.5Cr0.5N film; and the temperature interval provides sufficient kinetic energy for the sputtering clusters adsorbed on the substrate surface to form a high quality continuous film.
Preferably, in the step S3, the parameters of the scrubbing treatment are as follows: the nitrogen flow was 1.2sccm, nitrogenThe gas pressure was 0.02Torr or 0.05Torr. The application adopts moderate kinetic energy of the sputtering atomic group under the air pressure range of the nitrogen, which is beneficial to improving Ti 0.5 Cr 0.5 Crystalline quality of the N film.
Preferably, in the step S4, the parameters of the pre-sputtering process are as follows: the power of the power supply is 80W, and the pre-sputtering time is 10-30min. In the present application, the pre-sputtering is used to sufficiently remove the contaminated portion of the target surface and desorb the impurity gas on the target.
Preferably, in the step S4, the parameters of the sputtering process are as follows: the power of the power supply is 100W, and the sputtering time is 3h. The application adopts 100W power supply to carry out sputtering treatment, and the sputtering rate of the target material is moderate under the power supply range, which is beneficial to Ti 0.5 Cr 0.5 Epitaxial growth of N thin films.
Preferably, in the step S5, the step of cooling is as follows: cooling to 200 ℃ at a speed of 50 ℃/min.
Compared with the prior art, the application has the following advantages: the ferromagnetic film with the spontaneous exchange bias effect is obtained by the magnetron sputtering technology, the preparation process is simple, the application range is wide, the ferromagnetic film is tightly combined with industries such as electronics and information storage, and the like, and the ferromagnetic film has great application value in the fields such as superconducting quantum devices, novel information storages, spin electronic devices, and the like.
Drawings
FIG. 1 is a schematic diagram of the crystal structure of a single-crystal ferromagnetic thin film with spontaneous exchange bias effect according to the present application;
FIG. 2 is a high resolution X-ray diffraction 2 theta-omega scan of the spontaneous exchange bias effect single crystal ferromagnetic films prepared in examples 1 and 2 of the present application;
FIG. 3 is a reciprocal space scan of the X-ray diffraction pattern of the spontaneous exchange bias single crystal ferromagnetic films prepared in examples 1 and 2 of the present application;
FIG. 4 is an electron conductivity diagram of different orientations and an MR diagram of different orientations of the spontaneous exchange bias effect single crystal ferromagnetic films prepared in examples 1 and 2 of the present application;
FIG. 5 is a hysteresis loop diagram of the spontaneous exchange bias single crystal ferromagnetic films prepared in examples 1 and 2 of the present application at different temperatures;
FIG. 6 is an enlarged view of the hysteresis loop of the spontaneous exchange bias single crystal ferromagnetic thin film at 50Oe prepared in example 2 of the present application;
FIG. 7 is a graph showing zero field cooling and field cooling at different orientations of the spontaneous exchange bias effect single crystal ferromagnetic films prepared in examples 1 and 2 of the present application.
Detailed Description
In order that the above objects, features and advantages of the application will be readily understood, a more particular description of the application will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the application. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the application described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present application. The specification and examples of the present application are exemplary only.
FIG. 1 is a schematic diagram of the crystal structure of the single-crystal ferromagnetic thin film of the present application, as shown in FIG. 1, the crystal structure is a face-centered cubic rock salt structure.
The application provides a spontaneous exchange bias effect monocrystalline ferromagnetic film, which is formed by Ti 0.5 Cr 0.5 N is composed of a face-centered cubic rock salt structure, the ferromagnetic Curie temperature of the single-crystal ferromagnetic film is 95K, and the exchange bias field is 0-400Oe。
The preparation of the single-crystal ferromagnetic material in the application is based on TiN and CrN, both of which have the same face-centered cubic structure, so that the TiN and the CrN can easily form solid solution. In addition, crN has antiferromagnetic property at a Neel temperature of 273-286K, and part of CrN can be in solid solution with TiN to show ferromagnetism. The Ti dilution has a more pronounced weakening effect on the Cr-Cr antiferromagnetically related double exchange interaction than the ferromagnetically related superexchange interaction of Cr-N-Cr, thus yielding Ti 0.5 Cr 0.5 N single crystal ferromagnetic material.
The application also aims to provide a preparation method of the spontaneous exchange bias effect single-crystal ferromagnetic film, which specifically comprises the following steps:
s1, placing a monocrystalline substrate in an acetone and ethanol solution, ultrasonically cleaning for 5-15min, drying, and then sending into a sputtering chamber;
s2, firstly vacuumizing the back bottom of the sputtering chamber to 10 -7 Torr, then heating the single crystal substrate of step S1 to a sputtering temperature and keeping constant, the sputtering temperature being 1100 ℃;
s3, introducing nitrogen into the sputtering chamber to perform gas washing treatment, wherein the parameters of the gas washing treatment are as follows: the nitrogen flow is 1.2sccm, and the pressure of the nitrogen is 0.02Torr or 0.05Torr;
s4, taking titanium-chromium alloy with the molar ratio of Ti to Cr=1 to 1 of 2 inches as a target material, taking nitrogen as sputtering gas, closing a heat table baffle, performing pre-sputtering treatment under the condition that the power supply is 80W, opening the heat table baffle after the pre-sputtering treatment is finished, performing sputtering treatment on a monocrystalline substrate, wherein the power supply of the sputtering treatment is 100W, and the sputtering time is 3h, so as to obtain the monocrystalline film;
s5, turning off the radio frequency power supply, keeping the nitrogen pressure unchanged, and cooling to room temperature at the speed of 50 ℃/min.
In a specific embodiment, in step S1, the substrate is (001) and (111) oriented MgAl 2 O 4 A monocrystalline substrate.
The technical effects of the present application will be described below with reference to specific examples.
Example 1
And (3) cleaning a substrate: mgAl is added into 2 O 4 (001) Respectively placing the substrates in analytically pure acetone and ethanol solution, ultrasonically cleaning for 10min, drying by a nitrogen gun, and mounting the dried monocrystalline substrates on a heating table and conveying the monocrystalline substrates into a sputtering chamber;
magnetron sputtering: sequentially starting a mechanical pump and a molecular pump, and vacuumizing the back of the sputtering chamber to 10 -7 The Torr is turned on to heat, the temperature is set to 1100 ℃, the single crystal substrate is continuously baked for 30min after the temperature of the single crystal substrate is stabilized at 110 ℃, meanwhile, the flow rate of nitrogen gas is set to be 1.2sccm, a gas valve is regulated, the pressure of nitrogen gas in a sputtering chamber is kept to be stabilized at 0.05Torr,
when the temperature and the air pressure are stable, a radio frequency power supply is turned on, the power of the pre-sputtering power supply is set to be 80W, under the condition that a baffle plate of a heating table is closed, the power of the pre-sputtering power supply is set to be 100W after the pre-sputtering is carried out for 30min, the baffle plate of the heating table is turned on to formally start sputtering, after sputtering for 3h, the radio frequency power supply is turned off, the air pressure of original nitrogen is kept unchanged, the temperature is reduced at the speed of 50 ℃/min, and the temperature is naturally reduced after the temperature is reduced to 200 ℃, so as to obtain Ti 0.5 Cr 0.5 N (001) thin film.
Example 2
And (3) cleaning a substrate: mgAl is added into 2 O 4 (111) Respectively placing the substrates in analytically pure acetone and ethanol solution, ultrasonically cleaning for 10min, drying by a nitrogen gun, and mounting the dried monocrystalline substrates on a heating table and conveying the monocrystalline substrates into a sputtering chamber;
magnetron sputtering: sequentially starting a mechanical pump and a molecular pump, and vacuumizing the back of the sputtering chamber to 10 -7 The Torr is turned on to heat, the temperature is set to 1100 ℃, the single crystal substrate is continuously baked for 30min after the temperature of the single crystal substrate is stabilized at 110 ℃, meanwhile, the flow rate of nitrogen gas is set to be 1.2sccm, a gas valve is regulated, the pressure of nitrogen gas in a sputtering chamber is kept to be stabilized at 0.05Torr,
when the temperature and the air pressure are stable, a radio frequency power supply is started, the power of a pre-sputtering power supply is set to be 80W, under the condition that a baffle plate of a heating table is closed, the power of the radio frequency power supply is set to be 100W after the pre-sputtering is performed for 30min, the baffle plate of the heating table is started to formally start sputtering, after sputtering for 3h, the radio frequency power supply is turned off, and the air pressure of original nitrogen is kept notChanging, cooling at a speed of 50 ℃/min, naturally cooling to 200 ℃, and preparing Ti 0.5 Cr 0.5 N (111) film.
The results of the physical structure and physical characterization of the single-crystal ferromagnetic thin films obtained in examples 1 and 2 are shown in the figure.
The single-crystal ferromagnetic films obtained in examples 1 and 2 were subjected to high-resolution X-ray diffraction (XRD) diffraction analysis, and the results are shown in FIG. 2, in which (a) is a 2. Theta. -omega. Scan of the single-crystal ferromagnetic film obtained in example 1 of the present application, and (b) is a 2. Theta. -omega. Scan of the single-crystal ferromagnetic film obtained in example 2 of the present application, and as can be seen from FIG. 2, only Ti was present 0.5 Cr 0.5 N (001) characteristic peak, explaining Ti 0.5 Cr 0.5 N has excellent monocrystalline characteristics.
Ti oriented to (001) (shown in FIG. 3 a) and (111) (shown in FIG. 3 b), respectively 0.5 Cr 0.5 N film surrounds MgAl 2 O 4 (226) Reciprocal space scan analysis was performed near the diffraction peak, and the results are shown in fig. 3. Wherein the lower left is Ti 0.5 Cr 0.5 The diffraction peak of N, upper right, is the diffraction peak of substrate MAO. According to Ti 0.5 Cr 0.5 The position of the N diffraction peak in the graph is calculated to obtain (001) oriented Ti 0.5 Cr 0.5 The in-plane lattice constant a of the N film isThe out-of-plane lattice constant c is +.>(111) Orientation Ti 0.5 Cr 0.5 In-plane interplanar spacing d of N-films 11-2 Is->Out-of-plane interplanar spacing d 111 Is->
FIG. 4 shows the different results of the application according to example 1 and example 2An electrotransport and magneto-resistance (MR) map of the oriented monocrystalline film; wherein (a) is the relationship of the resistivity of the single crystal thin films produced in examples 1 and 2 of the present application with temperature; (b) MR diagrams of the single crystal thin films prepared in examples 1 and 2 of the present application; as can be seen from fig. 4a, the temperature dependence of the resistivity of the differently oriented films is different. A negative temperature coefficient of resistivity, i.e., a resistivity that decreases with increasing temperature, is observed in the (111) oriented film, exhibiting a semiconductor-like conductive behavior. When the temperature is lower than the Curie temperature T c When the temperature is higher than the curie temperature, the temperature dependence of the resistance is small. However, the resistivity of the (100) orientation first decreases with increasing temperature, and the electrical behavior of the sample changes significantly around 50K, increasing with increasing temperature. As can be seen from the magnetoresistance curves of fig. 4b, the films all exhibited significant hysteresis, indicating that the films exhibited ferromagnetic properties at low temperatures.
FIG. 5 shows hysteresis loop diagrams of the single crystal ferromagnetic films prepared in examples 1 and 2 according to the present application at different temperatures, wherein (a) is the hysteresis loop diagram of the (001) oriented single crystal film prepared in example 1 according to the present application at different temperatures; (b) Hysteresis loops of the (111) -oriented single-crystal ferromagnetic thin films prepared in example 2 of the present application at different temperatures.
FIG. 6 is an enlarged view of hysteresis loop of the single-crystal ferromagnetic thin film at 50Oe obtained in example 2 of the present application; from FIG. 5, it is clear that hysteresis is observed, indicating that the sample is ferromagnetic, ti 0.5 Cr 0.5 N saturation magnetization reaches 83emu/cc after 2K, and can be seen in the enlarged hysteresis loop of FIG. 6, ti 0.5 Cr 0.5 N (111) has obvious exchange bias phenomenon, and at the temperatures of 2K and 5K, the field cooling hysteresis loop is offset along the field axis to a certain extent, and the coercive field is increased.
FIG. 7 is a graph showing zero field cooling and field cooling for the single crystal ferromagnetic films of examples 1 and 2 of the present application at different orientations; (a) The single-crystal ferromagnetic thin film prepared in example 2 of the present application was magnetized in a magnetic field of 50Oe, and the sample was measured in a zero-field cooling and a field cooling modeTemperature dependence; (b) The single-crystal ferromagnetic thin film prepared in the embodiment 1 of the present application is the temperature dependence of sample magnetization measured in a zero-field cooling and field cooling mode under a magnetic field of 50 Oe; as can be seen from fig. 7, a larger magnetization is observed below 100K, with a peak near 50K. The two samples with different orientations have bifurcation in ZFC curve and FC curve around 50K, and irreversible behavior exists in the system, which indicates that ferromagnetic phase exists, ti 0.5 Cr 0.5 The FC curve of the N/MgAlO (111) film clearly rises at low temperatures indicating that spin glass states may be present in the film. From the figure it can also be concluded that T c 95K.
Although the present disclosure is disclosed above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications will fall within the scope of the disclosure.
Claims (10)
1. A spontaneous exchange bias effect single-crystal ferromagnetic thin film is characterized by comprising Ti 0.5 Cr 0.5 And N is composed of a face-centered cubic rock salt structure.
2. A spontaneous exchange bias effect single crystal ferromagnetic thin film according to claim 1, wherein the ferromagnetic curie temperature of the single crystal ferromagnetic thin film is 95K, the exchange bias field being 0-400Oe.
3. A method for preparing a spontaneous exchange bias effect single crystal ferromagnetic thin film according to claim 1 or 2, wherein the preparation method specifically comprises the following steps:
s1, cleaning a monocrystalline substrate and then sending the monocrystalline substrate into a sputtering chamber;
s2, vacuumizing a sputtering chamber, and then heating the monocrystalline substrate in the step S1 to a sputtering temperature and keeping constant;
s3, introducing nitrogen into the sputtering chamber for gas washing treatment;
s4, taking raw materials of Ti: cr=1:1 as a target material, taking nitrogen as sputtering gas, closing a heating table baffle, performing pre-sputtering treatment, and opening the heating table baffle after the pre-sputtering treatment is finished;
s5, turning off the radio frequency power supply, keeping the nitrogen pressure unchanged, and cooling to obtain the spontaneous exchange bias effect monocrystal ferromagnetic film.
4. A method for producing a single crystal ferromagnetic thin film with spontaneous exchange bias effect according to claim 3, wherein in said step S1, the single crystal substrate is subjected to a cleaning process comprising the steps of: and placing the monocrystalline substrate into an acetone and ethanol solution for ultrasonic cleaning for 5-15min, and drying.
5. The method for producing a single crystal ferromagnetic thin film according to claim 4, wherein in said step S1, the substrate is (001) and (111) oriented MgAl 2 O 4 A monocrystalline substrate.
6. A method for producing a single crystal ferromagnetic thin film with spontaneous exchange bias effect according to claim 3, wherein the specific operation of step S2 is as follows: firstly, the back bottom of the sputtering chamber is vacuumized to 10 -7 Torr, then the single crystal substrate of step S1 is heated to a sputtering temperature of 1100 ℃.
7. A method for producing a single crystal ferromagnetic thin film with spontaneous exchange bias effect according to claim 3, wherein in said step S3, the parameters of the purge treatment are as follows: the nitrogen gas flow was 1.2sccm, and the nitrogen gas pressure was 0.02Torr or 0.05Torr.
8. The method for preparing a single crystal ferromagnetic thin film with spontaneous exchange bias effect according to claim 7, wherein in the step S4, the parameters of the pre-sputtering process are as follows: the power of the power supply is 80W, and the pre-sputtering time is 10-30min.
9. The method for preparing a single crystal ferromagnetic thin film with spontaneous exchange bias effect according to claim 8, wherein in step S4, the parameters of the sputtering process are as follows: the power of the power supply is 100W, and the sputtering time is 3h.
10. A method for producing a single crystal ferromagnetic thin film with spontaneous exchange bias effect according to claim 3, wherein in step S5, the step of cooling is as follows: cooling to 200 ℃ at a speed of 50 ℃/min.
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