CN110581217B - Method for preparing double-layer perovskite manganese oxide film on monocrystalline silicon substrate by epitaxial growth - Google Patents
Method for preparing double-layer perovskite manganese oxide film on monocrystalline silicon substrate by epitaxial growth Download PDFInfo
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Abstract
The invention discloses a method for preparing double-layer perovskite manganese oxide on a monocrystalline silicon substrate by epitaxial growth by utilizing a buffer layerA method of forming a thin film material. The method comprises the following steps: (1) Adopts a sol-gel method to respectively prepare LaNiO required by experiments 3 And Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 A target material; (2) Deposition of LaNiO on single crystal silicon (100) substrates using pulsed laser deposition techniques 3 The film is used as a buffer layer, the deposition temperature is 600-700 ℃, the deposition oxygen pressure is 5Pa, the laser voltage is 23.0KV, the deposition rate is 3HZ, and the deposition times are 4000; annealing in situ for 5 min with Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 Using the block as a target material, continuously heating to 750 ℃, depositing oxygen pressure of 5Pa, laser voltage of 23.0KV, deposition rate of 3HZ, deposition times of 500-15000 times, and epitaxially growing Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 A film. The method has the advantages of simple process and strong controllability, and is suitable for industrial production.
Description
Technical Field
The invention relates to a method for preparing double-layer perovskite manganese oxide Pr (Sr) on a monocrystalline silicon substrate by epitaxial growth 0.1 Ca 0.9 ) 2 Mn 2 O 7 A method of thin film belongs to the technical field of magnetic materials.
Background
The double-layer perovskite manganese oxide can be regarded as infinite-layer perovskite manganese oxide (ABO) 3 Type) of Ruddelsden-Popper series A n+1 Mn n O 3n+1 In the case of n =2 in the compound, the structure is of two manganese oxides (MnO) 2 ) 2 The layers and the insulated AO rock salt layers are alternately stacked along the c axis and have a quasi-two-dimensional crystal structure. The material naturally has an insulating nonmagnetic rock salt layer in the crystal structure and is isolated in the middle of a perovskite layer with magnetic ordering, and due to the structural anisotropy, the material also has the property different from ABO 3 Magnetic and electric properties of the perovskite manganese oxide. Since the crystal orientation is randomly distributed in the polycrystalline bulk, the magnetic characteristics due to the anisotropy of the crystal structure are impaired. Theoretically, if the film material can be epitaxially grown on a substrate, the magnetic crystal of the material can be obviously increasedThe anisotropic property can enhance various magnetic properties of the material, such as exchange bias, magneto-resistance effect and the like. However, in most literature, single crystal SrTiO matched to the double-layered perovskite manganese oxide structure is used 3 、LaAlO 3 The double-layer perovskite manganese oxide thin film is epitaxially grown on the substrates, the manufacturing cost of the substrates is relatively expensive, and the cost of the synthesized double-layer perovskite manganese oxide thin film is high, so that the double-layer perovskite manganese oxide thin film is not beneficial to actual development and application.
In the practical application of the semiconductor industry, the monocrystalline silicon substrate produced in large scale is mostly used for preparing the magnetic thin film device, so that the preparation cost of the double-layer perovskite manganese oxide thin film can be greatly reduced, and the application in practical integrated circuits is facilitated. However, since the lattice of a single crystal silicon substrate does not match the perovskite structure, it is difficult to directly synthesize a thin film of a double-layer perovskite structure on such a substrate. Therefore, a method which is simple in preparation process, easy to control and suitable for realizing the epitaxial growth of the double-layer perovskite manganese oxide thin film on the monocrystalline silicon substrate in an industrialized mode is found, and meanwhile, the thin film can generate an obvious exchange bias effect under a certain condition and becomes a subject of general attention in the industry.
Disclosure of Invention
The invention aims to provide a method for preparing a double-layer perovskite manganese oxide film on a monocrystalline silicon substrate by epitaxial growth, which has simple process and strong controllability, and the prepared film can generate obvious exchange bias effect under certain conditions and is suitable for industrial production.
The idea of the invention is that a layer of LaNiO is first deposited on a monocrystalline silicon substrate by means of a pulsed laser deposition technique 3 The film is used as a buffer layer and then LaNiO 3 Epitaxial growth of double-layer perovskite manganese oxide Pr (Sr) on film 0.1 Ca 0.9 ) 2 Mn 2 O 7 Film, thereby realizing the epitaxial growth of double-layer perovskite manganese oxide Pr (Sr) on the monocrystalline silicon substrate 0.1 Ca 0.9 ) 2 Mn 2 O 7 Thin film, and the thin film system has obvious exchange bias effect.
Specifically, the method for preparing the double-layer perovskite manganese oxide film on the monocrystalline silicon substrate by epitaxial growth comprises the following steps:
(1) Adopts a sol-gel method to prepare LaNiO required by the experiment 3 And Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 A target material.
(a) Preparation of LaNiO required for experiments 3 A target material. Lanthanum nitrate, nickel nitrate and citric acid are weighed and proportioned according to the mass ratio of 1: 3, are sequentially dissolved in deionized water, then the citric acid is added, the mixture is subjected to water bath in a water bath kettle at the temperature of 80 ℃ for 4.5 hours, is stirred to obtain light green gel, and is dried in a drying oven at the temperature of 120 ℃ for 24 hours to obtain black fluffy substances; grinding, sintering at 800 deg.C for 5 hr to obtain black powder, grinding again, tabletting, and calcining at 1200 deg.C for 20-50 hr to obtain the desired LaNiO 3 A target material;
(b) Preparation of Pr (Sr) required for experiments 0.1 Ca 0.9 ) 2 Mn 2 O 7 A target material.
Weighing praseodymium oxide, strontium carbonate, calcium carbonate and manganese dioxide according to the mass ratio of 5: 12: 54: 60, and sequentially dissolving in deionized water while dropwise adding concentrated nitric acid; adding proper amount of citric acid and ethylene glycol, carrying out water bath in a water bath kettle at 80 ℃ for 24 hours, stirring to obtain a yellow brown gel, drying in a drying oven at 100 ℃ for 36 hours to obtain a black fluffy substance, grinding, and sintering at 600 ℃ for 5 hours to obtain black powder; grinding again, tabletting, and calcining at 1400 deg.C for 20-50 hr to obtain the desired Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 A target material.
(2) Growth of LaNiO 3 Buffer layer
Placing a single crystal Si (100) substrate into a preparation chamber of a pulse laser deposition system, and vacuumizing the preparation chamber of the pulse laser deposition system to less than or equal to 5 multiplied by 10 -4 Pa, with LaNiO 3 The block material is used as a target material, the deposition temperature is 600-700 ℃, the deposition oxygen pressure is 5Pa, the laser voltage is 23.0KV, the deposition rate is 3HZ, and the deposition times are 4000Growing LaNiO 3 Buffer layer, in-situ annealed for 5 minutes.
(3) Epitaxial growth of Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 Film(s)
With Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The block material is used as a target material, the temperature is continuously raised to 750 ℃, the deposition oxygen pressure is 5Pa, the laser voltage is 23.0KV, the deposition rate is 3HZ, the deposition frequency is 500-15000 times, and Pr (Sr) is epitaxially grown 0.1 Ca 0.9 ) 2 Mn 2 O 7 A film.
In the preparation method, the target material in the step (1) is LaNiO 3 And Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 A single phase material.
Preparation of LaNiO by sol-gel method in step (1) (a) 3 The target material is calcined at the high temperature of 1200 ℃ for 48 hours; (b) Preparation of Pr (Sr) by sol-gel method in (1) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The target material is calcined at the high temperature of 1400 ℃ for 48 hours. .
In the step (2), a buffer layer LaNiO 3 Has a thickness of 140-180nm, and Pr (Sr) in the step (3) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The thickness of the film is 20-660nm.
In the step (2), laNiO 3 The optimal deposition temperature for the buffer layer is 650 ℃.
In step (3), pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The optimal number of depositions of the film was 4000.
The invention has the following beneficial effects:
the double-layer perovskite manganese oxide film is an epitaxial film material, is simple to prepare and low in cost, and has an intrinsic exchange bias effect. The exchange coupling effect between the two phases changes along with the change of the deposition time, so that the exchange bias effect of the epitaxial film can be scheduled. The inventionA film of (a) which exhibits a characteristic value exchange bias field H of the magnitude of the exchange bias effect EB Can be adjusted by changing the deposition temperature of the bottom electrode and the deposition time of the top layer film.
Drawings
FIG. 1 shows a pure Si substrate (100) with only a deposited LaNiO buffer layer in example 6 of the present invention 3 Film and deposited Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 X-ray diffraction pattern of the film.
FIG. 2 shows Pr (Sr) in example 6 of the present invention 0.1 Ca 0.9 ) 2 Mn 2 O 7 A scanning electron micrograph of a cross section of the thin film (fig. 2 (a)) and an atomic force micrograph of the surface (fig. 2 (b)).
FIG. 3 shows Pr (Sr) in example 6 of the present invention 0.1 Ca 0.9 ) 2 Mn 2 O 7 The magnitude of the exchange bias field of the film sample was clearly observed from the graph, which is a hysteresis loop of the film at an applied cooling field of H =30000Oe and a temperature of T =2K (fig. 3 (a)), and an enlarged view of the low field (fig. 3 (b)) was taken from the graph.
Detailed Description
The following examples serve to illustrate the invention. It is to be understood that the drawings and the following detailed description are illustrative of the invention only and are not restrictive thereof. The invention is not limited to the embodiments described above, but rather, many modifications and variations may be made by one skilled in the art without departing from the scope of the invention. In addition, the specific formulation, time, temperature, etc. of the process parameters described below are also merely exemplary, and those skilled in the art can select appropriate values within the above-defined ranges.
Example 1
Depositing LaNiO on Si (100) substrate at 600 deg.C in sequence by pulse laser deposition 3 Film, top layer of Pr (Sr) deposited at 750 deg.C 0.1 Ca 0.9 ) 2 Mn 2 O 7 A film;
(1) Respectively calcining the mixture at the high temperature of 1200 ℃ and the high temperature of 1400 ℃ for 48 hours by adopting a sol-gel method to prepare LaNiO required by the experiment 3 And Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 A target material.
(2) Placing a single crystal Si (100) substrate into a preparation chamber of a pulse laser deposition system, and vacuumizing the preparation chamber of the pulse laser deposition system to be less than or equal to 5 multiplied by 10 -4 Pa, heating the substrate to 600 ℃ to obtain LaNiO 3 The block material is used as a target material, the laser voltage is 23.0KV, the deposition rate is 3HZ, and the deposition times are 4000. Annealing in situ for 5 min, heating to 750 deg.C, and adding Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The block material is used as a target material, the laser voltage is 23.0KV, the deposition rate is 3HZ, and the deposition times are 1000 times. Naturally cooling to room temperature after the deposition is finished, thereby preparing the Pr (Sr) with epitaxial growth 0.1 Ca 0.9 ) 2 Mn 2 O 7 Thin film of which LaNiO 3 The thickness of the film was 140nm, pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The thickness of the film was 60nm.
The magnetic properties of the film were measured using a magnetic measurement system-3 (MPMS-3). Under the cooling condition of H =30000Oe magnetic field and at the temperature of T =2K, measuring the magnetic hysteresis loop of the film sample, and finding that the magnetic hysteresis loop of the sample is shifted leftwards along the magnetic field level and has exchange bias effect, and the exchange bias field H EB 575 Oe. Wherein H EB = |H 1 +H 2 |/2，H 1 Is the intersection of the hysteresis loop with the left side of the abscissa, H 2 Is the intersection point of the hysteresis loop and the right side of the abscissa.
Example 2
Depositing LaNiO on Si (100) substrate at 650 deg.C 3 Film, top layer of Pr (Sr) deposited at 750 deg.C 0.1 Ca 0.9 ) 2 Mn 2 O 7 A film;
(1) Respectively calcining the mixture at the high temperature of 1200 ℃ and the high temperature of 1400 ℃ for 48 hours by adopting a sol-gel method to prepare LaNiO required by the experiment 3 And Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 A target material.
（2）Placing a single crystal Si (100) substrate into a preparation chamber of a pulse laser deposition system, and vacuumizing the preparation chamber of the pulse laser deposition system to be less than or equal to 5 multiplied by 10 -4 Pa, heating the substrate to 650 ℃ to obtain LaNiO 3 The block is used as a target material, the laser voltage is 23.0KV, the deposition rate is 3HZ, and the deposition times are 4000. Annealing in situ for 5 min, heating to 750 deg.C, and adding Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The block is used as a target material, the laser voltage is 23.0KV, the deposition rate is 3HZ, and the deposition times are 1000. Naturally cooling to room temperature after the deposition is finished, thereby preparing epitaxial Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 Thin film of which LaNiO 3 The thickness of the film was 150nm, pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The thickness of the film was 70nm.
The magnetic properties of the film were measured using a magnetic measurement system-3 (MPMS-3). Under the cooling condition of H =30000Oe magnetic field and at the temperature of T =2K, measuring the magnetic hysteresis loop of the film sample, and finding that the magnetic hysteresis loop of the sample is shifted leftwards along the magnetic field level and has exchange bias effect, and the exchange bias field H EB Is 700Oe. Wherein H EB = |H 1 +H 2 |/2，H 1 Is the intersection of the hysteresis loop with the left side of the abscissa, H 2 Is the intersection point of the hysteresis loop and the right side of the abscissa.
Example 3
Depositing LaNiO on Si (100) substrate at 700 deg.c successively by means of pulse laser deposition technology 3 Film, top layer of Pr (Sr) deposited at 750 deg.C 0.1 Ca 0.9 ) 2 Mn 2 O 7 A film;
(1) Respectively calcining the mixture at the high temperatures of 1200 ℃ and 1400 ℃ for 48 hours by adopting a sol-gel method to prepare LaNiO required by the experiment 3 And Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 A target material.
(2) Placing a single crystal Si (100) substrate into a preparation chamber of a pulse laser deposition system, and vacuumizing the preparation chamber of the pulse laser deposition system to be less than or equal to5×10 -4 Pa, heating the substrate to 700 ℃ to obtain LaNiO 3 The block is used as a target material, the laser voltage is 23.0KV, the deposition rate is 3HZ, and the deposition times are 4000. Annealing in situ for 5 min, heating to 750 deg.C, and adding Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The block material is used as a target material, the laser voltage is 23.0KV, the deposition rate is 3HZ, and the deposition times are 1000 times. Naturally cooling to room temperature after the deposition is finished, thereby preparing epitaxial Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 Thin film of which LaNiO 3 The thickness of the film is 160nm, pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The thickness of the film was 80nm.
The magnetic properties of the film were measured using a magnetic measurement system-3 (MPMS-3). Under the cooling condition of H =30000Oe magnetic field and at the temperature of T =2K, measuring the magnetic hysteresis loop of the film sample, and finding that the magnetic hysteresis loop of the sample is shifted leftwards along the magnetic field level and has exchange bias effect, and the exchange bias field is H EB 765Oe. Wherein H EB = |H 1 +H 2 |/2，H 1 Is the intersection of the hysteresis loop with the left side of the abscissa, H 2 Is the intersection point of the hysteresis loop and the right side of the abscissa.
Example 4
Depositing LaNiO on Si (100) substrate at 650 deg.C 3 Film, top layer of Pr (Sr) deposited at 750 deg.C 0.1 Ca 0.9 ) 2 Mn 2 O 7 A film;
(1) Respectively calcining the mixture at the high temperature of 1200 ℃ and the high temperature of 1400 ℃ for 48 hours by adopting a sol-gel method to prepare LaNiO required by the experiment 3 And Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 A target material.
(2) Placing a single crystal Si (100) substrate into a preparation chamber of a pulse laser deposition system, and vacuumizing the preparation chamber of the pulse laser deposition system to be less than or equal to 5 multiplied by 10 -4 Pa, heating the substrate to 650 ℃ to form LaNiO 3 The block material is used as a target material, the laser voltage is 23.0KV, the deposition rate is 3HZ,the number of depositions was 4000. Annealing in situ for 5 min, heating to 750 deg.C, and adding Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The block material is used as a target material, the laser voltage is 23.0KV, the deposition rate is 3HZ, and the deposition times are 500. Naturally cooling to room temperature after the deposition is finished, thereby preparing epitaxial Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 Thin film of which LaNiO 3 The thickness of the film was 150nm, pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The thickness of the film was 20nm.
The magnetic properties of the film were measured using a magnetic measurement system-3 (MPMS-3). Measuring the hysteresis loop of the film sample at the temperature of T =2K under the cooling condition of the H =30000Oe magnetic field, and finding that the hysteresis loop of the sample is shifted leftwards along the magnetic field level and has exchange bias effect, and the exchange bias field H EB Is 650Oe. Wherein H EB = |H 1 +H 2 |/2，H 1 Is the intersection of the hysteresis loop with the left side of the abscissa, H 2 Is the intersection point of the hysteresis loop and the right side of the abscissa.
Example 5
Depositing LaNiO on Si (100) substrate at 650 deg.C 3 Film, top layer of Pr (Sr) deposited at 750 deg.C 0.1 Ca 0.9 ) 2 Mn 2 O 7 A film;
(1) Respectively calcining the mixture at the high temperature of 1200 ℃ and the high temperature of 1400 ℃ for 48 hours by adopting a sol-gel method to prepare LaNiO required by the experiment 3 And Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 A target material.
(2) Placing a single crystal Si (100) substrate into a preparation chamber of a pulse laser deposition system, and vacuumizing the preparation chamber of the pulse laser deposition system to be less than or equal to 5 multiplied by 10 -4 Pa, heating the substrate to 650 ℃ to form LaNiO 3 The block material is used as a target material, the laser voltage is 23.0KV, the deposition rate is 3HZ, and the deposition times are 4000. Annealing in situ for 5 min, heating to 750 deg.C, and adding Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The block material is used as a target material, the laser voltage is 23.0KV, the deposition rate is 3HZ, and the deposition times are 2000. Naturally cooling to room temperature after the deposition is finished, thereby preparing epitaxial Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 Thin film of which LaNiO 3 The thickness of the film is 170nm, pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The thickness of the film was 80nm.
The magnetic properties of the thin film were measured using a magnetic measurement system-3 (MPMS-3). Under the cooling condition of H =30000Oe magnetic field and at the temperature of T =2K, measuring the magnetic hysteresis loop of the film sample, and finding that the magnetic hysteresis loop of the sample is shifted leftwards along the magnetic field level and has exchange bias effect, and the exchange bias field H EB Is 280Oe. Wherein H EB = |H 1 +H 2 |/2，H 1 Is the intersection of the hysteresis loop with the left side of the abscissa, H 2 Is the intersection point of the hysteresis loop and the right side of the abscissa.
Example 6
Depositing LaNiO on Si (100) substrate at 650 deg.C 3 Film, top layer of Pr (Sr) deposited at 750 deg.C 0.1 Ca 0.9 ) 2 Mn 2 O 7 A film;
(1) Respectively calcining the mixture at the high temperatures of 1200 ℃ and 1400 ℃ for 48 hours by adopting a sol-gel method to prepare LaNiO required by the experiment 3 And Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 A target material.
(2) Placing a single crystal Si (100) substrate into a preparation chamber of a pulse laser deposition system, and vacuumizing the preparation chamber of the pulse laser deposition system to be less than or equal to 5 multiplied by 10 -4 Pa, heating the substrate to 650 ℃ to form LaNiO 3 The block material is used as a target material, the laser voltage is 23.0KV, the deposition rate is 3HZ, and the deposition times are 4000. Annealing in situ for 5 min, heating to 750 deg.C, and adding Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The block material is used as a target material, the laser voltage is 23.0KV, the deposition rate is 3HZ, and the deposition times are 4000. Naturally cooling toRoom temperature to prepare epitaxial Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 Thin film of which LaNiO 3 The thickness of the film is 180nm, pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The thickness of the film was 200nm.
FIG. 1 shows the X-ray diffraction pattern of the above-mentioned film obtained according to example 6, from which it can be seen that the film is of epitaxial type. FIG. 2 shows a cross-sectional view of a scanning electron microscope and a surface view of an atomic force microscope of the above-mentioned thin film obtained according to example 2, from which it can be seen that the surface of the thin film is flat, the particles are uniform and the root mean square Roughness (RMS) is 1.041nm; the thickness of the buffer layer is 180nm as seen in the cross-sectional view, while the thickness of the double-layer perovskite thin film is 200nm.
The magnetic properties of the film were measured using a magnetic measurement system-3 (MPMS-3). Under the cooling condition of H =30000Oe magnetic field and at the temperature of T =2K, measuring the magnetic hysteresis loop of the film sample, and finding that the magnetic hysteresis loop of the sample is shifted leftwards along the magnetic field level and has exchange bias effect, and the exchange bias field H EB Is 890Oe. Wherein H EB = |H 1 +H 2 |/2，H 1 Is the intersection of the hysteresis loop with the left side of the abscissa, H 2 Is the intersection point of the hysteresis loop and the right side of the abscissa.
Example 7
Depositing LaNiO on Si (100) substrate at 650 deg.C 3 Film, top layer of Pr (Sr) deposited at 750 deg.C 0.1 Ca 0.9 ) 2 Mn 2 O 7 A film;
(1) Respectively calcining the mixture at the high temperature of 1200 ℃ and the high temperature of 1400 ℃ for 48 hours by adopting a sol-gel method to prepare LaNiO required by the experiment 3 And Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 A target material.
(2) Placing a single crystal Si (100) substrate into a preparation chamber of a pulse laser deposition system, and vacuumizing the preparation chamber of the pulse laser deposition system to be less than or equal to 5 multiplied by 10 -4 Pa, heating the substrate to 650 ℃ toLaNiO 3 The block is used as a target material, the laser voltage is 23.0KV, the deposition rate is 3HZ, and the deposition times are 4000. Annealing in situ for 5 min, heating to 750 deg.C, and adding Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The block material is used as a target material, the laser voltage is 23.0KV, the deposition rate is 3HZ, and the deposition times are 15000 times. Naturally cooling to room temperature after the deposition is finished, thereby preparing epitaxial Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 Thin film of which LaNiO 3 The thickness of the film is 180nm, pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The thickness of the film was 660nm.
The magnetic properties of the film were measured using a magnetic measurement system-3 (MPMS-3). Under the cooling condition of H =30000Oe magnetic field and at the temperature of T =2K, measuring the magnetic hysteresis loop of the film sample, and finding that the magnetic hysteresis loop of the sample is shifted leftwards along the magnetic field level and has exchange bias effect, and the exchange bias field H EB 875Oe. Wherein H EB = |H 1 +H 2 |/2，H 1 Is the intersection of the hysteresis loop with the left side of the abscissa, H 2 Is the intersection point of the hysteresis loop and the right side of the abscissa.
Claims (6)
1. A method for preparing a double-layer perovskite manganese oxide film on a monocrystalline silicon substrate by epitaxial growth is characterized by comprising the following steps:
(1) Adopts a sol-gel method to prepare LaNiO required by the experiment 3 And Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 A target material;
(a) Preparing LaNiO required by experiment 3 Target material
Lanthanum nitrate, nickel nitrate and citric acid are weighed according to the mass ratio of 1: 3, and
sequentially dissolving in deionized water, adding citric acid, water-bathing in 80 deg.C water bath for 4.5 hr, stirring to obtain light green gel, drying in 120 deg.C drying oven for 24 hr to obtain black fluffy substance, grinding, sintering at 800 deg.C for 5 hr to obtain black powder, grinding again to obtain powderAfter grinding, tabletting and calcining at 1200 ℃ for 20-50 hours to obtain the required LaNiO 3 A target material;
(b) Preparation of Pr (Sr) required for experiments 0.1 Ca 0.9 ) 2 Mn 2 O 7 Target material
Weighing praseodymium oxide, strontium carbonate, calcium carbonate and manganese dioxide according to the mass ratio of 5: 12: 54: 60, sequentially dissolving in deionized water while dropping concentrated nitric acid, adding appropriate amount of citric acid and ethylene glycol, water-bathing in a water bath kettle at 80 ℃ for 24 hours, stirring to obtain tawny gel, drying in a drying oven at 100 ℃ for 36 hours to obtain black fluffy substances, grinding, sintering at 600 ℃ for 5 hours to obtain black powder, grinding again, tabletting, and calcining at 1400 ℃ for 20-50 hours to obtain the required Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 A target material;
(2) Growing LaNiO 3 Buffer layer
Placing a single crystal Si (100) substrate into a preparation chamber of a pulse laser deposition system, and vacuumizing the preparation chamber of the pulse laser deposition system to be less than or equal to 5 multiplied by 10 -4 Pa, with LaNiO 3 The block material is used as a target material, the deposition temperature is 600-700 ℃, the deposition oxygen pressure is 5Pa, the laser voltage is 23.0KV, the deposition rate is 3HZ, the deposition times are 4000 times, and LaNiO grows 3 A buffer layer, annealing for 5 minutes in situ;
(3) Epitaxial growth of Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 Film(s)
With Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The block material is used as a target material, the temperature is continuously raised to 750 ℃, the deposition oxygen pressure is 5Pa, the laser voltage is 23.0KV, the deposition rate is 3HZ, the deposition frequency is 500-15000 times, and Pr (Sr) is epitaxially grown 0.1 Ca 0.9 ) 2 Mn 2 O 7 A film.
2. The method according to claim 1, wherein the target material in step (1) is LaNiO 3 And Pr (Sr) 0.1 Ca 0.9 ) 2 Mn 2 O 7 A single phase material.
3. The method of claim 1, wherein the LaNiO is prepared by sol-gel method in step (1) (a) 3 Calcining the target material at 1200 ℃ for 48 hours; (b) Preparation of Pr (Sr) by sol-gel method in (1) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The target material is calcined at a high temperature of 1400 ℃ for 48 hours.
4. The method of claim 1, wherein in step (2), the buffer layer LaNiO 3 Has a thickness of 140-180nm, and Pr (Sr) in the step (3) 0.1 Ca 0.9 ) 2 Mn 2 O 7 The thickness of the film is 20-660nm.
5. The method according to claim 1, wherein in the step (2), the deposition temperature is 650 ℃.
6. The method according to claim 1, wherein in the step (3), the number of depositions is 4000.
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| WO2008111274A1 (en) * | 2007-03-15 | 2008-09-18 | National University Corporation Toyohashi University Of Technology | Laminate structure on semiconductor substrate |
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