CN114150296B - Preparation method of rare earth manganese oxide film for near-room-temperature infrared imaging - Google Patents
Preparation method of rare earth manganese oxide film for near-room-temperature infrared imaging Download PDFInfo
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1245—Inorganic substrates other than metallic
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
Abstract
The invention discloses a preparation method of a rare earth manganese oxide film for near room temperature infrared imaging, which specifically comprises the following steps: substrate high-temperature annealing, substrate reduction, substrate activation, precursor configuration, precursor purification, substrate spin coating, substrate heat treatment and film sintering; the method of the invention can prepare the rare earth manganese oxide film with large area, high flatness and high TCR value in the range of near room temperature while ensuring the high fit of the component function of the rare earth manganese oxide film with the design value, thereby strengthening the performance basis of the rare earth manganese oxide film as an infrared detection imaging device and further widening the selection range of the sensitive material of the infrared detector.
Description
Technical Field
The invention belongs to the technical field of perovskite type thin film material preparation, and particularly relates to a preparation method of a rare earth manganese oxide thin film for near room temperature infrared imaging.
Background
The rare earth doped perovskite manganese-based oxide is a research hotspot of a strong-correlation electronic material in recent years, and the basic problem of condensed state physics is included. La 1-x Ca x MnO 3 As a classical manganese oxide system, the strong coupling action of multiple degrees of freedom (charge, orbit, spin and lattice) exists; meanwhile, each ordered phase and each disordered phase have a competitive coexistence relationship, so that the material has a unique electric transport behavior at the metal-insulation phase transition temperature (T) MI ) The material has high Temperature Coefficient of Resistance (TCR) nearby, and the excellent surface heat sensitivity of the material enables the material to be applied to the field of infrared detection imaging. The development trend of the material at present mainly comprises two directions: i) The TCR value is improved by adjusting components, optimizing the process and the like, so that the detection sensitivity, the imaging resolution and the like of the infrared device are improved; ii) raising T by improving microstructure or the like MI The temperature reaches the room temperature, so that the infrared device does not need to depend on an external cold source. Because the material needs to be applied to the micro device, the material needs to be two-dimensional.
At present, the preparation method of perovskite thin film can be divided into two categories of physical method and chemical method according to film forming reaction characteristics, and can be divided into vapor deposition and liquid deposition according to film forming component process. In the chemical deposition method: the vapor deposition method includes a general vapor deposition method, a metal organic chemical vapor deposition method and a plasma enhanced vapor deposition method; the liquid phase deposition method includes a sol-gel method, a metal organic solution decomposition method and a water bath method. The physical deposition method is basically a vapor deposition method including a sputtering deposition method (radio frequency magnetron sputtering and ion beam sputtering), an evaporation deposition method (thermal evaporation and electron beam evaporation), a pulsed laser deposition method, a molecular beam epitaxy method, and the like. Each of the above-mentioned preparation processes has its advantages and disadvantages. In general, the chemical deposition method has the advantages of lower preparation temperature, higher deposition rate, easy control of film components, better repeatability and large-scale manufacturing. The chemical deposition method has the disadvantages that the toxicity and the process parameters of alkoxide are difficult to adjust, the formed film is not compact enough, and an epitaxial film is not easy to obtain. The physical deposition method for preparing the film needs to be carried out in a vacuum environment, has high cleanliness and high film forming quality, can even prepare high-quality single crystal films and superlattice structures, and has the defects of expensive equipment, slow film forming time, easy occurrence of chemical component segregation and unsuitability for large-scale and large-area film manufacture. For the preparation of rare earth manganese oxide thin films, the methods commonly used are: chemical vapor deposition, pulsed laser deposition, sputtering, molecular beam epitaxy, and sol-gel-spin coating. Compared with other synthesis approaches, the sol-gel spin coating method has the following advantages: i) The sintering temperature required by the synthetic product material is low, so that the preparation threshold is greatly reduced; ii) the complexation in the sol-gel process can achieve uniformity at the molecular level; iii) The method has high process stability and simple and reliable synthesis process; iv) the material prepared by the sol-gel method has strong transportability and stable component functions.
The current route for preparing thin films by sol-gel spin coating mostly has the following problems: 1) In most processes at the present stage, pretreatment is less carried out on the substrate, for example, a bonding valence bond on the substrate is activated, so that the wettability of the substrate is greatly improved, and the spin coating adhesive force is improved; for example, the surface of the substrate lacks strong oxidizing property, the epitaxial growth preference of the liquid film in a coating form is not obvious in the high-temperature sintering process, the interface defects of the obtained film are more, and the resistance temperature coefficient of the material is influenced; 2) Most of the existing synthesis routes only carry out simple liquid impurity removal and have no gas impurity removal step. If qualitative filter paper is adopted for simple liquid phase filtration, the effect is poor; when the raw materials are subjected to complexation reaction, a long molecular chain polymer aggregate can be formed, but the aggregate is difficult to remove by common sieve mesh filtration, and in the subsequent heat treatment process of the aggregate, on one hand, the aggregate can be further increased and even the condition of preferential nucleation can occur, so that the surface flatness of the film is low, and the uniformity of the whole film forming is poor; on the other hand, the agglomerate contains a large amount of bubbles which do not overflow, and the bubbles will remain in the film forming to form space defects, which affect the resistance temperature coefficient of the material; 3) In the prior art, concentration ratio between metal cations and a chelating agent is less concerned when a precursor solution is prepared, particularly, the wettability of the solution on a substrate is influenced to a great extent by the pH value of the precursor solution, and meanwhile, the dynamic viscosity of the precursor solution is less regulated and unified, so that the film forming area is influenced.
Therefore, based on the above technical defects, in the technical field of perovskite thin film material preparation, there is still a need for research and improvement on the preparation method of the rare earth manganese oxide thin film for near room temperature infrared imaging, which is also a research focus and focus in the field at present, and is the starting point and the driving force of the present invention.
Disclosure of Invention
The invention aims to prepare the rare earth manganese oxide film with large area, high flatness and high TCR in the range of near room temperature while ensuring that the component functions of the rare earth manganese oxide film are highly consistent with the design values, strengthen the performance basis of the infrared detection imaging device and further widen the selection range of the sensitive materials of the infrared detector.
The preparation method of the rare earth manganese oxide film for near room temperature infrared imaging specifically comprises the following steps:
(1) And (3) substrate high-temperature annealing: placing a monolithic substrate on a corundum plate, wherein the contact surface of the substrate and the corundum plate is defined as a substrate B surface, the contact surface of the substrate and the corundum plate is not defined as a substrate A surface, the substrate is highly symmetrical round, the diameter of the substrate is 3-15mm, the thickness of the substrate is 0.3-2mm, and the corundum plate and the substrate are placed in a high-temperature heat treatment furnace to carry out annealing treatment on the substrate to obtain an annealed substrate, wherein the annealing can remove mechanical stress in the substrate, and the subsequent growth process of the thin film cannot be influenced by external stress;
(2) Substrate reduction: placing the single annealed substrate obtained in the step (1) on a hollow frame, wherein the center of the substrate is concentric with the center point of the hollow frame, the surface of the substrate A faces downwards, lowering the hollow frame into a reduction tank, hydrogen peroxide with the purity of 95-98% is filled in the reduction tank, immersing the substrate into the hydrogen peroxide, driving the hollow frame to drive the substrate to rotate and spin-wash circumferentially around the center of the circle, then performing spray-washing on the substrate, and performing reciprocating 3~4 times of the spin-washing and spray-washing operations to obtain the reduced substrate, reducing and removing original impurities and pollutants on the substrate, and greatly reducing the roughness of the surface of the substrate;
(3) Activating a substrate: purging the reduced substrate obtained in the step (2) by using a high-pressure air gun, wherein the air gun adopts high-purity nitrogen as a purging medium, then the substrate is placed on a spin coater, the surface of the substrate A faces upwards, the center of the circle of the substrate is concentric with the axis of a rotating shaft of the spin coater, the spin coater drives the substrate to rotate at a high speed, the rotation is divided into three stages, the surface of the substrate A in a high-speed rotating state is titrated with an activating solution in each stage, the titration unit of each stage is 2 to 5ml, then the substrate is sprayed and washed to obtain an activated substrate, the activation can greatly improve the surface wettability of the substrate, so that the liquid tension and the tension on the substrate can be dynamically balanced, and the subsequent liquid film coating and the stable existence of the subsequent liquid film are facilitated;
(4) Precursor preparation: preparing 30-85ml of initial solution, wherein the initial solution is a mixed solution of alcohols and high-purity deionized water with a volume ratio of 1-7-4, sequentially adding manganese nitrate, lanthanum nitrate, calcium nitrate and strontium chloride into the initial solution, dropwise adding 3-15ml of ethylene glycol, adding citric acid, dropwise adding 0.2-8ml of amines, wherein the concentration ratio of acid ions to metal ions is 2;
(5) Precursor purification: enabling a precursor solution with a uniformly dispersed medium to flow through an organic nylon filter head with the aperture of 0.1-0.35mm for filtering, wherein the filtering operation is to remove impurities and large-size aggregates in the solution, so that the thickness and the quality of a subsequent film are uniform, then placing the precursor solution in a vacuum cavity for negative-pressure defoaming operation, the defoaming vacuum degree is 0.5 KPa-4 MPa, the defoaming duration is 0.5-3 h, the defoaming environment temperature is 20-25 ℃, the defoaming operation is to discharge gas in the solution so as not to influence the subsequent operation, then placing the precursor solution in a sealed cavity for aging operation, the aging duration is 6-48h, the aging environment temperature is 15-20 ℃, obtaining a layered and homogenized precursor solution, and aging can enable the aggregates with different sizes to be layered in the solution, so that the subsequent operation and the uniformity of a product are guaranteed;
(6) Spin coating of a substrate: placing the activated substrate obtained in the step (3) on a spin coater, wherein the surface A of the substrate faces upwards, the center of the circle of the substrate is concentric with the axis position of a rotating shaft of the spin coater, titrating the layered and homogenized precursor solution obtained in the step (5) on the surface A of the substrate before starting the spin coater, wherein the titration unit is 0.5 to 9ml, starting the spin coater to drive the substrate to rotate at a high speed, and spreading and homogenizing the solution under the combined action of centrifugal force, liquid level tension and interface wettability to obtain a substrate coated with a liquid film;
(7) Substrate heat treatment: transferring the coated liquid film substrate obtained in the step (6) to a heat treatment table, attaching the surface B of the substrate to the table top, performing step heat treatment on the substrate and the liquid film coated on the surface A of the substrate, evaporating and removing non-target substances in the liquid film to obtain a substrate in an amorphous film layer, and purging the film layer through a aurilave;
(8) Repeating the steps (6) and (7) for 3 to 10 times to obtain an amorphous film with complete micro-morphology and controllable film thickness, wherein the film thickness dimension is 100nm to 5 mu m;
(9) Film sintering: and (3) placing the amorphous film obtained in the step (8) in a muffle furnace to carry out sintering operation, wherein the heating and cooling rates of the sintering operation are 2-20 ℃/min, the final sintering temperature is 550-1250 ℃, the heat preservation time of the final sintering stage is 1-6 h, and the sintering process can provide nucleation power and growth power for the amorphous film so that the amorphous film grows into crystals, thus obtaining the rare earth manganese oxide film.
Further optimizing, wherein the annealing treatment process in the step (1) is in a step shape, and a step-shaped heat preservation process with at least more than 2 stages is carried out, the annealing temperature rise rate is 5 to 10 ℃/min, the final annealing temperature is 600 to 1300 ℃, and the heat preservation time of the final annealing stage is 1 to 8h.
And (3) further optimizing, wherein the rotation speed of the spin washing in the step (2) is 25 to 50rap/min, the spin washing time is 2 to 15min, the spin washing water temperature is 20 to 25 ℃, the spray washing in the steps (2) and (3) is to spray wash the surface A of the substrate by using an atomized water gun to clean impurities, and the spray washing medium is high-purity deionized water.
Further optimization, the three stages of rotation described in step (3) are specifically: the rotation speed in the first stage is 200 to 800rap/min, the rotation time is 30 to 60s, the rotation speed in the second stage is 1000 to 2500rap/min, the rotation time is 20 to 40s, the rotation speed in the third stage is 3000 to 6000rap/min, and the rotation time is 10 to 20s; the activating solution in the step (3) is high-purity anhydrous alcohol and 98% concentrated nitric acid in a volume ratio of 2 to 10.
Further optimizing, wherein in the step (4), the magnetic stirring speed is 200 to 500rap/min, the stirring time is 2 to 12h, and the stirring temperature is 20 to 75 ℃; the dynamic viscosity of the precursor solution with the uniformly dispersed medium is 0.55 to 2.75Mpa.S, and the PH value of the precursor solution is 0.5 to 4.
And (3) further optimizing, wherein the high-speed rotation in the step (6) is divided into three stages, the rotation speed in the first stage is 300-700rap/min, the rotation time is 5-15s, the rotation speed in the second stage is 1100-2350rap/min, the rotation time is 5-20s, the rotation speed in the third stage is 3400-7200rap/min, and the rotation time is 15-55s.
Further optimizing, the step type heat treatment in the step (7) comprises the steps of preserving heat for 10 to 20min at 50 to 65 ℃ in the first stage, preserving heat for 10 to 15min at 95 to 185 ℃ in the second stage, and preserving heat for 10 to 15min at 265 to 340 ℃ in the third stage.
And (3) further optimizing, wherein the operating environment in the steps (2) to (8) is a glove box environment, the oxygen content of the glove box environment is less than or equal to 0.1ppm, and the water content is less than or equal to 0.1ppm.
Further preferably, the alcohols in step (4) include isopropanol, methanol and ethanol, and the amines include monoethanolamine, diethanolamine and ethanolamine.
And further optimizing, wherein the substrate is any one of a high-purity silicon substrate, a mica sheet, a high-purity quartz sheet and a sapphire sheet.
Compared with the prior art, the invention has the following innovation points:
(1) According to the invention, by optimizing the solvent ratio and increasing the organic matters to optimize the adaptation degree of the dynamic viscosity of the solution and the spin-coating rotation speed, on one hand, a film with a larger area can be prepared; on the other hand, the flatness of the liquid film is improved, and a foundation is laid for obtaining a thin film with high mirror surface degree subsequently; meanwhile, the pH value of the precursor solution is adjusted by adjusting the concentration ratio of the metal cations to the chelating agent, so that the wettability of the solution on the substrate is optimized.
(2) According to the invention, the substrate is sequentially subjected to treatments such as ordered annealing, reduction spin-washing, titration activation and the like, so that on one hand, the bonding valence bond on the substrate is activated, and the wettability and spin-coating adhesive force of the substrate are improved; on the other hand, the substrate is in a strong reduction state, which is beneficial to the formation of preferential epitaxial growth of the liquid film in the high-temperature sintering process, eliminates most interface defects and improves the resistance temperature coefficient of the material.
(3) The invention finishes the removal of liquid impurities and gas impurities successively by purifying the precursor. The organic nylon filter head with small aperture is used for adsorption and filtration, so that the macromolecular aggregate with long molecular chains formed in the complexing reaction can be removed, the possibility of abnormal nucleation and growth is reduced, the flatness and uniformity of the film are improved, and in addition, the bubbles contained in the aggregate are peeled through the design of negative pressure suction filtration, so that the space defect in the film forming is reduced.
Drawings
FIG. 1 is an atomic force microscope three-dimensional view of the film obtained in example 1;
FIG. 2 is an atomic force micrograph and section lines of the film obtained in example 1;
FIG. 3 is a temperature coefficient of resistance versus temperature curve of the film obtained in example 1;
FIG. 4 is an atomic force microscope three-dimensional view of the film obtained in example 2;
FIG. 5 is an atomic force micrograph and cross-sectional views of the thin film obtained in example 2;
FIG. 6 is a temperature coefficient of resistance versus temperature curve of the film obtained in example 2;
FIG. 7 is an atomic force microscope three-dimensional view of the film obtained in example 3;
FIG. 8 is an atomic force micrograph and section lines of the film obtained in example 3;
FIG. 9 is a temperature coefficient of resistance versus temperature curve of the film obtained in example 3;
Detailed Description
The invention will be described in further detail with reference to the drawings and the detailed description, but the scope of the invention is not limited thereto.
Example 1
The preparation method of the rare earth manganese oxide film of the embodiment specifically comprises the following steps:
(1) And (3) substrate high-temperature annealing: placing a single substrate of a high-purity silicon substrate on a corundum plate, wherein the contact surface of the substrate and the corundum plate is defined as a substrate B surface, the contact surface of the substrate, which is not in contact with the corundum plate, is defined as a substrate A surface, the substrate is highly symmetrical round and has the diameter of 3mm, the thickness of the substrate is 0.3mm, placing the corundum plate and the substrate into a high-temperature heat treatment furnace to carry out annealing treatment on the substrate, wherein the annealing treatment process is stepped, and a stepped heat preservation process of 2 stages is carried out, the annealing temperature rise rate is 5 ℃/min, the final annealing temperature is 600 ℃, and the heat preservation time of the final annealing stage is 1h, so that the annealed substrate is obtained.
(2) Substrate reduction: placing the single annealed substrate obtained in the step (1) on a hollow frame, wherein the center of the substrate is concentric with the center point of the hollow frame, the surface of the substrate A faces downwards, lowering the hollow frame into a reduction tank, filling hydrogen peroxide with the purity of 95-98% in the reduction tank, immersing the substrate in the hydrogen peroxide, and driving the hollow frame to rotate and spin-wash the substrate around the center of the circle in a circumferential manner, wherein the rotation rate of the spin-wash is 25rap/min, the spin-wash time is 2min, the water temperature of the spin-wash is 20 ℃, then performing spray-wash on the substrate, and performing the reciprocating 3 times of the spin-wash and spray-wash operation to obtain the reduced substrate; the spray rinsing is to use an atomized water gun to spray rinse the surface A of the substrate to clean impurities, and the spray rinsing medium is high-purity deionized water.
(3) Activating a substrate: purging the reduced substrate obtained in the step (2) by using a high-pressure air gun, wherein the air gun adopts high-purity nitrogen as a purging medium, then the substrate is placed on a spin-coating instrument, the A surface of the substrate faces upwards, the center of the circle of the substrate is concentric with the axis of a rotating shaft of the spin-coating instrument, the spin-coating instrument drives the substrate to rotate at a high speed, the rotation is divided into three stages, the rotation speed of the first stage is 200rap/min, the rotation time is 30s, the rotation speed of the second stage is 1000rap/min, the rotation time is 20s, the rotation speed of the third stage is 3000rap/min, and the rotation time is 10s; respectively titrating an activating solution to the surface A of the substrate in a high-speed rotation state in each stage, wherein the activating solution is high-purity absolute alcohol and 98% concentrated nitric acid with the volume ratio of 2:1, the titration unit in each stage is 2ml, and then spraying and washing the substrate to obtain an activated substrate; the spray washing is to spray wash the surface A of the substrate by using an atomized water gun to clean impurities, and the spray washing medium is high-purity deionized water.
(4) Precursor preparation: preparing 30ml of initial solution, wherein the initial solution is a mixed solution of isopropanol and high-purity deionized water with a volume ratio of 1:7, sequentially adding manganese nitrate, lanthanum nitrate, calcium nitrate and strontium chloride into the initial solution, dropwise adding 3ml of ethylene glycol, adding citric acid, wherein the concentration ratio of acid radical ions to metal ions is 2:1, dropwise adding 0.2ml of monoethanolamine to obtain a precursor solution with a molar concentration of 0.1mol/L, placing the precursor solution on a stirrer for magnetic stirring, wherein the magnetic stirring rate is 200rap/min, the stirring time is 2h, the stirring temperature is 20 ℃, and the precursor solution with a uniformly dispersed medium is obtained, the dynamic viscosity of the precursor solution is 0.55 Mpa.S, and the pH value is 0.5.
(5) Precursor purification: filtering a precursor solution with uniformly dispersed medium by an organic nylon filter head with the aperture of 0.1mm, then placing the precursor solution in a vacuum chamber to carry out negative-pressure defoaming operation, wherein the defoaming vacuum degree is 0.5KPa, the defoaming time is 0.5h, the defoaming environment temperature is 20 ℃, then placing the precursor solution in a sealed chamber to carry out aging operation, the aging time is 6h, and the aging environment temperature is 15 ℃, thus obtaining the layered and homogenized precursor solution;
(6) Spin coating of a substrate: placing the activated substrate obtained in the step (3) on a spin coater, wherein the surface A of the substrate faces upwards, the center of the circle of the substrate is concentric with the axis of a rotating shaft of the spin coater, titrating the surface A of the substrate with 0.5ml of the layered homogenized precursor solution obtained in the step (5) before the spin coater is started, starting the spin coater to drive the substrate to rotate at high speed, and dividing the high-speed rotation into three stages, wherein the rotation rate of the first stage is 300rap/min, the rotation time duration is 5s, the rotation rate of the second stage is 1100rap/min, the rotation time duration is 5s, the rotation rate of the third stage is 3400rap/min, and the rotation time duration is 15s, so as to obtain the substrate coated with the liquid film;
(7) Substrate heat treatment: transferring the coated liquid film substrate obtained in the step (6) to a heat treatment table, attaching the surface B of the substrate to a table top, performing step heat treatment on the substrate and the liquid film coated on the surface A of the substrate, wherein the step heat treatment procedure comprises the steps of heat preservation at 50 ℃ for 10min in the first stage, heat preservation at 95 ℃ for 10min in the second stage, heat preservation at 265 ℃ for 10min in the third stage, obtaining a substrate in an amorphous film layer, and purging the film layer through an ear washing ball;
(8) Repeating the steps (6) and (7) for 3 times to obtain an amorphous film with complete micro-morphology and controllable film thickness, wherein the film thickness is 100nm;
(9) Film sintering: and (3) placing the amorphous film obtained in the step (8) in a muffle furnace to carry out sintering operation, wherein the heating and cooling rates of the sintering operation are both 2 ℃/min, the final sintering temperature is 550 ℃, and the heat preservation time of the final sintering stage is 1h to obtain the rare earth manganese oxide film.
The operating environment in the steps (2) - (8) is a glove box environment, wherein the oxygen content of the glove box environment is less than or equal to 0.1ppm, and the water content of the glove box environment is less than or equal to 0.1ppm.
The TCR of the rare earth manganese oxide film obtained by the embodiment reaches 10.03294%/K；T MI Reach 270.135K, and are in a range close to room temperature; the surface roughness of the rare earth manganese oxide film is less than or equal to 273nm, and the surface area of the rare earth manganese oxide film is 20 to 650mm 2 。
Example 2
(1) And (3) substrate high-temperature annealing: placing a single substrate of a high-purity silicon substrate on a corundum plate, wherein the contact surface of the substrate and the corundum plate is defined as a substrate B surface, the contact surface of the substrate, which is not in contact with the corundum plate, is defined as a substrate A surface, the substrate is highly symmetrical round, the diameter of the substrate is 9mm, the thickness of the substrate is 1.1mm, and placing the corundum plate and the substrate into a high-temperature heat treatment furnace to carry out annealing treatment on the substrate to obtain an annealed substrate; the annealing treatment process is in a step shape, and a step-shaped heat preservation process with 3 stages is carried out, wherein the annealing temperature rise rate is 8 ℃/min, the final annealing temperature is 950 ℃, and the heat preservation time of the final annealing stage is 4h.
(2) Substrate reduction: placing the single annealed substrate obtained in the step (1) on a hollow frame, wherein the center of the substrate is concentric with the center point of the hollow frame, the surface of the substrate A faces downwards, lowering the hollow frame into a reduction tank, filling hydrogen peroxide with the purity of 95-98% in the reduction tank, immersing the substrate in the hydrogen peroxide, and driving the hollow frame to rotate and spin-wash the substrate around the center of the circle in a circumferential manner, wherein the rotation rate of the spin-wash is 37rap/min, the spin-wash time is 9min, the water temperature of the spin-wash is 22 ℃, then performing spray-wash on the substrate, and performing the reciprocating 3 times of the spin-wash and spray-wash operation to obtain the reduced substrate; the spray washing is to spray wash the surface A of the substrate by using an atomized water gun to clean impurities, and the spray washing medium is high-purity deionized water.
(3) Activating a substrate: purging the reduced substrate obtained in the step (2) by using a high-pressure air gun, wherein the air gun uses high-purity nitrogen as a purging medium, then the substrate is placed on a spin-coating instrument, the A surface of the substrate faces upwards, the center of the circle of the substrate is concentric with the axis of a rotating shaft of the spin-coating instrument, the spin-coating instrument drives the substrate to rotate at a high speed, the rotation is divided into three stages, the rotation speed of the first stage is 500rap/min, the rotation time is 45s, the rotation speed of the second stage is 1700rap/min, the rotation time is 30s, the rotation speed of the third stage is 4500rap/min, and the rotation time is 15s; respectively titrating an activating solution on the surface A of the substrate in a high-speed rotation state in each stage, wherein the activating solution is high-purity absolute alcohol and 98% concentrated nitric acid with the volume ratio of 5:1, the titration unit in each stage is 3ml, and then spraying and washing the substrate to obtain an activated substrate; the spray washing is to spray wash the surface A of the substrate by using an atomized water gun to clean impurities, and the spray washing medium is high-purity deionized water.
(4) Precursor preparation: preparing 55ml of initial solution, wherein the initial solution is a mixed solution of isopropanol and high-purity deionized water with a volume ratio of 1:7, sequentially adding manganese nitrate, lanthanum nitrate, calcium nitrate and strontium chloride into the initial solution, dropwise adding 9ml of ethylene glycol, adding citric acid, wherein the concentration ratio of acid radical ions to metal ions is 4:1, dropwise adding 4ml of monoethanolamine to obtain a precursor solution with the molar concentration of 1.2mol/L, placing the precursor solution on a stirrer for magnetic stirring, wherein the magnetic stirring speed is 350rap/min, the stirring time is 7h, the stirring temperature is 45 ℃, and the precursor solution with uniformly dispersed media is obtained, the dynamic viscosity of the precursor solution is 1.55Mpa · S, and the pH value is 2.
(5) Precursor purification: enabling a precursor solution with a uniformly dispersed medium to flow through an organic nylon filter head with the aperture of 0.2mm for filtering, then placing the precursor solution in a vacuum chamber for negative-pressure defoaming operation, wherein the defoaming vacuum degree is 24MPa, the defoaming time is 2h, the defoaming environment temperature is 22 ℃, then placing the precursor solution in a sealed chamber for aging operation, the aging time is 22h, and the aging environment temperature is 17 ℃ to obtain a homogenized precursor solution;
(6) Spin coating of a substrate: placing the activated substrate obtained in the step (3) on a spin coater, wherein the A surface of the substrate faces upwards, the center of the circle of the substrate is concentric with the axis position of a rotating shaft of the spin coater, titrating the A surface of the substrate with 5ml of layered homogenized precursor solution obtained in the step (5) before the spin coater is not started, starting the spin coater to drive the substrate to rotate at a high speed, wherein the high speed rotation is divided into three stages, the rotation rate of the first stage is 500rap/min, the rotation time duration of the first stage is 10s, the rotation rate of the second stage is 1700rap/min, the rotation time duration of the second stage is 12s, the rotation rate of the third stage is 5200rap/min, and the rotation time duration of the third stage is 35s, so that the substrate coated with the liquid film is obtained;
(7) Substrate heat treatment: transferring the coated liquid film substrate obtained in the step (6) to a heat treatment table, attaching the B surface of the substrate to a table top, and performing step heat treatment on the substrate and the liquid film coated on the A surface of the substrate, wherein the step heat treatment procedure comprises the steps of heat preservation at 57 ℃ for 15min in the first stage, heat preservation at 135 ℃ for 12min in the second stage and heat preservation at 300 ℃ for 12min in the third stage to obtain the substrate in the form of an amorphous film layer, and purging the film layer through an ear washing ball;
(8) Repeating the steps (6) and (7) for 6 times to obtain an amorphous film with complete micro-morphology and controllable film thickness, wherein the film thickness is 2 microns;
(9) Film sintering: and (5) placing the amorphous film obtained in the step (8) in a muffle furnace to carry out sintering operation, wherein the heating and cooling rates of the sintering operation are both 11 ℃/min, the final sintering temperature is 900 ℃, and the heat preservation time of the final sintering stage is 3h to obtain the rare earth manganese oxide film.
The operating environment in the steps (2) - (8) is a glove box environment, wherein the oxygen content of the glove box environment is less than or equal to 0.1ppm, and the water content of the glove box environment is less than or equal to 0.1ppm.
The TCR value of the rare earth manganese oxide film obtained in the embodiment reaches 20.2395%/K; t is MI Reach 252.4115K, and are in a range close to room temperature; the surface roughness of the rare earth manganese oxide film is less than or equal to 91nm, and the surface area of the rare earth manganese oxide film is 50-480 mm 2 。
Example 3
(1) And (3) substrate high-temperature annealing: placing a single substrate of a high-purity silicon substrate on a corundum plate, wherein the contact surface of the substrate and the corundum plate is defined as a substrate B surface, the contact surface of the substrate, which is not in contact with the corundum plate, is defined as a substrate A surface, the substrate is highly symmetrical round, the diameter of the substrate is 15mm, the thickness of the substrate is 2mm, and placing the corundum plate and the substrate into a high-temperature heat treatment furnace to carry out annealing treatment on the substrate to obtain an annealed substrate; the annealing treatment process is in a step shape, and a 4-step heat preservation process is carried out, wherein the annealing temperature rise rate is 10 ℃/min, the final annealing temperature is 1300 ℃, and the heat preservation time of the final annealing stage is 8h.
(2) Substrate reduction: placing the single annealed substrate obtained in the step (1) on a hollow frame, wherein the center of the circle of the substrate is concentric with the center point of the hollow frame, the surface of the substrate A faces downwards, lowering the hollow frame into a reduction tank, filling hydrogen peroxide with the purity of 95-98% in the reduction tank, immersing the substrate in the hydrogen peroxide, driving the hollow frame to drive the substrate to rotate and spin-wash circumferentially around the center of the circle of the hollow frame, wherein the rotation rate of the spin-wash is 50rap/min, the spin-wash time is 15min, the water temperature of the spin-wash is 25 ℃, then spraying the substrate, and performing the spin-wash and the spray-wash operations for 4 times to obtain the reduced substrate; the spray washing is to spray wash the surface A of the substrate by using an atomized water gun to clean impurities, and the spray washing medium is high-purity deionized water.
(3) Activating a substrate: purging the reduced substrate obtained in the step (2) by using a high-pressure air gun, wherein the air gun adopts high-purity nitrogen as a purging medium, then the substrate is placed on a spin-coating instrument, the A surface of the substrate faces upwards, the center of the circle of the substrate is concentric with the axis position of a rotating shaft of the spin-coating instrument, the spin-coating instrument drives the substrate to rotate at a high speed, the rotation is divided into three stages, the rotation speed of the first stage is 800rap/min, the rotation time is 60s, the rotation speed of the second stage is 2500rap/min, the rotation time is 40s, the rotation speed of the third stage is 6000rap/min, and the rotation time is 20s; respectively titrating an activating solution to the surface A of the substrate in a high-speed rotation state in each stage, wherein the activating solution is high-purity absolute alcohol and 98% concentrated nitric acid with the volume ratio of 10; the spray washing is to spray wash the surface A of the substrate by using an atomized water gun to clean impurities, and the spray washing medium is high-purity deionized water.
(4) Precursor preparation: preparing 85ml of initial solution, wherein the initial solution is a mixed solution of isopropanol and high-purity deionized water with a volume ratio of 4:1, sequentially adding manganese nitrate, lanthanum nitrate, calcium nitrate and strontium chloride into the initial solution, dropwise adding 15ml of ethylene glycol, adding citric acid, wherein the concentration ratio of acid radical ions to metal ions is 6:1, dropwise adding 8ml of monoethanolamine to obtain a precursor solution with the molar concentration of 2.4mol/L, placing the precursor solution on a stirrer to perform magnetic stirring, wherein the magnetic stirring rate is 500rap/min, the stirring time is 12h, the stirring temperature is 75 ℃, and the precursor solution with uniformly dispersed media is obtained, the dynamic viscosity of the precursor solution is 2.75 Mpa.S, and the pH value is 4.
(5) Precursor purification: enabling a precursor solution with a uniformly dispersed medium to flow through an organic nylon filter head with the aperture of 0.35mm for filtering, then placing the precursor solution in a vacuum chamber for negative-pressure defoaming operation, wherein the defoaming vacuum degree is 4MPa, the defoaming time is 3h, the defoaming environment temperature is 25 ℃, then placing the precursor solution in a sealed chamber for aging operation, the aging time is 48h, and the aging environment temperature is 20 ℃, so as to obtain a homogenized precursor solution;
(6) Spin coating of a substrate: placing the activated substrate obtained in the step (3) on a spin coater, wherein the A surface of the substrate faces upwards, the center of the circle of the substrate is concentric with the axis position of a rotating shaft of the spin coater, titrating the A surface of the substrate with 9ml of layered homogenized precursor solution obtained in the step (5) before the spin coater is not started, starting the spin coater to drive the substrate to rotate at a high speed, wherein the high speed rotation is divided into three stages, the first stage rotation speed is 700rap/min, the rotation time duration is 15s, the second stage rotation speed is 2350rap/min, the rotation time duration is 20s, the third stage rotation speed is 7200rap/min, and the rotation time duration is 55s, so that the substrate coated with the liquid film is obtained;
(7) Substrate heat treatment: transferring the coated liquid film substrate obtained in the step (6) to a heat treatment table, attaching the surface B of the substrate to a table top, performing step heat treatment on the substrate and the liquid film coated on the surface A of the substrate, wherein the step heat treatment procedure comprises the steps of heat preservation at 65 ℃ for 20min in the first stage, heat preservation at 185 ℃ for 15min in the second stage, heat preservation at 340 ℃ for 10 to 15min in the third stage, obtaining a substrate in an amorphous film layer, and purging the film layer through an ear washing ball;
(8) Repeating the steps (6) and (7) for 10 times to obtain an amorphous film with complete micro-morphology and controllable film thickness, wherein the film thickness is 5 mu m;
(9) Film sintering: and (3) placing the amorphous film obtained in the step (8) in a muffle furnace to carry out sintering operation, wherein the heating and cooling rates of the sintering operation are both 20 ℃/min, the final sintering temperature is 1250 ℃, and the heat preservation time of the final sintering stage is 6h, so that the rare earth manganese oxide film is obtained.
The operating environment in the steps (2) - (8) is a glove box environment, wherein the oxygen content of the glove box environment is less than or equal to 0.1ppm, and the water content of the glove box environment is less than or equal to 0.1ppm.
TCR of the rare earth manganese oxide film obtained in this exampleReach 12.76711%/K; t is MI Reach 263.3932K, and are in a range close to room temperature; the surface roughness of the rare earth manganese oxide film is less than or equal to 50nm, and the surface area of the rare earth manganese oxide film is 20-720 mm 2 。
Example 4
(1) And (3) substrate high-temperature annealing: placing a single-wafer substrate of a high-purity quartz plate on a corundum plate, defining the contact surface of the substrate and the corundum plate as a substrate B surface, defining the contact surface of the substrate, which is not in contact with the corundum plate, as a substrate A surface, wherein the substrate is highly symmetrical round, the diameter of the substrate is 3mm, and the thickness of the substrate is 0.3mm, and placing the corundum plate and the substrate into a high-temperature heat treatment furnace to carry out annealing treatment on the substrate to obtain an annealed substrate; the annealing treatment process is in a step shape, and a step-shaped heat preservation process with more than 2 stages is carried out, the annealing temperature rise rate is 5 ℃/min, the final annealing temperature is 600 ℃, and the heat preservation time of the final annealing stage is 1h.
(2) Substrate reduction: placing the single annealed substrate obtained in the step (1) on a hollow frame, wherein the center of the substrate is concentric with the center point of the hollow frame, the surface of the substrate A faces downwards, lowering the hollow frame into a reduction tank, filling hydrogen peroxide with the purity of 95-98% in the reduction tank, immersing the substrate in the hydrogen peroxide, and driving the hollow frame to rotate and spin-wash the substrate around the center of the circle in a circumferential manner, wherein the rotation rate of the spin-wash is 25rap/min, the spin-wash time is 2min, the water temperature of the spin-wash is 20 ℃, then performing spray-wash on the substrate, and performing the reciprocating 3 times of the spin-wash and spray-wash operation to obtain the reduced substrate; the spray rinsing is to use an atomized water gun to spray rinse the surface A of the substrate to clean impurities, and the spray rinsing medium is high-purity deionized water.
(3) Activating a substrate: purging the reduced substrate obtained in the step (2) by using a high-pressure air gun, wherein the air gun adopts high-purity nitrogen as a purging medium, then the substrate is placed on a spin-coating instrument, the A surface of the substrate faces upwards, the center of the circle of the substrate is concentric with the axis of a rotating shaft of the spin-coating instrument, the spin-coating instrument drives the substrate to rotate at a high speed, the rotation is divided into three stages, the rotation speed of the first stage is 200rap/min, the rotation time is 30s, the rotation speed of the second stage is 1000rap/min, the rotation time is 20s, the rotation speed of the third stage is 3000rap/min, and the rotation time is 10s; in each stage, respectively titrating the surface A of the substrate in a high-speed rotation state with an activating solution, wherein the activating solution is high-purity absolute alcohol and experimental pure hydrofluoric acid with the volume ratio of 3:1. The titration unit of each stage is 2ml, and then the substrate is sprayed and washed to obtain an activated substrate; the spray washing is to spray wash the surface A of the substrate by using an atomized water gun to clean impurities, and the spray washing medium is high-purity deionized water.
(4) Precursor preparation: preparing 30ml of initial solution, wherein the initial solution is a mixed solution of methanol and high-purity deionized water with a volume ratio of 1:7, sequentially adding manganese nitrate, lanthanum nitrate, calcium nitrate and strontium chloride into the initial solution, dropwise adding 3ml of ethylene glycol, adding citric acid, wherein the concentration ratio of acid radical ions to metal ions is 2:1, dropwise adding 0.2ml of ethanolamine to obtain a precursor solution with the molar concentration of 0.1mol/L, placing the precursor solution on a stirrer for magnetic stirring, wherein the magnetic stirring speed is 200rap/min, the stirring time is 2h, the stirring temperature is 20 ℃, and the precursor solution with uniformly dispersed media is obtained, the dynamic viscosity of the precursor solution is 0.55 Mpa.S, and the pH value is 0.5.
(5) Precursor purification: filtering a precursor solution with uniformly dispersed medium by an organic nylon filter head with the aperture of 0.1mm, then placing the precursor solution in a vacuum chamber to carry out negative-pressure defoaming operation, wherein the defoaming vacuum degree is 0.5KPa, the defoaming time is 0.5h, the defoaming environment temperature is 20 ℃, then placing the precursor solution in a sealed chamber to carry out aging operation, the aging time is 6h, and the aging environment temperature is 15 ℃, thus obtaining the layered and homogenized precursor solution;
(6) Spin coating of a substrate: placing the activated substrate obtained in the step (3) on a spin coater, wherein the A surface of the substrate faces upwards, the center of the circle of the substrate is concentric with the axis position of a rotating shaft of the spin coater, titrating the A surface of the substrate with 0.5ml of the layered homogenized precursor solution obtained in the step (5) before the spin coater is not started, starting the spin coater to drive the substrate to rotate at a high speed, wherein the high speed rotation is divided into three stages, the rotation rate of the first stage is 300rap/min, the rotation time duration is 5s, the rotation rate of the second stage is 1100rap/min, the rotation time duration is 5s, the rotation rate of the third stage is 3400rap/min, and the rotation time duration is 15s, so that the substrate coated with the liquid film is obtained;
(7) Substrate heat treatment: transferring the coated liquid film substrate obtained in the step (6) to a heat treatment table, attaching the surface B of the substrate to a table top, performing step heat treatment on the substrate and the liquid film coated on the surface A of the substrate, wherein the step heat treatment procedure comprises the steps of heat preservation at 50 ℃ for 10min in the first stage, heat preservation at 95 ℃ for 10min in the second stage, heat preservation at 265 ℃ for 10min in the third stage, obtaining a substrate in an amorphous film layer, and purging the film layer through an ear washing ball;
(8) Repeating the steps (6) and (7) for 3 times to obtain an amorphous film with complete microscopic appearance and controllable film thickness, wherein the film thickness is 100nm;
(9) Film sintering: and (3) placing the amorphous film obtained in the step (8) in a muffle furnace to carry out sintering operation, wherein the heating and cooling rates of the sintering operation are both 2 ℃/min, the final sintering temperature is 550 ℃, and the heat preservation time of the final sintering stage is 1h to obtain the rare earth manganese oxide film.
The operating environment in the steps (2) - (8) is a glove box environment, wherein the oxygen content of the glove box environment is less than or equal to 0.1ppm, and the water content of the glove box environment is less than or equal to 0.1ppm.
The surface area of the rare earth manganese oxide film obtained in the embodiment is 700 to 590mm 2 。
Example 5
(1) And (3) substrate high-temperature annealing: placing a single-wafer substrate of a high-purity quartz plate on a corundum plate, wherein the contact surface of the substrate and the corundum plate is defined as a substrate B surface, the contact surface of the substrate, which is not in contact with the corundum plate, is defined as a substrate A surface, the substrate is highly symmetrical round, the diameter of the substrate is 15mm, the thickness of the substrate is 2mm, and placing the corundum plate and the substrate into a high-temperature heat treatment furnace to carry out annealing treatment on the substrate to obtain an annealed substrate; the annealing treatment process is in a step shape, and a 4-step heat preservation process is carried out, wherein the annealing temperature rise rate is 10 ℃/min, the final annealing temperature is 1300 ℃, and the heat preservation time of the final annealing stage is 8h.
(2) Substrate reduction: placing the single annealed substrate obtained in the step (1) on a hollow frame, wherein the center of the circle of the substrate is concentric with the center point of the hollow frame, the surface of the substrate A faces downwards, lowering the hollow frame into a reduction tank, filling hydrogen peroxide with the purity of 95-98% in the reduction tank, immersing the substrate in the hydrogen peroxide, driving the hollow frame to drive the substrate to rotate and spin-wash circumferentially around the center of the circle of the hollow frame, wherein the rotation rate of the spin-wash is 50rap/min, the spin-wash time is 15min, the water temperature of the spin-wash is 25 ℃, then spraying the substrate, and performing the spin-wash and the spray-wash operations for 4 times to obtain the reduced substrate; the spray washing is to spray wash the surface A of the substrate by using an atomized water gun to clean impurities, and the spray washing medium is high-purity deionized water.
(3) Activating a substrate: purging the reduced substrate obtained in the step (2) by using a high-pressure air gun, wherein the air gun adopts high-purity nitrogen as a purging medium, then the substrate is placed on a spin-coating instrument, the surface A of the substrate faces upwards, the center of the circle of the substrate is concentric with the axis of a rotating shaft of the spin-coating instrument, the spin-coating instrument drives the substrate to rotate at a high speed, the rotation is divided into three stages, the rotation speed of the first stage is 800rap/min, the rotation time is 60s, the rotation speed of the second stage is 2500rap/min, the rotation time is 40s, the rotation speed of the third stage is 6000rap/min, and the rotation time is 20s; in each stage, respectively titrating an activating solution to the surface A of the substrate in a high-speed rotation state, wherein the activating solution is high-purity absolute alcohol and experimental pure hydrofluoric acid with the volume ratio of 15. Titrating the substrate by 5ml at each stage, and then spraying and washing the substrate to obtain an activated substrate; the spray washing is to spray wash the surface A of the substrate by using an atomized water gun to clean impurities, and the spray washing medium is high-purity deionized water.
(4) Precursor preparation: preparing 85ml of initial solution, wherein the initial solution is a mixed solution of 4:1 volume ratio ethanol and high-purity deionized water, sequentially adding manganese nitrate, lanthanum nitrate, calcium nitrate and strontium chloride into the initial solution, dropwise adding 15ml of ethylene glycol, adding citric acid, wherein the concentration ratio of acid radical ions to metal ions is 6:1, dropwise adding 8ml of ethanolamine to obtain a precursor solution with the molar concentration of 2.4mol/L, placing the precursor solution on a stirrer for magnetic stirring, wherein the magnetic stirring speed is 500rap/min, the stirring time is 12h, the stirring temperature is 75 ℃, and the precursor solution with uniformly dispersed media is obtained, the dynamic viscosity of the precursor solution is 2.75Mpa · S, and the pH value is 4.
(5) Precursor purification: enabling a precursor solution with a uniformly dispersed medium to flow through an organic nylon filter head with the aperture of 0.35mm for filtering, then placing the precursor solution in a vacuum chamber for negative-pressure defoaming operation, wherein the defoaming vacuum degree is 4MPa, the defoaming duration is 3h, the defoaming environment temperature is 25 ℃, then placing the precursor solution in a sealed chamber for aging operation, the aging duration is 48h, and the aging environment temperature is 20 ℃, so as to obtain a layered and homogenized precursor solution;
(6) Spin coating of a substrate: placing the activated substrate obtained in the step (3) on a spin coater, wherein the A surface of the substrate faces upwards, the center of the circle of the substrate is concentric with the axis position of a rotating shaft of the spin coater, titrating the A surface of the substrate with 9ml of layered homogenized precursor solution obtained in the step (5) before the spin coater is not started, starting the spin coater to drive the substrate to rotate at a high speed, wherein the high speed rotation is divided into three stages, the first stage rotation speed is 700rap/min, the rotation time duration is 15s, the second stage rotation speed is 2350rap/min, the rotation time duration is 20s, the third stage rotation speed is 7200rap/min, and the rotation time duration is 55s, so that the substrate coated with the liquid film is obtained;
(7) Substrate heat treatment: transferring the coated liquid film substrate obtained in the step (6) to a heat treatment table, attaching the B surface of the substrate to a table top, and performing step heat treatment on the substrate and the liquid film coated on the A surface of the substrate, wherein the step heat treatment procedure comprises the steps of heat preservation at 65 ℃ for 20min at the first stage, heat preservation at 185 ℃ for 15min at the second stage and heat preservation at 340 ℃ for 15min at the third stage to obtain a substrate in an amorphous film layer, and purging the film layer through an ear washing ball;
(8) Repeating the steps (6) and (7) for 10 times to obtain an amorphous film with complete micro-morphology and controllable film thickness, wherein the film thickness is 5 mu m; the operating environment in the steps (2) - (8) is a glove box environment, wherein the oxygen content of the glove box environment is less than or equal to 0.1ppm, and the water content of the glove box environment is less than or equal to 0.1ppm.
(9) Film sintering: and (3) placing the amorphous film obtained in the step (8) in a muffle furnace to carry out sintering operation, wherein the heating and cooling rates of the sintering operation are both 20 ℃/min, the final sintering temperature is 1250 ℃, and the heat preservation time of the final sintering stage is 6h, so that the rare earth manganese oxide film is obtained.
The surface area of the rare earth manganese oxide film obtained in the embodiment is 70-695mm 2 。
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the rare earth manganese oxide film for near room temperature infrared imaging is characterized by comprising the following steps:
(1) And (3) substrate high-temperature annealing: placing a monolithic substrate on a corundum plate, wherein the contact surface of the substrate and the corundum plate is defined as a substrate B surface, the contact surface of the substrate, which is not in contact with the corundum plate, is defined as a substrate A surface, the substrate is highly symmetrical round, the diameter of the substrate is 3-15mm, and the thickness of the substrate is 0.3-2mm, and placing the corundum plate and the substrate into a high-temperature heat treatment furnace to carry out annealing treatment on the substrate to obtain an annealed substrate;
(2) Substrate reduction: placing the single annealed substrate obtained in the step (1) on a hollow frame, wherein the center of the substrate is concentric with the center point of the hollow frame, the surface of the substrate A faces downwards, lowering the hollow frame into a reduction tank, hydrogen peroxide with the purity of 95-98% is filled in the reduction tank, immersing the substrate into the hydrogen peroxide, driving the hollow frame to drive the substrate to rotate and spin-wash circumferentially around the center of the circle, then performing spray-washing on the substrate, and performing reciprocating 3~4 times of the spin-washing and spray-washing operations to obtain the reduced substrate, wherein the original impurities and pollutants on the substrate can be removed by reduction, and the roughness of the surface of the substrate is greatly reduced;
(3) Activating a substrate: purging the reduced substrate obtained in the step (2) by using a high-pressure air gun, wherein the air gun uses high-purity nitrogen as a purging medium, then the substrate is placed on a spin-coating instrument, the surface of the substrate A faces upwards, the center of the substrate is concentric with the axis of a rotating shaft of the spin-coating instrument, the spin-coating instrument drives the substrate to rotate at a high speed, the rotation is divided into three stages, an activating solution is titrated on the surface of the substrate A in a high-speed rotation state in each stage, the titration unit of each stage is 2-5 ml, and then the substrate is subjected to spray cleaning to obtain an activated substrate;
(4) Precursor preparation: preparing 30-85ml of initial solution, wherein the initial solution is a mixed solution of alcohols and high-purity deionized water with a volume ratio of 1-4, adding manganese nitrate, lanthanum nitrate, calcium nitrate and strontium chloride into the initial solution in sequence, dropwise adding 3-15ml of ethylene glycol, adding citric acid, dropwise adding 0.2-8ml of amines, obtaining a precursor solution with a molar concentration of 0.1-2.4mol/L, placing the precursor solution on a stirrer, and magnetically stirring to obtain a precursor solution with a uniformly dispersed medium;
(5) Precursor purification: enabling a precursor solution with a uniformly dispersed medium to flow through an organic nylon filter head with the aperture of 0.1-0.35mm for filtration, then placing the precursor solution in a vacuum cavity for negative-pressure defoaming operation, wherein the defoaming vacuum degree is 0.5 KPa-4 MPa, the defoaming time is 0.5-3h, the defoaming environment temperature is 20-25 ℃, then placing the precursor solution in a sealed cavity for aging operation, the aging time is 6-48h, and the aging environment temperature is 15-20 ℃, so as to obtain a layered and homogenized precursor solution;
(6) Spin coating of a substrate: placing the activated substrate obtained in the step (3) on a spin coater, enabling the surface A of the substrate to face upwards, enabling the center of the circle of the substrate to be concentric with the axis position of a rotating shaft of the spin coater, titrating the layered homogenized precursor solution obtained in the step (5) on the surface A of the substrate before starting the spin coater, wherein the titration unit is 0.5-9ml, and starting the spin coater to drive the substrate to rotate at a high speed to obtain the substrate coated with the liquid film;
(7) Substrate heat treatment: transferring the coated liquid film substrate obtained in the step (6) to a heat treatment table, attaching the surface B of the substrate to the table top, performing step heat treatment on the substrate and the liquid film coated on the surface A of the substrate to obtain a substrate in an amorphous film layer, and purging the film layer through an aurilave;
(8) Repeating the steps (6) and (7) for 3 to 10 times to obtain an amorphous film with complete micro-morphology and controllable film thickness;
(9) Film sintering: and (3) placing the amorphous film obtained in the step (8) in a muffle furnace to carry out sintering operation, wherein the heating and cooling rates of the sintering operation are 2-20 ℃/min, the final sintering temperature is 550-1250 ℃, and the heat preservation time of the final sintering stage is 1-6 h to obtain the rare earth manganese oxide film.
2. The method for preparing a rare earth manganese oxide film for near-room temperature infrared imaging according to claim 1, wherein the method comprises the following steps: the annealing treatment process in the step (1) is in a step type, and a step type heat preservation process with more than 2 stages is carried out, wherein the annealing temperature rise rate is 5 to 10 ℃/min, the final annealing temperature is 600 to 1300 ℃, and the heat preservation time of the final annealing stage is 1 to 8h.
3. The method for preparing a rare earth manganese oxide film for near-room temperature infrared imaging according to claim 1, wherein the method comprises the following steps: the spin-washing in the step (2) is carried out at a rotation speed of 25 to 50rap/min for 2 to 15min and at a water temperature of 20 to 25 ℃, the spray-washing in the steps (2) and (3) is carried out by spraying the surface A of the substrate with an atomized water gun to clean impurities, and the spray-washing medium is high-purity deionized water.
4. The method for preparing a rare earth manganese oxide film for near-room temperature infrared imaging according to claim 1, wherein the method comprises the following steps: the three stages of rotation described in step (3) are specifically: the rotation speed in the first stage is 200 to 800rap/min, the rotation time is 30 to 60s, the rotation speed in the second stage is 1000 to 2500rap/min, the rotation time is 20 to 40s, the rotation speed in the third stage is 3000 to 6000rap/min, and the rotation time is 10 to 20s; the activating solution in the step (3) is high-purity anhydrous alcohol and 98% concentrated nitric acid in a volume ratio of 2 to 10, or high-purity anhydrous alcohol and experimental pure hydrofluoric acid in a volume ratio of 3 to 1 to 15.
5. The method for preparing the rare earth manganese oxide film for near-room temperature infrared imaging according to claim 1, wherein the method comprises the following steps: in the step (4), the magnetic stirring speed is 200-500rap/min, the stirring time is 2-12h, and the stirring temperature is 20-75 ℃.
6. The method for preparing a rare earth manganese oxide film for near-room temperature infrared imaging according to claim 1, wherein the method comprises the following steps: the high-speed rotation in the step (6) is divided into three stages, the rotation speed in the first stage is 300-700rap/min, the rotation time is 5-15s, the rotation speed in the second stage is 1100-2350rap/min, the rotation time is 5-20s, the rotation speed in the third stage is 3400-7200rap/min, and the rotation time is 15-55s.
7. The method for preparing the rare earth manganese oxide film for near-room temperature infrared imaging according to claim 1, wherein the method comprises the following steps: the step type heat treatment in the step (7) is carried out by carrying out heat preservation for 10 to 20min at 50 to 65 ℃ in the first stage, carrying out heat preservation for 10 to 15min at 95 to 185 ℃ in the second stage and carrying out heat preservation for 10 to 15min at 265 to 340 ℃ in the third stage.
8. The method for preparing a rare earth manganese oxide film for near-room temperature infrared imaging according to claim 1, wherein the method comprises the following steps: the operating environment in the steps (2) - (8) is a glove box environment, wherein the oxygen content of the glove box environment is less than or equal to 0.1ppm, and the water content of the glove box environment is less than or equal to 0.1ppm.
9. The method for preparing a rare earth manganese oxide film for near-room temperature infrared imaging according to claim 1, wherein the method comprises the following steps: the alcohols in the step (4) comprise isopropanol, methanol and ethanol, and the amines comprise monoethanolamine, diethanolamine and ethanolamine.
10. The method of preparing a rare earth manganese oxide film for near-room temperature infrared imaging according to any one of claims 1~9, comprising: the substrate is any one of a high-purity silicon substrate, a mica sheet, a high-purity quartz sheet and a sapphire sheet.
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| CN1887445A (en) * | 2005-06-30 | 2007-01-03 | 郑州大学 | Prepn process of magnesium alloy supported nanometer TiO2 photocatalyst film |
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