CN109097757B - Preparation method of praseodymium ion doped hafnium oxide ferroelectric film - Google Patents
Preparation method of praseodymium ion doped hafnium oxide ferroelectric film Download PDFInfo
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- CN109097757B CN109097757B CN201810813379.6A CN201810813379A CN109097757B CN 109097757 B CN109097757 B CN 109097757B CN 201810813379 A CN201810813379 A CN 201810813379A CN 109097757 B CN109097757 B CN 109097757B
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- hafnium oxide
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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
- C23C18/1204—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
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
Abstract
The invention discloses a preparation method of a praseodymium ion doped hafnium oxide ferroelectric film, which comprises the following steps: hafnium acetylacetonate and acetic acid were mixed, heated and stirred to clarify, and then cooled to room temperature to obtain a first solution. And sequentially adding praseodymium (III) nitrate hexahydrate and acetylacetone solution into the first solution, and then heating and stirring until the solution is clarified to obtain a second solution. And dripping the second solution on a platinum substrate to carry out N times of spin coating treatment operation, and then carrying out annealing operation to obtain the praseodymium ion doped hafnium oxide ferroelectric film, wherein N is a positive integer greater than or equal to 1. By implementing the embodiment of the invention, the praseodymium-doped hafnium oxide ferroelectric film can be prepared under the condition of not using other large-scale equipment such as a glove box, and the like, and the preparation method has the advantages of simple preparation process, low equipment cost and easy large-scale production.
Description
Technical Field
The invention relates to the technical field of ferroelectric film preparation, in particular to a preparation method of a praseodymium ion doped hafnium oxide ferroelectric film.
Background
Ferroelectric memories, which are one of the most promising new types of memories today, employ ferroelectric thin films as storage media. The traditional perovskite ferroelectric thin film material cannot meet the requirement of electronic devices for miniaturization development, so that the development of new storage medium materials is always focused on research subjects by various semiconductor forcing countries. The hafnium oxide ferroelectric film is a novel ferroelectric material which is perfectly compatible with the existing silicon process platform.
The inventor finds that the following technical problems exist in the preparation of the prior ferroelectric thin film in the process of implementing the invention: the existing processes for preparing hafnium oxide ferroelectric thin film materials mainly comprise an atomic layer deposition technology, a pulse laser deposition technology, a sputtering method and the like. The equipment and metal sources needed by the methods are expensive, the preparation process of the film is complex, and the preparation cost is high.
Disclosure of Invention
The embodiment of the invention provides a preparation method of a praseodymium ion doped hafnium oxide ferroelectric film, which can effectively solve the problems of complex preparation process and high preparation cost of the existing hafnium oxide ferroelectric film.
The embodiment of the invention provides a preparation method of a praseodymium ion doped hafnium oxide ferroelectric film, which comprises the following steps:
hafnium acetylacetonate and acetic acid were mixed, heated and stirred to clarify, and then cooled to room temperature to obtain a first solution.
And sequentially adding praseodymium (III) nitrate hexahydrate and acetylacetone solution into the first solution, and then heating and stirring until the solution is clarified to obtain a second solution.
And dripping the second solution on a platinum substrate to carry out N times of spin coating treatment operation, and then carrying out annealing operation to obtain the praseodymium ion doped hafnium oxide ferroelectric film. Wherein N is a positive integer greater than or equal to 1.
Further, the volume ratio of acetic acid to acetylacetone was 3: 2.
Further, the amount concentration of the metal ion species in the second solution was 0.1 mol/L, wherein the molar ratio of hafnium ions to praseodymium ions was 0.95: 0.05.
Further, the spin coating operation specifically comprises:
and dropwise adding the second solution on the platinum substrate, and carrying out spin coating for preset time by using a spin coater to obtain a first processed platinum substrate sample.
After the first processed platinum substrate sample was pyrolyzed and cooled, the spin-coating process operation was completed.
Further, after pyrolyzing and cooling the first processed platinum substrate sample, specifically:
and pyrolyzing the first processed platinum substrate sample in an air environment at the temperature of 150-350 ℃ for 5-10min, cooling to 150 ℃, and taking out.
Further, the annealing operation is specifically:
and annealing the platinum substrate subjected to the N times of spin coating processing operations at a first preset temperature, and then performing secondary annealing at a second preset temperature, wherein the first preset temperature is lower than the second preset temperature.
Further, the first preset temperature is 400 ℃, and the second preset temperature is 800 ℃.
According to the preparation method of the praseodymium ion doped hafnium oxide ferroelectric film provided by the embodiment of the invention, praseodymium (III) nitrate hexahydrate is used as a source of praseodymium metal ions, so that the praseodymium doped hafnium oxide ferroelectric film can be prepared under the condition that other large-scale equipment such as a glove box and the like are not used, the preparation process is simple, the equipment cost is low, and the large-scale production is easy.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing a praseodymium ion-doped hafnium oxide ferroelectric thin film according to an embodiment of the present invention.
Fig. 2 is a GIXRD pattern of a praseodymium ion-doped hafnium oxide ferroelectric thin film according to an embodiment of the present invention.
Fig. 3 shows a hysteresis loop and a capacitance-voltage curve of a praseodymium ion-doped hafnium oxide ferroelectric thin film according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Fig. 1 is a schematic flow chart of a method for preparing a praseodymium ion-doped hafnium oxide ferroelectric thin film according to an embodiment of the present invention, including:
and S101, mixing hafnium acetylacetonate and acetic acid, heating and stirring until the mixture is clear, and then cooling to room temperature to obtain a first solution.
And S102, adding praseodymium (III) nitrate hexahydrate and acetylacetone solution into the first solution in sequence, and then heating and stirring until the solution is clarified to obtain a second solution.
S103, dripping the second solution on the platinum substrate to carry out N times of spin coating treatment operation, and then carrying out annealing operation to obtain the praseodymium ion doped hafnium oxide ferroelectric film. Wherein N is a positive integer greater than or equal to 1.
Preferably, the volume ratio of acetic acid to acetylacetone is 3: 2.
Preferably, the amount of the metal ion species in the second solution is 0.1 mol/L, wherein the molar ratio of hafnium ions to praseodymium ions is 0.95: 0.05.
Preferably, the spin coating operation specifically comprises:
and dropwise adding the second solution on the platinum substrate, and carrying out spin coating for preset time by using a spin coater to obtain a first processed platinum substrate sample.
After the first processed platinum substrate sample was pyrolyzed and cooled, the spin-coating process operation was completed.
Preferably, after pyrolyzing and cooling the first processed platinum substrate sample, the method specifically comprises the following steps:
and (3) pyrolyzing the first processed platinum substrate sample at 150-350 ℃ for 5-10min in an air environment, cooling to 150 ℃, and taking out.
Preferably, the annealing operation is specifically:
and annealing the platinum substrate which finishes the N times of spin coating processing operations at a first preset temperature for 300 seconds, and then annealing at a second preset temperature for 100-150 seconds, wherein the first preset temperature is lower than the second preset temperature.
Preferably, the first preset temperature is 400 ℃ and the second preset temperature is 800 ℃.
In order to better illustrate the flow of the preparation process of the present invention, the process of the present invention is described in detail below:
step a, 0.5461835g of hafnium acetylacetonate was weighed using an analytical balance and poured into a beaker, and 6ml of acetic acid was further added. Sealing the beaker, and placing the beaker in a constant-temperature magnetic stirring water bath kettle for heating and stirring, wherein the heating temperature is 60 ℃. After stirring to clarify, 0.0217505g of praseodymium (III) nitrate hexahydrate, 4ml of acetylacetone were added in succession. And sealing the beaker again, placing the sealed beaker in a constant-temperature magnetic stirring water bath kettle, stirring the beaker at the temperature of 60 ℃ until the beaker is clear.
And b, dripping the clarified solution obtained in the step a on a platinum substrate with the size of 7mm by using a dropper with the specification of 1ml until the platinum substrate is completely covered. Followed by spinning in a spin coater at 500r/min for 14 seconds and then at 3000r/min for 30 seconds.
And c, putting the sample obtained in the step b into a rapid annealing furnace, pyrolyzing the sample in an air environment at the temperature of between 150 and 350 ℃ for 5 to 10min, cooling the sample to 150 ℃, and taking the sample out.
And d, repeating the step b and the step c for 5 times on the sample obtained in the step c to obtain a film sample.
And e, putting the film sample obtained in the step d into a rapid annealing furnace, and annealing for 300 seconds in an oxygen environment at the temperature of 400 ℃.
And f, putting the sample obtained in the step e into a rapid annealing furnace, annealing for 100-150 seconds in an oxygen environment at the temperature of 400 ℃, and cooling along with the furnace to obtain the praseodymium ion doped hafnium oxide ferroelectric film with the molar doping ratio of 5%.
By implementing the embodiment of the invention, the praseodymium-doped hafnium oxide ferroelectric film can be prepared under the condition of not using other large-scale equipment such as a glove box, so that the preparation process is simplified, the equipment cost is reduced, and the large-scale production is easy.
The foregoing is a preferred embodiment of the present invention, and it should be noted that it would be apparent to those skilled in the art that various modifications and enhancements can be made without departing from the principles of the invention, and such modifications and enhancements are also considered to be within the scope of the invention.
Claims (1)
1. A preparation method of a praseodymium ion doped hafnium oxide ferroelectric film is characterized by comprising the following steps:
mixing hafnium acetylacetonate and acetic acid, heating and stirring until the mixture is clear, and then cooling to room temperature to obtain a first solution;
sequentially adding praseodymium (III) nitrate hexahydrate and an acetylacetone solution into the first solution, and then heating and stirring until the mixture is clarified to obtain a second solution, wherein the mass concentration of metal ions in the second solution is 0.1 mol/L, the molar ratio of hafnium ions to praseodymium ions is 0.95:0.05, and the volume ratio of acetic acid to acetylacetone is 3: 2;
dripping the second solution on a platinum substrate to carry out N times of spin coating treatment operation, and then carrying out annealing operation to obtain the praseodymium ion doped hafnium oxide ferroelectric film;
wherein N is a positive integer greater than or equal to 1, and the spin coating operation specifically comprises:
dropwise adding the second solution on the platinum substrate, and carrying out spin coating for a preset time by a spin coater to obtain a first processed platinum substrate sample; pyrolyzing the first processed platinum substrate sample in an air environment at 150-350 ℃ for 5-10min, and cooling to 150 ℃ to finish the spin coating processing operation;
the annealing operation specifically comprises: carrying out primary annealing on the platinum substrate subjected to the N times of spin coating treatment operations at a first preset temperature, and then carrying out secondary annealing at a second preset temperature; the first preset temperature is 400 ℃, and the second preset temperature is 800 ℃.
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| CN111547767A (en) * | 2020-05-11 | 2020-08-18 | 湘潭大学 | Preparation method of multi-element composite doped hafnium oxide ferroelectric film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200606278A (en) * | 2004-08-05 | 2006-02-16 | Univ Nat Chiao Tung | Process for growing film of hafnium dioxide by liquid phase deposition |
| JP2017178833A (en) * | 2016-03-30 | 2017-10-05 | 東ソー株式会社 | Trinuclear hafniumoxo-alkoxo complex, and method for producing the same |
| CN108039408A (en) * | 2017-12-22 | 2018-05-15 | 湘潭大学 | A kind of preparation method of flexibility hafnium oxide based ferroelectric film |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200606278A (en) * | 2004-08-05 | 2006-02-16 | Univ Nat Chiao Tung | Process for growing film of hafnium dioxide by liquid phase deposition |
| JP2017178833A (en) * | 2016-03-30 | 2017-10-05 | 東ソー株式会社 | Trinuclear hafniumoxo-alkoxo complex, and method for producing the same |
| CN108039408A (en) * | 2017-12-22 | 2018-05-15 | 湘潭大学 | A kind of preparation method of flexibility hafnium oxide based ferroelectric film |
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