CN109097757A - A kind of preparation method of the hafnium oxide ferroelectric thin film of praseodymium ion doping - Google Patents
A kind of preparation method of the hafnium oxide ferroelectric thin film of praseodymium ion doping Download PDFInfo
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- CN109097757A CN109097757A CN201810813379.6A CN201810813379A CN109097757A CN 109097757 A CN109097757 A CN 109097757A CN 201810813379 A CN201810813379 A CN 201810813379A CN 109097757 A CN109097757 A CN 109097757A
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- 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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Abstract
The invention discloses a kind of preparation methods of the hafnium oxide ferroelectric thin film of praseodymium ion doping, comprising the following steps: mixes acetylacetone,2,4-pentanedione hafnium and acetic acid, heating stirring is then cooled to room temperature to clarifying and obtains the first solution.Praseodymium nitrate (III) hexahydrate is successively added in the first solution, acetylacetone,2,4-pentanedione solution, then heating stirring to clarification obtains the second solution.Second solution is added drop-wise to after carrying out the operation of n times spin-coat process on platinum substrate, then executes the hafnium oxide ferroelectric thin film that annealing operation obtains praseodymium ion doping, wherein N is the positive integer more than or equal to 1.By implementing the embodiment of the present invention, praseodymium doped hafnium oxide ferroelectric thin film can be prepared without using other large scale equipments such as glove boxes, preparation process is simple, equipment cost is low, is easy to large-scale production.
Description
Technical field
The present invention relates to the hafnium oxide ferroelectric thins that ferroelectric thin film preparation technical field more particularly to a kind of praseodymium ion are adulterated
The preparation method of film.
Background technique
Ferroelectric memory is one of novel memory devices most with prospects now, and ferroelectric thin film is used to be situated between as storage
Matter.Traditional perovskite ferroelectric thin-film material has not adapted to needs of the electronic device towards miniaturization, therefore develops new
Storage medium material always all by each semiconductor power be included in emphasis research topic.Hafnium oxide ferroelectric thin film is a kind of novel
, compatible with existing silicon technology platform perfection ferroelectric material.
The present inventor has found that there are following technologies to ask in the preparation of existing ferroelectric thin film in the practice of the invention
Topic: the existing technique for preparing hafnium oxide ferroelectric thin-flim materials is mainly technique for atomic layer deposition, pulsed laser deposition technique, splashes
Penetrate method etc..The equipment and source metal of these method needs are expensive, the complex process of the preparation of film, and preparation cost is high.
Summary of the invention
The embodiment of the present invention provides a kind of preparation method of the hafnium oxide ferroelectric thin film of praseodymium ion doping, can effectively solve
Existing hafnium oxide ferroelectric thin film preparation process is complicated, the high problem of preparation cost.
The embodiment of the invention provides a kind of preparation methods of the hafnium oxide ferroelectric thin film of praseodymium ion doping, comprising:
Acetylacetone,2,4-pentanedione hafnium and acetic acid are mixed, heating stirring is then cooled to room temperature to clarifying and obtains the first solution.
Praseodymium nitrate (III) hexahydrate is successively added in the first solution, acetylacetone,2,4-pentanedione solution, then heating stirring is to clear
It is clear to obtain the second solution.
By the second solution be added drop-wise on platinum substrate carry out the operation of n times spin-coat process after, then execute annealing operation obtain praseodymium from
The hafnium oxide ferroelectric thin film of son doping.Wherein, N is the positive integer more than or equal to 1.
Further, acetic acid and acetylacetone,2,4-pentanedione volume ratio are 3:2.
Further, the substance withdrawl syndrome of the second metal ion in solution is 0.1mol/L, wherein hafnium ion and praseodymium from
The molar ratio of son is 0.95:0.05.
Further, spin-coat process operates specifically:
The second solution is added dropwise on platinum substrate, and by after spin coating instrument spin coating preset time, obtaining the first processing platinum substrate
Sample.
After first processing platinum substrate sample is pyrolyzed and is cooled down, spin-coat process operation is completed.
Further, after the first processing platinum substrate sample being pyrolyzed and is cooled down, specifically:
Platinum substrate sample is handled by first, after being pyrolyzed 5-10min under 150 DEG C -350 DEG C of air environment, is cooled to 150
DEG C take out.
Further, annealing operation is executed specifically:
The platinum substrate for completing the operation of n times spin-coat process is annealed under the first preset temperature, then in the second preset temperature
Lower carry out double annealing, the first preset temperature are lower than the second preset temperature.
Further, the first preset temperature is 400 DEG C, and the second preset temperature is 800 DEG C.
The preparation method of the hafnium oxide ferroelectric thin film of a kind of praseodymium ion doping provided in an embodiment of the present invention, with praseodymium nitrate
(III) source of the hexahydrate as praseodymium metal ion can be prepared without using other large scale equipments such as glove boxes
Praseodymium doped hafnium oxide ferroelectric thin film, preparation process is simple, equipment cost is low, is easy to large-scale production.
Detailed description of the invention
Fig. 1 is a kind of stream of the preparation method of the hafnium oxide ferroelectric thin film of praseodymium ion doping provided in an embodiment of the present invention
Journey schematic diagram.
Fig. 2 is a kind of GIXRD figure of the hafnium oxide ferroelectric thin film of praseodymium ion doping provided in an embodiment of the present invention.
Fig. 3 be a kind of hafnium oxide ferroelectric thin film of praseodymium ion doping provided in an embodiment of the present invention ferroelectric hysteresis loop and
Capacitance-voltage curve.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Fig. 1 is a kind of stream of the preparation method of the hafnium oxide ferroelectric thin film of praseodymium ion doping provided in an embodiment of the present invention
Journey schematic diagram, comprising:
S101: acetylacetone,2,4-pentanedione hafnium and acetic acid are mixed, and it is molten to be then cooled to room temperature acquisition first to clarifying for heating stirring
Liquid.
S102: praseodymium nitrate (III) hexahydrate is successively added in the first solution, acetylacetone,2,4-pentanedione solution, then heating is stirred
It mixes to clarification and obtains the second solution.
S103: the second solution being added drop-wise to after carrying out the operation of n times spin-coat process on platinum substrate, then executes annealing operation acquisition
The hafnium oxide ferroelectric thin film of praseodymium ion doping.Wherein, N is the positive integer more than or equal to 1.
Preferably, acetic acid and acetylacetone,2,4-pentanedione volume ratio are 3:2.
Preferably, the substance withdrawl syndrome of the second metal ion in solution is 0.1mol/L, wherein hafnium ion and praseodymium ion
Molar ratio be 0.95:0.05.
Preferably, spin-coat process operates specifically:
The second solution is added dropwise on platinum substrate, and by after spin coating instrument spin coating preset time, obtaining the first processing platinum substrate
Sample.
After first processing platinum substrate sample is pyrolyzed and is cooled down, spin-coat process operation is completed.
Preferably, after the first processing platinum substrate sample being pyrolyzed and is cooled down, specifically:
Platinum substrate sample is handled by first, after being pyrolyzed 5-10min under 150 DEG C to 350 DEG C of air environment, is cooled to
150 DEG C of taking-ups.
Preferably, annealing operation is executed specifically:
The platinum substrate for completing the operation of n times spin-coat process is annealed 300 seconds under the first preset temperature, it is then default second
At a temperature of anneal 100-150 seconds, the first preset temperature be lower than the second preset temperature.
Preferably, the first preset temperature is 400 DEG C, and the second preset temperature is 800 DEG C.
The process of preparation method in order to better illustrate the present invention is below specifically described method of the invention:
Step a, it is poured into beaker after weighing 0.5461835g acetylacetone,2,4-pentanedione hafnium using assay balance, adds 6ml second
Acid.Heating stirring in temperature constant magnetic stirring water-bath is placed in after beaker is sealed, heating temperature is 60 DEG C.It stirs to clarify
Afterwards, 0.0217505g praseodymium nitrate (III) hexahydrate, 4ml acetylacetone,2,4-pentanedione are sequentially added.Perseverance is placed in after beaker is sealed again
It is stirred in warm magnetic agitation water-bath, temperature setting is 60 DEG C, is stirred to clarify.
Step b, the resulting clear solution drop of step a is taken to serve as a contrast in the platinum having a size of 7mm*7mm using the dropper that specification is 1ml
On bottom, until platinum substrate is completely covered.Then spin coating 14 seconds in the spin coating instrument that revolving speed is 500r/min, then in 3000r/
Spin coating 30 seconds under min revolving speed.
Step c, the resulting sample of step b is put into quick anneal oven, it is hot under 150 DEG C to 350 DEG C of air environment
150 DEG C are cooled to after solution 5-10min, is taken out.
Step d, it on the resulting sample of step c, is repeated 5 times by the sequence of step b and step c, obtains film sample.
Step e, the resulting film sample of step d is put into quick anneal oven, is moved back in the case where temperature is 400 DEG C of oxygen atmosphere
Fire 300 seconds.
Step f, the resulting sample of step e is put into quick anneal oven, is annealed in the case where temperature is 400 DEG C of oxygen atmosphere
100-150 seconds, furnace cooling was to get the hafnium oxide ferroelectric thin film to mole doping than the praseodymium ion doping for 5%.
By implementing the embodiment of the present invention praseodymium can be prepared without using other large scale equipments such as glove boxes
Hafnium oxide ferroelectric thin film is adulterated, so that simplified preparation process, reduction equipment cost are low, is easy to large-scale production.
It is the preferred embodiment of the present invention above, it is noted that for those skilled in the art,
Various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as this hair
Bright protection scope.
Claims (7)
1. a kind of preparation method of the hafnium oxide ferroelectric thin film of praseodymium ion doping characterized by comprising
Acetylacetone,2,4-pentanedione hafnium and acetic acid are mixed, heating stirring is then cooled to room temperature to clarifying and obtains the first solution；
Praseodymium nitrate (III) hexahydrate is successively added in first solution, acetylacetone,2,4-pentanedione solution, then heating stirring is to clear
It is clear to obtain the second solution；
Second solution is added drop-wise to after carrying out the operation of n times spin-coat process on platinum substrate, then executed described in annealing operation acquisition
The hafnium oxide ferroelectric thin film of praseodymium ion doping；Wherein, N is the positive integer more than or equal to 1.
2. a kind of preparation method of the hafnium oxide ferroelectric thin film of praseodymium ion doping as described in claim 1, which is characterized in that
The acetic acid and acetylacetone,2,4-pentanedione volume ratio are 3:2.
3. a kind of preparation method of the hafnium oxide ferroelectric thin film of praseodymium ion doping as claimed in claim 2, which is characterized in that
The substance withdrawl syndrome of second metal ion in solution is 0.1mol/L, wherein the molar ratio of hafnium ion and praseodymium ion is
0.95:0.05。
4. a kind of preparation method of the hafnium oxide ferroelectric thin film of praseodymium ion doping as claimed in claim 3, which is characterized in that
The spin-coat process operation specifically:
Second solution is added dropwise on the platinum substrate, and by after spin coating instrument spin coating preset time, obtaining the first processing platinum
Substrate sample；
After the first processing platinum substrate sample is pyrolyzed and is cooled down, the spin-coat process operation is completed.
5. a kind of preparation method of the hafnium oxide ferroelectric thin film of praseodymium ion doping as claimed in claim 4, which is characterized in that
It is described that the first processing platinum substrate sample is pyrolyzed and is cooled down, specifically:
The first processing platinum substrate sample is cooled to 150 after being pyrolyzed 5-10min under 150 DEG C -350 DEG C of air environment
DEG C take out.
6. a kind of preparation method of the hafnium oxide ferroelectric thin film of praseodymium ion doping as claimed in claim 5, which is characterized in that
The execution annealing operation specifically:
The platinum substrate for completing the n times spin-coat process operation is once annealed under the first preset temperature, then second
Double annealing is carried out under preset temperature；First preset temperature is lower than second preset temperature.
7. a kind of preparation method of the hafnium oxide ferroelectric thin film of praseodymium ion doping as claimed in claim 6, which is characterized in that
First preset temperature is 400 DEG C, and second preset temperature is 800 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111029244A (en) * | 2019-11-28 | 2020-04-17 | 湘潭大学 | Preparation method of cerium-doped hafnium oxide-based ferroelectric film and capacitor structure |
| CN111547767A (en) * | 2020-05-11 | 2020-08-18 | 湘潭大学 | Preparation method of multi-element composite doped hafnium oxide ferroelectric film |
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| 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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2018
- 2018-07-23 CN CN201810813379.6A patent/CN109097757B/en active Active
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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111029244A (en) * | 2019-11-28 | 2020-04-17 | 湘潭大学 | Preparation method of cerium-doped hafnium oxide-based ferroelectric film and capacitor structure |
| CN111547767A (en) * | 2020-05-11 | 2020-08-18 | 湘潭大学 | Preparation method of multi-element composite doped hafnium oxide ferroelectric film |
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