CN107902694A - A kind of quick low temperature liquid phase method for preparing zirconia film - Google Patents
A kind of quick low temperature liquid phase method for preparing zirconia film Download PDFInfo
- Publication number
- CN107902694A CN107902694A CN201711233373.3A CN201711233373A CN107902694A CN 107902694 A CN107902694 A CN 107902694A CN 201711233373 A CN201711233373 A CN 201711233373A CN 107902694 A CN107902694 A CN 107902694A
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- CN
- China
- Prior art keywords
- zirconium oxide
- zirconia film
- oxide precursor
- precursor solution
- film
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
Abstract
The invention belongs to material, chemistry and chemical field, more particularly to a kind of quick low temperature liquid phase method for preparing zirconia film.Include the following steps：Zirconyl nitrate is weighed, measures solvent, configuration concentration is the zirconium oxide precursor solution of 0.01 0.5 mol/Ls, and the zirconium oxide precursor solution of clear is formed by 0.1 3 magnetic agitations when small and ultrasonic disperse；(2) zirconium oxide precursor solution is coated to formation zirconium oxide precursor thin-film on cleaned substrate, is annealed by the light waves of 0.5 4.9 minutes, the temperature in light wave annealing process is 100 300 DEG C；Coating and annealing can be repeated several times to obtain the zirconia film of different-thickness requirement.Gained zirconia film performance of the invention is high, there is important application prospect in the devices such as transistor, solar cell, capacitor.Can be to avoid common pyrosol technique, process cycle length or expensive device etc. by the technique of the present invention, cost is low, is adapted to industrialization large-scale production.
Description
Technical field
The invention belongs to material, chemistry and chemical field, more particularly to a kind of quick Low Temperature Liquid for preparing zirconia film
Phase method, zirconia film have important application prospect in fields such as transistor, solar cell, capacitors.
Background technology
Zirconium oxide is a kind of important inorganic material.It is zirconia film hardness with good stability, higher, larger
Band gap, the corrosion-resistant and excellent optical property of rub resistance, make its microelectronic component, optical thin film, light laser application and
It is widely used in the fields such as memory material.Especially for metal-oxide-field effect of lsi core device
Transistor (Metal-Oxide-Semiconductor Field Effect Transistor, MOSFET) is answered, since it is special
Sign size constantly reduces, and traditional gate dielectric material silica causes the tunneling leakage of MOS drastically already close to physics limit
Increase, leverages the reliability and stability of device.In recent years, the high-ks such as zirconium oxide, aluminium oxide, and hafnium oxide
Material has attracted researchers' extensive concern.Wherein, zirconium oxide is due to higher dielectric constant (~ 20), larger forbidden band
Width, moderate valence band and conduction band offset, and the good thermal stability with silicon base, and as one kind of substitution silica
Very promising high dielectric constant material.
The method for preparing zirconia film at present is varied, mainly includes two major class of vapor phase method and liquid phase method.For example, magnetic
The methods of control sputtering, electron beam evaporation, atomic layer deposition and chemical vapor deposition, is all used to prepare zirconia film.Publication number
A kind of Zirconium silicon oxide thin film with high dielectric coefficient and preparation method are disclosed for the Chinese invention patent of CN101476104B：Using suitable
The ZrO of proportioning2And SiO2Ceramic target is made after sintering, then prepares high-dielectric coefficient zirconium silicon using pulsed laser deposition method
Oxygen film.However, these gas phase process usually require vacuumizing, cost is not only increased, and process cycle is very long, at least
A few houres or tens hours.In recent years, the liquid phase process such as sol-gel process, spray pyrolysis due to it is of low cost, operation is simple
And increasingly cause extensive concern and rapidly development.For example, the Chinese invention patent of Publication No. CN104599947A is public
A kind of zirconium oxide insulation film and preparation method thereof is opened：By the way that acetylacetone,2,4-pentanedione zirconium is dissolved in dimethylformamide, and add
Monoethanolamine, oleic acid are mixed and made into precursor solution as stabilizer, by the way that precursor solution is coated annealed place on substrate
Zirconium oxide insulation film is made in reason.The Chinese invention patent of Publication No. CN104009093A discloses a kind of high k dielectric layer water
The preparation method of property indium oxide film transistor：First acetylacetone,2,4-pentanedione zirconium is dissolved in dimethylformamide, while addition and acetyl
The monoethanolamine of acetone zirconium equimolar amounts forms precursor solution as stabilizer；Again on low-resistance silicon substrate after cleaning before spin coating
Drive liquid solution and obtain sample, sample is put into the sample after ultraviolet lighting handles to obtain photo-annealing is carried out under high-pressure sodium lamp；Then
Sample after photo-annealing is annealed to obtain film sample.Although liquid phase method can be made it can be seen from foregoing invention patent
The zirconia film of standby superior performance, but liquid phase method usually requires the high temperature of a few houres（Higher than 400 DEG C）Annealing, before just promoting
Drive body thin film to decompose and be densified, form fine and close pin-free zirconia film.Therefore, a kind of new fast low temperature solution is found
Technology technology of preparing, is particularly important and urgent for large-scale application of the zirconia film in various fields.
The content of the invention
It is an object of the invention to provide a kind of quick low temperature liquid phase method for preparing zirconia film, zirconium oxide is realized
Prepared by simple and efficient, it is easier to large-scale production and application.The innovative point of the present invention essentially consists in：New low temperature light wave is developed
Method efficiently synthesizes the zirconia film of high dielectric property.
Technical scheme, specifically includes following steps：
(1) zirconium oxide precursor solution is prepared：Zirconyl nitrate is weighed, measures solvent, configuration concentration is 0.01-0.5 mol/Ls
Zirconium oxide precursor solution, the oxidation zirconium precursor of clear is formed by magnetic agitations of 0.1-3 when small and ultrasonic disperse
Liquid solution；
(2) zirconium oxide precursor solution is coated to formation zirconium oxide precursor thin-film on cleaned substrate, by 0.5-
The light wave of 4.9 minutes is annealed, and the temperature in light wave annealing process is 100-300 DEG C；
(3) step 1 and 2 can be repeated several times to obtain the zirconia film of different-thickness requirement.
In the step of preparation method of the present invention (1), the solvent is ethylene glycol monomethyl ether, ethanol, water or ethylene glycol
One or both of more than.
In the step of preparation method of the present invention (2), the painting method for spin coating method, drop-coating, dip coating,
Spray-on process or ink-jet printing process.
In the step of preparation method of the present invention (2), the generation instrument of the light wave is the light-wave cooker as kitchen tools
Or the heating instrument with halogen lamp tube.
In the step of preparation method of the present invention (2), the substrate is rigid substrate, such as silicon chip, sheet glass；It is or soft
Property substrate, such as plastic sheet, sheet metal.
The beneficial effects of the invention are as follows：Present invention process is simply easy to operate, and raw material is cheap and easy to get, prepared zirconium oxide
Film performance is high, is expected to be applied in the devices such as transistor, solar cell, capacitor.Can by the technique of the present invention
To avoid common pyrosol technique, process cycle length or expensive device etc., cost is low, is adapted to industrialization large-scale production.
Brief description of the drawings
The present invention is further illustrated below in conjunction with the accompanying drawings.
Attached drawing 1 is the scanning electron microscopic picture of the zirconia film of one of embodiment, and scale is 500 nanometers in figure, shows institute
Obtaining film has the surface of uniform smooth.
Embodiment
The present invention is further illustrated with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1：
0.04 g zirconyl nitrates are weighed, measure 15 milliliters of ethanol solutions, configuration concentration is the zirconium oxide presoma of 0.01 mol/L
Solution, forms the zirconium oxide precursor solution of clear by 0.1 magnetic agitation when small and ultrasonic disperse.Before zirconium oxide
Drive liquid solution and be coated to formation zirconium oxide precursor thin-film on cleaned substrate, anneal by the light wave of 0.5 minute, light wave moves back
Temperature during fire is 100 DEG C, that is, obtains zirconia film.
Embodiment 2：
0.267 g zirconyl nitrates are weighed, measure 2 milliliters of ethylene glycol monomethyl ether solution, configuration concentration is the zirconium oxide of 0.5 mol/L
Precursor solution, forms the zirconium oxide precursor solution of clear by 3 magnetic agitations when small and ultrasonic disperse.Will oxidation
Zirconium precursor liquid solution is coated to formation zirconium oxide precursor thin-film on cleaned substrate, anneals by the light waves of 5 minutes, light wave
Temperature in annealing process is 200 DEG C, that is, obtains zirconia film.
Embodiment 3：
0.134 g zirconyl nitrates are weighed, measure 5 milliliters of aqueous solutions, configuration concentration is molten for the zirconium oxide presoma of 0.1 mol/L
Liquid, forms the zirconium oxide precursor solution of clear by 1 magnetic agitation when small and ultrasonic disperse.By zirconium oxide presoma
Solution is coated to formation zirconium oxide precursor thin-film on cleaned substrate, anneals by the light wave of 0.9 minute, and light wave is annealed
Temperature in journey is 150 DEG C, that is, obtains zirconia film.
Embodiment 4：
0.4 g zirconyl nitrates are weighed, measure 30 milliliters of ethylene glycol solutions, configuration concentration is the oxidation zirconium precursor of 0.05 mol/L
Liquid solution, forms the zirconium oxide precursor solution of clear by 2 magnetic agitations when small and ultrasonic disperse.Before zirconium oxide
Drive liquid solution and be coated to formation zirconium oxide precursor thin-film on cleaned substrate, anneal by the light waves of 3 minutes, light wave annealing
During temperature be 200 DEG C, that is, obtain zirconia film.
Embodiment 5：
2 g zirconyl nitrates are weighed, measure 10 milliliters of ethanol and 5 milliliters of aqueous solutions, configuration concentration is the zirconium oxide of 0.5 mol/L
Precursor solution, forms the zirconium oxide precursor solution of clear by 3 magnetic agitations when small and ultrasonic disperse.Will oxidation
Zirconium precursor liquid solution is coated to formation zirconium oxide precursor thin-film on cleaned substrate, anneals by the light waves of 2 minutes, light wave
Temperature in annealing process is 250 DEG C, that is, obtains zirconia film.
The embodiment of the present invention is described in above-described embodiment combination attached drawing, but not the present invention is protected
The limitation of scope.Those skilled in the art should understand that on the basis of technical scheme, those skilled in the art
Need not make the creative labor can make to the present invention various modifications or deformation, still protection scope of the present invention with
It is interior.
Claims (5)
- A kind of 1. quick low temperature liquid phase method for preparing zirconia film, it is characterised in that include the following steps：(1) zirconium oxide precursor solution is prepared：Zirconyl nitrate is weighed, measures solvent, configuration concentration is 0.01-0.5 mol/Ls Zirconium oxide precursor solution, the oxidation zirconium precursor of clear is formed by magnetic agitations of 0.1-3 when small and ultrasonic disperse Liquid solution；(2) zirconium oxide precursor solution is coated to formation zirconium oxide precursor thin-film on cleaned substrate, by 0.5- The light wave of 4.9 minutes is annealed, and the temperature in light wave annealing process is 100-300 DEG C；(3) step 1 and 2 can be repeated several times to obtain the zirconia film of different-thickness requirement.
- A kind of 2. quick cryogenic fluid method for preparing zirconia film according to claim 1, it is characterised in that：It is described Solvent be ethylene glycol monomethyl ether, more than ethanol, ethylene glycol, one or both of water.
- A kind of 3. quick cryogenic fluid method for preparing zirconia film according to claim 1, it is characterised in that：It is described Painting method is spin coating method, drop-coating, dip coating, spray-on process or ink-jet printing process.
- A kind of 4. quick cryogenic fluid method for preparing zirconia film according to claim 2, it is characterised in that：It is described The generation instrument of light wave be the light-wave cooker as kitchen tools, there is the heating instrument of halogen or similar fluorescent tube.
- A kind of 5. quick cryogenic fluid method for preparing zirconia film according to claim 2, it is characterised in that：It is described Substrate be rigid substrate, such as silicon chip, sheet glass；Or flexible substrate, such as plastic sheet, sheet metal.
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| CN201711233373.3A CN107902694A (en) | 2017-11-30 | 2017-11-30 | A kind of quick low temperature liquid phase method for preparing zirconia film |
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| CN201711233373.3A CN107902694A (en) | 2017-11-30 | 2017-11-30 | A kind of quick low temperature liquid phase method for preparing zirconia film |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109244237A (en) * | 2018-07-26 | 2019-01-18 | 华南理工大学 | A kind of multi-sheet printed method for improving solwution method zirconium oxide insulating layer performance |
| CN111171625A (en) * | 2020-01-06 | 2020-05-19 | 上海大学 | Rapid preparation method of ink, preparation method of thin film and preparation method of oxide thin film transistor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103608295A (en) * | 2011-07-14 | 2014-02-26 | Ltc有限公司 | Inorganic particle scattering film having good light-extraction performance |
| CN104599947A (en) * | 2014-12-24 | 2015-05-06 | 上海交通大学 | Zirconia insulation film and preparation method thereof |
| CN106431397A (en) * | 2016-09-14 | 2017-02-22 | 齐鲁工业大学 | Low-temperature solution preparation method of high-dielectric zirconium oxide thin film |
-
2017
- 2017-11-30 CN CN201711233373.3A patent/CN107902694A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103608295A (en) * | 2011-07-14 | 2014-02-26 | Ltc有限公司 | Inorganic particle scattering film having good light-extraction performance |
| CN104599947A (en) * | 2014-12-24 | 2015-05-06 | 上海交通大学 | Zirconia insulation film and preparation method thereof |
| CN106431397A (en) * | 2016-09-14 | 2017-02-22 | 齐鲁工业大学 | Low-temperature solution preparation method of high-dielectric zirconium oxide thin film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109244237A (en) * | 2018-07-26 | 2019-01-18 | 华南理工大学 | A kind of multi-sheet printed method for improving solwution method zirconium oxide insulating layer performance |
| CN111171625A (en) * | 2020-01-06 | 2020-05-19 | 上海大学 | Rapid preparation method of ink, preparation method of thin film and preparation method of oxide thin film transistor |
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Application publication date: 20180413 |