CN101100749A - Low temperature preparation method for alcohol heat assistant ferro-electricity film - Google Patents
Low temperature preparation method for alcohol heat assistant ferro-electricity film Download PDFInfo
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- CN101100749A CN101100749A CNA2007100442115A CN200710044211A CN101100749A CN 101100749 A CN101100749 A CN 101100749A CN A2007100442115 A CNA2007100442115 A CN A2007100442115A CN 200710044211 A CN200710044211 A CN 200710044211A CN 101100749 A CN101100749 A CN 101100749A
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Abstract
An invention relates to non-lead ferroelectric film by sol-gel process. It is alcohol heat associated low temperature preparation of ferroelectric film, carried out by: soaking coated films in alcohol solution at 2-5MPa and 120-300 deg.C for 10-30h, and sputtering electrodes onto them. The condition of the alcohol heating reaction is moderate with wide range of temperature regulation and low cost. Factors of the reaction, e.g. reaction temperature, time and pressure, solution components or pH value, etc., can be regulated to effectively control progress of crystal growth to obtain excellent materials. It avoids un-uniform components and their gradients caused by traditional water heating process.
Description
Technical field
The invention belongs to a kind of employing sol-gel method and prepare the non-lead ferro-electric film technical field.
Background technology
In the past few decades, various method for manufacturing thin film are used and prepare ferroelectric membranc, comprising: molecular beam evaporation extension (MBE) in different physical gas phase deposition technology plasma sputter deposition (PSD) and the sub-beam sputter-deposition of ion (IBSD), pulse laser flash distillation deposition (PLAD), electron beam or the electric furnace, metal organic chemical vapor deposition (MOCVD) method (MOCVD), chemical dissolution method (MOD for example: sol-gel process and metal organic deposit method)
[1-10]As everyone knows, all need film is carried out pyroprocessing (＞500 ℃) utilizing above method to prepare in the process of film.Pyroprocessing will cause the appearance of diffusion layer between film and electrode and electrode and the substrate for a long time.This class diffusion layer tends to worsen the dielectric properties of film.In addition, the variation of thermal stresses easily makes film produce be full of cracks, will certainly influence the reliability and stability that material uses like this.The existence of these problems has hindered this dielectric materials further promoting the use of in semiconductor technology, so the work of ferroelectric membranc low temperature preparation research has important practical significance.
Sol-gel with its stoichiometric ratio precise control, film forming area big and evenly, advantage such as the technological process temperature is low, equipment is simple and being adopted by people.And under hydrothermal condition, water or other solvent are in critical or supercritical state, and reactive behavior improves.Rerum natura and the chemical reaction performance of material in solvent all has very big change, so solvent thermal reaction differs from normality greatly.This method has become the important channel of materials such as synthetic ultra micron, monocrystalline.With the water ratio, alcohol critical temperature and emergent pressure will be low many,, make it to be in supercritical state and the supercritical liq that forms is the fluid that a kind of temperature and pressure is higher than its threshold value as reaction solvent with alcohol, that is be compressed to the gas that has near fluid density.Its feature is that viscosity and spread coefficient are near gas, and density and dissolving power and common liquid phase are seemingly, it is very responsive that this makes that its character such as viscosity, density, spread coefficient, solvating ability change with temperature and pressure, and transmission performance is excellent more as diffusibility, thermal conductivity etc.Therefore, supercritical environment can quicken chemical reaction, forms fine and close superfine crystal particle easily.Also do not utilize at present method that collosol and gel combines with pure heat at Pt/Ti/SiO
2The report of/Si growth non lead ferroelectric film.
Summary of the invention
Purpose of the present invention just provides a kind of at Pt/Ti/SiO
2The preparation method of the last low-temperature epitaxy non lead ferroelectric film of/Si.For reaching above-mentioned purpose, the concrete technical scheme that the present invention takes is as follows:
A kind of low temperature preparation method of alcohol heat assistant ferro-electricity film is with coated thin film dipped the processing in 120-300 ℃ alcoholic solution 10～30 hours, pressure 2-5Mpa, sputter top electrode then.
The low temperature preparation method of described alcohol heat assistant ferro-electricity film, its concrete steps can be taked following scheme:
Elder generation adopts sol-gel method preparation precursor solution, and the method for using the rotation coating then is at Pt/Ti/SiO
2Obtain the film of required thickness on/Si and the Ti substrate, again with this thin film dipped in 120-300 ℃ alcoholic solution, processing 10～30 hours, 2-5Mpa, at last thereon the surface sputtering gold as top electrode.
Among the present invention, adopting sol-gel method preparation precursor solution is known method, document Jiwei Zhai sees reference, XiYao.[J] .Applied Phsics letters.2004,84:3136-3138 and Jiwei Zhai, Haydn Chen.[J] .Applied Phsicsletters.2004,841162-1164.If preparation Ba is (Zr, Ti) O
3(BZT), Ba (Ti, Sr) O
3Film such as (BST), then utilize inorganic barium salt, strontium salt and organic zirconium, titanium etc., solvent is Glacial acetic acid, ethylene glycol ethyl ether and methyl ethyl diketone etc., (mol ratio is x: 1-x for Ba/Sr, the Zr/Ti etc. of preparation different mol ratio, wherein x is 0-0.90) precursor aqueous solution, the ultimate density of its precursor solution is controlled between the 0.2-0.4M.Use method of the present invention, experimental result film preferably has Ba (Zr, Ti) O
3(BZT), Ba (Ti, Sr) O
3(BST) and BaTiO
3(BT).
Among the present invention, the method that rotation applies is a prior art, and document Jiwei Zhai sees reference, Xi Yao.[J] .Applied Phsicsletters.2004,84:3136-3138 and Jiwei Zhai, Haydn Chen.[J] .Applied Phsics letters.004,841162-1164.When rotation applied, speed of rotation was 3000～4000 rev/mins, 10～30 seconds time.Gel-film is directly put into 300～400 ℃ environment, was placed 2～10 minutes, takes out postcooling to room temperature, applies one deck gel-film down, moves in circles up to the film that obtains desired thickness.Utilize the low characteristics of collosol and gel thermal treatment temp, handle at a lower temperature after rotation applies each time, its organism is decomposed fully.
Among the present invention, the temperature of alcoholic solution, heat treatment time, ionic concn, pressure etc. all can influence the size of grain growing, but temperature and pressure is the control factor of most critical.According to the requirement of different series thin films, the ionic species in the alcoholic solution is different with concentration, and ionic species is generally corresponding with contained species of metal ion in the film, and concentration is generally at 0.01-0.03mol/L.For example in the process of preparation BZT film, the ion that comprises in the alcoholic solution can be respectively: 0.01mol/L barium ion, 0.01mol/L zirconium ion, 0.01mol/L titanium ion and hydroxide ion etc.The pH value scope of used alcoholic solution is between 7-14.
Among the present invention, the method sputter gold that can adopt existing d.c. sputtering is as top electrode, and the diameter of top electrode is generally 0.1～0.5mm, thickness is generally 100～200nm.
Beneficial effect of the present invention:
(1) pure thermal rection condition is relatively gentleer, energy consumption is lower, suitability is wide.Can pass through temperature of reaction, time and pressure, reaction and crystal growth process are effectively controlled in the adjusting of factors such as the composition of solution and solution pH value, thereby obtain desirable material.
(2) the present invention can effectively avoid traditional and directly utilize the component gradient that hydrothermal method caused when low temperature prepares ferroelectric membranc in the titanium substrate and the phenomenon of composition inequality, thereby plays effective effect that improves material property.
(3) film Ba (Zr, Ti) O that utilizes the present invention to prepare
3(BZT), Ba (Ti, Sr) O
3(BST) and BaTiO
3(BT) etc. ferroelectric material belongs to nonlead system, in preparation process especially with the integrating process of Si technology in do not have plumbous pollution, and the scope of adjusting temperature is also than broad.
Description of drawings
Fig. 1 is that preparation is at Pt/Ti/SiO
2The X ray diffracting spectrum (XRD) of BT on the/Si (100)
Fig. 2 is that preparation is at Pt/Ti/SiO
2The X ray diffracting spectrum (XRD) of BZT on the/Si (100)
Fig. 3 is that preparation is at Pt/Ti/SiO
2The dielectric frequency spectrum (1kHz-1MHz) of BT on the/Si (100)
Fig. 4 is that preparation is at Pt/Ti/SiO
2The dielectric frequency spectrum (1kHz-1MHz) of BZT on the/Si (100)
Embodiment
Different material systems, the crystalline Tc is different, and the present invention can be with BaTiO
3, Ba (Ti
1-xZr
x) O
3, (Ba, Sr) TiO
3Etc. non-lead is that the Tc of ferroelectric material is controlled at 120-300 ℃, below is specific examples:
Example 1
Preparation Ba (Ti
1-xZr
x) O
3, (x=0-0.9) ferroelectric membranc:
The chemical feedstocks that is adopted is barium acetate [Ba (CH
3COO)
2], zirconium iso-propoxide [Zr (OC
3H
7)
4] and titanium isopropylate [Ti (OC
3H
7)
4], solvent is Glacial acetic acid and ethylene glycol ethyl ether.Earlier barium acetate (according to certain stoichiometric ratio) is heated to boiling in glacial acetic acid solution, stops heating after 5 minutes, and be cooled to room temperature, the mol ratio of Ba and Glacial acetic acid is 1: 10.Mixing solutions with zirconium iso-propoxide and titanium isopropylate, ethylene glycol ethyl ether and methyl ethyl diketone (AcAc) joins in the glacial acetic acid solution of baric again, wherein: the mol ratio of Ti and AcAc is 1: 2, (titanium isopropylate+zirconium iso-propoxide): the mol ratio of ethylene glycol ethyl ether is 1: 10.Add ethylene glycol ethyl ether at last the concentration of final solution is adjusted to 0.3M.Place and be used for preparing film after 24 hours.
Employed substrate is Pt/Ti/SiO
2/ Si (100) and Ti tinsel, wherein Pt, Ti, SiO
2With the thickness of Si sheet be respectively 150nm, 50nm, 150nm and 3500nm.The method that adopts rotation to apply prepares film, and speed of rotation is 3000 rev/mins, 15 seconds time.Gel-film is directly put into 350 ℃ tube furnace, was placed 5 minutes, takes out postcooling to room temperature, applies one deck gel-film down, moves in circles up to the film that obtains desired thickness.
At last with the thermal treatment 28 hours in 200 ℃ water heating kettle of this film.The volume of solvent alcohol is the 50-100 milliliter in the water heating kettle, and the ionic species in the solvent comprises respectively: 0.01mol/L barium ion, 0.01mol/L zirconium ion, 0.01mol/L titanium ion and hydroxide ion etc.Gold electrode is as top electrode in the method sputter of the d.c. sputtering of surface employing thereon then, and its diameter is that 0.5mm, thickness are about 100nm.
Example 2
Preparation BaTiO
3Ferroelectric membranc:
The chemical feedstocks that is adopted is barium acetate [Ba (CH
3COO)
2] and titanium isopropylate [Ti (OC
3H
7)
4], solvent is Glacial acetic acid and ethylene glycol ethyl ether.Earlier barium acetate (according to certain stoichiometric ratio) is heated to boiling in glacial acetic acid solution, stops heating after 5 minutes, and be cooled to room temperature, the mol ratio of Ba and Glacial acetic acid is 1: 10.Mixing solutions with titanium isopropylate, ethylene glycol ethyl ether and methyl ethyl diketone (AcAc) joins in the glacial acetic acid solution of baric, wherein again: the mol ratio of Ti and AcAc is 1: 2, titanium isopropylate: the mol ratio of ethylene glycol ethyl ether is 1: 10.Add ethylene glycol ethyl ether at last the concentration of final solution is adjusted to 0.3M.Place and be used for preparing film after 24 hours.
Employed substrate is Pt/Ti/SiO
2/ Si (100), wherein Pt, Ti, SiO
2With the thickness of Si sheet be respectively 150nm, 50nm, 150nm and 3500nm.The method that adopts rotation to apply prepares film, and speed of rotation is 3000 rev/mins, 15 seconds time.Gel-film is directly put into 350 ℃ tube furnace, was placed 5 minutes, takes out postcooling to room temperature, applies one deck gel-film down, moves in circles up to the film that obtains desired thickness.
With the thermal treatment 20 hours in 200 ℃ water heating kettle of this film.The volume of solvent alcohol is the 50-100 milliliter in the water heating kettle, and the ionic species in the solvent comprises respectively: 0.01mol/L barium ion, 0.01mol/L titanium ion and hydroxide ion etc.Gold electrode is as top electrode in the method sputter of the d.c. sputtering of surface employing thereon then, and its diameter is that 0.5mm, thickness are about 100nm.
Example 3
Preparation BaTiO
3Ferroelectric membranc:
The chemical feedstocks that is adopted is barium acetate [Ba (CH
3COO)
2] and titanium isopropylate [Ti (OC
3H
7)
4], solvent is Glacial acetic acid and ethylene glycol ethyl ether.Earlier barium acetate (according to certain stoichiometric ratio) is heated to boiling in glacial acetic acid solution, stops heating after 5 minutes, and be cooled to room temperature, the mol ratio of Ba and Glacial acetic acid is 1: 10.Mixing solutions with titanium isopropylate, ethylene glycol ethyl ether and methyl ethyl diketone (AcAc) joins in the glacial acetic acid solution of baric, wherein again: the mol ratio of Ti and AcAc is 1: 2, titanium isopropylate: the mol ratio of ethylene glycol ethyl ether is 1: 10.Add ethylene glycol ethyl ether at last the concentration of final solution is adjusted to 0.3M.Place and be used for preparing film after 24 hours.
Employed substrate is Pt/Ti/SiO
2/ Si (100), wherein Pt, Ti, SiO
2With the thickness of Si sheet be respectively 150nm, 50nm, 150nm and 3500nm.The method that adopts rotation to apply prepares film, and speed of rotation is 3000 rev/mins, 15 seconds time.Gel-film is directly put into 350 ℃ tube furnace, was placed 5 minutes, takes out postcooling to room temperature, applies one deck gel-film down, moves in circles up to the film that obtains desired thickness.
With the thermal treatment 20 hours in 120 ℃ water heating kettle of this film.The volume of solvent alcohol is the 50-100 milliliter in the water heating kettle, and the ionic species in the solvent comprises respectively: 0.01mol/L barium ion, 0.01mol/L titanium ion and hydroxide ion etc.Gold electrode is as top electrode in the method sputter of the d.c. sputtering of surface employing thereon then, and its diameter is that 0.5mm, thickness are about 100nm.
Claims (6)
1, a kind of low temperature preparation method of alcohol heat assistant ferro-electricity film the steps include: coated thin film dipped the processing in 120-300 ℃ alcoholic solution 10～30 hours, pressure 2-5Mpa, sputter top electrode then.
2, the low temperature preparation method of alcohol heat assistant ferro-electricity film as claimed in claim 1 is characterized in that: the precursor solution of film adopts the sol-gel method preparation, and the method for using the rotation coating then is at Pt/Ti/SiO
2Obtain the film of required thickness on/Si and the Ti substrate.
3, the low temperature preparation method of alcohol heat assistant ferro-electricity film as claimed in claim 1 is characterized in that: species of metal ion contained in the ionic species in the alcoholic solution and the film is corresponding.
4, the low temperature preparation method of alcohol heat assistant ferro-electricity film as claimed in claim 3 is characterized in that: the concentration of metal ions in the alcoholic solution is 0.01-0.03mol/L.
5, the low temperature preparation method of alcohol heat assistant ferro-electricity film as claimed in claim 1 is characterized in that: the pH value scope of alcoholic solution is between 7-14.
6, as the low temperature preparation method of the described arbitrary alcohol heat assistant ferro-electricity film of claim 1～5, it is characterized in that: used film is Ba (Zr, Ti) O
3, Ba (Ti, Sr) O
3Or BaTiO
3
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|---|---|---|---|
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| CN100558939C CN100558939C (en) | 2009-11-11 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011190A (en) * | 2010-12-22 | 2011-04-13 | 南京工业大学 | Method for preparing nanostructure barium strontium titanate ferroelectric film by utilizing nanocrystalline self assembly process |
| CN102184777A (en) * | 2011-04-11 | 2011-09-14 | 武汉理工大学 | BaTi2O5 thin-film capacitor for ferroelectric random access memory and manufacturing method thereof |
| CN102751094A (en) * | 2011-04-22 | 2012-10-24 | 中国科学院微电子研究所 | Ohmic contact-based ferroelectric thin film capacitor and preparation method thereof |
-
2007
- 2007-07-26 CN CNB2007100442115A patent/CN100558939C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011190A (en) * | 2010-12-22 | 2011-04-13 | 南京工业大学 | Method for preparing nanostructure barium strontium titanate ferroelectric film by utilizing nanocrystalline self assembly process |
| CN102184777A (en) * | 2011-04-11 | 2011-09-14 | 武汉理工大学 | BaTi2O5 thin-film capacitor for ferroelectric random access memory and manufacturing method thereof |
| CN102751094A (en) * | 2011-04-22 | 2012-10-24 | 中国科学院微电子研究所 | Ohmic contact-based ferroelectric thin film capacitor and preparation method thereof |
| CN102751094B (en) * | 2011-04-22 | 2015-08-05 | 华进半导体封装先导技术研发中心有限公司 | A kind of ferroelectric capacitor based on ohmic contact and preparation method thereof |
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| CN100558939C (en) | 2009-11-11 |
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Granted publication date: 20091111 Termination date: 20120726 |