CN106191821A - The preparation method of lanthanum-strontium-cobalt-oxygen conductive film material - Google Patents
The preparation method of lanthanum-strontium-cobalt-oxygen conductive film material Download PDFInfo
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- CN106191821A CN106191821A CN201610741618.2A CN201610741618A CN106191821A CN 106191821 A CN106191821 A CN 106191821A CN 201610741618 A CN201610741618 A CN 201610741618A CN 106191821 A CN106191821 A CN 106191821A
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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
- C23C18/16—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 reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1642—Substrates other than metallic, e.g. inorganic or organic or non-conductive semiconductor
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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
- C23C18/16—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 reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1675—Process conditions
- C23C18/1678—Heating of the substrate
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Abstract
The invention provides the preparation method of a kind of lanthanum-strontium-cobalt-oxygen conductive film material, the method includes the preparation of precursor solution, solvent acetic acid, deionized water, acetylacetone,2,4-pentanedione and solute lanthanum acetate, strontium acetate and cobaltous acetate will mix at a certain temperature with the concentration of 0.2 0.4M and the precursor solution sol evenning machine prepared thrown away and obtain dry film, then in rapid thermal anneler, temperature-gradient method carries out heat treatment, obtains the LSCO thin-film material of desired thickness.This film performance is excellent, and resistivity value is 0.95m Ω cm, and crystallite dimension is 50～100nm, and surface roughness is 2.7nm, does the electrode of ferroelectric memory with this thin film and measures system test through standard ferroelectricity, and 3 × 109Fatigue is not shown after secondary upset.Show that this thin-film material is suitable for doing the electrode of ferroelectric memory.
Description
The present invention relates to the preparation method of a kind of conductive metal oxide film material, particularly a kind of for ferroelectricity storage
The preparation method of the lanthanum-strontium-cobalt-oxygen conductive film material of device electrode material.
Lanthanum-strontium-cobalt-oxygen (La, Sr) CoO3(LSCO) conductive film material at room temperature has excellent electric conductivity because of it,
Can be widely used for the electrode of fuel cell, oxygen permeable membrane and ferroelectric memory and receive much concern.Owing to it has the crystalline substance of perovskite
Body structure and the Lattice Matching of the perovskite ferroelectric body with lead series, the fabulous fatigue properties improving ferroelectric memory.
Therefore, it is particularly well-suited to do the electrode of ferroelectric memory.In numerous LSCO conductive film material preparation methoies, chemical solution
Liquid method has plurality of advantages, if accurately controlling stoichiometric proportion, crystallization temperature is low, can prepare large area uniform film material
Deng.Chemical solution method generally has two kinds: one is metal-organic decomposition method, solute used acetate to be passed through and the new last of the ten Heavenly stems two
Acid carries out the chemical reaction of complexity and generates new sebacate, and solvent is dimethylbenzene, and toxic；Another kind is sol-gel process,
Being solute with nitrate, solvent is polyethylene alcohol and water, and this method is in film-forming process, and the nitrogen oxide gas of generation is poisonous
Property, it addition, the adhesion of the LSCO conductive film material prepared of this method and substrate is poor.So preparing lanthanum-strontium cobalt with the aforedescribed process
Oxygen conductive film material, complex process, cost are high, pollute environment, be unfavorable for business development.Referring specifically to:
Appl.Phys.Lett.64,1994, P3509-3511 and ThinSolidFilms, 341,1999, P13-17.
The purpose of the present invention is to propose to a kind of environmentally safe, the system of the LSCO conductive film material that operating procedure is easy
Preparation Method.
Have now found that lanthanum acetate [La (CH3COO)31.5H2O], strontium acetate [Sr (CH3COO)20.5H2O] and cobaltous acetate [Co
(CH3COO)24H2O] this kind of simple organic salt the most not deliquescence, water soluble and acetic acid, and will not produce and poisonous have
Pest matter.It is used to simplify precursor solution preparation ground operating procedure as solute, and synthesis is easier to, the elder generation of preparation
Driving liquid solution stable performance, the film performance made is excellent.
The preparation of thin-film material uses Organometallic Chemistry liquid phase deposition, and process is:
1. the preparation of precursor solution:
Solvent is acetic acid (CH3COOH), deionized water, stabilizer is acetylacetone,2,4-pentanedione (CH3COCH2COCH3), their body
Long-pending ratio is for 23-28: 4-6: 3-5.Solute is lanthanum acetate, strontium acetate, cobaltous acetate, and their mol ratio is 1: 1: 2, with 0.2-0.4M
Concentration is dissolved in solution.
The program of preparation is:
A. by above-mentioned preparation ratio, first by solvent acetic acid, water, solute lanthanum acetate, strontium acetate, cobaltous acetate mix, and are heated to
60-80 DEG C makes solute be completely dissolved.
The most again by acetylacetone,2,4-pentanedione (CH3COCH2COCH3) add mixing in above-mentioned mixed solution, it is heated to 100-120 DEG C,
100-120 minute time, make solution fully reflux, then the concentration of solution is adjusted to 0.2-0.4M, be i.e. made for stable
Precursor solution.
2. the preparation of thin-film material:
Dripping to, on substrate, uniformly be thrown away by solution with sol evenning machine by the precursor solution prepared, whirl coating speed is 3000-
6000 revs/min, the time is the 20-40 second, and solvent volatilizees rapidly and obtains dry film.Then dry film is placed in together with substrate short annealing
In stove, temperature-gradient method carries out heat treatment, i.e. at 150-200 DEG C, heats 2-4 minute, then at 320-360 DEG C, pyrolysis 2-4 divides
Clock, finally under 500-800 DEG C of high temperature, anneals 2-4 minute.Repeat said process, until obtaining the LSCO thin film of desired thickness
Material.
The accompanying drawing of the present invention is described as follows:
Fig. 1 is the surface topography map of LSCO conductive film material of the present invention；
Fig. 2 is resistance and the graph of relation of annealing temperature of LSCO conductive film material of the present invention；
Fig. 3 is the fatigue properties that LSCO conductive film material of the present invention makees the ferroelectric memory of hearth electrode.
Use the conductive film material prepared of the inventive method, there is following beneficial effect:
1., with this kind of simple organic salt of lanthanum acetate, strontium acetate and cobaltous acetate as raw material, greatly reduce raw-material
Cost, and whole technical process can operate in atmospheric environment, and avirulence, bring conveniently to operation so that it is be conducive to
Business is applied.
2., owing to adding stabilizer acetylacetone,2,4-pentanedione in the process for preparation of solution, the precursor solution performance making preparation is steady
Fixed, can deposit half a year.
3. the conductive film material electric conductivity that prepared by the present invention is good, and thin-film material is at 750 DEG C as can be seen from Figure 1
Annealing, resistivity is 0.95m Ω cm, it is adaptable to do the electrode of ferroelectric memory；Conductive film material table prepared by the present invention
Face pattern is good, and as can be seen from Figure 2 the crystal grain of thin film is relatively big, is 50～100nm, and surface roughness is less than 2.7nm；Can from Fig. 3
Going out the conductive film material prepared by the present invention, to do the electrode fatigue properties of ferroelectric memory splendid.
Embodiment:
1. the vessel used by cleaning:
The flask that will use, beaker, weighing botle, pipet, condenser etc. clean once with fresh chromic acid lotion, so
Rinse with tap water afterwards, then with deionized water rinsing 3 times.Cleaned vessel are standby after toasting 5 hours under conditions of 80 DEG C.
The preparation of 2.LSCO precursor solution:
First the lanthanum acetate of 1.7154 grams (0.005 moles), 1.0736 grams of (0.005 mole) acetic acid are weighed with electronic balance
Strontium and 2.4908 grams of (0.01 mole) cobaltous acetate are inserted in the flask of one 50 milliliters.Then the acetic acid of 25 milliliters is measured with pipet
With 5 ml deionized water, it is slowly added in flask.80 DEG C are heated to reflux to making them be completely dissolved.Then 4 are measured with pipet
Milliliter acetylacetone,2,4-pentanedione joins in flask, obtains the solution that a clarification Fructus Vitis viniferae is red.110 DEG C are refluxed 100 minutes, make solution mix
Uniformly.By evaporating part acetic acid and water, the concentration of solution is adjusted to 0.3M.The solution obtained filters in clean room, removes
Decontamination, standby after solution is placed 15 days.The precursor solution so obtained can stably be deposited 6 months.
Prepared by 3.LSCO conductive film material:
(1) Substrate treatment:
A () makees substrate with Si (100), clean substrate surface the most gently with cotton ball soaked in alcohol, to remove the Organic substance on surface.
B the substrate cleaned is put into equipped with in the beaker of acetone by (), clean 5 minutes in ultrasonic cleaning tank, further
Remove Organic substance.
C the most cleaned substrate is rinsed by () again with anhydrous alcohol, and dry at photoresist spinner.
D () uses a large amount of deionized water rinsing, repeat said process, until substrate surface no longer hangs the globule.
E () infrared drying is standby.
(2) spin coating of thin film
Drip to, on substrate, uniformly be thrown away by solution with sol evenning machine by the precursor solution glue head dropper prepared, whirl coating
Speed is 4000 revs/min, and the time is 30 seconds, and solvent volatilizees rapidly and obtains dry film.Then dry film is placed in together with substrate quickly
In annealing furnace, temperature-gradient method carries out heat treatment, i.e. at 180 DEG C, heats and removes solvent further in 3 minutes；Again at 350 DEG C, add
Heat removes organic group in 3 minutes；Last under 750 DEG C of high temperature, 3 minutes crystallization thin films of annealing.Repeat said process 4 times, can obtain
To the LSCO thin-film material that thickness is 120nm.It should be noted that: every layer film after annealing, when taking out annealing furnace, be protected
Card temperature is less than 300 DEG C, to prevent variations in temperature from causing the most greatly the thermal stress of thin film to have little time release.
4.LSCO thin-film material performance test:
Utilizing atomic force microscope and field emission scanning electron microscope to characterize surface topography and the thickness of thin film, Fig. 1 is
The surface topography map of the atomic force microscope of LSCO thin-film material, it can be seen that the crystallite dimension of LSCO thin film is 50～100nm, table
Surface roughness is 2.7nm.
Using four probe method to measure the surface resistivity of LSCO thin-film material, the conductive characteristic of thin-film material is shown in Fig. 2 curve,
As can be seen from the figure thin film available minimum resistivity value 0.95m Ω cm under the annealing temperature of 750 DEG C.
The fatigue properties of the ferroelectric memory on LSCO thin film are the types produced with Radiant Technologies company
Number measuring for RT66A standard ferroelectricity test system, Fig. 3 provides the Pt/PZT/LSCO ferroelectricity under the electric field of 167kV/cm
The fatigue properties of memorizer, it can be seen that 3 × 109After upset, do not show fatigue, it can thus be appreciated that LSCO thin film material prepared by the present invention
Material is suitable as the electrode material of ferroelectric memory.
Claims (2)
1. the preparation method of a lanthanum-strontium-cobalt-oxygen conductive film material, it is characterised in that specifically comprising the following steps that of this preparation method
(1). the preparation of precursor solution:
Solvent is acetic acid, deionized water, and stabilizer is acetylacetone,2,4-pentanedione, and their volume ratio is 23-28: 4-6: 3-5；Solute is vinegar
Acid lanthanum, strontium acetate, cobaltous acetate, their mol ratio is 1: 1: 2, is dissolved in solution with 0.2-0.4M concentration,
The program of preparation is:
A. by above-mentioned preparation ratio first by solvent acetic acid, water, solute lanthanum acetate, strontium acetate, cobaltous acetate mix, and are heated to 60-80
DEG C solute is made to be completely dissolved；
The most again acetylacetone,2,4-pentanedione is added in above-mentioned mixed solution and mix, be heated to 100-120 DEG C, 100-120 minute time, make
Solution fully refluxes, and then the concentration of solution is adjusted to 0.2-0.4M, is i.e. made for stable precursor solution,
(2). the preparation of thin-film material:
Dripping to, on substrate, uniformly be thrown away by solution with sol evenning machine by the precursor solution prepared, whirl coating speed is 3000-6000
Rev/min, the time is the 20-40 second, and solvent volatilizees rapidly and obtains dry film；Then dry film is placed in quick anneal oven together with substrate
Temperature-gradient method carries out heat treatment, i.e. at 150-200 DEG C, heats 2-4 minute, then at 320-360 DEG C, is pyrolyzed 2-4 minute,
After under 500-800 DEG C of high temperature, anneal 2-4 minute, repeat said process, until obtaining the LSCO thin-film material of desired thickness.
The preparation method of a kind of lanthanum-strontium-cobalt-oxygen conductive film material the most according to claim 1, it is characterised in that described
Substrate is Si material.
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| CN201610741618.2A CN106191821A (en) | 2016-08-26 | 2016-08-26 | The preparation method of lanthanum-strontium-cobalt-oxygen conductive film material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106782898A (en) * | 2017-03-12 | 2017-05-31 | 苏州南尔材料科技有限公司 | A kind of preparation method of silicon base neodymium strontium cobalt thin film |
| CN106847673A (en) * | 2017-03-12 | 2017-06-13 | 苏州南尔材料科技有限公司 | A kind of preparation method of silicon base zinc-oxide film |
| CN106920598A (en) * | 2017-03-12 | 2017-07-04 | 苏州南尔材料科技有限公司 | A kind of method for preparing tin oxide conductive film on a silicon substrate |
| CN110330685A (en) * | 2019-07-09 | 2019-10-15 | 成都爻能节能科技有限公司 | A kind of ceramic material and the energy saver made from the material |
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2016
- 2016-08-26 CN CN201610741618.2A patent/CN106191821A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106782898A (en) * | 2017-03-12 | 2017-05-31 | 苏州南尔材料科技有限公司 | A kind of preparation method of silicon base neodymium strontium cobalt thin film |
| CN106847673A (en) * | 2017-03-12 | 2017-06-13 | 苏州南尔材料科技有限公司 | A kind of preparation method of silicon base zinc-oxide film |
| CN106920598A (en) * | 2017-03-12 | 2017-07-04 | 苏州南尔材料科技有限公司 | A kind of method for preparing tin oxide conductive film on a silicon substrate |
| CN110330685A (en) * | 2019-07-09 | 2019-10-15 | 成都爻能节能科技有限公司 | A kind of ceramic material and the energy saver made from the material |
| CN110330685B (en) * | 2019-07-09 | 2021-07-30 | 成都爻能节能科技有限公司 | Ceramic material and energy-saving device made of same |
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Application publication date: 20161207 |