CN102659400B - Method for manufacturing pyrochlore phase bismuth titanate functional films on surfaces of glass substrates - Google Patents

Method for manufacturing pyrochlore phase bismuth titanate functional films on surfaces of glass substrates Download PDF

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CN102659400B
CN102659400B CN 201210128351 CN201210128351A CN102659400B CN 102659400 B CN102659400 B CN 102659400B CN 201210128351 CN201210128351 CN 201210128351 CN 201210128351 A CN201210128351 A CN 201210128351A CN 102659400 B CN102659400 B CN 102659400B
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ots
solution
film
monofilm
glass substrate
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CN102659400A (en
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夏傲
尹君
谈国强
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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Abstract

The invention provides a method for manufacturing pyrochlore phase bismuth titanate functional films on surfaces of glass substrates, which includes the following steps: manufacturing an OTS monofilm on a glass substrate; preparing a precursor solution with Bi and Ti, wherein the molar ratio of the Bi and Ti is (1.20 to 1.00) : 1;dissolving Bi(NO3)3.5H2O in a mixed solution composed of ethylene glycol and ethylene glycol methyl ether, dissolving Ti(OC4H9)4 in absolute ethyl alcohol, mixing and stirring two solutions evenly, maintaining total concentration of the solution to be 0.05 mol/L to 0.10 mol/L, and dropwise adding ammonia water to adjust pH values to prepare a Bi2Ti2O7 precursor solution; placing the glass substrate bearing the OTS monofilm in the precursor solution to obtain amorphous films; and preserving the amorphous films at a temperature of 500 DEG C to 560 DEG C for 2 hours to obtain crystal pyrochlore phase Bi2Ti2O7 films. The Bi2Ti2O7 films manufactured through the method has the advantages of being mature in crystal structure, high in purity, smooth and neat in surface, uniform and compact.

Description

A kind of method for preparing burnt green stone phase bismuth titanates function film at glass baseplate surface
Technical field
The present invention relates to the functional material preparation field, the green stone phase of particularly a kind of Jiao bismuth titanates (Bi 2Ti 2O 7) preparation method of film.
Background technology
Bismuth titanates series has different components and structure, as Bi 4Ti 3O 12, Bi 2Ti 2O 7, Bi 20Ti 2O 20Deng.Bi wherein 2Ti 2O 7Belong to pyrochlore structure, can regard by Ti-O octahedron and the mixing of Bi-O tetrahedral structure and form that chemical general formula is A as 2B 2O 7, lattice parameter is a=b=c=2.068, belongs to cubic system, thereby Bi 2Ti 2O 7Film does not have piezoelectricity and ferroelectricity, but it has higher dielectric constant.
Along with gate insulation layer (SiO in the semiconductor devices 2) continuous attenuate, occurred such as problems such as leakage current increase, device stability variation, one of approach that addresses these problems is to adopt the material of higher dielectric constant to replace SiO commonly used at present 2Gate insulation layer, therefore, people have carried out extensive studies to high dielectric constant material recently.Bi 2Ti 2O 7Film has higher relative dielectric constant (being about 150) and quite low leakage current, is in the high dielectric constant material of research at present, is hopeful to substitute to be used for senior MOS transistor traditional Si O 2One of material of gate insulation layer.Bi 2Ti 2O 7As the grid material of isolated gate FET, can improve the mutual conductance of isolated gate FET, reduce cut-in voltage, improve anti-breakdown characteristics, reduce device size.In addition, Bi 2Ti 2O 7Also at ferroelectric thin film PZT, PST and Bi 4Ti 3O 12Each process of system in, be used as cushion, to improve the electrical properties of film.
At present, relevant Bi 2Ti 2O 7The report of film is less, and reported method only has chemical solution deposition and pulsed laser deposition.Though the chemical solution deposition process is simple, and is with low cost, the uniformity of film and thickness are difficult to control.The advantage of pulsed laser deposition is that the quality of gained film is good, purity is high, good with the associativity of substrate, but process equipment comparatively complicated, need strict vacuum environment and process system, and cost costliness.
Summary of the invention
The object of the present invention is to provide and a kind ofly prepare the method for burnt green stone phase bismuth titanates function film, smooth, the even compact of Jiao Lvshi phase bismuth titanates function film smooth surface that this method is prepared at glass baseplate surface.
To achieve these goals, the present invention adopts following technical scheme:
A kind ofly prepare the method for burnt green stone phase bismuth titanates function film, may further comprise the steps at glass baseplate surface:
Step 1: glass substrate was used deionized water, absolute ethyl alcohol and acetone ultrasonic washing 10 minutes successively, nitrogen dries up the back and deposits 30s～20min to obtain the OTS monofilm in the mixed solution of octadecyl trichlorosilane and toluene, subsequently 120 ℃ down baking removing remained on surface solution, and then in ultraviolet light irradiation 40～60min down; The volume ratio of octadecyl trichlorosilane and toluene is 1:99 in the mixed solution of octadecyl trichlorosilane and toluene;
Step 2: with A mol Bi (NO 3) 35H 2O is dissolved in the mixed solution of being made up of isopyknic ethylene glycol and EGME, with B mol Ti (OC 4H 9) 4Be dissolved in the absolute ethyl alcohol, mix two solution then and stir making Bi in the solution 3+And Ti 4+Total concentration (being A+B) be 0.05mol/L～0.10mol/L, it is 2.5 that dropping ammonia is regulated the pH value, promptly gets Bi 2Ti 2O 7Precursor liquid; A:B=(1～1.2): 1;
Step 3: the Bi that the glass substrate that adheres to the OTS monofilm that step 1 is prepared places step 2 to prepare 2Ti 2O 7In the precursor liquid, obtain noncrystalline membrane at 50 ℃～70 ℃ deposit 14h by liquid deposition;
Step 4: dried noncrystalline membrane is put into Muffle furnace, be incubated 2h to obtain the burnt green stone phase Bi of crystalline state at 500-560 ℃ 2Ti 2O 7Film.
The present invention further improves and is: A:B=1.2:1.
The present invention further improves and is: Bi in the step 2 3+And Ti 4+Total concentration (being A+B) be 0.05mol/L.
Beneficial effect of the present invention is: adopting liquid phase self-assembled monolayer membrane technology, is the template agent with the OTS monofilm, induced growth Bi on the functional glass substrate 2Ti 2O 7Film is for Bi 2Ti 2O 7The preparation technology of film is a kind of brand-new trial, and this novel technology of preparing is a kind of innovation to technology itself not only, and can be to Bi 2Ti 2O 7The performance of film produces the influence of matter.The present invention adopts liquid phase self-assembled monolayer membrane technology, utilizes Bi (NO 3) 35H 2O and Ti (OC 4H 9) 4Being raw material, is the template agent with OTS, has successfully prepared Bi on glass substrate 2Ti 2O 7Film, the certain annealing in process of process obtains the Jiao Lvshi phase Bi of crystallization then 2Ti 2O 7Film.The advantage of this method is that film is arranged at the spontaneous formation of substrate surface original position, one-tenth key high-sequential, defective is few, adhesion is strong, and crystal development is complete, purity is high, and smooth smooth, the even compact of film surface.
Description of drawings
The Bi of Fig. 1 the present invention preparation 2Ti 2O 7The XRD figure spectrum of film.
The Bi of Fig. 2 the present invention preparation 2Ti 2O 7The FE-SEM photo of film.
The Bi of Fig. 3 the present invention preparation 2Ti 2O 7The EDS power spectrum of film.
The specific embodiment
Embodiment 1
The present invention is a kind of to prepare the method for burnt green stone phase bismuth titanates function film at glass baseplate surface, may further comprise the steps:
Step 1: the functionalization of substrate.Glass substrate was successively used deionized water, absolute ethyl alcohol and acetone ultrasonic washing respectively 10 minutes, nitrogen dries up the back in OTS(octadecyl trichlorosilane) and the mixed solution of toluene (volume ratio of OTS and toluene is 1:99) in deposit 30s～20min with acquisition OTS monofilm, toast 5 minutes down to remove remained on surface solution at 120 ℃ subsequently, shine 40min down in ultraviolet light again and realize the substrate surface functionalization.
Step 2: configuration precursor liquid.Considering that Bi is at high temperature volatile, is 1.20:1 preparation precursor liquid with Bi, Ti mol ratio.With Bi (NO 3) 35H 2O is dissolved in the mixed solution of being made up of 10ml ethylene glycol and 10ml EGME, Ti (OC 4H 9) 4Be dissolved in the 30ml absolute ethyl alcohol, mix two solution and stir Bi in the maintenance solution 3+And Ti 4+Total concentration be 0.05mol/L, dropping ammonia to pH value is 2.5, is mixed with Bi 2Ti 2O 7Precursor liquid.
Step 3: thin film deposition.The glass substrate that will adhere to the OTS monofilm places the Bi for preparing 2Ti 2O 7In the precursor liquid, obtain noncrystalline membrane at 60 ℃ of deposit 14h.
Step 4: the crystallization of film.Dried noncrystalline membrane is put into Muffle furnace, be incubated 2h to obtain the burnt green stone phase Bi of crystalline state at 500 ℃ 2Ti 2O 7Film.
Embodiment 2
The present invention is a kind of to prepare the method for burnt green stone phase bismuth titanates function film at glass baseplate surface, may further comprise the steps:
Step 1: the functionalization of substrate.Glass substrate was successively used deionized water, absolute ethyl alcohol and acetone ultrasonic washing respectively 10 minutes, nitrogen dries up the back in OTS(octadecyl trichlorosilane) and the mixed solution of toluene (volume ratio of OTS and toluene is 1:99) in deposit 30s～20min with acquisition OTS monofilm, toast 5 minutes down to remove remained on surface solution at 120 ℃ subsequently, shine 40min down in ultraviolet light again and realize the substrate surface functionalization.
Step 2: configuration precursor liquid.Considering that Bi is at high temperature volatile, is 1.20:1 preparation precursor liquid with Bi, Ti mol ratio.With Bi (NO 3) 35H 2O is dissolved in the mixed solution of being made up of 10ml ethylene glycol and 10ml EGME, Ti (OC 4H 9) 4Be dissolved in the 30ml absolute ethyl alcohol, mix two solution and stir Bi in the maintenance solution 3+And Ti 4+Total concentration be 0.05mol/L, dropping ammonia to pH value is 2.5, is mixed with Bi 2Ti 2O 7Precursor liquid.
Step 3: thin film deposition.The glass substrate that will adhere to the OTS monofilm places the precursor liquid for preparing, and obtains noncrystalline membrane at 60 ℃ of deposit 14h.
Step 4: the crystallization of film.Dried noncrystalline membrane is put into Muffle furnace, be incubated 2h to obtain the burnt green stone phase Bi of crystalline state at 520 ℃ 2Ti 2O 7Film.
Embodiment 3
The present invention is a kind of to prepare the method for burnt green stone phase bismuth titanates function film at glass baseplate surface, may further comprise the steps:
Step 1: the functionalization of substrate.Glass substrate was successively used deionized water, absolute ethyl alcohol and acetone ultrasonic washing respectively 10 minutes, nitrogen dries up the back in OTS(octadecyl trichlorosilane) and the mixed solution of toluene (volume ratio of OTS and toluene is 1:99) in deposit 30s～20min with acquisition OTS monofilm, toast 5 minutes down to remove remained on surface solution at 120 ℃ subsequently, shine 40min down in ultraviolet light again and realize the substrate surface functionalization.
Step 2: configuration precursor liquid.Considering that Bi is at high temperature volatile, is 1.20:1 preparation precursor liquid with Bi, Ti mol ratio.With Bi (NO 3) 35H 2O is dissolved in the mixed solution of being made up of 10ml ethylene glycol and 10ml EGME, Ti (OC 4H 9) 4Be dissolved in the 30ml absolute ethyl alcohol, mix two solution and stir Bi in the maintenance solution 3+And Ti 4+Total concentration be 0.05mol/L, dropping ammonia to pH value is 2.5, is mixed with Bi 2Ti 2O 7Precursor liquid.
Step 3: thin film deposition.The glass substrate that will adhere to the OTS monofilm places the precursor liquid for preparing, and obtains noncrystalline membrane at 60 ℃ of deposit 14h.
Step 4: the crystallization of film.Dried noncrystalline membrane is put into Muffle furnace, be incubated 2h to obtain the burnt green stone phase Bi of crystalline state at 540 ℃ 2Ti 2O 7Film.
Embodiment 4
The present invention is a kind of to prepare the method for burnt green stone phase bismuth titanates function film at glass baseplate surface, may further comprise the steps:
Step 1: the functionalization of substrate.Glass substrate was successively used deionized water, absolute ethyl alcohol and acetone ultrasonic washing respectively 10 minutes, nitrogen dries up the back in OTS(octadecyl trichlorosilane) and the mixed solution of toluene (volume ratio of OTS and toluene is 1:99) in deposit 30s～20min with acquisition OTS monofilm, toast 5 minutes down to remove remained on surface solution at 120 ℃ subsequently, shine 40min down in ultraviolet light again and realize the substrate surface functionalization.
Step 2: configuration precursor liquid.Considering that Bi is at high temperature volatile, is 1.20:1 preparation precursor liquid with Bi, Ti mol ratio.With Bi (NO 3) 35H 2O is dissolved in the mixed solution of being made up of 10ml ethylene glycol and 10ml EGME, Ti (OC 4H 9) 4Be dissolved in the 30ml absolute ethyl alcohol, mix two solution and stir Bi in the maintenance solution 3+And Ti 4+Total concentration be 0.05mol/L, dropping ammonia to pH value is 2.5, is mixed with Bi 2Ti 2O 7Precursor liquid.
Step 3: thin film deposition.The glass substrate that will adhere to the OTS monofilm places the precursor liquid for preparing, and obtains noncrystalline membrane at 60 ℃ of deposit 14h.
Step 4: the crystallization of film.Dried noncrystalline membrane is put into Muffle furnace, be incubated 2h to obtain the burnt green stone phase Bi of crystalline state at 560 ℃ 2Ti 2O 7Film.
Embodiment 5
The present invention is a kind of to prepare the method for burnt green stone phase bismuth titanates function film at glass baseplate surface, may further comprise the steps:
Step 1: the functionalization of substrate.Glass substrate was successively used deionized water, absolute ethyl alcohol and acetone ultrasonic washing respectively 10 minutes, nitrogen dries up the back in OTS(octadecyl trichlorosilane) and the mixed solution of toluene (volume ratio of OTS and toluene is 1:99) in deposit 30s～20min with acquisition OTS monofilm, toast 5 minutes down to remove remained on surface solution at 120 ℃ subsequently, shine 40min down in ultraviolet light again and realize the substrate surface functionalization.
Step 2: configuration precursor liquid.With Bi, Ti mol ratio is 1:1 preparation precursor liquid.With Bi (NO 3) 35H 2O is dissolved in the mixed solution of being made up of 10ml ethylene glycol and 10ml EGME, Ti (OC 4H 9) 4Be dissolved in the 30ml absolute ethyl alcohol, mix two solution and stir Bi in the maintenance solution 3+And Ti 4+Total concentration be 0.05mol/L, dropping ammonia to pH value is 2.5, is mixed with Bi 2Ti 2O 7Precursor liquid.
Step 3: thin film deposition.The glass substrate that will adhere to the OTS monofilm places the Bi for preparing 2Ti 2O 7In the precursor liquid, obtain noncrystalline membrane at 60 ℃ of deposit 14h.
Step 4: the crystallization of film.Dried noncrystalline membrane is put into Muffle furnace, be incubated 2h to obtain the burnt green stone phase Bi of crystalline state at 500 ℃ 2Ti 2O 7Film.
With the thing phase composition of XRD test implementation example 2 prepared film, with the pattern of SEM survey film surface, its result as depicted in figs. 1 and 2; The inventive method is utilized the liquid phase self-assembling technique, is template with OTS, can successfully make Jiao Lvshi phase Bi at glass baseplate surface 2Ti 2O 7Crystalline film, and smooth smooth, the even compact of film surface, crystallite dimension is about 0.3～0.5 μ m; And this technology is simple, and the experiment condition of requirement satisfies easily, and cost is lower.Fig. 3 is the prepared Bi of embodiment 2 2Ti 2O 7The EDS power spectrum of film, the atomic ratio of Bi and Ti is 1.05 in the film, meets Bi substantially 2Ti 2O 7Stoichiometric proportion.The EDS test result of film has proved that further the chemical composition of film is Bi 2Ti 2O 7, consistent with the XRD test result.
The above only is one embodiment of the present invention, it or not whole or unique embodiment, the conversion of any equivalence that those of ordinary skills take technical solution of the present invention by reading specification of the present invention is claim of the present invention and contains.

Claims (3)

1. one kind prepares the method for burnt green stone phase bismuth titanates function film at glass baseplate surface, it is characterized in that, may further comprise the steps:
Step 1: glass substrate was used deionized water, absolute ethyl alcohol and acetone ultrasonic washing 10 minutes successively, nitrogen dries up the back and deposits 30s～20min to obtain the OTS monofilm in the mixed solution of octadecyl trichlorosilane and toluene, subsequently 120 ℃ down baking removing remained on surface solution, and then in ultraviolet light irradiation 40～60min down; The volume ratio of octadecyl trichlorosilane and toluene is 1:99 in the mixed solution of octadecyl trichlorosilane (OTS) and toluene;
Step 2: with A mol Bi (NO 3) 35H 2O is dissolved in the mixed solution of being made up of isopyknic ethylene glycol and EGME, with B mol Ti (OC 4H 9) 4Be dissolved in the absolute ethyl alcohol, mix two solution then and stir making Bi in the solution 3+And Ti 4+Total concentration be 0.05mol/L～0.10mol/L, it is 2.5 that dropping ammonia is regulated the pH value, promptly gets Bi 2Ti 2O 7Precursor liquid; A:B=(1～1.2): 1;
Step 3: the Bi that the glass substrate that adheres to the OTS monofilm that step 1 is prepared places step 2 to prepare 2Ti 2O 7In the precursor liquid, obtain noncrystalline membrane at 50 ℃～70 ℃ deposit 14h by liquid deposition;
Step 4: dried noncrystalline membrane is put into Muffle furnace, be incubated 2h to obtain the burnt green stone phase Bi of crystalline state at 500-560 ℃ 2Ti 2O 7Film.
2. method according to claim 1 is characterized in that A:B=1.2:1.
3. method according to claim 1 is characterized in that, Bi in the step 2 3+And Ti 4+Total concentration be 0.05mol/L.
CN 201210128351 2012-04-27 2012-04-27 Method for manufacturing pyrochlore phase bismuth titanate functional films on surfaces of glass substrates Expired - Fee Related CN102659400B (en)

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