CN101376598A - Preparation of (020) preferred orientation bismuth titanate film - Google Patents

Preparation of (020) preferred orientation bismuth titanate film Download PDF

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CN101376598A
CN101376598A CNA2008101372468A CN200810137246A CN101376598A CN 101376598 A CN101376598 A CN 101376598A CN A2008101372468 A CNA2008101372468 A CN A2008101372468A CN 200810137246 A CN200810137246 A CN 200810137246A CN 101376598 A CN101376598 A CN 101376598A
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film
preparation
solution
preferred orientation
bismuth
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CN101376598B (en
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柯华
徐加焕
王文
陈林
贾德昌
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Harbin Institute of Technology
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Harbin Institute of Technology
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Abstract

The invention discloses a preparation method for the preferred orientation of bismuth titanate film, which relates to a preparation technique for a film material. The invention solves the problems of complex Bi4-xLaxTi3O12 film preparation technique, high crystallization temperature, rough surface, no preferred orientation, poor ferroelectric properties, low density and uneven particle size distribution in the prior art. The preparation method comprises the following steps: lanthanum nitrate and bismuth subnitrate are dissolved in acetic acid, and is mixed and stirred with tetrabutyl titanate solution provided with ethylene glycol solution to obtain Bi4-xLaxTi3O12 sol after the ethylene glycol solution is added, then the sol is spin-coated on a cleaned Pt/Ti/SiO2/Si substrate, dried and roasted, and after crystallization and heat treatment, the Bi4-xLaxTi3O12 film is obtained. The invention has the advantages of high film forming quality, low crystallization temperature, (020) preferred orientation, high ferroelectric properties, low cost and simple technique, thereby being suitable for industrialized production.

Description

The preparation method of a kind of (020) preferred orientation bismuth titanate film
Technical field
The invention belongs to the thin-film material field.
Background technology
Bismuth titanates (Bi 4Ti 3O 12) be a kind of ferroelectric material of excellent performance, because of it has unique electricity, optics and photoelectronics performance, wide application prospect is arranged at aspects such as modern microelectronics, MEMS (micro electro mechanical system), information storage.Studies show that the bismuth titanates (Bi that mixes lanthanum 4-xLa xTi 3O 12) having improved the ferroelectric properties of bismuth titanates to a great extent, fatigue property also obviously is better than the conventional iron electric material.But because the process temperature restrictions of large-scale integrated circuit is below 500 ℃, and adopt existing method to prepare the temperature of doped titanic acid bismuth thin film at present in most cases still more than 500 ℃, make coarse, the no preferred orientation of film surface, the poor ferroelectric property prepare, density is low, size distribution is uneven, complicated process of preparation, Tc height and unmanageable shortcoming.
Summary of the invention
The present invention seeks to prepare Bi in the prior art in order to solve 4-xLa xTi 3O 12Thin-film technique complexity, Tc height, surface irregularity, no preferred orientation, poor ferroelectric property, the problem that density is low and size distribution is uneven, and the preparation method of a kind of (020) preferred orientation bismuth titanate film is provided.
Preparation method's step of a kind of (020) preferred orientation bismuth titanate film is as follows: one, the mixture and the acetic acid of lanthanum nitrate and bismuth subnitrate are pressed 1: 10～80 mixed in molar ratio, slowly add mass percent concentration then and be 99.0%～99.8% ethylene glycol solution, make that the mol ratio of lanthanum ion and bismuth ion summation and ethylene glycol is 1: 5～18 in the solution, stirring at room 8～12min gets solution A; Two, be that 99.0%～99.8% ethylene glycol solution slowly adds in the tetrabutyl titanate with mass percent concentration, make that the mol ratio of bismuth ion and ethylene glycol is 1: 5～18 in the solution, stirring at room 8～12min, solution B; Three, solution A and solution B are mixed, stirring at room 20～40min gets Bi 4-xLa xTi 3O 12Colloidal sol; Four, with Pt/Ti/SiO 2/ Si substrate is supersound process 4～6min in acetone and dehydrated alcohol respectively, drying; Five, with Bi 4-xLa xTi 3O 12Colloidal sol is spun to the Pt/Ti/SiO that handled by sol evenning machine 2On/Si the substrate, with 1300～1700r/min spin coating 10s, again with dry at ambient temperature 4～6min behind 2800～3200r/min spin coating 15s, placing temperature again is dry 20～40min under 50～70 ℃ of conditions, gets film C; Six, film C is put into take out behind 580～620 ℃ of retort furnace roasting 8～12min and is cooled to room temperature, Bi 4-xLa xTi 3O 12Film; Lanthanum nitrate and bismuth subnitrate are according to Bi in the step 1 4-xLa xTi 3O 12Stoichiometric ratio takes by weighing, wherein 0＜X＜1.
Bi among the present invention 4-xLa xTi 3O 12Colloidal sol can further be prepared into Bi 4-xLa xTi 3O 12Nano-powder begins to generate the uhligite phase at 500 ℃; Bi 4-xLa xTi 3O 12Film presents (020) preferred orientation, and the preferred orientation degree of film is the highest during x=0.75.(020) preferred orientation will improve ferroelectric properties.Advantage of the present invention is to adopt Prepared by Sol Gel Method Bi 4-xLa xTi 3O 12Thin-film material, technology is simple, Tc is low, film density height, even particle distribution, surfaceness is little only is 5～10nm, and show as (020) preferred orientation, and can be in the substrate of big area or arbitrary shape film forming, can obtain the film that thickness is 80～300nm, and this thin-film ferroelectric superior performance is fit to suitability for industrialized production.
Description of drawings
Fig. 1 is embodiment 11 gained Bi 3.25La 0.75Ti 3O 12The XRD spectra of film, Fig. 2 is gained Bi in the embodiment 11 3.25La 0.75Ti 3O 12The atomic force micrograph of film film.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: preparation method's step of present embodiment (020) preferred orientation bismuth titanate film is as follows: one, the mixture and the acetic acid of lanthanum nitrate and bismuth subnitrate are pressed 1: 10～80 mixed in molar ratio, slowly add mass percent concentration then and be 99.0%～99.8% ethylene glycol solution, make that the mol ratio of lanthanum ion and bismuth ion summation and ethylene glycol is 1: 5～18 in the solution, stirring at room 8～12min gets solution A; Two, be that 99.0%～99.8% ethylene glycol solution slowly adds in the tetrabutyl titanate with mass percent concentration, make that the mol ratio of bismuth ion and ethylene glycol is 1: 5～18 in the solution, stirring at room 8～12min, solution B; Three, solution A and solution B are mixed, stirring at room 20～40min gets Bi 4-xLa xTi 3O 12Colloidal sol; Four, with Pt/Ti/SiO 2/ Si substrate is supersound process 4～6min in acetone and dehydrated alcohol respectively, drying; Five, with Bi 4-xLa xTi 3O 12Colloidal sol is spun to the Pt/Ti/SiO that handled by sol evenning machine 2On/Si the substrate, with 1300～1700r/min spin coating 10s, again with dry at ambient temperature 4～6min behind 2800～3200r/min spin coating 15s, placing temperature again is dry 20～40min under 50～70 ℃ of conditions, gets film C; Six, film C is put into take out behind 580～620 ℃ of retort furnace roasting 8～12min and is cooled to room temperature, Bi 4-xLa xTi 3O 12Film; Lanthanum nitrate and bismuth subnitrate are according to Bi in the step 1 4-xLa xTi 3O 12Stoichiometric ratio takes by weighing, wherein 0＜X＜1.
The Bi that obtains in the present embodiment step 3 4-xLa xTi 3O 12Colloidal sol, 60 ℃ down insulation place again and form xerogel under 100 ℃ of conditions after 2 days, be warmed up to 400 ℃ and be incubated 1h with the speed of 5 ℃/min then, be warmed up to 500 ℃ or 600 ℃ again and be incubated 1h again, take out after dropping to room temperature, Bi 4-xLa xTi 3O 12 nano-powders.
Embodiment two: not being both in the step 1 the mixture of lanthanum nitrate and bismuth subnitrate and acetic acid of present embodiment and embodiment one by 1: 40 mixed in molar ratio, slowly add mass percent concentration then and be 99.5% ethylene glycol solution, make that the mol ratio of lanthanum ion and bismuth ion summation and ethylene glycol is 1: 10 in the solution, stirring at room 10min.Other step and parameter are identical with embodiment one.
Embodiment three: not being both in the step 2 of present embodiment and embodiment one is that 99.5% ethylene glycol solution slowly adds in the tetrabutyl titanate with mass percent concentration, make that the mol ratio of bismuth ion and ethylene glycol is 1: 10 in the solution, stirring at room 10min.Other step and parameter are identical with embodiment one.
Embodiment four: present embodiment and embodiment one be not both that the stirring at room time is 30min in the step 3.Other step and parameter are identical with embodiment one.
Embodiment five: not being both in the step 4 of present embodiment and embodiment one with Pt/Ti/SiO 2/ Si substrate is supersound process 5min in acetone and dehydrated alcohol respectively.Other step and parameter are identical with embodiment one.
Embodiment six: not being both in the step 5 of present embodiment and embodiment one with 1500r/min spin coating 10s, again with 3000r/min spin coating 15s.Other step and parameter are identical with embodiment one.
Embodiment seven: present embodiment and embodiment one be not both dry at ambient temperature 5min in the step 5, placing temperature again is dry 30min under 60 ℃ of conditions.Other step and parameter are identical with embodiment one.
Embodiment eight: not being both in the step 6 of present embodiment and embodiment one put into film C to take out behind 600 ℃ of retort furnace roasting 10min and is cooled to room temperature.Other step and parameter are identical with embodiment one.
Embodiment nine: but present embodiment and embodiment one be not both the step 6 repetitive operation 2～10 times.Other step and parameter are identical with embodiment one.
Embodiment ten: but present embodiment and embodiment nine be not both the step 6 repetitive operation 6 times.Other step and parameter are identical with embodiment nine.
Embodiment 11: preparation method's step of present embodiment (020) preferred orientation bismuth titanate film is as follows: one, the mixture and the acetic acid of lanthanum nitrate and bismuth subnitrate are pressed 1: 40 mixed in molar ratio, slowly add mass percent concentration then and be 99.5% ethylene glycol solution, make that the mol ratio of lanthanum ion and bismuth ion summation and ethylene glycol is 1: 10 in the solution, stirring at room 10min gets solution A; Two, be that 99.5% ethylene glycol solution slowly adds in the tetrabutyl titanate with mass percent concentration, make that the mol ratio of bismuth ion and ethylene glycol is 1: 10 in the solution, stirring at room 10min, solution B; Three, solution A and solution B are mixed, stirring at room 30min gets Bi 4-xLa xTi 3O 12Colloidal sol; Four, with Pt/Ti/SiO 2/ Si substrate is supersound process 5min in acetone and dehydrated alcohol respectively, drying; Five, with Bi 4-xLa xTi 3O 12Colloidal sol is spun to the Pt/Ti/SiO that handled by sol evenning machine 2On/Si the substrate, with 1500r/min spin coating 10s, again with dry at ambient temperature 5min behind the 3000r/min spin coating 15s, placing temperature again is dry 30min under 60 ℃ of conditions, gets film C; Six, film C is put into take out behind 600 ℃ of retort furnace roasting 10min and is cooled to room temperature, Bi 3.25La 0.75Ti 3O 12Film; Wherein lanthanum nitrate and bismuth subnitrate are according to Bi in the step 1 3.25La 0.75Ti 3O1 2Stoichiometric ratio takes by weighing.
Gained Bi in the present embodiment 3.25La 0.75Ti 3O 12Film XRD test result as shown in Figure 1, Bi 3.25La 0.75Ti 3O 12Film presents (020), (111) preferred orientation, and through performance test, the ferroelectric-ferromagnetic performance of this film significantly improves; Bi 3.25La 0.75Ti 3O 12The atomic force micrograph of film as shown in Figure 2, Bi 3.25La 0.75Ti 3O 12The surfaceness of film is smaller only to be 5～10nm, film density height, even particle distribution.

Claims (8)

1, the preparation method of a kind of (020) preferred orientation bismuth titanate film, the preparation method's step that it is characterized in that (020) preferred orientation bismuth titanate film is as follows: one, the mixture and the acetic acid of lanthanum nitrate and bismuth subnitrate are pressed 1: 10～80 mixed in molar ratio, slowly add mass percent concentration then and be 99.0%～99.8% ethylene glycol solution, make that the mol ratio of lanthanum ion and bismuth ion summation and ethylene glycol is 1: 5～18 in the solution, stirring at room 8～12min gets solution A; Two, be that 99.0%～99.8% ethylene glycol solution slowly adds in the tetrabutyl titanate with mass percent concentration, make that the mol ratio of bismuth ion and ethylene glycol is 1: 5～18 in the solution, stirring at room 8～12min, solution B; Three, solution A and solution B are mixed, stirring at room 20～40min gets Bi 4-xLa xTi 3O 12Colloidal sol; Four, with Pt/Ti/SiO 2/ Si substrate is supersound process 4～6min in acetone and dehydrated alcohol respectively, drying; Five, with Bi 4-xLa xTi 3O 12Colloidal sol is spun to the Pt/Ti/SiO that handled by sol evenning machine 2On/Si the substrate, with 1300～1700r/min spin coating 10s, again with dry at ambient temperature 4～6min behind 2800～3200r/min spin coating 15s, placing temperature again is dry 20～40min under 50～70 ℃ of conditions, gets film C; Six, film C is put into take out behind 580～620 ℃ of retort furnace roasting 8～12min and is cooled to room temperature, Bi 4-xLa xTi 3O 12Film; Lanthanum nitrate and bismuth subnitrate are according to Bi in the step 1 4-xLa xTi 3O 12Stoichiometric ratio takes by weighing, wherein 0＜X＜1.
2, the preparation method of a kind of (020) according to claim 1 preferred orientation bismuth titanate film, it is characterized in that in the step 1 the mixture of lanthanum nitrate and bismuth subnitrate and acetic acid by 1: 40 mixed in molar ratio, slowly add mass percent concentration then and be 99.5% ethylene glycol solution, make that the mol ratio of lanthanum ion and bismuth ion summation and ethylene glycol is 1: 10 in the solution, stirring at room 10min.
3, the preparation method of a kind of (020) according to claim 1 preferred orientation bismuth titanate film, it is characterized in that in the step 2 with mass percent concentration being that 99.5% ethylene glycol solution slowly adds in the tetrabutyl titanate, make that the mol ratio of bismuth ion and ethylene glycol is 1: 10 in the solution, stirring at room 10min.
4, the preparation method of a kind of (020) according to claim 1 preferred orientation bismuth titanate film is characterized in that the stirring at room time is 30min in the step 3.
5, the preparation method of a kind of (020) according to claim 1 preferred orientation bismuth titanate film is characterized in that in the step 4 Pt/Ti/SiO 2/ Si substrate is supersound process 5min in acetone and dehydrated alcohol respectively.
6, the preparation method of a kind of (020) according to claim 1 preferred orientation bismuth titanate film is characterized in that in the step 5 with 1500r/min spin coating 10s, again with 3000r/min spin coating 15s.
7, the preparation method of a kind of (020) according to claim 1 preferred orientation bismuth titanate film is characterized in that dry at ambient temperature 5min in the step 5, and placing temperature again is dry 30min under 60 ℃ of conditions.
8, the preparation method of a kind of (020) according to claim 1 preferred orientation bismuth titanate film is characterized in that in the step 6 film C put into taking out behind 600 ℃ of retort furnace roasting 10min and is cooled to room temperature.
CN2008101372468A 2008-09-28 2008-09-28 Preparation of (020) preferred orientation bismuth titanate film Expired - Fee Related CN101376598B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103217458A (en) * 2012-11-14 2013-07-24 陕西科技大学 Method for preparing humidity-sensitive film
CN104529436A (en) * 2015-01-22 2015-04-22 哈尔滨工业大学 Preparation method of high-density Bi(4-x)NdxTi3O12 ferroelectric ceramic

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103217458A (en) * 2012-11-14 2013-07-24 陕西科技大学 Method for preparing humidity-sensitive film
CN104529436A (en) * 2015-01-22 2015-04-22 哈尔滨工业大学 Preparation method of high-density Bi(4-x)NdxTi3O12 ferroelectric ceramic
CN104529436B (en) * 2015-01-22 2016-05-18 哈尔滨工业大学 A kind of high-compactness Bi4-xNdxTi3O12The preparation method of ferroelectric ceramics

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