CN1821087A - Neodymium doped bismuth titanate nano line array ferro-electric storage material and its synthetic method - Google Patents
Neodymium doped bismuth titanate nano line array ferro-electric storage material and its synthetic method Download PDFInfo
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- CN1821087A CN1821087A CN 200610018483 CN200610018483A CN1821087A CN 1821087 A CN1821087 A CN 1821087A CN 200610018483 CN200610018483 CN 200610018483 CN 200610018483 A CN200610018483 A CN 200610018483A CN 1821087 A CN1821087 A CN 1821087A
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Abstract
The present invention relates to nanometer line array ferroelectric storage material of (Bi,Nd)4Ti<3O12 (BNT) epitaxially growing in c axis on the substrate and its synthesis process. It is synthesized through selecting substrate capable of matching the lattice of BNT material, magnetically controlled sputtering Au or Pt quantum dots as catalyst, compounding precursor solution containing Bi3, Nd3+ and Ti4+, and setting the precursor solution inside high pressure reactor to grow the BNT epitaxially growing in c axis under strictly controlled hydrothermal synthesis conditions. Using the nanometer line array in vertical record mode can raise the storing capacity greatly so as to reduce the device size. The ferroelectric nanometer line array is expected to substitute ferroelectric film used as storing medium.
Description
Technical field
The present invention relates to a kind of novel ferroelectric storage medium, particularly a kind of Nd-doped bismuth titanate that the high c axle of oriented growth is orientated on substrate [(Bi, Nd)
4Ti
3O
12, BNT] and nano line array ferro-electric storage material and synthetic method thereof.
Background technology
The ferroelectric memory material is the important materials that aspects such as modern microelectronics, MEMS (micro electro mechanical system), information storage are used, wherein bismuth titanates (Bi
4Ti
3O
12) be the simplest a kind of ferroelectric material of structure in the bismuth layer-like compound, have excellent electricity, optics and photoelectronics performance, at aspects such as modern microelectronics, MEMS (micro electro mechanical system), information storage wide application prospect is arranged, become the focus of current new function material research.Reported that at present employing MOCVD, Sol-Gel, RF-Sputtering, methods such as Plus Laser Deposition (PLD), ECRPlasmas Deposition prepare Bi
4Ti
3O
12Ferroelectric membranc, but adopt these methods all must pass through the high temperature crystallization process, the high temperature crystallization process can make the interface generation mutual diffusion mutually between substrate material and film, film and the electrode for a long time, sometimes even chemical reaction takes place, and institute's synthetic material piezoelectric activity is low, coercive field E
cHeight is unfavorable for polarization.Kind and method such as the A position doping orientation that change sample of people such as U.Chon by changing substrate prepared comparatively significantly BNT ferroelectric membranc of a, b orientation, and the ferroelectric properties of material obtains certain raising.Above-mentioned a, b orientation is flush type, because there is the critical size effect in the crystal grain of film, this will limit the raising of ferroelectric film memory storage density greatly, is difficult to satisfy the requirement of current high-density ferroelectric memory development.How further improving the storage density of ferroelectric memory, is the ardent targets of pursuing of people.
Summary of the invention
The neodymium doped bismuth titanate nano line array ferro-electric storage material and the growth synthetic method thereof that the purpose of this invention is to provide a kind of high storage density.
Synthetic method of the present invention is:
One, preparation contains Bi
3+, Nd
3+And Ti
4+Precursor solution, its prescription is:
1, bismuth oxide and nitrate 0.04～0.12mol/L thereof,
2, neodymium nitrate [Nd (NO
3)
3] 0.016～0.025mol/L,
3, titanium oxide and titanate 0.05～0.09mol/L thereof,
4, mineralizer 1.0～6.0mol/L,
5, organic formwork agent 0.005～0.1mol/L,
6, water 55.5mol/L,
Wherein, bismuth oxide and nitrate thereof are: bismuth oxide (Bi
2O
3), Bismuth trinitrate (Bi (NO
3)
35H
2O);
Titanium oxide and titanate thereof are: tetrabutyl titanate (Ti (OC
4H
9)
4), titanium tetrachloride (TiCl
4) and titanium dioxide (TiO
2);
Mineralizer is: sodium hydroxide (NaOH), potassium hydroxide (KOH);
Organic formwork agent is: polyoxyethylene glycol (PEG, molecular-weight average 9000-12500), polyvinyl alcohol (PVA-124), cetyl trimethylammonium bromide (CTAB, C
19H
42BrN), thymus nucleic acid (DNA).
Two, select monocrystal chip
Strontium titanate (the SrTiO that selects lattice parameter and BNT lattice parameter to be complementary
3) or ruthenic acid strontium (SrRuO
3) monocrystal chip, the surface is cleaned, and with magnetron sputtering method sputter gold (Au) or platinum (Pt) quantum dot on substrate.
Three, oriented growth
1, precursor solution for preparing and the monocrystal chip of handling well are put into high-pressure reaction vessel;
2, Heating temperature 175～℃ 2, pressure 2～3MPa;
3, through 24～96 hours hydro-thermal reactions.
Four, remove high pressure and take out substrate, washed 30 minutes with deionized water and dehydrated alcohol respectively, under 50～80 ℃ of conditions, dried by the fire 2～8 hours, characterize the performance of the high c axle orientation nano array ferro-electric storage material of growth.
When above-mentioned precursor solution is pressed formulated, should be through stirring fully and the ultra-sonic dispersion processing, the adding mineralizer is the crystallization that helps product, uses organic formwork agent can make Bi
3+, Nd
3+And Ti
4+Precursor solution mix, play " soft mode " effect simultaneously, be beneficial to the oriented growth of product under the condition of hydro-thermal.The raw material of above-mentioned prescription should be chemical pure or analytical pure.
This method growth synthetic neodymium doped bismuth titanate nano line array ferro-electric storage material, its nanowire diameter is relevant with the size that sputters at on-chip Au or Pt quantum dot, is generally 10～50 nanometers; The length of nano wire is relevant with the time of carrying out hydro-thermal reaction, is generally 1 micron～5 microns.
The present invention's synthetic neodymium doped bismuth titanate nano line array ferro-electric storage material of growing is a high c axle orientation, is implemented in large area deposition nano-wire array on the substrate, the product purity height of acquisition, and reduce the crystallization temperature of material greatly.As ferroelectric storage media, utilize the perpendicular recording pattern of nano-wire array can improve storage capacity on the device unit surface greatly it, its storage density can reach 1terabit/cm
2Thereby, device size is further reduced, will become ferro-electric storage material of new generation.
Embodiment
The prescription and the processing parameter (reactor volume 50ml, compactedness is 80%) of the synthetic neodymium doped bismuth titanate nano line array ferro-electric storage material of growth are described with embodiment below.
Embodiment one: with Bi (NO
3)
3, Nd (NO
3)
3And Ti (OC
4H
9)
4Be main raw material
| Sequence number | Raw material | Consumption/mol | Processing parameter |
| 1 2 3 4 5 6 | Bi(NO 3) 3·5H 2O Nd(NO 3) 3 Ti(OC 4H 9) 4 NaOH H 2O PEG | 0.00325 0.00085 0.003 0.04 2 2×10 -4 | 2℃ 24h 2MPa |
By the synthetic neodymium doped bismuth titanate nano line array ferro-electric storage material of aforementioned manner growth.
Embodiment two: with Bi
2O
3, Nd (NO
3)
3And TiO
2Be main raw material
| Sequence number | Raw material | Consumption/mol | Processing parameter |
| 1 2 3 4 5 6 | Bi 2O 3 Nd(NO 3) 3 TiO 2 KOH H 2O PVA | 0.001625 0.00085 0.003 0.2 2 2×10 -4 | 2℃ 72h 2MPa |
By the synthetic neodymium doped bismuth titanate nano line array ferro-electric storage material of aforementioned manner growth.
Embodiment three: with Bi (NO
3)
3, Nd (NO
3)
3And TiCl
4Be main raw material
| Sequence number | Raw material | Consumption/mol | Processing parameter |
| 1 2 3 4 5 6 | Bi(NO 3) 3·5H 2O Nd(NO 3) 3 TiCl 4 KOH H 2O CTAB | 0.00325 0.00085 0.003 0.08 2 4×10 -4 | 2℃ 36h 2MPa |
By the synthetic neodymium doped bismuth titanate nano line array ferro-electric storage material of aforementioned manner growth.
Embodiment four: with Bi
2O
3, Nd (NO
3)
3And TiCl
4Be main raw material
| Sequence number | Raw material | Consumption/mol | Processing parameter |
| 1 2 3 4 5 6 | Bi 2O 3 Nd(NO 3) 3 TiCl 4 NaOH H 2O DNA | 0.001625 0.00085 0.003 0.08 2 4×10 -4 | 2℃ 48h 3MPa |
By the synthetic neodymium doped bismuth titanate nano line array ferro-electric storage material of aforementioned manner growth.
In above-mentioned prescription and the processing parameter, sequence number 1,2 and 3 is main raw materials, and corresponding ionic concn should be controlled in certain scope, and too high meeting causes that the product crystallization is incomplete; Cross to hang down and then can not effectively synthesize the BNT nano wire, and in this prescription (Bi, Nd)
3+And Ti
4+Concentration should be controlled at 0.05～0.12mol/L.Sequence number 4 mineralizer for adding in the reaction, the amount of its type and interpolation will influence the crystallization degree of product, and the type and the addition of different main raw material requirement mineralizers are also different, such as with Bi (NO
3)
35H
2O, Nd (NO
3)
3And Ti (OC
4H
9)
4During for main raw material, the NaOH that selects 1mol/L is as mineralizer, and with Bi
2O
3, Nd (NO
3)
3And TiO
2During for main raw material, the KOH that then selects 5mol/L is as mineralizer etc.Sequence number 5 is to be used for hydro-thermal synthetic reaction medium, and the cumulative volume that finally is mixed with precursor solution should not surpass 80% of reactor volume.Sequence number 6 organic formwork agent for selecting, what of its kind and addition are very big to the oriented growth influence of nano wire.PVA and PEG in this prescription, CTAB plays similar template action to DNA respectively in synthetic, so add identical amount respectively.For the processing parameter in the hydrothermal reaction process, different main raw materials requires different temperature, pressure and reaction times.
Claims (6)
1, a kind of growth synthetic method of neodymium doped bismuth titanate nano line array ferro-electric storage material is characterized in that the growth method of closing is:
One, preparation contains Bi
3+, Nd
3+And Ti
4+Precursor solution, its prescription is:
1) bismuth oxide and nitrate 0.04～0.12mol/L thereof
2) neodymium nitrate [Nd (NO
3)
3] 0.016～0.025mol/L
3) titanium oxide and titanate 0.05～0.09mol/L thereof
4) mineralizer 1.0～6.0mol/L
5) organic formwork agent 0.005～0.1mol/L
6) water 55.5mol/L
Wherein, bismuth oxide and nitrate thereof are: bismuth oxide (Bi
2O
3), Bismuth trinitrate (Bi (NO
3)
35H
2O);
Titanium oxide and titanate thereof are: tetrabutyl titanate (Ti (OC
4H
9)
4), titanium tetrachloride (TiCl
4) and titanium dioxide (TiO
2);
Mineralizer is: sodium hydroxide (NaOH), potassium hydroxide (KOH);
Organic formwork agent is: polyoxyethylene glycol (PEG, molecular-weight average 9000-12500), polyvinyl alcohol (PVA-124), cetyl trimethylammonium bromide (CTAB, C
19H
42BrN), thymus nucleic acid (DNA);
Two, select monocrystal chip
Strontium titanate (the SrTiO that selects lattice parameter and BNT lattice parameter to be complementary
3) or ruthenic acid strontium (SrRuO
3) monocrystal chip, the surface is cleaned, and with magnetron sputtering method sputter gold (Au) or platinum (Pt) quantum dot on substrate;
Three, oriented growth
1) precursor solution for preparing and the monocrystal chip of handling well are put into high-pressure reaction vessel;
2) Heating temperature 175～℃ 2, pressure 2～3MPa;
3) through growth response in 24～96 hours.
Four, remove high pressure and take out substrate, washed 30 minutes with deionized water and dehydrated alcohol respectively, under 50～8 ℃ of conditions, dried by the fire 2～8 hours, characterize the performance of the high c axle orientation nano array ferro-electric storage material of growth.
2, the growth synthetic method of neodymium doped bismuth titanate nano line array ferro-electric storage material according to claim 1 is characterized in that precursor solution prescription and processing parameter are:
Sequence number Raw material Consumption/mol Processing parameter
1 2 3 4 Bi(NO
3)
3·5H
2O Nd(NO
3)
3 Ti(OC
4H
9)
4 NaOH
0.00325 0.00085 0.003 0.04 2℃ 24h 2MPa
5 6 H
2O PEG
2 2×10
-4
3, the growth synthetic method of neodymium doped bismuth titanate nano line array ferro-electric storage material according to claim 1 is characterized in that precursor solution prescription and processing parameter are:
Sequence number Raw material Consumption/mol Processing parameter
1 2 3 4 5 6 Bi
2O
3 Nd(NO
3)
3 TiO
2 KOH H
2O PVA
0.001625 0.00085 0.003 O.2 2 2×10
-4 2℃ 72h 2MPa
4, the growth synthetic method of neodymium doped bismuth titanate nano line array ferro-electric storage material according to claim 1 is characterized in that precursor solution prescription and processing parameter are:
Sequence number Raw material Consumption/mol Processing parameter
1 2 3 4 5 6 Bi(NO
3)
3·5H
2O Nd(NO
3)
3 TiCl
4 KOH H
2O CTAB
0.00325 0.00085 0.003 0.08 2 4×10
-4 2℃ 36h 2MPa
5, the growth synthetic method of neodymium doped bismuth titanate nano line array ferro-electric storage material according to claim 1 is characterized in that precursor solution prescription and processing parameter are:
Sequence number Raw material Consumption/mol Processing parameter
1 2 3 4 5 6 Bi
2O
3 Nd(NO
3)
3 TiCl
4 NaOH H
2O DNA
0.001625 0.00085 0.003 0.08 2 4×10
-4 2℃ 48h 3MPa
6, a kind of neodymium doped bismuth titanate nano line array ferro-electric storage material of growth synthetic method manufacturing according to claim 1 is characterized in that at strontium titanate (SrTiO
3) or ruthenic acid strontium (SrRuO
3) be to be orientated the large area deposition nano-wire array on the monocrystal chip by high c axle, its nanowire diameter is 10～50 nanometers, length is 1～5 micron.
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