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SOLUTION DERIVED LEAD SOLUTION DERIVED LEAD- FREE (Bi FREE (Bi 0.5 0.5 Na Na 0.5 0.5 )TiO )TiO 3 BaTiO BaTiO 3 (BNBT) (BNBT) THIN FILMS IN THE PROXIMITY OF THE MORPHOTROPIC PHASE THIN FILMS IN THE PROXIMITY OF THE MORPHOTROPIC PHASE BOUNDARY

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SLIDE 1

SOLUTION DERIVED LEAD SOLUTION DERIVED LEAD- FREE (Bi FREE (Bi0.5

0.5Na

Na0.5

0.5)TiO

)TiO3–BaTiO BaTiO3 (BNBT) (BNBT) THIN FILMS IN THE PROXIMITY OF THE MORPHOTROPIC PHASE THIN FILMS IN THE PROXIMITY OF THE MORPHOTROPIC PHASE BOUNDARY (MPB) BOUNDARY (MPB)

M.D. Mezcua, J. Ricote, D.Chateigner1, C. Gutiérrez-Lázaro, I. Bretos, R. Jiménez, R. Sirera2 and M.L. Calzada

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

M.L. Calzada

Instituto Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas (ICMM-CSIC). Cantoblanco. 28049 – Madrid. Spain.

1 Laboratoire de Cristallographie et Sciences des Matériaux (CRISMAT). Ecole Nationale Supérieure d'Ingénieurs de Caen

(ENSICAEN). Université de Caen. 14050 – Caen. France.

2 Departamento de Química y Edafología. Facultad de Ciencias. Universidad de Navarra. 31080 – Pamplona, Navarra.

Spain.

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SLIDE 2
  • 1. Index

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

slide-3
SLIDE 3
  • 1. Objectives
  • 1. Objectives

Solution derived lead-free… Solution derived lead-free…

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

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SLIDE 4
  • 1. Objectives
  • The main goal of this work is the study of

lead-free ferroelectric oxides based on the (1-x)(Bi0.5Na0.5)TiO3-xBaTiO3 (BNBT) system to replace the well known Pb(ZrxTi1-x)O3 (PZT) and the manufacturing of these materials as

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

thin films for its integration in microelectronic devices.

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SLIDE 5

Lead-free compositions to substitute lead based- on compositions (PZT)

  • 1. Objectives

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

Preparation of thin films

Integration of ferroelectric materials in the information technologies (ITRS 2011) Actual trends on the manufacturing of thin films

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SLIDE 6
  • 2. Introduction

2.Introduction

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

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SLIDE 7
  • 2. Introducción

MPB Solution derived lead-free… Solution derived lead-free…

BNT-BT Phase diagram (1-x)(Bi0.5Na0.5)TiO3-xBaTiO3 (BNBT) Solid solution Morphotropic phase boundary(MPB)

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

Thomas et al. Solid State Sci 2008; 10:934-940

MPB

Takenaka et al. Jpn J Appl Phys 1991; 30: 2236-39

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SLIDE 8
  • 2. Introduction
  • !

Towards the miniaturization of ferroelectric materials and their integration into microelectronic devices

High permitivity

DRAMs

Electro-optic activity

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

Piezoelectricity Pyroelectricity Ferroelectricity

NVFRAMs Infrared sensor Sensors Actuators

Ferroelectric films

  • Bretos. Ph. D Thesis UAM 2006
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SLIDE 9
  • 2. Introduction

773-813 K 528-673K

Rhombohedral phase Tetragonal phase Cubic phase

Bulk ceramic Bi0.5Na0.5TiO3

Increasing temperature

Rhombohedral Rhombohedral Tetragonal Tetragonal

Thomas et al.Solid State Science 2010; 12: 311-17

Solution derived lead-free… Solution derived lead-free…

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

Bi0.5Na0.5TiO3 0.89Bi0.5Na0.5TiO3- 0.11BaTiO3

Single-crystal X-ray diffraction

Rhombohedral phase with tetragonal inclusions Tetragonal

Tetragonal Tetragonal

0.90Bi0.5Na0.5TiO3- 0.10BaTiO3

Thin film

Jones et al. Acta Crystallogr B 2000; B56:426-30 Jones et al. Acta Crystallogr B 2002; B58:168-78 Cheng et al. Appl Phys Lett 2004; 85: 2319-21 Bretos et al. Mater Lett 2011; 65:2714-2716 Thomas et al.Solid State Science 2010; 12: 311-17

Displacement of the MPB composition Structural effects

The reason could be

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SLIDE 10
  • 3. Experimental Procedure
  • 3. Experimental procedure

Solution derived lead-free… Solution derived lead-free…

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

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SLIDE 11

CH3COOH + OH(CH2)3OH + H2O

Metallic Metallic precursor precursor Solvents Solvents Molar ratios 1.0:10.0 f Ti (IV) to any solvents 10.0 mol% of Bi(III) excess + 10.0 mol% of Na(I) excess Reflux in air for 8h

Na(OCOCH3).3H2O + Bi(OCOCH3)3 + Ti(CH3COCHCOCH3)2(OC3H7)2

Bi0.5Na0.5TiO3 Precursor sol

CH3CH2COOH + (CH3CH2CO)2O BaCO3 C4H9OH + CH 3COCH2COCH3

Reflux in air for 2 h Stirring at room temperature Stirring at room temperature

C4H9OH

Metallic Metallic precursor precursor Metallic Metallic precursor precursor Solvents Solvents Solvents Solvents Solvents Solvents

BaTiO3 Precursor solution Ti(OC4H10)

  • 3. Experimental procedure

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

Precursor sol (0.60 mol L-1) Precursor solution ( 0.30 mol L-1) Bi0.5Na0.5TiO3-BaTiO3 Precursor solution ( 0.60 mol L-1) C2H5OH

Solvent Solvent

Bi0.5Na0.5TiO3- BaTiO3 Precursor solution ( 0.20 mol L-1)

Hoffmann el al. J Eur Ceram Soci 1999: 19 ;1339-1343 Alonso et al. J Am Ceram Soci 2008; 92 [10]: 2218-25

slide-12
SLIDE 12

Bi0.5Na0.5TiO3 Precursor sol

(10%mol.exc. Bi2O3+10% mol. exc. NaO)

Bi0.5Na0.5TiO3 Precursor sol (BNTs) BaTiO3 Precursor solution (BT)

Stirring at room temperature(72 h)

Composition in the vicinity of the MPB

  • 3. Experimental procedure

BNBTs10.0 BNBTs5.5 BNBTs6.5 BNBTs8.0 BNBTs10.0 BNBT5.5 BNBT10.0 BNBT15.0

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Stoichiometric 10% mol. Bi(III) and Na(I) excesses

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

Crystalline powders Diluted solution to prepare the films by CSD

Dried ethanol

Annealed at 900ºC(1h)

Heat shock Slow cooling

Crystallization: RTP

Schwartz Cr Chim 2004; 7 :433-461

25ºC/ 60s Vacuum 25ºC/ 120s Oxygen 22s 650ºC/60s 22s 100ºC Refrigeration

Stoichiometric 10% mol. Bi(III) and Na(I) excesses

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SLIDE 13
  • 4. Results and discussion
  • 4. Results and discussion

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

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SLIDE 14

4.1 Crystalline powders

  • 4. Results and discussion

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

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SLIDE 15

Structural analysis by XRD

  • f the powders

Nominal composition Stoichiometric Excesses of NaO and Bi2O3 For different molar

  • 4. Results and discussion

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

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For different molar ratios of BNT/BT

Near to

Coexistence of these structures

Tetragonal Rhombohedral Morphotropic phase boundary (MPB)

Takenaka et al. Jpn J Appl Phys 1991; 30: 2236-39

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SLIDE 16

11)T )T )T (101)T (110)T (002)T (200)T 12)T 11)T

39.3 39.6 39.9 40.2 40.5

(111)T

Intensity (a.u.) 2θ(º)

(003)R (021)R

a)

46.0 46.5 47.0 Intensity (a.u.) 2θ(º)

(002)T (200)T (202)R b)

  • 4. Results and discussion

Structural analysis of the crystalline phase in the stoichiometric powders with different BNT/BT molar ratios

Step used 0.005º/5s Step used 0.005º/5s

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

20 30 40 50 60

* * * * * * * *

(202)R (111 (110)R

BNBTs10.0 BNBTs8.0 BNBTs6.5

Intensity (a.u.) 2θ(º)

BNBTs5.5

(101)R (001)T (100)T (012)R (021)R (003)R (0 (2 (102)T (201)T (210)T (113)R (211)R (11 (21 (104)R (122)R

* *

Step used 0.05º/3s

Step used 0.005º/5s Step used 0.005º/5s

Jones et al. Acta Crystallogr B 2000; B56:426-30 Jones et al. Acta Crystallogr B 2002; B58:168-78

JCPDS: 36-0640(Rhombohedral Bi0.5Na0.5TiO3) 05-0626(Tetragonal BaTiO3)

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SLIDE 17

(003)R (021)R (111)T

BNBTs6.5 Intensity (a.u.) BNBTs8.0

a)

46.0 46.5 47.0 Intensity (a.u.) 2θ (º) BNBTs6.5 BNBTs8.0

(200)T (202)R (002)T b)

  • 4. Results and discussion

Structural analysis of crystalline stoichiometric powders for different BNT/BT molar ratios

Deconvolution has been made using program V1-40 and the peaks have been fitted to seudo-voigt 2 function

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

SAMPLES MOLAR RATIOS BNT/ BT NOMINAL COMPOSITION (stoichiometric) CRYSTALLINE STRUCTURES OBTAINED FROM XRD PATTERNS BNBTs5.5 94.5/5.5 (Bi0.5Na0.5)0.945Ba0.055TiO3 Rhombohedral BNBTs6.5 93.5/6.5 (Bi0.5Na0.5)0.935Ba0.065TiO3 Rhombohedral + tetragonal (MPB) BNBTs8.0 92.0/8.0 (Bi0.5Na0.5)0.920Ba0.080TiO3 Rombohedral + tetragonal (MPB) BNBTs10.0 90.0/10.0 (Bi0.5Na0.5)0.900Ba0.100TiO3 Tetragonal

39.5 40.0 40.5 2θ (º) 46.0 46.5 47.0 2θ (º)

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SLIDE 18

01)T 00)T (101)T (110)T (111)T (002)T (200)T 112)T 211)T

39.2 39.6 40.1 40.5 41.0

(111)T

2θ(º) Intensity (a.u.)

(003)R (021)R a)

45.2 45.6 46.0 46.4 46.8 47.2

(202)R

Intensity (a.u.) 2θ

(002)T (200)T b)

  • 4. Results and discussion

Structural analysis of the crystalline powders containing excesses of Na(I) and Bi(III)

Step used 0.005º/5s

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

20 30 40 50 60

(211)R (113)R

BNBT15.0 BNBT10.0

2θ(º) Intensity (a.u.)

BNBT5.5

(101)R (001 (100 (012)R (110)R (1 (003)R (021)R (0 (2 (202)R (102)T (201)T (210)T (11 (21 (104)R (122)R

*

Step used 0.05º/3s

Step used 0.005º/5s Step used 0.005º/5s

Jones et al. Acta Crystallogr B 2000; B56:426-30 Jones et al. Acta Crystallogr B 2002; B58:168-78

JCPDS: 36-0640(Rhombohedral Bi0.5Na0.5TiO3) 05-0626(Tetragonal BaTiO3)

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SLIDE 19
  • 4. Results and discussion

Structural analysis of crystalline powders with excesses of Na(I) and Bi(III) for different BNT/BT molar ratios

39.2 39.6 39.9 40.3 40.6 41.0

(021)R (003)R (111)T

Intensity (a.u.)

BNBT10.0

a)

45.2 45.6 46.0 46.4 46.8 47.2

(202)R (200)T (002)T

BNBT10.0

Intensity (a.u.)

b) Deconvolution has been made using program V1-40 and the peaks have been fitted to seudo-voigt 2 function

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

SAMPLE MOLAR RATIOS BNBT/BT NOMINAL COMPOSITION (10%molar exceso Bi2O3+ 10%molar exceso NaO) CRYSTALLINE STRUCTURE OBTAINED FROM XRD PATTERNS BNBT5.5 94.5/5.5 (Bi0.5Na0.5)0.945Ba0.055TiO3 Rhombohedral BNBT10.0 90.0/10.0 (Bi0.5Na0.5)0.900Ba0.100TiO3 Rhombohedral+ tetragonal (MPB) BNBT15.0 85.0/15.0 (Bi0.5Na0.5)0.850Ba0.150TiO3 Tetragonal 39.2 39.6 39.9 40.3 40.6 41.0 2θ(º) 45.2 45.6 46.0 46.4 46.8 47.2 2θ(º)

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SLIDE 20

200 250 300 350 400

ture (ºC)

  • 4. Results and discussion

Determination of the morphotropic phase boundary (MPB) for the crystalline powders

Stoichiometric nominal composition Nominal composition containing excesses of Na(I) +Bi(III)

200 250 300 350 400

ture (ºC)

Cubic Tetragonal Cubic Tetragonal

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

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5 10 15 20 25 30

50 100 150 200

Temperatu (Bi0.5Na0.5)1-xBaxTiO3 (mol%)

Rout et al. J Ceram Soc Jpn 2009; 117 [7]: 797-800

5 10 15 20 25 30

50 100 150 200

Temperatu (Bi0.5Na0.5)1-xBaxTiO3 (mol%)

Tetragonal

Rhomboedral

MPB Tetragonal

Rhombohedral

MPB

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SLIDE 21

4.2 Thin films

  • 4. Results and discussion

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

Ferroelectric system in thin film form:

  • Lost by volatilization of Na(I)+Bi(III)
  • Change
  • f

the phase because

  • f

structural effects induced by the substrate

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SLIDE 22

1)

Pt (200) Pt (200) vskite Perovskite erovskite

Pt(111)

(111)

kite

(a.u.)

32.0 32.3 32.5 32.8 33.0 Perovskite R Perovskite T Intensity (a.u.) 2θ (º)

  • 4. Results and discussion

XRD patterns of BNBTs thin films without excesses of any metallic precursor

Step used 0.005º/5s

Reflections from the substrate

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

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Kβ Pt (111

20 25 30 35 40 45 50

Pt Perov Per

BixPt (1

Perovski

Intensity (a

BNBTs5.5 BNBTs6.5 BNBTs8.0 BNBTs10.0

2θ(º)

Step used 0.05º/3s Ba2+ has been incorporated into the structure

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SLIDE 23
  • 4. Results and discussion

Pt (200)

Perovskite Perovskite Perovskite

Pt(111)

  • vskite

a.u.)

t (111) t(111)

32.0 32.3 32.5 32.8 33.0

Intensity (a.u.)

2θ(º)

Perovskite T Perovskite R

XRD patterns of BNBT thin films with addition of Na(I) and Bi(III) excesses in the nominal composition

Step used 0.005º/5s

Reflections from the substrate

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

20 25 30 35 40 45 50

Perov

BNBT15.0 BNBT10.0

Intensity(a.u 2θ(º)

BNBT5.5

KβPt BixPt(

Step used 0.05º/3s Ba2+ has been incorporated into the structure

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SLIDE 24
  • 4. Results and discussion
  • 600
  • 400
  • 200

200 400 600 20 40 60

P(µC/cm

2)

BNBTs5.5 BNBTs6.5 BNBTs8.0 BNBTs10.0

Electrical measurement of BNBTs nominal stoichiometric thin films Cross-section and plan-view images of BNBTs nominal stoichiometric films

2m 2m 2m 2m

BNBTs5.5 BNBTs6.5

Solution derived lead-free… Solution derived lead-free…

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

  • 60
  • 40
  • 20

E (kV/cm)

2m 2m 2m 2m 2m

Sample BNBTs5.5 BNBTs6.5 BNBTs8.0 BNBTs10.0 Grain size 288 nm 194 nm 179 nm 119 nm Thickness 341 nm 459 nm 329 nm 435 nm BNBTs6.5 BNBTs8.0 BNBTs10.0

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SLIDE 25
  • 400
  • 200

200 400 30 60

BNBT15.0 BNBT10.0 BNBT5.5

P(µC/cm

2)

  • 4. Results and discussion

Electrical measurement of BNBT thin films with Na(I)+Bi(III) excesses in the nominal composition Cross-section and plan-view images of BNBT films containing excesses of Na(I)+Bi(III) in the nominal composition

2m 2m

BNBT5.5

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

  • 400
  • 200

200 400

  • 60
  • 30

E (kV/cm)

Sample BNBT5.5 BNBT10.0 BNBT15.0 Grain size 153 nm 170 nm 97 nm Thickness 559 nm 553 nm 550 nm

2m 2m 2m 2m

BNBT10.0 BNBT15.0

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SLIDE 26
  • 4. Results and discussion

20 40 60

P(µC/cm

2)

BNBT10.0 BNBTs5.5

Electrical measurements comparison between the best stoichiometric and the best not stoichiometric films

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

  • 600
  • 400
  • 200

200 400 600

  • 80
  • 60
  • 40
  • 20

E(kV/cm)

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SLIDE 27
  • 5. Conclusions
  • 5. Conclusions

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

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SLIDE 28
  • 5. Conclusions
  • The morphotropic phase boundary (MPB) of BNBT powders has

been situated for 93.5/6.5 and 92.0/8.0 ‘stoichiometric’ nominal

  • composition. Addition of Na(I) and Bi(III) excesses to the system leads

to a shift of the MPB for these powders to the 90.0/10.0 nominal composition.

  • The best ferroelectric response for BNBT films has been obtained

for the 90.0/10.0 composition with addition of Na(I) and Bi(III)

Solution derived lead-free BNBT thin films Solution derived lead-free BNBT thin films

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

for the 90.0/10.0 composition with addition of Na(I) and Bi(III) excesses to the respective precursor solution (Pr 23 µC/cm2 and Ps60 µC/cm2), the composition for which has identified the MPB in the crystalline powders.

  • Studies are in progress to elucidate the either intrinsic (e.g.

compositional effects) or extrinsic (e.g. scaling effects) driving nature

  • f the boundary displacement observed in these BNBT films with

respect to bulk counterparts.

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SLIDE 29

SOLUTION DERIVED LEAD SOLUTION DERIVED LEAD- FREE (Bi FREE (Bi0.5

0.5Na

Na0.5

0.5)TiO

)TiO3–BaTiO BaTiO3 (BNBT) (BNBT) THIN FILMS IN THE PROXIMITY OF THE MORPHOTROPIC PHASE THIN FILMS IN THE PROXIMITY OF THE MORPHOTROPIC PHASE BOUNDARY (MPB) BOUNDARY (MPB)

M.D. Mezcua, J. Ricote, D.Chateigner1, C. Gutiérrez-Lázaro, I. Bretos, R. Jiménez, R. Sirera2 and M.L. Calzada

Instituto de Ciencia Instituto de Ciencia de Materiales de Madrid de Materiales de Madrid

M.L. Calzada

Instituto Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas (ICMM-CSIC). Cantoblanco. 28049 – Madrid. Spain.

1 Laboratoire de Cristallographie et Sciences des Matériaux (CRISMAT). Ecole Nationale Supérieure d'Ingénieurs de Caen

(ENSICAEN). Université de Caen. 14050 – Caen. France.

2 Departamento de Química y Edafología. Facultad de Ciencias. Universidad de Navarra. 31080 – Pamplona, Navarra.

Spain.