Ferroelectric nanostructures and their processing issues

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Published on June 27, 2009

Author: ionelenadaniela

Source: slideshare.net

Ion Elena-Daniela Ferroelectric nanostructures and their processing issues

FE nanostructure s Processing issues Potential applications Ferroelectricit y, Ferroelectric materials F E nanostructure, Size limit in ferroelectricity Invasive and Non-invasive approach C haracterization of FE nanostructure Outline

FE nanostructure s

Processing issues

Potential applications

Ferroelectricit y, Ferroelectric materials

F E nanostructure, Size limit in ferroelectricity

Invasive and Non-invasive approach

C haracterization of FE nanostructure

Important Events 1921 Discovery of ferroelectricity in Rochelle Salt 40’s Barium titanate era 60’s Age of high science 80’s Age of integration 1990-present Age of miniaturization d ef = reversibility of the direction of the electric dipole by means of an applied electric field in a polar crystal Materials which exhibit ferroelectricity are called ferroelectric materials Ferroelectricit y

Ferroelectricit y

P i = d ijk  jk (Direct Effect)  ij  d kij    Converse Effect   P s =   T Ferroelectric materials 32 Sym m etry Points groups 21 Noncentrosymetric 20 Piezoelectric Polarized under stress 10 Pyroelectric Spontaneously polarized Subgroup Ferroelectric Spontaneously polarized Polarization reversible Tungsten Bronze Ox y gen Octahedral ABO 3 Pyrochlore Layer structure 11 Centrosymetric Non-piezoelectric Ceramic Perovskite

Ferroelectric materials

e.g. Perovskite oxide – ABO 3 BaTiO 3 , PbTiO 3 , Pb(Zr x Ti 1-x )O 3 ,

Reversible spontaneous polarization- 1 or 0 data bits (binary data storage media) Piezoelectric effect- Piezoelectric actuators, sonar detectors Pyroelectric effect Pyroelectric detectors for infrared detection, imaging, thermometry, ... Applications

3D -> 2D transition : bulk to thin film 2D -> 1D transition : thin film to wire 2D -> 0D transition : thin film to nanostructures Ferroelectric nanostructure s F. D. Morrison et al. Rev. Adv. Mater. Sci. 4 (2003) 114 Alexe et al. APL- 75, 1793, (1999) Ma et al. APL, 83, 3770 (2003) Luo et al. APL, 83, 3, 440, (2003) Yun et. al. Nano Letters, S1530, (2002 )

3D -> 2D transition : bulk to thin film

2D -> 1D transition : thin film to wire

2D -> 0D transition : thin film to nanostructures

Ferroelectric nanostructure s

Switching @ nanoscale P=10 µC/cm2, ε = 200 a = 10 nm  Q = P·S ≈ 6 0 e a = 2 nm  Q = P·S ≈ 3 e Size limit in ferroelectricity Rudinger et. al. Appl. Ph y s. A, 80, 1247 (2005) Factor s that influence the ferroelectric properties in nanostructure: Grain size, Mechanical bondary conditions, ... W c > k B T

Switching @ nanoscale

P=10 µC/cm2, ε = 200

a = 10 nm  Q = P·S ≈ 6 0 e

a = 2 nm  Q = P·S ≈ 3 e

Size limit in ferroelectricity

Electron Beam Direct Writing Focussed Ion Beam Patterning Lithography Methods NANOSTRU C TURE S Top-Down Focussed Ion Beam Patterning Electron Beam Direct Writing Lithography Methods Self-Patterning Chemical Routes Self-Patterning Physical Routes Bottom-Up Self-Patterning Physical Routes Self-Patterning Chemical Routes Invasive and Non-invasive appro a ch

Invasive and Non-invasive appro a ch

Focussed Ion Beam Patterning FIB equipment similar to SEM a highly focussed beam of gallium ions purposes: imaging, and micromachining nanopatterning - resolution ~ 20 nm gallium doping, damaged surface layer C.S. Ganpule et.al. APL 75, 409 (1999)

FIB equipment

similar to SEM

a highly focussed beam of gallium ions

purposes: imaging, and micromachining

nanopatterning - resolution ~ 20 nm

gallium doping, damaged surface layer

Electron Beam Direct Writing Alexe, Harnagea and Hesse, J. Electroceram. 12, 69 (2004) solution: metalorganic compounds (Sr-, Bi-, Pb-ethylhexanoate, Ti-, Zr-isopropylene and Ta-methoxide ) or metal colloids and solvent: xylene and 2-methoxiethanol patterning by scanning an electron beam Powerful method to prepare arrays of ferroelectric cells with lateral sizes down to 75nm Expensive equipment and time

solution: metalorganic compounds (Sr-, Bi-, Pb-ethylhexanoate, Ti-, Zr-isopropylene and Ta-methoxide ) or metal colloids and solvent: xylene and 2-methoxiethanol

patterning by scanning an electron beam

Powerful method to prepare arrays of ferroelectric cells with lateral sizes down to 75nm

Expensive equipment and time

Lithography Methods Photolithography Soft lithography  Nanoimprint Alexe, Harnagea and Hesse, J. Electroceram. 12, 69 (2004) Large-area and low-cost ferroelectric cells below 100nm in lateral size

Photolithography

Soft lithography  Nanoimprint

Self-Patterning Physical Routes Pulsed Laser Deposition Met.Org. Chem.Vap. Deposition Chemical Solution Deposition

Pulsed Laser Deposition 1. Laser radiation interaction with the target 2. Dynamic of the ablation 3. Transport of the ablated material to a charger and a furnace 4. Nucleation and growth Seol et al. - Appl. Phys. Lett., 81, 1894, 2002 Crystalline nanoparticles ~ 4-20nm Complex experimental set-up, low yield

Met.Org. Chem.Vap. Deposition Large surface coating area Used in combination with FIB, EBDW Expensive equipement Metal organic precursor: Tetraethyl lead - Pb(C 2 H 5 ) 4 Titanium isopropoxide: Ti(i-OC 3 H 7 ) 4 Zirconium tert-butoxide: Zr (t-OC 4 H 9 ) 4 M. Shimizu et.al.-Jpn. J. Apl. Phys, 33, 5168 (1994)

R.W. Schwartz et al. / C. R. Chimie 7 (2004) 433–461 Metal carboxylate: R-COOM M: Pb R: CH 3 -, C 2 H 5 - Metal alkoxide: M(OR) x M: Ti, Zr, ( OR ): (OC 3 H 7 ), (OC 4 H 9 ) Solvent: CH 3 OC 2 H 5 OH Chemical Solution Deposition (Sol-gel)

Self-Patterning Chemical Routes Pb(O 2 C 2 H 3 ) 2 R= [ H2O ]/ [Pb] Zr(OC 4 H 9 ) 4 pH=11 Ti(OC 4 H 9 ) 4 C 4 H 10 O BET: 58nm BET: 109nm BET: 144nm Cost-effective, various shapes Agglomeration (Sol-gel) 11 -PT- 15 11 -PZ- 15 11 - PZT- 15

Self-Patterning Chemical Routes Synthesis, Functionalization and surface treatment of Nanoparticles Marie-Isabelle Baraton/ ASP 2003 Alexe, Harnagea and Hesse, J. Electroceram. 12, 69 (2004) Microemulsion Removal of the surfactant Uniforme particles in nm range

Characterization of ferroelectric nanostructures P iezoresponse Scanning F orce M icroscopy (PFM) M. Alexe, C. Harnagea and D. Hesse, J. Electroceram. 12, 69 (2004) C.H. Ahn, K.M. Rabe, J.M. Tiscone, Science, 303, 488, ( 2004 )

P iezoresponse Scanning F orce M icroscopy (PFM)

Potential applications Many others to come!!!

Thank you for your attention!

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