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Taipei, Tip-based Nanofabrication, 19-21 October 2008Local Chemical Nanolithographies N f b i i d N d i
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Outline
Nanofabrication and Nanodevices
i). Background: Nanotechnology, SPM
ii). Local Oxidation Nanolithographyiii). Beyond Oxidation: organic liquids
iv). Nanopatterning
v). Molecular Architectures
vi). Si Nanowires
i) P ll l lith hvi). Parallel nanolithography
vii). Summary
Ricardo García
Instituto de Microelectrónica de Madrid
STM 1982STM and AFM atomic-scale AFM 1986Manipulation
RT AFMRT-AFMLT-STM
S. Morita GroupS. Morita GroupOsaka University (Japan)Osaka University (Japan)
Y Sugimoto M Abe S Hirayama N Oyabu O Custance Y Sugimoto M Abe S Hirayama N Oyabu O Custance Quantum corral, Fe on Cu(111) Crommie Lutz Y. Sugimoto, M. Abe, S. Hirayama, N. Oyabu, O. Custance, Y. Sugimoto, M. Abe, S. Hirayama, N. Oyabu, O. Custance,
and S. Moritaand S. Morita, , Nature MaterialsNature Materials 44 156 (2005).156 (2005).Cu(111) Crommie, Lutz, Eigler (1993)
SPM based Nanolithographies
Nanoshaving/grafting
g p
Local Oxidation NanolithographyDagata (1990)
(a)thermal mechanical
electrical chemistry
Nanoshaving/grafting
Dip-pen Nanolithography
Dagata (1990)
(b)
patterning direction
patterning direction(b)
C Mirkin (1999);
Thermomechanical writing/millipede
(c)
C. Mirkin (1999);
H. Butt (1995)Metal deposition
( )
G. Liu (1997)
Binnig et al. (1999)100 nm(1994)
STM oxidation of surfaces
n-Si(111):Hn-Si(111):H
200 nm
Dagata et al. Applied Physics Letters 56, 2001 (1990)
Atomic-scale manipulation in air, R. Garcia (1992)
g pp y ( )
Thundat et al. J. Vac. Sci. Technol. A 8, 3527 (1990)
*Low cost nanolithography for prototyping nanoscale devices: molecular recognition processes
*Ultimate pattern resolution in ambient conditionsp
200 nm
R. García, M. Calleja, F. Pérez-Murano, Appl. Phys. Lett. (1998)R. García, M. Calleja, H. Rohrer, J. Appl. Phys. 86, 1898 (1999);
oxides
polymer
oxides
Chem. Soc. Rev. 35, 29 (2006)carbides
Amplitude modulation AFM (AM-AFM)
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Amplitude modulation AFM (AM AFM)amplitude, phase-shift and resonance frequency
tip’s oscillationFree amplitude
External excitationExternal excitation
A= constant
Topography
500 nm
R. Garcia, R. Magerle, R. Perez, Nat. Mater. 7 (2007)
R. Garcia, R. Perez, Surf. Sci. Rep. 47, 197 (2002)
Instituto de Microelectrónica de Madrid
∫=SupS sU rdγsurface energy
1A∫=SupVdWU 2
1d12A
ξπsrVan der waals
⎞⎛ 1RT∫⎟⎠⎞
⎜⎝⎛=
Volm
C rH1ln
vRTU rdcondensation
energy
∫ EU 20 dεelectrostatic ∫−=VolE EU 20 d
2εε rrelectrostatic
energy
ΔU= surface+condensation+van der Waals+electrostatic energies
Gómez-Moñivas et al. Phys. Rev. Lett. 91, 56101 (2003)
García-Martín, García APL 88, 123115 (2006)
E=2 V/nmE=2 V/nm
time=75 ps
Meniscus height 3 nm
MD by F. Zerbetto and yT. Cramer, UBologna
Cramer, Zerbetto and Garcia, Langmuir (2008)
(b)(a) Local Oxidation Nanolithography
(N O id ti )
2H++2e- H2
(NanoOxidation)
M H O MO 2 H 2
(a) (b)
Niobium500 nmGaAs
M+nH2O MOn+2nH++2ne-
(c) (d)Si(100)( )
100 nm100 nm
Sagiv et al. Adv. Mater 12, 725 (2000)
Sugimura et al. Adv. Mater. 14, 524 (2002)
L t l L i 18 8375 (2002)
Titanium, Aluminum, carbon films, silicon nitride, InP, GaAs, Organosilanes...
Lee et al. Langmuir 18, 8375 (2002)
Local Chemical NanolithographyLocal Chemical Nanolithography
200 nm(c)100 nm(a) 100 nm(b)
Water 1-Octene Octane
After HF etching
Martínez&GarcíaMartínez&García, Nano Lett. 5, 1164 (2005)
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Nanopatterning: Minimum Feature SizeNanopatterning: Minimum Feature Size
Instituto de Microelectrónica de Madrid
Oxide size vs voltage and pulse duration
h tSiO
Wh=cte=1 nm
6
8
ght (
nm) 8 V
10 V12 V16 V20 V
h t
Si(100)
SiOx
60
75
0
2
4
oxid
e he
ig 24 V
30
45
60
10-4 10-3 10-2 10-1 1 10
time (s)
300 8 V10-3 8
40
15
100150200250
wid
th (n
m) 8 V
10 V12 V16 V20 V24 V
0.010.1
1 20
1612
050
100
10-4 10-3 10-2 10-1 1 10
oxid
e w
h~V (t/t0)γShort pulses and high voltages generate the best aspect ratio features
time (s)Calleja, García, APL 76, 3427 (2000)
100 nm 20012000
500 nm
0.4 nm
25 nm
a = 19.5 nm
100 nm1999Dagata 1990
spatial frequency
1999Dagata 1990
100 nm200 nm
200213 nm period
b20062006
10 nm period2006 6.2 nm period2007
50 nm(a)
5050500.3 nm 200 nm200 nm200 nm
20 nm
50 nm50 nm50 nm
25 nm
6 nm
Year Lattice periodicity nm
Feature size nm
Dagata 100 6 nm g1990
1999 40 20
2001 20 10
2 nm
1 nm
2002 13 10
2006 10 4
2007 6 2
1
R.V. Martinez, J. Martinez, N.S. Losilla, R. Garcia,Nano Letters 7, 1846 (2007) Areal density ~15 Tb/inch2
Elements by Local chemical Nanolithographiesy g pMasks, dielectric barriers and templates
iv). Applications
a. Templates for functional devices
b N ib. Nanowires
T l t f th th f ti l
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Templates for the growth of nanoparticles
* Single Molecule Magnets* Single-Molecule Magnets
* Conjugated Materials (TTF derivatives Sexithiophene)(TTF derivatives, Sexithiophene)
Local oxide charges
silicon
Instituto de Microelectrónica de Madrid
3. Growth of T6 on SiO2 stripes
Template growth of T6
PREFERENTIAL GROWTH ALONG THE STRIPES
1 μm 1 μm
500 nm 500 nm
T6
500 nm 500 nm
silicon
Local oxide
Collaboration F. Biscarini, CNR( Italy)
Laboratorio de Fuerzas y TúnelLaboratorio de Fuerzas y Túnel
Mn12O12(CH3COO)16(H2O)4
1 M Mn bet in CH CN acetonitrileRinsing in acetonitrile
Mn12O12(CH3COO)16(H2O)4
1μM Mn12bet in CH3 CN acetonitrileRinsing in acetonitrile
2
3 i
2 nm
= 3 min.
Instituto de Microelectrónica de MadridInstituto de Microelectrónica de Madrid
(a)
Template Growth of single molecule magnets Mn12
(a)
1 μm
(b)
500 nm
Outside the patterned area there are no molecules
500 nm
1 μm1 μm
Template Growth of single molecule magnets Mn12 : Dependence on deposition time
1 min 2 min 4 min
500 nm500 nm 500 nm
500 nm
Adv. Mater. 19, 291 (2007)
i ) A li tiiv). Applications
a. Molecular Architecturas
b. Si Nanowires as molecular recognition sensors
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Nanotransitor based on Si Nanowires
Back-gated nT
(111)54.7 º(100)
Instituto de Microelectrónica de Madrid
SILICON NANOWIRE TRANSISTORS
FORCETOOL LAB
C l Si i hit tComplex Si nanowires architectures
Two-level Si Nanowires
1010
µm1.(b)
1 µm
Instituto de Microelectrónica de Madrid
J. Martinez, R.V. Martinez and R. Garcia, Nano Lett. 8, 3636 (2008)
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20
1 µm
nmSi
1 µm
20 nm
VG=0 V
RTOT=Rc1+Rc2+RNW+Rext=3 MΩ (exp)L
Instituto de Microelectrónica de Madrid
ρ=0.01 Ωcm, L=7.22 μm, A=504 nm2 Ω== MALRNW 8.2ρ nominal
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A very small Si nanowire
Topography cross-section100
120
Au gate i60
80
100
ght [
nm]
Au gate nanowire
0
20
40
heig
0 50 100 150 200 250 300
X [nm]
Si nanowire
width (FWHM)=4 nm
height=37 nm
Reff~6.6 nm
B k t dI-V Characteristics
Instituto de Microelectrónica de Madrid
Back-gated J. Martinez, R.V. Martinez and R. Garcia, Nano Lett. 8, 3636 (2008)
Fabricación de Nanohilos, Destacado por los editores de Nature Materials en Noviembre de 2008,
J. Martinez, R.V. Martinez and R. Garcia, Nano Lett. 8, 3636 (2008)Artículo entre los 10 más leídos en Nano Letters en 2008en Nano Letters en 2008
U li l l Ch i l N lith hiUpscaling local Chemical Nanolithographies
PARALLEL NANOPATTERNING by Local Oxidation
Prototype 2006 Stamp holder
Prototype 2005
Patent: BO2003A000614
Cavallini et al., APL 83,5286 (2003);
Rev. Sci. Instrum. 77, 086106 (2006)
PARALLEL NANOPATTERNING by Local Oxidationy
Stamp
10 nm
400μm
Stamp
200 nm200 nm
1 nm
Imprint
3 μm 200 nm
Local Chemical Nanolithography: Nanofabrication method
ForceTool laboratory
g p ybased on the spatial confinement of chemical reactions
1000 nm 2.0µm1 µm
Nanofabrication funciotional devices
50 nm
µ
funciotional devicesgate
140nm
Instituto de Microelectrónica de MadridInstituto de Microelectrónica de Madrid
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Dr. JavierMartínez
Prof. Ricardo García
Dr. Fernando García Dr. MarcoChiesa Dr. Marta Tello
Dr. Christian Dietz
Ramsés V.Martínez
Elena TomásNuriaSánchez
CarlosGómez
J. R. LozanoJorge
Rodriguez
Funding
Spain: Ministerio de Ciencia e Innovación and
Sánchez Gómez
Instituto de Microelectrónica de Madrid
Comunidad de Madrid, CSIC
EU: BIODOT
