CEAC Summer Workshop on: Nanoanalysis, Monday & Tuesday, July 10 & 11, 2006 in the ETH main
building, Lecture hall: HG E 1.1, ETH Zentrum, 8092 Zürich, Switzerland,
Keynote lecture Morita Tuesday, 11.7. 09:00-10:00 Chair: V. Sandoghdar (ca. 45 (max. 50) minutes)
Site
-Specific Force
Site-Specific
Force Spectroscopy
Spectroscopy,, Atom
Atom
Manipulation
Manipulation and
and Artificial
Artificial Nanostructuring
Nanostructuring
Seizo Morita, Yoshiaki Sugimoto, Noriaki Oyabu, Ryuji Nishi,
Insook Yi, Yoshihide Seino, Oscar Custance and M.Abe
Graduate School of Engineering, Osaka University
Pablo Pou, Pavel Jelinek, Rubén Pérez
Universidad Autonoma de Madrid
In this review talk, we will introduce:
(1) History of NonContact (NC) AFM
(2) Principles and Performance of NC-AFM.
AFM
(3) Chemical Identification of Atom Species.
Species
Atom Selective Imaging and Atomic Force vs. Z distance
(4)&(5) Mechanical Atom Manipulation at LT and RT
(5) Vertical and (6) Lateral Atom Manipulation
Modification of Atomic Structure made of One Atom Species
(6) Atom Inlay at RT.
RT
Assembly of Nanostructure from Two Atom Species
1
(1) History of NonContact (NC) AFM
Attractive
(3) NonContact AFM
Force
Since 1995
[nondestructive]
Imaging
0
Dynamic
True Atomic Resolution
[Weak attractive force]
(2) Tapping
AFM/Cyclic
Contact
[Weak repulsive force]
noncontact
History of AFM NearContact AFM
Atom Manipulation
Displacement Sensor
Dynamic
Imaging
(1) Contact AFM
Since 1986
[destructive]
[Strong repulsive force]
Repulsive Force
Displacement Sensor
Atom Assembly
Displacement Sensor
cyclic contact
Displacement Sensor
contact
Dynamic
Precisely
controlled
NearContact
2
History
History of
of Noncontact
Noncontact AFM
AFM
Beginning of AFM: Simple contact AFM measurement
1986 Invention of Atomic Force Microscope (AFM)
AFM
G.Binnig, C.F.Quate and Ch.Gerber, Phys.Rev.Lett. Vol.56 (1986) pp.930-933.
1987 Lattice Image of Graphite obtained using SiO2 micro-cantilever under contact region
G.Binnig, Ch.Gerber, E.Stoll, T.R.Albrecht and C.F.Quate
Europhys.Lett, 3 (12) (1987) pp.1281-1286.
1988 Optical fiber-based interferometer AFM
D.Ruger, H.J.Mamin, R.Erlandsson, J.E.Stern and B.D.Terris,
Rev.Sci.Instrum. 53 (1988) 2337.
1990 Optical-beam-deflection AFM and lattice image of NaCl(001) under UHV
G.Meyer and N.M.Amer, Appl.Phys.Lett. 56 (1990) pp.2100-2101.
Dawn of Noncontact AFM with true atomic resolution
1991 Frequency modulation (FM) method combined with large amplitude and high Q
T.R.Albrecht, P.Grutter, D.Horne and D.Ruger, J.Appl.Phys. 69 (1991) 668.
1992 K and Br ions,
ions and monostep with atomic resolution of KBr(001) in UHV at 4.2K
3
F.J.Giessibl and G.Binnig, Ultramicroscopy, 42-44 (1992) pp.281-289, pp.7-15.
Beginning of Noncontact AFM with true atomic resolution
1995 Si(111)-(7x7) by noncontact AFM, F.J.Giessibl
Science 267 (1995) pp.68-71 [30 Aug.1994;
Aug.1994 accepted 31 Oct.1994]
In 1995, Achievement of
True Atomic Resolution
Si(111)-(7x7)
1995 Si(111)-(7x7) by noncontact AFM,
Si(111)-(7x7)
S.Kitamura and M.Iwatsuki,
M.Iwatsuki
Jpn.J.Appl.Phys. 34 (1995) pp.L145-L148
[Nov.14, 1994;
1994 Accepted Dec.6, 1994]
1995 Atomic point defects of InP(110) cleaved surface by noncontact AFM,
H.Ueyamam, M.Ohta, Y.Sugawara and S.Morita,
S.Morita
InP(110)
JpanJ.Appl.Phys. 34 (1995) pp.L1086-L1088 [May 31, 1995;
1995 accepted July 13, 1995]
1995 Defect Motion of Atomic point defects of InP(110),
Y.Sugawara, M.Ohta, H.Ueyamam and S.Morita,
S.Morita
Science 270 (1995) pp.1647-1648 [27 July, 1995;
1995 accepted 11 Oct, 1995]
1997 Dissipation image of NaCl(001) and by noncontact AFM, M.Bammerlin,
R.Luthi, E.Meyer, A.Baratoff, J.Lu, M.Guggisberg, Ch.Gerber, L.Howald
and H.-J.Guntherodt, Probe Microscopy, 1 (1997) pp.3-9.
1997 TiO2(110) by noncontact AFM,
K.Fukui, H.Onishi and Y.Iwasawa, Phys.Rev.Lett, 79 (1997) pp.4202-4205.
TiO2(110)
NaCl(001)
4
1998 First International Workshop on Noncontact Atomic Force Microscopy
Convention Center, Osaka University, July 21-July 23, 1998
Proceedings [Appl.Surf.Sci. 140 (3-4) (1999) pp.243-456]
456
C60/Si(111)
Metal
Ag(111)
Cu(111)
InAs(110)
Molecule
(a)
Far
Tip-to-Sample distance
Force Spectroscopy
Near
8 years ago
Graphite(0001) Ferroelectric
material
at 22 K
Layer material
Van der Waals Force
TGS
(b)
GaAs(110) GaAs(110)
Topography Charge Imaging by EFM
Si(111)
√3×√3-Ag
tip-to-sample distance dependence of
nc-AFM image
Topography
CPD Imaging by5 KPFM
Si(111)7x7 with Ag deposites
2004 Seventh International Conference on Noncontact Atomic Force Microscopy,
the University of Washington (UW), 12-15 September 2004, Seattle, USA
Proceedings [Nanotechnology, Vol.16, No.3 (2005) pp.S1-S137]
S137
This conference in Seattle was the first meeting held in USA.
nc-AFM
Atomic Resolution
STM
nc-AFM 2004
Atomic Resolution Beyond STM
Ge(105)-(1×2)
Ge(105)-(1×2)
Atom Discrimination (Chemical Identification)
Sn/Si(111)(√3×√3)R30º
Sn/Si(111)(7x7)
Si(001)c(4x2)
(-24Hz)
Sn/Si(111)-(2√3×2√3)
Imaging Molecules
Si(001)2x1
(-32Hz)
C12 monolayer under
an ambient condition (Q = 292)
Molecular and Submolecular
Resolution Even in Liquid
Control of Atomic Force and Atom Relaxation
Vertical
Atom Manipulation
before
after
[01-1]
a
Ge(111)-c(2x8)
b
c
78.6 K
d
Lateral
Atom Manipulation
“Atom Inlay”6
Embedded Atom Letters
First
-AFM
First English
English Book
Book on
on NC
NC-AFM
Citations 112 S.Morita, R.Wiesendanger and E.Meyer (eds.); “Noncontact Atomic Force
7
Microscopy”, Springer, NanoScience and Technology, the end of August (2002)
2002 pp.1-439
(2) Principles and Performance of NC- AFM
How
Resolution
How to
to Achieve
Achieve True
True Atomic
Atomic Resolution?
Resolution?
How to detect Weak Attractive Force?
Force
Cantilever
k
Tip
Sample
Detection of Frequency Shift
Displacement
Weak Attractive Force
atomic point defect
k + k ts
m
Kts<0
Noncontact AFM
Mechanical
Resonant
Oscillation
ω = 2πf =
m
Δν/ν=
10-6~10-7
Frequency Shift
∆ν
A0
Oscillation Amplitude
Dynamic
Mechanical
Resonant
Oscillation
ν0∼150kHz
ν
8
Oscillation Frequency of Cantilever
Schematic
-AFM
Schematic diagram
diagram of
of the
the NC
NC-AFM
How to detect Weak Attractive Force?
Fiber-Optic
Interferometer
1
2
∆ν Frequency
Shift
Image
AGC
Circuit
∆ν Feedback Loop
Phase Shifter
Z+δ Z
X,Y
Cantilever
Sample
δZ
Feedback
and Scan ∆Ζ
Circuits
Topography
Frequency Shift
∆ν
A0
Oscillation Amplitude
FM
Demodulator
ν0
ν
Oscillation Frequency
of Cantilever
NC-AFM using the FM detection method.
method
This system has three feedback loops.
loops
9
How
How to
to measure
measure energy
energy dissipation?
dissipation?
FM
Demodulator ∆ν Frequency Shift
Fiber-Optic
Interferometer
Image
1
2
δZ
Z+δ Z
Feedback
X,Y and Scan
Cantilever Circuits
Sample
p-GaAs(110)
NA=1.4x1019cm−3
∆Ζ
Topography
@RT
Constant
Amplitude
Mode
p-GaAs(110)
NA=1.4x1019cm−3
10
Excitation Voltage [mV]
@RT
∆ν Feedback Loop
Phase Shifter
Oscillation Amplitude [Å]
Constant
Excitation
Mode
AGC
Circuit
Where
Point
Where is
is Contact
Contact Point?
Point?
Where
Region
Where is
is Noncontact
Noncontact Region?
Region?
19 −3
p-GaAs(110) NA=1.4x10 cm
Constant Excitation Mode
Frequency Shift ∆ν(Hz)
Decay Length
Contact Point
Contact
Noncontact
L1~ 0.16nm
L2~ 1.1nm
9.5
2
-10
9.0
-10
1
1
2
z
z
(c) ~ 0.08nm
(b) ~ 0.1nm (a) ~ 0.4nm
0
-10-0.5
8.5
0
0.5
z
1.0
1.5
Tip-Sample Surface Distance Z[nm]
8.0
7.5
2.0
Oscillation Amplitude A0 [nm ]
@RT
11
Where
Resolution
Where can
can we
we obtain
obtain True
True Atomic
Atomic Resolution?
Resolution?
8Hz
20pm
p-GaAs(110) NA=1.4x10 cm
0.1Hz
0.25pm
1mHz
2.5fm
@RT
(a)z~0.4nm
(b)z~0.1nm 0.02 nm (c)z~0.08nm
∆ν = -31Hz
∆ν = -62Hz
∆ν = -70Hz
8 Hz
1.91Hz
4.57Hz
12.2Hz
19 −3
11.5nm
11.5nm
11.5nm
Journal of Crystal Growth, Vol.210, 408 (2000)
12
Home
-built RT
-UHV-NC-AFM
Home-built
RT-UHV-NC-AFM
Schematic Side View
☆ UHV: ~4×10-11Torr
AFM
Preparation
Chamber
Chamber
Load Lock
Chamber
Cantilever
(Sb-doped n+Si)
Ar+ Ion Sputtering
k=41-49N/m
ν0=169-172kHz
Q=38,000 in UHV
Tip Radius:5-10nm
A0=3nm-10nm
“Atom Inlay”13
Embedded Atom Letters
NonContact
-AFM)
NonContact AFM
AFM (NC
(NC-AFM)
High Resolution NC-AFM Images
DNA Image
Organic monolayers
7nmx7nm
B-DNA
Langmuir, 16 (3), 1349 -1353,
2000. T.Uchihashi, M.Tanigawa,
M.Ashino, Y. Sugawara,
K.Yokoyama, S.Morita, and
M.Ishikawa @RT
Adenine Molecules
Appl.Surf.Sci. Vol.157, No.4 (2000)
pp.244-250.T.Uchihashi, T.Ishida,
M.Komiyama, M.Ashino, Y.Sugawara,
M.Mizutani, K.Yokoyama, S.Morita, 14
H.Tokumoto and M.Ishikawa, @RT
NonContact
-AFM)
NonContact AFM
AFM (NC
(NC-AFM)
Atomically Resolved NC-AFM
Images @RT
Sn/Si(111)√3×√3
(111)
Sn
Ag(111)
Motion of Ag
atoms at step site
LiF(100)
Si
2nm×2nm
mosaic phase Sn=1/6
ML Sn:50% Si:50%
Metal
on Si(111)
38Åx38Å
Insulator
15
Novel
Novel Bottom
Bottom Up
Up Nanostructuring
Nanostructuring System
System
-Mechanical Assembly Using Many Atom Species-
AFM
Insulator is
observable
Evaporation of
many atom species
Si
In
Tip
Si
In
Displacement
sensor
Cantilever Deflection
Si
Chemical
Identification
Many atom species
Atomic force is
measurable
Displacement
sensor
Cantilever Deflection
Si
In
In
Selective
manipulation/
assembly
Novel nanomaterial/Novel nanodevice
with Novel function
Chemical Identification: Atomic force measurement of individual atoms
Strong bond
Selective atom
manipulation/assembly : Insulator
Covalent bond
RT&
RT 3D-structure
16
Ionic bond
Electronic device
(3) Chemical Identification of Atom Species
How
Identification
How to
to Achieve
Achieve Chemical
Chemical Identification?
Identification?
=> from topography with chemical contrast
(=Atom Selective Imaging)
=> from frequency shift vs. tip-sample
distance curve
(=>Force Curve and Potential Curve)
Y.Sugimoto, M.Abe, K.Yoshimoto, O.Custance, I.Yi and S.Morita; “Non-contact atomic
force microscopy study of the Sn/Si(111) mosaic phase”, Applied Surface Science,
Volume 241, Issues 1-2, 28 February (2005) pp.23-27.
M. Abe, Y. Sugimoto, O. Custance, and S. Morita, “Room-temperature reproducible spatial
force spectroscopy using atom-tracking technique”, Applied Physics Letters, Vol.87, Issue 17,
24 October (2005) pp.173503-1~173503-3.
Noriaki Oyabu, Pablo Pou, Yoshiaki Sugimoto, Pavel Jelinek, Masayuki Abe, Seizo Morita,
Rubén Pérez, and Óscar Custance; “Single Atomic Contact Adhesion and Dissipation in
Dynamic Force Microscopy”, Phys.Rev.Lett. Vol.96, No.10 (2006) 106101-1~106101-4.
Y.Sugimoto, P.Pou , O.Custance, P.Jelinek, S.Morita, R.Pérez and M.Abe, “Real topography,
atomic relaxations, and short-range chemical interactions in atomic force microscopy: The
17
case of the α-Sn(111)-(√3×√3)R30”, Phys.Rev.B, Vol.73 (2006) pp.205329-1~205329-9.
surfaces Sn
Sn Si(111)-(√3×√3)
Si
Sn NC-AFM images of Sn/
1/6ML mosaic phase
intermediate phase
pure phase1/3ML
7x7
Sn:1/6ML
Sn:50% Si:50%
1/4ML
Sn:75% Si:25%
1/3ML @RT
Sn:99% Si:1%
20nm
8nm
Sn
Si
Si
Sn
Sn
Si
18
Chemical
Chemical Identification
Identification and
and Histgram
Histgram of
of
Sn
/Si(111)√3×√3
intermixed
(111)
Sn/Si(111)√3×√3
intermixed surface
surface
pure phase (Sn:99% Si:1%)
:1%
mosaic phase (Sn:50% Si:50%)
:50%
Sn: 1/3ML
Sn
Si
22
20 Sn: 1/3ML
18
16 pure phase
Sn
14
Standard
deviation
12
σ=2pm
10
8
Clear
6
discrimination
4
Si
RT
2
0
-0.06
-0.04
-0.02
0.00
14
12
10
(a)
Relative height [nm]
Si
16
Counts
Counts
Sn
Sn: 1/6ML
8
6
4
2
Sn: 1/6ML
mosaic phase
Si
(b)
RT
Sn
Wide
Variation
？
0
0.02
-0.10 -0.08 -0.06 -0.04 -0.02 0.00
19 0.02
Relative height [nm]
Sn
Sn atom
atom effect
effect surrounding
surrounding Si
Si atom
atom on
on Si
Si atom
atom height
height
(a)
Z[Å]
1/6ML
mosaic
phase
Si-a
Sn
Si-b
0.1
0.0
-0.1
-0.2
-0.3
-0.4
-0.5
-0.6
-0.7
-0.8
-0.9
-1.0
-1.1
-1.2
-1.3
RT
2 Sn atoms
surround Si-b
5 Sn atoms Sn
surround Si-a
30pm
Charge transfer
Si-a
0
2
4
Si-b
=>
Change of
bonding force
(Bond order)
8 10 Z
12height
14 16 18
X [Å](Wave function)
6
No charge trnsfer
SP3
0.665
Si
nm
SP3
Si
Si
Si
Si
Si
Si
Si
Relative height (nm)
Sn effect surrounding Si/Sn atom on height
0.01
0.00
-0.01
-0.02
-0.03
-0.04
-0.05
-0.06
-0.07
-0.08
-0.09
-0.10
Charge transfer
10pm/surround Pz
Sn
ing
Sn
atom
Sn
Si
Si-b
Si
Sn
Sn: 1/6ML
0
1
SP2
Si-a
2
3
4
5
Number of Sn atoms
surrounding Si atom
6
Sn
Sn
P3
Sn
Si
Sn
Sn
20
NC-AFM
Si(111)-(√3x√3)
Sn
Si
NC-AFM images
images of
of Sn/
Sn/Si(111)-(√3x√3)
Tip-Sample distance dependence of
atom selective imaging
(a)
Si
(c)
(b)
Sn
Far
distance
Si
Sn
@RT
Si
Sn
Near
distance
21
SSFS
: SSite
ite SSpecific
pecific FForce
orce SSpectroscopy
pectroscopy
SSFS:
SSFS & averaging
100 curves
using Atom
Tracking Method
Sn Si
Long range force
0
-2
-4
-6
-8
-10
-12
-14
-16
-18
-20
-22
-24
Short Range Force
2
Sn
1
Si
0
-1
Covalent
Bonding Force
-2
-3
0
0
2
Imaging
-4
-6
@RT
Disappearance of
chemical contrast
-8
-10
-12
-14
height difference
-16
Si
-18
0
2
4
6
8 10 12 14 16 18 20
Tip-Sample Distance Z[Å]
Short Range Potential U[eV]
Sn
4
6
8 10 12 14 16 18 20 22 24
Tip-Sample Distance Z[Å]
-2
γ[fN √m]
Frequency Shift ∆f [Hz]
Short Range Force F[nN]
Sn/Si(111)-(√3x√3)
1
Short Range Potential
Atom height and
atom radius etc.
0
Sn
-1
Si
-2
Covalent Bonding
Potential
-3
0
2
4
6
8 10 12 14 16 18 20 2222
24
Tip-Sample Distance Z[Å]
Chemical Identification of Atom Species by AFM
2006
Insulating
Surface
2020
2005
Amorphous
2010
Subsurface
5 atom species 2015 3 atom species
(B/Si(111)）
in atom cluster
2007
3 atom species 2012 Isolated 3
Achieved
Force curve
adsorbed atom
2006 3 atom
Achievable
species
2015
species
2010
3-D recognition
NC-AFM
2 atom species
Indeterminate
NMR
Dissipation
2005
Sn/Ge(111) 2007
2003
-c(2×8)
2 atom species :
Si and Sb
NC-AFM
Intermixed
NC-AFM in liquid
in Si(111)
aperiodic atom
2004
5√3×5√32006
Sb: KPFM Sn/Si(111) 2 atom species :
distribution
√3×√3
NC-AFM in gas
NC-AFM
1999
InAs(110)
NC-AFM
78K&14K
2001年
CaF2(111)
NC-AFM
2000
“5 years ago”
Atomically
flat surface
2005
“Now”
Rough (or
amorphous) Periodic atom
surface
distribution
2010
“5 years later”
Year
2015
23
“10 years later” “Further”
First
First English
English Book
Book on
on SPM
SPM Roadmap
Roadmap
24 end
Seizo Morita, Osaka University, Japan (Ed.), Roadmap 2005 of Scanning Probe Microscopy, ca.the
of Aug. 2006 ca.255 p. 135 illus. Hardcover, NanoScience and Technology, ISBN 3-540-34314-8
Attractive
Force
NonContact AFM
Since 1995
[nondestructive]
Imaging
0
Displacement Sensor
Dynamic
True Atomic Resolution
[Weak attractive force]
Tapping AFM
/Cyclic Contact
[Weak repulsive force]
History of AFM
Displacement Sensor
cyclic contact
Contact AFM
Since 1986
[destructive]
NearContact AFM
Atom Manipulation
Atom Assembly
Displacement Sensor
Dynamic
Imaging
noncontact
Displacement Sensor
Dynamic
Precisely
controlled
NearContact
[Strong repulsive force]
Repulsive
Force
contact
25
(4) Mechanical Atom Manipulation
at LT and at RT
Vertical and Lateral Atom Manipulation
by
by Vertical
Vertical Contact
Contact Method
Method
Modification of Atomic Structure
made of One Atom Species
N.Oyabu, O.Custance, I.Yi, Y.Sugawara, and S.Morita; “Mechanical Vertical Manipulation
of Selected Single Atoms by Soft Nanoindentation Using Near Contact Atomic Force
Microscopy”, Phys.Rev.Lett., Vol.90, No.17 (2003), pp.176102-1~176102-4.
Noriaki Oyabu, Oscar Custance, Masayuki Abe, and Seizo Morita; “Mechanical Atom
Manipulation and Artificial Nanostructuring at Low Temperature”, e-Journal of Surface
Science and Nanotechnology (e-JSSNT), Vol.4 (2006) pp. 1-8.
R. Nishi, D. Miyagawa, H. Etou, Y. Seino, Insook Yi and S. Morita ; “NC-AFM study on
atomic manipulation on ionic crystal surface by nanoindentation”, Nanotechnology Vol.17
26
(2006) S142-S147.
How
How to
to manipulate
manipulate selected
selected individual
individual atoms
atoms
by
Mechanical Vertical
”
by using
using ““Mechanical
Vertical Contact
Contact”
Probe and sample were grounded
Step 1
Step 2
Noncontact imaging
Mechanical Contact
Step 3
Noncontact imaging
Clean Si tip
Ge(111)-c(2x8)
Ge(111)-c(2x8)
Ge(111)-c(2x8)
0
piezo-scanner extension
Feedback
Controller
Z piezo-scaneer
piezo-scanner extension
Approach
signal
Feedback
Controller
(B) Slow vertical contact*
experiment
0
time
Imaging distance
*Imaging distance is close to contact point
27
Home
-built LT
-UHV-NC-AFM
Home-built
LT-UHV-NC-AFM
Schematic Side View
Preparation
Chamber
AFM
Liq.He
Chamber
Liq.N2
Preparation
Chamber
Load Lock
Chamber
UHV: less than 1×10-10Torr
AFM
Load Lock
Chamber
Chamber
S.I.P
T.S.P
S.I.P
T.S.P
28
Si
Si Removal
Removal and
and Repair
Repair of
of Missing
Missing Si
Si
Adatom
Adatom Defect
Defect by
by Mechanical
Mechanical contact
contact
Si(111)7×7
78K
Deposition
Si
7×7
Si
(a)
1st Contact
(1) Before Selected Si
adatom Extraction
(b)
2nd Contact
(c)
(1) After Selected Si
adatom Extraction
[2] Before Repair of
Selected
Si adatom Defect
[2] After Repair of
Selected
Si adatom Defect
29
Mechanical frequency : 168.108kHz, Oscillation amplitude : 12.2nm, − ∆γ = −16 fN m
Vertical
Vertical and
and Lateral
Lateral Atom
Atom Manipulation
Manipulation
Ge(111)-c(2x8) 108x108Å
∆f=-20Hz @79K
Vertical Contact Method
Vertical
[110]
Equilateral Triangle
Extraction with Lateral
Crystal
Axis
1st Contact
(a)
Lateral
2nd Contact
(b)
Right Triangle
(c)
Vertical
Repair of Created
Atom Vacancy
Lateral Shift
3rd Contact
(d)
(e)
(f)
30
(5) Mechanical Atom Manipulation
at LT and at RT
Lateral Atom Manipulation
using
using the
the mechanical
mechanical raster
raster scan
scan
using
using the
the mechanical
mechanical vector
vector scan
scan
Modification of Atomic Structure
made of One Atom Species
N.Oyabu, Y.Sugimoto, M.Abe, O.Custance and S.Morita; “Lateral manipulation of single
atoms at semiconductor surfaces using atomic force microscopy”, Nanotechnology 16 (2005)
pp.S112–S117.
Noriaki Oyabu, Oscar Custance, Masayuki Abe, and Seizo Morita; “Mechanical Atom
Manipulation and Artificial Nanostructuring at Low Temperature”, e-Journal of Surface
Science and Nanotechnology (e-JSSNT), Vol.4 (2006) pp. 1-8.
R. Nishi, D. Miyagawa, H. Etou, Y. Seino, Insook Yi and S. Morita ; “NC-AFM study on
31
atomic manipulation on ionic crystal surface by nanoindentation”, Nanotechnology Vol.17
(2006) S142-S147.
Lateral
-AFM
Lateral manipulation
manipulation of
of single
single atoms
atoms with
with NC
NC-AFM
[110]
Ge(111)-c(2x8)
Crystal
Axis
Slow scan
a
b
c
Lateral Scan Method
Straight Walk
d
e
NonContact Image:
NearContact Image:
Direction of slow scan:
Imaging set point at Far distance
∆f = - –28 Hz => -0.8 nN
Weak attractive force
Direction of slow scan:
Imaging at near (closer) distance
∆f = –31 Hz => -1.0 nN
Strong attractive force
Raster scan
f
g
h
NC-AFM topographic images (2.2x3.5 )nm2
f0 = 167485.8 Hz A = 9.3 nm
KL = 33.6 N/m
T = 79 K Q = XX
k=33.2N/m=>∆Z=0.2nN/33.2N/m~6pm
First experimental evidence of the capability of NC-AFM technique
for performing lateral manipulation of atoms
Fast scan
We are deeply involved in developing lateral manipulation with NC-AFM technique
We have many results on lateral manipulation experiments
32
N. Oyabu, Y. Sugimoto, M. Abe, O. Custance, and S. Morita, Nanotechnology, 16 (2005) pp.S112–S117.
Ge(111)-c(2x8)
Lateral Scan Method
Low Temperature 78K
[110]
NonContact AFM Image
Slow scan
Lateral
-AFM
Lateral manipulation
manipulation of
of single
single atoms
atoms with
with NC
NC-AFM
Raster scan
Fast scan
NearContact AFM Image
Crystal
Axis
Before Lateral
Manipulation
Zigzag Walk of Adsorbed Atom
33
by Lateral Manipulation
(6) Atom Inlay at RT
Sn
Ge
@RT
Assembly of Nanostructure
from Two Atom Species
Yoshiaki Sugimoto, Masayuki Abe, Shinji Hirayama, Noriaki Oyabu, Oscar Custance and
Seizo Morita; “Atom inlays performed at room temperature using atomic force microscopy”,
Nature Materials, vol. 4, issue 2 (2005) pp.156-159.
N.Oyabu, Y.Sugimoto, M.Abe, O.Custance and S.Morita; “Lateral manipulation of single
atoms at semiconductor surfaces using atomic force microscopy”, Nanotechnology 16 (2005)
pp.S112–S117.
Yoshiaki Sugimoto, Óscar Custance, Masayuki Abe and Seizo Morita; “Site-Specific Force
Spectroscopy and Atom Interchange Manipulation at Room Temperature”, e-Journal of34
Surface Science and Nanotechnology (e-JSSNT), Vol.4 (2006) pp.376-383.
Lateral
Lateral Atom
Atom Interchange
Interchange Manipulation
Manipulation
Using
-Contact AFM
Using Near
Near-Contact
AFM
Ge(111)-c(2x8)
Crystal
Axis
[110]
NonContact AFM Image
NearContact AFM Image NonContact AFM Image
∆f=-7.2Hz
∆f=-7.0Hz
RT
Raster
Scan
∆f=-7.0Hz
①
②
Sn
∆f=-7.0Hz
NonContact AFM Image
(a)
(b)
(c)
35
A
Process of Nanostructuring of Atom Inlay
B
C
D
E
F
G
H
I
Sequence of topographic NC-AFM
images acquired during the process of
rearranging
single
atoms
for
constructing the symbol associated
with the Tin element by successive
well-controlled lateral manipulations
of tin adatoms embedded within the
plane of the Ge(111)-c(2x8) surface
using NC-AFM technique. (A) Initial
surface template for performing the
manipulation experiment. (B) to (H)
several intermediate stages creating
the letters and cleaning the
surrounding region by manipulating
adatoms one by one. A fixed
substitutional Sn adatom during the
whole construction process is
indicated by an arrow as reference. (I)
Letters of the symbol associated with
the Tin element. Image size was
7.7x7.7 nm2. The images were
performed
with
a
cantilever
oscillation amplitude value of 157 Å,
using a Si cantilever of 29.5 N/m
measured spring constant, at a
frequency shift values of –4.7 Hz (A),
–4.4 Hz (B and C), –4.2 Hz (D), –4.0
Hz (E, G, and H), –4.1 Hz (F) and –
4.6 Hz (I), with respect to a free
oscillation first mechanical resonant
frequency value of 160.450 kHz.
Within near 9 hours more than 120
single atom lateral manipulations.
@RT
Successive Imaging and Following Lateral Atom Manipulation36
Y. Sugimoto, M. Abe, S. Hirayama, N. Oyabu, O. Custance, and S. Morita, Nature Materials, vol. 4, issue 2 (2005), pp.156-159.
Atom
Preceding and
Atom Letters
Letters --Preceding
and Present
Present Achievements
AchievementsAdsorbed Atom
IBM
Xe
STM
Single Element: Xe Atom
4K
Ni
1990
IBM Almaden
D.M. Eigler & E.K. Schweizer, Nature 344, 524 (1990)
Vacancy
HCRL
STM
1991
Single Element: S Vacancy
S
RT Hitachi Central Research Lab.
Mo
Embedded Atom
S.Hosoki, S.Hosaka and T.Hasegawa,
Appl.Surf.Sci.60/61, 643 (1992).
Sn
AFM
2005 (Our Result)
Result
Two Elements: Sn and Ge Atoms
Sn
Ge
RT
Atom Inlay [Embedded Atom Letters]
Osaka University
37
Y.Sugimoto et al., Nature Materials,
vol. 4, issue 2, 156 (2005).
Embedded
-AFM
Embedded Atom
Atom Letters
Letters Figured
Figured by
by NC
NC-AFM
Movie: 9 hours with 120 times of lateral atom manipulation @ RT
Tip Induced Directional
Interchange of Sn and Ge
adatoms
Tip induced directional
thermal diffusion
Ge Atom
Sn Atom
Y. Sugimoto, M. Abe, S. Hirayama, N. Oyabu, O. Custance, and
S. Morita, Nature Materials, vol. 4, issue 2 (2005), pp.156-159.
How to use the vector scan?
AFM
Tip
Embed
ded Sn
Atom
Ge
Atom
38
“Atom Inlay”: Embedded Atom
Letters Figured by NC-AFM
Sn/Ge(111)-c(2x8)
Sn Atom
Ge Atom
@RT
39
Mechanical Atom Manipulation by AFM
2006 Atom
manipulation on
insulating surface
2006 Vertical
atom-interchange
manipulation: RT
2020 Assembly of
molecule using 2 atom
species
2015 Assembly of
atom cluster using
3 atom species
2012 Assembly of
atom device using
2006 Lateral atom 3 atom species
manipulation in 3
2011 Assembly by
atom species sample
Multi atom
atom manipulation in
species 2005 Lateral atom-interchange 2010 liquid
manipulation of Sn and Ge
Assembly by atom
adatoms and “Atom Inlay” in
manipulation in gas
Sn/Ge(111)-c(2×8): RT
2009 Atom
2005 Lateral atom
manipulation
manipulation of single
Achieved
in liquid
adsorbed atom on
2008
Single atom Ge(111)-c(2×8): 80K Atom manipulation
Achievable
in
gas
species 2003 Extraction and
Indeterminate
deposition of Si adatom
on Si(111)7×7 by vertical
atom manipulation: 78K
2000
“5 years ago”
2005
“Now”
2010
“5 years later”
2015
Year
40
“10 years later” “Further”
Here, we demonstrated three topics:
(1) Chemical Identification of atom species.
species
⇒ It can identify chemical species.
(2) Mechanical Atom Manipulation at LT/RT.
LT/RT
⇒ It can cut and form covalent bond.
(3) Atom Inlay at RT.
RT
Assembly of Nanostructure from Two Atom Species
Evaporation of
many atom species
Si
In
Tip
Si
In
Displacement
sensor
Cantilever Deflection
Si
Chemical
Identification
Many atom species
Displacement
sensor
Cantilever Deflection
Si
In
Selective
manipulation/
assembly
In
Novel nanomaterial/Novel nanodevice
with Novel function Nano-Alloys
41
Nano-Devices