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- あおし かやぬま
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1 AFM WPI-Advanced Institute for Materials Research (NIMS)
2 outline SPM,
3 STM/STS, AFM KPFM, SNOM,. What and how Does SPM see the sample???
4 2004~2007, 2009~ AFM 1A. 1B. AFM 1A 3A. AFM 3B. AFM AFM AFM DFTB PR-DFTB Observed SPM image Optimal Tip structure guess Optimal Sample structure guess
5 Inverse problem! Observed SPM image Optimal tip structure guess Optimal sample structure guess experiment Modeling of simulation Observed image Simulated image L.Gross, et al, SCIENCE, 325 (2009)1110 Quantitative comparison by the inner product method New experiments Improved models Model reconstruction with optimization/neural network approach
6 1. Rapid AFM simulator for tip sample image Calculated by Interaction Geometrical force condition AFM images by the geometrical method and the force method Using only geometrical condition The case of collagen The case of GroEL a few hours(ws) less than 1 sec(pc) M.Tsukada, K.Tagami, Q.Gao, and N.Watanabe, Current nanoscience 3 (2007)
7 Applications of the AFM simulator f = rf 0 = AFM image of pentacene by a CO tip Using classical force field, f 0 2kAπ 2π AFM image of DNA by C tip 0 F(A cosθ + L)cosθdθ fixed sample structure constant height calculation time 20 min with PC simulation DNA structure fixed constant frequency calculation time 3 hours with PC simulation experiment L.Gross, F.Mohn, N.Moll, P.Lilijeroth, G.Meyer, SCIENCE, 325 (2009)1110 simulation
8 Non-Contact AFM image of methyl group on Si(100)/H A. Masago et al, Jpn. J. Appl. Phys., 48, (2009) DFTB calculations 4. Quantum mechanical AFM/ STM /KPFM simulator on H atom 2π f0 f = F( Acos θ + L)cosθθ d 2kAπ 0 Frequency shift image Constant height 2π 1 2 h A L d = γ( cos θ+ )sin θ θ πω 0 0 2π 1 + FA ( cos θ + L)sinθθ d 2kAπ 0 Dissipation image on methyl
9 Nano-mechanical experiment on GFP (Green Fluorescent Protein) Force/nN 1 4 Remarkable quenching of fluorescence Structure by X-ray X Cromophore Tip height (nm) T Kodama, H.Ohtani and A.Ikai, Appl. Phys. Lett (2005) MD simulation of compression with a flat tip Force-distance curve Intensity A.U. Q.Gao, et al, Jpn.J. Appl.Phys., 45 (2006) L929 Wavelength/nm
10 Mechanism of suppression of light emission -Simulation of nano-mechanical experiments T Kodama, H.Ohtani and A.Ikai, Appl. Phys. Lett (2005) CM/MM ONIOM calculation energy Excited state Natural form Ground state After compression Hydrogen bond length Arg96 Wat1, wat2 Tip height( ) His148 On the compression, rotation barrier disappears Non-radiative processes take place Dihedral angle (deg) Emission suppressed
11 Theory and simulation of Kelvin Probe Force Microscopy(KPFM) A E F two conductors far from each other V CPD B E F q by approaching q V CPD With applied bias V qv qv VCPD V q CPD C z V qv C z V V CPD Contact potential difference VCPD is a global(averaged) quantity, but in KPFM experiment, it depends on the tip position?! How is the local contact potential VLCPD difference explained? 2 1 C z F VCPD V 2 z
12 What is the Local Contact Potential Difference VLCPD? T EF ( ) x x A common potential at X = X T EF ( ) The local contact potential difference Profile of surface potential E T F ( x) x= x E S F ( x) x x With approach without charge transfer S EF ( ) S T x E ( x) E ( x) V = LCPD F F ( ) S EF ( ) Contact Potential difference CPD S F T ( ) ( ) V = E E Local Contact Potential Difference V x = x x ( ) S ( ) T E E ( ) LCPD F F VLCPD ( x) is determined by nano-scale surface potential governed by local charge distribution, but approach of the tip and the sample modifies the local charge distribution. F
13 Simulation of KPFM Images What is the Local Contact Potential Difference Partitioned real space DFT based tight binding method PR-DFTB method +perturbation V For a given charge transfer solve electronic state of Tip with potential field of Sample solve electronic state of Sample with potential field of Tip q Electronic state charge T { ϕi }, ρt ( r) S { ϕi }, ρs ( r) Fermi level offset, i.e., applied bias and force are determined for this charge transfer, then B E q E q e V q V A F F LCPD V LCPD, local contact Potential difference determined perturbation for the chemical force
![6nm V [ ] LCPD V V [ V] Tip height 0.](/docs-images/88/115034306/images/14-2.jpg "4nm y LCPD Si4H9 tip x Si(100)c(4x2)")
14 KPFM image of Si(001)-c(4x2) -image of local contact potential differnceeffect of embedded imturity atoms y Tip height 0.6nm V [ ] LCPD V V [ V] Tip height 0.4nm y LCPD Si4H9 tip x Si(100)c(4x2) x impurity Al in Si(100)c(4x2) impurity P in Si(100)c(4x2) A.Masago et al, Phys. Rev. B 82 (2010)195433
15 ncafm ncafm 3DRISM MD
16 1)? 2)? 3)? 4) : h; ρ S(z) h(z) = EI(z) 2 2 t z z h(z) + F liq (z) 2 E; modulus I; : 2 v t + r r 1 Re ( v ) v = P + v Navier-Stokes Re;
17 Method for fluid dynamics on 2D Flow function Ψ v x ψ = + y v y ψ = x Velocity component of fluid vorticity ω ω = v v x y y x 2 ψ + 2 x 2 ψ = ω 2 y From Navier-Stokes eq. v + t r r 1 ( v ) v = P + v Re ω ψ ω = t x y ψ ω y x 2 1 ω + 2 Re x 2 ω y + 2 negligible Closed equation of solved by FEM ω Force felt by cantilever is given by F s ω = P + dl Re
18 (nm) nm Si water Hz) 15 m 20 m 10 m vacuum air 60 m 50 m 40 m 30 m khz radian) (khz) water µrad m 50 m 40 m 30 m 20 m 15 m 10 m vacuum air khz M.Tsukada, N.Watanabe, Jpn.J.Appl.Phys. 48 (2009)
19 - -
20 Visco-elastic free elastic free elastic (nm) adhesive adhesive Visco-adhesive (ps) Frequency (khz) elastic adhesive Visco-elastic Visco-adhesive f (h) = k(h h touch ) h < h touch f (h) = k(h h touch ) h < h touch h < h detach f (h) = k(h h touch ) γ v h< h touch f (h) = k(h h touch ) γ v h < h touch v < 0 h < h detach v > 0 h touch htouch h detouch h detouch
21 -
22 AFM ; CNT K.Tagami and M.Tsukada, e-j. Surf.Sci.Nanotech. 4 (2006)311 Tip Height
23 nc AFM MD MD 36A 42A 10,0)CNT TIP3P 6,338 : CHARMM 22 + CLAY ( modified ) : NAMD2.5 and 2.6 : 300 K : 2fs 2 A h M.Tsukada, N.Watanabe, M.Harada and K.Tagami, J. Vac. Sci. and Techn. B28 (2010) c4c1
24 Force-distance curve by MD simulation; mica in water by a CNT tip MD simulation Ontop Al Al M.Tsukada, et al, J. Vac. sci,. Technol. B 28, C4C Si Hollow site A Hollow site B O Ontop O Ontop Si Experiment A, B: ontop of hollow site C: ontop of Al atom D: ontop of Si atom E ontop of O atom K.Kobayashi, et al, Nanotechnology, submitted
25 O Al Si 3D SWCNT MD M.Tsukada et al, J. Vac. Sci. B28 (2010) c4c1 A, B: ontop of hollow site C: ontop of Al atom D: ontop of Si atom E ontop of O atom
26 Comparison between the theory and the experiment Experiment K.Kobayashi, et al, Nanotechnology, submitted Force map at a horizontal plane with a certain height Force map at the horizontal plane by 0.2nm closer from the left Force map at a vertical plane Including the dots of the left Theoretical Simulation M.Tsukada et al, J. Vac. Sci. B28 (2010) c4c1
27 水中マイカと CNT探針間の 水分子の分布 O原子 MDシミュレーションの 結果 O Al Si A, B: ontop of hollow site C: ontop of Al atom D: ontop of Si atom E ontop of O atom
28 K 50,000 step 150,000 step 1step=2fs 100,000 step 20,000 step
29 AFM (3D)- RISM h,c,ω N N N = h = ω c ω + ω c ρh ( kl ) αβ ω = δ αβ sin / kl ij ij ij convolution c ij = exp( βu 0 ij + t ij βφ ij ) 1 t ij 1 W ( R)= ρk B T dr ij 2 h ij r () t h c 2 cij r () 1 2 h ij ( ) F( R)= W R R ()c r ij () r β = 1 k B T R
30 3D-RISM Distribution O Distribution H +0.8e -0.8e M.Harada and M.Tsukada, Phys. Rev. B, 82 (2090) Distribution O Distribution H
31 O D-RISM tip 0.8e -0.8e
32 R 1 δ a R 2
33 AFM a δ = 1 R * 4E 1 3 * 3 F = a 16πγ E a 3R 4πγ R * 3 E a 2 2 ( ) 2 US = 2γπ a = U12 U1 U = + R R R ν 1 ν = + * E E1 E2 F δ / FC R 1 a R 2 2 9πγ R a0 = * E 2 a0 δ 0 = 3R Fc = 3πγ R 1/3 f vdw AH R = 2 6z δ / δ 0
34 U1 vac 2 vac : γ Surface energy for the detached state U = U + U ditach 1 vac 2 vac U For the case of wetting U1 2 Surface energy for the atached state U = tach U1 2 Adhesion energy U = U U adhesion ditach tach = U + U U 1 vac 2 detach 1 2 U adhesion = 2A u A u = A u water _ surf _ tension water _ surf _ tension water _ surf _ tension
35 2 2 2 ρsz () hz () = EIz () hz () t z z η( z) h( z) + F z V t z = 0.00 liq () TS Si _Cantilever : _400µ m 40µ m 0.4µ m R = 20nm ν = 0.01kHz amplitude: 200nm Sample(tip)YoungModulous: 60.0MPa(130GPa) adhesive_energy 2 ( γ ) = 10J/m z c δ s D.Wang et al, Macromolecules, (2010) 43, 3169 Visco-elastic effect? = 0.02 ns/m
36 研究協力者 田上勝規渡辺尚貴原田昌紀真砂啓吾妻広夫橋本直樹清水守 アドバンスソフトみずほ情報総研アドバンスソフト Advanced Algorithm & Systems Advanced Algorithm & Systems Advanced Algorithm & Systems Advanced Algorithm & Systems 科学技術振興機構研究成果展開事業 先端計測分析技術 機器開発 走査プローブ顕微鏡シミュレータ
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