4.

Scanning Probe Microscopies: Scanning Tunneling Microscopy (STM)

4.9.1

Before we can understand tunneling phenomena, we need to briefly look at the electronic structure of solids (e.g. see P.A. Cox, "The Electronic Structure and Chemistry of Solids" Oxford University Press, 1987 for details) As we move from single atom multiple atoms solid electronic properties change from atomic orbitals molecular orbitals band
1 atom 2 atoms * 10 atoms N atoms E

N(E)

Density of states (DOS), N(E), is number of energy levels between E and E + dE (stateseV-1) - States may have s, p, d, f or mixed (hybrid) character depending on origin Band is effectively (i) continuous and (ii) delocalized over solid - Bands may be separated by band-gaps of energy Eg

CEM 924

8.1

Spring 2001

- Width of band determined by magnitude of overlap between individual orbitals - Depending upon number of electrons and DOS, band may be filled, partially filled or empty - Top (partially-)filled band called valence band - Bottom empty band called conduction band
Empty Band Band-gap E g

Fermi level E F

Filled Band Insulator Semiconductor Metal

Energy level dividing filled-empty bands called Fermi level, EF 4.9.2 Surface Electronic Structure
free electron _

0 Workfunction

Vacuum Level E V

+ hole

Fermi Level E F

Energy level of (just) free electron called Vacuum level, EV Energy require to move electron from EF to EV at the surface called workfunction,
CEM 924 8.2 Spring 2001

Envisaged as attraction between departing electron and positive image state (hole) < 2eV (alkali metals) to > 5 eV (transition metal)

Workfunction varies between (i) materials (ii) crystal faces

Workfunction also sensitive to - adsorbates - external electric fields - reconstruction Workfunction presents a barrier to electron emission - near surface, electron behaves like a particle in a box 4.9.3 The Tunneling Effect

Solution of the Schrdinger equation inside and outside a solid with noninfinite walls H = E h d2 2m 2 = E dx h d 2 + V = E 2m dx2
CEM 924 8.3

inside solid outside solid (V = )

This has solutions in = Ae ikx + A'e ikx out = Be ik x + B' eik x

The wavefunction outside the solid consists of two parts: the Be-ikx part which is imaginary when E < V and the B'eikx part which is an exponentially decaying wave
E
V

Electron in solid EF

Exponential decay

x Barrier

- Electron density decays exponentially away from surface - Inverse decay length K (reciprocal of distance for density to fall to 1/e) K= 2 2 me h for K in -1 and in eV

= 0.51

- K 1-2 -1 for a typical metal

CEM 924

8.4

Spring 2001

Tunneling occurs if two metals are brought in close proximity (1 = 2)

Vacuum

Metal

1 EF d

BUT current flow equal in both directions? Apply potential V(ext) to one metal to drive electrons one way (metal 1 negative)
Metal 1 E Vacuum
V

Metal 2

1 EF V(ext)

long K short K

With metal 1 negative with respect to metal 2 (as above) - tunneling from filled states within V(ext) of EF in metal 1 empty states at EF in metal 2 With metal 1 positive with respect to metal 2 - tunneling from filled states within V(ext) of EF in metal 2 empty states at EF in metal 1

CEM 924

8.5

Spring 2001

Tunneling is sensitive to electronic structure - convolution of filled DOS of metal A (-) and empty DOS of metal B (+)

In addition to DOS, Itunnel depends of (i) height of barrier () and (ii) thickness of barrier (d): I tunnel = A exp 2 K d

For a typical metal (K = 1 ), current falls about an order of magnitude for an increase of 1.0 in d Consequences? (1) (2) very sensitive dependence of tunnel current on d - good "vertical" resolution if one metal is sharp tip, most of Itunnel will travel through pinnacle atom - good "lateral" resolution

Atomically sharp tip 99 % of current 90 % of current d

CEM 924

8.6

Spring 2001

4.9.4

Instrumentation for Scanning Tunneling Microscopy (STM)

z y x tip V I bias xyz control Electronics & computer

sample

Monoatomically sharp tip (W, Pt/Ir) mounted on 3-D positioner in air, liquid or vacuum - tip diameter has pronounced effect on image - sharp tips produced by mechanical cutting, ion beam milling or electrochemical etching Electronics control V (0-3 V) and measure I (1 pA-10 nA) - "resistance" of gap 107-1010 - sample-tip separation typically 2-5
Step-size Start

Computer controls movement of tip (x, y, z) in raster fashion on surface

1 pixel

y (slow)

CEM 924

8.7

Spring 2001

Computer converts each Itunnel measurement to pixel (color Itunnel) plotted versus x, y position to generate image

100 x 100 unfiltered Au(111) STM image 3-D scanner based on piezoelectric materials:
Natural + _ -y -x

_ +x +y

+ 4 sector tube scanner

Piezoelectric material has permanent dipole moment across unit cell PbZrTiO3 (PZT) If dipoles are oriented, material changes length in applied electric field - 10-4 to 10-7 % length change per V allows < 1 positioning
CEM 924 8.8 Spring 2001

4.9.5

STM Operating Modes

Two ways to operate: (1) Constant Height Mode

Tip-sample distance fixed - variation in Itunnel forms image Fast but only works for flat samples (2) Constant Current Mode
z

Keep Itunnel constant by moving tip up and down (feedback circuitry) - z movement becomes image Slower but works for rough surfaces Most common

CEM 924

8.9

Spring 2001

4.9.6

Applications of STM - Clean Surfaces Pt(111) surface (1 x 1 m) after heating in O2 (1 atm) at 600 C for 10 minutes Dissociation of O2 on the hot Pt surface probably causes the etching seen here Note the atomically flat terraces and monoatomic height steps See work of Gabor Somorjai (Berkeley) Atomic resolution (20 x 30 ) Au(111) surface Remember that STM probes the local density of states (LDOS) of the surface (and tip). In this case, the sample is biased negative 0.3 V and so we are (mostly) imaging the filled Au 4f states near the Fermi level.

CEM 924

8.10

Spring 2001

The so-called Pt(100) "hex" reconstruction Pt is a FCC metal so the (100) surface should show 4-fold symmetry. The reconstruction ranges over many but is largely based on the movement of different rows of atoms See Surf. Sci. 400 (1998) 290

Si(111) surface (200 x 200 ) showing the (7x7) reconstruction This structure puzzled scientists for many years before STM See early work of Robert Hamers (Wisconsin)

CEM 924

8.11

Spring 2001

4.9.7

Applications of STM - Adsorbate Covered Surfaces CH3(CH2)20CHOH on graphite - molecule "lays down" in all-trans configuration and headto-tail alignment Each H atom (only one per C atom, other points towards surface) appears as site of high Itunnel Dark trough is though to be position of -OH group See work of George Flynn (Columbia)

Mixed monolayer of Cophthalocyanine and Cuphthalocyanine Co(II) is d7 with halffilled dz2 band (band at EF) - appears bright in center of molecule Cu(II) is d9 with filled dz2 band - appears dark in center of molecule See work of Kerry Hipps (Washington State)

CEM 924

8.12

Spring 2001

C2H2 (acetylene) imaging and rotation on Cu(100) surface at different temperatures Rotation is activated at about 68 K See recent work of Wilson Ho (Cornell)

CEM 924

8.13

Spring 2001

4.9.8

Applications of STM - Manipulation and Chemistry

Several researchers have successfully moved atoms and molecules on surfaces using one of several methods - field effect - under influence of high electric field, polarizable molecule or atom can be made to jump from surface to tip or vice versa - dragging - vdW forces between close tip and adsorbate can be used to drag species Xe on Ni(110) at 4 K The first atom-by-atom manipulation See Nature 344 (1990) 524-526

Fe on Cu(111) Construction of a "quantum corral" and the visualization of electron standing waves near EF inside the corral See work by Don Eigler (IBM, Almaden)

CEM 924

8.14

Spring 2001

Recently, several groups have used electrons from tip to break intramolecular bonds Dissociation of two O2 molecules on Pt(111) at 50 K by increasing tunnel current Note that each molecule can be dissociated individually by positioning the STM tip above the molecule of interest See W. Ho et al Phys. Rev. Lett. 78, (1997) 4410-4413

4.9.9

Scanning Tunneling Spectroscopy (STS)

Many surface sensitive techniques give information about average atom of molecule Chemistry may be very position sensitive In principle, STM can map out electronic structure of surface with atomic precision - when tip is biased negative - get information about empty electronic states on surface - when tip is biased positive - get information about filled electronic states on surface
CEM 924 8.15 Spring 2001

- by changing bias can resolve "location" of individual electronic states

- between -0.15 and -0.6 V current due to dangling bond states in faulted half of unit cell - between -0.6 and -1.0 V current due to dangling bonds in second layer of atoms - between -1.6 and 2.0 V current due to Si-Si bonds

CEM 924

8.16

Spring 2001

Plot of Itunnel versus V (bias) provides information about local electronic (and even vibrational) structure - often plotted as I/V, dI/dV or d2I/dV2 curves

CEM 924

8.17

Spring 2001

4.10 Summary
"Real space" images Excellent lateral (<1 ) and vertical (<0.1 ) resolution Obtain information about surface unit cell size and symmetry or electronic structure - can directly image molecular orbitals Some spectroscopic information (STS) may allow identification Fast enough to allow some dynamic information Can both initiate and probe electron-induced chemistry BUT Complex and expensive instrumentation - especially UHV version Subject to noise (electrical, vibration) Image is convolution between tip and surface electronic structure - not truly a topographic measurement Must fabricate tips - dull tips or multiple tips create serious artifacts Only works for conductive samples - metals, semiconductors - though can tunnel through thin insulators (<20-30 )

CEM 924

8.18

Spring 2001

4.11 Scanning Probe Microscopies: Atomic Force and Related Microscopy (AFM)
Developed by Binnig, Quate and Gerber in 1986 from scanning tunneling microscope (STM) Relies on measuring forces between a sharp tip (< 100 diamater) and surface at very short distances (2-100 tip-surface separation) - tip supported on flexible cantilever 4.11.1 Surface Forces
Intermitant contact mode

Contact mode

Non-contact mode

(1) (2) (3)

Non-contact AFM vdW attraction 10-100 tip-surface separation Contact AFM e--e- repulsion <5 tip-surface separation Intermittent contact AFM (tapping mode AFM) 5-20 tip-surface separation

(1)

In contact mode: F(x) = k x Hooke's Law

Spring constant of cantilever is less than surface, cantilever bends

Cantilever F=-kx x

Pyramidal tip

Typical atom-atom k ~ 10 Nm-1, typical cantilever k 0.1-1 Nm-1 Total force on sample 10-6 to 10-8 N If spring constant of cantilever is greater than surface, surface deformed - nano-machining?

Deflection of tip measured by "beam bounce" method:

Position sensitive detector (PSD)

Piezoelectric positioners

or use of piezoelectric cantilever (resistance change with deformation)

CEM 924

8.20

Spring 2001

Can operate in two modes: (A) Constant force - z piezo moves sample to keep constant tip deflection accurate topography, but slow (limited by time constant of cantilever) (B) Constant height - keep z piezo fixed and measured deflection directly fast, but flat samples only

(2)

In non-contact mode:

Very small force on surface (~ 10-12 N) - tip-surface distance 10-100 - best for soft or elastic surfaces - least contamination - least destructive - long tip life Such small forces are difficult to measure using direct beam-bounce method use AC driven oscillating cantilever (100-1000 Hz frequency, 10-100 amplitude) - resonant frequency = 1 k 2 m

- k varies with external force gradient (dF(x)/dx) so frequency changes with external force - electronics adjust tip-surface distance to keep resonant frequency constant - constant tip force
CEM 924 8.21 Spring 2001

Contact and non-contact show similar topography except for soft/deformable materials

(3)

In intermittent contact (tapping) mode:

Similar to non-contact AFM using vibrating cantilever except at one extent tip "taps" into contact mode Useful for soft surfaces - less prone to external vibration/noise than noncontact - but will not image water layers (pierce) Less destructive than contact AFM and can image rougher samples

4.12 AFM and Other Scanning Probe Microscopies

Coat AFM tip with magnetic material - probe magnetic structure of surface Must collect data at different tip-surface separations - in non-contact mode (< 100 ) topography - in far non-contact mode (>100 ) magnetic field

(left) Contact AFM image of magnetic hard drive surface (right) same area but in MFM mode. Approximately 25 x 25 m
CEM 924 8.22 Spring 2001

4.12.2

Lateral Force Microscopy (LFM)

Measure both vertical and lateral (twisting) deflection of tip in contact mode AFM
A PSD B

Vertical deflection

Lateral deflection A B C D Vertical deflection

- gives information about friction (tribology) - but must acquire simultaneous AFM and LFM images to deconvolute twisting due to surface roughness
Direction of tip travel Material A Material B LFM Image

Direction of tip travel Material A LFM Image

CEM 924

8.23

Spring 2001

4.12.3

Instrumentation for AFM and Related Techniques

Cantilevers and tips are typically of Si3N4 or BN (hard) 100-200 m long, 0.1-2 m thick and 10-40 m wide k = 0.1-10 Nm-1, resonant = 1-100 kHz Fabricated by thin film growth on Si wafer
Silicon nitride

Si etch pit (pyramidal)

~20 m

Finished cantilever ~200 m

Shape of etch pit determines shape of tip - can be ~ 50 in diameter Shape of tip (aspect ratio) affects resolution - closest that two objects can be separated (50 % baseline)
High aspect (conical) tip Low aspect (pyramidal) tip

Tip path Surface

Sharper tip can be made by ion beam milling at grazing incidence or electron beam deposition and lateral resolution of AFM now approaching STM
CEM 924 8.24 Spring 2001

Scanning electron micrographs of a pyramidal and conical AFM tip.

An example of a double-tip artifact image 4.12.4 Applications of AFM Ambient tapping mode AFM of DNA strand on mica (1 x 1 m) Each DNA strand is 20 high and would be easily compressed using contact AFM See Digital Instruments (www.di.com)

CEM 924

8.25

Spring 2001

50 x 50 m tapping mode AFM of dried protozoan, Tetrahymena, showing cilia-covered body and mouth structures. The sample was dried onto a glass slide. See C. Mosher and E. Henderson, Iowa State University

Atomic resolution on NaCl(100) surface using a variant of contact mode UHV AFM - bright (high) spots correspond to Clions? Arrows mark positions of surface defects See work of H.-J. Gntherodt (University of Basel, CH)

CEM 924

8.26

Spring 2001

A 14 x 14 m non-contact AFM image of a screw dislocation in a single crystal of a long chain alkane (C36H74) See University of Bristol (UK) SPM group.

CEM 924

8.27

Spring 2001

4.13 Summary
Not limited to conducting samples - especially powerful for biological, organic and polymer samples Simpler instrumentation than STM Commercial tips and cantilevers Provides true topographic imaging Related AFM techniques can measure other physical properties hydrophobicity, magnetism, electrostatic charge, friction, elastic modulus Non-contact or tapping mode causes minimum damage to soft/fragile samples Recent results demonstrate atomic resolution using special tips (<2 lateral) BUT Noise, vibration sensitive Presence of water (capillary action) may distort image Contact mode can damage surface "Chemically blind" As with STM, tip shape convolutes into image Typical lateral resolution ~50

CEM 924

8.28

Spring 2001