V.

Characterization: Probing the Structure of Nanomaterials

Experimental observations and measurements of the structure and behavior of nanoscale materials are challenges that are being met successfully with a host of techniques involving Scanning Probe Microscopy, for the most part. [Springer Handbook of Nano-Technology, ed. Bharat Bhushan, 2004]

Methods for the Characterization of Nanoscale Materials

-Overview and motivation
-Introduction and terminology -Application to a system of interest -Microscopy (EM and SPM*) -Data collection, analysis and interpretation -Capabilities and Limitations
*(EM) Electron microscopy (scanning and transmission SEM and TEM) (SPM) Scanning probe microscopy (atomic force and scanning probe) Prepared by C. B. SCSU.

Overview and motivation

Purpose
Why is characterization necessary? Link to materials science and nanotechnology (what are the relevant structure-property relationships for the application?)

Focus
Nano-size materials and structures Examples nano-application: semiconductor industry. Semiconductor industry must specify info. of interest Advanced characterization techniques necessary

Present and future trends for application

Ultra small scale features represent challenges Know the limitations of characterization techniques Combine complementary methods

Correlation between Structure and Properties of Nano-materials

Relevant features of nano-structures:
Morphology form and structural properties
Thickness or surface roughness

Elemental/Chemical composition
Qualitative what is present? Quantitative how much is present?

Crystallographic structure and defects

Identify crystal structure; presence of defects

The challenge:
Methods for observing nanostructures
Optical Microscope SEM SPM

Sample operating environment Depth of field Depth of focus Resolution: x,y Resolution: z Magnification range Sample preparation required Characteristics required of sample

ambient liquid vacuum small medium ~0.2 m N/A 1X - 2 x 103X little

vacuum

large small 2 nm (TEM: 0.1nm) N/A 10X - 106X freeze drying, coating surface must not build up charge and sample must be vacuum compatible

ambient liquid vacuum medium small 0.1 - 3.0 nm 0.01 nm 5 x 102X 108X none
*1 nm = 0.000000001 m; 1 m = 0.000001 m
Resolution Human Eye ~0.1mm

sample must not be completely transparent to light wavelength used

sample must not have excessive variations in surface height

Energy Regimes for Material Characterization

Energy
1 eV 5 eV 10-20 eV 20eV 1keV 1 20 keV 100-300 keV

Example applications
Possessed by evaporated atoms arriving at a substrate Possessed by sputtered atoms arriving at a substrate Required to ionize neutral atoms (Ar ~ 15 eV) Possessed by emitted Auger electrons Possessed by Primary beams in SEM, AES, SIMS Possessed by primary beams of electrons in TEM

Characterization methods: Scanning Probe Microscopy(SPM)

SPM methods include scanning tunneling microscopy (STM) which exploits an electronic tunneling current, atomic force microscopy (AFM) which measures miniscule forces between the probe and sample, and transmission electron microscopy (TEM) whereby a beam of electrons is transmitted through an ultra thin specimen, and scanning electron microscope (SEM) which images electrons scattered from a surface.

Scanning Tunneling Microscope (STM)

STM was developed by Gerd Binning and colleagues in 1981 at the IBM Zurich Research laboratory (Nobel Prize, 1986)
" The STM image of Si(100) surface shown below Metallic tip

Sample

The STM as an Atom Manipulator

a STM image showing iron atoms adsorb on a copper (111) surface forming a "quantum corral

Atomic Force Microscopy (AFM)

The AFM was developed by Binning et al in 1985;

Flexible cantilever beam

Sample

AFM Modes of Operation

There are two distinct regions dominated by: attractive and repulsive interactions.

Contact mode -- repulsive mode Non Contact mode -- attractive more

Veeco Practical Guide to SPM (http://www.veeco.com/library/resources.php)

Transmission Electron Microscopy

Concept of transmission microscope

section of a cell of Bacillus subtilis, taken with a Tecnai T-12 TEM. The scale bar is 200nm.

Scanning Electron Microscopy (SEM)

Pollen grains taken on an SEM show the characteristic depth of field of SEM micrographs.

Electron Microscopy SEM vs. TEM

SEM sample

TEM

Some general Features of Electron Microscopy

Data Interpretation and limitations
Beam interactions image interpretation is complex Resolution limited by beam diameter and there are trade-offs between resolution and signal intensity. Sample preparation Sample must be thin enough for ebeam transparency.
Tip effects must be considered Resolution is limited by sample morphology Data interpretation is complex

Electron Microscopy at Nano-scale

Electron micrograph of typical silicon nanocomposite cross section showing uniform distribution of conductive carbon nanotube network. Photo courtesy of U.S. Air Force.

Data Collection
Atomic Force Microscope Scanning Electron Microscope

Transmission Electron Microscope

Imaging materials at the atomic scale -- Nanotechnology

Data Collection, Analysis and Interpretation

An example of Nanotechnology: Nano-scale imaging of a transistor gate

Conventional TEM (120kV)

HRES TEM (200kV)

metal insulator metal insulator

Semiconductor Semiconductor

50 nm scale

5 nm scale

Additional References
Sarid, Dror., Scanning Force Microscopy; Oxford Press Williams and Carter, Transmission Electron Microscopy, Plenum Press Scanning Electron Microscopy and X-Ray Microanalysis, Kluwer Academic/Plenum publishing

Kevex Corporation, Energy-Dispersive X-Ray Microanalysis

Briggs and Seah, Practical Surface Analysis, Wiley Wolf and Tauber, Silicon Processing for the VLSI Era, Lattice Press Park Scientific Instruments, A Practical Guide to Scanning Probe Microscopy