İmaging Tools

Atomic Force Microscope: Used for imaging, manipulating, and measuring matter at nanoscale. Uses a mechanical probe
to ‘sense’ the surface. Inventors, Greg Binnig and Heinrich Rohrer won the Nobel Prize for Physics in 1986. In contact mode
the tip contacts the surface through the adsorbed fluid layer on the sample surface. In tapping mode, the cantilever
oscillates at or slightly below its resonant frequency. The amplitude of oscillation typically ranges from 20 nm to 100 nm.
The tip lightly “taps” on the sample surface during scanning, contacting the surface at the bottom of its swing. Because
the forces on the tip change as the tip-surface separation changes, the resonant frequency of the cantilever is dependent
on this separation. In non-contact mode the cantilever oscillates near the surface of the sample but does not contact it.
The oscillation is at slightly above the resonant frequency. Van der Waals and other long-range forces decrease the
resonant frequency just above the surface. This decrease in resonant frequency causes the amplitude of oscillation to
decrease.

Scanning Tunneling Microscope: Used for imaging surfaces at the atomic level. Based on ‘quantum tunneling’. (Involves
a conducting tip through which electrons tunnel through) A device that obtains images of the atoms on the surfaces of
materials. The STM is not an optical microscope; instead, it works by detecting electrical forces with a probe that tapers
down to a point only a single atom across.
Transmission Electron Microscope: Uses electron beam to obtain information on the crystal structure of the material.
Uses electrostatic and electromagnetic lenses to focus the electron beam. Image is obtained from the scattering of
electrons from the material. TEM allows you to observe details as small as individual atoms, giving unprecedented levels
of structural information at the highest possible resolution. As it goes through objects it can also give you information
about internal structures, which SEM cannot provide. Morphology, size distribution, crystal structure, strain, defects,
chemical information down to atomic level and so on.
Scanning electron microscope (SEM): projects and scans a focused stream of electrons over a surface to create an image.
The electrons in the beam interact with the sample, thereby producing various signals that can be used to obtain
information about the surface's topography and composition.
Paul Alivisatos: One of the pioneers in quantum dots, where he made significant contributions on the synthesis techniques
and applications of QDs. Quantum dot (QD): Semiconductor nanocrystals that exhibit quantum mechanical properties.
Electronic properties are between bulk semiconductors and discrete molecules. QDs have applications in LEDs, diode
lasers, solar cells, transistors, etc. Using QDs for solar cells increases the solar power efficiency.
George Whitesides: Micro contact printing , Micro molding, Self-assembly, 3D microfabrication, Fabrication on non-planar
surfaces, Parallel micro fabrication with micro lens arrays
Calvin Quate: He is one of the inventers of AFM. Focuses on imaging and lithography applications of scanning
probes. Limitation of scanning probe imaging and lithography is throughput.
Stephen Chou: Nanoimprint lithography, 10 nm diameter holes, 40nm
Top-down approach: Nanomaterials are derived from a bulk substrate and obtained by the progressive removal of
material until the desired nanomaterial is obtained. Photolithography, Scanning lithography, E beam lithography.
Photolithography: Uses light (UV, deep UV, extreme UV or X ray) Resolution of contact mode photolithography is ~ 0.5
0.8 µm if UV light (360 460 nm) is used. For higher resolutions, extreme UV and X ray photolithography need to be used.
These are very expensive tools, mostly only used for mask production.
Scanning Lithography: Electrons and ions can be used to pattern appropriate resist films leading to features with nm
resolution. Using electrons→ E beam lithography, using ions→ Focused ion beam lithography, using scanning probes→
Scanning probe lithography
E-Beam Lithography: A tightly focused beam of electrons scans across the surface on an electron sensitive resist film, such
as PMMA. Patterns as small as 10nm can be generated. Serial process, therefore slow. Also requires a developing step.
Soft Lithography(Nanoimprint Lith.), Nanosphere Lithography
Scanning Probe Lithography: Uses small (<50nm) tips to generate nanostructures with atomic resolution. Uses a tip of an
AFM to selectively remove certain areas on a surface. IBM researchers were able to use STM tip to move atoms on a
surface to write their company logo in 1989. They used 35 Xe atoms.
Dip pen nanolithography: A type of scanning probe lithography though it is an additive technique. Uses the AFM tip to
deposit material on a surface with nanometer resolution.
Bottom-up approach: Nanomaterials are assembled on the substrate.
Molecular Beam Epitaxy: An evaporation method where one atomic layer at a time is deposited. Widely used in the
fabrication of semiconductor devices. Uses ultra-high vacuum (10 -8 Pa) with a deposition rate of 3000nm/hr. Absence of
carrier gases result in a high purity of grown films.
Process Monitoring, Testing, and Imaging
Interferometry: Measures thickness of thin films. Uses interference
phenomena for measurement→ Light is reflected at the interface
between materials (thin films) If refractive index of the film is known,
then film thickness can be inferred from frequency response. Frequency
sweep determines k.
Ellipsometry: Uses polarized light to measure thickness of thin films.
Linearly polarized light is made to reflect or transmit off a surface, and
the polarization of the resulting elliptically polarized light is then
examined. Layer thickness, morphology and chemical composition can be learned by this technique.
Profilometer: Sharp needle traces the surface of substrate. Has nm scale resolution. Normal force is held constant by z
axis positioning feedback loop. Output is not exactly the image of substrate profile→ it’s the convolution of profile with
needle tip. Measures surface profiles: Roughness, Waviness, Step height, Angle, Other surface characteristics. New
technology uses laser therefore there is no contact with the object Also this can measure high aspect ratio.
4 Point Probe: 4 collaterally placed, spring loaded Tungsten tips. Current is passed through
outer tips. Voltage is measured between inner tips Used to determine sample resistivity.
Probe Station: Binocular microscope with platform for micromanipulators. Micromanipulators
with sharp tips for electrical and mechanical probing of substrate.
Optical Microscopes: Advantages: Versatile, Convenient, Ease of use, relatively inexpensive
Disadvantages: Small focal depth, 2D view, Resolution limited by optical wavelength.
Electron Microscopes: Uses a beam of highly energetic electrons to inspect objects at a very small scale for getting
information on: Surface features of an object. Shape and size of the particles making up the object. Elements and
compounds that the object is composed. How atoms are arranged in the object. Basic steps involved in Electron
Microscopes (EMs): A stream of electrons is formed and accelerated toward the specimen using a positive electrical
potential. This stream is focused to a small, thin, coherent beam by using magnetic lens. This beam is focused onto the
sample using a magnetic lens. Interaction occur inside the irradiated sample, affecting the electron beam. Beam of highly
energetic is used to image objects at a very small scale. Overcomes fundamental limitation of resolution of light
ℎ
microscopes. Resolutions of 1nm are possible 𝜆 = 𝑚𝑣. Shows us that diffraction of electrons is like waves diffracting against
ℎ 1
crystals. (x rays). m=9.11*10-31kg. e=1.6*10-19 C. For V=10Kv v=5.93*107 m/s. 𝜆 = 𝑚𝑣 = 0.0123nm ////2 𝑚𝑣 2 = 𝑒𝑉

Transmission Electron Microscope: Virtual source produces a stream of monochromatic electrons (narrow band of
wavelength). Condenser lens form the stream into small, thin, coherent beam. Apertures eliminate high angle electrons.
Beam strikes specimen and parts of it are transmitted. Objective lens focus transmitted portion into an image. Projector
lens enlarge and display image on main screen.
Scanning Electron Microscope: Virtual source produces a stream of monochromatic electrons 1st condenser lens forms
beam and limits the amount of current. Apertures eliminate high angle electrons. 2nd condenser lens forms the beam into
smaller, thinner, more coherent beam. Scan coils scan the beam in a grid fashion. Objective lens focus beam onto the
specimen. Interactions occur in the sample. Interactions are displayed as pixels.
Specimen Interaction: Backscattered electrons: elastic collisions, image depends on the atomic number of specimens.
Secondary electrons: Receives high energy from high energy electron passing nearby and leaves sample with very small
energy. Materials emit characteristic X-rays when returning from excited state.
Focused Ion Beam: Like SEM but uses LMIS (Liquid Metal Ion Beam formed from the source is focused by ion optics, all
electromagnetic lenses. Can be used as a “drilling tool” to reveal cross section. Can also be a metal deposition tool. The
signal from sputtered ions is used to form an image.
Nano printing /Nanoparticle patterning
Current materials used widely in industry are silicon, gallium arsenide and zinc oxide. To make new devices and
applications, we need to increase the variety of materials we can use. In addition to materials, we would like to improve
portability, functionality, efficiency, and cost of existing devices by choosing new materials. Nanoparticles can be used in
sensing and electronics as new materials. They display remarkable difference in optics, electronics and physical properties
compared to bulk materials. Also, they have high surface to volume ratio making them suitable for applications in sensing,
catalysis, separations etc. To use nanoparticles for specific applications, it is important to be able to pattern them. There
are several methods to pattern nanoparticles. Metrics for patterning determine the requirements of these processes.
Versatility: Given process should be material independent, i.e. variety of materials can be patterned by using the same
process. High quality in pattern transfer: Structure of transferred pattern should be at high resolution, accurate,
controllable in aspect ratio. Alignment of subsequent layers
of features: Patterning more than one material might be
necessary; therefore, alignment accuracy is important. High
throughput: Ability to pattern over large areas with same
quality.
Traditional Methods: Uses photolithography to pattern
structures. Direct Photolithography: Patterning
nanoparticles by direct photolithography is challenging. This
is done by incorporating a polymer binder with
photoactivated crosslinker. Limits the versatility of the process. Removing the polymer binder might be difficult. Lift off:
Nanoparticles can be patterned by depositing them uniformly on the substrate using spin coating, evaporation of a
nanoparticle ink or other methods. It is difficult to remove photoresist without harming the nanoparticles, therefore this
process is also limited in materials. Thin Film Deposition and Etching: A photoresist etch mask is used for patterning.
Process should not affect the chemical properties of nanoparticles; therefore, it is not a versatile process.
Non-Traditional Methods: Inkjet Patterning: Ink droplets are ejected from a nozzle and directed at a substrate to form
patterns. Piezoelectric actuation or thermal actuation is used to eject ink. Several types of sensors, light emitting diodes,
transistors, etc. were made by using this method. Has several disadvantages despite its widespread usage. Lots of effort
is needed to engineer the ink for proper viscosity, stability and surface tension. Highly dependent on the material. Limited
throughput due to having a single nozzle to eject ink. Can only print thin films. Resolution limited with droplet size ~ 20µm.
Gravure Printing: Continuous, high throughput process capable of patterning
over large areas. Have been used in patterning organic thin film transistors,
electrical interconnects, antennas. Quality of patterning depends on the
precision of the gravure roller, property of the ink, interaction of ink and
surface. Reflow of the ink determines the ultimate size and morphology of the
features. Not possible to print 3D structures due to reflow.
Screen Printing: A mesh is used to support a stencil, that blocks ink selectively.
Ink is applied and a squeegee is used to apply mechanical force to press the
mesh on the substrate. Brief contact between mesh and substrate transfers the ink to the substrate. Not possible to obtain
3D structures and resolution is limited to 100µm.
Nanoimprint Lithography (NIL): Can produce
straight edges, high aspect ratio structures,
high resolution (50nm), has high throughput.
Residual layer becomes problematic.
Micromolding in Capillaries (MIMIC): Can
produce lines with width 300nm. Patterned
lines have straight sidewalls and uniform
heights. Aspect ratio ~1:1
Miscellaneous Methods
Fabrication of objects with complex inner structure is challenging with molding or 3D printing methods. Controlled shape
transformation can be used for this purpose, which is like Origami. In micro scale, special materials, which are capable of
controlled shape transformation can be used for achieving “folding”. Some shape changing materials: Hydrogels, Shape
memory polymers, Dielectric elastomers, Liquid crystal elastomers. A droplet of a nanoparticle solution is placed on the
surface of a thin and flexible PDMS surface, and the surface folds around the droplet under the effect of capillary forces.
Origami for Self Folded Grippers
Grippers were fabricated with flexible, prestressed bilayer hinges, connected to rigid segments. The prestressed bilayer
was constructed from e beam evaporated thin films of SiO and SiO2. The rigid segments were formed from thicker films
of e beam evaporated SiO. The concept relies on a spatial variation of thickness in the initial 2D structures to produce
engineered folding creases during the compressive buckling process, with capabilities in origami. Shape Memory
Polymers: Heating of sample with laser light allows site specific shape transformation. Photothermal or magnetothermal
effect of nano particles or dyes can play an important role in the production of heat in the presence of light or magnetic
field. Using photothermal wavelengths, which produces heat after absorbing light selectively by some special dyes
Sequential folding can be achieved by printing different color ink over the polystyrene sheet. Patterning metal
nano/microstructures on flexible substrates are not compatible with conventional techniques. A transfer layer can be
adapted.
Self Assembly: •‘Fabrication tool’ of nature. In natural biological processes, molecules self-assemble to create complex
structures with nanoscale precision. E.g. formation of the DNA double helix. In self-assembly, subunits spontaneously
organize and aggregate into stable, well defined structures through non covalent interaction. Intramolecular Forces:
Forces between atoms to form molecules. (e.g. ionic bond, covalent bond) Intermolecular Forces: Forces between
molecules. (e.g. Hyrdogen bonds, dipole dipole interactions, ion dipole forces, van der Waals forces, Debye force, etc.)
Self Assembled Monolayers: Easiest way to modify a surface. Molecules attach to the surface from the head side as this
reduces the surface energy. Until the surface is completely covered with molecules, the assembly continues. Common
head groups: thiols, silanes , phoshonates. Functional groups modify the surface wetting characteristics. E.g. OH, NH2,
COOH, SH groupsLipid Self Assembly: Lipid molecules have head that like water and tail that repel water. That’s how cell
membrane is made of. DNA Self Assembly: Sticky end of DNA strands are brought together to form 2D assemblies. A
sticky end is a short single-stranded overhang protruding from the end of a double-stranded helical DNA molecule. A
simple method for folding long, singlestranded DNA molecules into arbitrary two dimensional shapes. Numerous short
single strands of DNA direct the folding of a long, single strand of DNA into desired shapes.
Self Assembled Nanoparticles: Nanoparticles and rods can be assembled in solutions due to attractive forces in between
them such as hydrogen bonds, dipole dipole interaction. Nanoparticles can be patterned on a surface with self assembly.
For assembling nanoparticles, templates such as carbon nanotubes, viruses, DNA molecules.
Self-Assembly at Interfaces: Assembly of particles can be done at a liquid-liquid or liquid-solid interface if the total free
energy of the system is reduced. This type of assembly can be used to form capsules for drug delivery, or making of
membranes for filtering purposes. Assisted Self Assembly: Particles can also be assembled with electrostatic or magnetic
forces.
Applications of Self Assembled Nanoparticles: Major goal is to use highly sensitive property of nanoparticles such that
we can obtain more sensitive and compact devices, sensors, components, etc. E.g. A wavelength based protein detection.
Self Assembly in Microscale: Microcomponents can be assembled on a surface by manipulating wetting characteristics.
The substrate is prepared with hydrophobic alkanethiol coated gold binding sites.To perform assembly, a hydrocarbon oil,
which is applied to the substrate, wets exclusively the hydrophobic binding sites in water. 3D nanostructures of wires and
junctions formed by self assembly.