Micro to Nano Technologies

Do. Dr. Eylem Gven

Micro to Nano Technologies

Micro

- Prefix meaning one millionth, 1/1,000,000 Prefix meaning one billionth, 1/1,000,000,000

Nano

The Powers of 10

10+0 10-1 10-2 10-3 10-4 10-5 10-6 10-7 10-8 10-9 10-10 10-11 10-12 10-13 10-14 10-15 10-16 10-17 10-18

1 Meter 10 Centimeters 1 Centimeters 1 Millimeter 100 Microns 10 Microns 1 Micron 1,000 Angstroms 100 Angstroms 1 Nanometer 1 Angstrom 10 Pico meters 1 Pico meter 100 Fermis 10 Fermis 1 Fermi 0.1 Fermis 0.01 Fermis 0.001 Fermis

Perspective of Length Scale

Top Down
1 km Aircraft Carrier Boeing 747 Car Humans Laptop Butterfly 1 mm Gnat Size of a Microprocessor

1m

Resolving power of the eye ~ 0.2 mm Micromachines

1 m

Bottom Up 1 nm

Biological cell Nucleus of a cell Wavelength of Visible Light Smallest feature in microelectronic chips Nanostructures & Quantum Devices Proteins (5-50 nm) Width of DNA (2 nm) Size of an atom (0.1 nm)

Perspective of Size
Water molecules 3 atoms Protein molecules thousands of atoms water molecule DNA molecules millions of atoms Nanowires, carbon nanotubes millions of atoms

Carbon nanotube Molecule of DNA

www.iacr.bbsrc.ac.uk/notebook/ courses/guide/dnast.htm www.phys.psu.edu/~crespi/research/_carbon.1d/public student.biology.arizona.edu/.../ group2/crystallography.htm

Protein molecule

How Small is a nm?

1 m = one millionth of a meter 1 nm = one billionth of a meter 1/50,000 thickness of a hair! a string of 3 atoms If we shrunk all distances by 110,000,000,000 X The sun and earth would be separated by 1 m A football field would be 1 nm
110,000,000 km

Human hair thickness ~ 50 m 110 m

More than just size

Interesting phenomena: Chemical take advantage of large surface to volume ratio, interfacial and surface chemistry important, systems too small for statistical analysis Electronic quantum confinement, bandgap engineering, change in density of states, electron tunneling Magnetic giant magnetoresistance by nanoscale multilayers, change in magnetic susceptibility
http://pubweb.acns.nwu.edu/~mhe663/

STM of dangling bonds on a Si:H surface

b

Electron tunneling

More than just size

Interesting phenomena:
Mechanical improved strength hardness in light-weight nanocomposites and nanomaterials, altered bending, compression properties, nanomechanics of molecular Fluorescence of quantum dots structures of various sizes Optical absorption and fluorescence of nanocrystals, single photon phenomena, photonic bandgap engineering Fluidic enhanced flow properties with nanoparticles, nanoscale adsorbed films important Thermal increased thermoelectric Phonon tunneling performance of nanoscale materials, interfacial thermal resistance important.

Micro- and NanoManufacturing from Technology/Materials to Application

Electronics & Dispays Aerospace Automotive Textiles & Clothes

Pharmaceutical

Micro- and NanoManufacturing

Energy/ industry

Source: Sss MicroTec, Jenoptik, Kugler Przisionsschleifen, Trumpf Lasertechnik

Materials

Process-Technology

Microfabrication
Microfabrication is a top-down technique utilizing the following processes in sequential fashion (micrometer to milimeter range):

Film Deposition

CVD, PVD Optical exposure, PR Aqueous, plasma

Photolithography

Etching

Many of these techniques are useful, directly or indirectly in nanofabrication

Nanofabrication
Nanofabrication can generally be divided into two categories based on the approach (1-100 nm): Top-Down: Fabrication of device structures via monolithic processing on the nanoscale. Fabrication of device structures via systematic assembly of atoms, molecules or other basic units of matter.

Bottom-Up:

Current Micro Technologies

Photonics

- Optical Apertures and Flow Orifices Electronics Semiconductor chips, anodic bonding MEMS Micro Electro Mechanical Systems Communication Fiber optics, switching
interconnects
Biotechnology

- cell filtration, drug discovery

Current Nano Technologies

Molecular

the atomic level

manufacturing Precision down to Building advanced lightweight materials

Nanotubes Medicine

as well as advancements in LCD technologies circulatory system

Devices that will flow through the Assisting in vast improvements

Nanocomposites Electronics

in material compositions

integration with lithography

Advanced CMOS and silicon transistor

Micro scaling to Nano

mms://stream.techtv.com/windows/bigthinkers/20 02/bt020225b_165_0.asf

Micro/Nano Fabrication Techniques

Generalized Microfabrication

Taken from : http://mems.colorado.edu/c1.res.ppt/ppt/g.tutorial/ppt.htm

Photolithography
Clean wafer : to remove particles on the surface as well as any traces of organic, ionic, and metallic impurities Dehydration bake: to drive off the absorbed water on the surface to promote the adhesion of PR (photoresist) Coating : a) Coat wafer with adhesion promoting film (e.g., HMDS) (optional) b) Coat with photoresist Soft bake : to drive off excess solvent and to promote adhesion Exposure Post exposure bake (optional): to suppress standing wave-effect Develop Clean, Dry Hard bake: to harden the PR and improve adhesion to the substrate

Photolithography

Taken from : http://www2.ece.jhu.edu/faculty/andreou/495/2003/LectureNotes/Handout3a_PhotolithographyI.pdf

Additive Processes
Oxidation
Thermal Oxidation of Silicon is done in a furnace in wet or dry conditions

Additive Processes

Doping

The introduction of certain impurities in a semiconductor can change its electrical, chemical and even mechanical properties (microelectric industryfabrication of diodes and transistors). Purpose of Doping in MEMS - Creation of etch stop layers - Change restivity of the film (e.g. make piezoresistor, connecting wire) Dopants : to form N type region (Phosphorous, Arsenic), P type region (Boron) in silicon Doping Methods 1. Diffusion Dopants are diffused thermally into the substrate in furnace at 950 1280 0C. It is governed by Ficks Laws of Diffusion. 2. Ion Implantation Dopant ions bombarded into targeting substrate by high energy. Ion implantation are able to place any ion at any depth in sample.

Additive Processes
Physical Vapor Deposition (PVD)
The material to be deposited is transported from a source to the wafers, both being in the same chamber..

1. Evaporation
Deposition is achieved by evaporation or sublimation of heated metal onto substrate. This can be done either by resistance heating or by e-beam bombardment.

Thermal Evaporator

Additive Processes
Physical Vapor Deposition (PVD)
2. Sputtering
Sputtering is achieved by accelerated-high energy inert ion (Ar+) by DC or RF drive in plasma through potential gradient to bombard metallic target. Then the individual atoms of targeting material are removed from the surface and ejected toward the wafer. (deposited onto substrate placed on anode).

Additive Processes
Physical Vapor Deposition (PVD)

Additive Processes
Chemical Vapor Deposition (CVD)
All the deposition techniques using the reaction of chemicals in a gas phase to form the deposited thin film Materials deposited Polysilicon, silicon nitride (Si3N4), silicon oxide (SiOx), silicon carbide (SiC) etc. How does CVD Work? Gaseous reactants are introduced into chamber at elevated temperatures. Reactant reacts and deposits onto substrate Types of CVD LPCVD (Low Pressure CVD), PECVD (Plasma Enhanced CVD) Salient Features CVD results depend on pressure, gas, and temperature Can be diffusion or reaction limited Varies from film composition, crystallization, deposition rate and electrical and mechanical properties

Subtractive Processes
Thin film and bulk substrate etching is another fabrication step that is of fundamental importance to microfbrication.

Dry Etching
1. Dry Chemical Etching
HF Etching HF is a powerful etchant and hence, highly dangerous. XeF2 Etching 2XeF2+Si2Xe+SiF4 Isotropic etching (typically 1-3m/min) Does not attack aluminum, silicon dioxide, and silicon nitride

Subtractive Processes
Dry Etching
Plasma Etching

Reaction Mechanism Produce reactive species in gas-phase Adsorption, and diffuse over the surface

Reactive species diffuse to the solid Reaction Desorption Diffusion

Subtractive Processes
Dry Etching
3. Deep Reactive Ion Etching (DRIE)
A very high-aspect-ratio silicon etch method (usually > 30:1) BOSCH Process Etch rate is 1.5 4 m/min SF6 to etch silicon Approx. 10nm flourcarbon polymer (similar is plasma deposited using C4H8 Energetic ions (SF6+) remove protective polymer at the bottom trench

Subtractive Processes

DRIE Etched Pillars

Subtractive Processes
Wet Etching
Isotropic Wet Etching
Isotropic etchants etch in all directions at nearly the same rate. Commonly use chemical for Silicon is HNA (HF/HNO3/Acetic Acid) This results in a finite amount of undercutting

Subtractive Processes
Wet Etching
Anisotropic Wet Etching
Anisotropic etchants etch much faster in one direction than in another. Etchants are generally Alkali Hydroxides (KOH, NaOH, CeOH, ..) KOH on silicon Slower etch rate on (111) planes Higher etch rate on (100) and (110) planes (400 times more faster than the (111) plane) Typical concentration of KOH is around 40 wt% Reaction : Silicon (s) + Water + Hydroxide Ions Silicates + Hydrogen

Surface Micromachining

Example

1. Pumping membrane 3. Inlet 5. Large mesa 7. Bottom glass plate

2. Pumping chamber 4. Outlet 6. Upper glass plate 8. patterned thin layer (for improved fluidics)

An insulin pump fabricated by classic MEMS technology (Surface Micromachining)

What are Nanostructures?

At least one dimension is between 1 - 100 nm 2-D structures (1-D confinement): Thin films Planar quantum wells Superlattices 1-D structures (2-D confinement): Nanowires Quantum wires Nanorods Nanotubes 0-D structures (3-D confinement): Multi-wall carbon Nanoparticles nanotube Quantum dots Dimensionality, confinement depends on structure: Bulk nanocrystalline films Nanocomposites
http://www.aip.org/mgr/png/2003/186.htm

2 m

Si Nanowire Array

Si0.76Ge0.24 / Si0.84Ge0.16 superlattice

Thin Films
Nanoscale Thin Film Single two dimensional film, thickness < ~100 nm Electrons can be confined in one dimension; affects wavefunction, density of states Phonons can confined in one dimension; affects thermal transport Boundaries, interfaces affect transport

a
Bulk crystal Thin film

Substrate Free standing thin film

d
http://scsx01.sc.ehu.es/waporcoj/charla s/cursodoctorado/12

Thin Film Applications

Solid Fuel Cells: (nanostructured) thin film solid electrolytes and electrodes with high conductance Thin Film Transistors for liquid crystal displays: requires high mobility and flexible substrates Gas sensing applications Thin layers in electronic devices
100 nm sputtered YSZ film for solid oxide fuel cells

Wagner et al, Thin Solid Films, Vol. 490, pp. 12 19 (2003). http://www.bu.edu/mfg/pdf/Tuller.pdf

Amorphous Si TFT on a SiNx passivated polyimide foil

Nanowires
Solid, one dimensional Can be conducting, semiconducting, insulating Can be crystalline, low defects Can exhibit quantum confinement effects (electron, phonon) Narrowing wire diameter results in increase in 2 m band gap Narrowing wire diameter can result in Si Nanowire Array decrease in thermal conductivity New forms include core-shell and superlattice nanowires

Nanotube defined a long cylinder with inner and outer nm-sized diameters Nanowire defined a long, solid wire with nm diameter

Abramson et al, JMEMS (2003) Wu et al, Nanoletters, Vol. 2, 83 86 (2002)

Si/SiGe Nanowires

Nanowires Applications
Field effect transistors Thermoelectric materials Light emitting diodes Detectors Sensors Nanolasers Superlattice nanowires applications requiring

superlattices

in

http://www.photonics.com/spectra/tech/XQ/ ASP/techid.1525/QX/read.htm

Nanolaser from 100 nm CdSe nanowire 5 nm Si nanowire FET

Cui et al, Nanoletters, Vol. 3, 149 152 (2003).

Carbon Nanotubes
Carbon nanotube properties: One dimensional sheets of hexagonal network of carbon rolled to form tubes Approximately 1 nm in diameter Can be microns long Essentially free of defects Ends can be capped with half a buckyball Varieties include single-wall and multiwall nanotubes,ropes, bundles, arrays Structure (chirality, diameter) influences properties:

Multi-wall carbon nanotube Armchair Zigzag

Semiconducting vs. metallic Thermal, electrical conductance Mechanical strength, elasticity

http://physicsweb.org/article/world/11/1/9/1 http://www.aip.org/mgr/png/2003/186.htm

Chiral

Other Nanotubes
Boron nitride nanotubes Boron nitride Resistance to oxidation, suited nanotubes adopt various for high temperatures shapes Youngs modulus of 1.22 TPa (red=boron, Semiconducting blue=nitrogen): Predictable electronic properties independent of diameter and # of layers SiC nanotubes: Resistance to oxidation Suitable for harsh environments SiC nanotubes Can functionalize surface Si grown at NASA Glenn: atoms

http://www.grc.nasa.gov/WWW/RT2002/5000/5510lienhard.html http://pubs.acs.org/cen/topstory/7912/7912notw1.html

Nanoparticles/Quantum Dots
Zero-dimensional particle Radius of particle or cluster Surface effects/chemistry important 105 nm Radius < 100 nm < 106 atoms per nanoparticle 104 nm bulk Size smaller than critical length scales (e.g. mean free path, wavelength) 103 nm Nano/quantum physical phenomena present 102 nm Large nanoparticles have same structure as bulk; small may be different nanoparticles 10 nm Synthesis: RF plasma, chemical, thermolysis, pulsed laser 1 nm quantum dots Old examples molecules

Stained glass small metal oxide clusters comparable in size to the wavelength of light Photography small colloidal silver particles

1A

Nanoparticles/Quantum Dots

Metalic nanoparticles

Gradient of gold nanoparticles on a silica surface

http://www.bnl.gov/bnlweb/pubaf/pr/ 2002/bnlpr071802.htm Bapat et al, J Appl Phys, Vol. 94, 1969 1974 (2003) www.aveka.com

Si nanoparticle; singlecrystal; hexagonal shape

Nanoparticle Probes

Objective: To detect and kill individual cancer cells before they manifest as tumors using functionalized nanoparticles 5 to 10 nm particles (small enough to interact with intracellular markers) nanoparticles are coated and functionalized with antibodies, oligonucleotides, peptide ligands and drugs Introduced to body via bloodstream Look for markers inside cell by MRI or deliver agent or irradiate

Nanocomposites
Nanocomposite consists of two or more synthesized materials of which at least one has nanoscale dimensions Can exhibit enhanced chemical, optical, physical, mechanical properties as compared with constituent bulk Multiple material possibilities

Organic + organic Organic + inorganic Inorganic + inorganic

Nanoparticle or nanowire or nanotube + matrix material

Why nano and not micro? Micro also gives increase elastic modulus, but microparticles act as stress concentrators, decrease in strain to failure, decrease in strength and toughness

Nanocomposite Applications
Luminescent nanocomposites for optoelectronics Electronics (e.g. dielectric layers) Intracellular manipulation Thermoelectric materials High-strength, toughness structural materials Electrolytes in batteries Insulation Coatings Gas separation Fire barriers
TiO2-oligonucleotide nanocomposites hybridized with DNA for cellular manipulation
Paunesku et al, Nature Mats, Vol. 2, 343 346 (2003)

Merkel et al, Science, Vol. 296, 519 522 (2002)

Polymer containing 40 wt% silica particles for use as a gas separation membrane

What can we measure?

atomic species concentration composition diffusion segregation strain defects crystallinity surface roughness structure

properties mechanical electrical/optical magnetic Seebeck band coefficient failure yield gap carrier density tensile stiffness dielectri susceptibility electron strength c states magnetohardness modulus of constant elasticity conductivity resistance thermal conductivity specific heat

Atomic Force Microscopy

The optical microscope cannot see features smaller than ~half the wavelength of light Can we use something other than light and lenses? AFM basic components: Tip (<~10 nm diameter) on a cantilever Detector (generally position) Raster-scan (to drag tip) Force/height control Image processing software Lateral resolution 0.1 nm Vertical resolution 0.02 nm
Image of graphite using an AFM

AFM modes
contact mode non-contact mode

Tip angstroms from surface (repelled) Constant force Highest resolution May damage surface

Tip hundreds of angstroms from surface (attracted) Variable force measured Lowest resolution Non-destructive

tapping mode

Intermittent tip contact Variable force measured Improved resolution Non-destructive

Courtesy of F. Ernst

AFM images

Cu Nanowires

Ge islands on Si

K. Brunner et al. R. Adelung et al.

Courtesy of F. Ernst

Scanning Electron Microscopy

Instead of light, the SEM uses electrons to see 3-D images SEM operation: Air pumped out (vacuum) e- gun emits beam of high energy electrons e- beam focused via lenses Scanning coils move beam across sample Secondary electrons are knocked off surface Detector counts electrons Image given by # eResolution ~5 nm
Courtesy of F. Ernst

SEM and AFM images

SEM: Cu Nanowires

AFM: Cu Nanowires

R. Adelung et al.

Courtesy of F. Ernst

Transmission Electron Microscopy

A TEM works like a slide projector but with e- instead of light TEM operation: Air pumped out (vacuum) e- gun emits beam of high energy e e- beam focused via lenses Beam strikes sample and some e- are transmitted Transmitted e- are focused, amplified Image contrast enhanced by blocking out high-angle diffracted e Image passed through lenses and enlarged When image hits phosphor screen, light is generated Resolution ~<1 nm

sample

lens

Courtesy of F. Ernst

TEM of Ge on Si
HRTEM Cross-Sectional View

Courtesy of F. Ernst

TEM comparison

Standard TEM

High resolution TEM

Courtesy of F. Ernst