Lecture24 Lecture 24

Topdownandbottomupfabrication

Lithography (lithos stone / graphein to write)

City f Cit of words lithograph d lith h (Vito Acconci, 1999)

1930s lithography press

Photolithography

2( NA)

NA=numerical aperture

Electron-beam Lithography

Photolithography: Process flow

1. Apply photon sensitive polymer film to wafer via spin coating: -Positive resist: a polymeric resin and radiation sensitive molecules. Exposure causes chemical change to the sensitizer which promotes dissolution of the exposed resist in aqueous developer solution -Negative resist: sensitizer promotes polymer cross-linking in the l l k h resin, making exposed resist region insoluble to the developer 2. Soft bake: resist baked for 1/2hr at 80-90 C to drive off excess solvent in resist and to improve adhesion to the wafer 3. Mask alignment: most semiconductor deices are currently manufactured using deep UV projection photolithography

Lithography: Process flow

4. Development: resist-covered wafer is placed in contact with developer solution. solution Different dissolution rates of exposed and masked resist regions 5. Hard b k Hardens d l d resist l d bake: d developed layer ~12hr at 150 C h 6. Etching or deposition of material in regions of removed resist. Etching g p g g should remove the underlying layer more quickly than the resist 7. 7 Resist strip: combination of oxygen plasma etching and wet chemicals are used to remove the resist from the wafer

Resist materials

PMMA (poly(methyl methacrylate)) Positive resist

SU-8 Negative resist

Etching
1. Wet etching: i.e., removal of SiO2 layers using HF/H2O Wet etching tends to be isotropic Some etchants preferentially etch certain crystallographic a p a y a y a g ap planes faster than others 2. 2 Dry etching: Aniosotropic etching (vertical etch) Bombardment by energetic particles from the gas phase

1 m

1 m

Solution-based synthesis (metal & semiconducting nanoparticles)

While the specifics of each reaction differ greatly, the basic stages of solution chemistry are: 1. Solvate the reactant species and additives 2. Form stable solid nuclei from solution 3. Grow the solid particles by addition of material until the reactant species are consumed Basic Aim: Simultaneous formation of large numbers of stable nuclei. If further growth is to occur, it should happen independent of the nucleation step occur Key Challenge: Ostwald ripening || Need to use stabilizers

1857: Faraday - Reduction of [AuCl4]- with P in carbon disulfide produces a deep red solution

Turkevich Metal Nanoparticle Synthesis

Air-stable, water-soluble Au nanoparticles, diameters between 10 and 20 nm p Single phase synthesis Reduction of gold chloride with sodium tris-citrate in water

Nature, 1973

Why are metal nanoparticles cool?

20 nm

Reflection 2 nm

Transmission

Lycergus Cup (Roman), 4th century AD: Excitation of metal nanoparticles in goblet makes glass appear red

Metal nanoparticles support surface plasmons

20 m

Applications of metal nanoparticles: Cancer therapy

Atwater, The Power of Plasmonics, Scientific American

Applications of metal nanoparticles: sensing

Semiconducting Nanoparticle Synthesis

CdS, CdSe, ZnS, ZnSe, CdTe, ZnO, TiO2, etc. Example: CdSe Dimethylcadmium is dissolved in a mixture of trioctylphosphine (TOP) and trioctylphosphine oxide (TOPO). yp p ( ) Solution is heated and vigorously stirred Selenium source usually Se dissolved in TOP or TOPO is injected quickly and at room temperature widespread nucleation of TOPO-stabilized CdSe quantum dots The room-temperature Se-TOP solution prevents further nucleation or growth Reaction can be heated for further growth g

Semiconducting Nanoparticle Applications

Electric Field Sensors (i e neuron sensing) (i.e.,

J. Muller et al. Nano Letters 5 (2005), K. Becker et al. Nature Materials 5 (2006)

Optical Strain Sensors (i.e., cancer cell sensing)

compressed tetrapod uncompressed tetrapod
1.4, 1.9, 3.1, 3.9, 4.8, 4.6, 2.8, 1.8 GPa

20 nm

C. Choi et al. Nano Letters (in press)

Nanowire Growth: VLS Methods

From Willander, Zhao, & Nur, SPIE 2007

Carbon-based nanomaterials (nanotubes, bucky balls, etc)

Carbon allotropes require extreme synthetic techniques: Laser vaporization (fullerenes & nanotubes) Arc discharge methods (fullerenes & nanotubes) Pyrolysis (fullerenes & nanotubes) Chemical vapor deposition ( h l d (nanotubes) b ) The precursor (graphite) require significant dissociation energies prior to self-assembly (contains strong covalent bonds)